CN110255968A - For the nano composite dope and preparation method thereof in laser surface modification technique - Google Patents
For the nano composite dope and preparation method thereof in laser surface modification technique Download PDFInfo
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- CN110255968A CN110255968A CN201910697058.9A CN201910697058A CN110255968A CN 110255968 A CN110255968 A CN 110255968A CN 201910697058 A CN201910697058 A CN 201910697058A CN 110255968 A CN110255968 A CN 110255968A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
- C04B26/02—Macromolecular compounds
- C04B26/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00482—Coating or impregnation materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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Abstract
The embodiment of the invention discloses a kind of nano composite dope in laser surface modification technique, the nano composite dope includes aggregate and auxiliary material, wherein the aggregate includes nano-titanium oxide, oxide nano rare earth and/or Nanoalloy powder.The embodiment of the present invention uses oxide nano rare earth (CeO2) there is special role of the stable composite oxides coating to infrared laser high-absorbility；Nano-meter SiO_22Surfacing is kept after in laser melting coating and alloying process melted surface can solidify；The reunion of nanometer oxide material is substantially reduced matrix to the absorptivity and cracking resistance crack arrest effect of infrared laser, and preset coating material is made to lose indehiscent effect in expected increase light absorption and cladding process.Dispersing agent and cladding agent are added in above-mentioned nano composite dope, then can be reunited using the wet grinding of high-speed circulating big flow ultrafine nanometer to avoid the material of nano-oxide.
Description
Technical field
The present embodiments relate to engineering material process for modifying surface fields, and in particular to one kind is used for laser surface modification
Nano composite dope in technique and preparation method thereof.
Background technique
Laser Surface Treatment mainly utilizes physical effect caused by radiation of the laser of high-energy-density to metal surface,
It is brought rapidly up metal surface, generation phase transformation (LTH) even melts (LC, LA), gasifies (LSH), while certainly by metallic matrix
The heat transfer of body and be quickly cooled down even quickly solidification, or the high-strength plasma attack that by gasifying when generates reaches change metal
Surface texture, structure even ingredient, for example, addition alloying component, to obtain the light processing technology of excellent military service performance.Due to
Laser Surface Treatment process controllability is good, and heating region is small, small to matrix heat affecting, and workpiece deformation is small, can be laggard in finishing
Row, is especially suitable for the surface modification treatments such as complex-shaped part, hole, slot inner wall.
Wherein, it by the process of the luminous energy development of evil in febrile disease of laser, can be described with the classical model of free electron.Accordingly, laser removes
Except the reflective portion of metal surface, mainly by the Electron absorption in surface layer.The laser penetration depth of common metal is less than
0.1um.Energy increases after the energy of superficial layer Electron absorption laser photon, and in very short time (10-11~10-10S pass through in)
With lattice collisions, it is converted into the vibrational energy of lattice, causes the raising of material temperature, then according to the mechanism of heat transfer, thermal energy
It is propagated to material internal, heats material surface quickly, then itself is quickly cooled down, to change the tissue and property of material surface
Energy.Different materials have very big difference for the absorption and reflection of the photon of different wave length.Most metals are for 10.6 mum wavelengths
CO2The absorptivity of laser is all very low, and reflectivity is up to 70%-90%.The wavelength of semiconductor and optical-fiber laser ratio CO2Laser is short,
But metal is still lower to the absorptivity of this laser.
From the above mentioned, not pretreated metal surface not only causes most of preciousness to the strong reflection of laser beam
The loss of laser energy, and seriously threaten the health of operator.Therefore, when carrying out Laser Surface Treatment,
Surface must be pre-processed, to improve material to laser absorption rate.But the phosphatization and coating carbon black generallyd use for many years
Or there are a series of problems for the melanism method of graphite, and if absorptivity is lower, thermal stability is poor, absorptivity decline is increased with temperature,
Difficulty is removed, there is pollution.
Therefore, traditional Laser Surface Treatment absorbing coating is in LTH, LC, and in LA and LSH treatment process, extinction efficiency is still
Undesirable and laser cladding layer cracking sensitivity is larger, so as to cause being easy to crack in coating or the defects of gap.
Summary of the invention
For this purpose, the embodiment of the present invention provides a kind of nano composite dope in laser surface modification technique and its preparation
Method, to solve, Laser Surface Treatment absorbing coating absorptivity is low in the prior art, stability is poor and cracking resistance effect is poor is asked
Topic.
To achieve the goals above, the embodiment of the present invention provides the following technical solutions:
A kind of nano composite dope in laser surface modification technique, the nano composite dope include aggregate and auxiliary
Material, wherein the aggregate includes nano-titanium oxide, oxide nano rare earth and/or Nanoalloy powder.
Preferably, the aggregate further includes one of nano zine oxide, nano silicon oxide and nano chromium oxide or several
Kind.
Preferably, the oxide nano rare earth is nano-cerium oxide.
Preferably, the Nanoalloy powder includes nanometer WC/Co.
Preferably, the auxiliary material includes covering, dispersing agent, emulsifier, antirust agent, binder and solvent.
Preferably, the covering is polyethylene glycol；The antirust agent is sodium nitrite；The binder is PVA；It is described
Solvent is deionized water.
The embodiment of the present invention is also provided described in a kind of prepare for the nano composite dope in laser surface modification technique
Method, it is characterised in that including the auxiliary material is first mixed to form mixture with sand mill, the aggregate is then passed through into height
Speed circulation big flow nanometer wet grinding mill is fully dispersed, clads, obtains the nano composite dope after emulsification treatment, wherein institute
Stating aggregate includes nano-titanium oxide, oxide nano rare earth and/or Nanoalloy powder, wherein the Nanoalloy powder includes nanometer
WC/Co。
Preferably, the aggregate further includes one of nano zine oxide, nano silicon oxide and nano chromium oxide or several
Kind.
Preferably, the oxide nano rare earth is nano-cerium oxide.
In the embodiment of the present invention, it is tungsten carbide table using reunion sintering process that WC-Co, which is the cobalt-based coated composite powder of high rigidity,
Bread covers one layer of layer of metal cobalt as protection and bonding, the ability with fabulous anti-abrasive wear and resistance to high temperature oxidation.
It is also applied for plasma spraying or supersonic spray coating technique.
In the embodiment of the present invention, aggregate is most important component part in coating system, to for Laser Surface Treatment
It absorbs laser and crack resisting coating is especially most important.According to nano-metal-oxide to CO2Laser, optical fiber and semiconductor laser are inhaled
The characteristics of yield is higher and nano metal carbide proposes high-intensity anti-cracking crack arrest in LC and LA modified layer, further according to nanometer material
Quantum size effect, small-size effect, skin effect, the sink effect etc. given by the partial size of superfine are expected, with nano oxygen
The aggregate that nano-carbide is absorption and crack resisting coating is properly added based on compound, it decides that absorption and crack resisting coating can be high
Effect ground absorbs laser and effectively cracking resistance, under high power laser light irradiation, has thermal stability good, thermal conductivity is good, high temperature resistant, not instead
The features such as spray, selects a variety of nano-oxides and nano-carbide to carry out screening test, according to composite coating nano-dispersion,
The performance synthesis such as high absorptivity and crack resistance, storage stability relatively and optimize.
In the embodiment of the present invention, when composite coating is water paint, flash rusting can be generated by being applied to metal surface, thus compound
Anti- flash rusting agent is selected to be addressed in coating preparation.
In the embodiment of the present invention, nano-particles size is small, and the specific surface area of nanoscale super fine is quite big, surface
Free energy is high, thus nanoparticle is easily in soft-agglomerated state.This characteristic of nanoparticle determines that nano paint can not
As common pigments and fillers are just getable by simple mixture with base-material.In the dispersion process of nano paint preparation, nanoparticle
Sub- phase is dispersed with three processes to interrelate: 1, wetting and dispersing, i.e., with wetting agent, dispersing agent displacement originally in nanoparticle
The air etc. on surface, and get ready for dispersion and stabilization process；2, dispersion grinding, i.e., by high speed dispersion milling apparatus to receiving
Rice corpuscles apply high speed shearing force, make in soft-agglomerated state nanoparticle open become primary particle, while with dispersing agent,
Covering is adsorbed and is coated on around primary particle surface；3, stably dispersing, i.e. dispersing agent, covering, which are adsorbed and be coated on, to be received
Around rice corpuscles surface, with the shielding action of the repulsion and space steric effect of electric layer around nanometer primary particle surface, it will receive
Rice corpuscles stably dispersing.
In the embodiment of the present invention, in order to disperse nano material well, suitable dispersing agent is selected, selection
Dispersing agent P is a kind of anionic high molecular surfactant, is added in aqueous phase system.In continuous phase water, aqueous solution
It infiltrates scattered adsorption and spread can suitably reduce the surface energy of nanoparticle in nanoparticle surface completely, and make nanoparticle
Surrounding electric layer is negatively charged, makes so mutually exclusive between nanoparticle, and nanoparticle is prevented further to reunite.Simultaneously using cladding
Agent carries out the processing of surface cladding to nanoparticle, and the covering E of selection is a kind of non-ionic (polymeric surfactant),
It " can be permeated " to around nanoparticle surface in certain density aqueous solution, and form one layer of water around nanoparticle surface
Layer is closed, like coating upper one layer of very thin film, certain steric effect is generated between such nanoparticle, shielding weakens nanoparticle
Attraction between son stops the reunion each other of nanoparticle.Above-mentioned charge repels each other the synergistic effect of effect and steric effect, makes nanometer
The dispersibility and stability of nano-scale is presented in particle in coating.
The embodiment of the present invention has the advantages that
The embodiment of the present invention uses oxide nano rare earth (CeO2) have stable composite oxides coating to infrared laser height
The special role of absorptivity；Nano-meter SiO_22Keep surface flat after in laser melting coating and alloying process melted surface can solidify
It is whole；The reunion of nanometer oxide material is substantially reduced matrix to the absorptivity and cracking resistance crack arrest effect of infrared laser, makes preset painting
Layer material loses indehiscent effect in expected increase light absorption and cladding process.The embodiment of the present invention is big using high-speed circulating
The wet grinding of flow ultrafine nanometer can keep the nanometer extinction effect of nano material in preset coating composite material and receive
Rice cracking resistance crack arrest effect；In laser impact intensified, nano composite dope of the present invention is preferably used, it is ensured that generate in shock peening layer
High dislocation density and high residual compressive stress, so that the military service performance of critical mechanical components be made to reach the limit values.
Detailed description of the invention
It, below will be to embodiment party in order to illustrate more clearly of embodiments of the present invention or technical solution in the prior art
Formula or attached drawing needed to be used in the description of the prior art are briefly described.It should be evident that the accompanying drawings in the following description is only
It is merely exemplary, it for those of ordinary skill in the art, without creative efforts, can also basis
The attached drawing of offer, which is extended, obtains other implementation attached drawings.
Fig. 1 is the atomic force microscopy diagram of absorbing nano oxide paint provided in an embodiment of the present invention；
Fig. 2 is same absorbing nano oxide paint atomic force microscope partial analysis figure provided in an embodiment of the present invention；
Fig. 3 is the backscattered electron SEM photograph of laser wide-band cladding metal based alloys-WC provided in an embodiment of the present invention
Figure, wherein (a) is No. 1 sample, (b) is No. 2 samples；
Fig. 4 is the microscopic appearance of No. 1 sample cladding layer provided in an embodiment of the present invention, wherein (a) is cladding layer surface layer, (b)
(c) it is cladding layer subsurface for cladding layer subsurface, (d) is cladding layer and basal body interface.
Fig. 5 is the microscopic appearance of No. 2 sample cladding layers provided in an embodiment of the present invention, wherein (a) is cladding layer surface layer, (b)
(c) it is cladding layer subsurface for cladding layer subsurface, (d) is cladding layer and basal body interface.
Fig. 6 is the microscopic appearance (2000X) of cladding layer provided in an embodiment of the present invention, wherein (a) is No. 1 sample, (b) is 2
Number sample.
Specific embodiment
Embodiments of the present invention are illustrated by particular specific embodiment below, those skilled in the art can be by this explanation
Content disclosed by book is understood other advantages and efficacy of the present invention easily, it is clear that described embodiment is the present invention one
Section Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not doing
Every other embodiment obtained under the premise of creative work out, shall fall within the protection scope of the present invention.
Embodiment 1
It include aggregate and auxiliary material for the nano composite dope in laser surface modification technique in the embodiment of the present invention,
In, aggregate includes mass percent are as follows: 10% nano-cerium oxide, 15% nano-titanium oxide, 15% nano zine oxide；Accessory package
Include mass percent are as follows: 10% cladding agent polyethylene glycol, 10% dispersing agent P-19,5% emulsifier op-10,5% antirust agent nitrous
Acid is received, 5% bonding agent PVA, surplus are solvent deionized water.
The preparation method for the nano composite dope in laser surface modification technique of the embodiment of the present invention includes following
Step:
It is first 10% cladding agent polyethylene glycol, 10% dispersing agent P-19,5% emulsifier op-10,5% by mass percent
Antirust agent nitrite natrium, 5% bonding agent PVA, surplus are after solvent deionized water is mixed with sand mill, to form mixture；Then
10% nano-cerium oxide, 15% nano-titanium oxide, 15% nano zine oxide are added into mixture, using high-speed circulating nanometer
Grinder is fully dispersed, cladding, emulsifies, and forms finished product nano composite dope, finished product nano composite dope is poured into container
It is sealed spare.
Embodiment 2
It include aggregate and auxiliary material for the nano composite dope in laser surface modification technique in the embodiment of the present invention,
In, aggregate includes mass percent are as follows: 15% nano-cerium oxide, 18% nano-titanium oxide, 18% nano zine oxide；Accessory package
Include mass percent are as follows: 12% cladding agent polyethylene glycol, 12% dispersing agent P-19,8% emulsifier op-10,8% antirust agent nitrous
Acid is received, 15% bonding agent PVA, surplus are solvent deionized water.
The preparation method for the nano composite dope in laser surface modification technique of the embodiment of the present invention includes following
Step:
First the cladding of mass percent 12% agent polyethylene glycol, 12% dispersing agent P-19,8% emulsifier op-10,8% are prevented
Agent nitrite natrium, 15% bonding agent PVA, the surplus of becoming rusty are solvent deionized water, after being mixed with sand mill, form mixture；Then
15% nano-cerium oxide, 18% nano-titanium oxide, 18% nano zine oxide are added into mixture, using high-speed circulating nanometer
Grinder is fully dispersed, cladding, emulsifies, and forms finished product nano composite dope, finished product nano composite dope is poured into container
It is sealed spare.
Embodiment 3
It include aggregate and auxiliary material for the nano composite dope in laser surface modification technique in the embodiment of the present invention,
In, aggregate includes mass percent are as follows: 15% nano-titanium oxide, 15% nano chromium oxide, 20% common titanium oxide；Accessory package
Include mass percent are as follows: 12% cladding agent polyethylene glycol, 12% dispersing agent P-19,8% emulsifier op-10,8% antirust agent nitrous
Acid is received, 15% bonding agent PVA, surplus are solvent deionized water.
The preparation method for the nano composite dope in laser surface modification technique of the embodiment of the present invention includes following
Step:
First the cladding of mass percent 12% agent polyethylene glycol, 12% dispersing agent P-19,8% emulsifier op-10,8% are prevented
Agent nitrite natrium, 15% bonding agent PVA, the surplus of becoming rusty are solvent deionized water, after being mixed with sand mill, form mixture；Then
15% nano-titanium oxide, 15% nano chromium oxide, 20% common titanium oxide are added into mixture, using high-speed circulating nanometer
Wet grinding mill is fully dispersed, cladding, emulsifies, and forms finished product nano composite dope, finished product nano composite dope is poured into container
In be sealed it is spare.
Embodiment 4
It include aggregate and auxiliary material for the nano composite dope in laser surface modification technique in the embodiment of the present invention,
In, aggregate includes mass percent are as follows: 20% nano-titanium oxide, 20% nano chromium oxide, 25% common titanium oxide；Accessory package
Include mass percent are as follows: 10% cladding agent polyethylene glycol, 10% dispersing agent P-19,5% emulsifier op-10,5% antirust agent nitrous
Acid is received, 5% bonding agent PVA, surplus are solvent deionized water.
The preparation method for the nano composite dope in laser surface modification technique of the embodiment of the present invention includes following
Step:
First the cladding of mass percent 10% agent polyethylene glycol, 10% dispersing agent P-19,5% emulsifier op-10,5% are prevented
Agent nitrite natrium, 5% bonding agent PVA, the surplus of becoming rusty are solvent deionized water, after being mixed with sand mill, form mixture；Then to
20% nano-titanium oxide, 20% nano chromium oxide, 25% common titanium oxide are added in mixture, it is wet using high-speed circulating nanometer
Method grinder is fully dispersed, cladding, emulsifies, and forms finished product nano composite dope, finished product nano composite dope is poured into container
Be sealed it is spare.
Embodiment 5
It include aggregate and auxiliary material for the nano composite dope in laser surface modification technique in the embodiment of the present invention,
In, aggregate includes mass percent are as follows: 10% nano-titanium oxide, 10% nano-cerium oxide, 20% nanometer of WC/Co, 10% receives
Rice silica；Auxiliary material includes mass percent are as follows: 10% cladding agent polyethylene glycol, 10% dispersing agent P-19,5% polyoxyethylene nonylphenol ether-
10,5% antirust agent nitrite natrium, 5% bonding agent PVA, surplus are solvent deionized water.
The preparation method for the nano composite dope in laser surface modification technique of the embodiment of the present invention includes following
Step:
First the cladding of mass percent 10% agent polyethylene glycol, 10% dispersing agent P-19,5% emulsifier op-10,5% are prevented
Agent nitrite natrium, 5% bonding agent PVA, the surplus of becoming rusty are solvent deionized water, after being mixed with sand mill, form mixture；Then to
Be added in mixture: 10% nano-titanium oxide, 10% nano-cerium oxide, 20% nanometer of WC/Co, 10% nano silicon oxide are adopted
With high-speed circulating nanometer wet grinding mill it is fully dispersed, cladding, emulsification, formed finished product nano composite dope, finished product nanometer is answered
Close coating pour into container be sealed it is spare.
Embodiment 6
It include aggregate and auxiliary material for the nano composite dope in laser surface modification technique in the embodiment of the present invention,
In, aggregate includes mass percent are as follows: 15% nano-titanium oxide, 15% nano-cerium oxide, 25% nanometer of WC/Co, 15% receives
Rice silica；Auxiliary material includes mass percent are as follows: 12% cladding agent polyethylene glycol, 12% dispersing agent P-19,8% polyoxyethylene nonylphenol ether-
10,8% antirust agent nitrite natrium, 15% bonding agent PVA, surplus are solvent deionized water.
The preparation method for the nano composite dope in laser surface modification technique of the embodiment of the present invention includes following
Step:
First the cladding of mass percent 12% agent polyethylene glycol, 12% dispersing agent P-19,8% emulsifier op-10,8% are prevented
Agent nitrite natrium, 15% bonding agent PVA, the surplus of becoming rusty are solvent deionized water；Then it is added into mixture: 10% nano oxygen
Change titanium, 10% nano-cerium oxide, 20% nanometer of WC/Co, 10% nano silicon oxide is filled using high-speed circulating nanometer wet grinding mill
Dispersion, cladding, emulsification, form finished product nano composite dope, finished product nano composite dope are poured into being sealed in container
It is spare.
The absorptance and crack resistance of the nano composite dope of 1-6 of the embodiment of the present invention are preferable, are mainly used for LC and LA, and
Embodiment 1-4 is used equally for LTH, LC, LD and LSH, and wherein embodiment 5 and 6 comprehensive performance of embodiment are best.
The influence that test example 1, preparation method disperse nano composite dope
As shown in table 1, the comparison that preparation method disperses nano material.
Table 1
The embodiment of the present invention is dispersed and coats the nano-metal-oxide and carbide composite coating that handle to above-mentioned
Infrared spectrum analysis is carried out with Nicolet370Ft-IR infrared spectrometer.As depicted in figs. 1 and 2, to the nano-oxide of preparation
And carbide absorbing coating is measured characterization with AJ-III type atomic force microscope.It is found that nano-oxide and carbide apply
Material has reached nano-dispersion, the nano-oxide and carbide size range of absorbing coating.Optional three particles in Fig. 1: Asd=
51.976nm Ahd+46.874nm；Bsd=74.960nm Bhd=62.498nm；Csd=53.518nm Chd=
46.876nm.Respectively less than 100nm.
Test example 2, the absorptivity of nano composite dope
The embodiment of the present invention directly measures the laser transformation hardening for the metal sample for coating absorbing coating using metallographic method
The area in area, and calculated under laser treatment high temperature with this to CO2The absorptivity of laser, the method are published in by the present inventor
" metal heat treatmet ".Thus method, there are relational expressions between laser transformation hardening zone area and coating spectral absorption: S1/S2
=K (A1/A2) ..., A1, A2 and S1 in formula, S2 be respectively divided into two kinds of coatings absorptivity and corresponding laser transformation hardening
Area's area.COEFFICIENT K is the impact factor in addition to absorptivity to S1 and S2, if the laser treatment experimental condition phase of two kinds of coatings
Together, then known A1, S1, S2 can acquire A2.
Select GG15 steel as basis material, circular diameter 22mm, internal diameter 4mm, high 5mm.It is applied respectively on sample
The nano-oxide and carbide absorbing coating and ordinary oxide and carbide absorbing coating of the upper embodiment of the present invention, after dry
With HJ-3 type 2000W CO2Laser machine carries out laser scanning processing to it, laser power 1500W scanning speed 10mm/s,
Then metallographic sample preparation is carried out, in the area of laser transformation hardening zone arc of the metallography microscope under the microscope and on testing profile.It surveys
As shown in Table 2, the laser transformation hardening zone size of different absorbing coatings compares test result.
Table 2
L is arc hardening zone bottom edge length, and D is depth of the camber hardening zone bottom edge center to camber line.Calculate hardening zone face
The laser transformation hardening zone area ratio ordinary oxide absorbing coating of product, nano-oxide and carbide absorbing coating is big
6.33%.
Test example 3, nano composite dope have excellent cracking resistance effect in LC, LA
Table 3 measures the coating failure toughness K of composite coating prepared by embodiment 5 with EVANS indentation method1cTest result
Table 3 is the result for meeting paint coatings fracture toughness that the embodiment of the present invention 5 is measured with EVANS indentation method.Fracture
Toughness is to reflect that material resists the performance indicator of instable growth of crack, as shown in Table 3, surfacing Ni base WC/Co composite ceramic coat
Fracture toughness average value K1c=9MN/m-3/2, and in existing Vickers maximum load, laser melting coating adds nanometer
The cladding layer that WC/Co alloy powder coating obtains still flawless occurs, and laser melting coating adds nanometer WC/Co alloy powder coating
Cracking resistance effect.
The microscopic structure of laser melting coating addition nanometer WC/Co-Ni base and Fe base cladding layer obtained is as shown in figure 3, can
See that cladding layer has eliminated hole and crackle.And the form of above-mentioned Carbide Phases and it is distributed in high power SEM, such as Fig. 4 and Fig. 5 institute
Show, sample 1 can be formed be distributed in three-dimensional net structure+be in Dispersed precipitate the distribution of ultra-fine grain shape.When matrix and reinforced phase
Three-dimensional space contiguous network structure is formd in the composite, and is intersected when being intertwined, three-dimensional net structure
Reinforced phase obtains toughening because toughness possessed by the metal phase of winding is intersected therewith, and metal phase is then due to network reinforced phase bone
The rigid carrying of frame acts on and is enhanced, and the two is mutually relied on, mutual reinforcement, and resulting strengthening effect will be much better than to increase
The independent evenly dispersed situation in the base of strong phase particle.Sample 2 can be formed present dendroid and random geometry phase+
In the subparticle shape Carbide Phases of Dispersed precipitate, random geometry hardening constituent is uniformly distributed in matrix, and it is strong to form disperse
Change.
The nanometer WC/Co-Ni base and Fe based powders coating and matrix of the preset addition of the laser melting coating of the embodiment of the present invention
Related component in surface cladding binder course, substantially have passed through in laser cladding process or part have passed through dispersion, fusing, coagulate
Gu, chemical combination, the processes such as diffusion and convective mass transfer, can form that strengthening effect is extraordinary to be under the conditions of certain technological parameter
The Carbide Phases that dispersion-strengthened action is mutually played to matrix of the Carbide Phases of network structure and Dispersed precipitate.Due to laser melting coating
Process has very high degree of supercooling and cooling velocity, therefore reinforced phase, during quick cladding, size is possible to be limited in
Sub-micron (< 1 μm) or nanometer scale (≤100nm), along with the nanostructure WC/Co through being granulated that fore-put powder introduces is swashing
Light is possible to still have considerable part to remain nanoscale after quickly handling.Exist in the cladding layer of the embodiment of the present invention and quite counts
Scale≤100nm carbide particle of amount is as shown in Figure 6.
The laser melting coating addition nanometer WC/Co-Ni base of the embodiment of the present invention and the K1c of Fe base cladding layer compare surfacing Ni base
The K1c of nanometer WC/Co composite coating is significantly improved.And K1c is that the important of coating resistance cracking sentences play, K1c value height means
The cracking resistance of cladding layer is good.
The result shows that KC >=18.0MN m of laser melting coating NI base nano-composite coating-3/2, and surfacing NI base WC/CO is multiple
The KC average value for closing coating is 8.1MN m-3/2, in embodiment, formed in laser melting coating NI base nanometer WC/CO composite coating
It is the coating in the Carbide Phases of three-dimensional net structure distribution and in the synthesis humidification of the superfine carbide phase of Dispersed precipitate
The main reason for fracture toughness KC material more same than conventional surfacing, the KC of non-nano coating is significantly improved.
Application of the nano composite dope of the embodiment of the present invention in laser surface modification processing, in a variety of gold such as steel, iron
Belong to the composite coating for coating preparation of the embodiment of the present invention on sample, then carries out Laser Surface Treatment test, the embodiment of the present invention
Composite coating have not agglomerate, do not precipitate, apply, brush and spray and facilitate, it is pollution-free, have no irritating odor, without anti-when laser treatment
Spray is not burnt, and the advantages that facilitating is removed after laser treatment.
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(10) Zhang Yixin, the summary of the emulsion paint technological process of production, New Building Materials, in October, 2002.
(11) Liu Yanquan, the development of nano-material modified exterior wall latex paint, New Building Materials, in April, 2003.
(12) Chen Yunkui, infrared absorption spectroscopy and its application, publishing house, Shanghai Communications University.1993.
(13) nano-oxide coating, Shanghai Inst. of Technical Physics, Chinese Academy of Sciences's test report, 2003.5.20.
(14) method of stainless steel surface laser assembling NI base nanometer WC/CO composite deposite, patent of invention, the patent No.
ZL200410025437.7
(15) processing method of laser melting coating nano ceramic coat cracking resistance, patent of invention, the patent No.
ZL200310106499.X, international Patent classificating number C23C24/10.
Although above having used general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention are fallen within the scope of the claimed invention.
Claims (9)
1. a kind of nano composite dope in laser surface modification technique, which is characterized in that the nano composite dope packet
Include aggregate and auxiliary material, wherein the aggregate includes nano-titanium oxide, oxide nano rare earth and/or Nanoalloy powder.
2. as described in claim 1 for the nano composite dope in laser surface modification technique, which is characterized in that
The aggregate further includes one of nano zine oxide, nano silicon oxide and nano chromium oxide or several.
3. as described in claim 1 for the nano composite dope in laser surface modification technique, which is characterized in that
The oxide nano rare earth is nano-cerium oxide.
4. as described in claim 1 for the nano composite dope in laser surface modification technique, which is characterized in that
The Nanoalloy powder includes nanometer WC/Co.
5. as described in claim 1 for the nano composite dope in laser surface modification technique, which is characterized in that
The auxiliary material includes covering, dispersing agent, emulsifier, antirust agent, binder and solvent.
6. as claimed in claim 5 for the nano composite dope in laser surface modification technique, which is characterized in that
The covering is polyethylene glycol；The antirust agent is sodium nitrite；The binder is PVA；The solvent be go from
Sub- water.
7. a kind of prepare the method described in claim 1 for the nano composite dope in laser surface modification technique, spy
Sign is to include that the auxiliary material is first mixed to form mixture with sand mill, and the aggregate is then passed through high-speed circulating big flow
Nanometer wet grinding mill is fully dispersed, clads, obtains the nano composite dope after emulsification treatment, wherein the aggregate includes receiving
Rice titanium oxide, oxide nano rare earth and/or Nanoalloy powder, wherein the Nanoalloy powder includes nanometer WC/Co.
8. the method for claim 7, which is characterized in that
The aggregate further includes one of nano zine oxide, nano silicon oxide and nano chromium oxide or several.
9. the method for claim 7, which is characterized in that
The oxide nano rare earth is nano-cerium oxide.
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