CN109868474B - Laser cladding method of titanium alloy - Google Patents
Laser cladding method of titanium alloy Download PDFInfo
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- CN109868474B CN109868474B CN201910288714.XA CN201910288714A CN109868474B CN 109868474 B CN109868474 B CN 109868474B CN 201910288714 A CN201910288714 A CN 201910288714A CN 109868474 B CN109868474 B CN 109868474B
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Abstract
The invention provides a laser cladding method of titanium alloy, belonging to the field of metal surface engineering and high-temperature coating preparation, and the method comprises the following steps: mixing Mo25(NiCrBSiFe) powder and Ti3C2@MoS2The mixture of the composite powder, the Ni powder, the Si powder and the TiN powder is preset on the surface of the titanium alloy to form a preset coating; and carrying out laser cladding on the preset coating to obtain the titanium alloy with the cladding layer. The invention adopts Ti3C2@MoS2Composite powder as lubricating phase, Ti3C2@MoS2The invention has excellent antifriction performance and wear resistance, and simultaneously, the preset coating forms TiN, Ti-Mo, Ti-Ni and Ti-Si multi-component compounds after laser cladding, and the compounds can be used as hard reinforcing phases and have the functions of improving the hardness and wear resistance of the coating.
Description
Technical Field
The invention relates to the technical field of metal surface engineering and high-temperature coating preparation, in particular to a laser cladding method of a titanium alloy.
Background
The titanium alloy has high strength, good corrosion resistance and high heat resistance, and is widely used for manufacturing structural components in the fields of aerospace, petrochemical industry and biomedicine. However, titanium alloys have low surface hardness and poor wear resistance, and are greatly limited for use in special environments with severe wear and abrasion. The preparation of the special self-lubricating wear-resistant coating on the surface of the titanium alloy is one of effective ways for improving the wear resistance and expanding the application of the titanium alloy.
The laser cladding technology is a technological method for remarkably improving the wear resistance, corrosion resistance, heat resistance, oxidation resistance, electrical characteristics and the like of the surface of a base material by placing a coating material on the surface of a coated base body in different filling modes, simultaneously melting a thin layer on the surface of the base body through laser irradiation, and forming a surface coating which has extremely low dilution and is metallurgically combined with the base material after rapid solidification. The laser cladding technology has the advantages of high energy density, small heat input, small distortion, small heat affected zone, small workpiece deformation, metallurgical bonding with a matrix and the like, can be used for preparing a composite coating with high microhardness and excellent tribological performance, is widely applied to the fields of machine manufacturing and maintenance, automobile manufacturing, textile machinery, navigation, aerospace, petrochemical industry and the like, and is a new technology with high economic benefit.
High-autumn-performance et al adopt laser cladding technology to directly prepare Ti-Ni + TiN + MoS on the surface of titanium alloy2the/TiS self-lubricating composite coating (Hill-autumn, Yan Hua, Qinyang, Zhang-Peilai, Chenzheng Fei, Guogulan, for treating water, laser cladding Ti-Ni + TiN + MoS on the surface of titanium alloy2TiS self-lubricating composite coating, materials research report, 2018, 32 (12): 921-928), but the titanium alloy is not specially processed, and under special working conditions, the problems of poor wear resistance and short service life of a friction pair exist.
Disclosure of Invention
The invention aims to provide a laser cladding method of titanium alloy, which can greatly improve the wear resistance of the titanium alloy when the titanium alloy is processed by the method.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a laser cladding method of titanium alloy, which comprises the following steps:
mixing Mo25(NiCrBSiFe) powder and Ti3C2@MoS2The mixture of the composite powder, the Ni powder, the Si powder and the TiN powder is preset on the surface of the titanium alloy to form a preset coating; and carrying out laser cladding on the preset coating to obtain the titanium alloy with the cladding layer.
Preferably, the surface of the titanium alloy is provided with grooves.
Preferably, the depth of the groove is 0.7-1 mm.
Preferably, the groove is a trapezoidal groove.
Preferably, the Mo25(NiCrBSiFe) powder and Ti3C2@MoS2Quality of composite powder, Ni powder, Si powder and TiN powderThe ratio is 35-60: 10-25: 5-8: 3-7: 20-25.
Preferably, the Ti is3C2@MoS2The preparation of the composite powder comprises the following steps:
sintering the mixture of Ti powder, Al powder and TiC powder in inert atmosphere to obtain Ti3AlC2Powder; for the obtained Ti3AlC2Etching the powder to obtain Ti3C2；
Adjusting the pH value of the sulfur source and soluble molybdenum salt mixed solution to 1-2 to obtain an acidic mixed solution; mixing the acidic mixed solution with Ti3C2Mixing, carrying out hydrothermal reaction, and sequentially separating and drying the hydrothermal reaction product to obtain Ti3C2@MoS2And (3) composite powder.
Preferably, the temperature of the hydrothermal reaction is 180-250 ℃, and the time of the hydrothermal reaction is 10-60 h.
Preferably, the flow of protective gas for laser cladding is 17-25L/min, the power is 1700-3500W, the scanning speed is 5-12 mm/s, the defocusing amount is 30-40 mm, and the lap joint rate is more than 35%.
Preferably, after the laser cladding, the heat treatment of the titanium alloy with the cladding layer is further included.
Preferably, the heat treatment temperature is 650-950 ℃, and the heat treatment time is 3-7 h.
The invention provides a laser cladding method of titanium alloy, which comprises the following steps: mixing Mo25(NiCrBSiFe) powder and Ti3C2@MoS2The mixture of the composite powder, the Ni powder, the Si powder and the TiN powder is preset on the surface of the titanium alloy to form a preset coating; and carrying out laser cladding on the preset coating to obtain the titanium alloy with the cladding layer. The invention adopts Ti3C2@MoS2Composite powder as lubricating phase, Ti3C2@MoS2Has excellent antifriction performance and wear resistance, and the preset coating forms TiN, Ti-Mo, Ti-Ni and Ti-Si multi-component compounds after laser cladding, and the compounds can be used as hard reinforcing phases and have the function of improving the hardness and the wear resistance of the coatingThe invention can play the role of each functional unit in a synergistic way, thereby greatly improving the self-lubricating wear-resisting property of the alloy.
The results of the examples show that after the titanium alloy is subjected to the laser cladding treatment of the invention, in the abrasion test of the Co-WC hard alloy with the loading load of 10kg, the rotating speed of 150r/min and the time of 0.5h and the grinding ball of 20 percent, the abrasion loss is only 3.355-4.059 mg, while the abrasion loss of the untreated titanium alloy matrix is as high as 12.936mg, which indicates that the abrasion resistance of the titanium alloy is obviously improved after the titanium alloy is subjected to the laser cladding treatment of the invention.
In addition, the invention can further improve the bonding strength between the coating and the alloy matrix by arranging the groove on the surface of the titanium alloy, and solves the problems that the existing coating has weak bonding force with the matrix and the coating is easy to peel off.
Drawings
FIG. 1 is a schematic structural view of a titanium alloy of the present invention with trapezoidal grooves on its surface.
Detailed Description
The invention provides a laser cladding method of titanium alloy, which comprises the following steps:
mixing Mo25(NiCrBSiFe) powder and Ti3C2@MoS2The mixture of the composite powder, the Ni powder, the Si powder and the TiN powder is preset on the surface of the titanium alloy to form a preset coating; and carrying out laser cladding on the preset coating to obtain the titanium alloy with the cladding layer.
The invention has no special requirements on the type of the titanium alloy, and any type of titanium alloy can be used. In the present invention, the titanium alloy is preferably a Ti-6Al-4V titanium alloy, TB or TC series titanium alloy.
The present invention preferably includes pre-treating the titanium alloy prior to pre-loading the mixture onto the surface of the titanium alloy. In the present invention, the pretreatment preferably includes polishing and cleaning which are performed in sequence. The polishing of the invention can remove the oxide film on the surface of the titanium alloy. The present invention does not require any particular way of abrading and cleaning, as will be appreciated by those skilled in the art.
Before the mixture is preset on the surface of the titanium alloy, the invention preferably also comprises the step of processing a groove on the surface of the titanium alloy. According to the invention, the groove is processed on the surface of the titanium alloy, so that the bonding strength between the coating and the alloy matrix can be further improved, and the problems that the existing coating is weak in bonding force with the matrix and the coating is easy to peel off are solved.
In the invention, the depth of the groove is preferably 0.7-1 mm. The shape of the groove is not specially required, and the groove can be in any shape, such as a cuboid groove, a square groove, a trapezoidal groove, a semi-spherical groove or other irregular shapes. In the invention, the groove is preferably a trapezoidal groove, and as shown in fig. 1, the width of the notch of the trapezoidal groove is preferably 0.5-1 mm, more preferably 0.7-1 mm, and most preferably 1 mm; the width of the groove bottom is preferably 1-3 mm, more preferably 1.5-2.5 mm, and most preferably 2 mm; the depth of the trapezoid groove is preferably 0.7-1 mm, and more preferably 0.7 mm; the upper end opening distance of the adjacent trapezoid grooves is preferably 4-5 mm, and further preferably 4 mm. The invention has no special requirement on the length of the trapezoidal groove and does not exceed the length of the titanium alloy sample. In the present invention, each of the trapezoidal grooves is preferably machined to the same size. The trapezoidal grooves are preferably processed to be distributed in parallel. According to the invention, the size of the groove is controlled within the range, so that the bonding strength of the coating and the titanium alloy matrix is improved. The invention has no special requirement on the processing mode of the groove, and the processing mode known by the technicians in the field can be adopted.
The sequence of the pretreatment and the groove machining is not particularly limited, the titanium alloy can be pretreated firstly, and then the groove is machined on the surface of the titanium alloy; or processing a groove on the surface of the titanium alloy and then pretreating the titanium alloy.
After the pretreatment and groove machining, the invention comprises Mo25(NiCrBSiFe) powder and Ti3C2@MoS2And (3) presetting the mixture of the composite powder, the Ni powder, the Si powder and the TiN powder on the surface of the titanium alloy to form a preset coating.
In the invention, the Mo25(NiCrBSiFe) powder and Ti3C2@MoS2Composite powder, Ni powder, Si powder and TiN powderThe diameter is independently preferably less than 5 μm. The invention has no special requirements on the sources of the Mo25(NiCrBSiFe) powder, the Ni powder, the Si powder and the TiN powder, and can adopt commercial products which are well known by the technical personnel in the field. In the present invention, the Ti is3C2@MoS2The composite powder is preferably prepared by self, and the Ti is3C2@MoS2The preparation of the composite powder preferably comprises the following steps:
sintering the mixture of Ti powder, Al powder and TiC powder in inert atmosphere to obtain Ti3AlC2Powder; for the obtained Ti3AlC2Etching the powder to obtain Ti3C2；
Adjusting the pH value of the sulfur source and soluble molybdenum salt mixed solution to 1-2 to obtain an acidic mixed solution; mixing the acidic mixed solution with Ti3C2Mixing, carrying out hydrothermal reaction, and sequentially separating and drying the hydrothermal reaction product to obtain Ti3C2@MoS2And (3) composite powder.
The invention sinters the mixture of Ti powder, Al powder and TiC powder in inert atmosphere to obtain Ti3AlC2And (3) powder.
In the present invention, Ti is preferably used in an atomic ratio3AlxCyWeighing Ti powder, Al powder and TiC powder, and mixing, wherein the value of x is preferably 0.95-1.25, more preferably 1.0-1.2, and most preferably 1.1, the value of y is preferably 1.85-2.05, more preferably 1.9-2.0, and most preferably 1.95. The particle sizes of the Ti powder, the Al powder and the TiC powder are preferably less than 5 mu m independently. In the present invention, the mixing of the Ti powder, the Al powder, and the TiC powder is preferably ball milling mixing, and more preferably dry ball milling mixing. In the invention, the ball milling and mixing equipment is preferably a planetary ball mill, the ball milling and mixing time is preferably 0.5-2 h, the rotation speed of the ball milling and mixing is preferably 200-400 r/min, the filling coefficient is preferably 0.35-0.55, the ball milling and mixing atmosphere is preferably argon atmosphere, the ball milling body is preferably agate balls, and the ball milling tank is preferably a nylon ball milling tank.
After the mixture is obtained, the invention feeds the mixture in an inert atmosphereLine sintering to obtain Ti3AlC2And (3) powder.
According to the invention, the mixture is preferably placed in a graphite crucible for sintering, and further, graphite paper is preferably laid in the graphite crucible to prevent the mixture from polluting the graphite crucible in the sintering process. In the invention, the sintering temperature is preferably 1250-1350 ℃, and the sintering time is preferably 2-5 h. In the present invention, the inert atmosphere is preferably a vacuum atmosphere or an argon atmosphere. In the sintering process of the invention, all raw materials react to obtain Ti3AlC2And (3) powder.
To obtain Ti3AlC2After powdering, the invention is directed to the Ti3AlC2Etching the powder to obtain Ti3C2。
In the invention, the etching solution adopted by the etching is preferably a high-concentration sodium hydroxide solution, and the concentration of the high-concentration sodium hydroxide solution is preferably 30-50 wt.%. In the invention, the time of the etching treatment is preferably 24-72 h. According to the invention, the etching is preferably carried out under the oscillation condition, and the oscillation frequency is preferably 30-50 kHz. The etching treatment of the invention can remove Ti3AlC2Al in the powder is completely etched to form Ti with the shape of accordion3C2. Ti with accordion shape3C2When the titanium alloy is added into the titanium alloy, the titanium alloy has good friction and wear resistance.
After the etching treatment, the invention preferably further comprises filtering, cleaning and drying the etched product in sequence. The present invention does not require any particular embodiment of the filtration, washing and drying, and the filtration, washing and drying means known to those skilled in the art may be used.
The pH value of the mixed solution of the sulfur source and the soluble molybdenum salt is adjusted to be 1-2, and the acidic mixed solution is obtained.
In the present invention, the sulfur source and the soluble molybdenum salt are preferably mixed with water to obtain a mixed solution of the sulfur source and the soluble molybdenum salt. In the present invention, the sulfur source is preferably thiourea, and is more preferably thiourea which is not passivated; the soluble molybdenum salt is preferably sodium molybdate. In the invention, the molar ratio of S to Mo in the sulfur source and the soluble molybdenum salt is preferably 8-12: 2-4, and more preferably 10: 3. The invention has no special requirement on the dosage of the water, and can completely dissolve the sulfur source and the soluble molybdenum salt. According to the invention, the pH value of the mixed solution is preferably adjusted to 1-2, more preferably 1.2-1.5 by adopting ammonia water and/or hydrochloric acid.
To obtain an acidic mixed solution and Ti3C2Then, the invention mixes the acid mixed solution with Ti3C2Mixing, carrying out hydrothermal reaction, and then sequentially separating and drying the hydrothermal reaction product to obtain Ti3C2@MoS2And (3) composite powder.
In the present invention, the Ti is3C2Is preferably MoS270-90% of theoretical yield. The invention preferably adopts ultrasonic oscillation to lead the acidic mixed solution and Ti3C2Uniform mixing is achieved. The invention has no special requirements on the time and power of the ultrasonic oscillation and can realize uniform dispersion.
In the invention, the temperature of the hydrothermal reaction is preferably 180-250 ℃, more preferably 200-230 ℃, and most preferably 220 ℃; the time of the hydrothermal reaction is preferably 10-60 h, more preferably 13-50 h, and most preferably 16 h. In the hydrothermal reaction process, a sulfur source and soluble molybdenum salt react to generate MoS2Simultaneous hydrothermal reaction of formed MoS2Supported on Ti3C2Surface of Ti to form3C2@MoS2。
After the hydrothermal reaction, the hydrothermal reaction product is sequentially separated and dried to obtain Ti3C2@MoS2And (3) composite powder.
In the present invention, the separation is preferably a centrifugal separation. The invention has no special requirements on the rotating speed and time of the centrifugal separation and can realize solid-liquid separation. In the invention, the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 70-120 ℃. The invention has no special requirement on the vacuum drying time and can achieve complete drying.
To obtain Ti3C2@MoS2After the powder is compounded, the invention comprises Mo25(NiCrBSiFe) powder and Ti3C2@MoS2And (3) presetting the mixture of the composite powder, the Ni powder, the Si powder and the TiN powder on the surface of the titanium alloy to form a preset coating.
In the invention, the Mo25(NiCrBSiFe) powder and Ti3C2@MoS2The mass ratio of the composite powder, the Ni powder, the Si powder and the TiN powder is preferably 35-60: 10-25: 5-8: 3-7: 20-25, and more preferably 50:15:8:7: 20. The Mo25(NiCrBSiFe) powder and Ti are treated by the method3C2@MoS2The mixing mode of the composite powder, the Ni powder, the Si powder and the TiN powder has no special requirement, and the mixing mode known by the technicians in the field is adopted, and the dry ball milling mode is preferably adopted to realize the mixing of the materials. In the invention, the ball milling equipment is preferably a planetary ball mill, the ball milling time is preferably 2-4 h, the rotation speed of the ball milling is preferably 200-400 r/min, the filling coefficient is preferably 0.35-0.55, the ball milling mixed atmosphere is preferably argon atmosphere, the ball milling body is preferably agate balls, and the ball milling tank is preferably a nylon ball milling tank.
After the mixture is obtained, the mixture is preset on the surface of the titanium alloy to form a preset coating. In the present invention, the preset mode preferably includes: and uniformly mixing the mixture and the binder to obtain a binding material, and coating the binding material on the surface of the titanium alloy to form a preset coating.
In the present invention, the binder is preferably obtained by directly mixing cellulose acetate and diacetone alcohol; the mass percentage of cellulose acetate in the binder is preferably 5%. The invention has no special requirements on the mixing mode of the binder and the mixture, and the mixing mode is known to those skilled in the art, such as stirring and mixing. In the invention, the thickness of the preset coating is preferably 0.9-1.3 mm, and more preferably 1.0-1.2 mm. When the surface of the titanium alloy is provided with grooves, the thickness of the preset coating does not include the depth of the grooves, but the mixture is ensured to fill the grooves.
After the preset coating is formed, the invention carries out laser cladding on the preset coating to obtain the titanium alloy with the cladding layer.
In the invention, the flow of protective gas for laser cladding is preferably 17-25L/min, more preferably 18-23L/min, and most preferably 20L/min; the laser cladding power is preferably 1700-3500W, more preferably 2000-3000W, and most preferably 2500W; the scanning speed is preferably 5-12 mm/s, more preferably 7-10 mm/s, and most preferably 8 mm/s; the defocusing amount is preferably 30-40 mm, and is further preferably 35 mm; the lap joint ratio is preferably 35% or more, and more preferably 35 to 50%.
In the laser cladding process, metallurgical bonding and chemical bonding are generated between the preset coating and the titanium alloy matrix to form TiN, Ti-Mo, Ti-Ni and Ti-Si multi-component compounds which can be used as hard reinforcing phases and have the functions of improving the hardness and the wear resistance of the coating, thereby improving the wear resistance of the titanium alloy.
After laser cladding, the invention preferably further comprises heat treatment of the laser-clad titanium alloy. In the invention, the temperature of the heat treatment is preferably 650-950 ℃, more preferably 700-900 ℃, and most preferably 750 ℃; the time of the heat treatment is preferably 3-7 hours, and more preferably 3.5 hours. In the present invention, the atmosphere of the heat treatment is preferably a vacuum atmosphere or an argon atmosphere. The heat treatment of the invention can optimize the tissue structure and the component distribution of the titanium alloy cladding coating, thereby achieving the dual purposes of optimizing the structure and the performance.
The following will describe the titanium alloy laser cladding method provided by the present invention in detail with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Cutting a Ti-6Al-4V titanium alloy wire into samples with the sizes of 80mm multiplied by 10mm, then machining trapezoidal grooves which are distributed in parallel, wherein the width of a groove opening is 1mm, the width of a groove bottom is 2mm, the depth of the groove is 0.7mm, the distance of an opening at the upper end of each adjacent groove is 4mm, polishing the surface to remove an oxide film on the surface, and cleaning the surface by using ethanol;
(2) in atomic ratio of Ti3Al1.1C1.95Calculating and weighing Ti powder, Al powder and TiC powder, ball-milling and mixing for 1h by a dry method, wherein powder mixing ball-milling equipment is a planetary ball mill, the rotating speed of a main shaft of the ball mill is 300 revolutions per minute, the filling coefficient is 0.45, a ball-milling body is agate balls, a ball-milling tank is a nylon ball-milling tank, protecting with argon gas, then filling the ball-milled powder into a graphite crucible paved with graphite paper, sintering and preserving heat for 2h at 1300 ℃ in a vacuum furnace to obtain Ti3AlC2Powder; mixing Ti3AlC2Putting the powder into a polymer container, adding NaOH corrosive liquid with the mass concentration of 40% into the container, carrying out oscillation etching treatment for 24 hours, filtering, cleaning and drying to obtain Ti with the accordion shape3C2Powder;
(3) dissolving non-purified thiourea and sodium molybdate in deionized water at a millimole ratio of 10:3, adjusting pH to 1.5 after fully magnetic stirring, and adding Ti3C2Dispersing the powder by ultrasonic oscillation, then putting the mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into an oven, reacting for 16 hours at 220 ℃, then washing the powder by deionized water and absolute ethyl alcohol, carrying out centrifugal separation to collect a product, carrying out vacuum drying on the product, and finally obtaining the supported Ti at the drying temperature of 80 DEG C3C2@MoS2Composite powder;
(4) mo25(NiCrBSiFe) powder and supported Ti3C2@MoS2Weighing composite powder, Ni powder, Si powder and TiN powder according to a mass ratio of 50:15:8:7:20, performing dry ball milling for 2 hours, wherein powder mixing ball milling equipment is a planetary ball mill, the rotating speed of a main shaft of the ball mill is 350 revolutions per minute, the filling coefficient is 0.5, a ball mill body is an agate ball, a ball milling tank is a nylon ball milling tank and is protected by argon, then using a binder prepared from cellulose acetate and diacetone alcohol to preset the mixed powder on Ti-6Al-4V titanium alloy, ensuring that a trapezoid groove is filled, controlling the thickness to be 1.1mm, and finally placing the preset coating in a drying box to dry for 5 hours at 90 ℃ for later use;
(5) cladding by using a laser cladding machine under the protection of argon to obtain a composite coating, wherein the flow of protective gas is 20L/min, the power is 2500W, the scanning speed is 8mm/s, the defocusing amount is 35mm, and the lap joint rate is 35-50%;
(6) and (3) carrying out heat treatment on the titanium alloy coating, wherein the heat treatment temperature is 730 ℃, and the heat treatment time is 3.5h, so that the high-quality coating is finally obtained.
Example 2
(1) Cutting a Ti-6Al-4V titanium alloy wire into samples with the sizes of 80mm multiplied by 10mm, then machining trapezoidal grooves which are distributed in parallel, wherein the width of a groove opening is 1mm, the width of a groove bottom is 2mm, the depth of the groove is 0.7mm, the distance between the groove and an opening at the upper end of the groove is 4mm, polishing the surface to remove an oxide film on the surface, and cleaning the surface by using ethanol;
(2) in atomic ratio of Ti3Al1.1C1.95Calculating and weighing Ti powder, Al powder and TiC powder, ball-milling and mixing for 1h by a dry method, wherein powder mixing ball-milling equipment is a planetary ball mill, the rotating speed of a main shaft of the ball mill is 300 revolutions per minute, the filling coefficient is 0.45, a ball-milling body is agate balls, a ball-milling tank is a nylon ball-milling tank, protecting with argon gas, then filling the ball-milled powder into a graphite crucible paved with graphite paper, sintering and preserving heat for 2h at 1300 ℃ in a vacuum furnace to obtain Ti3AlC2Powder; mixing Ti3AlC2Putting the powder into a polymer container, adding NaOH corrosive liquid with the mass concentration of 40% into the container, carrying out oscillation etching treatment for 24 hours, filtering, cleaning and drying to obtain Ti with the accordion shape3C2Powder;
(3) dissolving non-purified thiourea and sodium molybdate in deionized water at a millimole ratio of 10:3, adjusting pH to 1.5 after fully magnetic stirring, and adding Ti3C2Dispersing the powder by ultrasonic oscillation, then putting the mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into an oven, reacting for 16 hours at 220 ℃, then washing the powder by deionized water and absolute ethyl alcohol, carrying out centrifugal separation to collect a product, carrying out vacuum drying on the product, and finally obtaining the supported Ti at the drying temperature of 80 DEG C3C2@MoS2Composite powder;
(4) mo25(NiCrBSiFe) powder and supported Ti3C2@MoS2Weighing the composite powder, Ni powder, Si powder and TiN powder according to the mass ratio of 50:15:8:7:20,performing dry ball milling for 2 hours, wherein powder mixing ball milling equipment is a planetary ball mill, the rotating speed of a main shaft of the ball mill is 350 revolutions per minute, the filling coefficient is 0.5, a ball milling body is an agate ball, a ball milling tank is a nylon ball milling tank, argon protection is performed, then mixed powder is preset on Ti-6Al-4V titanium alloy by using a binder prepared from cellulose acetate and diacetone alcohol, the filling of a trapezoidal groove is ensured, the thickness is controlled to be 1.1mm, and finally the preset coating is placed in a drying box and dried for 5 hours at 90 ℃ for standby application;
(5) cladding by using a laser cladding machine under the protection of argon to obtain a composite coating, wherein the flow of protective gas is 20L/min, the power is 2000W, the scanning speed is 10mm/s, the defocusing amount is 35mm, and the lap joint rate is 35-50%;
(6) and (3) carrying out heat treatment on the titanium alloy coating, wherein the heat treatment temperature is 850 ℃, and the heat treatment time is 4h, so that the high-quality coating is finally obtained.
Example 3
(1) Cutting a Ti-6Al-4V titanium alloy wire into samples with the sizes of 80mm multiplied by 10mm, then machining trapezoidal grooves which are distributed in parallel, wherein the width of a groove opening is 1mm, the width of a groove bottom is 2mm, the depth of the groove is 0.7mm, the distance between the groove and an opening at the upper end of the groove is 4mm, polishing the surface to remove an oxide film on the surface, and cleaning the surface by using ethanol;
(2) in atomic ratio of Ti3Al1.1C1.95Calculating and weighing Ti powder, Al powder and TiC powder, ball-milling and mixing for 1h by a dry method, wherein powder mixing ball-milling equipment is a planetary ball mill, the rotating speed of a main shaft of the ball mill is 300 revolutions per minute, the filling coefficient is 0.45, a ball-milling body is agate balls, a ball-milling tank is a nylon ball-milling tank, protecting with argon gas, then filling the ball-milled powder into a graphite crucible paved with graphite paper, sintering and preserving heat for 2h at 1300 ℃ in a vacuum furnace to obtain Ti3AlC2Powder; mixing Ti3AlC2Putting the powder into a polymer container, adding NaOH corrosive liquid with the mass concentration of 40% into the container, carrying out oscillation etching treatment for 24 hours, filtering, cleaning and drying to obtain Ti with the accordion shape3C2Powder;
(3) dissolving thiourea and sodium molybdate which are not purified in deionized water, wherein the millimole ratio of the thiourea to the sodium molybdate is 10:3, adjusting the pH value to 1.5 after fully magnetic stirring,then adding Ti3C2Dispersing the powder by ultrasonic oscillation, then putting the mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into an oven, reacting for 16 hours at 220 ℃, then washing the powder by deionized water and absolute ethyl alcohol, carrying out centrifugal separation to collect a product, carrying out vacuum drying on the product, and finally obtaining the supported Ti at the drying temperature of 80 DEG C3C2@MoS2Composite powder;
(4) mo25(NiCrBSiFe) powder and supported Ti3C2@MoS2Weighing composite powder, Ni powder, Si powder and TiN powder according to a mass ratio of 50:15:8:7:20, performing dry ball milling for 2 hours, wherein powder mixing ball milling equipment is a planetary ball mill, the rotating speed of a main shaft of the ball mill is 350 revolutions per minute, the filling coefficient is 0.5, a ball mill body is an agate ball, a ball milling tank is a nylon ball milling tank and is protected by argon, then using a binder prepared from cellulose acetate and diacetone alcohol to preset the mixed powder on Ti-6Al-4V titanium alloy, ensuring that a trapezoid groove is filled, controlling the thickness to be 1.1mm, and finally placing the preset coating in a drying box to dry for 5 hours at 90 ℃ for later use;
(5) cladding by using a laser cladding machine under the protection of argon to obtain a composite coating, wherein the flow of protective gas is 20L/min, the power is 3000W, the scanning speed is 12mm/s, the defocusing amount is 35mm, and the lap joint rate is 35-50%;
(6) and carrying out heat treatment on the titanium alloy coating, wherein the heat treatment temperature is 950 ℃, and the heat treatment time is 3h, so that the high-quality coating is finally obtained.
Example 4
(1) Cutting a Ti-6Al-4V titanium alloy wire into samples with the sizes of 80mm multiplied by 10mm, then machining trapezoidal grooves which are distributed in parallel, wherein the width of a groove opening is 0.6mm, the width of a groove bottom is 2.5mm, the depth of the groove is 0.8mm, the distance of an opening at the upper end of each adjacent groove is 4mm, polishing the surface to remove an oxide film on the surface, and cleaning the surface by using ethanol;
(2) in atomic ratio of Ti3Al1.2C2.05Calculating and weighing Ti powder, Al powder and TiC powder, ball-milling and mixing for 1h by a dry method, wherein the powder mixing ball-milling equipment is a planetary ball mill, the rotating speed of a main shaft of the ball mill is 300 r/min, the filling coefficient is 0.45, a ball mill body is agate balls,the ball milling tank is a nylon ball milling tank, argon is used for protection, then the ball milled powder is put into a graphite crucible paved with graphite paper, and sintering and heat preservation are carried out for 2 hours at 1300 ℃ in a vacuum furnace to obtain Ti3AlC2Powder; mixing Ti3AlC2Putting the powder into a polymer container, adding NaOH corrosive liquid with the mass concentration of 40% into the container, carrying out oscillation etching treatment for 24 hours, filtering, cleaning and drying to obtain Ti with the accordion shape3C2Powder;
(3) dissolving non-purified thiourea and sodium molybdate in deionized water at a millimole ratio of 10:3, adjusting pH to 1.5 after fully magnetic stirring, and adding Ti3C2Dispersing the powder by ultrasonic oscillation, then putting the mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into an oven, reacting for 16 hours at 220 ℃, then washing the powder by deionized water and absolute ethyl alcohol, carrying out centrifugal separation to collect a product, carrying out vacuum drying on the product, and finally obtaining the supported Ti at the drying temperature of 80 DEG C3C2@MoS2Composite powder;
(4) mo25(NiCrBSiFe) powder and supported Ti3C2@MoS2Weighing composite powder, Ni powder, Si powder and TiN powder according to a mass ratio of 35:25:8:7:25, performing dry ball milling for 2 hours, wherein powder mixing ball milling equipment is a planetary ball mill, the rotating speed of a main shaft of the ball mill is 350 revolutions per minute, the filling coefficient is 0.5, a ball mill body is an agate ball, a ball milling tank is a nylon ball milling tank and is protected by argon, then using a binder prepared from cellulose acetate and diacetone alcohol to preset the mixed powder on Ti-6Al-4V titanium alloy, ensuring that a trapezoid groove is filled, controlling the thickness to be 1.1mm, and finally placing the preset coating in a drying box to dry for 5 hours at 90 ℃ for later use;
(5) cladding by using a laser cladding machine under the protection of argon to obtain a composite coating, wherein the flow of protective gas is 20L/min, the power is 2500W, the scanning speed is 10mm/s, the defocusing amount is 30mm, and the lap joint rate is 35-50%;
(6) and (3) carrying out heat treatment on the titanium alloy coating, wherein the heat treatment temperature is 850 ℃, and the heat treatment time is 5h, so that the high-quality coating is finally obtained.
Example 5
(1) Cutting a Ti-6Al-4V titanium alloy wire into samples with the sizes of 80mm multiplied by 10mm, then machining trapezoidal grooves which are distributed in parallel, wherein the width of a groove opening is 0.7mm, the width of a groove bottom is 2.4mm, the depth of the groove is 0.7mm, the distance between the groove and an opening at the upper end of the groove is 4mm, polishing the surface to remove a surface oxide film, and cleaning the surface oxide film by using ethanol;
(2) in atomic ratio of Ti3Al1.2C2Calculating and weighing Ti powder, Al powder and TiC powder, ball-milling and mixing for 1h by a dry method, wherein powder mixing ball-milling equipment is a planetary ball mill, the rotating speed of a main shaft of the ball mill is 300 revolutions per minute, the filling coefficient is 0.45, a ball-milling body is agate balls, a ball-milling tank is a nylon ball-milling tank, protecting with argon gas, then filling the ball-milled powder into a graphite crucible paved with graphite paper, sintering and preserving heat for 2h at 1300 ℃ in a vacuum furnace to obtain Ti3AlC2Powder; mixing Ti3AlC2Putting the powder into a polymer container, adding NaOH corrosive liquid with the mass concentration of 40% into the container, carrying out oscillation etching treatment for 24 hours, filtering, cleaning and drying to obtain Ti with the accordion shape3C2Powder;
(3) dissolving non-purified thiourea and sodium molybdate in deionized water at a millimole ratio of 10:3, adjusting pH to 1.5 after fully magnetic stirring, and adding Ti3C2Dispersing the powder by ultrasonic oscillation, then putting the mixed solution into a stainless steel reaction kettle containing a polytetrafluoroethylene lining, putting the stainless steel reaction kettle into an oven, reacting for 16 hours at 220 ℃, then washing the powder by deionized water and absolute ethyl alcohol, carrying out centrifugal separation to collect a product, carrying out vacuum drying on the product, and finally obtaining the supported Ti at the drying temperature of 80 DEG C3C2@MoS2Composite powder;
(4) mo25(NiCrBSiFe) powder and supported Ti3C2@MoS2Weighing the composite powder, Ni powder, Si powder and TiN powder according to a mass ratio of 60:10:5:5:20, performing dry ball milling for 2 hours, wherein powder mixing ball milling equipment is a planetary ball mill, the rotating speed of a main shaft of the ball mill is 350 revolutions per minute, the filling coefficient is 0.5, a ball mill body is agate balls, a ball milling tank is a nylon ball milling tank, argon gas is used for protection, and then cellulose acetate and dipropylene are used for protectionThe mixed powder is preset on Ti-6Al-4V titanium alloy by using a bonding agent prepared by ketol, the trapezoid groove is ensured to be filled, the thickness is controlled to be 1.1mm, and finally the preset coating is dried in a drying oven at 90 ℃ for 5 hours for later use;
(5) cladding by using a laser cladding machine under the protection of argon to obtain a composite coating, wherein the flow of protective gas is 20L/min, the power is 3500W, the scanning speed is 12mm/s, the defocusing amount is 40mm, and the lap joint rate is 35-50%;
(6) and carrying out heat treatment on the titanium alloy coating, wherein the heat treatment temperature is 800 ℃, and the heat treatment time is 4h, so that the high-quality coating is finally obtained.
The titanium alloy treated in the examples 1-5 and the Ti-6Al-4V titanium alloy which is not subjected to laser cladding treatment are subjected to a friction wear test under the following test conditions: the loading load is 10kg, the rotating speed is 150r/min, the time is 0.5h, the grinding ball is 20 percent Co-WC hard alloy, and the test result is shown in table 1.
TABLE 1 Friction wear test results
| Numbering | microhardness/HV0.3 | Coefficient of friction | Abrasion loss/mg |
| Example 1 | 1169.4 | 0.3051 | 3.355 |
| Example 2 | 1158.6 | 0.3206 | 3.847 |
| Example 3 | 1075.2 | 0.3427 | 4.059 |
| Example 4 | 1226.3 | 0.3154 | 3.508 |
| Example 5 | 1183.1 | 0.3279 | 3.746 |
| Ti-6Al-4V titanium alloy matrix | 380 | 0.3745 | 12.936 |
As can be seen from Table 1, after the treatment by the methods of examples 1 to 5, the microhardness, the friction coefficient and the abrasion loss of the laser cladding multi-component composite coating on the surface of the titanium alloy are all significantly better than those of the titanium alloy substrate.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The laser cladding method of the titanium alloy is characterized by comprising the following steps of:
mixing Mo25(NiCrBSiFe) powder and Ti3C2@MoS2The mixture of the composite powder, the Ni powder, the Si powder and the TiN powder is preset on the surface of the titanium alloy to form a preset coating; and carrying out laser cladding on the preset coating to obtain the titanium alloy with the cladding layer.
2. Laser cladding method according to claim 1, wherein the surface of said titanium alloy is grooved.
3. The laser cladding method according to claim 2, wherein the depth of the groove is 0.7-1 mm.
4. Laser cladding method according to claim 2 or 3, wherein said groove is a trapezoidal groove.
5. Laser cladding method according to claim 1, wherein said Mo25(NiCrBSiFe) powder, Ti3C2@MoS2The mass ratio of the composite powder to the Ni powder to the Si powder to the TiN powder is 35-60: 10-25: 5-8: 3-7: 20-25.
6. Laser cladding method according to claim 1, wherein said Ti3C2@MoS2The preparation of the composite powder comprises the following steps:
sintering the mixture of Ti powder, Al powder and TiC powder in inert atmosphere to obtain Ti3AlC2Powder; for the obtained Ti3AlC2Etching the powder to obtain Ti3C2；
Adjusting the pH value of the sulfur source and soluble molybdenum salt mixed solution to 1-2 to obtain an acidic mixed solution; mixing the acidic mixed solution with Ti3C2Mixing, carrying out hydrothermal reaction, and sequentially separating and drying the hydrothermal reaction product to obtain Ti3C2@MoS2And (3) composite powder.
7. The laser cladding method according to claim 6, wherein the temperature of the hydrothermal reaction is 180-250 ℃ and the time of the hydrothermal reaction is 10-60 hours.
8. The laser cladding method of claim 1, wherein the flow of protective gas for laser cladding is 17-25L/min, the power is 1700-3500W, the scanning speed is 5-12 mm/s, the defocusing amount is 30-40 mm, and the overlapping rate is more than 35%.
9. The laser cladding method of claim 1, further comprising heat treating the titanium alloy with the cladding layer after laser cladding.
10. The laser cladding method according to claim 9, wherein the heat treatment temperature is 650-950 ℃ and the heat treatment time is 3-7 hours.
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Application publication date: 20190611 Assignee: Yantai Nuclear Power Intelligent Technology Research Institute Co.,Ltd. Assignor: Yantai Zhongxin Interconnection Energy Technology Co.,Ltd. Contract record no.: X2023980052343 Denomination of invention: A Laser Cladding Method for Titanium Alloy Granted publication date: 20201013 License type: Exclusive License Record date: 20231222 |