KR100489066B1 - Ni-Cr based metal powder composition for laser cladding and preparation method for valve sheet by using them - Google Patents
Ni-Cr based metal powder composition for laser cladding and preparation method for valve sheet by using them Download PDFInfo
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- KR100489066B1 KR100489066B1 KR10-2002-0043216A KR20020043216A KR100489066B1 KR 100489066 B1 KR100489066 B1 KR 100489066B1 KR 20020043216 A KR20020043216 A KR 20020043216A KR 100489066 B1 KR100489066 B1 KR 100489066B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3033—Ni as the principal constituent
- B23K35/304—Ni as the principal constituent with Cr as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K26/00—Working by laser beam, e.g. welding, cutting or boring
- B23K26/20—Bonding
- B23K26/21—Bonding by welding
- B23K26/211—Bonding by welding with interposition of special material to facilitate connection of the parts
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Abstract
본 발명은 엔진 실린더 헤드 밸브 시트용 금속분말 조성물 및 이를 이용한 엔진 밸브 시트의 제조방법에 관한 것으로, 더욱 상세하게는, 니켈, 크롬, 망간 및 철이 함유되어 있는 금속분말 조성물을 사용하여 레이저 클래딩(laser cladding)공법으로 엔진 밸브 시트를 제조함으로서 고온에서 내마모성, 내열성 및 내식성이 우수하여 기존의 엔진보다 엔진성능 및 내구성이 우수한 엔진을 제조할 수 있다. The present invention relates to a metal powder composition for an engine cylinder head valve seat and a method of manufacturing an engine valve seat using the same, and more particularly, to a laser cladding using a metal powder composition containing nickel, chromium, manganese and iron. By manufacturing the engine valve seat by the cladding method, it is possible to manufacture an engine having better engine performance and durability than a conventional engine because of excellent wear resistance, heat resistance and corrosion resistance at high temperatures.
Description
본 발명은 엔진 실린더 헤드 밸브 시트용 금속 분말 조성물 및 이를 이용한 밸브 시트의 제조방법에 관한 것으로, 더욱 상세하게는 니켈, 크롬, 망간, 규소 및 철이 함유되어 있는 금속분말 조성물을 사용하여 레이저 클래딩(laser cladding)공법으로 엔진 밸브 시트를 제조함으로서 고온에서 내마모성, 내열성 및 내식성이 우수하여 기존의 엔진보다 엔진성능 및 내구성이 우수한 엔진을 제조하는데 사용될 수 있다. The present invention relates to a metal powder composition for an engine cylinder head valve seat and a method for manufacturing a valve seat using the same, and more particularly, to a laser cladding using a metal powder composition containing nickel, chromium, manganese, silicon and iron. By manufacturing the engine valve seat by the cladding method, the wear resistance, heat resistance and corrosion resistance at high temperature can be used to produce an engine having better engine performance and durability than a conventional engine.
자동차의 엔진 실린더 헤드 밸브 시트는 흡, 배기 밸브의 개폐시 밸브와의 기밀성을 유지하여 연소실의 효율을 높이는 역할을 하게 되는데, 그 결과 엔진의 부품으로 밸브와의 접촉 및 마찰, 배기 가스에의 노출 등을 견뎌내어야 하기 때문에 약 400 ~ 700℃ 온도에 대한 내열성, 내마모성 및 내산화성이 요구된다.The engine cylinder head valve seat of the car maintains the airtightness with the valve when opening and closing the intake and exhaust valves, thereby increasing the efficiency of the combustion chamber. As a result, the parts of the engine are contacted with the valves, friction, and exposure to the exhaust gas. It is required to withstand the heat resistance, abrasion resistance and oxidation resistance to about 400 ~ 700 ℃ temperature is required.
밸브 시트에 관한 종래 기술로는 크게 밸브 시트링을 삽입하는 방법과 레이저 클래딩 공법에 의해 합금 분말을 헤드 밸브 부분에 직접 용융시켜 일체형 밸브 시트를 제조하는 방법이 있다.Conventionally related valve seats include a method of inserting a valve seat ring largely and a method of manufacturing an integrated valve seat by melting alloy powder directly to the head valve portion by a laser cladding method.
밸브 시트링을 삽입하는 방법은 연소실내 연소 전도율의 저하, 소재와 밸브시트간의 단열현상, 밸브시트의 냉각효율 저하 및 시트 링의 고온에서의 마모등의 단점이 있는 반면, 레이저 클래딩 공법에 의하는 경우에는 연소실내 연소 열전도율 향상, 소재와 시트간에 금속적 결합, 클래딩면 가공량 최소화로 인한 냉각수 경로의 근접설계 가능, 밸브 시트 냉각효율 향상 및 노킹 방지의 장점이 있으므로 엔진출력 및 토크의 향상을 가져오고 연비향상이 가능하다.The method of inserting the valve seat ring has disadvantages such as lower combustion conductivity in the combustion chamber, thermal insulation between the material and the valve seat, lower cooling efficiency of the valve seat, and wear at high temperatures of the seat ring. In this case, it is possible to improve the engine output and torque by improving the combustion thermal conductivity in the combustion chamber, the metallic coupling between the material and the seat, the close design of the coolant path by minimizing the amount of cladding surface, the improvement of the valve seat cooling efficiency, and the prevention of knocking. Fuel economy is possible.
종래 사용되는 레이저 클래딩(laser cladding)용 금속분말 조성물에는 구리를 기본성분으로 하는 구리합금 분말이 있으며 그 조성비율은 알루미늄 5.0 ~ 10.0중량%, 니켈 1.0 ~ 5.0 중량%, 철 1.0 ~ 4.0중량% 및 잔부가 구리인 분말 조성물과, 코발트 10 ~ 15중량%, 알루미늄 1.0 ~ 5.0중량%, 니켈 10 ~ 15중량%, 원소주기율표 Va족의 바나듐, 니오븀, 탄탈륨중의 1종 또는 2종이상 0.1 ~ 5.0중량%, 실리콘 1 ~ 5중량% 및 잔부가 구리인 분말 조성물, 코발트 10 ~ 15중량%, 알루미늄 1.0 ~ 5.0중량%, 철 4 ~ 8중량%, 니켈 10 ~ 15중량%, 원소주기율표 Va족의 바나듐, 니오븀, 탄탈륨 중의 1종 또는 2종이상 0.1 ~ 5.0중량%, 실리콘 1 ~ 5중량% 및 잔부가 구리인 분말 조성물등이 있다.Conventionally used metal powder compositions for laser cladding include copper alloy powder based on copper, and its composition ratio is 5.0 to 10.0 wt% aluminum, 1.0 to 5.0 wt% nickel, 1.0 to 4.0 wt% iron, and 10 to 15% by weight of cobalt, 1.0 to 5.0% by weight of aluminum, 10 to 15% by weight of nickel, one or two or more of vanadium, niobium and tantalum of the Periodic Table of the Element Va Powder composition with weight percent, silicon 1-5 weight percent and balance copper, 10-15 weight percent cobalt, 1.0-5.0 weight percent aluminum, 4-8 weight percent iron, 10-15 weight percent nickel, group Va of the Periodic Table of the Elements Vanadium, niobium, tantalum, and the like, or a powder composition of 0.1 to 5.0% by weight, silicon 1 to 5% by weight and the balance of copper.
상기한 구리계 금속분말 조성물들은 이산화탄소(CO2)레이저 클래딩에 적합하도록 최적화하여 개발된 분말로서 본원 발명에 사용된 Nd:YAG(이트륨-알루미늄 가닛)레이저를 이용한 용융에는 적합하지 않은바, Nd:YAG 레이저 용접에 적합한 금속분말 조성물의 필요성이 제기되어왔다.The above-described copper-based metal powder compositions are powders developed by optimizing for carbon dioxide (CO 2 ) laser cladding and are not suitable for melting using Nd: YAG (yttrium-aluminum garnet) laser used in the present invention. There has been a need for metal powder compositions suitable for YAG laser welding.
따라서, 본 발명의 목적은 자동차 엔진 밸브 시트를 제조하는데 있어서 종래 구리를 주성분으로 하는 CO2 레이저 클래딩용 금속분말보다는 Nd:YAG(이트륨-알루미늄 가닛)레이저 클래딩에 적합한 니켈 및 크롬을 주성분으로 하고 여기에 망간, 규소, 철등을 함유한 혼합 금속분말 조성물을 제공하고 이를 실린더 헤드의 홈에 주입하는 동시에 레이저를 주사하여 클래딩(cladding)함으로서 내열성, 내마모성 및 내부식성이 우수한 일체형 밸브시트를 제조하는 것이다.Accordingly, an object of the present invention is to produce nickel and chromium, which are suitable for Nd: YAG (yttrium-aluminum garnet) laser cladding, rather than metal powder for CO 2 laser cladding, which is conventionally made of copper, in the manufacture of automotive engine valve seats. The present invention provides a mixed metal powder composition containing manganese, silicon, iron, and the like, which is injected into a groove of a cylinder head, and simultaneously clad by scanning with a laser to produce an integrated valve seat having excellent heat resistance, abrasion resistance, and corrosion resistance.
상기 목적을 달성하기 위하여 본 발명은 고온에서도 우수한 기계적 성질을 가질 수 있으며 동시에 Nd:YAG 레이저 용접에 적합한 니켈-크롬계 금속분말 조성물을 제공한다.In order to achieve the above object, the present invention provides a nickel-chromium-based metal powder composition which can have excellent mechanical properties even at high temperatures and is suitable for Nd: YAG laser welding.
본 발명에서는 엔진 밸브 시트용 재료로 사용되는 금속분말 조성물을 제공하는데, 이들 조성물은 니켈(Ni), 크롬(Cr), 망간(Mn), 규소(Si), 철(Fe)분말을 혼합하여 이루어지는 것으로 YAG(이트륨-알루미늄 가닛)레이저에 의해 알루미늄 재질의 실린더 헤드 모재에 클래딩 된다.The present invention provides a metal powder composition to be used as a material for the engine valve seat, these compositions are made by mixing nickel (Ni), chromium (Cr), manganese (Mn), silicon (Si), iron (Fe) powder It is clad on an aluminum cylinder head base material by a YAG (yttrium-aluminum garnet) laser.
보다 상세하게는, 본 발명의 엔진 밸브 시트용 재료인 금속분말 조성물은 내부식성, 내열성 및 내마모성의 증가를 위해 니켈 36 ~ 40중량%, 크롬 15 ~ 19중량%, 망간 1 ~ 3중량%, 규소 1 ~ 3중량%, 철 40 ~ 45중량%으로 이루어진다.More specifically, the metal powder composition of the engine valve seat material of the present invention is 36 to 40% by weight of nickel, 15 to 19% by weight of chromium, 1 to 3% by weight of manganese, silicon to increase the corrosion resistance, heat resistance and wear resistance It consists of 1-3 wt% and 40-45 wt% iron.
상기 본 발명의 조성물중 니켈 성분은 내열성을 향상시켜 조직의 안정화를 가져오고 상기 성분이 부족할 경우 외부의 충격이나 열적 부하에 잘깨지는 성질을 갖는다. 따라서, 그 함유량을 36중량% 이하로 하면 외부 충격이나 열적 부하에 잘 깨지고, 40중량% 이상으로 하면 성능 대비 제조가격이 지나치게 비싸진다.크롬 성분은 내마모성이 우수해 코팅기능을 위해 첨가되며 윤활제의 역할을 한다. 상기 크롬 성분이 15중량% 이하이면 내마모성이 저하되고, 19중량% 이상이면 성능 대비 제조원가가 비싸지는 단점이 있다.망간 성분은 레이저 클래딩후에 밸브접촉면의 가공성(피삭성)향상을 위해 첨가하는데, 1중량% 이하이면 가공성 향상 효과가 매우 미미하고, 3중량% 이상이면 외부 충격에 잘 깨지므로 가공성은 향상되나 인성이 저하되므로, 망간 1 ~ 3중량%의 첨가가 바람직하다.철 성분은 내마모성를 증대하는 효과가 있으며, 40 ~ 45중량%에서 우수한 내마모성을 갖는다. 한편, 규소는 탈산제로서 결정입계에 편석입계 탄화물의 석출을 저지하고, 입계 산화층을 동시에 저감시키는 역할을 하는 것으로서, 1중량% 이하에서는 탈산효과가 매우 미미하고, 3중량% 이상에서는 입계에 편석되어 입계파괴의 원인이 된다.Nickel component in the composition of the present invention improves the heat resistance to bring about stabilization of the tissue and when the lack of the component has a property of being easily broken by external impact or thermal load. Therefore, when the content is less than 36% by weight, it is easily broken by external impact or thermal load, and when it is more than 40% by weight, the manufacturing price is too expensive compared to the performance. The chromium component is excellent in wear resistance and is added for the coating function. Play a role. If the chromium component is 15 wt% or less, wear resistance is lowered, and if the chromium component is 19 wt% or more, there is a disadvantage in that the manufacturing cost is high compared to the performance. If it is% or less, the effect of improving workability is very slight, and if it is 3% by weight or more, it is easily broken by external impact, so that the workability is improved, but toughness is lowered. Therefore, the addition of 1 to 3% by weight of manganese is preferred. There is, has excellent wear resistance at 40 to 45% by weight. On the other hand, silicon acts as a deoxidizer to prevent precipitation of segregated grain boundary carbides at the grain boundaries and to simultaneously reduce the grain boundary oxide layer. The deoxidation effect is very small at 1 wt% or less, and segregates at grain boundaries at 3 wt% or more. It can cause grain boundary destruction.
또한, 본 발명에서는 상기 금속분말 조성물을 이용하여 엔진 밸브 시트를 제조하는 방법을 제공한다.In addition, the present invention provides a method for producing an engine valve seat using the metal powder composition.
본 발명의 엔진 밸브 시트의 제조는 레이저 클래딩(laser cladding)공법에 의한 것으로서, 이는 에너지 밀도가 높은 특성을 갖는 레이저 빔을 조사하여 모재에 금속분말을 클래딩함으로써 엔진 헤드와 일체형으로 엔진 밸브시트를 제조하는 방법이다. 즉 상기의 혼합 금속분말을 알루미늄 재질의 실린더 헤드의 홈에 주입하고 여기에 레이저 빔을 조사하여, 모재에 금속분말이 클래딩되게 함으로써 엔진 헤드와 일체형의 엔진 밸브 시트를 제조한다.The manufacture of the engine valve seat of the present invention is by a laser cladding method, which produces an engine valve seat integrally with the engine head by cladding a metal powder on a base material by irradiating a laser beam having a high energy density characteristic. That's how. That is, the mixed metal powder is injected into the groove of the cylinder head made of aluminum, and the laser beam is irradiated thereon, so that the metal powder is clad on the base metal to produce an engine valve seat integral with the engine head.
본 발명의 엔진 밸브 시트의 제조는 종래의 CO2 레이저 대신 Nd:YAG레이저를 사용하는 방법을 제공한다.The manufacture of the engine valve seat of the present invention provides a method of using an Nd: YAG laser instead of a conventional CO 2 laser.
또한, 금속분말을 노즐을 통하여 엔진 밸브 시트 홈에 주입할 때 보호가스(shielding gas)를 공급하는데, 보호 가스는 금속분말의 이송을 원활하게 하며, 혼합 금속분말을 외부 공기로부터 차단하여 클래딩 가공시 금속분말이 산화되는 것을 방지하는 역할을 한다. 사용될 수 있는 보호가스로는 아르곤가스 또는 헬륨가스등이 있는데, 효율은 높으나 고가인 헬륨가스보다는 아르곤 가스가 주로 사용된다.In addition, when the metal powder is injected into the engine valve seat groove through the nozzle, a shielding gas is supplied. The protective gas facilitates the transfer of the metal powder, and blocks the mixed metal powder from the outside air to provide a cladding process. It serves to prevent the metal powder from oxidizing. Protective gases that can be used include argon gas or helium gas, argon gas is used rather than helium gas which is high in efficiency but expensive.
본 발명에서는 레이저 클래딩 가공에 사용되는 통상적인 장치를 제공하며, 그 일예를 도시하였는바, 이를 보다 상세히 설명하면 다음과 같다.The present invention provides a conventional apparatus used for laser cladding processing, an example thereof is illustrated, which will be described in more detail as follows.
도 1에 의하면, 레이저 클래딩 장치는 금속분말을 저장하고 소정 장소로 공급하는 혼합 금속분말 호퍼(4), 상기 혼합 금속분말 호퍼(4)에 공급된 금속분말을 실린더 헤드의 밸브시트 가공 위치로 공급하는 노즐(5), 이때 스쿠류(3)는 혼합 금속분말 호퍼(4)의 금속분말을 보호가스 공급호퍼(8)로 이송, 공급하며, 보호가스 공급호퍼(8)는 별도의 보호가스 주입수단에 의해 상부로부터 주입되는 보호가스와 상기 공급된 금속분말을 혼합하여 저장함으로서 금속분말의 이송을 원활하게 한다.According to Fig. 1, the laser cladding device supplies a mixed metal powder hopper 4 for storing and supplying a metal powder to a predetermined place, and supplying the metal powder supplied to the mixed metal powder hopper 4 to a valve seat processing position of the cylinder head. The nozzle 5, wherein the screw (3) transfers and supplies the metal powder of the mixed metal powder hopper (4) to the protective gas supply hopper (8), the protective gas supply hopper (8) is a separate protective gas injection means By mixing and storing the protective gas injected from the upper side and the supplied metal powder to facilitate the transfer of the metal powder.
보호가스 공급호퍼와 연통된 노즐(5)을 실린더 헤드의 밸브시트 가공위치로 조준하여 보호가스와 혼합된 금속분말을 배출하는데, 이 때 별도의 보호가스 공급수단인 보호가스 공급용 노즐(15)로부터 보호가스가 공급되어 배출되는 금속분말이 외부공기와 접촉하는 것을 차단하여 금속분말의 산화를 방지한다.Aim the nozzle (5) in communication with the protective gas supply hopper to the valve seat processing position of the cylinder head to discharge the metal powder mixed with the protective gas, wherein the protective gas supply nozzle (15) as a separate protective gas supply means Prevents the oxidation of the metal powder by preventing the metal powder from being supplied from the protective gas from coming into contact with external air.
이렇게 금속분말이 밸브시트 가공위치로 배출되는 과정에서, 레이저 공급원으로부터 투사되는 레이저 빔(7)을 반사미러(6)을 이용하여 상기 가공위치로 배출되는 금속분말을 조사하게 된다. 이 때 금속분말은 조사되는 레이저 빔(7)에 의해 클래딩된다.In the process of discharging the metal powder to the valve seat processing position, the metal powder discharged to the processing position is irradiated using the reflection mirror 6 with the laser beam 7 projected from the laser source. At this time, the metal powder is clad by the laser beam 7 irradiated.
이하 실시예에 의하여 본 발명을 자세히 설명한다. 단 하기의 실시예는 본 발명을 예시하는 것일 뿐, 본 발명이 실시예에 의하여 한정되는 것은 아니다.The present invention will be described in detail by the following examples. However, the following examples are merely to illustrate the present invention, the present invention is not limited by the examples.
니켈 38중량%, 크롬 17중량%, 망간 1중량%, 규소 1중량%, 철 43중량%의 함량비로 혼합 금속분말을 제조한 다음, 상기의 혼합 금속분말을 3.5KW 출력의 레이저 빔을 조사하여 정육면체의 알루미늄 재질에 밸브부분을 성형한 모재에 클래딩하였다. 보호가스로는 아르곤 가스를 사용하였다.The mixed metal powder was prepared in a content ratio of 38% by weight of nickel, 17% by weight of chromium, 1% by weight of manganese, 1% by weight of silicon, and 43% by weight of iron, and then the mixed metal powder was irradiated with a laser beam of 3.5KW output. The cladding was carried out on the base material formed by forming a valve part in an aluminum material of a cube. Argon gas was used as the protective gas.
상기한 방법으로 클래딩을 제조한 후 밸브를 체결하여 단체 마모시험을 실시하였다.After the cladding was manufactured by the above method, the valves were tightened to perform a single wear test.
상기한 레이저 클래딩에 따라 제조된 클래딩 층은 그 깊이가 1.0 ~ 1.2mm 으로 측정되었다. 클래딩 층의 경도는 300 ~ 400Hv 임을 확인하였다.The cladding layer prepared according to the above laser cladding had a depth of 1.0 to 1.2 mm. The hardness of the cladding layer was found to be 300 ~ 400Hv.
이상에서 살펴본 바와 같이, 본 발명에서는 니켈 및 크롬을 주성분으로하고 망간, 규소 및 철이 함유되어 있는 밸브시트 합금 조성물을 Nd:YAG 레이저 클래딩가공법에 의해 내마모성 및 내열성이 우수한 밸브 시트를 제조하였다. 레이저 클래딩은 에너지 밀도가 높은 레이저 빔의 특성을 이용한 기술로서 모재와 클래드층과의 접합이 매우 우수하여 접합강도가 높고 기존의 기술보다 단시간에 가공 생산할 수 있다는 장점이 있다. As described above, in the present invention, a valve seat alloy composition containing nickel and chromium as a main component, and containing manganese, silicon, and iron, was manufactured by Nd: YAG laser cladding processing to produce a valve seat having excellent wear resistance and heat resistance. Laser cladding is a technology that uses the characteristics of the laser beam with high energy density, and the bonding between the base material and the cladding layer is very excellent, and thus the bonding strength is high and the processing can be produced in a shorter time than the existing technology.
도 1은 본 발명의 레이저 클래딩 장치로 엔진 밸브 시트를 제조하는 방법의 일예를 나타내는 개략도이고, 1 is a schematic view showing an example of a method for manufacturing an engine valve seat with the laser cladding device of the present invention,
도 2는 본 발명의 레이저 클래딩 장치로 엔진 밸브 시트를 제조하는 방법의 일예를 나타내는 사시도이다.2 is a perspective view showing an example of a method of manufacturing an engine valve seat with the laser cladding device of the present invention.
1 : 가공 테이블(work table) 2 : 엔진 블록(engine block)1: work table 2: engine block
3 : 스크류 컨베어(screw conveyor) 4 : 호퍼(hopper)3: screw conveyor 4: hopper
5 : 노즐(nozzle) 6 : 반사미러(reflect mirror)5: Nozzle 6: Reflective Mirror
7 : 레이저 빔(laser beam) 8 : 보호가스 공급 호퍼7: laser beam 8: protective gas supply hopper
9 : 혼합 금속 분말 12 : 엔진 밸브 시트 홈9: mixed metal powder 12: engine valve seat groove
13 : 레이저 클래딩에 의한 엔진 밸브 시트13: engine valve seat by laser cladding
15 : 보호가스 공급용 노즐 (nozzle for shielding gas)15: nozzle for shielding gas
Claims (3)
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| US8733422B2 (en) | 2012-03-26 | 2014-05-27 | Apple Inc. | Laser cladding surface treatments |
| US10856443B2 (en) | 2018-06-06 | 2020-12-01 | Apple Inc. | Cladded metal structures for dissipation of heat in a portable electronic device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07109539A (en) * | 1993-08-19 | 1995-04-25 | Hitachi Metals Ltd | Fe-ni-cr-based superalloy, engine valve and knit mesh for exhaust gas catalyst |
| JPH11199987A (en) * | 1997-11-10 | 1999-07-27 | Hitachi Metals Ltd | Heat resistant alloy suitable for cold working |
| KR100267709B1 (en) * | 1997-12-09 | 2000-10-16 | 노건일 | A metal composition for engine valve seat, a method for manufacturing it, and an apparatus therefor |
| JP2001131770A (en) * | 1999-11-08 | 2001-05-15 | Nippon Parkerizing Co Ltd | Element wire for engine valve |
| KR20020019296A (en) * | 2000-09-05 | 2002-03-12 | 이계안 | Sintered alloy for valve seat manufactured by laser cladding |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH07109539A (en) * | 1993-08-19 | 1995-04-25 | Hitachi Metals Ltd | Fe-ni-cr-based superalloy, engine valve and knit mesh for exhaust gas catalyst |
| JPH11199987A (en) * | 1997-11-10 | 1999-07-27 | Hitachi Metals Ltd | Heat resistant alloy suitable for cold working |
| KR100267709B1 (en) * | 1997-12-09 | 2000-10-16 | 노건일 | A metal composition for engine valve seat, a method for manufacturing it, and an apparatus therefor |
| JP2001131770A (en) * | 1999-11-08 | 2001-05-15 | Nippon Parkerizing Co Ltd | Element wire for engine valve |
| KR20020019296A (en) * | 2000-09-05 | 2002-03-12 | 이계안 | Sintered alloy for valve seat manufactured by laser cladding |
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