CN100528419C - Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid - Google Patents
Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid Download PDFInfo
- Publication number
- CN100528419C CN100528419C CNB2008100330097A CN200810033009A CN100528419C CN 100528419 C CN100528419 C CN 100528419C CN B2008100330097 A CNB2008100330097 A CN B2008100330097A CN 200810033009 A CN200810033009 A CN 200810033009A CN 100528419 C CN100528419 C CN 100528419C
- Authority
- CN
- China
- Prior art keywords
- metal
- supercritical fluid
- situ
- powder
- cnt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000012530 fluid Substances 0.000 title claims abstract description 23
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 title claims abstract description 20
- 239000011156 metal matrix composite Substances 0.000 title claims abstract description 13
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- 239000000843 powder Substances 0.000 claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 9
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 229910045601 alloy Inorganic materials 0.000 claims description 5
- 239000000956 alloy Substances 0.000 claims description 5
- 238000000280 densification Methods 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000007731 hot pressing Methods 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 239000002905 metal composite material Substances 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 150000003624 transition metals Chemical group 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 239000004411 aluminium Substances 0.000 claims 2
- 229910000838 Al alloy Inorganic materials 0.000 claims 1
- 239000004215 Carbon black (E152) Substances 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 239000005022 packaging material Substances 0.000 claims 1
- 150000002739 metals Chemical class 0.000 abstract description 6
- 238000004663 powder metallurgy Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000003825 pressing Methods 0.000 abstract description 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 2
- 229910001250 2024 aluminium alloy Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- -1 electrodeposition Chemical compound 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明公开了一种超临界流体原位制备碳纳米管增强金属基复合材料的方法。本发明将碳源物质、催化剂和金属粉末加入到反应容器中,通过加热加压使碳源物质在400℃-600℃和5MPa-20MPa条件下形成超临界流体,并在金属粉末表面原位生成碳纳米管,得到碳纳米管与金属的复合粉末,然后再用粉末冶金方法制备碳纳米管增强金属基复合材料。本发明的方法可使碳纳米管在金属基复合材料中均匀分散,并且环境友好、简单高效,适用于批量生产。The invention discloses a method for in-situ preparation of a carbon nanotube-reinforced metal matrix composite material by a supercritical fluid. In the present invention, the carbon source material, catalyst and metal powder are added into the reaction vessel, and the carbon source material forms a supercritical fluid under the conditions of 400°C-600°C and 5MPa-20MPa by heating and pressing, and generates in situ on the surface of the metal powder Carbon nanotubes, composite powders of carbon nanotubes and metals are obtained, and then carbon nanotube-reinforced metal matrix composites are prepared by powder metallurgy. The method of the invention can uniformly disperse the carbon nanotubes in the metal matrix composite material, is environmentally friendly, simple and efficient, and is suitable for mass production.
Description
技术领域 technical field
本发明涉及一种复合材料技术领域的制备方法,具体是一种超临界流体原位制备碳纳米管增强金属基复合材料的方法。The invention relates to a preparation method in the technical field of composite materials, in particular to a method for in-situ preparation of carbon nanotube-reinforced metal matrix composite materials by supercritical fluid.
背景技术 Background technique
碳纳米管具有较小的密度和优异的力学、电学、热学等性能,是金属基复合材料中理想的强化相。但是由于碳纳米管之间存在很强的范德华力,极易产生团聚,导致碳纳米管在复合材料中很难均匀分散;正是这个原因,粉末冶金、搅拌铸造、无压渗透等传统方法制备的碳纳米管增强金属基复合材料,其性能远未达到预期的效果。另一方面,原位复合似乎可以解决碳纳米管分散的难题,这包括两个方面:其一,在碳纳米管存在的条件下原位生成金属,如电沉积、化学沉积等方法;其二,在金属存在的条件下原位生成碳纳米管,例如,经过对现有技术的文献检索发现,中国发明专利“气相沉积原位反应制备碳纳米管增强铝基复合材料的方法”(公开号CN 1730688A),该专利采用化学气相沉积的方法在金属粉末上原位制备碳纳米管,再利用粉末冶金方法制备碳纳米管增强铝基复合材料。该专利较好地解决了碳纳米管在金属基复合材料中的分散问题,但是设备要求高且工艺复杂,难以大规模应用。Carbon nanotubes have low density and excellent mechanical, electrical, and thermal properties, and are ideal strengthening phases in metal matrix composites. However, due to the strong van der Waals force between carbon nanotubes, it is easy to agglomerate, which makes it difficult to disperse carbon nanotubes uniformly in composite materials; for this reason, traditional methods such as powder metallurgy, stirring casting, and pressure-free infiltration The properties of carbon nanotube-reinforced metal matrix composites are far from the expected results. On the other hand, in-situ recombination seems to be able to solve the problem of carbon nanotube dispersion, which includes two aspects: first, in-situ generation of metals in the presence of carbon nanotubes, such as electrodeposition, chemical deposition and other methods; second , in-situ generation of carbon nanotubes in the presence of metals, for example, after searching the literature of the prior art, it was found that the Chinese invention patent "Method for preparing carbon nanotube-reinforced aluminum matrix composites by vapor deposition in-situ reaction" (publication number CN 1730688A), this patent adopts the method of chemical vapor deposition to prepare carbon nanotubes in situ on metal powder, and then utilizes powder metallurgy method to prepare carbon nanotubes reinforced aluminum-based composite materials. This patent better solves the problem of the dispersion of carbon nanotubes in metal matrix composites, but the equipment requirements are high and the process is complicated, making it difficult to apply on a large scale.
发明内容 Contents of the invention
本发明的目的在于针对现有技术的不足,提供一种简单、高效,具有规模化应用潜力的超临界流体原位制备碳纳米管增强金属基复合材料的方法。本发明借助超临界流体的独特性质显著促进原位生成碳纳米管的速率和纯度,获得碳纳米管均匀分散的金属基复合材料。The purpose of the present invention is to provide a method for preparing carbon nanotube-reinforced metal-matrix composite materials in situ with supercritical fluids that is simple, efficient, and has potential for large-scale application. The invention significantly promotes the rate and purity of the in-situ generation of carbon nanotubes by virtue of the unique properties of the supercritical fluid, and obtains a metal-based composite material in which the carbon nanotubes are uniformly dispersed.
本发明是通过以下技术方案实现的,本发明采用超临界流体技术在金属粉末表面原位生成碳纳米管,得到碳纳米管与金属的复合粉末后,再采用粉末冶金技术致密化处理得到碳纳米管增强金属复合材料。The present invention is achieved through the following technical solutions. The present invention uses supercritical fluid technology to generate carbon nanotubes in situ on the surface of metal powder, and after obtaining composite powder of carbon nanotubes and metals, adopts powder metallurgy technology to densify to obtain carbon nanotubes. Tube reinforced metal composites.
本发明方法包括以下步骤:The inventive method comprises the following steps:
(1)将碳源物质、催化剂和金属粉末的混合物加入到反应容器中,其中所述的碳源物质与金属粉末的摩尔比为0.1-3.0,所述的催化剂与金属粉末的摩尔比为0.01-0.1,通过加热加压使温度、压力分别达到400℃-600℃和5MPa-20MPa,使所述的碳源物质处于超临界流体状态并在金属粉末表面原位反应生成碳纳米管,待反应完成后分离固形物进行干燥,即得到碳纳米管与金属的复合粉末;(1) Add the mixture of carbon source material, catalyst and metal powder into the reaction vessel, wherein the molar ratio of the carbon source material to the metal powder is 0.1-3.0, and the molar ratio of the catalyst to the metal powder is 0.01 -0.1, through heating and pressurizing, the temperature and pressure reach 400°C-600°C and 5MPa-20MPa, respectively, so that the carbon source material is in a supercritical fluid state and reacts in situ on the surface of the metal powder to form carbon nanotubes, to be reacted After the completion, the solids are separated and dried to obtain a composite powder of carbon nanotubes and metals;
(2)将上一步所得复合粉末冷压成块体;(2) cold pressing the composite powder obtained in the previous step into a block;
(3)再对上一步所得块体进行致密化处理得到碳纳米管增强金属基复合材料。(3) Densifying the block obtained in the previous step to obtain a carbon nanotube-reinforced metal matrix composite.
所述致密化处理,是指在350℃-550℃、1000MPa-1500MPa下进行热压处理。The densification treatment refers to hot-pressing treatment at 350°C-550°C and 1000MPa-1500MPa.
本发明的主要步骤在耐热耐压的反应器中进行,以烃、醇、醚、酮、醛、酚中的一至多种化合物作为碳源物质,以过渡金属及其合金或化合物为催化剂,在超过所述碳源物质的临界温度和临界压力的条件下发生催化热解反应,在铝、铜、镁、钛等金属及其合金的粉末表面原位生成碳纳米管。The main steps of the present invention are carried out in a heat-resistant and pressure-resistant reactor, using one or more compounds in hydrocarbons, alcohols, ethers, ketones, aldehydes, and phenols as carbon source materials, and using transition metals and their alloys or compounds as catalysts, Catalytic pyrolysis reaction occurs under the condition of exceeding the critical temperature and critical pressure of the carbon source material, and carbon nanotubes are generated in situ on the powder surface of aluminum, copper, magnesium, titanium and other metals and their alloys.
本发明通过加热加压使碳源物质形成超临界流体,使碳纳米管的生成反应在超临界流体状态下进行。所谓超临界流体是指在临界温度和临界压力以上的流体,在超临界流体中气液两相性质非常接近,以至于无法分辨。本发明借助超临界流体超常的扩散和溶剂化能力,促进碳纳米管的生成速率和产率,从而提高金属基复合材料中原位碳纳米管的含量。In the invention, the carbon source material is heated and pressurized to form a supercritical fluid, so that the generation reaction of the carbon nanotube is carried out in the state of the supercritical fluid. The so-called supercritical fluid refers to the fluid above the critical temperature and critical pressure. In the supercritical fluid, the gas-liquid two-phase properties are so close that they cannot be distinguished. The invention promotes the generation rate and yield of carbon nanotubes by virtue of the extraordinary diffusion and solvation capabilities of the supercritical fluid, thereby increasing the content of the in-situ carbon nanotubes in the metal matrix composite material.
与现有技术相比,本发明具有以下优点:超临界流体是一种绿色环保的新技术,用以生成碳纳米管的反应条件温和、速度快,且设备工艺简便易行,因此本发明的方法适用于大批量制备碳纳米管原位增强金属基复合材料,且所得复合材料中碳纳米管分散均匀、含量可在0.1%-10%的范围内进行调控。Compared with the prior art, the present invention has the following advantages: supercritical fluid is a green and environmentally friendly new technology, the reaction conditions for generating carbon nanotubes are mild, the speed is fast, and the equipment and process are simple and easy, so the present invention The method is suitable for mass production of carbon nanotube in-situ reinforced metal matrix composite materials, and the carbon nanotubes in the obtained composite material are evenly dispersed and the content can be regulated within the range of 0.1%-10%.
具体实施方式 Detailed ways
下面结合实施例对本发明作详细说明,这些实施例是以本发明技术方案为前提,给出了详细的实施方式和具体的操作过程,但本发明的保护范围不限于下述的实施例。The present invention is described in detail below in conjunction with embodiment, these embodiments are based on the premise of the technical solution of the present invention, have provided detailed implementation and specific operation process, but protection scope of the present invention is not limited to following embodiment.
本发明中,所述的金属粉末为铝、铜、镁、钛及其合金粉末中的一至多种。以下实施例中采用的金属粉末均为400目,其中实施例1和实施例2为纯铝粉,实施例3为纯镁粉,实施例4为2024铝合金粉,实施例5为纯铝粉和纯镁粉以20∶1比例的混合粉末。以下实施例中采用五羰基铁作为催化剂,甲苯和乙醇作为碳源物质,其中甲苯的临界温度和临界压力分别为319℃、4.1MPa,乙醇的临界温度和临界压力分别为243℃、6.4MPa。In the present invention, the metal powder is one or more of aluminum, copper, magnesium, titanium and alloy powders thereof. The metal powders adopted in the following examples are all 400 mesh, wherein embodiment 1 and embodiment 2 are pure aluminum powder, embodiment 3 is pure magnesium powder, embodiment 4 is 2024 aluminum alloy powder, embodiment 5 is pure aluminum powder Mix powder with pure magnesium powder at a ratio of 20:1. In the following examples, iron pentacarbonyl is used as a catalyst, and toluene and ethanol are used as carbon sources, wherein the critical temperature and critical pressure of toluene are 319° C. and 4.1 MPa respectively, and the critical temperature and critical pressure of ethanol are 243° C. and 6.4 MPa respectively.
以下五个实施例在耐热耐压的反应容器中进行,将甲苯、乙醇、五羰基铁和铝粉加入到反应容器中,其中,甲苯和乙醇加起来与金属粉末的摩尔比为0.1-3.0,五羰基铁与金属粉末的摩尔比为0.01-0.1。通过加热加压使温度、压力分别达到400℃-600℃和5MPa-20Mpa,使甲苯、乙醇在超临界流体状态下反应1h,然后终止加热,待冷却到室温后打开反应容器分离固形物进行干燥即得到碳纳米管和金属复合粉末;先将所得复合粉末冷压成块体,然后在350℃-550℃、1000MPa-1500Mpa下进行热压致密化处理。The following five examples are carried out in a heat-resistant and pressure-resistant reaction vessel. Toluene, ethanol, iron pentacarbonyl and aluminum powder are added to the reaction vessel, wherein the molar ratio of the sum of toluene and ethanol to the metal powder is 0.1-3.0 , the molar ratio of iron pentacarbonyl to metal powder is 0.01-0.1. Make the temperature and pressure reach 400°C-600°C and 5MPa-20Mpa respectively by heating and pressurizing, make toluene and ethanol react in supercritical fluid state for 1 hour, then stop heating, open the reaction vessel to separate the solids for drying after cooling to room temperature The composite powder of carbon nanotube and metal is obtained; firstly, the obtained composite powder is cold-pressed into a block, and then subjected to hot-pressing densification treatment at 350°C-550°C and 1000MPa-1500Mpa.
用扫描电子显微镜和透射电子显微镜表征所得复合材料中碳纳米管的形貌和微观结构,确定所有实施例得到的均为多壁碳纳米管,管径分布在10nm-60nm之间。采用称重法计算所得复合材料中碳纳米管的质量含量,所得数据及相关工艺参数列于表1。Scanning electron microscopy and transmission electron microscopy were used to characterize the morphology and microstructure of the carbon nanotubes in the composite material, and it was determined that all the examples obtained were multi-walled carbon nanotubes with diameters ranging from 10nm to 60nm. The mass content of carbon nanotubes in the composite material was calculated by weighing method, and the obtained data and related process parameters are listed in Table 1.
表1.部分实施例中碳纳米管的质量含量及工艺条件Table 1. Mass content and process conditions of carbon nanotubes in some examples
注:a、b、c分别为甲苯、乙醇、五羰基铁相对于金属粉末的摩尔比。Note: a, b, and c are the molar ratios of toluene, ethanol, and iron pentacarbonyl relative to the metal powder, respectively.
Claims (5)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2008100330097A CN100528419C (en) | 2008-01-24 | 2008-01-24 | Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CNB2008100330097A CN100528419C (en) | 2008-01-24 | 2008-01-24 | Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid |
Publications (2)
Publication Number | Publication Date |
---|---|
CN101234427A CN101234427A (en) | 2008-08-06 |
CN100528419C true CN100528419C (en) | 2009-08-19 |
Family
ID=39918474
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CNB2008100330097A Expired - Fee Related CN100528419C (en) | 2008-01-24 | 2008-01-24 | Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN100528419C (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101818274A (en) * | 2010-04-17 | 2010-09-01 | 上海交通大学 | Preparation method of nanometer carbon-reinforced metal base composite material |
CN102002652B (en) * | 2010-12-08 | 2012-06-27 | 上海交通大学 | Carbon nano tube reinforced metal matrix composite material and in-situ preparation method thereof |
CN103128284B (en) * | 2013-03-15 | 2014-11-05 | 南昌航空大学 | Reinforced method of carbon nanotubes (CNTs) of laser-induced composite fused deposition gradient content for copper matrix composite materials |
CN116002666B (en) * | 2023-01-05 | 2024-06-11 | 青岛科技大学 | Continuous production device and method for in-situ preparation and dispersion integration of carbon nanotubes |
-
2008
- 2008-01-24 CN CNB2008100330097A patent/CN100528419C/en not_active Expired - Fee Related
Non-Patent Citations (2)
Title |
---|
催化剂结构与形态对碳纳米管生长的影响. 雷中兴,刘静,王建波,李轩科,汪厚植.新型炭材料,第18卷第4期. 2003 * |
超临界流体技术在介孔材料制备中的应用. 陈蓓怡,于文利,赵亚平.化工进展,第24卷第5期. 2005 * |
Also Published As
Publication number | Publication date |
---|---|
CN101234427A (en) | 2008-08-06 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN102002652B (en) | Carbon nano tube reinforced metal matrix composite material and in-situ preparation method thereof | |
CN100406596C (en) | Method for preparing carbon nanotube-reinforced aluminum matrix composites by vapor deposition in situ reaction | |
CN103924119B (en) | A kind of super-high heat-conductive graphite flakes/carbon/carbon-copper composite material and preparation method thereof | |
CN102383071B (en) | Method for preparing carbon nano tube enhanced titanium-base compound material by in-suit reaction | |
CN102242303B (en) | In-situ nano TiC ceramic particle reinforced copper based composite material and preparation method thereof | |
CN102260814A (en) | In situ nano TiC ceramic particle reinforced aluminum based composite material and preparation method thereof | |
CN102424919A (en) | Method for preparing carbon nanotube reinforced aluminum-based composite material | |
CN105385871A (en) | Preparing method of multielement nanometer composite strengthening thermal-resisting aluminum matrix composite | |
CN103993192A (en) | Method for reinforcing metal material through graphene | |
CN106521230B (en) | A kind of graphite flakes/carbon/carbon-copper composite material of vertical orientation heat transmission and preparation method thereof | |
CN110157931B (en) | A kind of nano-carbon reinforced metal matrix composite material with three-dimensional network structure and preparation method thereof | |
CN105734382A (en) | Superfine metalloceramics material and preparation method thereof | |
CN100528419C (en) | Method for in situ preparing carbon nano-tube reinforced metal-matrix composite material from supercritical fluid | |
CN101864547A (en) | Preparation method of uniformly dispersed carbon nanotube reinforced aluminum matrix composite | |
CN105218102B (en) | A kind of method that precursor process prepares SiC/TiC composite ceramics | |
CN102808141A (en) | Method for preparing carbon nanotubes reinforced Al-Mg alloy composite materials | |
CN109665848B (en) | A kind of ultra-high temperature SiC-HfB2 composite ceramic and its preparation method and application | |
CN102277533B (en) | In-situ nano TiC ceramic particle reinforced iron matrix composite material and preparation method thereof | |
CN103664194A (en) | Method for preparing non-oxide ceramic ultrafine powder based on solvent thermal polymerization reaction | |
CN109554564B (en) | A kind of preparation method of amorphous alloy particle and carbon nanotube reinforced aluminum matrix composite material | |
CN114713827A (en) | Hard alloy/metal ceramic powder for 3D printing and preparation method thereof | |
CN104131191A (en) | Preparation method of solid solution for pentabasic hard alloy | |
CN109652679B (en) | Carbon nanotube and endogenous nano TiC particle mixed reinforced aluminum-based composite material and preparation method thereof | |
CN106587063A (en) | Method for synthesizing titanium carbide through soft mechanical force chemical auxiliary microwaves | |
CN107116227B (en) | A kind of preparation method of ultrafine WC-Ni composite powder |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C17 | Cessation of patent right | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20090819 Termination date: 20120124 |