㕖ᐔⴧ᳓⚛᳇ᵹਛߦ߅ߌࠆ࠴࠲ࡦ㉄ൻ‛ߣㆫ⒖㊄ዻᷙว૕ߩㆶర෻ᔕ
⎇ⓥઍ⴫⠪੩ㇺᄢቇᎿቇ⎇ⓥ⑼᧚ᢱᎿቇኾ᡹ಎᢎ᝼ቝ↰ື਽1. ✜⸒
 ࠴࠲ࡦߪ㉄⚛ߣߩ㑆ߦᭂ߼ߡᒝ޿ⷫ๺ജࠍ᦭ߒ‫ߦࠄߐޔ‬㊄ዻ࠴࠲ࡦਛߦߪ㉄⚛߇ᄙ㊂ߦ
࿕ṁߔࠆߚ߼‫㉄ࡦ࠲࠴ޔ‬ൻ‛߆ࠄ㊄ዻ࠴࠲ࡦࠍ⋥ធขࠅ಴ߔߎߣߪ࿎㔍ߢ޽ࠆ‫ޕ‬࿑ 1 ߦ‫ޔ‬⒳‫㉄ࡦ࠲࠴ߩޘ‬ൻ‛߹ߚߪ᳓⚛ߣ᳓߇ᐔⴧߔࠆߣ߈ߩ㉄⚛ߩൻቇࡐ࠹ࡦࠪࡖ࡞ࠍ␜ߔ‫㉄ޕ‬ൻ‛ࠍ᳓⚛ㆶరߒߚ႐ว‫ޔ‬೽↢ᚑ‛ߩ᳓⫳᳇߇ࠟࠬႺ⤑ਛߦߣߤ߹ࠆߚ߼‫ޔ‬᳓⚛᳇ᵹਛߢ޽ߞߡ߽᳓⫳᳇ಽ࿶ pH2O ߪ 10-4 atm ⒟ᐲߢ޽ࠆ‫ޕ‬ᓥߞߡ‫ޔ‬ㅢᏱߩ᳓⚛ㆶరߢߪ‫߫߃଀ޔ‬᷷
ᐲ 1000 qC ߢߪ Ti3O5 ߇↢ᚑߔࠆߦ⇐߹ࠆ‫ޕ‬

࿑ 1 ⒳‫㉄ࡦ࠲࠴ߩޘ‬ൻ‛ห჻߹ߚߪ᳓⚛ߣ᳓߇ᐔⴧߔࠆᤨߩ㉄⚛ߩൻቇࡐ࠹ࡦࠪࡖ࡞ ߒ߆ߒ‫㉄ࡦ࠲࠴ޔ‬ൻ‛ࠍ࠴࠲ࡦߣߩⷫ๺ജ߇ᒝ޿㊄ዻߣߩ౒ሽਅߢ᳓⚛ㆶరߔࠆߣ‫࠴ޔ‬
࠲ࡦว㊄߇↢ᚑߔࠆߎߣ߇ႎ๔ߐࠇߡ޿ࠆ‫㉄ࡦ࠲࠴ޔ߫߃଀ޕ‬ൻ‛ߣ⊕㊄ߩᷙว૕ࠍ᳓⚛
ㆶరߔࠆߣ‫ޔ‬
Pt3Ti ߇↢ᚑߔࠆߎߣ߇ Worrel ߿ᒰ⎇ⓥࠣ࡞࡯ࡊߦࠃߞߡ⏕⹺ߐࠇߡ޿ࠆ[1,2]‫ޕ‬ߎߩࠃ߁ߥ᳓⚛ㆶరߦࠃࠆ࠴࠲ࡦ㉄ൻ‛߆ࠄߩ⋥ធว㊄ൻߪ‫ߣࡦ࠲࠴ޔ‬ว㊄ర⚛ߣߩⷫ๺ജߛߌߢߥߊ‫ޔ‬᳓⚛ߩㆶరജ߽㊀ⷐߣߥࠆ߇‫ޔ‬ㅢᏱߩ᳓⚛ߢߪߏߊ㒢ࠄࠇߚ㊄ዻߣߒ߆ว㧙㧙㊄ൻߒߥ޿‫ޔߢࠈߎߣޕ‬ㄭᐕ‫ޔ‬᳓⚛ࠃࠅᒝജߥㆶర೷ߣߒߡ㕖ᐔⴧ᳓⚛߇⌕⋡ߐࠇ‫࠲࠴ޔ‬ࡦ㉄ൻ‛ߩ㕖ᐔⴧ᳓⚛ㆶర߽⎇ⓥߐࠇߡ޿ࠆ[3-5]‫ޔߦ․ޕ‬ૐ᷷᳓⚛ࡊ࡜࠭ࡑࠍ↪޿ߡ TiO2⭯⤑ࠍㆶరߒߚ႐ว‫ޔ‬ㅢᏱߩ᳓⚛ㆶరߢߪᓧࠄࠇߥ޿ૐ⚖㉄ൻ‛ TiO ߹ߢㆶరߐࠇࠆߎߣ
߇ႎ๔ߐࠇߚ[5]‫㉄ࡦ࠲࠴ޔߢߎߘޕ‬ൻ‛ߩ⋥ធว㊄ൻᴺߣ㕖ᐔⴧ᳓⚛ㆶరࠍ⚵ߺวࠊߖ‫ޔ‬ᣂߚߥዷ㐿ࠍ⋡ᜰߒߚ‫⎇ᧄޕ‬ⓥߢߪ‫ⷫߩߣࡦ࠲࠴ޔ‬๺ജ߇㜞޿㊄ዻߣߒߡ࠾࠶ࠤ࡞ߦ⌕⋡ߒߚ‫ޕ‬࿑ 2 (a) ߦ‫ޔ‬ႎ๔ߐࠇߡ޿ࠆ Ti-Ni-O ♽⋧ᐔⴧ⁁ᘒ࿑ࠍ␜ߔ[6]‫ޕ‬࿑߆ࠄࠊ߆ࠆࠃ߁ߦ‫ޔ‬
Ni3Ti ⋧ߦߪ㉄⚛߇ᱴߤ࿕ṁߒߥ޿ߚ߼‫㉄ޔ‬ൻ‛߆ࠄ࠴࠲ࡦࠍ㊄ዻ⁁ᘒߢขࠅ಴ߔߣ޿߁ὐߢㇺว߇ࠃ޿‫ޔߦࠄߐޕ‬Ni3Ti ߪᒻ⁁⸥ᙘࠍ␜ߔታ↪᧚ߢ޽ࠆ Ni-Ti ว㊄ߩᲣว㊄߳ߩ೑↪
߇ᦼᓙߢ߈ࠆ‫ޔߚ߹ޕ‬㕖ᐔⴧ᳓⚛ߦߪ⋥ᵹ᡼㔚ࡊ࡜࠭ࡑ‫ޔ‬㜞๟ᵄࡊ࡜࠭ࡑ‫ޔ‬ㆊ಄ළේሶ⁁᳓⚛ߥߤ޿ߊߟ߆ߩ⒳㘃߇޽ࠆ߇‫↢⊒ޔ‬ᣇᴺߩ㆑޿ߦࠃࠆㆶరജߩᏅߦߟ޿ߡ߽⥝๧ᷓ޿‫ޕ‬ߘߎߢᧄ⎇ⓥߢߪ‫ ߕ߹ޔ‬Ni-Ti-O ♽⋧ᐔⴧ⁁ᘒ࿑߅ࠃ߮ൻቇࡐ࠹ࡦࠪࡖ࡞࿑ࠍ↪޿ߡ᳓⚛ㆶరߦߟ޿ߡߩᾲജቇ⊛⠨ኤࠍⴕߞߚᓟߦ‫ޔ‬ૐ᷷᳓⚛ࡊ࡜࠭ࡑㆶర߅ࠃ߮ㆊ಄ළේሶ⁁᳓⚛
ㆶరࠍⴕߞߚ‫ޕ‬

࿑ 2 (a) Ti-Ni-O ♽⋧ᐔⴧ⁁ᘒ࿑ (b) Ni(ss), Ni3Ti ߣ⒳‫㉄ࡦ࠲࠴ߩޘ‬ൻ‛ߩᐔⴧ㑐ଥࠍ࠺ࡈࠜ
࡞ࡔߒߚᮨᑼ࿑

2. ᾲജቇ⊛⠨ኤ ࿑ 2 (b) ߪ࿑ 2 (a) ߩ⎕✢ㇱࠍ᜛ᄢߒ‫㉄ࡦ࠲࠴ޔ‬ൻ‛ߣ࠾࠶ࠤ࡞࿕ṁ૕ Ni(ss) ߅ࠃ߮ Ni3Tiߩ⋧ᐔⴧ㑐ଥࠍ࠺ࡈࠜ࡞ࡔߒߚᮨᑼ࿑ߢ޽ࠆ‫㉄ࡦ࠲࠴ޕ‬ൻ‛߇ TiO2, TinO2n-1, Ti4O7 ߢ޽ࠆߣ߈ߪ‫⋧࡞ࠤ࠶࠾ޔ‬ਛ߳࠴࠲ࡦߪ߶ߣࠎߤ࿕ṁߒߥ޿߇‫ޔ‬Ti3O5, Ti2O3 ߣ࠴࠲ࡦߩේሶଔ߇ૐ㧙㧙ߊߥࠆߦᓥߞߡ‫ߣࠇߘޔ‬ᐔⴧߔࠆ࠾࠶ࠤ࡞⋧ਛߩ࠴࠲ࡦỚᐲ߇ᄢ߈ߊߥࠆ‫ޕ‬Ni3Ti ߣᐔⴧߒ߁ࠆ࠴࠲ࡦ㉄ൻ‛ߪ Ti2O3 ߹ߚߪ TiO ߢ޽ࠆ‫⋧ߩࠄࠇߎޕ‬ᐔⴧ㑐ଥࠍ⠨ᘦߒ‫౒࡞ࠤ࠶࠾ޔ‬ሽਅߦ߅ߌࠆ࠴࠲ࡦ㉄ൻ‛ߩ᳓⚛ㆶరࠍ⠨ኤߔࠆߚ߼‫ޔ‬Ti-Ni-O ♽ൻቇࡐ࠹ࡦࠪࡖ࡞࿑ࠍ૞ᚑߒߚ‫ޕ‬ ࿑ 3 ߦ᷷ᐲ 1000 qC ߦ߅ߌࠆ Ti-Ni-O ♽ൻቇࡐ࠹ࡦࠪࡖ࡞࿑ࠍ␜ߔ‫ޕ‬࿑ 3 (a) ࠍឬߊߦᒰߚࠅᔅⷐߥฦൻว‛ߩ↢ᚑࠡࡉ࠭ࠛࡀ࡞ࠡ࡯ߪ Barin ߩ୯ࠍ↪޿ߚ[7]‫ޕ‬࿑ 3 (b) ߪ࿑ 3 (a) ߩlog pO2 – log aTi ᐔ 㕙 ߳ ߩ ᛩ ᓇ ࿑ ߢ ‫[ ޔ‬Chattopadhyay], [Liang], [Barin] ߪ ‫ࠇ ߙ ࠇ ߘ ޔ‬
Chattopadhyay, Liang, Barin ߦࠃߞߡႎ๔ߐࠇߚ Ni3Ti ߩ↢ᚑࠡࡉ࠭ࠛࡀ࡞ࠡ࡯[6-8]ࠍ↪޿ߡ⸘▚ߒߚ‫ޔ‬Ni(ss) ⋧ߣ Ni3Ti ⋧߇ੑ⋧ᐔⴧߣߥࠆߣ߈ߩ࠴࠲ࡦߩൻቇࡐ࠹ࡦࠪࡖ࡞ࠍ␜ߔ‫ޕ‬࿑ࠃࠅ‫౒࡞ࠤ࠶࠾ޔ‬ሽਅߢ࠴࠲ࡦ㉄ൻ‛ࠍㆶరߔࠆ႐ว‫ޔ‬㕖ᐔⴧ᳓⚛ߩㆶరജ߇ TiO ߇ᐔⴧ⋧ߣߥࠆ⒟ᐲߢ޽ࠇ߫‫ޔ‬Ni(ss) ߪᐔⴧߒᓧߥ޿ߚ߼‫ޔ‬Ni3Ti ߇↢ᚑߔࠆߎߣ߇ࠊ߆ࠆ‫ޕ‬Huetࠄߦࠃࠆ⎇ⓥߦࠃࠇ߫‫ޔ‬ૐ᷷᳓⚛ࡊ࡜࠭ࡑߪߎߩ᧦ઙࠍḩߚߒߡ޿ࠆߣ⠨߃ࠄࠇࠆ‫ޕ‬

࿑ 3 (a) Ti-Ni-O ♽ൻቇࡐ࠹ࡦࠪࡖ࡞࿑ߩ 3 ᰴర⴫␜ (b) Ti-Ni-O ♽ൻቇࡐ࠹ࡦࠪࡖ࡞࿑ߩ
log pO2 – log aTi ᐔ㕙߳ߩᛩᓇ࿑

3. ታ㛎ᣇᴺ Ꮢ⽼ߩ㉄ൻ࠴࠲ࡦ(IV) ☳ᧃߣ࠾࠶ࠤ࡞☳ᧃࠍࡕ࡞Ყߢ 1 : 3 ߣߥࠆࠃ߁⸘㊂ߒ‫ࡒ࡞࡯ࡏޔ‬࡞ߦࠃߞߡ☳⎈ᷙวߒ‫ޔ‬ဋ⾰ߥᷙว☳ᧃࠍᓧߚ‫৻ࠍࠇߎޕ‬ゲ࿶❗ߒࡍ࡟࠶࠻ࠍ૞⵾ߒߚ‫ޕ‬ߎߩࡍ࡟࠶࠻ࠍ↪޿ߡ‫ޔ‬ૐ᷷᳓⚛ࡊ࡜࠭ࡑㆶర‫ޔ‬ㆊ಄ළේሶ⁁᳓⚛ㆶరࠍⴕߞߚ‫ߚ߹ޕ‬ኻ㧙㧙ᾖታ㛎ߣߒߡㅢᏱߩ᳓⚛ㆶర߽ⴕߞߚ‫ޕ‬ૐ᷷᳓⚛ࡊ࡜࠭ࡑㆶరߦߪ‫ޔ‬㜞๟ᵄࡊ࡜࠭ࡑ⊒↢ⵝ⟎ࠍ↪޿‫⹜ޔ‬ᢱ᷷ᐲߪ 800 qC ߣߒߚ‫ޕ‬ㆊ಄ළේሶ⁁᳓⚛ㆶరߦߪ‫࡯ࡗࠗࡢ࠻࠶ࡎޔ‬ᴺࠍ↪޿ߚ‫࡯ࡗࠗࡢ࠻࠶ࡎޕ‬ᴺߣߪ‫ޔ‬ේሶ⁁᳓⚛ࠍ↢ᚑߔࠆ◲ଢᴺߢ‫ޔ‬᳓⚛᳇ᵹਛߦ߅߆ࠇߚ㜞᷷ߩࡈࠖ࡜ࡔࡦ࠻ߩᾲࠛࡀ࡞ࠡ࡯ߦࠃߞߡ‫ޔ‬᳓⚛᳇ᵹਛߩ৻ㇱߩಽሶ⁁᳓⚛ࠍේሶ⁁᳓⚛߳⸃㔌ߐߖࠆ‫ޕ‬ේሶ⁁᳓⚛ߩౣ⚿ว෻ᔕߪᲧセ⊛ㆃ޿ߚ߼‫࠻ࡦࡔ࡜ࠖࡈޔ‬᷷ᐲߢߩᐔⴧ
⚵ᚑࠍ޽ࠆ⒟ᐲ⛽ᜬߒߚ⁁ᘒߢૐ᷷ߦ଻ᜬߐࠇߚ⹜ᢱߦ೔㆐ߔࠆ‫ࡢ࠻࠶ࡎޔߡߞ߇ߚߒޕ‬ࠗࡗ࡯ᴺߦࠃߞߡ‫◲ޔ‬ଢߦㆊ಄ළේሶ⁁᳓⚛ㆶరࠍⴕ߁ߎߣ߇ߢ߈ࠆ‫ޕ‬࿑ 4(a)ߦㆊ಄ළේሶ⁁᳓⚛ㆶరߦ↪޿ߚⵝ⟎ߩ᭎⇛࿑ࠍ␜ߔ‫⹜ޕ‬ᢱ᷷ᐲߪ 1000 qC ߣߒߚ‫ޕ‬࿑ 4 (b) ߦ␜ߔࠃ߁ߦ‫ߩ࠻ࡦࡔ࡜ࠖࡈޔ‬᷷ᐲߪ 2000 qC ߅ࠃ߮ 2500 qC ߣߒ‫⹜ޔ‬ᢱߣࡈࠖ࡜ࡔࡦ࠻ߣߩ〒㔌ߪ
5 cm ߣߒߚ‫࠻ࡦࡔ࡜ࠖࡈޕ‬᷷ᐲߪ⿒ᄖ✢᡼኿᷷ᐲ⸘ߦࠃߞߡ‫⹜ޔ‬ᢱ᷷ᐲߪᾲ㔚ኻߦࠃߞߡ᷹ቯߒߚ‫ޕ‬ㅢᏱߩ᳓⚛ㆶరߢߪ‫⹜ޔ‬ᢱ᷷ᐲࠍ 800qC ߅ࠃ߮ 1000 qC ߣߒ‫ޔ‬ㆊ಄ළේሶ⁁᳓⚛ߣหߓታ㛎ⵝ⟎ࠍ↪޿ߡ‫ࠍ࠻ࡦࡔ࡜ࠖࡈޔ‬ടᾲߖߕߦⴕߞߚ‫ޕ‬ㆶరታ㛎ᓟߩ⹜ᢱࠍ X ✢࿁᛬ᴺ (XRD)‫ޔ‬ᢳ౉኿ X ✢࿁᛬ᴺ (GI-XRD)‫⿛ޔ‬ᩏဳ㔚ሶ㗼ᓸ㏜ (SEM) ߅ࠃ߮ࠛࡀ࡞ࠡ࡯
ಽᢔဳⰯశ X ✢ಽశᴺ (EDX) ߦࠃߞߡಽᨆߒߚ‫ޕ‬

࿑ 4 (a) ㆊ಄ළේሶ⁁᳓⚛ㆶర߅ࠃ߮ㅢᏱߩ᳓⚛ㆶరߦ↪޿ߚታ㛎ⵝ⟎ߩᮨᑼ࿑ (b) ㆊ಄ළේሶ⁁᳓⚛ㆶరᤨߩࡈࠖ࡜ࡔࡦ࠻߅ࠃ߮⹜ᢱㄭறߩᮨᑼ࿑

4. ታ㛎⚿ᨐ ⴫ 1 ߦታ㛎᧦ઙ‫ޔ‬ታ㛎ᓟߩ⹜ᢱ߆ࠄ XRD ߹ߚߪ GI-XRD ߦࠃߞߡᬌ಴ߐࠇߚ෻ᔕ↢ᚑ⋧‫ޔ‬
EDX ߦࠃߞߡಽᨆߐࠇߚ Ni(ss) ⋧ਛߩ࠴࠲ࡦỚᐲࠍ߹ߣ߼ߚ‫ޔߢߎߎޕ‬ૐ᷷᳓⚛ࡊ࡜࠭ࡑㆶరታ㛎ࠍ P1‫ޔ‬ㆊ಄ළේሶ⁁᳓⚛ㆶరߢࡈࠖ࡜ࡔࡦ࠻᷷ᐲ 2000 qC ߩታ㛎ࠍ F1‫ޔ‬2500 qC ߩ㧙㧙ታ㛎ࠍ F2‫ޔ‬ㅢᏱߩ᳓⚛ㆶరߢ⹜ᢱ᷷ᐲ 800 qC ߩታ㛎ࠍ U1‫ޔ‬1000 qC ߩታ㛎ࠍ U2 ߣߒߚ‫ޕ‬
⴫ 1 ታ㛎᧦ઙ߅ࠃ߮ታ㛎ᓟߩ⹜ᢱಽᨆ⚿ᨐ
Exp. #

Thickness ofsample / mmReductant

Temperature / qC
Sample Filament

Treatmenttime / hProduct Phase

Concentration ofTi in N(ss) (at%)

Ni, TiO2 (XRD)

Not observed

Ni, Ti2O 3, TiO2 (GI-XRD)

Not observed

12Ni, Ti3O 5 (XRD)

1.6 r 0.4

12Ni, Ti3O 5, Ti4O7 (XRD)

1.9 r 0.4
Not observed
1.8 r 0.5

P12.4

Low temperature hydrogen plasma

800-

6F10.2

Supercooled monatomic hydrogen

1000

2000

F20.4

Supercooled monatomic hydrogen

1000

2500

U10.3

Usual hydrogen gas

800-

6Ni, TiO2 (XRD)

U20.2

Usual hydrogen gas

1000-12Ni, Ti4O 7 (XRD) ⹜ᢱ᷷ᐲߦ⌕⋡ߒ‫ޔ‬P1, U1 ߅ࠃ߮ F1, F2, U2 ߩ⚿ᨐࠍᲧセᬌ⸛ߔࠆ‫ޕ‬ ࿑ 5 ߪ⹜ᢱ᷷ᐲ 800 qC ߦ߅ߌࠆ‫ޔ‬ૐ᷷᳓⚛ࡊ࡜࠭ࡑㆶర೨ᓟ߅ࠃ߮ㅢᏱߩ᳓⚛ㆶరᓟߩ⹜ᢱߩታ૕౮⌀߅ࠃ߮⹜ᢱ⴫㕙ߩ SEM ௝ߢ޽ࠆ‫⹜ޕ‬ᢱ᷷ᐲ 800 qC ߢߩታ㛎ߢ޽ߞߡ߽‫ޔ‬ૐ᷷᳓⚛ࡊ࡜࠭ࡑㆶర P1 ߢߪ‫ޔ‬ㆶరᓟߦ⹜ᢱ⴫㕙߇㤥⦡ߦᄌൻߒߚߩߦኻߒ‫ޔ‬ㅢᏱߩ᳓⚛
ㆶర U1 ߢߪ‫ޔ‬ㆶరᓟߩ⹜ᢱ⴫㕙ߪἯ⦡ߢ‫ޔ‬ㆶర೨ߣ޽߹ࠅᄌൻ߇ߥ޿‫ޔ߅ߥޕ‬࿑ 5 (b) ߢ‫ޔ‬ࡍ࡟࠶࠻ߩἯ⦡ߩㇱಽߪ⹜ᢱࡎ࡞࠳࡯ߦࠃߞߡ᳓⚛ࡊ࡜࠭ࡑߦᦑߐࠇߡ޿ߥ߆ߞߚㇱಽߢ޽ࠆ‫ ⴫ޔߣࠇߎޕ‬1 ߩ GI-XRD ߩ⚿ᨐ߆ࠄ‫ޔ‬ૐ᷷᳓⚛ࡊ࡜࠭ࡑㆶరߢߪㅢᏱߩ᳓⚛ㆶరࠃࠅ࠴࠲ࡦߩේሶଔ߇ૐ޿࠴࠲ࡦ㉄ൻ‛߇ᓧࠄࠇࠆ߇‫⴫ޔ‬㕙ߩߺߦ㒢ࠄࠇࠆߎߣ߇ࠊ߆ࠆ‫ޕ‬

࿑ 5 ૐ᷷᳓⚛ࡊ࡜࠭ࡑㆶర೨ᓟߩታ૕౮⌀߅ࠃ߮⹜ᢱ⴫㕙ߩ SEM ௝ ࿑ 6 ߪ⹜ᢱ᷷ᐲ 1000 qC ߦ߅ߌࠆ‫ޔ‬ㅢᏱߩ᳓⚛ㆶర U2 ߅ࠃ߮ㆊ಄ළේሶ⁁᳓⚛ㆶర F1,㧙㧙

F2 ᓟߩ⹜ᢱߩ෻኿㔚ሶ௝ߢ޽ࠆ‫ޕ‬࿑ߩ⊕⦡ߣ㤥⦡ߩㇱಽߪߘࠇߙࠇ Ni(ss) ⋧ߣ࠴࠲ࡦ㉄ൻ‛⋧ߦ⋧ᒰߔࠆ‫ޕ‬EDX ߦࠃߞߡᓧࠄࠇߚ⹜ᢱ⴫㕙ߩ Ni(ss) ⋧ਛߩ࠴࠲ࡦỚᐲߦߪ‫ ⴫ޔ‬1 ߦ␜ߔࠃ߁ߦㆶర᧦ઙߦኻߒ᦭ᗧߥᏅ߇⷗ࠄࠇߥ޿‫ޕ‬ ߎߎߢ‫ޔ‬࿑ 2 ࠃࠅ‫ ߇ࡦ࠲࠴ޔ‬1.6 ~ 1.9 at% ࿕ṁߒߚ Ni(ss) ⋧ߣᐔⴧߔࠆ࠴࠲ࡦ㉄ൻ‛ߪ
Ti3O5 ߩߺߢ޽ࠆ‫ޕ‬Ti4O7 ߣᐔⴧߒ߁ࠆ Ni(ss) ⋧ਛߦߪ࠴࠲ࡦߪ߶ߣࠎߤ࿕ṁߒߥ޿‫ ⴫ޕ‬1ߦ␜ߔࠃ߁ߦ‫ޔ‬᷷ᐲ 1000 qC ߦ߅޿ߡㅢᏱߩ᳓⚛ㆶరࠍⴕߞߚ⹜ᢱ U2 ߢߪ‫ޔ‬XRD ߦࠃߞߡ࠴࠲ࡦ㉄ൻ‛⋧ߣߒߡ Ti4O7 ߩߺᬌ಴ߐࠇߚߦ߽㑐ࠊࠄߕ‫ޔ‬Ni(ss) ⋧ਛߦ࠴࠲ࡦ߇ 1.8 at%࿕ṁߒߡ߅ࠅ‫ޔ‬U2 ߢߪ࿑ 2 ߣ XRD‫ޔ‬EDX ಽᨆ⚿ᨐߦ⍦⋫߇޽ࠆߣ޿߃ࠆ‫ߩߎޕ‬⍦⋫ߦ㑐ߒߡߪᰴ┨ߢ⠨ኤߔࠆ‫ޕ‬

࿑ 6 ㆊ಄ළේሶ⁁᳓⚛ㆶరᓟߩ⹜ᢱ⴫㕙ߩ෻኿㔚ሶ௝

5. ⠨ኤ
5.1 ᷷ᐲ 1000 qC ߦ߅ߌࠆ᳓⚛ㆶరታ㛎 ᧄ⎇ⓥߢߪ‫⹜ޔ‬ᢱߩಽᨆߦ XRD ߅ࠃ߮ SEM-EDX ࠍ↪޿ߚ‫ޕ‬XRD ߢߪ‫⹜ޔ‬ᢱߦ X ✢ࠍ౉኿ߒߚߣ߈ߦ⊒↢ߔࠆ࿁᛬ X ✢ࠍᬌ಴ߔࠆߚ߼‫ޔ‬X ✢ߩଚ౉ᷓߐ߇ᬌ಴ᷓߐߣߥࠆ‫ޕ‬X✢ߩ࿕૕⹜ᢱ߳ߩଚ౉ᷓߐ Lx ߪᰴᑼߢ⴫ࠊߐࠇࠆ[9]‫ޕ‬Lx 㧩sinș
1ln2P1㧙G(1) ߎߎߢ‫ޔ‬T, Pߪߘࠇߙࠇ X ✢౉኿ⷺ‫⹜ޔ‬ᢱߩ✢ๆ෼ଥᢙߢ޽ࠅ‫ޔ‬G ߪ X ✢ࡊࡠࡈࠔࠗ࡞ߦ⃻ࠇࠆᖱႎߩ߁ߜ‫⹜ޔ‬ᢱߩ⴫㕙㗔ၞ߆ࠄߩᷓߐ Lx ߹ߢߩᖱႎߩභ߼ࠆഀวߢ‫ޔ‬0.99 ߣߒߚ‫ޕ‬ ৻ᣇ‫ޔ‬SEM-EDX ߢߪ‫⹜ޔ‬ᢱߦ㔚ሶ✢ࠍ౉኿ߒߚߣ߈ߦ⊒↢ߔࠆⰯశ X ✢ࠍᬌ಴ߔࠆߚ߼‫ޔ‬㔚ሶ✢ߩଚ౉ᷓߐ߇ᬌ಴ᷓߐߣߥࠆ‫ޕ‬㔚ሶ✢ߩ࿕૕⹜ᢱ߳ߩ౉኿ᷓᐲ Le ߪߘࠇߙࠇ‫ޔ‬ᰴᑼߢ⴫ࠊߐࠇࠆ[10]‫ޕ‬㧙㧙

AE5/30
Le = 5.025 × 10-12 Ȝ ȡZ8/9s(2) ߎߎߢ‫ޔ‬A, E0, U, Z ߪ‫ࠇߙࠇߘޔ‬ේሶ㊂‫ޔ‬㔚ሶ✢ߩ౉኿ࠛࡀ࡞ࠡ࡯‫ޔ‬ේሶ⇟ภߢ޽ࠆ‫߹ޕ‬ߚ‫ޔ‬Os ߪ⚻㛎⊛ߥቯᢙߢ 0.182 ߢ޽ࠆ‫ޕ‬ᑼ(1), (2) ࠃࠅ‫ޔ‬X ✢ߩ Ni ߣ TiO2 ߳ߩଚ౉ᷓߐߪ‫ޔ‬X ✢ߩ౉኿ⷺߦ߽ࠃࠆ߇‫ޔ‬7.4 Pm ߆ࠄ 27 Pm ߢ޽ࠅ‫ޔ‬㔚ሶ✢ߩ Ni ߳ߩଚ౉ᷓߐߪ 0.44 mmߢ޽ࠆ‫ޔࠅ߹ߟޕ‬XRD ߪ⹜ᢱߩᷓ޿ㇱಽߩ⋧߹ߢಽᨆߢ߈ࠆߩߦኻߒ‫ޔ‬SEM-EDX ߪ⹜ᢱ⴫㕙ߒ߆ಽᨆߢ߈ߥ޿‫ޔߢߎߘޕ‬ㅢᏱߩ᳓⚛ㆶరᓟ෸߮ㆊ಄ළේሶ⁁᳓⚛ㆶరᓟߩ Ni(ss)⋧ਛ࠴࠲ࡦỚᐲ߇ 1.6 at% ~ 1.9 at% ߢ޽ߞߚߎߣ߆ࠄ‫ޔ‬࿑ 2 ߩ⋧ᐔⴧ㑐ଥࠍၮߦ‫ޔ‬ㅢᏱߩ᳓⚛ㆶరᓟߩ⹜ᢱߦ߽ Ti3O5 ߇↢ᚑߒߡ޿ࠆߣ⠨߃ߚ‫ޕ‬XRD ߣ SEM-EDX ߩಽᨆᷓߐߩ㆑޿ࠍ⠨ᘦߔࠆߣ‫ޔ‬ㅢᏱߩ᳓⚛ㆶర߅ࠃ߮ㆊ಄ළේሶ⁁᳓⚛ㆶరᓟߩ⹜ᢱᢿ㕙ߪ࿑ 7 ߩࠃ߁ߦߥߞߡ޿ࠆߣផኤߢ߈ࠆ‫ޔߜࠊߥߔޕ‬ㅢᏱߩ᳓⚛ㆶరᓟߩ⹜ᢱ⴫㕙ߦߪ XRD ߢߪᬌ಴ߢ߈ߥ޿߶ߤ⭯޿ Ti3O5 ⋧߇↢ᚑߒ‫ޔߚ߹ޔ‬ㆊ಄ළේሶ⁁᳓⚛ㆶరᓟߩ⹜ᢱߢߪ‫ޔ‬Ყセ⊛ᷓ޿ㇱಽ߹ߢ Ti3O5 ⋧߇ᚑ㐳ߒߡ޿ߚߣ⠨߃ࠄࠇࠆ‫ޕ‬

࿑ 7 ⹜ᢱ᷷ᐲ 1000 qC ߦ߅ߌࠆㆶరታ㛎ᓟߩ⹜ᢱߩᢿ㕙ᮨᑼ࿑ એ਄ߩࠃ߁ߦ‫⹜ޔ‬ᢱ᷷ᐲ 1000 qC ߢߩㆶరታ㛎ߦ߅޿ߡߪ‫ޔ‬ㅢᏱߩ᳓⚛ㆶరߢ޽ߞߡ߽
㕖ᐔⴧ᳓⚛ㆶరߢ޽ߞߡ߽‫ޔ‬Ti3O5 ߇↢ᚑߒߚߣ⠨߃ࠄࠇࠆ‫⹜ޕ‬ᢱ⴫㕙ߢ♽߇ᐔⴧߦ㆐ߒߡ޿ࠆߣ⠨߃ߚ႐ว‫ޔ‬ㆶర᧦ઙߦࠃߞߡ Ni(ss) ਛߩ࠴࠲ࡦỚᐲߦ᦭ᗧߥᏅ߇ߥ޿ߎߣߪ‫♽ޔ‬ߩ࠴࠲ࡦߩൻቇࡐ࠹ࡦࠪࡖ࡞߇ㆶర᧦ઙߦࠃࠄߥ޿ߎߣࠍᗧ๧ߔࠆ‫㉄ࡦ࠲࠴ޔߦࠄߐޕ‬ൻ‛ਛߩ࠴࠲ࡦߩൻቇࡐ࠹ࡦࠪࡖ࡞ߪ‫ޔ‬Ni(ss) ⋧ਛߩ࠴࠲ࡦߩൻቇࡐ࠹ࡦࠪࡖ࡞ߦ╬ߒ޿‫ޕ‬ᓥߞߡ‫ޔ‬෻ᔕ↢ᚑ⋧ߢ޽ࠆ Ti3O5 ⋧ਛߩ㉄⚛ߩൻቇࡐ࠹ࡦࠪࡖ࡞߽ㆶర᧦ઙߦࠃࠄߥ޿‫ޕ‬એ਄߆ࠄ‫ޔ‬ㅢᏱߩ᳓⚛ߣㆊ಄ළේሶ⁁᳓⚛ߢߪ‫ޔ‬ᾲജቇ⊛ߥㆶరജߦߪᏅߣ޿߃ࠆ‫ޔߒ߆ߒޕ‬㧙㧙ㆊ಄ළේሶ⁁᳓⚛ߦߪ Ti3O5 ⋧ߩᚑ㐳ࠍଦߔㅦᐲ⺰⊛ߥㆶరജߩะ਄ലᨐ߇޽ࠆߎߣ߇␜ໂߐࠇࠆ‫ޕ‬

5.2 㕖ᐔⴧ᳓⚛ߦࠃࠆㆶర෻ᔕࡊࡠ࠮ࠬ ᓥ᧪‫ޔ‬㕖ᐔⴧ᳓⚛ߪ‫ޔ‬ዪᚲᐔⴧߦၮߠߊᾲജቇ⸘▚߆ࠄᾲജቇ⊛ߦ㜞޿ㆶరജࠍᜬߟߣߐࠇߡ߈ߚ[11]‫ޔ߫߃଀ޕ‬᷷ᐲ 1000 qC ߦ߅޿ߡේሶ⁁᳓⚛ಽ࿶߇ 10-2 atm‫ޔ‬᳓⫳᳇ಽ࿶߇
10-4 atm ߢ޽ࠆߣߔࠆߣ‫ޔ‬ᰴᑼߩᐔⴧߦࠃࠅ‫ߩ⚛㉄ޔ‬ൻቇࡐ࠹ࡦࠪࡖ࡞ߪ 946.1 kJ mol-1 ߣߥࠆ‫ޕ‬
4H + O2 Ђ 2H2O(3)RT ln pO2 = 2'Gq(H2O)  4'Gq(H) + RT ln pH2O2/pH4(4) ߎࠇߪ‫ޔ‬࿑ 1 ߦ 1 atm ߩ᳓⚛ߣ 10-4 atm ߩ᳓⫳᳇߇ᐔⴧߔࠆᤨߩ㉄⚛ߩൻቇࡐ࠹ࡦࠪࡖ࡞ࠃࠅᭂ߼ߡૐ޿‫ᧄޔߒ߆ߒޕ‬ታ㛎⚿ᨐߪ‫ޔ‬㕖ᐔⴧ᳓⚛ߩㆶరജ߇ߎߩࠃ߁ߥᾲജቇ⊛⹏ଔߦᓥࠊߥ޿ߎߣࠍ␜ໂߒߡ޿ࠆ‫ᧄޔߢߎߘޕ‬ታ㛎⚿ᨐࠍၮߦ࠴࠲ࡦ㉄ൻ‛ߦኻߔࠆ㕖ᐔⴧ᳓⚛ߩㆶరജࠍวℂ⊛ߦ⺑᣿ߢ߈ࠆࡕ࠺࡞ߣߒߡᰴߩࠃ߁ߥㆶర෻ᔕࡊࡠ࠮ࠬࠍ⠨߃ߚ‫ޕ‬ ߔߥࠊߜ‫㉄ࡦ࠲࠴ޔ‬ൻ‛ߩ㕖ᐔⴧ᳓⚛ߦࠃࠆㆶర෻ᔕߦߪ‫ޔ‬࿑ 8 ߦ␜ߔࠃ߁ߦ‫ޔ‬3 ߟߩࠛࡀ࡞ࠡ࡯⁁ᘒ i) High energy state, ii) Energy released state, iii) Equilibrium state ߇޽ࠅ‫⁁ߩߘޔ‬ᘒ㑆ࠍ 2 ߟߩࡊࡠ࠮ࠬ 1) Releasing energy process, 2) Relaxation process ߦࠃߞߡㆫ⒖ߔࠆ‫ޕ‬ㆶర෻ᔕೋᦼ⁁ᘒߢ޽ࠆ‫ޔ‬i) High energy state ߢߪ‫ޔ‬᳓⚛߇ᾲ߹ߚߪ㔚⏛႐ߦࠃߞߡബ⿠ߐࠇ‫ޔ‬ᄙᢙߩේሶ⁁᳓⚛߇ሽ࿷ߔࠆ‫⁁ߩߎޕ‬ᘒߪ‫ޔ‬᳓⚛߇ࠛࡀ࡞ࠡ࡯⊛ߦᭂ߼ߡਇ቟ቯߢ޽ࠆߚ
߼‫ࠍ࡯ࠡ࡞ࡀࠛߩߘޔ‬࿕૕⴫㕙ߢㅦ߿߆ߦ᡼಴ߔࠆ 2) Relaxation process ࠍ⚻ߡ‫ޔ‬ii) Energy
released state ߳ㆫ⒖ߔࠆ‫߈ߣߩߎޕ‬ᄢㇱಽߪᾲߣߒߡ᡼಴ߒ‫ޔ‬ಽሶ⁁᳓⚛߳ᚯࠆ‫ޔߒ߆ߒޕ‬৻ㇱߩේሶ⁁᳓⚛ߪ⹜ᢱ⴫㕙ߩ࠴࠲ࡦ㉄ൻ‛ࠍㆶరߒ᳓ࠍ↢ᚑߔࠆ‫ߩࡦ࠲࠴ޔ߈ߣߩߎޕ‬ේሶଔߪ᭽‫ߥޘ‬୯ࠍߣࠅ‫ޔ‬TiO ߿ Ti2O3 ߥߤ߇↢ᚑߔࠆ‫⁁ߩߎޕ‬ᘒ߇ Energy released state ߢ޽ࠆ‫ޕ‬Energy released state ߪㆶర෻ᔕਛᦼ⁁ᘒߦᒰߚࠅ‫ޔ‬Ḱ቟ቯ⁁ᘒߢ޽ࠆߚ߼‫ޔ‬2)Relaxation process ࠍ⚻ߡ‫ޔ‬ㆶర෻ᔕ⚳⁁ᘒߢ޽ࠆ iii) Equilibrium state ߳ㆫ⒖ߔࠆ‫ޕ‬Relaxationprocess ߪ‫⹜ޔ‬ᢱ⴫㕙ߦ↢ᚑߒߚ‫ߩࡦ࠲࠴ޔ‬ේሶଔ߇ૐ޿࠴࠲ࡦ㉄ൻ‛߇‫ࠬࠟޔ‬Ⴚ⤑ਛߩ᳓ಽሶ߹ߚߪ⹜ᢱᷓㇱߩ࠴࠲ࡦߩේሶଔ߇㜞޿࠴࠲ࡦ㉄ൻ‛ߣ෻ᔕߒ‫ޔ‬ᐔⴧ⁁ᘒ߳⥋ࠆࡊࡠ࠮ࠬߢ޽ࠆ‫ߩࠬ࠮ࡠࡊߩߎޕ‬ㅦᐲߪ⹜ᢱ᷷ᐲ߇㜞ߊߥࠆߣㅦߊߥࠆߣ⠨߃ࠄࠇࠆ‫ޔࠅ߹ߟޕ‬᷷ᐲ 800 qC એਅߢߪᲧセ⊛ㆃߊ‫ޔ‬᷷ᐲ 1000 qC એ਄ߢߪㅦ޿ߣ⠨߃ࠄࠇࠆ‫ޕ‬ᓥߞߡ‫⎇ᧄޔ‬ⓥߢⴕߞߚૐ᷷᳓⚛ࡊ࡜࠭ࡑㆶరߢߪ‫⹜ޔ‬ᢱ᷷ᐲ߇ 800 qC ߣૐ߆ߞߚߚ߼‫ޔ‬Relaxation㧙㧙

process ߇චಽㅴⴕߖߕ‫ޔ‬ታ㛎ᓟߩ⹜ᢱߦ Energy released state ߩ↢ᚑ‛ߢ޽ࠆ Ti2O3 ߇⃻ࠇߚߣ⠨߃ࠄࠇࠆ‫৻ޕ‬ᣇ‫ޔ‬ㆊ಄ළේሶ⁁᳓⚛ㆶరߢߪ‫⹜ޔ‬ᢱ᷷ᐲ߇ 1000 qC ߣ㜞߆ߞߚߚ߼‫ޔ‬
Relaxation process ߇ㅴⴕߒ‫ޔ‬Energy released state ߢ↢ᚑߒߚ࠴࠲ࡦߩේሶଔ߇ૐ޿࠴࠲ࡦ㉄ൻ‛߇ౣ㉄ൻߐࠇ⹜ᢱߩᷓ޿ㇱಽ߹ߢ Equilibrium state ߢ޽ࠆ Ti3O5 ߣߥߞߡ޿ߚߣ⠨߃ࠄࠇࠆ‫ޕ‬ ߐߡ‫ޔ‬㕖ᐔⴧ᳓⚛ㆶరߣห᭽ߦ‫ޔ‬㕖ᐔⴧ⁁ᘒߩൻቇ⒳ࠍ೑↪ߔࠆࡊࡠ࠮ࠬߣߒߡࡊ࡜࠭ࡑ⓸ൻ߇᜼ߍࠄࠇࠆ‫⓸ࡑ࠭࡜ࡊޕ‬ൻߪ෻ᔕㅦᐲ߇ㅦ޿ߛߌߢߥߊ‫ޔ‬ㅢᏱߩ⓸⚛ࠟࠬࠍ↪޿ߚ⓸ൻߢߪ↢ᚑߒߥ޿ൻว‛߇ᓧࠄࠇࠆ‫⓸ࡑ࠭࡜ࡊޕ‬ൻߦኻߒߡ߽‫৻ޔ‬ᐲḰ቟ቯ⋧ߢ޽ࠆ᭽‫⓸ߥޘ‬ൻ‛߇↢ᚑߒߚᓟߦ‫ޔ‬ᐔⴧ⋧߳✭๺ߐࠇࠆࡕ࠺࡞߇ឭ᩺ߐࠇߡ޿ࠆ[12]‫⎇ᧄޕ‬ⓥߢ
ឭ᩺ߒߚ㕖ᐔⴧ᳓⚛ㆶరߩ෻ᔕࡊࡠ࠮ࠬߪ‫⓸ࡑ࠭࡜ࡊޔ‬ൻߣᲧセߒߡ߽ᅷᒰߢ޽ࠆߣ⠨߃ࠄࠇࠆ‫ޕ‬

࿑ 8 㕖ᐔⴧ᳓⚛ㆶరߩ෻ᔕࡊࡠ࠮ࠬߣࠛࡀ࡞ࠡ࡯⁁ᘒ6. ⚿⸒
 ᧄ⎇ⓥߢߪ‫ޔ‬㕖ᐔⴧ᳓⚛ࠍ↪޿ߡ‫㉄ࡦ࠲࠴ޔ‬ൻ‛ߣㆫ⒖㊄ዻߣߩᷙว૕ࠍ‫ ߫߃଀ޔ‬Ni-Ti
ว㊄ߩࠃ߁ߥ‫ޔ‬ታ↪⊛ߥ࠴࠲ࡦว㊄߳⋥ធㆶరߔࠆࡊࡠ࠮ࠬߩ㐿⊒ࠍ⋡ᜰߒߚ‫ޕ‬ᱷᔨߥ߇ࠄ‫౒࡞ࠤ࠶࠾ޔ‬ሽਅߦ߅޿ߡ࠴࠲ࡦ㉄ൻ‛ࠍ㕖ᐔⴧ᳓⚛ㆶరߒߡ߽ Ni3Ti ࠍᓧࠆߎߣߪ಴᧪
ߥ߆ߞߚ‫ޔߒ߆ߒޕ‬ේሶ⁁᳓⚛߇ਥߚࠆㆶర૕ߢ޽ࠆૐ᷷᳓⚛ࡊ࡜࠭ࡑ߿ㆊ಄ළේሶ⁁᳓㧙㧙⚛ߩㆶరࡊࡠ࠮ࠬߦ㑐ߒߡ⥝๧ᷓ޿⍮⷗߇ᓧࠄࠇߚ‫ޔߜࠊߥߔޕ‬㕖ᐔⴧ᳓⚛ߪ‫ޔ‬ㅢᏱߩ᳓⚛ࠃࠅ߽ㅦᐲ⺰⊛ߦ㜞޿ㆶరജࠍ᦭ߒߡ޿ࠆ‫ޕ‬ㆶరᤨߩ⹜ᢱ᷷ᐲ߇ૐ޿႐ว‫ߩࡦ࠲࠴ޔ‬ේሶଔ߇ૐ޿࠴࠲ࡦ㉄ൻ‛߇ᓧࠄࠇࠆ߇‫ࡦ࠲࠴ޔ‬ේሶߩ᜛ᢔࠍᔅⷐߣߔࠆ⋥ធว㊄ൻᴺߦߪㆡߒߡ޿ߥ޿‫⹜ޔߚ߹ޕ‬ᢱ᷷ᐲ߇ૐ޿႐วߦᓧࠄࠇࠆ↢ᚑ‛ߪ㕖ᐔⴧ⋧ߢ޽ࠆ‫৻ޕ‬ᣇ‫ޔ‬ㆶరᤨߩ⹜ᢱ᷷ᐲ߇㜞޿႐ว‫ߩࡦ࠲࠴ޔ‬ේሶൻ߇ૐ޿࠴࠲ࡦ㉄ൻ‛߇৻ᐲߪ↢ᚑߔࠆ߇‫⋥ޔ‬ߜߦౣ㉄ൻߐࠇ‫ޔ‬ㅢᏱߩ᳓⚛ㆶరߣᄌࠊࠄߥ޿⋧ߒ߆ᓧࠄࠇߥ޿ߣ⠨߃ࠄࠇࠆ‫ޕ‬ૉߒ‫⹜ޔ‬ᢱߩᷓ޿ㇱಽ߹ߢㆶరߢ߈ࠆߚ߼‫ޔ‬ෘ޿⹜ᢱߦኻߒߡߪ㕖ᐔⴧ᳓⚛ㆶర߇᦭ലߢ޽ࠆߣ⠨߃ࠄࠇࠆ‫ޕ‬

7. ⻢ㄉ ᧄ⎇ⓥߦኻߒߏេഥ㗂߈߹ߒߚ‫⽷ޔ‬࿅ᴺੱJFE 21਎♿⽷࿅ߦෘߊᗵ⻢޿ߚߒ߹ߔ‫ޔ߅ߥޕ‬ᧄ⎇ⓥߩਥⷐㇱಽߪ‫ޔ‬੩ㇺᄢቇᄢቇ㒮↢㑐ᧄ⧷ᒄ᳁ߩᎿቇ⎇ⓥ⑼᧚ᢱᎿቇኾ᡹ߦ߅ߌࠆ
2008ᐕᐲୃ჻⺖⒟ߩ⎇ⓥ⺖㗴ߣߒߡⴕࠊࠇ߹ߒߚ‫ޕ‬ෳ⠨ᢥ₂
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