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Title:
METHOD OF FORMING A COMPOSITE, AND ASSOCIATED COMPOSITE AND APPARATUS
Document Type and Number:
WIPO Patent Application WO/2021/050078
Kind Code:
A1
Abstract:
A method of forming a consolidated fiber-reinforced thermoplastic composite is conducted in a double-belt press and includes heating an unconsolidated fiber-reinforced thermoplastic composite in a volume-controlled heating area to form a consolidated fiber-reinforced thermoplastic composite, and cooling the consolidated fiber reinforced thermoplastic composite in a constant-volume cooling area. The volume-controlled heating area includes a fixed roller module and is characterized by an initial belt separation, h1, and a final belt separation, h2, wherein the ratio of h1 to h2 is 5:1 to 10:1. The constant-volume cooling area includes a first cooling zone with a circulating roller module, and a second cooling zone with a fixed roller module. Also described are a consolidated fiber-reinforced thermoplastic composite prepared by the method, and an apparatus for conducting the method.

Inventors:
SOHN SUNGKYUN (US)
DIKEMAN ERIN (US)
KLINEDINST KEITH (US)
VERLAEK ROELAND LEONARDUS HUBERTUS MARIA (NL)
Application Number:
PCT/US2019/050931
Publication Date:
March 18, 2021
Filing Date:
September 13, 2019
Export Citation:
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Assignee:
SABIC GLOBAL TECHNOLOGIES BV (NL)
SOHN SUNGKYUN (US)
International Classes:
B29C70/50; B29C43/08; B29C43/54; B30B5/06; B30B15/34; B29C43/00; B29C43/48; B29C43/52; B29C43/58; C08J9/00; C08J9/28
Foreign References:
US4956140A1990-09-11
US20120065283A12012-03-15
GB2040801A1980-09-03
US20120065283A12012-03-15
Attorney, Agent or Firm:
BUCHANAN, J. Michael (US)
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Claims:
CLAIMS 1. A method of forming a consolidated fiber-reinforced thermoplastic composite, the method comprising: in a double belt press, heating an unconsolidated fiber-reinforced thermoplastic composite in a volume-controlled heating area comprising a fixed roller module and characterized by an initial belt separation, h1, and a final belt separation, h2, wherein a ratio of h1 to h2 is 5:1 to 10:1, and wherein the heating forms a consolidated fiber-reinforced thermoplastic composite; and cooling the consolidated fiber-reinforced thermoplastic composite in an isochoric cooling area, wherein the isochoric cooling area comprises a first cooling zone comprising a circulating roller module, and a second cooling zone comprising a fixed roller module, wherein the second cooling zone is downstream of the first cooling zone. 2. The method of claim 1, wherein the unconsolidated fiber-reinforced thermoplastic composite comprises reinforcing fibers, and matrix-component-precursor fibers; and the heating the unconsolidated fiber-reinforced thermoplastic composite comprises exposing the unconsolidated fiber-reinforced thermoplastic composite to a temperature effective to at least partially melt the matrix-component-precursor fibers but not the reinforcing fibers. 3. The method of claim 1 or 2, wherein the consolidated fiber-reinforced thermoplastic composite comprises reinforcing fibers, and a matrix comprising a matrix thermoplastic composition; and the cooling the consolidated fiber-reinforced thermoplastic composite comprises exposing the consolidated fiber-reinforced thermoplastic composite to a temperature effective to at least partially solidify the matrix thermoplastic composition. 4. The method of any one of claims 1-3, wherein the first cooling zone is characterized by a constant belt separation, h3, and wherein a ratio of h1 to h3 is 5:1 to 10:1. 5. The method of any one of claims 1-4, wherein the consolidated fiber-reinforced thermoplastic composite comprises, based on the total weight of the composite, 25 to 55 weight percent of reinforcing fibers, 35 to 65 weight percent of a polyimide, and 5 to 20 weight percent of a block polyestercarbonate-polysiloxane.

6. The method of claim 5, wherein the reinforcing fibers comprise glass fibers; the polyimide comprises a polyetherimide; and the block polyestercarbonate-polysiloxane comprises a polyester block comprising resorcinol ester units having the structure , a polycarbonate block comprising carbonate units having the structure wherein at least 60 percent of the total number of R1 groups are aromatic divalent groups, and a polysiloxane block comprising dimethylsiloxane units; wherein the block polyestercarbonate- polysiloxane comprises, based on total moles of carbonate and ester units, 70 to 90 mole percent of resorcinol ester units, 5 to 15 mole percent of carbonate units wherein R1 is 1,3-phenylene, and 5 to 15 mole percent of carbonate units wherein R1 is 2,2-bis(1,4-phenylene)propane, and further comprises, based on the weight of the block polyestercarbonate-polysiloxane, 0.2 to 4 weight percent dimethylsiloxane units. 7. An apparatus for forming a consolidated fiber-reinforced thermoplastic composite, the apparatus comprising: a double belt press comprising, a volume-controlled heating area comprising a fixed roller module and characterized by an initial belt separation, h1, and a final belt separation, h2, wherein a ratio of h1 to h2 is 5:1 to 10:1; and an isochoric cooling area comprising a first isochoric cooling zone comprising a circulating roller module, and a second isochoric cooling zone comprising a fixed roller module, wherein the second isochoric cooling zone is downstream of the first isochoric cooling zone.

Description:
METHOD OF FORMING A COMPOSITE, AND ASSOCIATED COMPOSITE AND APPARATUS BACKGROUND OF THE INVENTION [0001] Fiber-reinforced thermoplastics are increasingly used in the fabrication of interior parts for vehicles including aircraft, ships, and trains. For example, U.S. Patent Application Publication No. US 2012/0065283 A1 of Adjei et al. describes a nonwoven fabric prepared from reinforcing fibers, polyimide fibers, and polymeric binder fibers. Multiple layers of the nonwoven fabric are consolidated under elevated temperature and pressure to form a composite sheet that is optionally combined with a decorative film to form the vehicular interior part. Such parts exhibit advantageous properties including low weight, high flame retardancy, and low smoke generation. [0002] Consolidation of the nonwoven fabric layers is typically conducted on an isobaric (constant pressure) double belt press, in which the upper and lower belts provide a constant pressure on the processed substrate. Use of an isochoric (constant volume) double-belt press, in which the upper and lower belts provide a constant volume for the processed substrate, would have advantages including ease of operation, flexibility in product width (an isobaric process requires a product whose width exactly matches that of the belt), ease of process start-up and shut-down (for example, an isobaric process cannot tolerate a sudden substrate thickness change, as that could break the isobaric seal). However, relative to the use of an isobaric press, use of an isochoric press presents technical challenges, including generation of “flash” (squeezing of matrix polymer out the sides of the web, generation of “tail” (squeezing of matrix polymer out the back end of the web), and generation of wavy patterns on the surface of the consolidated composite. Thus, there is a desire for a consolidation process that utilizes a volume-controlled double-belt press rather than a pressure-controlled double belt press. BRIEF SUMMARY OF EMBODIMENTS OF THE INVENTION [0003] One embodiment is a method of forming a consolidated fiber-reinforced thermoplastic composite, the method comprising: in a double belt press, heating an unconsolidated fiber-reinforced thermoplastic composite in a volume-controlled heating area comprising a fixed roller module and characterized by an initial belt separation, h 1 , and a final belt separation, h2, wherein a ratio of h1 to h2 is 5:1 to 10:1, and wherein the heating forms a consolidated fiber-reinforced thermoplastic composite; and cooling the consolidated fiber- reinforced thermoplastic composite in an isochoric cooling area, wherein the isochoric cooling area comprises a first cooling zone comprising a circulating roller module, and a second cooling zone comprising a fixed roller module, wherein the second cooling zone is downstream of the first cooling zone. [0004] Another embodiment is a composite prepared by the method in any of its variations. [0005] Another embodiment is an apparatus for forming a consolidated fiber-reinforced thermoplastic composite, the apparatus comprising: a double belt press comprising, a volume- controlled heating area comprising a fixed roller module and characterized by an initial belt separation, h1, and a final belt separation, h2, wherein a ratio of h1 to h2 is 5:1 to 10:1; and an isochoric cooling area comprising a first isochoric cooling zone comprising a circulating roller module, and a second isochoric cooling zone comprising a fixed roller module, wherein the second isochoric cooling zone is downstream of the first isochoric cooling zone. [0006] These and other embodiments are described in detail below. BRIEF DESCRIPTION OF THE DRAWINGS [0007] Figure 1 is a schematic illustration of a melt spinning apparatus. [0008] Figure 2 is a schematic illustration of a papermaking apparatus. [0009] Figure 3 is a schematic illustration of a prior art isochoric consolidation apparatus. [0010] Figure 4 is a schematic illustration of a consolidation apparatus according to the invention. DETAILED DESCRIPTION OF THE INVENTION [0011] The present inventors have determined that generation of “flash,” generation of “tail,” and generation of wavy patterns on the surface of the consolidated composite are reduced or eliminated by heating an unconsolidated fiber-reinforced thermoplastic composite in a volume-controlled double-belt press with a heating area and a cooling area. The heating area has an initial belt separation substantially greater than the final belt separation, and the cooling area includes a first cooling zone with a circulating roller module and a second cooling zone with a fixed roller module. As is demonstrated in the working examples below, the heating zone belt separation feature and the cooling zone roller module features are both required to solve the technical problems. [0012] One embodiment is a method of forming a consolidated fiber-reinforced thermoplastic composite, the method comprising: in a double belt press, heating an unconsolidated fiber-reinforced thermoplastic composite in a volume-controlled heating area comprising a fixed roller module and characterized by an initial belt separation, h 1 , and a final belt separation, h2, wherein a ratio of h1 to h2 is 5:1 to 10:1, and wherein the heating forms a consolidated fiber-reinforced thermoplastic composite; and cooling the consolidated fiber- reinforced thermoplastic composite in an isochoric cooling area, wherein the isochoric cooling area comprises a first cooling zone comprising a circulating roller module, and a second cooling zone comprising a fixed roller module, wherein the second cooling zone is downstream of the first cooling zone. [0013] The method is conducted in an isochoric double-belt press, in which, at any given distance along the machine direction, the belt separation (and therefore the volume) is constant as a function of operation time. However, in the heating area, the belt separation decreases as a function of distance along the machine direction. For this reason, the belt separation in the heating area is described as “volume-controlled” rather than “constant volume,” even though the heating area is part of the isochoric (constant volume) double-belt press. [0014] The method comprises heating an unconsolidated fiber-reinforced thermoplastic composite in a volume-controlled heating area. The heating area is characterized by an initial belt separation, h1, and a final belt separation, h2, and the ratio of h1 to h2 is in the range of 5:1 to 10:1. In some embodiments, the ratio of h1 to h2 is in the range 6:1 to 9:1. The initial belt separation, h 1 , is measured in the heating area at the first distance along the machine direction at which the volume of the substrate is controlled by both belts. The final belt separation, h2, is measured in the heating area at the last distance along the machine direction at which the volume of the substrate is controlled by both belts. See Figure 4, described in detailed below, for an illustration of positions at which h 1 and h 2 are determined. [0015] In some embodiments of the method, the unconsolidated fiber-reinforced thermoplastic composite comprises reinforcing fibers, and matrix-component-precursor fibers; and the heating the unconsolidated fiber-reinforced thermoplastic composite comprises exposing the unconsolidated fiber-reinforced thermoplastic composite to a temperature effective to at least partially melt the matrix-component-precursor fibers but not the reinforcing fibers. [0016] As an example of at least partially melting the matrix-component-precursor fibers, those fibers can comprise a matrix component characterized by a matrix-component glass transition temperature, and the heating the unconsolidated fiber-reinforced thermoplastic composite can comprise exposing the unconsolidated fiber-reinforced thermoplastic composite to a temperature greater than the matrix-component glass transition temperature. [0017] As the substrate exits the heating zone, it is designated a consolidated fiber- reinforced thermoplastic composite. It then proceeds into a cooling area. The cooling area is isochoric, which in this context means that the belt separation is constant along the length of the cooling area. The cooling area comprises a first cooling zone comprising a circulating roller module. A circulating roller module includes a closed loop of closely spaced rollers, a portion of the loop being in contact with one of the two belts of the double-belt press. See Figure 4, where circulating roller modules 570 are in contact with belts 310. The closely spaced rollers of the circulating roller modules 570 rotate individually, and the closed loop of closely spaced rollers rotates so that the rollers in contact with the belts 310 are moving in the opposite direction as the belt (i.e., in Figure 4, the upper loop of closely spaced rollers is rotating clockwise, and the lower loop of closely spaced rollers is rotating counterclockwise). Compared to a fixed roller module, a circulating roller module provides more even pressure on the substrate. A circulating roller circulates at essentially the same linear speed as the belts. [0018] In some embodiments, the isochoric cooling area is characterized by a constant belt separation, h3, and the ratio of h1 to h3 is 5:1 to 10:1, or 6:1 to 9:1. The ratio of h1 to h3 corresponds to the overall substrate compression ratio of the process. [0019] After exiting the first cooling zone, the substrate enters a second cooling zone that includes a fixed roller module. The second cooling zone need not immediately follow the first cooling zone, as long as the second cooling zone is downstream from the first cooling zone. [0020] In some embodiments of the method, the consolidated fiber-reinforced thermoplastic composite comprises reinforcing fibers, and a matrix comprising a matrix thermoplastic composition; and the cooling the consolidated fiber-reinforced thermoplastic composite comprises exposing the consolidated fiber-reinforced thermoplastic composite to a temperature effective to at least partially solidify the matrix thermoplastic composition. [0021] As an example of at least partially solidifying the matrix thermoplastic composition, that composition can be characterized by a matrix thermoplastic composition glass transition temperature, and the cooling the consolidated fiber-reinforced thermoplastic composite can comprise exposing the unconsolidated fiber-reinforced thermoplastic composite to a temperature less than the matrix thermoplastic composition glass transition temperature. [0022] In a specific embodiment of the method, the consolidated fiber-reinforced thermoplastic composite comprises, based on the total weight of the composite, 25 to 55 weight percent of reinforcing fibers, 35 to 65 weight percent of a polyimide, and 5 to 20 weight percent of a block polyestercarbonate-polysiloxane. In a very specific embodiment of this method, the reinforcing fibers comprise glass fibers; the polyimide comprises a polyetherimide; and the block polyestercarbonate-polysiloxane comprises a polyester block comprising resorcinol ester units having the structure , a polycarbonate block comprising carbonate units having the structure , wherein at least 60 percent of the total number of R 1 groups are aromatic divalent groups, and a polysiloxane block comprising dimethylsiloxane units; wherein the block polyestercarbonate- polysiloxane comprises, based on total moles of carbonate and ester units, 70 to 90 mole percent of resorcinol ester units, 5 to 15 mole percent of carbonate units wherein R 1 is 1,3-phenylene, and 5 to 15 mole percent of carbonate units wherein R 1 is 2,2-bis(1,4-phenylene)propane, and further comprises, based on the weight of the block polyestercarbonate-polysiloxane, 0.2 to 4 weight percent dimethylsiloxane units. [0023] Another embodiment is a composite prepared by the method in any of its above- described variations. [0024] In a specific embodiment of the composite, the consolidated fiber-reinforced thermoplastic composite comprises, based on the total weight of the composite, 25 to 55 weight percent of reinforcing fibers, 35 to 65 weight percent of a polyimide, and 5 to 20 weight percent of a block polyestercarbonate-polysiloxane. In a very specific embodiment of this composite, the reinforcing fibers comprise glass fibers; the polyimide comprises a polyetherimide; and the block polyestercarbonate-polysiloxane comprises a polyester block comprising resorcinol ester units having the structure , a polycarbonate block comprising carbonate units having the structure wherein at least 60 percent of the total number of R 1 groups are aromatic divalent groups, and a polysiloxane block comprising dimethylsiloxane units; wherein the block polyestercarbonate- polysiloxane comprises, based on total moles of carbonate and ester units, 70 to 90 mole percent of resorcinol ester units, 5 to 15 mole percent of carbonate units wherein R 1 is 1,3-phenylene, and 5 to 15 mole percent of carbonate units wherein R 1 is 2,2-bis(1,4-phenylene)propane, and further comprises, based on the weight of the block polyestercarbonate-polysiloxane, 0.2 to 4 weight percent dimethylsiloxane units. [0025] Another embodiment is an apparatus for forming a consolidated fiber-reinforced thermoplastic composite, the apparatus comprising: a double belt press comprising, a volume- controlled heating area comprising a fixed roller module and characterized by an initial belt separation, h1, and a final belt separation, h2, wherein a ratio of h1 to h2 is 5:1 to 10:1; and an isochoric cooling area comprising a first isochoric cooling zone comprising a circulating roller module, and a second isochoric cooling zone comprising a fixed roller module, wherein the second isochoric cooling zone is downstream of the first isochoric cooling zone. [0026] The invention includes at least the following aspects. [0027] Aspect 1: A method of forming a consolidated fiber-reinforced thermoplastic composite, the method comprising: in a double belt press, heating an unconsolidated fiber- reinforced thermoplastic composite in a volume-controlled heating area comprising a fixed roller module and characterized by an initial belt separation, h 1 , and a final belt separation, h 2 , wherein a ratio of h1 to h2 is 5:1 to 10:1, and wherein the heating forms a consolidated fiber-reinforced thermoplastic composite; and cooling the consolidated fiber-reinforced thermoplastic composite in an isochoric cooling area, wherein the isochoric cooling area comprises a first cooling zone comprising a circulating roller module, and a second cooling zone comprising a fixed roller module, wherein the second cooling zone is downstream of the first cooling zone. [0028] Aspect 2: The method of aspect 1, wherein the unconsolidated fiber-reinforced thermoplastic composite comprises reinforcing fibers, and matrix-component-precursor fibers; and the heating the unconsolidated fiber-reinforced thermoplastic composite comprises exposing the unconsolidated fiber-reinforced thermoplastic composite to a temperature effective to at least partially melt the matrix-component-precursor fibers but not the reinforcing fibers. [0029] Aspect 3: The method of aspect 1 or 2, wherein the consolidated fiber-reinforced thermoplastic composite comprises reinforcing fibers, and a matrix comprising a matrix thermoplastic composition; and the cooling the consolidated fiber-reinforced thermoplastic composite comprises exposing the consolidated fiber-reinforced thermoplastic composite to a temperature effective to at least partially solidify the matrix thermoplastic composition. [0030] Aspect 4: The method of any one of aspects 1-3, wherein the first cooling zone is characterized by a constant belt separation, h 3 , and wherein a ratio of h 1 to h 3 is 5:1 to 10:1. [0031] Aspect 5: The method of any one of aspects 1-4, wherein the consolidated fiber- reinforced thermoplastic composite comprises, based on the total weight of the composite, 25 to 55 weight percent of reinforcing fibers, 35 to 65 weight percent of a polyimide, and 5 to 20 weight percent of a block polyestercarbonate-polysiloxane. [0032] Aspect 6: The method of aspect 5, wherein the reinforcing fibers comprise glass fibers; the polyimide comprises a polyetherimide; and the block polyestercarbonate-polysiloxane comprises a polyester block comprising resorcinol ester units having the structure , a polycarbonate block comprising carbonate units having the structure wherein at least 60 percent of the total number of R 1 groups are aromatic divalent groups, and a polysiloxane block comprising dimethylsiloxane units; wherein the block polyestercarbonate- polysiloxane comprises, based on total moles of carbonate and ester units, 70 to 90 mole percent of resorcinol ester units, 5 to 15 mole percent of carbonate units wherein R 1 is 1,3-phenylene, and 5 to 15 mole percent of carbonate units wherein R 1 is 2,2-bis(1,4-phenylene)propane, and further comprises, based on the weight of the block polyestercarbonate-polysiloxane, 0.2 to 4 weight percent dimethylsiloxane units. [0033] Aspect 7: A composite prepared by the method of any one of aspects 1-6. [0034] Aspect 8: A composite prepared by the method of aspect 5. [0035] Aspect 9: A composite prepared by the method of aspect 6. [0036] Aspect 10: An apparatus for forming a consolidated fiber-reinforced thermoplastic composite, the apparatus comprising: a double belt press comprising, a volume- controlled heating area comprising a fixed roller module and characterized by an initial belt separation, h 1 , and a final belt separation, h 2 , wherein a ratio of h 1 to h 2 is 5:1 to 10:1; and an isochoric cooling area comprising a first isochoric cooling zone comprising a circulating roller module, and a second isochoric cooling zone comprising a fixed roller module, wherein the second isochoric cooling zone is downstream of the first isochoric cooling zone. [0037] All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. Each range disclosed herein constitutes a disclosure of any point or sub-range lying within the disclosed range. [0038] The invention is further illustrated by the following non-limiting examples. EXAMPLES [0039] Materials used in these examples are summarized in Table 1. Table 1 [0040] The composition used to prepare block polyestercarbonate-polysiloxane containing fibers (PEC-Si fibers) is summarized in Table 2, where component amounts are expressed in weight percent based on the total weight of the composition. The composition was prepared by dry blending all components and adding the resulting mixture to the feed throat of a twin-screw extruder operating with zone temperatures ranging from 230 to 300 °C. The extrudate was cooled in water before being pelletized. Table 2 [0041] Pellets were dried at 80 to 120 °C for 6 to 12 hours before being fed to the hopper of a melt spinning apparatus. The melt spinning apparatus is schematically illustrated in Figure 1, where melt spinning apparatus 1 comprises extruder 5, in which dried pellets are converted to a melt, melt pump 10, which conveys the melt to spin pack 15, where it is filtered, then to spinneret 20, where multiple fibers are formed from the filtered melt. The fibers are immediately conveyed to quench section 30, where they are air-cooled and solidified. The cooled fibers then enter spin finish section 40, where a spin finish can be applied to the surface of the fibers. The fibers then traverse a sequence of godet pairs comprising first godets 50, second godets 60, and third godets 70, where the fibers are drawn (stretched). The fibers then enter winder section 80, where contact roller 90 facilitates formation of wound fiber 100 around one of two winding cores 110. [0042] In these experiments, the melt pump was operated at 10 centimeter 3 /revolution. Extruder and melt pump temperatures were 280 to 330 °C. A 144-hole, single-position spinneret was used. Spinneret holes (nozzles) were circular with a diameter of 0.8 millimeters. The length-to-diameter ratio of each spinneret was 4:1. A 325 U.S. mesh (44 micrometer opening) screen filter was used in the spinpack for filtration of the composition melt. After fibers exited the nozzles, they were solidified by quenching with air at ambient temperature (about 23 °C). Individual filaments were combined to form multi-filament threads, then a spin finish (an acrylamide copolymer in an oil-in-water emulsion, obtained as LUROL TM PS-11744 from Goulston) was applied to the multi-filament threads before they contacted the first godet. The draw down ratio was 280 to 550. Draw down ratio, which is unitless, is defined as the ratio of speed (in meters/minute) at which the melt exits the spinneret nozzles to the speed (in meters/minute) of the fiber at the first godet. The apparent shear rate was 170 to 1700 second -1 . Apparent shear rate (in units of second -1 ) is defined according to the equation wherein Q is the melt throughput per spinneret nozzle (in grams/second), R is the nozzle radius (in centimeters), and r is the polymer melt density (in grams/centimeter 3 ). The mechanical draw ratio was 0.95 to 1.2. Mechanical draw ratio, which is unitless, is defined as the ratio of the first godet speed (in meters/minute) to the winder speed (in meters/minute). The resulting threads, containing fibers of 8 denier per filament, were chopped to a length of about 12 millimeters for use in preparation of a nonwoven fabric. [0043] Formation of Nonwoven Fabric. A mixture of polyetherimide fibers (50 weight percent), PEC-Si fibers (10 weight percent), and chopped glass fibers (40 weight percent) was used to prepare a nonwoven fabric via a wet-laid papermaking) process. Figure 2 is a schematic illustration of a papermaking apparatus 200, which includes mixing tank 210, run tank 220, headbox 230, wire former 240, dryer 250, and winder 260. A fiber dispersion was prepared by dispersing 200 kilograms total of the three ingredient fibers in 200 kilograms of an aqueous solution containing a viscosity modifying agent. The viscosity modifying agent was a poly(acrylamide-co-diallyldimethylammonium chloride) solution, 10 weight percent in water, and it was used in an amount effective to provide the aqueous solution with a viscosity of 50 to 200 centipoise. The fiber dispersion was fed onto the wire mesh of a paper-making machine to form an aqueous suspension layer, and aqueous solution was drained to form a fiber layer. The fiber layer was transferred to a water washing section where viscosity modifier was washed from the fiber layer. The washed fiber layer was then transferred to a tunnel dryer, and finally to a winding section. Water was essentially eliminated from the mat by the sequence of gravity drainage through holes in the wire mesh, squeezing through several pairs of nip rollers, and heating in an ambient-pressure tunnel dryer, where the temperature was set to 280-300 °C and the drier residence time was 120-180 seconds.^^In this temperature range, the PEC-Si fibers melted and the polyetherimide fibers at least partially melted. Both types of fibers flowed, losing their fiber shape. If the tunnel dryer temperature is less than 280 °C, web tearing occurs. If it is less than 220 °C, not only is there web tearing, but the binder (PEC-Si) fibers do not get fully activated,^leading to a weak and locally torn fabric. This stage is referred to as binder activation, because the binder fibers melt, and the melted PEC-Si copolymer flows within the web to bind together the network of glass and polyetherimide fibers. This gives the network enough mechanical integrity to prevent it from falling apart in subsequent processing and handling. Using the above process steps, a 165 gram/meter 2 nonwoven fabric web was produced at a speed of 5 meters/minute. The nonwoven fabric web was wound on a core.^^When the roll was fully wound, the edges were trimmed to meet the target width, and the nonwoven fabric web was re-wound to a new core. [0044] Figure 3 is a schematic illustration of a prior art isochoric double-belt press consolidation apparatus, 300, in which circulation of belts 310 is controlled by drums 320. Substrate 360 enters heating area 325 (as an unconsolidated fiber-reinforced thermoplastic composite) at a belt separation, h1, and exits the hot zone at a belt separation, h2, where h1 = h2. The heating area 325 includes heaters 330 and fixed roller modules 350. From the heating area 325, the substrate proceeds to a cooling area 335 including cooler 340, and fixed roller module 350. The substrate 360 exits as a consolidated fiber-reinforced thermoplastic composite. [0045] Rectangular pieces 30.5 centimeters wide and 35.6 centimeters long (12 by 14 inches) were cut from the nonwoven roll. A total of eight layers of nonwoven were stacked together (collectively, “the substrate”) in preparation for consolidation to make a 1,320 gram/meter 2 composite. The consolidation operation used a 0.8 meter wide Sandvik SB isochoric double-belt press modified to be volume-controlled rather than isochoric in the heating area, and operating at a heating area temperature of 350-400 °C, a cooling area temperature of 40-180 °C (maintained by a temperature of 10-40 °C in coolers 340), and a speed of 1 meter/minute. Figure 4 is a schematic illustration of the double-belt press 500, in which circulation of belts 310 is controlled by drums 320. Substrate 560 enters heating area 325 (as an unconsolidated fiber-reinforced thermoplastic composite) at a belt separation, h 1 , and exits heating area 325 at a belt separation, h2, wherein the ratio of h1 to h2 is 5:1 to 10:1 (h1 and h2 are not shown to scale in Figure 4). The heating area 325 includes heaters 330 and fixed roller modules 350. From the heating area 325, the substrate proceeds to a cooling area 335 including coolers 340, and at least one circulating roller module 570, followed by at least one fixed roller module 350. The substrate 560 exits as a consolidated fiber-reinforced thermoplastic composite. [0046] Table 3 summarizes process variations and properties of the resulting consolidated fiber-reinforced thermoplastic composite. In Table 3, varying belt gap settings are presented as a function of zone, where zones are labeled Z1-Z5. Referring to Figure 4, Z1, Z2, and Z3 correspond to the three sections of heating area 325, each section having its own heaters 330 and fixed roller module 350; and Z4 and Z5 correspond to the two sections of cooling area 335, each section having its own cooler 340, the first section having circulating roller module 570, and the second section having a fixed roller module 350. Note that for Comparative Example 1, there are no gap values for the Z5 inlet and Z5 outlet because the apparatus did not include a Z5 section. In general for all processes, each section had a machine direction length of 1.0 meter, and sections were separated by a machine direction distance of 0.1 meter. In Table 3, “h1/h2” is the ratio of the heating area initial belt separation, h1, to the heating area final belt separation, h 2 ; and “h 1 /h 3 ” is the ratio of the heating area initial belt separation, h 1 , to the cooling area constant belt separation, h3. “Z4 CR?” refers to whether there is a circulating roller module in Zone 4; “yes” means that a circulating roller module is present in Zone 4; “no” means that a fixed roller module is present in Zone 4. A “Consolidation” rating of “Bad” means that the consolidated fiber-reinforced thermoplastic composite exhibits visually observable fibers on its surface and/or exhibits visually observable polymer-derived fibers in cross-section; a rating of “Good” means that neither of these defects was observed. “Flash?” refers to whether there is any flash present, where flash is defined as visually observable thermoplastic matrix material extending beyond the side (transverse direction) edges of the consolidated fiber-containing composite; “yes” means that flash is present, and “no” means that flash is absent. “Tail (cm)” refers to the length of the tail, defined as the length in centimeters of any thermoplastic matrix material extending beyond the trailing machine-direction edge of the consolidated fiber- containing composite. “Surface appearance” refers to the visual appearance of the top surface of the consolidated composite; “No wavy patterns” and “Wavy patterns” indicate the absence and presence, respectively, of visually observable wavy patterns on the surface. Flexural modulus values, expressed in megapascals (MPa) and were determined in the machine and transverse directions according to ISO 178:2010 at 23 °C using test articles cut from the consolidated composite and having dimensions 15.24 centimeters (6 inches) long by 2.54 centimeters (1 inch) wide by 1.2 millimeters thick.

[0047] The results, presented in Table 3, show that only the Example 1 consolidated composite, prepared in a process with an h1/h2 value in the range 5:1 to 10:1, as well as a circulating roller module in the first cooling zone, exhibited good consolidation, no wavy patterns, no flash, and no tail. Comparative Example 1 illustrates that wavy patterns resulted from a process including an hi/h2 value in the range 5:1 to 10:1, but lacking a circulating roller module (i.e., having a fixed roller module) in the first cooling zone. And Comparative Example 4 illustrates that wavy patterns and a 7.62 centimeter long tail resulted from a process having a circulating roller module in the first cooling zone, but having an hi/ha value below 5.

Table 3 Table 3 (cont.)