CN105000897B - A kind of ladle magnesia carbon brick protection materials and its application process - Google Patents
A kind of ladle magnesia carbon brick protection materials and its application process Download PDFInfo
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- CN105000897B CN105000897B CN201510443230.XA CN201510443230A CN105000897B CN 105000897 B CN105000897 B CN 105000897B CN 201510443230 A CN201510443230 A CN 201510443230A CN 105000897 B CN105000897 B CN 105000897B
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Abstract
The invention belongs to field of material technology, more particularly to a kind of ladle magnesia carbon brick protection materials and its application process, the raw material containing following percent by weight in the protection materials：Carbon black 8wt% 20%, lithium carbonate 7wt% 24wt%, boric acid 2wt% 8wt%, titanium dioxide 3wt% 13wt%, alundum (Al2O3) 2wt% 7wt%, boron nitride 1wt% 3wt%, chloride 0.2wt% 2wt%, cellulose 0.5wt% 1.5wt%, polyethylene glycol 2wt% 8wt%, pitch 1wt% 6wt%, the 3wt% of surfactant 0.1, balance of water.Shown protection materials form stabilization protection film on magnesia carbon brick surface, reduce the consumption of magnesia carbon brick, extend the service life of ladle, reduce production cost, and very easy to use.
Description
Technical field
The invention belongs to field of material technology, more particularly to a kind of ladle magnesia carbon brick protection materials and its application process.
Background technology
Ladle is the container for accepting molten steel before electric furnace or converter for steel mill, Foundry Works, inscribe refractory brick, the fire resisting
Brick is usually magnesia carbon brick.It by magnesia and carbon material is primary raw material, addition phenolic resin, pitch that magnesia carbon brick (MgO-C) is
Etc. the refractory material that carbonaceous bonding agent is suppressed.With coal gas as fuel baking to 1200 DEG C of left sides before high-temperature molten steel is loaded
The right side, lasts 12-24 hours.Wherein 100-500 DEG C of temperature range last it is most long, reach 2/3rds of whole baking time with
On.In 100-500 DEG C of baking process, the carbonaceous bonding agent in magnesia carbon brick is carbonized to form netted carbon skeleton, by refractory material
In magnesia particle, graphite particle is firmly combined together.At the same time, substantial amounts of water and other volatility gas are released
Body.But, the netted carbon skeleton for being carbonized and being formed by carbonaceous bonding agent more than 300 DEG C with atmosphere in oxygen, titanium dioxide
Carbon reacts to form CO2, the gaseous volatilization such as CO fall, formed thickness 20-30mm it is loose-decarburized layer of efflorescence.The decarburized layer is because of machinery
Vibrations are peeled off or are all washed into molten steel and slag when ladle receives the 1st stove molten steel and consumed.
So, how to prevent the carbon in magnesia carbon brick to be oxidized during ladle baking, the service life of magnesia carbon brick is improved,
It is the technical barrier for being badly in need of solving.
The content of the invention
It is an object of the invention to provide a kind of ladle magnesia carbon brick protection materials, this protection materials are coated in magnesia carbon brick
Surface, effectively prevents the carbon in magnesia carbon brick to be oxidized during ladle baking and destroy its structural strength, extension magnesia carbon brick
Service life.
It is a further object to provide the application process of above-mentioned ladle magnesia carbon brick protection materials.
In order to realize above technique effect, the present invention is to be achieved through the following technical solutions：
A kind of ladle magnesia carbon brick protection materials, it is characterised in that：Contain following percent by weight in the protection materials
Raw material：
Baking temperature of steel ladle be 300 DEG C -500 DEG C, the oxidation of the carbon black in protection materials, prevent oxygen, carbon dioxide to
The transmission on magnesia carbon brick surface.
The particle diameter of the carbon black is less than 20 μm, and average grain diameter is 2-5 μm.Preferably, the particle diameter of the carbon black is less than 10 μm.
The particle diameter of carbon black is smaller, and oxidation starting temperature is lower, but, as the particle diameter using raw material diminishes, dispersion can become difficult.Such as
Really its particle diameter is more than 20 μm, and beginning oxidizing temperature is high in carbon dioxide atmosphere, does not have at 300 DEG C, by carbon black itself
Start to aoxidize to protect the purpose of carbonaceous bonding agent in magnesia carbon brick.
Preferably, the content of the carbon black accounts for the 10wt%-17wt% of raw material total amount.The content of suitable activated carbon black,
Both can guarantee that oxidation is thorough, be uniformly dispersed again, moreover it is possible to which guarantee there are enough carbon blacks in 300 DEG C of -500 DEG C of temperature ranges by certainly
Carbon in body oxidation protection magnesia carbon brick is not oxidized, can be uniformly dispersed in protection materials again.
Lithium carbonate and acid reaction generation borates with low melting points lithium.If boric acid content is less than 2wt%, lithium borate component is too
Low, film softening temperature is high, it is impossible to activated carbon black is aoxidized the closing of pores to be formed at 500 DEG C or so, forms fine and close protection
Film；If its content is higher than 8wt%, when more than 300 DEG C, because the volatilization of excessive boron oxide causes protective film to come off.
If the content of lithium carbonate is less than 7wt%, excessive boric acid is remained in protection materials, in 300 DEG C or so the substantial amounts of volatilizations of boric acid
The peeling of protection film will be caused.If its content is higher than 24wt%, lithia-boric oxide glass phase softening temperature is too high, no
Beneficial to 500 DEG C or so the closures of protection membrane pores.
Preferably, boric acid addition is the 3wt%-6wt% of raw material gross weight；The addition of lithium carbonate is raw material gross weight
9wt%-17wt%.
Titanium dioxide is added as filmogen component, and the magnesia with magnesia carbon brick surface forms solid solution at high temperature,
Improve the compactness and heat resisting temperature of dense protective layer.If the content of titanium dioxide is less than 3wt%, the densification of protective film
Property is bad；If content of titanium dioxide is higher than 13wt%, will improve the softening temperature of protective film, be unfavorable in 500 DEG C of guarantors
Protect the closure of film hole.Preferably, the addition of titanium dioxide accounts for the 5wt%-10wt% of raw material total amount.
The particle diameter of the titanium dioxide is 0.5-2 μm, and the particle diameter of titanium dioxide is excessive, and its stability in aqueous is not
Good, long-term placement is also easy to produce precipitate and separate.
The boron nitride is hexagonal boron nitride, and its particle diameter is 1-10 μm.If its particle diameter is more than 10 μm, in aqueous
Stability is bad, and long-term placement is also easy to produce precipitate and separate.Particle diameter is less than 1 μm, is easily aoxidized in low temperature.
Alundum (Al2O3) is added as filmogen component, and the magnesia with magnesia carbon brick surface forms solid solution at high temperature
Body, improves the compactness and heat resisting temperature of dense protective layer.If the content of alundum (Al2O3) is less than 2wt%, protective film
Compactness it is bad；If alundum (Al2O3) content is higher than 7wt%, magnesium aluminate spinel is formed with magnesia at high temperature, caused
Sag of protecting coating.
Preferably, the addition of the alundum (Al2O3) accounts for the 2wt%-6wt% of raw material gross weight.
Chlorion is adsorbed in the micropore of carbon black, reduces the beginning oxidizing temperature of carbon black.The chloride is preferably chlorine
Change one or more in sodium, calcium chloride or magnesium chloride.In protection materials, the content of chloride is less than 0.2wt%, does not reach
Reduce the purpose that carbon black starts oxidizing temperature；If its content is higher than 2wt%, film is difficult drying at room temperature.Preferably, institute
State the 0.5wt% that chloride accounts for raw material total amount.
Adding cellulose prevents film from being ftractureed in drying process, improves adhesive force of the film on magnesia carbon brick surface.If
Its content is less than 0.5wt%, does not reach the purpose for improving film and the adhesive force on magnesia carbon brick surface；If its content is higher than
1.5wt%, protective coating mobility is bad, constructional difficulties.The cellulose is preferably lignocellulosic, and fibre length is less than
500μm。
Adding polyethylene glycol can increase the adhesive force of protection materials and oiliness magnesia carbon brick surface.If polyethyleneglycol content
Less than 2wt%, easily there is the uneven phenomenon of protection materials brushing in the poor adhesive force of protection materials and magnesia carbon brick.If its
Content is higher than 8wt%, can destroy the continuity of protection materials due to polyethylene glycol melting more than 60 DEG C.Preferably, it is described poly-
Ethylene glycol accounts for the 4wt%-7wt% of raw material total amount.The mean molecule quantity of the polyethylene glycol is 4000-8000.
The particle diameter of asphalt powder is less than 400 μm.Asphalt powder and carbon black are mixed and added into appropriate water, surfactant, are led to
Cross and be milled to less than 15 μm.
Preferably, the surfactant is sulfonate type anion surfactant.
Obtained ladle magnesia carbon brick protection materials of the invention are aqueous suspension shape dispersion liquid, and its apparent viscosity is 3200-
4000mPa·s。
The application process of ladle magnesia carbon brick protection materials prepared by the present invention, its step includes：Using brushing or spraying
Method, at room temperature, ladle magnesia carbon brick protection materials are coated in the surface of magnesia carbon brick, through drying, on magnesia carbon brick surface
The protection film layer that formation does not fall off；
Or it is painted on the magnesia carbon brick surface formation protection film layer for being baked to 200 DEG C.
Preferably, the quantity for spray of the protection materials or brushing amount are 0.8-1kg/m2。
The beneficial effects of the invention are as follows：
1st, ladle magnesia carbon brick protection materials of the invention form stabilization protection film, the protection film on magnesia carbon brick surface
Oxygen and carbon dioxide in room temperature into reducing atmosphere because of the oxidation of itself carbon in film within the temperature range of 500 DEG C is to magnesium
Carbon brick surface is transmitted, and the oxidation of carbon in magnesia carbon brick is greatly reduced；Within the temperature range of more than 500 DEG C, fine and close protection is formed thin
Film, prevents the infiltration of oxygen, carbon dioxide to magnesia carbon brick completely.
2nd, the protection materials can reduce the consumption of magnesia carbon brick, extend service life 10-20 times of ladle, reduce life
Produce cost.
3rd, the protection materials both can directly be brushed, be sprayed on oiliness magnesia carbon brick surface at room temperature, it is also possible to 200
DEG C or so be painted on magnesia carbon brick surface formed protection film, it is very easy to use.
Brief description of the drawings
Fig. 1 is the magnesium carbon for coating the ladle magnesia carbon brick protection materials and uncoated protection materials prepared in embodiment 1-6
The comparison diagram of brick sample practical decarburized depth.
Specific embodiment
With reference to embodiment, the invention will be further described：
The carbon black selection particle diameter used in following embodiments is less than 10 μm, the water paint charcoal that average grain diameter D50 is 3 μm
It is black；Titanium dioxide particle diameter is less than 2 μm, the titanium dioxide that average grain diameter D50 is 0.4 μm, alundum (Al2O3) particle diameter less than 0.5 μm, fibre
Lignocellulosic, the particle diameter hard pitch less than 100 μm of asphalt powder, boron nitride of the dimension element from fibre length less than 20 microns
From the hexagonal crystal powder that particle diameter is less than 5 μm；Other use chemical pure medicine, water self-control distilled water.
Embodiment 1
Comprising 10.0wt% carbon blacks in the raw material components of the ladle magnesia carbon brick protection materials, 16.0wt% lithium carbonates,
5.0wt% boric acid, 5.0wt% titanium dioxide, 4.0wt% alundum (Al2O3)s, 2.0wt% boron nitride, 0.5wt% calcium chloride,
1.5wt% lignocellulosics, 3.0wt% polyethylene glycol, 1.5wt% pitches, the surfactant of 2.5wt%, 49.0wt% water.
Calculated with protection materials dry film solid constituent, carbon black 20.6wt%, lithium carbonate 33.0wt%, boric acid 10.3wt%,
Titanium dioxide 10.3wt%, alundum (Al2O3) 8.2wt%, boron nitride 4.1wt%, calcium chloride 1.0wt%, lignocellulosic
3.1wt%, polyethylene glycol 6.2wt%, pitch 3.1wt%.
Embodiment 2
Comprising 14.0wt% carbon blacks in the raw material components of ladle magnesia carbon brick protection materials, 13.0wt% lithium carbonates,
4.0wt% boric acid, 5.0wt% titanium dioxide, 4.0wt% alundum (Al2O3)s, 2.0wt% boron nitride, 0.5wt% calcium chloride,
1.5wt% lignocellulosics, 3.0wt% polyethylene glycol, 1.4wt% pitches, the surfactant of 2.0wt%, 50.6wt% water.
Calculated with protection materials dry film solid constituent, carbon black 29.5wt%, lithium carbonate 27.4wt%, boric acid 8.4wt%, two
Titanium oxide 10.5wt%, alundum (Al2O3) 8.4wt%, boron nitride 4.2wt%, calcium chloride 1.1wt%, lignocellulosic
3.2wt%, polyethylene glycol 6.3wt%, pitch 3.0wt%.
Embodiment 3
Comprising 17.0wt% carbon blacks in the raw material components of ladle magnesia carbon brick protection materials, 11.0wt% lithium carbonates,
3.0wt% boric acid, 5.0wt% titanium dioxide, 4.0wt% alundum (Al2O3)s, 2.0wt% boron nitride, 0.5wt% calcium chloride,
1.4wt% lignocellulosics, 3.0wt% polyethylene glycol, 3.0wt% pitches, the surfactant of 1.7wt%, 47.4wt% water.
Calculated with protection materials dry film solid constituent, carbon black 33.4wt%, lithium carbonate 21.6wt%, boric acid 5.9wt%, two
Titanium oxide 9.8wt%, alundum (Al2O3) 7.9wt%, boron nitride 3.9wt%, calcium chloride 1.0wt%, lignocellulosic
2.8wt%, polyethylene glycol 5.9wt%, pitch 5.9wt%.
Embodiment 4
Comprising 14.0wt% carbon blacks in the raw material components of ladle magnesia carbon brick protection materials, 11.0wt% lithium carbonates,
3.0wt% boric acid, 8.0wt% titanium dioxide, 4.0wt% alundum (Al2O3)s, 2.0wt% boron nitride, 0.5wt% calcium chloride,
1.5wt% lignocellulosics, 5.0wt% polyethylene glycol, 1.5wt% pitches, the surfactant of 1.3wt%, 47.2wt% water.
Calculated with protection materials dry film solid constituent, carbon black 27.2wt%, lithium carbonate 21.4wt%, boric acid 5.8wt%, two
Titanium oxide 15.5wt%, alundum (Al2O3) 7.8wt%, boron nitride 3.9wt%, calcium chloride 1.0wt%, lignocellulosic
2.9wt%, polyethylene glycol 9.7wt%, pitch 2.9wt%.
Embodiment 5
Comprising 14.0wt% carbon blacks in the raw material components of ladle magnesia carbon brick protection materials, 11.0wt% lithium carbonates,
3.0wt% boric acid, 10.0wt% titanium dioxide, 2.0wt% alundum (Al2O3)s, 2.0wt% boron nitride, 0.5wt% calcium chloride,
0.5wt% lignocellulosics, 3.0wt% polyethylene glycol, 4.0wt% pitches, the surfactant of 2.0wt%, 48.0wt% water.
Calculated with protection materials dry film solid constituent, carbon black 28.0wt%, lithium carbonate 22.0wt%, boric acid 6.0wt%, two
Titanium oxide 20.0wt%, alundum (Al2O3) 4.0wt%, boron nitride 4.0wt%, calcium chloride 1.0wt%, lignocellulosic
1.0wt%, polyethylene glycol 6.0wt%, pitch 8.0wt%.
Embodiment 6
Comprising 14.0wt% carbon blacks in the raw material components of ladle magnesia carbon brick protection materials, 11.0wt% lithium carbonates,
3.0wt% boric acid, 6.0wt% titanium dioxide, 6.0wt% alundum (Al2O3)s, 2.0wt% boron nitride, 0.5wt% calcium chloride,
1.5wt% lignocellulosics, 3.0wt% polyethylene glycol, 1.5wt% pitches, the surfactant of 1.1wt%, 50.4wt% water.
Above protection materials dry film solid constituent is calculated, carbon black 28.8wt%, lithium carbonate 22.7wt%, boric acid 6.2wt%,
Titanium dioxide 12.4wt%, alundum (Al2O3) 12.4wt%, boron nitride 4.1wt%, calcium chloride 1.0wt%, lignocellulosic
3.1wt%, polyethylene glycol 6.2wt%, pitch 3.1wt%.
The protecting effect evaluation test of ladle magnesia carbon brick protection materials prepared by the present invention：By in same temperature, gas
Be coated with atmosphere the present invention preparation protection materials and uncoated protection materials magnesia carbon brick sample aoxidize in atmosphere after, with examination
The sample surface layer peeling thickness effect anti-oxidation to magnesia carbon brick to evaluate protection materials.
1) sample coating processing：
From phosphorus content cuts the X 100mm of 50 X 50 for 8wt% does not burn rectangle cylinder sample on magnesia carbon brick.Cut sample
When, it is ensured that at least there is the crude oil surface that two faces are magnesia carbon bricks along cylinder 100mm length directions.
Each sample along 100mm directions half, the part of about 50mm hairbrush makes in coating embodiment 1 to embodiment 6
Standby protection materials, second half surface is left intact.
The coating thickness of protection materials is about 1mm, and the sample after coating places natural drying in more than 2 hours at room temperature.
2) heated oxide：
Said sample is put into Muffle furnace, by programming rate set in advance, temperature, constant temperature time oxygen in atmosphere
Change.Heated oxide evaluation experimental is divided into two kinds of " room temperature is to 500 DEG C " and " room temperature is to 1200 DEG C ", evaluate respectively low-temperature bake and
The protecting effect of protective coating during high-temperature baking.
The heating procedure of " room temperature is to 500 DEG C " experiment：
By room temperature to after 100 DEG C, constant temperature 1 hour；Then, 500 DEG C are warming up to 120 DEG C/h of programming rate,
Constant temperature is cut off the electricity supply after 6 hours, cools to room temperature with the furnace.
The heating procedure of " room temperature is to 1200 DEG C " experiment：
By room temperature to after 100 DEG C, constant temperature 1 hour；Then, 500 DEG C are warming up to 120 DEG C/h of programming rate,
After constant temperature 2 hours, then 1200 DEG C are warming up to 5 DEG C/min of programming rate, constant temperature is cut off the electricity supply after 1 hour, is cooled to the furnace
Room temperature.
Sample is taken out from Muffle furnace, sample is tapped repeatedly on cement plate, the loose part in removal sample top layer, so
Full-size of the nubbin along original sample 50mm directions is determined afterwards.
When the maximum temperature of baking is 500 DEG C, the portion of residual of uncoated protection materials partially changes into cylindrical shape,
A diameter of 38-43mm, average out to 40.6mm, i.e. magnesia carbon brick specimen surface generate thickness for 3.5-6mm, average thickness because of oxidation
Come off from specimen surface for the decarburized layer of 4.7mm.The part of protection materials is coated with, most of protective coating is because shaking with examination
The loose partial exfoliation of sample, nubbin remains rectangular shape, and the length of side is 47-49mm, average out to 48.2mm, i.e. magnesia carbon brick examination
Sample surface comes off because oxidation generates the decarburized layer of 0.9mm from specimen surface.
So, under conditions of maximum temperature is heated in atmosphere for 500 DEG C, after magnesia carbon brick surface coating protection materials, its
The thickness of decarburized layer (surface porosity comes off) reduces more than 80%.
When the maximum temperature of baking is 1200 DEG C, the part of uncoated protective coating completely falls off, i.e. magnesia carbon brick sample
Because oxidation makes its structure destroy completely.The part of protection materials is coated with, protective coating maintains the original state into enamel-like, sample, sample
The length of side is also increased slightly because of the thickness of protective film.
In sum, after protection materials prepared by the magnesia carbon brick outer surface coating present invention, effectively prevent outside magnesia carbon brick
Surface generates the phenomenon of stratum disjunction because of oxidation, and the layer thickness variation that specifically comes off situation is as shown in Figure 1.
Embodiment 7
The protection materials of embodiment 2 are sprayed on 120 tons of slag linings of ladle, protection materials is evaluated to extension magnesia carbon brick
The effect in life-span.
It is that coating is sprayed on magnesium carbon by carrier with compressed air when about 200 DEG C of refractory surface temperature in ladle
Brick surface, along ladle inner wall circumference half or so sprayed protection material, second half does not spray protection materials, to compare.Protected material
The quantity for spray of material is 0.8-1kg/m2。
After protection materials spraying, ladle toasts 8 hours, through 5 hours was baked to 1200 DEG C again through less than 500 DEG C.The ladle
After processing 82 stove molten steel, magnesia carbon brick is changed.The thickness of measurement slag lining spray protective coating and the residual brick of non-spray protective coating.
Experimental result surface, in same ladle, same slag lining, the residual brick thickness of magnesia carbon brick is after spray protective coating
75-94mm, median are 84.5mm；Residual brick thickness 55-73mm, median without coating protective coating are 64.0mm.Coating
After the same terms use, the difference of residual brick thickness is 20.5mm to the magnesia carbon brick of protection materials and uncoated protection materials.According to every
Process 1 stove molten steel magnesia carbon brick thickness and reduce 1-2mm calculating, ladle service life can be made to extend 10-20 after sprayed protection material
It is secondary.
The above is presently preferred embodiments of the present invention, but the present invention should not be limited to disclosed in the embodiment
Content.So every do not depart from the lower equivalent or modification for completing of spirit disclosed in this invention, the model of present invention protection is both fallen within
Enclose.
Claims (10)
1. a kind of ladle magnesia carbon brick protection materials, it is characterised in that：Contain following percent by weight in the protection materials
Raw material：
The surfactant is sulfonate type anion surfactant.
2. ladle magnesia carbon brick protection materials according to claim 1, it is characterised in that：The particle diameter of the carbon black is less than 20
μm, average grain diameter is 2-5 μm.
3. ladle magnesia carbon brick protection materials according to claim 1, it is characterised in that：The particle diameter of the titanium dioxide is
0.5-2μm。
4. ladle magnesia carbon brick protection materials according to claim 1, it is characterised in that：The boron nitride is nitrogenized for six sides
Boron, its particle diameter is 1-10 μm.
5. ladle magnesia carbon brick protection materials according to claim 1, it is characterised in that：With opening for chloride reduction carbon black
Beginning oxidizing temperature, the chloride is one or more in sodium chloride, calcium chloride or magnesium chloride.
6. ladle magnesia carbon brick protection materials according to claim 1, it is characterised in that：The cellulose is wood fibre
Element, fibre length is less than 500 μm.
7. ladle magnesia carbon brick protection materials according to claim 1, it is characterised in that：The average mark of the polyethylene glycol
Son amount is 4000-8000.
8. ladle magnesia carbon brick protection materials according to claim 1, it is characterised in that：The protection materials are aqueous suspension
Shape dispersion liquid, its apparent viscosity is 3200-4000mPas.
9. the application process of the ladle magnesia carbon brick protection materials described in claim 1, its step includes：Using brushing or spraying
Method, at room temperature, ladle magnesia carbon brick protection materials are coated in the surface of magnesia carbon brick, through drying, on magnesia carbon brick surface
The protection film layer that formation does not fall off；
Or it is painted on the magnesia carbon brick surface formation protection film layer for being baked to 200 DEG C.
10. the application process of ladle magnesia carbon brick protection materials according to claim 9, it is characterised in that：The protection
The quantity for spray or brushing amount of material are 0.8-1kg/m2。
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| CN1052878A (en) * | 1989-12-27 | 1991-07-10 | 冶金部洛阳耐火材料研究院 | Anti-oxidation coating for graphite electrode |
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