WO2012135974A1 - Composite sulfide solid lubricating film and method thereof - Google Patents

Composite sulfide solid lubricating film and method thereof Download PDF

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Publication number
WO2012135974A1
WO2012135974A1 PCT/CN2011/000596 CN2011000596W WO2012135974A1 WO 2012135974 A1 WO2012135974 A1 WO 2012135974A1 CN 2011000596 W CN2011000596 W CN 2011000596W WO 2012135974 A1 WO2012135974 A1 WO 2012135974A1
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WIPO (PCT)
Prior art keywords
lubricating film
solid lubricating
film layer
sulfide solid
composite sulfide
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PCT/CN2011/000596
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French (fr)
Chinese (zh)
Inventor
韩彬
王勇
赵卫民
韩涛
李美艳
孙建波
万盛
薛敏鹏
Original Assignee
中国石油大学(华东)
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Application filed by 中国石油大学(华东) filed Critical 中国石油大学(华东)
Priority to PCT/CN2011/000596 priority Critical patent/WO2012135974A1/en
Priority to CN2011101507306A priority patent/CN102732880B/en
Publication of WO2012135974A1 publication Critical patent/WO2012135974A1/en

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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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/06—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases
    • C23C8/08—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using gases only one element being applied
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/06—Metal compounds
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-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
    • C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C8/02—Pretreatment of the material to be coated
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C10M2201/0653—Sulfides; Selenides; Tellurides used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/06—Metal compounds
    • C10M2201/065—Sulfides; Selenides; Tellurides
    • C10M2201/066—Molybdenum sulfide
    • C10M2201/0663—Molybdenum sulfide used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • the present invention relates to the field of metal material surface treatment technology, and in particular to a composite sulfide solid lubricant film layer and a preparation method thereof.
  • Solid lubrication refers to the use of solid powder, coating or composite materials instead of lubricating oil (fat) to isolate the friction surfaces that contact each other, relying on the low-shear characteristics of the solid lubricant material itself or its transfer film to reduce the movement between the auxiliary The purpose of friction and wear.
  • Solid powders, coatings or composites used for solid lubrication are collectively referred to as solid lubricants. Commonly used solid lubricants have a layered crystal
  • Laser cladding refers to placing a selected coating material on a coated substrate by different adding methods, heating by a high-energy density laser beam, melting the surface of the substrate, and rapidly solidifying, thereby forming a matrix on the surface of the substrate. Process for metallurgical bonding of surface coatings. Laser cladding uses a high-power laser beam to scan the metal surface and melt the selected material onto the metal surface to form a coating with high hardness, good wear resistance, and corrosion resistance.
  • Ni-based alloys have high hardness and wear resistance, can significantly improve the performance of materials, and have been widely used in improving the performance of parts.
  • FeSK, MoS 2 , WS 2 and other gram structures are close-packed hexagonal structures, which have low deformation resistance, easy sliding along the dense surface, strong plastic rheology, and can be used as a solid lubricant.
  • the sulphate lubricating film layer can be prepared by various methods, such as thermal spraying, low temperature ion osmosis, low temperature electrolytic osmosis, etc., and the structure and tribological properties of the sulfide layer formed by different processes are also greatly different.
  • the ideal friction surface should be the softest surface layer and have good lubricating properties, while the subsurface layer is hard and can form a good transition with the matrix, and the outermost layer is effectively supported without layering.
  • the Ni-based laser cladding cermet coating can form a metallurgical bond with the matrix, wherein the nickel-based alloy ensures the strength and corrosion resistance of the cladding layer, and the cermet phase can increase the hardness of the cladding layer, which can provide a comparison for the sulfurized layer. Hard and stable substrate.
  • the characteristics of laser cladding fast heating and rapid cooling make the cermet coating fine structure and many crystal defects, which promote the adsorption and diffusion of sulfur.
  • the cladding layer is rich in Fe, W, and Mo elements, and a composite sulfide solid lubricating film layer containing FeS, WS 2 and MoS 2 can be synthesized on the surface by osmosis treatment.
  • the laser cladding layer is a Ni-based cermet cladding layer rich in Fe, W, and Mo elements.
  • the sulfurized layer is a composite sulfide film layer containing FeS, WS 2 and MoS 2 .
  • the substrate is a metal material.
  • the technical content of the present invention is as follows:
  • the metal material is a steel material.
  • the technical content of the present invention further includes: (1) performing laser cladding treatment on the substrate to obtain a laser cladding layer;
  • the surface-treated laser cladding layer is subjected to sulfurizing treatment to obtain a seepage layer.
  • the technical content of the present invention is as follows:
  • the powder for laser cladding treatment in the step (1) includes Ni, Fe, Cr, Mo, WC, and the chemical composition is in weight percentage: WC is 10% to 35%, and Fe is 5% ⁇ 20%, Cr is 5% ⁇ 15%, Mo is 2% ⁇ 10%, and the rest is Ni60.
  • the technical content of the present invention is as follows:
  • the surface treatment in the step (2) includes fine grinding, mechanical polishing and ultrasonic cleaning, and the non-sulphurized surface is covered and shielded.
  • the technology of the present invention includes: the sulfurizing treatment in the step (3) is ion osmosis, liquid sulphur, gas sulphur or solid sulphur.
  • the ion osmosis is a substrate after the laser cladding is connected to the cathode, and the furnace wall is connected to the anode.
  • ITrro degree of vacuum
  • a high voltage direct current is applied between the anode and the cathode, and the temperature of the osmosis is increased. It is 170 ° C ⁇ 30 (TC, sulfur-containing gas is H 2 S, voltage is 500V ⁇ 900V, sulfurizing time is lh ⁇ 3h.
  • the composite sulfide solid lubricating film layer of the invention has good antifriction lubricating performance and can be used for Dry friction at higher loads and friction pairs with water or oil lubrication.
  • the present invention is a composite sulfide solid lubricating film layer formed by laser cladding Ni-based cermet coating after sulfurizing, and there is no obvious boundary between the two, so the structure is tight and the ability to bond with the cladding layer Strong.
  • Ni-based cermet laser cladding layer can achieve metallurgical bonding with the substrate, wherein the nickel-based alloy ensures the strength and corrosion resistance of the cladding layer, the ceramic phase can improve the hardness of the cladding layer, and the cermet can be a sulfurized layer Provide a hard and stable substrate.
  • the cermet coating has fine structure and many crystal defects, and promotes the adsorption and diffusion of sulfur.
  • the cladding layer is rich in Fe, W, Mo and other elements. After sulfurizing, a composite sulfide solid lubricating film layer containing sulfides such as FeS, WS 2 and MoS 2 is obtained, and the friction coefficient and the wear scar depth are small. And its structure is tight, with good wear resistance, corrosion resistance and friction reducing performance.
  • Figure 1 is a flow chart for preparing a composite sulfide solid lubricating film layer.
  • Fig. 2 is a schematic cross-sectional structural view of a composite sulfide solid lubricating film layer obtained by low temperature ion osmosis after laser cladding.
  • (a) shows a substrate
  • (b) shows a laser cladding layer
  • (c) shows a composite sulfide solid lubricant film layer.
  • Figure 3 is a graph of the coefficient of friction as a function of time before and after low temperature ion sulphurization.
  • the laser cladding layer is subjected to low-temperature ion osmosis treatment.
  • the substrate after laser cladding is connected to the cathode, and the furnace wall is connected to the anode.
  • the vacuum reaches lTrro, high-voltage direct current is applied between the anode and the cathode.
  • the percolation temperature is 170 ° C ⁇ 220 ° C
  • the gas containing gas is H 2 S gas
  • the voltage is 500V ⁇ 600V
  • the percolating time is 90min.
  • a Ni-based cermet cladding layer rich in Fe, W, Mo is obtained, the thickness of which is 0. 8mm ⁇ 1. 5 hidden. 001 ⁇ 0. 01 ⁇
  • a composite sulfide film containing FeS, WS 2 and MoS 2 having a thickness of 0. 001mm ⁇ 0. 01mm.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)

Abstract

Provided is a composite sulfide solid lubricating film, which comprises a laser cladded layer prepared by laser cladding the substrate and a sulfide layer prepared by sulfurizing the laser cladded layer, wherein the laser cladded layer is a Ni-based metal-ceramic layer, and the sulfide layer contains FeS, WS2 and MoS2. Also provided is a method for preparing the composite sulfide solid lubricating film.

Description

一种复合硫化物固体润滑膜层及其制备方法 技术领域 本发明涉及金属材料表面处理技术领域， 尤其是涉及一种复合硫化物 固体润滑膜层及其制备方法。  TECHNICAL FIELD The present invention relates to the field of metal material surface treatment technology, and in particular to a composite sulfide solid lubricant film layer and a preparation method thereof.
背景技术 为了提高零部件的减摩耐磨性能及使用寿命， 通常的方法是增加表面 硬度和添加润滑油， 然而这些措施并不总是可行的。 一方面， 工件表面硬 度的增加会使对偶件的磨损加剧； 另一方面高硬度会引起初性下降， 不利 于抵抗疲劳磨损。 而且在高温、 高压、 真空等特殊情况下， 润滑油不能发 挥作用。 采用固体润滑是克服以上不足的一种有效方法。 固体润滑是指利用固体粉末、 涂层或复合材料等代替润滑油 （脂）来 隔离相互接触的摩擦面， 依靠固体润滑剂材料本身或其转移膜的低剪切特 性， 以达到减少运动副间的摩擦和磨损的目的。 固体润滑所用的固体粉末、 涂层或复合材料统称为固体润滑剂。 常用的固体润滑剂有层状结构的晶体BACKGROUND OF THE INVENTION In order to improve the friction and wear resistance and service life of components, the usual method is to increase the surface hardness and add lubricating oil, but these measures are not always feasible. On the one hand, the increase in the hardness of the surface of the workpiece increases the wear of the counterpart; on the other hand, high hardness causes a drop in initiality and is not conducive to fatigue wear. Moreover, in special cases such as high temperature, high pressure, and vacuum, the lubricating oil cannot function. Solid lubrication is an effective way to overcome the above deficiencies. Solid lubrication refers to the use of solid powder, coating or composite materials instead of lubricating oil (fat) to isolate the friction surfaces that contact each other, relying on the low-shear characteristics of the solid lubricant material itself or its transfer film to reduce the movement between the auxiliary The purpose of friction and wear. Solid powders, coatings or composites used for solid lubrication are collectively referred to as solid lubricants. Commonly used solid lubricants have a layered crystal
(石墨、 FeS、 WS2、 MoS2 )， 质地较软的金属（Ag、 Pb、 Sn、 In ), 金属氧化 物、 氟化物、 磷酸盐等。 激光熔覆指以不同的添加方法在被熔覆的基体上放置选择的涂层材 料， 经高能密度激光束照射加热， 使之和基体表面熔化， 并快速凝固， 从 而在基材表面形成与基体为冶金结合的表面涂层的工艺过程。 激光熔覆采 用大功率激光束扫描金属表面， 将选定的材料熔化到金属表面， 形成具有 硬度高、 耐磨性好、 抗腐蚀等特性的涂覆层。 Ni基合金具有较高的硬度与 耐磨性， 可显著改善材料的性能， 在提高零件性能上已获得了广泛的应用 FeS、 MoS2、 WS2等石克化物属密排六方结构， 其变形抗力小， 易沿密排面 滑移， 塑性流变能力强， 可以作为固体润滑剂使用。 石克化物润滑膜层可由 多种方法制备， 如热喷涂、 低温离子渗硫、 低温电解渗硫等， 不同工艺方 法形成的硫化物层的结构和摩擦学性能也有较大的不同。 随着科学技术的发展， 现有的 FeS润滑涂层多为直接在钢铁基体上或 者在铁的涂层上进行渗硫得到， 而这种工艺加工出来的固体润滑涂层的润 滑性能已经不能满足一些特殊工况的要求， 因此， 固体润滑涂层的制备方 法有待于创新拓展。 (Graphite, FeS, WS 2 , MoS 2 ), softer metals (Ag, Pb, Sn, In), metal oxides, fluorides, phosphates, etc. Laser cladding refers to placing a selected coating material on a coated substrate by different adding methods, heating by a high-energy density laser beam, melting the surface of the substrate, and rapidly solidifying, thereby forming a matrix on the surface of the substrate. Process for metallurgical bonding of surface coatings. Laser cladding uses a high-power laser beam to scan the metal surface and melt the selected material onto the metal surface to form a coating with high hardness, good wear resistance, and corrosion resistance. Ni-based alloys have high hardness and wear resistance, can significantly improve the performance of materials, and have been widely used in improving the performance of parts. FeSK, MoS 2 , WS 2 and other gram structures are close-packed hexagonal structures, which have low deformation resistance, easy sliding along the dense surface, strong plastic rheology, and can be used as a solid lubricant. The sulphate lubricating film layer can be prepared by various methods, such as thermal spraying, low temperature ion osmosis, low temperature electrolytic osmosis, etc., and the structure and tribological properties of the sulfide layer formed by different processes are also greatly different. With the development of science and technology, the existing FeS lubricating coatings are mostly obtained by sulfurizing directly on the steel substrate or on the coating of iron, and the lubricating performance of the solid lubricating coating processed by this process can not be satisfied. The requirements of some special working conditions, therefore, the preparation method of solid lubricating coating needs to be expanded.
本发明根据摩擦理论， 理想的摩擦表面应当是最表层软， 具有良好的 润滑性能， 而亚表层硬并能形成与基体的良好过渡， 给最表层以有效的支 撑并不发生层状剥落。 Ni基激光熔覆金属陶瓷涂层可以与基体形成冶金结 合， 其中镍基合金保证熔覆层的强度和耐蚀性， 金属陶瓷相可以提高熔覆 层的硬度， 可以为渗硫层提供一个较硬并稳固的基体。 激光熔覆快热快冷 的特点使得金属陶瓷涂层组织细密、 晶体缺陷多， 对硫元素的吸附和扩散 有促进的作用。 熔覆层中富含 Fe、 W、 Mo元素， 通过渗^ L处理， 可以在其 表面合成含有 FeS , WS2和 MoS2的复合硫化物固体润滑膜层。 According to the friction theory, the ideal friction surface should be the softest surface layer and have good lubricating properties, while the subsurface layer is hard and can form a good transition with the matrix, and the outermost layer is effectively supported without layering. The Ni-based laser cladding cermet coating can form a metallurgical bond with the matrix, wherein the nickel-based alloy ensures the strength and corrosion resistance of the cladding layer, and the cermet phase can increase the hardness of the cladding layer, which can provide a comparison for the sulfurized layer. Hard and stable substrate. The characteristics of laser cladding fast heating and rapid cooling make the cermet coating fine structure and many crystal defects, which promote the adsorption and diffusion of sulfur. The cladding layer is rich in Fe, W, and Mo elements, and a composite sulfide solid lubricating film layer containing FeS, WS 2 and MoS 2 can be synthesized on the surface by osmosis treatment.
发明内容 本发明的目的在于提出一种具有良好减摩耐磨性能的复合硫化物固体 润滑膜层， 本发明的另一目的在于提供一种上述固体润滑膜层的制备方法， 采用的技术方案是： 一种复合石克化物固体润滑膜层， 其特征在于： 所述复 合石充化物固体润滑膜层包括首先对基体进行激光熔覆所得的激光熔覆层和 渗硫处理所得的渗硫层。 本发明的技术内容还有： 所述的激光熔覆层为富含 Fe、 W、 Mo元素的 Ni基金属陶瓷熔覆层。 SUMMARY OF THE INVENTION An object of the present invention is to provide a composite sulfide solid lubricating film layer having good antifriction and wear resistance. Another object of the present invention is to provide a method for preparing the above solid lubricating film layer, and the technical solution adopted is A composite smectite solid lubricating film layer, comprising: the composite stone-filled solid lubricating film layer comprising a laser cladding layer obtained by first laser-clading a substrate and a sulfurized layer obtained by sulfurizing treatment. According to the technical content of the present invention, the laser cladding layer is a Ni-based cermet cladding layer rich in Fe, W, and Mo elements.
本发明的技术内容还有： 所述的渗硫层为含有 FeS、 WS2及 MoS2的复合 硫化物膜层。 According to the technical content of the present invention, the sulfurized layer is a composite sulfide film layer containing FeS, WS 2 and MoS 2 .
本发明的技术内容还有： 所述的基体为金属材料。  The technical content of the present invention is as follows: The substrate is a metal material.
本发明的技术内容还有： 所述的金属材料为钢铁材料。  The technical content of the present invention is as follows: The metal material is a steel material.
本发明的技术内容还有： （1 )对所述基体进行激光熔覆处理， 得到激 光熔覆层；  The technical content of the present invention further includes: (1) performing laser cladding treatment on the substrate to obtain a laser cladding layer;
( 2 )在所述激光熔覆层上进行表面处理；  (2) performing surface treatment on the laser cladding layer;
( 3 )对表面处理过的激光熔覆层进行渗硫处理得到渗流层。  (3) The surface-treated laser cladding layer is subjected to sulfurizing treatment to obtain a seepage layer.
本发明的技术内容还有： 所述的步骤（1 ) 中激光熔覆处理用粉末包括 Ni、 Fe、 Cr、 Mo、 WC, 化学成分以重量百分比计： WC为 10% ~ 35%, Fe 为 5% ~ 20%, Cr为 5% ~ 15%, Mo为 2% ~ 10%, 其余为 Ni60。  The technical content of the present invention is as follows: The powder for laser cladding treatment in the step (1) includes Ni, Fe, Cr, Mo, WC, and the chemical composition is in weight percentage: WC is 10% to 35%, and Fe is 5% ~ 20%, Cr is 5% ~ 15%, Mo is 2% ~ 10%, and the rest is Ni60.
本发明的技术内容还有： 所述的步骤（2 ) 中表面处理包括精磨、 机械 抛光及超声波清洗， 非渗硫面要进行覆盖、 屏蔽处理。  The technical content of the present invention is as follows: The surface treatment in the step (2) includes fine grinding, mechanical polishing and ultrasonic cleaning, and the non-sulphurized surface is covered and shielded.
本发明的技术内 有： 所述的步骤（3 ) 中渗硫处理为离子渗硫、 液 体渗硫、 气体渗硫或固体渗硫。  The technology of the present invention includes: the sulfurizing treatment in the step (3) is ion osmosis, liquid sulphur, gas sulphur or solid sulphur.
本发明的技术内容还有： 所述离子渗硫是将激光熔覆后的基体接阴极， 炉壁接阳极， 当真空度达到 ITrro 时， 在阳极和阴极之间加高压直流电， 渗石克温度为 170°C ~ 30(TC， 含硫气体为 H2S， 电压为 500V ~ 900V， 渗硫时 间为 lh ~ 3h。 The technical content of the invention is as follows: the ion osmosis is a substrate after the laser cladding is connected to the cathode, and the furnace wall is connected to the anode. When the degree of vacuum reaches ITrro, a high voltage direct current is applied between the anode and the cathode, and the temperature of the osmosis is increased. It is 170 ° C ~ 30 (TC, sulfur-containing gas is H 2 S, voltage is 500V ~ 900V, sulfurizing time is lh ~ 3h.
本发明复合硫化物固体润滑膜层具有良好的减摩润滑性能， 可以用于 较高载荷的干摩擦及有水或油润滑条件下的摩擦副。 The composite sulfide solid lubricating film layer of the invention has good antifriction lubricating performance and can be used for Dry friction at higher loads and friction pairs with water or oil lubrication.
本发明的优点及有益效果：  Advantages and advantages of the present invention:
1、 本发明为激光熔覆 Ni 基金属陶瓷涂层经渗硫后其上形成的复合硫 化物固体润滑膜层， 且二者之间没有明显界限， 因此其结构紧密， 与熔覆 层结合能力强。  1. The present invention is a composite sulfide solid lubricating film layer formed by laser cladding Ni-based cermet coating after sulfurizing, and there is no obvious boundary between the two, so the structure is tight and the ability to bond with the cladding layer Strong.
2、 Ni基金属陶瓷激光熔覆层可以实现与基体的冶金结合，其中镍基合 金保证熔覆层的强度和耐蚀性， 陶瓷相可以提高熔覆层的硬度， 金属陶瓷 可以为渗硫层提供一个较硬并稳固的基体。 金属陶瓷涂层组织细密、 晶体 缺陷多， 对硫元素的吸附和扩散有促进的作用。  2, Ni-based cermet laser cladding layer can achieve metallurgical bonding with the substrate, wherein the nickel-based alloy ensures the strength and corrosion resistance of the cladding layer, the ceramic phase can improve the hardness of the cladding layer, and the cermet can be a sulfurized layer Provide a hard and stable substrate. The cermet coating has fine structure and many crystal defects, and promotes the adsorption and diffusion of sulfur.
3、 熔覆层中富含 Fe、 W、 Mo等元素， 渗硫后得到含有 FeS、 WS2及 MoS2 等硫化物的复合硫化物固体润滑膜层， 其摩擦系数和磨痕深度都较小， 并 且其结构紧密， 具有良好的耐磨、 耐蚀及减摩润滑的性能。 3. The cladding layer is rich in Fe, W, Mo and other elements. After sulfurizing, a composite sulfide solid lubricating film layer containing sulfides such as FeS, WS 2 and MoS 2 is obtained, and the friction coefficient and the wear scar depth are small. And its structure is tight, with good wear resistance, corrosion resistance and friction reducing performance.
附图说明 DRAWINGS
图 1为复合硫化物固体润滑膜层的制备流程图。  Figure 1 is a flow chart for preparing a composite sulfide solid lubricating film layer.
图 2 为激光熔覆后低温离子渗硫处理得到的复合硫化物固体润滑膜层 的剖面结构示意图。 （a )表示基体， （b )表示激光熔覆层， （c )表示复合 硫化物固体润滑膜层。  Fig. 2 is a schematic cross-sectional structural view of a composite sulfide solid lubricating film layer obtained by low temperature ion osmosis after laser cladding. (a) shows a substrate, (b) shows a laser cladding layer, and (c) shows a composite sulfide solid lubricant film layer.
图 3为低温离子渗硫前后的摩擦系数随时间变化的曲线。  Figure 3 is a graph of the coefficient of friction as a function of time before and after low temperature ion sulphurization.
具体实施方式 detailed description
本发明的实施工艺步骤如下：  The steps of the implementation process of the present invention are as follows:
1. 自制富含 Fe、 W、 Mo的 Ni基金属陶瓷粉末， 烘干后在 45号钢基体 表面预置 1. 5mm ~ 2. 5mm厚的粉末， 然后进行激光熔覆处理， 具体工艺参数 为： 5kW横流 C02激光加工系统， 功率为 3400W - 3600W, 扫描速度为 180 mm/min ~ 200麵 /min。 1. Make Ni-based cermet powder rich in Fe, W, Mo. After drying, pre-set the powder of 1. 5mm ~ 2. 5mm on the surface of 45 steel substrate, then carry out laser cladding treatment, specific process parameters For: 5kW cross-flow C0 2 laser processing system, power is 3400W - 3600W, scanning speed is 180 mm / min ~ 200 / min.
2. 对激光熔覆层进行表面处理， 包括精磨、 机械抛光及超声波清洗， 非渗硫面要进行覆盖、 屏蔽等处理。  2. Surface treatment of the laser cladding layer, including fine grinding, mechanical polishing and ultrasonic cleaning. The non-sulphurized surface should be covered and shielded.
3. 对激光熔覆层进行低温离子渗^ ·处理， 其是将激光熔覆后的基体接 阴极， 炉壁接阳极， 当真空度达到 lTrro 时， 在阳极和阴极之间加高压直 流电。渗 ^温度为 170°C ~ 220°C，含石克气体为 H2S气体，电压在 500V ~ 600V, 渗石克时间为 90min。 3. The laser cladding layer is subjected to low-temperature ion osmosis treatment. The substrate after laser cladding is connected to the cathode, and the furnace wall is connected to the anode. When the vacuum reaches lTrro, high-voltage direct current is applied between the anode and the cathode. The percolation temperature is 170 ° C ~ 220 ° C, the gas containing gas is H 2 S gas, the voltage is 500V ~ 600V, and the percolating time is 90min.
经过以上工艺后， 获得富含 Fe、 W、 Mo元素的 Ni基金属陶瓷熔覆层， 其厚度为 0. 8mm ~ 1. 5隱。渗硫后得到含有 FeS、 WS2及 MoS2的复合硫化物膜， 其厚度为 0. 001mm ~ 0. 01mm。 After the above process, a Ni-based cermet cladding layer rich in Fe, W, Mo is obtained, the thickness of which is 0. 8mm ~ 1. 5 hidden. 001毫米至0. 01毫米。 After the sulphide, a composite sulfide film containing FeS, WS 2 and MoS 2 , having a thickness of 0. 001mm ~ 0. 01mm.
比较金属陶瓷熔覆层渗流前后干摩擦条件下的摩擦学性能。 测试结果： 如图 3所示为金属陶瓷熔覆层和复合硫化物固体润滑膜层在干摩擦条件下 摩擦系数随时间变化曲线。 从图 3 可以看出， 复合硫化物固体润滑膜层的 摩擦系数初始值很小， 然后随时间逐渐增大， 最终趋于稳定状态， 此时 μ =0. 65。 并且在整个实验过程中， 复合硫化物固体润滑膜层的摩擦系数始终 低于金属陶瓷熔覆层。  Compare the tribological properties of the cermet cladding layer under dry friction before and after seepage. Test results: As shown in Fig. 3, the friction coefficient of the cermet cladding layer and the composite sulfide solid lubricant layer under dry friction conditions with time. It can be seen from Fig. 3 that the initial value of the friction coefficient of the composite sulfide solid lubricating film layer is small, and then gradually increases with time, and finally tends to be stable, and μ = 0.65. And throughout the experiment, the friction coefficient of the composite sulfide solid lubricating film layer is always lower than that of the cermet cladding layer.
当然， 上述说明并非对本发明的限制， 本发明也不仅限于上述举例， 本技术领域的普通技术人员在本发明的实质范围内所做出的变化、 改型、 添加或替换， 也属于本发明的保护范围。  The above description is not intended to limit the invention, and the invention is not limited to the above examples, and variations, modifications, additions or substitutions made by those skilled in the art within the scope of the invention also belong to the invention. protected range.

Claims

权 利 要 求 Rights request
1.一种复合石克化物固体润滑膜层， 其特征在于： 所述复合 υ化物固体润滑 膜层包括首先对基体进行激光熔覆所得的激光熔覆层和渗硫处理所得的渗 疏层。 A composite ruthenium solid lubricating film layer comprising: a composite layer of a laser-clad layer obtained by laser cladding a substrate and a permeable layer obtained by a sulfurizing treatment.
2.按照权利要求 1 所述的复合硫化物固体润滑膜层， 其特征在于： 所述的 激光熔覆层为富含 Fe、 W、 Mo元素的 Ni基金属陶瓷熔覆层。  The composite sulfide solid lubricating film layer according to claim 1, wherein the laser cladding layer is a Ni-based cermet cladding layer rich in Fe, W, and Mo elements.
3.按照权利要求 1 所述的复合硫化物固体润滑膜层， 其特征在于： 所述的 渗硫层为含有 FeS、 WS2及 MoS2的复合硫化物膜层。 The composite sulfide solid lubricating film layer according to claim 1, wherein the sulfurized layer is a composite sulfide film layer containing FeS, WS 2 and MoS 2 .
4.按照权利要求 1 所述的复合硫化物固体润滑膜层， 其特征在于： 所述的 基体为金属材料。  The composite sulfide solid lubricating film layer according to claim 1, wherein the substrate is a metal material.
5.按照权利要求 4 所述的复合硫化物固体润滑膜层， 其特征在于： 所述的 金属材料为钢铁材料。  The composite sulfide solid lubricating film layer according to claim 4, wherein the metal material is a steel material.
6. 按照权利要求 1所述的复合硫化物固体润滑膜层的制备方法， 其特征在 于： 所述制备方法的步骤包括：  6. The method of preparing a composite sulfide solid lubricating film layer according to claim 1, wherein: the steps of the preparation method comprise:
( 1 )对所述基体进行激光熔覆处理， 得到激光熔覆层；  (1) performing laser cladding treatment on the substrate to obtain a laser cladding layer;
( 2 )在所述激光熔覆层上进行表面处理；  (2) performing surface treatment on the laser cladding layer;
( 3 )对表面处理过的激光熔覆层进行渗硫处理得到渗流层。  (3) The surface-treated laser cladding layer is subjected to sulfurizing treatment to obtain a seepage layer.
7. 按照权利要求 6所述的复合硫化物固体润滑膜层的制备方法， 其特征在 于： 所述的步骤（1 ) 中激光熔覆处理用粉末包括 Ni、 Fe、 Cr、 Mo、 WC, 化 学成分以重量百分比计： WC为 10% ~ 35%, Fe为 5% ~ 20%, Cr为 5% ~ 15%, Mo为 2% - 10%, 其余为 Ni 60。  The method for preparing a composite sulfide solid lubricating film layer according to claim 6, wherein: the powder for laser cladding treatment in the step (1) comprises Ni, Fe, Cr, Mo, WC, and chemistry. The composition is in weight percent: WC is 10% ~ 35%, Fe is 5% ~ 20%, Cr is 5% ~ 15%, Mo is 2% - 10%, and the rest is Ni 60.
8. 按照权利要求 6所述的复合硫化物固体润滑膜层的制备方法， 其特征在 于： 所述的步骤（2 ) 中表面处理包括精磨、 机械抛光及超声波清洗， 非渗 硫面要进行覆盖、 屏蔽处理。 8. A method of preparing a composite sulfide solid lubricating film layer according to claim 6, characterized in that The surface treatment in the step (2) includes fine grinding, mechanical polishing and ultrasonic cleaning, and the non-sulphurizing surface is covered and shielded.
9. 按照权利要求 6所述的复合硫化物固体润滑膜层的制备方法， 其特征在 于： 所述的步骤（3 ) 中渗硫处理为离子渗硫、 液体渗硫、 气体渗硫或固体 渗疏。  The method for preparing a composite sulfide solid lubricating film layer according to claim 6, wherein: the sulfurizing treatment in the step (3) is ion osmosis, liquid sulphur, gas sulphur or solid osmosis. sparse.
10. 按照权利要求 9 所述的复合硫化物固体润滑膜层的制备方法， 其特征 在于： 所述离子渗硫是将激光熔覆后的金属基体接阴极， 炉壁接阳极， 当 真空度达到 ITrro 时， 在阳极和阴极之间加高压直流电， 渗硫温度为 170 °C ~ 300°C， 含硫气体为 H2S， 电压为 500V ~ 900V， 渗石克时间为 lh ~ 3h。 10. The method for preparing a composite sulfide solid lubricating film layer according to claim 9, wherein: the ion sulphur is a metal substrate connected to the cathode after the laser cladding, and the furnace wall is connected to the anode, and the vacuum degree is reached. In ITrro, high-voltage direct current is applied between the anode and the cathode. The sulfurizing temperature is 170 °C ~ 300 °C, the sulfur-containing gas is H 2 S, the voltage is 500V ~ 900V, and the seepage time is lh ~ 3h.
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