CN101481553A - Normal temperature cured self-assembly composite nano oxide anti-corrosive paint - Google Patents
Normal temperature cured self-assembly composite nano oxide anti-corrosive paint Download PDFInfo
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Abstract
The invention relates to a nanometer antiseptic paint and provides a nanometer composite oxide antiseptic paint for various metal substrates. After the paint is used for treated metal, the coating can be solidified at the normal temperature and has excellent antiseptic property. The composite oxide comprises nanometer silicon dioxide sol and nanometer titanium dioxide sol. After the coating is dried, nanometer particles of the composite oxide subject to the modification of fluorocarbon-type silane coupling agent and other types of organic silane coupling agent undergo self-assembly to form a dense coating with a thickness of 1-5 microns.
Description
Technical field:
The invention belongs to paint field, particularly nano paint is used for field of metal surface treatment, obtains a kind of self-assembly composite nano oxide anti-corrosive paint of ambient cure.
Background technology:
The use of metal runs through the whole historical dynasty of the China and the world.The all well-known bronze work of summer merchant develop into the Chinese, bronze utensil, iron weapon.Its development promotes the renewal in dynasty advances, and is one of important witness of Chinese history development.Yet now, corrosion of metal has brought the waste of mineral products, and a series of problems such as the pollution of environment cause far-reaching influence for the economy of daily life and relevant enterprise.
Corrosion of metal is metal caused destruction or rotten under the effect of environment.So-called environment is meant the material with metallic contact, the for example air that exists of nature, seawater, fresh water, soil etc., and produce, other starting material and the product of life usefulness, because these materials and metal generation chemical action or electrochemical action cause corrosion of metal, make metal generation corrosive part, become compound by simple substance character, and phenomenon such as get rusty, ftracture, bore a hole, become fragile.Metallic corrosion almost relates to each department of national economy, every field on a large scale.Get rusty in atmosphere as hardware; The naval vessel suffers the corrosion of seawater and microorganism; Burying oil transportation, the gas transmission line on ground bores a hole because of the corrosion of soil and bacterium; Steel Yin Gaowen and airborne oxygenizement and produce a large amount of oxide skin in the operation of rolling; Chemical machinery is owing to often contact with severe corrosive acid, alkali, salt medium, and carry out under the high temperature of being everlasting, high pressure, high flow rate again, thereby corrodes even more serious.This brings immeasurable loss for the relevant enterprise of national economy.In recent years, Chinese Important Project project, urban infrastructure construction etc. are because the loss that metallic corrosion causes has reached 5,000 hundred million yuan every year.
The classification of metallic corrosion
By the corrosion process branch, mainly contain chemical corrosion and galvanic corrosion.Chemical corrosion is that metal and surrounding medium directly chemical action take place and the damage that produces, does not have electric current to produce in corrosion process.For example metal is in the pyritous air or the corrosion in the chlorine, and nonelectrolyte is to corrosion of metal etc.Galvanic corrosion is that metal in electrolyte solution electrochemical action takes place and the damage that causes, has electric current to produce in corrosion process.The medium that causes galvanic corrosion can both conduct electricity.For example, the corrosion of metal in media such as acid, alkali, salt, soil, seawater.
Therefore, the corrosionproof protection processing often need be carried out in the metallic surface.Be used for up to now metallic corrosion protection the most successful be sexavalent chrome (chromic salt) the conversion film technology that has last 100 years history always; this technology is widely used in the multiple metal of many industrial circles such as space flight and aviation, electronics, automobile, machinery, chemical industry and other production and the corrosion protection of alloy, usually also as the criterion of all other conversion film technology.; research in recent years shows; sexavalent chrome is a kind of carcinogenic substance relevant with Human Lung Cancer, and the antiseptic use of sexavalent chrome metallic surface causes serious pollution, the mankind are produced the destiny that serious Health hazard is being faced with necessary its use of cancellation environment.
Past, another one method for anticorrosion treatment commonly used was a bonderizing.Because the phosphoric acid film has increased sticking power, make paint and melts combine firm.So the bonderizing of metal can improve its corrosion resisting property greatly, be a kind of common surface treatment method.In order to obtain better effect, potassium bichromate commonly used is carried out passivation, makes it to seal pin hole, prevents atmospheric oxidation after the phosphatization.This is a kind of traditional effective technology.But, producing phosphorous, chromium waste liquid in the parkerizing process, phosphorization technology is because of relating to carcinogenic substances such as heavy metal such as zinc, nickel, manganese, chromium and nitrite simultaneously, and environmental issues such as phosphatization slag, waste water give prominence to, and perplexing each application enterprise always.In addition, because of sharp rising of heavy metal resources price, the cost pressure that phosphorization technology faces also obviously strengthens.It is reported, exhaustion along with resources such as phosphorus, nickel, zinc, China carries out automobile industry's cleaner production and coating standard since on December 1st, 2006, the phosphatization liquid that phosphorization technology is used has carried out various restrictions, as requires it not contain nitrite and heavy metal contaminants, the low solid slag of low temperature etc.For this reason, seek the new technology that clean environment firendly does not reduce surface treatment properties simultaneously again, become pressing for of application circle.
Aluminum alloy surface must or produce the metal oxide layer of one deck rough porous with acid etch (Acid etching) with anode electrolysis (anodizing) in acid solution, so can possess the function of basic corrosion protection, could adhere or japanning with solid.This method has been continued to use for many years, though effect is pretty good, but method is too complicated, very serious to the pollution of environment simultaneously, especially wherein the acid solution of use (such as chromic acid etc.) has been that United Nations's health organization and Environmental Protection Agency (EPA) expressly will ban use of in several years, these cleanup acid treatment, or anode electrolysis all must except waste water resource, more cause the pollution of downstream environment with big water gaging flushing.Though this method has many shortcomings, solve problem yet can not find other replacement scheme for many years.
The silane technology is the recent development direction of metal finishing, has environmental protection, the unrivaled advantage of conventional art such as energy-conservation and simple to operate.The silane technology adopts ultra-thin organic coating to substitute traditional crystal type phosphatization protective layer; the organic coating of this ultrafine similar phosphatization crystalline tridimensional network is adsorbed on the metal; with metal substrate and paint coatings good sticking power is arranged all, thereby reach good application surface treatment effect.
At present, the silane process for treating surface in the North America, the fields such as household electrical appliances, electronics and IT products and automobile component of the Western European countries have begun commercial application.The silane technology is expected to progressively substitute present phosphorization treatment technology.
United States Patent (USP) 5,498,481 have described with 1, and the hydrolysis of 2-two (triethoxy is silica-based) ethane prepares 3% silylation nano paint, and the 80-120 degree toasted 10 minutes down, but antiseptic power is not high.And only be applicable to aluminium alloy base material.Can not be separately as corrosion protection coating.
United States Patent (USP) 6,827,981 have described with vinyl silanes and aminosilane hydrolysis and have prepared 5% silylation nano paint, and antiseptic power has certain effect.The 80-120 degree toasted 10 minutes down, but only was applicable to aluminium alloy base material, was not suitable for other metal.
United States Patent (USP) 20050179011 has been described with two-[r-(triethoxysilicane) propyl group]-tetrasulfide and aminosilane hydrolysis and has been prepared 5% silylation nano paint, and antiseptic power has effect preferably, but only is applicable to aluminium alloy base material, is not suitable for other metal.In order to guarantee preservative effect, must increase electrophoretic layer.
United States Patent (USP) 6,403,164 have described and have used tetraethoxysilance, and aminopropyl triethoxysilane and nano silicon are the nano paint of main component, and baking under 160 degree has certain preservative effect.
In sum, the clean surface treatment process based on nano silicon has bright development prospect.But prior art all will be toasted under high temperature and middle temperature, is difficult to big part is carried out surface treatment, increases energy consumption simultaneously.In addition, prior art also exists the nano coating voidage height of formation, and coat-thickness is not enough, and antiseptic property is not good, and the construction levelling property is poor, problems such as film forming instability.
Summary of the invention:
The objective of the invention is to overcome above-mentioned not enough problem, a kind of nano composite oxide corrosion protection coating that is used for various metal substrates is provided, composite oxides comprise nano silicon dioxide sol and nano titanic oxide sol.Composite nanoparticle formed coating after fluorine carbon silane coupling agent and other a few class organo-silicon coupling agents modifications has only the thickness of 1-5um, and this coating is solidified at normal temperatures, reaches the purpose of excellent antiseptic property.
Nano silicon dioxide sol: raw waters such as nanometer titanium dioxide silicon precursor such as tetraethoxy are separated the transparent and stabilized nano silicon dioxide granule that obtains be dispersed in the solvent.
Nano titanic oxide sol: under the effect of hydrolysis control agent methyl ethyl diketone, the transparent and stabilized nano TiO 2 particles that hydrolysis obtains is dispersed in the solvent with raw materials such as nano-TiO 2 precursor such as tetrabutyl titanates.
Self-assembly: nanoparticle is after coupling agent is modified, and nanoparticle evenly is arranged on the metal substrate, and the orderly arrangement unanimity of the coupling agent of modifying outwardly.
The nano silicon that uses among the present invention is 20nm particle diameter particle, and bead size distribution 50% is the mono-dispersed nano oxide sol.Usually nanoparticle ratio in coating accounts for 5-25% (wt%).
Among the present invention, being raw material with the tetraethoxy, is solvent with ethanol, carefully regulates the amount of hydrolyst and the amount of water, and can access uniform nano silicon is the monodispersed particle of 20nm particle diameter, is evenly distributed on and forms colloidal sol in the solvent.Usually tetraethoxy and alcoholic acid weight ratio are 1:10.Catalyzer is a phosphoric acid, and the weight percent concentration in water is 0.5%.Usually the water add-on is that the weight percent of tetraethoxy is 10-50%, and the reaction times is 1-10 hour, and temperature of reaction is a room temperature.
Among the present invention, being raw material with the tetrabutyl titanate, is solvent with ethanol, and methyl ethyl diketone is a complexing agent, prepares uniform nano titanic oxide sol.The stirring reaction time is 10 minutes, and temperature of reaction is a room temperature.Usually, the weight ratio of ethanol and tetrabutyl titanate is 2-4:1, and the weight ratio of tetrabutyl titanate and methyl ethyl diketone is 2-8:1.The weight ratio of tetrabutyl titanate and water is 10:1.
The present invention is unexpected to find that above-mentioned nano titanic oxide sol can increase substantially the hardness and the antiseptic property of pure nanometer titanium dioxide silicon coating.Usually the weight ratio of nano titanic oxide sol and nano silicon dioxide sol is 1:3-8.Body series is the nano composite oxide system, and this compound system is dispersed in the system two kinds of nanometer beads, and the combination of nano-titania particle catalytic nanometer silicon dioxide granule improves the hardness and the antiseptic property of pure nanometer titanium dioxide silicon coating.But after the nano-titania particle too high levels, nano titanic oxide sol is easily reunited, and coating is opaque.
In order further to improve system ambient cure performance of the present invention and antiseptic property, the present invention has used fluorine carbon silane coupling agent and other a few class organo-silicon coupling agents.Long-chain organic fluorine group is received nanoparticle surface, and nanoparticle is after coupling agent is modified in coating, and nanoparticle evenly is arranged on the metal substrate, and the orderly arrangement unanimity of the coupling agent of modifying outwardly.Described silane coupling agent is: ten difluoro heptyl propyl trimethoxy silicanes, the isocyanic acid propyl-triethoxysilicane, γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, Y-aminopropyl methyldiethoxysilane, two-[Y-(triethoxysilicane) propyl group]-tetrasulfide, two-[γ-(triethoxysilicane) propyl group]-disulphide, gamma-mercaptopropyltriethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane.Usually silane coupling agent ratio in coating accounts for 5-30% (wt%).Be a kind of, also plurality of silane coupling agents.
Macromolecule resin among the present invention is the organic hydroxy silicate resin of band functional group.Usually silicone resin ratio in coating accounts for 5-25%.
Solvent is an ethanol.
Above-mentioned relevant nanoparticle is mixed with above-mentioned relevant silane coupling agent; stir under the room temperature]-10 hours, obtain the corresponding nanoparticle that silane coupling agent is modified, mix with above-mentioned silicone resin solution then; obtain nano anticorrosive coating; after being used for metal substrate, this coating ambient cure, rete densification; holiday is few; the corrosion thing is difficult to by coating, arrives at protected ground, reaches the purpose of excellent antiseptic property.
Description of drawings:
Fig. 1: mimic nano molecular structure iron of the present invention
Fig. 2: the atomic force microscope photo of nanometer anticorrosive coating of the present invention
Fig. 3: mono-dispersed nano TiO 2 sol of the present invention
Fig. 4: the stereoscan photograph of nanometer anticorrosive coating of the present invention
Fig. 5: the ultimate analysis of nanometer anticorrosive coating of the present invention
Fig. 6: ferrous material has or not the difference (NSS 100 hours) (black is the non-processor part) of nanometer anticorrosive coating
Fig. 7: magnesian has or not the difference (NSS 70 hours) (black is the non-processor part) of nanometer anticorrosive coating
Fig. 8: the aluminum alloy materials nanometer anticorrosive coating is handled after the photo of salt mist experiment after 190 hours
Embodiment:
Embodiment 1:
10 gram tetraethoxys are dissolved in the 100 gram dehydrated alcohols, acetum 5 grams of adding 0.5%, normal temperature stirred 5 hours down, add ten difluoro heptyl propyl trimethoxy silicanes, 1 gram, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan 1 gram continues normal temperature and stirred 1 hour down, because these two kinds of silane coupling agents are in the modification of corresponding nanoparticle surface, make the nanoparticle self-assembly, form fine and close coating at metal material surface.The model configuration of nanometer anticorrosive coating and atomic force microscope photo are seen Fig. 1,2, and the uniform nanoparticle self-assembly of particle diameter forms fine and close coating, and the sample ambient cure is after three days, and the salt mist experiment of this coating on aluminium alloy reaches 70 hours.
Embodiment 2:
10 gram tetraethoxys are dissolved in the 100 gram dehydrated alcohols, add 0.5% acetum 5 grams, normal temperature stirred 5 hours down.Obtain nano silicon dioxide sol.0.6 gram methyl ethyl diketone is dissolved in the 10 gram alcohol, adds 2 gram tetrabutyl titanates then, stirs after 5 minutes and to add 0.2 gram deionized water, stir and obtained in 1 hour transparently being dispersed in the solvent with the stabilized nano TiO 2 particles.After two kinds of above-mentioned colloidal sols mixing, add ten difluoro heptyl propyl trimethoxy silicanes, 3 grams, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan 2 grams, continuing normal temperature stirred 1 hour down, because these two kinds of silane coupling agents are in the modification of corresponding nanoparticle surface, make the nanoparticle self-assembly, form fine and close coating at metal material surface.Titanium dioxide nano-particle SEM photo is seen Fig. 3.After the sample ambient cure three days, the salt mist experiment of this coating on aluminium alloy reaches 170 hours.
Embodiment 3:
10 gram tetraethoxys are dissolved in the 100 gram dehydrated alcohols, acetum 3 grams of adding 0.5%, normal temperature stirred 10 hours down, add ten difluoro heptyl propyl trimethoxy silicanes, 1 gram, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan 2 grams, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane 1 gram, because these two kinds of silane coupling agents make the nanoparticle self-assembly in the modification of corresponding nanoparticle surface, form fine and close coating at metal material surface.In order further to improve the thickness of coating, add again 2 grams hydroxy silicon oil.The stereoscan photograph of nanometer anticorrosive coating is seen Fig. 4.After the sample ambient cure three days, the salt mist experiment of this coating on magnesium alloy materials reaches 50 hours.
Embodiment 4:
10 gram tetraethoxys are dissolved in the 100 gram dehydrated alcohols, add 0.5% acetum 4 grams, normal temperature stirred 5 hours down.Obtain nano silicon dioxide sol.0.6 gram methyl ethyl diketone is dissolved in the 10 gram alcohol, adds 1.2 gram tetrabutyl titanates then, stirs after 5 minutes and to add 0.12 gram deionized water, stir and obtained in 1 hour transparently being dispersed in the solvent with the stabilized nano TiO 2 particles.After two kinds of above-mentioned colloidal sols mixing, add ten difluoro heptyl propyl trimethoxy silicanes, 3 grams, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan 2 grams, continuing normal temperature stirred 1 hour down, because these two kinds of silane coupling agents are in the modification of corresponding nanoparticle surface, make the nanoparticle self-assembly, form fine and close coating at metal material surface.Fig. 5 is seen in the ultimate analysis of coating.After the sample ambient cure three days, the salt mist experiment of this coating on aluminium alloy reaches 130 hours.
Embodiment 5:
10 gram tetraethoxys are dissolved in the 100 gram dehydrated alcohols, add 0.5% acetum 1 gram, normal temperature stirred 1 hour down.Obtain nano silicon dioxide sol.0.3 gram methyl ethyl diketone is dissolved in the 10 gram alcohol, adds 2 gram tetrabutyl titanates then, stirs after 5 minutes and to add 0.2 gram deionized water, stir and obtained in 1 hour transparently being dispersed in the solvent with the stabilized nano TiO 2 particles.After two kinds of above-mentioned colloidal sols mixing, add ten difluoro heptyl propyl trimethoxy silicanes, 1 gram, two-[γ-(triethoxysilicane) propyl group]-disulphide 1 gram, continuing normal temperature stirred 1 hour down, because these two kinds of silane coupling agents are in the modification of corresponding nanoparticle surface, make the nanoparticle self-assembly, form fine and close coating at metal material surface.After the sample ambient cure three days, this coating reaches 100 hours at the salt mist experiment of ferrous material.Sample photo behind the salt mist experiment is seen Fig. 6.
Embodiment 6:
10 gram tetraethoxys are dissolved in the 100 gram dehydrated alcohols, acetum 3 grams of adding 0.5%, normal temperature stirred 5 hours down, add ten difluoro heptyl propyl trimethoxy silicanes, 2 grams, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan 2 grams, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane 3 grams, because these two kinds of silane coupling agents make the nanoparticle self-assembly in the modification of corresponding nanoparticle surface, form fine and close coating at metal material surface.In order further to improve the thickness of coating, add again 2 grams hydroxy silicon oil.The stereoscan photograph of nanometer anticorrosive coating is seen Fig. 4.After the sample ambient cure three days, the salt mist experiment of this coating on magnesium alloy materials reaches 70 hours.Sample photo behind the salt mist experiment is seen Fig. 7.
Embodiment 7:
10 gram tetraethoxys are dissolved in the 100 gram dehydrated alcohols, add 0.5% acetum 5 grams, normal temperature stirred 8 hours down.Obtain nano silicon dioxide sol.1.5 gram methyl ethyl diketones are dissolved in the 10 gram alcohol, add 3 gram tetrabutyl titanates then, stirs after 5 minutes and to add 0.3 gram deionized water, stir and obtained in 1 hour transparently being dispersed in the solvent with the stabilized nano TiO 2 particles.After two kinds of above-mentioned colloidal sols mixing, add ten difluoro heptyl propyl trimethoxy silicanes, 3 grams, two-[γ-(triethoxysilicane) propyl group]-disulphide 1.5 grams, continuing normal temperature stirred 1 hour down, because these two kinds of silane coupling agents are in the modification of corresponding nanoparticle surface, make the nanoparticle self-assembly, form fine and close coating at metal material surface.After the sample ambient cure three days, the salt mist experiment of this coating on aluminium alloy reaches 190 hours.Sample photo behind the salt mist experiment is seen Fig. 8.
Claims (7)
1. nano anticorrosive coating that is used for various metal substrates, it is characterized in that providing a kind of nano composite oxide protective system that is used for various metal substrates, after this coating was used for processed metal, its coating was curable at normal temperatures, and excellent antiseptic property is arranged; The composite oxides nanoparticle comprises nano silicon dioxide sol and nano titanic oxide sol, and nanoparticle is dispersed in the solvent after fluorine carbon silane coupling agent and other a few class organo-silicon coupling agents modifications; The dense coating of coating dry back self-assembly on the ground formation thickness of 1-5um.
2. in the claim 1 in the nanoparticle, nano silicon dioxide sol is to be raw material with the tetraethoxy, with ethanol is solvent, the careful amount of hydrolyst and the amount of water of regulating, can access uniform nano silicon is the monodispersed particle of 20nm particle diameter, is evenly distributed on and forms colloidal sol in the solvent; Usually tetraethoxy and alcoholic acid weight ratio are 1: 10; Catalyzer is a phosphoric acid, and the weight percent concentration in water is 0.5%; Usually the water add-on is the weight ratio 10-50% of tetraethoxy, and the reaction times is 1-10 hour, and temperature of reaction is a room temperature.
3. in the claim 1 in the nanoparticle, nano titanic oxide sol is to be raw material with the tetrabutyl titanate, is solvent with ethanol, and methyl ethyl diketone is a complexing agent, preparation stabilized nano TiO 2 sol; The stirring reaction time is 1 hour, and temperature of reaction is a room temperature; Usually, the weight ratio of ethanol and tetrabutyl titanate is 2-6:1, and the weight ratio of tetrabutyl titanate and methyl ethyl diketone is 2-8:1, and the weight ratio of tetrabutyl titanate and water is 10:1.
4. in the claim 1 in the nanoparticle, the weight ratio of nano titanic oxide sol and nano silicon dioxide sol is 1:3-8.
5. the silane coupling agent in the claim 1 is: ten difluoro heptyl propyl trimethoxy silicanes, the isocyanic acid propyl-triethoxysilicane, γ-An Bingjisanyiyangjiguiwan, N-(β-aminoethyl)-γ-An Bingjisanjiayangjiguiwan, Y-aminopropyl methyldiethoxysilane, two-[Y-(triethoxysilicane) propyl group]-tetrasulfide, two-[γ-(triethoxysilicane) propyl group]-disulphide, gamma-mercaptopropyltriethoxysilane, γ-(methacryloxypropyl) propyl trimethoxy silicane, γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane.Be a kind of in the system, the also mixture of plurality of silane coupling agents; Silane coupling agent ratio in coating accounts for weight percent 5-30%.
6. the macromolecule resin in the claim 1 is the silicone resin of band functional group, is 10000 hydroxy silicon oil as molecular weight.Usually silicone resin ratio in coating accounts for weight percent 1-10%.
7. the solvent in the claim 1 is an ethanol.
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