CN112979230B - Polypropylene fiber reinforced red mud-based polymer material and preparation method thereof - Google Patents
Polypropylene fiber reinforced red mud-based polymer material and preparation method thereof Download PDFInfo
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- CN112979230B CN112979230B CN202110497622.XA CN202110497622A CN112979230B CN 112979230 B CN112979230 B CN 112979230B CN 202110497622 A CN202110497622 A CN 202110497622A CN 112979230 B CN112979230 B CN 112979230B
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
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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
- C04B12/00—Cements not provided for in groups C04B7/00 - C04B11/00
- C04B12/005—Geopolymer cements, e.g. reaction products of aluminosilicates with alkali metal hydroxides or silicates
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
- C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/10—Production of cement, e.g. improving or optimising the production methods; Cement grinding
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Abstract
The invention relates to the field of red mud-based polymer materials in building materials, in particular to a polypropylene fiber reinforced red mud-based polymer material and a preparation method thereof. The geopolymer material is composed of 600-800 parts of Bayer process red mud, 200-400 parts of coal-based metakaolin, 750-850 parts of alkali-activated agent and 2-8 parts of polypropylene fiber; wherein the length of the polypropylene fiber is more than or equal to 6mm, and the diameter is 30-35 mu m. The invention solves the key problems of low flexural strength, small toughness, large drying shrinkage and the like of the red mud base polymer. This is attributable to the bridging ability of the polypropylene fibers and the strong bond with the geopolymer matrix, the highest flexural strength, the markedly improved brittle failure under pressure of the fiber reinforced geopolymer material produced, the increased toughness and the presence of significant residual strength; the drying shrinkage of 90d is reduced.
Description
Technical Field
The invention relates to the field of red mud-based polymer materials in building materials, in particular to a polypropylene fiber reinforced red mud-based polymer material and a preparation method thereof.
Background
Red mud is an industrial waste discharged in the production process of alumina and is named as red mud. According to statistics, 1-2 tons of red mud is produced per 1 ton of alumina, and the total discharge amount of the red mud is more than 27 hundred million tons. The red mud has higher alkalinity and contains more heavy metals, so the utilization rate is always lower. Geopolymers are novel inorganic gelling materials formed by the reaction of an alkali-activator and an aluminosilicate starting material. The preparation of the red mud base polymer by taking red mud as a raw material is one of the most effective ways for solving the problem of red mud accumulation. However, as with most ceramic materials, the red mud base polymer has main defects of small toughness, low flexural strength, large drying shrinkage and the like, which can prevent the popularization and application of the base polymer. The polypropylene fiber is a synthetic fiber and has the advantages of low price, high strength, good toughness, easy dispersion, corrosion resistance and the like. The polypropylene fiber is doped into the geopolymer, so that the defects can be effectively overcome, the performance of the red mud-based polymer is improved, the application range of the red mud-based polymer is enlarged, and the method has a positive pushing effect on realizing the practical engineering application of the red mud-based polymer.
Disclosure of Invention
The invention provides a polypropylene fiber reinforced red mud base polymer material and a preparation method thereof, and aims to solve the problems of low toughness, low flexural strength, large drying shrinkage and the like of the red mud base polymer.
The invention is realized by the following technical scheme: the polypropylene fiber reinforced red mud base polymer material consists of the following raw materials in parts by weight, 600-800 parts of Bayer process red mud, 200-400 parts of coal-based metakaolin, 750-850 parts of alkali excitant and 2-8 parts of polypropylene fiber; the total Si/Al in all raw materials is 1.2, the Na/Al is 1.0, and the mass ratio of water to solid is 0.5; wherein the length of the polypropylene fiber is more than or equal to 6mm, and the diameter is 30-35 mu m.
As a further improvement of the technical scheme of the invention, the average grain size of the Bayer process red mud is 2.64 mu m, and the specific surface area is 2270m 2 /kg。
As a further improvement of the technical scheme of the invention, the average particle size of the coal-based metakaolin is 1.34 mu m, and the specific surface area is 4480m 2 /kg。
As a further improvement of the technical scheme of the invention, the alkali-activated agent is formed by mixing distilled water, sodium hydroxide and sodium silicate solution.
As the technical proposal of the inventionFurther improves the modulus of the water glass to be 3.0-3.3, and the SiO in the water glass 2 The content of Na is more than or equal to 20 percent 2 The content of O is more than or equal to 8 percent.
As a further improvement of the technical scheme of the invention, the tensile strength of the polypropylene fiber is 460MPa, the elastic modulus is 3.5GPa, and the ultimate tensile rate is 30%.
In order to clear out the explanation, the invention further provides a preparation method of the polypropylene fiber reinforced red mud base polymer material, which comprises the following steps:
(1) The high-speed gas generated by the high-pressure air gun is utilized to fully blow off the agglomerated polypropylene fibers;
(2) Accurately weighing Bayer process red mud and coal-series metakaolin according to parts by weight, adding the red mud and the coal-series metakaolin into a mortar stirrer, fully stirring for 2min, adding polypropylene fibers, stirring for 2min, adding an alkali excitant after the fibers are uniformly dispersed, and continuously stirring for 3min to form uniformly mixed fiber reinforced geopolymer slurry;
(3) Pouring the fiber reinforced geopolymer slurry into a steel mould, vibrating for 1min on a vibrating table, sealing the mould by using a preservative film, solidifying for 24h at room temperature, and demoulding;
(4) And (3) placing the demoulded fiber reinforced geopolymer in a standard curing box for curing to 28d, thus obtaining the polypropylene fiber reinforced red mud-based geopolymer material.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention can prepare the geopolymer cementing material by utilizing industrial waste red mud on a large scale, and realize the resource utilization of industrial waste.
(2) The invention solves the key problems of low flexural strength, small toughness, large drying shrinkage and the like of the red mud base polymer. This is attributable to the bridging ability of the polypropylene fibers and the strong bond with the geopolymer matrix, the highest flexural strength of the prepared fiber-reinforced geopolymer material at 28d was increased by 27.0% over the fiber-free geopolymer; the compressive brittle fracture condition is obviously improved, the toughness is enhanced, and obvious residual strength exists; the drying shrinkage of 90d is reduced by at most 58.3%.
(3) The preparation process is carried out at normal temperature and normal pressure, and the preparation process is environment-friendly.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram showing the comparison of the red mud base polymer without fiber in comparative example 1 with the compression fracture morphology of a polypropylene fiber reinforced red mud base polymer in example 1 of the present invention.
Fig. 2 is a flow chart of a preparation method of a polypropylene fiber reinforced red mud base polymer material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be described in detail below. It will be apparent that the described embodiments are only some, but not all, embodiments of the invention. All other embodiments, based on the examples herein, which are within the scope of the invention as defined by the claims, will be within the scope of the invention as defined by the claims.
The raw materials and the instruments used in the invention are as follows:
bayer process red mud: is obtained from certain aluminum plant of Shanxi Hejin, and has average particle diameter of 2.64 μm and specific surface area of 2270m 2 Kg, the main chemical component is SiO 2 、Al 2 O 3 、CaO、Na 2 O and Fe 2 O 3 。
Coal-based metakaolin: from Xin Jin Yu Xin Shanxi, industry Co., ltd, an average particle diameter of 1.34 μm and a specific surface area of 4480m 2 Kg, the main chemical component is SiO 2 And Al 2 O 3 。
Alkali-exciting agent: is composed of 70 parts by mass of distilled water, 80 parts by mass of sodium hydroxide and 640 parts by mass of water glass solution. Wherein, the sodium hydroxide is analytically pure, and the purity is more than or equal to 94 percent. The modulus of the water glass is 3.0-3.3, and the SiO in the water glass 2 The mass percentage content of Na is more than or equal to 20 percent 2 The mass percentage content of O is more than or equal to 8 percent.
Polypropylene fibers: the length is more than or equal to 6mm, the diameter is 30-35 mu m, the tensile strength is 460MPa, the elastic modulus is 3.5GPa, and the ultimate elongation is 30%.
High pressure air gun: model number of Xin epitaxial compressor Co., ltd.): ZB-0.14/8; the flow rate of the high-velocity gas generated by the high-pressure air gun is not particularly limited, as long as the agglomerated polypropylene fibers can be sufficiently blown off.
The compressive strength, flexural strength and shrinkage test criteria in the invention are as follows:
placing the test block for compression resistance and fracture resistance test in a standard curing box for curing until the test block is 28d; according to the standard GJ/T70-2009 ' basic performance test method Standard of building mortar ' of the industry Standard of the people's republic of China, a universal tester is used for testing the compressive strength and the flexural strength of a polypropylene fiber reinforced red mud base polymer test block.
After standard curing of the test block for shrinkage test for 3d, the initial length was recorded, and then placed in a dry box at a temperature of 20.+ -. 2 ℃ and a relative humidity of 60.+ -. 5%. According to the execution standard JCT 603-2004 cement mortar dry shrinkage test method of the building material industry of the people's republic of China, a digital dial indicator is used for recording and testing the drying shrinkage condition of the polypropylene fiber reinforced red mud base polymer.
The preparation method of the polypropylene fiber reinforced red mud base polymer material provided by the invention comprises the following steps:
(1) The high-speed gas generated by the high-pressure air gun is utilized to fully blow off the agglomerated polypropylene fibers;
(2) Accurately weighing Bayer process red mud and coal-series metakaolin according to parts by weight, adding the red mud and the coal-series metakaolin into a mortar stirrer, fully stirring for 2min, adding polypropylene fibers, stirring for 2min, adding an alkali excitant after the fibers are uniformly dispersed, and continuously stirring for 3min to form uniformly mixed fiber reinforced geopolymer slurry;
(3) Pouring the fiber reinforced geopolymer slurry into a 40mm multiplied by 160mm steel mould, vibrating for 1min on a vibrating table, sealing the mould by using a preservative film, solidifying for 24h at room temperature, and demoulding;
(4) And (3) placing the demoulded fiber reinforced geopolymer in a standard curing box for curing to 28d, thus obtaining the polypropylene fiber reinforced red mud-based geopolymer material.
In the above preparation method, the total Si/Al (molar ratio) in all the raw materials was 1.2, na/Al (molar ratio) was 1.0, and the mass ratio of water to solid was 0.5.
In the present invention, the bayer process red mud is 600 to 800 parts by weight, preferably 650 to 750 parts by weight, and more preferably 700 parts by weight. The weight part of the coal-based metakaolin is 200-400 parts, preferably 250-350 parts, and more preferably 300 parts. The alkali-activated agent is 750 to 850 parts by weight, preferably 780 to 800 parts by weight, and more preferably 790 parts by weight. The polypropylene fiber is 2 to 8 parts by weight, preferably 3 to 6 parts by weight, more preferably 4 parts by weight.
The polypropylene fiber reinforced red mud base polymer material provided by the invention solves the key problems of low flexural strength, small toughness, large drying shrinkage and the like of the red mud base polymer. Experiments prove that the polypropylene fiber can improve the flexural strength of the geopolymer, enhance the toughness and effectively reduce the drying shrinkage. In addition, experiments show that the flexural strength of the geopolymer of the polymer can be effectively improved, the toughness is enhanced, and the drying shrinkage rate can be effectively reduced only when the length of the polypropylene fiber is more than or equal to 6 mm.
For a clearer description of the present invention, the following examples are provided for illustration.
Example 1:
the formula comprises the following components: 700 parts of Bayer process red mud, 300 parts of coal-based metakaolin, 70 parts of distilled water, 80 parts of sodium hydroxide, 640 parts of sodium silicate solution and 4 parts of polypropylene fibers are prepared. Wherein the length of the polypropylene fiber is 9mm.
Preparing a sample: pouring the Bayer process red mud and the coal-series metakaolin mixture into a mortar stirrer for fully mixing for 2min; adding the dispersed polypropylene fibers, stirring for 2min, adding the alkali-activated agent, stirring for 3min at a rotating speed of 150r/min to form uniformly mixed slurry, and filling the slurry into a steel mould with the thickness of 40mm multiplied by 160 mm. And (3) vibrating the mixture on a mortar vibrating table, scraping the mixture by using a scraper, and standing the mixture at room temperature for 24 hours for molding to obtain the geopolymer cementing material.
Example 2:
the formula comprises the following components: 700 parts of Bayer process red mud, 300 parts of coal-based metakaolin, 70 parts of distilled water, 80 parts of sodium hydroxide, 640 parts of sodium silicate solution and 6 parts of polypropylene fibers are prepared. Wherein the length of the polypropylene fiber is 12mm.
The procedure for preparation and testing of the test block was the same as in example 1.
Comparative example 1:
the procedure of example 1 was repeated except that the control group 1 was a red mud-based polymer without polypropylene fibers, and the formulation and test block were prepared and tested. The compressive strength of the geopolymer is 45.80MPa, the peak strain is 2.66%, and the geopolymer has no residual strength basically; the flexural strength was 4.56MPa and the 90d dry shrinkage value was 19.2mm/m.
Comparative example 2:
the procedure of preparation and test of the formulation and test block was the same as in example 1 except that the polypropylene fiber was prepared using a red mud base polymer having a length of 3mm as a control group 2. The compressive strength of the geopolymer is 43.35MPa, the peak strain is 2.95%, and the residual strength is 5.7MPa; the flexural strength was 4.73MPa and the 90d dry shrinkage value was 16.3mm/m.
The results of the compression test of the geopolymers of the examples and comparative examples at the 28d age are shown in table 1.
TABLE 1
| Project | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 |
| Compressive Strength/MPa | 42.29 | 38.17 | 45.80 | 43.35 |
| Peak strain/% | 3.56 | 3.23 | 2.66 | 2.95 |
| Residual Strength/MPa | 18.98 | 13.72 | Without any means for | 5.7 |
The results of the flexural test of the geopolymers of the examples and comparative examples at the age of 28d are shown in table 2.
TABLE 2
| Project | Example 1 | Example 2 | Comparative example 1 | Comparative example 2 |
| Flexural Strength/MPa | 5.79 | 5.39 | 4.56 | 4.73 |
The 90d dry shrinkage values of the geopolymers of the examples and comparative examples are shown in Table 3.
TABLE 3 Table 3
The comparison shows that: the fiber reinforced red mud base polymer prepared in the embodiment 1 has excellent mechanical properties, compared with the geopolymer without polypropylene fibers, the compressive strength is slightly reduced, but the peak strain is increased by 33.8%, the residual strength is greater than 18MPa, which shows that the brittle failure problem is remarkably improved, the flexural strength is improved by 27.0%, and meanwhile, the drying shrinkage of the red mud base polymer is reduced to a certain extent; example 2 incorporation of polypropylene fibers was more effective in reducing the dry shrinkage of red mud based polymers, which was reduced by 58.3% as compared to the non-polypropylene fiber-incorporated geopolymer, while improving flexural strength to some extent and toughness of the red mud based polymer. In example 2, the length of the polypropylene fiber is 12mm, and in comparative example 2, the length of the polypropylene fiber is 3mm, and the comparison of the two shows that the too small length of the polypropylene fiber has no obvious effect on reducing the drying shrinkage of the red mud base polymer.
Based on the two preferable proportions, the blending amount and the length of the polypropylene fiber are reasonably adjusted, and the requirements on the performance of the geopolymer under different working conditions can be met.
The fiber reinforced geopolymer prepared by the embodiment takes red mud as a main raw material, changes waste into valuable, effectively utilizes industrial waste, has good bonding performance between the selected polypropylene fiber and the geopolymer matrix, ensures the excellent performance of the material, has lower price than other reinforced fibers, reduces the preparation cost of the fiber reinforced geopolymer, and is beneficial to popularization and application. The whole preparation process of the polypropylene fiber reinforced geopolymer has simple process, low carbon and environmental protection, and is beneficial to the protection of ecological environment.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and any person skilled in the art will readily recognize that variations or substitutions are within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (6)
1. The application of polypropylene fibers in reducing the drying shrinkage of a red mud-based polymer material is characterized in that the red mud-based polymer material is prepared from the following raw materials, by weight, 600-800 parts of Bayer process red mud, 200-400 parts of coal-based metakaolin, 750-850 parts of alkali-activated agent and 2-8 parts of polypropylene fibers; the total Si/Al in all raw materials is 1.2, the Na/Al is 1.0, and the mass ratio of water to solid is 0.5; wherein the length of the polypropylene fiber is more than or equal to 9mm, and the diameter is 30-35 mu m;
the preparation method of the red mud base polymer material comprises the following steps:
(1) The high-speed gas generated by the high-pressure air gun is utilized to fully blow off the agglomerated polypropylene fibers;
(2) Accurately weighing Bayer process red mud and coal-series metakaolin according to parts by weight, adding the red mud and the coal-series metakaolin into a mortar stirrer, fully stirring for 2min, adding polypropylene fibers, stirring for 2min, adding an alkali excitant after the fibers are uniformly dispersed, and continuously stirring for 3min to form uniformly mixed fiber reinforced geopolymer slurry;
(3) Pouring the fiber reinforced geopolymer slurry into a steel mould, vibrating for 1min on a vibrating table, sealing the mould by using a preservative film, solidifying for 24h at room temperature, and demoulding;
(4) And (3) placing the demoulded fiber reinforced geopolymer in a standard curing box for curing to 28d, thus obtaining the red mud base geopolymer material.
2. The use according to claim 1, wherein the bayer process red mud has an average particle size of 2.64 μm and a specific surface area of 2270m 2 /kg。
3. The use according to claim 1, wherein the coal-based metakaolin has an average particle size of 1.34 μm and a specific surface area of 4480m 2 /kg。
4. The use according to claim 1, wherein the alkali-activator is mixed from distilled water, sodium hydroxide and water glass solution.
5. The use according to claim 1, wherein the water glass has a modulus of 3.0 to 3.3, and wherein the water glass comprises SiO 2 The content of Na is more than or equal to 20 percent 2 The content of O is more than or equal to 8 percent.
6. The use according to claim 1, wherein the polypropylene fiber has a tensile strength of 460MPa, an elastic modulus of 3.5GPa and an ultimate elongation of 30%.
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