JPS59227770A - Black zirconia base sintered body and manufacture - Google Patents
Black zirconia base sintered body and manufactureInfo
- Publication number
- JPS59227770A JPS59227770A JP58100650A JP10065083A JPS59227770A JP S59227770 A JPS59227770 A JP S59227770A JP 58100650 A JP58100650 A JP 58100650A JP 10065083 A JP10065083 A JP 10065083A JP S59227770 A JPS59227770 A JP S59227770A
- Authority
- JP
- Japan
- Prior art keywords
- black
- zirconia
- sintered body
- based sintered
- metals
- 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.)
- Granted
Links
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】
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って時計
用外装部品、ネクタイピン、ブロー４、カフスボタン等
の装飾品用材料から釣り異部品、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。DETAILED DESCRIPTION OF THE INVENTION The present invention provides a black sintered body that maintains the excellent corrosion resistance, toughness, and heat resistance of zirconia, thereby making it possible to produce exterior parts for watches, tie pins, blow 4s, cufflinks, etc. The present invention relates to a black zirconia-based sintered body suitable for wear-resistant materials including ornamental materials, fishing parts, sliding parts, etc., and a method for producing the same.
従来、装飾品用材料は、耐食性及び耐スクラッチ性が要
求されることから高級品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ＡｚｚＱａ −ＴｉＣ基焼結体が実用化されて
いる。この内ｗｃ基焼結合金は、比重が大ぎくて携帯用
装飾品としては不向きであり、Ｗｃ基焼結合金及びＴｉ
ｃ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、Ａｚ２０３−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。Conventionally, materials for decorative items are required to have corrosion resistance and scratch resistance, so hard alloys have been mainly used for high-grade items. Among decorative materials for luxury goods, WC-based sintered alloys, Tic-based sintered alloys, and AzzQa-TiC-based sintered bodies are mainly used as black decorative materials. Of these, Wc-based sintered alloys have too large a specific gravity and are unsuitable for use as portable accessories; Wc-based sintered alloys and Ti
The C-based sintered alloy has a dull gray color and does not fully satisfy the market's needs, and the Az203-Tic-based sintered body has a black color but has poor gloss in a mirror state. Due to its low toughness, there is a problem that defects occur during the processing process of products.
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。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.
本発明は、変態によっ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。The present invention combines CaO with zirconia, which has been considered to be a difficult material to handle due to volume changes caused by transformation.
Ｍｏ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っ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
であって、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。It is a sintered body mainly made of zirconia, which has a stable phase even at low temperatures by containing a stabilizer of low valence oxides such as Mo and Y2O3. 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. The black sintered body has a component of 0.05 to 50
It is a sintered body consisting of zirconia containing a black coloring agent in a volume percent and a remaining stabilizer, and inevitable impurities. The black coloring agent used here includes various metals, alloys, solid solutions, and compounds, but it is dense and has a high specular gloss.
“In order to obtain a sintered body with high hardness and high toughness, it is recommended to use at least one metal and/or alloy selected from metals of groups 4a, 5a, 6a of the periodic table and iron group metals, which are high melting point metals. , or 4a of the periodic table.
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。Preferably, at least one compound selected from carbides, borides, silicides, and mutual solid solutions of group 5a and 6a metals, and furthermore, these 4a.
５ａ 、６ａ族金属及び鉄族金属の中から選択された１
種以上の金属および／または合金と４ａ。1 selected from group 5a, group 6a metals and iron group metals
4a with one or more metals and/or alloys;
５ａ 、６ａ族金属の灰化物、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
の化合物とであってもよい。It may also be at least one compound selected from ashes, borides, silicides, and mutual solid solutions of metals of Groups 5a and 6a.
本発明の黒色系ジルコニア基焼結抹は、ＣａＯ。The black zirconia-based sintered powder of the present invention is 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って、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（よジルコニア中の酸素が介在した固相反応に
よっ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っ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ジルコニア基焼結
体が得られる。これらの黒色系着色剤は、特に周期律表
の６ａ族金属、６ａ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っ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２ｏ％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。A sintered body made of zirconia containing a stabilizer such as MgO and Y2O3 and a black colorant, the black colorant being selected from group 4a, 5a, 6a metals and iron group metals of the periodic table. In the case of one or more metals and/or alloys, reaction sintering occurs due to a solid phase reaction mediated by oxygen in zirconia, promoting sintering, and creating a dense and tough black zirconia-based sintered body. is obtained, and at this time, if an iron group metal is contained, the effect of promoting sinterability will be even stronger.Also, the black colorant may be a carbide or boride of a group 4a, 5a, or 6a metal of the periodic table. , silica, and a mutual solid solution of these, reaction sintering occurs through a solid phase reaction mediated by oxygen in zirconia and nonmetallic elements in the black colorant. This produces a black zirconia-based sintered body that is dense, highly hard, and has high toughness. When the compound is one or more of the group 6a metal carbides, borides, silicides, and solid solutions containing these, the reaction with oxygen in zirconia becomes even easier, and the reaction occurs at low temperatures. It tends to promote sintering.If carbon and/or graphite is added to these black colorants in an amount of 20% or less by volume, it has the effect of further promoting sintering and also controls the black color tone. In addition, sintered bodies made of 20% by volume or more of these black colorants, zirconia containing residual stabilizers, and unavoidable impurities are electrically conductive to the extent that electrical discharge machining is possible, making them suitable for use in watches. Suitable for materials with complex shapes that require electrical discharge machining, such as exterior parts.
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、ビ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／ｃｆｆｌの圧力で粉末
圧粉体を直接真空又は不活性ガス中で１５００〜１８０
０℃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 ’Ｃ以下の温度で
予備焼結した後機械加工によって成形体とし、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。ホットプレス焼結では混合粉末を黒鉛型モ
ールドに充填して、５０〜４００ｋｇ／ｃｎｔ の圧力
を付加しなから１４００−１６００’Ｃの温度で１〜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ットプ
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、１５００〜１
８００℃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。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 pulverized with a solvent such as alcohol, acetone, hexane, etc. together with zirconia balls, alumina balls, vinyl-coated steel balls, etc. to form a mixed powder. This mixed powder is directly molded into a powder compact at a pressure of 1 to 4 tons/cffl in a vacuum or inert gas at a pressure of 1500 to 180 ton/cffl.
Either sintering at a temperature of 0°C for a holding time of 1 to 5 hours, or pre-sintering the powder compact in an inert gas at a temperature of 1000'C or less and then machining it into a compact. It can be made into a sintered body by a normal sintering method in which it is sintered in vacuum or inert gas at a temperature of 1500 to 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 a pressure of 50 to 400 kg/cnt is applied, and then the mold is heated at a temperature of 1400 to 1600'C to create a state where it is isolated from the atmosphere. Sintering may be performed in air, vacuum, or a non-oxidizing gas atmosphere, but considering the degree of wear and tear of the graphite mold, it is preferable to sinter in a low vacuum or inert gas. The sintered bodies sintered by these normal sintering methods or hot press sintering methods are heated at 1000 to 2000 atmospheres and 1500 to 1
Hot isostatic pressing (HIP), which involves holding at a temperature of 800° C. for 1 to 2 hours, can also be used.
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。Next, the reason for limiting the numerical value of the black zirconia-based sintered body of the present invention will be described.
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１１＜、５
０体猿％を超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。If the black colorant is less than 0.05% by volume, the zirconia sintered body, which is originally close to white, will be colored deep black.
If the amount exceeds 0%, the inherent properties of zirconia will deteriorate and it will become difficult to sinter, so the black colorant should be used at 0%.
．． 05-50% by volume.
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
方法を実施例に従って具体的に説明する。The black zirconia-based sintered body of the present invention and the method for producing the same will be specifically explained below according to Examples.
実施例１
４．５体積％ＭｇＯ含有ＺｒＯ２粉末（ＭＳＺ）と平均
粒度０．５〜１．５ μｍのＴｉ 、Ｚｒ、Ｈｆ、Ｔａ
、Ｎｂ。Example 1 ZrO2 powder (MSZ) containing 4.5% MgO by volume and Ti, Zr, Hf, Ta with an average particle size of 0.5 to 1.5 μm
, 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
ル溶媒の入っ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／ｍ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ｍ戒、焼結条件を
第１表に示した。V, W, Mo, Cr, Ni, and Co powders were blended in a predetermined ratio as starting materials and pulverized and mixed in a ZrO2 ball and a urethane-lined cylinder containing an alcohol solvent. After drying, the mixed powder was molded under a pressure of 2 t/m and sintered at a temperature of 1500 to 1800° C. for 1 to 4 hours in Ar gas or vacuum. Table 1 shows the formulation and sintering conditions for each sample.
以下余白
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０．５〜１．５ ｔｔ ｍの４ａ 、 ５ａ
、 ６ａ族金属の炭化物、硼化物、硫化物の各種粉末を
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。Below are blank spaces Example 2 ZrO2 powder containing various stabilizers used in Example 1 and 4a and 5a with an average particle size of 0.5 to 1.5 tt m
, various powders of carbides, borides, and sulfides of Group 6a metals were blended in predetermined proportions as starting materials, and samples were sintered using the same manufacturing method as in Example 1. Table 2 shows the composition and sintering conditions of each sample.
以下余白
実施例３
実施例１の試料Ｎｃｉ、１，２，３，４．５と実施例２
の試料風１１，１２，１３，１５．１７の本発明の焼結
体に従来品のＷＣ基焼結合金ｆｉ、ＴｉＣ基焼結合金０
、Ａｚ２０３−ＴｉＣ基焼結体すな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
試料の一面を鐘面状態に仕上げて色調の観察と人工汗に
よる耐食試験を行った。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
試験を行った。以上の各結果を第３表に示した。Below are blank spaces Example 3 Samples Nci of Example 1, 1, 2, 3, 4.5 and Example 2
Sample winds 11, 12, 13, 15.
In addition to the Az203-TiC-based sintered body for comparison, the mechanical properties of hardness, transverse rupture strength, and whether or not electrical discharge machining is possible were determined, and one side of each sample was finished in a bell-shaped state to observe the color tone and perform artificial A corrosion resistance test using 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 values is created. The test was conducted. The above results are shown in Table 3.
以下余白
以上の結果から本発明の黒色系ジルコニア基焼結体は、
人工汗台こ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。From the results shown below, the black zirconia-based sintered body of the present invention is
Artificial sweat stand has excellent corrosion resistance, glossy black color, high hardness and high toughness, so it can be used not only as a decorative material but also for dies, nozzles, and slides that take advantage of the abrasion resistance and low friction coefficient of zirconia. It is a material with high industrial value and can be used as wear-resistant parts.
Claims (5)
定化剤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。(1) A black zirconia-based sintered body comprising zirconia containing 0.05 to 50% by volume of a black colorant and the remainder of a stabilizer, and unavoidable impurities.
ａ 。 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。(2) The above black colorant is 4a and 5 of the periodic table.
a. The black zirconia-based sintered body according to claim 1, characterized in that it is at least one metal and/or alloy selected from group 6a metals and iron group metals.
。 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。(3) The above black coloring agent is 4a and 5a of the periodic table.
. Claims 1 and 2 are characterized in that they are at least one compound selected from group 6a metal carbides, borides, silicides, and mutual solid solutions thereof.
The black zirconia-based sintered body described in Section 1.
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。(4) The black zirconia according to claims 1, 2, and 3, which contains 20% or less of carbon and/or graphite based on the black colorant. Base sintered body.
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ｌ５００℃〜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。(5) Sintering a mixture of 0.05 to 50% by volume black colorant powder and zirconia powder containing a stabilizer by raising the temperature to 1500°C to 1800°C in a vacuum or an inert gas atmosphere. A method for producing a characterized black 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 true JPS59227770A (en) | 1984-12-21 |
| JPH0323505B2 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) |
Cited By (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 |
| EP0259498A1 (en) * | 1986-03-03 | 1988-03-16 | Sigmax Ltd. | Bar code label |
| US5059562A (en) * | 1988-04-14 | 1991-10-22 | Kyocera Corporation | Colored zirconia ceramics and process for preparation thereof |
| US5118457A (en) * | 1988-04-14 | 1992-06-02 | 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 |
Cited By (6)
| 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 |
| JPH0566335B2 (en) * | 1985-09-05 | 1993-09-21 | Nippon Tungsten | |
| EP0259498A1 (en) * | 1986-03-03 | 1988-03-16 | Sigmax Ltd. | Bar code label |
| US5059562A (en) * | 1988-04-14 | 1991-10-22 | Kyocera Corporation | Colored zirconia ceramics and process for preparation thereof |
| US5118457A (en) * | 1988-04-14 | 1992-06-02 | Kyocera Corporation | Colored zirconia ceramics and process for preparation thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0323505B2 (en) | 1991-03-29 |
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