JPH044991B2 - - Google Patents
Info
- Publication number
- JPH044991B2 JPH044991B2 JP58132487A JP13248783A JPH044991B2 JP H044991 B2 JPH044991 B2 JP H044991B2 JP 58132487 A JP58132487 A JP 58132487A JP 13248783 A JP13248783 A JP 13248783A JP H044991 B2 JPH044991 B2 JP H044991B2
- Authority
- JP
- Japan
- Prior art keywords
- decorative
- weight
- corrosion resistance
- tic
- 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 - Lifetime
Links
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052709 silver Inorganic materials 0.000 claims description 14
- 239000004332 silver Substances 0.000 claims description 14
- 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 12
- 239000000919 ceramic Substances 0.000 claims description 11
- 229910003470 tongbaite Inorganic materials 0.000 claims description 3
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 claims 1
- 230000007797 corrosion Effects 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 8
- 239000011651 chromium Substances 0.000 description 7
- 238000005245 sintering Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 6
- 239000011195 cermet Substances 0.000 description 5
- 238000002845 discoloration Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 210000004243 sweat Anatomy 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 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
- 238000005452 bending Methods 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 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
- 238000004040 coloring Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical compound [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000001737 promoting effect Effects 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
- C04B35/5611—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides based on titanium carbides
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/5607—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on refractory metal carbides
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Ceramic Products (AREA)
Description
本発明は炭化チタン（TiC）から成る装飾用硬
質銀色セラミツクスの耐食性の改良に関するもの
である。
近時、TiC、WC等の炭化物を主成分とした装
飾用硬質銀色材料が硬度及び強度に優れた特性を
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。
しかしながら、これらの焼結体は焼結促進を目
的としてNi、Co等の金属元素が焼結助剤として
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つた。
本発明者は上記事情に鑑み、鋭意研究に努めた
ところ、TiCの原料粉末に対し、特定の比率で炭
化クロム（Cr3C2）粉末を焼結助剤として加え、
成形後、焼成したところ、耐食性が改良され、好
適な装飾用硬質銀色セラミツクスが得られること
を知見した。
本発明は上記知見に基づき、耐食性の優れた装
飾用硬質銀色セラミツクスを提供することを目的
とする。
本発明の装飾用硬質銀色セラミツクスはTiCを
主成分とし、Cr3C2を0.1〜40重量％含有させたこ
とを特徴とするものである。
本発明の装飾用硬質銀色セラミツクスにおいて
は、TiCを主原料とし、Cr3C2が焼結助剤として
添加されるが、その添加量は0.1重量％未満また
は40重量％を超えると、焼結不良になるため、
0.1〜40重量％、好適には３〜20重量％の範囲に
設定されることが重要である。
TiC及びCr3C2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、原料粉末をセラミツクボールやサーメツトボ
ールなど硬質ボールで粉砕すればよい。例えば、
サーメツトボールであれば、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。
上記に従い、TiCの原料粉末にCr3C2の原料粉
末を加えた混合物を加圧成形し、1500〜1700℃、
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た装飾用硬質銀色セラミツ
クスが得られる。
次に本発明を実施例に基づき説明する。
〔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7μ
ｍ）を添加し、樹脂性ポツト中へ入れ、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、この混合物の乾燥後、パラフインを
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５時間
行つた。
かくして得られた焼結体を鏡面研摩し、色調、
並びに抗折強度、ビツカース硬度（Hv）及び耐
食性を試験した。
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）を行つた。
これらの結果は第１表に示す通りである。
The present invention relates to improving the corrosion resistance of decorative hard silver ceramics made of titanium carbide (TiC). In recent years, decorative hard silver materials mainly composed of carbides such as TiC and WC have been widely used as decorative members because of their excellent hardness and strength. However, these sintered bodies contain metal elements such as Ni and Co as sintering aids for the purpose of promoting sintering.
Because of the localized batteries that occur between metals, corrosion progresses and, for example, there is a problem in that the coloring of the decorative member is impaired due to discoloration due to sweat or the like. In view of the above circumstances, the present inventor made extensive research efforts and found that chromium carbide (Cr 3 C 2 ) powder was added as a sintering aid to TiC raw material powder in a specific ratio.
After molding and firing, it was found that the corrosion resistance was improved and a hard silver ceramic suitable for decoration could be obtained. Based on the above findings, the present invention aims to provide decorative hard silver ceramics with excellent corrosion resistance. The decorative hard silver ceramic of the present invention is characterized by having TiC as a main component and containing 0.1 to 40% by weight of Cr 3 C 2 . In the decorative hard silver ceramics of the present invention, TiC is the main raw material, and Cr 3 C 2 is added as a sintering aid, but if the amount added is less than 0.1% by weight or exceeds 40% by weight, sintering will occur. Because it becomes defective,
It is important that the amount is set in the range of 0.1 to 40% by weight, preferably 3 to 20% by weight. Regarding the particle size of TiC and Cr3C2 raw powder,
In either case, the thickness is preferably 5 μm or less, preferably 2 μm or less. Then, as mentioned above, in order to obtain a suitable particle size, the raw material powder may be ground with a hard ball such as a ceramic ball or a cermet ball. for example,
If the balls are made of cermet balls, metal components will be mixed in due to their wear, so it is desirable to select grinding balls that have as little wear as possible. According to the above, a mixture of TiC raw material powder and Cr 3 C 2 raw material powder was press-molded and heated at 1500-1700℃.
By performing the firing in a vacuum furnace at 10 -1 to 10 -5 torr for 1 to 5 hours, decorative hard silver ceramics with excellent corrosion resistance can be obtained. Next, the present invention will be explained based on examples. [Example] Cr 3 C 2 powder (average particle size 7μm) was added to TiC raw powder (average particle size 1μm) according to the mixing ratio shown in Table 1.
m) was added, placed in a resin pot, and mixed and ground together with zirconia balls in acetone for 42 hours. Next, after drying this mixture, 4% by weight of paraffin was added and pressure molded at 1.5 ton/cm 2 . After removing the binder, it was fired in a vacuum oven at 1600° C. and 10 −4 torr for 5 hours. The sintered body thus obtained is polished to a mirror finish, and the color tone and
In addition, bending strength, Vickers hardness (Hv) and corrosion resistance were tested. The bending strength was measured according to the three-point bending test method of JIS-R-1601, and the corrosion resistance test was conducted by soaking the standard components of human sweat in artificial sweat, and by soaking in salt water ( Salt water spray test (JIS-Z-
2371-76). These results are shown in Table 1.
【表】
＊印を付した試料番号のものは本発明の範
囲外のものである。
＊＊印を付した硬度は焼結不良のため測定不
能であることを示している。
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。
第１表より明らかなように、耐食性試験の結
果、試料番号２〜７では変色及び腐食が全くな
く、色調劣化の全くない優れた装飾部材となるこ
とがわかり、試料番号８、並びに比較例として示
した如く、在来のNi10重量％含有のTiCサーメ
ツトや、Mo2C20重量％とNi20重量％含有のTiC
サーメツトでは変色または腐食が認められ、徐々
に色調が劣化することが判つた。そして、試料番
号１及び８では焼結不良となり、強度及び硬度が
著しく劣り、装飾部材として不適であつた。
本実施例の銀色セラミツクスは在来の銀色サー
メツトに比べ、装飾部材として何ら支障のない強
度を維持しつつ、硬度が著しく優れていることが
判り、そして、Cr3C2の含有量が少ないほど比重
の減少傾向があり、且つ銀白色から銀色への色調
変化があることが認められた。
また、Cr3C2の含有量が焼結体中、0.1〜40重量
％の範囲であれば、原料粉砕用硬質ボールに、ア
ルミナボールなど他のセラミツクボール、もしく
はサーメツトボールを使用した場合でも、ボール
の摩耗に伴う不可避不純物の混入量ができるだけ
少なければ耐食性に優れ、且つ硬度が充分に大き
くなつたことが認められ、そして、Cr3C2の含有
量が少ないほど比重が小さくなるとともに、銀白
色から銀色へ色調が変化し、優れた銀色装飾部材
が提供できることが確かめられた。
以上の通り、本発明の装飾用硬質銀色セラミツ
クスは在来の銀色サーメツトに比べ、装飾用途
上、何ら支障のない強度を示し、且つ耐食性、硬
度が著しく改良され、その結果、長期に亘り、腐
食やキズを発生しないため、壁材、時計ケース、
ブローチ、記念メダル、ボタンなどの装飾用部材
として賞用される。[Table] Sample numbers marked with * are outside the scope of the present invention.
The hardness marked with ** indicates that it cannot be measured due to poor sintering.
In the table, regarding the results of the corrosion resistance test, both the sweat resistance test and the salt spray test obtained similar results, and the ○ mark indicates that the decorative member has no discoloration or corrosion and no color deterioration. , × indicates that discoloration or corrosion is observed, the color tone gradually deteriorates, and the material is unsuitable as a decorative member. As is clear from Table 1, as a result of the corrosion resistance test, it was found that samples No. 2 to 7 had no discoloration or corrosion at all, and were excellent decorative members with no color deterioration. As shown, conventional TiC cermet containing 10% Ni by weight and TiC containing 20% by weight Mo 2 C and 20% Ni by weight
It was found that discoloration or corrosion was observed in the cermet, and the color tone gradually deteriorated. Samples Nos. 1 and 8 had poor sintering and were significantly inferior in strength and hardness, making them unsuitable as decorative members. It was found that the silver ceramic of this example has significantly superior hardness compared to conventional silver cermets while maintaining sufficient strength to be used as a decorative member . It was observed that the specific gravity tended to decrease and the color changed from silvery white to silvery. Furthermore, if the content of Cr 3 C 2 is in the range of 0.1 to 40% by weight in the sintered body, even if other ceramic balls such as alumina balls or cermet balls are used as hard balls for crushing raw materials, It is recognized that if the amount of unavoidable impurities mixed in due to ball wear is as small as possible, corrosion resistance will be excellent and hardness will be sufficiently large, and the lower the Cr 3 C 2 content, the lower the specific gravity, It was confirmed that the color tone changed from silver-white to silver, and that an excellent silver decorative member could be provided. As described above, compared to conventional silver cermets, the decorative hard silver ceramics exhibits strength that does not pose any problem in decorative applications, and has significantly improved corrosion resistance and hardness, resulting in long-term corrosion resistance. Because it does not cause scratches or scratches, it can be used on wall materials, watch cases,
It is used as decorative materials such as brooches, commemorative medals, and buttons.
Claims (1)
〜40重量％含有させたことを特徴とする装飾用硬
質銀色セラミツクス。1 Titanium carbide is the main component, and chromium carbide is 0.1
A decorative hard silver ceramic characterized by containing ~40% by weight.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58132487A JPS6027651A (en) | 1983-07-19 | 1983-07-19 | Dressing hard silver-color ceramics |
| DE19843426176 DE3426176C2 (en) | 1983-07-19 | 1984-07-16 | Hard silver ceramic for decorative purposes and method for producing such a hard silver ceramic |
| CH347984A CH660175A5 (en) | 1983-07-19 | 1984-07-17 | HARD SILVER CERAMIC FOR DECORATION PURPOSES. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58132487A JPS6027651A (en) | 1983-07-19 | 1983-07-19 | Dressing hard silver-color ceramics |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6027651A JPS6027651A (en) | 1985-02-12 |
| JPH044991B2 true JPH044991B2 (en) | 1992-01-30 |
Family
ID=15082518
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58132487A Granted JPS6027651A (en) | 1983-07-19 | 1983-07-19 | Dressing hard silver-color ceramics |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JPS6027651A (en) |
| CH (1) | CH660175A5 (en) |
| DE (1) | DE3426176C2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU5159485A (en) * | 1984-12-24 | 1986-07-03 | Todoroki, Itaru | Sintered titanium carbo-nitride-chromium carbide ceramics |
| JPS63230569A (en) * | 1987-03-20 | 1988-09-27 | イビデン株式会社 | Tic sintered body and manufacture |
| JP2742607B2 (en) * | 1989-08-07 | 1998-04-22 | 京セラ株式会社 | Hard silver ceramics for decoration |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2765227A (en) * | 1950-12-16 | 1956-10-02 | Sintercast Corp America | Titanium carbide composite material |
-
1983
- 1983-07-19 JP JP58132487A patent/JPS6027651A/en active Granted
-
1984
- 1984-07-16 DE DE19843426176 patent/DE3426176C2/en not_active Expired - Lifetime
- 1984-07-17 CH CH347984A patent/CH660175A5/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| CH660175A5 (en) | 1987-03-31 |
| JPS6027651A (en) | 1985-02-12 |
| DE3426176C2 (en) | 1993-09-30 |
| DE3426176A1 (en) | 1985-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JPS6029443A (en) | Golden sintered alloy for decoration | |
| GB2132600A (en) | Zirconia type black decorative article and process for production thereof | |
| JPS61106743A (en) | Ornamental silver color sintered alloy | |
| KR100239844B1 (en) | Sintered alloy of golden color | |
| US4511665A (en) | Decorative hard golden ceramic article | |
| KR100943931B1 (en) | Sintered alloy and method of manufacturing the same | |
| KR100385208B1 (en) | Silver Sintered Product and Manufacturing Method Thereof | |
| JPH044991B2 (en) | ||
| JPH06228703A (en) | Gold-colored sintered compact and its production | |
| JP2742607B2 (en) | Hard silver ceramics for decoration | |
| JP3020663B2 (en) | Seal | |
| JP3231873B2 (en) | Silver sintered alloy and method for producing the same | |
| JP2722118B2 (en) | Titanium carbide based silver sintered alloy | |
| WO2016186232A1 (en) | Cermet alloy for jewelry and method for producing same | |
| JP3255700B2 (en) | Gold sintered alloy | |
| JPS58136743A (en) | Golden sintered alloy for decoration | |
| JPS5933660B2 (en) | Decorative golden sintered alloy | |
| JPH059643A (en) | Golden sintered alloy | |
| JP3481777B2 (en) | Gold sintered body | |
| JPH0753605B2 (en) | Method for manufacturing titanium nitride sintered body | |
| JPH08157990A (en) | Silver-colored sintered compact and its production | |
| JP3255767B2 (en) | Golden sintered body and method for producing the same | |
| JPH0763500A (en) | Arrowhead | |
| JPH06172889A (en) | Golden sintered alloy and its production | |
| JPS6227031B2 (en) |