CN110760845A - Anti-oxidation high-hardness wear-resistant coating on titanium alloy surface and preparation method thereof - Google Patents
Anti-oxidation high-hardness wear-resistant coating on titanium alloy surface and preparation method thereof Download PDFInfo
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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
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- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
- C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
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- C22C14/00—Alloys based on titanium
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0047—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
- C22C32/0052—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides
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Abstract
The invention belongs to the field of titanium alloy surface engineering, and particularly relates to an anti-oxidation high-hardness wear-resistant coating on a titanium alloy surface and a preparation method thereof. The coating is prepared by a coaxial powder feeding laser cladding technology; the cladding powder is counted by mass and comprises 75 wt% of TC4 and 25 wt% of NiCr-Cr3C2And (3) powder. The coaxial powder feeding laser cladding technology can accurately control the forming quality, reduce the finish machining workload in the coating application process and improve the efficiency. Cr (chromium) component3C2The powder has low melting point, no unmelted particles exist in the processing process, and simultaneously Cr3C2The powder has good normal temperature and high temperature hardness, and the composite powder NiCr-Cr3C2Ni capable of providing elements required for forming a reinforcing phase in a laser cladding process and providing solid solution strengthening of a matrix,Cr element. The Ti6Al4V powder relieves the overlarge thermal physical property difference between the reinforcing phase and the base material, and can play a certain deformation buffering role.
Description
Technical Field
The invention belongs to the field of titanium alloy surface engineering, and particularly relates to an anti-oxidation high-hardness wear-resistant coating on a titanium alloy surface and a preparation method thereof.
Background
The titanium alloy has the characteristics of small density, high specific strength and strong corrosion resistance, is widely applied to the field of aviation, aerospace, ships and ocean engineering equipment, and plays an irreplaceable role in the aspects of equipment evolution and light weight. In the case of aircraft, the aircraft fuselage material is gradually transitioning from traditional aluminum alloy materials to Carbon Fiber Reinforced Plastics (CFRP), and some of the steel components that are subjected to high strength, such as frames and joints, are also replaced with titanium alloys to reduce weight. This is because the titanium alloy has the characteristics of light weight and high strength, and simultaneously has physical properties similar to those of the carbon fiber reinforced material, and can avoid potential corrosion when used as a joint material. In addition, the titanium alloy can be used as an engine material, and is mainly used as components of fans, compressor blades and the like which are used at lower temperature (<600/° C). Ti-6Al-4V (TC4) is the most widely used titanium alloy, has excellent specific strength, excellent corrosion resistance and fracture toughness, and good weld workability and ability to withstand extreme temperatures, and can be strengthened by heat treatment. The poor frictional wear performance of the surface of the titanium alloy is a bottleneck limiting the development of the titanium alloy, and in order to improve the frictional wear performance of the surface of the titanium alloy, some related patents for preparing a wear-resistant coating on the surface of the titanium alloy exist at present, and are specifically shown in table 1.
TABLE 1 patents relating to wear-resistant coatings on titanium alloy surfaces
In the above table, the patent nos. 1 and 2 both adopt chemical plating to prepare the wear-resistant coating, so that the method has complicated steps, and more acidic and alkaline reagents used in the preparation process have great toxicity to the environment and human body; the patent No. 3 requires cold spraying of H13 powder in laser cladding processing, the powder needs special treatment and preparation, and the spraying step is relatively complicated; the cladding powder of the patent No. 4 is TiNiCoCrVSi multicomponent alloy powder, and the phase in the coating is relatively complex, so that the defects of poor deformation coordination capability among phases, easy occurrence of cracks and the like can be faced, and rare earth elements are needed to improve the coating quality; the patent No. 5 prepares the laser wear-resistant coating through a preset powder method, acidic, alkaline and toxic reagents can be contacted in the preparation process of the preset powder, so that great potential safety hazards exist, the forming control of the preset powder method is difficult, the volatilization of a binder in the processing process can cause the coating to generate defects, and the coating of the preset coating is easy to fall off.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a titanium alloy surface oxidation-resistant high-hardness wear-resistant coating capable of improving the friction and wear performance of the titanium alloy surface and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following specific technical scheme:
an anti-oxidation high-hardness wear-resistant coating on the surface of a titanium alloy is prepared by a coaxial powder feeding laser cladding technology; the cladding powder is counted by mass and comprises 75 wt% of TC4 and 25 wt% of NiCr-Cr3C2And (3) powder.
Furthermore, the chemical components of the TC4 powder measured by mass percentage comprise 89.27 wt% of Ti, 6.22 wt% of Al, 4.32 wt% of V, and the balance of Fe, C, H, O and N.
Further, the NiCr-Cr3C2The measured chemical components of the powder are counted by mass percent and comprise 19.59 weight percent of Ni, 10.28 weight percent of C and the balance of Cr.
Furthermore, the particle size distribution of the TC4 powder is 53-150 mu m.
Further, the NiCr-Cr3C2The particle size distribution of the mixed powder is 100-150 μm.
Further, the preparation method of the anti-oxidation high-hardness wear-resistant coating on the surface of the titanium alloy comprises the following steps,
s1, detecting the purchased Ti6Al4V base material and the cladding powder to ensure the cladding quality;
s2, performing sand blasting treatment on the base material to be clad, wherein the surface of the test block after sand blasting is roughDegree RaAbout 1.98 to 2.07 μm; placing the test block subjected to sand blasting into alcohol, performing ultrasonic cleaning for 2-5 min, blow-drying, and placing into an argon protection box with the purity of 99.9%;
s3, putting the cladding powder into a ball mill according to the proportion, performing ball milling and powder mixing for more than 12 hours, putting the mixed powder into a vacuum drying oven, drying at the constant temperature of 80 ℃ for more than 10 hours, and taking out the powder from the constant temperature drying oven and putting the powder to a powder feeder before cladding;
and S4, cladding the cladding powder on the test block to be clad by adopting a coaxial powder feeding laser.
Further, the cladding parameters of S4 are specifically: the multi-channel lap joint rate is 50%, the laser focal length is 16mm, the laser power is 700-1100W, the scanning speed is 0.4m/min, the powder feeding amount is 1.4r/min, the spot diameter is 3.0mm, the powder feeding gas is helium, the gas flow rate is 7.0L/min, argon protection is adopted in the whole process of the cladding process, and the gas flow rate is 8-15L/min.
The invention has the advantages and positive effects that:
the invention provides an anti-oxidation high-hardness wear-resistant coating on the surface of a titanium alloy and a preparation method thereof. The coaxial powder feeding laser cladding technology can accurately control the forming quality, reduce the finish machining workload in the coating application process and improve the efficiency. Cr (chromium) component3C2The powder has low melting point, no unmelted particles exist in the processing process, and simultaneously Cr3C2The powder has good normal temperature and high temperature hardness, and the composite powder NiCr-Cr3C2Can provide elements required for forming a reinforcing phase in the laser cladding process and can also provide Ni and Cr elements for solid solution strengthening of a matrix. The Ti6Al4V powder relieves the overlarge thermal physical property difference between the reinforcing phase and the base material, and can play a certain deformation buffering role.
In addition, compared with the method of preparing the wear-resistant coating on the surface of the titanium alloy by chemical plating, the method has the advantages that the dosage of strong-oxidation, strong-corrosiveness and toxic chemical reagents is less, and the toxicity to human bodies and the environment in the operation process is reduced; the method has the advantages of fewer working procedures, simple operation and easy realization, and can improve the titaniumThe surface of the alloy has wear resistance, and the service cycle of the titanium alloy component is prolonged; the phase in the invention is simple, wherein the reinforcing phase TiCxThe surface hardness of the titanium alloy is improved, and the functions of wear resistance and oxidation resistance are realized; the defects of cracks, air holes and the like in the invention are obviously changed along with the increase of the laser power, and the influence of the power on the laser cladding macroscopic quality is favorably researched by scientific researchers.
Drawings
FIG. 1 is a diagram showing the morphology of the mixed powders in examples 1 to 3 of the present invention;
FIG. 2 is a graph showing the results of dye penetrant inspection of the surface of a clad specimen in examples 1-3 of the present invention; a. example 1; b. example 2; c. example 3;
fig. 3 is a graph showing the result of X-ray diffraction measurement of a cladding sample in example 3 of the present invention using an X-ray diffractometer model D8 ADVANCE;
FIG. 4 is a graph showing the results of the statistics of the reinforcing phases of the samples of examples 1-3 using an OLYMPUS metallographic microscope;
FIG. 5 is a graph showing the results of the porosity statistics of the samples of examples 1-3 using an OLYMPUS metallographic microscope;
FIG. 6 is a graph showing the results of scanning electron microscopy using HITACHI S-3000 on the macro morphology of the cladding samples of examples 1-3; a. example 1; b. example 2; c. example 3;
FIG. 7 is a graph showing the results of the microstructure morphology of the cladding samples of examples 1-3 using a HITACHI S-3000 scanning electron microscope; a. example 1; b. example 2; c. example 3;
FIG. 8 is the results of elemental analysis of Ni and Cr for the coating of example 3 using a JXA-8530F Plus type field emission electron probe spectrometer; a. ni element; b. cr element;
FIG. 9 shows the results of microhardness testing of the coating of example 3 using a KB30SR-FA digital Vickers hardness tester.
Detailed Description
For a further understanding of the contents, features and effects of the present invention, the following examples are illustrated in the accompanying drawings and described in the following detailed description:
the invention discloses a titanium alloyThe gold surface is an oxidation-resistant high-hardness wear-resistant coating, and the coating is prepared by a coaxial powder feeding laser cladding technology; the cladding powder is counted by mass and comprises 75 wt% of TC4 and 25 wt% of NiCr-Cr3C2And (3) powder.
The coaxial powder feeding laser cladding technology can accurately control the forming quality, reduce the finish machining workload in the coating application process and improve the efficiency.
The TC4 material is Ti-6Al-4V, belongs to (α + β) type titanium alloy, has good comprehensive mechanical properties, can improve the compatibility of cladding powder and titanium-based material by TC4 powder, avoids cracks caused by overlarge differences of physicochemical properties such as linear expansion coefficient, thermal conductivity and the like, relieves overlarge thermophysical property differences between a reinforcing phase and a base material by the Ti6Al4V powder, and can play a certain role in deformation buffering.
NiCr-Cr3C2Is a ceramic mixed material, has lower melting point and density, does not have unmelted particles in the processing process, and simultaneously Cr3C2The powder has good normal temperature and high temperature hardness, and the composite powder NiCr-Cr3C2Can provide elements required for forming a reinforcing phase in the laser cladding process, can provide Ni and Cr elements for solid solution strengthening of a matrix, and is an anti-friction and wear-resistant material with excellent comprehensive performance;
preferably, the measured chemical components of the Ti6Al4V powder are counted by mass percentage, and comprise 89.27 wt% of Ti, 6.22 wt% of Al, 4.32 wt% of V and the balance of Fe, C, H, O and N; the particle size distribution of the powder is 53-150 μm.
Preferably, said NiCr-Cr3C2The measured chemical components of the powder are counted according to mass percentage, the measured chemical components comprise 19.59 wt% of Ni, 10.28 wt% of C and the balance of Cr, and the particle size distribution of the powder is 100-150 mu m.
The invention also discloses a preparation method of the anti-oxidation high-hardness wear-resistant coating on the surface of the titanium alloy, which comprises the following steps:
s1, detecting the purchased Ti6Al4V base material and the cladding powder to ensure the cladding quality;
s2, preprocessing a base material to be clad;
s3, preprocessing the cladding powder;
and S4, cladding the cladding powder on the test block to be clad by adopting a coaxial powder feeding laser.
In S1, firstly, cleaning stains on the surface of the titanium alloy plate to be processed by absolute ethyl alcohol, and cutting the base material to be cladded into cladding test blocks of 100 multiplied by 10mm by an electric spark cutting machine;
preprocessing a cladding test block in S2, specifically: carrying out sand blasting treatment on the test block to be cladded to remove a surface oxide layer and dirt, simultaneously improving the roughness of the test block to be cladded, improving the absorption rate of laser energy, and improving the surface roughness R of the test block after sand blastingaAbout 1.98 to 2.07 μm; and (3) putting the test block subjected to sand blasting into alcohol, carrying out ultrasonic cleaning for 2-5 min, then blow-drying, and putting into an argon protection box with the purity of 99.9%.
Preprocessing the cladding powder in S3, specifically: putting the cladding powder into a ball mill according to the proportion for ball milling and powder mixing, wherein the powder mixing time is more than 12h, putting the mixed powder into a vacuum drying oven, drying at the constant temperature of 80 ℃ for more than 10h, and taking out the powder from the constant temperature drying oven and putting the powder into a powder feeder before cladding processing so as to ensure the flowability of the powder.
S4, cladding the cladding powder on the test block to be clad by adopting a coaxial powder feeding laser, wherein the cladding parameters are as follows: the multi-pass lap joint rate is 50%, the laser focal length is 16mm, the laser power is 700/900/1100W, the scanning speed is 0.4m/min, the powder feeding amount is 1.4r/min, the diameter of a light spot is 3.0mm, the powder feeding gas is helium, the gas flow rate is 7.0L/min, argon gas is adopted for protection in the whole process of cladding, and the gas flow rate is 8-15L/min.
Example one
The concrete scheme of the scheme is 75 wt% of TC4 and 25 wt% of NiCr-Cr3C2And preparing the laser cladding coating with the laser power of 700W according to the steps.
Example two
The concrete scheme of the scheme is 75 wt% of TC4 and 25 wt% of NiCr-Cr3C2And preparing the laser cladding coating with the laser power of 900W according to the steps.
EXAMPLE III
The scheme isThe concrete scheme is 75 wt% TC4+25 wt% NiCr-Cr3C2And preparing the laser cladding coating with the laser power of 1100W according to the steps.
Test examples
The morphology of the mixed powder is shown in figure 1; the TC4 powder is spherical powder, the NiCr-Cr3C2 powder is spherical-like powder, the two kinds of powder ensure good fluidity during cladding processing, and the two kinds of powder are uniformly mixed, so that the cladding quality can be ensured.
The results of the dye penetrant flaw detection of the surface of the clad specimens of examples 1 to 3 are shown in FIG. 2; it can be seen that the cracks on the surface of the cladding sample are gradually reduced along with the increase of the power, the power is 1100W (example 3), the cracks are well inhibited, and the implementation effect is best.
The X-ray diffraction detection result of the cladding sample is shown in FIG. 3, and it can be seen that the phase in the cladding layer is ceramic reinforced phase TiCx, and the base phase is α -Ti.
The reinforcing phases of the samples are counted by a metallographic microscope, and the result is shown in fig. 4; statistics were performed on the porosity and the results are shown in fig. 5: the amount of reinforcing phase determines the oxidation and abrasion resistance of the coating, and generally, the greater the amount of reinforcing phase, the better the performance of the laser cladding. It goes without saying that the more pores, the poorer the macroscopic quality of the coating and the poorer the properties of the coating. When the power is 1100W (example 3), the number of the reinforcing phases in the cladding layer is the largest, the porosity is the lowest, and the implementation effect is the best.
The macroscopic morphology result of the cladding sample is shown in fig. 6; it can be seen that, as the laser power is increased, cracks and pores in the cross section of the cladding layer are effectively suppressed, and the effect is the best at 1100W (example 3).
The microstructure morphology is shown in fig. 7: it can be seen that the enhanced phase TiCx morphology of the coating transitions from granular to dendritic with increasing power, but cracks still exist at lower power, so overall consideration is optimal at power 1100 (example 3).
As shown in fig. 8: the Ni and Cr elements in the cladding layer are uniformly distributed in the substrate, so that the solid solution strengthening effect can be achieved, and the hardness of the coating is increased.
As shown in fig. 9: the microhardness of the coating of example three was tested using a digital microhardness tester with a load of 500g and a dwell time of 12s, and it was found that the microhardness of the cladding was about 1.4 times that of Ti6Al4V, and that there was a relatively smooth transition between the cladding and the substrate.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and all simple modifications, equivalent changes and modifications made to the above embodiment according to the technical spirit of the present invention are within the scope of the technical solution of the present invention.
Claims (7)
1. The anti-oxidation high-hardness wear-resistant coating on the surface of the titanium alloy is characterized in that: the coating is prepared by a coaxial powder feeding laser cladding technology; the cladding powder is counted by mass and comprises 75 wt% of TC4 and 25 wt% of NiCr-Cr3C2And (3) powder.
2. The titanium alloy surface oxidation-resistant high-hardness wear-resistant coating according to claim 1, characterized in that: the actual measurement chemical components of the TC4 powder are counted according to mass percentage and comprise 89.27 wt% of Ti, 6.22 wt% of Al, 4.32 wt% of V and the balance of Fe, C, H, O and N.
3. The titanium alloy surface oxidation-resistant high-hardness wear-resistant coating according to claim 1, characterized in that: the NiCr-Cr3C2The measured chemical components of the powder are counted by mass percent and comprise 19.59 weight percent of Ni, 10.28 weight percent of C and the balance of Cr.
4. The titanium alloy surface oxidation-resistant high-hardness wear-resistant coating according to claim 1, characterized in that: the particle size distribution of the TC4 powder is 53-150 mu m.
5. The titanium alloy surface oxidation-resistant high-hardness wear-resistant coating according to claim 1, characterized in that: the NiCr-Cr3C2The particle size distribution of the mixed powder is 100-150 μm.
6. The method for preparing the anti-oxidation high-hardness wear-resistant coating on the surface of the titanium alloy as claimed in any one of claims 1 to 5, characterized in that: comprises the following steps of (a) carrying out,
s1, detecting the purchased Ti6Al4V base material and the cladding powder to ensure the cladding quality;
s2, performing sand blasting treatment on the base material to be clad, and performing sand blasting on the surface roughness R of the test blockaAbout 1.98 to 2.07 μm; placing the test block subjected to sand blasting into alcohol, performing ultrasonic cleaning for 2-5 min, blow-drying, and placing into an argon protection box with the purity of 99.9%;
s3, putting the cladding powder into a ball mill according to the proportion, performing ball milling and powder mixing for more than 12 hours, putting the mixed powder into a vacuum drying oven, drying at the constant temperature of 80 ℃ for more than 10 hours, and taking out the powder from the constant temperature drying oven and putting the powder to a powder feeder before cladding;
and S4, cladding the cladding powder on the test block to be clad by adopting a coaxial powder feeding laser.
7. The method for preparing the anti-oxidation high-hardness wear-resistant coating on the surface of the titanium alloy as claimed in claim 6, wherein the method comprises the following steps: the cladding parameters of S4 are specifically as follows: the multi-channel lap joint rate is 50%, the laser focal length is 16mm, the laser power is 700-1100W, the scanning speed is 0.4m/min, the powder feeding amount is 1.4r/min, the spot diameter is 3.0mm, the powder feeding gas is helium, the gas flow rate is 7.0L/min, argon protection is adopted in the whole process of the cladding process, and the gas flow rate is 8-15L/min.
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| CN111593342A (en) * | 2020-06-10 | 2020-08-28 | 中国航发北京航空材料研究院 | Powder for repairing TC4 rotating shaft and rocker arm abrasion defects through laser cladding and process method |
| CN116352078A (en) * | 2023-03-22 | 2023-06-30 | 长沙航空职业技术学院(空军航空维修技术学院) | Laser additive repairing process |
| CN116623060A (en) * | 2023-07-26 | 2023-08-22 | 内蒙古工业大学 | Laser additive alloy based on CrCoVWYC powder, composite coating and preparation method of composite coating |
| WO2024120548A1 (en) * | 2023-07-26 | 2024-06-13 | 内蒙古工业大学 | Laser additive alloy based on nitialvcmo powder, and composite coating and preparation method for composite coating |
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| WO2024120548A1 (en) * | 2023-07-26 | 2024-06-13 | 内蒙古工业大学 | Laser additive alloy based on nitialvcmo powder, and composite coating and preparation method for composite coating |
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