CN1172168A - Ultra-hard alloy for wrist watch and decoration - Google Patents
Ultra-hard alloy for wrist watch and decoration Download PDFInfo
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- CN1172168A CN1172168A CN 96110830 CN96110830A CN1172168A CN 1172168 A CN1172168 A CN 1172168A CN 96110830 CN96110830 CN 96110830 CN 96110830 A CN96110830 A CN 96110830A CN 1172168 A CN1172168 A CN 1172168A
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Abstract
The present invention relates to an ultra-hard alloy which inhibits skin allergy owing to harmful heavy metals and has high anti-corrosion property and hardness. The alloy comprises 1-40% by weight of TiC, TiN, or a mixture thereof, 0.05-1.0% by weight of Co, Ni or a mixture thereof, and remaining part of inevitable impurities and WC. The alloy may additionally contain 0.1-5.0% by weight of one or more component (s) selected from a group consisting of TaC, NbC, HfC, ZrC, Mo2C, Cr3C2 and VC.
Description
The present invention relates to be used for the superhard alloy of wrist-watch and extraneous adornment parts, particularly, the present invention relates to suppress allergic, solidity to corrosion and the glossiness of improving machined surface due to the harmful heavy metal and improve superhard alloy in order to the hardness of strengthening scratch resistance.
Usually, wrist-watch or the material that is used for the extraneous adornment parts should have gratifying its high rigidity that obtains high scratch resistance, anti-sweat corrosive solidity to corrosion and the performance such as diamagnetic of making.
As the conventional alloys with these prerequisites, Japan special permission prospectus spy opens clear 59-13045 and had once announced a kind of alloy, and this alloy has improved can shock proof toughness and guarantee that it has solidity to corrosion.
Contain a large amount of gold (costing an arm and a leg), cobalt (global storage abundance is limited), carbide and nitride in conventional alloys described in the above-mentioned patent application.Therefore, production cost is high.
In addition, though require high rigidity for improving scratch resistance as the extraneous adornment parts time, the hardness of this conventional alloys (Hv) has only 1030～1100.
In addition, wherein use a large amount of nickel (it is a kind of deleterious heavy metal to human body) can cause allergic.
And then, in superhard alloy, the bondd influence of phase (binding phase) of chemical property such as solidity to corrosion.
Because matrix metal causes the corrosion of superhard alloy mutually, can improve its corrosion resisting property mutually by eliminating bonding.
The object of the invention is, overcome above-mentioned shortcoming and provide a kind of no agglutinating superhard alloy, this alloy to have less solidity to corrosion and glossiness and enhanced hardness because of the skin hypersensitivity due to the contained harmful heavy metal, improved machined surface with scratch resistance.
Alloy of the present invention comprises Co, the Ni of TiC, the TiN of 1～40 (weight) % or its mixture, 0.05～1.0 (weight) % or its mixture, its surplus is unavoidable impurities and WC.
What also can add 0.1～5.0 (weight) % in alloy of the present invention is selected from TaC, NbC, VC, ZrC, HfC, Mo
2C, Cr
3C
2In one or more carbide.
In superhard alloy of the present invention, add a small amount of TaC, NbC, VC, ZrC, HfC, Mo
2C and/or Cr
3C
2Be in order to suppress brilliant material growth; And add TiC is in order to alleviate the weight of final material; Adding TiN is the performance for reinforced alloys.
As everyone knows, be in the superhard alloy of base the time when nitrogen adds with the WC-TiC composition, be suppressed at the crystalline substance material growth of the mononitride phase during the sintering and make the fine alloy structure, so can improve the intensity and the antioxidant property of alloy greatly.
According to the present invention, the very a spot of bonding phase of logical adding (cobalt, nickel or its mixture) and implement sintering circuit, thus under lower sintering temperature, also can obtain having satisfactory texture, and imporosity and do not have the complete alloy of brilliant material growth almost.
If the content of bonding phase is too low, then since the grain growing increase of carbide and structure become ununiformity and can not meet the demands.
On the other hand,,, hardness is increased to some extent, but carbon content reduces, thereby increase the formation of harmful η-phase and hardness and the glossiness that reduces the surface then as routine techniques if the content of bonding phase is too high.
Although can only use Co bonding phase,, use the mixing bonding of Co and Ni more satisfactory mutually for improving the stability of alloy strength and alloy.
Like this, first feature of alloy of the present invention is to have the glossiness of superior machined surface than other wrist-watch or finishing material.
This is because the structure of alloy of the present invention does not bond mutually and contains very thin and uniform carbide, thereby avoid uneven bonding (small ununiformity, it is caused than less wear by than the overwear vt. of soft part and higher hardness part when alloy surface weares and teares).
Owing to the carbide of high rigidity mutually and the inhomogeneous bonding in its surface that causes of the nonhomogeneous hardness of the matrix metal of soft between mutually, and make the glossiness of conventional superhard alloy low.
Secondly, alloy of the present invention has than the about 1400-1800 of general superhard alloy hardness (Hv) (under above-mentioned Japan special permission publication number 59-13045 situation, hardness only 1030～1100) much higher hardness (2200Hv or higher) therefore, has good scratch resistance.
Although conventional superhard alloy, its hardness reduces when the bonding phasor increases, the alloy of the present invention phase that almost do not bond, and have high rigidity.
The 3rd, alloy of the present invention contains very a spot of bonding phase, so can not produce because of containing the caused problem of harmful heavy metal or allergic.
The 4th, alloy of the present invention has low-down magnetic (nonmagnetic in fact), and therefore, it belongs to non-magnetic material.
For example, the magneticsaturation value of alloy of the present invention be about WC-10 (weight) %Co superhard alloy 5%.
The 5th, alloy of the present invention has very superior solidity to corrosion.
The corrosion of superhard alloy be because of the bonding phase corrosion caused.Therefore, the material of the present invention that contains the phase that bonds does not hardly cause the main cause of corrosive, therefore, has superior solidity to corrosion.
The present invention will be described by following examples now.
Embodiment
Consider surface gloss and sintering character, the present invention adopts quite fine grain raw material powder, wherein: WC≤2 μ m, TiC and TiN≤1.5 μ m, TaC, NbC, VC≤1 μ m, Co is 1 μ m, Ni is 4 μ m.Its composition is shown in the following table 1.
The mixing of raw material (powder) is to carry out with wet method, and wherein, the feed molar ratio of ball and powder is 3.5: 1, and mixing rate is 88rpm, and mixing time is 48 hours.
The sintering of alloy is under vacuum, 1450 ℃ of sintering 1 hour.
It is to carry out under 1330 ℃ and argon gas atmosphere (1200 normal atmosphere) that HIP (hot isostatic press) handles.
Listed solidity to corrosion is to identify by the turbidity of observing the alloy surface of dipping after 48 hours in the solution with the listed component of table 2 on table 1.
Table 1 alloying constituent and physicals
| Alloying constituent (weight %) | |||||||||
| ???WC | ?TiC | ?TiN | ??TaC | ???NbC | ??HfC | ??Mo 2C | ?ZrC | ||
| The present invention | ??1 | ??95.0 | ??3 | ??2 | |||||
| ??2 | ??95.0 | ??3 | ??2 | ||||||
| ??3 | ??90.0 | ??6 | ??4 | ||||||
| ??4 | ??95.0 | ??3 | ??2 | ||||||
| ??5 | ??86.8 | ??12 | ??0.84 | ??0.36 | |||||
| ??6 | ??86.8 | ??23 | ??0.84 | ??0.38 | |||||
| ??7 | ??80.2 | ??18 | ??1.26 | ??0.54 | |||||
| ??8 | ??73.6 | ??24 | ??1.68 | ??0.72 | |||||
| ??9 | ??68.0 | ??29 | ??2.03 | ??0.87 | |||||
| ??10 | ??86.8 | ??6 | ??6 | ??1.20 | |||||
| ??11 | ??73.6 | ??12 | ??12 | ??2.40 | |||||
| ??12 | ??86.8 | ??6 | ??6 | ??0.84 | ??0.36 | ||||
| ??13 | ??80.2 | ??9 | ??9 | ??1.26 | ??0.54 | ||||
| ??14 | ??80.2 | ??10 | ??8 | ??0.76 | ??0.54 | ||||
| ??15 | ??96.0 | ??3 | |||||||
| ??16 | ??87.6 | ??12 | ??0.4 | ||||||
| ??17 | ??80.2 | ??18 | ??0.1 | ??1.5 | ??0.1 | ||||
| ??JP ??59- ??13045 | ??14 | ??75-85 | |||||||
| ??15 | ??65-75 | ??10 | |||||||
| ??16 | ??50- ??68 | ??20 | |||||||
| ??17 | ??33- ??43 | ??VC12 | ??25 | ||||||
| Alloying constituent (weight %) | Density (g/cm 3) | Hardness (Hv) | Solidity to corrosion | ||||||
| ???Cr 3???C 2 | ???VC | ???Co | ??Ni | ?AU | |||||
| The present invention | ??1 | ??0.3 | ??14.63 | ??2128 | Good | ||||
| ??2 | ??0.5 | ??14.62 | ??2081 | ???＂ | |||||
| ??3 | ??1.0 | ??13.92 | ??2004 | Well | |||||
| ??4 | ??0.3 | ??14.64 | ??2206 | Good | |||||
| ??5 | ??0.3 | ??12.28 | ??2210 | ???＂ | |||||
| ??6 | ??0.3 | ??0.1 | ??12.30 | ??2250 | ???＂ | ||||
| ??7 | ??0.3 | ??11.11 | ??2222 | ???＂ | |||||
| ??8 | ??0.3 | ??10.17 | ??2220 | ???＂ | |||||
| ??9 | ??0.3 | ??9.45 | ??2205 | ???＂ | |||||
| ??10 | ??0.3 | ??12.26 | ??2200 | ???＂ | |||||
| ??11 | ??0.3 | ??10.15 | ??2208 | ???＂ | |||||
| ??12 | ??0.5 | ??12.26 | ??2175 | ???＂ | |||||
| ??13 | ??1.0 | ??11.10 | ??2113 | Well | |||||
| ??14 | ??0.5 | ??1.0 | ??11.05 | ??2110 | ???＂?? | ||||
| ??15 | ??0.5 | ??0.5 | ??14.60 | ??2050 | ???＂ | ||||
| ??16 | ??0.3 | ??12.27 | ??2200 | Good | |||||
| ??17 | ??0.1 | ??1.3 | ??0.1 | ??11.10 | ??2188 | ???＂ | |||
| ?JP ?59- ?1304 ?5 | ??14 | ??2-3 | ??3-7 | ?10- ?15 | ??1055- ??1090 | ||||
| ??15 | ??2-3 | ??3-7 | ?15 | ??1050- ??1075 | |||||
| ??16 | ??2 | ??7-10 | ?13- ?18 | ??1040- ??1100 | |||||
| ??17 | ??7-12 | ?13- ?18 | ??1030- ??1080 | ||||||
The composition of table 2 etchant solution
| Edible salt | Sodium-chlor | Ammoniacal liquor (28%) | Lactic acid (85%) | Distilled water |
| 9.9g/l | ?0.88g/l | ?0.07ml/l | ?0.2ml/l | ?1l |
As mentioned above, superhard alloy of the present invention surface smoothness, hardness, solidity to corrosion, density, non magnetic, separate each side such as toxicity and all have premium properties, therefore, it is as wrist-watch and to decorate with material be prominent.In addition, it can be widely used in the product scope that requires high anti-corrosion and high rigidity, such as nozzle, the model that is used for disc, mechanical sealing member, optical lens etc.
Claims (2)
1, be used for the superhard alloy of wrist-watch and decoration, it contains, TiC, TiN or its mixture of 1～40 (weight) %, and Co, the Ni of 0.05～1.0 (weight) % or its mixture, its surplus are unavoidable impurities and WC.
2, be used for the superhard alloy of wrist-watch and decoration, it contains, TiC, TiN or its mixture of 1～40 (weight) %, and Co, the Ni of 0.05～1.0 (weight) % or its mixture, 0.1～5.0 (weight) % are selected from TaC, NbC, HfC, ZrC, Mo
2C, Cr
3C
2With one or more carbide of VC, its surplus is unavoidable impurities and WC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96110830 CN1172168A (en) | 1996-07-30 | 1996-07-30 | Ultra-hard alloy for wrist watch and decoration |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 96110830 CN1172168A (en) | 1996-07-30 | 1996-07-30 | Ultra-hard alloy for wrist watch and decoration |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1172168A true CN1172168A (en) | 1998-02-04 |
Family
ID=5120928
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96110830 Pending CN1172168A (en) | 1996-07-30 | 1996-07-30 | Ultra-hard alloy for wrist watch and decoration |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1172168A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419105C (en) * | 2005-02-04 | 2008-09-17 | 李北 | Metal ceramic material and formation technology |
| CN101151386B (en) * | 2005-03-28 | 2010-05-19 | 京瓷株式会社 | Ultra-hard alloy and cutting tool |
| WO2010135859A1 (en) * | 2009-05-25 | 2010-12-02 | Li Bei | Accurate shaping method for metal ceramic material |
| CN102951904A (en) * | 2012-11-21 | 2013-03-06 | 邓湘凌 | Corrosion resistant high temperature resistant car pressurizing turbo material |
| CN103060652A (en) * | 2013-01-25 | 2013-04-24 | 地质矿产部无锡钻探工具厂 | High-temperature-resistant alloy and production process thereof |
| CN104755446A (en) * | 2012-10-09 | 2015-07-01 | 山特维克知识产权股份有限公司 | Low-binder wear-resistant hard metal |
| CN104884653A (en) * | 2013-01-16 | 2015-09-02 | 并木精密宝石株式会社 | Decorative member |
| CN106119655A (en) * | 2016-08-11 | 2016-11-16 | 宁波市鄞州亚大汽车管件有限公司 | A kind of oil pipe plug |
| CN108117392A (en) * | 2017-12-04 | 2018-06-05 | 株洲夏普高新材料有限公司 | Corrosion resistant non-bond cemented carbide and preparation method thereof |
| CN108642361A (en) * | 2018-06-11 | 2018-10-12 | 顾亚新 | A kind of high strength and high hardness ceramic material and its production technology |
| CN110904375A (en) * | 2019-12-10 | 2020-03-24 | 泰州永航精密铸造有限公司 | Alloy with good corrosion resistance for yacht and preparation method thereof |
| CN111378886A (en) * | 2018-12-28 | 2020-07-07 | 自贡硬质合金有限责任公司 | Ultra-fine grain hard alloy and preparation method thereof |
| CN111663067A (en) * | 2020-06-04 | 2020-09-15 | 杭州科技职业技术学院 | Hard alloy material for 3D printing and preparation process thereof |
| CN111918978A (en) * | 2018-03-29 | 2020-11-10 | 京瓷株式会社 | Cemented carbide, coated tool and cutting tool |
| CN111996431A (en) * | 2020-08-10 | 2020-11-27 | 苏州新锐合金工具股份有限公司 | Cemented carbide without binding phase and preparation method thereof |
-
1996
- 1996-07-30 CN CN 96110830 patent/CN1172168A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100419105C (en) * | 2005-02-04 | 2008-09-17 | 李北 | Metal ceramic material and formation technology |
| CN101151386B (en) * | 2005-03-28 | 2010-05-19 | 京瓷株式会社 | Ultra-hard alloy and cutting tool |
| WO2010135859A1 (en) * | 2009-05-25 | 2010-12-02 | Li Bei | Accurate shaping method for metal ceramic material |
| CN104755446A (en) * | 2012-10-09 | 2015-07-01 | 山特维克知识产权股份有限公司 | Low-binder wear-resistant hard metal |
| US9624417B2 (en) | 2012-10-09 | 2017-04-18 | Sandvik Intellectual Property Ab | Low binder, wear resistant hard metal |
| CN104755446B (en) * | 2012-10-09 | 2016-11-16 | 山特维克知识产权股份有限公司 | The wear-resisting hard metal of low binding agent |
| CN102951904B (en) * | 2012-11-21 | 2015-03-25 | 邓湘凌 | Corrosion resistant high temperature resistant car pressurizing turbo material |
| CN102951904A (en) * | 2012-11-21 | 2013-03-06 | 邓湘凌 | Corrosion resistant high temperature resistant car pressurizing turbo material |
| CN104884653A (en) * | 2013-01-16 | 2015-09-02 | 并木精密宝石株式会社 | Decorative member |
| CN103060652A (en) * | 2013-01-25 | 2013-04-24 | 地质矿产部无锡钻探工具厂 | High-temperature-resistant alloy and production process thereof |
| CN106119655A (en) * | 2016-08-11 | 2016-11-16 | 宁波市鄞州亚大汽车管件有限公司 | A kind of oil pipe plug |
| CN108117392A (en) * | 2017-12-04 | 2018-06-05 | 株洲夏普高新材料有限公司 | Corrosion resistant non-bond cemented carbide and preparation method thereof |
| CN111918978A (en) * | 2018-03-29 | 2020-11-10 | 京瓷株式会社 | Cemented carbide, coated tool and cutting tool |
| CN111918978B (en) * | 2018-03-29 | 2022-11-25 | 京瓷株式会社 | Cemented carbide, coated cutting tool and cutting tool |
| CN108642361A (en) * | 2018-06-11 | 2018-10-12 | 顾亚新 | A kind of high strength and high hardness ceramic material and its production technology |
| CN111378886A (en) * | 2018-12-28 | 2020-07-07 | 自贡硬质合金有限责任公司 | Ultra-fine grain hard alloy and preparation method thereof |
| CN111378886B (en) * | 2018-12-28 | 2021-12-07 | 自贡硬质合金有限责任公司 | Ultra-fine grain hard alloy and preparation method thereof |
| CN110904375A (en) * | 2019-12-10 | 2020-03-24 | 泰州永航精密铸造有限公司 | Alloy with good corrosion resistance for yacht and preparation method thereof |
| CN111663067A (en) * | 2020-06-04 | 2020-09-15 | 杭州科技职业技术学院 | Hard alloy material for 3D printing and preparation process thereof |
| CN111996431A (en) * | 2020-08-10 | 2020-11-27 | 苏州新锐合金工具股份有限公司 | Cemented carbide without binding phase and preparation method thereof |
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