阅读说明：本技术 由非卷曲织物形成复合制品的方法 (Method of forming a composite article from a non-crimped fabric ) 是由 V·R·艾塔拉朱 W·R·罗杰斯 于 2019-04-24 设计创作，主要内容包括：用于形成复合制品的方法包括提供非卷曲织物(NCF),非卷曲织物包括通过缝线保持在接头处的多个纤维层,其中缝线表现出相对于纤维层较低的对热和/或UV光的结构耐受性,使用热或UV光在一个或多个区域中选择性地降解缝线,将NCF悬垂在成型制品上,将聚合物基质材料施加到悬垂的NCF,并且固化聚合物基质材料以形成成型复合制品。缝线可以在NCF的区域中降解,当悬垂在成型制品上时,NCF的区域对应于成型制品的拓扑特征。降解缝线可包括破坏缝线。纤维层可包括碳纤维、玻璃纤维和/或玄武岩纤维。成型制品可以是工具和/或汽车部件。NCF可以是双轴NCF。(A method for forming a composite article includes providing a non-crimped fabric (NCF) comprising a plurality of fibrous layers held at a joint by stitches, wherein the stitches exhibit a lower structural resistance to heat and/or UV light relative to the fibrous layers, selectively degrading the stitches in one or more regions using heat or UV light, draping the NCF over a shaped article, applying a polymeric matrix material to the draped NCF, and curing the polymeric matrix material to form the shaped composite article. The suture may degrade in the region of the NCF that corresponds to the topological feature of the shaped article when draped over the shaped article. Degrading the suture may include breaking the suture. The fibrous layer may comprise carbon fibers, glass fibers and/or basalt fibers. The shaped article may be a tool and/or an automotive part. The NCF may be a biaxial NCF.)

1. A method for forming a composite article, the method comprising:

providing a non-crimped fabric (NCF) comprising a plurality of fibrous layers held at a joint by a stitch, wherein the stitch exhibits a lower structural resistance to heat and/or UV light relative to the fibrous layers;

selectively degrading the sutures in one or more regions using heat or UV light;

suspending the NCF over a shaped article;

applying a polymeric matrix material to the pendulous NCF; and is

Curing the polymer matrix material to form a shaped composite article.

2. A method for forming a composite article, the method comprising:

providing a non-crimped fabric (NCF) comprising a plurality of fibrous layers held at a joint by a stitch, wherein the stitch exhibits a lower structural heat resistance relative to the fibrous layers;

selectively degrading the suture in one or more regions using heat;

suspending the NCF over a shaped article;

applying a polymeric matrix material to the pendulous NCF; and is

Curing the polymer matrix material to form a shaped composite article.

3. A method for forming a composite article, the method comprising:

providing a non-crimped fabric (NCF) comprising a plurality of fibrous layers held at a joint by stitches, wherein the stitches exhibit a lower structural resistance to UV light relative to the fibrous layers;

selectively degrading the sutures in one or more regions using UV light;

suspending the NCF over a shaped article;

applying a polymeric matrix material to the pendulous NCF; and is

Curing the polymer matrix material to form a shaped composite article.

4. The method of any of the preceding claims, wherein the suture degrades in a region of the NCF that corresponds to a topological feature of the shaped article when draped over the shaped article.

5. The method of any of the above claims, wherein degrading the suture comprises disrupting the suture.

6. The method of any of the preceding claims, wherein the fibrous layer comprises carbon fibers, glass fibers, and/or basalt fibers.

7. The method of any of the preceding claims, wherein the shaped article comprises an automotive part.

8. The method of any of the above claims, wherein the NCF comprises a biaxial NCF.

9. The method of any of the above claims, wherein the suture comprises one or more polyamides, one or more polyesters, polyurethanes, one or more rayon materials, polypropylene, one or more polyglycolic acids, one or more polyvinyl alcohols, and combinations thereof.

10. The method of any of the above claims, wherein the suture is selectively degraded by contacting the NCF with a heated forming roller or heated forming stamp, or by a laser, a raster induction heating tool, or an atmospheric plasma.

Background

There is an increasing interest in replacing high performance lightweight reinforced composite components and structures comprising a polymer matrix with suitable reinforcement materials for metal components in vehicles. Suitable polymers are typically thermosetting materials such as epoxy, vinyl ester or polyester, or thermoplastic materials such as polypropylene or polyamide, and suitable reinforcing materials include structural fibres such as carbon fibres, glass fibres or aramid fibres. Such fibers may be randomly oriented and aligned or registered in one or more preferred directions.

For textile applications, the aligned fibers may constitute one of two textile structures for ease of application: woven or nonwoven fabrics, which are commonly referred to as uncrimped or stitch-bonded fabrics. Woven fabrics employ tows in a first orientation that are alternately positioned above and below tows of fibers in a second orientation, typically about 90 ° from the first orientation. The braid may be tight, with adjacent tows spaced about 1 mm or less apart, or loose, with adjacent tows spaced up to about 10 mm apart.

Non-crimp fabrics comprise a number of spaced apart fiber rovings that may simply be placed alongside one another in a layer and secured and locked in place by stitching, using, for example, polyester yarns. Such stitches typically extend over the length and width of the reinforcement layer and are typically accomplished by a stitch beam incorporating a plurality of needles and having appropriate movement to accomplish simple chain stitches and other more complex stitches, such as warp knit stitches. In many cases, multiple coextensive layers are stacked on top of each other and the rovings of all the layers are secured in a single stitching operation. Typically, the layers are placed with the fiber orientations of adjacent layers rotated with respect to each other so that the in-plane properties in the multilayer reinforcement are less directional or more isotropic than in each layer alone. The weight of each layer is determined by the volume of the roving and the spacing between adjacent roving bundles. These nonwoven reinforcements are known as stitchbonded fabrics or non-crimped fabrics, commonly abbreviated as NCF.

Such textile reinforcements, woven or non-woven, may be impregnated with a suitable polymeric resin, placed in a mold, shaped, and then cured, typically at moderately elevated temperatures (e.g., 150 ℃) to form the desired polymeric composite. It should be appreciated that the sequence of operations listed above may be modified for different molding processes. For example, the fabric may be placed in a tool (i.e., a mold) having impregnated resin, or the resin may be added after the fabric enters the mold by resin impregnation, resin transfer molding, or structural resin injection molding. Thermoplastic or thermoset sheets or materials having blended strands of thermoplastic and reinforcing fibers may also be used.

Disclosure of Invention

A method for forming a composite article is provided and includes providing a non-crimped fabric (NCF). The NCF includes a plurality of fibrous layers held at a joint by stitches, and the stitches exhibit a lower structural resistance to heat and/or UV light relative to the fibrous layers. The method next includes selectively degrading the sutures in one or more regions using heat or UV light, draping the NCF over the shaped article, applying a polymeric matrix material to the draped NCF, and curing the polymeric matrix material to form the shaped composite article. The suture may degrade in the region of the NCF that corresponds to the topological feature of the shaped article when draped over the shaped article. The suture may degrade in the region of the NCF that corresponds to a feature that exhibits topological variation in more than one dimension when draped over the shaped article. Degrading the suture may include breaking the suture. The fibrous layer may comprise carbon fibers, glass fibers and/or basalt fibers. The shaped article may be a tool. The shaped article may be an automotive part. The NCF may be a biaxial NCF.

Other methods for forming composite articles are provided and include providing a non-crimped fabric (NCF). The NCF may include multiple fibrous layers held at the joint by stitches, and the stitches may exhibit lower structural heat resistance relative to the fibrous layers. The method next includes selectively degrading the sutures in the one or more regions using heat, draping the NCF over the shaped article, applying a polymeric matrix material to the draping NCF, and curing the polymeric matrix material to form the shaped composite article. The fibrous layer may comprise carbon fibers, glass fibers and/or basalt fibers. The suture may include one or more polyamides, one or more polyesters, polyurethanes, one or more rayon materials, polypropylene, one or more polyglycolic acids, one or more polyvinyl alcohols, and combinations thereof. The sutures may be selectively degraded by contacting the NCF with a heated forming roller or heated forming die. The forming roller or forming die may include a forming portion that is heated to at least the melting point of the stitches. The suture may be selectively degraded by a laser, a grating induction heating tool, or an atmospheric plasma.

Other methods for forming composite articles are provided and include providing a non-crimped fabric (NCF). The NCF includes multiple fibrous layers held at the joint by stitches, and the stitches exhibit lower structural resistance to UV light relative to the fibrous layers. The method next includes selectively degrading the sutures in the one or more regions using UV light, draping the NCF over the shaped article, applying a polymeric matrix material to the draping NCF, and curing the polymeric matrix material to form the shaped composite article. The sutures may be selectively degraded using UV light by applying a mask to the NCF and exposing the mask to UV light, wherein the mask includes one or more apertures corresponding to regions of the NCF where suture degradation is desired. The sutures may be selectively degraded by a shielded UV light source. The fibrous layer may comprise carbon fibers, glass fibers and/or basalt fibers. The suture may include one or more polyamides, one or more polyesters, polyurethanes, one or more rayon materials, polypropylene, one or more polyglycolic acids, one or more polyvinyl alcohols, and combinations thereof.

Drawings

FIG. 1A shows a top view of a woven fabric according to one or more embodiments;

FIG. 1B shows a perspective view of a non-crimped fabric according to one or more embodiments;

fig. 2A shows a top view of an uncrimped fabric having stitches applied in a chain or columnar pattern in accordance with one or more embodiments;

FIG. 2B shows a top view of a non-crimped fabric with stitches applied in a warp knit pattern in accordance with one or more embodiments;

fig. 2C shows a top view of a non-crimped fabric with stitches applied in a hybrid chain/warp knit pattern in accordance with one or more embodiments;

FIG. 3 illustrates a block diagram of a method for forming a composite article according to one or more embodiments;

FIG. 4A illustrates a perspective view of a tool that can be used as a molded article according to one or more embodiments; and

figure 4B shows a top view of an NCF blank that may be draped over a tool.

Detailed Description

Fiber reinforced polymer composite articles are finding increasing application where low quality and high strength are required. Typically, the composite reinforcement material itself is a composite of several distinct, usually coextensive, layers of reinforcing fibers, stacked or layered on top of each other. The reinforcing material may be aligned woven or non-woven fibers or may be continuous or chopped randomly arranged and positioned fibers. Illustrative examples of such reinforcement materials are shown in fig. 1A-B and may include, but are not limited to, carbon fibers, glass fibers, and aramid fibers, among others, as described below.

FIG. 1A shows a portion of a woven reinforcement material 10 including warp fibers 12 arranged in tows 14, the tows 14 being alternately positioned above and below weft fibers 16 arranged in tows 18. Fig. 1B shows a four-layer or "four-axis" non-crimp fabric (NCF)20 in which layers of rovings or "layers" 25, 27, 29, 31 respectively contain oriented, spaced apart rovings 24, 26, 28, 30, each NCF20 containing fibers 22 (shown only once for clarity) laid in a layered fashion and secured by stitches 32. The stitches 32 shown are a hybrid chain/warp knit pattern, but many different stitch patterns may be employed. By way of non-limiting example, fig. 2A shows a top view of NCF20 with stitches 32 applied in a chain or columnar pattern, fig. 2B shows a top view of NCF20 with stitches 32 applied in a warp knit pattern, and fig. 2C shows a top view of NCF20 with stitches 32 applied in a mixed chain/warp knit pattern.

NCFs are commonly used to form composite articles, which typically include NCFs embedded in a cured polymer matrix. To form the composite article, the NCF is first draped over the shaped article to establish the desired end geometry of the composite article, and then the polymeric matrix material is applied to the NCF and cured. Provided herein are methods for forming a composite article comprising NCFs that improve the drapability of NCFs during formation and thus reduce undesirable wrinkling and defects in the composite article.

Fig. 3 illustrates a block diagram of a method 300 for forming a composite article. The method 300 will be described in conjunction with the NCF20 of fig. 2B, but those skilled in the art will appreciate that the method 300 is not so limited. The method 300 includes: providing 310 an NCF20, selectively degrading 320 sutures 32 in one or more regions, draping 330 the NCF20 over a shaped article, applying 340 a polymeric matrix material to the draping NCF20, and curing 350 the polymeric matrix material to form a shaped composite article. The method may also optionally include separating 360 the shaped article from the shaped composite article.

NCF20 may comprise a multi-axial NCF (e.g., a two-axis, three-axis, four-axis NCF) comprising a plurality of layers. One common example of a biaxial NCF is a 2-ply fiber set arranged at +/-45 ° and-45 °. Other biaxial NCFs include fiber groups arranged at 0 ° and 90 °, fiber groups arranged at + 30 ° and-30 °, fiber groups arranged at + 60 ° and-60 °, and fiber groups arranged at asymmetric angles, e.g., 0 ° and + 45 °. Common examples of triaxial NCFs are 3-ply fiber sets arranged at 0 °, + 60 °, and-60 °. Common examples of four-axis NCFs are 4-ply fiber sets arranged at 0 °, + 45 °, and 90 °. It should be understood that the terms non-crimp fabric, stitch-bonded fabric, NCF fabric, or aligned fiber layers as used herein include the number of layers, the number of orientations, the angular arrangement of the fibers within any layer, and the variation in fiber density in each orientation.

The fibers 22 of NCF20 may include carbon fibers, glass fibers (e.g., fiberglass, quartz), basalt fibers, aramid fibers, Polyphenylenebenzobisoxazole (PBO) fibers, polyethylene fibers (e.g., Ultra High Molecular Weight Polyethylene (UHMWPE)), polypropylene fibers (e.g., high strength polypropylene), natural fibers (e.g., cotton, flax, cellulose, spider silk), and combinations thereof.

The polymer matrix may comprise any suitable thermoplastic or thermosetting resin. The thermoplastic resin may include: vinyl chloride resin, vinylidene chloride resin, vinyl acetate resin, polyvinyl alcohol resin, polystyrene resin, acrylonitrile styrene resin, acrylonitrile-butadiene-styrene resin, acrylic resin, methacrylate resin, polyethylene resin, polypropylene resin, polyamide resin (PA6, PA11, PA12, PA46, PA66, PA610), wholly or partially aromatic polyamide resin, polyacetal resin, polycarbonate resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polyacrylate resin, polyphenylene ether resin, polyphenylene sulfide resin, polysulfone resin, polyethersulfone resin, polyetheretherketone resin, polylactide resin, or any combination or copolymer of these resins. The thermosetting resin may include: benzoxazines, Bismaleimides (BMIs), cyanate esters, epoxies, Phenolics (PFs), polyacrylates (acrylics), Polyimides (PIs), unsaturated polyesters, Polyurethanes (PURs), vinyl esters, silicones, or any combination or copolymer of these resins.

The method 300 includes providing 310 an NCF20, the NCF20 including a plurality of fibrous layers held at a joint by stitches 32. In some embodiments, NCF20 comprises a biaxial NCF, such as those described above. The suture 32 exhibits a higher specific vulnerability than the fibers 22 of each layer of the NCF 20. Specific vulnerabilities may include, for example, structural resistance to heat, UV light, chemicals, or tension. In one embodiment, the stitches 32 exhibit a lower structural resistance to heat and/or UV light relative to the fiber layers of the NCF 20. In one embodiment, the stitches 32 exhibit a lower structural resistance to heat relative to the fibrous layers of the NCF 20. In one embodiment, the suture 32 exhibits a lower structural resistance to UV light relative to the fiber layer of the NCF 20.

The method 300 then includes selectively degrading 320 the suture 32 in one or more regions using a method that exploits the particular vulnerability of the suture 32. Thus, for example, in embodiments where the suture 32 exhibits a lower structural resistance to heat and/or UV light relative to the fiber layers of the NCF20, heat or UV light may be used to achieve selective degradation 320 of the suture 32. Degradation 320 may include melting, breaking, or otherwise structurally damaging suture 32 to the extent that the desired fluidity is achieved in close proximity to the NCF fiber. For example, in some embodiments, degrading may include reducing the elasticity of the suture. In some embodiments, the suture may exhibit lower strength than commonly used threadlines, such that the threadlines suitably break under tension. For example, a common polyester suture for NFC 20 may have a dtex (mass in grams per 10,000 meters of filament) of about 33. Thus, in some embodiments, the NFC 20 may include a suture 32, the suture 32 including, for example, about 10-15 decitex.

In embodiments where the suture 32 exhibits a lower structural resistance to heat relative to the fibrous layer of the NCF20, the suture 32 may be selectively degraded 320 using heat. Suitable suture materials include polyamide, polyester, cotton, silk, polytetrafluoroethylene, viscose rayon, polypropylene, polyacrylate, flax, wool, aramid fiber, aluminum silicate, polyglycolic acid, polyvinyl alcohol, and polycarbonate polymers, among others. Suture materials particularly suitable for this embodiment may include one or more polyamides, one or more polyesters, polyurethanes, one or more rayon materials, polypropylene, one or more polyglycolic acids, one or more polyvinyl alcohols, and combinations thereof.

In some embodiments, the NCF desirably includes fibers having a degradation temperature significantly higher than the degradation temperature of the suture material. Such fibrous materials may include one or more of carbon fibers, glass fibers, and basalt fibers, as well as other fibers described above. In one embodiment, the NCF comprises carbon fiber and polyamide suture. In one embodiment, the NCF includes fiberglass and polyamide suture. In one embodiment, the NCF includes basalt fibers and polyamide sutures. In one embodiment, the NCF comprises carbon fiber and polyester stitching. In one embodiment, the NCF includes fiberglass and polyester suture. In one embodiment, the NCF includes basalt fibers and polyester sutures. In one embodiment, the NCF comprises carbon fiber and viscose rayon suture. In one embodiment, the NCF includes fiberglass and viscose rayon suture. In one embodiment, the NCF comprises carbon fiber and polypropylene suture. In one embodiment, the NCF includes fiberglass and polypropylene sutures. In one embodiment, the NCF comprises carbon fiber and polyurethane stitching. In one embodiment, the NCF comprises fiberglass and polyurethane stitching. In one embodiment, the NCF includes carbon fiber and polyglycolic acid suture. In one embodiment, the NCF includes fiberglass and polyglycolic acid suture.

In some embodiments, the NCF may be in contact with heated forming rollers or heated forming stamps, each forming roller or heated forming stamp including at least one forming portion. The rollers or stamp formations may protrude from the tubular surface of the rollers or orthogonal faces of the stamp such that they will contact the NCF20 in areas where suture degradation is desired. The forming roller or die is heated to a selected temperature to achieve the desired degradation of the suture 32. The stamp or roller may be heated completely or the forming section may be selectively heated. The temperature to which the roller or die is heated prior to contacting the NCF20 can include at least the melting point of the suture, for example. In other embodiments, the suture 32 may be selectively degraded by a laser, a grating induction heating tool, an atmospheric plasma, and other heat sources capable of achieving the desired degradation of the suture 32.

Suture materials that are particularly susceptible to laser heating may include polymeric materials such as polyamide, polyester, and viscose rayon, among others. Sutures that are particularly susceptible to induction heating may include polymer sutures that include small metal particles (e.g., particles having an average diameter of about 10nm to about 20 μm). The metal particles may comprise, for example, iron and/or nickel. Suture materials that are particularly susceptible to plasma heating include polymeric materials that can degrade upon exposure to reactive oxygen species. Some such materials may include polyamides, polyesters, viscose rayon, polyurethane, polyglycolic acid, and polyvinyl alcohol.

Similarly, in embodiments where the suture 32 exhibits a lower structural resistance to UV light relative to the fiber layers of the NCF20, UV light may be used to achieve selective degradation 320 of the suture 32. The UV light source may comprise any device configured to provide sufficiently high energy UV light, such as short wave UV lamps, gas discharge lamps, UV emitting LEDs, and the like. In some embodiments, the UV light discharge range will desirably be in the UVC range (e.g., about 100nm to about 280nm) such that there is sufficient energy to degrade the absorbing polymeric material. In some embodiments, a cover with suture-degrading apertures is applied to NCF20, and the cover is subsequently exposed to UV light, such that the UV light contacts NCF20 only in the area directly below the cover apertures. Additionally or alternatively, the UV light source itself may be shielded to focus the emission of UV light in a desired direction to achieve a specific degradation of the suture 32.

Suture materials that are particularly susceptible to UV light may include, for example, polyamides, polyesters, and polyacrylates. In some embodiments, suture materials that are particularly susceptible to UV light may include polymeric materials and UV light additives that are capable of absorbing UV light and degrading to produce small organic radicals. Without being limited to a particular degradation mechanism, in some embodiments, such radicals may abstract hydrogen atoms from the polymeric suture material and reduce its structural integrity. Examples of such UV additives include, inter alia, 2-dimethoxy-2-phenylacetophenone, phenyl ketals (e.g., benzil dimethyl ketal), hydroxyacetophenone, α -hydroxyalkylphenone, acylphosphine oxides (2,4, 6-trimethylolbenzoyldiphenylphosphine oxide), α -aminoalkylphenones, and azobisisobutyronitrile.

Similarly, in embodiments where the suture material is particularly susceptible to particular chemicals (e.g., acids or bases) relative to the fiber layer of the NCF20, selective degradation 320 of the suture 32 may be achieved using the particular chemicals. For example, sutures comprising polyesters, polyamides, polyurethanes, polyglycolic acid, and/or polyvinyl alcohol are particularly susceptible to degradation by strong acids (e.g., hydrochloric acid, sulfuric acid, and nitric acid) and strong bases (e.g., potassium hydroxide and sodium hydroxide) that will depolymerize the suture material.

After selectively degrading 320 sutures 32, method 300 includes draping 330 NCF20 over the molded article. The shaped article may be another aspect of the tool and/or the composite article. For example, the NCF may be laid on an automotive part that will be integrated with the molded composite article after curing 350. In such an embodiment, the component is reinforced. In such an embodiment, the automotive component would provide at least a portion of the tooling used to form the composite component. The stitches 32 of the NCF20 selectively degrade in the region of the NCF20, which corresponds to the topological feature of the NCF20 when draped over the shaped article. In particular, the stitches 32 of the NCF20 selectively degrade in the regions of the NCF20 that correspond to features thereof that exhibit topological variations in more than one dimension when draped over a shaped article. For example, a corner formed by two planes exhibits topological variation in only one dimension relative to one of the planes and causes minimal wrinkling of the NCF20 when the NCF20 overhangs thereon. Conversely, the corner formed by the three planes exhibits a topological change in 2 dimensions relative to one of the planes and causes a higher degree of wrinkling of the NCF20 when the NCF20 overhangs thereon.

Fig. 4A shows a perspective view of a tool 400 that may be used to form an article. Figure 4B shows a top view of the NCF blank 401, the NCF blank 401 may overhang 330 the tool 400. The NCF blank 401 may be hung 330 on the tool 400 such that the NCF blank perimeter 410 is aligned with the location 411 of the tool 400. Region 405 identifies a region of the tool 400 having topological features that adversely affect the overhang 330 of the NCF blank 401. Thus, the stitches 32 of NCF blank 401 may be selectively degraded 320 in regions 415, 416, 417, and 418 to accommodate this topological feature of tool 400. For example, the stitches 32 of the region 419 may remain substantially intact. Those skilled in the art will appreciate that the tool 400 and NCF blank 401 are provided for illustrative purposes only, and that the methods and articles described herein are not intended to be limited to their geometries.

After the NCF20 is draped 330 over the shaped article, a polymer matrix (e.g., one of the polymer matrices described above) is applied 340 to the draped NCF20 and cured 350 to form a shaped composite article. For example, applying 340 the polymer matrix to the NCF20 may include impregnating the NCF20 with a sufficient amount of the polymer matrix to wet all of the fibers 22 thereof. If the shaped article is a tool, the method 300 may further include separating 360 the tool from the shaped composite article.

The practice of the present invention has been described with reference to certain preferred embodiments, which are intended to be illustrative rather than limiting. The full scope of the invention is only limited and limited by the appended claims.