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Design and microstructural control of new hydrogen permeation alloys fir hydrogen membrane reactor

氢膜反应器新型氢渗透合金的设计与微观结构控制

基本信息

批准号：
14350363
负责人：
AOKI Kiyoshi
金额：
$ 9.54万
依托单位：
Kitami Institute of Technology
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2002
资助国家：
日本
起止时间：
2002 至 2004
项目状态：
已结题

项目摘要

Pd-Ag alloys are commercially used as a hydrogen separation and purification alloy, but they are too expensive and scarce in resources. Then, it is strongly desired the development of low cost and high performance hydrogen permeation alloy. Hydrogen permeability φ of 5A metals are higher than that of Pd-Ag alloys, but they suffer from the severe hydrogen embrittlement. That is, the high φ value is incompatible with high resistance to the hydrogen embrittlement in single-phase alloys. The present authors have proposed new hydrogen permeation alloys on the basis of the concept of duplex phases. Firstly, the relation between microstructures and φ has been investigated in the as-cast Nb-Ti-Ni alloys. The Nb_<39>Ti_<31>Ni_<30> alloy consisting of the primary bcc-(Nb, Ti) phase and the eutectic {(Nb, Ti)+TiNi} one shows the highest φ=1.93x10^<-8> [mol H_2 m^<-1> s^<-1> Pa^<-0.5>] at 673 K, which is higher than that of Pd. Furthermore, φ is measurable in the Nb-rich Nb-Ti-Ni alloys on the straight line connecting the eutectic point and the primary phase. φ increases with increasing Nb content and the amount of the primary phase. The most Nb-rich Nb_<68>Ti_<17>Ni_<15> alloy, consisting of the 26vol% eutectic phase and the 74vol% primary phase, shows the highest φ of 4.91x10^<-8> (mol H_2 m^<-1>s^<-1>Pa^<-0.5>). In addition, φ of the eutectic Nb-Zr-Ni alloys containing the primary phases ZrNi or bcc (Nb, Zr) has been measured. φ of the Nb_<20>Zr_<40>Ni_<40> alloy containing the primary bcc-(Nb, Zr) phase (18 vol %) is 2.73x10^<-8> [mol H_2 m^<-1> s^<-1>Pa^<-0.5>] at 673 K. These values are higher than that of pure Pd and of the Nb_<39>Ti_<31>Ni_<30> alloy. The present works strongly indicates that multiphase alloys containing eutectic structures, which suppress the hydrogen embrittlement, are promising as novel hydrogen permeation alloy membranes.

Pd-Ag合金在商业上用作氢分离和纯化合金，但是它们太昂贵并且资源稀缺。因此，开发低成本、高性能的渗氢合金势在必行。5A合金的氢渗透率φ比Pd-Ag合金高，但氢脆严重。也就是说，高φ值与单相合金中的高抗氢脆性不相容。本文作者在双相概念的基础上提出了新型氢渗透合金。首先，研究了铸态Nb-Ti-Ni合金的显微组织与φ的关系。由<39><31><30>初生bcc-（Nb，Ti）相和共晶{（Nb，Ti）+TiNi}相组成的Nb_ Ti_ Ni_合金在673 K时具有最高的φ= 1.93 × 10 ~（10）^<-8>[mol H_2 m^<-1>s^<-1>Pa^<-0.5>]，高于Pd的φ。此外，在富Nb的Nb-Ti-Ni合金中，φ在连接共晶点和初生相的直线上是可测量的。φ随Nb含量和初生相数量的增加而增加。最富Nb的Nb_<68>Ti_<17>Ni_2<15>合金由26vol%的共晶相和74vol%的初生相组成，具有最高的φ值4.91 × 10 ~（-2）<-8>（mol H_2·m ~（2·<-1>s）·<-1>Pa ~（2·）<-0.5>）。此外，还测定了含有ZrNi或bcc（Nb，Zr）初生相的Nb-Zr-Ni共晶合金的φ。含<20><40><40>18vol%初生bcc-（Nb，Zr）相的Nb_ Zr_ Ni_2合金在673 K时的φ为2.73 × 10 ~（-2）<-8>[mol H_2·m ~（2+）·s ~（2+<-1>）·<-1>Pa ~（2<-0.5>+）]。这些值高于纯Pd和Nb_<39>Ti_<31>Ni_<30>2合金。目前的工作强烈表明，含有共晶结构的多相合金，抑制氢脆，是有前途的新型透氢合金膜。