⺰ᢥZr(Mn0.5Cr0.5)2 ߩᵴᕈൻߣ᳓⚛ๆ෼᜼േේ ᱜᙗ 1)㧘⩆㊁ ᘕᐔ 2)㧘⷏᧛ సᒾ 2)㧘᧻ጊ ᡽ᄦ 1)1) ንጊᄢቇ ᳓⚛ห૏૕⑼ቇ⎇ⓥ࠮ࡦ࠲࡯‫ޥ‬930-8555 ንጊᏒ੖⑔ 31902) ንጊᄢቇ Ꮏቇㇱ‫ޥ‬930-8555 ንጊᏒ੖⑔ 3190

Activation of Zr(Mn0.5Cr0.5)2 and its hydrogen absorption behavior
Masanori Hara1), Shinpei Ogino2), Katsuhiko Nishimura2),
Masao Matsuyama1)
Hydrogen Isotope Research Center, University of Toyama
Gofuku 3190, Toyama 930-8555, JAPAN
Faculty of Engineering, University of Toyama
Gofuku 3190, Toyama 930-8555, JAPAN(Received November 17, 2011; accepted March 9, 2012)
AbstractTo obtain the isotherms of Zr(Mn1-xCrx)2 - H system, the activation process
was studied. The Zr(Mn0.5Cr0.5)2 sample prepared was heated at 873 K for 2 hrs in
vacuum as the activation process for isotherm measurements. The isotherm atambient temperature had a single plateau. However, the width of the plateau region
decreased in the course of repetitive isotherm measurements, and the plateau
disappeared by the 5th measurement. The disappearance of the plateau region
would be explained by the surface poisoning due to the chromium oxide yielded by
the activation process.

1㧝㧚✜⸒
 ZrMn2ว㊄ߪ᳓⚛ๆ⬿ว㊄ߣߒߡ⍮ࠄࠇߡ޿ࠆ[1-4]㧚ߎߩว㊄ߩ᳓⚛ൻ‛↢ᚑߩᾲജ
ቇ․ᕈࠍᄌൻߐߖࠆߚ߼ߦ㧘Mnࠍઁߩర⚛ߢ⟎឵ߐߖࠆߎߣ߇ᐢߊⴕࠊࠇߡ޿ࠆ[5]㧚
଀߃߫㧘ZrMn2ߩMnࠍCoߢ⟎឵ߔࠆߎߣߦࠃࠅ᳓⚛ๆ෼ᐔⴧ࿶ജ߇㜞ߊߥࠅ㧘ZrMn2ߢߪ৻Ბߩࡊ࡜࠻࡯㗔ၞ߇CoߦࠃࠆMnߩ⟎឵ߦࠃࠅੑᲑߩࡊ࡜࠻࡯㗔ၞࠍᜬߟࠃ߁
ߦߥࠆߎߣ߇ႎ๔ߐࠇߡ޿ࠆ[6]㧚ߒ߆ߒ㧘Crߢ⟎឵ߒߚ㓙ߩᾲജቇ․ᕈߩᄌൻߪ߶ߣ
ࠎߤ⍮ࠄࠇߡ޿ߥ޿㧚ߘߎߢ㧘Zr(Mn1-xCrx)2ว㊄ߩ᳓⚛ๆ෼․ᕈࠍ᷹ቯߒ㧘Crᷝടߩᓇ㗀ࠍ⹏ଔߒ㧘ZrMn2߳ߩర⚛ᷝടߩലᨐࠍ᣿ࠄ߆ߦߔࠆߎߣ߇ᦼᓙߐࠇࠆ㧚 ੹࿁㧘Zr(Mn1-xCrx)2ว㊄ߩ᳓⚛ๆ෼╬᷷✢ߩ᷹ቯߦవ┙ߜ㧘Zr(Mn0.5Cr0.5)2ว㊄ߩᵴᕈൻߦ㑐ߔࠆ໧㗴ὐߣߘߩᄬᵴ․ᕈࠍᬌ⸛ߒߚ㧚㧞㧚ታ㛎ᣇᴺ㧞㧚㧝 Zr(Mn0.5Cr0.5)2 ߩ⺞⵾ Zr(Mn0.5Cr0.5)2ࠍ⹜ᢱߣߒߡ⺞⵾ߒߚ㧚Უ᧚ߦߪ99.7 %ߩZr㧔ࡈ࡞࠙࠴ൻቇ␠⵾㧕㧘99.9 %ߩMn㧔࡟ࠕࡔ࠲࡝࠶ࠢ␠⵾㧕෸߮99.99 %ߩCr㧔ࡈ࡞࠙࠴ൻቇ␠⵾㧕ࠍ↪޿ߚ㧚ߎࠇࠄᲣ᧚ࠃࠅZrࠍ10.290 g㧘Mnࠍ6.3614 g 㧘Crࠍ5.9010 gߪ߆ࠅߣࠅ㧘㉄⚛ࠥ࠶࠲࡯↪ߩࠫ࡞ࠦ࠾࠙ࡓߣߣ߽ߦࠕ࡞ࠧࡦࠕ࡯ࠢṁ⸃Ἱߦ౉ࠇߚ㧚Ἱౝࠍ1×10-3 Paએਅ߹ߢឃ᳇ࠍߒߚᓟ㧘ࠕ࡞ࠧࡦࠍዉ౉ߒߚ㧚Უ᧚ߩṁ⸃ߦవ┙ߜ㧘㉄⚛ࠥ࠶࠲࡯↪ߩࠫ࡞ࠦ࠾࠙ࡓࠍࠕ࡯ࠢṁ⸃ߒ㧘ࠕ࡞ࠧࡦਛߦᱷ⇐ߔࠆ㉄⚛ߩૐᷫࠍ࿑ߞߚ㧚ᰴ޿ߢ㧘Უ᧚ߩṁ⸃ߣ෻ォࠍਃ࿁➅ࠅ㄰ߒ㧘⹜ᢱߩZr(Mn0.5Cr0.5)2ࠍᓧߚ㧚ߎߩ⹜ᢱߩ৻ㇱߪᯏ᪾⊛ߦ☳⎈ߒ☳ᧃߣߒ㧘᳓⚛ๆ෼╬᷷✢ߩ᷹ቯߦ↪޿ߚ㧚

2 Fig.1ߦ⺞⵾ߒߚ
Zr(Mn0.5Cr0.5)2ߩ☳ᧃX✢࿁᛬ࡄ࠲࡯ࡦࠍ␜ߔ㧚᷹ⷰߐࠇߚ࿁᛬ࡇ࡯ࠢߪ౐ᣇ᥏ߢ
ᜰᢙઃߌ߇ߐࠇ[7]㧘ᓧࠄࠇߚᩰሶቯᢙߪa=5.032×10-10㨙㧘c=8.260×10-10 㨙ߢ޽ߞߚ㧚ߥ߅㧘44°ઃㄭߦᜰᢙઃ
ߌߢ߈ߥ޿ࡇ࡯ࠢ߇᷹ⷰߐ

Fig. 1. X-ray diffraction pattern of Zr(Mn0.5Cr0.5)2

ࠇߚ㧚Table 1ߦᓧࠄࠇߚᩰ

prepared by argon arc-melting. The pattern wastaken using Cu-Kα line.

ሶቯᢙߣႎ๔ߐࠇߡ޿ࠆZrMn2෸߮ZrCr2ߩᩰሶቯᢙࠍ␜ߔ[7-11]㧚ᓧࠄࠇߚ୯ߪႎ๔୯ߦㄭ޿୯ࠍ␜ߒߡ߅ࠅ㧘⺞⵾ߒߚ⹜ᢱߪZr(Mn0.5Cr0.5)2ߢ޽ࠆߣ್ᢿߒߚ㧚

Table 1. Crystal structure of Zr(Mn0.5Cr0.5)2
Zr(Mn0.5Cr0.5)2

Crystal structure

Lattice constant/mreference

hexagonal

a=5.032x10-10This work

c=8.260x10-10ZrMn2

a=5.041x10-10

hexagonal

8c=8.249x10-10ZrMn2

a=5.026x10-10

hexagonal

9c=8.258x10-10
ZrCrMna=5.07x10-10

hexagonal

7c=8.323x10-10
ZrCr2

a=5.102x10-10

hexagonal

10c=8.294x10-10
ZrCr2

a=5.096x10-10

hexagonal

c=8.26x10-10311㧞㧚㧞 ᳓⚛ๆ෼╬᷷✢ߩ᷹ቯ ⹜ᢱߩ᳓⚛ๆ෼╬᷷✢ߩ᷹ቯߦߪ㜞⌀ⓨⵝ⟎ࠍ૶↪ߒߚ㧚ឃ᳇♽ߦߪࡠ࡯࠲࡝࡯ࡐࡦࡊߣ࠲࡯ࡏಽሶࡐࡦࡊࠍ஻߃㧘᳓⚛ᐔⴧ࿶ജߩ᷹ቯߦߪࠠࡖࡄࠪ࠲ࡦࠬࡑࡁࡔ࡯࠲࡯ࠍ૶↪ߒߚ㧚 ⍹⧷⵾ߩ෻ᔕ▤ߦ1.8 gߩ⹜ᢱࠍ౉ࠇ㧘㜞⌀ⓨⵝ⟎ߦขࠅઃߌ㧘෻ᔕኈེౝࠍ1.3×10-5Pa߹ߢឃ᳇ߒߚ㧚ᵴᕈൻಣℂߣߒߡ873 Kߢ2ᤨ㑆ߩ⌀ⓨടᾲࠍⴕߞߚ㧚ቶ᷷߹ߢ಄ළ
ᓟ㧘㊀᳓⚛ߩๆ෼╬᷷✢ࠍ᷹ቯߒߚ㧚ߎߩ╬᷷✢ߩ᷹ቯߪ㧘෻ᔕኈེౝߦ㗅ᰴ㊀᳓⚛ࠍᷝടߒߡ޿߈㧘ᐔⴧ࿶ജࠍ᷹ቯߔࠆߎߣߦࠃࠅⴕߞߚ㧚᷹ቯᓟ㧘873 Kߢ2ᤨ㑆ߩടᾲࠍ⌀ⓨਛߦߡⴕ޿⣕᳓⚛ൻߒ㧘➅ࠅ㄰ߒ㊀᳓⚛ߩๆ෼╬᷷✢ࠍ᷹ቯߒߚ㧚㧟㧚⚿ᨐߣ⠨ኤ ➅ࠅ㄰ߒ᳓⚛ๆ෼╬᷷✢ࠍ᷹ቯߒߚ㓙ߩᄌൻࠍ Fig. 2 ߦ␜ߔ㧚ߥ߅㧘433K ߢⴕߞߚ 4 ࿁⋡ߩ᷹ቯࠍߩߙ߈㧘޿ߕࠇ߽ቶ
᷷ߢ᷹ቯࠍⴕߞߚ㧚᳓⚛ๆ෼ࠍߪߓ߼ߡⴕߞߚ႐วߩ╬᷷✢ߦߪ㧘ቶ᷷ߢ 1 kPa ߩᐔⴧ᳓⚛
࿶ജࠍᜬߟࡊ࡜࠻࡯㗔ၞ߇[D]/[Zr(Mn0.5Cr0.5)2]<2 ߩ▸࿐ߢⷰኤߐࠇߚ㧚ߘߩᓟ㧘873K ߢ

Fig. 2. Change in isotherm curves with repetitive

2 ᤨ㑆ߩ⌀ⓨടᾲߦࠃࠆ⣕᳓⚛

measurements at ambient temperature.

4ൻߣ᷹ቯࠍ➅ࠅ㄰ߔߦᓥ޿ࡊ࡜࠻࡯㗔ၞߪ᷹ቯᲤߦ⁜ߊߥߞߚ㧚ߎߩේ࿃ߣߒߡ㧘᳓⚛ๆ෼ߩㅦᐲ߇ᷫዋߒߚߚ߼㧘ᐔⴧߦ㆐ߔࠆᤨ㑆߇㐳ߊߥࠅ㧘ᐔⴧ࿶ജࠍ᷹ቯߒߡ޿ߥ޿੐߇⠨߃ࠄࠇߚ㧚ߘߎߢ㧘෻ᔕㅦᐲࠍჇടߐ
ߖࠆߚ߼ߦ 433K ߢ 4 ࿁⋡ߩ╬᷷✢᷹ቯࠍⴕߞߚ㧚ߘߩ⚿ᨐ㧘ࡊ࡜࠻࡯㗔ၞ߇ࠊߕ߆ߦ⷗ࠄࠇߚ㧚ߒ߆ߒ㧘ቶ᷷ߢߩ᷹ቯߢ޽ࠆ 5 ࿁⋡ߢߪࡊ࡜࠻࡯㗔ၞߪ᷹ⷰߐࠇߥ߆ߞߚ㧚ߘߩᓟ㧘⌀ⓨFig. 3. Change in X-ray diffraction patterns ofടᾲߦࠃࠆ⣕᳓⚛ൻߣ╬᷷

Zr(Mn0.5Cr0.5)2. These patterns were taken using
Cu-kα line. The pattern of the as-prepared sample in✢ߩ᷹ቯࠍⴕߞߡ߽ೋᦼߩ

Fig. 3(a) was assigned as shown in Fig. 1

ࠃ߁ߥࡊ࡜࠻࡯㗔ၞߪ⃻ࠇheated for 20 hrs at 873 K in vacuum gave Fig. 3(b).
Fig.

3(c)

wasobtainedfromThe sample
thesampleߥ߆ߞߚ㧚dehydrogenation by vacuum heating after isotherm ࡊ࡜࠻࡯㗔ၞߩᶖᄬߩේmeasurements (see Fig. 2).

࿃ࠍᬌ⸛ߔࠆߚ߼ߦ㧘20ᤨ㑆ߩ⌀ⓨടᾲࠍⴕߞߚ⹜ᢱߣ╬᷷✢᷹ቯᓟߩ⹜ᢱߦߟ޿ߡX✢࿁᛬ࡄ࠲࡯ࡦߩ᷹ቯࠍⴕߞߚ㧚Fig. 3ߦߘߩ⚿ᨐࠍ␜ߔ㧚Fig. 3(a)ߪ⌀ⓨടᾲ╬ߩಣ
ℂࠍᣉߒߡ޿ߥ޿⹜ᢱ㧘Fig㧚3(b)ߪ873Kߢ20ᤨ㑆ߩ⌀ⓨടᾲࠍᣉߒߚ⹜ᢱ㧘Fig. 3(c)ߪFig. 2ߦ␜ߒߚ᳓⚛ๆ෼╬᷷✢ߩ᷹ቯ⚳ੌᓟߦ⌀ⓨടᾲߦࠃࠅ⣕᳓⚛ൻߒߚ⹜ᢱߢ޽5

ࠆ㧚Fig. 3(b)ߦ␜ߔ873Kߢ20ᤨ㑆⌀ⓨടᾲࠍⴕߞߚ⹜ᢱߩ࿁᛬ࡄ࠲࡯ࡦߪࠕ࡯ࠢṁ⸃ߦࠃࠅ⺞⵾ߒߚ࿁᛬ࡄ࠲࡯ࡦ㧔Fig. 3(a))ߣ৻⥌ߒߡ߅ࠅ㧘⌀ⓨടᾲߦࠃࠅว㊄⋧ߩಽ⸃ߪ⿠ߎࠄߥ޿ߎߣ߇ಽ߆ߞߚ㧚߹ߚ㧘᳓⚛ๆ෼╬᷷✢ߩ᷹ቯࠍⴕߞߚ⹜ᢱߩ࿁᛬ࡄ࠲
࡯ࡦ㧔Fig3.(c))߽⺞⵾ᓟߩ࿁᛬ࡄ࠲࡯ࡦߣ৻⥌ߒߚ㧚ߎࠇߪ㧘⌀ⓨടᾲߣ╬᷷✢ߩ᷹ቯߩ➅ࠅ㄰ߒߢߪว㊄⋧ߩಽ⸃߇⿠ߎࠄߥ޿ߎߣࠍ␜ߒߡ޿ࠆ㧚හߜ㧘╬᷷✢ߩ᷹ቯࠍ➅ࠅ㄰ߒⴕ߁ߎߣߦࠃࠅࡊ࡜࠻࡯㗔ၞ߇ᷫዋߒߚߩߪว㊄⋧ߩಽ⸃ߢߥߊ㧘ઁߩⷐ࿃ߦࠃࠆߎߣ߇᣿ࠄ߆ߣߥߞߚ㧚ㅢᏱ㧘㊄ዻߣ᳓⚛ಽሶߩ෻ᔕߦࠃࠆ㊄ዻ᳓⚛ൻ‛ߩ↢ᚑߪ㧘(1)㊄ዻ⴫㕙ߢߩ᳓⚛ಽሶߩๆ⌕ߣ⸃㔌ߦࠃࠆ᳓⚛ේሶߩ↢ᚑ㧘(2)↢ᚑߒߚ᳓⚛ේሶߩ
㊄ዻౝ߳ߩ᜛ᢔ㧘(3)᳓⚛ේሶߣ㊄ዻߩ෻ᔕࠃࠆේሶߩౣ㈩೉ߣ᳓⚛ൻ‛⋧ߩᚑ㐳ߢ߅ߎࠆ㧚ߎߎߢ㧘ว㊄⋧⥄りߩᄌൻ߇ߥ޿ߩߢ㧘(3)ߩㆊ⒟߇᳓⚛ๆ෼ࠍ㒖ኂߒߡ޿ࠆⷐ࿃ߢߪߥ޿ߣ⠨߃ࠄࠇࠆ㧚(2)ߩㆊ⒟ߪ᳓⚛ේሶ߇㊄ዻ⴫㕙ߢ↢ᚑߒߡ޿ࠇ߫㧘ኈᤃߦ⿠ߎࠆߎߣ߇⍮ࠄࠇߡ޿ࠆ㧚એ਄ߩߎߣ߆ࠄ㧘㊄ዻ⴫㕙ߢ᳓⚛ේሶ߇↢ᚑߒߥ޿ߎߣ߇᳓⚛ๆ෼ࠍ㒖ኂߒߡ޿ࠆⷐ࿃ߣߥߞߡ޿ࠆߣ␜ໂߐࠇߚ㧚 ߘߎߢ㧘⴫㕙⚵ᚑࠍ⿛ᩏ㔚ሶ㗼ᓸ㏜ߦ஻߃ࠄࠇߚX✢ಽᨆⵝ⟎ߦࠃࠅర⚛ಽᨆࠍⴕߞߚ㧚ߘߩ⚿ᨐࠍTable 2ߦ␜ߔ㧚ߥ߅㧘⴫㕙ߩర⚛⚵ᚑࠍZrߦኻߒߡⷙᩰൻߒߚ㧚ടᾲ೨ᓟߢว㊄ߩ᭴ᚑర⚛ߢ޽ࠆ㧘ࠫ࡞ࠦ࠾࠙ࡓ㧘ࡑࡦࠟࡦ㧘ࠢࡠࡓߩ⚵ᚑߦᄢ߈ߥᄌൻߪ⷗ࠄࠇߥ߆ߞߚ㧚৻ᣇ㧘㉄⚛ߩഀว߇ᄢ߈ߊߥߞߡ޿ࠆߎߣ߇ಽ߆ߞߚ㧚ߎߩ㉄⚛⚵ᚑߩჇᄢߪ⴫㕙ࠍⷒ߁㉄ൻ‛߇↢ᚑߒߚߎߣߦኻᔕߔࠆߣ⠨߃ࠄࠇࠆ㧚හߜ㧘(1)ߩㆊ⒟ߩ⹜ᢱ⴫㕙ߢߩ᳓⚛ಽሶߩ⸃㔌ࠍ㒖ኂߒߡ޿ߚߩߪ㊄ዻ㉄ൻ‛ߩ↢ᚑ߇ⷐ࿃ߢ޽ࠆߣ

Table 2. Surface composition of Zr(Mn0.5Cr0.5)2 before and after heat treatment
OxygenManganese

Chromium

Zirconium

Before heat treatment

0.13

1.08

1.13

1.00

After heat treatment

0.86

0.98

1.14

1.00

6ផ᷹ߐࠇࠆ㧚ߎߩⷰὐࠃࠅ᭴ᚑర⚛ߩ㉄ൻ‛ߦߟ޿ߡᬌ⸛ߒߚ㧚Zr-Oߩ⋧࿑[12]ࠃࠅ㧘Zrߪ473 K⒟ᐲߢ8 at.%⒟ᐲߩ㉄⚛࿕ኈ㒢ࠍᜬߟߎߣ߇⍮ࠄࠇߡ޿ࠆ㧚ߎߩߚ߼㧘ടᾲߦࠃࠅ⴫㕙ߩ㉄⚛ࠍ࿕ኈߐߖࠆߎߣ߇ߢ߈ࠆ㧚Mn߽ห᭽ߦ2 at.%⒟ᐲߩ㉄⚛࿕ኈ㒢ࠍᜬߟ[13]㧚ߎߩߚ߼㧘ZrMn2ߪ873 Kߢ2ᤨ㑆ߩ⌀ⓨടᾲߦࠃࠅᵴᕈൻࠍⴕ߁ߎߣ߇ߢ߈ࠆߣ⠨߃ࠄࠇࠆ㧚ߒ߆ߒ㧘Crߪ㉄⚛ࠍ࿕ኈߖߕ㧘Cr2O3ࠍ↢ᚑߔࠆ[14]㧚߹ߚ㧘Cr2O3
ߪ߈ࠊ߼ߡ቟ቯߥ㉄ൻ‛ߢ޽ࠅ2600 K⒟ᐲߩടᾲߢ߽ಽ⸃ߒߥ޿㧚ߎߩߚ߼㧘Cr2O3
߇⴫㕙ߦടᾲߣߣ߽ߦ↢ᚑߒ㧘᳓⚛ๆ෼ࠍ㒖ኂߒߡ޿ࠆߣ⠨߃ࠄࠇࠆ㧚ઁߩਃర♽ว㊄
ߢ޽ࠆZr(Mn1-xCox)2ว㊄ߢߪ㧘873 Kߢ2ᤨ㑆ߩടᾲࠍ➅ࠅ㄰ߒߡ߽ኈᤃߦᵴᕈൻߢ߈㧘ౣ⃻ᕈߩ޽ࠆ╬᷷✢ࠍ᷹ቯߢ߈ߚ[6]㧚Co-Oߩ⋧࿑[15]ࠃࠅ㧘Coߪ0.01 at%⒟ᐲߩ㉄⚛
ࠍࠊߕ߆ߦ࿕ኈߔࠆߎߣ߇␜ߐࠇߡ޿ࠆ㧚ߒ߆ߒ㧘ߘߩṁ⸃㊂ߪࠊߕ߆ߢ޽ࠆ㧚৻ᣇ㧘↢ᚑߔࠆ㉄ൻ‛ߪCr2O3ߦᲧߴૐ޿Ⲣὐࠍ߽ߜ㧘298.15KߢߩGibbs⥄↱ࠛࡀ࡞ࠡ࡯ᄌൻߪCoOᒰߚࠅߢ-214.22 kJ/molߢ޽ࠅ[16]㧘Cr2O3ߪ-1058.1kJ/molߢ޽ࠆ[16]㧚CoOߪCr2O3⋧ߦᲧߴਇ቟ቯߥ㉄ൻ‛ߢ޽ࠆ㧚ߟ߹ࠅ㧘➅ࠅ㄰ߒᵴᕈൻ߇ߢ߈ߚว㊄ߢߪ㧘᭴ᚑߔࠆర⚛ߪ޿ߕࠇ߽㉄⚛ࠍ࿕ኈߔࠆర⚛ߢ޽ࠆ߆㧘㉄⚛ࠍ࿕ኈߒߥ޿ర⚛ߩ㉄ൻ‛ߩ቟ቯᕈ߇ૐ޿ߎߣ߇ಽ߆ߞߚ㧚 એ਄ߩߎߣࠃࠅ㧘Zr(Mn0.5Cr0.5)2ว㊄ࠍ➅ࠅ㄰ߒᵴᕈൻߔࠆߦߟࠇ㧘᳓⚛ๆ෼߇⷗ࠄࠇߥߊߥࠆ⃻⽎ߪ㧘ࠢࡠࡓ㉄ൻ‛߇ടᾲߦࠃࠅ⴫㕙ߦᒻᚑߔࠆߣ⠨߃ࠆߎߣߦࠃࠅ⺑᣿ߢ߈ࠆߎߣ߇᣿ࠄ߆ߣߥߞߚ㧚ߟ߹ࠅ㧘Zr(Mn0.5Cr0.5)2ว㊄ࠍ➅ࠅ㄰ߒᵴᕈൻߐߖࠆߚ߼ߦߪ㧘⌀ⓨਛߢߩടᾲߦࠃࠆᵴᕈൻߪㆡಾߢߥ޿㧚㧠㧚⚿⺰ Zr(Mn0.5Cr0.5)2 ว㊄ࠍ⌀ⓨടᾲߦࠃࠅᵴᕈൻߒߚᓟߩ᳓⚛ๆ෼᜼േߣᵴᕈൻߩ➅ࠅ㄰ߒߦࠃࠆᄬᵴㆊ⒟ࠍ᷹ቯߒߚ㧚ߘߩ⚿ᨐ㧘ᦨೋߩᵴᕈൻᓟߩ᳓⚛ๆ෼╬᷷✢ߩ᷹ቯߢߪ㧘7᣿⍎ߥࡊ࡜࠻࡯㗔ၞ߇᷹ⷰߐࠇߚ㧚ߒ߆ߒ㧘ᵴᕈൻࠍ➅ࠅ㄰ߒ᷹ቯߔࠆߦߟࠇࡊ࡜࠻࡯
㗔ၞߪ⁜ߊߥࠅ㧘ᵴᕈൻߣ╬᷷✢ߩ᷹ቯࠍ 5 ࿁➅ࠅ㄰ߔߣࡊ࡜࠻࡯㗔ၞߪ᷹ⷰߐࠇߥߊ
ߥߞߚ㧚ߒ߆ߒ㧘X ✢࿁᛬ࡄ࠲࡯ࡦߦߪᵴᕈൻࠍ➅ࠅ㄰ߒߚᓟߩ⹜ᢱߣᒰೋߩว㊄ߢߪ㆑޿߇⷗ࠄࠇߥ߆ߞߚ㧚ߎߩߚ߼㧘᳓⚛ๆ෼㊂ߩᷫዋߪว㊄⴫㕙ߢ᳓⚛ߩ⸃㔌߇㒖ኂߐࠇߡ޿ࠆߎߣߦࠃࠆߣ⠨߃ࠄࠇߚ㧚⴫㕙ߩర⚛ಽᨆࠍⴕߞߚߣߎࠈ㧘ᵴᕈൻࠍ➅ࠅ㄰ߔߎߣߦࠃࠅ㧘ว㊄⴫㕙ߩ㉄⚛㊂߇Ⴧടߒߡ޿ࠆߎߣ߇ಽ߆ߞߚ㧚Zr(Mn0.5Cr0.5)2 ߩ᭴ᚑర⚛ߢ޽ࠆࠫ࡞ࠦ࠾࠙ࡓ㧘ࡑࡦࠟࡦ෸߮ࠢࡠࡓߣ㉄⚛ߩ⋧࿑ࠃࠅ㧘ࠫ࡞ࠦ࠾࠙ࡓ㧘ࡑࡦࠟࡦߢߪ㉄⚛ࠍ࿕ኈߔࠆ߇㧘ࠢࡠࡓߪ㉄ൻ‛ࠍ↢ᚑߒ㉄⚛ࠍ࿕ኈߒߥ޿ߎߣ߇ಽ߆ߞߚ㧚ࠃߞߡ㧘ᵴᕈൻࠍ➅ࠅ㄰ߔߎߣߦࠃࠅ᳓⚛ๆ෼߇⷗ࠄࠇߥߊߥࠆߩߪ㧘⴫㕙ߦࠢࡠࡓ㉄ൻ‛߇↢ᚑߒ㧘᳓⚛ߩ⸃㔌ࠍ㒖ኂߔࠆߚ߼᳓⚛ๆ෼߇⷗ࠄࠇߥߊߥࠆߎߣ߇᣿ࠄ߆ߣߥߞߚ㧚ෳ⠨ᢥ₂[1] N. Nishimiya, Mat. Res. Bull., 21(1986)1025-1037.
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