DEVICES AND METHODS FOR AMBIENT PRESSURE CARBON DIOXIDE FREEZE DRYING AND COMPOSITE MATERIALS MADE THEREFROM

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application is a continuation in part of International Application No. PCT/US 2016/05961 1 , filed October 29, 2016, which claims the benefit of U.S. Provisional Application No. 62/248,162, filed on October 29, 2015, and U.S. Provisional Application No. 62/248,194, filed on October 29, 2015. The entire disclosures of each of the above applications are incorporated herein by reference.

FIELD

[0002] The present disclosure relates to a system, device, and method for dehydrating porous materials and, more particularly, to a system, device, and method for freeze drying various materials with porous structures that may be filled with one or more solvents. The one or more solvents can be exchanged or replaced with liquid and/or supercritical carbon dioxide, and the liquid and/or supercritical carbon dioxide sublimes to produce hydrated but structurally preserved materials.

[0003] The present disclosure also relates to a system, device, and method for creating aerogel composites and, more particularly, to a system, device, and method for casting aerogel particle and plastic mixtures into a mold to make a molded sample and drying the molded sample to create a product suitable for use or that may be processed further.

BACKGROUND

[0004] This section provides background information related to the present disclosure which is not necessarily prior art.

[0005] Supercritical drying is a process for removing liquid in a precise manner and is used in a variety of applications that include drying spices, decaffeinating coffee, producing aerogels and preparing biological specimens. Supercritical drying is used to avoid damage to solid structures that is caused by surface tension of liquid that is in contact with the solid structures when the liquid crosses the phase boundary from a liquid state to a gas state. Using supercritical drying, liquid transitions to gas without crossing the phase boundary by passing through what is referred to as a supercritical region. In the supercritical region, the distinction between gas and liquid ceases to apply and the densities of the liquid phase and the gas phase are the same at the critical point of drying.

[0006] Fluids suitable for supercritical drying include carbon dioxide, nitrous oxide and supercritical water. Water is not typically used however, because of heat damage and corrosiveness issues. Thus, in most processes, acetone is used to wash all water away (acetone is commonly used because of the complete miscibility of acetone and water), and the acetone is then washed away using high pressure liquid carbon dioxide. Next, the liquid carbon dioxide is heated until the temperature rises above the critical point as shown in Figure 1 . Figure 1 illustrates a phase diagram for carbon dioxide. Thereafter, pressure is gradually released to allow the gas to escape, leaving behind a dried product.

[0007] Supercritical drying is known to be a time consuming process. As described in U.S. Patent Application Publication No. 2004/0087670 A1 to Lee et al., each batch requires about 40 hours of extractor time. It takes approximately 5-20 minutes to place wet gels, i.e., the "sol" gel, in an extractor, and after the extractor is filled with liquid carbon dioxide, it takes approximately 30 hours to replace the solvent in the gel with liquid carbon dioxide. Solvent exchange is time consuming because of a combination of the rate of diffusivity of the solvent, the rate of diffusivity of liquid carbon dioxide, and the solute solubility of the liquid carbon dioxide. Approximately 2-2.5 hours are required to heat the extractor above the critical point of carbon dioxide (1070 psi or 7378 kPa and 31 .06 ^) to ensure that the rate of heating is low enough to avoid causing damage to the solid structure. After being heated, a thermal stabilization period occurs, which requires approximately 30 minutes. Thermal stabilization is followed by depressurization, which takes approximately 6 hours and serves to vent off carbon dioxide gas. Thus, in total, approximately 40 hours are required to dry each batch of samples.

[0008] Another method commonly used to dry a product without causing the liquid to cross the boundary from the liquid phase to the gas phase is via freeze-drying. In freeze-drying, the liquid is frozen solid and pressure is reduced such that drying occurs by crossing the solid-gas boundary. Freeze-drying is also known as lyophilization or cryodesiccation, and is a dehydration process commonly used in the food and pharmaceutical industries to preserve perishable items and/or to make transportation of items more convenient. [0009] In freeze-drying, sometimes the product to be frozen is pretreated, followed by freezing. Next a primary drying phase occurs that includes lowering pressure using a partial vacuum and supplying enough heat to the material to allow the ice to sublime. During this primary drying phase, it is expected that about 95% of the water, in the form of ice, is sublimated from the material. This phase is typically slow, e.g., several days, because if too much heat is added the material's structure may be altered. It is difficult to accurately determine the temperature at which the material's structure will alter, thus heat is applied gradually.

[0010] During a secondary drying phase, unfrozen water molecules are targeted for removal. This phase depends on the material's adsorption isotherms, but the general idea is to raise the temperature higher than the primary drying phase to break any physio-chemical interactions that have been formed between the water molecules and the frozen material. Pressure is also typically lowered to encourage desorption. After freeze-drying is complete, the vacuum is usually broken with an inert gas. This freeze-drying process is inefficient, however, due to the limited rate at which heat can be introduced because too much heat too quickly may cause the sample to melt or become damaged in areas that are near the source of heat.

[0011] As stated above, an aerogel may be dried using supercritical drying. An aerogel is a synthetic material that is porous and lightweight. Aerogels are derived from a gel where the liquid component of the gel has been replaced with a gas. A variety of chemical compounds can be used to make aerogels by extracting the liquid component of the gel using supercritical drying, which allows the liquid to be slowly dried away without causing the solid matrix of the gel to collapse from capillary action. Aerogels do not have a designated material or chemical formula, but represent a group of materials with a certain geometric structure.

[0012] To produce an aerogel, first a colloidal suspension of solid particles is created, known as a "sol". For example, a liquid alcohol such as ethanol may be mixed with a silicon alkoxide precursor to create a silica aerogel. A hydrolysis reaction form particles of silicon dioxide causes a sol solution to form. Thereafter, the oxide suspension begins to undergo condensation reactions that create metal oxide bridges that link the dispersed colloidal particles. Once interlinking has stopped, a gel is formed. This can be time consuming, thus catalysts are typically used to improve processing speeds. Next, removal of liquid occurs. When liquid is allowed to evaporate from gels, these gels are referred to as xerogels. Xerogels has low porosities due to the surface tension (capillary action) that destroys the gel network, as set forth above. Thus, supercritical drying is used, as set forth above, to achieve high porosities. However, as stated above, the time and expense associated with heating and depressurizing a vessel that contains the same and supercritical carbon dioxide is time consuming and requires a pressure vessel throughout. Thus, there is a need for a process of drying sol gels faster and that circumvents the use of a pressure vessel through the drying process while still maintaining the integrity of the micro, meso and/or macroporous structure that is being dried.

[0013] While ambient pressure drying is known for drying aerogels, known ambient pressure drying methods include capping the negatively charged surface groups, such as hydroxyl groups, of gel networks with positively charged capping agents such as methyltrimethoxysilane. The solvent in the gel is then replaced with a different solvent, usually an aprotic solvent such as hexane, which has a low surface tension and is positively charged, and then gently removing the positively charged solvents, such as hexane, using inter-repulsive charges (i.e., using the principle that likes will repel likes). In this way, the harmful effects of surface tension that are caused by a liquid transitioning to a vapor or gas are mitigated. However, this process is not seen as an improvement over supercritical drying of aerogels because of the additional chemicals and solvents required, and because the end result of ambient pressure drying is typically aerogels that are opaque and that exhibit higher density and higher thermal conductivity.

[0014] Thus, there remains a need in the art for a way to dry samples such as sol gels and aerogels that does not require supercritical drying and that does not suffer from the drawbacks of known ambient pressure drying techniques as set forth above. SUMMARY

[0015] This section provides a general summary of the disclosure, and is not a comprehensive disclosure of its full scope or all of its features.

[0016] The current technology provides a method for drying a porous structure. The method includes transferring the porous structure to a pressure chamber, wherein the porous structure comprises a plurality of pores and a first solvent disposed in and about the plurality of pores. The method also includes flushing the pressure chamber with CO ₂ until CO ₂ replaces at least a portion of the first solvent in and about at least a portion of the pores, rapidly decreasing the temperature inside the pressure chamber to cause freezing of the CO ₂ in and about the at least a portion of the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided, and removing the CO2 by subliming to yield a dried porous structure.

[0017] The current technology also provides a method for rapidly drying a porous structure. The method includes transferring the porous structure to a pressure chamber, wherein the porous structure has a plurality of pores and a first solvent disposed in and about the plurality of pores, introducing CO2 within the pressure chamber, raising the temperature and the pressure within the pressure chamber to generate supercritical CO ₂ (sCO ₂ ), rapidly flushing the pressure chamber with sCO ₂ until sCO ₂ replaces at least a portion of the first solvent in and about at least a portion of the pores, depressurizing chamber by rapidly decreasing the temperature inside the pressure chamber, wherein the SCO ₂ condenses to a liquid and solidifies in and about the at least a portion of the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided, and removing the CO2 by subliming to yield a dried porous structure.

[0018] The current technology also provides a method for impregnating and drying a porous structure. The method includes transferring the porous structure to a pressure chamber, wherein the porous structure comprises a plurality of pores and a first solvent disposed in and about the plurality of pores, flushing the pressure chamber with CO ₂ until CO ₂ replaces at least a portion of the first solvent in and about at least a portion of the pores, raising the temperature and the pressure within the pressure chamber to generate supercritical CO2 (SCO2), impregnating the porous structure with at least a first impregnating agent by introducing a first mixture including SCO2 and the at least first impregnating agent into the drying chamber, wherein the first impregnating agent is not present in the porous structure prior to the transferring, rapidly decreasing the temperature inside the pressure chamber to cause freezing of the first mixture in and about the at least a portion of pores of the porous structure, wherein the first impregnating agent is loaded into the porous structure and the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided, and selectively removing the CO2 by subliming to yield a dried porous structure containing the at least first impregnating agent.

[0019] The current technology also provides a method of preserving a porous material having primary or secondary amines. The method includes transferring the porous structure to a pressure chamber, wherein the porous structure have a plurality of pores and a first solvent disposed in and about the plurality of pores, contacting the porous structure with CO2, converting the primary or secondary amines to carbamates that protect the porous structure from the CO2, rapidly decreasing the temperature inside the pressure chamber to cause freezing of the CO ₂ in and about the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided, removing the CO2 by subliming, and converting the carbamates back into primary or secondary amines.

[0020] The current technology also provides a composite material. The composite material has a porous aerogel matrix and a plurality of reinforcing agents uniformly dispersed therein. The composite material is made by a process that includes disposing a plurality of reinforcing agents into a first solvent to generate a first mixture, dissolving a polymer in a second solvent to generate a first solution, combing the first mixture with the first solution to generate a precursor material including the first solvent and the second solvent, pouring the precursor material into a mold having a predetermined shape, and evaporating off at least a portion of at least one of the first solvent or the second solvent until the precursor material has a desired viscosity. The method then includes a step of either exchanging at least a portion of the remaining first and second solvents with CO2 or a third solvent miscible with CO2 wherein the polymer is insoluble in third solvent, or freezing the remaining first solvent and second solvent in the precursor material, and exchanging the first and second solvents with a the third solvent. Drying the precursor material without exposing the precursor material to a liquid-gas interface yields the composite material.

[0021] The current technology also provides a method for purifying nonporous structures having an amine wherein the amine is at least one of a primary amine or a secondary amine. The method includes dispersing the substance in a liquid in a pressure vessel, reversibly reacting liquid CO2 (LCO2) or supercritical CO2 (SCO2) with the at least one amine to form at least one negatively charged carbamate group, wherein the at least one carbamate group reduces the effects of surface tension of negatively charged CO ₂ molecules when substances are exposed to a gas/liquid interface, rapidly decreasing the temperature inside the pressure chamber to cause freezing of the CO2 in and about the at least a portion of the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided, removing the CO ₂ by subliming to yield a dried porous structure, and removing the at least one negatively charged carbamate group after the subliming.

[0022] The current technology also provides a method of depressurizing a vessel containing liquid CO ₂ or supercritical fluid. The method includes depressurizing the vessel and converting liquid or supercritical CO2 to solid CO2, such that the formation of gas bubbles within the vessel is minimized or avoided.

[0023] The current technology also provides a method of sterilizing a material. The method includes transferring the material to a pressure vessel, pressurizing the vessel by introducing CO ₂ in a gas, liquid, or supercritical state until the pressure inside the vessel is between 7-1000 Mpa, maintaining the pressure inside the pressure vessel for at least 10 minutes, rapidly depressurizing the vessel by cooling the vessel until the pressure inside the vessel reaches about atmospheric pressure to form a coating of dry ice about the material, wherein the coating of dry ice is at least 10 atoms thick, removing the material having a coating of dry ice from the pressure vessel, and removing the dry ice by sublimation at a pressure of at least about 1 atm.

[0024] The current technology also provides a method of dehydrating a material, wherein the material has a structure including bound and/or free water molecules. The method includes transferring the material to a pressure vessel, injecting and flowing through the pressure vessel a fluidized mixture including CO ₂ and at least one other hydrophobic compound, the at least one other hydrophobic compound being at least partially miscible or partially soluble in the CO ₂ , and having a density of less than or equal to about 1 .0 g/cm ³ , and displacing the bound and/or free water molecules from the material with the fluidized mixture.

[0025] The current technology also provides a method for preserving a biological organ. The organ is porous and has a first solvent disposed in and about the pores. The method includes transferring the biological organ to a pressure chamber, wherein the biological organ is porous and has a first solvent disposed in and about the pores, flushing the pressure chamber with CO ₂ until CO ₂ replaces at least a portion of the first solvent in and about at least a portion of the pores, rapidly decreasing the temperature inside the pressure chamber to cause freezing of the CO ₂ in and about the at least a portion of the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided, and removing the CO ₂ by subliming to yield a preserved organ. [0026] The current technology also provides a method for producing a mold. The method includes transferring a structure having a predetermined shape to a pressure chamber, wherein the structure comprises a plurality of pores and a first solvent disposed in and about the plurality of pores, flushing the pressure chamber with CO ₂ until CO ₂ replaces at least a portion of the first solvent in and about at least a portion of the pores, rapidly decreasing the temperature inside the pressure chamber to cause freezing of the CO ₂ in and about the at least a portion of the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided, and removing the CO ₂ by subliming to yield a mold having the predetermined shape. The mold is suitable, for example, for lost foam casting.

[0027] The current technology also provides a method for making a composite material including a porous aerogel matrix and a plurality of reinforcing agents uniformly dispersed therein. The method includes disposing a plurality of reinforcing agents into a first solvent to generate a first mixture; dissolving a polymer in a second solvent to generate a first solution; combing the first mixture with the first solution to generate a precursor material including the first solvent and the second solvent; pouring the precursor material into a mold having a predetermined shape; and evaporating off at least a portion of at least one of the first solvent or the second solvent until the precursor material has a desired viscosity. The method also includes performing at least one of exchanging at least a portion of the remaining first and second solvents with CO ₂ or a third solvent miscible with CO ₂ wherein the polymer is insoluble in third solvent, and freezing the remaining first solvent and second solvent in the precursor material, and exchanging the first and second solvents with the third solvent; and drying the precursor material without exposing the precursor material to a liquid-gas interface to yield the composite material.

[0028] The current technology also provides a composite material including a porous plastic matrix, a porous aerogel matrix; and a plurality of reinforcing agents uniformly dispersed therein. The composite material is made by a process that includes disposing a plurality of reinforcing agents into a first solvent to generate a first mixture; dissolving a polymer in a second solvent to generate a first solution; disposing a plurality of aerogel matrix precursors into a third solvent to generate a second mixture, wherein the polymer is insoluble in the third solvent; combining the first mixture and the second mixture with the first solution to generate a precursor material including the first solvent, the second solvent, and the third solvent; transferring the precursor material into a mold having a predetermined shape; and evaporating at least a portion of at least one of the first solvent, the second solvent, or the third solvent from the precursor material until the precursor material has a desired viscosity. The method also includes performing at least one of exchanging at least a portion of the remaining first, second, and third solvents with CO ₂ , and freezing the remaining first solvent, second solvent, and third solvent in the precursor material, and exchanging the first, second solvent, and third solvents with a fourth solvent; and drying the precursor material, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided.

[0029] The current technology also provides a porous plastic aerogel composite having a predetermined shape. The porous plastic aerogel composite is made by a method that includes cutting, grinding milling, crushing, heating, or swelling a shaped porous plastic aerogel composite to form a plurality of plastic aerogel composite particles; adding a first polymr to the plastic aerogel composite particles to form a first mixture; placing the first mixture into a pressure chamber; heating and pressurizing the first mixture of particles to impregnate the pores of porous plastic aerogel with a first plastic polymer and to generate a heated and pressurized mixture; extruding the heated and pressurized mixture into a mold having a predetermined shape to generate an extruded mixture; cooling the extruded mixture; and removing the extruded mixture to yield a plastic porous plastic aerogel composite matrix having a defined shape.

[0030] The current technology also provides a metal aerogel composite that includes a metal, a plurality of aerogel matrices, and a plurality of reinforcing agents. The metal aerogel composite is made by a process that includes placing a shaped porous plastic aerogel composite containing dispersed particles into a high temperature mold; placing a suitable refractory material in and around at least a portion of the shaped porous plastic aerogel composite; replacing a plastic portion of the shaped porous plastic aerogel composite contained within the mold with a molten metal by pouring a molten metal over, above and around the shaped porous plastic aerogel composite to vaporize the plastic portion; allowing the mold sufficient time to cool and for the molten metal to solidify; and removing the metal aerogel composite from the refractory material.

[0031] In one form, the present disclosure provides for a method of drying a porous structure. The method can include the step of transferring a first porous structure to a first pressure vessel, wherein the first porous structure comprises a plurality of pores. The method can include the step of connecting the first pressure vessel to a first docking station for fluid communication therewith. The method can include the step of flowing an amount of a drying material from the first docking station into the first pressure vessel, the drying material being in a liquid state or a supercritical state. The method can include the step of disconnecting the first pressure vessel from the first docking station. The method can include the step of moving the first pressure vessel to a second docking station apart from the first docking station. The method can include the step of connecting the first pressure vessel to the second docking station for fluid communication therewith. The method can include the step of flowing an amount of a cooling fluid from the second docking station to a cooling system of the first pressure vessel to freeze the drying material within the first pressure vessel. The method can include the step of disconnecting the first pressure vessel from the second docking station. The method can include the step of moving the first pressure vessel away from the second docking station. The method can include the step of depressurizing the first pressure vessel. The method can include the step of unloading the frozen drying material from the first pressure vessel.

[0032] According to a further embodiment, the method can further include the step of transferring a second porous structure to a second pressure vessel, wherein the second porous structure comprises a plurality of pores. The method can include the step of connecting the second pressure vessel to the first docking station for fluid communication therewith after the first pressure vessel is disconnected from the first docking station. The method can include the step of flowing an amount of the drying material from the first docking station into the second pressure vessel, the drying material being in a liquid state or a supercritical state.

[0033] According to a further embodiment, the method can further include the step of disconnecting the second pressure vessel from the first docking station. The method can include the step of moving the second pressure vessel to the second docking station after the first pressure vessel is disconnected from the second docking station. The method can include the step of connecting the second pressure vessel to the second docking station for fluid communication therewith. The method can include the step of flowing an amount of the cooling fluid from the second docking station to a cooling system of the second pressure vessel to freeze the drying material within the second pressure vessel. The method can include the step of disconnecting the second pressure vessel from the second docking station. The method can include the step of moving the second pressure vessel away from the second docking station. The method can include the step of depressurizing the second pressure vessel. The method can include the step of unloading the frozen drying material from the second pressure vessel.

[0034] According to a further embodiment, the drying material can be CO2.

[0035] According to a further embodiment, after disconnecting the first pressure vessel from the first docking station and before moving the first pressure vessel to the second docking station, the method can include the steps of moving the first pressure vessel to an intermediate docking station, connecting the first pressure vessel to the intermediate docking station for fluid communication therewith, flowing an amount of the drying material from the intermediate docking station into the first pressure vessel, the drying material being in a liquid state or a supercritical state, and disconnecting the first pressure vessel from the intermediate docking station.

[0036] According to a further embodiment, the method can further include the step of removing the drying material from the first porous structure by sublimating the drying material.

[0037] In another form, the present disclosure provides for a device for drying a porous structure. The device can include a cart, a pressure vessel, a first port, and a second port. The cart can include a base and a support structure fixedly coupled to the base. The pressure vessel can define an interior chamber disposed about a first axis and extending longitudinally along the first axis. The pressure vessel can hold a drying material in a liquid state or a supercritical state within the interior chamber and at a pressure above atmospheric pressure. The pressure vessel can be coupled to the support structure for rotation relative to the support structure about a second axis that is perpendicular to the first axis. The first port can be in fluid communication with the interior chamber proximate to a top of the interior chamber. The first port can extend externally of the pressure vessel. The second port can be in fluid communication with the interior chamber proximate to a bottom of the interior chamber. The second port can extend externally of the pressure vessel.

[0038] According to a further embodiment, the device can further include a plurality of wheels rotatably coupled to the base of the cart and configured to support the cart.

[0039] According to a further embodiment, the device can further include an inlet port, an outlet port, and a first cooling coil. The first cooling coil can be disposed within the interior chamber. The first cooling coil can be coupled to the inlet port and the outlet port for fluid communication therewith. The inlet and outlet ports can be external to the pressure vessel.

[0040] According to a further embodiment, the first cooling coil can be coupled to the inlet port via a first quick connect and the first cooling coil can be coupled to the outlet port via a second quick connect.

[0041] According to a further embodiment, the device can further include an insulating cover and a cooling coil. The insulating cover can be disposed about an exterior surface of the pressure vessel. The cooling coil can be disposed about the pressure vessel between the insulating cover and the exterior surface of the pressure vessel.

[0042] According to a further embodiment, the device can further include a heating element disposed about the exterior of the pressure vessel between the insulating cover and the exterior of the pressure vessel.

[0043] According to a further embodiment, the device can further include a compressor and a controller. The compressor and the controller can be supported by the cart. The controller can control operation of the compressor. An outlet of the compressor can be coupled to the first port for fluid communication therewith.

[0044] According to a further embodiment, the device can further include a mixing device disposed within the interior chamber and configured to stir a contents of the interior chamber.

[0045] According to a further embodiment, the mixing device can include a motor disposed within the interior chamber.

[0046] According to a further embodiment, the motor can include oil-free bearings.

[0047] According to a further embodiment, the motor can include a filter membrane that is permeable to sCO2 within the interior chamber, but impermeable to a solute or particles contained or carried by sCO2 within the interior chamber.

[0048] In another form, the present teachings provide for a device for drying a porous structure including a first cylindrical body, a second cylindrical body, a first nut, a first port, a second port, and a shelf. The first cylindrical body can have a first proximal end, a first distal end, and a first bore disposed about a first axis and extending axially through the first proximal end and the first distal end. The first proximal end can include a first mating face. The second cylindrical body can have a second proximal end, a second distal end, and a second bore disposed about the first axis and extending axially through the second proximal end and the second distal end. The first and second bores can cooperate to define a circumferential periphery of an interior chamber. The second proximal end can include a plurality of external threads and a second mating face. The first nut can be rotatably coupled to the first proximal end and configured to threadably engage the plurality of external threads on the second proximal end to sealingly engage the first mating face with the second mating face. The first port can be open to the interior chamber proximate to a top of the interior chamber. The first port can be open to an exterior of the device. The second port can be open to the interior chamber proximate to a bottom of the interior chamber. The second port can be open to the exterior of the device. The shelf can be disposed within the interior chamber and configured to support the porous structure to be dried within the interior chamber.

[0049] According to a further embodiment, the first mating face can be a convex surface and the second mating face can be a concave surface.

[0050] According to a further embodiment, the first distal end can include a third mating face that is a concave surface adapted to sealingly engage a convex surface of a lid or a third cylindrical body.

[0051] According to a further embodiment, the first distal end can include a third mating face that is a convex surface adapted to sealingly engage a concave surface of a lid or a third cylindrical body.

[0052] According to a further embodiment, the second distal end can include a third mating face that is a convex surface adapted to sealingly engage a concave surface of a lid or a third cylindrical body.

[0053] According to a further embodiment, the second distal end can include a third mating face that is a concave surface adapted to sealingly engage a convex surface of a lid or a third cylindrical body.

[0054] According to a further embodiment, the device can further include a third cylindrical body and a second nut. The third cylindrical body can have a third proximal end, a third distal end, and a third bore disposed about the first axis and extending axially through the third proximal end and the third distal end. The first, second, and third bores can cooperate to define the circumferential periphery of the interior chamber. The second distal end can include a third mating face and the third proximal end can include a fourth mating face. The second nut can be rotatably coupled to one of the second distal end or the third proximal end and is configured to threadably engage a plurality of external threads on the other of the second distal end or the third proximal end to sealingly engage the third mating face with the fourth mating face.

[0055] According to a further embodiment, the device can further include a first inlet port, a first outlet port, and a first cooling coil. The first cooling coil can be disposed within the interior chamber. The first cooling coil can be coupled to the first inlet port and the first outlet port for fluid communication therewith. The first inlet port and the first outlet port can be external to the interior chamber.

[0056] According to a further embodiment, the first cylindrical body can include a first intermediate portion disposed between the first proximal end and the first distal end. The first inlet port and the first outlet port can extend radially through the first intermediate portion.

[0057] According to a further embodiment, the first inlet port and the first outlet port can be quick disconnect ports.

[0058] According to a further embodiment, the device can further include an insulating cover and a cooling coil. The insulating cover can be disposed about an exterior surface of the first cylindrical body. The cooling coil can be disposed about the first cylindrical body between the insulating cover and the exterior surface of the first cylindrical body.

[0059] According to a further embodiment, the device can further include a heating element disposed about the exterior surface of the first cylindrical body between the insulating cover and the exterior surface of the first cylindrical body.

[0060] According to a further embodiment, the device can further include a lid and a second nut. The second nut can be rotatably coupled to the lid and can threadably enagage a plurality of threads formed on the first distal end of the first cylindrical body to sealingly couple the first cylindrical body to the lid.

[0061] According to a further embodiment, the first nut can include a plurality of radially outward extending protrusions.

[0062] According to a further embodiment, each of the radially outward extending protrusions can include a threaded bore. Each threaded bore can be perpendicular to the first axis.

[0063] According to a further embodiment, each of the radially outward extending protrusions can include a support rod bore. Each support rod bore can be parallel to the first axis and can extend axially through each protrusion. [0064] In another form, the present teachings provide for a device for drying a porous structure including a pressure vessel and a first shelf. The pressure vessel can hold a drying material in a liquid state or a supercritical state and at a pressure above atmospheric pressure. The pressure vessel can include a first outer cylindrical body, an outer sleeve, and an inner sleeve. The first outer cylindrical body can include a bore disposed about a first axis. The outer sleeve can be received in the bore of the first outer cylindrical body. The outer sleeve can include a bore disposed about the first axis. The inner sleeve can be axially slidably received in the bore of the outer sleeve. The inner sleeve can include a bore disposed about the first axis. The first shelf can be disposed within the bore of the inner sleeve and can support a first amount of the porous structure within the bore of the inner sleeve.

[0065] According to a further embodiment, the device can further include a cooling coil, a first cooling inlet, and a first cooling outlet. The cooling coil can be disposed within the bore of the inner sleeve. The first cooling inlet can be in fluid communication with the cooling coil. The first cooling inlet can extend through an exterior wall of the pressure vessel. The first cooling outlet can be in fluid communication with the cooling coil. The first cooling outlet can extend through the exterior wall of the pressure vessel.

[0066] According to a further embodiment, the first cooling inlet and the first cooling outlet can extend radially through the inner sleeve, the outer sleeve, and the first outer cylindrical body.

[0067] According to a further embodiment, the first cooling coil can be fixedly coupled to a bottom side of the first shelf.

[0068] According to a further embodiment, the device can further include a second shelf and a second cooling coil. The second shelf can be disposed within the bore of the inner sleeve and configured to support a second amount of the porous structure within the bore of the inner sleeve. The second shelf can be coupled to the first shelf. The second cooling coil can be coupled to the first cooling coil for fluid communication therewith. The second cooling coil can be fixedly coupled to a bottom side of the second shelf.

[0069] According to a further embodiment, the first outer cylindrical body can include a plurality of interior threads and the outer sleeve can include a plurality of exterior threads that threadably engage the interior threads of the first outer cylindrical body. [0070] According to a further embodiment, one of the outer sleeve or the inner sleeve can include a notch and the other of the outer sleeve or the inner sleeve can include a track received in the notch. The track and the notch can cooperate to permit the inner sleeve to slide axially relative to the outer sleeve while inhibiting relative rotation between the inner and outer sleeves.

[0071] In another form, the present teachings provide for a device for drying a porous structure including a pressure vessel, an insulating cover, a cooling inlet, a cooling coil, and a valve. The pressure vessel can define an interior chamber disposed about a first axis and extending longitudinally along the first axis. The pressure vessel can hold a drying material in a liquid state or a supercritical state within the interior chamber and at a pressure above atmospheric pressure. The insulating cover can be disposed about a first exterior surface of the pressure vessel. The cooling inlet can receive a cooling fluid. The cooling coil can be disposed about the first exterior surface between the insulating cover and the first exterior surface. The cooling coil can be coupled to the cooling inlet for fluid communication therewith. The valve can include a valve inlet, a first valve outlet, and a second valve outlet. The valve inlet can be coupled to the cooling coil for fluid communication therewith. The first valve outlet can be open to a cavity defined by the insulating cover and the first exterior surface. The second valve outlet can be open to an exterior of the insulating cover. The valve can selectively be operated in a first mode, and a second mode. In the first mode, the valve can permit fluid communication between the valve inlet and the first valve outlet and not permit fluid communication between the valve inlet and the second valve outlet. In the second mode, the valve can permit fluid communication between the valve inlet and the second valve outlet and not permit fluid communication between the valve inlet and the first valve outlet.

[0072] According to a further embodiment, the device can further include a heating element disposed about the first exterior surface between the insulating cover and the first exterior surface.

[0073] According to a further embodiment, the heating element can be an electric resistance heating element.

[0074] According to a further embodiment, the heating element can be in contact with the first exterior surface.

[0075] According to a further embodiment, the heating element can be in contact with the cooling coil. [0076] Further areas of applicability will become apparent from the description provided herein. The description and specific examples in this summary are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure. DRAWINGS

[0077] The drawings described herein are for illustrative purposes only of selected embodiments and not all possible implementations, and are not intended to limit the scope of the present disclosure.

[0078] Fig. 1 is a phase diagram of CO ₂ ;

[0079] Fig. 2 is a flow chart showing a conventional method for drying a porous structure;

[0080] Fig. 3 is a flow chart showing a first method for drying a porous structure according to various aspects of the current technology;

[0081] Fig. 4 is a flow chart showing a second method for drying a porous structure according to various aspects of the current technology;

[0082] Fig. 5 is a flow chart showing a third method for drying a porous structure according to various aspects of the current technology;

[0083] Fig. 6A is a graphic illustration of a first device for drying a porous structure according to various aspects of the current technology;

[0084] Fig. 6B is a graphic illustration showing perspective view of the first device shown in Fig. 6A;

[0085] Fig. 6C is a graphic illustration of a shelf that is disposed in the interior of the device shown in Fig. 6B;

[0086] Fig. 7 is a graphic illustration of a process for making a composite material according to various aspects of the current technology;

[0087] Fig. 8A is a micrograph showing a surface of an aerogel produced according to various aspects of the current technology at a first magnification;

[0088] Fig. 8B is a micrograph showing the aerogel of Fig. 8A at a second magnification;

[0089] Fig. 9 is a summary report showing Brunauer-Eimmett-Teller (BET) results for an aerogel made according to various aspects of the current technology;

[0090] Fig. 10A is a micrograph showing dried placental tissue produced according to various aspects of the current technology at a first magnification; [0091] Fig. 10B is a micrograph showing the dried placental tissue of Fig. YA at a second magnification;

[0092] Fig. 10C is a micrograph showing the dried placental tissue of Fig. YA at a third magnification; and

[0093] Fig. 10D is a micrograph showing the dried placental tissue of Fig. YA at a fourth magnification;

[0094] Fig. 1 1 is a graphic illustration of a second device for drying a porous structure and a plurality of stations according to various aspects of the present disclosure;

[0095] Fig. 12 is a perspective view of the second device of Fig. 1 1 , illustrating a vessel assembly and a cart from a first viewpoint;

[0096] Fig. 13 is a perspective view of the second device of Fig. 12, illustrated from a second viewpoint;

[0097] Fig. 14 is a perspective view of the second device of Fig. 12, illustrated from a third viewpoint;

[0098] Fig. 15 is a perspective view of the second device of Fig. 12, illustrated from a fourth viewpoint;

[0099] Fig. 16 is a perspective view similar to Fig. 14, illustrating the vessel assembly in a second configuration relative to the cart;

[0100] Fig. 17 is a perspective view of a portion of the vessel assembly of Fig. 16;

[0101] Fig. 18 is a perspective sectional view of the portion of the vessel assembly of Fig. 17;

[0102] Fig. 19 is a perspective view illustrating exploded and assembled views of a segment of the vessel assembly of Fig. 17;

[0103] Fig. 20 is a perspective view similar to Fig. 19, illustrating a second configuration of the segment of the vessel assembly of Fig. 17;

[0104] Fig. 21 is an exploded perspective view of a female end of the vessel assembly of Fig. 17, illustrating a sleeve assembly and a shelf assembly in accordance with the present disclosure;

[0105] Fig. 22 is an exploded perspective view of a male end of the vessel assembly of Fig. 17, illustrating a sleeve assembly and a shelf assembly similar to the sleeve assembly and the shelf assembly of Fig. 21 ; [0106] Fig. 23 is a top plan view of the female end, sleeve assembly, and shelf assembly of Fig. 21 ;

[0107] Fig. 24 is a top plan view of a tongue and groove joint of the sleeve assembly of Fig. 21 ;

[0108] Fig. 25 is a perspective view of the shelf assembly of Fig. 21 ;

[0109] Fig. 26 is a perspective view of the shelf assembly of Fig. 21 illustrated from a second viewpoint;

[0110] Fig. 27 is a partially exploded perspective view of a portion of a cooling system of the shelf assembly of Fig. 21 ;

[0111] Fig. 28 is an exploded perspective view of a shelf of the shelf assembly of Fig. 21 ;

[0112] Fig. 29 is a partial sectional view of the vessel assembly of Fig. 12;

[0113] Fig. 30 is a partially exploded perspective view of a male portion of the vessel assembly of Fig. 12, illustrating a cooling system of the male portion;

[0114] Fig. 31 is a perspective view of a female portion of the vessel assembly of Fig. 12, illustrating a cooling system of the female portion;

[0115] Fig. 32 is a perspective view of a portion of the cooling system of Fig. 31 ;

[0116] Fig. 33 is a partial sectional perspective view of a bottom of the vessel assembly of Fig. 12;

[0117] Fig. 34 is a partial sectional perspective view of the bottom of the vessel assembly of Fig. 12, illustrated from a second viewpoint;

[0118] Fig. 35 is a perspective view of a top of the vessel assembly of Fig. 12;

[0119] Fig. 36 is a perspective view of a portion of the top of the vessel assembly illustrated in Fig. 35;

[0120] Fig. 37 is a perspective view of a third device for drying a porous structure and a plurality of stations according to various aspects of the present disclosure, illustrating a second vessel assembly and a second cart;

[0121] Fig. 38 is a perspective view of the third device of Fig. 37, illustrated from a second viewpoint;

[0122] Fig. 39 is a perspective view of the third device of Fig. 37, illustrated from a third viewpoint;

[0123] Fig. 40 is a perspective view of a portion of the third device of Fig. 37, illustrating a cooling system;

[0124] Fig. 41 is a perspective view of a top of the vessel assembly of Fig. 37; [0125] Fig. 42 is a perspective view of a portion of the top of the vessel assembly of Fig. 41 ;

[0126] Fig. 43 is a perspective view of a bottom of the cart of Fig. 37;

[0127] Fig. 44 is a perspective view of an arrangement of a plurality of the third devices of Fig. 37;

[0128] Fig. 45 is a perspective view of a fourth device for drying a porous structure and a plurality of stations according to various aspects of the present disclosure;

[0129] Fig. 46 is a perspective sectional view of a portion of a vessel assembly of a third configuration, illustrated in an exploded position;

[0130] Fig. 47 is a perspective sectional view of a portion of the vessel assembly of Fig. 46, illustrated in a connected position;

[0131] Fig. 48 is a perspective sectional view of a portion of a vessel assembly of a fourth configuration, illustrated in a connected position;

[0132] Fig. 49 is a perspective sectional view of a portion of a vessel assembly of a fifth configuration, illustrated in a connected position; and

[0133] Fig. 50 is a perspective sectional view of a portion of a vessel assembly of a sixth configuration, illustrated in a connected position.

[0134] Corresponding reference numerals indicate corresponding parts throughout the several views of the drawings.

DETAILED DESCRIPTION

[0135] Example embodiments are provided so that this disclosure will be thorough, and will fully convey the scope to those who are skilled in the art. Numerous specific details are set forth such as examples of specific compositions, components, devices, and methods, to provide a thorough understanding of embodiments of the present disclosure. It will be apparent to those skilled in the art that specific details need not be employed, that example embodiments may be embodied in many different forms and that neither should be construed to limit the scope of the disclosure. In some example embodiments, well-known processes, well-known device structures, and well- known technologies are not described in detail.

[0136] The terminology used herein is for the purpose of describing particular example embodiments only and is not intended to be limiting. As used herein, the singular forms "a," "an," and "the" may be intended to include the plural forms as well, unless the context clearly indicates otherwise. The terms "comprises," "comprising," "including," and "having," are inclusive and therefore specify the presence of stated features, elements, compositions, steps, integers, operations, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof. Although the open-ended term "comprising," is to be understood as a non-restrictive term used to describe and claim various embodiments set forth herein, in certain aspects, the term may alternatively be understood to instead be a more limiting and restrictive term, such as "consisting of" or "consisting essentially of." Thus, for any given embodiment reciting compositions, materials, components, elements, features, integers, operations, and/or process steps, the present disclosure also specifically includes embodiments consisting of, or consisting essentially of, such recited compositions, materials, components, elements, features, integers, operations, and/or process steps. In the case of "consisting of," the alternative embodiment excludes any additional compositions, materials, components, elements, features, integers, operations, and/or process steps, while in the case of "consisting essentially of," any additional compositions, materials, components, elements, features, integers, operations, and/or process steps that materially affect the basic and novel characteristics are excluded from such an embodiment, but any compositions, materials, components, elements, features, integers, operations, and/or process steps that do not materially affect the basic and novel characteristics can be included in the embodiment.

[0137] Any method steps, processes, and operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated, unless specifically identified as an order of performance. It is also to be understood that additional or alternative steps may be employed, unless otherwise indicated.

[0138] When a component, element, or layer is referred to as being "on," "engaged to," "connected to," or "coupled to" another element or layer, it may be directly on, engaged, connected or coupled to the other component, element, or layer, or intervening elements or layers may be present. In contrast, when an element is referred to as being "directly on," "directly engaged to," "directly connected to," or "directly coupled to" another element or layer, there may be no intervening elements or layers present. Other words used to describe the relationship between elements should be interpreted in a like fashion {e.g., "between" versus "directly between," "adjacent" versus "directly adjacent," etc.). As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

[0139] Spatially or temporally relative terms, such as "before," "after," "inner," "outer," "beneath," "below," "lower," "above," "upper," and the like, may be used herein for ease of description to describe one element or feature's relationship to another element(s) or feature(s) as illustrated in the figures. Spatially or temporally relative terms may be intended to encompass different orientations of the device or system in use or operation in addition to the orientation depicted in the figures.

[0140] Throughout this disclosure, the numerical values represent approximate measures or limits to ranges to encompass minor deviations from the given values and embodiments having about the value mentioned as well as those having exactly the value mentioned. All numerical values of parameters (e.g., of quantities or conditions) in this specification, including the appended claims, are to be understood as being modified in all instances by the term "about" whether or not "about" actually appears before the numerical value. "About" indicates that the stated numerical value allows some slight imprecision (with some approach to exactness in the value; approximately or reasonably close to the value; nearly). If the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning, then "about" as used herein indicates at least variations that may arise from ordinary methods of measuring and using such parameters.

[0141] In addition, disclosure of ranges includes disclosure of all values and further divided ranges within the entire range, including endpoints and sub-ranges given for the ranges. As referred to herein, ranges are, unless specified otherwise, inclusive of endpoints and include disclosure of all distinct values and further divided ranges within the entire range. Thus, for example, a range of "from A to B" or "from about A to about B" is inclusive of A and of B.

[0142] Example embodiments will now be described more fully with reference to the accompanying drawings. Methods for drying porous structures

[0143] Unexpectedly, it has been found that it is possible to preserve the innate porous structure of a material by replacing the solvent in the porous structure of material with liquid or supercritical CO ₂ , subsequently solidifying the CO ₂ contained in the pores of the solvent, and the subliming solidified CO ₂ from the pores of said material(s) at pressures greater to or equal to ambient pressure to yield a dehydrated material whose porous structured is preserved. Alternatively sublimation of CO ₂ from the pores of the material(s) can occur, however it was found through the course of discovery that reducing the pressure during sublimation can lead to fusion of CO2 crystals, which intern can cause damage and cracking to materials being dried. More particularly, it was unexpectedly found that said method of drying can be carried out in a single step outside of a vessel at any temperature above -80 C at atmospheric pressure in any low moisture without the need for a vacuum.

[0144] Without being bound by theory, it is believed that the aforementioned benefits of the present method are associated with the fact that the porous structure of the material remains preserved throughout the dehydration process, especially when said material contains primary or secondary amines. It is believed that said primary and secondary amines present in the material form reversible carbamates bonds with CO ₂ that protect said material from potentially damaging effects of exposure to surface tension due to the repulsive negative charge between the negatively charged carboxylate and free CO ₂ molecules. Furthermore it is believed that the reduction in the effects of surface tension during dehydration is also afforded to nonporous structures which also contain a significant amount of primary and secondary amines.

[0145] Without being bound by theory, the materials, whose pores are filled with and surrounded by supercritical CO ₂ , are further preserved when said supercritical CO ₂ is quickly cooled below the freezing temperature of CO ₂ . It is believed that rapidly transitioning Supercritical CO ₂ through the liquid state into a solid leads to smaller crystallization due to the broader distribution of the CO ₂ during the supercritical state, whose behavior in said state closely resembles that of CO ₂ in its gaseous state.

[0146] While those skilled in the art will recognize that supercritical carbon dioxide is known for its effectiveness in removing solvents, some attributes of supercritical carbon dioxide can be potentially detrimental to the samples being dried. For example, elastomers may be adversely affected due to supercritical carbon dioxide induced swelling. Thus, controlling the density of liquid carbon dioxide to rapidly displace solvents by chilling the liquid carbon dioxide with frozen carbon dioxide may help to avoid the potentially damaging effects that may occur using supercritical carbon dioxide. Because of these density variations, not all materials are suitable for drying using supercritical carbon dioxide. Yet, many substances that are undesirably affected by supercritical carbon dioxide are relatively unaffected by liquid carbon dioxide because of its lower diffusivity and solvation properties. Thus, depending on the samples being dried, the process 20 or the process 30 may be selected.

[0147] For example, supercritical carbon dioxide may be avoided when samples may be adversely affected, but is otherwise desirable and may be used because the diffusivity is much faster compared to liquid carbon dioxide.

[0148] The aforementioned benefits of the present method are associated with the fact that the porous structure of the material remains preserved throughout solidification process without the use of cryoprotectants. Furthermore it is claimed that aforementioned method of drying is able to be carried out at a pressure greater than or equal too atmospheric pressure but not exceeding 5.1 1 atm, at temperatures above the -78.5 °C. More preferably said method of drying is carried out in a single step outside a pressure vessel at atmospheric pressure and temperatures above -78.5 °C, with the maximum temperature limited only by the decomposition temperature of the material(s) being dried. More preferably a method consisting of a single drying phase that occurs in a low moisture or moisture free environment, without the use of absorbent or fluidized beds. More preferably a method is claimed in which sublimation of CO ₂ from and around the material is carried out at standard atmospheric temperature and pressure in a moisture free environment without the use of any additional heating equipment.

[0149] Therefore, the current technology provides true ambient pressure lyophilization.

[0150] Accordingly, one aspect of the present technology relates to a method of freeze-drying wherein dehydration of the porous material occurs via solvent exchange directly with liquid or supercritical CO ₂ , with or without the addition of a co-solvent. More preferably the present technology relates to a method of freeze-drying where in dehydration of the porous material occurs via solvent exchange with an intermediate solvent(s) which are subsequently replaced by liquid or supercritical CO ₂ . Furthermore the present technology relates to a method of freeze-drying where in the solvent(s) in the pores of a material are replaced by liquid or supercritical CO ₂ ; with CO ₂ solvent replacing the preponderance of the solvent(s) in and around the pores of said material prior to solidification. The term "solvent" includes liquids and compositions in a supercritical state. As used herein, a "porous structure" refers to any material, body, or structure that comprises at least one pore. The at least one pore may be a micropore having an average diameter of less than about 2 nm, a mesopore having an average diameter of greater than or equal to about 2 nm to less than or equal to about 50 nm, a macropore having an average diameter of greater than or equal to about 50 nm, or a combination thereof.

[0151] In one embodiment of this technology, the material(s) to be processed are placed in a pressure vessel and submerged beneath a protective solvent. Pressure vessel is maintained at a temperature that is suitable for the introduction of liquid CO ₂ into vessel while material(s) remain immersed in a solvent which protects said solid material(s) from exposure to a gas-liquid interface caused by the volatilization of initial CO ₂ from liquid to gas form as it enters said pressure vessel. For materials that are incompatible with supercritical CO ₂ , liquid CO ₂ is used as the solvent. Upon filling pressure vessel with liquid CO ₂ , a drain at the bottom of the vessel is opened and CO ₂ / solvent are drained from vessel while ensuring material(s) are continuously submerged beneath liquid solvent. Liquid CO ₂ continuously pumped into and through pressure vessel at a temperature range which insures the density of liquid CO ₂ is less than the solvent it is displacing. Alternatively supercritical CO ₂ may be used. Liquid CO ₂ is used to initially fill pressure vessel. The vessel is then heated to a pressure and temperature above the critical point of CO ₂ . Upon reaching a supercritical state inside pressure vessel, more supercritical CO ₂ is continuously injected at the top of said pressure vessel, while CO ₂ and solvents are simultaneously drained at the bottom of the vessel. Supercritical CO ₂ being injected into vessel is done so at a temperature and pressure that are equal or greater too the temperature and pressure inside vessel.

[0152] In one embodiment of this technology, the material(s) to be processed are placed in a pressure vessel and submerged beneath a protective solvent. Pressure vessel is maintained at a temperature that is suitable for the introduction of liquid CO ₂ into vessel while material(s) remain immersed in a solvent which protects said solid material(s) from exposure to a gas-liquid interface caused by the volatilization of initial CO ₂ from liquid to gas form as it enters said pressure vessel. For materials that are incompatible with supercritical CO ₂ , liquid CO ₂ is used as the solvent. Upon filling pressure vessel with liquid CO ₂ , a drain at the bottom of the vessel is opened and CO ₂ / solvent are drained from vessel while ensuring material(s) are continuously submerged beneath liquid solvent. Liquid CO ₂ continuously pumped into and through pressure vessel at a temperature range which insures the density of liquid CO ₂ is less than the solvent it is displacing. Alternatively supercritical CO ₂ may be used. Liquid CO ₂ is used to initially fill pressure vessel. The vessel is then heated to a pressure and temperature above the critical point of CO ₂ . Upon reaching a supercritical state inside pressure vessel, more supercritical CO ₂ is continuously injected at the top of said pressure vessel, while CO ₂ and solvents are simultaneously drained at the bottom of the vessel. Supercritical CO ₂ being injected into vessel is done so at a temperature and pressure that are equal or greater too the temperature and pressure inside vessel.

[0153] In a third embodiment of the method of the technology, the material(s) are inserted into a heated unpressurized pressure vessel, the walls of which are maintained at a temperature above the critical temperature of CO ₂ . Material(s) may be placed in the pressure vessel without immersing said materials in a protective solvent or additional solvent, so long as no problem with unwanted drying of the material(s) occurs during loading. If the material(s) would suffer damage due to drying during loading, then they can be loaded with solvent, preferably inside a container that is inserted into the pressure vessel. Alternatively, the material(s) can be loaded into an extractor that has previously been filled with saturated vapor of the solvent to prevent drying of material(s) surfaces. The loading process for material(s) is generally performed either by lowering the material(s) into a vertical chamber or by horizontally inserting them into a horizontally-positioned extractor, i.e. by opening the lid or one side of the pressure vessel. The loading process for micron or millimeter sized material(s) is generally performed by introducing the micron or millimeter sized material(s) in solvent or a carrier gas, pouring by gravity or pumping into the extractor through a valve or opening. If the materials are not loaded with additional solvent, the extractor is then filled with extra solvent in liquid or gaseous form and at a temperature about or above the critical temperature to be used in the eventual supercritical extraction as described further below.

[0154] The next step is the removal of the solvent, both any free solvent surrounding the material(s) and that solvent contained within material(s) pores. In the prior art, this has been done either by extraction of the solvent with liquid CO ₂ (or other suitable fluid.) or as described in M. J. van Bommell et al, supra, with supercritical CO ₂ .

[0155] In the current method, the removal begins in any of several ways in which the material(s) are at a temperature that is about or above the process temperature but at a pressure below the eventual process pressure. The solvent removal from the material(s) is then completed by addition of a supercritical fluid, e.g. CO ₂ .

[0156] For example, if the material(s) in the extractor are surrounded by solvent outside the material(s), that solvent (referred to as "free solvent") can be drained by opening a valve at the bottom of the extractor. If the material(s) and solvent are in a container within the extractor, it is preferred that the container be opened both on top and bottom to enhance fluid flow. Then the extractor is pressurized by injecting into the extractor gaseous CO ₂ at a temperature above the critical temperature and at a pressure that is below the critical pressure. The gaseous CO ₂ is above the critical temperature and it has a much lower density than the liquid solvent. The gaseous CO ₂ is fed prefer-ably from the top and will form a bubble space gradually expanding from the top to squeeze the free solvent toward the bottom of the extractor where it is discharged. The free solvent is preferably continually separated from the gas and recovered. Once the bulk of the solvent has been discharged, the gaseous CO ₂ injection stops. At this point in the process, the temperature inside the extractor is substantially the same as that which will be used in the eventual supercritical solvent extraction process and the pressure is slightly below the critical pressure. Next the supercritical extraction of the solvent from within the material(s) is performed by feeding supercritical CO ₂ (or other supercritical extraction fluid) into the extractor, either from the top or the bottom, to remove by diffusion the solvent inside the material(s). Supercritical CO ₂ has a solute diffusivity that is about 10 times higher than that of liquid CO ₂ while having a viscosity that is only about one tenth that of liquid CO ₂ . Thus the diffusion/infiltration/extraction is more rapid with supercritical CO ₂ than with liquid CO ₂ . As the supercritical CO ₂ feeding continues, the extractor pressure increases beyond the critical pressure and all of the CO ₂ inside the pressure vessel turns supercritical.

[0157] Once the pressure vessel has become filled with supercritical C0 ₂ , supercritical CO ₂ containing extracted solvent is continually drained from the bottom of the extractor, since it is of higher density than pure supercritical CO ₂ . The supercritical CO ₂ injection does not create any violent fluid motion since the extractor is already near, i.e. within about 1380 kPa, preferably about 345 kPa, and most preferably about 69 kPa of the supercritical process pressure. For supercritical CO ₂ the pressure must be above 7,378 kPa. Preferably it is about 7,585 to 12,41 1 kPa. The injection process does not create any thermal shock because the temperatures of the solvent, material(s), and the supercritical CO ₂ are all practically identical.

[0158] An alternative when the material(s) are in free solvent in the pressure vessel avoids the initial draining of the solvent. Rather, the clearance volume of the extractor is directly pressurized by injecting gaseous CO ₂ at about or above the critical temperature but below the critical pressure, into the clearance space below the top of the extractor and above the top surface of the solvent covering the material(s). The CO ₂ injection continues until the pressure builds beyond the critical pressure and all of the CO ₂ turns supercritical. At this point injection of supercritical CO ₂ begins and a valve at or near the bottom of the extractor is opened to allow discharge of the solvent. In this case the supercritical CO ₂ that forms an expanding "bubble" from the top, simultaneously removing mostly free solvent along with a small amount of the solvent within the material(s), by forcing the solvent out the bottom of the extractor. After the supercritical pressure is reached, then the solvent is drained by the further infusion of supercritical CO ₂ into the top of the pressure vessel at substantially the same temperature as the material(s) /solvent. This process does not create any violent fluid motion since the clearance volume above the solvent is already pressurized to just below the critical pressure and the material(s) are immersed in the solvent when supercritical CO ₂ is first present within the pressure vessel. The injection process does not create any thermal shock because the temperatures of the solvent, material(s) and the supercritical CO ₂ are all substantially the same.

[0159] An alternative to the addition of gaseous CO ₂ into the clearance volume is the direct injection of supercritical CO ₂ into that space while the space is at about the desired supercritical temperature. In this case, the supercritical CO ₂ will initially expand into the clearance space and cool down until the pressure builds up to and beyond the critical pressure. Since the material(s) pores are immersed in and protected by the solvent when the supercritical CO ₂ is added and it expands into the clearance volume, there will be no thermal or fluid dynamic shock.

[0160] A further alternative when the material(s) (either by themselves or on a carrying tray) are loaded into an extractor without excess solvent is the use of gaseous CO ₂ to pre-pressurize the pressure vessel to just below the critical pressure, followed by injection of supercritical CO ₂ into the pressure vessel. The gaseous CO ₂ pre- pressurization does not create any violent fluid motion since it occurs gradually. The supercritical CO ₂ injection does not create any violent fluid motion since the extractor is already substantially at the process pressure. The supercritical CO ₂ injection does not create any thermal shock because the temperatures of the solvent, material(s) and the supercritical CO ₂ are all practically identical.

[0161] Another aspect of the current technology relates to a method of removing the CO2 solvent within and around the pores of a material by quickly solidifying the CO ₂ solvent contained in and around the pores of material(s) without subjecting the solid structures of the material(s) to a gas-liquid interface, thus avoiding damage imposed by capillary stress.

[0162] All prior art regarding supercritical drying relates a method in which supercritical solvents are expelled from within and around the pores of a material and within the pressure vessel to the exterior of pressure vessel by opening a vent on said vessel. Generally involves slowly expanding the supercritical fluid inside the pressure vessel while maintaining a temperature above the critical temperature of CO ₂ . Failure to maintain CO ₂ in its supercritical state during the venting process causes condensation of CO ₂ and subsequently exposes solid parts of the porous structure of said material(s) to liquid-gas interface. The aforementioned exposure can result in structural damage to porous networks within material(s) and lead to shrinkage as well as inactivation of said material(s).

[0163] Methods for drying porous structures have been described. For example, Fig. 2 is a flow chart diagram of a known method 10 for supercritical drying of one or more samples that include a structure with a porous network. At box 12, the one or more samples, which are in a solvent such as water, undergo a solvent exchange with a liquid that is miscible with liquid carbon dioxide. As used herein, the term "miscible" refers to a liquid that is at least partially soluble in a second liquid. Such solvents include acetone, ethanol and methanol. Next, the one or more solvents in the solvent miscible with liquid carbon dioxide are placed in a high pressure chamber, such as an extractor, and the solvent is then flushed out and replaced with liquid carbond dioxide at box 14. This process is complete when all of the solvent that is miscible with liquid carbon dioxide is replaced with liquid carbon dioxide.

[0164] At box 16, the liquid carbon dioxide and the one or more samples that are in the high pressure chamber are heated and pressurized to a point that is above the critical state of carbon dioxide. This causes the carbon dioxide to enter into the supercritical state as described above, meaning that the surface tension of carbon dioxide in the liquid phase is the same as carbon dioxide in the gas phase. Next, the temperature of the high pressure chamber is maintained constant and pressure is slowly decreased by venting off the supercritical carbon dioxide. As stated above, this process requires approximately 40 hours and must be carried out in a high pressure chamber such as an extractor or drying chamber.

[0165] Figure 3 is a flow chart diagram 20 of a process for drying one or more samples such that the porous structure is not damaged by surface tension and that does not require a lengthy drying process in a high pressure chamber as is required in the known process of Figure 2. The structure of the one or more samples may be nonporous, porous, or a combination thereof. If porous, the pores of the samples may be microporous, mesoporous, macroporous or a combination thereof. At box 22, the one or more samples, which are in a suitable solvent such as water undergo solvent exchange to replace the, the solvent with a different solvent that is miscible with liquid carbon dioxide. For example, water may be exchanged and replaced with acetone, ethanol or methanol. At box 24, the samples in the miscible solvent are placed in a vessel and flushed with liquid carbon dioxide until the liquid carbon dioxide replaces most or all of the solvent. Alternatively, the samples in the first solvent may be placed in the vessel where the first solvent is exchanged with the second solvent that is miscible with liquid carbon dioxide, and then liquid carbon dioxide may be introduced to flush away most or all of the second solvent. Once the liquid carbon dioxide has replaced most or all of the miscible solvent in the vessel that includes the one or more samples, the vessel is quickly cooled to a temperature that is below the freezing point of carbon dioxide to encase the samples in frozen carbon dioxide, i.e., to encase the samples in dry ice, at box 26. This may be done by flash freezing the samples and the liquid carbon dioxide with liquid nitrogen, or by cooling the samples and the liquid carbon dioxide in any other suitable manner. Next the frozen samples in the dry ice matrix are removed from the vessel and allowed to dry in a suitable manner, e.g., by subliming at ambient pressure at a suitable temperature, at box 28. Suitable temperatures range from temperatures that are above approximately -78.5 °C at 1 atm and/or above 56.6 °C at 5.1 1 atm. Alternatively, sublimation may occur by increasing temperature at ambient pressure, or by exposing the samples in the dry ice matrix to a pressure below ambient pressure with or without the addition of heat. Higher temperatures may be used according to the process 20 compared to typical freeze- drying, as described in detail above, because frozen carbon dioxide, i.e., dry ice, cannot exist as a liquid at pressures that are five times atmospheric pressure or lower. Typical freeze-drying, which is used to remove water and not carbon dioxide, requires lower temperatures to avoid water melting, i.e., to prevent water from transitioning from the solid phase to the liquid phase, which may damage the samples due to capillary forces.

[0166] Figure 4 is a flow chart diagram of a process 30 for drying one or more samples such that the porous structure of the one or more samples is not damaged by surface tension. Similar to the process 20, the process 30 does not require a lengthy drying process in a high pressure chamber as is required in the known process 10. The structure of the one or more samples may be nonporous, porous, or a combination thereof. If porous, the pores of the samples may be microporous, mesoporous, macroporous or a combination thereof. At box 32, the one or more samples, which are in a suitable solvent such as water, undergo solvent exchange to replace the solvent with a different solvent that is miscible with supercritical carbon dioxide. For example, water may be exchanged and replaced with acetone, ethanol, or methanol. At box 34, the samples in the miscible solvent are placed in a vessel and flushed with supercritical carbon dioxide until the supercritical carbon dioxide replaces most or all of the solvent. Alternatively, the samples in the first solvent may be placed in the vessel where the first solvent is exchanged with the second solvent that is miscible with supercritical carbon dioxide, and then supercritical carbon dioxide may be introduced to flush away most or all of the second solvent. Once the supercritical carbon dioxide has replaced most or all of the miscible solvent, the vessel is quickly cooled to a temperature that is below the freezing point of carbon dioxide to encase the samples in dry ice at box 36. This may be done by flash freezing the samples and the supercritical carbon dioxide with liquid nitrogen, or by cooling the samples and the supercritical carbon dioxide in any other suitable manner. Next, the frozen samples in the dry ice matrix are removed from the vessel and allowed to dry in a suitable manner, e.g., by subliming at ambient pressure and a suitable temperature, at box 38. Suitable temperatures are approximately -78.5 °C and above. Alternatively, sublimation may occur by increasing temperature at ambient pressure, or by exposing the samples in the dry ice matrix to a pressure below ambient pressure with or without the addition of heat. High temperatures may be used according to the process 30 compared to typical freeze- drying, as described above, because frozen carbon dioxide cannot exist as a liquid at pressure that are five times atmospheric pressure or lower. Typical freeze-drying, which is used to remove water and not carbon dioxide, requires lower temperature to avoid water melting, i.e., to prevent water from transitioning from the solid phase to the liquid phase, which may damage the samples due to capillary forces.

[0167] Using the process 20 or the process 30 described above, drying may be done simply at ambient pressure and temperature, thereby eliminating the need for depressurization over time in a suitable high pressure chamber or drying chamber, as is required in supercritical drying. Furthermore, controlled temperature and pressure are not required for sublimation when using the process 20 or the process 30, as is required using typical freeze-drying techniques. The process 20 and the process 30 are each capable of drying samples, i.e., subliming carbon dioxide at ambient pressure and temperature, without damaging the porous structure of the one or more samples. Thus, the process 20 and the process 30 circumvent the liquid phase to gas phase boundary of liquid carbon dioxide by freezing the one or more samples in liquid or supercritical carbon dioxide, and thereafter drying by subliming, meaning the carbon dioxide transitions from a solid phase to a gas phase.

[0168] Without being bound by any particular theory, it is believed that the use of carbon dioxide as described herein utilizes a reversible reaction between carbon dioxide and primary and secondary amines of the one or more samples to produce carbamates. Such reactions produce an amine group with NH ₂ COO ^" or NHCOOH. Using this reversible reaction protects the reactivity of the amine residues in enzymes such as Lysine by acting as a capping agent that is capable of removing itself at ambient pressures. Thus, it is presumed that this reaction acts as a protective agent due to the negative charge associated with the carbamate, as both hydroxyl groups and COO ^" groups can have a greater negative charge than the carbon dioxide molecule has around oxygen atoms. The negative charge between the carbamate and electronegative groups of the carbon dioxide molecules are believed to employ the repulsive forces described above in known ambient pressure drying techniques, where positively charged surface groups repel the positively charged solvent to reduce the damage from surface tension during evaporation. Because of the reversible reaction described above, the process 20 and the process 30 can minimize or avoid the undesirable effects of surface tension caused by exposure to a gas-liquid interface that the samples may encounter during the solvent exchange or freezing process, as well as the activity of the primary and secondary amine groups and the local repulsive forces between the carbamate groups which is thought to influence the effects of localized crystallization of carbon dioxide around the carbamates during freezing by increasing local anisotropy around them.

[0169] Production of pharmaceutical particles and compounds through other supercritical processes such as rapid expansion of supercritical solutions (RESS) and Supercritical Antisolvent process (SAS) is known. These processes are widely used, but suffer from the dispersibility of particles produced by these methods. Rapidly expanding a solution saturated with compounds is effective for creating particles, but exposure of the particles in solution to a gas-liquid interface during expansion is known to result in amorphous particles with a high degree of agglomeration. Dispersibility has been shown to be an important factor that affects these particles' ability to be successfully reconstituted subsequent to production. One embodiment of the present technology pertains to a method of purifying and producing particles with amine groups, such as those widely used in pharmaceuticals by rapidly condensing a supercritical fluid containing a porous or nonporous structure that can avoid agglomeration issues that are typical in conventional rapid expansion techniques.

[0170] Using the process 20 or the process 30, samples with pore sizes that are microporous are unexpectedly capable of being dried at ambient pressure and temperature without damaging the structure of the samples after being processed as described above. Accordingly, samples may be processed faster and require less time in specialized apparatuses such as high pressure chambers, thereby reducing the cost to manufacture the samples. Additionally, cooling of the liquid or supercritical carbon dioxide to just below the freezing point as described in the process 20 and the process 30 means that the vessel used must operate at pressures between 80 - 1 ,000 psi, whereas known supercritical drying methods require a high pressure chamber that must operate at 1 ,100 psi and above. While under a pressure that is between 80 and 1 ,000 psi, the density of liquid carbon dioxide increases, thereby allowing it to more readily displace solvents from the pores of the one or more samples during the solvent exchange process because if carbon dioxide is more dense than the solvent it is replacing the carbon dioxide can displace the solvent it is replacing to the top of the vessel, depending on the miscibility of the solvent being replaced with carbon dioxide, using a continuous hydrostatic flow of carbon dioxide being injected into the vessel such that the carbon dioxide is injected at a pressure that is higher than the pressure inside the vessel. The increase in density of the carbon dioxide and pressure of the vessel may also help to move a solvent that is less dense than carbon dioxide out of a drain, which may be located at the bottom of the vessel. This is particularly true if the solvent being displaced with the liquid carbon dioxide is not miscible with carbon dioxide, even though the solvent is less dense.

[0171] Those of ordinary skill in the art will recognize the advantages of employing liquid CO ₂ as solvent for ambient pressure freezing in the case of materials that are sensitive to supercritical CO ₂ conditions. Furthermore, there are several well- known ancillary benefits to utilizing of for a process employing CO ₂ at subcritical conditions. Operation at lower pressures can significantly reduce the cost of pressure vessel construction. Those of ordinary skill in the art will recognize that the cost of constructing large scale supercritical drying apparatus system scale exponentially with size of the vessel system constructed. It is known that supercritical CO ₂ apparatuses capable with internal volume sizes equal to or greater than 400 liters can cost over $2,000,000. The through put of said system has further deterred the wide spread adoption of supercritical CO ₂ technologies for a wide variety of applications.

[0172] While reduced pressures of subcritical CO ₂ systems offerees potential benefits of reduced equipment costs, those of ordinary skill in the art will further recognize that the employment of liquid CO ₂ has several inherent draw backs. US 6670402 B1 noted that when utilizing liquid CO ₂ as to replace the initial solvent present in the pores of gels in a 40 liter reactor for preparation five high quality crack-free aerogel monolith panels each of which is 5"χ9"χ1 ", the total processing time required was approximately 40 hours; with 30 hours and 6 hours necessary to conduct proper solvent exchange and depressurization respectively.

[0173] The dramatic difference in solvation and physical properties between CO ₂ in its liquid and supercritical state have been well studied. Generally speaking, supercritical CO ₂ (sCO ₂ ) behaves like a lipophilic solvent but, compared to liquid solvents, it has the advantage that its selectivity or solvent power is adjustable and can be set to values ranging from gas-like to liquid-like. A small amount of a co-solvent increases the ability of supercritical carbon dioxide to dissolve polar compounds. The addition of just a small quantity of co-solvent enhances the solubilizing power of the supercritical carbon dioxide, making it possible to extract much more polar molecules. Typical co-solvents include: methanol, ethanol, and water as well as fluorinated solvents, alcohols, hydrocarbons, ethers, ketones, amines, and mixtures of the above as non-limiting examples.

[0174] Most importantly however the employing Supercritical CO ₂ results in a process where the potential for damage to a porous structure resulting from surface tension in the presence of a gas liquid interface due can completely be eliminated while simultaneously utilizing a fluid that has a of diffusivity of CO ₂ is usually greater than equal to 10 ¹ greater than liquid CO ₂ . The combined results for an exponential decrease in processing time and increase in throughput with a more versatile solvent that eliminates major limiting factors when utilizing liquid CO ₂ to produce ambient pressure lyophilization for a preponderance of applications regarding porous structures. Some embodiments of this application pertain to a method of lyophilization deploying liquid CO ₂ as a solvent for materials that are adversely affected by Supercritical CO ₂ . More preferably this system pertains to a rapid scalable method of employing Supercritical CO ₂ as a solvent for rapid ambient pressure CO ₂ sublimation drying due because exponentially increased solvation, diffusivity, lack of surface tension, and the overall fact that in practice liquid CO ₂ is not economical to justify its employment.

[0175] Further examples of the differences between utilizing Supercritical CO ₂ as a solvent opposed to liquid CO ₂ we demonstrated by that demonstrated rapid depressurization of aerogel materials containing only liquid CO ₂ in and around their soft porous aerogels structures at rates of more than 4 bars a minute resulted in irreversible damage to the porous structure of said gel due the presence of surface tension in liquid CO ₂ as the initial phase, while rapid depressurization of Supercritical CO ₂ allowed for preservation of soft gels structure.

[0176] Those of ordinary skill in the art will recognize the advantages of employing liquid CO ₂ as solvent for ambient pressure freezing in the case of materials that are sensitive to supercritical CO ₂ conditions. Furthermore, there are several well- known ancillary benefits to utilizing a process employing CO ₂ at subcritical conditions. Operation at lower pressures can significantly reduce the cost of pressure vessel construction. Those of ordinary skill in the art will recognize that the cost of constructing large scale supercritical drying apparatus system scale exponentially with size of the vessel system constructed. It is known that supercritical CO ₂ apparatuses with internal volume sizes equal to or greater than 400 liters can cost over $2,000,000. The through put of such systems has further deterred the wide spread adoption of supercritical CO ₂ technologies for a wide variety of applications.

[0177] While reduced pressures of subcritical CO ₂ systems offers potential benefits of reduced equipment costs, those of ordinary skill in the art will further recognize that the employment of liquid CO ₂ in conventional systems has several inherent draw backs. It has been noted that when utilizing liquid CO ₂ to replace the initial solvent present in pores of gels in a 40 liter reactor for preparation of five high quality crack-free aerogel monolith panels, each of which is 5"χ9"χ1 ", the total processing time required was approximately 40 hours; with 30 hours and 6 hours necessary to conduct proper solvent exchange and depressurization, respectively.

[0178] Employing SCO ₂ results in a process where the potential for damage to a porous structure resulting from surface tension in the presence of a gas-liquid interface can completely be eliminated while simultaneously utilizing a fluid that has a of diffusivity of CO ₂ is usually greater than equal to 10 fold greater than that of liquid CO ₂ . The combined results for an exponential decrease in processing time and increase in throughput with a more versatile solvent that eliminates major limiting factors when utilizing liquid CO2 to produce ambient pressure lyophilization for a preponderance of applications regarding porous structures. Some embodiments of this application pertain to a method of lyophilization employing liquid CO ₂ as a solvent for materials that are adversely affected by SCO2. More preferably this system pertains to a rapid scalable method of employing SCO2 as a solvent for rapid ambient pressure CO2 sublimation drying due to exponentially increased solvation, diffusivity, lack of surface tension, and the overall fact that in practice liquid CO ₂ is not economical to justify its employment in conventional systems.

[0179] As examples of the differences between utilizing SCO2 as a solvent opposed to liquid CO ₂ , it has been demonstrated that rapid depressurization of aerogel materials containing only liquid CO ₂ in and around soft porous aerogels structures at rates of more than 4 bars a minute resulted in irreversible damage to the porous structure of the aerogel due the presence of surface tension in liquid CO2 as the initial phase, while rapid depressurization of Supercritical CO ₂ allowed for preservation of soft gels structure.

[0180] Freezing, or solidification, is a phase transition in which a liquid turns into a solid when its temperature is lowered below its freezing point. Most liquids freeze by crystallization, formation of crystalline solid from the uniform liquid. Crystallization consists of two major events, nucleation and crystal growth. Nucleation is the step wherein the molecules start to gather into clusters, on the nanometer scale, arranging in a defined and periodic manner that defines the crystal structure. The crystal growth is the subsequent growth of the nuclei that succeed in achieving the critical cluster size. Nucleation is the first step in the formation of either a new thermodynamic phase or a new structure via self-assembly or self-organization.

[0181] Those skilled in the art will recognize that this size, distribution and morphology of ice crystals is predominantly influenced by determined the freezing rate and nucleation rate. It is well known that faster freezing rates result in the formation of smaller ice crystals. Faster nucleation rates lead to a high number of nuclei formation, which are known to produce greater number of crystals with of smaller sizes.

[0182] The surface area of a droplet is determined by the liquids contact angle between the droplet surface and a material. Those skilled in the art will recognize that the contact angle is conventionally measured through the liquid, where a liquid-vapor interface meets a solid surface; quantifies the wettability of a solid surface by a liquid via the Young equation. Reduction in the contact angle results in a decrease in the surface area. Those skilled in the art will realize this effect reduces the barrier and hence results in faster nucleation on surfaces with smaller contact angles.

[0183] Without wishing to be bound by a theory it is believed that in some embodiments the lack of contact angle a between a solid porous material containing fluid having at least a portion of its molecules occupying a supercritical phase prior to the onset of rapid cooling results in the formation of liquid droplets on the surface said pores that have a reduced nucleation barrier resulting in faster formation of smaller crystal sized during the subsequent crystallization.

[0184] Furthermore without wishing to be bound by a particular theory it is believed that crystallization of CO2 on and about the surface of the porous structure(s) from CO2 molecules in a liquid or supercritical phase results in a protective layer of solid CO2 molecules that can further reduce the contact angle between liquid CO2 in and around the structure of the porous material. This is advantageous when the porous materials surface initial surface structures contain free groups exhibiting a higher positive charge and attraction forces to liquid CO2 molecules when incipient unsolidified layer of CO2 molecules on their surface are absent.

[0185] Furthermore, it is knowing that the molecular distribution of CO2 molecules in their supercritical phase are more dispersed than those occupying a liquid phase, but less disperse than those in a gas phase. Thus, one embodiment pertains to a method of drying where in the pores of a fluid containing a preponderance of CO2 have at least a portion of its molecules occupying a supercritical phase will result in a greater dispersion of smaller CO2 crystals in and around a said porous material compared to those devoid of CO2 molecules in a supercritical phase.

[0186] Fig. 5 provides another method 40 for drying a porous structure. The porous structure can be any porous structure known in the art, such as a vehicle frame, a vehicle body, a vehicle body panel, a unibody, a casing, a housing, a biological organ, a biological tissue, a bone, a cell or plurality of cells, cellular machinery, non-living biological machinery, enzymes, drug carrying devices, energy storage devices, energy capture devices, energy generation materials, capacitors, gas sensing devices, gas storage devices, gas permeable membranes, liquid membranes, cell membranes, filters, edibles, tissues, load bearing materials, construction materials, insulating materials, paints, sealing materials, liquid absorbents, foams, micro particles, nanoparticles, defective two dimensional and multi-layer materials, fibers, nanofibers, fibrous composites, and composite materials as non-limiting examples. The biological organ can be any organ, including organs transported for transplantation, including eyes, brains, hearts, lungs, livers, skin, pancreases, large and small bowels, gall bladders, bladders, kidneys, thymuses, thyroids, stomachs, and esophagus's as non- limiting examples. In some embodiments, the porous structure is mold having a predetermined shape that can be used for casting applications, such as for example, lost foam casting.

[0187] In box 43, the method comprises transferring the porous structure to a pressure chamber. The porous structure has a plurality of pores, i.e., micropores, mesopores, macropores, or combinations thereof, and a first solvent disposed in and about the plurality of pores. The first solvent is any solvent that is miscible with liquid CO ₂ (LCO ₂ ). Suitable solvents include acetone, acetonitrile, acetic acid, amyl alcohol, benzene, carbon tetrachloride, chlorobenzene, chloroform, cyclo-cresylic acid, hexane, isopropyl alcohol, di-methyl formamide, ethanol, ethyl Acetate, furfural, furfuryl alcohol, methanol, n-butane, n-heptane, n-hexane, pyridine, and combinations thereof as non- limiting examples. In some embodiments, the porous structure is transferred into a pressure chamber and the first solvent is introduced or flushed into the pressure chamber whereby the first solvent is disposed in and about the plurality of pores. For example, the pressure chamber may become filled with the first solvent, such that the porous structure becomes submerged in the first solvent.

[0188] In various embodiments, the porous structure is constructed or manufactured in a solvent or is washed in a solved. Accordingly, in box 41 the method 40 optionally includes contacting the porous structure with a second solvent that may or may not be miscible with LCO ₂ . The second solvent may be, as non-limiting examples, 2-methoxyethanol, 2,6,10,14-tetramethyl pentadecane, acetone, acetonitrile, alcohols, amyl alcohol, amyl acetate, aniline , n-butanol, sec-butanol, tert-butanol, chlorex, cyclohexanol, C1 -C6 alcohols, cyclohexanone, cresylic acid, dimethylsulfoxide, N,N- dimethylacetamide, Ν,Ν-dimethylformamide, ethanol, furfural, furfuryl alcohol, 1 - propanol, pyridine, hexane, hexanes, n-hexane, hydrocarbons, isopropanol, methanol, methoxyethanol, N-methylpyrollidone, nitrobenzene, pentanol, liquid SO2, quinolone, water, xylene, and combinations thereof. In box 42, the method 40 optionally includes exchanging the second solvent with the first solvent. Exchanging the second solvent with the first solvent may be performed, for example, by transferring the porous structure from a first vessel containing the second solvent to a second vessel containing the first solvent or by removing the porous structure from a first vessel containing the second solvent and transferring the porous structure to the pressure chamber. Introducing the first solvent into the pressure chamber as described above causes the porous structure to become submerged in the first solvent, which thereby exchanges the second solvent with the first solvent.

[0189] In box 44, the method 40 comprises flushing the pressure chamber with CO ₂ until CO ₂ replaces at least a portion of the first solvent in and about at least a portion of the pores. At least a portion of the first solvent includes greater than about 75% of the first solvent, such as from greater than or equal to about 80% to less than or equal to about 100%, from greater than or equal to about 85% to less than or equal to about 100%, from greater than or equal to about 90% to less than or equal to about 100%, from greater than or equal to about 95% to less than or equal to about 100%, or from greater than or equal to about 98% to less than or equal to about 100% of the first solvent. At least a portion of the plurality of pores includes greater than about 75% of the pores, such as from greater than or equal to about 80% to less than or equal to about 100%, from greater than or equal to about 85% to less than or equal to about 100%, from greater than or equal to about 90% to less than or equal to about 100%, from greater than or equal to about 95% to less than or equal to about 100%, or from greater than or equal to about 98% to less than or equal to about 100% of the pores. Flushing the pressure chamber with CO ₂ comprises flushing the chamber with LCO ₂ , supercritical CO ₂ (sCO ₂ ), or a combination thereof.

[0190] In some embodiments, flushing the pressure chamber with CO ₂ in box 44 of the method 40 comprises flushing the chamber with LCO ₂ and raising the temperature and the pressure within the pressure chamber to generate sCO ₂ . For example, sCO ₂ can be generated in the pressure chamber by raising the temperature to a temperature of greater than or equal to about 31 .1 ° C to less than or equal to about 145 ° C while previously, simultaneously, or subsequently raising the pressure to a pressure of greater than or equal to about 1071 psi to less than or equal to about 145,100 psi. As one of ordinary skill in the art would know, these temperatures and pressures can be varied by supplying a secondary solvent. The phase diagram of Fig. 1 provides a region or various pressures and temperatures in which sCO ₂ can be formed. [0191] As the pressure chamber is flushed with CO ₂ , the first solvent is removed from the chamber.

[0192] Referring again to Fig. 5, in box 46 the method 40 comprises rapidly freezing the CO ₂ . In various embodiments, rapidly freezing the CO ₂ includes rapidly decreasing the temperature inside the pressure chamber to cause freezing of the CO ₂ in and about the at least a portion of the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided. Rapidly decreasing the temperature inside the pressure chamber is performed by introducing a liquid into the pressure chamber, wherein the liquid has a freezing point below the freezing point of CO ₂ . The liquid can be, as non-limiting examples, liquid nitrogen or liquid helium.

[0193] In some embodiments, introducing a liquid into the pressure chamber comprises circulating a liquid about the interior of the pressure chamber. Circulation a liquid about the interior of the pressure chamber includes circulating liquid through an interior jacket than lines an interior wall that defines the pressure chamber and/or circulating a liquid through a conduit that extends about and around the interior of the pressure chamber. In some embodiments, the conduit is associated with at least one shelf that is disposed within the pressure chamber. For example, the shelf may include a solid or mesh surface composed of a plastic or metal material and the conduit can extend through the surface or be close to or in contact with the surface. In other embodiments, an exterior jacket surrounds an outer surface of the pressure chamber and the liquid is flushed through the jacket to thereby cool the interior of the pressure chamber. Any combination of the conduit, interior jacket, and exterior jacket may be used to cool the pressure chamber such that the CO ₂ freezes.

[0194] As described above, rapidly decreasing the temperature inside the pressure chamber comprises decreasing the temperature inside the pressure chamber to cause rapid freezing of the CO ₂ in and about the at least a portion of the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided. The at last a portion of the pores includes greater than about 75% of the pores, such as from greater than or equal to about 80% to less than or equal to about 100%, from greater than or equal to about 85% to less than or equal to about 100%, from greater than or equal to about 90% to less than or equal to about 100%, from greater than or equal to about 95% to less than or equal to about 100%, or from greater than or equal to about 98% to less than or equal to about 100% of the pores. The rapidly decreasing the temperature inside the pressure chamber comprises cooling the interior of the pressure chamber at a rate of greater than or equal to about 0.5 ° C/min to less than or equal to about 20 ° C/min, greater than or equal to about 1 ° C/min to less than or equal to about 15 ° C/min, greater than or equal to about 5 ° C/min to less than or equal to about 10 ° C/min, greater than or equal to about 1 ° C/min to less than or equal to about 5 ° C/min, or greater than or equal to about 5 ° C/min to less than or equal to about 10 ° C/min.

[0195] Rapidly decreasing the temperature inside the pressure chamber causes the pressure inside the pressure chamber to decrease. Therefore, the method includes decreasing the pressure within the pressure chamber. The pressure inside the pressure chamber decreases from a pressure associate with generating the SCO2 to a pressure of less than or equal to about 1 100 psi, less than or equal to about 750 psi, less than or equal to about 500 psi, less than or equal to about 250 psi, less than or equal to about 100 psi, less than or equal to about 75 psi, less than or equal to about 50 psi, less than or equal to about 25 psi, less than or equal to about 10 psi, less than or equal to about 5 psi, or less than or equal to about 1 psi. In some embodiment, decreasing the pressure includes decreasing the pressure from a pressure associated with generating supercritical CO ₂ to less than or equal to about 75 psi.

[0196] Rapidly decreasing the temperature inside the pressure chamber causes depressurization of the pressure chamber, and the rate of depressurization of the pressure chamber is accelerated by simultaneously expanding CO ₂ from within the pressure chamber CO ₂ outside the pressure chamber at a rate greater than or equal to 0.001 Mpa/minute and less than or equal to 2.0 Mpa/minute.

[0197] After the CO ₂ is frozen, the porous structure is incubated within the pressure chamber for a time of less than about 48 hours, less than about 24 hours, less than about 12 hours, less than about 6 hours, less, than about 5 hours, less than about 4 hours, less than about 3 hours, less than about 2 hours, less than about 1 hour, less than about 30 minutes, less, than about 10 minutes, less, than 5 minutes, or less than 1 mintue, such as a time of greater than or equal to about 30 seconds to less than or equal to about 48 hours.

[0198] In box 48 of Fig. 5, the method 40 comprises removing the CO2 from the porous structure, such as, for example, by subliming. Removing of the CO2 from the porous structure yields a dried porous structure. Subliming is performed at ambient temperature, room temperature (room temperature is about 25 ° C) or at a temperature above the freezing point of CO2, i.e., above -78.5 ° C. Moreover, removing the CO ₂ by subliming is performed at a pressure of greater than or equal to about ambient pressure to less than or equal to about 5.1 atm. Sublimation may be initiated by releasing the pressure within the pressure chamber and opening the pressure chamber, such that the interior of the pressure chamber equilibrates with the external environment. Alternatively, or in addition to opening the pressure chamber, the porous structure can be removed from the pressure chamber such that sublimation occurs at ambient or room temperature. The porous structure can also be transferred to an oven having a temperature of greater than about room temperature to accelerate sublimation.

[0199] In various embodiments, the porous structure comprises primary or secondary amines. Such a structure can be, for example, a polymer or a biological tissue or cell. IN such embodiments, the CO ₂ reacts with the primary or secondary amines to form carbamates. However, the carbamates are converted back to primary or secondary amines during or after the subliming. In some embodiments, the carbamates are converted back to primary or secondary amines at a pressure of greater than or equal to about 0.001 atm and less than or equal to about 5.1 atm and at a temperature of greater than or equal to about 28 ° C and less than or equal to about 400 ° C. Accordingly, the current technology provides a method of preserving a porous material comprising primary or secondary amines. The method comprises transferring the porous material to a pressure chamber, wherein the porous material comprises a plurality of pores and a first solvent disposed in and about the plurality of pores, contacting the porous material with CO ₂ , converting the primary or secondary amines to carbamates that protect the porous structure from the CO ₂ , rapidly decreasing the temperature inside the pressure chamber to cause freezing of the CO ₂ in and about the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided, removing the CO ₂ by subliming, and converting the carbamates back into primary or secondary amines. The steps of the methods are performed as described above.

[0200] The current technology also provides a method of sterilizing a material. The method comprises transferring the material to a pressure vessel, pressurizing the vessel by introducing CO ₂ in a gas, liquid, or supercritical state until the pressure inside the vessel is between 7-1000 Mpa; maintaining the pressure inside the pressure vessel for at least 10 minutes, rapidly depressurizing the vessel by cooling the vessel until the pressure inside the vessel reaches about atmospheric pressure to form a coating of dry ice about the material, wherein the coating of dry ice is at least 10 atoms thick, removing the material having a coating of dry ice from the pressure vessel, and removing the dry ice by sublimation at a pressure of at least about 1 atm. In some embodiments, the rapidly depressurizing, the pressurizing and maintaining are repeated at least one time prior a final rapid depressurization. The method can also include, during or after the pressurizing, agitating the contents of the pressure vessel with a fluid dynamic or sonochemical force.

[0201] In various embodiments, the pressure vessel comprises a wall and the pressure vessel is cooled by lowering the temperature of the wall with a cooling element. In other embodiments, rapidly depressurizing the vessel comprises exposing the wall to a cryogenic fluid that is not CO2, and simultaneously venting the CO2 from within the pressure vessel to the exterior of the pressure vessel. In yet other embodiments, the pressure vessel is cooled by rapidly venting CO ₂ inside the vessel at a rate fast enough to solidify at least one CO ₂ molecule in or around material.

[0202] When the CO2 is supercritical CO2 (SCO2) and wherein the distribution of CO2 molecules in the SCO2 have greater diffusivity and distribution of CO2 molecules in liquid CO ₂ , but lower diffusivity and distribution than CO ₂ molecules in CO ₂ gas, such that the sCO ₂ is rapidly solidified to retard the growth of large crystals. Therefore, the rate of the rapid solidification of the SCO2 is utilized to selectively control nucleation and growth of CO2 crystals and to rupture microbes residing in pores of the material. SCO2, with its molecules spaced far apart similar to a gas phase is quickly solidified, templating materials to induce nano-porous structures wherein said method avoids the formation of larger crystals due to the increased dispersion of the CO2 molecules prior to solidification

[0203] The current technology also provides a method of dehydrating a material having a structure comprising bound and/or free water molecules. The method comprises transferring the material to a pressure vessel, injecting and flowing through the pressure vessel a fluidized mixture comprising CO2 and at least one other hydrophobic compound, the at least one other hydrophobic compound being at least partially miscible or partially soluble in the CO ₂ , and having a density of less than or equal to about 1 .0 g/cm ³ , and agitating the material and fluidized mixture with ultrasonic irradiation and/or a shear liquid force to enhance the displacing the bound and/or free water molecules from the material with the fluidized mixture. The method can also include agitating the material and fluidized mixture with ultrasonic irradiation and/or a shear liquid force to enhance the displacing the bound and/or free water molecules from the material with the fluidized mixture.

Drying devices

[0204] Fig. 6A is an isometric side view of a vessel 50 that may be used in any method of drying a porous material described herein. The vessel 50 includes a chamber 52 and a rapid opening door 54 on an end 56. While depicted as a generally cylindrical shape, the chamber 52 and the rapid opening door 54 may be any suitable geometry. The chamber 52 and the rapid opening door 54 may be made of any suitable material that is capable of withstanding cryogenic temperatures, e.g., materials that are suitable for Dewar flasks such as a glass material protected by a metal outer layer or insulated materials such as metals. The rapid opening door 54 is constructed out of material(s) that can withstand cryogenic temperatures without seizing, and may include built-in localized heating coils that can reverse contraction or seizing. In some embodiments, the rapid door 54 is insulated. Samples that are submerged in a solvent are placed inside the vessel 50 as described above. For example, once the samples have had their solvent exchanged with a solvent that is miscible with liquid carbon dioxide (see for example box 22 of Figure 3) or a solvent that is miscible with supercritical carbon dioxide (see for example box 32 of Figure 4), the samples are ready to be loaded into the vessel 50. When the samples are sealed inside, the chamber 52 is flushed with liquid carbon dioxide or supercritical carbon dioxide using a solvent inlet line 62 that feeds into a top portion of the chamber 52. The solvent(s) being flushed from the samples exit the chamber 52 through a drain valve 60. After flushing is complete, the samples are ready to be cryogenically frozen.

[0205] The samples cannot be immersed into a cryogenic fluid because surface tension that may result could collapse the structure of the sample(s). Thus, a cryogenic fluid is introduced into conduits or coils within the chamber 52 to reduce the temperature within the chamber 52 to rapidly freeze the samples therein by using a heating/cooling inlet line 64. The cryogenic fluid exits the chamber 52 using a heating/cooling outlet line 66.

[0206] Fig. 6B is an end-view of the end 56 of the vessel 50 that illustrates the internal components of the chamber 52. The heating/cooling line 64 that feeds cryogenic fluid into the chamber 52 feeds into coils 78 associated with one or more shelves 76 as is described in detail below. Once the cryogenic fluid passes through the coils 78 of the shelf 76 oriented on a top row, a connector line 72 may be used to feed the cryogenic fluid into one or more of the shelves 76 that are below the top row. The heating/cooling outlet line 66 receives the cryogenic fluid after the cryogenic fluid has passed through one or more shelves 76 and the heating/cooling outlet line 66 carries the cryogenic fluid out of the chamber 52. While a cryogenic fluid is fed into and out of the chamber 52 using the heating/cooling inlet line 64 and the heating/cooling outlet line 66, any suitable fluid may be fed into and out of the chamber 52 using the heating/cooling inlet line 64 and the heating/cooling outlet line 66 to provide heating and cooling functions. For example, a fluid that supplies heat may be provided through the heating/cooling inlet line 64 and the heating/cooling outlet line 66 during sublimation of the processes 20 and 30 described above.

[0207] Pressure is maintained or changed as desired in the vessel 50 using pressure release valves 58 and the drain 60. For example, the pressure release valves 58 are used to maintain ambient pressure after the samples and carbon dioxide have been frozen to ensure that the solidified carbon dioxide sublimes without transitioning into liquid carbon dioxide. A solvent source 70 provides a solvent to the solvent inlet line 62 such as a solvent that is flushed away by carbon dioxide, or a solvent that is liquid or supercritical carbon dioxide. Although not shown for the sake of clarity, suitable pumps are included to provide the solvent to the solvent inlet line 62 and the cryogenic fluid to the heating/cooling inlet line 64, and a suitable injector is included to inject the solvent into the chamber 52 Temperature sensor(s), pressure sensor(s) and various computing devices and related hardware and software components/architecture may be included to carry out the process 20 and the process 30 using the vessel 50.

[0208] Fig. 6C is a bottom side view of three shelves 76 connected in series such that the size of each row of the shelves 76 may be varied to suit a batch size of samples being loaded therein. Each of the shelves 76 include coils 78. The coils 78 of each shelf 76 include a male connector 84 at one end and a female connector 86 at an opposite end such that each of the shelves 76 may be connected as shown, and also connected to the heating/cooling inlet line 64, the connector line 72 and/or the heating/cooling outlet line 66 so that the shelves 76 may be loaded into the chamber 52 as shown in Fig. 6B. Each shelf 76 includes a top plate 68 that rests on the coils 78. Alternatively, the coils 78 may be formed in a bottom side of the top plate 68 of each shelf 76. The top plate 68 may be a solid plate that is made from a suitable material, or may be made of a porous material that allows solvents to pass through but does not allow the samples to pass through, such as a 500 mesh stainless steel shelving.

[0209] Returning to Fig. 6B, a removable shelf 82 that rests on ledges 80 may be included in the chamber 52. The removable shelf 82 may be loaded with dry ice prior to loading samples in the vessel 50 so that when liquid carbon dioxide is introduced into the chamber 52 the temperature of the liquid carbon dioxide is reduced to change the density of the liquid carbon dioxide to a density that is higher than the solvent it is replacing. Liquid carbon dioxide has a unique and dramatic increase in density with decreasing temperature, e.g., at 20 °C the density of liquid carbon dioxide is approximately 0.773 g/ml and at -20 °C, the density of liquid carbon dioxide is approximately 1 .032 g/ml (compare to water, which has a density of 1 .00 g/ml). In contrast, supercritical carbon dioxide has a lower density of approximately 0.468 - 0.662 g/ml at approximately 30-40 °C and a pressure of approximately 73.3 - 120 bars. Thus, liquid carbon dioxide will enter the samples and push the previous solvent, which is lighter, up and out.

[0210] The samples are located below the dry ice holder so that the carbon dioxide being introduced using the solvent inlet line 62 is converted to liquid carbon dioxide (if not in liquid form). This also provides a basis for limiting a maximum height of samples so that during freezing, when the liquid carbon dioxide is condensing to a solid carbon dioxide, the level of the frozen carbon dioxide does not drop below the samples. This ensures that the samples remain immersed in solvent during freezing to avoid any potential flashing of carbon dioxide (i.e., expanding from a liquid to a gas due to increased free space above the samples caused by the condensing of solid carbon dioxide). With respect to pressure considerations, some samples may not be suitable for higher pressures or may be altered by supercritical carbon dioxide in an undesirable manner. By controlling the temperature and density of carbon dioxide, the pressure inside the vessel 50 may be reduced and controlled over a broad range of pressures, which allows the vessel 50 to purge with liquid carbon dioxide more quickly relative to when the vessel 50 was first filled with liquid carbon dioxide by continuously injecting carbon dioxide at a higher pressure than the pressure inside the vessel 50 and at a rate that is proportional to or greater than the rate at which the liquid carbon dioxide is being simultaneously drained through the drain valve 60. This also allows for the ability to control the density of the carbon dioxide being continuously injected into the vessel 50 relative to the solvent that the liquid carbon dioxide is replacing, e.g., acetone. In this way, the process 20 described above is optimized to work with a wide range of solvents that are miscible, immiscible, more dense than, or less dense than, liquid carbon dioxide. The drain valve 60 is shown as a single drain at the bottom of the vessel 50, however, one or more drains may be located at various heights of the pressure vessel 50 to allow for the removal of solvents as described herein.

[0211] While those skilled in the art will recognize that supercritical carbon dioxide is known for its effectiveness in removing solvents, some attributes of supercritical carbon dioxide can be potentially detrimental to the samples being dried. For example, elastomers may be adversely affected due to supercritical carbon dioxide induced swelling. Thus, controlling the density of liquid carbon dioxide to rapidly displace solvents by chilling the liquid carbon dioxide with frozen carbon dioxide may help to avoid the potentially damaging effects that may occur using supercritical carbon dioxide. Because of these density variations, not all materials are suitable for drying using supercritical carbon dioxide. Yet, many substances that are undesirably affected by supercritical carbon dioxide are relatively unaffected by liquid carbon dioxide because of its lower diffusivity and solvation properties. Thus, depending on the samples being dried, the process 20 or the process 30 may be selected.

[0212] By adding dry ice to the shelf 82, loading the samples, sealing the chamber 52 and adding solvent while the dry ice gently pressurizes the chamber 52, the pressure increase and temperature decrease that occurs increases the density of liquid carbon dioxide that is in the chamber 52 and/or being added to the chamber 52. One main application of the dry ice on the shelf 82 is to ensure that the tendency of liquid carbon dioxide that is being injected/pumped into the chamber 52 on the solvent inlet line 62 to flash is reduced, thereby further avoiding the risk of exposing samples to the adverse effects of surface tension of the incoming carbon dioxide. By default, the dry ice also pre-pressurizes the vessel by increasing the partial pressure from dry ice that sublimes from the time the vessel 50 is sealed to the time that liquid or supercritical carbon dioxide is injected. This again reduces the tendency of incoming carbon dioxide to flash, because it is more likely to stay in liquid form when cooled and the vapor pressure is higher. Because liquid carbon dioxide is heavier than air, it also can displace any trace amounts of air (which may contain minute amounts of moisture) that enters the vessel during the loading process. The air being displaced may be vented out one of the vents 58. Additionally, by lowering the temperature and pressure requirements of the vessel 50, the cost of constructing the vessel 50 is less costly compared to the equipment used in known supercritical carbon dioxide drying techniques.

[0213] When using supercritical carbon dioxide, the addition of dry ice to the shelf 82 may be skipped as desired. Supercritical carbon dioxide may be introduced using the solvent inlet line 62, or liquid carbon dioxide may be introduced using the solvent inlet line 62 and thereafter the liquid carbon dioxide heated and pressurized thereafter to transition the liquid carbon dioxide to supercritical carbon dioxide. For example, supercritical carbon dioxide may be avoided when samples may be adversely affected, but is otherwise desirable and may be used because the diffusivity is much faster compared to liquid carbon dioxide. Additionally, dry ice may be skipped or reduced if temperatures do not need to be lowered to increase the density of carbon dioxide. However, dry ice is also used to pre-cool the vessel 50 to reduce the need to rely on vessel walls to control temperature.

[0214] To reduce processing time of samples, the samples in the solvent may be placed in the vessel 50 at atmospheric pressure and sealed inside. The temperature may be raised or lowered as desired to be used with the process 20 or the process 30, and carbon dioxide that is approximately the same temperature as the samples inside the vessel 50 may be introduced into the vessel 50 to avoid the damaging effects of thermal shock. Once the carbon dioxide has washed away all or most of any previous solvents, the pressure inside the vessel 50 may be increased to transition the carbon dioxide to a supercritical state and during simultaneous filling/draining when the carbon dioxide is continuously being injected into the vessel 50 at a pressure that is equal to or greater than the pressure inside the vessel 50, as stated above. This helps to reduce processing time because the vessel 50 maintains a relatively constant hydrostatic pressure throughout the vessel 50, which accelerates processing because the force of the injected carbon dioxide helps to purge the vessel 50 of any previous solvents.

Composites and methods for making composites

[0215] The current technology provides a composite material comprising a porous aerogel matrix and a plurality of reinforcing agents uniformly dispersed therein. The composite material has a reinforcing agent:aerogel matrix ratio of from greater than or equal to about 0.5:99.5 to less than or equal to about 99.5:0.5. The composite material may be used for any purpose known in the art, such as for a vehicle frame, a vehicle body, a vehicle body panel, a unibody, a casing, a housing,

[0216] The porous aerogel matrix is composed of any organic or inorganic material known in the art, such as, silica, metal and metalloid oxides, metal chalcogenides, metals, metalloids, amorphous carbon, graphitic carbon, diamond, discrete nanoscale objects, organic polymers, biopolymers, polyurea, a polyurethane, a polyisocyanate, a polyisocyanurate, a polyimide, a polyamide, a polybenzoxazine, a polyacrylonitrile, a polyetheretherketone, a polyetherketoneketone, a polybenzoxazole, a phenolic polymer, a resorcinol-formaldehyde polymer, a melamine-formaldehyde polymer, a resorcinol-melamine-formaldehyde polymer, a furfural-formaldehyde polymer, an acetic-acid-based polymer, a polymer-crosslinked oxide, a silica- polysaccharide polymer, a silica-pectin polymer, a polysaccharide, amorphous carbon, graphitic carbon, graphene, diamond, boron nitride, an alginate, a chitin, a chitosan, a pectin, a gelatin, a gelan, a gum, a cellulose, a virus, a biopolymer, an ormosil, an organic-inorganic hybrid material, a rubber, a polybutadiene, a poly(methylpentene), a polypentene, a polybutene, a polyethylene, a polypropylene, a carbon nanotube, a boron nitride nanotube, two-dimensional boron nitride, and combinations thereof as non-limiting examples. In some embodiments, suitable matrix materials may be reinforced with a fiber, a fibrous batting, aligned fibers, chopped fibers, or another suitable material. In some of these embodiments, the fiber comprises silica, glass, carbon, a polymer, poly(acrylonitrile), oxidized poly(acrylonitrile), poly(p-phenylene-2,6- benzobisoxazole) (e.g., ZYLON ^® polyoxazole manufactured by Toyobo Corp. (Japan) ), poly(paraphenylene terephthalamide) (e.g., KEVLAR ^® para-aramid manufactured by DuPont (Wilmington, DE) ), ultrahigh molecular weight polyethylene (e.g., SPECTRA ^® ultrahigh molecular weight polyethylene manufactured by Honeywell (Morris Plains, NJ) or DYNEEMA ^® ultrahigh molecular weight polyethylene manufactured by Royal DSM (Netherlands)), poly(hydroquinone diimidazopyridine) (e.g., M5), polyamide (e.g., NYLON ^® ), natural cellulose, synthetic cellulose, silk, viscose (e.g., rayon ), a biologically-derived fiber, a biologically-inspired fiber, a ceramic, alumina, silica, zirconia, yttria- stabilized zirconia, hafnia, boron, metal/metalloid carbide (e.g., silicon carbide), metal/metalloid nitride (e.g., boron nitride), nanotubes, carbon nanotubes, carbon nanofibers, boron nitride nanotubes, oxide nanotubes as non- limiting examples. Metalloids include boron, silicon, germanium, arsenic, antimony, tellurium, polonium and combinations thereof as non-limiting examples. Metals include lithium, sodium, potassium, rubidium, cesium, francium, beryllium, magnesium, calcium, strontium, barium, radium, aluminum, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, tin, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, thallium, lead, bismuth, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, lawrencium, the transactinide metals and combinations thereof as non- limiting examples. Discrete nanoscale objects include carbon nanotubes, boron nitride nanotubes, viruses, semiconducting quantum dots, graphene, and combinations thereof as non-limiting examples.

[0217] The reinforcing agents are fibers, particles, two-dimensional materials, or nanotubes and are composed of an aerogel, carbon, a polymer, a glass, a metal, or a combination thereof.

[0218] The composite material has a thermal conductivity of less than or equal to about 50 mW/m-K, less than or equal to about 40 mW/m-K, less than or equal to about 30 mW/m-K, less than or equal to about 25 mW/m-K, less than or equal to about 20 mW/m-K, or less than or equal to about 15 mW/m-K. The composite material has a compressive modulus of greater than or equal to about 1 GPa, greater than or equal to about 10 GPa, greater than or equal to about 25 GPa, greater than or equal to about 100 GPa, greater than or equal to about 300 GPa, or greater than or equal to about 500 GPa. The composite material has a density of greater than or equal to about 0.05 g/cm ³ to less than or equal to about 3.5 g/cm ³ . In some embodiments, the composite material is elecrrcially conductive and has a conductivity of from greater than or equal to 10 ^"3 ohms/sq and less than or equal to about 10 ¹² ohms/sq.

[0219] The composite material is made by a process according to the present technology. The process includes disposing a plurality of reinforcing agents into a first solvent to generate a first mixture. The first solvent can be any suitable solvent, such as acetone, acetonitrile, acetic acid, amyl alcohol, benzene, carbon tetrachloride, chlorobenzene, chloroform, cyclo-cresylic acid, hexane, isopropyl alcohol, N,N-dimethyl formamide, ethanol, ethyl acetate, furfural, furfuryl alcohol, methanol, n-butane, n- heptane, n-hexane, pyridine, and combinations thereof. The process also includes dissolving a polymer in a second solvent to generate a first solution. The second solvent can be 2-methoxyethanol, 2,6,10,14-tetramethyl pentadecane, acetone, acetonitrile, alcohols, amyl alcohol, amyl acetate, aniline, n-butanol, sec-butanol, tert- butanol, chlorex, cyclohexanol, C1 -C6 alcohols, cyclohexanone, cresylic acid, dimethylsulfoxide, N,N-dimethylacetamide, Ν,Ν-dimethylformamide, ethanol, furfural, furfuryl alcohol, n-propanol, pyridine, hexane, hexanes, n-hexane, hydrocarbons, isopropanol, methanol, methoxyethanol, N-methylpyrrolidone, nitrobenzene, pentanol, liquid SO2, quinolone, water, xylene, or a combination thereof. The polymer may be any polymer described herein, including polyesters (including polyethylene terephthalate (PET)), polyurethane, polyolefin, poly(acrylic acid) (PAA), poly(methyl acrylate) (PMA), epoxy, poly(methyl methacrylate) (PMMA), acrylonitrile butadiene styrene (ABS), polyimides, polyamides (including polycaprolactam (nylon)), polylactic acid (PLA), polybenzimidazole, polycarbonate, polyether sulfone (PES), polyetherether ketone (PEEK), polyetherimide (PEI), polyethylene (PE; including ultra-high molecular weight polyethylene (UHMWPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and cross-lined polyethylene (PEX)), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), co-polymers thereof, and combinations thereof.

[0220] The process then includes combining the first mixture with the first solution to generate a precursor material comprising the first solvent and the second solvent. The process comprises pouring the precursor material into a mold having a predetermined shape, and evaporating off at least a portion of at least one of the first solvent or the second solvent until the precursor material has a desired viscosity or consistency. In some embodiments, the evaporating is performed until the viscosity is such that the precursor material holds a shape. In other embodiments, the evaporating is performed, but the precursor material remains substantially fluidic.

[0221] The process then includes a step of either exchanging at least a portion of the remaining first and second solvents with CO2 or a third solvent miscible with CO ₂ wherein the polymer is insoluble in third solvent, or freezing the remaining first solvent and second solvent in the precursor material, and exchanging the first and second solvents with a the third solvent.

[0222] The process also includes drying the precursor material without exposing the precursor material to a liquid-gas interface to yield the composite material. Drying can be performed by any method described herein. [0223] A similar method for producing a composite material comprising a porous plastic matrix, a porous aerogel matrix, and a plurality of reinforcing agents uniformly dispersed therein is also provided. The method comprises disposing a plurality of reinforcing agents into a first solvent to generate a first mixture; dissolving a polymer in a second solvent to generate a first solution; disposing a plurality of aerogel matrix precursors into a third solvent to generate a second mixture, wherein the polymer is insoluble in the third solvent; combining the first mixture and the second mixture with the first solution to generate a precursor material comprising the first solvent, the second solvent, and the third solvent; transferring the precursor material into a mold having a predetermined shape; evaporating at least a portion of at least one of the first solvent, the second solvent, or the third solvent from the precursor material until the precursor material has a desired viscosity; performing at least one step selected from the group consisting of exchanging at least a portion of the remaining first, second, and third solvents with CO ₂ , and freezing the remaining first solvent, second solvent, and third solvent in the precursor material, and exchanging the first, second solvent, and third solvents with a fourth solvent; and drying the precursor material, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided. The third solvent can be 2-methoxyethanol, 2,6,10,14- tetramethyl pentadecane, acetone, acetonitrile, alcohols, amyl alcohol, amyl acetate, aniline, n-butanol, n-butanol, sec-butanol, tert-butanol, chlorex, cyclohexanol, C1 -C6 alcohols cyclohexanone, cresylic acid, dimethylsulfoxide, dimethylacetamide, dimethylformamide, ethanol, furfural, furfuryl alcohol, n-propanol , pyridine, hexane, hexanes, n-hexane, hydrocarbons, isopropanol, methanol, methoxyethanol, N- methylpyrrolidone, nitrobenzene, pentanol, liquid SO2, quinolone, water, xylene, or a combination thereof.

[0224] Fig. 7 is a flow diagram of a similar process 100 for synthesizing aerogel plastic composites. As used herein, an "aerogel" refers to a solid porous gel matrix, such as, for example, a sol gel, in which a liquid component within the solid porous gel matrix has been removed without exposing the solid porous gel matrix to a gas-liquid interface. At a Step 1 , a first container 1 12 is used to create aerogel microparticles 1 16 that are suspended in a suitable solvent 1 14, such as ethanol. At a Step 2, the solvent 1 14 of the container 1 12 is removed by washing such that the aerogel microparticles 1 16 are suspended in a dissolving solvent 1 18 that is capable of dissolving plastic. For example, the dissolving solvent 1 18 may be any solvent that is suitable, such as acetonitrile, dichloromethane, etc., or a combination thereof. Preferably, the dissolving solvent 1 18 has a lower boiling point than a dissolving solvent 124, described below.

[0225] In a second container 120 at a Step 3, a plastic material 122 is dissolved in the dissolving solvent 124 that may be the same or may be different from the dissolving solvent 1 18 used in the container 1 12. If the dissolving solvent 124 is different from the dissolving solvent 1 18, it is preferable that the dissolving solvent 124 be readily miscible with the dissolving solvent 1 18. For example, the solvent 124 may be acetonitrile.

[0226] At an Optional Step, a container 126 may be prepared that includes a filler 128, such as graphene, suspended in a filler solvent 130. The filler solvent 130 may be any solvent that is at least relatively miscible with the dissolving solvent 1 18 and the dissolving solvent 124, and that is capable of dissolving the plastic material 122 being used, e.g., the filler solvent 130 may be dichloromethane. At a Step 4, the contents from the container 1 12 and the contents of the container 120 (and optionally the contents of the container 126) are mixed together in a container 132 to mix the aerogel microparticles 1 16, the dissolved plastic material 122 (and optionally the filler 128) to predetermined ratios. Exemplary ratios include, but are not limited to 10/90% aerogel microparticles 90-10% plastic material. After an approximately uniform mixture is achieved, the container 132 is brought to a boil to boil off the dissolving solvent(s) 1 18, 124 (and optionally the solvent 130) until the consistency of the mixture is a slurry that is viscous enough to be cast into a mold 140 to create a molded sample 136 from the viscous slurry at a Step 5. Once the molded sample 136 is in the mold 140 at the Step 5, removal of the dissolving solvent(s) 1 18, 124 (and optionally the solvent 30) may continue via evaporation until a desired consistency is achieved at a Step 6. Once the desired consistency is achieved at the Step 6, any remaining solvent(s) 1 18, 124 (and optionally the solvent 130) in the molded sample 136 is/are exchanged with a solvent 138 that is miscible with liquid or supercritical carbon dioxide, a solvent that is capable of being replaced with or displaced with liquid or supercritical carbon dioxide, a solvent that is liquid or supercritical carbon dioxide, or a combination thereof, at a Step 7a.

[0227] In an alternate embodiment, instead of exchanging the remaining solvent(s) 1 18, 124 (and optionally 130) in the molded sample 136 with the solvent 138 at the Step 7a, the molded sample 136 may be exposed to a temperature that is below the freezing point of any of the dissolving solvent(s) 1 18, 124 (and optionally 130) that remain in the molded sample 136 at a Step 7b-1 , and after the molded sample 136 is frozen, solvent exchange may be carried out with the solvent 138 at a Step 7b-2. Preferably, the solvent 138 is a solvent that the plastic material 122 is insoluble with. Additionally, during the Step 7b-2 it may be necessary to keep the temperature of the solvent 138 below the freezing point of the solvent(s) 1 18, 124 (and optionally 130) that remains in the molded sample 136. The solvent exchange being carried out at the Step 7b-2 occurs successfully even though the molded sample 36 is frozen because the solvents 1 18, 124 in the frozen sample 136 are capable of being replaced or swept away by the solvent 138, which is miscible with the dissolving solvents 1 18 and 124. The frozen dissolving solvents 1 18 and 124 are dissolved by the cooled solvent 138 and the plastic material 122 is not because the plastic material 122 of the molded sample 136 is insoluble with the solvent 138, as stated above. Thus, the molded sample 136 retains the molded shape during the solvent exchange of the Step 7b-2.

[0228] After solvent exchange has replaced most or all of the solvent(s) 1 18, 124 (and optionally 130) with the solvent 138 at the Step 7a or the Step 7b-2, the molded sample 136 is dried via supercritical drying or ambient pressure carbon dioxide freeze drying as described above at a Step 8. Ambient pressure carbon dioxide freeze drying includes using liquid or supercritical carbon dioxide as the solvent 138 and freezing the molded sample 136 in the solvent 138 followed by drying in a low humidity environment at ambient pressure and a suitable temperature. The result at the Step 8 is a molded sample 136 that includes the aerogel microparticles 1 16 and plastic material 122 (and optionally the filler 128). The ratio of the aerogel microparticles 1 16 and the plastic material 122 (and optionally the filler 128) may be varied and may be such that the majority of a matrix of the molded sample 136 is comprised of the aerogel microparticles 1 16. The molded sample 136 may be used in lost foam or investing casting processes to form molten metal/metal oxides. For example, high temperature resistance aerogel microparticles such as silica, alumina, carbon, metal oxide, etc. that are highly dispersed in a plastic material (and optionally a filler, such as a few layer three-dimensional or two-dimensional graphene, graphene oxide, carbon nanotubes, can be dispersed in a third solvent, being similar or different from the first or second solvent, and incorporated to the the first and second solvent or a mixture therefor of etc.) and that are suitable for use with molten metal may be used such that when molten metal is introduced to the composite the molten metal replaces the plastic portions of the molded sample to create a composite that includes aerogel microparticles (and optionally the filler) that are dispersed throughout the metal, i.e., create a metal/aerogel microparticle (and optionally filler) composite. The final composite may need to have the remaining plastic burned out in a manner that is similar to lost wax casting.

[0229] The molded sample 136 using the process 100 described above is capable of producing highly dispersed aerogel microparticles 1 16 throughout the entirety of the molded sample 136. Further, if the filler material 128 has been included, the filler material 128 is also dispersed throughout the molded sample 136, and the filler material 128 may be functionalized such that the filler material 128 crosslinks with the aerogel microparticles 1 16 or the plastics 122 during the mixing and/or casting phase. Such crosslinking may be performed with or without the addition of a catalyst. For example, aerogel microparticles 1 16 that are decorated with amines and/or plastics such as poly lactic acid with diol groups can crosslink with fillers that are functionalized with reactive isocyanate groups.

[0230] The molded sample 136 may be utilized directly after drying, or the molded sample 136 may undergo further processing such that additional plastics are added. For example, the molded sample 136 may be placed in a different container or mold, and thereafter molten plastic may be introduced into the different container with the molded sample 136 and the final product may be removed before or after the additional molten plastic that was introduced has completely solidified to further reinforce the molded sample 136. For example, the molded sample 136 may be made from the aerogel microparticles 1 16 and the plastic material 122 that is poly styrene (PS) or poly lactic acid (PLA), which are well-suited templates for metal casting processes such as lost foam, lost wax and/or lost investment casting procedures. Although there are known methods for producing composites suitable for metal casting procedures and the like, these known processes are incapable of achieving dispersion of aerogel microparticles and/or fillers that are capable of producing final metal composites with relatively uniform dispersed phases. Those skilled in the art will recognize that the formation of known composites that are used in metal castings are formed through dry mixing, as stated above. It was found unexpectedly through the course of experimentation that the process 100 described above creates a composite with a plastic phase that remains ideal for such metal casting processes, and that retains a porous structure that can mimic a porous structure that is consistent with known foamed plastics. [0231] Furthermore, while some metal composites are known, achieving metal composites that contain high loading of contents of filler particles has remained a long standing challenge. Dispersing particles in metal is difficult due to the density discrepancy and high temperatures of molten metals. Furthermore, low density metals have further remained elusive. The combined thermal and density properties of aerogels make them an attractive solution for solving many of the long standing issues with metal composites, just as the incorporation of metals to aerogel materials are ideal for resolving many of the long standing issues regarding the know fragility of aerogel materials and composites. However due to the density discrepancy between aerogels and metals, synthesis of these composites has yet to be realized. One embodiment described herein pertains to the manufacturing of metal aerogel composites that can have high loading of up to at least about 80% v/v or at least about 90% v/v highly of dispersed aerogel particles and reinforcement materials.

[0232] In another embodiment of the method 100 described above, plastic may be added to the molded sample 136 when solid carbon dioxide is still present in pores of the molded sample 136 by using molten plastic to remove the solid carbon dioxide. Additional filler materials, such as graphene, graphene oxide, carbon nanotubes, cellulose nanocrystals as well as other two and three dimensional materials, may also be added and dispersed with the aerogel microparticles 1 16 of the molded sample 136 while the molded sample 136 is drying at the Step 8 via any suitable technique such as melt blending or other non-dissolved thermoplastic mixing techniques. For example, plastic may be injected into the molded sample 136 or may be cast onto the molded sample 136 while the molded sample 136 is drying. The molten plastic that is being added provides additional heat that accelerates and/or completes drying of the molded sample 136 to yield a composite of dried aerogel particles, plastics, and possibly fillers, that make up the molded sample 136. The dispersion of the aerogel microparticles 1 16, the plastic material 122 (and optionally the fillers 128) can be controlled through manual packing or arrangement of the aerogel microparticles 1 16 in the container 1 12 and/or the fillers 128 in the container 126 prior to mixing with the plastic material 122 of the container 120. This technique allows for a novel approach to control the final composition of the molded sample 136, particularly when the molded sample 136 is a thin film and the dispersion of the aerogel microparticles 1 16 are similar to that of lost foam, wax and/or an investment casting process that is typically used in metal casting. Just as the process of metal casting relies on the ability of molten metal to vaporize mediums used as a template, the process 100 described above utilizes the ability of plastics to vaporize solid carbon dioxide that is in and around the molded sample 36.

[0233] Alternatively, the aerogel microparticles 1 16 may be dried as described above, and the dried aerogel microparticles 1 16 may be added to a dissolved plastic by stirring, agitation, sheer mixing and/or ultrasonication, a melted plastic by stirring, agitation, sheer mixing and/or ultrasonication or to plastic microparticles by stirring, agitation, sheer mixing and/or ultrasonication. In yet another embodiment, aerogel microparticles 1 16 may be dried and thereafter mixed with dry ice, i.e., solid carbon dioxide, while still frozen in a dry ice matrix. For example, the dried aerogel microparticles 1 16 may be mixed with crushed dry ice (solid carbon dioxide) to form a "slurry" that does not include liquid. The mixture/slurry is cast or packed into a mold the same way that crushed ice with glitter may be packed into a cookie cutter/ice tray.

Examples

[0234] Embodiments of the present technology are further illustrated through the following non-limiting examples.

Example 1

[0235] A polyamide aerogel was synthesized using a solution of m- phenylenediamine (mPDA) (6.832 g, 63.20 mmol) in N-methylpyrrolidinone (NMP) (179.96 mL), which was cooled to 5 °C using an ice water bath. Terephthaloyl chloride (TPC) (12.44 g, 61 .14 mmol) was added in one portion as a solid and the cooled solution was allowed to stir for 25 minutes. 1 , 3, 5-benzenetricarbonyl trichloride (BTC) was added and the mixture was vigorously stirred for 5 minutes before being poured into four 20 mL cylindrical molds lined with Teflon and five small rectangular silicone molds. Gelation occurred within 5 minutes. After aging overnight at room temperature, the monolith samples were removed from the molds and placed in 500 mL jars of acetone. This was followed by seven solvent exchanges as 24 hour intervals to ensure that all of the NMP was removed from the gels. Upon successful solvent exchange, the samples were placed in a container of acetone and then into the vessel 50 described above. Once closed inside the vessel 50, the vessel 50 was partially filled with acetone using the solvent inlet line 62 to ensure that the samples were safely submerged in the acetone. Thereafter liquid carbon dioxide was added to the vessel 50 using the solvent inlet line 62 and draining and filling of the vessel 50 was performed as described above to flush the acetone from the container and samples therein. The shelf 82 was also filled with dry ice as described above. The draining and filling was performed at a proportional rate such that the vessel 50 was substantially filled throughout the filling and draining process, and was continued for 5-10 minutes at a time followed by rest periods of 1 -12 hours over the course of 72 hours. Importantly, during the process the samples were continuously submerged in a solvent in the container, i.e., were not exposed to a liquid/gas interface. After the acetone from the containers had been replaced with liquid carbon dioxide, liquid nitrogen was flowed through the coils 78 as described above to rapidly freeze the samples and the liquid carbon dioxide. After a sufficient amount of time has passed to allow for freezing of the liquid carbon dioxide in the containers, the containers are quickly removed so that the solid carbon dioxide does not transition to liquid. The vents 58 may be used to ensure that the pressure inside the vessel 50 remains below a point that allows for solid carbon dioxide to revert back to a liquid. For example, the pressure may be depressurized to approximately 1 atm before opening the door 54. The samples thereafter were dried at a temperature above -80 °C in a fume hood operating under low humidity conditions such as 0-30% humidity. Although optional, in this example heat was added by placing the samples in an oven at or above 160 °C to accelerate sublimation. A vacuum was not used, although this also is an option to speed up sublimation.

[0236] Figs. 8A and 8B show scanning electron microscopy (SEM) images of the polyamide aerogel of Example 1 above.

[0237] These SEM images show network preservation was achieved that is comparable to those produced through known methods of supercritical drying. SEM 1 .1 also clearly shows retention structures in the nanometer range, which is far smaller than the known minimum crystal size of carbon dioxide crystals (which is about 1 micron or roughly ten times the scale bar shown in the photos).

[0238] Fig. 9 shows Brunauer-Eimmett-Teller (BET) results for the polyamide aerogel of Example 1 .

[0239] The BET results clearly indicate the presence of microporous structures that are approximately 2 nm or smaller, indicating that the process described above dries the samples without damaging the structure of the samples.

Example 2 [0240] Placenta tissue samples in ethanol underwent solvent exchange with ethanol and a container with the placenta tissue in ethanol was placed in the vessel 50. Liquid carbon dioxide was introduced into the vessel and flooding and draining was carried out as described in Example 1 to displace the ethanol. Once most or all of the ethanol was removed from the samples, the samples were rapidly frozen as set forth above. The samples were thereafter removed from the vessel 50 and dried at ambient temperature and pressure overnight in a low humidity environment.

[0241] Figs. 10A-10D show SEM images of the placenta tissue samples of Example 2.

[0242] The SEM images show that the placenta tissue nano-porous structure is preserved and is smaller than 1 micron, indicating that the process described above provides a method for drying samples in a way that does not damage the porous structure, including the microporous structure. Example 3

[0243] The following describes an example for making aerogel microparticles and three exemplary options for mixing the aerogel microparticles with plastic material and processing the mixture to a final product. The example and the options described below are not intended to limit the scope of the application, as they are merely examples.

[0244] To make aerogel microparticles, 5 imL of methyltrimethoxysilane (MTMS), 0.05 g of hexadecyl trimethyl ammonium bromide (CTAB), and 15 mL of deionized water are mixed for twenty minutes under vigorous stirring until the solution is homogenous. Thereafter, ammonium hydroxide is added to the mixture and stirring is continued for several minutes using, for example, a stirring rate of 1000 rpm/minute. At a stirring rate of 1000 rpm/minute, the sol (aqueous phase) was poured into hexane (oil phase) at a volume ratio of 0.3 to form a water-in-oil (W/O) emulsion. Subsequently, droplets of the dispersed phase are formed under continuous stirring. After approximately 10 minutes, gelation of the dispersed phase took place, and stirring was stopped because the emulsion converted into a dispersion of spherical gel particles in the oil phase. Next, filtration and washing with acetonitrile were performed to isolate the gel microspheres from the emulsion system, as well as to remove the residual surfactant and chemicals. [0245] As an Option 1 for the plastic material, and in a container that is separate from the aerogel microparticles, 4 grams of polylactic acid (PLA) filament was dissolved in 50 imL of acetonitrile. The aerogel microparticles were then added to the mixture of the dissolved PLA/acetronitrile and mixed via ultrasonication, mechanical stirring, or high-shear mixing. Additionally (and optionally), 4 mg of graphene oxide nanoplates are added and dispersed via ultrasonication. After the mixture is homogenized, the suspension of aerogel microparticles, PLA, and graphene oxide are cast into a mold of a desired shape. Subsequent to casting, the mixture was rapidly frozen while still in the mold. After freezing the molded mixture is taken out of the mold while still frozen and placed into a dry ice/acetone bath, where the temperature of the bath is kept below the freezing point of acetonitrile, i.e., kept below approximately -45 °C). Acetone is miscible with acetonitrile and will dissolve the solid acetonitrile and eventually replace it. PLA, however, is insoluble in acetone and thus the shape of the mold is retained after acetonitrile is replaced by the acetone. Samples were then placed in a custom drying vessel, such as a vessel described herein, where liquid or supercritical carbon dioxide is used to replace the acetone in the molded mixture shortly before the molded mixture is frozen and sublimed.

[0246] As an option 2, in a container that is separate from the aerogel microparticles 4 grams of PLA filament are dissolved in 50 imL of dichloromethane. After being thoroughly washed in acetonitrile, the aerogel particles in the first container were diluted in 20 imL of acetonitrile and added to the mixture of dissolved PLA/dichloromethane and mixed via ultrasonication, mechanical stirring, or high-shear mixing. Additionally, 4 mg of graphene oxide nanoplates were dispersed therein via ultrasonication. After the mixture has homogenized, the suspension of aerogel microparticles, the PLA and the graphene oxide are cast into a mold of a desired shape. After being cast into the mold, the molded mixture is solidified by raising the temperature to slowly evaporate some of the dichloromethane, which has a lower boiling point than acetonitrile. Once solidified, the molded mixture is placed in a bath of pure acetone. Acetone is used because PLA is forced to precipitate. Once the acetone has replaced the acetonitrile/dichloromethane, the molded mixture is placed in the custom drying vessel described , such as a vessel described herein, where liquid or supercritical carbon dioxide is used to replace the acetone in and around the molded mixture. Thereafter, the molded mixture is frozen and sublimed as described herein. [0247] As an Option 3, 4 grams of PLA are dissolved in 50 imL of acetonitrile in a container that is separate from the aerogel microparticles. After being thoroughly washed in the acetonitrile, the aerogel microparticles described above are added to the container of the dissolved PLA in acetonitrile and mixed via ultrasonication, mechanical stirring, or high shear mixing. Additionally, 4 mg of graphene oxide nanoplates in 5 imL of a soluble solvent such as acetonitrile are dispersed into the container of the dissolved PLA and aerogel microparticles and dispersed via ultrasonication. The combined mixture is cast into a desired mold and heated to remove enough acetonitrile to cause solidification of the molded mixture. Once solidified, the molded mixture is placed in a bath of pure acetone. After replacing acetonitrile that is in and around the solidified molded mixture with acetone, the molded mixture is placed in a custom drying vessel and liquid or supercritical carbon dioxide is used to replace the acetone. Thereafter, the molded mixture and the liquid or supercritical carbon dioxide are frozen and sublimed, as set forth above.

[0248] After drying each of the molded mixtures as set forth in Options 1 -

3, the molded mixture may be utilized as is or may be refined further and added to other plastic materials at desired concentrations and utilized as a filler material.

Example 4

[0249] As shown in Figs. 1 1 -50, the current technology also provides the following systems, methods, and devices. System

[0251] The current technology provides a modular system 1006 for drying porous materials under high pressures.

[0252] With specific reference to Fig. 1 1 , the system 1006 can include at least one drying vessel (e.g., device 1010), at least one docking station or pumping station 1014, and at least one controller 1018 (best shown in Fig. 12). In the example provided, the system 1006 includes a plurality of the devices 1010, a first pumping station 1014a, a second pumping station 1014b, and a third pumping station 1014c, collectively and generally referred to herein as the pumping station(s) 1014. In the example provided, the second pumping station 1014b can be optional, as explained in greater detail below. Thus, in an alternative configuration, the system 1006 can be such that it includes the first pumping station 1014a and the third pumping station 1014c, without including the second pumping station 1014b.

[0253] The device 1010 can include a vessel assembly 1022 and a cart 1026. The vessel assembly 1022 and the cart 1026 are described in greater detail below, but in general, the vessel assembly 1022 can include an internal pressure chamber and a port that is configured to be coupled to a conduit from the pumping station 1014a, 1014b, or 1014c, for fluid communication therewith. The device 1010 can also include a pneumatic regulator configured to regulate the pressure within the vessel assembly 1022 and a temperature regulator configured to regulate the temperature within the vessel assembly 1022.

[0254] The pumping stations 1014 can include at least one source of drying material. The source of drying material can be, for example, at least one source of liquid, at least one source of SCO2, or a combination thereof. The source of drying material can have a port that is in fluid communication with a drying material conduit of the vessel assembly 1022.

[0255] The vessel assembly 1022 can be removably coupled to the pumping stations 1014 by removably coupling the drying material conduit to the port of the pumping station 1014. Therefore, the device 1010 can be in fluid communication with drying material in the pumping station 1014. The controller 1018 (best shown in Fig. 12) can be a controller (e.g., a processor) on the device 1010. In an alternative configuration, the controller can be located on the pumping stations 1014, remotely, or a combination of on the device 1010, on the pumping stations 1014, and/or remotely. Thus, the device 1010 can also be in controllable communication (e.g., electrical communication, or wireless communication) with the pumping station 1014 by a wire or wireless transmitters/receivers to transmit commands and/or data between the pumping station 1014 and the device 1010.

[0256] In the example provided, when the device 1010 is coupled to the first pumping station 1014a, the controller 1018 (best shown in Fig. 12) can send command signals to introduce a predetermined amount of drying material into the vessel assembly 1022. For example, the controller 1018 (best shown in Fig. 12) can open a valve and/or operate a pump to fill the inner pressure chamber of the vessel assembly 1022 with liquid CO2 or sCO2.

[0257] After the vessel assembly 1022 has been filled with the drying material at the first pumping station 1014a, the device 1010 may then be uncoupled from the first pumping station 1014a and moved away from the first pumping station 1014a. The device 1010 may then perform various operations apart from the first pumping station 1014a. For example, the controller 1018 (best shown in Fig. 12) can operate a heating or cooling system to control conditions within the vessel assembly 1022 and to run supercritical states operations such as those described herein. For example, the heating system can apply heat to the vessel assembly 1022. The first pumping station 1014a is also then available to receive a second one of the devices 1010. Through this configuration, any number of devices 1010 can be loaded with the drying material at the first pumping station 1014a and quickly disconnected and removed to then operate independently of the first pumping station 1014a, thus decreasing idle time of the pumping stations 1014 and devices 1010 and allowing for increased production capacity.

[0258] After the device 1010 has been disconnected from the first pumping station 1014a, the device 1010 can be optionally moved to the second pumping station 1014b and coupled for fluid communication to the second pumping station 1014b. At the second pumping station 1014b, the pressure chamber in the vessel assembly 1022 can be flushed with fresh drying material (e.g., liquid CO2 or sCO2). Flushing the device 1010 with fresh drying material can remove residual solvent from the chamber. After being flushed with fresh drying material, the device 1010 can be disconnected from the second pumping station 1014b.

[0259] After the device 1010 has been disconnected from the first pumping station 1014a, or the optional second pumping station 1014b, the device 1010 can be moved to the third pumping station 1014c and coupled for fluid communication with the third pumping station 1014c. At the third pumping station 1014c, the vessel assembly 1022 can be frozen (e.g., via the cooling system), depressurized, and then unloaded. At the third pumping station 1014c, the cooling system of the vessel assembly 1022 can receive cooling fluid (e.g., liquid nitrogen or liquid helium) from the third pumping station 1014c to freeze the drying material within the internal pressure chamber. After the cooling fluid is received from the third pumping station 1014c, the device 1010 can be disconnected from the third pumping station 1014c and can be depressurized and unloaded apart from the third pumping station 1014c. Thus, another one of the devices 1010 can be coupled to the third pumping station 1014c while the previous device is unloaded and the frozen product sublimates. The frozen product can sublimate separate from the device 1010 such that the device 1010 can be reloaded with new porous material to be dried while the previous frozen product sublimates.

Method

[0260] The current technology also provides a method for drying a porous material using a modular system, such as the modular system 1006. The method comprises transferring a porous material into a pressure chamber of a drying vessel, removably coupling the drying vessel to a pumping station, activating the pumping station to fill the pressure chamber with a drying material, and uncoupling the drying vessel from the pumping station.

[0261] When more than one porous material is to be dried, the method includes, transferring a second porous material into a second pressure chamber of a second drying vessel, removably coupling the second drying vessel to the pumping station after the first drying vessel is uncoupled from the pumping station, activating the pumping station to fill the second pressure chamber with a drying material, and uncoupling the second drying vessel from the pumping station.

[0262] When a drying vessel is uncoupled from the pumping station, it can perform various operations, such as regulating the temperature and pressure within the pressure chamber via a controller of the drying vessel. In this manner, a plurality of drying vessels can be filled with drying materials at the same pumping station and uncoupled from the pumping station to operate independently of each other.

Devices

[0263] The current technology also provides a drying vessel that is configured to be used with a drying system, such as the system described above. In general, the drying vessel is contrasted by coupling a first unit to a second unit with a connector. In various embodiments, the first unit has one of a male end or a female end and the second unit has the other of a male end or a female end. The connecter may be, for example, a union nut that couples and hermetically seals the first and second units together. The drying vessel includes ports that configured to quickly and removably receive a conduit. Such ports are referred to herein as "quick connect ports."

[0264] The current technology also provides a sleeve that is insertable into a drying vessel, such as the drying vessel provided herein. The sleeve includes a housing that defines a cylindrical hollow interior. An interior surface of the cylindrical housing includes threading. The sleeve also includes a cylindrical lining having threading on an outer surface. The threading of the cylindrical sleeve negatively corresponds to the threading of the housing, such that the cylindrical lining can be screwed into the housing.

[0265] The housing and lining both include ports that are configured to communicate with an external environment. For example, the ports can correspond to the quick connect ports of the drying vessel described above. Therefore, a drying material may be introduced into a hollow chamber defined by the lining by way of the ports.

[0266] The current technology also provides a shelving system. The shelving system includes a planar sheet having a top surface and a bottom surface. The sheet may be, for example, a mesh or grated sheet. The sheet is in communication with a cooling element. The cooling element can be, for example, a conduit or a coil. In some embodiments, the cooling element is disposed horizontally against the bottom surface of the sheet to define a coolable shelf. In other embodiment, the cooling element is disposed between two sheets to define a coolable shelf.

[0267] The cooling element includes a port that is configured to removably receive a conduit. At a first end, the conduit is in communication with an external environment, such as, for example, by way of the ports of the sleeve and drying vessel. [0268] In some embodiments, the shelving system includes conduit units that are configured to be easily and removably coupled to other conduit units. The conduit units also include quick connect ports that can be removably coupled to ports on the cooling element. The conduit unit can be removably coupled to a first shelf, and a second conduit unit can be removably coupled to the first conduit unit and to a second shelf. Accordingly, the shelfing system can be manipulated to include more or fewer shelves as needed.

[0269] When coupled to the cooling element, the conduit units are in fluid communication with the cooling element. Moreover, the shelving system is configured to fit within the pressure chamber of the drying vessel described herein, or within the hollow chamber of the sleeve described herein. Therefore, when the shelving system is transferred to the drying vessel, a cold liquid, such as liquid nitrogen or liquid helium, can be introduced through the conduit units and through the cooling element to thereby decrease the temperature within drying unit.

[0270] With specific reference to Figures 12-15, the device 1010 is illustrated in greater detail. The cart 1026 can include a base 1 1 10, and a support structure 1 1 14. In the example provided, the cart 1026 can also include the controller 1018, a separator tank or expansion tank 1 1 18, and a booster pump 1 122. The cart 1026 can also optionally include a CO2 container (not specifically shown) that can be configured to hold a volume of CO2 (e.g., LCO2 or sCO2) at pressure. The booster pump 1 122 can be any suitable pump configured to recompress non-super critical CO2 to sCO2. An inlet of the separator 1 1 18 can be in fluid communication with the bottom of the vessel assembly 1022 via a conduit. The separator 1 1 18 can be configured to separate CO2 from other materials, such as solvents flushed out from the vessel assembly 1022 with the CO2. The outlet of the separator 1 1 18 can be in fluid communication with the booster pump 1 122 to provide CO2 from the separator 1 1 18 to the booster pump 1 122. The booster pump 1 122 can be in fluid communication with the vessel assembly 1022, but proximate to the top of the vessel assembly 1022 to provide sCO2 back into the interior of the vessel assembly 1022. Thus, the booster pump 1 122 can operate to maintain the CO2 within the vessel assembly 1022 in the supercritical state. An in-line heating element and charging/discharging valve 1 124 can also be optionally connected between the compressor 1 122 and the vessel assembly 1022. The heating element and charging/discharging valve 1 124 can be configured to heat the sCO2 stream to raise the pressure of the sCO2 to a pressure above that inside the vessel assembly 1022. The controller 1018 can be configured to control operation of the booster pump 1 122 and/or the heating element and charging/discharging valve 1 124 as needed. The controller 1018, booster pump 1 122, and separator 1 1 18 can be fixedly mounted to the base 1 1 10 or the support structure 1 1 14.

[0271] The base 1 1 10 can support the rest of the device 1010 above the ground and for movement relative to the ground. In the example provided, the base 1 1 10 can include a plurality of wheels or casters 1 126 which can allow the device 1010 to roll from one location to another, such as between pumping stations 1014 (Fig. 1 1 ). In the example provided, the base 1 1 10 has a bottom aperture 1 130 through which various conduits and/or cords can extend.

[0272] The support structure 1 1 14 is a rigid structure that can include a first support 1 134 and a second support 1 138. The first and supports 1 134, 1 138 can be fixedly coupled to opposite sides of the base 1 1 10 to be spaced apart from each other to form an open space therebetween. The first and supports 1 134, 1 138 can extend up from the base 1 1 10 such that top members 1 142 of the first and supports 1 134, 1 138 are spaced apart from each other and the top members 1 142 are spaced apart from the base 1 1 10.

[0273] The vessel assembly 1022 can include at least one vessel unit 1 146, a top lid assembly 1 150, a bottom lid assembly 1 154, a frame structure 1 158, at least one insulating cover 1 162, a cooling system 1 166, and a heating system 1 170. The vessel assembly 1022 can include a plurality of the vessel units 1 146 coupled together to form one longitudinal interior chamber, as described in greater detail below. The vessel assembly 1022 is supported above the ground by the support structure 1 1 14 and is coupled to the support structure 1 1 14 for rotation relative thereto about a pivot axis 1 174 that extends through the top members 1 142 of the support structure 1 1 14. In the example provided, one of the vessel units 1 146 (e.g., at a center of the vessel assembly 1022) is fixedly coupled to a ring 1 178 that has a pair of pivot rods 1 182. The pivot rods 1 182 extend radially outward from diametrically opposite sides of the ring 1 178 and each pivot rod 1 182 is supported by one of the top members 1 142 of the support structure 1 1 14. The pivot rods 1 182 can be rotatably coupled to one of the top members 1 142 and/or rotatably coupled to the ring 1 178 such that the support structure 1 1 14 supports the vessel assembly 1022 above the ground and above the base 1 1 10 for rotation relative to the cart 1026 about the pivot axis 1 174. The vessel assembly 1022 is illustrated in a first or vertical position in Figures 12-15, in which a longitudinal axis of the vessel assembly 1022 is transverse (e.g., perpendicular) to the ground. The vessel assembly 1022 can be rotated about the pivot axis 1 174 to a second or horizontal position, as illustrated in Figure 16, wherein the longitudinal axis of the vessel assembly 1022 can be generally parallel to the ground.

[0274] With additional reference to Figures 17-19, each vessel unit 1 146 can be a generally hollow cylindrical body disposed about a longitudinal axis 1210 (i.e., the longitudinal axis of the vessel assembly 1022). Each vessel unit 1 146 can have a female portion 1214, a male portion 1218, a central portion 1222, and a nut 1226. The female portion 1214 and the male portion 1218 can be fixedly coupled together by the central portion 1222. The female portion 1214, male portion 1218, and central portion 1222 can have a central bore that defines an interior chamber 1230. The central portion 1222 can be a generally annular body that is fixedly (e.g., welded) to proximal ends of the male portion 1218 and the female portion 1214. The central portion 1222 can include a first inlet port 1234 and a first outlet port 1238 that extend through the central portion to be open to the interior chamber 1230 and the exterior of the vessel unit 1 146 to permit fluid communication therethrough. In the example provided, the central portion 1222 also includes a second inlet port 1242 and a second outlet port 1246 that extend through the central portion to be open to the interior chamber 1230 and the exterior of the vessel unit 1 146 to permit fluid communication therethrough.

[0275] Adjacent ones of the vessel units 1 146 can be positioned coaxially such that the male portion 1218 of one vessel unit 1 146 abuts the female portion 1214 of another vessel unit 1 146 and the two vessel units 1 146 are releasably coupled together by the nut 1226 so that the corresponding interior chambers 1230 are in fluid communication.

[0276] With specific reference to Figures 17 and 18, the male portion 1218 can include a cylindrical first outer surface 1250, a second outer surface 1254, and a convex surface 1258. The second outer surface 1254 is disposed between the cylindrical first outer surface 1250 and the convex surface 1258 and extends radially outward of the cylindrical first outer surface 1250 to form a shelf surface 1262. The convex surface 1258 can be frusto-conical or spherical for example.

[0277] The nut 1226 can have a generally cylindrical body 1266 disposed coaxial with the male portion 1218. In the example provided, the nut 1226 includes a plurality of nut protrusions 1270 that extend radially outward from the cylindrical body 1266. These nut protrusions 1270 can be configured to permit a user to easily rotate the nut 1226 about the longitudinal axis 1210 by a user's hands or a tool (not shown). In an alternative configuration, not specifically shown, the nut protrusions 1270 can be replaced with surfaces configured to be gripped by a tool (not shown), such as the exterior flat surfaces a traditional hex-nut, for example.

[0278] The nut 1226 can have a central bore that has a first diameter at one end and a plurality of internal threads 1274 at the opposite end. The first diameter can be greater than the diameter of the cylindrical first outer surface 1250, but less than the diameter of the second outer surface 1254. The outermost diameter of the internal threads 1274 can be greater than the diameter of the second outer surface 1254. Thus, the end of the nut 1226 with the first diameter can be disposed about the cylindrical first outer surface 1250 and the end of the nut 1226 with the internal threads 1274 can be disposed about the second outer surface 1254 and the convex surface 1258, such that an interior of the nut 1226 defines a mating shelf surface 1278 that can engage the shelf surface 1262 of the male portion 1218 to prevent axial movement of the nut 1226 in one direction, while permitting rotation of the nut 1226 about the longitudinal axis 1210. The internal threads 1274 can extend axially beyond the convex surface 1258.

[0279] The female portion 1214 can include a plurality of external threads 1282 and a concave surface 1286 (e.g., frusto-conical or spherical). The concave surface 1286 is configured to mate with and sealingly engage the convex surface 1258 of the male portion 1218. The external threads 1282 can be disposed coaxially about the concave surface 1286 and are configured to threadably engage the internal threads 1274 of the nut 1226. Thus, the concave surface 1286 can be coaxially aligned with the convex surface 1258 and the nut can threadably engage the external threads 1282 to draw the male portion 1218 and the female portion 1214 together until the concave surface 1286 forms a seal with the convex surface 1258. Thus, two or more of the vessel units 1 146 can be coupled together to form a single interior chamber capable of holding pressurized fluid. While only two vessel units 1 146 are illustrated as connected in Figures 12-16 and 19, three or more vessel units 1 146 can be connected in this manner to produce longer chambers.

[0280] In the configuration shown in Figure 19, examples of two types of lids are illustrated, e.g., a male lid 1288 and a female lid 1290. One end of the male lid 1288 can include the male portion 1218, while the other end of the male lid 1288 can be closed. One of the nuts 1226 can rotatably engage the male lid 1288 and threadably engage a terminal one of the female portions 1282 to cap the vessel unit 1 146 at the female portion 1282. One end of the male lid 1290 can include the female portion 1214, while the other end of the female lid 1290 can be closed. One of the nuts 1226 can rotatably engage a terminal one of the male portions 1218 and threadably engage the external threads 1282 of the female lid 1290 to cap the vessel unit 1 146 at the male portion 1218.

[0281] With additional reference to Figure 20, an alternative construction of the vessel units is illustrated. In the construction shown in Figure 20, the vessel assembly 1022 can include a male vessel unit 1310 and a female vessel unit 1314. The male vessel unit 1310 and the female vessel unit 1314 can be similar to the vessel units 1 146 (Figures 12-19), except as otherwise shown and described herein. The male vessel units 1310 can include two of the male portions 1218 fixedly coupled together by one of the central portions 1222. The female vessel unit 1314 can include two of the female portions 1214 fixedly coupled together by one of the central portions 1222. Similarly, the one of the nuts 1226 can connect one male portion 1218 of the male vessel unit 1310 to the female portion 1214 of one female vessel unit 1314, while another of the nuts 1226 can connect the other male portion 1218 to the female portion 1214 of another female vessel unit 1314. Additional male vessel units 1310 and female vessel units 1314 can be coupled together to produce longer chambers. In an alternative construction, not specifically shown, the male vessel units 1310 and/or the female vessel units 1314 can be coupled to the vessel units 1 146 (Figures 12-16) in any suitable combination to produce a vessel assembly 1022 of a desired length and configuration.

[0282] With additional reference to Figures 21 -24, the female portion 1214 and the male portion 1218 can each further include a sleeve assembly 1410 and a shelf assembly 1414. The sleeve assembly 1410 can include an outer sleeve 1418 and an inner sleeve 1422. The outer sleeve 1418 can be a hollow cylindrical body having a plurality of external threads 1424 on the outer surface of the outer sleeve 1418. The external threads 1424 can be configured to threadably engage with a plurality of internal threads 1426 disposed about the interior of the female portion 1214 or the interior of the male portion 1218. Thus, the outer sleeve 1418 can be threadably received within the central bore of the interior chamber 1230. An internal surface of the outer sleeve 1418 can define a plurality of slots 1430 (shown in Figures 23 and 24) that extend longitudinally parallel to the longitudinal axis 1210. The outer sleeve 1418 can include a pair of apertures 1434. Each aperture 1434 can align with one of the ports 1234, 1238, 1242, 1246.

[0283] The inner sleeve 1422 can be a hollow cylindrical body having an external surface that defines a plurality of tracks 1438 or splines (shown in Figures 23 and 24). The tracks 1438 can slidably fit within the slots 1430 such that the inner sleeve 1422 can slide axially into the outer sleeve 1418 while being constrained from rotating relative to the outer sleeve 1418. The slots 1430 and tracks 1438 can have a generally loose slip fit, such that thermal expansion/contraction of the inner sleeve 1422 and the outer sleeve 1418 does not inhibit the axially sliding of the inner sleeve 1422 across a wide range of temperatures including those experienced during exposure to LCO2, sCO2, or the freezing of the product as described herein. The inner sleeve 1422 can include a pair of apertures 1442. Each aperture 1442 can align with one of the apertures 1434 of the outer sleeve 1418. In an alternative construction, not specifically shown, the outer sleeve 1418 can have a plurality of internal splines that extend radially inward to mate with matching spline features on the inner sleeve 1422.

[0284] The cylindrical body of the female portion 1214, the male portion 1218, and the central portion 1222 can be formed of a first material, such as steel for example, while the inner sleeve 1422 can be formed of a different material, such as stainless steel for example. The outer sleeve 1418 can also be formed of stainless steel, though other materials can be used.

[0285] The shelf assembly 1414 can be received within the inner sleeve 1422. With additional reference to Figures 25-28, the shelf assembly 1414 can include a plurality of shelves 1510, and a shelf cooling tube assembly 1514. The shelves 1510 can be generally disc-shaped. In the example provided, five shelves 1510 are illustrated, though more or fewer shelves can be used. The shelves 1510 can be formed of a porous material, such as a wire mesh for example. Each shelf 1510 can have a top disc 1518 for supporting the product to be dried. The shelf cooling tube assembly 1514 can include an inlet 1522, an outlet 1526, a plurality of connecting tubes 1530, and a cooling coil 1534 (e.g., a section of tubing that follows a serpentine path below each shelf 1510). In the example provided, each shelf 1510 can also include a bottom disc 1538 to provide separation between the product to be dried on a lower shelf 1510 and the cooling coil 1534 above it.

[0286] The inlet 1522 can align with one of the ports 1234, 1238, 1242, 1246. The outlet 1526 can align with another one of the ports 1234, 1238, 1242, 1246. The inlet 1522, outlet 1526, and ports 1234, 1238, 1242, 1246 can be quick disconnect type couplings such that the inlet 1522 and outlet 1526 can easily snap or otherwise connect in a sealed configuration with the corresponding port 1234, 1238, 1242, 1246 to permit fluid communication between the ports 1234, 1238, 1242, 1246 and the shelf cooling tube assembly 1514. In the example provided, the inlet 1522 can be connected for fluid communication with an inlet of the cooling coil 1534 of the top one of the shelves 1510. The outlet of the cooling coil 1534 can be connected to one of the connecting tubes 1530 that couples the top cooling coil 1534 for fluid communication with the inlet of the next highest cooling coil 1534, and so on, until the lowest cooling coil 1534 of the shelf assembly 1414. The outlet of the lowest cooling coil 1534 can be connected to the outlet 1526 for fluid communication therewith.

[0287] In the example provided, quick disconnect type couplings can be used to connect the inlet 1522, outlet 1526, connecting tubes 1530, and cooling coils 1534, in order to provide ease of assembly and modularity of the shelf assembly 1414. Thus, a cooling fluid (e.g., liquid nitrogen or liquid helium) can be flowed through the ports 1234, 1238, 1242, 1246 and through the shelf cooling tube assembly 1514 to cool the sCO2 and product within the interior chamber 1230.

[0288] In the example provided, the inner sleeves 1422 of adjacent female portions 1214 and male portions 1218 can abut each other when fully assembled such that the adjacent inner sleeves 1422 can seal together to form a continuous inner sleeve. Thus, the inner sleeves 1422 can form a barrier (e.g., stainless steel) between the contents of the vessel units 1 146 (e.g., sCO2) and the outer sleeve 1418, and the interiors of the male or female portions 1214 or 1218 so that the interior of the vessel units 1 146 can be a sterile environment.

[0289] With additional reference to Figures 46 and 47, a perspective sectional view of a portion of a vessel unit 4610 of a different configuration is illustrated. The vessel unit 4610 can be similar to the vessel unit 1 146, except as otherwise shown or described herein. The vessel unit 4610 can include a male portion 4614 a female portion 4618 and a nut (e.g., nut 1226). In the example provided, the male portion 4614 includes a flat face 4622 and a convex face 4626, while the female portion 4618 can include a flat face 4630 and a concave face 4634. When fully assembled, the flat faces 4622 and 4630 can abut and form a seal together and/or the convex and concave faces 4626 and 4634 can contact and form a seal together. Alternatively, the male and female portions 4614, 4618 can be configured similar to the male and female portions 1218, 1222 described above.

[0290] The male portion 4614 can have an inner sleeve 4638 that can be similar to the inner sleeve 1422, except as otherwise shown or described herein. The female portion 4618 can also have an inner sleeve 4642 that can be similar to the inner sleeve 1422, except as otherwise shown or described herein. The inner sleeve 4638 of the female portion 4618 can have a terminal end face 4646 that can be recessed axially from the flat face 4622. The inner sleeve 4642 of the female portion 4618 can have a terminal end face 4650 that can be axially extended from the flat face 4630. When the male and female portions 4614, 4618 are fully assembled, the terminal end face 4650 can extend axially within the male portion 4614 and can abut and seal with the terminal end face 4646. Thus, the terminal end faces 4646, 4650 can contact at a location axially within the male portion 4614 to form a continuous barrier of the inner sleeves 4638, 4842.

[0291] In an alternative configuration, not specifically shown, the terminal end face 4650 of the female portion 4618 can be recessed axially from the flat face 4630 and the terminal end face 4646 of the male portion 4614 can be axially extended from the flat face 4622. When the male and female portions 4614, 4618 are fully assembled, the terminal end face 4646 can extend axially within the female portion 4618 and can abut and seal with the terminal end face 4650. Thus, the terminal end faces 4646, 4650 can contact at a location axially within the female portion 4618 to form a continuous barrier of the inner sleeves 4638, 4842.

[0292] With additional reference to Figure 48, a perspective sectional view of a portion of a vessel unit 4810 of a different configuration is illustrated. The vessel unit 4810 can be similar to the vessel unit 4610, except as otherwise shown or described herein. The vessel unit 4810 can include a male portion 4814, a female portion 4818 and a nut (e.g., nut 1226). In the example provided, the male portion 4814 includes a flat face 4822 and a convex face 4826, while the female portion 4818 can include a flat face 4830 and a concave face 4834. When fully assembled, the flat faces 4822 and 4830 can abut and form a seal together and/or the convex and concave faces 4826 and 4834 can contact and form a seal together. Alternatively, the male and female portions 4814, 4818 can be configured similar to the male and female portions 1218, 1222 described above. [0293] The male portion 4814 can have an inner sleeve 4838 that can be similar to the inner sleeve 4638 except as otherwise shown or described herein. The female portion 4818 can also have an inner sleeve 4842 that can be similar to the inner sleeve 4642, except as otherwise shown or described herein. The inner sleeve 4838 of the male portion 4814 can have a terminal end face 4846 that can be recessed axially from the flat face 4822. The inner sleeve 4842 of the female portion 4818 can have a terminal end face 4850 that can be axially extended from the flat face 4830. In the example provided, a seal member 4852 can be disposed axially between the terminal end faces 4846, 4850 to form a seal between the inner sleeves 4838, 4842. In the example provided, the seal member 4852 can be coupled to the terminal end face 4846, and disposed axially between the terminal end face 4846 and the flat face 4822. Alternatively, the seal member 4852 can be coupled to the terminal end face 4850. When the male and female portions 4814, 4818 are fully assembled, the terminal end face 4850 can extend axially within the male portion 4814 and can abut and seal with the seal member 4852, which seals with the terminal end face 4846. Thus, a continuous barrier of the inner sleeves 4838, 4842 can exist.

[0294] In an alternative configuration, not specifically shown, the terminal end face 4850 of the female portion 4818 can be recessed axially from the flat face 4830 and the terminal end face 4846 of the male portion 4814 can be axially extended from the flat face 4822. When the male and female portions 4814, 4818 are fully assembled, the terminal end face 4846 can extend axially within the female portion 4818 and can abut and seal with the terminal end face 4850. Thus, the terminal end faces 4846, 4850 can contact at a location axially within the female portion 4818 to form a continuous barrier of the inner sleeves 4838, 4842.

[0295] With additional reference to Figure 49, a perspective sectional view of a portion of a vessel unit 4910 of a different configuration is illustrated. The vessel unit 4910 can be similar to the vessel unit 4610, except as otherwise shown or described herein. The vessel unit 4910 can include a male portion 4914, a female portion 4918 and a nut (e.g., nut 1226). In the example provided, the male portion 4914 includes a flat face 4922 and a convex face 4926, while the female portion 4918 can include a flat face 4930 and a concave face 4934. When fully assembled, the flat faces 4922 and 4930 can abut and form a seal together and/or the convex and concave faces 4926 and 4934 can contact and form a seal together. Alternatively, the male and female portions 4914, 4918 can be configured similar to the male and female portions 1218, 1222 described above.

[0296] The male portion 4914 can have an inner sleeve 4938 that can be similar to the inner sleeve 4638 except as otherwise shown or described herein. The female portion 4918 can also have an inner sleeve 4942 that can be similar to the inner sleeve 4642, except as otherwise shown or described herein. The inner sleeve 4942 of the female portion 4918 can have a terminal end face 4950 that can be recessed axially from the flat face 4930. The inner sleeve 4938 of the male portion 4914 can have a terminal end face 4946 that can be axially extended from the flat face 4926. The inner sleeve 4938 can have a boss or groove 4954 about the outer circumference of the inner sleeve 4938 at the portion that is axially outward of the flat face 4922. In other words, the inner sleeve 4938 can have an outermost diameter that is reduced at the portion that extends axially from the male portion 4914.

[0297] In the example provided, a seal member 4952 can be disposed about the groove 4954 and be received in the groove 4954. The seal member 4952 can be a compressible or resilient material (e.g., rubber or polymer) that can have an uncompressed outermost diameter that can be greater than an inner diameter of the female portion 4918 where the inner sleeve 4942 is recessed. In the example provided, the seal member 4952 can have an un-expanded innermost diameter that can be less than or equal to an outermost diameter of the boss or groove 4954 such that the seal member 4952 can be retained on the boss or groove 4954 by the radial resilience of the seal member 4954. When the male and female portions 4914, 4918 are fully assembled, the terminal end face 4946 can extend axially within the female portion 4918 and can abut the terminal end face 4950. The seal member 4952 can seal with the inner diameter of the female portion 4918 at the recess. The seal member 4952 can also be configured to abut against the terminal end face 4950 to form a seal therewith. Thus, a continuous barrier of the inner sleeves 4838, 4842 can exist. The seal member can also aid in assembly of the male and female portions 4914, 4918 by resisting relative rotation between the male and female portions 4914, 4918 when tightening the nut (e.g., nut 1226).

[0298] In an alternative configuration, not specifically shown, the terminal end face 4946 of the male portion 4914 can be recessed axially from the flat face 4922 and the terminal end face 4950 of the female portion 4918 can be axially extended from the flat face 4930. When the male and female portions 4914, 4918 are fully assembled, the terminal end face 4950 can extend axially within the male portion 4914 and can abut and the terminal end face 4946 and the seal member 4952 can be disposed about a boss or groove (similar to the boss or groove 4954) around the inner sleeve 4942 and seal with the inner circumference of the male portion 4914 at the recess. Thus, the terminal end faces 4946, 4950 can contact at a location axially within the male portion 4914 to form a continuous barrier of the inner sleeves 4938, 4942.

[0299] With additional reference to Figure 50, a perspective sectional view of a portion of a vessel unit 5010 of a different configuration is illustrated. The vessel unit 5010 can be similar to the vessel units 4610, 4810, 4910 except as otherwise shown or described herein. The vessel unit 5010 can include a male portion 5014, a female portion 5018 and a nut (e.g., nut 1226). In the example provided, the male portion 5014 includes a flat face 5022 and a convex face 5026, while the female portion 5018 can include a flat face 5030 and a concave face 5034. When fully assembled, the flat faces 5022 and 5030 can abut and form a seal together and/or the convex and concave faces 5026 and 5034 can contact and form a seal together. Alternatively, the male and female portions 5014, 5018 can be configured similar to the male and female portions 1218, 1222 described above.

[0300] The male portion 5014 can have an inner sleeve 5038 that can be similar to the inner sleeves 4638, 4838, 4938 except as otherwise shown or described herein. The female portion 5018 can also have an inner sleeve 5042 that can be similar to the inner sleeves 4642, 4842, 4942 except as otherwise shown or described herein. The inner sleeve 5042 of the female portion 5018 can have a terminal end face 5050 that can be recessed axially from the flat face 5030. The inner sleeve 5038 of the male portion 5014 can have a terminal end face 5046 that can be axially extended from the flat face 5026. The inner sleeve 5038 can have a boss or groove 5054 about the outer circumference of the inner sleeve 5038 at the portion that is axially outward of the flat face 5022. In other words, the inner sleeve 5038 can have an outermost diameter that is reduced at the portion that extends axially from the male portion 5014.

[0301] In the example provided, a seal member 5052 can be disposed about the groove 5054 and be received in the groove 5054. The seal member 5052 can be a compressible or resilient material (e.g., rubber or polymer) that can have an uncompressed outermost diameter that can be greater than an inner diameter of the female portion 5018 where the inner sleeve 5042 is recessed. In the example provided, the seal member 5052 can have an un-expanded innermost diameter that can be less than or equal to an outermost diameter of the boss or groove 5054 such that the seal member 5052 can be retained on the boss or groove 5054 by the radial resilience of the seal member 5054. The seal member 5054 can also include a portion that extends axially outward of the terminal end face 5046 and overlap radially with the terminal end face 5046. In the example provided the seal member 5054 has an innermost diameter that is approximately equal to the innermost diameter of the inner sleeve 5038. When the male and female portions 5014, 5018 are fully assembled, the terminal end face 5046 can extend axially within the female portion 5018 and can compress the seal member 5054 against the terminal end face 5050 to form a seal therebetween. The seal member 5052 can also seal with the inner diameter of the female portion 5018 at the recess. Thus, a continuous barrier of the inner sleeves 5038, 5042 can exist. The seal member can also aid in assembly of the male and female portions 5014, 5018 by resisting relative rotation between the male and female portions 5014, 5018 when tightening the nut (e.g., nut 1226).

[0302] In an alternative configuration, not specifically shown, the terminal end face 5046 of the male portion 5014 can be recessed axially from the flat face 5022 and the terminal end face 5050 of the female portion 5018 can be axially extended from the flat face 5030. When the male and female portions 5014, 5018 are fully assembled, the terminal end face 5050 can extend axially within the male portion 5014 and can compress the seal member against the terminal end face 5046 and the seal member 5052 can be disposed about a boss or groove (similar to the boss or groove 5054) around the inner sleeve 5042 and seal with the inner circumference of the male portion 5014 at the recess. Thus, a continuous barrier of the inner sleeves 5038, 5042 can be formed.

[0303] While the embodiments shown in Figures 46-50 illustrate the inner sleeves 4642, 4646, 4842, 4846, 4942, 4946, 5042, 5046 as directly connected to the male or female portions 4614, 4618, 4814, 4818, 4914, 4918, 5014, 5018, the an outer sleeve can be disposed between the inner sleeves and the female portions, similar to the outer sleeve 1422 (Figures 21 -24).

[0304] Returning to Figures 12-16, the frame structure 1 158 can include a plurality of securement rods 1610. When the vessel units 1 146 are assembled, the nut protrusions 1270 can be configured to be aligned. Each securement rod 1610 can then be fixedly and removably coupled to aligned nut protrusions 1270 and extend axially between the aligned nut protrusions 1270 to prevent relative rotation of the nuts 1226. In the example provided, each securement rod 1610 extends through bores in each aligned nut protrusion 1270 and is fixed axially in place by nuts that thread onto the securement rods 1610 and engage the nut protrusions 1270, though other configurations can be used.

[0305] Returning to Figure 19, each of the nut protrusions 1270 can also include a bore 1272 that extends radially inward relative to the longitudinal axis 1210. The axes (not shown) of the bores 1272 can be perpendicular to the longitudinal axis 1210. Each bore 1272 can include a plurality of interior threads. These bores 1272 permit rods (not specifically shown) with mating threads to be threaded into the bores 1272 in order to provide additional leverage when turning the nut 1226. Furthermore, hot fluid or gas can be pumped through the bores 1272 to heat the nut 1226 to a different temperature than the rest of the vessel unit 1 146. This differential heating can help free up the nut 1226 after the freezing processes to assist in turning the nut 1226 without heating the entire vessel unit 1 146. These bores 1272 can further be used to thread in attachment members (not specifically shown, e.g., threaded lunette rings or hooks) configured to permit the vessel unit 1 146 to be lifted by these attachment members. One of the bores 1272 on one nut 1226 can also be connected by pipe or rod (not specifically shown) to permit two of the nuts 1226 to be rotated at the same time.

[0306] With additional reference to Figures 29-32, the cooling system 1 166 and heating system 1 170 are illustrated in greater detail. Figure 29 illustrates the vessel assembly 1022 with the insulating cover or cover 1 162 partially cut away to more clearly show the cooling system 1 166 and heating system 1 170. Figure 30 illustrates the male portion 1218 of one of the vessel units 1 146 with the insulating cover exploded away to more clearly show the cooling system 1 166 and the heating system 1 170. Figure 31 illustrates the female portion 1214 of one of the vessel units 1 146 with the insulating cover 1 162 removed to more clearly show the cooling system 1 166 and the heating system 1 170.

[0307] The cooling system 1 166 can generally include a cooling coil 1714 that is a tube or conduit has an inlet 1718 and an outlet 1722 and coils around the vessel units 1 146. In the example provided, each male portion 1218 and female portion 1214 has its own cooling system 1 166, though other configurations can be used. The cooling coil 1714 can coil around the corresponding male portion 1218 or female portion 1214 between the outer cylindrical surface of the male or female portion 1218, 1214 (e.g., surface 1250) and the insulating cover 1 162. The cooling inlet 1718 can extend through an aperture in the insulating cover 1 162 and be configured to be in fluid communication with a cooling fluid supply (e.g., liquid nitrogen or liquid helium), such as at the third pumping station 1014c for example. The cooling outlet 1722 can be external to the insulating cover 1 162 and can be selectively opened to the atmosphere via a valve 1726. The valve 1726 can be controlled by the controller 1018. Thus, the cooling fluid can flow through the cooling coil and be flashed to the atmosphere to cool the vessel unit 1 146.

[0308] In an alternative construction, the cooling outlet 1722 can be internal to the insulating cover 1 162 and can be selectively opened to the space between the insulating cover 1 162 and the vessel unit 1 146. Thus, the cooling fluid can flow through the cooling coil 1714 and be flashed to the space between the vessel unit 1 146 and the insulating cover 1 162 to cool the vessel unit 1 146 and effectively create a Dewar's Flask system. In an alternative configuration, the valve 1726 is 3-way or other valve configured to be operable in a closed mode, a first open mode, and a second open mode. In the closed mode, the valve 1726 is closed to prevent flow of fluid therethrough. In the first open mode, the valve 1726 can be open to the space between the vessel unit 1 146 and the insulating cover 1 162 to flash the cooling fluid thereto. In the second open mode, the valve 1726 can be open to the atmosphere exterior of the insulating cover 1 162 to flash the cooling fluid thereto.

[0309] In the configurations described above where the cooling fluid is flashed to the space between the vessel unit 1 146 and the insulating cover 1 162, the cooling fluid can fill the space therebetween and then be vented to the atmosphere exterior of the insulating cover 1 162, such as through a vent. Alternatively, the cooling fluid can be recovered from the space between the vessel unit 1 146 and the insulating cover 1 162 by a recovery conduit to be re-used by the cooling fluid supply (e.g., the third pumping station 1014c).

[0310] The heating system 1 170 can include a heating element 1730 disposed between the insulating cover 1 162 and the vessel unit 1 146. In the example provided, the heating element 1730 is an electric resistance element (e.g., heating tape or pad). The heating element 1730 can be wrapped around the vessel unit 1 146, such as in direct contact with the outer surface of the vessel unit 1 146, or can be wrapped around and in direct contact with the cooling coil 1714, though other configurations can be used. The heating system 1 170 can be controlled by the controller 1018. [0311] With additional reference to Figures 33 and 34, the bottom lid assembly 1 154 is illustrated in greater detail. The bottom lid assembly 1 154 can be generally configured to seal the bottom of the interior chamber 1230. The bottom lid assembly 1 154 can include a mating portion 1810, a bottom plug 1814. In the example provided, the bottom lid assembly 1 154 also includes a mixing device 1822 and an ultrasonic transducer 1818, though these elements can be optional. A proximal end 1826 of the mating portion 1810 can be similar to the male portion 1218 or the female portion 1214, depending on the configuration of the lowest one of the vessel units 1 146, and can sealingly connect to the lowest one of the vessel units 1 146. In the example provided, the proximal end 1826 of the mating portion 1810 is similar to the female portion 1214. A distal end 1830 of the mating portion 1810 can be a cylindrical body configured to be closed or capped by the bottom plug 1814. In the example provided, the interior of the distal end 1830 is threaded and the bottom plug 1814 has mating threads such that the bottom plug 1814 is sealingly threaded into the mating portion 1810.

[0312] The bottom plug 1814 can include an outlet port 1834 that can be open to the interior chamber 1230 and can be in fluid communication with a valve 1838. The valve 1838 can be operable in a closed mode, a first open mode, and a second open mode. In the closed mode, the valve 1838 can prevent fluid from exiting the interior chamber 1230 through the outlet port 1834. In the first open mode, the valve 1838 can permit fluid communication from the outlet port 1834 to the inlet of the booster pump 1 122. In the second open mode, the valve 1838 can permit fluid communication from the outlet port 1834 to the atmosphere, or to a recovery device (e.g. at one of the pumping stations 1014). The bottom plug 1814 can also include one or more sealed ports 1842 through which electrical power can be supplied to the mixing device 1822 and/or the ultrasonic transducer 1818.

[0313] In the example provided, the mixing device 1822 can include a motor 1846 disposed within the interior chamber 1230 and coupled to a stirring member (not shown) within the interior chamber 1230. The motor 1846 can be an electric motor. The motor 1846 can be a supercritical CO2 submersible motor. For example, the motor 1846 can use bearings that are capable of being lubricated by sCO2, such as self- lubricated bearings, journals, gas lubricated bearings, and/or oil free bearings for example, since traditional motors (e.g., with oil lubricated bearings) would be incompatible with sCO2 because sCO2 increases diffusivity and can act as a solvent of the oils. This configuration can reduce costs by eliminating expensive shaft seals that otherwise would seal rotary shafts that extend through the vessel. Without such seals, the maximum stirring rpm and pressure in the interior chamber 1230 can be higher, and the expected lifespan can be extended. The rotor or stator of the motor 1846 can optionally have encapsulated, potted, lamented, or coated windings. The motor 1846 can also optionally include a protective membrane or filter 1848 that permits CO2 to enter the interior of the motor 1826, while inhibiting particulates or solutes contained by or carried by the sCO2 from entering the interior of the motor 1826 and contacting the core motor elements. Such a membrane or filter 1828 can be either a porous or non- porous material. Thus, only the sCO2 is allowed contact with the core elements of the motor 1846 and the sCO2 can lubricate those core elements of the motor 1846.

[0314] Furthermore, since the motor 1846 can be located within the interior chamber 1230, extended drive shafts are not needed, which can reduce the power requirements of the motor 1846. Since the motor 1846 utilizes oil-free bearings, and sCO2 is generally inert, the motor 1846 can be disposed within the interior chamber 1230 without being sealed within a motor housing, such that the motor elements (stator/rotor/bearings/etc.) can be in direct contact with the sCO2. Being in direct contact with the sCO2 can also help cool the motor 1846 during operation. While described as being an electrically powered motor, the motor 1846 could alternatively be pneumatically powered, so long as the motor 1846 utilizes oil-free bearings as described above.

[0315] Alternatively, the mixing device 1822 can include a magnetic stirrer within the interior chamber 1230 to stir the LCO2 or sCO2, that is caused to rotate by a motor located external to the interior chamber 1230. The ultrasonic transducer 1818 can be configured to detect conditions within the interior chamber 1230.

[0316] With additional reference to Figure 35 and 36, the top lid assembly 1 150 can be generally configured to close and seal the top of the interior chamber 1230 (i.e., at an uppermost one of the vessel units) and to be easily removable in order to unseal and open the top of the interior chamber 1230 to remove the frozen product. The top lid assembly 1 150 can include an upper plug 1850, a support frame 1854, and a plurality of securement rings 1858. The upper plug 1850 can be configured to fit within the open end of the top of the interior chamber 1230 (i.e., at the uppermost one of the vessel units 1 146) and can be configured to form a seal with the vessel unit 1 146 to seal the interior chamber 1230. The upper plug 1850 can be configured to slide relative to the vessel unit 1 146 along the longitudinal axis of the vessel unit 1 146, or to threadably engage a top one of the nuts 1226. An inlet 1862, pressure relief vent 1866, and a pressure gage 1870 (shown in Figures 12-14) can be coupled to the upper plug 1850 to be in fluid communication with the interior chamber 1230.

[0317] The support frame 1854 can have a top portion 1874, a pair of frame rails 1878, an upper bracket 1882, and a lower bracket 1886. A first side of the top portion 1874 can overlap with the top of the upper plug 1850 and can be fixedly coupled to the top of the upper plug 1850. A second side of the top portion 1874 can be fixedly coupled to the frame rails 1878. The frame rails 1878 can be fixedly coupled to middle portions of the upper and lower brackets 1882, 1886. Opposite ends of the upper bracket 1882 can include upper apertures 1890. Opposite ends of the lower bracket 1886 can include lower apertures 1894. One of the securement rods 1610 can be slidably received through one of the upper apertures 1890 and one of the lower apertures 1894, while another one of the securement rods 1610 can be slidably received through the other one of the upper apertures 1890 and the other one of the lower apertures 1894.

[0318] The securement rings 1858 can have internal threads that can threadably engage external threads on the securement rods 1610. In the example provided, there are four securement rings 1858, each one corresponding to one of the upper or lower apertures 1890, 1894 of the upper or lower brackets 1882, 1886. The securement rings 1858 can support the upper and lower brackets 1882, 1886. When the securement rings 1858 are rotated, they can drive the upper and lower brackets 1882, 1886 up or down to open or close the top lid assembly 1 150. The securement rings 1858 can be easily rotated manually by an operator, such as by hand or using a tool, or can be configured to be rotated by motors for automatic opening and closing of the top lid assembly 1 150.

[0319] With additional reference to Figures 37-44 a device 2010 of a different construction is illustrated. The device 2010 can be similar to the device 1010, except as otherwise shown or described herein. In the example provided, the device 2010 includes a vessel assembly 2014 coupled to a cart 2018. The cart 2018 can include a base 2022 including a plurality of wheels 2026. The vessel assembly 2014 can include a single pressure vessel 2030, as compared to the modular pressure vessel units 1 146 of the device 1010 (Figures 12-36). The vessel assembly 2014 can be fixedly mounted to the cart 2018. A controller 2034 (e.g., a PLC, or touch screen device that can be similar to controller 1018) can be mounted to the cart 2018 and configured to display status of the device 2010 and to receive input commands to control the device 2010. The controller 2034 can allow the pressure vessel 2030 to achieve supercritical fluid state independently of traditional fixed pumping stations. The vessel assembly 2014 can also include a handle 2038 that can be fixedly coupled to the pressure vessel 2030 for assisting movement of the cart 2018 and for aiding positioning the pressure vessel 2030 horizontally in needed for unloading. In the example provided the handle 2038 is a T-shaped handle, with the base of the "T" shape being fixedly attached to the pressure vessel 2030, though other configurations can be used.

[0320] The vessel assembly 2014 can include a top lid 21 10. In the example provided, the top lid 21 10 can be a screw on top that can screw into the pressure vessel 2030, though other configurations can be used to seal the top opening of the pressure vessel 2030. In the example provided, the top of the pressure vessel 2030 has a hammer union opening, including a hammer union nut 21 14 (e.g., similar to nut 1226) that can screw into the top lid 21 10. Thus, rotation of the hammer union nut 21 14 can drive the top lid 21 10 up to open the pressure vessel 2030.

[0321] In the example provided, the top lid 21 10 can include an inlet port 21 18, a pressure relief valve 2122, and a pressure gage 2126. The inlet port 21 18 can be configured to be coupled to a source of drying material, such as sCO2 from one of the pumping stations 1014a, 1014b, 1014c (Figure 1 1 ). The bottom of the vessel assembly 2014 can include a drain port 2130 that can be in fluid communication with the interior of the pressure vessel 2030. The drain port 2130 can have a valve 2134 and can be in fluid communication with a sight glass 2138. The sight glass 2138 can extend up along an exterior of the vessel assembly 2014 and be connected back into the interior of the pressure vessel 2030 proximate to the top of the vessel assembly 2014. The sight glass 2138 can include a section that is transparent or translucent to permit visual inspection of the level of drying material within the pressure vessel 2030 without opening the pressure vessel 2030.

[0322] Similar to the device 1010 (Figures 12-36), the vessel assembly 2014 can include a cooling system 2210 and a heating system 2214, and an insulating cover 2218. The cooling system 2210 can generally include a cooling coil 2222 that is a tube or conduit has an inlet 2226 and an outlet 2230 and coils around the pressure vessel 2030. The cooling coil 2222 can coil around the pressure vessel 2030 between the outer cylindrical surface of the pressure vessel 2030 and the inner cylindrical surface of the insulating cover 2218. The cooling inlet 2226 can extend through an aperture in the insulating cover 2218 and be configured to be in fluid communication with a cooling fluid supply (e.g., liquid nitrogen or liquid helium), such as at the third pumping station 1014c (Figure 1 1 ) for example. The cooling outlet 2230 can be external to the insulating cover 2218 and can be selectively opened to the atmosphere via a valve 2234. The valve 2234 can be controlled by the controller 2034. Thus, the cooling fluid can flow through the cooling coil and be flashed to the atmosphere to cool the pressure vessel 2030.

[0323] In an alternative construction, the cooling outlet 2230 can be internal to the insulating cover 2218 and can be selectively opened to the space between the insulating cover 2218 and the pressure vessel 2030. Thus, the cooling fluid can flow through the cooling coil 2222 and be flashed to the space between the pressure vessel 2030 and the insulating cover 2218 to cool the pressure vessel 2030 and effectively create a Dewar's Flask system. In an alternative configuration, the valve 2234 is 3-way or other valve configured to be operable in a closed mode, a first open mode, and a second open mode. In the closed mode, the valve 2234 is closed to prevent flow of fluid therethrough. In the first open mode, the valve 2234 can be open to the space between the pressure vessel 2030 and the insulating cover 2218 to flash the cooling fluid thereto. In the second open mode, the valve 2234 can be open to the atmosphere exterior of the insulating cover 2218 to flash the cooling fluid thereto.

[0324] In the configurations described above where the cooling fluid is flashed to the space between the pressure vessel 2030 and the insulating cover 2218, the cooling fluid can fill the space therebetween and then be vented to the atmosphere exterior of the insulating cover 2218, such as through a vent. Alternatively, the cooling fluid can be recovered from the space between the pressure vessel 2030 and the insulating cover 2218 by a recovery conduit to be re-used by the cooling fluid supply (e.g., the third pumping station 1014c).

[0325] The heating system 2214 can include a heating element 2238 disposed between the insulating cover 2218 and the pressure vessel 2030. In the example provided, the heating element 2238 is an electric resistance element (e.g., heating tape or pad). The heating element 2238 can be wrapped around the pressure vessel 2030, such as in direct contact with the outer surface of the pressure vessel 2030, or can be wrapped around and in direct contact with the cooling coil 2222, though other configurations can be used. The heating system 2214 can be controlled by the controller 2034. [0326] The vessel assembly 2014 can include interior shelves within the pressure vessel 2030 that can be similar to the shelf assembly 1414 shown and described above with reference to Figures 25-28. The vessel assembly 2014 can include a pair of ports 2310, 2314 that can be in fluid communication with the shelves within the pressure vessel 2030 to provide cooling fluid to flow through the cooling coils (e.g., cooling coil 1534) of the shelves.

[0327] As best shown in Figure 43, the bottom of the cart 2018 can also include an ultrasonic transducer 2318 and an optional mixing device, such as a magnetic stirrer or motor disposed within the pressure vessel 2030, configured to agitate the contents of the pressure vessel 2030. The mixing device can be similar to the mixing device 1822 described above.

[0328] The controller 2034 can control, for example, the heating system 2214, the cooling system 2210, thermocouples and temperature regulators, mass flow meters of metering valves, ultrasonic probes (that can be mounted externally or internally), the mixing device, and the ultrasonic transducer 2318. The controller 2034 can additionally be coupled with other ones of the devices 2010 (e.g., via wires, or wirelessly) to allow a series of the devices 2010 to coordinate pressure vessel conditions, or operate different conditions simultaneously, as best shown in Figure 44.

[0329] With additional reference to Figure 45, a device 3010 of an alternative construction is illustrated. The device 3010 can be similar to the device 1010 (Figures 12-36), except as shown or described herein. In the example provided, the device 3010 includes a pressure vessel assembly 3014 and a cart 3018, similar to the device 1010. The pressure vessel assembly 3014 can include a series of connected hammer unions 3022. The hammer unions 3022 can be similar to those described above with reference to the device 1010. The cart 3018 can include a plurality of cradles 3026, wheels 3030, and a controller 3034. The cradles 3026 can be semi-circular in shape, with the concave side facing up and the wheels 3030 being attached to the convex side of the cradles 3026. The hammer unions 3022 can be supported by the concave side of the cradles 3026, such that the pressure vessel assembly 3014 can be supported horizontally relative to the ground.

Recitation of Exemplary Embodiments

[0330] The following is a recitation of embodiments exemplifying the methods, devices, and compositions of the present technology. 1 . A method for drying a porous structure, the method comprising:

transferring the porous structure to a pressure chamber, wherein the porous structure comprises a plurality of pores and a first solvent disposed in and about the plurality of pores;

flushing the pressure chamber with CO ₂ until CO ₂ replaces at least a portion of the first solvent in and about at least a portion of the pores;

rapidly decreasing the temperature inside the pressure chamber to cause freezing of the CO ₂ in and about the at least a portion of the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided; and

removing the CO ₂ by subliming to yield a dried porous structure.

2. The method according to embodiment 1 , wherein the first solvent is miscible with liquid CO ₂ (LCO ₂ ).

3. The method according to embodiment 1 , wherein the first solvent is selected from the group consisting of acetone, acetonitrile, acetic acid, amyl alcohol, benzene, carbon tetrachloride, chlorobenzene, chloroform, cyclo-cresylic acid, hexane, isopropyl alcohol, dimethylformamide, ethanol, ethyl acetate, furfural, furfuryl alcohol, methanol, n-butane, n-heptane, n-hexane, pyridine, and combinations thereof.

4. The method according to embodiment 1 , wherein the flushing the pressure chamber with CO ₂ until CO ₂ replaces at least a portion of the first solvent in and about at least a portion of the pores comprises flushing the pressure chamber with CO ₂ until CO ₂ replaces greater than or equal to about 90% to less than or equal to about 100% of the first solvent in and about the at least a portion of the pores.

5. The method according to embodiment 1 , wherein the flushing the pressure chamber with CO ₂ comprises flushing the chamber with liquid CO ₂ (LCO ₂ ), supercritical CO ₂ (sCO ₂ ), or a combination thereof.

6. The method according to embodiment 1 , wherein the flushing the pressure chamber with CO ₂ comprises flushing the chamber with liquid CO ₂ (LCO ₂ ) and the method further comprises: raising the temperature and the pressure within the pressure chamber to generate supercritical CO ₂ (sCO ₂ ).

7. The method according to embodiment 6, wherein the raising the temperature and the pressure within the pressure chamber comprises raising the temperature to greater than or equal to about 31 .1 ° C to less than or equal to about 145 ° C and raising the pressure to greater than or equal to about 1071 psi to less than or equal to about 145,000 psi. 8. The method according to embodiment 7 wherein depressurizing the pressure chamber containing supercritical CO2 comprises:

rapidly decreasing the temperature inside the pressure chamber causing supercritical CO ₂ (sCO ₂ ) to condense to a liquid and solidify in and about the at least a portion of the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided.

9. The method according to embodiment 6 where in the supercritical CO ₂ (sCO ₂ ) in and about at least a portion of the pores of the porous structure affects the size and distribution of solidified CO ₂ crystals.

10. The method according to embodiment 6, wherein direct condensation of CO ₂ from the supercritical CO ₂ results in rapid nucleation of CO ₂ crystals on and about a surface of the porous structure. 1 1 . The method according to embodiment 10, wherein rapid condensation and solidification of CO ₂ molecules from sCO ₂ affects the growth and direction of CO ₂ nanocrystals.

12. The method according to embodiment 1 , wherein the flushing the pressure chamber with CO ₂ comprises flushing the pressure chamber with liquid CO ₂ , and the freezing of the CO ₂ in and about the at least a portion of the pores comprises forming at least one layer comprising a single molecule of CO ₂ on a surface of the porous structure, such that a first contact angle between the liquid CO ₂ and a surface the porous structure covered with frozen CO ₂ is less than a second contact angle between liquid CO ₂ and a surface of the porous structure that is not covered with frozen

13. The method according to embodiment 12, wherein the reduced contact angle between the liquid CO2 and the surface or the porous structure minimizes shrinkage caused by exposure of the porous structure to a vapor liquid interface.

14. The method according to embodiment 1 , wherein rapidly decreasing the temperature inside the pressure chamber is performed by introducing a liquid into the pressure chamber that has a freezing point below the freezing point of CO ₂ .

15. The method according to embodiment 12, wherein rapidly decreasing the temperature inside the pressure chamber is performed by introducing a cryogenic fluid into the pressure chamber, wherein the cryogenic fluid is liquid nitrogen or liquid helium.

16. The method according to embodiment 12, wherein the introducing a liquid into the pressure chamber comprises circulating a liquid about the interior of the pressure chamber through a conduit. 17. The method according to embodiment 1 , wherein the rapidly decreasing the temperature inside the pressure chamber comprises cooling the interior of the pressure chamber at a rate of greater than or equal to about 0.2 ° C per minute to less than or equal to about 20 ° C per minutes. 18. The method according to embodiment 1 , wherein the rapidly decreasing the temperature inside the pressure chamber causes the pressure inside the pressure chamber to decrease.

19. The method according to embodiment 18, wherein the rapidly decreasing the temperature causes the pressure inside the pressure chamber to decrease from a pressure associated with generating supercritical CO ₂ to less than or equal to about 75 psi. 20. The method according to embodiment 1 , wherein rapidly decreasing the temperature inside the pressure chamber causes depressurization of the pressure chamber, and wherein the rate of depressurization of the pressure chamber is accelerated by simultaneously expanding CO ₂ from within the pressure chamber CO ₂ outside the pressure chamber at a rate greater than or equal to 0.001 Mpa/minute and less than or equal to 2.0 Mpa/minute.

21 . The method according to embodiment 1 , wherein the removing the CO ₂ by subliming is performed at ambient temperature and pressure.

22. The method according to embodiment 1 , wherein the removing the CO ₂ by subliming is performed at a temperature of greater than or equal to about ambient temperature to less than or equal to about 400° C. 23. The method according to embodiment 1 , wherein the removing the CO ₂ by subliming is performed at a pressure of greater than or equal to about ambient pressure to less than or equal to about 5.1 atm.

24. The method according to embodiment 1 , wherein prior to the flushing, the method further comprises:

exchanging a second solvent disposed in and about the pores of the porous structure with the first solvent.

25. The method according to embodiment 1 , wherein the plurality of pores are a plurality of micropores, a plurality of mesopores, a plurality of macropores, or a combination thereof.

26. The method according embodiment 1 , wherein the porous structure further comprises a primary or secondary amines.

27. The method according to embodiment 26, wherein the CO ₂ reacts with the primary or secondary amines to generate carbamates. 28. The method according to embodiment 27, wherein the carbamates are converted back to primary or secondary amines during or after the subliming.

29. The method according to embodiment 27, wherein the carbamates are converted back to primary or secondary amines at a pressure of greater than or equal to about 0.001 atm and less than or equal to about 5.1 atm.

30. The method according to embodiment 27, wherein the carbamates are converted back to primary or secondary amines at a temperature of greater than or equal to about 28 ° C and less than or equal to about 400 ° C.

31 . A method for rapidly drying a porous structure, the method comprising: transferring the porous structure to a pressure chamber, wherein the porous structure comprises a plurality of pores and a first solvent disposed in and about the plurality of pores;

introducing CO2 within the pressure chamber;

raising the temperature and the pressure within the pressure chamber to generate supercritical CO ₂ (sCO ₂ );

rapidly flushing the pressure chamber with SCO2 until SCO2 replaces at least a portion of the first solvent in and about at least a portion of the pores;

depressurizing chamber by rapidly decreasing the temperature inside the pressure chamber, wherein the SCO ₂ condenses to a liquid and solidifies in and about the at least a portion of the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided; and

removing the CO ₂ by subliming to yield a dried porous structure.

32. The method according to embodiment 31 , wherein the first solvent is soluble in supercritical CO ₂ . 33. The method according to embodiment 31 , wherein the first solvent is selected from the group consisting of acetone, acetonitrile, acetic acid, amyl alcohol, benzene, carbon tetrachloride, chlorobenzene, chloroform, cyclo-cresylic acid, hexane, isopropyl alcohol, dimethylformamide, ethanol, ethyl acetate, furfural, furfuryl alcohol, methanol, n-butane, n-heptane, n-hexane, pyridine, and combinations thereof. 34. The method according to embodiment 31 , wherein the introducing CO ₂ within the pressure chamber comprises introducing liquid CO2 into the pressure chamber and wherein the SCO2 is generated from the liquid CO2.

35. The method according to embodiment 31 , wherein the rapidly flushing the pressure chamber with SCO2 comprises:

raising the temperature and the pressure within the pressure chamber to generate the sCO ₂ ; and

circulating a stream of sCO ₂ about the pressure chamber,

wherein the circulating stream of SCO2 accelerates a rate of replacing the first solvent with the SCO2.

36. The method according to embodiment 31 , wherein the plurality of pores are a plurality of micropores, a plurality of mesopores, a plurality of macropores, or a combination thereof.

37. The method according embodiment 31 , wherein the porous structure further comprises a primary or secondary amines.

38. The method according to embodiment 37, wherein the CO ₂ reacts with the primary or secondary amines to generate carbamates.

39. The method according to embodiment 38, wherein the carbamates are converted back to primary or secondary amines during or after the subliming.

40. The method according to embodiment 38, wherein the carbamates are converted back to primary or secondary amines at a pressure of greater than or equal to about 0.001 atm and less than or equal to about 5.1 atm.

41 . The method according to embodiment 38, wherein the carbamates are converted back to primary or secondary amines at a temperature of greater than or equal to about 28 ⁰ C and less than or equal to about 400 ⁰ C. 42. A method for impregnating and drying a porous structure, the method comprising:

transferring the porous structure to a pressure chamber, wherein the porous structure comprises a plurality of pores and a first solvent disposed in and about the plurality of pores;

flushing the pressure chamber with CO ₂ until CO ₂ replaces at least a portion of the first solvent in and about at least a portion of the pores;

raising the temperature and the pressure within the pressure chamber to generate supercritical CO ₂ (sCO ₂ );

impregnating the porous structure with at least a first impregnating agent by introducing a first mixture comprising sCO ₂ and the at least first impregnating agent into the drying chamber, wherein the first impregnating agent is not present in the porous structure prior to the transferring;

rapidly decreasing the temperature inside the pressure chamber to cause freezing of the first mixture in and about the at least a portion of pores of the porous structure, wherein the first impregnating agent is loaded into the porous structure and the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided; and

selectively removing the CO ₂ by subliming to yield a dried porous structure containing the at least first impregnating agent.

43. The method according to embodiment 42, wherein the first solvent is a liquid miscible with sCO ₂ . 44. The method according to embodiment 42, wherein the first solvent is selected from the group consisting of at least acetone, acetonitrile, acetic acid, amyl alcohol, benzene, carbon tetrachloride, chlorobenzene, chloroform, cyclo-cresylic acid, hexane, isopropyl alcohol, dimethylformamide, ethanol, ethyl acetate, furfural, furfuryl alcohol, methanol, n-butane, n-heptane, n-hexane, pyridine, or a combination thereof.

45. The method according to embodiment 42, wherein the first impregnating agent comprises at least a composition that is solid or liquid at ambient pressure and temperature and being at least partially soluble in sCO ₂ and liquid CO ₂ , but insoluble in gaseous CO ₂ . 46. The method according to embodiment 42, wherein the first impregnating agent comprises at least a substance that is solid or liquid at ambient pressure and temperature and being at least partially soluble in SCO2, but insoluble in liquid CO2 and gaseous CO ₂ .

47. The method according to embodiment 42, wherein the impregnating agent is precipitated into the porous structure during the freezing of supercritical CO2 within and about the porous structure.

48. The method according to embodiment 42, wherein the impregnating agent is trapped in the porous structure during the freezing of SCO2 and remains impregnated within and around the porous structure after selectively removing at least 50% of the frozen CO ₂ via sublimation.

49. The method according to embodiment 42, wherein the impregnating agent is trapped in the porous structure during the freezing of sCO ₂ and remains impregnated within and around the porous structure after selectively removing at least 70% of the frozen CO2 via sublimation.

50. The method according to embodiment 42, wherein the impregnating agent is trapped in the porous structure during the freezing of sCO ₂ and remains impregnated within and around the porous structure after selectively removing at least 90% of the frozen CO2 via sublimation.

51 . The method according to embodiment 42, wherein the impregnating agent is trapped in the porous structure during the freezing of SCO2 and remains impregnated within and around the porous structure after selectively removing at least 50% of the frozen CO ₂ via sublimation at a temperature of greater than or equal to about -78 ° C to less than or equal to about 250 ° C and at a pressure equal to or greater than about 1 atm to less than or equal to about 5.1 atm. 52. The method according to embodiment 42, wherein the plurality of pores are a plurality of micropores, a plurality of mesopores, a plurality of macropores, or a combination thereof. 53. The method according embodiment 42, wherein the porous structure further comprises a primary or secondary amines.

54. The method according to embodiment 53, wherein the CO ₂ reacts with the primary or secondary amines to generate carbamates.

55. The method according to embodiment 54, wherein the carbamates are converted back to primary or secondary amines during or after the subliming.

56. The method according to embodiment 54, wherein the carbamates are converted back to primary or secondary amines at a pressure of greater than or equal to about 0.001 atm and less than or equal to about 5.1 atm.

57. The method according to embodiment 54, wherein the carbamates are converted back to primary or secondary amines at a temperature of greater than or equal to about 28 ⁰ C and less than or equal to about 400 ⁰ C.

58. A method of preserving a porous material comprising primary or secondary amines, the method comprising:

transferring the porous structure to a pressure chamber, wherein the porous structure comprises a plurality of pores and a first solvent disposed in and about the plurality of pores;

contacting the porous structure with CO ₂ ;

converting the primary or secondary amines to carbamates that protect the porous structure from the CO ₂ ;

rapidly decreasing the temperature inside the pressure chamber to cause freezing of the CO ₂ in and about the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided; removing the CO ₂ by subliming; and

converting the carbamates back into primary or secondary amines. 59. A composite material comprising:

a porous aerogel matrix; and

a plurality of reinforcing agents uniformly dispersed therein.

60. The composite material according to embodiment 59, wherein the porous aerogel matrix is composed of a polymer selected from the group consisting of polyesters (including polyethylene terephthalate (PET)), polyurethane, polyolefin, poly(acrylic acid) (PAA), poly(methyl acrylate) (PMA), expoxy, poly(methyl methacrylate) (PMMA), acrylonitrile butadiene styrene (ABS), polyimides, polyamides (including polycaprolactam (nylon)), polylactic acid (PLA), polybenzimidazole, polycarbonate, polyether sulfone (PES), polyetherether ketone (PEEK), polyetherimide (PEI), polyethylene (PE; including ultra-high molecular weight polyethylene (UHMWPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), and cross- lined polyethylene (PEX)), polyphenylene oxide (PPO), polyphenylene sulfide (PPS), polypropylene (PP), polystyrene (PS), polyvinyl chloride (PVC), polytetrafluoroethylene (PTFE), co-polymers thereof, and combinations thereof

61 . The composite material according to embodiment 59, wherein the porous aerogel matrix is composed of a polymer selected from the group consisting of a metal nanoparticle, a metalloid nanoparticle, a metal chalcogenide, a metalloid chalcogenide, a carbonizable polymer, a polyurea, a formaldehyde polymer, a polypentene, a polybutene, a resorcinol-melamine-formaldehyde polymer, a furfural-formaldehyde polymer, a resole, a novolac, an polyisocyanurate, acetic-acid-based polymer, a polysaccharide, a glycoprotein, a proteoglycan, collagen, a protein, a polypeptide, a nucleic acid, amorphous carbon, graphitic carbon, graphene, diamond, polyacrylamide, a phenolic polymer, a resorcinol-formaldehyde polymer, a melamine-formaldehyde polymer, a polypentene, a in, a gelan, a gum, an agarose, an agar, a cellulose, an organic-inorganic hybrid material, a rubber, a polybutadiene, a poly(methyl pentene), a polyester, a polyether polymer, a polymer-crosslinked oxide, a silica-polysaccharide polymer, a silica-pectin, a polyether ketone, polybutene, a polytetrafluoroethylene, a polyethylene, a polypropylene, an alginate, a chitin, a chitosan, a pectin, a gelatketone, a polyurethane, a polyisocyanate, a polyimide, a polyamide, a polyacrylonitrile, a polycyclopentadiene, a polybenzoxazine, and combinations thereof. 62. The composite material according to embodiment 59, wherein the reinforcing agents are fibers, particles, two-dimensional materials, or nanotubes. 63. The composite material according to embodiment 59, wherein the fibers, particles, two-dimensional materials, or nanotubes are composed of an aerogel, carbon, a polymer, a glass, a metal, or a combination thereof.

64. The composite material according to embodiment 59, wherein the composite material is a vehicle frame or a vehicle panel.

65. The composite material according to embodiment 59, wherein the composite material is a part of a vehicle. 66. The composite material according to embodiment 59, wherein the composite material has a reinforcing agent:aerogel matrix ratio of greater than or equal to about 0.5:99.5 to less than or equal to about 99.5:0.5. 66 and a porous plastic matrix: aerogel matrix ratio of greater than or equal to about 0.5:99.5 to less than or equal to about 99.5:0.5.

67. The composite material according to embodiment 59, wherein the composite material has a porous plastic aerogel matrix:reinforcing agent ratio of greater than or equal to about 0.5:99.5 to less than or equal to about 99.99:0.01 . 68. The composite material according to embodiment 59, wherein the porous plastic matrix comprises a network of micropores, mesopores, macropores, or a combination thereof.

69. The composite material according to embodiment 59, wherein at least about 40% of the porous plastic matrix is defined by macropores.

70. The composite material according to embodiment 59, wherein the composite material has a thermal conductivity of less than about 50 mW/m-K. 71 . The composite material according to embodiment 59, where in composite material has a compressive modulus of greater than about 1 GPa.

72. The composite according to embodiment 59, where in the composite material has a density of greater than or equal to about 0.05 g/cm ³ to less than or equal to about 3.5 g/cm ³ .

73. The composite according to embodiment 59, where in the composite material is electrically conductive and has a conductivity of from greater than or equal to 10 ^"3 ohm/sq and less than or equal to about 10 ¹² ohm/sq.

74. The composite material according to embodiment 59, made by a process comprising:

disposing a plurality of reinforcing agents into a first solvent to generate a first mixture;

dissolving a polymer in a second solvent to generate a first solution;

combing the first mixture with the first solution to generate a precursor material comprising the first solvent and the second solvent;

pouring the precursor material into a mold having a predetermined shape;

evaporating off at least a portion of at least one of the first solvent or the second solvent until the precursor material has a desired viscosity;

performing a step selected from the group consisting of:

exchanging at least a portion of the remaining first and second solvents with CO ₂ or a third solvent miscible with CO ₂ wherein the polymer is insoluble in third solvent, and

freezing the remaining first solvent and second solvent in the precursor material, and exchanging the first and second solvents with the third solvent; and

drying the precursor material without exposing the precursor material to a liquid- gas interface to yield the composite material.

75. The composite material made according to the process of embodiment 74, wherein the drying the precursor material without exposing the precursor material to a liquid-gas interface comprises: rapidly decreasing the temperature of the CO ₂ or third solvent to cause freezing in and about at least a portion of the pores, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided; and removing the CO ₂ by subliming to yield the composite material.

76. The composite material made according to the process of embodiment 74, wherein the first solvent is the same as the second solvent.

77. The composite material made according to the process of embodiment 74, wherein the first solvent is acetone, acetonitrile, acetic acid, alcohol, amyl alcohol, benzene, carbon tetrachloride, chlorobenzene, chloroform, cyclo-cresylic acid, hexane, isopropyl alcohol, dimethylformamide, ethanol, ethyl Acetate, furfural, furfuryl alcohol, methanol, n-butane, n-heptane, n-hexane, pyridine, or a combination thereof. 78. The composite material made according to the process of embodiment

74, wherein the second solvent is 2-methoxyethanol, 2,6,10,14-tetramethyl pentadecane, acetone, acetonitrile, alcohols, amyl alcohol, amyl acetate, aniline , n- butanol, n-butanol, sec-butanol, tert-butanol, chlorex, cyclohexanol, C1 -C6 alcohols cyclohexanone, cresylic acid, dimethylsulfoxide, dimethylacetamide, dimethylformamide, ethanol, furfural, furfuryl alcohol, 1 -propanol , pyridine, hexane, hexanes, n-hexane, hydrocarbons, isopropanol, methanol, methoxyethanol, N- methylpyrrolidone, nitrobenzene, pentanol, liquid SO2, quinolone, water, xylene, or a combination thereof. 79. The composite material made according to the process of embodiment

74, wherein the process further comprises:

performing at least one of agitating, mixing, stirring, and swirling the precursor material prior to the pouring. 80. A composite material comprising a porous plastic matrix, a porous aerogel matrix; and a plurality of reinforcing agents uniformly dispersed therein made by a process comprising:

disposing a plurality of reinforcing agents into a first solvent to generate a first mixture; dissolving a polymer in a second solvent to generate a first solution; disposing a plurality of aerogel matrix precursors into a third solvent to generate a second mixture, wherein the polymer is insoluble in the third solvent;

combining the first mixture and the second mixture with the first solution to generate a precursor material comprising the first solvent, the second solvent, and the third solvent;

transferring the precursor material into a mold having a predetermined shape; evaporating at least a portion of at least one of the first solvent, the second solvent, or the third solvent from the precursor material until the precursor material has a desired viscosity;

performing at least one step selected from the group consisting of

exchanging at least a portion of the remaining first, second, and third solvents with CO ₂ , and

freezing the remaining first solvent, second solvent, and third solvent in the precursor material, and exchanging the first, second solvent, and third solvents with a fourth solvent; and

drying the precursor material, such that the formation of gas bubbles and exposure of the porous structure to a gas-liquid interface are minimized or avoided. 81 . The composite material made according to the process of embodiment

80, wherein the second solvent is m-chlorobenzene, cyclohexane, cyclohexanone, ethyl chloride, ethyl ether, furfuryl alcohol, isopropyl ether, ketones, methyl acetate, methyl chloride, methyl ethyl ketone, methylene chloride, n-octane, n-pentane, tetrahydrofuran, trichloroethylene, triethanol Amine, 1 ,1 -dichloroethane, acetone, 1 ,2,4- trichlorobenzene, 1 ,1 -dichloroethane, acetone, 1 ,2,4-trichlorobenzene, or a combination thereof.

82. The composite material made according to the process of embodiment 78, wherein the third solvent is 2-methoxyethanol, 2,6,10,14-tetramethyl pentadecane, acetone, acetonitrile, alcohols, amyl alcohol, amyl acetate, aniline , N-butanol, N- butanol, Sec-butanol, le/t-butanol, chlorex, cyclohexanol, C1 -C6 alcohols cyclohexanone, cresylic acid, dimethylsulfoxide, dimethylacetamide, N,N- dimethylformamide, ethanol, furfural, furfural alcohol, 1 -propanol , pyridine, hexane, hexanes, n-hexane, hydrocarbons, isopropanol, methanol, methoxyethanol, N- methylpyrrolidone, nitrobenzene, pentanol, liquid SO ₂ , quinolone, water, xylene, or a combination thereof

83. The composite material made according to the process of embodiment 78, wherein first solvent is m-chlorobenzene, cyclohexane, cyclohexanone, ethyl chloride, ethyl ether, furfuryl alcohol, isopropyl ether, ketones, methyl acetate, methyl chloride, methyl ethyl ketone, methylene chloride, n-octane, n-pentane, tetrahydrofuran, trichloroethylene, triethanolamine, 1 ,1 -dichloroethane, acetone, 1 ,2,4-trichlorobenzene, 1 ,1 -dichloroethane, methoxyethanol, 2,6,10,14-tetramethyl pentadecane, acetone, acetonitrile, alcohols, amyl alcohol, amyl acetate, aniline , n-butanol, sec-butanol, tert- butanol, chlorex, cyclohexanol, C1 -C6 alcohols cyclohexanone, cresylic acid, dimethylsulfoxide, dimethylacetamide, dimethylformamide, ethanol, furfural, furfuryl alcohol, 1 -propanol , pyridine, hexane, hexanes, N-hexane, hydrocarbons, isopropanol, isopropanol, methanol, methoxyethanol, N-methylpyrrolidone, nitrobenzene, pentanol, liquid SO2, quinolone, water, xylene, or a combination thereof

84. The composite material made according to the process of embodiment 80, the process further comprising:

performing at least one of agitating, mixing, stirring, sonicating, and or swirling the precursor material prior to the transferring.

85. The composite material made according to the process of embodiment 80, wherein the porous plastic matrix is generated during the freezing. 86. A porous plastic aerogel composite having a predetermined shape comprising:

a first plastic polymer;

a porous plastic aerogel. 87. A method of producing a porous plastic aerogel composite comprising: cutting, grinding milling, crushing, heating, or swelling a shaped porous plastic aerogel composite to form a plurality of plastic aerogel composite particles;

adding a first polymer to the plastic aerogel composite particles to form a first mixture; placing the first mixture into a pressure chamber;

heating and pressurizing the first mixture of particles to impregnate the pores of porous plastic aerogel with a first plastic polymer and to generate a heated and pressurized mixture;

extruding the heated and pressurized mixture into a mold having a predetermined shape to generate an extruded mixture;

cooling the extruded mixture; and

removing the extruded mixture to yield a plastic porous plastic aerogel composite matrix having a defined shape.

88. The method according to embodiment 87, wherein the first polymer comprises polyester, polyethylene terephthalate, polyethylene, high-density polyethylene, polyvinyl chloride (polyvinylidene chloride, low-density polyethylene polypropylene, polystyrene , acrylonitrile butadiene styrene , polycarbonate, polyurethanes, maleimide, melamine formaldehyde, plastarch material, phenolics, polyepoxide, polyetheretherketone, polyetherimide , polyimide, polylactic acid , polymethylmethacrylate, polytetrafluoroethylene, furan, silicone, polysulfone, or a combination thereof.

89. A metal aerogel composite comprising of

a metal;

a plurality or aerogel matrices; and

a plurality of reinforcing agents. 90. A method of producing the composite material according to embodiment 89, the method comprising:

placing a shaped porous plastic aerogel composite containing dispersed particles into a high temperature mold;

placing a suitable refractory material in and around at least a portion of the shaped porous plastic aerogel composite;

replacing a plastic portion of the shaped porous plastic aerogel composite contained within the mold with a molten metal by pouring a molten metal over, above and around the shaped porous plastic aerogel composite to vaporize the plastic portion; allowing the mold sufficient time to cool and for the molten metal to solidify; and removing the metal aerogel composite from the refractory material.

91 . The composite according to embodiment 89, wherein the composite comprises a plastic residual portion of greater than equal to about 0.00001 wt% and less than or equal to about 5 wt%.

92. The composite according to embodiment 89, where in the composite comprises a plurality of aerogel matrices at a concentration of greater than or equal to about 0.05 wt% to less than or equal to about 90 wt.%.

93. The composite according to embodiment 89, where in the composite comprises reinforcing materials at a concentration of greater than or equal to about 0.005 wt% to less than or equal to about 90 wt.%. 94. The composite according to embodiment 89, wherein the composite comprises a metal content of greater than or equal to about 0.005 wt% to less than or equal to 90 wt%.

95. The composite according to embodiment 89, where in the aerogel matrices and reinforcing materials are dispersed throughout the composite.

[0331] The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations are not to be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.

[0332] In this application, including the definitions below, the term "module" or the term "controller" may be replaced with the term "circuit." The term "module" may refer to, be part of, or include: an Application Specific Integrated Circuit (ASIC); a digital, analog, or mixed analog/digital discrete circuit; a digital, analog, or mixed analog/digital integrated circuit; a combinational logic circuit; a field programmable gate array (FPGA); a programmable logic controller (PLC); a processor circuit (shared, dedicated, or group) that executes code; a memory circuit (shared, dedicated, or group) that stores code executed by the processor circuit; other suitable hardware components that provide the described functionality; or a combination of some or all of the above, such as in a system-on-chip.

[0333] The module may include one or more interface circuits. In some examples, the interface circuits may include wired or wireless interfaces that are connected to a local area network (LAN), the Internet, a wide area network (WAN), or combinations thereof. The functionality of any given module of the present disclosure may be distributed among multiple modules that are connected via interface circuits. For example, multiple modules may allow load balancing. In a further example, a server (also known as remote, or cloud) module may accomplish some functionality on behalf of a client module.

[0334] The term code, as used above, may include software, firmware, and/or microcode, and may refer to programs, routines, functions, classes, data structures, and/or objects. The term shared processor circuit encompasses a single processor circuit that executes some or all code from multiple modules. The term group processor circuit encompasses a processor circuit that, in combination with additional processor circuits, executes some or all code from one or more modules. References to multiple processor circuits encompass multiple processor circuits on discrete dies, multiple processor circuits on a single die, multiple cores of a single processor circuit, multiple threads of a single processor circuit, or a combination of the above. The term shared memory circuit encompasses a single memory circuit that stores some or all code from multiple modules. The term group memory circuit encompasses a memory circuit that, in combination with additional memories, stores some or all code from one or more modules.

[0335] The term memory circuit is a subset of the term computer-readable medium. The term computer-readable medium, as used herein, does not encompass transitory electrical or electromagnetic signals propagating through a medium (such as on a carrier wave); the term computer-readable medium may therefore be considered tangible and non-transitory. Non-limiting examples of a non-transitory, tangible computer-readable medium are nonvolatile memory circuits (such as a flash memory circuit, an erasable programmable read-only memory circuit, or a mask read-only memory circuit), volatile memory circuits (such as a static random access memory circuit or a dynamic random access memory circuit), magnetic storage media (such as an analog or digital magnetic tape or a hard disk drive), and optical storage media (such as a CD, a DVD, or a Blu-ray Disc).

[0336] The apparatuses and methods described in this application may be partially or fully implemented by a special purpose computer created by configuring a general purpose computer to execute one or more particular functions embodied in computer programs. The functional blocks, flowchart components, and other elements described above serve as software specifications, which can be translated into the computer programs by the routine work of a skilled technician or programmer.

[0337] The computer programs include processor-executable instructions that are stored on at least one non-transitory, tangible computer-readable medium. The computer programs may also include or rely on stored data. The computer programs may encompass a basic input/output system (BIOS) that interacts with hardware of the special purpose computer, device drivers that interact with particular devices of the special purpose computer, one or more operating systems, user applications, background services, background applications, etc.

[0338] The computer programs may include: (i) descriptive text to be parsed, such as HTML (hypertext markup language) or XML (extensible markup language), (ii) assembly code, (iii) object code generated from source code by a compiler, (iv) source code for execution by an interpreter, (v) source code for compilation and execution by a just-in-time compiler, etc. As examples only, source code may be written using syntax from languages including C, C++, C#, Objective C, Haskell, Go, SQL, R, Lisp, Java®, Fortran, Perl, Pascal, Curl, OCaml, Javascript®, HTML5, Ada, ASP (active server pages), PHP, Scala, Eiffel, Smalltalk, Erlang, Ruby, Flash®, Visual Basic®, Lua, and Python®.

[0339] None of the elements recited in the claims are intended to be a means- plus-function element within the meaning of 35 U.S.C. §1 12(f) unless an element is expressly recited using the phrase "means for," or in the case of a method claim using the phrases "operation for" or "step for."

[0340] Although the terms first, second, third, etc. may be used herein to describe various elements, components, regions, layers and/or sections, these elements, components, regions, layers and/or sections should not be limited by these terms. These terms may be only used to distinguish one element, component, region, layer or section from another region, layer or section. Terms such as "first," "second," and other numerical terms when used herein do not imply a sequence or order unless clearly indicated by the context. Thus, a first element, component, region, layer or section discussed below could be termed a second element, component, region, layer or section without departing from the teachings of the example embodiments.