CN106967985A - A kind of aqueous chromium-free anticorrosive paint and preparation method thereof - Google Patents
A kind of aqueous chromium-free anticorrosive paint and preparation method thereof Download PDFInfo
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- CN106967985A CN106967985A CN201710333338.2A CN201710333338A CN106967985A CN 106967985 A CN106967985 A CN 106967985A CN 201710333338 A CN201710333338 A CN 201710333338A CN 106967985 A CN106967985 A CN 106967985A
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F13/00—Inhibiting corrosion of metals by anodic or cathodic protection
- C23F13/02—Inhibiting corrosion of metals by anodic or cathodic protection cathodic; Selection of conditions, parameters or procedures for cathodic protection, e.g. of electrical conditions
- C23F13/06—Constructional parts, or assemblies of cathodic-protection apparatus
- C23F13/08—Electrodes specially adapted for inhibiting corrosion by cathodic protection; Manufacture thereof; Conducting electric current thereto
- C23F13/12—Electrodes characterised by the material
- C23F13/14—Material for sacrificial anodes
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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
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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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
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The present invention relates to Metal surface anti-corrosion technical field of coatings there is provided a kind of aqueous chromium-free anticorrosive paint and preparation method thereof, its raw material count by weight including：150 300 parts of aluminium zinc-magnesium silicon multicomponent alloy powder, 5 20 parts of modified nano powder, 50 100 parts of epoxy silane coupling, 5 15 parts of chelating type phosphate titanium coupling agent, 60 120 parts of ethylene glycol, 25 200 parts of silane hydrolyzate auxiliary agent, 4 6.5 parts of thickener, 0.5 1 parts of defoamer, 18 36 parts of polysorbas20,9 18 parts of phosphomolybdate, quaternary ammonium salt titanate esters are 10 30 parts, and wherein aluminium zinc-magnesium silicon multicomponent alloy powder includes aluminium, magnesium, silicon, zinc and auxiliary element.The aqueous chromium-free anticorrosive paint antiseptic property is good, and hardness is high.
Description
Technical field
The present invention relates to Metal surface anti-corrosion technical field of coatings, in particular to a kind of aqueous chromium-free anticorrosive paint
And preparation method thereof.
Background technology
Engineer equipment is often corroded by salt fog, airflow scouring in coastal waters and ocean, and Service Environment is exceedingly odious, marine climate resistant
The long-life problems demand of corrosion resistant coating is solved.At present, hot dip Al-Zn-Si alloys and Dacromet/steel have turned into domestic exogenous wind
Electric metal part marine climate resistant corrosion long-life protection mainstream technology.
But, hot galvalizing alloy coating process, equip more complicated, technological temperature it is high (>800 DEG C), easily cause part oxidation change
Flue dust, dust, metal fever steam contamination are serious in shape, and operating process；In addition, wearability is not enough, erosion resistance is not strong；No
Being applicable the processing of large area workpiece and field work is restricted its application.Dacroment (Dacromet) is also known as zinc-chromium coating, is
A kind of coating of high anticorrosive property energy.Compared with the techniques such as traditional electrogalvanizing, galvanizing, with environmental pollution it is small, protection
Performance is good, without hydrogen embrittlement, high temperature resistant the features such as, be referred to as " green production " technology of surface treatment.But in traditional Dacroment liquid also
Contain about 2% Cr6+, Cr VI strong toxicity, to human and environment harm greatly.Some related laws and regulations are promulgated both at home and abroad
Come the use for limiting or forbidding Cr VI, therefore, surface treatment Trend of Chrome-free turns into global development trend.
Both at home and abroad in recent years on the basis of research Dacroment corrosion resistance mechanism, the ions of Cr containing sexavalence in formula are actively found
The substitute of chromate, has born first fruit, but formulation for coating material and technique still need to further optimization, and corrosion fatigue life must enter one
Step is improved.Wherein, aqueous chromium-free Aluminum Coating as Dacroment (zinc-aluminium chrome coating) substitute, without using organic solvent, no
It is a kind of more environmentally-friendly surface treatment system containing poisonous metal (such as nickel, lead, barium and mercury) and Cr VI or trivalent chromium.
In order to improve the anti-corrosive properties of aqueous chromium-free zinc-aluminium masking liquid system, made using a variety of organic/inorganic many kinds of substance compounding
With, but painting cost is added while performance boost, and bring larger difficulty to the compatibility and stability of system.Cause
This, only can not meet requirement by improvement chromic anhydride substitute materials to improve the corrosion resistance of Non-chromium Zn-al Coating.Traditional Chrome-free
Aluminum Coating using zinc-aluminium mixed powder as pigment, Aluminum Coating have concurrently spelter coating cathodic protection ability and aluminized coating it is high resistance to
Corrosion energy, and its corrosion resistance strengthens with the raising of aluminium content within the specific limits.Zinc powder and aluminium powder in high alumina powder content masking liquid
Be completely dispersed uniform extremely difficult, inevitably there is local aluminium powder enrichment phenomenon, cause local significantly poor zinc, it is chloride from
In sub- corrosive environment, Pin Xin areas can not provide effective cathodic protection, and this can cause the Aluminum Coating premature failure of high aluminium content.
The protection mechanism of rich aluminium aqueous chromium-free Aluminum Coating is mainly the passivation of corrosion products film in the invention of prior art, and applies
Layer sacrificial anode effect is weaker, and the effect of coating sacrificial anode is weaker, and coating marine climate resistant corrosion life can be caused significantly to drop
It is low.
The content of the invention
The invention provides a kind of aqueous chromium-free anticorrosive paint, it is intended to improves existing aqueous chromium-free Aluminum Coating and contains in aluminium
Sacrificial anode effect is weaker under conditions of amount is high causes coating antiseptic property under chloride ion-containing corrosive environment is more general to ask
Topic.
Present invention also offers a kind of preparation method of aqueous chromium-free anticorrosive paint, it is intended to which preparing can improve existing
Sacrificial anode effect is weaker under conditions of aluminium content is high causes coating in chloride ion-containing corrosive environment for aqueous chromium-free Aluminum Coating
The anticorrosive paint for the problem of lower antiseptic property is more general.
What the present invention was realized in：
A kind of aqueous chromium-free anticorrosive paint, its raw material count by weight including：Aluminium zinc-magnesium silicon multicomponent alloy powder 150-
300 parts, 5-20 parts of modified nano powder, 50-100 parts of epoxy silane coupling, 5-15 parts of chelating type phosphate titanium coupling agent,
60-120 parts of ethylene glycol, 25-200 parts of silane hydrolyzate auxiliary agent, 4-6.5 parts of thickener, 0.5-1 parts of defoamer, polysorbas20 18-36
Part, 9-18 parts of phosphomolybdate, quaternary ammonium salt titanate esters are 10-30 parts, and wherein aluminium zinc-magnesium silicon multicomponent alloy powder includes aluminium, magnesium, silicon, zinc
And auxiliary element, aluminium, magnesium, silicon, the mass ratio of zinc and auxiliary element are 55.5-75：3.2-9.6：0.35-5.7：18.22-
40.87：0.08-5.5, auxiliary element is Ni, Mn, Ti, Ag, Zr, La, Ce, Pr, Nd, Sc, Er and Y at least one.
A kind of method for preparing above-mentioned aqueous chromium-free anticorrosive paint, including：
Polysorbas20, chelating type phosphate titanium coupling agent, quaternary ammonium salt titanate esters and ethylene glycol are dissolved in the first deionized water
Agitating solution is to thick；Continue whipping process in sequentially add modified nano powder, aluminium zinc-magnesium silicon multicomponent alloy powder and
Defoamer is uniform to slurry, and adds into uniform slurry epoxy silane coupling, silane hydrolyzate auxiliary agent, phosphomolybdate
The aqueous solution and thickener.
The beneficial effects of the invention are as follows：The aqueous chromium-free anticorrosive paint that the present invention is obtained by above-mentioned design, in use, this
Invent the coating that the aqueous chromium-free anticorrosive paint provided by alloy in the inner there is preferable composition proportion its coating is formed
With higher aluminium content ensure that it is higher it is corrosion proof under the premise of, maintaining corrosion products film there is preferably passivation to make
On the basis of, the effect of coating sacrificial anode is further increased so that even if coating aluminium content height is not easy to occur spot corrosion,
Corrosion resisting property of the coating under chloride ion-containing environment is significantly improved, while the assistant metal element added can be carried further
The hardness and corrosion resistance of high coating.The method for the preparation aqueous chromium-free anticorrosive paint that the present invention is provided, can be prepared above-mentioned anti-
The aqueous chromium-free anticorrosive paint that corrosive nature is good, hardness is high.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer
Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment
The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, are the conventional production that can be obtained by commercially available purchase
Product.
Aqueous chromium-free anticorrosive paint provided in an embodiment of the present invention and preparation method thereof is specifically described below.
A kind of aqueous chromium-free anticorrosive paint, its raw material count by weight including：Aluminium zinc-magnesium silicon multicomponent alloy powder 150-
300 parts, 5-20 parts of modified nano powder, 50-100 parts of epoxy silane coupling, 5-15 parts of chelating type phosphate titanium coupling agent,
60-120 parts of ethylene glycol, 25-200 parts of silane hydrolyzate auxiliary agent, 4-6.5 parts of thickener, 0.5-1 parts of defoamer, polysorbas20 18-36
Part, 9-18 parts of phosphomolybdate, quaternary ammonium salt titanate esters are 10-30 parts, and wherein aluminium zinc-magnesium silicon multicomponent alloy powder includes aluminium, magnesium, silicon, zinc
And auxiliary element, aluminium, magnesium, silicon, the mass ratio of zinc and auxiliary element are 55.5-75：3.2-9.6：0.35-5.7：18.22-
40.87：0.08-5.5, auxiliary element is Ni, Mn, Ti, Ag, Zr, La, Ce, Pr, Nd, Sc, Er and Y at least one.Aqueous nothing
Each composition interacts under conditions of with preferably ratio in chromium anticorrosive paint so that aqueous chromium-free anti-corrosion paint shape
Into the good hardness of coating antiseptic performance it is high.
Mg elements can reduce the corrosion potential of alloy coat in Al-Zn-Si alloys, and the cathodic protection for improving coating is made
With Mg2Si compares MgZn2More longlasting cathodic protection mutually can be provided.And auxiliary element is added in alloyed powder and is conducive to improving painting
Expect the corrosion resistance and hardness of coating being made.
Further, aluminium zinc-magnesium silicon multicomponent alloy powder is flakey, and the alloyed powder of flakey is parallel to each other or overlapping arrangement,
A lot of scale protective barrier is formed, delays corrosive medium to reach the time of substrate surface through coating, so as to substantially prolongs
The service life of base material.Further, the aluminium zinc-magnesium silicon multicomponent alloy powder piece footpath of the flakey is less than 20 μm, and piece thickness is less than 0.5 μ
M, draw ratio is more than 30.The coating physical shielding that the alloyed powder of the flakey of this size arranges even closer formation each other is made
It is higher with more preferable, hardness.
The hardness of Non-chromium Zn-al Coating is low, anti-blown sand aggressivity is poor, under the premise of corrosion resistance coating is not reduced, and adds
Some nanometer of hard particles are to improve the mechanical property of coating, but nanoparticle surface can be high, easily reunites, in medium
In be difficult to disperse, the nano-particle of reunion can increase the porosity of coating, decline the barrier propterty of coating.Therefore, to avoid
Because of the phenomenon of nanoparticle spontaneous reunion because of surface energy height, the present invention uses modified nano powder.It is nano powder modified to refer to
Particle surface is handled with material, chemical method, purposefully changes the physicochemical properties of particle surface, such as surface is former
Response characteristic such as sublayer structure and functional group, surface hydrophobic, electricity, chemisorbed etc..Modified nano-powder, which has, to be divided
Scattered property is good, and good surface activity, compatibility is good, the advantages of performance such as fast light, UV resistant, heat-resisting, weather-proof is good.
Further, modified nano powder includes modified nano-ZnO powder and modified Nano TiO2Powder, modified Nano two
Titanium oxide powder inherently has high antiseptic property, and modified zinc oxide can prevent powder from the phenomenon reunited and change occur
Learn property stable.Further, modified nano-ZnO powder and modified Nano TiO2The mass ratio of powder is 1:1-3, the ratio
Modified nano-ZnO powder and modified Nano TiO2Powder, which cooperates, can strengthen the stability and anti-corrosive properties of paint coatings.
Polysorbas20 alias polyoxyethylene 20 sorbitan monolaurate, molecular formula C58H114O26, it is sorbierite and one
Dehydration, double dehydration compounds and laurate exist by every mole of sorbierite and its anhydro compounds and about 20 moles of oxirane
It is condensed and is made under alkalescence condition.Thickener is a kind of auxiliary rheological agents, can not only thicken coating, prevents from flowing in construction
Phenomenon is hung, and the excellent mechanical performance of coating and bin stability can be assigned.For the relatively low water paint of viscosity, it is
A very important analog assistant.Defoamer, which is added into mixed solution, can reduce surface tension, suppress foam and produce or eliminate
Foam is produced.
Using Al-Zn-Mg-Si multicomponent alloy powders because it has said ratio, coating is set to realize alloy coat sacrifice
The best of breed of anode cathode protection mechanism and corrosion product passivation mechanisms, and Al-Zn-Mg-Si multicomponent alloy powders with it is above-mentioned
The mating reaction of each component is being maintained on the basis of corrosion products film has preferable passivation, further increases coating
The effect of sacrificial anode, significantly improves corrosion resistance of the coating under chloride environment.
Coupling agent is referred to as " molecular bridge ", to improve the interface interaction between inorganic matter and organic matter, so as to carry significantly
The performance of high composite, such as physical property, electrical property, hot property, optical property, antiseptic property, while being also prevented from it
Its medium improves interface state, is conducive to the ageing-resistant of product, proof stress and electrical insulation capability to contacting permeation.And above-mentioned idol
Connection agent with the component of when composition for the performance of the more preferably enhancing aqueous chromium-free anticorrosive paint of the invention provided.Chelating
Type phosphate titanium coupling agent makees adhesive promoter in component, can strengthen the adhesive force of coating.And the quaternary ammonium salt in component
Titanate esters can not only be used for crosslinking agent also can be as coupling agent, and it can make water paint, ink adhesion enhancing.Due to silanes
Coupling agent is most common coupling agent, in the case of from silane coupling agent, and hydrolysis auxiliary agent selection silane hydrolyzate auxiliary agent is used
To help silane hydrolyzate.Hydrolyze auxiliary agent：To promote the auxiliary agent that other compositions are hydrolyzed in component.Preferably, silane hydrolyzate auxiliary agent is
Methanol or ethanol.Methanol and ethanol are most commonly seen auxiliary agent and cheap easy purchase.It should be noted that in the present invention
Other embodiment in silane hydrolyzate auxiliary agent can also be other small molecule unit alcohol.
A kind of method for preparing aqueous chromium-free anticorrosive paint, including：
S1, polysorbas20, chelating type phosphate titanium coupling agent, quaternary ammonium salt titanate esters and ethylene glycol is dissolved in the first deionized water
Middle agitating solution is to thick.
First, using 150-300 parts of balance precise aluminium zinc-magnesium silicon multicomponent alloy powder, 5-20 parts of modified nano powder,
50-100 parts of epoxy silane coupling, 5-15 parts of chelating type phosphate titanium coupling agent, 60-120 parts of ethylene glycol, silane hydrolyzate are helped
25-200 parts of agent, 4-6.5 parts of thickener, 0.5-1 parts of defoamer, 18-36 parts of polysorbas20,9-18 parts of phosphomolybdate, quaternary ammonium salt titanium
Acid esters be 10-30 part and deionized water it is enough be positioned in the dry environment of laboratory be used to it is standby.
It is the first deionized water to take a part of deionized water, by polysorbas20, chelating type phosphate titanium coupling agent, quaternary ammonium salt titanium
Acid esters and ethylene glycol, are dissolved in the first deionized water in 20-30 DEG C of agitating solution of room temperature or water-bath to thick, stir to sticky
Each composition is well mixed substantially during shape.
S2, continue whipping process in sequentially add modified nano powder, aluminium zinc-magnesium silicon multicomponent alloy powder and defoamer
It is uniform to slurry.
Specifically, continue above-mentioned viscous liquid being stirred under conditions of 20-30 DEG C of room temperature or water-bath, and according to
Secondary load weighted modified nano powder, aluminium zinc-magnesium silicon multicomponent alloy powder and defoamer to the slurry that added into reaction vessel mixes equal
It is even.
S3 simultaneously adds epoxy silane coupling, silane hydrolyzate auxiliary agent, the aqueous solution of phosphomolybdate into uniform slurry
And thickener.
Specifically, continue stirring under conditions of 20-30 DEG C of room temperature or water-bath to well mixed slurry, and add thereto
Enter the aqueous solution and thickener of epoxy silane coupling, silane hydrolyzate auxiliary agent, phosphomolybdate.
Preferably, it is with the mode in the uniform slurry of silane hydrolyzate auxiliary agent addition by epoxy silane coupling：By ring
TMOS coupling agent is dissolved in the second deionized water with silane hydrolyzate auxiliary agent is well mixed to obtain transparent settled solution, will be transparent clear
Clear solution, the aqueous solution of phosphomolybdate and thickener are sequentially added to be continued to stir in uniform slurry.Preferably, the second deionization
The mass ratio of water, silane hydrolyzate auxiliary agent and epoxy silane coupling is 2-3.5：0.5-2:1, when the second deionized water, silane
The ratio of auxiliary agent and epoxy silane coupling is hydrolyzed in this scope most beneficial for enough silanol monomers are obtained, to ensure silane
Quality of forming film of the coupling agent in material surface.
The feature and performance to the present invention are described in further detail with reference to embodiments.
Embodiment 1
It is 55.5 to weigh aluminium, magnesium, silicon, zinc and manganese mass ratio:3.2:0.35:18.22:0.08 aluminium zinc-magnesium silicon multicomponent alloy
Powder 150g, modified nano-ZnO powder and modified Nano TiO2The mass ratio of powder is 1:1 modified nano powder 5g, γ-shrink
Glycerine ether oxygen propyl trimethoxy silicane 100g, chelating type phosphate titanium coupling agent 5g, ethylene glycol 60g, methanol 50g, thickener
4g, defoamer 0.5g, polysorbas20 18g, sodium phosphomolybdate 9g, quaternary ammonium salt titanate esters are 10g, deionized water 963.5g.Wherein aluminium zinc
Magnesium silicon multicomponent alloy powder piece footpath is less than 20 μm, and piece thickness is less than 0.5 μm, and draw ratio is more than 30.
By chelating type phosphate titanium coupling agent, polysorbas20, quaternary amine titanate esters are added sequentially to 613.5g's with ethylene glycol
In first deionized water, it is stirred at room temperature to clear viscous shape；Sequentially add modified nano-ZnO powder and modified Nano
TiO2Powder stirs 40min, then adds aluminium zinc-magnesium silicon multicomponent alloy powder and defoamer, persistently stirs 60min equal to slurry
It is even；γ-glycidyl ether oxygen propyl trimethoxy silicane and methanol are dissolved in the deionized waters of 350g second, stirred at room temperature
Mix, until obtaining the hydrolyzed silane solution of clear, this hydrolyzed silane solution is added 30min to two is stirred in above-mentioned uniform slurry
After person is well mixed, then adds thereto and add thickener after the solution that sodium phosphomolybdate is configured to is sufficiently stirred for and continue stirring 5
Aqueous chromium-free anticorrosive paint is obtained after hour.
After obtained aqueous chromium-free anti-corrosion paint to matrix surface, the preliminary drying 8-10min at 110 DEG C then divides
Do not solidify 25min at 290 DEG C, finally obtain nano modification Chrome-free high alumina Al-Zn-Mg-Si alloy coats.
It is 0 grade to survey adhesion by the gained coating cross-hatching of embodiment 1, and 12-15 μm of coating layer thickness, resistance to 10% salt solution exceedes
160d, salt spray test is more than 1950h, and hardness enters table 2 more than 210HV0.005, and by data record.
Embodiment 2
It is 75 to weigh aluminium, magnesium, silicon, zinc and silver-colored mass ratio:9.6:5.7:40.87:5.5 aluminium zinc-magnesium silicon multicomponent alloy powder
210g, modified nano-ZnO powder and modified Nano TiO2The mass ratio of powder is 1:3 modified nano powder 16g, β-(3,4-
Epoxycyclohexyl) ethyl trimethoxy silane 50g, chelating type phosphate titanium coupling agent 15g, ethylene glycol 80g, ethanol 100g, increase
Thick dose of 5g, defoamer 0.7g, polysorbas20 22g, phosphomolybdic acid potassium 18g, quaternary ammonium salt titanate esters are 15g, deionized water 618.3g.Its
Middle aluminium zinc-magnesium silicon multicomponent alloy powder piece footpath is less than 20 μm, and piece thickness is less than 0.5 μm, and draw ratio is more than 30.
By chelating type phosphate titanium coupling agent, polysorbas20, quaternary amine titanate esters and ethylene glycol are added sequentially to 468.3g the
In one deionized water, it is stirred at room temperature to clear viscous shape；Sequentially add modified nano-ZnO powder and modified Nano TiO2
Powder stirs 30min, then adds aluminium zinc-magnesium silicon multicomponent alloy powder and defoamer, persistently stirs 30min uniform to slurry；Will
β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane and methanol are dissolved in the deionized waters of 150g second, are stirred at room temperature,
Hydrolyzed silane solution up to obtaining clear, will stir 20min both in the above-mentioned uniform slurry of this hydrolyzed silane solution addition
After well mixed, then add thickener is added after the solution that sodium phosphomolybdate is configured to is sufficiently stirred for and to continue stirring 6 small thereto
When after obtain aqueous chromium-free anticorrosive paint.
After obtained aqueous chromium-free anti-corrosion paint to matrix surface, the preliminary drying 8-10min at 110 DEG C then divides
Do not solidify 25min at 290 DEG C, then solidify 25min at 290 DEG C or so respectively, finally obtain nanometer modified aqueous Chrome-free high alumina
Al-Zn-Mg-Si corrosion-inhibiting coatings.
It is 0 grade to survey adhesion by the gained coating cross-hatching of embodiment 2, and coating layer thickness is about 12-15 μm, resistance to 10% salt solution
More than 150d, salt spray test is more than 1910h, and hardness is more than 214HV0.005.And data record is entered into table 2.
Embodiment 3
It is 56 to weigh aluminium, magnesium, silicon, zinc, nickel and ytterbium mass ratio:4.4:4:20.23:5.5:0.5 aluminium zinc-magnesium silicon is polynary to be closed
Bronze 300g, modified nano-ZnO powder and modified Nano TiO2The mass ratio of powder is 1:3 modified nano powder 20g, γ-
Glycidyl ether oxygen propyl trimethoxy silicane 100g, chelating type phosphate titanium coupling agent 5g, methanol 100g, ethylene glycol 120g,
Thickener 6.5g, defoamer 1g, polysorbas20 36g, sodium phosphomolybdate 18g, quaternary ammonium salt titanate esters are 30g, deionized water 613.5g.
Wherein aluminium zinc-magnesium silicon multicomponent alloy powder piece footpath is less than 20 μm, and piece thickness is less than 0.5 μm, and draw ratio is more than 30.
By chelating type phosphate titanium coupling agent, polysorbas20, quaternary amine titanate esters and ethylene glycol are added sequentially to 263.5g the
In one deionized water, it is stirred at room temperature to clear viscous shape；Sequentially add modified nano-ZnO powder and modified Nano TiO2
Powder stirs 40min, then adds aluminium zinc-magnesium silicon multicomponent alloy powder and defoamer, persistently stirs 60min uniform to slurry；Will
γ-glycidyl ether oxygen propyl trimethoxy silicane and methanol are dissolved in the deionized waters of 350g second, are stirred at room temperature, until
The hydrolyzed silane solution of clear is obtained, this hydrolyzed silane solution is added into stirring 30min in above-mentioned uniform slurry mixes both
After uniform, then after adding thereto and adding thickener after the solution that sodium phosphomolybdate is configured to is sufficiently stirred for and continue stirring 5 hours
Obtain aqueous chromium-free anticorrosive paint.
After obtained aqueous chromium-free anti-corrosion paint to matrix surface, the preliminary drying 8-10min at 110 DEG C then divides
Do not solidify 25min at 290 DEG C, then solidify 25min at 290 DEG C or so respectively, finally obtain nanometer modified aqueous Chrome-free high alumina
Al-Zn-Mg-Si-Ni-Y corrosion-inhibiting coatings.
When by the gained coating cross-hatching of embodiment 3, to survey adhesion be 0 grade, 12-15 μm of coating layer thickness, resistance to 10% salt solution surpasses
145 are crossed, salt spray test is more than 1850h, and hardness is more than 209HV0.005.And data record is entered into table 2.
Embodiment 4
It is 65 to weigh aluminium, magnesium, silicon, zinc, Ti and Zr mass ratioes:9.5:5.5:19.26:0.5:1 aluminium zinc-magnesium silicon is polynary to be closed
Bronze 200g, modified nano-ZnO powder and modified Nano TiO2The mass ratio of powder is 1:1 modified nano powder 20g, β-
(3,4- epoxycyclohexyl) ethyl trimethoxy silane 50g, chelating type phosphate titanium coupling agent 15g, methanol 50g, ethylene glycol
80g, thickener 5g, defoamer 0.8g, polysorbas20 18g, sodium phosphomolybdate 12g, quaternary ammonium salt titanate esters are 30g, deionized water
619.2g.Wherein aluminium zinc-magnesium silicon multicomponent alloy powder piece footpath is less than 20 μm, and piece thickness is less than 0.5 μm, and draw ratio is more than 30.
By chelating type phosphate titanium coupling agent, polysorbas20, quaternary amine titanate esters and ethylene glycol are added sequentially to 519.2g the
In one deionized water, it is stirred at room temperature to clear viscous shape；Sequentially add modified nano-ZnO powder and modified Nano TiO2
Powder stirs 30min, then adds aluminium zinc-magnesium silicon multicomponent alloy powder and defoamer, persistently stirs 30min uniform to slurry；Will
β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane and methanol are dissolved in the deionized waters of 100g second, are stirred at room temperature,
Hydrolyzed silane solution up to obtaining clear, will stir 20min both in the above-mentioned uniform slurry of this hydrolyzed silane solution addition
After well mixed, then add thickener is added after the solution that sodium phosphomolybdate is configured to is sufficiently stirred for and to continue stirring 6 small thereto
When after obtain aqueous chromium-free anticorrosive paint.
After obtained aqueous chromium-free anti-corrosion paint to matrix surface, preliminary drying 8-10min, then exists at 110 DEG C
290 DEG C or so solidification 25min, finally obtain nanometer modified aqueous Chrome-free high alumina Al-Zn-Mg-Si-Ti-Zr corrosion-inhibiting coatings.
When by the gained coating cross-hatching of embodiment 4, to survey adhesion be 0 grade, 12-15 μm of coating layer thickness, resistance to 10% salt solution surpasses
150d is crossed, salt spray test is more than 1900h, and hardness is more than 215HV0.005.And data record is entered into table 2.
Embodiment 5
It is 70 to weigh aluminium, magnesium, silicon, zinc, La and Y mass ratioes:4.6:0.5:30:0.5:1 aluminium zinc-magnesium silicon multicomponent alloy powder
150g, modified nano-ZnO powder and modified Nano TiO2The mass ratio of powder is 1:1 modified nano powder 10g, β-(3,4-
Epoxycyclohexyl) ethyl trimethoxy silane 50g, chelating type phosphate titanium coupling agent 10g, methanol 50g, ethylene glycol 60g, thickening
Agent 4.5g, defoamer 1g, polysorbas20 20g, sodium phosphomolybdate 10g, quaternary ammonium salt titanate esters are 10g, deionized water 779.5g.Wherein
Aluminium zinc-magnesium silicon multicomponent alloy powder piece footpath is less than 15 μm, and piece thickness is less than 0.5 μm, and draw ratio is more than 60.
By chelating type phosphate titanium coupling agent, polysorbas20, quaternary amine titanate esters and ethylene glycol are added sequentially to 629.5g the
In one deionized water, it is stirred at room temperature to clear viscous shape；Sequentially add modified nano-ZnO powder and modified Nano TiO2
Powder stirs 30min, then adds aluminium zinc-magnesium silicon multicomponent alloy powder and defoamer, persistently stirs 60min uniform to slurry；Will
β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane and methanol are dissolved in the deionized waters of 150g second, are stirred at room temperature,
Hydrolyzed silane solution up to obtaining clear, will stir 20min both in the above-mentioned uniform slurry of this hydrolyzed silane solution addition
After well mixed, then add thickener is added after the solution that sodium phosphomolybdate is configured to is sufficiently stirred for and to continue stirring 10 small thereto
When after obtain aqueous chromium-free anticorrosive paint.
After obtained aqueous chromium-free anti-corrosion paint to matrix surface, the preliminary drying 15min at 95 DEG C, then 285
Solidify 30min at DEG C, finally obtain nanometer modified aqueous Chrome-free high alumina Al-Zn-Mg-Si-La-Y corrosion-inhibiting coatings.
By the gained coating cross-hatching of embodiment 5 survey adhesion be 0 grade, at 12-15 μm, resistance to 10% salt solution more than 145d,
Neutral salt spray test is more than 1850h, and hardness is more than 205HV0.005.And data record is entered into table 2.
Embodiment 6
The present embodiment and the operations condition of embodiment 1 are essentially identical, and difference is：Aluminium zinc-magnesium silicon multicomponent alloy powder
230g, wherein aluminium, magnesium, silicon, zinc, Ce mass ratio are 66:5.7:5.1:40:1.2, modified nano-ZnO powder 6g, modified Nano
TiO2Powder 11g, γ-glycidyl ether oxygen propyl trimethoxy silicane 82g, chelating type phosphate titanium coupling agent 12g, ethylene glycol
100g, ethanol 164g, thickener 5.5g, defoamer 0.8g, polysorbas20 23g, sodium phosphomolybdate 13g, quaternary ammonium salt titanate esters are 22g,
Deionized water 494.7g, wherein containing the second deionized water 164g.
By 12-15 μm of coating layer thickness after the completion of obtained aqueous chromium-free anti-corrosion paint to matrix surface and solidification, survey
Each performance indications of coating are recorded into table 2.
Embodiment 7
The present embodiment and the operations condition of embodiment 2 are essentially identical, and difference is：Aluminium zinc-magnesium silicon multicomponent alloy powder
250g, wherein aluminium, magnesium, silicon, zinc, Sc, Ce mass ratio are 71:8:0.9:32:0.07:0.12, modified nano-ZnO powder 5 changes
Property nano-TiO2Powder 12g, γ-glycidyl ether oxygen propyl trimethoxy silicane 61g, chelating type phosphate titanium coupling agent 14g,
Ethylene glycol 65g, ethanol 60g, thickener 4.5g, defoamer 0.75g, polysorbas20 34g, sodium phosphomolybdate 11g, quaternary ammonium salt titanate esters
For 26g, deionized water 609.25g, wherein containing the second deionized water 152.5g.
By 12-15 μm of coating layer thickness after the completion of obtained aqueous chromium-free anti-corrosion paint to matrix surface and solidification, survey
Each performance indications of coating are recorded into table 2.
Embodiment 8
The present embodiment and the operations condition of embodiment 3 are essentially identical, and difference is：Aluminium zinc-magnesium silicon multicomponent alloy powder
168g, wherein aluminium, magnesium, silicon, zinc, Nd, Pr mass ratio are 59:4.2:4.2:25:0.17:0.24, modified nano-ZnO powder 3,
Modified Nano TiO2Powder 9g, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane 70g, chelating type phosphate titanium coupling agent
6g, ethylene glycol 77g, ethanol 35g, thickener 5g, defoamer 0.7g, polysorbas20 25g, sodium phosphomolybdate 16g, quaternary ammonium salt titanate esters
For 18g, deionized water 707.3g, wherein containing the second deionized water 140g.
By 12-15 μm of coating layer thickness after the completion of obtained aqueous chromium-free anti-corrosion paint to matrix surface and solidification, survey
Each performance indications of coating are recorded into table 2.
Embodiment 9
The present embodiment and the operations condition of embodiment 4 are essentially identical, and difference is：Aluminium zinc-magnesium silicon multicomponent alloy powder
270g, wherein aluminium, magnesium, silicon, zinc, Nd, Pr, Ni, Mn, Ti mass ratio are 74:5.8:2:27:1.2:1.1:0.24:0.1:2,
Modified nano-ZnO powder 4g, modified Nano TiO2Powder 8g, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane 96g, chela
Mould assembly phosphate titanium coupling agent 9g, ethylene glycol 110g, methanol 160g, thickener 5.5g, defoamer 0.7g, polysorbas20 24g, phosphorus
Sodium molybdate 15g, quaternary ammonium salt titanate esters are 24g, deionized water 561.8g, wherein containing the second deionized water 288g.
By 12-15 μm of coating layer thickness after the completion of obtained aqueous chromium-free anti-corrosion paint to matrix surface and solidification, survey
Each performance indications of coating are recorded into table 2.
Embodiment 10
The present embodiment and the operations condition of embodiment 5 are essentially identical, and difference is：Aluminium zinc-magnesium silicon multicomponent alloy powder
270g, wherein aluminium, magnesium, silicon, zinc, Ce, Pr, Nd mass ratio are 73:4.8:2.5:33:1.3:1.1:0.34, modified nano-ZnO
Powder 5, modified Nano TiO2Powder 6g, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane 100g, chelating type phosphate
Titanium coupling agent 8g, ethylene glycol 80g, methanol 200g, thickener 4.5g, defoamer 0.6g, polysorbas20 21g, sodium phosphomolybdate 14g, season
Ammonium salt titanate esters are 23g, deionized water 467.9g, wherein containing the second deionized water 200g.
By 12-15 μm of coating layer thickness after the completion of obtained aqueous chromium-free anti-corrosion paint to matrix surface and solidification, survey
Each performance indications of coating are recorded into table 2.
Embodiment 11- 20 embodiments of embodiment are similar to Example 1, and its difference is that each component content is different.
Each alloying component of embodiment 11- embodiments 20 difference is as follows：
Aluminium zinc-magnesium silicon multicomponent alloy powder content and mass ratio of each component are respectively：300g, wherein Al in embodiment 1:Mg:
Si:Zn:Ni:Y=56:3.4:4:33:3:0.5；280g, wherein Al in embodiment 2:Mg:Si:Zn:Mn:Ce=57:8:4:31:
0.05:1；260g, wherein Al in embodiment 3:Mg:Si:Zn:La:Er=60:3.4:1.6:33:2:0.01；In embodiment 4
250g, wherein Al:Mg:Si:Zn:Ni:Mn=62:3.4:1.6:33:5:0.05；230g, wherein Al in embodiment 5:Mg:Si:
Zn:Ti:Zr=63:8:4:24.5:0.5:0.01；220g, wherein Al in embodiment 6:Mg:Si:Zn:Ni:Mn=64:3.4:
1.6:30.9:0.05:0.05；200g, wherein Al in embodiment 7:Mg:Si:Zn:Ti:Er=65:9.5:5.5:18.5:0.5:
1；180g, wherein Al in embodiment 8:Mg:Si:Zn:Ti:Ce=68:8:4:19:0.5:0.5；150g in embodiment 9, wherein
Al:Mg:Si:Zn:La:Y=70:4.6:0.5:24.78:0.02:0.1；150g, wherein Al in embodiment 10:Mg:Si:Zn:La
=72:3.4:1.6:22.1:0.9.Other component quality are as shown in table 1 in embodiment 11- embodiments 20：
Each component contents (g) of embodiment 11-20 of table 1
Embodiment 11-20 reclaimed waters enzymolysis auxiliary agent selects ethanol or methanol, and epoxy silane coupling selects β-(3,4- epoxide rings
Hexyl) ethyl trimethoxy silane or γ-glycidyl ether oxygen propyl trimethoxy silicane, that to be used in preparation process goes
Ionized water is taken as needed, wherein the second deionized water meets the quality of the second deionized water：The quality of silane hydrolyzate auxiliary agent：
Quality=2-3.5 of epoxy silane coupling：0.5-2:1.
It is pointed out that in other embodiments of the invention, the composition of auxiliary element can be Ni, Mn, Ti, Ag,
At least one of Zr and RE any combination, are not enumerated herein.
Experimental example
By 12-15 μm of coating of Dacroment be designated as 21 with a certain commercially available 12-15 μm of Non-chromium Zn-al Coating be designated as 22 with the present invention
The embodiment 1-20 of offer determines various performance parameters, record data to table 2 together.
After the completion of obtained aqueous chromium-free anti-corrosion paint to matrix surface and solidification, each performance indications note of coating is surveyed
Typing table 2.
Each embodiment of table 2 and experimental example coating performance parameter
Analyze upper table to understand, the hardness for removing Dacromet/steel is not less than the coating of coating of embodiment of the present invention coating
Hardness beyond, the indices that Dyclo paint and commercial coating coat the coating to be formed are provided compared with the embodiment of the present invention
The coated coating formed of aqueous chromium-free anticorrosive paint indices it is poor.Aqueous chromium-free provided by the present invention as can be seen here
Anticorrosive paint corrosion resistance and hardness are preferable.
In summary, the aqueous chromium-free anticorrosive paint that the present invention is provided by alloy in the inner there is preferable composition proportion to make
The coating that is formed of its coating is being maintained on the basis of corrosion products film has preferable passivation in the course of the work, enter
One step increases the effect of coating sacrificial anode, significantly improves the anti-local corrosion ability of coating, while the assistant metal member added
Element can further improve the hardness and corrosion resistance of coating.And the method for the aqueous chromium-free anticorrosive paint that the present invention is provided,
The aqueous chromium-free anticorrosive paint that Corrosion Protection is good, hardness is high can be prepared.
The preferred embodiment of the present invention is the foregoing is only, is not intended to limit the invention, for this area
For technical staff, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made is any
Modification, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (10)
1. a kind of aqueous chromium-free anticorrosive paint, it is characterised in that its raw material count by weight including：Aluminium zinc-magnesium silicon is polynary to be closed
150-300 parts of bronze, 5-20 parts of modified nano powder, 50-100 parts of epoxy silane coupling, the coupling of chelating type phosphate titanium
5-15 parts of agent, 60-120 parts of ethylene glycol, 25-200 parts of silane hydrolyzate auxiliary agent, 4-6.5 parts of thickener, 0.5-1 parts of defoamer, tween
20 18-36 parts, 9-18 parts of phosphomolybdate, quaternary ammonium salt titanate esters be 10-30 parts, wherein the aluminium zinc-magnesium silicon multicomponent alloy powder bag
Include aluminium, magnesium, silicon, zinc and auxiliary element, the aluminium, the magnesium, the silicon, the mass ratio of the zinc and the auxiliary element are
55.5-75：3.2-9.6：0.35-5.7：18.22-40.87：0.08-5.5, the auxiliary element be Ni, Mn, Ti, Ag, Zr,
La, Ce, Pr, Nd, Sc, Er and Y at least one.
2. aqueous chromium-free anticorrosive paint according to claim 1, it is characterised in that the aluminium zinc-magnesium silicon multicomponent alloy powder is
Flakey.
3. aqueous chromium-free anticorrosive paint according to claim 2, it is characterised in that the aluminium zinc-magnesium silicon of flakey is polynary
Alloyed powder piece footpath is less than 20 μm, and piece thickness is less than 0.5 μm, and draw ratio is more than 30.
4. aqueous chromium-free anticorrosive paint according to claim 1, it is characterised in that the modified nano powder includes being modified
Nano ZnO powder and modified Nano TiO2Powder.
5. aqueous chromium-free anticorrosive paint according to claim 4, it is characterised in that the modified nano-ZnO powder and institute
State modified Nano TiO2The mass ratio of powder is 1:1-3.
6. aqueous chromium-free anticorrosive paint according to claim 1, it is characterised in that the silane hydrolyzate auxiliary agent is small molecule
Unit alcohol.
7. aqueous chromium-free anticorrosive paint according to claim 6, it is characterised in that institute's small molecule unit alcohol is methanol or second
Alcohol.
8. a kind of method for preparing the aqueous chromium-free anticorrosive paint as described in claim any one of 1-7, it is characterised in that bag
Include：
The polysorbas20, the chelating type phosphate titanium coupling agent, the quaternary ammonium salt titanate esters and the ethylene glycol are dissolved in the
Agitating solution is to thick in one deionized water；
The modified nano powder, the aluminium zinc-magnesium silicon multicomponent alloy powder are sequentially added in whipping process is continued and described is disappeared
Infusion is uniform to slurry；
And add the epoxy silane coupling, the silane hydrolyzate auxiliary agent, the phosphomolybdic acid into the uniform slurry
The aqueous solution of salt and the thickener.
9. method according to claim 8, it is characterised in that by the epoxy silane coupling and silane hydrolyzate auxiliary agent
It is dissolved in the second deionized water and is well mixed to obtain transparent settled solution, by the transparent settled solution, the water of the phosphomolybdate
Solution and the thickener are sequentially added in the uniform slurry.
10. method according to claim 9, it is characterised in that second deionized water, the silane hydrolyzate auxiliary agent with
The mass ratio of the epoxy silane coupling is 2-3.5：0.5-2:1.
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| CN117210080A (en) * | 2023-10-19 | 2023-12-12 | 青岛中氟氟碳材料有限公司 | Preparation method and application of anti-pollution water-based paint for inner wall of high-speed rail |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242686A (en) * | 2013-03-28 | 2013-08-14 | 南京航空航天大学 | High-corrosion-resistant water soluble zinc aluminium multielement alloy-based nano anticorrosion paint as well as preparation method and application thereof |
-
2017
- 2017-05-12 CN CN201710333338.2A patent/CN106967985A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242686A (en) * | 2013-03-28 | 2013-08-14 | 南京航空航天大学 | High-corrosion-resistant water soluble zinc aluminium multielement alloy-based nano anticorrosion paint as well as preparation method and application thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117210080A (en) * | 2023-10-19 | 2023-12-12 | 青岛中氟氟碳材料有限公司 | Preparation method and application of anti-pollution water-based paint for inner wall of high-speed rail |
| CN117210080B (en) * | 2023-10-19 | 2024-03-29 | 青岛中氟氟碳材料有限公司 | Preparation method and application of anti-pollution water-based paint for inner wall of high-speed rail |
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Application publication date: 20170721 |