impression material or structure comprising a fibrous reinforcement layer and a curable liquid resin

专利摘要:
IMPROVEMENTS IN LAMINATES OR RELATED TO THE SAME This is a process for the preparation of a prepreg, comprising overlapping a resin on a unidirectional fibrous reinforcement layer comprising a plurality of bundles, each comprising a plurality of parallel filaments on a layer impregnated with unidirectional fibrous reinforcement resin comprising a plurality of bundles, each comprising a plurality of parallel filaments, in which the overlapping laminate is compressed to such an extent that the resin penetrates the interstices between the bundles, but penetrates the voids within the bundles less than 22 to 60% by volume of the bundles.
公开号:BR112014017498B1
申请号:R112014017498-9
申请日:2013-01-25
公开日:2020-12-08
发明作者:Pascal Perillat-Collomb；Uwe Karner；Ronald Maarten Pols；Johannes Moser
申请人:Hexcel Holding Gmbh；
IPC主号:

专利说明:

[001] The present invention relates to fiber-reinforced materials comprising fibers and thermosetting resins, and, in particular, materials that are produced by stacking layers comprising reinforcement fiber and a curable resin, and subsequently curing the resin within of the stack to provide an integral laminar structure of several layers of fiber reinforcement encapsulated by the cured resin. laminar structures are strong and light and are well-known and find many uses in industrial applications, such as automotive, aerospace and marine applications, and also in wind turbine hulls, such as the housings used for the production of turbine blades, stringers and the root ends of the stringers. They are also used for sporting goods, such as skis, skateboards, surfboards, windsurfing, among others.
[002] The fibrous material used can comprise bundles or woven or nonwoven fabrics, and will be chosen according to the end use and the desired properties of the laminate. The present invention is particularly concerned with systems in which the reinforcement fiber consists of bundles with multiple unidirectional filaments, such as a plurality of substantially parallel bundles, and each bundle comprises a plurality of substantially individual parallel filaments. Examples of fibrous materials that can be used include fiberglass, carbon fiber and Aramid. Similarly, the thermosetting resin that is used may depend on the use for which the laminate is intended and the required properties. Examples of suitable thermosetting resins include polyurethane resins and epoxy resins. The present invention is particularly related to systems employing liquid thermosetting epoxy resins.
[003] Molding materials comprising mixtures of fibrous material and thermosetting resins are sometimes known as "Prepegs" and can be prepared by impregnating the fibrous material with the resin in liquid form. Some resins are liquid at room temperature and, therefore, impregnation can be obtained at room temperature. However, it is generally preferred to heat the resin to reduce its viscosity to assist in impregnation. Other resins are semi-solid or solid at room temperature and are melted to allow impregnation of the fibrous material with a liquid resin.
[004] The impregnation of the fibrous material can be achieved by depositing the resin in a support layer, for example, passing the support layer through a bath of liquid resin and covering the resin in the support layer by means of a blade doser. The surface of the support layer carrying the resin can then be brought into contact with the fibrous material and pressed into the fibrous layer to obtain impregnation of the fibrous layer with the resin. Alternatively, a moving film or resin can be placed with a movable support layer and then placed in contact with a fibrous layer on a pair of heated pressure rollers. In most previous applications, it is preferred to employ two layers of resin, one on each side of the fibrous layer to produce a “sandwich” structure to which pressure is applied to make the resin flow into the fibrous layer to completely impregnate the layer so it forms a conventional prepreg, so that the layer largely contains fibers that are fully embedded in resin and no air remains in the layer.These prepregs have a resin content in the prepreg ranging from 25 to 45% by weight of the prepreg. components highly subject to stress, the void content of laminates formed from prepreg molding materials is significant for performance, since each void is a possible point of defect that decreases mechanical properties. Prepregs require prepregs that produce a low reproducible void content, but at the same time, have satisfactory handling properties.
[005] Air may be trapped during the manufacture of the prepreg molding material and during lamination in the prepreg multilayer mold into a multilayer stack that forms the mold.
[006] The impregnation of the fibrous material with the liquid resin as discussed above can introduce some air into the prepreg assembly of the fibrous layer and the resin during the impregnation of the fibrous reinforcement, unless this process is controlled very carefully. The air that is trapped during the manufacture of the prepreg assembly is difficult to remove once the prepreg is laminated to form the mold and the mold is processed, whereby the thermoset resin begins to cure. When the fibrous material comprises bundles with multiple unidirectional filaments, the air may be within the bundles themselves or in the interstices between the bundles. The presence of such air in the prepreg invariably results in voids in the final laminate. Therefore, it is important to minimize the formation of air bubbles within the resin fiber assembly during and after impregnation and before the resin begins to cure.
[007] Air also tends to be captured between the layers of prepregs due to their sticky surfaces. It is common to process the lamination of prepregs under vacuum (usually in a vacuum bag or autoclave) to remove air from the piles of laminates. Generally, it is not possible to completely remove trapped interlaminar air and intralaminate air (air within a single layer of prepreg) from conventional prepregs and manufacture laminates that have uniform properties over the length and breadth of the laminate.
[008] Document 1 595 689 discloses a prepreg assembly comprising a fibrous reinforcement and a thermally curable resin, in which the resin is impregnated in the fibrous reinforcement. A mesh is adhered to the outer surface of a conventional fully impregnated prepreg so that the mesh is applied over the prepreg to such an extent that less than half the circumference of the mesh filaments becomes coated with the prepreg resin. This material has the disadvantage that the molding quality of the cured laminate depends on the impregnation quality of the fibrous reinforcement, since the mesh cannot remove all trapped intralaminate air. In addition, we found that, for large piles of laminates, typically more than 20 individual prepreg liners, this material is less effective in removing interlaminar and intralaminate air.
[009] PCT Publication WO 00/27632 focuses on preventing air from becoming trapped either inside a layer of molding material (A prepreg) or between additional layers, particularly when a heavy fiber such as a 1200 g / m2 unidirectional tape is used as the fibrous reinforcement. The solution offered by WO 00/27632 is to provide a multi-layer molding material which can be a prepreg comprising a layer of resin material joined to at least one surface of a fibrous layer. According to one embodiment, the fibrous layer can be partially impregnated by the resin layer. This material has the disadvantage of being intrinsically unstable. If the material is stored for any period of time before it is rolled into the mold, the liquid resin migrates to the fibrous material, which in turn results in the loss of the material's air-removing properties once the dry areas of the fibrous material are saturated with resin. In addition, we found that, for large piles of laminates, typically more than 20 individual prepreg liners, this material is less effective in removing interlaminar and intralaminate air.
[010] US Patent 5,756,206 relates to flexible low volume prepreg bundles produced by powder coating techniques. The powder is applied to a beam and partially fused to adhere to the beam to form a discontinuous coating on the beam that helps the air in the towpreg's core to escape while consolidating the towpregs into composite parts. This material has the disadvantage that it is very laborious to manufacture large moldings, and therefore it is uneconomical to laminate large composite parts using individual bundles. Furthermore, this material is unstable with respect to the resin ratio for reinforcement, since the resin reinforcement ratio is distorted as the material is handled. Furthermore, during handling and storage, the resin is additionally impregnated in the bundles, which results in the loss of the material's ventilation capabilities.
[011] The present invention aims to eliminate or at least mitigate the problems described above and / or provide improvements in general.
[012] According to the invention, a molding material or structure and a process as defined in any of the accompanying claims is provided. The present invention relates to a molding material or structure that can be molded to produce laminates with a reduced number of voids. In addition, the invention relates to a process in which a liquid curable resin is applied to a layer of fibrous material to provide a molding material in a way that the presence of voids in the final molded product produced from the material is reduced. The invention is particularly useful in applications where a final laminate is obtained from a stack of a plurality of layers comprising fiber and thermosetting resins, such as a stack containing at least 20 of such layers. The invention is aimed at minimizing the presence of voids due to the air trapped inside the prepregs and also the air trapped between the stacked prepregs.
[013] In one embodiment, a molding material or structure is provided comprising a fibrous reinforcement layer and a curable liquid resin, wherein the fibrous reinforcement comprises a plurality of bundles, each bundle comprising a plurality of filaments, wherein the resin it is provided at least partially between the interstices between the bundles of the fibrous reinforcement to provide an air ventilation path at least within the bundles. The interior of the bundles is at least partially resin-free to provide an air ventilation path to allow air to be removed during the processing of the material or structure.
[014] In another aspect of the invention, the molding material or structure comprises leaves of fibrous reinforcing material that provide air ventilation paths. The bundles are structural of the reinforcement fibers, so, in practice, they serve multiple purposes: on the one hand, they provide air ventilation paths, and on the other, they provide structural reinforcement. This has the important advantage that no material is added or included in the impression material to only provide the function of air ventilation.
[015] The interstitial resin ensures that the material has an adequate structure at room temperature to allow manipulation of the material. This is achieved due to the fact that, at room temperature (23 ° C), the resin has a relatively high viscosity, typically in the range of 1000 to 100,000 Pa.s, more typically in the range of 5000 Pa.s to 500,000 Pa.s . In addition, the resin can be sticky. Stickiness is a measure of a prepreg's adhesion to a tool surface or other prepreg plies in an assembly. Stickiness can be measured in relation to the resin itself or in relation to the prepreg according to the method as revealed in "Experimental analysis of prepreg tack", Dubois et al, (LaMI) UBP / IFMA, March 5, 2009. This publication reveals that stickiness can be measured objectively and repeatedly using the equipment as described therein and measuring the maximum detachment force for a probe that is placed in contact with the resin or prepreg at an initial pressure of 30N at a constant temperature of 0 ° C30 ° C and which is subsequently displaced at a rate of 5 mm / min. For these probe contact parameters, the F / Fref tackiness for the resin is in the range of 0.1 to 0.6, where Fref = 28.19N and F is the maximum detachment force. For a prepreg, the F / Fref stickiness is in the range of 0.1 to 0.45 for F / Fref, where Fref = 28.19N and F is the maximum detachment force. However, a fibrous blanket, grid or fibrous support mesh can also be located on at least one outer surface of the fibrous reinforcement to further improve the integrity of the material or structure during handling, storage and processing.
[016] In a further embodiment, the material or structure comprises non-impregnated bundles and at least partially impregnated bundles. Preferably, the reinforcement comprises non-impregnated bundles (“dry bundles”) and completely impregnated bundles. The fibrous reinforcement layer comprises air ventilation bundles at least partially embedded in fibrous reinforcement at least partially impregnated. The partially impregnated fibrous reinforcement may be a unidirectional reinforcement or a braided fibrous reinforcement or a non-braided fibrous reinforcement.
[017] The material or structure can be formed from two or more separate layers of fibrous reinforcement, one layer being impregnated with resin and the other layer being non-impregnated or substantially non-impregnated, the two layers being joined so that the resin is present between the interstices of the bundles. Preferably, the layers are joined so that the non-impregnated or substantially non-impregnated bundles are at least partially embedded between impregnated bundles. The layers may comprise unidirectional bundles, the bundles of each layer being substantially parallel. The two layers can be joined by compression so that all unidirectional bundles are in the same plane or substantially in the same plane. One or more additional fibrous layers can also be combined with the joined layers.
[018] In a further aspect of the invention, the impregnated and non-impregnated bundles can be co-located to form a single fibrous reinforcement plane. The longitudinal axes of the impregnated and non-impregnated bundles in a fibrous reinforcement layer or sheet can be parallel to each other and all of their axes can be located in a single plane.
[019] In a further embodiment, the material or structure may comprise joined layers of impregnated and non-impregnated bundles, the longitudinal axes of the impregnated and non-impregnated bundles being located in the same plane. In a further embodiment, the material or structure may comprise joined layers of impregnated and non-impregnated bundles, the material comprising between 10 to 70% dry bundles, preferably 20 to 60% dry bundles and, more preferably, 30 50% dry bundles, more preferably 33 to 50% dry bundles. The material or structure may additionally comprise one or more meshes, as defined herein.
[020] The material or structure may have a concentration of resin impregnation ranging from 20 to 50% by weight, preferably from 30 to 40% by weight, and more presently, from 32 to 38% by weight of the material or structure.
[021] The interstices between the bundles may comprise filaments. The interstices may comprise single-strand filaments or bundle filaments on both sides of the interstices. The interstices containing bundle filaments form an integral structure of the material or molding structure so that it can be manipulated, rolled and / or stored without distortion of the fiber orientation and the resin to fiber volume ratio and / or the Weight. This ensures that the material is stable, as opposed to materials that are conventionally known.
[022] In a further embodiment, the resin may be provided on the first side of the fibrous reinforcement and at least partially penetrate the interstices between the bundles of the fibrous reinforcement to leave the inside of the bundles at least partially free of resin.
[023] The present invention, therefore, provides a molding material or structure comprising a unidirectional fibrous reinforcement layer and a curable liquid resin, wherein the fibrous reinforcement comprises a plurality of multiple filament bundles, wherein the resin is provided in the first side of the fibrous reinforcement and at least partially penetrates the interstices between the bundles of the fibrous reinforcement and leaves the interior of the bundles at least partially free of resin.
[024] In a further embodiment, the invention provides a molding material or structure comprising a fibrous reinforcement layer and a curable liquid resin, wherein the fibrous reinforcement layer comprises a plurality of bundles with multiple unidirectional filaments, wherein the resin is provided on a first side of the fibrous reinforcement layer and where the interstices between the bundles are at least partially impregnated with the resin and the resin penetrates no more than partially into the individual bundles and the second side of the fibrous reinforcement layer is at least partially resin-free. In a further embodiment, the fibrous web or mesh is adhered to the fibrous layer by light pressure, so that less than half the circumference of the web or mesh fibers are coated with resin. In another embodiment, the molding material or structure is supplied with a fibrous blanket or support mesh on one or both sides of the structure.
[025] In another embodiment, the fibrous blanket or mesh may be located in the interstices between the bundles. In a preferred embodiment, the mesh is arranged at least on the first side of the fibrous reinforcement layer, so that part of the mesh is in the interstices between the mesh in the interstices provides a ventilation path in the intra-laminar and inter-laminar directions. This makes it possible to extract any trapped air or other gaseous matter in the x, y and z direction of the material. This is advantageous when multiple layers of the molding material form a laminated structure.
[026] Another benefit of this embodiment is that the application of a single fibrous blanket or mesh results in a product that is essentially symmetrical. This allows the material to be applied regardless of its orientation in relation to the lamination. Another benefit of an essentially symmetrical material is that it can be applied from a cylinder or spool to a laminate or pile of laminates in consecutive back and forth movements, whereas an asymmetric material should only be deposited in the frontal movement while the backward movement must then be used to return the cylinder or spool to its original position. A laminate or pile formed with a symmetrical material can therefore be formed more quickly and efficiently.
[027] The fibrous mesh or blanket is preferably of large mesh opening diameter and can be formed from any suitable material, but thermoplastic yarns are preferred. The main requirement of the yarn material is that it has a melting point similar to or greater than the prepreg gelling temperature so that the yarn does not melt during the curing process. Preferably, the difference between the melting point of the yarn and the gelation point of the matrix should be at least 10 ° C. Suitable materials for the mesh include polyester (76 - 1100 dtex), such as poly (ethylene terephthalate) and poly (butylene terephthalate) and copolymers thereof, polyamide (110-700 dtex), such as nylon 6, nylon 66, nylon 11 and nylon 12, polyethersulfone, polypropylene, viscose cut wire (143 - 100 dtex), meta and para-amide (Kevlar 29 220-1100 dtex) and Nomex T-430 2201300 dtex, glass 220-1360 dtex), jute (2000 dtex), linen (250-500 dtex), cotton (200-500 dtex) and combinations of one or more of these. Such material is available under the trade name Bafatex by Bellingroth GmbH. The filaments that form the mesh preferably have a substantially round cross section. The filament diameters can be in the range of 100 to 1000 micrometers, preferably from 200 to 600 micrometers, and more preferably, from 300 to 400 micrometers. If the diameters of the mesh fiber are too large, then the mechanical properties of the laminate may be adversely affected. For example, both interlaminar shear strength and compression strength have been found to decrease.
[028] An important aspect of the invention is that the filaments of the fibrous mesh or blanket are not fully impregnated by the resin. This helps in ventilating the interlaminar air between the prepreg layers. The degree to which the mesh filaments are coated with resin can be expressed by the degree of impregnation (DI). The DI indicates to what degree the mesh circumference the filaments are covered with resin. Therefore, an impregnation index of 1.0 means that the filaments are fully impregnated by the resin and an impregnation index of 0.5 indicates that half the circumference of the grid filaments is coated by the resin. The invention requires that the mesh filaments be covered with the prepreg resin to a minimum degree, just sufficient for the mesh to adhere to the prepreg to ensure safe handling. However, 50% of the filament circumference or more should not be covered by the resin in order to ensure the proper supply of air exhaust ducts. Therefore, expressed as a "degree of impregnation", the invention requires that the degree of impregnation be between> 0 and <0.5, and preferably between 0.2 and 0.3.
[029] To ensure that the outer ends of the air channels supplied along the mesh filaments do not become obstructed by the prepreg resin, the mesh must extend externally beyond the edges of the prepreg. Preferably, the mesh should project over the edges of the prepreg by 2 to 30 mm, in particular, by 10 to 20 mm.
[030] In another embodiment, a fibrous mesh or blanket may be present on one or both surfaces of the molding material or structure.
[031] A release paper coated with polyethylene or silicone can be placed as a protective layer on one or both sides of the pre-mesh assembly.
[032] The structure of the mesh is of importance and consists of two main elements. In the 0o or warp direction, the yarns are used to primarily stabilize the yarns that are aligned in other directions, even when under tension in a rolled cylinder. Other yarns, which extend in a transversal direction to the warp yarns, form parallelograms. In general, the grid forms a crude network in which the parallel filaments of the parallelogram have a distance of 3 to 60, preferably 10 to 35, and more preferably, 20 to 300 mm from each other.
[033] For the escape of air, the short channels for the lateral edges of the prepreg formed by the filaments in the approximately transverse direction are of importance. Preferably, the mesh should include parallelograms with lateral lengths of 10 to 35 mm, where the minor angle of the parallelogram is between 50o and 80o, preferably between 65o and 75o. Therefore, the mesh should preferably comprise filaments in the longitudinal direction, which is the forward direction of the sheet, and filaments in the direction approximately transverse to the forward direction of the sheet. With such a mesh construction during the pressure molding of the prepreg laminations, also advancing in the longitudinal direction, the air will first advance along the longitudinal filaments to a point, where the longitudinal filament meets a filament in the transverse direction, from where the air will escape out along a filament in the transverse direction. These filaments in the transverse direction create a short outward path. In this regard, the angle between the filaments in the longitudinal direction and the filaments in the approximately transverse direction is also of practical importance.
[034] In a further embodiment, the invention provides a stack of such molding materials or structures.
[035] In another embodiment, the invention provides a process for the preparation of a prepreg or a "semipreg" comprising superimposing a curable liquid resin on a unidirectional fibrous reinforcement layer comprising a plurality of bundles, each comprising a plurality of parallel filaments to form an overlapping structure, in which the overlapping structure is compressed to the point that the resin penetrates the interstices between the bundles and penetrates the voids within the bundles at less than 22 to 60% by volume of the bundle volume, particularly from 22 to 55% of the volume, more particularly from 22 to 50% of the volume, preferably from 25 to 45% of the volume, and more preferably from 25 to 42% of the volume or from 25 to 35% of the beam volume.
[036] The molding material or structure of the invention can be characterized by its resin content and / or its fiber volume and resin volume and / or by its degree of impregnation, as measured by the water absorption test.
[037] The resin and fiber content of uncured molding materials or structures is determined in accordance with ISO 1 1667 (method A) for molding materials or structures that contain fibrous material that does not comprise unidirectional carbon. The resin and fiber content of uncured molding materials or structures containing unidirectional carbon fiber material is determined in accordance with DIN EN 2559 A (code A). The resin and fiber content of cured molding materials or structures containing carbon fiber material is determined in accordance with DIN EN 2564 A.
[038] The fiber and resin volume percentage of a prepreg molding material or structure can be determined from the fiber and resin weight percentage by dividing the weight percentage by the respective density of the resin and carbon fiber.
[039] The percentage of impregnation of a bundle or fibrous material that is impregnated with resin is measured by means of a water absorption test.
[040] The water absorption test is performed as follows. Six prepreg strips are cut, with dimensions of 100 (+/- 2) mm x 100 (+/- 2) mm. Any backing sheet material is removed. Samples are weighed to the nearest 0.001 g (W1). The strips are located between aluminum plates reinforced with PTFE so that 15 mm of the prepreg strip protrudes from the assembly of plates reinforced with PTFE at one end and so the orientation of the fiber of the prepreg extends along the projecting part. A clamp is placed at the opposite end, and 5 mm of the projecting part are immersed in water with a temperature of 23oC, relative air humidity of 50% +/- 35%, and at an ambient temperature of 23oC. After 5 minutes of immersion, the sample is removed from the water and any external water is removed with blotting paper. The sample is then weighed again W2. The percentage of water absorption WPU (%) is then calculated by averaging the measured weights for the six samples as follows: WPU (%) = [(<W2> - <W1>) / <W1>) x100 . The WPU (%) indicates the degree of resin impregnation (DRI).
[041] The same method can be performed for individual bundles - in this case, multiple bundles (typically 25 to 50) are located between the PTFE reinforced plates and are treated in the same way by immersion in water, and the% WPU is then calculated for the beams by calculating the average values for W1 and W2 as indicated above.
[042] Typically, the values for the resin content by weight for the uncured prepreg of the invention are in the ranges of 15 to 70% by weight of the prepreg, from 18 to 68% by weight of the prepreg, from 20 to 65% by weight of prepreg, from 25 to 60% by weight of prepreg, from 25 to 55% by weight of prepreg, from 25 to 50% by weight of prepreg, from 25 to 45% by weight of prepreg, from 25 to 40% by weight of prepreg, from 25 to 35% by weight of prepreg, from 25 to 30% by weight of prepreg, from 30 to 55% by weight of prepreg, from 35 to 50% by weight of prepreg and / or combinations of the intervals mentioned above.
[043] Typically, the values for the volume resin content for the uncured prepreg of the invention are in the ranges of 15 to 70% by volume of the prepreg, 18 to 68% by volume of the prepreg, from 20 to 65% in prepreg volume, from 25 to 60% in prepreg volume, from 25 to 55% in prepreg volume, from 25 to 50% in prepreg volume, from 25 to 45% in prepreg volume, from 25 to 40% in volume of prepreg, from 25 to 35% in volume of prepreg, from 25 to 30% in volume of prepreg, from 30 to 55% in volume of prepreg, from 35 to 50% in volume of prepreg and / or combinations of intervals mentioned above.
[044] Finally, the values for the resin content by volume for the uncured prepreg of the invention are in the ranges of 15 to 70% by volume of the prepreg, from 18 to 68% by volume of the prepreg, from 20 to 65% in prepreg volume, from 25 to 60% in prepreg volume, from 25 to 55% in prepreg volume, from 25 to 50% in prepreg volume, from 25 to 45% in prepreg volume, from 25 to 40% in volume of prepreg, from 25 to 35% in volume of prepreg, from 25 to 30% in volume of prepreg, from 30 to 55% in volume of prepreg, from 35 to 50% in volume of prepreg and / or combinations of intervals mentioned above. The values for the resin content by weight for the uncured prepreg bundles of the invention are in the beech from 15 to 70% by weight of the prepreg bundle, from 18 to 68% by weight of the prepreg bundle, from 20 to 65% by weight of the prepreg bundle, from 25 to 60% by weight of the prepreg bundle, from 25 to 55% by weight of the prepreg bundle, from 25 to 50% by weight of the prepreg bundle, from 25 to 45% by weight of the prepreg bundle, from 25 to 40% by weight of the prepreg bundle, from 25 to 35% by weight of the prepreg bundle, from 25 to 30% by weight of the prepreg bundle, from 30 to 55% by weight of the bundle prepreg, from 35 to 50% by weight of the prepreg bundle and / or combinations of the ranges mentioned above.
[045] The water absorption values for the uncured prepreg material and mold bundles of the invention can be in the range of 1 to 90%, 5 to 85%, 10 to 80%, 15 to 75%, 15 to 70%, 15 to 60%, 15 to 50%, 15 to 40%, 15 to 35%, 15 to 30%, 20 to 30%, 25 to 30% and / or combinations of the ranges mentioned above. In a further embodiment, the invention provides a process in which a layer of unidirectional fibrous bundles that are fully impregnated with liquid resin is superimposed on a layer of unidirectional unidirectional fibrous bundles and on the consolidated structure so that the resin penetrates the spaces between the non-impregnated bundles, but leave the spaces between the filaments within the bundles at least partially non-impregnated. A fibrous blanket or support mesh can be provided on one or both sides of the structure, preferably before consolidation.
[046] The term prepreg or semipreg is used here to describe a molding material or structure in which the fibrous material has been impregnated with the liquid resin to the desired degree and that the liquid resin is substantially uncured.
[047] The bundles employed in the present invention are made up of a plurality of individual filaments. There can be thousands of individual filaments in a single bundle. The bundle and the filaments within the bundle are generally unidirectional with the individual filaments aligned substantially parallel. In a preferred embodiment, the bundles within the molding material or structure of the invention are substantially parallel to each other and extend along the direction of travel employed for processing the structure. Typically, the number of filaments in a bundle can range from 2,500 to 10,000 to 50,000 or more. Bundles of about 25,000 carbon filaments are available from Toray and bundles of around 50,000 carbon filaments are available from Zoltek.
[048] Leaving the interior of the bundles at least partially free of resin provides an air ventilation path or structure, so that air that may be present in the bundles from the beginning or that may be introduced during impregnation with the liquid resin it is not trapped inside the structure by the resin and can escape during the preparation and consolidation of the prepreg. Air can escape along the length of the bundles and also through the second side of the fibrous layer if the resin impregnation is such that part or all of the surface of the second side of the fibrous layer is not carrying resin. Furthermore, the provision of the spaces between the filaments of the bundles will allow the air trapped between the prepregs during pile formation to escape particularly, if, in addition, one side of the prepreg is not entirely coated with resin.
[049] The prepregs of the present invention can be produced from normally available epoxy resins that can contain a hardener, and, optionally, an accelerator. In a preferred embodiment, the epoxy resin is free of a traditional hardener, such as diciandiamide, and in particular, we have found that these desirable prepregs can be obtained by using a urea-derived or urea-based agent in the absence of a hardener, such as diciandiamide. The relative amount of curing agent and epoxy resin to be used will depend on the reactivity of the resin and the nature and amount of the fibrous reinforcement in the prepreg. Typically, 0.5 to 10% by weight of the urea-based or urea-based curing agent based on the weight of the epoxy resin is used.
[050] Laminates produced from the prepregs of the present invention may contain less than 3% by volume of voids, or less than 1% by volume and voids, typically less than 0.5% by volume and particularly less than 0.1 % by volume, more particularly less than 0.07% by volume based on the total volume of the laminate as measured by microscopic analysis of 20 spaced cross sections measuring 30 x 40 mm in cross section (5 cm spacing) of a cured laminate sample . The cross section is polished and analyzed under a microscope with a viewing angle of 4.5 to 3.5 mm to determine the surface area of the voids in relation to the total surface area of each cross section of the sample and the average of these measurements for the number of cross sections. This method for determining the void fraction is used within the context of this application, although alternative and standardized methods are available, such as DIN EN 2564. However, these methods are expected to provide comparative results with respect to microscopic analysis, as outlined on here. In addition, the maximum void size is evaluated in each viewing angle section and the average of that number is calculated for the 20 samples. The average void surface area is assumed to be the void content value per volume. We verify that fractions or void levels that reach a value of not less than 0.06% and 0.01% by volume have been reached,
[051] The prepregs of the present invention are typically used in a location other than where they are manufactured, and therefore require handling capabilities. Therefore, it is preferred that they be dry or as dry as possible and have low surface tackiness. Therefore, it is preferred to use high viscosity liquid curable resins. The invention has the additional benefit that the prepregs of the invention have improved storage stability compared to fully impregnated prepregs.
[052] The prepreg is preferably provided with one or more support sheets to facilitate the handling of the material and / or the rolling of the material. The backing sheet may comprise a polyolefin-based material, such as polyethylene, polypropylene and / or copolymers thereof. The backing sheet can comprise embossing. This has the advantage of giving the prepreg an air vent surface structure. The air ventilation surface structure comprising etched channels that allow air to escape during processing. This is particularly useful as it prevents trapping between tarpaulins, since the air between tarpaulins is effectively removed through the surface air ventilation channels. In order to produce final laminates with substantially uniform mechanical properties, it is important that the structural fibers and the epoxy resin are mixed to provide a substantially homogeneous prepreg. This requires uniform distribution of structural fibers within the prepreg to provide a substantially continuous matrix of resin surrounding the fibrous bundles while leaving the interstices within the bundles at least partially free of resin. The preferred prepregs of the present invention contain a low level of voids between the bundles. Therefore, it is preferred that each uncured prepreg and the prepreg stack have a water absorption value between 15% to 30%, preferably between 16 to 30%. 26% and / or combinations of the values mentioned above. The water absorption test determines the degree of impermeability or impregnation between the unidirectional bundles of the prepregs of the present invention and is determined as described hereinabove.
[053] The prepregs of the present invention should be laminated with other composite materials (for example, other prepregs that may also be in accordance with the present invention or may be other prepregs) to produce a curable laminate or stack of prepregs. Prepreg is typically produced as a prepreg roll and, because of the sticky nature of such materials, a backing sheet is generally provided to allow the roll to be extended at the time of use. Thus, preferably, the prepreg according to the invention comprises a support sheet on an external face.
[054] The prepregs of the present invention are produced by impregnating the fibrous material with the epoxy resin. The viscosity of the resin and the conditions employed for impregnation are chosen so as to allow the desired degree of impregnation. It is preferred that, during impregnation, the resin has a viscosity of 0.1 Pa.sa 100 Pa.s, preferably 6 to 100 Pa.s, more preferably 18 to 80 Pa.s, and even more preferably, from 20 to 50 Pa.s. In order to increase the rate of impregnation, the process can be carried out at an elevated temperature so that the viscosity of the resin is reduced. However, it should not be so hot for a sufficient period of time that premature curing of the resin occurs. Thus, the impregnation process is preferably carried out at temperatures in the range of 40 ° C to 110 ° C, more preferably, 60 ° C to 80 ° C. It is preferred that the resin content of the prepregs is such that, after curing, the structure contains 30 to 40% by weight, preferably 31 to 37% by weight, more preferably 32 to 35% by weight of the resin. The relative amount of resin and multiple filament bundle, the speed of the impregnation line, the viscosity of the resin and the density of the multiple filament bundles must be correlated to achieve the desired degree of impregnation between the bundles and leave spaces between the individual filaments inside the bundles that are not occupied by the resin. The resin can be spread on the outer surface of a cylinder and coated with paper or other support material to produce a curable resin layer. The resin composition can then be placed in contact with the multiple filament bundles for impregnation, possibly by passing through the cylinders. The resin can be present in one or two sheets of support material, which are placed in contact with one or both sides of the bundles and consolidated, such as by passing them through heated consolidation cylinders to cause the desired degree of impregnation . Alternatively, the resin can be applied by means of a resin bath leading the bundles through the resin (direct fiber impregnation). The resin may also comprise a solvent that is evaporated after impregnating the fiber bundles.
[055] In the impregnation processes, the resin can be kept in liquid form in a resin bath, being a resin that is liquid at room temperature or being melted if it is a resin that is solid or semi-solid at room temperature. The liquid resin can then be applied to a support using a metering blade to produce a resin film in a release layer, such as paper or polyethylene film. The fiber bundles can then be placed on the resin, and optionally, a second layer of resin can be provided over the fiber bundles and then consolidated.
[056] In an additional embodiment, a fibrous layer impregnated with resin can be superimposed on a substantially free layer of resin from unidirectional bundles and the combination pressed together so that the resin from the impregnated layer passes to the free layer of resin so that the resin between the bundles, but leave at least part of the interstices within the bundles at least partially free of resin.
[057] In this embodiment, a layer comprising unidirectional fiber bundles with a high degree of liquid resin impregnation can be superimposed on a layer of substantially un-impregnated unidirectional fiber bundles and the structure consolidated so that the liquid resin passes from the layer impregnated to the substantially un-impregnated layer to cause partial impregnation. Partial impregnation results in resin between the bundles and leaves spaces between the filaments of the bundles that do not contain resin. The partial impregnation may be such that the layer side of the substantially un-impregnated bundles away from the resin containing layer remains dry or partially dry. Alternatively, it can be moistened according to the molding conditions to be employed to cure a pile of prepregs.
[058] A backing sheet can be applied both before and after resin impregnation. However, it is typically applied before or during impregnation, as it can provide a non-stick surface on which the pressure necessary to cause the resin to impregnate the fibrous layer will be applied. The epoxy resin used in the preparation of the prepreg preferably has an Epoxy Equivalent Weight (EEW) in the range of 150 to 1500, preferably a high reactivity, such as an EEW in the range of 200 to 500, and the resin composition comprises the resin and an accelerator or curing agent. Suitable epoxy resins may comprise combinations of two or more epoxy resins selected from monofunctional, difunctional, trifunctional and / or tetrafunctional resins.
[059] Suitable difunctional epoxy resins, for example, include those based on: bisphenol F diglycidyl ether, bisphenol A diglycidyl ether (optionally brominated), phenol and cresol epoxy novolacs, glycidic ethers of phenol adducts -aldelido, glycidyl ethers of aliphatic diols, diglycidyl ether, diglycidyl ether of diethylene glycol, aromatic epoxy resins, aliphatic polyglycidyl ethers, epoxidized olefins, brominated resins, aromatic glycidic amines, glycidic acidic amide, glycolic acidic and heterocyclic amine glycidyl compounds or any combination thereof.
[060] Difunctional epoxy resins can be chosen from diglycidyl ether or bisphenol F, diglycidyl ether from bisphenol A, diglycidyl dihydroxy naphthalene, or any combination thereof.
[061] Suitable tri-functional epoxy resins, by way of example, may include those based on phenol and cresol epoxy novolacs, glycidyl ethers of phenol-aldehyde adducts, aromatic epoxy resins, aliphatic triglycidyl ethers, diallytic triglycidic ethers, polyglycidic amines , heterocyclic glycidyl imidines and amides, glycidyl ethers, fluorinated epoxy resins, or any combination thereof. Suitable tri-functional epoxy resins are available from Huntsman Advanced Materials (Monthey, Switzerland) under the trade names MY0500 and MY0510 (triglycidyl para-aminophenol) and MY0600 and MY0610 (triglycidyl meta-aminophenol). Triglycidyl meta-aminophenol is also available from Sumitomo Chemical Co. (Osaka, Japan) under the trade name ELM-120.
[062] Suitable tetrafunctional epoxy resins include N, N, N ', N'-tetraglycidyl-m-xylenediamine (commercially available from Mitsubishi Gas Chemical Company under the name Tetrad-X, and as Erisys GA-240 from CVC Chemicals) , and N, N, N ', N'-tetraglycidylmethylenedianiline (e.g., MY0720 and MY0721 from Huntsman Advanced Materials). Other suitable multifunctional epoxy resins include DEN438 (from Dow Chemicals, Midland, Ml) DEN439 (from Dow Chemicals), Araldite ECN 1273 (from Huntsman Advanced Materials), and Araldite ECN 1299 (from Huntsman Advanced Materials). The epoxy resin composition preferably also comprises one or more urea-based curing agents, and it is preferred to use 0.5 to 10% by weight based on the weight of the epoxy resin of a curing agent, more preferably 1 to 8% by weight, more preferably 2 to 8% by weight. The preferred urea-based materials are the range of materials available under the trade name Urone®. In addition to a curing agent, a suitable accelerator, such as a latent amine based curing agent, such as dicycopolyamide (DICY).
[063] Therefore, the present invention provides a prepreg molding material to manufacture a fiber reinforced composite material, the prepreg comprising a fibrous reinforcement layer fully impregnated by a matrix resin material, wherein the resin material has a storage module G 'from 3 x 105 Pa to 1 x 108 Pa and a loss module G' 'from 2 x 106 Pa to 1 x 108Pa.
[064] Preferably, the resin material has a storage module G 'of 1 x 106 Pa to 1 x 107 Pa, more preferably, from 2 x 106 Pa to 4 x 106 Pa.
[065] Preferably, the resin material has a storage module G 'from 5 x 106 Pa to 1 x 107 Pa, more preferably, from 7 x 106 Pa to 9 x 106 Pa.
[066] Preferably, the resin material has a complex viscosity from 5 x 105 Pa to 1 x 107 Pa.s, more preferably, from 7.5 x 105 Pa to 5 x 106 Pa.s.
[067] Preferably, the resin material has a complex viscosity of 1 x 106 Pa to 2 x 106 Pa.s, more preferably, 5 x 30 Pa.s at 80 ° C. Preferably, the resin material has a viscosity of 10 to 25 Pa.s at 80 ° C. Preferably, the resin material is an epoxy resin.
[068] We found that the properties of the storage module and loss module mentioned above allow the air ventilation structure to remain in place during the handling, storage and lamination of the prepreg molding material or structure until processing begins, when the laminate pile is heated to temperatures above 40 ° C and a vacuum pressure is applied, even if multiple plies (piles of 20, 30, 40, 60 or even more plies) have been laminated.
[069] Preferably, the prepreg molding material is elongated in a longitudinal direction thereof and the fibrous reinforcement is unidirectional along the longitudinal direction of the prepreg. Preferably, the opposite major surfaces of the prepreg molding material or structure are engraved with an arrangement of channels thereon.
[070] The behavior of thermosetting prepreg materials is highly viscoelastic at typical laminating temperatures employed. The elastic solid part stores deformation energy as a recoverable elastic potential, whereas a viscous liquid flows irreversibly under the action of external forces.
[071] This complex viscosity is obtained using a rheometer to apply an oscillation experiment. From this, the G * complex module is derived as the complex oscillation that is applied to the material is known (Principles of Polymerization, John Wiley & Sons, New York, 1981).
[072] In viscoelastic materials, the stress and deformation will be out of phase by a delta angle. The individual contributions that form the complex viscosity are defined as G '(Storage Module) = G * x cos (delta); G "(Loss Module) = G * x sin (delta). This relationship is illustrated in Figure 8 of WO 2009/118536.
[073] G * is the complex module. G 'refers to how elastic the material is and defines its stiffness. G ’’ refers to how viscous a material is and defines the damping, and liquid non-recoverable flow response of the material.
[074] For a purely elastic solid (glassy or rubbery), G ”= 0 and the delta phase angle is 0o, and for a purely viscous liquid, G '= 0 and the delta phase angle is 90o.
[075] The G loss module "indicates irreversible flow behavior and a material with a high G loss module" is also desirable to prevent early creep flow and maintain an open air path for longer. Therefore, the resin used in the prepregs of the present invention has a high storage modulus and a high loss modulus, and therefore a high complex modulus, at a temperature corresponding to a typical lamination temperature, such as room temperature ( 20 ° C).
[076] The resin material preferably has a delta phase angle such that the delta value increases by at least 25oC over a temperature range of 10 to 25oC. Optionally, the delta phase angle value increases by 25 to 70 ° C over a temperature range of 10 to 25 ° C. Optionally, the value of the delta phase angle between the complex module G * and the storage module G 'increases by a value of 35 to 65oC over a temperature range of 10 to 25oC. Optionally, the value of the delta phase angle is not greater than 70o and / or at least 50 degrees at least one value within the temperature range of 12.5 to 25oC.
[077] In this specification, the viscoelastic properties, that is, the storage module, the loss module and the complex viscosity of the resin used in the prepregs of the present invention were measured at the application temperature (that is, a lamination temperature of 20 ° C) using an AR Instruments rheometer from TA Instruments with disposable 25 mm diameter aluminum plates. The measurements were carried out with the following configurations: an oscillation test at a decreasing temperature reducing from 40 ° C to -10 ° C to 2 ° C / mm with a controlled displacement of 1 x 10 "4 rads at a frequency of 1 Hz and a gap of 1000 micrometers.
[078] Typically, the rigidity of the viscoelastic prepreg is characterized by the resin exhibiting a high elastic rheological response. The resin rheology is characterized by a resin storage module G ', preferably between 3 x 10 5 Pa and 1 x 10 8 Pa at 20 ° C, more preferably from 1 x 10 6 Pa to 1 x 10 7 Pa, even more preferably, from 2 x 10 6 Pa to 4 x 10 6 Pa. The larger the storage module at room temperature, the better the air transport properties of the prepreg stack. However, the upper limit of the storage module is limited, as otherwise the prepreg would become too stiff and develop a tendency to break as the prepreg is being rolled, even at the smooth curvature typical of a turbine stringer. wind power.
[079] In the manufacture of a structural member in the form of a stringer or beam using the prepreg molding material or structure of the present invention, preferably the resin has a high loss modulus G '' between 2 x 106 Pa and 1 x 108 Pa at 20 ° C, more preferably, from 5 x 106 Pa to 1 x 107 Pa, even more preferably, from 7 x 106 Pa to 9 x 106 Pa.
[080] The resin material preferably has a high complex viscosity at 20 ° C from 5 x 105 Pa to 1 x 107 Pa.s, more preferably, from 7.5 x 10 5 Pa to 5 x 10 6 Pa.s, even more preferably, from 1 x 10 6 Pa to 2 x 10 6 Pa.s.
[081] Furthermore, as indicated above, the viscosity of the resin in the impression material is relatively high. This determines that, prior to the curing stage, which is typically carried out at an elevated temperature, for example, at a temperature greater than 75 ° C, a typical curing temperature being 80 ° C or higher, the resin exhibits low flow properties or even despicable. The resin material preferably has a viscosity of 5 to 30 Pa.s at 80 ° C, more preferably, 10 to 25 Pa.s at 80 ° C. In this specification, the viscosity of the resin flow during the curing cycle was measured using a Ta Instruments AR2000 rheometer with disposable 25 mm diameter aluminum plates. The measurement was performed with the following configurations: increasing temperature from 30 to 130 ° C 2oC / mm with a shear stress of 3.259Pa, gap: 1000 micrometers.
[082] The term “interstices” is used in this application to define the space or volume that is present between adjacent bundles. This space or volume may comprise filaments of one or more adjacent bundles. The space or volume can be filled when the fibrous material is impregnated, either partially or completely.
[083] It is generally thought that the interstices are important to allow ventilation of interlaminar or intralaminate air trapped from laminate moldings. Surprisingly, we found that the interstices can be filled with resin, while the bundles themselves, when not fully impregnated, as confirmed, for example, by water absorption measurements, allow ventilation of both interlaminar and intralaminate air. This results in impression materials that have a very low void content, as confirmed by the experiments in this order.
[084] Furthermore, we have found that, for the resin properties as defined here, the molding material of the invention is very stable during manufacture, storage, handling and lamination, so that the ventilation structure in the bundles (and through of the recording by a backing sheet) can remain in place until an advanced stage during the processing of the laminate stack when the temperature is typically raised to values above 60 ° C.
[085] The multi-filament bundles used in the present invention may comprise selectively fused continuous or discontinuous (i.e., broken by drawing). Filaments can be formed from a wide variety of materials, such as carbon, basaltic fiber, graphite, glass, metallized polymers, aramid and mixtures thereof. Glass bundles and carbon fibers are preferred, with bundles of carbon fiber being preferred for wind turbine hulls over 40 meters in length, such as 50 to 60 meters. Structural fibers are individual bundles formed from a multiplicity of unidirectional individual fibers. Typically, the fibers will have a circular or quasi-circular cross section, with a diameter for carbon in the range of 3 to 20 µm, preferably 5 to 12 µm. For other fibers, including glass, the diameter can be in the range of 3 to 600 µm, preferably from 10 to 100 µm. Different bundles can be used in different prepregs according to the invention and different prepregs can be used together to produce a cured laminate according to the required properties of the cured laminate. The reinforcement fibers can be synthetic or natural fibers or any other form of material or combination of materials that, combined with the resin composition of the invention, form a composite product. The fibrous reinforcement mat can be supplied by means of fiber spools which are unwound or from a fabric roll. Examples of fibers include glass, carbon, graphite, boron, ceramic and aramid. The preferred fibers are carbon and glass fibers. Hybrid or mixed fiber systems can also be contemplated. The use of selectively staple or fissured fibers (that is, broken by stretching) can be advantageous to facilitate the lamination of the product according to the invention and to improve its ability to be molded. Although a unidirectional fiber alignment is preferable, other shapes can also be used. Typical textile shapes include plain textile fabrics, knitted fabrics, twill fabrics and satin fabrics. It is also possible to contemplate the use of layers of non-braided or non-crimped fibers. The surface mass of the fibers within the fibrous reinforcement is generally 80 to 4000 g / m2, preferably 100 to 2500 g / m2, and particularly preferably 150 to 2000 g / m2. The number of carbon filaments per bundle can vary from 3000 to 320,000, again, preferably from 6,000 to 160,000 and more preferably, from 12,000 to 48,000. For fiberglass reinforcements, 600-2400 tex fibers are particularly suited.
[086] Examples of unidirectional fiber bundle layers are formed from HexTow® carbon fibers, which are available through Hexcel Corporation. HexTow® carbon fibers suitable for use in the production of unidirectional fiber bundles include: IM7 carbon fibers, which are available as bundles that contain 6,000 or 12,000 filaments and weigh 0.223 g / m and 0.446 g / m, respectively; carbon fibers IM8-IM10, which are available as bundles that contain 12,000 filaments and weigh from 0.446 g / m to 0.324 g / m; and AS7 carbon fibers, which are available in bundles that contain 12,000 filaments and weigh 0.800 g / m, bundles containing up to 80,000 or 50,000 (50,000) filaments can be used, such as those containing around 25,000 filaments available through Toray and those containing around 50,000 filaments available through Zoltek. The bundles typically have a width of 3 to 7 mm and are fed for impregnation in equipment that employs to retain the bundles and keep them parallel and unidirectional.
[087] The bundles of the prepregs will be impregnated with the epoxy resin so that the resin is present between the bundles, but does not fill the spaces between the individual filaments within the bundles, although part of the resin may pass into these spaces during the impregnation. The impregnation can be controlled so that the first side of the bundle layer is moistened by the resin, while the second side remains dry. Alternatively, both sides can be moistened by the resin, as long as the resin does not fill all the spaces between the individual filaments within the bundles. The prepregs of the present invention are predominantly composed of resin and multiple filament bundles.
[088] A stack of prepregs for preparing cured laminates can contain more than 40 layers of prepreg, typically more than 60 layers, and sometimes more than 80 loved ones, some or all of which can be prepregs according to the present invention. One or more of the prepreg layers in the stack can be cured or pre-cured by partially processing the resin in the prepreg layer. However, it is preferred that all prepregs are in accordance with the invention. Typically, the pile will have a thickness of 1 cm to 10 cm, preferably 2 cm to 8 cm, more preferably 3 to 6 cm.
[089] Epoxy resins can become brittle after curing, and stiffening materials can be included with the resin to provide durability, although they can result in an undesirable increase in the resin's viscosity. As described alternatively in Co-pending Order No. EP11195218.0, the stiffening material can be fed as a separate layer, such as a veil.
[090] When the additional stiffening material is a polymer, it must be insoluble in the matrix epoxy resin at room temperature and the high temperatures at which the resin is cured. Depending on the melting point of the thermoplastic polymer, it can melt or soften to varying degrees during curing of the resin at elevated temperatures and solidify again as the cured laminate is cooled. Suitable thermoplastics must not dissolve in the resin, and include thermoplastics, such as polyamides (PAS), polyethersulfone (PES) and polyetherimide (PEI). Polyamides, such as nylon 6 (PA6) and nylon 12 (PA12) and mixtures thereof, are preferred.
[091] Once prepared, the prepreg can be rolled up so that it can be stored for a period of time. It can then be rolled out and cut as desired, and optionally laminated with other prepregs to form a stack of prepregs in a mold or in a vacuum bag, which is subsequently placed in a mold and cured.
[092] Once prepared, the prepreg or stack of prepregs is cured by exposure to a high temperature, and optionally, high pressure, to produce a cured laminate. As discussed above, the prepregs of the present invention can provide excellent mechanical properties without requiring the high pressures found in an autoclave process. Thus, in a further aspect, the invention relates to a process for curing the thermosetting resin within a prepreg or stack of prepregs as described herein, the process involving exposing the prepreg or stack of prepregs to a temperature sufficient to induce curing of the thermoset resin composition and is preferably carried out at a pressure of less than 3.0 bar absolute.
[093] The curing process can be carried out at a pressure of less than 2.0 bar absolute, preferably less than 1 bar absolute. In a particularly preferred embodiment, the pressure is less than the atmospheric pressure. The curing process can be carried out at one or more temperatures in the range of 80 to 200 ° C, for a time sufficient to cure the thermoset resin composition to the desired degree.
[094] Curing at a pressure close to atmospheric pressure can be achieved by the so-called vacuum bag technique. This involves placing the prepreg or stack of prepregs in an airtight bag and creating a vacuum inside the bag. This has the effect that the prepreg pile is subjected to a consolidation pressure that reaches atmospheric pressure, depending on the degree of vacuum applied.
[095] Once cured, the prepreg or stack of prepregs becomes a composite laminate, suitable for use in a structural application, for example, an aerospace structure or a wind turbine blade.
[096] Such composite laminates may comprise structural fibers at a level of 45% to 75% by volume (fraction of fiber volume), preferably from 55% to 70% by volume, more preferably, from 58% to 65% by volume. volume (DIN EN 2564 A).
[097] The unique properties of the light weight layers, such as stranded and non-stranded fibrous layers, and other similarly structured thermoplastic polymer layers used in this invention, make it possible to cure laminates using such layers in an out-of-process process. autoclave. This relatively low pressure and low cost curing process can be used because the damage tolerance (for example, Compression After Impact - DAI) of the cured laminate is not substantially less than the damage tolerance achieved using the highest pressure and the larger expenses of an autoclave. In contrast, curing outside the autoclave of laminates that have zones between sheets stiffened with insoluble thermoplastic particles produces cured laminates that have damage tolerances that are significantly reduced.
[098] The invention has applicability in the production of a wide variety of materials. A particular use is in the production of wind turbine blades and stringers. Typical wind turbine blades comprise two long hulls that come together to form the outer surface of the blade and a supporting stringer inside the blade that extends at least partially along the length of the blade. The hulls and stringer can be produced by curing the prepregs or piles of prepregs of the present invention.
[099] The length and shape of the shells vary, but the tendency is to use longer shovels (which require larger structures), which, in turn, may require thicker structures and a special sequence of prepregs within the pile to be cured . This imposes special requirements on the materials from which they are prepared. Prepregs based on bundles of carbon fibers of unidirectional multiple filaments are preferred for shovels of 30 meters or more, particularly those of 40 meters or more, such as 45 to 65 meters. The length and shape of the shells can also lead to the use of different prepregs within the pile from which the structures are produced and can also lead to the use of different prepregs along the length of the structure. Due to its size and complexity, the preferred process for the manufacture of wind energy components, such as shells and stringers, consists of supplying the appropriate prepregs inside a vacuum bag, which is placed in a mold and heated to the temperature of cure. The bag can be evacuated before or after being placed into the mold.
[0100] The reduction in the number of voids in the laminates is particularly useful for providing structures and / or stringers and / or stringer tables for wind turbine blades with uniform mechanical properties. Particularly, the stringers and their parts are subject to high loads. Any reduction in void content greatly improves the mechanical performance of these parts. This, in turn, allows the parts to be built with a reduced weight (for example, by reducing the number of layers of prepregs) compared to a similar part that would have a higher void content. Furthermore, in order to withstand the conditions to which the wind turbine structures are subjected during use, it is desirable that the cured prepregs from which the hulls and stringers are produced have a high Tg, and preferably, a Tg greater than 90 ° C.
[0101] The invention will now be illustrated with reference to the accompanying drawings, in which:
[0102] Figure 1 is a schematic illustration of a molding material or structure according to an embodiment of the invention;
[0103] Figure 2 is a schematic illustration of a molding material or structure according to another embodiment of the invention;
[0104] Figure 3 is a schematic illustration of a process according to an embodiment of the invention;
[0105] Figure 4 is a schematic illustration of a molding material or structure according to another embodiment of the invention;
[0106] Figure 5 is a schematic illustration of a process according to another embodiment of the invention; and
[0107] Figure 6 is a schematic illustration of a stack or assembly of molding material according to another embodiment of the invention.
[0108] Figure 1 shows a molding material or structure 20 comprising a fibrous reinforcement layer 24 and a curable liquid resin 22, wherein the fibrous reinforcement comprises a plurality of bundles, each bundle comprising a plurality of filaments, wherein the resin is provided at least partially between the interstices 22 between the bundles of the fibrous reinforcement 24 to provide an air ventilation path at least within the bundles.
[0109] The interior of bundles 24 is at least partially free of resin. The interstices comprise both resin 22 and filaments of the adjacent bundles 24. The fibrous reinforcement layer 24 comprises air ventilation bundles at least partially embedded in fibrous reinforcement at least partially impregnated.
[0110] In Figure 1, the production method of this material is illustrated in (a) and (b). First, a layer of resin 22 is placed in contact with the unidirectional fibrous reinforcement material 24 on one side. The resin layer is pressed onto the reinforcement material 24 so that the resin penetrates at least partially into the interstices between the bundles of the fibrous reinforcement to leave the inside of the bundles at least partially free of resin. A porous fibrous fibrous mesh or mat (not shown) can subsequently be adhered to one or both sides of the molding material 20, whereby the fibrous mesh or mat is substantially non-impregnated with resin to assist in the removal of both interlaminar and intralaminar during the processing of the impression material when applied in a pile. Figure 2 shows another impression material according to the invention. This material 40 comprises a fibrous reinforcement layer comprising unidirectional fibers 44, 42 and a curable liquid resin, wherein the fibrous reinforcement comprises a plurality of bundles 44, 42, each comprising a plurality of filaments, wherein the bundles are substantially not -pregnated 42 or substantially impregnated 44 with resin, to form interstices containing resin between bundles 42, 44. The interstices contain both resin and filaments of impregnated 44 and non-impregnated bundles 42. A porous fibrous fibrous mesh or blanket 46 is subsequently adhered to one side of the impression material 40, whereby the mesh or fibrous mat 46 is substantially free of resin to assist in the removal of both interlaminar and intralaminate air during the processing of impression material 40 when applied in a pile. Material 40 is manufactured according to process 100, as shown in Figure 3. A unidirectional fibrous reinforcement layer egeate 102 is conducted between the compression cylinders 108. On either side of reinforcement 102, a resin film 105, 104 is provided, so that resin 104, 105 is compressed into the fibrous reinforcement material to substantially fully impregnate the bundles of 102 unidirectional fibrous reinforcement (“wet bundles”). In a subsequent stage, a non-impregnated fibrous unidirectional reinforcement layer (“dry bundles”) 110 is conducted between the compression cylinders 112. The compression cylinders press the dry fibrous unidirectional bundles between the fully impregnated bundles so that it is produced a structure in which the dry bundles sit between the wet bundles. As a result of compression, the dry bundles will become partially impregnated with resin, so that interstices containing resin are formed between the bundles. The interstices also contain filaments from adjacent bundles. A fibrous mesh or blanket 116, as described hereinabove, is additionally applied to the material by compression cylinders 112. Figure 4 shows another embodiment of a molding material or structure according to the invention. This material 60 comprises a fibrous reinforcement layer comprising unidirectional fibers 64, 62 and a curable liquid resin, wherein the fibrous reinforcement comprises a plurality of bundles 64,62, 42, each comprising a plurality of filaments, wherein the bundles are substantially non-impregnated 42 or substantially impregnated 64 with resin, to form interstices containing resin between bundles 62, 64. The interstices contain both resin and filaments in the impregnated 64 and non-impregnated bundles 62, and also contain the porous fibrous mesh or blanket 66, whereby the mesh is substantially non-impregnated with resin to assist in the removal of both interlaminar and intralaminate air during the processing of molding material 60 when applied to a stack.
[0111] Material 60 is manufactured according to process 200 illustrated in Figure 5. A unidirectional fibrous non-impregnated reinforcement layer 202 is conducted between compression cylinders 208. On either side of reinforcement 202, a film of resin 205, 204 is provided, so that resin 104, 105 is compressed into the fibrous reinforcement material to substantially fully impregnate the bundles of the unidirectional fibrous reinforcement 202 ("wet bundles"). In a subsequent stage, a non-impregnated fibrous unidirectional reinforcement layer (“dry bundles”) 210 is conducted between compression cylinders 212. In addition, a fibrous mesh or blanket 216, as described here above, is applied between the dry bundles 210 and the wet bundles. The compression cylinders press the dry fibrous unidirectional bundles and the fibrous mesh or blanket between the fully impregnated bundles so that a structure is produced in which the dry bundles settle between the wet bundles and so the mesh is also present in the interstices that extend to the other surface of the material 60. As a result of compression, the dry bundles will become partially impregnated with resin, so that interstices containing resin are formed between the bundles. The interstices also contain filaments from adjacent bundles.
[0112] The mesh assists in the ventilation of any interlaminar and / or intralaminate air in the x, y directions (transverse and longitudinal directions) and z direction (cross tarpaulin direction). This embodiment also has the advantage that only one mesh is necessary for produce a symmetrical impression material.
[0113] Reinforcement materials suitable for the embodiments as shown in Figures 1 to 5 include unidirectional fibrous reinforcement from 400 to 1000 gsm. A suitable resin material is M9.6, as supplied by Hexcel.
[0114] Tests were carried out using a fibrous layer comprising parallel unidirectional bundles of carbon fibers. Comparative Examples
[0115] Sixty sheets of prepreg fully impregnated with unidirectional carbon fabric (600 gsm, 50 thousand filaments per bundle) with a resin content of 35% by weight were laminated to form a 35 mm thick cured laminate.
[0116] The type of matrix resin was M9.6GF, available from Hexcel, Pascing, Austria. The prepregs were fully impregnated by applying a resin film of M9.6GF resin to each side of the unidirectional fibrous layer and compressing that resin in the fibrous layer (2-film process). A lamination was prepared from the fully impregnated fabric as prepared above (2 films). Other comparative laminations were prepared from the above prepreg with a 2 gsm (g / m2) polyamide mesh weighing as supplied by Bafatex GmbH present on one side of the prepreg (2 films, 1 mesh) and on both sides prepreg (2 films, 2 meshes). Each of the laminations contained 60 prepreg sheets. All laminations of the prepregs in the piles were “mirrored” as outlined in Figure 6, see 304. This means that the subsequent canvas prepregs were turned upside down in orientation with respect to the previous prepreg canvas in the lamination. In contrast, in a “waffle” type lamination, each of the prepreg sheets is applied in the same orientation, see 302.
[0117] The lamination was subsequently pre-compacted and vacuum cured at a pressure of 0.1 bar, and then cut and tested for air voids. A two-stage curing cycle was used, in which the temperature was slowly raised to 85 ° C for 2 hours and 15 minutes and then maintained at 85 ° C for an additional 1.5 hours. This was followed by an additional temperature ramp to 120 ° C for 1.5 hours with a second temperature maintained at 120 ° C for 1 hour. This was followed by cooling to 90 ° C, and preferably below 60 ° C is desirable before removing the cured laminate from the mold. Examples of the invention
[0118] Examples of the invention were prepared by forming the material as a film prepreg as shown in Figure 1 (a, b) as follows.
[0119] A prepreg molding material of the invention was prepared by applying an M9.6GF resin film on one side of the same unidirectional fibrous layer (600 gsm of carbon fiber - 50 thousand filaments per bundle) and compression of this resin in the fibrous layer (1 film process) to form a product containing resin in the interstices of the bundles while maintaining air ventilation paths within the bundles. The prepreg of a film also contained 34% resin by weight. In one embodiment, no mesh was applied (1 film, no mesh). In other embodiments, a mesh was applied on the “dry side” of the prepreg (1 film, mesh on the dry side), a mesh was applied on the side where the resin was applied (1 layer of film and a mesh on the wet side), and two meshes were applied on each side (1 film, 2 meshes). The meshes had the same properties as the meshes in the comparative examples (2 gsm, supplied by Bafatex). The prepregs of the invention were laminated to form a 60-ply laminate molding, where the plies were in the spread laminate or in the "waffle" assembly as defined above.
[0120] The laminate molding pile was then processed in the same way as the comparative examples. The cured laminate pile had a thickness of 35 mm.
[0121] Cuts were obtained from the piles of laminates to measure the average void content (%) and the maximum void size (mm2) obtaining 10 cuts of each laminate at spaced intervals, polishing the cuts and measuring the void content and the void size under a microscope as previously described. The laminates thus produced were examined for void content and the results were as follows:


[0122] Table 1. Void content and maximum void size Tests 1 to 6 Examples of the invention. Tests 7 to 9 comparative examples.
[0123] Additional examples of the invention were prepared by producing the materials illustrated in Figures 2 and 4 by the processes illustrated in Figures 3 and 5, respectively. The material in Figure 2, as described above, was produced by pressing dry fibrous unidirectional bundles of a unidirectional carbon fiber containing 50,000 filaments per bundle and having a sex weight of 600 g / m2 between bundles fully impregnated with the same fibrous unidirectional bundles dried using compression cylinders so that a structure is produced on which dry bundles sit between wet bundles. The resin, again, was M9.6GF, as supplied by Hexcel. As a result of the compression, the dry bundles were partially impregnated with resin so that interstices containing resin are formed between the bundles. One mesh (same polyamide mesh, weight of 2 g / m2, as supplied by Bafatex) was then adhered to the assembly of dry and impregnated bundles by compressing a layer of mesh over the assembly using additional compression cylinders. The material illustrated in Figure 4 was formed using a similar process, and using the same materials, again using unidirectional bundles of a unidirectional carbon fiber containing 50 thousand filaments per bundle and having a dry weight of 600 g / m2, the same material mesh and the same M9.6GF resin. However, in this material, the mesh was driven through the first set of compression cylinders between the dry and fully impregnated fiber bundles, as shown in Figure 5, before the fully impregnated bundles and the dry fibrous bundles were combined.
[0124] The materials of the Examples were prepared with different percentages of dry fibers in relation to the total fiber content; these were 50%, 33% and 25% dry fiber content, for the materials assembled according to Figure 2 (mesh on one side of the set of dry and wet bundles) and according to Figure 4 (mesh between the set of dry and wet bundles). Water absorption tests were performed on each of the samples to assess the degree of impregnation, using the procedure described above.

[0125] Table 2 Water absorption test for prepregs formed with different percentages of dry bundles.
[0126] As is evident from Table 2, the bundles have water absorption values between 15 and 30%, which indicates the presence of individual filaments in the bundles that remain free of resin. We believe that the presence of these filaments ensures that interlaminar and intralaminate air can be removed, thus acting as an air removal structure or gas ventilation network, which in turn results in cured compounds with a void content. reduced.
[0127] The prepregs of the examples above were assembled in piles of laminates comprising 60 tarpaulins. The piles of laminates were then cured using the same method as for the comparative examples. Cuts were obtained from the laminate piles to measure the average void content (%) by obtaining 10 cuts from each laminate at spaced intervals, polishing the cuts and measuring the void content under a microscope as described previously (Table 3).

[0128] Table 3. Void content for piles of laminates with different percentages of dry bundles
[0129] Table 3 illustrates that ventilation in the examples above is considerably improved when compared to comparative examples. We believe that this reduced void content is achieved through improved inter- and intra-laminar ventilation. Improved ventilation is provided by the resin-free paths within the bundles and mesh.
[0130] Therefore, a molding or prepreg material or structure containing a resin and a fibrous reinforcement is provided, the fibrous reinforcement comprising bundles, where the resin is present between the bundles while the inside of the bundles provides a path for ventilation of air during the processing of the material or structure or prepreg.

权利要求:
Claims (9)
[0001]
1.Moulding material or structure comprising a fibrous reinforcement layer and a curable liquid resin, CHARACTERIZED by the fact that the fibrous reinforcement comprises a plurality of bundles, each bundle comprising a plurality of filaments, wherein the resin is provided at least partially between the interstices of the bundles of fibrous reinforcement; and wherein the interstices comprise filaments of adjacent bundles that form the interstices; and in addition, the fibrous reinforcement comprises un-impregnated bundles and at least partially impregnated bundles, to provide an air ventilation path at least within the un-impregnated bundles.
[0002]
2. Molding material or structure according to claim 1, CHARACTERIZED by the fact that the fibrous reinforcement layer comprises air ventilation bundles at least partially embedded in the fibrous reinforcement at least partially impregnated.
[0003]
3. Molding material or structure according to claim 1 or 2, CHARACTERIZED by being provided with a fibrous blanket or mesh.
[0004]
4.Moulding material or structure according to any one of the preceding claims, CHARACTERIZED by the fact that the fibrous reinforcement layer comprises unidirectional fibers and in which resin is provided on one first side of the unidirectional fiber layer, and the second side of the fibrous reinforcement layer is at least partially free of resin.
[0005]
5. Molding material or structure according to claim 4, CHARACTERIZED by the fact that the second side of the fibrous layer is sticky.
[0006]
6. Molding material or structure according to claim 4, CHARACTERIZED by the fact that the first side of the fibrous layer is more sticky than the second side of the fibrous layer.
[0007]
7. Molding material or structure, according to any of the preceding claims, CHARACTERIZED by the fact that it has a water absorption value between 15% and 30%, the WPU being measured by cutting strips of molding material with dimensions of 100 ( +/- 2) mm x 100 (+/- 2) mm; weighing the samples close to the nearest 0.001 g (W1); locating the strips between reinforced PTFE aluminum plates so that 15 mm of the strip protrudes from the assembly of reinforced PTFE plates at one end and where the orientation of the strip fiber extends along the projecting part; placing a clamp on the opposite end, and immersing 5 mm of the projecting part in water with a temperature of 23oC, relative air humidity of 50% +/- 35%, and at an ambient temperature of 23oC; removing the sample after 5 minutes of immersion, and removing any external water with blotting paper; weighing the sample to stabilize W2; calculating the average of the measured weights for the six samples and calculating WPU (%) = [(<W2> - <W1>) / <W1>) x100.
[0008]
8. Molding material or structure according to claim 7, CHARACTERIZED for having a water absorption value between 17% and 26%.
[0009]
9.Moulding material or structure according to any one of the preceding claims, CHARACTERIZED by comprising 70% to 60% fibrous material by weight of the molding material and 30% to 40% curable liquid resin by weight of the material molding.

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同族专利:

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公开号 | 公开日

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US20150017853A1|2015-01-15|

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EP2807017A1|2014-12-03|

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WO2013110111A1|2013-08-01|

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NZ625769A|2016-06-24|

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AU2013212521B2|2017-09-21|

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BR112014017498A8|2017-07-04|

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CN108248063A|2018-07-06|

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NZ719662A|2017-08-25|

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BR112014017498A2|2017-06-13|

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CN104105589A|2014-10-15|

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AU2013212521A1|2014-06-26|

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法律状态:
2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-11-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-09-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-08| 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 25/01/2013, OBSERVADAS AS CONDICOES LEGAIS. |

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2021-11-16| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 9A ANUIDADE. |

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2022-03-08| B24J| Lapse because of non-payment of annual fees (definitively: art 78 iv lpi, resolution 113/2013 art. 12)|Free format text: EM VIRTUDE DA EXTINCAO PUBLICADA NA RPI 2654 DE 16-11-2021 E CONSIDERANDO AUSENCIA DE MANIFESTACAO DENTRO DOS PRAZOS LEGAIS, INFORMO QUE CABE SER MANTIDA A EXTINCAO DA PATENTE E SEUS CERTIFICADOS, CONFORME O DISPOSTO NO ARTIGO 12, DA RESOLUCAO 113/2013. |

优先权:

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ATA90/2012|2012-01-25|

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AT902012|2012-01-25|

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PCT/AT2013/050023|WO2013110111A1|2012-01-25|2013-01-25|Improvements in or relating to laminates|

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