WO2021056934A1 - Reinforced concrete internal curing high-water-absorption microsphere material and preparation method therefor - Google Patents
Reinforced concrete internal curing high-water-absorption microsphere material and preparation method therefor Download PDFInfo
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- WO2021056934A1 WO2021056934A1 PCT/CN2020/072209 CN2020072209W WO2021056934A1 WO 2021056934 A1 WO2021056934 A1 WO 2021056934A1 CN 2020072209 W CN2020072209 W CN 2020072209W WO 2021056934 A1 WO2021056934 A1 WO 2021056934A1
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- WIPO (PCT)
- Prior art keywords
- reinforced concrete
- stirring
- microsphere material
- internal curing
- superabsorbent
- Prior art date
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- 239000004005 microsphere Substances 0.000 title claims abstract description 51
- 239000000463 material Substances 0.000 title claims abstract description 50
- 239000011150 reinforced concrete Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000010521 absorption reaction Methods 0.000 title abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 34
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 25
- 229920001661 Chitosan Polymers 0.000 claims abstract description 17
- 229960000583 acetic acid Drugs 0.000 claims abstract description 17
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 17
- 235000010489 acacia gum Nutrition 0.000 claims abstract description 13
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229960002089 ferrous chloride Drugs 0.000 claims abstract description 11
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims abstract description 11
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 12
- 229920000084 Gum arabic Polymers 0.000 claims description 12
- 239000000205 acacia gum Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- MRIZMKJLUDDMHF-UHFFFAOYSA-N cumene;hydrogen peroxide Chemical compound OO.CC(C)C1=CC=CC=C1 MRIZMKJLUDDMHF-UHFFFAOYSA-N 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000002250 absorbent Substances 0.000 claims description 8
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 claims description 7
- 230000002745 absorbent Effects 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000000725 suspension Substances 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000002131 composite material Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- JNGZXGGOCLZBFB-IVCQMTBJSA-N compound E Chemical compound N([C@@H](C)C(=O)N[C@@H]1C(N(C)C2=CC=CC=C2C(C=2C=CC=CC=2)=N1)=O)C(=O)CC1=CC(F)=CC(F)=C1 JNGZXGGOCLZBFB-IVCQMTBJSA-N 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 230000000630 rising effect Effects 0.000 claims description 3
- 241000978776 Senegalia senegal Species 0.000 claims 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims 1
- 239000004568 cement Substances 0.000 abstract description 23
- 230000007704 transition Effects 0.000 abstract description 2
- 239000001785 acacia senegal l. willd gum Substances 0.000 abstract 1
- YQHLDYVWEZKEOX-UHFFFAOYSA-N cumene hydroperoxide Chemical compound OOC(C)(C)C1=CC=CC=C1 YQHLDYVWEZKEOX-UHFFFAOYSA-N 0.000 abstract 1
- 239000004567 concrete Substances 0.000 description 58
- 238000002156 mixing Methods 0.000 description 16
- 230000000694 effects Effects 0.000 description 11
- 230000036571 hydration Effects 0.000 description 10
- 238000006703 hydration reaction Methods 0.000 description 10
- 244000215068 Acacia senegal Species 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- JLDKGEDPBONMDR-UHFFFAOYSA-N calcium;dioxido(oxo)silane;hydrate Chemical compound O.[Ca+2].[O-][Si]([O-])=O JLDKGEDPBONMDR-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- -1 glutaric acid Aldehydes Chemical class 0.000 description 2
- 239000004574 high-performance concrete Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ZORQXIQZAOLNGE-UHFFFAOYSA-N 1,1-difluorocyclohexane Chemical compound FC1(F)CCCCC1 ZORQXIQZAOLNGE-UHFFFAOYSA-N 0.000 description 1
- JJMDTERTPNYIGZ-UHFFFAOYSA-N 2-cyclohexylacetaldehyde Chemical compound O=CCC1CCCCC1 JJMDTERTPNYIGZ-UHFFFAOYSA-N 0.000 description 1
- UWAOHFMOWBQIJH-UHFFFAOYSA-N 3-cyclopentylpropanal Chemical compound O=CCCC1CCCC1 UWAOHFMOWBQIJH-UHFFFAOYSA-N 0.000 description 1
- 240000007472 Leucaena leucocephala Species 0.000 description 1
- 235000010643 Leucaena leucocephala Nutrition 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- GPKFMIVTEHMOBH-UHFFFAOYSA-N cumene;hydrate Chemical compound O.CC(C)C1=CC=CC=C1 GPKFMIVTEHMOBH-UHFFFAOYSA-N 0.000 description 1
- 230000006196 deacetylation Effects 0.000 description 1
- 238000003381 deacetylation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 239000011372 high-strength concrete Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000001593 sorbitan monooleate Substances 0.000 description 1
- 235000011069 sorbitan monooleate Nutrition 0.000 description 1
- 229940035049 sorbitan monooleate Drugs 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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Images
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
- 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
- C04B14/02—Granular materials, e.g. microballoons
- C04B14/04—Silica-rich materials; Silicates
- C04B14/06—Quartz; Sand
- C04B14/062—Microsilica, e.g. colloïdal silica
-
- 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
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/24—Macromolecular compounds
- C04B24/26—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C04B24/2641—Polyacrylates; Polymethacrylates
-
- 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
- C04B40/0046—Premixtures of ingredients characterised by their processing, e.g. sequence of mixing the ingredients when preparing the premixtures
Definitions
- the invention relates to the field of building materials, to concrete internal curing materials, in particular to a reinforced concrete internal curing high water-absorbing microsphere material and a preparation method.
- SAP as a new type of internal curing material, with its unique water absorption and water retention properties, acts as a reservoir inside the concrete, accompanied by the difference in humidity, pressure and pH value between the inside and outside of SAP particles during the hydration process of cement It will gradually release the water to maintain the internal relative humidity of the cement-based composite material at a higher level. The subsequent hydration of the cementitious material will not stop due to lack of water.
- the early self-drying and shrinkage cracking phenomenon of the cement-based material It can be effectively relieved and controlled, and the negative impact on other properties of concrete is much lower than the former. Therefore, SAP has become an internal maintenance material that has been continuously researched and applied in recent years. However, due to the limited current technology, the influence of SAP on the strength of concrete is very controversial. In addition, after SAP is incorporated, the workability of concrete becomes worse, and it cannot be effectively controlled during the hydration process of cement concrete. The release rate of water.
- the purpose of the present invention is to provide a reinforced concrete internal curing superabsorbent microsphere material and a preparation method, which solves the problem of the existing absorbent material, which causes the strength of concrete to decrease on the basis of ensuring the water absorption performance.
- the present invention adopts the following technical solutions to achieve:
- a reinforced concrete internal curing super absorbent microsphere material which is characterized in that it is made of the following raw materials: nano silica, chitosan, glutaraldehyde, acacia, methacrylic acid, glacial acetic acid, cumene Hydrogen oxide, ferrous chloride and sodium ethoxide.
- the invention also has the following technical features:
- the average particle size of the nano-silica is 20 nm.
- the present invention also protects a method for preparing the reinforced concrete internal curing superabsorbent microsphere material, which adopts the above-mentioned formula of the reinforced concrete internal curing superabsorbent microsphere material.
- the method specifically includes the following steps:
- Step 1 Weigh the ingredients according to the formula weight
- Step 2 Disperse nano-silica in water, configure it into a nano-silica suspension with a mass concentration of 3%, and stir;
- Step 3 Dilute glacial acetic acid with water into a dilute solution of glacial acetic acid with a mass concentration of 1%;
- Step 4 Mix chitosan and gum arabic, add the dilute solution of glacial acetic acid with a mass concentration of 1% prepared in step 3, and stir to form a dilute acid solution A of chitosan and gum arabic;
- Step 5 add methacrylic acid to water, configure it as a dilute solution with a mass concentration of 15%, add sodium ethoxide and cool to room temperature, while continuing to stir, add cumene hydrogen peroxide and ferrous chloride to fully dissolve Then the mixture B is prepared;
- Step 6 add cyclopentane and Span 80 to the container, stir at constant temperature to form oil phase C;
- Step 7 adding the nano-silica suspension prepared in step 2 to oil phase C, protecting with inert gas, stirring at a constant temperature, and continuously stirring, adding the dilute acid solution A and glutaraldehyde prepared in step 4, liters Mix liquid D with rapid stirring;
- Step 8 adding the mixture B prepared in step 5 to the mixed solution D prepared in step 7 and reacting to obtain a compound E;
- step 9 the composite E prepared in step 8 is taken out, washed with a solvent, and after the solvent is volatilized, a reinforced concrete inner curing superabsorbent microsphere material is prepared.
- the stirring adopts magnetic stirring, and the stirring time is 20 minutes.
- step 4 the stirring adopts magnetic stirring, and the stirring time is 30 minutes.
- step 6 the constant temperature is a constant temperature water bath environment of 30°C; the stirring is 200 r/min for 20 minutes.
- Span 80 is 5% to 8% of the mass fraction of cyclopentane.
- step 7 the inert gas protection is nitrogen; the constant temperature is 40°C constant temperature water bath environment; the stirring is 200r/min stirring for 10min; the rising speed stirring is 400r/min stirring for 30min .
- the temperature is controlled between 40°C and 45°C during the whole process of the reaction, and the reaction time is 6h.
- step 9 the solvent is absolute ethanol, and the washing is performed 3 to 5 times.
- the present invention has the following technical effects:
- the nano-silica component in the reinforced concrete internal curing superabsorbent microspheres provided by the present invention has a spherical, flocculent and net-like quasi-particle structure, which can not only provide concrete internal curing superabsorbent microspheres
- the framework of nano-silica has pozzolanic activity and chemically reacts with calcium hydroxide (CH) to generate additional calcium silicate hydrate (CSH).
- CSH is the main component to enhance the strength and density of cement-based hardened paste. Due to its pozzolanic activity, silica particles reduce the content of Ca(OH) 2 in the slurry and its grain size.
- the nucleation effect promotes the formation of CSH gels from C 3 S and C 2 S, and the filling effect makes it as a nano-filler. Fill the gaps between CSH gels. Therefore, the pozzolanic activity, nucleation effect and filling effect of nano-silica can promote the early hydration of cement, improve the transition zone between cement paste and aggregate, modify the internal microstructure of cement-based materials, reduce porosity, and improve mechanical properties .
- the chitosan molecule in the reinforced concrete internal curing superabsorbent microspheres provided by the present invention is a natural polymer with active amino groups in the structure and high chemical activity.
- the structure contains a large number of hydrophilic groups, which will swell to a certain extent in a solution with high water content, which can not only provide a network skeleton for the graft polymerization of organic monomers during the synthesis process of superabsorbent microspheres for curing in concrete, but also Improve the degree of polymerization of the polymerization reaction and increase the liquid absorption rate of the internally cured super absorbent microspheres.
- Glutaraldehyde can undergo a cross-linking reaction with glutaraldehyde, and the cross-linking reaction mainly occurs between molecules and also occurs within molecules.
- the cross-linked product is stable and generally not easy to dissolve.
- chitosan has good emulsification, film-forming properties and spheroidizing properties, which can effectively mention the synthesis effect of curing superabsorbent microspheres in concrete.
- the organic monomer methacrylic acid in the reinforced concrete internal curing superabsorbent microspheres provided by the present invention is continuously grafted and polymerized, and the nano-silica is continuously filled and packaged, which can significantly improve the internal curing material Aspiration rate.
- the excellent liquid absorption and storage effects can more effectively adjust the humidity distribution inside the concrete to a certain extent, ensure the water demand of the concrete in the hydration process, and promote the secondary cement and mineral admixtures. Hydration.
- the second time can effectively improve the hydration degree of cement-based materials and optimize the internal pores of concrete. Therefore, the preparation of reinforced concrete internal curing superabsorbent microspheres made by the present invention greatly contributes to the strength, durability and service life of cement concrete.
- Fig. 1 is an SEM image of the reinforced concrete internal curing superabsorbent microsphere material of the present invention.
- Span 80 namely sorbitan monooleate.
- the average particle size of nano silica is 20nm, the silica content is ⁇ 99%, the specific surface area is 150-200m 2 /g, and the pH is 4-7.
- the chitosan is food grade, and the degree of deacetylation is 80% to 90%.
- This example provides a reinforced concrete internal curing superabsorbent microsphere material, in parts by weight, including the following raw materials: 8% nano silica, 20% chitosan, 30% glutaric acid Aldehydes, 5% gum arabic, 25% methacrylic acid, 3.3% glacial acetic acid, 0.5% cumene hydrogen peroxide, 0.2% ferrous chloride, 8% sodium ethoxide.
- Step 1 Weigh the ingredients according to the formula weight
- Step 2 Disperse nano-silica in water, configure it into a nano-silica suspension with a mass concentration of 3%, and stir;
- the stirring adopts magnetic stirring, and the stirring time is 20 minutes.
- Step 3 Dilute glacial acetic acid with water into a dilute solution of glacial acetic acid with a mass concentration of 1%;
- Step 4 Mix chitosan and gum arabic, add the dilute solution of glacial acetic acid with a mass concentration of 1% prepared in step 3, and stir to form a dilute acid solution A of chitosan and gum arabic;
- step 4 the stirring adopts magnetic stirring, and the stirring time is 30 minutes.
- Step 5 add methacrylic acid to water, configure it as a dilute solution with a mass concentration of 15%, add sodium ethoxide and cool to room temperature, while continuing to stir, add cumene hydrogen peroxide and ferrous chloride to fully dissolve Then the mixture B is prepared;
- Step 6 add cyclopentane and Span 80 to the container, stir at constant temperature to form oil phase C;
- step 6 the constant temperature is a constant temperature water bath environment of 30°C; the stirring is 200 r/min for 20 minutes.
- Span 80 is 5% to 8% of the mass fraction of cyclopentane.
- Step 7 adding the nano-silica suspension prepared in step 2 to oil phase C, protecting with inert gas, stirring at a constant temperature, and continuously stirring, adding the dilute acid solution A and glutaraldehyde prepared in step 4, liters Mix liquid D with rapid stirring;
- step 7 the inert gas protection is nitrogen; the constant temperature is 40°C constant temperature water bath environment; the stirring is 200r/min stirring for 10min; the rising speed stirring is 400r/min stirring for 30min .
- Step 8 adding the mixture B prepared in step 5 to the mixed solution D prepared in step 7 and reacting to obtain a compound E;
- the temperature is controlled between 40°C and 45°C during the whole process of the reaction, and the reaction time is 6h.
- step 9 the composite E prepared in step 8 is taken out, washed with a solvent, and after the solvent is volatilized, a reinforced concrete inner curing superabsorbent microsphere material is prepared.
- step 9 the solvent is absolute ethanol, and the washing is performed 3 to 5 times.
- the SEM image of the reinforced concrete internal curing superabsorbent microsphere material prepared in this example is shown in FIG. 1.
- the mixing amount is 0.2% of the cement mixing amount.
- the 7d compressive strength of the resulting concrete is the benchmark concrete strength. 110%, 28d compressive strength is 123% of the benchmark concrete strength, the fluidity of 60min concrete is increased by 18% compared to the benchmark concrete, and the autogenous shrinkage of 28d concrete is reduced by 65% compared to the benchmark concrete.
- This example provides a reinforced concrete internal curing super absorbent microsphere material, in parts by weight, including the following raw materials: 9% nano silica, 18% chitosan, 25% glutaric acid Aldehydes, 4.4% gum arabic, 30% methacrylic acid, 5% glacial acetic acid, 0.4% cumene hydrogen peroxide, 0.2% ferrous chloride, 8% sodium ethoxide.
- the preparation method of the reinforced concrete inner-curing superabsorbent microsphere material of this embodiment is the same as the preparation method of the reinforced concrete inner-curing superabsorbent microsphere material in Example 1.
- the SEM image of the reinforced concrete internal curing superabsorbent microsphere material prepared in this example is shown in FIG. 1.
- the mixing amount is 1.8% of the cement mixing amount
- the 7d compressive strength of the resulting concrete is the benchmark concrete strength 108%
- 28d compressive strength is 123% of the benchmark concrete strength
- the fluidity of 60min concrete is increased by 20% compared to the benchmark concrete
- the autogenous shrinkage of 28d concrete is reduced by 60% compared to the benchmark concrete.
- This example provides a reinforced concrete internal curing superabsorbent microsphere material, in parts by weight, including the following raw materials: 10% nano silica, 19% chitosan, 28% glutaric acid Aldehydes, 4% gum arabic, 27% methacrylic acid, 3.3% glacial acetic acid, 0.5% cumene hydrogen peroxide, 0.2% ferrous chloride, 8% sodium ethoxide.
- the preparation method of the reinforced concrete inner-curing superabsorbent microsphere material of this embodiment is the same as the preparation method of the reinforced concrete inner-curing superabsorbent microsphere material in Example 1.
- the SEM image of the reinforced concrete internal curing superabsorbent microsphere material prepared in this example is shown in FIG. 1.
- the mixing amount is 0.25% of the cement mixing amount
- the 7d compressive strength of the resulting concrete is the benchmark concrete strength 112%
- 28d compressive strength is 128% of the benchmark concrete strength
- the fluidity of 60min concrete is increased by 30% relative to the benchmark concrete
- the autogenous shrinkage of the 28d concrete is reduced by 69% relative to the benchmark concrete.
- This example provides a reinforced concrete internal curing superabsorbent microsphere material, in parts by weight, including the following raw materials: 10% nano-silica, 15% chitosan, 30% glutaric acid Aldehydes, 4.4% gum arabic, 30% methacrylic acid, 5% glacial acetic acid, 0.5% cumene hydrogen peroxide, 0.1% ferrous chloride, 5% sodium ethoxide.
- the preparation method of the reinforced concrete inner-curing superabsorbent microsphere material of this embodiment is the same as the preparation method of the reinforced concrete inner-curing superabsorbent microsphere material in Example 1.
- the SEM image of the reinforced concrete internal curing superabsorbent microsphere material prepared in this example is shown in FIG. 1.
- the mixing amount is 0.3% of the cement mixing amount
- the 7d compressive strength of the resulting concrete is the benchmark concrete strength 102%
- 28d compressive strength is 130% of the benchmark concrete strength
- the fluidity of 60min concrete is increased by 35% relative to the benchmark concrete
- the autogenous shrinkage of 28d concrete is reduced by 70% compared to the benchmark concrete.
- the high-absorbent microspheres cured in the strong concrete can significantly increase the compressive strength of the concrete.
- the 28d compressive strength is more than 120% of the benchmark concrete strength.
- the fluidity of 60min concrete has also been significantly improved.
- the internal curing material can also greatly reduce the autogenous shrinkage of concrete. Therefore, the strong concrete internal curing superabsorbent microspheres of the present invention have good applicability, can effectively solve the problems in the current concrete curing process, and have broad application prospects.
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- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
Disclosed are a reinforced concrete internal curing high-water-absorption microsphere material and a preparation method therefor. The microsphere material is prepared from the following raw materials: nano silica, chitosan, glutaraldehyde, arabic gum, methacrylic acid, glacial acetic acid, isopropyl benzene hydroperoxide, ferrous chloride and sodium ethoxide. Same modifies the microstructure inside a cement-based material by improving a transition region between a cement paste and an aggregate, whereby the porosity is reduced and the mechanical properties are improved.
Description
本发明涉及建筑材料领域，涉及混凝土内养护材料，具体涉及一种增强型混凝土内养护高吸水微球材料及制备方法。The invention relates to the field of building materials, to concrete internal curing materials, in particular to a reinforced concrete internal curing high water-absorbing microsphere material and a preparation method.
混凝土凭借其优良的力学性能、较高的耐久性等优点，以及显著的经济、社会和环境效益，被广泛应用在跨海大桥、高速铁路、高层建筑等工程中。然而，随着我国经济高速发展，新的建筑风格对混凝土提出了更高的要求。现在的建筑讲求更高、更大、寿命长，这就要求混凝土的耐久性要更好，承载能力更大。高性能混凝土较普通混凝土而言，其很多性能指标都高于普通混凝土，但通常高性能混凝土均具有低水胶比、掺加高活性矿物掺合料等特性，导致其早期水化快，内部相对湿度下降快。同时由于其自身密实的结构，外部养护水很难进入其内部，后期水泥水化所需水分无法得到补充，导致水泥基复合材料化学收缩、自干燥和自收缩现象尤为严重，大大提高了混凝土早期开裂的敏感性，在工程应用中造成巨大障碍。Relying on its excellent mechanical properties, high durability and other advantages, as well as significant economic, social and environmental benefits, concrete is widely used in sea-crossing bridges, high-speed railways, high-rise buildings and other projects. However, with the rapid development of my country's economy, new architectural styles have put forward higher requirements for concrete. Today's buildings demand higher, larger, and long life, which requires concrete to have better durability and greater bearing capacity. Compared with ordinary concrete, high-performance concrete has many performance indicators higher than ordinary concrete. However, high-performance concrete usually has the characteristics of low water-binder ratio and high-active mineral admixtures, which causes its early hydration to be fast and internal The relative humidity drops quickly. At the same time, due to its own compact structure, it is difficult for external curing water to enter the interior, and the water required for later cement hydration cannot be replenished, which leads to severe chemical shrinkage, self-drying and self-shrinkage of cement-based composites, which greatly improves the early concrete The susceptibility to cracking creates huge obstacles in engineering applications.
基于当代混凝土自身结构特点，目前普遍研究认为在混凝土内部提供水源供其后期水化，即内养护技术是针对高强混凝土早期收缩开裂问题最可行有效的方法。2003年国际材料与结构研究实验联合会RILEM将内养护定义为“向混凝土内引入能够作为养护的水”，并将养护材料分为两类——轻骨料(LAW)和高吸水树脂(SAP)。SAP作为一种新型的内养护材料，凭借其独特的吸水性能和保水性能，在混凝土内部起到一个蓄水池的作用，伴随着水泥水化过程中 SAP颗粒内外湿度差、压力差及pH值等的变化，其会逐步释水使水泥基复合材料的内部相对湿度维持在较高水平，后续胶凝材料的水化不会因缺水而停止，水泥基材料早期自干燥和收缩的开裂现象能得到有效缓解和控制，同时对混凝土其他性能的消极影响远低于前者。因而SAP成为近年来不断研究和应用的内养护材料。但因为目前的技术有限，SAP的掺入对混凝土强度的影响存在很大的争议性，另外，SAP的掺入后，混凝土的工作性变差，且不能有效控制其在水泥混凝土水化过程中的释水速率。Based on the structural characteristics of contemporary concrete, it is generally believed that providing water inside the concrete for later hydration, that is, the internal curing technology is the most feasible and effective method for the early shrinkage and cracking of high-strength concrete. In 2003, the International Federation of Materials and Structure Research and Experiments RILEM defined internal curing as "introducing water that can be used as curing into concrete", and divided the curing materials into two categories-light aggregate (LAW) and super absorbent resin (SAP) ). SAP, as a new type of internal curing material, with its unique water absorption and water retention properties, acts as a reservoir inside the concrete, accompanied by the difference in humidity, pressure and pH value between the inside and outside of SAP particles during the hydration process of cement It will gradually release the water to maintain the internal relative humidity of the cement-based composite material at a higher level. The subsequent hydration of the cementitious material will not stop due to lack of water. The early self-drying and shrinkage cracking phenomenon of the cement-based material It can be effectively relieved and controlled, and the negative impact on other properties of concrete is much lower than the former. Therefore, SAP has become an internal maintenance material that has been continuously researched and applied in recent years. However, due to the limited current technology, the influence of SAP on the strength of concrete is very controversial. In addition, after SAP is incorporated, the workability of concrete becomes worse, and it cannot be effectively controlled during the hydration process of cement concrete. The release rate of water.
发明内容Summary of the invention
针对现有技术存在的不足，本发明的目的在于，提供一种增强型混凝土内养护高吸水微球材料及制备方法，解决现有的吸收材料，在保证吸水性能的基础上，导致混凝土强度下降的技术问题。In view of the shortcomings of the prior art, the purpose of the present invention is to provide a reinforced concrete internal curing superabsorbent microsphere material and a preparation method, which solves the problem of the existing absorbent material, which causes the strength of concrete to decrease on the basis of ensuring the water absorption performance. Technical issues.
为了解决上述技术问题，本发明采用如下技术方案予以实现：In order to solve the above technical problems, the present invention adopts the following technical solutions to achieve:
一种增强型混凝土内养护高吸水微球材料，其特征在于，包括以下原料制成：纳米二氧化硅、壳聚糖、戊二醛、阿拉伯胶、甲基丙烯酸、冰乙酸、异丙苯过氧化氢、氯化亚铁和乙醇钠。A reinforced concrete internal curing super absorbent microsphere material, which is characterized in that it is made of the following raw materials: nano silica, chitosan, glutaraldehyde, acacia, methacrylic acid, glacial acetic acid, cumene Hydrogen oxide, ferrous chloride and sodium ethoxide.
具体的，以重量份数计，包括以下原料制成：8％～10％的纳米二氧化硅，15％～20％的壳聚糖，25％～30％的戊二醛，4％～5％的阿拉伯胶，25％～30％的甲基丙烯酸，3.3％～5％的冰乙酸，0.4％～0.5％的异丙苯过氧化氢，0.1％～0.2％的氯化亚铁，5％～8％的乙醇钠，原料的重量份数之和为100％。Specifically, in parts by weight, including the following raw materials: 8%-10% nano silica, 15%-20% chitosan, 25%-30% glutaraldehyde, 4%-5 % Gum arabic, 25%-30% methacrylic acid, 3.3%-5% glacial acetic acid, 0.4%-0.5% cumene hydrogen peroxide, 0.1%-0.2% ferrous chloride, 5% ~8% of sodium ethoxide, the total weight of raw materials is 100%.
本发明还具有如下技术特征：The invention also has the following technical features:
所述的纳米二氧化硅的平均粒径为20nm。The average particle size of the nano-silica is 20 nm.
本发明还保护一种增强型混凝土内养护高吸水微球材料的制备方法，该方法采用如上所述的增强型混凝土内养护高吸水微球材料的配方。The present invention also protects a method for preparing the reinforced concrete internal curing superabsorbent microsphere material, which adopts the above-mentioned formula of the reinforced concrete internal curing superabsorbent microsphere material.
该方法具体包括以下步骤：The method specifically includes the following steps:
步骤一，按配方重量称取各原料；Step 1: Weigh the ingredients according to the formula weight;
步骤二，将纳米二氧化硅分散于水中，将其配置成质量浓度为3％的纳米二氧化硅悬浮液，搅拌；Step 2: Disperse nano-silica in water, configure it into a nano-silica suspension with a mass concentration of 3%, and stir;
步骤三，将冰乙酸用水稀释成质量浓度为1％的冰乙酸稀溶液；Step 3: Dilute glacial acetic acid with water into a dilute solution of glacial acetic acid with a mass concentration of 1%;
步骤四，将壳聚糖和阿拉伯胶混合，加入步骤三制得的质量浓度为1％的冰乙酸稀溶液，搅拌形成壳聚糖和阿拉伯胶的稀酸溶液A；Step 4: Mix chitosan and gum arabic, add the dilute solution of glacial acetic acid with a mass concentration of 1% prepared in step 3, and stir to form a dilute acid solution A of chitosan and gum arabic;
步骤五，将甲基丙烯酸加入水中，配置成质量浓度为15％的稀溶液，加入乙醇钠并冷却至室温，持续搅拌的过程中，加入异丙苯过氧化氢和氯化亚铁，充分溶解后制得混合物B；Step 5, add methacrylic acid to water, configure it as a dilute solution with a mass concentration of 15%, add sodium ethoxide and cool to room temperature, while continuing to stir, add cumene hydrogen peroxide and ferrous chloride to fully dissolve Then the mixture B is prepared;
步骤六，将环戊烷和Span 80加入容器中，恒温搅拌形成油相C；Step 6, add cyclopentane and Span 80 to the container, stir at constant temperature to form oil phase C;
步骤七，将步骤二制得的纳米二氧化硅悬浮液加入至油相C，惰性气体保护，恒温搅拌，持续搅拌的过程中，加入步骤四制得的稀酸溶液A和戊二醛，升速搅拌制得混合液D；Step 7, adding the nano-silica suspension prepared in step 2 to oil phase C, protecting with inert gas, stirring at a constant temperature, and continuously stirring, adding the dilute acid solution A and glutaraldehyde prepared in step 4, liters Mix liquid D with rapid stirring;
步骤八，将步骤五制得的混合物B加入至步骤七制得的混合液D中反应后制得复合物E；Step 8, adding the mixture B prepared in step 5 to the mixed solution D prepared in step 7 and reacting to obtain a compound E;
步骤九，将步骤八制得的复合物E取出，用溶剂洗涤，溶剂挥发后制得增强型混凝土内养护高吸水微球材料。In step 9, the composite E prepared in step 8 is taken out, washed with a solvent, and after the solvent is volatilized, a reinforced concrete inner curing superabsorbent microsphere material is prepared.
步骤二中，所述的搅拌采用磁力搅拌，搅拌时间为20mim。In the second step, the stirring adopts magnetic stirring, and the stirring time is 20 minutes.
步骤四中，所述的搅拌采用磁力搅拌，搅拌时间为30mim。In step 4, the stirring adopts magnetic stirring, and the stirring time is 30 minutes.
步骤六中，所述的恒温为30℃的恒温水浴环境；所述的搅拌为以200r/min搅拌20min。In step 6, the constant temperature is a constant temperature water bath environment of 30°C; the stirring is 200 r/min for 20 minutes.
步骤六中，所述的油相C中，Span 80为环戊烷质量分数的5％～8％。In step 6, in the oil phase C, Span 80 is 5% to 8% of the mass fraction of cyclopentane.
步骤七中，所述的惰性气体保护为通氮气；所述的恒温为40℃恒温水浴环境；所述的搅拌为以200r/min搅拌10min；所述的升速搅拌为以400r/min搅拌30min。In step 7, the inert gas protection is nitrogen; the constant temperature is 40°C constant temperature water bath environment; the stirring is 200r/min stirring for 10min; the rising speed stirring is 400r/min stirring for 30min .
步骤八中，所述的反应的整个过程中温度控制在40～45℃之间，反应时间为6h。In the eighth step, the temperature is controlled between 40°C and 45°C during the whole process of the reaction, and the reaction time is 6h.
步骤九中，所述的溶剂为无水乙醇，洗涤3～5次。In step 9, the solvent is absolute ethanol, and the washing is performed 3 to 5 times.
本发明与现有技术相比，具有如下技术效果：Compared with the prior art, the present invention has the following technical effects:
(Ⅰ)本发明所提供的增强型混凝土内养护高吸水微球中纳米二氧化硅成分本身呈微结构为球形，絮状和网状的准颗粒结构，不仅可以提供混凝土内养护高吸水微球的骨架，纳米二氧化硅具有火山灰活性，与氢氧化钙(CH)发生化学反应，生成额外的水化硅酸钙(C-S-H)，C-S-H为增强水泥基硬化浆体强度及密度的主要成分。二氧化硅颗粒由于其火山灰活性降低了浆体中Ca(OH)
2的含量及其晶粒尺度，晶核效应促进了C
3S及C
2S生成C-S-H凝胶，填充效应使其作为纳米填料填充于C-S-H凝胶之间的空隙。因此，纳米二氧化硅的火山灰活性、晶核效应和填充效应能够促进水泥早期水化、改善水泥浆体与骨料的过渡区，修饰水泥基材料内部的微观结构，降低孔隙率，提高力学性能。
(I) The nano-silica component in the reinforced concrete internal curing superabsorbent microspheres provided by the present invention has a spherical, flocculent and net-like quasi-particle structure, which can not only provide concrete internal curing superabsorbent microspheres The framework of nano-silica has pozzolanic activity and chemically reacts with calcium hydroxide (CH) to generate additional calcium silicate hydrate (CSH). CSH is the main component to enhance the strength and density of cement-based hardened paste. Due to its pozzolanic activity, silica particles reduce the content of Ca(OH) 2 in the slurry and its grain size. The nucleation effect promotes the formation of CSH gels from C 3 S and C 2 S, and the filling effect makes it as a nano-filler. Fill the gaps between CSH gels. Therefore, the pozzolanic activity, nucleation effect and filling effect of nano-silica can promote the early hydration of cement, improve the transition zone between cement paste and aggregate, modify the internal microstructure of cement-based materials, reduce porosity, and improve mechanical properties .
(Ⅱ)本发明所提供的增强型混凝土内养护高吸水微球中的壳聚糖分子是一种天然高分子，结构中存在活泼的氨基，化学活性高好。结构中含有大量的亲水基团，在含水量高的溶液中都会有一定程度的溶胀，不仅可以为混凝土内养护高吸水微球合成过程中为有机单体的接枝聚合反应提供网络骨架，提高聚合反应的聚合度，增加内养护高吸水微球的吸液倍率。戊二醛可以与戊二醛发生交联反应，其交联反应主要发生在分子间，在分子内也有发生。交联化产物 性质稳定，一般不易溶解。另外，壳聚糖具有很好的乳化性、成膜性和成球性，可以有效的提到混凝土内养护高吸水微球的合成效果。(II) The chitosan molecule in the reinforced concrete internal curing superabsorbent microspheres provided by the present invention is a natural polymer with active amino groups in the structure and high chemical activity. The structure contains a large number of hydrophilic groups, which will swell to a certain extent in a solution with high water content, which can not only provide a network skeleton for the graft polymerization of organic monomers during the synthesis process of superabsorbent microspheres for curing in concrete, but also Improve the degree of polymerization of the polymerization reaction and increase the liquid absorption rate of the internally cured super absorbent microspheres. Glutaraldehyde can undergo a cross-linking reaction with glutaraldehyde, and the cross-linking reaction mainly occurs between molecules and also occurs within molecules. The cross-linked product is stable and generally not easy to dissolve. In addition, chitosan has good emulsification, film-forming properties and spheroidizing properties, which can effectively mention the synthesis effect of curing superabsorbent microspheres in concrete.
(Ⅲ)本发明所提供的增强型混凝土内养护高吸水微球中有机单体甲基丙烯酸不断的发生接枝、聚合，对纳米二氧化硅不断的进行填充包裹，可以显著提高内养护材料的吸液倍率。另外，较优异的吸液、蓄液作用，在一定程度上可以更为有效地调整混凝土内部的湿度分布，保证了混凝土在水化过程中的需水量，促进水泥和矿物掺合料的二次水化。二次可以有效提高水泥基材料的水化程度，优化混凝土的内部孔隙。因此将本发明制备增强型混凝土内养护高吸水微球不论是对水泥混凝土的强度、耐久性以及使用寿命等方面都有很大的贡献。(Ⅲ) The organic monomer methacrylic acid in the reinforced concrete internal curing superabsorbent microspheres provided by the present invention is continuously grafted and polymerized, and the nano-silica is continuously filled and packaged, which can significantly improve the internal curing material Aspiration rate. In addition, the excellent liquid absorption and storage effects can more effectively adjust the humidity distribution inside the concrete to a certain extent, ensure the water demand of the concrete in the hydration process, and promote the secondary cement and mineral admixtures. Hydration. The second time can effectively improve the hydration degree of cement-based materials and optimize the internal pores of concrete. Therefore, the preparation of reinforced concrete internal curing superabsorbent microspheres made by the present invention greatly contributes to the strength, durability and service life of cement concrete.
(Ⅳ)本发明的整个制备工艺流程也相对较为简单，不需要专业的技术人员操作指导，只需要按照本发明的叙述操作进行即可。(IV) The entire preparation process of the present invention is relatively simple, and does not require professional technical personnel to operate and guide, and only needs to operate according to the description of the present invention.
图1是本发明的增强型混凝土内养护高吸水微球材料SEM图。Fig. 1 is an SEM image of the reinforced concrete internal curing superabsorbent microsphere material of the present invention.
以下结合实施例对本发明的具体内容作进一步详细解释说明。The specific content of the present invention will be further explained in detail below in conjunction with the embodiments.
需要说明的是，本申请中：It should be noted that in this application:
Span 80，即山梨糖醇酐单油酸酯。Span 80, namely sorbitan monooleate.
纳米二氧化硅的平均粒径为20nm，二氧化硅含量≥99％，比表面积为150～200m
2/g，pH为4～7。
The average particle size of nano silica is 20nm, the silica content is ≥99%, the specific surface area is 150-200m 2 /g, and the pH is 4-7.
所述的壳聚糖为食品级，脱乙酰度为80％～90％。The chitosan is food grade, and the degree of deacetylation is 80% to 90%.
以下给出本发明的具体实施例，需要说明的是本发明并不局限于以下具体实施例，凡在本申请技术方案基础上做的等同变换均落入本发明的保护范围。Specific embodiments of the present invention are given below. It should be noted that the present invention is not limited to the following specific embodiments, and all equivalent transformations made on the basis of the technical solutions of the present application fall within the protection scope of the present invention.
实施例1：Example 1:
本实施例给出一种增强型混凝土内养护高吸水微球材料，以重量份数计，包括以下原料制成：8％的纳米二氧化硅，20％的壳聚糖，30％的戊二醛，5％的阿拉伯胶，25％的甲基丙烯酸，3.3％的冰乙酸，0.5％的异丙苯过氧化氢，0.2％的氯化亚铁，8％的乙醇钠。This example provides a reinforced concrete internal curing superabsorbent microsphere material, in parts by weight, including the following raw materials: 8% nano silica, 20% chitosan, 30% glutaric acid Aldehydes, 5% gum arabic, 25% methacrylic acid, 3.3% glacial acetic acid, 0.5% cumene hydrogen peroxide, 0.2% ferrous chloride, 8% sodium ethoxide.
本实施例的增强型混凝土内养护高吸水微球材料的制备方法，该方法具体包括以下步骤：The preparation method of the reinforced concrete inner curing super water-absorbing microsphere material of this embodiment specifically includes the following steps:
步骤一，按配方重量称取各原料；Step 1: Weigh the ingredients according to the formula weight;
步骤二，将纳米二氧化硅分散于水中，将其配置成质量浓度为3％的纳米二氧化硅悬浮液，搅拌；Step 2: Disperse nano-silica in water, configure it into a nano-silica suspension with a mass concentration of 3%, and stir;
步骤二中，所述的搅拌采用磁力搅拌，搅拌时间为20mim。In the second step, the stirring adopts magnetic stirring, and the stirring time is 20 minutes.
步骤三，将冰乙酸用水稀释成质量浓度为1％的冰乙酸稀溶液；Step 3: Dilute glacial acetic acid with water into a dilute solution of glacial acetic acid with a mass concentration of 1%;
步骤四，将壳聚糖和阿拉伯胶混合，加入步骤三制得的质量浓度为1％的冰乙酸稀溶液，搅拌形成壳聚糖和阿拉伯胶的稀酸溶液A；Step 4: Mix chitosan and gum arabic, add the dilute solution of glacial acetic acid with a mass concentration of 1% prepared in step 3, and stir to form a dilute acid solution A of chitosan and gum arabic;
步骤四中，所述的搅拌采用磁力搅拌，搅拌时间为30mim。In step 4, the stirring adopts magnetic stirring, and the stirring time is 30 minutes.
步骤五，将甲基丙烯酸加入水中，配置成质量浓度为15％的稀溶液，加入乙醇钠并冷却至室温，持续搅拌的过程中，加入异丙苯过氧化氢和氯化亚铁，充分溶解后制得混合物B；Step 5, add methacrylic acid to water, configure it as a dilute solution with a mass concentration of 15%, add sodium ethoxide and cool to room temperature, while continuing to stir, add cumene hydrogen peroxide and ferrous chloride to fully dissolve Then the mixture B is prepared;
步骤六，将环戊烷和Span 80加入容器中，恒温搅拌形成油相C；Step 6, add cyclopentane and Span 80 to the container, stir at constant temperature to form oil phase C;
步骤六中，所述的恒温为30℃的恒温水浴环境；所述的搅拌为以200r/min搅拌20min。In step 6, the constant temperature is a constant temperature water bath environment of 30°C; the stirring is 200 r/min for 20 minutes.
步骤六中，所述的油相C中，Span 80为环戊烷质量分数的5％～8％。In step 6, in the oil phase C, Span 80 is 5% to 8% of the mass fraction of cyclopentane.
步骤七，将步骤二制得的纳米二氧化硅悬浮液加入至油相C，惰性气体保护，恒温搅拌，持续搅拌的过程中，加入步骤四制得的稀酸溶液A和戊二醛，升速搅拌制得混合液D；Step 7, adding the nano-silica suspension prepared in step 2 to oil phase C, protecting with inert gas, stirring at a constant temperature, and continuously stirring, adding the dilute acid solution A and glutaraldehyde prepared in step 4, liters Mix liquid D with rapid stirring;
步骤七中，所述的惰性气体保护为通氮气；所述的恒温为40℃恒温水浴环境；所述的搅拌为以200r/min搅拌10min；所述的升速搅拌为以400r/min搅拌30min。In step 7, the inert gas protection is nitrogen; the constant temperature is 40°C constant temperature water bath environment; the stirring is 200r/min stirring for 10min; the rising speed stirring is 400r/min stirring for 30min .
步骤八，将步骤五制得的混合物B加入至步骤七制得的混合液D中反应后制得复合物E；Step 8, adding the mixture B prepared in step 5 to the mixed solution D prepared in step 7 and reacting to obtain a compound E;
步骤八中，所述的反应的整个过程中温度控制在40～45℃之间，反应时间为6h。In the eighth step, the temperature is controlled between 40°C and 45°C during the whole process of the reaction, and the reaction time is 6h.
步骤九，将步骤八制得的复合物E取出，用溶剂洗涤，溶剂挥发后制得增强型混凝土内养护高吸水微球材料。In step 9, the composite E prepared in step 8 is taken out, washed with a solvent, and after the solvent is volatilized, a reinforced concrete inner curing superabsorbent microsphere material is prepared.
步骤九中，所述的溶剂为无水乙醇，洗涤3～5次。In step 9, the solvent is absolute ethanol, and the washing is performed 3 to 5 times.
本实施例制得的增强型混凝土内养护高吸水微球材料的SEM图如图1所示。使用时，直接将该增强型混凝土内养护高吸水微球与水泥一起加入到拌合设备中进行拌合，掺量为水泥掺量的0.2％，所得混凝土的7d抗压强度为基准混凝土强度的110％，28d抗压强度为基准混凝土强度的123％，60min混凝土的流动度相对于基准混凝土增加18％，28d混凝土的自收缩相对于基准混凝土减小了65％。The SEM image of the reinforced concrete internal curing superabsorbent microsphere material prepared in this example is shown in FIG. 1. When in use, directly add the reinforced concrete internal curing superabsorbent microspheres together with cement to the mixing equipment for mixing. The mixing amount is 0.2% of the cement mixing amount. The 7d compressive strength of the resulting concrete is the benchmark concrete strength. 110%, 28d compressive strength is 123% of the benchmark concrete strength, the fluidity of 60min concrete is increased by 18% compared to the benchmark concrete, and the autogenous shrinkage of 28d concrete is reduced by 65% compared to the benchmark concrete.
实施例2：Example 2:
本实施例给出一种增强型混凝土内养护高吸水微球材料，以重量份数计，包括以下原料制成：9％的纳米二氧化硅，18％的壳聚糖，25％的戊二醛，4.4％ 的阿拉伯胶，30％的甲基丙烯酸，5％的冰乙酸，0.4％的异丙苯过氧化氢，0.2％的氯化亚铁，8％的乙醇钠。This example provides a reinforced concrete internal curing super absorbent microsphere material, in parts by weight, including the following raw materials: 9% nano silica, 18% chitosan, 25% glutaric acid Aldehydes, 4.4% gum arabic, 30% methacrylic acid, 5% glacial acetic acid, 0.4% cumene hydrogen peroxide, 0.2% ferrous chloride, 8% sodium ethoxide.
本实施例的增强型混凝土内养护高吸水微球材料的制备方法与实施例1中的增强型混凝土内养护高吸水微球材料的制备方法相同。The preparation method of the reinforced concrete inner-curing superabsorbent microsphere material of this embodiment is the same as the preparation method of the reinforced concrete inner-curing superabsorbent microsphere material in Example 1.
本实施例制得的增强型混凝土内养护高吸水微球材料的SEM图如图1所示。使用时，直接将该增强型混凝土内养护高吸水微球与水泥一起加入到拌合设备中进行拌合，掺量为水泥掺量的1.8％，所得混凝土的7d抗压强度为基准混凝土强度的108％，28d抗压强度为基准混凝土强度的123％，60min混凝土的流动度相对于基准混凝土增加20％，28d混凝土的自收缩相对于基准混凝土减小了60％。The SEM image of the reinforced concrete internal curing superabsorbent microsphere material prepared in this example is shown in FIG. 1. When in use, directly add the reinforced concrete internal curing superabsorbent microspheres together with cement to the mixing equipment for mixing, the mixing amount is 1.8% of the cement mixing amount, and the 7d compressive strength of the resulting concrete is the benchmark concrete strength 108%, 28d compressive strength is 123% of the benchmark concrete strength, the fluidity of 60min concrete is increased by 20% compared to the benchmark concrete, and the autogenous shrinkage of 28d concrete is reduced by 60% compared to the benchmark concrete.
实施例3：Example 3:
本实施例给出一种增强型混凝土内养护高吸水微球材料，以重量份数计，包括以下原料制成：10％的纳米二氧化硅，19％的壳聚糖，28％的戊二醛，4％的阿拉伯胶，27％的甲基丙烯酸，3.3％的冰乙酸，0.5％异丙苯过氧化氢，0.2％氯化亚铁，8％乙醇钠。This example provides a reinforced concrete internal curing superabsorbent microsphere material, in parts by weight, including the following raw materials: 10% nano silica, 19% chitosan, 28% glutaric acid Aldehydes, 4% gum arabic, 27% methacrylic acid, 3.3% glacial acetic acid, 0.5% cumene hydrogen peroxide, 0.2% ferrous chloride, 8% sodium ethoxide.
本实施例的增强型混凝土内养护高吸水微球材料的制备方法与实施例1中的增强型混凝土内养护高吸水微球材料的制备方法相同。The preparation method of the reinforced concrete inner-curing superabsorbent microsphere material of this embodiment is the same as the preparation method of the reinforced concrete inner-curing superabsorbent microsphere material in Example 1.
本实施例制得的增强型混凝土内养护高吸水微球材料的SEM图如图1所示。使用时，直接将该增强型混凝土内养护高吸水微球与水泥一起加入到拌合设备中进行拌合，掺量为水泥掺量的0.25％，所得混凝土的7d抗压强度为基准混凝土强度的112％，28d抗压强度为基准混凝土强度的128％，60min混凝土的流动度相对于基准混凝土增加30％，28d混凝土的自收缩相对于基准混凝土减小了69％。The SEM image of the reinforced concrete internal curing superabsorbent microsphere material prepared in this example is shown in FIG. 1. When in use, the reinforced concrete internal curing superabsorbent microspheres and cement are directly added to the mixing equipment for mixing, the mixing amount is 0.25% of the cement mixing amount, and the 7d compressive strength of the resulting concrete is the benchmark concrete strength 112%, 28d compressive strength is 128% of the benchmark concrete strength, the fluidity of 60min concrete is increased by 30% relative to the benchmark concrete, and the autogenous shrinkage of the 28d concrete is reduced by 69% relative to the benchmark concrete.
实施例4：Example 4:
本实施例给出一种增强型混凝土内养护高吸水微球材料，以重量份数计，包括以下原料制成：10％的纳米二氧化硅，15％的壳聚糖，30％的戊二醛，4.4％的阿拉伯胶，30％的甲基丙烯酸，5％的冰乙酸，0.5％异丙苯过氧化氢，0.1％氯化亚铁，5％乙醇钠。This example provides a reinforced concrete internal curing superabsorbent microsphere material, in parts by weight, including the following raw materials: 10% nano-silica, 15% chitosan, 30% glutaric acid Aldehydes, 4.4% gum arabic, 30% methacrylic acid, 5% glacial acetic acid, 0.5% cumene hydrogen peroxide, 0.1% ferrous chloride, 5% sodium ethoxide.
本实施例的增强型混凝土内养护高吸水微球材料的制备方法与实施例1中的增强型混凝土内养护高吸水微球材料的制备方法相同。The preparation method of the reinforced concrete inner-curing superabsorbent microsphere material of this embodiment is the same as the preparation method of the reinforced concrete inner-curing superabsorbent microsphere material in Example 1.
本实施例制得的增强型混凝土内养护高吸水微球材料的SEM图如图1所示。使用时，直接将该增强型混凝土内养护高吸水微球与水泥一起加入到拌合设备中进行拌合，掺量为水泥掺量的0.3％，所得混凝土的7d抗压强度为基准混凝土强度的102％，28d抗压强度为基准混凝土强度的130％，60min混凝土的流动度相对于基准混凝土增加35％，28d混凝土的自收缩相对于基准混凝土减小了70％。The SEM image of the reinforced concrete internal curing superabsorbent microsphere material prepared in this example is shown in FIG. 1. When in use, directly add the reinforced concrete internal curing superabsorbent microspheres together with cement to the mixing equipment for mixing, the mixing amount is 0.3% of the cement mixing amount, and the 7d compressive strength of the resulting concrete is the benchmark concrete strength 102%, 28d compressive strength is 130% of the benchmark concrete strength, the fluidity of 60min concrete is increased by 35% relative to the benchmark concrete, and the autogenous shrinkage of 28d concrete is reduced by 70% compared to the benchmark concrete.
从以上实施例可以看出，该强型混凝土内养护高吸水微球可以显著提高混凝土的抗压强度，四组实施例中28d抗压强度均为基准混凝土强度的120％以上。60min混凝土的流动性也得到了显著改善。另外，该内养护材料也可很大程度上减小混凝土的自收缩。因此，本发明的强型混凝土内养护高吸水微球具有良好的适用性，能有效解决当前混凝土养护过程中的问题，具有广阔的应用前景。It can be seen from the above examples that the high-absorbent microspheres cured in the strong concrete can significantly increase the compressive strength of the concrete. In the four groups of examples, the 28d compressive strength is more than 120% of the benchmark concrete strength. The fluidity of 60min concrete has also been significantly improved. In addition, the internal curing material can also greatly reduce the autogenous shrinkage of concrete. Therefore, the strong concrete internal curing superabsorbent microspheres of the present invention have good applicability, can effectively solve the problems in the current concrete curing process, and have broad application prospects.
Claims (9)
- 一种增强型混凝土内养护高吸水微球材料，其特征在于，以重量份数计，包括以下原料制成：8％～10％的纳米二氧化硅，15％～20％的壳聚糖，25％～30％的戊二醛，4％～5％的阿拉伯胶，25％～30％的甲基丙烯酸，3.3％～5％的冰乙酸，0.4％～0.5％的异丙苯过氧化氢，0.1％～0.2％的氯化亚铁，5％～8％的乙醇钠，原料的重量份数之和为100％。A reinforced concrete internal curing super absorbent microsphere material, which is characterized in that, in parts by weight, it comprises the following raw materials: 8%-10% nano-silica, 15%-20% chitosan, 25%～30% glutaraldehyde, 4%～5% gum arabic, 25%～30% methacrylic acid, 3.3%～5% glacial acetic acid, 0.4%～0.5% cumene hydrogen peroxide , 0.1% to 0.2% of ferrous chloride, 5% to 8% of sodium ethoxide, the total weight of raw materials is 100%.
- 如权利要求1所述的增强型混凝土内养护高吸水微球材料，其特征在于，所述的纳米二氧化硅的平均粒径为20nm。The reinforced concrete internal curing superabsorbent microsphere material according to claim 1, wherein the average particle size of the nano-silica is 20 nm.
- 一种增强型混凝土内养护高吸水微球材料的制备方法，其特征在于，该方法采用如权利要求1至2任一权利要求所述的增强型混凝土内养护高吸水微球材料的配方；该方法具体包括以下步骤：A method for preparing a reinforced concrete internal curing superabsorbent microsphere material, characterized in that the method adopts the formula of the reinforced concrete internal curing superabsorbent microsphere material according to any one of claims 1 to 2; the The method specifically includes the following steps:步骤一，按配方重量称取各原料；Step 1: Weigh the ingredients according to the formula weight;步骤二，将纳米二氧化硅分散于水中，将其配置成质量浓度为3％的纳米二氧化硅悬浮液，搅拌；Step 2: Disperse nano-silica in water, configure it into a nano-silica suspension with a mass concentration of 3%, and stir;步骤三，将冰乙酸用水稀释成质量浓度为1％的冰乙酸稀溶液；Step 3: Dilute glacial acetic acid with water into a dilute solution of glacial acetic acid with a mass concentration of 1%;步骤四，将壳聚糖和阿拉伯胶混合，加入步骤三制得的质量浓度为1％的冰乙酸稀溶液，搅拌形成壳聚糖和阿拉伯胶的稀酸溶液A；Step 4: Mix chitosan and gum arabic, add the dilute solution of glacial acetic acid with a mass concentration of 1% prepared in step 3, and stir to form a dilute acid solution A of chitosan and gum arabic;步骤五，将甲基丙烯酸加入水中，配置成质量浓度为15％的稀溶液，加入乙醇钠并冷却至室温，持续搅拌的过程中，加入异丙苯过氧化氢和氯化亚铁，充分溶解后制得混合物B；Step 5, add methacrylic acid to water, configure it as a dilute solution with a mass concentration of 15%, add sodium ethoxide and cool to room temperature, while continuing to stir, add cumene hydrogen peroxide and ferrous chloride to fully dissolve Then the mixture B is prepared;步骤六，将环戊烷和Span 80加入容器中，恒温搅拌形成油相C；Step 6, add cyclopentane and Span 80 to the container, stir at constant temperature to form oil phase C;步骤七，将步骤二制得的纳米二氧化硅悬浮液加入至油相C，惰性气体保护，恒温搅拌，持续搅拌的过程中，加入步骤四制得的稀酸溶液A和戊二醛，升速搅拌制得混合液D；Step 7, adding the nano-silica suspension prepared in step 2 to oil phase C, protecting with inert gas, stirring at a constant temperature, and continuously stirring, adding the dilute acid solution A and glutaraldehyde prepared in step 4, liters Mix liquid D with rapid stirring;步骤八，将步骤五制得的混合物B加入至步骤七制得的混合液D中反应后制得复合物E；Step 8, adding the mixture B prepared in step 5 to the mixed solution D prepared in step 7 and reacting to obtain a compound E;步骤九，将步骤八制得的复合物E取出，用溶剂洗涤，溶剂挥发后制得增强型混凝土内养护高吸水微球材料。In step 9, the composite E prepared in step 8 is taken out, washed with a solvent, and after the solvent is volatilized, a reinforced concrete inner curing superabsorbent microsphere material is prepared.
- 如权利要求3所述的增强型混凝土内养护高吸水微球材料的制备方法，其特征在于，步骤二中，所述的搅拌采用磁力搅拌，搅拌时间为20mim；步骤四中，所述的搅拌采用磁力搅拌，搅拌时间为30mim。The method for preparing superabsorbent microsphere material for reinforced concrete internal curing according to claim 3, characterized in that, in step 2, the stirring adopts magnetic stirring, and the stirring time is 20 millimeters; in step 4, the stirring Using magnetic stirring, the stirring time is 30mim.
- 如权利要求3所述的增强型混凝土内养护高吸水微球材料的制备方法，其特征在于，步骤六中，所述的恒温为30℃的恒温水浴环境；所述的搅拌为以200r/min搅拌20min。The method for preparing superabsorbent microsphere material for reinforced concrete internal curing according to claim 3, characterized in that, in step 6, the constant temperature is 30°C in a constant temperature water bath environment; the stirring is performed at 200 r/min Stir for 20min.
- 如权利要求3所述的增强型混凝土内养护高吸水微球材料的制备方法，其特征在于，步骤六中，所述的油相C中，Span 80为环戊烷质量分数的5％～8％。The preparation method of reinforced concrete internal curing super absorbent microsphere material according to claim 3, characterized in that, in step 6, in the oil phase C, Span 80 is 5% to 8% of the mass fraction of cyclopentane. %.
- 如权利要求3所述的增强型混凝土内养护高吸水微球材料的制备方法，其特征在于，步骤七中，所述的惰性气体保护为通氮气；所述的恒温为40℃恒温水浴环境；所述的搅拌为以200r/min搅拌10min；所述的升速搅拌为以400r/min搅拌30min。The method for preparing superabsorbent microsphere material for reinforced concrete internal curing according to claim 3, characterized in that, in step 7, the inert gas protection is nitrogen gas; the constant temperature is a constant temperature water bath environment of 40°C; The stirring is 200 r/min for 10 minutes; the rising speed stirring is 400 r/min for 30 minutes.
- 如权利要求3所述的增强型混凝土内养护高吸水微球材料的制备方法，其特征在于，步骤八中，所述的反应的整个过程中温度控制在40～45℃之间，反应时间为6h。The method for preparing superabsorbent microsphere material for reinforced concrete internal curing according to claim 3, characterized in that, in step 8, the temperature during the whole process of the reaction is controlled between 40°C and 45°C, and the reaction time is 6h.
- 如权利要求3所述的增强型混凝土内养护高吸水微球材料的制备方法，其特征在于，步骤九中，所述的溶剂为无水乙醇，洗涤3～5次。The method for preparing superabsorbent microsphere material for internal curing of reinforced concrete according to claim 3, characterized in that, in step 9, the solvent is absolute ethanol, and it is washed 3 to 5 times.
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| CN110606690A (en) * | 2019-09-23 | 2019-12-24 | 长安大学 | Enhanced concrete internal curing high water absorption microsphere material and preparation method thereof |
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| CN110606690A (en) | 2019-12-24 |
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