CN1142557C - 具有半导性阻水膨胀层的电缆 - Google Patents

具有半导性阻水膨胀层的电缆 Download PDF

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CN1142557C
CN1142557C CNB988125668A CN98812566A CN1142557C CN 1142557 C CN1142557 C CN 1142557C CN B988125668 A CNB988125668 A CN B988125668A CN 98812566 A CN98812566 A CN 98812566A CN 1142557 C CN1142557 C CN 1142557C
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CN1306668A (zh
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S·拜利
A·巴莱基
L·凯米
L·巴尔克尼
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Gscp Arsenal (lux) Ii Saar
Price Miln Lux Ii Co
Pirelli and C SpA
Prysmian Cavi e Sistemi Energia SRL
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B9/00Power cables
    • H01B9/02Power cables with screens or conductive layers, e.g. for avoiding large potential gradients
    • H01B9/027Power cables with screens or conductive layers, e.g. for avoiding large potential gradients composed of semi-conducting layers
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00Insulated conductors or cables characterised by their form
    • H01B7/17Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/28Protection against damage caused by moisture, corrosion, chemical attack or weather
    • H01B7/282Preventing penetration of fluid, e.g. water or humidity, into conductor or cable
    • H01B7/285Preventing penetration of fluid, e.g. water or humidity, into conductor or cable by completely or partially filling interstices in the cable
    • H01B7/288Preventing penetration of fluid, e.g. water or humidity, into conductor or cable by completely or partially filling interstices in the cable using hygroscopic material or material swelling in the presence of liquid
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A30/00Adapting or protecting infrastructure or their operation
    • Y02A30/14Extreme weather resilient electric power supply systems, e.g. strengthening power lines or underground power cables

Abstract

具有金属屏蔽和一半导性阻水膨胀层的电缆,特别是为中压或高压电力输电或配电的电缆。膨胀层的功能有三:其一是能均匀和弹性地吸收电缆使用中热循环引起的电缆包覆层膨胀和收缩的径向辐射力,因而能阻止金属屏蔽的变形或破裂;其二是保证电缆芯和金属屏蔽间的电连续性;其三是在例如金属屏蔽可能的破裂时能有效地避免湿气和/或水沿电缆芯渗透或传播。第三功能是在膨胀层中加入水溶胀性材料得到的。

Description

具有半导性阻水膨胀层的电缆
                      发明领域
本发明涉及一种电缆,特别涉及具有半导性阻水膨胀层的中压或高压输电或配电电缆。在本发明说明书中,“中压”一词系指约1KV-约30KV之间的电压,“高压”一词系指大于30KV的电压。
                      背景技术
中压或高压电源的输电或配电电缆通常由包覆有第一半导性内层、绝缘层和半导性外层的金属导电体组成。在一些室外的应用中(特别是需要水密时),电缆是被包覆在金属屏蔽(通常是铝屏蔽或铜屏蔽)中的,是由连续的管子形成的,或是用金属薄片形成管形,再加以熔焊或焊封,以便使其不渗水。
在电缆的生产、安装或使用过程中,金属屏蔽可能出现裂隙或刺孔,引起湿气、甚至是水渗透入电缆芯,同时在绝缘层中形成电化学树状结晶,破坏了绝缘。
此问题的可能解决办法提供于USP 4,145,567中,其中描述了一高压电缆,它的半导性外层的外部围绕着一层泡沫塑料材料的可压缩层,以防止外部湿气进入绝缘层,因而避免了电化学树状结晶的形成。按照其公开的内容,金属屏蔽最好对可压缩层保持一些压力,这样就不会有空气或其它流体沿可压缩层和金属屏蔽间的界面流动。防止流体沿电缆流动的另一保障是将金属屏蔽粘合在可压缩层上。可压缩层最好是半导性的。
金属屏蔽可因电缆受到的热循环引起破裂,热循环是电缆承受日常输送的电流强度变化并且电缆中的温度也相应地在室温和最大工作温度之间(例如20℃-90℃)变化的结果。这些热循环引起电缆包覆层的膨胀和相继的收缩,最后在金属屏蔽上产生径向辐射力。因此金属屏蔽承受了机械变形,并在屏蔽和半导性外层之间形成空隙,这样便可能产生非均匀性电场。在极度情况下,这些变形可导致屏蔽的破裂,特别是在熔焊或用封接方式连接的情况下,并因此完全失掉了屏蔽功能。
此问题的可能解决方法提供在USP 5,281,757中,其中金属屏蔽对于相邻的层是自由移动的,并有用黏合剂粘合在一起的重叠的边缘部分,黏合剂允许重叠的边缘部分在电缆的热循环过程中互相之间作相对运动。在金属屏蔽和电缆芯之间可采用如上述USP 4,145,567中所公开的衬垫层。需要时,衬垫层可以是水溶胀性带子或是水溶胀性粉末,以代替泡沫塑料材料。
根据申请人的经验,诸如USP 4,145,567和USP 5,281,757中所述的那些电缆设计是不能完全令人满意的。首先,如USP 4,145,567中所公开的金属屏蔽和电缆芯之间存在的可压缩层不能充分有效地避免湿气或水沿电缆的渗透和传播。事实上,要得到有效的阻水作用,在USP 5,281,757中建议使用水溶胀性带子或粉末以代替可压缩层。但是,在金属屏蔽下引入水溶胀性材料会引起严重的电学问题。在实际上,金属屏蔽除了对水和/或湿气的渗透构成屏障外,还给予了重要的电学功能并需要与半导性外层进行电学接触。金属屏蔽的第一个功能是在电缆的内部建立一个均匀的径向电场,同时消除电缆外部的电场。它的进一步功能是支持短路电流。
诸如金属屏蔽下的水溶胀性材料之类的绝缘材料的存在不能保证电缆芯和金属屏蔽间的电学连续性。再者,从生产和处理的观点看,水溶胀性带子或自由流动的水溶胀性粉末的使用存在许多缺点。特别是水溶胀性带子的使用包括了明显的成本增加和生产率的降低,因为带子很贵并意味着在电缆的生产过程中要增加包覆工段。另一方面,自由流动的水溶胀性粉末的存在使电缆的生产和安装变得十分繁琐。
最后,为减弱热循环对金属屏蔽的作用同时又避免湿气和/或水沿电缆传播而设计的本技术领域中已知的电缆提供有纵向V-形槽的半导性外层,槽中充填了粉末状水溶胀性材料。V-形几何形状一方面应保证半导层与金属屏蔽间的电接触,另一方面应由生成半导层的材料帮助热膨胀的弹性恢复。
但是,纵向槽的生产包括使用厚度大的(约2mm或更大)半导层,因而增加了成本和电缆的总重量。加之所要求的半导层的几何形状一般是用精密的挤出加工来完成的,其中使用了适当设计的模具。实际上,根据申请人的经验,在这种挤出过程中不可避免地形成几何形状不规则的槽。这些几何形状的不规则性能使施于金属屏蔽上的压力产生非均匀分布,并因此阻止半导层去正确执行径向辐射力的弹性吸收功能。
因此,上述现有技术的电缆不能有效地解决避免电缆芯内部的湿气和/或水分的渗透和传播问题以及由于电缆热循环引起的金属屏蔽可能的变形或破裂问题,同时在金属屏蔽和电缆芯之间保持正常的电接触。
                发明内容和具体实施方式
申请人现已发现,上述的问题可以有效地用如下的方法来解决:在金属屏蔽之下插入一层有半导性并包括一水溶胀性材料的膨胀型聚合材料。此层材料能够有弹性地和均匀地吸收电缆使用时受热循环所引起的膨胀和收缩的径向辐射力,同时保证了电缆和金属屏蔽间必须的电连续性。再者,分散在膨胀层中的水溶胀性材料的存在能够有效地阻止湿气和/或水分,因此就避免了使用水溶胀性带子或自由流动的水溶胀性粉末。
因此,本发明的第一方面涉及包括一导体、至少一个绝缘层、一层外部的金属屏蔽和一层置于金属屏蔽之下的膨胀型聚合材料层的电缆,其特征在于膨胀型聚合材料层是半导性的并包括一水溶胀性材料。
下面的“膨胀型聚合材料层”将简要地以“膨胀层”表示。
在本发明说明书和权利要求书中,“膨胀型聚合材料”应理解为在此材料中有预定的“自由”空间百分数,即此空间没有被聚合物所占据而是被气体或空气所占据。
一般,膨胀型聚合物中的自由空间百分数是以膨胀度(G)一词表示的,用下列的公式来定义:
                 G=(d0/de-1)×100式中d0代表非膨胀型聚合物密度;de代表膨胀型聚合物的表观密度。
本发明膨胀层的膨胀度根据所使用的特定聚合材料和要求得到的包覆厚度而有较宽范围的变化。预测膨胀度,以便保证电缆由热膨胀和收缩产生的径向辐射力能被弹性吸收并同时保持半导性性能。一般,膨胀度的范围可为5%-500%,优选10%-200%。
本发明的膨胀层厚度至少等于0.1mm,优选0.2-2mm,甚至更优选0.3-1mm。厚度低于0.1mm时,在实际上是很难生产的,并且在任何情况下只能对变形做有限的补偿。厚度大于2mm时,虽然在原则上没有任何功能上的缺点,但当任何特定的要求能有理地说明增加的成本时是可以使用的。
根据优选,本发明的电缆也包括一置于绝缘包层和膨胀层之间的密实半导层。
“密实半导层”一词应理解为由非膨胀型半导性材料(即膨胀度基本上为零的材料)制成的层。
申请人认为,密实半导层能有效地执行阻止部分放电并因而损害电缆的功能。这种放电是由绝缘包层和膨胀层的界面表面中的任何不规则性引起的。这一功能甚至可用一非常薄的半导层来完成,即其厚度约为0.1mm或更小的半导层。但从实际的观点看,厚度为0.2-1mm是优选的,甚至更优选0.2-0.5mm。
如上所示,膨胀层包括水溶胀性材料。如申请人进行的试验所示,膨胀层能掺合大量的水溶胀性材料,当膨胀层置于与湿气或水接触时,掺合的水溶胀性材料能够膨胀,因而能有效地执行它的阻水功能。
水溶胀性材料一般是细分的形式,特别是粉末形式。构成水溶胀性粉末的颗粒的优选粒径不大于250μm,平均粒径为10-100μm。粒径为10-50μm的颗粒的较优选用量为粉末总重量的至少50%(重量)。
水溶胀性材料一般由聚合物链上有亲水基团的均聚物或共聚物组成,例如交联的并至少是部分成盐的聚丙烯酸(例如C.F.StockhausenGmbH的产品Cabloc或Grain Processing Co.的Waterlock);与丙烯酰胺和丙烯酸钠的共聚物混合的淀粉或其衍生物(例如Henkel AG的SGP吸收剂聚合物);羧甲基纤维素钠(例如Hercules Inc.的产品B1anose)。
要得到有效的阻水作用,包括在膨胀层中的水溶胀性材料的量一般是5-120phr,优选15-80phr(phr=相对100重量份基聚合物所用的重量份)。
图1所示为本发明电缆的具体实施方案的横截面,为单极类型,适合于中压电力传输。
此电缆包括导体(1)、半导性内层(2)、绝缘层(3)、密实半导层(4)、膨胀层(5)、金属屏蔽(6)和一外保护层(7)。
导体(1)一般由金属线组成,优选的金属线是铝或铜,是用常规的技术编织在一起的。金属屏蔽(6),通常是用铝或铜制成,也可使用铅,是由连续的金属管或用金属片加工成管状,然后熔焊或用粘合材料封接,制成以使其成为水密性的。金属屏蔽(6)通常包裹了外保护层(7),外保护层(7)是用交联或非交联的聚合材料组成,例如聚氯乙烯(PVC)或聚乙烯(PE)。
构成膨胀层的聚合材料可以是任何类型的可膨胀的聚合物,诸如聚烯烃、不同烯烃的共聚物、烯烃与烯属不饱和酯的共聚物、聚酯、聚碳酸酯、聚砜、酚型树脂、尿型树脂以及它们的混合物。适合的聚合物之例有:聚乙烯(PE),特别是低密度聚乙烯(LDPE)、中密度聚乙烯(MDPE)、高密度聚乙烯(HDPE)、线型低密度聚乙烯(LLDPE)、超低密度聚乙烯(ULDPE),聚丙烯(PP),弹性乙烯/丙烯共聚物(EPR)或乙烯/丙烯/二烯三元共聚物(EPDM),天然橡胶,丁基橡胶,乙烯/乙烯酯共聚物,例如乙烯/乙酸乙烯酯共聚物(EVA),乙烯/丙烯酸酯共聚物,特别是乙烯/丙烯酸甲酯(EMA)、乙烯/丙烯酸乙酯(EEA)和乙烯/丙烯酸丁酯(EBA),乙烯/α-烯烃热塑性共聚物,聚苯乙烯,丙烯腈/丁二烯/苯乙烯(ABS)  树脂,卤化聚合物,特别是聚氯乙烯(PVC),聚氨酯(PUR),聚酰胺,芳香族聚酯,诸如聚对苯二甲酸乙二醇酯(PET)或聚对苯二甲酸丁二醇酯(PBT)以及它们的共聚物或机械混合物。
优选的聚合材料是烯烃聚合物或基于乙烯和/或丙烯的共聚物,并特别选自:
(a)乙烯与烯属不饱和酯的共聚物,例如乙酸乙烯酯,或乙酸丁酯,其中不饱和酯的量一般在5-80%(重量),优选10-50%(重量);
(b)乙烯与至少一种C3-12α-烯烃和可选一种二烯的弹性共聚物,优选乙烯/丙烯(EPR)或乙烯/丙烯/二烯的共聚物,一般具有下列的组成:35-90%(摩尔)乙烯;10-65%(摩尔)α-烯烃;0-10%(摩尔)二烯(例如1,4-己二烯或5-亚乙基-2-降冰片烯);
(c)乙烯与至少一种C4-12α-烯烃和可选一种二烯的共聚物,优选的α-烯烃是1-己烯、1-辛烯等,其密度一般为0.86-0.90克/厘米3,其组成如下:75-97%(摩尔)乙烯;3-25%(摩尔)α-烯烃;0-5%(摩尔)二烯;
(d)用乙烯/C3-12α-烯烃共聚物改性的聚丙烯,其中聚丙烯与乙烯/C3-12α-烯烃共聚物之间的重量比在90/10-10/90,优选80/20-20/80。
例如市售产品Elvax(Du Pont)、Levaprene(Bayer)和Lotryl(Elf-Atochem)属于(a)类;Dutral(Enichem)或Nordel(Dow-Du Pont)属于(b)类;属于(c)类的是Engage(Dow-Du Pont)或Exact(Exxon);而以乙烯/α-烯烃共聚物改性的聚丙烯是以商标名Moplen或Hifax(Montell),或Fina-Pro等提供商品销售的。
在(d)类中特别优选的是热塑性弹性体,包括有连续的热塑性聚合物(例如聚丙烯)基质和细粒的(粒径一般为1-10μm数量级)的固化弹性聚合物(例如交联的EPR或EPDM,分散于热塑性基质中)。弹性聚合物可以非固化状态掺合在热塑性基质中,然后加入适量的交联剂在加工中进行化学交联。另外,弹性聚合物也可以分别固化,然后以细颗粒形式分散于热塑性基质中。这种类型的热塑性弹性体叙述于例如US4,104,210或EP-324,430中。这些热塑性弹性体是优选的,因为它们证明在电缆热循环的整个工作温度范围弹性吸收径向辐射力是特别有效的。
本技术领域中已知的制备半导性聚合物组合物的产品可以用来使聚合材料具有半导性能,特别可以使用的是导电炭黑,例如导电的炉法炭黑或乙炔炭黑等。炭黑的表面积一般大于20m2/g,通常为40-500m2/g。有利的是可以使用表面积至少为900m2/g的高导炭黑,诸如商业上已知的商品名为KetjenblackEC(Akzo Chemie NV)的炉法炭黑。
加入到聚合物基质中的炭黑量根据聚合物和所用的炭黑类型、要求到达的膨胀度、膨胀剂等而有所不同。因此,炭黑的量应给予膨胀材料足够的半导性能,特别是要能得到在室温下膨胀材料的体积电阻率小于500Ωm,优选小于20Ωm。典型的炭黑量可在1-50%(重量)范围,优选3-30%(重量),相对于聚合物的重量。
在绝缘包层和膨胀层之间选择性存在的密实半导层以及半导性内层(均为密实类型)是按已知的技术制备的,特别是用挤出法。聚合材料和炭黑选自上述膨胀层所用的聚合材料和炭黑。
绝缘层最好以聚烯烃用挤出法制备,聚烯烃选自上述膨胀层所用的聚烯烃,特别是聚乙烯、聚丙烯、乙烯/丙烯共聚物等。挤出后,材料最好用已知技术进行交联,例如用过氧化物或通过硅烷。
膨胀层可用含半导性填料和阻水材料的聚合材料在电缆芯上用挤出法来制备。电缆芯即导体(1)、半导性内层(2)、绝缘层(3)和选择性使用的密实半导层(4)的总成。电缆芯本身也可用挤出法制备,特别是用已知技术中的三层挤出法。
聚合材料可按本技术领域中已知的方法与半导性填料、水溶胀性材料和其它选择性使用的常规添加剂混合。混合的进行可用例如有切割转子(Banbury)或互穿转子类型的密闭式混合机,或在诸如共捏合机(Buss)类型或同向旋转或反向旋转的双螺杆类型连续混合机中进行。
聚合物的膨胀常在挤出阶段中进行。膨胀的产生可用加入适合的膨胀剂(即在特定的温度和压力条件下能释放气体的试剂)的化学方式,或用直接将气体高压注入挤出机的机筒的物理方式。将膨胀剂加入聚合材料最好是如上所述在加入填料和其它添加剂之后进行,并相继将混合物冷却至膨胀剂的分解温度以下,以避免聚合物早期膨胀。膨胀剂在挤出过程中(例如通过挤出机料斗)加入聚合组合物是特别有利的。
适合的膨胀剂之例有:偶氮二碳酰胺、对甲苯磺酰肼、有机酸(例如柠檬酸)与碳酸盐和/或碳酸氢盐(例如碳酸氢钠)的混合物等。
高压注入挤出机机筒的气体之例有:氮、二氧化碳、空气、低沸烃(例如丙烷或丁烷)、卤代烃(例如二氯甲烷、三氯氟甲烷、1-氯-1,1-二氟乙烷)等,或者它们的混合物。
机头中的模具直径最好略小于欲得到的有膨胀包层的电缆的最终直径,因此在挤出机外的聚合物的膨胀便使电缆到达所要求的直径。挤出温度的选择主要决定于聚合物基质的性质、膨胀剂和所要求的膨胀度。通常,不低于140℃的挤出温度是优选的,以达到足够的膨胀度。
膨胀型聚合材料可以交联或不交联。交联可用已知技术在挤出和膨胀阶段后进行,特别是在自由基引发剂(例如有机过氧化物,诸如过氧化二枯基)存在下用加热的方法进行。另外,可以通过硅烷进行交联,它允许使用诸如上述的那些聚合物,特别是聚烯烃,它们与包括至少有一个可水解基团(例如三烷氧基硅烷基,特别是三甲氧基硅烷基)的硅烷单元共价结合。硅烷单元的接枝可用硅烷化合物用自由基反应来进行。硅烷化合物有:例如甲基三乙氧基硅烷、二甲基二乙氧基硅烷、乙烯基二甲氧基硅烷等。交联是在水和交联催化剂存在下进行的。交联催化剂有:例如有机钛酸盐或羧酸金属盐。二月桂酸二丁锡(DBTL)是优先选择的。
一经膨胀层制备好后,就将电缆包覆在金属屏蔽中。根据最佳具体实施方案,在无作用力时,膨胀层的直径是大于金属屏蔽的内径的,在施以金属屏蔽后,这样便使膨胀层得到一个预压度。此预压度使膨胀层和金属屏蔽之间到达最佳接触成为可能,并且在绝缘层的热收缩阶段过程中能使膨胀层的任何残余变形或金属屏蔽的某种程度的塑性变形得到恢复。
最后,金属屏蔽可以用保护层包裹,保护层可用例如聚合材料(常用聚氯乙烯或聚乙烯)经挤出而得到。
下面是几个说明性实施例,以对本发明进一步描述。
实施例1-2
制备了适合于形成本发明膨胀层的一些混合物。各组成示于表1(phr)。混合物的组分在一Banbury密闭式混合机(工作容积1.2升)中混合在一起。首先加入基料聚合物,经一短期加工后,加入炭黑、水溶胀性粉末和其它添加剂(膨胀剂除外)。
混合进行约6分钟,其提取材料的最终温度约为150℃。混合结束时在混合物中加入膨胀剂,提取材料事先冷却至100℃,以免膨胀剂预先分解致使聚合物的膨胀不可控制。然后将混合物用一尺寸为200×200mm、厚度为3mm的框架在160℃下压缩模塑。加入的混合物量应使之得到1mm厚的初始层,以便留有足够的空间让聚合物膨胀。对如此得到的试块测定的特性如下:
…表观密度,然后按上面所给的公式计算膨胀度(已知非膨胀材料的密度);
…室温下的体积电阻率。
数据示于表1。
将一些样品放入水中,观察到了水溶胀性粉末立即膨胀至体积约为初始体积的3倍。
实施例3
按照图1的结构,用实施例1中的聚合组合物生产了中压电缆。聚合组合物按实施例1制备,但不加膨胀剂,以避免组合物早期膨胀。膨胀剂只在挤出时加入,如下所述。
要在其上沉积膨胀层的电缆芯包括横截面为70mm2的铝导体,包覆以在悬垂线上用过氧化物交联的下列各层:
…半导性内层,由含炭黑的EPR制成(厚0.5mm);
…绝缘层,由高岭土填充的EPR制成(厚5.5mm);
…半导性外层(密实),由含35%(重量)的N 472炭黑的EVA制成(厚0.5mm)。
在这样的电缆芯(外直径约23mm)上积附膨胀层时,用构型为25D的80mm单螺杆挤出机。挤出机装有具有纵向沟槽的机筒初始段、箱型进料喉和长25D的有螺线的卸料螺杆。供料区料的螺槽深度为9.6mm,最终段为7.2mm,其总螺杆压缩比约为1∶1.33。
在挤出机的下游使用了一装有双接合线传送带的电加热垂直挤出头。使用如下的组装模具:直径24mm的口模;直径24mm的环形压缩模。口模选择的目的要使欲被包覆的电缆芯易于通过,其直径比欲被包覆的电缆芯直径约大1mm;另一方面,环形模的选择,其直径咯小于要得到的产品的最终直径,以阻止材料在挤出头内部膨胀。
挤出机和挤出头的加热情况如下(℃):
料喉 螺杆 1区 2区 3区 4区 5区 6区
20 中温 160 170 180 185 190 195 200 200
欲被包覆的电缆芯的挤出速度设定为所要求的膨胀材料厚度的函数。在本例中使用了1.2m/min的线速度。在这些条件下纪录了下列的挤出参数:
        挤出机旋转速度:1.2rpm;
        热半成品直径: 25.0mm;
        冷半成品直径:24.8mm。
将半成品在空气中冷却,避免直接与冷水接触,这样就不会引发阻水粉末的突然再溶胀问题。随后将得到的半成品绕在卷轴上。
材料在电缆芯上积附厚度约1mm。将此材料用化学方法进行膨胀,在挤出机料斗中加入约2%的膨胀剂HydrocerolCF 70(羧酸+碳酸氢钠)。
测定如此得到的膨胀层样品的电导率和膨胀度。测得的膨胀率约为20%。
也进行了在水存在下材料的膨胀试验(阻水作用):由于有水溶胀性粉末的存在,材料溶胀至其体积约为初始体积的3倍。
实施例4
使用热塑性弹性体作为基材料生产本发明的膨胀层。其组成列于表1(包括仅在挤出过程中加入的膨胀剂)。混合是在同样的Banbury混合机中进行,如实施例1-2所述。混合时间约10分钟,提取材料的最后温度约195℃。混合后将材料造粒并封于塑料袋中以避免吸收湿气。
实施例5
按图1的结构图用实施例4的聚合组合物组生产中压电缆。
电缆芯由横截面为150mm2和直径14.0mm的铝导体组成,包覆以如下各层,在catenary线上用过氧化物交联:
…半导性内层:Borealis产品LE 0595(厚0.6mm);
…XLPE制成的绝缘层(厚4.65mm);
…半导性外层(密实):Borealis产品LE 0595(厚0.4mm)。
按实施例3所述的技术挤出将膨胀层积附在电缆芯(外径约25.3mm)上。使用30mm单螺杆挤出机,构型24D,口模直径25.7mm,环形压缩模直径26.1mm,其热状况(℃)如下:
料喉 螺杆 1区 2区 3区
20 浮动 190 200 210 200 200
膨胀剂在挤出过程中通过挤出机料斗加入。线速度为2.9m/min,螺杆速度为56rpm。挤出和冷却后膨胀层的厚度为0.65mm。
然后将这样得到的电缆包以上漆的铝带(厚0.2mm),其重叠的边缘用黏合剂粘合。最后用挤出法用PVC制成一外保护层。
按照说明NF C 33-233(1998年3月)将两段3米长的最终电缆在热循环下进行渗水试验。在除去中心部分(长50mm)的外包覆层暴露出半导性外层(4)后,将电缆样品浸入水中并在室温下保持24小时,然后承受10次热循环,每次8小时(4小时用环形电路沿导体加热至100℃,然后4小时冷却)。试验结束时,水通过切割处从一端渗入20cm,从另一端渗入25cm,因而主要在说明书要求的范围(电缆样品的两端无水出现)。
                             表1
    实施例     1     2     3
 Elvax470     100     --     --
 Elvax265     --     100     --
 ProfaxPF 814     --     --     20
 SantopreneRC8001     --     --     80
 Ketjenblack    EC300     20     20     10
 Irganox1010     0.5     0.5     0.2
 IrganoxPS802     --     --     0.4
 WaterlockJ550     40     40     25
 HydrocerolCF70     2     2     2
 d0(g/cm3)     1.15     1.15     1.012
 de(g/cm3)     0.95     0.95     0.86
 膨胀度(%)     21     21     17.7
 体积电阻率(Ωm)     <15     <15     2
Elvax470(Du Pont):乙烯/乙酸乙烯酯共聚物(EVA)(18%VA,熔体指数0.7);
Elvax265(Du Pont):EVA共聚物(28%VA,熔体指数3.0);
ProfaxPF 814(Montell):全同立构丙烯均聚物(MFI=3g/10’-ASTM D 1238);
SantopreneRC8001(Monsanto):热塑性弹性体(89%w固化EPR,11%聚丙烯);
KetjenblackEC(Akzo Chemie):高导炉法炭黑;
WaterlockJ550(Grain Processing Co.):磨细的交联聚丙烯酸(部分成盐)(直径10-45μm的颗粒大于50%w);
HydrocerolCF70(Boeheringer Ingelheim):羧酸/碳酸氢钠膨胀剂;
Irganox1010:四[3-(3,5-二叔丁基-4-羟苯基)丙酸]季戊四醇酯(Ciba-Geigy);
IrganoxPS802 FL:硫代二丙酸二硬脂基酯(DSTDP)(Ciba-Geigy)。

Claims (27)

1.电缆,包括一导体、至少一个绝缘层、一个外部的金属屏蔽和一层置于金属屏蔽之下的聚合材料膨胀层,其特征在于聚合材料膨胀层是半导性的并包括一水溶胀性材料,其中膨胀层有预定的膨胀度,以保证电缆热膨胀和收缩的径向辐射力的弹性吸收和保持半导性能,和其中膨胀层的室温下的膨胀材料的体积电阻率低于500Ωm。
2.权利要求1所述的电缆,其中膨胀层的膨胀度为5%-500%。
3.权利要求2所述的电缆,其中膨胀层的膨胀度为2%-200%。
4.前述任一项所述的电缆,其中膨胀层的厚度至少为0.1mm。
5.权利要求4所述的电缆,其中膨胀层的厚度为0.2-2mm。
6.权利要求1-3任一项所述的电缆,也包括置于绝缘包覆层和膨胀层之间的密实半导层。
7.权利要求6所述的电缆,其中密实半导层的厚度为0.1-1mm。
8.权利要求7所述的电缆,其中密实半导层的厚度为0.2-0.5mm。
9.权利要求1-3任一项所述的电缆,其中水溶胀性材料是粉末形式。
10.权利要求9所述的电缆,其中水溶胀性材料是粒径不大于250μm、平均粒径为10-100μm的粉末形式。
11.权利要求10所述的电缆,其中在水溶胀性材料中粒径为10-50μm的颗粒的量为粉末总重量的至少50%重量。
12.权利要求1-3任一项的电缆,其中水溶胀性材料是沿聚合链上有亲水基团的均聚物或共聚物。
13.权利要求1-3任一项所述的电缆,其中相对于100重量份的聚合物材料,所用的水溶胀性材料的存在量为5-120重量份。
14.权利要求13所述的电缆,其中相对于100重量份的聚合物材料,所用的水溶胀性材料的存在量为15-80重量份。
15.权利要求1-3任一项所述的电缆,其中构成膨胀层的聚合材料是选自下列的可膨胀的聚合物:聚烯烃、不同烯烃的共聚物、烯烃和烯属不饱和酯的共聚物、聚酯、聚碳酸酯、聚砜、酚型树脂、脲型树脂,以及它们的混合物。
16.权利要求15所述的电缆,其中聚合材料是烯烃聚合物或基于乙烯和/或丙烯的共聚物。
17.权利要求16所述的电缆,其中聚合材料选自:
(a)乙烯与烯属不饱和酯的共聚物,其中不饱和酯的量在5-80%重量;
(b)乙烯与至少一种C3-12α-烯烃和可选使用的二烯的弹性共聚物,具有下列的组成:35-90%摩尔乙烯;10-65%摩尔α-烯烃;0-10%摩尔二烯;
(c)乙烯与至少一种C4-12α-烯烃和可选使用的二烯的共聚物,其密度为0.86-0.90克/厘米3
(d)用乙烯/C3-12α-烯烃共聚物改性的聚丙烯,其中聚丙烯与乙烯/C3-12α-烯烃共聚物之间的重量比在90/10-10/90。
18.权利要求17所述的电缆,其中聚合材料是包括一热塑性聚合物的连续基质和分散在热塑性聚合物中的固化弹性聚合物细粒的热塑性弹性体。
19.权利要求1-3任一项所述的电缆,其中膨胀层包括预定量的导电炭黑。
20.权利要求19所述的电缆,其中导电炭黑的表面积至少为20m2/g。
21.权利要求20所述的电缆,其中炭黑的表面积至少为900m2/g。
22.权利要求19所述的电缆,其中炭黑的存在量为5-80%重量。
23.权利要求22所述的电缆,其中炭黑的存在量为10-70%重量。
24.权利要求1-3任一项所述的电缆,其中膨胀层是用挤出法得到的。
25.权利要求24所述的电缆,其中膨胀层的膨胀是在挤出过程中加入膨胀剂得到的。
26.权利要求24所述的电缆,其中膨胀层的膨胀是在挤出过程中高压注射气体得到的。
27.权利要求1-3任一项所述的电缆,其中膨胀层的直径在无力作用下大于金属屏蔽的内径,以便在施以金属屏蔽后得到预定的膨胀层预压度。
CNB988125668A 1997-12-22 1998-12-17 具有半导性阻水膨胀层的电缆 Expired - Fee Related CN1142557C (zh)

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JP2001527267A (ja) 2001-12-25
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DE69814921T2 (de) 2004-03-11
HK1032141A1 (en) 2001-07-06
CN1306668A (zh) 2001-08-01
HUP0100055A3 (en) 2001-07-30
HU223024B1 (hu) 2004-03-01
DK1042763T3 (da) 2003-09-22
ATE241204T1 (de) 2003-06-15
HUP0100055A2 (hu) 2001-05-28
PT1042763E (pt) 2003-09-30
CA2315694C (en) 2006-10-03
US6455769B1 (en) 2002-09-24
WO1999033070A1 (en) 1999-07-01
DE69814921D1 (de) 2003-06-26
CA2315694A1 (en) 1999-07-01
EP1042763B1 (en) 2003-05-21

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