CN111560794B - 一种耐弯折复合云母纸带及其制备方法 - Google Patents

一种耐弯折复合云母纸带及其制备方法 Download PDF

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CN111560794B
CN111560794B CN202010400301.9A CN202010400301A CN111560794B CN 111560794 B CN111560794 B CN 111560794B CN 202010400301 A CN202010400301 A CN 202010400301A CN 111560794 B CN111560794 B CN 111560794B
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吴海峰
赵建虎
苏潜
赵俊军
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Hunan Ruida Mica New Materials Co ltd
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Abstract

本发明公开了一种耐弯折复合云母纸带，包括云母纸基带以及成型于云母纸基带表面的改性PMIA绝缘纸，所述云母纸基带与所述改性PMIA绝缘纸之间还成型有石墨烯膜片，所述石墨烯膜片为镀铜石墨烯膜片或者镀镍石墨烯膜片，表面开有阵列排布的镂空孔，石墨烯膜片双面浸胶，以通过热压成型方式使云母纸基带与改性PMIA绝缘纸成型为一体；所述云母纸基带包括2～3层云母纸单片层，且相邻的云母纸单片层之间均匀填充有纳米纤丝化纤维素；而所述改性PMIA绝缘纸为经过硅烷偶联剂KH550改性后掺加有纳米级SiO2与TiO2粉末制成的PMIA绝缘纸。本发明相比于传统云母纸带具有较佳的表面强度和耐弯折性能，集填充、补强、导热、散热等功能于一体。

Description

一种耐弯折复合云母纸带及其制备方法
技术领域
本发明涉及绝缘云母制品领域，具体为一种具有较佳物理性能的耐弯折复合云母纸带及其制备方法。
背景技术
云母作为一类自然生成的层状硅酸盐类矿物，具有优良的物理性能和电气性以及在高温状态下仍保持以上性能的特性，同时具有完全的化学惰性、抗高电压、耐电晕放电和防辐射的特性，在电气行业具有广泛的应用。
云母纸产品作为目前云母最广泛的应用途径之一，其具有电气强度高，介质损耗低，表面电阻和体积电阻高的特性。而云母纸带作为云母纸的一种二次加工产品，是一种在云母纸的基础上增加机械支撑层(通常为化纤布或聚酯膜)的纸带结构，工艺上可以单独制备，也可以由具有相应层结构的云母纸卷裁切制成，其通常的作用方式是对导体进行包绕，如在耐火电线、电缆、耐高温电线和耐辐射电线的线芯表面进行包绕，起到耐火绝缘作用。
现有技术的云母纸带主要以云母为主要原料，经热化学或水力剥分破碎成细小云母鳞片，在制成浆抄纸，经造纸湿法抄造制备。虽然云母纸带由于本身的结构和材料特性本身富有弹性，且具有很大的耐剪切力和抗张强度等优异的物理性能，但在进行线芯或者其他导体包绕加工的过程中由于是直接包绕在相关导体的表面，会随线芯或者导体本身在使用过程中的位移会产生移位和磨损，导致抗弯折和抗张强度下降，在使用一段时间后，若对线芯或者导体进行持续弯折或者弯折程度较大，依然会造成云母纸带弯折破裂，影响使用效果、机械性能以及电气绝缘性能。
发明内容
本发明所解决的技术问题在于提供一种耐弯折复合云母纸带及其制备方法，以解决上述背景技术中的缺点。
本发明所解决的技术问题采用以下技术方案来实现：
一种耐弯折复合云母纸带，包括云母纸基带以及成型于云母纸基带表面的改性PMIA绝缘纸，所述云母纸基带与所述改性PMIA绝缘纸之间还成型有石墨烯膜片，所述石墨烯膜片为镀铜石墨烯膜片或者镀镍石墨烯膜片，表面开有阵列排布的镂空孔，石墨烯膜片双面浸胶，以通过热压成型方式使云母纸基带与改性PMIA绝缘纸成型为一体；所述云母纸基带包括2～3层云母纸单片层，且相邻的云母纸单片层之间均匀填充有纳米纤丝化纤维素；而所述改性PMIA绝缘纸为经过硅烷偶联剂KH550改性后掺加有纳米级SiO2与TiO2粉末制成的PMIA绝缘纸。
作为进一步限定，耐弯折复合云母纸带的总厚度为0.8mm～1.5mm，而所述云母纸基带采用的云母纸为天然白云母纸或者天然金云母纸，厚度为0.5～1mm，且厚度不小于云母纸带的总厚度的1/2。
作为进一步限定，所述云母纸单片层之间的纳米纤丝化纤维素的填充量为单层云母纸单片层单位面积内克重的15～20％。
作为进一步限定，所述石墨烯膜片的表面镂空率为8～15％。
作为进一步限定，所述石墨烯膜片的表面胶层厚度不超过30μm。
作为进一步限定，所述石墨烯膜片的表面胶层中采用的粘结剂材料为无机粘结剂。
作为进一步限定，所述云母纸单片层中的云母纸单片层均为云母鳞片的粒径控制在-50目～+200目的细浆云母纸，以获得较佳的表面张力。
作为进一步限定，所述云母纸单片层中的云母纸单片层自改性PMIA绝缘纸外侧向改性PMIA绝缘纸侧采用的原料云母鳞片粒径连续变小以获得表面张力的连续变化。
作为进一步限定，所述改性PMIA绝缘纸是以间位芳纶纤维为原料，通过加入硅烷偶联剂KH550中进行改性处理后，与间位芳纶浆粕均匀混合制浆，然后在浆料中加入纳米级SiO2与TiO2粉末，通过超声分散后进行抄浆制纸获得的成品绝缘纸；且在该绝缘纸制备过程中，作为原料的间位芳纶纤维包括占质量比1/3的单丝长度9～12mm的长间位芳纶纤维单丝以及质量比2/3的单丝长度5～7mm的短间位芳纶纤维单丝。
一种耐弯折复合云母纸带的制备方法，具体包括以下操作步骤：
S1、选择天然白云母与天然金云母作为原料，依次进行水洗、烘干得到干云母片，将上述干云母片煅烧后随炉冷却后至室温后，投送至高压水力破碎机中利用水力破碎剥分成云母鳞片；
S2、将破碎后的云母鳞片进行洗涤和过滤筛分，选取合适粒径的云母鳞片制浆，并利用圆网云母纸机进行抄造，抄造过程中上浆过程分两次或者三次进行，每次上浆进行两重或者三重圆网上浆，每次上浆过程完成后在对应的云母纸单片层表面喷涂纳米纤丝化纤维素；
S3、将步骤S2获得的云母纸通过脱水、烘干，即可得到云母纸基带；
S4、将符合条件的间位芳纶纤维通过硅烷偶联剂KH550进行改性处理后用去离子水冲洗，然后与芳纶浆粕按照3:2～2:1的比例进行混合；同时，将纳米SiO2粉末与纳米TiO2粉末加入去离子水中分散均匀后加入上述浆液中利用超声分散设备辅助继续进行超声分散处理，处理完毕后用制纸设备成型，得到改性PMIA绝缘纸；
S5、将带镂空孔的石墨烯膜片进行双面上胶处理，铺放于步骤S3获得的云母纸基带表面，然后在石墨烯膜片表面铺放改性PMIA绝缘纸，在改性PMIA绝缘纸表面热压成型，成型后裁边即得到成品云母纸带。
作为进一步限定，在步骤S4中，纳米SiO2粉末与纳米TiO2粉末的加入比例为3:1～5:1，加入总量为间位芳纶纤维的5‰～12‰。
有益效果：本发明的耐弯折复合云母纸带具有较佳的电气性能，并通过云母纸基带与改性PMIA绝缘纸的复合，使其兼备云母绝缘纸和芳纶纤维绝缘纸的优点，具有良好的柔韧性，高强度、高耐磨、抗撕裂性能，在保证结构稳定性和抗张性能的同时具有抗弯折能力，尤其适合于作为高性能导体的表面包绕材料，来辅助提高相应导体的使用性能。
附图说明
图1为本发明较佳实施例的结构示意图。
其中：1、改性PMIA绝缘纸；2、表面胶层；3、石墨烯膜片；4、云母纸单片层；5、纤维素填充层；6、镂空孔。
具体实施方式
为了使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体图示，进一步阐述本发明。
在下述实施例中，本技术领域技术人员可以理解，除非另外定义，这里使用的所有术语(包括技术术语和科学术语)具有与本申请所属领域中的普通技术人员的一般理解相同的意义。还应该理解的是，诸如通用字典中定义的那些术语应该被理解为具有与现有技术的上下文中的意义一致的意义，并且除非像这里一样定义，不会用理想化或过于正式的含义来解释。
参见图1的耐弯折复合云母纸带的实施例，耐弯折复合云母纸带包括云母纸基带以及成型于云母纸基带表面的改性PMIA绝缘纸1，在本实施例中，耐弯折复合云母纸带的总厚度为1.2mm，包括三层云母纸单片层4，三层云母纸单片层4厚度均为0.2mm，均为天然白云母纸，而用于制作云母纸单片层4的云母鳞片粒径均控制在-50目～+200目范围内，且云母纸单片层自改性PMIA绝缘纸外侧向改性PMIA绝缘纸侧采用的原料云母鳞片粒径连续变小以获得表面张力的连续变化。三层云母纸单片层4两两之间均匀填充有纳米纤丝化纤维素填充成型的纤维素填充层5，纤维素填充层5的纳米纤丝化纤维素的填充量为单层云母纸单片层单位面积内克重的17.5％，三层云母纸单片层4与成型于三层云母纸单片层4之间的两层纤维素填充层5共同构成云母纸基带，其厚度之和为0.7mm。
而改性PMIA绝缘纸是以间位芳纶纤维为原料，其中包括占质量比1/3的单丝长度9～12mm的长间位芳纶纤维单丝以及质量比2/3的单丝长度5～7mm的短间位芳纶纤维单丝，上述间位芳纶纤维通过加入硅烷偶联剂KH550中进行改性处理后，与间位芳纶浆粕均匀混合制浆，然后在浆料中加入纳米级SiO2与TiO2粉末，通过超声分散后进行抄浆制纸获得的厚度为0.45mm的成品绝缘纸。
而在改性PMIA绝缘纸1与云母纸基带之间还成型有石墨烯膜片3，该石墨烯膜片3为镀铜石墨烯膜片，石墨烯膜片3上开有阵列排布的镂空孔6，其表面镂空率为8％，石墨烯膜片3双面表面均以无机粘结剂为原料涂覆有一层厚度为20～25μm的表面胶层2，并在改性PMIA绝缘纸1与云母纸基带表面通过热压成型方式压制成成品耐弯折复合云母纸带。
上述耐弯折复合云母纸带通过以下方式制得：
制备时选择天然白云母作为原料，依次进行水洗、烘干得到干云母片，将上述干云母片煅烧后随炉冷却后至室温后，投送至高压水力破碎机中利用水力破碎剥分成云母鳞片，将云母鳞片进行洗涤和过滤筛分，选取-50目～+200目范围内的云母鳞片，并将上述云母鳞片继续破碎，并按粒径大小进行三个级别的分组，分别作为原料加水或者其他常用造纸助剂兑成浓度为6～9％的浆液。
利用圆网云母纸机进行抄造，抄造时进行三次上浆，首先将粒径最大的一组云母鳞片原料制成的浆粕进行两重圆网上浆，然后将粒径中等的一组云母鳞片原料制成的浆粕进行两重圆网上浆，在将粒径最小的一组云母鳞片原料制成的浆粕进行两重圆网上浆，每次上浆过程完成后在对应的云母纸单片层表面喷涂纳米纤丝化纤维素，控制上浆的浆量以控制云母纸单片层4的厚度，并控制纳米纤丝化纤维素的用量以符合要求，获得的云母纸通过脱水、烘干，即可得到云母纸基带。
将符合条件的间位芳纶纤维进行混合后通过硅烷偶联剂KH550进行改性处理，然后用去离子水冲洗，然后将间位芳纶纤维与芳纶浆粕按照3:2～2:1的比例进行混合；同时，将纳米SiO2粉末与纳米TiO2粉末加入去离子水中，控制加入比例为4:1，加入量为间位芳纶纤维的7‰，用分散机在2000rad/min的转速条件下，进行15～20min的粗分散，粗分散完成后，加入上述混合物浆粕中，利用超声分散设备辅助继续进行超声分散处理，控制超声分散条件为：3000rad/min、超声频率35KHz，超声功率50W，进行30～45min的超声分散，处理完毕后用圆网造纸机成型，得到厚度为0.45mm的改性PMIA绝缘纸基础材料纸，将上述改性PMIA绝缘纸基础材料进行裁剪，即得成品改性PMIA绝缘纸1。
将带镂空孔的石墨烯膜片3进行双面上胶处理得到带表面胶层2的石墨烯膜片3，铺放于云母纸基带表面，然后在石墨烯膜片3表面铺放改性PMIA绝缘纸1，在改性PMIA绝缘纸1表面进行热压，热压温度为270℃，热压压力为15Mpa，经过热压将纸张含水量脱至0.2～0.5％，取出后裁边即得到成品云母纸带。
本实施例的耐弯折复合云母纸的实施例，首先通过将云母纸基带进行三层成型，通过层间云母鳞片粒径的连续变小以获得表面张力的连续变化，并通过纳米纤丝化纤维素的填充来改善层间性能，保证整体稳定性。
通过间位芳纶(PMIA)绝缘纸作为符合加强材料，通过硅烷偶联剂KH550改性提高其表面性能，使得改性PMIA绝缘纸的空间交联结构更加稳定，而纳米SiO2粒子本身能通过诱导力与间位芳纶纤维分子间的结合的特性，在这种改性PMIA绝缘纸的空间结构条件下，使纳米粉末颗粒与间位芳纶纤维分子进行更有效的结合，提高改性PMIA绝缘纸的延展性和韧性，增加材料的刚性和抗压缩性，还能降低间位芳纶纤维链运动的剧烈程度，提升芳纶纤维的热稳定性。
而三层结构的云母纸基带与改性PMIA绝缘纸的结合能有效改善复合云母纸带的整体力学性能，在合理配比厚度的情况下，控制云母纸基带的厚度比值，能在保证云母纸的电学性能的前提下保证复合云母纸带力学性能的提升效果相对最好，其可塑性和延展性得到增强，且在云母纸基带侧在内、改性PMIA绝缘纸在外的条件下对导体进行包绕的情况下，使其云母纸基带的贴合面的可塑性和延展性得到增强，而具有纳米SiO2与TiO2粒子的改性PMIA绝缘纸则能在外侧面提供延展性和可弯折性能。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。

Claims (7)

1.一种耐弯折复合云母纸带，其特征在于，包括云母纸基带以及成型于云母纸基带表面的改性PMIA绝缘纸，所述云母纸基带与所述改性PMIA绝缘纸之间还成型有石墨烯膜片，所述石墨烯膜片为镀铜石墨烯膜片或者镀镍石墨烯膜片，表面开有阵列排布的镂空孔，石墨烯膜片双面浸胶，以通过热压成型方式使云母纸基带与改性PMIA绝缘纸成型为一体；所述云母纸基带包括2～3层云母纸单片层，且相邻的云母纸单片层之间均匀填充有纳米纤丝化纤维素；
所述石墨烯膜片的表面镂空率为8～15％，且所述石墨烯膜片的表面胶层厚度不超过30μm；
所述改性PMIA绝缘纸通过以下方式制得：
以间位芳纶纤维为原料，通过加入硅烷偶联剂KH550中进行改性处理后，与间位芳纶浆粕均匀混合制浆，然后在浆料中加入纳米级SiO2与TiO2粉末，通过超声分散后进行抄浆制纸获得的改性PMIA绝缘纸；
在所述改性PMIA绝缘纸制备过程中，作为原料的间位芳纶纤维包括占质量比1/3的单丝长度9～12mm的长间位芳纶纤维单丝以及质量比2/3的单丝长度5～7mm的短间位芳纶纤维单丝。
2.根据权利要求1所述的耐弯折复合云母纸带，其特征在于，耐弯折复合云母纸带的总厚度为0.8mm～1.5mm，而所述云母纸基带的厚度为0.5～1mm，且不小于云母纸带的总厚度的1/2。
3.根据权利要求1所述的耐弯折复合云母纸带，其特征在于，所述云母纸基带采用的云母纸为天然白云母纸或者天然金云母纸。
4.根据权利要求1所述的耐弯折复合云母纸带，其特征在于，所述云母纸单片层之间的纳米纤丝化纤维素的填充量为单层云母纸单片层单位面积内克重的15～20％。
5.根据权利要求1所述的耐弯折复合云母纸带，其特征在于，所述云母纸单片层中的云母纸单片层均为云母鳞片的粒径控制在-50目～+200目的细浆云母纸。
6.根据权利要求1所述的耐弯折复合云母纸带，其特征在于，所述云母纸单片层中的云母纸单片层自改性PMIA绝缘纸外侧向改性PMIA绝缘纸侧采用的原料云母鳞片粒径连续变小。
7.一种耐弯折复合云母纸带的制备方法，用于制备具有如权利要求1所述技术特征的耐弯折复合云母纸带，该制备方法具体包括以下操作步骤：
S1、选择天然白云母与天然金云母作为原料，依次进行水洗、烘干得到干云母片，将上述干云母片煅烧后随炉冷却后至室温后，投送至高压水力破碎机中利用水力破碎剥分成云母鳞片；
S2、将破碎后的云母鳞片进行洗涤和过滤筛分，选取合适粒径的云母鳞片制浆，并利用圆网云母纸机进行抄造，抄造过程中上浆过程分两次或者三次进行，每次上浆进行两重或者三重圆网上浆，每次上浆过程完成后在对应的云母纸单片层表面喷涂纳米纤丝化纤维素；
S3、将步骤S2获得的云母纸通过脱水、烘干，即可得到云母纸基带；
S4、将符合条件的间位芳纶纤维通过硅烷偶联剂KH550进行改性处理后用去离子水冲洗，然后与芳纶浆粕按照3:2～2:1的比例进行混合；同时，将纳米SiO2粉末与纳米TiO2粉末加入去离子水中分散均匀后加入上述浆液中利用超声分散设备辅助继续进行超声分散处理，处理完毕后用制纸设备成型，得到改性PMIA绝缘纸；其中，纳米SiO2粉末与纳米TiO2粉末的加入比例为3:1～5:1，加入总量为间位芳纶纤维的5‰～12‰；
S5、将带镂空孔的石墨烯膜片进行双面上胶处理，铺放于步骤S3获得的云母纸基带表面，然后在石墨烯膜片表面铺放改性PMIA绝缘纸，在改性PMIA绝缘纸表面热压成型，成型后裁边即得到成品云母纸带。
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