CN108753103A - Corrosion-inhibiting coating liquid of magnesium and magnesium alloy organic and inorganic and preparation method thereof and painting method - Google Patents
Corrosion-inhibiting coating liquid of magnesium and magnesium alloy organic and inorganic and preparation method thereof and painting method Download PDFInfo
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- CN108753103A CN108753103A CN201810517866.8A CN201810517866A CN108753103A CN 108753103 A CN108753103 A CN 108753103A CN 201810517866 A CN201810517866 A CN 201810517866A CN 108753103 A CN108753103 A CN 108753103A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/20—Metallic substrate based on light metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical Treatment Of Metals (AREA)
- Paints Or Removers (AREA)
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Abstract
The invention discloses corrosion-inhibiting coating liquid of a kind of magnesium and magnesium alloy organic and inorganic and preparation method thereof and painting method, ingredient is macromolecule polymer solution and the metal-rare-earth oxide insoluble in solution；The content of high molecular polymer is 30-75%, and the content of high molecular polymer curing agent is 24.5-60%, and the content of rare-earth oxide is 0.5-10%.Painting method is：Pre-treatment is carried out to magnesium alloy；Magnesium or magnesium alloy are applied into organic-inorganic composite coating；The material of coat coating is dried；By the hot setting in an oven of the material after drying.The Organic-inorganic composite coating of magnesium and Mg alloy surface has excellent corrosion resistance, stability and persistence.
Description
Technical field
The present invention relates to metal corrosion and protection fields, especially the corrosion protection to magnesium and magnesium alloy, are related to content and are
Corrosion-inhibiting coating liquid and its synthetic method, and formed coating corrosion-inhibiting coating method.More particularly, this application involves impartings
The high molecular polymer of magnesium and the lasting Corrosion Protection of magnesium alloy-rare-earth oxide coating composition, uses such painting
Feed composition forms the magnesium of coating and the coating of the method for magnesium alloy and magnesium and magnesium alloy with lasting Corrosion Protection.
Background technology
The density of magnesium alloy is low, about 1.75g/cm, while it has specific strength, specific stiffness, higher than elasticity modulus and easy
In recycling the advantages of, have good casting character and cut processing performance.Therefore from the 1990s, magnesium and magnesium alloy by
In its unique performance, it is known as " 21 century green engineering material ".
Meanwhile magnesium is a kind of rich secondary element that aluminium and iron are only second in the earth's crust, reserves 2.7%, mainly with magnesium mine
The form of stone exists.And China's magnesium resource reserves account for about the 22.5% of global total amount, former magnesium yield reaches 35.4 ten thousand tons within 2003,
It ranks first in the world.2000, " Magnesium Alloy Development is applied and industrialization " was put into the great item of the Department of Science and Technology " 15 " Ministry of Science and Technology
Mesh, country, government and research department are even more to pay much attention in terms of magnesium alloy.It can be said that magnesium and magnesium alloy materials have very
Wide application prospect.
But magnesium alloy disadvantage is exactly that corrosion resistance is poor, is easy to aoxidize in the natural environment, on surface
Loose oxidation film is generated, especially just occurs the phenomenon that corrosion nigrescence quickly in a humidity environment, leads to each of magnesium alloy
Item performance is affected, and causes magnesium alloy use scope to receive limitation, hinders the further use of magnesium alloy.For this purpose,
Will be used for magnesium alloy widely applied in engineering material on condition that solve magnesium alloy etching problem.
Inventor notices marine mammal, such as cetacean in the course of the study, they can be good at avoiding body
The loss of liquid, other than its internal circulation system is for the balance of osmotic pressure, their skin also has certain protective effect.
First, skin is living individual with external environment into the barrier of row information and mass exchange, is executed in the vital movement of animal
The particularity of multiple functions, skin also tends to adaptability of the reflection organism to environment, wherein participating in maintaining the interior steady of organism
Surely it is very important one of physiological function.Japha earliest studies the anatomical structure of cetacean skin, finds cetacean
Epidermis thickens extremely.Other than a small number of cetaceans have the tactile hairs of specialization on head or rhynchodaenm, cetacean skin without hair and hair follicle, and
And without sweat gland and sebaceous glands.The work(of epidermis thickened and although the degeneration of body of gland makes the skin of cetacean lose salt excretion
Can, but can preferably keep apart body fluid and external environment, provide certain guarantee for cetacean itself homeostasis.Cetacean
Skin can be divided into epidermis, skin corium and subcutaneous tissue.Epidermis is made of basal layer, stratum aculeatum and outer layer, and without stratum granulosum
And hyaline layer.The incomplete angling of okioplast, by the cell composition of the gradual angling of multilayer, cell elongation is in flat, because it contains
There are a large amount of phospholipid and glycolipid substance, important role is provided for cetacean skin；Stratum aculeatum is relatively thick, and cell is by depth
Layer becomes fusiformis and flat, cell turgidity fibrinogen and pigment granule, lipid particles, membrane-coating granules etc. to shallow-layer from column
More, intracellular or intercellular particulate matter may play certain effect in terms of adjusting the permeability of water and salt.By
The excitation of this bionical strategy, inventor's thinking in Mg alloy surface by building one layer of height with ocean Cetacean skin
Molecular coatings.This coating has the general character of ocean mammalian skin, that is, forms fine and close protective layer, completely cuts off metallic matrix
The contact between extraneous corrosive environment.What is more important, inventor it is expected to obtain a kind of with whale globefish class skin stratum aculeatum
The polymeric coating layer of structure, containing being similar to cell turgidity fibrinogen, pigment granule, lipid particles and membrane-coating granules in the coating
Substance, adjust the contact relation between high molecular polymer and external environment so that the coating has more perfect anti-corrosion
Corrosion energy.
Invention content
It is a kind of important to apply protective coating in metal surface by surface treatment or certain coating process technology
Corrosion protection method can completely cut off connecing between metal and corrosive environment by generating a kind of passive film with protective value
It touches, improves, improves the corrosion resistance of metal and its alloy material with this.The method that it is generally included is：Chemical composition coating
Method, chemical deposit method, galvanoplastic, anodic protection method, organic coating, gas phase protection, composite coating.Wherein organic coating is
The simplest means that anti-corrosion protection is carried out to metal are usually added in the coating to further increase the corrosion resistance of coating
Some fillers.
These fillers are often that some are micron even nano particle, since particle has high specific surface area, surface
Atom has high unsaturation, therefore the surface-active of nano-particle is very big, leads to certain organic polymers, such as ring
Oxygen resin, polydimethylsiloxaneresins resins, polyvinylidene fluoride, polyurethane etc. form much with nano-particle on interface
More than the effect of Van der Waals force, there is relatively good compatibility, forms ideal interface.In the wear-resisting of high molecular polymer
Property, tensile strength, impact strength, heat decomposition temperature etc. have greatly improved above, greatly strengthen the power of high molecular polymer
Learn performance.
Further, since the electrical insulation capability of most macromolecule polymers is fine, with other materials it is compound after, generally can
Its good electrical insulation capability is kept, while the mechanical property, caking property, corrosion resistance etc. of composite material can be increased again,
Particularly with the addition of conductive material, can obtain with the relatively high composite material of dielectric constant, moreover it is possible to improve its dielectric loss,
Dielectric loss than general at present conductor and organic polymer is much smaller.
Metallic rare earth elements can hinder O2Transport and electronics transmission so that cathode reaction is inhibited by certain, and
Cathode reaction is the rate determining step of entire corrosion process, and reaction rate reduction can lead to shuffling for corrosion potential, metallic matrix
General corrosion rate can substantially reduce.Moreover, nearest the study found that the presence of rare earth element can so that corrosion is micro-
The active site of the anode and cathode reaction of battery is inhibited simultaneously, that is to say, that and it can not only inhibit cathode reaction,
It can inhibit anode reaction.
Therefore, it using some rare-earth oxide particles as filler, is added in high molecular polymer, has and it is expected
To a kind of at low cost, corrosion resistance, the good and convenient composite coating technology of preparation process, can widely extend to entire work
Industry manufacturing field.
The purpose of the present invention is to provide a kind of Organic-inorganic composite paintings for metal with good Corrosion Protection
Layer, includes preparation and its painting method of coating solution, is particularly directed to magnesium and magnesium alloy.In the chemical composition of the coating solution not
Containing heavy metal or fluoride, toxicity is low, environmental-friendly and cost economy.In addition, by the coating solution in magnesium and magnesium alloy material
The film layer that material surface is formed has good corrosion resistance and excellent stability.
A kind of magnesium of the present invention and the corrosion-inhibiting coating liquid of magnesium alloy organic and inorganic, ingredient and mass percent are：
High molecular polymer 30-75%
High molecular polymer curing agent 24.5-60%
Rare-earth oxide 0.5-10%
The high molecular polymer selects bisphenol A type epoxy resin, polydimethylsiloxaneresins resins, polyvinylidene fluoride
Or polyurethane；The rare-earth oxide selects nano ceric oxide；The average grain diameter of the nano ceric oxide is
50-500 nanometers；High molecular polymer curing agent selects polyamide or polyetheramine.
The preparation method of the magnesium of the present invention and the corrosion-inhibiting coating liquid of magnesium alloy organic and inorganic, includes the following steps：
(1) high molecular polymer is dissolved according to the ratio of 30-75 in toluene solution；
(2) high molecular polymerization being added to rare-earth oxide powder according to the ratio of 0.5-10% in step (1)
In object solution, stirring, ultrasonic disperse 15-40 minutes forms dispersion liquid；
(3) high molecular polymer curing agent is added in the dispersion liquid of above-mentioned steps (2) according to the ratio of 24.5-60%,
Ultrasonic disperse 15-40 minutes cures 2-40 minutes, obtains etch-proof coating solution.
The painting method of the magnesium of the present invention and the corrosion-inhibiting coating liquid of magnesium alloy organic and inorganic, includes the following steps：
(1) magnesium or magnesium alloy are pre-processed；
(2) the corrosion-inhibiting coating liquid that magnesium or Mg alloy surface are coated to organic and inorganic, forms organic-inorganic composite coating；
(3) magnesium or magnesium alloy for being coated with Organic-inorganic composite coating are dried 1-12 hours；
(4) by the magnesium or magnesium alloy hot setting Organic-inorganic composite coating in an oven after drying.
Being pre-processed to magnesium or magnesium alloy for step (1), includes the following steps：
(1a) polishes magnesium or magnesium alloy, removes the oxide layer on surface；
(1b) is cleaned by ultrasonic using acetone, absolute ethyl alcohol, and scavenging period is 5-30 minutes；
(1c) will clean later magnesium or magnesium alloy is placed in 0.5-2 moles every liter of lye, 30-110 degrees Celsius of hydro-thermal,
Reaction 0.5-12 hours then utilizes washes of absolute alcohol, obtains the magnesium or magnesium alloy after surface is modified.
Magnesium after processing or magnesium alloy, on the surface that microcosmic upper formation is coarse, while the flatness of entire plane all arrives
Certain promotion enhances the physisorption of coating solution so that the adhesive force of epoxy coating liquid greatly promotes, i.e.,
Make to can be good at that magnesium alloy is protected to exempt to be corroded in 0.6 mole every liter of sodium chloride solution.What is more important, it is entire to locate
Reason process is not related to any heavy metal or harmful chemical solvent, inorganic ions, and simple to operate, low energy consumption, operation letter
It is single, it can be directly used for industrial production.
Painting method of the present invention can form high molecular polymer-titanium dioxide in magnesium and magnesium alloy matrix surface
The organic coating of the compound of cerium.High molecular polymer itself is a kind of extraordinary corrosion inhibiter, and a kind of common metal
Surface anticorrosion coating material.High molecular polymer and ceria are, and high scores combined by physisorption
Sub- polymer, the chemical stability of ceria are relatively good, and after pretreatment, substrate surface forms the coarse table on microcosmic
Face so that be closely linked between coating and substrate, be less likely to occur to fall off in water body environment.Matrix is formed in this way
Very strong shielding properties.Ceria can reduce the electrochemical reaction activity of coating simultaneously, and the protection to extend coating is made
Use the time.Composite coating makes the corrosion rate of magnesium and magnesium alloy bright by the collective effect of high molecular polymer and ceria
It is aobvious to reduce, significantly extend protective effect time of the coating for metallic substrates.
The mode coated described in step (2) includes spin coating, spraying, dip-coating, blade coating, brushing etc., and its object is to be formed
The coating of stable uniform, specific mode of operation do not limit.
Dry mode described in step (3) may include natural drying at room temperature, low temperature drying, it is infrared dry, vacuum
Drying at room temperature or vacuum dehydrating at lower temperature etc., its object is to be coating surface drying.
Beneficial effects of the present invention：
Organic-inorganic composite coating solution in metal surface of the present invention is free of chromate or fluoride.Compared with existing
Magnesium and magnesium alloy anticorrosion treatment technology, the coating solution it is non-toxic, effect on environment degree is low, belongs to environmentally friendly product,
It disclosure satisfy that the environmental protection standard of field of industrial production.
Magnesium of the present invention and Organic-inorganic composite coating solution used for magnesium alloy, which are formed by erosion shield, to be had well
Corrosion resistance and excellent stability.
The cost of magnesium of the present invention and Organic-inorganic composite coating solution used for magnesium alloy is low, can be pushed away on a large scale
Extensively to industrial production and manufacturing field.
The painting method of magnesium and magnesium alloy of the present invention is simple and practicable, is suitable for stablizing life on a variety of production lines
Production.
Description of the drawings
Fig. 1 is the microstructure photo before the magnesium matrix surface of embodiment A1 is pre-processed.
Fig. 2 is the microstructure photo after the magnesium matrix surface of embodiment A1 is pre-processed.
Fig. 3 is the X-ray diffraction spectrogram in relation to cerium oxide particles in embodiment A1-A4.
Fig. 4 is the X-ray photoelectron spectroscopic analysis spectrogram on magnesium matrix surface in embodiment A1-A4.
Fig. 5 is tissue of the magnesium matrix surface after 0.6 mole of every liter of sodium chloride solution impregnates 7 days in embodiment A1-A4
Photo.
Tissue of the Mg alloy surface that Fig. 6 is comparative example B1 after 0.6 mole of every liter of sodium chloride solution impregnates 7 days shines
Piece.
Fig. 7 is the TAFEL curves of embodiment A1-A4 and comparative example B1, B2.
Specific implementation mode
Embodiment A1-A4 is all made of the preparation that following general step carries out magnesium matrix surface Organic-inorganic composite coating：
(1) magnesium matrix surface is pre-processed, which includes：
(1a) uses the carborundum paper polishing magnesium matrix surface of 1500 mesh and polishes；
(1b) is respectively adopted acetone and absolute ethyl alcohol and carries out ultrasonic cleaning, cleaning to magnesium matrix surface at ambient temperature
Time is 5-30 minutes；
(1c) magnesium matrix is in 0.2-2 moles every liter of sodium hydroxide solution, under 30-110 degrees Celsius of hydrothermal condition
Reaction 0.5-12 hours utilizes washes of absolute alcohol afterwards.
(2) magnesium matrix is applied by the way of spin coating and is covered with Organic-inorganic composite coating solution, the ingredient of coating solution is toluene
Bisphenol A epoxide resin, nano ceric oxide particle and epoxy hardener polyetheramine in solution；Wherein bisphenol A epoxide resin
Mass content is 30-75%, and the content of curing agent is 24.5-60%, and the content of ceria is 0.5-10%.It is specifically made
It is standby that steps are as follows：
Bisphenol A epoxide resin is dissolved according to the ratio of 30-75% in toluene by (2a), and it is molten to form bisphenol A epoxide resin
Liquid；
Nano ceric oxide powder is added to the bisphenol A epoxide resin of step (2a) by (2b) according to the ratio of 0.5-10%
In solution, stirring, ultrasonic disperse 5-60 minutes；
Curing agent polyetheramine or polyamides is added according to the ratio of 24.5-60% in (2c) in the dispersion liquid of above-mentioned steps (2b)
Amine, ultrasonic disperse 5-60 minutes cure 2-40 minutes, obtain etch-proof coating solution.
For ceria in step (2), the preparation method of embodiment A1-A2 is all different：
The preparation process of ceria in A1：
The solution is added drop-wise in stirring, 1-5 by the ethanol solution of the cerous nitrate of 0.1-0.5 moles every liter of configuration
The double of a certain amount of 5-30wt% are added in the ammonium hydroxide-ethanol solution in mole every liter of ammonium hydroxide-ethanol solution in advance
Oxygen water.Rate of addition is 0.5-6 milliliters per minute, until the color of suspension is brown, centrifuges precipitation.It is deposited in baking
In case after drying, grinding is sent into Muffle furnace and is roasted 1-4 hours for 250-600 degrees Celsius.
The preparation process of ceria in A2：
A certain amount of octadecylamine is added in ethanol-water solution, cerous chlorate is added after to be dissolved, is filled using ethylenediamine
When pH adjusting agent and viscosity modifier, it is 7 to 8 to adjust pH, utilizes hydrothermal reaction kettle after stirring 1-6 hours, is taken the photograph in 120-200
It is reacted 36-82 hours in family name's degree.After reaction, precipitation is centrifuged, it is dry in baking oven with acetone, hot ethanol, water washing,
Grinding is sent into Muffle furnace and is roasted 3-12 hours for 200-600 degrees Celsius.
The preparation process of ceria in A3：
Urea and cerous nitrate are added in water, after to be dissolved, a certain amount of hydrogen peroxide is added, until solution colour is dark
It is orange, it is sent into hydrothermal reaction kettle, is reacted 6-24 hours at 100-250 degrees Celsius.Precipitation is centrifuged, is washed with water, ethyl alcohol,
Vacuum oven.
The preparation process of ceria in A4：
The cerous nitrate aqueous solution for configuring a certain amount of 0.05-0.3 moles every liter, precipitating reagent is done using ammonium hydroxide, is acutely being stirred
Lower addition ammonium hydroxide is mixed, until the pH of solution is 7-10, is kept stirring 20-90 minutes.Precipitation is centrifuged, is washed with water, ethyl alcohol
It washs, oven drying, grinds, roasted 2-6 hours in 250-700 DEG C of Muffle furnace.
For step (2), the embodiment for not adding ceria is named as B1, used as a comparison case by us.
(3) it is coated with the magnesium matrix of machine-inorganic composite coating liquid, dries 12 hours under field conditions (factors), makes coating table
Face surface drying.
(4) the later magnesium matrix of drying is sent into heat cure 1-10 hours in 60-140 degrees Celsius of baking oven, be sent into later
Heat cure 1-5 hours in 150-200 degrees Celsius of baking oven.
Fig. 1 is the microstructure photo before the magnesium matrix surface of embodiment A1-A4 is pre-processed.Fig. 2 is embodiment
The magnesium matrix surface of A1-A4 pre-processed after microstructure photo.Fig. 4 is the X on magnesium matrix surface in embodiment A1-A4
Ray photoelectron spectroscopic analysis spectrogram.Fig. 7 is the TAFEL curves of embodiment A1-A4 and comparative example B1.
By the comparison of Fig. 1 and Fig. 2 it can be found that after pretreatment, magnesium matrix surface generates some microcellular structures,
These structures are conducive to epoxy resin and are preferably combined with magnesium matrix, the physical shielding effect of reinforced epoxy.It is advantageous simultaneously
In the interface compatibility for increasing epoxy resin and magnesium matrix, the adhesive force of reinforced epoxy so that coating can be more longlasting
It plays a role.
Embodiment A1-A4 and comparative example B1, B2 are sampled, wherein B1 is the magnesium matrix for only coating epoxy resin, B2
For magnesium matrix.Embodiment A1-A4 and comparative example B1, B2 are individually positioned in 0.6 mole every liter of sodium chloride solution and impregnated, is soaked
Bubble temperature is room temperature, and soaking time is 7 days, takes out embodiment and comparative example after impregnating 7 days, TAFEL curves is retested, to sentence
Disconnected corrosion condition.
Fig. 7, to issuing a certificate, by the compound epoxy coating of ceria, there is better electrochemistry in terms of electrochemistry
Shielding action has extraordinary protective action for the corrosion of magnesium matrix.
Fig. 5 and Fig. 6 are shown, after 0.6 mole every liter of sodium chloride solution impregnates 7 days, the magnesium of embodiment A1-A4
Serious corrosion does not occur for matrix surface.It reviews, is had occurred on the surface of comparative example B1 (non-dioxide composite cerium particle)
Serious corrosion, and also corrosion product precipitation is covered on the surface of magnesium matrix, it can be seen that and the later magnesium of plated film closes
Gold utensil has more excellent corrosion resistance.
Claims (7)
1. the corrosion-inhibiting coating liquid of a kind of magnesium and magnesium alloy organic and inorganic, it is characterised in that：Its ingredient and mass percent are：
High molecular polymer 30-75%
Polymeric consolidator 24.5-60%
Rare-earth oxide 0.5-10%.
2. the corrosion-inhibiting coating liquid of a kind of magnesium according to claim 1 and magnesium alloy organic and inorganic, it is characterised in that：It is described
High molecular polymer can be bisphenol A type epoxy resin, polydimethylsiloxaneresins resins, polyvinylidene fluoride or polyurethane；
The rare-earth oxide selects nano ceric oxide；The average grain diameter of the nano ceric oxide is received for 50-500
Rice.
3. the preparation method of the corrosion-inhibiting coating liquid of magnesium described in claim 1 and magnesium alloy organic and inorganic, includes the following steps：
(1) high molecular polymer is dissolved according to the ratio of 30-75% in toluene solution；
(2) high molecular polymer being added to rare-earth oxide powder in step (1) according to the ratio of 0.5-10% is molten
In liquid, stirring, ultrasonic disperse 15-40 minutes forms dispersion liquid；
(3) high molecular polymer curing agent is added in the dispersion liquid of above-mentioned steps (2) according to the ratio of 24.5-60%, ultrasound
Dispersion 15-40 minutes cures 2-40 minutes, obtains etch-proof coating solution.
4. the painting method of the corrosion-inhibiting coating liquid of magnesium described in claim 1 and magnesium alloy organic and inorganic, includes the following steps：
(1) magnesium or magnesium alloy are pre-processed；
(2) the corrosion-inhibiting coating liquid that magnesium or Mg alloy surface are coated to organic and inorganic, forms organic-inorganic composite coating；
(3) magnesium or magnesium alloy for being coated with Organic-inorganic composite coating are dried 1-12 hours；
(4) by the magnesium or magnesium alloy hot setting Organic-inorganic composite coating in an oven after drying.
5. the painting method of the corrosion-inhibiting coating liquid of magnesium according to claim 4 and magnesium alloy organic and inorganic, feature exist
In：Being pre-processed to magnesium or magnesium alloy for step (1), includes the following steps：
(1a) polishes magnesium or magnesium alloy, removes the oxide layer on surface；
(1b) is cleaned by ultrasonic using acetone, absolute ethyl alcohol, and scavenging period is 5-30 minutes；
(1c) will clean later magnesium or magnesium alloy is placed in 0.5-2 moles every liter of lye, 30-110 degrees Celsius of hydro-thermal, reaction
0.5-12 hours, washes of absolute alcohol is then utilized, obtains the magnesium or magnesium alloy after surface is modified.
6. the painting method of the corrosion-inhibiting coating liquid of magnesium according to claim 4 and magnesium alloy organic and inorganic, feature exist
In：The mode coated described in step (2) is spin coating, spraying, dip-coating, blade coating or brushing.
7. the painting method of the corrosion-inhibiting coating liquid of magnesium according to claim 4 and magnesium alloy organic and inorganic, feature exist
In：Dry mode described in step (3) be naturals drying at room temperature, low temperature drying, it is infrared dry, vacuum drying at room temperature or very
Empty low temperature drying.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111136977A (en) * | 2019-12-20 | 2020-05-12 | 苏州福斯特光伏材料有限公司 | Lithium battery flexible packaging material and preparation method thereof |
| CN111940258A (en) * | 2020-06-16 | 2020-11-17 | 中国建材国际工程集团有限公司 | Corrosion-resistant coating on surface of magnesium alloy building template and preparation method thereof |
| CN113073365A (en) * | 2021-03-25 | 2021-07-06 | 北京冬曦既驾科技咨询有限公司 | High-corrosion-resistance magnesium alloy electroplated layer and preparation method thereof |
| CN115678383A (en) * | 2022-11-08 | 2023-02-03 | 河南大学 | Preparation method and application of magnesium alloy surface photodynamic antibacterial anticorrosive coating |
| CN116082916A (en) * | 2022-12-20 | 2023-05-09 | 广州三孚新材料科技股份有限公司 | Efficient anti-corrosion hole sealing liquid for magnesium alloy surface and application thereof |
-
2018
- 2018-05-26 CN CN201810517866.8A patent/CN108753103A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111136977A (en) * | 2019-12-20 | 2020-05-12 | 苏州福斯特光伏材料有限公司 | Lithium battery flexible packaging material and preparation method thereof |
| CN111940258A (en) * | 2020-06-16 | 2020-11-17 | 中国建材国际工程集团有限公司 | Corrosion-resistant coating on surface of magnesium alloy building template and preparation method thereof |
| CN113073365A (en) * | 2021-03-25 | 2021-07-06 | 北京冬曦既驾科技咨询有限公司 | High-corrosion-resistance magnesium alloy electroplated layer and preparation method thereof |
| CN115678383A (en) * | 2022-11-08 | 2023-02-03 | 河南大学 | Preparation method and application of magnesium alloy surface photodynamic antibacterial anticorrosive coating |
| CN115678383B (en) * | 2022-11-08 | 2023-12-15 | 河南大学 | Preparation method and application of photodynamic antibacterial anticorrosive coating on magnesium alloy surface |
| CN116082916A (en) * | 2022-12-20 | 2023-05-09 | 广州三孚新材料科技股份有限公司 | Efficient anti-corrosion hole sealing liquid for magnesium alloy surface and application thereof |
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