JP2742607B2 - Hard silver ceramics for decoration - Google Patents
Hard silver ceramics for decorationInfo
- Publication number
- JP2742607B2 JP2742607B2 JP1204265A JP20426589A JP2742607B2 JP 2742607 B2 JP2742607 B2 JP 2742607B2 JP 1204265 A JP1204265 A JP 1204265A JP 20426589 A JP20426589 A JP 20426589A JP 2742607 B2 JP2742607 B2 JP 2742607B2
- Authority
- JP
- Japan
- Prior art keywords
- decoration
- strength
- weight
- tic
- hard silver
- 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 - Fee Related
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 15
- 239000000919 ceramic Substances 0.000 title claims description 15
- 229910052709 silver Inorganic materials 0.000 title claims description 15
- 239000004332 silver Substances 0.000 title claims description 15
- 238000005034 decoration Methods 0.000 title claims description 6
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 claims description 13
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 10
- 229910003470 tongbaite Inorganic materials 0.000 claims description 2
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 claims 1
- 238000005260 corrosion Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 13
- 239000011651 chromium Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 210000004243 sweat Anatomy 0.000 description 4
- 238000002845 discoloration Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000011195 cermet Substances 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- GVEHJMMRQRRJPM-UHFFFAOYSA-N chromium(2+);methanidylidynechromium Chemical compound [Cr+2].[Cr]#[C-].[Cr]#[C-] GVEHJMMRQRRJPM-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は炭化チタン（TiC）を主成分とする装飾用銀
色セラミックスの強度の改良に関するものである。DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to an improvement in the strength of a decorative silver ceramic mainly composed of titanium carbide (TiC).
［発明の背景］ 近時、TiCを主成分とした装飾用硬質銀色材料が硬度
に優れた特性を有しているため、装飾用部材として広範
に賞用されている。BACKGROUND OF THE INVENTION In recent years, a decorative hard silver material mainly composed of TiC has been widely used as a decorative member because of its excellent hardness.
［発明が解決しようとする問題点］ しかしながら、通常TiC自体は難焼結性であり焼結促
進を目的としてNi,Co等の金属元素が結合金属として添
加されているため金属部分もしくは炭化物・金属間で発
生する局部電池のため、腐食が進行し、例えば、汗など
により変色するなどして装飾用部材の呈色が損われると
いう難点があった。[Problems to be Solved by the Invention] However, TiC itself is generally difficult to sinter, and a metal element such as Ni or Co is added as a bonding metal for the purpose of promoting sintering. Because of the local battery generated between the cells, there is a problem that the corrosion progresses and the coloration of the decorative member is impaired by, for example, discoloration due to sweat or the like.
そこで、本発明者等は先に特開昭60−27651号におい
てTiCの原料粉末に対し、特定の比率で炭化クロム（Cr3
C2）粉末を加え、形成後、焼結したところ、耐食性が改
良され且つ焼結性の良好な装飾用硬質銀色セラミックス
が得られることを提案したが、強度の点で未だ不十分で
あった。Therefore, the present inventors have previously described in Japanese Patent Application Laid-Open No. 60-27651 a chromium carbide (Cr 3
C 2 ) It was proposed that a powdery hard silver ceramic with improved corrosion resistance and good sinterability could be obtained when powder was added and formed and then sintered, but it was still insufficient in strength. .
本発明者等は更に鋭意研究に努めたところ、上記組成
に更にY2O3、希土類酸化物の中の１種類以上の粉末を焼
結助剤として加えたところ、耐食性を劣化させることな
く、強度の優れた装飾用硬質銀色セラミックスが得られ
ることを知見した。The present inventors have conducted further intensive research, and further added Y 2 O 3 , one or more powders of rare earth oxides as a sintering aid to the above composition, without deteriorating corrosion resistance, It has been found that a hard silver ceramic for decoration having excellent strength can be obtained.
本発明は上記知見に基づき、耐食性が優れ且つ硬度、
強度ともに優れた装飾用硬質銀色セラミックスを提供す
ることを目的とする。The present invention is based on the above findings, excellent corrosion resistance and hardness,
An object of the present invention is to provide a hard silver ceramic for decoration having excellent strength.
本発明の装飾用硬質銀色セラミックスは、TiCを75重
量％以上、Cr3C2を３〜20重量％、Y2O3あるいは希土類
酸化物のうちの１種以上を0.05〜15重量％含有させたこ
とを特徴とするものである。Decorative hard silver ceramics of the present invention, TiC and 75 wt% or more, Cr 3 C 2 3 to 20% by weight, is contained 0.05 to 15% by weight of one or more of the Y 2 O 3 or rare earth oxides It is characterized by having.
本発明の装飾用硬質銀色セラミックスによれば、TiC
を原料とし、これにCr3C2が添加されるが、TiC量は75重
量％以上含有することが重要である。これは、TiCが75
重量％よりも少なくなるとTiC自体が本来有する硬度が
低下するからである。またCr3C2は焼結性向上のため３
〜20重量％の範囲に設定されることが重要である。According to the decorative hard silver ceramic of the present invention, TiC
Is used as a raw material, and Cr 3 C 2 is added to the raw material. It is important that the TiC content is 75% by weight or more. This is TiC 75
This is because if it is less than the weight%, the hardness inherent in TiC itself decreases. Cr 3 C 2 is used to improve sinterability.
It is important that it be set in the range of ~ 20% by weight.
また、焼結助剤として加えられるY2O3あるいは希土類
酸化物のうちの１種以上の化合物は、その添加量が0.05
重量％未満では焼結促進の効果無く、15重量％を越える
と逆に焼結不良又は、色調が損なわれるために0.05〜15
重量％、好適には１〜10重量％の範囲に設定されること
が重要である。The amount of one or more compounds selected from the group consisting of Y 2 O 3 and rare earth oxides added as a sintering aid is 0.05%.
If it is less than 15% by weight, there is no effect of promoting sintering, and if it exceeds 15% by weight, on the contrary, poor sintering or color tone is impaired.
It is important that it is set in the range of 1% by weight, preferably 1 to 10% by weight.
TiC、Cr3C2及びY2O3希土類酸化物の原料粉末の粒径に
ついては、いずれも５μｍ以下がよく、好適には２μｍ
以下がよい。そして、上記の如く、適正な粒径にするた
め、原料粉末をセラミックボールやサーメットボールな
ど硬質ボールで粉砕すればよい。例えば、サーメットボ
ールであれば、その摩耗により金属成分も混入されるた
め、その摩耗量ができるだけ少ない粉砕ボールを選ぶの
が望ましい。The particle size of the raw material powder of TiC, Cr 3 C 2 and Y 2 O 3 rare earth oxide is preferably 5 μm or less, and more preferably 2 μm or less.
The following is good. Then, as described above, the raw material powder may be ground with a hard ball such as a ceramic ball or a cermet ball in order to obtain an appropriate particle size. For example, in the case of a cermet ball, a metal component is mixed by the abrasion, so that it is desirable to select a pulverized ball having the smallest possible wear amount.
上記に従い、TiCの原料粉末にCr3C2とY2O3、希土類酸
化物のうち１種以上の原料粉末を加えた混合物を加圧焼
成し、1400〜1700℃、10-1〜10-5torrの真空炉において
１〜５時間焼成を行うと耐食性に優れ且つ硬度、強度と
もに優れた装飾用硬質銀色セラミックスが得られる。According to the above, a mixture obtained by adding one or more raw material powders of Cr 3 C 2 , Y 2 O 3 , and rare earth oxides to the raw material powder of TiC is fired at 1400 to 1700 ° C., 10 −1 to 10 −. When firing in a 5 torr vacuum furnace for 1 to 5 hours, a decorative hard silver ceramic having excellent corrosion resistance and excellent hardness and strength can be obtained.
［実施例］ 第１表に示す通りの混合比率により、TiC原料粉末
（平均粒径１μｍ）にCr3C2粉末（平均粒径７μｍ）及
びY2O3、希土類酸化物（平均粒径１〜２μｍ）を添加
し、樹脂性ポット中へ入れ、ジルコニアボールとともに
アセトン中、42時間混合粉砕した。次いで、この混合物
を乾燥後、パラフィンを４重量％加え、1.5ton/cm2で加
圧成形し、脱バインダ後、1600℃、10-4torrの真空炉焼
成を１〜５時間行った。[Examples] According to the mixing ratios shown in Table 1, a TiC raw material powder (average particle diameter 1 μm) was mixed with Cr 3 C 2 powder (average particle diameter 7 μm), Y 2 O 3 , and rare earth oxide (average particle diameter .About.2 .mu.m), put into a resin pot, and mixed and pulverized together with zirconia balls in acetone for 42 hours. Next, after drying this mixture, paraffin was added at 4% by weight, pressure-molded at 1.5 ton / cm 2 , and after removing the binder, firing in a vacuum furnace at 1600 ° C. and 10 -4 torr was performed for 1 to 5 hours.
かくして得られた焼結体を鏡面研磨し、色調並びに抗
折強度、ビッカース硬度（Hv）及び耐食性を試験した。The thus obtained sintered body was mirror-polished and tested for color tone and bending strength, Vickers hardness (Hv) and corrosion resistance.
抗折強度の測定はJIS−Ｒ−1601の３点曲げ試験法に
従い、耐食性試験については、人間の汗の標準的な成分
を人工的に作成した人工汗に浸すという耐汗試験、及び
塩水（４％w/v）を霧状にして吹き掛けるという塩水噴
霧試験（JIS−Ｚ−2371−76）を行った。The flexural strength was measured according to the three-point bending test method of JIS-R-1601. The corrosion resistance test was performed by immersing a standard component of human sweat into artificially created artificial sweat. (4% w / v) in a salt spray test (JIS-Z-2371-76).
これらの結果は第１表に示す通りである。 These results are shown in Table 1.
表中、耐食性試験の結果については、耐汗試験及び塩
水噴霧試験のいずれにも同様の結果を得ており、○印は
変色及び腐食が全くなく、色調劣化の全くない装飾部材
であることを示し、×印は変色または腐食が認められ、
徐々に色調が劣化し、装飾部材として不適であることを
示す。 In the table, regarding the results of the corrosion resistance test, similar results were obtained in both the sweat resistance test and the salt spray test, and the mark ○ indicates that the decorative member had no discoloration or corrosion and had no color deterioration. Indicates that discoloration or corrosion was observed,
The color tone gradually deteriorates, indicating that it is unsuitable as a decorative member.
第１表より明らかなように、Cr3C2あるいはY2O3、希
土類酸化物を添加していないNo.1、２では強度が低く、
実用的でない。As is clear from Table 1, the strength was low in Nos. 1 and 2 in which Cr 3 C 2 or Y 2 O 3 and rare earth oxide were not added,
Not practical.
また、希土類酸化物の量が多いNo.8では強度が不十分
で且つ色調が灰白色となり、装飾用としては不適であ
る。In addition, No. 8 having a large amount of rare earth oxide has insufficient strength and color tone is grayish white, which is not suitable for decoration.
Cr3C2の代わりに一般的に用いられているMo2Cでは強
度か低く、希土類酸化物の代わりに結合金属として最も
使用されているNiを用いたNo.10、11では耐蝕性が悪
く、色調の変化が認められた。Mo 2 C, which is commonly used instead of Cr 3 C 2 , has a low strength, and No. 10 and 11 using Ni, which is the most commonly used binding metal instead of rare earth oxide, have poor corrosion resistance A change in color tone was observed.
これに対し、本発明のNo.3〜７の銀色セラミックスは
在来の銀色セラミックスに比べ、耐食性、高強度を維持
しつつ、強度が著しく優れていることが判った。On the other hand, it was found that the silver ceramics of Nos. 3 to 7 of the present invention were significantly superior in strength while maintaining corrosion resistance and high strength as compared with conventional silver ceramics.
尚、本発明銀色セラミックスの焼結方法は、その他に
ホットプレスまたはHIPを用いても何ら問題がない。In the method of sintering the silver ceramics of the present invention, there is no problem even if hot pressing or HIP is used.
［発明の効果］ 以上の通り、本発明の装飾用硬質銀色セラミックスは
従来の銀色セラミックスに比べ、耐食性、高強度を劣化
させることなく強度が著しく改良され、その結果、長期
に亘り、腐食やキズを発生せず且つ強度の要求される時
計ケースなどの装飾用部材として賞用される。[Effects of the Invention] As described above, the hard silver ceramic for decoration of the present invention has significantly improved strength, without deteriorating corrosion resistance and high strength, as compared with conventional silver ceramics. This is a prize as a decorative member such as a watch case that does not generate any strength and requires strength.
Claims (1)
３〜20重量％、Y2O3あるいは希土類酸化物のうちの１種
以上を0.05〜15重量％含有させたことを特徴とする装飾
用硬質銀色セラミックス。1. A titanium carbide 75% by weight or more, chromium carbide 3-20% by weight, characterized in that one or more were contained 0.05 to 15 wt% of Y 2 O 3 or rare earth oxides Hard silver ceramic for decoration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1204265A JP2742607B2 (en) | 1989-08-07 | 1989-08-07 | Hard silver ceramics for decoration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1204265A JP2742607B2 (en) | 1989-08-07 | 1989-08-07 | Hard silver ceramics for decoration |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0369561A JPH0369561A (en) | 1991-03-25 |
| JP2742607B2 true JP2742607B2 (en) | 1998-04-22 |
Family
ID=16487605
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1204265A Expired - Fee Related JP2742607B2 (en) | 1989-08-07 | 1989-08-07 | Hard silver ceramics for decoration |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2742607B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4727081B2 (en) * | 2001-07-30 | 2011-07-20 | 株式会社ニフコ | Seat belt guide |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6027651A (en) * | 1983-07-19 | 1985-02-12 | 京セラ株式会社 | Dressing hard silver-color ceramics |
| JPH0816028B2 (en) * | 1986-07-31 | 1996-02-21 | 日本特殊陶業株式会社 | Highly tough ceramic sintered body, ceramic tool and method for manufacturing sintered body |
| JPH08729B2 (en) * | 1987-09-24 | 1996-01-10 | 秩父小野田株式会社 | Titanium carbide sintered body |
-
1989
- 1989-08-07 JP JP1204265A patent/JP2742607B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0369561A (en) | 1991-03-25 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |