CN103435322A - Preparation method of high-temperature-resistant ceramic base polymer - Google Patents

Preparation method of high-temperature-resistant ceramic base polymer Download PDF

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Publication number
CN103435322A
CN103435322A CN2013103599157A CN201310359915A CN103435322A CN 103435322 A CN103435322 A CN 103435322A CN 2013103599157 A CN2013103599157 A CN 2013103599157A CN 201310359915 A CN201310359915 A CN 201310359915A CN 103435322 A CN103435322 A CN 103435322A
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preparation
ceramic
sample
mold
raw material
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李琴
徐燕
崔皓
孙增青
陶德晶
翟建平
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Nanjing University
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Nanjing University
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00Technologies for solid waste management
    • Y02W30/50Reuse, recycling or recovery technologies
    • Y02W30/91Use of waste materials as fillers for mortars or concrete

Abstract

The invention provides a preparation method of a high-temperature-resistant ceramic base polymer. The preparation method comprises the following steps: (1) performing ultrasonic cleaning on recycled waste ceramic; putting the cleaned ceramic raw material into a ball mill; performing ball milling on the ceramic raw material, so as to enable the average particle size of the ceramic raw material to be lowered to 10-50 micron; (2) adding an excitant solution into the levigated ceramic; adjusting the liquid/solid ratio of the excitant solution to the ceramic powder to be (0.3-0.5): 1; fully stirring the mixture; pouring the reagent into an alkaline-resistant mold; placing the mold on an electric vibrating table; vibrating the mold for 3-10 min; (3) sealing the mold after the mold is vibrated; performing demolding after the mold is placed at the room temperature or in a maintenance box at 20-60 DEG C for 24 hours; (4) continuing to maintain the demolded sample at the room temperature to 60 DEG C for a scheduled age, i.e. 3-28 days; drying the sample to obtain the ceramic base polymer. The ceramic base polymer prepared according to the preparation method has good mechanical property and high-temperature resistance property. Through the adoption of the preparation method, the problem of waste ceramic treatment is solved.

Description

A kind of preparation method of refractory ceramics based geopolymer
Technical field
The present invention relates to a kind of inorganic polymer material, specifically a kind of preparation method of refractory ceramics based geopolymer.
Background technology
Waste ceramic is as a kind of common solid waste, present stage the waste old ceramics recovery utilization rate of China low, its bulk deposition or landfill, not only waste soil, causes serious environmental pressure simultaneously, so its environmental protection recycling problem remains further to be solved.
Based geopolymer is the inorganic polymer material that a class has amorphous three-dimensional netted silicon-oxy tetrahedron and aluminum-oxygen tetrahedron structure, has the part advantage of inorganic materials and organic polymer concurrently.Because traditional strength of cement is less than 50MPa, and resistance to elevated temperatures is poor, is not suitable for being applied to the withstand voltage high temperature resistant occasion that particular requirement is arranged.On the other hand, due to silicon-aluminium component that waste ceramic contains some amount, can be used as in theory preparing the starting material of geopolymer, but its practical application is at present there are no relevant report.
Summary of the invention
The present invention is in order to solve the problem that the waste old ceramics recovery utilization rate is low, provides a kind of and take waste ceramic and prepare the method for refractory ceramics based geopolymer as raw material.
The preparation method of refractory ceramics based geopolymer of the present invention comprises the following steps:
1), by the waste ceramic ultrasonic cleaning of reclaiming, remove the impurity of surface adhesion;
2) ceramic raw material after cleaning is put into to the ball mill ball milling, makes its volume average particle size D[4,3] be down to the 10-50 micron;
3) exciting agent solution is joined in levigate pottery, Gu make the liquid of exciting agent solution and ceramic powder/than being (0.3-0.5): 1;
4) reaction system in step 3) is fully stirred, then reactant is poured in alkali-proof mould, mould is placed in to vibration 3-10 minute on electric vibration table;
5) by the die sealing after vibration treatment, at room temperature or be placed in maintaining box in 20-60 ℃ of lower maintenance demoulding after 24 hours; Sample after the demoulding continues extremely to be scheduled to the length of time in room temperature to 60 ℃ lower maintenance, and 3-28 days, make the ceramics base polymkeric substance after oven dry.
Further improve described step 2) in exciting agent be the alkali hydroxide soln that concentration is the 5-15 mol/L, or the modulus alkali metal silicate solutions that is 1.0-3.0, or both mixing solutionss.
Further improve, described alkali metal silicate solutions is that alkali metal silicate is received solution.
Further improve the mixture that described basic metal is sodium, potassium or sodium and potassium.
Beneficial effect of the present invention is:
1, the refractory ceramics based geopolymer of preparing has good mechanical property and resistance to elevated temperatures, and its 28 days compressive strengths surpass 71 MPa, under 1000 ℃ of conditions roasting after 2 hours ultimate compression strength still can reach 58 MPa.The field that is expected at mining, water conservancy construction, national defence and marine drilling platform etc., the material compressive property be had relatively high expectations replaces traditional cement material.
2, present method simultaneously also provides a feasible approach that utilizes for increasing but waste ceramic that still lack effective normal temperature method of disposal at present.
The accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph through the ceramic powder of ball-milling processing;
Fig. 2 is ceramics base polymers scanning of materials Electronic Speculum figure.
Embodiment
The raw material that the present invention uses: pottery, alkali-activator (sodium hydroxide or potassium hydroxide or its mixture, water glass or potassium silicate or its mixture) solution.Below in conjunction with specific embodiment, the invention will be further described
Embodiment 1:
1) by pollutents such as the plastics of the first ultrasonic cleaning removal of the waste ceramic reclaimed surface adhesion, paper scrap, metals, reduce its impact on follow-up preparation technology and ground polymers material.
2) ceramic raw material after cleaning is put into to the ball mill ball milling, makes its volume average particle size D[4,3] be down to the 10-50 micron.
3) with sodium base water glass and sodium hydroxide preparation modulus, be 1.0 water glass exciting agent solution.Gu by the water glass exciting agent solution of preparation and levigate pottery by liquid/than be 0.5 mix and stir after the steel mould of packing into.The mould that reactant is housed is placed on electric vibration table and vibrates 5 minutes to get rid of bubble, then by die sealing.
4) sealed mold is moved in the thermostatic curing case, 60 ℃ of lower maintenance demouldings after 24 hours.Sample after the demoulding continues maintenance 28 days under 60 ℃.
The sample that 5) will arrive curing age is placed in 40 ℃ of electric heating convection oven dries, and obtains the ceramics base polymkeric substance.With the 300KN pressing machine, the maintenance sample of 28 days is carried out the mensuration of ultimate compression strength, the results are shown in Table 1.
The sample that 6) will reach curing age is placed in 60 ℃ of electric drying oven with forced convections and dries 2 hours, sample after drying is placed in to retort furnace to be calcined 2 hours under 1000 ℃ of conditions, with the 300KN pressing machine, sample is carried out the mensuration of ultimate compression strength after naturally cooling, the results are shown in Table 1.
 
Embodiment 2:
1) by pollutents such as the plastics of the first ultrasonic cleaning removal of the waste ceramic reclaimed surface adhesion, paper scrap, metals, reduce its impact on follow-up preparation technology and ground polymers material.
2) ceramic raw material after cleaning is put into to the ball mill ball milling, makes its volume average particle size D[4,3] be down to the 10-50 micron.
3) the water glass exciting agent solution that is 1.2 with sodium base water glass and sodium hydroxide preparation modulus.Gu by the water glass exciting agent solution of preparation and levigate pottery by liquid/than be 0.5 mix and stir after the steel mould of packing into.The mould that reactant is housed is placed on electric vibration table and vibrates 5 minutes to get rid of bubble, then by die sealing.
4) sealed mold is moved in the thermostatic curing case, 60 ℃ of lower maintenance demouldings after 24 hours.Sample after the demoulding continues maintenance 28 days under 60 ℃.
The sample that 5) will arrive curing age is placed in 40 ℃ of electric heating convection oven dries, and obtains the ceramics base polymkeric substance.With the 300KN pressing machine, the maintenance sample of 28 days is carried out the mensuration of ultimate compression strength, the results are shown in Table 1.
The sample that 6) will reach curing age is placed in 60 ℃ of electric drying oven with forced convections and dries 2 hours, sample after drying is placed in to retort furnace to be calcined 2 hours under 1000 ℃ of conditions, with the 300KN pressing machine, sample is carried out the mensuration of ultimate compression strength after naturally cooling, the results are shown in Table 1.
 
Embodiment 3:
1) by pollutents such as the plastics of the first ultrasonic cleaning removal of the waste ceramic reclaimed surface adhesion, paper scrap, metals, reduce its impact on follow-up preparation technology and ground polymers material.
2) ceramic raw material after cleaning is put into to the ball mill ball milling, makes its volume average particle size D[4,3] be down to the 10-50 micron.
3) the water glass exciting agent solution that is 1.4 with sodium base water glass and sodium hydroxide preparation modulus.Gu by the water glass exciting agent solution of preparation and levigate pottery by liquid/than be 0.5 mix and stir after the steel mould of packing into.The mould that reactant is housed is placed on electric vibration table and vibrates 5 minutes to get rid of bubble, then by die sealing.
4) sealed mold is moved in the thermostatic curing case, 60 ℃ of lower maintenance demouldings after 24 hours.Sample after the demoulding continues maintenance 28 days under 60 ℃.
The sample that 5) will arrive curing age is placed in 40 ℃ of electric heating convection oven dries, and obtains the ceramics base polymkeric substance.With the 300KN pressing machine, the maintenance sample of 28 days is carried out the mensuration of ultimate compression strength, the results are shown in Table 1.
The sample that 6) will reach curing age is placed in 60 ℃ of electric drying oven with forced convections and dries 2 hours, sample after drying is placed in to retort furnace to be calcined 2 hours under 1000 ℃ of conditions, with the 300KN pressing machine, sample is carried out the mensuration of ultimate compression strength after naturally cooling, the results are shown in Table 1.
 
Embodiment 4:
1) by pollutents such as the plastics of the first ultrasonic cleaning removal of the waste ceramic reclaimed surface adhesion, paper scrap, metals, reduce its impact on follow-up preparation technology and ground polymers material.
2) ceramic raw material after cleaning is put into to the ball mill ball milling, makes its volume average particle size D[4,3] be down to the 10-50 micron.
3) water glass that is 1.2 with sodium base water glass and potassium hydroxide preparation modulus-potassium complex excitation agent solution.Gu by the water glass-potassium complex excitation agent solution of preparation and levigate pottery by liquid/than be 0.5 mix and stir after the steel mould of packing into.The mould that reactant is housed is placed on electric vibration table and vibrates 5 minutes to get rid of bubble, then by die sealing.
4) sealed mold is moved in the thermostatic curing case, 60 ℃ of lower maintenance demouldings after 24 hours.Sample after the demoulding continues maintenance 28 days under 60 ℃.
The sample that 5) will arrive curing age is placed in 40 ℃ of electric heating convection oven dries, and obtains the ceramics base polymkeric substance.With the 300KN pressing machine, the maintenance sample of 28 days is carried out the mensuration of ultimate compression strength, the results are shown in Table 1.
The sample that 6) will reach curing age is placed in 60 ℃ of electric drying oven with forced convections and dries 2 hours, sample after drying is placed in to retort furnace to be calcined 2 hours under 1000 ℃ of conditions, with the 300KN pressing machine, sample is carried out the mensuration of ultimate compression strength after naturally cooling, the results are shown in Table 1.
 
Embodiment 5:
1) by pollutents such as the plastics of the first ultrasonic cleaning removal of the waste ceramic reclaimed surface adhesion, paper scrap, metals, reduce its impact on follow-up preparation technology and ground polymers material.
2) ceramic raw material after cleaning is put into to the ball mill ball milling, makes its volume average particle size D[4,3] be down to the 10-50 micron.
3) the sodium hydroxide exciting agent solution that is 10 mol/L with the solid sodium hydroxide compound concentration.Gu by the sodium hydroxide exciting agent solution of preparation and levigate pottery by liquid/than be 0.5 mix and stir after the steel mould of packing into.The mould that reactant is housed is placed on electric vibration table and vibrates 5 minutes to get rid of bubble, then by die sealing.
4) sealed mold is moved in the thermostatic curing case, 60 ℃ of lower maintenance demouldings after 24 hours.Sample after the demoulding continues maintenance 28 days under 60 ℃.
The sample that 5) will arrive curing age is placed in 40 ℃ of electric heating convection oven dries, and obtains the ceramics base polymkeric substance.With the 300KN pressing machine, the maintenance sample of 28 days is carried out the mensuration of ultimate compression strength, the results are shown in Table 1.
The sample that 6) will reach curing age is placed in 60 ℃ of electric drying oven with forced convections and dries 2 hours, sample after drying is placed in to retort furnace to be calcined 2 hours under 1000 ℃ of conditions, with the 300KN pressing machine, sample is carried out the mensuration of ultimate compression strength after naturally cooling, the results are shown in Table 1.
 
Embodiment 6:
1) by pollutents such as the plastics of the first ultrasonic cleaning removal of the waste ceramic reclaimed surface adhesion, paper scrap, metals, reduce its impact on follow-up preparation technology and ground polymers material.
2) ceramic raw material after cleaning is put into to the ball mill ball milling, makes its volume average particle size D[4,3] be down to the 10-50 micron.
3) the potassium hydroxide exciting agent solution that is 10 mol/L with the solid potassium hydroxide compound concentration.Gu by the potassium hydroxide exciting agent solution of preparation and levigate pottery by liquid/than be 0.5 mix and stir after the steel mould of packing into.The mould that reactant is housed is placed on electric vibration table and vibrates 5 minutes to get rid of bubble, then by die sealing.
4) sealed mold is moved in the thermostatic curing case, 60 ℃ of lower maintenance demouldings after 24 hours.Sample after the demoulding continues maintenance 28 days under 60 ℃.
The sample that 5) will arrive curing age is placed in 40 ℃ of electric heating convection oven dries, and obtains the ceramics base polymkeric substance.With the 300KN pressing machine, the maintenance sample of 28 days is carried out the mensuration of ultimate compression strength, the results are shown in Table 1.
The sample that 6) will reach curing age is placed in 60 ℃ of electric drying oven with forced convections and dries 2 hours, sample after drying is placed in to retort furnace to be calcined 2 hours under 1000 ℃ of conditions, with the 300KN pressing machine, sample is carried out the mensuration of ultimate compression strength after naturally cooling, the results are shown in Table 1.
 
Embodiment 7:
1) by pollutents such as the plastics of the first ultrasonic cleaning removal of the waste ceramic reclaimed surface adhesion, paper scrap, metals, reduce its impact on follow-up preparation technology and ground polymers material.
2) ceramic raw material after cleaning is put into to the ball mill ball milling, makes its volume average particle size D[4,3] be down to the 10-50 micron.The complex excitation agent solution that is 10 mol/L with solid sodium hydroxide and potassium hydroxide compound concentration.
3) Gu by the complex excitation agent solution of preparation and levigate pottery by liquid/than be 0.5 mix and stir after the steel mould of packing into.The mould that reactant is housed is placed on electric vibration table and vibrates 5 minutes to get rid of bubble, then by die sealing.
4) sealed mold is moved in the thermostatic curing case, 60 ℃ of lower maintenance demouldings after 24 hours.Sample after the demoulding continues maintenance 28 days under 60 ℃.
The sample that 5) will arrive curing age is placed in 40 ℃ of electric heating convection oven dries, and obtains the ceramics base polymkeric substance.With the 300KN pressing machine, the maintenance sample of 28 days is carried out the mensuration of ultimate compression strength, the results are shown in Table 1.
The sample that 6) will reach curing age is placed in 60 ℃ of electric drying oven with forced convections and dries 2 hours, sample after drying is placed in to retort furnace to be calcined 2 hours under 1000 ℃ of conditions, with the 300KN pressing machine, sample is carried out the mensuration of ultimate compression strength after naturally cooling, the results are shown in Table 1.
 
Table 1 effect parameter
Figure 2013103599157100002DEST_PATH_IMAGE002
The concrete application approach of the present invention is a lot, and the above is only the preferred embodiment of the present invention, should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvement, these improvement also should be considered as protection scope of the present invention.

Claims (4)

1. the preparation method of a refractory ceramics based geopolymer is characterized in that comprising the following steps:
1), by the waste ceramic ultrasonic cleaning of reclaiming, remove the impurity of surface adhesion;
2) ceramic raw material after cleaning is put into to the ball mill ball milling, makes its volume average particle size D[4,3] be down to the 10-50 micron;
3) exciting agent solution is joined in levigate pottery, Gu make the liquid of exciting agent solution and ceramic powder/than being (0.3-0.5): 1;
4) reaction system in step 3) is fully stirred, then reactant is poured in alkali-proof mould, mould is placed in to vibration 3-10 minute on electric vibration table;
5) by the die sealing after vibration treatment, at room temperature or be placed in maintaining box in 20-60 ℃ of lower maintenance demoulding after 24 hours; Sample after the demoulding continues extremely to be scheduled to the length of time in room temperature to 60 ℃ lower maintenance, and 3-28 days, make the ceramics base polymkeric substance after oven dry.
2. the preparation method of refractory ceramics based geopolymer according to claim 1, it is characterized in that: described step 2), exciting agent is the alkali hydroxide soln that concentration is the 5-15 mol/L, the alkali metal silicate solutions that perhaps modulus is 1.0-3.0, or both mixing solutionss.
3. the preparation method of refractory ceramics based geopolymer according to claim 2 is characterized in that: described alkali metal silicate solutions is that alkali metal silicate is received solution.
4. the preparation method of refractory ceramics based geopolymer according to claim 2, is characterized in that: the mixture that described basic metal is sodium, potassium or sodium and potassium.
CN2013103599157A 2013-08-19 2013-08-19 Preparation method of high-temperature-resistant ceramic base polymer Pending CN103435322A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1983003093A1 (en) * 1982-03-08 1983-09-15 Michel Davidovics Method for manufacturing decorated, enamelled ceramic by monofiring, with geopolymer silico-aluminates
CN102584323A (en) * 2012-02-06 2012-07-18 广西大学 Geopolymeric light porous material and preparation method thereof
CN102633449A (en) * 2012-05-03 2012-08-15 南京大学 High-strength glass base polymer and preparation method thereof
WO2012134679A2 (en) * 2011-03-07 2012-10-04 3M Innovative Properties Company Hollow microspheres

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1983003093A1 (en) * 1982-03-08 1983-09-15 Michel Davidovics Method for manufacturing decorated, enamelled ceramic by monofiring, with geopolymer silico-aluminates
WO2012134679A2 (en) * 2011-03-07 2012-10-04 3M Innovative Properties Company Hollow microspheres
CN102584323A (en) * 2012-02-06 2012-07-18 广西大学 Geopolymeric light porous material and preparation method thereof
CN102633449A (en) * 2012-05-03 2012-08-15 南京大学 High-strength glass base polymer and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
王恩等: "工业固体废弃物制备地质聚合物技术的原理与发展", 《矿产综合利用》, no. 02, 30 April 2005 (2005-04-30) *
鲍健强: "《循环经济概论》", 28 February 2009, article "生产与消费之间的社会循环体系" *

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Application publication date: 20131211