CN106585388A - 一种电力车辆受电弓滑板用复合材料及其制备方法 - Google Patents

一种电力车辆受电弓滑板用复合材料及其制备方法 Download PDF

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CN106585388A
CN106585388A CN201611116863.0A CN201611116863A CN106585388A CN 106585388 A CN106585388 A CN 106585388A CN 201611116863 A CN201611116863 A CN 201611116863A CN 106585388 A CN106585388 A CN 106585388A
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copper
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electric vehicle
mesh
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CN106585388B (zh
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方华婵
肖鹏
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Central South University
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    • B60—VEHICLES IN GENERAL
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    • B60L5/00—Current collectors for power supply lines of electrically-propelled vehicles
    • B60L5/18—Current collectors for power supply lines of electrically-propelled vehicles using bow-type collectors in contact with trolley wire
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    • C23C16/26—Deposition of carbon only
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    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
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Abstract

一种电力车辆受电弓滑板用复合材料及其制备方法，增强体为由碳纤维与铜网构成的三维复合编织体，以镀铜石墨粉为导电耐磨填料，经CVI沉积、树脂加压浸渍增密，以及高温热处理制备获得的受电弓滑板材料。该复合材料使用碳纤维与铜网的三维复合编织，实现了金属铜在复合材料中形成互为连通状的网络结构，为在载流状态下电子的运动提供了低电阻通道，采用高温烧结，使铜的三维网络结构连续性更好，且材料整体致密度的大幅提高，加上石墨的引入，提高了材料整体的润滑性能，减小了铜网与接触网导线摩擦时导致的导线大幅磨损，在提高整体导电性和机械性能的同时，显著降低其对接触网导线的磨损。本发明具有优良的摩擦性能和机械性能，不仅自身耐磨寿命长，而且对接触网导线的磨损小，从而确保了电力机车的安全运行。

Description

一种电力车辆受电弓滑板用复合材料及其制备方法
技术领域
本发明涉一种电力车辆受电弓滑板用金属型碳纤维增强碳复合材料及其制备方法；属于电力车辆设备制备技术领域。
背景技术
作为电力机车导入电能、获取动力的重要受流部件，受电弓滑板的质量和机电性能对电力机车的受流状况及接触导线的寿命具有重要影响。目前，国内外广泛使用的受电弓滑板主要有纯碳滑板和浸铜碳滑板。纯碳滑板具有自润滑性能，耐磨性好，但是其自身机械强度低，使用过程中易折断、掉块，而且石墨的电阻较大、集电容量小，导致接触区温度高，易引起导线过热氧化腐蚀，加速导线磨损。浸铜碳滑板由于浸渍了熔融铜，因此导电性远优于纯碳滑板，但抗冲击强度仍不能满足高速运行的列车的需要，且对接触网铜导线的粘着磨损相当严重。而且需在1000℃以上，几百个大气压力下加压浸渍成型，因此对生产设备要求苛刻，且制备工艺复杂、产品均匀性不好、成品率低、生产成本高。随着电气化铁路的高速化、重载化的发展，弓网系统的震动幅度必然增加，滑板受到弓网的冲击力更大，离线现象将更频繁，对受电弓滑板的要求更加荀刻，因此今后的受电弓滑板材料必须兼备导电优良、抗冲击强度高、减磨性好以及耐弧性等优点。
碳基纤维复合材料滑板既有碳系滑板的自润滑和对导线磨耗小、密度小等优点，又利用了金属纤维的高强度和低电阻来提高机械强度和降低电阻率，而不必像粉末冶金滑板那样使用外部润滑脂，并且可显著减少滑板对接触导线的磨损，可以满足电力机车受电弓滑板轻量化、耐磨以及载流稳定的要求。目前，日本新研制出的碳基纤维复合材料滑板在一些线路上取得了良好的效果，已逐渐取代粉末冶金滑板，部分用于辅助滑板，以期实现在21世纪新干线速度达到350km/h高速化的目标。
金属型碳纤维复合材料具有低电阻率、高热容量和低成本等优点，是下一代理想受电弓滑板材料之一。中国发明专利CN1468891A公开了一种电力机车受电弓用碳纤维增强碳滑板，采用短切碳纤维为增强材料，石墨、电解铜粉/铜纤维为导电填料，耐高温新型改性酚醛树脂为粘结剂，经热压成型。这种受电弓滑板材料电阻率小、抗冲击性较高，摩擦磨损性能好，对接触导线磨损程度小，但是机械强度不高，且制备工艺复杂。中国发明专利CN1178745 A公开了一种碳纤维增强碳基复合材料制备的电力机车受电弓滑板，以镀铜碳粉为基体材料，短碳纤维为增强剂，热固性树脂为粘结剂，经冷压和热压固化成型。这种受电弓滑板材料摩擦磨损性能好，对接触导线磨损程度小，但是机械强度也不高。中国发明专利申请号200710017899.8公开了一种电力机车用碳/碳受电弓滑板，以针刺无纬布为预制体，经化学气相沉积热解碳后，再通过树脂浸渍-碳化，以及高温石墨化得到C/C复合材料。这种受电弓滑板材料制备工艺简单、压缩强度高、抗冲击性较好，但是机械强度不高。中国发明专利CN 103192718 B公开了一种受电弓滑板用复合材料及其制备方法，采用碳纤维与铜丝的三维编织体，经化学气相沉积和树脂浸渍-碳化工艺制备的碳滑条。中国发明专利申请号201510909260.5公开了一种电力机车用金属型C/C复合材料碳滑条，以将单层0°无纬碳布，碳纤维网胎、石墨粉、铜材构成了碳纤维和铜网三维整体毡为预制体，经化学气相沉积热解碳后，再通过树脂浸渍-碳化工艺得到C/C-Cu复合材料。以上两种受电弓滑板材料制备工艺简单、抗冲击性较好，申请专利201510909260.5中进一步加入石墨粉，提高了整体的润滑性能和致密度，但铜的三维网络结构连续性仍较低，整体致密度较低，机械强度不高，而且铜网与导线摩擦时点接触导致对导线的磨损增大。
发明内容
本发明的目的在于提供一种受电弓滑板用复合材料，旨在解决现有技术提供的受电弓滑板制备工艺复杂、产品综合性能不稳定、制造困难、使用可靠性较低的问题。
本发明一种受电弓滑板用复合材料，是由单层0°无纬碳布，碳纤维网胎、镀铜石墨粉采用接力式针刺法在垂直于铺层方向引入碳纤维束制成碳纤维与铜网的三维复合整体毡；
进一步，碳纤维与铜网的三维复合整体毡所含铜网的体积百分含量为10％～25％，碳纤维的体积百分含量为72％～87％，镀铜石墨粉的质量百分含量为5％～15％；
进一步，制备三维复合整体毡时，选用的是导电性能优良的紫铜网，铜网的目数为20～100目，丝径为0.05～0.2mm；
进一步，所使用的镀铜石墨粉的粒度不大于200微米，镀铜石墨粉中铜的质量分数为30％～70％，石墨的质量分数为30％～70％。
本发明的另一目的在于提供一种电力车辆受电弓滑板用复合材料的制备方法，该制备方法包括以下步骤：
步骤一，将单层0°无纬碳布，碳纤维网胎、镀铜石墨粉、单层90°无纬碳布、碳纤维网胎、镀铜石墨粉、单层0°无纬碳布依次循环叠加后，采用接力式针刺的方法在垂直于铺层方向引入碳纤维束制成碳纤维与铜网的三维复合整体毡；
步骤二，采用丙烯、天然气、甲烷中的至少一种作为碳源气体，以氮气、氢气中的至少一种作为稀释气体，碳源气体和稀释气体的体积比为(0.8-1.2)：(2.8-3.2)，对碳纤维/铜网的三维复合整体毡进行化学气相沉积，沉积温度为820～1000℃，沉积时间为300～500小时；
步骤三，将沉积有热解碳的碳纤维/铜网的三维复合整体毡置于40-80℃的聚合物浸渍液中，1～3MPa下加压浸渍处理1～3小时后，升温至180～210℃固化处理2.5～3.5小时；之后进行碳化处理，碳化温度为830～880℃，单次碳化处理40～60小时；按浸渍-固化-碳化处理的方式循环操作直至得到需要的复合材料。
步骤四，浸渍-碳化后的材料在氢气气氛保护下，于900～980℃高温热处理1～3小时，得到最终的金属型碳纤维增强碳复合材料。
本发明与现有技术相比，其优点与积极效果在于：
1、受电弓滑板用复合材料增强体选用碳纤维与铜网的三维编织体，实现了金属铜在复合材料中形成互为连通状的网络结构，为在载流状态下电子的运动提供了低电阻“通道”。
2、镀铜石墨粉的引入既提高了耐磨性及抗电弧侵蚀性能，还提高了铜的三维网络结构的连续性和材料的致密度，制备的金属型碳纤维增强碳复合材料具有优良的摩擦性能和机械性能，不仅自身耐磨寿命长，而且对接触网导线的磨损小
发明专利CN 103192718 B仅使用碳纤维和铜网的三维复合整体毡进行CVI、浸渍-碳化获得的复合材料，虽然采用CVI热解碳包覆固结双网络构架的“结点”，但沉积的热解碳数量极为有限，导致材料整体的致密度较低，机械性能较差，铜的三维网络结构的连续性较差，运行时，铜网与导线接触时点接触导致对导线的磨损大幅提高。在碳纤维和铜网针刺时，单独加入石墨粉，虽然一定程度提高了材料的整体的润滑性能和致密度，但是由于石墨粉之间未形成连接，导致铜和碳的三维网络结构连续性较差，材料的致密度仍较低，因而对接触网导线的磨损仍较明显。
在碳纤维和铜网针刺时，单独加入铜粉，由于铜粉硬度较高，导致整体毡编制时针刺难度增大，因而本专利采用镀铜石墨粉替代铜粉和石墨粉，这类粉末的硬度适中，易于针刺，且镀铜石墨粉经900～980℃高温处理，石墨颗粒外层的铜粉产生烧结，形成铜和石墨的连续体，不仅提高了铜的三维网络结构的连续性，且材料整体致密度大幅提高，材料导电性能提高。复合材料致密度的提高，铜网被连续铜固定加上石墨粉的润滑作用，运行时，铜网与导线点接触导致导线的磨损大幅降低，在提高了复合材料整体的导电性和机械性能的同时，对导线的磨损显著降低。
具体实施方式：
对比例1：
中国发明专利CN 103192718 B“一种受电弓滑板用复合材料及其制备方法”制备了铜丝质量分数为25％，摩擦面上Cu的面积百分比为15％，坯体密度为1.0g/cm3的毡体，通过化学气相沉积和浸渍-碳化处理，获得最终密度为1.84g/cm3的Cf/Cu-C复合材料，其电阻率为8.12μΩ·m，抗压强度为168MPa、抗弯强度为121MPa，洛氏硬度为53HRC，自制的载流摩擦磨损机上进行载流摩擦磨损试验，实验电流为200A，载荷为65N，磨损时间为3min。测得其最高电弧高度为9mm，磨损量为0.3953g，载流摩擦磨损率为1.1*10-6g/(m*N)。
对比例2：
中国申请专利201510909260.5“一种金属型C/C复合材料碳滑条的制备方法”，采用丝径0.12mm、40目铜丝，质量含量为23％的紫铜网、质量分数10％的石墨粉、碳纤维，制成密度为0.94g/cm3的2.5D碳纤维针刺整体毡，通过化学气相渗透工艺制备了密度为1.72g/cm3的C/C-Cu复合材料，经过两次树脂浸渍-碳化工艺，制备了密度为1.96g/cm3的C/C-Cu复合材料。其电阻率为2.4μΩ·m，经测试，其抗压强度为171MPa、抗弯强度为139MPa，肖氏硬度为70，HP34401A载流量试验台上进行载流摩擦磨损试验，实验电流为500A，载荷为70N，速度为300km/h。重量磨耗比为210g/万机车公里，对接触线磨耗比0.020mm2/万机车公里。
实施例1：
采用丝径0.12mm、40目、质量分数为12％的紫铜网、质量分数为8％镀铜石墨粉(质量分数为30％的石墨，质量分数为70％的铜)、碳纤维，制成密度为0.90g/cm3的2.5D碳纤维/铜网针刺整体毡，通过化学气相渗透工艺制备了密度为1.75g/cm3的C/C-Cu复合材料，经过两次树脂浸渍-碳化工艺和高温处理，制备了密度为2.10g/cm3的C/C-Cu复合材料。
本实施例中的金属型碳纤维增强碳复合材料主要通过以下步骤制备得到：
(1)首先，采用日本东丽公司(Toray)生产的PAN型T700(12K)碳纤维制成网胎和无纬布，将单层0°无纬布、网胎层、镀铜石墨粉(粒度为150微米)、紫铜网、单层90°无纬布、网胎层、镀铜石墨粉、紫铜网、单层0°无纬布依次循环叠加，然后，采用接力式针刺的方法制成密度为0.90g/cm3的碳纤维/铜网针刺整体毡。
(2)采用丙烯为碳源气体，氮气为稀释气，丙烯与氮气的体积比为1:3，采用化学气相渗透法对预制体在860℃下沉积热解碳，沉积310小时后制得密度为1.75g/cm3的C/C-Cu复合材料。
(3)沉积后的C/C-Cu放入真空-压力浸渍罐中，以呋喃树脂为浸渍剂，采用高压浸渍工艺处理。试样应先预热，浸渍温度为60℃，浸渍压力为2MPa，保压时间为1.5小时。之后，升温至200℃，保温约3小时进行固化。固化后转碳化炉进行碳化处理，碳化温度为850℃。循环两次后，材料密度达到2.01g/cm3。
(4)浸渍-碳化后的样件在氢气保护下，920℃高温处理2小时，材料密度达到2.10g/cm3。
其电阻率为3.2μΩ·m，经测试，其抗压强度为195MPa、抗折强度为146MPa，肖氏硬度为90，HP34401A载流量试验台上进行载流摩擦磨损试验，实验电流为500A，载荷为70N，速度为300km/h。重量磨耗比为195g/万机车公里，对接触线磨耗比0.012mm2/万机车公里。
实施例2：
采用丝径0.15mm、50目、质量分数为18％的紫铜网、质量分数为12％镀铜石墨粉(质量分数为45％的石墨，质量分数为55％的铜)、碳纤维，制成密度为1.15g/cm3的2.5D碳纤维/铜网针刺整体毡，通过化学气相渗透工艺制备了密度为1.85g/cm3的C/C-Cu复合材料，经过两次树脂浸渍-碳化工艺和高温处理，制备了密度为2.20g/cm3的C/C-Cu复合材料。
本实施例中的金属型碳纤维增强碳复合材料主要通过以下步骤制备得到：
(1)首先，采用日本东丽公司(Toray)生产的PAN型T700(12K)碳纤维制成网胎和无纬布，将单层0°无纬布、网胎层、镀铜石墨粉(粒度为100微米)、紫铜网、单层90°无纬布、网胎层、镀铜石墨粉、紫铜网、单层0°无纬布依次循环叠加，然后，采用接力式针刺的方法制成密度为1.15g/cm3的碳纤维/铜网针刺整体毡。
(2)采用丙烯为碳源气体，氮气为稀释气，丙烯与氮气的体积比为1:3，采用化学气相渗透法对预制体在900℃下沉积热解碳，沉积350小时后制得密度为1.85g/cm3的C/C-Cu复合材料。
(3)沉积后的C/C-Cu放入真空-压力浸渍罐中，以呋喃树脂为浸渍剂，采用高压浸渍工艺处理。试样应先预热，浸渍温度为60℃，浸渍压力为2MPa，保压时间为2小时。之后，升温至200℃，保温约3小时进行固化。固化后转碳化炉进行碳化处理，碳化温度为860℃。循环两次后，材料密度达到2.15g/cm3。
(4)浸渍-碳化后的样件在氢气保护下，950℃高温处理1.5小时，材料密度达到2.20g/cm3。
其电阻率为2.0μΩ·m，经测试，其抗压强度为185MPa、抗折强度为154MPa，肖氏硬度为86，HP34401A载流量试验台上进行载流摩擦磨损试验，实验电流为500A，载荷为70N，速度为300km/h。重量磨耗比为198g/万机车公里，对接触线磨耗比0.013mm2/万机车公里。
实施例3：
采用丝径0.12mm、100目、质量分数为23％的紫铜网、质量分数为4％镀铜石墨粉(质量分数为40％的石墨，质量分数为60％的铜)、碳纤维，制成密度为1.25g/cm3的2.5D碳纤维/铜网针刺整体毡，通过化学气相渗透工艺制备了密度为1.98g/cm3的C/C-Cu复合材料，经过两次树脂浸渍-碳化工艺和高温处理，制备了密度为2.35g/cm3的C/C-Cu复合材料。
本实施例中的金属型碳纤维增强碳复合材料主要通过以下步骤制备得到：
(1)首先，采用日本东丽公司(Toray)生产的PAN型T700(12K)碳纤维制成网胎和无纬布，将单层0°无纬布、网胎层、镀铜石墨粉(粒度为150微米)、紫铜网、单层90°无纬布、网胎层、镀铜石墨粉、紫铜网、单层0°无纬布依次循环叠加，然后，采用接力式针刺的方法制成密度为1.25g/cm3的碳纤维/铜网针刺整体毡。
(2)采用丙烯为碳源气体，氮气为稀释气，丙烯与氮气的体积比为1:3，采用化学气相渗透法对预制体在950℃下沉积热解碳，沉积400小时后制得密度为1.98g/cm3的C/C-Cu复合材料。
(3)沉积后的C/C-Cu放入真空-压力浸渍罐中，以呋喃树脂为浸渍剂，采用高压浸渍工艺处理。试样应先预热，浸渍温度为70℃，浸渍压力为3MPa，保压时间为1小时。之后，升温至200℃，保温约3小时进行固化。固化后转碳化炉进行碳化处理，碳化温度为880℃。循环两次后，材料密度达到2.30g/cm3。
(4)浸渍-碳化后的样件在氢气保护下，970℃高温处理1小时，材料密度达到2.35g/cm3。
其电阻率为1.2μΩ·m，经测试，其抗压强度为188MPa、抗折强度为147MPa，肖氏硬度为84，HP34401A载流量试验台上进行载流摩擦磨损试验，实验电流为500A，载荷为70N，速度为300km/h。重量磨耗比为185g/万机车公里，对接触线磨耗比0.011mm2/万机车公里。自制的载流摩擦磨损机上进行载流摩擦磨损试验，实验电流为200A，载荷为70N，磨损时间为10min。测得磨损量为0.2048g，载流摩擦磨损率为0.7*10-7g/(m*N)。
比较实施例3和对比例1、2可以看出，在铜含量相近的情况下，本工艺制备的金属型碳纤维增强碳复合材料的电阻率降低明显，机械强度提高，自身磨损量降低，对导线的磨损量降低明显。

Claims (10)

1.一种电力车辆受电弓滑板用复合材料，所述复合材料由单层0°无纬碳布，碳纤维网胎、镀铜石墨粉、单层90°无纬碳布、碳纤维网胎、镀铜石墨粉、单层0°无纬碳布依次循环叠加后，采用接力式针刺的方法在垂直于铺层方向引入碳纤维束制成碳纤维与铜网的三维复合整体毡；所述碳纤维与铜网三维复合整体毡中，含铜网的体积百分含量为10％～25％，碳纤维的体积百分含量为72％～87％，镀铜石墨粉的质量百分含量为5％～15％。
2.根据权利要求1所述的一种电力车辆受电弓滑板用复合材料，其特征在于：铜网选用导电性能优良的紫铜网，铜网的目数为20～100目，丝径为0.05～0.2mm。
3.根据权利要求1所述的一种电力车辆受电弓滑板用复合材料，其特征在于：镀铜石墨粉的粒度小于等于200微米，镀铜石墨粉中铜的质量分数为30％～70％，石墨的质量分数为30％～70％。
4.一种电力车辆受电弓滑板用复合材料的制备方法，其特征在于；包括下述步骤：
步骤一
将单层0°无纬碳布，碳纤维网胎、镀铜石墨粉、单层90°无纬碳布、碳纤维网胎、镀铜石墨粉、单层0°无纬碳布依次循环叠加后，采用接力式针刺的方法在垂直于铺层方向引入碳纤维束制成碳纤维与铜网的三维复合整体毡；所述碳纤维与铜网三维复合整体毡中，镀铜石墨粉的质量百分含量为5％～15％；
步骤二
将步骤一所得碳纤维与铜网的三维复合整体毡，依次通过化学气相沉积热解碳处理和聚合物浸渍-碳化工艺处理，得到金属型碳纤维增强碳复合材料预成品；
步骤三
在氢气保护气氛下，于900～980℃，对步骤二所得预成品进行高温热处理，处理时间1～3小时，得到金属型碳纤维增强碳复合材料。
5.根据权利要求4所述的一种电力车辆受电弓滑板用复合材料的制备方 法，其特征在于：步骤一中，所使用的镀铜石墨粉的粒度小于等于200微米，镀铜石墨粉中铜的质量分数为20％～70％，石墨的质量分数为30％～80％。
6.根据权利要求5所述的一种电力车辆受电弓滑板用复合材料的制备方法，其特征在于：步骤一中，所述碳纤维与铜网的三维复合整体毡中，铜网的体积百分含量为10％～25％，碳纤维的体积百分含量为72％～87％。
7.根据权利要求6所述的一种电力车辆受电弓滑板用复合材料的制备方法，其特征在于：步骤一中，所使用铜网的目数为20～100目，丝径为0.05～0.2mm，材质为紫铜。
8.根据权利要求4所述的一种电力车辆受电弓滑板用复合材料的制备方法，其特征在于：步骤二中，化学气相沉积热解碳处理工艺参数是采用丙烯、天然气、甲烷中的至少一种作为碳源气体，以氮气、氢气中的至少一种作为稀释气体，碳源气体和稀释气体的体积比为(0.8-1.2)：(2.8-3.2)，对碳纤维/铜网的三维复合整体毡进行化学气相沉积热解碳处理，沉积温度为820～1020℃，沉积时间为300～500小时。
9.根据权利要求8所述的一种电力车辆受电弓滑板用复合材料的制备方法，其特征在于：步骤二中，聚合物浸渍-碳化工艺处理工艺参数是：按浸渍-固化-碳化处理的方式循环操作直至得到得到金属型碳纤维增强碳复合材料预成品；所述浸渍是在40～80℃的聚合物浸渍液中，1～3MPa下加压浸渍处理1～3小时；所述固化是在180～210℃固化处理2.5～3.5小时；所述碳化处理温度为830～880℃，单次碳化处理40～60小时。
10.根据权利要求4-9任意一项所述的一种电力车辆受电弓滑板用复合材料制备方法，其特征在于：步骤三中，氢气气氛下，于900～980℃，对步骤二所得预成品进行高温热处理1～3小时，得到金属型碳纤维增强碳复合材料。
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