CN103086688B - Method for preparing artificial stone by modifying magnesium oxychloride cement with metakaolin-aluminum dihydrogen phosphate composite modifier - Google Patents
Method for preparing artificial stone by modifying magnesium oxychloride cement with metakaolin-aluminum dihydrogen phosphate composite modifier Download PDFInfo
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- CN103086688B CN103086688B CN201310025455.4A CN201310025455A CN103086688B CN 103086688 B CN103086688 B CN 103086688B CN 201310025455 A CN201310025455 A CN 201310025455A CN 103086688 B CN103086688 B CN 103086688B
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- oxychloride cement
- metakaolin
- magnesia oxychloride
- dihydrogen phosphate
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Abstract
The invention discloses a method for preparing artificial stone by modifying magnesium oxychloride cement with a metakaolin-aluminum dihydrogen phosphate composite modifier. The method comprises the following steps: mixing MgO and an MgCl2 solution with the Baume degree of 25.0-32.0 degrees Be according to the proportion of 1.0: 0.8-1.0: 1.2 to prepare magnesium oxychloride cement slurry; and doping 1.0%-15.0% of the metakaolin and 1.0%-10.0% of the aluminum dihydrogen phosphate into the magnesium oxychloride cement slurry as a composite modifier to prepare compound modified magnesium oxychloride cement slurry. In percentage by weight, 0.1%-80.0% of marble waste stone dust or granite waste stone dust aggregate and 99.9%-20.0% of the compound modified magnesium oxychloride cement slurry are mixed and uniformly stirred, then the mixture is injected into a mold so as to mold and prepare the magnesium oxychloride-based artificial stone, and the magnesium oxychloride-based artificial stone has the flexural strength softening coefficient being above 0.88 and high water resistance.
Description
Technical field
The present invention relates to a kind of magnesia oxychloride cement based artificial stone, particularly relate to a kind of metakaolin and aluminium dihydrogen phosphate of utilizing and improve as composite modifier the method that magnesia oxychloride cement is prepared rostone, rostone prepared by the method, has effectively improved the water tolerance of rostone.
Background technology
Magnesia oxychloride cement has that fast solidifying, intensity are high, High anti bending strength, easily and the advantage such as organism combination, and goods heat insulation property, flame retardant resistance, processability etc. are better, are a kind of high performance inorganic coagulation materials.But the poor water resistance of magnesia oxychloride cement own, badly influences the life cycle of magnesia oxychloride cement based artificial stone, has also hindered the widespread use of magnesia oxychloride cement.
Some Chinese scholars are also being done a little research aspect improvement magnesia oxychloride cement.Dehua Deng etc. are with the research of phosphoric acid, soluble phosphate modified magnesium oxychloride cement water tolerance, folding strength coefficient of softening can reach 0.75 (The mechanism for soluble phosphates to improve the water resistance of magnesium oxychloride cement[J] .Cement and Concrete Research, 2003 (33): 1311-1317).Jianquan Li and BA Hengjing etc. also have similar research (BA Hengjing, GUAN Hui.Influence of MgO/MgCl with phosphoric acid salt modified magnesium oxychloride cement water tolerance
2molar Ratio on Phase Stability of Magnesium Oxychloride Cement[J] .Journal of Wuhan University of Technolotgy-Mater.2009 (12): 476-481; Jianquan Li, Guozhong Li, Yanzhen Yu.The influence of compound additive on magnesium oxychloridecement/urban refuse floor tile[J] .Construction and Building Materials, 2008 (22): 521-525) in addition, also have research with flyash modified magnesia oxychloride cement water tolerance (Yan Zhen first magnesium modified cement and production of articles practical technique [M]. Beijing: Chemical Industry Press, 2006:142-233).Though above-mentioned method of modifying can improve the water tolerance of magnesia oxychloride cement to a certain extent, folding strength coefficient of softening is the highest only reaches 0.75 for it, still fails the fine needs that meet practical application.
Summary of the invention
The object of the present invention is to provide a kind of metakaolin and aluminium dihydrogen phosphate composite modifier modified magnesium oxychloride cement water tolerance utilized, itself and waste material of stone are prepared to the method that folding strength coefficient of softening reaches more than 0.88 enhanced water resistance magnesia oxychloride cement based artificial stone.
Present method will be with metakaolin and the composite modified magnesia oxychloride cement of aluminium dihydrogen phosphate, utilize the acting in conjunction of metakaolin and aluminium dihydrogen phosphate, make the hydrate of magnesia oxychloride cement can be in water stable existence more, thereby improved magnesia oxychloride cement and magnesia oxychloride cement based artificial stone water tolerance, its folding strength coefficient of softening is reached more than 0.88.In magnesia oxychloride cement, add after metakaolin and aluminium dihydrogen phosphate composite modifier, can effectively suppress Mg in magnesia oxychloride cement
2+, Cl
-stripping in water, after immersion, magnesia oxychloride cement hydrate still can keep former 518 crystal phase structures to exist, hardening of cement body structure is energy stable existence in water, thereby the water tolerance of the chlorine oxygen magnesium based artificial stone after modification is largely increased, and folding strength coefficient of softening reaches more than 0.88.The present invention utilizes composite modifier to improve magnesia oxychloride cement water tolerance; and utilize waste material of stone to prepare magnesia oxychloride cement based artificial stone, and both improved the work-ing life of chlorine oxygen magnesium based artificial stone, make full use of again waste material of stone; protection of the environment, the purposes of expansion magnesia oxychloride cement and goods thereof.
The object of the invention is achieved through the following technical solutions:
A method of preparing rostone with metakaolin and the composite modified magnesia oxychloride cement of aluminium dihydrogen phosphate, comprises the steps and processing condition:
(1) by MgO and degree Beaume, be the MgCl of 25～32 ° of B é
2solution, is mixed with magnesia oxychloride cement slurry by 1: 0.8～1: 1.2 part by weight; The weight of magnesia oxychloride cement slurry of take is benchmark, by weight percentage, then using 1%～15% metakaolin and 1%～10% aluminium dihydrogen phosphate as composite modifier, is incorporated into and in magnesia oxychloride cement slurry, prepares composite modified magnesia oxychloride cement slurry;
(2) take the gross weight of raw material is benchmark, by weight percentage, by casting after composite modified magnesia oxychloride cement slurry mixing and stirring described in 10%～70.0% stone grain or polishing stone flour and 90%～30.0%, make rostone, natural curing 28 days; Described stone grain diameter is 5mm～20mm, and by weight percentage, described stone grain or polishing stone flour water ratio are all lower than 20%.
For further realizing the object of the invention, described metakaolin is preferably kaolin and within 0.5-2.5 hour, makes through 600 ℃～900 ℃ calcinings.Described stone grain or polishing stone flour derive from marble or grouan.Described polishing stone flour is the waste stone dust that processing of stone polishing process produces.The weight of magnesia oxychloride cement slurry of take is benchmark, and by weight percentage, the consumption of described metakaolin is preferably 5%～10%.
Tool of the present invention has the following advantages and beneficial effect:
(1) the present invention is usingd metakaolin and aluminium dihydrogen phosphate as composite modifier, makes magnesia oxychloride cement can effectively suppress Mg in water
2+, Cl
-stripping, after immersion, hydrate can be good at keeping 518 crystal phase structures, hardening of cement body structure stable existence in water, making has good water tolerance after the immersion of magnesia oxychloride cement based artificial stone.
(2) waste material that the present invention has utilized stone material cutting, polishing to produce is prepared magnesia oxychloride cement based artificial stone, is conducive to environment protection, turns waste into wealth;
(3) utilize composite modifier modification, can effectively improve the water tolerance of magnesia oxychloride cement, make magnesia oxychloride cement application more extensive.Preparedly obtain high magnesia oxychloride cement based artificial stone and there is better water tolerance, extended work-ing life;
Accompanying drawing explanation
Fig. 1 is the front modified magnesium oxychloride cement hydrate X ray powder crystal diffraction spectrogram of immersion;
Fig. 2 is 28 days post-modification magnesia oxychloride cement hydrate X ray powder crystal diffraction spectrograms of immersion.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the scope of protection of present invention is not limited to the scope of embodiment statement.
Embodiment 1
A method of preparing rostone with metakaolin and the composite modified magnesia oxychloride cement of aluminium dihydrogen phosphate, comprises the steps and processing condition:
(1) kaolin is calcined at 600 ℃ and within 2.5 hours, made metakaolin.
(2) by MgO and degree Beaume, be the MgCl of 28 ° of B é
2solution, is mixed with magnesia oxychloride cement slurry by 1: 1.2 part by weight.The weight of magnesia oxychloride cement slurry of take is benchmark, by weight percentage, then using 10% metakaolin and 5% aluminium dihydrogen phosphate as composite modifier, is incorporated into and in magnesia oxychloride cement slurry, prepares composite modified magnesia oxychloride cement slurry.
(3) take the gross weight of all raw materials is benchmark, by weight percentage, after 10% marble barren rock grain aggregate (particle diameter is 5mm～20mm) and 90% above-mentioned composite modified magnesia oxychloride cement slurry are mixed in proportion and are stirred, casting prepares rostone, natural curing 28 days, detecting its folding strength is 29.6MPa.
(4) natural curing after 28 days prepared rostone put into tap water maintenance 28 days again, after testing, its folding strength is 28.1MPa, before and after curing in water, to be coefficient of softening be 0.95 to folding strength ratio.
The present embodiment adds after metakaolin and aluminium dihydrogen phosphate composite modifier in magnesia oxychloride cement, can effectively suppress Mg in magnesia oxychloride cement
2+, Cl
-stripping in water, after immersion, magnesia oxychloride cement hydrate still can keep 518 crystal phase structures to exist.Fig. 1 is the front modified magnesium oxychloride cement hydrate X ray powder crystal diffraction spectrogram of immersion; Fig. 2 is 28 days post-modification magnesia oxychloride cement hydrate X ray powder crystal diffraction spectrograms of immersion.Before and after soaking as seen from two figure, modified magnesium oxychloride cement hydrate all be take 518 crystal phase structures as principal crystalline phase.Explanation is after modification, and the crystalline phase of magnesia oxychloride cement hydrate is energy stable existence in water, thereby the water tolerance of the chlorine oxygen magnesium based artificial stone after modification is largely increased, and coefficient of softening reaches 0.95.Coefficient of softening is folding strength ratio before and after curing in water, and coefficient of softening is higher shows that product Strength Changes after curing in water is less, and water tolerance is higher.The coefficient of softening of the magnesia oxychloride cement based artificial stone that the present invention is prepared is reported higher than research at present, is illustrated that its water tolerance is better.Owing to being only processing parameter difference in the reasonable scope, below in embodiment concrete coefficient of softening and the present embodiment of rostone also very approaching, before and after immersion, modified magnesium oxychloride cement hydrate X ray powder crystal diffraction spectrogram and Fig. 1 are basic identical.
Embodiment 2
A method of preparing rostone with metakaolin and the composite modified magnesia oxychloride cement of aluminium dihydrogen phosphate, comprises the steps and processing condition:
(1) kaolin is calcined at 750 ℃ and within 2.0 hours, made metakaolin.
(2) by MgO and degree Beaume, be the MgCl of 25 ° of B é
2solution, is mixed with magnesia oxychloride cement slurry in 1: 0.8 ratio.The weight of magnesia oxychloride cement slurry of take is benchmark, by weight percentage, then using 1% metakaolin and 1% aluminium dihydrogen phosphate as composite modifier, is incorporated into and in magnesia oxychloride cement slurry, prepares composite modified magnesia oxychloride cement slurry.
(3) take the weight of all raw materials is benchmark, by weight percentage, after 40.0% grouan waste stone dust (moisture is 15%) and 60.0% above-mentioned composite modified magnesia oxychloride cement slurry are mixed in proportion and are stirred, casting prepares rostone, natural curing 28 days, detecting its folding strength is 25.4MPa.
(4) natural curing after 28 days prepared rostone put into tap water maintenance 28 days again, detecting its folding strength is 23.1MPa, before and after curing in water, to be coefficient of softening be 0.91 to folding strength ratio.
Embodiment 3
A method of preparing rostone with metakaolin and the composite modified magnesia oxychloride cement of aluminium dihydrogen phosphate, comprises the steps and processing condition:
(1) kaolin is calcined at 900 ℃ and within 0.5 hour, made metakaolin.
(2) by MgO and degree Beaume, be the MgCl of 32 ° of B é
2solution, is mixed with magnesia oxychloride cement slurry in 1: 1.2 ratio.The weight of magnesia oxychloride cement slurry of take is benchmark, by weight percentage, then using 15% metakaolin and 10% aluminium dihydrogen phosphate as composite modifier, is incorporated into and in magnesia oxychloride cement slurry, prepares composite modified magnesia oxychloride cement slurry.
(3) take the weight of all raw materials is benchmark, by weight percentage, after 70.0% grouan barren rock grain aggregate (particle diameter is 5～20mm) and 30.0% above-mentioned composite modified magnesia oxychloride cement slurry are mixed in proportion and are stirred, casting prepares rostone, natural curing 28 days, detecting its folding strength is 10.2MPa.
(4) natural curing after 28 days prepared rostone put into tap water maintenance 28 days again, detecting its folding strength is 9.0MPa, before and after curing in water, to be coefficient of softening be 0.88 to folding strength ratio.
Embodiment 4
A method of preparing rostone with metakaolin and the composite modified magnesia oxychloride cement of aluminium dihydrogen phosphate, comprises the steps and processing condition:
(1) kaolin is calcined at 800 ℃ and within 1.5 hours, made metakaolin.
(2) by MgO and degree Beaume, be the MgCl of 30 ° of B é
2solution, is mixed with magnesia oxychloride cement slurry by 1: 1.1 part by weight.The weight of magnesia oxychloride cement slurry of take is benchmark, by weight percentage, then using 10% metakaolin and 8% aluminium dihydrogen phosphate as composite modifier, is incorporated into and in magnesia oxychloride cement slurry, prepares composite modified magnesia oxychloride cement slurry.
(3) take the weight of all raw materials is benchmark, by weight percentage, after 50.0% marble waste stone dust (moisture is 10%) and 50.0% above-mentioned composite modified magnesia oxychloride cement slurry are mixed in proportion and are stirred, casting prepares rostone, natural curing 28 days, detecting its folding strength is 15.8MPa.
(4) natural curing after 28 days prepared rostone put into tap water maintenance 28 days again, detecting its folding strength is 14.1MPa, before and after curing in water, to be coefficient of softening be 0.89 to folding strength ratio.
Claims (4)
1. with metakaolin and the composite modified magnesia oxychloride cement of aluminium dihydrogen phosphate, prepare a method for rostone, it is characterized in that comprising the steps and processing condition:
(1) by MgO and degree Beaume, be the MgCl of 25～32 ° of B é
2solution, is mixed with magnesia oxychloride cement slurry by 1:0.8～1:1.2 part by weight; The weight of magnesia oxychloride cement slurry of take is benchmark, by weight percentage, then using 1%～15% metakaolin and 1%～10% aluminium dihydrogen phosphate as composite modifier, is incorporated into and in magnesia oxychloride cement slurry, prepares composite modified magnesia oxychloride cement slurry; Described metakaolin be kaolin through 600 ℃～900 ℃ calcinings 0.5 ?within 2.5 hours, make;
(2) take the gross weight of raw material is benchmark, by weight percentage, by casting after composite modified magnesia oxychloride cement slurry mixing and stirring described in 10%～70.0% stone grain or polishing stone flour and 90%～30.0%, make rostone, natural curing 28 days; Described stone grain diameter is 5mm～20mm, and by weight percentage, described stone grain or polishing stone flour water ratio are all lower than 20%.
2. the method for preparing rostone with metakaolin and the composite modified magnesia oxychloride cement of aluminium dihydrogen phosphate according to claim 1, is characterized in that: described stone grain or polishing stone flour derive from marble or grouan.
3. the method for preparing rostone with metakaolin and the composite modified magnesia oxychloride cement of aluminium dihydrogen phosphate according to claim 1 and 2, is characterized in that: described polishing stone flour is the waste stone dust that processing of stone polishing process produces.
4. the method for preparing rostone with metakaolin and the composite modified magnesia oxychloride cement of aluminium dihydrogen phosphate according to claim 1, it is characterized in that: the weight of magnesia oxychloride cement slurry of take is benchmark, by weight percentage, the consumption of described metakaolin is 5%～10%.
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