CN102875176A - Refractory mortar for silicon carbide-carbon composite brick and preparation method - Google Patents
Refractory mortar for silicon carbide-carbon composite brick and preparation method Download PDFInfo
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Abstract
The invention relates to a refractory mortar for silicon carbide-carbon composite brick and a preparation method. According to the refractory mortar, silicon carbide particles, fine powder, silicon dioxide micro powder, clay, phenolic resin powder and carbon black are served as raw materials; furan resin and furfuryl alcohol are served as bonding agents; after the phenolic resin powder and the carbon black are added to refractory mortar powder, the mortar has excellent adhering strength after being burnt at a middle temperature and a high temperature. The silicon dioxide micro powder and the clay are synchronously added in the refractory mortar powder, thus, the mortar has high thixotropy and high vibration liquidity. The mixing liquid adopting the furan resin and the furfuryl alcohol is served as a bonding agent, so that shortcomings that a water system bonding agent, a carborundum brick and a carbon brick are poor in wettability, a phenolic resin bonding agent is high in viscosity, and construction is improperly carried out can be avoided. The refractory mortar provided by the invention has the advantages of being high in construction performance, and high in bonding strength after being dried and burnt; and the refractory mortar can be applied to adhering the carborundum brick and the carbon brick to prepare a silicon carbide-carbon composite brick for an aluminium electrolysis groove, and also can be used for bonding carborundum bricks.
Description
Technical field
The invention belongs to technical field of inorganic nonmetallic materials, be specifically related to a kind of silicon carbide-composite carbon brick with refractory mortar and preparation method, this mud is used for bonded silicon carbide brick and brick fuel to prepare aluminum electrolyzing cell used silicon carbide-composite carbon brick.
Background technology
Maximizing gradually of aluminium cell requires the sidepiece building materials to have high, the good advantages such as oxidation-resistance, heat-shock resistance and erosion resistance of physical strength under thermal conductivity height, the high temperature.The silicon nitride combined silicon carbide brick has hardness height, the heat-shock resistance that wear resistance is good, density is high, intensity is high, resistivity is high, thermal conductivity is high, good, the good advantages such as chemical stability, has replaced the first-selection that brick fuel becomes aluminum cell side lining material.
The expensive aluminium cell investment cost that makes of silicon nitride combined silicon carbide brick is higher, and the high thermal conductivity of this material is helped phenomenon so that the roasting and starting initial stage produces red stove easily because electrolyte temperature is higher.Silicon carbide-composite carbon brick side-wall material obtains using more and more widely during the nearly last ten years, the advantage that this compound side-wall material provides brick fuel or any single-material of silicon carbide brick not to possess.The effect of silicon carbide brick is to improve erosion resistance, oxidation-resistance and high heat conductivility in the compound side-wall material of silicon carbide-charcoal; The effect of brick fuel is to be convenient to processing, and larger design flexibility can be provided.The complex form of silicon carbide brick and brick fuel has multiple, below is two kinds of modal complex methods:
Silicon carbide brick places huyashi-chuuka (cold chinese-style noodles) (silicon carbide brick is towards the sidepiece box hat): best thermal conduction is provided, and has prevented the oxygenizement of air.When not having other material between silicon carbide and box hat, it is the most effective to keeping stable sidepiece ledge.
Silicon carbide brick places hot side (silicon carbide brick is towards fused electrolyte): the erosion of anti-molten cryolitic and the best protection layer of chemical reaction are provided.
No matter adopt which kind of complex method, all need refractory mortar that silicon carbide brick and brick fuel are bonded together, the quality of quality of mud fluid will directly have influence on the composite brick performance.Mud seam is the weak link of body of heater normally, so the chemical constitution of refractory mortar preferably is better than refractory brick; Refractory mortar must have good flowability and plasticity-so that construction; Refractory mortar has good wettability to refractory brick, has certain cohesive strength, so that masonry is become integral body; Has the close thermal expansivity of good volume stability and masonry, in order to avoid break away from mutually when being heated.
Mentioned a kind of composite block binding agent of exempting to dry (being refractory mortar) in national unshape refractory academic meeting paper collection " development of the aluminum electrolytic bath side wall composite block binding agent of the exempting to dry " literary compositions in 2009.Utilize carborundum powder, the useless brick powder of self-produced silicon nitride combined silicon carbide, Suzhou soil to be raw material, add 20% micropowder bonded agent A, 40% setting accelerator solution B is made, cold conditions adhesive bending strength behind its seasoning 24h is 1.85MPa, and the cold conditions adhesive bending strength behind the seasoning 72h is 2.78MPa.Do not provide the intensity index after oven dry and high temperature burn in the literary composition.
Patent of invention 200610151968.X " composite sludge for aluminum electrolytic cell and production method thereof " has proposed a kind of composite sludge, mixed powder comprises silicon carbide, crystalline flake graphite, industrial silica fume, well as clay fines, and the mixed adhesive solution composition is: the special-purpose resol of refractory materials, Resins, epoxy and solidifying agent and industrial spirit.Intensity is greater than 10MPa after 110 ℃ of bakings of prepared mud.
The described refractory mortar of above-mentioned article and patent all contains clay.Clay is the common component of refractory mortar, is mainly used to improve thixotropy and the smear of mud, makes it be easy to construction.Also added the micropowder bonded agent in the prepared mud of unsetting meeting article in 2009, micro mist is filled in the space of particle packing generation, has reduced the required wedding agent add-on of mud, has improved slip fluidity, makes it have higher intensity.
Wedding agent contains water in " development of the aluminum electrolytic bath side wall composite block binding agent of exempting to dry " literary composition.Because refractory mortar institute bonded silicon carbide brick is that non-oxidized substance material, brick fuel are hydrophobic material, this bi-material is not easy by water-wet, thereby binding agent is relative with its bonding properties relatively poor, the water based inorganic wedding agent produced a small amount of contraction owing to moisture evaporation and high temperature generate a small amount of liquid phase after particularly high temperature burnt, make refractory mortar and brick fuel bonding properties variation, thereby be easier to the contact surface cracking from brick fuel and mud.By comparison, the used resol of patent of invention 200610151968.X is that main organic bond has good wettability to brick fuel and silicon carbide brick, penetrate into easily in bonded the pore, brick fuel and silicon carbide brick better can be combined, make composite brick have higher cohesive strength.Weak point is that resol is that main wedding agent oneself viscosity is larger, smears difficulty, poor adhesion, so that the defectives such as adhesive surface internal porosity are more, is difficult to guarantee the stability of composite brick quality.Adopt the mud of organic bond not shrink with the temperature rising is basic, waterbinding agent high temperature can not occur containing and burn rear and brick fuel obscission, but with the gradually carbonization of temperature rising resin, discharge a large amount of fugitive constituents, make to have formed increased number of stomata in the mud, thereby reduced adhesive property after its high temperature burns.
Composite brick as selecting the organic bond that a kind of carbon residue amount is high, viscosity is lower, had then both guaranteed the wettability good with silicon carbide brick and brick fuel with refractory mortar, can guarantee construction quality again.In mud, as adding the higher SOLID ORGANIC additive of some carbon residue amounts, then can improve to a certain extent the bonding strength that improves after refractory mortar high temperature burns.As in mud, add one slightly, the carbon containing matter of nano particle size, then can strengthen the carbon network that forms under the organic bond high temperature, to improve the cohesive strength after refractory mortar high temperature burns.
Summary of the invention
A kind of silicon carbide-composite carbon brick refractory mortar that purpose of the present invention is developed for existing problem in the above-mentioned prior art just.
Technical scheme proposed by the invention is: the furane resin that the present invention adopts that viscosity is lower, carbon yield and resol approach are as the main component of wedding agent, and add furfuryl alcohol and dilute, so that mud has high wettability and good application property; The present invention is by adding the phenol-formaldehyde resin powder that decomposition temperature is high, the carbon residue amount is high in mud, improved the heat resisting temperature of organic bond, reduce the disadvantageous effect of residual lower increased number of stomata after the wedding agent fugitive constituent is got rid of, improved composite brick medium and high temperature cohesive strength; The present invention adds carbon black in refractory mortar, can improve the workability that improves mud, plays simultaneously the effect of similar nucleus, has strengthened the carbon network that the resin charing forms, and has improved the adhesive property after high temperature burns.
Add clay in the refractory mortar and can improve thixotropic property, but be unfavorable for improving mobile.Fine silica powder can obviously improve the flowability of mud, but causes easily the mud trickling and make the mud tack time long.The present invention adds fine silica powder and clay simultaneously, thereby makes mud have good thixotropy and vibrational flow, is convenient to the preparation of composite brick bonding.
Silicon carbide-composite carbon brick of the present invention adopts silicon-carbide particle and fine powder as main raw material with refractory mortar; Add simultaneously fine silica powder and clay, and add FB heat-resistant fireproof thermosetting phenol-formaldehyde resin powder, carbon black; Adopt the wedding agent of furane resin and furfuryl alcohol mixed preparing.
The mass percent of refractory mortar raw material of the present invention is as follows:
Silicon-carbide particle 35～55%
Carbide fine powder 30～50%
Fine silica powder 2～6%
Clay 3～7%
Phenol-formaldehyde resin powder 3～6%
Carbon black 0.5～1%.
In the present invention, the chemical ingredients of silicon-carbide particle and fine powder requires to be SiC 〉=97.0% that the silicon-carbide particle size range is 0.4 ~ 0.074mm, the granularity requirements＜0.074mm of carbide fine powder.
Described fine silica powder Chemical Composition requires SiO
2〉=92.0%, median size requires≤1 μ m.Clay is soft clay, and chemical ingredients requires (Al
2O
3+ SiO
2) 〉=80%, Fe
2O
3≤ 1.5%, median size requires≤44 μ m.
Described phenol-formaldehyde resin powder is a kind of boron modified phenolic resin, and the main chain decomposition temperature is more than 500 ℃, oxygen index 48. 5～49.Granularity requirements＜0.074mm.Manufacturer is that the trade mark is:
The FB heat-resistant fireproof thermosetting phenol-formaldehyde resin powder that the sky, Bengbu high-temperature resin Materials Co., Ltd produces, the trade mark is FB88# and FB89#, granularity requirements＜0.074mm.
The Shaanxi back-fire relief polymkeric substance company limited of navigating very much produces THC series plastics (FB resin) powder, and the trade mark is THC-400, THC-800, TH-389, TH-390 and TH-391; Toughness FBB half ether type thermosetting boron-containing phenolic resin powder, the trade mark is FBB-400, FBB-800, FBB-389, FBB-390 and FBB-391.
Described carbon black is middle particle pyrolysis method carbon black, i.e. N900 series carbon black.
It is Technical furfurylalcohol that described furane resin are used self-hardening furan resin, furfuryl alcohol for casting.Wedding agent is the mixed solution of furane resin and furfuryl alcohol, the mass ratio 1:1 ~ 1:2 of furane resin and furfuryl alcohol.
Silicon carbide-composite carbon brick with the preparation process of refractory mortar is: at first with silicon-carbide particle and fine powder, fine silica powder, clay, phenol-formaldehyde resin powder and carbon black proportionally weighing and fully mix after, prepare the refractory mortar powder; Secondly, furane resin and furfuryl alcohol are mixed according to a certain percentage, prepare the refractory mortar wedding agent; The adding wedding agent stirs and makes slip consistency reach 32 ~ 38mm in prepared refractory mortar powder, namely makes silicon carbide-composite carbon brick refractory mortar of the present invention.
The present invention has the following advantages:
1, furane resin and furfuryl alcohol mixed solution are done the prepared refractory mortar of wedding agent and are had the good wet performance, and viscosity is low, have good workability, and cohesive strength is high.
2, FB heat-resistant fireproof thermosetting phenol-formaldehyde resin powder has improved the medium and high temperature cohesive strength of mud so that the cohesive strength of refractory mortar can remain to comparatively high temps.
3, nucleation has been played in the adding of an amount of carbon black, has strengthened the charcoal network of resin formation under the high temperature.
4, add when fine silica powder and clay, make mud have good thixotropy and vibrational flow, be convenient to the composite brick bonding, make mud full easily.
Embodiment
Characteristics of the present invention are to substitute traditional water system wedding agent or resol with furane resin and furfuryl alcohol mixed solution, thermostable phenolic resin powder and carbon black in the refractory mortar powder, have been added, and add simultaneously fine silica powder and clay, prepared mud has excellent workability, cohesive strength after higher oven dry and high temperature burn.The refractory mortar of developing is bonded together silicon carbide brick and brick fuel, prepares the silicon carbide-composite carbon brick of excellent performance.For proving absolutely characteristics of the present invention, now be illustrated for example, but the present invention is not limited to following embodiment.Specific embodiment is as follows:
Embodiment 1: refractory mortar powder each component proportioning is (mass percent) silicon-carbide particle 37%, carbide fine powder 50%, fine silica powder 2%, and clay 7%, phenol-formaldehyde resin powder 3%, carbon black 1% is weighed powder in proportion and is mixed.The powder that mixes is added furane resin and furfuryl alcohol mass ratio 1:1 wedding agent and stir, adjust the wedding agent add-on and make slip consistency reach 36mm, namely make required refractory mortar.
Embodiment 2: refractory mortar powder each component proportioning is (mass percent) silicon-carbide particle 54.5%, carbide fine powder 30%, fine silica powder 6%, and clay 5%, phenol-formaldehyde resin powder 4%, carbon black 0.5% is weighed powder in proportion and is mixed.The powder that mixes is added furane resin and furfuryl alcohol mass ratio 1:2 wedding agent and stir, adjust the wedding agent add-on and make slip consistency reach 38mm, namely make required refractory mortar.
Embodiment 3: refractory mortar powder each component proportioning is (mass percent) silicon-carbide particle 45%, carbide fine powder 44.2%, fine silica powder 3%, and clay 4%, phenol-formaldehyde resin powder 3%, carbon black 0.8% is weighed powder in proportion and is mixed.It is the 2/3(mass ratio that the powder that mixes is added an amount of furans/furfuryl alcohol) wedding agent and stir, adjust the wedding agent add-on and make slip consistency reach 32mm, namely make required refractory mortar.
Embodiment 4: refractory mortar powder each component proportioning is (mass percent) silicon-carbide particle 35%, carbide fine powder 49.5%, fine silica powder 6%, and clay 3%, phenol-formaldehyde resin powder 6%, carbon black 0.5% is weighed powder in proportion and is mixed.It is the 1/2(mass ratio that the powder that mixes is added an amount of furans/furfuryl alcohol) wedding agent and stir, adjust the wedding agent add-on and make slip consistency reach 37mm, namely make required refractory mortar.
Embodiment 5: refractory mortar powder each component proportioning is (mass percent) silicon-carbide particle 55%, carbide fine powder 34.4%, fine silica powder 4%, and clay 3%, phenol-formaldehyde resin powder 3%, carbon black 0.6% is weighed powder in proportion and is mixed.It is the 1/1(mass ratio that the powder that mixes is added an amount of furans/furfuryl alcohol) wedding agent and stir, adjust the wedding agent add-on and make slip consistency reach 34mm, namely make required refractory mortar.
Embodiment 6: refractory mortar powder each component proportioning is (mass percent) silicon-carbide particle 40%, carbide fine powder 45.5%, fine silica powder 5%, and clay 4%, phenol-formaldehyde resin powder 5%, carbon black 0.5% is weighed powder in proportion and is mixed.It is the 2/3(mass ratio that the powder that mixes is added an amount of furans/furfuryl alcohol) wedding agent and stir, adjust the wedding agent add-on and make slip consistency reach 36mm, namely make required refractory mortar.
Claims (10)
1. silicon carbide-composite carbon brick refractory mortar adopts silicon-carbide particle and fine powder as main raw material; It is characterized in that: adopt furane resin as the wedding agent of main component and furfuryl alcohol mixed preparing, so that mud has high wettability and good application property; Add the phenol-formaldehyde resin powder that decomposition temperature is high, the carbon residue amount is high in the raw material of described refractory mortar, improved the heat resisting temperature of organic bond, reduce the disadvantageous effect of residual lower increased number of stomata after the wedding agent fugitive constituent is got rid of, improved composite brick medium and high temperature cohesive strength; Add carbon black in the raw material of described refractory mortar, can improve the workability that improves mud, play simultaneously the effect of similar nucleus, strengthened the carbon network that the resin charing forms, improved the adhesive property after high temperature burns.
2. according to a kind of silicon carbide-composite carbon brick refractory mortar claimed in claim 1, it is characterized in that: add simultaneously fine silica powder and clay in the raw material of described refractory mortar, thereby make mud have good thixotropy and vibrational flow, be convenient to the preparation of composite brick bonding.
3. according to a kind of silicon carbide-composite carbon brick refractory mortar claimed in claim 1, it is characterized in that: the mass percent of the raw material of described refractory mortar is as follows:
Silicon-carbide particle 35～55%
Carbide fine powder 30～50%
Fine silica powder 2～6%
Clay 3～7%
Phenol-formaldehyde resin powder 3～6%
Carbon black 0.5～1%.
4. according to a kind of silicon carbide-composite carbon brick refractory mortar claimed in claim 1, it is characterized in that: the mass ratio 1:1 ~ 1:2 of described furane resin and furfuryl alcohol.
5. according to claim 1 or 4 described a kind of silicon carbide-composite carbon brick refractory mortares, it is characterized in that: it is Technical furfurylalcohol that described furane resin are used self-hardening furan resin, described furfuryl alcohol for casting.
6. according to claim 1 or 3 described a kind of silicon carbide-composite carbon brick refractory mortares, it is characterized in that: the chemical ingredients of described silicon-carbide particle and fine powder requires to be SiC 〉=97.0%, the silicon-carbide particle size range is 0.4 ~ 0.074mm, the granularity requirements＜0.074mm of carbide fine powder.
7. according to claim 2 or 3 described a kind of silicon carbide-composite carbon brick refractory mortares, it is characterized in that: described fine silica powder Chemical Composition requires SiO
2〉=92.0%, median size requires≤1 μ m, and clay is soft clay, and chemical ingredients requires (Al
2O
3+ SiO
2) 〉=80%, Fe
2O
3≤ 1.5%, median size requires≤44 μ m.
8. according to claim 1 or 3 described a kind of silicon carbide-composite carbon brick refractory mortares, it is characterized in that: described carbon black is middle particle pyrolysis method carbon black, i.e. N900 series carbon black.
9. according to claim 1 or 3 described a kind of silicon carbide-composite carbon brick refractory mortares, it is characterized in that: described resol is a kind of boron modified phenolic resin, and the main chain decomposition temperature is more than 500 ℃, oxygen index 48. 5～49, granularity requirements＜0.074mm.
10. the described a kind of silicon carbide of claim 1-composite carbon brick is with the preparation method of refractory mortar, it is characterized in that: with silicon-carbide particle and fine powder, fine silica powder, clay, phenol-formaldehyde resin powder and carbon black proportionally weighing and fully mix after, prepare the refractory mortar powder; With furane resin and furfuryl alcohol as requested ratio mix, prepare the refractory mortar wedding agent; The adding wedding agent stirs and makes slip consistency reach 32 ~ 38mm in prepared refractory mortar powder, namely makes described silicon carbide-composite carbon brick refractory mortar.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105095672A (en) * | 2015-08-26 | 2015-11-25 | 中国一冶集团有限公司 | Calculation method for linear change rate of dried and burnt refractory mortar |
| CN106085320A (en) * | 2016-06-16 | 2016-11-09 | 宜兴新威利成耐火材料有限公司 | Aluminum electrolyzing cell used composite brick bonding agent and preparation method thereof |
| CN107434418A (en) * | 2017-07-26 | 2017-12-05 | 武汉科技大学 | A kind of carbonaceous mud and preparation method thereof |
| CN111440004A (en) * | 2020-05-19 | 2020-07-24 | 河北昊兴耐火炉料有限公司 | Nano composite material carbon pressed sealing material for blast furnace |
| CN112028613A (en) * | 2020-09-02 | 2020-12-04 | 江苏苏嘉集团新材料有限公司 | Magnesia carbon brick using catalyst-added phenolic resin |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105095672A (en) * | 2015-08-26 | 2015-11-25 | 中国一冶集团有限公司 | Calculation method for linear change rate of dried and burnt refractory mortar |
| CN106085320A (en) * | 2016-06-16 | 2016-11-09 | 宜兴新威利成耐火材料有限公司 | Aluminum electrolyzing cell used composite brick bonding agent and preparation method thereof |
| CN107434418A (en) * | 2017-07-26 | 2017-12-05 | 武汉科技大学 | A kind of carbonaceous mud and preparation method thereof |
| CN111440004A (en) * | 2020-05-19 | 2020-07-24 | 河北昊兴耐火炉料有限公司 | Nano composite material carbon pressed sealing material for blast furnace |
| CN111440004B (en) * | 2020-05-19 | 2022-04-15 | 河北昊兴耐火炉料有限公司 | Nano composite material carbon pressed sealing material for blast furnace |
| CN112028613A (en) * | 2020-09-02 | 2020-12-04 | 江苏苏嘉集团新材料有限公司 | Magnesia carbon brick using catalyst-added phenolic resin |
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