阅读说明：本技术 一种高耐热腐性涂层封孔剂 (A kind of high heat resistance corruption coating sealing reagent ) 是由 郭熙海 于 2019-08-02 设计创作，主要内容包括：本发明公开了一种高耐热腐性涂层封孔剂,属于封孔剂技术领域。本发明以酸处理玄武岩,再进行氧化,并用表面活性物质提高其活性,使用有机硅增强与其它大分子物质间的结合度,在受热时产生气体散发热量,通过水热法在其缝隙纵向形成勃姆石成分进行纳米级填补,使耐高温性能得以提升,改善热腐蚀性能,完成对涂层孔隙的封填；利用巯基乙酸对蛭石表面的Lewis酸等活性中心或活性基团发生反应,受高温作用时,显著降低颗粒间的表面张力,并能形成很好的封孔效果；以镁、铝金属盐作为原料,通过水热法制具有良好吸附性类水滑石成分,并通过络合作用产生螯合,提高耐热腐性能。本发明解决了目前常用涂层封孔剂存在着耐高温热腐蚀性较差的问题。(The invention discloses a kind of high heat resistance corruption coating sealing reagents, belong to hole sealing agent technical field.The present invention handles basalt with acid, it is aoxidized again, and its activity is improved with surface reactive material, use the conjugation between organosilicon enhancing and other macromolecular substances, gas is generated when heated and distributes heat, and boehmite ingredient progress nanoscale is longitudinally formed in its gap by hydro-thermal method and is filled up, can be promoted heat-resisting quantity, improve hot corrosion resistance, completes the packing to coating porosity；It is reacted using thioacetic acid to the acid isoreactivity center Lewis on vermiculite surface or active group, when by high temperature action, significantly reduces intergranular surface tension, and good sealing of hole effect can be formed；There is good dispersiveness houghite ingredient using magnesium, aluminum metal salt by hydro-thermal method fixture as raw material, and chelating is generated by complexing, improves heat-resisting rotten performance.The present invention solves the problems, such as current common coatings hole sealing agent, and there is high temperature heat-resistant corrosivity is poor.)

1. a kind of high heat resistance corruption coating sealing reagent, according to the mass fraction, including following component: 3 ~ 7 parts of sodium tungstates, 0.2 ~ 0.5 Part defoaming agent, 1 ~ 4 part of dispersing agent, 25 ~ 50 parts of water, which is characterized in that further include: 30 ~ 50 parts of compound hole sealing base-materials, 15 ~ 25 parts Booster action material.

2. a kind of high heat resistance corruption coating sealing reagent according to claim 1, which is characterized in that the compound hole sealing base-material Preparation method includes the following steps:

(1) in 70 ~ 85 DEG C, 1:12 ~ 20 take basalt, hydrochloric acid solution mixing in mass ratio, and heat preservation is filtered while hot, collect filter residue The mixing of periodic acid solution is added in 1:10 in mass ratio ~ 15, keeps the temperature in 80 ~ 90 DEG C, cooling, filtering, collects filter cake washing, dry, It collects dried object and takes 15 ~ 30 parts of dried objects, 2 ~ 5 parts of vinyltriethoxysilane, 3 ~ 7 parts of cetyls according to the mass fraction Trimethylammonium bromide, 6 ~ 10 parts of dehydrated alcohol grindings, obtain abrasive；

(2) according to parts by weight, 30 ~ 40 parts of abrasives, 17 ~ 23 parts of polyvinyl alcohol, 15 ~ 20 parts of dimethyl acetamides, 4 ~ 7 parts are taken Methacryl hydroxypropyltrimonium chloride, 50 ~ 70 parts of water mixing, lead to nitrogen protection, stir in 100 ~ 120 DEG C, cooling, from The heart collects centrifugation object 1:6 in mass ratio ~ 10 and reagent A mixing is added, and in 50 ~ 65 DEG C of insulated and stirreds, filter cake calcining is collected in filtering, Calcined material is obtained, calcined material is taken to pulverize and sieve, collects sieving particle to get compound hole sealing base-material.

3. a kind of high heat resistance corruption coating sealing reagent according to claim 2, which is characterized in that the examination in the step (2) Agent A: 1:2 ~ 4:30 ~ 50 take sodium metaaluminate, urea, water mixing to get reagent A in mass ratio.

4. a kind of high heat resistance corruption coating sealing reagent according to claim 1, which is characterized in that the system of the booster action material Standby: in 30 ~ 45 DEG C, 12 ~ 16:1 in mass ratio takes reagent B, waterglass mixing, obtains mixture, takes mixture that mixture matter is added The auxiliary agent of amount 10 ~ 15%, closed to be warming up to 120 ~ 145 DEG C, insulation reaction obtains reaction material, releases closed, addition reaction material quality 3 ~ 7% additive, the pretreatment vermiculite of reaction material quality 7 ~ 13% are mixed, and rotary evaporation is to get booster action material.

5. a kind of high heat resistance corruption coating sealing reagent according to claim 4, which is characterized in that the reagent B: by weight Number meter takes 5 ~ 8 parts of magnesium nitrates, 2 ~ 5 parts of aluminum nitrates, 6 ~ 10 parts of zinc nitrates, 150 ~ 200 parts of water mixing, obtains mixing saline solution, take mixing Carbamide mixing is added to get reagent B in saline solution 20 ~ 30:1 in mass ratio.

6. a kind of high heat resistance corruption coating sealing reagent according to claim 4, which is characterized in that the auxiliary agent: in mass ratio 3 ~ 6:1 takes potassium rhodanate, sodium citrate mixing to get auxiliary agent.

7. a kind of high heat resistance corruption coating sealing reagent according to claim 4, which is characterized in that the additive: in 30 ~ 40 DEG C, it takes fatty alcohol polyoxyethylene ether 3 ~ 7:1 in mass ratio that triethanolamine mixing is added, obtains mixture, take mixture in mass ratio Hydroxyethyl cellulose, epoxy resin mixing is added to get additive in 10:1:2 ~ 5.

8. a kind of high heat resistance corruption coating sealing reagent according to claim 4, which is characterized in that the pretreatment vermiculite: in 20 ~ 25 DEG C, vermiculite is taken to pulverize and sieve, takes sieving particle 1:3 in mass ratio ~ 7 that dimethylformamide is added and be uniformly mixed, be warming up to 30 ~ 45 DEG C, the sodium bisulfate mixing of 30 ~ 55% thioacetic acid of sieving granular mass, the granular mass 12 ~ 20% that is sieved is added, it is close It closes, in 110 ~ 125 DEG C of insulation reactions, obtains reactant, take reactant 20 ~ 35:1 in mass ratio that vulcanized sodium mixing is added, heat preservation is cold But, it filters, filter residue is taken to wash, it is dry to get pretreatment vermiculite.

9. a kind of high heat resistance corruption coating sealing reagent according to claim 1, which is characterized in that the defoaming agent: pressing quality Take polyoxyethyl propyl polyoxyethanyl glycerin ether, dimethyl silicone polymer mixing to get defoaming agent than 1:3 ~ 7.

10. a kind of high heat resistance corruption coating sealing reagent according to claim 1, which is characterized in that the dispersing agent: pressing quality Take vinyl pair stearic amide, polyacrylamide mixing to get dispersing agent than 2 ~ 5:1.

Technical field

The present invention relates to hole sealing agent technical fields, and in particular to a kind of high heat resistance corruption coating sealing reagent.

Background technique

Aluminium element is that most wide one of element is distributed in nature.Fine aluminium quality is soft, density is small, ductility is good, plasticity is high, It can carry out various machinings and have good electric conductivity and thermal conductivity, electric conductivity is only second to, and purposes is very extensive.Due to The intensity of fine aluminium is low, could only be made as structural material by by its alloying, obtaining the aluminium alloy that density is small, intensity is high With.Aluminum alloy materials have a series of excellent physics, chemistry, mechanics and processing performance, can satisfy from kitchen meal apparatus to point End science and technology is drilled industry to a variety of requirements of all trades and professions such as transportation and aerospace from building dress, is passed through in its people It is used widely in the every field of Ji.

Aluminium is the active substance of chemical property, and surface will form one layer of oxide thin layer film in air, this layer of oxidation film exists There is good corrosion resistance in dry atmosphere, but in the atmosphere of pollution and water, seawater, soil and various corrosive mediums, does not then have Enough protective values.Therefore, aluminium and aluminum alloy surface require to be surface-treated in many cases, and anodic oxidation is that aluminium closes The most common surface treatment means of gold.This method is that aluminium alloy is immersed in the oxidation such as acidic electrolysis bath such as sulfuric acid, oxalic acid, phosphoric acid Pass to certain additional positive current in liquid, aluminum alloy surface can be formed one layer with amorphous alumina be mainly form, thickness Up to tens microns of hard coating.Anode oxide film have double-layer structure, internal layer is thin and compact, claim barrier layer, outer layer be compared with Thick porous layer, this porous layer have excellent adsorption capacity, often as the bottom of aluminium coloring or the mistake of outer overcoat layer Cross layer, but anti-corrosion capability, weatherability, stain resistance, etc. cannot all reach requirement, therefore consider from practical application, aluminium sun The micropore of pole oxidation film must be closed.The anode oxide film of non-sealing of hole makes to be exposed to due to the area in a large amount of micropore holes The effective surface area of workpiece or sample in environment increases by tens times and arrives hundreds of times, and corresponding corrosion rate also greatly increases thus Add.Therefore anodizing of aluminium film is in addition to individual such as abrasion-resistive hard oxidation films, from corrosion resistance and stain resistance consideration is improved, all It must carry out sealing pores.

Industrial relatively common common sealing of hole operating method has 4 kinds: high temperature hole sealing, cold seal hole, medium temperature sealing of hole, organic matter Sealing of hole.

High temperature hole sealing, high temperature hole sealing are called boiling water sealing hole, are the oxidation film (Al by aluminum products surface₂O₃) hydration it is anti- Vigorous nurse body, vigorous nurse body good corrosion resistance should be generated, and the expansion of oxidation film molecular volume seals oxide-film micropore when hydration reaction It closes.Cold seal hole, cold seal hole do not need to heat, and can operate at room temperature, so being called room temperature sealing of hole.Generally use fluorine in cold seal hole Change nickel, relies primarily on the nickel ion of positive divalent and the fluorine ion of negative one valence.

Medium temperature sealing of hole, medium temperature sealing of hole refer to a kind of temperature of the sealing of hole sealing of hole between the two in high temperature hole sealing and cold seal hole Technology, main hole sealing agent are nickel acetate, and stability is good, is easy to control.

Organic matter sealing of hole coats one layer of organic polymer coating on aluminium material oxidation film.

At present in aluminum alloy anode oxidative work-up technique, in order to reduce the voidage and adsorption capacity of anode oxide film, It is a large amount of using low temperature pore sealing agent mild in containing, the hole sealing agent sealing of hole is fast, easy to operate, dyestuff when sealing of hole can be effectively prevented It leaches, impurity permission is big, and sealing of hole weightlessness is minimum, and properties of product and appearance are attained by requirement.But due to nickeliferous metal Gadget is contacted with human skin for a long time, and can dissociate Ni out under the effect of human body sweat stain²⁺, disturb skin and itch, induce Allergic contact Dermatitis is forbidden to use by many countries, and has put into effect relevant limitation standard, thus exploitation can volume production without nickel hole-sealing technology at For the task of top priority.There are many relevant report about no nickel hole sealing technology, but comparative maturity: fluotitanate without nickel medium temperature Hole sealing agent.This hole sealing agent is potassium fluotitanate 5-10g/l, cyclohexanone 0.05-0.15g/l, isoamyl alcohol 0.05-0.15g/l.The envelope Temperature of hole agent when carrying out sealing of hole is 55-65 DEG C, and the processing time is 1.0-1.5um/min.Although the hole sealing agent solves Injury of the nickel to human body and the pollution to environment, but coating sealing reagent has that high temperature heat-resistant corrosivity is poor.

Summary of the invention

The technical problems to be solved by the invention: for current common coatings hole sealing agent there is high temperature heat-resistant corrosivity compared with The problem of difference, provides a kind of high heat resistance corruption coating sealing reagent.

In order to solve the above technical problems, the present invention is using technical solution as described below:

A kind of high heat resistance corruption coating sealing reagent, according to the mass fraction, including following component: 3 ~ 7 parts of sodium tungstates, 0.2 ~ 0.5 part Defoaming agent, 1 ~ 4 part of dispersing agent, 25 ~ 50 parts of water, further includes: 30 ~ 50 parts of compound hole sealing base-materials, 15 ~ 25 parts of booster action material.

The preparation method of the compound hole sealing base-material, includes the following steps:

(1) in 70 ~ 85 DEG C, 1:12 ~ 20 take basalt, hydrochloric acid solution mixing in mass ratio, and heat preservation is filtered while hot, collect filter residue The mixing of periodic acid solution is added in 1:10 in mass ratio ~ 15, keeps the temperature in 80 ~ 90 DEG C, cooling, filtering, collects filter cake washing, dry, It collects dried object and takes 15 ~ 30 parts of dried objects, 2 ~ 5 parts of vinyltriethoxysilane, 3 ~ 7 parts of cetyls according to the mass fraction Trimethylammonium bromide, 6 ~ 10 parts of dehydrated alcohol grindings, collect abrasive；

(2) according to parts by weight, 30 ~ 40 parts of abrasives, 17 ~ 23 parts of polyvinyl alcohol, 15 ~ 20 parts of dimethyl acetamides, 4 ~ 7 parts are taken Methacryl hydroxypropyltrimonium chloride, 50 ~ 70 parts of water mixing, lead to nitrogen protection, stir in 100 ~ 120 DEG C, cooling, from The heart collects centrifugation object 1:6 in mass ratio ~ 10 and reagent A mixing is added, and in 50 ~ 65 DEG C of insulated and stirreds, filter cake calcining is collected in filtering, Calcined material is obtained, calcined material is taken to pulverize and sieve, collects sieving particle to get compound hole sealing base-material.

Reagent A in the step (2): 1:2 ~ 4:30 ~ 50 take sodium metaaluminate, urea, water mixing to get examination in mass ratio Agent A.

The preparation of the booster action material: in 30 ~ 45 DEG C, 12 ~ 16:1 in mass ratio takes reagent B, waterglass mixing, obtains mixed Material is closed, takes mixture that the auxiliary agent of mixture quality 10 ~ 15% is added, closed to be warming up to 120 ~ 145 DEG C, insulation reaction must react Material releases closed, the pretreatment vermiculite mixing of the additive, reaction material quality 7 ~ 13% of addition reaction material quality 3 ~ 7%, rotation Turn evaporation to get booster action material.

The reagent B: according to parts by weight, 5 ~ 8 parts of magnesium nitrates, 2 ~ 5 parts of aluminum nitrates, 6 ~ 10 parts of zinc nitrates, 150 ~ 200 are taken Part water mixing, obtains mixing saline solution, takes mixing saline solution 20 ~ 30:1 in mass ratio that carbamide mixing is added to get reagent B.

The auxiliary agent: 3 ~ 6:1 in mass ratio takes potassium rhodanate, sodium citrate mixing to get auxiliary agent.

The additive: in 30 ~ 40 DEG C, taking fatty alcohol polyoxyethylene ether 3 ~ 7:1 in mass ratio that triethanolamine mixing is added, Mixture is obtained, takes mixture 10:1:2 in mass ratio ~ 5 that hydroxyethyl cellulose, epoxy resin mixing is added to get additive.

The pretreatment vermiculite: in 20 ~ 25 DEG C, taking vermiculite to pulverize and sieve, and sieving particle 1:3 in mass ratio ~ 7 is taken to be added two Methylformamide is uniformly mixed, and is warming up to 30 ~ 45 DEG C, and 30 ~ 55% thioacetic acid, the sieving particle matter of sieving granular mass is added Amount 12 ~ 20% sodium bisulfate mixing, it is closed, in 110 ~ 125 DEG C of insulation reactions, obtain reactant, take reactant in mass ratio 20 ~ Vulcanized sodium mixing is added in 35:1, keeps the temperature, cooling, and filtering takes filter residue to wash, dry to get pretreatment vermiculite.

The defoaming agent: 1:3 ~ 7 take polyoxyethyl propyl polyoxyethanyl glycerin ether, dimethyl silicone polymer mixing in mass ratio, Up to defoaming agent.

The dispersing agent: 2 ~ 5:1 in mass ratio takes the double stearic amides of vinyl, polyacrylamide mixing to get dispersion Agent.

The present invention is compared with other methods, and advantageous effects are:

(1) present invention first handles basalt with acid, then aoxidizes to it, and improves its activity with surface reactive material, uses Conjugation between organosilicon enhancing and other macromolecular substances, also, using polyvinyl alcohol ingredient to basalt fine fraction It is wrapped up, then polymer is modified using long chain cation active material, increase its positive ion density, form sun Ionomer is uniformly distributed wherein, and under high temperature action, cationic polymer can decompose, and the gas of generation can disappear Except the segment polarity group on surface, while the gas discharged distributes heat, and generates micro-pore on its surface, and reagent A Being added, which then can be longitudinally formed boehmite ingredient progress nanoscale in its gap by hydro-thermal method, fills up, so that its high temperature resistance It is promoted, and hot corrosion resistance can be improved, complete the packing to coating porosity；

(2) present invention reacts to the acid isoreactivity center Lewis on vermiculite surface or active group using thioacetic acid, passes through Covalent bond and electrostatic interaction, so that sulfur-containing group and internal free metal ion form stable complex, and can be with inside Other ingredients keep good compatibility, and the expansion that occurs of when vermiculite is heated can also reinforce plugging action effect, it is internal its Its substance play filling effect, using fatty alcohol polyoxyethylene ether, triethanolamine etc. combine epoxy resin additive, can by When high temperature action, intergranular surface tension is significantly reduced, emulsion foam effect is played to a certain extent, is formed tiny and not The air bubble of perforation, and the continuity of this hole sealing agent internal capillaries is destroyed, open hole is become to the hole of occlusion, it is special It is not to continue to can speed up defoaming, and good sealing of hole effect can be formed under heat effect；

(3) present invention has good dispersiveness houghite ingredient by hydro-thermal method fixture using magnesium, aluminum metal salt as raw material, Contained sodium citrate in middle auxiliary agent, containing there are three carboxyl in molecular structure, can in water-heat process with the houghite of formation Ingredient occur complexing, formed metal-chelating particle, improve hydrotalcite ingredient dispersion stabilization, the nucleation of induced crystal and Crystallization process, and the ion can be arranged in hydrotalcite layers in a manner of single vertical, obtain the biggish class neatly of specific surface area Stone ingredient facilitates the promotion of heat-resisting rotten performance, the present invention is for normal at present convenient for the contact action between enhancing and other components It there is a problem that high temperature heat-resistant corrosivity is poor with coating sealing reagent, improvement is significant, has a good application prospect.

Specific embodiment

Additive: in 30 ~ 40 DEG C, take fatty alcohol polyoxyethylene ether 3 ~ 7:1 in mass ratio be added triethanolamine mixing 30 ~ 60min obtains mixture, takes mixture 10:1:2 in mass ratio ~ 5 that hydroxyethyl cellulose, epoxy resin mixing is added to get addition Agent.

Reagent A: 1:2 ~ 4:30 ~ 50 take sodium metaaluminate, urea, water mixing to get reagent A in mass ratio.

Reagent B: according to parts by weight, 5 ~ 8 parts of magnesium nitrates, 2 ~ 5 parts of aluminum nitrates, 6 ~ 10 parts of zinc nitrates, 150 ~ 200 parts of water are taken Mixing, obtains mixing saline solution, takes mixing saline solution 20 ~ 30:1 in mass ratio that carbamide mixing is added to get reagent B.

Auxiliary agent: 3 ~ 6:1 in mass ratio takes potassium rhodanate, sodium citrate mixing to get auxiliary agent.

Dispersing agent: 2 ~ 5:1 in mass ratio takes the double stearic amides of vinyl, polyacrylamide mixing to get dispersing agent.

Defoaming agent: in mass ratio 1:3 ~ 7 take polyoxyethyl propyl polyoxyethanyl glycerin ether, dimethyl silicone polymer mixing to get Defoaming agent.

It pre-processes vermiculite: in 20 ~ 25 DEG C, vermiculite being taken to sieve with 100 mesh sieve in pulverizer crushing, take sieving particle in mass ratio 1: 3 ~ 7, which are added dimethylformamide, is uniformly mixed, and is warming up to 30 ~ 45 DEG C, 30 ~ 55% thioacetic acid, the mistake of sieving granular mass is added The sodium bisulfate mixing of granular mass 12 ~ 20% is sieved, it is closed, in 110 ~ 125 DEG C of 1 ~ 3h of insulation reaction, reactant is obtained, reactant is taken Vulcanized sodium mixing is added in 20 ~ 35:1 in mass ratio, keeps the temperature 40 ~ 60min, cooled to room temperature, and filtering takes filter residue to wash with water After 2 ~ 4 times, in 50 ~ 65 DEG C of dry 4 ~ 8h to get pretreatment vermiculite.

The preparation method of compound hole sealing base-material, includes the following steps:

(1) in 70 ~ 85 DEG C, the hydrochloric acid solution that 1:12 ~ 20 take basalt in mass ratio, mass fraction is 12% is mixed, with 400 ~ 700r/min keeps the temperature 1 ~ 3h, filters while hot, and the periodic acid solution for collecting filter residue 1:10 in mass ratio ~ 15 addition concentration 1mol/L is mixed It closes, in 80 ~ 90 DEG C of 45 ~ 60min of heat preservation, cooled to room temperature, filtering moves to baking after collection filter cake is washed with water 2 ~ 4 times Case collects dried object and takes 15 ~ 30 parts of dried objects, 2 ~ 5 parts of three ethoxies of vinyl according to the mass fraction in 65 ~ 80 DEG C of dry 3 ~ 5h Base silane, 3 ~ 7 parts of cetyl trimethylammonium bromides, 6 ~ 10 parts of dehydrated alcohols collect abrasive in 3 ~ 5h of mortar grinder；

(2) according to parts by weight, 30 ~ 40 parts of abrasives, 17 ~ 23 parts of polyvinyl alcohol, 15 ~ 20 parts of dimethyl acetamides, 4 ~ 7 parts are taken Methacryl hydroxypropyltrimonium chloride, 50 ~ 70 parts of water are mixed in reaction kettle, lead to nitrogen protection, in 100 ~ 120 DEG C with 350 ~ 550r/min stir 3 ~ 5h, cooled to room temperature, move to centrifuge with 3000 ~ 4000r/min be centrifuged 12 ~ 25min, collect from Heart object 1:6 in mass ratio ~ 10 is added reagent A and mixes in container, and in 50 ~ 65 DEG C of 25 ~ 55min of insulated and stirred, filter cake is collected in filtering In 500 ~ 700 DEG C of 2 ~ 4h of calcining, obtain calcined material, take calcined material in pulverizer crush, cross 150 meshes, collect sieving particle to get Compound hole sealing base-material.

The preparation of booster action material: in 30 ~ 45 DEG C, 12 ~ 16:1 in mass ratio takes reagent B, waterglass to mix in reaction kettle, Mixture is obtained, takes mixture that the auxiliary agent of mixture quality 10 ~ 15% is added, closed reactor is warming up to 120 ~ 145 DEG C of insulation reactions 20 ~ 35h obtains reaction material, and releasing is closed, and the additive of reaction material quality 3 ~ 7%, the pretreatment leech of reaction material quality 7 ~ 13% is added Stone mixing, with 2000 ~ 4000r/min stir 40 ~ 60min after, in 60 ~ 75 DEG C of rotary evaporations to original volume 30 ~ 45% to get Booster action material.

A kind of high heat resistance corruption coating sealing reagent, according to the mass fraction, including following component: 3 ~ 7 parts of sodium tungstates, 0.2 ~ 0.5 part of defoaming agent, 1 ~ 4 part of dispersing agent, 25 ~ 50 parts of water, 30 ~ 50 parts of compound hole sealing base-materials, 15 ~ 25 parts of booster action material.