JPS62288166A - Manufacture of tungsten carbide-oxide composite sintered body - Google Patents
Manufacture of tungsten carbide-oxide composite sintered bodyInfo
- Publication number
- JPS62288166A JPS62288166A JP61128666A JP12866686A JPS62288166A JP S62288166 A JPS62288166 A JP S62288166A JP 61128666 A JP61128666 A JP 61128666A JP 12866686 A JP12866686 A JP 12866686A JP S62288166 A JPS62288166 A JP S62288166A
- Authority
- JP
- Japan
- Prior art keywords
- powder
- sintered body
- tungsten carbide
- composite sintered
- oxide composite
- 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
Links
- 239000002131 composite material Substances 0.000 title claims description 18
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 title claims description 17
- 229910052721 tungsten Inorganic materials 0.000 title claims description 16
- 239000010937 tungsten Substances 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten(iv) oxide Chemical compound O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 claims description 25
- 239000000843 powder Substances 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical class O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 2
- 239000002245 particle Substances 0.000 description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Abstract
(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
３、発明の詳細な説明
産業上の利用分野
本発明は、超硬工具や高温構造材または各種機能材料と
して用いられる炭化タングステン−酸化物複合焼結体の
製造方法に関する。Detailed Description of the Invention 3. Detailed Description of the Invention Industrial Application Field The present invention relates to a method for manufacturing a tungsten carbide-oxide composite sintered body used as a cemented carbide tool, high-temperature structural material, or various functional materials. .
従来の技術
従来、炭化タングステン−酸化物複合焼結体は、まず金
属タングステンまたはその酸化物に炭素粉末または固形
炭素を混合し高温で反応させることによって合成した炭
化タングステン粉末と酸化物粉末を十分に混合した後高
温高圧下で焼結させることによって製造していた。Conventional technology Conventionally, tungsten carbide-oxide composite sintered bodies have been produced by first mixing metal tungsten or its oxide with carbon powder or solid carbon and reacting the mixture at high temperature to fully combine tungsten carbide powder and oxide powder. It was manufactured by mixing and then sintering at high temperature and pressure.
発明が解決しようとする問題点
この方法は、製造工程が長く複雑であるため不純物が混
入しやすく、シかもエネルギー消費が非常に大きかった
。Problems to be Solved by the Invention In this method, the manufacturing process is long and complicated, so impurities are likely to be mixed in, and energy consumption is extremely large.
問題点を解決するための手段
還元用金属粉末（反応後ぼは酸化物となる）と、炭素と
、二酸化タングステン（ＷＯ２）粉末（反応後には炭化
タングステンになる）とからなる混合物の成形体に圧力
をかけた状態で、その成形体の一部を強熱点火して燃焼
反応を起こさせ、この化学反応によって炭化タングステ
ン（α−ＷＣやβ−Ｗ２Ｃ）と酸化物の粒子を合成し、
反応熱によってこれらの粒子を焼結して炭化タングステ
ン−酸化物複合焼結体を得る。Means to solve the problem A molded body of a mixture of reducing metal powder (which becomes an oxide after reaction), carbon, and tungsten dioxide (WO2) powder (which becomes tungsten carbide after reaction). Under pressure, a part of the compact is ignited at high heat to cause a combustion reaction, and this chemical reaction synthesizes tungsten carbide (α-WC and β-W2C) and oxide particles.
These particles are sintered by the heat of reaction to obtain a tungsten carbide-oxide composite sintered body.
作用
本発明によれば、加圧下で成形体に点火するだけで、高
密度の炭化タングステン−酸化物複合焼結体が容易に得
られる。従って従来の炭化タングステンと酸化物の粉末
を用いて作成する焼結体の製造方法と比較して、極めて
省エネルギーであり、しかも得られる焼結体もきわめて
高純度である。According to the present invention, a high-density tungsten carbide-oxide composite sintered body can be easily obtained simply by igniting the compact under pressure. Therefore, compared to the conventional method for producing a sintered body using tungsten carbide and oxide powder, this method is extremely energy-saving, and the resulting sintered body is also of extremely high purity.
実施例
実施例１
出発原料として粒径１０μｍ以下のジルコニウム粉末、
平均粒径２μ謬の二酸化タングステン（ＷＯ２）粉末、
それにアセチレンを原料とするカーボンブラックを用い
、それらを１：１：１のモル比で混合後、直径１０ｉ■
、高さｌＯｍｎ＋の柱状にプレス成形した。この成形体
を炭化ケイ米製の型材を用いた一軸加圧真空ホットプレ
スを用いて焼結を行った。成形体への着火は、タングス
テンフィラメントに通電することによって行った。試料
を室温・真空（１＋ｎｎ＋Ｈｇ）雰囲気・０．１ＧＰａ
の圧力条件下で、着火用ヒーターに通電して反応を開始
させた。得られた焼結体をＸ線回折を用いて同定したと
ころα型炭化タングステン（α−ＷＣ）と正方晶系の酸
化ジルコニウム（ｔ−Ｚｒ０２）と単科晶系の酸化ジル
コニウム（ｍ−Ｚｒ０２）の回折線しか見られなかった
。またこの焼結体の相対密度は、９０％であった。また
、ｔ−Ｚｒ０ｑとｍ−ＺｒＯ２の比率は約１：ｌであっ
た。Examples Example 1 Zirconium powder with a particle size of 10 μm or less as a starting material,
Tungsten dioxide (WO2) powder with an average particle size of 2 μm,
Using carbon black made from acetylene as a raw material, after mixing them at a molar ratio of 1:1:1,
, and press-molded into a columnar shape with a height of lOmn+. This molded body was sintered using a uniaxial pressure vacuum hot press using a mold made of silicon carbide rice. The molded body was ignited by energizing the tungsten filament. Sample at room temperature, vacuum (1+nn+Hg) atmosphere, 0.1GPa
The reaction was started by energizing the ignition heater under the following pressure conditions. The obtained sintered body was identified using X-ray diffraction, and it was found to be α-type tungsten carbide (α-WC), tetragonal zirconium oxide (t-Zr02), and monocrystalline zirconium oxide (m-Zr02). Only diffraction lines were visible. Further, the relative density of this sintered body was 90%. Further, the ratio of t-Zr0q and m-ZrO2 was approximately 1:l.
このプロセスの化学反応式は次のとおりである。The chemical reaction equation for this process is as follows.
Ｚ ｒ ＋ Ｗ Ｏ２＋Ｃ＋ Ｚ ｒ Ｏ２＋Ｗ にの
反応においては、ＺｒによるＷＯ２の還元を基本にして
、還元されたＷ金属がＣと反応してＷＣになる。このと
きの反応熱が大きいので外部から加熱しな（ても試料が
高１ｍ （２０００℃程度まで上昇する）になり、しか
も加圧しているのでＺｒＯ２粒子とＷＣ粒子が焼結して
Ｚ ｒ Ｏ２Ｗ Ｃ複合焼結体が得られるのである。In the reaction to Z r + W O2+C+ Z r O2+W , the reduced W metal reacts with C to become WC based on the reduction of WO2 by Zr. Since the reaction heat at this time is large, no external heating is required (even if the sample becomes 1 m high (up to about 2000°C), and the pressure is applied, the ZrO2 particles and WC particles are sintered and ZrO2W A C composite sintered body is obtained.
表１には他の試料についての実験結果もあわせて示した
。この表では、複合焼結体の相対密度が９０％以上の試
料にはセラミックス基板等として十分に実用化可能なの
で○印を、相対密度が８５％から９０％の間の試料は非
常に低いコストで製造でき、実用化の可能性があるので
Δ印を、相対密度が８５％以下の試料は、実用化の可能
性がないと考えられるのでＸ印とした。比較例（試料７
と８）で示したようにタングステン原料としてＷ Ｏ３
を用いた場合には、反応が激しくしかも反応時の体積収
縮が非常に大きいので、得られる複合焼結体の相対密度
が低いことがわかる。それに対してＷＯ２を用いると得
られる焼結体の相対密度が高くなる。これは、Ｗ Ｏ２
を出発原料をとして用いるとＷ Ｏ２を用いる場合に比
較して反応時に発生する熱量が小さい（それでも室温で
十分反応する）が、反応時の体積収縮が非常に小さいの
で試料にスムーズにプレスの圧力が伝達でき、そのため
得られる複合焼結体の相対密度が高くなるものと考えら
れる。Table 1 also shows experimental results for other samples. In this table, samples with a relative density of 90% or more of the composite sintered body are marked with a circle because they can be put to practical use as ceramic substrates, etc., and samples with a relative density between 85% and 90% have a very low cost. A sample with a relative density of 85% or less is marked with an X because it is considered that there is no possibility of practical use. Comparative example (sample 7
and 8), W O3 is used as a tungsten raw material.
When using this method, the reaction is intense and the volumetric contraction during the reaction is very large, so it can be seen that the relative density of the resulting composite sintered body is low. On the other hand, when WO2 is used, the resulting sintered body has a higher relative density. This is W O2
When using WO2 as a starting material, the amount of heat generated during the reaction is smaller than when using WO2 (the reaction is still sufficient at room temperature), but the volumetric shrinkage during the reaction is very small, so the pressing pressure can be applied smoothly to the sample. It is thought that the relative density of the obtained composite sintered body becomes high.
表１の試料２と３および５と６は還元金属と炭素と二酸
化タングステンの他にさらにコバルト金属粉末を加えた
場合である。コバルト金属を用いるといずれの試料も加
えない場合に比べて得られる複合焼結体の相対密度が高
（なっていることがわかる（９５％以上）。Samples 2, 3, 5, and 6 in Table 1 are cases in which cobalt metal powder was further added in addition to the reduced metal, carbon, and tungsten dioxide. It can be seen that when cobalt metal is used, the relative density of the composite sintered body obtained is higher (95% or more) than when neither sample is added.
実施例２
出発原料として粒径１０μｍ以下のジルコニウム粉末、
平均粒径２μｍの二酸化タングステン粉末（ＷＯ２）、
それにアセチレンを原料とするカーボンブラックを用い
、それらを２．２．１のモル比で混合後、実施例１と同
様のプロセスで処理した。得られた焼結体をＸ線回折を
用いて同定したところβ型の炭化タングステン（β−Ｗ
２Ｃ）と正方晶系の酸化ジルコニウム（ｔ−ＺｒＯ２）
と単斜晶系の酸化ジルコニウム（ｍ−ＺｒＯ２）の回折
線しか見られなかった。またこの焼結体の相対密度は、
９０％であった。また、ｔ−ＺｒＯ２とｍ−ＺｒＯ２の
比率は実施例１の場合と同様に約１＝１であった。Example 2 Zirconium powder with a particle size of 10 μm or less as a starting material,
Tungsten dioxide powder (WO2) with an average particle size of 2 μm,
Carbon black made from acetylene was used therein, and after mixing them at a molar ratio of 2.2.1, the same process as in Example 1 was carried out. The obtained sintered body was identified using X-ray diffraction and was found to be β-type tungsten carbide (β-W
2C) and tetragonal zirconium oxide (t-ZrO2)
Only the diffraction lines of monoclinic zirconium oxide (m-ZrO2) were observed. Also, the relative density of this sintered body is
It was 90%. Further, the ratio of t-ZrO2 and m-ZrO2 was approximately 1=1 as in Example 1.
本実施例の場合も実施例１と同様に酸化タングステン原
料としてＷ Ｏｓを用いると得られた焼結体の相対密度
は７８％であり、酸化ジルコニウムもすべて単斜晶系で
あった。In this example, as in Example 1, when W 2 Os was used as the tungsten oxide raw material, the relative density of the obtained sintered body was 78%, and all of the zirconium oxide was monoclinic.
このプロセスの化学反応式はを以下に示した。The chemical reaction formula for this process is shown below.
２Ｚｒ＋２ＷＯ２＋Ｃ＋２ＺｒＯ２＋Ｗ２ Ｃ発明の効
果
本発明の製造方法によれば、還元金属の粉末と炭素と二
酸化タングステンとからなる混合物の成形体に圧力をか
けた状態で、その成形体の一部を強熱点火して燃焼反応
を起こさせるだけで高密度炭化タングステン−酸化物複
合焼結体が作製できる。従って、本発明の製造方法によ
れば、従来の炭化タングステン粉末と酸化物粉末を用い
た製造方法に比較してはるかに低温のプロセスで、つま
り、きわめて小さなエネルギーで炭化タングステン−酸
化物複合焼結体が作製できる。しかも、得られた焼結体
は、従来の製造方法によって作製した焼結体と全（変わ
らない特性を有している。2Zr + 2WO2 + C + 2ZrO2 + W2 C Effects of the Invention According to the manufacturing method of the present invention, a part of the molded body is ignited under high heat while pressure is applied to a molded body of a mixture of reduced metal powder, carbon, and tungsten dioxide. A high-density tungsten carbide-oxide composite sintered body can be produced simply by causing a combustion reaction. Therefore, according to the manufacturing method of the present invention, the tungsten carbide-oxide composite sintering process is performed at a much lower temperature than the conventional manufacturing method using tungsten carbide powder and oxide powder, that is, with extremely low energy. A body can be created. Moreover, the obtained sintered body has properties that are completely the same as those of the sintered body produced by the conventional manufacturing method.
Claims (6)
粉末とからなる成形体を、加圧条件下でその成形体の一
部に点火して燃焼過程を開始させ、その後の金属粉末と
二酸化タングステン粉末と炭素の反応及び生成した炭化
タングステンと酸化物の焼結を、燃焼過程の結果発生す
る熱によって進行させる炭化タングステン−酸化物複合
焼結体の製造方法。(1) A molded body made of reducing metal powder, carbon, and tungsten dioxide powder is ignited in a part of the molded body under pressurized conditions to start the combustion process, and then the metal powder and tungsten dioxide powder are ignited. A method for producing a tungsten carbide-oxide composite sintered body, in which the reaction between powder and carbon and the sintering of the generated tungsten carbide and oxide are advanced by heat generated as a result of the combustion process.
程を開始させることを特徴とする特許請求の範囲第１項
記載の炭化タングステン−酸化物複合焼結体の製造方法
。(2) A method for producing a tungsten carbide-oxide composite sintered body according to claim 1, characterized in that the compact is ignited under conditions of pressurization and heating to start a combustion process.
コニウム粉末のうちのいずれかである特許請求の範囲第
１項記載の炭化タングステン−酸化物複合焼結体の製造
方法。(3) The method for producing a tungsten carbide-oxide composite sintered body according to claim 1, wherein the reducing metal powder is either aluminum powder or zirconium powder.
粉末と、コバルト金属粉末とからなる成形体を、加圧条
件下でその成形体の一部に点火して燃焼過程を開始させ
、その後の還元用金属粉末と二酸化タングステン粉末と
炭素の反応及び生成した炭化タングステン、酸化物、そ
れにコバルト金属の焼結を、燃焼過程の結果発生する熱
によって進行させる炭化タングステン−酸化物複合焼結
体の製造方法。(4) A part of the compact made of reducing metal powder, carbon, tungsten dioxide powder, and cobalt metal powder is ignited under pressurized conditions to start the combustion process, and the subsequent Production of a tungsten carbide-oxide composite sintered body in which the reaction of reducing metal powder, tungsten dioxide powder, and carbon and the sintering of the generated tungsten carbide, oxide, and cobalt metal proceed with the heat generated as a result of the combustion process. Method.
程を開始させることを特徴とする特許請求の範囲第４項
記載の炭化タングステン−酸化物複合焼結体の製造方法
。(5) The method for producing a tungsten carbide-oxide composite sintered body according to claim 4, characterized in that the compact is ignited under conditions of pressurization and heating to start a combustion process.
コニウム粉末のうちのいずれかである特許請求の範囲第
４項記載の炭化タングステン−酸化物複合焼結体の製造
方法。(6) The method for producing a tungsten carbide-oxide composite sintered body according to claim 4, wherein the reducing metal powder is either aluminum powder or zirconium powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61128666A JPS62288166A (en) | 1986-06-03 | 1986-06-03 | Manufacture of tungsten carbide-oxide composite sintered body |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61128666A JPS62288166A (en) | 1986-06-03 | 1986-06-03 | Manufacture of tungsten carbide-oxide composite sintered body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62288166A true JPS62288166A (en) | 1987-12-15 |
Family
ID=14990437
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61128666A Pending JPS62288166A (en) | 1986-06-03 | 1986-06-03 | Manufacture of tungsten carbide-oxide composite sintered body |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62288166A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02212347A (en) * | 1989-02-10 | 1990-08-23 | Toyota Central Res & Dev Lab Inc | Production of composite material and composition as starting material |
| WO2001030722A1 (en) * | 1999-10-27 | 2001-05-03 | Nippon Tungsten Co., Ltd. | Wc-base composite ceramic sintered compact |
-
1986
- 1986-06-03 JP JP61128666A patent/JPS62288166A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02212347A (en) * | 1989-02-10 | 1990-08-23 | Toyota Central Res & Dev Lab Inc | Production of composite material and composition as starting material |
| WO2001030722A1 (en) * | 1999-10-27 | 2001-05-03 | Nippon Tungsten Co., Ltd. | Wc-base composite ceramic sintered compact |
| US6551954B1 (en) * | 1999-10-27 | 2003-04-22 | Nippon Tungsten Co., Ltd. | WC-base composite ceramic sintered compact |
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