CN105371100B - 一种复合材料容器及其复合材料层的成型方法 - Google Patents

一种复合材料容器及其复合材料层的成型方法 Download PDF

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CN105371100B
CN105371100B CN201410438888.7A CN201410438888A CN105371100B CN 105371100 B CN105371100 B CN 105371100B CN 201410438888 A CN201410438888 A CN 201410438888A CN 105371100 B CN105371100 B CN 105371100B
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composite material
fiber
container
composite
material layer
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CN105371100A (zh
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杨明高
匡欢
李美林
张宏
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Sinoma Science and Technology Suzhou Co Ltd
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Priority to CN201410438888.7A priority Critical patent/CN105371100B/zh
Priority to PCT/CN2015/078938 priority patent/WO2016029718A1/zh
Priority to KR1020177005905A priority patent/KR20170042307A/ko
Priority to PE2017000266A priority patent/PE20170637A1/es
Priority to CA2956336A priority patent/CA2956336C/en
Publication of CN105371100A publication Critical patent/CN105371100A/zh
Priority to US15/442,707 priority patent/US20170167661A1/en
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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
    • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/56—Winding and joining, e.g. winding spirally
    • B29C53/562—Winding and joining, e.g. winding spirally spirally
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C53/00—Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/56—Winding and joining, e.g. winding spirally
    • B29C53/58—Winding and joining, e.g. winding spirally helically
    • B29C53/581—Winding and joining, e.g. winding spirally helically using sheets or strips consisting principally of plastics material
    • B29C53/582—Winding and joining, e.g. winding spirally helically using sheets or strips consisting principally of plastics material comprising reinforcements, e.g. wires, threads
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B29K2105/0854—Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands or yarns in the form of a non-woven mat
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Abstract

本发明公开一种复合材料容器的复合材料层成型方法，一连续纤维按一预定角度缠绕于一内胆外表面形成至少一层复合材料层；在该复合材料层的的层间和/或内表面和/或外表面上加入一添加物，用于防止该复合材料层沿纤维方向开裂。

Description

一种复合材料容器及其复合材料层的成型方法
技术领域
本发明涉及一种气体运输技术，尤其涉及一种复合材料容器及其复合材料层的成型方法。
背景技术
现有技术中针对天然气、氢气、氦气等气体的运输，主要是通过提高存储压力的方式来实现运输。随着气体工业的发展，对气体存储运输容器(气瓶)的压力需求也在不断提高。
现有技术中所生产的高压复合容器(气瓶)，其内胆通常为金属材料制成。为了增加复合容器(气瓶)的容积和承压力，通常的做法是用高压无缝金属管采用端头旋压缩颈方法加工成内胆，并在内胆的外表面缠绕一层高强度纤维材料，利用高强度纤维材料的拉力来增强内胆的承压力。现有技术中，由于采用纤维缠绕成型工艺成型的表面具有复合材料层的容器(气瓶)不可避免在施压后会出现沿着纤维方向的开裂或龟裂。随着使用次数的增加和特定环境的影响，这些开裂或龟裂会有扩展的趋势，严重的更会使整个复合材料层开裂。
有鉴于此，现有技术中急需要一种新的技术能有效减少或消除复合材料层的开裂。
发明内容
为了克服现有技术中存在的缺陷，本发明提供一种减少甚至消除复合材料层开裂的复合材料容器及其复合材料层的成型方法。
为了实现上述发明目的，本发明公开一种复合材料容器的复合材料层成型方法，一连续纤维按一预定角度缠绕于一内胆外表面形成至少一层复合材料层；在该复合材料层的的层间和/或内表面和/或外表面上加入一添加物，用于防止该复合材料层沿开裂。
更进一步地，该添加物位于两层复合材料层之间。
更进一步地，该添加物为织物或非织物。
更进一步地，该添加物的形状为纤维状、片状、絮状、块状。
更进一步地，该添加物由金属或非金属材料制成。
更进一步地，该添加物由纤维类材料组成。该纤维类材料由以下材料中的一种或多种组成：碳纤维、玻璃纤维、芳纶纤维、聚酯纤维、金属纤维。
更进一步地，该连续纤维沿环向缠绕该内胆外表面。
更进一步地，该连续纤维沿螺旋状缠绕该内胆外表面。
本发明同时公开一种复合材料容器，该复合材料容器包括一内胆和一复合材料层，该复合材料层由如权利要求1至9任意一项该的方法制成。
与现有技术相比较，本发明所提供的复合材料容器及其复合材料层的成型技术，在容器缠绕复合材料层内部起纵向(轴向)补强作用，可有效防止复合材料开裂或龟裂的产生；同时可以有效防止容器长期使用过程中缠绕复合材料层表面沿纤维缠绕的方向开裂或龟裂的延伸。这在一定程度上稳定了容器的性能，从而提高了容器在使用过程中的安全性。
附图说明
关于本发明的优点与精神可以通过以下的发明详述及所附图式得到进一步的了解。
图1是本发明所涉及的复合材料容器的结构示意图；
图2是本发明所涉及的复合材料容器的局部放大示意图。
具体实施方式
下面结合附图详细说明本发明的具体实施例。
由于现有采用纤维环向缠绕成型工艺成型的复合材料容器(或称气瓶)，由于内置的金属内胆和金属内胆的外表面所缠绕的复合材料层彼此间的收缩率不一致。气瓶在反复充装的过程中，气瓶的长度会有延伸，由于金属材料的延展性明显强于复合材料的延展性，因此在气瓶反复重装的过程中，金属延伸的长度远远超过复合材料延伸的长度，这样就会造成复合材料表面层的环向开裂。因此在施压后会出现沿着纤维方向的开裂或龟裂，随着使用次数的增加和特定环境的影响，这些开裂或龟裂会有扩展的趋势，严重的会使整个复合材料层开裂。因此，本发明的目的在于提供一种复合材料容器及其复合材料层的成型方法能有效抑制连续纤维层的开裂。
本发明根据力学分析计算纤维环向缠绕时与其匹配的纵向力，在复合材料层成型过程中将此增强技术应用其中，实现容器在施压受力过程中，当气瓶的复合材料层沿纤维方向开裂时，提供一个与开裂方向相垂直的拉力，从而改善表面的开裂现象以及长期的开裂延伸现象。
如图1所示，图1是本发明所涉及的复合材料容器的结构示意图。该复合材料容器可以是用于容纳高压气体的瓶子，也可以是容纳高压气体、液体、固体的管道。图1是本发明的其中一种实施方式，该实施方式中该容器2优质无缝钢管制成，钢管的两端采用端头旋压缩颈方法加工为两个瓶口3。瓶口3内置螺纹用于固定前端塞和后端塞。其中前端塞上设置进气出气阀门，后端塞上设置一安全泄放装置(图中未示出)。在另一实施方式中，该钢瓶也可以仅包含一个端口。
该钢瓶2的外表面上包括一复合材料层1。复合材料层1通常有连续纤维沿环向(a方向)绕制而成。复合材料层1可以仅覆盖钢瓶2的部分表面，也可以覆盖钢瓶2的全部表面，包括瓶口3的外表面一律覆盖。图1所示出的复合材料容器是一种典型的环向缠绕式的复合材料容器。环向缠绕的特点在于连续纤维的绕制角度与气瓶的轴向(b方向)几乎垂直。环向缠绕的气瓶容易出现的技术问题在于，当瓶内充满高压气体时，由于金属内胆和复合材料层两者的收视率不一致，导致复合材料层出现环向(a方向)的开裂。本发明通过在纵向提供一个补偿力，以克服环向开裂。
在另一种实施方式中，复合材料容器采用全缠绕或大角度缠绕方式。当采用全缠绕或大角度缠绕的时候，在沿连续纤维平行的方向会出现裂纹，根据本发明所提供的技术方案，需要在与连续纤维垂直的角度提供一个补偿力，以克服开裂。
如图2所示，图2是本发明所涉及的复合材料容器的局部放大示意图。与现有技术不一致的是，本发明所提供的复合材料层1除了包括连续纤维10外，还包括一添加物11。这是为了在复合材料层成型过程中增加一个与环向拉力相匹配的纵向(图1中的b方向)力。用以实现容器在施压受力过程中，给于环向开裂一个纵向拉力，从而改善表面的开裂现象以及长期的开裂延伸现象。
在一种较佳的实施例中，连续纤维10和添加物11是连续成型的，即一层连续纤维10上面或下面覆盖一层添加物11。添加物11可以是织物也可以是非织物。其中织物是指由两条以上的织线交叉和绕结后形成的材料。添加物11可以是纤维状物，可以是絮状物，也可以是块状物、片状物。如果是纤维状物，则该添加物11的排列方向沿纵向平行或与纵向呈一定角度延伸。
添加物11可以由碳纤维、玻璃纤维、芳纶纤维、聚酯纤维、金属纤维制成。碳纤维(carbon fiber，简称CF)，是一种含碳量在95％以上的高强度、高模量纤维的新型纤维材料。它是由片状石墨微晶等有机纤维沿纤维轴向方向堆砌而成，经碳化及石墨化处理而得到的微晶石墨材料。碳纤维包括但不限于为聚丙烯腈基碳纤维、沥青基碳纤维、粘胶基碳纤维、酚醛基碳纤维、气相生长碳纤维。玻璃纤维(glass fiber或fiberglass)是指成分为二氧化硅、氧化铝、氧化钙、氧化硼、氧化镁、氧化钠等经高温熔制、拉丝、络纱、织布等工艺形成的材料。玻璃纤维包括但不限于无碱玻璃纤维、中碱玻璃纤维、高碱玻璃纤维、高强玻璃纤维、高模量玻璃纤维、高硅氧玻璃纤维、耐碱玻璃纤维以及其他玻璃纤维。芳纶纤维全称为聚对苯二甲酰对苯二胺纤维(Aramid fiber)，包括对位芳酰胺纤维(PPTA)和间位芳酰胺纤维(PMIA)。金属纤维(Steel Fiber)主要是指由金属(铁，铁合金、钢等)造成的金属纤维，以切断细钢丝法、冷轧带钢剪切、钢锭铣削或钢水快速冷凝法制成长径比(纤维长度与其直径的比值,当纤维截面为非圆形时,采用换算等效截面圆面积的直径)为40～80的纤维。
本发明还同时提供一种复合材料的成型方法，通过在环向缠绕容器缠绕复合材料成型过程中加入纤维织物实现，这里所述的纤维织物范围较为广泛，如：碳纤维织物，玻璃纤维织物，芳纶纤维织物或其混合纤维强物等；也包括预浸基体树脂的纤维织物。首先在选择纤维织物时，其表面浸润剂必须与缠绕用连续纤维体系和树脂体系相容，这样在成型过程中纤维织物、缠绕用连续纤维和树脂基体通过固化形成整体缠绕复合材料层，在施压条件下作为一整体承载载荷。同时在长期使用过程中不会因为两种材料而出现分层等现象影响气瓶的使用寿命；其次，采用平铺的方式将纤维织物铺覆于经分析计算的某层(可以是底层至最外层中的任何一层)环向缠绕层之上，用树脂基体将其均匀浸透(如果选用预浸基体树脂纤维织物可省略这浸透过程)，铺覆完成后继续环向缠绕，将铺覆的纤维织物平整的缠绕于缠绕层之间。纤维织物铺覆位置和层数均可通过分析计算和产品实际情况进行调整。
以下将具体提供一种制造如本发明所涉及的复合材料容器的方法，首先根据设计容量选取配套长度的高压无缝钢管制成内胆，再将内胆定位在一个旋转支架的旋转轴上，再在内胆表面制备高强度复合材料层。
复合材料层制备步骤，选用与缠绕用连续纤维和树脂基体相容的表面浸润剂，将纤维织物、缠绕用连续纤维和树脂基体、表面浸润剂通过固化形成整体缠绕复合材料层。
缠绕时根据表1中的参数将纤维浸渍树脂基体缠绕至环形容器(内胆)上。
Figure BDA0000562861510000061
表1
缠绕至特定层时，停止缠绕，将添加物铺覆于所述的复合材料特定层上。该特定层可以是第n层(n为自然数)。本领域普通技术人员可以通过气瓶设计结构尺寸和关键点、线的布置，以及结构的对称性等参数，设定特定层的位置。
连续纤维层缠绕在内胆表面时可以沿环向缠绕，也可以与环向呈一定角度缠绕(螺旋缠绕)。缠绕过程中增加的添加物铺覆的方向，可以垂直于环向90°力方向铺覆，或以与气瓶轴线30°力方向铺覆等。
缠绕完成后，复合材料层固化采用水平旋转方式阶梯式温度固化方式，在95～155℃的阶梯温度下固化4～5小时，在其过程中气瓶水平旋转，保证整个过程中气瓶表面含胶量均匀。
以内胆外径为406mm,总长为2140mm的环缠气瓶为对照样品，未充装前该气瓶直线段长度为1650mm经历25MPa工作压力反复充放15000次后，气瓶内胆的直线段长度变为1670mm，金属内胆长度变化达到20mm，而复合材料层直线段的长度变化甚微。由于两者长度变化严重不一致，因此复合材料层便出现了很明显的环向开裂现象，最宽的单条环向裂缝宽度能达到7mm。
以加入添加物的内胆外径为406mm,总长为2140mm的环缠气瓶为对照样品。在经历25MPa工作压力反复充放15000次后，气瓶内胆的直线段长度由1650mm变为1670mm，金属内胆长度变化达到20mm。气瓶内胆的变化率仍然达到1.2％。但是由于对纵向力进行补偿，加入添加物的环缠气瓶的外表面仅有比较均匀的环向裂纹，裂纹最宽宽度不足2mm。
本说明书中所述的只是本发明的较佳具体实施例，以上实施例仅用以说明本发明的技术方案而非对本发明的限制。凡本领域技术人员依本发明的构思通过逻辑分析、推理或者有限的实验可以得到的技术方案，皆应在本发明的范围之内。

Claims (5)

1.一种复合材料容器的复合材料层成型方法，其特征在于，一连续纤维按一预定角度缠绕于一内胆外表面形成至少一层复合材料层；在所述复合材料层的层间和/或内表面和/或外表面上加入一用于防止所述复合材料层开裂的添加物，所述添加物为织物或非织物，所述添加物的形状为纤维状、片状、絮状或块状，所述添加物由纤维类材料组成，所述纤维类材料由以下材料中的一种或多种组成：碳纤维、玻璃纤维、芳纶纤维、聚酯纤维、金属纤维。
2.如权利要求1所述的复合材料层成型方法，其特征在于，所述添加物位于两层复合材料层之间。
3.如权利要求1所述的复合材料层成型方法，其特征在于，所述连续纤维沿环向缠绕所述内胆外表面。
4.如权利要求1所述的复合材料层成型方法，其特征在于，所述连续纤维沿螺旋状缠绕所述内胆外表面。
5.一种复合材料容器，其特征在于，所述复合材料容器包括一内胆和一复合材料层，所述复合材料层由如权利要求1至4任意一项复合材料层成型方法制成，其中，缠绕过程中，添加物铺覆的方向为垂直于环向90°力方向铺覆。
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