CN109137031A - 一种金属基陶瓷复合材料及制备方法 - Google Patents
一种金属基陶瓷复合材料及制备方法 Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 23
- 239000002184 metal Substances 0.000 title claims abstract description 23
- 239000011159 matrix material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 50
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000002994 raw material Substances 0.000 claims abstract description 30
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 28
- 229910052582 BN Inorganic materials 0.000 claims abstract description 27
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 25
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 16
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 15
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims abstract description 13
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- 238000003756 stirring Methods 0.000 claims description 18
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- 239000000463 material Substances 0.000 claims description 12
- 239000011684 sodium molybdate Substances 0.000 claims description 12
- 235000015393 sodium molybdate Nutrition 0.000 claims description 12
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 12
- 239000010936 titanium Substances 0.000 claims description 12
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- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
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- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 abstract 1
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- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- 229910001145 Ferrotungsten Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- IGOJDKCIHXGPTI-UHFFFAOYSA-N [P].[Co].[Ni] Chemical compound [P].[Co].[Ni] IGOJDKCIHXGPTI-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- OWUGOENUEKACGV-UHFFFAOYSA-N [Fe].[Ni].[W] Chemical compound [Fe].[Ni].[W] OWUGOENUEKACGV-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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Abstract
一种金属基陶瓷复合材料及制备方法，属于复合材料技术领域。其特征在于：所述的金属制件的部分或全部表面覆有一层陶瓷复合层，所述的陶瓷复合层的原料包括以下重量份组成：硫酸镍60~80份、硫酸钴3~7份、钨酸钠1~3份、磷酸5~9份、碳化硅3~6份、硼化钛3~6份、氮化硼4.5~18份、柠檬酸30~35份、亚磷酸9~18份、光亮剂0.7~1.5份。制备方法为用不锈钢作为阳极，用金属制件作为阴极在电流条件下完成复合。本发明复合完成后金属制件表面平整但防滑，在制成石油机械后，方便抓握，完成对接、拆卸等操作时更加方便、准确。
Description
技术领域
一种金属基陶瓷复合材料及制备方法，属于复合材料技术领域。
背景技术
在石油机械技术领域，偏磨及腐蚀现象较为严重，针对石油机械的表面处理工艺，目前还没有一种既能够防腐耐磨又兼具成本低廉的表面处理技术。 随着石油资源的不断消耗，致使开采石油的环境越来越恶劣，对石油设备的耐腐蚀、耐摩擦性能要求也越来越高。
传统的表面处理技术主要是电镀铬技术，电镀铬由于其污染性强，并且其耐腐蚀性能不高，其应用受到限制。 近年发展的钨合金电镀技术，比如铁钨合金、镍钨合金、铁镍钨合金、镍钨磷合金等，经过控制可以得到非晶合金钨。 钨不能单独的从水溶液中电沉积出来，但可以和铁族元素（铁、镍、钴） 一起诱导共沉积出来，得到上述种类的钨合金。 钨合金的耐腐蚀性能远优于电镀铬层，但是，这些镀种存在脆性大（尤其铁钨合金）、表面有微裂纹、镀厚有针孔等缺陷，并且耐磨性能差于电镀铬层，这些问题限制了其应用范围。
还有一种钴镍磷电镀技术，即在抽油杆等部件上通过电镀的方式增加电镀层，能够形成较高的硬度，且现有技术中还在电镀液中增加了碳化硅组分，来降低镀层的脆性。但是传统的钴镍磷镀层的表面光滑度太高，防滑性能较差，尤其是在石油机械领域，在表面沾油后操作时很难抓握，在完成对接、拆卸等操作时，增加了操作难度。
发明内容
本发明要解决的技术问题是：克服现有技术的不足，提供一种防滑、耐磨、抗振的金属基陶瓷复合材料及制备方法。
本发明解决其技术问题所采用的技术方案是：该金属基陶瓷复合材料，包括金属制件，其特征在于：所述的金属制件表面覆有一层陶瓷复合层，所述的陶瓷复合层的原料包括以下重量份组成：硫酸镍 60~80 份、硫酸钴 3~7 份、钼酸钠1~3份、磷酸 5~9 份、碳化硅3~6份、硼化钛3~6份、氮化硼4.5~18份、柠檬酸 30~35份、亚磷酸9~18份、光亮剂 0.7~1.5份。
本发明旨在提供一种防滑、耐磨、抗振的金属基陶瓷复合材料，陶瓷复合层的原料配方在通过电化学的方式复合到金属制件表面后，不但能够大大的提高金属制件的强度，而且在剧烈的振动下具有悠久的寿命，硬度高、耐磨，最主要的，复合完成后金属制件表面平整但防滑，在制成石油机械后，方便抓握，完成对接、拆卸等操作时更加方便、准确。
优选的，所述的陶瓷复合层的原料包括以下重量份组成：硫酸镍 66~80 份、硫酸钴 5~6 份、钼酸钠1.5~2份、磷酸6~7.5份、碳化硅4~5份、硼化钛4~5份、氮化硼4.8~10.8份、柠檬酸 32~33份、亚磷酸12~16份、光亮剂 1~1.2份。优选的重量份组成能能够同时达到最好的耐磨和防滑效果。
优选的，所述的硫酸镍和硫酸钴的质量比为14~16:1。优选的三种主物料的质量比能够达到更好的抗振和耐磨效果。
更优选的，所述的硫酸镍和硫酸钴的质量比为15:1。最优选的三种主物料的质量比能够达到本发明最好的抗振和耐磨效果。
优选的，所述的磷酸与亚磷酸的质量比为1:2~2.2。优选的磷酸与亚磷酸的质量比在进行电化学复合式，复合效率更高，达到同样厚度的复合层所需的时间更少。
优选的，所述的碳化硅和硼化钛的质量比为1:1，所述的碳化硅和硼化钛的总质量与氮化硼的质量比为1:0.8~0.9。优选的碳化硅、硼化钛和氮化硼的配比能够同时达到更好的耐磨和防滑效果。
一种金属基陶瓷复合材料的制备方法，其特征在于：包括以下步骤 ：
1） 将碳化硅、硼化钛、氮化硼和磷酸在400rpm~700 rpm转速的混炼机内混炼20 min ~40min，上述物料完成混炼后加入其余原料，然后加入原料总质量4.5~7倍量的水搅拌均匀；
2）搅拌条件下加热至 60℃~80℃的温度后保温；用不锈钢作为阳极，用金属制件作为阴极，分别接通电源；在电流密度为 5 A/dm2~12A/dm2的条件下完成金属制件表面陶瓷复合层的复合。
本发明的制备方法中需要先将碳化硅、硼化钛、氮化硼和磷酸混炼，再与其他物料一起制成溶液进行电化学反应，这样才能保证在本发明的大电流密度下，高效的完成金属基陶瓷复合材料的复合，同时保证本材料具有优异的抗振性能和防滑性能。
优选的，步骤2）中所述加热至65℃~80℃，所述的电流密度为 5A/dm2~11.5A/dm2。优选的反应条件配合本发明上述优选的配方能够达到本发明的最佳效果。
与现有技术相比，本发明的所具有的有益效果是：本发明旨在提供一种防滑、耐磨、抗振的金属基陶瓷复合材料及制备方法，本发明的制备方法中需要先将碳化硅、硼化钛、氮化硼和磷酸混炼，再与其他物料一起制成溶液进行电化学反应，这样才能保证在本发明的大电流密度下，高效的完成金属基陶瓷复合材料的复合，同时保证本材料具有优异的抗振性能和防滑性能。本发明特殊配比和配方的金属基陶瓷复合层在经过本发明的制备方法通过电化学的方式复合到金属制件表面后，不但能够大大的提高金属制件的强度，而且在剧烈的振动下具有悠久的寿命，硬度高、耐磨，最主要的，复合完成后金属制件表面平整但防滑，在制成石油机械后，方便抓握，完成对接、拆卸等操作时更加方便、准确。
具体实施方式
下面结合具体实施例对本发明做进一步说明，其中实施例1为最佳实施。
实施例1
1）按重量份组成硫酸镍 78份、硫酸钴 5.2 份、钼酸钠1.7份、磷酸6.8份、碳化硅4.5份、硼化钛4.5份、氮化硼7.2份、柠檬酸 32.5份、亚磷酸14.3份、光亮剂 1.1份备料；
2） 备料后将碳化硅、硼化钛、氮化硼和磷酸在600 rpm转速的混炼机内混炼25min，完成混炼后加入其余原料，然后加入原料总质量5倍量的水搅拌均匀；
3）搅拌条件下加热至 67℃的温度后保温；用不锈钢作为阳极，用4mm厚钢管作为阴极，分别接通电源；在电流密度为11.5A/dm2的条件下完成金属制件表面陶瓷复合层的复合。
实施例2
1）按重量份组成：硫酸镍 75.6 份、硫酸钴 5.4 份、钼酸钠1.5份、磷酸6.2份、碳化硅5份、硼化钛5份、氮化硼8份、柠檬酸 32份、亚磷酸12.4份、光亮剂 1份备料；
2） 备料后将碳化硅、硼化钛、氮化硼和磷酸在500 rpm转速的混炼机内混炼30min，上述物料完成混炼后加入其余原料，然后加入原料总质量6倍量的水搅拌均匀；
3）搅拌条件下加热至65℃的温度后保温；用不锈钢作为阳极，用4mm厚钢管作为阴极，分别接通电源；在电流密度为11.5A/dm2的条件下完成金属制件表面陶瓷复合层的复合。
实施例3
1）按重量份组成：硫酸镍80 份、硫酸钴 5份、钼酸钠2份、磷酸7份、碳化硅4份、硼化钛4份、氮化硼7.2份、柠檬酸33份、亚磷酸15.4份、光亮剂1.2份备料；
2） 备料后将碳化硅、硼化钛、氮化硼和磷酸在600 rpm转速的混炼机内混炼25min，上述物料完成混炼后加入其余原料，然后加入原料总质量5.5倍量的水搅拌均匀；
3）搅拌条件下加热至68℃的温度后保温；用不锈钢作为阳极，用4mm厚钢管作为阴极，分别接通电源；在电流密度为11A/dm2的条件下完成金属制件表面陶瓷复合层的复合。
实施例4
1）按重量份组成：硫酸镍 66份、硫酸钴 5 份、钼酸钠2份、磷酸6份、碳化硅5份、硼化钛4份、氮化硼10.8份、柠檬酸 32份、亚磷酸16份、光亮剂 1份备料；
2） 备料后将碳化硅、硼化钛、氮化硼和磷酸在500 rpm转速的混炼机内混炼28min，上述物料完成混炼后加入其余原料，然后加入原料总质量5.6倍量的水搅拌均匀；
3）搅拌条件下加热至66℃的温度后保温；用不锈钢作为阳极，用4mm厚钢管作为阴极，分别接通电源；在电流密度为12A/dm2的条件下完成金属制件表面陶瓷复合层的复合。
实施例5
1）按重量份组成：硫酸镍80 份、硫酸钴6 份、钼酸钠1.5份、磷酸7.5份、碳化硅4份、硼化钛5份、氮化硼4.8份、柠檬酸33份、亚磷酸12份、光亮剂1.2份备料；
2） 备料后将碳化硅、硼化钛、氮化硼和磷酸在600 rpm转速的混炼机内混炼35min，上述物料完成混炼后加入其余原料，然后加入原料总质量5倍量的水搅拌均匀；
3）搅拌条件下加热至 67℃的温度后保温；用不锈钢作为阳极，用4mm厚钢管作为阴极，分别接通电源；在电流密度为11A/dm2的条件下完成金属制件表面陶瓷复合层的复合。
实施例6
1）按重量份组成硫酸镍 60份、硫酸钴 3份、钼酸钠3份、磷酸5份、碳化硅6份、硼化钛3份、氮化硼18份、柠檬酸 30份、亚磷酸18份、光亮剂 0.7份备料；
2） 备料后将碳化硅、硼化钛、氮化硼和磷酸在400rpm转速的混炼机内混炼40min，上述物料完成混炼后加入其余原料，然后加入原料总质量7倍量的水搅拌均匀；
3）搅拌条件下加热至 60℃的温度后保温；用不锈钢作为阳极，用4mm厚钢管为阴极，分别接通电源；在电流密度为 10 A/dm2的条件下完成金属制件表面陶瓷复合层的复合。
实施例7
1）按重量份组成硫酸镍80 份、硫酸钴7 份、钼酸钠1份、磷酸9 份、碳化硅3份、硼化钛6份、氮化硼4.5份、柠檬酸35份、亚磷酸9份、光亮剂1.5份备料；
2） 备料后将碳化硅、硼化钛、氮化硼和磷酸在700 rpm转速的混炼机内混炼20 min，上述物料完成混炼后加入其余原料，然后加入原料总质量4.5倍量的水搅拌均匀；
3）搅拌条件下加热至70℃的温度后保温；用不锈钢作为阳极，用4mm厚钢管作为阴极，分别接通电源；在电流密度为 10 A/dm2的条件下完成金属制件表面陶瓷复合层的复合。
对比例1
原料配比和制备过程同实施例1，不同的是原料中没有添加相应量的钼酸钠。
对比例2
原料配比和制备过程同实施例1，不同的是原料中没有添加相应量的硼化钛和氮化硼。
对比例3
原料配比和制备过程同实施例1，不同的是步骤2）中直接将所有的原料一同加水后搅拌均匀。
各实施例和对比例所制备的金属基陶瓷复合材料的性能测试结果见表1。
表1金属基陶瓷复合材料的性能测试结果
。
表1中测定防滑性能的方法为：将实施例或对比例所制备的陶瓷复合钢管用相同的金属夹提起，在钢管下端挂重物，记录钢管开始发生滑动时所挂重物的质量；钢管开始发生滑动时所挂重物的质量越大，则说明防滑性能越好。
以上所述，仅是本发明的较佳实施例而已，并非是对本发明作其它形式的限制，任何熟悉本专业的技术人员可能利用上述揭示的技术内容加以变更或改型为等同变化的等效实施例。但是凡是未脱离本发明技术方案内容，依据本发明的技术实质对以上实施例所作的任何简单修改、等同变化与改型，仍属于本发明技术方案的保护范围。
Claims (8)
1.一种金属基陶瓷复合材料，包括金属制件，其特征在于：所述的金属制件的部分或全部表面覆有一层陶瓷复合层，所述的陶瓷复合层的原料包括以下重量份组成：硫酸镍 60~80 份、硫酸钴 3~7 份、钼酸钠1~3份、磷酸 5~9 份、碳化硅3~6份、硼化钛3~6份、氮化硼4.5~18份、柠檬酸 30~35份、亚磷酸9~18份、光亮剂 0.7~1.5份。
2.根据权利要求1所述的一种金属基陶瓷复合材料，其特征在于：所述的陶瓷复合层的原料包括以下重量份组成：硫酸镍 66~80 份、硫酸钴 5~6 份、钼酸钠1.5~2份、磷酸6~7.5份、碳化硅4~5份、硼化钛4~5份、氮化硼4.8~10.8份、柠檬酸 32~33份、亚磷酸12~16份、光亮剂 1~1.2份。
3.根据权利要求1所述的一种金属基陶瓷复合材料，其特征在于：所述的硫酸镍和硫酸钴的质量比为14~16:1。
4.根据权利要求1所述的一种金属基陶瓷复合材料，其特征在于：所述的硫酸镍和硫酸钴的质量比为15:1。
5.根据权利要求1所述的一种金属基陶瓷复合材料，其特征在于：所述的磷酸与亚磷酸的质量比为1:2~2.2。
6.根据权利要求1所述的一种金属基陶瓷复合材料，其特征在于：所述的碳化硅和硼化钛的质量比为1:1，所述的碳化硅和硼化钛的总质量与氮化硼的质量比为1:0.8~0.9。
7.一种权利要求 1~6所述的金属基陶瓷复合材料的制备方法，其特征在于：包括以下步骤 ：
1） 将碳化硅、硼化钛、氮化硼和磷酸在400rpm~700 rpm转速的混炼机内混炼20 min ~40min，上述物料完成混合后加入其余原料，然后加入原料总质量4.5~7倍量的水搅拌均匀；
2）搅拌条件下加热至 60℃~80℃的温度后保温；用不锈钢作为阳极，用金属制件作为阴极，分别接通电源；在电流密度为 5 A/dm2~12A/dm2的条件下完成金属制件表面陶瓷复合层的复合。
8.根据权利要求7所述的一种金属基陶瓷复合材料的制备方法，其特征在于：步骤2）中所述加热至65℃~80℃，所述的电流密度为 5A/dm2~11.5A/dm2。
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