CN107099796B - A kind of titanium-based laser cladding coating and preparation method thereof - Google Patents
A kind of titanium-based laser cladding coating and preparation method thereof Download PDFInfo
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- CN107099796B CN107099796B CN201710285323.3A CN201710285323A CN107099796B CN 107099796 B CN107099796 B CN 107099796B CN 201710285323 A CN201710285323 A CN 201710285323A CN 107099796 B CN107099796 B CN 107099796B
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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
- C23C24/00—Coating starting from inorganic powder
- 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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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C30/00—Alloys containing less than 50% by weight of each constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- 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
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Abstract
The present invention discloses a kind of titanium-based laser cladding coating and preparation method thereof, its laser cladding coating raw material includes the powder of following mass percent: C:4% ~ 7%, W:12% ~ 16%, Al:27% ~ 32%, B:2% ~ 5%, V:3% ~ 5%, Be:0.3% ~ 0.8%, surplus Ti；Coating preparation is carried out using laser melting coating；The coating hardness that laser melting coating of the present invention obtains is higher, has good wearability and corrosion resistance under high-temperature work environment；There is no slag inclusion or bubble inside the high-temperature wear resistant coating that titanium alloy surface obtains, cladding layer and matrix conjugation are high.
Description
Technical field
The invention belongs to laser melting and coating technique field, in particular to a kind of titanium-based laser cladding coating and preparation method thereof.
Background technique
Titanium is a kind of important metal material to grow up in 20th century, with specific strength is high, corrosion resistance is good, heat resistance
The advantages that high, this makes titanium alloy obtain a large amount of application under severe working environment.Other performances of titanium alloy, such as toughness
It is good, nonmagnetic, fusing point is high, the rudimentary resistance to bioerodible of thermal expansion coefficient etc., also there is considerable meaning in certain fields.
Titanium or titanium alloy has extensive use in fields such as Aeronautics and Astronautics, naval vessel, weapons, nuclear energy.The application of titanium alloy is initially used for navigating
Empty industry, mainly aircraft engine, rack, undercarriage and rocket-powered missile.Aluminium alloy is most widely used one kind in industry
Non-ferrous metal structural material has been widely applied in Aeronautics and Astronautics, automobile, machine-building, ship and chemical industry.But usually
In the case of titanium, the wearability of aluminium alloy and high temperature oxidation resistance it is poor, will affect its service life.Increase by one in its alloy surface
Laminated gold plating can enhance the wear-resistant and resistance to corrosion on its surface well, while can be used to repair impaired table
Face.
104004998 B of patent CN discloses one kind and passes through corona discharge preparation on the surface TC4
The method of the titanium-based amorphous coating of Ti46Zr20V12Cu5Be17 has been made the amorphous coating of large area in titanium alloy surface, has been obtained
The amorphous coating obtained has good wearability；105400240 A of patent CN discloses a kind of phosphoric acid for titanium group high temperature protection
Salt coating and preparation method thereof；105603483 A of patent CN discloses a kind of preparation side of titanium-base alloy high-temperature oxidation resistant coating
Method is prepared for one layer of Ti on TiAl alloy surface by way of plating3Al alloy coat achieves good high-temperature oxidation resistant
Property.From the point of view of current patent disclosure situation, it is related to using titanium-base alloy as coating and preparation method thereof and few.
Titanium-base alloy at high temperature, is still able to maintain excellent elevated temperature strength, high temperature hardness, high temperature wear resistant, oxygen resistant to high temperatures
Change and the comprehensive performances such as heat fatigue.Wherein laser melting coating is also known as laser cladding or laser cladding, it is by adding in substrate surface
Add required cladding material (Ni-based, cobalt-based, ferrous alloy, tungsten carbide composite), and will be melt using high-energy-density laser beam
Whiting end rapidly solidification together with substrate surface thin layer forms one kind with cladding material in metallurgical bonding coating in substrate surface
Green process for modifying surface.Currently, laser melting coating is mainly used to coat or repair various metal parts, to significantly improve base's table
The performances such as wearability, corrosion resistance, heat resistance and the inoxidizability in face, thus achieve the purpose that surface is modified or repairs, it is both full
Requirement of the foot to material surface particular characteristic, and saved a large amount of noble elements.
But the characteristics of heat quenching anxious there is nonequilibrium solidification process because of laser melting coating, the microstructure of surface cladding layer of formation easily produces
The defects of raw crackle and stomata, the industrial applications of laser melting and coating technique are caused to be subject to certain restrictions, for the performance for making cladding layer
It is improved, many scholars start to explore the mode that rare earth is added in the powder to improve coating performance, due to rare earth cost mistake
Height, by save the cost, the invention proposes replace rare earth modified coating with Be element.
Summary of the invention
The present invention provides a kind of titanium-based laser cladding coating and preparation method thereof, and it is excellent and compound to be desirably to obtain high-temperature behavior
The compact coating of layer.
A kind of titanium-based laser cladding coating, laser cladding coating raw material include the powder of following mass percent: C:4% ~
7%, W:12% ~ 16%, Al:27% ~ 32%, B:2% ~ 5%, V:3% ~ 5%, Be:0.3% ~ 0.8%, surplus Ti.
The average particle size of the powder is 70 ~ 100 μm.
Another object of the present invention is to provide the preparation methods of the titanium-based laser cladding coating, comprising the following steps:
(1) metal base surface is polished bright and clean and cleaned up, specifically, metal base surface is beaten with 400 mesh sand paper
It is polished with 600 mesh sand paper after mill, is then cleaned with acetone again；
(2) proportionally prepare cladding coating raw material powder, raw material powder is made after mixing by vacuum ball milling method
It is dry using drying box；
(3) by the preset powder of powder of step (2) in metal base surface, fore-put powder is with a thickness of 1 ~ 2mm；
(4) laser melting coating is carried out to the fore-put powder of step (3), so that preset powder melts simultaneously with metallic matrix surface layer,
To form laser cladding coating in matrix surface.
Step (1) metallic matrix is titanium alloy substrate or alloy matrix aluminum.
Step (2) the vacuum ball milling parameter is that rotational speed of ball-mill is 50 ~ 75r/min, and ratio of grinding media to material is 14:1 ~ 21:1, ball milling
Time is 2.5h ~ 3.5h.
Step (2) drying temperature is 80 ~ 140 DEG C, and drying time is 2 ~ 6h.
Step (4) described high power CO2The output power of laser is 3.0 ~ 4.0kW, and selected spot diameter is
3mm, focal length 20mm, scanning speed are 300 ~ 450mm/min, and protective gas is argon gas, and gas flow is 4 ~ 7L/min.
The invention has the following advantages that
(1) the high-temperature wear resistant coating hardness that laser melting coating obtains is higher, under the working environment of high temperature, has good resistance to
Mill property and corrosion resistance.
(2) without slag inclusion or bubble inside the high-temperature wear resistant coating obtained, cladding layer and matrix conjugation are high.
(3) raw material powder is that suitable tungsten and carbon are incorporated in titanium-aluminium alloy, and the addition of tungsten is dissolved Titanium base further
Strengthen, carbon, boron and titanium produce TiC, TiB under the high temperature conditions2Particle, these hard phase Dispersed precipitates produce in Titanium base
Raw precipitation strength effect, furthermore a small amount of Be element can make alloy coat performance be increased dramatically, and make it have excellent
Elevated temperature strength and high temperature hardness, and tungsten and vanadium help to improve the high-temperature oxidation resistance of material, therefore titanium, aluminium, tungsten, carbon alloy
With comprehensive performances such as excellent high temperature wear resistant, resistance to high temperature oxidation and heat fatigues.
Detailed description of the invention
Fig. 1 is 1 cladding layer metallographic structure of the embodiment of the present invention；
Fig. 2 is 2 cladding layer metallographic structure of the embodiment of the present invention；
Fig. 3 is 3 cladding layer metallographic structure of the embodiment of the present invention；
Fig. 4 is 4 cladding layer metallographic structure of the embodiment of the present invention；
Fig. 5 is 5 cladding layer metallographic structure of the embodiment of the present invention；
Fig. 6 is different embodiments of the invention microhardness curve.
Specific embodiment
Below by embodiment, invention is further described in detail, but the scope of the present invention is not limited in described
Hold.
Embodiment 1
The present embodiment titanium-based laser cladding coating raw material include the powder of following mass percent: C powder 4.00%, W powder
13.00%, Ti powder 50.20%, Al powder 27.00%, B powder 2.40%, V powder 3.00%, Be powder 0.40%, C powder, W powder, Ti powder, Al powder, B
Powder, V powder, Be powder average particle size be 85 μm；Various elements powder is weighed using electronics, the gross mass of mixed-powder is 80g.
The preparation method of the present embodiment titanium-based laser cladding coating, comprising the following steps:
(1) titanium alloy TC 4 is chosen as cladding matrix, first uses the polishing of 400 mesh sand paper to be beaten again with 600 mesh sand paper on its surface
It polishes clean, then dips acetone soln with absorbent cotton and clean up；
(2) after weighing proportionally by each component raw material powder, it is uniformly mixed raw material powder by vacuum ball milling method, very
The rotational speed of ball-mill of empty ball milling is 50r/min, ratio of grinding media to material 15:1, Ball-milling Time 3h, and ball milling is carried out after mixing using drying box
It is dry, 130 DEG C of drying temperature, drying time 2.5h；
(3) mixed-powder after step (2) drying is uniformly layered on to the titanium alloy of step (1) by the way of preset powder
TC4 matrix surface, fore-put powder is with a thickness of 1.5mm；
(4) high power CO is used2Laser carries out laser irradiation, the output work of laser to the fore-put powder of step (3)
Rate is 3500w, and selected spot diameter is 3mm, and focal length 20mm, scanning speed 350mm/min, protective gas is argon
Gas, gas flow 4L/min are applied so that fore-put powder melts simultaneously with matrix skin to form laser melting coating in matrix surface
Layer.
Cladding coating after the present embodiment laser melting coating is corroded using hydrofluoric acid solution, obtains cladding layer metallographic photograph
Piece, as shown in Figure 1, it is known that cladding layer compact structure；Using the micro- hard of HVS-1000A type microhardness tester measurement cladding layer
Degree, wherein cladding layer different location measures five values, and removes maximal and minmal value and be averaged later, as shown in fig. 6, test
The results show that average hardness reaches 1052HV after laser melting coating, it is improved significantly compared with substrate.
Embodiment 2
The present embodiment titanium-based laser cladding coating raw material include the powder of following mass percent: C powder 5.00%, W powder
14.00%, Ti powder 46.70%, Al powder 28.00%, B powder 2.00%, V powder 4.00%, Be powder 0.30%, C powder, W powder, Ti powder, Al powder, B
Powder, V powder, Be powder average particle size be 70 μm；And various elements powder quality, the gross mass of mixed-powder are weighed using electronic scale
For 80g.
The preparation method of the present embodiment titanium-based laser cladding coating, comprising the following steps:
(1) titanium alloy T C6 is chosen as cladding matrix, first uses the polishing of 400 mesh sand paper to be beaten again with 600 mesh sand paper on its surface
It polishes clean, then dips acetone soln with absorbent cotton and clean up；
(2) after weighing proportionally by each component raw material powder, it is uniformly mixed raw material powder by vacuum ball milling method, very
The rotational speed of ball-mill of empty ball milling be 55r/min, ratio of grinding media to material 14:1, Ball-milling Time 2.8h, ball milling mix after using drying box into
Row drying, 140 DEG C of drying temperature, drying time 2h；
(3) mixed-powder after step (2) drying is uniformly layered on to the titanium alloy of step (1) by the way of preset powder
TC6 matrix surface, fore-put powder is with a thickness of 1mm；
(4) high power CO is used2Laser carries out laser irradiation, the output work of laser to the fore-put powder of step (3)
Rate is 3000w, and selected spot diameter is 3mm, and focal length 20mm, scanning speed 400mm/min, protective gas is argon
Gas, gas flow 5L/min are applied so that fore-put powder melts simultaneously with matrix skin to form laser melting coating in matrix surface
Layer.
Cladding coating after the present embodiment laser melting coating is corroded using hydrofluoric acid solution, obtains cladding layer metallographic photograph
Piece, as shown in Figure 2, it is known that cladding layer compact structure；Using the micro- hard of HVS-1000A type microhardness tester measurement cladding layer
Degree, wherein cladding layer different location measures five values, and removes maximal and minmal value and be averaged later, as shown in fig. 6, test
The results show that average hardness reaches 1013HV after laser melting coating, opposite substrate obtains larger raising.
Embodiment 3
The present embodiment titanium-based laser cladding coating raw material include the powder of following mass percent: C powder 7.00%, W powder
12.00%, Ti powder 44.80%, Al powder 28.00%, B powder 3.40%, V powder 4.30%, Be powder 0.50%, C powder, W powder, Ti powder, Al powder, B
Powder, V powder, Be powder average particle size be 90 μm；And various elements powder quality, the gross mass of mixed-powder are weighed using electronic scale
For 80g.
The preparation method of the present embodiment titanium-based laser cladding coating, comprising the following steps:
(1) it chooses aluminium alloy 7050 and is used as cladding matrix, first use the polishing of 400 mesh sand paper again with 600 mesh sand paper on its surface
It polishes bright and clean, then dips acetone soln with absorbent cotton and clean up；
(2) after weighing proportionally by each component raw material powder, it is uniformly mixed raw material powder by vacuum ball milling method, very
The rotational speed of ball-mill of empty ball milling is 60r/min, ratio of grinding media to material 17:1, Ball-milling Time 2.5h；Ball milling mix after using drying box into
Row drying, 100 DEG C of drying temperature, drying time 5h；
(3) mixed-powder after step (2) drying is uniformly layered on to the aluminium alloy of step (1) by the way of preset powder
7050 matrix surfaces, fore-put powder is with a thickness of 2mm；
(4) high power CO is used2Laser carries out laser irradiation, the output work of laser to the fore-put powder of step (3)
Rate is 4000w, and selected spot diameter is 3mm, and focal length 20mm, scanning speed 400mm/min, protective gas is argon
Gas, gas flow 6L/min are applied so that fore-put powder melts simultaneously with matrix skin to form laser melting coating in matrix surface
Layer.
Cladding layer after the present embodiment laser melting coating is corroded using hydrofluoric acid solution, obtains cladding layer metallographic photograph
Piece, as shown in Figure 3, it is known that cladding layer compact structure；Using the micro- hard of HVS-1000A type microhardness tester measurement cladding layer
Degree, wherein cladding layer different location measures five values, and removes maximal and minmal value and be averaged later, as shown in fig. 6, test
The results show that average hardness reaches 1083HV after laser melting coating, it is improved significantly compared with base material.
Embodiment 4
The present embodiment titanium-based laser cladding coating raw material include the powder of following mass percent: C powder 6.00%, W powder
16.00%, Ti powder 35.20%, Al powder 32.00%, B powder 5.00%, V powder 5.00%, Be powder 0.80%, C powder, W powder, Ti powder, Al powder, B
Powder, V powder, Be powder average particle size be 100 μm；And various elements powder quality, total matter of mixed-powder are weighed using electronic scale
Amount is 80g.
The preparation method of the present embodiment titanium-based laser cladding coating, comprising the following steps:
(1) titanium alloy TC 4 is chosen as cladding matrix, first uses the polishing of 400 mesh sand paper to be beaten again with 600 mesh sand paper on its surface
It polishes clean, then dips acetone soln with absorbent cotton and clean up；
(2) after weighing proportionally by each component raw material powder, it is uniformly mixed raw material powder by vacuum ball milling method, very
The rotational speed of ball-mill of empty ball milling is 75r/min, ratio of grinding media to material 21:1, Ball-milling Time 3.5h；Ball milling mix after using drying box into
Row drying, 80 DEG C of drying temperature, drying time 6h；
(3) mixed-powder after step (2) drying is uniformly layered on to the titanium alloy of step (1) by the way of preset powder
TC4 matrix surface, fore-put powder is with a thickness of 1.5mm；
(4) high power CO is used2Laser carries out laser irradiation, the output work of laser to the fore-put powder of step (3)
Rate is 4000w, and selected spot diameter is 3mm, and focal length 20mm, scanning speed 450mm/min, protective gas is argon
Gas, gas flow 7L/min are applied so that fore-put powder melts simultaneously with matrix skin to form laser melting coating in matrix surface
Layer.
Cladding layer after the present embodiment laser melting coating is corroded using hydrofluoric acid solution, obtains cladding layer metallographic photograph
Piece, as shown in Figure 4, it is known that cladding layer compact structure；Using the micro- hard of HVS-1000A type microhardness tester measurement cladding layer
Degree, wherein cladding layer different location measures five values, and removes maximal and minmal value and be averaged later, as shown in fig. 6, test
The results show that average hardness reaches 1095HV after laser melting coating, it is increased dramatically compared with substrate.
Comparative example
The present embodiment titanium-based laser cladding coating C powder 4.00%, W powder 13.00%, Ti powder 50.60%, Al powder 27.00%, B powder
2.40%, V powder 3.00%, C powder, W powder, Ti powder, Al powder, B powder, V powder average particle size be 85 μm；And it is weighed using electronic scale various
Element powders quality, the gross mass of mixed-powder are 80g.
The preparation method of the present embodiment titanium-based laser cladding coating, comprising the following steps:
(1) titanium alloy TC 4 is chosen as cladding matrix, first uses the polishing of 400 mesh sand paper to be beaten again with 600 mesh sand paper on its surface
It polishes clean, then dips acetone soln with absorbent cotton and clean up；
(2) after weighing proportionally by each component raw material powder, it is uniformly mixed raw material powder by vacuum ball milling method, very
The rotational speed of ball-mill of empty ball milling is 50r/min, ratio of grinding media to material 15:1, Ball-milling Time 3h, and ball milling is carried out after mixing using drying box
It is dry, 130 DEG C of drying temperature, drying time 2.5h；
(3) mixed-powder after step (2) drying is uniformly layered on to the titanium alloy of step (1) by the way of preset powder
TC4 matrix surface, fore-put powder is with a thickness of 1.5mm；
(4) laser irradiation, the output work of laser are carried out using fore-put powder of the high-power co2 laser to step (3)
Rate is 3500w, and selected spot diameter is 3mm, and focal length 20mm, scanning speed 350mm/min, protective gas is argon
Gas, gas flow 4L/min are applied so that fore-put powder melts simultaneously with matrix skin to form laser melting coating in matrix surface
Layer.
Cladding layer after the present embodiment laser melting coating is corroded using hydrofluoric acid solution, obtains cladding layer metallographic photograph
Piece, as shown in Figure 5, it is known that cladding layer compact structure, but its compactness does not have embodiment 4 good；It is micro- using HVS-1000A type
Hardness tester measure cladding layer microhardness, wherein cladding layer different location measure five value, and remove maximal and minmal value it
After be averaged, as shown in fig. 6, test result is shown, average hardness reaches 919HV after laser melting coating, obtains obviously compared with substrate
It improves, but for adding embodiment 1-4, effect is poor.
Claims (7)
1. a kind of titanium-based laser cladding coating, which is characterized in that laser cladding coating raw material include following mass percent
Powder: C:4% ~ 7%, W:12% ~ 16%, Al:27% ~ 32%, B:2% ~ 5%, V:3% ~ 5%, Be:0.3% ~ 0.8%, surplus Ti.
2. titanium-based laser cladding coating according to claim 1, which is characterized in that the average particle size of the powder is 70 ~ 100
μm。
3. the preparation method of titanium-based laser cladding coating described in claim 1, which comprises the following steps:
(1) metal base surface is polished bright and clean and cleaned up, specifically, after metal base surface is polished with 400 mesh sand paper
It is polished with 600 mesh sand paper, is then cleaned with acetone again；
(2) proportionally prepare cladding coating raw material powder, vacuum ball milling is dry after mixing；
(3) powder of step (2) is preset at metal base surface, fore-put powder is with a thickness of 1 ~ 2mm；
(4) laser melting coating is carried out to the fore-put powder of step (3), so that preset powder melts simultaneously with metallic matrix surface layer, in base
Body surface face forms laser cladding coating.
4. the preparation method of titanium-based laser cladding coating according to claim 3, which is characterized in that step (1) described metal
Matrix is titanium alloy substrate or alloy matrix aluminum.
5. the preparation method of titanium-based laser cladding coating according to claim 3, which is characterized in that step (2) described vacuum
Ball milling parameter is that rotational speed of ball-mill is 50 ~ 75r/min, and ratio of grinding media to material is 14:1 ~ 21:1, and Ball-milling Time is 2.5h ~ 3.5h.
6. the preparation method of titanium-based laser cladding coating according to claim 3, which is characterized in that step (2) described drying
Temperature is 80 ~ 140 DEG C, and drying time is 2 ~ 6h.
7. the preparation method of titanium-based laser cladding coating according to claim 3, which is characterized in that step (4) described laser
Cladding uses high power CO2Laser carries out, and output power is 3.0 ~ 4.0kW, and spot diameter 3mm, focal length 20mm are swept
Retouching speed is 300 ~ 450mm/min, and protective gas is argon gas, and gas flow is 4 ~ 7L/min.
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| US4459328A (en) * | 1981-12-21 | 1984-07-10 | Gte Products Corporation | Articles coated with wear-resistant titanium compounds |
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| US4411960A (en) * | 1981-12-21 | 1983-10-25 | Gte Products Corporation | Articles coated with wear-resistant titanium compounds |
| US4459328A (en) * | 1981-12-21 | 1984-07-10 | Gte Products Corporation | Articles coated with wear-resistant titanium compounds |
| CN101139709A (en) * | 2006-09-08 | 2008-03-12 | 北京有色金属研究总院 | Method for acquiring highly-adaptive abrasion-proof titanium-based composite material on titanium alloy surface |
| CN102226279A (en) * | 2011-06-13 | 2011-10-26 | 山东电力研究院 | Method for preparing titanium diboride and titanium carbide enhanced iron-based wear resistant composite paint |
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| "WC颗粒增强钛基复合涂层的组织和高温磨损性能研究";杨光等;《应用激光》;20130831;第33卷(第4期);第366页左栏第1段-倒数第2段，表1 |
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