CN104630682A - Method for refining hot-dipping coating material by employing laser heat treatment - Google Patents

Method for refining hot-dipping coating material by employing laser heat treatment Download PDF

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Publication number
CN104630682A
CN104630682A CN201510034261.XA CN201510034261A CN104630682A CN 104630682 A CN104630682 A CN 104630682A CN 201510034261 A CN201510034261 A CN 201510034261A CN 104630682 A CN104630682 A CN 104630682A
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hot
laser
coating material
dip
plating
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胡伟东
吴广新
张捷宇
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University of Shanghai for Science and Technology
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University of Shanghai for Science and Technology
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Priority to CN201510034261.XA priority Critical patent/CN104630682A/en
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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
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/285—Thermal after-treatment, e.g. treatment in oil bath for remelting the coating

Abstract

The invention discloses a method for refining a hot-dipping coating material by employing laser heat treatment. The method comprises the following steps: preparing the hot-dipping coating material on the surface of an apparatus; carrying out laser remelting treatment on the coating material surface by the heat action of the laser to melt alloy on the coating surface; refining crystalline grains of hot-dipping coating alloy through quick cooling, wherein when the laser remelting treatment is performed on the hot-dipping coating material, the laser power for laser remelting selection is 1.0-2.0kw; the laser beam scanning speed is 10-20mm/s; and the diameters of light spots are 1-3mm. The crystalline grains of the coating are refined by a laser remelting method to improve the surface property of the coating material. According to the technology, the surface quality of the coating material can be effectively improved; the application range can be expanded; and the requirements of industrial production can be met.

Description

The method of LASER HEAT TREATMENT refinement hot-dip coating material
Technical field
The present invention relates to a kind of heat treating method of material surface, particularly a kind of heat treating method of material surface coating, apply hot-dip coated intensifying technology field.
Background technology
Galvanizing is the major portion in hot dip process product, and its industrial production history is long, and product production is large, and applied range, coating has good corrosion resistance nature.Aluminium coat is silvery white in color, and has the decorative appearance performance being better than zinc coating, has excellent atmospheric corrosion resistance, good heat reflection performance.Zinc layers of aluminizing has been concentrated simultaneously and has been aluminized and zinc-plated advantage, and it has the excellent weather-resistant performance of alclad sheet, preferably high temperature resistance and heat reflection and good welding property; Simultaneously it has the good trimming of galvanized sheet and cut electro-chemical protection and good plasticity concurrently, and has gratifying distinguished silvery white plating and spend surface.In hot dip aluminum plating zinc coating, the mainly Zn-5Al-RE coating (Galfan coating) be most widely used and Zn-55Al-1.6Si coating (Galvalume coating is called for short GL).Main based on hot-dip coated solidity to corrosion in application in the past, be widely used in building, automobile and other industries.But along with the development of social demand, the market of hot-dip coating material also expands, and is applied to appliance industry gradually, as bread toaster, refrigerator, baking oven etc. thereupon.This just has higher requirement to its surface quality, such as better aesthetic property, planarization, machining property etc.Grain refining is one of important means improving metallic substance comprehensive mechanical property, and we by carrying out grain refining process to hot-dip coating, can make the surface quality of coating material be improved, widening its range of application.
In actual production process, the modal method of hot-dip coating grain refining is in plating solution, add the grain-refining agent of titanium or titaniferous.For aluminum-zinc alloy crystal grain thinning field, as in the patent No. be US5571566 patent in composition be Al 55%, Zn 43.4%, Al-Ti excellent intermediate alloy is added as grain-refining agent in the plating solution of Si 1.6%, and for example the patent No. be in the patent of EP1428898 to composition be Al 55%, Zn 43.4%, Al-Ti-B master alloy is added in the plating solution of Si 1.6%, above two patents all with the addition of the grain-refining agent of titaniferous in plating solution, grain-refining agent drastically increases nucleation rate, refinement crystal grain effectively, the more uniform coating of formative tissue, make the raising that the solidity to corrosion of coating and high temperature oxidation resistance obtain in various degree.But in situ production process, when adding titaniferous grain-refining agent in plating solution, also there are some problems, if certain steel production enterprise domestic is in hot dip aluminum plating zinc production process, often there is zinc and spend uneven and that cadmia is too much phenomenon.This defect directly concerns the surface quality of coating, has influence on the aesthetic property of coating greatly, causes product to demote and processes, even cause this batch products to cancel.In addition also there is thinning effect instability, high in cost of production weak point as Al-Ti Master alloy refiners, the crystal grain therefore adopting suitable method to carry out refinement hot-dip coating has become a kind of trend.
Laser remolten utilizes the high-duty density of laser moment that skin layer is melted, and the matrix being in low temperature has very strong thermal conductivity, can cause great condensate depression, makes molten bath rapid solidification, obtains superfine crystal particle and makes surface strengthening.Be, in the patent of CN102560054A, laser remolten process has been carried out to workpiece in patent publication No., effective refinement crystal grain of workpiece surface processing layer, increases substantially the wear resistance of material, thermotolerance and erosion resistance, and workpiece surface is smooth, attractive in appearance, there is good surface property; Be carry out laser remolten, anneal to high melting point alloy in the patent of CN101575690A in patent publication No., it is very refined that result obtains crystal grain, homogeneous microstructure, fine and close alloy material, thus improve the performance of material each side.In addition, laser remolten can also make alloy strength increase, microsegregation reduces, has non-equilibrium phase generation etc., and these can play effective surface strengthening.
For adding the thinning method of grain-refining agent, laser remolten complete processing is simple, good in refining effect, and belongs to noncontact processing, and machined material does not stress, indeformable.In addition laser remolten does not need to add other materials in coating material, therefore can not produce waste residue, waste gas, waste water.Therefore laser remolten has good application prospect in hot-dip coating grain refining, but finds after consulting relevant document that the research at present in laser remolten refinement hot-dip coating crystal grain is then not reported so far.
Summary of the invention
In order to solve prior art problem, the object of the invention is to the deficiency overcoming prior art existence, a kind of method of LASER HEAT TREATMENT refinement hot-dip coating material is provided, laser remelting process is adopted to carry out refinement coating crystal grain, to improve the surface properties of coating material, this technique can effectively improve coating material surface quality, widens its range of application, meets the needs of suitability for industrialized production.
Create object for reaching foregoing invention, the present invention adopts following technical proposals:
A kind of method of LASER HEAT TREATMENT refinement hot-dip coating material, after hot-dip coated material is prepared on the surface of device, the heat effect of recycling laser carries out laser remolten process to coating material surface, melt coating surface alloy, subsequently again by cooling the grain refining making hot-dip coating alloy rapidly, when when carrying out laser remolten process to hot-dip coated material, the laser power that laser remolten is selected is 1.0 ~ 2.0kw, laser beam flying speed is 10 ~ 20mm/s, and spot diameter is 1 ~ 3mm.
As the preferred technical scheme of the present invention, when hot-dip coated material is prepared on the surface of device, comprise the substrate material surface mechanical treatment of device, surface degreasing, washing, pickling successively, wash again, preheating, immersion plating and a series of process of cooling, obtain that there is hot-dip coated device.
As the present invention's preferred technical scheme further, when hot-dip coated material is prepared on the surface of device, comprise the steps:
A. by the substrate material surface of device through 0 #~ 6 #after sand paper is polished step by step, remove the substrate material surface oxide film of device;
B., under 85 DEG C of conditions, making the surface of the device of the cleaning obtained in described step a immerse solute total mass concentration is NaOH and Na of 10% 2oil removing in the basic solution of CO3, soaks after 15 minutes and is taken out by device, and with the surface of warm distilled water flushing device;
C. under 20 DEG C of conditions, functional quality concentration be 15% the surface of HCl solution to the device obtained in described step a eliminate rust, soak and take out again after 15 minutes, then use the distilled water flushing of room temperature clean;
D. weighted plating solution ingot metal is positioned in crucible, and crucible is put into immersion plating stove, then pass into the H of 5L/min 2and N 2mixed gas, mixed gas contains the H of 10% according to volume ratio 2, ensure the body of heater pressure-fired of immersion plating stove, then by the melt temperature of crucible heating to corresponding plating solution ingot metal, after ingot metal melts completely, namely obtain hot-dip plating metal plating solution; As preferred technical scheme, when device cools after leaving hot-dip plating metal plating solution completely, preferably adopt water-cooled or air cooling mode; Described plating solution ingot metal preferably adopts zinc ingot metal, aluminium zinc silicon ingot or aluminium zinc ingot metal;
E. before the device obtained in described step c being immersed plating solution, at upper furnace preheating 10min, then device is immersed in the hot-dip plating metal plating solution prepared in described steps d, after reaching the setting immersion plating time, vertically device is mentioned, the speed of mentioning of device is 0.09m/s, after device leaves hot-dip plating metal plating solution completely, namely cools subsequently.
As the present invention's preferred technical scheme further, when carrying out laser remolten process to the coating material surface of device, adopt CO 2crossing current continuous wave laser, utilizes CO 2the hot spot that crossing current continuous wave laser is formed processes coating material, and make the matrix surface of device form molten bath, then through cooling rapidly, the matrix surface of device forms new layer of metal layer.
The present invention compared with prior art, has following apparent outstanding substantive distinguishing features and remarkable advantage:
1. adopt the method for LASER HEAT TREATMENT of the present invention to hot-dip coating carry out grain refining have simple to operate, processing efficiency is high, save operation, the advantage such as save production cost;
2. the coating material homogeneous microstructure obtained after adopting process of the present invention is fine and closely woven, and grain refining effect is good, can improve the surface quality of coating material.
3. the present invention relates to field of laser heat treatment, adopt laser remolten to melt coating surface alloy after conventional hot dip operation, cooling carrys out the crystal grain of refinement hot-dip coating alloy rapidly subsequently, improves its weave construction, thus improves the over-all properties of coating material.Compared with existing grain refinement technology, as compared with master alloy such as interpolation Al-Ti-B, Al-Ti-C etc., present invention process can the crystal grain of effective refinement surface-treated layer, and raising coating material surface quality, widens its range of application.
Accompanying drawing explanation
Fig. 1 is the schema of the method for the embodiment of the present invention one laser remolten refinement hot-dip coating alloy grain.
Fig. 2 is the setting drawing of the embodiment of the present invention one laser remolten refinement hot-dip coating alloy grain.
Embodiment
Details are as follows for the preferred embodiments of the present invention:
embodiment one:
In the present embodiment, see Fig. 1 and Fig. 2, a kind of method of laser remolten refinement hot-dip coating alloy grain, concrete steps are as follows: wash a pickling one in device surface mechanical treatment one oil removing one and wash preheating one immersion plating one water-cooled.Be fixed on by hot dip process plate on X-Y movable plate 6, the laser beam 1 of setting power sends from laser apparatus, beat device matrix 5 on the surface, form a circular hot spot on surface.Due to the heat effect of laser, matrix 5 surface forms molten bath 3.Simultaneously, X-Y movable plate 6 be with kinetoplast 5 in the x, y direction movement make laser form a rule along scanning direction v to matrix to melt, lap between last molten road and Hou Yirong road is overlap, finally form new one deck alloy layer 2 at matrix surface, thus the surface treatment realized hot-dip coating 4 material, as shown in Figure 1.Laser re-melting process adopts 2kwCO 2crossing current continuous wave laser carries out re melting process to sample surfaces, utilizes CO 2laser apparatus forms hot spot, adopts this hot spot to scan coatingsurface.Due to the heat effect of laser, sample surfaces forms molten bath 3, finally realizes laser remolten.Through the thing phase of the post analysis remelted layer of laser remolten, composition, microtexture and performance.
Hot dip process experiment is as follows:
Device surface mechanical treatment one oil removing one is washed a pickling one and is washed preheating one immersion plating one water-cooled.Concrete steps are:
(1) 45 of size 100mm × 30mm × 1mm are got #steel plate sample, by its surface through 0 #~ 6 #sand paper is polished step by step, removes surface film oxide; (2) at the 10%(NaOH+Na of 85 DEG C 2cO3) oil removing in the aqueous solution, soaks after 15 minutes and takes out, and with warm distilled water flushing; (3) eliminate rust in the 15%HCl solution of 20 DEG C, soak after 15 minutes and take out, and with the distilled water flushing of room temperature; (4) weighted zinc ingot metal (composition is 99.9%Zn, and all the other are trace element) is positioned in crucible, and crucible is put into self-control immersion plating stove, pass into the 10%H of 5L/min 2+ N 2mixed gas, ensures body of heater pressure-fired, by crucible heating to 520 DEG C, after alloy pig melts completely, can carry out hot dip process experiment; (5), before sample immerses plating solution, at upper furnace preheating 10min, then sample is immersed in plating solution, after reaching the regulation immersion plating time, vertically sample is mentioned.Mentioning speed is 0.09m/s.Carry out water-cooled subsequently.
Subsequently laser remolten is carried out to hot dip galvanizing plate, laser power adopts 1.5kw, laser beam flying speed 15mm/s, spot diameter is 2mm, laser makes workpiece surface reach Material Melt temperature, remove laser facula after melting completely Deng sample surfaces, the sample after laser remolten can be obtained after its naturally cooling.Adopt sem observation coating surface and section structure situation afterwards.In the present embodiment, in laser remolten operation when laser beam irradiation is to material surface, laser is become heat energy by absorbed, skin-material is heated intensification, and material surface is melted, when laser beam is cut-off or after removing, material surface cooling rate is very fast, can realize the grain refining of coating.After laser remolten process, with surface and the cross-sectional morphology of electronics scanning electron microscopic observation hot dip process plate.
embodiment two:
The present embodiment is substantially identical with embodiment one, and special feature is:
In the present embodiment, hot dip process experiment is as follows:
Specimen surface mechanical treatment one oil removing one is washed a pickling one and is washed preheating one immersion plating one water-cooled.Concrete steps are:
(1) this step is identical with embodiment one; (2) this step is identical with embodiment one; (3) this step is identical with embodiment one; (4) weighted aluminium zinc silicon ingot (composition is 55%Al-43.3%Zn-1.6%Si) is positioned in crucible, and crucible is put into self-control immersion plating stove, pass into the 10%H of 5L/min 2+ N 2mixed gas, ensures body of heater pressure-fired, by crucible heating to 600 DEG C, after alloy pig melts completely, can carry out hot dip process experiment; (5) this step is identical with embodiment one.
Laser remolten is carried out subsequently to GL is hot-dip coated, laser power adopts 1kw, laser beam flying speed 10mm/s, spot diameter 3mm, laser makes workpiece surface reach Material Melt temperature, Deng sample surfaces melt completely after remove laser facula, the sample after laser remolten can be obtained after its naturally cooling, adopt sem observation coating surface and section structure situation afterwards.
embodiment three:
The present embodiment and previous embodiment are substantially identical, and special feature is:
Hot dip process experiment is as follows:
Specimen surface mechanical treatment one oil removing one is washed a pickling one and is washed preheating one immersion plating one water-cooled.Concrete steps are:
(1) this step is identical with embodiment one; (2) this step is identical with embodiment one; (3) this step is identical with embodiment one; (4) weighted aluminium zinc ingot metal (composition is 5%Al, 0.03% RE, and surplus is Zn) is positioned in crucible, and crucible is put into self-control immersion plating stove, pass into the 10%H of 5L/min 2+ N 2mixed gas, ensures body of heater pressure-fired, by crucible heating to 430 DEG C, after alloy pig melts completely, can carry out hot dip process experiment; (5) this step is identical with embodiment one.
Laser remolten is carried out subsequently to Galfan is hot-dip coated, laser power adopts 2kw, laser beam flying speed 20mm/s, spot diameter 1mm, laser makes workpiece surface reach Material Melt temperature, remove laser facula after melting completely Deng sample surfaces, the sample after laser remolten can be obtained after its naturally cooling.Adopt sem observation coating surface and section structure situation afterwards.
By reference to the accompanying drawings the embodiment of the present invention is illustrated above; but the invention is not restricted to above-described embodiment; multiple change can also be made according to the object of innovation and creation of the present invention; change, the modification made under all spirit according to technical solution of the present invention and principle, substitute, combination, to simplify; all should be the substitute mode of equivalence; as long as goal of the invention according to the invention; only otherwise deviate from know-why and the inventive concept of the method for LASER HEAT TREATMENT refinement hot-dip coating material of the present invention, all protection scope of the present invention is belonged to.

Claims (6)

1. the method for a LASER HEAT TREATMENT refinement hot-dip coating material, it is characterized in that: after hot-dip coated material is prepared on the surface of device, the heat effect of recycling laser carries out laser remolten process to coating material surface, melt coating surface alloy, subsequently again by cooling the grain refining making hot-dip coating alloy rapidly, when when carrying out laser remolten process to hot-dip coated material, the laser power that laser remolten is selected is 1.0 ~ 2.0kw, laser beam flying speed is 10 ~ 20mm/s, and spot diameter is 1 ~ 3mm.
2. the method for LASER HEAT TREATMENT refinement hot-dip coating material according to claim 1, it is characterized in that: when hot-dip coated material is prepared on the surface of device, comprise the substrate material surface mechanical treatment of device, surface degreasing, washing, pickling successively, wash again, preheating, immersion plating and a series of process of cooling, obtain that there is hot-dip coated device.
3. the method for LASER HEAT TREATMENT refinement hot-dip coating material according to claim 2, is characterized in that, when hot-dip coated material is prepared on the surface of device, comprise the steps:
A. by the substrate material surface of device through 0 #~ 6 #after sand paper is polished step by step, remove the substrate material surface oxide film of device;
B., under 85 DEG C of conditions, making the surface of the device of the cleaning obtained in described step a immerse solute total mass concentration is NaOH and Na of 10% 2oil removing in the basic solution of CO3, soaks after 15 minutes and is taken out by device, and with the surface of warm distilled water flushing device;
C. under 20 DEG C of conditions, functional quality concentration be 15% the surface of HCl solution to the device obtained in described step a eliminate rust, soak and take out again after 15 minutes, then use the distilled water flushing of room temperature clean;
D. weighted plating solution ingot metal is positioned in crucible, and crucible is put into immersion plating stove, then pass into the H of 5L/min 2and N 2mixed gas, mixed gas contains the H of 10% according to volume ratio 2, ensure the body of heater pressure-fired of immersion plating stove, then by the melt temperature of crucible heating to corresponding plating solution ingot metal, after ingot metal melts completely, namely obtain hot-dip plating metal plating solution;
E. before the device obtained in described step c being immersed plating solution, at upper furnace preheating 10min, then device is immersed in the hot-dip plating metal plating solution prepared in described steps d, after reaching the setting immersion plating time, vertically device is mentioned, the speed of mentioning of device is 0.09m/s, after device leaves hot-dip plating metal plating solution completely, namely cools subsequently.
4. according to the method for LASER HEAT TREATMENT refinement hot-dip coating material described in any one in claims 1 to 3, it is characterized in that: when carrying out laser remolten process to the coating material surface of device, adopting CO 2crossing current continuous wave laser, utilizes CO 2the hot spot that crossing current continuous wave laser is formed processes coating material, and make the matrix surface of device form molten bath, then through cooling rapidly, the matrix surface of device forms new layer of metal layer.
5. the method for LASER HEAT TREATMENT refinement hot-dip coating material according to Claims 2 or 3, is characterized in that: in described steps d, when device cools after leaving hot-dip plating metal plating solution completely, adopts water-cooled or air cooling mode.
6. the method for LASER HEAT TREATMENT refinement hot-dip coating material according to Claims 2 or 3, it is characterized in that: in described steps d, described plating solution ingot metal is zinc ingot metal, aluminium zinc silicon ingot or aluminium zinc ingot metal.
CN201510034261.XA 2015-01-23 2015-01-23 Method for refining hot-dipping coating material by employing laser heat treatment Pending CN104630682A (en)

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Cited By (4)

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CN106181238A (en) * 2016-07-14 2016-12-07 浙江工贸职业技术学院 Different parts at homogeneous materials component constructs the method for different thicknesses grain structure
CN114729437A (en) * 2019-11-29 2022-07-08 日本制铁株式会社 Zn-Al-Mg hot-dip coated steel sheet
CN115233131A (en) * 2022-06-17 2022-10-25 武汉凌云光电科技有限责任公司 Method for laser cladding and polishing after immersion tin plating of nonferrous metal
EP4079923A4 (en) * 2019-12-18 2022-12-07 Posco Hot dip alloy coated steel material having excellent anti-corrosion properties and method of manufacturing same

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106181238A (en) * 2016-07-14 2016-12-07 浙江工贸职业技术学院 Different parts at homogeneous materials component constructs the method for different thicknesses grain structure
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EP4079923A4 (en) * 2019-12-18 2022-12-07 Posco Hot dip alloy coated steel material having excellent anti-corrosion properties and method of manufacturing same
CN115233131A (en) * 2022-06-17 2022-10-25 武汉凌云光电科技有限责任公司 Method for laser cladding and polishing after immersion tin plating of nonferrous metal

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Application publication date: 20150520