U.S. patent application number 12/529136 was filed with the patent office on 2010-04-15 for hydrogen-permeable alloy, and hydrogen-permeable film and its production method.
This patent application is currently assigned to HITACHI METALS, LTD. Invention is credited to Masahiro Tobise, Akihiro Toji, Toshihiro Uehara, Kazuhiro Yamamura.
Application Number | 20100092333 12/529136 |
Document ID | / |
Family ID | 39759455 |
Filed Date | 2010-04-15 |
United States Patent
Application |
20100092333 |
Kind Code |
A1 |
Yamamura; Kazuhiro ; et
al. |
April 15, 2010 |
HYDROGEN-PERMEABLE ALLOY, AND HYDROGEN-PERMEABLE FILM AND ITS
PRODUCTION METHOD
Abstract
A hydrogen-permeable Nb--Ti--Ni alloy having a composition
represented by Nb.sub.100-x-yTi.sub.xNi.sub.y, wherein
10.ltoreq.x.ltoreq.60, and 10.ltoreq.y.ltoreq.50 by atomic %, with
an oxygen content of 1000 ppm or less in an as-cast state, which
comprises (a) a hydrogen-permeable primary phase containing 70
atomic % or more of Nb and 10 atomic % or less of Ni, and (b) a
eutectic phase having a particle phase comprising Nb and Ti as main
components with a small Ni content and having an average particle
size of about 5 .mu.m or less, which is dispersed in a matrix phase
comprising 60 atomic % or more in total of Ni and Ti and having
hydrogen embrittlement resistance, the alloy having a structure
substantially free from an intermetallic compound phase.
Inventors: |
Yamamura; Kazuhiro;
(Kumagaya-shi, JP) ; Tobise; Masahiro;
(Kumagaya-shi, JP) ; Uehara; Toshihiro;
(Yasugi-shi, JP) ; Toji; Akihiro; (Yasugi-shi,
JP) |
Correspondence
Address: |
SUGHRUE MION, PLLC
2100 PENNSYLVANIA AVENUE, N.W., SUITE 800
WASHINGTON
DC
20037
US
|
Assignee: |
HITACHI METALS, LTD
Minato-ku, Tokyo
JP
|
Family ID: |
39759455 |
Appl. No.: |
12/529136 |
Filed: |
March 7, 2008 |
PCT Filed: |
March 7, 2008 |
PCT NO: |
PCT/JP2008/054176 |
371 Date: |
October 6, 2009 |
Current U.S.
Class: |
420/417 ;
164/76.1; 420/426; 420/441 |
Current CPC
Class: |
C22F 1/18 20130101; C22F
1/00 20130101; C22C 1/06 20130101; C22C 27/02 20130101; B01D
67/0039 20130101; Y02E 60/50 20130101; C01B 3/503 20130101; H01M
4/94 20130101; B01D 69/02 20130101; B01D 2256/16 20130101; B01D
2325/20 20130101; B01D 2325/24 20130101; C22C 19/03 20130101; B01D
71/022 20130101; B01D 53/228 20130101; C22C 30/00 20130101; B01D
67/0074 20130101 |
Class at
Publication: |
420/417 ;
420/426; 420/441; 164/76.1 |
International
Class: |
C22C 14/00 20060101
C22C014/00; C22C 27/02 20060101 C22C027/02; C22C 19/03 20060101
C22C019/03; B22D 21/00 20060101 B22D021/00; B22D 23/00 20060101
B22D023/00 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 9, 2007 |
JP |
2007-060189 |
Claims
1. A hydrogen-permeable Nb--Ti--Ni alloy comprising a
hydrogen-permeable phase and a hydrogen-embrittlement-resistant
phase, which has an oxygen content (measured in an as-cast state)
of 1000 ppm or less.
2. The hydrogen-permeable alloy according to claim 1, which has a
primary phase having an oxygen content (measured by EPMA) of 2000
cps or less.
3. The hydrogen-permeable alloy according to claim 1, which has
Vickers hardness of 270 HV or less.
4. A hydrogen-permeable film produced by heat-treating and rolling
the hydrogen-permeable alloy recited in claim 1.
5. A hydrogen-permeable Nb--Ti--Ni alloy having a composition
represented by Nb.sub.100-x-yTi.sub.xNi.sub.y, wherein
10.ltoreq.x.ltoreq.60, and 10.ltoreq.y.ltoreq.50 by atomic %, with
an oxygen content of 1000 ppm or less in an as-cast state, which
comprises (a) a hydrogen-permeable primary phase containing 70
atomic % or more of Nb and 10 atomic % or less of Ni, and (b) a
eutectic phase having a particle phase comprising Nb and Ti as main
components with a small Ni content and having an average particle
size of about 5 .mu.m or less, which is dispersed in a matrix phase
comprising 60 atomic % or more in total of Ni and Ti and having
hydrogen embrittlement resistance, said alloy having a structure
substantially free from an intermetallic compound phase.
6. A method for producing a hydrogen-permeable film having a
thickness of 0.01-1 mm, comprising heat-treating and rolling a cast
alloy body having a composition represented by
Nb.sub.100-x-yTi.sub.xNi.sub.y, wherein 10.ltoreq.x.ltoreq.60, and
10.ltoreq.y.ltoreq.50 by atomic %, and an oxygen content of 1000
ppm or less.
7. A method for producing a hydrogen-permeable film having a
composition represented by Nb.sub.100-x-yTi.sub.xNi.sub.y, wherein
10.ltoreq.x.ltoreq.60, and 10.ltoreq.y.ltoreq.50 by atomic %, and a
thickness of 0.01-1 mm, comprising the steps of (1) mixing alloy
materials comprising Nb metal, Ti metal and Ni metal each having an
oxygen content of 1000 ppm or less, with 30-1000 ppm of a
deoxidizer based on the entire weight of said alloy materials, (2)
melting said alloy materials in an atmosphere obtained by
evacuating to 6.times.10.sup.-3 Pa or less and then introducing an
inert gas, to produce a cast alloy body having an oxygen content of
1000 ppm or less, and (3) repeatedly annealing and rolling said
cast alloy body to a thickness of 0.01-1 mm.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to a hydrogen-permeable alloy
having high hydrogen permeability and hydrogen embrittlement
resistance and good rollability, a hydrogen-permeable film formed
by the hydrogen-permeable alloy, and its production method.
BACKGROUND OF THE INVENTION
[0002] Hydrogen used for fuel cells is at present produced by
reforming methane, methanol, etc. However, this method generates
impurity gases such as CO, CO.sub.2, H.sub.2O, etc. in addition to
hydrogen. Among them, CO deactivates fuel cell electrodes.
Therefore, impurity gases should be removed from hydrogen produced
by reforming methods. Known as a method for easily purifying
hydrogen is a separation method using a hydrogen-permeable metal
film. Hydrogen-permeable films practically used at present are
Pd--Ag alloy films. However, because the Pd--Ag alloy films
disadvantageously contain expensive, rare Pd, it is expected that
they cannot be supplied to meet all future demand of fuel cells.
Accordingly, metal films substituting for the Pd--Ag alloy films
are desired.
[0003] A hydrogen-permeable alloy having high hydrogen permeability
and hydrogen embrittlement resistance was developed by combining V,
Nb or Ta having high hydrogen permeability in a simple substance
form, with other metals such as Ti, Zr, Hf, Ni, Co, etc. to a
multi-phase alloy (Summary of the 2006, Autumn Meeting of The Japan
Institute of Metals, page 171). As described in JP 2005-232491, JP
2006-274298, and "Materia Japan," Vol. 45, No. 3 (2006), pp.
186-191, Nb--Ti--Ni alloys have excellent hydrogen permeability and
hydrogen embrittlement resistance. The Nb--Ti--Ni alloys suitable
as hydrogen-permeable alloys are two-phase alloys having (a) a
primary phase containing 70 atomic % or more of Nb [represented by
(Nb,Ti)p because of small Ni content], and (b) a eutectic phase
comprising a phase containing 60 atomic % or more in total of Ni
and Ti (represented by NiTi because of small Nb content) and a
phase containing a lot of Nb other than the primary phase
[represented by (Nb,Ti)e because of small Ni content].
[0004] However, because the Nb--Ti--Ni alloy contains Nb and Ti
extremely reactable with oxygen, brittle intermetallic compounds
are likely formed by incorporating oxygen from an atmosphere in its
mass-production method, in which it is cast in a large furnace, and
heat-treated and rolled to a thin plate. With intermetallic
compounds, the Nb--Ti--Ni alloy has low hydrogen permeability and
hydrogen embrittlement resistance as well as low rollability. Also,
the intermetallic compounds make cast alloy bodies brittle
depending on their compositions.
[0005] To suppress the formation of intermetallic compounds in the
Nb--Ti--Ni alloy, a high-vacuum melting atmosphere has
conventionally been used. It has been found, however, that mere
melting in vacuum fails to provide Nb--Ti--Ni alloys with such a
low oxygen content as to be suitable for hydrogen-permeable
alloys.
OBJECT OF THE INVENTION
[0006] Accordingly, an object of the present invention is to
provide a hydrogen-permeable Nb--Ti--Ni alloy having a sufficiently
low oxygen content to have excellent hydrogen permeability and
hydrogen embrittlement resistance and improved rollability, a
hydrogen-permeable apparatus formed by such Nb--Ti--Ni alloy, and a
method for producing a hydrogen-permeable film.
DISCLOSURE OF THE INVENTION
[0007] As a result of intensive research in view of the above
object, the inventors have found that to suppress the formation of
brittle intermetallic compounds acting to lower rollability, it is
necessary to highly reduce an oxygen content in the Nb--Ti--Ni
alloy, and that to this end, it is necessary to reduce oxygen
contents in alloy materials and an atmosphere as much as possible,
and add a deoxidizer to an alloy material melt to remove oxygen
therefrom. The present invention has been completed based on such
finding.
[0008] Thus, the hydrogen-permeable Nb--Ti--Ni alloy of the present
invention comprises a hydrogen-permeable phase and a
hydrogen-embrittlement-resistant phase, and has an oxygen content
(measured in an as-cast state) of 1000 ppm or less. It preferably
has a primary phase having an oxygen content (measured by EPMA) of
2000 cps (counts per second) or less.
[0009] With the oxygen content of 1000 ppm or less, the cast alloy
body has Vickers hardness of 270 HV or less and good
rollability.
[0010] The hydrogen-permeable alloy preferably has a composition
represented by Nb.sub.100-x-yTi.sub.xNi.sub.y, wherein
10.ltoreq.x.ltoreq.60, and 10.ltoreq.y.ltoreq.50 by atomic %.
[0011] The hydrogen-permeable Nb--Ti--Ni alloy according to a
preferred embodiment of the present invention has a composition
represented by Nb.sub.100-x-yTi.sub.xNi.sub.y, wherein
10.ltoreq.x.ltoreq.60, and 10.ltoreq.y.ltoreq.50 by atomic %, with
an oxygen content of 1000 ppm or less in an as-cast state, and
comprises (a) a hydrogen-permeable primary phase containing 70
atomic % or more of Nb and 10% or less of Ni, and (b) a eutectic
phase having a particle phase comprising
[0012] Nb and Ti as main components with a small Ni content and
having an average particle size of about 5 .mu.m or less, which is
dispersed in a matrix phase comprising 60 atomic % or more in total
of Ni and Ti and having hydrogen embrittlement resistance, the
alloy having a structure substantially free from an intermetallic
compound phase.
[0013] The hydrogen-permeable film of the present invention can be
obtained by heat-treating and rolling the above hydrogen-permeable
alloy. The hydrogen-permeable film preferably has a thickness of
0.01-1 mm.
[0014] The method of the present invention for producing a
hydrogen-permeable film comprises heat-treating and rolling a cast
alloy body having a composition represented by
Nb.sub.100-x-yTi.sub.xNi.sub.y, wherein 10.ltoreq.x.ltoreq.60, and
10.ltoreq.y.ltoreq.50 by atomic %, and having an oxygen content of
1000 ppm or less.
[0015] While melting the cast alloy body of the present invention
in vacuum or in a non-oxidizing atmosphere, oxygen is removed from
an alloy material melt with a deoxidizer. The deoxidizer is
preferably C, Al, Mg, Ca, etc. The amount of the deoxidizer
introduced into the melt is preferably 30-1000 ppm based on
Nb+Ti+Ni. To remove an oxygen gas from a melting atmosphere, a
getter material is preferably used. The getter material is
preferably metal V or Ti.
[0016] To reduce an oxygen content in the alloy, the heat treatment
of the cast alloy body is conducted preferably in a hydrogen
atmosphere.
[0017] The method for producing a hydrogen-permeable film having a
composition represented by Nb.sub.100-x-yTi.sub.xNi.sub.y, wherein
10.ltoreq.x.ltoreq.60, and 10.ltoreq.y.ltoreq.50 by atomic %, and a
thickness of 0.01-1 mm according to a preferred embodiment of the
present invention comprises the steps of (1) mixing alloy materials
comprising Nb metal, Ti metal and Ni metal each having an oxygen
content of 1000 ppm or less, with 30-1000 ppm of a deoxidizer based
on the entire weight of the alloy materials, (2) melting the alloy
materials in an inert gas atmosphere evacuated to 6.times.10.sup.-3
Pa or less to produce a cast alloy body having an oxygen content of
1000 ppm or less, and (3) repeatedly annealing and rolling the cast
alloy body to a thickness of 0.01-1 mm.
BRIEF DESCRIPTION OF THE DRAWINGS
[0018] FIG. 1 is a graph showing the relation between an oxygen
content and Vickers hardness in a cast Nb--Ti--Ni alloy.
[0019] FIG. 2 is a graph showing the relation between an oxygen
content and elongation in a cast Nb--Ti--Ni alloy.
[0020] FIG. 3 is a graph showing the relation between an oxygen
content and tensile strength in a cast Nb--Ti--Ni alloy.
[0021] FIG. 4 is a graph showing the X-ray diffraction patterns of
the cast Nb--Ti--Ni alloys of Example 2 and Comparative Examples 2
and 4.
[0022] FIG. 5 is a graph showing the relation between an oxygen
content and an NiTi.sub.2 phase content in a cast Nb--Ti--Ni
alloy.
[0023] FIG. 6 is a graph showing the relation between an oxygen
content and the relative intensity of a Nb.sub.40Ti.sub.15Ni.sub.45
phase peak in an X-ray diffraction pattern of a cast Nb--Ti--Ni
alloy.
[0024] FIG. 7 is a SEM photograph showing the structure of the cast
Nb--Ti--Ni alloy of Example 3.
[0025] FIG. 8 is a SEM photograph showing the structure of the cast
Nb--Ti--Ni alloy of Comparative Example 4.
[0026] FIG. 9 is a graph showing the EPMA analysis results of the
cast Nb--Ti--Ni alloy of Example 3.
[0027] FIG. 10 is a graph showing the EPMA analysis results of the
cast Nb--Ti--Ni alloy of Comparative Example 4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[1] Composition And Structure of Nb--Ti--Ni Alloy
[0028] The hydrogen-permeable Nb--Ti--Ni alloy of the present
invention has a composition represented by
Nb.sub.100-x-yTi.sub.xNi.sub.y, wherein 10.ltoreq.x.ltoreq.60,
10.ltoreq.y.ltoreq.50, by atomic %. When Ti is less than 10 atomic
%, the cast alloy body is so brittle that it cannot easily be
rolled. When Ti is more than 60 atomic %, the alloy has low
hydrogen permeability. When Ni is less than 10 atomic %, the alloy
has high hydrogen permeability, though it is easily embrittled with
hydrogen. When Ni exceeds 50 atomic %, the cast alloy body becomes
so mechanically brittle that its rolling is difficult. the Ti
content x is preferably 20-40 atomic %, and the Ni content y is
preferably 20-40 atomic %.
[0029] The hydrogen-permeable Nb--Ti--Ni alloy has a two-phase
structure comprising (a) a primary phase [expressed by (Nb,Ti)p,
wherein p means "primary phase"] containing 70 atomic % or more of
Nb and 10% or less of Ni, and (b) a eutectic phase [expressed by
NiTi+(Nb,Ti)e] comprising a phase (expressed by NiTi) containing 60
atomic % or more in total of Ni and Ti, and a phase [expressed by
(Nb,Ti)e, wherein e means "eutectic"] containing Nb as a main
component with a small Ni content.
[0030] The primary phase is a bcc crystal, in which hydrogen is
dissolved and diffused, thereby exhibiting hydrogen permeability.
The primary phase preferably has an average particle size of 7-20
.mu.m. The particle size of each primary phase is expressed by a
diameter of a circle having the same area as that of the primary
phase. The percentage of the primary phase in the alloy structure
(corresponding to an area ratio determined on an electron
photomicrograph) is preferably 30% or more. Though not restrictive,
the upper limit of the percentage of the primary phase is
practically 90%, particularly about 80%.
[0031] The NiTi phase constituting the eutectic phase matrix
typically has a composition comprising 30-55 atomic % of Ni, 30-55
atomic % of Ti, and 5-15 atomic % of Nb, particularly 40-55 atomic
% of Ni, 40-55 atomic % of Ti, and 5-15 atomic % of Nb, to exhibit
hydrogen embrittlement resistance. The (Nb,Ti)e phase dispersed in
the NiTi phase has a composition comprising Nb and Ti as main
components, a Nb content being from 70 atomic % to about 40 atomic
% like in the primary phase, with a small Ni content. In the cast
alloy body, the eutectic phase has a laminar structure in which the
NiTi phase and the (Nb,Ti)e phase are in laminar alignment, but
after heat treatment, a (Nb,Ti)e particle phase having an average
particle size of about 5 .mu.m or less, particularly 0.5-3 .mu.m,
is dispersed in the NiTi phase as shown in FIG. 7.
[0032] 10 atomic % or less, preferably 5 atomic % or less, of Ni
may be substituted by Ag, Cr, Cu, Ga, Zn or Fe. 10 atomic % or less
of Ti may be substituted by other 4A-group elements. 10 atomic % or
less of Nb may be substituted by other 5A-group elements.
[0033] When the oxygen content in the cast alloy body becomes
higher than 1000 ppm, a phase (expressed by NiTi.sub.2) having a
Ti/Ni atomic ratio about 2 times that in the NiTi phase, and a
Nb.sub.40Ni.sub.15Ti.sub.45 phase appear in the eutectic phase. The
NiTi.sub.2 phase generally has a composition comprising 20-40
atomic % of Ni, 40-60 atomic % of Ti, and 10-20 atomic % of Nb.
These intermetallic compound phases harden the cast alloy body,
resulting in extremely low elongation, so that the cast alloy body
has extremely reduced rollability. Accordingly, substantially no
intermetallic compound phases comprising the NiTi.sub.2 phase and
the Nb.sub.40Ni.sub.15Ti.sub.45 phase preferably exist in the
structure of the cast Nb--Ti--Ni alloy. The term "substantially no
intermetallic compound phases" used herein means that the
percentage of the intermetallic compound phases in the alloy
structure is 5% or less by weight.
[0034] To meet the above structure conditions, the cast alloy body
should have an oxygen content of 1000 ppm or less. The oxygen
content of 1000 ppm or less suppresses the formation of the
NiTi.sub.2 phase, resulting in high mechanical strength. The oxygen
content of the cast alloy body is preferably 800 ppm or less, more
preferably 500 ppm or less. Though the lower limit of the oxygen
content is not particularly restricted, the oxygen content of less
than 20 ppm is not practical because it requires increase in the
number of steps, strict condition control, etc. in industrial mass
production. When the hydrogen-permeable film is produced by heat
treatment and rolling, increase in the oxygen content by heat
treatment is 300 ppm or less.
[0035] The primary phase in the cast Nb--Ti--Ni alloy of the
present invention should have an oxygen content (measured by EPMA)
of 2000 cps (counts per second) or less. The measurement of the
oxygen content is conducted as follows. Characteristic X-ray
(K.alpha. line) generated by the measurement of a minor-polished
alloy sample by an electron probe microanalyzer (EPMA-1610,
available from Shimadzu Corporation) is diffracted by an analyzing
crystal, and received by a proportional counter to count
characteristic X rays inherent to oxygen, thereby measuring the
oxygen content in the primary phase. The accelerating voltage is 20
kV, and the sample current is 50 nA. The analyzing crystal is
pentaerythritol crystal for NbL.alpha. line, and LiF crystal for
NiK.alpha. line and TiK.alpha. line, and artificial crystal LS7A
(available from Shimadzu Corporation) for OK.alpha. line. The
diameter of electron beams is 1 .mu.m. Measurement is conducted in
a range of 50 .mu.m with measuring time of 1 second per one point
and a step width of 0.2 .mu.m. Oxygen contents are measured in
arbitrarily selected five primary phases each having a maximum
diameter of 10 .mu.m or more, and averaged.
[2] Production Method of Nb--Ti--Ni Alloy
[0036] Alloy materials may be melted in vacuum or in an inert gas
atmosphere by an arc-melting method, a
high-frequency-induction-melting method, an electron-beam-melting
method, a laser-melting method, a levitation-melting method, etc.
Materials for a crucible used for melting the alloy materials are
preferably ceramics such as zirconia, calcia and boron nitride,
carbon, water-cooled copper, etc.
[0037] The alloy materials are preferably metals with as high
purity as possible. The amount of oxygen in each of Nb, Ti and Ni
metals is preferably 1000 ppm or less, more preferably 500 ppm or
less. To reduce the oxygen content, each metal material may be
heat-treated at 800.degree. C. to 1200.degree. C. for about 0.5-50
hours in hydrogen.
[0038] To reduce the oxygen content in the melting atmosphere, it
is preferable to reduce the pressure of the atmosphere
sufficiently, particularly to 6.times.10.sup.-3 Pa or less, before
melting. More preferably, one or more steps of substituting the
atmosphere with an inert gas such as Ar, and evacuating it are
conducted after pressure reduction. The inert gas atmosphere, in
which melting is conducted, may be atmospheric or reduced-pressure
air, for instance, at about 40 kPa.
[0039] When the atmosphere has a large oxygen content, a lot of
oxygen may be dissolved in the alloy melt. Accordingly, it is
preferable to remove an oxygen gas from the atmosphere as much as
possible. To this end, a getter material made of a metal easily
absorbing oxygen (Ti, V, etc.) is melted in another vessel in a
melting apparatus before melting, so that it can absorb an oxygen
gas.
[0040] A deoxidizer such as C, Al, Mg, Ca, etc. is added to the
melt to remove oxygen coming from the alloy materials. The
deoxidizer dissolved in the melt reacts with oxygen to form slag,
which floats on the surface. The amount of the deoxidizer added is
preferably slightly smaller than a stoichiometric amount calculated
from the oxygen content in the alloy material mixture (for
instance, 90% or less), to prevent the deoxidizer from remaining in
the resultant cast alloy body. Specifically, the amount of the
deoxidizer added is preferably 30-1000 ppm, more preferably 50-300
ppm, based on the entire weight of the alloy materials. When the
deoxidizer is less than 30 ppm, oxygen cannot sufficiently be
removed from the melt. When it exceeds 1000 ppm, the deoxidizer
remains in the resultant cast alloy body, deteriorating hydrogen
permeability and rollability. The slag on the melt surface may be
removed before solidification, or removed from the solidified cast
alloy body surface by a grinder.
[0041] The cast Nb--Ti--Ni alloy thus obtained to have an oxygen
content reduced to 1000 ppm or less is substantially free from
intermetallic compounds deteriorating rollability, and has Vickers
hardness of 270 HV or less, so that it can be easily rolled.
[3] Hydrogen-Permeable Film
[0042] To form a hydrogen-permeable film from the cast Nb--Ti--Ni
alloy of the present invention, the cast alloy body is annealed and
rolled. The cast alloy body may be hot-forged before rolling. The
rolling may be a combination of hot rolling and cold rolling. In
the case of cold rolling, a rolling ratio by one operation is
preferably 30-70%. Because cold rolling causes hardening, annealing
is conducted at a temperature of 900.degree. C. or higher,
particularly 1000.degree. C. or higher, to provide the alloy with
rollability by recrystallization. The annealing atmosphere is
preferably hydrogen. A time period of one annealing operation may
be about 0.1-10 hours. To conduct rolling and annealing
alternately, the thickness of the cast alloy body can be reduced to
0.01-1 mm, suitable for a hydrogen-permeable film. The total
rolling ratio [=(original thickness-final thickness)/original
thickness] can be 70% or more, further 80% or more, particularly
90% or more.
[0043] The resultant hydrogen-permeable film is preferably
heat-treated at 900-1100.degree. C. for 0.5-300 hours in vacuum or
in a non-oxidizing atmosphere. This heat treatment provides the
film with improved hydrogen permeability.
[0044] The present invention will be explained in further detail by
Examples below without intention of restricting the present
invention thereto.
EXAMPLE 1
[0045] As alloy materials, pure Nb metal (oxygen content: 10 ppm),
pure Ti metal (oxygen content: 140 ppm) and pure Ni metal (oxygen
content: 40 ppm) were mixed to a composition of
Ni.sub.30Nb.sub.40Ti.sub.30 (atomic %), and metal Ca as a
deoxidizer was added to the mixture in an amount of 200 ppm based
on the alloy materials. The resultant mixture was charged into a
first water-cooled copper crucible in a vacuum arc-melting
apparatus. Metal Ti as a getter material for removing oxygen from
an atmosphere was charged into a second water-cooled copper
crucible in the vacuum arc-melting apparatus. The amount of the
getter material was 70% by mass based on the alloy materials.
[0046] After reducing the pressure of the atmosphere in the vacuum
arc-melting apparatus to 4.0.times.10.sup.-3 Pa, an Ar gas was
introduced, and evacuation was conducted again to
4.0.times.10.sup.-3 Pa. Thereafter, an Ar gas (purity: 99.99%) at
40 kPa was introduced into the apparatus. The getter material was
arc-melted to absorb an oxygen gas in the atmosphere. The alloy
materials were then melted to a cast alloy body. To provide a
uniform alloy composition, an operation of reversing, melting and
solidifying the cast alloy body was repeated 5 times. The resultant
cast alloy body was annealed at 1000.degree. C. in a hydrogen
gas.
EXAMPLE 2
[0047] A cast Nb--Ti--Ni alloy body was produced from Nb metal
(oxygen content: 20 ppm), Ti metal (oxygen content: 250 ppm) and Ni
metal (oxygen content: 40 ppm) as alloy materials, in the same
manner as in Example 1 except for changing the amount of the getter
material to 60% by mass, and the vacuum degree in the vacuum
arc-melting apparatus to 5.0.times.10.sup.-3 Pa.
EXAMPLE 3
[0048] A cast Nb--Ti--Ni alloy body was produced from Nb metal
(oxygen content: 40 ppm), Ti metal (oxygen content: 250 ppm) and Ni
metal (oxygen content: 60 ppm) as alloy materials, in the same
manner as in Example 1 except for changing the amount of the getter
material to 50% by mass, and the vacuum degree in the vacuum
arc-melting apparatus to 5.0.times.10.sup.-3 Pa.
EXAMPLE 4
[0049] A cast Nb--Ti--Ni alloy body was produced from Nb metal
(oxygen content: 40 ppm), Ti metal (oxygen content: 250 ppm) and Ni
metal (oxygen content: 60 ppm) as alloy materials, in the same
manner as in Example 1 except for changing the vacuum degree in the
vacuum arc-melting apparatus to 5.0.times.10.sup.-3 Pa without
using a getter material.
COMPARATIVE EXAMPLE 1
[0050] A cast Nb--Ti--Ni alloy body was produced from Nb metal
(oxygen content: 1600 ppm), Ti metal (oxygen content: 1050 ppm) and
Ni metal (oxygen content: 80 ppm) as alloy materials, in the same
manner as in Example 1 except for changing the amount of the getter
material to 50% by mass, and the vacuum degree of the atmosphere to
8.0.times.10.sup.-3 Pa, without using a deoxidizer.
COMPARATIVE EXAMPLE 2
[0051] A cast Nb--Ti--Ni alloy body was produced from Nb metal
(oxygen content: 2300 ppm), Ti metal (oxygen content: 500 ppm) and
Ni metal (oxygen content: 80 ppm) as alloy materials, in the same
manner as in Example 1 except for changing the amount of the getter
material to 50% by mass, and the vacuum degree of the atmosphere to
6.7.times.10.sup.-3 Pa, without using a deoxidizer.
COMPARATIVE EXAMPLE 3
[0052] A cast Nb--Ti--Ni alloy body was produced from Nb metal
(oxygen content: 2300 ppm), Ti metal (oxygen content: 1050 ppm) and
Ni metal (oxygen content: 80 ppm) as alloy materials, in the same
manner as in Example 1 except for changing the amount of the getter
material to 50% by mass, and the vacuum degree of the atmosphere to
9.3.times.10.sup.-3 Pa, without using a deoxidizer.
COMPARATIVE EXAMPLE 4
[0053] A cast Nb--Ti--Ni alloy body was produced from Nb metal
(oxygen content: 2300 ppm), Ti metal (oxygen content: 1050 ppm) and
Ni metal (oxygen content: 80 ppm) as alloy materials, in the same
manner as in Example 1 except for changing the vacuum degree of the
atmosphere to 6.7.times.10.sup.-2 Pa without using a deoxidizer and
a getter material.
[0054] Each cast alloy body of Examples 1-4 and Comparative
Examples 1-4 was melted in an inert gas, and its oxygen content was
measured by an infrared absorption method. The X-ray diffraction
pattern of each cast alloy body was measured. Assuming that each
cast body of Examples 1-4 and Comparative Examples 1-2 had a
structure having a (Nb,Ti)p phase, a NiTi phase, a (Nb,Ti)e phase,
and a NiTi.sub.2 phase, the NiTi.sub.2 phase content was calculated
from the X-ray diffraction pattern by Rietveld analysis. In
Comparative Examples 3 and 4 in which a Nb.sub.40Ti.sub.15Ni.sub.45
phase appeared, a relative intensity of a
Nb.sub.40Ti.sub.15Ni.sub.45 phase peak to a (Nb,Ti) peak was
calculated. Further, each cast alloy body was measured with respect
to Vickers hardness, and elongation and tensile strength by a
tensile test at 900.degree. C. The measurement results are shown in
Table 1 together with the production conditions of cast alloy
bodies.
TABLE-US-00001 TABLE 1 Oxygen Content Getter Vacuum (ppm) in
Material Degree of Alloy Materials (% by Atmosphere Deoxidizer No.
Nb Ti Ni mass) (Pa) (ppm) Example 1 10 140 40 70 4.0 .times.
10.sup.-3 200 Example 2 20 250 40 60 5.0 .times. 10.sup.-3 200
Example 3 40 250 60 50 5.0 .times. 10.sup.-3 200 Example 4 40 250
60 None 5.0 .times. 10.sup.-3 200 Comparative 1600 1050 80 50 8.0
.times. 10.sup.-3 None Example 1 Comparative 2300 500 80 50 6.7
.times. 10.sup.-3 None Example 2 Comparative 2300 1050 80 50 9.3
.times. 10.sup.-3 None Example 3 Comparative 2300 1050 80 None 6.7
.times. 10.sup.-2 None Example 4 Oxygen Content (ppm) in Cast
Vickers NiTi.sub.2 Content No. Alloy Body Hardness (HV) (% by
weight) Example 1 110 206 1.37 Example 2 230 220 2.17 Example 3 400
235 3.91 Example 4 580 238 4.02 Comparative 1030 245 9.23 Example 1
Comparative 1920 253 16.69 Example 2 Comparative 2240 274 --
Example 3 Comparative 5000 449 -- Example 4 Relative Intensity of
Tensile Test at 900.degree. C. Nb.sub.40Ti.sub.15Ni.sub.45 Peak
Elongation Tensile Strength No. (arbitrary unit) (%) (MPa) Example
1 0 26 411 Example 2 0 23 402 Example 3 0 22 381 Example 4 0 22 370
Comparative 0 20 321 Example 1 Comparative 0 19 314 Example 2
Comparative 9.7 1.6 273 Example 3 Comparative 12.8 0.7 236 Example
4
[0055] FIG. 1 shows the relation between Vickers hardness and an
oxygen content in the cast alloy bodies of Examples 1-4 and
Comparative Examples 1-4. As the oxygen content increased, the
Vickers hardness tended to increase. The cast alloy body of
Comparative Example 3 had increased hardness because of the
precipitation of a Nb.sub.40Ti.sub.15Ni.sub.45 phase even if the
oxygen content was small. Increase in the Vickers hardness was
presumably caused by the existence of brittle intermetallic
compounds. FIGS. 2 and 3 respectively show the dependence of
elongation and tensile strength on the oxygen content. As the
oxygen content increased, the elongation and the tensile strength
tended to decrease.
[0056] Each cast alloy body was hot-rolled to a 2-mm-thick test
piece, which was cold-rolled at a rolling ratio of 50%, annealed at
1000.degree. C. for 1 hour, and cold-rolled again to a total
rolling ratio of 80%. The resultant hydrogen-permeable film was as
thick as 0.4 mm. The hydrogen-permeable films of Examples 1-4 were
free from cracking, etc., though those of Comparative Examples 1-4
were cracked in their edges. Particularly the cast alloy bodies of
Comparative Examples 3 and 4 could not be rolled at a rolling ratio
of 70% or more.
[0057] FIG. 4 shows the X-ray diffraction patterns of the cast
alloy bodies of Example 2 and Comparative Examples 2 and 4. EPMA
measurement revealed that the NiTi phase had a composition of
Ni.sub.48.7Ti.sub.42.5Nb.sub.8.8, and that the NiTi.sub.2 phase had
a composition of Ni.sub.33.1Ti.sub.52.5Nb.sub.14.4. Although the
cast alloy body of Example 2 contained substantially no NiTi.sub.2
phase, the cast alloy body of Comparative Example 2 contained a
NiTi.sub.2 phase. The cast alloy body of Comparative Example 4
contained a Nb.sub.40Ti.sub.15Ni.sub.45 phase in addition to a
NiTi.sub.2 phase.
[0058] FIG. 5 shows the relation between an oxygen content and the
relative intensity of a NiTi.sub.2 phase in each cast alloy body.
It is clear from FIG. 5 that decrease in the oxygen content leads
to decrease in the NiTi.sub.2 phase content. FIG. 6 shows the
relation between an oxygen content and the relative intensity of a
Nb.sub.40Ti.sub.15Ni.sub.45 phase in each cast alloy body. Although
the cast alloy bodies of Examples 1-4 and Comparative Examples 1
and 2 having an oxygen content of 1920 ppm or less did not have a
Nb.sub.40Ti.sub.15Ni.sub.45 phase affecting rollability extremely
adversely, those of Comparative Examples 3 and 4 having an oxygen
content of 2240 ppm and 5000 ppm, respectively, had a
Nb.sub.40Ti.sub.15Ni.sub.45 phase.
[0059] Although the cast alloy bodies of Comparative Examples 1 and
2 having an oxygen content of 1030 ppm and 1920 ppm, respectively,
did not have a Nb.sub.40Ti.sub.15Ni.sub.45 phase, they contained a
relatively large amount of a NiTi.sub.2 phase adversely affecting
rollability. It is clear from above that to suppress the formation
of the Nb.sub.40Ti.sub.15Ni.sub.45 phase and the NiTi.sub.2 phase,
the oxygen content should be 1000 ppm or less.
[0060] FIGS. 7 and 8 are SEM photographs showing the cross section
structures of the cast alloy bodies of Example 3 and Comparative
Example 4. Although the cast alloy body of Example 3 having an
oxygen content of 400 ppm had a primary phase (Nb,Ti)p and a
eutectic phase [NiTi phase+(Nb,Ti)e phase], it had substantially no
NiTi.sub.2 phase and Nb.sub.40Ti.sub.15Ni.sub.45 phase. On the
other hand, the cast alloy body of Comparative Example 4 having an
oxygen content of 5000 ppm had large amounts of NiTi.sub.2 and
Nb.sub.40Ti.sub.15Ni.sub.45 phases, together with a primary phase
(Nb,Ti)p and a eutectic phase [NiTi phase+(Nb,Ti)e phase].
[0061] The composition of the primary phase (Nb,Ti)p in the cast
alloy bodies of Examples 1 and 3 and Comparative Example 2 was
analyzed by SEM-EDX. The results are shown in Table 2.
TABLE-US-00002 TABLE 2 Ni Nb Ti Oxygen No. (atomic %) (atomic %)
(atomic %) Content (ppm) Example 1 5.03 81.76 13.21 110 Example 3
4.48 84.50 11.02 400 Comparative 3.19 88.85 7.96 1920 Example 2
[0062] The comparison of the compositions of primary phases in
Examples 1 and 3 and Comparative Example 2 revealed that as the
oxygen content increased, the primary phase had a higher Nb
concentration, resulting in drastic decrease in the Ti
concentration. This appears to be due to the fact that as the
oxygen content increased, Ti migrated from the primary phase to the
eutectic phase. Presumably because Ti coming out of the primary
phase reacted with a NiTi phase in the eutectic phase, the
NiTi.sub.2 phase increased.
[0063] With respect to the cast alloy bodies of Example 3 and
Comparative
[0064] Example 4, the EPMA analysis results are shown in FIGS. 9
and 10, in which the axis of abscissas represents a scanning
distance, and the axis of ordinates represents the relative peak
intensities of Nb, Ti, Ni and O. It should be noted that to include
the data of all elements in one graph, the relative intensities do
not have correlations with the concentrations of elements. The
oxygen content (averaged cps determined from arbitrary 7 points) in
the primary phase (Nb,Ti)p was 1849 cps in Example 3, and 2242 cps
in Comparative Example 4.
[0065] In the cast alloy body of Example 3 having a small oxygen
content, oxygen exists predominantly in the primary phase, while in
the cast alloy body of Comparative Example 4 having a large oxygen
content, the oxygen content in the primary phase increased only
slightly. On the other hand, the oxygen content in a eutectic phase
remarkably increased in Comparative Example 4. It is thus
considered that a NiTi.sub.2 phase and a
Nb.sub.40Ti.sub.15Ni.sub.45 phase capable of incorporating a large
amount of oxygen were formed.
[0066] Among cast alloy bodies having a composition of
Nb.sub.100-x-yTi.sub.xNi.sub.y (atomic %), an alloy in which x=20,
and y=40, an alloy in which x=40, and y=20, an alloy in which x=20,
and y=20, and an alloy in which x=40, and y=40 were evaluated with
respect to rollability under the same conditions as in Example 1.
As a result, it was found that alloys were rolled at high rolling
ratios as long as they had an oxygen content of 1000 ppm or
less.
EFFECT OF THE INVENTION
[0067] Because the hydrogen-permeable Nb--Ti--Ni alloy of the
present invention has an oxygen content adjusted to 1000 ppm or
less in an as-cast state, it has good rollability and excellent
hydrogen permeability and hydrogen embrittlement resistance, with
the formation of intermetallic compounds substantially suppressed.
Accordingly, a thin, hydrogen-permeable film having excellent
hydrogen permeability and hydrogen embrittlement resistance can be
mass-produced by a low-cost method by which rolling is conducted
after casting a Nb--Ti--Ni alloy. The Nb--Ti--Ni alloy with such a
low oxygen content can be obtained by removing oxygen from its melt
with a deoxidizer in an atmosphere containing a reduced amount of
an oxygen gas.
* * * * *