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    • 专利摘要:
    TOOL AND METHOD FOR AUTOMATIC TAPE DEPOSITION, PREPREG FOR AUTOMATIC TAPE PLACEMENT, METHOD FOR PREPARATION OF A MOLD TOOL, AND, COMFORTABLE COMFORTABLE TOOL WITH COMFORTABLE COMFORTABLE COMPOSITE. € A prepared mold tool having a thermoplastic surface layer polymer coating (50) on the mold surface of the prepared mold tool or prepreg having a thermoplastic surface layer polymer coating on the surface of prepreg reinforced with thermoplastic fiber are described that improve the first fold deposition of prepregs of composites reinforced with thermoplastic fiber on mold tools for prepreg formation or placement Tape in situ. Composite parts reinforced with thermoplastic fiber resulting from a thermoplastic composite material reinforced with thermoplastic fiber having structural reinforcing fibers with one or more high performance polymers, and a coating of a thermoplastic surface layer polymer that forms a polymer blend with the high-performance polymers of the composite material reinforced with thermoplastic fiber thus providing improved properties, and methods for producing and using the same, are the provided here.
    公开号:BR112015008752B1
    申请号:R112015008752-3
    申请日:2013-10-17
    公开日:2021-02-23
    发明作者:James Francis Pratte；Scott Alfred Rogers
    申请人:Cytec Industries Inc；
    IPC主号:
    专利说明:

    BACKGROUND OF THE INVENTION
    [001] Field of the Invention The object of the present invention relates to composite materials reinforced with thermoplastic plastic fibers and particularly the application of a coating layer to a molding tool to form composite or to a thermoplastic material reinforced with prepreg composite fiber. to improve the first prepreg deposit layer on the composite prepreg forming tool forming or in situ automated deposit tape placement. The in situ application of the polymer coating of the surface layer during or before automated deposition can also provide a beneficial interlaminar resin between each layer between each layer of fiber reinforced thermoplastic composite material. The polymer coating of the surface layer is preferably thermoplastic particles applied by plasma spraying to the mold or prepreg tool to form a substantially molten layer of thermoplastic particles. More particularly, in certain embodiments, the present invention relates to layered fiber-reinforced thermoplastic prepreg for use in fast rolling and forming processes where said fiber-reinforced thermoplastic prepreg is useful in the aerospace industry and other high-end industrial / automotive applications. performance.
    [002] Description of the Related Art. Reinforced thermoplastic and thermoplastic materials have wide application in, for example, the aerospace, automotive, industrial / chemical, and sporting goods industries. Thermosetting resins are impregnated in the fiber reinforcing material before curing, while resinous materials are low in viscosity. Thermoset composites suffer from disadvantages, including transformation problems related to the removal of trapped or volatile air so that a vacuum-free matrix is produced. Thermoset composites made by the prepreg method require long curing times with alternating pressures, to control the flow of the resin as it cures to avoid bubbles in the matrix. While traditional fabrication of structures used hand placement of thermostable prepreg pleats on a tool, the current fabrication of large structures uses robotic placement of the thermosetting composite material in the tool to increase the production rate. The overall production rate for a structural component is limited by long curing in the autoclave process step and related operations to prepare the material for that process step. Some high-volume processes, such as resin infusion, avoid the prepreg step, but still require special equipment and materials along with constant monitoring of the process over the duration of the curing time (for example, US Patents 4,132,755, and 5,721,034).
    [003] Thermoplastic resin compositions are more difficult to impregnate in the fiber reinforcing material, due to their relatively higher viscosity than thermostable resin compositions. On the other hand, thermoplastic resin compositions offer a number of advantages over thermostable resin compositions. For example, thermoplastic prepregs can be more quickly manufactured in articles and fabrication and with fiber reinforced thermoplastic composite materials can use robotic and automated deposit tape of the fiber reinforced thermoplastic composite material in a mold tool to increase the rate of production. This can be by means of a multistage robotic arm that preheats the previous layer of fiber-reinforced thermoplastic composite material before heating and depositing the subsequent layer of fiber-reinforced thermoplastic composite material on top of it.
    [004] Thermoplastic resins are long-chain polymers of high molecular weight that are highly viscous when melted and are often non-Newtonian in their flow behavior. Thus, while thermosets have viscosities in the range of 100 to 5000 centipoise (0.1 to 5 Pa * s), thermoplastics have melting viscosities ranging from 5,000 to 20,000,000 centipoise (5 to 20,000 Pa * s), and more typically 20,000 to 1,000,000 centipoise (20 to 1000 Pa * s). Despite the viscosity difference of three orders of magnitude between thermosetting and thermoplastics, some processes have been applied in both types of dies for the lamination of fibrous materials.
    [005] Fiber reinforced plastic materials can be manufactured by first impregnating the fiber reinforcement with resin to form a prepreg, then consolidating two or more prepregs into a laminate, optionally with additional forming steps. Some processes apply fusion directly to the fibers. A tape can be made by coating a dry web of fibers collimated with the polymer and applying a heating process that forces the polymer into and around the fibers (for example, see U.S. Pat. Nos. 4,549,920 and 4,559,262). Another process used to coat and impregnate a dry screen of collimated fibers is to pull the screen through an aqueous paste of fine particles of thermoplastic polymers in which the polymeric particles are trapped within the filament bundles. Subsequent heat and pressure in the process boil the water, and then the polymer melts to force it into and around the filament bundles. This process is described in US Patents 6,372,294, 5,725,710, 4,883,552 and 4,792,481. A modification of the aqueous paste impregnation process is to eliminate the use of water and surfactant as dispersing agents for the polymer particles and, instead, electrostatically charge the particles in a fluidized air bed to trap the particles in the filament bundle. Subsequent heat and pressure zones melt the polymer to coat / impregnate the filament bundle, as disclosed in US Patent 5,094,883. Thus, for those skilled in the art, there are several methods for coating and / or impregnating a fibrous substrate taking into account the available equipment process and the appropriate selection of the shape of the polymeric product (flakes, fine powder, film, non-woven veil, pellets) and melting viscosity.
    [006] Both thermoplastic and thermoset composites can be formed into thin, flexible sheets or strips, referred to as tape. This allows the composite components to be formed by depositing the composite tape on a molding tool, with the thickness of the component being locally varied according to the number of layers of composite tape deposited and also the direction of one or more layers of the tape being controllable, in order to control the final structural properties of the formed composite component. The deposited components are then “consolidated”, a process whose case involves heating the composite structure so that the thermostable plastic or thermoplastic matrix softens to a sufficient degree to form a single unified matrix, and the application of sufficient pressure for the softened matrix to expel any trapped air from the matrix.
    [007] In terms of final structural properties, thermoplastic composites have superior impact and damage resistance properties than thermoset composites and are generally more rigid and more resistant to chemical attack, which are preferred properties within aerospace applications. In addition, since thermoplastic composites can be repeatedly reheated and remolded, they are inherently recyclable, which is an increasingly important factor.
    [008] However, thermosetting composite tape has a property that, in relation to the deposition process, currently makes it the material of choice for use in components in aerospace composite materials. This property is that the thermoset tape is inherently sticky, or is said to have adhesion. This stickiness allows the thermosetting tape to adhere to both mold surfaces in a complex manner, often necessary for composite components in the aerospace industry, and also for separate layers of the thermosetting tape to adhere to each other once the initial layer has been applied to the mold surface, thus making the deposition process relatively easy and convenient to physically manage.
    [009] In contrast, the thermoplastic composite tape is non-sticky. Therefore, it is problematic to make the thermoplastic composite tape adhere to the surfaces of the complex mold during the deposition process. Existing deposition techniques combine local consolidation and melting of the thermoplastic composite material to allow the initial base layer to be constructed only once the base layer is firmly attached to the surface of the mold tool. The previously proposed solutions to this problem have included the application of a separate double-sided adhesive tape as an initial layer for the mold surface to which the first layer of the thermoplastic tape composite adheres later. Likewise, it has also been proposed to spray an adhesive on the surface of the mold. Although both proposed solutions allow the first layer of the thermoplastic tape composite to be successfully applied to the mold surfaces with complex shapes, they introduce their own problem of how to subsequently remove the composite component formed from the mold when the process deposition is complete, since the component is now effectively bonded to the surface of the mold. Consequently, it is still presently preferable to use thermosetting composite materials despite the superior physical properties provided by thermoplastic composite materials.
    [0010] The known methods for the manufacture of composite articles include manual and automated manufacturing. Manual fabrication involves manual cutting and placement of material by a technician on a mandrel surface. This manufacturing method is time-consuming and expensive, and can possibly result in a lack of uniformity in deposition.
    [0011] Automation manufacturing techniques include flat ribbon laminating machines (FTLM) and contour ribbon laminating machines (CTLM). Typically, both FTLM and CTLM employ a solitary composite material dispenser that runs along the work surface over which the composite material is to be applied. The composite material is generally applied in a single line (of composite material) at a time to create a layer of the desired width and length. The additional layers can then be built on top of a previous layer to provide deposition with a desired thickness. FTLM typically applies composite material to a flat transfer sheet; the transfer and deposition sheet are subsequently removed from the FTLM and placed on a tool, mold or mandrel. In contrast, CTLM typically applies composite material directly to the work surface of a tool, the mold or mandrel. FLTM and CTLM machines are also known as automated tape deposition (ATL) and automated fiber placement (AFP) machines, with the dispenser commonly referred to as a tape head.
    [0012] The productivity of ATL / AFP machines is dependent on machine parameters, composite deposition characteristics, and material characteristics. The machine parameters, such as start / stop time, stroke transition time, and cut / add folds determine the total time of the ribbon head in the ATL / AFP material is deposited on the mandrel. Composite deposition characteristics, such as localized bend constructions and part dimensions, also influence the total productivity of ATL / AFP machines.
    [0013] The ideal process for creating thermoplastic parts is in-situ manufacturing in which a part is created by robotically placing and consolidating the thermoplastic materials for the molding tool in a single step. Thermoplastic composite materials are devoid of adhesion, which complicates the use of manual and automated deposition operations, especially the first bend, against the surface of the molding tool.
    [0014] The key material factors that influence the productivity of the ATL / AFP machine are similar for a thermosetting composite resin composite, when compared with a thermoplastic matrix composite, there are still some fundamental differences. For thermosetting resin matrix composites, the key factors are the levels of resin impregnation, the surface coverage, and "stickiness". Stickiness is the level of adhesion necessary to maintain the position of the tape / trailer on the tool or deposition after it has been deposited on it. Due to the unreacted nature of the thermosetting resin, the AFP / ATL process is usually carried out at room temperature, but in a humidity controlled room due to the sensitivity to humidity on the material's tackiness level. Among other impacts, stickiness affects the ability to deposit the first layer of material onto the tool. First fold deposition of thermoplastic materials is hampered by the lack of stickiness to keep the first layer below the tool.
    [0015] The first fold of composite to be placed against any tool requires some adhesive or other force to position the material and keep it against gravity or rigidity of the material. When thermosetting materials are used, the polymer that is above Tg in the deposition head will provide this strength. When the matrix resin is a high performance thermoplastic, this temperature Tg is substantially higher and substantially above room temperature. Heating the molding tool, providing a vacuum source, using a lower temperature film or using a solvated thermoplastic polymer to provide the restraining force are all methods currently used. Each of these methods has limitations in terms of cost, tool complexity, variation in part dimensions or requires hazardous solvents for practice.
    [0016] A method known to overcome the limitation of low tackiness in the manufacture of thermoplastics is to provide a mold tool made of a porous material and apply a negative pressure to the porous material in order to create a negative pressure on the surface of the mold, whereby the thermoplastic composite material is held against the surface of the mold, due to the negative pressure on the surface of the mold when the first layer of thermoplastic composite material is placed on the surface of the mold. The thermoplastic material can then be consolidated and heated to form the thermoplastic composite material (see, for example, US Patent Publication Application No. 2011/0005666).
    [0017] Thermoplastic matrix composites have key factors similar to the thermosetting matrix composites for productivity of the ATL / AFP machine, but the thermoplastic polymer tape is devoid of tackiness under ambient conditions. Thermoplastics generally have low surface energies, a high glass transition temperature ("Tg"), making adhesion at room temperature unlikely. In addition, thermoplastic matrices are of high performance in their glass state at room temperature, making the molecular diffusion mechanism for tackiness virtually impossible. Thus, tackiness is achieved in thermoplastic composites dynamically by applying additional energy in the form of thermal, ultrasound, optical (laser), and / or electromagnetic (induction) energy to depositing wire and entering, to raise the temperature of the above materials their softening and / or melting temperatures, in order to facilitate the molecular diffusion of polymer chains to occur between the two surfaces. Once the polymer chains have been diffused over the entire surface, the additional energy added to the materials must be removed to a level that will avoid distortion of the laminate deposition once the lamination pressure of the ATL / AFP head is removed. . This rapid flow of energy into and out of deposition becomes desirable from an energy use and deposition speed to carry out this process step at the lowest possible temperature and energy, without compromising the temperature performance of the resulting composite part .
    [0018] Consolidation is typically necessary to remove voids that result from the resin's inability to fully displace air from the fiber bundle, trailer, or roving during the processes that were used to impregnate the fibers with resin. Individually impregnated traveling wires, trailers, pleats, or layers of prepregs are usually consolidated by heat and pressure by autoclaving. The consolidation step has generally required the application of high pressures and high temperatures under vacuum for relatively long periods of time. In addition, the consolidation process step using an autoclave or in an oven requires a “bagging” operation to provide deposition with a sealed membrane over the tool to allow the vacuum to be applied to remove air and to supply the pressure differential required for consolidation purposes in the autoclave. This process step further reduces the total productivity of the composite part operation. Thus, for a thermoplastic composite it would be advantageous to consolidate in-situ from an empty composite while laminating the tape to the substrate with the machine / AFP ATL. This process is generally referred to as ATL / AFP in situ and the material used in that process is called grade tape in situ.
    [0019] In general, thermoplastic composites have been of limited success to date, due to a variety of factors including high processing temperatures (currently around 400 ° C), high pressures, and the long molding times required to produce laminates from good quality. Most efforts have been focused on combining high-performance polymers for structural fibers that have only exacerbated process problems. Since the time period normally required to consolidate the prepreg folds properly determines the production rate for the part, it would be desirable to achieve the best consolidation in the shortest amount of time. In addition, lower consolidation pressures or temperatures and shorter consolidation times will result in a less expensive manufacturing process due to reduced energy consumption per molding part and other manufacturing benefits.
    [0020] Thus, the fiber-reinforced thermoplastic materials and methods available for the production of stiffened light composites require improvements. Thermoplastic materials having improved process speeds in automated deposition machines and lower processing temperatures and having no autoclave or furnace step would be a useful advance in the technique and could find rapid acceptance in the high performance aerospace and automotive industries, among others. Summary of the Invention
    [0021] The present invention provides a mold tool prepared with a polymer coating of the surface layer releasably adhered to the mold surface of the mold tool. The mold tool is a non-porous metal mold that has a mold surface with a texture and a release film adhered to the textured mold surface of the mold tool and the surface coating polymer layer adhered to the release film . The polymer coating of the surface layer is preferably a plurality of thermoplastic particles applied to the surface of the mold by plasma spray creating a substantially fused layer of thermoplastic particles. The prepared mold tool assists in the placement and adhesion of the first fold of a fiber-reinforced thermoplastic composite material, such as a thermoplastic prepreg, a unidirectional thermoplastic tape or canvas, fiber tow / preg, or fabric, or non-woven materials, such as a mat or veil. Thermoplastic prepregs are traditionally applied by hand deposition while unidirectional thermoplastic tapes are applied by placing tape in automated deposition in situ against a mold tool.
    [0022] The present invention also involves a method for the preparation of a mold tool prepared for the first deposit bend, providing a solid metal, non-porous molding tool that has a mold surface, the application of a texture to a mold surface of the mold tool, the application of a release film to the surface of the mold that has a texture and finally application of a polymer coating of the surface layer by plasma spraying of thermoplastic particles on the release film on the surface of the mold tool mold that has the texture.
    [0023] Another embodiment of the present invention provides a prepreg prepared having fiber-reinforced thermoplastic composite material with a surface layer polymer coating adhered to one or both surfaces of the composite material. The polymer coating of the surface layer is preferably a plurality of thermoplastic particles applied to the surface of fiber-reinforced thermoplastic composite materials by plasma spraying to create a substantially fused layer of thermoplastic particles on the surface. The prepared prepreg assists in placing the first fold of fiber-reinforced thermoplastic composite material on a mold surface of a mold tool and can further improve the interlaminate properties of the resulting composite part between layers of composite material.
    [0024] The present invention also involves a method for preparing the prepreg prepared by providing a fiber-reinforced thermoplastic composite material, such as a thermoplastic prepreg or unidirectional thermoplastic tape and then applying a layer polymer coating surface by plasma spraying of thermoplastic particles on one or both surfaces of the fiber-reinforced thermoplastic composite material.
    [0025] In the present invention, the surface polymer coating layer provides a chemistry compatible with that placed against the mold tool that maintains dimensions, decreases the temperature requirement for adhesion, and allows the use of hybrid polymer and optional inclusion conductive coatings for lightning in the polymer coating of the surface layer. This compatible chemistry of the present invention improves the adhesion of the first fold of fiber-reinforced thermoplastic composite material to the mold surface of the mold tool, while maintaining the ease of separation of the composite part resulting from the mold tool. When the resulting composite part is removed from the mold tool, the polymer coating of the surface layer will transfer to the resulting composite part as a surface skin that can impart desirable characteristics to the resulting composite part. Such desirable characteristics, such as fire, corrosion or wear protection, can come from multifunctional additives for the polymer coating of the surface layer.
    [0026] Of particular importance is that the surface layer polymer coating is a high performance thermoplastic material, such as poly (ether-ether-ketone) (“PEEK”) or poly (ether-ketone-ketone) (“ PEKK ”).
    [0027] The present invention aims to improve the deposition of the first bend by reducing the failure of the composite part due to the disconnection of material against the mold tool during processing, as well as improving the chemical compatibility in the high performance thermoplastic polymer. . Concepts including rapid crystallization or amorphous materials, as well as discrete metal layers and mixtures of earth fibers are possible. In addition, this discovery also reduces the starting capital and cost investment facility to produce large composites.
    [0028] The present invention also provides methods for manufacturing a resulting thermoplastic composite part with a thickness in the range of 25 to 400 microns that has better processing times in ATL machines and manufacturing equipment.
    [0029] Therefore, the invention described in detail here provides, in one aspect, a mold tool prepared having a surface layer polymer coating of at least one high performance polymer, and a prepared prepreg having layer polymer coating. surface on one or both surfaces.
    [0030] In another aspect, the invention relates to articles of manufacture made of thermoplastic composites according to the invention described herein. Such articles are useful, for example, in the aircraft / aerospace industries, among others.
    [0031] In situ grade thermoplastic composite material tapes for use in an automatic tape deposit or automated fiber laying machine are also provided.
    [0032] These and other features and advantages of the present invention will become apparent from the following detailed description of the various aspects of the invention, taken in conjunction with the accompanying Figures and Examples. Brief Description of Drawings
    [0033] FIG. 1A is a side plan view of an embodiment of the present invention, illustrating the configuration of the prepared tool (10), including the non-porous metal mold tool (20), the textured mold surface (30) of the mold tool, the release film (40) and the surface layer polymer coating (50).
    [0034] FIG. 1B is a perspective view of the embodiment of FIG. 1a illustrating the configuration of the prepared tool (10), including the non-porous metal mold tool (20), the textured mold surface (30) of the mold tool, and a sealer and applied release film (40) and the polymer coating of the surface layer (50) shown as substantially molten thermoplastic particles after application by plasma spray.
    [0035] FIG. 2A illustrates a perspective view of the in situ application of the polymer coating of the surface layer (50) from a plasma spray head (70) to a non-porous metal tool (20), followed by the application of a first folding of fiber-reinforced thermoplastic composite material (60) and compacted by an AFP / ATL deposition bearing (80).
    [0036] FIG. 2B further illustrates a perspective view of the in situ application of the interlaminar layer of thermoplastic (90) (for example, thermoplastic particles) from a plasma spray head (70) to a previously applied thermoplastic composite tape material ( 60), followed by the application of a subsequent fold of fiber-reinforced thermoplastic composite material (60) and compacted by an ATL deposition roller (80) providing interlaminar layer of applied thermoplastic (90) in situ between the layers of reinforced thermoplastic composite material with fiber during automated tape deposition.
    [0037] FIG. 3 illustrates a planar side view of a surface layer polymer coating applied to the surface of a thermoplastic composite prepreg by plasma spraying a thermoplastic polymer coating (50) from a plasma spray head (70) onto one or both surfaces of a composite material (60) to form a plasma-coated thermoplastic composite material (100).
    [0038] FIG. 4A illustrates the mean spacing of local profile peaks of a high temperature mold tool and a thermoplastic surface layer polymer coating using a profilometer.
    [0039] FIG. 4B illustrates the spacing of the peaks on the y axis. Detailed Description of the Invention
    [0040] The present invention provides a mold tool prepared with a polymer coating of the surface layer applied to the surface of the mold side of the mold tool release to improve the adhesion of the first fold of fiber-reinforced thermoplastic composite material to the surface of the mold. mold.
    [0041] Figure 1a illustrates a said embodiment of the present invention providing the configuration of a prepared tool (10), including the non-porous metal mold tool (20) with a textured mold surface (30), a release film (40) and a polymer coating of the surface layer (50) removably applied to the release film. Figure 1b illustrates a said embodiment of the present invention providing the prepared tool (10), detailing the surface layer polymer coating (50) shown as molten thermoplastic particles substantially applied by plasma spray.
    [0042] It is important to note that the polymer coating of the surface layer (50) can be applied to the mold surface on the mold tool release side (20) through the use of plasma spray during automated tape deposition situ. Continuous plasma spraying of the surface layer polymer during automated tape deposition on top of an anterior fold of fiber-reinforced composite material (60) provides a thermoplastic interlaminar layer (90) that can impart beneficial properties, such as hardening to resulting composite part.
    [0043] Figure 2a illustrates in situ application of the polymer coating of the surface layer (50), as thermoplastic particles from a plasma spray head (70) to a non-porous metal mold tool (20) and , then, the application of the composite material reinforced with thermoplastic fiber (60) and compacted by an ATL deposition roller (80).
    [0044] Figure 2b further illustrates the continued plasma spraying of polymer from the surface layer by plasma spray head (70) during the deposition of the automated tape thus providing an interlaminar layer of thermoplastic (90), and then application of a subsequent fold of fiber-reinforced thermoplastic composite material (60) compacted with an ATL deposition roller (80). The continued application of the polymer coating of the surface layer, as a thermoplastic from a plasma spray head (70) over an anterior fold of thermoplastic fiber-reinforced composite material (60) and then a subsequent fold of thermoplastic composite material (60) applied and compacted by an ATL deposition roller (80) provides an applied thermoplastic layer (90) in situ between the layers of fiber reinforced thermoplastic composite material and subsequently applied thermoplastic fiber reinforced composite material during the automated tape deposit.
    [0045] The interlaminar thermoplastic layer (90) and the polymer coating of the surface layer (50) are each high-performance thermoplastic polymers, and may be the same or different materials and may contain the same or different multifunctional additives . This versatility in the selection of the high performance thermoplastic polymer in particular allows the selection of the ideal materials for the surface layer coating (50) and the interlaminar layer (90).
    [0046] Likewise, the first fold of fiber-reinforced composite material (60) and the subsequent folds of fiber-reinforced composite material (60) are each of compatible material, but can be the same or different compositions, depending desired properties for each layer.
    [0047] Alternatively, the present invention provides prepreg prepared with a polymer coating of the surface layer applied directly to one or more surfaces of a thermoplastic fiber-reinforced composite prepreg material to improve adhesion of the first fold of the reinforced composite material with thermoplastic fiber to the mold surface of the mold tool and to further provide a beneficial interlaminar layer for the resulting composite part.
    [0048] Figure 3 illustrates a prepreg (100) prepared by applying a surface layer polymer coating (50) to both surfaces of a thermoplastic fiber-reinforced composite material (60), by spraying particle plasma thermoplastics from a plasma spray head (70) to the surfaces of a fiber-reinforced composite material (60), thereby forming the prepared prepreg (100). Depending on the performance of the required resulting composite part, the polymer coating of the surface layer can be the same or different on each side of the prepared prepreg (100).
    [0049] The prepared tool (10) of the present invention incorporates a surface layer polymer coating (50) which is removably adhered to the mold surface of a mold tool (20). Preferably, a release film (40) is interposed between the mold surface of the mold tool (20) and the surface layer polymer coating (50). In addition, for optimal control of the adhesion of the polymer coating from the surface layer (50) to the mold surface, the mold surface of the mold tool (20) is a textured surface (30). Prepared tool (10) can be used to deposit composite material reinforced with fiber by hand or by ATL as may be desired. Prepared tool (10) provides for the ideal controlled adhesion of the first fold of fiber reinforced composite material with during or application by hand or ATL.
    [0050] Figure 2a illustrates the deposition of a first fold of fiber-reinforced composite material (60), by placing the automated tape deposition on the mold surface of the mold tool (20). When using a tape prepreg as the fiber-reinforced composite material (60), a plasma spray head (70) will spray thermoplastic particles on the mold surface, forming the surface layer polymer coating (50) on the mold surface for preparing the mold surface of the mold tool (20). Subsequently, an ATL deposit roll (80) deposits and removably adheres the fiber-reinforced composite prepreg tape (60) to the polymer coating of the surface layer (50) on the mold surface of the mold tool ( 20). The continued application of this process is illustrated by figure 2b, in which subsequent layers of fiber-reinforced composite material (60) are applied by spraying thermoplastic particles on the surface of a previously bonded layer of fiber-reinforced composite material (60), using a plasma spray head (70), and then applying with an ATL deposition roller (80) a subsequent fold of fiber-reinforced composite material to create a layer of interlaminar thermoplastic (90). This thermoplastic interlaminar layer (90) can provide beneficial curing or other multifunctional benefits as desired.
    [0051] Prepreg (100) of the present invention is prepared by applying a surface layer polymer coating (50) to one or both surfaces of a fiber-reinforced composite material (60) directly before or during in situ deposition of fiber-reinforced composite material (60). A stream of fiber-reinforced composite material (60) is passed between one or more plasma spray heads (70) which applies the polymer coating of the surface layer (50) to one or both sides of the composite material (60) , thereby forming the prepared prepreg (100). This prepared prepreg (100) can then be applied directly to a mold tool or a prepared tool (10) by deposition by hand or by ATL as desired, and is removably adhered to the mold surface of the mold tool or prepared tool (10). Prepared prepreg (100) can be applied as a prepreg tape by an ATL deposition roller, as shown in Figure 2a, without the need for a separate plasma spray head (70) to apply a first fold of fiber-reinforced composite material having a polymer coating of the surface layer (50) adjacent the mold surface of the mold tool (20). The mold surface is preferably a textured mold surface (30). Prepared prepreg (100) can save production costs and create more uniform production conditions, providing the same potential multifunctional benefits. If the polymer coating of the surface layer (50) is applied to both surfaces of a fiber-reinforced composite material (60), the coating (50) on each surface can have the same or different compositions.
    [0052] Various methods of applying surface layer polymer coating (50) are available and are known in the art, such as by spraying a solvent-based polymer solution onto the mold surface of a metal mold tool , by hand application of a water-based paste, a plasma spray application, or a powder coating and electrostatic melting method, among others.
    [0053] A particularly preferred embodiment of the present invention provides for the application of plasma spray of polymer from the surface layer onto the mold surface of a mold tool (20) forming a prepared tool (10), as illustrated in Figures 1a and 1b, or directly on the fiber-reinforced composite material (60) as shown in Figure 3 to form prepared prepreg (100). When the surface layer polymer coating (50) is applied with a plasma spray gun, the surface layer polymer is introduced into the plasma gun in the form of solid particles, the thermoplastic particles preferably having a diameter D90 (where ninety percent of the particles are smaller than the number, in volume) from 90 to 180 μm and more preferably 150-185 μm. The particles are applied using a low speed, high plasma temperature.
    [0054] The preferred polymer particle of the high performance polymer surface layer is PEEK polymer.
    [0055] The surface layer polymer coating (50) is substantially continuous, but may be discontinuous at lower levels of thickness along the surface of the mold, in particular, depending on the level of roughness of the textured surface (30 ) to which it is applied. It is desired to be continuous over at least 50% of the mold surface, and more preferably at least 90% of the mold surface and ideally, at least 98% of the mold surface. When a plasma spray head (70) is used to apply the polymer coating of the surface layer (50), the heated thermoplastic particles impact and adhere to the mold surface as molten particles and the resulting surface coating layer (50 ) can appear as a plurality of batch granules that are well fused into thermoplastic particles, but not all are melted together, forming the partially batch film.
    [0056] The size of the high performance polymer particles is D90 from about 100 μm to about 400μm. Preferably, the polymer particle sizes are in the D90 range of about 125 μm to about 250 μm, and more preferably from about 150 to about 200 μm for optimal plasma spray application results. When applied, the high performance polymer particles are exposed to a plasma spray head temperature in the range of about 1800 ° F to about 2000 ° F at a speed of about 350 to about 400 meters / second with the nozzle section of the plasma spray applicator vent port.
    [0057] Useful commercially available plasma spray applicator includes the Praxair SG 10 plasma spray applicator or a Sulzer Metco plasma spray applicator. The high-performance polymer is introduced into the plasma spray head as a solid particle. The plasma spray applicator then directs the solid particles into the plasma jet stream to heat and accelerate the particles at a high speed.
    [0058] For best performance, the mold tool (20) is preheated to about 250 ° F (121 ° C) to assist in adhesion of the surface layer polymer coating (50) to the mold surface the mold tool (20).
    [0059] For the preparation of a prepared mold tool, plasma spraying must apply the polymer coating of the surface layer (50) to the mold surface of the mold tool (20) with a thickness in the range of 0.001 to 0.010 inches thick layer. In some embodiments, the thickness of the polymer coating of the surface layer (50) is more preferably about 0.002 inches. This thickness is intended to assist in the adhesion of the first layer, without adding significant weight to the resulting composite part.
    [0060] In preparing a prepared prepreg (100), the plasma spray must apply a polymer coating of the surface layer (50) to a fiber-reinforced thermoplastic composite material (60) with a thickness of about 0.0005 at about 0.010 inches per layer. In some embodiments, the thickness of the surface polymer layer can be from about 0.001 to about 0.008 inches per layer.
    [0061] Surface polymer layer coating (50) can be removably applied to the mold surface of the mold tool (20) to allow effective release of the resulting composite part from the mold surface of the mold tool . While a difficulty with automated tape deposition of thermoplastic fiber-reinforced composite materials is ineffective in adhering the first fold to the mold surface of the mold tool, the polymer coating of the thermoplastic surface layer should not adhere as strongly to the mold surface. of the mold tool so that when removal is attempted, the polymer coating of the thermoplastic surface layer is compromised and the resulting thermoplastic composite part is damaged. This is especially important when the thermoplastic surface layer polymer coating contains any multifunctional agent as described herein to further improve the surface properties of the resulting thermoplastic composite part.
    [0062] For the purposes of this invention, the polymer coating of the thermoplastic surface layer is said to be removably applied when the resulting thermoplastic composite part made in a mold tool with a polymer coating of the thermoplastic surface layer releases from the mold tool with a slight to modest pressure, as long as the polymer coating of the surface layer does not loosen during the automated deposit in situ of the thermoplastic fiber reinforced composite material.
    [0063] The polymer of the thermoplastic surface layer (50) on the mold surface of the mold tool (20) can improve the surface quality and properties of the resulting thermoplastic composite part as it is removed from the mold tool due to the qualities of the resin-rich thermoplastic surface layer polymer coating, the improved surface texture, and optional multifunctional additives that can be incorporated into it.
    [0064] The surface layer polymer coating (50) may comprise a high performance polymer chosen from slow crystallization, semicrystalline polymer or an amorphous polymer (or mixtures thereof), such that the polymer coating of thermoplastic surface layer (50) forms a miscible and / or compatible mixture with the high performance thermoplastic polymer of the fiber-reinforced thermoplastic composite material (60). The surface layer polymer coating (50) can be any of the high performance thermoplastic polymers described herein, which is applied to the mold surface of the mold tool (20) for improved first-fold deposition processing, as described herein. , or applied directly to one or both surfaces of the fiber-reinforced thermoplastic composite material (60), prior to the application of the mold tool.
    [0065] The morphology of the high performance thermoplastic polymer can be amorphous and / or a slow crystallization (i.e., low crystallinity - typically less than 20% crystallinity) of the semi-crystalline polymer. Mixtures of amorphous and semi-crystalline polymers are also contemplated for use as a surface layer polymer coating (50). In certain embodiments, the high performance thermoplastic polymer for coating the thermoplastic surface layer polymer (50) is chosen from polyarylethylketones (PAEK), polyetherimide (PEI), polyimides, PAEK copolymer with PEI and / or polyethersulfone (PES) and / or polyphenylenesulfide (PPS), and PAEK mixtures with one or more of PEI, PES, PPS and / or polyimides.
    [0066] In particular embodiments, for example, polymer coating of thermoplastic surface layer includes PAEK chosen from polyetheretherketone (PEEK) or polyetheretherketone (PEKK) and mixtures with, but not limited to, diphenylsulfone. When the polymer of the thermoplastic surface layer includes PEKK, the T: I ratio of PEKK ranges from about 0: 100 to about 70:30, in order to maintain the low crystallization speed of the polymer of the surface layer. In a particular embodiment, the polymer T: I ratio of the thermoplastic surface layer uses CYPEK® DS que which has a T: I ratio of between about 0: 100 to about 70:30. Suitable PEKK polymers available for use with the present invention include, among others, those commercially available from Cytec Industries Inc., Woodland Park NJ, such as CYPEK® DS-E or CYPEK® DS-M and CYPEK® HT.
    [0067] The surface layer polymer coating (50) can also include one or more multifunctional agents chosen to improve the characteristics of the resulting thermoplastic composite part, such as electrical conductivity, strength, oxygen permeability, crystallization rate and / or solvent resistance of the resulting thermoplastic composite part. Such multifunctional agents can be in the form of a metallic coating and / or micro and / or nano-particles.
    [0068] Multifunctional agents of the optional surface layer polymer coating (50) may include one or more of the materials, such as, but not limited to, impact modifiers, release agents, lubricants, thixotropes, antioxidants, UV absorbers, stabilizers heat, flame retardants, pigments, dyes, layered dyes for impact damage indicators, non-fibrous reinforcements and fillers, nano-graphite platelets, to improve the crystallinity rate and mitigate wrinkling, nano-clays to improve solvent resistance , nano-metals (such as nickel fibrils), interleaving particle for impact hardening, CVD veil fabrics in OML light interleaving, fiber or polymer veils to improve impact performance, surface finishes to help remove air as pressure is applied by the ATL machine, and high flow surface coatings to accelerate reptation by curing through the entire region fold.
    [0069] The mold tool (20) can be of any non-porous high temperature tool including metals. Metal tools, preferably stainless steel, invar or low carbon steel, as is known to a person skilled in the art, are suitable. The mold surface of the mold tool (20) may be of stainless steel capable of withstanding the high processing temperatures required for the manufacture of composite parts reinforced with thermoplastic fibers and low CTE, but it is preferably invar. High temperature tooling is able to withstand processing temperatures up to 800 ° F (427 ° C). Mold tool (20) can be a 0.120 thick or 0.063 ”304 stainless steel plate invar 36. However, the stainless steel plate may not be as effective as invar due to the higher CTE differential, which can cause delamination during processing of the thermoplastic fiber reinforced composite material from the mold surface of the mold tool.
    [0070] The mold tool (20) must be a solid, impermeable material, which is non-porous. The mold tool (20) must not allow air or gas to flow through its mold surface.
    [0071] The textured mold surface (30) is preferably created on the mold surface of the mold tool (20) in order to improve the mechanical adhesion of the polymer from the surface layer (50) to the mold tool (20 ), in an effort to overcome the differential CTE delamination of the fiber-reinforced thermoplastic composite material (60) and the polymer coating of the surface layer (50) from the mold surface of the mold tool (20). The textured mold surface (30) appears to provide a mechanical lock between the mold tool (20) and the surface layer polymer coating (50), as well as improving adhesion, in order to overcome differences in the coefficient of thermal expansion between the surface layer polymer coating (50) and the mold tool (20). Very little texture and mechanical blocking will be insufficient to overcome the CTE differential, resulting in the polymer coating of the surface layer (50) easily peeling off the mold tool (20) during manufacture. Too much surface stroke of the textured mold (30) can result in a surface layer polymer coating (50) that can be difficult to release and remove without causing damage to the surface layer polymer coating (50) in an attempt to remove the composite part resulting from the mold tool.
    [0072] The textured mold surface (30) can be added by many means, such as blasting, grinding, Blanchard grinding, glass ball detonation, serration, or other means for the texture of the mold surface to accept the release film (40). Creation of the textured mold surface (30) can be achieved by a method such as sandblasting with a grain size of about 20 grit to about 180 grit, and more preferably from 40 grit to 120 grit. In particular, about 120 grit of aluminum oxide or about 40-60 grit glass beads provide a uniform surface texture and are preferred with 40-60 grit glass beads being ideal. The preferred methods of applying an appropriate texture are sandblasting with 120 grit aluminum oxide or 40-60 grit glass spheres.
    [0073] The suitable texture for a particular combination of a mold surface of the mold tool (20) and the polymer coating of the surface layer (50) can be optimized by a person skilled in the art to identify the most appropriate level of texture for a particular surface layer polymer coating (50) and a mold tool (20). A person skilled in the art will be able to identify the most appropriate level of texture for the type of mold tool material and the polymer coating material of the surface layer to overcome the CTE differences involved to support sufficient adhesion while maintaining the ability to detachment of the resulting composite part.
    [0074] A method of quantifying an adequate level of texture is by measuring the profile elements of a textured mold surface (30). Both a greater average spacing of profile elements and a greater depth of profile elements are the appropriate means to distinguish the preferred levels of texture. Both profiled elements must be appropriate for the texture to be suitable.
    [0075] The high temperature mold tool and a thermoplastic surface layer polymer coating, an invar .063 sheet 36 coating with a PEKK surface layer polymer coating, has been tested with a stylus tip surface TR200 profilometer diamond by Time Group Inc., inductance-type surface roughness tester. The surface profilometer uses a diamond stylus that is moved at a controlled speed along the sample surface, to detect material characteristics. These parameters are measured in a flat sample by placing the device on top of the sample. This is a test carried out at normal room temperature and humidity and the mold tool must be tested at room temperature. The profilometer is placed over the sample in the x direction (defined as parallel to the edge of the test bench) and the assay is started using the play arrow key and all parameters are recorded in the X direction. The profilometer is then repositioned perpendicular to the previous test and the test is repeated to record all parameters for the Y direction.
    [0076] This RSM calculation is illustrated in Formula 1, with RY illustrated in Formula 2. As can be seen in Table 1, below, a maximum height combination of peak-to-peak measurement profile has been found to be the best texture feature ideal. Higher values than those presented in Table 1 can be obtained and used. However, higher values can negatively increase mechanical adhesion, impact the size of the resulting composite part, and distort tolerances. Table 1 -

    [0077] The mold release film (40) can be applied to the mold surface of the mold tool (20) after applying the surface texture of the mold (30) to the mold tool to cover evenly and evenly the mold surface of the mold tool (20). The mold release film (40) further provides the appropriate releasable adhesion of the polymer coating of the surface layer (50) to the mold surface of the mold tool (20). The mold release film (40) can only partially cover the textured mold surface (30) of the mold tool (20), as long as it covers that recommended by the mold release manufacturer.
    [0078] The mold release film (40) acts as an interface between the textured mold surface (30) of the mold tool (20) and the surface layer polymer coating (50). The mold release film (40) also provides a chemical bond to contain the surface layer polymer coating (50) on the surface of the mold, thus maintaining optimal adhesion and subsequent detachment of the surface layer polymer coating to the mold surface during the application of the thermoplastic fiber reinforced composite material. The mold release film (40) is also sufficiently robust to survive the intense heat and conditions of the deposition process such that it provides a release layer to separate the polymer coating from the surface layer (50) from the mold tool (20) once the resulting composite part has been cured.
    [0079] Mold release film materials are commercially available and are advertised as capable of releasing the product from a mold tool after processing. Suitable commercial mold release films include Hysol Frekote 800, AXEL 21RM, AXEL 21LS, and AXEL W-4005. The release agent is preferably high temperature AXEL W-4005 applied and tempered by the manufacturer's specifications.
    [0080] The mold tool (20) in conjunction with the mold release film (40) can then be heated to "temper" as recommended by the supplier.
    [0081] A sealer can optionally be applied to the mold surface of the mold tool (20), as recommended by the mold tool manufacturer before applying the mold release film (40) to further increase releasable adhesion of the polymer coating of the surface layer (50) and allow the release of the composite part resulting from the mold surface.
    [0082] The fiber reinforced composite material (60) is structural reinforcement fiber material, pre-impregnated with an appropriate high performance thermoplastic polymer matrix resin. These are generally classified as ribbon, woven cloth, non-woven cloth, paper, and mixtures thereof.
    [0083] Structural reinforcement fibers suitable for fiber reinforcement include any of the commercially available structural fibers, such as carbon fibers, Kevlar® fibers, glass fibers, aramid fibers, and mixtures thereof. In a preferred embodiment, the fibrous structural reinforcement fiber is a carbon fiber based on polyacrylonitrile (PAN).
    [0084] The fibrous structural reinforcement can be configured on a unidirectional tape (uni-tape), non-woven mat or veil, tow fiber, or fabric material. Tape prepreg generally refers to unidirectional structural reinforcement fibers that extend along a single axis of the strip material. Prepreg tape is generally used for ATL deposition applications. The term "fabric" generally refers to structural reinforcement fibers defined along at least two distinct axes within the strip material. Fabric is commercially available as biaxial, tri-axial and quad-axial, indicating fibers that span two, three, or four different axes, respectively. The fibers can optionally be woven with another, or they can be manufactured as a non-woven fabric. Prepreg fabric materials are generally used for hand deposition applications.
    [0085] The fiber reinforced composite material (60) contains any fiber reinforcing the fibrous structure described herein that has been impregnated with at least one high performance thermoplastic polymer by any method of manufacture / impregnation known to those skilled in the art. Suitable impregnation methods are known to those skilled in the art and include, for example and without limitation, hot melt impregnation, aqueous paste impregnation, powder coating, extrusion film lamination, and combinations thereof.
    [0086] The high performance thermoplastic polymer for coating the surface layer (50) and the high performance thermoplastic polymer as the matrix resin for the fiber reinforced thermoplastic composite material (60) can be the same or different materials or their combinations.
    [0087] The term "high performance polymer" is intended to refer to any thermoplastic polymer that has a melting temperature (Tm) greater than or equal to 280 ° C and a process temperature (TProcess) greater than or equal to 310 ° C. In certain embodiments, the high-performance polymer is chosen from polyarylethylketones (PAEK), PAEK mixtures, polyimides, and polyphenylenesulfides (PPS).
    [0088] In certain embodiments, PAEK is chosen from polyetheretherketone (PEEK), polyetheretherketone acetone (PEEKK), polyetheretherketone (PEKK), polyetheretherketone (PEK), and polyetheretherketoneketone (PEKKEK). In still other embodiments, the high performance polymer is a PAEK mixture having polyetherimide, polyphenylene sulfide and / or polyethersulfone mixed with one or more polyarylethylketones.
    [0089] Polyarylethylketones are well known to those skilled in the composite art and include, but are not limited to, APC-2® PEEK, CYPEK®-FC and / or CYPEK®-HT, all commercially available from Cytec Industries Inc., Woodland Park, New Jersey.
    [0090] The resin content of the high performance thermoplastic polymer resin in the fiber-reinforced composite material (60) ranges from about 26% to about 90% by weight of the total thus providing composite material (60) with a module resin of 500 ksi or more and toughness to interlaminar fracture of 600 J / m2 or higher, as measured by G1c. The viscosity of the high performance polymer is adjusted so that a good wet filament is obtained. Ultimately, the high-performance polymer of the fiber-reinforced composite material as part of a polymer matrix and forms a polymer blend with the polymer coating of the surface layer (50) when the materials are brought into contact. As used herein, the term "polymeric mixture" includes mixtures of miscible and compatible polymers as these terms are known and understood by those skilled in the art to which the invention belongs.
    [0091] The resulting thermoplastic composite parts formed by the present invention can be formed using various articles formed using rapid lamination and forming processes including, but not limited to, placing thermoplastic tape / trailer in situ the stiffened wing and fuselage skins, molding by continuous compression (CCM) and rolling process for reinforcement fabrication, double pressure belt to prepare consolidated flat panels and aircraft floor panels, cylindrical structures of filament damage in situ, and fusion bonding and welding of assembly composite.
    [0092] The following examples are provided to assist a person skilled in the art to better understand certain embodiments of the present invention. These examples are for the purpose of illustration and are not to be construed as limiting the scope of the various embodiments of the present invention. Example 1 - sprayed solvent-based PEI polymer solution applied to the tool
    [0093] A PEI polymer formulation, GE Ultem 1000P 10% plus 90% Dioxylane was sprayed in plasma onto the mold surface of a steel mold tool that had a release film using an HVLP applicator.
    [0094] To test the transfer of PEI / Dioxilane from the first fold of fiber-reinforced thermoplastic composite, an almost isotropic 8-fold panel was created using APC PEKK / AS-4 uni-tape material. The panel was processed with a hood plate at an autoclave temperature of 720 ° F (382 ° C) and 100 psi of N2. The panel showed some superficial anomalies on the coated face. Example 2 - water-based paste applied by hand to the tool
    [0095] The technique of direct application by hand was tried using a mixture that includes surfactant, water, hydrosize (calibration) and thermoplastic, as follows: 1) dimensioning 90% / PEKK 10%. 2) water D.I. 80% / 10% Surfactant / PEI-Diox. 10% premix solution. 3) 80% DI water / 10% surfactant / 10% PEKK. 4) dimensioning 80% / PEI powder 10% / 10% surfactant). The layer polymer surface of the resulting water-based paste thermoplastic surface shrinks rapidly over the mold surface of the mold tool and has not reached a suitable bond for metal mold tool. The polymer coating of the surface layer peeled off very easily with minimal friction. Example 3 - PEK polymer sprayed on plasma over mold tool
    [0096] To give a coating directly on the mold surface of a mold tool applied with a sealer and release film, a plasma spray coating was performed using a Praxair SG 100 plasma gun and PEK polymer introduced into the jet stream to heat and accelerate the high-speed material. Initially, it was difficult to maintain the adhesion between the sealed / released tool and the PEK polymer, when the tool was allowed to cool to room temperature, probably caused by the difference in CTE (coefficient of thermal expansion) of the mold tool and the polymer coating of the layer of thermoplastic surface on the smooth surface of the mold of the mold tool. It appears that the skin coating released from the tool (Hysol® Frekote® GP sealing agent and Frekote® 800 release agent). Example 4 - plasma sprayed PEK polymer on the textured mold surface of the mold tool
    [0097] To improve the adhesion of PEK polymer spray on plasma, a subsequent panel was sandblasted with 120 grit aluminum oxide and release coated with Frekote® 800. A much better coating application was achieved.
    [0098] To test how the PEK plasma sprayed coatings transferred to a laminate, two 8-fold quasi-isotropic panels were created using APC PEKK / AS-4 uni-tape material. The panels were treated with a hood plate at an autoclave temperature of 720 ° F (382 ° C) and 100 psi of N2.
    [0099] The resulting panels showed some uneven surface texture and thickness of polymer coating of the surface layer. Some areas of the surface coating can be scraped from the resulting thermoplastic fiber reinforced composite part. The mold surface of the mold tool was cleaned after the autoclave cycle, indicating that the mold release was effective. Example 5 - PEK polymer plasma spray coating over prepreg
    [00100] Plasma spraying was also performed on APC-uni-tape samples to provide a path for adding material to the outside of a thermoplastic material. Two coated weights were deposited to test the process control. Only one side of the tape was coated. Transverse resin shrinkage and ribbon wrinkling were noted.
    [00101] The unique capabilities of this process offer beneficial uses, such as combinations of materials, including ceramic, metallic materials and polymer mixtures that would be difficult to produce by other means. Alloy metal coatings can provide better electrical conductivity by lightning and edge glare reduction. Example 6
    [00102] Parts of thermoplastic composites are processed at high temperatures and require stable tool materials. The processing cycle for PEKK-FC uni-tape panels exceeds 730 ° F (388 ° C) which requires an alloy tool. For this series of experiments, the tooling was 0.120 '' thick of 304 stainless steel plate.
    [00103] Various surface finishes were tried during this experiment. The standard smooth panel was a 0.125 '' thick stainless steel plate that had been sanded with sandpaper 120 and cleaned with solvent. The textured surface treatments used included 120 grit aluminum oxide and blasting 40-60c grit glass beads. These surfaces increased the mechanical blockage of the first-fold coating to the release coating material. It is believed that the surface also broke the resin film, creating thick and thin areas that reduce the effect of resin wrinkling on tool adhesion. The blown glass ball tool is recommended for plasma spraying, but has not yet been tried. The advantage of texture is that it helps to retain the coating during processing.
    [00104] Zyvax Sealer GP was initially used to seal stainless steel plates. This has been shown to interact with the Frekote® 800 to produce a surface with an extremely easy release. This causes the coating to slip prematurely into the tool. After this was discovered, the sealer was mechanically removed from all surfaces and discontinued.
    [00105] The first mold release evaluated was Hysol® Frekote® 800. This solvent-based system is known to offer release at processing temperatures above 400 ° C. The release was rubbed onto the stainless steel surface and allowed to air dry, and then the plasma tools were sprayed with thermoplastic. Initial coating used PEI / dioxilane spray and showed a tendency to peel the tool with minimal abrasion. Mold release Kant-Stik Cure-Fast was later tested and also demonstrated to have an easy release surface. This release has been difficult to process above 750 ° F (399 ° C).
    [00106] The AXEL 21RM mold release was then used without a gauge and appeared to have a more “tight” surface than any of the previous versions. It is a solvent-based system. Axel 21RM is the preferred release available for this application. It works without a sealer to provide good adhesion to the surface without being too slippery. The water-based version, W4005, was also attempted to compare with the AXEL 21RM, but proved to be sensitive to abrasion with small release “balls” evident after some abrasion on the tool's finger.
    [00107] According to the recommendations of the release manufacturer, the tools were heated up to the temperature of use (735 ° F, 391 ° C) to temper the release for the tool. Tempering the tool allows the release to be cured for the tool before entering into service. This step was included to prevent the first solvent from first deposition using the PEI / dioxylane solution from lifting the mold release film. Example 7
    [00108] To give a coating directly on a coated release tool, a plasma spray coating was performed using a plasma gun and PEK polymer introduced into the jet stream to heat and accelerate the material at high speed. The PEK polymer is fed to the plasma gun using a fluidized bed feeder system.
    [00109] This time, the tool has been preheated to 250 ° F (121 ° C) to help the polymer adhere to the tool's surface. A Praxair SG 100 plasma gun was used to deposit approximately 2 mils of PEK polymer into the tool. This temporarily deposits the powder on the tool. The powder coated stainless steel tools were then processed in an electric oven at 750 ° F (399 ° C) to melt the polymer and create a layer of molten polymer.
    [00110] To improve the adhesion of the plasma spray, a subsequent panel was sandblasted with 120 grit aluminum oxide and release coated with Hysol® Frekote® 800. The ribbon image frame was placed over the tool to create a central panel rough and a smooth perimeter. This frame was intended to show the effect of roughness transitions on the surface in the deposition materials of the first fold. This also provides a smooth area to mask super spraying of the tool.
    [00111] To test how the coatings sprayed with PEK plasma transferred to a laminate, an 8-fold quasi-isotropic panel was created using APC PEKK / AS-4 uni-tape material. The panel was processed with a hood plate at an autoclave temperature of 720 ° F (382 ° C) and 100 psi of N2. The resulting panel showed some uneven texture and thickness of the coating. The coated tool surfaces were cleaned after the autoclave cycle, indicating that the mold release was effective.
    [00112] Film lamination using bi or tri-layer thermoplastic tape in situ. A small press was heated to between 290 ° C and 410 ° C. Kapton film is coated with a release agent and, with the press at the desired temperature; a two- or three-layer configuration is sandwiched between two pieces of Kapton film coated with release agent, thereby forming a deposit. The deposition is placed between the two 3''X 3 '’plates of the stainless steel hood of the press together with a thermocouple. The stack is inserted into the press and 1,000 pounds of pressure is applied and maintained for a period of 10 to 30 seconds. The pressure and top plate is then released and the stack is removed to cool under a cold press (1000 pounds per 1 minute).
    [00113] In view of the description and examples above, a person skilled in the art will be able to practice disclosure as claimed without undue experimentation.
    [00114] Although the previous description has shown, described and pointed out the fundamental innovative characteristics of the present teachings, it will be understood that various omissions, substitutions and changes in the shape of the device's detail, as illustrated, as well as their uses, can be done by those experts in the technique, without departing from the scope of the present teachings. Therefore, the scope of the present teachings should not be limited to the previous description, but should be defined by the appended claims.
    权利要求:
    Claims (6)
    [0001]
    1. Method for depositing automated tape of composite material reinforced with thermoplastic fiber (60) in situ, characterized by the fact that it comprises: providing a non-porous mold tool (20) that has a mold surface (30); applying a release film (40) on the mold surface (30) of the mold tool (20); introducing a plurality of thermoplastic surface layer polymer particles into a plasma spray gun; plasma spray the polymer particles of the thermoplastic surface layer on the release film (40) to form a polymer coating of the thermoplastic surface layer (50) on the mold tool (20) during deposition of the first layer IN SITU tape of composite material reinforced with thermoplastic fiber (60) having a first surface in contact with the polymer coating of the thermoplastic surface layer (50) and a second surface; plasma spray the polymer particles of the thermoplastic surface layer onto the second surface of the first layer of thermoplastic fiber-reinforced composite materials (60) while depositing the IN SITU tape of a subsequent layer of thermoplastic fiber-reinforced composite material (60) having a first surface and a second surface to form an interlaminar layer of thermoplastic polymer (90) between the second surface of the first layer of fiber-reinforced thermoplastic composite material (60) and the first surface of the subsequent layer of thermoplastic composite material reinforced with fiber (60); and spraying with continuous plasma the polymer particles from the thermoplastic surface layer onto the subsequent layer of thermoplastic fiber-reinforced composite materials (60) while depositing the IN SITU tape until the desired number of layers of thermoplastic fiber-reinforced composite material (60 ) is applied to form an interlaminar layer of thermoplastic polymer (90) between each layer of fiber-reinforced thermoplastic composite material.
    [0002]
    2. Method according to claim 1, characterized by the fact that the polymer of the thermoplastic surface layer (50) is chosen from polyaryethylketones (PAEK), polyetherimide (PEI), polyimides, PAEK copolymer with PEI and / or polyethersulfone (PES ) and / or polyphenylenesulfide (PPS), and PAEK mixtures with one or more PEI, PES, PPS and / or polyimides.
    [0003]
    3. Method according to claim 1 or 2, characterized by the fact that the polymer of the thermoplastic surface layer (50) is chosen from PEK, PEKK, PEEK or their mixtures.
    [0004]
    Method according to any one of claims 1 to 3, characterized in that the polymer of the thermoplastic surface layer (50) further comprises one or more multifunctional agents.
    [0005]
    Method according to any one of claims 1 to 4, characterized in that the polymer of the thermoplastic surface layer (50) is a discontinuous plurality of well-fused thermoplastic particles releasably adhered to the release film (40) .
    [0006]
    Method according to any one of claims 1 to 5, characterized in that the polymer particle of the thermoplastic surface layer has a D90 diameter size of 90 to 180μm before plasma spraying.
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    法律状态:
    2018-03-06| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-13| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-03-20| B06I| Publication of requirement cancelled [chapter 6.9 patent gazette]|Free format text: ANULADA A PUBLICACAO CODIGO 6.6.1 NA RPI NO 2462 DE 13/03/2018 POR TER SIDO INDEVIDA. |
    2019-11-26| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-02-02| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-02-23| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 17/10/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201261715438P| true| 2012-10-18|2012-10-18|
    US61/715,438|2012-10-18|
    PCT/US2013/065400|WO2014062900A1|2012-10-18|2013-10-17|Surface engineering of thermoplastic materials and tooling|
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