CN109228596A - 一种储气囊体 - Google Patents

一种储气囊体 Download PDF

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CN109228596A
CN109228596A CN201810728929.4A CN201810728929A CN109228596A CN 109228596 A CN109228596 A CN 109228596A CN 201810728929 A CN201810728929 A CN 201810728929A CN 109228596 A CN109228596 A CN 109228596A
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gas storage
layer
butyl rubber
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CN109228596B (zh
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刘羽熙
荆祥海
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Lianyungang Jingwei Composite New Material Co ltd
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Chuzhou University
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Abstract

本发明提供一种柔性深水气体储存囊体材料，其组成包括高气体阻隔的塑料内层、高强度纤维中层和阻水防附着塑料外层三部分组成。本发明提供的囊体材料具有防水、气密性高、可反复回收使用以及耐刮擦和防生物附着的特性，适用于长期在水下储存高压气体。

Description

一种储气囊体
技术领域
本发明涉及一种储存设备技术领域，具体涉及一种储气囊体。
背景技术
在存储气体时，比较现实的方法是在压缩条件下将气体存储于耐压容器内。耐高压气体钢瓶作为最为常用的高压气体储存容器，被广泛用于各类气体的暂时存储，但是高压钢瓶存在造价高、容易被腐蚀、有潜在爆炸危险等缺点。
柔性塑料囊体也是一种普遍应用气体存放容器，相对于高压钢瓶气体存储技术，该存储方法具有造价低、耐腐蚀、回收方便等优点。但是高分子材料耐压性能不足，一般只能在接近大气压力下在应用于气体的大量储存时，这通常会占用大量的空间。利用柔性塑料囊体和深水产生的水压相结合可以克服高分子材料耐压性能不足的缺点，在水资源丰富的区域实现气体的压缩储存。
柔性塑料囊体应用于水下气体高压储存时，囊体本身需要具备以下四个条件：（1）囊体材料具备高气体和水汽阻隔性能，保证在气体和长期存储过程中不漏气和不渗水；（2）囊体材料必须具有耐弯折性，保证在囊体充气-排气过程中，囊体壁的弯折和屈服不能对气体阻隔和水汽阻隔性能产生负面影响；（3）囊体材料具备耐刮擦特性；（4）囊体外壁必须具有防生物附着性能，防止在水下留置过程中表面滋生大量水生物体。尽管通过多层复合的方式很容易实现所述部分必要性能。令人遗憾的是，条件（1）和条件（2）之间存在着一定的相互矛盾。这是因为，对于具备高阻隔性能高分子材料而言，诸如聚对苯二甲酸乙二醇酯、芳香尼龙、聚偏氯乙烯以及蒸镀涂层等，它们不具备耐弯折性。而在深水区域进行的重复性充气-排气过程中所造成的囊体不规则弯折现象通常会导致弯折区域有银纹的产生，从而造成阻隔性能的降低。采用折叠囊体可以从一定程度上缓解银纹的产生，但是在深水区域的高水压力使得囊体难以按照折叠线折叠排气。而对于耐弯折的高分子材料，虽然在囊体反复充气-排气过程，它们不会因为弯折导致材料阻隔性能的变化，但是它们的玻璃化转变温度较高，高分子链的活动性较强，气体阻隔性能就严重不足。
因此提供一种高阻隔的耐弯折囊体材料是本领域亟待解决的技术问题。
发明内容
本发明提供了一种柔性储气囊体，其由高气体阻隔材料制成的塑料内层、由高强度纤维制成的中层和由阻水防附着塑料制成的外层，由于设置成采用不同材料制成而成不同层，使得本发明的柔性储气囊体在满足高气体和水汽阻隔性能的同时，还能保证具有优良的耐弯折性。
本发明采用以下技术方案实现：
一种柔性储气囊体，其由高气体阻隔材料制成的塑料内层、由高强度纤维制成的中层和由阻水防附着塑料制成的外层。
优选地，所述塑料内层由内至外依次包括包含聚全氟乙烯丙烯共聚物的子内层、粘结层、包含丁基橡胶的子外层组成；
优选地，所述中层包含凯芙拉编织纤维布、碳纤维编织纤维布或者超高分子量聚乙烯纤维布，所述中层的厚度为1000~2000μm。
优选地，所述外层包含硅橡胶和质量份为1~5%的微米氧化铜，所述外层的硬度是45~65A。
优选地，所述子内层的厚度为20~200μm，所述粘结层的厚度为50~1000μm，所述子外层厚度为1~10 mm。
优选地，所述子外层由质量份70~95的丁基橡胶和5~30份的氧化石墨烯制备而成。
优选地，丁基橡胶乳液经过阴离子、阳离子表面活性剂乳化后，再由纳米层状硅酸盐水溶液进行涂覆并高温硫化后制备成所述粘结层。
优选地，所述丁基橡胶乳液由100质量份的丁基橡胶和0.5~3份的过氧化物制备而成。
在符合本领域常识的基础上，上述各优选条件，可任意组合，即得本发明各较佳实例。
本发明的积极有益效果：
本发明的柔性储气囊体由高气体阻隔材料制成的塑料内层、由高强度纤维制成的中层和由阻水防附着塑料制成的外层，由于设置成采用不同材料制成而成不同层，使得本发明的柔性储气囊体在满足高气体和水汽阻隔性能的同时，还能保证具有优良的耐弯折性。
附图说明
图1为本发明的储气囊体的横截面视图。
附图标记说明：
图1中 1为塑料内层，2为中层，3为外层。
具体实施方式
下面对本发明的实施例作详细说明，本实施例在以本发明技术方案为前提下进行实施，给出了详细的实施方式和具体的组成部分。根据上述发明内容对本发明所做的一些非本质的改进和调整仍属于本发明的保护范围。
实施例1
1.制备丁基橡胶乳液
将10份丁基橡胶，0.3份过氧化二异丙苯溶于正己烷中，加入0.5份十六烷基三甲基氯化铵，充分溶解后高速剪切下缓慢注入3份纳米蒙脱土分散水中，得到丁基橡胶乳液。
2.制作粘结层和全氟乙烯丙烯内层
将1000μm厚的全氟乙烯丙烯(FEP)膜经过等离子体处理后，喷涂上经过表面活性剂乳化的丁基橡胶乳液并经过高温硫化后，得到粘结层和FEP内层。
3.制备塑料内层和中层
将丁基橡胶70份、过氧化二异丙苯2份、28份硅烷偶联剂KH-550以及5份氧化石墨烯充分混炼后，开练成2mm后片，与粘结层和凯夫拉纤维布压合之后再于160℃硫化30min，得到高气体阻隔的塑料内层和耐刮擦高强度中层。
4.制备外层
将上述囊体材料表面涂覆1000μm厚的液体硅橡胶，室温固化后得到柔性深水气体储存囊体。
实施例2
与上述实施例1的制备过程基本相同，所不同的是，本实施例中采用聚对苯二甲酸乙二醇酯内层、高强度凯夫拉纤维中层以及氧化铜/硅橡胶外层制备深水气体储存囊体材料。
实施例3
本实施例中，其将实施实例1中的丁基橡胶阻隔层中的石墨烯更换为炭黑，无防附着涂层，其它均相同；
实施例4
1. 制备丁基橡胶乳液
将10份丁基橡胶，0.3分过氧化二异丙苯溶于正己烷中，加入0.5份十六烷基三甲基氯化铵，充分溶解后高速剪切下缓慢注入3份纳米蒙脱土分散水中，得到丁基橡胶乳液。
2. 制作粘结层和全氟乙烯丙烯内层
1000μm厚的全氟乙烯丙烯(FEP)膜经过等离子体处理后，喷涂上经过表面活性剂乳化的丁基橡胶乳液并经过高温硫化后，得到粘结层和FEP内层。
3. 制备塑料内层和中层
将丁基橡胶70份、过氧化二异丙苯2份、28份硅烷偶联剂KH-550、5份氧化石墨烯以及2份羟丙基淀粉充分混炼后，开练成2mm后片，与粘结层和凯夫拉纤维布压合之后再于160℃硫化30min，得到高气体阻隔的塑料内层和耐刮擦高强度中层。
4. 制备外层
将上述囊体材料表面涂覆1000μm厚的液体硅橡胶，室温固化后得到柔性深水气体储存囊体。
实施例5
1. 制备丁基橡胶乳液
将10份丁基橡胶，0.3分过氧化二异丙苯溶于正己烷中，加入0.5份十六烷基三甲基氯化铵，充分溶解后高速剪切下缓慢注入3份纳米蒙脱土分散水中，得到丁基橡胶乳液。
2. 制作粘结层和全氟乙烯丙烯内层
1000μm厚的全氟乙烯丙烯(FEP)膜经过等离子体处理后，喷涂上经过表面活性剂乳化的丁基橡胶乳液并经过高温硫化后，得到粘结层和FEP内层。
3. 制备塑料内层和中层
将丁基橡胶70份、过氧化二异丙苯2份、28份硅烷偶联剂KH-550、5份氧化石墨烯、2份羟丙基淀粉以及2份环氧氯丙烷充分混炼后，开练成2mm后片，与粘结层和凯夫拉纤维布压合之后再与160℃硫化30min，得到高气体阻隔的塑料内层和耐刮擦高强度中层。
4. 制备外层
将上述囊体材料表面涂覆1000μm厚的液体硅橡胶，室温固化后得到柔性深水气体储存囊体。
实验结果
以下采用由上述实施例制备而成的柔性储气囊体进行水下存储测试：
采用上述实施例制备的气体储存囊体材料制备成1 m的球形囊体，配重后投放于30 m湖水下，经由管道冲入空气至3 atm，关闭阀门后保持一个月后测试囊体内的气体剩余量；囊体表面的生物附着量；排空气体后回收囊体，观测囊体内的渗水情况；反复充气-排气10次后，观测囊体的完整性。
表1 实施例1~3的囊体材料性能测试结果
实施例号 气体剩余量 生物附着 渗水情况 可回收性
1 95% 基本无 无 是
2 96% 基本无 内层潮湿 变形严重
3 90% 明显 无 是
4 97% 基本无 无 是
5 99% 无 无 是
可见，采用实施例5的方法和成分制成的储气囊体在防水、气密性高、可反复回收使用以及耐刮擦和防生物附着等方面可以获得最好的平衡点，最适合长期在水下储存高压气体。
虽然以上描述了本发明的具体实施方式，但是本领域的技术人员应当理解，这些仅是举例说明，本发明的保护范围是由所附权利要求书限定的。本领域的技术人员在不背离本发明的原理和实质的前提下，可以对这些实施方式做出多种变更或修改，但这些变更和修改均落入本发明的保护范围。

Claims (8)

1.一种柔性储气囊体，其特征在于：所述柔性储气囊体由高气体阻隔材料制成的塑料内层、由高强度纤维制成的中层和由阻水防附着塑料制成的外层。
2.根据权利要求1所述的柔性储气囊体，其特征在于，所述塑料内层由内至外依次包括包含聚全氟乙烯丙烯共聚物的子内层、粘结层、包含丁基橡胶的子外层组成。
3.根据权利要求1所述的柔性储气囊体，其特征在于，所述中层包含凯芙拉编织纤维布、碳纤维编织纤维布或者超高分子量聚乙烯纤维布，所述中层的厚度为1000~2000μm。
4.根据权利要求1所述的柔性储气囊体，其特征在于，所述外层包含硅橡胶或质量份为1~5%的微米氧化铜，所述外层的硬度是45~65A。
5. 根据权利要求2所述的柔性储气囊体，其特征在于，所述子内层的厚度为20~200μm，所述粘结层的厚度为50~1000μm，所述子外层厚度为1~10 mm。
6.根据权利要求2所述的柔性储气囊体，其特征在于，所述子外层由包括质量份70~95的丁基橡胶和5~30份的氧化石墨烯制备而成。
7.根据权利要求2所述的柔性储气囊体，其特征在于，丁基橡胶乳液经过阴离子、阳离子表面活性剂乳化后，再由纳米层状硅酸盐水溶液进行涂覆并高温硫化后制备成所述粘结层。
8.根据权利要求7所述的柔性储气囊体，其特征在于，所述丁基橡胶乳液由包括100质量份的丁基橡胶和0.5~3份的过氧化物制备而成。
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