CN113716908A - Modified calcium sulfate whisker reinforced geopolymer and preparation method thereof - Google Patents
Modified calcium sulfate whisker reinforced geopolymer and preparation method thereof Download PDFInfo
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- CN113716908A CN113716908A CN202111196957.4A CN202111196957A CN113716908A CN 113716908 A CN113716908 A CN 113716908A CN 202111196957 A CN202111196957 A CN 202111196957A CN 113716908 A CN113716908 A CN 113716908A
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- calcium sulfate
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- geopolymer
- modified calcium
- whiskers
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical class [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 73
- 229920000876 geopolymer Polymers 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 48
- 239000003513 alkali Substances 0.000 claims abstract description 33
- 239000012190 activator Substances 0.000 claims abstract description 32
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 25
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims abstract description 25
- 235000019801 trisodium phosphate Nutrition 0.000 claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 20
- -1 phosphoric acid Trisodium modified calcium sulfate Chemical class 0.000 claims abstract description 14
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 235000019353 potassium silicate Nutrition 0.000 claims abstract description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 27
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 17
- 238000001723 curing Methods 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 16
- 229920000642 polymer Polymers 0.000 claims description 12
- 239000012744 reinforcing agent Substances 0.000 claims description 10
- 238000000465 moulding Methods 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000003828 vacuum filtration Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 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 3
- 238000000034 method Methods 0.000 claims description 3
- 239000003245 coal Substances 0.000 claims description 2
- 239000010881 fly ash Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 abstract description 4
- 238000005411 Van der Waals force Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 abstract description 3
- 235000019700 dicalcium phosphate Nutrition 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 238000005728 strengthening Methods 0.000 abstract 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004568 cement Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910018512 Al—OH Inorganic materials 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000007788 liquid 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
- 239000003607 modifier Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000011414 polymer cement Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229920001909 styrene-acrylic polymer Polymers 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
- C04B28/006—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 mineral polymers, e.g. geopolymers of the Davidovits type
-
- 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
- C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
- C04B14/38—Fibrous materials; Whiskers
- C04B14/383—Whiskers
-
- 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
- C04B7/00—Hydraulic cements
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/14—Cements containing slag
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
-
- 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
- C04B7/00—Hydraulic cements
- C04B7/24—Cements from oil shales, residues or waste other than slag
- C04B7/243—Mixtures thereof with activators or composition-correcting additives, e.g. mixtures of fly ash and alkali activators
-
- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
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- 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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/2015—Sulfate resistance
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- 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
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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Abstract
本发明公开了一种改性硫酸钙晶须增强地聚合物及其制备方法，所述改性硫酸钙晶须增强地聚合物包括如下重量份的原料：100份硅铝质原料，35‑80份碱激发剂，1‑3份增强剂；碱激发剂由0‑20份的氢氧化钠与80‑100份的模数为1.2‑3.4的水玻璃混合制备而成；所述增强剂为磷酸三钠改性硫酸钙晶须。本发明的磷酸三钠改性后的硫酸钙晶须，表面会附着单分子层的磷酸氢钙薄膜，从而降低了晶须间的范德华力，阻止了晶须的再团聚，使硫酸钙晶须能够均匀独立的分布在地聚合物基体中；同时，会在晶须表面形成的大量羟基(‑OH)，其羟基可参与地聚合物的缩聚反应，实现晶须与地聚合物的有效结合，本发明制备的地聚合物力学性能、耐高温和耐酸性能优良。
The invention discloses a modified calcium sulfate whisker-enhanced geopolymer and a preparation method thereof. The modified calcium sulfate whisker-enhanced geopolymer comprises the following raw materials in parts by weight: 100 parts of silicon-alumina raw materials, 35-80 parts by weight parts of alkali activator, 1-3 parts of strengthening agent; the alkali activator is prepared by mixing 0-20 parts of sodium hydroxide and 80-100 parts of water glass with a modulus of 1.2-3.4; the strengthening agent is phosphoric acid Trisodium modified calcium sulfate whiskers. The calcium sulfate whiskers modified by trisodium phosphate of the present invention have a monomolecular layer of calcium hydrogen phosphate film attached to the surface, thereby reducing the van der Waals force between the whiskers, preventing the re-agglomeration of the whiskers, and making the calcium sulfate whiskers It can be evenly and independently distributed in the geopolymer matrix; at the same time, a large number of hydroxyl groups (‑OH) will be formed on the surface of the whiskers, and their hydroxyl groups can participate in the polycondensation reaction of the geopolymer to realize the effective combination of the whiskers and the geopolymer, The geopolymer prepared by the invention has excellent mechanical properties, high temperature resistance and acid resistance.
Description
Technical Field
The invention relates to a geopolymer and a preparation method thereof, in particular to a geopolymer reinforced by modified calcium sulfate whiskers and a preparation method thereof.
Background
Geopolymers are a new class of high performance inorganic polymer cements, one of the most promising alkali-activated cements. Due to the special inorganic condensed three-dimensional oxide network structure, the geopolymer material has better high-temperature performance and mechanical performance than high-molecular materials, cement, ceramics and metals in many aspects. On the other hand, the energy consumption and the waste discharge amount of the preparation process of the geopolymer material are very low, and the geopolymer material is a sustainable-development green environment-friendly material. The geopolymer has many excellent properties, such as good mechanical properties, small shrinkage and expansion rate, corrosion resistance and remarkable heat insulation effect, and therefore, can be used as a cementing material to replace cement. However, when it is used as a cement substitute, it has problems of high brittleness and low fracture-compression ratio. And thus the application is limited.
In the prior art, many scholars have carried out modification research on geopolymers, for example, the Chinese patent application No. 201910537921.4 discloses a geopolymer toughened by styrene-acrylic emulsion and a preparation method thereof; the Chinese invention patent of application number 201810203132.2 discloses an epoxy resin toughened metakaolin-based polymer and a preparation method thereof; the chinese patent application No. 201611127977.5 discloses a chitosan modified geopolymer gelled material; the Chinese patent application No. 201910062137.2 discloses a super high toughness geopolymer and its preparation method, wherein the toughening agent is polyvinyl alcohol fiber; leather from a performance study of polyvinyl alcohol-modified geopolymer composites was published by yunity et al; and so on. The modifiers used in the above patents or articles are all polymer materials, but polymer materials have the defects of easy aging, no high temperature resistance and the like.
In addition, after the geopolymer is hydrated and hardened, a hardened body has more harmful holes with the hole diameter of 50-200 nm, so that not only is the strength influenced, but also the comprehensive performances such as frost resistance, durability and the like of the geopolymer are influenced, and the popularization and application of the geopolymer are restricted.
However, the micro-nano material has a very small size, a particle diameter of substantially less than 100 μm, a large specific surface area and a large surface energy, so that the acting force between particles (such as van der waals force, electrostatic force, liquid bridge force, and the like) is large relative to the gravity thereof, and the micro-nano material is stored in a natural state and often exists in an agglomerated form, so that the micro-nano material has more limitations in use.
The calcium sulfate whisker is a micron-sized short fiber, and is a novel inorganic toughening material with excellent performances such as high modulus, high strength, low defect, high melting point and the like. The reinforcing and toughening material has the characteristics of high length-diameter ratio of the traditional fiber, small size of the micro-nano material, low production and purchase cost and high cost performance. However, the whisker is easy to agglomerate and not easy to disperse, and how to realize surface modification of the whisker, reduce the surface energy of the whisker and reduce the molecular force among particles, the modified whisker can be dispersed in an alkaline solution, and can form good surface bonding with a geopolymer at the same time, and a space skeleton structure is better formed by being wrapped by a geopolymer matrix, which is a problem to be solved in application.
As described above, the present patent application has been made to solve the main problems of brittle polymers, poor durability, and difficulty in dispersion of whiskers, and to achieve good surface bonding between whiskers and geopolymers.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a geopolymer reinforced by modified calcium sulfate whiskers, which has high strength and good toughness and improves the dispersibility of the modified whiskers in the geopolymer; the invention also aims to provide a preparation method of the geopolymer reinforced by the modified calcium sulfate whiskers.
The technical scheme is as follows: the modified calcium sulfate whisker reinforced geopolymer comprises the following raw materials in parts by weight: 100 parts of a silicon-aluminum raw material, 35-80 parts of an alkali activator and 1-3 parts of a reinforcing agent; the alkali activator is prepared by mixing 0-20 parts of sodium hydroxide and 80-100 parts of water glass with the modulus of 1.2-3.4; the reinforcing agent is trisodium phosphate modified calcium sulfate whisker. The alkali activator is preferably prepared by mixing 20 parts of sodium hydroxide and 80 parts of water glass solution with the modulus of 1.2-3.4.
Further, the alumino-silica raw material is selected from any one or more of fly ash, metakaolin, coal gangue or slag.
Further, the preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: and adding calcium sulfate whiskers into the trisodium phosphate aqueous solution, uniformly mixing, carrying out vacuum filtration, washing, drying, grinding and granulating to obtain the trisodium phosphate modified calcium sulfate whiskers.
Furthermore, the concentration of the trisodium phosphate aqueous solution is 0.010-0.020mol/L, and the mass ratio of the trisodium phosphate aqueous solution to the calcium sulfate whisker is 200: 3-5.
The preparation method of the modified calcium sulfate whisker reinforced geopolymer comprises the following steps:
(1) mixing the silicon-aluminum raw material, the modified calcium sulfate whisker and the alkali activator, stirring at a low speed, and then stirring at a high speed to obtain slurry;
(2) and injecting the slurry into a mold for molding, then maintaining, demolding, and continuously maintaining at room temperature for 3-28 days to obtain the product.
Further, in the step (1), the rotation speed of the slow stirring is 10-50 r/min, and the time is 2-3 min.
Further, in the step (1), the rotation speed of the rapid stirring is 100-200 r/min, and the time is 2-3 min.
Further, in the step (2), the curing method before demolding is: curing for 20-30 h under the conditions of 20-50 ℃ and relative humidity of 90-95%.
The preparation principle of the trisodium phosphate modified calcium sulfate whisker is as follows: dissolving trisodium phosphate in deionized water will produce hydrolysis reaction to produce hydrogen phosphate radical (HPO)4 2-) (formula 1), the hydrogen phosphate radical is easy to generate ion substitution reaction with calcium sulfate on the surface of the whisker to replace SO4 2-And a calcium hydrogen phosphate film (formula 2) is formed on the surface of the whisker, and a large amount of hydroxyl (-OH) capable of participating in early reaction of the geopolymer is formed on the surface of the whisker. The schematic diagram of whisker modification is shown in figure 2. After inorganic modification, the surface of the whisker is activated, so that the whisker is easy to disperse in a geopolymer, and can participate in deconstruction-polycondensation reaction of the geopolymer, so that the connection strength of the whisker and the geopolymer is improved, and the modification effect of the whisker on the geopolymer is improved.
The invention takes a silicon-aluminum material as a main raw material, sodium silicate as an alkali activator and trisodium phosphate modified calcium sulfate whisker as a reinforcing agent. Calcium sulfate whisker modified by trisodium phosphate has the surface attached with monomolecular layer of calcium hydrogen phosphate (CaHPO)4) The film can reduce Van der Waals force among the whiskers, prevent the reunion of the calcium sulfate whiskers in the geopolymer matrix, and enable the calcium sulfate whiskers to be uniformly and independently distributed in the geopolymer matrix, and in addition, a large number of hydroxyl groups (-OH) formed on the surfaces of the whiskers can be subjected to hydrolytic polycondensation reaction with Si-OH and Al-OH generated before the polycondensation reaction of the geopolymer, so that the whiskers are effectively combined with the geopolymer, and the stability of the mechanical property of the modified whisker/geopolymer composite material is improved. The modified whiskers are uniformly dispersed in the geopolymer matrix, so that pores in the geopolymer are effectively filled, and meanwhile, the growth of cracks in the geopolymer is inhibited, and a bridging effect is achieved. In situ polymerizationWhen the object is subjected to the action of external force load, the crack grows to break or pull out the whisker, a large amount of energy is consumed, and the mechanical property of the geopolymer can be effectively improved. The calcium sulfate whisker has a high melting point of 1450 ℃, has good heat resistance and a low heat conductivity coefficient, and can absorb most of heat when a geopolymer is in a high-temperature environment, so that the influence of the environmental temperature on the geopolymer is reduced, and the heat resistance of the geopolymer composite material is improved. Because the calcium sulfate whisker contains SO4 2-In an acidic environment, can resist a part of SO4 2-Erosion of (2). The calcium sulfate whisker fills the pores of partial polymers, so that the porosity of the geopolymer is reduced, the Na element is slowly separated out, and the durability of the geopolymer in an acid environment is improved.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the modified whisker reinforced geopolymer has the advantages of good mechanical property, high temperature resistance and sulfate corrosion resistance, and effectively solves the problems of high brittleness, poor mechanical property and poor durability of the traditional geopolymer.
Drawings
FIG. 1 is a flow chart of the preparation of modified whiskers of the present invention;
figure 2 is a schematic model of the modification of whiskers of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
In the following examples, the main chemical composition of the alumino-silica feedstock is SiO2、Al2O3The silicon-aluminum ratio is 2.5; the balance being Fe2O3、CaO、MgO、Na2O、K2O、TiO2(ii) a Not limited thereto.
Example 1
A modified calcium sulfate whisker reinforced polymer comprises the following raw materials in parts by weight:
100 parts of a silicon-aluminum raw material, 60 parts of an alkali activator and 1 part of a reinforcing agent;
the preparation method of the alkali activator comprises the following steps: mixing 20 parts of sodium hydroxide and 80 parts of water glass with the modulus of 3.4, adjusting the concentration by using deionized water, stirring until sodium hydroxide solids are completely dissolved, and standing for 24 hours to obtain the alkali activator.
The preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: adding 15 parts of calcium sulfate whisker into 1000 parts of 0.010-concentration trisodium phosphate solution, placing the mixture on a magnetic stirrer, stirring for 5min, performing ultrasonic treatment for 5min to obtain uniform modified whisker mixed solution, performing vacuum filtration to obtain modified whisker powder cake, washing and filtering the modified whisker powder cake for 2 times by using pure water, placing the modified whisker powder cake in an oven at 120 ℃ for 24h, drying water, and grinding to obtain modified calcium sulfate whisker powder.
The preparation method of the modified calcium sulfate whisker reinforced geopolymer comprises the following steps:
(1) mixing a silicon-aluminum raw material, modified calcium sulfate whisker powder and an alkali activator, then stirring at a low speed (the rotating speed is 10r/min and the time is 2min), and then stirring at a high speed (the rotating speed is 100r/min and the time is 2min) to obtain slurry;
(2) and injecting the slurry into a mold for molding, curing for 24 hours at the temperature of 20 ℃ and the relative humidity of 90 percent, demolding, and continuously curing for 3 days at room temperature to obtain the product.
Example 2
A modified calcium sulfate whisker reinforced polymer comprises the following raw materials in parts by weight:
100 parts of a silicon-aluminum raw material, 60 parts of an alkali activator and 1.5 parts of a reinforcing agent;
the preparation method of the alkali activator comprises the following steps: mixing 20 parts of sodium hydroxide and 80 parts of water glass with the modulus of 3.4, adjusting the concentration by using deionized water, stirring until sodium hydroxide solids are completely dissolved, and standing for 24 hours to obtain the alkali activator.
The preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: adding 25 parts of calcium sulfate whisker into 1000 parts of 0.020-concentration trisodium phosphate solution, placing the mixture on a magnetic stirrer, stirring for 30min, performing ultrasonic treatment for 30min to obtain uniform modified whisker mixed solution, performing vacuum filtration to obtain modified whisker powder cake, washing and filtering the modified whisker powder cake for 3 times by using pure water, placing the modified whisker powder cake in a 120-DEG C drying oven for 48h, drying water, and grinding to obtain modified calcium sulfate whisker powder.
The preparation method of the modified calcium sulfate whisker reinforced geopolymer comprises the following steps:
(1) mixing a silicon-aluminum raw material, modified calcium sulfate whisker powder and an alkali activator, then stirring at a low speed (the rotating speed is 50r/min, the time is 2min), and then stirring at a high speed (the rotating speed is 200r/min, the time is 2min) to obtain slurry;
(2) and injecting the slurry into a mold for molding, curing for 24 hours at the temperature of 25 ℃ and the relative humidity of 95%, demolding, and continuously curing for 28 days at room temperature to obtain the high-strength high-toughness high-strength high-toughness high-strength steel.
Example 3
A modified calcium sulfate whisker reinforced polymer comprises the following raw materials in parts by weight:
100 parts of a silicon-aluminum raw material, 60 parts of an alkali activator and 2 parts of a reinforcing agent;
the preparation method of the alkali activator comprises the following steps: mixing 20 parts of sodium hydroxide and 80 parts of water glass with the modulus of 3.4, adjusting the concentration by using deionized water, stirring until sodium hydroxide solids are completely dissolved, and standing for 24 hours to obtain the alkali activator.
The preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: adding 20 parts of calcium sulfate whisker into 1000 parts of 0.015-concentration trisodium phosphate solution, placing the mixture on a magnetic stirrer, stirring for 20min, performing ultrasonic treatment for 20min to obtain uniform modified whisker mixed solution, performing vacuum filtration to obtain modified whisker powder cake, washing and filtering the modified whisker powder cake for 3 times by using pure water, placing the modified whisker powder cake in an oven at 120 ℃ for 36h, drying water, and grinding to obtain modified calcium sulfate whisker powder.
The preparation method of the modified calcium sulfate whisker reinforced geopolymer comprises the following steps:
(1) mixing a silicon-aluminum raw material, modified calcium sulfate whisker powder and an alkali activator, then stirring at a low speed (the rotating speed is 30r/min and the time is 2min), and then stirring at a high speed (the rotating speed is 150r/min and the time is 2min) to obtain slurry;
(2) and injecting the slurry into a mold for molding, curing for 24 hours at 23 ℃ under the condition that the relative humidity is 92%, demolding, and continuously curing for 14 days at room temperature to obtain the high-strength high-toughness high-strength high-toughness high-strength steel.
Example 4
A modified calcium sulfate whisker reinforced polymer comprises the following raw materials in parts by weight:
100 parts of a silicon-aluminum raw material, 60 parts of an alkali activator and 2.5 parts of a reinforcing agent;
the preparation method of the alkali activator comprises the following steps: mixing 20 parts of sodium hydroxide and 80 parts of water glass with the modulus of 3.4, adjusting the concentration by using deionized water, stirring until sodium hydroxide solids are completely dissolved, and standing for 24 hours to obtain the alkali activator.
The preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: same as in example 1.
The preparation method of the modified calcium sulfate whisker reinforced geopolymer comprises the following steps:
(1) mixing a silicon-aluminum raw material, modified calcium sulfate whisker powder and an alkali activator, stirring at a low speed (the rotating speed is 10-50 r/min, the time is 2min), and then stirring at a high speed (the rotating speed is 100-200 r/min, the time is 2min) to obtain slurry;
(2) and (3) injecting the slurry into a mold for molding, then curing for 24 hours at the temperature of 20-25 ℃ and the relative humidity of 90-95%, demolding, and continuously curing for 3-28 days at room temperature to obtain the high-strength high-toughness high-strength high-toughness.
Example 5
A modified calcium sulfate whisker reinforced polymer comprises the following raw materials in parts by weight:
100 parts of a silicon-aluminum raw material, 60 parts of an alkali activator and 3 parts of a reinforcing agent;
the preparation method of the alkali activator comprises the following steps: mixing 20 parts of sodium hydroxide and 80 parts of water glass with the modulus of 3.4, adjusting the concentration by using deionized water, stirring until sodium hydroxide solids are completely dissolved, and standing for 24 hours to obtain the alkali activator.
The preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: same as in example 2.
(1) Mixing a silicon-aluminum raw material, modified calcium sulfate whisker powder and an alkali activator, stirring at a low speed (the rotating speed is 10-50 r/min, the time is 2min), and then stirring at a high speed (the rotating speed is 100-200 r/min, the time is 2min) to obtain slurry;
(2) and injecting the slurry into a mold for molding, then curing for 24 hours at the temperature of 20-25 ℃ and the relative humidity of 90-95%, demolding, and continuously curing for 3-28 days at room temperature to obtain the high-strength high-toughness high-strength high-toughness high-.
Comparative example
A method for preparing a geopolymer: mixing and stirring a water glass solution (modulus is 3.3) and sodium hydroxide at room temperature in a weight ratio of 4:1 until the sodium hydroxide solid is completely dissolved, and standing for 24 hours to obtain an alkali activator; mixing 100 parts by weight of silicon-aluminum raw material and 60 parts by weight of alkali activator into slurry, injecting the slurry into a mold for molding, curing for 24 hours at the temperature of 25 ℃ and the relative humidity of more than 90%, demolding, and continuously curing for 3-28 days to obtain the geopolymer sample.
The flexural strength, compressive strength and flexural ratio of the geopolymers of examples and comparative examples after curing at 28d and 800 ℃ were as shown in Table 1 below.
TABLE 1 Strength
From table 1, compared with the comparative example, the compressive strength and the flexural strength of the geopolymer prepared by the example of the invention are obviously improved compared with the comparative example, the modified calcium sulfate whiskers are doped into the geopolymer in different doping amounts, the strength improvement is different, the flexural ratio can reflect the toughness of the product from the side, and the doping of the calcium sulfate whiskers obviously improves the toughness of the geopolymer from the flexural ratio. After calcination at 800 ℃, the compressive strength and the flexural strength of the geopolymer-based composite material of the embodiment of the invention are as high as 1 time of those of a comparison sample, which shows that the high temperature resistance is good.
Table 2 shows the pore structure parameters for example 1 and the control. It can be seen from table 2 that the harmful pores in the example samples after the modified calcium sulfate whiskers are incorporated are greatly reduced, thereby being beneficial to improving the strength and toughness of the geopolymer.
TABLE 2 pore structure parameters
The calcium sulfate whisker is doped to play a filling role, improve the macroscopic mechanical property of the geopolymer, improve the sulfate erosion resistance of the geopolymer and improve the durability of the geopolymer in an acid environment.
Claims (8)
1. The modified calcium sulfate whisker reinforced polymer is characterized by comprising the following raw materials in parts by weight: 100 parts of a silicon-aluminum raw material, 35-80 parts of an alkali activator and 1-3 parts of a reinforcing agent; the alkali activator is prepared by mixing 0-20 parts of sodium hydroxide and 80-100 parts of water glass with the modulus of 1.2-3.4; the reinforcing agent is trisodium phosphate modified calcium sulfate whisker.
2. The modified calcium sulfate whisker reinforced geopolymer of claim 1, wherein the silica-alumina raw material is selected from any one or more of fly ash, metakaolin, coal gangue or slag.
3. The modified calcium sulfate whisker reinforced polymer of claim 1, wherein the trisodium phosphate modified calcium sulfate whisker is prepared by the following method: and adding calcium sulfate whiskers into the trisodium phosphate aqueous solution, uniformly mixing, carrying out vacuum filtration, washing, drying, grinding and granulating to obtain the trisodium phosphate modified calcium sulfate whiskers.
4. The modified calcium sulfate whisker reinforced polymer as claimed in claim 3, wherein the concentration of the aqueous solution of trisodium phosphate is 0.010-0.020mol/L, and the mass ratio of the aqueous solution of trisodium phosphate to the calcium sulfate whiskers is 200: 3-5.
5. The method for preparing the modified calcium sulfate whisker reinforced polymer according to claims 1 to 4, characterized by comprising the following steps:
(1) mixing the silicon-aluminum raw material, the modified calcium sulfate whisker and the alkali activator, stirring at a low speed, and then stirring at a high speed to obtain slurry;
(2) and injecting the slurry into a mold for molding, then maintaining, demolding, and continuously maintaining at room temperature for 3-28 days to obtain the product.
6. The preparation method according to claim 5, wherein in the step (1), the rotation speed of the slow stirring is 10-50 r/min, and the time is 2-3 min.
7. The preparation method according to claim 5, wherein in the step (1), the rotation speed of the rapid stirring is 100-200 r/min, and the time is 2-3 min.
8. The production method according to claim 5, wherein in the step (2), the curing method before the mold release is: curing for 20-30 h under the conditions of 20-50 ℃ and relative humidity of 90-95%.
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| CN114988735A (en) * | 2022-06-27 | 2022-09-02 | 武汉理工大学 | A kind of method that utilizes low activity solid waste to prepare phosphoric acid base polymer |
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