CN108411298B - A kind of method of laser melting coating nano metal composite coating - Google Patents
A kind of method of laser melting coating nano metal composite coating Download PDFInfo
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- CN108411298B CN108411298B CN201810286496.1A CN201810286496A CN108411298B CN 108411298 B CN108411298 B CN 108411298B CN 201810286496 A CN201810286496 A CN 201810286496A CN 108411298 B CN108411298 B CN 108411298B
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- metal composite
- cladding layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C24/00—Coating starting from inorganic powder
- C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
- C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
Abstract
The invention discloses a kind of methods of laser melting coating nano metal composite coating, it is that paste titanium hydroxide nano material is prepared with sol-gel method, it is formed coated in substrate material surface to be processed to cladding layer after being mixed with urea and graphite, laser irradiation scanning is to cladding layer to form titanium nitride nano metal composite coating cladding in substrate material surface.The present invention generates hard nitride coatings with laser irradiation on the basis of reacting in situ, realizes the high strength bond between cladding layer and basis material, obtains the cladding layer of no chemical residues, flawless, pore-free and satisfactory mechanical property.
Description
Technical field
The invention belongs to technical field of metal material surface treatment, are related to a kind of in metal material surface coating Metal Substrate pottery
The method of porcelain coating, especially a kind of coating method of coating based on laser melting and coating technique.
Background technique
Laser melting and coating technique, which refers to, places the coating material of selection, warp in coated matrix surface in a manner of different fillers
Laser irradiation is allowed to melt simultaneously with matrix surface a thin layer, and form that dilution is extremely low after quickly solidifying and basis material at
The surface covering of metallurgical bonding, the work of wear-resisting so as to improve substrate material surface, anti-corrosion, heat-resisting, anti-oxidant and electrical characteristic etc.
Process.
Currently, according to the addition manner of coating material, by laser melting and coating process method be divided into fore-put powder method with synchronize give
Two kinds of powder method.Fore-put powder method is that the material to be coated passes through the methods of plating, chemical plating, plasma spraying and manual adhesive
It is preset in metal surface, then through laser irradiation cladding;Synchronous powder feeding system method is directly by metal powder painting in laser emission institute
On the mobile molten bath formed, coating is disposably formed.
Laser melting and coating technique is mainly used in: 1, surface carried out to material and is modified, such as gas turbine blade, and roll, gear
Deng;2, product surface is repaired, such as rotor, mold etc..Relevant information shows that repairing back part intensity can achieve original by force
90% or more of degree, and 1/5 of expense less than resetting, and shorten maintenance time.
Report in document about laser melting and coating process method emerges one after another.But up to the present, laser cladding layer is special
It is not that laser melting coating ceramic on metal layer still remains crackle and stomata problem in some problems, especially cladding layer.
Laser cladding process is the process of a dynamic fusing, small-sized due to molten bath, not there is only phenomenon of Heat,
Also convection current, mass transfer etc. are existed simultaneously, they are uniform by macro morphology, segregation, tissue and the ingredient for directly affecting molten bath
Property and other Physical Metallurgy performances.Therefore, in the various traditional oxide ceramic powders of cladding, carbide composite powder, metal-
The element density of each component is inconsistent during ceramic powders, in molten bath and other physical property difference, will lead to cladding layer and goes out
It is now unevenly distributed as hard and re-melt deposit welding and gas hole defect caused by dendrite is coarse.
Since the eighties in last century, the crackle and gas hole defect problem of laser melting coating metal matrix ceramic composite coating are always section
The personnel of grinding endeavour the technical issues of solving the problem of and are most difficult to overcome.Although having obtained to varying degrees centainly
Improve, but do not obtain effective solution scheme still, crackle and stomata problem become limitation laser melting coating cermet and apply
Layer moves towards practical biggest obstacle.
Summary of the invention
The object of the present invention is to provide a kind of methods of laser melting coating nano metal composite coating, to be existed using this method
Metal base surface obtains flawless, pore-free, the high surfaces intensity of free from admixture and the cladding coating of hardness.
The method of laser melting coating nano metal composite coating provided by the present invention is:
In alcohol solvent system, using acetic acid as catalyst, it is catalyzed isopropyl titanate and ethanol synthesis, it is solidifying by colloidal sol-
Titanium hydroxide nano material paste is prepared in glue method;
According to titanium hydroxide nano material 60~88%, urea 10~33%, graphite 2~7% mass ratio, by the paste
Titanium hydroxide nano material be uniformly mixed with urea and graphite, the surface coated in basis material to be processed, formed to cladding
Layer;
Under inert environments, is scanned with laser irradiation to cladding layer, the titanium hydroxide of non-crystalline is made to nitrogenize to form titanium nitride
Nano metal composite coating, cladding is in substrate material surface.
The above method of the present invention can be such that the titanium hydroxide of non-crystalline nitrogenizes in substrate material surface, form hardness and be up to
The titanium nitride nano metal composite coating of 27GPa.
In above-mentioned reaction process, oxidation of coal is+4 as oxidant by urea and amorphous titanium hydroxide nano material
The titanium hydroxide of+4 valences and is reduced to the+titanium nitride of trivalent, high-rate laser Shu Ze by the carbon dioxide of valence, and carbon is as reducing agent
Provide energy required for above-mentioned reaction.Wherein, urea is the source of nitrogen, and carbon is then that control degree of oxidation and laser are inhaled
The key component of yield.
In reaction process, the titanium dioxide first synthesized can refine the titanium nitride particles finally generated as precursor, thus
Improve the intensity of coating.In turn, the heat that above-mentioned reaction process generates causes micro- thawing of matrix skin, finally coating with
One layer of new intermediate layer is formed between matrix, becomes mark of the matrix in conjunction with coating high strength.
In above-mentioned reaction process, cladding layer temperature of control laser irradiation scanning when cladding layer is 1400~1700 DEG C.
The change of cladding layer temperature, influences whether the output power of laser, so that the cladding effect of cladding layer is influenced, so that cracking
And hole defect.
In the above method of the present invention, the applied thickness to cladding layer should be controlled within the scope of 2~5mm.
Further, the above-mentioned reaction of the present invention preferably carries out under the inert environments built with argon gas.
In the method for the invention, scan velocity V=5~8mm/s of the preferably described laser irradiation.
In the above method of the present invention, it is also necessary to first be pre-processed to the basis material to be processed, including to be processed
Substrate material surface is polished to remove material surface oxide, and uses acetone cleaning oil removing and drying.
Basis material to be processed of the present invention includes titanium alloy, aluminium alloy or carbon steel.
The above method of the present invention is suitable for compound in the substrate material surface laser melting coating nano metal of 10~20mm of thickness
Object coating.
The present invention is combined using sol-gel technique with temperature control laser processing technology, on the basis of reacting in situ, fortune
Hard nitride coatings are generated with laser irradiation paste nanostructured composites, are realized between cladding layer and basis material
High strength bond obtains the cladding layer of no chemical residues, flawless, pore-free and satisfactory mechanical property.
Detailed description of the invention
Fig. 1 is the section micro-structure diagram of cladding layer obtained by embodiment 1 (A) and comparative example 1 (B).
Fig. 2 is that cladding layer temperature is respectively cladding layer cross section micro-structure diagram under 1300 DEG C (A) and 1700 DEG C (B).
Specific embodiment
Following embodiments are only the preferred technical solution of the present invention, are not used to carry out any restrictions to the present invention.For
For those skilled in the art, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made
Any modification, equivalent substitution, improvement and etc., should all be included in the protection scope of the present invention.
Embodiment 1.
The TC4 sample of 20 × 20 × 20mm of specification is taken, after carrying out coarse grinding treatment to its surface with 100 mesh abrasive paper for metallograph, is used
Acetone cleaning to remove degreasing, wipe it is net, then with alcohol wipe, dry up, obtain pretreated TC4 basis material.
Isopropyl titanate 20g, dehydrated alcohol 25mL, water 4mL, 10% acetic acid solution 3mL are added in beaker, at room temperature strongly
Stirring makes Titanium alkoxides hydrolysis, polycondensation form titanium hydroxide colloidal sol, heats to form titanium hydroxide nanogel paste.
10g paste titanium hydroxide nanogel is weighed, 1.14g urea is added and 0.2g graphite is uniformly mixed, even application
In above-mentioned pretreated TC4 substrate material surface, formed with a thickness of 5mm to cladding layer.
It is coated with integrally being put into the protective device filled with Ar gas to the TC4 basis material of cladding layer, setting swashs
The laser power that light irradiates scanning means is 2000W, spot diameter 1.5mm, scanning speed 8mm/s, with 50% scanning overlapping rate
Laser irradiation is scanned to cladding layer, and uses temperature control system of semiconductor laser thermostatic control cladding layer during the scanning process
Temperature is 1700 DEG C.Under the high laser energy, by reacting with urea, graphite, the titanium hydroxide of non-crystalline is nitrogenized into shape
At titanium nitride nano metal composite coating, cladding is in TC4 substrate material surface.
Bond strength is to measure the important indicator of cladding coating quality.The present embodiment is referring to " laser melting coating ceramic layer combines
Ionization meter and flaw shape are at analysis " cladding in (Ma Xianyao etc., Chinese laser, 1993, Vol.20, No.1,73-77)
Layer bond strength measuring method, using four-point bending method, by sample load on WJ-10 type universal testing machine, measurement is molten
The bond strength of coating and basis material.Acoustic emission signal is measured using 4610SA type single channel instrument, to there is first burst
Basis of the property count of acoustic emission event as cladding layer material damage, records corresponding loadP max , can be calculated according to formula
The bond strength of the present embodiment basis material and cladding layer is 265.31MPa.
Cladding layer hardness is to measure the main indicator of material comprehensive performance.The present embodiment uses HVS-1000 digital display sclerometer
The hardness of TC4 sample cross is detected, Adjustment Tests power is 1.98N, bearer duration 20s, transversal along cladding layer
It is from outward appearance to inner essence got ready in face.Vertical direction makes a call to a point every 0.3mm, and horizontal direction makes a call to three points, is averaged, melted
The firmness change trend curve of coating from outward appearance to inner essence.According to hardness curve it can be concluded that the hardness of the present embodiment cladding coating compared with
Height is located at 2312.34~2758.33HV0.2Between.
Comparative example 1.
The pretreatment TC4 basis material of Example 1 swashs in the preset titanium nitride nano powder in its surface according to embodiment 1
Light cladding parameter and atmospheric condition carry out laser melting coating.
According to 1 test method of embodiment, bond strength and cladding layer hardness between basis material and cladding layer are detected.Inspection
It surveys the results show that the bond strength of this comparative example basis material and cladding layer is 200.34MPa, the cladding layer that the surface TC4 is formed
Hardness is located at 1806.21~1994.02HV0.2Between.According to detection data as can be seen that 1 cladding layer hardness of embodiment and and base
The bond strength of body material is obviously higher than comparative example 1.
The cladding layer cross-sectional metallographic organization chart of embodiment 1 and comparative example 1 is set forth in Fig. 1.As seen from the figure, implement
The dense structure of laser cladding coating, flawless and gas hole defect under example 1 (A) reaction in-situ.And comparative example 1 (B) conventional laser
Occur a large amount of hole defects in the tissue of cladding coating.
Comparative example 2.
The laser power that laser irradiation scanning means is arranged is 1500W, and thermostatic control cladding layer temperature is 1300 DEG C,
His technical process and technological parameter are with embodiment 1, in TC4 substrate material surface reaction in-situ laser melting coating titanium nitride nano metal
Composite coating.
It can be seen that cladding layer temperature of the embodiment 1 (B) at 1700 DEG C from the cladding layer cross-sectional metallographic organization chart of Fig. 2
When lower progress reaction in-situ, obtained laser cladding coating dense structure's property is higher, not cracked and gas hole defect, and compares
After being reduced to 1300 DEG C compared with example 2 (A) cladding layer temperature, the cladding effect of cladding layer is affected, so that producing crackle and hole
Defect.
Embodiment 2.
The TC4 sample of 20 × 20 × 15mm of specification is taken, after carrying out coarse grinding treatment to its surface with 100 mesh abrasive paper for metallograph, is used
Acetone cleaning to remove degreasing, wipe it is net, then with alcohol wipe, dry up, obtain pretreated TC4 basis material.
Isopropyl titanate 15g, dehydrated alcohol 19mL, water 3mL, 10% acetic acid solution 2mL are added in beaker, at room temperature strongly
Stirring makes Titanium alkoxides hydrolysis, polycondensation form titanium hydroxide colloidal sol, heats to form titanium hydroxide nanogel paste.
8g paste titanium hydroxide nanogel is weighed, 1.07g urea is added and 0.5g graphite is uniformly mixed, even application exists
Above-mentioned pretreated TC4 substrate material surface is formed with a thickness of 3mm to cladding layer.
It is coated with integrally being put into the protective device filled with Ar gas to the TC4 basis material of cladding layer, setting swashs
The laser power that light irradiates scanning means is 1800W, spot diameter 1.5mm, scanning speed 6mm/s, with 30% scanning overlapping rate
Laser irradiation is scanned to cladding layer, and uses temperature control system of semiconductor laser thermostatic control cladding layer during the scanning process
Temperature is 1500 DEG C.Under the high laser energy, by reacting with urea, graphite, the titanium hydroxide of non-crystalline is nitrogenized into shape
At titanium nitride nano metal composite coating, cladding is in TC4 substrate material surface.
Through detecting, the bond strength of the present embodiment basis material and cladding layer is 253.42MPa, and cladding coating hardness is located at
2245.16~2554.40HV0.2Between.
Under the conditions of identical laser melting coating, laser melting coating directly is carried out using titanium nitride nano powder, detection cladding applies
Layer hardness is located at 1548.22~1774.34HV0.2Between, the bond strength of basis material and cladding layer is 160.14MPa.
Embodiment 3.
The TC4 sample of 20 × 20 × 10mm of specification is taken, after carrying out coarse grinding treatment to its surface with 100 mesh abrasive paper for metallograph, is used
Acetone cleaning to remove degreasing, wipe it is net, then with alcohol wipe, dry up, obtain pretreated TC4 basis material.
Isopropyl titanate 10g, dehydrated alcohol 13mL, water 1.56mL, 10% acetic acid solution 1mL are added in beaker, at room temperature by force
Strong stirring, makes Titanium alkoxides hydrolysis, polycondensation form titanium hydroxide colloidal sol, and heat treatment is solidifying to form titanium hydroxide nanometer paste
Glue.
5g paste titanium hydroxide nanogel is weighed, 2.75g urea is added and 0.6g graphite is uniformly mixed, even application exists
Above-mentioned pretreated TC4 substrate material surface is formed with a thickness of 2mm to cladding layer.
It is coated with integrally being put into the protective device filled with Ar gas to the TC4 basis material of cladding layer, setting swashs
The laser power that light irradiates scanning means is 1600W, spot diameter 1.5mm, scanning speed 5mm/s, with 20% scanning overlapping rate
Laser irradiation is scanned to cladding layer, and uses temperature control system of semiconductor laser thermostatic control cladding layer during the scanning process
Temperature is 1400 DEG C.Under the high laser energy, by reacting with urea, graphite, the titanium hydroxide of non-crystalline is nitrogenized into shape
At titanium nitride nano metal composite coating, cladding is in TC4 substrate material surface.
Through detecting, the bond strength of the present embodiment basis material and cladding layer is 224.81MPa, and cladding coating hardness is located at
2064.32~2350.45HV0.2Between.
Under the conditions of identical laser melting coating, laser melting coating directly is carried out using titanium nitride nano powder, detection cladding applies
Layer hardness is located at 1201.76~1346.56HV0.2Between, the bond strength of basis material and cladding layer is 120.12MPa.
Claims (6)
1. a kind of method of laser melting coating nano metal composite coating, which comprises
In alcohol solvent system, using acetic acid as catalyst, it is catalyzed isopropyl titanate and ethanol synthesis, passes through sol-gel method
Titanium hydroxide nano material paste is prepared;
According to titanium hydroxide nano material 60~88%, urea 10~33%, graphite 2~7% mass ratio, by the hydrogen paste
Titanium dioxide nano material is uniformly mixed with urea and graphite, the surface coated in basis material to be processed, is formed to cladding layer;
It under inert environments, is scanned with laser irradiation to cladding layer, and controlling coat temperature fusion is 1400~1700 DEG C, makes non-knot
The titanium hydroxide of crystalline state nitrogenizes to form titanium nitride nano metal composite coating, and cladding is in substrate material surface.
2. the method for laser melting coating nano metal composite coating according to claim 1, it is characterized in that described to cladding
The applied thickness of layer is 2~5mm.
3. the method for laser melting coating nano metal composite coating according to claim 1, it is characterized in that the method is also
Including pre-processing to the basis material to be processed, the pretreatment includes polishing substrate material surface to be processed
And cleaning oil removing, drying.
4. the method for laser melting coating nano metal composite coating according to claim 1, it is characterized in that described wait locate
Reason basis material is titanium alloy, aluminium alloy or carbon steel.
5. the method for laser melting coating nano metal composite coating according to claim 1, it is characterized in that described matrix material
Material with a thickness of 10~20mm.
6. the method for laser melting coating nano metal composite coating according to claim 1, it is characterized in that the inertia ring
Border is argon atmosphere.
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CN101812684A (en) * | 2010-04-19 | 2010-08-25 | 姚建华 | Method for preparing metal surface laser strengthened coat |
CN105562932A (en) * | 2016-03-07 | 2016-05-11 | 福建工程学院 | Method for carrying out lap-jointing on laser cladding composite coating by adopting friction-stir welding technology |
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CN101812684A (en) * | 2010-04-19 | 2010-08-25 | 姚建华 | Method for preparing metal surface laser strengthened coat |
CN105562932A (en) * | 2016-03-07 | 2016-05-11 | 福建工程学院 | Method for carrying out lap-jointing on laser cladding composite coating by adopting friction-stir welding technology |
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