CN105364068A - Manufacturing method for three-dimensional graphene in-situ clad-copper composite material - Google Patents
Manufacturing method for three-dimensional graphene in-situ clad-copper composite material Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 68
- 239000010949 copper Substances 0.000 title claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 51
- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 17
- 238000004519 manufacturing process Methods 0.000 title 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 230000009467 reduction Effects 0.000 claims abstract description 28
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 20
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000000498 ball milling Methods 0.000 claims abstract description 14
- 229910052786 argon Inorganic materials 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 8
- 230000001681 protective effect Effects 0.000 claims abstract description 7
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 4
- 150000001879 copper Chemical class 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- 239000010959 steel Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 19
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009825 accumulation Methods 0.000 abstract description 2
- 239000011159 matrix material Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- 238000004663 powder metallurgy Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002674 ointment Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/16—Metallic particles coated with a non-metal
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Abstract
本发明涉及一种三维石墨烯原位包覆铜复合材料的制备方法。将钢球：铜粉：聚甲基丙烯酸甲酯以按质量比150：10:0.1加入球磨罐中，抽真空后充满氩气；经球磨制得铜/聚甲基丙烯酸甲酯粉末；将制得的铜/聚甲基丙烯酸甲酯粉末在管式炉中还原；还原温度设为800℃，还原气氛为氢气，保护性气氛为氩气；还原时间为10min；聚甲基丙烯酸甲酯被催化成石墨烯，由于铜粉堆积的效果，得到原位生长的三维石墨烯包覆铜的复合材料。由于二维石墨烯的平面结构会导致复合材料的各向异性，在力学性能上不能保证各向同性的性能。原位生长的三维石墨烯包覆铜的复合材料，可保证块体复合材料的各向同性性能。
The invention relates to a preparation method of a three-dimensional graphene in-situ coated copper composite material. Put steel ball: copper powder: polymethyl methacrylate into the ball mill tank at a mass ratio of 150:10:0.1, and fill it with argon after vacuuming; the copper/polymethyl methacrylate powder is obtained by ball milling; the prepared The obtained copper/polymethyl methacrylate powder is reduced in a tube furnace; the reduction temperature is set to 800°C, the reducing atmosphere is hydrogen, and the protective atmosphere is argon; the reduction time is 10min; polymethyl methacrylate is catalyzed Graphene, due to the effect of copper powder accumulation, the in-situ grown three-dimensional graphene-coated copper composite material is obtained. Since the planar structure of 2D graphene will lead to anisotropy of composite materials, isotropic performance cannot be guaranteed in terms of mechanical properties. In situ grown three-dimensional graphene-coated copper composites that ensure isotropic properties of bulk composites.
Description
技术领域technical field
本发明涉及一种利用粉末冶金原位合成三维石墨烯包覆铜复合材料的方法，属于粉末冶金技术领域。The invention relates to a method for in-situ synthesis of a three-dimensional graphene-coated copper composite material by using powder metallurgy, and belongs to the technical field of powder metallurgy.
背景技术Background technique
铜是一种导电性、延展性、导热性都很好的材料，广泛应用于电气、机械和国防等工业。美中不足的是，铜材的强度很低，在电子器件(例如PCB板)的应用上由于强度不够高而产生种种问题，例如寿命缩短，易于损坏等。随着社会发展以及能源的紧张，人们对于轻质高强的材料出现了更多的需求，铜基复合材料是一种理想的材料来实现这些要求。在高强度铜材(例如强度可高达1500MPa的铍青铜)的制备上，传统的方法借助于合金化法以及添加第二项颗粒得以实现，但是铜合金强度的提高是建立在导电、导热等性能下降的基础上。复合材料法同样适用于铜材的制备，根据复合材料设计法则(Ec＝(1-f)Em+fEp)，第二相的添加在实现强化效果的同时，还可以克服基体材料的一些不足，从而获得轻质高强的铜材，克服传统方法的不足。Copper is a material with good electrical conductivity, ductility and thermal conductivity, and is widely used in industries such as electrical, mechanical and national defense. The fly in the ointment is that the strength of copper is very low. In the application of electronic devices (such as PCB boards), the strength is not high enough to cause various problems, such as shortened lifespan and easy damage. With the development of society and the shortage of energy sources, people have more demands for lightweight and high-strength materials, and copper-based composite materials are an ideal material to meet these requirements. In the preparation of high-strength copper materials (such as beryllium bronze with a strength of up to 1500MPa), the traditional method is achieved by means of alloying and adding the second particle, but the improvement of the strength of copper alloys is based on electrical and thermal conductivity. drop basis. The composite material method is also applicable to the preparation of copper materials. According to the composite material design rule (Ec=(1-f)Em+fEp), the addition of the second phase can not only achieve the strengthening effect, but also overcome some shortcomings of the matrix material. In order to obtain lightweight and high-strength copper materials, the shortcomings of traditional methods can be overcome.
单层碳原子的石墨烯作为一种新型的材料，除了在能源方面的应用，它具有优良的力学性能，是目前为止发现的最为坚硬的材料。近十年来，用石墨烯作为增强相来实现增强机体材料的研究层出不穷。As a new type of material, graphene with a single layer of carbon atoms has excellent mechanical properties and is the hardest material discovered so far. In the past ten years, there have been endless researches on using graphene as a reinforcing phase to realize enhanced body materials.
目前很多研究着眼于把石墨烯片直接和铜粉进行球磨混合，但是这会造成石墨烯的团聚并对石墨烯造成损伤。这是目前石墨烯增强金属基材料做遇到的瓶颈所在，如何做到石墨烯在金属基体中均匀分散以及结构完好是目前研究的焦点。At present, many studies focus on directly mixing graphene sheets with copper powder, but this will cause graphene agglomeration and damage graphene. This is the current bottleneck in the development of graphene-enhanced metal-based materials. How to achieve uniform dispersion of graphene in the metal matrix and a sound structure is the focus of current research.
在此之前，研究人员利用在铜片上旋涂PMMA薄膜，然后经过还原可制备石墨烯。该项发明采用“短时球磨-退火还原”法作为一种原位合成的方法，可以先将固体碳源在铜粉表面上的均匀分散，由于铜粉堆积的效果，还原催化过程中碳原子在铜粉表面生成三维石墨烯，得到原位生长的三维石墨烯包覆铜的复合材料。与传统在铜片表面原位催化所生长的二维石墨烯有所不同，在复合材料中，由于二维石墨烯的平面结构会导致复合材料的各向异性，在力学性能上不能保证各向同性的性能。Prior to this, researchers used spin-coated PMMA films on copper sheets and then reduced them to prepare graphene. This invention adopts the "short-time ball milling-annealing reduction" method as an in-situ synthesis method, which can firstly disperse the solid carbon source evenly on the surface of the copper powder. Three-dimensional graphene is generated on the surface of copper powder, and a composite material of in-situ grown three-dimensional graphene-coated copper is obtained. Different from the traditional two-dimensional graphene grown by in-situ catalysis on the surface of copper sheets, in composite materials, due to the anisotropy of the composite material due to the planar structure of two-dimensional graphene, the mechanical properties cannot guarantee anisotropy. same-sex performance.
发明内容Contents of the invention
本发明的目的在于提供一种简单易行的粉末冶金原位合成石墨烯/铜复合材料的方法。该方法能够有效克服传统外加石墨烯片所带来的问题，该方法过程简单，所制得复合材料力学性能优良。The object of the present invention is to provide a simple and easy powder metallurgy method for synthesizing graphene/copper composite material in situ. The method can effectively overcome the problems caused by the traditional addition of graphene sheets, the process of the method is simple, and the obtained composite material has excellent mechanical properties.
为实现上述目的，本发明是通过以下技术方案加以实现的，一种原位合成三维石墨烯包覆铜复合材料的方法，其特征包括以下过程：To achieve the above object, the present invention is achieved through the following technical solutions, a method for in-situ synthesis of three-dimensional graphene-coated copper composites, characterized in that it comprises the following processes:
(1)球磨铜粉和聚甲基丙烯酸甲酯：(1) Ball milled copper powder and polymethyl methacrylate:
将钢球：铜粉：聚甲基丙烯酸甲酯以按质量比150：10:0.1加入球磨罐中，抽真空后充满氩气作为保护性气氛；经过球磨，制得分散均匀的铜—聚甲基丙烯酸甲酯粉末；Add steel balls: copper powder: polymethyl methacrylate into the ball mill tank at a mass ratio of 150:10:0.1, and fill it with argon as a protective atmosphere after vacuuming; after ball milling, uniformly dispersed copper-polymethyl methacrylate is obtained. Methyl acrylate powder;
(2)铜—聚甲基丙烯酸甲酯复合粉末的还原(2) Reduction of copper-polymethyl methacrylate composite powder
将步骤(1)制得的铜—聚甲基丙烯酸甲酯复合粉末在管式炉中进行还原处理；还原温度设定在800℃，还原气氛为氢气，保护性气氛为氩气；还原时间为10min；聚甲基丙烯酸甲酯被催化成石墨烯，得到原位生长的三维石墨烯包覆铜的复合材料；The copper-polymethyl methacrylate composite powder that step (1) makes is carried out reduction treatment in tube furnace; Reduction temperature is set at 800 ℃, reduction atmosphere is hydrogen, and protective atmosphere is argon; Reduction time is 10min; polymethyl methacrylate is catalyzed into graphene, and a three-dimensional graphene-coated copper composite material grown in situ is obtained;
优选步骤为：The preferred steps are:
步骤1)球磨条件为400-600转/分；球磨2-4h。Step 1) The ball milling condition is 400-600 rpm; ball milling 2-4h.
步骤2)气体流量设定在100-200ml/min。Step 2) The gas flow rate is set at 100-200ml/min.
本发明具有以下优点：首先直接采用球磨的方式，使固体碳源PMMA在铜片表面实现较为均匀的负载，保证碳源的来源。由于铜粉堆积的效果，还原催化过程中碳原子在铜粉表面生成三维石墨烯，得到原位生长的三维石墨烯包覆铜的复合材料。同时，该法有利于解决石墨烯在铜基体中的分散情况。三维石墨烯原位包覆铜复合材料的制备方法的成功可以同时保证石墨烯与铜基体之间的良好界面，同时能够保证块体复合材料的各向同性性能。原位生长的三维石墨烯/铜基复合材料解决了石墨烯在金属集体中分散的难题，利用球磨法和粉末冶金法原位生长石墨烯，并且实现了对铜基体材料的强化，对于高强铜材在电子器件上的应用有着较好的前景。The invention has the following advantages: firstly, the ball milling method is directly used, so that the solid carbon source PMMA can be loaded evenly on the surface of the copper sheet, and the source of the carbon source can be guaranteed. Due to the effect of copper powder accumulation, carbon atoms generate three-dimensional graphene on the surface of copper powder during the reduction catalysis process, and an in-situ grown three-dimensional graphene-coated copper composite material is obtained. At the same time, this method is beneficial to solve the dispersion of graphene in the copper matrix. The success of the preparation method of 3D graphene in situ-coated copper composites can simultaneously ensure a good interface between graphene and copper matrix, and at the same time can guarantee the isotropic properties of the bulk composites. The three-dimensional graphene/copper-based composite material grown in situ solves the problem of graphene dispersing in metal collectives. Graphene is grown in situ by ball milling and powder metallurgy, and the strengthening of copper matrix materials is realized. For high-strength copper The application of materials in electronic devices has a good prospect.
附图说明Description of drawings
图1为实施例1中球磨过后的扫描照片。Fig. 1 is the scanned photograph after ball milling in embodiment 1.
图2a为实施例1中还原后得到的三维石墨烯包覆铜复合材料的扫描照片。Figure 2a is a scanning photo of the three-dimensional graphene-coated copper composite material obtained after reduction in Example 1.
图2b为实施例1中还原后得到的三维石墨烯包覆铜复合材料的透射照片。Fig. 2b is a transmission photo of the three-dimensional graphene-coated copper composite obtained after reduction in Example 1.
图2c为实施例1中除去还原后得到的三维石墨烯包覆铜复合材料的铜基体后三维石墨烯的透射照片。2c is a transmission photo of three-dimensional graphene after removing the copper matrix of the three-dimensional graphene-coated copper composite material obtained in Example 1 after reduction.
图2d为实施例1中除去还原后得到的三维石墨烯包覆铜复合材料的铜基体后三维石墨烯的透射照片，照片中显示石墨烯的层数为5-6层左右。Figure 2d is a transmission photo of three-dimensional graphene after removing the copper matrix of the three-dimensional graphene-coated copper composite material obtained after reduction in Example 1. The photo shows that the number of layers of graphene is about 5-6.
图2e为实施例1中除去还原后得到的三维石墨烯包覆铜复合材料的铜基体后三维石墨烯的AFM测试结果，测试结果显示石墨烯的厚度约为1.28nm，大约为5层左右的石墨烯。Figure 2e is the AFM test result of three-dimensional graphene after removing the copper matrix of the three-dimensional graphene-coated copper composite material obtained after reduction in Example 1. The test results show that the thickness of graphene is about 1.28nm, which is about 5 layers Graphene.
图2f为实施例1中除去还原后得到的三维石墨烯包覆铜复合材料的铜基体后三维石墨烯的XRD测试结果。其中曲线1和2分别代表石墨烯/铜复合材料和纯铜，除去两条曲线中纯铜的特征峰，1图中11°处的峰为石墨烯的特征峰，证明石墨烯的存在。Fig. 2f is the XRD test result of three-dimensional graphene after removing the copper matrix of the three-dimensional graphene-coated copper composite material obtained after reduction in Example 1. Wherein curves 1 and 2 represent graphene/copper composite material and pure copper respectively, remove the characteristic peak of pure copper in two curves, the peak at 11 ° place in figure 1 is the characteristic peak of graphene, proves the existence of graphene.
具体实施方式detailed description
下面结合实施例进一步说明本发明，这些实施例只用于说明本发明，并不限制本发明。The present invention is further described below in conjunction with examples, and these examples are only for illustrating the present invention, do not limit the present invention.
实施例1：将钢球：铜粉：聚甲基丙烯酸甲酯以按质量(g)比150：10:0.1放入到球磨罐中，充入氩气作为保护气氛。在行星式球磨机中经过低速短时球磨(400-600转/分，球磨2h)。球磨结果如图1所示；球磨后的聚甲基丙烯酸甲酯/铜粉末在管式炉中进行还原处理。还原温度设定在800℃，还原气氛为氢气(气体流量设定在100-200ml/min)，保护性气氛为氩气(气体流量设定在100-200ml/min)。还原时间为10min。还原后得到的三维石墨烯包覆铜复合材料的扫描照片如图2a所示，还原后得到的三维石墨烯包覆铜复合材料的透射照片如图2b所示，除去还原后得到的三维石墨烯包覆铜复合材料的铜基体后三维石墨烯的透射照片如图2c所示，除去还原后得到的三维石墨烯包覆铜复合材料的铜基体后三维石墨烯的透射照片如图2d所示，照片中显示石墨烯的层数为5-6层左右；除去还原后得到的三维石墨烯包覆铜复合材料的铜基体后三维石墨烯的AFM测试结果如图2e所示，测试结果显示石墨烯的厚度约为1.28nm，大约为5层左右的石墨烯；除去还原后得到的三维石墨烯包覆铜复合材料的铜基体后三维石墨烯的XRD测试结果如图2f所示，其中曲线1和2分别代表石墨烯/铜复合材料和纯铜，除去两条曲线中纯铜的特征峰，1图中11°处的峰为石墨烯的特征峰，证明石墨烯的存在。Example 1: Put steel balls: copper powder: polymethyl methacrylate in a mass (g) ratio of 150:10:0.1 into a ball mill jar, and fill it with argon as a protective atmosphere. Go through low-speed short-time ball milling (400-600 rpm, ball milling 2h) in a planetary ball mill. The ball milling results are shown in Figure 1; the polymethyl methacrylate/copper powder after ball milling was subjected to reduction treatment in a tube furnace. The reduction temperature is set at 800°C, the reducing atmosphere is hydrogen (the gas flow is set at 100-200ml/min), and the protective atmosphere is argon (the gas flow is set at 100-200ml/min). The reduction time is 10min. The scanning photo of the three-dimensional graphene-coated copper composite obtained after reduction is shown in Figure 2a, and the transmission photo of the three-dimensional graphene-coated copper composite obtained after reduction is shown in Figure 2b, except for the three-dimensional graphene obtained after reduction The transmission photo of the three-dimensional graphene after the copper matrix of the copper composite material is shown in Figure 2c, and the transmission photo of the three-dimensional graphene after the copper matrix of the three-dimensional graphene-coated copper composite material obtained after removal is shown in Figure 2d. The photo shows that the number of layers of graphene is about 5-6 layers; after removing the copper matrix of the three-dimensional graphene-coated copper composite material obtained after reduction, the AFM test results of three-dimensional graphene are shown in Figure 2e, and the test results show that graphene The thickness of the three-dimensional graphene is about 1.28nm, which is about 5 layers of graphene; the XRD test results of the three-dimensional graphene after removing the copper matrix of the three-dimensional graphene-coated copper composite material obtained after reduction are shown in Figure 2f, where curves 1 and 2 represents the graphene/copper composite material and pure copper respectively. The characteristic peak of pure copper in the two curves is removed, and the peak at 11° in the figure 1 is the characteristic peak of graphene, which proves the existence of graphene.
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| CN106270485A (en) * | 2016-08-18 | 2017-01-04 | 天津大学 | A kind of preparation method of spherical copper powder surface in situ growing three-dimensional Graphene |
| CN106711454A (en) * | 2016-11-28 | 2017-05-24 | 荆门市格林美新材料有限公司 | Preparation method of graphene cladded cobalt powder composite material |
| CN107574326A (en) * | 2017-08-25 | 2018-01-12 | 天津大学 | The method that original position prepares graphene nanometer sheet/copper/aluminium composite material with mud/brick laminated construction |
| CN108145169A (en) * | 2017-11-27 | 2018-06-12 | 中国船舶重工集团公司第七二五研究所 | A kind of high-strength highly-conductive graphene enhancing Cu-base composites and preparation method and application |
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| CN106270485A (en) * | 2016-08-18 | 2017-01-04 | 天津大学 | A kind of preparation method of spherical copper powder surface in situ growing three-dimensional Graphene |
| CN106711454A (en) * | 2016-11-28 | 2017-05-24 | 荆门市格林美新材料有限公司 | Preparation method of graphene cladded cobalt powder composite material |
| CN107574326A (en) * | 2017-08-25 | 2018-01-12 | 天津大学 | The method that original position prepares graphene nanometer sheet/copper/aluminium composite material with mud/brick laminated construction |
| CN108145169A (en) * | 2017-11-27 | 2018-06-12 | 中国船舶重工集团公司第七二五研究所 | A kind of high-strength highly-conductive graphene enhancing Cu-base composites and preparation method and application |
| CN108611511A (en) * | 2018-05-08 | 2018-10-02 | 上海理工大学 | A kind of three-dimensional intercommunication CNTs/Cu composite material and preparation methods |
| CN108611511B (en) * | 2018-05-08 | 2019-08-09 | 上海理工大学 | A kind of three-dimensional intercommunication CNTs/Cu composite material and preparation method |
| CN109694967A (en) * | 2019-01-14 | 2019-04-30 | 广西大学 | A kind of preparation method of copper/graphene composite material |
| CN109694967B (en) * | 2019-01-14 | 2020-12-25 | 广西大学 | Preparation method of copper/graphene composite material |
| CN110358940A (en) * | 2019-07-04 | 2019-10-22 | 天津大学 | 3D printing fabricated in situ three-dimensional grapheme enhances nickel-base composite material preparation method |
| CN113073227A (en) * | 2021-03-25 | 2021-07-06 | 南昌工程学院 | Preparation method of high-conductivity deformed Cu-Fe series in-situ composite material |
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