CN104446647A - Spray process based method for improving water resistance of magnesium oxychloride cement products - Google Patents
Spray process based method for improving water resistance of magnesium oxychloride cement products Download PDFInfo
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- CN104446647A CN104446647A CN201410667333.XA CN201410667333A CN104446647A CN 104446647 A CN104446647 A CN 104446647A CN 201410667333 A CN201410667333 A CN 201410667333A CN 104446647 A CN104446647 A CN 104446647A
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- oxychloride cement
- magnesium oxychloride
- solution containing
- phosphate
- containing phosphate
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Abstract
The invention discloses a spray process based method for improving the water resistance of magnesium oxychloride cement products. The method comprises the following steps: S101. preparing a phosphorus-containing solution comprising one or more phosphate ions in monohydrogen phosphate, dihydrogen phosphate and orthophosphate; S102. spraying the phosphorus-containing solution onto the surfaces of the molded and demolded magnesium oxychloride cement products. The method has the beneficial effects that decomposition of hydration products of magnesium oxychloride cement can be delayed, and the water resistance of the magnesium oxychloride cement products can be improved; meanwhile, the setting time of the magnesium oxychloride cement paste can not be lengthened, the cohesion among the hydration products of magnesium oxychloride cement can not be weakened, and the strength of the products can not be affected.
Description
Technical field
The present invention relates to a kind of improvement technique of magnesium oxychloride cement product, particularly relate to a kind of method of the improvement magnesium oxychloride cement product water resisting property based on spraying method.
Background technology
Magnesia oxychloride cement is a kind of special kinds cement, because it is invented, so also known as Sorel cement in 1867 by Frenchman's Sorel (Sorel).Meanwhile, it is main component with magnesium oxide, and people are also called magnesia cement traditionally.In many enterprises, the feature that people are main raw material according to it with magnesium oxide and magnesium chloride two kinds of magnesium compounds, is simply referred to as again two magnesium cement.Usually, people are also accustomed to being referred to as magnesite binding material, magnesia cement, because his main raw material light-burning magnesium powder giobertite calcining forms.
Water resisting property is the principal element affecting magnesia oxychloride cement application.The characteristic of main hydration products easy corrosion in water of magnesia oxychloride cement makes its Application Areas be restricted.Admixture can make the erosion rate of hydrated product reduce, and improves the water resisting property of magnesia oxychloride cement to a certain extent.In actual production, the normal admixture used can be divided into chemical admixture (being mainly phosphoric acid salt and vitriol etc.) and mineral admixture (flyash, slag, silicon ash) etc.The effect that wherein phosphoric acid or phosphoric acid salt improve water resisting property is better than vitriol, is water resistant admixture the most frequently used at present.Usually, the phosphoric acid measured or phosphoric acid salt are joined in bittern (magnesium chloride) solution, after fully dissolving, mix with light-magnesite powder and other raw material, stirring pulping, obtain magnesia oxychloride cement slurry.According to customer need, magnesia oxychloride cement slurry is placed in the magnesite product that mould is prepared into different shapes and purposes.When producing magnesite product, phosphoric acid or phosphatic addition are generally 0.5% ~ 1% (massfraction) of light-magnesite powder.When singly mixing phosphoric acid or the phosphoric acid salt of 1%, the coefficient of softening that magnesium oxychloride cement product soaks at normal temperatures 28 days after maintenance can bring up to more than 0.8.If mix phosphoric acid (or phosphoric acid salt) and mineral admixture in magnesia oxychloride cement again, water resisting property can be more excellent.
When prior art uses phosphoric acid or phosphoric acid salt to improve the water resisting property of magnesia oxychloride cement, can cause extend the time of coagulation of slurry on the one hand, the mechanical properties such as the ultimate compression strength of product can be made on the other hand to reduce.Particularly in the winter of cold, temperature can be reduced to less than 10 DEG C, and consecutive low temperature.When temperature is lower than 10 DEG C, magnesia oxychloride cement time of coagulation of only starching can significant prolongation, and adds phosphoric acid with this understanding again or phosphoric acid salt will extend the time of coagulation of slurry further.Thus, winter, low temperature can cause striking time when producing magnesite product to extend, and even made slurry harden and can not form removal.Thus use phosphoric acid or phosphoric acid salt can reduce production efficiency as the Technology of water repellent agent in the production process in winter at present and even affect normal production.
Summary of the invention
In view of this, the invention provides a kind of method of the improvement magnesium oxychloride cement product water resisting property based on spraying method, the method can delay the decomposition of magnesia oxychloride cement hydrated product, improves the water resisting property of magnesium oxychloride cement product; The time of coagulation of magnesia oxychloride cement slurry can not be extended simultaneously, the cohesive force between magnesia oxychloride cement hydrated product can not be weakened, namely can not affect the intensity of goods.
In order to reach above-mentioned goal of the invention, present invention employs following technical scheme:
Based on a method for the improvement magnesium oxychloride cement product water resisting property of spraying method, comprise step:
S101, prepare solution containing phosphate, in described solution containing phosphate, comprise one or more phosphate anions in phosphoric acid one hydrogen root, dihydrogen phosphate and ortho-phosphoric acid root;
S102, described solution containing phosphate is sprayed at the surface of the magnesium oxychloride cement product after shaping and demoulding.
Preferably, in described solution containing phosphate, the concentration of phosphate anion is 2ug/ml ~ 1000mg/ml.
Preferably, in described solution containing phosphate, the concentration of phosphate anion is 2ug/ml ~ 50mg/ml.
Preferably, in described solution containing phosphate, the concentration of phosphate anion is 50mg/ml ~ 1000mg/ml.
Preferably, in described solution containing phosphate, the concentration of phosphate anion is 250mg/ml ~ 1000mg/ml.
Preferably, in described solution containing phosphate, the concentration of phosphate anion is 50mg/ml ~ 250mg/ml.
Preferably, the phosphorus source of preparing solution containing phosphate be selected from phosphoric acid, monohydric phosphate, dihydrogen phosphate, orthophosphoric acid salt one or more.
Preferably, by spraying equipment, described solution containing phosphate is sprayed on the surface of the magnesium oxychloride cement product after shaping and demoulding.
Preferably, by handwork, described solution containing phosphate is applied in the surface of the magnesium oxychloride cement product after shaping and demoulding.
Compared with prior art, the use spraying method provided in the embodiment of the present invention will spray to the surface of magnesium oxychloride cement product containing P solution (phosphoric acid or phosphoric acid salt), make phosphate radical form adsorption layer on the top layer (comprising article outer surface and inner bore surface) of hydrated product, so with the Mg on hydrated product surface
2+form Mg-P coordinate bond, reduce or eliminate hydrated product surface Mg
2+with extraneous H
2o contacts and forms the active site position of Mg-O key, thus reach delay hydrated product decompose, improve the object of magnesium oxychloride cement product water resisting property.
In addition, in the method, solution containing phosphate is ability and the surface interaction of hydrated product after magnesia oxychloride cement shaping and demoulding, thus can not affect the hydration process of magnesia oxychloride cement, can not extend the time of coagulation of slurry; Further, be not dispersed in magnesia oxychloride cement slurry containing P solution, thus can not be mingled with or be adsorbed between hydrated product yet, the cohesive force between hydrated product can not be weakened, namely can not affect the intensity of goods.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the method for the improvement magnesium oxychloride cement product water resisting property based on spraying method that the embodiment of the present invention provides.
Embodiment
Below in conjunction with accompanying drawing, by embodiment, the present invention will be further described.
Consult Fig. 1, the method for the improvement magnesium oxychloride cement product water resisting property based on spraying method provided in this embodiment comprises step:
S101, prepare solution containing phosphate, in described solution containing phosphate, comprise one or more phosphate anions in phosphoric acid one hydrogen root, dihydrogen phosphate and ortho-phosphoric acid root.
S102, described solution containing phosphate is sprayed at the surface of the magnesium oxychloride cement product after shaping and demoulding.
Wherein, the phosphorus source of preparing solution containing phosphate be selected from phosphoric acid, monohydric phosphate, dihydrogen phosphate, orthophosphoric acid salt one or more.
Wherein, by spraying equipment, described solution containing phosphate can be sprayed on the surface of the magnesium oxychloride cement product after shaping and demoulding; Also by handwork, described solution containing phosphate can be applied in the surface of the magnesium oxychloride cement product after shaping and demoulding.
After improving according to the water resisting property of above method to magnesium oxychloride cement product, the coefficient of softening of magnesium oxychloride cement product increases substantially, and even can improve more than 100%.
Embodiment 1
(1) solution containing phosphate is prepared.The phosphorus source of preparing solution containing phosphate in the present embodiment is phosphoric acid, prepares the solution containing phosphate that phosphorus acid ion concentration is 2ug/ml.
(2) magnesia oxychloride cement aquation is shaped to the product with concrete shape.Wherein the proportioning raw materials of magnesia oxychloride cement is active MgO: MgCl
2: H
2o=7:1:15.
(3) after magnesium oxychloride cement product shaping and demoulding, be the solution containing phosphate of 2ug/ml by phosphorus acid ion concentration, be sprayed on the surface of magnesium oxychloride cement product by spraying equipment, dry.
(4), when the goods dried in step (3) being soaked 24 in the water-bath of 65 DEG C, recording coefficient of softening is 0.46.As a comparison, under similarity condition, the coefficient of softening without the goods of spraying solution containing phosphate is 0.32.Thus, improve 43.8% according to the coefficient of softening of magnesium oxychloride cement product after the present embodiment spraying solution containing phosphate.
Embodiment 2
(1) solution containing phosphate is prepared.The phosphorus source of preparing solution containing phosphate in the present embodiment is potassium primary phosphate, prepares the solution containing phosphate that phosphorus acid ion concentration is 50ug/ml.
(2) magnesia oxychloride cement aquation is shaped to the product with concrete shape.Wherein the proportioning raw materials of magnesia oxychloride cement is active MgO: MgCl
2: H
2o=7:1:15.
(3) after magnesium oxychloride cement product shaping and demoulding, be the solution containing phosphate of 50ug/ml by phosphorus acid ion concentration, be applied in the surface of magnesium oxychloride cement product by handwork, dry.
(4), when the goods dried in step (3) being soaked 24 in the water-bath of 65 DEG C, recording coefficient of softening is 0.60.With under similarity condition without compared with the goods spraying solution containing phosphate, improve 87.5% according to the coefficient of softening of magnesium oxychloride cement product after the present embodiment spraying solution containing phosphate.
Embodiment 3
(1) solution containing phosphate is prepared.The phosphorus source of preparing solution containing phosphate in the present embodiment is dipotassium hydrogen phosphate, prepares the solution containing phosphate that phosphorus acid ion concentration is 50mg/ml.
(2) magnesia oxychloride cement aquation is shaped to the product with concrete shape.Wherein the proportioning raw materials of magnesia oxychloride cement is active MgO: MgCl
2: H
2o=7:1:15.
(3) after magnesium oxychloride cement product shaping and demoulding, be the solution containing phosphate of 50mg/ml by phosphorus acid ion concentration, be sprayed on the surface of magnesium oxychloride cement product by spraying equipment, dry.
(4), when the goods dried in step (3) being soaked 24 in the water-bath of 65 DEG C, recording coefficient of softening is 0.66.With under similarity condition without compared with the goods spraying solution containing phosphate, improve 106.3% according to the coefficient of softening of magnesium oxychloride cement product after the present embodiment spraying solution containing phosphate.
Embodiment 4
(1) solution containing phosphate is prepared.The phosphorus source of preparing solution containing phosphate in the present embodiment is Tripotassium phosphate, prepares the solution containing phosphate that phosphorus acid ion concentration is 1000mg/ml.
(2) magnesia oxychloride cement aquation is shaped to the product with concrete shape.Wherein the proportioning raw materials of magnesia oxychloride cement is active MgO: MgCl
2: H
2o=7:1:15.
(3) after magnesium oxychloride cement product shaping and demoulding, be the solution containing phosphate of 1000mg/ml by phosphorus acid ion concentration, be sprayed on the surface of magnesium oxychloride cement product by spraying equipment, dry.
(4), when the goods dried in step (3) being soaked 24 in the water-bath of 65 DEG C, recording coefficient of softening is 0.63.With under similarity condition without compared with the goods spraying solution containing phosphate, improve 96.9% according to the coefficient of softening of magnesium oxychloride cement product after the present embodiment spraying solution containing phosphate.
Embodiment 5
(1) solution containing phosphate is prepared.The phosphorus source of preparing solution containing phosphate in the present embodiment is the mixture of potassium primary phosphate and dipotassium hydrogen phosphate (can mix according to arbitrary proportion), prepares the solution containing phosphate that phosphorus acid ion concentration is 250mg/ml.
(2) magnesia oxychloride cement aquation is shaped to the product with concrete shape.Wherein the proportioning raw materials of magnesia oxychloride cement is active MgO: MgCl
2: H
2o=7:1:15.
(3) after magnesium oxychloride cement product shaping and demoulding, be the solution containing phosphate of 250mg/ml by phosphorus acid ion concentration, be sprayed on the surface of magnesium oxychloride cement product by spraying equipment, dry.
(4), when the goods dried in step (3) being soaked 24 in the water-bath of 65 DEG C, recording coefficient of softening is 0.52.With under similarity condition without compared with the goods spraying solution containing phosphate, improve 62.5% according to the coefficient of softening of magnesium oxychloride cement product after the present embodiment spraying solution containing phosphate.
It should be noted that, in above embodiment, the proportioning raw materials of magnesia oxychloride cement is active MgO: MgCl
2: H
2o=7:1:15, only illustrates at this, should not be construed as limitation of the invention.Method provided by the invention is also used in the magnesia oxychloride cement of other proportioning raw materials.
In sum, compared with prior art, the use spraying method provided in the embodiment of the present invention will spray to the surface of magnesium oxychloride cement product containing P solution (phosphoric acid or phosphoric acid salt), make phosphate radical form adsorption layer on the top layer (comprising article outer surface and inner bore surface) of hydrated product, so with the Mg on hydrated product surface
2+form Mg-P coordinate bond, reduce or eliminate hydrated product surface Mg
2+ion and extraneous H
2o contacts and forms the active site position of Mg-O key, thus reach delay hydrated product decompose, improve the object of magnesium oxychloride cement product water resisting property.
In addition, in the method, solution containing phosphate is ability and the surface interaction of hydrated product after magnesia oxychloride cement shaping and demoulding, thus can not affect the hydration process of magnesia oxychloride cement, can not extend the time of coagulation of slurry; Further, be not dispersed in magnesia oxychloride cement slurry containing P solution, thus can not be mixed between hydrated product yet, the cohesive force between hydrated product can not be weakened, namely can not affect the intensity of goods.
The above is only the embodiment of the application; it should be pointed out that for those skilled in the art, under the prerequisite not departing from the application's principle; can also make some improvements and modifications, these improvements and modifications also should be considered as the protection domain of the application.
Claims (9)
1., based on a method for the improvement magnesium oxychloride cement product water resisting property of spraying method, it is characterized in that, comprise step:
S101, prepare solution containing phosphate, in described solution containing phosphate, comprise one or more phosphate anions in phosphoric acid one hydrogen root, dihydrogen phosphate and ortho-phosphoric acid root;
S102, described solution containing phosphate is sprayed at the surface of the magnesium oxychloride cement product after shaping and demoulding.
2. the method for the improvement magnesium oxychloride cement product water resisting property based on spraying method according to claim 1, is characterized in that, in described solution containing phosphate, the concentration of phosphate anion is 2ug/ml ~ 1000mg/ml.
3. the method for the improvement magnesium oxychloride cement product water resisting property based on spraying method according to claim 1, is characterized in that, in described solution containing phosphate, the concentration of phosphate anion is 2ug/ml ~ 50mg/ml.
4. the method for the improvement magnesium oxychloride cement product water resisting property based on spraying method according to claim 1, is characterized in that, in described solution containing phosphate, the concentration of phosphate anion is 50mg/ml ~ 1000mg/ml.
5. the method for the improvement magnesium oxychloride cement product water resisting property based on spraying method according to claim 1, is characterized in that, in described solution containing phosphate, the concentration of phosphate anion is 250mg/ml ~ 1000mg/ml.
6. the method for the improvement magnesium oxychloride cement product water resisting property based on spraying method according to claim 1, is characterized in that, in described solution containing phosphate, the concentration of phosphate anion is 50mg/ml ~ 250mg/ml.
7., according to the method for the arbitrary described improvement magnesium oxychloride cement product water resisting property based on spraying method of claim 1-6, it is characterized in that, the phosphorus source of preparing solution containing phosphate be selected from phosphoric acid, monohydric phosphate, dihydrogen phosphate, orthophosphoric acid salt one or more.
8. the method for the improvement magnesium oxychloride cement product water resisting property based on spraying method according to claim 1, be is characterized in that, by spraying equipment, described solution containing phosphate is sprayed on the surface of the magnesium oxychloride cement product after shaping and demoulding.
9. the method for the improvement magnesium oxychloride cement product water resisting property based on spraying method according to claim 1, be is characterized in that, by handwork, described solution containing phosphate is applied in the surface of the magnesium oxychloride cement product after shaping and demoulding.
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Citations (7)
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|---|---|---|---|---|
| US4352694A (en) * | 1980-07-18 | 1982-10-05 | Norcem A.S. | Process of producing sorel cement |
| CN1034912A (en) * | 1988-02-10 | 1989-08-23 | 湖南大学 | Magnesia oxychloride cement that has excellent water-resistance and magnesite concrete |
| CN1070627A (en) * | 1991-09-16 | 1993-04-07 | 山东省新材料研究所 | Modified magnesium oxychloride cement and goods thereof |
| CN1225344A (en) * | 1998-11-20 | 1999-08-11 | 中国科学院上海硅酸盐研究所 | Inorganic and flame-retardant type composite slab and method for mfg. same |
| CN101007725A (en) * | 2007-01-29 | 2007-08-01 | 王惠陵 | Water-resistant chlorine oxygen magnesium silicon series composite material and its preparing process |
| EP1923374A1 (en) * | 2006-11-16 | 2008-05-21 | Lafarge | Process for treating concrete |
| CN102757256A (en) * | 2012-07-18 | 2012-10-31 | 公安部四川消防研究所 | Incombustible organic/inorganic porous waterproof thermal-insulation composite material and preparation method thereof |
-
2014
- 2014-11-20 CN CN201410667333.XA patent/CN104446647B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4352694A (en) * | 1980-07-18 | 1982-10-05 | Norcem A.S. | Process of producing sorel cement |
| CN1034912A (en) * | 1988-02-10 | 1989-08-23 | 湖南大学 | Magnesia oxychloride cement that has excellent water-resistance and magnesite concrete |
| CN1070627A (en) * | 1991-09-16 | 1993-04-07 | 山东省新材料研究所 | Modified magnesium oxychloride cement and goods thereof |
| CN1225344A (en) * | 1998-11-20 | 1999-08-11 | 中国科学院上海硅酸盐研究所 | Inorganic and flame-retardant type composite slab and method for mfg. same |
| EP1923374A1 (en) * | 2006-11-16 | 2008-05-21 | Lafarge | Process for treating concrete |
| CN101007725A (en) * | 2007-01-29 | 2007-08-01 | 王惠陵 | Water-resistant chlorine oxygen magnesium silicon series composite material and its preparing process |
| CN102757256A (en) * | 2012-07-18 | 2012-10-31 | 公安部四川消防研究所 | Incombustible organic/inorganic porous waterproof thermal-insulation composite material and preparation method thereof |
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