CN117715742A - 包含拉挤的圆柱形元件的储器 - Google Patents

包含拉挤的圆柱形元件的储器 Download PDF

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Publication number
CN117715742A
CN117715742A CN202280052752.5A CN202280052752A CN117715742A CN 117715742 A CN117715742 A CN 117715742A CN 202280052752 A CN202280052752 A CN 202280052752A CN 117715742 A CN117715742 A CN 117715742A
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CN
China
Prior art keywords
cylindrical element
polyamide
tank
fibers
fibres
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
Application number
CN202280052752.5A
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English (en)
Inventor
G·霍奇斯泰特尔
T·萨瓦尔特
A·巴博
A·萨利尼尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Arkema France SA
Original Assignee
Arkema France SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of CN117715742A publication Critical patent/CN117715742A/zh
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/30Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/32Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core on a rotating mould, former or core
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C63/00Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/24Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using threads
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
    • F17CVESSELS 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
    • F17C1/00Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge
    • F17C1/02Pressure vessels, e.g. gas cylinder, gas tank, replaceable cartridge involving reinforcing arrangements
    • F17C1/04Protecting sheathings
    • F17C1/06Protecting sheathings built-up from wound-on bands or filamentary material, e.g. wires
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C53/00Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/56Winding and joining, e.g. winding spirally
    • B29C53/58Winding and joining, e.g. winding spirally helically
    • B29C53/581Winding and joining, e.g. winding spirally helically using sheets or strips consisting principally of plastics material
    • B29C53/582Winding and joining, e.g. winding spirally helically using sheets or strips consisting principally of plastics material comprising reinforcements, e.g. wires, threads
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C53/00Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/56Winding and joining, e.g. winding spirally
    • B29C53/58Winding and joining, e.g. winding spirally helically
    • B29C53/583Winding and joining, e.g. winding spirally helically for making tubular articles with particular features
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C53/00Shaping by bending, folding, twisting, straightening or flattening; Apparatus therefor
    • B29C53/56Winding and joining, e.g. winding spirally
    • B29C53/58Winding and joining, e.g. winding spirally helically
    • B29C53/60Winding and joining, e.g. winding spirally helically using internal forming surfaces, e.g. mandrels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C63/00Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor
    • B29C63/02Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material
    • B29C63/04Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material by folding, winding, bending or the like
    • B29C63/08Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material by folding, winding, bending or the like by winding helically
    • B29C63/10Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material by folding, winding, bending or the like by winding helically around tubular articles
    • B29C63/105Lining or sheathing, i.e. applying preformed layers or sheathings of plastics; Apparatus therefor using sheet or web-like material by folding, winding, bending or the like by winding helically around tubular articles continuously
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C70/003Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised by the matrix material, e.g. material composition or physical properties
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06Fibrous reinforcements only
    • B29C70/10Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/16Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of substantial or continuous length
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/30Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
    • B29C70/34Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
    • B29C70/347Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation combined with compressing after the winding of lay-ups having a non-circular cross-section, e.g. flat spiral windings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/50Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/521Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement before the die
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/28Shaping operations therefor
    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/50Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC] or cross moulding compounds [XMC]
    • B29C70/52Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/525Component parts, details or accessories; Auxiliary operations
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B60K15/00Arrangement in connection with fuel supply of combustion engines or other fuel consuming energy converters, e.g. fuel cells; Mounting or construction of fuel tanks
    • B60K15/03Fuel tanks
    • B60K15/03006Gas tanks
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/04Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
    • H01M8/04082Arrangements for control of reactant parameters, e.g. pressure or concentration
    • H01M8/04201Reactant storage and supply, e.g. means for feeding, pipes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F17STORING OR DISTRIBUTING GASES OR LIQUIDS
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    • F17C2201/0109Shape cylindrical with exteriorly curved end-piece
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F17C2201/00Vessel construction, in particular geometry, arrangement or size
    • F17C2201/05Size
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Abstract

本发明涉及用于容纳加压的流体的储器,其包含:‑至少一个圆柱形元件,其由拉挤的纤维材料制成,所述纤维材料用热塑性基体浸渍,‑第一端工件,其放置在至少一个圆柱形元件的一端处以便封闭所述元件,以及‑第二端工件,其放置在至少一个圆柱形元件的另一端处,其提供有孔口,所述孔口旨在允许所述流体的进入和离开,以及‑至少一个额外的纤维加强物,其部分地或完全地包封所述圆柱形元件以及任选地端工件,所述额外的纤维加强物中含有的纤维沿着与所述圆柱形元件的纵向轴线不同的轴线定位,相对于所述储器中含有的基体和纤维的体积,所述储器的总纤维含量在40体积%和70体积%之间。

Description

包含拉挤的圆柱形元件的储器
本发明涉及旨在容纳加压的流体的罐(tank,油箱)。本发明还涉及其制造工艺,以及其用于储存、运输和/或分配流体,特别是氢的用途。
当前,生态转型正趋于减少油消耗,以及促进污染较少类型的能量的使用。从这个观点来说,氢是特别研究的流体之一。特别地,发现燃料单元电池(cell)车辆正形成大量探讨研究的对象。
在该领域,关于这样的车辆的大量生产的困难之一是所述罐的设计。这是因为这些车辆所携带的所述氢罐经受可范围最高达700bar的工作压力,以及必须满足重要的安全要求,以尽可能地限制碰撞、意外冲击或火灾的后果。例如,当所述罐在涉及所述车辆的意外期间损坏时,或者当火器所发射的抛射体穿行通过所述罐时,对于所述罐而言,期望逐渐释放其压力,没有严重地爆炸或者爆裂。这同样适用于由于所述车辆起火而导致的所述罐中容纳的气体的温度提高的事件中。
一个重要的优势会是,其可容易地插入到汽车主体中、尤其是电池(battery)组中,替代电池的全部或者一部分。
另一个目的是对于这样的罐,使得可以以合理的成本在工业上获得,所述合理的成本例如是对于机动车辆应用而言可接受的成本。
进一步地,对于氢罐所要求的压力限制意指从机械的观点来说在这样的罐中可以容纳任何其他在化学上非侵蚀性的流体。
从文件FR 2 923 575,已知有用于高压下流体的储存的罐,所述罐具有圆柱形一般形状和圆形截面,所述罐包含,在沿其轴线的其每一端处的金属盖,环绕所述盖的衬里以及环绕所述衬里的由用热固性树脂浸渍的纤维制成的结构层。
还从文件WO2017/199193,已知有由复合物材料制成的罐,其包含管状元件,分别插入到所述管状元件的端中的两个盖,以及环绕所述管状元件和所述盖的圆周层。所述圆周层由用树脂浸渍的缠绕的纤维形成。所述管状元件包含由纵向层环绕的塑料管,所述纵向层基本上由平行布置于树脂基体中的纤维组成,所述平行纤维在所述塑料管的纵向轴线的方向上取向。
这些“常规的”复合物气体储存罐,对于典型地大于10升的体积,一般地展现大于或等于150mm的在圆柱形部件中的内径。
相反地,“适形(conformable,顺应性)”或其他“多形态”气体储存罐一般地由相互连接的封闭管的组装件构成。这些多形态的罐是通过组装具有小直径的、典型地有小于150mm的内径的复合物管制造的。
然而,尚未良好地定义最佳技术方案以高效地制造该类型的储存罐,特别是用于在高压下的储存,用于氢的储存罐。
通过可以具有半球形穹顶的形状的盖封闭所述管要求纤维在所述管的轴线上理想地定位,以维持这些穹顶,但鉴于所述穹顶的半球形形状,所述纤维不能在所述管的轴线上严格地对齐,这对其有效性是不利的,并且使得有必要使用比可以设想的严格的最低限度更多量的纤维,如果其确实在所述管的轴线上对齐的话。
进一步地,当所述管的直径变得太小、典型地小于150mm时,则用展现如下曲率半径的穹顶封闭所述管就变得复杂:所述曲率半径足够大到在围绕所述罐缠绕所述纤维期间不产生问题。
此外,这些管的生产速率相对较慢,涉及生产衬里,然后围绕该衬里特定地缠绕一次或多次所述纤维,以及封闭所述管。
最后,最常见的复合物罐解决方案使用基于热固性树脂、特别是环氧类型的热固性树脂的复合物加强物。事实上,这些复合物一般地是微裂的,其使得用厚和重的衬里以确保所述罐的密封性必不可少。热固性复合物、特别是环氧化物的微裂对其机械强度是有害的,以及使得有必要增加碳纤维的含量和由此所述罐的成本。
在所述复合物加强物是通过湿丝缠绕制造的情形中,该缺点与另外的缺点相结合。这是因为该类型的工艺由于在加工期间不存在高压,导致高孔隙度。
最后,基于热固性树脂、特别是环氧树脂的复合物罐不能再循环。
因此,需要承受高压的罐,其生产相对容易和简单,并且其可再循环。
本发明针对用于容纳加压的流体的罐,其包含:
-至少一个圆柱形元件,其由拉挤的纤维材料制成,所述纤维材料用热塑性基体浸渍,
-放置在至少一个圆柱形元件的一端处将其封闭的第一盖,以及
-放置在至少一个圆柱形元件的另一端处的第二盖,其安装有孔口,所述孔口旨在使得所述流体的进入和离开成为可能,以及
-至少一个额外的纤维加强物,其部分地或完全地、优选完全地环绕所述圆柱形元件,以及任选地盖,
所述额外的纤维加强物中含有的纤维在与所述圆柱形元件的纵向轴线不同的轴线上定位,
相对于所述罐中含有的基体和纤维的体积,所述罐的纤维的总含量在40体积%和70体积%之间。
本发明还涉及用于制造如上定义的罐的工艺,其特征在于其包含以下相继的阶段:
(a)拉挤所述圆柱形元件,
(b)在(a)阶段结束时获得的圆柱形元件的端处放置所述盖,
(c)沉积所述额外的纤维增强物。
最后,本发明涉及如上定义的罐用于储存、运输和/或分配流体的用途,所述流体诸如气体,其呈压缩形式、呈液体形式、或者呈低温压缩形式,以及特别是氢、天然气、LPG、LNG、压缩空气、氮或氧的流体。
附图的简要说明
[图1]是阐明根据本发明的用于罐的圆柱形元件的制备工艺的图,所述圆柱形元件由拉挤的纤维材料制成,所述纤维材料用热塑性基体浸渍,所述圆柱形元件带有额外的纤维加强物。
[图2]是阐明根据本发明的用于制备用于罐的圆柱形元件的另一工艺的图,所述圆柱形元件由拉挤的纤维材料制成,所述纤维材料用热塑性基体浸渍,所述圆柱形元件带有额外的纤维加强物。
发明详述
本发明的其他特征、方面、主题和优点在阅读接下来的描述后将变得更加清楚明显。
规定在本说明书中使用的“从...到...”和“在...和...之间”应理解为包括每一个所提及的限值。
根据本发明的罐包含:
-至少一个圆柱形元件,其由拉挤的纤维材料制成,所述纤维材料用热塑性基体浸渍,
-放置在至少一个圆柱形元件的一端处将其封闭的第一盖,以及
-放置在至少一个圆柱形元件的另一端处的第二盖,其安装有孔口,所述孔口旨在使得所述流体的进入和离开成为可能,以及
-至少一个额外的纤维加强物,其部分地或完全地、优选完全地环绕所述圆柱形元件,以及任选地盖,
所述额外的纤维加强物中含有的纤维沿着与所述圆柱形元件的纵向轴线不同的轴线定位,
相对于所述罐中含有的基体和纤维的体积,所述罐的纤维的总含量在40体积%和70体积%之间。
所述圆柱形元件是根据拉挤工艺制造的。因此,其由用热塑性基体浸渍的纤维组成。拉挤是一般地连续的工艺,其通过在所述圆柱形元件的轴线上的模头对所述纤维施加牵引,所述纤维不必然在所述牵引的轴线上取向。拉挤涵盖浸渍干纤维,例如干纤维的编织物(braid)、干纤维的织物(fabric)或单向的粗纱。其还涵盖以共混的纤维的、预浸渍的纤维的、用树脂预浸渍的编织物的成型(profiled)元件的形式的加工。根据后一种情况,可以在拉挤阶段之前预浸渍所述纤维。
一般地,现有技术的管由称为“衬里”的管(其随后用纤维覆盖)组成。事实上,根据本发明的罐包含圆柱形元件,其已经包含纤维。根据本发明的罐的这方面是高度有利的。这是因为通过拉挤制造圆柱形元件是有生产成效的,即使对于厚的元件,因为所述圆柱形元件的整个体积是连续地并且在单个阶段中所生产的。此外,在所述圆柱形元件中掺入所述纤维使得可省去在所述管的轴线上沉积浸渍的纤维加强物。这是因为该沉积阶段相对较慢,并且不总容易控制。
根据本发明的一个实施方案,特别是根据目标流体的类型,根据本发明的罐可含有衬里。然而,该衬里并非必不可少。
纤维
关于所述纤维材料的组成纤维,特别地有无机、有机或植物来源的呈粗纱形式的纤维。
有利地,每个粗纱的纤维数为,对于碳纤维,大于或等于12K,大于24K,特别是大于或等于50K,尤其是24K-36K。
有利地,对于玻璃纤维的基重为,对于每个粗纱,大于或等于1200tex,特别是小于或等于4800tex,尤其是1200-2400tex。
在所述无机来源的纤维中,可提及例如碳纤维、玻璃纤维、玄武岩或玄武岩基纤维、二氧化硅纤维或碳化硅纤维。在所述有机来源的纤维中,可提及例如基于热塑性或热固性聚合物的纤维,例如半芳香族聚酰胺纤维、芳纶纤维或聚烯烃纤维。优选地,其基于无定形热塑性聚合物,并且展现的玻璃化转变温度Tg高于浸渍基体的组成热塑性聚合物或聚合物共混物的Tg(当所述聚合物或聚合物共混物为无定形的时),或者高于浸渍基体的组成热塑性聚合物或聚合物共混物的M.p.(当所述聚合物或聚合物共混物为半结晶的时)。有利地,其基于半结晶热塑性聚合物,并且展现的熔点M.p.高于浸渍基体的组成热塑性聚合物或聚合物共混物的Tg(当所述聚合物或聚合物共混物为无定形的时),或者高于浸渍基体的组成热塑性聚合物或聚合物共混物的M.p.(当所述聚合物或聚合物共混物为半结晶的时)。因此,在最终复合物的被热塑性基体浸渍期间,所述纤维材料的组成有机纤维没有熔化的风险。在所述植物来源的纤维中,可以提及基于亚麻、汉麻(hemp)、木质素、竹子、丝(特别是蜘蛛丝)、剑麻和其他纤维素纤维(特别是粘胶纤维)的天然纤维。这些植物来源的纤维可以纯的形式使用、经过处理或者涂有涂层,目的是有利于热塑性聚合物基体的粘附和浸渍。
其也可以对应于带有支撑纱线的纤维。
这些组成纤维可以单独或作为混合物使用。因此,有机纤维可以与无机纤维混合,以便用热塑性聚合物浸渍,以及形成浸渍的纤维材料。
有机纤维的粗纱可以具有多种基重。此外,其可呈现多种几何形状。
所述纤维以连续纤维的形式提供,其构成2D织物、非织造布(NCF)、单向纤维(UD)或非织造布的编织物或粗纱。所述纤维材料的组成纤维可另外地呈这些各种不同几何形状的加强纤维的混合物的形式。优选地,包括在圆柱形元件的拉挤的纤维材料中的纤维是干纤维的编织物。
优选地,所述纤维材料选自玻璃纤维、碳纤维、玄武岩和玄武岩基纤维。根据第一有利的实施方案,所述纤维材料选择自玻璃纤维。根据第二有利的实施方案,所述纤维材料选择自碳纤维。根据第三有利的实施方案,所述纤维材料选择自玄武岩基纤维。
有利地,所述纤维以一个粗纱或若干粗纱的形式使用。
热塑性基体
术语“热塑性”或“热塑性塑料”应理解为意指如下的材料:其在环境温度下一般为固体,其可以是半结晶或无定形的,并且其在温度升高期间,特别是当其为无定形的时在通过其玻璃化转变温度(Tg)后变软,并且在较高温度下流动,或者当其为半结晶的时其在通过其“熔化”点(M.p.)时可展现出明显的熔化,并且其在温度降低到其结晶点以下(对于半结晶聚合物)和其玻璃化转变温度以下(对于无定形聚合物)期间再次变为固体。
所述玻璃化转变温度,以下表示为Tg,以及所述熔化点,以下表示为M.p.,分别根据标准ISO 11357-2:2013和11357-3:2013通过差示扫描量热法(DSC)确定。
所述热塑性聚合物可以是无定形聚合物,其展现出高于或等于50℃、特别是高于或等于100℃、尤其是高于或等于120℃、特别是高于或等于140℃的玻璃化转变温度Tg,或者是半结晶热塑性聚合物,其熔化点M.p.高于150℃。
所述基体被描述为“热塑性”,其意指所述基体的主要组分是热塑性聚合物或者热塑性聚合物的共混物。
有利地,所述至少聚酰胺选自:聚(芳基醚酮)(PAEK),特别是聚(醚醚酮)(PEEK);聚(芳基醚酮酮)(PAEKK),特别是聚(醚酮酮)(PEKK);芳香族聚醚酰亚胺(PEI);聚芳基砜,特别是聚苯基砜(PPSU);聚芳基硫醚,特别是聚苯基硫醚(PPS);聚酰胺(PA),特别是半芳香族聚酰胺(聚邻苯二甲酰胺),其任选地通过脲单元改性;PEBA,其M.p.高于150℃;聚丙烯酸酯,特别是聚甲基丙烯酸甲酯(PMMA);聚烯烃,其排除聚丙烯;聚乳酸(PLA);聚乙烯醇(PVA);含氟聚合物,特别是聚偏氟乙烯(PVDF)或聚四氟乙烯(PTFE)或聚氯三氟乙烯(PCTFE);聚氯乙烯(PVC)和丙烯腈-丁二烯-苯乙烯(ABS)聚合物,及其共混物,特别是PEKK和PEI的共混物,优选地从90-10重量%到60-40重量%,特别地从90-10%重量到70-30重量%。
有利地,所述至少热塑性聚合物选自聚酰胺、脂肪族聚酰胺、脂环族聚酰胺和半芳香族聚酰胺(聚邻苯二甲酰胺)、PEKK、PEI以及PEKK和PEI的共混物。
用于定义聚酰胺的命名法描述在标准NF EN ISO 1874-1:2011,“Plastics-Polyamide(PA)Moulding and Extrusion Materials-Part 1:Designation”,特别是在第3页(表1和表2),并且为本领域技术人员所熟知。
所述聚酰胺可以是均聚酰胺或共聚酰胺或这些的共混物。
对于必须承受高温度的罐,根据本发明有利地使用聚(芳基醚酮)PAEK,如聚(醚酮)PEK,聚(醚醚酮)PEEK,聚(醚酮酮)PEKK,聚(醚酮醚酮酮)(PEKEKK)或具有高玻璃化转变温度Tg的PA。
有利地,所述聚酰胺选自脂肪族聚酰胺、脂环族聚酰胺和半芳香族聚酰胺(聚邻苯二甲酰胺)。
有利地,所述脂肪族聚酰胺选自聚酰胺6(PA6)、聚酰胺11(PA11)、聚酰胺12(PA12)、聚酰胺66(PA66)、聚酰胺46(PA46)、聚酰胺610(PA610)、聚酰胺612(PA612)、聚酰胺1010(PA1010)、聚酰胺1012(PA1012)、聚酰胺11/1010(PA11/1010)和聚酰胺12/1010(PA12/1010),或这些的共混物,或这些的共聚酰胺,以及嵌段共聚物、特别是聚酰胺/聚醚(PEBA)共聚物,并且所述半芳香族聚酰胺是任选地通过脲单元改性的半芳香族聚酰胺,特别是PAMXD6和PA MXD10,或者式X/YAr的半芳香族聚酰胺,如在EP 1 505 099中所述,特别是式A/XT的半芳香族聚酰胺,其中:
-A选自从氨基酸获得的单元、从内酰胺获得的单元和对应于式(Ca二胺).(Cb二酸)的单元,其中a代表所述二胺的碳原子数,以及b代表所述二酸的碳原子数,a和b各自在4和36之间、有利地在9和18之间,所述(Ca二胺)单元选自直链或支链脂肪族二胺、脂环族二胺和烷基芳香族二胺,以及所述(Cb二酸)单元选自直链或支链脂肪族二酸、脂环族二酸和芳香族二酸;
-XT表示从Cx二胺和对苯二甲酸(T)的缩聚获得的单元,其中x代表所述Cx二胺的碳原子数,x在6-36之间,有利地在9-18之间。有利地,半芳香族聚酰胺为式A/6T、A/9T、A/10T或A/11T的,A如上定义,特别是聚酰胺PA 6/6T,PA 66/6T,PA 6I/6T,PA MPMDT/6T,PA11/10T,PA 11/6T/10T,PA MXDT/10T,PA MPMDT/10T,PA BACT/10T,PA BACT/6T,PA BACT/10T/6T或者PA 11/BACT/10T;T对应于对苯二甲酸,MXD对应于间苯二甲胺,MPMD对应于甲基五亚甲基二胺,以及BAC对应于双(氨基甲基)环己烷。
有利地,所述热塑性聚合物是半结晶聚合物。
有利地,所述半晶聚合物展现诸如Tg≥80℃、特别是Tg≥100℃、尤其是≥120℃、特别是≥140℃的玻璃化转变温度以及≥150℃的M.p.。
在后一种情况中,所述至少半结晶聚酰胺选自:聚(芳基醚酮)(PAEK),特别是聚(醚醚酮)(PEEK);聚(芳基醚酮酮)(PAEKK),特别是聚(醚酮酮)(PEKK);芳香族聚醚酰亚胺(PEI);聚芳基砜,特别是聚苯基砜(PPSU);聚芳基硫醚,特别是聚苯基硫醚(PPS);聚酰胺(PA),特别是半芳香族聚酰胺(聚邻苯二甲酰胺),其任选地通过脲单元改性;聚丙烯酸酯,特别是聚甲基丙烯酸甲酯(PMMA);聚烯烃,其排除聚丙烯;聚乳酸(PLA);聚乙烯醇(PVA);聚氯乙烯(PVC)和丙烯腈-丁二烯-苯乙烯(ABS)聚合物,及其共混物,特别是PEKK和PEI的共混物,优选地从90-10重量%到60-40重量%,特别地从90-10%重量到70-30重量%。
更有利地,在后一种情况中,所述至少热塑性聚合物选自聚酰胺、脂肪族聚酰胺、脂环族聚酰胺和半芳香族聚酰胺(聚邻苯二甲酰胺)、PEKK、PEI以及PEKK和PEI的共混物。
浸渍的拉挤的纤维材料
在浸渍的材料(也被称为“即用型”材料)中,浸渍热塑性聚合物或热塑性聚合物的共混物围绕所述纤维均一地和均匀地分布。在这种类型的材料中,浸渍热塑性聚合物必须在所述纤维内尽可能均匀地分布,以便获得最少的孔隙,也就是说,所述纤维之间的最少的空隙。特别地,这种类型的材料中孔隙的存在可以起应力的集中点的作用(例如在机械拉伸应力下放置期间),并且其然后形成浸渍的纤维材料的破损(failure)的起始点并且在机械上削弱它。所述聚合物或聚合物的共混物的均匀分布因此提高了由这些浸渍的纤维材料形成的复合物材料的机械强度和均匀性。
有利地,相对于拉挤的浸渍的纤维材料的体积,在所述拉挤的浸渍的纤维材料中纤维的含量为45体积%-70体积%、优选地50体积%-70体积%、优选地50体积%-60体积%、特别地54体积%-60体积%。
纤维的含量的测量一般可以通过所述圆柱形元件的横截面的图像分析(特别是使用显微镜或相机或数码相机),经由将所述纤维的表面积除以所述圆柱形元件的表面积(浸渍的表面积加上孔隙的表面积)来进行。为了获得良好品质的图像,优选地在标准抛光树脂中涂覆沿其横向的方向切割的圆柱形元件,并用标准方案抛光,使得可用显微镜以至少6倍放大观察所述样品。待分析的图像尺寸在所述纤维的直径的10-12倍之间。拍取在不同的位置(截面)处的5-40张图像。取所有图像的平均值,并按体积重新计算。
对于在所述额外的纤维加强物的部件中纤维的含量的测量,如果这是基于用热塑性基体浸渍的连续纤维的纤维材料,则进行相同的测量,除了其是在垂直于所述额外的纤维加强物的纤维的方向的截面上。
如果所述纤维是碳纤维,碳纤维的含量的测量可根据ISO 14127:2008确定。
如果所述纤维是玻璃纤维,纤维的含量的测量根据ISO 1172:1999确定。
有利地,所述浸渍的纤维材料的孔隙度小于10%、特别是小于5%、尤其是小于2%。
应该注意的是,很难达到零的孔隙度,因而,有利地,所述孔隙度大于0%但小于上述程度。
所述孔隙度对应于闭口孔隙度,并且其可以通过电子显微镜来确定,或者作为如在EP3 418 323的实施例部分所述的所述浸渍的纤维材料的理论密度和实验密度之间的相对偏差来确定。
所述复合物材料是密封性的、惰性的和对加压的流体的内部压力有抗性的。
优选地,根据本发明的罐包含纤维材料,其包含,作为纤维的选自玻璃纤维、碳纤维、玄武岩纤维和玄武岩基纤维的纤维,以及作为热塑性基体的选自聚酰胺、脂肪族聚酰胺、脂环族聚酰胺、半芳香族聚酰胺(聚邻苯二甲酰胺)、PEKK、PEI以及PEKK和PEI的共混物的聚合物。
浸渍的纤维材料由此通过拉挤以圆柱体的形式制造。
根据一个实施方案,所述圆柱形元件的内径可以在50-150mm之间。该直径尺寸特别针对用于电池组的罐,例如用于汽车或拖车底盘。
根据另一实施方案,所述圆柱形元件的内径可以大于150mm。该直径尺寸特别针对氢运输拖车罐。
所述圆柱形元件的长度可以在25cm-10m之间,优选地在50cm-3m之间。本领域技术人员将知道如何根据所述罐的预期目的调整所述圆柱形元件的尺寸。
根据另一实施方案,所述罐的壁的厚度与其内径的比值可以在0.05-0.20之间、优选在0.08-0.12之间。
根据本发明的罐包含在其端处的两个盖。这些盖一般地由金属制成,优选地由铝合金制成。
第一盖放置在至少一个圆柱形元件的一端处封闭它。其由此构成所述罐的底部。
第二盖放置在至少一个圆柱形元件的另一端处,其安装有孔口,所述孔口旨在使得所述流体的进入和离开成为可能。其可以是阀门。
根据本发明的罐的一个实施方案,放置在至少一个圆柱形元件的一端处将其封闭的第一盖还可以安装有孔口,所述孔口旨在使得所述流体的进入和离开成为可能。
所述盖可以具有半球形穹顶形状或圆锥形形状。
可在所述盖和所述圆柱形元件之间放置弹性体密封物,以确保所述罐的密封性。
额外的纤维加强物
根据本发明的罐还包含至少一个额外的纤维加强物,其部分地或完全地,特别是完全地环绕所述圆柱形元件和任选地盖。
在本发明的意义内,术语“纤维加强物”理解为意指包含在最终部件上赋予更大机械强度的纤维的材料。
所述额外的纤维加强物选自干连续纤维、基于用热塑性基体浸渍的连续纤维的纤维材料、及其混合物。
当所述额外的纤维加强物是干纤维时,后者可以选自上述定义的那些。
当所述额外的纤维加强物是基于用热塑性基体浸渍的连续纤维的纤维材料时,其可以与构成所述圆柱形元件的纤维材料相同或不同。
当所述额外的纤维加强物是基于用热塑性基体浸渍的连续纤维的纤维材料时,所述罐的纤维的总含量,其相对于所述罐中所含有的基体和纤维的体积在40体积%-70体积%之间,将拉挤的热塑性-浸渍的纤维材料的基体和所述额外的纤维加强物的基体考虑在内。换句话说,相对于所述罐中含有的基体和纤维的体积,所述罐的纤维的总含量在40体积%和70体积%之间。
根据一个实施方案,所述额外的纤维加强物选自干纤维的编织物、用热塑性树脂浸渍的纤维带的编织物、及其混合物。
因此,根据第一实施方案,所述纤维材料中包括的纤维可以是干纤维的编织物,以及所述额外的纤维加强物也可以是干纤维的编织物。
根据第二实施方案,所述纤维材料中包括的纤维可以是连续纤维的粗纱,以及所述额外的纤维加强物也可以是干纤维的编织物。
根据第三实施方案,所述纤维材料中包括的纤维可以是纤维的编织物,以及所述额外的纤维加强物也可以是干连续纤维的粗纱。
根据第四实施方案,所述纤维材料中包括的纤维可以是纤维的编织物,以及所述额外的纤维加强物也可以是被浸渍的连续纤维的粗纱。
根据第五实施方案,所述纤维材料中包括的纤维可以是连续纤维的粗纱,以及所述额外的纤维加强物也可以是被浸渍的连续纤维的粗纱。
所述额外的纤维加强物的热塑性基体可以与所述圆柱形元件的热塑性基体相同或不同。优选地,所述圆柱形元件的热塑性基体是与所述额外的纤维加强物的热塑性基体完全地或部分地可混的。这种完全的或部分的可混性使得可增加所述圆柱形元件的壁和所述额外的纤维加强物的层之间的粘附。
根据本发明的特定实施方案,所述罐可包含圆柱形元件,其热塑性基体由PVC制成,以及纤维加强物,其聚合物基体由丙烯酸类(acrylic,亚克力)制成。
根据本发明的另一特定实施方案,所述罐可包含圆柱形元件,其热塑性基体由ABS制成,以及纤维加强物,其聚合物基体由丙烯酸类制成。
根据本发明的还另一特定实施方案,所述罐可包含圆柱形元件,其热塑性基体由聚酰胺制成,以及纤维加强物,其聚合物基体由聚邻苯二甲酰胺制成。
优选地,所述额外的纤维加强物的热塑性基体展现高于150℃的熔化点。
优选地,所述额外的纤维加强物的热塑性基体展现高于80℃、优选地高于100℃并且更特别地高于120℃的玻璃化转变温度。
更特别地,所述额外的纤维加强物的热塑性基体展现高于150℃的熔化点和高于80℃、优选地高于100℃并且更特别地高于120℃的玻璃化转变温度。
所述纤维加强物的层的厚度可以在0.5mm和10mm之间、优选地在0.5mm和5mm之间。
相对于所述基体和所述纤维的体积的总和,纤维的总含量在40体积%和70体积%之间、优选地在50体积%和70体积%之间。
在本发明的含义内,术语“纤维的总含量”理解为意指在所述罐中(也就是说在所述圆柱形元件中和在所述额外的纤维加强物中)含有的纤维的含量的总和。
所述额外的纤维加强物包含沿与所述圆柱形元件的纵向轴线不同的轴线定位的纤维,优选地相对于所述圆柱形元件的纵向轴线成+/-10°和+/-89°之间的角度,优选地,与所述圆柱形元件的轴线成+/-25°和+/-89°之间的角度,更优选地在+/-45°和+/-89°之间。
换句话说,所述圆柱形元件的纵向轴线构成0°轴线,以及所述额外的加强物的纤维方向构成第二轴线。这两条轴线之间的角度如上所定义。+/-符号指示所述额外的纤维加强物的纤维向右还是向左定位,其取决于所述圆柱形元件的轴线。
已经观察到,在不同的轴线上沉积纤维加强物使得可提高对所述罐的壁的内部压力的抗性。
优选地,所述圆柱形元件的材料中包括的纤维的一部分在所述圆柱形元件的纵向轴线上定位。更特别地,所述圆柱形元件的材料中包括的所有的纤维都沿着所述圆柱形元件的轴线定位。
根据一个实施方案,所述罐可包含由热塑性树脂的一个或多个层构成的第二圆柱形元件,其不包含纤维,也被称为衬里。该第二圆柱形元件可以使得可提高所述罐的密封性。其还可以使得可提高所述罐的对压力的抗性,实际上甚至可强化最终部件的化学抗性。
换句话说,根据本发明的罐可以包含衬里,然后,上面的如上定义的圆柱形元件,然后如上定义的额外的纤维加强物。
所述罐的长度和直径可以更大或更小。这些尺寸根据所要储存的流体和将要接收所述罐的结构体而变化。
优选地,根据本发明的罐包含:
-一个或多个圆柱形元件,其纤维在所述圆柱形元件的轴线上定位,以及
-一个或多个额外的纤维加强物,其纤维在不同于所述圆柱形元件的轴线的轴线上定位,以及
通过压接(crimping)将所述盖固定至所述圆柱形元件的端。根据该实施方案,所述盖不是半球形形状的。
在本发明的含义内,术语“压接”理解为意指将所述额外的纤维加强物压碎(crushed)或压平(flattened)在盖上。
优选地,所述额外的纤维加强物是部分地或完全地,优选完全地环绕所述圆柱形元件的层,其事先已经被压平在所述盖上,所述层由用热塑性树脂浸渍的纤维材料制成。
根据特别地优选的实施方案,根据本发明的罐包含:
-一个或多个圆柱形元件,其纤维在所述圆柱形元件的轴线上定位,以及
-额外的纤维加强物,其纤维在相对于所述圆柱形元件的轴线+/-45°和+/-89°之间定位。
根据另一实施方案,根据本发明的罐包含:
-一个或多个圆柱形元件,在所述纤维材料中所包括的其纤维为编织物,
-一个或多个额外的纤维加强物,其纤维为干的或浸渍的纤维的编织物,所述干的或浸渍的纤维的编织物沿着不同于所述圆柱形元件的编织物的轴线的轴线定位。
根据一个实施方案,根据本发明的罐可包含若干连接在一起的圆柱形元件,并且展示小于250mm、优选地小于150mm的内径。根据该实施方案,所述罐包含:
-第一盖,其放置在至少一个圆柱形元件的一端处封闭它,然后
-圆柱形元件,其由拉挤的纤维材料制成,所述纤维材料用热塑性基体浸渍,然后
-连接工件,其使得所述流体的进入和离开以及与相邻的圆柱形元件的连接成为可能,然后
-圆柱形元件,其由拉挤的纤维材料制成,所述纤维材料用热塑性基体浸渍;
该顺序:圆柱形元件-连接工件,可根据需要重复若干次;然后
最终盖,其放置在至少一个圆柱形元件的另一端处,其安装有孔口,所述孔口旨在使得流体从整个的所述罐的进入和离开成为可能。
本发明还涉及用于制造根据本发明的罐的工艺。所述工艺包含以下相继的阶段:
(a)拉挤所述圆柱形元件,
(b)在(a)阶段结束时获得的圆柱形元件的端处放置所述盖,
(c)沉积所述额外的纤维增强物。
根据一个实施方案,所述额外的纤维加强物的沉积的阶段可以通过将额外的纤维加强物的带围绕所述圆柱形元件及其盖缠绕来进行。该沉积可以在一定的机械应力下进行,以便在所述盖和所述圆柱形元件上施加压力。
根据另一实施方案,所述盖展现小于所述圆柱形元件的内径的外径。所述盖由此可以插入到所述圆柱形元件中。在此情形中,所述纤维加强物仅缠绕所述圆柱形元件。这是因为后者已经环绕了所述盖。
最后,本发明涉及根据本发明的罐用于储存、运输和/或分配流体的用途,所述流体诸如气体,其呈压缩形式、呈液体形式、或者呈低温压缩形式,以及特别是氢、天然气、LPG、LNG、压缩空气、氮或氧的流体。
附图说明
通过图1可以示出根据本发明的工艺。
图1示出了拉挤工艺。元件1是挤出的管(如圆柱形元件),其将使得可以对最终拉挤的元件给出形状。干纤维3离开由纱架2支撑的卷轴并且送入到浸渍区4中。该区4包含液体树脂的浴,或者用于注射所述树脂的头。拉挤模头5引导拉挤的浸渍的纤维,得到所拉挤的层6。拉挤的浸渍的纤维经历由加热元件7生成的加热。卷轴8支撑所述额外的纤维加强物,其将根据角度9围绕拉挤的管缠绕。整个拉挤的管由拉具(pullers,拉动器)10拉动。拉挤的管随后由切割装置11切割。
图2示出了另一拉挤工艺。元件21是挤出的管,其将使得可以对最终拉挤的元件给出形状。用纤维23浸渍的纤维离开由纱架22支撑的卷轴并且送入到拉挤模头24中。后者引导浸渍的纤维并且使其相符(conforms,顺应),得到拉挤的层25。拉挤的浸渍的纤维经历由加热元件26生成的加热。卷轴27支撑所述额外的纤维加强物,其将根据角度28围绕所拉挤的管缠绕。整个拉挤的管由拉具29拉动。拉挤的管随后由切割装置30切割。
实施例
实施例1
通过拉挤,在0.5m/min的速率下,借助于熔体浸渍工艺,使用连接到单螺杆挤出机的管状模头,制造展现170mm的外径和2mm的厚度的圆形截面的复合物管。用于所述拉挤的树脂是低粘度的聚酰胺11的等级(参考号FMNO),其使得可获得所述纤维的良好的浸渍。该聚酰胺11树脂展现190℃的M.p.(根据标准ISO 11357-3:2013测量),以及在所述拉挤模头中的温度为250℃。所使用的纤维是由SGL销售的50K碳纤维,其参考号Sigrafil C-T50 4.8/280T140。所述纤维含量为45体积%(相对于拉挤的管的体积的纤维含量)。在所述拉挤模头中的纤维的取向仅仅地沿着所述管的轴线。
所述管被切割成1.5m的长度。在所述管的两端的每一个处放置长度为20mm的两个盖。在所述盖和所述管之间的界面处放置品牌的密封性密封物。这些盖由具有80mm的直径的铝圆柱体组成,其钻有M25螺纹孔,使得可以与在氢中使用的标准连接器相联接。
由Hyosung H2550 G10碳纤维组成的、未用树脂浸渍的额外的加强物(即,干纤维加强物)围绕拉挤的管螺旋地缠绕4mm的厚度,以便承受由管中的内部压力强加在所述盖上的力。随后,由干纤维组成的纤维加强物以与所述管的轴线成85°缠绕4mm的厚度。在这些端的一个处用M25螺纹塞将所述管封闭,然后在环境温度下加压直至爆裂。所测得的爆裂压力为1600bar。
实施例2
通过拉挤,在0.5m/min的速率下,借助于熔体浸渍工艺,使用连接到单螺杆挤出机的管状模头,制造展现170mm的外径和2mm的厚度的圆形截面的复合物管。用于所述拉挤的树脂是低粘度的聚酰胺11的等级(参考号FMNO),其使得可获得所述纤维的良好的浸渍。该聚酰胺11树脂展现190℃的M.p.(根据标准ISO 11357-3:2013测量),以及在所述拉挤模头中的温度为250℃。所使用的纤维是由SGL销售的50K碳纤维,其参考号Sigrafil C-T50 4.8/280T140。所述纤维含量为45体积%(相对于拉挤的管的体积的纤维含量)。在所述拉挤模头中的纤维的取向仅仅地沿着所述管的轴线。
所述管被切割成1.5m的长度。在所述管的两端的每一个处放置长度为20mm的两个盖。在所述盖和所述管之间的界面处放置品牌的密封性密封物。这些盖由具有80mm的直径的铝圆柱体组成,其钻有M25螺纹孔,使得可以与在氢中使用的标准连接器相联接。
由具有1/2”的宽度的复合物带组成的额外的纤维加强物围绕拉挤的管螺旋地缠绕4mm的厚度,以便承受由管中的内部压力强加在所述盖上的力。随后,所述复合物带垂直于所述管的轴线缠绕4mm的厚度(鉴于所述带的宽度和拉挤的管的直径,所述纤维的角度为约85°)。所述复合物带由Hyosung H2525 G10碳纤维构成,所述碳纤维浸渍有展现50℃的玻璃化转变温度(根据标准ISO 11357-2:2013通过DSC测量)的聚酰胺11类型的树脂(参考号FMNO)。所述纤维含量为55体积%(相对于所述复合物带的体积)。借助于Solo品牌的带有激光加热的自动沉积工艺,在270℃的温度下和在0.3m/s的速率下,采用所述复合物带。
在这些端的一个处用M25螺纹塞将所述管封闭,然后在环境温度下加压直至爆裂。所测得的爆裂压力为1670bar。
实施例3
通过拉挤,在0.5m/min的速率下,借助于熔体浸渍工艺,使用连接到单螺杆挤出机的管状模头,制造展现170mm的外径和2mm的厚度的圆形截面的复合物管。用于所述拉挤的树脂是低粘度的聚酰胺11的等级(参考号FMNO),其使得可获得所述纤维的良好的浸渍。该聚酰胺11树脂展现190℃的M.p.(根据标准ISO 11357-3:2013测量),以及在所述拉挤模头中的温度为250℃。所使用的纤维是由SGL销售的50K碳纤维,其参考号C-T50 4.8/280T140。所述纤维含量为45体积%(相对于拉挤的管的体积的纤维含量)。在所述拉挤模头中的纤维的取向仅仅地沿着所述管的轴线。
拉挤的管切割成具有1.5m的长度的段。每个段沿着所述管的轴线在其端处切割成具有40mm的长度的条,以及这些端加热到150℃并且成型至覆盖两个盖,所述盖具有20mm的长度,放置在所述管的两端的每一个处。这些盖由具有80mm的直径的铝圆柱体组成,其钻有M25螺纹孔,使得可以与在氢中使用的标准连接器相联接。
额外的纤维加强物,其由具有1/2”的宽度的复合物带组成,围绕所述管垂直于其轴(鉴于所述带的宽度和拉挤的管的直径,所述纤维的角度为约85°)并且以6mm的厚度缠绕。该带也围绕所述管的端缠绕(通过用于所述纤维的相同的缠绕角度),其在所述金属盖上成型,以便进行所述盖的压接。所述复合物带由Hyosung H2525 G10碳纤维构成,所述碳纤维浸渍有展现140℃的玻璃化转变温度(根据标准ISO 11357-2:2013通过DSC测量)的PA11/BACT/10T类型的树脂。所述纤维含量为55体积%(相对于所述复合物带的体积)。借助于Solo品牌的带有激光加热的自动沉积工艺,在330℃的温度下和在0.3m/s的速率下,采用所述复合物带。
制造相同类型的两个管,并且借助于具有30mm的直径、配备有M25螺纹盖的连接器将其连接到一起,以及所述管中的一个在其端的一个处通过M25螺纹塞封闭。由此所形成的罐展现60l的体积,并在23℃的温度下进行压力测试:所测得的爆裂压力为1750bar。

Claims (24)

1.用于容纳加压的流体的罐,其包含:
-至少一个圆柱形元件,其由拉挤的纤维材料制成,所述纤维材料用热塑性基体浸渍,
-放置在至少一个圆柱形元件的一端处将其封闭的第一盖,以及
-放置在至少一个圆柱形元件的另一端处的第二盖,其安装有孔口,所述孔口旨在使得所述流体的进入和离开成为可能,以及
-至少一个额外的纤维加强物,其部分地或完全地环绕所述圆柱形元件以及任选地盖,
所述额外的纤维加强物中含有的纤维沿着与所述圆柱形元件的纵向轴线不同的轴线定位,
相对于所述罐中含有的基体和纤维的体积,所述罐的纤维的总含量在40体积%和70体积%之间。
2.如权利要求1所述的罐,其特征在于所述额外的纤维加强物选自干连续纤维、基于用热塑性基体浸渍的连续纤维的纤维材料、及其混合物。
3.如权利要求1或2所述的罐,其特征在于所述额外的纤维加强物包含纤维,所述纤维相对于所述圆柱形元件的轴线成在+/-10°和+/-89°之间的角度定位。
4.如权利要求1-3任一项所述的罐,其特征在于所述圆柱形元件的材料中包括的纤维的一部分在所述圆柱形元件的纵向轴线上定位。
5.如权利要求1、3和4任一项所述的罐,其特征在于所述额外的纤维加强物选自干连续纤维的编织物、用热塑性树脂浸渍的纤维带的编织物、及其混合物。
6.如权利要求1-5任一项所述的罐,其特征在于用于制造所述圆柱形元件的拉挤的纤维材料的纤维是干纤维的编织物。
7.如权利要求2-6任一项所述的罐,其特征在于所述额外的纤维加强物是部分地或完全地环绕所述圆柱形元件的层,其事先已经被压平在所述盖上,所述层由用热塑性树脂浸渍的纤维材料制成。
8.如权利要求2-7任一项所述的罐,其特征在于所述圆柱形元件的热塑性基体是与所述额外的纤维加强物的热塑性基体完全地或部分地可混的。
9.如权利要求2-8任一项所述的罐,其特征在于所述额外的纤维加强物的热塑性基体展现高于150℃的熔化点和/或高于80℃的玻璃化转变温度。
10.如前述权利要求任一项所述的罐,其特征在于所述圆柱形元件的热塑性基体主要含有热塑性聚合物或热塑性聚合物的共混物。
11.如权利要求10所述的罐,其特征在于所述热塑性聚合物选自聚(芳基醚酮)(PAEK),特别是聚(醚醚酮)(PEEK);聚(芳基醚酮酮)(PAEKK),特别是聚(醚酮酮)(PEKK);芳香族聚醚酰亚胺(PEI);聚芳基砜,特别是聚苯基砜(PPSU);聚芳基硫醚,特别是聚苯基硫醚(PPS);聚酰胺(PA),特别是半芳香族聚酰胺(聚邻苯二甲酰胺),其任选地通过脲单元改性;PEBA,其M.p.高于150℃;聚丙烯酸酯,特别是聚甲基丙烯酸甲酯(PMMA);聚烯烃,其排除聚丙烯;聚乳酸(PLA);聚乙烯醇(PVA);含氟聚合物,特别是聚偏氟乙烯(PVDF)或聚四氟乙烯(PTFE)或聚氯三氟乙烯(PCTFE);聚氯乙烯(PVC)和丙烯腈-丁二烯-苯乙烯(ABS)聚合物,及其共混物。
12.如权利要求10所述的罐,其特征在于所述热塑性聚合物选自聚酰胺、脂肪族聚酰胺、脂环族聚酰胺和半芳香族聚酰胺(聚邻苯二甲酰胺)、PEKK、PEI以及PEKK和PEI的共混物。
13.如权利要求10所述的罐,其特征在于所述热塑性聚合物选自脂肪族聚酰胺、脂环族聚酰胺和半芳香族聚酰胺(聚邻苯二甲酰胺)。
14.如权利要求10所述的罐,其特征在于所述热塑性聚合物选自聚酰胺6(PA6)、聚酰胺11(PA11)、聚酰胺12(PA12)、聚酰胺66(PA66)、聚酰胺46(PA46)、聚酰胺610(PA610)、聚酰胺612(PA612)、聚酰胺1010(PA1010)、聚酰胺1012(PA1012)、聚酰胺11/1010(PA11/1010)和聚酰胺12/1010(PA12/1010),或这些的共混物或这些的共聚酰胺。
15.如权利要求10所述的罐,其特征在于所述热塑性聚合物选自式A/XT的半芳香族聚酰胺,其中:
-A选自从氨基酸获得的单元、从内酰胺获得的单元和对应于式(Ca二胺).(Cb二酸)的单元,其中a代表所述二胺的碳原子数,以及b代表所述二酸的碳原子数,a和b各自在4和36之间、有利地在9和18之间,所述(Ca二胺)单元选自直链或支链脂肪族二胺、脂环族二胺和烷基芳香族二胺,以及所述(Cb二酸)单元选自直链或支链脂肪族二酸、脂环族二酸和芳香族二酸;
-XT表示从Cx二胺和对苯二甲酸的缩聚获得的单元,其中x代表所述Cx二胺的碳原子数,x在6-36之间,有利地在9-18之间。
16.如权利要求10所述的罐,其特征在于所述热塑性聚合物选自式A/6T、A/9T、A/10T或A/11T的半芳香族聚酰胺,A为如上所定义,特别是聚酰胺PA 6/6T,PA 66/6T,PA 6I/6T,PAMPMDT/6T,PA 11/10T,PA 11/6T/10T,PA MXDT/10T,PA MPMDT/10T,PA BACT/10T,PA BACT/6T,PA BACT/10T/6T或者PA 11/BACT/10T;T对应于对苯二甲酸,MXD对应于间苯二甲胺,MPMD对应于甲基五亚甲基二胺,以及BAC对应于双(氨基甲基)环己烷。
17.如前述权利要求任一项所述的罐,其特征在于所述纤维材料选自玻璃纤维、碳纤维、玄武岩纤维和玄武岩基纤维。
18.如前述权利要求任一项所述的罐,其特征在于其包含若干相互连接的圆柱形元件并且展示小于250mm、优选地小于150mm的内径。
19.如前述权利要求任一项所述的罐,其特征在于其包含,在所述圆柱形元件内部,由热塑性树脂的一个或多个层构成的第二圆柱形元件,其不包含纤维。
20.如前述权利要求任一项所述的罐,其特征在于所述罐含有衬里。
21.用于制造如前述权利要求任一项所定义的罐的工艺,其特征在于其包含以下相继的阶段:
(a)拉挤所述圆柱形元件,
(b)在(a)阶段结束时获得的圆柱形元件的端处放置所述盖,
(c)沉积所述额外的纤维增强物。
22.如权利要求21所述的工艺,其特征在于所述额外的纤维加强物的沉积的阶段通过将额外的纤维加强物的带围绕所述圆柱形元件及其盖缠绕来进行。
23.如权利要求22所述的工艺,其特征在于所述沉积在一定的机械应力下进行,以便在所述盖和所述圆柱形元件上施加压力。
24.如权利要求1-xx任一项所定义的罐用于储存、运输和/或分配流体的用途,所述流体诸如气体,其呈压缩形式、呈液体形式、或者呈低温压缩形式,以及特别是氢、天然气、LPG、LNG、压缩空气、氮或氧的流体。
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