JPS6350383A - Coated zro2 base ceramics and manufacture - Google Patents
Coated zro2 base ceramics and manufactureInfo
- Publication number
- JPS6350383A JPS6350383A JP61193701A JP19370186A JPS6350383A JP S6350383 A JPS6350383 A JP S6350383A JP 61193701 A JP61193701 A JP 61193701A JP 19370186 A JP19370186 A JP 19370186A JP S6350383 A JPS6350383 A JP S6350383A
- Authority
- JP
- Japan
- Prior art keywords
- zro
- coating layer
- ceramics
- coated
- ceramic
- 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
- 239000000919 ceramic Substances 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title claims description 5
- 239000011247 coating layer Substances 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 6
- 150000001247 metal acetylides Chemical class 0.000 claims description 5
- 150000004767 nitrides Chemical class 0.000 claims description 5
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000005121 nitriding Methods 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims 2
- 238000005255 carburizing Methods 0.000 claims 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- BYFGZMCJNACEKR-UHFFFAOYSA-N aluminium(i) oxide Chemical compound [Al]O[Al] BYFGZMCJNACEKR-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- 229910010067 TiC2 Inorganic materials 0.000 description 1
- 229910008251 Zr2O2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Compositions Of Oxide Ceramics (AREA)
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) [Abstract] This bulletin contains application data before electronic filing, so abstract data is not recorded.
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、表面に硬質被覆層を有するＺｒＯ，系セラミ
ックスおよびその製造方法に関し、刃物、ダイス、射出
成形工具、バルブ、ポンプ部品等の耐摩用工具、あるい
は時計ケース、ネクタイピン等の装飾部品に用いられて
有効な被覆ＺｒＯ２系セラミックスおよびその製造方法
に関する。Detailed Description of the Invention [Industrial Application Field] The present invention relates to ZrO ceramics having a hard coating layer on the surface and a method for manufacturing the same, and relates to a wear-resistant material for blades, dies, injection molding tools, valves, pump parts, etc. The present invention relates to coated ZrO2-based ceramics that are effective for use in decorative parts such as tools, watch cases, tie clips, etc., and a method for producing the same.
ＺｒＯ，系セラミックスの中には、強靭性に優れたもの
があり、特にＹ２Ｏ，を添加した場合に高強度、ＭｇＯ
又はＣｅＯ２を添加した場合に高靭性が得られ、刃物や
ダイス等の工具に応用が検討されている。Some ZrO-based ceramics have excellent toughness, and especially when Y2O is added, they have high strength and MgO
Alternatively, high toughness can be obtained by adding CeO2, and its application to tools such as knives and dies is being considered.
従来、刃物やダイス等の耐摩耗性を要求される分野にお
いては、超硬合金が主として用いられており、一方Ｚ
ｒ Ｏｘ系セラミックスは、超硬合金に比べ硬さが低い
ため耐摩耗性が劣るという問題点を有していた。本願発
明は以上の問題点に着目してなされたもので、耐摩耗性
の向上を図ったＺ ｒ ０２系セラミツクスおよびその
製造方法の提供を目的とする。Conventionally, cemented carbide has been mainly used in fields that require wear resistance such as blades and dies, but on the other hand, Z
rOx ceramics have a problem of inferior wear resistance because of their lower hardness than cemented carbide. The present invention was made in view of the above problems, and aims to provide Z r 02 ceramics with improved wear resistance and a method for manufacturing the same.
（問題点を解決するための手段〕
本願発明は、Ａ １２０３５−６０ｗｔ％、残部Ｙ２０
．、ＭｇＯ，ＣｅＯ，等の安定化剤を含有したＺｒＯ，
とからなるＺｒＯ２系セラミックスの表面にＴｉ、 Ｚ
ｒ、Ｈｆ、Ｖ、Ｎｂの窒化物、炭化物および炭窒化物の
１種又は２種以上より構成され、膜厚１０μｍ以下の被
覆層を設けることにより前記問題点を解決するものであ
る。(Means for solving the problem) The present invention consists of A 12035-60wt%, the balance Y20
．． , ZrO containing stabilizers such as MgO, CeO, etc.
Ti, Z on the surface of ZrO2 ceramics consisting of
The above-mentioned problem is solved by providing a coating layer composed of one or more of nitrides, carbides, and carbonitrides of r, Hf, V, and Nb and having a thickness of 10 μm or less.
なお、ＺｒＯ，系セラミックスとしては強靭なセラミッ
クスであることが必要で、そのためには。In addition, it is necessary that the ZrO-based ceramic be a strong ceramic.
Ｚｒ２Ｏ２が主として正方品の結晶構造がらなり、かつ
焼結体結晶粒径が３μｍ以下であることが望ましい。It is desirable that Zr2O2 mainly has a tetragonal crystal structure and that the crystal grain size of the sintered body is 3 μm or less.
本願発明被覆ＺｒＯ，系セラミックスは、あらかじめ前
記ＺｒＯ２系セラミックスを窒化性ガス、炭化性ガスの
１種又は２種以上の分圧が合計で、１×１０″〜９ Ｘ
１Ｏ−１ｔｏｒｒの雰囲気中、４００〜７００℃で１
０分間〜３時間保持してＴＬ Ｚｒ、Ｈｆ、Ｖ、Ｎｂの
窒化物、炭化物および炭窒化物の１種又は２種以上被覆
層を蒸着法により形成することにより製造される。The ZrO-based ceramic coated with the present invention is prepared by preheating the ZrO2-based ceramic to a total partial pressure of one or more of nitriding gas and carbonizing gas of 1×10″ to 9×
1 at 400-700℃ in an atmosphere of 1O-1torr
It is manufactured by holding for 0 minutes to 3 hours and forming a coating layer of one or more of nitrides, carbides, and carbonitrides of TL Zr, Hf, V, and Nb by vapor deposition.
本願発明の母材となるＺｒＯ，系セラミックスとシテは
、ＡｌｚＯａ ５−６０ｗｔ％、残部Ｙ、 ０３、Ｍ
ｇ ＯｌＣｅ Ｏ、等の安定化剤を含有し、主として正
方品の結晶構造からなる強靭なＺｒＯ，系セラミックス
が用いられる。ここで、Ａ１□０３は以下の二つの効果
を有する。ZrO-based ceramics and shite, which are the base materials of the present invention, contain 5-60 wt% AlzOa, the balance Y, 03, M.
A strong ZrO-based ceramic containing a stabilizer such as gOlCeO and mainly having a square crystal structure is used. Here, A1□03 has the following two effects.
（１）母材の高硬度化を図る
（２）被覆層と母材との密着強度向上を図る。すなわち
、Ａｌ２Ｏ，を含有しないＺｒＯ２は熱膨張率が１１×
１０−Ｇ程度で被覆層となるＴｉＮ、ＺｒＮ等のそれと
差が大きいが、Ａｌ、０３を含有せしめることにより熱
膨張率が９〜１０と低下し前記被覆層のそれに近い値と
なり密着強度向上が図れるものである。(1) To increase the hardness of the base material. (2) To improve the adhesion strength between the coating layer and the base material. In other words, ZrO2 that does not contain Al2O has a coefficient of thermal expansion of 11×
Although there is a large difference from that of TiN, ZrN, etc. which becomes the coating layer at about 10-G, by containing Al and 03, the coefficient of thermal expansion decreases to 9 to 10, which is close to that of the coating layer, and the adhesion strength is improved. It is something that can be achieved.
なお、 Ａｌ□Ｏ１は５νｔ％未満では、母材の熱膨張
率の低下に効果が小さく、また、６０ｗｔ％を越えると
母材の強靭性が低下するため、Ａ１□Ｏ１は５−６０シ
ｔ％に限定する。Note that if Al□O1 is less than 5 νt%, it will have little effect on reducing the coefficient of thermal expansion of the base material, and if it exceeds 60wt%, the toughness of the base material will decrease. %.
また、焼結体の結晶粒径は小さい方が強靭性及び研磨後
の表面光沢性に優れ良好であり、そのためには３μｍ以
下とする必要がある。Further, the smaller the crystal grain size of the sintered body, the better the toughness and surface gloss after polishing, and for this purpose, it is necessary to make it 3 μm or less.
次すこ本願発明における被覆層について説明する。Next, the coating layer in the present invention will be explained.
第１表には、ＺｒＯ，および被覆層となる物質の硬さく
ＨＶ ）、熱膨張率を示す。本願発明では、Ｚ ｒ
Ｏ、、系セラミックスの表面に第１表に示すＴｊＮ、Ｔ
ｉＣ，ＺｒＮ等の硬質の物質を被覆することにより耐摩
耗性の向上を図るものである。なお、被覆層の厚さが１
０μｍを越えると被覆層の靭性が低下し、耐層工具とし
て使用した場合に、剥離による摩耗が起こりやすくなる
ため被覆層の厚さは１０μｍ以下とする。Table 1 shows the hardness (HV) and coefficient of thermal expansion of ZrO, the material forming the coating layer. In the present invention, Z r
O,, TjN, T shown in Table 1 on the surface of ceramics
The wear resistance is improved by coating with a hard material such as iC or ZrN. Note that the thickness of the coating layer is 1
When the thickness exceeds 0 μm, the toughness of the coating layer decreases, and wear due to peeling tends to occur when used as a layer-resistant tool, so the thickness of the coating layer is set to 10 μm or less.
また、本願発明によると母材のＺｒＯ２系セラミックス
表面にＴｉＮ、ＴｉＣ等の窒化物、炭化物が密着性良く
被覆されるものであるが、これは蒸着中にＴｉの一部が
Ｚ ｒ Ｏ２と反応してＴｉＣ２などを形成し、これら
と蒸着物質であるＴｉＮ、ＴｉＣ等が強固に結合するた
めではないかと推定する。Furthermore, according to the present invention, nitrides and carbides such as TiN and TiC are coated with good adhesion on the surface of the ZrO2-based ceramic base material, but this is because part of the Ti reacts with ZrO2 during vapor deposition. It is presumed that this is due to the formation of TiC2 and the like, which are strongly bonded to the vapor deposited substances such as TiN and TiC.
とくに、蒸着の前段階で、あるいは蒸着時にＮ２、ＮＨ
３などの窒化性ガスやＣＨ４，Ｃ，Ｈ，などの炭化性ガ
スあるいはこれらの混合ガス雰囲気中で温度４００〜７
００℃１時間１０分間〜３時間保持すれば、密着性の良
い被覆が形成される。この場合反応性ガスは合計の分圧
がＩ Ｘ １０−’ ｔｏｒｒ未満では、効果が実質
的に現われず、一方、９ Ｘ １０−’ ｔｏｒｒを越
えると反応膜がポーラスになって逆に密着性が低下する
ので、Ｉ Ｘ １０−４〜９ Ｘ １Ｏ−１−ｔｏｒｒ
となるように流量調整を行なう。In particular, N2, NH
At a temperature of 400 to 7 in an atmosphere of nitriding gas such as 3, carbonizing gas such as CH4, C, H, or a mixed gas of these.
If the temperature is maintained at 00° C. for 1 hour and 10 minutes to 3 hours, a coating with good adhesion will be formed. In this case, if the total partial pressure of the reactive gas is less than I x 10-' torr, the effect will not be substantially exhibited, whereas if it exceeds 9 x 10-' torr, the reaction film will become porous and the adhesion will deteriorate. decreases, so I X 10-4~9 X 1O-1-torr
Adjust the flow rate so that
第 １ 表
〔実施例〕
Ａｌ、０．２０ｔｚｔ％残部Ｙ、０３を３ｍ０１％含有
したＺｒＯ２からなるＺｒＯ２系セラミックスにホロー
カソード方式のイオンブレーティングによりＴ ｉ Ｎ
の被覆処理を行なった。条件は、温度６００℃、Ｎ２分
圧： ４ Ｘ １０−’ ｔｏｒｒで保持時間を１時間
とした。Table 1 [Example] TiN was applied to ZrO2-based ceramics made of ZrO2 containing 3m01% of Al, 0.20tzt% balance Y, and 03 by hollow cathode ion blating.
A coating treatment was performed. The conditions were a temperature of 600°C, a N2 partial pressure of 4 x 10-' torr, and a holding time of 1 hour.
膜厚は被覆処理後切断し顕微鏡で測定した。After coating, the film was cut and measured using a microscope.
そして、耐摩耗性の評価は大端式の摩耗テストで行なっ
た。条件はリング材を５Ｏ３３０４、摺速度０．７４ｍ
／ｓ、最終荷重２．１ｋｇ、摺動距離６００ ｍで比摩
耗量を測定することにより評価した。その結果を第２表
に示すが、本発明にかかるＮｏ、３−６の被覆ＺｒＯ，
系セラミックスは良好な耐摩耗性を示すことがわかる６
第２表
※：○印は本発明
Ｘ印は比較例
〔発明の効果〕
以上説明のごとく１本発明によるとＺ ｒ Ｏ２系セラ
ミツクスの耐摩耗性を向上させることが可能となり、刃
物、ダイス等の工具へ適用した場合に耐久性が向上し、
また本発明被覆ＺｒＯ２系セラミックスは、表面光沢を
有し装飾品としても使用可能であり、工業上有益である
。The wear resistance was evaluated using a large end type wear test. Conditions are ring material 5O3304, sliding speed 0.74m
/s, a final load of 2.1 kg, and a sliding distance of 600 m. The evaluation was made by measuring the specific wear amount. The results are shown in Table 2, and No. 3-6 coating ZrO according to the present invention,
It can be seen that ZrO2-based ceramics exhibit good wear resistance6 Table 2 *: ○ indicates the present invention X indicates comparative examples [effects of the invention] As explained above, 1 According to the present invention, the It is possible to improve abrasion resistance, and when applied to tools such as knives and dies, durability is improved.
Furthermore, the coated ZrO2 ceramic of the present invention has a glossy surface and can be used as a decorative item, which is industrially useful.
Claims (1)
、ＭｇＯ、ＣｅＯ＿２等の安定化剤を含有したＺｒＯ＿
２とからなるＺｒＯ＿２系セラミックスの表面にＴｉ、
Ｚｒ、Ｈｆ、Ｖ、Ｎｂの窒化物、炭化物および炭窒化物
の１種又は２種以上より構成され膜厚１０μｍ以下の被
覆層を有することを特徴とする被覆ＺｒＯ＿２系セラミ
ックス。 ２ ＺｒＯ＿２が主として正方晶の結晶構造からなり、
かつ焼結体結晶粒径が３μｍ以下である特許請求の範囲
第１項記載の被覆ＺｒＯ＿２系セラミックス。 ３ Ａｌ＿２Ｏ＿３５〜６０ｗｔ％、残部Ｙ＿２Ｏ＿３
、ＭｇＯ、ＣｅＯ＿２等の安定化剤を含有したＺｒＯ＿
２とからなるＺｒＯ＿２系セラミックスの表面にＴｉ、
Ｚｒ、Ｈｆ、Ｖ、Ｎｂの窒化物、炭化物および炭窒化物
の１種又は２種以上の被覆層を形成するにあたり、前記
ＺｒＯ＿２系セラミックスを窒化性ガス、炭化性ガスの
１種又は２種以上の分圧が合計で１×１０＾−＾４〜９
×１０＾−＾１ｔｏｒｒの雰囲気中、４００〜７００℃
で１０分間〜３時間保持して被覆層を形成することを特
徴とする被覆ＺｒＯ＿２系セラミックスの製造方法。[Claims] 1 Al_2O_35-60wt%, balance Y_2O_3
, MgO, ZrO_ containing stabilizers such as CeO_2
Ti on the surface of ZrO_2 ceramics consisting of
A coated ZrO_2-based ceramic comprising one or more of nitrides, carbides, and carbonitrides of Zr, Hf, V, and Nb, and having a coating layer with a thickness of 10 μm or less. 2 ZrO_2 mainly has a tetragonal crystal structure,
The coated ZrO_2 ceramic according to claim 1, wherein the sintered body has a crystal grain size of 3 μm or less. 3 Al_2O_35-60wt%, remainder Y_2O_3
, MgO, ZrO_ containing stabilizers such as CeO_2
Ti on the surface of ZrO_2 ceramics consisting of
In forming a coating layer of one or more of nitrides, carbides, and carbonitrides of Zr, Hf, V, and Nb, the ZrO_2-based ceramics are heated with one or more of nitriding gases and carburizing gases. The total partial pressure is 1×10^-^4~9
×10^-^1torr atmosphere, 400~700℃
A method for manufacturing coated ZrO_2-based ceramics, characterized by forming a coating layer by holding the ceramic for 10 minutes to 3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61193701A JP2530623B2 (en) | 1986-08-19 | 1986-08-19 | Coated ZrO 2 system ceramics and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61193701A JP2530623B2 (en) | 1986-08-19 | 1986-08-19 | Coated ZrO 2 system ceramics and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6350383A true JPS6350383A (en) | 1988-03-03 |
| JP2530623B2 JP2530623B2 (en) | 1996-09-04 |
Family
ID=16312347
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61193701A Expired - Lifetime JP2530623B2 (en) | 1986-08-19 | 1986-08-19 | Coated ZrO 2 system ceramics and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2530623B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0947490A1 (en) * | 1998-03-12 | 1999-10-06 | Asulab S.A. | Zirconia based article, its use as wear resistant part of a wristwatch and method for its production |
| US6270907B1 (en) | 1998-03-10 | 2001-08-07 | Asulab S.A. | Zirconia based article, use of such an article as a wear resistant exterior part for a wristwatch and method for obtaining such an article |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61158883A (en) * | 1984-12-28 | 1986-07-18 | 日本特殊陶業株式会社 | Coated zirconia base sintered body |
-
1986
- 1986-08-19 JP JP61193701A patent/JP2530623B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61158883A (en) * | 1984-12-28 | 1986-07-18 | 日本特殊陶業株式会社 | Coated zirconia base sintered body |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6270907B1 (en) | 1998-03-10 | 2001-08-07 | Asulab S.A. | Zirconia based article, use of such an article as a wear resistant exterior part for a wristwatch and method for obtaining such an article |
| US6368468B1 (en) | 1998-03-10 | 2002-04-09 | Asulab S.A. | Zirconia based article, use of such an article as a wear resistant exterior part for a wristwatch and method for obtaining such an article |
| EP0947490A1 (en) * | 1998-03-12 | 1999-10-06 | Asulab S.A. | Zirconia based article, its use as wear resistant part of a wristwatch and method for its production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2530623B2 (en) | 1996-09-04 |
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