CN107601927B - Preparation method of high water ratio phosphorus-containing magnesium oxychloride cement beneficial to improving early strength - Google Patents
Preparation method of high water ratio phosphorus-containing magnesium oxychloride cement beneficial to improving early strength Download PDFInfo
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- CN107601927B CN107601927B CN201710924070.XA CN201710924070A CN107601927B CN 107601927 B CN107601927 B CN 107601927B CN 201710924070 A CN201710924070 A CN 201710924070A CN 107601927 B CN107601927 B CN 107601927B
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- oxychloride cement
- magnesium
- magnesium oxychloride
- phosphorus
- early strength
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- 239000004568 cement Substances 0.000 title claims abstract description 41
- IQYKECCCHDLEPX-UHFFFAOYSA-N chloro hypochlorite;magnesium Chemical compound [Mg].ClOCl IQYKECCCHDLEPX-UHFFFAOYSA-N 0.000 title claims abstract description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910001868 water Inorganic materials 0.000 title claims abstract description 29
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 239000011574 phosphorus Substances 0.000 title claims abstract description 15
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 230000009286 beneficial effect Effects 0.000 title claims description 4
- 239000002002 slurry Substances 0.000 claims abstract description 13
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 60
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 43
- 239000000395 magnesium oxide Substances 0.000 claims description 31
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 30
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 12
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- PLMFYJJFUUUCRZ-UHFFFAOYSA-M decyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCC[N+](C)(C)C PLMFYJJFUUUCRZ-UHFFFAOYSA-M 0.000 claims description 6
- 230000002940 repellent Effects 0.000 claims description 6
- 239000005871 repellent Substances 0.000 claims description 6
- 239000003093 cationic surfactant Substances 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000013053 water resistant agent Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 8
- 238000006703 hydration reaction Methods 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000001723 curing Methods 0.000 description 21
- 239000002699 waste material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000011398 Portland cement Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010881 fly ash Substances 0.000 description 1
- 239000010438 granite Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000010908 plant waste Substances 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention belongs to the field of modification of magnesium oxychloride cement, and particularly relates to a preparation method of high water ratio phosphorus-containing magnesium oxychloride cement, which is favorable for improving early strength, and comprises the following steps: the specific surfactant is added during the preparation of the magnesium oxychloride cement slurry to promote the early hydration reaction of the magnesium oxychloride cement, accelerate the hydration reaction, reduce the setting time and ensure that the prepared magnesium oxychloride cement can obtain higher strength in the early curing period.
Description
Technical Field
The invention belongs to the field of modification of magnesium oxychloride cement, and particularly relates to a preparation method of high water ratio phosphorus-containing magnesium oxychloride cement, which is favorable for improving early strength.
Background
Magnesium oxychloride cement is an air-hardening cement gel material different from the traditional hydraulic portland cement, is widely concerned and applied after being invented by Sorel, a swedish scientist in 1867, has more excellent performances due to the benefit of the magnesium oxychloride cement compared with the traditional portland cement, and has excellent performances of high strength, early strength, corrosion resistance, wear resistance, low heat conductivity coefficient, good fireproof performance and the like; moreover, the magnesium oxychloride cement has important effects on energy conservation and environmental protection, and the magnesium oxychloride cement product does not need wet curing, steaming, drying and other thermal equipment, so that the energy consumption can be effectively reduced. However, some obvious defects of moisture absorption, halogen return, poor water resistance and the like of the magnesium oxychloride cement greatly hinder the further development of the magnesium oxychloride cement, and in order to solve the defects, students at home and abroad make many researches and make great progress.
On the other hand, industrial production in salt lake areas can generate a large amount of by-product magnesium chloride, which is bound to cause resource waste if not effectively utilized, and in addition, many other by-products and wastes of industrial production, such as power plant waste fly ash, engineering waste sawdust, granite waste and the like, can also cause material waste and environmental pollution if not properly treated. In recent research on magnesium oxychloride cement, such wastes are often added to magnesium oxychloride cement, so that the performance of magnesium oxychloride is improved while the industrial wastes are effectively utilized. The proportion of water in the magnesium oxychloride cement is required to be increased while a large amount of industrial waste is mixed so as to obtain better fluidity and operability, but the excessively high proportion of water in the magnesium oxychloride cement can cause the slowing of setting time and the reduction of strength. The existence of the problems can influence the application and development of the magnesium oxychloride cement in practical engineering.
Disclosure of Invention
The invention provides a preparation method of high water ratio phosphorus-containing magnesium oxychloride cement, which is beneficial to improving early strength and aims to solve the problems that in the prior art, magnesium oxychloride cement which is completely different from the traditional portland cement in chemical composition, in particular high water ratio magnesium oxychloride cement slurry designed for doping various additives and magnesium oxychloride cement added with phosphoric acid and soluble phosphate as water resistance have low early strength and slow setting speed: the specific surfactant is added to promote the early hydration reaction of the magnesium oxychloride cement when the magnesium oxychloride cement slurry is prepared, so that the hydration reaction speed is accelerated, the setting time is shortened, the prepared magnesium oxychloride cement can obtain higher strength at the early curing stage,
the method comprises the following specific steps:
(1) adding the phosphorus-containing water-resistant agent into the magnesium chloride solution and fully stirring;
(2) adding a surfactant into the mixture obtained in the step (1) and fully stirring,
wherein the surfactant is a cationic surfactant of CTAB or DTAB;
(3) adding light-burned magnesia into the mixture obtained in the step (2), fully stirring to form magnesium oxychloride cement slurry, pouring the slurry into a mould for curing, demoulding and continuously curing in the air,
in the light-burned magnesia, the mass fraction of magnesia is more than or equal to 50 percent, and the mass fraction of active magnesia is more than or equal to 50 percent,
the molar ratio of the active magnesium oxide to solute magnesium chloride and solvent water in the magnesium chloride solution in the step (1) is 5-8: 1: 13 to 28 of the total weight of the steel,
the phosphorus-containing water repellent agent is phosphoric acid, sodium dihydrogen phosphate or ammonium dihydrogen phosphate, the addition amount is 0.5-1.5 percent of the total mass of the magnesium oxide,
the addition amount of the surfactant is 0.5-2 per mill of the total mass of the magnesium oxide.
Detailed Description
Example 1
In the light-burned MgO powdered material used in this example, the active MgO content was 63% by mass and the total MgO content was 84.27% by mass,
according to the molar ratio of active magnesium oxide, magnesium chloride and water of 6: 1: 16. the dosage of the water repellent agent phosphoric acid is 1 percent of the mass of the magnesium oxide, the dosage of CTAB is 1 per mill of the mass of the magnesium oxide,
(1) dissolving magnesium chloride in water, adding phosphoric acid, mixing to obtain a uniform solution,
(2) adding a surfactant CTAB into the solution obtained in the step (1) and fully stirring,
(3) adding light-burned magnesium oxide into the mixture obtained in the step (2), fully stirring to form magnesium oxychloride cement slurry, pouring the slurry into a stainless steel mould with the thickness of 40mm multiplied by 160mm, curing for 1 day, demoulding, and continuously curing in the air, wherein the compressive strength after curing for 7 days is 50Mpa, the content of free magnesium chloride in the system is obviously reduced in the process, the mass content of free magnesium chloride in the system is 4.01% after curing for 7 days, and the scheme also shows that the hydration reaction speed of magnesium chloride is accelerated.
Example 2
The light-burned magnesia powder used in this example was the same as in example 1,
according to the molar ratio of active magnesium oxide, magnesium chloride and water of 7: 1: 20. the dosage of the water repellent agent phosphoric acid is 1 percent of the mass of the magnesium oxide, the dosage of CTAB is 1 per mill of the mass of the magnesium oxide,
(1) dissolving magnesium chloride in water, adding phosphoric acid, mixing to obtain a uniform solution,
(2) adding a surfactant CTAB into the solution obtained in the step (1) and fully stirring,
(3) adding light-burned magnesium oxide into the mixture obtained in the step (2), fully stirring to form magnesium oxychloride cement slurry, pouring the slurry into a stainless steel mould with the thickness of 40mm multiplied by 160mm, curing for 1 day, demoulding, and continuously curing in the air, wherein the compressive strength after curing for 7 days is 42MPa, the content of free magnesium chloride in the system is obviously reduced in the process, and the mass content of the free magnesium chloride in the system is 5.22% after curing for 7 days.
Example 3
The light-burned magnesia powder used in this example was the same as in example 1,
according to the molar ratio of active magnesium oxide, magnesium chloride and water of 6.5: 1: 20. the dosage of the water repellent agent phosphoric acid is 1 percent of the mass of the magnesium oxide, the dosage of the DTAB is 1.5 thousandth of the mass of the magnesium oxide,
(1) dissolving magnesium chloride in water, adding phosphoric acid, mixing to obtain a uniform solution,
(2) adding a surfactant DTAB into the solution obtained in the step (1) and fully stirring,
(3) adding light-burned magnesium oxide into the mixture obtained in the step (2), fully stirring to form magnesium oxychloride cement slurry, pouring the slurry into a stainless steel mould with the thickness of 40mm multiplied by 160mm, curing for 1 day, demoulding, and continuously curing in the air, wherein the compressive strength after curing for 7 days is 45Mpa, the content of free magnesium chloride in the system is obviously reduced in the process, and the mass content of the free magnesium chloride in the system is 4.98% after curing for 7 days.
Comparative example 1
The magnesium oxychloride cement prepared is the same as in example 1 except that CTAB is not added.
The compressive strength after curing for 7 days is 36Mpa, and the mass content of the free magnesium chloride in the system is 4.73 percent, compared with the example 1, the strength is low, and the content of the free magnesium chloride is high.
Comparative example 2
The magnesium oxychloride cement prepared is the same as that in example 2 except that CTAB is not added.
The compressive strength after curing for 7 days is 30Mpa, and the mass content of the free magnesium chloride in the system is 5.8 percent, compared with the example 2, the strength is low, and the content of the free magnesium chloride is high.
Comparative example 3
The magnesium oxychloride cement prepared was the same as in example 3 except that DTAB was not added.
The compressive strength after curing for 7 days is 30Mpa, and the mass content of the free magnesium chloride in the system is 5.76 percent, compared with the example 3, the strength is low, and the content of the free magnesium chloride is high.
Comparative example 4
The "CTAB" was replaced with equimolar amounts of "sodium hexadecylsulfonate", and the rest was the same as in example 1.
The compressive strength after curing for 7 days is 32Mpa, and the mass content of the free magnesium chloride in the system is 5.31 percent, compared with the example 1, the strength is low, and the content of the free magnesium chloride is high.
Comparative example 5
The "CTAB" was replaced with "P123" of equal mass, and the rest was the same as in example 1.
The compressive strength after curing for 7 days is 34Mpa, and the mass content of the free magnesium chloride in the system is 5.74 percent, compared with the example 1, the strength is low, and the content of the free magnesium chloride is high.
Claims (5)
1. A preparation method of high water ratio phosphorus-containing magnesium oxychloride cement beneficial to improving early strength is characterized by comprising the following steps: the preparation method comprises the specific steps of,
(1) adding the phosphorus-containing water-resistant agent into the magnesium chloride solution and fully stirring;
(2) adding a cationic surfactant CTAB or DTAB into the mixture obtained in the step (1) and fully stirring;
(3) and (3) adding light-burned magnesium oxide into the mixture obtained in the step (2), fully stirring to form magnesium oxychloride cement slurry, pouring the slurry into a mould, curing, demoulding and continuing to cure.
2. The method of claim 1 for preparing a high water ratio phosphorus-containing magnesium oxychloride cement which facilitates early strength improvement, wherein: in the light-burned magnesia, the mass fraction of magnesia is more than or equal to 50 percent, and the mass fraction of active magnesia is more than or equal to 50 percent.
3. The method of claim 2 for preparing a high water ratio phosphorus-containing magnesium oxychloride cement which facilitates an increase in early strength, wherein: the molar ratio of the active magnesium oxide to solute magnesium chloride and solvent water in the magnesium chloride solution in the step (1) is 5-8: 1: 13 to 28.
4. The method of claim 1 for preparing a high water ratio phosphorus-containing magnesium oxychloride cement which facilitates early strength improvement, wherein: the phosphorus-containing water repellent agent is phosphoric acid, sodium dihydrogen phosphate or ammonium dihydrogen phosphate, and the addition amount of the phosphorus-containing water repellent agent is 0.5-1.5 percent of the total mass of the magnesium oxide.
5. The method of claim 2 for preparing a high water ratio phosphorus-containing magnesium oxychloride cement which facilitates an increase in early strength, wherein: the addition amount of CTAB or DTAB of the cationic surfactant is 0.5-2 per mill of the total mass of the magnesium oxide.
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| CN108129044A (en) * | 2018-02-06 | 2018-06-08 | 河北科技大学 | A kind of method for improving magnesia oxychloride cement water resistance |
| CN111646490A (en) * | 2020-05-08 | 2020-09-11 | 中国科学院青海盐湖研究所 | Method for preparing active magnesium oxide from carbide slag and method for preparing magnesium cement |
| CN112794662B (en) * | 2021-01-14 | 2022-04-26 | 常州大学 | Preparation method of hydrophobic magnesium oxychloride cement with high strength and high softening coefficient |
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| CN101104294B (en) * | 2007-07-26 | 2010-12-08 | 武汉工程大学 | Application of magnesia oxychloride cement |
| CN102134746B (en) * | 2011-02-28 | 2012-12-19 | 武汉理工大学 | Preparation method of alkali type magnesium chloride whisker |
| US8603237B2 (en) * | 2012-04-05 | 2013-12-10 | Premier Magnesia, Llc | Method and compositions for improving performance properties of magnesium oxychloride cements |
| CN106517837B (en) * | 2016-10-17 | 2018-10-16 | 常州大学 | A kind of preparation method for the phosphorous magnesium oxychloride cement being conducive to early strength raising |
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