CROSS REFERENCE TO RELATED APPLICATION

[0001] This application claims the benefit of U.S. Provisional Patent Application Serial No. 62/150,532, filed on April 21, 2015, the disclosure of which is hereby incorporated by reference.

FIELD OF THE DISCLOSURE

[0002] The present disclosure generally relates to a method of forming a hose assembly for conveying fluids and a method of forming the hose assembly.

BACKGROUND OF THE DISCLOSURE

[0003] Hose assemblies for conveying fuel and other corrosive fluids are well known in the art. These types of hose assemblies are exposed to a variety of fluids, such as foods, fuel mixtures, fuel additives, and chemicals, in addition to being exposed to extreme pressures, temperatures, and environmental conditions. Further, these hose assemblies are subjected to physical stresses, such as bending, repeated movement, and forces. Accordingly, these hose assemblies should be resistant to chemical and physical degradation.

[0004] These types of hose assemblies typically include a hose formed from polymeric material and one or more reinforcing layers. Mono- or multi-layer hoses formed from polymeric materials generally have low tensile strength, which often causes the hose to have low hoop strength. Consequently, the hose can be susceptible to kinking and other problems. As such, reinforcing layers are added to these hose assemblies to provide additional strength, durability, and kink resistance.

[0005] However, methods of forming hose assemblies including one or more reinforcing layers are often complex and costly. As each individual reinforcing layer is added, a binding emulsion composition or a tie layer is typically required to bond the individual reinforcing layers together. As such, the method typically includes many complicated steps and precludes use of reinforcing layers without additional applications of the binding emulsion composition or tie layers. Also, the binding emulsion composition or tie layer can fail to facilitate consistent wetting of the hose and the reinforcing layers, which consequently can cause the hose to delaminate from the reinforcing layers, which, in turn, can cause the hose to kink or even tear. Further, hose assemblies including one or more reinforcing layers often exhibit reduced flexibility, bendability, and deformation after exposure to elevated temperatures. As such, there remains an opportunity to develop an efficient and cost-effective method of forming a hose assembly that is resistant to kinking, flexible, bendable, resistant to deformation after thermal conditioning at higher temperatures, and durable, e.g. exhibits cohesive/destructive delamination of the reinforcing layer from the hose.

SUMMARY OF THE DISCLOSURE

[0006] A hose assembly is disclosed. The hose assembly comprises a core tube having an inner and an outer peripheral surface and a reinforcing layer disposed about the outer peripheral surface of the core tube. The reinforcing layer comprises a reinforcing yam and an integral reinforcing member comprising metal which are braided together. The reinforcing yam has a diameter DY and the integral reinforcing member has a diameter DRM. A ratio of DY to DRM is from about 3 : 2 to about 8: 1.

[0007] A method of forming the hose assembly is also disclosed. The method comprises the steps of extruding the core tube and braiding the reinforcing yam and the integral reinforcing member about the outer peripheral surface of the core tube to form the reinforcing layer.

[0008] The hose assembly is resistant to kinking, flexible, bendable, and durable, e.g. exhibits cohesive/destructive delamination of the reinforcing layer from the hose. Further, the hose assembly is particularly strong but not overly bulky because the reinforcing layer includes the integral reinforcing member. Further, the method of forming the hose assembly is efficient and cost-effective.

BRIEF DESCRIPTION OF THE DRAWINGS

[0009] Advantages of the present disclosure will be readily appreciated as the same becomes better understood by reference to the following detailed description when considered in connection with the accompanying drawings.

[0010] Figure 1 is a perspective view of a hose assembly as a fuel line in an automobile.

[0011] Figure 2 is a partial cross-sectional perspective view of a hose assembly comprising a core tube and a reinforcing layer having an integral reinforcing member therein, the reinforcing layer disposed about an outer peripheral surface of the core tube.

[0012] Figure 3 is a cross-sectional view of a first embodiment of an integral reinforcing member having a polymeric coating disposed thereon.

[0013] Figure 4 is a cross-sectional view of a second embodiment of an integral reinforcing member having a polymeric coating disposed thereon. [0014] Figure 5 is a partial cross-sectional perspective view of an embodiment of the hose assembly comprising the core tube and the reinforcing layer having two integral reinforcing members therein.

[0015] Figure 6 is a partial cross-sectional perspective view of a hose assembly comprising a core tube, a reinforcing layer comprising a first and second portion with an integral reinforcing member disposed between the first and second portions.

[0016] Figure 7 is a partial cross-sectional perspective view of a hose assembly comprising a core tube, a first reinforcing layer having a first integral reinforcing member therein disposed about the core tube, and a second reinforcing layer disposed about the first reinforcing layer, the second reinforcing layer having a second integral reinforcing member therein.

[0017] Figure 8 is a partial cross-sectional perspective view of a hose assembly comprising a core tube, a reinforcing layer having an integral reinforcing member therein, and a supplemental reinforcing layer disposed about the reinforcing layer.

[0018] Figure 9 is a partial cross-sectional perspective view of a hose assembly comprising a core tube, a reinforcing layer having two integral reinforcing members therein, and a supplemental reinforcing layer disposed about the reinforcing layer.

[0019] Figure 10 is a partial cross-sectional perspective view of a hose assembly comprising a core tube, a supplemental reinforcing layer disposed about the core tube, and a reinforcing layer having an integral reinforcing member therein disposed about the supplemental reinforcing layer.

[0020] Figure 11A is perspective view of a braider with 11 spools of a reinforcing yam and 1 spool of an integral reinforcing member braiding a reinforcing layer about an outer peripheral surface of a core tube to form an embodiment of a hose assembly.

[0021] Figure 1 IB is a partial side view of the hose assembly of Figure 11 A having the reinforcing layer comprising the reinforcing yam and the reinforcing fiber.

[0022] Figure 11C is a side view of the hose assembly of Figure 1 IB having a protective layer disposed about an outer peripheral surface of the reinforcing layer.

[0023] Figure 1 ID is a cross-sectional view of the hose assembly of Figure 11C having the core tube, the reinforcing layer, and the protective layer.

[0024] Figure 12A is a perspective view of a braider with 10 spools of a reinforcing yam and 2 spools of an integral reinforcing member braiding a reinforcing layer about an outer peripheral surface of a core tube to form an embodiment of a hose assembly. [0025] Figure 12B is a partial side view of the hose assembly of Figure 12A having the reinforcing layer comprising the reinforcing yam and the reinforcing fiber.

[0026] Figure 12C is a side view of the hose assembly of Figure 12B having a protective layer disposed about an outer peripheral surface of the reinforcing layer.

[0027] Figure 12D is a cross-sectional view of the hose assembly of Figure 12C having the core tube, the reinforcing layer, and the protective layer.

[0028] The drawings are illustrative of the invention, and it is to be understood that the drawings are not necessarily to scale and the components within each individual drawing are not necessarily to scale. To this end, the drawings are intended to be descriptive and not limiting in nature. Many modifications and variations of the drawings are possible in light of the teachings below.

DETAILED DESCRIPTION

[0029] Referring to the Figures wherein like numerals indicate like or corresponding parts throughout the several views, a hose assembly 10 is generally shown. The hose assembly 10 comprises a core tube 12 having an inner and an outer peripheral surface 14, 16 and a reinforcing layer 18 disposed about the outer peripheral surface 16 of the core tube 12. The reinforcing layer 18 comprises a reinforcing yam 20 and an integral reinforcing member 22 comprising metal which are braided together.

[0030] The hose assembly 10 is typically used for conveying fluids, such as fuels, chemicals, etc. The hose assembly 10 is particularly suitable for use in the transportation industry, e.g. in vehicles. Figure 1 shows the hose assembly 10 utilized as a fuel line in an automobile. However, it is to be appreciated that the hose assembly 10 is not limited to the transportation industry. For example, the hose assembly 10 can be utilized in the chemical industry, the food industry, and any other suitable industry.

[0031] Referring to Figure 2, the hose assembly 10 includes the core tube 12 defining a tubular configuration along an axis Z. The core tube 12 is resistant to chemical and thermal degradation. The inner peripheral surface 14 of the core tube 12 can be smooth, such that minimal turbulence is created as fluid flows therethrough or can be textured for various reasons. The outer peripheral surface 16 of the core tube 12 can be smooth or textured.

[0032] The core tube 12 is formed from a polymeric material. In one embodiment, the core tube 12 comprises one or more layers. The core tube 12 can be a monolayer core tube 12 or a multilayer core tube 12. Suitable, non-limiting examples of the polymeric material which can be used to form the one or more layers of the core tube 12 include polyethylene, polypropylene, polyvinylchloride, polyethyleneterephtalate (PET), polybutyleneterepthalate (PBT), polyamides, fiuoropolymers, or copolymers thereof. Suitable, non-limiting examples of particular fiuoropolymers include polytetrafluoroethylene ("PTFE"), Fluorinated Ethylene Propylene ("FEP"), Perfluoroalkoxy ("PFA"), and ethylenetetrafluoroethylene ("ETFE"). Suitable, non- limiting examples of particular polyamides include PA11, PA12, PA610, PA612, PA1010, PA6, PA66, PA1110T, PA1212T, and blends thereof.

[0033] In various embodiments, the core tube 12 is the multilayer core tube 12 wherein the layers comprise different materials, and, thus, provide advantages associated with the different materials. For example, the multilayer core tube 12 can comprise an inner layer which is thermally stable and an outer layer which softens during formation of the hose assembly 10 so that a reinforcing layer 18 embeds in the outer layer to provide excellent adhesion between the reinforcing layer 18 and the core tube 12. As another example, the multilayer core tube 12 may include an inner layer comprising fluorocarbon polymer that defines the inner peripheral surface 14, which is resistant to chemical and thermal degradation, and an outer layer comprising polyamide that defines the outer peripheral surface 16, which is durable and provides excellent high temperature resistance.

[0034] In some embodiments, the hose assembly 10 includes a surface treatment. The surface treatment is disposed on the outer peripheral surface 16 of the core tube 12. Suitable surface treatments include, but are not limited to, a coupling agent, a primer, and/or various other surface treatments such as physical, chemical, plasma, or corona etching. If applied, the surface treatment is typically applied to the outer peripheral surface 16 of the core tube 12 to facilitate bonding of materials thereto.

[0035] In various embodiments, the core tube 12 is electrically conductive. The core tube 12 can also include an integral conductor along a length of the core tube 12 for preventing build up of electrical charge. As fluid flows through the core tube 12, electrical charges tend to build throughout the length of the core tube 12. In order to prevent these electrical charges from accumulating, in various embodiments, the core tube 12 has the integral conductor, which functions as an integral longitudinal conductive means coextensive with the length of the core tube 12 for conducting an electrical charge. [0036] In one specific embodiment, the integral conductor is a conductive strip of carbon black, e.g. the core tube 12 has a conductive strip of carbon black. Carbon black is electrically conductive and will dissipate any electrical charges built up by the fluid. This is done by using carbon black about the core tube 12. It should be appreciated that other conductive material may be used to form the integral conductor.

[0037] In some embodiments, the core tube 12 is the multilayer core tube 12 comprising a conductive inner layer and a non-conductive outer layer. In one specific embodiment, the core tube 12 is the multilayer core tube 12 comprising PTFE formed from an inner material (e.g. conductive PTFE) and an outer material (e.g. non-conductive PTFE) and, thus, the inner peripheral surface 14 of the monolayer core tube 12 is conductive. In another embodiment, a monolayer core tube 12 can comprise the conductive means, e.g. can be formed from conductive PTFE.

[0038] In one preferred embodiment, the core tube 12 is multilayer and the innermost layer (or liner, as it is sometimes referred to in the art) comprises PTFE. In such an embodiment, the core tube 12 is typically conductive.

[0039] In another preferred embodiment, the core tube 12 is monolayer and comprises PTFE. In such an embodiment, the core tube 12 is typically non-conductive.

[0040] In most embodiments, the reinforcing layer 18 is not electrically conductive. As such, electrical charges applied to the reinforcing layer 18 will not be conducted throughout the hose assembly 10 or to the fluid passing through the interior of the core tube 12.

[0041] Still referring to Figure 2, the hose assembly 10 further includes the reinforcing layer 18 for increasing the strength, durability, and bending properties of the hose assembly 10. The reinforcing layer 18 is disposed about the outer peripheral surface 16 of the core tube 12. The reinforcing layer 18 comprises the reinforcing yam 20 and the integral reinforcing member 22 braided about the outer peripheral surface 16 of the core tube 12. The reinforcing yam 20 has a diameter DY and the integral reinforcing member 22 has a diameter DRM. A ratio of DY to DRM is from about 3:2 to about 8: 1, alternatively from about 2: 1 to about 4: 1.

[0042] The reinforcing layer 18 typically covers greater than about 30, alternatively greater than about 40, alternatively greater than about 50, alternatively greater than about 60, alternatively greater than about 70, alternatively greater than about 80, alternatively greater than about 90, alternatively greater than about 95, % of the outer peripheral surface 16 of the core tube 12.

[0043] As set forth above, the reinforcing layer 18 comprises the reinforcing yam 20 that are braided, helically wound, knitted, or wrapped about the outer peripheral surface 16 of the core tube 12. The reinforcing layer 18 can comprise one or more different types of the reinforcing yam 20. The reinforcing yam 20 can be monofilament, multifilament, or staple yam. The reinforcing yarn 20 typically comprises multiple filaments of a reinforcing fiber (i.e. is a multifilament yam). The reinforcing yam 20 can include one or more types of the reinforcing fiber. The reinforcing fiber typically comprises a polymer, a ceramic, a fiberglass, a metal, or combinations thereof. In one embodiment, the reinforcing yam 20 comprises E-glass fibers. In another embodiment, the reinforcing yarn 20 comprises E-glass and aramid (polyamide) fibers.

[0044] Examples of suitable glass reinforcing fiber include, but are not limited to, E- glass (alumina-calcium-borosilicate), S2 glass (magnesium-alumino-silicate), C glass (calcium borosilicate), R glass (calcium-alumino-silicate), silica, quartz, and combinations thereof. Examples of other suitable reinforcing fibers include, but are not limited to, Basalt fiber, ceramic fiber, para aramid fiber (e.g. TWARON® and KEVLAR® fiber), meta aramid fiber (e.g. Nomex® fiber), semi-aromatic aramid fiber, and combinations thereof. Of course, as is set forth above, one or more different types of reinforcing fiber can be used, i.e., blends of any of the reinforcing yam 20 described herein can be used.

[0045] In some embodiments, the reinforcing yam 20 comprises a polymer, a ceramic, a fiberglass, a metal, or combinations thereof, which are coated with a polymeric binder 24.

[0046] In a preferred embodiment, the reinforcing yam 20 comprises E-glass fiber. Reinforcing yam 20 comprising fiberglass provides strength to reinforce the core tube 12 and thermal stability at elevated temperatures, which is beneficial for use in high temperature environments, e.g. under the hood of vehicles.

[0047] In various embodiments, the reinforcing yam 20 has a diameter of from about 0.05 to about 0.2, alternatively from about 0.06 to about 0.16, alternatively from about 0.6 to about 0.7, alternatively from about 0.7 to about 0.8, alternatively from about 0.8 to about 0.9, alternatively from about 0.9 to about 0.1, alternatively from about 0.12 to about 0.17, inches. [0048] As is also set forth above, the reinforcing layer 18 comprises the integral reinforcing member 22.

[0049] The integral reinforcing member 22 can be (1) disposed on an inner peripheral surface 14 of the reinforcing layer 18, (2) braided, helically wound, knitted, or wrapped with the reinforcing yam 20 about the outer peripheral surface 16 of the core tube 12 within the reinforcing layer, or (3) can be disposed on an outer peripheral surface 16 of the reinforcing layer 18.

[0050] In a preferred embodiment, the integral reinforcing member 22 is braided, helically wound, knitted, or wrapped with the reinforcing yarn 20 about the outer peripheral surface 16 of the core tube 12. As such, the integral reinforcing member 22 is typically helically wrapped around the outer peripheral surface 16 of the core tube 12 within the reinforcing layer 18.

[0051] Of course, the reinforcing layer 18 can comprise one or more integral reinforcing members 22. The integral reinforcing member 22 improves the crush resistance, flexibility, durability, and kink resistance of the hose assembly 10. It is preferred that the integral reinforcing member 22 have a tensile modulus which is higher than the tensile modulus of the reinforcing yam 20 (e.g. glass fibers) of the braided reinforcing layer 18. In various embodiments, the integral reinforcing member 22 comprises a polymer, a fiberglass, a ceramic, a glass, a metal, or combinations thereof. In a preferred embodiment the integral reinforcing member 22 comprises metal.

[0052] In preferred embodiments the integral reinforcing member 22 comprises metal. Suitable metals include, but are not limited to, aluminum, steel, stainless steel, and other alloys known in the art. In one preferred embodiment, the integral reinforcing member 22 comprises stainless steel. Suitable steels include, but are not limited to, 302, 304, 305, 314, 316, 321, 330, 347, 430, Monel, and Inconel. Stainless steel typically has a tensile modulus of about 180 GPa, whereas most polymers typically have a tensile modulus of less than 10 GPa. In contrast, glass fibers typically have a tensile modulus of from about 50 to about 90 GPa, while Aramid fiber typically has a tensile modulus of about 70 to about 112 GPa.

[0053] In one preferred embodiment, the integral reinforcing member 22 comprises austenitic bright annealed 304 steel wire. Austenitic bright annealed 304 steel wire is preferred because of its ability to be bent with minimal spring back. In addition, without being bound by theory, we believe that the bright annealed 304 steel wire allows for the formation of various embodiments of the hose assembly 10 which have minimal spring back and can be thermally formed into a particular shape. Once thermally formed, the hose assembly 10 retains its thermally formed shape with minimal spring back.

[0054] In some alternative embodiments the integral reinforcing member 22 comprises a polymeric material which is rigid and also resistant to chemical and thermal degradation. Suitable polymeric materials include, but are not limited to, polyamide, polyethylene, polypropylene, polyphthalamide, and polyphenylene sulfide. In other alternative embodiments, the integral reinforcing member 22 comprises a mineral material or a ceramic material which is rigid and also resistant to chemical and thermal degradation.

[0055] In many embodiments, the integral reinforcing member 22 is coated with a polymeric coating 23. The polymeric coating 23 can comprise, consist essentially of, or consist of any polymer known in the art. The polymeric coating 23 can comprise, consist essentially of, or consist of fiuoropolymer, polyamide, silicone, polyethylene, polypropylene, polyvinylchloride, polyethylene terephthalate, and polybutylene terephthalate. However, the polymeric coating 23 typically comprises, consists essentially of, or consists of a fiuoropolymer and/or a polyamide. Suitable non-limiting examples of fiuoropolymer include polytetrafluoroethylene, ethylene tetrafluoroethylene, fluorinated ethylenepropylene, polyvinylidine fluoride, perfluoroalkoxy fluorocarbons, polychlorotrifluoroethylene, and combinations thereof. Suitable non-limiting examples of polyamide include PA11, PA12, PA610, PA612, PA1010, PA6, PA66, PA1110T, and PA1212T, and combinations thereof.

[0056] In some embodiments, the polymeric coating 23 has a softening temperature (point) and/or a melting temperature (point) of from about 200 to about 400, alternatively from about 200 to about 350, alternatively from about 200 to 310, °C. In some such embodiments, the softening temperature and/or the melting temperature is less than a softening temperature and/or a melting temperature of the reinforcing fibers of the reinforcing yam 20. In some such embodiments, the hose assembly 10 can be heated during manufacturing such that the polymeric coating 23 melts to bind/form a robust bond between the integral reinforcing member 22 and the reinforcing yam 20. In other such embodiments, the polymeric coating 23 melts to bind (1) the reinforcing fibers within the reinforcing yam 20 together, (2) the reinforcing yam 20 and the integral reinforcing member 22 together, and (3) the reinforcing yam 20 and the and the integral reinforcing member 22 to the outer peripheral surface 16 of the core tube 12. [0057] In some embodiments, the polymeric coating 23 has a coefficient of friction (COF) of from about 0.05 to about 0.5, alternatively about 0.09 to about 0.4. In such embodiments, the COF allows for the integral reinforcing member 22 to be braided about an exterior surface of the hose assembly 10 with the reinforcing yam 20 on conventional braiding equipment. In other words, the polymeric coating 23 of the integral reinforcing member 22 reduces the friction during the braiding process.

[0058] The integral reinforcing member 22 can have a cross-sectional profile of any suitable configuration, such as a circle, an oval, or any type of ellipse, a closed parabolic shape, a quadrilateral, or any other type of polygon. In a preferred embodiment, the cross-sectional profile of integral reinforcing member 22 is circular. The diameter of the integral reinforcing member 22 can vary depending on the application.

[0059] In various embodiments, the integral reinforcing member 22 has a diameter of from about 5 to about 200, alternatively from about 10 to about 180, alternatively from about 15 to about 160, alternatively from about 20 to about 140, mils. Alternatively, in various embodiments, the integral reinforcing member 22 has a diameter of from about 0.01 to about 0.1, alternatively from about 0.01 to about 0.08, inches.

[0060] For example, in some embodiments, the integral reinforcing member 22 comprises a metal coated with the polymeric coating 23. In one embodiment, the integral reinforcing member 22 is coated with PTFE. In another embodiment, the integral reinforcing member 22 is coated with PFA. In some embodiments, the integral reinforcing member 22 comprises metal in an amount of from about 60 to about 99, alternatively from about 70 to about 95, % by volume, and the polymeric coating 23 in an amount of from about 1 to about 40, alternatively from about 5 to about 30, % by volume, based on 100% of the volume of the integral reinforcing member 22.

[0061] The polymeric coating 23 typically has a nominal thickness e.g. from about 0.5 to about 200 mils. Referring now to Figure 3, a cross-sectional view of the integral reinforcing member 22 comprising bright annealed 304 stainless steel metal and the polymeric coating 23 comprising PFA is shown. The integral reinforcing member 22 has a diameter of 36 mils, 22 mils of which are attributed to the metal portion of the integral reinforcing member 22 and 14 mils of which are attributed to the polymeric coating 23 comprising PFA. Referring now to Figure 4, a cross-sectional view of the integral reinforcing member 22 comprising bright annealed 304 stainless steel metal and polymeric coating 23 comprising PFA is shown. The integral reinforcing member 22 has a diameter of 118 mils, 100 mils of which are attributed to the metal portion of the integral reinforcing member 22 and 18 mils of which are attributed to the polymeric coating 23 comprising PFA.

[0062] Referring now to the reinforcing layer 18, the reinforcing layer 18 comprises, consists essentially of, or consists of the reinforcing yam 20 and the integral reinforcing member 22 braided, helically wound, knitted, or wrapped about the core tube 12.

[0063] In some embodiments, the integral reinforcing member 22 and/or the reinforcing yam 20 can have an adhesion promoter applied thereto. The organopolysiloxane adhesion promoter can be applied to the fibers of the reinforcing layer 18 to improve (1) adhesion of the reinforcing layer 18 to the core tube 12, and/or (2) the adhesion of the reinforcing fibers of the reinforcing yam 20 to one another, and/or (3) the adhesion of the integral reinforcing member 22 to the reinforcing yarn 20 and/or (4) the adhesion of the reinforcing layer 18 (and braids thereof) to an outer layer (e.g. a silicone jacket).

[0064] In some embodiments, the reinforcing layer 18 covers greater than 30, alternatively greater than 40, alternatively greater than 50, alternatively greater than 60, alternatively greater than 70, alternatively greater than 80, alternatively greater than 90, alternatively greater than 95, % of the outer peripheral surface 16 of the core tube 12. In one embodiment, the reinforcing layer 18 covers about 50% of the outer peripheral surface 16 of the core tube 12. In another embodiment, the reinforcing layer 18 covers about 100% of the outer peripheral surface 16 of the core tube 12.

[0065] In some embodiments, the reinforcing layer 18 comprises from about 60 to about 99, alternatively from about 80 to about 98, percent by volume of the reinforcing yam 20 and from about 1 to about 40, alternatively from about 2 to 20, percent by volume of the integral reinforcing member 22. The percent by volume set forth is based on 100% of the volume of the reinforcing layer 18.

[0066] In various embodiments from about 1 to about 10, alternatively from about 1 to about 8, alternatively from about 1 to about 4, alternatively from about 1 to about 2, integral reinforcing members 22 can be helically wrapped about or within the braided reinforcing yarn 20 to form the reinforcing layer 18. In some embodiments, the reinforcing layer 18 comprises from about 2 to about 8, alternatively from 2 to 4 strands (often referred to in the art as "ends") of the integral reinforcing member 22, and from about 2 to about 22, alternatively from 2 to 12, alternatively from 2 to 10, strands of the reinforcing yam 20, which are braided together. [0067] The number of reinforcing members 22 included in the reinforcing layer 18 is typically dependent on number ends used to make the reinforcing layer. For example, in some embodiments, 1 end of the reinforcing member 22 can be used on a 12 carrier deck (as is shown in figure 11 A) on a 24 carrier braider. As another example, in some embodiments, 2 ends of wire reinforcement on a 12 carrier deck on a 24 carrier braider. Braiders are typically manufactured in any multiple of 4 carriers with the most common sizes being, 8, 12, 16, 24, 48, 64, 72, 96, & 144 carriers. Typically the more carriers, the larger the hose diameter.

[0068] As set forth above, the reinforcing layer 18 can comprise one or more integral reinforcing members 22. That is, one or more integral reinforcing members 22 can be helically wrapped around the outer peripheral surface 16 of the core tube 12 within the reinforcing layer 18. To this end, the pitch at which the integral reinforcing member 22 is helically wrapped around the core tube 12 (within the reinforcing layer 18) can vary. In some embodiments where the reinforcing layer 18 comprises more than 1 end of the integral reinforcing member 22, the integral reinforcing members 22 can be braided such that the integral reinforcing members 22 do not cross one another in the reinforcing layer 18. In other embodiments where the reinforcing layer 18 comprises more than 1 end of the integral reinforcing member 22, the integral reinforcing members 22 can be braided such that the integral reinforcing members 22 cross one another in the reinforcing layer 18 at an angle of from about 30 to about 70, alternatively from about 40 to about 60°. For example, Figure 5 is a partial cross-sectional perspective view of an embodiment of the hose assembly 10 comprising the core tube 12 and the reinforcing layer 18 having two integral reinforcing members 22 therein. In the embodiment of Figure 5, the two integral reinforcing members 22 cross one another and provide "cross-reinforcement".

[0069] In one embodiment, the reinforcing layer 18 comprises a first portion 18A, a second portion 18B, and the integral reinforcing member 22 disposed therebetween. Referring now to Figure 6, in such an embodiment, the integral reinforcing member 22 is helically disposed about the first portion 18A and the second portion 18B is then braided over the first portion 18A with the integral reinforcing member 22 therebetween to form the reinforcing layer 18. That is, in Figure 6 a partial cross-sectional perspective view of the hose assembly 10 comprising the core tube 12, a reinforcing layer 18 comprising a first and second portion with an integral reinforcing member 22 disposed between the first and second portions. [0070] The integral reinforcing member 22 (or members) improves the crush resistance, flexibility, durability, and kink resistance of the hose assembly 10. The hose assembly 10 performs well in impulse tests. The integral reinforcing member 22 is integral with the reinforcing layer 18 and this increases the cohesive strength of the hose assembly 10 and reduces likelihood that the hose assembly 10 will kink or fail during use. Further, a number of the integral reinforcing members 22 and a configuration (e.g. parallel or crossed) of the integral reinforcing members 22 can be tailored to and optimized for specific hose applications.

[0071] Referring now to Table 1, various, non-limiting and exemplary configurations of the reinforcing layer 18 can be braided comprising ends of the reinforcing yarn 20 and the integral reinforcing member 22 having the dimensions (e.g. diameters disclosed). All dimensions in Table 1 are set forth in inches. DY is referred to as a "lay-flat" diameter because it is measured by measuring the width of the braid as it "lays flat" on an outer peripheral surface (e.g. the outer peripheral surface 16 of the core tube 12) of the hose assembly 10. As is seen in Table 1, a ratio of DY to DRM is from about 3:2 to about 8: 1, alternatively from about 2: 1 to about 4: 1.

TABLE 1

Hose Assembly 10 0.4375 0.0403 0.085 2.1

Hose Assembly 11 0.5 0.0446 0.094 2.1

Hose Assembly 12 0.875 0.0718 0.1515 2.1

[0072] The hose assembly 10 can include one or more of the reinforcing layer 18. Referring now to Figure 7, a partial cross-sectional perspective view of an embodiment of the hose assembly 10 comprising the core tube 12, a first reinforcing layer 18-1 having an integral reinforcing member 22 therein, and a second reinforcing layer 18-2 having an integral reinforcing member 22 therein is shown. In the embodiment of Figure 7, the hose assembly 10 includes a core tube 12, a first reinforcing layer 18-1 having an first integral reinforcing member 22-1 therein disposed about the core tube 12, and a second reinforcing layer 18-2 disposed about the first reinforcing layer 18-1, said second reinforcing layer 18-2 having a second integral reinforcing member 22-2 therein.

[0073] The hose assembly 10 can also include one or more supplemental reinforcing layers 26. The supplemental reinforcing layer 26 is the same as the reinforcement layer described above but it does not include the integral reinforcing member 22. That is, the supplemental reinforcing layer 26 comprises ends of reinforcing yarn 20 in place of ends of the integral reinforcing member 22. The supplemental reinforcing layer 26 can be formed as described immediately above or from various other embodiments known in the art. The type and amount of the supplemental reinforcing layer 26 included in the hose assembly 10 depends on the intended use of the hose assembly 10.

[0074] For example, Figure 8 is a partial cross-sectional perspective view of an embodiment of the hose assembly 10 comprising the core tube 12, the reinforcing layer 18 having the integral reinforcing member 22 therein disposed about the core tube 12, and a supplemental reinforcing layer 26 disposed about the reinforcing layer 18 having the integral reinforcing member 22 therein. As another example, Figure 9 is a partial cross-sectional perspective view of another embodiment of the hose assembly 10 comprising the core tube 12, the reinforcing layer 18 having two integral reinforcing members 22 disposed about the core tube 12, and a supplemental reinforcing layer 26 disposed about the reinforcing layer 18 which provides "cross-reinforcement". [0075] As an alternative example, Figure 10 is a partial cross-sectional perspective view of an embodiment of the hose assembly 10 comprising the core tube 12, the supplemental reinforcing layer 26 disposed about the core tube 12, and the reinforcing layer 18 having the integral reinforcing member 22 therein disposed about an outer peripheral surface 16 of the reinforcing layer 18. In the embodiment of Figure 10, the reinforcing layer 18 can still be considered to be disposed about the core tube 12 despite the intervening supplemental reinforcing layer 26.

[0076] The hose assembly 10 can include a protective layer 28. The hose assembly 10 can also include one or more of the protective layer 28. The type and amount of protective layers 28 included in the hose assembly 10 depends on the intended use of the hose assembly 10.

[0077] In a typical embodiment the protective layer 28 is disposed about an exterior surface of the reinforcing layer 18. In some embodiments, the hose assembly 10 includes a protective layer 28 comprising a fluoropolymer. In some embodiments, the hose assembly 10 includes a protective layer 28 comprising a silicone. In some embodiments, the hose assembly 10 includes two protective layers 28, a first protective layer 28 comprising a fluoropolymer, and a second protective layer 28 comprising silicone.

[0078] In some embodiments, the protective layer 28 can be formed with the polymeric binder 24, e.g. comprising a fluoropolymer and other components. In many embodiments, the polymeric binder 24 of the protective layer 28 penetrates into indentations and gaps in the outer peripheral surface 16 of the reinforcing layer 18. As described previously, different embodiments of the reinforcing layer 18 cover varying percentages of the outer peripheral surface 16 of the core tube 12 so that more or less of the polymeric binder 24 can penetrate into the reinforcing layer 18. That is, in some embodiments, the polymeric binder 24 which is used to form the protective layer 28 is disposed about the exterior surface of the reinforcing layer 18 and penetrates into apertures in the reinforcing layer 18.

[0079] The polymeric binder 24 typically comprises a polymer. Suitable polymers include, but are not limited to, polyethylene, polypropylene, polyvinylchloride, PET, PBT, polyamide, fluoropolymer, and copolymers thereof. In a preferred embodiment, the polymeric binder 24 comprises a fluoropolymer and/or a polyamide. Examples of suitable fiuoropolymers include, but are not limited to, PTFE, FEP, PFA, and ETFE. In yet another embodiment, the polymeric binder 24 comprises a polyamide. Examples of suitable poly amides include, but are not limited to, PA11, PA12, PA610, PA612, PA1010, PA6, PA66, PA1110T, PA1212T, and blends thereof.

[0080] In preferred embodiments, the polymeric binder 24 is applied in an emulsion, e.g., the hose assembly 10 having the reinforcing yam 20 and the integral reinforcing member 22 disposed thereabout is dipped in an emulsion comprising the polymeric material and then heated to form the reinforcing layer 18.

[0081] In some embodiments the polymeric coating 23 which is coated on the integral reinforcing member 22 and melts upon heating to form the reinforcing layer 18 having the integral reinforcing member 22 therein can function as the polymeric binder 24.

[0082] In some embodiments, the polymeric binder 24 is formed from binding fibers. The use of binding fiber is described in PCT/US2013/070317 and PCT/US2013/070342, both filed November 15, 2013, the entirety of which is incorporated by reference herein. That is, in some embodiments, the reinforcing layer 18 is formed from binding fibers. If binder 24 fibers are used to form the reinforcing layer 18, the reinforcing layer 18 can be formed from one or more different types of binding fibers. The binding fibers are typically in the form of monofilament strands or multifilament yam. Examples of polymers suitable for the binding fibers include, but are not limited to, polyethylene, polypropylene, polyvinylchloride, PET, PBT, polyamide, fluoropolymer, and copolymers thereof.

[0083] Various applications and combinations of the polymeric binder 24 described above have been contemplated and can be used in the hose assembly 10. For example, a protective layer 28 can be formed on the hose assembly 10 via application of the polymeric binder 24 via emulsion, and the polymeric coating 23 which is coated on the integral reinforcing member 22 can also melt upon heating effectively functioning as polymeric binder 24 in the hose assembly 10. As another example, a hose assembly 10 can be formed with a polymeric binder 24 and also binding fibers. As a final example, the polymeric binder 24 can originate as the polymeric coating 23 which is coated on the integral reinforcing member 22 without the use of the emulsion comprising the polymeric binder 24 or polymeric binder 24 fibers.

[0084] In other embodiments, the protective layer 28 can comprise a silicone layer (e.g. a silicone rubber jacket). The silicone rubber jacket of this embodiment comprises a silicone. Of course, the silicone rubber jacket can comprise one or more types of silicone. In one embodiment, the silicone comprises a polyalkylsiloxane such as polydimehtylsiloxane ("PDMS"). In another embodiment, the silicone comprises a silicone having halide functional groups (e.g. a fluoro silicone). In yet another embodiment, the silicone comprises a silicone having phenyl functional groups (e.g. phenyl silicone). The silicone can be room temperature vulcanizing ("RTV") silicone, which cures at room temperature, or high temperature vulcanizing ("HTV") silicone, which cures at temperatures greater than 100°C. In one embodiment, the silicone rubber jacket comprises HTV silicone (either a high consistency rubber ("HCR") or a liquid silicone rubber ("LSR")).

[0085] Of course, if the hose assembly 10 includes layers in addition to the reinforcing layer 18, the protective layer 28 can be disposed about an exterior surface of the hose assembly 10, e.g. about an outer peripheral surface 16 of a supplemental reinforcing layer 26. That is, there can be intervening layers between the reinforcing layer 18 and the protective layer 28.

[0086] The various layers of the hose assembly 10 described herein can be included in the hose assembly 10 in varying order. To this end, the reinforcing layer does not have to be adjacent to and disposed about the core tube 12 - there can be intervening layers. Likewise, the protective layer 28 does not have to be the outermost layer of the hose assembly 10. For example, a protective layer 28 could be disposed between the core tube 12 and the reinforcing layer 18 or, as another example; the protective layer 28 could be disposed between the reinforcing layer 18 and the supplemental reinforcing layer 26.

[0087] The hose assembly 10 has an inner diameter, an outer diameter, and a length. The inner diameter, the outer diameter, and the length of the hose assembly 10 can vary depending on the intended use of the hose assembly 10. For example, the hose assembly 10 can have an inner diameter of two inches for use in applications that require transfer of greater volumes of fluid or an inner diameter of a half of an inch for use in applications that require transfer of lesser volumes of fluid.

[0088] The hose assembly 10 can further include a coupling (not shown). Typically the coupling is adapted to engage at least one end of the hose assembly 10 for interconnecting the hose assembly 10 to a fluid source, such as fuel tanks. It is to be appreciated that any suitable coupling can be used with the hose assembly 10.

[0089] A method of forming a hose assembly 10 is disclosed. The method includes the steps of extruding the core tube 12 and braiding the reinforcing yam 20 and the integral reinforcing member 22 about the outer peripheral surface 16 of the core tube 12 to form the reinforcing layer 18.

[0090] As set forth above, the method includes the step of extruding the core tube 12. The core tube 12 is just as described above. The core tube 12 is extruded to the desired dimensions using melt, paste, or any other extrusion technique known in the art. Of course, in various embodiments the core tube 12 is a multilayer core tube 12 which can be formed with techniques known in the art, such as co-extrusion techniques. In other embodiments, the core tube 12 is the monolayer core tube 12 formed via a paste extrusion.

[0091] As is also set forth above, the method also includes the step of forming the reinforcing layer 18 from the reinforcing yam 20 and the integral reinforcing member 22. More specifically, the step of braiding the reinforcing yarn 20 and the integral reinforcing member 22 about the outer peripheral surface 16 of the core tube 12 to form the reinforcing layer 18. The reinforcing layer 18 can comprise various configurations of the reinforcing yam 20 (including various types of reinforcing fiber), and various configurations of the integral reinforcing member 22.

[0092] The method includes the step of disposing the reinforcing yam 20 and the integral reinforcing member 22 about the outer peripheral surface 16 of the core tube 12 to form a reinforced core tube 12 which is, in a typical embodiment, heated to form the reinforcing layer 18. In one embodiment, the step of forming the reinforcing layer 18 is conducted on braiding equipment which includes from 1 to 4 carriers which can braid from 2 to 24 braids about the outer peripheral surface 16 of the core tube 12. The braiding equipment disposes the reinforcing yam 20 and the integral reinforcing member 22 about the outer peripheral surface 16 of the core tube 12. The reinforcing yam 20, the integral reinforcing member 22, and the polymeric binder 24 fiber (if included) is typically disposed about the outer peripheral surface 16 of the core tube 12 via braiding, helically winding, knitting, twisting, or wrapping with the equipment. The core tube 12 can be extruded and the braids of reinforcing fiber 20, the integral reinforcing member 22, and the polymeric binder 24 fiber (if included) disposed about the outer peripheral surface 16 of the core tube 12 in a single step (in-line) or in two separate steps.

[0093] In one embodiment, the reinforcing layer 18 is formed with the braiding equipment such that the majority of the bobbins braid the reinforcing yam 20 comprising glass reinforcing fiber and/or polymeric binder 24 fiber, and a minority of bobbins braid the integral reinforcing member 22 comprising stainless steel or fluoropolymer coated stainless steel coated wire. The integral reinforcing member 22 is preferably braided about the outer peripheral surface 16 of the core tube 12 such that integral reinforcing member 22 forms a helix about the outer peripheral surface 16 of the core tube 12, but the integral reinforcing member 22 does not cross over itself.

[0094] In many embodiments, the integral reinforcing member 22 braided about the outer peripheral surface 16 of the core tube 12 is contained within the braids of the reinforcing layer 18, in a spiral configuration, at a frequency that is sufficient to provide improved kink resistance performance. In such embodiments, the reinforcing layer 18 (having the integral reinforcing member 22 therein) is bonded to the core tube 12 sufficiently to withstand the tension forces created by the integral reinforcing member 22.

[0095] In some embodiments, as is described above, "cross reinforcement", i.e., reinforcement which is on a plane perpendicular to the Z axis is included in the hose assembly 10. It is believed that cross-reinforcement creates a "cage effect" to further reinforce the hose assembly 10. The cross reinforcement can be metal wire or the like. For example, the cross reinforcement can be stainless steel wire or soft annealed stainless steel wire. In a preferred embodiment, the cross reinforcement is formed from soft annealed stainless steel wire. In such a preferred embodiment, it is believed that the increase in the force to bend of the hose assembly 10 with cross reinforcement would not be too much and the spring back of the hose assembly 10 would be less of a concern. Of course, such an embodiment is thermally formable.

[0096] In various embodiments, the reinforcing yam 20, the integral reinforcing member 22, and the polymeric binder 24 fiber (if included) are braided on braiding equipment with from about 1 to about 48 carriers/bobbins. In one embodiment, the braiding equipment utilizes an upper deck which braids 6 to 14 braids of any combination. For example, the upper deck can braid 9 braids/ends comprising reinforcing fiber (the same or different) and 3 ends of the integral reinforcing member 22 (the same or different). The braids can comprise any combination of the reinforcing yarn 20, the integral reinforcing member 22, and binding fibers. Such equipment can also utilize a lower deck which braids 6 to 14 ends of any combination, just as explained with respect to the upper deck above. [0097] In one embodiment, the reinforcing layer 18 is formed with a braider whereby the upper deck disposes/braids 12 yams (9 reinforcing yams 20 comprising glass reinforcing fiber and PFA binding 24 fiber, and 3 ends of the integral reinforcing member 22 comprising austenitic bright annealed 304 stainless steel wire coated with PFA binder 24, 6 ends of glass reinforcing fiber 20, and 1 end of aramid reinforcing fiber 20) about the outer peripheral surface 16 of the core tube 12. In this embodiment, the lower deck disposes/braids 12 yams (the yams formed from 13 ends of glass reinforcing fiber 20 and 1 end of aramid reinforcing fiber 20) about the outer peripheral surface 16 of the core tube 12. Stated differently, in some embodiments a 24 carrier braider with 12 bobbins on the top deck and 12 bobbins on the lower deck is used to dispose the reinforcing layer 18 having the integral reinforcing member 22 therein about the outer peripheral surface 16 of the core tube 12.

[0098] Referring now to Figures 11 A - 1 ID, the steps of disposing the reinforcing layer 18 about the core tube 12 and then forming the protective layer 28 are shown for one embodiment of the method of forming a particular embodiment of the hose assembly 10. In Figure 11A a braider with 11 spools of the reinforcing yam 20 and 1 spool of the integral reinforcing member 22 braiding the reinforcing layer 18 about the outer peripheral surface 16 of the core tube 12 is shown. Figure 1 IB is a partial side view of the hose assembly 10 of Figure 11A having the reinforcing layer 18 comprising the reinforcing yam 20 and the integral reinforcing member 22 braided about the outer peripheral surface 16 (not shown) of the core tube 12 (not shown). Figure 11C is a side view of the hose assembly 10 of Figure 1 1B having the protective layer 28 applied thereon via an emulsion comprising the polymeric binder 24. Figure 11D is a cross- sectional view of the hose assembly of Figure 11 C having the core tube 12, the reinforcing layer 18 disposed about the outer peripheral surface 16 of the core tube 12, and the protective layer 28 comprising the polymeric binder 24 disposed about an outer peripheral surface 16 of said reinforcing layer 18.

[0099] Referring now to Figures 12A - 12D, the steps of disposing the reinforcing layer 18 about the core tube 12 and then forming the protective layer 28 are shown for one embodiment of the method of forming a particular embodiment of the hose assembly 10. In Figure 12A a braider with 10 spools of the reinforcing yam 20 and 2 spools of the integral reinforcing member 22 braiding the reinforcing layer 18 about the outer peripheral surface 16 of the core tube 12 is shown. Figure 12B is a partial side view of the hose assembly 10 of Figure 12A having the reinforcing layer 18 comprising the reinforcing yarn 20 and the integral reinforcing member 22 braided about the outer peripheral surface 16 (not shown) of the core tube 12 (not shown). Figure 12C is a side view of the hose assembly 10 of Figure 12B having the protective layer 28 applied thereon via an emulsion comprising the polymeric binder 24. Figure 12D is a cross- sectional view of the hose assembly of Figure 12C having the core tube 12, the reinforcing layer 18 disposed about the outer peripheral surface 16 of the core tube 12, and the protective layer 28 comprising the polymeric binder 24 disposed about an outer peripheral surface 16 of said reinforcing layer 18.

[00100] In various embodiments known in the art, a first dip in the polymeric binder 24 or an adhesion promoter can be used to improve the adhesion between the core tube 12 and the reinforcing layer 18. The method disclosed herein can employ such a dip. Alternatively, the method can be free of this first dip step. Because of the hose construction disclosed herein, in particular the integral reinforcing member 22, the strength and durability of the hose is excellent without use of a first dip step.

[00101] In many embodiments, the method includes the step of applying a polymeric binder 24, e.g. the hose assembly 10 having the reinforcing yam 20 and the integral reinforcing member 22 disposed thereabout is dipped or immersed in an emulsion comprising the polymeric binder 24, and is then heated (as described immediately below) to form the hose assembly 10. The polymeric binder 24 penetrates into the reinforcing layer and also forms a protective layer 28 on an outer peripheral surface 16 of the hose assembly 10.

[00102] Various embodiments of the reinforcing layer 18 comprise from about 65 to about 98, alternatively from about 75 to about 95 percent by volume reinforcing yam 20, and from about 2 to about 35, alternatively from about 15 to about 35, percent by volume of the polymeric binder 24, and from about 5 to about 33, alternatively from about 5 to about 17, percent by volume integral reinforcing member 22. As is described above, in various embodiments from about 1 to about 10, alternatively from about 1 to about 8, alternatively from about 1 to about 4, alternatively from about 1 to about 2, integral reinforcing members 22 can be helically wrapped about or within the braided reinforcing yam 20 to form the reinforcing layer 18.

[00103] The method may also include the step of heating the hose assembly 10 to melt the polymeric binder 24, and form the reinforcing layer 18. The polymeric binder 24 can be introduced to the hose assembly 10 via use of the integral reinforcing member 22 having polymeric binder 24 coated thereon, binding fibers, spraying the polymeric binder 24, and/or dipping the hose assembly 10 in the polymeric binder 24. The hose assembly 10 is typically heated to a temperature of greater than about 100, alternatively greater than about 150, alternatively greater than about 200, alternatively greater than about 250, alternatively greater than about 300, alternatively from about 300 to about 450, alternatively from about 300 to about 400, °C to thermally bond the layers of the hose assembly 10.

[00104] After the step of heating, the hose assembly 10 is typically cooled to control physical properties of the core tube 12 by controlling the crystallinity of the polymeric materials (polymeric binder 24 and core tube 12 materials) and to maintain the inner diameter and the outer diameter of the core tube 12. Upon cooling, the polymeric binder 24 solidifies, helping make the integral reinforcing member 22 integral with the reinforcing layer 18.

[00105] The method optionally includes the step of pressurizing an interior cavity of the core tube 12 with a fluid such as water, an inert gas (e.g. nitrogen), or air, through an inlet and an outlet (each end of the hose assembly 10) during the step of heating the hose assembly 10. The cavity of the hose assembly 10 is typically pressurized to a pressure of up to about 500 (3447), alternatively from about 5 to about 100 (34.5 to 689.5), alternatively from about 10 to about 75 (68.9 to 517.1), alternatively from about 20 to about 60 (137.9 to 413.7), PSI (kPa). The step of pressurizing the hose assembly 10 maintains the dimensional integrity of the core tube 12 during the step of heating and also facilitates adhesion of the reinforcing layer 18 to the core tube 12 because the pressure forces the fixed braid against the outer peripheral surface 16 of the core tube 12. It is believed that this step facilitates softening of the outer peripheral surface 16 of the core tube 12 and, thus, improves the adhesion of the reinforcing layer 18 to the outer peripheral surface 16 of the core tube 12 while maintaining the dimensional integrity of the internal cavity of the hose assembly 10.

[00106] The method optionally includes the step of further cross-linking the polymeric binder 24. The polymeric binder 24 can be cross-linked with heat, ultraviolent radiation (UV), electron beam, and combinations thereof. The step of cross-linking is typically conducted subsequent to the step of heating the hose assembly 10. If the step of cross- linking is conducted prior to the step of heating the hose assembly 10, the polymeric binder 24 may not flow well into the braid interstices.

[00107] Once formed, the hose assembly 10 can be thermally formed or bent into a finished shape. The reinforcing layer 18 having the integral reinforcing member 22 therein does not create stress in the hose assembly 10, is resilient, and does not change its formed shape over time.

[00108] The hose assembly 10 of the subject disclosure, including the embodiments of the previous three paragraphs, exhibits an excellent bond between the outer peripheral surface 16 of the core tube 12 and the reinforcing layer 18. That is, in many embodiments, the bond is typically so strong that the reinforcing layer 18 cannot be separated or delaminated from the core tube 12 without destroying the hose assembly 10. Without being bound by theory, it is believed that the strength of this bond is the result of the integral reinforcing member 22.

[00109] It is to be understood that the appended claims are not limited to express any particular compounds, compositions, or methods described in the detailed description, which may vary between particular embodiments which fall within the scope of the appended claims. With respect to any Markush groups relied upon herein for describing particular features or aspects of various embodiments, it is to be appreciated that different, special, and/or unexpected results may be obtained from each member of the respective Markush group independent from all other Markush members. Each member of a Markush group may be relied upon individually and or in combination and provides adequate support for specific embodiments within the scope of the appended claims.

[00110] It is also to be understood that any ranges and subranges relied upon in describing various embodiments of the present disclosure independently and collectively fall within the scope of the appended claims, and are understood to describe and contemplate all ranges including whole and/or fractional values therein, even if such values are not expressly written herein. One of skill in the art readily recognizes that the enumerated ranges and subranges sufficiently describe and enable various embodiments of the present disclosure, and such ranges and subranges may be further delineated into relevant halves, thirds, quarters, fifths, and so on. As just one example, a range "of from 0.1 to 0.9" may be further delineated into a lower third, i.e., from 0.1 to 0.3, a middle third, i.e., from 0.4 to 0.6, and an upper third, i.e., from 0.7 to 0.9, which individually and collectively are within the scope of the appended claims, and may be relied upon individually and/or collectively and provide adequate support for specific embodiments within the scope of the appended claims. In addition, with respect to the language which defines or modifies a range, such as "at least," "greater than," "less than," "no more than," and the like, it is to be understood that such language includes subranges and/or an upper or lower limit. As another example, a range of "at least 10" inherently includes a subrange of from at least 10 to 35, a subrange of from at least 10 to 25, a subrange of from 25 to 35, and so on, and each subrange may be relied upon individually and/or collectively and provides adequate support for specific embodiments within the scope of the appended claims. Finally, an individual number within a disclosed range may be relied upon and provides adequate support for specific embodiments within the scope of the appended claims. For example, a range "of from 1 to 9" includes various individual integers, such as 3, as well as individual numbers including a decimal point (or fraction), such as 4.1, which may be relied upon and provide adequate support for specific embodiments within the scope of the appended claims.

[00111] The present disclosure has been described in an illustrative manner, and it is to be understood that the terminology which has been used is intended to be in the nature of words of description rather than of limitation. Many modifications and variations of the present disclosure are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims, the present disclosure may be practiced otherwise than as specifically described.