CN1012621B - Antioxidation protective coating for carbon articles - Google Patents
Antioxidation protective coating for carbon articlesInfo
- Publication number
- CN1012621B CN1012621B CN 88101899 CN88101899A CN1012621B CN 1012621 B CN1012621 B CN 1012621B CN 88101899 CN88101899 CN 88101899 CN 88101899 A CN88101899 A CN 88101899A CN 1012621 B CN1012621 B CN 1012621B
- Authority
- CN
- China
- Prior art keywords
- bed material
- topcoating
- coating
- oxide
- paint
- 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 an antioxidation paint for carbon products, which is suitable to be painted on carbon products and graphite products used at high temperature and perform the functions antioxidation and protection. The antioxidation paint is especially suitable for graphite electrodes for making steel in electric-arc furnaces. In the present invention, refractory oxides, etc. are used as raw materials so as to make nonconductive ceramic paint, and the nonconductive ceramic paint can be respectively used as base paint and surface paint to be painted on the electrode surface below the clamping head of the electrode, or used as both base paint and surface paint to be painted on the electrode surface. The antioxidation paint has the advantages of strong antioxidation performance, large thermal adhesive force, high severe cold resistance, high severe heat resistance, low price, etc. When used, the antioxidation paint can reduce the unit consumption of the electrode by 15 to 25%.
Description
The invention belongs to the oxidation resistant paint field of carbon product, be applicable to be coated on the carbon element and graphite product that uses under the hot conditions, play the antioxidant defense effect, be specially adapted to the electric-arc furnace steelmaking Graphite Electrodes.
Characteristics such as graphite is in by having good conductivity, and high temperature resistant and hot strength is big are widely used in fields such as metallurgy, chemical industry.But it is poor that the weakness of graphite maximum is a scale resistance.Be oxidation in 450 ℃ warm air, along with the raising of temperature, oxidation rate is aggravated gradually.So temperature up to the electric furnace arrangement for producing steel more than 1600 ℃ in, the loss of the surface oxidation of Graphite Electrodes is very serious.In addition, because surface oxidation, pole strength reduces, and causes lead rupture, and this has also increased the consumption of electrode.Consumption of electrode is very important productive capacity of steel-making cost.
Graphite Electrodes is the high energy consumption product, and the production Graphite Electrodes is heated to 2300 ℃ except that needing 1000～1250 ℃ of roastings 12～23 days, still needing to switch on and carries out graphitization processing, and work in-process need power consumption 5000～10000 degree/tons when greying.This shows, no matter reduce consumption of electrode, still all have crucial meaning from energy-conservation aspect from reducing steel-making cost.
Studying both at home and abroad for many years always and how to prevent that Graphite Electrodes from surface oxidation at high temperature taking place.The usefulness that the sixties begin to grow up contains the electrically conducting coating that raw materials such as metallic aluminium are made, be coated on the Graphite Electrodes, because conductive coating performance is poor, cause Graphite Electrodes and metal electrode dop (play fixed electorde and electrode is gone in the three-phase supply transporting) loose contact, cause dozen arc and seriously burn out the electrode dop, influenced normal STEELMAKING PRODUCTION; And electro-conductive materials such as containing metal aluminium cause the production cost of coating higher.The non-conductive antioxidant coating of foreign study is coated in the following graphite electrode surface of electrode dop in recent years, has avoided electrode card head position to beat arc.But the deficiency of this type coating maximum is to stick on the graphite base insecurely at present, easily produces the crack under situations such as thermal vibration, and coating comes off from electrode surface.
The working conditions of Graphite Electrodes in electric arc furnace is very abominable, furnace high-temperature, oxygen enrichment (melting of metal phase oxygen blast gas is fluxed); Electrode ceaselessly moves up and down to regulate best power supply position; When adding metal charge (as steel scrap etc.) and tapping, thermode need rise among the air that is exposed to room temperature.Thereby require electrode coating not only to have outside good high temperature resistance, severe cold and hot tolerance and the certain mechanical strength, also needing has good adhesive power with electrode.
European patent EP 0134769 has proposed use mullite, SiC and SiO
2The blackwash of making, though can on carbon product, form good fire-resistant oxidation resistant coating, but only rely on the akin performance of thermal expansivity of the thermal expansivity and the carbon product of coating, be difficult to guarantee that the coating protection film does not come off from graphite electrode surface under the steel-making severe condition, so this coating does not obtain in industrial application.
The present invention is intended to overcome above-mentioned deficiency, seeks a kind of carbon product antioxidant coating more economic, effective and easy to use.The present invention is non-conductive refractory coating, is coated in the following graphite electrode surface of electrode dop.
Coating of the present invention is made up of bed material and topcoating two portions.The bed material major ingredient is a boride, and slurry is made in water transfer, and wherein boride content is that 2～60%(is 100% in bed material); The topcoating major ingredient is the high-temperature flame-proof oxide compound, carbide or nitride and binding agent, and wherein refractory oxide content is 40～95%, carbide or nitride are 1～50%, binding agent is that 0.2～30%(is all in topcoating 100% butt).
Boride in the bed material can be one or more mixtures in boron oxide, boric acid, borate (as borax, boron magnesium ore deposit etc.) and the boron-containing glass etc.Refractory oxide in the topcoating can be alchlor, silicon-dioxide, magnesium oxide and corresponding rock ore deposit (as high-al clay, quartz, silica, magnesia etc.), wherein one or more mixtures.Carbide can be silicon carbide, titanium carbide, norbide etc., and nitride can be boron nitride, titanium nitride etc., wherein any one or more than one mixture.Binding agent can be with sulphite, phosphoric acid, borax, contain
Binding agent (as silicon sol, water glass, potassium silicate etc.) and organic binder bond (as methylcellulose gum, polyvinyl alcohol, dextrin etc.), wherein any one cheap binding agent.
The optimum content of boride is that 3～35%(is 100% in bed material in the bed material); The optimum content of refractory oxide is 45～80% in the topcoating, and carbide or amount of nitrides are 4～35%, and all the other are binding agent, (in topcoating 100% butt).
When invention is used to make steel the topcoating of Graphite Electrodes, because Electric furnace steel making field condition harshness, the steel mill's electrode that has is washed away when very serious by mechanical vibration and hot gas flow, can consider in bed material, to add refractory filler, as alchlor, silicon-dioxide, magnesium oxide, and corresponding rock ore deposit; Add-on is that 0～40%(is 100% in bed material), make slurry.Like this when primer, bed material can be coated with thicker, to strengthen cohesive action; And refractory body is arranged in the bed material, can guarantee the high temperature resistant property that coating is overall.
For improving the physical and chemical performance of topcoating, it is very favourable adding a small amount of additive.As adding calcium oxide, ferric oxide etc. in right amount for the sintering character that improves coating; For improving the suspension of coating, can add clay, sepiolite etc.; For improving the high temperature spreadability of coating, can add surfactants such as chromic oxide, titanium oxide, vanadium oxide; For improving the anti-slag ability of coating, can add barium thing (as hydrated barta, barium carbonate etc.) and ferrosilicon.For improving the resistance to elevated temperatures of coating, can add zirconium dioxide or zircon etc.The add-on of additive is in 0～20% scope, (in topcoating 100% butt).
Refractory oxide, carbide, nitride and additive particle size are 200～320 orders.
Under hot conditions; binding agent in the top coat can volatilize or participate in chemical reaction and lose cohesive action, and it is to be difficult to guarantee that coating does not come off from electrode surface that the protective membrane that has been subjected to thermal sintering to form firm compact only relies on the thermal expansivity of coating and Graphite Electrodes close.For this reason, the middle layer that between Graphite Electrodes and top coat, must have one deck to play the thermal caking effect, this layer material can be wetting graphite adhesive surface coating again simultaneously.Boride is exactly optimal raw material.The boride fusing point is low, can wetting Graphite Electrodes during fusion, and in electric arc furnace, can generate norbide with graphite; Boride is again a ceramic raw material simultaneously, can with material chemical combination such as aluminum oxide, silicon oxide and magnesium oxide.So the boride bottom can play the effect that fire-resistant oxidation resistant coating is sticked to graphite electrode surface when high temperature.And boride raw material abundance, low price.
Using method of the present invention: at first need electrode surface is cleaned out, bed material is coated in the following position of electrode surface electrode dop, treat the dried back of bed material or dried slightly, just can be coated with second layer topcoating, upper layer can use after doing.Coated electrode can be cold electrode.Also can be thermode.Coating method can be with brushing, spray, smear or the impregnating way.The bed material coating thickness is 0.005～0.05mm, and the topcoating coating thickness is 0.10～0.30mm.
Big industrial production scene, technician and workman wish that generally technological process simplifies better and better.The present invention also can apply coating this twice with bed material, surface material, is reduced to coating one time.Disposable coating is made slurry for the boride in the bed material is joined among the topcoating.
The blackwash proportioning is formed (Wt%)
Example 1, be bed material with boride and a small amount of fire resistant infilling, with Na
2SiO
Be binding agent
Bed material: H
3BO
320, Na
2B
4O
711, SiO
26, Al
2O
32,
All the other are water.
Topcoating: SiO
270.2, Al
2O
30.64 CaO 1.1, Fe
2O
30.66, TiO
20.1 SiC 18.2, Na
2SiO
49.1 it is an amount of to add water.
Example 2, being bed material with the boric acid aqueous solution, is binding agent with the S-WAT.
Bed material: 3%H
3BO
3The aqueous solution.
Topcoating: MgO 50.7, Al
2O 0.65, SiO
23.0,
CaO 3.0，Fe
2O
32.0，Cr
2O
32.55，
SiC 33.3, Na
2SO
34.8 it is an amount of to add water.
Example 3, add a certain amount of Al with boride (borax and boric acid)
2O
3Being bed material, is binding agent with phosphoric acid.
Bed material: H
3BO
315, Na
2B
4O
78, Al
2O
316,
SiO
24, all the other are water.
Topcoating: Al
2O
366.8, SiO
25.0 CaO 4.2, Fe
2O
33.2,
TiO
23.5 SiC 4.3, H
3PO
413, it is an amount of to add water.
Example 4, there is not a defective material of bed material.
Al
2O
345, SiC 27.5, H
3BO
211.0, Na
2B
4O
716.5 it is an amount of to add water
Experiment is carried out in retort furnace.Graphite sample is of a size of φ 40 * 5mm.At first the oil stain on the sample is removed totally, applied the bed material in the above-mentioned 1-3 example then respectively, treat the bed material seasoning or respectively will corresponding surface after drying in oven, material is coated on the sample.The top layer is placed on sample on the fire-resistant main frame after doing, and places the retort furnace internal heating.At 1000 ℃, observe the covering protection situation of sample top layer in the time of 1200 ℃ to graphite sample; Constant temperature stopped heating when temperature was raised to 1350 ℃ after half an hour, took out sample, observe again the coating protection film form situation and with the firm degree of the bonding of graphite sample.Experimental result sees Table 1.
The industry expanding test is carried out in certain Iron And Steel Company.The metal Intake Quantity of electric furnace is respectively 17 tons and 22 tons, and electrode diameter is respectively φ 350mm and φ 400mm.Show through trimestral commerical test, use the present invention can reduce consumption of electrode significantly, and low price, nontoxic, non-stimulated smell, simple to operation, need not increase complex apparatus, help industry and apply.
Because coating of the present invention is bonding good to Graphite Electrodes, all do not come off when low temperature and high temperature, so coating does not need every stove to apply.Experiment is to spray when more renewing the gap of electrode, does not need counter electrode to carry out any processing after being coated with and just can use immediately.Use is after 36 hours continuously in stove for coated electrode, and electrode takes out when changing can find that still coating sticks to graphite electrode surface securely, and Yong Tie is also extremely difficult sometimes removes residual coating totally.Because the oxidation resistant coating of electrode surface has protected graphite electrode surface not oxidized, so reduced consumption of electrode.Use the present invention can save electrode and reach 15～25%.The industrial experiment statistics sees Table 2.
Table 1 blackwash experimental result
After the coating situation sample cooling on coating graphite sample surface
Coating and graphite
The bonding situation of 1000 ℃ 1200 ℃ 1350 ℃ of constant temperature of classification after half an hour
Example 1 surface is coated with surface coating film forming densification, and the specimen surface bonding firmly
The complete non-oxidation of layer unbroken layer
Example 2 is the same with coating the film forming densification, and sample circumference localized membrane is easy to
The crest line position has the local molten phenomenon of losing to peel off
Only about at this position graphite oxidation
1mm。
Example 3 the same samples all are capped, and the surface nothing is tightly bonded, and is coated with
Oxidation, the densification of coating protection cuticula.Layer extremely difficulty is peeled off
Example is 4 the same, and (constant temperature half bonding firmly
Hour)
Surface film
Vitreous,
The sample table
The face anaerobic
Change
Graphitization oxygen graphite oxygen sample does not almost burn up, and weightless 85%.
Coating burning burning
Consumption of electrode was added up before and after table 2 used coating
The electrode surface electric stove metal is average every day
Coating situation Intake Quantity electrode diameter sacrificial electrode is counted electrode saving amount
(ton) (mm) (props up) (%)
Coating 2.5 0
Be coated with topcoating, 17 350 2.3 8
Primer not
Primer and table 2.0 20
Coating materials
Claims (7)
1, a kind of carbon product antioxidant coating that contains refractory materials and binding agent is characterized in that coating is made up of bed material and topcoating, and the composition of bed material is the water slurry of boride, boride content 2～60% (is 100% in bed material); Topcoating is made up of refractory oxide, carbide or nitride and binding agent, refractory oxide content 40～95%, and carbide or amount of nitrides are 1～50%, binder content 0.2～30% (all in topcoating 100% butt).
2, coating according to claim 1 is characterized in that the boride in the said bed material is any one or more mixtures such as boron oxide, boric acid, borate, boron-containing glass; Refractory oxide is alchlor, silicon-dioxide, magnesium oxide and corresponding rock ore deposit (as high-al clay, kaolin, quartz, magnesia etc.) any one or more than one mixture in the said topcoating; Said carbide is silicon carbide, titanium carbide, norbide etc., and nitride is any one or more mixtures such as boron nitride, titanium nitride; Said binding agent is sulphite, phosphoric acid, borax, contains SiO
2Binding agent (as silicon sol, water glass, potassium silicate etc.) and organic binder bond (as methylcellulose gum, polyvinyl alcohol, dextrin etc.), wherein any one.
3, coating according to claim 1 and 2, the optimum content that it is characterized in that boride in the bed material is that 3～35%(is 100% in bed material), the optimum content of refractory oxide is 45～80% in the topcoating, carbide or nitride optimum content are 4～35%, and all the other are binding agent (in topcoating 100% butt).
4, coating according to claim 1 and 2 is characterized in that can adding in the bed material an amount of fire-resistant stopping composition, and content is that 0～40%(is 100% in bed material).
5, by claim 1 or 2 described coating, it is characterized in that can adding in the topcoating additives is calcium oxide, ferric oxide; Chromic oxide, titanium oxide, vanadium oxide; Clay, sepiolite; Barium thing, ferrosilicon; Zirconium dioxide, zircon etc. any one or a few, add-on is that 0～20%(is in topcoating 100% butt).
6, by claim 1 or 2 described coating, it is characterized in that refractory oxide, carbide or nitride and additive particle size are 200～320 orders.
7, a kind of special method of carbon product antioxidant coating is characterized in that in the topcoating only needing to add in the bed material boride and makes slurry, needs add separately bed material when being coated with again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88101899 CN1012621B (en) | 1988-04-07 | 1988-04-07 | Antioxidation protective coating for carbon articles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88101899 CN1012621B (en) | 1988-04-07 | 1988-04-07 | Antioxidation protective coating for carbon articles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1036395A CN1036395A (en) | 1989-10-18 |
| CN1012621B true CN1012621B (en) | 1991-05-15 |
Family
ID=4831935
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88101899 Expired CN1012621B (en) | 1988-04-07 | 1988-04-07 | Antioxidation protective coating for carbon articles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1012621B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061367C (en) * | 1996-06-21 | 2001-01-31 | 日本帕卡濑精株式会社 | Aqueous lubricant for cold working of metal materials |
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-
1988
- 1988-04-07 CN CN 88101899 patent/CN1012621B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1061367C (en) * | 1996-06-21 | 2001-01-31 | 日本帕卡濑精株式会社 | Aqueous lubricant for cold working of metal materials |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1036395A (en) | 1989-10-18 |
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