CN104152895B - A kind of preparation technology of titanium alloy surface intermetallic compound base ceramic composite coating - Google Patents
A kind of preparation technology of titanium alloy surface intermetallic compound base ceramic composite coating Download PDFInfo
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- CN104152895B CN104152895B CN201410404997.7A CN201410404997A CN104152895B CN 104152895 B CN104152895 B CN 104152895B CN 201410404997 A CN201410404997 A CN 201410404997A CN 104152895 B CN104152895 B CN 104152895B
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Abstract
The invention discloses a kind of preparation technology of titanium alloy surface intermetallic compound base ceramic composite coating, comprise step as follows: cladding material powder mixes by (1), mixed powder water glass solution furnishing pasty state, then evenly titanium alloy surface is coated on, coat-thickness is 0.5-1.0mm, air-dry; (2) carry out laser melting coating to the coating of titanium alloy surface, laser power is 800-1200W, and the sweep velocity of laser is 2.5-7.5mm/s, and blowing argon gas is protected, and protection air pressure is 0.2-0.4MPa, and the spot diameter of laser is fixed as 4mm.Do are in cladding material mixed powder, each component and massfraction thereof: Ti 25-65%, Al 20-60%, Si 5-30%, Y
2o
30-3%; Or Ti 25-65%, Al 20-60%, Si 5-30%, B
4c 2-40%, Y
2o
30-3%; Or Ti 25-65%, Al 20-60%, Si 5-30%, TiC 5-40%, Y
2o
30-3%.Compound coating prepared by the present invention can significantly improve the microhardness of titanium alloy, improves the wear resistance of titanium alloy member, expands the use range of titanium alloy component.
Description
Technical field
The present invention relates to the preparation technology of the wear-resisting compound coating of a kind of titanium alloy surface, concrete, relate to a kind of Laser Cladding on Titanium Alloy intermetallic compound base Ceramic Composite wear-resistant coating and preparation technology thereof.
Background technology
The advantages such as titanium alloy is little with its density, specific tenacity is high, corrosion resisting property is good, are widely used at the industrial circle such as aerospace and petrochemical complex.But the further application that titanium alloy hardness is low, the shortcoming such as to wear no resistance limits it.How to improve hardness and the wear resistance of titanium alloy, expand its range of application, cause the concern of domestic and international investigation of materials personnel.Improve the most cost-effective method of performance such as titanium alloy surface hardness and wear resistance to titanium alloy surface modification.Laser melting and coating technique, as a kind of metal surface properties modification technology, can effectively improve titanium alloy surface performance, thus expand its use range.
Laser melting coating by adding cladding material at substrate surface, and utilizes the laser beam of high-energy-density to make it the method for consolidation together with substrate surface thin layer, is the filling cladding layer of metallurgical binding at substrate surface formation and its.Stupalith has excellent wear-resisting, corrosion-resistant and antioxidant property and high chemical stability, surface hardness and the wear resistance of titanium alloy can be increased substantially, but because ceramic phase fragility is large, do not mate with the thermal expansivity of titanium alloy substrate, bonding strength is low, under high thermal stresses and phase-change organization's stress, very easily produce tiny crack, even cause cladding layer brittle flaking off.Current Laser Cladding on Titanium Alloy material generally adopts metal/ceramic composite system, and this compound system significantly can reduce the unrelieved stress in cladding layer, reduces the tendency occurring tiny crack in cladding layer, is easy to the laser cladding layer obtaining excellent performance.
Therefore, the selection of cladding material and cladding system is very crucial for the surface modification of titanium alloy material, and less about the report of Laser Cladding on Titanium Alloy Ti/Al/Si and hard ceramic phase at present.
Summary of the invention
The object of this invention is to provide the wear-resisting compound coating of a kind of titanium alloy surface and preparation technology thereof, this compound coating can significantly improve the microhardness of titanium alloy, improves the wear resistance of titanium alloy member, expands the use range of titanium alloy component.
For achieving the above object, the present invention adopts following technical scheme:
A preparation technology for titanium alloy surface intermetallic compound base ceramic composite coating, comprises step as follows:
(1) mixed by cladding material powder, mixed powder tamanori furnishing pasty state, is then evenly coated on titanium alloy surface, and coat-thickness is 0.5-1.0mm, air-dry;
(2) carry out laser melting coating to the coating of titanium alloy surface, laser power is 800-1200W, and the sweep velocity of laser is 2.5-7.5mm/s, and blown inert gas is protected, and protection air pressure is 0.2-0.4MPa.
Wherein, in step (1), in described cladding material mixed powder, each component and massfraction thereof are: Ti25-65%, Al20-60%, Si5-30%, Y
2o
30-3%; Or Ti25-65%, Al20-60%, Si5-30%, B
4c2-40%, Y
2o
30-3%; Or Ti25-65%, Al20-60%, Si5-30%, TiC5-40%, Y
2o
30-3%.
In step (1), described titanium alloy is Ti-6Al-4V titanium alloy.
In step (2), described tamanori is water glass solution.
Preferably, in step (2), in described mixed powder, the massfraction of each component is: Ti30-60%, Al25-55%, Si8-25%, Y
2o
30.2-2.8%; Or Ti30-60%, Al25-55%, Si8-25%, B
4c4-35%, Y
2o
30.2-2.8%; Or Ti30-60%, Al25-55%, Si8-25%, TiC8-35%, Y
2o
30.2-2.8%.
Preferred further, in step (2), in described mixed powder, the massfraction of each component is: Ti35-55%, Al30-50%, Si10-20%, Y
2o
30.5-2.5%; Or Ti35-55%, Al30-50%, Si10-20%, B
4c8-30%, Y
2o
30.5-2.5%; Or Ti35-55%, Al30-50%, Si10-20%, TiC15-30%, Y
2o
30.5-2.5%.
In step (2), the volume proportion of described water glass solution is water glass: water=1:3; The addition of water glass solution is instill 3-10 in every 1g cladding material mixed powder to drip (1mL is 20).
Beneficial effect of the present invention:
(1) the present invention adopts metal-powder Ti and Al and non-metal powder Si powder to carry out multiple elements design laser melting coating at titanium alloy surface under open ar gas environment, prepares with Ti
5si
3, Ti
5si
4and TiSi
2be main strengthening phase mutually etc. ceramic hard, with TiAl, Ti
3the intermetallic compounds such as Ali are high rigidity, the antiwear composite ceramic coating of assisted and strengthened phase, define good metallurgical binding between coating and matrix.
(2) there is reaction in-situ, i.e. [Ti]+[Si] → [Ti in the Ti in laser cladding process in Si and molten bath
5si
3], [Ti
5si
3]+[Si] → [Ti
5si
4] and [Ti
5si
4]+[Si] → [TiSi
2].Ti with Al reaction generates Ti-Al intermetallic compound and is present in cladding layer together with Ti-Si compound, forms compound coating.The ratio of Ti-Al, Ti-Si in cladding layer is closed in adjustment, it can be made mutually to pin down in process of growth, can improve the concentration and distribution of compound in cladding layer, obtain the composite ceramic coat of superior performance.Ti-6Al-4V alloy microhardness after the present invention adopts Ti, Al and Si powder laser melting coating under open Ar environment is about matrix hardness (320-360HV
0.2) 3-4 doubly, when added load is 10kg, the wear weight loss of 40 minutes is about the 1/3-1/4 of matrix.
(3) the present invention introduces appropriate ceramic phase B further in cladding powder
4c or TiC, B
4c occurs to decompose at cladding process, with Ti in molten bath, reaction in-situ occurs, generate the hard phases such as TiB and TiC, and the single TiC ceramic phase added plays the effect of dispersion-strengthened, the hardness of intermetallic compound base coating can be improved further, improve the performance of laser cladding layer.Ti-6Al-4V alloy adopts Ti, Al, Si and B through the present invention under open Ar environment
4after the cladding of C powder laser, microhardness is about matrix hardness (320-360HV
0.2) 4-5 doubly, when added load is 10kg, the average abrasion weightlessness of 10 minutes is about the 1/4-1/5 of matrix.
(4) nanometer Y
2o
3be high melting compound, out-phase forming core point can be become, nucleation rate is accelerated, causes grain refining, Y
2o
3also dendrite gap can be made to reduce, the growth retardation of dentrite, therefore refinement dendritic structure, tissue becomes even compact.Rare earth element can accelerate the flowing of liquid metal in addition, reduces component segregation, ceramic phase is more easily permeated in dynamic metal, forms Metal-metal bonded compound, thus be combined with matrix stronger with metal.Appropriate rare earth oxide Y
2o
3the effect of obvious crystal grain thinning can be played, thus obtain the higher cladding layer of dense structure, hardness and wear resistance.In laser cladding process, part Y
2o
3y and O can be decomposed into
2.Rare earth element y can be adsorbed on crystal boundary, hinders crystal boundary to move, can also reduce surface tension and the Critical nucleation radius of liquid metal, improve nucleation rate, thus thinning microstructure.There is not the Y decomposed in part
2o
3as heterogeneous forming core core, nucleation rate can be improved, the tiny Y of part
2o
3particle also can hinder the growth of crystal.Rare earth element can accelerate the flowing of liquid metal in addition, reduces component segregation, ceramic phase is more easily penetrated in metal, forms Metal-metal bonded compound with metal, thus be combined with matrix stronger.Although a large amount of Y
2o
3add the hardness that can improve cladding layer, but the fragility of cladding layer can be increased, be unfavorable for the raising of its wear resistance.B
4c (or TiC) powder and rare earth oxide Y
2o
3while be added with to be beneficial to and improve the microhardness of cladding layer and wear resistance, appropriate B
4c (or TiC) can improve hardness and the wear resistance of cladding layer further, and Y
2o
3then can thinning microstructure, improve the comprehensive mechanical property of coating, research shows, adds 10wt.%B
4c (or 20wt.%TiC powder) and 1wt.%Y
2o
3microhardness is about 4 times of Ti-6Al-4V alloy substrate hardness, and shows better wear resistance, and the average weightlessness of wearing and tearing 10min is about 1/5 of the average weightlessness of Ti-6Al-4V matrix.
Accompanying drawing explanation
Fig. 1 a-Fig. 1 e is the X-ray diffractogram of laser melting coating sample prepared by embodiment of the present invention 1-5, and wherein Fig. 1 a is embodiment 1, Fig. 1 b be embodiment 2, Fig. 1 c be embodiment 3, Fig. 1 d be embodiment 4, Fig. 1 e is embodiment 5;
Fig. 2 is the laser cladding layer cross-sectional structure shape appearance figure of the embodiment of the present invention 1;
Fig. 3 a-Fig. 3 e is laser melting coating sample cladding layer shape appearance figure prepared by embodiment of the present invention 1-5, and wherein Fig. 3 a is embodiment 1, Fig. 3 b be embodiment 2, Fig. 3 c be embodiment 3, Fig. 3 d be embodiment 4, Fig. 3 e is embodiment 5;
Fig. 4 is the hardness profile of laser melting coating sample prepared by embodiment of the present invention 1-5;
Fig. 5 is the wear weight loss amount of the laser cladding layer prepared of embodiment of the present invention 2-4 and titanium alloy substrate;
Fig. 6 is the X-ray diffractogram of laser melting coating sample prepared by embodiment 6;
Fig. 7 a is the tissue topography figure bottom the laser melting coating compound coating of embodiment 3 preparation;
Fig. 7 b is the tissue topography figure bottom the laser melting coating compound coating of embodiment 6 preparation;
Fig. 8 is laser cladding layer hardness value distribution curve prepared by embodiment 3 and embodiment 6;
Fig. 9 is embodiment 6 (Ti-35Al-15Si-1Y
2o
3) the laser cladding layer wear weight loss distribution curve prepared;
Figure 10 is the X-ray diffractogram of laser melting coating sample prepared by embodiment 7 ((50Ti-35Al-15Si)-10TiC);
Figure 11 is TiC crystal distribution schematic diagram in the cladding layer prepared of embodiment 7 ((50Ti-35Al-15Si)-10TiC)
Figure 12 is laser melting coating sample hardness value distribution curve prepared by embodiment 7 ((50Ti-35Al-15Si)-10TiC);
Figure 13 is the laser melting coating sample abrasion loss distribution curve that embodiment 3 (50Ti-35Al-15Si) is prepared with embodiment 7 ((50Ti-35Al-15Si)-10TiC);
Figure 14 is embodiment 9 ((50Ti-35Al-15Si)-20TiC-1Y
2o
3) X-ray diffractogram of laser melting coating sample prepared;
Figure 15 a is that schematic diagram is organized in cladding layer middle part prepared by embodiment 8 ((50Ti-35Al-15Si)-20TiC);
Figure 15 b is embodiment 9 ((50Ti-35Al-15Si)-20TiC-1Y
2o
3) the cladding layer middle part of preparing organizes schematic diagram;
Figure 16 is embodiment 9 ((50Ti-35Al-15Si)-20TiC-1Y
2o
3) the cladding layer hardness value distribution curve prepared;
Figure 17 is embodiment 8 ((50Ti-35Al-15Si)-20TiC) and embodiment 9 ((50Ti-35Al-15Si)-20TiC-1Y
2o
3) the cladding layer wear weight loss distribution curve prepared;
Figure 18 is embodiment 10 ((50Ti-35Al-15Si)-5B
4the X-ray diffractogram of the laser melting coating sample C) prepared;
Figure 19 is embodiment 10 ((50Ti-35Al-15Si)-5B
4c) the cladding layer hardness value distribution curve prepared;
Figure 20 is embodiment 3 (50Ti-35Al-15Si) and embodiment 10 ((50Ti-35Al-15Si)-5B
4c) the cladding layer wear weight loss distribution curve prepared;
Figure 21 is embodiment 12 ((50Ti-35Al-15Si)-10B
4c-1Y
2o
3) X-ray diffractogram of laser melting coating sample prepared;
Figure 22 a is embodiment 11 ((50Ti-35Al-15Si)-10B
4schematic diagram is organized in the cladding layer middle part of C) preparing;
Figure 22 b is embodiment 12 ((50Ti-35Al-15Si)-10B
4c-1Y
2o
3) the cladding layer middle part of preparing organizes schematic diagram;
Figure 23 is embodiment 12 ((50Ti-35Al-15Si)-10B
4c-1Y
2o
3) the cladding layer hardness value distribution curve prepared;
Figure 24 is embodiment 11 ((50Ti-35Al-15Si)-10B
4and embodiment 12 ((50Ti-35Al-15Si)-10B C)
4c-1Y
2o
3) the cladding layer wear weight loss distribution curve prepared.
Embodiment
The present invention is further illustrated in conjunction with the embodiments, should be noted that following explanation is only to explain the present invention, not limiting its content.
Embodiment 1
A kind of titanium alloy surface intermetallic compound base ceramic composite coating, adopt Al/Ti metal-powder, Si non-metal powder mixed powder as cladding material, utilize laser melting and coating technique to be prepared from, concrete steps are as follows:
(1) Ti-6Al-4V titanium alloy specimen surface is cleaned out, adopt Wire EDM become the Wear specimens of the metallographic specimen of 10mm × 10mm × 10mm and 30mm × 10mm × 10mm after cleaning, dry stand-by;
(2) take cladding material powder, and mixed by powder, in mixed powder, the massfraction of each component is Ti50%, Al40%, Si10%, (being abbreviated as 50Ti-40Al-10Si);
(3) by cladding material mixed powder water glass solution furnishing pasty state, in water glass solution, the volume ratio of water glass and water is 1:3, the addition of water glass solution is instill 8 in every 1g cladding material powder, then titanium alloy-based surface is evenly coated on, coat-thickness controls at 0.6mm, keeps thickness even, natural air drying;
(4) carry out laser melting coating to the above-mentioned sample dried, laser power is chosen as 900W, and the sweep velocity of laser is 5mm/s, and blowing argon gas is protected, and protection air pressure is 0.2MPa, and the spot diameter of laser is fixed as 4mm.
The X-ray diffractogram of the laser melting coating sample that the present embodiment obtains is shown in Fig. 1 a, and laser cladding layer cross-sectional structure figure is shown in Fig. 2, and laser melting coating sample cladding layer shape appearance figure is shown in Fig. 3 a.
Embodiment 2
The massfraction of component each in cladding material mixed powder is adjusted to Ti40%, Al45%, Si15%, and preparation method is with embodiment 1.The X-ray diffractogram of the laser melting coating sample that the present embodiment obtains is shown in Fig. 1 b.
Embodiment 3
The massfraction of component each in cladding material mixed powder is adjusted to Ti50%, Al35%, Si15%, and preparation method is with embodiment 1.The X-ray diffractogram of the laser melting coating sample that the present embodiment obtains is shown in Fig. 1 c.
Embodiment 4
The massfraction of component each in cladding material mixed powder is adjusted to Ti60%, Al25%, Si15%, and preparation method is with embodiment 1.The X-ray diffractogram of the laser melting coating sample that the present embodiment obtains is shown in Fig. 1 d.
Embodiment 5
The massfraction of component each in cladding material mixed powder is adjusted to Ti50%, Al30%, Si20%, and preparation method is with embodiment 1.The X-ray diffractogram of the laser melting coating sample that the present embodiment obtains is shown in Fig. 1 e.
Adopt continuous wave laser to scan sample prepared by embodiment 1-5, in scanning process, blow argon shield molten bath and laser apparatus lens barrel.
X-ray diffraction (XRD) analytical results shows, main containing Ti in titanium alloy surface laser Ti-Al-Si diversification cladding coating
5si
3, Ti
5si
4, TiSi
2deng ceramic phase, Ti
3the intermetallic compounds such as Al and TiAl, as shown in Fig. 1 a to Fig. 1 e.In laser cladding process, the laser beam of high-energy-density acts on specimen surface, fore-put powder and surface layer is melted, forms small molten bath, in molten bath, reaction in-situ occurs, generate above-mentioned strengthening compound.
In laser cladding process, as metallographic phase, Al and Ti partial reaction generates intermetallic compound strengthening phase, Ti and Si reaction generates hard ceramic phase, is distributed in the substrate of metal formation, forms the composite structure similar with concrete.The plasticity and toughness of the high rigidity of ceramic phase and the good of metallographic phase match, and significantly can improve the performance of cladding layer.
As shown in Figure 2, cladding layer cross-sectional structure pattern, molten bath is the crescent shape of the thin thick middle in both sides, coating pore-free and crackle, and coatings and substrate is metallurgical binding, junction smoother.It is the tissue topography of each sample crucible zone of the cladding material powder preparation of different ratio as Fig. 3 a to Fig. 3 e, as shown in Figure 3 a, weave construction is dentrite and some irregular bulk crystals, weave construction is short and small dendrite and some irregular block crystalline substances as shown in Figure 3 b, weave construction is as shown in Figure 3 c uniform gritty texture, and the structure organization shown in Fig. 3 d, Fig. 3 e is flat crystal.Along with the increase of the mass percent of Si in powder mixture ratio, weave construction is refinement gradually, organizes fine uniform the most when the mass percentage of Si reaches 15%, and when the content of Si increases further, structure starts coarsening.In order to tissue of optimizing structure further, when content one timing of Si powder, when the mass percent of Ti powder reaches 50%, structure is the most tiny.
The microhardness of the cladding coating of the cladding material powder preparation of different ratio as shown in Figure 4, under 0.2kg load, tests under the condition of loading time 10s.As seen from the figure, the microhardness of each sample is apparently higher than the microhardness of titanium alloy substrate.The microhardness of 50Ti-35Al-15Si cladding coating is the highest, and maximum can reach 1230HV
0.2, be about Ti-6Al-4V matrix hardness (320-360HV
0.2) 3.5 times, cladding layer thickness is about 0.9mm, and the region of distance cladding layer 0.9-1.1mm is the zone of transition between cladding layer and matrix, and distance cladding surface significantly reduces more than microhardness after 1.1mm.The microhardness of 50Ti-40Al-10Si cladding coating is minimum, and microhardness scope is at 782-950HV
0.2, be about the 2-3 of Ti-6Al-4V matrix hardness doubly, cladding layer thickness is about 0.7mm, and distance cladding surface significantly reduces more than microhardness after 0.7mm.The microhardness scope of 40Ti-35Al-15Si cladding layer is 897-1168HV
0.2, cladding layer thickness is about 0.9mm, and distance cladding surface significantly reduces more than microhardness after 0.9mm.Relatively, the region of distance cladding layer 0.8 ~ 1.0mm is the zone of transition between cladding layer and matrix to the durometer level of 60Ti-25Al-15Si and 50Ti-30Al-20Si, increases hardness drop to matrix hardness gradually with distance.Because coated powder proportioning is different, the microhardness of laser cladding layer is not identical yet, and along with the increase of Si powder content, the microhardness of cladding layer increases, the Ti produced in cladding layer
5si
3and TiSi
2ceramic phase increases.But when Si content is more than 15%, the microhardness value of cladding layer reduces, because Si powder content increases, the tissue change in coating causes greatly hardness to reduce.
As shown in Figure 5, the abrasion loss of laser cladding layer, when added load is 10kg, when the time is 10min, the wear weight loss amount of laser cladding layer is all starkly lower than the wear weight loss amount of titanium alloy substrate.The average abrasion amount of every ten minutes of 40Ti-45Al-15Si cladding layer is 0.0170g is 1/3 of titanium alloy substrate average abrasion amount 0.0514g.The average abrasion amount of 50Ti-35Al-15Si cladding layer is 0.0152g is 1/3.5 of titanium alloy substrate average abrasion amount.The average abrasion amount of 60Ti-25Al-15Si cladding layer is 0.0186g is 1/2.8 of titanium alloy substrate average abrasion amount.Illustrate and to be significantly improved relative to matrix by the wear resistance of alloy surface after Laser Cladding Treatment.The wear resistance of 50Ti-35Al-15Si cladding layer is best, and because the microhardness of 50Ti-35Al-15Si cladding layer is the highest, the homogeneous microstructure of its cladding layer is tiny, good toughness.
Embodiment 6
A kind of titanium alloy surface intermetallic compound base ceramic composite coating, adopt Al/Ti metal-powder, Si non-metal powder, rare earth oxide mixture as cladding material, utilize laser melting and coating technique to be prepared from, concrete steps are as follows:
(1) Ti-6Al-4V titanium alloy specimen surface is cleaned out, adopt Wire EDM become the Wear specimens of the metallographic specimen of 10mm × 10mm × 10mm and 30mm × 10mm × 10mm after cleaning, dry stand-by;
(2) take cladding material powder, and mixed by powder, in mixed powder, the massfraction of each component is Al35%, Si15%, Y
2o
31%, surplus is Ti, is abbreviated as Ti-35Al-15Si-1Y
2o
3;
(3) by cladding material mixed powder water glass solution furnishing pasty state, in water glass solution, the volume ratio of water glass and water is 1:3, the addition of water glass solution is instill 10 in every 1g cladding material powder, then titanium alloy-based surface is evenly coated on, coat-thickness controls at 0.6mm, keeps thickness even, natural air drying;
(4) carry out laser melting coating to the above-mentioned sample dried, laser power is chosen as 900W, and the sweep velocity of laser is 5mm/s, and blowing argon gas is protected, and protection air pressure is 0.2MPa, and the spot diameter of laser is fixed as 4mm.
Adopt continuous wave laser to scan sample, in scanning process, blow argon shield molten bath and laser apparatus lens barrel.
Use Ti-35Al-15Si-1Y
2o
3the mixed powder microstructure that obtains composite ceramic coat after titanium alloy surface carries out laser melting coating be Ti
5si
3, Ti
5si
4, TiSi
2, Al
2o
3and TiO
2deng ceramic phase, Ti
3the intermetallic compounds such as Al and TiAl, as shown in Figure 6.
Fig. 7 a is the tissue topography figure bottom the laser melting coating compound coating of embodiment 3 preparation, Fig. 7 b is the tissue topography figure bottom the laser melting coating compound coating of embodiment 6 preparation, tissue shown in Fig. 7 (b) is finer and close than the homogeneous microstructure shown in Fig. 7 (a), and crystal grain is tiny.This is because nanometer Y
2o
3be high melting compound, out-phase forming core point can be become, nucleation rate is accelerated, causes grain refining, Y
2o
3also dendrite gap can be made to reduce, the growth retardation of dentrite, therefore refinement dendritic structure, tissue becomes even compact.Rare earth element can accelerate the flowing of liquid metal in addition, reduces component segregation, ceramic phase is more easily permeated in dynamic metal, forms Metal-metal bonded compound, thus be combined with matrix stronger with metal.
Composite ceramic coat of the present invention can improve microhardness and the wear resistance of titanium alloy, Ti-35Al-15Si-1Y
2o
3the average microhardness of composite ceramic coat is about 1150HV
0.2, as shown in Figure 8, bring up to TC
4about 3.5 times of alloy substrate hardness, cladding layer thickness is about 0.9mm, and the region of distance cladding layer 0.9-1.2mm is the zone of transition between cladding layer and matrix, increases hardness drop to matrix hardness gradually with distance.Ti-35Al-15Si-1Y
2o
3the compound coating every ten minutes average abrasion amount under the load of 10kg is 0.0135g, and be 1/3.8 of titanium alloy substrate average abrasion amount, result as shown in Figure 9.
Embodiment 7
A kind of titanium alloy surface intermetallic compound base ceramic composite coating, adopt Al/Ti metal-powder, Si non-metal powder, ceramic hard phase mixture as cladding material, utilize laser melting and coating technique to be prepared from, concrete steps are as follows:
(1) Ti-6Al-4V titanium alloy specimen surface is cleaned out, adopt Wire EDM become the Wear specimens of the metallographic specimen of 10mm × 10mm × 10mm and 30mm × 10mm × 10mm after cleaning, dry stand-by;
(2) take cladding material powder, and mixed by powder, in mixed powder, the massfraction of each component is (Ti-Al-Si) 90%, TiC10%; (Ti-Al-Si) in powder, the massfraction of the massfraction of Ti to be the massfraction of 50%, Al be 35%, Si is 15%.Be abbreviated as (50Ti-35Al-15Si)-10TiC;
(3) by cladding material mixed powder water glass solution furnishing pasty state, in water glass solution, the volume ratio of water glass and water is 1:3, the addition of water glass solution is instill 5 in every 1g cladding material powder, then titanium alloy-based surface is evenly coated on, coat-thickness controls at 0.6mm, keeps thickness even, natural air drying;
(4) carry out laser melting coating to the above-mentioned sample dried, laser power is chosen as 900W, and the sweep velocity of laser is 5mm/s, and blowing argon gas is protected, and protection air pressure is 0.2MPa, and the spot diameter of laser is fixed as 4mm.
Adopt continuous wave laser to scan sample, in scanning process, blow argon shield molten bath and laser apparatus lens barrel.
The microstructure obtaining composite ceramic coat with the mixed powder of (50Ti-35Al-15Si)-10TiC after titanium alloy surface carries out laser melting coating is Ti
5si
3, Ti
5si
4, TiSi
2, and ceramic phase and the Ti such as TiC
3the intermetallic compounds such as Al and TiAl as shown in Figure 10.
As shown in figure 11, TiC with tiny dentrite form Dispersed precipitate in the coating.Composite ceramic coat of the present invention can improve microhardness and the wear resistance of titanium alloy, and the highest microhardness of 50Ti-35Al-15Si-10TiC composite ceramic coat is about 1283HV
0.2, as shown in figure 12, about 3.5 times that bring up to Ti-6Al-4V alloy substrate hardness, cladding layer thickness is about 0.8mm, and the region of distance cladding layer 0.8-1.0mm is the zone of transition between cladding layer and matrix, increases hardness drop to matrix hardness gradually with distance.(50Ti-35Al-15Si)-10TiC composite ceramic layer every ten minutes average abrasion the amount under the load of 10kg is 0.0131g, is 1/3.9 of titanium alloy substrate average abrasion amount, as shown in figure 13.
Embodiment 8
A kind of titanium alloy surface intermetallic compound base ceramic composite coating, adopt Al/Ti metal-powder, Si non-metal powder, TiC ceramic powder mixture as cladding material, utilize laser melting and coating technique to be prepared from, concrete steps are as follows:
(1) Ti-6Al-4V titanium alloy specimen surface is cleaned out, adopt Wire EDM become the Wear specimens of the metallographic specimen of 10mm × 10mm × 10mm and 30mm × 10mm × 10mm after cleaning, dry stand-by;
(2) take cladding material powder by certain quality proportioning, and powder is mixed;
(3) by cladding material mixed powder water glass solution furnishing pasty state, the volume ratio of water glass and water is 1:3, the addition of water glass solution is instill 3 in every 1g cladding material powder, then titanium alloy-based surface is evenly coated on, gauge control is at 0.6mm, keep thickness even, natural air drying;
(4) carry out laser melting coating to the above-mentioned sample dried, laser power is chosen as 900W, and the sweep velocity of laser is 5mm/s, and blowing argon gas is protected, and protection air pressure is 0.2MPa, and the spot diameter of laser is fixed as 4mm.
In cladding material mixed powder described in above-mentioned steps (2), the massfraction of each component is (50Ti-35Al-15Si) 80%, TiC20%, is abbreviated as (50Ti-35Al-15Si)-20TiC.
Adopt continuous wave laser to scan sample, in scanning process, blow argon shield molten bath and laser apparatus lens barrel.
Embodiment 9
A kind of titanium alloy surface intermetallic compound base ceramic composite coating, adopts Al/Ti metal-powder, Si non-metal powder, TiC ceramic powder and Y
2o
3rare earth oxide mixture is as cladding material, and utilize laser melting and coating technique to be prepared from, concrete steps are as follows:
(1) Ti-6Al-4V titanium alloy specimen surface is cleaned out, adopt Wire EDM become the Wear specimens of the metallographic specimen of 10mm × 10mm × 10mm and 30mm × 10mm × 10mm after cleaning, dry stand-by;
(2) take cladding material powder by certain quality proportioning, and powder is mixed;
(3) by cladding material mixed powder water glass solution furnishing pasty state, the volume ratio of water glass and water is 1:3, the addition of water glass solution is instill 6 in every 1g cladding material powder, then titanium alloy-based surface is evenly coated on, gauge control is at 0.6mm, keep thickness even, natural air drying;
(4) carry out laser melting coating to the above-mentioned sample dried, laser power is chosen as 900W, and the sweep velocity of laser is 5mm/s, and blowing argon gas is protected, and protection air pressure is 0.2MPa, and the spot diameter of laser is fixed as 4mm.
In cladding material mixed powder described in above-mentioned steps (2), the massfraction of each component is (50Ti-35Al-15Si) 79%+TiC20%+Y
2o
31%, be abbreviated as (50Ti-35Al-15Si)-20TiC-1Y
2o
3.
Adopt continuous wave laser to scan sample, in scanning process, blow argon shield molten bath and laser apparatus lens barrel.
With (50Ti-35Al-15Si)-20TiC-1Y
2o
3the mixed powder microstructure that obtains composite ceramic coat after titanium alloy surface carries out laser melting coating be Ti
5si
3, Ti
5si
4, TiSi
2with ceramic phase and Ti such as TiC
3the intermetallic compounds such as Al and TiAl, as shown in figure 14.Figure 15 a is that schematic diagram is organized in cladding layer middle part prepared by embodiment 8 ((50Ti-35Al-15Si)-20TiC); Figure 15 b is embodiment 9 ((50Ti-35Al-15Si)-20TiC-1Y
2o
3) the cladding layer middle part of preparing organizes schematic diagram, Figure 15 b crystal is more tiny relative to Figure 15 a, this is because appropriate rare earth oxide Y
2o
3the effect of obvious crystal grain thinning can be played.A small amount of Y
2o
3introducing can optimize the tissue of cladding layer, improve the performance of cladding layer further.Under laser beam effect, Y
2o
3part is decomposed, and the Y of formation, as surface active element, easily at Grain Boundary Segregation, suppresses the movement of crystal boundary.In addition, the undecomposed Y of part
2o
3can also as heterogeneous forming core core.Each factor acting in conjunction above, makes Laser Cladding on Titanium Alloy cermet composite coating show higher hardness and wear resistance.
Composite ceramic coat of the present invention can improve microhardness and the wear resistance of titanium alloy, (50Ti-35Al-15Si)-20TiC-1Y
2o
3the highest microhardness of composite ceramic coat is about 1430HV
0.2, as shown in figure 16, about 4 times that bring up to Ti-6Al-4V alloy substrate hardness.(50Ti-35Al-15Si)-20TiC-1Y
2o
3the composite ceramic layer every ten minutes average abrasion amount under the load of 10kg is 0.0104g, is 1/4.8 of titanium alloy substrate average abrasion amount, as shown in figure 17.
Embodiment 10
A kind of titanium alloy surface intermetallic compound base ceramic composite coating, adopts Al/Ti metal-powder, Si non-metal powder, B
4c ceramic powder mixture is as cladding material, and utilize laser melting and coating technique to be prepared from, concrete steps are as follows:
(1) Ti-6Al-4V titanium alloy specimen surface is cleaned out, adopt Wire EDM become the Wear specimens of the metallographic specimen of 10mm × 10mm × 10mm and 30mm × 10mm × 10mm after cleaning, dry stand-by;
(2) take cladding material powder by certain quality proportioning, and powder is mixed;
(3) by cladding material mixed powder water glass solution furnishing pasty state, the volume ratio of water glass and water is 1:3, the addition of water glass solution is instill 4 in every 1g cladding material powder, then titanium alloy-based surface is evenly coated on, gauge control is at 0.6mm, keep thickness even, natural air drying;
(4) carry out laser melting coating to the above-mentioned sample dried, laser power is chosen as 900W, and the sweep velocity of laser is 5mm/s, and blowing argon gas is protected, and protection air pressure is 0.2MPa, and the spot diameter of laser is fixed as 4mm.
Cladding material mixed powder massfraction described in above-mentioned steps (2) is respectively (50Ti-35Al-15Si) 95%+B
4c5%, is abbreviated as (50Ti-35Al-15Si)-5B
4c.
Adopt continuous wave laser to scan sample, in scanning process, blow argon shield molten bath and laser apparatus lens barrel.
With (50Ti-35Al-15Si)-5B
4the microstructure that the mixed powder of C obtains composite ceramic coat after titanium alloy surface carries out laser melting coating is Ti
5si
3, Ti
5si
4, TiSi
2, TiB, TiB
2, ceramic phase and the Ti such as SiC and TiC
3the intermetallic compounds such as Al and TiAl as shown in figure 18.
(50Ti-35Al-15Si)-5B
4the highest microhardness of C composite ceramic coat is about 1240HV
0.2, be about 3.5 times of Ti-6Al-4V matrix hardness, as shown in figure 19.(50Ti-35Al-15Si)-5B
4the average abrasion amount of C composite ceramic layer is 0.0130g, is 1/3.9 of titanium alloy substrate average abrasion amount, as shown in figure 20.
Embodiment 11
A kind of titanium alloy surface cermet composite coating, adopts Al/Ti metal-powder, Si non-metal powder and B
4the mixture of C ceramic hard phase is as cladding material, and utilize laser melting and coating technique to be prepared from, concrete steps are as follows:
(1) Ti-6Al-4V titanium alloy specimen surface is cleaned out, adopt Wire EDM become the Wear specimens of the metallographic specimen of 10mm × 10mm × 10mm and 30mm × 10mm × 10mm after cleaning, dry stand-by;
(2) take cladding material powder by certain quality proportioning, and powder is mixed;
(3) by cladding material mixed powder water glass solution furnishing pasty state, the volume ratio of water glass and water is 1:3, the addition of water glass solution is instill 6 in every 1g cladding material powder, then titanium alloy-based surface is evenly coated on, gauge control is at 0.6mm, keep thickness even, natural air drying;
(4) carry out laser melting coating to the above-mentioned sample dried, laser power is chosen as 900W, and the sweep velocity of laser is 10mm/s, and blowing argon gas is protected, and protection air pressure is 0.3MPa, and the spot diameter of laser is fixed as 4mm.
Cladding material mixed powder massfraction described in above-mentioned steps (2) is (50Ti-35Al-15Si) 90%+B
4c10%, is abbreviated as (50Ti-35Al-15Si)-10B
4c.
Adopt continuous wave laser to scan sample, in scanning process, blow argon shield molten bath and laser apparatus lens barrel.
Embodiment 12
A kind of titanium alloy surface intermetallic compound base ceramic composite coating, adopts Al/Ti metal-powder, Si non-metal powder, B
4c ceramic powder and Y
2o
3rare earth oxide mixture is as cladding material, and utilize laser melting and coating technique to be prepared from, concrete steps are as follows:
(1) Ti-6Al-4V titanium alloy specimen surface is cleaned out, adopt Wire EDM become the Wear specimens of the metallographic specimen of 10mm × 10mm × 10mm and 30mm × 10mm × 10mm after cleaning, dry stand-by;
(2) take cladding material powder by certain quality proportioning, and powder is mixed;
(3) by cladding material mixed powder water glass solution furnishing pasty state, the volume ratio of water glass and water is 1:3, the addition of water glass solution is instill 5 in every 1g cladding material powder, then titanium alloy-based surface is evenly coated on, gauge control is at 0.6mm, keep thickness even, natural air drying;
(4) carry out laser melting coating to the above-mentioned sample dried, laser power is chosen as 900W, and the sweep velocity of laser is 5mm/s, and blowing argon gas is protected, and protection air pressure is 0.2MPa, and the spot diameter of laser is fixed as 4mm.
Cladding material mixed powder massfraction described in above-mentioned steps (2) is (50Ti-35Al-15Si) 89%+B
4c10%+Y
2o
31%, be abbreviated as (50Ti-35Al-15Si)-10B
4c-1Y
2o
3.
Adopt continuous wave laser to scan sample, in scanning process, blow argon shield molten bath and laser apparatus lens barrel.
With (50Ti-35Al-15Si)-10B
4c-1Y
2o
3the mixed powder microstructure that obtains composite ceramic coat after titanium alloy surface carries out laser melting coating be Ti
5si
3, Ti
5si
4, TiSi
2, TiB, TiB
2, SiC, TiC, Al
2o
3and TiO
2deng ceramic phase and Ti
3the intermetallic compounds such as Al and TiAl as shown in figure 21.
Figure 22 a is embodiment 11 ((50Ti-35Al-15Si)-10B
4schematic diagram is organized in the cladding layer middle part of C) preparing; Figure 22 b is embodiment 12 ((50Ti-35Al-15Si)-10B
4c-1Y
2o
3) the cladding layer middle part of preparing organizes schematic diagram; Tissue shown in Figure 22 b is finer and close than the homogeneous microstructure shown in Figure 22 a, and crystal grain is tiny.
Appropriate rare earth oxide Y
2o
3the effect of obvious crystal grain thinning can be played.A small amount of Y
2o
3introducing can optimize the tissue of cladding layer, improve the performance of cladding layer further.Under laser beam effect, Y
2o
3part is decomposed, and the Y of formation, as surface active element, easily at Grain Boundary Segregation, suppresses the movement of crystal boundary.In addition, the undecomposed Y of part
2o
3can also as heterogeneous forming core core.Each factor acting in conjunction above, makes organizing of Laser Cladding on Titanium Alloy cermet composite coating dense.
Composite ceramic coat of the present invention can improve microhardness and the wear resistance of titanium alloy, (50Ti-35Al-15Si)-10B
4c-1Y
2o
3the highest microhardness of composite ceramic coat is about 1362HV
0.2, as shown in figure 23, about 4 times that bring up to TC4 alloy substrate hardness.(50Ti-35Al-15Si)-10B
4c-1Y
2o
3the composite ceramic layer every ten minutes average abrasion amount under the load of 10kg is 0.0107g, and be 1/4.8 of titanium alloy substrate average abrasion amount, result as shown in figure 24.
Claims (10)
1. a preparation technology for titanium alloy surface intermetallic compound base ceramic composite coating, is characterized in that, comprises step as follows:
(1) mixed by cladding material powder, mixed powder tamanori furnishing pasty state, is then evenly coated on titanium alloy surface, and coat-thickness is 0.5-1.0mm, air-dry;
(2) carry out laser melting coating to the coating of titanium alloy surface, laser power is 800-1200W, and the sweep velocity of laser is 2.5-7.5mm/s, and blown inert gas is protected, and protection air pressure is 0.2-0.4MPa;
Wherein, in step (1), in described cladding material mixed powder, each component and massfraction thereof are: Ti25-65%, Al20-60%, Si5-30%, Y
2o
30-3%; Or Ti25-65%, Al20-60%, Si5-30%, B
4c2-40%, Y
2o
30-3%; Or Ti25-65%, Al20-60%, Si5-30%, TiC5-40%, Y
2o
30-3%.
2. the preparation technology of a kind of titanium alloy surface intermetallic compound base ceramic composite coating as claimed in claim 1, is characterized in that, before the coating of cladding material mixed powder, clear up titanium alloy surface, and wipe clean, dry up.
3. the preparation technology of a kind of titanium alloy surface intermetallic compound base ceramic composite coating as claimed in claim 1, is characterized in that, in step (1), described tamanori is water glass solution.
4. the preparation technology of a kind of titanium alloy surface intermetallic compound base ceramic composite coating as claimed in claim 3, is characterized in that, the volume proportion of described water glass solution is water glass: water=1:3.
5. the preparation technology of a kind of titanium alloy surface intermetallic compound base ceramic composite coating as described in claim 3 or 4, is characterized in that, the addition of water glass solution is instill 3-10 in every 1g cladding material mixed powder to drip.
6. the preparation technology of a kind of titanium alloy surface intermetallic compound base ceramic composite coating as claimed in claim 1, is characterized in that, in step (2), the spot diameter of laser scanning is 4mm.
7. the preparation technology of a kind of titanium alloy surface intermetallic compound base ceramic composite coating as claimed in claim 1, it is characterized in that, in step (1), in described mixed powder, each component and massfraction thereof are: Ti30-60%, Al25-55%, Si8-25%, Y
2o
30.2-2.8%; Or Ti30-60%, Al25-55%, Si8-25%, B
4c4-35%, Y
2o
30.2-2.8%; Or Ti30-60%, Al25-55%, Si8-25%, TiC8-35%, Y
2o
30.2-2.8%.
8. the preparation technology of a kind of titanium alloy surface intermetallic compound base ceramic composite coating as claimed in claim 1, is characterized in that, in step (1), in described mixed powder, each component and massfraction thereof are: Ti35-55%, Al30-50%, Si10-20%, Y
2o
30.5-2.5%; Or Ti35-55%, Al30-50%, Si10-20%, B
4c8-30%, Y
2o
30.5-2.5%; Or Ti35-55%, Al30-50%, Si10-20%, TiC15-30%, Y
2o
30.5-2.5%.
9. the preparation technology of a kind of titanium alloy surface intermetallic compound base ceramic composite coating as claimed in claim 1, it is characterized in that, concrete steps are as follows:
(1) titanium alloy specimen surface is cleaned out, dry stand-by;
(2) take cladding material powder, and mixed by powder, in mixed powder, each component and massfraction thereof are Ti50%, Al35%, Si15%;
(3) by cladding material mixed powder water glass solution furnishing pasty state, in water glass solution, the volume ratio of water glass and water is 1:3, the addition of water glass solution is instill 3-10 in every 1g cladding material powder to drip, then titanium alloy-based surface is evenly coated on, coat-thickness controls at 0.5-1.0mm, natural air drying;
(4) carry out laser melting coating to sample, laser power is chosen as 900W, and the sweep velocity of laser is 5mm/s, and blowing argon gas is protected, and protection air pressure is 0.2MPa, and the spot diameter of laser is fixed as 4mm.
10. the preparation technology of a kind of titanium alloy surface intermetallic compound base ceramic composite coating as claimed in claim 1, it is characterized in that, concrete steps are as follows:
(1) titanium alloy specimen surface is cleaned out, dry stand-by;
(2) take cladding material powder, and mixed by powder, in mixed powder, each component and massfraction thereof are Al35%, Si15%, Y
2o
31%, surplus is Ti;
(3) by cladding material mixed powder water glass solution furnishing pasty state, in water glass solution, the volume ratio of water glass and water is 1:3, the addition of water glass solution is instill 3-10 in every 1g cladding material powder to drip, then titanium alloy-based surface is evenly coated on, coat-thickness controls at 0.5-1.0mm, natural air drying;
(4) carry out laser melting coating to sample, laser power is chosen as 900W, and the sweep velocity of laser is 5mm/s, and blowing argon gas is protected, and protection air pressure is 0.2MPa, and the spot diameter of laser is fixed as 4mm.
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