CN106947983B - Intercalation Zn-Al alloy powder and its zinc-aluminium of preparation collaboration anticorrosive paint and method - Google Patents

Intercalation Zn-Al alloy powder and its zinc-aluminium of preparation collaboration anticorrosive paint and method Download PDF

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CN106947983B
CN106947983B CN201710204363.0A CN201710204363A CN106947983B CN 106947983 B CN106947983 B CN 106947983B CN 201710204363 A CN201710204363 A CN 201710204363A CN 106947983 B CN106947983 B CN 106947983B
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zinc
aluminium
intercalation
electro
deposition
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CN106947983A (en
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廖有为
杨焰
旷春桃
车轶材
廖阳飞
肖邵博
万长鑫
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Hunan Jinpan New Material Science & Technology Co Ltd
Central South University of Forestry and Technology
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Hunan Jinpan New Material Science & Technology Co Ltd
Central South University of Forestry and Technology
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/04Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes
    • C09D175/14Polyurethanes having carbon-to-carbon unsaturated bonds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • C09D5/10Anti-corrosive paints containing metal dust
    • C09D5/103Anti-corrosive paints containing metal dust containing Al
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08Anti-corrosive paints
    • C09D5/10Anti-corrosive paints containing metal dust
    • C09D5/106Anti-corrosive paints containing metal dust containing Zn
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/24Electrically-conducting paints
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40Additives
    • C09D7/45Anti-settling agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

Intercalation Zn-Al alloy powder and its zinc-aluminium of preparation collaboration anticorrosive paint and method, the intercalation Zn-Al alloy powder are made of following methods: (1) mixing zinc chloride molten-salt electrolysis liquid and aluminium chloride molten-salt electrolysis liquid, stirring obtains fused salt mixt electrolyte;(2) using copper sheet as cathode, graphite is anode, the electro-deposition in fused salt mixt electrolyte;(3) copper sheet is taken out, is rinsed, deposit cleaning, filtering, vacuum drying obtain intercalation Zn-Al alloy powder.The zinc-aluminium collaboration anticorrosive paint includes the intercalation Zn-Al alloy powder, organic solvent, anti-settling agent and electroconductive resin.The preparation method is to mix the intercalation Zn-Al alloy powder with organic solvent, and anti-settling agent is added in stirring, adds electroconductive resin,.The alloy pattern and microalloying degree of intercalation allumen of the present invention are controllable;It is applied to zinc-aluminium collaboration anticorrosive paint, more existing galvanizing by dipping, zinc aluminum anticorrosive paint antiseptic property are more preferable;The method of the present invention low energy consumption, low pollution.

Description

Intercalation Zn-Al alloy powder and its zinc-aluminium of preparation collaboration anticorrosive paint and method
Technical field
The present invention relates to a kind of Zn-Al alloy powder and its anticorrosive paints and method of preparation, and in particular to a kind of intercalation zinc Al alloy powder and its zinc-aluminium instead of galvanizing by dipping of preparation cooperate with anticorrosive paint and method.
Background technique
Fused salt electro-deposition prepares electro-deposition coating, is in the inorganic salts, organic salt or ionic liquid of melting, using outer The voltage and current added, and control current density, obtain a kind of preparation process of the coat of metal or alloy powder on substrate, The problems such as aquation, hydrolysis and liberation of hydrogen is not present in fused salt electrodeposition process, pollution-free, has been widely used at present.Fused salt electro-deposition Method is used to plate earliest alclad on steel substrate, and because plated layer compact, thickness is controllable, low energy consumption due to rapid proliferation, then grind Study carefully discovery to form alloy between iron and aluminium during the deposition process and realize close attachment by the metallic bond in alloy, then theoretically It only need to change substrate, fused salt electrodeposition process can be used to obtain refined metals powder or prepare alloying pellet.From last century 80 It is gradually mature using fused salt electrodeposition process preparation nickel aluminum alloy, zinc/ferroalloy technique from age, it is 2007 or so, external Zinc/Al alloy powder is prepared.But alloy is prepared using fused salt electrodeposition process, allotment gold can only be passed through before the deposition Belong to molten-salt electrolysis liquid concentration to control the content of each metal in alloy, the metal proportion being unable to accurately control in alloy.In addition, molten The powder of salt electrodeposition process preparation is in prong shape more, and heap poststack bedding void is larger, it is difficult to play the side such as anti-corrosion, anti-halobios adhersion The effectiveness in face.
In the heavily contaminated environment that heavy industry pollution and adjoint extreme natural environment are formed, Steel structure equipment corrosion is fast Speed, annual therefore caused loss have been more than the summation of the loss as caused by the disasters such as fire, earthquake.Conventional hot-dip zinc produces Product have both cathodic protection and shielding action, and Wear resistance and Anti corrosion is good, easily weld, and adhesion property is excellent, and surface-brightening is beautiful, thus quilt The industries such as traffic, building, electric power, the energy, automobile, petrochemical industry, household electrical appliances are widely used in, are most widely used in global range Steel structure anti-corrosion technology.
Though hot dip galvanized product has longer service life and lower validity period maintenance cost, the limitation of itself Property it is also same obvious.For example, (1) galvanizing by dipping energy consumption is high, 500 DEG C or more need to be heated to, therefore process not can avoid oxygen The defect that rate is high, porosity is high, causes use process point corrosion easily occur, leaves security risk;(2) galvanizing by dipping is difficult to Thickness of coating is controlled, the processing of precision component is not used to;(3) surface treatment of hot dip galvanized product requires high, and technique is cumbersome, Both production cycle and the cost for having improved galvanizing by dipping are also easily introduced impurity and cause potential hazard.In addition, galvanizing by dipping produced Cheng Zhonghui escapes plurality of heavy metal dust, strong acid steam, and welding endangers operator's health, and country has put into effect phase thus Pass policy limits this production technology of galvanizing by dipping.Therefore, for various comprehensive to performance, production technology, policy, environment etc. Conjunction is considered, and galvanizing by dipping is not the appropriate method for being anticorrosion of steel structure.
Anticorrosive coating is one of the most effective means for alleviating corrosion, easy to use, cheap.Anticorrosive coating kind Various, the most excellent with cold-applied zinc, cold-applied zinc dry film Zn content is higher than 96%, and corrosion resistance, heat resistance, durability are all very prominent Out, gray but after cold-applied zinc brushing, does not have the metallic luster of the bright silver of zinc.And such as a kind of water of CN103952026 A( Dissolubility zinc aluminum anticorrosive paint and preparation method thereof), a kind of chromium-free zinc aluminum anticorrosive paint of CN101899254 A(and preparation method), High watersoluble modified anticorrosive paint of intercalation of CN105820677 A(a kind of nanoscale environmental protection and preparation method thereof) etc. patents and its turn The product of change then improves the appearance of anticorrosive paint, but this measure sacrifice by way of introducing bright metal, reducing zinc content Part antiseptic property.This kind of zinc aluminum anticorrosive paint is only added into resin using zinc, aluminium as filler by a certain percentage, due to zinc Powder, the partial size of aluminium powder, shape are different, gap easily occur between particle after the drying, it is difficult to guarantee the consistency of dry coating, also easily The phenomenon that causing coating shedding.Simultaneously as the corrosion potential of zinc-aluminium is different, corrosion rate is different, it is also difficult to realize zinc-aluminium Collaboration antisepsis.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, providing a kind of ratio can Control, the adjustable intercalation Zn-Al alloy powder of pattern.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, are provided a kind of resistance to Salt fog, heat-resisting, impact resistance is excellent, and paint film adhesion, flexibility are good, convenient for construction, surface aesthetic, the zinc-aluminium of environmental protection and energy saving Cooperate with anticorrosive paint.
The further technical problems to be solved of the present invention are to overcome drawbacks described above of the existing technology, provide one kind The preparation method of the controllable zinc-aluminium collaboration anticorrosive paint of simple process, content.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of intercalation Zn-Al alloy powder, by following Method is made:
(1) zinc chloride molten-salt electrolysis liquid and aluminium chloride molten-salt electrolysis liquid are mixed, is stirred evenly, obtain fused salt mixt electrolysis Liquid;
(2) using copper sheet as cathode, graphite is anode, is placed in fused salt mixt electrolyte obtained by step (1) and carries out electro-deposition;
(3) copper sheet after step (2) electro-deposition is taken out, is rinsed with water copper sheet, will rinse lower deposit clean, Filtering, vacuum drying, obtain intercalation Zn-Al alloy powder.
Preferably, in step (1), the zinc chloride molten-salt electrolysis liquid by amides compound and anhydrous zinc chloride with mole 1:1.11~1.20 more more preferable than 1:1.1~1.5() be formulated, the aluminium chloride molten-salt electrolysis liquid by amides compound with Anhydrous aluminum chloride is more preferable 1:1.2~1.4 1:1.0~1.5(with molar ratio) it is formulated.When the molten-salt electrolysis liquid is prepared Mixing speed be 400~800r/min.
Preferably, the amides compound is one or more of formamide, propionamide or carbamide etc..
Preferably, in step (1), the zinc chloride molten-salt electrolysis liquid and aluminium chloride molten-salt electrolysis liquid are with mass ratio 1:1~2 Mixing.Ratio by changing zinc chloride, aluminium chloride fused salt electrodeposit liquid is the zinc-aluminium content in controllable alloy, if zinc chloride The ratio of molten-salt electrolysis liquid is excessively high, then easily causes zinc deposition too fast, if the ratio of aluminium chloride molten-salt electrolysis liquid is excessively high, easily cause Al deposition is too fast, and ratio is bad to will result directly in intercalation degree deficiency, it is difficult to prepare satisfactory alloy.
Preferably, in step (1), the speed of the stirring is the more preferable 250~400r/min of 200~800r/min(). Within the scope of the mixing speed, that is, it may make and stir evenly, and can prevent solution from splashing.
Preferably, in step (2), the electro-deposition uses constant potential mode, specifically: initial electro-deposition current potential is- More preferable 40~the 50min of 0.15~-0.45V, 30~60min(of electro-deposition) after, switching electro-deposition current potential be -0.15~- More preferable 40~the 50min of 0.45V, 30~60min(of electro-deposition) after, then switching back into electro-deposition current potential is -0.15~-0.45V, such as This cyclic switching electro-deposition current potential carries out the more preferable 5~7h of 4~8h(of electro-deposition).The i.e. changeable zinc-aluminium of alternate change sedimentation potential It is co-deposited situation, realizes zinc, the growth of aluminium alloy crystal grain intercalation, and then control alloy pattern and microalloying degree.
Preferably, in step (3), the deposit, that is, intercalation allumen;Cleaning way is successively to be rushed with acetone, clear water Deposit;Filtering refers to that the deposit that will be rinsed is filtered >=2 times with teflon membrane filter.
Intercalation allumen of the present invention during the preparation process, by molten salt solvent ratio, deposition voltage, sedimentation time etc. The adjusting of factor, changes the content of each element in zinc/aluminium alloy, and zinc/aluminium alloy is made to show different shape.
It is as follows that the present invention further solves technical solution used by its technical problem: a kind of zinc-aluminium collaboration anticorrosive paint, Including following raw material: anticorrosive packing, organic solvent, anti-settling agent and electroconductive resin;The anticorrosive packing is intercalation zinc-aluminium conjunction Bronze end or the mixture with one or both of zinc powder, aluminium powder.
Preferably, the parts by weight of zinc-aluminium collaboration each raw material of anticorrosive paint are as follows: 50~120(of anticorrosive packing more preferable 70 ~100), 5~30 parts of organic solvent (more preferable 15~25 parts), 1~5 part of anti-settling agent (more preferable 1.5~3.0 parts), conductive tree 10~60 parts of rouge (more preferable 35~55 parts);Wherein, the intercalation Zn-Al alloy powder 15~80 is contained in the anticorrosive packing Part, 0~40 part of zinc powder, 0~20 part of aluminium powder.
Preferably, the partial size of the intercalation Zn-Al alloy powder is 3~5 μm, purity >=99.995%, in oval featheriness Or oval flakey.Intercalation allumen of the present invention refers to zinc, aluminium interbed alloy.
Preferably, the organic solvent be the molten acid anhydride acetic acid esters of butyl, glycol ethyl ether acetate ester, isophorone, butyl butyrate, One or more of dimethylbenzene or dimethylformamide etc..
Preferably, the anti-settling agent is one in polyamide wax, polyolefin-wax, castor oil derivative or organobentonite etc. Kind is several.
Preferably, the electroconductive resin is the resin containing conductive filler graphene, wherein graphene is in electroconductive resin Mass content be 0.5~1.5%.
Preferably, the resin in the electroconductive resin is in epoxy resin, polystyrene, polyurethane or acrylic resin The composite modified resin of one or two or in which two kinds of resins.Resin in the electroconductive resin is more preferably propylene Sour modified polyurethane.
Zinc-aluminium collaboration anticorrosive paint of the present invention can be applied in anticorrosive paint system.
It is as follows that the present invention further solves technical solution used by its technical problem: a kind of zinc-aluminium collaboration anticorrosive paint Preparation method, comprising the following steps: anticorrosive packing is mixed with organic solvent, anti-settling agent is added in whipping process, is stirred It mixes uniformly, adds electroconductive resin, stir evenly,.
Preferably, the mixing speed before addition electroconductive resin is 500~700r/min, is added after electroconductive resin Mixing speed is 1000~1500r/min.
Beneficial effects of the present invention are as follows:
(1) present invention prepares intercalation allumen using electrodeposition process, not using metal deposition rates each under different potentials Same feature is co-deposited situation by alternate change sedimentation potential to change zinc-aluminium, realizes that zinc, the intercalation of aluminium alloy crystal grain are raw It is long, and a variety of path comprehensively control alloy patterns and micro- conjunctions such as sedimentation potential, electrodeposition time, molten-salt electrolysis salt ratio can be passed through Aurification degree;By the intercalation allumen be applied to anticorrosive paint, more existing galvanizing by dipping, zinc aluminum anticorrosive paint, Under C4 environment described in ISO12944-2-1998 standard, the protection time limit of anticorrosive paint of the present invention can be increased to by existing 15 years 20 years;
(2) zinc-aluminium intercalation alloy content can reach 90% or more in dry film after zinc-aluminium of the present invention collaboration corrosion protective coating technology, and Zinc-aluminium ratio is adjustable controllable in alloy, within surface drying time 0.5h, does solid work within time 2h, salt spray resistance, heat-resisting, impact resistance Excellent, paint film adhesion, flexibility are good, and the mode that brushing can be used is constructed, easy to operate, and surface aesthetic is bright, product thickness Controllably, it is easy to repair, there is preferable decorative performance, it is friendly to environment and operator, it is applied with existing galvanizing by dipping, zinc-aluminium anti-corrosion Material is compared, and zinc-aluminium collaboration anticorrosive paint of the present invention avoids the defect of the high porosity of zinc aluminum anticorrosive paint, efficiently solves zinc Aluminium cooperates with Anticorrosion;
(3) inventive process avoids high energy consumption, the high pollution problems in galvanizing by dipping dope preparing process.
Detailed description of the invention
Fig. 1 is the SEM figure under 1 intercalation Zn-Al alloy powder, 10 μm of scales of the embodiment of the present invention;
Fig. 2 is the SEM figure under 1 intercalation Zn-Al alloy powder, 1 μm of scale of the embodiment of the present invention.
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Acrylic acid modified polyurethane used in the embodiment of the present invention contains graphene 1%, according to 103265661 A of CN The method preparation of embodiment 1 in " a kind of the cladding that film is zinc-plated and electroconductive resin ";The examination of chemistry used in the embodiment of the present invention Agent is obtained by routine business approach unless otherwise specified.
Reference example 1
The preparation method of zinc chloride molten-salt electrolysis liquid is: by 90 parts of formamides, 120 parts of carbamides and 480 parts of anhydrous chlorinations Zinc stirs evenly under the speed of 600r/min,;The molar ratio of the amides compound and anhydrous zinc chloride is 1.13: 1。
The preparation method of aluminium chloride molten-salt electrolysis liquid is: by weight, by 90 parts of formamides, 120 parts of carbamides and 399 parts Anhydrous aluminum chloride stirs evenly under the speed of 600r/min,;Mole of the amides compound and anhydrous aluminum chloride Than for 1.34:1.
Reference example 2
The preparation method of zinc chloride molten-salt electrolysis liquid is: by weight, by 90 parts of formamides, 146 parts of propionamides and 480 parts Anhydrous zinc chloride stirs evenly under the speed of 500r/min,;Mole of the amides compound and anhydrous zinc chloride Than for 1.13:1.
The preparation method of aluminium chloride molten-salt electrolysis liquid is: by weight, by 90 parts of formamides, 146 parts of propionamides and 390 parts Anhydrous aluminum chloride stirs evenly under the speed of 500r/min,;Mole of the amides compound and anhydrous aluminum chloride Than for 1.37:1.
Reference example 3
The preparation method of zinc chloride molten-salt electrolysis liquid is: by weight, by 146 parts of propionamides, 120 parts of carbamides and 480 Part anhydrous zinc chloride stirs evenly under the speed of 700r/min,;The amides compound and anhydrous zinc chloride rub You are than being 1.13:1.
The preparation method of aluminium chloride molten-salt electrolysis liquid is: by weight, by 146 parts of propionamides, 120 parts of carbamides and 390 Part anhydrous aluminum chloride stirs evenly under the speed of 700r/min,;The amides compound and anhydrous aluminum chloride rub You are than being 1.37:1.
Intercalation Zn-Al alloy powder embodiment 1
(1) 1 zinc chloride molten-salt electrolysis liquid of 100kg reference example and 1 aluminium chloride molten-salt electrolysis liquid of 160kg reference example are mixed, It is stirred evenly under the revolving speed of 300r/min, obtains fused salt mixt electrolyte;
(2) using copper sheet as cathode, graphite is anode, is placed in fused salt mixt electrolyte obtained by step (1), and it is heavy to carry out electricity Product, the electro-deposition use constant potential mode, specifically: initial electro-deposition current potential is -0.20V, after electro-deposition 45min, switching Electro-deposition current potential is -0.40V, and after electro-deposition 45min, then switching back into electro-deposition current potential is -0.20V, and such cyclic switching electricity is heavy Product current potential carries out electro-deposition 6h;
(3) copper sheet after step (2) electro-deposition is taken out, is rinsed with water copper sheet, first use the deposit under rinsing Acetone, clear water successively rinse, then by the deposit rinsed teflon membrane filter filter 23, vacuum drying obtains intercalation Zn-Al alloy powder 1, partial size are 3~5 μm, purity >=99.995%.
By Fig. 1,2 it is found that the how oval flakey of the alloy powder deposited, the oval featheriness in part are dividing In the scanning electron microscope that resolution is 1 μm, it can be seen that the metal powder surface of deposition is coarse, and there are many places protrusions, shows deposition process In, alloy is to continue what growth around was formed using deposited particle as crystal grain.
Intercalation Zn-Al alloy powder embodiment 2
(1) 2 zinc chloride molten-salt electrolysis liquid of 100kg reference example and 2 aluminium chloride molten-salt electrolysis liquid of 100kg reference example are mixed, It is stirred evenly under the revolving speed of 250r/min, obtains fused salt mixt electrolyte;
(2) using copper sheet as cathode, graphite is anode, is placed in fused salt mixt electrolyte obtained by step (1), and it is heavy to carry out electricity Product, the electro-deposition use constant potential mode, specifically: initial electro-deposition current potential is -0.40V, after electro-deposition 40min, switching Electro-deposition current potential is -0.20V, and after electro-deposition 40min, then switching back into electro-deposition current potential is -0.40V, and such cyclic switching electricity is heavy Product current potential carries out electro-deposition 5h;
(3) copper sheet after step (2) electro-deposition is taken out, is rinsed with water copper sheet, first use the deposit under rinsing Acetone, clear water successively rinse, then by the deposit rinsed teflon membrane filter filter 23, vacuum drying obtains intercalation Zn-Al alloy powder 2, partial size are 3~5 μm, purity >=99.995%.
Intercalation Zn-Al alloy powder embodiment 3
(1) 3 zinc chloride molten-salt electrolysis liquid of 100kg reference example and 3 aluminium chloride molten-salt electrolysis liquid of 100kg reference example are mixed, It is stirred evenly under the revolving speed of 350r/min, obtains fused salt mixt electrolyte;
(2) using copper sheet as cathode, graphite is anode, is placed in fused salt mixt electrolyte obtained by step (1), and it is heavy to carry out electricity Product, the electro-deposition use constant potential mode, specifically: initial electro-deposition current potential is -0.40V, after electro-deposition 50min, switching Electro-deposition current potential is -0.20V, and after electro-deposition 50min, then switching back into electro-deposition current potential is -0.40V, and such cyclic switching electricity is heavy Product current potential carries out electro-deposition 7h;
(3) copper sheet after step (2) electro-deposition is taken out, is rinsed with water copper sheet, first use the deposit under rinsing Acetone, clear water successively rinse, then the deposit rinsed teflon membrane filter is filtered 4 times, and vacuum drying obtains intercalation Zn-Al alloy powder 3, partial size are 3~5 μm, purity >=99.995%.
Zinc-aluminium cooperates with anticorrosive paint Examples 1 to 4
Zinc-aluminium cooperates with anticorrosive paint Examples 1 to 4 raw material and its quality proportioning as shown in table 1.
1 zinc-aluminium of table cooperates with anticorrosive paint Examples 1 to 4 raw material and its quality proportioning table
Note: "-" expression is not added in table.
The preparation method Examples 1 to 4 of zinc-aluminium collaboration anticorrosive paint
According to table 1, respectively according to the raw material of Examples 1 to 4 and quality, anticorrosive packing is mixed with organic solvent, It is stirred under the revolving speed of 600r/min, anti-settling agent is added in whipping process, continue to stir with the revolving speed of 600r/min equal to dispersion It is even, electroconductive resin is added, is stirred evenly under the revolving speed of 1300r/min,.
Comparative example 1
(1) using copper sheet as cathode, graphite is anode, is placed in 651g aluminium chloride molten-salt electrolysis liquid, and electro-deposition is carried out, described Electro-deposition uses constant potential mode, in the case where electro-deposition current potential is -0.20V, electro-deposition 6h;
(2) copper sheet after step (1) electro-deposition is taken out, is rinsed with water copper sheet, by the deposit under rinsing with third Ketone, clear water successively rinse, then the deposit rinsed teflon membrane filter is filtered 2 times, and vacuum drying obtains refined aluminum Powder.
Refining aluminium powder obtained by 78kg is mixed with the molten acid anhydride acetic acid esters of 8kg butyl and 12kg butyl butyrate, 600r/min's It is stirred under revolving speed, 1.6kg polyamide wax and 0.4kg castor oil derivative is added in whipping process, continue to turn with 600r/min Speed stirring adds 50kg acrylic acid modified polyurethane, stirs evenly under the revolving speed of 1300r/min, obtain anti-to being uniformly dispersed Rotten coating.
Comparative example 2
(1) using copper sheet as cathode, graphite is anode, is placed in 732g zinc chloride molten-salt electrolysis liquid, and electro-deposition is carried out, described Electro-deposition uses constant potential mode, in the case where electro-deposition current potential is -0.40V, electro-deposition 6h;
(2) copper sheet after step (1) electro-deposition is taken out, is rinsed with water copper sheet, by the deposit under rinsing with third Ketone, clear water successively rinse, then by the deposit rinsed teflon membrane filter filter 23, vacuum drying obtains zinc concentrate Powder.
Refining zinc powder obtained by 78kg is mixed with the molten acid anhydride acetic acid esters of 8kg butyl and 12kg butyl butyrate, 600r/min's It is stirred under revolving speed, 1.6kg polyamide wax and 0.4kg castor oil derivative is added in whipping process, continue to turn with 600r/min Speed stirring adds 50kg acrylic acid modified polyurethane, stirs evenly under the revolving speed of 1300r/min, obtain anti-to being uniformly dispersed Rotten coating.
Comparative example 3
78kg zinc powder is mixed with the molten acid anhydride acetic acid esters of 8kg butyl and 12kg butyl butyrate, is stirred under the revolving speed of 600r/min Mix, 1.6kg polyamide wax and 0.4kg castor oil derivative be added in whipping process, continue to stir with the revolving speed of 600r/min to It is uniformly dispersed, adds 50kg acrylic acid modified polyurethane, stirred evenly under the revolving speed of 1300r/min, obtain anticorrosive paint.
Respectively by Examples 1 to 4 zinc-aluminium cooperate with anticorrosive paint, 1~3 anticorrosive paint of comparative example according to standard spray in 20 × On 40mm tinplate, control film thickness is 40 μm.Detect corresponding project according still further to following examination criteria: paint film adhesion (draws lattice Method): GB 9286-88;Paint film wearability (500g, 1000 turns): GB 1768-89;Relative density: GB 6750-86;Rotation is viscous Degree: GB 9751-88;Quality of materials solid content: GB 1725-79(89);Drying time (surface drying/do solid work): GB 1728-79 (89);Impact resistance: GB 1732-93;(abbreviation A, value are flat to friction plate (ball blast is not coated with material) anti-slip coefficient μ in table 1 Mean value), friction plate (50 μm of ball blast+sprayed on material) anti-slip coefficient μ (abbreviation B, value are average value in table 1), friction plate (70 μm of ball blast+sprayed on material) anti-slip coefficient μ (abbreviation C, value are average value in table 1): GB 50205-2001;Salt spray resistance Test: ASTM B117-94;Color and appearance: GB 1729-79.
The performance test results of each detection project are as shown in table 2.
2 Examples 1 to 4 zinc-aluminium of table cooperates with the performance test results after anticorrosive paint, 1~3 anticorrosive paint film of comparative example Table
By the performance test results after Examples 1 to 4 coating film in table 2 it is found that as zinc-aluminium intercalation alloy powder contains Amount reduces, and zinc powder, content of aluminium powder increase, and drying time improves, and corrosion resistance is declined and finally close to pure containing zinc The effect of coating, this shows that the anticorrosion ability of zinc-aluminium intercalation alloy powder is better than pure zinc and zinc/aluminium mixed system, and incites somebody to action Examples 1 to 4 with after 1~3 coating film of comparative example color and appearance compare, zinc-aluminium intercalation alloy powder is in film Still possess the shine characteristics of its raw material aluminium, there is certain decorative effect.
As shown in Table 2, the wearability of zinc-aluminium collaboration anticorrosive paint Examples 1 to 4 of the present invention is all between 1 refined aluminum of comparative example Between 3 zinc powder of powder and comparative example, this shows zinc-aluminium intercalation alloy to the wearability of film between pure zinc and fine aluminium;But it compares The corrosion resistance of salt spray test, zinc-aluminium intercalation alloy powder is better than pure zinc and fine aluminium, this shows that alloy powder is effectively realized Zinc, aluminium it is compound, form new potential difference internal, effectively hinder the appearance of corrosion phenomenon and the deterioration of extent of corrosion.
To sum up, zinc-aluminium intercalation alloy powder hardness between pure zinc and fine aluminium, after coating, can effectively adhere to In base layer of resin and play wear-resistant effect;Zinc, aluminium component in zinc-aluminium intercalation alloy powder are evenly distributed, and are formed in inside New potential difference, further can hinder electronics to conduct, and effectively hinder the appearance of corrosion phenomenon and the deterioration of extent of corrosion;Together When, zinc-aluminium intercalation alloy powder still possesses the shine characteristics of its raw material aluminium in film, has certain decorative effect.

Claims (10)

1. a kind of preparation method of intercalation Zn-Al alloy powder, which comprises the following steps:
(1) zinc chloride molten-salt electrolysis liquid and aluminium chloride molten-salt electrolysis liquid are mixed, stirs evenly, obtains fused salt mixt electrolyte;
(2) using copper sheet as cathode, graphite is anode, is placed in fused salt mixt electrolyte obtained by step (1) and carries out electro-deposition;It is described Electro-deposition uses constant potential mode, specifically: initial electro-deposition current potential is -0.15~-0.45V, after 30~60min of electro-deposition, Switching electro-deposition current potential is -0.15~-0.45V, after 30~60min of electro-deposition, then switch back into electro-deposition current potential be -0.15~- 0.45V, such cyclic switching electro-deposition current potential carry out 4~8h of electro-deposition;It is different with the electro-deposition current potential after switching before switching;
(3) copper sheet after step (2) electro-deposition is taken out, is rinsed with water copper sheet, the deposit cleaning under rinsing, mistake Filter, vacuum drying, obtain intercalation Zn-Al alloy powder.
2. the preparation method of intercalation Zn-Al alloy powder according to claim 1, it is characterised in that: in step (1), the chlorine Change zinc molten-salt electrolysis liquid to be formulated by amides compound and anhydrous zinc chloride with molar ratio 1:1.1~1.5, the aluminium chloride Molten-salt electrolysis liquid is formulated by amides compound and anhydrous aluminum chloride with molar ratio for 1:1.0~1.5.
3. the preparation method of intercalation Zn-Al alloy powder according to claim 1 or claim 2, it is characterised in that: in step (1), institute It states zinc chloride molten-salt electrolysis liquid and is mixed with aluminium chloride molten-salt electrolysis liquid with mass ratio 1:1~2;The speed of the stirring be 200~ 800r/min。
4. a kind of zinc-aluminium cooperates with anticorrosive paint, which is characterized in that including following raw material: anticorrosive packing, organic solvent, anti-settling agent and Electroconductive resin;The anticorrosive packing be one of claims 1 to 3 gained intercalation Zn-Al alloy powder or in zinc powder, aluminium powder One or two kinds of mixtures.
5. zinc-aluminium cooperates with anticorrosive paint according to claim 4, which is characterized in that the parts by weight of each raw material are as follows: anticorrosive packing 50~120 parts, 5~30 parts of organic solvent, 1~5 part of anti-settling agent, 10~60 parts of electroconductive resin;Wherein, contain in the anticorrosive packing It has the right to require one of 1~3 15~80 parts of gained intercalation Zn-Al alloy powder, 0~40 part of zinc powder, 0~20 part of aluminium powder.
6. zinc-aluminium according to claim 4 or 5 cooperates with anticorrosive paint, it is characterised in that: the intercalation Zn-Al alloy powder Partial size is 3~5 μm, purity >=99.995%, in oval featheriness or oval flakey;The organic solvent is the molten acid anhydride second of butyl One or more of acid esters, glycol ethyl ether acetate ester, isophorone, butyl butyrate, dimethylbenzene or dimethylformamide;It is described Anti-settling agent is one or more of polyamide wax, polyolefin-wax, castor oil derivative or organobentonite.
7. zinc-aluminium according to claim 4 or 5 cooperates with anticorrosive paint, it is characterised in that: the electroconductive resin is to contain conduction The resin of filler graphene, wherein mass content of the graphene in electroconductive resin is 0.5~1.5%;In the electroconductive resin Resin be answering for one or both of epoxy resin, polystyrene, polyurethane or acrylic resin or in which two kinds of resins Close modified resin.
8. zinc-aluminium cooperates with anticorrosive paint according to claim 6, it is characterised in that: the electroconductive resin is to contain conductive filler The resin of graphene, wherein mass content of the graphene in electroconductive resin is 0.5~1.5%;Tree in the electroconductive resin Rouge is that one or both of epoxy resin, polystyrene, polyurethane or acrylic resin or in which two kinds of the compound of resin change Property resin.
9. the preparation method of the collaboration anticorrosive paint of the zinc-aluminium according to one of claim 4~8, which is characterized in that including following Step: anticorrosive packing is mixed with organic solvent, anti-settling agent is added in whipping process, is stirred evenly, adds conductive tree Rouge stirs evenly,.
10. according to claim 9 zinc-aluminium collaboration anticorrosive paint preparation method, it is characterised in that: be added electroconductive resin it Preceding mixing speed is 500~700r/min, and the mixing speed after addition electroconductive resin is 1000~1500r/min.
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