KR920006806B1 - Preparation method of calcined body made by al2o3-ticx - Google Patents
Preparation method of calcined body made by al2o3-ticx Download PDFInfo
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Abstract
Description
본 발명은 고경도금속 절삭공구로 사용되는 Al2O3-TiCx계 절삭공구 소결체의 제조방법에 관한 것이다.The present invention relates to a method for producing a sintered Al 2 O 3 -TiC x -based cutting tool used as a hard metal cutting tool.
일반적으로 Al2O3-TiCx계 세라믹 절삭공구는 내마모성 및 기존의 Al2O3세라믹 공구에 비해 인성이 우수하기 때문에 고경도금속 절삭용으로 개발된 이후에 큰 호평을 받고 있으나, Al2O3-TiCx계는 그 성능면에 있어서는 우수하나, 소결시키기 어려운 난소결특성을 갖고 있는 바, 예컨대, 이들은 세라믹 소재가 갖는 취약특성과 고온소결을 필요로 하는 난(難)소결체이기 때문에 이들의 소결특성 향상과 절삭능력의 증가를 위한 연구가 현재 끊임없이 진행되어 오고 있는 실정이 있다.In general, Al 2 O 3 -TiC based ceramic cutting tool x is very popular since the high hardness developed for metal cutting because of its excellent wear resistance and toughness than the conventional Al 2 O 3 ceramic, but the tool, Al 2 O The 3 -TiC x system has an excellent sintering property in terms of its performance, but is difficult to sinter. For example, since the 3 -TiC x system is an sintered body that requires fragility and high temperature sintering of ceramic materials, In order to improve the sintering characteristics and increase the cutting capacity, there is a situation that is constantly being conducted.
이에 따라 최근에는 Al2O3-TiC 절삭공구의 성능을 향상시키기 위해 미국특허 제4,416,840호 및 미국특허 제4,407,968호에서는 TiC 대신 TiCx(x=0.65 내지 0.95)를 20 내지 40체적% 범위내로 첨가 사용함으로써 소결온도의 저하 및 소결체의 치밀화 등의 특성을 향상시켜 Al2O3-TiC 소결체의 구조결함을 개선시키고자 하였다. 그러나 이 방법으로 제조된 소결체는 소결분위기와 온도 등에 따라 TiCx결정중 x의 비율변동이 심하여 각 제품간의 품질변동이 심한 단점을 갖고 있었다.Accordingly, in order to improve the performance of Al 2 O 3 -TiC cutting tools, US Pat. Nos. 4,416,840 and 4,407,968 add TiC x (x = 0.65 to 0.95) in the range of 20 to 40% by volume instead of TiC. In order to improve the structural defects of the Al 2 O 3 -TiC sintered body by improving the characteristics such as lowering of the sintering temperature and densification of the sintered body. However, the sintered body manufactured by this method had a disadvantage of severe quality variation between the products due to the severe variation of the ratio of x in the TiC x crystal depending on the sintering atmosphere and temperature.
또, 상기와 같은 난점들을 개선하기 위해서 열압축법이나 HIP법(hot isostatatic pressing) 또는 1900℃까지 고온으로 승온시키는 소결법 등을 응용하기도 하였고, 그 이외에도 각종 소결첨가제를 첨가 이용하는 방법도 있었다. 예컨대, 일특공 소 62-45194호, 일특개 소 56-63870호 및 일특개 소 62-153159호 등에서는 Y2O3를 첨가하여 소결성을 향상시키고, 일특개 소 62-32151호에서는 Dy2O3를, 일특공 소 49-1444호에서는 MgO를 소결보조제로 첨가하는 방법으로 소결하곤하였다. 그러나, 열압축법은 일축가압에 의해 소결체를 생산하기 때문에 소결체 형상을 다양화하는데 제약이 많았고 다양한 형상을 제조하기 위해서는 가공비가 많이 드는 단점이 있었다. 또, 고온으로 급승온하는 방법에 의한 소결체 제조는 급승온에 따른 열충격에 의해 소결체 표면에 균열이 가거나 소결온도가 고온인 관계로 소결체가 휘거나 소결체의 미세구조가 조대화됨에 따라 내마모 및 인성저하 등의 특성저하를 유발하였다. 특히, 소결장비인 발열체 및 소결로의 수명단축도 야기시켰으며, 제조단가도 상승하게 되는 단점이 있었다.In addition, in order to improve the above-mentioned difficulties, a thermal compression method, a HIP method (hot isostatatic pressing), or a sintering method of heating up to a high temperature of 1900 ° C. has been applied. In addition, there have been methods of adding various sintering additives. For example, one small commando No. 62-45194, JP-yl, etc. The cattle No. 56-63870 and JP-day bovine 62-153159 discloses the addition of Y 2 O 3 to improve the sintering property, one small-Open No. 62-32151 No. Dy 2 O 3 was used to sinter by adding MgO as a sintering aid. However, since the thermal compression method produces a sintered body by uniaxial pressurization, there are many limitations in diversifying the sintered body shape, and there are disadvantages in that processing costs are high to manufacture various shapes. In addition, the production of sintered body by the method of rapidly rising to high temperature is abrasion and toughness as the sintered body is bent or the microstructure of the sintered body is coarsened due to the cracks on the surface of the sintered body due to the thermal shock caused by the rapid temperature rise or the sintering temperature is high Deterioration such as degradation was caused. In particular, it also caused a shortening of the life of the heating element and the sintering furnace sintering equipment, there was a disadvantage that the manufacturing cost is also increased.
한편, Y2O3나 Dy2O3, MgO 등을 첨가하는 소결체 제조방법에서는 Y2O3, Dy2O3및 MgO 등이 Al2O3와 반응하여 쉽게 취약특성을 드러내거나 절삭시 열화온도를 낮추는 액상을 만들거나, 절삭공구에 나쁜 영향을 주는 열팽창계수가 다른 3Y2O3·5Al2O3고용체인 YAG(yttrium aluminium garnet)등 제2상의 광물들이 결정입자 사이에 생성되어 고속절삭시 발생하는 열충격에 의해 깨어지는 취약특성을 갖고 있었다.On the other hand, in the sintered body manufacturing method to which Y 2 O 3 , Dy 2 O 3 , MgO, etc. are added, Y 2 O 3 , Dy 2 O 3 and MgO, etc. react with Al 2 O 3 to easily show fragile characteristics or deteriorate during cutting. 2nd phase minerals are created between the crystal grains, such as 3Y 2 O 3 · 5Al 2 O 3 solid solution, which produces a liquid that lowers the temperature or has a different coefficient of thermal expansion, which adversely affects the cutting tool. It had a fragile property that was broken by the thermal shock that occurred during the operation.
이에 본 발명에서는 상기와 같은 품질변동이 적으면서도 소결온도 저하 및 치밀한 소결체를 얻는 방법에 대해 예의 연구한 결과, TiC 분말을 첨가하는 대신 TiC와 유사한 TiO2와 WC를 일정비율로 첨가하여 소결중에 TiCx로 변화되게 함으로써 소결성을 더욱 향상시켜 절삭공구의 기계적 요구특성에 나쁜 영향을 주게 되는 결정입자의 조대화를 방지할 수 있으며, 소결성도 증가시키면서 최종 소결체에서 치밀한 Al2O2-TiCx계(x=0.7 내지 0.9)가 될 수 있도록 하는 Al2O2-TiC는 절삭공구 소결체의 제조방법을 제공하는데 그 목적이 있는 것이다.Therefore, in the present invention, as a result of intensive sintering temperature reduction and a method of obtaining a compact sintered body with little quality fluctuations as described above, instead of adding TiC powder, TiO 2 and WC similar to TiC are added at a constant rate, and TiC during sintering. By changing to x , the sinterability can be further improved to prevent coarsening of crystal grains, which adversely affect the mechanical properties of the cutting tool, and the dense Al 2 O 2 -TiC x system ( Al 2 O 2 -TiC to be x = 0.7 to 0.9) is to provide a method for producing a cutting tool sintered object is to.
이하, 본 발명을 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in detail.
본 발명은 Al2O3: TiC : TiO2: WC가 20 내지 80 : 1 내지 30 : 1 내지 10중량%로 이루어진 소결체 원료혼합물을 Ar 가스분위기하에서 1600 내지 1700℃의 낮은 온도에서 소결하고 HIP 처리하여 Al2O2-TiCx계(x=0.7 내지 0.9)계가 치밀한 Al2O3-TiCx계 절삭공구 소결체의 제조방법인 것이다.In the present invention, a sintered body raw material mixture composed of Al 2 O 3 : TiC: TiO 2 : WC is 20 to 80: 1 to 30: 1 to 10% by weight under sintering under Ar gas atmosphere at a low temperature of 1600 to 1700 ° C. and HIP treatment. The Al 2 O 2 -TiC x system (x = 0.7 to 0.9) system is a method for producing a compact Al 2 O 3 -TiC x system cutting tool sintered body.
이하 본 발명을 더욱 상세히 설명하면 다음과 같다.Hereinafter, the present invention will be described in more detail.
본 발명은 Al2O3-TiC간의 반응성을 향상시키기 위해서 TiC 분말을 첨가하는 대신 TiC와 유사한 TiO2와 WC를 일정비율로 첨가하여 소결중에 TiCx(x=0.7 내지 0.9)로 변화되도록 하였고, 또, 통상적으로 알려진 MgO 및 Y2O3등의 소결보조제를 첨가하며, 소결도중에 제2의 광물이 생성되는 것을 방지하기 위해서 제2광물생성 억제제인 ZrO2, Mo2C를 0.1 내지 5중량% 첨가하여 YAG 등의 광물생성이 방지되도록 하므로써 고속절삭시에 발생되는 열충격에 견딜 수 있는 내열충격성이 향상된 Al2O3-TiCx계 절삭공구 소결체를 제조하는 방법인 것이다.In order to improve the reactivity between Al 2 O 3 -TiC, instead of adding TiC powder, TiC 2 and WC similar to TiC were added at a constant rate to change TiC x (x = 0.7 to 0.9) during sintering. In addition, conventionally known sintering aids such as MgO and Y 2 O 3 is added, and 0.1 to 5% by weight of ZrO 2 and Mo 2 C, which are second mineral formation inhibitors, in order to prevent the formation of a second mineral during sintering. It is a method of manufacturing an Al 2 O 3 -TiC x -based cutting tool sintered body having improved thermal shock resistance that can withstand thermal shock generated during high-speed cutting by adding minerals such as YAG by preventing addition.
일반적으로 알려진 Al2O3-TiC의 계면반응은 다음과 같이 나타낼 수 있다.Generally known interfacial reaction of Al 2 O 3 -TiC can be expressed as follows.
Al2O3(S)+TiC+2C(S)=Al2O(g)+2CO(g)Al 2 O 3 (S) + TiC + 2C (S) = Al 2 O (g) + 2CO (g)
Al2O3(S)+TiC(S)=Al2O(g)+TiO(S)+CO(g)Al 2 O 3 (S) + TiC (S) = Al 2 O (g) + TiO (S) + CO (g)
Al2O3(S)+2/3 TiC(S)=Al2O(g)+2/3 TiO2(S)+2/3 CO(g)Al 2 O 3 (S) +2/3 TiC (S) = Al 2 O (g) +2/3 TiO 2 (S) +2/3 CO (g)
Al2O3(S)+C(S)=Al2O2(g)+CO(g)Al 2 O 3 (S) + C (S) = Al 2 O 2 (g) + CO (g)
Al2O3(S)+C(S)=2Al2O(g)+CO(g)Al 2 O 3 (S) + C (S) = 2Al 2 O (g) + CO (g)
여기서 (S)는 고체상, (g)는 기체상을 의미한다.Here, (S) means a solid phase and (g) means a gas phase.
상기 반응식에서 가스를 발생시키는 주물질은 Al2O3와 TiC 또는 그라파이트로의 사용시 발생되는 유리탄소이며, 이때 소결온도가 높을수록 반응성이 향상되어 가스량이 증가하게 된다.The main material generating gas in the above reaction formula is glass carbon generated when Al 2 O 3 and TiC or graphite are used. In this case, the higher the sintering temperature, the higher the reactivity, and the amount of gas increases.
이렇게 가스발생량이 증가하게 되면 세라믹 소결체 내부에 기공이 많아지게 되어 기계적 특성이 저하되므로, 본 발명에서는 가스발생 생성요인중의 하나인 TiC의 첨가량을 종래의 40 내지 80중량%이던 것을 10 내지 30중량%로 낮추어 가스발생량을 종전의 1/3수준으로 감소시켰다.When the gas generation amount is increased in this way, since the pores increase in the ceramic sintered body and the mechanical properties are deteriorated, in the present invention, the addition amount of TiC, which is one of the gas generation generation factors, is 40 to 80% by weight of 10 to 30% by weight. By lowering to%, the gas generation was reduced to the previous level.
그리고 소결온도를 낮추어 가스발생량을 줄이고자 통상 알려진 MgO, Y2O3를 0.1 내지 5중량%로 첨가하였고 여기에 Al2O3와 TiC의 계면반응을 촉진시키는 TiO2를 TiC대신 1 내지 30중량%로 첨가하여 소결온도를 더욱 낮추었으므로 그 결과 내열충격성, 인성 및 기계적 강도가 우수한 치밀한 Al2O2-TiCx계(x=0.7 내지 0.9) 소결체를 얻을 수 있었다.In order to reduce the amount of gas generated by lowering the sintering temperature, conventionally known MgO and Y 2 O 3 were added at 0.1 to 5% by weight, and TiO 2 , which promotes the interfacial reaction between Al 2 O 3 and TiC, was 1 to 30% instead of TiC. Since the sintering temperature was further lowered by adding%, the result was a compact Al 2 O 2 -TiC x system (x = 0.7 to 0.9) sintered body having excellent thermal shock resistance, toughness and mechanical strength.
또한, 여기에 WC를 1 내지 10중량%로 첨가하여 소결시 TiO2와 반응시켜 고온에서 일정한 TiCx(x=0.7 내지 0.9) 결정을 생성하게 함으로써 종전의 Al2O3-TiCx계의 단점인 고속절삭시 발생하는 약 1200 내지 1300℃의 고열에 의해 깨지던 것을 개선하여 내열충격성을 향상시켜 수명을 약 30% 이상 연장시켰다. 그리고, 종전 Al2O3-TiCx계의 단점중 YAG 등의 제2의 광물생성에 의해 내열충격성이 급격히 저하되는 것을 방지하기 위해서 본 발명에서는 ZrO2, Mo2C를 0.1 내지 5중량% 첨가하여 제2광물의 생성을 억제함으로써 내열충격성과 내열마모성을 더욱 향상시켰다.In addition, WC is added in an amount of 1 to 10% by weight to react with TiO 2 during sintering to produce a constant TiC x (x = 0.7 to 0.9) crystal at a high temperature, which is a disadvantage of the conventional Al 2 O 3 -TiC x system. Phosphorus was improved by cracking due to high temperature of about 1200 to 1300 ° C. generated during high-speed cutting, thereby improving thermal shock resistance and extending the life by about 30% or more. In addition, in order to prevent the thermal shock resistance from dropping rapidly due to the second mineral generation such as YAG among the disadvantages of the conventional Al 2 O 3 -TiC x system, 0.1 to 5 wt% of ZrO 2 and Mo 2 C are added. By further suppressing the formation of the second mineral, the thermal shock resistance and the thermal wear resistance were further improved.
또한, 첨가되어 TiCx로 전이하고 남아 있는 TiO2는 Al2O3와 TiCx와의 결합도를 향상시키고, 미량의 Y2O3, ZrO2, Mo2C, WC가 기계적 특성 즉, 인성, 기계적 강도, 내마모성 및 열적충격성 등의 상승효과를 나타내게 된다.In addition, TiO 2 , which is added and transitioned to TiC x , enhances the bonding between Al 2 O 3 and TiC x , and trace amounts of Y 2 O 3 , ZrO 2 , Mo 2 C, and WC are mechanical properties, that is, toughness, It shows synergistic effects such as mechanical strength, wear resistance and thermal shock resistance.
이와 같은 본 발명의 효과로 절삭공구용 소결체의 내칩(chipping)성이 대폭 향상되었고, 고속절삭시 야기되는 피삭체와의 마찰력을 WC가 WO로 전이되면서 감소시키고, 열적 충격도 완화시켜 고온윤활 특성을 나타내는 우수한 고속 절삭용 공구재료로 사용가능하게 되었다.As a result of the present invention, the chipping resistance of the sintered compact for cutting tools is greatly improved, and the frictional force with the workpiece, which is caused during high-speed cutting, is reduced as WC is transferred to WO, and the thermal shock is also alleviated so that the high temperature lubrication characteristic It can be used as an excellent high speed cutting tool material.
본 발명의 소결체에 인성을 더욱 증진시키기 위해서는 일특공 소 56-9473호 일특개 소 51-5214호 등에서 첨가사용한 Mo와 NiO 등을 첨가사용하면 좋다. 이는 Mo와 NiO가 결정입자 성장을 억제하는 역할을 하는데 일반적으로 기계적 특성이 결정입자 크기에 반비례하기 때문이다. 또한, 상기 조성에 Co, Fe, Ni 및 이들의 산화물을 소량 첨가시켜도 소결특성 등이 향상됨을 알 수 있다.In order to further improve the toughness of the sintered compact of the present invention, Mo and NiO, etc. added in Japanese Patent Application Laid-Open No. 56-9473 and Japanese Patent Application Laid-Open No. 51-5214 may be used. This is because Mo and NiO play a role in inhibiting grain growth because mechanical properties are generally inversely proportional to grain size. In addition, it can be seen that even when a small amount of Co, Fe, Ni and oxides thereof are added to the composition, the sintering characteristics and the like are improved.
한편, 본 발명의 조성물의 입자크기가 미세함과 동시에 충분히 이론밀도에 도달하는 치밀한 소결체를 얻기 위해 소결 후 HIP를 실시하였다. 이때 HIP의 조건은 Ar 가스분위기하에서 1500 내지 2000㎫, 1400 내지 1700℃에서 20 내지 60분정도 실시하였다. 이때, HIP 처리전에 소결체의 밀도는 95% TD(true density) 이상 되도록 하였으며, 그 후 HIP 처리를 통하여 100% TD에 도달하는 치밀한 소결체를 얻을 수 있었다.On the other hand, HIP was performed after sintering in order to obtain a dense sintered body in which the particle size of the composition of the present invention was fine and reached a sufficient theoretical density. At this time, the conditions of HIP were performed at 1500 to 2000 MPa and 1400 to 1700 ° C. for about 20 to 60 minutes under Ar gas atmosphere. At this time, the density of the sintered body before the HIP treatment was to be 95% TD (true density) or more, and after that was obtained a dense sintered body reaching 100% TD through HIP treatment.
이와 같은 본 발명을 실시예에 의거 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail based on the embodiment as follows.
[실시예 1∼8]EXAMPLES 1-8
평균입경이 0.5 내지 1㎛인 각 원료분말들을 다음 표 1의 배합조성과 같이 Al2O3, TiC, TiO2, WC로 조합된 원료에 소결조제로 Y2O3, MgO, 제2광물억제제로 Mo2C, ZrO2를 각각 첨가한 것을 조합원료로 하였다.Y 2 O 3 , MgO, and second mineral inhibitors were sintered as raw materials in which each raw material powder having an average particle diameter of 0.5 to 1 μm was combined with Al 2 O 3 , TiC, TiO 2 , and WC, as shown in Table 1 below. As a combination raw material, Mo 2 C and ZrO 2 were respectively added.
이들 조합원료를 WC 보올과 단자를 사용하여 24시간 동안 균일하게 혼합하였다. 이때 혼합용매는 메탄올을 사용하였다. 혼합후 건조된 분말은 450㎏/㎠ 압력으로 성형체를 제조한 다음 성형체를 성형체와 동일조성의 분말속에 매몰시켜 Ar 가스 분위기에서 다음 표 1과 같은 낮은 온도에서 1시간 동안 소결시켜 Al2O3-TiCx계 소결체를 얻은 다음, HIP 처리하였다. HIP 처리된 시편은 빅커스 인덴터를 이용하여 Hv와 KIC를 측정하였으며, 절삭시험을 실시하였다. 피삭체는 하이크롬강(HRC 60)을 선택하였고, 직경은 304㎜ 롤을 사용하였다. 절삭조건은 RPM 170, 피이드(feed) 0.1㎜/rev., 깊이 0.5㎜로 하여 절삭수명이 다할 때까지 절삭특성을 살펴보았다.These combinations were uniformly mixed for 24 hours using WC bowls and terminals. In this case, methanol was used as the mixed solvent. By sintering for 1 hour at low temperature, such as the following table 1 and then mixing the dried powder was buried to a method of preparing a molded article by 450㎏ / ㎠ pressure and then formed body in the powder molded body with the same composition in an Ar gas atmosphere, Al 2 O 3 - A TiC x -based sintered body was obtained and then HIP treated. HIP treated specimens were measured for Hv and KIC using a Vickers indenter, and the cutting test was performed. The workpiece was selected from high chrome steel (HRC 60), and a diameter of 304 mm roll was used. The cutting conditions were RPM 170, feed 0.1 mm / rev, depth 0.5 mm, and the cutting characteristics were examined until the end of cutting life.
이때 공구의 수명은 공구의 과다마모 또는 깨짐현상에 의한 과다한 불꽃 등의 이상 절삭현상이 나올 때까지 피삭체의 길이방향 가공길이로 판단하였다.In this case, the tool life was determined as the length of the workpiece in the longitudinal direction until the abnormal cutting phenomenon such as excessive sparking caused by excessive wear or cracking of the tool emerged.
본 발명의 시험결과와 종래 제품과의 비교예를 표 1에 나타내었다.Table 1 shows a comparative example between the test results of the present invention and a conventional product.
이 실험결과로 알 수 있듯이 본 발명이 비교예보다 소결온도를 50 내지 100℃ 정도 낮출 수 있으며, 절삭수명인 절삭가공 길이가 30 내지 100% 향상되는 우수한 Al2O3-TiCx계 절삭공구임을 알 수 있었다.As can be seen from the experimental results, the present invention can lower the sintering temperature by 50 to 100 ° C. than the comparative example, and it is an excellent Al 2 O 3 -TiC x type cutting tool that has a cutting life of 30 to 100%. Could know.
[표 1]TABLE 1
Claims (3)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019900002361A KR920006806B1 (en) | 1990-02-24 | 1990-02-24 | Preparation method of calcined body made by al2o3-ticx |
| JP2288612A JPH03247555A (en) | 1990-02-24 | 1990-10-29 | Manufacture of al3o3-ticx sintered body for cutting rool |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1019900002361A KR920006806B1 (en) | 1990-02-24 | 1990-02-24 | Preparation method of calcined body made by al2o3-ticx |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR910015508A KR910015508A (en) | 1991-09-30 |
| KR920006806B1 true KR920006806B1 (en) | 1992-08-20 |
Family
ID=19296388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1019900002361A KR920006806B1 (en) | 1990-02-24 | 1990-02-24 | Preparation method of calcined body made by al2o3-ticx |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH03247555A (en) |
| KR (1) | KR920006806B1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485425A (en) * | 2019-01-04 | 2019-03-19 | 燕山大学 | A kind of tungsten carbide composite and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5314568A (en) * | 1976-07-26 | 1978-02-09 | Hitachi Ltd | Photolithography treatment system device |
| JPS6041017B2 (en) * | 1978-06-13 | 1985-09-13 | 日本特殊陶業株式会社 | Ceramic sintered body for cutting tools and its manufacturing method |
| US4396724A (en) * | 1981-05-26 | 1983-08-02 | General Electric Co. | Ceramic composition |
| JPS58185477A (en) * | 1982-04-21 | 1983-10-29 | 三菱マテリアル株式会社 | High speed cutting ceramic for cutting tool |
-
1990
- 1990-02-24 KR KR1019900002361A patent/KR920006806B1/en not_active IP Right Cessation
- 1990-10-29 JP JP2288612A patent/JPH03247555A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109485425A (en) * | 2019-01-04 | 2019-03-19 | 燕山大学 | A kind of tungsten carbide composite and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH03247555A (en) | 1991-11-05 |
| KR910015508A (en) | 1991-09-30 |
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