CN1281876A - Modified inorganic phosphate coating material - Google Patents
Modified inorganic phosphate coating material Download PDFInfo
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- CN1281876A CN1281876A CN 99115029 CN99115029A CN1281876A CN 1281876 A CN1281876 A CN 1281876A CN 99115029 CN99115029 CN 99115029 CN 99115029 A CN99115029 A CN 99115029A CN 1281876 A CN1281876 A CN 1281876A
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Abstract
The present invention relates to a modified inorganic phosphate coating material, it is a new coating system formed from two kinds of film-forming materials of inorganic phosphate and organics which are combined together and possesses more complete comprehensive performance. Its zinc (aluminium)-enriched coating material is a long-acting anti-corrosion coating for various metal components, and possesses excellent cathodic protection function and anti-corrosion property, and excellent heat resistance, resistance to weathering, adhesive force and flexibility. Its coating process is simple and convenient, it can be directly coated on the surface with slight corrosion, specially it is applicable to protection of large-size metal components.
Description
In modern industrial society, metallic corrosion is a serious problems, and particularly the large-scale steel and iron member that uses in abominable corrosive environment is all the more so.For a long time; the main coating (common name paint) that applies based on organic binder that relies on carries out Metal Protection; but the protection life-span of this class coating is not long; that paint exists is thermo-labile, easily wear out, easily go mouldy, in ocean etc. abominable deadly defect such as protection effect difference in the corrosive environment, so people have been developed inorganic materials guard technologies such as hot spray (or soaking) zinc (or aluminium), silicate zinc-rich paint, phosphoric acid salt richness aluminum paint.Inorganic coating all can be high temperature resistant, aging, do not go mouldy, but also possess the electro-chemical protection function, therefore can reach the purpose of long-lasting protection.It is extremely tight that but inorganic paint is coated with the pre-treatment requirement, generally all requires base material is carried out extremely strict oil removing, rust cleaning surface-conditioning, and surperficial blast reaches the Sa2.5 level at least, and the difficulty of construction is also considerably beyond common japanning.In addition, the matching performance of mechanical property such as the sticking power of inorganic coating, snappiness and finish paint also all is lower than organic coating.
Mentioned a kind of inorganic aluminum coating in the United States Patent (USP) 3248251, it is the representative with the rich aluminum coating of phosphoric acid salt of water as solvent, it can long term operation under the high temperature below 600 ℃, there is not catabiosis, iron and steel is had fabulous barrier propterty, is the main protective coating of various countries' aircraft engine iron and steel parts.But its main drawback is can not be from doing, and the coated technique difficulty is big, thereby has limited its range of application.
In application number is 97107671.5 Chinese patent application, proposed in inorganic phosphate coating material, to replace water as solvent with liquid alcohol and liquid ketone, + 2 ,+3 the superphosphate of valency metal is dissolved in and wherein forms viscous glue solution, this glue again with a certain amount of solia particle mutually proportioning mix and make coating.This coating can be at room temperature from doing, and coated technique is easy, and it is simple to be coated with pre-treatment, and can be with the rust coating.Rich zinc (rich aluminium) coating of the inorganic phosphate of this a new generation has kept the corrosion resistance nature height of original inorganic phosphate protective coating, remarkable galvanic protection ability, heat-resisting, anti-solvent, advantage such as aging, and has enlarged its range of application.But mechanical propertys such as this adhesive force of coatings, snappiness, shock resistance can't meet the demands, and still need to improve.
Purpose of the present invention is exactly to create a kind of so new coating system; it can with phosphate-based inorganic filming substance and specific organic binder well blend in a kind of coating; make like this new coating of making have simultaneously inorganic phosphate coating material can be with rust coating, corrosion resistance nature height, remarkable galvanic protection ability, heat-resisting, anti-solvent, advantage such as wear out; simultaneously have the high mechanical property suitable again, thereby open the brand-new coating system of a generation with organic coating.This new coating system has than existing inorganic phosphate coating material and organic coating over-all properties more fully, by better barrier propterty and the composite modified coating that can form numerous different prescriptions to adapt to various needs.
In the prior art, the research of inorganic salt chemical conduct is confined to the chemical reaction of inorganic salt in the aqueous solution or fused salt more, seldom studies its chemical conduct in organic solution, this is because most inorganic salt are difficult to be dissolved in organic solvent.Application number is that 97107671.5 Chinese patent application has broken through this limitation, furtherd investigate acid inorganic phosphate at polar organic solvent---the chemical conduct in the pure and mild ketone, thereby invented can ambient cure the inorganic phosphate protective coating.Purpose of the present invention is exactly to be on the basis of 97107671.5 Chinese patent at application number, further creates the new coating system that a kind of inorganic phosphate film forming matter and organic binder combine.For reaching this purpose, just must solve the compatible problem of blend of the film forming matter of above-mentioned two kinds of character great disparities.Its prerequisite is that this two classes film forming matter can uniform mixing be an one in a kind of solvent, and forms intact and firm filming in the paint solidification film process.Yet, many organic binders can only be dissolved in the mixed solution of non-polar solvent or nonpolar and polar solvent, therefore it is not enough only studying the chemical conduct of acid inorganic phosphate in polar solvent, and the inorganic phosphate film forming matter also can be dissolved in the same organic solvent.
Have now found that as inorganic phosphate coating material main body film forming matter+2 ,+3 valency superphosphates, as long as adopt dihydrogen phosphate, monohydric phosphate, acid polyphosphoric acid salt and part free phosphoric acid, and do not adopt phosphoric acid normal salt, keep the suitable ratio between each component, and make the mole number ratio of total phosphorus (P) amount and total metal content in the superphosphate remain on 1.5-9: in 1 the scope and H
+/ PO
4 3-〉=1, just can be so that should not only can dissolve (or dispersion) in organic solvents such as polar alcohol or ketones by the acidity inorganic phosphate, also can dissolve (or disperse) in the miscible solvent of polar solvent and non-polar solvent, thereby make the compatible possibility that becomes of acid inorganic phosphate film forming matter, reach purpose of the present invention with most organic binder blend.The superphosphate film forming matter that above-mentioned dihydrogen phosphate, monohydric phosphate, acid polyphosphoric acid salt are formed should comprise the above-mentioned three kinds of superphosphates that adopt phosphoric acid normal salt (or metal oxide, oxyhydroxide, metal-powder) and a certain amount of phosphoric acid to generate through chemical reaction.Though can make raw material with phosphoric acid normal salt, in fact there has not been phosphoric acid normal salt in this situation in the solution after transforming, so this situation also should comprise within the scope of the present invention.As long as above-mentioned acid polyphosphoric acid salt comprises polyphosphate, the catenate ultra-phosphates and the ring-type polymetaphosphate vitreum of straight chain, in a word the phosphoric acid salt H in the binding agent
+/ PO
4 3-〉=1 is superphosphate.Acid polyphosphoric acid salt can directly add, and also simple superphosphate can be obtained through heating self polycondensation.Total phosphorus in the superphosphate proposed by the invention (P) amount and+2 ,+the mole number ratio of 3 total metal contents remains on 1.5-9: in 1 the scope, the lower limit of this scope is to determine like this, in the monohydric phosphate of+divalent metal, phosphorus (P) is 1: 1 with the ratio of metal ion, in the monohydric phosphate of+3 valency metals, phosphorus (P) is 1.5: 1 with the ratio of metal ion.In the phosphoric acid normal salt of+divalent metal, phosphorus (P) is 0.67: 1 with the ratio of metal ion, and in the phosphoric acid normal salt of+3 valency metals, phosphorus (P) is 1: 1 with the ratio of metal ion.If in the dissolved phosphate solution, there is phosphoric acid normal salt, phosphorus (P) is inevitable less than 1.5: 1 with the ratio of metal ion, stipulate the lower limit of this ratio, also just guaranteed in the acid phosphatase salts solution (or colloidal sol) not phosphoric acid normal salt, thereby kept it can be in the solubility in organic mixing solutions.The upper limit of above-mentioned ratio mainly is what and the coating acidity that limits free phosphoric acid at 9: 1, and this is narrated in the back again.
Through experiment confirm, all can be dissolved in the organic binder of organic solvent, comprise Resins, epoxy, epoxy fat, acrylic resin, various vinyl resins, polyvinyl acetal resin, urethane, aminoresin, Synolac, oil-based resin, raw lacquer, resol, polyvinylidene fluoride resin, silicone resin, polyamide resin, polyether resin, coumarone indene resin, petroleum resin, xylene resin, tetraethyl silicate, the partial hydrolysis tetraethyl silicate, various rubber resins, chlorosulfonated polyethylene resin, various Mierocrystalline celluloses, pitch, rosin, rosin processing resin, shellac, siccative oil, various organic binders such as clorafin and modifier thereof can adopt wherein one or more organic binders to realize in suitable mixed organic solvents by suitable ratio and+2, the superphosphate viscous glue solution blend of+3 valency metals is compatible and form the coating system of new generation that new organic binder and inorganic filming substance combine.
The addition of organic binder is at least+2 ,+total amount of the superphosphate of 3 valency metals 5%, otherwise just be difficult for demonstrating effect, there are following four kinds of situations in both mutual reactions.
First kind of situation is not produce tangible reaction mutually basically, and for example pitch and above-mentioned superphosphate just belong to this situation.
Second kind of situation is that reaction takes place significantly to be cross-linked with each other between filmogen, for example between Resins, epoxy and the above-mentioned superphosphate this reaction arranged.
The third situation belongs to complex reaction, and for example the metal ion in polyvinyl butyral resin energy and the phosphoric acid salt produces complex reaction.
The 4th kind of situation belongs to short mutually coagulates or catalysis, for example acid phosphatase salt pair Synolac be solidified with katalysis, basic resins such as polyamide resin can impel the phosphoric acid salt film forming matter to solidify again.
According to different needs, adopt different components and ratio to allocate, can obtain the coating of various applicable performances.In order to guarantee the stability of coating in storage period and working life, those can be reacted each other easily the separately packing and the storage of component of (or short coagulating), remix before using.
The cited various organic binders and+2 in front ,+reaction of superphosphate in mixed solvent of 3 valency metals, be included in basically in above-mentioned four kinds of situations, also there are above-mentioned four kinds of situations that reaction has simultaneously in the blended filmogen certainly.In a word,, can both form suitable coating, thereby realize that organic binder and acid inorganic phosphate film forming matter combine, and form new coating system as long as the allotment of the ratio between each component is appropriate.
Though adding inorganics (for example phosphoric acid normal salt, chromic salt) in organic coating is using already, but this class inorganics only joins in the organic coating as solid pigment, they do not dissolve in coating and do not play filming function yet, perhaps resemble and add some phosphoric acid wash primer and the primer for rusty surface, the base material iron and steel is played phosphatization or transforms rust, and the main body film forming matter of coating remains organic binder.Difference of the present invention be the film forming matter main body be+2 ,+superphosphate of 3 valency metals, add organic binder, only be to improve the performance of inorganic filming substance rather than replace it.Certainly also can be by same principle, with+2 ,+superphosphate of 3 valency metals joins in the coating that organic binder is a main body and improves its performance, but at this moment+2 ,+superphosphate of 3 valency metals also adds wherein as the part of membrane-forming agent, rather than, therefore belong to diverse category with the phosphoric acid normal salt solid pigment that in organic coating, adds used in the prior art as the solid pigment adding.
For narrate convenient for the purpose of, coating of the present invention is called binding agent with the viscous glue solution of film forming matter in the coating and solvent composition, the solids component in the coating is called solia particle.
In its binding agent of coating of the present invention, phosphorus (or phosphate radical) and+2, the mole number ratio of+3 metals is 1.5～9: select in 1 scope, preferably remain on 2-7: in 1 scope, phosphate content and+2, when the ratio of+3 metal contents is big, the acidity of coating is bigger, ratio hour, the acidity of coating also a little less than, the steel substrate that rust is arranged for the surface, preferably be coated with the acid high coating of one deck earlier, for example use phosphate radical and+2, the mole number ratio of+3 metals is the coating of 9: 1 (binder formula four), the effect that this coating dissolving transforms iron rust is stronger, after treating this layer coating drying, apply acid moderate coating again and (for example use the binding agent of prescription one, wherein phosphate radical and+2, the mole number ratio of+3 metals is 6.39: 1).Should adopt acid more weak binding agent to prepare coating for passive solia particle.Need the coated non-metallic base material or apply passive metal base also to adopt acid low coating (for example phosphate radical and+2 in the binding agent ,+the mole number ratio of 3 valence metal ions is 1.5: 1).Should adopt anhydrous or moisture low organic solvent for the stronger binding agent of acidity.Can prolong the shelf life of coating like this.Acid more weak binding agent, the speed of response of it and aluminium (or zinc) powder or other powder is lower, and the shelf life of coating is also longer.Shelf life and raising anticorrosion ability in order to prolong coating can also add the metal inhibitor that contains chromium and do not contain chromium in coating, its consumption is less than 1mol/L.
If in the binding agent+2 ,+metal ions such as 3 valency master metal chromium, magnesium, zinc, calcium, strontium, aluminium, iron, manganese, barium, lead, copper, tin and molybdenum, chromium wherein is selected from+3 valency chromium ions or in phosphoric acid solution, obtain+3 valency chromium ions with reductive agent reduction+6 valency chromium.Liquid alcohol in the binding agent is selected from ethanol, methyl alcohol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol and liquid polyol etc., and their mixture.Liquid ketone in the binding agent is selected from acetone, butanone, pimelinketone, methylcyclohexanone, isophorone, diacetone alcohol etc. and their mixture.Except liquid alcohol and liquid ketone, other organic solvent in mixed solvent comprises aliphatic hydrocarbon, aromatic hydrocarbon, lipid solvent, alcohol ether and solvent of ether ester type and replacement hydrocarbon solvent and their mixture.The content of the solvent in the binding agent can change according to different needs, ultrafine solids particulate very low for density and that particle diameter is very little should adopt rarer binding agent to come prepared paint, at this moment solvent can be up to 95% in the coating, in order to adapt to some special requirement, when for example doing bonding use, can only add a small amount of solvent (for example 5% solvent), for the ease of transportation with store, also solubilizing agent is not added solvent before use again.The total content of phosphorus in the coating (P) is 0.3～10mol/L, the total amount of metal ion is 0.05～6.2mol/L, the content of solvent is not more than 95%, in solvent, the total content of liquid alcohol and liquid ketone (weight) should be not less than superphosphate total content (weight), otherwise coating is difficult for being uniformly dispersed.In solvent, can contain less water, but can not surpass 20% of solvent gross weight, otherwise coating is with instability.
Solia particle in the coating is a magnesium for corrosion-resistant coating, zinc, metal-powder such as aluminium or be the powdered alloy of base and zinc powder or the Zinc alloy powder of crossing through Passivation Treatment with these metals, zinc covering aluminium powder and zincizing aluminium powder, for conductive coating is Graphite Powder 99, carbon black, silver or silver close full powder, copper or copper alloy powder, zinc or Zinc alloy powder and other powder that can conduct electricity, for solid lubricant coating is graphite, boron nitride, molybdenumdisulphide, tungsten disulfide, talcum powder, plumbous oxide and other powdered lubricant end are refractory oxide for refractory coating, refractory nitride, refractory carbides, refractory silicide and other heat-resisting powder.For underwater antifouling coating is the oxide compound of metals such as copper, tin, lead.Can also add the ultrafine powder of some diameters in the coating, in order to the viscosity of adjusting coating with impel coating curing less than the oxide compound of metals such as 1 micron aluminium, silicon, titanium, chromium.In order to improve the coating corrosion-resistant life, can also in coating, add some solid pigments, for example zinc-chrome yellow, zinc phosphate, aluminum phosphate, aluminium triphosphate, strontium yellow, yellow ultramarine, baryta yellow, lead chromate, barium metaborate, red lead, iron oxide red, Yun Tie, wustite, mica, glass flake and pigment dyestuff are to adapt to different needs.The shape of the solia particle that coating is contained is not limit, but all should be able to pass through 100 eye mesh screens, preferably by 325 eye mesh screens.The consumption of solia particle is decided on different purposes, and every liter of contained solia particle amount of coating is selected in 0～3000 gram scope, preferably 300～1200 grams.Can not add the solid particulate as the varnish time spent.
Adopt zinc powder or Zinc alloy powder, can slow down the sacrifice loss of coating, improve the protection effect of coating through Passivation Treatment.Can select chromating or chromium-free deactivation for use.When adopting chromating, the compound that the composition of passive film mainly is made up of one or more metals in the metals such as zinc, strontium, barium, calcium, lead, trivalent chromium and oxygen and sexavalent chrome.
After the oxide compound of metal (or alloy) powder such as the zinc in the solia particle, aluminium, magnesium and these metals, hydroxide powder and the adhesive gelatin reaction, make the superphosphate in the glue change complete water-fast neutral phosphonic hydrochlorate into.Can be after this coating completely solidified in the various organic or inorganic coatings of its surface-coated to adapt to different needs.
In order to strengthen the conversion capability of coating to iron rust, in this coating, can add an amount of converting agent of iron rust, for example yellow prussiate of potash, Weibull or other converting agent of iron rust, wherein the potassium ion of yellow prussiate of potash is the monovalence metal, it and phosphatase reaction generate potassium phosphate salt.The monovalence metal phosphate all is a water soluble salt, and it can reduce the performance of coating, therefore should reduce its addition as far as possible.For this reason, the mole number of maintenance monovalence metal is no more than the contained metal molar of whole phosphoric acid salt and counts 10% of total amount.In addition, also can add in the coating+phosphoric acid salt of 4 valency metals, for example+4 the compound of valency manganese and titanium.But+4 valency metals are generally unstable, therefore should control its content, keep+4 valency metal molar numbers to be no more than the contained metal molar of whole phosphoric acid salt and count 30% of total amount.
In order to improve the performance of coating, can also add various coatings additive(s)s.As increase iron chelator---laccol etc.; As increase film toughener---gallic acid, pyrogallol, pyrocatechol etc.; As increase flow agent---silicone oil etc.; As increase antisettling agent---organic bentonite, polyethylene wax, synthesizing superfine silicon-dioxide etc.
Discuss technique effect of the present invention below in conjunction with coating processes.At first an advantage is that coating coating processes of the present invention is easy, thereby it has the utmost point scope of application widely.Owing to this coating can dissolve slight iron rust or oxide film and micro-grease and moisture content, therefore allow to exempt the preceding blast of coating and handle base material, add that coating can be at room temperature from doing and curing, this has just simplified coating processes greatly.Methods such as this coating can adopt brush, rolls, spray apply; determine the number of plies of coating and the thickness of coating according to actual needs; do not exist and resemble the phenomenon that has been coated with thick the existing silicate zinc-rich coating can cracking to come off; it can apply repeatedly according to actual needs fully and obtain very thick coating, thereby obtains the higher galvanic protection life-span.Also can be coated with very thinly (for example adopting zinc flake can make thick coating), to adapt to some needs less than 10 μ m.Adopt the zinc powder coatings formulated to apply the back and put several minutes coatings with regard to surface drying in the air of room temperature, coating was done solid work in about 1 hour.Spelter coating after the curing has electroconductibility and solidity to corrosion preferably.The aluminum coating curing speed is slower, in order to accelerate the curing speed of aluminum coating, the aluminum coating after the dry hardening can be heated to 400～650 °F rapidly, several minutes undercoat with regard to completely solidified.Because there is the oxide film of one deck densification on the aluminium powder surface, thereby the aluminum coating after solidifying is still non-conductive, can adopt various thermals source that coating is heated rapidly to fusing point near aluminium, and make the aluminum coating conduction in the several seconds; Also can adopt aluminium powder in the aluminum coating after the mechanical presses method makes curing to be communicated with and conduct electricity.If adopt aluminium zinc alloy powder, zinc covering aluminium powder or zincizing aluminium powder to replace pure aluminium powder, just possess electroconductibility after can making the coating self-vulcanizing, and have the advantage of aluminum coating and spelter coating concurrently.Coating after the curing not only is insoluble to cold water and also is insoluble to 100 ℃ boiling water, and the long period of soaking of anti-various oils, can swelling or rotten.This coating also has very high thermotolerance (aluminum coating thermotolerance for example of the present invention reaches 1100), oxidation-resistance and weathering resistance.Aluminum coating body resistivity of the present invention has only 1 Ω m, be ten thousand of existing silicate zinc-rich coating body resistivity/to 1,000,000/, because the high conductivity and the negative potential of coating, thereby obtain fabulous galvanic protection function.Introduce the performance measured result of spelter coating of the present invention below:
| Interventions Requested | Detected result | The method of inspection | Remarks | |
| Time of drying | Surface drying, min | ????＜5 | GB1728-79 second method | |
| Do solid work h | ????＜1 | GB1728-79 first method | ||
| Resistance to salt water (21d) | Do not have and peel off, bubble, get rusty | GB1763-79 first method | ||
| Salt fog resistance (7d) | Do not have and peel off, bubble, get rusty | GB/T1771-91 | Dried film thickness 50 μ m have carried out 7000 hours still non-corrodings | |
| Thermotolerance (400 ± 10 ℃, 4h) | No aliquation, come off and ftracture | GB1735-79 | ||
| Heat-resisting salt water-based (80 ℃, 2h) | Do not have and peel off, bubble | GB1763-79 second method | ||
| Sticking power, level | ????1 | GB1720-79 | ||
| Snappiness, mm | ????1 | GB/T1731-93 | ||
| Shock-resistance, kgcm | ????50 | GB/T1732-93 | ||
| Anti-kerosene (21d) | No aliquation, come off and ftracture | GB/T1734-93 first method | ||
| Anti-diesel oil (21d) | No aliquation, come off and ftracture | GB/T1734-93 first method | ||
| Petrol-resistance (21d) | No aliquation, come off and ftracture | GB/T1734-93 first method | ||
| Anti-1% Seconary Alkane Sulphonate Sodium solution, 48h | No aliquation, come off and ftracture | GB1763-79 first method | ||
| Cross-hatching sticking power, level | ????1 | ?GB9286-88 | ||
| Draw back method sticking power | ????5.44MpaA | ?GB5210-85 | ||
| Wear resistance (500g, 500 change) | Weightless 0.075 gram | ?GB1768-79(89) | ||
Introduce some embodiments of the present invention below, they are some typical case's representatives, do not comprise full content of the present invention, therefore should not be construed as limitation of the present invention.(1) preparation of binding agent
A phosphoric acid diamino chromium [Cr (H fills a prescription
2PO
4)
3] 0.24mol phosphoric acid (H
3PO
4) 0.84mol magnesium oxide (MgO) 0.0004mol water (H
2O) 40g polyvinyl butyral resin 10g methylethylketone (CH
3COC
2H
5) 200g ethanol (C
2H
5OH) to 1L
Prescription bisphosphate aluminium (AlPO
4) 0.67mol primary magnesium phosphate [Mg (H
2PO
4)
23H
2O] 0.1mol phosphoric acid (H
3PO
4) 0.7ml zinc oxide (ZnO) 0.03mol water (H
2O) 10g silicone resin liquid (60%) 20g pimelinketone [CH
2(CH
2)
4CO 120g ethanol (C
2H
5OH) to 1L
Prescription triphosphoric acid dihydro chromium [Cr (H
2PO
4)
3] 0.15mol phosphoric acid (H
3PO
4) 0.6mol aluminium hydroxide AL (OH)
30.02mol petroleum pitch 70g dimethylbenzene C
5H
4(CH
3)
2120g pimelinketone [CH
2(CH
2)
4CO] 60g methylethylketone (CH
3COC
2H
5) 60g ethanol (C
2H
5OH) to 1L
Four biphosphate chromium [Cr (H fill a prescription
2PO
4)
3] 0.15mol phosphoric acid (H
3PO
4) 1.08mol magnesium oxide (MgO) 0.02mol yellow prussiate of potash [K
4Fe (CN)
63H
2O] 2g polyvinyl butyral resin 10g ethanol (C
2H
5OH) to the implementation example of 1L (2) applying coating
Embodiment one
Binding agent (by prescription one) 1L
Zinc powder (particle diameter 5～10 μ m) 1200g
Be coated in 3 carbon steel test pieces of light rust about 45～55 μ m of coat-thickness after stirring evenly.Coating was placed in the air of room temperature after 7 days, drew " X " with sharp device on coating and exposed to matrix steel, placed the salt fog cabinet of 5%Nacl to keep 95 °F, the no iron rust appearance through 1000 hours.
Embodiment two
Binding agent (by prescription two) 1L
Aluminium powder (particle diameter 4～5 μ m ball-type aluminium powders) 420g
Be coated in 8 thick carbon steel test pieces of 1mm about 55～65 μ m of coat-thickness after stirring evenly.Dried in the air under the room temperature 1 hour, the dry hardening of coating, nail is scraped, and with oxyacetylene torch test piece is burnt fast to dark red, and the about 0.2-0.5 Ω of coating body resistivity m is surveyed in the cooling back, gets 2 test pieces along 90 ° of the curvature bendings of diameter 8mm, and coating does not come off.Get other 3 test pieces by embodiment 1 similarity condition and carry out salt-fog test no iron rust appearance in 1000 hours.Get 3 remaining test pieces and make thermal test, excellent through 100 hours coatings of 1050 bakings.
Embodiment three
Binding agent (by prescription two) 1L
Graphite (colloid powder) 250g
Magnesium oxide (particle diameter is less than 1 μ m) 0.2mol
Aluminium hydroxide (particle diameter is less than 1 μ m) 0.15mol
Ethanol 0-800ml
Be coated on nonmetallic surfaces such as pottery, glass or plastics, placed 2 hours under the room temperature, then 400 bakings 30 minutes, the coating conduction is good, and has lubrication.Be applied to the equadag coating on the pottery, anti-1500 high temperature.
Embodiment four
Replace 250g graphite with the 500g boron nitride, other is coated on the high temperature steel with embodiment three, and coating has well lubricated and antifriction function, and coating can anti-1800 °F not be broken in 50 hours.
Embodiment five
Replace graphite with 500g molybdenumdisulphide, other is coated on the steel part with embodiment three, and coating has well lubricated and antifriction function.
Embodiment six
Replace graphite with the 700g aluminum oxide, other is applied on the stainless steel with embodiment three, coating ability high temperature and heat-blocking action is arranged more than 1500.
Embodiment seven
Aluminium zinc powder with 940g (95%Zn 5%AL) replaces zinc powder, and other is with embodiment one, and the corrosion resisting property of coating is better than spelter coating.
Embodiment eight
Aluminium zinc powder with 630g (55%AL, 43.5%Zn, 1.5% silicon) replaces the 420g aluminium powder, and other is with embodiment two.The every performance of coating and the aluminum coating of example two are very approaching, but the galvanic protection function is not better than aluminum coating in having the corrosive medium of chlorion.
Embodiment nine
Increase the 2g strontium yellow in embodiment one, other can prolong the protection life-span of spelter coating with example one.
Embodiment ten
A moment is soaked in the steel test piece in the gasoline that contains 0.1% machine oil, taking out to dry in the test piece of back has the skim oil film, and according to carrying out salt-fog test behind same coating of embodiment one and the method applying coating, effect is identical with example one.
Embodiment 11
Press the test piece of embodiment one and example two applying coatings and soak taking-up after 3000 hours in kerosene, coating is as excellent as before, and every after tested performance is constant.
Embodiment 12
Binding agent (by prescription four) 1L
Zinc powder 1200g
Be coated with one deck coating (conversion iron rust) at the steel piece surface that rust is arranged earlier by above-mentioned prescription, and then be coated with the two or three layer by embodiment one, effect is with embodiment one.
Embodiment 13
Press embodiment one, add 50 gram glass flakes in the coating, can improve the water-repellancy and the hardness of coating.
Embodiment 14
Press embodiment one, add 5 gram superfine silicon dioxides in the coating, the zinc powder in the coating is difficult for precipitation, is convenient to construction.
Claims (11)
1. coating, it is made up of binding agent and solia particle, the binding agent that it is characterized in that coating by add organic binder+2 ,+superphosphate dissolving (or dispersion) formed viscous glue solutions in mixed organic solvents of 3 valency metals, wherein contained superphosphate comprises dihydrogen phosphate, monohydric phosphate, acid polyphosphoric acid salt and part free phosphoric acid, and the mole number ratio of phosphorus in superphosphate (P) and total metal content is 1.5-9: 1 and H
+/ PO
4 3-〉=1, the weight of organic binder is no less than 5% of phosphoric acid salt gross weight in the binding agent, the mixed coating of binding agent and solia particle, be coated on the base material after, along with the volatilization of solvent, dry voluntarily and sclerosis forms coating.
2. by the described coating of claim 1, in its binding agent, be 0.3-10mol/L in the acid phosphatase salts contg of phosphorus (P), the total amount of metal ion is 0.05-6.2mol/L, the content of organic solvent is not more than 95% (weight ratio).
3. by the described coating of claim 1, its mixed organic solvents is selected from ethanol, methyl alcohol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol, Pentyl alcohol, primary isoamyl alcohol, liquid polyol, acetone, butanone, pimelinketone, methylcyclohexanone, isophorone, diacetone alcohol, aliphatic hydrocarbon, aromatic hydrocarbon, lipid solvent, pure ether solvent, solvent of ether ester type, replacement hydrocarbon solvent and their mixture.
4. by the described coating of claim 1, in its organic solvent, the total content of liquid alcohol and liquid ketone (weight) is not less than the gross weight of the contained superphosphate of coating, and the content of water is not more than 20% of solvent gross weight.
5. by the described coating of claim 1, coating is added with+1 or+phosphoric acid salt of 4 valency metals, wherein+1 the mole number of valency metal is no more than the contained metal molar of whole phosphoric acid salt and counts 10% of total amount, and wherein+4 the mole number of valency metal is no more than the contained metal molar of whole phosphoric acid salt and counts 30% of total amount.
6. by the described coating of claim 1, wherein+2 ,+superphosphate of 3 valency metals is selected from superphosphate of metals such as magnesium, zinc, aluminium, calcium, strontium, iron, manganese, barium, lead, copper, tin, chromium, molybdenum and composition thereof.
7. by the described coating of claim 1, solia particle wherein is selected from metal-powder and the non-metal powder and their mixture of different shape, and all solids particulate should be able to pass through 100 eye mesh screens.The solia particle amount that every liter of binding agent should add is the 0-3000 gram.
8. by the described coating of claim 1, solia particle wherein is selected from aluminium powder, Al alloy powder, zinc powder, Zinc alloy powder, the magnesium powder, the magnesium alloy powder, the zinc powder of passivation (Zinc alloy powder), the zinc covering aluminium powder, the zincizing aluminium powder, the oxide compound of aluminium, the oxide compound of silicon, titanyl compound, the oxide compound of chromium, the oxide compound of copper, the oxide compound of tin, plumbous oxide compound, zinc-chrome yellow, zinc phosphate, aluminum phosphate, aluminium triphosphate, strontium yellow, yellow ultramarine, baryta yellow, lead chromate, barium metaborate, red lead, iron oxide red, Yun Tie, wustite, mica, glass flake and pigment dyestuff, and the mixture of above-mentioned two or more solia particles.
9. by the described coating of claim 8, wherein there is the protective membrane that one deck chromating or non-chromate passivation form on the zinc powder of passivation (Zinc alloy powder) surface.
10. by the described coating of claim 1, wherein organic binder is selected from Resins, epoxy, acrylic resin, various vinyl resins, polyvinyl acetal resin, urethane, aminoresin, Synolac, oil-based resin, raw lacquer, resol, polyvinylidene fluoride resin, silicone resin, polyamide resin, polyether resin, coumarone indene resin, petroleum resin, xylene resin, tetraethyl silicate, the partial hydrolysis tetraethyl silicate, various rubber resins, chlorosulfonated polyethylene resin, various Mierocrystalline celluloses, pitch, rosin, shellac, siccative oil, clorafin and their mixture.
11. by the described coating of claim 1, wherein various auxiliary agents be can be added with, yellow prussiate of potash, tannic acid, laccol, gallic acid, pyrogallol, pyrocatechol, synthesizing superfine silicon-dioxide, organic bentonite, silicone oil, polyethylene wax and other various coating used additives are selected from.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99115029 CN1128188C (en) | 1999-07-21 | 1999-07-21 | Modified inorganic phosphate coating material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 99115029 CN1128188C (en) | 1999-07-21 | 1999-07-21 | Modified inorganic phosphate coating material |
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| Publication Number | Publication Date |
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| CN1281876A true CN1281876A (en) | 2001-01-31 |
| CN1128188C CN1128188C (en) | 2003-11-19 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 99115029 Expired - Fee Related CN1128188C (en) | 1999-07-21 | 1999-07-21 | Modified inorganic phosphate coating material |
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| CN (1) | CN1128188C (en) |
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