CN113716908B - Modified calcium sulfate whisker reinforced geopolymer and preparation method thereof - Google Patents

Modified calcium sulfate whisker reinforced geopolymer and preparation method thereof Download PDF

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CN113716908B
CN113716908B CN202111196957.4A CN202111196957A CN113716908B CN 113716908 B CN113716908 B CN 113716908B CN 202111196957 A CN202111196957 A CN 202111196957A CN 113716908 B CN113716908 B CN 113716908B
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calcium sulfate
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whisker
geopolymer
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魏铭
张长森
焦宝祥
孙楠
韩朋德
蔡安兰
蔡树元
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Newmat Plastics Technology Shanghai Co ltd
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Yancheng Institute of Technology
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B28/006—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing mineral polymers, e.g. geopolymers of the Davidovits type
    • C—CHEMISTRY; METALLURGY
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    • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
    • C04B14/38—Fibrous materials; Whiskers
    • C04B14/383—Whiskers
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
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    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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    • C04B7/00—Hydraulic cements
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    • C04B2111/20—Resistance against chemical, physical or biological attack
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    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
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    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention discloses a modified calcium sulfate whisker reinforced geopolymer and a preparation method thereof, wherein the modified calcium sulfate whisker reinforced geopolymer comprises the following raw materials in parts by weight: 100 parts of a silicon-aluminum raw material, 35-80 parts of an alkali activator and 1-3 parts of a reinforcing agent; the alkali activator is prepared by mixing 0-20 parts of sodium hydroxide and 80-100 parts of water glass with the modulus of 1.2-3.4; the reinforcing agent is trisodium phosphate modified calcium sulfate whisker. The calcium sulfate whisker modified by trisodium phosphate has the advantages that a monomolecular layer of calcium hydrophosphate film is attached to the surface of the calcium hydrophosphate whisker, so that the van der Waals force among the whiskers is reduced, the reunion of the whiskers is prevented, and the calcium sulfate whisker can be uniformly and independently distributed in a geopolymer matrix; meanwhile, a large amount of hydroxyl (-OH) can be formed on the surface of the whisker, the hydroxyl can participate in the polycondensation reaction of the geopolymer, the effective combination of the whisker and the geopolymer is realized, and the geopolymer prepared by the method has excellent mechanical property, high temperature resistance and acid resistance.

Description

Modified calcium sulfate whisker reinforced geopolymer and preparation method thereof
Technical Field
The invention relates to a geopolymer and a preparation method thereof, in particular to a geopolymer reinforced by modified calcium sulfate whiskers and a preparation method thereof.
Background
Geopolymers are a new type of high performance inorganic polymer cement and are one of the most promising alkali-activated cements. Due to the special inorganic condensed three-dimensional oxide network structure, the geopolymer material has better high-temperature performance and mechanical performance than high-molecular materials, cement, ceramics and metals in many aspects. On the other hand, the energy consumption and the waste discharge amount of the preparation process of the geopolymer material are very low, and the geopolymer material is a sustainable-development green environment-friendly material. The geopolymer has many excellent properties, such as good mechanical properties, small shrinkage and expansion rate, corrosion resistance and remarkable heat insulation effect, and therefore, can be used as a cementing material to replace cement. However, when it is used as a cement substitute, it has problems of high brittleness and low breaking pressure ratio. And thus the application is limited.
In the prior art, many scholars have carried out modification research on geopolymers, for example, the Chinese patent application No. 201910537921.4 discloses a geopolymer toughened by styrene-acrylic emulsion and a preparation method thereof; the Chinese invention patent with application number 201810203132.2 discloses an epoxy resin toughened metakaolin-based polymer and a preparation method thereof; the chinese patent application No. 201611127977.5 discloses a chitosan-modified geopolymer cementitious material; the Chinese invention patent with application number 201910062137.2 discloses an ultrahigh-toughness geopolymer and a preparation method thereof, wherein the used toughening agent is polyvinyl alcohol fiber; leather from a performance study of polyvinyl alcohol-modified geopolymer composites was published by yunity et al; and so on. The modifiers used in the above patents or articles are all polymer materials, but polymer materials have the defects of easy aging, no high temperature resistance and the like.
In addition, after the geopolymer is hydrated and hardened, a hardened body has more harmful holes with the pore diameter of 50-200 nm, so that not only the strength is influenced, but also the comprehensive performances such as frost resistance, durability and the like are influenced, and the popularization and application of the geopolymer are restricted.
However, the micro-nano material has a very small size, a particle diameter of substantially less than 100 μm, a large specific surface area and a large surface energy, so that the acting force between particles (such as van der waals force, electrostatic force, liquid bridge force, and the like) is large relative to the gravity thereof, and the micro-nano material is stored in a natural state and often exists in an agglomerated form, so that the micro-nano material has more limitations in use.
The calcium sulfate whisker is a micron-sized short fiber, and is a novel inorganic toughening material with excellent performances such as high modulus, high strength, low defect, high melting point and the like. The composite fiber has the characteristics of high length-diameter ratio of the traditional fiber, small size of a micro-nano material, low production and purchase cost and extremely high cost performance. However, the whisker is subject to the problems of easy agglomeration and difficult dispersion, and how to realize the surface modification of the whisker, reduce the surface energy of the whisker and reduce the molecular force between particles, and the modified whisker can be dispersed in an alkaline solution, and can form good surface bonding with a geopolymer at the same time, so that the whisker is better wrapped by a geopolymer matrix to form a space skeleton structure, which is a problem to be solved in application.
As described above, the present patent application has been made to solve the main problems of brittle polymers, poor durability, and difficulty in dispersion of whiskers, and to achieve good surface bonding between whiskers and geopolymers.
Disclosure of Invention
The invention aims to: the invention aims to provide a geopolymer reinforced by modified calcium sulfate whiskers, which has high strength and good toughness and improves the dispersibility of the modified whiskers in the geopolymer; the invention also aims to provide a preparation method of the geopolymer reinforced by the modified calcium sulfate whiskers.
The technical scheme is as follows: the modified calcium sulfate whisker reinforced geopolymer comprises the following raw materials in parts by weight: 100 parts of a silicon-aluminum raw material, 35-80 parts of an alkali activator and 1-3 parts of a reinforcing agent; the alkali activator is prepared by mixing 0-20 parts of sodium hydroxide and 80-100 parts of water glass with the modulus of 1.2-3.4; the reinforcing agent is trisodium phosphate modified calcium sulfate whisker. The alkali activator is preferably prepared by mixing 20 parts of sodium hydroxide and 80 parts of water glass solution with modulus of 1.2-3.4.
Further, the alumino-silica raw material is selected from any one or more of fly ash, metakaolin, coal gangue or slag.
Further, the preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: and adding calcium sulfate whiskers into the trisodium phosphate aqueous solution, uniformly mixing, and then carrying out vacuum filtration, washing, drying, grinding and granulating to obtain the trisodium phosphate modified calcium sulfate whiskers.
Furthermore, the concentration of the trisodium phosphate aqueous solution is 0.010-0.020mol/L, and the mass ratio of the trisodium phosphate aqueous solution to the calcium sulfate whisker is 200:3-5.
The preparation method of the modified calcium sulfate whisker reinforced geopolymer comprises the following steps:
(1) Mixing the silicon-aluminum raw material, the modified calcium sulfate whisker and the alkali activator, stirring at a low speed, and then stirring at a high speed to obtain slurry;
(2) And injecting the slurry into a mold for molding, then curing, demolding, and continuously curing for 3-28 days at room temperature to obtain the product.
Further, in the step (1), the rotation speed of the slow stirring is 10-50 r/min, and the time is 2-3 min.
Further, in the step (1), the rotation speed of the rapid stirring is 100-200 r/min, and the time is 2-3 min.
Further, in the step (2), the curing method before demolding is: curing for 20-30 h under the conditions of 20-50 ℃ and relative humidity of 90-95 percent.
The preparation principle of the trisodium phosphate modified calcium sulfate whisker is as follows: dissolving trisodium phosphate in deionized water will produce hydrolysis reaction to produce hydrogen phosphate radical (HPO) 4 2- ) (formula 1), the hydrogen phosphate radical is easy to generate ion substitution reaction with calcium sulfate on the surface of the whisker to replace SO 4 2- And a calcium hydrogen phosphate film (formula 2) is formed on the surface of the whisker, and a large amount of hydroxyl (-OH) capable of participating in early reaction of the geopolymer is formed on the surface of the whisker. The schematic diagram of whisker modification is shown in figure 2. After inorganic modification, the surface of the whisker is activated, so that the whisker is easy to disperse in geopolymer, and can participate in the deconstruction-polycondensation reaction of geopolymer, so that the connection strength of the whisker and the geopolymer is improved, and the modification effect of the whisker on the geopolymer is improved.
Figure BDA0003303379650000031
Figure BDA0003303379650000032
The invention takes a silicon-aluminum material as a main raw material, sodium silicate as an alkali activator and trisodium phosphate modified calcium sulfate whisker as a reinforcing agent. Calcium sulfate whisker modified by trisodium phosphate has the surface attached with monomolecular layer of calcium hydrogen phosphate (CaHPO) 4 ) The film can reduce Van der Waals force among the whiskers, prevent the reunion of the calcium sulfate whiskers in the geopolymer matrix, and enable the calcium sulfate whiskers to be uniformly and independently distributed in the geopolymer matrix, and in addition, a large number of hydroxyl groups (-OH) formed on the surfaces of the whiskers can be subjected to hydrolytic polycondensation reaction with Si-OH and Al-OH generated before the polycondensation reaction of the geopolymer, so that the whiskers are effectively combined with the geopolymer, and the stability of the mechanical property of the modified whisker/geopolymer composite material is improved. The modified whiskers are uniformly dispersed in the geopolymer matrix, so that pores in the geopolymer are effectively filled, and meanwhile, the growth of cracks in the geopolymer is inhibited, and a bridging effect is achieved. When the geopolymer receives the action of external load, the crack grows to break or pull out the crystal whisker, a large amount of energy is consumed, and the mechanical property of the geopolymer can be effectively improved. The calcium sulfate whisker has a high melting point of 1450 ℃, has good heat resistance and a low heat conductivity coefficient, and can absorb most of heat when a geopolymer is in a high-temperature environment, so that the influence of the environmental temperature on the geopolymer is reduced, and the heat resistance of the geopolymer composite material is improved. Because the calcium sulfate whisker contains SO 4 2- In an acidic environment, can resist a part of SO 4 2- Erosion of (2). The calcium sulfate whiskers fill the pores of part of the geopolymer, so that the porosity of the geopolymer is reduced, the Na element is slowly separated out, and the durability of the geopolymer in an acid environment is improved.
Has the beneficial effects that: compared with the prior art, the invention has the following remarkable advantages: the modified whisker reinforced geopolymer has the advantages of good mechanical property, high temperature resistance and sulfate corrosion resistance, and effectively solves the problems of high brittleness, poor mechanical property and poor durability of the traditional geopolymer.
Drawings
FIG. 1 is a flow chart of the preparation of modified whiskers of the present invention;
figure 2 is a schematic model of the modification of whiskers of the present invention.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
In the following examples, the main chemical composition of the silicon-aluminum material is SiO 2 、Al 2 O 3 The silicon-aluminum ratio is 2.5; the balance being Fe 2 O 3 、CaO、MgO、Na 2 O、K 2 O、TiO 2 (ii) a Not limited thereto.
Example 1
A modified calcium sulfate whisker reinforced geopolymer comprises the following raw materials in parts by weight:
100 parts of a silicon-aluminum raw material, 60 parts of an alkali activator and 1 part of a reinforcing agent;
the preparation method of the alkali activator comprises the following steps: mixing 20 parts of sodium hydroxide and 80 parts of water glass with the modulus of 3.4, adjusting the concentration by using deionized water, stirring until sodium hydroxide solid is completely dissolved, and standing for 24 hours to obtain the alkali activator.
The preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: adding 15 parts of calcium sulfate whisker into 1000 parts of 0.010-concentration trisodium phosphate solution, placing the mixture on a magnetic stirrer, stirring for 5min, performing ultrasonic treatment for 5min to obtain uniform modified whisker mixed solution, performing vacuum filtration to obtain modified whisker powder cake, washing and filtering the modified whisker powder cake for 2 times by using pure water, placing the modified whisker powder cake in an oven at 120 ℃ for 24h, drying water, and grinding to obtain modified calcium sulfate whisker powder.
The preparation method of the modified calcium sulfate whisker reinforced geopolymer comprises the following steps:
(1) Mixing a silicon-aluminum raw material, modified calcium sulfate whisker powder and an alkali activator, then stirring at a low speed (the rotating speed is 10r/min and the time is 2 min), and then stirring at a high speed (the rotating speed is 100r/min and the time is 2 min) to obtain slurry;
(2) And injecting the slurry into a mold for molding, curing for 24 hours at the temperature of 20 ℃ and the relative humidity of 90 percent, demolding, and continuously curing for 3 days at room temperature to obtain the product.
Example 2
A modified calcium sulfate whisker reinforced polymer comprises the following raw materials in parts by weight:
100 parts of a silicon-aluminum raw material, 60 parts of an alkali activator and 1.5 parts of a reinforcing agent;
the preparation method of the alkali activator comprises the following steps: mixing 20 parts of sodium hydroxide and 80 parts of water glass with the modulus of 3.4, adjusting the concentration by using deionized water, stirring until sodium hydroxide solids are completely dissolved, and standing for 24 hours to obtain the alkali activator.
The preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: adding 25 parts of calcium sulfate whisker into 1000 parts of 0.020-concentration trisodium phosphate solution, placing the mixture on a magnetic stirrer, stirring for 30min, performing ultrasonic treatment for 30min to obtain uniform modified whisker mixed solution, performing vacuum filtration to obtain modified whisker powder cake, washing and filtering the modified whisker powder cake for 3 times by using pure water, placing the modified whisker powder cake in a 120-DEG C drying oven for 48h, drying water, and grinding to obtain modified calcium sulfate whisker powder.
The preparation method of the modified calcium sulfate whisker reinforced geopolymer comprises the following steps:
(1) Mixing the silicon-aluminum raw material, the modified calcium sulfate whisker powder and the alkali activator, then stirring at a low speed (the rotating speed is 50r/min, and the time is 2 min), and then stirring at a high speed (the rotating speed is 200r/min, and the time is 2 min) to obtain slurry;
(2) Injecting the slurry into a mould for molding, then curing for 24 hours at the temperature of 25 ℃ and under the relative humidity of 95 percent, demolding, and maintaining at room temperature for 28 days.
Example 3
A modified calcium sulfate whisker reinforced polymer comprises the following raw materials in parts by weight:
100 parts of a silicon-aluminum raw material, 60 parts of an alkali activator and 2 parts of a reinforcing agent;
the preparation method of the alkali activator comprises the following steps: mixing 20 parts of sodium hydroxide and 80 parts of water glass with the modulus of 3.4, adjusting the concentration by using deionized water, stirring until sodium hydroxide solids are completely dissolved, and standing for 24 hours to obtain the alkali activator.
The preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: adding 20 parts of calcium sulfate whiskers into 1000 parts of 0.015-concentration trisodium phosphate solution, placing the mixture on a magnetic stirrer, stirring for 20min, performing ultrasonic treatment for 20min to obtain a uniform modified whisker mixed solution, performing vacuum filtration to obtain a modified whisker powder cake, washing and filtering the modified whisker powder cake for 3 times by using pure water, placing the modified whisker powder cake in an oven at 120 ℃ for 36h, drying water, and grinding to obtain modified calcium sulfate whisker powder.
The preparation method of the modified calcium sulfate whisker reinforced geopolymer comprises the following steps:
(1) Mixing a silicon-aluminum raw material, modified calcium sulfate whisker powder and an alkali activator, then stirring at a low speed (the rotating speed is 30r/min and the time is 2 min), and then stirring at a high speed (the rotating speed is 150r/min and the time is 2 min) to obtain slurry;
(2) Injecting the slurry into a mould for molding, then curing for 24 hours at the temperature of 23 ℃ under the condition that the relative humidity is 92 percent, demolding, and maintaining at room temperature for 14 days.
Example 4
A modified calcium sulfate whisker reinforced polymer comprises the following raw materials in parts by weight:
100 parts of a silicon-aluminum raw material, 60 parts of an alkali activator and 2.5 parts of a reinforcing agent;
the preparation method of the alkali activator comprises the following steps: mixing 20 parts of sodium hydroxide and 80 parts of water glass with the modulus of 3.4, adjusting the concentration by using deionized water, stirring until sodium hydroxide solids are completely dissolved, and standing for 24 hours to obtain the alkali activator.
The preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: same as in example 1.
The preparation method of the modified calcium sulfate whisker reinforced geopolymer comprises the following steps:
(1) Mixing a silicon-aluminum raw material, modified calcium sulfate whisker powder and an alkali activator, then stirring at a low speed (the rotating speed is 10-50 r/min, the time is 2 min), and then stirring at a high speed (the rotating speed is 100-200 r/min, the time is 2 min) to obtain slurry;
(2) And injecting the slurry into a mold for molding, then curing for 24 hours at the temperature of 20-25 ℃ and the relative humidity of 90-95%, demolding, and continuously curing for 3-28 days at room temperature to obtain the high-strength high-toughness high-strength concrete.
Example 5
A modified calcium sulfate whisker reinforced polymer comprises the following raw materials in parts by weight:
100 parts of a silicon-aluminum raw material, 60 parts of an alkali activator and 3 parts of a reinforcing agent;
the preparation method of the alkali activator comprises the following steps: mixing 20 parts of sodium hydroxide and 80 parts of water glass with the modulus of 3.4, adjusting the concentration by using deionized water, stirring until sodium hydroxide solids are completely dissolved, and standing for 24 hours to obtain the alkali activator.
The preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: same as in example 2.
(1) Mixing a silicon-aluminum raw material, modified calcium sulfate whisker powder and an alkali activator, then slowly stirring (the rotating speed is 10-50 r/min, the time is 2 min), and then quickly stirring (the rotating speed is 100-200 r/min, the time is 2 min) to obtain slurry;
(2) Injecting the slurry into a mold for molding, then curing for 24 hours at the temperature of 20-25 ℃ and the relative humidity of 90-95%, demolding, and continuously curing for 3-28 days at room temperature to obtain the product.
Comparative example
A method for preparing a geopolymer: mixing and stirring a water glass solution (modulus of 3.3) and sodium hydroxide at room temperature in a weight ratio of 4; mixing 100 parts by weight of silicon-aluminum raw material and 60 parts by weight of alkali activator into slurry, injecting the slurry into a mold for molding, curing for 24 hours at the temperature of 25 ℃ and the relative humidity of more than 90%, demolding, and continuously curing for 3-28 days to obtain the geopolymer sample.
The flexural strength, compressive strength and flexural ratio of the geopolymers of examples and comparative examples after curing at 28d and 800 ℃ were as shown in Table 1 below.
TABLE 1 Strength
Figure BDA0003303379650000061
As can be seen from Table 1, compared with the comparative examples, the compressive strength and the flexural strength of the geopolymer prepared by the examples of the invention are obviously improved compared with the comparative examples, the modified calcium sulfate whiskers are doped into the geopolymer in different doping amounts, the strength improvement is different, the flexural ratio can reflect the toughness of the product from the side, and the doping of the calcium sulfate whiskers obviously improves the toughness of the geopolymer from the flexural ratio. After calcination at 800 ℃, the compressive strength and the flexural strength of the geopolymer-based composite material of the embodiment of the invention are as high as 1 time of those of a comparison sample, which shows that the high temperature resistance is good.
Table 2 shows the pore structure parameters for example 1 and the control. It can be seen from table 2 that the harmful pores in the example samples after the modified calcium sulfate whiskers are incorporated are greatly reduced, thereby being beneficial to improving the strength and toughness of the geopolymer.
TABLE 2 pore structure parameters
Figure BDA0003303379650000071
The calcium sulfate whisker is doped to play a role in filling, improve the macroscopic mechanical property of the geopolymer, improve the sulfate erosion resistance of the geopolymer and improve the durability of the geopolymer in an acid environment.

Claims (5)

1. The modified calcium sulfate whisker reinforced polymer is characterized by comprising the following raw materials in parts by weight: 100 parts of a silicon-aluminum raw material, 60 parts of an alkali activator and 1 part of a reinforcing agent, wherein the silicon-aluminum raw material is selected from one or more of fly ash, metakaolin, coal gangue or slag; the preparation method of the alkali activator comprises the following steps: mixing 20 parts of sodium hydroxide and 80 parts of water glass with the modulus of 3.4, adjusting the concentration by using deionized water, stirring until sodium hydroxide solids are completely dissolved, and standing for 24 hours to obtain an alkali activator; the reinforcing agent is trisodium phosphate modified calcium sulfate whisker, and the preparation method of the trisodium phosphate modified calcium sulfate whisker comprises the following steps: adding 15 parts of calcium sulfate whiskers into 1000 parts of trisodium phosphate solution with the concentration of 0.010mol/L, placing the mixture on a magnetic stirrer, stirring for 5min, performing ultrasonic treatment for 5min to obtain uniform modified whisker mixed solution, performing vacuum filtration to obtain modified whisker powder cakes, washing and filtering the modified whisker powder cakes for 2 times by using pure water, placing the modified whisker powder cakes in an oven at 120 ℃ for 24h, drying water, and grinding to obtain modified calcium sulfate whisker powder.
2. The method for preparing the modified calcium sulfate whisker reinforced polymer according to claim 1, comprising the following steps:
(1) Mixing the silicon-aluminum raw material, the modified calcium sulfate whisker and the alkali activator, stirring at a low speed, and then stirring at a high speed to obtain slurry;
(2) And injecting the slurry into a mold for molding, then curing, demolding, and continuously curing for 3 to 28d under the room temperature condition to obtain the coating.
3. The preparation method according to claim 2, wherein in the step (1), the rotation speed of the slow stirring is 10 to 50r/min, and the time is 2 to 3min.
4. The preparation method according to claim 2, wherein in the step (1), the rotation speed of the rapid stirring is 100 to 200r/min, and the time is 2 to 3min.
5. The production method according to claim 2, wherein in the step (2), the curing method before the mold release is: curing for 20 to 30h under the conditions of 20 to 50 ℃ and relative humidity of 90 to 95 percent.
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