CN117447115A - Composite retarder and application thereof in magnesium phosphate cement-based material - Google Patents
Composite retarder and application thereof in magnesium phosphate cement-based material Download PDFInfo
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- CN117447115A CN117447115A CN202311003535.XA CN202311003535A CN117447115A CN 117447115 A CN117447115 A CN 117447115A CN 202311003535 A CN202311003535 A CN 202311003535A CN 117447115 A CN117447115 A CN 117447115A
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- China
- Prior art keywords
- retarder
- phosphate cement
- magnesium phosphate
- zinc acetate
- magnesium
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- 239000004137 magnesium phosphate Substances 0.000 title claims abstract description 179
- 229960002261 magnesium phosphate Drugs 0.000 title claims abstract description 179
- 229910000157 magnesium phosphate Inorganic materials 0.000 title claims abstract description 179
- 235000010994 magnesium phosphates Nutrition 0.000 title claims abstract description 179
- GVALZJMUIHGIMD-UHFFFAOYSA-H magnesium phosphate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GVALZJMUIHGIMD-UHFFFAOYSA-H 0.000 title claims abstract description 177
- 239000004568 cement Substances 0.000 title claims abstract description 175
- 239000002131 composite material Substances 0.000 title claims abstract description 161
- 239000000463 material Substances 0.000 title claims abstract description 104
- 238000003756 stirring Methods 0.000 claims abstract description 81
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 73
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000004246 zinc acetate Substances 0.000 claims abstract description 56
- 238000002156 mixing Methods 0.000 claims abstract description 50
- 239000000843 powder Substances 0.000 claims abstract description 32
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000008247 solid mixture Substances 0.000 claims abstract description 8
- 238000007580 dry-mixing Methods 0.000 claims abstract description 5
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 120
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 111
- 229910021538 borax Inorganic materials 0.000 claims description 109
- 239000004328 sodium tetraborate Substances 0.000 claims description 109
- 239000000395 magnesium oxide Substances 0.000 claims description 107
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 104
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 95
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 95
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 91
- 229960000314 zinc acetate Drugs 0.000 claims description 54
- 238000002360 preparation method Methods 0.000 claims description 48
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 34
- 239000004327 boric acid Substances 0.000 claims description 34
- 150000001875 compounds Chemical class 0.000 claims description 30
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000004576 sand Substances 0.000 claims description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 13
- 229910019142 PO4 Inorganic materials 0.000 claims description 11
- 239000010452 phosphate Substances 0.000 claims description 11
- 239000010456 wollastonite Substances 0.000 claims description 10
- 229910052882 wollastonite Inorganic materials 0.000 claims description 10
- 239000010881 fly ash Substances 0.000 claims description 9
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 6
- 239000012767 functional filler Substances 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 238000004146 energy storage Methods 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 239000011232 storage material Substances 0.000 claims description 3
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical group [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 claims description 3
- 230000000996 additive effect Effects 0.000 claims description 2
- 229940057499 anhydrous zinc acetate Drugs 0.000 claims description 2
- 239000002956 ash Substances 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 239000010802 sludge Substances 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
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims 1
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims 1
- 235000019838 diammonium phosphate Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 43
- 230000000979 retarding effect Effects 0.000 abstract description 26
- 239000007787 solid Substances 0.000 abstract description 24
- 239000000203 mixture Substances 0.000 abstract description 14
- 235000012245 magnesium oxide Nutrition 0.000 description 105
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical group OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 100
- 230000000052 comparative effect Effects 0.000 description 43
- 238000005303 weighing Methods 0.000 description 25
- 230000003321 amplification Effects 0.000 description 21
- 238000003199 nucleic acid amplification method Methods 0.000 description 21
- 238000012360 testing method Methods 0.000 description 12
- CDMADVZSLOHIFP-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane;decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 CDMADVZSLOHIFP-UHFFFAOYSA-N 0.000 description 11
- 239000011083 cement mortar Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000004570 mortar (masonry) Substances 0.000 description 5
- 231100000989 no adverse effect Toxicity 0.000 description 4
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 4
- LWNCNSOPVUCKJL-UHFFFAOYSA-N [Mg].[P] Chemical compound [Mg].[P] LWNCNSOPVUCKJL-UHFFFAOYSA-N 0.000 description 3
- 239000004567 concrete Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000012782 phase change material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- 206010003591 Ataxia Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000001804 chlorine Chemical class 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000013521 mastic Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- DGVVJWXRCWCCOD-UHFFFAOYSA-N naphthalene;hydrate Chemical compound O.C1=CC=CC2=CC=CC=C21 DGVVJWXRCWCCOD-UHFFFAOYSA-N 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920005646 polycarboxylate Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 239000000941 radioactive substance Substances 0.000 description 1
- 229910052704 radon Inorganic materials 0.000 description 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010455 vermiculite Substances 0.000 description 1
- 229910052902 vermiculite Inorganic materials 0.000 description 1
- 235000019354 vermiculite Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- HRSADIZPZPRZEI-UHFFFAOYSA-L zinc;diacetate;hydrate Chemical class O.[Zn+2].CC([O-])=O.CC([O-])=O HRSADIZPZPRZEI-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
- C04B28/344—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders the phosphate binder being present in the starting composition solely as one or more phosphates
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to a composite retarder and application thereof in a magnesium phosphate cement-based material, and the application method comprises the following three methods: 1) Dry-mixing the composite retarder powder with solid components of the magnesium phosphate cement-based material, and then adding mixing water for stirring and application; 2) Fully stirring, mixing and dissolving zinc acetate and water, and then adding the mixture into a solid mixture of magnesium phosphate cement-based materials doped with borate for stirring and application; 3) And fully stirring, mixing and dissolving zinc acetate, borate and mixing water, and then adding the mixture into a solid mixture of the magnesium phosphate cement-based material for stirring and application. Compared with the prior art, the composite retarder has obvious retarding effect, can greatly prolong the setting time of the magnesium phosphate cement-based material, can realize the effective regulation and control of the setting time of the magnesium phosphate cement-based material from tens of minutes to tens of hours, and meets the actual application demands.
Description
Technical Field
The invention relates to the field of preparation and application of magnesium phosphate cement-based materials, in particular to a composite retarder and application thereof in the magnesium phosphate cement-based materials.
Background
The magnesium phosphate cement is a special cementing material, and is widely applied to rush-construction and rush-repair engineering in the civil engineering field, such as airport runways, highways, concrete bridges, military building engineering, deep sea engineering and the like, and is applied to the curing safety treatment of heavy metals, active metals, medium-low radioactive substances and the like in the environmental field because of the advantages of quick setting, high early strength, small shrinkage, good adhesion with old concrete, low pH value of a hardening matrix pore solution, good capability of curing heavy metals and medium-low radioactive nuclear wastes and the like. In addition, in recent years, there are many other new applications of magnesium phosphate cement-based materials, such as 3D printing cement-based inks, fuel cell bipolar plates, graphene/magnesium phosphate cement structure supercapacitors, bioengineering repair materials, and the like.
However, too fast setting of the magnesium phosphate cement-based material may also result in too short a practical application operating time, resulting in failure to meet construction or other performance operating requirements. At present, borates (boric acid and borax) are traditional retarders of magnesium phosphate cement-based materials, however, the retarding effect of borates is limited. Therefore, in recent years, various other chemical reagents are sequentially used in magnesium phosphate cement-based materials for delaying cement coagulation, such as the compound retarder in the patent of application numbers 201310393211.1 and 201510808706.5, and the like, although the retarding effect is improved to a certain extent, the compound retarder contains chloride salt, so that corrosion is easily caused on exposed steel bars in the repairing engineering, and the durability of the repaired engineering is affected. In addition, although the patents of application numbers 202110124840.9, 202110855364.8 and 202111273586.5 do not contain chloride, the retarding effect of the magnesium phosphate cement-based material is limited, and the actual construction or other implementation operation requirements cannot be well met.
In summary, a great deal of mixing and application of the magnesium phosphate cement-based material in practical engineering are in need of a novel retarder capable of effectively prolonging the setting time, so that the setting time of the magnesium phosphate cement-based material can be effectively regulated and controlled according to different practical working condition demands.
Disclosure of Invention
The invention aims to solve the problems and provide a composite retarder and application thereof in magnesium phosphate cement-based materials, wherein zinc acetate and borate are used as the composite retarder, the novel composite retarder has remarkable retarding effect, and the setting time of the magnesium phosphate cement-based materials can be effectively regulated and controlled from tens of minutes to more than ten hours according to actual different working condition requirements.
The aim of the invention is achieved by the following technical scheme:
a first object of the present invention is to provide a composite retarder comprising zinc acetate and borate; the composite retarder is used for preparing magnesium phosphate cement-based materials.
Further, the composite retarder comprises zinc acetate and borate.
Further, the ratio of the mass of the zinc acetate to the mass of the borate is 1:9 to 9:1.
further preferably, the ratio of zinc acetate to borate is 1: 3. 1: 1. 3:1.
Further, the zinc acetate is zinc acetate dihydrate, anhydrous zinc acetate or other zinc acetate hydrates; the borate is borax or boric acid.
Further preferably, the zinc acetate is zinc acetate dihydrate.
Further preferably, the borate is borax.
Further, the composite retarder is prepared into a composite retarder powder by dry-mixing zinc acetate and borate according to a specified mass ratio to prepare a magnesium phosphate cement-based material, or zinc acetate is dissolved in water and borate is directly added to prepare a magnesium phosphate cement-based material, or zinc acetate and borate are dissolved in water according to a specified mass ratio to prepare a magnesium phosphate cement-based material.
The second object of the invention is to provide the application of the composite retarder in the magnesium phosphate cement-based material, and the composite retarder is used in the preparation of the magnesium phosphate cement-based material.
Further, the magnesium phosphate cement-based material comprises magnesium oxide, phosphate and the composite retarder.
Further preferably, the magnesium phosphate cement-based material further comprises an admixture, aggregate, functional filler, other additives.
Further, the mixing amount of the composite retarder is 0.5-10% of the total mass of the magnesium oxide and the phosphate.
Further preferably, the blending amount of the composite retarder is 0.5-5% of the total mass of the magnesium oxide and the phosphate.
Further, the specific methods of use of the compound retarder include three (but are not limited to):
method one (method 1): dry-mixing the composite retarder powder with solid components of the magnesium phosphate cement-based material, and then adding mixing water for stirring and application;
method two (method 2): and (3) fully stirring, mixing and dissolving zinc acetate and mixing water, and then adding the mixture into a solid mixture of the magnesium phosphate cement-based material doped with borate, and stirring and applying the mixture.
Method three (method 3): and fully stirring, mixing and dissolving zinc acetate, borate and mixing water, and then adding the mixture into a solid mixture of the magnesium phosphate cement-based material for stirring and application.
Optionally, the preparation of the composite retarder for the magnesium phosphate cement-based material comprises the following steps:
and dry-mixing the composite retarder powder with other components except the composite retarder in the magnesium phosphate cement-based material, and then adding mixing water for stirring.
Further, the preparation method of the composite retarder powder comprises the steps of mixing zinc acetate and borate according to a set proportion, and then uniformly stirring by using a mortar.
Optionally, the preparation of the composite retarder for the magnesium phosphate cement-based material comprises the following steps:
zinc acetate and water are fully stirred, mixed and dissolved, and then added into a solid mixture of other components except the compound retarder in the magnesium phosphate cement-based material doped with borate, and stirred.
Optionally, the preparation of the composite retarder for the magnesium phosphate cement-based material comprises the following steps:
and fully stirring, mixing and dissolving zinc acetate, borate and mixing water, and then adding the mixture into a solid mixture of the magnesium phosphate cement-based material for stirring and application.
Further, the magnesia is a dead burned magnesia.
Further, the phosphate comprises one or more of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, and ammonium dihydrogen phosphate.
Further, the admixture comprises one or more of fly ash, mineral powder, wollastonite (wollastonite powder), metakaolin, diatomite, regenerated micro powder (regenerated powder), garbage incineration ash, sludge and the like;
further, the aggregate comprises one or more of natural sand aggregate (natural sand), machine-made sand, recycled aggregate, artificial aggregate, and the like.
Further, the natural sand aggregate may be natural sand.
Further, the functional filler comprises one or more of phase change energy storage materials, glass beads, titanium dioxide and the like.
Further, the phase-change energy storage material comprises one or more of phase-change microcapsules, diatomite/paraffin composite phase-change materials, expanded vermiculite/paraffin composite phase-change materials and the like.
Further, the other additive includes a water reducing agent and the like.
Further, the water reducer comprises one or more of naphthalene water reducer, polycarboxylate water reducer and the like.
Further, the magnesium phosphorus molar ratio (M/P molar ratio) is 1:1 to 12:1. magnesium to phosphorus molar ratio is the molar ratio of the materials that burn the magnesium oxide and phosphate again.
Further, the water-to-solid ratio (W/S) is 0.1 to 0.6. The water in the water-solid ratio refers to mixing water, and the solid refers to the sum of magnesium oxide, phosphate, admixture and the composite retarder.
Compared with the prior art, the invention has the following advantages:
1. the composite retarder has obvious retarding effect on the magnesium phosphate cement-based material, can enable the setting time of the magnesium phosphate cement-based material to exceed 10 hours, and has the retarding effect improved by 11-55 times compared with the result of doping the traditional retarder borax, and is far better than the retarding effect of other retarders used in the prior literature report and patents.
2. The composite retarder can effectively regulate and control the setting time of the magnesium phosphate cement-based material within tens of minutes to more than ten hours by adjusting the mixing amount while prolonging the setting time of the magnesium phosphate cement-based material, is suitable for different actual working condition demands, and greatly expands the actual application scene of the magnesium phosphate cement-based material.
3. The composite retarder has no adverse effect on the durability of the reinforced concrete structure, and can effectively solve the problem of corrosion of the existing chlorine salt-containing composite retarder on exposed steel bars in the repaired engineering.
4. The composite retarder provided by the invention can be suitable for different magnesium-phosphorus mole ratios and water-solid ratios, and can be used in combination with admixture, aggregate, functional filler, other types of additives and the like, and has no adverse effect on the retarding effect.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications could be made by those skilled in the art without departing from the inventive concept. These are all within the scope of the present invention.
The applicant considers in conception history that: borate acts on magnesium oxide to generate refractory substances to wrap magnesium oxide particles so as to delay magnesium oxide reaction, zinc acetate mainly acts on phosphate so as to slow down the phosphate reaction speed, and synergistic effect exists between the magnesium oxide and the zinc acetate so as to lead the retarding effect to be far superior to that of singly mixing the magnesium oxide particles.
In the technical scheme, the characteristics of preparation means, materials, structures or composition ratios and the like which are not explicitly described are regarded as common technical characteristics disclosed in the prior art.
In the following examples of the invention, all materials are commercially available.
The following examples and comparative examples mainly include two indexes for measuring setting time and compressive strength of magnesium phosphate cement-based materials. Wherein, the setting time is carried out by referring to GB/T1346-2011 'method for testing water consumption, setting time and stability of cement standard consistency', and the compressive strength is carried out by referring to GB/T17671-1999 'method for testing cement mortar strength'.
The magnesia was selected from the group consisting of calcined magnesia available from ataxia-south radon refractory limited.
The phosphate is selected as industrial grade potassium dihydrogen phosphate, the purity is more than or equal to 98wt%, and the phosphate is purchased from Liyun gang Guangsu Utility company.
The retarder of the invention comprises the following three selected raw materials, which are all purchased from Shanghai Michlin Biochemical technology Co., ltd:
Zinc acetate dihydrate, white crystal, purity not less than 99wt%;
boric acid, white powder, purity more than or equal to 99.5wt%;
borax is white powder, and the purity is more than or equal to 99.5wt%.
Fly ash, metakaolin, wollastonite powder, reclaimed powder and natural sand are all commercial products, and the reclaimed powder refers to the industry standard of JG/T573-2020 reclaimed micro powder for concrete and mortar. The admixture and aggregate are not improvements of the present application, and in the following examples and comparative examples, the admixture and aggregate are added only to verify that the composite retarder of the present application is suitable for magnesium phosphate cement systems incorporating different admixtures or aggregates, and specific compositions of fly ash, metakaolin, wollastonite powder, recycled powder, and natural sand are not described in detail.
In order to verify the effectiveness and applicability of the composite retarder of the invention to magnesium phosphate cement-based materials in different magnesium-phosphorus (M/P) molar ratios, water-solid ratios (W/S), composite retarder components and blending amounts, blending materials, aggregates and the like, the following comparative examples and examples were carried out.
Example 1
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The retarder consists of zinc acetate dihydrate and boric acid, wherein the ratio of the zinc acetate dihydrate to the boric acid is 3:1, the zinc acetate dihydrate to the boric acid is used as a composite retarder No. 1, the composite retarder No. 1 which is 2.26% of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate is weighed, the zinc acetate dihydrate and the boric acid are respectively placed, and mixing water which is 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the composite retarder is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) The magnesium oxide, the monopotassium phosphate and the boric acid are weighed, dry-mixed for 60 seconds until the magnesium oxide, the monopotassium phosphate and the boric acid are uniformly mixed, then zinc acetate solution is added, the mixture is stirred slowly for 90 seconds, the mixture is stirred rapidly for 90 seconds, and the magnesium phosphate cement paste is obtained after stirring, and the obtained setting time and the amplification result of the setting time of the magnesium phosphate cement using borax as a retarder under the same proportion are shown in Table 2.
Example 2
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The retarder consists of zinc acetate dihydrate and boric acid, wherein the ratio of the zinc acetate dihydrate to the boric acid is 1:1, the zinc acetate dihydrate to the boric acid is taken as a composite retarder No. 2, the composite retarder No. 2 which is 2.26% of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate is weighed, the zinc acetate dihydrate and the boric acid are respectively placed, and mixing water which is 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the composite retarder is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate and boric acid for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the setting time and the result of the amplification of the setting time of the magnesium phosphate cement using boric acid as retarder in the same proportion are shown in Table 2, and the results of the compressive strength are shown in Table 3.
Example 3
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The retarder consists of zinc acetate dihydrate and boric acid, wherein the ratio of the zinc acetate dihydrate to the boric acid is 1:3, the zinc acetate dihydrate to the boric acid is used as a composite retarder No. 3 of the invention, the composite retarder No. 3 of the invention, which is 2.26% of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, is weighed, the zinc acetate dihydrate and the boric acid are respectively placed, and mixing water, which is 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the composite retarder, is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate and boric acid for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using boric acid as retarder in the same ratio are shown in Table 2.
Example 4
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the zinc acetate dihydrate to the borax is taken as a composite retarder No. 4, the composite retarder No. 4 which is 2.26% of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate is weighed, the zinc acetate dihydrate and the borax are respectively placed, and mixing water which is 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the composite retarder is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate and borax for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the setting time and the result of the amplification of the setting time of the magnesium phosphate cement using boric acid as retarder in the same proportion are shown in Table 2, and the results of the compressive strength are shown in Table 3.
The method employed in this example is method 2.
Example 5
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the composite retarder No. 4 is weighed, the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate is 2.26%, the zinc acetate dihydrate and the borax are mixed in a mortar, and mixing water with the total mass of 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the composite retarder is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
and adding the weighed composite retarder into magnesium oxide and potassium dihydrogen phosphate, stirring for 60s until the mixture is uniformly mixed, adding clear water, stirring for 90s at a low speed, and stirring for 90s at a high speed to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder in the same proportion are shown in Table 2.
The method employed in this example is method 1.
Example 6
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the composite retarder No. 4 is prepared by weighing 2.26% of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, the zinc acetate dihydrate and the borax are respectively placed, and mixing water with the total mass of 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the composite retarder is prepared.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
and adding the weighed compound retarder, namely zinc acetate dihydrate and borax, into the weighed mixed water, stirring until the zinc acetate dihydrate and borax are completely dissolved, dry-stirring for 60s in magnesium oxide and potassium dihydrogen phosphate until the magnesium oxide and the potassium dihydrogen phosphate are uniformly mixed, adding the prepared compound retarder solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder in the same proportion are shown in Table 2.
The method employed in this example is method 3.
Example 7
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 1:1. The retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the composite retarder No. 4 is prepared by weighing 2.26% of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, the zinc acetate dihydrate and the borax are respectively placed, and mixing water with the total mass of 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the composite retarder is prepared.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate and borax for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder in the same proportion are shown in Table 2.
Example 8
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), and the composite retarder applicable to the magnesium phosphate cement system is weighed according to the molar ratio of magnesium oxide to potassium dihydrogen phosphate M/P of 8:1. The retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the retarder No. 4 of the invention, which is 2.26% of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, is weighed, the zinc acetate dihydrate and the borax are respectively placed, and water with the total mass of 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the composite retarder is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate dihydrate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate and borax for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder in the same proportion are shown in Table 2.
Example 9
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 12:1. The retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the composite retarder No. 4 is prepared by weighing 2.26% of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, the zinc acetate dihydrate and the borax are respectively placed, and mixing water with the total mass of 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the composite retarder is prepared.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate and borax for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder in the same proportion are shown in Table 2.
Example 10
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The compound retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the No. 4 compound retarder of the invention, which is 2.26 percent of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, is weighed, the zinc acetate dihydrate and the borax are respectively placed, and mixing water, which is 0.18 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the compound retarder, is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate and borax for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder in the same proportion are shown in Table 2.
Example 11
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The compound retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the No. 4 compound retarder of the invention, which is 2.26 percent of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, is weighed, the zinc acetate dihydrate and the borax are respectively placed, and mixing water, which is 0.25 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the compound retarder, is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate and borax for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder in the same proportion are shown in Table 2.
Example 12
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The compound retarder consists of zinc acetate dihydrate and boric acid, wherein the ratio of the zinc acetate dihydrate to the boric acid is 1:1, the No. 2 compound retarder of the invention with the mass sum of magnesium oxide and potassium dihydrogen phosphate being 1.08 percent is weighed, the zinc acetate dihydrate and borax are respectively placed, and mixing water with the mass of 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the compound retarder is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate and boric acid for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the result of the amplification of the setting time of the magnesium phosphate cement using borax as retarder (2.26%) in the same proportion are shown in Table 2, and the result of the compressive strength is shown in Table 3.
Example 13
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The compound retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the No. 4 compound retarder of the invention, which is 1.08 percent of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, is weighed, the zinc acetate dihydrate and the borax are respectively placed, and mixing water, which is 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate and the compound retarder, is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate and borax for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder (2.26%) at the same ratio are shown in table 2.
Example 14
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The fly ash is selected as an admixture, the mixing amount is 10% of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, the composite retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the composite retarder No. 4 of the invention, which is 2.26% of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, is weighed, the zinc acetate dihydrate and the borax are respectively placed, and mixing water, which is 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate, the fly ash and the composite retarder, is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate, fly ash and borax for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder in the same proportion are shown in Table 4.
Example 15
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The method comprises the steps of selecting metakaolin as a blending material, mixing 10% of the sum of magnesium oxide and potassium dihydrogen phosphate, wherein the composite retarder consists of zinc acetate dihydrate and borax, the ratio of the zinc acetate dihydrate to the borax is 1:1, weighing the composite retarder No. 4 with the sum of the magnesium oxide and the potassium dihydrogen phosphate being 2.26%, placing the zinc acetate and the borax respectively, and weighing mixing water with the total mass of 0.22 times that of the magnesium oxide, the potassium dihydrogen phosphate, the metakaolin and the composite retarder.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate, metakaolin and borax for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder in the same proportion are shown in Table 4.
Example 16
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The wollastonite powder is selected as a blending material, the mixing amount is 10 percent of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, the composite retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the composite retarder No. 4 of the invention, which is 2.26 percent of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, is weighed, the zinc acetate dihydrate and the borax are respectively placed, and mixing water, which is 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate, the wollastonite powder and the composite retarder, is weighed.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) The measured magnesium oxide, potassium dihydrogen phosphate, wollastonite powder and borax are dried and stirred for 60s until the mixture is uniform, then zinc acetate solution is added, the mixture is stirred for 90s at a low speed and is stirred for 90s at a high speed, and the magnesium phosphate cement paste is obtained, and the measured setting time results are shown in Table 4.
Example 17
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The method comprises the steps of selecting regenerated powder as a blending material, mixing 10% of the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate, wherein the composite retarder consists of zinc acetate dihydrate and borax, the ratio of the zinc acetate dihydrate to the borax is 1:1, weighing the composite retarder No. 4 with the sum of the mass of magnesium oxide and the mass of potassium dihydrogen phosphate being 2.26%, placing the zinc acetate dihydrate and the borax respectively, and weighing mixing water with the total mass of 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate, the regenerated powder and the composite retarder.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate, the regenerated powder and borax for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement paste. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder in the same proportion are shown in Table 4.
Example 18
The embodiment provides a preparation method of a composite retarder (composite retarder applicable to a magnesium phosphate cement system), which comprises the steps of weighing magnesium oxide and potassium dihydrogen phosphate according to a molar ratio of M/P of 4:1. The composite retarder consists of zinc acetate dihydrate and borax, wherein the ratio of the zinc acetate dihydrate to the borax is 1:1, the composite retarder No. 4 is prepared by weighing magnesium oxide and potassium dihydrogen phosphate, the zinc acetate dihydrate and the borax are respectively placed, natural sand is selected as fine aggregate to prepare magnesium phosphate cement mortar, and the sand cement ratio is 80% of the natural sand which is 80% of the total mass of the magnesium oxide, the potassium dihydrogen phosphate, the regenerated powder and the composite retarder, and mixing water which is 0.22 times of the total mass of the magnesium oxide, the potassium dihydrogen phosphate, the regenerated powder and the composite retarder.
Method of use (application) in the preparation of magnesium phosphate cement-based materials:
(1) Adding the weighed zinc acetate dihydrate into the weighed mixed water, and fully stirring until the zinc acetate dihydrate is dissolved in the water to prepare a zinc acetate solution;
(2) And (3) dry stirring the measured magnesium oxide, potassium dihydrogen phosphate, natural sand and borax for 60s until the materials are uniformly mixed, adding a zinc acetate solution, slowly stirring for 90s, and rapidly stirring for 90s to obtain the magnesium phosphate cement mortar. The results of the measured setting time and the amplification of the setting time of the magnesium phosphate cement using borax as retarder in the same proportion are shown in Table 4.
Comparative example 1
In order to verify that the composite retarder of the invention has more excellent retarding effect compared with the traditional retarder applied to a magnesium phosphate cement system at present, the traditional retarder borax (sodium tetraborate decahydrate) is adopted as a comparative example of the invention, the M/P molar ratio is 4, the borax doping amount is 2.26 percent of the total mass of magnesium oxide and potassium dihydrogen phosphate, and the water-solid ratio is 0.22. The setting time and compressive strength results of the magnesium phosphate cement paste are shown in tables 2 and 3, respectively.
Comparative example 2
In order to verify that the composite retarder has more excellent retarding effect compared with the traditional retarder applied to a magnesium phosphate cement system at present, the traditional retarder boric acid is adopted as a comparison example of the invention, the M/P molar ratio is 4, the boric acid doping amount is 2.26 percent of the total mass of magnesium oxide and potassium dihydrogen phosphate, and the water-solid ratio is 0.22. The setting time and compressive strength results of the magnesium phosphate paste are shown in tables 2 and 3, respectively.
Comparative example 3
In order to verify that the composite retarder has more excellent retarding effect compared with the traditional retarder of the current magnesium phosphate cement system when the M/P molar ratio is 1, the traditional retarder borax (sodium tetraborate decahydrate) is adopted as a comparative example of the composite retarder, the M/P molar ratio is 1, the borax doping amount is 2.26% of the total mass of magnesium oxide and potassium dihydrogen phosphate, and the water-solid ratio is 0.22. The setting time results for the magnesium phosphate paste are shown in Table 2.
Comparative example 4
In order to verify that the composite retarder has more excellent retarding effect compared with the traditional retarder of the current magnesium phosphate cement system when the M/P molar ratio is 8, the traditional retarder borax (sodium tetraborate decahydrate) is adopted as a comparative example of the composite retarder, the M/P molar ratio is 8, the borax doping amount is 2.26% of the total mass of magnesium oxide and potassium dihydrogen phosphate, and the water-solid ratio is 0.22. The setting time results for the magnesium phosphate paste are shown in Table 2.
Comparative example 5
In order to verify that the composite retarder has more excellent retarding effect compared with the traditional retarder of the current magnesium phosphate cement system when the M/P molar ratio is 12, the traditional retarder borax (sodium tetraborate decahydrate) is adopted as a comparative example of the composite retarder, the M/P molar ratio is 12, the borax doping amount is 2.26% of the total mass of magnesium oxide and potassium dihydrogen phosphate, and the water-solid ratio is 0.22. The setting time results of the magnesium phosphate cement paste are shown in Table 2.
Comparative example 6
In order to verify that the composite retarder has more excellent retarding effect compared with the traditional retarder of the current magnesium phosphate cement system when the water-solid ratio is 0.18, the traditional retarder borax (sodium tetraborate decahydrate) is adopted as a comparative example of the composite retarder, the M/P molar ratio is 4, the borax doping amount is 2.26 percent of the total mass of magnesium oxide and potassium dihydrogen phosphate, and the water-solid ratio is 0.18. The setting time results of the magnesium phosphate cement paste are shown in Table 2.
Comparative example 7
In order to verify that the composite retarder has more excellent retarding effect compared with the traditional retarder of the current magnesium phosphate cement system when the water-solid ratio is 0.25, the traditional retarder borax (sodium tetraborate decahydrate) is adopted as a comparative example of the composite retarder, the M/P molar ratio is 4, the borax doping amount is 2.26 percent of the total mass of magnesium oxide and potassium dihydrogen phosphate, and the water-solid ratio is 0.25. The setting time results of the magnesium phosphate cement paste are shown in Table 2.
Comparative example 8
In order to verify that the composite retarder has more excellent retarding effect compared with the traditional retarder of the existing magnesium phosphate cement system when the fly ash admixture is doped, the traditional retarder borax (sodium tetraborate decahydrate) is adopted as a comparative example of the invention, the M/P molar ratio is 4, the water-solid ratio is 0.25, and the doping amount of the borax and the fly ash is 2.26% and 10% of the total mass of the magnesium oxide and the potassium dihydrogen phosphate. The setting time results of the magnesium phosphate cement paste are shown in Table 4.
Comparative example 9
In order to verify that the composite retarder has more excellent retarding effect compared with the traditional retarder of the current magnesium phosphate cement system when the metakaolin admixture is doped, the traditional retarder borax (sodium tetraborate decahydrate) is adopted as a comparative example of the composite retarder, the M/P molar ratio is 4, the water-solid ratio is 0.25, and the doping amount of the borax and the metakaolin is 2.26% and 10% of the total mass of the magnesium oxide and the monopotassium phosphate. The setting time results of the magnesium phosphate cement paste are shown in Table 4.
Comparative example 10
In order to verify that the composite retarder has more excellent retarding effect compared with the traditional retarder of the current magnesium phosphate cement system when the wollastonite powder admixture is doped, the traditional retarder borax (sodium tetraborate decahydrate) is adopted as a comparative example of the composite retarder, the M/P molar ratio is 4, the water-solid ratio is 0.25, and the doping amount of the borax and the wollastonite powder is 2.26% and 10% of the total mass of the magnesium oxide and the monopotassium phosphate. The setting time results of the magnesium phosphate cement paste are shown in Table 4.
Comparative example 11
In order to verify that the composite retarder has more excellent retarding effect compared with the traditional retarder of the current magnesium phosphate cement system when the regenerated powder admixture is doped, the traditional retarder borax (sodium tetraborate decahydrate) is adopted as a comparative example of the composite retarder, the M/P molar ratio is 4, the water-solid ratio is 0.25, and the doping amount of the borax and the regenerated powder is 2.26% and 10% of the total mass of the magnesium oxide and the potassium dihydrogen phosphate. The setting time results of the magnesium phosphate cement paste are shown in Table 4.
Comparative example 12
In order to verify that the composite retarder has more excellent retarding effect than the traditional retarder of the existing magnesium phosphate cement system when aggregate (natural sand) is added, the traditional retarder borax (sodium tetraborate decahydrate) is adopted as a comparative example of the composite retarder, the M/P molar ratio is 4, the water-solid ratio is 0.25, the borax addition amount is 2.26% of the total mass of magnesium oxide and potassium dihydrogen phosphate, and the ratio of natural sand to the total mass of magnesium oxide, potassium dihydrogen phosphate and borax, namely the mastic ratio is 80%. The setting time results of the magnesium phosphate cement mortar are shown in Table 4.
Four different combinations of the composite retarder of the present invention used in the examples are shown in table 1, no. 1: 75% zinc acetate dihydrate +25% boric acid; the compound retarder of the invention No. 2: 50% zinc acetate dihydrate +50% boric acid; the compound retarder of the invention No. 3: 25% zinc acetate dihydrate +75% boric acid; the compound retarder of the invention No. 3: 50% zinc acetate dihydrate +50% borax. The above ratio is the mass ratio of the different components.
Table 1 the composition and proportions of the compound retarder of the invention.
| Numbering device | Zinc acetate dihydrate (%) | Boric acid (%) | Borax (%) |
| The composite retarder No. 1 of the invention | 75 | 25 | 0 |
| The invention relates to a compound retarder No. 2 | 50 | 50 | 0 |
| The invention relates to a compound retarder No. 3 | 25 | 75 | 0 |
| The composite retarder No. 4 of the invention | 50 | 0 | 50 |
The results of the tests on setting time of magnesium phosphate cement paste with different M/P molar ratios, water-solid ratios, retarder types/amounts are shown in Table 2.
Table 2 results of tests of setting time of magnesium phosphate cement paste with different M/P molar ratios, water-to-solid ratios, retarder types/amounts.
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The results of the compressive strength test of the magnesium phosphate cement paste of some comparative examples and examples are shown in Table 3.
Table 3 compressive strength test results of magnesium phosphate cement paste.
The results of the tests of magnesium phosphate cement paste and mortar setting time of some of the comparative examples and examples incorporating different admixtures and aggregates are shown in Table 4.
Table 4 test results of magnesium phosphate cement paste and mortar setting time for different admixtures and aggregates.
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As can be seen from the test results of comparative examples and examples in tables 1 to 4:
(1) Compared with the comparative examples (comparative examples 1, 3-8) added with borax retarder under the same proportion, the magnesium phosphate cement paste (examples 1-11) using the composite retarder of the invention has the advantages that the setting time is increased by 32-864 min, and the amplification is 267% -5567%; examples 12 and 13, compared with comparative example 1, show that the setting time is increased by 68 and 15min and the setting time is increased by 567% and 125% respectively even though the mixing amount of the retarder in examples 12 and 13 is 50% of that in comparative example 1, and the setting effect of the compound retarder of the invention is very remarkable.
(2) The test results of examples 7, 8 and 9 and comparative examples 3, 4 and 5 show that the retarder has obvious retarding effect under the M/P molar ratio of 1-12; the test results of examples 10 and 11 and comparative examples 6 and 7 show that the composite retarder has obvious retarding effects under different water-solid ratios.
(3) Compared with comparative examples 8-11, examples 14-17 doped with different admixtures have the advantages that the setting time is increased by 157-258 min, the amplification is 924-1518%, and the composite retarder is suitable for magnesium phosphate cement systems doped with different admixtures and has the effect far better than that of traditional retarder borax.
(4) Compared with comparative example 12, the setting time of example 18 doped with aggregate (natural sand) is increased by 107min, and the amplification is 713%, which shows that the composite retarder is also applicable to magnesium phosphate cement mortar doped with aggregate, and the effect is far better than that of the traditional retarder borax.
(5) As is apparent from the compressive strength test results of comparative examples 1, 2 and examples 2, 4, 12 in table 3, example 11, i.e., comparative example 2 using boric acid retarder alone, had a compressive strength of magnesium phosphate cement paste 7d of composite retarder No. 2 of the present invention and an amount of 1.08% added, which was lower by only 2.4MPa than comparative example 1 using borax, but increased setting time by 567% and 129% as compared with comparative examples 1 and 2, respectively. Therefore, the composite retarder can multiply improve the setting time of the magnesium phosphate cement paste under a smaller mixing amount, and has little adverse effect on the compressive strength of the magnesium phosphate cement. The setting times of the magnesium phosphate cements in examples 2 and 4 were prolonged to 680min and 253min, respectively, wherein the amplification of example 2 was up to 55.7 times as compared with comparative example 1, and the 7d compressive strength thereof was reduced by 28% and 29% as compared with comparative example 1, respectively, thereby showing that the composite retarder of the present invention greatly improved the setting time of the magnesium phosphate cement while still having less influence on the compressive strength.
(6) The setting times of examples 4, 5 and 6 are improved by 2008%, 267% and 1883% respectively compared with the setting time of the borax alone in the same proportion, which shows that the setting time of the retarder of the invention can be greatly improved under all three using methods, but the setting time of the example 4 of the using method 2 is better than that of the example 5 of the using method 1 and the example 6 of the using method 3, so that the compound setting retarder of the invention more suggests the using method 2 to exert the maximum setting effect of the compound setting retarder of the invention under the condition of permission.
In conclusion, the composite retarder provided by the invention remarkably improves the setting time of the magnesium phosphate cement-based material, has a retarding effect remarkably superior to that of the traditional single borate (borax and boric acid), can be used in combination with cement admixture, aggregate, functional filler and other additives, and has no adverse effect on the retarding effect; and the method has no adverse effect on the mechanical properties of the magnesium phosphate cement-based material, and can meet the requirements of mixing, operation and strength of the rapid magnesium phosphate cement-based material in practical application.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The composite retarder is characterized by comprising zinc acetate and borate;
the composite retarder is used for preparing magnesium phosphate cement-based materials.
2. The compound retarder according to claim 1, wherein the mass ratio of zinc acetate to borate is 1:9 to 9:1.
3. a compound retarder according to claim 1, wherein the zinc acetate is anhydrous zinc acetate or zinc acetate hydrate;
the borate is borax or boric acid.
4. Use of a composite retarder according to claims 1-3 in the preparation of magnesium phosphate cement-based materials, characterized in that the composite retarder is used in the preparation of magnesium phosphate cement-based materials.
5. The use of a composite retarder in a magnesium phosphate cement-based material according to claim 4, wherein the magnesium phosphate cement-based material comprises magnesium oxide, phosphate, the composite retarder;
the mixing amount of the composite retarder is 0.5-10% of the total mass of the magnesium oxide and the phosphate.
6. The use of a composite retarder in a magnesium phosphate cement-based material according to claim 5, wherein the use of the composite retarder in the preparation of a magnesium phosphate cement-based material comprises the steps of:
And dry-mixing the composite retarder powder with other components except the composite retarder in the magnesium phosphate cement-based material, and then adding mixing water for stirring.
7. The use of a composite retarder in a magnesium phosphate cement-based material according to claim 5, wherein the use of the composite retarder in the preparation of a magnesium phosphate cement-based material comprises the steps of:
zinc acetate and water are fully stirred, mixed and dissolved, and then added into a solid mixture of other components except the compound retarder in the magnesium phosphate cement-based material doped with borate, and stirred.
8. The use of a composite retarder in a magnesium phosphate cement-based material according to claim 5, wherein the use of the composite retarder in the preparation of a magnesium phosphate cement-based material comprises the steps of:
zinc acetate and borate are mixed with water to be dissolved, and then added into a solid mixture of magnesium phosphate cement-based materials to be stirred.
9. The use of a composite retarder according to claim 5 in magnesium phosphate cement-based materials, wherein the magnesium phosphate cement-based materials further comprise admixtures, aggregates, functional fillers, other additives.
10. The use of a composite retarder in a magnesium phosphate cement-based material according to claim 9, wherein the phosphate comprises one or more of potassium dihydrogen phosphate, dipotassium hydrogen phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate;
the admixture comprises one or more of fly ash, mineral powder, wollastonite, metakaolin, diatomite, regenerated micro powder, garbage incineration ash and sludge;
the aggregate comprises one or more of natural sand aggregate, machine-made sand aggregate, recycled aggregate and artificial aggregate;
the functional filler comprises one or more of phase change energy storage materials, glass beads and titanium dioxide;
the other additive comprises a water reducing agent.
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