⺰ ᢥᄙⷺࡃ࡟࡞ࡊ࡜࠭ࡑ⴫㕙ᡷ⾰ᴺߦࠃࠆ㊄ዻ࠴࠲ࡦᓸ☸ሶߩ⴫㕙⓸ൻ㩷᧻ේ ࿻૓‫ޔ‬࿪㊁ 㓷᢯‫ޔ‬੗਄ శᶈ‫ޔ‬㒙ㇱ ቁਯንጊᄢቇ᳓⚛ห૏૕⑼ቇ⎇ⓥ࠮ࡦ࠲࡯‫ ޥ‬ንጊᏒ੖⑔ Surface Nitridation of Titanium Particles
by Polygonal-Barrel Plasma Treatment System㩷

Keisuke Matsubara, Masato Danno, Mitsuhiro Inoue, Takayuki Abe
Hydrogen isotope research center, University of Toyama
Gofuku 3190, Toyama 930-8555, Japan(Received December 12, 2011; accepted March 9, 2012)
Abstract
We demonstrated surface nitridation of titanium particles using the polygonal barrel-plasma treatment
system. In order to verify the formation of TiN, a Ti plate was treated in our plasma treatment system. Thecolor of the Ti plate changed from metallic to gold as a result of N2 plasma treatment. Glow discharge
optical emission spectrometry of the plasma-treated Ti plate confirmed that nitrogen was inserted. From
XPS measurements, it was also found that the nitrogen in the sample was ascribed to the formation of Ti-Nbonds. It should be noted that the X-ray diffraction patterns of the Ti plate before and after the plasma
treatment showed only the reflection peaks of Ti metal, supporting that the Ti-N bond formation occurred
only on the surface of the plate. Subsequently, N2 plasma treatment was applied to Ti particles. The plasmatreatment using a swinging motion of the barrel containing Ti particles changed the color of the particles
uniformly from gray to brown. The UV-VIS absorbance spectrum of the plasma-treated Ti particles wassimilar to that of the plasma-treated Ti plate. This result was considered a proof of the Ti-N bond formationon Ti particles achieved by the polygonal-barrel plasma treatment system.

1. ✜⸒ ⓸ൻ࠴࠲ࡦߪૐ៺ᡂଥᢙ‫ޔ‬㜞⎬ᐲ‫ޔ‬㜞ᒁߞ߆߈⠴ᕈ‫ޔ‬㊄⦡‫ޔ‬㜞Ⲣὐ‫ޔ‬ૐ㔚᳇ᛶ᛫ߣ޿߁․ᕈ߆
ࠄᐢߊ೑↪ߐࠇߡ޿ࠆ᧚ᢱߢ޽ࠆ‫ߩߘޕ‬ਛߢ߽⓸ൻ࠴࠲ࡦᓸ☸ሶߪⶄว᧚ߩᯏ᪾⊛࡮㔚᳇⊛․ᕈߩะ਄ࠍ⋡⊛ߣߒߚࡈࠖ࡜࡯߿ᷝട೷ߣߒߡലᨐ⊛ߥᕈ⢻ࠍ᦭ߔࠆ [1-3]‫ޕ‬ ⓸ൻ࠴࠲ࡦᓸ☸ሶߪ⃻࿷‫ࡦ࠲࠴ߪ޿ࠆ޽ࡦ࠲࠴ޔ‬ൻว‛ࠍࠕࡦࡕ࠾ࠕਛߢ㜞᷷ಣℂߔࠆᣇᴺ[4]‫ޔ‬෸߮ࡔࠞࡁࠤࡒࠞ࡞ᴺ[5, 6]ߣ๭߫ࠇࠆᚻᴺߢਥߦ⺞⵾ߐࠇߡ޿ࠆ‫ߩࠇߕ޿ޔࠄ߇ߥߒ߆ߒޕ‬ᚻᴺ߽⺞⵾ᤨߦടᾲ޽ࠆ޿ߪᷙ✵ߦࠃߞߡ☸ሶᒻ⁁߇ᄌൻߔࠆ‫ߩࠄࠇߎޔ߼ߚߩߘޕ‬ᚻᴺߢ⺞⵾ߒߚ⓸ൻ࠴࠲ࡦᓸ☸ሶࠍ☸ᓘ߿ᒻ⁁ߩ೙ᓮ߇ᔅ㗇ߥ⎇⏴೷߿లႯ೷‫ߦ࡯ࠨ࡯ࡍࠬޔ‬ᔕ↪ዷ㐿ߢ߈ߥ޿‫ޕ‬ ߘߎߢᚒ‫ޔߪޘ‬ಾ೥Ꮏౕ╬ߩ⠴ਭᕈࠍะ਄ߐߖࠆߚ߼ߦᎿᬺ⊛ߦ↪޿ࠄࠇߡ޿ࠆࡊ࡜࠭ࡑ⴫㕙
ಣℂᛛⴚߦᵈ⋡ߒߚ‫ߩߎޕ‬ᚻᴺࠍ↪޿ߡᒻ⁁߇೙ᓮߐࠇߚ㊄ዻ࠴࠲ࡦᓸ☸ሶ⴫㕙ࠍ⓸ൻߔࠇ߫‫ޔ‬਄⸥ߒߚᓥ᧪ߩ⓸ൻ࠴࠲ࡦᓸ☸ሶ⺞⵾ᴺߩ໧㗴ࠍ⸃᳿ߢ߈ࠆ‫ߦߢ߹ࠇߎޔࠄ߇ߥߒ߆ߒޕ‬ႎ๔ߐࠇߡ޿ࠆࠟࠬᵹㅢਅߦ߅ߌࠆࡊ࡜࠭ࡑಣℂᴺ[7, 8]ߢߪᓸ☸ሶߩੑᰴ☸ሶࠍ☳⎈ߢ߈ߕ‫ޔ‬ဋ৻ߥ⴫㕙ಣℂ߇࿎㔍ߢ޽ࠆ‫ޔߚ߹ޕ‬ᓸ☸ሶࠍᠣᜈߔࠆߚ߼ߦ౞╴ᒻߩ࿁ォኈེࠍⵝ஻ߒߚࡊ࡜࠭ࡑಣℂᴺ߽ႎ๔ߐࠇߡ޿ࠆ߇[9, 10]‫ޔ‬౞╴ኈེߩ࿁ォߢߪᓸ☸ሶߪኈེౝߩౝოࠍṖࠅ⪭ߜࠆߛߌߢੑᰴ☸ሶߩ☳⎈߹ߢ⥋ࠄߥ޿‫ޕ‬ ߎߩ໧㗴ࠍ⸃᳿ߔࠆߚ߼ߦ‫ᦨޔ‬ㄭᚒ‫ޟߪޘ‬ᄙⷺࡃ࡟࡞ࡊ࡜࠭ࡑ⴫㕙ᡷ⾰ᴺ‫ࠍޠ‬㐿⊒ߒߚ[11]‫ߎޕ‬ߩⵝ⟎ߪᚒ‫߇ޘ‬એ೨㐿⊒ߒߚ‫ޟ‬ᄙⷺࡃ࡟࡞ࠬࡄ࠶࠲࡝ࡦࠣᴺ‫[ޠ‬12]ߩᓸ☸ሶᠣᜈᯏ᭴ࠍ᦭ߔࠆ‫ߎޕ‬ߩᯏ᭴ߦ߅޿ߡᓸ☸ሶߪᠣᜈߐࠇࠆߛߌߢߥߊ‫࡞࡟ࡃޔ‬ౝო߳ߩⴣ⓭ߦࠃࠅੑᰴ☸ሶ߆ࠄ৻ᰴ☸
ሶߦ☳⎈ߐࠇࠆ‫⚿ߩߘޕ‬ᨐ‫ᧄޔ‬ᚻᴺߦࠃࠅ㉄ൻ࠴࠲ࡦᓸ☸ሶ⴫㕙ࠍဋ৻ߦ⓸⚛࠼࡯ࡊߔࠆߎߣߦᚑഞߒߡ޿ࠆ[11]‫⎇ᧄޔߢߎߘޕ‬ⓥߢߪ‫ޔ‬ᄙⷺࡃ࡟࡞ࡊ࡜࠭ࡑ⴫㕙ᡷ⾰ᴺߦࠃࠆᄙⷺࡃ࡟࡞ࡊ࡜࠭ࡑ⴫㕙ᡷ⾰ᴺߦࠃࠆ㊄ዻ࠴࠲ࡦᓸ☸ሶߩ⴫㕙⓸ൻಣℂࠍᬌ⸛ߒߚ‫ޕ‬
2. ታ㛎
2.1 ⹜ᢱߩ⺞⵾
 Figure 1 ߦᧄ⎇ⓥߢ↪޿ߚᓸ☸ሶࡊ࡜࠭ࡑ⴫
㕙ᡷ⾰ⵝ⟎ߩ᭎⇛࿑ࠍ␜ߔ‫⌀ߪ⟎ⵝߩߎޕ‬ⓨ࠴ࡖࡦࡃ࡯ౝߦࠟࠬࠍଏ⛎ߔࠆࠟࠬଏ⛎㔚ᭂߣ☳૕ࠍ౉ࠇࠆ 6 ⷺࡃ࡟࡞߆ࠄ᭴ᚑߐࠇߡ޿ࠆ‫ޕ‬⹜ᢱߩ⺞⵾ߪએਅߩࠃ߁ߦⴕߞߚ‫ޕ‬㊄ዻ࠴࠲ࡦ᧼(࠾࡜ࠦ 15151.5 mm)‫ ߪߊߒ߽ޔ‬1.5 g ߩ㊄ዻ࠴࠲ࡦᓸ☸ሶ(ᄢ㒋࠴࠲࠾࠙ࡓ TILOP 45,☸ᓘ: 45 µm એਅ)ࠍࡃ࡟࡞ౝߦᛩ౉ߒ‫⌀ޔ‬ⓨ࠴ࡖࡦࡃ࡯ౝࠍ 1.010-3 Pa એਅߦߥࠆ߹ߢ⌀ⓨឃ᳇ߒߚ‫ߩߘޕ‬ᓟ‫⚐(ࠬࠟ⚛⓸ޔ‬ᐲ㧦99.9998 %)ࠍዉ౉ߒ‫ޔ‬250 kHz 㜞๟ᵄ㔚Ḯࠍ↪޿ߡᚲቯߩ
ᤨ㑆(㊄ዻ࠴࠲ࡦ᧼: 10 min, ㊄ዻ࠴࠲ࡦᓸ☸ሶ:Figure 1 Schematic representation of theplasma-treatment system.

4 h)ߢࡊ࡜࠭ࡑಣℂࠍⴕߞߚ‫ޕ‬RF ಴ജ‫ࠬࠟ⚛⓸ޔ‬࿶ߪߘࠇߙࠇ 300 W‫ޔ‬10 Pa ߦ⸳ቯߒߚ‫ߩߎޕ‬ᤨ‫ޔ‬㊄ዻ࠴࠲ࡦ᧼ࠍ↪޿ߚ႐วߪ 6 ⷺࡃ࡟࡞ࠍ࿕ቯ‫ޔ‬㊄ዻ࠴࠲ࡦᓸ☸ሶࠍࡊ࡜࠭ࡑಣℂߔࠆ႐วߪࡃ࡟࡞ࠍ࿕ቯ‫ⷺߪ޿ࠆ޽ޔ‬ᐲr75°‫ޔ‬࿁ォㅦᐲ 5 rpm ߦߡᝄࠅሶㆇേߐߖߚ‫ࡑ࠭࡜ࡊޕ‬ಣℂᓟ‫ޔ‬⓸⚛ࠟࠬࠍᵈᗧᷓߊዉ౉ߒߡ࠴ࡖࡦࡃ࡯ౝߩ࿶ജࠍᄢ᳇࿶ߦᚯߒ‫⹜ޔ‬ᢱࠍขࠅ಴ߒߚ‫ޕ‬
2.2 ⺞⵾⹜ᢱߩ‛ᕈ⹏ଔ ⴫㕙ಣℂߒߚ⹜ᢱਛߩ⓸⚛ߩᷓߐᣇะಽᏓߪࠣࡠ࡯᡼㔚⊒శಽశⵝ⟎(GD-OES; ၳ႐⵾૞ᚲGD-Profiler2)ࠍ↪޿ߡ᷹ቯߒߚ‫ࠆߌ߅ߦ࡞ࠗࠔࡈࡠࡊޕ‬ᷓߐߪಽᨆ∥ᷓߐߣ᷹ቯᤨ㑆߆ࠄ឵▚ߒߚ‫ޕ‬X ✢శ㔚ሶಽశಽᨆ(XPS; ࠕ࡞ࡃ࠶ࠢࡈࠔࠗᩣᑼળ␠ Quantum2000)ߢߪ‫⹜ޔ‬ᢱߦ฽߹ࠇࠆ⓸⚛
ේሶߩ⚿ว⁁ᘒࠍ⹏ଔߒߚ‫ޔᤨߩߎޕ‬Ar ࠛ࠶࠴ࡦࠣߔࠆߎߣߢ‫⴫ᦨޔ‬㕙߆ࠄ⚂ 200 nm ߹ߢߩ⓸⚛ߩಽᏓ߽᳞߼ߚ‫⹜ޕ‬ᢱߩ⚿᥏᭴ㅧߪ X ✢࿁᛬᷹ቯ(XRD; PHILIPS PW1825/00)ߦࠃࠅ⸃ᨆߒߚ‫ޕ‬⹜ᢱߩశๆ෼ࠬࡍࠢ࠻࡞ߪนⷞ⚡ᄖಽశశᐲ⸘(UV-VIS; ᣣᧄಽశ V-560i RM)ࠍ↪޿ߡ‫ޔ‬᜛ᢔ෻
኿ᴺߦࠃࠅ᷹ቯߒߚ‫ޕ‬UV-VIS ࠬࡍࠢ࠻࡞ߩࡃ࠶ࠢࠣ࡜࠙ࡦ࠼ߪ⎫㉄ࡃ࡝࠙ࡓࠍ૶↪ߒߡ⵬ᱜߒ‫ޔ‬ᓸ☸ሶ⹜ᢱߩ᷹ቯߪ⍹⧷⓹ઃ߈☳૕ኾ↪࠮࡞ߦኽ౉ߒߡⴕߞߚ‫ޕ‬3. ⚿ᨐ
3.1 ㊄ዻ࠴࠲ࡦ᧼ߦኻߔࠆ⓸⚛ࡊ࡜࠭ࡑಣℂ ࡊ࡜࠭ࡑ⴫㕙ಣℂߦࠃࠆ㊄ዻ࠴࠲ࡦߩ⓸ൻߩนุࠍᬌ⸛ߔࠆߚ߼ߦ‫ޔ‬㊄ዻ࠴࠲ࡦ᧼ߩ⴫㕙ಣℂ(a)(b)ࠍⴕߞߚ‫ޕ‬Figure 2 ߦ(a)⓸⚛ࡊ࡜࠭ࡑಣℂ೨‫ޔ‬෸߮(b)ಣℂᓟߩ㊄ዻ࠴࠲ࡦ᧼ߩᄖⷰ౮⌀ࠍ␜ߔ‫ᧂޕ‬ಣℂ⹜ᢱߪ㊄ዻ⦡ߢ޽ߞߚߩߦኻߒ‫࠭࡜ࡊ⚛⓸ޔ‬ࡑಣℂᓟߩ⹜ᢱߪ㊄⦡ࠍ๒ߒߚ‫࠭࡜ࡊ⚛⓸ߩߎޕ‬ࡑಣℂᓟߩ⦡⋧ߪ‫⓸ޔ‬ൻ࠴࠲ࡦߦ㘃ૃߔࠆ‫ߎߘޕ‬ߢ‫⓸ޔ‬ൻ࠴࠲ࡦᒻᚑࠍ᣿ࠄ߆ߦߔࠆߚ߼ߦ⓸⚛ࡊ࡜࠭ࡑಣℂ೨ᓟߩ⹜ᢱߩ‛ᕈࠍ᷹ቯߒߚ‫ޕ‬ ⹜ᢱਛߩ⓸⚛ߩᷓߐᣇะಽᏓࠍ⺞ߴࠆߚ߼‫ᧂޔ‬
ಣℂ⹜ᢱ‫ޔ‬෸߮⓸⚛ࡊ࡜࠭ࡑಣℂ⹜ᢱߩ GD-OES᷹ቯࠍⴕߞߚ‫ޕ‬ᓧࠄࠇߚࡊࡠࡈࠔࠗ࡞ࠍ Figure 3

Figure 2 Photographs of (a) as-received Tiplate, (b) N2 plasma-treated Ti plate.

ߦ␜ߔ(a: ᧂಣℂ‫ޔ‬b: ಣℂᓟ)‫ޕ‬ਔ⠪ࠍᲧセߔࠆߣ‫ޔ‬ಣℂᓟߩ⹜ᢱߦ߅޿ߡᷓߐ 50 nm ઃㄭࠍࡇ࡯ࠢߣߔࠆ‫ޔ‬ಣℂ೨ߦߪߥ޿⓸⚛ߩಽᏓ߇⹺߼ࠄࠇࠆ‫⚿ߩߎޕ‬ᨐߪ‫ࡑ࠭࡜ࡊ⚛⓸ޔ‬ಣℂߦࠃࠅ⹜ᢱౝ߳⓸⚛߇ଚ౉ߒߚߎߣࠍ␜ߒߡ޿ࠆ‫ޔߚ߹ޕ‬Figure 4 ߦ␜ߔ⓸⚛ࡊ࡜࠭ࡑಣℂ⹜ᢱߩ XPS ᷹ቯߩ⚿ᨐࠍ⷗ࠆߣ‫ޔ‬29㨪145 nm ߦ Ti-N ⚿วߦᏫዻߢ߈ࠆ N1s ࡇ࡯ࠢ߇ 396.8 eV ߦ⹺߼ࠄࠇࠆ[13]‫ޕ‬ߎࠇࠄߩ⚿ᨐ߆ࠄ‫ࡑ࠭࡜ࡊ⚛⓸ޔ‬ಣℂߦࠃࠅ㊄ዻ࠴࠲ࡦ⴫㕙ߦ⓸ൻ࠴࠲ࡦ߇ᒻᚑߒߚߎߣ߇ࠊ߆
ࠆ‫ޔࠄ߇ߥߒ߆ߒޕ‬Figure 4 ߩ Ti-N ࡇ࡯ࠢߪ⹜ᢱౝㇱ߳ⴕߊ⒟ᒝᐲ߇ૐਅߒ‫ޔ‬174 nm ߢᶖṌߔࠆ‫ޕ‬ߎࠇߪ⓸ൻ࠴࠲ࡦߩᒻᚑ߇ 174 nm ᧂḩߢ޽ࠆߎߣࠍ␜ໂߒ‫⚿ߩߎޔ‬ᨐߦ GD-OES ᷹ቯߩ⓸⚛ಽᏓ߽╓วߒߡ޿ࠆ‫ޔ߅ߥޕ‬Figure 4 ߢߪ⹜ᢱᦨ⴫㕙ߩ N1s ࡇ࡯ࠢ߇࠴࠲ࡦ㉄⓸ൻ‛ߩᒻᚑߦ⿠࿃

ߔࠆ 396.2 eV ߦࠪࡈ࠻ߒߡ޿ࠆ[13]‫ޔߚ߹ޕ‬O1s ࡇ࡯ࠢߪᦨ⴫㕙ߢߩߺ Ti-O ⚿วߩᒻᚑߦၮߠߊ
530eV ઃㄭߦⷰኤߐࠇ‫ޔ‬ᷓߐ 29 nm એ㒠ߢߪᩰሶ㑆㉄⚛ߦၮߠߊ 531.5eV ઃㄭ߳ࠪࡈ࠻ߒߚ[14]‫ޕ‬ߎࠇࠄߩ⚿ᨐߪ‫⴫ᦨޔ‬㕙߆ࠄ 29nm ᧂḩߩ㗔ၞߢ⓸ൻ࠴࠲ࡦߩ৻ㇱ߇㉄ൻߐࠇߡ޿ࠆߎߣࠍ␜ໂ
ߔࠆ‫ޕ‬
203nm
174nm

Intensity / arb. unit

Intensity / arb. unit

(b)

(a)
0100

200

300

145nm
116nm
87nm
58nm
29nm
0nm

400 399 398 397 396 395 394 393

Depth / nm

Binding energy / eV

Figure 3 GD-OES depth profiles of nitrogen for(a) as-received Ti plate, (b) N2 plasma-treated Ti plate.

Figure 4 XPS N1s spectra ofplasma-treated sample at various depth.

㊄ ዻ࠴ ࠲ࡦ᧼ ߩ⚿ ᥏᭴ㅧ ߩᄌ ൻࠍ⹏ ଔߒߚ ‫ޕ‬
Figure 5 ߦ(a)ᧂಣℂ⹜ᢱ‫ޔ‬෸߮(b) ⓸⚛ࡊ࡜࠭ࡑಣℂ⹜ᢱߩ XRD ࡄ࠲࡯ࡦࠍ␜ߔ‫⚿ߩߘޕ‬ᨐ‫ߕ޿ޔ‬ࠇߩ⹜ᢱߦ߅޿ߡ߽‫ޔ‬Ti(100)‫ޔ‬Ti (002)‫ޔ‬Ti (101)‫ޔ‬Ti (102)‫ޔ‬Ti (110)ߦᏫዻߐࠇࠆ࿁᛬ࡇ࡯ࠢߩߺ߇
2θ=35.1‫ޔ‬38.3‫ޔ‬40.1‫ޔ‬53.0‫ޔ‬63.0°ઃㄭߦ⹺߼ࠄࠇ

Intensity / arb. unitߐࠄߦ‫ޔ‬XRD ᷹ቯߦࠃࠅ⓸⚛ࡊ࡜࠭ࡑಣℂߦࠃࠆ(a)(b)ߚ[6]‫ࡑ࠭࡜ࡊ⚛⓸ߪࠇߎޕ‬ಣℂ߇㊄ዻ࠴࠲ࡦ᧼ߩࡃ࡞ࠢ᭴ㅧߦ߶ߣࠎߤᓇ㗀ߒߥ޿ߎߣࠍ⴫ߔ‫ߟޕ‬߹ࠅ‫⓸ޔ‬ൻ࠴࠲ࡦߩᒻᚑ߇⴫㕙ߩߺߢ⿠ߎࠆߣ⸒
߃ࠆ‫ޕ‬30 35 40 45 50 55 60 65 70
2θ / deg.

Figure 5 XRD patterns of (a) as-received Tiplate, (b) N2 plasma-treated Ti plate.

3.2 ㊄ዻ࠴࠲ࡦᓸ☸ሶߦኻߔࠆ⓸⚛ࡊ࡜࠭ࡑಣℂ ⛯޿ߡ‫ޔ‬ᄙⷺࡃ࡟࡞ࡊ࡜࠭ࡑ⴫㕙ᡷ⾰ᴺࠍ↪޿ߡ‫ޔ‬㊄ዻ࠴࠲ࡦᓸ☸ሶߦኻߔࠆ⓸⚛ࡊ࡜࠭ࡑಣℂࠍⴕߞߚ‫ߩ࡞࡟ࡃߩᤨ⵾⺞ޕ‬ᝄࠅሶㆇേߩലᨐࠍ⏕⹺ߔࠆߚ߼‫ࡑ࠭࡜ࡊ⚛⓸ޔ‬ಣℂߪࡃ࡟࡞ࠍ
࿕ቯߒߚ႐วߣᝄࠅሶㆇേߐߖߚ႐วߢⴕߞߚ‫ޕ‬Figure 6(a)ߪಣℂ೨‫(ޔ‬b)෸߮(c)ߪߘࠇߙࠇࡃ࡟
࡞ࠍ࿕ቯ‫ޔ‬෸߮ᝄࠅሶㆇേߐߖߚ⓸⚛ࡊ࡜࠭ࡑಣℂᓟߩ㊄ዻ࠴࠲ࡦᓸ☸ሶߩ౮⌀ࠍ␜ߒߡ޿ࠆ‫ޕ‬
ᧂಣℂߩ㊄ዻ࠴࠲ࡦᓸ☸ሶߪἯ⦡ߢ޽ࠆߩߦኻߒ‫ࠍ࡞࡟ࡃޔ‬ᝄࠅሶㆇേߐߖߡ⓸⚛ࡊ࡜࠭ࡑಣℂߒߚ⹜ᢱߪᓸ☸ሶ߇᣿⏕ߥⶊ⦡ߦᄌൻߒߚ‫ߒޕ‬

1 cm߆ߒߥ߇ࠄ‫ࠍ࡞࡟ࡃޔ‬࿕ቯߒߚ႐วߢߪ⦡⋧ߩᄌൻߪߏߊ௖߆ߢ޽ߞߚ‫ޕ‬Figure 6(b*)ߪࡃ࡟࡞

(a)ࠍ࿕ቯߒߚ⓸⚛ࡊ࡜࠭ࡑಣℂ⋥ᓟߩ౮⌀ࠍ␜ߒ(b)(c)

ߡ޿ࠆ‫⹜ޕ‬ᢱో૕ߩ߁ߜ⴫ጀߩߏߊ৻ㇱߩᓸ☸
ሶߪⶊ⦡ߢ޽ߞߚ߇‫ޔ‬ౝㇱߩᄢㇱಽߩᓸ☸ሶߪἯ⦡ߩ߹߹ߢ޽ߞߚ‫ޕ‬Figure 6(b)ߩ⦡⋧ᄌൻ߇௖

1 cm(b*)߆ߢ޽ߞߚߩߪ‫ߊߏޔ‬ዋ㊂ߩⶊ⦡ߩᓸ☸ሶ߇ᄙ㊂ߩἯ⦡ߩᓸ☸ሶߦࠃࠅᏗ㉼ߐࠇߚߚ߼ߢ޽ࠅ‫ޔ‬ᓸ☸ሶ⹜ᢱ߇ਇဋ৻ߦࡊ࡜࠭ࡑಣℂߐࠇߚߎߣࠍ␜ߔ‫⚿ߩߎޕ‬ᨐ߆ࠄ‫ޔ‬㊄ዻ࠴࠲ࡦᓸ☸ሶ⴫㕙ࠍဋ৻ߦ⓸⚛ࡊ࡜࠭ࡑಣℂߔࠆߚ߼ߦߪ‫࡟ࡃޔ‬࡞ߩᝄࠅሶㆇേߦࠃࠆᓸ☸ሶᠣᜈ߇ᔅ㗇ߢ޽ࠆߎߣ߇ࠊ߆ࠆ‫ޕ‬ ߎߎߢ‫ޔ‬㊄ዻ࠴࠲ࡦᓸ☸ሶߦ߅ߌࠆ⓸ൻ࠴࠲ࡦᒻᚑࠍ⹏ଔߔࠆߚ߼ߦ UV-VIS ࠍ᷹ቯߒ‫ޔ‬㊄ዻ࠴࠲ࡦ᧼⹜ᢱߩ⚿ᨐߣᲧセߒߚ‫ޕ‬ᓧࠄࠇߚ⚿ᨐ
ࠍ Figure 7 ߦ␜ߔ‫ޕ‬㊄ዻ࠴࠲ࡦᓸ☸ሶߩ႐ว‫ޔ‬

Figure 6 Photographs of (a) as-received Ti particles,(b) N2 plasma-treated Ti particles using fixed barrel,(c) N2 plasma-treated Ti particles using oscillating
barrel and (b*) Ti particles in the barrel after N2plasma-treatment using fixed barrel.

⓸⚛ࡊ࡜࠭ࡑಣℂߔࠆߣ 400nm ઃㄭࠍ㗂ὐߣߒߡో૕⊛ߦๆశᐲ߇Ⴧടߒߚ(Figure 7-a)‫⚿ߩߎޕ‬ᨐߪ Figure 7(b)ߦ␜ߔ㊄ዻ࠴࠲ࡦ᧼ߩ UV-VIS ߣ㘃ૃߔࠆ‫ޔࠅ߹ߟޕ‬Figure 6 ߢㅀߴߚ㊄ዻ࠴࠲ࡦᓸ☸ሶߩ⦡⋧ߩᄌൻߪᓸ☸ሶ⴫㕙ߦ⓸ൻ࠴࠲ࡦ߇
ᒻᚑߒߚߎߣࠍ෻ᤋߔࠆߣផ᷹ߐࠇࠆ‫ޔߒ߆ߒޕ‬Figure 1 ߢㅀߴߚࠃ߁ߦ‫ࡑ࠭࡜ࡊޔ‬ಣℂᓟߩ㊄ዻ࠴࠲ࡦ᧼߇㊄⦡ߦᄌൻߒߚߩߦኻߒ‫ޔ‬Figure 6(c)ߦ␜ߔࡊ࡜࠭ࡑಣℂᓟߩ㊄ዻ࠴࠲ࡦᓸ☸ሶߪⶊ⦡

400(a)
after plasma-treatment

as-received

500

600

700

Wavelength / nm

800

Absorbance / arb. unit

Absorbance / arb. unitߢ޽ࠆ‫ߩ⋧⦡ߩߎޕ‬㆑޿ߪ‫ޔ‬ᓸ☸ሶ⴫㕙ߢᒁ߈⿠ߎߐࠇߚశᢔੂߦࠃࠆ߽ߩߣ⠨߃ࠄࠇࠆ‫ޕ‬400(b)
after plasma-treatment

as-received

500

600

700

800

Wavelength / nm

Figure 7 UV-VIS spectra of (a) Ti particles and (b) Ti plates, before and after N2 plasma-treatment.

 એ਄ߩ⚿ᨐ߆ࠄ‫ޔ‬ᄙⷺࡃ࡟࡞ࡊ࡜࠭ࡑ⴫㕙ᡷ⾰ᴺߪ㊄ዻ࠴࠲ࡦᓸ☸ሶ⴫㕙ߦ⓸ൻ࠴࠲ࡦጀࠍᒻᚑߔࠆߩߦ᦭ലߢ޽ࠆߣ⸒߃ࠆ‫⃻ޔࠄ߇ߥߒ߆ߒޕ‬Ბ㓏ߢߪᓸ☸ሶ⴫㕙ߦᒻᚑߐࠇߚ⓸ൻ࠴࠲ࡦጀߩ᭴ㅧ‫ޔ‬෸߮ᷓߐᣇะߩ⍮⷗ߪᓧࠄࠇߡ޿ߥ޿‫ࠍࠄࠇߎޕ‬᣿ࠄ߆ߦߔࠆߚ߼ߦ੹ᓟ‫ࠆߥࠄߐޔ‬ᬌ⸛ࠍⴕ߁੍ቯߢ޽ࠆ‫ޕ‬
4. ߹ߣ߼ ᧄ⎇ⓥߢߪ‫ޔ‬ᄙⷺࡃ࡟࡞ࡊ࡜࠭ࡑ⴫㕙ᡷ⾰ᴺࠍ↪޿ߡ㊄ዻ࠴࠲ࡦ᧼‫ޔ‬෸߮㊄ዻ࠴࠲ࡦᓸ☸ሶߦኻߔࠆ⓸⚛ࡊ࡜࠭ࡑಣℂࠍⴕߞߚ‫ࡑ࠭࡜ࡊ⚛⓸ޕ‬ಣℂࠍᣉߒߚ㊄ዻ࠴࠲ࡦ᧼ߪ‫ᧂޔ‬ಣℂߩ㊄ዻ⦡
߆ࠄ㊄⦡߳ߩᄌൻ߇⹺߼ࠄࠇߚ‫ޕ‬GD-OES ߩ⚿ᨐߪಣℂߦࠃߞߡ⓸⚛ේሶ߇⹜ᢱਛߦଚ౉ߒߚߎߣࠍ␜ߒߚ‫ޔߚ߹ޕ‬ห⹜ᢱߩ XPS ᷹ቯ߆ࠄ‫ࡑ࠭࡜ࡊ⚛⓸ޔ‬ಣℂߦࠃࠅዉ౉ߐࠇߚ⓸⚛ේሶߪᦨ⴫ጀߢߪ࠴࠲ࡦ㉄⓸ൻ‛ࠍᒻᚑߒߡ޿ࠆ߽ߩߩ‫ޔ‬ౝㇱߢߪ⓸ൻ࠴࠲ࡦࠍᒻᚑߒߡ޿ࠆߎߣ߇᣿ࠄ߆ߣߥߞߚ‫ࡑ࠭࡜ࡊ⚛⓸ޔ߅ߥޕ‬ಣℂ೨ᓟߩ㊄ዻ࠴࠲ࡦ᧼߆ࠄᓧࠄࠇߚ XRD ࡄ࠲࡯ࡦߪ‫߽ࠇߕ޿ޔ‬㊄ዻ࠴࠲ࡦߦᏫዻߐࠇࠆࡇ࡯ࠢߩߺࠍ␜ߒ‫⓸ޔ‬ൻ࠴࠲ࡦߩᒻᚑ߇⴫㕙ጀߢߩߺ⿠ߎߞߡ޿ࠆߎߣ߇ಽ߆ߞߚ‫৻ޕ‬ᣇ‫ᧄޔ‬ᚻᴺࠍ↪޿ߚ㊄ዻ࠴࠲ࡦᓸ☸ሶߦኻߔࠆ⓸⚛ࡊ࡜࠭ࡑಣℂߢߪ‫ࠍ࡞࡟ࡃޔ‬ᝄࠅሶㆇേߔࠆߎߣߢ‫ᧂ߇⋧⦡ޔ‬ಣℂߩἯ⦡߆ࠄဋ৻ߥⶊ⦡߳ᄌൻߒߚ‫ࡑ࠭࡜ࡊޔߚ߹ޕ‬ಣℂߒߚ㊄ዻ࠴࠲ࡦᓸ☸ሶߩๆశࠬࡍࠢ࠻࡞ߪ᧼⁁⹜ᢱߣ㘃ૃߒߡ޿ߚ‫⚿ߩߎޕ‬ᨐߪ‫ޔ‬਄⸥ߒߚ㊄ዻ࠴࠲ࡦᓸ☸ሶߩ⦡⋧ᄌൻ߇⓸ൻ࠴࠲ࡦᒻᚑߦ⿠࿃ߔࠆߎߣࠍ⴫ߔ‫ޕ‬એ਄ߩ⚿ᨐ߆ࠄ‫ޔ‬㊄ዻ࠴࠲ࡦᓸ☸ሶߦኻߔࠆ⓸⚛ࡊ࡜࠭ࡑಣℂߦࠃࠅ‫⹜ޔ‬ᢱ⴫㕙ߦ⓸ൻ࠴࠲ࡦጀߩᒻᚑ߇น⢻ߢ޽ࠆߣ⚿⺰ߢ߈ࠆ‫ޕ‬
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