WO2015149384A1 - 一种石墨烯/金属复合板材的制备方法 - Google Patents

一种石墨烯/金属复合板材的制备方法 Download PDF

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WO2015149384A1
WO2015149384A1 PCT/CN2014/075217 CN2014075217W WO2015149384A1 WO 2015149384 A1 WO2015149384 A1 WO 2015149384A1 CN 2014075217 W CN2014075217 W CN 2014075217W WO 2015149384 A1 WO2015149384 A1 WO 2015149384A1
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graphene
polyvinyl alcohol
metal
prepare
mixed slurry
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PCT/CN2014/075217
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English (en)
French (fr)
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燕绍九
杨程
洪起虎
刘大博
戴圣龙
林左鸣
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中国航空工业集团公司北京航空材料研究院
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Application filed by 中国航空工业集团公司北京航空材料研究院 filed Critical 中国航空工业集团公司北京航空材料研究院
Priority to GB1618613.2A priority Critical patent/GB2544645B/en
Publication of WO2015149384A1 publication Critical patent/WO2015149384A1/zh
Priority to US15/281,790 priority patent/US9878528B2/en

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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F41—WEAPONS
    • F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
    • F41H5/00—Armour; Armour plates
    • F41H5/02—Plate construction
    • F41H5/04—Plate construction composed of more than one layer
    • F41H5/0442—Layered armour containing metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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    • B32B9/005—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile
    • B32B9/007—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising one layer of ceramic material, e.g. porcelain, ceramic tile comprising carbon, e.g. graphite, composite carbon
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    • B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
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    • B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0036—Heat treatment
    • B32B38/004—Heat treatment by physically contacting the layers, e.g. by the use of heated platens or rollers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • B32B9/04—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B9/041—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00 comprising such particular substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material of metal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/194—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • B05D2202/25—Metallic substrate based on light metals based on Al
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/30—Change of the surface
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    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure

Definitions

  • the invention relates to a method for preparing a graphene/metal composite board, and belongs to the technical field of composite materials.
  • Graphene is a new type of two-dimensional nanomaterial with a strength of up to l. OlTpa, which is 100 times that of structural steel and a density of 1/5 of structural steel. Under the background that traditional methods have been difficult to increase the strength of metal materials, graphene has become another important direction for reinforced metal materials.
  • Graphene is a monolayer or a molecular layer of a sheet-like structure with a length ranging from 20 ⁇ m to 50 ⁇ m.
  • the main preparation methods are physical methods and chemical methods. Currently, a large number of graphenes are prepared by chemical methods on the market. Due to the low density of graphene, the strength of the metal material is increased while the density of the material is lowered.
  • graphene also has excellent properties such as ultra-high electron mobility (200,000 cm2/V ⁇ S), electrical conductivity, thermal conductivity (5000 W/m ⁇ K), and Young's modulus (l lOOGPa), so the graphene composite
  • metal materials such as aluminum, titanium, and magnesium, it is expected that a composite material having a light weight, high strength, and a combination of structural functions such as electrical conductivity and heat conduction can be obtained.
  • the invention provides a method for preparing a graphene/metal composite board according to the above prior art situation, which adopts a slurry method to prepare a high-strength graphene composite metal sheet, and the graphene slurry is sprayed by a spraying process. Coating on the surface of the metal sheet, and then preparing a high-strength graphene composite sheet by a hot rolling process, the high-strength Graphene composite sheets have excellent engineering application prospects in light armor materials, aviation and aerospace.
  • the method for preparing the graphene/metal composite sheet is characterized in that: the method is:
  • the graphene/polyvinyl alcohol mixed slurry is applied to the upper and lower surfaces of the metal sheet by spraying, and the thickness of the coating layer is greater than 100 ⁇ m;
  • the graphene metal sheets obtained by the step (6) are bonded together to form a graphene composite metal sheet by hot rolling.
  • the hot rolling method allows the graphene to be uniformly dispersed into the matrix of the metal sheet, which significantly increases the strength of the sheet metal.
  • the method adopts ultrasonic vibration to prepare a monodisperse graphene homogeneous solution, and then mixes monodisperse graphene with a polyvinyl alcohol solution to prepare graphene/polyethylene.
  • the alcohol mixed slurry is composited with a metal plate by using a graphene/polyvinyl alcohol mixed slurry, and the dispersibility of the graphene can be ensured;
  • the graphene composite sheet is prepared by stacking, which is beneficial to the uniform dispersion of graphene into the substrate of the sheet, and exerts the reinforcing effect of graphene;
  • graphene has better toughness than reinforcing materials such as SiC.
  • Graphene can also have a lubricating effect during rolling, which is beneficial to roll forming of metal;
  • the present invention achieves molecular bonding of graphene and a metal plate, and can better retain the intrinsic physical properties of graphene and metal materials;
  • the process of the invention is simple, easy to realize the preparation of large-scale and large-sized graphene composite plates, and reduces the production cost, and has excellent engineering application prospects in the fields of light armor materials, aviation and aerospace.
  • Embodiment 1 Embodiment 1
  • the graphene aluminum alloy sheet obtained by the step (6) is subjected to hot rolling at a hot rolling temperature of 440 ° C to 480 ° C to prepare a graphene composite aluminum alloy sheet.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Nanotechnology (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Fluid Mechanics (AREA)

Abstract

一种石墨烯/金属复合板材的制备方法，首先将单分散的石墨烯溶液与聚乙烯醇溶液均匀混合制备出石墨烯/聚乙烯醇混合浆料，然后通过喷涂的方式将石墨烯/聚乙烯醇混合浆料喷涂到金属板材的上、下表面，之后加热去除涂层中的聚乙烯醇，最后将多块金属板材叠加后采用热轧的方式制备出石墨烯复合板材。通过使用石墨烯/聚乙烯醇混合浆料与金属板材复合，石墨烯的分散性可以得到保证，之后采用热轧的工艺有利于石墨烯均匀地分散到板材基体中，发挥石墨烯的强化效果。所述方法能够在较好地保留石墨烯和金属材料本征物性的前提下实现了石墨烯与金属板材的分子结合，而且工艺简单，易于实现大批量大尺寸的石墨烯复合板材的制备，降低生产成本，在轻质装甲材料及航空、航天等领域均具有优异的工程应用前景。

Description

一种石墨烯 /金属复合板材的制备方法
技术领域
本发明是一种石墨烯 /金属复合板材的制备方法，属于复合材料 技术领域。
技术背景
石墨烯是一种新型二维纳米材料， 其强度高达 l. OlTpa, 是结 构钢的 100倍， 而密度却是结构钢的 1/5。在传统的工艺方法已很难 提高金属材料强度的背景下， 石墨烯成为了增强金属材料的又一重 要方向。 石墨烯为单分子层或几个分子层的片状结构，长度范围在 20μηι〜50μηι之间，主要的制备方法有物理法和化学法，目前市场上普 遍采用化学法制备大批量的石墨烯。 由于石墨烯密度小， 提高金属 材料强度的同时还能降低材料的密度。 同时石墨烯还具有超高的电 子迁移率 ( 200000cm2/V · S ) 、 电导率、 热导率（5000W/m · K)、 杨 氏模量 （l lOOGPa) 等优异性能， 因此将石墨烯复合到铝、 钛、 镁等 金属材料中， 预期可以得到轻质高强、 兼备导电、 导热等功能特性 的结构功能一体化的复合材料。
由于石墨烯与金属材料之间的性质差异很大， 导致石墨烯与金 属基体材料很难复合成型， 对现有技术文件检索发现， 国内外的石 墨烯增强金属基复合材料主要采用的是将石墨烯粉末与金属粉末混 合， 采用粉末冶金的工艺制备石墨烯增强材料。 而关于利用石墨烯 浆料制备石墨烯复合金属板材方面的报道却没有。
发明内容
本发明正是针对上述现有技术状况而设计提供了一种石墨烯 / 金属复合板材的制备方法， 该方法采用浆料法制备高强度石墨烯复 合金属板材， 通过喷涂的工艺将石墨烯浆料涂覆在金属板材表面， 之后通过热轧的工艺制备高强度的石墨烯复合板材， 这种高强度的 石墨烯复合板材在轻质装甲材料及航空、 航天等领域均具有优异的 工程应用前景。
本发明的目的是通过以下技术方案来实现的：
该种石墨烯 /金属复合板材的制备方法， 其特征在于： 该方法的 歩骤是：
(1) 将 50g的聚乙烯醇加入到 450ml蒸馏水中， 加热到 100°C， 采用机械搅拌， 配置聚乙烯醇溶液；
(2) 将 25g石墨烯加入到 475ml蒸馏水中，利用超声细胞粉碎仪 制备出石墨烯溶液， 超声细胞粉碎仪的工作时间超过 30分钟；
(3) 将歩骤 (1)配置的聚乙烯醇溶液与歩骤 (2)制备出的石墨烯溶 液均匀混合， 形成石墨烯 /聚乙烯醇混合浆料；
(4) 将金属板材进行表面活化处理后，采用喷涂的方式将石墨烯 /聚乙烯醇混合浆料涂覆到金属板材的上、 下表面， 涂层的厚度大于 100μ m;
(5) 采用真空烧结的方式或着在氩气的保护气氛下去除金属板 材表面涂层中的聚乙烯醇， 真空烧结的温度为 500°C， 得到石墨烯金 属板材；
(6) 将不少于两块的石墨烯金属板材上、下面互相贴合叠加在一 起后， 采用热等静压的方式使金属板材粘结到一起；
(7) 对歩骤 (6)得到的多层粘结在一起的石墨烯金属板材进行热 轧， 制备出石墨烯复合金属板材。 热轧的方式可以使石墨烯均匀的 分散到金属板材的基体中， 显著提高金属板材的强度。
本发明具有的优点和有益效果是：
第一， 本方法采用超声振荡的方式制备出单分散石墨烯均匀溶 液， 之后将单分散石墨烯与聚乙烯醇溶液混合制备出石墨烯 /聚乙烯 醇混合浆料， 使用石墨烯 /聚乙烯醇混合浆料与金属板材复合， 石墨 烯的分散性可以得到保证；
第二， 通过叠轧的方式制备石墨烯复合板材， 有利于石墨烯均 匀的分散到板材基体中， 发挥石墨烯的强化效果；
第三， 石墨烯相比于 SiC等增强材料具有更好的韧性， 在轧制 过程中石墨烯还能具有润滑的效果， 有利于金属的轧制成型；
第四， 本发明实现了石墨烯与金属板材的分子结合， 且能够较 好的保留石墨烯和金属材料的本征物性；
第五， 本发明工艺简单， 易于实现大批量大尺寸的石墨烯复合 板材的制备， 降低生产成本， 在轻质装甲材料及航空、 航天等领域 均具有优异的工程应用前景。
具体实施方式
以下将结合实施例对本发明技术方案作进一歩地详述： 实施例 1
该种石墨烯 /金属复合板材的制备方法的歩骤是：
(1) 将 50g的聚乙烯醇加入到 450ml蒸馏水中， 加热到 100 °C， 采用机械搅拌， 配置聚乙烯醇溶液；
(2) 将 25g石墨烯加入到 475ml蒸馏水中，利用超声细胞粉碎仪 制备出单分散的石墨烯溶液， 超声细胞粉碎仪的工作时间超过 30分 钟；
(3) 将歩骤 (1)配置的聚乙烯醇溶液与歩骤 (2)制备出的石墨烯溶 液均匀混合， 形成石墨烯 /聚乙烯醇混合浆料；
(4) 选择 3〜5块厚度为 lmm〜4mm铝合金板材或者选择 6〜10 块厚度为 lmm〜2mm铝合金板材，将铝合金板材进行表面活化处理后， 去除氧化皮， 清洁干燥， 采用喷涂的方式将石墨烯 /聚乙烯醇混合浆 料涂覆到铝合金板材的上、 下表面， 喷涂分 10次完成， 每次喷涂厚 度约 10μ m， 涂层的总厚度为 100μ ηι〜120μ m ;
(5) 采用真空烧结的方式或着在氩气的保护气氛下去除铝合金 板材表面涂层中的聚乙烯醇， 真空烧结的温度为 500°C， 得到石墨烯 铝合金板材；
(6) 将多块石墨烯铝合金板材上、 下面互相贴合叠加在一起后， 采用热等静压的方式使铝合金板材粘结到一起， 热等静压的温度为 480°C， 压力为 l lOMpa, 时间为 2小时；
(7) 对歩骤 (6)得到的多层粘结在一起的石墨烯铝合金板材进行 热轧， 热轧温度为 440°C〜480°C， 制备出石墨烯复合铝合金板材。

Claims

权 利 要 求 书
1. 一种石墨烯 /金属复合板材的制备方法， 其特征在于： 该方 法的歩骤是：
(1) 将 50g的聚乙烯醇加入到 450ml蒸馏水中， 加热到 100°C， 采用机械搅拌， 配置聚乙烯醇溶液；
(2) 将 25g石墨烯加入到 475ml蒸馏水中，利用超声细胞粉碎仪 制备出石墨烯溶液， 超声细胞粉碎仪的工作时间超过 30分钟；
(3) 将歩骤 (1)配置的聚乙烯醇溶液与歩骤 (2)制备出的石墨烯溶 液均匀混合， 形成石墨烯 /聚乙烯醇混合浆料；
(4) 将金属板材进行表面活化处理后，采用喷涂的方式将石墨烯 /聚乙烯醇混合浆料涂覆到金属板材的上、 下表面， 涂层的厚度大于 100μ m;
(5) 采用真空烧结的方式或着在氩气的保护气氛下去除金属板 材表面涂层中的聚乙烯醇， 真空烧结的温度为 500°C， 得到石墨烯金 属板材；
(6) 将不少于两块的石墨烯金属板材上、下面互相贴合叠加在一 起后， 采用热等静压的方式使金属板材粘结到一起；
(7) 对歩骤 (6)得到的多层粘结在一起的石墨烯金属板材进行热 轧， 制备出石墨烯复合金属板材。
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