CN103614722A - Laser alloying layer on titanium alloy surface and preparation process thereof - Google Patents
Laser alloying layer on titanium alloy surface and preparation process thereof Download PDFInfo
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- CN103614722A CN103614722A CN201310705480.7A CN201310705480A CN103614722A CN 103614722 A CN103614722 A CN 103614722A CN 201310705480 A CN201310705480 A CN 201310705480A CN 103614722 A CN103614722 A CN 103614722A
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Abstract
The invention relates to a laser alloying layer on a titanium alloy surface and a preparation process thereof. Titanium or titanium alloy is used as a matrix material, and BN or BN and graphite powder are used as a coating material which is applied to the matrix material; a continuous laser is used for scanning a sample, wherein the service power is 800-1,200W, the diameter of a light spot is kept at 4mm, and the scanning speed is 2-10mm/s; in a scanning process of a laser beam, argon is blown to protect a molten pool and a laser lens barrel, and the argon pressure is kept at 0.2-0.4MPa. In the invention, the BN and graphite powder have similar structure and relatively good compatibility; after laser treatment, possible residual BN and graphite particles on the alloying layer can realize an antifriction effect to a certain degree; the surface of the alloying layer is relatively flat, the microstructure is dense, and the hardness is remarkably improved over the matrix.
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 modification technology field.
Background technology
Titanium and alloy thereof 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, thereby but it exists hardness lower and easily produce the shortcomings such as adhesive wear their premium properties is not in full use.
Laser alloying is a kind of novel method that metal material surface partial modification is processed, 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 adding melt simultaneously, mix with body material top layer, forms in a short period of time certain thickness surface alloying layer.The nonequilibrium process of rapidly solidification can make to reach very high degree of supersaturation in the tissue of alloying element after solidifying, thereby forms compound and saturated solid solution that common alloyage process is difficult to obtain, obtains the surface alloying layer with property.
With the method replacement Integral alloy of surface alloying, to save metals resources, be one of the important research content of material supplier author in world wide always.Conventional surface alloying process is exactly thermo-chemical treatment, utilizes the diffusion under high temperature to make alloying element infiltrate matrix, to obtain surface alloying layer, and not only power consumption, and also efficiency is very low.Laser alloying adopts high energy beam laser as thermal source, by rapid melting and rapid solidification, realizes efficiently the surface alloying of matrix metal.
Laser alloying has following advantages:
(1) laser radiation energy high concentration, can carry out long-distance communications by air.
(2) be a kind of immediate processing method, capacity usage ratio is high.
(3) the accurate power ratio control of energy and rate of heating, after processing, matrix metal distortion is little.
(4) can make inaccessible and local region alloying, and utilize the dark focusing of laser, on irregular part, can obtain the uniform alloying degree of 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 property, 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 to improve its wear resistance, TiC, TiN compound-material below carbide chip surface spraying a layer thickness 5～12 μ m.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, can cause some deficiency, thereby not reach required performance requriements.For example, laser Ti Alloying forms TiC, easily in alloying layer, forms flourishing dendritic crystal, thereby causes alloying layer toughness to decline, and is easy to crack.Nitride laser easily forms crackle too, thereby reduces wear resistance and the corrosion resisting property of alloying layer.
Summary of the invention
The object of the invention is to 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 take titanium or titanium alloy is body material, usining BN or BN and Graphite Powder 99 is coated on body material as coated material, by laser alloying, makes, and 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 μ m～30 μ m, and purity is all higher than 99%.
The preparation technology of above-mentioned titanium alloy surface laser alloying coating, comprises that step is as follows:
(1) body material is cut into block sample, on surface, mills out groove, groove through polishing, clean, dry up, stand-by;
(2) coated material is mixed, or mix while guaranteeing two kinds of powder and mix with ball mill;
(3) use water glass solution the even pasty state of mixed powder furnishing, be evenly coated in base metal surface groove, keep coat-thickness even, dry rear stand-by;
(4) adopt continuous wave laser to scan sample; use power is 800～1200W, and spot diameter remains 4mm, sweep velocity 2～10mm/s; in laser beam flying process, blow argon gas with protection molten bath and laser apparatus lens barrel, ar pressure keeps 0.2～0.4MPa.
Above-mentioned steps preferably cuts into body material to be of a size of 10 * 10 * 12mm in (1)
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.3～0.6mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated alcohol, dries up, stand-by.
Water glass and distilled water volume ratio=1:3 in the middle water glass solution of above-mentioned steps (3), average 3～10 of water glass solutions for every gram of mixed powder.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, carries out laser boron, nitrogen, carbon composite alloying on titanium or titanium alloy surface, under certain processing parameter, prepares the alloying layer of high rigidity and microtexture excellence.The BN that the present invention uses is six side BN, is graphite structure, be commonly called as white graphite, and the industrial lubricant that is commonly used for, its concrete composition is as shown in table 1.Adopt it as coated material, to carry out titanium and alloy surface laser alloying thereof, because titanium can react the compounds such as TiB, TiN that generate high rigidity with B, N element, and undecomposed BN can remain in alloying layer, plays to a certain extent the effect of antifriction.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 has had and increased substantially compared with matrix.
(2) laser alloying layer tissue is mainly the hard ceramic phases such as TiB, TiN, TiC that distributing on sosoloid, and these ceramic phases are restriction mutually 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 effect that the BN that alloying layer may be residual and graphite granule can play antifriction to a certain extent, similar with the effect of Graphite in Cast Iron.
(4) cost is lower, and the prices such as the material B N of employing, C 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; (a) alloying layer and (d) alloying layer top, (c) alloying layer middle part, matrix junction (b) alloying layer bottom;
The Hardness Distribution curve 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; (a) alloying layer and (d) alloying layer top, (c) alloying layer middle part, matrix junction (b) alloying layer bottom;
The Hardness Distribution curve 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, (a) alloying layer and alloying layer top, matrix junction (b) (c) alloying layer middle part;
The Hardness Distribution curve 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, (a) (c) alloying layer bottom, alloying layer top (b) alloying layer middle part;
The Hardness Distribution curve 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, (a) (c) alloying layer bottom, alloying layer top (b) alloying layer middle part;
The Hardness Distribution curve of Figure 13 Ti-6Al-4V surface BN+65.9wt.%C laser alloying coating;
The Hardness Distribution curve of Figure 14 Ti-6Al-4V surface BN laser alloying coating;
The Hardness Distribution curve of Figure 15 Ti-6Al-4V surface BN laser alloying coating;
The XRD diffracting spectrum of the pure Ti of Figure 16 surface BN+49.2wt.%C laser alloying coating;
The microstructure morphology of the pure Ti of Figure 17 surface BN+49.2wt.%C laser alloying coating, (a) bottom (b) overlap joint middle layer, region (c);
The Hardness Distribution curve of the pure Ti of Figure 18 surface BN+49.2wt.%C laser alloying coating;
The microstructure morphology at BN+19.5wt.%C laser alloying coating middle part, the pure Ti of Figure 19 surface; (a) low power pattern (b) high power pattern;
The Hardness Distribution curve of the pure Ti of Figure 20 surface BN+19.5wt.%C laser alloying coating;
The Hardness Distribution curve of the pure Ti of Figure 21 surface BN+19.5wt.%C laser alloying coating;
The XRD diffracting spectrum of the pure Ti of Figure 22 surface BN laser alloying coating;
The microstructure morphology of the pure Ti of Figure 23 surface BN laser alloying coating; (a) bottom (b) overlap joint middle layer, region (c);
The Hardness Distribution curve of the pure Ti of Figure 24 surface BN laser alloying coating.
Embodiment
Below in conjunction with embodiment, further illustrate.
Embodiment 1
Take Ti-6Al-4V as being body material, and coated material quality group used becomes BN powder 67.4%, Graphite Powder 99 32.6%.
(1) with wire cutting machine tool, body material is cut into and is of a size of 10 * 10 * 12mm
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.5mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated 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, the even pasty state of mixed powder furnishing, be evenly coated to base metal surface, in the groove described in above-mentioned steps (1), keep even thickness, dry rear stand-by.
(3) adopt continuous wave laser to scan (available instrument HJ-4 type crossing current CO to sample
2gas laser, rated output 1500W), use power is 1000W, and spot diameter remains 4mm, and sweep velocity 5mm/s blows argon gas with protection molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Alloying layer to preparation carries out Analysis of components, microstructure observation and hardness test.
Fig. 1 is the XRD analysis result of sample under embodiment 1 laser technology.Alloying layer is mainly by TiN, TiC, Ti
3b
4compound forms.The BN powder adding can decompose, and reacts respectively with carbon with matrix, forms TiN, TiC, Ti after rapid solidification
3b
4, C
0.3n
0.7the compounds such as Ti.Coating strengthening mechanism is mainly the dispersion-strengthened that these compounds cause.In addition, residual a certain amount of graphite also 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).The tissue of alloying layer bottom is mainly dendroid, may be to form with epitaxial growth mechanism.Dendritic arm is perpendicular to trunk direction Parallel Growth, and the needle-like that around distributes and block precipitated phase, as shown in Fig. 2 (b).
Laser alloying coating middle part is mainly irregular herring-bone form tissue, and the more acicular structure that also distributes therebetween, as shown in Fig. 2 (c).This point is carried out to a composition analysis known, herring-bone form is organized and is mainly contained Ti, N element, and substrate microstructure mainly contains 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 of main acicular structure by cellular structure and distribution therebetween forms, and has 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
Take Ti-6Al-4V as being body material, and coated material quality group used becomes BN powder 50.8%, Graphite Powder 99 49.2%.
(1) with wire cutting machine tool, body material is cut into and is of a size of 10 * 10 * 12mm
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.5mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated 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, the even pasty state of mixed powder furnishing, be evenly coated to base metal surface, in the groove described in above-mentioned steps (1), keep even thickness, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, using power is 1000W, and spot diameter remains 4mm, and sweep velocity 5mm/s blows argon gas with protection molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Alloying layer to preparation carries out Analysis of components, microstructure observation and hardness test.
Fig. 4 is the XRD analysis result of sample under embodiment 2 laser technologies.As seen from the figure, alloying layer is mainly by TiN, TiC, Ti
3b
4compound forms, than embodiment 1, and many again Ti in this alloying layer
3alC intermetallic compound may be due to due to the content of graphite in coating increases.Coating in embodiment is carried out to Observation of Histological Structure, find that organizing of alloying layer also presents gradient gradual change, as shown in Figure 5.It should be noted that a large amount of gritty textures has appearred in coating middle part, 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 is occurring in alloying layer, 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.
Hardness to embodiment 2 alloying layers is tested, and result as shown in Figure 6.Find the too high levels of graphite and be unfavorable for the raising of alloying layer hardness, make on the contrary its hardness decrease, this is likely too high due to graphite fusing point, and absorbed a large amount of energy a large amount of adding of graphite, makes in laser beam flying process chemical reaction in molten bath be obstructed.The generation of the hard phase such as TiC, TiN is restricted, and causes alloying layer lower hardness.
Embodiment 3
Take Ti-6Al-4V as being body material, and coated material quality group used becomes BN powder 80.5%, Graphite Powder 99 19.5%.
(1) with wire cutting machine tool, body material is cut into and is of a size of 10 * 10 * 12mm
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.5mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated 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, the even pasty state of mixed powder furnishing, be evenly coated to base metal surface, in the groove described in above-mentioned steps (1), keep even thickness, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, using power is 1000W, and spot diameter remains 4mm, and sweep velocity 5mm/s blows argon gas with protection molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Alloying layer to preparation carries out Analysis of components, microstructure observation and hardness test.
Fig. 7 is the XRD analysis result of sample under embodiment 3 laser technologies.Coating is also mainly by TiN, TiC, Ti
3b
4compound forms, but has obviously increased hard phase TiB.The analysis of the microhardness below can see, the hardness after BN+19.5%C coating alloy obviously increases, and is exactly probably because the generation of TiB is caused.This compound itself is hard phase, is fine acicular, can refinement and reinforced metal.
Microtexture to embodiment 3 alloying layers is observed, as shown in Figure 8.The combination of alloying layer and matrix is better, organizes also comparatively densification, and has occurred a large amount of acicular structure in the middle part of alloying layer, in conjunction with XRD result, infers 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 comparatively mild.
Embodiment 4
Take Ti-6Al-4V as being body material, and coated material quality group used becomes BN powder 40.8%, Graphite Powder 99 59.2%.
(1) with wire cutting machine tool, body material is cut into and is of a size of 10 * 10 * 12mm
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.5mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated 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, the even pasty state of mixed powder furnishing, be evenly coated to base metal surface, in the groove described in above-mentioned steps (1), keep even thickness, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, using power is 900W, and spot diameter remains 4mm, and sweep velocity 3mm/s blows argon gas with protection molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Alloying layer to preparation carries out microstructure observation and hardness test.
Figure 10 is the tissue topography at embodiment 4 each positions of laser alloying coating, and cladding layer top forms with tiny TiC dendrite and some needle-like titanium borides, and top, owing to being protected the cooling effect of gas, is organized comparatively tiny.
Having there is larger strip phase in middle part, molten bath, should be the boride (TiB of titanium
2), this molten bath, position lifetime is longer, and the strip of separating out 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, there is no obvious dentrite and thick strip phase.Tissue that it should be noted that 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, illustrate under the technique adopting at this embodiment, although the content of graphite is more, also can obtain the laser alloying coating that hardness is higher.
Embodiment 5
Take Ti-6Al-4V as being body material, and coated material quality group used becomes BN powder 34.1%, Graphite Powder 99 65.9%.
(1) with wire cutting machine tool, body material is cut into and is of a size of 10 * 10 * 12mm
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.5mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated 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, the even pasty state of mixed powder furnishing, be evenly coated to base metal surface, in the groove described in above-mentioned steps (1), keep even thickness, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, using power is 1000W, and spot diameter remains 4mm, and sweep velocity 3mm/s blows argon gas with protection molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Alloying layer to preparation carries out microstructure observation and hardness test.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 the laser BN/C alloying layer that visible suitable processing parameter has excellent microstructure and property for acquisition is most important.
Embodiment 6
Take Ti-6Al-4V as being body material, and coated material used is pure BN powder.
(1) with wire cutting machine tool, body material is cut into and is of a size of 10 * 10 * 12mm
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.5mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated alcohol, dries up, stand-by.
(2) use water glass solution the even pasty state of mixed powder furnishing, be evenly coated to base metal surface,, in the groove described in above-mentioned steps (1), keep even thickness, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, using power is 1200W, and spot diameter remains 4mm, and sweep velocity 5mm/s blows argon gas with protection molten bath and laser apparatus lens barrel, ar pressure 0.4MPa in laser beam flying process.
Alloying layer to preparation carries out Analysis of components, microstructure observation and hardness test, and hardness test result as shown in figure 14.
Embodiment 7
Take Ti-6Al-4V as being body material, and coated material used is pure BN powder.
(1) with wire cutting machine tool, body material is cut into and is of a size of 10 * 10 * 12mm
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.4mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated alcohol, dries up, stand-by.
(2) use water glass solution the even pasty state of mixed powder furnishing, be evenly coated to base metal surface,, in the groove described in above-mentioned steps (1), keep even thickness, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, using power is 1200W, and spot diameter remains 4mm, and sweep velocity 7.5mm/s blows argon gas with protection molten bath and laser apparatus lens barrel, ar pressure 0.4MPa in laser beam flying process.
Alloying layer to preparation carries out hardness test, and hardness test result as shown in figure 15.
Take pure titanium as being body material, and coated material quality group used becomes BN powder 50.8%, Graphite Powder 99 49.2%.
(1) with wire cutting machine tool, body material is cut into and is of a size of 10 * 10 * 12mm
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.5mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated 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, the even pasty state of mixed powder furnishing, be evenly coated to base metal surface, in the groove described in above-mentioned steps (1), keep even thickness, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, using power is 900W, and spot diameter remains 4mm, and sweep velocity 5mm/s blows argon gas with protection molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Alloying layer to preparation carries out Analysis of components, microstructure observation and hardness test.
Figure 16 is the XRD diffracting spectrum of embodiment 4 alloying layers.Result shows, mainly has 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, the diffraction spacing of adding some phase that may exist in coating is very approaching, must reduce and with standard diffracting spectrum, coatingsurface carried out the reliability of qualitative analysis, it is very difficult making the demarcation at other close and weak peaks.In calibration result, there is not the oxide compound of coating respective element, illustrate that in laser cladding process, argon gas has played good protection effect.Figure 17 is the tissue topography of alloying layer after the laser alloying of BN-graphite under ar gas environment.In bottom, molten bath, similar to single track laser alloying, present epitaxy mode, there is comparatively significantly border.In interlayer region, because the heat affecting being overlapped causes homogeneous microstructure tiny, present fine particle shape.There is the tissue of particulate state and two kinds of patterns of fine acicular in overlap joint region, doubtful is eutectic growth.During composite alloying, between different Compound Phases, grow, mutually pin down, thereby reduced 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.The alloying element solid solution of laser alloying rear section produces solution strengthening in alloying layer, and molten bath rapid solidification makes the tiny generation refined crystalline strengthening of the crystal grain after alloying crystallization and TiC, TiN, TiB, TiB
2deng hard phase, play the effect of second-phase strengthening, hard phase disperse educt also has the effect of crystal grain thinning.Pure titanium matrix 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
Take pure titanium as being body material, and coated material quality group used becomes BN powder 80.5%, Graphite Powder 99 19.5%.
(1) with wire cutting machine tool, body material is cut into and is of a size of 10 * 10 * 12mm
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.5mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated 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, the even pasty state of mixed powder furnishing, be evenly coated to base metal surface, in the groove described in above-mentioned steps (1), keep even thickness, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, using power is 900W, and spot diameter remains 4mm, and sweep velocity 5mm/s blows argon gas with protection molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Alloying layer to preparation carries out microstructure observation and hardness test.
Figure 19 is the microstructure morphology at BN+19.5wt.%C laser alloying coating middle part, pure titanium surface, can find out, alloying layer middle part is organized comparatively even, mirco structure is observed the growth phase mutual inhibition system of finding some needle-like precipitated phases, Particle Phase and massive phase 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 for result, and maximum hardness is at 1600HV
0.2～1760HV
0.2between.
Embodiment 10
Take pure titanium as being body material, and coated material quality group used becomes BN powder 34.1%, Graphite Powder 99 65.9%.
(1) with wire cutting machine tool, body material is cut into and is of a size of 10 * 10 * 12mm
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.5mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated 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, the even pasty state of mixed powder furnishing, be evenly coated to base metal surface, in the groove described in above-mentioned steps (1), keep even thickness, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, using power is 950W, and spot diameter remains 4mm, and sweep velocity 7.5mm/s blows argon gas with protection molten bath and laser apparatus lens barrel, ar pressure 0.3MPa in laser beam flying process.
Alloying layer to preparation carries out hardness test.
Alloying layer hardness to 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 the fluctuation of Hardness Distribution curve is larger, as shown in figure 21.
Embodiment 11
Take pure titanium as being body material, and coated material used is pure BN powder.
(1) with wire cutting machine tool, body material is cut into and is of a size of 10 * 10 * 12mm
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.4mm.Groove floor is removed the impurity such as oxide skin through sand papering, clean respectively through gasoline, dehydrated alcohol, dries up, stand-by.
(2) use water glass solution the even pasty state of mixed powder furnishing, be evenly coated to base metal surface,, in the groove described in above-mentioned steps (1), keep even thickness, dry rear stand-by.
(3) adopt continuous wave laser to scan sample, using power is 900W, and spot diameter remains 4mm, and sweep velocity 5mm/s blows argon gas with protection molten bath and laser apparatus lens barrel, ar pressure 0.2MPa in laser beam flying process.
Alloying layer to preparation carries out Analysis of components, microstructure observation and hardness test.
Figure 22 is pure Ti surface laser alloying BN coating X-ray diffractogram, there is no the appearance of carbide in this alloying layer, mainly has Ti, TiB, TiB
2, the phase such as TiN.Because nitrogen content is relatively many, also more trend is complicated for nitride, 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.In this coating, there is no Graphite Powder 99, there is no dendritic TiC in the tissue after alloying, thereby alloying organizes and more trend towards bar-shapedly and granular, weave construction is also more even, and zone of transition also has obvious line of delimitation, sees Figure 23 (a).After alloying, top layer compound is dendritic and with a small amount of point-like, and zone of transition has formed more spiculation compound.In interlayer region, laser technical parameters is better, and fine microstructures presents granularly, from Figure 23 (c), can obviously observe.The growth alternate with matrix titanium of the boride of titanium and nitride, restriction mutually, thus suppressed excessively growing up of compound.In overlap joint region, 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 matrix (hardness 110～130HV
0.2) be significantly improved.
Claims (7)
1. a titanium alloy surface laser alloying coating, it take titanium or titanium alloy is body material, usining BN or BN and Graphite Powder 99 is coated on body material as coated material, by laser alloying, makes, and the mass percent of coated material is BN powder 100～30%, Graphite Powder 99 0～70%.
2. 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. 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. a kind of titanium alloy surface laser alloying coating according to claim 1, is characterized in that, described BN and the granularity of Graphite Powder 99 are 1 μ m～30 μ m, and purity is all higher than 99%.
5. the preparation technology of a kind of titanium alloy surface laser alloying coating claimed in claim 1, is characterized in that, comprises that step is as follows:
(1) body material is cut into block sample, on surface, mills out groove, groove through polishing, clean, dry up, stand-by;
(2) coated material is mixed, or mix while guaranteeing two kinds of powder and mix with ball mill;
(3) use water glass solution the even pasty state of mixed powder furnishing, be evenly coated in base metal surface groove, keep coat-thickness even, dry rear stand-by;
(4) adopt continuous wave laser to scan sample; use power is 800～1200W, and spot diameter remains 4mm, sweep velocity 2～10mm/s; in laser beam flying process, blow argon gas with protection molten bath and laser apparatus lens barrel, ar pressure keeps 0.2～0.4MPa.
6. the preparation technology of a kind of titanium alloy surface laser alloying coating according to claim 5, is characterized in that, step preferably cuts into body material to be of a size of 10 * 10 * 12mm in (1)
3block sample, on 12mm * 10mm face, broad ways mills out 8mm * 10mm, the groove of dark 0.3～0.6mm.
7. the preparation technology of a kind of titanium alloy surface laser alloying coating according to claim 5, is characterized in that, water glass and distilled water volume ratio=1:3 in the middle water glass solution of step (3), average 3～10 of water glass solutions for every gram of mixed powder.
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| CN108103496A (en) * | 2017-12-15 | 2018-06-01 | 福建工程学院 | A kind of preparation method of cookware non-stick pan dope layer |
| CN112593231A (en) * | 2020-12-16 | 2021-04-02 | 北京航空航天大学 | Method for preparing Ag-containing antibacterial particles on surface of pure titanium or titanium alloy |
| CN113136540A (en) * | 2021-04-09 | 2021-07-20 | 贵州师范大学 | Preparation method of titanium alloy nano composite gradient strengthening layer |
| CN114774912A (en) * | 2022-04-29 | 2022-07-22 | 西安建筑科技大学 | Preparation method for generating self-lubricating ceramic high-temperature wear-resistant coating in situ by laser cladding |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106756998A (en) * | 2016-12-07 | 2017-05-31 | 山东大学苏州研究院 | A kind of Ni-based cladding layer of Laser Cladding on Titanium Alloy and its preparation technology |
| CN108103496A (en) * | 2017-12-15 | 2018-06-01 | 福建工程学院 | A kind of preparation method of cookware non-stick pan dope layer |
| CN112593231A (en) * | 2020-12-16 | 2021-04-02 | 北京航空航天大学 | Method for preparing Ag-containing antibacterial particles on surface of pure titanium or titanium alloy |
| CN112593231B (en) * | 2020-12-16 | 2021-10-26 | 北京航空航天大学 | Method for preparing Ag-containing antibacterial particles on surface of pure titanium or titanium alloy |
| CN113136540A (en) * | 2021-04-09 | 2021-07-20 | 贵州师范大学 | Preparation method of titanium alloy nano composite gradient strengthening layer |
| CN114774912A (en) * | 2022-04-29 | 2022-07-22 | 西安建筑科技大学 | Preparation method for generating self-lubricating ceramic high-temperature wear-resistant coating in situ by laser cladding |
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