JPH0526753B2 - - Google Patents
Info
- Publication number
- JPH0526753B2 JPH0526753B2 JP22247786A JP22247786A JPH0526753B2 JP H0526753 B2 JPH0526753 B2 JP H0526753B2 JP 22247786 A JP22247786 A JP 22247786A JP 22247786 A JP22247786 A JP 22247786A JP H0526753 B2 JPH0526753 B2 JP H0526753B2
- Authority
- JP
- Japan
- Prior art keywords
- sintered body
- golden
- partially stabilized
- stabilized zirconia
- zirconia 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
- 239000000919 ceramic Substances 0.000 claims description 15
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 claims description 14
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000010304 firing Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000000465 moulding Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910052582 BN Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Description
【発明の詳細な説明】
産業上の利用分野
本発明は装飾用硬質黄金色のセラミツクスの製
造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for producing decorative hard golden ceramics.
従来の技術
近年、窒化チタン（TiN）、窒化ジルコニウム
（ZrN）、炭化タンタル（TaC）などの第1V、Ｖ
族遷移金属の炭化物、窒化物および炭窒化物を主
成分とし、鉄（Fe）、コバルト（Co）、ニツケル
（Ni）、モリブデン（Mo）などの結合用金属を添
付した焼結金属は、金色の色調に加え、高硬度お
よび高強度という優れた特性を有しているため、
装飾用部材として広範囲に使用されている。Conventional technology In recent years, 1V, V
Sintered metals whose main components are carbides, nitrides, and carbonitrides of group transition metals, and which are accompanied by bonding metals such as iron (Fe), cobalt (Co), nickel (Ni), and molybdenum (Mo), have a golden color. In addition to its color tone, it has excellent properties such as high hardness and high strength.
It is widely used as a decorative member.
しかしながら、TiN、ZrN、TaCなどは単独
では焼結が大変難しく、かつ高硬度高強度焼結体
を得るために、前記結合用金属が焼結助剤として
添付されており、これにより、焼結合金中に存在
する金属成分の腐食が進行して装飾用部材の色調
が損われるという問題があり、この問題を解決す
るために、特開昭60−36378号公報において、
ZrNを主成分とし、アルミナ（Al2O3）、ジルコ
ニア（ZrO2）の少なくとも一種を0.1〜30重量％
含有させたことを特徴とするセラミツクスが提案
されている。 However, it is very difficult to sinter TiN, ZrN, TaC, etc. alone, and in order to obtain a high hardness and high strength sintered body, the above-mentioned bonding metal is attached as a sintering aid. There is a problem that corrosion of the metal components present in gold progresses and the color tone of decorative members is impaired.
Main component is ZrN, and 0.1 to 30% by weight of at least one of alumina (Al 2 O 3 ) and zirconia (ZrO 2 )
Ceramics have been proposed that are characterized by containing.
発明が解決しようとする問題点
しかし、上記特開昭60−36378号公報において
開示されているセラミツクスではZrNを70〜99.9
重量％も使用しなければならないため高価なもの
となつている。また、CVD法を行なうための装
置は非常に高価であり、操作が複雑である。Problems to be Solved by the Invention However, in the ceramics disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 60-36378, ZrN is
Since it is necessary to use weight percentages, it is expensive. Furthermore, equipment for carrying out the CVD method is very expensive and complicated to operate.
本発明は上記問題点を解決するものであり、通
常の焼成用炉（大気、真空、窒素雰囲気）を使用
して耐食性の優れた、安価な装飾用硬質黄金色の
セラミツクスを製造する方法を提供することを目
的とするものである。 The present invention solves the above-mentioned problems, and provides a method for manufacturing inexpensive decorative hard golden ceramics with excellent corrosion resistance using a normal firing furnace (air, vacuum, nitrogen atmosphere). The purpose is to
問題点を解決するための手段
上記問題点を解決するため、本発明は、部分安
定化ジルコニア焼結体を四窒化三ケイ素
（Si3N4）、窒化アルミニウム（AlN）、窒化ホウ
素（BN）の１種の粉末、または２種あるいは３
種の混合粉末にて被覆し、窒素（N2）雰囲気下
で加熱する工程を設けるようにしたものである。Means for Solving the Problems In order to solve the above problems, the present invention provides a partially stabilized zirconia sintered body made of trisilicon tetranitride (Si 3 N 4 ), aluminum nitride (AlN), boron nitride (BN). 1 type of powder, or 2 types or 3 types of
The method includes a step of coating the seed with a mixed powder of seeds and heating it in a nitrogen (N 2 ) atmosphere.
作 用
上記方法により、部分安定化ジルコニア焼結体
を用いることで、従来のように焼結合金中に存在
する結合用金属成分の腐食により装飾用部材の色
調が損なわれることのない高硬度高強度の焼結体
を得ることができ、しかもZrNを大量に使うよう
なこともなく、通常の焼成用炉（大気、真空、窒
素雰囲気）を使用できるので、耐食性に優れた硬
質黄金色のセラミツクスを安価に製造できる。Effect By using the partially stabilized zirconia sintered body using the above method, it is possible to create a high-hardness, high-quality decorative member that will not lose its color tone due to the corrosion of the bonding metal components present in the sintered alloy, unlike conventional sintered alloys. It is possible to obtain a strong sintered body, and it also does not require the use of large amounts of ZrN, and can be used in ordinary firing furnaces (air, vacuum, nitrogen atmosphere), making it a hard, golden-yellow ceramic with excellent corrosion resistance. can be manufactured at low cost.
実施例
以下、本発明の一実施例について説明する。加
熱はいずれも焼成用炉（大気、真空、窒素雰囲
気）にて行なう。Example An example of the present invention will be described below. All heating is performed in a firing furnace (air, vacuum, nitrogen atmosphere).
実施例 １
ジルコニア（ZrO2）に安定化剤としてイツト
リウム(Y)の酸化物を固溶させ、金型−軸成形後、
湿式ラバープレス成形により製造されたZrO2成
形体を大気中で1450℃に加熱し、部分安定化ジル
コニア焼結体を形成する。次に、この部分安定化
ジルコニア焼結体を0.06torr以下の真空下にて再
び10時間、1450℃にて加熱して黒色の焼結体を形
成する。そして、この黒色の焼結体を四窒化三ケ
イ素（Si3N4）粉末にて被覆し、窒素（N2）気流
の下で10時間、1750℃にて加熱すると、黄金色の
セラミツクスが形成される。Example 1 Yttrium (Y) oxide was dissolved as a stabilizer in zirconia (ZrO 2 ), and after mold-shaft molding,
A ZrO 2 molded body produced by wet rubber press molding is heated to 1450°C in the atmosphere to form a partially stabilized zirconia sintered body. Next, this partially stabilized zirconia sintered body is heated again at 1450° C. for 10 hours under a vacuum of 0.06 torr or less to form a black sintered body. This black sintered body was then coated with trisilicon tetranitride (Si 3 N 4 ) powder and heated at 1750°C for 10 hours under a nitrogen (N 2 ) stream, forming a golden-yellow ceramic. be done.
実施例 ２
実施例１と同様に部分安定化ジルコニア焼結体
を形成し、この部分安定化ジルコニア焼結体を
0.06torr以下の真空下にて10時間、1450℃にて加
熱して黒色の焼結体を形成する。そして、この黒
色の焼結体を窒化アルミニウム（AlN）粉末に
て被覆し、窒素（N2）気流の下で10時間、1750
℃にて加熱すると、黄金色のセラミツクスが形成
される。Example 2 A partially stabilized zirconia sintered body was formed in the same manner as in Example 1, and this partially stabilized zirconia sintered body was
A black sintered body is formed by heating at 1450°C for 10 hours under a vacuum of 0.06 torr or less. This black sintered body was then coated with aluminum nitride (AlN) powder and heated at 1750 °C for 10 hours under a nitrogen (N 2 ) stream.
When heated at ℃, a golden yellow ceramic is formed.
実施例 ３
実施例１と同様に部分安定化ジルコニア焼結体
を形成し、この部分安定化ジルコニア焼結体の表
面に窒化ホウ素（BN）スプレーにてBNを塗布
し、N2の気流の下で10時間、1750℃にて加熱す
ると、黄金色のセラミツクスが形成される。Example 3 A partially stabilized zirconia sintered body was formed in the same manner as in Example 1, and BN was applied to the surface of the partially stabilized zirconia sintered body using boron nitride (BN) spray, and the mixture was heated under a stream of N 2 . When heated at 1750℃ for 10 hours, a golden yellow ceramic is formed.
実施例 ４
実施例１と同様に部分安定化ジルコニア焼結体
を形成し、この部分安定化ジルコニア焼結体の表
面に窒化ホウ素（BN）スプレーにてBNを塗布
し、Si3N4粉末中に埋め込み、N2気流の下で10時
間、1750℃にて加熱すると、黄金色のセラミツク
スが形成される。Example 4 A partially stabilized zirconia sintered body was formed in the same manner as in Example 1, and boron nitride (BN) was applied to the surface of the partially stabilized zirconia sintered body using boron nitride (BN ) spray. When heated at 1750°C for 10 hours under a stream of N2 , a golden-yellow ceramic is formed.
また、上記実施例以外でも、Si3N4、AlN、
BNの２種あるいは３種を組み合わせた混合粉末
にて部分安定化ジルコニア焼結体を被覆し、上記
と同様加熱処理をすると、黄金色のセラミツクス
が形成される。 In addition, in addition to the above examples, Si 3 N 4 , AlN,
When a partially stabilized zirconia sintered body is coated with a mixed powder of two or three types of BN and heat treated in the same manner as above, a golden-yellow ceramic is formed.
上記方法で得られた全ての黄金色のセラミツク
スをジルコニア（ZrO2）を浸食する沸騰濃塩酸
中に100時間浸漬し、４mm幅、40mm長さ、３mm高
さの長方体に加工し、曲げ強度を測定したとこ
ろ、曲げ強度の減少は認められなかつた。他方、
黄金色の処理をしなかつた試料では７％の曲げ強
度の減少が認められた。これらのことから、本実
施例で形成された黄金色のセラミツクスの表面に
は窒化ジルコニウム（ZnN）の皮膜が形成され
ていることが確認された。 All the golden ceramics obtained by the above method were immersed for 100 hours in boiling concentrated hydrochloric acid that erodes zirconia (ZrO 2 ), processed into rectangular bodies with a width of 4 mm, a length of 40 mm, and a height of 3 mm, and then bent. When the strength was measured, no decrease in bending strength was observed. On the other hand,
A 7% decrease in bending strength was observed in the sample without the golden treatment. From these results, it was confirmed that a zirconium nitride (ZnN) film was formed on the surface of the golden ceramics formed in this example.
このように、ジルコニアを主成分として、通常
の焼成用炉にて耐食性の優れた装飾用硬質黄金色
のセラミツクスを製造できる。 In this way, it is possible to produce decorative hard gold-colored ceramics with excellent corrosion resistance using zirconia as the main component in a normal firing furnace.
なお、ZrO2成形体の安定化剤としては、イツ
トリウム(Y)のほかに、カリウム（Ca）、マグネシ
ウム（Mg）、セリウム（Ce）などの酸化物を使
用することができ、またZrO2成形体の成形方法
としてはラバープレス法のほかに、鋳込み成形
法、プレス成形法などを用いることができる。 In addition to yttrium (Y), oxides such as potassium (Ca), magnesium (Mg), and cerium (Ce) can be used as stabilizers for ZrO 2 moldings . As a method for forming the body, in addition to the rubber press method, a casting method, a press molding method, etc. can be used.
また、部分安定化ジルコニア焼結体を真空下で
加熱する実施例１、実施例２の工程は、部分安定
化ジルコニア焼結体内に存在する空気、主に酸素
（O2）を少しでも排出しておく目的で行なうもの
であり、必ずしも必要ではない。N2気流下での
加熱温度は、低いと黄金色の反応はなく、また高
すぎると強度が低下する傾向があり、最適な加熱
温度は1400℃〜1800℃である。 In addition, the process of Example 1 and Example 2 in which the partially stabilized zirconia sintered body is heated under vacuum eliminates even the slightest amount of air, mainly oxygen (O 2 ), present inside the partially stabilized zirconia sintered body. This is done for the purpose of preserving the information, and is not necessarily necessary. If the heating temperature under a N2 stream is low, there will be no golden reaction, and if it is too high, the strength will tend to decrease, so the optimal heating temperature is 1400℃ to 1800℃.
発明の効果
以上本発明によれば、通常の焼成用炉を使用し
て、耐食性に優れ、安価な装飾用硬質、黄金色の
セラミツクスを製造することができる。Effects of the Invention As described above, according to the present invention, it is possible to produce decorative hard, golden-colored ceramics that are excellent in corrosion resistance and are inexpensive, using an ordinary firing furnace.
Claims (1)
素（Si3N4）、窒化アルミニウム（AlN）、窒化ホ
ウ素（BN）の１種の粉末、または２種あるいは
３種の混合粉末にて被覆し、窒素（N2）雰囲気
下で加熱する工程を有するセラミツクスの製造方
法。1 A partially stabilized zirconia sintered body is coated with one type of powder, or a mixed powder of two or three of trisilicon tetranitride (Si 3 N 4 ), aluminum nitride (AlN), and boron nitride (BN). , a method for producing ceramics comprising a step of heating in a nitrogen (N 2 ) atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22247786A JPS6374984A (en) | 1986-09-19 | 1986-09-19 | Manufacture of ceramics |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP22247786A JPS6374984A (en) | 1986-09-19 | 1986-09-19 | Manufacture of ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6374984A JPS6374984A (en) | 1988-04-05 |
| JPH0526753B2 true JPH0526753B2 (en) | 1993-04-19 |
Family
ID=16783031
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP22247786A Granted JPS6374984A (en) | 1986-09-19 | 1986-09-19 | Manufacture of ceramics |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6374984A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2620279B2 (en) * | 1988-02-03 | 1997-06-11 | 住友電気工業株式会社 | Method for producing colored ceramic sintered body |
| US5679611A (en) * | 1996-10-09 | 1997-10-21 | Eastman Kodak Company | Ceramic article containing a core comprising tetragonal zirconia and a shell comprising zirconium nitride |
| US5672302A (en) * | 1996-10-09 | 1997-09-30 | Eastman Kodak Company | In-situ surface nitridation of zirconia ceramics |
-
1986
- 1986-09-19 JP JP22247786A patent/JPS6374984A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6374984A (en) | 1988-04-05 |
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