CN115279576A - 罐 - Google Patents
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- Publication number
- CN115279576A CN115279576A CN202180020876.0A CN202180020876A CN115279576A CN 115279576 A CN115279576 A CN 115279576A CN 202180020876 A CN202180020876 A CN 202180020876A CN 115279576 A CN115279576 A CN 115279576A
- Authority
- CN
- China
- Prior art keywords
- resin
- fiber bundles
- layer
- impregnated
- liner
- 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.)
- Pending
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- 239000000835 fiber Substances 0.000 claims abstract description 182
- 229920005989 resin Polymers 0.000 claims abstract description 93
- 239000011347 resin Substances 0.000 claims abstract description 93
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- 238000004804 winding Methods 0.000 claims abstract description 13
- 230000002787 reinforcement Effects 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 24
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- 239000010410 layer Substances 0.000 description 117
- 238000000465 moulding Methods 0.000 description 16
- 238000009730 filament winding Methods 0.000 description 14
- 229920000049 Carbon (fiber) Polymers 0.000 description 11
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- 238000005259 measurement Methods 0.000 description 11
- 239000011342 resin composition Substances 0.000 description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 7
- 238000005470 impregnation Methods 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229920002430 Fibre-reinforced plastic Polymers 0.000 description 4
- 230000006835 compression Effects 0.000 description 4
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- 239000003822 epoxy resin Substances 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- -1 aromatic urea compound Chemical class 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
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- XMTQQYYKAHVGBJ-UHFFFAOYSA-N 3-(3,4-DICHLOROPHENYL)-1,1-DIMETHYLUREA Chemical compound CN(C)C(=O)NC1=CC=C(Cl)C(Cl)=C1 XMTQQYYKAHVGBJ-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PMMYEEVYMWASQN-DMTCNVIQSA-N Hydroxyproline Chemical compound O[C@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-DMTCNVIQSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 238000011156 evaluation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003915 liquefied petroleum gas Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
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- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- B29C53/60—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels
- B29C53/602—Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels for tubular articles having closed or nearly closed ends, e.g. vessels, tanks, containers
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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Abstract
罐,其具有作为内壳的内衬和覆盖所述内衬的外表面的增强层,其中,所述增强层是通过将已含浸树脂的纤维束连续地卷绕于所述内衬的周围而形成的,所述增强层由配置在所述内衬侧的环箍层和螺旋层构成,在卷绕于所述环箍层的相邻的所述已含浸树脂的纤维束之间设有间隙,并且在所述螺旋层中相邻的所述已含浸树脂的纤维束的无间隙地卷绕的部位至少存在一处,构成所述罐的所述树脂的韧性值为1.0MPa·m0.5以上。本发明提供无需已含浸树脂的纤维束的高精度配置及对已含浸树脂的纤维束间的间隙进行检测的装置等的价廉的罐及制造方法。
Description
技术领域
本发明涉及纤维增强塑料(Fiber Reinforced Plastic,FRP)制的罐。
背景技术
FRP是将树脂以增强纤维增强而得到的复合材料,与铁、铝等金属材料比较为轻量,但能够发挥与金属材料相同以上的强度及刚性,因此被广泛使用。
FRP能够成型为平板、H形状、筒状体等多种形状。其中的作为贮藏高压的气体或液体的罐使用的罐通常通过长丝缠绕(Filament Winding)成型来制造。长丝缠绕成型法是一边对卷绕于线轴的纤维束施加张力一边连续地将其放出,在使其含浸固化性树脂后将纤维束卷绕于内衬以形成增强层的成型方法。
在使用长丝缠绕成型法制作的罐中,存在成型时的纤维束间的间隙导致耐压力降低的情况。因此,通常将相邻的纤维束以纤维间无间隙的方式重叠地成型。但是,若是这一方法,则在纤维束彼此重叠的部分和不重叠的部分产生凹凸,施加于纤维束的张力产生差异,在所施加的张力低的纤维束中发生松弛,纤维束的排列错乱。其结果,存在罐的耐压力降低的情况。
因此,例如专利文献1中提出了下述方法:准备在宽度方向上具有厚度差的纤维束,将所述纤维束的薄的部分彼此重叠地成型,致力于使纤维束以能够避免产生由纤维束重叠形成的凹凸的方式重叠。另外,专利文献2中提出了通过将扁平的纤维束变形为四边形状而使得成型时的带之间不产生间隙的方法。另外,专利文献3中提出了对长丝缠绕成型时的带间的间隙进行检测的方法。
现有技术文献
专利文献
专利文献1:日本特开2015-209887号公报
专利文献2:日本特开2012-140997号公报
专利文献3:日本特开2017-7104号公报
发明内容
发明要解决的课题
但是,在同时要求生产速度的状况下,很难实现如专利文献1那样使纤维束的侧面对合而无间隙地卷绕、如专利文献2那样在工序内使扁平的纤维束变形为四边形状。另外,如专利文献3所记载,对长丝缠绕成型时的纤维束间的间隙进行检测的方法需要检测装置,可能导致罐的成本升高。
因而,本发明鉴于上述背景,提供无需以往进行的将纤维束高精度地配置的作业、对纤维束间的间隙进行检测的装置等的价廉的罐。
用于解决课题的手段
为了解决上述课题,本发明的罐具有下述构成。即,
罐,其具有作为内壳的内衬和覆盖所述内衬的外表面的增强层,在所述罐中,所述增强层是通过将已含浸树脂的纤维束连续地卷绕于所述内衬的周围而形成的,所述增强层由配置在所述内衬侧的环箍层和螺旋层构成,在卷绕于所述环箍层的相邻的所述已含浸树脂的纤维束之间设有间隙,并且在所述螺旋层中相邻的所述已含浸树脂的纤维束的无间隙地卷绕的部位至少存在一处,构成所述罐的所述树脂的韧性值为1.0MPa·m0.5以上。
优选的是,本发明的罐中,所述间隙仅设置于与所述内衬接触的所述环箍层。
优选的是,本发明的罐中,从在卷绕于所述环箍层的相邻的已含浸树脂的纤维束之间设置的间隙露出的面积的总和相对于所述内衬的主干部表面积而言的比率大于0%且小于50%。
优选的是,对于本发明的罐而言,在将所述间隙的最小值设为Lmin(mm)、将最大值设为Lmax(mm)、将与所述间隙相邻的已含浸树脂的纤维束的平均宽度设为W(mm)时,所述罐满足0≤Lmin/W<0.5且0.01<Lmax/W<0.5的关系。
优选的是,本发明的罐的所述Lmin及W满足0.01<Lmin/W<0.5的关系。
优选的是,本发明的罐在卷绕于所述环箍层的相邻的已含浸树脂的纤维束之间无间隙的部位存在一处以上。
优选的是,本发明的罐在所述增强层中包含的所述树脂的重量比例为21%~30%。
优选的是,本发明的罐在所述已含浸树脂的纤维束中包含的树脂的粘度在25℃时为10~150Pa·s。
发明效果
根据本发明,能够提供无需以往进行的高精度地配置已含浸树脂的纤维束的作业及对已含浸树脂的纤维束间的间隙进行检测的装置等的价廉的罐。
附图说明
图1是示出罐的剖视图的一例的概略图。
图2的(a)是示出罐的环箍层的一例的概略图,(b)是示出罐的螺旋层的一例的概略图。
图3是示出罐的层叠构成的一例的概略图。
图4是示出在与内衬接触的环箍层设有纤维束间隙的罐的一例的概略图。
图5是示出在与内衬接触的环箍层中设有一处以上无纤维束间隙的部位的罐的一例的概略图。
图6是示出罐的制造工序的一例的概略图。
具体实施方式
以下依次说明本发明的实施方式。本实施方式是实施本发明的一例,本发明并非限定于本实施例方式。
本发明的罐101是具有作为内壳的内衬102和覆盖内衬102的外表面的增强层103的罐101,增强层103是通过将已含浸树脂的纤维束403连续地卷绕于内衬102的周围而形成的,增强层103由配置在内衬102侧的环箍层201和螺旋层203构成,在卷绕于环箍层201的相邻的已含浸树脂的纤维束之间设有间隙402,并且在螺旋层203中相邻的已含浸树脂的纤维束403的无间隙地卷绕的部位至少存在一处,构成罐101的树脂的韧性值为1.0MPa·m0.5以上。
图1中示出罐101的剖视图。内衬102具有圆筒状的主干部和设置在主干部的两端且与开口部连续设置的穹顶状的镜部。罐101为了保持填充于内部的气体而优选使用具有阻气性的铝、钢铁、树脂等。
增强层103由通过将已含浸树脂的纤维束连续地卷绕于内衬102的周围而形成的构造形成,能够实现罐101的耐压力。
另外,增强层103由配置在内衬102侧的环箍层和螺旋层构成。能够通过将环箍层和螺旋层以需要的层数、角度组合而层叠为需要的厚度,从而实现需要的耐压力。在此,对环箍层及螺旋层进行说明。
图2的(a)示出环箍层201的一例的概略图。环箍层201是将已含浸树脂的纤维束403相对于所述内衬的轴向204以80°以上且110°以下的角度卷绕并层叠于内衬102的圆筒状的主干部而成。以图2的(a)所示的层叠角度从主干部的一端到另一端卷绕已含浸树脂的纤维束,使覆盖主干部整体的成型图案形成为环箍卷,将其单位设为一层。重复形成环箍卷而得到需要的环箍层厚度。罐的圆周方向202的耐压力由层叠的环箍层201的厚度决定。
接下来,在图2的(b)中示出螺旋层203的一例的概略图。螺旋层203是将已含浸树脂的纤维束403相对于内衬的轴向204以大于0°且小于80°或大于110°且小于180°的角度卷绕层叠而成。将以层叠角度从镜部覆盖主干部整体的成型图案形成为螺旋卷,并将其单位设为一层。重复形成螺旋卷而得到需要的螺旋层厚度。罐的轴向204的耐压力由层叠的螺旋层203的厚度决定。
像这样将环箍层201与螺旋层203组合,能够得到图3所示的罐101。
另外,在本发明中,重要的是在卷绕于环箍层201的相邻的已含浸树脂的纤维束之间设有间隙402,并且在螺旋层203中相邻的所述已含浸树脂的纤维束403的无间隙地卷绕的部位至少存在一处。
为了确保罐101破坏时的安全性,如KHKS0121(2016)中所记载的那样要求破坏的起点为主干部。为了实现该要求,关于气体填充时增强层103产生的压力,通常将增强层103的厚度设计为罐的圆周方向202的压力高于罐的轴向204的压力,破坏的起点成为主干部。
因此,若环箍层201的已含浸树脂的纤维束403未均匀地卷绕、即排列错乱,则已含浸树脂的纤维束403的强度实现变得不充分,存在未按照如所设计的那样在主干部破坏的情况。特别是,若卷绕于内衬102的已含浸树脂的纤维束403重合,则在已含浸树脂的纤维束403重叠的部分与不重叠的部分产生张力差,张力低的已含浸树脂的纤维束403松弛而纤维排列错乱。因此,在卷绕于环箍层201的相邻的已含浸树脂的纤维束之间设有间隙402的重要的。若未采用这样的构成,则无法消除已含浸树脂的纤维束403的重叠,已含浸树脂的纤维束403产生张力差,无法使纤维排列整齐。
此外,在螺旋层203中,至少存在一处相邻的已含浸树脂的纤维束403的无间隙地卷绕的部位的重要的。虽然在螺旋层203内设有间隙具有使纤维排列整齐的作用,但若间隙增多,则连结的间隙作为大型缺陷存在,缺陷成为起点,罐101的耐压力降低。在气体填充时,由于作用于螺旋层203的压力比环箍层201低,因此即使螺旋层203的纤维排列错乱,也不会导致罐101破坏,因此使得螺旋层203内至少存在一处相邻的已含浸树脂的纤维束的无间隙地卷绕的部位的重要的。若未采用该构成,则无法在增强层103整体内阻止间隙连结。
此外,构成罐101的树脂的韧性值为1.0MPa·m0.5以上是重要的。优选树脂的韧性值为1.4MPa·m0.5以上。若树脂的韧性值小于1.0MPa·m0.5,则已含浸树脂的纤维束403之间的间隙成为破坏的起点,罐101的耐压力降低。需要说明的是,树脂的韧性值的优选上限为3.0MPa·m0.5,更加优选为2.6MPa·m0.5。若树脂的韧性值的上限为上述优选的范围,则能够抑制受到压力时产生的裂纹的传播,容易确保罐101需要的耐压性。
另外,在本发明中,优选已含浸树脂的纤维束之间的间隙402仅设置在与内衬102接触的环箍层201。就气体填充时罐增强层103产生的压力而言,内层高于外层,与内衬102接触的层承受最大的压力。因此,优选在成为破坏的起点的与内衬102的接触面上配置环箍层201。需要说明的是,与在设置于最内层的环箍层201上设置的螺旋层203相比位于外层侧的增强层无需与环箍层201/螺旋层203一并在已含浸树脂的纤维束403间设有间隙。其理由在于,与最内层相比,外层侧的增强层受到的压力低,因此已含浸树脂的纤维束403的排列错乱对于耐压力的影响低。
另外,在本发明中,优选的是,相对于作为内壳的内衬102的主干部表面积而言,从在卷绕于所述环箍层201的相邻的已含浸树脂的纤维束403之间设置的间隙露出的面积(以下存在称为“纤维束间的间隙面积”的情况)的总和的比率大于0%且小于50%。更加优选所述比率大于0.01%且小于45%。若上述比率大于上述优选的范围,则能够在环箍层201中确保间隙,同时环箍层201的间隙不易变为大的缺陷,能够有效防止耐压力降低。
在此,使用图4说明纤维束间的间隙面积及作为内壳的内衬102的主干部面积的测定方法。内衬102由位于作为罐直体部与曲面的边界的线即切线401的内侧的圆筒状的主干部和与设置于所述主干部的两端的开口部连续设置的穹顶状的镜部构成。内衬102的主干部面积是切线401内侧的圆筒状的主干部面积,已含浸树脂的纤维束之间的间隙402的面积是从所述主干部面积减去已含浸树脂的纤维束403的卷绕面积的面积。前述这些面积能够在将已含浸树脂的纤维束403卷绕于内衬102时使长丝缠绕成型机暂时停止来测定。在获取到内衬102的外观图像后,使用图像软件、计量工具计算纤维束间的间隙面积和作为内壳的内衬的主干部面积。在基于图像计算面积的情况下,既可以是使用色调差等算法的自动程序,也可以以目视修整图像。另外,无需以一个图像显示出内衬102整体,也可以将多个图像连结。需要说明的是,在成型中无法进行已含浸树脂的纤维束之间的间隙402的测定的情况下,也可以将固化后的罐分解来测定已含浸树脂的纤维束403的宽度与已含浸树脂的纤维束之间的间隙402。具体来说,在将罐101沿着罐的轴向204切断并使内衬102与增强层103分离后,从内衬102侧获取增强层103的图像,计算纤维束间的间隙面积和作为内壳的内衬102的主干部面积。需要说明的是,若保持增强层103的形态,则也可以向层间施加力或加热将树脂烧除来分离增强层103。
另外,在本发明中,优选的是,在将设置于增强层103的已含浸树脂的纤维束之间的间隙402的最小值设为Lmin(mm)、将该已含浸树脂的纤维束之间的间隙402的最大值设为Lmax(mm)、将与所述已含浸树脂的纤维束之间的间隙402相邻的已含浸树脂的纤维束403的平均宽度设为W(mm)时,所述罐满足0≤Lmin/W<0.5且0.01<Lmax/W<0.5的关系。在Lmin/W及Lmax/W满足上述优选的下限的情况下,即使由所卷绕的已含浸树脂的纤维束403的松弛引起的线宽变化、由固化中的树脂渗出引起的已含浸树脂的纤维束403的位置移动,也不易形成已含浸树脂的纤维束403重叠的部位,能够稳定地形成已含浸树脂的纤维束之间的间隙402。另外,在Lmin/W及Lmax/W满足上述优选的上限的情况下,已含浸树脂的纤维束之间的间隙402不易变为大的缺陷,能够有效防止耐压力降低。更加优选Lmin/W的下限大于0.01,进一步优选大于0.05。更加优选Lmax/W的下限大于0.05,进一步优选大于0.06。更加优选Lmin/W的上限小于0.45,进一步优选小于0.4。更加优选Lmax/W的上限小于0.45,进一步优选小于0.4。
在此,使用图5说明已含浸树脂的纤维束之间的间隙402及已含浸树脂的纤维束403的宽度的测定方法。已含浸树脂的纤维束之间的间隙402及已含浸树脂的纤维束403的宽度能够在将已含浸树脂的纤维束403卷绕于内衬102时使长丝缠绕成型机暂时停止来测定。目视找出已含浸树脂的纤维束之间的间隙的最大间隙(以下存在称为“最大间隙”的情况)601并进行计测。只要能够测定间隙,游标卡尺、激光仪等方法没有限制。以找出的最大间隙为起点,沿着内衬的轴向204观察已含浸树脂的纤维束之间的间隙402,将所述最大间隙601的宽度设为Lmax,将与所述最大间隙601位于同一轴向204上的已含浸树脂的纤维束之间的间隙的最小间隙(以下存在称为“最小间隙”的情况)603的宽度设为Lmin。接下来,测定与所述最大间隙601相邻的已含浸树脂的纤维束403的宽度(两处),并且以相同的方法测定与最小间隙603相邻的已含浸树脂的纤维束403的宽度。将上述宽度的4点的测定值取平均,设为已含浸树脂的纤维束403的平均宽度W。然后,使用所得到的Lmin及Lmax、W计算Lmin/W和Lmax/W。在此,在沿着内衬的轴向204在已含浸树脂的纤维束间存在重叠605的情况下,将Lmin定义为0。其中,在Lmin为0的情况下,已含浸树脂的纤维束403的平均宽度W仅是与最大间隙相邻的已含浸树脂的纤维束403的宽度(两处)的平均值。此外,在最大已含浸树脂的纤维束的间隙的两端的树脂含浸纤维束403没有间隙的情况下,已含浸树脂的纤维束403的平均宽度W定义为无。需要说明的是,在已含浸树脂的纤维束403的平均宽度W为无的情况下,测定部位的Lmin/W及Lmax/W均设为无值。接下来,以从作为测定起点的间隙沿着内衬圆周方向202大致旋转移动1°的位置为起点,以前述方法从该起点沿着内衬的轴向204测定Lmin/W及Lmax/W。针对内衬的圆周方向202全周重复进行该测定,在所得到的全部测定值中,求出最小的Lmin/W和最大的Lmax/W。需要说明的是,在全部测定位置,在已含浸树脂的纤维束403没有间隙的情况下,Lmin/W和Lmax/W均定义为0。
另外,在本发明中,关于环箍层201中设置的已含浸树脂的纤维束之间的间隙402,无间隙地卷绕的部位存在一处以上是重要的。若在环箍层201中设有间隙,则已含浸树脂的纤维束403没有重叠,因此能够对已含浸树脂的纤维束403施加均匀的张力并使纤维排列整齐,但是,存在在受到压力时产生的裂纹在罐101整体中传播,在低压力下破坏的情况。因此,若未使无间隙地卷绕的部位存在一处以上,则无法抑制裂纹扩展以提高罐101的耐压性。
另外,在本发明中,优选的是,增强层103中包含的所述树脂的重量比例(=已含浸树脂的纤维束403中的基体树脂重量/已含浸树脂的纤维束403整体重量)为21~30%。更加优选增强层103中包含的所述树脂的重量比例为22.5~28.5%。若增强层103中包含的所述树脂的重量比例为上述优选的范围,则已含浸树脂的纤维束403内的树脂量充分,在已含浸树脂的纤维束403间设置的间隙不易作为空隙残留,能够有效防止耐压力降低,另一方面,卷绕于内衬时已含浸树脂的纤维束403不易扩宽,容易稳定地形成间隙。
另外,就本发明使用的树脂粘度而言,优选25℃时的树脂的粘度为10~150Pa·s。若所述树脂粘度为上述优选的范围,则卷绕于内衬时已含浸树脂的纤维束403不易扩宽而容易稳定地形成间隙,另一方面,树脂的含浸容易,且设置于已含浸树脂的纤维束403间的间隙难以作为空隙残留,能够有效防止耐压力降低。
在此,说明本发明使用的纤维束和树脂。
作为构成本发明中使用的纤维束的纤维,能够举出玻璃纤维、碳纤维、石墨纤维、芳纶纤维、硼纤维、氧化铝纤维及碳化硅纤维等。也能够将两种以上的上述增强纤维混合使用。为了获得更高强度的成型品,纤维束使用碳纤维是优选的方式。
在本发明中,能够对应于用途使用所有种类的碳纤维,但为了获得具有高强度的成型品,优选使用基于JIS R 7601(1986)中记载的方法的纤维束拉伸试验中的拉伸弹性模量为3~8GPa的碳纤维。
另外,作为本发明中使用的树脂,优选使用液状的树脂。具体来说,为了使罐获得需要的耐热性、耐环境性能,优选为包含环氧树脂树脂和固化剂的环氧树脂树脂组合物。另外,为了缩短固化时间,也可以适当添加固化催化剂。
图6示出本发明使用的长丝缠绕成型装置的一例。图6是说明本发明的罐的制造方法中的成型流程的一例的整体构成的概略图。
成型流程701主要示出依次配置有执行从线轴702送出纤维束703的送出工序的退卷辊704、包含执行使树脂含浸于纤维束703的树脂含浸工序的树脂含浸辊705、树脂含浸槽706及引导辊707的树脂含浸部、执行对含浸树脂后的纤维束703进行卷绕的卷绕工序的供料入口708、将内衬102及成型装置与内衬102连接的固定轴709的情况。需要说明的是,在图7中仅示出一个线轴702,但并非限定于此,能够配置多个线轴702。
作为线轴702,也可以使用预先在其他工序中含浸树脂而得的预浸丝束(towpreg)。在使用预浸丝束的情况下,能够省略树脂含浸工序。
本发明制造的罐不限于氢气汽车、天然气汽车,能够适当用于船舶、航空器等及固定在地上使用的固定型、医院、消防员使用的空气呼吸器。另外,作为使用该罐保管的物质,可以是氮、氧、氩、液化石油气及氢等气体,也能够举出将所述物质液化得到的物质等。
实施例
<罐中使用的树脂的破坏韧性值的评价方法>
在将罐中使用的固化前的树脂在真空中脱泡后,在利用6mm厚的“特氟龙(注册商标)”制的间隔件设定厚度为6mm的模具中,以实施例及比较例中记载的时间和温度使之固化,制得厚度为6mm的树脂固化板。在将所得到的树脂固化板加工为ASTM D5045-99中记载的试验片形状后,按照ASTM D5045-99实施SENB试验。此时,试样数n=16,采用其平均值作为破坏韧性值。
<罐中使用的树脂粘度的评价方法>
按照JIS Z8803(2011)中的“圆锥-平板形旋转粘度计中的粘度测定方法”,使用安装有标准锥形转子(1°34’×R24)的E型粘度计(东机产业(株)制TVE-22HT),在设定为25℃的状态下,以5转/分钟的旋转速度测定罐中使用的固化前的树脂的粘度,采用该粘度的5次的平均值。
<预浸丝束的制作方法>
使用具备经轴架、湿润辊、轧辊、络纱机的预浸丝束制造装置,在碳纤维“TORAYCA”(注册商标)的单面涂布调节为25℃温度的树脂组合物后,使其通过轧辊而使所述树脂组合物浸至纤维束内部,制得预浸丝束。预浸丝束的线轴的初始张力设为600~1000gf、卷绕比设为6~10,以成为卷绕宽度为230~260mm的圆筒型的方式,将2300m卷绕于纸管。
<纤维束间的间隙面积及作为内壳的内衬的主干部面积的测定方法>
在成型中使长丝缠绕成型机暂时停止后,使用相机(IXY650、Canon制)获取卷绕有已含浸树脂的纤维束的内衬的照片。每当使内衬沿圆周方向旋转90°、180°、270°旋转时实施该作业,获取照片。使用图像处理软件ImageJ(http://imagej.nih.gov/ij/)读取所获取的图像,目视判断已含浸树脂的纤维束部分并使用该软件的polygon及Measure计算面积。接下来,以相同的方法根据图像计算内衬的主干部面积。之后,从内衬主干部面积减去已含浸树脂的纤维束面积来计算纤维束间的间隙面积。进行相同的处理,根据所获取的其余图像计算纤维束间的间隙面积及内衬的主干部面积。最后,将计算出的面积取平均,根据所获取的其余图像得到纤维束间的间隙面积内衬的主干部面积。
<已含浸树脂的纤维束之间的间隙的最小值Lmin、该间隙的最大值Lmax、与所述间隙相邻的已含浸树脂的纤维束的平均宽度W的计算>
在成型中使长丝缠绕成型机暂时停止后,目视找出最大部位,使用游标卡尺(袖珍型游标卡尺100mm、Shinwa测定制)测定所述部位的宽度。以该间隙为起点沿着内衬的轴向观察已含浸树脂的纤维束的间隙,测定已含浸树脂的纤维束之间的间隙的最大值(Lmax)及已含浸树脂的纤维束之间的间隙的最小值(Lmin)。接下来,测定与Lmax相邻的已含浸树脂的纤维束的宽度(两处),并以相同的方法测定与Lmin相邻的已含浸树脂的纤维束的宽度。将上述宽度的4点的测定值取平均,作为已含浸树脂的纤维束的平均宽度W。其中,在测定部位没有纤维束之间的间隙的最小值(Lmin)的情况下,将其间隙设为0,另外,已含浸树脂的纤维束的平均宽度设为仅是与最大间隙相邻的已含浸树脂的纤维束的宽度(两处)的平均值。另外,在已含浸树脂的纤维束的间隙的最大值的两端的已含浸树脂的纤维束没有间隙的情况下,已含浸树脂的纤维束的平均宽度定义为无。需要说明的是,在无已含浸树脂的纤维束的平均宽度的情况下,测定部位的Lmin/W及Lmax/W均设为无值,不包含在测定结果中。接下来,以从作为起点的间隙沿着内衬圆周方向旋转移动大致1°的部位为起点,从该起点沿着内衬的轴向观察已含浸树脂的纤维束的间隙,将已含浸树脂的纤维束之间的间隙的最大值设为Lmax,将已含浸树脂的纤维束之间的间隙的最小值设为Lmin。然后,使用前述方法测定已含浸树脂的纤维束的宽度W,计算Lmin/W及Lmax/W。针对内衬圆周整体重复进行该测定,在所得到的结果中,计算最大的Lmax/W及最小的Lmin/W。需要说明的是,在测定范围的全周上已含浸树脂的纤维束没有间隙的情况下,Lmin/W、Lmax/W均定义为0。
<强度利用率的计算方法>
以KHKS0121(2005)中记载的方法对罐中赋予水压来进行破裂试验,计测破裂时的压力。按照MIL-HDBK-17-3F第3卷(共5卷)17HUNE 2002 5.3.5.3.1(e)式,计算罐的强度(以下称为计算强度),通过下述算式计算罐的强度利用率。
强度利用率(%)=(破裂时的压力/计算强度)×100
以下,基于实施例详细说明本发明。
(实施例1)
将88质量份的“jER(注册商标)”828、12质量份的“DENACOL(注册商标)”EX821、4质量份的作为末端羧基改性丙烯酸系橡胶的“Hypro(注册商标)”1300×8、17质量份的“kaneace(注册商标)”MX125、7.4质量份的作为双氰胺的DICY7T、2.7质量份的作为芳香族脲化合物的DCMU99搅拌、混合,制得树脂组合物。
对于该树脂组合物,基于“罐中使用的树脂的破坏韧性值的评价方法”评价破坏韧性值为2.1MPa·m0.5。使用该树脂组合物和碳纤维“TORAYCA(注册商标)”T910SC-36K-50C制作树脂含量为24%的预浸丝束。需要说明的是,所使用的碳纤维的线束强度为6200MPa。在长丝缠绕成型装置中设置外径为160mm的7.5L的铝制内衬,将所述预浸丝束卷绕于内衬整体。作为第一层,卷绕厚度0.79mm的相对于内衬的轴向成89°、91°的环箍层。此时,通过使得相邻的预浸丝束不重叠地配置,从而在第一层中设有周期性间隙。此时,按照“已含浸树脂的纤维束间间隙的最小值Lmin、该间隙的最大值Lmax、与所述间隙相邻的已含浸树脂的纤维束的平均宽度W的计算”计算Lmin/W、Lmax/W,Lmin/W为0.1、Lmax/W为0.44。作为第2层,卷绕厚度1.07mm的相对于内衬的轴向成18°、162°的螺旋层。进而,作为第3层,卷绕0.52mm的相对于内衬的轴向成89°、91°的环箍层,制得中间体。使所述中间体在固化炉中旋转,于150℃使之固化2小时以制得罐。
按照“强度利用率的计算方法”计算所得到的罐的强度利用率。强度利用率为98.3%、破裂压力为71.5MPa、计算强度为72.7MPa。
(实施例2)
将21质量份的“jER(注册商标)”828、67质量份的“jER(注册商标)”806、5质量份的“EPOTOHTO(注册商标)”YDF-2001、7质量份的作为二甲苯二胺型环氧树脂的TETRAD-X、7质量份的“kaneace(注册商标)”MX-125、5质量份的作为双氰胺的DICY7T、4质量份的作为芳香族脲化合物的DCMU99搅拌、混合,制得树脂组合物。
对于该树脂组合物,按照“罐中使用的树脂的破坏韧性值的评价方法”,评价破坏韧性值为1.6MPa·m0.5。使用该树脂组合物和碳纤维“TORAYCA(注册商标)”T720SC-36K-50C制作树脂含量为24%的预浸丝束。需要说明的是,所使用的碳纤维的线束强度为5800MPa。在长丝缠绕成型装置中设置外径为160mm的7.5L的铝制内衬,将所述预浸丝束卷绕于内衬整体。作为第一层,卷绕厚度0.79mm的相对于内衬的轴向成89°、91°的环箍层。此时,按照“已含浸树脂的纤维束间间隙的最小值Lmin、该间隙的最大值Lmax、与所述间隙相邻的已含浸树脂的纤维束的平均宽度W的计算”计算Lmin/W、Lmax/W,Lmin/W为0.19、Lmax/W为0.45。作为第2层,卷绕厚度1.07mm的相对于内衬的轴向成18°、162°的螺旋层。进而,作为第3层,卷绕0.52mm的相对于内衬的轴向成89°、91°的环箍层,制得中间体。使所述中间体在固化炉中旋转,于110℃使之固化10小时以制得罐。
按照“强度利用率的计算方法”计算所得到的罐的强度利用率。强度利用率为108.5%、破裂压力为73.8MPa、计算强度为68.0MPa。
(实施例3)
除了将第一层的环箍层的已含浸树脂的纤维束以各自分开0.5mm的间隙的方式成型的以外,以与实施例1相同的方法制作罐。此时,由于已含浸树脂的纤维束的宽度不均匀而在第一层的环箍层内形成纤维束重叠的5处“无间隙部位”。此时,按照“已含浸树脂的纤维束之间的间隙的最小值Lmin、该间隙的最大值Lmax、与所述间隙相邻的已含浸树脂的纤维束的平均宽度W的计算”计算Lmin/W、Lmax/W,Lmin/W为0、Lmax/W为0.1。
接下来,按照“强度利用率的计算方法”计算所得到的罐的强度利用率。强度利用率为102.1%、破裂压力为74.2MPa、计算强度为72.7MPa。
(比较例1)
除了将第一层的环箍层的已含浸树脂的纤维束以各自重叠2.5mm的方式成型以外,以与实施例1相同的方法制作罐。此时,由于在第一层的环箍层内无间隙,因此按照“已含浸树脂的纤维束之间的间隙的最小值Lmin、该间隙的最大值Lmax、与所述间隙相邻的已含浸树脂的纤维束的平均宽度W的计算”的定义,Lmin/W、Lmax/W均为0。
按照“强度利用率的计算方法”计算所得到的罐的强度利用率。强度利用率为90.6%、破裂压力为65.9MPa、计算强度为72.7MPa,若存在已含浸树脂的纤维束的重叠,则结果为强度利用率下降。
(比较例2)
将75质量份的“jER(注册商标)”828、40质量份的GAN(日本火药工业制)、8质量份的作为固化剂的DICY7T(三菱化学制)、2质量份的作为固化助剂的DCMU搅拌、混合,制得树脂组合物。
对于该树脂组合物,按照“罐中使用的树脂的破坏韧性值的评价方法”评价破坏韧性值为0.72MPa·m0.5。使用该树脂组合物和碳纤维“TORAYCA(注册商标)”T720SC-36K-50C制作树脂含量为24%的预浸丝束。需要说明的是,所使用的碳纤维的线束强度为5800MPa。在长丝缠绕成型装置中设置外径为160mm的7.5L的铝制内衬,将所述预浸丝束卷绕于内衬整体。作为第一层,卷绕厚度0.79mm的相对于内衬的轴向成89°、91°的环箍层。此时,按照“已含浸树脂的纤维束之间的间隙的最小值Lmin、该间隙的最大值Lmax、与所述间隙相邻的已含浸树脂的纤维束的平均宽度W的计算”计算Lmin/W、Lmax/W,Lmin/W为0.09、Lmax/W为0.32。作为第2层,卷绕厚度1.07mm的相对于内衬的轴向成18°、162°的螺旋层。进而,作为第3层,卷绕0.52mm的相对于内衬的轴向成89°、91°的环箍层,制得中间体。使所述中间体在固化炉中旋转,于110℃使之固化10小时以制得罐。
按照“强度利用率的计算方法”计算所得到的罐的强度利用率。强度利用率为79.0%、破裂压力为53.7MPa、计算强度为68.0MPa,在已含浸树脂的纤维束间有间隙的情况下,若破坏韧性值低,则结果为强度利用率下降。
附图标记说明
101:罐
102:内衬
103:增强层
201:环箍层
202:圆周方向
203:螺旋层
204:罐轴向
401:切线
402:已含浸树脂的纤维束之间的间隙
403:已含浸树脂的纤维束
601:已含浸树脂的纤维束之间的间隙的最大间隙
602:内衬轴向
603:与601位于同一轴向上的已含浸树脂的纤维束之间的间隙的最小间隙
604:内衬圆周方向
605:已含浸树脂的纤维束的重叠
701:成型流程
702:线轴
703:纤维束
704:退卷辊
705:树脂含浸辊
706:树脂含浸槽
707:引导辊
708:供料入口
709:固定轴
Claims (8)
1.罐,其具有作为内壳的内衬和覆盖所述内衬的外表面的增强层,其中,所述增强层是通过将已含浸树脂的纤维束连续地卷绕于所述内衬的周围而形成的,所述增强层由配置在所述内衬侧的环箍层和螺旋层构成,在卷绕于所述环箍层的相邻的所述已含浸树脂的纤维束之间设有间隙,并且在所述螺旋层中相邻的所述已含浸树脂的纤维束的无间隙地卷绕的部位至少存在一处,构成所述罐的所述树脂的韧性值为1.0MPa·m0.5以上。
2.根据权利要求1所述的罐,其中,所述间隙仅设置于与所述内衬接触的所述环箍层。
3.根据权利要求1或2所述的罐,其中,从在卷绕于所述环箍层的相邻的已含浸树脂的纤维束之间设置的间隙露出的面积的总和相对于所述内衬的主干部表面积而言的比率大于0%且小于50%。
4.根据权利要求1至3中任一项所述的罐,其中,在将所述间隙的最小值设为Lmin(mm)、将最大值设为Lmax(mm)、将与所述间隙相邻的已含浸树脂的纤维束的平均宽度设为W(mm)时,所述罐满足0≤Lmin/W<0.5且0.01<Lmax/W<0.5的关系。
5.根据权利要求4所述的罐,其中,所述Lmin及W满足0.01<Lmin/W<0.5的关系。
6.根据权利要求1至3中任一项所述的罐,其中,在卷绕于所述环箍层的相邻的已含浸树脂的纤维束之间无间隙的部位存在一处以上。
7.根据权利要求1至6中任一项所述的罐,其中,在所述增强层中包含的所述树脂的重量比例为21%~30%。
8.根据权利要求1至7中任一项所述的罐,其中,在所述已含浸树脂的纤维束中包含的树脂的粘度在25℃时为10~150Pa·s。
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CN108312571A (zh) * | 2017-01-16 | 2018-07-24 | 丰田自动车株式会社 | 罐的制造方法以及罐 |
US20180229449A1 (en) * | 2017-02-10 | 2018-08-16 | Toyota Jidosha Kabushiki Kaisha | Gas tank and method of manufacturing gas tank |
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