CN112830752A - High-performance phosphogypsum fiber composite material and preparation method thereof - Google Patents
High-performance phosphogypsum fiber composite material and preparation method thereof Download PDFInfo
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- CN112830752A CN112830752A CN202110019873.7A CN202110019873A CN112830752A CN 112830752 A CN112830752 A CN 112830752A CN 202110019873 A CN202110019873 A CN 202110019873A CN 112830752 A CN112830752 A CN 112830752A
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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
- C04B28/14—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 calcium sulfate cements
- C04B28/142—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements
- C04B28/143—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 calcium sulfate cements containing synthetic or waste calcium sulfate cements the synthetic calcium sulfate being phosphogypsum
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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
- C04B2111/00017—Aspects relating to the protection of the environment
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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
- 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
Abstract
The invention discloses a high-performance phosphogypsum fiber composite material and a preparation method thereof. The invention optimizes the matrix mixing proportion of the phosphogypsum composite material by using a close packing design method, and then adds organic fibers into the optimized matrix to prepare the high-performance phosphogypsum fiber composite material. The matrix of the composite material comprises the following components in parts by weight: 100 parts of semi-hydrated phosphogypsum, 5-50 parts of slag powder, 5-40 parts of fly ash, 5-20 parts of cement, 0.05-0.5 part of special gypsum retarder, 0.1-0.5 part of polycarboxylic acid water reducer and 40-120 parts of water. The organic fiber content of the composite material is 0.001-0.0006 (by volume fraction). The high-performance ardealite fiber composite material has the characteristics of good construction performance, high strength, water resistance, moisture resistance and low density, and has a wide application range.
Description
Technical Field
The invention relates to the technical field of building materials, in particular to a high-performance phosphogypsum fiber composite material and a preparation method thereof.
Background
The annual emission of phosphogypsum in China reaches about 5000 million tons, and due to the bottleneck of resource utilization technology, the accumulated inventory exceeds 2 million tons. At present, the comprehensive utilization rate of the phosphogypsum is only about 30 percent. The phosphogypsum is treated by adopting two modes of open-air stacking and dumping into the sea, so that a large amount of land is required to be occupied, and other harmful substances such as phosphorus, fluorine and the like contained in the phosphogypsum can pollute the atmosphere, soil and underground water around dangerously. How to treat and utilize the phosphogypsum is a problem to be solved urgently.
After proper purification treatment, phosphogypsum is dried, calcined to remove free water and crystal water, and then aged to prepare semi-hydrated gypsum (namely building gypsum). The gypsum board can be used as raw material to produce building material products such as gypsum boards, paper-surface gypsum boards, gypsum blocks or hollow laths and the like. The phosphogypsum building material product generally has the characteristics of light weight, sound insulation, heat insulation, shock resistance, low shrinkage rate, automatic fine adjustment of indoor humidity, strong processability, simple and convenient construction method and the like, and is one of effective ways for recycling the phosphogypsum. However, the semi-hydrated phosphogypsum also has the defects of low strength, low softening coefficient, large brittleness and the like, and the application range of the semi-hydrated phosphogypsum in the field of building materials is limited.
Disclosure of Invention
The invention aims to solve the technical problem of providing a high-performance phosphogypsum fiber composite material so as to solve the problem that the existing phosphogypsum is difficult to utilize.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention provides a high-performance phosphogypsum fiber composite material which comprises a matrix and fibers doped in the matrix, wherein the matrix consists of the following components in parts by weight:
the fiber content of the composite material is 0.001-0.0006 in terms of volume fraction.
Further, in the composite material, the matrix is preferably composed of the following components in parts by weight:
the fiber content of the composite material is preferably 0.002-0.0004 by volume fraction.
Further, the hemihydrate phosphogypsum is alpha-type hemihydrate phosphogypsum.
Further, the particle size range of the semi-hydrated phosphogypsum is 8-1000 μm, and the average particle size is 35-55 μm.
Further, the slag powder is one of S95 slag powder or S105 slag powder.
Furthermore, the special retarder for gypsum is a vegetable protein retarder, and the retarding time is more than 30 min.
Further, the water reducing rate of the polycarboxylic acid water reducing agent is more than or equal to 25%.
Further, the water is tap water.
Further, the organic fiber is polyvinyl alcohol fiber or polypropylene fiber, and the length of the organic fiber is 3mm-12 mm.
On the other hand, the invention discloses a preparation method of the high-performance phosphogypsum fiber composite material, which comprises the following steps: firstly, carrying out close packing design on the base body mixture ratio to obtain an optimized mixture ratio; and mixing the components according to the optimized proportion, adding fiber, and uniformly stirring to obtain the high-performance phosphogypsum fiber composite material.
Further, the specific steps of the close-packing design are as follows:
(1) establishing a compact packing model of the matrix according to a Dinger-Funk equation to determine the volume ratio of each solid component in the matrix during compact packing;
(2) determining the water-glue ratio; the water-to-glue ratio is 0.5-0.7;
(3) adding a polycarboxylic acid water reducing agent into the matrixes, and measuring the fluidity of each matrix under different water reducing agent mixing amounts to determine the water reducing agent saturated mixing amount of the matrixes;
(4) the actual mixing amount of the water reducing agent is tested around the saturated mixing amount of the water reducing agent under the guidance of the saturated mixing amount of the water reducing agent of the matrix, and the component proportion is selected as the optimal formula when the mixing amount of the water reducing agent is minimum on the premise of ensuring the fluidity and high strength of the phosphogypsum-based material.
Further, the Dinger-Funk equation is as follows:
wherein P (D) is the percentage of accumulated undersize particles; d is the current particle size, mu m; dminIs the minimum particle size, μm; dmaxIs the maximum particle size; mu m; q is a distribution coefficient, and the value range of q is 0.22-0.25.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention optimizes the matrix mixing ratio of the phosphogypsum composite material by using a close packing design method, and adds organic fibers into the optimized matrix, thereby preparing the phosphogypsum fiber composite material with high compressive strength and high ductility. The matrix mixing ratio is optimized by adopting a close packing theory, so that the powder and the fine aggregate in the matrix are reasonably matched according to the particle size distribution, the system packing porosity is obviously reduced, and the packing density of the phosphogypsum is improved, thereby being beneficial to improving the strength of the phosphogypsum; by doping the organic fiber in the matrix, the strength of the phosphogypsum can be further improved.
2. The high-performance ardealite fiber composite material has the characteristics of good construction performance, high strength, water resistance, moisture resistance and low density, and has a wide application range, such as: indoor engineering construction, building exterior wall decoration, rapid repair engineering and the like. The method can be used for reducing the phosphogypsum which is an industrial solid waste into industrial construction to promote the development of circular economy, and has important social, environmental and economic significance.
Drawings
FIG. 1 is a graph showing particle size distributions of base raw materials used in examples 1 to 3 of the present invention and comparative examples 1 to 3;
FIG. 2 is a graph of a close-packing model of matrix composites used in examples 1-3 of the present invention.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
As described in the background art, phosphogypsum is subjected to proper purification treatment, then is dried and calcined to remove free water and crystal water, and then is aged to prepare semi-hydrated gypsum (namely building gypsum). The gypsum board can be used as raw material to produce building material products such as gypsum boards, paper-surface gypsum boards, gypsum blocks or hollow laths and the like. The phosphogypsum building material product generally has the characteristics of light weight, sound insulation, heat insulation, shock resistance, low shrinkage rate, automatic fine adjustment of indoor humidity, strong processability, simple and convenient construction method and the like, and is one of effective ways for recycling the phosphogypsum. However, the semi-hydrated phosphogypsum also has the defects of low strength, low softening coefficient, large brittleness and the like, and the application range of the semi-hydrated phosphogypsum in the field of building materials is limited.
In order to solve the problem, the invention provides a high-performance phosphogypsum fiber composite material, wherein a matrix of the composite material consists of the following components in parts by weight: 100 parts of semi-hydrated phosphogypsum, 5-50 parts of slag powder, 5-40 parts of fly ash, 5-20 parts of cement, 0.05-0.5 part of special gypsum retarder, 0.1-0.5 part of polycarboxylic acid water reducer and 40-120 parts of water. The organic fiber content of the composite material is 0.001-0.0006 (by volume fraction).
In the composite material, the semi-hydrated phosphogypsum is an industrial solid waste, is green and environment-friendly, and is used as the most main cementing material in a system. The cement is a hydraulic substance, can change the slurry composition, reduce the solubility and improve the softening coefficient; and simultaneously, the hydration product calcium hydroxide of the cement is alkaline, so that the pH value in the slurry can be adjusted to an environment which is most suitable for crystal growth, the growth of dihydrate gypsum crystals in the phosphogypsum is facilitated, the hydration product forms a mutually overlapped compact structure, and the strength of the material is improved. The mineral powder is calcium-aluminum-silicon material, on one hand, the mineral powder can react with gypsum to generate ettringite so as to reduce the content of crystal water in the product and further reduce the heat conductivity coefficient of the material, and on the other hand, the slag powder can react with calcium hydroxide to generate volcanic ash to generate calcium silicate hydrate (C-S-H gel) so as to improve the strength of the material. The fly ash has a fine particle size, can fill gaps of other cementing materials, enables slurry to be more compact, improves durability of the materials, can provide aluminum-silicon compounds for the whole system, is beneficial to generating more C-S-H gel, and improves strength and softening coefficient of the materials.
In a preferred embodiment of the present invention, the matrix of the composite material consists of the following components in parts by weight: 100 parts of semi-hydrated phosphogypsum, 10-35 parts of slag powder, 10-35 parts of fly ash, 5-10 parts of cement, 0.1-0.2 part of special gypsum retarder, 0.15-0.35 part of polycarboxylic acid water reducer and 50-90 parts of water. The organic fiber content of the composite material is 0.002-0.0004 (by volume fraction).
In the invention, the hemihydrate phosphogypsum is preferably alpha-type hemihydrate phosphogypsum. The particle size range of the selected semi-hydrated phosphogypsum is preferably 8-1000 μm, and the average particle size is preferably 35-55 μm.
In the invention, the slag powder is preferably one of S95 slag powder or S105 slag powder, and each performance of the slag powder meets the technical index requirements of standard GB/T18046-2008 on the slag powder.
In the invention, the cement is Portland cement, and all the performances of the cement meet the requirements of national standards on Portland cement.
In the invention, the retarder special for gypsum is preferably a vegetable protein retarder, and the retarding time of the retarder is more than 30 min.
In the present invention, the polycarboxylic acid-based water reducing agent preferably has a water reducing rate of 25% or more.
In the present invention, the water is preferably tap water.
In the invention, the organic fiber is polyvinyl alcohol fiber or polypropylene fiber, and the length is 3mm-12 mm.
The present invention is further described below in conjunction with specific examples to enable those skilled in the art to better understand the present invention and to practice it, but the examples are not intended to limit the present invention.
In the following examples, the phosphogypsum hemihydrate is alpha type phosphogypsum hemihydrate, the particle size range is 8-1000 μm, and the average particle size is 35-55 μm. The slag powder is one of S95 slag powder or S105 slag powder, each performance of the slag powder meets the technical index requirements of standard GB/T18046-2008 on the slag powder, each performance of the portland cement meets the requirements of national standard on the portland cement, the special retarder for gypsum is a vegetable protein retarder, the water reduction rate of the polycarboxylic acid water reducer is more than or equal to 25%, and water is tap water. The organic fiber is polyvinyl alcohol fiber or polypropylene fiber.
Examples 1 to 3 and comparative examples 1 to 3
According to the proportion in the table 1, the components are uniformly mixed to obtain the phosphogypsum composite material.
TABLE 1 raw material mixing ratios of examples 1 to 3 and comparative examples 1 to 3
| Phosphogypsum | Slag powder | Cement | Fly ash | Retarder | Water reducing agent | Water (W) | |
| Example 1 | 100 | 12.5 | 6.25 | 12.5 | 0.1 | 0.30 | 62.5 |
| Example 2 | 100 | 28.6 | 7.1 | 14.3 | 0.1 | 0.16 | 71.4 |
| Example 3 | 100 | 33.3 | 8.3 | 33.3 | 0.1 | 0.23 | 83.3 |
| Comparative example 1 | 100 | 0 | 0 | 0 | 0.1 | 0 | 70 |
| Comparative example 2 | 100 | 25 | 0 | 0 | 0 | 0 | 87.5 |
| Comparative example 3 | 100 | 12.5 | 6.25 | 12.5 | 0.1 | 0 | 87.5 |
The phosphogypsum composite materials prepared in examples 1-3 and comparative examples 1-3 are tested for compressive strength and softening coefficient by referring to methods in GB/T9776-2008 and DBJ52/T093-2019, and the obtained results are shown in Table 2.
TABLE 2 Performance test results of examples 1 to 3 and comparative examples 1 to 3
From the results of table 2, it can be seen that the phosphogypsum fibre composite of the examples shows higher compressive strength than the comparative example, and the strength after soaking in water of the phosphogypsum fibre composite of the examples is also significantly higher than the comparative example. Therefore, the phosphogypsum fiber composite material disclosed by the invention shows excellent mechanical properties and waterproof and moistureproof properties, can be applied to the fields of indoor engineering construction, building exterior wall decoration, rapid repair engineering and the like, and can realize resource utilization of phosphogypsum.
The above-mentioned embodiments are merely preferred embodiments for fully illustrating the present invention, and the scope of the present invention is not limited thereto. The equivalent substitution or change made by the technical personnel in the technical field on the basis of the invention is all within the protection scope of the invention. The protection scope of the invention is subject to the claims.
Claims (10)
1. The high-performance phosphogypsum fiber composite material is characterized by comprising a matrix and fibers doped in the matrix; the matrix consists of the following components in parts by weight:
the fiber content of the composite material is 0.001-0.0006 in terms of volume fraction.
2. The high-performance phosphogypsum fibre composite material according to claim 1, characterized in that the matrix consists of the following components in parts by weight:
according to volume fraction, the fiber content in the composite material is 0.002-0.0004.
3. A high performance phosphogypsum fibre composite material according to claim 1 or 2, characterized in that the hemihydrate phosphogypsum is alpha-hemihydrate phosphogypsum.
4. A high performance phosphogypsum fibre composite material according to claim 3, characterised in that the particle size range of the hemihydrate phosphogypsum is 8-1000 μm with an average particle size of 35-55 μm.
5. The high-performance phosphogypsum fibre composite material according to claim 1 or 2, characterized in that the slag powder is one of S95 slag powder or S105 slag powder.
6. The high-performance phosphogypsum fiber composite material as claimed in claim 1, wherein the retarder special for gypsum is a vegetable protein retarder, and the retardation time is more than 30 min.
7. The high-performance phosphogypsum fiber composite material as claimed in claim 1, wherein the water-reducing rate of the polycarboxylic acid water-reducing agent is more than or equal to 25%.
8. The high-performance phosphogypsum fibre composite material according to claim 1, characterized in that the water is tap water.
9. The high-performance phosphogypsum fibre composite material according to claim 1, characterized in that the fibres are polyvinyl alcohol fibres or polypropylene fibres.
10. The method for preparing a high performance phosphogypsum fibre composite according to any of claims 1-9, characterized in that it comprises: firstly, carrying out close packing design on the base body proportion to obtain an optimal base body proportion; and mixing the components according to the optimal matrix proportion, adding fibers, and uniformly stirring to obtain the high-performance phosphogypsum fiber composite material.
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Cited By (2)
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| CN113582653A (en) * | 2021-09-01 | 2021-11-02 | 贵州贵诚磷石膏有限公司 | Special ardealite curb and preparation method thereof |
| CN114213045A (en) * | 2021-12-15 | 2022-03-22 | 江苏大学 | Phosphogypsum-based cement based on industrial waste and preparation method thereof |
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Application publication date: 20210525 |