CN101812684B - Method for preparing metal surface laser strengthened coat - Google Patents
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Abstract
The invention discloses a method for preparing a metal surface laser strengthened coat, which comprises the following steps: preparing uniformly mixed powder of titanium dioxide hydrate and graphite powder by using a wet chemistry method; pre-placing the mixed powder on the surface of a basal body; and irradiating the surface of the basal body by using laser as a heat source under an argon atmosphere to form a molten pool, performing a carbon-thermal chemical reaction on the pre-placed mixed powder under a high-temperature environment to generate titanium carbide, and finally forming a titanium carbide composite coat on the surface of the basal body. In the same way, the method is also suitable for preparing a TiN enhanced composite coat by mixing hydrated oxide thereof and graphite by the wet chemistry method, then mixing the mixture and urea to form pre-placed powder and cladding the pre-placed powder on the basal body by laser. The surface of the enhanced coat prepared by the technical scheme is smooth, and has no cracks or pores; enhancing particles are uniformly distributed in the coat; the enhanced coat and the basal body are metallurgically combined; and the mixed powder prepared by adopting the wet chemistry method is uniformly mixed, ensures complete reaction, and is suitable for industrial popularization and application.
Description
Technical field
The invention belongs to the metal composite field, particularly relate to a kind of method for preparing in-situ formation of TiC or TiN compound coating, the enhancing compound coating of the present invention's preparation is applicable to the surface strengthening of mould, instrument and other easy-abrasion part.
Background technology
At each industrial sector, many mechanisms are in its normal use, because its working-surface frequently contacts, clashes into workpiece to be machined, can cause to a certain degree the abrasion of mould top layer, degrade, and in the course of time, a whole set of mould can lose efficacy because of overwear vt..Industry member often need spend a large amount of manpowers, financial resources and time, and the element of scrapping too early because of overwear vt. is replaced.If these elements use wimet to make, can improve its work-ing life, still, so also will spend great cost.
Present solution is to prepare one deck strengthening layer to improve its abrasion resistance properties at industrial element surface.The method for preparing strengthening layer is a lot, like surface chemistry DIFFUSION TREATMENT (nitrogenize or iron carbide sill etc.).Using these technological shortcomings is to carry out heat treated to whole element; This is human and material resources, the financial resources of consume significant not only; Also can cause the variation of component size and the decline of overall performance, and after surface treatment, also need further carry out follow-up thermal treatment work.
Ceramic reinforced phase titanium carbide, titanium nitride etc. have characteristics such as hardness height, fusing point is high, chemicalstability is good, are that good heat resistant and wear resistant decreases material.To greatly improve its wearability at base member surface preparation one deck ceramic phase strengthening layer, thus the work-ing life of prolonged mechanical device.At present, the research for preparing this kind strengthening layer mainly concentrates on chemical vapor deposition (CVD) and ion plating method, and preparing strengthening layer with these methods need carry out under comparatively high temps, and this overall performance to body material will exert an influence; Strengthening layer with the preparation of these methods just is deposited on matrix surface simultaneously, with the bonding force of matrix can not be satisfactory.
It is high to prepare strengthening phase compound coating cost to above method; Problems such as strengthening layer and body material bonding strength are not high, the patent No. are that 92105630 Chinese patent discloses a kind of employing electric-arc thermal spray coating technology at base metal surface spraying preparation titanium nitride strengthened coat.Its principle is to adopt titanium wire as the titanium source, replaces air as propulsive gases with highly purified nitrogen, and in the electric-arc thermal spray coating process, the titanium of atomizing just reacts with nitrogen in flight course, generates the titanium nitride compound.When the fused titanium nitride drops onto the element surface that is applying, solidify, just form the hard titanium nitride coating of one deck, thereby prevent component abrasion and corrosion.This method is with respect to chemical vapour deposition, plasma spraying, and is with low cost, and in addition, electric arc spraying is as long as spend several minutes, and with respect to technologies such as chemical vapour depositions, the time shortens greatly.But by the effect that does not reach metallurgical binding between the titanium nitride strengthening layer of this method preparation and the matrix; The unstable problem of bonding force still is not resolved; Above patent in principle, is a utilization electric-arc thermal spray coating technology; React through titanium and stable nitrogen and to prepare titanium carbide, this needs very high energy.
Other scholar (R.L.Sun of Institutes Of Technology Of Tianjin; Y.W.Lei, W.Niu.Laser clad TiCreinforced NiCrBSi composite coatings on Ti-6Al-4V alloy using a CWCO2 laser [J] .Surface & Coatings Technology 203 (2009) 1395-1399) adopt the method for laser melting coating to strengthen compound coating at Ti-6Al-4V surface preparation titanium carbide.Working method is: mix TiC powder and NiCrBSi powder by 1: 3 volume ratio, with organic binder bond mixed powder is preset to matrix surface again, select the laser parameter of an optimization to handle initialization layer then, prepare titanium carbide and strengthen Ni base composite coating.Because the disperse of strengthening phase titanium carbide granule is in strengthening layer, therefore for body material, the hardness and the wear resistance of strengthened coat all improve a lot; Simultaneously because matrix fusing in the lasing process; Titanium carbide granule is in the matrix surface deposition of fusing; Form certain gradient at strengthening layer to matrix; Be equivalent between strengthening layer and matrix, adding one deck transition layer, make to form metallurgical binding between strengthening layer and the matrix that bonding force improves greatly.But the defective of this method is: at first, there are differences between the thermal expansivity between strengthening layer and the matrix, easy of crack influences the bonding force at both interfaces; Secondly, the titanium carbide fusing point is higher, and density is little, and in the preparation coating procedure, the titanium carbide granule of molten state is embedded in coatingsurface easily, makes that the coating roughness of preparation is bigger; At last, titanium carbide granule gathers group easily in cladding process, influence the coating performance homogeneity.
Some scholars (Jongmin Lee of the Pohang University of Korea S; Kwangjun Euh; Jun CheolOh, Sunghak Lee.Microstructure and hardness improvement ofTiC/stainless steel surface composites fabricated by high-energyelectron beam Irradiation [J] .Materials Science and Engineering A323 (2002) 251-259) adopt the mode of high-power electron beam scanning to strengthen compound coating at AISI 304 stainless steel base surface preparation titanium carbides.Working method is: with mol ratio 1: 1 pure titanium valve and carbon black powder are mixed, be preset at stainless steel-based surface then, handle with high-power electron beam and preset the surface, the reaction through titanium and carbon dust forms titanium carbide and prepares titanium carbide reinforcement compound coating.With titanium carbide strengthening layer any surface finish, the flawless of this method preparation, pore-free, and because titanium carbide is reaction in formation, in coating, find to have to gather a phenomenon.But the defective of this method is: at first, pure ti powder price is higher relatively, and oxidation is taking place easily; Secondly, be with the unusual difficulty of these two kinds of powder uniform mixing, the inhomogeneous reaction generation that will influence the strengthening phase titanium carbide of powder, cause simultaneously coating performance at region memory in difference, influence overall performance.
Some scholars (Yang Sen, Zhong Minlin, the Liu Wenjin of Tsing-Hua University.Laser melting coating prepares the Ni/TiC in-situ authigenic and becomes compound coating and tissue thereof to form rule research [J].Use laser, 2002,22 (2): 105～108) mode of employing laser melting coating has obtained the compound coating of reaction in generation TiC on 45 steel surfaces.Working method is to mix Ni60 powder, titanium valve and carbon dust in advance by a certain percentage, is preset in matrix surface with sticker then, obtains strengthening layer through laser treatment again; The strengthening layer macroscopic quality of Experiment Preparation is intact, defectives such as flawless and pore, and reinforcing particle is evenly distributed in coating, and strengthened coat and matrix are metallurgical binding.But; The defective of this method is: at first; Strengthening phase TiC is that element ti and Elements C are passed through the direct bonded of atom; Its general equation formula is: Ti+C → TiC because the structure of the TiC crystalline structure that forms and metal Ti and graphite is all inequality, is not easy abundant reaction so the energy of reaction needed is higher; Secondly, adopt the manual mixed powder of milling, mixed effect is undesirable; Only suitable few experiments can't be applied in industry, and; The reaction that powder is inhomogeneous will to influence the strengthening phase titanium carbide generates, cause simultaneously coating performance at region memory in difference, influence overall performance.
Summary of the invention
In order to solve above-mentioned technical problem; The preparation method who the purpose of this invention is to provide a kind of metal surface laser strengthened coat; Adopt strengthened coat any surface finish, flawless and the pore of this method preparation, and reinforcing particle is evenly distributed in coating, strengthened coat and matrix are metallurgical binding; And adopt wet chemical method to prepare mixed powder and mix, guarantee abundant reaction, be suitable for applying in the industry.
In order to reach above-mentioned purpose, the technical scheme below the present invention has adopted:
A kind of preparation method of metal surface laser strengthened coat comprises the steps:
(1) prepares hydrated titanium dioxide and the mixed uniformly mixed powder of Graphite Powder 99 with wet chemistry method;
(2) above-mentioned mixed powder is preset at matrix surface;
(3) in argon gas atmosphere, form molten bath as thermal source at matrix surface irradiation with laser, the carbon thermal chemical reaction takes place and generates titanium carbide in the mixed powder that presets in the pyritous environment, finally prepare TiC composite coating at matrix surface.
Wet chemistry method; Being the precipitator method, is exactly under solution state, the material of different chemical composition to be mixed, and in mixed solution, adds the throw out that suitable precipitation agent can obtain the homogeneous of various compositions; Again throw out is carried out drying or calcination, thereby make the corresponding powder particle.Adopt the hydrated titanium dioxide and the Graphite Powder 99 mixed powder of wet chemistry method preparation in this programme; Can guarantee two kinds of composition uniform mixing, ratio suitably, combine closely between particle, and this mixed powder is in stable condition is convenient to deposit or mixes with other materials, so not only cost is lower; And do not need under the mechanical ball milling condition, just can two kinds of powders be mixed; Carbothermic reduction reaction generation TiC is faster under lasing, and particle is tiny, is evenly distributed; This programme is through the mode of laser reinforcing preset coating, and reaction in generates titanium carbide, thereby obtains strengthening layer, because TiO in the fore-put powder
22H
2O and C combine closely, and reaction beginning temperature obviously reduces.
In the prior art; Make titanium valve and carbon dust very high through external heat source through the formation temperature that Ti+C → TiC reaction generates TiC; Major cause is following: (the belonging to the solution-type reaction) that the reaction formula of the TiC that reaction generates takes place after the titanium metal particles fuse; And the fusing point of titanium is 1678 ℃, so its temperature of reaction is at least about 1700 ℃.And in this programme process, forming TiC is the result of carbon thermal response, TiO
2Be reduced into the oxide compound of a series of Ti, obtain TiO at last, the C atom realizes that through among the displacement TiO 0 TiC generates then, and therefore in the end in the process, its lattice form does not change from TiO to TiC, and its total reaction equation is: Ti (OH)
4+ 3C → TiC+2H
2O+2CO is because carbon thermal response (TiO
2And solid solid reaction between the C) generates being reflected at 1400 ℃ and just can beginning of TiC; Generate TiC to 1475 ℃ of big quantitative responses of beginning; So with respect to prior art, this programme is lower to the starting temperature of reaction needed, its reaction can also be more prone to and fully carry out; Wherein reason can be thought: because the structure of TiC crystalline structure and metal titanium and graphite is all inequality, so the energy that the building-up reactions of pure element needs is higher; And the carbon thermal response is constant to TiC process crystalline structure from TiO at last, therefore, has reduced the energy requirement of reaction, has reduced the contraction and the cracking that expands and cause of reaction process.
The carbon thermal chemical reaction is carried out in being full of the gas storehouse of argon gas in the above-mentioned steps (3), and argon flow amount is 15～20L/min.
Simultaneously; The method for preparing titanium carbide enhancing compound coating that the present invention adopted is applicable to that also preparation TiN strengthens compound coating, can its hydrous oxide and graphite be mixed with wet chemistry method; Under protective gas atmosphere, select for use laser melting coating to matrix, to prepare then.For example, be used to prepare the complex intensifying layer of TiN strengthening layer or TiN and TiC, specifically comprise the steps:
(1) prepares hydrated titanium dioxide and the mixed uniformly mixed powder of Graphite Powder 99 with wet chemistry method;
(2) above-mentioned mixed powder and urea are mixed with deionized water, and be preset at matrix surface;
(3) in nitrogen atmosphere; Form molten bath as thermal source at matrix surface irradiation with laser; Carbothermal reduction-nitridation reaction takes place and generates titanium nitride in mixed powder that presets and urea in the pyritous environment, the complex intensifying that finally prepares titanium nitride compound coating or titanium nitride and titanium carbide at matrix surface is coating mutually.
Adopt the mixed powder of hydrated titanium dioxide and Graphite Powder 99 to mix the fore-put powder as laser reinforcing with urea in this scheme, the reactional equation of its process is:
4Ti(OH)
4+2CON
2H
4+C→4TiN+3CO
2+12H
2O
Under the general perfect condition, can think through above-mentioned prepared in reaction TiN strengthening layer; But in this prepared in reaction titanium nitride process, because the carbon content of carbothermic reduction reaction process need need be excessive, in this case, excessive carbon will continue to generate TiC with Ti (OH) 4 reactions, and therefore, the strengthening layer of reaction generation is actual to be TiC and TiN composite bed.Above-mentioned reaction process is carried out in nitrogen atmosphere, helps the generation of titanium nitride.The carbon thermal chemical reaction is carried out in being full of the gas storehouse of nitrogen in this scheme step (3), and nitrogen flow is 15～20L/min.
As preferably; Said step (1) in the such scheme comprising: the homodisperse suspension-s of preparation graphite; Again metatitanic acid fourth fat, metatitanic acid isopropyl ester or titanium isopropylate are added dropwise in the graphite suspension; And stir, then with solution filter, dry, obtain hydrated titanium dioxide and the mixed uniformly mixed powder of Graphite Powder 99 after milling.Wherein, metatitanic acid fourth fat, metatitanic acid isopropyl ester or titanium isopropylate can with the water hydrolytic reactions, net reaction is following: M (OR)
n+ nH
2O → M (OH)
n+ nROH, OR wherein are alkoxyl group, in preparation mixed powder process, and M (OR)
nCan be metatitanic acid fourth fat, also can be metatitanic acid isopropyl ester, titanium isopropylate.
Pre-configured graphite aaerosol solution can guarantee that graphite is evenly distributed in the solution, behind dropping metatitanic acid fourth fat, metatitanic acid isopropyl ester or the titanium isopropylate, and the Ti (OH) that they generate through hydrolysis reaction
4The graphite granule that micelle runs in the water just produces adhesion, can accomplish that like this both mixing are more even, combines tightr between particle.
For the carbon thermal response that helps in the subsequent step is abundant, in the mixed powder of above-mentioned steps (1) preparation hydrated titanium dioxide be preferably 1: 5 with the molar weight ratio of Graphite Powder 99～1: 8.Preset coating thickness is 0.1～0.3mm in the said step (2).
As preferably, adopt Pulse Nd in the said step (3): YAG laser carries out intensified process to initialization layer, and electric current is 200～280A, and pulsewidth is 2～4ms, frequency 15～40Hz, and scanning speed is 30～60mm/min.
With respect to prior art, the present invention has following advantage:
1. this law technology is simple, and cost is low, and raw material availability is high, and preparation coating strengthening effect is good, and the strengthening layer microhardness is 850HV in the prior art
0.2, strengthening layer microhardness of the present invention is up to 1150HV
0.2, and strengthening layer any surface finish, flawless and pore, reinforcing particle is evenly distributed in coating, and strengthened coat and matrix are metallurgical binding.
2. this law adopts wet chemistry method mixing titanium oxide and Graphite Powder 99, makes its mixing more even, and is not easy to produce pollution; Their contact area is also very big simultaneously, and this not only can make the carbon thermal response speed up, and has also reduced temperature of reaction, has reduced the chance of reaction product grain growth, and titanium oxide and Graphite Powder 99 are reacted more fully, has improved efficient, has practiced thrift resource.
3. the present invention adopts the method for laser irradiation to prepare the TiC compound coating.Laser can instantaneously provide high-energy, and it is temperature required to reach reaction, makes that the speed of response that forms wild phase is very fast, because the molten bath speed of cooling is fast, makes reaction product crystal grain have little time to grow up simultaneously, and disperse is in strengthening layer.
Description of drawings
Fig. 1 is the process flow sheet of embodiment 1;
Fig. 2 is the experimental installation structural representation of embodiment 1;
Fig. 3 is the XRD analysis figure on the strengthened coat surface of embodiment 1.
Embodiment
Do a detailed explanation below in conjunction with the accompanying drawing specific embodiments of the invention.
Embodiment 1:
The preparation method of a kind of metal surface laser strengthened coat as shown in Figure 1 comprises the steps:
(1) prepares hydrated titanium dioxide and the mixed uniformly mixed powder of Graphite Powder 99 with wet chemistry method;
(2) above-mentioned mixed powder is preset at matrix surface;
(3) in argon gas atmosphere; Form molten bath as thermal source at matrix surface irradiation with laser; The carbon thermal chemical reaction takes place and generates titanium carbide in the mixed powder that presets in the pyritous environment, finally prepare densification, even, flawless TiC composite coating at matrix surface.
Step (1): uniform mixing hydrated titanium dioxide and Graphite Powder 99;
Through the butyl(tetra)titanate hydrolysis, can obtain the hydrated titanium dioxide deposition.The liposoluble of metatitanic acid fourth is made into the solution of proper concn in absolute ethyl alcohol, under normal temperature, normal pressure, magnetic agitation condition, is added dropwise in the homodisperse capable ink powder aaerosol solution, make the thorough hydrolysis of metatitanic acid fourth fat, its hydrolysis general equation is following:
Ti(OC
4H
9)
4+4H
2O→Ti(OH)
4+4C
4H
9OH；
After continuing to stir, fully stir after-filtration, remove impurity and moisture, avoid the generation of hard aggregation, the hydrated titanium dioxide (Ti (OH) that is uniformly mixed after oven dry is milled then
4) and the graphite powder.The mol ratio of hydrated titanium dioxide and graphite is 1 in the filtrate: (5～8) (present embodiment is 1: 8).Prepare in the process of composite granule Ti (OH) in the above
4Micelle generates in hydrolysis reaction, runs into above graphite granule in the water just adheres to, and simultaneously because even magnetic agitation, makes the Ti (OH) of generation
4The probability that micelle runs into graphite granule is tending towards equal, therefore, can think that both are uniform mixing.
Step (2): above-mentioned mixed powder is preset at matrix surface;
Preset coating thickness is 0.1～0.3mm (present embodiment is 0.3mm).
Step (3): strengthen the preparation of compound coating;
Laser irradiation process experiment structure drawing of device is as shown in Figure 2; Mainly be made up of laser apparatus 1 and gas storehouse 2, wherein three-way interface 3 places are an inlet, two outlets; Inlet 5 links to each other with the argon bottle reducing valve; An outlet connects argon shield case (gas storehouse 2), and protection sample 4 is not oxidized in the laser reinforcing process, and can be through regulating atmosphere in the air pressure size control guard box; Another outlet connects laser apparatus 1 with the protection eyeglass, keeps laser apparatus inside and guard box internal pressure in a basic balance.
Body material is polished; Put into reaction warehouse after the oil removal treatment, in reaction warehouse, feed argon gas and discharge the air in the reaction warehouse, argon flow amount be the 15-20 liter/minute; Select for use then mixed powder that laser will go up a step preparation through the mode cladding of presetting to matrix; Under the argon gas that flows, naturally cool to room temperature then, obtain titanium carbide and strengthen compound coating.Can be through strengthening phase particulate size and reaction efficiency in the laser technical parameters control strengthening layer.So these parameters of choice all have fundamental influence to particle diameter, the output of reacting strengthening phase in the strengthening layer of back, select reasonable parameter extremely important.
The reaction equation that the present invention forms titanium carbide is:
Because it is to produce CO that the carbon thermal response generates the process of titanium carbide, therefore, according to the chemical reaction equilibrium condition, suitably improves nitrogen partial pressure, reduces the CO dividing potential drop, helps reaction and develop to producing the titanium carbide direction.
Obtain compact structure, excellent property, become the titanium carbide of metallurgical binding to strengthen compound coating with matrix through above-mentioned steps, the strengthening layer degree of depth is 250 μ m, and surface hardness reaches 1150HV
0.2, Fig. 3 is the XRD analysis on strengthening layer surface, can be known that by map analysis strengthening layer is mainly by Fe, TiC, FeTiO
3Form.
Embodiment 2:
A kind of preparation method of metal surface laser strengthened coat comprises the steps:
1. get 2g graphite with absolute ethyl alcohol wetting after, join in the 400ml deionized water, and handle certain hour with ultrasonic dispersing, prevent to reunite between the graphite granule, thereby obtain homodisperse graphite granule suspension-s.
2. get the 10ml titanium isopropylate and join in the 100ml absolute ethyl alcohol, stir after 15 minutes, be added drop-wise in the homodisperse graphite suspension, make the thorough hydrolysis of titanium isopropylate, and evenly be attached on the dispersive graphite granule.((mol ratio of titanium oxide and graphite is 1: 5) continued the powerful after-filtration that stirs, and uses earlier the deionized water wash filtrate, removes impurity, uses absolute ethanol washing twice again, then filtrate dried by the fire 8 hours under 70 ℃ of conditions, mills, sieves.
3. to 45 steel matrix oil removings, rust cleaning, hydrated titanium dioxide that makes and the mixed uniformly powder of Graphite Powder 99 are preset at matrix surface, put into reaction warehouse then; The logical argon gas exhausted air of going up, argon flow amount is 15L/min, selects Pulse Nd at last for use: YAG laser carries out irradiation to coating; Parameter is electric current 250A; Pulsewidth 2.5ms, frequency 18Hz, scanning speed 50mm/min.
Obtain compact structure, excellent property, become the titanium carbide of metallurgical binding to strengthen compound coating with matrix through above-mentioned steps, the strengthening layer degree of depth is 200 μ m, and surface hardness reaches 1100HV
0.2
Embodiment 3:
A kind of preparation method of metal surface laser strengthened coat comprises the steps:
(1) prepares hydrated titanium dioxide and the mixed uniformly mixed powder of Graphite Powder 99 with wet chemistry method;
(2) above-mentioned mixed powder and urea are mixed with deionized water, and be preset at matrix surface;
(3) in nitrogen atmosphere; Form molten bath as thermal source at matrix surface irradiation with laser; Carbothermal reduction-nitridation reaction takes place and generates titanium nitride in mixed powder that presets and urea in the pyritous environment, the complex intensifying that finally prepares titanium nitride and titanium carbide at matrix surface is coating mutually.
Concrete preparation process is following:
1. get 2g graphite with absolute ethyl alcohol wetting after, join in the 400ml deionized water, and handle certain hour with ultrasonic dispersing, prevent to reunite between the graphite granule, thereby obtain homodisperse graphite granule suspension-s.
2. get the 10ml titanium isopropylate and join in the 100ml absolute ethyl alcohol, stir after 15 minutes, be added drop-wise in the homodisperse graphite suspension, make the thorough hydrolysis of titanium isopropylate, and evenly be attached on the dispersive graphite granule.(it is excessive that this experiment carbon content needs, and the mol ratio of therefore getting titanium oxide and graphite is 1: 5) continues the powerful after-filtration that stirs; Use earlier the deionized water wash filtrate, remove impurity, use twice of absolute ethanol washing again; Then filtrate was dried by the fire 8 hours under 70 ℃ of conditions, mill, sieve.
3. to 45 steel matrix oil removings, rust cleaning, with the hydrated titanium dioxide that makes (Ti (OH)
4), Graphite Powder 99 and urea mixes with deionized water, and is preset at matrix surface, puts into reaction warehouse then; The logical nitrogen exhausted air of going up, the stream of nitrogen gas amount is 20L/min, selects Pulse Nd at last for use: YAG laser carries out irradiation to coating; Parameter is electric current 230A; Pulsewidth 2.5ms, frequency 18Hz, scanning speed 60mm/min.
Obtain compact structure, excellent property, become the titanium nitride of metallurgical binding to strengthen compound coating with matrix through above-mentioned steps, the strengthening layer degree of depth is 200 μ m, and surface hardness reaches 1060HV
0.2.
Claims (6)
1. the preparation method of a metal surface laser strengthened coat is characterized in that, comprises the steps:
(1) prepares hydrated titanium dioxide and the mixed uniformly mixed powder of Graphite Powder 99 with wet chemistry method;
(2) above-mentioned mixed powder is preset at matrix surface;
(3) in argon gas atmosphere, form molten bath as thermal source at matrix surface irradiation with laser, the carbon thermal chemical reaction takes place and generates titanium carbide in the mixed powder that presets in the pyritous environment, finally prepare TiC composite coating at matrix surface;
Wherein, Said step (1) comprising: the homodisperse suspension-s of preparation graphite; Again butyl(tetra)titanate, isopropyl titanate or titanium isopropylate are added dropwise in the graphite suspension; And stir, then with solution filter, dry, obtain hydrated titanium dioxide and the mixed uniformly mixed powder of Graphite Powder 99 after milling; Adopt Pulse Nd in the said step (3): YAG laser carries out intensified process to initialization layer, and electric current is 200～280A, and pulsewidth is 2～4ms, frequency 15～40Hz, and scanning speed is 30～60mm/min.
2. the preparation method of a metal surface laser strengthened coat is characterized in that, comprises the steps:
(1) prepares hydrated titanium dioxide and the mixed uniformly mixed powder of Graphite Powder 99 with wet chemistry method;
(2) above-mentioned mixed powder and urea are mixed with deionized water, and be preset at matrix surface;
(3) in nitrogen atmosphere; Form molten bath as thermal source at matrix surface irradiation with laser; Carbothermal reduction-nitridation reaction takes place and generates titanium nitride in mixed powder that presets and urea in the pyritous environment, the complex intensifying that finally prepares titanium nitride compound coating or titanium nitride and titanium carbide at matrix surface is coating mutually;
Wherein, Said step (1) comprising: the homodisperse suspension-s of preparation graphite; Again butyl(tetra)titanate, isopropyl titanate or titanium isopropylate are added dropwise in the graphite suspension; And stir, then with solution filter, dry, obtain hydrated titanium dioxide and the mixed uniformly mixed powder of Graphite Powder 99 after milling; Adopt Pulse Nd in the said step (3): YAG laser carries out intensified process to initialization layer, and electric current is 200～280A, and pulsewidth is 2～4ms, frequency 15～40Hz, and scanning speed is 30～60mm/min.
3. the preparation method of a kind of metal surface laser strengthened coat according to claim 1 and 2 is characterized in that, hydrated titanium dioxide is 1: 5～8 with the molar weight ratio of Graphite Powder 99 in the mixed powder of said step (1) preparation.
4. the preparation method of a kind of metal surface laser strengthened coat according to claim 1 and 2 is characterized in that, preset coating thickness is 0.1～0.3mm in the said step (2).
5. the preparation method of a kind of metal surface laser strengthened coat according to claim 1 is characterized in that, the carbon thermal chemical reaction is carried out in being full of the gas storehouse of argon gas in the said step (3), and argon flow amount is 15～20L/min.
6. the preparation method of a kind of metal surface laser strengthened coat according to claim 2 is characterized in that, the carbon thermal chemical reaction is carried out in being full of the gas storehouse of nitrogen in the said step (3), and nitrogen flow is 15～20L/min.
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