CN103614722B - A kind of titanium alloy surface laser alloying coating and preparation technology thereof - Google Patents
A kind of titanium alloy surface laser alloying coating and preparation technology thereof Download PDFInfo
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- CN103614722B CN103614722B CN201310705480.7A CN201310705480A CN103614722B CN 103614722 B CN103614722 B CN 103614722B CN 201310705480 A CN201310705480 A CN 201310705480A CN 103614722 B CN103614722 B CN 103614722B
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Abstract
The present invention relates to a kind of titanium alloy surface laser alloying coating and preparation technology thereof; it with titanium or titanium alloy for body material; using BN or BN and Graphite Powder 99 as coating material application on body material; continuous wave laser is adopted to scan sample; use power is 800 ~ 1200W, and spot diameter remains 4mm, sweep velocity 2 ~ 10mm/s; blow argon gas in laser beam flying process to protect molten bath and laser apparatus lens barrel, ar pressure keeps 0.2 ~ 0.4MPa.BN of the present invention, Graphite Powder 99 structural similitude, consistency is better, and after laser treatment, the BN that alloying layer may remain and graphite granule can play the effect of antifriction to a certain extent, alloying layer surface ratio is more smooth, and microtexture is fine and close, and hardness comparatively matrix has had and increases substantially.
Description
Technical field
The present invention relates to a kind of titanium alloy surface laser alloying coating and preparation technology thereof, belong to metal material surface strengthening and technical field of modification.
Background technology
Titanium and titanium alloys because specific tenacity is high, corrosion resistance nature and the advantage such as low-temperature performance is good, be widely used in industrial every field, but its to there is hardness lower and easily produce the shortcomings such as adhesive wear thus their premium properties is not in full use.
Laser alloying is a kind of novel method of metal material surface partial modification process, it is one of most active field in the research of current Laser Surface Modification Technology, it utilizes high-energy-density laser beam to make the alloying element of interpolation melt with body material top layer simultaneously, mix, and forms certain thickness surface alloying layer in a short period of time.The nonequilibrium process of rapidly solidification can make to reach very high degree of supersaturation in alloying element tissue after solidification, thus forms compound and saturated solid solution that common alloyage process is difficult to obtain, obtains the surface alloying layer with property.
Replace Integral alloy to be one of the important research content of material supplier author in world wide to save metals resources by the method for surface alloying always.Conventional surface alloying process is exactly thermo-chemical treatment, namely utilizes the diffusion under high temperature to make alloying element infiltrate matrix, to obtain surface alloying layer, not only consume energy, and efficiency is very low.Laser alloying adopts high energy beam laser as thermal source, by rapid melting and rapid solidification, realizes the surface alloying of matrix metal efficiently.
Laser alloying has following advantages:
(1) laser radiation energy high concentration, carries out long-distance communications by air.
(2) be a kind of immediate processing method, capacity usage ratio is high.
(3) can accurately control power and rate of heating, after process, matrix metal distortion is little.
(4) region alloying that is inaccessible and local can be made, and utilize the dark focusing of laser, irregular part can obtain uniform alloying depth.
Laser alloying method both can change the chemical composition of material surface, changed again its heterogeneous microstructure and physical condition, made body material obtain the alloying layer with excellent surface performance, had good development prospect.
The elements such as titanium and boron, nitrogen, carbon can form TiB
2, the compound such as TiB, TiN and TiC.These compounds are metal of bonding coated material, and fusing point is high, fragility is low, interface bond strength is high, interaction trend is strong, has good over-all properties, are commonly used to improve the strong hardness of metallic matrix, the performance such as wear-resisting and corrosion-resistant.Such as, in order to improve the hardness on cutter (blade) surface and improve its wear resistance, at TiC, TiN compound-material of carbide chip surface spraying a layer thickness less than 5 ~ 12 μm.TiN coated chip TiN hardness is 2000HV; TiC coated chip, hardness can reach 3200HV, and wear resistance is good.
If but carry out the laser surface alloying of single-material, some can be caused not enough, thus do not reach required performance requriements.Such as, laser Ti Alloying forms TiC, in alloying layer, easily forms flourishing dendritic crystal, thus cause alloying layer toughness to decline, and be easy to crack.Nitride laser easily forms crackle too, thus reduces wear resistance and the corrosion resisting property of alloying layer.
Summary of the invention
The object of the invention is overcome prior art deficiency and a kind of titanium alloy surface laser alloying coating is provided.
Another object of the present invention is to provide a kind of preparation technology of titanium alloy surface laser alloying coating.
The technical scheme that the present invention takes is:
A kind of titanium alloy surface laser alloying coating, it with titanium or titanium alloy for body material, using BN or BN and Graphite Powder 99 as coating material application on body material, obtained by laser alloying, the mass percent of coated material is BN powder 100 ~ 30%, Graphite Powder 99 0 ~ 70%.
Described coated material mass percent composition is preferably BN powder 85 ~ 40%, Graphite Powder 99 15 ~ 60%.
Described coated material mass percent forms more preferably BN powder 70 ~ 40%, Graphite Powder 99 30 ~ 60%.
Described BN and the granularity of Graphite Powder 99 are 1 μm ~ 30 μm, and purity is all higher than 99%.
The preparation technology of above-mentioned titanium alloy surface laser alloying coating, comprises step as follows:
(1) body material is cut into block sample, mills out groove on surface, groove through polishing, cleaning, dry up, stand-by;
(2) coated material is mixed, or mix when guaranteeing two kinds of powder with ball mill mixing;
(3) use water glass solution mixed powder furnishing homogeneous paste, even application, in base metal surface groove, keeps uniform coating thickness, dries rear stand-by;
(4) continuous wave laser is adopted to scan sample; use power is 800 ~ 1200W, and spot diameter remains 4mm, sweep velocity 2 ~ 10mm/s; blow argon gas in laser beam flying process to protect molten bath and laser apparatus lens barrel, ar pressure keeps 0.2 ~ 0.4MPa.
Preferably body material is cut in above-mentioned steps (1) and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.3 ~ 0.6mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
Water glass and distilled water volume ratio=1:3, on average every gram of mixed powder water glass solution 3 ~ 10 in the middle water glass solution of above-mentioned steps (3).Namely step (3) coat-thickness is the thickness (0.3 ~ 0.6mm) of step (1) further groove, and the present invention controls the thickness of preset coating by the groove of milling different depths in advance.
The chemical constitution (wt.%) of table 2-3 boron nitride powder
The present invention utilizes boron nitride (BN) and graphite (C) powder as coated material, laser boron, nitrogen, carbon composite alloying is carried out on titanium or titanium alloy surface, under certain processing parameter, prepare high rigidity and the alloying layer of microtexture excellence.The BN that the present invention uses is hexagonal AlN, is graphite structure, is commonly called as white graphite, is industrially commonly used for lubricant, and its concrete composition is as shown in table 1.Adopt it to carry out titanium and titanium alloys surface laser alloying as coated material, because titanium can react the compounds such as TiB, the TiN generating high rigidity with B, N element, and undecomposed BN can remain in alloying layer, plays the effect of antifriction to a certain extent.Effect and the BN of graphite are similar, and except generating TiC, unnecessary graphite also can play antifriction function, improves the tribological property of matrix.
The invention has the beneficial effects as follows:
(1) alloying layer surface ratio is more smooth, and microtexture is fine and close, and hardness comparatively matrix has had and increases substantially.
(2) laser alloying layer tissue is mainly and is dispersed with the hard ceramic phases such as TiB, TiN, TiC on sosoloid, and these ceramic phases mutually restrict in process of growth, is of value to the improvement of alloying layer structures.
(3) BN, Graphite Powder 99 structural similitude, consistency is better, and after laser treatment, the BN that alloying layer may remain and graphite granule can play the effect of antifriction to a certain extent, similar with the effect of Graphite in Cast Iron.
(4) cost is lower, and the prices such as material B N, the C of employing are lower, and for laser alloying, cost performance is higher.
Accompanying drawing explanation
The XRD diffracting spectrum of Fig. 1 Ti-6Al-4V surface BN+32.6wt.%C laser alloying coating;
The microstructure morphology of Fig. 2 Ti-6Al-4V surface BN+32.6wt.%C laser alloying coating; (d) alloying layer top in the middle part of (c) alloying layer bottom (a) alloying layer and matrix junction (b) alloying layer;
The hardness profile of Fig. 3 Ti-6Al-4V surface BN+32.6wt.%C laser alloying coating;
The XRD diffracting spectrum of Fig. 4 Ti-6Al-4V surface BN+49.2wt.%C laser alloying coating;
The microstructure morphology of Fig. 5 Ti-6Al-4V surface BN+49.2wt.%C laser alloying coating; (d) alloying layer top in the middle part of (c) alloying layer bottom (a) alloying layer and matrix junction (b) alloying layer;
The hardness profile of Fig. 6 Ti-6Al-4V surface BN+49.2wt.%C laser alloying coating;
The XRD diffracting spectrum of Fig. 7 Ti-6Al-4V surface BN+19.5wt.%C laser alloying coating;
The microstructure morphology of Fig. 8 Ti-6Al-4V surface BN+19.5wt.%C laser alloying coating, in the middle part of (a) alloying layer and matrix junction (b) alloying layer top (c) alloying layer;
The hardness profile of Fig. 9 Ti-6Al-4V surface BN+19.5wt.%C laser alloying coating;
The microstructure morphology of Figure 10 Ti-6Al-4V surface BN+59.2wt.%C laser alloying coating, (c) alloying layer bottom in the middle part of (a) alloying layer top (b) alloying layer;
The hardness profile of Figure 11 Ti-6Al-4V surface BN+59.2wt.%C laser alloying coating;
The microstructure morphology of Figure 12 Ti-6Al-4V surface BN+65.9wt.%C laser alloying coating, (c) alloying layer bottom in the middle part of (a) alloying layer top (b) alloying layer;
The hardness profile of Figure 13 Ti-6Al-4V surface BN+65.9wt.%C laser alloying coating;
The hardness profile of Figure 14 Ti-6Al-4V surface BN laser alloying coating;
The hardness profile of Figure 15 Ti-6Al-4V surface BN laser alloying coating;
The XRD diffracting spectrum of Figure 16 pure Ti surface BN+49.2wt.%C laser alloying coating;
The microstructure morphology of Figure 17 pure Ti surface BN+49.2wt.%C laser alloying coating, (b) overlapping regions (c) middle layer, (a) bottom;
The hardness profile of Figure 18 pure Ti surface BN+49.2wt.%C laser alloying coating;
Microstructure morphology in the middle part of the BN+19.5wt.%C laser alloying coating of Figure 19 pure Ti surface; (a) low power pattern (b) high power pattern;
The hardness profile of Figure 20 pure Ti surface BN+19.5wt.%C laser alloying coating;
The hardness profile of Figure 21 pure Ti surface BN+19.5wt.%C laser alloying coating;
The XRD diffracting spectrum of Figure 22 pure Ti surface BN laser alloying coating;
The microstructure morphology of Figure 23 pure Ti surface BN laser alloying coating; (b) overlapping regions (c) middle layer, (a) bottom;
The hardness profile of Figure 24 pure Ti surface BN laser alloying coating.
Embodiment
Further illustrate below in conjunction with embodiment.
Embodiment 1
Using Ti-6Al-4V as body material, coated material quality group used becomes BN powder 67.4%, Graphite Powder 99 32.6%.
(1) with wire cutting machine tool body material cut into and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.5mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
(2) with ball mill, the BN of above-mentioned mass percent and Graphite Powder 99 are mixed, with water glass solution mixed powder furnishing homogeneous paste, even application to base metal surface, in the groove namely described in above-mentioned steps (1), keep thickness even, dry rear stand-by.
(3) continuous wave laser is adopted to scan (available instrumentation HJ-4 type crossing current CO to sample
2gas laser, rated output 1500W), use power is 1000W, and spot diameter remains 4mm, sweep velocity 5mm/s, blows argon gas to protect molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Analysis of components, microstructure observation and hardness test are carried out to the alloying layer of preparation.
Fig. 1 is the XRD analysis result of sample under embodiment 1 laser technology.Alloying layer is primarily of TiN, TiC, Ti
3b
4compound forms.The BN powder added can decompose, and reacts respectively, form TiN, TiC, Ti after rapid solidification with carbon with matrix
3b
4, C
0.3n
0.7the compounds such as Ti.The mainly dispersion-strengthened that causes of these compounds of coating strengthening mechanism.In addition, also remain a certain amount of graphite in alloying layer, these graphite can play the effect of antifriction in part military service process.
Fig. 2 is the tissue topography of embodiment 1 laser alloying coating.Alloying layer is combined comparatively tight with matrix, matrix, because of the rapid quenching effect of laser beam, is mainly needle type martensite, as shown in Fig. 2 (a).Tissue bottom alloying layer is mainly dendroid, may be to be formed with epitaxial growth mechanism.Dendritic arm is perpendicular to trunk direction Parallel Growth, and distribution needle-like and lumpy precipitate phase around, as shown in Fig. 2 (b).
Be mainly irregular herring-bone form tissue in the middle part of laser alloying coating, also distribute more acicular structure therebetween, as shown in Fig. 2 (c).Carry out a composition analysis to this point known, herring-bone form tissue is mainly containing Ti, N element, and substrate microstructure mainly containing Ti element, in conjunction with X-ray diffraction analysis result above, can infer that herring-bone form tissue should be the nitride into Ti.
The tissue topography on the top layer that Fig. 2 (d) is laser alloying coating, this layer primarily of cellular structure and distribute therebetween acicular structure composition, have no obvious treeing.
As shown in Figure 3, alloying layer hardness is up to 1574HV to the microhardness distribution of laser surface alloying BN+32.6wt.%C coating
0.2, far away higher than matrix hardness 372HV
0.2.
Embodiment 2
Using Ti-6Al-4V as body material, coated material quality group used becomes BN powder 50.8%, Graphite Powder 99 49.2%.
(1) with wire cutting machine tool body material cut into and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.5mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
(2) with ball mill, the BN of above-mentioned mass percent and Graphite Powder 99 are mixed, with water glass solution mixed powder furnishing homogeneous paste, even application to base metal surface, in the groove namely described in above-mentioned steps (1), keep thickness even, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, use power to be 1000W, spot diameter remains 4mm, sweep velocity 5mm/s, blows argon gas to protect molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Analysis of components, microstructure observation and hardness test are carried out to the alloying layer of preparation.
Fig. 4 is the XRD analysis result of sample under embodiment 2 laser technology.As seen from the figure, alloying layer is primarily of TiN, TiC, Ti
3b
4compound forms, compared to embodiment 1, and many again Ti in this alloying layer
3alC intermetallic compound may be caused by the content increase due to graphite in coating.Observation of Histological Structure is carried out to the coating in embodiment, finds that organizing of alloying layer also presents gradient, as shown in Figure 5.It should be noted that and occurred a large amount of gritty textures in the middle part of coating, as shown in Figure 5.The existence of these crystalline particulate phases is not only closely related with the temperature distribution of alloying layer, also relevant with the characteristic of Laser Surface Treatment.In laser beam flying process, complicated physical-chemical reaction occurs in alloying layer, and because molten bath lifetime is shorter, in molten bath, the growth of crystallization phases and the diffusion of alloying element are restricted, and cause the tissue of alloying layer to present areal distribution.
Test the hardness of the 2-in-1 aurification layer of embodiment, result as shown in Figure 6.Find the too high levels of graphite and be unfavorable for the raising of alloying layer hardness, its hardness is made to decrease on the contrary, this is likely too high due to graphite fusing point, and adding of a large amount of graphite absorbs a large amount of energy, to make in laser beam flying process chemical reaction in molten bath be obstructed.The generation of the hard phases such as TiC, TiN is restricted, and causes alloying layer hardness to reduce.
Embodiment 3
Using Ti-6Al-4V as body material, coated material quality group used becomes BN powder 80.5%, Graphite Powder 99 19.5%.
(1) with wire cutting machine tool body material cut into and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.5mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
(2) with ball mill, the BN of above-mentioned mass percent and Graphite Powder 99 are mixed, with water glass solution mixed powder furnishing homogeneous paste, even application to base metal surface, in the groove namely described in above-mentioned steps (1), keep thickness even, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, use power to be 1000W, spot diameter remains 4mm, sweep velocity 5mm/s, blows argon gas to protect molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Analysis of components, microstructure observation and hardness test are carried out to the alloying layer of preparation.
Fig. 7 is the XRD analysis result of sample under embodiment 3 laser technology.Coating is also primarily of TiN, TiC, Ti
3b
4compound forms, but significantly increases hard phase TiB.The analysis of the microhardness below can be seen, the hardness after BN+19.5%C coating alloy obviously increases, probably due to TiB generation caused by.This compound itself is hard phase, in fine acicular, and can refinement and reinforced metal.
The microtexture of embodiment 3 alloying layer is observed, as shown in Figure 8.The combination of alloying layer and matrix is better, organizes also comparatively fine and close, and has occurred a large amount of acicular structure in the middle part of alloying layer, in conjunction with XRD result, infer that it is TiB.
Involutory aurification layer tissue is observed, and finds that alloying layer hardness reaches as high as 1700HV
0.2above, and changes in hardness is comparatively mild.
Embodiment 4
Using Ti-6Al-4V as body material, coated material quality group used becomes BN powder 40.8%, Graphite Powder 99 59.2%.
(1) with wire cutting machine tool body material cut into and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.5mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
(2) with ball mill, the BN of above-mentioned mass percent and Graphite Powder 99 are mixed, with water glass solution mixed powder furnishing homogeneous paste, even application to base metal surface, in the groove namely described in above-mentioned steps (1), keep thickness even, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, use power to be 900W, spot diameter remains 4mm, sweep velocity 3mm/s, blows argon gas to protect molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Microstructure observation and hardness test are carried out to the alloying layer of preparation.
Figure 10 is the tissue topography at each position of embodiment 4 laser alloying coating, and cladding layer top is with tiny TiC dendrite and some needle-like titanium borides composition, and top, owing to being subject to the cooling effect protecting gas, is organized comparatively tiny.
There is larger strip phase in the middle part of molten bath, should be the boride (TiB of titanium
2), this molten bath, position lifetime is longer, and the strip of precipitation has the long period to grow up mutually.Bottom, molten bath is mainly particulate state precipitated phase, and due to the chilling action of matrix, precipitated phase is comparatively tiny, does not have obvious dentrite and thick strip phase.It should be noted that the tissue at this position presents certain directivity, relevant with the direction of heat flow in alloying process.
Hardness test shows, alloying layer maximum hardness is about 1580HV
0.2, under the technique adopted is described, although the content of graphite is more, the higher laser alloying coating of hardness also can be obtained in this embodiment.
Embodiment 5
Using Ti-6Al-4V as body material, coated material quality group used becomes BN powder 34.1%, Graphite Powder 99 65.9%.
(1) with wire cutting machine tool body material cut into and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.5mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
(2) with ball mill, the BN of above-mentioned mass percent and Graphite Powder 99 are mixed, with water glass solution mixed powder furnishing homogeneous paste, even application to base metal surface, in the groove namely described in above-mentioned steps (1), keep thickness even, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, use power to be 1000W, spot diameter remains 4mm, sweep velocity 3mm/s, blows argon gas to protect molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Microstructure observation and hardness test are carried out to the alloying layer of preparation.As shown in figure 12, alloying layer organize comparatively fine and close.Involutory aurification layer carries out hardness test, and result shows, the maximum hardness of cladding layer is about 1860HV
0.2, as shown in figure 13, comparing matrix hardness has had and has increased substantially, and processing parameter suitable is as seen most important for obtaining the laser BN/C alloying layer with excellent microstructure and property.
Embodiment 6
Using Ti-6Al-4V as body material, coated material used is pure BN powder.
(1) with wire cutting machine tool body material cut into and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.5mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
(2) use water glass solution mixed powder furnishing homogeneous paste, even application, to base metal surface, in the groove namely described in above-mentioned steps (1), keeps thickness even, dries rear stand-by.
(3) adopt continuous wave laser to scan sample, use power to be 1200W, spot diameter remains 4mm, sweep velocity 5mm/s, blows argon gas to protect molten bath and laser apparatus lens barrel, ar pressure 0.4MPa in laser beam flying process.
Carry out Analysis of components, microstructure observation and hardness test to the alloying layer of preparation, hardness test result as shown in figure 14.
Embodiment 7
Using Ti-6Al-4V as body material, coated material used is pure BN powder.
(1) with wire cutting machine tool body material cut into and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.4mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
(2) use water glass solution mixed powder furnishing homogeneous paste, even application, to base metal surface, in the groove namely described in above-mentioned steps (1), keeps thickness even, dries rear stand-by.
(3) adopt continuous wave laser to scan sample, use power to be 1200W, spot diameter remains 4mm, sweep velocity 7.5mm/s, blows argon gas to protect molten bath and laser apparatus lens barrel, ar pressure 0.4MPa in laser beam flying process.
Carry out hardness test to the alloying layer of preparation, hardness test result as shown in figure 15.
Embodiment 8
Using pure titanium as body material, coated material quality group used becomes BN powder 50.8%, Graphite Powder 99 49.2%.
(1) with wire cutting machine tool body material cut into and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.5mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
(2) with ball mill, the BN of above-mentioned mass percent and Graphite Powder 99 are mixed, with water glass solution mixed powder furnishing homogeneous paste, even application to base metal surface, in the groove namely described in above-mentioned steps (1), keep thickness even, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, use power to be 900W, spot diameter remains 4mm, sweep velocity 5mm/s, blows argon gas to protect molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Analysis of components, microstructure observation and hardness test are carried out to the alloying layer of preparation.
Figure 16 is the XRD diffracting spectrum of embodiment 4 alloying layer.Result shows, mainly there is Ti, TiB, TiB in alloying layer
2, the phase such as TiN, TiC.Because the formation mutually of this powdered alloy itself is very complicated, the nonequilibrium process of laser alloying causes metastable phase to be separated out, add the diffraction spacing of some thing phase that may exist in coating closely, must reduce the reliability of with standard diffraction collection of illustrative plates, coatingsurface being carried out to qualitative analysis, it is very difficult for making the demarcation at other close and weak peaks.There is not the oxide compound of coating respective element in calibration result, illustrate that in laser cladding process, argon gas serves good protected effect.Figure 17 is the tissue topography of alloying layer after the laser alloying of BN-graphite under ar gas environment.Bottom molten bath, similar to single track laser alloying, present epitaxial growth regime, have comparatively significantly border.In interlayer region, cause due to the heat affecting overlapped homogeneous microstructure tiny, present fine particle shape.There is the tissue of particulate state and fine acicular two kinds of patterns in overlapping regions, doubtful is eutectic growth.During composite alloying, grow between different Compound Phases, mutually pin down, thus decrease the formation of flourishing dendrite, refinement alloying layer structures.Figure 18 is BN+ graphite laser alloying coating microhardness distribution curve along depth direction on cross section.As can be seen from the figure the hardness of alloying layer, heat affected zone and matrix reduces gradually along the degree of depth, finally reaches the hardness of matrix.Laser alloying rear section alloying element is solid-solution in alloying layer and produces solution strengthening, and molten bath rapid solidification makes the tiny generation refined crystalline strengthening of the crystal grain after alloying crystallization and TiC, TiN, TiB, TiB
2play the effect of second-phase strength Deng hard phase, hard phase disperse educt also has the effect of crystal grain thinning.Pure Titanium base hardness is greatly about 110 ~ 130HV
0.2between, the maximum hardness after boron carbon nitrogen composite alloying can reach 2500HV
0.2left and right.
Embodiment 9
Using pure titanium as body material, coated material quality group used becomes BN powder 80.5%, Graphite Powder 99 19.5%.
(1) with wire cutting machine tool body material cut into and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.5mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
(2) with ball mill, the BN of above-mentioned mass percent and Graphite Powder 99 are mixed, with water glass solution mixed powder furnishing homogeneous paste, even application to base metal surface, in the groove namely described in above-mentioned steps (1), keep thickness even, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, use power to be 900W, spot diameter remains 4mm, sweep velocity 5mm/s, blows argon gas to protect molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Microstructure observation and hardness test are carried out to the alloying layer of preparation.
Figure 19 is the microstructure morphology in the middle part of the BN+19.5wt.%C laser alloying coating of pure titanium surface, can find out, organize comparatively even in the middle part of alloying layer, mirco structure observes the growth phase mutual inhibition system of some needle-like precipitated phase, Particle Phase and the massive phases found wherein, and this is conducive to the optimization of alloying layer structures and the lifting of performance.Involutory aurification layer carries out hardness test, and as shown in figure 20, Hardness Distribution is comparatively mild, and maximum hardness is at 1600HV for result
0.2~ 1760HV
0.2between.
Embodiment 10
Using pure titanium as body material, coated material quality group used becomes BN powder 34.1%, Graphite Powder 99 65.9%.
(1) with wire cutting machine tool body material cut into and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.5mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
(2) with ball mill, the BN of above-mentioned mass percent and Graphite Powder 99 are mixed, with water glass solution mixed powder furnishing homogeneous paste, even application to base metal surface, in the groove namely described in above-mentioned steps (1), keep thickness even, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, use power to be 950W, spot diameter remains 4mm, sweep velocity 7.5mm/s, blows argon gas to protect molten bath and laser apparatus lens barrel, ar pressure 0.3MPa in laser beam flying process.
Hardness test is carried out to the alloying layer of preparation.
The alloying layer hardness of embodiment 10 is tested, result shows, the hardness value of alloying layer is lower, likely relevant with processing parameter, the excessive power density that causes of sweep velocity is lower, chemical reaction in alloying layer is carried out insufficient, the generation of the hard phases such as TiB, TiC, TiN is suppressed, and causes hardness value on the low side (only up to 1430HV
0.2), and hardness profile fluctuation is comparatively large, as shown in figure 21.
Embodiment 11
Using pure titanium as body material, coated material used is pure BN powder.
(1) with wire cutting machine tool body material cut into and be of a size of 10 × 10 × 12mm
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.4mm.Groove floor removes the impurity such as oxide skin through sand papering, respectively through gasoline, washes of absolute alcohol, dries up, stand-by.
(2) use water glass solution mixed powder furnishing homogeneous paste, even application, to base metal surface, in the groove namely described in above-mentioned steps (1), keeps thickness even, dries rear stand-by.
(3) adopt continuous wave laser to scan sample, use power to be 900W, spot diameter remains 4mm, sweep velocity 5mm/s, blows argon gas to protect molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Analysis of components, microstructure observation and hardness test are carried out to the alloying layer of preparation.
Figure 22 is pure Ti surface laser alloying BN coating X-ray diffractogram, does not have the appearance of carbide, mainly there is Ti, TiB, TiB in this alloying layer
2, the phase such as TiN.Because nitrogen content is relatively many, nitride also more tends to complicated, occurs Ti
2the phases such as N.
Figure 23 is the tissue topography of alloying layer after BN laser lap alloying under ar gas environment.Without Graphite Powder 99 in this coating, do not have dendritic TiC in the tissue after alloying, thus alloying is organized and is more trended towards bar-shaped and granular, and weave construction is also more even, and zone of transition also has obvious line of delimitation, sees Figure 23 (a).After alloying, skim compound is dendritic and with a small amount of point-like, zone of transition then defines more acicular compounds.In interlayer region, laser technical parameters is better, and fine microstructures, presents granular, can obviously observe from Figure 23 (c).The growth alternate with matrix titanium nitride of the boride of titanium, mutually restricts, thus inhibits excessively growing up of compound.In overlapping regions, see Figure 23 (b), present two-phase hybrid state, by ultimate analysis, known black region is mainly matrix Ti composition, and white light tone region is ceramic phase.Figure 24 is the Hardness Distribution on the pure titanium surface after laser BN alloying, and as seen from the figure, the maximum hardness of alloying layer can reach 2150HV
0.2left and right, compares pure Titanium base (hardness 110 ~ 130HV
0.2) be significantly improved.
Claims (4)
1. the preparation technology of a titanium alloy surface laser alloying coating, it with titanium or titanium alloy for body material, using BN and Graphite Powder 99 as coating material application on body material, obtained by laser alloying, the mass percent of coated material is BN powder 100 ~ 30%, Graphite Powder 99 0 ~ 70%; It is characterized in that, comprise step as follows:
(1) body material is cut into block sample, mills out groove on surface, groove through polishing, cleaning, dry up, stand-by;
(2) coated material is mixed, or mix when guaranteeing two kinds of powder with ball mill mixing;
(3) use water glass solution mixed powder furnishing homogeneous paste, even application, in base metal surface groove, keeps uniform coating thickness, dries rear stand-by;
(4) adopt continuous wave laser to scan sample, use power to be 800 ~ 1200W, spot diameter remains 4mm; sweep velocity 2 ~ 10mm/s; blow argon gas in laser beam flying process to protect molten bath and laser apparatus lens barrel, ar pressure keeps 0.2 ~ 0.4MPa
Described BN and the granularity of Graphite Powder 99 are 1 μm ~ 30 μm, and purity is all higher than 99%;
Water glass and distilled water volume ratio=1:3, on average every gram of mixed powder water glass solution 3 ~ 10 in the middle water glass solution of step (3).
2. the preparation technology of a kind of titanium alloy surface laser alloying coating according to claim 1, is characterized in that, described coated material consists of BN powder 85 ~ 40%, Graphite Powder 99 15 ~ 60%.
3. the preparation technology of a kind of titanium alloy surface laser alloying coating according to claim 1, is characterized in that, described coated material is BN powder 70 ~ 40%, Graphite Powder 99 30 ~ 60%.
4. the preparation technology of a kind of titanium alloy surface laser alloying coating according to claim 1, is characterized in that, is preferably cut into by body material and be of a size of 10 × 10 × 12mm in step (1)
3block sample, 12mm × 10mm face mills out 8mm × 10mm in the width direction, the groove of dark 0.3 ~ 0.6mm.
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| TC4钛合金表面激光熔覆C与BN粉末原位生成复合涂层;蒋松林等;《激光与红外》;20100531;第40卷(第5期);第460页第1-3段 * |
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