Ta粉の同時脱酸･窒化に関する予備的実験

第4章実験結果及び考察

4.8 Ta粉の同時脱酸･窒化に関する予備的実験

Table 4‑19は､ Ta ‑ N Exp. 1‑4の実験状況及び結果をまとめたものである. Ta‑N Exp. I‑3においては実験前の試料重量と比較して､いずれも約 2%の減少が認められた.またそれに対して､ Ta ‑ N Exp. 4では約2%の重

量の増加が認められた｡このほか､窒素ゲッタ‑としてチャンバー内に入れ

ておいたスポンジチタンも､ 0.116 g (初期重量比で約0.2%)の増加が見ら

れたo ここで､実験3.5で得られたサンプルのm結果をJCPDSカードデ

ータ(Ta2N : 26‑0985､ Ta : 04‑0788､ Mg,N2 : 35‑0778)からの参照パターン､及

びカブトンフイルムのみのXRDパターンとともにFig. 4141に､またTable4‑20

にはサンプルのm解析で確認された相をまとめて示す｡本来Taの窒化物

相として合成の目標にしたのはTaNであるが､ Fig.4‑41のTa‑N Exp. I‑3 において確認された相はTa2Nであった.これは､ Fig. 1‑1のエリンガム図に

示すように､アルゴン雰囲気中の様に窒素ポテンシャルが非常に小さい場合

では､ 1200 Kを含む非常に広い温度範囲においてTaNに対してTa,̲Nが常に

安定に存在することに起因すると考えられる｡したがって､初期Ta量に対する､混合したMg,N2から供給された窒素量は丁度2倍であったと考えられ､

最終的なサンプルの組成もそれに対応して変化したと思われる｡またFig. 4‑

41には､恥‑N Exp14の結果をサンプル表面におけるnDパターン(Ta‑N Exp･ 4･l)と､窒化の影響が及ばないと思われるサンプル内部のXRDパター

ン(Ta‑N Exp･412)とに分けて示してある. Ta‑N Exp.4全体としてはサンプル重量の微小な増加が認められたが(Table4‑19参照)､ Fig. 4141のTa‑N Expl 4･1‑4･2からは､ Taの皿パターンのみが認められたので､他の試料

への窒素の影響は非常に小さかったと考えられる｡スポンジチタンの重量増加を含めた､チャンバー内の試料の全体の重量増加量は､試料全体の重量減

少量の40･3 %であり､残りの減少分はFig･ 4‑41においてMgのnDパター

ンが明瞭に認められなかったことや､ 1200Kという高温において比較的長時間反応させた実験条件を考慮すると､ Mg等がチャンバー内壁やスポンジチタンに蒸着した可能性が考えられる.今回の実験ではMg,N2からTa ‑の窒素の移動･置換を明らかにするためにアルゴンフローの雰囲気内で行ったが､

Ta‑N Expl 1‑3において､ Ta粉の窒化は明瞭に認められたD したがって本

実験結果は､この窒化法を窒素ポテンシャルを上昇させた(pN2 ≧ I )窒素

雰囲気内で行うことにより､現在用いられている方法で合成された製品に比

べ､更に窒化ムラの少ない､良質の窒化タンタル(主としてTaN)粉を得る

可能性について､基礎科学的根拠を与えると判断出来る｡詳細は今後の課題

である｡

Table 4‑1 Result ofLi,N preparation by nitriding lithium metal rods.

(Reaction: 3 Li(S) + I/2 N2(g) ‑Li3N(S))

starting Li PN2 Change･ Obtained Li,N

Ex#p'uIw:eLiinhat:l &NZ/at‑ 竜示Lt:/I;笥デ+

Calc.* A氏erex Calc. ARer ex

1 45.59 ‑7.25 ‑6.93 76.25 76.44 1 00.25 2 63.57 ‑10.11 ‑9.87 106.16 106.48 100.30 3 87･40 ‑13.90 ‑13･76 145.95 146.52 100.39 4 45.47 ‑7.23 ‑6.95 75.94 75,93 99.99

* Calculated by assumlng COnStant Chamber temperature 3 13. 15 K.

(Actualtemperature is T= 298 ‑ 365 K and the volume of chamber is VchdTl.W=

3.$76り

'Calculated from weight change before and after niIriding.

Table 4‑2 Result ofnitrides,'complex nitrides, and alloys synthesis.

EX#p

Ayerage reaction Chemical reaction temperature,

Ta,i /K

Reacted N, amount (Calc.)(I) (ARerexp.)(2) nN,,C/mol nN,..Ae /mol

5 3 Mg+N2‑Mg3N2

6 Li,N+Mg+ 1 /3 N2‑LiMgN+2/3 Li,N

7 1/3Li3N+Mg+I/3N2‑LiMgN

8 1 /3Li‑7N+3 Mg+N2‑LiMgN+2/3 Mg3N2

9 5/3Li,N+Al+1/2N2‑Li3AIN2+2/3Li,N 1 O Li3N+Al+ 1 /2N21･‑Li3AIN2

ll Li3N+5/3Al+5/6N2‑Li3AlN2+2/3 AIN

1 2' aLi3N+b(Li‑Al alloy)*+cN2

1‑Li,AIN2+2/3 Li,N

1 3' a'Li,N+b '(Li‑Al alloy)*+C'N2 ーLi3AIN2

1 4' a"Li,N+b"(Li‑Al al loy) '+C"N2

0.686 0.393 0.087 0.093 0.152 0.154 0.439 0.437 0.112 0.154 0.158 0.182 0.188 0.185 0.144 0.163

0.203 0.207

0.241 0.235 ーLi3AIN2+2/3 AIN

4/3 Li3N+LiGa+2/3N2

‑一Li3 GaN2+2/3 L i 3N

2/3 Li3N+LiGa+2/3N2

ーLijGaN2

4/9Li3N+5/3 LiGa+ 1 0/9N,

ーLi.1 GaN2+2/3 GaN

0.235(3) 0. 1 38(3XJ)

0.235(1'') 0. 1 38(･W)

0.235(3) 0. 1 381'3XJ)

Li+Gal‑LiGa 890 2Li+Ga‑Li2Ga 78 5

( I) Calculated Liom the weight of starting metal, and stoichiometric reaction.

(2) Calculated from dle Weight change of the saJnPIc before and aRermitriding.

(3)Total nitrogen amount for exp. #15, 16, and 17.

(4) Detemined fromthe pressure change of nitrogen during nitriding.

+ : Followlmg are approximate values.

a=l･383, b=l･852, C=0･642, 0'=0.716, b'=1.R52, C'=0.642, 0''=0.527. b"=3.086, C''=1.070

* : Li‑82wt.%Al (Li‑541nOl%Al)

Table 413 Phases identified by Xm in the obtained samples.

Exp･ Phases and composition Phases identified Note

# b

5 Mg3N2 Mg,N,, Mg

6 LiMgN ‑ 40m01%Li,N LiMgN, Li,N, (MgjN,) Represented as

AinFig. 3‑3

7 LiMgN LiMgN, 0.i3N), Represented as (Mg3N2) B in Fig. 3‑3 8 LiMgN ‑ 40m01% LiMgN, Mg3N2 Represented as

Mg3N, C in Fig. 3‑3

9 Li3AlN2‑40m01%Li,N Li,AlN2, Li3N, (N2) Representedas

AinFig. 3‑4

1 0 Li3AlN2 Li,AIN2, (AlN) Represented as

B inFig. 3‑4

11 Li3AIN2 ‑ 40m01% 〟N Li3AIN2, 〟N Represented as

12 Li3AlN2140m01%Li,N Li3AIN2,Li,N, (N2) Representedas

AinFig. 3‑4

1 3 Li,AIN2 Li3AIN,̲, (AIN) Represented as

B inFig, 3‑4

14 Li,AIN2 ‑ 40m01% AIN Li,AIN2, AIN Represented as

15 Li,GaN2 ‑ 40m01% Li,NLi,GaN2, Li,N, (LiGa), Represented as (GaN?) A in Fig. 3‑5 16 Li3GaN2 Li̲,GaNつ, (LiGa), (GaN) Represented as

B inFig. 3‑5

17 Li3GaN2 ‑ 40m01% GaN Li,GaN2, GaN, (LiGa) Represented as

I 8 LiGa LiGa I 9‡ Li2Ga Li2Ga, (Li3Ga2)

Table 4‑4 Result ofequiJibrium experiment for phase diagram studies for the

system Li‑Mg‑N (900 K, 9 days).

Sample Startlng material Phases identified Note

#+ composition by Xm

① Li3N ‑ 25.0m01%Mg

② Li3N ‑ 42.9m01%Mg

③ Li3N ‑ 56.3m01%Mg

④ Li,N‑66.7moJ%Mg

⑤ Li3N ‑ 75.0m01%Mg

@ Li,N l 81.8m01%Mg

⑦ Li3N ‑ 87.5m01%Mg

⑧ Li3N ‑ 92.3m01%Mg

Li3N, LiMgN * Li3N,LiMgN * Mg.,N2,LiMgN *

Mg, Mg3N2 Mg, Mg3N2 Mg, Mg3N2 Mg, Mg3N2 Mg, Mg3N2

Numbers in circle are corresponding to those

the町Stem Li‑Mg‑N at 900K (Fig. 3‑3).

represented in temaJy pltase diagmm for

* : Metal litl血m was slightly identified by Xm.

Table 415 Result of equilibrium experiment for phase diagram studies for the

system Li‑Al‑N (900 K, 10 days).

Sample Starting material

#+ composition

=====:==================

① Li3N ‑ 25.0m01%Al

② Li3N ‑ 42.9m01%Al (卦 Li.,N ‑ 56.3m01%Al

@ Li,N ‑ 66.7m01%Al

⑤ Li3N ‑ 75.0m01%Al

⑥ Li.,N ‑ 81.8m01%Al

⑦ Li3N ‑ 87.5m01%AI

⑧ Li3N ‑ 92.3m01%Al

Phases identified

by Xm

....i.i..i.=■

l■■■■■■ll■ll■■■■■■■l■■‑lllllll■

Li3N,Li,AlN2 Li3AlN2, LiAl Li3AlN,̲, LiAl, 0.i,Al2)(.), G.i,All)(2)

Li,AlN2, LiAl, 0.i3Al2)(I), G.i,Al.)(2)

LijAIN2, LiAl, 〟N

Note

LiAl, AIN &

LiAl, AIN 丘

(I) :Also identified b

(2) : AJso identified by Xm as an incomplete equilibrium phase.

+ : Numbers in circle are corresponding to山ose represented in temary pllaSe diagram for d一e町Stem Li‑Al‑N at 900K (Fig. 3‑4).

* : Metal li血ium was slightly identified bv XRD.

A : Metal alulninum was slightly identified by XRD.

y Xm as an incomplete equilibrium pllaSe･

Table 4‑6 Result ofequilibrium experiment for phase diagram studies for the

system Li‑Ga‑N (700 K, 8 days).

Sample Starting material Phases identified Note

#+ composition by Xm

(む Li,N‑50.0m01%LiGa

② Li3N‑71.5m01%LiGa

@ Li,N185.0m01%LiGa

④ Li3GaN2 ‑

50.0 m01%Li2Ga

⑤ Li3GaN2 ‑

80.0 m01%Li2Ga

⑥ Li3GaN2 ‑

95.0 m01%Li,Ga

Li3N, LiGa Li3N, LiGa Li3N, LiGa Li3N, Li3GaN2, LiGa

LiGa,Li,Ga2, (Li2Ga)M, *

(Li3GaN2)(2)

Li2Ga, Li,,Ga2, *

( 1) : Also identified by nD as anきncomplete equilibrium pllaSe･

(2) :Also identified by XRD as an Incomplete equilibrium phase.

': Numbers in circle are corresponding to those represel一ted ill lemary pllaSe diagmm for

the systemLi‑Ga‑N at 700K (Fig. 3‑5).

* : Li仙ummitJjde was slightly identified by XRD.

Table 4‑7 Impedance ofLi3N measured by FRAwith afrequency of 1002.37 Hz., and its calculated ionic conductlVlty.

Temperature, Impedance, Conductivity( I )

T/ K IZl / ohm qT/ Sm‑.K

0 0 0 0 0 0 0 0 0 0

′0 7 00 9 0

1.13×103 I.69× 102

31.6 0.852 0.198

17.9

1.40X 102

8.59× 10三 3.58× 104 1.72×105

(I) : The size of the Li3N pellet is 15･5 1Tun in dialneter and 6･4 1nJn in tllickness (Au,N

= 1･89 × 10'4 m2･ /L13N = 6･40× 10･) ln ).

Table 4‑8 Impedance ofLiMgN measured by FRA with a fTrequency of lOO2.37 Hz., and its calculated ionic conductlVlty.

Temperature, Impedance, Conductivity( I )

T/K lq /ohm qT/ Sm‑lK

0 0 0 0 0 0 0 0 0 0 7 00 q′ 0 1

1 1

1.60× loヰ

3.26X 103

7.88× 103

17.42X 102 2.86X 102

I.16 6.51 3.03 35.7

1.02X 10:

(1) : The size oftlleLiMgNpellet is 15･5 1nm in diameter and 5･O ITun im tldckness ( ALlh.gN

‑ 1189× 10･4m2･ /LIMsN ≡ 5･00× 10･3m )･

Table 4‑9 Impedance ofLi3AIN2 measured by FRA with a frequency of lOO2.37 Hz., and its calculated ionic conductlVlty.

Temperature, Impedance, ConductlVlty(u

T/K lq /ohm qT/ Sm'.K

0 0 0 0 0 0 0 0 0 0 7 00 0ノ 0 1

1 1

5.66× loョ 1.54× loョ 5.52× 102 I.32× 102

61.9

4.91 20.6 64.8

3.01 × 102

7.06X 102

(1) : The size of the Li'AlN2 Pellet is 15･5 mm in diameter and 7･5 ITun in tllickness ( Au,4'N,

‑ l･89× 10J m2･ /uJNN2= 7･50× 10‑3m )･

Table 4‑10 Impedance ofLi..GaN, measured by FRA with a fTrequency of lOO2.37 Hz., and its calculated ionic conductivity.

Temperature, Impedance, ConductivityM

T/K lq /ohm qT/ Sm‑IK

0 0 0 0 0 0 0 0

5 ′0 7 00 5.62× 105 4.91 ×104 I.23×104 3.00× loll

1.89X 10‑:

0.259 I.20 5.65

(1) : The size oftheLi3GaN2 pellet is 15･5 mm in diameter and 4･O mJn in thicklleSS ( ALL,GaN,

= l･89× 10‑4 m2･ /uJGaNZ=4･00× 1013m )･

Table 4‑1 1 Summary of ionic conductlVlty measurement Ofnitride and temary complex nitrides carried out in this study.

Conductivit

"aterial Taenmgpe?rF/uke ( qL,o/gsqmTK,

U.印.uK/ Sm･l q.a約.日に/ Sm･1

Li3N 600‑ 1000 ‑6210/T+ll.23 0.2 1.07 LiMgN 700‑1100 ‑3480/T+ 4.95 1.66XI0‑3 8.14XIO‑, Li3AIN2 700‑1100 ‑4240/r+ 6.67 7.01×10‑3 2.58×10･三 Li3GaN2 500‑ 800 ‑3270/㍗+ 4.80 1.71×10‑3 7.06×10‑3

Table 4112 Thermodynamic properties ofLiMgN obtained &om E.m.f.

measurement.

Temperature, Number of the

Average E･m･f･(I), EE.m.f.a,i / V Standard deviation, T/K E･m･f･ m/easured (error :+̀2', ‑(3') 2qsd'4'/V

0 0 0 0 0 0 00 q/ 0

1 2 4 2 0.119

0･137 (十0.003, ‑0.003) 0･ 144 (+0.048, ‑0.024) 172 (+0.035, ‑0.035)

(1) Red (positive) line is connected to Mg,N, side and black (negative) line is connected to Li,N side.

(2) Error diqerence tome maximum value.

(3) EJTOr diqerence tothemimimum value.

(4) De丘mitionfor qs.d. : qst.. ‑ ( M(X2) ‑ M2(X) )'r2 ,where M(X) is a mean valuefor x一.

Table 4‑13 Thermodynamic properties ofLi,AlN2 Obtained from E.m.f.

measurement.

Temperature･ Number of the Average E.m･f･(I), EEmf..,i. / V Standard deviation,

T/K E･m･f･ measured (+error : +(3), ‑̀3)) 2q血(J'/V

700 800 900 1000 1100

2 4 ′0 5 4 0･189 (+0.017, ‑0.017) 0･284 (+0.013, ‑0.012) 0.679 (+0.196, ‑0.235) 0･263 (+0.042, ‑0.057) 0.217 (+0.016, ^‑0.023)

0.034 0.022 0.260 0.078 0.030 (1 ) Red (positive) line is connected loAlN side and black (negative) line is connected to LilN side.

(2) Error difference to the maximum value.

(3) Error di飴rence tothe minimum value.

(4) Defimition for qs,d. : qs.d. ‑ ( M(X2) ‑ M2(X) ).a ,where M(X) is a mean valuefor x,.

Table 4‑14 Thermodynamic properties ofLi,GaN, obtained舟om E.m.f.

meaSurement.

Temperature, Number of the Average E･m.f.(I), Standard deviation, T/K E･m･f･ measured EEmf,M./V 2qsd(,‑)/V

500 600 700 800 (850)

円いhHJ

1 1 1 I 1

lH川■Ju

0.269 0.128 0.0940 0.0320 (0.000)

( 1) Red (positive) line is corLneCted to GaN side a)ld black (nega山′e) line is corLneCted to Li,N side.

(2) Derlnition for qs,J : qstd ‑ ( M(X2) ‑ M2(X) )tn ,where M(X) is a mean value far x,.

Table 4‑15 The obtained E･m･f･ value and the calculated value of △Go,･,. and △GT′.I.I

cn?.TiPJeesx Tempe/r;ture･T 等･ ′Ak,GmO.,ii･l ′k?mG.uli･.

LiMgN Li3AIN2 Li3GaN2

0 0 0 0 0 0

0ノ 9 7 0.137 ‑13.9 ‑122 0.679 ‑198 ‑466 0.0940 ‑27.4 ‑128

Table 4‑16 The calculatedminimumpN2 under existence ofcomplex nitride･

complex Temperature, T LogPmlnNz.MN,.,L叫(1) LogPmmN,,LIMxNy(三) nitrides / 氏

LiMgN 900 ‑10. 1 ‑10. I Li3AIN2 900 ‑23,4 ‑25.0 Li‑GaN, 700 ̲1. 10 ̲3. 10

(I)JrnNZ,MN,JLiMxN, lSmimiInum paJlial nitrogen POtential under MN,･,LiMxN, co ‑ e･dstence･

(2) P'u■NZ叫N, lS minimum由･tialmitrogen potential for LiMxN, complexmitride･

Table 4‑17 Result ofI=i,GaN2 / GaN sample synthesis for new GaN synthesis study

Average reaction Reacted N, amount

Chemical reaction temperature, (calc.)(1) (ARer exp.)(:)

Tave･/K nN2,C/mol nN.,Ae /mol

20 2LiGa+ 1 /3 Li3N十4/3N2

‑Lil GaN2+GaN 3 LiGa+2N2

ーLi3GaN2+2 GaN

3 LiGa+3 Ga+7/2N,

ーLi3GaN,+5 GaN

1040 0.096 0.037

1040 0.13

1040 0.14

( 1) Calculated丘omthe weight of starting metal, and stoiclliolnetric reaction.

(2) Calculated丘om the weight change of the sample before and aRer nitriding.

(3) Not available.

Table 4‑18 Phases identified by XRD in the obtained samples･

Exp. Phases and composition Phases identified Note

# bv Xm

20 Li.,GaN2 ‑

50.0m01% GaN

21 Li5GaN2 ‑

66.7m01% GaN

22 Li3GaNっ‑

83.3mol% GaN

Li,GaN2,LiGa, (GaN?)

Li3GaN2, LiGa, (GaN?)

Li,GaN2, LiGa, GaN (1)

( 1) Fe and Fe3Ga was slightly detected by XRD.

Table 4‑19 Result of the‑samples for Ta powder nitriding study.

Exp#

Average reaction Weight change,

Chemical reaction temperature, A W / %

Tave / K (I)(:)

Ta‑N 1 Ta+1/2Mg,N2‑TaN+3/2Mg

Ta‑N 2 2Ta+1/2Mg,N21‑TaN+Ta+3/2Mg Ta‑N 3 10Ta十1/2Mg,N2‑TaN+9Ta+3/2Mg

Ta‑N 4 Ta‑Ta

1200 ‑2.3 1 1200 ‑1.74 1200 ‑0.201 1200 +0.206

(I) Percentage of weight change versusthe sample weight in the begiming.

(2) (‑) stands for decrement and (+) stands for increment.

Table 4‑20 Phases identified by XRD in the obtained samples･

Exp･ Phases and composition Phases identified

# b

Ta‑N 1 Ta‑N 2 Ta‑N 3

Ta̲N 4. 1(I)

1もーN 4.2(2)

TaN ‑ 60.0 m01%Mg

TaN ‑ 28.6 m01%Ta ‑ 42.9 m01%Mg TaN ‑ 78.3 m01%Ta ‑ 13.0 m01%Mg

Ta Ta

Ta2N, Ta, Mg3N2 Ta,̲N, Ta, (Mg3N2) Ta2N, Ta, (Mg3N2)

Ta Ta (I) Obtained from suTfacial part of the sample for Ta ‑ N Exp. No. 4.

(2) Obtained from irLner Cen血I part oftlte salllPle for Ta ‑ N Exp. No. 4.

eJ/cOLXNNdtaJnSSaJJ

㈱

^2 1^0 5^{0 0}

0 0 0 0 5 1

0 0 0 0 0 0 0

8765432 00＼tlOJnleJad∈ei

桝

l･2 0･8 0･4 0･O N10∈＼NNLtno∈eNPOIUeatJ

EthHu

nlU

1 0 20 30 40 50xl 03

Time, I/S

10 20 30 40 50xlO3

Time, i/S

ILIT

Theoreticaーamoutofnitrogennecessaryfornitriding(1.09molN2).

Chargedtithiummetat:45.59g(6.57mol)

lObtajnedlithiumnitride:76.44g(Theo.amout76.25g)

10 20 30 40 50xl 03

Time. I/S

Fi且 41 1 (a) Chan野Ofchn心er pressure during nibiding oflithum n℃tal rods

(Exp. #1inTable4‑1 ).

O)) Change ofchnもer tempeTatuPe dtqing FeaCdon ( Exp. #1 ).

(.m?)ZE倉sualuJ

(4m2)r倉suo王

制

(.n.e)r倉suo三

一HLリ

rHJHU

('n.e)rh!suo王

㈹

xll/lJITI

×(Exp.#1)Sample+Kaptonnlm

× × × × lJl 浮粭ﾆ邃､5 E33 ﾓ sS鋳

××××× ｣】LJ▲.̲ー▲̲

一.【ー1‑‑‑‑‑一一

20 30 40 50 60 70 80 90 1 00

2β (dog.)

Kapbn刑m

40 50 60 70 80 90 1 00

2♂ (°eg.)

rlJILll

Li3N(JCPDS30‑0759)

lllLllJlf

40 50 60 70 80 90 1 00

2β (dog.)

J l 免ﾆﾆﾆﾆﾂ

Li(JCPDS15‑0401)

..A.(.l.A.

40 50 60 70 80 90 1 00

2β (dog.)

Fig･ 412 (a) Xm pattem of the obtainedLi3N sample ( hp. #linTable 411 )

+ Kapton恥(b) Kapton GJnt (C) Reference pattem ofLi3N, and

(d) Reference pattem ofLi.

(.nd)][^)!suoluI

(.nre)I‑A)!suoIUl (･コ･且r^)!suoluI

30 40 50 60

Angle. 20(deg.)

70 80

ll .I.l 白停 I ■l 免ﾂﾓ └5 E3｣3Rﾓ ssｒ貭 I^免ﾂ

20 30 40 50 60 70 80

Angle. 2β(°eg.)

tl ..H 免ﾆﾆﾂ

Mg(JCPDS:04J770)

.lJllllll

20 30 40 50 60 70 80

AngLe, 20(deg.)

Fig. 4‑3 ¶le Xm result of the obtained powder.

(a) Obtained M亀N2 pOWder･

O)) Mg3N2 reference pattem (JCPDS 3 5‑0778)･

(.m2)Zt^)!Sualur

㈱

^(lJJJ MgN

32tl ≡ FQ lコI ▲≡ぎー▼〉 ▲ぎ ● I 埜､ﾆ磐t

●:Li3N rl Z

tD ‑̲●̲▲一息血丘‑■̲∫̲.‑̲A.̲▲.‑ P〜

｢一一.■'■tl‑‑一一‑‑ll

('n.e)r^)!suoIU[

桝

(.n.e)r^)!SuoluI

LHrhu

lHH1日U

Mg3N2Nl 剿ﾆﾄ､｢

≡ ゴ▲ 凵ﾟぎzS 埜 vﾄﾔﾆ磐t萃

rl ･ztDn ≡ 披

≡ PO

tn ≡

A̲̲崩.▲ふ̲A̲̲̲.A̲▲̲̲▲̲L

l 8示迄耳耳 ( 爾ﾘ爾

120 140

I ▲+ 冤lーl

Exp.#8▲:LiM9N

+:M93N2

+仙‑h血出k4J,,J+良

‑1‑‑‑■一■ー‑一一一■■■l‑

20 40 60 80 100 120 140

2β (de9.)

(.nd)r^)!sualu[

㈹

Kapton film

40 60 80 100 120 140

2β(°eg.)

Figl 4‑4 The Xm result of the samples prepared for E.m.f studies, of which

composition is correspondingto (a) A, (b) B, and (C) CinFig. 3‑3.

The Xm pattem ofkapton h is also shown as (d).

(.nd)r^)!suotuJ

㈱

^1‑llflJ

Exp.#12▲:Li3AIN2

●zN ▲ 偵､ﾆ墜茲 8 8 ﾈﾂ

20 30 40 50 60 70 80 90

2β (dog.)

(.nre)I‑At!suoIUI

桝

(.n.e)rAt!suoluf

CnrHu

ilU

(.つ.且＼‑ゝl!Sualur

㈹

I l ｴ繒 lll Exp.#13lA:Lj,AIN2 ▲▲葦▲▲▲

20 30 40 50 60 70 80 90

2β(dog.)

lJftll

▲Exp.#11▲:Li3AIN2

▲ ▲ I :A一N +++▲

20 30 40 50 60 70 80 90

2β(°eg.)

Kapton刷m

30 40 50 60

2β (°eg.)

70 80 90

Figl 4‑5 The Xm result ofdle Samples prepared for E.rn.f studies, of which

composidon is correspondingto (a) A,仲) B, and (C) CinFig 3‑4.

The Xm pattem ofkaptonfilmis also shown as (d).

(.nd)Zt^)!suolul

榊

^IJJIIl

Exp.#15▲:Li3GaN2

●:Li3N

rL.

毒A‖.壁..A.̲A

l一一一一一一一一一一一

20 30 40 50 60 70 80 90

2β(°eg.)

(.nd)rAt!suatu]

㈹

(Jnd)ZL^l!SuStu一

一11LHu

IH一JHU

(.nre)I(At!suolu1

㈹

IIIIJl

一一 ≡ 巾 O 丼u6 B Exp.#16lA:Li,GaN2l z▲8

tq.J

I 筈｢ o▲L▲̲ ｢‑

20 30 40 50 60 70 80 90

2β(°eg.)

tlllll

Exp.#17^:Li3GaN2

d O :コ諜､v

▲

壁七壁.壁.hL.. l 一.

20 30 40 50 60 70 80 90

2β(de9.)

lllIJL

KaptonfiLm Jー'‑'ーT一一一一‑1.‑‑‑一一,

30 40 50 60 70 80 90

2β(°eg.)

Fig. 4‑6 刀le XRD result of the samples prepared for E.m.i: studies, of which composidon is correspondingto (a) A,仲) B, and (C) CinFig･ 3‑5･

The Xm pattem ofkaptonfih is also shown as (d)･

(4m2)rAl!SuOlu[

20 30 40 50 60 70 80

2β(°eg.)

(.n'e)ZtAl!SuOlu一

20 30 40 50 60

20(deg.) (.nd)rAt!Suolul

nrhH一

rHJHU

TJ 白 Jl

A̲.L‑A Kaptonfilm

l'1'ー1T‑‑一一, '一一日 =一一一一一‑ ｨ耳耳ﾘ

20 30 40 50 60 70 80

2β(°eg.)

Fig･ 4‑7 The nD pattem of the obtained (a)LiGa sample and (b) Li2Ga sample

prepared for equhbrium experimentinphase dhgramstudies.

The XRD pattem ofkapton h is also shown as (C).

(.n.e)Zt^l!SUOluI

I 劔lJIJ

① ② ③ ㊨ ⑤ ⑥ ⑦ ⑧ ﾂ● ̲1. 儉i3N+LiMgN(+Lj) ●▲▲●▲▲▲▲▲▲▲▲ ､ﾈ.t粨 Dﾖs4 Dﾆ磐t粨 DﾖwB

● ● ● ● 劔･̲.̲ll./...::.lLi.3:"'.T.:."I.'三i':.

◆ ◆◆◆◆ 劔日.Mg3N2'LiMヲN('u)

◆◆▲▲▲▲▲ ◆◆◆◆◆◆◆'A'J'..ナ'!.◆.◆◆◆◆.'..̲チ̲̲....I̲'̲.'....̲.

● ◆◆◆ 劔Mg+Mg3N2(+Li) ●●〇%●◆〇〇〇〇〇〇〇〇〇〇〇〇 '◆◆◆◆◆◆tfIf̲.!{LL〜̲'..̲'̲チ.̲...̲'̲.'HH.

◆ 凵 ◆◆◆◆ 劭..Mg+Mg3N2(+Li) ○ ◆.◆◆◆..▲む.̲.†T̲.:{:'.I.千..!士....'̲.1...̲

○ ◆ ◆ ｲ ...Mg+M93N2(+Lj) ○○◆○○.〇〇〇〇〇〇〇〇〇〇 ◆◆◆◆◆t'†◆†'1:小.:1'.◆..!L....亡.i....i

◆ 凵 ◆◆◆◆ .Mg+Mg3N2(+Li)

｡ヽ｡.｡.｡.｡.｡.｡.｡.

◆◆◆◆◆...十..◆.◆{◆◆〜...!′....十.◆...‑

◆ ..'‑'.｡.｡..｡.‥｡.｡..M9'.M5)3N.2('Li). ･.◆◆◆◆◆..̲.二.̲.̲..I.'̲..'1.̲....̲.̲...◆...◆.

Jllll

20 40 60 80 100 120 140

An9le, 2β/ °eg.

Fig･ 4‑8 XRD results obtained斤om the equirbrium experiment forthe system Li‑Mg‑N at 900K and reference pattems丘om JCPDS cards.

(.m2)I(At!SuOluf

① ② ③ ㊨ ⑤ ⑥ ⑦ ⑧ 免ﾆﾄ幡ﾂ

L.:Li,N▲‥Li,AIN20:LiAl.‥AtNf

'Li3N+Li3AIN2(+Li) ▲▲●●▲▲▲▲▲ ●●▲▲▲●●●▲▲

A3..A..Li3A.rN2+.Li.Al(+Li) b○○▲A‑▲○○▲○▲

■■

草書.喜寿仍ﾒ粨ｨ粐粐菷ﾂ#(ﾘf剃｢Ｕﾆ鋳

〇〇〇〇〇〇

1ー

卜も

互.享.冒.仁.茎.‥ALi3A.,T.2:LT.. 1■

Li3AIN2+LiA一+AIN ◆○

▲◆▲▲▲◆ 諦褸れﾒ

.苛苛. 犯ﾂｴﾄ竄ｴﾂｸｲﾈｨ

LiAJ+AIN(+Al) ○

+苛苛◆◆◆○◆○◆○○

LiAJ+AIN(+Al) ○ +苛苛◆◆◆○◆○○

llllll

20 30 40 50 60 70 80 90

An9te, 2β/ °eg.

Fig･ 4‑9 ⅩRD result obtained丘om the equ止ibrium experiment for the system

Li‑Al‑N at 900K and reference patterns qom JCPDS cards.

② ③ ④

(.m2)ZLAt!sualu[

⑤ ⑥

20 30 40 50 60 70 80 90

A咽Ie, 2β/ °eg.

Fig 4‑ 10 Ⅹm resuks obtained G･omthe equibrium experiment forthe system

Li‑Ga‑N at 700K and reference patterns 80m JCPDS cards･

1/2 N2 (g)

[Li‑Mg‑Nsystenat900K

1/3 LiMgN (S)

1/4 Li3N (S)

@ :Composition of samples

br phase diagram studies

ロ:Composition of electrodes

br E.m.f. studies

1/5 Mg3N2 (S)

Fig･ 4‑I 1 Ternary phase di喝ram f♭r the system Li‑Mg‑N at 900K

obtained from the XRD results of the equilibrium experiment･

Mg (S)

1/2 N2 (g)

LトAトNSystem at900K

1/6 Li3AIN2 (S)

(∋ :Composition of samp一es

br phase diagram studies

□ ‥tomposition of electrodes

br E.m.f. studies

1/2 LiAl (ら)

Fig. 4‑12 Ternary phase diagram for the system Li‑Al‑N at 900K

obtained from the XRD results of the equilibrium experiment･

Al (S)

1/2 N2 (9)

Li‑Ga‑NSystemat700K

1/6 Li3GaN2 (S)

Li (I)

(a :Composition of samples

for phase diagram studies

[∃ :composition of eJectrodes fわr E.m.f. studies

1/2 GaN (S)

1/3Li2Ga(S) ＼.1/2LiGa(S)

1/5 Li3Ga2 (S)

Fig･ 4‑13 Ternary phase diagram for the system Li‑Ga‑N at 700K obtained from the XRD results of the equilibrium experiment

GaM

54321 (NL̲ ∈SJ1D)P601■^)!^!tDnPuOU

1.2 1.4 1.6

1000 r 1 / K‑1

Fig･ 4‑ 14 Temperature dependence of ionic conductivityofLi3N

measured by FRAwith a舟equency of 1002.37 Hz

(Nt･ ∈SJ1D)1D601(A)!^!73nPuOU

4 2 0

‑ : This study

‑ ‑ ‑: Ref.data

ヽヽ

ヽ

JogoT=‑2980/T+7･14 ヽヽ

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

1000 T‑1 /K‑1

Fig･ 4‑ 1 5 Comparison of regression lirkBfor obtainedLi3N ionic conducdvity data

and data G'omref: 33). .

(NL･ UJSJJD)JD601&^1!^!PnPuO3

2 2 5 .0

ー･5 川 o･5 0･0

0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5

1000 r‑1 / K‑1

Fig. 4‑ 16 Tempera山re dependence of ionic conductivityofLiMgN measured by FRA with a丘equency of lOO2･37 Hz

(Nt･ ∈SJP)JD6oJI^1!^!IDnPuOO

2 1

0 ▲ー

つ▲ 3

‑ : This study

一一一: Ret.data

ヽヽ

logdT=‑3470/T+5.ll ヽ､

1.0 1.5 2.0 2.5

1000 r‑1 / K‑1

Fig 4‑ 17 Comparison of regression he for obtained LiMgN ionic conducdvity data and data Com ref: 12).

(NL̲ ESJ1D)JD6ott^)!^竜nPuO3

5 . 0 5 . 0 2 2 1 1

0.9 1.0 1.1 1.2 1.3 1.4 1.5

1000 r‑1 /K‑1

Fig 4‑ I 8 Temperature dependence ofio血conductivity ofLi3AlN2 meastJred by FRAwitha Bequency of 1002.37 H乙

(Nt̲ UJSJP)1D60lIAt!^!tDnPUOO

4 2

2 4

1.0 1.5 2.0 2.5 3.0 3.5

1000 r‑1 / K‑1

Fig･ 4‑ 19 Comparison ofregressk)nlinefor obtained Li3AlN2 ionic conductivitydata

and data丘om ref 12) 20). LiAlCl4 ionic conducdvitydata G'om ref: 34) is

also showninthis Ggure.

=== ; ; ;

(NL̲ ∈SJJD)1D6olt^)!^葛nPUOU

JlJl

ヽヽﾃ､ 'F 匁VFF F

ヽヽヽヽヽ ‑､ヽ l 辻ﾒﾓ･&Vw&W76柳貳匁Vf & 'F 匁VFF F

ヽヽ

ヽ

､一

ヽヽ

logdT=‑3270/T+4.80､､

ヽ

lll

1.2 1.4 1.6 1.8 2.0

1000 r‑1 / K‑1

Fig･ 4‑20 Temperature dependence of ionic conductivityofLi3GaN2

meastqed by FRAwith a 6.equency of 1002.37 Hz

(0420

(Nt. ∈SJ1D)JD6ott^)!^!tDnPUOO _lll 價I

ヽヽヽヽ '‑...､..tI.. ヽヽ lt 蔦･&Vw&W72 onlineforLi3Ndata

･‑.:Re9reSS 薬v貳匁Vf $ﾆ磐t襷 F

一.‑:Regress 柳貳匁Vf $ﾆ斐&F F

‑...:Re9reSS 柳貳匁Vf $ﾆ v F F

ヽ

T>..:.‑.

●●●‑●

●､●

●‑●

一一●

●‑●

l暮l一一一

0.8 1.0 1.2 1.4 1.6 1.8 2.0

1000 r‑1 / K‑1

Fig. 4‑21 Regression lines for ionic conductMtyofnitride and termry complex nitrides measuredinthis study.

o･2｡ o･1 8 0･1 6 …

>＼gt').∈山

lll

●:Obtaineddata 凵｡■ ■■ ■■ 一■ ■■ IP ■■ I

‑‑:Regressionlineforobtaineddat?

E=‑1.45×10‑2+1.65×104T一

■■

一■

■■

̲圭‑‑一

■■

一■

●′

一lー

800 900 1000 1 100

Temperature. r/ K

Fig･ 4‑22 Result of the E･m･f meastJrement OfLi‑Mg‑N system for

battery ceu of the three Phases equ此rium con･esponding

to l'land 2..inFig. 2‑14.

ドキュメント内ナイトライドメタラジー:窒化物の熱力学と新合成法の開発 (ページ 74-117)

第4章 実験結果及び考察

4.8 Ta粉の同時脱酸･窒化に関する予備的実験

量の増加が認められた｡このほか､窒素ゲッタ‑としてチャンバー内に入れ

れたo ここで､実験3.5で得られたサンプルのm結果をJCPDSカードデ

にはサンプルのm解析で確認された相をまとめて示す｡本来Taの窒化物

示すように､アルゴン雰囲気中の様に窒素ポテンシャルが非常に小さい場合

安定に存在することに起因すると考えられる｡したがって､初期Ta量に対 する､混合したMg,N2から供給された窒素量は丁度2倍であったと考えられ､

最終的なサンプルの組成もそれに対応して変化したと思われる｡またFig. 4‑

への窒素の影響は非常に小さかったと考えられる｡スポンジチタンの重量増 加を含めた､チャンバー内の試料の全体の重量増加量は､試料全体の重量減

実験結果は､この窒化法を窒素ポテンシャルを上昇させた(pN2 ≧ I )窒素

雰囲気内で行うことにより､現在用いられている方法で合成された製品に比

べ､更に窒化ムラの少ない､良質の窒化タンタル(主としてTaN)粉を得る

可能性について､基礎科学的根拠を与えると判断出来る｡詳細は今後の課題

Ex#p'uIw:eLiinhat:l &NZ/at‑ 竜示Lt:/I;笥デ+

Ayerage reaction Chemical reaction temperature,

4/3 Li3N+LiGa+2/3N2

2/3 Li3N+LiGa+2/3N2

4/9Li3N+5/3 LiGa+ 1 0/9N,

* : Li‑82wt.%Al (Li‑541nOl%Al)

B inFig. 3‑4

B inFig, 3‑4

=====:==================

by Xm

(Li3GaN2)(2)

T/K lq /ohm qT/ Sm‑lK

(1) : The size oftlleLiMgNpellet is 15･5 1nm in diameter and 5･O ITun im tldckness ( ALlh.gN

T/K lq /ohm qT/ Sm'.K

"aterial Taenmgpe?rF/uke ( qL,o/gsqmTK,

Temperature, Number of the

(I)JrnNZ,MN,JLiMxN, lSmimiInum paJlial nitrogen POtential under MN,･,LiMxN, co ‑ e･dstence･

‑Lil GaN2+GaN 3 LiGa+2N2

3 LiGa+3 Ga+7/2N,

Li3GaN2, LiGa, (GaN?)

Ta‑N 1 Ta‑N 2 Ta‑N 3

eJ/cOLXNNdtaJnSSaJJ

㈱

桝

制

㈹

Kapbn刑m

lllLllJlf

Fig･ 412 (a) Xm pattem of the obtainedLi3N sample ( hp. #linTable 411 )

tl ..H 免ﾆﾆﾂ

(.m2)Zt^)!Sualur

㈱

桝

㈹

Figl 4‑4 The Xm result of the samples prepared for E.m.f studies, of which

composition is correspondingto (a) A, (b) B, and (C) CinFig. 3‑3.

The Xm pattem ofkapton h is also shown as (d).

㈱

桝

㈹

Figl 4‑5 The Xm result ofdle Samples prepared for E.rn.f studies, of which

The Xm pattem ofkaptonfilmis also shown as (d).

榊

㈹

㈹

Exp.#17^:Li3GaN2

壁七壁.壁.hL.. l 一.

The Xm pattem ofkaptonfih is also shown as (d)･

Fig･ 4‑7 The nD pattem of the obtained (a)LiGa sample and (b) Li2Ga sample

The XRD pattem ofkapton h is also shown as (C).

(.m2)I(At!SuOluf

① ② ③ ㊨ ⑤ ⑥ ⑦ ⑧ 免ﾆﾄ幡ﾂ

互.享.冒.仁.茎.‥ALi3A.,T.2:LT.. 1■

(.m2)ZLAt!sualu[

Li‑Ga‑N at 700K and reference patterns 80m JCPDS cards･

1/2 N2 (g)

[Li‑Mg‑Nsystenat900K

1/3 LiMgN (S)

1/4 Li3N (S)

@ :Composition of samples

br phase diagram studies

ロ:Composition of electrodes

br E.m.f. studies

1/5 Mg3N2 (S)

Mg (S)

1/2 N2 (g)

第4章実験結果及び考察

安定に存在することに起因すると考えられる｡したがって､初期Ta量に対する､混合したMg,N2から供給された窒素量は丁度2倍であったと考えられ､

への窒素の影響は非常に小さかったと考えられる｡スポンジチタンの重量増加を含めた､チャンバー内の試料の全体の重量増加量は､試料全体の重量減