CN106867645A - 一种含石墨烯的拉丝液及其制备方法 - Google Patents
一种含石墨烯的拉丝液及其制备方法 Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 91
- 238000005491 wire drawing Methods 0.000 title claims abstract description 86
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 10
- 150000002148 esters Chemical class 0.000 claims abstract description 10
- HJVAFZMYQQSPHF-UHFFFAOYSA-N 2-[bis(2-hydroxyethyl)amino]ethanol;boric acid Chemical compound OB(O)O.OCCN(CCO)CCO HJVAFZMYQQSPHF-UHFFFAOYSA-N 0.000 claims abstract description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 9
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims abstract description 9
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims abstract description 9
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- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 241000722946 Acanthocybium solandri Species 0.000 claims abstract description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
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- 229910002804 graphite Inorganic materials 0.000 claims description 3
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- 238000000034 method Methods 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
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- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
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- 229910001128 Sn alloy Inorganic materials 0.000 abstract description 4
- 238000005336 cracking Methods 0.000 abstract description 4
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
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- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
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- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
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- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229940068041 phytic acid Drugs 0.000 description 1
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- 239000000467 phytic acid Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
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- UPMFZISCCZSDND-JJKGCWMISA-M sodium gluconate Chemical compound [Na+].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O UPMFZISCCZSDND-JJKGCWMISA-M 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明公开了一种含石墨烯的拉丝液及其制备方法,属于金属加工技术领域。该拉丝液由下列重量比例的原料制成:石墨烯分散液0.5~10%,丙二醇1~5%,季戊四醇油酸酯1~3%,聚乙二醇200 0.5~5%,水溶性钛酸酯0.1~1%,三乙醇胺硼酸酯0.1~2%,甲基苯并三氮唑0.1~1%,OP‐10 0.1~5%,去离子水余量。本发明拉丝液中添加了石墨烯,具有优异润滑性和导热性,在金属丝拉制过程中,贴覆在金属丝表面的石墨烯,在金属丝变形过程中可压入其表面,增加表面完整性,有效抑制变形开裂或断丝现象,提高金属丝的变形能力,增强线材产品丝表面光亮度和抗腐蚀能力,可广泛用作锡合金、铜、铝等金属丝的拉丝液。
Description
技术领域
本发明公开了一种含石墨烯的拉丝液及其制备方法。属于金属加工技术领域。
背景技术
拉丝工艺是金属加工中一种常见工艺,是指金属线材在压力和拉力作用下强行通过磨具,获得所要求的截面积形状和尺寸的技术加工方法。常见的产品有铜丝、铝丝和锡合金丝。拉丝液是拉丝工艺中必不可少的辅助剂,它主要的作用是在金属丝拉拔过程中起到润滑作用,同时保护线材、模具,达到良好的拉丝效果,拉丝液的品质直接影响到拉丝产品效果,性能优良的拉丝液可起到保护模具,提高拉丝效率,提高线材产品的品质。
人们往往通过使用或添加特定的组分来提高拉丝液的润滑作用,以达到如上目的。如专利201510011056.1添加氰尿酸三聚氰胺,专利201410126717.0添加硅溶胶,专利201410126163.3通过使用环烷油和季戊四醇油酸酯作为基础油,并配以植酸和葡萄糖酸钠,提高拉丝液的润滑能力;专利201310493959.9、201310493753.6和201410433714.1添加的纳米氮化铝,专利201510011053.8添加的纳米二氧化钛,201410126274.5添加的纳米活性炭,专利201510011059.5添加的纳米石墨,均在一定程度上提高了拉丝液的润滑能力。
石墨烯是一种具有六角结构的二维材料,它的厚度大约为0.335nm,根据制备方式的不同而存在不同的起伏,通常在垂直方向的高度大约1nm左右,水平方向宽度大约10nm到25nm,因而石墨烯具有很好的贴覆性能,且具有优异的润滑作用。本发明拉丝液中添加的石墨烯在金属丝拉制过程中,石墨烯贴覆在金属丝表面,一方面显著提高金属丝表面的润滑性,减少金属碎屑的剥落,另一方面,金属丝在变形过程中石墨烯被压入金属表面,提高金属丝表面完整性,和抗开裂和断丝的能力,从而提高金属丝的变形能力,增强线材产品表面光亮度和抗腐蚀能力。可广泛用于锡合金、铜、铝等金属丝的拉制过程,特别适用于难拉拔的焊锡丝的制备。
石墨烯具有优异的导热性能,导热系数高达5300W/m,远高于碳纳米管和金刚石,本发明拉丝液中添加的石墨烯,有效提高拉丝液的整体导热性,使拉丝过程产生的热量迅速得到传递,避免拉丝液由于局部温度过高造成的变质,延长拉丝液的使用寿命。
发明内容
本发明公开的一种含石墨烯的拉丝液及其制备方法,所述拉丝液由下列重量比例的原料制成:石墨烯分散液0.5~10%,丙二醇1~5%,季戊四醇油酸酯1~3%,聚乙二醇200 0.5~5%,水溶性钛酸酯0.1~1%,三乙醇胺硼酸酯0.1~2%,甲基苯并三氮唑0.1~1%,OP‐10 0.1~5%,去离子水余量。
所述拉丝液的更优重量百分比组成为:石墨烯分散液1~5%,丙二醇2~3%,季戊四醇油酸酯1.5~2%,聚乙二醇200 0.5~2%,水溶性钛酸酯0.3~0.5%,三乙醇胺硼酸酯0.1~1%,甲基苯并三氮唑0.1~0.5%,OP‐10 0.1~1%,去离子水余量。
所述含石墨烯的拉丝液,为了使石墨烯能够更好的分散在拉丝液中,需要预先制备获得石墨烯分散液,而后将石墨烯分散液分散到拉丝液中。所述石墨烯分散液,由下列重量比例的原料组成:石墨烯0.5~10%,N‐甲基吡咯烷酮1~5%,聚乙烯吡咯烷酮2~6%,十六烷基三甲基溴化铵1~5%,硅烷偶联剂0.1~1%,去离子水余量。
所述石墨烯分散液由以下步骤制成:1)将N‐甲基吡咯烷酮、聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、硅烷偶联剂、去离子水混合均匀,在50~60℃条件下充分溶解;2)将石墨烯加入溶解好的溶液中,用高速剪切机在10000~12000rpm转速下处理60min,即得石墨烯分散液。
本发明公开的一种含石墨烯的拉丝液,由以下步骤制成:1)将丙二醇、季戊四醇油酸酯、聚乙二醇200、水溶性钛酸酯、三乙醇胺硼酸酯、甲基苯并三氮唑、OP‐10、去离子水混合均匀,在70~80℃下充分溶解;2)将石墨烯分散液在800~1000rpm转速下边搅拌边缓缓加入溶解好的溶液中,搅拌45min即得拉丝液。
本发明所公开的一种含石墨烯的拉丝液,其优点在于:石墨烯了提高拉丝液的润滑性,减少对金属丝和拉丝模具的损耗。在金属丝拉制过程中,拉丝液中的石墨烯在金属丝通过磨具过程中,会贴覆在金属丝表面,提高金属丝表面的润滑性,并且在金属丝拉伸过程中,贴覆在表面的石墨烯对金属丝起到保护作用,石墨烯之间的润滑作用可提高金属丝表面的变形能力,有效避免金属屑的剥落和线材表面的开裂,提高线材产品表面光亮度和耐腐蚀性。另外,石墨烯有效提高了拉丝液的整体导热性,使拉丝过程产生的热量迅速得到传递,避免拉丝液由于局部温度过高造成的变质,延长拉丝液的使用寿命。
本发明所公开的一种含石墨烯的拉丝液,可用于但不限于在锡合金、铜、铝等金属丝的拉丝过程中使用。锡合金包括但不限于SnAg3.0Cu0.5、SnAg0.3Cu0.7、SnCu0.7、Sn63Pb37、SnBi58、SnBi30Cu0.5等。
附图说明
图1为显微镜(×200)下观察的石墨烯拉丝液生产的SnAg3.0Cu0.5锡丝;
图2为显微镜(×200)下观察的传统拉丝液生产的SnAg3.0Cu0.5锡丝。
具体实施例
实施例1:
拉丝液(各组分重量百分含量,%)
石墨烯分散液(各组分重量百分含量,%)
石墨烯分散液制备方法:1)将称量好的N‐甲基吡咯烷酮、聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、硅烷偶联剂、去离子水置于容器中,混合均匀,在50~60℃条件下充分溶解;2)将石墨烯加入溶解好的溶液中,用高速剪切机在10000~12000rpm转速下处理60min,即得石墨烯分散液。
拉丝液制备方法:1)将称量好的丙二醇、季戊四醇油酸酯、聚乙二醇200、水溶性钛酸酯、三乙醇胺硼酸酯、甲基苯并三氮唑、OP‐10、去离子水置于容器中,混合均匀,在70~80℃下充分溶解;2)将石墨烯分散液在800~1000rpm转速下边搅拌边缓缓加入溶解好的溶液中,搅拌45min即得拉丝液。
制备的拉丝液可作为SnAg3.0Cu0.5、SnAg0.3Cu0.7、SnCu0.7、SnPb37等锡丝的拉丝液。该拉丝液在常温下可储存1年,换液周期达10个月,远长于传统拉丝液3个月的换液周期。相对于传统的拉丝液,在拉丝过程中,锡丝无金属屑剥落现象,表面无开裂情况,生产的锡丝产品表面平整、光亮。
本实施例所述拉丝液生产的直径为0.8mm的SnAg3.0Cu0.5锡丝,在200倍显微镜下观察锡丝表面,如图1所示。
实施例2:
拉丝液(各组分重量百分含量,%)
石墨烯分散液(各组分重量百分含量,%)
石墨烯分散液和拉丝液的制备方法同实施例1,所制备的拉丝液可作为SnAg3.0Cu0.5、SnAg0.3Cu0.7、SnCu0.7、SnPb37等锡丝的拉丝液。
实施例3:
拉丝液(各组分重量百分含量,%)
石墨烯分散液(各组分重量百分含量,%)
石墨烯分散液和拉丝液的制备方法同实施例1,所制备的拉丝液可作为SnAg3.0Cu0.5、SnAg0.3Cu0.7、SnCu0.7、SnPb37等锡丝的拉丝液。
实施例4:
拉丝液(各组分重量百分含量,%)
石墨烯分散液(各组分重量百分含量,%)
石墨烯分散液和拉丝液的制备方法同实施例1,所制备的拉丝液可作为SnBi58、SnBi30Cu0.5等锡丝的拉丝液。
实施例5:
石墨烯分散液(各组分重量百分含量,%)
石墨烯分散液和拉丝液的制备方法同实施例1,所制备的拉丝液可作为铜丝的拉丝液。
实施例6:
拉丝液(各组分重量百分含量,%)
石墨烯分散液(各组分重量百分含量,%)
石墨烯分散液和拉丝液的制备方法同实施例1,所制备的拉丝液可作为铜丝的拉丝液。
实施例7:
拉丝液(各组分重量百分含量,%)
石墨烯分散液(各组分重量百分含量,%)
石墨烯分散液和拉丝液的制备方法同实施例1,所制备的拉丝液可作为铝丝的拉丝液。
实施例8:
拉丝液(各组分重量百分含量,%)
石墨烯分散液(各组分重量百分含量,%)
石墨烯分散液和拉丝液的制备方法同实施例1,所制备的拉丝液可作为铝丝的拉丝液。
比较例1:
拉丝液(各组分重量百分含量,%)
本对比例为传统类型的拉丝液,制备方法:1)将称量好的丙二醇、季戊四醇油酸酯、聚乙二醇200、水溶性钛酸酯、三乙醇胺硼酸酯、甲基苯并三氮唑、OP‐10、N‐甲基吡咯烷酮、聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、硅烷偶联剂和去离子水置于容器中,混合均匀,在70~80℃下充分溶解得到拉丝液。
用本对比例生产的直径为0.8mm的SnAg3.0Cu0.5锡丝,在200倍显微镜下观察锡丝表面,如图2所示。与实施例1中生产的锡丝比较,显然添加了石墨烯的拉丝液较传统拉丝液生产的锡丝表面更加平整、光亮。
Claims (6)
1.一种含石墨烯的拉丝液,其特征在于:所述拉丝液含有石墨烯组分。
2.根据权利要求1所述的含石墨烯的拉丝液,其特征在于,所述拉丝液的重量百分比组成为:石墨烯分散液0.5~10%,丙二醇1~5%,季戊四醇油酸酯1~3%,聚乙二醇200 0.5~5%,水溶性钛酸酯0.1~1%,三乙醇胺硼酸酯0.1~2%,甲基苯并三氮唑0.1~1%,OP‐10 0.1~5%,去离子水余量。
3.根据权利要求2所述的含石墨烯的拉丝液,其特征在于,所述拉丝液的重量百分比组成为:石墨烯分散液1~5%,丙二醇2~3%,季戊四醇油酸酯1.5~2%,聚乙二醇200 0.5~2%,水溶性钛酸酯0.3~0.5%,三乙醇胺硼酸酯0.1~1%,甲基苯并三氮唑0.1~0.5%,OP‐10 0.1~1%,去离子水余量。
4.根据权利要求2所述的含石墨烯的拉丝液,其特征在于:所述石墨烯分散液的重量百分比组成为:石墨烯0.5~10%,N‐甲基吡咯烷酮1~5%,聚乙烯吡咯烷酮2~6%,十六烷基三甲基溴化铵1~5%,硅烷偶联剂0.1~1%,去离子水余量。
5.根据权利要求4所述的含石墨烯的拉丝液,其特征在于,所述石墨烯分散液由以下步骤制成:
(1)将N‐甲基吡咯烷酮、聚乙烯吡咯烷酮、十六烷基三甲基溴化铵、硅烷偶联剂、去离子水混合均匀,在50~60℃条件下充分溶解;
(2)将石墨烯加入溶解好的溶液中,用高速剪切机在10000~12000rpm转速下处理60min,即得石墨烯分散液。
6.一种权利1‐5任意一项所述的含石墨烯的拉丝液的制备方法,其特征在于,所述含石墨烯的拉丝液由以下步骤制成:
1)中将丙二醇、季戊四醇油酸酯、聚乙二醇200、水溶性钛酸酯、三乙醇胺硼酸酯、甲基苯并三氮唑、OP‐10、去离子水混合均匀,在70~80℃下充分溶解;
2)将石墨烯分散液在800~1000rpm转速下搅拌边缓缓加入溶解好的溶液中,搅拌45min即得拉丝液。
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