• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    CURABLE PRE-IMPREGNATE, PRE-IMPREGNATE STACK, CURED COMPOSITE LAMINATE, AIRCRAFT BODY STRUCTURE AND PROCESS FOR MANUFACTURING A PRE-IMPREGNATE A curable prepreg comprising a structural layer of conductive fibers and a first layer of thermosetting resin. , the resin layer comprising thermoplastic particles and glassy carbon particles providing improved electrical conductivity and excellent mechanical properties.
    公开号:BR112012003936B1
    申请号:R112012003936-9
    申请日:2010-09-02
    公开日:2020-11-03
    发明作者:John Cawse；Martin Simmons
    申请人:Hexcel Composites Ltd；
    IPC主号:
    专利说明:

    Technical Field
    [001] The present invention relates to improvements in the electromagnetic response of composite materials, particularly to provide greater resistance to damage caused by lightning. Foundations
    [002] Composite materials have well-documented advantages over traditional building materials, in particular in providing excellent mechanical properties at very low material densities. As a result, the use of these materials is becoming increasingly widespread and their areas of application range from "industrial" and "sports and leisure" to high-performance aerospace components.
    [003] Prepregs, comprising a fiber arrangement impregnated with resin, such as epoxy resin, are widely used in the generation of such composite materials. Typically, a number of layers of such prepregs are "laid-up" as desired and the resulting laminate is cured, typically by exposure to elevated temperatures, to produce a cured composite laminate.
    [004] A common composite material consists of a laminate of a plurality of layers of prepreg fibers, for example carbon fibers, interspersed with layers of resin. Although the carbon fibers have some electrical conductivity, the presence of interlayered layers means that it is only displayed in the composite in the laminate plane. The electrical conductivity in the direction orthogonal to the surface of the laminate, the so-called Z direction, is low.
    [005] This lack of conductivity in the Z direction is generally accepted to contribute to the vulnerability of laminated composite materials to electromagnetic hazards, such as lightning. Lightning can cause damage to the composite material, which can be quite extensive, and can be catastrophic if it occurs in an aircraft structure in flight. This is, therefore, a particular problem for aerospace structures made from such composite materials.
    [006] In addition, composites for use in aerospace applications must meet the most demanding standards in mechanical properties. Thus, any improvement in conductivity should not negatively impact the mechanical properties.
    [007] A wide variety of techniques and methods have been suggested in the prior art to provide lightning protection for such composite materials, typically involving the addition of conductive elements at the expense of increasing the weight of the composite material.
    [008] In WO 2008/056123 significant improvements were made in lightning resistance, without significantly increasing the weight or affecting the mechanical properties, through the inclusion of conductive metallic particles in the interlayered resin layers so that they contact the fiber layers adjacent and create an electrical path in the z direction.
    [009] EP 2053078 A1 teaches a prepreg comprising conductive particles and thermoplastic particles. There is a strong preference for conductive metal or coated metal particles.
    [0010] However, the introduction of metal in prepregs, was considered to be undesirable, due to the possibility of corrosion effects, the risks of explosion and differences in the thermal expansion coefficient of the materials. Summary of the Invention
    [0011] The invention relates to a curable prepreg which comprises a structural layer of conductive fibers and a first outer layer of thermosetting resin, the layer of resin comprising thermoplastic particles and glassy carbon particles.
    [0012] The inventors have found that the glassy carbon particles in the first outer layer have the effect that when a plurality of such prepregs are stacked together, producing a prepreg pile comprising a plurality of layers of conductive fibers separated by interlayered layers of resin, high conductivity in the Z direction is achieved while also retaining the excellent mechanical properties provided by the interleaved structure. Furthermore, as the conductive particles are not metallic, the problems associated with the use of metal in the prior art are overcome.
    [0013] It is believed that the excellent mechanical properties provided by the Interleaved structure are due to its laminar arrangement. The glassy carbon particles are located in the Interleaved layers and act to provide an electrical connection between the adjacent layers of conductive fibers. Thus, preferably at least 90% by weight of the glassy carbon particles are located in the outer resin layer or intercalated resin layer if a stack of such prepregs is formed.
    Thus, in another aspect, the invention also relates to a prepreg pile, comprising a plurality of prepregs as defined herein and thus comprising a plurality of structural layers of conductive fibers and a plurality of intercalated layers of resin formed by the first outer layer.
    [0015] For example, such a stack may comprise 4 to 200 structural layers with a corresponding number of layers of resin. Suitable interleaved structures are disclosed in EP 0274899.
    [0016] In a preferred embodiment, the prepreg comprises a second layer of external resin, forming the face of the prepreg not formed by the first external layer. The second outer layer will generally be of the same composition as the first outer layer, and preferably having the same thickness as the first outer layer. In this embodiment, a first and second outer layers combine to become the interleaved layer when a plurality of such prepregs are stacked together.
    [0017] Such interleaved layers preferably have an average thickness of 15 to 50 micrometers. If the prepreg comprises only a first outer layer of resin, then the entire Interlayer layer is formed in the prepreg pile and thus preferably also has an average thickness of 15 to 50 micrometers. If the prepreg has both a first and a second outer layer of resin, then it combines to form the interspersed layer, and therefore the combined thickness of the first and second outer layer of resin is 15 to 50 micrometers.
    [0018] Once formed, a prepreg pile is cured by exposure to high temperature and pressure, optionally high, to produce a cured laminate. Known curing methods can be employed, such as the vacuum bag, autoclave or press curing methods.
    [0019] The thermoplastic particles provide resistance to the resulting laminate and can be made from a wide range of materials, such as polyamides, copolyamides, polyimides, aramids and polyketones, polyetheretherketones, polyarylene ethers, polyesters, polyurethanes and polysulfones. Preferably, the thermoplastic particles comprise polyamide. Preferred materials include polyamide 6, polyamide 6/12 and polyamide 12.
    [0020] Thermoplastic particles can be present in a wide range of levels, however, it has been found that a level of 5 to 20% based on the total resin in the prepreg, preferably 10 to 20% is preferred. Preferably, at least 90% by weight of the thermoplastic particles are located in the outer resin layer or intercalated resin layer if a stack of such prepregs is formed.
    [0021] Thermoplastic particles can be spherical or non-spherical, pink or non-porous. However, porous non-spherical hardener particles, even irregular, have been shown to provide good results, particularly with impact resistance. For example, particles with a sphericity of 0.5 to 0.9 are preferred.
    [0022] Sphericity is a measure of how spherical a particle is. It is the surface area of a sphere with the same volume as the particle divided by the surface area of the particle. Thus, for spherical particles the sphericity is 1. It can be shown that given ψ = (6Vp) 2 / 3TT1 / 3 / Ap, where Vp is the particle volume and Ap is the surface area of the particle.
    [0023] Another convenient measure of particle shape is the aspect ratio. This is defined here as the ratio of the largest cross-sectional diameter to the smallest cross-sectional diameter. Thus, a spherical particle will have an aspect ratio of 1: 1. The thermoplastic particles preferably have an aspect ratio of 3: 1 to 1.2: 1.
    [0024] Preferably, the thermoplastic particles have an average D50 particle size of from 5 to 50 micrometers, preferably from 10 to 30 micrometers.
    [0025] Carbon comes in many forms, such as graphite flakes, graphite powder, graphite particles, graphene sheets, fullerenes, carbon black and carbon nanofibers. However, only glass (or vitreous) carbon particles are suitable for use in the invention. The glassy carbon is typically non-graphitic and is at least 70% sp2 bound, preferably at least 80%, more preferably at least 90% and most preferably, essentially 100% sp2 bound.
    [0026] Glassy carbon particles are very difficult and do not disintegrate during mixing operations with the resin. The glassy carbon particles have very low or no porosity and are all solid and are not hollow. Hollow particles, although lighter, can compromise the mechanical properties of the composite by introducing empty spaces.
    [0027] The glassy carbon particles are intended to bridge the adjacent layers of fiber layers. However, many such particles can have a negative impact on the mechanical properties of the resulting laminate. Thus, the glassy carbon particles are preferably present at a level of 0.3 to 2.0% by weight based on the total resin in the prepreg, preferably from 0.5 to 1.5% by weight, more preferably from 0.5 to 1.0% by weight.
    [0028] Preferably, the glassy carbon particles have an average D50 particle size of 10 to 50 micrometers, more preferably 20 to 40 micrometers.
    [0029] It has been found that a particularly narrow particle size distribution is particularly advantageous, and therefore preferably at least 50% by weight of the glassy carbon particles are within 5 micrometers of average particle size.
    [0030] Glassy carbon particles can be spherical or non-spherical. However, spherical glassy carbon particles have been found to provide excellent conductivity and good particle resistance. For example, particles with a sphericity of at least 0.95 are preferred. In other words, the glassy carbon particles preferably have an aspect ratio of less than 1.1: 1.
    [0031] In order for the glassy carbon particles to provide a transition function, the ratio of the average particle size of the carbon particles to the average interlayer thickness is 0.9: 1 to 1.5: 1, plus preferably from 1: 1 to 1.3: 1.
    [0032] It was found that the ratio between the amounts of thermoplastic particles and glassy carbon particles is important to achieve both good conductivity and good toughness. Thus, preferably the weight ratio of thermoplastic particles to the glassy carbon particles is preferably from 3: 1 to 50: 1, more preferably from 3: 1 to 40: 1, more preferably from 5: 1 to 30: 1 , even more preferably from 8: 1 to 20: 1.
    [0033] The fibers in the structural fiber layers can be unidirectional, woven or multiaxial. Preferably, the fibers are unidirectional and their orientation will vary throughout the stack of prepreg and / or laminate, for example, arranging the fibers in the neighboring layers to be orthogonal to each other in a so-called 0/90 arrangement, meaning the angles between layers of neighboring fibers. Other mechanisms, such as 0 / +45 / -45 / 90 are perfectly possible among many other modalities.
    [0034] The fibers may comprise cracking (i.e., stretch-broken), selectively discontinuous or continuous fibers.
    [0035] Conductive fibers can be made from a wide variety of materials, such as metallized glass, carbon, graphite, metallized polymers and their mixtures. Carbon fibers are preferred.
    [0036] The thermosetting resin can be selected from those conventionally known in the art, such as phenol-formaldehyde, urea-formaldehyde, 1,3,5-triazine-2,4,6-triamine (melamine), bismaleimide resins epoxy, vinyl ester resins, benzoxazine resins, polyesters, unsaturated polyesters, cyanate ester resins, or mixtures thereof.
    [0037] Particularly preferred are epoxy resins, for example, monofunctional, difunctional or trifunctional or tetrafunctional epoxy resins. Preferred difunctional epoxy resins are include diglycidyl ether of bisphenol F (e.g., Araldite GY 281), diglycidyl ether of bisphenol A, naphthalene dihydroxy diglycidyl, and mixtures thereof. A highly preferred epoxy resin is a trifunctional epoxy resin having at least one meta-substituted phenyl ring in its main structure, for example, Araldite MY 0600. A preferred tetrafunctional epoxy resin is tetraglycidyl diphenylmethane (for example, Araldite MY721). A mixture of di- and tri-functional epoxy resins is also highly preferred.
    [0038] The thermosetting resin can also comprise one or more curing agents. Suitable curing agents include anhydrides, particularly polycarboxylic anhydrides; amines, particularly aromatic amines, for example, 1,3-diaminobenzene, 4,4'-diamino, and particularly sulfones, for example 4,4'-diaminodiphenyl sulfone (4,4 'DDS), and 3,3' -diaminodiphil sulfone (3,3 'DDS), and phenol-formaldehyde resins. Preferred curing agents are amino sulfones, particularly 4.4 'DDS and 3.3' DDS.
    [0039] Further examples of the type and design of the resin and fibers can be found in WO 2008/056123.
    [0040] The prepregs according to the invention are typically manufactured by placing a layer of structural fibers in contact with one or more layers of resin, typically at an elevated temperature so that the resin flows into the interstices between the fibers and impregnate them.
    [0041] In one embodiment, a mixture of resin and thermoplastic particles and glassy carbon particles is prepared. This mixture is then made into a sheet and placed in contact with one or both sides of the structural fibers. Due to the size of the particles, they do not impregnate the fibers with the resin and are instead filtered to remain in an outer resin layer. As this involves only one resin application step, this process is called a one-step process.
    [0042] In another embodiment, resin without the particles is transformed into a sheet and placed in contact with one or both sides of the structural fibers. This resin impregnates the fibers and leaves little or nothing on the outer faces. Subsequently, the resins containing the thermoplastic particles and glassy carbon particles are brought into contact with one or both sides of the impregnated structural fibers. This mixture remains on the outside and no longer impregnates the fibers. Since two stages of resin application are involved, this process is called a two-stage process.
    [0043] The two-stage process is preferred as it tends to provide a better-ordered laminate due to the particles not breaking the fibers. This can result in superior mechanical properties.
    [0044] It is further preferred that the two-stage process is applied to a prepreg with both first and second outer layers of resin. In this modality, two layers of resin are placed in contact with the two faces of the structural fibers. The resin impregnates the fibers and leaves little or nothing on the outer faces. Subsequently, the resin containing the thermoplastic particles and glassy carbon particles is brought into contact with both sides of the impregnated structural fibers. This process is referred to as a four film process because four resin films are applied.
    [0045] The present invention is particularly suitable for applications in the aerospace industry, particularly in the formation of aircraft body panels.
    [0046] Just like lightning resistance, it is also desirable to reduce or avoid a phenomenon known as "edge brightness" following lightning. This is caused by an accumulation of electrical charge at the ends of a composite structure and can become a source of ignition.
    [0047] It has been found that composite materials for use in aircraft body structures can suffer from such edge gloss problems. This is a particularly dangerous problem if composite materials are intended to form part of a fuel tank construct.
    [0048] Thus, the invention is ideally suited to provide a cured laminated composite component of an aircraft fuel tank construct.
    [0049] The invention will now be illustrated by way of example and with reference to the following figures, in which
    [0050] Figure 1 is an image of a cross section through a cured composite laminate according to the present invention.
    [0051] Figure 2 is an image of a cross section through another composite laminate cured according to the present invention.
    [0052] Figure 3 is an image of a cross section through an additional cured composite laminate according to the invention. Examples
    [0053] Prepreg rolls (10 m x 0.3 m) with different amounts and types of carbon particles were produced. A prepreg without any glassy carbon was included for comparison.
    [0054] Seven resistance panels in the form of 12 ply laminates (2.1x103 N / m) were produced using 0/90 lay-up and cured at 180 ° C for 2 hours in an autoclave at a pressure of 3 bar (0 , 3MPa). Table 1 below shows the results of prepreg resistance containing the carbon microspheres, and one containing zero microspheres for comparison. Resistance was measured by cutting square samples from the panel (35 mm x 35 mm) and coating each square side with gold. Electrodes were placed over the coated samples and then, using a power supply to provide a current (A) the voltage was determined. Resistance was calculated using Ohm's law (R = V / l). Table 1
    [0055] Araldite MY 0600 and GY 281 are available from Huntsman, United Kingdom. PES 5003P is available from Sumitomo. Orgasol DNatl 1002D is available from Arkema. 4,4'DDS is available from Huntsman, United Kingdom.
    [0056] The first type of carbon particles is 20 to 50 pm Type I from Alfa Aesar (USA) and are highly spherical with a sphericity of more than 0.99 and an average d50 particle size of 30.1 pm . The second type of carbon particles is 20-50 pm Sigradur G from HTW Hochtemperatur-Workstoffe GmbH and is irregular with a sphericity of about 0.65 and an average d50 particle size of 29.3 pim. The third type of carbon particles are also 20-50 pm from HTW and are highly spherical with a sphericity of more than 0.99 and an average d50 particle size of 30.5 pm. The particle size was measured using a Malvern Instruments Mastersizer using a lens ranging from 300 mm and a beam length of 2.40 mm.
    [0057] It can be seen that the laminates comprising the glassy carbon particles show a significant drop in electrical resistance. It is also noticeable that the drop in resistance is more significant for spherical particles than for irregular particles. It is believed to be due to less contacts being made between adjacent structural layers with the irregular particles.
    [0058] Figures 1,2 and 3 show a cross section through the cured laminate according to examples 4, 3 and 6, respectively.
    [0059] The images show layers of unidirectional carbon fibers aligned on page 10 and unidirectional carbon fibers aligned along page 12. Separating the carbon fiber and resin interlayer layers 14. Dispersed with the resin interlayer 14 are particles harder irregular shapes. Also dispersed within the interlayer are highly spherical glassy carbon particles 16.
    Medida utilizando uma máquina de teste diferente.[0060] A variety of mechanical tests were performed on batches produced according to Examples 3, 7 and Comparative Example 8. The results are shown below in Table 2. Table 2 Measured using a different testing machine.
    [0061] It can be seen that the addition of the glassy carbon particles according to the invention does not have a significant impact on the mechanical properties.
    权利要求:
    Claims (17)
    [0001]
    1. Curable prepreg, CHARACTERIZED by the fact that it comprises a structural layer of conductive fibers and a first external layer of thermosetting resin, the layer of resin comprising thermoplastic particles and glassy carbon particles, in which the glassy carbon particles are present at a level of 0.3 to 2.0% by weight based on the total resin in the prepreg, where the ratio of the average particle size of the carbon particles to the average thickness of the interlayer is 0.9: 1 to 1.5: 1, and where the weight ratio of thermoplastic particles to glassy carbon particles is 3: 1 to 50: 1.
    [0002]
    2. Prepreg, according to claim 1, CHARACTERIZED by the fact that it comprises a second layer of external resin, forming the face of the prepreg not formed by the first external layer.
    [0003]
    3. Pre-impregnated, according to claim 1 or 2, CHARACTERIZED by the fact that the total thickness of the first and, if present, second, outer resin layers is 15 to 50 micrometres.
    [0004]
    4. Prepreg, according to any one of claims 1 to 3, CHARACTERIZED by the fact that the thermoplastic particles comprise polyamide.
    [0005]
    5. Prepreg, according to claim 4, CHARACTERIZED by the fact that the thermoplastic particles comprise polyamide 6, polyamide 6/12, polyamide 12 or mixtures thereof.
    [0006]
    6. Prepreg according to any one of claims 1 to 5, CHARACTERIZED by the fact that the thermoplastic particles are present at a level of 5 to 20% based on the total resin in the prepreg.
    [0007]
    7. Prepreg, according to any one of claims 1 to 6, CHARACTERIZED by the fact that the thermoplastic particles have a sphericity of 0.5 to 0.9.
    [0008]
    8. Prepreg, according to any one of claims 1 to 7, CHARACTERIZED by the fact that the thermoplastic particles have an average particle size d50 of 5 to 50 micrometers.
    [0009]
    9. Prepreg according to any one of claims 1 to 8, CHARACTERIZED by the fact that the glassy carbon particles are present at a level of 0.5 to 1.5% by weight based on the total resin in the pre -impregnated.
    [0010]
    10. Prepreg according to any one of claims 1 to 9, CHARACTERIZED by the fact that the glassy carbon particles have an average particle size d50 of 10 to 50 micrometers.
    [0011]
    11. Prepreg, according to any one of claims 1 to 10, CHARACTERIZED by the fact that at least 50% by weight of the glassy carbon particles are within 5 micrometers of the average particle size.
    [0012]
    12. Prepreg according to any one of claims 1 to 11, CHARACTERIZED by the fact that the glassy carbon particles have a sphericity of at least 0.95.
    [0013]
    13. Prepreg according to any one of claims 1 to 12, CHARACTERIZED by the fact that the ratio of the average particle size of the carbon particles to the average thickness of the interlayer is from 1: 1 to 1.3: 1 .
    [0014]
    14. Prepreg according to any one of claims 1 to 13, CHARACTERIZED by the fact that the weight ratio of thermoplastic particles to glassy carbon particles is from 3: 1 to 40: 1.
    [0015]
    15. Prepreg according to any one of claims 1 to 14, CHARACTERIZED by the fact that the resin comprises a difunctional epoxy resin.
    [0016]
    16. Prepreg, according to any one of claims 1 to 15, CHARACTERIZED by the fact that the resin comprises a trifunctional epoxy resin having at least one meta-substituted phenyl ring in its main structure.
    [0017]
    17. Prepreg according to any one of claims 1 to 16, CHARACTERIZED by the fact that the resin comprises an aminosulfone curing agent.
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
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    2019-06-25| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
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    2021-08-10| B21F| Lapse acc. art. 78, item iv - on non-payment of the annual fees in time|Free format text: REFERENTE A 11A ANUIDADE. |
    2021-11-30| 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 2640 DE 10-08-2021 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:
    申请号 | 申请日 | 专利标题
    GB0915366.9|2009-09-04|
    GB0915366A|GB2473226A|2009-09-04|2009-09-04|Composite materials|
    PCT/GB2010/051452|WO2011027160A1|2009-09-04|2010-09-02|Improvements in composite materials|
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