KR0142934B1 - Carbide Alloys for Watches - Google Patents
Carbide Alloys for WatchesInfo
- Publication number
- KR0142934B1 KR0142934B1 KR1019950003078A KR19950003078A KR0142934B1 KR 0142934 B1 KR0142934 B1 KR 0142934B1 KR 1019950003078 A KR1019950003078 A KR 1019950003078A KR 19950003078 A KR19950003078 A KR 19950003078A KR 0142934 B1 KR0142934 B1 KR 0142934B1
- Authority
- KR
- South Korea
- Prior art keywords
- alloy
- hardness
- cemented carbide
- phase
- mixture
- Prior art date
Links
- 239000000956 alloy Substances 0.000 title abstract description 24
- 229910045601 alloy Inorganic materials 0.000 title abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 abstract description 13
- 238000005260 corrosion Methods 0.000 abstract description 13
- 201000004624 Dermatitis Diseases 0.000 abstract description 6
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 5
- 210000000707 wrist Anatomy 0.000 abstract 1
- 239000000463 material Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 150000001247 metal acetylides Chemical class 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 230000007547 defect 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
- 238000005498 polishing Methods 0.000 description 2
- 230000003746 surface roughness Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
- C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
- C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
Abstract
본 발명은 손목시계용 외장부품에서 유해 중금속 함유에 의한 피부 알레르기 발생을 억제하고 내식성 및 경도를 향상시킨 초경함금에 관한 것으로 TiC, TiN 중 1종 또는 그 혼합이 1~40중량%, NbC, TaC중 1종 또는 그 혼합이 0.1~5.0중량%이고, 나머지는 불가피한 불순물과 WC로 조성됨을 특징으로 하는 손목시계용 외장부품 초경합금에 관한 기술이다.The present invention relates to a cemented carbide alloy that suppresses the occurrence of skin allergies due to the presence of harmful heavy metals and improves the corrosion resistance and hardness in the exterior parts for wristwatches, and includes 1 to 40 wt% of TiC, TiN, or a mixture thereof, NbC, TaC. One or a mixture thereof is 0.1 to 5.0% by weight, and the remainder is a technology related to a cemented carbide alloy for wrist watches, characterized in that the composition is composed of inevitable impurities and WC.
Description
본 발명은 손목시계용 외장부품의 초경합금에 관한 것으로, 특히 유해 중금속 함유에 의한 피부알레르기 발생을 억제함과 동시에 내식성 및 가공면의 광택도를 개선하고 경도를 높여 내스크라치(Scratch)성을 향상시키는데 적합한 초경합금에 관한 것이다.The present invention relates to a cemented carbide of a wristwatch exterior part, and particularly to suppress skin allergy caused by the presence of harmful heavy metals, to improve the corrosion resistance and glossiness of the processed surface, and to increase the hardness to improve scratch resistance. It relates to a suitable cemented carbide.
일반적으로, 시계용 외장부품에 요구되는 조건으로는내 Scratch성을 갖기 위한 높은경도, 땀에 대한 내식성, 비자화성 등을 들 수 있다.In general, conditions required for watch exterior parts include high hardness for having scratch resistance, corrosion resistance to sweat, non-magnetic resistance, and the like.
이러한 조건을 갖기 위한 종래의 시계 외장부품용 합금으로서는 일본공개특허공보소 59-13045가 알려지고 있는데, 이는 내충격성을 갖게 하기 위해 인성을 향상시키고 내식성을 확보하는데 있다.Japanese Patent Laid-Open Publication No. 59-13045 is known as a conventional alloy for watch exterior parts having such a condition, which is intended to improve toughness and secure corrosion resistance in order to have impact resistance.
이와 같은 종래 합금은 Au(10~18wt%)-Ni(3~7wt%)-Co(2~4wt%-WC(나머지)로 하거나, NbC(10wt%)-Au(10~15wt%)-Co(2~4wt%)-TaC(나머지), TiN(20wt%)-Au(13~18wt%)-Ni(7`10wt%)-Co(2wt%)-NbC(25wt%)-VC(12wt%)-Au(13-18wt%)-nI(7-12wt%)-Tin(나머지)로 조성되고 그에 따른 경도(Hv)는 1,030~1,100 정도의 값을 나타내고 있다.Such conventional alloys may be Au (10-18 wt%)-Ni (3-7 wt%)-Co (2-4 wt% -WC (rest) or NbC (10 wt%)-Au (10-15 wt%)-Co (2 ~ 4wt%)-TaC (rest), TiN (20wt%)-Au (13 ~ 18wt%)-Ni (7`10wt%)-Co (2wt%)-NbC (25wt%)-VC (12wt% ) -Au (13-18wt%)-nI (7-12wt%)-Tin (rest), and the resulting hardness (Hv) is about 1,030 ~ 1,100.
이와 같은 합금은 전반적으로 고가인 Au를 다량 함유시키고 있으며 또한 Co는 세계적으로 그 분포량이 한정되고 있는 전략원소로써 그 사용량이 많음에 따라 제조원가의 상승요인이 되고 있다.Such alloys generally contain a large amount of expensive Au, and Co is a strategic element whose distribution is limited in the world.
뿐만 아니라 외장부품으로써 내 Scratch 성을 갖기 위해서는 높은 경도가 요구되는데도 불구하고 그 경도가(Hv)가 1,030~1,100에 불과하다.In addition, despite the high hardness required to have scratch resistance as an exterior part, its hardness (Hv) is only 1,030 ~ 1,100.
한편, 절삭공구용 초경합금으로서는 일본국 특개평 5-230589를비롯한 특개평 2-71904등이 알려지고 있는데, 이들은 (Ti,Ta,Nb 등)의 산화물, 질화물, 탄질화물 중 1종 이상이 0.1~30wt%, 여기에 결합상금속으로서 Co, Ni 중 1종 이상이 4.0~30wt%이고, 나머지는 WC을 기본으로 하고 있다.On the other hand, as a cemented carbide for cutting tools, Japanese Patent Application Laid-Open No. Hei 2-71904, including Japanese Patent Application Laid-open No. Hei 5-230589, is known. These include 0.1 ~ 1 or more of oxides, nitrides, carbonitrides (Ti, Ta, Nb, etc.). 30 wt%, here, as a binding metal, at least one of Co and Ni is 4.0 to 30 wt%, and the rest is based on WC.
그러나 이와 같은 절삭공구의 용도에 사용되고 있는 재료는 경도를 요하면서도 피부알레르기성, 내식성, 경면 광택성을 요하는 손목시계 외장부품용 소재로 사용하는데는 결합상 금속(Co,Ni)의 첨가량이 많아 Co에 따른 제조원가를 비롯한 다음과 같은 문제점이 있다.However, the materials used for the cutting tool are hard to add, but the amount of the combined metal (Co, Ni) is high in the case for watch exterior parts requiring skin allergy, corrosion resistance, and mirror gloss. There are the following problems including manufacturing costs according to Co.
즉, Ni은 원소자체가 인체에 유해한 중금속이라서 손목시계용 외장부품으로 사용할 때는 사람에 따라 피부알레르기를 유발시킬 수 있는 문제가 있으며, 또한 내식성과 같은 화학적 성질도 결합상 금속의 영향을 받는다.That is, Ni is a heavy metal that is harmful to the human body, and when used as a watch exterior part, Ni may cause skin allergies, and chemical properties such as corrosion resistance are also affected by the binding phase metal.
뿐만 아니라 결합상금속이 많으면(상기 선행기술들을 binder 초경합금이라한다) 경도가 저하되고 또한 경면의 광택도도 떨어지게 되므로 시계외장부품용에 적용하는데는 문제점이 있다.In addition, when there are many binding phase metals (the above prior arts are called binder cemented carbides), the hardness is lowered and the glossiness of mirror surfaces is also lowered.
본 발명은 상기한 종래의 문제점을 해결하기 위해 안출한 것으로, 결합상이 없는 binderless 초경합금을 개발함으로써 유해중금속 함유에 의한 피부알레르기 발생을 억제함과 함께 내식성 및 가공면의 강택도를 개선하고 경도를 높여 내 Scratch성이 향상된 특성을 갖는 초경합금을 제공하는데 그 목적이 있다.The present invention has been made to solve the above-mentioned problems, by developing a binderless cemented carbide without binding phase to suppress the skin allergy caused by the inclusion of harmful heavy metals while improving the corrosion resistance and hardness of the processed surface and increase the hardness Its purpose is to provide a cemented carbide with improved scratch resistance.
이와 같은 목적달성을 위한 본 발명은 Tic, Tin 중 1종 또는 그 혼합이 1~40wt%, NbC, TaC중 1종 또는 그 혼합이 0.1~5.0wt%, Co, Ni 중 1종 또는 그 혼합이 0.05~1.0wt%이고, 나머지는 불가피한 불순물과 WC로 조성된다.The present invention for achieving the above object is 1 to 40wt% of Tic, Tin or a mixture thereof, 1 to 40wt% of NbC, TaC or 0.1 to 5.0wt% of its mixture, Co, Ni or a mixture thereof 0.05-1.0 wt%, the remainder is composed of inevitable impurities and WC.
본 발명에서 TaC와 NbC는 입성장(grain growth)의 억제를 위하여 소량 첨가한 것이고, 또한 소재의 결량화를 위하여 TiC를, 합금의 성능 향상을 위하여 TiN을 첨가하였다.In the present invention, TaC and NbC are added in small amounts to suppress grain growth, and also TiC is added for defects in the material and TiN is added for improving the performance of the alloy.
TiC와 TiN의 첨가량이 1wt% 이하면 경도 값이 떨어지고, 40wt% 이상이면 강도 값이 떨어진다.If the addition amount of TiC and TiN is less than 1wt%, the hardness value is lowered, and if it is 40wt% or more, the strength value is lowered.
이미 알려진 바와 같이 WC-TiC를 기본 조성으로 하는 초경합금에 질소를 첨가하면 소결동안 탄질화물상의 입성장이 억제되어 합금조직이 미세하게 되므로 합금의 강도가 크게 증가하고 내산화성이 향상된다.As already known, the addition of nitrogen to the cemented carbide based on WC-TiC inhibits the growth of carbonitride phase during sintering, resulting in a fine alloy structure, which greatly increases the strength of the alloy and improves oxidation resistance.
본 발명은 매우 소량의(0.05~1.0wt%)의 결합상을 첨가(Co,Ni 중 1종 또는 혼합)하여 소결을 행하므로써 비교적 낮은 온도에서 기공이 없고 입성장이 거의 없는 미세한 조직의 완전한 합금을 얻을 수 있다.The present invention sinters by adding a very small amount (0.05 to 1.0 wt%) of a combined phase (one of Co and Ni or mixed) to form a perfect alloy of fine structure with no pores and little grain growth at a relatively low temperature. You can get it.
이와 같은 결합상의 함량이 너무 적을 경우(0.05wt% 이하)결합상의 함량감소에 따라 탄화물량이 많게 되어 탄화물의 입성장이 심하고 조직이 불균일하여 바람직하지 못하다.If the content of such a binder phase is too small (0.05wt% or less), the carbide content increases due to the decrease in the content of the binder phase, which is not preferable because of the grain growth of carbides and uneven structure.
한편 그 함량이 많아지면(1.0wt% 이상)종래 기술처럼 합금의 강도는 다소 증가하나 탄소량이 적어져서 유해한 η상(etaphase)의 형성이 증가하고 경도가 저하되며 경면의 광택도도 떨어진다.On the other hand, if the content is increased (more than 1.0wt%), the strength of the alloy is slightly increased as in the conventional technology, but the amount of carbon decreases, which increases the formation of harmful eta phase, decreases the hardness, and reduces the glossiness of the mirror.
또한 Co 결합상만을 사용할 수 있으나 바람직하게는 Co, Ni 혼합결합상을 사용하므로써 합금의 강도를 높일 수 있고 안정화시킬 수 있다.In addition, only Co-bonded phase can be used, but preferably, by using Co, Ni mixed-bonded phase, the strength of the alloy can be increased and stabilized.
이상에서와 같이 합금의 특징으로는 첫째, 다른 손목시계 소재에 비하여 가공면의 광택도가 탁월하다.As described above, the alloy features, firstly, superior glossiness of the processed surface compared to other wristwatch materials.
이는 본 합금의 조직이 결합상이 거의 없어 매우 미세하고 균일한 탄화물로만 이루어졌으므로 표면에 위상적인 결함(합금의 표면연마시 경도가 낮은 부분은 많이 연마되고 경도가 높은 부분은 적게 연마되어 발생되는 미세한 요철)이 없기 때문이다.This is because the structure of this alloy is composed of only very fine and uniform carbides because there are few bonding phases. Therefore, the topological defects on the surface (fine unevenness caused by polishing a lot of low hardness and a small part of high hardness during surface polishing of the alloy) ) Is missing.
일반적인 초경합금에서는 고경도의 탄화물상과 저경도의 결합금속상 사이에 경도차이가 있으므로 인하여 표면에 위상적인 결함이 생겨 광택도가 떨어진다.In general cemented carbides, there is a hardness difference between the hard carbide phase and the hard metal bond phase, resulting in a phase defect on the surface, resulting in poor gloss.
둘째, 일반적인 초경합금의 경도(Hv)는 약 1400~1800(상기한 일본특개소 59-13045의경우는 1,030~1,100에 불과함)인데 비하여 본 발명은 경도가 2200Hv 이상으로 훨씬 높은 경도를 가지므로 내 Scrath성이 우수하다.Secondly, the hardness (Hv) of a general cemented carbide is about 1400-1800 (only 1,030-1,100 in the case of Japanese Patent Laid-Open 59-13045). Excellent in sex
초경합금의 경도는 결합상의 양이 많을수록 떨어지는데 본 합금은 결합상이 거의 없으므로 높은 경도를 가질 수 있는 것이다.The hardness of the cemented carbide decreases as the amount of bonding phase increases, but this alloy has high bonding strength because there is almost no bonding phase.
셋째, 본 발명 합금은 결합상의 첨가량이 극히 적기 때문에(0.05~1.0wt%) 소재에 유해한 중금속 함유에 따른 문제점이 없으며 소재가 피부에 접촉되어도 피부 알레르기가 발생하지 않는다.Third, the alloy of the present invention is extremely small (0.05 ~ 1.0wt%) because of the addition amount of the binding phase is not a problem due to the harmful heavy metals contained in the material and skin allergy does not occur even if the material is in contact with the skin.
넷째, 본 발명 합금은 자성도 무시할 수 있을 정도로 매우 낮아 비자성소재의 범주에 든다.Fourth, the alloy of the present invention is so low that negligible magnetic, it falls into the category of nonmagnetic materials.
예를 들어 본 발명 합금의 자기포화값은 WC~10wt% Co 초경합금의 자기포화값에 비하여 5% 내외의 값을 가진다.For example, the self-saturation value of the alloy of the present invention has a value of about 5% compared to the self-saturation value of the WC ~ 10wt% Co cemented carbide.
다섯째, 본 합금은 내식성이 매우 우수하다.Fifthly, the alloy has excellent corrosion resistance.
초경합금에 있어서 소재 부식의 발생하는 것은 소재에 함유되어 있는 결합상이 부식되기 때문이다.Corrosion of materials occurs in cemented carbides because the bonding phase contained in the materials corrodes.
따라서 결합상이 거의 없는 본 발명 소재는 부식의 근본적인 원인이 제거되므로 인하여 내식성이 우수하다.Therefore, the present invention material having almost no binding phase is excellent in corrosion resistance because the underlying cause of corrosion is eliminated.
다음은 실시예에 따라 설명한다.The following is described according to the embodiment.
[실시예]EXAMPLE
본 발명에 사용된 원료분말은 면조도(광택도) 및 소결성을 고려하여 비교적 미립의 분말(WC:2μm 이하, TiC, Tin:1.5μm 이하, TaC, NbC:1μm 이하, Co:1μm, Ni:4μm)을 사용하였으며 (표 1)과 같은 합금조성비로 하였다.Raw powder used in the present invention is relatively fine powder (WC: 2μm or less, TiC, Tin: 1.5μm or less, TaC, NbC: 1μm or less, Co: 1μm, Ni: 4μm in consideration of surface roughness (glossiness) and sinterability) ) Was used as the alloy composition ratio as shown in (Table 1).
원료분말의 혼합은 습식으로 행하였는데 이 때 볼(Ball)과 분말의 장입비는 3,5:1로 하였으며 혼합속도는 88rpm으로 하여 48시간 동안 혼합을 행하였다.The mixing of the raw powder was performed in a wet manner, and the mixing ratio of the balls and the powder was 3,5: 1, and the mixing speed was 88 rpm, and the mixing was performed for 48 hours.
합금의 소결은 진공소결 분위기 하에서 1450℃의 온도로 1시간동안 행하였다.Sintering of the alloy was performed for 1 hour at a temperature of 1450 ° C. under vacuum sintering atmosphere.
그리고 HIP(Hot Isostatic Pfress)처리는 1330℃, 1200기압의 아르곤(Ar)가스 분위기 하에서 행하였다.HIP (Hot Isostatic Pfress) treatment was performed under an argon (Ar) gas atmosphere at 1330 ° C. and 1200 atm.
상기한 (표 1)에 있어서 내식성 평가는 (표 2)와 같은 성질을 가지는 용액에 합금을 48시간 동안 담근 후 합금표면의 흐려짐 정도를 보고 판단하였다.In Table 1, the corrosion resistance was evaluated by immersing the alloy in a solution having the properties as shown in Table 2 for 48 hours and then looking at the degree of clouding of the alloy surface.
이상에서와 본 발명의 초경합금은 손목시계부품 소재로써 요구되는 특성인 면조도, 경도, 내식성, 밀도, 비자성, 해독성 등에서 뛰어난 성능을 보이므로 손목시계용 소재로 각광을 받을 수 있으며 또한 내식성과 고경도가 요구되는 분사노즐, Compact disc의 금형, mechanical seals, optical lens등의 부분에도 널리 응용될 것으로 기대된다.As described above, the cemented carbide according to the present invention exhibits excellent performance in surface roughness, hardness, corrosion resistance, density, nonmagnetic properties, detoxification, and the like, which are required as a watch component material, and thus can be spotlighted as a watch material. It is expected to be widely applied to parts such as injection nozzles, compact disc molds, mechanical seals, optical lenses, etc., which are required.
Claims (1)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950003078A KR0142934B1 (en) | 1995-02-17 | 1995-02-17 | Carbide Alloys for Watches |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019950003078A KR0142934B1 (en) | 1995-02-17 | 1995-02-17 | Carbide Alloys for Watches |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR960031633A KR960031633A (en) | 1996-09-17 |
| KR0142934B1 true KR0142934B1 (en) | 1998-08-17 |
Family
ID=19408322
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019950003078A KR0142934B1 (en) | 1995-02-17 | 1995-02-17 | Carbide Alloys for Watches |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR0142934B1 (en) |
-
1995
- 1995-02-17 KR KR1019950003078A patent/KR0142934B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| KR960031633A (en) | 1996-09-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100436327B1 (en) | Sintered hard alloy | |
| JP2009540129A (en) | Sintered carbide with precision structure | |
| EP1462534A1 (en) | Compositionally graded sintered alloy and method of producing the same | |
| JPH03170637A (en) | Sintered carbonitride alloy | |
| KR102738187B1 (en) | Superhard alloy, cutting tool and method for manufacturing superhard alloy | |
| US4902651A (en) | Material for magnetic head substrate member | |
| JP5851826B2 (en) | WC-based cemented carbide for cutting tools having excellent plastic deformation resistance at high temperatures, coated cutting tools, and methods for producing the same | |
| US4701381A (en) | Composite materials and products | |
| KR0142934B1 (en) | Carbide Alloys for Watches | |
| JPH0447021B2 (en) | ||
| JPS63109139A (en) | Titanium carbide sintered alloy for cutting tool parts | |
| JPS5949297B2 (en) | Hard sintered alloy for decorative parts | |
| JPH1046282A (en) | Cemented carbide for wristwatch and ornament | |
| JP7618329B1 (en) | Sintered alloys and dies | |
| JPS6059195B2 (en) | Manufacturing method of hard sintered material with excellent wear resistance and toughness | |
| JP3231873B2 (en) | Silver sintered alloy and method for producing the same | |
| JP4540791B2 (en) | Cermet for cutting tools | |
| JPS61201750A (en) | sintered hard alloy | |
| JP3232599B2 (en) | High hardness cemented carbide | |
| JPS5891145A (en) | Titanium oxide-base colored sintered alloy | |
| JP3031106B2 (en) | Hard ultrafine particle dispersed ceramic metal composite | |
| JPS5916946A (en) | Outer part of watch | |
| JPS6311645A (en) | Nitrogen-containing sintered hard alloy and its manufacturing method | |
| JP2002105577A (en) | Decorative member and its production method | |
| JPS597341B2 (en) | Hard sintered alloy with excellent corrosion resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| PA0109 | Patent application |
Patent event code: PA01091R01D Comment text: Patent Application Patent event date: 19950217 |
|
| PA0201 | Request for examination |
Patent event code: PA02012R01D Patent event date: 19950217 Comment text: Request for Examination of Application |
|
| PG1501 | Laying open of application | ||
| E902 | Notification of reason for refusal | ||
| PE0902 | Notice of grounds for rejection |
Comment text: Notification of reason for refusal Patent event date: 19971226 Patent event code: PE09021S01D |
|
| E701 | Decision to grant or registration of patent right | ||
| PE0701 | Decision of registration |
Patent event code: PE07011S01D Comment text: Decision to Grant Registration Patent event date: 19980305 |
|
| GRNT | Written decision to grant | ||
| PR0701 | Registration of establishment |
Comment text: Registration of Establishment Patent event date: 19980406 Patent event code: PR07011E01D |
|
| PR1002 | Payment of registration fee |
Payment date: 19980406 End annual number: 3 Start annual number: 1 |
|
| PG1601 | Publication of registration | ||
| LAPS | Lapse due to unpaid annual fee | ||
| PC1903 | Unpaid annual fee |
Termination category: Default of registration fee Termination date: 20020110 |