CN115974510B - Fluorine-phosphorus composite gypsum self-leveling, preparation method and application thereof - Google Patents
Fluorine-phosphorus composite gypsum self-leveling, preparation method and application thereof Download PDFInfo
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- 239000010440 gypsum Substances 0.000 title claims abstract description 158
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 158
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- ZHQXROVTUTVPGO-UHFFFAOYSA-N [F].[P] Chemical compound [F].[P] ZHQXROVTUTVPGO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 99
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims abstract description 58
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000010439 graphite Substances 0.000 claims abstract description 33
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 33
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 27
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 27
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 27
- 235000011116 calcium hydroxide Nutrition 0.000 claims abstract description 27
- 150000004683 dihydrates Chemical class 0.000 claims abstract description 25
- 239000004568 cement Substances 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 229920003023 plastic Polymers 0.000 claims abstract description 23
- 239000004033 plastic Substances 0.000 claims abstract description 23
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 238000000498 ball milling Methods 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 229920000459 Nitrile rubber Polymers 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 17
- -1 polypropylene Polymers 0.000 claims abstract description 17
- 239000010881 fly ash Substances 0.000 claims abstract description 16
- 229910021487 silica fume Inorganic materials 0.000 claims abstract description 15
- 239000004743 Polypropylene Substances 0.000 claims abstract description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 229920001155 polypropylene Polymers 0.000 claims abstract description 14
- 239000004576 sand Substances 0.000 claims abstract description 14
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000005086 pumping Methods 0.000 claims abstract description 10
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- 239000000839 emulsion Substances 0.000 claims abstract description 6
- 230000009466 transformation Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 4
- 229940095564 anhydrous calcium sulfate Drugs 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 238000012986 modification Methods 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 239000002367 phosphate rock Substances 0.000 claims description 3
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 2
- 239000010436 fluorite Substances 0.000 claims description 2
- 239000002440 industrial waste Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 239000004566 building material Substances 0.000 abstract description 2
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 abstract 2
- 239000002585 base Substances 0.000 description 19
- 239000004570 mortar (masonry) Substances 0.000 description 18
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 10
- 239000005038 ethylene vinyl acetate Substances 0.000 description 8
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000010276 construction Methods 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000005336 cracking Methods 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 229920001084 poly(chloroprene) Polymers 0.000 description 6
- 229940095672 calcium sulfate Drugs 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 239000012615 aggregate Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036571 hydration Effects 0.000 description 2
- 238000006703 hydration reaction Methods 0.000 description 2
- 238000001238 wet grinding Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 239000011083 cement mortar Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011505 plaster Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012783 reinforcing fiber Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/91—Use of waste materials as fillers for mortars or concrete
Landscapes
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The invention relates to the technical field of building materials, in particular to a self-leveling and preparation method and application of fluorine-phosphorus composite gypsum. The fluorine-phosphorus composite gypsum self-leveling comprises the following raw materials in parts by weight: 80-85 parts of modified fluorophosphite composite gypsum powder, 5-10 parts of fly ash cement, 1-3 parts of redispersible emulsion powder, 0.5-2.5 parts of slaked lime, 2-8 parts of fine river sand, 1-2 parts of silica fume powder, 1-3 parts of polypropylene short fiber and 0.5-2 parts of water reducer; the preparation method of the modified fluorine-phosphorus composite gypsum powder comprises the steps of adding phosphogypsum, fluorine gypsum, slaked lime and micro-powder graphite into a ball mill, and adding water as a ball milling medium for ball milling to obtain dihydrate gypsum slurry; pumping the dihydrate gypsum slurry into an autoclave, adding citric acid and sodium dodecyl benzene sulfonate, uniformly mixing, completing crystal transformation to obtain a feed liquid of the hemihydrate gypsum, centrifugally dewatering, washing and drying the feed liquid, adding liquid nitrile rubber and micro powder graphite, and grinding and modifying the hemihydrate gypsum powder. Can solve the problem of degumming of PVC plastic floor and self-leveling base material, and the problem that the moisture is not easy to reach the standard after the self-leveling base material is hardened.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a self-leveling and preparation method and application of fluorine-phosphorus composite gypsum.
Background
PVC plastic floor boards are becoming popular in hospitals, schools, office buildings, markets and other places with large human flow because of the characteristics of ultra-light weight, wear resistance, skid resistance, noise prevention and the like. The PVC plastic floor is a flexible material and has a thinner thickness, so that the PVC plastic floor has a higher requirement on the flatness of the ground base material. The gypsum self-leveling is a mortar material for leveling indoor ground, which is prepared from gypsum, aggregate and chemical additives. Compared with cement mortar self-leveling, the gypsum self-leveling cementing material has the advantages of good heat resistance and heat preservation, easiness in construction, low shrinkage after hardening and the like, the thickness of the gypsum self-leveling construction can reach 10cm at one time, and the gypsum self-leveling cementing material has good application prospect as a leveling base layer of a PVC plastic floor with high flatness requirements.
The existing gypsum self-leveling is used for leveling PVC plastic floors and has the following general problems: the adhesion force between the PVC plastic floor and the self-leveling is poor, and the floor is easy to degumm and edge-warping; PVC is airtight, in order to avoid the decrease of the strength of the base material caused by aggregation of residual moisture at the bottom of the self-leveling, the requirement on the dry moisture content of gypsum self-leveling is higher (below 0.5%), and in order to shorten the construction period, it is also not preferable to use a method of increasing the ventilation quantity or increasing the temperature to achieve the satisfactory moisture content, because the difference between the dry and bottom drying rates of the self-leveling surface is increased, so that the self-leveling strength is reduced, and the base material is easy to crack. In view of this, the present invention has been made.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the fluorine-phosphorus composite gypsum self-leveling and the preparation method thereof, which can improve the degumming problem of PVC plastic floors and self-leveling base materials and solve the problem that the water content of gypsum after self-leveling construction is difficult to reach the construction requirement of the PVC plastic floors.
The invention adopts the technical scheme that the self-leveling fluorine-phosphorus composite gypsum is provided and consists of the following raw materials in parts by weight: 80-85 parts of modified fluorophosphite composite gypsum powder, 5-10 parts of fly ash cement, 1-3 parts of redispersible emulsion powder, 0.5-2.5 parts of slaked lime, 2-8 parts of fine river sand, 1-2 parts of silica fume powder, 1-3 parts of polypropylene short fiber and 0.5-2 parts of water reducer;
The preparation method of the modified fluorophosphoric composite gypsum powder comprises the following steps:
Firstly, adding phosphogypsum, fluorgypsum, slaked lime and micro-powder graphite into a ball mill, adding water as a ball milling medium, and performing ball milling reaction for 5-20 hours at a ball-material ratio of 5-10:1 and a rotating speed of 300-500rpm to obtain dihydrate gypsum slurry;
Step two: pumping the dihydrate gypsum slurry into an autoclave, adding citric acid and sodium dodecyl benzene sulfonate, uniformly mixing, performing an autoclaved reaction for 5-10 hours at the temperature of 120-130 ℃ to finish crystal transformation to obtain a semi-hydrated gypsum feed liquid, centrifugally dehydrating, washing and drying the feed liquid, and adding liquid nitrile rubber and micro-powder graphite into the obtained semi-hydrated gypsum powder to perform grinding modification to obtain the product.
The self-leveling hardening of gypsum is mainly to hydrate by means of semi-hydrated gypsum to form dihydrate gypsum. The addition of the fly ash cement can improve the strength, workability and water resistance of the product; and the fly ash cement has less water and better crack resistance. The flexible gel formed by the redispersible emulsion powder and the fly ash cement can form an interpenetrating network structure together, thereby reducing the generation of microcracks at the interface of aggregate and gypsum slurry and improving the tensile bonding strength of the product. The fine river sand and the silica fume powder are used as aggregate and filler, so that the fluidity is increased, and the silica fume powder has the functions of expansibility and crack reduction. The polypropylene fiber is used as the reinforcing fiber, has good diastole, can be uniformly distributed in the base material, and improves the strength of gypsum powder.
Phosphogypsum and fluorogypsum adopted by the application are industrial byproduct gypsum, wherein the phosphogypsum is a byproduct of phosphoric acid production from phosphorite, and the main components are as follows: 20-70% of dihydrate gypsum, 2-8% of phosphoric acid, undegraded phosphate rock, a small amount of alkali metal salt and the like. The fluorogypsum is industrial waste residue after preparing hydrofluoric acid by a fluorite concentrated sulfuric acid method, and comprises the following main components: 85-95% of anhydrous calcium sulfate and 1-5% of calcium fluoride, and the main uses of the fluorine gypsum and phosphogypsum are currently as cement preparation. The fluorine gypsum and the phosphogypsum contain a large amount of calcium sulfate, but contain more impurities, the preparation strength of the self-leveling gypsum is lower when the self-leveling gypsum is directly used for self-leveling gypsum, the hydration rates of the calcium sulfate from different sources are obviously different, the self-leveling base material is difficult to maintain, and cracks are easy to generate on the surface of the base material. According to the application, phosphogypsum and fluorogypsum which are industrial byproducts are used as calcium sulfate sources, graphite micropowder is added in wet grinding, the graphite micropowder has antistatic and lubricating effects, the electrostatic effects among different sources of gypsum powder can be reduced, the agglomeration of the gypsum powder is reduced, the mixing uniformity of phosphogypsum and fluorogypsum is promoted, the slaked lime can neutralize the residual acid in phosphogypsum, and anhydrous calcium sulfate is stimulated to hydrate to obtain the dihydrate gypsum. The dihydrate gypsum slurry obtained by grinding can be directly transferred into an autoclave without treatment, autoclaved crystal transformation is carried out under the action of crystal transformation agent citric acid and dispersant sodium dodecyl benzene sulfonate, gypsum powder can be purified by filtering and washing the slurry after crystal transformation, most of water-soluble impurities are removed, and the adhesion between the product surface crystallization of the impurities and PVC plastic floor is prevented from being influenced by the crystallization of the impurities after water evaporation. The obtained semi-hydrated gypsum powder is ground by utilizing liquid nitrile rubber and micro-powder graphite, and the liquid nitrile rubber molecules contain strong polar functional groups, so that the compatibility between gypsum self-leveling and PVC plastic floor can be improved, and the semi-hydrated gypsum powder is not easy to fall off after sizing. The liquid nitrile rubber can also enable micro powder graphite to be attached to the surface of semi-hydrated gypsum powder, when gypsum self-leveling water is added for size mixing, the micro powder graphite on the surface of the gypsum powder can reduce the electrostatic effect between calcium sulfate molecules and free water, is beneficial to release and volatilization of internal moisture, optimizes the composition and proportion of a self-leveling formula, and finally enables a self-leveling base material to be dried quickly to a water content of below 0.5%. The micro powder graphite and the liquid nitrile rubber can also improve the water resistance of the self-leveling base material.
Further, in the first step, the adding amount of the fluorine gypsum is 10-20% of the weight of the phosphogypsum, the using amount of the slaked lime is 2-6% of the weight of the phosphogypsum, the using amount of the micro powder graphite is 1-2% of the weight of the phosphogypsum, and the ratio of the material to the water is 2-4:10.
Further, the granularity of the micro powder graphite in the step one is 100-300 meshes, the price of the micro powder graphite with the granularity is low, the micro powder graphite particles can be further refined by wet grinding, and satisfactory lubrication and antistatic effects can be achieved.
Further, the usage amount of the liquid nitrile rubber in the second step is 1-5% of the weight of the semi-hydrated gypsum powder, the granularity of the micro-powder graphite is 400 meshes, and the usage amount of the micro-powder graphite is 0.3-0.8% of the weight of the semi-hydrated gypsum powder. The usage amount of the liquid nitrile rubber is not excessively large, for example, the addition amount of the liquid nitrile rubber is excessively large, so that the hydration of the semi-hydrated gypsum can be inhibited.
Further, the water reducer is a polycarboxylic acid high-performance water reducer or a sulfamate high-efficiency water reducer.
The invention also provides a preparation method of the fluorophosphoric composite gypsum self-leveling, which adopts the following steps: according to the formula amount, adding the modified fluorine-phosphorus composite gypsum powder, fly ash cement, redispersible emulsion powder, slaked lime, silica fume powder and a water reducing agent into a high-speed mixer, uniformly mixing, and then adding the fine river sand and the polypropylene short fiber for continuous uniform mixing.
The self-leveling of the fluorine-phosphorus composite gypsum is suitable for being used as a leveling base material of a PVC plastic floor, so the invention also provides application of the self-leveling of the fluorine-phosphorus composite gypsum in the leveling base material of the PVC plastic floor. The PVC plastic floor and the plaster self-leveling paving method can be realized by adopting a method commonly used in the field.
Compared with the prior art, the invention has the beneficial effects that:
According to the invention, graphite micropowder and liquid nitrile rubber with strong polar functional groups are utilized to modify the fluorophosphoric composite gypsum powder, so that raw and auxiliary material components and proportions are optimized, the self-leveling of the obtained gypsum and the PVC plastic floor have good affinity, the peel strength is greatly improved, the problem that the water content of the self-leveling construction gypsum is difficult to reach the construction requirement of the PVC plastic floor is solved, and the water content of the self-leveling water content of 5d can reach below 0.5%.
The method can fully utilize precious calcium sulfate resources in the industrial byproduct gypsum to obtain gypsum self-leveling with high added value, the self-leveling performance of the gypsum obtained by the method can reach JC/T1023-2021 standard, the dependence on natural gypsum products is reduced, the economic value is more remarkable, and the problems of land occupation and environmental pollution of the byproduct gypsum are alleviated.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The methods are conventional methods unless otherwise specified, and the starting materials are commercially available from the public sources unless otherwise specified.
Example 1
The formula (weight portion) of the fluorine-phosphorus composite gypsum self-leveling mortar comprises the following components: 82 parts of modified fluorine phosphorus composite gypsum powder, 42.5 parts of fly ash cement PF, 2 parts of ethylene-vinyl acetate copolymer, 1.5 parts of slaked lime, 6 parts of fine river sand, 1.5 parts of silica fume powder, 2 parts of polypropylene short fiber and 1 part of polycarboxylic acid high-performance water reducer;
the preparation method of the fluorine-phosphorus composite gypsum self-leveling mortar comprises the following steps:
(1) Preparation of modified fluorophosphoric composite gypsum powder
Adding phosphogypsum, 20% of phosphogypsum by weight of fluorgypsum, 3.5% of slaked lime by weight of phosphogypsum and 1% of micro powder graphite by weight of phosphogypsum into a ball mill, adding water as a ball milling medium according to a water-to-material ratio of 3:10, adding grinding balls according to a ball-to-material ratio of 5:1, and performing ball milling reaction for 10 hours at a rotating speed of 350rpm to hydrate gypsum powder to obtain dihydrate gypsum slurry.
Step two: pumping the dihydrate gypsum slurry into an autoclave, adding citric acid accounting for 1% of the phosphogypsum by weight as a crystal transferring agent, adding sodium dodecyl benzene sulfonate accounting for 0.5% of the phosphogypsum by weight, uniformly mixing, performing an autoclave reaction at 120-130 ℃ for 7 hours, then completing crystal transferring to obtain semi-hydrated gypsum feed liquid, performing centrifugal dehydration, washing and drying on the feed liquid, adding liquid nitrile rubber accounting for 3% of the dry gypsum raw material by weight and 400-mesh micro powder graphite accounting for 2 hours, and grinding.
(2) According to the formula amount, adding modified fluorine phosphorus composite gypsum powder, fly ash cement, ethylene-vinyl acetate copolymer, slaked lime, silica fume powder and polycarboxylic acid high-performance water reducer into a high-speed mixer, mixing for 30min at a stirring speed of 800rpm, adding fine river sand and polypropylene short fibers, and continuously mixing for 10min at a stirring speed of 500rpm to obtain the modified fluorine phosphorus composite gypsum powder.
(3) The obtained gypsum self-leveling base material has a water cement ratio of 0.26:1, a fluidity of 215mm in 30min, an absolute dry breaking strength of 7.5MPa, an absolute dry compressive strength of 27.6MPa, no cracking and a dimensional change rate of 0.032 percent by adopting a JC/T1023-2021 method. The water content after 5d was measured according to the method in ASTM4263 and found to be 0.35%. The peel strength of the PVC plastic floor and the self-leveling base material (the glue adopts neoprene) is 8.5N/cm according to the GB 2792-2014 method.
Example 2
The formula (weight portion) of the fluorine-phosphorus composite gypsum self-leveling mortar comprises the following components: 80 parts of modified fluorine phosphorus composite gypsum powder, 42.5 parts of fly ash cement PF, 1.5 parts of ethylene-vinyl acetate copolymer, 1.2 parts of slaked lime, 5 parts of fine river sand, 1.5 parts of silica fume powder, 3 parts of polypropylene short fiber and 1.2 parts of polycarboxylic acid high-performance water reducer;
the preparation method of the fluorine-phosphorus composite gypsum self-leveling mortar comprises the following steps:
(1) Preparation of modified fluorophosphoric composite gypsum powder
Adding phosphogypsum, 20% of phosphogypsum by weight of fluorgypsum, 3.8% of slaked lime by weight of phosphogypsum and 1.2% of micro-powder graphite by weight of phosphogypsum into a ball mill, adding water as a ball milling medium according to a water-to-material ratio of 3:10, adding grinding balls according to a ball-to-material ratio of 5:1, and performing ball milling reaction for 8 hours at a rotating speed of 500rpm to hydrate gypsum powder to obtain dihydrate gypsum slurry.
Step two: pumping the dihydrate gypsum slurry into an autoclave, adding citric acid accounting for 1.2% of the phosphogypsum by weight as a crystal transferring agent, adding sodium dodecyl benzene sulfonate accounting for 0.8% of the phosphogypsum by weight, uniformly mixing, performing autoclave treatment at 120-130 ℃ for 7 hours, performing crystal transferring to obtain semi-hydrated gypsum feed liquid, performing centrifugal dehydration, washing and drying on the feed liquid, adding liquid nitrile rubber accounting for 3.2% of the dry gypsum feed material by weight and 400-mesh micro powder graphite accounting for 2 hours, and grinding.
(2) According to the formula amount, adding modified fluorine phosphorus composite gypsum powder, fly ash cement, ethylene-vinyl acetate copolymer, slaked lime, silica fume powder and polycarboxylic acid high-performance water reducer into a high-speed mixer, mixing for 30min at a stirring speed of 800rpm, adding fine river sand and polypropylene short fibers, and continuously mixing for 10min at a stirring speed of 500rpm to obtain the modified fluorine phosphorus composite gypsum powder.
(3) The self-leveling performance of the obtained gypsum is tested by adopting a method in JC/T1023-2021 gypsum-based self-leveling mortar according to the water-cement ratio of 0.26:1, the fluidity of 30min is 214mm, the absolute dry breaking strength is 7.2MPa, the absolute dry compressive strength is 26.8MPa, no cracking is caused, and the dimensional change rate is 0.038%. The water content after 5d was measured according to the method in ASTM4263 and found to be 0.32%. The peel strength of the PVC plastic floor and the self-leveling base material (the glue adopts neoprene) is 8.7N/cm according to the GB 2792-2014 method.
Example 3
The formula (weight portion) of the fluorine-phosphorus composite gypsum self-leveling mortar comprises the following components: 80 parts of modified fluorine phosphorus composite gypsum powder, 42.5 parts of fly ash cement PF, 1 part of ethylene-vinyl acetate copolymer, 1 part of slaked lime, 8 parts of fine river sand, 1 part of silica fume powder, 1 part of polypropylene short fiber and 1.2 parts of polycarboxylic acid high-performance water reducer;
the preparation method of the fluorine-phosphorus composite gypsum self-leveling mortar comprises the following steps:
(1) Preparation of modified fluorophosphoric composite gypsum powder
Adding phosphogypsum, fluorogypsum accounting for 10% of the phosphogypsum, slaked lime accounting for 4% of the phosphogypsum and micro-powder graphite accounting for 1.8% of the phosphogypsum into a ball mill, adding water according to a water-to-material ratio of 3:10 as a ball milling medium, adding grinding balls according to a ball-to-material ratio of 5:1, and performing ball milling reaction for 10 hours at a rotating speed of 350rpm to hydrate gypsum powder to obtain dihydrate gypsum slurry.
Step two: pumping the dihydrate gypsum slurry into an autoclave, adding citric acid accounting for 1.2% of the phosphogypsum by weight as a crystal transferring agent, adding sodium dodecyl benzene sulfonate accounting for 0.8% of the phosphogypsum by weight, uniformly mixing, performing autoclave treatment at 120-130 ℃ for 7 hours, performing crystal transferring to obtain semi-hydrated gypsum feed liquid, performing centrifugal dehydration, washing and drying on the feed liquid, adding liquid nitrile rubber accounting for 3.5% of the dry gypsum feed material by weight and 400-mesh micro powder graphite accounting for 2 hours, and grinding.
(2) According to the formula amount, adding modified fluorine phosphorus composite gypsum powder, fly ash cement, ethylene-vinyl acetate copolymer, slaked lime, silica fume powder and polycarboxylic acid high-performance water reducer into a high-speed mixer, mixing for 30min at a stirring speed of 800rpm, adding fine river sand and polypropylene short fibers, and continuously mixing for 10min at a stirring speed of 500rpm to obtain the modified fluorine phosphorus composite gypsum powder.
(3) The self-leveling performance of the obtained gypsum is tested by adopting a method in JC/T1023-2021 gypsum-based self-leveling mortar according to the water-cement ratio of 0.26:1, the fluidity for 30min is 209mm, the absolute dry breaking strength is 7.6MPa, the absolute dry compressive strength is 27.9MPa, no cracking is caused, and the dimensional change rate is 0.029%. The water content after 5d was measured according to the method in ASTM4263 and found to be 0.31%. The peel strength of the PVC plastic floor and the self-leveling base material (the glue adopts neoprene) is 9.1N/cm according to the GB 2792-2014 method.
Example 4
The formula (weight portion) of the fluorine-phosphorus composite gypsum self-leveling mortar comprises the following components: 85 parts of modified fluorophosphite composite gypsum powder, 42.5 parts of fly ash cement PF 42.7 parts, 3 parts of ethylene-vinyl acetate copolymer, 2.5 parts of slaked lime, 5 parts of fine river sand, 1 part of silica fume powder, 1 part of polypropylene short fiber and 1.5 parts of sulfamate high-efficiency water reducer;
the preparation method of the fluorine-phosphorus composite gypsum self-leveling mortar comprises the following steps:
(1) Preparation of modified fluorophosphoric composite gypsum powder
Adding phosphogypsum, 20% of phosphogypsum by weight of fluorgypsum, 3.8% of slaked lime by weight of phosphogypsum and 1.2% of micro-powder graphite by weight of phosphogypsum into a ball mill, adding water as a ball milling medium according to a water-to-material ratio of 3:10, adding grinding balls according to a ball-to-material ratio of 5:1, and performing ball milling reaction for 10 hours at a rotating speed of 350rpm to hydrate gypsum powder to obtain dihydrate gypsum slurry.
Step two: pumping the dihydrate gypsum slurry into an autoclave, adding citric acid accounting for 1.2% of the phosphogypsum by weight as a crystal transferring agent, adding sodium dodecyl benzene sulfonate accounting for 0.8% of the phosphogypsum by weight, uniformly mixing, performing autoclave treatment at 120-130 ℃ for 7 hours, performing crystal transferring to obtain semi-hydrated gypsum feed liquid, performing centrifugal dehydration, washing and drying on the feed liquid, adding liquid nitrile rubber accounting for 2% of the dry gypsum feed material by weight and 400-mesh micro powder graphite accounting for 2 hours, and grinding.
(2) According to the formula amount, adding modified fluorine phosphorus composite gypsum powder, fly ash cement, ethylene-vinyl acetate copolymer, slaked lime, silica fume powder and polycarboxylic acid high-performance water reducer into a high-speed mixer, mixing for 30min at a stirring speed of 800rpm, adding fine river sand and polypropylene short fibers, and continuously mixing for 10min at a stirring speed of 500rpm to obtain the modified fluorine phosphorus composite gypsum powder.
(3) The self-leveling performance of the obtained gypsum is tested by adopting a method in JC/T1023-2021 gypsum-based self-leveling mortar according to the water-cement ratio of 0.26:1, the fluidity of 30min is 215mm, the absolute dry breaking strength is 7.3MPa, the absolute dry compressive strength is 26.4MPa, no cracking exists, and the dimensional change rate is 0.035%. The water content after 5d was measured according to the method in ASTM4263, and was 0.34%. The peel strength of the PVC plastic floor and the self-leveling base material (the glue adopts neoprene) is 7.9N/cm according to the GB 2792-2014 method.
Comparative example 1
The preparation method of the fluorophosphite self-leveling mortar provided in the embodiment 2 is characterized in that modified fluorophosphite powder is prepared by adopting the following method:
Adding phosphogypsum, fluorgypsum and slaked lime into a ball mill, adding water as a ball milling medium, and performing ball milling reaction for 8 hours at a ball ratio of 5:1 and a rotating speed of 500rpm to obtain dihydrate gypsum slurry. The adding amount of the fluorine gypsum is 20% of the weight of the phosphogypsum, the using amount of the slaked lime is 3.8% of the weight of the phosphogypsum, and the ratio of the material to the water is 3:10;
step two: pumping the dihydrate gypsum slurry into an autoclave, adding citric acid accounting for 1.2% of the phosphogypsum weight as a crystal transferring agent, adding sodium dodecyl benzene sulfonate accounting for 0.8% of the phosphogypsum weight, uniformly mixing, performing autoclave treatment at 120-130 ℃ for 7 hours, performing crystal transferring to obtain semi-hydrated gypsum feed liquid, and performing centrifugal dehydration, washing, drying and grinding on the feed liquid for 2 hours.
The self-leveling performance of the obtained gypsum is tested by adopting a method in JC/T1023-2021 gypsum-based self-leveling mortar according to the water-cement ratio of 0.26:1, the fluidity for 30min is 212mm, the absolute dry breaking strength is 6.7MPa, the absolute dry compressive strength is 25.4MPa, no cracking is caused, and the dimensional change rate is 0.039%. The water content after 5 days was 0.84% and the water content after 10 days was 0.72% as measured by the method in ASTM 4263. The peel strength of the PVC plastic floor and the self-leveling base material (the glue adopts neoprene) is 2.4N/cm according to the GB 2792-2014 method.
Comparative example 2
The preparation method of the fluorophosphite self-leveling mortar provided in the embodiment 2 is characterized in that modified fluorophosphite powder is prepared by adopting the following method:
adding phosphogypsum, 20% of phosphogypsum by weight and 3.8% of slaked lime by weight into a ball mill, adding water as a ball milling medium according to a water-to-material ratio of 3:10, adding grinding balls according to a ball-to-material ratio of 5:1, and performing ball milling reaction for 8 hours at a rotating speed of 500rpm to hydrate gypsum powder to obtain dihydrate gypsum slurry.
Step two: pumping the dihydrate gypsum slurry into an autoclave, adding citric acid accounting for 1.2% of the phosphogypsum weight as a crystal transferring agent, adding sodium dodecyl benzene sulfonate accounting for 0.8% of the phosphogypsum weight, uniformly mixing, performing autoclave treatment at 120-130 ℃ for 7 hours, performing crystal transferring to obtain semi-hydrated gypsum feed liquid, performing centrifugal dehydration, washing and drying on the feed liquid, and adding liquid nitrile rubber accounting for 3.2% of the weight of the semi-hydrated gypsum into the obtained semi-hydrated gypsum for grinding for 2 hours.
The self-leveling performance of the obtained gypsum is tested by adopting a method in JC/T1023-2021 gypsum-based self-leveling mortar according to the water-cement ratio of 0.26:1, the fluidity of 30min is 210mm, the absolute dry breaking strength is 6.3MPa, the absolute dry compressive strength is 24.2MPa, no cracking is caused, and the dimensional change rate is 0.041%. The water content after 5 days was 0.79% and the water content after 10 days was 0.65% as measured in accordance with the method in ASTM 4263. The peel strength of the PVC plastic floor and the self-leveling base material (the glue adopts neoprene) is 8.4N/cm according to the GB 2792-2014 method.
Comparative example 3
The preparation method of the fluorophosphite self-leveling mortar provided in the embodiment 2 is characterized in that modified fluorophosphite powder is prepared by adopting the following method:
Adding phosphogypsum, 20% of phosphogypsum by weight of fluorgypsum, 3.8% of slaked lime by weight of phosphogypsum and 1.2% of micro-powder graphite by weight of phosphogypsum into a ball mill, adding water as a ball milling medium according to a water-to-material ratio of 3:10, adding grinding balls according to a ball-to-material ratio of 5:1, and performing ball milling reaction for 10 hours at a rotating speed of 350rpm to hydrate gypsum powder to obtain dihydrate gypsum slurry.
Step two: pumping the dihydrate gypsum slurry into an autoclave, adding citric acid accounting for 1.2% of the phosphogypsum by weight as a crystal transferring agent, adding sodium dodecyl benzene sulfonate accounting for 0.8% of the phosphogypsum by weight, uniformly mixing, performing autoclave treatment at 120-130 ℃ for 7 hours, performing crystal transferring to obtain semi-hydrated gypsum feed liquid, performing centrifugal dehydration, washing and drying on the feed liquid, adding liquid nitrile rubber accounting for 8% of the dry gypsum raw material by weight and 400-mesh micro powder graphite by weight, and grinding for 2 hours.
The obtained gypsum self-leveling is subjected to performance test by adopting a method in JC/T1023-2021 gypsum-based self-leveling mortar according to a water-cement ratio of 0.26:1, the fluidity is 218mm in 30min, the absolute dry breaking strength is 3.2MPa, and the absolute dry compression strength is 15.2MPa. The gypsum prepared by the method has poor self-leveling strength.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same; while the application has been described in detail with reference to the preferred embodiments, those skilled in the art will appreciate that: modifications and equivalents of some of the features of the specific embodiments of the present application may be made, and they are all included in the scope of the present application as claimed.
Claims (7)
1. The fluorine-phosphorus composite gypsum self-leveling agent is characterized by comprising the following raw materials in parts by weight: 80-85 parts of modified fluorophosphite composite gypsum powder, 5-10 parts of fly ash cement, 1-3 parts of redispersible emulsion powder, 0.5-2.5 parts of slaked lime, 2-8 parts of fine river sand, 1-2 parts of silica fume powder, 1-3 parts of polypropylene short fiber and 0.5-2 parts of water reducer;
The preparation method of the modified fluorophosphoric composite gypsum powder comprises the following steps:
Firstly, adding phosphogypsum, fluorgypsum, slaked lime and micro-powder graphite into a ball mill, adding water as a ball milling medium, and performing ball milling reaction for 5-20 hours at a ball-material ratio of 5-10:1 and a rotating speed of 300-500rpm to obtain dihydrate gypsum slurry;
Step two: pumping the dihydrate gypsum slurry into an autoclave, adding citric acid and sodium dodecyl benzene sulfonate, uniformly mixing, performing an autoclaved reaction for 5-10 hours at the temperature of 120-130 ℃ to finish crystal transformation to obtain a semi-hydrated gypsum feed liquid, centrifugally dehydrating, washing and drying the feed liquid, and adding liquid nitrile rubber and micro-powder graphite into the obtained semi-hydrated gypsum powder to perform grinding modification to obtain the product;
The adding amount of the fluorine gypsum in the first step is 10-20% of the weight of the phosphogypsum, the using amount of the slaked lime is 2-6% of the weight of the phosphogypsum, the using amount of the micro powder graphite is 1-2% of the weight of the phosphogypsum, and the material-water ratio is 2-4:10;
The use amount of the liquid nitrile rubber in the second step is 1-5% of the weight of the semi-hydrated gypsum powder, the granularity of the micro-powder graphite is 400 meshes, and the use amount of the micro-powder graphite is 0.3-0.8% of the weight of the semi-hydrated gypsum powder.
2. The fluorophosphoric composite gypsum self-leveling of claim 1, wherein said micronized graphite particles of step one have a particle size of 100-300 mesh.
3. The fluorophosphoric composite gypsum self-leveling agent according to claim 1, wherein the water reducing agent is a polycarboxylic acid high-performance water reducing agent or sulfamate-based high-efficiency water reducing agent.
4. The self-leveling fluorine phosphogypsum composite gypsum according to claim 1, wherein the phosphogypsum is a byproduct of phosphoric acid production from phosphorite, and the main components of the phosphogypsum are 20-70% of dihydrate gypsum and 2-8% of phosphoric acid.
5. The self-leveling fluorine-phosphorus composite gypsum according to claim 1, wherein the fluorine gypsum is industrial waste residue obtained after preparing hydrofluoric acid by a fluorite concentrated sulfuric acid method, and the main components of the fluorine-phosphorus composite gypsum are 85-95% of anhydrous calcium sulfate and 1-5% of calcium fluoride.
6. The method for preparing the fluorophosphoric composite gypsum self-leveling according to any one of claims 1 to 5, which is characterized in that the method comprises the following steps: according to the formula amount, adding the modified fluorine-phosphorus composite gypsum powder, fly ash cement, redispersible emulsion powder, slaked lime, silica fume powder and a water reducing agent into a high-speed mixer, uniformly mixing, and then adding the fine river sand and the polypropylene short fiber for continuous uniform mixing.
7. Use of the fluorophosphoric composite gypsum self-leveling of any one of claims 1-5 as a PVC plastic floor leveling substrate.
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| CN105482181A (en) * | 2015-12-15 | 2016-04-13 | 中冠电缆有限公司 | Oil-resistant and anti-cracking modification composite cis-polybutadiene cable material and preparing method thereof |
| CN105924118A (en) * | 2016-05-09 | 2016-09-07 | 马振义 | Phosphogypsum and fluorgypsum compounded machine coating mortar and preparation method thereof |
| CN112028504A (en) * | 2020-08-25 | 2020-12-04 | 湖州市菱湖三狮水泥有限公司 | Composite cement and preparation method thereof |
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| FR1432197A (en) * | 1964-05-01 | 1966-03-18 | Natural Rubber Producer S Res | Plaster-based composition |
| CN105482181A (en) * | 2015-12-15 | 2016-04-13 | 中冠电缆有限公司 | Oil-resistant and anti-cracking modification composite cis-polybutadiene cable material and preparing method thereof |
| CN105924118A (en) * | 2016-05-09 | 2016-09-07 | 马振义 | Phosphogypsum and fluorgypsum compounded machine coating mortar and preparation method thereof |
| CN112028504A (en) * | 2020-08-25 | 2020-12-04 | 湖州市菱湖三狮水泥有限公司 | Composite cement and preparation method thereof |
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