JPH0323505B2 - - Google Patents
Info
- Publication number
- JPH0323505B2 JPH0323505B2 JP58100650A JP10065083A JPH0323505B2 JP H0323505 B2 JPH0323505 B2 JP H0323505B2 JP 58100650 A JP58100650 A JP 58100650A JP 10065083 A JP10065083 A JP 10065083A JP H0323505 B2 JPH0323505 B2 JP H0323505B2
- Authority
- JP
- Japan
- Prior art keywords
- black
- zirconia
- sintered body
- based sintered
- sintering
- 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 68
- 239000003086 colorant Substances 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 238000005245 sintering Methods 0.000 claims description 18
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 12
- 150000002739 metals Chemical class 0.000 claims description 11
- 239000003381 stabilizer Substances 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 7
- 239000006104 solid solution Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 229910021332 silicide Inorganic materials 0.000 claims description 6
- 150000001247 metal acetylides Chemical class 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- -1 iron group metals Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 238000010304 firing Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 9
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 210000004243 sweat Anatomy 0.000 description 5
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- 239000011812 mixed powder Substances 0.000 description 4
- 230000001737 promoting effect Effects 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009760 electrical discharge machining Methods 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000001513 hot isostatic pressing Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- BPJYAXCTOHRFDQ-UHFFFAOYSA-L tetracopper;2,4,6-trioxido-1,3,5,2,4,6-trioxatriarsinane;diacetate Chemical compound [Cu+2].[Cu+2].[Cu+2].[Cu+2].CC([O-])=O.CC([O-])=O.[O-][As]1O[As]([O-])O[As]([O-])O1.[O-][As]1O[As]([O-])O[As]([O-])O1 BPJYAXCTOHRFDQ-UHFFFAOYSA-L 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Description
本発明は、ジルコニアの優れた耐食性、靭性及
び耐熱性を維持しながら黒色系の焼結体にするこ
とによつて時計用外装部品、ネクタイピン、ブロ
ーチ、カウスボタン等の装飾品用材料から釣り具
部品、摺動部品等を含む耐摩耗性材料に適するよ
うにした黒色系ジルコニア基焼結体及びその製造
方法に関する。
従来、装飾品用材料は、耐食性及び耐スクラツ
チ性が要求されることから高級用には主として硬
質合金が使用されている。高級品向けの装飾品用
材料の内、黒色系装飾品用材料には主としてWC
基焼結合金、TiC基焼結合金及びAl2O3−TiC基
焼結体が実用化されている。この内WC基焼結合
金は、比重が大きくて携帯用装飾品としては不向
きであり、WC基焼結合金及びTiC基焼結合金は
くすんだ灰色系の色調であるために市場の要望を
充分に満足していなく、Al2O3−TiC基焼結体は
黒色系の色調であるが鏡面状態での光沢が悪いこ
とと靭性が低いために製品の加工工程等で欠損が
生じるという問題がある。
本発明の黒色系ジルコニア基焼結体は、上述の
ような問題点を解決したもので耐食性、靭性及び
耐熱性に優れたジルコニアに黒色系着色剤を添加
して緻密で光沢及び色調の良好な黒色系焼結体を
提供するところにある。
本発明は、変態によつて体積変化を伴うために
取扱い難い材料とされていたジルコニアにCaO、
MgO及びY2O3等の低原子価酸化物の安定化剤を
含有固溶させることによつて低温でも安定相が存
在するジルコニアを主体にした焼結体である。即
ち、安定化剤を含むジルコニアに黒色系着色剤を
添加して焼結性を考慮すると共に安定化剤を含む
ジルコニア本来の諸特性を低下させない緻密で鏡
面光沢の良好な高硬度高靭性の焼結体であつて、
この黒色系焼結体の成分は、0.05〜50体積％の黒
色系着色剤と残り安定化剤を含むジルコニアと不
可避的不純物とからなる焼結体である。ここで使
用する黒色系着色剤は種々の金属、合金、固溶体
及び化合物があるが緻密で鏡面光沢の良好な高硬
度高靭性の焼結体を得るために高融点金属である
周期律表の4a、5a、6a族金属及び鉄族金属の中
から選択された少なくとも１種以上の金属およ
び／または合金がよく、又は周期律表の4a、5a、
6a族金属の炭化物、硼化物、硅化物及びこれら
の相互固溶体の中から選択された少なくとも１種
以上の化合物がよく、更にこれらの4a、5a、6a
族金属及び鉄族金属の中から選択された１種類以
上の金属および／または合金と4a、5a、6a族金
属の炭化物、硼化物、硅化物及びこれらの相互固
溶体の中から選択された少なくとも１種以上の化
合物とであつてもよい。
本発明の黒色系シルコニア基焼結体は、CaO、
MgO及びY2O3等の安定化剤を含んだジルコニア
と黒色系着色剤とからなる焼結体であつて、この
黒色系着色剤が周期律表の4a、5a、6a族金属及
び鉄族金属から選択された１種以上の金属およ
び／または合金の場合にはジルコニア中の酸素が
介在した固相反応によつて反応焼結が生じて焼結
を促進し緻密で高靭性な黒色系ジルコニア基焼結
体が得られ、このときに鉄族金属が含有している
と一層焼結性の促進効果が強くなる。又、黒色系
着色剤が周期律表の4a、5a、6a族金属の炭化物、
硼化物、硅化物及びこれらの相互固溶体の中から
選択された少なくとも１種以上の化合物である場
合にはジルコニア中の酸素と黒色系着色剤中の非
金属元素が介在した固相反応によつて反応焼結が
生じて焼結を促進し、緻密で高硬度高靭性な黒色
系シルコニア基焼結体が得られる。これらの黒色
着色剤は、特に周期律表の6aの族金属、6aの族
金属を含む合金又は6a族金属の炭化物、硼化物、
硅化物及びこれらを含む固溶体等の化合物の中の
１種以上である場合にはジルコニア中の酸素との
反応がより一層容易になつて低温側で反応が生じ
焼結を促進する傾向にある。これらの黒色系着色
剤に対して体積％で20％以下のカーボンおよび／
または黒鉛を含有させると更に焼結を促進する効
果があると共に黒色系の色調コントロールが容易
となる、又、これらの黒色系着色剤を20体積％以
上と残り安定化剤を含むジルコニアと不可避的不
純物とからなる焼結体は、放電加工が可能な程度
の導電性が生じるので時計用外装部品等の放電加
工が必要になるような複雑な形状用の材料に適し
ている。
本発明の黒色系ジルコニア基焼結体の製造方法
は出発原料として使用する安定化剤を含むジルコ
ニア及び黒色系着色剤は出来るだけ微細な粉末が
望ましく、この安定化剤を含むジルコニア粉末と
黒色系着色剤粉末をウレタン内張りしたシリンダ
ーの中に混在させて、ジルコニア製ボール、アル
ミナ製ボール、ヒニール被覆のスチールボール等
と一緒にアルコール、アセトン、ヘキサン等の溶
媒と共に混合粉砕して混合粉末とする。この混合
粉末を金型モールドにて１〜4ton／cm2の圧力で粉
末圧粉体を直接真空又は不活性ガス中で1500〜
1800℃の温度、１〜５時間の保持時間で焼結する
か又は粉末圧粉体を不活性ガス中で1000℃以下の
温度で予備焼結した後機械加工によつて成形体と
し、この成形体を真空又は不活性ガス中で1500〜
1800℃の温度、１〜５時間の保持時間で焼結する
普通焼結方法で焼結体にすることができる。この
普通焼結方法は、微細な黒色系着色剤が酸化され
易いのとジルコニアが還元雰囲気に弱いために高
真空又は不活性ガス雰囲気中で焼結するが特に焼
結炉の構造等を考慮すると不活性ガス雰囲気が望
ましい。ホツトプレス焼結では混合粉末体を黒鉛
型モールドに充填して、50〜400Kg／cm2の圧力を
付加しながら1400〜1600℃の温度で１〜５時間の
保持時間で焼結する。このときの雰囲気は、試料
である粉末圧粉体が黒鉛型モールドによつて大気
と遮断されるような状態になるために大気中、真
空中又は非酸化性ガス雰囲気中でも良いが黒鉛型
モールドの消耗度合を考慮すると低真空又は不活
性ガス中で焼結するのが望ましい。これらの普通
焼結方法又はホツトプレス焼結方法にて焼結した
焼結体を靭性の向上及び緻密化を目的として1000
〜2000気圧、1500〜1800℃の温度で１〜２時間保
持を行う熱間静水圧加圧法（HIP）も併用するこ
とができる。
次に本発明の黒色系ジルコニア基焼結体の数値
限定した理由について述べる。
黒色系着色剤が0.05体積％未満では本来白色系
に近いジルコニア焼結体が深遠な黒色系に着色し
難く、50体積％を越えて多くなるとジルコニア本
来の諸特性が低下すると共に焼結し難くなるため
に黒色系着色剤は0.05〜50体積％と定めた。
以下に本発明の黒色系ジルコニア基焼結体及び
その製造方法を実施例に従つて具体的に説明す
る。
実施例 １
平均粒度0.2〜0.3μｍで３体積％Y2O3含有の
ZrO2粉末（YSZ）と平均粒度0.5〜1μｍで４体積
％CaO含有のZrO2粉末（CSZ）と平均粒度0.8〜
1.0μｍで4.5体積％MgO含有ZrO2粉末（MSZ）と
平均粒度0.5〜1.5μｍのTi、Zr、Hf、Ta、Nb、
Ｖ、Ｗ、Mo、Cr、Ni、Co粉末を出発原料とし
て所定の割合に配合し、ZrO2系ボール、アルコ
ール溶媒の入つたウレタン内張りのシリンダーに
て粉砕混合した。乾燥後、混合粉末を2t／cm2の加
圧力で成形し、Arガス中又は真空中で1500〜
1800℃の温度で１〜４時間焼結した。各試料の配
合組成、焼結条件を第１表に示した。
The present invention is a method of making zirconia into a black sintered body while maintaining its excellent corrosion resistance, toughness, and heat resistance. The present invention relates to a black zirconia-based sintered body suitable for wear-resistant materials including tool parts, sliding parts, etc., and a method for producing the same. Conventionally, materials for decorative items are required to have corrosion resistance and scratch resistance, so hard alloys have been mainly used for high-grade materials. Among decorative materials for luxury goods, black decorative materials are mainly WC.
A base sintered alloy, a TiC-based sintered alloy, and an Al 2 O 3 -TiC-based sintered body have been put into practical use. Of these, WC-based sintered alloys have a high specific gravity and are unsuitable for use as portable accessories, while WC-based sintered alloys and TiC-based sintered alloys have dull gray tones, so they do not meet market demands. Although the Al 2 O 3 -TiC-based sintered body has a black color, it has poor gloss in a mirror state and low toughness, which causes defects in the product processing process. be. The black zirconia-based sintered body of the present invention solves the above-mentioned problems, and is made by adding a black coloring agent to zirconia, which has excellent corrosion resistance, toughness, and heat resistance. The purpose is to provide a black sintered body. The present invention utilizes CaO,
It is a sintered body mainly made of zirconia, which has a stable phase even at low temperatures due to the solid solution containing stabilizers of low valence oxides such as MgO and Y 2 O 3 . In other words, a black coloring agent is added to zirconia containing a stabilizer to take into consideration sintering properties, and the sintering process is made to be dense, specular, and highly tough, with good sinterability and without degrading the inherent properties of the zirconia containing the stabilizer. It is a unity,
The components of this black sintered body are zirconia containing 0.05 to 50% by volume of a black colorant, the remainder containing a stabilizer, and inevitable impurities. The black coloring agent used here includes various metals, alloys, solid solutions, and compounds, but in order to obtain a high hardness and high toughness sintered body that is dense and has good specular gloss, we use a high melting point metal, 4a of the periodic table. , 5a, 6a group metals and iron group metals and/or alloys, or 4a, 5a,
At least one compound selected from group 6a metal carbides, borides, silicides, and mutual solid solutions thereof is preferable, and furthermore, these 4a, 5a, 6a
One or more metals and/or alloys selected from group metals and iron group metals, and at least one selected from carbides, borides, silicides, and mutual solid solutions of group 4a, 5a, and 6a metals. There may be more than one type of compound. The black zirconia-based sintered body of the present invention includes CaO,
It is a sintered body made of zirconia containing stabilizers such as MgO and Y 2 O 3 and a black colorant, and the black colorant is a metal of groups 4a, 5a, 6a of the periodic table and iron group. In the case of one or more metals and/or alloys selected from metals, reactive sintering occurs due to solid phase reaction mediated by oxygen in zirconia, promoting sintering and producing dense and tough black zirconia. A base sintered body is obtained, and if an iron group metal is contained at this time, the effect of promoting sinterability becomes even stronger. In addition, the black colorant is a carbide of a group 4a, 5a, or 6a metal of the periodic table,
In the case of at least one compound selected from borides, silicides, and mutual solid solutions thereof, the solid phase reaction mediated by oxygen in zirconia and nonmetallic elements in the black colorant Reactive sintering occurs and promotes sintering, resulting in a dense, highly hard, and highly tough black silconia-based sintered body. These black colorants are in particular metals of group 6a of the periodic table, alloys containing metals of group 6a or carbides, borides,
When it is one or more of compounds such as silicides and solid solutions containing these, the reaction with oxygen in zirconia becomes even easier, and the reaction tends to occur at low temperatures, promoting sintering. These black colorants contain less than 20% carbon and/or
Or, if graphite is included, it has the effect of further promoting sintering and makes it easier to control the black color tone.Also, if these black colorants are contained at 20% by volume or more, it is unavoidable that zirconia containing the remaining stabilizer is added. A sintered body made of impurities exhibits conductivity to the extent that electrical discharge machining is possible, so it is suitable for materials with complex shapes that require electrical discharge machining, such as exterior parts for watches. In the method for producing a black zirconia-based sintered body of the present invention, it is desirable that the zirconia containing a stabilizer and the black colorant used as starting materials be powders as fine as possible. Colorant powder is mixed in a cylinder lined with urethane, and mixed and ground with a solvent such as alcohol, acetone, hexane, etc. together with zirconia balls, alumina balls, steel balls coated with nylon, etc. to form a mixed powder. This mixed powder is directly molded into a powder compact at a pressure of 1 to 4 ton/cm 2 in a vacuum or inert gas at a pressure of 1500 to 400 ton/cm2.
Sinter at a temperature of 1800°C for a holding time of 1 to 5 hours, or pre-sinter the powder compact in an inert gas at a temperature of 1000°C or less and then machine it into a compact. Body in vacuum or inert gas for 1500~
It can be made into a sintered body by a normal sintering method in which it is sintered at a temperature of 1800°C for a holding time of 1 to 5 hours. This normal sintering method is sintered in a high vacuum or inert gas atmosphere because the fine black coloring agent is easily oxidized and zirconia is weak in reducing atmosphere, but especially considering the structure of the sintering furnace, etc. An inert gas atmosphere is preferred. In hot press sintering, the mixed powder is filled into a graphite mold and sintered at a temperature of 1400 to 1600° C. for a holding time of 1 to 5 hours while applying a pressure of 50 to 400 kg/cm 2 . The atmosphere at this time may be air, vacuum, or a non-oxidizing gas atmosphere, since the powder green compact that is the sample is isolated from the atmosphere by the graphite mold. Considering the degree of wear and tear, it is desirable to sinter in a low vacuum or in an inert gas. The sintered bodies sintered by these ordinary sintering methods or hot press sintering methods are
Hot isostatic pressing (HIP), which involves holding at ~2,000 atmospheres and a temperature of 1,500 to 1,800°C for 1 to 2 hours, can also be used. Next, the reason for limiting the numerical value of the black zirconia-based sintered body of the present invention will be described. If the black colorant is less than 0.05% by volume, the zirconia sintered body, which is originally close to white, will be difficult to color into a deep black color, and if it exceeds 50% by volume, the original properties of zirconia will deteriorate and it will be difficult to sinter. To achieve this, the black coloring agent was set at 0.05 to 50% by volume. The black zirconia-based sintered body of the present invention and the method for producing the same will be specifically described below with reference to Examples. Example 1 Containing 3% by volume Y 2 O 3 with an average particle size of 0.2 to 0.3 μm
ZrO 2 powder (YSZ) and ZrO 2 powder (CSZ) containing 4% CaO with an average particle size of 0.5-1 μm and an average particle size of 0.8-1 μm
ZrO2 powder (MSZ) containing 4.5 vol% MgO at 1.0 μm and Ti, Zr, Hf, Ta, Nb, with an average particle size of 0.5-1.5 μm,
V, W, Mo, Cr, Ni, and Co powders were mixed as starting materials in a predetermined ratio, and pulverized and mixed in a urethane-lined cylinder containing a ZrO 2 ball and an alcohol solvent. After drying, the mixed powder is molded with a pressure of 2t/ cm2 and heated to 1500~
Sintering was carried out at a temperature of 1800°C for 1 to 4 hours. Table 1 shows the composition and sintering conditions of each sample.
【表】【table】
【表】
実施例 ２
実施例１で使用した各種安定化剤を含むZrO2
粉末と平均粒度0.5〜1.5μｍの4a、5a、6a族金属
の炭化物、硼化物、硅化物の各種粉末を出発原料
として所定の割合に配合し、実施例１と同様の製
造方法で試料を焼結した。各試料の配合組成、焼
結条件を第２表に示した。[Table] Example 2 ZrO 2 containing various stabilizers used in Example 1
Powder and various powders of carbides, borides, and silicides of group 4a, 5a, and 6a metals with an average particle size of 0.5 to 1.5 μm were mixed as starting materials in a predetermined ratio, and a sample was sintered using the same manufacturing method as in Example 1. concluded. The composition and sintering conditions of each sample are shown in Table 2.
【表】
実施例 ３
実施例１の試料No.１、２、３、４、５と実施例
２の試料No.11、12、13、15、17の本発明の焼結体
に従来品のWC基焼結合金(A)、TiC基焼結合金(B)、
Al2O3−TiC基焼結体(C)を比較用に加えて硬さ、
抗折力の機械的性質と放電加工の可否を求め、更
に各試料の一面を鏡面状態に仕上げて色調の観察
と人工汗による耐食試験を行つた。人工汗は、塩
化ナトリウム、硫化ナトリウム、尿素、アンモニ
ア水、乳酸からなるもので、この内乳酸の添加量
を調整してPHの異なる人工汗を作り、このPHの異
なる人工汗による各試料の耐食性試験を行つた。
以上の各試験を第３表に示した。[Table] Example 3 The sintered bodies of the present invention of Samples Nos. 1, 2, 3, 4, and 5 of Example 1 and Samples Nos. 11, 12, 13, 15, and 17 of Example 2 were combined with the conventional products. WC-based sintered alloy (A), TiC-based sintered alloy (B),
In addition to the Al 2 O 3 −TiC-based sintered body (C) for comparison, the hardness,
The mechanical properties of the transverse rupture force and the feasibility of electric discharge machining were determined, and one side of each sample was finished to a mirror finish, color tone was observed, and a corrosion resistance test using artificial sweat was conducted. Artificial sweat consists of sodium chloride, sodium sulfide, urea, aqueous ammonia, and lactic acid. By adjusting the amount of lactic acid added, artificial sweat with different PH is created, and the corrosion resistance of each sample due to this artificial sweat with different PH is evaluated. I conducted a test.
The above tests are shown in Table 3.
【表】
以上の結果から本発明の黒色系ジルコニア基焼
結体は、人工汗による耐食性が優れており、色調
も光沢のある黒色で高硬度高靭性であることから
装飾用材料以外にも耐摩耗性及びジルコニアの低
摩擦係数をいかしたダイス、ノズル、摺動部品等
の耐摩耗用部品としても利用できる産業上利用価
値の高い材料である。[Table] From the above results, the black zirconia-based sintered body of the present invention has excellent corrosion resistance due to artificial sweat, has a glossy black color, and has high hardness and toughness, so it can be used as a material other than decorative materials. It is a material with high industrial value that can be used as wear-resistant parts such as dies, nozzles, and sliding parts, taking advantage of the abrasion resistance and low coefficient of friction of zirconia.
Claims (1)
を含むジルコニアと不可避的不純物とからなるこ
とを特徴とする黒色系ジルコニア基焼結体。 ２ 上記黒色系着色剤が周期律表の4a、5a、6a
族金属及び鉄族金属の中から選択された少なくと
も１種以上の金属および／または合金であること
を特徴とする特許請求の範囲第１項記載の黒色系
ジルコニア基焼結体。 ３ 上記黒色系着色剤が周期律表の4a、5a、6a
族金属の炭化物、硼化物、硅化物及びこれらの相
互固溶体の中から選択された少なくとも１種以上
の化合物であることを特徴とする特許請求の範囲
第１項及び第２項記載の黒色系ジルコニア基焼結
体。 ４ 上記黒色系着色剤に対して20％以下のカーボ
ンおよび／または黒鉛を含有していることを特徴
とする特許請求の範囲第１項、第２項及び第３項
記載の黒色系ジルコニア基焼結体。 ５ 0.05〜50体積％黒色系着色剤粉末と安定化剤
を含むジルコニア粉末との混合物を真空又は不活
性ガス雰囲気中で1500℃〜1800℃に昇温して焼結
することを特徴とする黒色系ジルコニア基焼結体
の製造方法。[Scope of Claims] 1. A black zirconia-based sintered body comprising zirconia containing 0.05 to 50% by volume of a black colorant and a remaining stabilizer, and unavoidable impurities. 2 The above black colorants are 4a, 5a, and 6a of the periodic table.
The black zirconia-based sintered body according to claim 1, characterized in that the black zirconia-based sintered body is at least one metal and/or alloy selected from group metals and iron group metals. 3 The above black colorants are 4a, 5a, and 6a of the periodic table.
The black zirconia according to claims 1 and 2, which is a compound of at least one selected from group metal carbides, borides, silicides, and mutual solid solutions thereof. Base sintered body. 4. The black zirconia-based firing according to claims 1, 2, and 3, which contains 20% or less of carbon and/or graphite based on the black colorant. Body. 5. Black color characterized by sintering a mixture of 0.05 to 50 volume % black colorant powder and zirconia powder containing a stabilizer by raising the temperature to 1500°C to 1800°C in a vacuum or inert gas atmosphere. A method for producing a zirconia-based sintered body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58100650A JPS59227770A (en) | 1983-06-06 | 1983-06-06 | Black zirconia base sintered body and manufacture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58100650A JPS59227770A (en) | 1983-06-06 | 1983-06-06 | Black zirconia base sintered body and manufacture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59227770A JPS59227770A (en) | 1984-12-21 |
| JPH0323505B2 true JPH0323505B2 (en) | 1991-03-29 |
Family
ID=14279695
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58100650A Granted JPS59227770A (en) | 1983-06-06 | 1983-06-06 | Black zirconia base sintered body and manufacture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59227770A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6090872A (en) * | 1983-10-25 | 1985-05-22 | 京セラ株式会社 | Zirconia black color dressing member |
| JPS6256362A (en) * | 1985-09-05 | 1987-03-12 | 日本タングステン株式会社 | Zirconia sintered body |
| JPH0434541Y2 (en) * | 1986-03-03 | 1992-08-17 | ||
| US5118457A (en) * | 1988-04-14 | 1992-06-02 | Kyocera Corporation | Colored zirconia ceramics and process for preparation thereof |
| US5059562A (en) * | 1988-04-14 | 1991-10-22 | Kyocera Corporation | Colored zirconia ceramics and process for preparation thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59105055A (en) * | 1982-12-07 | 1984-06-18 | Kyocera Corp | Zirconia coloring material |
-
1983
- 1983-06-06 JP JP58100650A patent/JPS59227770A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59105055A (en) * | 1982-12-07 | 1984-06-18 | Kyocera Corp | Zirconia coloring material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59227770A (en) | 1984-12-21 |
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