CN102066827B - 贮气罐和贮气罐的制造方法 - Google Patents

贮气罐和贮气罐的制造方法 Download PDF

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CN102066827B
CN102066827B CN2009801236818A CN200980123681A CN102066827B CN 102066827 B CN102066827 B CN 102066827B CN 2009801236818 A CN2009801236818 A CN 2009801236818A CN 200980123681 A CN200980123681 A CN 200980123681A CN 102066827 B CN102066827 B CN 102066827B
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oxide layer
resin interlining
interlining
resin
gas tank
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CN102066827A (zh
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江森作马
四户大希
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Toyota Motor Corp
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Toyota Motor Corp
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17—STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17C—VESSELS FOR CONTAINING OR STORING COMPRESSED, LIQUEFIED OR SOLIDIFIED GASES; FIXED-CAPACITY GAS-HOLDERS; FILLING VESSELS WITH, OR DISCHARGING FROM VESSELS, COMPRESSED, LIQUEFIED, OR SOLIDIFIED GASES
    • F17C1/00—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/02—Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge involving reinforcing arrangements
    • F17C1/04—Protecting sheathings
    • F17C1/06—Protecting sheathings built-up from wound-on bands or filamentary material, e.g. wires
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C63/00—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/24—Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using threads
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C53/56—Winding and joining, e.g. winding spirally
    • B29C53/58—Winding and joining, e.g. winding spirally helically
    • B29C53/60—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels
    • B29C53/62—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels rotatable about the winding axis
    • B29C53/66—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels rotatable about the winding axis with axially movable winding feed member, e.g. lathe type winding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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  • Engineering & Computer Science (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
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  • Sustainable Energy (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Filling Or Discharging Of Gas Storage Vessels (AREA)
  • Moulding By Coating Moulds (AREA)
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Abstract

本发明提供一种对氢气等的分子小的气体也可确保高的气体阻挡性的贮气罐。在FRP层的内侧具有树脂衬里的高压贮气罐中，在树脂衬里的内面形成氧化层。通过长丝缠绕法将增强纤维卷绕在树脂衬里的外面时，预先将空气封入树脂衬里的内部，在接着的热固化增强纤维形成FRP层时，热氧化树脂衬里的内面来形成氧化层。

Description

贮气罐和贮气罐的制造方法
技术领域
本发明涉及贮气罐(gas tank)和贮气罐的制造方法。
背景技术
在搭载于例如汽车等车辆上的燃料电池系统中，使用高压贮气罐作为燃料气体的供给源。这种贮气罐，使用例如在树脂衬里(内容器)的外面形成有增强层的贮气罐(参照专利文献1)。增强层，一般通过FW(长丝缠绕)法将含有树脂的纤维卷绕在树脂衬里的外面，其后通过热固化来形成。
上述贮气罐，为了防止由透过所导致的燃料气体的泄漏，要求高的气体阻挡性。作为确保气体阻挡性的方法，在专利文献2中公开了：在贮气瓶的内壳的内表面形成氟树脂的被膜，防止作为燃料气体的天然气的透过。
现有技术文献
专利文献1：日本特开2006-242247号公报
专利文献2：日本特开平8-1813号公报
发明内容
但是，上述方法，虽然能够确保对分子比较大的天然气的气体阻挡性，但对于氢气等分子比较小的气体不能得到充分的气体阻挡性。
本发明是鉴于该点而完成的，其目的是提供对氢气等的分子小的气体也能够确保高的气体阻挡性的贮气罐和该贮气罐的制造方法。
用于达到上述目的的本发明，是在增强层的内侧具有树脂衬里的贮气罐，其特征在于，上述树脂衬里形成有氧化层。
根据本发明，即使对氢气等的分子小的气体也可利用氧化层来确保高的气体阻挡性。
也可以在上述树脂衬里的内面形成上述氧化层。在这种情况下，可抑制罐内部的气体透过树脂衬里自身，因此能够防止由气体所导致的树脂衬里的劣化。
上述氧化层可以形成为50～100μm的厚度。通过将氧化层形成为该厚度，能够充分确保气体阻挡性，并且还能维持树脂衬里整体的延展的特性。通过维持树脂衬里整体的延展的特性，可以柔软地应对由热变形和/或载荷所导致的变形，能够确保贮气罐的强度。
上述氧化层可以是与上述树脂衬里相同的树脂的氧化层。在这种情况下，氧化层为与树脂衬里相同的母材，因此可以相同程度地进行例如由热变形和/或载荷所导致的变形。因此，例如树脂衬里与氧化层的粘合性变高。
上述氧化层可以通过氧化上述树脂衬里来形成。在这种情况下，氧化层不会从树脂衬里剥离。
上述树脂衬里可以由聚酰胺系树脂形成。在这种情况下，氧化层的气体阻挡层进一步提高。
上述贮气罐可以是用于贮存氢气的贮气罐。氢气由于分子比较小因此容易透过，将本发明所涉及的贮气罐用于氢气的贮存用途的效果大。
另一观点涉及的本发明，是贮气罐的制造方法，其特征在于，具有：将含有氧的气体封入树脂衬里的内部，采用长丝缠绕法将增强纤维卷绕在上述树脂衬里的外面的工序；和在将上述树脂衬里的外面的增强纤维热固化而形成增强层的同时，将上述树脂衬里的内面热氧化而形成氧化层的工序。
在这种情况下，能够一边在树脂衬里的外面形成增强层一边在树脂衬里的内面形成氧化层，因此能够利用现有的工序简单地制造具有氧化层的贮气罐。
上述贮气罐的制造方法，还具有：在卷绕上述增强纤维的工序之前，注射成型出上述树脂衬里，其后将上述树脂衬里加热处理的工序，在上述加热处理的工序中，可以向上述树脂衬里的内部供给含有氧的气体，将上述树脂衬里的内面热氧化。
上述树脂衬里的内面的热氧化，可以在空气气氛内在130℃的温度下进行10～20小时。在这种情况下，能够实现气体阻挡性和延展性这两方面都优异的树脂衬里。另外，在对上述树脂衬里进行加热处理的工序中进行热氧化的情况下，将形成上述增强层时的热氧化和加热处理树脂衬里时的热氧化合在一起的合计时间为10～20小时。
根据本发明，针对氢气等的分子小的气体也能够确保高的气体阻挡性。
附图说明
图1是搭载有高压贮气罐的燃料电池汽车的示意图。
图2是表示高压贮气罐的概略构成的纵截面图。
图3是高压贮气罐的壁部的放大纵截面图。
图4是表示高压贮气罐的制造方法的主要工序的流程图。
图5是表示对树脂衬里进行加热处理的工序的情况的说明图。
图6是表示将树脂纤维卷绕于树脂衬里的工序的情况的说明图。
图7是表示将树脂纤维热固化的工序的情况的说明图。
图8是表示将树脂纤维热固化的工序的加热温度的变动的说明图。
图9是验证在各种条件下形成的氧化层的气体阻挡性和延展性的实验结果。
具体实施方式
以下，参照附图，对本发明的优选的实施方式进行说明。图1是搭载有本实施方式所涉及的贮气罐的燃料电池汽车1的示意图。
在燃料电池汽车1中，在车身的后部搭载有例如3个高压贮气罐2。高压贮气罐2构成燃料电池系统3的一部分，可通过气体供给线4将燃料气体从各高压贮气罐2供给到燃料电池5。贮存在高压贮气罐2中的燃料气体为可燃性的高压气体，例如为氢气。另外，高压贮气罐2不仅可适用于燃料电池汽车1，而且可适用于电动汽车、混合动力汽车等的车辆，还可适用于各种移动体(例如船舶、飞机、机器人等)和定置设备(住宅、大厦)。
图2是表示高压贮气罐2的概略构成的纵截面图。高压贮气罐2具有例如大致椭圆体的罐主体10、安装在该罐主体10的纵向的两端部的金属盖部11、12。
罐主体10具有例如双层结构，具有内侧的树脂衬里20和作为覆盖该树脂衬里20的外面的增强层的FRP(纤维增强塑料；Fiber ReinforcedPlastics)层21。
树脂衬里20具有与罐主体10大致相同的大致椭圆体形状。树脂衬里20由例如尼龙6、尼龙6，6等的聚酰胺系树脂形成。树脂衬里20具有例如3mm左右的厚度。
FRP层21由含有树脂的纤维形成。FRP层21的树脂，可使用例如环氧树脂、改性环氧树脂或不饱和聚酯树脂等。另外，作为纤维，可以使用碳纤维、金属纤维等。
在树脂衬里20的内面的整个面上形成有氧化层22。图3是放大了高压贮气罐2的壁部的说明图。氧化层22如后述那样是通过使树脂衬里20的内面的树脂氧化来形成的。氧化层22，相对于例如3mm左右的厚度的树脂衬里20，形成为例如50～100μm左右的厚度。
接着，对如以上那样构成的高压贮气罐2的制造方法进行说明。图4是表示该制造方法的主要工序的一例的流程图。
首先，注射成型出树脂衬里20(图4的工序S1)。例如，使聚酰胺系树脂流入模具中，成型出2个大致半椭圆体，将它们熔合，成型出树脂衬里20。通过该注射成型，可成型出厚度均匀的树脂衬里20。
接着，树脂衬里20例如如图5所示那样在加热室30中在规定的条件下被加热处理(退火处理)。在该退火处理中，例如将作为含有氧的气体的空气40供给到树脂衬里20的内部。退火处理，例如在内部压力为大气压、温度为130℃左右的条件下进行5小时左右。由此，在树脂衬里20的残余应力被除去的同时，树脂衬里20的内表面的一部分被热氧化(图4的工序S2)。
退火处理结束之后，树脂衬里20如图6所示那样被设置在纤维卷绕装置50的旋转支撑部51。在该旋转支撑部51上连接有例如与作为含有氧的气体的空气的贮气瓶52连通的气体供给管53，可将贮气瓶52的空气通过气体供给管53和旋转支撑部51供给到树脂衬里20内。
若由旋转支撑部51支撑树脂衬里20，则通过该旋转支撑部51的旋转，将树脂衬里20旋转，聚酰胺系的树脂纤维F被卷绕在树脂衬里20的外面。树脂纤维F，在上游部被浸渗热塑性树脂，其后由纤维引导部54进行角度调整，被卷绕于树脂衬里20。此时，通过气体供给管53将空气供给、封入到树脂衬里20内。由此，可以防止由于树脂纤维F的卷绕而使树脂衬里20凹陷。这样，以规定的厚度将树脂纤维F卷绕在树脂衬里20的整个外面(图4的工序S3)。
在树脂纤维F的卷绕工序之后，高压贮气罐2如图7所示那样在加热炉60中被热处理。高压贮气罐2例如如图8所示那样在90℃左右进行预加热，其后，在130℃左右进行正式加热5～15小时左右。通过该正式加热，树脂纤维F被热固化，形成FRP层21。另外，如图7所示，通过正式加热，由树脂衬里20的内部的空气70热氧化树脂衬里20的内面的树脂，在树脂衬里20的内面形成50～100μm左右的厚度的氧化层22(图4的工序S4)。其后，高压贮气罐2被冷却。这样，制造出在树脂衬里20的内面具有氧化层22的高压贮气罐2。
在此，对在树脂衬里的内面具有氧化层的贮气罐的气体阻挡性和延展性进行验证。图9表示验证在各种条件下的树脂衬里的氢气透过量的实验和验证各条件下的氧化层的抗拉强度、断裂延伸率的实验的结果。
实验，在没有氧化层(99.9％氦气环境下、130℃、15小时的热氧化)、有氧化层的(A)(大气环境下、130℃、5小时的热氧化)、有氧化层的(B)(大气环境下、130℃、15小时的热氧化)、有氧化层的(C)(大气环境下、130℃、50小时的热氧化)的条件下进行。
根据图9，可以确认：有氧化层的(A)、(B)、(C)的情况下，与没有氧化层的情况相比，氢气的透过量大幅度减少。另外，可以确认：按照有氧化层的(A)、(B)、(C)的顺序，即热氧化时间越长则氢气的透过量越少。另外，可以确认：一般地气体阻挡性和延展性具有折衷的关系，若气体阻挡性提高则延展性降低，但关于有氧化层的(A)～(C)的抗拉强度和断裂延伸率，不会在整体上大幅度恶化，有氧化层的(A)、(B)比有氧化层的(C)优异。另外，图9的抗拉强度和断裂延伸率的相对比较，是将没有氧化层的情况设为1来对各个有氧化层的(A)、(B)、(C)进行相对比较的。
根据该实验，可以确认：通过形成氧化层，对氢气等的分子小的气体的气体阻挡性提高。另外，可以确认：通过在与有氧化层的(B)的条件接近的130℃下热氧化10～20小时左右，可得到气体阻挡性高且延展性也不会降低的氧化层。
根据上述的本实施方式，由于树脂衬里20形成有氧化层22，因此对氢气等的分子小的气体也可以确保高的气体阻挡性。
然而，在记载在上述的专利文献2(日本特开平8-1813号公报)的使用氟树脂的被膜的方法中，在吹塑成型贮气瓶时，通过使用含有氟的氮气作为吹入气体来形成氟树脂的被膜。但是，以这种做法实际形成氟树脂的被膜会要求高温高压等的严格条件，需要多个工序，制造不容易。另外，在该方法中，担心在由于某种原因氟树脂被分解了的情况下产生有害的氟化合物。与此相对，根据本实施方式，能够简单地形成氧化层22，因此可以容易地制造高压贮气罐2。另外，由于为氧化层22，因此即使万一分解也难以产生有害的化合物，能够提高安全性。
另外，在上述实施方式中，由于在树脂衬里20的内面形成有氧化层22，因此可抑制罐内部的气体透过树脂衬里20自身，因此能够防止由气体所导致的树脂衬里20的劣化。
由于氧化层22形成为50～100μm的厚度，因此能够确保高的气体阻挡性，并且还能够充分确保树脂衬里20整体的延展的特性。通过确保树脂衬里20整体的延展的特性，能够确保高压贮气罐2的充分的强度。
由于氧化层22为由树脂衬里20的树脂形成的氧化层，因此氧化层22为与树脂衬里20相同的母材，能够以相同程度进行由例如热变形和/或载荷所导致的变形。因此，例如树脂衬里20和氧化层22的粘合性变高。
在日本特开2006-316934号公报中公开了在树脂衬里的内面设置金属层。在这种情况下，金属层和树脂衬里的粘合性、剥离性成为问题，但根据本实施方式，氧化层22是使树脂衬里20氧化而形成的，因此氧化层22和树脂衬里20的粘合性高，氧化层22不会从树脂衬里20剥离。
根据上述实施方式，树脂衬里20由聚酰胺系树脂形成，因此氧化层22的气体阻挡性进一步变高。认为这是因为：在聚酰胺系树脂被氧化了时，树脂的分子结构三维化，致密性提高的缘故。在例如尼龙6，6的情况下，羧基的α位的亚甲基被氧化而变为酮，变化成为具有烯醇基的化合物，该化合物与别的聚酰胺的氨基末端反应，环化而成为三维的结构。
在上述的实施方式中记载的高压贮气罐2的制造方法中，在树脂衬里20的外面卷绕树脂纤维F的工序中，将空气70封入树脂衬里20的内部，在热固化树脂纤维F的工序中，将树脂衬里20的内面热氧化而能够形成氧化层22，因此能够利用现有的工序，简单地制造具有氧化层22的高压贮气罐2。
另外，在上述实施方式中，在注射成型出树脂衬里20，其后对该树脂衬里20进行退火处理的工序中，也将空气40供给到树脂衬里20的内部，使树脂衬里20的内面热氧化。通过这样进行，利用注射成型后的树脂衬里20的加热处理，能够形成氧化层22的一部分，因此能够更加高效地形成氧化层22。
在上述实施方式中，将树脂衬里20的退火处理时的热氧化(图4的工序S2)和树脂纤维F的热固化时的热氧化(图4的工序S4)合计在一起，在空气气氛内在130℃下进行10～20小时的树脂衬里20的热氧化。通过这样进行，如在上述的实验中验证了的那样，能够实现气体阻挡性和延展性这两方面均优异的树脂衬里20。
以上参照附图对本发明的优选实施方式进行了说明，但本发明不限于该例。显然，本领域普通技术人员在记载在权利要求书中的思想的范畴内，能够想到各种的变更例或修正例，就这些变更例或修正例而言，可理解为也当然属于本发明的技术范围。
例如，在以上的实施方式中，为了形成氧化层22而供给到树脂衬里20内的气体为空气，但只要是含有氧的气体，则也可以是氧气等的其他的气体。另外，树脂衬里20的材质不限于聚酰胺系树脂，也可以是聚乙烯树脂、乙烯-乙烯醇共聚树脂(EVOH)、或其他的热塑性树脂等的其他的树脂。
此外，在以上的实施方式中，在树脂衬里20的注射成型后的退火处理时也热氧化了树脂衬里20的内面，但在该阶段未必需要进行热固化，也可以仅在树脂纤维F热固化时进行。另外，在以上的实施方式中，在树脂衬里20的内面形成了氧化层22，但也可以在树脂衬里20的外面和/或中间层形成氧化层22。
附图标记说明
2  高压贮气罐；
20 树脂衬里；
21 FRP层；
22 氧化层；
F  树脂纤维。

Claims (9)

1.一种贮气罐，是在增强层的内侧具有树脂衬里的贮气罐，所述树脂衬里形成有氧化层，所述氧化层是与所述树脂衬里相同的树脂的氧化层。
2.根据权利要求1所述的贮气罐，其特征在于，在所述树脂衬里的内面形成有所述氧化层。
3.根据权利要求1或2所述的贮气罐，其特征在于，所述氧化层形成为50～100μm的厚度。
4.根据权利要求1或2所述的贮气罐，其特征在于，所述氧化层是通过对所述树脂衬里进行氧化而形成的。
5.根据权利要求4所述的贮气罐，其特征在于，所述树脂衬里是采用聚酰胺系树脂形成的。
6.根据权利要求1或2所述的贮气罐，是用于贮存氢气的贮气罐。
7.一种贮气罐的制造方法，其特征在于，具有：
将含有氧的气体封入树脂衬里的内部，采用长丝缠绕法将增强纤维卷绕在所述树脂衬里的外面的工序；和
在将所述树脂衬里的外面的增强纤维热固化而形成增强层的同时，将所述树脂衬里的内面热氧化而形成氧化层的工序。
8.根据权利要求7所述的贮气罐的制造方法，其特征在于，在卷绕所述增强纤维的工序之前，还具有注射成型出所述树脂衬里、其后将所述树脂衬里加热处理的工序，
在所述加热处理的工序中，还向所述树脂衬里的内部供给含有氧的气体，将所述树脂衬里的内面热氧化。
9.根据权利要求7或8所述的贮气罐的制造方法，其特征在于，所述树脂衬里的内面的热氧化在空气气氛内在130℃的温度下进行10～20小时。
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