成果報告書詳細
管理番号20120000000278
タイトル*平成23年度中間年報 水素先端科学基礎研究事業 水素先端科学基礎研究 水素に対して耐性に優れた適用材料の研究開発
公開日2013/3/20
報告書年度2011 - 2011
委託先名日本合成化学工業株式会社
プロジェクト番号P06026
部署名新エネルギー部
和文要約和文要約等以下本編抜粋:
1.研究開発の内容及び成果等
本研究開発は、「70MPa水素耐性を有するガスバリア材の最適化検討と2015年水素ステーション機器への応用可能性の初年度中での明確化」と平成23年度?平成24年度における「高機能化高圧水素ガス多層樹脂配管、高圧水素ガス多層樹脂ホースの耐久性材料設計指針の策定」からなる。平成23年度の研究開発内容及び成果は、次の通りである。
検討案件
【高圧水素ガス多層樹脂配管、高圧水素多層樹脂ホースの耐久性制御因子の把握】
高圧水素に直接さらされるナイロン11 等からなる多層樹脂ホース等の最内層に水素ガスに対して高いガスバリア性を有する層を導入出来れば、ナイロン11 層中に拡散・溶存する水素濃度を低減でき、その結果、硬化・脆化・亀裂進展等の経年変化を大幅に抑制できる可能性がある。ガスバリア層を中間層乃至最内層とした多層樹脂配管、多層樹脂ホースの耐久性及び10000回以上の充填対応(3年の連続使用想定回数)可能な高気密化(水素ガスバリア性)及びブリスタ生成の抑制を目指し、平成23年度に以下の項目を実施した。
【具体的な実施項目及び成果】
1 . ナイロン1 1 層への高圧水素ガス吸収量軽減効果の確認と7 0 M P a 下で必要な水素ガスバリア層の厚みの見積もり。
平成22年度成果物である水素耐性を有する表1記載のベース樹脂を元に柔軟性を付与する為にポリマーアロイ化を実施した。
英文要約Fundamental Research Project on Advanced Hydrogen Science (FY2010-FY2012) FY2011Annual Report The research and development of applicable material that is resistant to hydrogen gas

To utilize the hydrogen for vehicles, flexible high-pressure hose is one of the key components that need to be developed for 70MPa high-pressure hydrogen supply system. Fiber-reinforced nylon is expected as a main material for the flexible high-pressure hose. However, we consider nylon layer can be damaged by the dissolved hydrogen because of direct contact of hydrogen. That is, we presume a crack growth in nylon layer that deteriorates durability of the hose occurs. We presume that we can prevent this crack growth in nylon layer by placing the high hydrogen gas barrier layer at the inner layer of flexible high-pressure hose. Therefore, in 2010 we designed optimum amorphous polyvinyl alcohol for high-pressure hydrogen gas barrier materials that is used for laminating with nylon. In 2011,we worked on development of gas barrier resin that can follow deformation of resin hose when 70MPa high-pressure hydrogen is charged into hose. The main content of the study is summarized as follows.

(1)Evaluation of the hydrogen dissolution amount under 70MPa high pressure hydrogen gas

Amorphous polyvinyl alcohol is the best gas barrier property in all resins, but amorphous polyvinyl alcohol is hard resin because of its high Tg. And so, we had to develop the gas barrier resin that can follow deformation of resin hose when 70MPa high-pressure hydrogen is charged into hose. In order to improve the physical properties of amorphous polyvinyl alcohol,
polymer alloy of amorphous polyvinyl alcohol and a soft component was developed. Matrix component and domain component is as follows.

(Matrix component)
Amorphous polyvinyl alcohol which has the T1C (13C spin-lattice relaxation time) of a long time component in amorphous phase.

(Domain component)
Fluorocarbon resin, nylon11, nylon1 and so on.

We evaluated the hydrogen dissolution amount into the resin under 70MPa high-pressure. Amorphous polyvinyl alcohol gave lower hydrogen dissolution amount than nylon. Fluorocarbon resin has no good gas barrier property, but we confirmed the hydrogen dissolution amount into fluorocarbon resin was far less than that of nylon.

(2) Hydrogen resistance properties of polymer alloy
Polymer alloy consists of amorphous polyvinyl alcohol and fluorocarbon resin (tan δ=-100 deg C) showed good flexibility without deteriorating hydrogen resistance properties.
Even after amorphous polyvinyl alcohol and its polymer alloy were repeatedly exposed to 70MPa high-pressure hydrogen gas, we did not confirm any mechanical changes. The influence on higher-order structure in amorphous phase was also in negligible level.

We are now working on proof test of the fiber reinforced multilayer resin hose for the purpose of formulating design manual for the flexible high-pressure hose for the next fiscal year.


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