CN106461156A - 用于复合材料压力容器的塑料衬里 - Google Patents
用于复合材料压力容器的塑料衬里 Download PDFInfo
- Publication number
- CN106461156A CN106461156A CN201580027875.3A CN201580027875A CN106461156A CN 106461156 A CN106461156 A CN 106461156A CN 201580027875 A CN201580027875 A CN 201580027875A CN 106461156 A CN106461156 A CN 106461156A
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- CN
- China
- Prior art keywords
- layer
- plastic lining
- plastic
- impervious barrier
- lining
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
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Abstract
本发明提出了一种用于氢气存储的塑料衬里,该塑料衬里包括:第一防渗层(3),被配置为作为与氢气接触的内部层的第二防渗层(7),至少一个被布置在第一和第二防渗层之间的中间层,其中第二防渗层(7)具有比所述至少一个中间层更低的氢气渗透率,使得第二防渗层(7)减缓氢气迁移到所述至少一个中间层中。
Description
技术领域
本发明涉及一种用于复合材料压力容器的塑料衬里。具体地,本发明涉及一种用于氢气存储的塑料衬里。
背景技术
一些车辆使用压缩气体、尤其是氢气作为燃料。通常,这样的车辆配备有复合材料压力容器。通常,该复合材料压力容器包括用于氢气存储的衬里。
金属和非金属衬里两者都被使用,但非金属衬里因为其更轻的重量是优选的。
非金属衬里可以是单层类型或多层类型的。通常,单层类型的衬里包括单一聚酰胺层。通常,多层类型的衬里包括具有6个层的结构:内部的基于热塑性材料(优选地:HDPE)的层、第一粘着剂层、包括防渗树脂(优选地:EVOH)的层、第二粘着剂层、再次研磨料层,以及外部的基于热塑性材料的层。
外部丝线缠绕施加在衬里周围。该丝线缠绕的形式可以是缠绕在衬里外部周围的碳纤维丝线复合材料。
已经发现这些已知的衬里受聚合物中相对高的氢气渗透率的困扰。氢气可能会集中在聚合物内的某些区域中。该累积在压力释放时产生气泡。该气泡的形成在本文中被称作“起泡”。该起泡可以导致衬里的损坏,该损坏的形式为衬里的开裂或机械降解。
鉴于上述缺陷,存在对改进的用于氢气存储的衬里的需求。
发明内容
为了在保持衬里的机械特征(强度、柔性和重量)的同时克服该缺陷,本发明提出了一种用于氢气存储的衬里,该衬里包括:
-第一防渗层,
-第二防渗层,该层是与氢气直接接触的内部层,
-至少一个中间层,被布置在第一和第二防渗层之间,
其中,第二防渗层具有比所述至少一个中间层更低的氢气渗透率,使得第二防渗层减缓氢气迁移到所述至少一个中间层内。
由此,提出了一种具有受控扩散率的多层结构衬里。更准确地说,提出了一种这样的多层结构衬里,其中,中间层被第二防渗层(即内部层)保护。该中间层在一侧与第一防渗层接触,在另一侧与第二防渗层接触。根据本发明,该内部层(即与氢气直接接触的层)具有比中间层(一层或多层)更低的氢气渗透率(这例如是因为更高的结晶度),以减缓氢气迁移到该多层结构内(即降低扩散速率)。换句话说,该内部层(即第二防渗层)作为扩散延迟层。使用这样的扩散延迟层允许保护衬里免受由于起泡造成的开裂效果。
要指出的是,物质穿过媒质的质量转移的驱动力是由该物质在该媒质中的浓度梯度造成的,这导致物质通量。该通量与浓度梯度相关,质量扩散率被定义为通量和梯度之间的关系中的比例系数。扩散率越高,物质就越快地移动到媒质中。
在一个具体实施方式中,在第一和第二防渗层之间布置有单一层(即中间层)。在该实施方式中,该单一层可以例如是基于热塑性材料的层。
在另一具体实施方式中,在第一和第二防渗层之间布置有至少一个基于热塑性材料的层和至少一个粘着剂层。在该实施方式中,夹在第一和第二防渗层之间的基于热塑性材料的层和粘着剂层(一层或多层)的结构形成中间层。
术语“热塑性材料”被理解为指包括热塑性弹性体在内的任何热塑性聚合物及其混合物。术语“聚合物”被理解为既指均聚物也指共聚物(尤其是二元或三元共聚物),例如无规共聚物、线性嵌段共聚物、其它嵌段共聚物,以及接枝共聚物等。
基于热塑性材料的层的塑料通常是聚烯烃。优选地,该聚烯烃是聚乙烯。使用高密度聚乙烯(HDPE)能够获得良好的结果。
该多层结构包括第一防渗层。优选地,该第一防渗层由具有低乙烯含量的乙烯/乙烯醇共聚物(EVOH)制成。
优选地,该内部层(即第二防渗层)由从以下清单中选择的材料制成:聚偏二氟乙烯(PVDF)、聚乙烯氯化物(PVDC)、乙烯/乙烯醇共聚物(EVOH)、芳香族尼龙、脂肪族尼龙、无定形尼龙、聚对苯二甲酸乙二醇酯(PET)、LCP和丙二醇藻酸盐(PGA)。在将EVOH材料用作内部层的情况下,乙烯/乙烯醇共聚物的乙烯含量可以高于用作防渗层的EVOH材料中的乙烯含量。
由于具有非常低的氢气渗透率的EVOH材料的脆性,不能够将这样的材料布置在与氢气接触的表面处作为内部防渗层。这样的EVOH等级更位于结构的中心(即第一防渗层)。相反地,与第一防渗层相比具有更高的氢气渗透率的EVOH材料位于表面处,作为内部防渗层。这防止了中间层中的起泡效应。第一防渗层的氢气渗透率比内部层的氢气渗透率低至少20%。
在另一具体实施方式中,内部层的形式可以是PVOH覆层。例如,该PVOH覆层可以通过热喷涂来获得。
在另一具体实施方式中,内部层可以通过在基于HDPE的层上施加表面处理(例如氟化或磺化)来获得。
在另一具体实施方式中,内部层可以是接枝马来酸酐,以增强与通常由金属制成的(复合材料压力容器的)衬里凸起部的结合。
在一个特别有利的实施方式中,内部层可以还包括填料,诸如例如纤维性填料(碳纤维、天然纤维、玻璃纤维等)、玻璃(空心的)球、2D填料(粘土诸如蒙脱石,蛭石,滑石,碳化合物诸如石墨烯和膨胀石墨)或玻璃(通常空心的)球和粉末(碳黑、硫酸钡、被粉碎的粘土和滑石)。将这样的填料添加到内部层(例如基于PVDF的层)中提供了迷宫效应,由此降低氢气扩散速率。
可选地,可以在内部层中添加一个或更多个的极性基团,以增强其结晶度,由此减低氢气扩散速率。
内部层优选地尽可能地薄,以尽可能地保持衬里的机械特征(强度、柔性和重量)。
在一个具体实施方式中,该多层结构衬里的厚度介于0.5mm和5mm之间,优选地介于0.75mm和4mm之间,更优选地大于或等于1mm。由此,通过具有这样的厚度,该多层结构衬里具有减小的重量和优化的内部体积,允许结构更容易地集成到车辆架构中。
本发明的另一方面在于提供了生产该塑料衬里的第一方法,该第一方法包括以下步骤:
-挤出成型多层型坯管,该多层型坯管具有第一防渗层、至少一个中间层和具有比该至少一个中间层更低的氢气渗透率的内部层(即第二防渗层);
-将该型坯管夹入空心型腔模具;
-对型坯吹气使其抵着型腔;以及
-将模制好的塑料衬里从模具中取出。
本发明的另一方面在于提供了生产该塑料衬里的第二方法,该第二方法包括以下步骤:
-挤出成型具有第一防渗层和至少一个中间层的多层型坯管;
-将该型坯管夹入空心型腔模具;
-对该型坯吹气使其抵着型腔;
-将模制好的塑料衬里从模具中取出;以及
-给该模制好的塑料衬里的内壁覆上具有比所述至少一个中间层更低的氢气渗透率的内部层(即第二防渗层)。
在一个可替代的实施方式中,该塑料衬里可以通过使用注射模制来形成。例如,该塑料衬里的各个层可以被共注射或按顺序地注射。
与中间层相比,根据本发明的内部层具有低的氢气渗透率。渗透率是扩散率和溶解度的乘积。根据一个替代方案,提出了一种用于氢气存储的塑料衬里,其包括至少一个中间层和具有比所述至少一个中间层更低的氢气溶解度的内部层。在这样的替代方案中,该内部层具有比中间层更低的氢气溶解度和比中间层更高的氢气扩散率(只要得到的渗透率低于中间层的渗透率就可以)。
如上所述,衬里可以被设计为不仅用作流体屏障,还用作当使用那种方法来制造容器时丝线缠绕期间的芯轴。在丝线缠绕过程期间,必须在被浸渍的纤维上施加大的压力以获得复合材料结构的良好封装,从而防止导致压力容器破裂的气泡。市场上现有的解决方案在于厚的衬里,这显著地增加了压力容器的重量并由此增大了燃料消耗。
本发明的另一方面在于,提供一种用于氢气存储的塑料衬里,该塑料衬里具有减小的厚度,但同时保持了良好的机械强度以支持丝线缠绕过程,并且不损害在丝线缠绕过程或其它任何允许围绕衬里封装复合材料增强物以制造复合材料压力容器的过程之后的结构衬里完好性。
本发明的一个主题因此在于一种用于氢气存储的塑料衬里,其包括至少一个中间层和至少一个基于增强热塑性材料复合物(composition)的层。
与非增强材料相比,该增强热塑性材料复合物增大模量10%。
增强热塑性材料复合物本身是已知的,但将这样的复合物用在用于氢气存储的衬里的多层结构中不是已知的。
根据本发明的塑料衬里可以包括一个或更多个具有增强热塑性材料复合物的层。
在本发明的范围内,术语“增强”被理解为指包括处于散布的状态(即形式为与塑料混合的“自由”颗粒,而不是像在编织织物或毡垫中那样被编织或缠绕的颗粒(纤维)(一种或多种)那样)的增强物(或其混合物)(一种或多种),其量使得这些增强物对该复合物的机械特性具有显著的影响。在这里要区分(i)微观填料/增强物,对于这样的填料/增强物,对特性的显著影响是通过高填充水平(一般高于10%)来获得的,和(ii)纳米填料,对于纳米填料,大的特性变化是通过仅百分之几的增强物来获得的。
通常,这些增强物是纤维性增强物(碳纤维、天然纤维、玻璃纤维等)、珠子(例如玻璃珠,其通常是空心的珠子)或颗粒(例如滑石、粘土、蒙脱石、蛭石、膨胀石墨、石墨烯)。增强物优选地是纤维。粉末(碳黑、白垩、滑石、硫酸钡等)一般不被认为是本发明范围内的增强物,当然,能够对复合物的机械特性具有显著影响的粉末是例外。玻璃纤维、尤其是短和长玻璃纤维在本发明的范围内给出良好的结果。对于短纤维,已经通过将基于E类型玻璃(尤其是具有施胶剂(sizing agent)和/或增容剂例如PE-g-MAH的)的、直径介于10和20μm之间并且初始长度介于2和8mm之间的纤维散布在HDPE中,获得了良好的结果。
根据一个优选的变型,玻璃纤维被选作增强物,并且以10-50%的量被包含(优选地均匀地被包含,通常通过在挤出机中混合以制造母料粒料)。
在一个有利的实施方式中,根据本发明的塑料衬里包括至少一个中间层、具有比所述至少一个中间层更低的氢气渗透率的内部层,以及至少一个基于增强热塑性材料复合物的层。
优选地,该增强热塑性材料复合物的层不是多层结构的内部层。
优选地,该增强热塑性材料复合物的层是多层结构的外部层。在另一具体实施方式中,该增强热塑性材料复合物的层可以是多层结构的中间层。
使用这样的增强热塑性材料复合物的层允许减小衬里的厚度(尤其是中间层(一层或多层)的厚度),由此减小整个存储系统的重量、减少纤维卷绕圈数,并改善在车辆上的封装(对于车辆上的给定空间,更大的可用体积)。
附图说明
通过以下依赖于图1至图4的例子,非限制性地示出了本发明。在这些图中,相同的层具有相同的附图标记。
具体实施方式
图1是一个根据本发明的第一具体实施方式的塑料衬里的多层结构的示意性横截面视图。如图1所示,该塑料衬里可以包括基于PVDF的内部层7、第一粘着剂层6、基于HDPE的中间层5、第二粘着剂层4、基于EVOH的防渗层3、第三粘着剂层2和基于HDPE的外部层1。
结合了PVDF层和EVOH层的多层结构的优点在于增强了防渗效果(即减小/消除气体渗透的风险),同时有效地保护衬里免受由于起泡造成的开裂效果。
图2是一个根据本发明的第二具体实施方式的塑料衬里的多层结构的示意性横截面视图。如图2所示,该塑料衬里可以包括基于PVDF的内部层7、第一粘着剂层6、基于HDPE的中间层5、第二粘着剂层4、基于EVOH的防渗层3、第三粘着剂层2、再次研磨料层8和基于HDPE的外部层1。
术语“再次研磨料”被理解为指通过碾碎在制造空心体例如燃料储箱/管或根据本发明的塑料衬里的各个阶段获得的残料、或通过在这样的物品的使用寿命终止时碾碎这样的物品而获得的塑料。
图3是一个根据本发明的第三具体实施方式的塑料衬里的多层结构的示意性横截面视图。如图3所示,该塑料衬里可以包括基于PVDF的内部层7、粘合层5’、第一粘着剂层4、基于EVOH的防渗层3、第二粘着剂层2和基于HDPE的外部层1。
在本发明的第四具体实施方式(未示出)中,塑料衬里可以包括基于PVDF的内部层、粘着剂层和基于聚酰胺的外部层。
术语“聚酰胺”被理解为指任何基于酰胺单元的均聚物、任何包括至少两种不同的酰胺单元的共聚物,以及任何在重量上包括至少50%的来自于酰胺的单元的共聚物。该定义的酰胺单元是通过打开环状聚酰胺的环还是通过二羧酸与二胺的缩聚来获得的是无关紧要的。作为可以被使用的聚酰胺的例子,可以非限制性地提到:PPA(聚邻苯二甲酰胺)、PA-6、PA-11、PA-12和n-mXD6(聚丙烯酰胺)。PA-6通常是优选的。
在本发明的一个变型中,基于PVDF的内部层可以被基于EVOH的内部层代替。
图4是一个根据本发明的第四具体实施方式的塑料衬里的多层结构的示意性横截面视图。如图4所示,该塑料衬里可以包括基于HDPE的内部层16、第一粘着剂层15、基于EVOH的防渗层14、第二粘着剂层13、再次研磨料层12和基于增强热塑性材料复合物的外部层11。
本发明还涉及一种包括如上所述的塑料衬里的复合材料压力容器。
本发明还涉及一种包括如上所述的塑料衬里的车辆。
本发明的塑料层尤其适于氢气存储。
在另一具体实施方式中,本发明的塑料衬里被用于其它类型的气体的存储,尤其是用于压缩天然气的存储。
Claims (16)
1.用于氢气存储的塑料衬里,其包括:
-第一防渗层(3),
-第二防渗层(7),其被配置为与氢气接触的内部层,
-至少一个中间层,其被布置在所述第一和第二防渗层之间,
其中所述第二防渗层(7)具有比所述至少一个中间层更低的氢气,使得所述第二防渗层(7)减缓氢气向所述至少一个中间层中的迁移。
2.如权利要求1所述的塑料衬里,其中所述第二防渗层(7)具有比所述第一防渗层(3)更高的氢气渗透率。
3.如权利要求1和2中任一项所述的塑料衬里,其中所述第一防渗层(3)的氢气渗透率比所述内部层(7)的氢气渗透率低至少20%。
4.如权利要求1至3中任一项所述的塑料衬里,其中所述第一防渗层(3)由乙烯含量比所述内部层(7)的乙烯含量更低的乙烯/乙烯醇共聚物(EVOH)制成。
5.如权利要求1至4中任一项所述的塑料衬里,其中所述内部层(7)由从以下清单中选择的材料制成:聚偏二氟乙烯(PVDF)、聚乙烯氯化物(PVDC)、芳香族尼龙、脂肪族尼龙、无定形尼龙、聚对苯二甲酸乙二醇酯(PET)、LCP、丙二醇藻酸盐(PGA)和乙烯含量比所述第一防渗层(3)的乙烯含量更高的乙烯/乙烯醇共聚物(EVOH)。
6.如权利要求1至5中任一项所述的塑料衬里,其中所述内部层包含填料。
7.如权利要求1至5中任一项所述的塑料衬里,其中所述内部层包含极性基团。
8.如权利要求1至7中任一项所述的塑料衬里,其中该塑料衬里包括至少一个基于增强热塑性材料复合物的层。
9.如权利要求1所述的塑料衬里,其中该塑料衬里包括基于PVDF的内部层(7)、第一粘着剂层(6)、基于HDPE的中间层(5)、第二粘着剂层(4)、基于EVOH的防渗层(3)、第三粘着剂层(2),以及基于HDPE的外部层(1)。
10.如权利要求1所述的塑料衬里,其中该塑料衬里包括基于PVDF的内部层(7)、第一粘着剂层(6)、基于HDPE的中间层(5)、第二粘着剂层(4)、基于EVOH的防渗层(3)、第三粘着剂层(2)、再次研磨料层(8)和基于HDPE的外部层(1)。
11.如权利要求1所述的塑料衬里,其中该塑料衬里包括基于PVDF的内部层(7)、基于改性塑料的层(5’)、第一粘着剂层(4)、基于EVOH的防渗层(3)、第二粘着剂层(2)和基于HDPE的外部层(1)。
12.如权利要求1所述的塑料衬里,其中该塑料衬里包括基于PVDF的内部层、粘着剂层和基于聚酰胺的外部层。
13.生产具有多层式壁的塑料衬里的方法,该方法包括以下步骤:
-挤出成型多层型坯管,该多层型坯管具有第一防渗层、至少一个中间层和具有比所述至少一个中间层更低的氢气渗透率的内部层;
-将所述型坯管夹入空心型腔模具;
-对所述型坯吹气使其抵着所述空心型腔;以及
-将模制好的塑料衬里从所述模具中取出。
14.生产具有多层式壁的塑料衬里的方法,该方法包括以下步骤:
-挤出成型具有第一防渗层和至少一个中间层的多层型坯管;
-将所述型坯管夹入空心型腔模具;
-对所述型坯吹气使其抵着所述型腔;
-将模制好的塑料衬里从所述模具中取出;以及
-给所述模制好的塑料衬里的内部壁覆上内部层,所述内部层具有比所述至少一个中间层更低的氢气渗透率。
15.复合材料压力容器,该复合材料压力容器包括如权利要求1至12中任一项所述的塑料衬里。
16.车辆,该车辆包括如权利要求1至12中任一项所述的塑料衬里。
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PCT/EP2015/064195 WO2015197661A1 (en) | 2014-06-24 | 2015-06-24 | Plastic liner for a composite pressure vessel. |
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EP2960053A1 (en) | 2015-12-30 |
EP3160745A1 (en) | 2017-05-03 |
KR102541099B1 (ko) | 2023-06-07 |
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US20180149312A1 (en) | 2018-05-31 |
WO2015197661A1 (en) | 2015-12-30 |
EP3160745B1 (en) | 2024-08-14 |
JP6803753B2 (ja) | 2020-12-23 |
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