KR20020096921A - An abrasion-resistant thermal-sprayed coating for a sliding member - Google Patents

An abrasion-resistant thermal-sprayed coating for a sliding member Download PDF

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KR20020096921A
KR20020096921A KR1020020033280A KR20020033280A KR20020096921A KR 20020096921 A KR20020096921 A KR 20020096921A KR 1020020033280 A KR1020020033280 A KR 1020020033280A KR 20020033280 A KR20020033280 A KR 20020033280A KR 20020096921 A KR20020096921 A KR 20020096921A
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metal
solid lubricant
sliding member
wear
coated
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KR1020020033280A
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KR100501985B1 (en
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아마노히데끼
오미야다까오
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닛뽕 피스톤 링 가부시끼가이샤
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/067—Metallic material containing free particles of non-metal elements, e.g. carbon, silicon, boron, phosphorus or arsenic
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F5/00—Piston rings, e.g. associated with piston crown
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16J—PISTONS; CYLINDERS; SEALINGS
    • F16J9/00—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction
    • F16J9/26—Piston-rings, e.g. non-metallic piston-rings, seats therefor; Ring sealings of similar construction characterised by the use of particular materials

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)

Abstract

PURPOSE: Provided is a wear-resistant sprayed coating film having no possibility of causing embrittlement and reduction in oil retentivity and formed on the sliding surface of a sliding member, such as piston ring and cylinder. CONSTITUTION: A sprayed coating film(3) is obtained by using a powder mixture consisting of powder of a hard material(5), powder of a metal constituting a matrix(6), and particles of a metal-coated solid lubricant and plasma spraying it onto the sliding surface of the sliding member. In the sprayed coating film(3), copper-coated graphite particles(4) are used as the powder of the metal-coated solid lubricant and the content of the copper-coated graphite particles(4) is made to 0.1 to 10 mass%.

Description

미끄럼 부재용 내마모성 용사피막{AN ABRASION-RESISTANT THERMAL-SPRAYED COATING FOR A SLIDING MEMBER}Abrasion resistant thermal spray coating for sliding members {AN ABRASION-RESISTANT THERMAL-SPRAYED COATING FOR A SLIDING MEMBER}

본 발명은 내연기관의 피스톤 링, 실린더 라이너등의, 미끄럼 부재용 내마모성 용사피막에 관한 것이다.TECHNICAL FIELD This invention relates to the wear-resistant thermal spray coating for sliding members, such as a piston ring and a cylinder liner of an internal combustion engine.

알려진 것처럼, 내연기관용 미끄럼부재의 미끄럼면을 피복하는 내마모성 용사피막은, 세라믹등의 경질재료 분말, 몰리브덴등의 매트릭스를 형성하는 금속분말, 그리고 플루오르화 칼슘등의 고체윤활제 분말을 함유하는 혼합물을 상기 미끄럼부재의 미끄럼면상에 용사함으로써 형성된다.As is known, the wear-resistant thermal spray coating covering the sliding surface of the sliding member for an internal combustion engine comprises a mixture containing a hard material powder such as ceramic, a metal powder forming a matrix such as molybdenum, and a solid lubricant powder such as calcium fluoride. It is formed by thermal spraying on the sliding surface of the sliding member.

용사피막은 일본 특허공개공보 제 08-253877 호를 통해 공지되어 있으며, 상기 공보에서 피막은, 고체윤활제로서 금속피복흑연입자를 피막혼합물의 10 내지 20 질량%로 사용한다. 이렇게 공지된 용사피막은 입도분석 -88+44 ㎛ 값으로 특징되는 크기분포를 갖는 흑연입자를 가지며, 상기 피막혼합물에 피복금속으로서의 니켈을 약 75 질량%, 그리고 고체윤활제로서의 흑연을 약 25 질량% 함유하고 있다.A thermal spray coating is known from Japanese Patent Application Laid-Open No. 08-253877, wherein the coating uses 10 to 20% by mass of metal-coated graphite particles as a solid lubricant. The known thermal spray coatings have graphite particles having a size distribution characterized by a particle size analysis of -88 + 44 μm, wherein the coating mixture contains about 75 mass% of nickel as a coating metal and about 25 mass% of graphite as a solid lubricant. It contains.

무피복 흑연입자 대신에 금속피복 흑연입자를 사용하면, 용사공정시 흑연의 산화 및 분해문제는 해소되지만, 금속피복 흑연을 다량으로 사용한 내마모성 용사피막은, 그 사용에 의해 얻어지는 마찰계수의 감소효과에 비해 용사피막 강도의 감소가 극히 크다는 점에서 사용상의 결점을 갖고 있다. 더욱이, 고속산소화염(HVOF)용사를 사용하는 경우, 피막의 다공율이 5체적% 미만이 되어 보유성(保油性)이 불량하다는 다른 결점이 있다.If metal-coated graphite particles are used in place of uncoated graphite particles, the problem of oxidation and decomposition of graphite in the thermal spraying process will be solved. Compared to the above, the thermal spray coating has a significant decrease in the strength of the spray coating. Moreover, when using a high-speed oxygen flame (HVOF) spray, there is another drawback that the film has a porosity of less than 5% by volume, resulting in poor retention.

본 발명은 이러한 문제들을 해결하고자 만들어 졌다. 그래서 본 발명의 목적은, 경질재료로서의 세라믹 분말, 매트릭스를 형성하는 금속분말, 및 고체윤활제 분말로서의 금속피복 고체윤활제 입자로 구성된 혼합물을, 내연기관의 피스톤링과 실린더 라이너등의 미끄럼부재의 미끄럼면상에 용사하여 형성되는 내마모성 용사피막으로서, 취성에 민감하지도 않고 보유성도 불량하지 않은 내마모성 용사피막을 제공하는 것이다.The present invention has been made to solve these problems. Accordingly, an object of the present invention is to provide a mixture composed of ceramic powder as a hard material, metal powder to form a matrix, and metal-coated solid lubricant particles as a solid lubricant powder, on a sliding surface of a sliding member such as a piston ring and a cylinder liner of an internal combustion engine. It is a wear-resistant thermal spray coating formed by thermal spraying on a non-sensitive brittle and poor retention.

도 1 은 본 발명의 실시형태에 따라 형성된 용사피막을 갖는 피스톤링의 부분확대 단면도이다.1 is a partially enlarged cross-sectional view of a piston ring having a thermal spray coating formed according to an embodiment of the present invention.

도 2 는 평면미끄럼 마찰마모의 시험에 사용되는 회전식 시험기의 대략도이다.2 is a schematic view of a rotary tester used in the testing of planar sliding frictional wear.

도면 부호의 설명Explanation of reference numerals

1:피스톤링2:모재1: Piston ring 2: Base material

3:용사피막4:구리피복 흑연입자3: spray coating 4: copper coated graphite particles

5:경질재료 입자6:매트릭스5: hard material particle 6: matrix

11:시편12:상대물Psalms 12: Psalms 12

P:면압P: Surface pressure

상술한 목적을 달성하기 위해, 본 발명은 경질재료 분말, 매트릭스를 형성하는 금속분말, 및 금속피복 고체윤활제의 분말로 구성된 혼합물을 미끄럼부재의 미끄럼면상에 용사하여 형성되는 미끄럼부재용 내마모성 용사피막을 제공하되, 상기 피막혼합물이 0.1 내지 10 질량% 미만의 한정된 범위내에서 금속피복 고체윤활제 입자를 포함하도록 한다.In order to achieve the above object, the present invention provides a wear-resistant spray coating for a sliding member formed by spraying a mixture composed of a hard material powder, a metal powder forming a matrix, and a powder of a metal-coated solid lubricant on a sliding surface of the sliding member. Provided, wherein the coating mixture comprises less than 0.1 to less than 10% by mass of metallized solid lubricant particles.

금속피복 고체윤활제 입자의 함량을 상기와 같이 한정한 이유는, 0.1 질량% 미만인 경우에는, 윤활효과가 충분하지 못하고, 10 질량% 이상인 경우에는, 피막이 취약하고 마찰계수의 개선효과가 적기 때문이다. 윤활효과를 향상시키기 위해서는, 1 질량% 이상으로 조절하는 것이 바람직하다. 또한, 피막강도의 관점에서는 8 질량% 이하로 조절하는 것이 바람직하다.The reason for limiting the content of the metal-coated solid lubricant particles as described above is that when less than 0.1% by mass, the lubricating effect is insufficient, and when it is 10% by mass or more, the coating is weak and the effect of improving the coefficient of friction is small. In order to improve a lubricating effect, it is preferable to adjust to 1 mass% or more. Moreover, it is preferable to adjust to 8 mass% or less from a viewpoint of film strength.

또한, 본 발명에 따르면, 상기 금속피복 고체윤활제 입자들은 금속피복 흑연입자의 10 내지 50 질량% 의 한정된 범위내에서 고체 윤활제를 함유한다. 그 이유는, 10 질량% 미만인 경우에는, 윤활효과가 충분하지 않으며, 50 질량% 를 초과하는 경우에는, 용사할 때 고체윤활제 입자의 잔여량이 감소되어, 그 결과 상기 미끄럼부재의 상대물(counterpart)의 마모량이 증가하기 때문이다.Further, according to the present invention, the metallized solid lubricant particles contain a solid lubricant within a limited range of 10 to 50% by mass of the metallized graphite particles. The reason is that when less than 10% by mass, the lubricating effect is not sufficient, and when it exceeds 50% by mass, the residual amount of solid lubricant particles when sprayed is reduced, resulting in a counterpart of the sliding member. This is because the wear amount of the is increased.

본 발명에 따른 피막혼합물에 사용된 고체윤활제 입자는 흑연(C), 황화망간(MnS), 플루오루화 흑연, 플루오르화 칼슘(CaF2), 질화 붕소(BN), 이황화 몰리브덴(MoS2), 및 이황화 텅스텐으로 구성된 군으로부터 선택된 일 재료일수 있으며, 이들 중 가공성의 견지에서 흑연이 사용되는 것이 바람직하다.The solid lubricant particles used in the film mixture according to the present invention are graphite (C), manganese sulfide (MnS), graphite fluoride, calcium fluoride (CaF 2 ), boron nitride (BN), molybdenum disulfide (MoS 2 ), and It may be one material selected from the group consisting of tungsten disulfide, of which graphite is preferably used in view of workability.

고체윤활제 입자를 금속으로 피복하는 방법은 화학적, 전기화학적, 및 기계적 도금법, 가스환원방법, 그리고 기계적융합법을 포함할 수 있다. 본 발명에 따른 고체윤활제 입자를 피복하는데 사용되는 금속은 구리, 니켈, 은, 코발트, 및 몰리브덴으로 구성된 군으로부터 선택된 하나의 재료일 수 있으며, 이들 중 금속도금능력의 입장에서 구리(Cu)가 사용되는 것이 바람직하다.The method of coating the solid lubricant particles with metal may include chemical, electrochemical, and mechanical plating methods, gas reduction methods, and mechanical fusion methods. The metal used to coat the solid lubricant particles according to the present invention may be one material selected from the group consisting of copper, nickel, silver, cobalt, and molybdenum, of which copper (Cu) is used in view of metal plating ability. It is desirable to be.

피막혼합물에 사용되는 경질재료는 크롬, 텅스텐, 몰리브덴, 및 바나듐의 탄화물, 산화물, 질화물, 및 탄질화물로 이루어진 군으로부터 선택될 수 있으며, 이들중 본 발명에 따르면, 상대물 비공격성(즉, 용사피막을 갖는 미끄럼부재와 미끄럼결합을 하는 상대물에 대한 비공격성)의 견지에서, 산화크롬(Cr2O3)이나 탄화크롬(CrC)을 사용하는 것이 바람직하다.The hard material used in the coating mixture may be selected from the group consisting of carbides, oxides, nitrides, and carbonitrides of chromium, tungsten, molybdenum, and vanadium, among which, according to the present invention, the relative non-attack (i.e., spraying) In view of the non-aggression property of the sliding member having the film and the counterpart of the sliding member, it is preferable to use chromium oxide (Cr 2 O 3 ) or chromium carbide (CrC).

매트릭스를 형성하는 피막혼합물에 사용되는 금속은 몰리브덴, 니켈-크롬합금, 코발트, 코발트-크롬합금, 니켈-몰리브덴 합금, 및 코발트-니켈합금으로 구성된 군으로부터 선택될 수 있으며, 이들중 본 발명에 따르면, 내마모성 및 내스커핑(scuffing)성의 관점에서, 몰리브덴(Mo) 및 니켈-크롬(Ni-Cr)합금을 함께 사용하는 것이 바람직하다.The metal used in the coating mixture forming the matrix may be selected from the group consisting of molybdenum, nickel-chromium alloy, cobalt, cobalt-chromium alloy, nickel-molybdenum alloy, and cobalt-nickel alloy, among which, according to the present invention From the viewpoint of wear resistance and scuffing resistance, it is preferable to use molybdenum (Mo) and nickel-chromium (Ni-Cr) alloys together.

또한, 용사피막의 다공율은, 플라즈마용사에 의해 5 내지 15 체적%의 범위내로 한정되는 것이 바람직하다. 그 이유는, 상기 다공율이 5 체적% 미만이면 보유성이 불량하며, 다공율이 15 체적% 를 초과하면 용사피막이 취약해져, 피막강도가 극히 저하되기 때문이다.In addition, it is preferable that the porosity of the thermal sprayed coating is limited to the range of 5-15 volume% by plasma spraying. This is because if the porosity is less than 5% by volume, the retention is poor, and if the porosity is more than 15% by volume, the thermal spray coating is brittle and the film strength is extremely reduced.

상술한 것처럼, 본 발명에 따른 용사피막에 의하면, 취성을 일으키는 피막강도의 저하는 발생하지 않으며 또한 피막내 보유성도 불량하지 않다. 또한, 본 발명에 따른 용사피막은, 향상된 저 마찰계수를 가질뿐만 아니라 내마모성, 내스커핑성, 및 상대물 비공격성도 우수하다.As described above, according to the thermal spray coating according to the present invention, there is no decrease in film strength that causes brittleness and no poor film retention. In addition, the thermal spray coating according to the present invention has not only an improved low coefficient of friction but also excellent wear resistance, scuffing resistance, and counterattack resistance.

도 1 을 참조하여, 본 발명에 따른 용사피막을 피스톤링과 관련하여, 이하에 서술하겠다.With reference to FIG. 1, the thermal spray coating which concerns on this invention is demonstrated below with respect to a piston ring.

도 1 에 도시된 피스톤링 (1) 에는 그 모재 (2) 의 외주 미끄럼면상에 형성된 용사피막 (3) 이 있다. 상기 용사피막 (3) 은, 40 내지 80 질량%의 몰리브덴 분말, 10 내지 50 질량%의 니켈-크롬합금 분말, 1 내지 20 질량%의 산화크롬이나 탄화크롬, 0.1 내지 10 질량%의 구리피복 흑연입자로 구성된 혼합물을 플라즈마-용사하여 형성된 것이다.The piston ring 1 shown in FIG. 1 has a thermal sprayed coating 3 formed on the outer circumferential sliding surface of the base material 2. The thermal spray coating (3) comprises 40 to 80 mass% molybdenum powder, 10 to 50 mass% nickel-chromium alloy powder, 1 to 20 mass% chromium oxide or chromium carbide, and 0.1 to 10 mass% copper clad graphite. A mixture of particles is formed by plasma-spraying.

상기 구리피복 흑연입자는 10 내지 50 질량% 의 흑연을 갖는 구리피복을 구비하며, 10 내지 106 ㎛ 의 크기분포를 갖는다.The copper coated graphite particles have a copper coating having 10 to 50% by mass of graphite, and have a size distribution of 10 to 106 μm.

용사피막 (3) 의 횡단면을 통해 볼수 있는 것처럼, 상기 피막혼합물은 0.1 내지 10 질량% 의 구리피복 흑연입자 (4) 를 구비하며, 이 구리피복 흑연입자는 상기 피막혼합물에 걸쳐 거의 고르게 분산되어있기 때문에, 구리피복 흑연입자 (4) 에 의해 발생하는 용사피막 (3) 의 강도저하는 거의 없다. 더욱이, 용사피막(3) 의 산화크롬 또는 탄화크롬의 경질재료 입자 (5) 가, 몰리브덴과 니켈-크롬 합금으로 형성된 매트릭스 (6) 내에 고르게 분산되어 있어서, 상기 용사피막 (3) 의 상대물 공격성이 낮다. 더욱이, 플라즈마-용사로 형성된 상기 용사피막 (3) 의 다공율은 5 내지 15 질량% 이므로, 다공율과 흑연 상(相)의 상승효과로 인해, 상기 용사피막 (3) 은 마찰저항이 작고 내마모성 및 내스커핑성이 우수하다.As can be seen through the cross section of the thermal sprayed coating 3, the coating mixture comprises 0.1 to 10% by mass of copper coated graphite particles 4, which copper coated graphite particles are almost evenly dispersed throughout the coating mixture. Therefore, there is almost no decrease in strength of the thermal sprayed coating 3 generated by the copper-coated graphite particles 4. Furthermore, the hard material particles 5 of chromium oxide or chromium carbide of the thermal sprayed coating 3 are evenly dispersed in the matrix 6 formed of molybdenum and nickel-chromium alloys, so that the relative aggressiveness of the thermal sprayed coating 3 is prevented. Is low. Furthermore, since the porosity of the thermal sprayed coating 3 formed by plasma-spray is 5 to 15% by mass, the thermal sprayed coating 3 has a low frictional resistance and abrasion resistance due to the synergistic effect of the porosity and the graphite phase. And scuffing resistance is excellent.

(용사피막의 실시예와 그 시험의 설명)(Example of a thermal spray coating and explanation of the test)

본 발명의 용사피막을, 실시예, 비교예 및 종래예에 대하여 행한 몇몇 시험과 연관하여 이하에서 더 자세히 서술하겠다.The thermal spray coating of the present invention will be described in more detail below in connection with some tests performed on Examples, Comparative Examples and Conventional Examples.

아래 표 1 에 도시된 것처럼, 시편 No.1 및 Mo.2 는 금속피복 고체윤활제를 함유하지 않은, HVOF(No.1) 또는 플라즈마(No.2)용사가공에 의해 형성된 피막을 갖는 종래예이다. 시편 No.3 내지 No.15 는 본 발명의 실시예에 따른, 금속피복 고체윤활제 입자를 함유한 플라즈마-용사 피막의 실시예이다. 마지막으로, 시편 No.16 내지 No.19 는 금속피복 고체윤활제를 함유한 플라즈마용사 피막의 비교예로서, 상기 비교예와 실시예는 피막혼합물내의 금속피복 고체윤활제의 함량비 또는 금속피복 고체윤활제내의 고체윤활제의 함량비가 서로 다르다.As shown in Table 1 below, Specimens No. 1 and Mo. 2 are conventional examples having a film formed by HVOF (No. 1) or plasma (No. 2) spraying, which do not contain a metal-coated solid lubricant. . Specimens No. 3 to No. 15 are examples of plasma-spray coatings containing metallized solid lubricant particles, according to embodiments of the present invention. Finally, Specimens No. 16 to No. 19 are comparative examples of plasma sprayed coatings containing metal-coated solid lubricants, and the comparative examples and examples contained the content ratio of the metal-coated solid lubricants in the coating mixture or the metal-coated solid lubricants The content ratio of the solid lubricants is different.

피막혼합물내의 경질재료의 종류 및 함량비(질량%), 피막혼합물의 매트릭스의 종류 및 함량비(질량%), 피막혼합물내의 금속피복 고체윤활제의 종류 및 함량비(질량%), 금속피복 고체윤활제내의 고체윤활제의 함량비(질량%), 피막의 다공율, 및 용사방법이 표 1 에 나타나 있다. 용사피막을 형성하는데 사용된 구리피복 흑연입자의 흑연은 입상이었다.Type and content ratio (mass%) of the hard materials in the coating mixture, type and content ratio (mass%) of the matrix of the coating mixture, type and content ratio (mass%) of the metal coating solid lubricant in the coating mixture, metal coating solid lubricant The content ratio (mass%) of the solid lubricant in the inside, the porosity of the film, and the spraying method are shown in Table 1. The graphite of the copper-coated graphite particles used to form the thermal spray coating was granular.

표 1 에서, 경질재료의 열(列)에서, % 는 피막혼합물에 함유된 경질재료의 질량%를 의미한다. 매트릭스 열에서, Mo 및 Ni-Cr합금 값은 매트릭스를 형성하는 금속 및 그 매트릭스내에서의 그 금속의 조성을 나타낸다. 금속피복 고체윤활제 열중 종류에서, 앞부분은 피복하는 금속을 나타내고 뒷부분은 피복된 고체윤활제를 나타내며(예를 들어, Cu-C 는 금속피복 고체윤활제로서 Cu 가 피복된 C(흑연)을 의미한다 ), % 는 피막혼합물에 함유된 금속피복 고체윤활제의 질량%를 의미하며, SL% 는 금속피복 고체윤활제에 함유된 고체윤활제의 질량%를 의미한다. 용사방법의 열에서, HV 는 HVOF법을 의미하며, Plas 는 플라즈마법을 의미한다. 비고(備考)열에서, Cnv, Emb, 및 Cmp 는 각각, 종래예, 실시예, 및 비교예를 의미한다.In Table 1, in the heat of the hard material,% means the mass% of the hard material contained in the coating mixture. In the matrix row, the Mo and Ni—Cr alloy values represent the metal forming the matrix and the composition of the metal within the matrix. Metallized Solid Lubricant In the thermal class, the front part represents the metal being covered and the back part is the coated solid lubricant (e.g. Cu-C means Cu coated C (graphite) as the metallized solid lubricant), % Means mass% of the metal-coated solid lubricant contained in the coating mixture, and SL% means mass% of the solid lubricant contained in the metal-coated solid lubricant. In the thermal spraying method, HV means HVOF method and Plas means plasma method. In the remarks column, Cnv, Emb, and Cmp mean a conventional example, an example, and a comparative example, respectively.

플라즈마 용사를 위한 조건은 다음과 같다.Conditions for plasma spraying are as follows.

사용된 용사 건: Sulzer Metco 사에서 제조된 9MB 플라즈마 건,Spray gun used: 9MB plasma gun manufactured by Sulzer Metco,

전압: 60-70 V,Voltage: 60-70 V,

전류: 500 A.Current: 500 A.

HVOF 용사를 위한 조건은 다음과 같다.The conditions for HVOF spraying are as follows.

사용된 용사 건: Sulzer Metco 사에서 제조된 다이아몬드 제트 건(상품명),Spray gun used: Diamond Jet Gun (trade name) manufactured by Sulzer Metco,

연료가스: 프로판-산소(1:7).Fuel gas: propane-oxygen (1: 7).

각 시편에 스커핑 시험, 마모시험, 및 상대물-공격성 시험을 실시했다.Each specimen was subjected to a scuffing test, abrasion test, and counter-attack test.

(스커핑 시험)(Scuffing test)

도 2 에 도시된 바와 같이, 평면미끄럼 마찰마모용 회전식 시험기를 사용하여 각 시편의 스커핑 임계 면압(area pressure)을 측정했다. 일정한 속도로 회전하는 상대물 (12) 의 회전면에 각 시편 (11) 을 일정한 시간동안 소정의 면압(P)하에 접촉을 유지시켜, 스커핑이 발생한 때의 면압을 임계 면압으로 했다. 압력조작은, 초기 압력을 2.45 MPa 로 설정하여, 30분의 제 1 주기후에 4.9 MPa 로 압력을 증가시키고, 이후에 매 5분마다 0.98 MPa 씩 압력을 점차 증가시키는, 방법으로 하였다.As shown in FIG. 2, the scuffing critical area pressure of each specimen was measured using a rotary tester for planar sliding frictional wear. Each specimen 11 was kept in contact with the rotating surface of the counterpart 12 rotating at a constant speed under a predetermined surface pressure P for a predetermined time, and the surface pressure at the time of scuffing was set as the critical surface pressure. The pressure operation was performed by setting the initial pressure to 2.45 MPa, increasing the pressure to 4.9 MPa after the first 30 minute period, and then gradually increasing the pressure by 0.98 MPa every 5 minutes.

시험조건은 다음과 같았다.The test conditions were as follows.

미끄럼속도: 5 m/sec,Sliding speed: 5 m / sec,

윤활유: SAE30 + 백등유(1:1),Lubricant: SAE30 + White Kerosene (1: 1),

공급된 윤활유의 양: 초기외에는 무급유The amount of lubricant supplied: no oil other than initial

대상물: 타카로이(tarkalloy)(일본 Piston Ring Co., Ltd. 의 상품명으로 알려진 붕소 주철).Object: tarkalloy (boron cast iron known under the trade name of Piston Ring Co., Ltd., Japan).

(마모시험 및 대상물-공격성 시험)(Wear test and object-attack test)

도 2 에 도시된 바와 같이, 평면미끄럼 마찰마모용 회전식 시험기를 사용하여 각 시편의 마모깊이 및 대상물의 마모깊이를 측정하였다. 일정한 속도로 회전하는 상대물 (12) 의 회전면에 각 시편 (11) 을 일정한 시간동안 소정의 면압(P)하에 접촉을 유지시켰다. 윤활유를 회전하는 상대물 (12) 상에 떨어뜨렸다.As shown in FIG. 2, the wear depth of each specimen and the wear depth of the object were measured using a rotary tester for flat sliding frictional wear. Each specimen 11 was kept in contact with the rotating surface of the counterpart 12 rotating at a constant speed under a predetermined surface pressure P for a predetermined time. Lubricating oil was dropped on the rotating counterpart 12.

시험조건은 다음과 같았다.The test conditions were as follows.

미끄럼속도: 6 m/sec,Sliding speed: 6 m / sec,

면압: 6 MPa,Surface pressure: 6 MPa,

윤활유: Spinox-2 베어링유(일본 Mitsubishi Oil Corporation 의 상품명으로 알려진 베어링유),Lubricant: Spinox-2 bearing oil (a bearing oil known under the trade name of Mitsubishi Oil Corporation in Japan),

유온: 60±10℃Oil temperature: 60 ± 10 ℃

공급된 윤활유의 양: 10-4m3/min,Amount of lubricant supplied: 10 -4 m 3 / min,

시험시간: 80시간,Exam time: 80 hours

대상물: 타카로이(tarkalloy)(일본 Piston Ring Co., Ltd. 의 상품명으로 알려진 붕소 주철).Object: tarkalloy (boron cast iron known under the trade name of Piston Ring Co., Ltd., Japan).

시편 No.1 의 스커핑 임계면압, 시편의 마모량 및 대상물의 마모량의 측정값을 각각 100으로 설정하였을때의 각 시편에 대한 측정결과가 표 1 에 도시되어 있다.Table 1 shows the measurement results for each specimen when the measured values of the scuffing critical surface pressure of specimen No. 1, the wear amount of the specimen, and the wear amount of the object were set to 100, respectively.

상기 결과로부터, 실시예가 내스커핑성, 내마모성, 및 상대물 비공격성에 있어서 종래예 및 비교예보다 우수하다는 것을 확인할 수 있다.From the above results, it can be confirmed that the Examples are superior to the conventional and comparative examples in scuffing resistance, abrasion resistance, and counterattack resistance.

상술한 것처럼, 본 발명에 따른 내마모성 용사피막은, 경질재료분말, 매트릭스를 형성하는 금속분말, 및 금속피복 고체윤활제분말의 혼합물을 플라즈마-용사함으로써 형성되지만, 금속피복 고체윤활제로서 10 질량% 이상의 금속피복 흑연을 갖는 종래의 용사피막과는 달리, 용사피막에서의 상기 금속피복 고체윤활제의 함량비는 10질량% 미만이다.As described above, the wear-resistant sprayed coating according to the present invention is formed by plasma-spraying a mixture of a hard material powder, a metal powder forming a matrix, and a metal-coated solid lubricant powder, but the metal-coated solid lubricant is 10% by mass or more of metal. Unlike the conventional thermal spray coating with coated graphite, the content ratio of the metal-coated solid lubricant in the thermal spray coating is less than 10 mass%.

따라서, 본 발명에 따른 용사피막은, 피막이 취약하지 않다는 점에서 명백하고 우수한 잇점을 갖는다. 더욱이, 본 발명에 따른 용사피막은, 다공율과 고체윤활제 상과의 상승효과로 인해, 마찰저항이 작으며, 내스커핑성, 내마모성, 및 상대물 비공격성에서 우수한 잇점을 갖는다.Therefore, the thermal spray coating according to the present invention has a clear and excellent advantage in that the coating is not fragile. Moreover, the thermal spray coating according to the present invention has a small frictional resistance due to the synergistic effect between the porosity and the solid lubricant phase, and has excellent advantages in scuffing resistance, wear resistance, and counterattack resistance.

이상, 본 발명의 기초적인 신규한 특징들을 바람직한 실시형태에 적용하여 설명하고 도시하였으나, 당업자라면 본 발명의 범위를 벗어나지 않고서 그러한 실시형태에 다양한 수정이나 변화를 가할 수 있다는 것을 이해할 수 있을 것이다. 따라서, 본 발명은 여기에 첨부된 청구범위에만 한정되는 것은 아니다.While the above-described novel features of the present invention have been described and illustrated by applying them to preferred embodiments, those skilled in the art will understand that various modifications or changes can be made to such embodiments without departing from the scope of the present invention. Accordingly, the invention is not limited to only the claims appended hereto.

Claims (8)

경질재료 분말, 매트릭스를 형성하는 금속분말, 및 고체윤활제 분말로 구성된 혼합물을 미끄럼부재의 미끄럼면에 용사함으로써 형성되는 미끄럼부재용 내마모성 용사피막으로서,A wear resistant thermal spray coating for a sliding member formed by spraying a mixture composed of a hard material powder, a metal powder forming a matrix, and a solid lubricant powder on a sliding surface of the sliding member, 상기 혼합물은, 상기 고체윤활제로서, 금속피복 고체윤활제 입자를 상기 혼합물의 0.1 내지 10 질량% 미만으로 포함하는 미끄럼부재용 내마모성 용사피막.The mixture is a wear-resistant thermal spray coating for a sliding member comprising, as the solid lubricant, metal-coated solid lubricant particles in less than 0.1 to 10% by mass of the mixture. 제 1 항에 있어서, 상기 금속피복 고체윤활제 입자는 도금법에 의한 금속피복 흑연입자이며, 상기 피복금속은 구리, 니켈, 은, 코발트, 및 몰리브덴으로 구성된 군으로부터 선택된 일 재료인 것을 특징으로 하는 미끄럼부재용 내마모성 용사피막.2. The sliding member according to claim 1, wherein the metal-coated solid lubricant particles are metal-coated graphite particles by a plating method, and the coating metal is one material selected from the group consisting of copper, nickel, silver, cobalt, and molybdenum. Dragon wear-resistant spray coating. 제 2 항에 있어서, 상기 금속피복 흑연입자는 상기 금속피복 흑연입자의 10 내지 50 질량%의 흑연을 함유하는 것을 특징으로 하는 미끄럼부재용 내마모성 용사피막.The wear-resistant thermal spray coating for sliding members according to claim 2, wherein the metal-coated graphite particles contain 10 to 50% by mass of graphite of the metal-coated graphite particles. 제 1 항에 있어서, 상기 금속피복 고체윤활제 입자는 구리피복 고체윤활제 입자이며, 상기 고체윤활제 입자는 흑연, 황화 망간, 플루오르화 흑연, 플루오르화 칼슘, 질화 붕소, 이황화 몰리브덴, 및 이황화 텅스텐으로 구성된 군으로부터 선택된 일 재료인 것을 특징으로 하는 미끄럼부재용 내마모성 요사피막.The group of claim 1, wherein the metal-coated solid lubricant particles are copper-coated solid lubricant particles, and the solid lubricant particles are composed of graphite, manganese sulfide, graphite fluoride, calcium fluoride, boron nitride, molybdenum disulfide, and tungsten disulfide. A wear-resistant anti-foaming film for a sliding member, characterized in that the material is selected from. 제 4 항에 있어서, 상기 구리피복 고체윤활제 입자는 상기 구리피복 고체윤활제 입자의 10 내지 50 질량%의 고체윤활제를 함유하는 것을 특징으로 하는 미끄럼부재용 내마모성 용사피막.The wear-resistant thermal spray coating for a sliding member according to claim 4, wherein the copper-coated solid lubricant particles contain 10 to 50% by mass of a solid lubricant of the copper-coated solid lubricant particles. 제 1 항 내지 제 5 항 중 어느 한 항에 있어서, 상기 용사피막은 상기 혼합물의 5 내지 15 체적%의 다공율을 갖도록 플라즈마 용사에 의해 형성되는 것을 특징으로 하는 미끄럼부재용 내마모성 용사피막.The wear-resistant sprayed coating for sliding member according to any one of claims 1 to 5, wherein the thermal sprayed coating is formed by plasma spraying so as to have a porosity of 5 to 15% by volume of the mixture. 제 1 항 내지 제 5 항 중 어느 한 항에 있어서, 상기 경질재료는 산화크롬이거나 탄화크롬이며, 상기 매트릭스를 형성하는 금속은 몰리브덴과 니켈-크롬합금인 것을 특징으로 하는 미끄럼부재용 내마모성 용사피막.The wear-resistant thermal spray coating for a sliding member according to any one of claims 1 to 5, wherein the hard material is chromium oxide or chromium carbide, and the metal forming the matrix is molybdenum and nickel-chromium alloy. 제 6 항에 있어서, 상기 경질재료는 산화크롬이거나 탄화크롬이며, 상기 매트릭스를 형성하는 금속은 몰리브덴과 니켈-크롬합금인 것을 특징으로 하는 미끄럼부재용 내마모성 용사피막.7. The wear-resistant thermal spray coating for a sliding member according to claim 6, wherein the hard material is chromium oxide or chromium carbide, and the metal forming the matrix is molybdenum and nickel-chromium alloy.
KR10-2002-0033280A 2001-06-15 2002-06-14 An abrasion-resistant thermal-sprayed coating for a sliding member KR100501985B1 (en)

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