JPH034509B2 - - Google Patents
Info
- Publication number
- JPH034509B2 JPH034509B2 JP59100895A JP10089584A JPH034509B2 JP H034509 B2 JPH034509 B2 JP H034509B2 JP 59100895 A JP59100895 A JP 59100895A JP 10089584 A JP10089584 A JP 10089584A JP H034509 B2 JPH034509 B2 JP H034509B2
- Authority
- JP
- Japan
- Prior art keywords
- reaction
- sintering
- powder
- sintered body
- sintered
- 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.)
- Expired - Lifetime
Links
- 238000005245 sintering Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 5
- 239000011812 mixed powder Substances 0.000 claims 1
- 229910052755 nonmetal Inorganic materials 0.000 claims 1
- 230000000737 periodic effect Effects 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 229910006249 ZrSi Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910016006 MoSi Inorganic materials 0.000 description 1
- 229910008484 TiSi Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000007723 die pressing method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Description
【発明の詳細な説明】
(イ) 技術分野
本発明は特に大型で均質なセラミツク焼結体を
得る方法としてセラミツク成形体の内部より焼結
を進行させる方法に関する。DETAILED DESCRIPTION OF THE INVENTION (a) Technical Field The present invention particularly relates to a method of proceeding sintering from the inside of a ceramic molded body as a method of obtaining a large and homogeneous ceramic sintered body.
(ロ) 従来技術とその問題点
セラミツクスはその秀れた物理的・化学的特性
によつて耐摩、耐食用途を始め、構造材料、機能
材料等広い範囲にわたつて実用化されている。セ
ラミツクスを製造する方法としては、ほとんどの
場合、粉末の成形を行なつたのち、焼結する方法
が採用されている。焼結は、大気中、ガス、雰囲
気中、真空中等の雰囲気中で外部から加熱し粉末
のもつ表面エネルギーを利用したり、低温で液相
を生成する物質を添加し、液相の表面張力を利用
して焼結を進行させる等の方法がとられる。(b) Prior art and its problems Due to its excellent physical and chemical properties, ceramics have been put to practical use in a wide range of applications, including wear and corrosion resistance, structural materials, and functional materials. In most cases, ceramics are manufactured by molding powder and then sintering it. Sintering is performed by heating the powder externally in an atmosphere such as air, gas, atmosphere, or vacuum to utilize the surface energy of the powder, or by adding a substance that generates a liquid phase at low temperatures to reduce the surface tension of the liquid phase. Methods such as utilizing this material to advance sintering are taken.
これらの方法に共通の問題としては、成形体の
外部から熱を加えることから、熱勾配の発生によ
る破壊あるいは、焼結体内部でのガスのトラツ
プ、焼結体表面の粒成長等が指摘されている。 Problems common to these methods include damage caused by thermal gradients, gas trapping inside the sintered body, and grain growth on the surface of the sintered body because heat is applied from the outside of the sintered body. ing.
(ハ) 発明の開示
本発明者らは、均一な組成・構造をもつセラミ
ツクスを得るために、種々の検討を行なつた結
果、成形体内部から焼結を進行させることによつ
て、従来技術による焼結体の欠点を解消し得るこ
とを見い出したものである。すなわち、セラミツ
クスの多くは、発熱反応によつて生成することに
着目し実験した結果、成形体内部に一且反応が開
始すると、外部から加熱がなくとも、あるいはわ
ずかな加熱で、連続的に反応が表面まで進行し、
焼結体となることを見い出したものである。(C) Disclosure of the Invention The present inventors have conducted various studies in order to obtain ceramics with a uniform composition and structure. As a result, the present inventors have succeeded in improving the conventional technology by proceeding sintering from inside the compact. It has been discovered that the drawbacks of sintered bodies can be overcome. In other words, as a result of experiments focusing on the fact that most ceramics are produced through exothermic reactions, we found that once a single reaction starts inside the molded product, the reaction continues without external heating or with only a small amount of heating. progresses to the surface,
It was discovered that the material becomes a sintered body.
本発明によつて得られる焼結体としては、炭化
物としてTiC、ZrC、HfC、VC、NbC、Ta2C、
TaC、窒化物としてMg3N2、BN、Ａ｜Ｎ、
Si3N4、TiN、ZrN、HfN、VN、NbN、TaN、
硼化物としてTiB2、TaB2、珪化物としてTiSi3、
ZrSi、ZrSi2、MoSi2等であり、さらにこれから
選ばれた２種以上の混合物、不定比化合物であつ
てもよい。 The sintered body obtained by the present invention includes carbides such as TiC, ZrC, HfC, VC, NbC, Ta 2 C,
TaC, Mg 3 N 2 as nitride, BN, A｜N,
Si 3 N 4 , TiN, ZrN, HfN, VN, NbN, TaN,
TiB 2 , TaB 2 as borides, TiSi 3 as silicides,
These include ZrSi, ZrSi 2 , MoSi 2 , etc., and may also be a mixture of two or more selected from these, or a non-stoichiometric compound.
成形体組成物としては、たとえば炭化物であれ
ば、金属元素と炭素の混合物、金属酸化物と炭素
の混合物等を使用できる。窒化物の場合、窒素ガ
ス中で反応をおこさせることで目的を達すること
が出来るのである。 As the molded body composition, for example, in the case of a carbide, a mixture of a metal element and carbon, a mixture of a metal oxide and carbon, etc. can be used. In the case of nitrides, this goal can be achieved by causing a reaction in nitrogen gas.
また金属元素と炭素の混合物を窒素ガス、ある
いはアンモニアガス中で反応させることで金属炭
窒化物を得るなど、これらの組み合わせも、もち
ろん可能である。 Of course, a combination of these is also possible, such as obtaining a metal carbonitride by reacting a mixture of a metal element and carbon in nitrogen gas or ammonia gas.
次に、成形体組成物としては、粉末の混合後通
常の方法で成形されるが、反応性の点から、成形
体密度を調整することが望ましい。すなわち、雰
囲気との反応を必要としない場合は高圧成形で行
ない、雰囲気との反応を必要とする場合は低密度
成形体とする。 Next, the molded body composition is molded by a conventional method after mixing the powders, but it is desirable to adjust the density of the molded body from the viewpoint of reactivity. That is, if a reaction with the atmosphere is not required, high-pressure molding is used, and if a reaction with the atmosphere is required, a low-density molded product is used.
成形体は焼結を開始させる部分に、ヒーターを
埋め込み加熱することで反応を開始させる等の方
法で、成形体内部から焼結を進行させる。さら
に、外部より加熱し、外部からも焼結を進める、
反応熱に加えて外部から熱を供給し反応を継続さ
せる方法も有効である。 Sintering is progressed from inside the molded body by a method such as embedding a heater in the part of the molded body where sintering is to be started and heating it to start the reaction. Furthermore, by heating from the outside and proceeding with sintering from the outside,
It is also effective to supply heat from outside in addition to the reaction heat to continue the reaction.
また、得られた焼結体を再加熱しさらに焼結を
進行させる、HIPするなどの方法も有効である。 Also effective are methods such as reheating the obtained sintered body to further advance sintering, and HIPing.
以下実施例をあげて説明する。 This will be explained below by giving examples.
実施例 １
Ti粉末とＣ粉末（カーボン粉末）をモル比で
１：１となる様に混合後5t／cm2の圧力でCIP（静
水圧プレス）した。得られた型押体は、寸法がお
よそφ30×30Hmmであつた。型押体に穴あけし、
カーボンヒーターを埋め込み、真空槽内に装入し
た。外部よりヒーターに入電し、TiとＣの反応
をおこさせたところ、ひき続いてTiとＣの反応
が反応熱で連続しておこり、成形体内部から表面
に向かつて順次焼結が進行し、約φ25×25Hmmの
焼結体を得た。Example 1 Ti powder and C powder (carbon powder) were mixed at a molar ratio of 1:1 and then subjected to CIP (hydrostatic pressing) at a pressure of 5 t/cm 2 . The obtained embossed body had dimensions of approximately φ30×30Hmm. Drill a hole in the embossed body,
A carbon heater was embedded and placed in a vacuum chamber. When power was applied to the heater from the outside to cause a reaction between Ti and C, the reaction between Ti and C occurred continuously due to the reaction heat, and sintering progressed sequentially from the inside of the compact to the surface. A sintered body of approximately φ25×25Hmm was obtained.
TiCの焼結体はTiC粉末の型押焼結によつて
は、緻密な焼結体を得難いことから、本法による
焼結がきわめて有効であることがわかる。 Since it is difficult to obtain a dense TiC sintered body by die pressing sintering of TiC powder, it is clear that sintering by this method is extremely effective.
実施例 ２
実施例１と同様の条件で、Zr＋Ｃ、Ta＋Ｃ、
Ti＋2B、Ti＋Siの組み合わせで本発明による焼
結を実施したところ、いずれも緻密質の焼結体を
得た。またTi＋Ｃの組み合わせで窒素ガス中に
おいて反応させたところ、TiC0.7N0.3の固溶体か
らなる焼結体を得た。Example 2 Under the same conditions as Example 1, Zr+C, Ta+C,
When the combinations of Ti+2B and Ti+Si were sintered according to the present invention, dense sintered bodies were obtained in both cases. When a combination of Ti and C was reacted in nitrogen gas, a sintered body consisting of a solid solution of TiC 0.7 N 0.3 was obtained.
実施例 ３
Ti、Ta、Ｃをそれぞれモル比で１：１：２の
組成に混合後実施例１と同様の条件で焼結を実施
したところ、Ti0.5Ta0.5Ｃの固溶体からなる焼結
体を得た。Example 3 After mixing Ti, Ta, and C in a molar ratio of 1:1:2, sintering was performed under the same conditions as in Example 1. As a result, a sintered body consisting of a solid solution of Ti 0.5 Ta 0.5 C was obtained. I got it.
実施例 ４
TiとＣをモル比で１：１となるように混合後
さらにNi粉を５重量パーセント添加して粉末混
合物を得た。混合物を5t／cm2でCIPしてφ300×
300Hの成形体を得た。得られた成形体にカーボ
ンヒーターを埋め込み、発熱させたところ成形体
中心部より焼結が進行し、得られた焼結体は内部
にポアが極めて少ない焼結体であつた。一方、
TiC−５重量パーセントNi組成物を同様に5t／cm2
圧力でCIPし、1450℃で焼成したところ内部にポ
ーラス部が存在する不均一な焼結体となつた。Example 4 After mixing Ti and C at a molar ratio of 1:1, 5% by weight of Ni powder was added to obtain a powder mixture. CIP the mixture at 5t/ cm2 to φ300×
A 300H molded body was obtained. When a carbon heater was embedded in the obtained compact and heat was generated, sintering proceeded from the center of the compact, and the obtained sintered compact had very few pores inside. on the other hand,
Similarly, TiC-5 weight percent Ni composition was 5t/cm 2
When CIP was performed under pressure and fired at 1450℃, a non-uniform sintered body with porous parts inside was obtained.
実施例 ５
Si粉末を5t／cm2でCIPしてφ100×200Hmmの成
形体を得た。得られた成形体にカーボンヒーター
を埋め込み、窒素ガス圧を200気圧に保持した圧
力容器中で、カーボンヒーターを発熱させたとこ
ろ、成形体中心部より焼結が進行し、Si3N4の焼
結体が得られた。Example 5 Si powder was subjected to CIP at 5t/cm 2 to obtain a molded body of φ100×200Hmm. A carbon heater was embedded in the obtained compact, and when the carbon heater was heated in a pressure vessel with nitrogen gas pressure maintained at 200 atm, sintering progressed from the center of the compact, and the Si 3 N 4 sintered. A concretion was obtained.
Claims (1)
よび／または金属元素粉末と雰囲気ガスとが発熱
反応を起し、引続き連続的に反応する混合物を含
む成型体の内部を局部的に加熱して反応を開始さ
せ、引続いてその反応熱によつて順次表面にむか
つて反応を進行させ焼結体とすることを特徴とす
るセラミツクスの焼結方法。 ２ 金属元素が周期律表第、第ａ、第ａ、
第ａ族元素から選ばれた少くとも１種の元素で
あり、非金属元素がＢ、Ｃ、Ｎ、Siから選ばれた
少くとも１種の元素であることを特徴とする特許
請求の範囲第１項記載のセラミツクスの焼結方
法。[Scope of Claims] 1. The inside of a molded body containing a mixture in which a mixed powder of a metal element and a non-metal element and/or a metal element powder and an atmospheric gas cause an exothermic reaction and continuously react. A method for sintering ceramics, characterized in that a reaction is started by heating locally, and then the reaction is sequentially progressed to the surface by the heat of the reaction to form a sintered body. 2 The metal elements are the periodic table, a, a,
The claim 1 is characterized in that the nonmetallic element is at least one element selected from Group A elements, and the nonmetallic element is at least one element selected from B, C, N, and Si. A method for sintering ceramics according to item 1.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59100895A JPS60246271A (en) | 1984-05-18 | 1984-05-18 | Ceramic sintering process |
| DE3588005T DE3588005T2 (en) | 1984-05-18 | 1985-05-17 | Process for sintering ceramic bodies with a distributed metal reinforcement. |
| DE8585303474T DE3584475D1 (en) | 1984-05-18 | 1985-05-17 | METHOD FOR SINTERING CERAMIC BODIES AND CERAMIC BODIES PRODUCED BY SAME WITH A DISTRIBUTED METAL REINFORCEMENT. |
| EP91102739A EP0435854B1 (en) | 1984-05-18 | 1985-05-17 | Method of sintering metal-dispersed reinforced ceramics |
| EP85303474A EP0165707B1 (en) | 1984-05-18 | 1985-05-17 | Method of sintering ceramics and metal-dispersed reinforced ceramics obtained thereby |
| US07/158,115 US4906295A (en) | 1984-05-18 | 1988-02-16 | Dispersed reinforced ceramics |
| US07/392,287 US4965044A (en) | 1984-05-18 | 1989-08-11 | Method of sintering ceramics and metal dispersed reinforced ceramics obtained thereby |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59100895A JPS60246271A (en) | 1984-05-18 | 1984-05-18 | Ceramic sintering process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60246271A JPS60246271A (en) | 1985-12-05 |
| JPH034509B2 true JPH034509B2 (en) | 1991-01-23 |
Family
ID=14286069
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59100895A Granted JPS60246271A (en) | 1984-05-18 | 1984-05-18 | Ceramic sintering process |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60246271A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2949586B2 (en) * | 1988-03-07 | 1999-09-13 | 株式会社日立製作所 | Conductive material and manufacturing method thereof |
-
1984
- 1984-05-18 JP JP59100895A patent/JPS60246271A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60246271A (en) | 1985-12-05 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |