JPS61183437A - High strength sintered alloy and its production - Google Patents
High strength sintered alloy and its productionInfo
- Publication number
- JPS61183437A JPS61183437A JP60022655A JP2265585A JPS61183437A JP S61183437 A JPS61183437 A JP S61183437A JP 60022655 A JP60022655 A JP 60022655A JP 2265585 A JP2265585 A JP 2265585A JP S61183437 A JPS61183437 A JP S61183437A
- Authority
- JP
- Japan
- Prior art keywords
- solid solution
- sintered alloy
- powder
- carbonitride
- carbonitride solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は８周期律表４ａ、５ａ、６ａ族金属、特に４ａ
族金属のＴｆを主体とし、更に６ａ族金属のＷを少なく
とも含む炭窒化物焼結合金及びその製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention is directed to metals of groups 4a, 5a, and 6a of the 8 periodic table, especially metals of groups 4a and 4a of the periodic table.
The present invention relates to a carbonitride sintered alloy mainly containing Tf, a group metal, and further containing at least W, a group 6a metal, and a method for producing the same.
（従来の技術）
従来、周期律表４ａ、５ａ、６ａ族金属の化合物と鉄族
金属を主体にした焼結合金として、超硬合金又はサーメ
ットがある。この内、サーメー。(Prior Art) Conventionally, cemented carbide or cermet has been used as a sintered alloy mainly composed of compounds of metals of groups 4a, 5a, and 6a of the periodic table and iron group metals. Among these, Thermae.
トとして注目されているのにＴｉを主体にした化合物と
鉄族金属からなる焼結合金がある。サーメットとしては
、まずＴ ｉ ＣにＭｏ又はＭｏ２Ｃを添加してなる（
Ｔｉ、Ｍｏ）Ｃ固溶体と鉄族金属からなる炭化物系焼結
合金が開発され、Ｔｉｃに比べて（Ｔｉ、Ｍｏ）Ｃが鉄
族金属との濡れ性の向上に寄与したことによって成る程
度実用化されている。しかし、焼結合金中の（Ｔｉ、Ｍ
ｏ）Ｃ固溶体結晶粒子は、均賀相でなく中芯部がＴｉに
富んだ固溶体相であるのに対し外周部がＭｏに富んだ固
溶体相であるために鉄族金属との濡れ性に向上した反面
、外周部の硬さ及び強度の低下が生じるという問題があ
る。この炭化物系焼結合金を改良したものとして、主と
してＴｉＣにＴｉＮ又はＴ ｆ Ｎ ＣとＭｏ，Ｍｏ２
Ｃ又はｗｃを添加してなる炭窒化物固溶体と鉄族金属か
らなる炭窒化物系焼結合金が多数提案され、例えば特願
昭４９−６９６２４号は、１つの改良方向を提案したも
のである。Sintered alloys consisting of Ti-based compounds and iron group metals are attracting attention as potential targets. Cermet is first made by adding Mo or Mo2C to TiC (
A carbide-based sintered alloy consisting of a Ti, Mo)C solid solution and an iron group metal was developed, and its practical use was achieved because (Ti, Mo)C contributed to improved wettability with iron group metals compared to Tic. has been done. However, (Ti, M
o) The C solid solution crystal particles are not a Jyuga phase, but have a Ti-rich solid solution phase in the core, while the outer periphery is a Mo-rich solid solution phase, which improves wettability with iron group metals. However, there is a problem in that the hardness and strength of the outer periphery are reduced. As an improved version of this carbide-based sintered alloy, mainly TiC is combined with TiN or T f N C and Mo, Mo2
Many carbonitride-based sintered alloys made of a carbonitride solid solution added with C or WC and an iron group metal have been proposed; for example, Japanese Patent Application No. 49-69624 proposes one improvement direction. .
（発明が解決しようとする問題点）
従来のサーメットの内、例えば特願昭４９−６９６２４
号の炭窒化物系焼結合金は、炭化物系焼結合金における
硬さ及び強度低下に対して成る程度改良できたものであ
る。しかし、焼結合金の構成要件の１つである炭窒化物
固溶体の結晶構造は、均質相でなく、焼結粒子の中芯部
がチタン及び窒素に富む炭窒化物固溶体からなり、結晶
粒子の外周部がＷやＭｏの６ａ族金属に富み窒素に乏し
い炭窒化物固溶体からなっているために常温における強
度がまだ満足できるものでなく、シかも高温において熱
衝撃や高負荷が生じると結晶内の中芯部と外周部の境界
部に歪が生じたり又は転位が生じて強度不足になり破壊
しゃすくなるという問題がある。(Problems to be solved by the invention) Among the conventional cermets, for example, Japanese Patent Application No. 49-69624
The carbonitride-based sintered alloy of No. 1 can be improved to a certain degree in contrast to the decrease in hardness and strength of carbide-based sintered alloys. However, the crystal structure of carbonitride solid solution, which is one of the constituent elements of sintered alloys, is not a homogeneous phase, but the center of the sintered particles consists of carbonitride solid solution rich in titanium and nitrogen, and Because the outer periphery is made of a carbonitride solid solution rich in group 6a metals such as W and Mo and poor in nitrogen, the strength at room temperature is still unsatisfactory. There is a problem in that strain or dislocation occurs at the boundary between the central core and the outer periphery, resulting in insufficient strength and susceptibility to fracture.
本発明は、上記のような問題点を解決したもので、特に
焼結合金の構成要件の１つである炭窒化物固溶体相の各
結晶粒子を均質にすると共にもう１つの構成要件である
鉄族金属と炭窒化物固溶体相との濡れ性を高めることに
よって焼結合金の硬度を低下させずに強度を著しく高め
ることができた炭窒化物焼結合金及びその製造方法の提
供を目的とするものである。The present invention solves the above-mentioned problems, and in particular, makes each crystal grain of the carbonitride solid solution phase, which is one of the constituent elements of a sintered alloy, homogeneous, and also makes iron, which is another constituent element, homogeneous. The purpose of the present invention is to provide a carbonitride sintered alloy whose strength can be significantly increased without reducing the hardness of the sintered alloy by increasing the wettability between the group metal and the carbonitride solid solution phase, and a method for producing the same. It is something.
（発明を解決するための手段）
本発明者らは、Ｔｉを主体とした炭窒化物固溶体と鉄族
金属からなる焼結合金の強度向上を目的に、まずＴｆ（
Ｃ，Ｎ）と周期律表４ａ。(Means for Solving the Invention) The present inventors first aimed at improving the strength of a sintered alloy consisting of a Ti-based carbonitride solid solution and an iron group metal.
C, N) and periodic table 4a.
５ａ、６ａ族金属の炭化物又は窒化物とからなる固溶体
を作製し、これら固溶体とＮｉとの濡れ性を真空、不活
性ガス又は窒素雰囲気中で調べた所、特に６ａ族元素を
含んだ炭窒化物固溶体が良い濡れ性を示し、この日ａ族
元素比率の増大に従って濡れ性が向上すること並びにこ
れら固溶体中の非金属元素に対する窒素の比率（Ｎｉｃ
、Ｎ）が増加すると６ａ族元素の中でもＣｒ又はＭｏを
含んだ固溶体は単調に濡れ性が低下するのに対してＷを
含んだ固溶体は濡れ性が向上することを確認したことに
よって本発明を完成するに至ったものである。Solid solutions consisting of carbides or nitrides of group 5a and 6a metals were prepared, and the wettability of these solid solutions with Ni was investigated in vacuum, inert gas, or nitrogen atmosphere. Solid solutions of Nic metals show good wettability, and the wettability improves as the ratio of group A elements increases, and the ratio of nitrogen to nonmetallic elements in these solid solutions (Nic
, N) increases, the wettability of solid solutions containing Cr or Mo among Group 6a elements decreases monotonically, whereas the wettability of solid solutions containing W improves. It has been completed.
すなわち、本発明の高強度焼結合金は。That is, the high strength sintered alloy of the present invention is.
（Ｍｉｘ 、Ｍ２Ｙ 、Ｍ３Ｚ ） （ＣＩ 、 Ｎｎ
） ｐで表示される炭窒化物固溶体相７０〜９７体積
％と、残りＦｅ、Ｃｏ、Ｎｉの中の少なくとも１種の結
合相と不可避的不純物とでなる焼結合金であって、前記
炭窒化物固溶体相の各結晶粒子が均質な固溶体である。(Mix, M2Y, M3Z) (CI, Nn
) A sintered alloy consisting of 70 to 97% by volume of a carbonitride solid solution phase represented by p, the remainder being at least one binder phase among Fe, Co, and Ni and unavoidable impurities, wherein the carbonitride solid solution phase is Each crystal grain of the substance solid solution phase is a homogeneous solid solution.
但し、前記炭窒化物固溶体相を表示する式中、ＭｌはＴ
ｉ又はＴｉとＺ 、ｒ及び／又はＨｆを示し、Ｍ２はＶ
、Ｎｂ、Ｔａの中の少なくとも１種を示し、Ｍ３はＷ又
はＷとＭｏ及び／又はＣｒを示す、Ｘ、Ｙ、Ｚは、それ
ぞれＭｌ 、Ｍ２ 、Ｍ３のモル比を示し、ｍ、ｎはそ
れぞれＣ（炭素）、Ｎ（窒素）のモル比を示し、ＰはＭ
ｌ 、Ｍ２ 、Ｍ３を合計した金属元素１モルに対する
Ｃ、Ｎを合計した非金属元素のモル比を示し、これらは
Ｘ＋Ｙ＋Ｚ＝ １ 、ｍ＋ ｎ＝ １ 。However, in the formula representing the carbonitride solid solution phase, Ml is T
i or Ti and Z, r and/or Hf, M2 is V
, Nb, and Ta; M3 represents W or W and Mo and/or Cr; X, Y, and Z represent the molar ratio of Ml, M2, and M3, respectively; m and n are Each shows the molar ratio of C (carbon) and N (nitrogen), P is M
It shows the molar ratio of non-metallic elements, which is the sum of C and N, to 1 mole of metal elements, which is the sum of l, M2, and M3, and these are X+Y+Z=1, m+n=1.
０．７≦Ｐ≦１．１．０≦Ｙ≦０．２゜０．０５≦Ｚ≦
０．５（Ｘ＝ｎ）。0.7≦P≦1.1.0≦Y≦0.2゜0.05≦Z≦
0.5 (X=n).
０．１≦ｎ≦０．５の関係を満足する。The relationship 0.1≦n≦0.5 is satisfied.
本発明の高強度焼結合金は、Ｔｉを主体にしてＷをも含
有した炭窒化物固溶体と鉄族金属からなる焼結合金であ
り、この固溶体と鉄族金属の中の特に、Ｎｉ及びＣＯと
の濡れ性がすぐれているために易焼結性があって巣孔の
少ない焼結合金である。また、窒素を含有した固溶体で
あることから焼結時に炭窒化物固溶体の粒成長が抑制さ
れ、特にＮｉｃ−ｓ比率が増大するに従って粒成長抑制
効果も高くなり、しかも６ａ族元素のＷが含有された固
溶体であることから一層粒成長抑制効果が著しく微細粒
組織の焼結合金となる。この微細粒組織の炭窒化物固溶
体の平均粒径が２ｐｍ以下の球状、望ましくは１４ｍ以
下の球状にすることによって一層高強度のすぐれた焼結
合金になる。The high-strength sintered alloy of the present invention is a sintered alloy consisting of a carbonitride solid solution mainly composed of Ti and also containing W, and an iron group metal. It is a sintered alloy that is easy to sinter and has few pores due to its excellent wettability. In addition, since it is a nitrogen-containing solid solution, the grain growth of the carbonitride solid solution is suppressed during sintering, and in particular, as the Nic-s ratio increases, the grain growth suppressing effect increases. Since it is a solid solution, the effect of suppressing grain growth is even greater, resulting in a sintered alloy with a fine grain structure. By forming the carbonitride solid solution having a fine grain structure into a spherical shape with an average particle size of 2 pm or less, preferably 14 m or less, an excellent sintered alloy with even higher strength can be obtained.
本発明の高強度焼結合金において、数値限定を行なった
理由は、
（Ｍｉｘ 、 Ｍ２ｙ 、 Ｍ３Ｚ ） （Ｃｍ 、
Ｎｎ ） ｐで表示される炭窒化物固溶体と鉄族金属と
の濡れ性を調べた所１例えば
（Ｔ ｉｘ 、 Ｗｚ ） （ＣＩ、 Ｎｎ ）
０．９５ 固溶体とＮｉとの濡れ性は、縦軸に接触角
、横軸に’／Ｃ−Ｎ比率すなわちｎとして表示すると第
１図の結果が１１られ、この第１図の結果からＷを含む
６ａ族元素の比率を示すＺは、鉄族金属との濡れ性を高
めるために、０．０５≦Ｚが必要であり、逆にＺを多く
すると６ａ族金属の炭化物が焼結時に固溶体から解離し
て粗大粒子として析出し、焼結合金の強度低下となるた
めに
０．０５≦Ｚ≦０．５（Ｘ−ｎ）と定めたものである。The reason for the numerical limitations in the high-strength sintered alloy of the present invention is as follows: (Mix, M2y, M3Z) (Cm,
Nn ) When we investigated the wettability of carbonitride solid solution represented by p with iron group metals 1 For example, (T ix , Wz ) (CI, Nn )
0.95 The wettability of a solid solution with Ni is expressed as the contact angle on the vertical axis and the '/C-N ratio, or n, on the horizontal axis. Z, which indicates the ratio of group 6a elements contained, needs to be 0.05≦Z in order to improve wettability with iron group metals.Conversely, when Z is increased, carbides of group 6a metals are removed from solid solution during sintering. This is determined to be 0.05≦Z≦0.5 (X−n) because it dissociates and precipitates as coarse particles, reducing the strength of the sintered alloy.
また、炭窒化物固溶体中の５ａ族元素は、微量含有する
と焼結合金の高温強度の向上に効果があるが逆に多量含
有すると巣孔が発生し易くなるためにＯ≦Ｙ≦０．２と
定めたものである。さらに、炭窒化物固溶体の非金属元
素中の窒素の比率は、第１図の結果からｎ≦０．５が望
ましく、逆にｎが少なくなると焼結時に炭窒化物固溶体
の粒成長抑制効果が弱くなるために
０．１≦ｎ≦０．５と定めたものである。化学量論組成
の炭窒化物固溶体と鉄族金属との焼結合金にすることが
望ましいが非化学量論組成の炭窒化物固溶体と鉄族金属
との焼結合金においても作用効果に大差なく、特に金属
元素に対して非金属元素が少なくなり過ぎると硬さの低
下や強度低下が生じ、逆に多くなり過ぎると巣孔が多く
発生して強度低下となることから金属元素に対する非金
属元素の比率は、０．７≦Ｐ≦１．１と定めたものであ
る。In addition, when the group 5a element in the carbonitride solid solution is contained in a small amount, it is effective in improving the high-temperature strength of the sintered alloy, but on the other hand, when it is contained in a large amount, pores are likely to occur, so O≦Y≦0. This is what has been established. Furthermore, the ratio of nitrogen in the non-metallic elements of the carbonitride solid solution is preferably n≦0.5 from the results shown in Figure 1; conversely, when n is small, the effect of suppressing the grain growth of the carbonitride solid solution during sintering is reduced. This is set as 0.1≦n≦0.5 in order to make it weaker. Although it is desirable to use a sintered alloy of a carbonitride solid solution with a stoichiometric composition and an iron group metal, there is no significant difference in the effect of a sintered alloy of a carbonitride solid solution with a non-stoichiometric composition and an iron group metal. In particular, if the amount of nonmetallic elements is too small compared to metal elements, the hardness and strength will decrease, and if the amount is too large, many pores will be generated and strength will be reduced. The ratio is set as 0.7≦P≦1.1.
本発明の高強度焼結合金の製造方法は。The method for producing a high strength sintered alloy of the present invention is as follows.
（ＭＩＸ 、 Ｍ２Ｙ 、 Ｍ３Ｚ ） （ＣＩ 、
Ｎｎ ） ｐで表示される炭窒化物固溶体粉末とＦｅ、
Ｃｏ。(MIX, M2Y, M3Z) (CI,
Nn) Carbonitride solid solution powder represented by p and Fe,
Co.
Ｎｉの中の少なくとも１種の粉末との混合粉末を圧粉体
又は成形体とした後５〜１００Ｔｏｒｒの窒素中で１３
００℃〜１６００℃に加熱して焼結する方法である。但
し、ＭｌはＴｉ又はＴｉとＺｒ及び／又はＨｆを示し、
Ｍ２はＶ、Ｎｂ。The mixed powder with at least one type of Ni powder is made into a green compact or compact, and then heated in nitrogen at 5 to 100 Torr for 13 min.
This is a method of heating and sintering at 00°C to 1600°C. However, Ml represents Ti or Ti and Zr and/or Hf,
M2 is V, Nb.
Ｔａの中の少なくとも１種を示し、Ｍ３はＷ又はＷとＭ
ｏ及び／又はＣｒを示す、Ｙ、Ｚは。represents at least one kind of Ta, M3 is W or W and M
Y and Z represent o and/or Cr.
それぞれＭｌ 、Ｍ２ 、Ｍ３のモル比を示し、ｍ。Indicates the molar ratio of Ml, M2, and M3, respectively, and m.
ｎはそれぞれＣ（炭素）、Ｎ（窒素）のモル比を示し、
ＰはＭｌ 、Ｍ２ 、Ｍ３を合計した金属元素１モルに
対するＣ、Ｎを合計した非金属元素のモル比を示し、こ
れらはｘ＋ｙ＋ｚ＝ １ 。n indicates the molar ratio of C (carbon) and N (nitrogen), respectively,
P represents the molar ratio of the nonmetallic elements, which are the sum of C and N, to 1 mole of the metal elements, which are the sum of Ml, M2, and M3, and these are x+y+z=1.
ｍ＋ｎ＝１．０．７ ≦Ｐ≦ １ 、１ 。m+n=1.0.7 ≦P≦1, 1.
０≦Ｙ≦０．２ 。0≦Y≦0.2.
０．０５≦Ｚ≦０．５（Ｘ−ｎ）。0.05≦Z≦0.5 (X−n).
０．１≦ｎ≦０．５の関係を満足する。The relationship 0.1≦n≦0.5 is satisfied.
この本発明の高強度焼結合金の製造方法について、更に
具体的に説明すると、出発原料として用いる
（ＭＩＸ 、 Ｍ２Ｙ 、 Ｍ３Ｚ ） （Ｃｍ 、
Ｎｎ ） ｐで表示される炭窒化物固溶体粉末は、２Ｉ
Ｌｍ以下の固溶体粉末を使用するのがよく、更に微細粒
子を使用する程焼結を促進することから望ましいことで
ある。また、出発原料としての固溶体粉末は、均質な固
溶体粉末にすることが特に１重要なことである。均質な
固溶体粉末を得るためには、目的とする固溶体粉末の組
成となる炭化物、窒化物。To explain more specifically the method for producing the high-strength sintered alloy of the present invention, (MIX, M2Y, M3Z) (Cm,
The carbonitride solid solution powder represented by Nn) p is 2I
It is preferable to use a solid solution powder having a particle diameter of Lm or less, and it is more desirable to use finer particles because sintering is accelerated. Furthermore, it is particularly important that the solid solution powder used as the starting material be a homogeneous solid solution powder. In order to obtain a homogeneous solid solution powder, carbides and nitrides that have the composition of the desired solid solution powder are required.
炭窒化物などの金属化合物粉末、例えば０゜７終ｍ程度
に微粉砕したＴｉＣ，ＴｉＮ。Metal compound powder such as carbonitride, for example TiC, TiN finely pulverized to about 0°7 mm.
Ｔ１ＣＮ、（Ｔｉ 、Ｗ）Ｃ，ＷＣ，Ｍｏ２Ｃ。T1CN, (Ti, W)C, WC, Mo2C.
ＴａＣ、ＴａＮ 、（Ｔｉ 、Ｔａ）Ｃ。TaC, TaN, (Ti, Ta)C.
（Ｔｉ 、Ｔａ、Ｗ）Ｃ，ＮｂＣなどの周期律表４ａ、
５ａ、６ａ族金属の化合物から必要に応じて組合わせて
配合し、この配合粉末を混合粉砕するときに不可避的不
純物の混入、特にＦｅ族族金属９朋
いように例えば、粉砕効果が低下するけれども混合粉砕
容器としてはラバーなどで内張すしたり、混合粉砕のた
めのポール等も表面被着するなどと考慮する必要がある
．このようにして得た混合粉末を０．５〜５気圧の窒素
雰囲気で１６００℃以上，望ましくは１８００℃以上，
２時間保持により固溶処理して未固溶の化合物の混在や
金属の混在のない均質な固溶体粉末とする必要がある。Periodic table 4a such as (Ti, Ta, W)C, NbC,
Compounds of group 5a and group 6a metals are blended as necessary, and when this blended powder is mixed and pulverized, unavoidable impurities are mixed in, especially Fe group metals, for example, the pulverizing effect is reduced. However, as a mixing and grinding container, it is necessary to take into consideration things such as lining it with rubber, etc., and attaching poles for mixing and grinding to the surface. The mixed powder thus obtained is heated at 1600°C or higher, preferably 1800°C or higher, in a nitrogen atmosphere of 0.5 to 5 atm.
It is necessary to carry out a solid solution treatment by holding for 2 hours to obtain a homogeneous solid solution powder free of unmixed compounds and metals.
このようにして得た均質な炭窒化物固溶体粉末に鉄族金
属粉末を配合し、この配合粉末を混合粉砕するときは混
合粉砕時の容器内壁及びポール表面からの摩耗による金
属及び金属化合物などの不純物の混入を出来るだけ避け
るためにステンレス又は耐熱合金からなる容器には超硬
合金又はラバーなどを内張すしたり、もしくは超硬合金
製容器又は超硬合金製容器にラバーなどを内張すして使
用することが望ましく、混合粉砕のためのポール等も同
様の考慮をして使用することが望ましい。When the homogeneous carbonitride solid solution powder thus obtained is blended with iron group metal powder and this blended powder is mixed and pulverized, metals and metal compounds, etc., are removed by abrasion from the inner wall of the container and the pole surface during the mixed pulverization. To avoid contamination with impurities as much as possible, containers made of stainless steel or heat-resistant alloys should be lined with cemented carbide or rubber, or containers made of cemented carbide or cemented carbide should be lined with rubber, etc. It is desirable to use a pole, etc. for mixing and grinding with the same consideration.
このとき、粉砕効果を高めるのと粉末の表面酸化を防ぐ
ためには、アセトン、ヘキサン、ベンゼン、アルコール
等の有機溶媒を容器の中に入れて湿式混合粉砕するのが
よい．混合粉砕した混合粉末の成形は，混合粉末を黒鉛
モールドに充填して雰囲気を充分にコントロールしてホ
ットプレスする方法，又は混合粉末にパラフィン、カン
ファ等の成形助剤を添加して必要ならば顆粒状にした後
金型モールドに充填して加圧成形したり、もしくはラバ
ープレス等の静水圧加圧によって成形する．このように
して成形した粉末圧粉体を直接焼結したり，又は粉末圧
粉体を焼結温度よりも低い温度で雰囲気を充分にコント
ロールしながら予備焼結した後切断，研削，切削等の機
械加工を施してから焼結することもできる。At this time, in order to enhance the grinding effect and prevent surface oxidation of the powder, it is best to place an organic solvent such as acetone, hexane, benzene, alcohol, etc. in a container and perform wet mixing and grinding. The mixed and pulverized powder mixture can be molded by filling it into a graphite mold and hot-pressing it with a well-controlled atmosphere, or by adding molding aids such as paraffin and camphor to the mixed powder and forming granules if necessary. After forming into a shape, it is filled into a metal mold and press-formed, or it is formed using hydrostatic pressure such as a rubber press. The powder compact formed in this way can be directly sintered, or the powder compact can be pre-sintered at a temperature lower than the sintering temperature while fully controlling the atmosphere, and then subjected to cutting, grinding, cutting, etc. It is also possible to perform machining and then sintering.
本発明の高強度焼結合金の製造工程の内、焼結は，脱酸
素の促進と脱窒素の防止による雰囲気コントロールをし
て焼結する必要がある．脱酸素の促進に効果のある焼結
雰囲気は、水素などの還元性ガス及び窒素であり、脱窒
素の防止に効果のある焼結雰囲気は窒素である．このこ
とから焼結雰囲気は、窒素又は窒素と水素の混合ガス中
で焼結するのが脱酸素の促進と脱窒素の防止による均質
な炭窒化物固溶体を含む焼結合金の製造方法として望ま
しいものである．この内、作業性及び調整の容易性から
窒素ガス雰囲気による焼結が望ましく、特に窒素分圧が
５Ｔｏｒｒ未満では脱酸素の促進と脱窒素の防止効果が
弱く、窒素分圧が１００Ｔｏｒｒを超えると焼結時に窒
素が合金中に取り込まれて巣孔として残存することから
窒素ガス雰囲気中の窒素分圧は５Ｔｏｒｒ−１００Ｔｏ
ｒｒにすることが望ましい．焼結温度は、液相の生じる
温度以上であればよいが高温度になり過ぎると粒成長が
生じるので１３００℃〜１６００℃が望ましい．このよ
うな条件で焼結したものを熱間静水圧加圧法（Ｈ Ｉ
Ｐ）によって再処理することにより一層緻密で高強度焼
結合金にすることもできる。In the manufacturing process of the high-strength sintered alloy of the present invention, sintering requires atmosphere control to promote deoxidation and prevent denitrification. The sintering atmosphere that is effective in promoting deoxidation is a reducing gas such as hydrogen and nitrogen, and the sintering atmosphere that is effective in preventing denitrification is nitrogen. For this reason, sintering in nitrogen or a mixed gas of nitrogen and hydrogen is the preferred method for producing a sintered alloy containing a homogeneous carbonitride solid solution by promoting deoxidation and preventing denitrification. It is. Among these, sintering in a nitrogen gas atmosphere is preferable from the viewpoint of workability and ease of adjustment.In particular, when the nitrogen partial pressure is less than 5 Torr, the effect of promoting deoxidation and preventing denitrification is weak, and when the nitrogen partial pressure exceeds 100 Torr, sintering is Since nitrogen is taken into the alloy during solidification and remains as pores, the nitrogen partial pressure in the nitrogen gas atmosphere is 5 Torr-100To
It is desirable to set it to rr. The sintering temperature should be at least the temperature at which a liquid phase occurs, but if the temperature is too high, grain growth will occur, so a temperature of 1300°C to 1600°C is preferable. The product sintered under these conditions is subjected to hot isostatic pressing (HI).
By reprocessing with P), a more dense and high-strength sintered alloy can be obtained.
（作用）
本発明の高強度焼結合金は、微細粒子の炭窒化物固溶体
と鉄族金属とからなり、しかもこの炭窒化物固溶体が均
質な結晶粒子であることから高温又は高負荷が作用する
場合でも結晶粒内型又は転位などが生じ難いために強度
がすぐれている。(Function) The high-strength sintered alloy of the present invention is composed of a carbonitride solid solution of fine particles and an iron group metal, and since the carbonitride solid solution is a homogeneous crystal grain, it cannot be subjected to high temperatures or high loads. Even in the case of steel, it has excellent strength because it is difficult for intragrain type or dislocation to occur.
′ また、Ｔｉを主体にした４ａ族金属に少なくとも
Ｗを含む炭窒化物固溶体であることから、この固溶体と
鉄族金属との濡れ性がすぐれたものになり一層強度を陶
土しているものである。' Also, since it is a carbonitride solid solution containing at least W in a group 4a metal mainly composed of Ti, the solid solution has excellent wettability with iron group metals, making it even stronger. be.
本発明の高強度焼結合金の製造方法は、均質な炭窒化物
固溶体粉末と鉄族金属粉末とを出発原料とするもので、
この均質な炭窒化物固溶体が焼結時に分解又は再固溶し
たり、もしくは炭窒化物固溶体から分離再析出が生じな
く、均質な炭窒化物固溶体と鉄族金属との焼結合金が得
られる製造方法である。The method for producing a high-strength sintered alloy of the present invention uses homogeneous carbonitride solid solution powder and iron group metal powder as starting materials,
This homogeneous carbonitride solid solution does not decompose or re-dissolve during sintering, or separate and re-precipitate from the carbonitride solid solution, and a homogeneous sintered alloy of carbonitride solid solution and iron group metal can be obtained. This is the manufacturing method.
（実施例） 実施例１ 平均粒度が１〜２ｇｍ内にあるＴｉｃ。(Example) Example 1 Tic with an average particle size within 1-2 gm.
ＴｉＮ、ＴａＣ，ＷＣＣ粒粉末重量％テＴ ｉ Ｃ：Ｔ
ｉＮ：ＴａＣ：ＷＣ＝５０：２０： １５：１５に秤
量し、アセトン溶媒を用いて４８時間ボールミル混合し
た。この混合粉末を乾燥後２Ｘ２Ｘ２■のペレットに成
形し、２気圧の窒素雰囲気中で１９００℃２時間保持に
より固溶体化処理を行なった。得られた固溶体は、
全炭素量１１．５５％、遊離炭素量０．０７％。TiN, TaC, WCC grain powder weight %TeTiC:T
It was weighed out at iN:TaC:WC=50:20:15:15, and mixed in a ball mill for 48 hours using an acetone solvent. After drying, this mixed powder was formed into 2×2×2×2 pellets, and solid solution treatment was carried out by holding the pellets at 1900° C. for 2 hours in a nitrogen atmosphere of 2 atm. The obtained solid solution had a total carbon content of 11.55% and a free carbon content of 0.07%.
結合窒素量４．２４％、酸素量０．１７％で示性式が（
Ｔ ｉｏ、ｓａ、 Ｔ ａｏ ０６． ｗｏ、ｏ６）
（Ｃ０，７６゜Ｎｏ ７４） ｏ、ｑ５ で表現さ
れる均質な炭窒化物固溶体であった。この炭窒化物固溶
体粉末を粗粉砕し、さらにボールミルにより平均粒度１
．５ＩＬｍの微粉末とした。この微粉末の炭窒化物固溶
体とＮｉ粉末との混合比が異なる粉末をアセトン溶媒に
よる湿式でもって４８時間ボールミル混合した。この混
合粉末を乾燥後２％パラフィンを添加してＪＩＳ規格に
よる抗折力試験片及び５ＮＰ４３２形状にプレス成形し
、この成形体を５０Ｔｏｒｒの窒素雰囲気中で１４００
″ｃｉ時間保持して焼結した。得られた焼結合金の硬さ
及び抗折力を測定し、焼結合金の組成と共に第１表に示
した。このようにして作製した本発明の焼結合金に対し
て従来より市販されているＴＥＮ添加サーメットを比較
として第１表に併記した。この第１表の内５本発明の焼
結合金試料Ｎｏ２ 、Ｎｏ３ 、ｈｂ４と比較品尚ｌを
５ＮＰ４３２形状でもって被削材５４８Ｃ，切削速度１
５０ｍ／ｓｉｎ 、 ９］込み量１．５ｍｍ、送り速度
０ 、３ ａｍ／ｒｅｖの条件で１０分間旋削したとき
の平均逃げ面摩耗量（ＶＢ）並びに被削材ＳＣＭ４４０
．切削速度１００ ｓ／ｓｉｎ 。The specific formula is (
T io, sa, T ao 06. wo, o6)
(C0,76°No 74) It was a homogeneous carbonitride solid solution expressed by o, q5. This carbonitride solid solution powder was coarsely pulverized and further milled with an average particle size of 1
．． It was made into a fine powder of 5ILm. The powders having different mixing ratios of the fine carbonitride solid solution and the Ni powder were mixed in a wet ball mill for 48 hours using an acetone solvent. After drying this mixed powder, 2% paraffin was added and press molded into a transverse rupture strength test piece and 5NP432 shape according to JIS standard, and this molded body was heated to 1400 in a nitrogen atmosphere of 50 Torr.
The hardness and transverse rupture strength of the obtained sintered alloy were measured and shown in Table 1 along with the composition of the sintered alloy. Conventionally available TEN-added cermets for the alloy are listed in Table 1 for comparison.In Table 1, five sintered alloy samples of the present invention No. 2, No. 3, and hb4 and a comparative product, 5NP432, are listed. Due to the shape, the work material is 548C, the cutting speed is 1
50 m/sin, 9] Average flank wear amount (VB) and work material SCM440 when turning for 10 minutes under the conditions of depth 1.5 mm, feed rate 0, 3 am/rev
．． Cutting speed: 100 s/sin.
切込み場２厘■、ｌ刃当りの速度０．３厘腸／１ｏｏｔ
ｈの条件でフライス切削したときの各試料の欠損までの
切削長さを測定して同じく第１表に併記した。Cutting area 2 cm, speed per blade 0.3 cm/1oot
When milling was performed under the conditions of h, the cutting length of each sample to the point of defect was measured and is also listed in Table 1.
以下 余白
尚１本発明品Ｎｏ４と比較品Ｎｏｌの炭窒化物固溶体の
結晶粒子を走査オージェ電子分光法で測定した所、本発
明品Ｍ４は各結晶粒子が均質な炭窒化物固溶体であった
のに対して比較品ＮＯ１は各結晶粒子が２相構造からな
っていることが確認できた。Margin Note 1: When the crystal grains of the carbonitride solid solution of the invention product No. 4 and the comparative product No. 1 were measured by scanning Auger electron spectroscopy, it was found that the invention product M4 was a carbonitride solid solution in which each crystal grain was homogeneous. On the other hand, it was confirmed that each crystal grain of comparative product No. 1 had a two-phase structure.
実施例２ 実施例１で用いた各粉末とＮｂＣ，ＺｒＣ。Example 2 Each powder used in Example 1, NbC, and ZrC.
ＶＣ，Ｍｏ２ Ｃ，Ｃｒ３Ｃ２粉末を用いて実施例１と
同様にして第２表に示す各種の炭窒化物固溶体粉末を一
作製した。この各種の炭窒化物固溶体粉末にＮｉ又はＮ
ｉとＣｏからなる鉄族金属粉末を１０体積％加えて実施
例１と同様に混合、成形。Various carbonitride solid solution powders shown in Table 2 were prepared in the same manner as in Example 1 using VC, Mo2 C, and Cr3C2 powders. Ni or N is added to these various carbonitride solid solution powders.
10% by volume of iron group metal powder consisting of i and Co was added and mixed and molded in the same manner as in Example 1.
焼結して焼結合金を得た。得られた各種の焼結合金の諸
特性を実施例１と同様にして調べて、その結果を第３表
に示した。A sintered alloy was obtained by sintering. The various properties of the various sintered alloys obtained were investigated in the same manner as in Example 1, and the results are shown in Table 3.
実施例３ モ均粒度１〜ＺｕＬｍ内にあるＴｉＣ。Example 3 TiC having an average particle size of 1 to ZuLm.
Ｔ ｉ Ｎ 、ＷＣ、Ｍｏ２Ｃ各粉末を用いて実施例１
と同様にして非金属元素であるＣ、！−Ｎの比率の異な
る （Ｔ ｉ ｏ ａ 、 Ｗｏ １５．
Ｍ ０００５）（Ｃｍ Ｎｎ ） ０．９５
の炭窒化物固溶体粉末を作製した。こうして得たＮ／Ｃ
３Ｎが０．１，０．２゜０．３，０．４である各種の炭
窒化物固溶体粉末に１３体積％Ｎｉ粉末を加えて実施例
１と同様に混合、成形、焼結して未発明の焼結合金を得
た。Example 1 using T i N, WC, and Mo2C powders
Similarly, C, which is a nonmetallic element,! -Different ratios of N (Tio a, Wo 15.
M 0005) (Cm Nn ) 0.95
A carbonitride solid solution powder was prepared. N/C obtained in this way
13% by volume Ni powder was added to various carbonitride solid solution powders with 3N of 0.1, 0.2°, 0.3, 0.4, and mixed, molded, and sintered in the same manner as in Example 1. A sintered alloy of the invention was obtained.
この本発明の焼結合金に比較して平均粒度ｌ〜ｚｐｍ内
にあるＴ ｉＣ、Ｔ ｉ Ｎ 、 Ｗ Ｃ、Ｍ Ｏ２Ｃ
各粉末に１３体積％Ｎｉ粉末を加えて実施例１と同様に
混合、成形、焼結して’／Ｃ−Ｎが０．１゜０．２，０
゜３，０．４で本発明の焼結合金の同Ｍ１１＆の各種比
較焼結合金を作製した。この本発明の焼結合金と比較焼
結合金の抗折力強度と合金組織を調べた。抗折力強度の
結果は、第２図に示した。また、合金組織を走査オージ
ェ電子分光法で観察した所、未発明の焼結合金は均質な
炭窒化物固溶体であったのに対して比較焼結合金は２相
構造の炭窒化物固溶体であった。Compared to the sintered alloy of the present invention, T i C, T i N, W C, M O2C whose average particle size is within l~zpm
13% by volume Ni powder was added to each powder, mixed, molded, and sintered in the same manner as in Example 1 until the '/C-N was 0.1°0.2,0
Various comparison sintered alloys of the same M11& of the sintered alloy of the present invention were prepared at a temperature of 3.0.4. The transverse rupture strength and alloy structure of the sintered alloy of the present invention and a comparative sintered alloy were investigated. The transverse rupture strength results are shown in Figure 2. Furthermore, when the alloy structure was observed using scanning Auger electron spectroscopy, it was found that the uninvented sintered alloy was a homogeneous carbonitride solid solution, whereas the comparative sintered alloy was a carbonitride solid solution with a two-phase structure. Ta.
（発明の効果）
本発明の高強度焼結合金は、炭窒化物固溶体と結合相と
の濡れ性がすぐれており、しかも）＆ Ｉ化物固溶体が
均質な結晶粒子からなっているために塑性変形、歪及び
転位に対して耐える作用が高くて高強度を発揮するもの
である。このことから本発明の焼結合金は、旋削工具は
勿論のことフライス工具から刃先の鋭角なドリル、ミク
ロンドリルを含めた穴あけ工具など各種の切削用工具と
して使用できる。また１紙、磁気テープ等の切断用スリ
ッターからドツトビン、スノースパイクチップ、ゴルフ
スパイクチップ、ボールなどの衝撃の加わる用途からゲ
ージ、ノズル、メカニカルシールなどの各種耐摩耗用工
具としても産業上有用な材料である。(Effects of the Invention) The high-strength sintered alloy of the present invention has excellent wettability between the carbonitride solid solution and the binder phase, and also has low plastic deformation because the carbonitride solid solution is composed of homogeneous crystal grains. It has high resistance to strain and dislocation, and exhibits high strength. Therefore, the sintered alloy of the present invention can be used not only as a turning tool but also as various cutting tools such as a milling tool, a drill with an acute cutting edge, and a drilling tool including a micron drill. It is also an industrially useful material, from slitters for cutting paper, magnetic tape, etc., to dot bins, snow spike tips, golf spike tips, balls, and other impact applications, to gauges, nozzles, mechanical seals, and other wear-resistant tools. It is.
第１図は。
（Ｔｉｘ 、Ｖ’ｉｔ ） （Ｃｍ 、 Ｎｎ
） ｏ ｑｓ炭窒化物固溶体における’／１．ｗ及びＮ
／Ｃ０Ｈの比率を変えた固溶体とＮｉとの濡れ性を２０
Ｔｏｒｒ窒素雰囲気中１４００℃で調べた結果である。
第２図は、実施例３に示した
（Ｔ ｉｏ ｓ 、 Ｗｏ １５． Ｍｏｏ ａ
ｓ） （Ｃｍ 。
Ｎｎ ） ａ ｑ５炭窒化物固溶体と１３体精％Ｎｉの
焼結合金における本発明の焼結合金と比較焼結合金との
Ｎ／Ｃ，Ｎ ｋ！ｃ率と抗折力強度の結果である。
特許出願人 東芝タンガロイ株式会社
第１ 図
打２図
？ヨ讐、ｓ （ｒＦ−串ジFigure 1 is. (Tix, V'it) (Cm, Nn
) o qs '/1 in carbonitride solid solution. w and N
The wettability of solid solutions with different ratios of /C0H and Ni was 20
These are the results of an investigation at 1400° C. in a Torr nitrogen atmosphere. FIG. 2 is shown in Example 3 (Tios, Wo 15. Moo a
s) (Cm.Nn) aq5 N/C, Nk! of the sintered alloy of the present invention and the comparative sintered alloy in the sintered alloy of carbonitride solid solution and 13% Ni. These are the results of c-rate and transverse rupture strength. Patent Applicant Toshiba Tungaloy Corporation Figure 1 Figure 2? Yo enemy, s (rF-kushiji
Claims (1)
９７体積％と、残りＦｅ、Ｃｏ、Ｎｉの中の少なくとも
１種の結合相と不可避的不純物とでなる焼結合金であっ
て、前記炭窒化物固溶体相の各結晶粒子が均質な固溶体
であることを特徴とする高強度焼結合金。 （Ｍ１＿Ｘ、Ｍ２＿Ｙ、Ｍ３＿Ｚ）（Ｃｍ、Ｎｎ）＿Ｐ
・・・・（Ａ） 但し、Ｍ１はＴｉ又はＴｉとＺｒ及び／又はＨｆを示し
、Ｍ２はＶ、Ｎｂ、Ｔａの中の少なくとも１種を示し、
Ｍ３はＷ又はＷとＭｏ及び／又はＣｒを示す。Ｘ、Ｙ、
Ｚは、それぞれＭ１、Ｍ２、Ｍ３のモル比を示し、ｍ、
ｎはそれぞれＣ（炭素）、Ｎ（窒素）のモル比を示し、
ＰはＭ１、Ｍ２、Ｍ３を合計した金属元素１モルに対す
るＣ、Ｎを合計した非金属元素のモル比を示し、これら
はＸ＋Ｙ＋Ｚ＝１、ｍ＋ｎ＝１、０．７≦Ｐ≦１．１、
０≦Ｙ≦０．２、 ０．０５≦Ｚ≦０．５（Ｘ−ｎ）、 ０．１≦ｎ≦０．５の関係を満足する。 （２）上記炭窒化物固溶体相の平均粒径が２μｍ以下の
球状であることを特徴とする特許請求の範囲第１項記載
の高強度焼結合金。 （３）次式（Ｂ）で表示される炭窒化物固溶体粉末とＦ
ｅ、Ｃｏ、Ｎｉの中の少なくとも１種の粉末との混合粉
末を圧粉体又は成形体とした後５〜１００Ｔｏｒｒの窒
素中で１３００℃〜１６００℃に加熱して焼結すること
を特徴とする高強度焼結合金の製造方法。 （Ｍ１＿Ｘ、Ｍ２＿Ｙ、Ｍ３＿Ｚ）（Ｃｍ、Ｎｎ）＿Ｐ
・・・・（Ｂ） 但し、Ｍ１はＴｉ又はＴｉとＺｒ及び／又はＨｆを示し
、Ｍ２はＶ、Ｎｂ、Ｔａの中の少なくとも１種を示し、
Ｍ３はＷ又はＷとＭｏ及び／又はＣｒを示す。Ｘ、Ｙ、
Ｚは、それぞれＭ１、Ｍ２、Ｍ３のモル比を示し、ｍ、
ｎはそれぞれＣ（炭素）、Ｎ（窒素）のモル比を示し、
ＰはＭ１、Ｍ２、Ｍ３を合計した金属元素１モルに対す
るＣ、Ｎを合計した非金属元素のモル比を示し、これら
はＸ＋Ｙ＋Ｚ＝１、ｍ＋ｎ＝１、０．７≦Ｐ≦１．１、
０≦Ｙ≦０．２、 ０．０５≦Ｚ≦０．５（Ｘ−ｎ）、 ０．１≦ｎ≦０．５の関係を満足する。 （４）上記炭窒化物固溶体粉末が均質な結晶粒子からな
る固溶体粉末であることを特徴とする特許請求の範囲第
３項記載の高強度焼結合金の製造方法。[Claims] (1) Carbonitride solid solution phase 70~ represented by the following formula (A)
A sintered alloy consisting of 97% by volume, the remaining binder phase of at least one of Fe, Co, and Ni and unavoidable impurities, wherein each crystal grain of the carbonitride solid solution phase is a homogeneous solid solution. A high-strength sintered alloy characterized by: (M1_X, M2_Y, M3_Z) (Cm, Nn)_P
...(A) However, M1 represents Ti or Ti and Zr and/or Hf, M2 represents at least one of V, Nb, and Ta,
M3 represents W or W and Mo and/or Cr. X, Y,
Z represents the molar ratio of M1, M2, M3, m,
n indicates the molar ratio of C (carbon) and N (nitrogen), respectively,
P indicates the molar ratio of the non-metallic element, which is the sum of C and N, to 1 mole of the metal element, which is the sum of M1, M2, and M3, and these are X+Y+Z=1, m+n=1, 0.7≦P≦1.1,
The following relationships are satisfied: 0≦Y≦0.2, 0.05≦Z≦0.5 (X-n), and 0.1≦n≦0.5. (2) The high-strength sintered alloy according to claim 1, wherein the carbonitride solid solution phase has a spherical shape with an average particle size of 2 μm or less. (3) Carbonitride solid solution powder expressed by the following formula (B) and F
The mixed powder with at least one kind of powder among E, Co, and Ni is made into a green compact or a compact, and then heated to 1300°C to 1600°C in nitrogen at 5 to 100 Torr and sintered. A method for producing high-strength sintered alloys. (M1_X, M2_Y, M3_Z) (Cm, Nn)_P
...(B) However, M1 represents Ti or Ti and Zr and/or Hf, M2 represents at least one of V, Nb, and Ta,
M3 represents W or W and Mo and/or Cr. X, Y,
Z represents the molar ratio of M1, M2, M3, m,
n indicates the molar ratio of C (carbon) and N (nitrogen), respectively,
P indicates the molar ratio of the non-metallic element, which is the sum of C and N, to 1 mole of the metal element, which is the sum of M1, M2, and M3, and these are X+Y+Z=1, m+n=1, 0.7≦P≦1.1,
The following relationships are satisfied: 0≦Y≦0.2, 0.05≦Z≦0.5 (X-n), and 0.1≦n≦0.5. (4) The method for producing a high-strength sintered alloy according to claim 3, wherein the carbonitride solid solution powder is a solid solution powder consisting of homogeneous crystal grains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60022655A JPS61183437A (en) | 1985-02-07 | 1985-02-07 | High strength sintered alloy and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60022655A JPS61183437A (en) | 1985-02-07 | 1985-02-07 | High strength sintered alloy and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS61183437A true JPS61183437A (en) | 1986-08-16 |
Family
ID=12088854
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60022655A Pending JPS61183437A (en) | 1985-02-07 | 1985-02-07 | High strength sintered alloy and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61183437A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004525848A (en) * | 2001-02-22 | 2004-08-26 | シーメンス アクチエンゲゼルシヤフト | Method for producing scintillator ceramic and use of said scintillator ceramic |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55141543A (en) * | 1979-04-17 | 1980-11-05 | Sumitomo Electric Ind Ltd | Mo-containing hard alloy |
| JPS5651201A (en) * | 1979-06-04 | 1981-05-08 | Uss Eng & Consult | Method and device for purifying waste gas |
| JPS599140A (en) * | 1982-07-09 | 1984-01-18 | Mitsubishi Metal Corp | Production of sintered material for cutting tool having excellent high-temperature characteristic |
| JPS59129751A (en) * | 1983-01-13 | 1984-07-26 | Mitsubishi Metal Corp | Superheat-resistant sintered alloy and its production |
-
1985
- 1985-02-07 JP JP60022655A patent/JPS61183437A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55141543A (en) * | 1979-04-17 | 1980-11-05 | Sumitomo Electric Ind Ltd | Mo-containing hard alloy |
| JPS5651201A (en) * | 1979-06-04 | 1981-05-08 | Uss Eng & Consult | Method and device for purifying waste gas |
| JPS599140A (en) * | 1982-07-09 | 1984-01-18 | Mitsubishi Metal Corp | Production of sintered material for cutting tool having excellent high-temperature characteristic |
| JPS59129751A (en) * | 1983-01-13 | 1984-07-26 | Mitsubishi Metal Corp | Superheat-resistant sintered alloy and its production |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004525848A (en) * | 2001-02-22 | 2004-08-26 | シーメンス アクチエンゲゼルシヤフト | Method for producing scintillator ceramic and use of said scintillator ceramic |
| US7303699B2 (en) | 2001-02-22 | 2007-12-04 | Siemens Aktiengesellschaft | Method for producing a scintillator ceramic |
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