CN106011700B - 碳化硼‑碳化硅晶须增韧高强度铜基复合材料的制备方法 - Google Patents
碳化硼‑碳化硅晶须增韧高强度铜基复合材料的制备方法 Download PDFInfo
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- 239000010949 copper Substances 0.000 title claims abstract description 55
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 48
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 37
- 230000003014 reinforcing effect Effects 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title abstract description 9
- 229910052580 B4C Inorganic materials 0.000 title abstract 7
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 title abstract 7
- 239000000843 powder Substances 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 28
- 238000011065 in-situ storage Methods 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- 238000007731 hot pressing Methods 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000005245 sintering Methods 0.000 claims abstract description 4
- 239000000470 constituent Substances 0.000 claims abstract description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 30
- 229910052796 boron Inorganic materials 0.000 claims description 30
- 239000000758 substrate Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 229910011255 B2O3 Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229950000845 politef Drugs 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000000498 ball milling Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011812 mixed powder Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910003978 SiClx Inorganic materials 0.000 description 2
- PPWPWBNSKBDSPK-UHFFFAOYSA-N [B].[C] Chemical compound [B].[C] PPWPWBNSKBDSPK-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011797 cavity material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 210000000214 mouth Anatomy 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
- C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/02—Alloys containing metallic or non-metallic fibres or filaments characterised by the matrix material
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C49/00—Alloys containing metallic or non-metallic fibres or filaments
- C22C49/14—Alloys containing metallic or non-metallic fibres or filaments characterised by the fibres or filaments
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture Of Alloys Or Alloy Compounds (AREA)
- Powder Metallurgy (AREA)
Abstract
本发明属于有色金属复合材料领域,尤其是一种采用纳米碳化硼‑碳化硅晶须来增韧高强度铜基复合材料的方法。原位生成碳化硼‑碳化硅晶须增韧高强度铜基复合材料粉末由高强度铜基复合基体材料粉末和纳米碳化硼‑碳化硅晶须粉末组成,采用机械混合法使高强度铜基复合基体粉末与纳米碳化硼‑碳化硅晶须粉末均匀混合,真空烧结热压锭通过挤压变形获得原位生成纳米碳化硼‑碳化硅晶须增韧高强度铜基复合材料。本发明因原位生成纳米碳化硼‑碳化硅晶须增韧铜基复合材料具有强韧性,同时耐磨性、强度显著提高,尤其适合于高速铁路高强度电缆、高端装备制造业等。尤其适合于刀具、模具和航空航天等材料的应用。
Description
技术领域
本发明属于有色金属复合材料领域,尤其是一种采用纳米碳化硼-碳化硅晶须来增韧高强度铜基复合材料的方法。
背景技术
铜及铜合金材料由于具有良好的导电、导热、耐腐蚀性以及良好的塑性加工性能和较高的强度,目前广泛应用于电力电缆、电工、电机、高端装备制造等工业部门。由于铜及铜合金材料强度和硬度较钢铁材料差距较大,而且在自然界含量较少,因此,随着科技和工业的进步,对铜及铜合金的力学性能提出了更高的要求。因此,开发具有高的强度,同时又具有优良的塑性加工性能的铜合金十分必要。
通常采用晶粒细化法、合金化以及复合材料法实现提高铜合金的力学性能。晶粒细化法可有效提高铜合金的力学性能,但是该工艺目前还不能实现产业化,无法规模化生产。采用合金化也可提高铜合金的力学性能,但是添加了大量贵金属元素,造成铜合金生产成本居高不下。因此,采用颗粒增强,尤其是近年来出现的晶须增强、增韧的方法可有效获得高强度铜基复合材料。
基于上述目的,采用在铜基复合材料体粉末中原位生成纳米碳化硼-碳化硅晶须晶须来增韧纯铜材料的方法。本发明的高强度纯铜基体材料的化学成分及重量百分比为Cu:99.99%。然后在基体纯铜材料粉末中添加碳化硼-碳化硅晶须粉末,最终通过原位法制备高强度、高韧性的纯铜材料。
发明内容
本发明专利的目的是:在于克服上述现有技术不足,提供一种加工工艺稳定、生产成本低廉、无污染排放、可在常规条件下组织生产的碳化硼-碳化硅晶须增韧高强度纯铜材料,较传统的纯铜材料具有更好的强度、硬度,较常规纯铜材料的韧性大幅提升。
本发明提供了一种原位生成碳化硼-碳化硅晶须增韧高强度纯铜材料,其特征在于:该材料沿挤压流线形成定向排列的碳化硼-碳化硅晶须和高强度纯铜基体材料组成,晶须直径为300-800nm,原位增强相的体积总量在0.05-0.10。
本发明是通过以下技术方案:原位生成碳化硼-碳化硅晶须增韧高强度纯铜材料粉末由高强度纯铜基体材料粉末和碳化硼-碳化硅晶须粉末组成,然后采用机械混合法使高强度纯铜基体粉末与碳化硼-碳化硅晶须粉末均匀混合,混合粉末冷压实后在10-6托真空条件下逐步加热除气,然后在450-600℃,50-200Mpa条件下真空烧结1-10小时,热压锭400-500℃通过带背压的模具通道拐角为100o的等通道侧向挤压(ECAP)变形。测试表明所获得的原位生成碳化硼-碳化硅晶须增韧高强度纯铜材料具有高强韧性。
方案所需材料按如下具体步骤制备:
(1)碳化硼-碳化硅晶须的制备:
原位生成碳化硼-碳化硅晶须粉末的制备工艺为:碳化硼-碳化硅晶须前驱体材料化学成分为:聚四氯乙烯,B2O3,Si,C,Mn,NaCl,其重量配比为:(45.4~48.2):(45.4~48.2):(45.6~50.8):(45.6~50.8):(0.1~0.9):(1.0~8.1)。将按比例配制的能够生成碳化硼-碳化硅晶须的先驱体复合粉末加无水乙醇于球磨机中进行机械化球磨24小时,获得具有200-800nm晶粒尺寸超细先驱体复合粉末,将粉末装入石墨容器中,在氩气气氛保护和1450℃-1600℃的温度条件下,保温120min-240min合成。
2B2O3+7C=(加热)B4C+6CO
Si+C=(加热)SiC
(2)高强度纯铜基体材料粉末制备:
本发明的高强度纯铜基体材料的化学成分及重量百分比为Cu:99.99%,夹杂元素总量不大于0.01%。将高强度纯铜粉末加无水乙醇于球磨机中进行机械化球磨24小时,获得具有50-150μm晶粒尺寸超细粉末。
本发明为获得最佳的综合力学性能和学腐蚀性能,严格控制杂质的含量:Cu的纯净度大于等于99.99% ;夹杂元素总量不大于0.01%。
(3)碳化硼-碳化硅晶须与高强度纯铜基体材料混合粉末:
碳化硼-碳化硅晶须粉末在高强度纯铜材料中的重量含量为5-10%,将碳化硼-碳化硅晶须与高强度纯铜基体材料按重量百分比为(5-10):(95-90)的比例配制为碳化硼-碳化硅晶须增韧高强度纯铜材料粉末。
该原位生成碳化硼-碳化硅晶须增韧高强度纯铜材料无需专用设备,在常规铜合金厂即可组织生产,本发明投资少,见效快,能快速收回投资成本。
与现有铸造高强度纯铜技术相比,原位生成碳化硼-碳化硅晶须增韧高强度纯铜的制备方法具有如下优点:
(1)具有强韧性、耐磨性、强度显著提高,间隔2小时挤压试样的力学性能差小于6%,这将有利于大批量、小尺寸口腔材料的稳定生产。增强颗粒尺寸细小,分布均匀,组织稳定性高,与在高强度纯铜基体结合良好。材料的室温韧性、硬度和耐磨性能显著提高,尤其适合于高速铁路高强度电缆、高端装备制造业等。
(2)合金组织稳定性好,不会分解有毒气体或有毒溶解物,本发明因增强颗粒是与高强度纯铜颗粒在真空中原位反应生成,生产的工艺稳定性高。
具体实施方式
下面给出本发明的最佳实施例:按高强度纯铜基体材料的化学成分及重量百分比为: Cu:99.99%,夹杂元素总量不大于0.01%。将按比例配制的高强度纯铜粉末加无水乙醇于球磨机中进行机械化球磨24小时,获得具有50-150μm晶粒尺寸超细粉末。将碳化硼-碳化硅晶须前驱体材料化学成分为:聚四氯乙烯,B2O3,Si,C,Mn,NaCl,其重量配比为:(45.4~48.2):(45.4~48.2):(45.6~50.8):(45.6~50.8):(0.1~0.9):(1.0~8.1)。将按比例配制的能够生成碳化硼-碳化硅晶须的先驱体复合粉末加无水乙醇于球磨机中进行机械化球磨24小时,获得具有200-800nm晶粒尺寸超细先驱体复合粉末。将碳化硼-碳化硅晶须与高强度纯铜基体材料按重量百分比为8:92的比例配制为碳化硼-碳化硅晶须增韧高强度纯铜材料粉末。然后采用机械混合法使高强度纯铜基体粉末与碳化硼-碳化硅晶须粉末均匀混合,混合粉末冷压实后在10-6托真空条件下逐步加热除气,然后在550℃,150Mpa条件下真空烧结2小时,热压锭在450℃通过模具通道拐角为120o的等通道弯角挤压(ECAP)变形。然后进行T6处理,并进行性能测试。测试表明所获得的原位生成碳化硼-碳化硅晶须增韧高强度纯铜材料具有高强韧性。该工艺下可获得高强度中等塑性高强度纯铜( 抗拉强度为453MPa,屈服强度为417MPa,延伸率为39% )。
Claims (1)
1.碳化硼-碳化硅晶须增韧高强度铜基复合材料的制备方法,其特征是由高强度纯铜基体材料粉末和纳米碳化硼-碳化硅晶须粉末组成,然后采用机械混合法使高强度纯铜基体粉末与纳米碳化硼-碳化硅晶须粉末均匀混合,真空烧结热压锭通过带背压的等通道侧向挤压变形获得原位生成纳米碳化硼-碳化硅晶须增韧高强度纯铜材料;
(a)高强度纯铜基体材料的化学成分及重量百分比为Cu:99.99%,夹杂元素总量不大于0.01%;
(b)碳化硼-碳化硅晶须前驱体材料化学成分为:聚四氯乙烯,B2O3,Si,C,Mn,NaCl,其重量配比为:(45.4~48.2):(45.4~48.2):(45.6~50.8):(45.6~50.8):(0.1~0.9):(1.0~8.1)。
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