JPH0157074B2 - - Google Patents
Info
- Publication number
- JPH0157074B2 JPH0157074B2 JP57231174A JP23117482A JPH0157074B2 JP H0157074 B2 JPH0157074 B2 JP H0157074B2 JP 57231174 A JP57231174 A JP 57231174A JP 23117482 A JP23117482 A JP 23117482A JP H0157074 B2 JPH0157074 B2 JP H0157074B2
- Authority
- JP
- Japan
- Prior art keywords
- zirconia
- black
- toughness
- firing
- decorative member
- 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
Links
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 90
- 238000010304 firing Methods 0.000 claims description 19
- 239000003381 stabilizer Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 230000001590 oxidative effect Effects 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 4
- 239000000049 pigment Substances 0.000 description 17
- 239000002932 luster Substances 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910002077 partially stabilized zirconia Inorganic materials 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 238000000465 moulding Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 4
- 229910002076 stabilized zirconia Inorganic materials 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229910026551 ZrC Inorganic materials 0.000 description 2
- OTCHGXYCWNXDOA-UHFFFAOYSA-N [C].[Zr] Chemical compound [C].[Zr] OTCHGXYCWNXDOA-UHFFFAOYSA-N 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000004040 coloring Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
Description
【発明の詳細な説明】
本発明はジルコニア素地に顔料を含有させない
で黒色化したジルコニア系黒色装飾部材の製造方
法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a black zirconia decorative member in which a zirconia base material is blackened without containing a pigment.
従来、アルミナセラミツクスに顔料を含有させ
た黒色装飾部材が利用され、例えば時計ケースや
文字盤などの時計関連部品等に賞用されていた
が、アルミナ系装飾部材では、焼結後の鏡面研摩
に伴い、微細な結晶が欠落するという難点があつ
た。加えて、結晶及び粒界の全般にわたり、多く
の空隙があるため、鏡面研摩をしても滑らかで深
みのある艶を有した鏡面が現出しないという装飾
部材として好ましくない欠点があつた。 Conventionally, black decorative parts made of alumina ceramics containing pigments have been used for watch-related parts such as watch cases and dials. As a result, there was a problem that fine crystals were missing. In addition, since there are many voids throughout the crystals and grain boundaries, a smooth, deep, glossy mirror surface cannot be obtained even after mirror polishing, which is undesirable as a decorative member.
しかも、このアルミナ系装飾部材は強度に優れ
ているものの、不注意に落としたりして対物衝撃
が加わると、割れ易いという欠点も有し、言わ
ば、靭性に劣つていた。 Moreover, although this alumina-based decorative member has excellent strength, it also has the disadvantage that it is easily broken if it is accidentally dropped and subjected to an object impact, and thus has poor toughness.
上記の問題に対し、本発明者は先に、ジルコニ
ア素地に顔料を含有させたジルコニア系装飾部材
を提案した。 In order to solve the above problem, the present inventor previously proposed a zirconia-based decorative member in which a pigment is contained in a zirconia base.
即ち、ジルコニア素地に顔料を含有させると、
顔料成分に応じ、アルミナ系装飾部材と同傾向の
呈色となり、且つ、ジルコニア系装飾部材はアル
ミナ系装飾部材に比べ、鏡面研摩後、滑らかで深
みのある艶を有した鏡面となり、好適な有色装飾
部材になつたのに加え、特に部分安定化ジルコニ
ア系装飾部材については曲げ強度及び靭性特性が
飛躍的に向上したため、強度の向上とともに割れ
易いなどの欠点が解消され、極めて信頼性の高い
装飾部材となつた。 That is, when a pigment is contained in a zirconia base,
Depending on the pigment component, the coloration tends to be the same as that of alumina-based decorative members, and compared to alumina-based decorative members, zirconia-based decorative members have a mirror surface with a smoother and deeper luster after mirror polishing, making them suitable for coloring. In addition to being used as a decorative component, the bending strength and toughness of partially stabilized zirconia decorative components have been dramatically improved, which has improved strength and eliminated shortcomings such as easy cracking, making it an extremely reliable decorative component. It became a component.
しかしながら、黒色装飾部材に関してジルコニ
アを主成分とした母材にCr、Co、Mn、及びNi
の酸化物から成る黒色顔料を含有させると、強度
及び靭性特性が劣化するという難点があり、しか
も、安価な装飾部材を提供するためにも顔料成分
を含まない黒色装飾部材とするのが望ましい。 However, for black decorative members, Cr, Co, Mn, and Ni are added to the base material mainly composed of zirconia.
If black pigments made of oxides of black pigments are contained, there is a problem that the strength and toughness characteristics deteriorate.Moreover, in order to provide inexpensive decorative members, it is desirable to use black decorative members that do not contain pigment components.
本発明者は上述の点に鑑み、鋭意研究を重ねた
結果、ジルコニアを鏡面研摩すると滑らかで深み
のある艶を有した鏡面になり、且つ、強度及び靭
性特性が向上して好適な装飾部材となつたのに加
え、顔料を含まないジルコニア母材を非酸化性雰
囲気、好ましくは還元性雰囲気で焼成することに
より、ジルコニアの還元が進行して黒色が発現さ
れ、その結果、先の顔料を含むジルコニア系黒色
装飾部材に匹敵する程、優れた黒色の鏡面を呈
し、且つ、強度及び靭性特性が一段と向上するこ
とを見い出すに至つた。 In view of the above points, the present inventor has conducted intensive research and found that mirror polishing of zirconia produces a mirror surface with a smooth, deep luster, and improves strength and toughness, making it suitable for decorative members. In addition to NATSUTANO, by firing the zirconia base material that does not contain pigment in a non-oxidizing atmosphere, preferably a reducing atmosphere, the reduction of zirconia progresses and a black color is developed, and as a result, the zirconia matrix containing the pigment described above is developed. It has been discovered that it exhibits an excellent black mirror surface comparable to that of zirconia-based black decorative members, and further improves strength and toughness properties.
本発明者は上記知見に基づき、焼結後、鏡面研
摩により、滑らかで深みのある艶を有した鏡面を
現出させ、外部応力が加わつても破壊しない高靭
性のジルコニア系黒色装飾部材を提供するに際
し、黒色顔料を使用しないで焼成条件を限定する
ことで黒色装飾部材が得られ、その結果、安価
で、且つ、強度及び靭性特性の向上したジルコニ
ア系黒色装飾部材の製造方法を提供することを目
的とするものである。 Based on the above findings, the present inventors provide a highly tough zirconia-based black decorative member that exhibits a smooth, deep, glossy mirror surface by mirror polishing after sintering, and does not break even when external stress is applied. To provide a method for manufacturing a zirconia-based black decorative member which is inexpensive and has improved strength and toughness characteristics, whereby the black decorative member is obtained by limiting firing conditions without using a black pigment. The purpose is to
本発明のジルコニア系黒色装飾部材の製造方法
は、ジルコニアを主成分とした母材と、該母材中
に含有されたY2O3、MgO、CeO2及びCaOから選
ばれた安定化剤の少なくとも一種とから成る未焼
結成形体を1400乃至1600℃の温度で且つ非酸化性
雰囲気中で成形体が黒色になるように焼成し、次
いで得られる焼結体を鏡面研摩することを特徴と
するものである。 The method for producing a zirconia-based black decorative member of the present invention includes a base material mainly composed of zirconia, and a stabilizer selected from Y 2 O 3 , MgO, CeO 2 and CaO contained in the base material. A green compact consisting of at least one of the following is fired at a temperature of 1400 to 1600°C in a non-oxidizing atmosphere so that the compact becomes black, and the resulting sintered body is then mirror-polished. It is something.
先ずジルコニア焼結体はアルミナ焼結体に比し
て空隙（Void）の含有率が少なく、従つてジル
コニア焼結体を黒色装飾部材とすることにより、
滑らかで深みのある艶をもつた鏡面を現出させる
ことが可能となる。 First, the zirconia sintered body has a lower void content than the alumina sintered body, so by using the zirconia sintered body as a black decorative member,
It is possible to create a mirror surface with a smooth, deep luster.
純粋なジルコニアは安定であるが、1000℃前後
で相転移を起こし、体積変化に伴い、焼結体を破
壊に至らしめる。したがつて、Y2O3、MgO、
CeO、CaO等の安定化剤を加え、その添加量に応
じて部分安定化ジルコニアもしくは安定化ジルコ
ニアが作られている。とりわけ、部分安定化ジル
コニアでマルテンサイト変態により、靭性特性が
著しく向上し、またアルミナセラミツクスと比
べ、一段と抗折強度が改善される。 Although pure zirconia is stable, it undergoes a phase transition at around 1000°C, which causes the sintered body to break due to the change in volume. Therefore, Y 2 O 3 , MgO,
Stabilizers such as CeO and CaO are added to produce partially stabilized zirconia or stabilized zirconia depending on the amount added. In particular, the martensitic transformation of partially stabilized zirconia significantly improves toughness, and further improves flexural strength compared to alumina ceramics.
ジルコニア焼結体を黒色に着色するのに普通に
考えられる方法は、ジルコニアを主成分とした母
材にCr、Co、Mn及びNiの酸化物から成る黒色
顔料を含有させる方法があるが、この場合には強
度及び靭性特性が劣化するという難点がある。こ
れに対して本発明においてはジルコニア成形体の
焼結時に、焼結体自体の中に黒色成分を形成させ
ることにより、このような強度や靭性の劣化を防
止しつつ、しかも黒色の鏡面の形成が可能となる
ものである。 A commonly thought method for coloring a zirconia sintered body black is to add a black pigment consisting of oxides of Cr, Co, Mn and Ni to a base material mainly composed of zirconia. In some cases, there is a disadvantage that the strength and toughness properties deteriorate. In contrast, in the present invention, by forming a black component in the sintered body itself during sintering of the zirconia molded body, such deterioration of strength and toughness can be prevented, and a black mirror surface can be formed. is possible.
Y2O3、MgO、CeO2、CaO等の安定化剤は、一
般的に言つてジルコニア当り３乃至55モル％の量
で且つジルコニアを部分安定化乃至安定化させる
に十分な量で使用する。具体的な使用量は安定化
剤の種類によつても相違するが、例えば次のよう
なものである。 Stabilizers such as Y 2 O 3 , MgO, CeO 2 , CaO, etc. are generally used in an amount of 3 to 55 mol % based on zirconia, and in an amount sufficient to partially stabilize or stabilize zirconia. . Although the specific amount used varies depending on the type of stabilizer, for example, it is as follows.
ジルコニアに対しY2O3の成分比が3mol％以上
9mol％未満の範囲であれば部分安定化ジルコニ
アとなり、９乃至55mol％の範囲で安定化ジルコ
ニアとなる。 The component ratio of Y 2 O 3 to zirconia is 3 mol% or more
If the content is less than 9 mol%, it will be partially stabilized zirconia, and if it is in the range of 9 to 55 mol%, it will be stabilized zirconia.
また、ジルコニアに対しCaOの成分比が８乃至
12mol％の範囲であれば好ましい部分安定化ジル
コニアとなり、16乃至29mol％の範囲で安定化ジ
ルコニアとなる。ジルコニアに対しMgOの成分
比が16乃至26mol％の範囲であれば部分安定化ジ
ルコニアとなる。 In addition, the component ratio of CaO to zirconia is 8 to 8.
Partially stabilized zirconia is preferable when the content is in the range of 12 mol%, and stabilized zirconia is obtained when the content is in the range of 16 to 29 mol%. If the component ratio of MgO to zirconia is in the range of 16 to 26 mol%, partially stabilized zirconia will be obtained.
ジルコニア粉末及び、安定化剤の粒径について
は特に制約はないが、通常約2.0μm以下、好まし
くは1.0μm以下がよい。 There are no particular restrictions on the particle size of the zirconia powder and the stabilizer, but it is usually about 2.0 μm or less, preferably 1.0 μm or less.
ジルコニアと安定化剤との組合せに加えて、本
発明の効果を損わない範囲でシリカ、アルミナ、
チタニア等の焼結促進剤等を配合し得る。 In addition to the combination of zirconia and a stabilizer, silica, alumina,
A sintering accelerator such as titania may be added.
本発明によれば、上述した粉末を均密に混合
し、この混合粉末をそれ自体公知の加圧成形手段
で成形する。この成形に際して、ワツクス類等の
バインダーを用いることもできる。成形時の圧力
は、焼結成形体中のVoidが可及的に小さくなる
ように設定する。 According to the present invention, the above-mentioned powders are mixed homogeneously, and this mixed powder is molded by a pressure molding means known per se. In this molding, a binder such as wax can also be used. The pressure during molding is set so that voids in the sintered compact are as small as possible.
この成形体を、1400乃至1600℃の温度で且つ非
酸化性雰囲気中で成形体が黒色となるように焼成
する。非酸化性雰囲気での焼成としては、真空中
での焼成、窒素、アルゴン等の不活性ガス雰囲気
での焼成、更に水素や炭素などの還元性雰囲気焼
成、最も好適には炭素含有雰囲気での焼成を挙げ
ることができる。 This molded body is fired at a temperature of 1400 to 1600° C. in a non-oxidizing atmosphere so that the molded body becomes black. Firing in a non-oxidizing atmosphere includes firing in a vacuum, firing in an inert gas atmosphere such as nitrogen or argon, further firing in a reducing atmosphere such as hydrogen or carbon, and most preferably firing in a carbon-containing atmosphere. can be mentioned.
この焼成により、焼成条件に応じて、ジルコニ
アの還元生成物、炭化ジルコニウム或いは炭素の
少なくとも１種から成る黒色成分が焼結成形体中
に生成し、これにより黒色で、しかも深みのある
艶をもつた鏡面の形成が可能となる。一般に真空
中焼成や不活性ガス中焼成では、鏡面の黒色の程
度が低く、炭素含有雰囲気での焼成では黒色の程
度が高い。これは炭素含有雰囲気での焼成では、
ジルコニア還元生成物が増大し、または、炭素の
成形体への侵入によつて炭化ジルコニウム或いは
炭素の黒色成分の含有量が増大するためであろ
う。 Through this firing, a black component consisting of at least one of zirconia reduction products, zirconium carbide, or carbon is generated in the sintered compact depending on the firing conditions, which gives it a black color and a deep luster. A mirror surface can be formed. Generally, when fired in a vacuum or in an inert gas, the blackness of the mirror surface is low, and when fired in a carbon-containing atmosphere, the blackness is high. This is due to firing in a carbon-containing atmosphere.
This may be due to an increase in the zirconia reduction product or an increase in the content of the black component of zirconium carbide or carbon due to the intrusion of carbon into the compact.
この焼成温度として1400〜1600℃がよい。1400
℃以下であれば焼結せず、1600℃以上あれば黒色
化しても強度及び靭性特性が劣り、特に装飾部材
に不向となり、好ましくは1450〜1550℃の範囲が
よい。 The firing temperature is preferably 1400 to 1600°C. 1400
If it is below 1,600°C, it will not sinter, and if it is above 1,600°C, even if it turns black, the strength and toughness properties will be poor, making it particularly unsuitable for decorative members.The temperature is preferably in the range of 1,450 to 1,550°C.
本発明の好適態様においては、非酸化性の焼成
雰囲気中に、カーボンブラツクの如き炭素を投入
して、ジルコニア成形体の焼結に伴なつて、炭素
を焼結体中に侵入させるようにする。 In a preferred embodiment of the present invention, carbon such as carbon black is introduced into the non-oxidizing firing atmosphere so that the carbon penetrates into the sintered body as the zirconia molded body is sintered. .
焼成時間はジルコニア成形体の焼結と黒色化と
が十分に行われるようなものであり、一般に30分
乃至５時間が適当であり、更に焼成後、50乃至
500℃／時間の降温速度で冷却していくのが望ま
しい。 The firing time is such that the zirconia molded body is sufficiently sintered and blackened, and generally 30 minutes to 5 hours is appropriate, and after firing, 50 minutes to 5 hours is appropriate.
It is desirable to cool down at a rate of 500°C/hour.
得られるジルコニア焼結体を鏡面研摩して、時
計ケース、文字盤等の黒色装飾部品とする。 The resulting zirconia sintered body is mirror-polished to produce black decorative parts such as watch cases and dials.
次に本発明につき、部分安定化ジルコニアの実
施例により詳細に説明する。 Next, the present invention will be explained in detail using examples of partially stabilized zirconia.
実施例 １
高純度のジルコニア粉末100重量部に対し、安
定化剤Y2O3を5.7重量部を加え、更に水100重量
部を加えて振動ミルにて３日間粉砕し、乾燥し
た。これを120メツシユに通し、パラフインワツ
クスを添加し、更に80メツシユに通した。この混
合物を成形圧1ton／cm2で５×５×50mmの形状に成
形し、脱バインダ後、焼成温度1500℃、２時間で
真空焼成し、次いで、200℃／時間の降温速度で
冷却した。Example 1 To 100 parts by weight of high-purity zirconia powder, 5.7 parts by weight of the stabilizer Y 2 O 3 was added, and further 100 parts by weight of water were added, and the mixture was ground in a vibration mill for 3 days and dried. This was passed through a 120 mesh, paraffin wax was added, and further passed through an 80 mesh. This mixture was molded into a shape of 5 x 5 x 50 mm at a molding pressure of 1 ton/cm 2 , and after removing the binder, it was vacuum fired at a firing temperature of 1500°C for 2 hours, and then cooled at a cooling rate of 200°C/hour.
かくして得られた焼結体を鏡面研摩したとこ
ろ、いずれもアルミナ系黒色部材に比べ容易に研
摩が出来、この鏡面の性状を確かめたところ、滑
らかで深みのある艶を有した鏡面となり、好適な
装飾部材となることが判つた。 When the sintered bodies thus obtained were mirror-polished, they were all easier to polish than alumina-based black materials, and when the properties of the mirror surfaces were checked, they were smooth and had a deep luster, making them ideal. It was found that it can be used as a decorative member.
次に、これらの焼結体の抗折強度及び靭性を測
定した。 Next, the bending strength and toughness of these sintered bodies were measured.
抗折強度の測定はJIS R1601の３点曲げ試験法
に、靭性の測定は焼結体がマイクロクラツクの成
長により破壊する際の臨界応力拡大係数が焼結体
の靭性特性としてS.E.N.B（Single Edge
Notched Beam）法に、それぞれ従つた。その
結果、曲げ強度は100Kg／mm2、靭性は12MN／
m3/2となり、部分安定化ジルコニアの好適な特性
値が得られた。 The bending strength is measured using the JIS R1601 three-point bending test method, and the toughness is measured using the SENB (Single Edge
Notched Beam) method. As a result, the bending strength was 100Kg/mm 2 and the toughness was 12MN/
m 3/2 , and suitable characteristic values for partially stabilized zirconia were obtained.
実施例 ２
実施例１と同じ製作条件でH2もしくは炭素含
有の還元性雰囲気で焼成した場合、実施例１と同
様に滑らかで深みのある艶を有した鏡面となつた
ばかりか、深い黒光りを有するようになり、実施
例１に比べ、黒色度は一段と増大した。Example 2 When fired in a reducing atmosphere containing H 2 or carbon under the same manufacturing conditions as Example 1, it not only became a mirror surface with a smooth and deep luster as in Example 1, but also had a deep black luster. As a result, the degree of blackness was further increased compared to Example 1.
また、曲げ強度及び靭性特性はそれぞれ100
Kg／mm2及び12MN／m3/2となり、何ら特性の劣化
は認められなかつた。 In addition, the bending strength and toughness properties are each 100
Kg/mm 2 and 12 MN/m 3/2 , and no deterioration of properties was observed.
次に、ジルコニア粉末に安定化剤と共に、周知
の黒色顔料を含有させ焼結した。ジルコニア系黒
色装飾部材を比較例として述べる。 Next, a well-known black pigment was added to the zirconia powder along with a stabilizer, and the powder was sintered. A zirconia-based black decorative member will be described as a comparative example.
比較例
高純度のジルコニア粉末100重量部に対し、安
定化剤Y2O35.3重量部、並びに周知の黒色顔料と
してCr、Co、Mn及びNiの酸化物粉末を合計し
て15重量部加え、湿式粉砕後、乾燥した。これを
120メツシユに通し、パラフインワツクスを添加
し、更に80メツシユに通した。この混合物を成形
圧1ton／cm2で５×５×50mmの形状に成形し、脱バ
インダ後、焼成温度1450℃の真空炉で焼成した。Comparative Example To 100 parts by weight of high-purity zirconia powder, 5.3 parts by weight of a stabilizer Y 2 O 3 and a total of 15 parts by weight of Cr, Co, Mn and Ni oxide powders as well-known black pigments were added, After wet grinding, it was dried. this
It was passed through a 120-mesh mesh, paraffin wax was added, and it was further passed through an 80-mesh mesh. This mixture was molded into a shape of 5 x 5 x 50 mm at a molding pressure of 1 ton/cm 2 , and after removing the binder, it was fired in a vacuum furnace at a firing temperature of 1450°C.
かくして得られた焼結体は実施例２で得られた
焼結体と同様に滑らかで深みのある艶を有した鏡
面に加え、黒色度が増大した深い黒光りを有して
いたが、曲げ強度及び靭性特性はそれぞれ35Kg／
mm2及び3MN／m3/2となり、いずれも著しく劣つ
ていた。 The sintered body thus obtained had a mirror surface with a smooth, deep luster, as well as a deep black luster with increased blackness, similar to the sintered body obtained in Example 2, but the bending strength was and toughness properties are respectively 35Kg/
mm 2 and 3 MN/m 3/2 , both of which were significantly inferior.
以上の実施例及び比較例から明らかなように、
本発明のジルコニア系黒色装飾部材では先に述べ
た効果、即ち、アルミナ系黒色部材に比べ、鏡面
研摩後、滑らかで深みのある艶を有した鏡面にな
るという効果に加えて、顔料を含むジルコニア系
黒色装飾部材に比べて、顔料を含有しない結果、
曲げ強度及び靭性特性が飛躍的に大きくなつた。
更に、実施例２のように還元性雰囲気焼成では強
度及び靭性特性を劣化させないで黒色度が増大し
た、所謂、深い黒光りが加わり、装飾部材として
一段と好適になつた。 As is clear from the above examples and comparative examples,
The zirconia-based black decorative member of the present invention has the above-mentioned effect, that is, a mirror surface with a smooth and deep luster after mirror polishing compared to an alumina-based black member. As a result of not containing pigments compared to black decorative materials,
The bending strength and toughness properties have increased dramatically.
Furthermore, as in Example 2, firing in a reducing atmosphere increased the degree of blackness without deteriorating the strength and toughness characteristics, giving it a so-called deep black luster, making it even more suitable as a decorative member.
また、本発明者は前記実施例の他、安定化剤
CaO、MgO等についても実験したところ、本実
施例１及び２と同様に優れた黒色鏡面、並びに曲
げ強度及び靭性特性の向上が確認できた。 In addition to the above-mentioned examples, the present inventor has also
When experiments were conducted using CaO, MgO, etc., it was confirmed that similar to Examples 1 and 2, an excellent black mirror surface and improvements in bending strength and toughness were obtained.
更に、安定化ジルコニア系黒色部材については
安定化剤の添加量を前記実施例よりも大幅に多く
し、即ち、ジルコニア粉末に対しY2O3の成分比
９乃至55mol％、またCaOの成分比を16乃至
29mol％にし、この組成からなる未焼結成形体を
非酸化性雰囲気、好ましくは還元性雰囲気で焼成
し、次いで鏡面研摩することにより、黒光りの加
わつた、深みのある艶を有した黒色鏡面が得られ
た。 Furthermore, for the stabilized zirconia-based black member, the amount of stabilizer added was significantly larger than in the above example, that is, the component ratio of Y 2 O 3 to the zirconia powder was 9 to 55 mol%, and the component ratio of CaO was increased. 16 to
29 mol%, and by firing the unfired compact made of this composition in a non-oxidizing atmosphere, preferably a reducing atmosphere, and then mirror-polishing, a black mirror surface with a deep luster with black luster can be obtained. It was done.
上述の通り、本発明のジルコニア系黒色装飾部
材の製造方法によれば部分安定化ジルコニアの高
強度及び高靭性という優れた特性を利用し、装飾
部材として強度の向上とともに、割れ易いなどの
対物衝撃に強くなり、しかも黒色顔料を含む在来
のジルコニア系黒色装飾部材よりも一段と高強
度、高靭性となり、信頼性の高い装飾部材が提供
できることになつた。 As mentioned above, according to the method for producing a zirconia-based black decorative member of the present invention, the excellent properties of high strength and high toughness of partially stabilized zirconia are utilized, and as well as improving the strength as a decorative member, it also reduces the resistance to objective impacts such as easy breakage. It has become possible to provide a highly reliable decorative member that has higher strength and toughness than conventional zirconia-based black decorative members containing black pigment.
更に、本発明のジルコニア系黒色装飾部材の製
造方法では顔料を含まないため、安価な装飾部材
が提供されるという利点も有する。 Furthermore, since the method for producing a zirconia-based black decorative member of the present invention does not contain any pigment, it also has the advantage of providing an inexpensive decorative member.
Claims (1)
に含有されたY2O3、MgO、CeO2及びCaOから選
ばれた安定化剤の少なくとも一種とから成る未焼
結成形体を1400乃至1600℃の温度で且つ非酸化性
雰囲気中で成形体が黒色になるように焼成し、次
いで得られる焼結体を鏡面研摩することを特徴と
するジルコニア系黒色装飾部材の製造方法。1. An unsintered compact consisting of a base material mainly composed of zirconia and at least one stabilizer selected from Y 2 O 3 , MgO, CeO 2 and CaO contained in the base material. A method for manufacturing a zirconia-based black decorative member, which comprises firing the molded body in a non-oxidizing atmosphere at a temperature of 1600° C. so that the molded body becomes black, and then mirror-polishing the obtained sintered body.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57231174A JPS59121165A (en) | 1982-12-25 | 1982-12-25 | Manufacture of zirconia black dressing member |
| DE3346497A DE3346497C2 (en) | 1982-12-25 | 1983-12-22 | Process for producing a black jewelry item based on zirconium dioxide |
| FR8320579A FR2538314B1 (en) | 1982-12-25 | 1983-12-22 | BLACK ZIRCONIA DECORATIVE ARTICLE AND PROCESS FOR ITS PREPARATION |
| CH6872/83A CH654770A5 (en) | 1982-12-25 | 1983-12-23 | BLACK ZIRCONIA DECORATIVE ARTICLE AND PROCESS FOR ITS PREPARATION. |
| GB08334352A GB2132600B (en) | 1982-12-25 | 1983-12-23 | Zirconia type black decorative article and process for production thereof |
| US06/564,694 US4656145A (en) | 1982-12-25 | 1983-12-23 | Zirconia type black decorative article and process for production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57231174A JPS59121165A (en) | 1982-12-25 | 1982-12-25 | Manufacture of zirconia black dressing member |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59121165A JPS59121165A (en) | 1984-07-13 |
| JPH0157074B2 true JPH0157074B2 (en) | 1989-12-04 |
Family
ID=16919472
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57231174A Granted JPS59121165A (en) | 1982-12-25 | 1982-12-25 | Manufacture of zirconia black dressing member |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59121165A (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61136960A (en) * | 1984-12-06 | 1986-06-24 | 日立化成工業株式会社 | Manufacture of black zirconia ceramics |
| JPH07110785B2 (en) * | 1985-10-02 | 1995-11-29 | 京セラ株式会社 | Method for producing brown zirconia sintered body |
| JPH01126285A (en) * | 1987-11-10 | 1989-05-18 | Ngk Insulators Ltd | Zirconia coated ceramic tool |
| JP5954830B2 (en) * | 2013-03-04 | 2016-07-20 | 株式会社ソディック | Surface modification method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58181766A (en) * | 1982-04-14 | 1983-10-24 | 東レ株式会社 | Zirconia sintered body |
-
1982
- 1982-12-25 JP JP57231174A patent/JPS59121165A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58181766A (en) * | 1982-04-14 | 1983-10-24 | 東レ株式会社 | Zirconia sintered body |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59121165A (en) | 1984-07-13 |
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