CN117024166A - 一种碳-碳复合材料受电弓滑板及其制备方法 - Google Patents
一种碳-碳复合材料受电弓滑板及其制备方法 Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000000463 material Substances 0.000 claims abstract description 67
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 39
- 235000015895 biscuits Nutrition 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- 239000010426 asphalt Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000003825 pressing Methods 0.000 claims abstract description 18
- 238000004898 kneading Methods 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000007598 dipping method Methods 0.000 claims abstract description 14
- 239000006229 carbon black Substances 0.000 claims abstract description 12
- 239000000571 coke Substances 0.000 claims abstract description 12
- 239000002006 petroleum coke Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000005096 rolling process Methods 0.000 claims abstract description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 50
- 239000004917 carbon fiber Substances 0.000 claims description 50
- 238000003756 stirring Methods 0.000 claims description 48
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 33
- 238000001035 drying Methods 0.000 claims description 30
- 238000005406 washing Methods 0.000 claims description 30
- 229910021389 graphene Inorganic materials 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000007789 sealing Methods 0.000 claims description 10
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 8
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 238000005098 hot rolling Methods 0.000 abstract description 5
- 230000010354 integration Effects 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 description 16
- 238000012360 testing method Methods 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 6
- 150000001721 carbon Chemical class 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000002679 ablation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 230000003137 locomotive effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241001391944 Commicarpus scandens Species 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
- C04B35/83—Carbon fibres in a carbon matrix
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- B60—VEHICLES IN GENERAL
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- B60L5/00—Current collectors for power supply lines of electrically-propelled vehicles
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Abstract
本发明公开了一种碳‑碳复合材料受电弓滑板的制备方法,其特征在于,包括如下步骤:将石油焦、沥青焦、炭黑混合均匀,混捏处理后加入改性氧化石墨烯,混捏处理得到混料;将混料与改性碳纤维加入到热辊轧机中,反复辊轧得到辊轧料;将辊轧料捏碎后加入到压制机中压制成型,得到素坯;将素坯加入到烧结炉中,在N2气氛下焙烧得到烧结体;将烧结体放入浸渍罐中,加入熔融的中温沥青进行浸渍,得到浸渍料;重复烧结和浸渍过程2~3次,得到碳‑碳复合材料受电弓滑板;制备得到的碳‑碳复合材料轻量化、一体化程度高,具有优异的各向同性,电阻率和接触电阻低,抗冲击强度高,表现出良好的减磨自润滑性能以及耐热耐电弧性能。
Description
技术领域
本发明涉及受电弓滑板技术领域,具体涉及一种碳-碳复合材料受电弓滑板及其制备方法。
背景技术
电气化是铁路和城市轨道交通未来发展的趋势,我国对电气化铁路的建设也进入了新时期,因此对弓网系统的性能有了更高的要求。电气化列车动力的主要来源是弓网系统提供的电力,而弓网系统包括接触导电网和受电弓(滑板)两部分,接触网导线的材质大多采用铜质合金材料,但作为从接触网线导入电能至电力机车的受电弓滑板主要经历了纯金属滑板、粉末冶金滑板、纯碳滑板、浸金属碳滑板、金属基复合材料滑板和无机非金属基复合材料滑板等发展过程。
纯碳滑板滑动时电磁噪声小,且耐高温,耐电弧性强,不易和接触导线发生焊附现象,但是碳滑板机械强度低,耐冲击性差,运行中遇到导线硬点易折断和破碎,碳滑板固有电阻大,接触温度高,有可能引起导线过热氧化,加速导线磨耗;浸金属碳滑板具有纯碳滑板对导线磨耗小和耐弧性强的特点,同时导电性和机械强度比纯碳滑板均有所提高,但是,浸金属碳滑板的机械强度,尤其是抗冲击强度有待进一步提高。
炭-炭复合材料是碳纤维增强碳基体的复合材料,具有高强高模、密度小、热膨胀系数小、抗腐蚀、抗热冲击、化学稳定性好、结构性能可设计性等一系列良好性能,是一种优异的热结构-功能一体化的工程材料。由于炭-炭复合材料具有优良的耐摩擦磨损性能、力学性能和导电性能,已成为一种优异的新型摩擦集电材料。
中国专利文献CN201710337141.6公开了一种受电弓滑板材料的制备方法,首先将镍粉等粉碎、压制后煅烧,得到活化陶瓷粉末,随后将膨胀石墨与沼液混合发酵,经微生物作用向膨胀石墨内引入活性位点,并经原位沉积,向膨胀石墨内部引入耐电弧烧蚀的稀土金属,再将甲基三氯硅烷作为碳化硅前驱体,在高温作用下分解产生碳化硅,通过碳化硅与硼化锆作用形成能自愈的玻璃态ZrO2-SiO2,从而使材料的抗氧化耐烧蚀性能提高,最后与树脂等混合、压制、煅烧制得受电弓滑板材料;但是该受电弓滑板材料抗冲击强度较低,电阻率和接触电阻偏高。
随着铁路列车的不断提速,原有的受电弓滑板零件已经不能满足现在高速和准高速机车的使用要求,为了解决上述滑板存在的不足,急需要开发出一种耐电弧、磨耗小、导电性强、耐腐蚀和耐热性优良的滑板来替换原有滑板。
发明内容
为了解决现有技术存在的不足,本发明的目的在于提供一种碳-碳复合材料受电弓滑板及其制备方法,制备得到的受电弓滑板材料电阻率和接触电阻低,抗冲击强度高,具有良好的减磨自润滑性能以及耐热耐电弧性能。
为了实现上述目的,本发明采用如下技术方案:
一种碳-碳复合材料受电弓滑板的制备方法,包括如下步骤:
(1)将石油焦、沥青焦、炭黑混合均匀,在110~130℃下混捏处理0.5~1h;然后加入改性氧化石墨烯,升温至120~140℃,混捏处理1~2h,得到混料;
(2)将混料与改性碳纤维加入到已预热至130~150℃的热辊轧机中,反复辊轧0.5~1h,得到0.5~0.8mm厚的辊轧料;
(3)将辊轧料捏碎后加入到压制机中压制成型,得到素坯;
(4)将素坯加入到烧结炉中,在N2气氛下焙烧,冷却至室温得到烧结体;
(5)将烧结体放入浸渍罐中,抽真空,然后加入熔融的中温沥青进行浸渍,得到浸渍料;
(6)重复步骤(4)的烧结和步骤(5)的浸渍过程2~3次,得到碳-碳复合材料受电弓滑板。
优选的,步骤(1)中,石油焦、沥青焦、炭黑、改性氧化石墨烯的重量比为5~15:30~50:25~40:10~20;步骤(2)中,混料与改性碳纤维的重量比为100:8~15;步骤(3)中,压制条件为15~20MPa、120~130℃下压制1~2h;步骤(4)中,焙烧条件为900~1100℃下焙烧3~5d;步骤(5)中,抽真空至3~5torr,浸渍条件为140~160℃、2~5MPa下浸渍8~12h。
优选的,步骤(1)中,改性氧化石墨烯的制备方法包括如下步骤:
a、将氧化石墨烯分散至KMnO4/H2SO4混合液中,搅拌然后静置,将产物过滤、洗涤、干燥,然后将其加入到乙醇水溶液中,搅拌并超声分散,得到氧化石墨烯分散液;
b、将去离子水与无水乙醇混合,加入36wt%浓盐酸调节pH至2~3,然后加入钛酸四丁酯,搅拌1~2h,得到TiO2溶胶;
c、将去离子水与无水乙醇混合,加入36wt%浓盐酸调节pH至2~3,然后加入正硅酸乙酯,搅拌1~2h,得到SiO2溶胶;将TiO2溶胶与SiO2溶胶混合,50~60℃下搅拌6~8h,得到TiO2/SiO2溶胶;
d、将TiO2/SiO2溶胶滴加入氧化石墨烯分散液中,密封搅拌反应,将产物抽滤、洗涤、干燥,得到改性氧化石墨烯。
优选的,步骤(2)中,改性碳纤维的制备方法包括如下步骤:
S1、将碳纤维浸渍入丙酮中,反应结束后,将产物洗涤、干燥,然后将碳纤维浸入KH550水溶液中,恒温浸泡,将产物洗涤、干燥,得到预处理碳纤维;
S2、将预处理碳纤维、FeCl3·6H2O分散于去离子水中,边搅拌边加入水合肼,超声分散,然后密封搅拌反应,将产物过滤、洗涤、干燥,得到改性碳纤维。
优选的,步骤a中,KMnO4/H2SO4混合液中KMnO4的浓度为0.1~0.5mol/L,H2SO4的浓度为0.1~0.2mol/L;搅拌10~20min,然后静置30~60min;乙醇水溶液的浓度为20~40wt%,搅拌超声时间0.5~1h。
优选的,步骤b中,去离子水、无水乙醇、钛酸四丁酯的重量比为10:6~12:8~15;步骤c中,去离子水、无水乙醇、正硅酸乙酯的重量比为10:8~10:6~12,TiO2溶胶与SiO2溶胶的体积比为1~2:1。
优选的,步骤d中,TiO2/SiO2溶胶与氧化石墨烯分散液的体积比为1~2:3,氧化石墨烯分散液中氧化石墨烯质量分数为20~30wt%;TiO2/SiO2溶胶2~4h滴完,搅拌反应条件为120~140℃下水热反应12~18h。
优选的,步骤S1中,反应条件为70~80℃下反应30~60min;KH550水溶液的浓度为5~10wt%,碳纤维与KH550水溶液的重量比为1:4~6;恒温浸泡条件为60~80℃下浸泡2~3h。
优选的,步骤S2中,预处理碳纤维、FeCl3·6H2O、去离子水、水合肼的重量比为10:2~4:30~50:1~3;超声分散时间4~6h,搅拌反应条件为140~160℃下反应6~8h。
本发明还要求保护一种所述制备方法制备得到的碳-碳复合材料受电弓滑板。
与现有技术相比,本发明具有如下有益效果:
1)本发明提供了一种碳-碳复合材料受电弓滑板,主要原料是石油焦、沥青焦、炭黑、改性氧化石墨烯、改性碳纤维,通过混捏、辊轧、焙烧、浸渍等工艺,制备得到的碳-碳复合材料轻量化、一体化程度高,具有优异的各向同性,电阻率和接触电阻低,抗冲击强度高,表现出良好的减磨自润滑性能以及耐热耐电弧性能。
2)本发明提供了一种改性氧化石墨烯,首先利用KMnO4/H2SO4混合液改善氧化石墨烯的黏附特性和键合情况,为后续纳米TiO2及纳米SiO2的原位生成做准备;纳米材料比表面积大且表面能极高,因此有很强的团聚性,本发明首先制备得到TiO2溶胶和纳米SiO2溶胶,通过原位生成使其均匀分布在氧化石墨烯表面,后续又以氧化石墨烯为碳源,以气氛中的N2为氮源,高温条件下在界面处原位反应生成TiN、TiNC、SiC、Si3N4等纳米晶须或颗粒,不仅提高了碳-碳复合材料的致密度,同时起到了增强、增韧、提高耐磨性的作用。
3)本发明提供了一种改性碳纤维,首先利用丙酮除去碳纤维表面的疏水涂层,使其具有亲水性,然后利用KH550对碳纤维进行改性,一方面使其表面活化,增加碳纤维表面的反应位点,有利于后续纳米Fe3O4的包覆,另一方面,通过KH550将-NH2和有机长链接枝到碳纤维表面,能够改善碳纤维与油性碳基体之间的相容性,增强碳纤维与基体界面处的电导性能;后续又利用水合肼做还原剂将纳米Fe3O4负载在碳纤维表面,能够削弱碳纤维的团聚,使碳纤维均匀分布在碳基体中形成导电通路,从而降低复合材料的电阻率;碳纤维具有高的比强度和比模量,改性后的碳纤维能够充分发挥其补强效果,有效提高滑板材料的抗折抗压强度和韧性。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚,以下结合实施例,对本发明作进一步的详细说明。当然,此处所描述的具体实施例仅仅用于解释本发明,并不用于限定本发明。
如无特殊说明外,本发明中的化学试剂和材料均通过市场途径购买或通过市场途径购买的原料合成。
石油焦:粒度为-325目,水分≤1%,灰分≤1%,采用低硫熟焦块状;
沥青焦:真密度≥2.10g/cm3,灰分≤0.5%,挥发分<0.8%;
中温沥青:软化点为105~112℃,甲苯不溶物为25~28%,喹啉不溶物为6~12%;结焦值≥58%,挥发份为50~55%;
炭黑:电阻率为0.6~1.0μΩ·m,粒径为45~60μm;
氧化石墨烯:拉伸模量≤1.01TPa,极限强度≤116GPa;
碳纤维为短切碳纤维,长度为1~5mm,优选为2~3mm。
下面通过具体实施例,来对本发明作进一步的说明。
实施例1
一种碳-碳复合材料受电弓滑板的制备方法,包括如下步骤:
(1)将氧化石墨烯分散至KMnO4/H2SO4混合液(KMnO4的浓度为0.3mol/L,H2SO4的浓度为0.15mol/L)中,搅拌20min然后静置60min,将产物过滤、洗涤、干燥,然后将其加入到40wt%乙醇水溶液中,搅拌并超声分散1h,得到氧化石墨烯分散液;
(2)将10kg去离子水与12kg无水乙醇混合,加入36wt%浓盐酸调节pH至3,然后加入15kg钛酸四丁酯,搅拌2h,得到TiO2溶胶;
(3)将10kg去离子水与10kg无水乙醇混合,加入36wt%浓盐酸调节pH至3,然后加入12kg正硅酸乙酯,搅拌2h,得到SiO2溶胶;将20L TiO2溶胶与10L SiO2溶胶混合,60℃下搅拌8h,得到TiO2/SiO2溶胶;
(4)将20LTiO2/SiO2溶胶滴加入30L 20wt%氧化石墨烯分散液中,4h滴完,密封、140℃下水热反应18h,将产物抽滤、洗涤、干燥,得到改性氧化石墨烯;
(5)将碳纤维浸渍入丙酮中,80℃下反应60min,将产物洗涤、干燥,然后将1kg碳纤维浸入6kg 10wt%KH550水溶液中,80℃下恒温浸泡3h,将产物洗涤、干燥,得到预处理碳纤维;
(6)将10kg预处理碳纤维、4kg FeCl3·6H2O分散于50kg去离子水中,边搅拌边加入3kg水合肼,超声分散6h,然后密封、160℃下搅拌反应8h,将产物过滤、洗涤、干燥,得到改性碳纤维;
(7)将10kg石油焦、40kg沥青焦、30kg炭黑混合均匀,在120℃下混捏处理1h;然后加入15kg改性氧化石墨烯,升温至130℃,混捏处理1.5h,得到混料;
(8)将100kg混料与12kg改性碳纤维加入到已预热至140℃的热辊轧机中,反复辊轧1h,得到0.8mm厚的辊轧料;
(9)将辊轧料捏碎后加入到压制机中,在17MPa、125℃下压制1.5h压制成型,得到素坯;
(10)将素坯加入到烧结炉中,在N2气氛、1000℃下焙烧4d,冷却至室温得到烧结体;
(11)将烧结体放入浸渍罐中,抽真空至4torr,然后加入熔融的中温沥青进行浸渍,在150℃、4MPa下浸渍10h,得到浸渍料;
(12)重复步骤(10)的烧结和步骤(11)的浸渍过程2次,得到碳-碳复合材料受电弓滑板。
实施例2
一种碳-碳复合材料受电弓滑板的制备方法,包括如下步骤:
(1)将氧化石墨烯分散至KMnO4/H2SO4混合液(KMnO4的浓度为0.3mol/L,H2SO4的浓度为0.15mol/L)中,搅拌10min然后静置30min,将产物过滤、洗涤、干燥,然后将其加入到20wt%乙醇水溶液中,搅拌并超声分散0.5h,得到氧化石墨烯分散液;
(2)将10kg去离子水与6kg无水乙醇混合,加入36wt%浓盐酸调节pH至2,然后加入8kg钛酸四丁酯,搅拌1h,得到TiO2溶胶;
(3)将10kg去离子水与8kg无水乙醇混合,加入36wt%浓盐酸调节pH至2,然后加入6kg正硅酸乙酯,搅拌1h,得到SiO2溶胶;将10L TiO2溶胶与10L SiO2溶胶混合,50℃下搅拌6h,得到TiO2/SiO2溶胶;
(4)将10LTiO2/SiO2溶胶滴加入30L 20wt%氧化石墨烯分散液中,2h滴完,密封、120℃下水热反应12h,将产物抽滤、洗涤、干燥,得到改性氧化石墨烯;
(5)将碳纤维浸渍入丙酮中,70℃下反应30min,将产物洗涤、干燥,然后将1kg碳纤维浸入4kg 5wt%KH550水溶液中,60℃下恒温浸泡2h,将产物洗涤、干燥,得到预处理碳纤维;
(6)将10kg预处理碳纤维、2kg FeCl3·6H2O分散于30kg去离子水中,边搅拌边加入1kg水合肼,超声分散4h,然后密封、140℃下搅拌反应6h,将产物过滤、洗涤、干燥,得到改性碳纤维;
(7)将10kg石油焦、40kg沥青焦、30kg炭黑混合均匀,在120℃下混捏处理1h;然后加入15kg改性氧化石墨烯,升温至130℃,混捏处理1.5h,得到混料;
(8)将100kg混料与12kg改性碳纤维加入到已预热至140℃的热辊轧机中,反复辊轧1h,得到0.8mm厚的辊轧料;
(9)将辊轧料捏碎后加入到压制机中,在17MPa、125℃下压制1.5h压制成型,得到素坯;
(10)将素坯加入到烧结炉中,在N2气氛、1000℃下焙烧4d,冷却至室温得到烧结体;
(11)将烧结体放入浸渍罐中,抽真空至4torr,然后加入熔融的中温沥青进行浸渍,在150℃、4MPa下浸渍10h,得到浸渍料;
(12)重复步骤(10)的烧结和步骤(11)的浸渍过程2次,得到碳-碳复合材料受电弓滑板。
实施例3
一种碳-碳复合材料受电弓滑板的制备方法,包括如下步骤:
(1)将氧化石墨烯分散至KMnO4/H2SO4混合液(KMnO4的浓度为0.3mol/L,H2SO4的浓度为0.15mol/L)中,搅拌15min然后静置45min,将产物过滤、洗涤、干燥,然后将其加入到30wt%乙醇水溶液中,搅拌并超声分散1h,得到氧化石墨烯分散液;
(2)将10kg去离子水与10kg无水乙醇混合,加入36wt%浓盐酸调节pH至2.5,然后加入12kg钛酸四丁酯,搅拌1.5h,得到TiO2溶胶;
(3)将10kg去离子水与9kg无水乙醇混合,加入36wt%浓盐酸调节pH至2.5,然后加入10kg正硅酸乙酯,搅拌1.5h,得到SiO2溶胶;将15LTiO2溶胶与10L SiO2溶胶混合,55℃下搅拌7h,得到TiO2/SiO2溶胶;
(4)将15LTiO2/SiO2溶胶滴加入30L 20wt%氧化石墨烯分散液中,2~4h滴完,密封、130℃下水热反应15h,将产物抽滤、洗涤、干燥,得到改性氧化石墨烯;
(5)将碳纤维浸渍入丙酮中,75℃下反应45min,将产物洗涤、干燥,然后将1kg碳纤维浸入5kg 8wt%KH550水溶液中,70℃下恒温浸泡2.5h,将产物洗涤、干燥,得到预处理碳纤维;
(6)将10kg预处理碳纤维、3kg FeCl3·6H2O分散于40kg去离子水中,边搅拌边加入2kg水合肼,超声分散5h,然后密封、150℃下搅拌反应7h,将产物过滤、洗涤、干燥,得到改性碳纤维;
(7)将10kg石油焦、40kg沥青焦、30kg炭黑混合均匀,在120℃下混捏处理1h;然后加入15kg改性氧化石墨烯,升温至130℃,混捏处理1.5h,得到混料;
(8)将100kg混料与12kg改性碳纤维加入到已预热至140℃的热辊轧机中,反复辊轧1h,得到0.8mm厚的辊轧料;
(9)将辊轧料捏碎后加入到压制机中,在17MPa、125℃下压制1.5h压制成型,得到素坯;
(10)将素坯加入到烧结炉中,在N2气氛、1000℃下焙烧4d,冷却至室温得到烧结体;
(11)将烧结体放入浸渍罐中,抽真空至4torr,然后加入熔融的中温沥青进行浸渍,在150℃、4MPa下浸渍10h,得到浸渍料;
(12)重复步骤(10)的烧结和步骤(11)的浸渍过程2次,得到碳-碳复合材料受电弓滑板。
对比例1
一种碳-碳复合材料受电弓滑板的制备方法,包括如下步骤:
(1)将碳纤维浸渍入丙酮中,80℃下反应60min,将产物洗涤、干燥,然后将1kg碳纤维浸入6kg 10wt%KH550水溶液中,80℃下恒温浸泡3h,将产物洗涤、干燥,得到预处理碳纤维;
(2)将10kg预处理碳纤维、4kg FeCl3·6H2O分散于50kg去离子水中,边搅拌边加入3kg水合肼,超声分散6h,然后密封、160℃下搅拌反应8h,将产物过滤、洗涤、干燥,得到改性碳纤维;
(3)将10kg石油焦、40kg沥青焦、30kg炭黑混合均匀,在120℃下混捏处理1h;然后加入15kg氧化石墨烯,升温至130℃,混捏处理1.5h,得到混料;
(4)将100kg混料与12kg改性碳纤维加入到已预热至140℃的热辊轧机中,反复辊轧1h,得到0.8mm厚的辊轧料;
(5)将辊轧料捏碎后加入到压制机中,在17MPa、125℃下压制1.5h压制成型,得到素坯;
(6)将素坯加入到烧结炉中,在N2气氛、1000℃下焙烧4d,冷却至室温得到烧结体;
(7)将烧结体放入浸渍罐中,抽真空至4torr,然后加入熔融的中温沥青进行浸渍,在150℃、4MPa下浸渍10h,得到浸渍料;
(8)重复步骤(6)的烧结和步骤(7)的浸渍过程2次,得到受电弓滑板。
对比例2
一种碳-碳复合材料受电弓滑板的制备方法,包括如下步骤:
(1)将氧化石墨烯分散至KMnO4/H2SO4混合液(KMnO4的浓度为0.3mol/L,H2SO4的浓度为0.15mol/L)中,搅拌20min然后静置60min,将产物过滤、洗涤、干燥,然后将其加入到40wt%乙醇水溶液中,搅拌并超声分散1h,得到氧化石墨烯分散液;
(2)将10kg去离子水与12kg无水乙醇混合,加入36wt%浓盐酸调节pH至3,然后加入15kg钛酸四丁酯,搅拌2h,得到TiO2溶胶;
(3)将10kg去离子水与10kg无水乙醇混合,加入36wt%浓盐酸调节pH至3,然后加入12kg正硅酸乙酯,搅拌2h,得到SiO2溶胶;将20L TiO2溶胶与10L SiO2溶胶混合,60℃下搅拌8h,得到TiO2/SiO2溶胶;
(4)将20LTiO2/SiO2溶胶滴加入30L 20wt%氧化石墨烯分散液中,4h滴完,密封、140℃下水热反应18h,将产物抽滤、洗涤、干燥,得到改性氧化石墨烯;
(5)将10kg石油焦、40kg沥青焦、30kg炭黑混合均匀,在120℃下混捏处理1h;然后加入15kg改性氧化石墨烯,升温至130℃,混捏处理1.5h,得到混料;
(6)将100kg混料与12kg碳纤维加入到已预热至140℃的热辊轧机中,反复辊轧1h,得到0.8mm厚的辊轧料;
(7)将辊轧料捏碎后加入到压制机中,在17MPa、125℃下压制1.5h压制成型,得到素坯;
(8)将素坯加入到烧结炉中,在N2气氛、1000℃下焙烧4d,冷却至室温得到烧结体;
(9)将烧结体放入浸渍罐中,抽真空至4torr,然后加入熔融的中温沥青进行浸渍,在150℃、4MPa下浸渍10h,得到浸渍料;
(10)重复步骤(8)的烧结和步骤(9)的浸渍过程2次,得到受电弓滑板。
将实施例1~3、对比例1~2制备所得受电弓滑板进行物理性能测试,体积密度参考JB/T 8133.14-2013《电炭制品物理化学性能试验方法第14部分:体积密度》,采用四探针法在高精度电阻率测试仪中测量材料的电阻率(试样尺寸3mm×4mm×36mm,测试方向平行于纤维层),抗折强度参考JB/T 8133.7-2013《电炭制品物理化学性能试验方法第7部分:抗折强度》,抗压强度参考JB/T 8133.8-2013《电炭制品物理化学性能试验方法第8部分:抗压强度》,冲击韧性测试在电子万能试验机上进行(试样尺寸为5×5×55mm,加载方向垂直于纤维层),具体数据见表1。
表1受电弓滑板材料物理性能数据
将实施例1~3、对比例1~2制备所得受电弓滑板加工成尺寸为120mm×34.5mm×25mm的长方体试样,在环-块式试验机上进行环-块式高速载流摩擦磨损试验,受电弓滑板与接触线接触(接触压力为70N±10N),试验台带动接触线按250km/h的速度旋转,同时在受电弓滑板与接触线间通以500A电流。记录受电弓滑板高度磨耗比、重量磨耗比、对接触线磨耗比,具体数据见表2。
表2受电弓滑板材料磨耗性能数据
以上所述,仅为本发明较佳的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,根据本发明的技术方案及其发明构思加以等同替换或改变,都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种碳-碳复合材料受电弓滑板的制备方法,其特征在于,包括如下步骤:
(1)将石油焦、沥青焦、炭黑混合均匀,在110~130℃下混捏处理0.5~1h;然后加入改性氧化石墨烯,升温至120~140℃,混捏处理1~2h,得到混料;
(2)将混料与改性碳纤维加入到已预热至130~150℃的热辊轧机中,反复辊轧0.5~1h,得到0.5~0.8mm厚的辊轧料;
(3)将辊轧料捏碎后加入到压制机中压制成型,得到素坯;
(4)将素坯加入到烧结炉中,在N2气氛下焙烧,冷却至室温得到烧结体;
(5)将烧结体放入浸渍罐中,抽真空,然后加入熔融的中温沥青进行浸渍,得到浸渍料;
(6)重复步骤(4)的烧结和步骤(5)的浸渍过程2~3次,得到碳-碳复合材料受电弓滑板。
2.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,石油焦、沥青焦、炭黑、改性氧化石墨烯的重量比为5~15:30~50:25~40:10~20;步骤(2)中,混料与改性碳纤维的重量比为100:8~15;步骤(3)中,压制条件为15~20MPa、120~130℃下压制1~2h;步骤(4)中,焙烧条件为900~1100℃下焙烧3~5d;步骤(5)中,抽真空至3~5torr,浸渍条件为140~160℃、2~5MPa下浸渍8~12h。
3.根据权利要求1所述的制备方法,其特征在于,步骤(1)中,改性氧化石墨烯的制备方法包括如下步骤:
a、将氧化石墨烯分散至KMnO4/H2SO4混合液中,搅拌然后静置,将产物过滤、洗涤、干燥,然后将其加入到乙醇水溶液中,搅拌并超声分散,得到氧化石墨烯分散液;
b、将去离子水与无水乙醇混合,加入36wt%浓盐酸调节pH至2~3,然后加入钛酸四丁酯,搅拌1~2h,得到TiO2溶胶;
c、将去离子水与无水乙醇混合,加入36wt%浓盐酸调节pH至2~3,然后加入正硅酸乙酯,搅拌1~2h,得到SiO2溶胶;将TiO2溶胶与SiO2溶胶混合,50~60℃下搅拌6~8h,得到TiO2/SiO2溶胶;
d、将TiO2/SiO2溶胶滴加入氧化石墨烯分散液中,密封搅拌反应,将产物抽滤、洗涤、干燥,得到改性氧化石墨烯。
4.根据权利要求1所述的制备方法,其特征在于,步骤(2)中,改性碳纤维的制备方法包括如下步骤:
S1、将碳纤维浸渍入丙酮中,反应结束后,将产物洗涤、干燥,然后将碳纤维浸入KH550水溶液中,恒温浸泡,将产物洗涤、干燥,得到预处理碳纤维;
S2、将预处理碳纤维、FeCl3·6H2O分散于去离子水中,边搅拌边加入水合肼,超声分散,然后密封搅拌反应,将产物过滤、洗涤、干燥,得到改性碳纤维。
5.根据权利要求2所述的制备方法,其特征在于,步骤a中,KMnO4/H2SO4混合液中KMnO4的浓度为0.1~0.5mol/L,H2SO4的浓度为0.1~0.2mol/L;搅拌10~20min,然后静置30~60min;乙醇水溶液的浓度为20~40wt%,搅拌超声时间0.5~1h。
6.根据权利要求3所述的制备方法,其特征在于,步骤b中,去离子水、无水乙醇、钛酸四丁酯的重量比为10:6~12:8~15;步骤c中,去离子水、无水乙醇、正硅酸乙酯的重量比为10:8~10:6~12,TiO2溶胶与SiO2溶胶的体积比为1~2:1。
7.根据权利要求3所述的制备方法,其特征在于,步骤d中,TiO2/SiO2溶胶与氧化石墨烯分散液的体积比为1~2:3,氧化石墨烯分散液中氧化石墨烯质量分数为20~30wt%;TiO2/SiO2溶胶2~4h滴完,搅拌反应条件为120~140℃下水热反应12~18h。
8.根据权利要求4所述的制备方法,其特征在于,步骤S1中,反应条件为70~80℃下反应30~60min;KH550水溶液的浓度为5~10wt%,碳纤维与KH550水溶液的重量比为1:4~6;恒温浸泡条件为60~80℃下浸泡2~3h。
9.根据权利要求4所述的制备方法,其特征在于,步骤S2中,预处理碳纤维、FeCl3·6H2O、去离子水、水合肼的重量比为10:2~4:30~50:1~3;超声分散时间4~6h,搅拌反应条件为140~160℃下反应6~8h。
10.一种如权利要求1~9任一项所述制备方法制备得到的碳-碳复合材料受电弓滑板。
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