CN100379895C - Process for mechanical plating zinc based rare earth alloy - Google Patents
Process for mechanical plating zinc based rare earth alloy Download PDFInfo
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- CN100379895C CN100379895C CNB2005100487418A CN200510048741A CN100379895C CN 100379895 C CN100379895 C CN 100379895C CN B2005100487418 A CNB2005100487418 A CN B2005100487418A CN 200510048741 A CN200510048741 A CN 200510048741A CN 100379895 C CN100379895 C CN 100379895C
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- 238000007747 plating Methods 0.000 title claims abstract description 174
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 90
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 70
- 239000011701 zinc Substances 0.000 title claims abstract description 64
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 61
- 239000000956 alloy Substances 0.000 title claims abstract description 61
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 56
- 230000008569 process Effects 0.000 title claims abstract description 52
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 39
- -1 rare earth metal salts Chemical class 0.000 claims abstract description 51
- 229910052751 metal Inorganic materials 0.000 claims abstract description 32
- 239000002184 metal Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 19
- 239000010959 steel Substances 0.000 claims abstract description 19
- 238000005275 alloying Methods 0.000 claims abstract description 13
- 239000012266 salt solution Substances 0.000 claims abstract description 5
- 238000005728 strengthening Methods 0.000 claims abstract description 4
- 239000011248 coating agent Substances 0.000 claims description 112
- 238000000576 coating method Methods 0.000 claims description 112
- 239000000843 powder Substances 0.000 claims description 36
- 229910052782 aluminium Inorganic materials 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 18
- 239000000654 additive Substances 0.000 claims description 17
- 230000000996 additive effect Effects 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 15
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000004411 aluminium Substances 0.000 claims description 12
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 11
- 230000000694 effects Effects 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 230000002787 reinforcement Effects 0.000 claims description 10
- 229910000691 Re alloy Inorganic materials 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 238000002203 pretreatment Methods 0.000 claims description 7
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 6
- 229910007570 Zn-Al Inorganic materials 0.000 claims description 6
- 238000007714 electro crystallization reaction Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 239000011707 mineral Substances 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 239000008199 coating composition Substances 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 229910000611 Zinc aluminium Inorganic materials 0.000 abstract description 3
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract 2
- 239000013543 active substance Substances 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000008719 thickening Effects 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 32
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 230000007935 neutral effect Effects 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 239000007921 spray Substances 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 241000221535 Pucciniales Species 0.000 description 6
- 239000012190 activator Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000007689 inspection Methods 0.000 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000005554 pickling Methods 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 5
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 5
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 5
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000003628 erosive effect Effects 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 238000005272 metallurgy Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 235000011150 stannous chloride Nutrition 0.000 description 3
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 3
- 241000195493 Cryptophyta Species 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 235000015320 potassium carbonate Nutrition 0.000 description 2
- 229910001950 potassium oxide Inorganic materials 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000013517 stratification Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910018134 Al-Mg Inorganic materials 0.000 description 1
- 229910018467 Al—Mg Inorganic materials 0.000 description 1
- 241001504664 Crossocheilus latius Species 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
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- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
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- 239000011780 sodium chloride Substances 0.000 description 1
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- 231100000331 toxic Toxicity 0.000 description 1
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Images
Abstract
The present invention provides a method for forming zinc based rare earth alloy plating (Zn-RE and Zn-Al-RE) on the surface of a steel part by a mechanical plating method, which belongs to the technical field of surface plating of steel materials. The method comprises the processes of treating workpieces before plating, building base layers, thickening alloying plating, strengthening the plating, etc. The mechanical plating method is adopted, the workpieces are loaded in a plating barrel which is filled with impact media and water after the workpieces are treated before being plated; then, zinc powder, stannous salt solutions and composite rare earth metal salt solutions are added, the plating barrel is rotated, and an alloy base layer is formed on the surface of steel base bodies; surface active liquids, deposited active agents, composite rare earth metal salts, and zinc power or zinc-aluminium alloy power are added, and the alloy plating is thickened; finally, water is added, the plating barrel is rotated, and the plating structure is strengthened. The present invention has the advantages of little pollution, small energy consumption, metal saving and favorable properties of the obtained plating.
Description
Technical field:
The present invention relates to a kind of method of using the method for mechanical plating at steel-iron components surface formation zinc based rare earth alloy coating (Zn-RE, Zn-Al-RE), belong to the coating surface Technology field of ferrous materials.
Technical background: at present, steel surface rot-resistant agent technology is hot dip process and plating, and the steel products that adopt zinc and zinc-aluminum alloy coating to carry out surfacecti proteon reach 30～40% of year output of steel in developed country, China is 10% at present, and increases with the amount in year 6%.Be impractical in the steel product of long service, the surfacecti proteon of part because galvanization coating is thin, therefore, adopting the zinc-base and the Zn-Al alloy of hot dip process is main protective coating.In recent years give priority to multi-elements alloying coating in the hot dip process field both at home and abroad, on steel plate, steel wire and part goods, substituted traditional zinc coating substantially.Wherein the Zn-5%Al alloy has better manufacturability, then can suppress grain boundary corrosion effectively as adding rare earth; Zn-Al-RE, Zn-Al-Mg alloy are the high anti-corrosion alloy for hot-dip of various countries' develop actively; Galfan alloy (Zn-5%Al-0.03～0.1%La or Ce) erosion resistance is 2～3 times of conventional galvanizing.Each alloying element in the hot dip process zinc-base alloy has played the effects such as wettability that suppress dendritic growth, reduce surface tension, suppress grain boundary corrosion, reduce alloy melting point increase flowability, improve erosion resistance and oxidation-resistance, increase alloy and mother metal respectively.They generally add with master alloy, and the control of its composition is subjected to the influence of each constituent element physics, chemical property and metallurgy condition (as fusing point, proportion, oxidization burning loss, temperature and plating assistant agent).In alloy for hot-dip, add rare earth metal, solidify, the effect of crystallization effect, structure, erosion resistance and the outward appearance of improving coating also had good effect except playing to improve; Rare earth metal forms coating generally with master alloy or dissolve in plating assistant agent and enter zinc pond and zinc-base alloy liquid generation fusion with workpiece to be plated at surface of steel workpiece generation crystallization reaction.As seen, Zinc-based multi-element alloy is the good protective coating that is applicable to iron and steel and process practical proof.Though hot dip process is a kind of method that obtains these coating, but in the stable control of implementation procedure, also there are many difficult points and shortcoming, big as energy consumption, raw material consumption, raw materials used toxic, easily cause environmental pollution etc., seen many drawbacks from the viewpoint of cleaner production, iron and steel plating piece plating back also has hydrogen embrittlement and annealing softening phenomenon.Also there were the factor that is unfavorable for Composition Control in metallurgy, electrocrystallization process when in addition, hot dip process or plating formed coating.
Mechanical plating (Mechanical Plating) is to utilize physics, chemisorption deposition and mechanical collision under normal temperature, normal pressure, makes metal powder form a kind of process of surface treatment of coating on the steel-iron components surface.Typical mechanical plating craft is putting into mechanically operated plating tube through the part that plates pre-treatment, add entry and impact media (glass ball), rotating one of plating tube formation and have collision and rub the fluidised form environment of stone roller effect with the hands.Add metal powder and medicament according to predetermined thickness of coating, under the acting in conjunction of chemical agent and mechanical collision, make the surface of part form coating.The raw materials used nontoxicity of mechanical plating, environment is easily administered, but implementation procedure does not have industrial pollution, plating no hydrogen embrittlement in back and annealing softening phenomenon.Though mechanical plating has these advantages, the intensity of gained coating, hardness are a little less than hot dip process; Glossiness is not as electro-galvanizing; Add rare earth element in mechanical plating, the technology that obtains zinc based rare earth alloy coating yet there are no other report.After testing, find in the mechanical plating zinc based rare earth alloy forming process, different when effect that rare earth metal plays the performance and the structure of coating forming process, coating and crystallization shape layer, show as: help forming fine and smooth fine and close alloy layer tissue.Be present in the appearance luster that rare earth element in the coating has improved coating effectively, can present silver color and silver color silks and satins face effect.Adopt saline soak method, outdoor exposure method, neutral salt spray test method, humid heat test method to detect the anti-corrosion and weather resisteant of coating, the corrosion resistance nature with hot dip process like the constituent class and galvanization coating under the identical situation of thickness of coating is suitable.In the mechanical plating zinc based rare earth alloy forming process, rare earth element adds too much can cause the partially poly-absorption of metal powder at the plating piece edge, influences the homogeneity of coating.
Summary of the invention:
The object of the invention is to overcome the deficiencies in the prior art, provide that a kind of gained coating performance is good, energy consumption is little, pollute less, save the process for mechanical plating zinc based rare earth alloy of metal, adopt the method for mechanical plating on the steel-iron components surface, to obtain zinc based rare earth alloy coating.
The object of the invention technical scheme is: comprise that workpiece plating pre-treatment, basic unit set up, the process for mechanical plating zinc based rare earth alloy of processes such as alloying coating thickens, coating reinforcement, it is characterized in that not by metallurgical and electrocrystallization process, under normal temperature, non-pressurized condition, adopt the mechanical plating method on the steel product surface, to form zinc based rare earth alloy coating; At first workpiece is plated pre-treatment, remove piece surface greasy dirt and oxide skin after, with pack into plating tube of workpiece, and the impact media of 1～2 times of the workpiece of in tube, packing into and an amount of water, add pH value to 1～2 that mineral acid is adjusted plating bath simultaneously; Set up basic unit subsequently, in the plating tube that rotates, add zinc powder, tin salt and compound rare-earth metal salt solution, on the steel substrate surface, form the Zn-Sn-RE alloy basic unit of 1～2 micron of one deck; Carry out alloying coating after basic unit sets up and thicken process, keeping rotation of plating tube and acidic bath pH value is 1～2, form one and promote alloy powder absorption-sedimentary environment, again according to needing Coating composition, add zinc powder or Zn-Al alloy powder, and add the compound rare-earth metal-salt, and rotate the plating tube, make workpiece surface under the impact effect of impact media, form the alloy layer of desired thickness; Coating feeds in raw material, thicken finish after, in the plating tube, add clear water to submergence workpiece and impact media, the plating tube rotated 3～5 minutes, make structure of plating layer reinforcement, appearance light, then plating piece, impact media and plating bath are toppled over and the plating tube, separate, clean plating piece and impact media, check warehouse-in behind the moisture on oven dry plating piece surface, impact media returns use.The compound rare-earth metal-salt that adds is that its weight percent composition is Ce (SO by chlorate, the vitriol synthetic water-soluble additive of rare earth metals such as La, Ce, Pr, Nd
4) 1～20%, La-RECl
35～40%, CeCl
36H
2O 10～30%, Ms-RECl
36H
2O 20～60%; When setting up basic unit, the circumscribed circle linear velocity that the plating tube rotates is 60～80 meters/minute; Alloying coating thicken and the coating strengthening process in, the rotating speed retention wire speed of plating tube is 40～70 meters/minute.When forming Zn-Sn-RE alloy basic unit, in the zinc powder of adding, tin salt and the compound rare-earth metal-salt gross weight, the compound rare-earth metal-salt accounts for 0.01～1%, and tin salt accounts for 1～3%, and all the other are Zn; Thicken process at alloying coating,, obtain zinc based rare earth alloy coating (Zn-RE) or zinc-base Al rare earth alloy coating (Zn-Al-RE) by adding compound rare-earth metal-salt and zinc powder or Zn-Al alloy powder; When coating was zinc based rare earth alloy layer (Zn-RE), the compound rare-earth metal-salt accounted for 0.01～1% in adding gross weight, and all the other are zinc powder; When coating was zinc-base Al rare earth alloy layer (Zn-Al-RE), aluminium powder was 1～5% in adding gross weight, and the compound rare-earth metal-salt is 0.05～2%, and all the other are zinc powder.The metal zinc that adds, metallic zinc content are greater than 94%, and maximum particle diameter is less than 8 microns or cross 1200 orders; The metallic aluminium powder that adds, metallic aluminium content are greater than 93%, and maximum particle diameter is less than 30 microns or cross 400 orders; Generally take gradation reinforced when coating thickens, reinforced intensity control is in 3～10 microns thickness of coating of per 3～5 minutes depositions.The consumption of metal powder is relevant with the thickness of coating by plating surface-area and desire plating of plating piece, and for Zn-RE coating, the consumption of zinc powder is 65～75g/ (m
210 μ m); For Zn-Al-RE coating, the consumption of zinc, aluminum metal powder is 60～70g/ (m
210 μ m).
The present invention adopts the mechanical plating method, not by metallurgical and electrocrystallization process, under normal temperature, non-pressurized condition, on the steel product surface, form zinc based rare earth alloy coating, its technological process comprises that workpiece plating pre-treatment, basic unit set up, alloying coating thickens, coating reinforcement etc.At first workpiece is plated pre-treatment, the greasy dirt that the steel-iron components surface of adopting chemical method or oxidation style to remove to be plated attaches, after overpickling or Shot Blasting eliminate the oxide skin of workpiece surface, with pack into plating tube of workpiece, and in tube, pack into 1～2 times impact media and an amount of water (impact media is the glass ball that uses of standard machinery plating etc., the volume that adds is 1～2 times of workpiece volume, the add-on of water generally gets final product with submergence workpiece and impact media), add pH value to 1～2 (mineral acid can be sulfuric acid, phosphoric acid etc.) that mineral acid is adjusted plating bath simultaneously.Set up basic unit subsequently, in the plating tube that rotates, add zinc powder, tin salt (as stannous sulfate, tin protochloride) and compound rare-earth metal salt solution, the plating tube keeps the circumscribed circle linear velocity at 60～80 meters/minute when rotating, on the steel substrate surface, form the Zn-Sn-RE alloy basic unit of 1～2 micron of one deck, in adding zinc powder, tin salt and compound rare-earth metal-salt gross weight, the compound rare-earth metal-salt accounts for 0.01～1%, and tin salt accounts for 1～3%, and all the other are Zn.
Can carry out alloying coating after basic unit sets up and thicken process, keeping rotation of plating tube and acidic bath pH value is 1～2, adding (can be adopted among the Chinese patent ZL93105628.4 and fill a prescription one by kinds of surface promoting agent compound activation solution, the volume percent composition is: Oleum Cocois 14～16%, salt of wormwood 1～2%, 50% concentration hydrogen potassium oxide 10～13%, the third three pure 2～3%, water 67～72%), form one and promote alloy powder absorption-sedimentary environment; Add zinc powder or Zn-Al alloy powder according to required Coating composition again, and add the multiple rare earth metal salt compound additive of employing, under the impact effect of impact media, form zinc based rare earth alloy coating (Zn-RE) or zinc-base Al rare earth alloy coating (Zn-Al-RE) simultaneously.When coating was zinc based rare earth alloy layer (Zn-RE), the compound rare-earth metal-salt accounted for 0.01～1% in adding total amount by weight, and all the other are zinc powder; When coating was zinc-base Al rare earth alloy layer (Zn-Al-RE), aluminium powder was 1～5% in adding total amount by weight, and the compound rare-earth metal-salt is 0.05～2%, and all the other are zinc powder.Generally take gradation reinforced when coating thickens, reinforced intensity can be controlled at 3～10 microns thickness of coating of per 3～5 minutes depositions, and the coating outward appearance of the reinforced big acquisition of intensity is coarse generally speaking, otherwise then smooth.According to the situation of plating piece, the rotating speed retention wire speed of plating tube is at 40～70 meters/minute.Reinforced the finishing that coating thickens adds clear water to submergence workpiece and impact media in plating tube, the plating tube rotated 3～5 minutes, makes that structure of plating layer is strengthened, the appearance light; Then plating piece, impact media and plating bath are toppled over and the plating tube, separate, clean plating piece and impact media, check warehouse-in behind the moisture on plating piece oven dry surface, impact media returns use.
In the technological process, the metal zinc of adding, metallic zinc content are greater than 94%, and maximum particle diameter is less than 8 microns or cross 1200 orders; The metallic aluminium powder that adds, metallic aluminium content is greater than 93%, and form can be a sheet or granular, and maximum particle diameter is less than 30 microns or cross 400 orders; The compound rare-earth metal-salt that adds is that its weight percent composition is Ce (SO by chlorate, the vitriol synthetic water-soluble additive of rare earth metals such as La, Ce, Pr, Nd
4) 1～20%, La-RECl
35～40%, CeCl
36H
2O 10～30%, Ms-RECl
36H
2O 20～60%; After these rare earth metal salts synthesize water-soluble additive, add with metal zinc and aluminium powder.The consumption of metal powder is relevant with the thickness of coating by plating surface-area and desire plating of plating piece, and for Zn-RE coating, the consumption of zinc powder is 65～75g/ (m
210 μ m); For Zn-Al-RE coating, the consumption of zinc, aluminum metal powder is 60～70g/ (m
210 μ m).Test shows, after the metal zinc refinement, promptly adopt maximum particle diameter less than 10 microns, when particle size range is 0.1～10 micron a superfine metal zinc powder, at aspects such as chemically reactive, specific surface area, adsorptivity, viscous deformation very big variation having taken place, provides advantageous conditions for forming the densified metal layer body.
The present invention adopts the method for mechanical plating, make metal powder in plating bath at first enrichment become the algae bulk, be adsorbed onto workpiece surface deposition stratification subsequently, under the impact effect of impact media,, form coating gradually through densification and distortion; In the process of mass transfer, the change of state of desiring metallizing is: Gu Gu →, whole process is at room temperature carried out, the unitary elasticity of particulate, viscous deformation only take place in the metal of forming coating, and the reconstruct of particulate mutual alignment, the atom reorganization of wide range of structures does not take place, and with particle metal dense accumulation stratification body; The adding of compound rare-earth metal-salt, in the plating bath environment, form the water-solubility rare-earth metal ion, improve the wettability of metal zinc and aluminium powder and plating bath, change the enriched character of metal fine powder, make it tend to form tiny algae group, and improve the absorption deposition characteristics, and make metal powder evenly adsorb and form planar deposition, make finally that coating is smooth, bright, good uniformity.Thulium can also suppress the tendency that Zn-based plating layer color under the atmospheric exposure state becomes ash after coating forms, improved the erosion resistance of coating, further improve the outward appearance of mechanical plating zinc-base alloy layer, make flash plating (＜20 microns) present the silver color satin face, thickness coating (＞50 microns) presents the smooth outward appearance of silver color.
The present invention adopts the method for mechanical plating to obtain zinc based rare earth alloy coating, can avoid hot dip process or electroplate the factor that is unfavorable for Composition Control of metallurgy, electrocrystallization process when forming coating, simultaneously can less energy-consumption, reduce and pollute, save metal.
Metal powder can be metallic zinc, aluminium, zinc-aluminium or other non-ferrous metal and alloy.Because whole process is under normal temperature, normal pressure, mechanical plating can directly form zinc base alloy coating main body without metallurgy or electrocrystallization process, and can in forming the process of coating, add rare earth metal salt and obtain zinc based rare earth alloy coating, but be a kind of save energy and non-ferrous metal, be applicable to the process for cleanly preparing of steel surface protection.
Description of drawings:
Fig. 1 is a process flow diagram of the present invention.
Embodiment:
Below will the present invention is described in further detail by specific embodiment.
Embodiment 1: motorway protective grating high strength holding bolt 400kg, and by the long-pending 24.4m of surfacing
2, desire plating Zn-RE coating, thickness is greater than 50 microns.Workpiece is poured into after acid pickling and rust removing, clear water rinsing in the plating tube, packs into and the isopyknic glass ball of workpiece in the plating tube, adds water to submergence workpiece and glass ball (about 100 liters), rotates the plating tube and makes workpiece and glass ball thorough mixing, and is ready before the plating.Add concentration and be 300 milliliters in 98% sulfuric acid, making bath pH value is 1, forms mixed liquor in the plating tube.Add 1560 gram maximum particle diameters less than 8 microns or cross the ultra-fine pure zinc powder of 1200 purposes, add account for add zinc powder, Ya Xi and compound rare-earth metal-salt gross weight 1% the compound rare-earth metal-salt (consist of 1%Ce (SO
4), 40%La-RECl
3, 10%CeCl
36H
2O, 49%Ms-RECl
36H
2O) Pei Zhi water-soluble additive is 100 milliliters, and weight ratio concentration is 1800 milliliters of 8% the stannous sulfate aqueous solution, make the plating tube with 70 meters/minute linear velocities rotate on workpiece, form after 5 minutes one 1.5 micron thickness, Zn-Sn-RE alloy basic unit uniformly.In mixed liquor, add 1700 milliliters of compound surface activators then and (see Chinese patent ZL93105628.4 prescription one, the volume percent composition is: Oleum Cocois 14～16%, salt of wormwood 1～2%, 50% concentration hydrogen potassium oxide 10～13%, the third three pure 2～3%, water 67～72%), 390 milliliters of rare earth metal salt synthetic water-soluble additive (be the compound rare-earth metal-salt, what add when composition is set up with front basic unit is the same); Entering afterwards and repeating the reinforced zinc coating stage that thickens, every interval added in 3 minutes metallic zinc content greater than 94%, maximum particle diameter is less than 8 microns or cross ultra-fine pure zinc powder 1560 grams of 1200 purposes, rotates the plating tube with 60 meters/minute linear velocities, amount to reinforced 5 times; Adding 100 milliliters of sulfuric acid therebetween, after feeding in raw material for the third time is 1 with the pH value that keeps mixed liquor.Coating thickens whole reinforced finishing, and adds 30 premium on currency in the plating tube, rolls to make coating reinforcement, light in 3 minutes.Mixed liquor cleans, separates workpiece and glass ball by pouring out in the plating bucket, Workpiece inspection, drying, warehouse-in, and the glass ball returns use.Zinc-plated whole process 34 minutes, spherical crown head and the thread segment end surface measurement thickness of survey requirement to bolt is pressed in the plating back, measures 58 microns on spherical crown head through thickness tester; 53 microns of end faces (requiring any mean value at 3 greater than 50 microns), the coating uniform outer appearance is good.480 hours no red rusts of neutral salt spray test.
Embodiment 2: common metric system M16 nut 200kg, and by the long-pending 14m of surfacing
2, desire plating Zn-RE coating, thickness is greater than 40 microns.Workpiece is poured into after acid pickling and rust removing, clear water rinsing in the plating tube, packs into and the isopyknic glass ball of workpiece in the plating tube, adds water to submergence workpiece and glass ball (about 80 liters), rotates the plating tube and makes workpiece and glass ball thorough mixing, and is ready before the plating.Add concentration and be 240 milliliters in 98% sulfuric acid, making bath pH value is 2, forms mixed liquor in the plating tube.Adding 800 gram maximum particle diameters are less than 8 microns or cross the ultra-fine pure zinc powder of 1200 purposes, add account for add zinc powder, tin salt and compound rare-earth metal-salt gross weight 0.01% the compound rare-earth metal-salt (consist of 20%Ce (SO4), 5%La-RECl3,30%CeCl3 6H2O, 45%Ms-RECl
36H
2O) Pei Zhi water-soluble additive is 200 milliliters, and weight ratio concentration is 1200 milliliters of 10% the stannous sulfate aqueous solution, make the plating tube with 70 meters/minute linear velocities rotate on workpiece, form after 5 minutes one 1.5 micron thickness, Zn-Sn-RE alloy basic unit uniformly.In mixed liquor, add 1200 milliliters of compound surface activators (Chinese patent ZL93105628.4 prescription one then, see embodiment 1), 400 milliliters of rare earth metal salt synthetic water-soluble additive (be the compound rare-earth metal-salt, what add when composition is set up with front basic unit is the same); Entering afterwards and repeating the reinforced zinc coating stage that thickens, every interval added that metallic zinc content is 94%, maximum particle diameter is less than 8 microns or cross ultra-fine pure zinc powder 830 grams of 1200 purposes in 4 minutes, rotated the plating tube with 70 meters/minute linear velocities, amounted to reinforced 4 times.Coating thickens whole reinforced finishing, and adds 20 premium on currency in the plating tube, rolls to make coating reinforcement, light in 3 minutes.Mixed liquor cleans, separates workpiece and glass ball by pouring out in the plating bucket, Workpiece inspection, drying, warehouse-in, and the glass ball returns use.Zinc-plated whole process 20 minutes, survey requirement is pressed to nut outer surface measuring thickness in the plating back, measures through thickness tester, and galvanized layer thickness is greater than 40 microns; The coating uniform outer appearance is good.400 hours no red rusts of neutral salt spray test.
Embodiment 3: ￠ 16 compression spring 200kg, and by the long-pending 20m of surfacing
2, desire plating Zn-RE coating, 40 microns of thickness.Workpiece is poured into after acid pickling and rust removing, clear water rinsing in the plating tube, packs into and the isopyknic glass ball of workpiece in the plating tube, adds water to submergence workpiece and glass ball (about 100 liters), rotates the plating tube and makes workpiece and glass ball thorough mixing, and is ready before the plating.Add concentration and be 400 milliliters in 98% sulfuric acid, making bath pH value is 1.5, forms mixed liquor in the plating tube.Adding 600 gram maximum particle diameters are less than 8 microns or cross the ultra-fine pure zinc powder of 1200 purposes, add account for add zinc powder, tin salt and compound rare-earth metal-salt gross weight 0.05% the compound rare-earth metal-salt (consist of 2%Ce (SO4), 23%La-RECl3,15%CeCl3 6H2O, 60%Ms-RECl3 6H
2O) Pei Zhi water-soluble additive is 130 milliliters, and weight ratio concentration is 1600 milliliters of 10% the stannous sulfate aqueous solution, make the plating tube with 70 meters/minute linear velocities rotate on workpiece, form after 5 minutes one 1.5 micron thickness, Zn-Sn-RE alloy basic unit uniformly.In mixed liquor, add 1600 milliliters of compound surface activators (Chinese patent ZL93105628.4 prescription one then, see embodiment 1), 450 milliliters of rare earth metal salt synthetic water-soluble additive (be the compound rare-earth metal-salt, what add when composition is set up with front basic unit is the same); Entering afterwards and repeating the reinforced zinc coating stage that thickens, every interval added that metallic zinc content is 95%, maximum particle diameter is less than 8 microns or cross ultra-fine pure zinc powder 1250 grams of 1200 purposes in 4 minutes, rotated the plating tube with 60 meters/minute linear velocities, amounted to reinforced 4 times.Coating thickens whole reinforced finishing, and adds 20 premium on currency in the plating tube, rolls to make coating reinforcement, light in 4 minutes.Mixed liquor cleans, separates workpiece and glass ball by pouring out in the plating bucket, Workpiece inspection, drying, warehouse-in, and the glass ball returns use.Zinc-plated whole process 20～22 minutes, the plating back is measured thickness by survey requirement to the compression spring surface, measures through thickness tester, and galvanized layer thickness is greater than 40 microns; Coating is even.420 hours no red rusts of neutral salt spray test.
Embodiment 4: 150 kilograms of car door latch, and by the long-pending 15m of surfacing
2, desire plating Zn-Al-RE coating, 20 microns of thickness.Workpiece is poured into after acid pickling and rust removing, clear water rinsing in the plating tube, goes into and the isopyknic glass ball of workpiece at the plating wound packages, adds water to submergence workpiece and glass ball (about 60 liters), rotates the plating tube and makes workpiece and glass ball thorough mixing, and is ready before the plating.Add concentration and be 200 milliliters in 98% sulfuric acid, making bath pH value is 1, forms mixed liquor in the plating tube.Adding contains 3%Al, all the other are the metal powder of Zn (maximum particle diameter is less than 30 microns or cross 400 orders) 390 grams, add account for add metal powder, compound rare-earth metal-salt gross weight 0.05% the compound rare-earth metal-salt (consist of 15%Ce (SO4), 35%La-RECl3,30%CeCl3 6H2O, 20%Ms-RECl3 6H
2O) 40 milliliters of Pei Zhi water-soluble additive and weight ratio concentration are 900 milliliters of 10% the stannous sulfate aqueous solution, make the plating tube with 80 meters/minute linear velocity rotate on workpiece, form after 5 minutes one 1 micron thickness, Zn-Al-RE alloy basic unit uniformly.Continuous back adds 900 milliliters of compound surface activators (Chinese patent ZL93105628.4 prescription one is seen embodiment 1), 160 milliliters of rare earth metal salt synthetic water-soluble additive (composition is with front basic unit establishment stage) in mixed liquor.Enter later on and repeat the reinforced zinc coating stage that thickens, every interval added and contains all the other metal powder 390 grams for Zn of 3%Al in 3 minutes, rotated the plating tube with 70 meters/minute linear velocities, amounted to reinforced 4 times.Behind whole reinforced finishing, add 30 premium on currency in the plating tube, rolling made coating reinforcement, light in 5 minutes.Mixed liquor is by pouring out in the plating bucket.Clean, separate workpiece and glass ball, Workpiece inspection, drying, warehouse-in, the glass ball returns use.23 microns of zinc layer mean thicknesss, the coating uniform outer appearance is good, zinc-plated whole process 28 minutes.240 hours no red rusts of neutral salt spray test.
Embodiment 5: garage door 8, and " iron square hinge 120kg is by the long-pending 11.75m of surfacing
2, desire plating Zn-Al-RE coating, 40 microns of thickness.Workpiece is poured into after acid pickling and rust removing, clear water rinsing in the plating tube, goes into and the isopyknic glass ball of workpiece at the plating wound packages, adds water to submergence workpiece and glass ball (about 80 liters), rotates the plating tube and makes workpiece and glass ball thorough mixing, and is ready before the plating.Adding concentration and be 98% phosphoric acid, to make bath pH value for 300 milliliters be 2, forms mixed liquor in the plating tube.Adding contains 4%Al, and all the other are the metal powder of Zn (maximum particle diameter is less than 30 microns or cross 400 orders) 410 grams, add account for add metal powder, compound rare-earth metal-salt gross weight 2% the compound rare-earth metal-salt (consist of 10%Ce (SO4), 40%La-RECl3,20%CeCl3 6H2O, 30%Ms-RECl3 6H2O) 60 milliliters of Pei Zhi water-soluble additive and weight ratio concentration are 600 milliliters of 8% the tin protochloride aqueous solution, make the plating tube with 60 meters/minute linear velocities rotate on workpiece, form after 5 minutes one 1.5 micron thickness, Zn-Al-RE alloy basic unit uniformly.After continuous, in mixed liquor, add 700 milliliters of compound surface activators (seeing Chinese patent ZL93105628.4, prescription one), 120 milliliters of rare earth metal salt synthetic water-soluble additive (composition is with basic unit's establishment stage).Enter later on and repeat the reinforced zinc coating stage that thickens, every interval added zinc powder 410 grams that contain 3%Al in 5 minutes, rotated the plating tube with 40 meters/minute linear velocities, amounted to reinforced 4 times.Behind whole reinforced finishing, add 40 premium on currency in the plating tube, rolling made coating reinforcement, light in 5 minutes.Mixed liquor by pouring out in the plating bucket, is cleaned, separates workpiece and glass ball, Workpiece inspection, drying, warehouse-in, the glass ball returns use.43 microns of zinc layer mean thicknesss, the coating uniform outer appearance is good, zinc-plated whole process 34 minutes.460 hours no red rusts of neutral salt spray test.
Embodiment 6: common metric system M12 nut 100 kg, and by the long-pending 9m of surfacing
2, desire plating Zn-Al-RE coating, 30 microns of thickness.Workpiece is poured into after acid pickling and rust removing, clear water rinsing in the plating tube, goes into and the isopyknic glass ball of workpiece at the plating wound packages, adds water to submergence workpiece and glass ball (about 60 liters), rotates the plating tube and makes workpiece and glass ball thorough mixing, and is ready before the plating.Adding concentration and be 98% phosphoric acid, to make bath pH value for 200 milliliters be 1, forms mixed liquor in the plating tube.Add and to contain 3%Al all the other are the metal powder of Zn (maximum particle diameter is less than 30 microns or cross 400 orders) 300 grams, adding account for add metal powder, compound rare-earth metal-salt gross weight 1% the compound rare-earth metal-salt (consist of 1%Ce (SO
4), 40%La-RECl
3, 10%CeCl
36H
2O, 49%Ms-RECl
36H
2O) 80 milliliters of Pei Zhi water-soluble additive and weight ratio concentration are 720 milliliters of 10% the tin protochloride aqueous solution, make the plating tube with 60 meters/minute linear velocities rotate on workpiece, form after 5 minutes one 1.5 micron thickness, Zn-Al-RE alloy basic unit uniformly.After continuous, in mixed liquor, add 750 milliliters of compound surface activators (seeing Chinese patent ZL93 105628.4, prescription one), 200 milliliters of rare earth metal salt synthetic water-soluble additive (composition is with basic unit's establishment stage).Enter later on and repeat the reinforced zinc coating stage that thickens, every interval added zinc powder 530 grams that contain 3%Al in 5 minutes, rotated the plating tube with 40 meters/minute linear velocities, amounted to reinforced 3 times.Behind whole reinforced finishing, add 20 premium on currency in the plating tube, rolling made coating reinforcement, light in 5 minutes.Mixed liquor by pouring out in the plating bucket, is cleaned, separates workpiece and glass ball, Workpiece inspection, drying, warehouse-in, the glass ball returns use.31 microns of zinc layer mean thicknesss, the coating uniform outer appearance is good, zinc-plated whole process 20 minutes.280 hours no red rusts of neutral salt spray test.
Claims (4)
1. process for mechanical plating zinc based rare earth alloy, comprise that workpiece plating pre-treatment, basic unit set up, alloying coating thickens, the coating strengthening process, it is characterized in that not by metallurgical and electrocrystallization process, under normal temperature, non-pressurized condition, adopt the mechanical plating method on the steel product surface, to form zinc based rare earth alloy coating; At first workpiece is plated pre-treatment, remove piece surface greasy dirt and oxide skin after, with pack into plating tube of workpiece, and the impact media of 1～2 times of the workpiece of in tube, packing into and an amount of water, add pH value to 1～2 that mineral acid is adjusted plating bath simultaneously; Set up basic unit subsequently, in the plating tube that rotates, add zinc powder, tin salt and compound rare-earth metal salt solution, on the steel substrate surface, form the Zn-Sn-RE alloy basic unit of 1～2 micron of one deck; Carry out alloying coating after basic unit sets up and thicken process, keeping rotation of plating tube and acidic bath pH value is 1～2, form one and promote alloy powder absorption-sedimentary environment, again according to needing Coating composition, add zinc powder or Zn-Al alloy powder, and add the compound rare-earth metal-salt, and rotate the plating tube, make workpiece surface under the impact effect of impact media, form the alloy layer of desired thickness; Coating feeds in raw material, thicken finish after, in the plating tube, add clear water to submergence workpiece and impact media, the plating tube rotated 3～5 minutes, make structure of plating layer reinforcement, appearance light, then plating piece, impact media and plating bath are toppled over and the plating tube, separate, clean plating piece and impact media, check warehouse-in behind the moisture on oven dry plating piece surface, impact media returns use;
The compound rare-earth metal-salt of described adding is that its weight percent composition is Ce (SO by the chlorate of La, Ce, Pr, Nd rare earth metal, vitriol synthetic water-soluble additive
4) 1～20%, La-RECl
35～40%, CeCl
36H
2O 10～30%, Ms-RECl
36H
2O 20～60%; When setting up basic unit, the circumscribed circle linear velocity that the plating tube rotates is 60～80 meters/minute; Alloying coating thicken and the coating strengthening process in, the rotating speed retention wire speed of plating tube is 40～70 meters/minute.
2. process for mechanical plating zinc based rare earth alloy according to claim 1, when it is characterized in that forming Zn-Sn-RE alloy basic unit, in the zinc powder of adding, tin salt and the compound rare-earth metal-salt gross weight, the compound rare-earth metal-salt accounts for 0.01～1%, tin salt accounts for 1～3%, and all the other are Zn; Thicken process at alloying coating,, obtain zinc based rare earth alloy coating (Zn-RE) or zinc-base Al rare earth alloy coating (Zn-Al-RE) by adding compound rare-earth metal-salt and zinc powder or Zn-Al alloy powder; When coating was zinc based rare earth alloy layer (Zn-RE), the compound rare-earth metal-salt accounted for 0.01～1% in adding gross weight, and all the other are zinc powder; When coating was zinc-base Al rare earth alloy layer (Zn-Al-RE), aluminium powder was 1～5% in adding gross weight, and the compound rare-earth metal-salt is 0.05～2%, and all the other are zinc powder.
3. process for mechanical plating zinc based rare earth alloy according to claim 1 and 2, its feature are at the metal zinc that adds, and metallic zinc content is greater than 94%, and maximum particle diameter is less than 8 microns or cross 1200 orders; The metallic aluminium powder that adds, metallic aluminium content are greater than 93%, and maximum particle diameter is less than 30 microns or cross 400 orders; Generally take gradation reinforced when coating thickens, reinforced intensity control is in 3～10 microns thickness of coating of per 3～5 minutes depositions.
4. process for mechanical plating zinc based rare earth alloy according to claim 1 is characterized in that the consumption of metal powder is relevant with the thickness of coating by plating surface-area and desire plating of plating piece, and for Zn-RE coating, the consumption of zinc powder is 65～75g/ (m
210 μ m); For Zn-Al-RE coating, the consumption of zinc, aluminum metal powder is 60～70g/ (m
210 μ m).
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| CN102477553B (en) * | 2010-11-25 | 2015-05-20 | 北京中科三环高技术股份有限公司 | Surface treatment method for mechanical plating of neodymium iron boron workpiece |
| CN102409335B (en) * | 2011-12-01 | 2013-09-11 | 昆明理工大学 | Deposition activator for mechanical plating of Zn-Sn alloy |
| CN110319796B (en) * | 2019-06-20 | 2021-05-11 | 东南大学 | Method for detecting thickness of coating on surface of titanium-plated diamond particle |
| CN112501604A (en) * | 2020-10-09 | 2021-03-16 | 江苏百德特种合金有限公司 | Surface coating processing technology of high-strength fastener |
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Assignee: Maanshan Dingtai Rare Earth& New Materials Co., Ltd. Assignor: Kunming University of Science and Technology Contract record no.: 2011340000176 Denomination of invention: Process for mechanical plating zinc based rare earth alloy Granted publication date: 20080409 License type: Exclusive License Open date: 20060621 Record date: 20110726 |
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