Preparation method and application of the multicomponent composite sulfides lubricant film
10934612 ยท 2021-03-02
Assignee
Inventors
Cpc classification
B22F7/08
PERFORMING OPERATIONS; TRANSPORTING
C23C8/00
CHEMISTRY; METALLURGY
C23C8/40
CHEMISTRY; METALLURGY
B22F2999/00
PERFORMING OPERATIONS; TRANSPORTING
B22F7/08
PERFORMING OPERATIONS; TRANSPORTING
C22C30/00
CHEMISTRY; METALLURGY
C10N2030/06
CHEMISTRY; METALLURGY
B22F1/17
PERFORMING OPERATIONS; TRANSPORTING
B22F7/062
PERFORMING OPERATIONS; TRANSPORTING
B22F7/062
PERFORMING OPERATIONS; TRANSPORTING
C23C28/02
CHEMISTRY; METALLURGY
B22F10/25
PERFORMING OPERATIONS; TRANSPORTING
B22F10/25
PERFORMING OPERATIONS; TRANSPORTING
B22F2999/00
PERFORMING OPERATIONS; TRANSPORTING
Y02P10/25
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
B22F9/04
PERFORMING OPERATIONS; TRANSPORTING
Abstract
The invention relates to a multi-component composite sulfide solid lubricating film prepared by sulfurizing the surface of a high-entropy alloy. The high-entropy alloy is composed of five metal elements of Co, Cr, Fe, Ni and Mo or six metal elements of Co, Cr, Fe, Ni, Mo and W. The multi-component composite sulfide solid lubricating film of the invention is mainly applied to the friction pair surface of mechanical equipment, the lubricating film and the sulfurized base have high bonding strength, and multi-component composite sulfide solid lubricating films containing different sulfide lubricating phases can be chose and prepared according to the service environment of equipment.
Claims
1. A multi-component composite sulfide solid lubricating film prepared by sulfurizing the surface of an alloy, wherein the alloy consists of five metal elements of Co, Cr, Fe, Ni and Mo or six metal elements of Co, Cr, Fe, Ni, Mo and W, and the atomic mole percentage of each element ranges from 5% to 35%; the sulfurizing method is a low-temperature ion sulfurization, and the low-temperature ion sulfurization is carried out at a vacuum degree of 10 tor, a pulse voltage of 550V-700V, a sulfurization temperature of 180 C.-280 C., in the presence of hydrogen sulfide gas as sulfurization gas and hydrogen and argon as protective gas; and the thickness of the multi-component composite sulfide solid lubricating film is 3-5 m.
2. The multi-component composite sulfide solid lubricating film according to claim 1, wherein the low-temperature ion sulfurization treatment specifically comprises: placing the alloy on a cathode tower in an ion sulfurization furnace body, allowing the alloy to be connected to a cathode of the ion sulfurization furnace and a furnace wall to be connected to an anode, starting a vacuum pump, applying a pulse voltage of 550V-700V between the anode and cathode when the vacuum degree reaches 10 tor, introducing hydrogen and a small amount of argon into the furnace to produce a glow discharge phenomenon, bombarding the surface of the alloy near the cathode at a high speed by the obtained hydrogen ions and argon ions; and when the sulfurization temperature is between 180 C. and 280 C., and the temperature in the furnace reaches 180 C.-280 C., introducing hydrogen sulfide to sulfurize the alloy of the cathode, wherein the temperature holding time in sulfurization is for 2-2.5 hours.
3. A metal workpiece with high wear resistance, wherein the multi-component composite sulfide solid lubricating film according to claim 1 is attached to the surface of the metal workpiece.
4. The metal workpiece with high wear resistance according to claim 3, wherein the metal workpiece is a sliding bearing, a low-speed gearbox gear, a stamping die, a rock drill piston, or a cylinder sleeve.
5. A preparation method of the metal workpiece with high wear resistance according to claim 3, comprising the following steps: (1) mixing the alloy metal powder uniformly and then ball milling to a particle size of 300 meshes; (2) carrying out surface treatment on a base material, and cladding the alloy metal powder prepared in step (1) on the surface of the base material by laser cladding technology; (3) fine grinding and polishing to a surface roughness of 0.4 um; and (4) carrying out the low-temperature ion sulfurization technology for sulfurization treatment.
6. The method according to claim 5, wherein the low-temperature ion sulfurization treatment specifically comprises: placing the alloy on a cathode tower in an ion sulfurization furnace body, allowing the alloy to be connected to a cathode of the ion sulfurization furnace and a furnace wall to be connected to an anode, starting a vacuum pump, applying a pulse voltage of 550V-700V between the anode and cathode when the vacuum degree reaches 10tor, introducing hydrogen and a small amount of argon into the furnace to produce a glow discharge phenomenon, bombarding the surface of the alloy near the cathode at a high speed by the obtained hydrogen ions and argon ions; and when the temperature in the furnace reaches 180 C. -280 C., introducing hydrogen sulfide to sulfurize the alloy of the cathode, wherein the sulfurization temperature is between 180 C. and 280 C., and the temperature holding time in sulfurization is 2-2.5 hours.
Description
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
(1)
(2) where 1preplaced highentropy alloy powder 2protective gas 3laser head 4laser beam 5high-entropy alloy coating 6base material;
(3)
(4) where 1control cabinet 2voltage control system 3gasket 4cathode tower 5anode plate 6furnace body 7temperature sensor 8vacuum pump 9gas control valve 10hydrogen 11argon 12hydrogen sulfide 13vacuum tester;
(5)
(6)
(7)
(8)
(9)
(10)
(11)
(12)
DETAILED DESCRIPTION OF THE INVENTION
(13) The above-mentioned contents of the invention will be further described in detail through the specific implementation solutions provided in the following embodiments. Those skilled in the art should understand that the scope of the above-mentioned subject matter of the invention is limited to the following embodiments. Any technology implemented on the basis of the above-mentioned contents of the invention belongs to the scope of the invention.
(14) The experimental methods adopted in the following embodiments, unless otherwise specified, are conventional methods; the reagents, materials, instruments and the like used in the following embodiments, if not specifically stated, are commercially available.
(15) I. Processing equipment and material sources used in the application examples of the invention:
(16) 1. The laser cladding equipment is a DL-5 kW cross-flow carbon dioxide laser produced by Shenyang Dalu Laser Group. Different types of laser processing equipment produced by other manufacturers can also be applied to the invention. The invention focuses on a process method for preparing a multi-component composite sulfide solid lubricating film, and there is no special requirement for the equipment.
(17)
(18) 2. The ion sulfurization equipment is the LDMC-15A multifunctional ion chemical heat treatment furnace developed by Wuhan Shoufa Environmental Protection Equipment Co., Ltd. It uses hydrogen sulfide with a purity of 99.9% as the reaction gas, and hydrogen and argon as auxiliary gases.
(19) As shown in
(20) The base material used in the application example of the invention is Q235 steel, and the metal powder is pure metal powder with a purity of 99.9% and a particle size of 300 meshes produced by Nangong Yingtai Metal Material Co., Ltd.
(21) The comparative material high-entropy alloy coating and FeS film used in this application example are all prepared by laser cladding and ion sulfurization technology, which are all existing technologies.
(22) II. Method and equipment used for measuring the bonding strength between the solid lubricating film and the sulfurized base in the application example of the invention
(23) In the examples of the invention, the scratch method is used to measure the bonding strength between the ion sulfurized coating and the laser clad coating. The measurement equipment uses the nano scratch instrument developed by the Lanzhou Institute of Physical Chemistry of the Chinese Academy of Sciences. A smooth scriber is used to scribe the surface of the film obtained by ion sulfurization. When the film is detached from the base, the friction coefficient between the scriber and the contact surface increases, and at this time, the increase rate of the frictional force will change suddenly. Therefore, the load applied when the increase rate of the frictional force changes significantly is the critical load, which is the bonding strength between the sulfide film and the clad coating base. During the test, the pressure loading range is 0-50 N, the loading speed is 50 N/min, and the scratch length is 5 mm.
(24) 3. The tribological property test method and equipment used under dry friction conditions in the application examples of the invention
(25) Under dry friction conditions, the ball-disk friction test is used to test the tribological properties of the application examples of the invention. The friction property test equipment uses the WTM-2E type controlled environmental ball-disk friction and wear tester developed by the Institute of Physical Chemistry of the Chinese Academy of Sciences in Lanzhou. The GCr15 steel ball with a diameter of 6 mm and hardness of HRC65 is used in sample loading. The lower samples are Q235 steel, high-entropy alloy coating, and a high-entropy alloy coating with FeS film, FeS/WS.sub.2 film and various sulfide solid lubricating films prepared on the surface, with a diameter of 40 mm and a thickness of 6 mm. During the experiment, the upper sample is fixed and the lower sample is fixed on the disc sample table. During the experiment, the disc rotates with a friction diameter of 12 mm, a friction speed of 0.2 m/s, and a fixed load of 5 N. The experiment is carried out under dry friction conditions, the experiment temperature is 25 C.-35 C., the air humidity for the experiment is 60%-75%, and the experiment time is 1 hour. The friction coefficient is automatically collected by the test system that comes with the tester. The sample is fully ultrasonic cleaned before and after wear and weighed using a FA2204 electronic balance with an accuracy of 0.1 mg. The weight loss before and after wear is used as the wear loss. The average value of three experiments is regarded as the weight loss.
Example 1. Preparation of FeS/MoS.SUB.2 .Composite Sulfide Solid Lubricating Film
(26) (1) According to the type of sulfides (FeS and MoS.sub.2) contained in the solid lubricating film to be prepared, the laser clad high-entropy alloy powder containing Fe and Mo elements was designed. In order to ensure the hardness and corrosion resistance of the clad coating, CoCrFeNiMo alloy powder was chose and prepared.
(27) (2) The powder material used Co, Cr, Fe, Ni, and Mo metal powder with a purity of 99.9%, was weighed according to equimolar ratio, uniformly mixed, ball milled for 2 hours using a ball mill, and then screened with a 300 mesh metal sieve.
(28) (3) The surface of Q235 base steel was polished and cleaned to remove oxide scale and oil stains.
(29) (4) The laser cladding technology was carried out on the powder obtained in step (2) to prepare the laser clad CoCrFeNiMo high-entropy alloy coating on the surface of the base material obtained in step (3). By changing the laser cladding power and scanning speed, the high-entropy alloy coating in line with the use requirement was obtained. Specifically, the high-entropy alloy coating is prepared by laser cladding on the surface of the base material using the preplaced-powder method, the preplaced-powder thickness is 1 mm, the laser beam adopts a 10 mm1 mm rectangular spot, and the multi-pass cladding overlap rate is 30%, the laser cladding power is 2800 W, and the scanning speed is 150 mm/min.
(30) (5) The coating obtained in step (4) is subjected to fine grinding and polishing treatment, and the surface roughness is 0.4 m.
(31) (6) the low-temperature ion sulfurization is carried out on the coating obtained in step (5). The high-entropy alloy coating was placed on a cathode tower in an ion sulfurization furnace body, the sample was connected to the cathode of the ion sulfurization furnace and the furnace wall was connected to the anode, a vacuum pump was started, a pulse voltage of 640V was applied between the anode and cathode when the vacuum degree reached 10 tor, hydrogen and a small amount of argon were introduced into the furnace to produce a glow discharge phenomenon, and the obtained hydrogen ions and argon ions bombarded the surface of the CoCrFeNiMo high-entropy alloy coating near the cathode at a high speed; and when the temperature in the furnace reached 250 C., hydrogen sulfide was introduced to sulfurize the high-entropy alloy coating of the cathode at 250 C., wherein the temperature holding time in sulfurization was 2.5 hours; the volume ratio of hydrogen sulfide to hydrogen to argon was 30:200:10. The temperature holding time in sulfurization refers to the temperature holding time after hydrogen sulfide gas was introduced; the thickness of the finally prepared FeS/MoS.sub.2 composite sulfide solid lubricating film was 3.4 m.
(32) X-Ray Photoelectron Spectroscopy Analysis:
(33)
(34) Effect Test:
(35) The tribological properties of the CoCrFeNiMo high-entropy alloy coating and the CoCrFeNiSi high-entropy alloy coating and the FeS lubricating film prepared on the surface and the FeS/MoS.sub.2 composite sulfide solid lubricating film prepared in Application Example 1 were compared under dry friction conditions.
(36) Test results: As shown in
(37)
(38) It can be seen from
(39) It can be seen from
(40) In summary, the FeS/MoS.sub.2 composite sulfide solid lubricating film prepared by the invention has excellent lubricating performance under dry friction conditions. Therefore, the FeS/MoS.sub.2 composite sulfide solid lubricating film has more outstanding lubricating performance than that of the high-entropy alloy coating before sulfurization and the FeS single-phase solid lubricating film on the surface of the high-entropy alloy coating and has stable and excellent friction reduction and wear resistance.
(41) Bonding Strength Test:
(42) The bonding strength between the FeS/MoS.sub.2 composite sulfide solid lubricating film and the surface of the CoCrFeNiMo high-entropy alloy coating was tested. The test results are shown in
(43) TABLE-US-00001 TABLE 1 Qualitative evaluation criteria on bonding strength Bonding strength (N) 0-10 10-25 25-40 40-60 60-80 80-100 >100 Qualitative Worse Poor General Good Better Best Metal- evaluation lurgical bonding
Example 2. Preparation of FeS/MoS.SUB.2./WS.SUB.2 .Composite Sulfide Solid Lubricating Film
(44) (1) According to the type of sulfides (FeS, MoS.sub.2, and MoS.sub.2) contained in the solid lubricating film to be prepared, the laser clad high-entropy alloy powder containing Fe, Mo and W elements was designed. In order to ensure the hardness and corrosion resistance of the clad coating, CoCrFeNiMoW alloy powder was chose and prepared.
(45) (2) The powder material used Co, Cr, Fe, Ni, Mo and W metal powder with a purity of 99.9%, was weighed according to equimolar ratio, uniformly mixed, ball milled for 2 hours using a ball mill, and then screened with a 300-mesh metal sieve.
(46) (3) The surface of Q235 base steel was polished and cleaned to remove oxide scale and oil stains.
(47) (4) The laser cladding technology was carried out on the powder obtained in step (2) to prepare the laser clad CoCrFeNiMoW high-entropy alloy coating on the surface of the base material obtained in step (3). Specifically, the high-entropy alloy coating is prepared by laser cladding on the surface of the base material using the preplaced-powder method, the preplaced-powder thickness is 1 mm, the laser beam adopts a 10 mm1 mm rectangular spot, and the multi-pass cladding overlap rate is 30%, the laser cladding power is 3100 W, and the scanning speed is 150 mm/min.
(48) (5) The coating obtained in step (4) is subjected to fine grinding and polishing treatment, and the surface roughness is 0.4 m.
(49) (6) the low-temperature ion sulfurization is carried out on the coating obtained in step (5).
(50) The high-entropy alloy coating was placed on a cathode tower in an ion sulfurization furnace body, the sample was connected to the cathode and the furnace wall was connected to the anode, a vacuum pump was started, a pulse voltage of 640V was applied between the anode and cathode when the vacuum degree reached 10 tor, hydrogen and a small amount of argon were introduced into the furnace to produce a glow discharge phenomenon, and the obtained hydrogen ions and argon ions bombarded the surface of the CoCrFeNiMoW high-entropy alloy coating near the cathode at a high speed; and when the temperature in the furnace reached 250 C., hydrogen sulfide was introduced to ion sulfurize the high-entropy alloy coating of the cathode at 250 C., wherein the temperature holding time in sulfurization was 2.5 hours; the volume ratio of hydrogen sulfide to hydrogen to argon in sulfurization was 30:200:10. The temperature holding time in sulfurization refers to the temperature holding time after hydrogen sulfide gas was introduced; the thickness of the finally prepared FeS/MoS.sub.2 composite sulfide solid lubricating film was 3.6 m.
(51) X-Ray Photoelectron Spectroscopy Analysis:
(52)
(53) Effect Test:
(54) The tribological properties of the CoCrFeNiMoW high-entropy alloy coating and the CoCrFeNiW high-entropy alloy coating and the FeS/WS.sub.2 lubricating film prepared on the surface are compared with the tribological properties of the FeS/MoS.sub.2/WS.sub.2 composite sulfide solid lubricating film prepared in Application Example 2 under dry friction conditions.
(55) Test results:
(56)
(57) It can be seen from
(58) It can be seen from
(59) In summary, the FeS/MoS.sub.2/WS.sub.2 composite sulfide solid lubricating film prepared by the invention has excellent lubricating performance under dry friction conditions, and with stable and excellent friction reduction and wear resistance. Therefore, the FeS/MoS.sub.2/WS.sub.2 composite sulfide solid lubricating film has more outstanding lubricating performance than that before vulcanization and that of other films, and has stable and excellent friction reduction and wear resistance.
(60) Bonding Strength Test:
(61) The bonding strength between the FeS/MoS.sub.2/WS.sub.2 composite sulfide solid lubricating film and the CoCrFeNiMoW high-entropy alloy coating surface was tested. The test results are shown in
(62) The above descriptions are only preferred embodiments of the invention, and are not intended to limit the invention in other forms. Any person familiar with the profession may use the technical content disclosed above to change or modify them into the equivalent embodiments of equivalent changes. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the invention without departing from the content of the technical solutions of the invention still belong to the protection scope of the technical solution of the invention.