Background technology
Current China building energy consumption has accounted for 30% of total energy consumption, and building energy conservation has become the emphasis of energy-saving and emission-reduction.Development of new heat-preserving energy-saving wall material, the heat-insulating property improving exterior wall is significant to realizing building energy conservation.A large amount of engineering practice proves, wall thermal insulation technology is the optimal path realizing building energy conservation heat insulation.
Under construction green energy conservation society tide promotes, people improve increasingly to the expectation of building energy conservation and pursuit, have employed various body of wall retaining design as bulk external insulation system, bulk folder (filling out) core architecture and sheet material class composite thermal insulation system.But organic insulation material is easy to burning, there is safety problem.Development of new inorganic energy-saving heat preserving material of construction is imperative.
Foamed ceramic material is developed to meet this demand.Foamed ceramic material, owing to having low density, high intensity, high refractoriness, good heat-shock resistance and low thermal conductivity, is suitable as high temperature insulating refractory materials.Foamed ceramic material has building thermal-insulation energy-saving, not to fire and the multiple effect such as sound insulation completely, is the outer wall material of a new generation, will plays great function for building energy conservation.
Template leaves hole by the ablation of pore-forming material or decomposition, and porosity is usually less than 70%, is unfavorable for the porous ceramic film material preparing lower thermal conductivity.Polymeric sponge method utilizes foam impregnation ceramic size, burning-off organic foam after dry, thus obtaining the porous ceramic film material with an organic foam reciprocal form structure, the porous ceramic film material structure prepared is intercommunicating pore structure, should not be used as lagging material.
The main method preparing foamed ceramic (porous ceramics) at present has powder green bodies foaming and slurry foaming, usual employing whipping agent and a large amount of raw ore raw materials, complex process, firing temperature is high, cost is higher, not easily manufacture large size foamed ceramic (porous ceramics) plate continuously, its purposes is restricted.Simultaneously in existing foamed ceramic preparation process, crosslinking degree is wayward, cause stupalith high-strength not or intensity distribution uneven, foaming back aperture size is uneven, unstable properties.
In order to the intensity strengthening porous ceramic film material adopts crosslinking to make porous ceramic film material be cross-linked usually.Existing porous ceramic film material is all adopt chemical crosslink technique.Chemical crosslink technique utilizes the chemical cross-linking agent decomposes in raw material and starting material generation chemical reaction and is cross-linked.This method degree of crosslinking is not high, technique is wayward, and the foam structure quality defect of the foam materials obtained.
Radiation cross-linking process cross-linking efficiency is high, do not need to add linking agent, so technique also easily controls, and the foam structure quality of resulting product is good.
Summary of the invention
In order to the existing ceramic plate intensity of satisfied raising, reduce costs, improve the demand of ceramic plate quality, embodiments provide a kind of preparation method of high-strength light energy-saving pottery porcelain plate.The method does not use chemical cross-linking agent to change cross-linking radiation into, and crosslinking process is easily controlled, and crosslink material is even, and ceramic plate intensity is greatly improved; The ceramic plate simultaneously using a kind of foaming agent composotion to obtain not only steeps uniform pore diameter, and the distribution of abscess in ceramic plate is also even, makes ceramic plate stable performance, even intensity.
In order to realize foregoing invention object, the invention provides a kind of preparation method of high-strength light energy-saving pottery porcelain plate, comprising the following steps:
(1) by tapioca flour 75 ~ 85 DEG C of gelatinizations 0.5 ~ 1 hour, then in gelatinization tapioca flour, vinylformic acid, poly aspartic acid and nucite phosphoric acid ester is added, vinylformic acid: gelatinization tapioca flour: poly aspartic acid: nucite phosphoric acid ester mass ratio is the obtained mixed serum I in 0.3 ~ 0.9:2.1 ~ 2.7:1:0.1 ~ 0.4, and the mixed serum I of 20 ~ 80wt% and the water of 20 ~ 80wt% are mixed to form mixed serum II; Adjustment pH value is 8.5 ~ 10 must mixed serum III; Waste and old ceramic tile being ground to form granularity is that ceramic powder and the described mixed serum III of 0.01 ~ 0.15 μm adds ballstone and grind in 70 ~ 80:20 ~ 30 by weight percentage after fully mixing, and makes ceramic size mixture A;
(2) in ceramic size mixture A, then pour nitrogen vigorous stirring displacement simultaneously oxygen wherein, 1 ~ 8wt% whipping agent that addition accounts for mixed serum I is added in abundant stirring backward ceramic size mixture A, continue stirring and obtain pre-mixture B in 1 ~ 2 minute, wherein whipping agent is: sodium lauryl sulphate, bicarbonate of ammonia, polyoxyethylene glycol, 4, 4'-bis--sulfonyl hydrazide phenyl ether, diphenylmethylene sorbyl alcohol and 2, the mixture of 2'-methylene radical-bis-(4.6-di-tert-butyl-phenyl) sodium phosphate, its mass ratio is 1 ~ 2:4 ~ 10:5 ~ 8:2 ~ 3:0.05 ~ 0.1:0.05 ~ 0.2,
(3) pre-mixture B is placed under nitrogen protection
60in Co gamma-ray irradiation field, irradiation dose is 6 ~ 20kGy, then at the temperature of 70 ~ 120 DEG C, 10 minutes ~ 4 hours curing moldings are incubated, then the demoulding is dry, make the water ratio of base substrate lower than below 0.5wt%, calcined by dried base substrate, calcining temperature is 900 DEG C ~ 1200 DEG C, calcination time 0.5 ~ 2 hour.
Described in described step (2), whipping agent addition accounts for 1 ~ 4wt% of mixed serum I.
Described vinylformic acid: gelatinization tapioca flour: poly aspartic acid: nucite phosphoric acid ester mass ratio is 0.3:2.1:1:0.2; Described whipping agent is: sodium lauryl sulphate, bicarbonate of ammonia, polyoxyethylene glycol, 4,4'-bis--sulfonyl hydrazide phenyl ether, diphenylmethylene sorbyl alcohol and 2, the mixture of 2'-methylene radical-bis-(4.6-di-tert-butyl-phenyl) sodium phosphate, its mass ratio is 1:5:5:2:0.1:0.2.
Described vinylformic acid: gelatinization tapioca flour: poly aspartic acid: nucite phosphoric acid ester mass ratio is 0.5:2.4:1:0.4; Described whipping agent is: sodium lauryl sulphate, bicarbonate of ammonia, polyoxyethylene glycol, 4,4'-bis--sulfonyl hydrazide phenyl ether, diphenylmethylene sorbyl alcohol and 2, the mixture of 2'-methylene radical-bis-(4.6-di-tert-butyl-phenyl) sodium phosphate, its mass ratio is 1.5:8:7:3:0.07:0.1.
Described vinylformic acid: gelatinization tapioca flour: poly aspartic acid: nucite phosphoric acid ester mass ratio is 0.9:2.7:1:0.1; Described whipping agent is: sodium lauryl sulphate, bicarbonate of ammonia, polyoxyethylene glycol, 4,4'-bis--sulfonyl hydrazide phenyl ether, diphenylmethylene sorbyl alcohol and 2, the mixture of 2'-methylene radical-bis-(4.6-di-tert-butyl-phenyl) sodium phosphate, its mass ratio is 2:4:6:2:0.05:0.2.
The beneficial effect that the technical scheme that the embodiment of the present invention provides is brought is:
1, the intensity of ceramic plate is high, and density is little, has saved cost greatly;
2, the foaming back aperture size of ceramic plate evenly, stable performance.
Embodiment
, unstable properties uneven for existing ceramic plate foaming back aperture size, the problem that intensity is not high, the invention provides a kind of preparation method of high-strength light energy-saving pottery porcelain plate, comprises the following steps:
(1) by tapioca flour 75 ~ 85 DEG C of gelatinizations 0.5 ~ 1 hour, then in gelatinization tapioca flour, vinylformic acid, poly aspartic acid and nucite phosphoric acid ester is added, vinylformic acid: gelatinization tapioca flour: poly aspartic acid: nucite phosphoric acid ester mass ratio is the obtained mixed serum I in 0.3 ~ 0.9:2.1 ~ 2.7:1:0.1 ~ 0.4, and the mixed serum I of 20 ~ 80wt% and the water of 20 ~ 80wt% are mixed to form mixed serum II; Adjustment pH value is 8.5 ~ 10 must mixed serum III; Waste and old ceramic tile being ground to form granularity is that ceramic powder and the described mixed serum III of 0.01 ~ 0.15 μm adds ballstone and grind in 70 ~ 80:20 ~ 30 by weight percentage after fully mixing, and makes ceramic size mixture A;
(2) in ceramic size mixture A, then pour nitrogen vigorous stirring displacement simultaneously oxygen wherein, 1 ~ 8wt% whipping agent that addition accounts for mixed serum I is added in abundant stirring backward ceramic size mixture A, continue stirring and obtain pre-mixture B in 1 ~ 2 minute, wherein whipping agent is: sodium lauryl sulphate, bicarbonate of ammonia, polyoxyethylene glycol, 4, 4'-bis--sulfonyl hydrazide phenyl ether, diphenylmethylene sorbyl alcohol and 2, the mixture of 2'-methylene radical-bis-(4.6-di-tert-butyl-phenyl) sodium phosphate, its mass ratio is 1 ~ 2:4 ~ 10:5 ~ 8:2 ~ 3:0.05 ~ 0.1:0.05 ~ 0.2,
(3) pre-mixture B is placed under nitrogen protection
60in Co gamma-ray irradiation field, irradiation dose is 6 ~ 20kGy, then at the temperature of 70 ~ 120 DEG C, 10 minutes ~ 4 hours curing moldings are incubated, then the demoulding is dry, make the water ratio of base substrate lower than below 0.5wt%, calcined by dried base substrate, calcining temperature is 900 DEG C ~ 1200 DEG C, calcination time 0.5 ~ 2 hour.
Embodiment 1
(1) by tapioca flour 80 DEG C of gelatinizations 0.7 hour, then in gelatinization tapioca flour, vinylformic acid, poly aspartic acid and nucite phosphoric acid ester is added, its mass ratio is vinylformic acid: gelatinization tapioca flour: poly aspartic acid: nucite phosphoric acid ester mass ratio is that 0.3:2.1:1:0.2 obtains mixed serum I, and the mixed serum I of 25wt% is mixed to form mixed serum II with the water of 75wt%; Adjustment pH value is 9 must mixed serum III; Waste and old ceramic tile is ground to form granularity be 0.01 ~ 0.15 μm ceramic powder and described mixed serum III by weight percentage 70:30 add ballstone after fully mixing and grind, make ceramic size mixture A;
(2) in ceramic size mixture A, then pour nitrogen vigorous stirring displacement simultaneously oxygen wherein; the 2wt% whipping agent that addition accounts for mixed serum I is added in abundant stirring backward ceramic size mixture A; continue stirring and obtain pre-mixture B in 1 minute; wherein whipping agent is: sodium lauryl sulphate; bicarbonate of ammonia; polyoxyethylene glycol; 4; 4'-bis--sulfonyl hydrazide phenyl ether; diphenylmethylene sorbyl alcohol and 2; the mixture of 2'-methylene radical-bis-(4.6-di-tert-butyl-phenyl) sodium phosphate, its mass ratio is 1:5:5:2:0.1:0.2;
(3) pre-mixture B is placed under nitrogen protection
60in Co gamma-ray irradiation field, irradiation dose is 8kGy, then at the temperature of 90 DEG C, is incubated 3 hours curing moldings, then the demoulding is dry, makes the water ratio of base substrate lower than below 0.5wt%, is calcined by dried base substrate, calcining temperature is 1200 DEG C, calcination time 0.5 hour.
This light foamed ceramic plate unit weight is 0.3g/cm3, and folding strength is 23Mpa.
Embodiment 2
(1) by tapioca flour 85 DEG C of gelatinizations 0.5 hour, then in gelatinization tapioca flour, vinylformic acid, poly aspartic acid and nucite phosphoric acid ester is added, its mass ratio is vinylformic acid: gelatinization tapioca flour: poly aspartic acid: nucite phosphoric acid ester mass ratio is that 0.5:2.4:1:0.4 obtains mixed serum I, and the mixed serum I of 50wt% is mixed to form mixed serum II with the water of 50wt%; Adjustment pH value is 9.5 must mixed serum III; Waste and old ceramic tile is ground to form granularity be 0.01 ~ 0.15 μm ceramic powder and described mixed serum III by weight percentage 75:25 add ballstone after fully mixing and grind, make ceramic size mixture A;
(2) in ceramic size mixture A, then pour nitrogen vigorous stirring displacement simultaneously oxygen wherein; the 1wt% whipping agent that addition accounts for mixed serum I is added in abundant stirring backward ceramic size mixture A; outer continuation stirring obtains pre-mixture B in 1 minute; wherein whipping agent is: sodium lauryl sulphate; bicarbonate of ammonia; polyoxyethylene glycol; 4; 4'-bis--sulfonyl hydrazide phenyl ether; diphenylmethylene sorbyl alcohol and 2; the mixture of 2'-methylene radical-bis-(4.6-di-tert-butyl-phenyl) sodium phosphate, its mass ratio is 1.5:8:7:3:0.07:0.1;
(3) pre-mixture B is placed under nitrogen protection
60in Co gamma-ray irradiation field, irradiation dose is 10kGy, then at the temperature of 80 DEG C, is incubated 4 hours curing moldings, then the demoulding is dry, makes the water ratio of base substrate lower than below 0.5wt%, is calcined by dried base substrate, calcining temperature is 900 DEG C, calcination time 2 hours.
This light foamed ceramic plate unit weight is 0.28g/cm3, and folding strength is 23.8Mpa.
Embodiment 3
(1) by tapioca flour 75 DEG C of gelatinizations 1 hour, then in gelatinization tapioca flour, vinylformic acid, poly aspartic acid and nucite phosphoric acid ester is added, its mass ratio is vinylformic acid: gelatinization tapioca flour: poly aspartic acid: nucite phosphoric acid ester mass ratio is that 0.9:2.7:1:0.1 obtains mixed serum I, and the mixed serum I of 70wt% is mixed to form mixed serum II with the water of 30wt%; Adjustment pH value is 9 must mixed serum III; Waste and old ceramic tile is ground to form granularity be 0.01 ~ 0.15 μm ceramic powder and described mixed serum III by weight percentage 80:20 add ballstone after fully mixing and grind, make ceramic size mixture A;
(2) in ceramic size mixture A, then pour nitrogen vigorous stirring displacement simultaneously oxygen wherein; the 3wt% whipping agent that addition accounts for mixed serum I is added in abundant stirring backward ceramic size mixture A; continue stirring and obtain pre-mixture B in 1 minute; wherein whipping agent is: sodium lauryl sulphate; bicarbonate of ammonia; polyoxyethylene glycol; 4; 4'-bis--sulfonyl hydrazide phenyl ether; diphenylmethylene sorbyl alcohol and 2; the mixture of 2'-methylene radical-bis-(4.6-di-tert-butyl-phenyl) sodium phosphate, its mass ratio is 2:4:6:2:0.05:0.2;
(3) pre-mixture B is placed under nitrogen protection
60in Co gamma-ray irradiation field, irradiation dose is 15kGy, then at the temperature of 120 DEG C, is incubated 1 hour curing molding, then the demoulding is dry, makes the water ratio of base substrate lower than below 0.5wt%, is calcined by dried base substrate, calcining temperature is 100 DEG C, calcination time 1 hour.
This light foamed ceramic plate unit weight is 0.31g/cm3, and folding strength is 24Mpa.
The present invention is cooperated by combination of monomers, blowing agent combination and x ray irradiation x, and the unit weight effectively reducing ceramic plate has saved cost, and the intensity of ceramic plate is improved.Then change the x ray irradiation x of the 3rd step into conventional chemical cross-linking agent N below, N-methylene radical acrylamide, carries out simultaneous test.
Simultaneous test 1:
(1) by tapioca flour 80 DEG C of gelatinizations 0.7 hour, then in gelatinization tapioca flour, vinylformic acid, poly aspartic acid and nucite phosphoric acid ester is added, its mass ratio is vinylformic acid: gelatinization tapioca flour: poly aspartic acid: nucite phosphoric acid ester mass ratio is that 0.3:2.1:1:0.2 obtains mixed serum I, and the mixed serum I of 25wt% is mixed to form mixed serum II with the water of 75wt%; Adjustment pH value is 9 must mixed serum III; Waste and old ceramic tile is ground to form granularity be 0.01 ~ 0.15 μm ceramic powder and described mixed serum III by weight percentage 70:30 add ballstone after fully mixing and grind, make ceramic size mixture A;
(2) in ceramic size mixture A, then pour nitrogen vigorous stirring displacement simultaneously oxygen wherein, the 2wt% whipping agent that addition accounts for mixed serum I is added in abundant stirring backward ceramic size mixture A, additional 0.02wt% linking agent N, N-methylene radical acrylamide, additional 0.06wt% initiator and 0.06% catalyzer continue stirring and obtain pre-mixture B in 1 minute, wherein whipping agent is: sodium lauryl sulphate, bicarbonate of ammonia, polyoxyethylene glycol, 4, 4'-bis--sulfonyl hydrazide phenyl ether, diphenylmethylene sorbyl alcohol and 2, the mixture of 2'-methylene radical-bis-(4.6-di-tert-butyl-phenyl) sodium phosphate, its mass ratio is 1:5:5:2:0.1:0.2,
(3) heated up under nitrogen protection by pre-mixture B, then at the temperature of 90 DEG C, soaking time is 3 hours curing moldings, and then the demoulding is dry; make the water ratio of base substrate lower than below 0.5wt%; calcined by dried base substrate, calcining temperature is 1200 DEG C, calcination time 0.5 hour.
This light foamed ceramic plate unit weight is 0.31g/cm3, and folding strength is 18Mpa.
Then change whipping agent into conventional sodium carbonate below, the x ray irradiation x of the 3rd step is changed into conventional chemical cross-linking agent N, N-methylene radical acrylamide, carries out simultaneous test.
Simultaneous test 2:
(1) by tapioca flour 80 DEG C of gelatinizations 0.7 hour, then in gelatinization tapioca flour, vinylformic acid, poly aspartic acid and nucite phosphoric acid ester is added, its mass ratio is vinylformic acid: gelatinization tapioca flour: poly aspartic acid: nucite phosphoric acid ester mass ratio is that 0.3:2.1:1:0.2 obtains mixed serum I, and the mixed serum I of 25wt% is mixed to form mixed serum II with the water of 75wt%; Adjustment pH value is 9 must mixed serum III; Waste and old ceramic tile is ground to form granularity be 0.01 ~ 0.15 μm ceramic powder and described mixed serum III by weight percentage 70:30 add after ballstone grinds after fully mixing, make ceramic size mixture A;
(2) in ceramic size mixture A, then pour nitrogen vigorous stirring displacement simultaneously oxygen wherein; the 2wt% whipping agent sodium carbonate that addition accounts for mixed serum I is added in abundant stirring backward ceramic size mixture A; additional 0.02wt% linking agent N; N-methylene radical acrylamide, additional 0.06wt% initiator and 0.06% catalyzer continue stirring and obtain pre-mixture B in 1 minute;
(3) heated up under nitrogen protection by pre-mixture B, then at the temperature of 90 DEG C, soaking time is 3 hours curing moldings, and then the demoulding is dry; make the water ratio of base substrate lower than below 0.5wt%; calcined by dried base substrate, calcining temperature is 1200 DEG C, calcination time 0.5 hour.
This light foamed ceramic plate unit weight is 0.61g/cm3, and folding strength is 19Mpa.
By the performance of pottery obtained, contrast with the performance of the pottery of three embodiments above, can illustrate and adopt blowing agent combination of the present invention to coordinate with x ray irradiation x, the pottery prepared can be made, unit weight reduces a lot, cost-saving, intensity improves simultaneously, improves the performance of ceramic plate.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.