CN104388931A - Method for amorphous-nanocrystallization of surface of titanium alloy by virtue of laser machining - Google Patents
Method for amorphous-nanocrystallization of surface of titanium alloy by virtue of laser machining Download PDFInfo
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- CN104388931A CN104388931A CN201410759195.8A CN201410759195A CN104388931A CN 104388931 A CN104388931 A CN 104388931A CN 201410759195 A CN201410759195 A CN 201410759195A CN 104388931 A CN104388931 A CN 104388931A
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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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Abstract
The invention discloses a method for amorphous-nanocrystallization of the surface of a titanium alloy by virtue of laser machining. The method comprises the steps of before laser nanocrystallization, cleaning the surface of the titanium surface, and cleaning and drying the surface of the titanium surface; uniformly mixing Stellite12 substrate powder and B4C and Sb mixed powder according to a certain mass ratio to prepare pasty mixed powder by using a sodium silicate solution (Na2O.nSiO2), wherein the substrate powder is Stellite12, the dimension of the substrate powder is 1 to 370 microns, and the dimension of the B4C and Sb mixed powder is 4 to 400 microns; uniformly coating the surface of the titatnium alloy with the pasty mixed powder to form a coating which is 0.3 mm to 2 mm thick, and naturally air-drying the coating; performing laser alloying treatment on the surface, with the preformed coating, of the titanium alloy with a laser beam, laterally blowing argon for protection in a perpendicular scanning process of the laser beam, and simultaneously coaxially blowing argon to protect a lens barrel, wherein process parameters comprise laser power of 450 to 3,000 W, scanning speed of 1 to 18 mm/s, light spot diameter of 1 to 9mm and argon protection pressure of 0.1 to 1.2 MPa. According to the method, amorphous-nanometer laser alloyed coating can be obtained, and compared with a titanium alloy substrate, the hardness and abrasion resistance of the amorphous-nanometer laser alloyed coating are remarkably improved.
Description
Technical field
The present invention relates to a kind of method realizing titanium alloy surface amorphous-nanometer, belong to material surface strengthening technical field.Improve at titanium alloy surface Sb the method that Stellite base TiB2-TiC strengthens laser alloying coating abrasion performance and surface topography in particular to a kind of.
Background technology
Titanium alloy has high specific strength, and the advantage such as high ratio modulus and excellent corrosion resistance, is widely used in the fields such as aerospace.But titanium alloy surface wears no resistance, limit the performance of its potential.Laser alloying is a kind of novel process for modifying surface, can significantly improve material surface performance, repair mainly for wear out failure material, the feature such as have that efficiency is high, speed is fast, environmental protection is pollution-free and after process workpiece performance is good.Amorphous alloy, as a kind of type material, has high-yield strength, the large excellent properties such as elastic strain limit and high-wearing feature; Nanocrystalline because of its special structure and dimensional effect, there is the excellent properties that general material is difficult to obtain, as high-wearing feature and high-temperature oxidation etc.And in recent years, along with the develop rapidly of nano material, nanotechnology starts to be applied to Surface Engineering, defines " nano surface work " frontier, and be subject to the great attention of the domestic and international military as a kind of special utilisation technology.Stellite alloy, namely usually said CoCrW(Mo) alloy or cobalt base alloy are a kind of Wimet of wear-resistant and resistance to high temperature oxidation.Joined by appropriate Stellite in laser alloying coating, coating will have high rigidity, the feature such as corrosion-resistant, wear-resisting and heat-resisting.It is the effective way improving the performances such as the wear-resisting and resistance to high temperature oxidation of titanium alloy surface that laser alloying ceramic particle strengthens compound coating, and alloying coating and titanium alloy substrate can be made to produce metallurgical binding, and formation has the coating of good obdurability.Various inefficacy part can be repaired, as aero engine turbine blades etc. by laser alloying technology.Sb is to the nanometer process of Stellite base laser alloying coating, and being the process that the nano particles such as such as CoSb and CoCr utilizing Sb to generate at laser molten pool situ are grown up to suppress other Crystallization Phases, is also the process of a large amount of nanocrystalline generation.And CoSb is nanocrystalline has high diffusivity in high temperature molten bath, easily causes lattice distortion, make coating generation aSi∶H film.
For these reasons, the present invention proposes one can reduce production cost, strengthens the material surface laser amorphous nano treatment process of titanium alloy surface hardness and wear resistance.Direct water glass solution is by Stellite 12-B
4c-Sb mixed powder uniform stirring becomes pasty state to be coated on titanium alloy surface, then carries out Laser Alloying Treatment.Because base material titanium alloy is to the diluting effect of laser molten pool, a large amount of Ti enters in laser molten pool by base material, can with many chemical element generation chemical reactions in laser molten pool, generate such as TiB
2, TiC etc. has the compound of wear resistance.Stereoscan photograph shows, Stellite 12-B
4c-Sb laser alloying coating texture is even, flawless and pore produce (see
fig. 1).
Adopt the hardness of HV-1000 type microhardness tester testing laser alloying coating, load is 200 g, and the loading time is 5 seconds, inwardly measures a hardness value every 0.12 mm from sample top layer.Adopt the abrasion resistance of MM200 determination of wear testing machine alloying coating.Preferred dimension is
Φthe YG6 Wimet emery wheel of 40 × 12, rotating speed 400 r/min, load is 2 ~ 8 kg.
Wear volume: measured a wear scar width or wear weight loss every 10 minutes in wearing test; Wear scar width adopts volume measurement microscope, averages as measuring result after multi-site determination.Utilize following formula proximate calculation wear volume.
V=l{r
2arcsin
-}
In formula: V is wear volume, unit is mm
3;
L is polishing scratch length (i.e. specimen width), unit mm;
B is wear scar width, mm;
R is wheel radius, mm.
After laser alloying, Stellite 12-B
4c-Sb laser alloying coating hardness can reach 1300 ~ 1400 HV
0.2(see
fig. 2)
.
Stellite 12-B
4c-Sb laser alloying coating has higher hardness and good polishing machine and weave construction, and the wear volume of this alloying coating is that the 1/12(of TA15 alloy base material is shown in
fig. 3with
table 1).
table 1 isstellite 12-B
4c-Sb laser alloying coating and TA15 wearing test result
Summary of the invention
The present invention is directed to titanium alloy surface Stellite base TiB
2-TiC strengthens the defect that laser alloying coating morphology is uneven and wear resisting property is unstable, is added and makes the further amorphous-nanometer of laser alloying coating, thus improve coating morphology and wear resistance by Sb.This technology can be applicable to airplane parts manufacture in and all many-sides such as aviation field parts reparation.
Concrete steps of the present invention:
(1) by the Stellite 12 of certain mass ratio and B
4the even furnishing pasty state of C, Sb mixed powder water glass solution; Described base powder is Stellite 12 size 1 ~ 370 μm, B
4c and Sb powder size 4 ~ 400 μm;
(2) pasty state mixed powder is coated in titanium alloy surface equably, coat-thickness 0.3 ~ 2 mm, natural air drying;
(3) carry out laser alloying with the titanium alloy specimen surface of laser beam to above-mentioned preset coating, in laser beam vertical sweep process, side direction coaxially blows argon shield molten bath and lens barrel; Processing parameter: laser power 450 ~ 3000 W, sweep velocity 1 ~ 18 mm/s, spot diameter 1 ~ 9 mm, argon shield air pressure 0.1 ~ 1.2 MPa.
Can titanium alloy surface be cleared up before mixed powder coating, and wipe clean, dry up.
The modulus of the water glass solution in described step (1) is 2.2 ~ 3.7.
Titanium alloy described in step (2) can be TA15 the trade mark titanium alloy such as TA2.
In mixed powder described in step (2), each composition and massfraction thereof: B
4c4%-36%, Sb2%-9%, surplus is Stellite 12.The wherein nominal chemical composition of Stellite 12: C1.40, Cr29.50, Si1.45, W8.25, Fe3.00, Mo1.00, Ni3.00, Mn1.00, remaining is Co.
The present invention is at argon gas as under protection gas condition, specimen surface generation laser alloying.In laser alloying process, sample keeps original movement velocity constant.After the complete laser alloying of specimen surface occurs, by laser shutdown, after two seconds, shielding gas is closed.Rear reason of closing protection gas is to make protection gas adequately protect to specimen surface.
The present invention can obtain wear resistance and the good titanium alloy surface strengthened coat of surface topography.The present invention has the advantages such as technique is simple and convenient, suitability is strong, easy to utilize.
figure of description
Fig. 1 is titanium alloy surface Stellite 12-B
4macroscopical SEM picture of C-Sb laser alloying coating;
Fig. 2 is Stellite 12-B
4the microhardness distribution of C-Sb laser alloying coating;
Fig. 3 is Stellite 12-B
4the wear volume of C-Sb laser alloying coating and TA15 titanium alloy.
Embodiment
embodiment 1:
TA15 alloy is cut into length 35 mm, width 10 mm, thickness 10 mm rectangular parallelepiped.Before mixed powder coating, cleaning titanium alloy surface, and wipe clean, dry up; Then, by the Stellite 12 of massfraction 81%, the B of massfraction 15%
4the Sb mixed powder laser alloying of C, massfraction 4% is on its mm face, 35 mm × 10.
Concrete technology step:
(1), before laser alloying, treat alloying surface with No. 240 sand papering TA15 titanium alloys, make its surfaceness reach Ra 2.5 μm; Then be that 10% aqueous sulfuric acid carries out pickling to this surface by volume percent, pickling time 5 ~ 10 min; After pickling, with clear water rinse, with alcohol by clean for this surface wipes, dry up;
(2) configure the water glass solution of 20 milliliters with glass test tube, in this water glass solution, pure water glass and volume of water configure
Ratio is 1:3, namely measures the pure water glass of 5 milliliters and the water of 15 milliliters, stirs in glass test tube;
(3) on balance, take Stellite 12 powdered alloy 0.81g, B respectively
4c powder 0.15g, Sb0.4g, pour in small beaker by load weighted powder, is that this mixed powder uniform stirring is become pasty state by the water glass solution of 2.2 ~ 3.7 with modulus.Stellite 12 base powder size 10 ~ 200 μm, B
4c, Sb powder size 20 ~ 300 μm;
(4) pasty state mixed powder is coated in titanium alloy surface equably, thickness 0.8 mm of coating, natural air drying;
(5) carry out Laser Alloying Treatment with the titanium alloy specimen surface of laser beam to above-mentioned preset coating, in laser beam vertical sweep process, side direction coaxially blows argon shield molten bath and lens barrel; Processing parameter: laser power 800 W, sweep velocity 6 mm/s, spot diameter 4 mm, argon shield air pressure 0.4 MPa;
(6) concrete steps: the sample dried is positioned over the position facing Laser emission mouth, by protection gas port just to the titanium alloy coatingsurface before laser alloying.After position is adjusted, with the spanner of adjusting sample position parallel on laser apparatus, sample and laser apparatus emission port are pulled open certain distance, then allow sample as early as possible to laser spout with 2.5 mm/s speed uniform motion.When sample will move to protection gas port, open protection gas in advance.When sample will move to Laser emission mouth, open laser transmitter in advance.Subsequently under the protection of protection gas, specimen surface generation laser alloying.Protection air to close by laser shutdown, closes after having there is laser alloying reaction completely by specimen surface after a second, and rear closedown protects the reason of gas to be to be make protection gas protect fully specimen surface.After laser alloying, specimen surface hardness can reach 1350 ~ 1400 HV
0.2,the 1/11(that laser alloying coating wear volume is about TA15 is shown in
table 2);
table 2stellite 12-B
4c-Sb laser alloying coating and TA15 base material wearing test result
embodiment 2:
TA2 alloy is cut into the rectangular parallelepiped of length 30 mm, width 10 mm, thickness 10 mm.Before mixed powder coating, cleaning titanium alloy surface, and wipe clean, dry up.Then, by massfraction 85%Stellite 12, massfraction 10%B
4the mixed powder laser alloying of C, massfraction 5%Sb is on its mm face, 30 mm × 10.
Concrete technology step:
(1) before laser alloying, treat laser alloying surface with No. 240 sand papering TA2 titanium alloys, make its surfaceness reach Ra 2.5 μm; Then be that 10% aqueous sulfuric acid is treated laser alloying surface and cleaned by volume percent, pickling time is 5 ~ 10 min; After pickling, with clear water rinse, with alcohol by workpiece surface wiped clean fusion, dry up;
(2) water glass solution of 40 milliliters is configured with glass test tube, the pure water glass in this water glass solution and the volume of water
Allocation ratio is 1:3, namely measures the pure water glass of 10 milliliters and the water of 30 milliliters, stirs in glass test tube;
(3) on balance, take Stellite 12 powdered alloy 0.85 g, B respectively
4c powder 0.10 g, Sb powder 0.5 g, pours in small beaker by load weighted powder, is that this mixed powder uniform stirring is become pasty state by the water glass solution of 2.2 ~ 3.7 with modulus.The size of Stellite 12 powder 20 ~ 100 μm, B
4c, Sb powder size 40 ~ 200 μm;
(4) pasty state mixed powder is coated in titanium alloy surface equably, the thickness of coating is 0.6 mm, natural air drying;
(5) carry out laser alloying with the titanium alloy specimen surface of laser beam to above-mentioned preset coating, in laser beam vertical sweep process, side direction coaxially blows argon shield molten bath and lens barrel; Processing parameter: laser power 900 W, sweep velocity 4 mm/s, spot diameter 4 mm, argon shield air pressure is 0.6 MPa;
(6) concrete steps: the sample dried is placed on the position facing Laser emission mouth, will protect gas port just to swashing
Titanium alloy coatingsurface before photosynthetic aurification.After position is adjusted, with the spanner of adjusting sample position parallel on laser apparatus, sample and laser apparatus emission port are pulled open certain distance, then allow sample as early as possible to laser spout with 4 mm/s speed uniform motion.When sample will move to protection gas port, open protection gas in advance.When sample will move to Laser emission mouth, open laser transmitter in advance.Subsequently under the protection of protection gas, specimen surface generation laser alloying.Protection air to close by laser shutdown, closes after having there is laser alloying reaction completely by specimen surface after a second, and rear closedown protects the reason of gas to be to be make protection gas protect fully specimen surface.After laser alloying, specimen surface hardness can reach 1400 ~ 1450 HV
0.2, the 1/14(that the wear volume of laser alloying coating is about TA2 matrix is shown in
table 3).
table 3stellite 12-B
4c-Sb laser alloying coating and TA2 base material wearing test result
Claims (2)
1. made a method for titanium alloy surface amorphous-nanometer by laser processing, comprise the following steps;
(1) by the base powder of certain mass ratio and Stellite 12 and B
4c, Sb mixed powder water glass solution (Na
2onSiO
2) even furnishing pasty state; Described base powder is Stellite 12 intermetallic compound, base powder size 1 ~ 370 μm, B
4c and Sb powder size 4 ~ 400 μm;
(2) pasty state mixed powder is coated in TA2 or TA15 titanium alloy surface equably, coat-thickness 0.3 ~ 2 mm, natural air drying;
(3) carry out laser alloying with the titanium alloy specimen surface of laser beam to above-mentioned preset coating, in laser beam vertical sweep process, side direction coaxially blows argon shield molten bath and lens barrel; Processing parameter is laser power 450 ~ 3000 W, sweep velocity 1 ~ 18 mm/s, spot diameter 1 ~ 9 mm, and argon shield air pressure is 0.1 ~ 1.2 MPa.
2. a kind of method being made titanium alloy surface amorphous-nanometer by laser processing according to claim 1, it is characterized in that, in the mixed powder described in step (2), each composition quality mark is: B
4c4% ~ 36%, Sb2% ~ 9%, surplus is Stellite 12.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107723511A (en) * | 2017-08-29 | 2018-02-23 | 山东建筑大学 | A kind of method of the laser gain material manufacture nanocrystalline modified gradient composite of quasi-crystalline substance |
| CN110711922A (en) * | 2018-07-13 | 2020-01-21 | 山东建筑大学 | Method for additive manufacturing of stainless steel through MIG (metal-inert gas) fuse and surface treatment |
| CN112663054A (en) * | 2021-01-13 | 2021-04-16 | 山东建筑大学 | Method for preparing nickel-coated graphite powder modified protective layer by titanium alloy laser |
| CN113070576A (en) * | 2021-05-08 | 2021-07-06 | 吉林大学 | Method for preparing micro-nano periodic structure on surface of amorphous alloy by nanosecond laser irradiation |
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| CN103600066A (en) * | 2013-11-20 | 2014-02-26 | 毛桂林 | Cobalt-base alloy powder special for continuous-wave fiber laser cladding |
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| CN103600066A (en) * | 2013-11-20 | 2014-02-26 | 毛桂林 | Cobalt-base alloy powder special for continuous-wave fiber laser cladding |
| CN103695898A (en) * | 2013-12-19 | 2014-04-02 | 山东大学 | Titanium alloy surface metal ceramic composite coating and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107723511A (en) * | 2017-08-29 | 2018-02-23 | 山东建筑大学 | A kind of method of the laser gain material manufacture nanocrystalline modified gradient composite of quasi-crystalline substance |
| CN107723511B (en) * | 2017-08-29 | 2019-05-17 | 山东建筑大学 | A kind of method of the laser gain material manufacture nanocrystalline modified gradient composite material of quasi-crystalline substance- |
| CN110711922A (en) * | 2018-07-13 | 2020-01-21 | 山东建筑大学 | Method for additive manufacturing of stainless steel through MIG (metal-inert gas) fuse and surface treatment |
| CN112663054A (en) * | 2021-01-13 | 2021-04-16 | 山东建筑大学 | Method for preparing nickel-coated graphite powder modified protective layer by titanium alloy laser |
| CN113070576A (en) * | 2021-05-08 | 2021-07-06 | 吉林大学 | Method for preparing micro-nano periodic structure on surface of amorphous alloy by nanosecond laser irradiation |
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Application publication date: 20150304 |