CN102085724A - Wet fully-winding and curing process for preparing hydrogen cylinder with carbon fiber lining - Google Patents

Wet fully-winding and curing process for preparing hydrogen cylinder with carbon fiber lining Download PDF

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Publication number
CN102085724A
CN102085724A CN2009101998156A CN200910199815A CN102085724A CN 102085724 A CN102085724 A CN 102085724A CN 2009101998156 A CN2009101998156 A CN 2009101998156A CN 200910199815 A CN200910199815 A CN 200910199815A CN 102085724 A CN102085724 A CN 102085724A
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China
Prior art keywords
carbon fiber
curing
wet method
hydrogen storage
curing process
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CN2009101998156A
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Chinese (zh)
Inventor
童喆益
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SHANGHAI COMPOSITE HIGH-TECH DEVELOPMENT Co Ltd
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SHANGHAI COMPOSITE HIGH-TECH DEVELOPMENT Co Ltd
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Priority to CN2009101998156A priority Critical patent/CN102085724A/en
Publication of CN102085724A publication Critical patent/CN102085724A/en
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Abstract

The invention relates to a wet fully-winding and curing process for preparing a hydrogen cylinder with a carbon fiber lining, which comprises the following steps of: (1) weighing 100 weight parts of epoxy resin, 30 to 60 parts of curing agent and 10 to 20 parts of additive and adding the epoxy resin, the additive and the curing agent into an glue mixing tank in turn; (2) stirring with a stirrer for 8 to 10 minutes continuously, directionally and uniformly to obtain mixed glue; (3) slowly pouring the mixed glue into an impregnation tank; (4) allowing fibers to pass through the impregnation tank under the action of a tensioner to combine the fibers and the glue together, and performing wet winding which is to spirally and circularly wind the mixture on the surface of the aluminum lining so as to completely cover the surface of the aluminum lining; and (5) placing the winded hydrogen cylinder into a curing furnace for curing, and obtaining the product. Compared with the prior art, the process has the advantages that: the cured products have no air bubbles, are susceptible to infiltration, do not turn yellow and the like.

Description

A kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder
Technical field
The present invention relates to a kind of hydrogen storage cylinder, especially relate to a kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder.
Background technology
Present high-pressure hydrogen storage mainly contains the metal hydrogen storage vessel, the metal inner lining fiber twines three types in hydrogen storage vessel, full composite hydrogen occluding container.
Metal hydrogen storage vessel: by hydrogen there being the metal of certain resistance to corrosion constitute.Because metal strength is limited,, can only increase container thickness for improving container work pressure.But this can increase the manufacture difficulty of container, and causes manufacturing deficiency easily.Simultaneously, metal material density is bigger, and container mass is big, and the unit mass hydrogen-storage density is lower.
Filament wound structure: in order to improve the bearing capacity of container, and alleviate quality, the metal inner lining filament wound structure occurred.Metal inner lining is not born the pressure loading effect in this structure, only plays the sealing function of splendid attire hydrogen.Inner lining material is stainless steel or aluminium alloy normally.Pressure loading is born by carbon fiber, glass fibre or carbon fiber-glass fiber composite fibre that skin twines.Because fibre strength is much higher than common metal, and proportion is little, can alleviate the quality of container.Be subjected to the restriction of fiber winding process, this technology has also experienced from single hoop twines, and hoop+vertically twine is to the evolution of the compound winding of multi-angle.Along with the raising of fiber quality and updating of winding process, when improving the container bearing capacity, alleviated the quality of container.
Full composite fibre winding arrangement: except that attenuate fiber reinforcement layer thickness,, also can go on foot and alleviate container mass, improve the unit mass hydrogen-storage density by alleviating the liner quality.By Optimal Structure Designing, improve processing technology, now developed the full composite fibre winding arrangement of engineering thermoplastic materials inner lining structure.But the shortcoming of this structure is: anti-external impact ability is low; Along with temperature and pressure raises, the infiltration capacity of gases such as hydrogen increases; Connect mouth junction weak link often with metal, easily leak.
Existing wet method is twined and curing process manufacturing fibrous composite hydrogen storage cylinder is easy to generate problems such as bubble, xanthochromia, layering, and hydrogen storage cylinder will carry very high pressure, and product ftractures after pressurization easily.
Summary of the invention
Purpose of the present invention is exactly full the winding and curing process of wet method that provides a kind of in order to overcome the defective that above-mentioned prior art exists and solidify the back product and do not have bubble, is easy to soak into, can not take place the preparation carbon fiber aluminum liner hydrogen storage cylinder of xanthochromia.
Purpose of the present invention can be achieved through the following technical solutions: a kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder is characterized in that this technology may further comprise the steps:
(1) takes by weighing epoxy resin 100 weight portions, curing agent 30-60 weight portion, additive 10-20 weight portion, join in the packing element by the order input of epoxy resin, additive, curing agent;
(2) carrying out continuously-directional with agitator at the uniform velocity stirs and obtained colloid mixture in 8-10 minute;
(3) slowly drop into mixed colloid in the steeping vat;
(4) under the tensioner effect, fiber by steeping vat, is combined the back with fiber and twines and complete metallized aluminum inner bag surface with the form of spiral and hoop with colloid, carry out wet method and twine;
(5) gas cylinder that winding is finished is put into curing oven and is cured and promptly gets product.
Described epoxy resin comprises commercially available bisphenol A type epoxy resin E-51, novolac epoxy resin F-51 or brominated epoxy resin.
Described curing agent comprises aliphatic cyclic amine curing agent IPDA, MDA or ethylenediamine.
Described additive comprises defoamer, flexibilizer and promoter, and the consumption of described defoamer is the 1-3 weight portion, and the consumption of described flexibilizer is the 8-14 weight portion, and the consumption of described promoter is the 1-3 weight portion.
Described defoamer comprises polysiloxanes, polyoxyethylene or tributyl phosphate, described flexibilizer comprises acrylonitrile-butadiene rubber, haloflex or acrylonitrile-butadiene-styrene copolymer (ABS), and described promoter comprises benzyl dimethylamine or N tert butyl benzothiazole 2 sulfenamide.
The mixing speed of described agitator is 200-500 rev/min.
Fiber described in the step (4) is a carbon fiber, and the volume content of this carbon fiber is 60-80%.
Being cured step in the curing oven described in the step (5) comprises:
(1) temperature with curing oven was warmed up to 80 ℃-90 ℃ from room temperature in 20-30 minute;
(2) 80 ℃-90 ℃ insulations 40-80 minute;
(3) in 20-30 minute, the furnace temperature of curing oven is raised to 130 ℃-140 ℃ from 80 ℃-90 ℃;
(4) 130 ℃-140 ℃ insulations 170-200 minute;
(5) be cooled to room temperature naturally.
Compared with prior art, the present invention has the following advantages:
(1) product after the curing does not have bubble;
(2) the formula system manufacturability is strong, is easy to soak into, can be in the abundant combination of fiber;
Xanthochromia can not take place in (3) product water white transparency;
(4) the formula system cohesive force is big, and it is little to solidify post-shrinkage ratio, the hardness height, and good toughness, the percentage elongation height can not ftracture under the product high pressure.
The specific embodiment
The present invention is described in detail below in conjunction with specific embodiment.
Embodiment 1
The wet method that is used for carbon fiber aluminum liner hydrogen storage cylinder is complete twines and the curing process method, and this method comprises following processing step:
(1) be the commercially available bisphenol A type epoxy resin E-51 of 100kg by the prescription requirement, polysiloxanes 2kg, acrylonitrile-butadiene rubber 10kg, benzyl dimethylamine 2kg, aliphatic cyclic amine curing agent IPDA55kg, according to bisphenol A type epoxy resin E-51, polysiloxanes, acrylonitrile-butadiene rubber, benzyl dimethylamine, the whole solvent inputs of the order of aliphatic cyclic amine curing agent IPDA are joined in the packing element;
(2) carry out the fair speed of continuously-directional with agitator and stirred 8~10 minutes, the mixing speed of described agitator is 300 rev/mins;
(3) to be mixedly slowly drop into colloid in the steeping vat after evenly;
(4) under the tensioner effect, fiber by steeping vat, is closed form winding and the complete metallized aluminum inner bag surface of back (carbon fiber volume content is 70%) with spiral and hoop with fiber and gluing, carry out wet method and twine;
(5) gas cylinder that winding is finished is put into curing oven and is cured, and may further comprise the steps:
1. 25 fens clock times are raised to 90 ℃ with furnace temperature from room temperature
2. 90 ℃ are incubated 60 minutes;
3. 25 fens clock times are raised to 135 ℃ with furnace temperature from 90 ℃;
4. 135 ℃ are incubated 180 minutes;
5. be cooled to room temperature naturally.
(6) from stove, take out, measure weight, packing.
Embodiment 2
A kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder, this technology may further comprise the steps:
(1) claim that 100kg gets novolac epoxy resin F-51, polyoxyethylene 1kg, haloflex 8kg, benzyl dimethylamine 1kg, MDA 30kg, order input is joined in the packing element successively;
(2) carry out continuously-directional with agitator and at the uniform velocity stir and obtained colloid mixture in 8-10 minute, the mixing speed of described agitator is 200 rev/mins;
(3) slowly drop into mixed colloid in the steeping vat;
(4) under the tensioner effect, fiber is passed through steeping vat, fiber is combined the back to be twined and complete metallized aluminum inner bag surface with the form of spiral and hoop with colloid, carrying out wet method twines, described fiber is a carbon fiber, cumulative volume in fiber and colloid is 100%, and the volume content of this carbon fiber is 60%;
(5) gas cylinder that winding is finished is put into curing oven and is cured, and curing schedule is as follows:
(a) temperature with curing oven was warmed up to 80 ℃ from room temperature in 20 minutes;
(b) 80 ℃ of insulations 40 minutes;
(c) in 20 minutes, the furnace temperature of curing oven is raised to 130 ℃ from 80 ℃;
(d) 130 ℃ of insulations 170 minutes;
(e) be cooled to room temperature naturally.
(6) from curing oven, take out, measure weight, packing.
Embodiment 3
A kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder, this technology may further comprise the steps:
(1) claim 100kg brominated epoxy resin, tributyl phosphate 3kg, acrylonitrile-butadiene-styrene copolymer (ABS) 14kg, N tert butyl benzothiazole 2 sulfenamide 3kg, ethylenediamine 30kg, order input is joined in the packing element successively;
(2) carry out continuously-directional with agitator and at the uniform velocity stir and obtained colloid mixture in 8-10 minute, the mixing speed of described agitator is 500 rev/mins;
(3) slowly drop into mixed colloid in the steeping vat;
(4) under the tensioner effect, fiber is passed through steeping vat, fiber is combined the back to be twined and complete metallized aluminum inner bag surface with the form of spiral and hoop with colloid, carrying out wet method twines, described fiber is a carbon fiber, cumulative volume in fiber and colloid is 100%, and the volume content of this carbon fiber is 80%;
(5) gas cylinder that winding is finished is put into curing oven and is cured, and curing schedule is as follows:
(a) temperature with curing oven was warmed up to 90 ℃ from room temperature in 30 minutes;
(b) 90 ℃ of insulations 80 minutes;
(c) in 30 minutes, the furnace temperature of curing oven is raised to 140 ℃ from 90 ℃;
(d) 140 ℃ of insulations 200 minutes;
(e) be cooled to room temperature naturally.
(6) from curing oven, take out, measure weight, packing.

Claims (8)

1. a wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder is twined and curing process entirely, it is characterized in that this technology may further comprise the steps:
(1) takes by weighing epoxy resin 100 weight portions, curing agent 30-60 weight portion, additive 10-20 weight portion, join in the packing element by the order input of epoxy resin, additive, curing agent;
(2) carrying out continuously-directional with agitator at the uniform velocity stirs and obtained colloid mixture in 8-10 minute;
(3) slowly drop into mixed colloid in the steeping vat;
(4) under the tensioner effect, fiber by steeping vat, is combined the back with fiber and twines and complete metallized aluminum inner bag surface with the form of spiral and hoop with colloid, carry out wet method and twine;
(5) gas cylinder that winding is finished is put into curing oven and is cured and promptly gets product.
2. a kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder according to claim 1 is characterized in that described epoxy resin comprises commercially available bisphenol A type epoxy resin E-51, novolac epoxy resin F-51 or brominated epoxy resin.
3. a kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder according to claim 1 is characterized in that described curing agent comprises aliphatic cyclic amine curing agent IPDA, MDA or ethylenediamine.
4. a kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder according to claim 1, it is characterized in that, described additive comprises defoamer, flexibilizer and promoter, the consumption of described defoamer is the 1-3 weight portion, the consumption of described flexibilizer is the 8-14 weight portion, and the consumption of described promoter is the 1-3 weight portion.
5. a kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder according to claim 4, it is characterized in that, described defoamer comprises polysiloxanes, polyoxyethylene or tributyl phosphate, described flexibilizer comprises acrylonitrile-butadiene rubber, haloflex or acrylonitrile-butadiene-styrene copolymer (ABS), and described promoter comprises benzyl dimethylamine or N tert butyl benzothiazole 2 sulfenamide.
6. a kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder according to claim 1 is characterized in that the mixing speed of described agitator is 200-500 rev/min.
7. a kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder according to claim 1 is characterized in that the fiber described in the step (4) is a carbon fiber, and the volume content of this carbon fiber is 60-80%.
8. a kind of full winding and curing process of wet method for preparing carbon fiber aluminum liner hydrogen storage cylinder according to claim 1 is characterized in that, is cured step in the curing oven described in the step (5) and comprises:
(1) temperature with curing oven was warmed up to 80 ℃-90 ℃ from room temperature in 20-30 minute;
(2) 80 ℃-90 ℃ insulations 40-80 minute;
(3) in 20-30 minute, the furnace temperature of curing oven is raised to 130 ℃-140 ℃ from 80 ℃-90 ℃;
(4) 130 ℃-140 ℃ insulations 170-200 minute;
(5) be cooled to room temperature naturally.
CN2009101998156A 2009-12-02 2009-12-02 Wet fully-winding and curing process for preparing hydrogen cylinder with carbon fiber lining Pending CN102085724A (en)

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Application Number Priority Date Filing Date Title
CN2009101998156A CN102085724A (en) 2009-12-02 2009-12-02 Wet fully-winding and curing process for preparing hydrogen cylinder with carbon fiber lining

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103972553A (en) * 2014-04-03 2014-08-06 上海华篷防爆科技有限公司 Hydrogen storage device made of iron-base alloy composite material
CN105291410A (en) * 2015-11-01 2016-02-03 北京工业大学 Winding and curing process for preparing composite gas cylinder for breathing apparatus
CN112303478A (en) * 2020-10-30 2021-02-02 陕西碳能新材料有限责任公司 Fireproof flame-retardant vehicle-mounted high-pressure hydrogen storage cylinder and manufacturing method thereof
CN113883408A (en) * 2021-08-31 2022-01-04 海鹰空天材料研究院(苏州)有限责任公司 Ultrahigh-pressure fully-wound gas cylinder with aluminum alloy inner container and manufacturing method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1563781A (en) * 2004-04-08 2005-01-12 上海交通大学 50-litres hydrogen composite cylinder having carbon fiber wholly-wound, reinforced aluminum lining
JP2005036918A (en) * 2003-07-16 2005-02-10 Samtec Kk High pressure tank using highly rigid fiber and its manufacturing method
CN1690143A (en) * 2004-04-28 2005-11-02 宝山钢铁股份有限公司 Aqueous self-bonding coating for electrical steel
CN1948818A (en) * 2006-11-06 2007-04-18 哈尔滨工业大学 High pressure hydrogen storage bottle made of PBO fiber and carbon fiber mixed composite material and preparation method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005036918A (en) * 2003-07-16 2005-02-10 Samtec Kk High pressure tank using highly rigid fiber and its manufacturing method
CN1563781A (en) * 2004-04-08 2005-01-12 上海交通大学 50-litres hydrogen composite cylinder having carbon fiber wholly-wound, reinforced aluminum lining
CN1690143A (en) * 2004-04-28 2005-11-02 宝山钢铁股份有限公司 Aqueous self-bonding coating for electrical steel
CN1948818A (en) * 2006-11-06 2007-04-18 哈尔滨工业大学 High pressure hydrogen storage bottle made of PBO fiber and carbon fiber mixed composite material and preparation method

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孟剑: "碳纤维复合材料高压储氢容器力学模型分析与抗疲劳研究", 《中国优秀硕士学位论文全文数据库工程科技Ⅱ辑》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103972553A (en) * 2014-04-03 2014-08-06 上海华篷防爆科技有限公司 Hydrogen storage device made of iron-base alloy composite material
CN105291410A (en) * 2015-11-01 2016-02-03 北京工业大学 Winding and curing process for preparing composite gas cylinder for breathing apparatus
CN112303478A (en) * 2020-10-30 2021-02-02 陕西碳能新材料有限责任公司 Fireproof flame-retardant vehicle-mounted high-pressure hydrogen storage cylinder and manufacturing method thereof
CN112303478B (en) * 2020-10-30 2022-05-03 陕西碳能新材料有限责任公司 Fireproof flame-retardant vehicle-mounted high-pressure hydrogen storage cylinder and manufacturing method thereof
CN113883408A (en) * 2021-08-31 2022-01-04 海鹰空天材料研究院(苏州)有限责任公司 Ultrahigh-pressure fully-wound gas cylinder with aluminum alloy inner container and manufacturing method thereof

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Application publication date: 20110608