CN101479636A - 抗漏电的芳族聚酰胺纱 - Google Patents
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Abstract
本发明涉及一种芳族聚酰胺长丝纱，其具有包含有机物质的整理剂成分，如此选择在所述整理剂中的有机物质的量，以便在20℃下作为在水中的50wt％的整理剂成分测量时，所述整理剂具有0.2mS/cm至200mS/cm的电导率，并且如此选择在所述纱上的所述整理剂的量，以便所述纱具有4×104至1.2×107欧姆·cm的电阻率。本发明还涉及一种用所述芳族聚酰胺长丝纱的束加强的ADSS线缆，以及一种制造所述ADSS线缆的方法。
Description
技术领域
本发明涉及一种具有整理剂(finish)成分的抗漏电(antitracking)芳族聚酰胺长丝纱以及由其制成的ADSS(全介质自承式)线缆(cable)。
背景技术
ADSS线缆已使用多年，主要用于其中需要基础结构的快速实现的区域中。其优点在于，可以在高电压输电线路处进行安装而不关断线路电压。
在电线杆之间安装ADSS线缆。由于高电压导体的电场，所产生的空间电势可容易地达到最高达15kV的水平。只要ADSS线缆的表面电阻足够高，在跨度的中间与电线杆(线缆在此接地)之间的空间电势差就不引起任何显著的电流。
对ADSS线缆的野外试验表明，当由于雾和露而使灰尘层变得潮湿时，灰尘层的产生可以导致表面电阻的显著降低。这使得几毫安的电流能够流过沉积的层。当该层变干燥时，可以在线缆表面上形成第一干燥区(干燥带)。与潮湿层相比，该干燥带具有极高的表面电阻。从而，在干燥带两段之间沿着线缆长度产生的电势差降低。因此，将发生对线缆外皮(sheath)有损伤的电弧放电。线缆制造商已经十分注意该问题，并且已经实施了减轻该问题的贯彻措施。公知抗漏电外皮材料的引入极大地改善了外皮材料对抗放电的抵抗性。尽管有该改善，在极端含尘环境中(例如在沙漠中)ADSS线缆的寿命是不足够的。
EP 214480公开了对ADSS线缆的另一改进，其描述了在线缆外皮之下提高芳族聚酰胺纱的电导率。由于线缆外皮与导电纱的电容性耦合，放电较不强烈。注意到，为了排除对从事线缆安装工作的人员的身体危险，流过芳族聚酰胺纱的电流应该不太大。
通过在线缆生产期间在芳族聚酰胺纱上施加特殊的胶质(jelly)，使得芳族聚酰胺纱导电。已经证明，在ADSS线缆中，很难确保导电胶质沿着加强纱恒定且均匀分布。结果，这样的ADSS线缆的寿命缩短。
普通的ADSS线缆包含芯、加强的芳族聚酰胺纱以及外皮。芯包含光纤且可以被形成为中心管款式，该款式是在石油-胶质中包含光纤的中空管。在另一款式中，在玻璃纤维成分周围的1层或2层中具有5至18个中空管(疏松管款式)。中空管在石油-胶质中包含光纤。这样的疏松管款式可具有围绕其的内护套(jacket)，该内护套通常由聚乙烯制成。
对于关键性的应用，外护套由对火花有较好抵抗性的特殊聚合物(抗漏电聚合物)制成。
芳族聚酰胺纱特别地可用于中和张力。张力是通过重量和安装压力，以及通过风和冰层的存在而产生的。外皮保护芳族聚酰胺纱和在线缆的内部中的其它元件不受日光和水的影响。
由于水移动到线缆的最低点，因此后者很重要。当其结冰时，演变为显著的压缩力，这导致光纤的信号损耗。光纤还对氢和水蒸汽敏感，也导致信号损耗。
当线缆在外侧包含灰尘层时，可以形成火花(干燥带电弧放电)。
即使在非常短的周期例如一周内，这些火花也会损伤外皮。当在外护套中形成孔时，芳族聚酰胺受影响，于是线缆会断裂。
发明内容
我们现在已经发现一种使得芳族聚酰胺纱导电的不同方法，其确保在ADSS线缆中整理剂沿着加强纱均匀分布。
为此，本发明涉及一种用芳族聚酰胺长丝纱加强的ADSS线缆，该芳族聚酰胺长丝纱具有包含有机物质的整理剂成分，如此选择在所述整理剂中的有机物质的量，以便在20℃下作为在水中的50wt％的整理剂成分测量时，所述整理剂具有0.2mS/cm至200mS/cm的电导率，并且如此选择在所述纱上的所述整理剂的量，以便所述纱具有4×104至1.2×107欧姆·cm的电阻率。
在另一实施例中，本发明还涉及新颖的芳族聚酰胺长丝纱本身，其可以被用于制造利用这样的芳族聚酰胺纱加强的ADSS线缆。
本方法与现有技术方法的区别在于，在被嵌入ADSS线缆之前，对1000至40000dtex的加强芳族聚酰胺纱束进行分别处理，并且使用包含特定导电有机物质的整理剂，而不是处理ADSS线缆本身。通过用整理剂处理单独的(individual)芳族聚酰胺纱束来替代在线缆中整个加强芳族聚酰胺材料，发现可以获得向纱束中更好的渗透以及更均匀的分布。结果，电流未受到由线缆中差的或者未被处理的纱部分的存在引起的干扰。
已发现，当在芳族聚酰胺长丝纱上施加包含导电有机物质(COS)的整理剂时，其电学纱电阻减小。根据整理剂的量、整理剂中有机物质的量以及所施加的有机物质的导电率，处理后的纱可被用作ADSS线缆中的抗漏电纱。
在旋涂工艺期间或者在单独的工艺步骤中，导电有机物质可以被施加到湿润或干燥的纱上作为旋涂整理剂(在干燥之前或之后，原剂或者用溶剂例如水稀释的)。
该纱的电阻率不太低，以避免对于在高电压输电线路上的工人而言危险的情况(例如触电死)，并且避免在缆塔处不希望的温度升高。另一方面，电阻率不太高，以具有足够的抗漏电性能。
已经发现，在ADSS线缆中，用这样的整理剂处理后的芳族聚酰胺长丝纱呈现优良的抗漏电性能，其中该整理剂包含有机导电物质且具有4×104至1.2×107欧姆·cm、更优选7×104至1×106欧姆·cm的电阻率。通过应用本领域公知的且下面将在此描述的简单且普通的电学测量，可以容易地调整整理剂中有机物质的量以及施加到纱上的所述整理剂的量，以获得所需的电导率以及电阻率。可以通过本领域已知的简单的电导率测量本身来非常容易地确定所施加的整理剂的合适的量。当确定了整理剂溶液的电导率时，技术人员可以根据特定用途的需要来施加所需的整理剂的量。
需要这样的在整理剂中的导电有机物质的量，在20℃下作为在水中的50wt％的整理剂成分测量时，该整理剂给出0.2mS/cm至200mS/cm的电导率。更优选整理剂具有1mS/cm至50mS/cm的电导率。
给出所需的电导率和电阻率的纱上整理剂的特别合适的量在1至30wt％的范围内，更优选在8-22wt％的范围内。wt％是相对于不具有整理剂和潮气的纱的总重量而言的。
用于本发明中的合适的有机物质为具有可静态充电的酸基或碱基、或者其盐的材料。也可以使用非离子组分。具有酸基的材料优选为脂肪酸、(烷基)磷酸酯、(烷基)膦酸酯、(烷基)磺酸酯、(烷基)硫酸酯、以及其盐。具有碱基的材料优选为胺化合物、咪唑衍生物和季铵化合物、以及其盐。特别优选的材料是(烷基)磷酸酯、(烷基)膦酸酯的盐、以及季铵化合物。酸基优选为羧酸基、膦酸基或磺酸基。碱基优选为胺基团。特别优选的材料是脂肪酸、碳酸、(环)烷基磷酸酯、(环)烷基膦酸酯、(环)烷基硫酸酯、(环)烷基磺酸酯、咪唑啉衍生物等。特别合适的是具有80至800、优选130至600、最优选190至450的电荷密度的有机物质。电荷密度被定义为被有机物质分子中的可充电基的数量除的有机物质的分子量。
芳族聚酰胺纱优选由聚对苯二甲酰对苯二胺(PPTA)制成，但也可以包含少量的其它单体。优选的芳族聚酰胺具有至少90GPa的模量。
通过本领域已知的常规方法在纱上施加COS。可以在溶液中施加COS。溶剂可以为任何合适的溶剂，例如水、酒精、醚、四氢呋喃、丙酮、苯、甲苯、乙酸乙酯、二氯甲烷等。最优选地，应用COS本身，即未被稀释。
本发明还涉及这些纱在线缆中的使用以及包括所述纱的线缆，所述线缆具有与由未经处理的芳族聚酰胺纱制成的线缆相同的机械特性。本发明特别地可用于ADSS线缆中。
具体实施方式
用于ADSS线缆的寿命测试的工序
将长度为1m的两个线绕的端连接(所谓的中国指套(Chinesefingers))附接到6m长度的样品ADSS线缆。例如，通过液压缸，对该线缆施加3.5kN的张力。以与水平面成3°的角度安装该线缆。在该线缆上方大约1m处，安装高电压框架(场电极)。在线缆的下端，安装公知的环形(torodical)场电极。通过200pF的电容器，该电极被连接到高电压框架。可以对高电压框架施加交流高电压。在室(chamber)的高端上安装电流监视器。监视器的另一侧连接到地。
在其中可以通过通风器随意更换空气的室中安装线缆和所提到的其它装置。
接下来，在0.5mm的层中对在端连接之间的线缆样品施加由50％的表I的固体和50％的水构成的糊膏。接下来，打开通风器，直到所施加的层变干(至少3个小时)。
在该准备之后，可以开始分成循环的测量。
首先，在通风器关断的条件下，在测试室的气氛中喷涂具有0.4g/l的氯化钠的水，持续4分钟。这使得在线缆上的沉积层的潮气完全饱和。接下来，该室被通风4分钟，以完全排出潮气。现在在通风器仍然接通的条件下，对高电压框架施加30kV的高电压。(这感应出至少1.5mA的流过线缆外侧的电流)。由于线缆被干燥过，电流降低，并且在ADSS线缆的外侧，尤其在上端连接的附近，出现火花。然而，如果该电流显著降低(低于0.5mA)，不再出现火花，并且在24分钟之后关断高电压。关断通风器，并且通过喷涂氯化钠溶液而再次开始下一循环。
每天一次停止测量循环至少4小时，以允许所沉积的层完全干燥。在这段时间期间或者当打火花时的电流增大时，在上端连接的附近检查线缆的护套。如果护套以芳族聚酰胺变得可见的这样的方式被破坏，则结束测试程序，并记录循环的次数。
表1 沉积层的成分
| 组分 | 质量百分率 |
| 氯化钠 | 3％ |
| 石膏 | 10％ |
| 白垩 | 32％ |
| 粘土 | 50％ |
| 水泥 | 5％ |
用于确定整理剂的电导率的工序
确定根据本发明的整理剂成分的电导率的合适工序如下。
在烧杯中倒入将被测试的足量的整理剂水溶液(50wt％的水和50wt％的COS)。随后，在20℃的温度下根据DIN标准38404 Teil 8(9.1985)确定该溶液的电导率。
当包含COS的整理剂具有比50wt％低或高的水含量时，通过分别添加软化水或者在低于100℃的高温下在搅拌之下在热板上加热来蒸发水，将整理剂溶液的浓度调整为50wt％。对于电导率的测量，使用电导率测量计型inoLab of the Wissenschaftlich-Technische GmbH，Weilheim，Germany。
通过Karl Fischer法确定整理剂溶液的水含量。在由Eugen Scholz编著、Springer-Verlag在1984年出版的“Karl Fischer Titration，Methodenzur Wasserbestimmung”中，给出了对通过Karl Fischer试剂来确定水的确切描述。
用于确定电阻率的工序
对于芳族聚酰胺纱的电阻率的确定，使用包括被两个聚四氟乙烯杆(rod)隔开的两个铜棒(bar)的样品-夹具。这些棒相互之间的距离为52mm。被测试的纱(优选在7600与11000dtex之间)围绕着两个铜棒被缠绕数圈(优选在11与15之间)，该两个铜棒与DC高压电源和Keithley静电计连接。在20℃和65％的相对湿度下在铜棒之上施加500V的电压之后，利用Keithley静电计确定电流。根据欧姆定律、铜棒之间的纱长度、纱连接的数量以及纱的截面积，计算出纱的电阻率。
利用下面的非限制性实例，进一步示例本发明。
实例1
对商业可得的高模量
D2200(9660 dtex/f 6000)的纱封装进行下面的处理。滚动展开该纱封装，同时使得该纱依次在液体敷料器(liquidapplicator)之上通过且经过热风炉(温度为200℃，停留时间为10秒)。接着，以30m/min的速度将处理后的芳族聚酰胺纱缠绕到封装中。利用液体敷料器和计量泵，用包含COS的整理剂a1(表A)处理该纱。利用溶剂甲苯来稀释该整理剂，以实现整理剂的均匀分布。在热处理期间，溶剂甲苯蒸发。测量出处理后的纱的电阻率。
接着，制造光纤线缆，其在石油-胶质中包含被光玻璃纤维填充的中心管，并且用处理后的芳族聚酰胺纱进行加强。为此，将厚度为2mm的抗漏电聚合物的护套挤压在具有6mm外径的中心管周围，该中心管被包封在27(×9660 dtex/f 6000)根处理后的纱中。线缆的外径为约12mm。
实例2(比较实例)
在挤压工艺期间，使用以下工序制造与实例1相同的光纤线缆。被光玻璃纤维和石油-胶质填充的中心管被包封在27根高模量
D2200纱(9660 dtex/f 6000)中。使用漏斗(funnel)在加强纱上投配整理剂a2，并且将线缆拖曳穿过磨具，从而实现整理剂的均匀分布。最后，将抗漏电的护套挤压在线缆周围。
在测试间中，对具有同量的COS和加强材料的实例1和2的光纤线缆进行测试。其结果示于表B中。很明显，当利用包含COS的整理剂处理单独的(individual)芳族聚酰胺纱而不是线缆中大量的芳族聚酰胺时，获得具有较好的抗漏电性能的光纤线缆。
实例3至5
在实例3至5中，执行几乎相同的工序，以产生如在实例1中所述的光纤线缆。仅仅改变COS的量和类型，并且替代稀释的整理剂，采用整理剂本身(表A)。结果，可以省略纱干燥处理。
结果示于表C中。
其表明，当分别用包含COS的整理剂处理加强的芳族聚酰胺纱时，可以获得改善的抗漏电性。
表A 包含导电有机物质的整理剂的成分
LA 
是磷酸异壬基酯、二乙醇胺盐(60-80％)和聚乙二醇异壬基苯酚(<25％)的混合物，供应商为Info-Lab Ltd.，Limerick，Ireland。
甲苯是芳族烃(溶剂)，供应商为Sigma-Aldrich，Saint Louis，USA。
表B 测试结果
表C 测试结果
Claims (13)
1.一种芳族聚酰胺纱，具有包含有机物质的整理剂成分，如此选择在所述整理剂中的有机物质的量，以便在20℃下作为在水中的50wt％的整理剂成分测量时，所述整理剂具有0.2mS/cm至200mS/cm的电导率，并且如此选择在所述纱上的所述整理剂的量，以便所述纱具有4×104至1.2×107欧姆·cm的电阻率。
2.根据权利要求1的芳族聚酰胺纱，其中如此选择在所述整理剂中的有机物质的量，以便所述整理剂具有1mS/cm至50mS/cm的电导率。
3.根据权利要求1或2的芳族聚酰胺纱，其中如此选择在所述整理剂中的有机物质的量和在所述纱上的所述整理剂的量，以获得电阻率为7×104至1×106欧姆·cm的纱。
4.根据权利要求1-3中任何一项的芳族聚酰胺纱，其中所述纱包含1至30wt％、优选8至22wt％的所述整理剂成分。
5.根据权利要求1-4中任何一项的芳族聚酰胺纱，其中所述有机物质包含至少一种静态可充电的可为盐形式的酸基或碱基。
6.根据权利要求5的芳族聚酰胺纱，其中所述有机物质包含羧酸酯、膦酸酯、磷酸酯、磺酸酯、硫酸酯和胺基团中的至少一种，或者其中所述有机物质为咪唑衍生物或季铵化合物。
7.根据权利要求6的芳族聚酰胺纱，其中所述有机物质为(烷基)膦酸酯、(烷基)磷酸酯的盐，或者为季铵化合物。
8.根据权利要求1-7中任何一项的芳族聚酰胺纱，其中所述芳族聚酰胺为聚对苯二甲酰对苯二胺(PPTA)。
9.根据权利要求8的芳族聚酰胺纱，其中所述芳族聚酰胺具有大于90GPa的模量。
10.一种利用权利要求1-9中任何一项的芳族聚酰胺纱的束加强的ADSS线缆。
11.根据权利要求10的ADSS线缆，其中单独的纱的束具有1000至40000dtex的线密度。
12.根据权利要求10或11的ADSS线缆，其中外护套由抗漏电的聚合物制成。
13.一种用于制造权利要求10至12中任何一项的ADSS线缆的方法，其中用包含有机物质的整理剂成分处理芳族聚酰胺纱，其中如此选择在所述整理剂中的有机物质的量，以便在20℃下作为在水中的50wt％的整理剂成分测量时，所述整理剂具有0.2mS/cm至200mS/cm的电导率，并且其中如此选择在所述纱上的所述整理剂的量，以使所述纱具有4×104至1.2×107欧姆·cm的电阻率，并且此后将所述纱的束嵌入线缆中，所述线缆包括常用于ADSS线缆的构件。
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