CN101210121A - Method for preparing high-temperature antioxidation protection coating by using attapulgite clay - Google Patents
Method for preparing high-temperature antioxidation protection coating by using attapulgite clay Download PDFInfo
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- CN101210121A CN101210121A CNA2007103024192A CN200710302419A CN101210121A CN 101210121 A CN101210121 A CN 101210121A CN A2007103024192 A CNA2007103024192 A CN A2007103024192A CN 200710302419 A CN200710302419 A CN 200710302419A CN 101210121 A CN101210121 A CN 101210121A
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Abstract
The invention relates to a method for preparing high-temperature anti-oxidation protective paint by adopting attapulgite clay. The method comprises the following steps that: firstly, attapulgite clay mineral is chosen and crushed as well as sieved by a 100 mesh sieve to obtain attapulgite clay powder; next, the attapulgite clay powder and glass powder as well as carbon powder are uniformly mixed proportionally; finally, deionized water is taken as solvent, Na2Sio3 is taken as caking agent, sodium hexametahposphate is taken as dispersant, and the high-temperature anti-oxidation protective paint is prepared by the ultrasonic agitation. The protective paint made by the method provided by the invention can be widely applicable to the high-temperature anti-oxidation protection of quenched and tempered steel, spring steel, mold steel, high-speed steel and rolling bearing steel.
Description
Technical field
The present invention relates to a kind of method of utilizing attapulgite clay to prepare high-temperature antioxidation protection coating, belong to the manufacturing technology of protective cover in the material processing field.
Background technology
In recent years, China's iron and steel output surpassed 100,000,000 tons in continuous 6 years, had become world steel big country.Iron And Steel Industry is the important industry of China always, and it all has tremendous influence to industries such as communications and transportation, mining, refractory materials, building, automobile, shipbuilding, metal products, mechano-electronics.Though change has taken place the situation based on traditional raw material now, iron and steel is still the structured material of China's fundamental construction and the material of output maximum.Because steel produces oxidation in hot rolling, forging, heat treatment process such as modified, form a large amount of oxide skins.Data shows that the deal of these oxide skins accounts for 7～10% of output of steel.Ferrous materials can be made into various parts and complexes through mechanical workout, has increased added value, if because of the high temperature oxidation premature failure, the financial loss that causes is compared particularly huge with raw-material value.Therefore national governments all pay much attention to this, give investment respectively, in the hope of seeking the effective way that reduces or retrieve a loss as much as possible.At present, the researching high-temperature antioxidation protection coating is exactly one of its main direction.
The oxidation of ferrous materials mainly be because oxygen at high temperature with metal generation oxidative reaction.The coating that applies generally is porous non-tight zone, and under the normal temperature atmospheric condition, the oxidisability composition in the atmosphere can spread by the porous coating of this layer, and oxidation resistant coating does not have the effect of isolation from oxygen voltinism atmosphere.When coating is heated; rising along with Heating temperature; coating is dewatered drying gradually; and then the beginning sintering, the pore size in the coating constantly reduces, and porosity reduces gradually; ventilation property descends; thickness of coating decreasing, when temperature reached the coating softening temperature, coating began softening fusion; coating porosity sharply reduces; density increases, and along with temperature further raises, the coating fusion is liquid; form air-locked; fine and close; liquid glass phase adhesion layer; at this moment, coating forms effective oxygen diffusion barrier, has stoped the further diffusion of oxygen; simultaneously; because the thermal expansivity of coating and matrix differs bigger, when this will make coating fall back to room temperature behind high temperature protection, is easy to come off from matrix surface.
High-temperature antioxidation protection coating belongs to a kind of of special type fire coating, is the earliest to propose similar notion by fritz's Cronin (Corning).Coating protection is simple because of its technology, cost is low, easy to use, applied widely, workpiece need not be cased, save advantages such as electric energy has improved productivity, improved labor condition, thereby in the metal fever processing, obtained increasingly extensive application.In recent years, high temperature anti-oxidation coating had been carried out number of research projects both at home and abroad.Adopting at present more in the world is the T of Berkatekt coating (English Patent) and domestic development
1～T
7Glass coating; though above-mentioned coating has the better protecting effect to iron and steel in hot procedure; but wherein contain organic solvents such as toluene or trieline mostly; cost height not only; toxicity is big; and most of coatings difficult removal after hot-work, must just can remove by additional process, thereby increase cost.
Domestic protective cover adopts silicate material mostly at present, mainly adds pottery, binding agent, additive, tinting material, suspension agent, solvent etc. by glass, pottery or glass and forms.In heat-processed, along with the rising of temperature, coating will be softened and fusion gradually, and they form continuous fine and close thin layer at steel surface, and the blocking-up external agency contacts with matrix, slows down or end the oxidation of matrix.Melten glass the blocking-up external agency in, also will with matrix surface generation physics (or) chemical reaction, it is sticked on the matrix, the combined process of a kind of often physical chemistry of its bonding and mechanical bond.Owing to there is bonding action, after the hot-work, coating still with the matrix tight adhesion, can remove through other complete processing for no follow-up mach material need, thereby increase cost, restricted the popularization and the use of protective cover.
Attapulgite clay has good rheological, higher thermal expansivity, performance such as thermostability, good plasticity-and higher specific surface area preferably, and its main chemical compositions is SiO
2, Al
2O
3, MgO etc., approaching with the composition of typical supercoat, can be used for the high-temperature antioxidation protection coating of development of new.
Summary of the invention
The objective of the invention is to: a kind of method of utilizing attapulgite clay to prepare high-temperature antioxidation protection coating is provided; adopt this method to obtain high-temperature antioxidation protection coating; can effectively promote the economic value added of attapulgite clay on the one hand; on the other hand good, the eco-friendly water-soluble high-temperature antioxidation protection coating of a kind of coating property is used for that industrial production can economize on resources effectively, the energy, the protection environment.
Technical solution of the present invention is: at first, with attapulgite clay mineral through ore dressing, 100 orders of pulverizing, sieve obtain the attapulgite clay powder, are designated hereinafter simply as recessed native powder; Then, recessed native powder, glass powder, carbon dust are carried out uniform mixing in proportion; At last, be solvent with the deionized water, Na
2SiO
3Be binding agent, Sodium hexametaphosphate 99 is a dispersion agent, makes high-temperature antioxidation protection coating through ultrasonic agitation.
A kind of utilization in the method that attapulgite clay prepares high-temperature antioxidation protection coating of the present invention, this method comprises following concrete steps:
(1) attapulgite clay mineral obtains the attapulgite clay powder through ore dressing, pulverizing, mistake 100 mesh sieves;
(2) adopt ball milling method to carry out uniform mixing recessed native powder, glass powder, carbon dust, by 10 parts of mass ratioes, its concave soil powder accounts for 8-9 part, and glass powder accounts for 1-1.5 part, and carbon dust accounts for 0-1.0 part;
(3) ratio in compound anharmonic ratio 10～20: 1 adds binding agent Na
2SiO
3, add sodium hexametaphosphate dispersant in the ratio of compound anharmonic ratio 100～90: 1, by mixture volume than 1: 5～15 ratio adding solvent deionized water, formation water-soluble high-temperature antioxidation protection coating under the mode of ultrasonic agitation.
A kind of utilization in the method that attapulgite clay prepares high-temperature antioxidation protection coating of the present invention, the median size of the recessed native powder in this high-temperature antioxidation protection coating, glass powder, carbon dust is 2～5 μ m.
The technical progress that the present invention obtains is:
(1) this high-temperature antioxidation protection coating is a kind of water soluble paint, does not contain organic solvent, and environmentally safe is to human body toxicological harmless effect;
(2) this high-temperature antioxidation protection coating is applicable to the high-temp antioxidizing protection processing in 500～1050 ℃ of temperature ranges, can be widely used in the high-temp antioxidizing protection of quenched and tempered steel, spring steel, die steel, rapid steel and rolling bearing steel etc., save a large amount of ferrous materials and the energy, have huge economic and market application foreground widely;
(3) good fluidity of this high-temperature antioxidation protection coating is difficult for precipitation, can adopt various coating processes such as brushing, spraying or dip-coating to be applied on the steel;
(4) this high-temperature antioxidation protection coating apply and pyroprocessing after, coating have good protection against oxidation performance and from workpiece surface from stripping performance, follow-up mechanical workout is had no effect.
Embodiment
The invention is further illustrated by the following examples.
Embodiment 1, the application of high-temperature antioxidation protection coating in Cr12 cold-work die steel spheriodization process thereof
At first, attapulgite clay mineral is obtained the attapulgite clay powder through ore dressing, pulverizing, mistake 100 mesh sieves; Then, adopt ball milling method to carry out uniform mixing in 8: 1: 1 ratio of mass ratio recessed native powder, glass powder, carbon dust; At last, add binding agent Na in 10: 1 ratio of compound anharmonic ratio
2SiO
3Add sodium hexametaphosphate dispersant with 100: 1 ratio, press mixture volume and added solvent deionized water, under the mode of ultrasonic agitation, obtain water soluble paint than 1: 5.
The Cr12 die steel blank of handling needing protection needs the sample top layer of applying coating with flint paper or file polishing, to remove the loose little prominent body of layer or surface that gets rusty in top layer, guarantees the even coating of coating; With hairbrush is that the sort of of common paint usefulness brushed surface at workpiece equably with above-mentioned coating, treat to repeat to brush 2 times after the seasoning, seasoning or at 50 ℃ the oven dry back is standby down; Carbide annealing process according to routine; there is the Cr12 die steel blank of supercoat to put into heat treatment furnace brushing and carries out 860 ℃ of isothermal spheroidizing 6～8h; behind the furnace cooling to 550 ℃ fast air cooling to room temperature, and with residual a small amount of protective cover of steel brush cleaning workpiece surface.
Embodiment 2, the application of high-temperature antioxidation protection coating in 60Si2Mn spring steel average tempering technology
At first, attapulgite clay mineral is obtained the attapulgite clay powder through ore dressing, pulverizing, mistake 100 mesh sieves; Then, adopt ball milling method to carry out uniform mixing in 8.5: 1.2: 0.3 ratio of mass ratio recessed native powder, glass powder, carbon dust; At last, add binding agent Na in 15: 1 ratio of compound anharmonic ratio
2SiO
3Add sodium hexametaphosphate dispersant with 95: 1 ratio, press mixture volume and added solvent deionized water, under the mode of ultrasonic agitation, obtain water soluble paint than 1: 10.
To with the sample top layer of flint paper or file polishing need applying coating, remove the little prominent body of workpiece surface, through the 60Si2Mn spring steel workpiece of quench treatment to guarantee the even coating of coating; With spray gun above-mentioned coating is sprayed on the surface of workpiece equably, treats to repeat to spray 3 times after the seasoning, seasoning or at 50 ℃ the oven dry back is standby down; The 60Si2Mn spring steel workpiece that is coated with supercoat is put into heat treatment furnace carry out 500 ℃ of average tempering 2～4h, and cool to room temperature with the furnace, with a small amount of protective cover of steel brush cleaning workpiece remained on surface.
Embodiment 3, the application of high-temperature antioxidation protection coating in 40Cr quenched and tempered steel high-temperature tempering process
At first, attapulgite clay mineral through ore dressing, pulverizing, mistake 100 mesh sieves, is obtained the attapulgite clay powder; Then, recessed native powder, glass powder, carbon dust are 9: 1.0: 0 ratio, adopt ball milling method to carry out uniform mixing in mass ratio; At last, add binding agent Na in 20: 1 ratio of compound anharmonic ratio
2SiO
3Add sodium hexametaphosphate dispersant with 90: 1 ratio, press mixture volume and added solvent deionized water, under the mode of ultrasonic agitation, obtain water soluble paint than 1: 15.
To with the sample top layer of flint paper or file polishing need applying coating, remove the little prominent body of workpiece surface, through the 40Cr quenched and tempered steel workpiece of quench treatment to guarantee the even coating of coating; With spray gun above-mentioned coating is sprayed on the surface of workpiece equably, treats to repeat to spray 3 times after the seasoning, seasoning or at 50 ℃ the oven dry back is standby down; The 40Cr quenched and tempered steel workpiece that is coated with supercoat is put into heat treatment furnace carry out 1050 ℃ of high tempering 2h, and furnace cooling is to room temperature, with a small amount of protective cover of steel brush cleaning workpiece remained on surface.
Embodiment 4, the application of high-temperature antioxidation protection coating in W18Cr4V rapid steel conventional annealing technology
At first, attapulgite clay mineral is obtained the attapulgite clay powder through ore dressing, pulverizing, mistake 100 mesh sieves; Then, be that 8.0: 1.5: 0.5 ratio adopts ball milling method to carry out uniform mixing with recessed native powder, glass powder, carbon dust in mass ratio; At last, add binding agent Na in 15: 1 ratio of compound anharmonic ratio
2SiO
3Add sodium hexametaphosphate dispersant with 100: 1 ratio, press mixture volume and added solvent deionized water, under the mode of ultrasonic agitation, obtain water soluble paint than 1: 5.
To with the sample top layer of flint paper or file polishing need applying coating, remove the little prominent body of workpiece surface, through the W18Cr4V rapid steel workpiece of quench treatment to guarantee the even coating of coating; The workpiece direct impregnation in coating, is taken out after 1 minute, treat seasoning after, repeat dip-coating 2 times, seasoning or at 50 ℃ the oven dry back is standby down; The W18Cr4V rapid steel workpiece that scribbles supercoat is put into heat treatment furnace carries out 880 ℃ of conventional annealing 6～8h, behind the furnace cooling to 500 ℃ fast water-cooled to room temperature, and with a small amount of protective cover of steel brush cleaning workpiece remained on surface.
Claims (3)
1. a method of utilizing attapulgite clay to prepare high-temperature antioxidation protection coating is characterized in that: at first, attapulgite clay mineral is obtained the attapulgite clay powder through ore dressing, pulverizing, mistake 100 mesh sieves, be designated hereinafter simply as recessed native powder; Then, recessed native powder, glass powder, carbon dust are carried out uniform mixing in proportion; At last, be solvent with the deionized water, Na
2SiO
3Be binding agent, Sodium hexametaphosphate 99 is a dispersion agent, makes high-temperature antioxidation protection coating through ultrasonic agitation.
2. a kind of method of utilizing attapulgite clay to prepare high-temperature antioxidation protection coating as claimed in claim 1 is characterized in that this method comprises following concrete steps:
(1) attapulgite clay mineral obtains the attapulgite clay powder through ore dressing, pulverizing, mistake 100 mesh sieves;
(2) adopt ball milling method to carry out uniform mixing recessed native powder, glass powder, carbon dust, by 10 parts of mass ratioes, its concave soil powder accounts for 8-9 part, and glass powder accounts for 1-1.5 part, and carbon dust accounts for 0-1.0 part;
(3) ratio in compound anharmonic ratio 10～20: 1 adds binding agent Na
2SiO
3, add sodium hexametaphosphate dispersant in the ratio of compound anharmonic ratio 100～90: 1, by mixture volume than 1: 5～15 ratio adding solvent deionized water, formation water-soluble high-temperature antioxidation protection coating under the mode of ultrasonic agitation.
3. a kind of method of utilizing attapulgite clay to prepare high-temperature antioxidation protection coating as claimed in claim 1 is characterized in that: the median size of the recessed native powder in this high-temperature antioxidation protection coating, glass powder, carbon dust is 2～5 μ m.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2007103024192A CN100564458C (en) | 2007-12-24 | 2007-12-24 | A kind of method of utilizing attapulgite clay to prepare high-temperature antioxidation protection coating |
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| CNB2007103024192A CN100564458C (en) | 2007-12-24 | 2007-12-24 | A kind of method of utilizing attapulgite clay to prepare high-temperature antioxidation protection coating |
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| CN101210121A true CN101210121A (en) | 2008-07-02 |
| CN100564458C CN100564458C (en) | 2009-12-02 |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914248A (en) * | 2010-09-02 | 2010-12-15 | 淮阴工学院 | Preparation method of PS-TiO2-ATP organic/inorganic composite film |
| CN102312065A (en) * | 2011-09-21 | 2012-01-11 | 镇江忆诺唯记忆合金有限公司 | Method for preventing GCr 15 steel surface oxidation |
| CN102391696A (en) * | 2011-09-21 | 2012-03-28 | 镇江忆诺唯记忆合金有限公司 | High-temperature anti-oxidation coating based on attapulgite clay (ATP) |
| CN103014270A (en) * | 2012-12-17 | 2013-04-03 | 南京信息工程大学 | Steel and iron high temperature oxidation-resistant coating and preparation method thereof |
| CN104945963A (en) * | 2015-07-06 | 2015-09-30 | 武汉科技大学 | Alloy steel die spraying material for copper plate casting and preparation method thereof |
| CN111117308A (en) * | 2019-12-31 | 2020-05-08 | 河钢股份有限公司承德分公司 | High-temperature-resistant anti-oxidation coating and preparation method and application thereof |
| CN112403520A (en) * | 2019-08-22 | 2021-02-26 | 昌吉学院 | Preparation and application of vermiculite supported phosphotungstic acid green catalyst |
| CN114402085A (en) * | 2019-07-10 | 2022-04-26 | 普瑞斯矿业有限公司 | Mixture for coating metal substrate |
-
2007
- 2007-12-24 CN CNB2007103024192A patent/CN100564458C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101914248A (en) * | 2010-09-02 | 2010-12-15 | 淮阴工学院 | Preparation method of PS-TiO2-ATP organic/inorganic composite film |
| CN101914248B (en) * | 2010-09-02 | 2012-01-25 | 淮阴工学院 | Preparation method of PS-TiO2-ATP organic/inorganic composite film |
| CN102312065A (en) * | 2011-09-21 | 2012-01-11 | 镇江忆诺唯记忆合金有限公司 | Method for preventing GCr 15 steel surface oxidation |
| CN102391696A (en) * | 2011-09-21 | 2012-03-28 | 镇江忆诺唯记忆合金有限公司 | High-temperature anti-oxidation coating based on attapulgite clay (ATP) |
| CN103014270A (en) * | 2012-12-17 | 2013-04-03 | 南京信息工程大学 | Steel and iron high temperature oxidation-resistant coating and preparation method thereof |
| CN104945963A (en) * | 2015-07-06 | 2015-09-30 | 武汉科技大学 | Alloy steel die spraying material for copper plate casting and preparation method thereof |
| CN114402085A (en) * | 2019-07-10 | 2022-04-26 | 普瑞斯矿业有限公司 | Mixture for coating metal substrate |
| CN112403520A (en) * | 2019-08-22 | 2021-02-26 | 昌吉学院 | Preparation and application of vermiculite supported phosphotungstic acid green catalyst |
| CN111117308A (en) * | 2019-12-31 | 2020-05-08 | 河钢股份有限公司承德分公司 | High-temperature-resistant anti-oxidation coating and preparation method and application thereof |
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| CN100564458C (en) | 2009-12-02 |
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