CN115477483B - Carbonized reinforced super sulfate cement and preparation method thereof - Google Patents
Carbonized reinforced super sulfate cement and preparation method thereof Download PDFInfo
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- CN115477483B CN115477483B CN202211166004.8A CN202211166004A CN115477483B CN 115477483 B CN115477483 B CN 115477483B CN 202211166004 A CN202211166004 A CN 202211166004A CN 115477483 B CN115477483 B CN 115477483B
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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
- 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
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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
- C04B7/00—Hydraulic cements
- C04B7/36—Manufacture of hydraulic cements in general
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Abstract
The invention discloses carbonized reinforced super sulfate cement, which comprises, by mass, 60-85 parts of mineral powder, 10-35 parts of gypsum, 0-10 parts of alkali-exciting agent, 0-5 parts of nano silicon dioxide, 0-1 part of water reducer and 0-1 part of polyamide-amine dendritic macromolecule. Meanwhile, the preparation method can be used for modifying the defect of the carbonization degradation of the super sulfate, and the carbonization reinforcement of the super sulfate cement is realized by a nano modification technology. The invention can provide technical support for large-scale popularization and application of the super sulfate cement.
Description
Technical Field
The invention belongs to the field of cement preparation, and particularly relates to carbonized reinforced super-sulfate cement and a preparation method thereof.
Background
The super sulfate cement is a hydraulic cementing material prepared from 75-85% (mass fraction, the following is the same) of slag, 10-20% of sulfate such as gypsum and the like and 1-5% of alkaline components (such as clinker, calcium hydroxide and the like) by grinding together or grinding separately and mixing. The production process can consume a large amount of industrial waste, CO 2 The discharge amount is only 10% of that of Portland cement, and the energy consumption is reduced by 80% -90%, so that the low-carbon cement is a typical low-carbon gel material.
The main hydration products of the super-sulfate cement are crystalline ettringite (AFt) and colloidal hydrated calcium aluminosilicate gel (C-A-S-H), wherein the AFt is extremely easy to carbonize and decompose, so that the whole structure of the super-sulfate cement is degraded, se:Sub>A sand forming phenomenon occurs, and popularization and application of the super-sulfate cement are severely restricted.
Currently, alkaline substances and the like are mainly incorporated by reducing the water-to-ash ratio. However, lowering the water-to-ash ratio can only delay the process of carbonization degradation, and the decomposition of AFt and carbonization degradation phenomena are still unavoidable. DopingThe addition of alkaline substances can increase the curing CO of the super sulfate system to a certain extent 2 The carbonization speed is delayed; however, an excessive amount of alkaline material will significantly reduce the mechanical properties of the hypersulfated cement.
Disclosure of Invention
In order to solve the defects of the background technology, the invention provides the carbonization strengthening super-sulfate cement and the preparation method thereof, the method can be used for modifying the defects of the carbonization degradation of the super-sulfate, and the carbonization strengthening of the super-sulfate cement is realized by a nano modification technology. The invention can provide technical support for large-scale popularization and application of the super sulfate cement.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the carbonized reinforced super sulfate cement consists of mineral powder 60-85 weight portions, gypsum 10-35 weight portions, alkali excitant 0-10 weight portions, nanometer silica 0-5 weight portions, water reducing agent 0-1 weight portions and polyamide-amine dendritic polymer 0-1 weight portions.
Further, the carbonized reinforced super sulfate cement comprises, by mass, 70-80 parts of mineral powder, 15-25 parts of gypsum, 0-6 parts of alkali-exciting agent, 0-3 parts of nano silicon dioxide, 0-0.5 part of water reducer and 0-0.5 part of polyamide-amine dendrimer.
Further, the polyamide-amine dendrimer is a 0.5 generation dendrimer, and the synthesis method comprises the following steps: accurately weighing 12.0g of ethylenediamine, adding 40g of methanol into ethylene glycol, and stirring at 25 ℃ for 10 min; then 137.60g of methyl acrylate is slowly added dropwise at 25 ℃, and after the addition is finished, the mixture is reacted for 24 hours at the constant temperature of 25 ℃; the reaction mixture was distilled under reduced pressure at 50℃and 133.3. 133.3 Pa to give ethylenediamine-nucleated 0.5-generation dendrimer 0.5-PAMAM.
The preparation method of the carbonized and reinforced super-sulfate cement comprises the following steps:
(1) Preparation of nano silicon dioxide dispersion liquid: dispersing nano silicon dioxide by using an ultrasonic cell grinder, and cooling by using ice water bath in the dispersing process;
(2) Weighing silicate cement, mineral powder, gypsum, a water reducing agent and polyamide-amine dendritic macromolecules of an alkali-exciting agent according to a mixing proportion, and fully stirring the mixture and nano silicon dioxide dispersion liquid in a paste stirrer, wherein the stirring procedure is that firstly, slow stirring is carried out for 120s, stopping stirring is carried out for 15s, and then, fast stirring is carried out for 120s; maintaining after stirring uniformly, and demoulding;
(3) After the test block is cured to 28d, the test block is transferred into a carbonization box for carbonization. The carbonization conditions are as follows: the temperature is 18-22 ℃, the relative humidity is 65-75%, and the CO 2 The concentration was 5%.
The beneficial effects of the invention are as follows:
the invention provides a method for simultaneously improving the mechanical property and the carbonization resistance of a hypersulfated cement, which comprises the following steps:
1) The content of an easily carbonized component AFt in the super sulfate cement is reduced, the content of se:Sub>A difficult carbonized component C-A-S-H gel in se:Sub>A product is increased, and the carbonization resistance is improved;
2) The micro-nano structure of the easily carbonized component AFt is modified, so that the carbonization resistance of the easily carbonized component AFt is improved;
3) Modifying the microstructure of the carbonized product of AFt to gel the carbonized product and strengthen the integral structure of the super-sulfate cement.
Drawings
FIG. 1 shows the strength development law of each group of samples (T3 indicates 3 days of carbonization, and T7 indicates 7 days of carbonization).
Detailed Description
The present invention will be further described in detail with reference to the following examples in order to better understand the aspects of the present invention and to make the above-mentioned objects, features and advantages of the present invention more apparent to those skilled in the art.
Example 1
(1) Raw materials:
gypsum (Natural gypsum, desulfurized gypsum, phosphogypsum, etc.)
Mineral powder (S95, S105, etc.)
Fly ash (first-grade or second-grade fly ash)
Alkali-activator (general purpose Portland cement, slaked lime, quicklime, etc.)
Nano silicon dioxide (grain size 5-100nm, siO) 2 The content is more than 99 percent, the specific surface areaGreater than 200 m 2 /g）
Water reducer (polycarboxylate water reducer, naphthalene series water reducer)
Polyamide-amine (PAMAM) dendrimers
(2) The preparation method of the sample comprises the following steps:
preparation of nano silicon dioxide dispersion liquid: dispersing nano silicon dioxide by using an ultrasonic cell grinder, and cooling by using ice water bath in the dispersing process.
Synthesis of 0.5 generation dendrimer: accurately weighing 12.0g (0.20 mol) of ethylenediamine, adding 40g of methanol into ethylene glycol, and stirring at 25 ℃ for 10 min; then 137.60g (1.60 mol) of methyl acrylate was slowly added dropwise at 25℃and after completion of the addition, the mixture was allowed to react at a constant temperature of 25℃for 24 hours. The reaction mixture was distilled under reduced pressure at 50℃and 133.3. 133.3 Pa to give ethylenediamine-nucleated 0.5-generation dendrimer 0.5-PAMAM.
The water reducer can be prepared together with the nano silicon dioxide dispersion liquid, and can also be added during stirring.
The ordinary Portland cement (42.5), mineral powder, gypsum, water reducer and 0.5-PAMAM dendrimer are weighed according to the mix proportion design and fully stirred with the nano silicon dioxide dispersion liquid in a paste mixer, and the stirring procedure is that firstly, slow stirring is carried out for 120s, then, the stirring is carried out for 15s, and then, the stirring is carried out for 120s. After stirring uniformly, putting the mixture into a mould with the thickness of 40mm multiplied by 40mm, transferring the mixture into a curing box (20+/-3 ℃ and RH is more than or equal to 95%) for curing after compacting, demoulding after 1d, and testing the compressive strength of the sample according to the cement mortar strength test method (GB/T17671-2021) after the sample is cured to a certain age.
After the test block is cured to 28 days, the test block is transferred into a carbonization box, and the temperature is 18-22 ℃, the relative humidity is 65-75 percent, and CO is carried out 2 The sample was subjected to carbonization in an environment of 5% concentration, and at a certain age of carbonization, the compressive strength of the sample was measured according to the method for testing cement mortar strength (GB/T17671-2021).
As can be seen from FIG. 1, the strength rapidly decreases after carbonization of conventional super-sulfate cement without nano-silica and 0.5-PAMAM dendrimer. The single doped nano silica (comparative group 1, 2) can significantly improve the 28-day compressive strength of the ultra-sulfur cement, while the compressive strength is proportional to the amount of doped nano silica, and is optimal in the case of doping 3% of nano silica (comparative group 2). And after the nano silicon dioxide modified super sulfur cement is carbonized, the strength is not reduced, the reverse rising is avoided, and the carbonization resistance is obviously improved. Simultaneously, the nano silicon dioxide and 0.5-PAMAM dendrimer (comparative groups 3, 4 and 5) are doped, so that the mechanical property of the nano silicon dioxide modified super sulfate cement is slightly reduced, but the mechanical property after carbonization can be obviously improved. The mechanical properties are optimal when the amount of incorporated 0.5-PAMAM dendrimer is 0.3% (comparative group 4).
Therefore, the nano silicon dioxide can obviously improve the mechanical property, and has the main effects of improving the content of C-A-S-H gel in the hypersulfated cement stone, thereby improving the mechanical property and the carbonization resistance; the main function of the 0.5-PAMAM dendrimer is to gel the carbonized product instead of crystallizing, so as to achieve the effect of carbonization reinforcement.
Claims (3)
1. The application method of the carbonized and reinforced super-sulfate cement is characterized by comprising the following steps of:
(1) Preparation of nano silicon dispersion: dispersing nano SiO using ultrasonic cell grinder 2 The dispersion process adopts ice water bath for cooling;
(2) Weighing alkali excitant, silicate cement, mineral powder, gypsum, water reducer, polyamide-amine dendritic macromolecule according to a mixing proportion, and fully stirring with the nano dispersion liquid in a paste stirrer, wherein the stirring procedure is that firstly, slow stirring is carried out for 120s, stopping stirring is carried out for 15s, and then, fast stirring is carried out for 120s; maintaining after stirring uniformly, and demoulding;
(3) After the test block is maintained for 28 days, transferring the test block into a carbonization box for carbonization;
the carbonized reinforced super sulfate cement consists of 60-85 parts of mineral powder, 10-35 parts of gypsum, 0-10 parts of alkali-exciting agent, 3-5 parts of nano silicon dioxide, 0-1 part of water reducer and polyamide-amine dendritic macromolecules in parts by mass; the amount of polyamide-amine dendrimer was 0.3%.
2. The method for applying the carbonized reinforced super sulfate cement according to claim 1, wherein the polyamide-amine dendrimer is a 0.5 generation dendrimer, and the synthesis method comprises the following steps: accurately weighing 12.0g of ethylenediamine, adding 40g of methanol into ethylene glycol, and stirring at 25 ℃ for 10 min; then 137.60g of methyl acrylate is slowly added dropwise at 25 ℃, and after the addition is finished, the mixture is reacted for 24 hours at the constant temperature of 25 ℃; the reaction mixture was distilled under reduced pressure at 50℃and 133.3. 133.3 Pa to give ethylenediamine-nucleated 0.5-generation dendrimer 0.5-PAMAM.
3. The method of using a carbonized reinforced super sulfate cement as set forth in claim 1, wherein the conditions of the carbonization are: the temperature is 18-22 ℃, the relative humidity is 65-75%, and the CO 2 The concentration was 5%.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03193652A (en) * | 1989-12-21 | 1991-08-23 | Asahi Glass Co Ltd | Hydraulic hardened body |
| CN106007793A (en) * | 2016-05-18 | 2016-10-12 | 武汉理工大学 | Method for improving frost resistance of excess-sulfate phosphogypsum slag cement product |
| CN107827379A (en) * | 2017-11-28 | 2018-03-23 | 唐山北极熊建材有限公司 | High anti-folding ultra-sulphate cement and preparation method thereof |
| MX2017013820A (en) * | 2017-10-27 | 2019-04-29 | Centro De Investig Y De Estudios Avanzados Del I P N | Cement and supersulfated composites based on volcanic igneous rocks. |
| CN112321182A (en) * | 2020-12-03 | 2021-02-05 | 嘉华特种水泥股份有限公司 | Sulphoaluminate cement, cementing material and slurry for repairing airport runways |
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- 2022-09-23 CN CN202211166004.8A patent/CN115477483B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03193652A (en) * | 1989-12-21 | 1991-08-23 | Asahi Glass Co Ltd | Hydraulic hardened body |
| CN106007793A (en) * | 2016-05-18 | 2016-10-12 | 武汉理工大学 | Method for improving frost resistance of excess-sulfate phosphogypsum slag cement product |
| MX2017013820A (en) * | 2017-10-27 | 2019-04-29 | Centro De Investig Y De Estudios Avanzados Del I P N | Cement and supersulfated composites based on volcanic igneous rocks. |
| CN107827379A (en) * | 2017-11-28 | 2018-03-23 | 唐山北极熊建材有限公司 | High anti-folding ultra-sulphate cement and preparation method thereof |
| CN112321182A (en) * | 2020-12-03 | 2021-02-05 | 嘉华特种水泥股份有限公司 | Sulphoaluminate cement, cementing material and slurry for repairing airport runways |
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