CN106366419B - 一种xlpe电缆绝缘材料 - Google Patents
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
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- XHQSLVIGPHXVAK-UHFFFAOYSA-K iron(3+);octadecanoate Chemical compound [Fe+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XHQSLVIGPHXVAK-UHFFFAOYSA-K 0.000 description 1
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/04—Ingredients characterised by their shape and organic or inorganic ingredients
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
- H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
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Abstract
一种XLPE电缆绝缘材料，包括以下重量份的组分：低密度聚乙烯80‑100份，铁氧体纳米颗粒0.5‑2份，炭黑10‑20份，抗氧剂0.1‑3份，稳定剂1‑3份，溶剂10‑20份；其中所述铁氧体纳米颗粒按照以下方法制备：配制Ni2+、Fe3+摩尔比为1‑3:1的混合溶液，并加入分子筛，在常温下搅拌12‑36h，经抽滤洗涤，烘干后放入马弗炉中升温至800‑1100℃焙烧1‑6h；然后将焙烧后的产物置于氢氟酸溶液中，搅拌2‑3h，固体样品经过滤、洗涤、烘干后即得到镍铁氧体纳米管。本发明所述电缆绝缘材料能够有效抑制绝缘材料中空间电荷的积聚，并且提高空间电荷注入的电场阈值，降低空间电荷限制电流(SCLC)引起的绝缘材料电导率增大的效应。
Description
技术领域
本发明涉及一种XLPE电缆绝缘材料及其制备方法，尤其是一种添加改性纳米颗粒的XLPE电缆绝缘材料。
背景技术
随着电力***的不断发展壮大，电网***日趋复杂，交流输电***暴露出一些固有的缺点，特别是远距离交流输电受到同步运行稳定性的限制，在这种情况下，直流输电技术重新引起人们重视。尤其是可关断器件的电压源换流器和PWM技术的发展，避免了XLPE电缆的极性翻转，促进了柔性直流输电的发展。柔性直流输电技术(轻型直流输电技术)具有可控性能高、设计施工方便环保、占地小及换流站间无需通信等优点，在可再生资源并网、分布式发电并网、孤岛供电、城市电网供电等方面具有明显优势。与交流电缆相比，由于绝缘介质的直流电气强度高于交流电气强度，在相同尺寸下直流电缆输电容量是交流电缆输电容量的2倍，输送相同的功率直流电缆所用线材仅为交流电缆所用线材的1/2～2/3。
目前，国际上直流电缆成功用于商业运行业绩最好的是ABB公司的电缆产品，最高电压等级达320kV。其它国家的绝缘电缆发展概况大致如下：法国Nexans公司采用聚乙烯绝缘，电缆的电压等级为500kV，无运行经验；意大利的Pirelli公司采用交联聚乙烯绝缘，电缆的电压等级为250kV，仅用于电压换流***，无运行经验；法国Sagem公司采用LDPE为电缆绝缘，电压等级为400kV，参加法国电力公司的直流输电项目研究；日本Viscas公司采用交联聚乙烯绝缘，额定电压为500kV，无商业运行经验。
交联聚乙烯内部存在大量的局域态，作为高压直流电缆绝缘时会造成内部空间电荷集聚，电场畸变，加速绝缘材料的电老化，缩短绝缘材料的使用寿命，尤其是当绝缘内的异极性空间电荷积累比较多时可能会引发绝缘材料的击穿，使绝缘失效。交联聚乙烯材料发生老化时，结构会发生变化，如化学键断裂、介质微孔增多或长出树枝状结构等，这些缺陷将使介质中的陷阱数目增多，电场的作用下会引起空间电荷聚集。
XLPE直流电缆作为直流输电不可缺少的一部分，空间电荷一直是制约直流电缆发展的关键问题。为了更好地解决空间电荷问题，许多学者针对影响空间电荷分布的不同因素进行了大量研究。常规的抑制空间电荷方法包括通过掺杂添加剂、共混、接枝、共聚等。添加剂种类有很多，大致可以分为无机添加剂、有机添加剂、成核剂、自由基清除剂、抗热/大气老化剂等。例如在低聚乙烯(LDPE)中加入三糖梨醇能有效降低球晶尺寸，减少晶界缺陷的形成；在LDPE中加入氯化聚乙烯(CPE)或乙烯/丙烯酸共聚物(EAA)质量分数约为1％时，能有效降低空间电荷效应和体积电阻率，提高直流预压短路树枝的起始电压；加入1％的Ba-TiO3到聚乙烯中，能有效改善聚乙烯中的空间电荷效应，提高直流预压短路的击穿强度和直流击穿强度；将1％左右的电压稳定剂添加入聚乙烯中，能够减少老化过程中大分子自由基的生成，减少深陷阱的产生，提高聚合物的绝缘寿命。
发明内容
铁氧体MFe2O4(M为二价金属元素)是一类重要的无机非金属材料，具有高熔点、高机械强度、低介电常数和优良的光学性能，在催化、电化学、磁热性能、工业耐火和导弹制导***窗口等领域有着广泛应用。近些年来，铁氧体作为搪瓷、陶瓷的着色材料、气敏材料、磁性吸波材料、催化材料等应用均有报道。该类材料的传统制备方法是高温煅烧混合金属氧化物或氢氧化物，但由于烧结作用的发生，所得产物粒径较大且分布不均，限制了其进一步的应用。利用硬模板法将形成铁氧体的金属离子首先吸附到主体材料表面或孔道内壁，然后经过系列物理化学过程，在主体材料表面形成铁氧体，然后再将硬模板剂去除，这样就可以得到较大比表面和特定孔道结构的铁氧体，从而可以避免均相合成以及高温焙烧过程所带来的产物粒径较大、比表面积较低的问题。
本发明首次提出将铁氧体纳米颗粒应用于电缆绝缘材料，尤其是XLPE绝缘体中，其特点是铁氧体纳米粒子通过表面改性，填充到交联聚乙烯中，束缚空间电荷，从而延长电力电缆的寿命达1-5倍。它具有技术先进、安全稳定的优点。
一种包含铁氧体纳米颗粒的XLPE电缆绝缘材料，包括以下重量份的组分：
低密度聚乙烯80-100份，铁氧体纳米颗粒0.5-2份，炭黑10-20份，抗氧剂0.1-3份，稳定剂1-3份，溶剂10-20份。
所述溶剂是环己烷、甲苯、正辛烷、碳酸二甲酯、碳酸二乙酯中的一种；所述稳定剂是石油磺酸锌、硬脂酸铁、硬脂酸锌中的一种或多种；所述抗氧剂是抗氧剂1010、抗氧剂1024、抗氧剂1035、抗氧剂264和DNP中的任一种或几种的混合物。
所述铁氧体纳米颗粒按照以下方法制备：配制Ni2+、Fe3+摩尔比为1-3:1的混合溶液，并加入分子筛，在常温下搅拌12-36h，经抽滤洗涤，烘干后放入马弗炉中升温至800-1100℃焙烧1-6h；然后将焙烧后的产物置于氢氟酸溶液中，搅拌2-3h，固体样品经过滤、洗涤、烘干后即得到镍铁氧体纳米管。
所述分子筛优选是MCM、ZSM系列分子筛，更优选是MCM-41或ZSM-15。
以氧化铁和氧化镍折算，所述分子筛质量为氧化铁和氧化镍质量之和的1-10倍，优选是3-6倍。
包含铁氧体纳米颗粒的XLPE电缆绝缘材料的制备方法，包括以下步骤：按比例将线性低密度聚乙烯、抗氧剂以及炭黑一同放入密炼机在100-120℃中混炼30-50min；将交联剂加入密炼机后进行保温混炼，得到高压直流电缆半导屏蔽电材料，所述的保温混炼是指在120-135℃的温度下混炼20-30min。
本发明有效抑制绝缘材料中空间电荷的积聚，并且提高空间电荷注入的电场阈值，降低空间电荷限制电流(SCLC)引起的绝缘材料电导率增大的效应。
具体实施方式
下面结合具体实施例对发明的技术方案进行详细说明。
实施例中所述铁氧体纳米颗粒按照以下方法制备：配制Ni2+、Fe3+摩尔比为2:1的混合溶液，并加入分子筛，在常温下搅拌12h，经抽滤洗涤，烘干后放入马弗炉中升温至800℃焙烧6h；然后将焙烧后的产物置于氢氟酸溶液中，搅拌2h，固体样品经过滤、洗涤、烘干后即得到镍铁氧体纳米管。
实施例1
低密度聚乙烯80份，铁氧体纳米颗粒0.5份，炭黑10份，抗氧剂0.5份，稳定剂2份，溶剂10份。
实施例2
低密度聚乙烯100份，铁氧体纳米颗粒1份，炭黑10份，抗氧剂0.1份，稳定剂1份，溶剂20份。
对比例1
低密度聚乙烯80份，炭黑10份，抗氧剂0.5份，稳定剂2份，溶剂10份。
对比例2
低密度聚乙烯100份，炭黑10份，抗氧剂0.1份，稳定剂1份，溶剂20份。
对实施例和对比例进行老化试验和击穿电压测试，结果如下表所示：
| 实施例1 | 实施例2 | 对比例1 | 对比例2 | |
| 老化试验(h) | 35.2 | 36.4 | 29.5 | 28.7 |
| 击穿试验(kV) | 28.6 | 27.5 | 18.5 | 17.3 |
本发明可用其他的不违背本发明的精神或主要特征的具体形式来概括。本发明的所有实施方案都只能认为是对本发明的说明而不是限制，凡是根据本发明的技术内容所作出的任何细微修改或等同替换，都属于本发明的技术方案之内。
Claims (5)
1.一种XLPE电缆绝缘材料，包括以下重量份的组分：低密度聚乙烯80-100份，铁氧体纳米颗粒0.5-2份，炭黑10-20份，抗氧剂0.1-3份，稳定剂1-3份，溶剂10-20份；其中所述铁氧体纳米颗粒按照以下方法制备：配制Ni2+、Fe3+摩尔比为1-3:1的混合溶液，并加入分子筛，在常温下搅拌12-36h，经抽滤洗涤，烘干后放入马弗炉中升温至800-1100℃焙烧1-6h；然后将焙烧后的产物置于氢氟酸溶液中，搅拌2-3h，固体样品经过滤、洗涤、烘干后即得到镍铁氧体纳米管。
2.如权利要求1所述的XLPE电缆绝缘材料，其特征在于所述溶剂是环己烷、甲苯、正辛烷、碳酸二甲酯、碳酸二乙酯中的一种。
3.如权利要求1所述的XLPE电缆绝缘材料，其特征在于所述稳定剂是石油磺酸锌、硬脂酸铁、硬脂酸锌中的一种或多种。
4.如权利要求1所述的XLPE电缆绝缘材料，其特征在于所述抗氧剂是抗氧剂1010、抗氧剂1024、抗氧剂1035、抗氧剂264和DNP中的任一种或几种的混合物。
5.如权利要求1所述的XLPE电缆绝缘材料，其特征在于所述分子筛是MCM、ZSM系列分子筛。
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