CN1014066B - Oxidation preventive coating for heating the blank plates of silicon steels - Google Patents
Oxidation preventive coating for heating the blank plates of silicon steelsInfo
- Publication number
- CN1014066B CN1014066B CN 88101985 CN88101985A CN1014066B CN 1014066 B CN1014066 B CN 1014066B CN 88101985 CN88101985 CN 88101985 CN 88101985 A CN88101985 A CN 88101985A CN 1014066 B CN1014066 B CN 1014066B
- Authority
- CN
- China
- Prior art keywords
- coating
- silicon steel
- heating
- paint
- antioxidation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Abstract
The present invention relates to a MgO-Cr2O3 series antioxidation paint for heating silicon steel plate blanks. Industrial magnesite sand is used as the principal raw material. The antioxidation paint has the advantages of simple preparation technique and low cost. When the antioxidation paint is used, plate blanks do not need to be cleaned. The antioxidation paint has favorable heat conducting capability and high temperature resistance; when the antioxidation paint is used, the heating time for the plate blanks can not be extended, and the antioxidation paint does not have harmful effect on the quality of the finished silicon steel; the antioxidation paint can effectively prevent oxidation and burning loss of the silicon steel when the silicon steel is heated; and meanwhile, the antioxidation paint can increase the operating rate of heating furnaces and greatly increase the once rolling quantity of the silicon steel. Since the high temperature resistance of the antioxidation paint is excellent, the antioxidation paint is suitable for producing and using high-grade orientating silicon steel.
Description
The invention relates to the blank plates of silicon steels oxidation preventive coating for heating.This coating is that main raw material adds small amounts of pigment level chromium sesquioxide, silicate frit material and inorganic, organic bond is mixed with industrial magnesia.
Before the present invention, domestic have Shanghai Silicate Inst., Chinese Academy of Sciences to develop, anti-oxidant, the anti-decarburizing coating of several manufacturer production such as Huangyan, Zhejiang silicate chemical plant.When using this class coating, at first will adopt methods such as sandblast, polishing and solvent cleaning to carry out surface treatment to workpiece, working conditions be relatively harsher, and can only use 1300 ℃ of following temperature, price more expensive again (ten thousand yuan/ton of 2-10) therefore, is domesticly only used at heat treatment industry at present.Abroad, having introduced Si-SiC on the 1811st～1817 page of the wide field system iron of Japanese Nippon Steel place " iron と steel " No15 in 1985 is the directional silicon steel slab oxidation preventive coating for heating.But such coating is not suitable at burning heavy oil and does with water vapor to use in the process furnace of atomizing medium.This be since SiC at high temperature with furnace gas in water vapor acting after can severe oxidation decompose, cause breakdown of coating and lose provide protection.Also have (day) spy to open clear 60-262919(and see U.S.'s " chemical abstracts ", 104(16), the 134031K) MgO-SiO of the middle Kawasaki Iron And Steel Company exploitation of introducing
2-Cr
2O
3-Ni, Mo, Cr are the directional silicon steel slab oxidation preventive coating for heating.This coating is to adopt the fusion method of spray plating to form coating, the coating processes more complicated, and consume a large amount of noble metal powders.
Purpose of the present invention is exactly that preparation is adapted at burning heavy oil and makes the blank plates of silicon steels antioxidizing paint that uses in the process furnace of atomizing medium with water vapor, and requires the production of coating and use that technology is simple, cost is low, oxidation-protective effect good.
In order to reach above-mentioned purpose of the present invention, invented MgO-Cr
2O
3Be the blank plates of silicon steels oxidation preventive coating for heating, its proportioning (by weight) is: 80～90% common magnesia (or useless magnesia brick powder) and electrosmelted magnesite clinker; 4～7% clay silicate frit material; 4～8% industrial chromium sesquioxides; 3～5% tripoly phosphate sodium STPPs; Mix after the batching, add (accounting for compound weight) 4～6% sodium polyacrylates, 30～40% water.
Silicon steel, particularly directional silicon steel slab need long-time heating in 1200～1400 ℃ of high temperature, owing to contain the Si about 1.5～3% in the silicon steel, form with fayalite (2FeOSiO when heating
2) be the iron scale of major ingredient, its fusing point is 1205 ℃, therefore, iron scale becomes slag and accumulates in furnace bottom during heating, has reduced the lumber recovery of silicon steel and the operating rate of process furnace.The present invention selects MgO and Cr for use
2O
3As the major ingredient of coating, be because magnesium chromium matter coating has excellent anti-2FeOSiO
2Silicon steel liquid slag erosive ability.General antioxidizing paint mainly is by dystectic oxide compound (or non-oxidized substance) stupalith and low melting glass phase composite; and the ratio of glassy phase is up to 30～70%; so that under use temperature, form a kind of full-bodied melt film, thereby play a protective role.But general glassy phase is through can't stand 2FeOSiO
2The erosion of liquid phase, coating is destroyed easily.Therefore, antioxidizing paint of the present invention has changed traditional method, and not a large amount of glassy phases that adopt are just in order to regulate MgO-Cr
2O
3Be the thermal characteristics of coating, introduced the silicate high temperature frit of a spot of genus devitrified glass character.
MgO-Cr of the present invention
2O
3Be that coating has good anti-oxidation performance, this is when going into stove owing to blank plates of silicon steels, MgO-Cr
2O
3Be that coating also can not densified sintering product in the short period and form protective layer, simultaneously charging temperature up to 1200 ℃ about, the blank plates of silicon steels surface still can the micro-2FeOSiO of very fast generation
2Liquid phase, and to coating penetration, diffusion, and the low-melting-point material in the coating, as Na
2O, P
2O
5Deng also in coating, spreading.The two interpenetrate and diffusion makes coating densification soon.According to actual measurement, the thickness of close base steel tight zone has only 0.015～0.06mm.Along with the prolongation of heat-up time, 2FeOSiO
2Liquid phase is further to coating penetration.But in nearly 300 minutes long-time high-temperature heating process, the thickness of scattering and permeating layer also has only 0.5～0.6mm.The porosity of this tight zone is few, and the aperture is generally 5～25 microns.Therefore, coating can stop oxygen and silicon steel generation oxygenizement effectively.
MgO-Cr
2O
3The chemical stability that is coating is good, has both had good anti-oxidant scum erosive ability, can adapt under strong oxidizing atmosphere again and use.When containing water vapor in the furnace atmosphere, to MgO-Cr
2O
3Be that coating has no adverse effects, also can promote MgO grain growth and intensified-sintered on the contrary, rapid densification has good action to MgO matter coating.Therefore, MgO-Cr
2O
3Be that coating can be fit to burning heavy oil and uses with the process furnace that water vapor is made atomizing medium.
MgO-Cr of the present invention
2O
3Be that MgO in the coating derives from common magnesia (being brickmaking magnesia), electrosmelted magnesite clinker or useless magnesia brick, wherein the result of use with electrosmelted magnesite clinker is best.But in order to reduce the coating cost, available common brickmaking magnesia (MgO content is about 90% magnesia) instead of part electrosmelted magnesite clinker.If prepare coating with useless magnesia powder, can also improve the hydration resistance of coating, prolong the duration of service of liquid coating.With magnesium oxide is the coating of major ingredient, also can not reduce its resistance to elevated temperatures after having absorbed a large amount of ferric oxide.Therefore, needn't clear up the secondary oxidation iron layer of steel slab surface when applying coating, thereby simplify spraying coating process greatly.In addition,, suffer the erosion of liquid slag, also can not influence the provide protection of whole coating even local defect in use appears in coating.
The main chemical of the common magnesia that the present invention selects for use is (by weight percentage): 89～90%MgO, 4～4.5%SiO
2, 1.5～2%CaO, 1～1.3%Fe
2O
3; The main chemical of electrosmelted magnesite clinker is (by weight percentage): 96～97% MgO, 0.9～1.1%SiO
2, 1～1.3%CaO, 0.4～0.6%Fe
2O
3
The magnesia powder that the present invention uses (or useless magnesia brick powder) method for processing is as follows: earlier magnesia is broken into the particle less than 50mm through jaw crusher, impurity sort outs such as the iron in will expecting then, carbon, deliver to and further be crushed to less than 5mm fine particle in the cone crusher, at last with the fine powder of tube mill grinding and processing one-tenth less than 0.088mm.
The electrosmelted magnesite clinker method for processing is among the present invention: thick, middle fragmentation is identical with the working method of common magnesia, and fine crushing equipment then adopts the vibration mill of making grinding element with corundum, and powder has 80% at least less than 0.047mm.
Clay silicate frit material of the present invention, clay and frit ratio (by weight) are 80～90: 20～10.Clay is low with potassium, sodium content, and the strong kaolin of plasticity-is for well.The selected kaolin of the present invention is that Chinese Suzhou produces, and in addition, all there is production on ground such as Chinese Jiangxi, Hunan, Guangdong.The method for preparing frit material raw material is: get (by weight) 24% quartz, 15% feldspar, 12% calcite, 14.5% zircon, 7% zinc oxide, 3% kaolin, 9% boric acid, 7% borax, 3% saltpetre, 4.2% talcum, 1.5% red lead, be crushed to after the mixing less than 1.68mm, drop in the high-temperature melting furnace and be heated to 1370～1390 ℃, after treating that all raw materials all melt fully, again melt is put into cold water and carry out shrend, arrive less than the 0.088mm dry for standby with the ball mill wet-milling at last.The used clay of the present invention is a raw clay, and the employing traditional method is processed into the fine powder less than 0.088mm.Then by clay: frit is that 80～90: 20～10 mixed evenly promptly becomes clay silicate frit compound.
The used clay main chemical of the present invention (weight percent) is: 50.7%SiO
2, 30.3%Al
2O
3, 0.6% Fe
2O
3, 0.7% K
2O+Na
2O, 0.5% MgO+CaO, 0.3%TiO
2, burning decrement 15.64%.
The Chemical Composition (no igloss, weight percent) of the silicate frit batching that the present invention is used is: 45～55%SiO
2, 4～5%Al
2O
3, 7～9%CaO, 1～2%MgO, 5～7%Na
2O+K
2O, 7～9%ZnO, 1～2%PbO, 10～12% ZrO
2, 7～10%B
2O
3
The present invention adopts the contain Cr of industrial chromium sesquioxide as coating
2O
3Raw material is with Cr
2O
3For well, granularity should be less than 0.047mm greater than 96% industrial chromium sesquioxide for content.If replace industrial chromium sesquioxide with chromite, the anti-oxidation performance of coating is relatively poor.Introduce Cr in the coating
2O
3, can reduce the thermal expansivity of magnesia coating on the one hand, can reduce the osmosis of molten slag on the other hand in MgO matter coating, therefore can stop 2FeOSiO effectively
2Liquid phase improves the use properties of coating to the erosion of coating.
The used tripoly phosphate sodium STPP of the present invention is commercially available technical pure product, wherein P
2O
5Content is 56～60%.
Coating of the present invention is that the powder that adopts above-mentioned working method preparation is got by weight ratio: common magnesia (or useless magnesia brick) powder and electrosmelted magnesite clinker 80～90%, clay silicate frit compound 4～7%, 4～8% industrial chromium sesquioxides, 3～5% tripoly phosphate sodium STPPs, these four kinds of raw materials are sent to mixed in sand mill or the ball mill 20～30 minutes, sieve through 80～100 eye mesh screens then, sealing, packing is promptly made powder-type coating.Before steel silicon slab coating coating, add 4～6% sodium polyacrylates and 30～40% water (accounting for the powder gross weight) in the powder-type coating.Making liquid slip in agitated pool can spray.The molecular weight of sodium polyacrylate is with 3000 to 5000 for well, and content is 20～25%.Sodium polyacrylate with Cao Jing chemical plant, Kingsoft, Shanghai and Tianjin chemical research institute produce for well.
Coating of the present invention is all obtained positive effect in comparing the application of test and industrial production, be illustrated with embodiment below.
Embodiment one
Coating formula (by weight): 60% brickmaking magnesia powder, granularity require 80% fine powder less than 0.047mm less than 0.088mm and 25% electrofusion magnesia powder; 5% clay silicate frit material, granularity is less than 0.088mm; 4% tripoly phosphate sodium STPP; 6% industrial chromium sesquioxide, granularity is less than 0.047mm; Add (accounting for the powder gross weight) 5% sodium polyacrylate, 30% water.
Coating is used for silicon steel production, and coated weight is 0.8Kg/m
2(powder weight), heating condition are 1200 to 1390 ℃, and heating is 270 minutes in air, and the result: uncoated coating steel plate scaling loss amount is 14.3Kg/m
2, applying coating steel plate scaling loss amount is 1Kg/m
2, reducing burn out rate is 93%.
Embodiment two
Coating formula (by weight): 62% useless magnesia brick powder, granularity be less than 0.088mm, 23% electrofusion magnesia powder, and wherein 50% less than 0.047mm; 4.8% clay silicate frit material, granularity is less than 0.088mm; 4% tripoly phosphate sodium STPP; 6.2% industrial chromium sesquioxide, granularity is less than 0.047mm; Add (accounting for the powder gross weight) 5% sodium polyacrylate and 40% water.
Heating installation: walking beam heating furnace, the heavy oil of making atomizing medium with water vapor is fuel.
Coating coated weight: 1Kg/m
2(mean value); Heating condition: 1200～1380 ℃, heated 240～300 minutes.Produce 6400 tons of slabs: do not use the average 28Kg/m of coating slab scaling loss amount
2, use the average 6.8Kg/m of this coating slab scaling loss amount
2, reducing burn out rate is 70%～92%.Reduce furnace bottom slag amount 54%; Reduction of erection time 36%; Improve one time amount of rolling 23～40%.
Embodiment three
Coating formula (by weight): 75% brickmaking magnesia powder, granularity is less than 0.088mm; 10% electrosmelted magnesite clinker fine powder, granularity is less than 0.047mm; 5% clay silicate frit material, granularity is less than 0.088mm; 4% tripoly phosphate sodium STPP; 6% industrial chromium sesquioxide, granularity is less than 0.047mm; Add (accounting for the powder gross weight) 5% sodium polyacrylate and 40% water.
Application conditions is also obtained good result with example two.
In the foregoing description two, three, the slab time inside furnace is close when not using coating, when shorten to about 220 minutes heat-up time, also can guarantee to burn steel quality.Through the mensuration of finished product material iron loss and magnetic strength two big indexs, qualification rate has improved 7.5% before using coating.This shows that coating of the present invention has good heat-conducting, uses can not prolong slab heat-up time behind the coating and increase energy consumption, and the silicon steel end properties is had no adverse effects.Because this coating resistance to elevated temperatures is outstanding, also can play a protective role in the heat-processed for a long time to blank plates of silicon steels, therefore more suitable for the high name oriented blank plates of silicon steels of Heating temperature height, time inside furnace length, the effect that reduces oxidization burning loss is also more obvious.
Claims (4)
1, a kind of blank plates of silicon steels oxidation preventive coating for heating, its proportioning (by weight) is: 80～85% common magnesia (or useless magnesia brick powder) and electrosmelted magnesite clinker; 4～7% clay silicate frit material; 4～8% industrial chromium sesquioxides; 3～5% tripoly phosphate sodium STPPs; Add (accounting for compound weight) 4～6% sodium polyacrylates, 30～40% water.
2, coating according to claim 1 is characterized in that raw clay and frit ratio (by weight) are 80～90: 20～10 in the clay silicate frit material.
3, coating according to claim 1 and 2 is characterized in that the Chemical Composition (no igloss, weight percent) of silicate frit material is: 45～55% SiO
2, 4～5% Al
2O
3, 7～9% CaO, 1～2% MgO, 5～7% Na
2O+K
2O, 7～9%ZnO, 1～2%PbO, 10～12% ZrO
2, 7～10% B
2O
2
4, coating according to claim 1 and 2 is characterized in that the main chemical (weight percent) of clay is 50.7%SiO
2, 30.3%Al
2O
3, 0.6%Fe
2O
3, 0.7%K
2O+Na
2O, 0.5%MgO+CaO, 0.3%TiO
2, burning decrement 15.64%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88101985 CN1014066B (en) | 1988-04-09 | 1988-04-09 | Oxidation preventive coating for heating the blank plates of silicon steels |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88101985 CN1014066B (en) | 1988-04-09 | 1988-04-09 | Oxidation preventive coating for heating the blank plates of silicon steels |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1036396A CN1036396A (en) | 1989-10-18 |
| CN1014066B true CN1014066B (en) | 1991-09-25 |
Family
ID=4831975
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88101985 Expired CN1014066B (en) | 1988-04-09 | 1988-04-09 | Oxidation preventive coating for heating the blank plates of silicon steels |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1014066B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1109721C (en) * | 1999-09-24 | 2003-05-28 | 重庆钢铁(集团)有限责任公司 | Paint |
| CN100532466C (en) * | 2006-04-21 | 2009-08-26 | 中国科学院过程工程研究所 | High temperature common mild steel anti-oxidation coating and application thereof |
| CN101426938B (en) * | 2007-01-31 | 2010-06-02 | 中国科学院过程工程研究所 | An anti-oxidation coating for steel and method of protecting steel from oxidation |
| CN101736138B (en) * | 2009-12-23 | 2012-03-21 | 北京科技大学 | Antioxidant coating applied to high-temperature alloy heat treatment |
| CN102815952A (en) * | 2012-08-02 | 2012-12-12 | 本钢第三轧钢厂 | Antioxidation coating for high temperature billet |
| CN102924983B (en) * | 2012-10-08 | 2015-11-25 | 天津市永信盛隆科技有限公司 | A kind of graphite electrode anit-oxidizing gradient cladding and preparation method thereof |
-
1988
- 1988-04-09 CN CN 88101985 patent/CN1014066B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1036396A (en) | 1989-10-18 |
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