CN101792294A - Light thermal-shield refractory castable - Google Patents
Light thermal-shield refractory castable Download PDFInfo
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- CN101792294A CN101792294A CN201010137501A CN201010137501A CN101792294A CN 101792294 A CN101792294 A CN 101792294A CN 201010137501 A CN201010137501 A CN 201010137501A CN 201010137501 A CN201010137501 A CN 201010137501A CN 101792294 A CN101792294 A CN 101792294A
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
- C04B20/107—Acids or salts thereof
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
- C04B20/10—Coating or impregnating
- C04B20/1055—Coating or impregnating with inorganic materials
- C04B20/1074—Silicates, e.g. glass
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/06—Aluminous cements
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Abstract
The invention relates to a light thermal-shield refractory castable comprising the following components in percentage by weight: 40-60% of light aggregate, 10-20% of capacitance mullite, 5-10% of kyanite powder, 5-10% of high-aluminium clinker powder, 3-8% of silica micro powder, 3-8% of alpha-Al2O3 micro powder, 5-10% of high-aluminium cement, 0.5-10% of high-aluminium refractory fibre containing zirconium, 1.5-4% of thermal-shield steel fibre, 0.1-1% of melamine and 0.05-0.1% of organic anti-explosion fibre, wherein the granularity of the capacitance mullite is less than or equal to 1 mm, both the granularity of the silica micro powder and the granularity of the alpha-Al2O3 micro powder are less than or equal to 5 mu m, and the chemical modified light aggregate is obtained by drying after the light aggregate is dipped in inorganic chemical solution or sol. The light thermal-shield refractory castable of the invention can improve the service life of a furnace roller, lowers production consumption cost, reduces non-working hours caused by exchanging rollers and improves production efficiency.
Description
Technical field
The present invention relates to refractory materials, be specifically related to unshape refractory, especially for the light thermal-shield refractory castable of CSP roller hearth heating furnace roller.
Background technology
The CSP roller hearth type heating furnace is the linking device between thinslab casting and the thin slab continuous mill; the quality of its serviceability will directly have influence on the normal operation of whole production line; its furnace roller is being undertaken the support of slab in the stove and the driving task of advancing; Working environment is the most abominable; be in the zone of temperature for a long time up to 1100～1250 ℃; the furnace atmosphere complexity; the continuous heavy loading running of long-term 24h; thereby; the four road heating resisting metal collars that furnace roller is arranged by outer wall play and support and the effect that drives slab; and be equipped with the refractory heat-insulating protective layer between the outer wall collars, play the protection furnace roller; reduce the water-cooled thermosteresis; the effect that increases the service life.In actual production process; according to processing requirement and rhythm of production; furnace roller needs constantly to change the size and the sense of rotation of rotating speed; thereby; protective layer not only is subjected to the effect of rotary centrifugal force and sweep of gases in the furnace roller rotary course; simultaneously, also be subjected to slab advance fast in and frequent impact and friction and the mechanical impact force that produces between the collars.Therefore; furnace roller is most important, the most flimsy key equipment in the CSP roller hearth type heating furnace mechanical means; its online amount is big, price is high; and usually cause furnace roller short work-ing life because of the breakage of refractory heat-insulating protective layer; not only increased the production consuming cost; also, reduced production efficiency because frequent roll change has increased the non-activity duration.Because be subjected to the restriction of external furnace roller patented technology, domestic CSP roller hearth heating furnace roller major part is from external integral inlet, its refractory heat-insulating protective layer material mainly contains following two kinds:
The method that first kind of refractory fibre rope wrapping of adopting the built-in heat resisting alloy wire adds the refractory fibre paint spay-coating is made, the furnace roller of producing as the employed German RHI of Baogang's CSP roller hearth type heating furnace company.(reference: Li Jingwen, Yang Junxuan, the application of ceramic fiber on the CSP of Baogang process furnace, Baogang's science and technology, 2004 (2), 16-17﹠amp; 41) this furnace roller has the advantage that thermal conductivity is low, thermal and insulating performance is good, unit weight is light and power consumption is few, but it is very high to raw-material specification of quality such as refractory fibre rope, refractory fiber spraying material and heat resisting alloy wires, complex manufacturing technology causes cost higher; The furnace roller thermal insulation layer of producing and the bonding strength of the body of roll are low, anti-mechanical vibration poor performance, washing away of non-refractory flue gas, simultaneously spray fiber crystallization efflorescence meeting different with the fiber rope shrinkage rates and fiber self causes thermofin cracking, layering and comes off under the hot conditions; The iron scale that falls in the slab operational process is bonded at surface and its generation chemical reaction of refractory fibre, not only refractory fibre is caused chemical erosion, make also that its hardening becomes fragile, elasticity reduces, further quickened the breakage of fibrous insulating layer, caused furnace roller actual service life far below design level.
Second kind is adopted refractory castable to make, the furnace roller of producing as the employed Italian Dexing of Ma Gang and Wuhan Iron and Steel Plant CSP roller hearth type heating furnace company.For the furnace roller of first kind of form, this furnace roller manufacture craft is simple, anti-mechanical vibration ability and anti-sweep of gases ability are stronger, but exist various problems in the process of using: 1) mould material unit weight is big, the weight of furnace roller and the power consumption of rotation have been increased, and damage roll shaft easily by pressure, shortened the work-ing life of furnace roller bearing; 2) the Italian Dexing company this furnace roller mould material of producing is owing to adopt aluminous cement as wedding agent, the phenomenon that in 900～1200 ℃ of mesophilic ranges, has serious strength degradation, making that furnace roller refractory castable in rotation process is easier ftractures, comes off, and causes furnace roller shorter actual service life; 3) the heavy refractory castable thermal conductivity height of Cai Yonging, heat-proof quality is relatively poor, causes that the furnace roller thermal load increases, thermosteresis is serious, wall-cooling surface fouling, cooling intensity descend, and causes the average working temperature of furnace roller to raise.At the problems referred to above, " a kind of refractory castable that is used for furnace rollers of roller bottom furnace " (Granted publication CN100408515C) discloses a kind of by electrofused mullite, flint clay, mullite, trichroite, kyanite, ultrafine silica powder, alumina powder, high-alumina cement, Stainless Steel Fibre, explosion-proof fiber, tripoly phosphate sodium STPP, the heavy refractory castable that water is formed, by improving the thermal shock resistance of furnace roller refractory castable, reached to a certain extent and improved pouring layer cracking and the effect of peeling off, but still existed heavy refractory castable unit weight big, thermal conductivity is higher, deficiencies such as heat-proof quality difference.
By the analysis of the Working environment of above-mentioned CSP roller hearth heating furnace roller and furnace roller thermal insulation protection layer as can be seen, owing to be in temperature up in 1100～1250 ℃ the roller hearth type heating furnace for a long time, the furnace roller thermal insulation protection layer material must have certain refractoriness; The O of each section in the stove
2Bigger with CO content fluctuation range, and thereby reducing atmosphere can cause the maximum operation (service) temperature of inorganic fibre crystallization efflorescence under relatively low temperature reduction inorganic fibers, and the content of stove entrance water vapour is higher, the atmosphere complexity, high-temperature vapor corrodes serious to anti-material, therefore, material must have the certain high temperature resistance chemical erosion and the ability of anti-sweep of gases; The inner logical water coolant of furnace roller, internal-external temperature difference is very big, and material not only must have less thermal conductivity, reduces the thermal losses that water coolant is taken away, and possesses excellent heat insulation property, also must have good thermal shock resistance energy; According to processing requirement and rhythm of production, furnace roller needs constantly to change the size and the sense of rotation of rotating speed, insulating refractory casting material not only is subjected to the effect of rotary centrifugal force in the furnace roller rotary course, also be subjected to slab advance fast in and frequent impact and friction and the mechanical impact force that produces between the collars, therefore, material must have certain anti-mechanical vibration ability; Furnace roller is rotated by the driving of motor, insulating refractory casting material proportion is crossed the weight of conference increase furnace roller and the power consumption of rotation, and damage bearing easily by pressure, have a strong impact on the work-ing life of furnace roller bearing, therefore, under the prerequisite that satisfies other use propertieies requirements, the proportion of the lightening material of should trying one's best.And above-mentioned two kinds of furnace roller thermal insulation protection layer forms all are difficult to satisfy simultaneously all use properties requirements of above CSP roller hearth heating furnace roller, thereby the problems referred to above occurred in the process that reality is used.
At present CSP roller hearth heating furnace roller refractory heat-insulating protective layer adopts the refractory fibre rope wrapping of built-in heat resisting alloy wire to add the method for refractory fibre paint spay-coating and two kinds of forms of method of heavy refractory castable casting, all can not all satisfy simultaneously furnace roller use in light, the use properties requirements such as heat-proof quality is good, good thermal shock stability, anti-mechanical vibration ability, anti-sweep of gases ability is strong and high temperature resistance chemical erosion ability is strong of the prerequisite unit weight of institute.Shortcomings such as therefore in the process that reality is used, there is complex manufacturing technology in the former, cost is higher, intensity is low, anti-mechanical vibration poor performance, and non-refractory sweep of gases and pyrochemistry corrode, work-ing life is lower; The latter exists unit weight greatly, easily to damage shortcomings such as roll shaft, thermal conductivity are higher, heat-proof quality difference by pressure.
Summary of the invention
Technical problem to be solved by this invention is: a kind of light thermal-shield refractory castable is provided, compare with the existing light thermal-shield refractory castable that is used for the CSP roller hearth heating furnace roller, light thermal-shield refractory castable of the present invention can improve the furnace roller life-span, reduce the production consuming cost, reduce the non-activity duration that roll change causes, enhance productivity.
The present invention is adopted solution to be by the problem of the above-mentioned proposition of solution:
A kind of light thermal-shield refractory castable, it comprises following components in weight percentage:
The chemical modification aglite, 40～60%; Electrofused mullite, 10～20%; The aquamaine stone flour, 5～10%; High-alumina powder clinker, 5～10%; Fine silica powder, 3～8%; α-Al
2O
3Micro mist, 3～8%; High-alumina cement, 5～10%; Contain the zirconium high-alumina refractory fiber, 0.5～10%; Heat-resistant steel fiber, 1.5～4%; Trimeric cyanamide, 0.1～1%; Organic explosion-proof fiber, 0.05～0.10%;
The granularity of described electrofused mullite is smaller or equal to 1mm; The granularity of fine silica powder and α-Al
2O
3The granularity of micro mist is all smaller or equal to 5 μ m;
Described chemical modification aglite is that aglite soaks after drying and forms in inorganic chemistry solution or colloidal sol.
In the such scheme, described inorganic chemistry solution or colloidal sol are a kind of in aluminium dihydrogen phosphate aqueous solution, phosphate aqueous solution, silicon sol, aluminium colloidal sol, the sial complex sol.
In the such scheme, the weight concentration of described aluminium dihydrogen phosphate aqueous solution is 25～40%, and the weight concentration of described phosphate aqueous solution is 30～60%, the weight concentration 15～25% of described silicon sol, aluminium colloidal sol, sial complex sol.
In the such scheme, aglite is lightweight bauxites aggregate or light-weight mullite aggregate in the described chemical modification aglite; Al in the described lightweight bauxites aggregate
2O
3Weight content be 40～80%.
In the such scheme, described chemical modification aglite is made of two kinds of grain compositions that granularity is respectively 3～5mm and 1～3mm, wherein, granularity is that the chemical modification aglite weight of 3～5mm accounts for 15～25% of light thermal-shield refractory castable gross weight, and the chemical modification aglite weight that granularity is respectively 1～3mm accounts for 25～40% of light thermal-shield refractory castable gross weight.
In the such scheme, the described length that contains the zirconium high-alumina refractory fiber is 3～10mm.
Use properties requirements such as the enforcement of the present invention by the multiple technologies means, the light thermal-shield refractory castable of development can be good at satisfying that the prerequisite unit weight of CSP roller hearth heating furnace roller refractory heat-insulating protective layer institute is light, heat-proof quality is good, good thermal shock stability, anti-mechanical vibration ability, anti-sweep of gases ability is strong and high temperature resistance chemical erosion ability is strong.
By aglite being adopted inorganic chemistry solution or colloidal sol soak the method that modification is handled; inorganic chemistry solution and colloidal sol all can be penetrated into porous aggregate particulate inside by hole; repair the aggregate internal tiny crack; and it is more concentrated to distribute around hole; strengthened hole matrix on every side; not only solved the strength degradation problem that aglite causes owing to the crackle for preparing and the transportation moderately gusty air causes; increased the intensity of aggregate; also increased the bonding strength between aggregate and the matrix; significantly improve the anti-folding and the ultimate compression strength of lightweight heat-proof mould material integral body, strengthened the anti-mechanical vibration ability and the anti-sweep of gases ability of furnace roller thermal insulation protection layer.
By using high-alumina cement, silicon-dioxide and α-Al2O3 micro mist is as combined binder, introduce hydration combination and cohesion in conjunction with two kinds of setting and harden mechanism, not only utilize the hydration reaction and the resultant of aluminous cement to form the crystallization rack and make mould material acquisition intensity, form colloidal particle after also utilizing fine silica powder to meet water, when micelle surface electrostatic repulsion during less than its gravitation, condense combination by means of Van der Waals force, dry back forms siloxane network and sclerosis acquisition intensity takes place, along with the temperature moral raises, key in the siloxane network between silicon and the oxygen does not rupture, so intensity also improves constantly; On the other hand, utilize silicon-dioxide and α-Al
2O
3The micro mist specific surface area is big, cooperates dispersion agent to make pour mass populated, and pore structure is even, and the much holes of micropore are few, improved the intensity of material; In addition, the α-Al of siloxane network structure and its parcel under the high temperature
2O
3Micro mist reacts and generates the staggered mullite crystal of needle-like, has further improved medium and high temperature strength.Thereby avoided adopting pure calcium aluminate cement in conjunction with the time drated calcium aluminate secondary monocalcium aluminate, calcium dialuminateization in 900～1200 ℃ of mesophilic ranges cause volumetric shrinkage and form internal porosity and problem that the strength of materials that causes reduces.
According in the heat-resistant steel fiber, the more excellent more excellent characteristics of zirconium high-alumina refractory fiber medium and high temperature performance that contain of low temperature use properties, by adding heat-resistant steel fiber simultaneously and containing two kinds of fibers of zirconium high-alumina refractory fiber, the enhancing, the toughening effect that utilize its drawing effect in matrix to be produced have reached the whole purpose that improves anti-mechanical vibration ability of furnace roller mould material and toughness in wide temperature range.
By adding thermal expansivity is little, creep rate is low electrofused mullite, containing multiple modes such as zirconium high-alumina refractory fiber and an amount of organic explosion-proof fiber, utilize the hole and the length 3～10mm that form after the fusing in bake process of organic explosion-proof fiber, volatilization and the oxidation to contain the uniform distribution of zirconium high-alumina refractory fiber in material, absorb energy effectively, the crackle that stops thermal stresses to cause further expands, and reaches the purpose that improves furnace roller mould material thermal shock resistance.
By select lightweight bauxites aggregate or light-weight mullite aggregate for use with vesicular structure and add 0.5～10 weight part thermal conductivity less contain the zirconium high-alumina refractory fiber, reached raising furnace roller heat-insulating property, reduce the thermosteresis that water coolant is taken away, reduce volume density simultaneously, reduce the weight of furnace roller and the power consumption of rotation, alleviate purpose the furnace roller bearing wear.
Aquamaine stone flour by adding 5～10 weight parts utilizes irreversible mullite and the free SiO of being decomposed under the kyanite high temperature as swelling agent
2And the generation volumetric expansion, offsetting mould material high temperature lower volume shrinks, and reaches the purpose that prevents thermal expansion between mould material and the metal body of roll from not match the cast bed of material that causes ftractures and come off.
By adding trimeric cyanamide as dispersion agent, improved the dispersiveness of mould material, improved workability; After aglite adopts chemical reagent (aluminium dihydrogen phosphate, phosphoric acid, silicon sol, aluminium colloidal sol or sial complex sol) to soak the modification processing simultaneously, sealed part holes, make the material water-intake rate descend, reduced the construction amount of water of mould material, also improved workability.
By the integrated application of above-mentioned multiple technologies means, light thermal-shield refractory castable unit weight involved in the present invention is light, when furnace roller uses rotational power consumption few, the little long service life of bearing load; Mould material has higher basic, normal, high temperature intensity, and the furnace roller thermal insulation protection layer in use has good anti-mechanical vibration ability, toughness and anti-sweep of gases ability; The mould material good thermal shock stability makes furnace roller take place to be difficult for when sharply changing cracking taking place or peeling off in furnace temperature; Mould material aggregate porous lightization, thermal conductivity is little, and furnace roller thermal insulation protection layer heat-proof quality is good, and the thermal losses that water coolant is taken away is little; Pouring forming technology is simple to operation, and the construction amount of water is little, and workability is good, and employed various raw materials all can be bought from the market, make that furnace roller construction cost and raw materials cost are lower.Finally reach the raising furnace roller life-span, reduced the production consuming cost, reduced the non-activity duration that roll change causes, the purpose of enhancing productivity.
Description of drawings
The mould material sample that Fig. 1 adopts silicon sol to soak the modification processing for aggregate is finished the photo in kind of folding strength test back section;
The mould material sample that Fig. 2 handles for the aggregate non-modified is finished the photo in kind of folding strength test back section;
The mould material sample that Fig. 3 handles for aggregate adopts silicon sol to soak modification (1100 ℃ * 3h) Micro-Structure Analysis shows: bonding state is good between aggregate and the matrix;
The mould material sample that Fig. 4 handles for the aggregate non-modified (1100 ℃ * 3h) microtexture shows: big crack is arranged, in conjunction with not tight between porous aggregate particle and matrix;
Fig. 5 is No. 1 aggregate (a not soaking) microtexture sem photograph (* 100);
Fig. 6 is No. 1 aggregate (a not soaking) microtexture sem photograph (* 500);
Fig. 7 is No. 1 aggregate (a not soaking) microtexture sem photograph;
Fig. 8 indicates "+" position energy spectrometer to measure microcell constituent content (No. 1 aggregate) among Fig. 7;
Fig. 9 is regional Al unit's vegetarian noodles distribution shown in Figure 7 (No. 1 aggregate);
Figure 10 is region S i unit's vegetarian noodles distribution shown in Figure 7 (No. 1 aggregate);
Figure 11 is regional O unit's vegetarian noodles distribution shown in Figure 7 (No. 1 aggregate);
Figure 12 is regional P unit's vegetarian noodles distribution shown in Figure 7 (No. 1 aggregate);
Figure 13 is No. 2 aggregates (aluminium dihydrogen phosphate immersion) microtexture sem photographs (* 100);
Figure 14 is No. 2 aggregates (aluminium dihydrogen phosphate immersion) microtexture sem photographs (* 500);
Figure 15 is that regional energy spectrometer shown in the square frame is measured microcell constituent content (No. 2 aggregates) among Figure 14;
Figure 16 is No. 2 aggregates (aluminium dihydrogen phosphate immersion) microtexture sem photographs (* 500);
Figure 17 is that position a energy spectrometer (EDX) is measured microcell constituent content (No. 2 aggregates) among Figure 16; Wherein, the Ti element derives from the TiO in the specimen preparation process
2The polishing agent;
Figure 18 is that position b energy spectrometer (EDX) is measured microcell constituent content (No. 2 aggregates) among Figure 16;
Figure 19 is regional P unit's vegetarian noodles distribution shown in Figure 16 (No. 2 aggregates);
Figure 20 is No. 3 aggregates (phosphoric acid dip) microtexture sem photographs (* 500);
Figure 21 is No. 3 aggregates (phosphoric acid dip) microtexture sem photographs (* 1000);
Figure 22 is No. 3 aggregates (phosphoric acid dip) microtexture sem photograph (* 1000, the backscattered electron imaging);
Figure 23 is regional P unit's vegetarian noodles distribution (No. 3 aggregates) shown in the square frame among Figure 21;
Figure 24 is O, Al, Si and P element line distribution (No. 3 aggregates) in the zone shown in the straight line;
Figure 25 is No. 4 aggregates (silicon sol immersion) microtexture sem photographs (* 100);
Figure 26 is No. 4 aggregates (silicon sol immersion) microtexture sem photographs (* 500);
Figure 27 is No. 4 aggregates (silicon sol immersion) microtexture sem photographs (* 1000);
Figure 28 is that position a energy spectrometer (EDX) is measured microcell constituent content (No. 4 aggregates) among Figure 27; Wherein, the Ti element derives from the TiO in the specimen preparation process
2The polishing agent;
Figure 29 is that position b energy spectrometer (EDX) is measured microcell constituent content (No. 4 aggregates) among Figure 27;
Figure 30 is O, Al and Si element line distribution (No. 4 aggregates) in the zone shown in the straight line.
Embodiment
Below in conjunction with specific embodiment the present invention is made detailed explanation.
Embodiment 1:
Prepare 1006 kilograms of roller hearth heating furnace roller light thermal-shield refractory castables: its raw material is formed and weight percent is: chemical modification aglite 50%, wherein: granularity is that the chemical modification aglite weight of 3～5mm accounts for 20% of chemical modification aglite gross weight, and the chemical modification aglite weight that granularity is respectively 1～3mm accounts for 30% of chemical modification aglite gross weight.Electrofused mullite (0～1mm) 10%; Kyanite (granularity≤180 orders) 5%; One-level high-alumina powder clinker (granularity≤180 orders) 8%; Fine silica powder (granularity≤5 μ m) 6%; α-Al
2O
3Micro mist (granularity≤5 μ m) 8%; Al80 high-alumina cement 7%; (length that contains the zirconium high-alumina refractory fiber is 3～10mm to contain zirconium high-alumina refractory fiber 3.4%.); Heat-resistant steel fiber 2%; Trimeric cyanamide 0.5%; Polypropylene fibre 0.1%.
Above-mentioned raw materials by the prescription weighing, is stirred in the adding agitator, add a certain amount of water more gradually, form the mould material of good fluidity.This kind mould material is added in the furnace roller mould, adopt the vibration process for forming moulding, the demoulding after 3 days, the furnace roller after the demoulding can use 400 ℃ of bakings in 24 hours.
The chemical modification aglite for the lightweight bauxites aggregate adopt aluminium dihydrogen phosphate (40wt%), phosphoric acid (60wt%) aqueous solution, silicon sol (25wt%), aluminium colloidal sol (25wt%) or sial complex sol (25wt%) soak 24 hours, dry in the shade with baking processing after get; Al in the described lightweight bauxites aggregate
2O
3Weight content be 40～80%.
Adopt the mould material of aluminium dihydrogen phosphate aqueous solution (40wt%), phosphate aqueous solution (60wt%), silicon sol (25wt%), aluminium colloidal sol (25wt%) or sial complex sol (25wt%) immersion modification processing to make the sample of 40 * 40 * 160mm size respectively the lightweight bauxites aggregate, with respect to the sample that uses the mould material preparation of not soaking aggregate, strength at normal temperature improves 1.8,1.2,4.5,2.2 and 3 times, and cold crushing strength improves 1.4,1.2,2.7,1.8 and 2.1 times.The anti-photo of testing the back section of reckoning the actual amount after a discount of sample that is soaked the modification processing by aggregate employing silicon sol contrasts (shown in Fig. 1-2) as can be seen, aglite adopts the mould material sample section after silicon sol soaks can significantly see the surface of fracture of a large amount of particless of aggregates, and the mould material sample section that the aggregate non-modified is handled only can be seen the surface of fracture of several aggregates, after illustrating that aggregate adopts the silicon sol immersion treatment, combining between aggregate and the matrix is more tight, reached the purpose that improves anti-folding of material and ultimate compression strength, further Micro-Structure Analysis has also confirmed above-mentioned conclusion (as shown in Figure 3-4).
Adopt scanning electronic microscope and energy spectrometer to analyze by microtexture and the element distribution of the lightweight bauxites aggregate being adopted aluminium dihydrogen phosphate, phosphoric acid or silica aqueous solution soak front and back, explained that further aglite soaks the mechanism of modification by chemical reagent.
The preparation of scanning electronic microscope sample: choose 4 parts of lightweight bauxites aggregates, wherein 3 parts are used aluminium dihydrogen phosphate (40wt%), phosphoric acid (50wt%) or silicon sol (25wt%) to soak respectively 24 hours, pull the back 120 ℃ of bakings 18 hours of drying in the shade out, 1350 ℃ of thermal treatment is 3 hours then, remains 1 part and does not carry out immersion treatment; Do not soak, adopt 4 parts of samples that aluminium dihydrogen phosphate, phosphoric acid or silicon sol soak through Resins, epoxy inlay, after grinding and buffing handles, make the mating plate sample, be numbered aggregate respectively 1,2,3, No. 4, behind surface spray carbon, use the scanning electronic microscope (Quanta 400) of configuration energy depressive spectroscopy to analyze, as not adding specified otherwise, the electronic scanning electromicroscopic photograph all adopts the secondary electron imaging.
The microtexture and the microcell element of No. 1 aggregate (not soaking) distribute shown in Fig. 5-12.Stereoscan photograph (Fig. 5-7) shows that sample is typical cell texture, and inside exists many defectives and crackle, and microcell ultimate analysis (Fig. 8) shows mainly by Si, Al, three kinds of O elementary composition, does not have the P element, and first vegetarian noodles distributes shown in Fig. 9-12.
The microtexture of No. 2 aggregates (aluminium dihydrogen phosphate immersion) and microcell element distribute shown in Figure 13-19.Stereoscan photograph (Figure 13-14) shows that sample is similarly typical cell texture, for No. 1 sample, void content descends to some extent, the particle that a large amount of particle diameters are 0.5-2 μ m (zone shown in square frame among Figure 14) has appearred in skeleton matrix inside, and tight with matrix bond, microcell ultimate analysis (as shown in figure 15) shows that these particulate components are Al
2O
3By the stereoscan photograph of bigger magnification and microcell ultimate analysis (shown in Figure 16-18) as can be seen: occurred certain compound in the grayish matrix (position shown in a among Figure 16) and assembled (spot of Dark grey shown in the b among Figure 16), microcell ultimate analysis (as shown in figure 17) shows that light grey matrix mainly contains Al, Si, four kinds of elements of P, O, all calculate, then wherein contain Al according to oxide compound
2O
3, SiO
2And P
2O
5Be respectively 38.92wt%, 47.00wt% and 7.40wt%, the microcell ultimate analysis (as shown in figure 18) of Dark grey speckle regions shows that this zone mainly contains Al, Si, four kinds of elements of P, O, all calculates according to oxide compound, then wherein contains Al
2O
3, SiO
2And P
2O
5Be respectively 40.32wt%, 6.21wt% and 53.47wt%, mol ratio is 45.17%, 11.80% and 43.03%, should the main thing in zone be AlPO mutually as can be seen
4, illustrate that the Dark grey spot in the matrix is AlPO
4Enrichment.
Microtexture by above No. 2 aggregates (aluminium dihydrogen phosphate aqueous solution immersion) and microcell ultimate analysis be as can be seen: with respect to No. 1 aggregate, lightweight bauxites aggregate matrix inside has occurred a large amount of and matrix bond corundum (α-Al closely
2O
3) particle (particle diameter is 0.5-2 μ m), and AlPO has appearred in matrix inside
4Enrichment.After 24 hours, phosphate dihydrogen aluminum solution has been penetrated into porous aggregate particulate inside by hole to these phenomenons explanation aglites through aluminium dihydrogen phosphate (40wt%) aqueous solution soaking, because solution is acid (PH=1), with the Al mutually of non-corundum in the aggregate
2O
3Part reacts and generates Al (H
2PO
4)
3And Al
2(HPO
4)
3, when aggregate through drying in the shade, 120 ℃ the baking 18 hours after, during again through 1350 ℃ of thermal treatments, along with the rising of temperature, phosphoric acid salt (Al (H
2PO
4)
3And Al
2(HPO
4)
3) generate polyphosphoric acid salt and four polymetaphosphate, when being higher than 1000 ℃, temperature just begins to resolve into AlPO4 and P
2O
5, P
2O
5After the volatilization, AlPO
4Left behind and enrichment has taken place in aggregate inside; Further distribute (as shown in figure 19) as can be seen by the face of P element in the zone shown in Figure 16, be distributed in the P element set hole around, the zone that micropore is many more, the distribution of P element is just many more, the matrix around the micropore has been strengthened in this distribution.Simultaneously, non-corundum phase Al in the aggregate
2O
3Active increasing is converted into α-Al in 3 hours rear sections of 1350 ℃ of thermal treatments after acid phosphatase aluminum dihydrogen solution-treated
2O
3, the micron particles form with particle diameter 0.5-2 μ m in the aggregate matrix exists, and firm with the aggregate matrix bond, and skeleton structure has been played strengthening effect.
The observations of above-mentioned scanning electronic microscope and the micro-zone analysis of energy spectrometer show that all aluminium dihydrogen phosphate has been penetrated into porous aggregate particulate inside by hole, have not only repaired tiny crack, have strengthened hole matrix on every side, have increased the intensity of aggregate; Its acidic solution is also for non-corundum phase Al in the aggregate
2O
3Played activation, made and in follow-up heat treatment process, change α-Al into
2O
3Micron particle has played enhancement to skeleton structure equally.
The microtexture of No. 3 aggregates (phosphate aqueous solution immersion) and microcell element distribute shown in Figure 20-24.Stereoscan photograph (Figure 20-22) is though the demonstration sample is a cell texture, but there are evident difference in its microtexture and No. 1 sample (not soaking aggregate), the aggregate matrix is because the erosion of phosphoric acid becomes uneven, illustrate highly acid phosphoric acid not only with the Al of aggregate surface
2O
3Reaction generates various aluminate or phosphates, also enters aggregate inside via hole by osmosis, and with the Al of aggregate inside
2O
3React, simultaneously the aluminate or phosphate that generates of part deposit to hole around (shown in the stereoscan photograph of Figure 22 backscattered electron imaging), during through 1350 ℃ of thermal treatments, along with the rising of temperature, various aluminate or phosphates have experienced following chemical reaction process: aluminate or phosphate → lose free-water → lose crystal water → AlPO
4Begin to separate out, polyphosphoric acid salt and four polymetaphosphate form gradually → polyphosphoric acid salt and four polymetaphosphate resolve into AlPO
4And P
2O
5(Gu) → P
2O
5The remaining AlPO in (gas) volatilization back
4Further by among Figure 21 shown in the square frame in the zone face of P element distribute (as shown in figure 23) as can be seen, the P element all has distribution in whole substrate, it is the most concentrated to distribute in the peripheral region of hole, the zone that hole is many more, the distribution of P element is just many more; Line by the P element distributes (as shown in figure 24) as can be seen, apart from the zone about hole edge, the right 25 μ m, the content of P element is higher, shows that further aggregate passed through phosphoric acid dip after 24 hours, and phosphoric acid has been penetrated into inner and and the Al of porous aggregate particulate by hole
2O
3Reaction generates aluminate or phosphate, is converted into AlPO after 1350 ℃ of thermal treatments
4, concentrate the edge that is distributed in hole, strengthened hole matrix on every side, increased the intensity of aggregate, the aluminate or phosphate of Sheng Chenging has been repaired the tiny crack of aggregate inside to a certain extent simultaneously, and skeleton structure has been played enhancement.
The microtexture of No. 4 aggregates (silicon sol immersion) and microcell element distribute shown in Figure 25-30.Stereoscan photograph (Figure 25-27) shows that sample is similarly typical cell texture, for No. 1 sample, void content is not significant to be changed, the microcell ultimate analysis (as shown in figure 28) of position a shows that this microcell matrix mainly contains Al, Si, three kinds of elements of O among Figure 27, all calculate, then wherein contain Al according to oxide compound
2O
3And SiO
2Be respectively 54.12wt% and 40.52wt%; Line by the Si element distributes (as shown in figure 30) as can be seen, the local height that the scope internal ratio abporal lacuna of the content of Si element about From Left hole edge 30 μ m is far away, after showing that aggregate soaks 24 hours through silicon sol, silicon sol has been penetrated into porous aggregate particulate inside by hole, and it is more to distribute around hole, this infiltration of silicon sol and distribution mode have been strengthened the matrix around the hole, have increased the intensity of aggregate.Scanning electron microscopic observation is found simultaneously; the particle that a large amount of particle diameters are 2-8 μ m (zone and shown in Figure 27 shown in square frame among Figure 26) has appearred in aggregate matrix inside; and tight with matrix bond, the ultimate analysis of particulate microcell shown in the b of position (as shown in figure 29) shows that these particle chemical ingredientss are Al among Figure 27
2O
3, it forms available following mechanism and explains: silicon sol has been penetrated into porous aggregate particulate inside by hole, because employed silicon sol is alkalescence (PH=10-11), to the SiO in the aggregate
2Existence is than the obvious corrosion effect, on the one hand SiO in the aggregate
2Destroy original microtexture after the corrosion, made Al
2O
3Isolated out, on the other hand, because the infiltration absorption and the cohesive action of silicon sol, microtexture to breakage is in time repaired, therefore do not find in the observation of scanning electronic microscope that aggregate vesicular microtexture takes place obviously to change, but this corrosion of silicon sol and the process of reparation are to Al
2O
3Played the effect of surface active, 1350 ℃ of thermal treatments after 3 hours, the non-corundum phase Al that the surface is activated
2O
3Part is converted into α-Al
2O
3, the micron particles form with particle diameter 2-8 μ m in the aggregate matrix exists, and firm with the aggregate matrix bond, and skeleton structure has been played strengthening effect.
From the Comprehensive analysis results of above-mentioned scanning electronic microscope and energy spectrometer as can be seen: aluminium dihydrogen phosphate, phosphoric acid or silicon sol soak after modification handles aglite, all can be penetrated into porous aggregate particulate inside by hole, repair the aggregate internal tiny crack, and it is more concentrated to distribute around hole, strengthen hole matrix on every side, increased the intensity of aggregate.Not only improve the mechanical property and the surface property of aglite, also improved the bonding state between aggregate and the powder, reached the purpose that improves the physicochemical properties such as anti-mechanical vibration ability, toughness and anti-sweep of gases ability of lightweight heat-proof mould material; In addition, the aggregate water-intake rate descends after the immersion treatment, has reduced the construction amount of water of lightweight heat-proof mould material, has improved the workability of mould material.
Embodiment 2:
Prepare 1095.5 kilograms of roller hearth heating furnace roller light thermal-shield refractory castables: its raw material is formed and weight percent is: chemical modification aglite 40%, wherein granularity is that the chemical modification aglite weight of 3～5mm accounts for 15% of light thermal-shield refractory castable gross weight, the chemical modification aglite weight that granularity is respectively 1～3mm accounts for 25% of light thermal-shield refractory castable gross weight, the chemical modification aglite for the lightweight bauxites aggregate adopt aluminium colloidal sol (15～25wt%) soak 24 hours, dry in the shade with baking processing after get; Electrofused mullite (0～1mm) 15%; Kyanite (granularity≤180 orders) 10%; One-level high-alumina powder clinker (granularity≤180 orders) 5%; Fine silica powder (granularity≤5 μ m) 8%; α-Al
2O
3Micro mist (granularity≤5 μ m) 4%; Al80 high-alumina cement 5%; Contain zirconium high-alumina refractory fiber 10%; Heat-resistant steel fiber 1.95%; Trimeric cyanamide 1%; Polypropylene fibre 0.05%.Above-mentioned raw materials by the prescription weighing, is stirred in the adding agitator, add a certain amount of water gradually, form the mould material of good fluidity.This kind mould material is added in the furnace roller mould, adopt the vibration process for forming moulding, the demoulding after 3 days, the furnace roller after the demoulding can use 400 ℃ of bakings in 24 hours.
Embodiment 3:
Prepare 1017 kilograms of roller hearth heating furnace roller light thermal-shield refractory castables: its raw material is formed and weight percent is: chemical modification aglite 40%, wherein granularity be 3～5mm and 1～3mm be respectively 15% and 25%, the chemical modification aglite for the lightweight bauxites aggregate adopt the sial complex sol (15～25wt%) soak 24 hours, dry in the shade with baking processing after get; Electrofused mullite (0～1mm) 20%; Kyanite (granularity≤180 orders) 6%; One-level high-alumina powder clinker (granularity≤180 orders) 10%; Fine silica powder (granularity≤5 μ m) 6.3%; α-Al
2O
3Micro mist (granularity≤5 μ m) 3%; Al80 cement 10%; Contain zirconium high-alumina refractory fiber 0.5%; Heat-resistant steel fiber 4%; Trimeric cyanamide 0.1%; Polypropylene fibre 0.1%.Above-mentioned raw materials by the prescription weighing, is stirred in the adding agitator, add a certain amount of water gradually, form the mould material of good fluidity.This kind mould material is added in the furnace roller mould, adopt the vibration process for forming moulding, the demoulding after 3 days, the furnace roller after the demoulding can use 400 ℃ of bakings in 24 hours.
Embodiment 4:
Prepare 1016 kilograms of roller hearth heating furnace roller light thermal-shield refractory castables: its raw material is formed and weight percent is: chemical modification aglite 50%, wherein granularity be 3～5mm and 1～3mm be respectively 15% and 35%, the chemical modification aglite for the lightweight bauxites aggregate adopt aluminium dihydrogen phosphate aqueous solution (25～40wt%) soak 24 hours, dry in the shade with baking processing after get; Electrofused mullite (0～1mm) 12%; Kyanite (granularity≤180 orders) 5%; One-level high-alumina powder clinker (granularity≤180 orders) 5%; Fine silica powder (granularity≤5 μ m) 8%; α-Al
2O
3Micro mist (granularity≤5 μ m) 7.4%; Al80 cement 6%; Contain zirconium high-alumina refractory fiber 4%; Heat-resistant steel fiber 2%; Trimeric cyanamide 0.5%; Polypropylene fibre 0.1%.Above-mentioned raw materials by the prescription weighing, is stirred in the adding agitator, add a certain amount of water gradually, form the mould material of good fluidity.This kind mould material is added in the furnace roller mould, adopt the vibration process for forming moulding, the demoulding after 3 days, the furnace roller after the demoulding can use 400 ℃ of bakings in 24 hours.
Embodiment 5:
Prepare 1056 kilograms of roller hearth heating furnace roller light thermal-shield refractory castables: its raw material is formed and weight percent is: chemical modification aglite 60%, wherein granularity be 3～5mm and 1～3mm be respectively 20% and 40%, the chemical modification aglite for the lightweight bauxites aggregate adopt phosphate aqueous solution (30～60wt%) soak 24 hours, dry in the shade with baking processing after get; Electrofused mullite (0～1mm) 10%; Kyanite (granularity≤180 orders) 5%; One-level high-alumina powder clinker (granularity≤180 orders) 10%; Fine silica powder (granularity≤5 μ m) 3%; α-Al
2O
3Micro mist (granularity≤5 μ m) 3%; Al80 cement 5%; Contain zirconium high-alumina refractory fiber 1.9%; Heat-resistant steel fiber 1.5%; Trimeric cyanamide 0.5%; The organic explosion-proof fiber 0.1% of KDF-II or KDF-III type.Above-mentioned raw materials by the prescription weighing, is stirred in the adding agitator, add a certain amount of water gradually, form the mould material of good fluidity.
Embodiment 6:
Prepare 1006 kilograms of roller hearth heating furnace roller light thermal-shield refractory castables, it is similar to Example 1 to fill a prescription, and difference is to be used for aglite and uses the light-weight mullite aggregate, and (15～25wt%) soak modification handles to use silicon sol.Raw material by the prescription weighing, is stirred in the adding agitator, add a certain amount of water gradually, form the mould material of good fluidity.This kind mould material is added in the furnace roller mould, adopt the vibration process for forming moulding, the demoulding after 3 days, the furnace roller after the demoulding can use 400 ℃ of bakings in 24 hours.
The present invention is not limited to above-mentioned preferred forms, and anyone should learn the structural changes of making under enlightenment of the present invention, and every have identical or close technical scheme with the present invention, all falls within protection scope of the present invention.
Claims (6)
1. light thermal-shield refractory castable, it is characterized in that: it comprises following components in weight percentage:
The chemical modification aglite, 40～60%; Electrofused mullite, 10～20%; The aquamaine stone flour, 5～10%; High-alumina powder clinker, 5～10%; Fine silica powder, 3～8%; α-Al
2O
3Micro mist, 3～8%; High-alumina cement, 5～10%; Contain the zirconium high-alumina refractory fiber, 0.5～10%; Heat-resistant steel fiber, 1.5～4%; Trimeric cyanamide, 0.1～1%; Organic explosion-proof fiber, 0.05～0.10%;
The granularity of described electrofused mullite is smaller or equal to 1mm; The granularity of fine silica powder and α-Al
2O
3The granularity of micro mist is all smaller or equal to 5 μ m;
Described chemical modification aglite is that aglite soaks after drying and forms in inorganic chemistry solution or colloidal sol.
2. light thermal-shield refractory castable as claimed in claim 1 is characterized in that: described inorganic chemistry solution or colloidal sol are a kind of in aluminium dihydrogen phosphate aqueous solution, phosphate aqueous solution, silicon sol, aluminium colloidal sol, the sial complex sol.
3. light thermal-shield refractory castable as claimed in claim 2, it is characterized in that: the weight concentration of described aluminium dihydrogen phosphate aqueous solution is 25～40%, the weight concentration of described phosphate aqueous solution is 30～60%, the weight concentration 15～25% of described silicon sol, aluminium colloidal sol, sial complex sol.
4. light thermal-shield refractory castable as claimed in claim 1 is characterized in that: aglite is lightweight bauxites aggregate or light-weight mullite aggregate in the described chemical modification aglite; Al in the described lightweight bauxites aggregate
2O
3Weight content be 40～80%.
5. light thermal-shield refractory castable as claimed in claim 1, it is characterized in that: described chemical modification aglite is made of two kinds of grain compositions that granularity is respectively 3～5mm and 1～3mm, wherein, granularity is that the chemical modification aglite weight of 3～5mm accounts for 15～25% of light thermal-shield refractory castable gross weight, and the chemical modification aglite weight that granularity is respectively 1～3mm accounts for 25～40% of light thermal-shield refractory castable gross weight.
6. light thermal-shield refractory castable as claimed in claim 1 is characterized in that: the described length that contains the zirconium high-alumina refractory fiber is 3～10mm.
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|---|---|---|---|
| CN2010101375016A CN101792294B (en) | 2010-03-30 | 2010-03-30 | Light thermal-shield refractory castable |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101375016A CN101792294B (en) | 2010-03-30 | 2010-03-30 | Light thermal-shield refractory castable |
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| CN101792294B CN101792294B (en) | 2012-05-30 |
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| CN103017537A (en) * | 2012-12-14 | 2013-04-03 | 安徽省枞阳县旭阳金属颜料有限公司 | Aluminum melting furnace |
| CN103265302A (en) * | 2013-06-03 | 2013-08-28 | 武汉钢铁(集团)公司 | Refractory castable for side protecting plate of converter as well as production method and application of refractory castable |
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