WO2019227474A1 - 厚度方向导电的层压复合材料及其制造方法 - Google Patents

厚度方向导电的层压复合材料及其制造方法 Download PDF

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Publication number
WO2019227474A1
WO2019227474A1 PCT/CN2018/089571 CN2018089571W WO2019227474A1 WO 2019227474 A1 WO2019227474 A1 WO 2019227474A1 CN 2018089571 W CN2018089571 W CN 2018089571W WO 2019227474 A1 WO2019227474 A1 WO 2019227474A1
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Prior art keywords
conductive
fiber
fibers
composite material
interlayer
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PCT/CN2018/089571
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English (en)
French (fr)
Inventor
益小苏
肖勇民
陆明彦
刘晓玲
廖庆华
从小晔
朱晨凯
马学刚
Original Assignee
北京美格美沃科技有限公司
宁波诺丁汉新材料研究院有限公司
宁波诺丁汉大学
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Application filed by 北京美格美沃科技有限公司, 宁波诺丁汉新材料研究院有限公司, 宁波诺丁汉大学 filed Critical 北京美格美沃科技有限公司
Priority to US17/059,743 priority Critical patent/US20220270780A1/en
Priority to PCT/CN2018/089571 priority patent/WO2019227474A1/zh
Publication of WO2019227474A1 publication Critical patent/WO2019227474A1/zh

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Definitions

  • the present disclosure relates to a laminated composite material that is electrically conductive in the thickness direction, a method of manufacturing the same, and applications.
  • Thermosetting resin-based laminated composites are widely used in the manufacture of aircraft bodies. As the material of the aircraft fuselage, shock resistance is one of its most critical properties. While using various methods to improve the impact resistance of thermosetting resin-based laminated composite materials, it is also necessary to improve the ability to shield electronic interference and the ability to protect against lightning strikes.
  • An embodiment of the present invention provides a laminated composite material that is electrically conductive in the thickness direction
  • the laminated composite material that is electrically conductive in the thickness direction includes: laminated multilayer carbon fibers, interposed between the multilayer carbon fibers, and covering the multilayer A carbon fiber and a curable resin bonding the multilayer carbon fibers into one body, and a conductive material, the conductive material including at least one of the following: conductive fibers woven with the carbon fibers; interlayer conductive films; interlayers Conductive Z-pin; and interlayer conductive particles, the volume percentage of the carbon fiber in the thickness-conducting laminated composite material being ⁇ 40 vol%.
  • the conductive fiber is interwoven and / or parallel woven with the carbon fiber.
  • the conductive fiber is interwoven with the carbon fiber; in a direction perpendicular to the length of the conductive fiber, each of the conductive fibers includes 1-5 conductive fibers; and the diameter of the conductive fiber is 0.005mm-0.5mm.
  • each of the conductive fibers includes 3 of the conductive fibers; the diameter of the conductive fibers is 0.01 mm-0.3 mm.
  • the conductive fiber is woven in parallel with the carbon fiber; the parallel woven includes intra-knitting and / or inter-knitting; in a direction perpendicular to the length of the conductive fiber, each 10 mm includes 1- 5 said conductive fibers; the diameter of said conductive fibers is 0.05mm-0.5mm.
  • each 10 mm in a direction perpendicular to the length of the conductive fiber, includes 3 of the conductive fibers; and the diameter of the conductive fiber is 0.01 mm-0.3 mm.
  • the conductive fiber includes at least one of a surface metallized glass fiber, a surface metallized organic fiber, a surface metallized carbon nanotube yarn, and an ultra-fine metal fiber.
  • the interlayer conductive film includes: a surface-metallized porous polymer film, a surface-metallized non-woven fabric, a surface-metallized fabric, a surface-metallized paper, and a surface-metallized At least one of polymer foam.
  • the thickness of the interlayer conductive film is 0.01 mm-0.2 mm.
  • the interlayer conductive Z-pin includes a surface metallized composite material Z-pin or a metal Z-pin, and the Z-pin is interposed between two adjacent layers of the carbon fibers. Curable resin, but does not penetrate the curable resin between the two adjacent layers of the carbon fiber.
  • the interlayer conductive particles include surface metallized polymer particles, surface metallized inorganic grains, surface metallized hollow glass microspheres, metal particles, and the surface metallized
  • the diameters of the polymer particles, the surface metallized inorganic crystal grains, and the metal particles are 10 ⁇ m to 50 ⁇ m; and the diameter of the surface metallized hollow glass microspheres is 50 ⁇ m to 100 ⁇ m.
  • the interlayer conductive particles include a surface metallized zinc oxide whisker (ZnO Whisker), and an outer dimension of the surface metallized zinc oxide whisker is 50 ⁇ m-250 ⁇ m.
  • ZnO Whisker surface metallized zinc oxide whisker
  • the conductive material includes: a conductive fiber woven with the carbon fiber and an interlayer conductive film.
  • the curable resin includes epoxy resin, vinyl resin, bismaleimide, polyimide, unsaturated polyester, and benzoxazine.
  • An embodiment of the present invention also provides a method for manufacturing a laminated composite material that is conductive in the thickness direction, including:
  • the volume percentage of the carbon fiber in the laminated conductive material in the thickness direction is ⁇ 40 vol%
  • the method further includes a step of setting a conductive material;
  • the step of setting a conductive material includes at least one of the following: before the step 1), the conductive fiber and the carbon fiber are woven with each other; in the step 1) After that, before step 2), or after step 2), before step 3), interlayer conductive film is inserted; after step 2), before step 3), interlayer conductive Z is set. -pin; after the step 1), before the step 2), or after the step 2), before the step 3), interlayer conductive particles are added.
  • the step of providing a conductive material includes: before the step 1), weaving conductive fibers and the carbon fibers with each other; and after the step 1) Before the step 2), or after the step 2) and before the step 3), an interlayer conductive film is inserted.
  • the conductive fiber in each of the layers of the laminated multi-layer carbon fiber, is cross-woven and / or parallel-woven with the carbon fiber.
  • the conductive fiber is interwoven with the carbon fiber; in a direction perpendicular to the length of the conductive fiber, 1-5 conductive fibers are included every 10 mm; The diameter of the conductive fiber is 0.005mm-0.5mm.
  • three conductive fibers are included every 10 mm in a direction perpendicular to the length of the conductive fibers; and the diameter of the conductive fibers is 0.1 mm-0.3 mm.
  • the conductive fiber is woven in parallel with the carbon fiber; the parallel woven includes intra-knitting and / or inter-knitting; in a direction perpendicular to the length of the conductive fiber
  • Each 10mm includes 1-5 said conductive fibers; the diameter of said conductive fibers is 0.005mm-0.5mm.
  • the conductive fiber includes 3 conductive fibers per 10 mm in a direction perpendicular to the length of the conductive fiber; the conductive fiber has a diameter of 0.01 mm to 0.3 mm.
  • the conductive fibers include surface metallized glass fibers, surface metallized organic fibers, surface metallized carbon nanotube yarns, and ultrafine metal fibers. At least one.
  • the interlayer conductive film includes: a surface-metallized porous polymer film, a surface-metallized non-woven fabric, a surface-metallized fabric, and a surface-metallized At least one of paper and surface metallized polymer foam.
  • the thickness of the interlayer conductive film is 0.01 mm-0.2 mm.
  • the inter-layer conductive Z-pin includes a surface metallized composite material Z-pin or a metal Z-pin, and the Z-pin is pierced into two adjacent layers. Curable resin between the carbon fibers, but does not penetrate the curable resin between the two adjacent layers of the carbon fibers.
  • the interlayer conductive particles include surface metalized polymer particles, surface metallized inorganic grains, surface metallized hollow glass microbeads, metal particles,
  • the diameter of the surface metallized polymer particles, the surface metallized inorganic crystal grains, and the metal particles are 10 ⁇ m to 50 ⁇ m; the diameter of the surface metallized hollow glass microspheres is 50 ⁇ m to 100 ⁇ m.
  • the interlayer conductive particles include surface metallized zinc oxide whiskers (ZnO Whisker), and the surface metallized zinc oxide whiskers have an outer size of 50 ⁇ m. -250 ⁇ m.
  • the curable resin includes epoxy resin, vinyl resin, bismaleimide, polyimide, unsaturated polyester, benzoxazine .
  • FIG. 1 is an external view of a cross-woven layer of a silver-coated polyester fiber and a carbon fiber according to an embodiment of the present invention
  • FIG. 2 is a SEM photograph of a silver-coated nylon non-woven fabric according to an embodiment of the present invention
  • FIG. 3 is a schematic flowchart of a method for inserting a Z-pin between layers according to an embodiment of the present invention
  • FIG. 5 is a cross-sectional view of a laminate material with zinc oxide whiskers walked between layers in accordance with an embodiment of the present invention
  • FIG. 6 is a dot-matrix diagram of conductive silver paste printed on a T300 carbon fiber plain weave fabric provided by an embodiment of the present invention.
  • thermosetting resin-based laminated composite material Since the main structure of the thermosetting resin-based laminated composite material is usually a non-conductive polymer material, the ability of the thermosetting resin-based laminated composite material to shield from electronic interference and the protection against lightning strikes are generally poor. In order to improve the ability to shield electronic interference and lightning strike protection, it is necessary to improve the conductive property of the thermosetting resin-based laminated composite material, especially the conductive property in the thickness direction. However, currently existing technologies tend to impair the impact resistance of the thermosetting resin-based laminated composite material while improving its electrical conductivity. Therefore, the present disclosure provides an attempt to provide a laminated composite material that can both improve the conductivity of a thermosetting resin-based laminated composite material without impairing or even improving its impact resistance.
  • Example 1 Conductive laminated composite material in thickness direction, including conductive fiber interwoven with carbon fiber
  • a polyester fiber is prepared, and a layer of metallic silver is vapor-deposited on the surface of the polyester fiber to obtain a polyester fiber whose surface is covered with silver (that is, the surface is metallized).
  • the internal body material of the conductive fiber it is not limited to the above-mentioned polyester fiber, and other similar materials such as glass fiber, organic fiber, carbon nanotube filament, etc. can be used; the method of surface metallization is also not It is limited to the above-mentioned vapor deposition method, and other methods such as electroless plating and brush coating can also be used.
  • the metal covering the surface of the inner body material of the conductive fiber is not limited to silver, and other conductive metals such as copper and nickel are also used. be usable.
  • the silver-coated polyester fiber obtained above was cross-woven with T700 unidirectional carbon fiber fabric (made by Toray) (also known as unidirectional weaving), and each 10 mm included 3 in a direction perpendicular to the length of the silver-coated polyester fiber.
  • the silver-coated polyester fiber has a diameter of 0.3 mm, and a cross-knitted layer of the silver-coated polyester fiber and T700 carbon fiber is obtained, and its appearance is shown in FIG. 1.
  • the multilayer of the silver-coated polyester fiber and the T700 carbon fiber cross-woven layer are superimposed.
  • the surface of the silver-coated polyester fiber has slightly raised conductive contact points, when the two layers of the silver-coated polyester fiber are When superimposed with the T700 carbon fiber cross-woven layer, these contact points make contact with each other, forming a current path in the thickness direction.
  • the curable resin may also use other curable resins such as vinyl resin, bismaleimide, polyimide, unsaturated polyester, benzoxazine, etc. ;
  • the above prepreg method can also use conventional prepreg methods such as dry method, wet method and the like.
  • Example 2 Conductive laminated composite material in thickness direction, including conductive fiber interwoven with carbon fiber
  • the method for manufacturing a conductive laminate composite material in the thickness direction in this embodiment is basically the same as that in Embodiment 1, except that the diameter and the weaving density of the silver-coated polyester fiber are perpendicular to the silver-coated polyester fiber.
  • each 10 mm includes 4 silver-coated polyester fibers; the diameter of the silver-coated polyester fibers is 0.4 mm.
  • the measured vertical resistance of the finally obtained thickness-conducting laminated composite material with a multimeter is about 2 ohms.
  • Example 1 since the diameter and weaving density of the silver-coated polyester fiber are increased, the current path in the thickness direction of the laminated composite material is more, and thus the resistance is further reduced.
  • the resistance in the thickness direction of the laminated composite material will be further reduced.
  • the diameter and weaving density of the silver-coated polyester fiber cannot be increased indefinitely because the excessive use of the silver-coated polyester fiber will squeeze the space of the carbon fiber, resulting in a reduction in the amount of carbon fiber, thereby Ultimately affect the strength of the laminated composite. It is determined through experiments that the proper range of the amount of conductive fibers used is: in the direction perpendicular to the length of the conductive fibers, 1-5 conductive fibers are included for every 10 mm; the diameter of the conductive fibers is 0.05 mm-0.5 mm.
  • Example 3 Conductive laminated composite material in the thickness direction, including conductive fibers woven in parallel with carbon fibers (also known as "in-plane” woven)
  • the method of manufacturing a laminated composite material with conductive in the thickness direction in this embodiment is basically the same as that in Embodiment 1, except that Embodiment 1 uses a unidirectional carbon fiber fabric, while this embodiment uses a non-unidirectional carbon fiber (plain weave). ) Fabric (or in-plane blended fabric). The conductive fibers are mixed into the non-unidirectional carbon fiber (plain weave) fabric, and the weaving method includes intra-beam weaving or inter-beam weaving to obtain a non-unidirectional carbon fiber-conductive fiber fabric.
  • the intra-bundle weaving refers to weaving the conductive fibers into the carbon fiber bundle (commingling), that is, the conductive fibers and the carbon fibers are in close contact in the bundle; and the inter-bundle weaving refers to
  • the conductive fiber is not woven into the carbon fiber bundle, but is mixed with the carbon fiber bundle into a plain weave, that is, the conductive fiber is not in close contact with the carbon fiber.
  • the diameter and braid density of the conductive fiber determine the thickness-wise conductivity of the final conductive laminated composite material.
  • the measured vertical resistance of the thickness-conductive conductive laminated composite material obtained with a multimeter is about 2 ohms in the vertical direction. .
  • the interlayer conductive film may be, for example, a surface metallized planar material such as a surface metallized porous polymer film, a surface metallized non-woven fabric, a surface metallized fabric, a surface metallized paper, or a surface metallized Polymer foam, etc.
  • a surface metallized planar material such as a surface metallized porous polymer film, a surface metallized non-woven fabric, a surface metallized fabric, a surface metallized paper, or a surface metallized Polymer foam, etc.
  • it may be a thin or ultra-thin, ultra-fine porous metal fiber felt, a metal fiber fabric, or a metal foam.
  • a non-woven nylon fabric with a silver surface is prepared, which has a thickness of about 53 ⁇ m and an areal density of about 16 g / m 2 .
  • the diameter of nylon fiber is about 10-18 ⁇ m.
  • the entire surface of the non-woven fabric was chemically silver-coated, and the area density of the silver-coated silver was 11.6 g / m 2 .
  • the measured square resistance value of the silver-coated nylon non-woven fabric was 0.08 ⁇ , and the SEM photograph is shown in FIG. 2.
  • Insert the silver-coated nylon non-woven fabric obtained above into one layer of T700 unidirectional carbon fiber fabric (made by Toray) (the so-called "insertion” can be an equal area insertion, that is, the same layer as the carbon fiber layer) Or can also be selectively laminated), 12 layers of the T700 unidirectional carbon fiber fabric with a silver non-woven fabric coated with silver on the surface are stacked to make a so-called laminated "preform”, and then The liquid epoxy resin cured at 120 ° C. is impregnated with the above-mentioned laminated preform, so-called “liquid molding”, and then the epoxy resin is heated to its curing temperature to achieve curing, and finally a laminated composite material with conductive thickness is obtained.
  • the electrical conductivity and interlayer fracture toughness of the test are listed in Tables 1 and 2 below.
  • the conductivity of the laminate without interlayer conductive film except for the non-woven non-woven silver-coated nylon surface, which is the same as this example
  • the interlayer fracture toughness were also tested.
  • 2vol% graphite Conductivity of olefin conductive modified laminate replacement of silver-coated nylon nonwoven fabric with 2 vol% graphene.
  • R x is the conductivity along the direction of the carbon fiber in the plane of the laminate
  • R y is the conductivity that is perpendicular to the direction of the carbon fiber in the plane of the laminate
  • R z is perpendicular to the plane of the laminate (that is, the thickness direction) Conductivity.
  • the laminated material of this embodiment has greatly reduced R x , R y , R z , and the reduction of R y , R z is particularly significant.
  • Table 2 the interlaminar fracture toughness of the laminate of this embodiment is greatly improved compared with the laminate without an interlayer conductive film (G IC : I-type interlayer fracture toughness; G IIC : II-type interlayer fracture toughness).
  • Example 5 Conductive laminated composite material in thickness direction, including interlayer conductive Z-pin
  • Z-pins can usually be made with a surface metallized composite material or the metal material itself; the shape of the Z-pin can also be flexibly designed, such as T-shaped pins or pins with "barbed” to increase the conductivity in the thickness direction At the same time, it also strengthens the mechanical connection performance.
  • the surface metallized carbon fiber composite material is used as the Z-pin. Referring to the process shown in FIG. 3, the Z-pin is inserted into the curable resin between two adjacent layers of carbon fibers, but does not penetrate through The curable resin between two adjacent layers of carbon fibers is described.
  • the density of Z-pin affects the electrical conductivity in the thickness direction of the composite. The higher the density of Z-pin, the higher the electrical conductivity of the composite; the density of Z-pin also affects the mechanical properties of the composite. Increasing the density of Z-pin will reduce the composite In-plane mechanical properties of materials.
  • Example 6 Laminated Composite Material Conducting in the Thickness Direction Including Interlayer Conductive Particles
  • conductive particles can also be dispersed between the layers.
  • the materials of the conductive particles are mainly metallized three-dimensional materials such as polymerized metal particles on the surface, and inorganic whiskers with metalized surfaces.
  • particles that are electrically conductive, such as metal particles can be used directly.
  • the method of dispersing the conductive particles is not limited, and may be, for example, surface growth, scattering of a vibrating screen, and the like.
  • One special case is the growth of conductive zinc oxide (ZnO) whiskers on the surface of the prepreg.
  • ZnO conductive zinc oxide
  • Zinc oxide whiskers (ZnO Whisker) grown on a carbon fiber epoxy prepreg (brand: CCF300 / 5228), where (d) is a partial enlargement of (c).
  • Zinc oxide whiskers (ZnO Whisker) have electrical conductivity. If zinc oxide whiskers (ZnO Whisker) are metallized in advance, their conductivity is higher.
  • Figure 5 is an interlayer cross section of the CCF300 / 5228 epoxy composite after curing. Zinc oxide whiskers are clearly visible. These conductive zinc oxides not only electrically connect the carbon fiber layup, but also strengthen the interlayer connection and improve the interlayer of the composite material. toughness.
  • Example 7 Laminated Composite Material Conducting in the Thickness Direction Including Interlayer Conductive Particles
  • the conductive particles are uniformly distributed on the surface of the substrate, such as a uniform surface lattice.
  • the molding of this composite material can be liquid molding, but it is particularly suitable for prepreg autoclave molding. Obviously, the areal density of the conductive particles will affect the conductivity of the composite material, especially the thickness direction.
  • Figure 6 shows the conductive silver paste dot matrix printed on T300 carbon fiber plain weave. This conductively treated fabric can be used to form a conductive composite material in a liquid state. The measured conductivity in the thickness direction of this composite material is about 10 S / cm.
  • Example 8 Conductive laminated composite material in the thickness direction including both conductive fibers and an interlayer conductive film
  • Step 1) is similar to Example 1, except that a layer of metallic silver is vapor-deposited on the surface of the glass fiber to obtain a silver-coated conductive fiber with a diameter of 0.01 mm.
  • the silver-coated conductive fibers were used as weft yarns to weave with domestic T300 unidirectional carbon fibers (Shandong Weihai Guangwei) to form conductive unidirectional fiber cloth. In the direction perpendicular to the length of the silver-coated conductive fiber, 5 silver-coated conductive fibers are included every 10 mm.
  • Step 2) Similar to Example 6, a silver-coated nylon non-woven fabric was used as the conductive film.
  • the thickness was about 30 ⁇ m and the areal density was about 9 g / m 2.
  • the nylon fiber diameter was about 10-15 ⁇ m. Area density is 10g / m 2 .
  • the conductive unidirectional fiber cloth obtained in the above step 1 and the conductive film obtained in the above step 2 alternately, that is, a layer of conductive film, a layer of conductive unidirectional fiber cloth, a layer of conductive film, and a layer Conductive unidirectional fiber cloth, a layer of conductive film, a layer of conductive unidirectional fiber cloth, this cycle is repeated, a total of 11 times, and finally, the conductive film is used as the outermost layer to obtain a conductive composite material preform (a total of 12 layers) Conductive film, 11 layers of conductive unidirectional fiber cloth, alternately layered, the outermost two sides are conductive film).
  • the above-mentioned conductive composite material preform is placed in a metal closed mold, the volume fraction of carbon fiber is controlled to about 50%, and the liquid epoxy resin cured at 180 ° C. is liquid-formed and cured to finally obtain a laminated composite material that is conductive in the thickness direction.
  • the conductivity is as high as about 150 S / m
  • G IC is as high as about 1000 J / m 2
  • G IIC is as high as about 2500 J / m 2 .
  • This embodiment combines the "conductive fiber woven with carbon fibers" of Example 1 and the "interlayer conductive film" of Example 6.
  • the thickness direction conductivity of the final product obtained is higher than that of Examples 1 and 6.
  • the interlayer fracture toughness (G IC : Type I interlayer fracture toughness; G IIC : Type II interlayer fracture toughness) is also improved compared to Examples 1 and 6.

Abstract

一种厚度方向导电的层压复合材料，包括：层叠的多层碳纤维、处于多层碳纤维之间、包覆多层碳纤维并将多层碳纤维粘接为一体的可固化树脂、以及导电材料，导电材料包括以下的至少一种：与碳纤维编织在一起的导电纤维；层间导电膜；层间导电Z-pin；以及层间导电颗粒，碳纤维占厚度方向导电的层压复合材料的体积百分比≥40vol％。这种厚度方向导电的层压复合材料的厚度方向导电性能、面内导电性能和电功传输性能都高于传统的层压复合材料。

Description

厚度方向导电的层压复合材料及其制造方法 技术领域
本公开涉及厚度方向导电的层压复合材料、其制造方法及应用。
背景技术
热固性树脂基层压复合材料被广泛应用在飞机机体的制造上。作为飞机机身的制造材料，抗冲击能力是其最关键的性能之一。在采用各种方式提高热固性树脂基层压复合材料的抗冲击能力的同时，还需要提高屏蔽电子干扰的能力以及雷击保护能力。
发明内容
本发明的实施例提供一种厚度方向导电的层压复合材料，所述厚度方向导电的层压复合材料包括：层叠的多层碳纤维、处于所述多层碳纤维之间、包覆所述多层碳纤维并将所述多层碳纤维粘接为一体的可固化树脂、以及导电材料，所述导电材料包括以下的至少一种：与所述碳纤维编织在一起的导电纤维；层间导电膜；层间导电Z-pin；以及层间导电颗粒，所述碳纤维占所述厚度方向导电的层压复合材料的体积百分比≥40vol％。
在一种实施方式中，例如，在所述层叠的多层碳纤维的每一层中，所述导电纤维与所述碳纤维交叉编织和/或平行编织。
在一种实施方式中，例如，所述导电纤维与所述碳纤维交叉编织；在垂直于所述导电纤维长度方向上，每10mm包括1-5根所述导电纤维；所述导电纤维的直径为0.005mm-0.5mm。
在一种实施方式中，例如，在垂直于所述导电纤维长度方向上，每10mm包括3根所述导电纤维；所述导电纤维的直径为0.01mm-0.3mm。
在一种实施方式中，例如，所述导电纤维与所述碳纤维平行编织；所述平行编织包括束内编织和或束间编织；在垂直于所述导电纤维长度方向上，每10mm包括1-5根所述导电纤维；所述导电纤维的直径为0.05mm-0.5mm。
在一种实施方式中，例如，在垂直于所述导电纤维长度方向上，每10mm 包括3根所述导电纤维；所述导电纤维的直径为0.01mm-0.3mm。
在一种实施方式中，例如，所述导电纤维包括表面金属化的玻璃纤维、表面金属化的有机纤维、表面金属化的碳纳米管纱线、以及超细金属纤维中的至少一种。
在一种实施方式中，例如，所述层间导电膜包括：表面金属化的多孔高分子膜、表面金属化的无纺布、表面金属化的织物、表面金属化的纸、表面金属化的高分子泡沫中的至少一种。
在一种实施方式中，例如，所述层间导电膜的厚度为0.01mm-0.2mm。
在一种实施方式中，例如，所述层间导电Z-pin包括表面金属化的复合材料Z-pin或者金属Z-pin，所述Z-pin扎入两层相邻的所述碳纤维之间的可固化树脂，但又不穿透所述两层相邻的所述碳纤维之间的可固化树脂。
在一种实施方式中，例如，所述层间导电颗粒包括表面金属化的高分子颗粒、表面金属化的无机晶粒、表面金属化的空心玻璃微珠、金属颗粒，所述表面金属化的高分子颗粒、所述表面金属化的无机晶粒、所述金属颗粒的直径为10μm-50μm；所述表面金属化等空心玻璃微珠的直径为50μm-100μm。
在一种实施方式中，例如，所述层间导电颗粒包括表面金属化的氧化锌晶须(ZnO Whisker)，所述表面金属化的氧化锌晶须的外形尺寸为50μm-250μm。
在一种实施方式中，例如，所述导电材料包括：与所述碳纤维编织在一起的导电纤维和层间导电膜。
在一种实施方式中，例如，所述可固化树脂包括环氧树脂、乙烯基树脂、双马来酰亚胺、聚酰亚胺、不饱和聚酯、苯并恶嗪。
本发明的实施例还提供一种厚度方向导电的层压复合材料的制造方法，包括：
1)将多层碳纤维叠层铺放，得到层叠的多层碳纤维；
2)将所述层叠的多层碳纤维预浸可固化树脂，得到层叠的多层碳纤维预浸料；
3)固化所述可固化树脂，在最终获得的厚度方向导电的层压复合材料中，所述碳纤维占所述厚度方向导电的层压复合材料的体积百分比≥40vol％；
其中，所述方法还包括设置导电材料的步骤；所述设置导电材料的步骤 包括以下至少之一：在所述步骤1)之前，将导电纤维与所述碳纤维相互编织；在所述步骤1)之后、所述步骤2)之前，或者所述步骤2)之后、所述步骤3)之前，插入层间导电膜；在所述步骤2)之后、所述步骤3)之前，设置层间导电Z-pin；在所述步骤1)之后、所述步骤2)之前，或者所述步骤2)之后、所述步骤3)之前，加入层间导电颗粒。
在一种实施方式中，例如，在所述方法中，所述设置导电材料的步骤包括：在所述步骤1)之前，将导电纤维与所述碳纤维相互编织；和在所述步骤1)之后、所述步骤2)之前，或者所述步骤2)之后、所述步骤3)之前，插入层间导电膜。
在一种实施方式中，例如，在所述方法中，在所述层叠的多层碳纤维的每一层中，所述导电纤维与所述碳纤维交叉编织和/或平行编织。
在一种实施方式中，例如，在所述方法中，所述导电纤维与所述碳纤维交叉编织；在垂直于所述导电纤维长度方向上，每10mm包括1-5根所述导电纤维；所述导电纤维的直径为0.005mm-0.5mm。
在一种实施方式中，例如，在所述方法中，在垂直于所述导电纤维长度方向上，每10mm包括3根所述导电纤维；所述导电纤维的直径为0.1mm-0.3mm。
在一种实施方式中，例如，在所述方法中，所述导电纤维与所述碳纤维平行编织；所述平行编织包括束内编织和或束间编织；在垂直于所述导电纤维长度方向上，每10mm包括1-5根所述导电纤维；所述导电纤维的直径为0.005mm-0.5mm。
在一种实施方式中，例如，在所述方法中，在垂直于所述导电纤维长度方向上，每10mm包括3根所述导电纤维；所述导电纤维的直径为0.01mm-0.3mm。
在一种实施方式中，例如，在所述方法中，所述导电纤维包括表面金属化的玻璃纤维、表面金属化的有机纤维、表面金属化的碳纳米管纱线、以及超细金属纤维中的至少一种。
在一种实施方式中，例如，在所述方法中，所述层间导电膜包括：表面金属化的多孔高分子膜、表面金属化的无纺布、表面金属化的织物、表面金属化的纸、表面金属化的高分子泡沫中的至少一种。
在一种实施方式中，例如，在所述方法中，所述层间导电膜的厚度为0.01mm-0.2mm。
在一种实施方式中，例如，在所述方法中，所述层间导电Z-pin包括表面金属化的复合材料Z-pin或者金属Z-pin，所述Z-pin扎入两层相邻的所述碳纤维之间的可固化树脂，但又不穿透所述两层相邻的所述碳纤维之间的可固化树脂。
在一种实施方式中，例如，在所述方法中，所述层间导电颗粒包括表面金属化的高分子颗粒、表面金属化的无机晶粒、表面金属化的空心玻璃微珠、金属颗粒，所述表面金属化的高分子颗粒、所述表面金属化的无机晶粒、所述金属颗粒的直径为10μm-50μm；所述表面金属化等空心玻璃微珠的直径为50μm-100μm。
在一种实施方式中，例如，在所述方法中，所述层间导电颗粒包括表面金属化的氧化锌晶须(ZnO Whisker)，所述表面金属化的氧化锌晶须的外形尺寸为50μm-250μm。
在一种实施方式中，例如，在所述方法中，所述可固化树脂包括环氧树脂、乙烯基树脂、双马来酰亚胺、聚酰亚胺、不饱和聚酯、苯并恶嗪。
附图说明
为了更清楚地说明本发明实施例的技术方案，下面将对实施例的附图作简单地介绍，显而易见地，下面描述中的附图仅仅涉及本发明的一些实施例，而非对本发明的限制。
图1是本发明一实施例提供的覆银的聚酯纤维与碳纤维交叉编织的层的外观图；
图2是本发明一实施例提供的表面覆银的尼龙无纺布的SEM照片；
图3是本发明一实施例提供的在层间插入Z-pin的方法流程示意图；
图4是本发明一实施例提供的在环氧预浸料上生长的氧化锌晶须(ZnO Whisker)SEM照片；
图5是本发明一实施例提供的层间散步了氧化锌晶须的层压材料剖面图；
图6是本发明一实施例提供的T300碳纤维平纹织物上印刷的导电银浆 点阵图。
具体实施方式
为使本发明实施例的目的、技术方案和优点更加清楚，下面将结合本发明实施例的附图，对本发明实施例的技术方案进行清楚、完整地描述。显然，所描述的实施例是本发明的一部分实施例，而不是全部的实施例。基于所描述的本发明的实施例，本领域普通技术人员在无需创造性劳动的前提下所获得的所有其他实施例，都属于本发明保护的范围。
除非另作定义，本公开所使用的技术术语或者科学术语应当为本发明所属领域内具有一般技能的人士所理解的通常意义。
由于热固性树脂基层压复合材料的主体结构通常是不导电的高分子材料，因而热固性树脂基层压复合材料的屏蔽电子干扰的能力以及雷击保护能力通常较差。为提高屏蔽电子干扰能力以及雷击保护能力，需要提高热固性树脂基层压复合材料的导电性能，特别是厚度方向上的导电性能。但是，当前已有的技术在提高热固性树脂基层压复合材料的导电性能的同时，往往会损害其抗冲击能力。因此，本公开提供试图提供一种层压复合材料，既可以改善热固性树脂基层压复合材料的导电性能，又能够不损害甚至提高其抗冲击能力。
值得指出，这种厚度方向导电的层压复合材料的面内导电性能和电功传输性能也高于传统的层压复合材料。
实施例1厚度方向导电的层压复合材料，包括与碳纤维交叉编织的导电纤维
制作导电纤维。准备聚酯纤维，在所述聚酯纤维表面气相沉积一层金属银，得到表面覆银(即表面金属化)的聚酯纤维。需要说明的是，作为导电纤维的内部主体材料，并不限于上述的聚酯纤维，其他类似材料例如玻璃纤维、有机纤维、碳纳米管长丝等，都可以使用；表面金属化的方法也不限于上述的气相沉积法，其他方法例如化学镀、刷涂等方法，也可使用；覆盖在上述导电纤维的内部主体材料表面的金属也不限于银，其他的导电金属例如铜、镍等材料也可使用。
将上述得到的覆银的聚酯纤维与T700单向碳纤维织物(东丽产)交叉 编织(又称单向编织)，在垂直于所述覆银的聚酯纤维长度方向上，每10mm包括3根所述覆银的聚酯纤维；所述覆银的聚酯纤维的直径为0.3mm，得到覆银的聚酯纤维与T700碳纤维交叉编织的层，其外观如图1所示。将多层所述覆银的聚酯纤维与T700碳纤维交叉编织的层叠加，由于所述覆银的聚酯纤维表面具有微微凸起的导电接触点，当两层所述覆银的聚酯纤维与T700碳纤维交叉编织的层叠加时，这些接触点相互接触，就构成了厚度方向上的电流通路。用万用表测量两层织物垂直方向的电阻，实测电阻值接近0欧姆。
将8层所述覆银的聚酯纤维与T700碳纤维交叉编织的层叠加，然后将上述叠加的层预浸环氧树脂，加热至120℃固化所述环氧树脂，得到厚度方向导电的层压复合材料。用万用表实测其垂直方向的电阻约为3欧姆。
需要说明的是，所述可固化树脂除环氧树脂外，还可以使用其他可固化树脂如乙烯基树脂、双马来酰亚胺、聚酰亚胺、不饱和聚酯、苯并恶嗪等；上述预浸方法也可采用常规的预浸方法如干法、湿法等。
实施例2厚度方向导电的层压复合材料，包括与碳纤维交叉编织的导电纤维
本实施例制造厚度方向导电的层压复合材料的方法基本与实施例1相同，不同之处在于所述覆银的聚酯纤维的直径和编织密度：在垂直于所述覆银的聚酯纤维长度方向上，每10mm包括4根所述覆银的聚酯纤维；所述覆银的聚酯纤维的直径为0.4mm。用万用表实测最终获得的厚度方向导电的层压复合材料的垂直方向的电阻约为2欧姆。与实施例1相比，由于增加了覆银的聚酯纤维的直径和编织密度，层压复合材料厚度方向上的电流通路更多，因而电阻进一步下降。可以推测，进一步增加所述覆银的聚酯纤维的直径和编织密度，层压复合材料厚度方向上的电阻还将进一步减小。但是，不能无限度地增加所述覆银的聚酯纤维的直径和编织密度，原因在于，过多地使用所述覆银的聚酯纤维会挤压碳纤维的空间，导致碳纤维用量的减少，从而最终影响层压复合材料的强度。通过试验确定，导电纤维使用量的适当范围是：在垂直于所述导电纤维长度方向上，每10mm包括1-5根所述导电纤维；所述导电纤维的直径为0.05mm-0.5mm。
实施例3厚度方向导电的层压复合材料，包括与碳纤维平行编织(又称“面内”编织)的导电纤维
本实施例制造厚度方向导电的层压复合材料的方法基本与实施例1相同，不同之处在于，实施例1使用的是单向碳纤维织物，而本实施例使用的是非单向的碳纤维(平纹)织物(或称面内混编织物)。将导电纤维混杂织入上述非单向的碳纤维(平纹)织物，织入的方式包括束内织入或束间织入等，获得非单向的碳纤维-导电纤维织物。所述束内织入是指将所述导电纤维混杂编织入所述碳纤维束内部(commingling)，即所述导电纤维与所述碳纤维在束内紧密接触；而所述束间织入是指所述导电纤维不编织入所述碳纤维束内部，而是与碳纤维束混杂编织进平纹织物，即所述导电纤维与所述碳纤维并不紧密接触。同样的，所述导电纤维的直径和编织密度决定了最终导电的层压复合材料厚度方向的导电率，用万用表实测最终获得的厚度方向导电的层压复合材料的垂直方向的电阻约为2欧姆。
实施例4厚度方向导电的层压复合材料，包括层间导电膜
制作层间导电膜。所述层间导电膜例如可以是表面金属化的平面材料如：表面金属化的多孔高分子膜、表面金属化的无纺布、表面金属化的织物、表面金属化的纸、表面金属化的高分子泡沫等。例如可以是薄或超薄、超细的多孔金属纤维毡、金属纤维织物或金属泡沫。本实施例制备了表面覆银的尼龙无纺布，其厚度约53μm，面密度约16g/m 2。其中尼龙纤维直径约10-18μm。整个无纺布表面化学覆银，覆银的面密度11.6g/m 2。实测该表面覆银的尼龙无纺布的四方电阻值为0.08Ω，其SEM照片如附图2所示。
将上述得到的表面覆银的尼龙无纺布一一插入T700单向碳纤维织物(东丽产)层间(所谓“插入”，可以是等面积插入，即与碳纤维铺层一样地叠层铺放；或者也可以是选择性地叠层铺放)，将12层所述插入了表面覆银的尼龙无纺布的T700单向碳纤维织物叠加，制成所谓的叠层“预制体”，然后用120℃固化的液态环氧树脂浸渍上述叠层的预制体，即所谓“液态成型”，再加热该环氧树脂至其固化温度，实现固化，最终得到厚度方向导电的层压复合材料。测试其导电率及层间断裂韧性，分别列于下述表1和表2。作为对比，同时还测试了无层间导电膜的层压材料(除了没有插入表面覆银的尼龙无纺布外，其它均与本实施例相同)的导电率和层间断裂韧性，2vol％石墨烯导电改性层压材料(将表面覆银的尼龙无纺布替换为2vol％石墨烯)的导电率。表1中R x是层压材料平面内沿碳纤维方向的导电率，R y是层压材 料平面内垂直于碳纤维方向的导电率，而R z是垂直于层压材料平面(也即厚度方向)的导电率。由表1可见，本实施例的层压材料与无层间导电膜的层压材料相比，R x、R y、R z都大大减小，R y、R z减小得程度尤其明显。从表2可见，本实施例的层压材料与无层间导电膜的层压材料相比，层间断裂韧性大大提升(G IC：I型层间断裂韧性；G IIC：II型层间断裂韧性)。
表1 本实施例、作为对比的无层间导电膜的层压材料以及2vol％石墨烯导电改性层压材料的导电率
Figure PCTCN2018089571-appb-000001
表2 本实施例、作为对比的无层间导电膜的层压材料的层间断裂韧性
Figure PCTCN2018089571-appb-000002
实施例5厚度方向导电的层压复合材料，包括层间导电Z-pin
制作层间导电Z-pin。通常可以用表面金属化的复合材料或者金属材料本身制作Z-pin；Z-pin的形状也可以灵活设计，例如T型销钉或者是带“倒刺”的销钉等，在提高厚度方向上导电率的同时，也加强了力学连接性能。本实施例中采用表面金属化的碳纤维复合材料作为Z-pin，参照附图3所示的过程，将Z-pin扎入相邻的两层碳纤维之间的可固化树脂，但不穿透所述相邻的两层碳纤维之间的可固化树脂。Z-pin的密度影响复合材料厚度方向的导电性，Z-pin的密度越高则复合材料导电性越高；Z-pin的密度也影响复合材料的力学性能，Z-pin密度提高会降低复合材料的面内力学性能。
实施例6厚度方向导电的层压复合材料，包括层间导电颗粒
制作层间导电颗粒。为了提升层压材料厚度方向的导电率，特别是进一步提升导电织物叠层复合材料厚度方向的导电率，还可以在各铺层之间散布导电颗粒。导电颗粒的材料主要是金属化的立体材料如表面金属化的高分子 颗粒、表面金属化的无机晶须等。甚至，可以直接选用本身导电的颗粒，例如金属颗粒。导电颗粒的散布方法不限，例如可以是表面生长、振动筛网撒落等。其中，一个特例是在预浸料表面生长导电的氧化锌(ZnO)晶须。附图4是在碳纤维环氧预浸料(牌号为CCF300/5228)上生长的氧化锌晶须(ZnO Whisker)SEM照片，其中(d)是(c)的局部放大。氧化锌晶须(ZnO Whisker)具有导电性，如果预先对氧化锌晶须(ZnO Whisker)进行金属化处理，其导电率更高。图5是在CCF300/5228环氧复合材料固化后层间剖面，氧化锌晶须清晰可见，这些导电氧化锌不仅电连接了碳纤维铺层，而且强化了层间连接，提高了复合材料的层间韧性。
实施例7厚度方向导电的层压复合材料，包括层间导电颗粒
与实施例6类似的，另一个特例就是导电颗粒在基材表面的图形化均布，例如均匀表面点阵等。这种复合材料的成型可以是液态成型、但特别适合预浸料热压罐成型。显然，导电粒子的面密度将影响该复合材料的导电率、特别是厚度方向的导电率。图6是在T300碳纤维平纹织物上印刷的导电银浆点阵。这种导电化处理的织物可以液态成型导电复合材料，实测这种复合材料厚度方向的导电率约为10S/cm。
实施例8厚度方向导电的层压复合材料，同时包括导电纤维和层间导电膜
步骤1)与实施例1类似，但采用玻璃纤维表面气相沉积一层金属银，得到表面覆银的导电纤维，其直径为0.01mm。将该表面覆银的导电纤维作为纬纱，与国产T300单向碳纤维(山东威海光威)编织成导电的单向纤维布。在垂直于所述表面覆银的导电纤维长度方向上，每10mm包括5根所述表面覆银的导电纤维。
步骤2)与实施例6类似，采用表面覆银的尼龙无纺布作为导电膜，其厚度约30μm，面密度约9g/m 2，其中尼龙纤维直径约10-15μm，覆银后的导电膜面密度10g/m 2。
将上述步骤1所得的导电的单向纤维布与上述步骤2所得的导电膜一层一层交替地铺放，即一层导电膜、一层导电的单向纤维布，一层导电膜、一层导电的单向纤维布，一层导电膜、一层导电的单向纤维布，如此循环反复，共11次，最后，再以导电膜作为最外层，得到导电复合材料预制体(共12 层导电膜，11层导电的单向纤维布，交替铺层，最外层两个面均为导电膜)。
将上述的导电复合材料预制体置入金属闭合模具，控制碳纤维体积分数约50％，用180℃固化的液态环氧树脂液态成型、固化，最终得到厚度方向导电的层压复合材料。测试其厚度方向导电率高达约150S/m，G IC高达约1000J/m 2，G IIC高达约2500J/m 2。本实施例结合了实施例1的“与碳纤维编织在一起的导电纤维”以及实施例6的“层间导电膜”，最终得到的产品的厚度方向的导电率比实施例1、6都要高，并且层间断裂韧性(G IC：I型层间断裂韧性；G IIC：II型层间断裂韧性)与实施例1、6相比也都有提高。
以上所述仅是本发明的示范性实施方式，而非用于限制本发明的保护范围，本发明的保护范围由所附的权利要求确定。

Claims (28)

  1. 一种厚度方向导电的层压复合材料，所述厚度方向导电的层压复合材料包括：层叠的多层碳纤维、处于所述多层碳纤维之间、包覆所述多层碳纤维并将所述多层碳纤维粘接为一体的可固化树脂、以及导电材料，所述导电材料包括以下的至少一种：与所述碳纤维编织在一起的导电纤维；层间导电膜；层间导电Z-pin；以及层间导电颗粒，所述碳纤维占所述厚度方向导电的层压复合材料的体积百分比≥40vol％。
  2. 根据权利要求1所述的厚度方向导电的层压复合材料，其中，在所述层叠的多层碳纤维的每一层中，所述导电纤维与所述碳纤维交叉编织和/或平行编织。
  3. 根据权利要求2所述的厚度方向导电的层压复合材料，其中，所述导电纤维与所述碳纤维交叉编织；在垂直于所述导电纤维长度方向上，每10mm包括1-5根所述导电纤维；所述导电纤维的直径为0.005mm-0.5mm。
  4. 根据权利要求3所述的厚度方向导电的层压复合材料，其中，在垂直于所述导电纤维长度方向上，每10mm包括3根所述导电纤维；所述导电纤维的直径为0.01mm-0.3mm。
  5. 根据权利要求2所述的厚度方向导电的层压复合材料，其中，所述导电纤维与所述碳纤维平行编织；所述平行编织包括束内编织和或束间编织；在垂直于所述导电纤维长度方向上，每10mm包括1-5根所述导电纤维；所述导电纤维的直径为0.05mm-0.5mm。
  6. 根据权利要求5所述的厚度方向导电的层压复合材料，其中，在垂直于所述导电纤维长度方向上，每10mm包括3根所述导电纤维；所述导电纤维的直径为0.01mm-0.3mm。
  7. 根据权利要求1-6的任一项所述的厚度方向导电的层压复合材料，其中，所述导电纤维包括表面金属化的玻璃纤维、表面金属化的有机纤维、表面金属化的碳纳米管纱线、以及超细金属纤维中的至少一种。
  8. 根据权利要求1所述的厚度方向导电的层压复合材料，其中，所述层间导电膜包括：表面金属化的多孔高分子膜、表面金属化的无纺布、表面金属化的织物、表面金属化的纸、表面金属化的高分子泡沫中的至少一种。
  9. 根据权利要求1或8所述的厚度方向导电的层压复合材料，其中，所述层间导电膜的厚度为0.01mm-0.2mm。
  10. 根据权利要求1所述的厚度方向导电的层压复合材料，其中，所述层间导电Z-pin包括表面金属化的复合材料Z-pin或者金属Z-pin，所述Z-pin扎入两层相邻的所述碳纤维之间的可固化树脂，但又不穿透所述两层相邻的所述碳纤维之间的可固化树脂。
  11. 根据权利要求1所述的厚度方向导电的层压复合材料，其中，所述层间导电颗粒包括表面金属化的高分子颗粒、表面金属化的无机晶粒、表面金属化的空心玻璃微珠、金属颗粒，所述表面金属化的高分子颗粒、所述表面金属化的无机晶粒、所述金属颗粒的直径为10μm-50μm；所述表面金属化等空心玻璃微珠的直径为50μm-100μm。
  12. 根据权利要求11所述的厚度方向导电的层压复合材料，其中，所述层间导电颗粒包括表面金属化的氧化锌晶须(ZnO Whisker)，所述表面金属化的氧化锌晶须的外形尺寸为50μm-250μm。
  13. 根据权利要求1所述的厚度方向导电的层压复合材料，其中，所述导电材料包括：与所述碳纤维编织在一起的导电纤维和层间导电膜。
  14. 根据权利要求1-13的任一项所述的厚度方向导电的层压复合材料，其中，所述可固化树脂包括环氧树脂、乙烯基树脂、双马来酰亚胺、聚酰亚胺、不饱和聚酯、苯并恶嗪。
  15. 一种厚度方向导电的层压复合材料的制造方法，包括：
    1)将多层碳纤维叠层铺放，得到层叠的多层碳纤维；
    2)将所述层叠的多层碳纤维预浸可固化树脂，得到层叠的多层碳纤维预浸料；
    3)固化所述可固化树脂，在最终获得的厚度方向导电的层压复合材料中，所述碳纤维占所述厚度方向导电的层压复合材料的体积百分比≥40vol％；
    其中，所述方法还包括设置导电材料的步骤；
    所述设置导电材料的步骤包括以下至少之一：
    在所述步骤1)之前，将导电纤维与所述碳纤维相互编织；在所述步骤1)之后、所述步骤2)之前，或者所述步骤2)之后、所述步骤3)之前，插入层间导电膜；在所述步骤2)之后、所述步骤3)之前，设置层间导电Z-pin； 在所述步骤1)之后、所述步骤2)之前，或者所述步骤2)之后、所述步骤3)之前，加入层间导电颗粒。
  16. 根据权利要求15所述的方法，其中，所述设置导电材料的步骤包括：在所述步骤1)之前，将导电纤维与所述碳纤维相互编织；和在所述步骤1)之后、所述步骤2)之前，或者所述步骤2)之后、所述步骤3)之前，插入层间导电膜。
  17. 根据权利要求15或16所述的方法，其中，在所述层叠的多层碳纤维的每一层中，所述导电纤维与所述碳纤维交叉编织和/或平行编织。
  18. 根据权利要求17所述的方法，其中，所述导电纤维与所述碳纤维交叉编织；在垂直于所述导电纤维长度方向上，每10mm包括1-5根所述导电纤维；所述导电纤维的直径为0.005mm-0.5mm。
  19. 根据权利要求18所述的方法，其中，在垂直于所述导电纤维长度方向上，每10mm包括3根所述导电纤维；所述导电纤维的直径为0.1mm-0.3mm。
  20. 根据权利要求17所述的方法，其中，所述导电纤维与所述碳纤维平行编织；所述平行编织包括束内编织和或束间编织；在垂直于所述导电纤维长度方向上，每10mm包括1-5根所述导电纤维；所述导电纤维的直径为0.005mm-0.5mm。
  21. 根据权利要求20所述的方法，其中，在垂直于所述导电纤维长度方向上，每10mm包括3根所述导电纤维；所述导电纤维的直径为0.01mm-0.3mm。
  22. 根据权利要求15-21的任一项所述的方法，其中，所述导电纤维包括表面金属化的玻璃纤维、表面金属化的有机纤维、表面金属化的碳纳米管纱线、以及超细金属纤维中的至少一种。
  23. 根据权利要求15所述的方法，其中，所述层间导电膜包括：表面金属化的多孔高分子膜、表面金属化的无纺布、表面金属化的织物、表面金属化的纸、表面金属化的高分子泡沫中的至少一种。
  24. 根据权利要求15或23所述的方法，其中，所述层间导电膜的厚度为0.01mm-0.2mm。
  25. 根据权利要求15所述的方法，其中，所述层间导电Z-pin包括表面 金属化的复合材料Z-pin或者金属Z-pin，所述Z-pin扎入两层相邻的所述碳纤维之间的可固化树脂，但又不穿透所述两层相邻的所述碳纤维之间的可固化树脂。
  26. 根据权利要求15所述的方法，其中，所述层间导电颗粒包括表面金属化的高分子颗粒、表面金属化的无机晶粒、表面金属化的空心玻璃微珠、金属颗粒，所述表面金属化的高分子颗粒、所述表面金属化的无机晶粒、所述金属颗粒的直径为10μm-50μm；所述表面金属化等空心玻璃微珠的直径为50μm-100μm。
  27. 根据权利要求15所述的方法，其中，所述层间导电颗粒包括表面金属化的氧化锌晶须(ZnO Whisker)，所述表面金属化的氧化锌晶须的外形尺寸为50μm-250μm。
  28. 根据权利要求15-27的任一项所述的方法，其中，所述可固化树脂包括环氧树脂、乙烯基树脂、双马来酰亚胺、聚酰亚胺、不饱和聚酯、苯并恶嗪。
PCT/CN2018/089571 2018-06-01 2018-06-01 厚度方向导电的层压复合材料及其制造方法 WO2019227474A1 (zh)

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