CN112079593B - Siloxane modified super-hydrophobic geopolymer anticorrosive material and preparation method thereof - Google Patents

Siloxane modified super-hydrophobic geopolymer anticorrosive material and preparation method thereof Download PDF

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CN112079593B
CN112079593B CN202010753267.3A CN202010753267A CN112079593B CN 112079593 B CN112079593 B CN 112079593B CN 202010753267 A CN202010753267 A CN 202010753267A CN 112079593 B CN112079593 B CN 112079593B
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siloxane
geopolymer
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CN112079593A (en
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闫东明
阮圣倩
陈士堃
朱嵘华
刘毅
田野
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Zhejiang University ZJU
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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
    • 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
    • C04B24/40—Compounds containing silicon, titanium or zirconium or other organo-metallic compounds; Organo-clays; Organo-inorganic complexes
    • C04B24/42—Organo-silicon compounds
    • 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
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/27—Water resistance, i.e. waterproof or water-repellent materials
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

Abstract

The invention discloses a siloxane modified super-hydrophobic geopolymer anticorrosive material which comprises the following raw materials in parts by weight: 70-90 parts of silicon-aluminum mineral raw material, 75-100 parts of alkali activator, 2-3 parts of polydimethylsiloxane, 4-5 parts of methyl hydrogen-containing silicone oil, 0.1-0.2 part of silane coupling agent, 4-6 parts of nano magnesium hydroxide powder, 7-10 parts of nano silicon dioxide powder, 3-5 parts of short fiber, 1-2 parts of calcium lignosulfonate and 1-1.5 parts of grinding aid. The invention also discloses a preparation method of the siloxane modified super-hydrophobic geopolymer anticorrosive material. The invention utilizes the method of modifying and combining the substrate and the surface super-hydrophobic by siloxane, and combines the surface chemical structure modification of the substrate and the modification of nano-scale roughness and micro-scale roughness, thereby improving the super-hydrophobic and high corrosion resistance of the compact high-strength geopolymer material; the addition of the raw materials, the nano materials and the short fibers ensures that the material has high strength, compact structure and strong durability, and the super-hydrophobic modification realizes the resistance of the material to ion erosion, substance dissolution, freeze-thaw damage and the like.

Description

Siloxane modified super-hydrophobic geopolymer anticorrosive material and preparation method thereof
Technical Field
The invention belongs to the technical field of novel building materials, and particularly relates to a siloxane modified super-hydrophobic geopolymer anticorrosive material and a preparation method thereof.
Background
With the improvement of the state engineering level, wading engineering buildings represented by ocean engineering are rapidly developed. However, the conventional cement-based building materials are difficult to obtain ideal effects in durability because the wading buildings are continuously contacted with the water environment and are subjected to long-term destructive action of wind, waves and currents. As a new green and environment-friendly building material, geopolymers attract extensive research of worldwide scholars by virtue of excellent performance characteristics of rapid and controllable setting and hardening, high strength and adhesion, strong durability and the like.
Geopolymers are used as inorganic nonmetallic materials, the matrix of the geopolymers is hydrophilic, and the durability of the geopolymers is also influenced by the water property. Since many disruptions occur in the presence of water, such as dissolution of material, sulfate attack, salt crystallization, freeze-thaw cycling, and the like. In the traditional method, the mode of adding admixture and reducing the water-to-glue ratio is adopted to improve the compactness of a matrix and reduce defects, but the method cannot avoid the invasion of water-carrying harmful substances. Hydrophobic protective coatings provide some protection to the material, but are limited due to the short service life and poor resistance to mechanical damage. Therefore, on the basis of the compact and complete material, the hydrophilic and hydrophobic properties of the polymer matrix are changed by using the siloxane additive, and the roughness of the surface and the inside of the material is enhanced by using the nylon net and the nano filler, so that the water absorption and the permeability of the material are weakened.
In the existing research, the chinese patent with application number CN 201510638847.7 is "a metakaolin based geopolymer with super-hydrophobic surface and its preparation method", which is to paint or spray a liquid hydrophobic modifier on the surface of the metakaolin based geopolymer, only to modify the geopolymer from the surface, which is difficult to withstand the mechanical damage.
The Chinese patent with the application number of CN 201611115484.X is a preparation method of a waterproof and noncombustible fly ash/metakaolin-based insulation board, and the method selects various aggregates and polystyrene waterproof materials, but the method has poor hydrophobic effect and more material defects, and is difficult to achieve ideal waterproof performance.
Chinese patent No. CN 201911076304.5 discloses a waterproof paint for cement-based floor polymer, its preparation method and equipment, wherein the waterproof paint is prepared by spraying chemical substances such as phenol, ester, alcohol, alkanone and resin in a stirring kettle. However, the organic waterproof coating has limited service life and poor bonding performance with building materials, and is difficult to achieve long-term hydrophobic effect.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a siloxane modified super-hydrophobic geopolymer anticorrosive material, which is improved from hydrophobic modification of an internal matrix to chemical structure and physical roughness of the surface to obtain the geopolymer anticorrosive material with super-hydrophobic property.
The technical scheme adopted by the invention for solving the technical problems is as follows: the siloxane modified super-hydrophobic geopolymer anticorrosive material comprises the following raw materials in parts by weight: 70-90 parts of silicon-aluminum mineral raw material, 75-100 parts of alkali activator, 2-3 parts of polydimethylsiloxane, 4-5 parts of methyl hydrogen-containing silicone oil, 0.1-0.2 part of silane coupling agent, 4-6 parts of nano magnesium hydroxide powder, 7-10 parts of nano silicon dioxide powder, 3-5 parts of short fiber, 1-2 parts of calcium lignosulfonate and 1-1.5 parts of grinding aid.
Preferably, the silicon-aluminum mineral raw material is a compound material and comprises 45-55 parts of metakaolin, 15-20 parts of fly ash and 10-15 parts of silica fume.
Preferably, the alkali activator is a compound material and comprises 15-20 parts of sodium hydroxide solid, 45-55 parts of sodium silicate solution and 15-25 parts of deionized water, and the total water content is 40-50%.
Preferably, the sodium silicate solution is a mixed solution of sodium silicate and deionized water, wherein SiO is2With Na2The molar mass ratio of O is 3-4.
Preferably, the polydimethylsiloxane has a viscosity of 50 to 200 stokes; the main component of the methyl hydrogen-containing silicone oil is polymethylhydrosiloxane, and the effective component is more than 95%; the effective component of the silane coupling agent is more than 95 percent.
Preferably, the particle size of the nano magnesium hydroxide powder is 20-100 nanometers, and the purity is more than 99%.
Preferably, the particle size of the nano silicon dioxide powder is 10-30 nanometers, and the purity is more than 99 percent.
Preferably, the short fiber is one or the combination of more than two of silicon carbide fiber, basalt fiber and carbon fiber, the average diameter is 20-50 micrometers, and the length is 2-6 millimeters.
Preferably, the calcium lignosulfonate has a purity of greater than 95%.
The invention also discloses a preparation method of the siloxane modified super-hydrophobic geopolymer anticorrosive material, which comprises the following steps:
1) preparation of alkali activator: mixing 15-20 parts of sodium hydroxide solid, 45-55 parts of sodium silicate solution and 15-25 parts of deionized water, stirring until the mixture is uniform and clear, pouring the mixture into a plastic container, and sealing and storing for 12-24 hours to obtain an alkali activator;
2) preparation of the siloxane-fiber-alkali activator solution: mixing 2-3 parts of polydimethylsiloxane, 0.1-0.2 part of silane coupling agent, 3-5 parts of short fiber and the alkali activator obtained in the step 1), and performing ultrasonic dispersion for 60-90 minutes at 50-60 Hz to obtain a siloxane-fiber-alkali activator solution;
3) preparation of solid raw materials: mixing 70-90 parts of a silicon-aluminum mineral raw material, 4-6 parts of nano magnesium hydroxide powder, 7-10 parts of nano silicon dioxide powder, 1-2 parts of calcium lignosulphonate and 1-1.5 parts of a grinding aid in proportion, stirring and grinding for 40-60 minutes to obtain a solid raw material;
4) preparing a nylon net with hydrogen-containing silicone oil: soaking a 400-mesh nylon net with 1000 meshes in methyl hydrogen-containing silicone oil for 12-24 hours, wiping the nylon net with a paper towel until the surface is dry before the preparation test, and then placing the nylon net at the bottom of a mold;
5) preparation of geopolymer slurry: mixing the siloxane-fiber-alkali activator solution obtained in the step 2) with the solid raw material obtained in the step 3), and mechanically stirring at the rotating speed of 800-;
6) pouring the geopolymer slurry obtained in the step 5) into a mold with the bottom padded with the hydrogen-containing silicone oil nylon net obtained in the step 4) for curing, and firstly, carrying out water-retaining curing in an oven or a vacuum drying oven at the temperature of 40-65 ℃ for 24-48 hours. Demoulding, removing the nylon net, and naturally curing at room temperature for 3-14 days.
The silicon-aluminum mineral raw material and the alkali activator are compounded in an ideal proportion to prepare the material with high polymerization degree, high density of matrix structure and high mechanical strength. Metakaolin and fly ash are used as main raw materials, and the mixing is favorable for filling pores of the material and reducing the porosity of macropores; the silica fume has the filling function, can improve the fluidity of slurry and promote the dispersion and reaction of solid raw materials. Polydimethylsiloxane and silane coupling agents are used for a geopolymer material matrix, and hydrophobic modification is carried out on the surface chemical structure of the material matrix. The nylon net treated by the methyl hydrogen silicone oil contains abundant siloxane due to hydrogen bonds, so that the sample prepared by the nylon net can enable the surface of the material to contain the polymethyl hydrogen siloxane, and the polymethyl hydrogen siloxane can further grow on the original hydrophobic surface. Meanwhile, the concave-convex structure of the nylon net ensures that the surface obtains micron-level roughness, thereby further enhancing the hydrophobic capability of the material. The nano magnesium hydroxide powder can be used as a nano filler, can form nano-scale raised crystals in geopolymerization reaction to increase the nano roughness of a matrix, can resist geopolymer shrinkage, reduce crack generation and enhance the mechanical property and durability of the material. The nano silicon dioxide powder can be used as a filler to increase the nano roughness of the matrix and is beneficial to improving the strength of the material. The short fibers are used as micron-sized protrusions to provide roughness required by hydrophobicity, the toughness and the strength of the material are greatly improved, and crack generation is reduced. The calcium lignosulfonate is used as a surfactant, is beneficial to promoting the dispersion of various substances, and can also enhance the strength and durability of the whole material.
The invention has the beneficial effects that: 1) the invention innovatively utilizes the method of siloxane for modifying and combining the substrate and the surface superhydrophobic property, combines the modification of the surface chemical structure of the substrate and the modification of the nano-scale roughness and the micro-scale roughness, and improves the superhydrophobic property and the high corrosion resistance of the compact high-strength geopolymer material; 2) the addition of the raw materials, the nano materials and the short fibers ensures that the material has high strength, compact structure and strong durability, so that the super-hydrophobic modification realizes the resistance of the material to ion erosion, substance dissolution, freeze-thaw damage and the like, and promotes the rapid development of the field of high-strength durable building materials; 3) the waste raw materials such as fly ash and silica fume are utilized, the product manufacturing period is short, the process is green and safe, the conditions such as high temperature and the like are not needed, and the strategic requirements of energy conservation, environmental protection and sustainable development are met; 4) the invention can be used as a hydrophobic corrosion-resistant new material to be applied to the fields of common buildings, marine wading engineering and extreme environment buildings.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
A siloxane-modified super-hydrophobic geopolymer anticorrosive material comprises 45 parts of metakaolin, 20 parts of fly ash, 10 parts of silica fume, 15 parts of sodium hydroxide solids, 50 parts of a sodium silicate solution, 18 parts of deionized water, 2 parts of polydimethylsiloxane, 5 parts of methyl hydrogen-containing silicone oil, 0.1 part of a silane coupling agent, 5 parts of nano magnesium hydroxide powder, 10 parts of nano silicon dioxide powder, 2 parts of silicon carbide fibers, 2 parts of basalt fibers, 1 part of calcium lignosulfonate and 1 part of a grinding aid.
SiO in sodium silicate solution2With Na2The molar mass ratio of O is 3; polydimethylsiloxane viscosity was 100 stokes; the average grain diameter of the nano magnesium hydroxide powder is 35 nanometers; the average grain diameter of the nano silicon dioxide powder is 15 nanometers; the average diameter of the silicon carbide fiber is 20 micrometers, and the average length of the silicon carbide fiber is 6 millimeters; the basalt fibers had an average diameter of 45 micrometers and an average length of 5 millimeters.
A preparation method of siloxane modified super-hydrophobic geopolymer anticorrosive material comprises the following steps:
1) preparation of alkali activator: mixing 15 parts of sodium hydroxide solid, 50 parts of sodium silicate solution and 10 parts of deionized water, stirring until the mixture is uniform and clear, pouring the mixture into a plastic container, and sealing and storing for 12 hours to obtain an alkali activator;
2) preparation of the siloxane-fiber-alkali activator solution: mixing 2 parts of polydimethylsiloxane, 0.1 part of silane coupling agent, 2 parts of silicon carbide fiber, 2 parts of basalt fiber and the alkali activator obtained in the step 1), and performing 50 Hz ultrasonic dispersion for 90 minutes to obtain a siloxane-fiber-alkali activator solution;
3) preparation of solid raw materials: mixing 45 parts of metakaolin, 20 parts of fly ash, 10 parts of silica fume, 5 parts of nano magnesium hydroxide powder, 10 parts of nano silicon dioxide powder, 1 part of calcium lignosulfonate and 1 part of grinding aid in proportion, stirring and grinding for 60 minutes to obtain a solid raw material;
4) preparing a nylon net with hydrogen-containing silicone oil: soaking a 800-mesh nylon net in methyl hydrogen-containing silicone oil for 24 hours, wiping the nylon net with a paper towel before a preparation test until the surface is dry, and then placing the nylon net at the bottom of a mold;
5) preparation of geopolymer slurry: mixing the siloxane-fiber-alkali activator solution obtained in the step 2) with the solid raw material obtained in the step 3), and mechanically stirring at the rotating speed of 1200 revolutions per minute for 30 minutes to obtain geopolymer slurry;
6) preparing a sample: pouring the geopolymer slurry obtained in the step 5) into a mold with the bottom padded with the hydrogen-containing silicone oil nylon net obtained in the step 4) for curing, and firstly maintaining for 36 hours in an oven or a vacuum drying oven at the temperature of 60 ℃ in a water-retaining manner. And (4) after demolding and nylon net removal treatment, naturally curing for 7 days at room temperature to obtain the product.
Example two
A siloxane-modified super-hydrophobic geopolymer anticorrosive material comprises 50 parts of metakaolin, 15 parts of fly ash, 10 parts of silica fume, 18 parts of sodium hydroxide solids, 48 parts of a sodium silicate solution, 15 parts of deionized water, 2.5 parts of polydimethylsiloxane, 5 parts of methyl hydrogen-containing silicone oil, 0.15 part of a silane coupling agent, 6 parts of nano magnesium hydroxide powder, 8 parts of nano silicon dioxide powder, 2 parts of silicon carbide fibers, 1 part of carbon fibers, 1 part of calcium lignosulfonate and 1 part of a grinding aid.
SiO in sodium silicate solution2With Na2The molar mass ratio of O is 3.5; polydimethylsiloxane viscosity was 50 stokes; the average grain diameter of the nano magnesium hydroxide powder is 40 nanometers; the average grain diameter of the nano silicon dioxide powder is 20 nanometers; the average diameter of the silicon carbide fiber is 20 micrometers, and the average length of the silicon carbide fiber is 6 millimeters; the carbon fibers had an average diameter of 12 microns and an average length of 6 millimeters.
A preparation method of siloxane modified super-hydrophobic geopolymer anticorrosive material comprises the following steps:
1) preparation of alkali activator: mixing 18 parts of sodium hydroxide solid, 48 parts of sodium silicate solution and 15 parts of deionized water, stirring until the mixture is uniform and clear, pouring the mixture into a plastic container, and sealing and storing for 12 hours to obtain an alkali activator;
2) preparation of the siloxane-fiber-alkali activator solution: mixing 2.5 parts of polydimethylsiloxane, 0.15 part of silane coupling agent, 2 parts of silicon carbide fiber, 1 part of carbon fiber and the alkali activator obtained in the step 1), and performing 50 Hz ultrasonic dispersion for 90 minutes to obtain a siloxane-fiber-alkali activator solution;
3) preparation of solid raw materials: mixing 50 parts of metakaolin, 15 parts of fly ash, 10 parts of silica fume, 6 parts of nano magnesium hydroxide powder, 8 parts of nano silicon dioxide powder, 1 part of calcium lignosulfonate and 1 part of grinding aid in proportion, stirring and grinding for 60 minutes to obtain a solid raw material;
4) preparing a nylon net with hydrogen-containing silicone oil: soaking a 400-mesh nylon net in methyl hydrogen-containing silicone oil for 24 hours, wiping the nylon net with a paper towel before a preparation test until the surface is dry, and then placing the nylon net at the bottom of a mold;
5) preparation of geopolymer slurry: mixing the siloxane-fiber-alkali activator solution obtained in the step 2) with the solid raw material obtained in the step 3), and mechanically stirring at the rotating speed of 1200 revolutions per minute for 30 minutes to obtain geopolymer slurry;
6) preparing a sample: pouring the geopolymer slurry obtained in the step 5) into a mold with the bottom padded with the hydrogen-containing silicone oil nylon net obtained in the step 4) for curing, and firstly maintaining for 36 hours in an oven or a vacuum drying oven at the temperature of 60 ℃ in a water-retaining manner. And (4) after demolding and nylon net removal treatment, naturally curing for 7 days at room temperature to obtain the product.
EXAMPLE III
SiO in sodium silicate solution2With Na2The molar mass ratio of O is 3; the siloxane-modified super-hydrophobic geopolymer anticorrosive material comprises 55 parts of metakaolin, 15 parts of fly ash, 10 parts of silica fume, 20 parts of sodium hydroxide solid, 50 parts of sodium silicate solution, 15 parts of deionized water, 3 parts of polydimethylsiloxane, 5 parts of methyl hydrogen-containing silicone oil, 0.2 part of silane coupling agent, 6 parts of nano magnesium hydroxide powder, 10 parts of nano silicon dioxide powder, 1 part of silicon carbide fiber, 1 part of basalt fiber, 1 part of carbon fiber, 1.5 parts of calcium lignosulfonate and 1 part of grinding aid.
Polydimethylsiloxane viscosity was 50 stokes; the average grain diameter of the nano magnesium hydroxide powder is 40 nanometers; the average grain diameter of the nano silicon dioxide powder is 25 nanometers; the average diameter of the silicon carbide fiber is 20 micrometers, and the average length of the silicon carbide fiber is 6 millimeters; the basalt fiber has an average diameter of 45 micrometers and an average length of 5 millimeters; the carbon fibers had an average diameter of 12 microns and an average length of 6 millimeters.
A preparation method of siloxane modified super-hydrophobic geopolymer anticorrosive material comprises the following steps:
1) preparation of alkali activator: mixing 20 parts of sodium hydroxide solid, 50 parts of sodium silicate solution and 15 parts of deionized water, stirring until the mixture is uniform and clear, pouring the mixture into a plastic container, and sealing and storing for 12 hours to obtain an alkali activator;
2) preparation of the siloxane-fiber-alkali activator solution: mixing 3 parts of polydimethylsiloxane, 0.2 part of silane coupling agent, 1 part of silicon carbide fiber, 1 part of basalt fiber, 1 part of carbon fiber and the alkali activator obtained in the step 1), and performing 60 Hz ultrasonic dispersion for 90 minutes to obtain a siloxane-fiber-alkali activator solution;
3) preparation of solid raw materials: mixing 55 parts of metakaolin, 15 parts of fly ash, 10 parts of silica fume, 6 parts of nano magnesium hydroxide powder, 10 parts of nano silicon dioxide powder, 1.5 parts of calcium lignosulfonate and 1 part of grinding aid in proportion, stirring and grinding for 60 minutes to obtain a solid raw material;
4) preparing a nylon net with hydrogen-containing silicone oil: soaking a 1000-mesh nylon net in methyl hydrogen-containing silicone oil for 24 hours, wiping the nylon net with a paper towel before a preparation test until the surface is dry, and then placing the nylon net at the bottom of a mold;
5) preparation of geopolymer slurry: mixing the siloxane-fiber-alkali activator solution obtained in the step 2) with the solid raw material obtained in the step 3), and mechanically stirring at the rotating speed of 1200 revolutions per minute for 30 minutes to obtain geopolymer slurry;
6) preparing a sample: pouring the geopolymer slurry obtained in the step 5) into a mold with the bottom padded with the hydrogen-containing silicone oil nylon net obtained in the step 4) for curing, and firstly maintaining for 36 hours in an oven or a vacuum drying oven at the temperature of 60 ℃ in a water-retaining manner. And (4) after demolding and nylon net removal treatment, naturally curing for 7 days at room temperature to obtain the product.
Comparative example four
A polymer material comprises 50 parts of metakaolin, 15 parts of fly ash, 10 parts of silica fume, 18 parts of sodium hydroxide solid, 48 parts of sodium silicate solution, 15 parts of deionized water, 6 parts of nano magnesium hydroxide powder, 8 parts of nano silicon dioxide powder, 1 part of silicon carbide fiber, 1 part of basalt fiber, 1 part of carbon fiber, 1.5 parts of calcium lignosulfonate and 1 part of grinding aid.
SiO in sodium silicate solution2With Na2The molar mass ratio of O is 3.5; the average grain diameter of the nano magnesium hydroxide powder is 45 nanometers; the average grain diameter of the nano silicon dioxide powder is 20 nanometers; the average diameter of the silicon carbide fiber is 20 micrometers, and the average length of the silicon carbide fiber is 6 millimeters; the basalt fiber has an average diameter of 45 micrometers and an average length of 5 millimeters; the carbon fibers had an average diameter of 12 microns and an average length of 6 millimeters.
The preparation method of the geopolymer material comprises the following steps:
1) preparation of alkali activator: mixing 18 parts of sodium hydroxide solid, 48 parts of sodium silicate solution and 15 parts of deionized water, stirring until the mixture is uniform and clear, pouring the mixture into a plastic container, and sealing and storing for 12 hours to obtain an alkali activator;
2) preparation of fiber-alkali activator solution: mixing 1 part of silicon carbide fiber, 1 part of basalt fiber, 1 part of carbon fiber and the alkali activator obtained in the step 1), and performing 60 Hz ultrasonic dispersion for 90 minutes to obtain a fiber-alkali activator solution;
3) preparation of solid raw materials: mixing 50 parts of metakaolin, 15 parts of fly ash, 10 parts of silica fume, 6 parts of nano magnesium hydroxide powder, 8 parts of nano silicon dioxide powder, 1 part of calcium lignosulfonate and 1 part of grinding aid in proportion, stirring and grinding for 60 minutes to obtain a solid raw material;
4) preparation of geopolymer slurry: mixing the fiber-alkali activator solution obtained in the step 2) and the solid raw material obtained in the step 3), and mechanically stirring at the rotating speed of 1200 rpm for 30 minutes to obtain geopolymer slurry;
5) preparing a sample: pouring the geopolymer slurry obtained in the step 4) into a common mould for curing, and firstly, maintaining for 36 hours in an oven or a vacuum drying oven with the temperature of 60 ℃. And (4) after demolding treatment, naturally curing for 7 days at room temperature to obtain the product.
Comparative example five
A polymer material comprises 55 parts of metakaolin, 15 parts of fly ash, 10 parts of silica fume, 20 parts of sodium hydroxide solid, 50 parts of sodium silicate solution, 15 parts of deionized water, 3 parts of polydimethylsiloxane, 0.2 part of silane coupling agent, 6 parts of nano magnesium hydroxide powder, 10 parts of nano silicon dioxide powder, 1 part of silicon carbide fiber, 1 part of basalt fiber, 1 part of carbon fiber, 1.5 parts of calcium lignosulfonate and 1 part of grinding aid.
SiO in sodium silicate solution2With Na2The molar mass ratio of O is 3; polydimethylsiloxane viscosity was 50 stokes; the average grain diameter of the nano magnesium hydroxide powder is 40 nanometers; the average grain diameter of the nano silicon dioxide powder is 25 nanometers; the average diameter of the silicon carbide fiber is 20 micrometers, and the average length of the silicon carbide fiber is 6 millimeters; the basalt fiber has an average diameter of 45 micrometers and an average length of 5 millimeters; the carbon fibers had an average diameter of 12 microns and an average length of 6 millimeters.
The preparation method of the geopolymer material comprises the following steps:
1) preparation of alkali activator: mixing 20 parts of sodium hydroxide solid, 50 parts of sodium silicate solution and 15 parts of deionized water, stirring until the mixture is uniform and clear, pouring the mixture into a plastic container, and sealing and storing for 12 hours to obtain an alkali activator;
2) preparation of the siloxane-fiber-alkali activator solution: mixing 3 parts of polydimethylsiloxane, 0.2 part of silane coupling agent, 1 part of silicon carbide fiber, 1 part of basalt fiber, 1 part of carbon fiber and the alkali activator obtained in the step 1), and performing 60 Hz ultrasonic dispersion for 90 minutes to obtain a siloxane-fiber-alkali activator solution;
3) preparation of solid raw materials: mixing 55 parts of metakaolin, 15 parts of fly ash, 10 parts of silica fume, 6 parts of nano magnesium hydroxide powder, 10 parts of nano silicon dioxide powder, 1.5 parts of calcium lignosulfonate and 1 part of grinding aid in proportion, stirring and grinding for 60 minutes to obtain a solid raw material;
4) preparation of geopolymer slurry: mixing the fiber-alkali activator solution obtained in the step 2) and the solid raw material obtained in the step 3), and mechanically stirring at the rotating speed of 1200 rpm for 30 minutes to obtain geopolymer slurry;
5) preparing a sample: pouring the geopolymer slurry obtained in the step 4) into a common mould for curing, and firstly, maintaining for 36 hours in an oven or a vacuum drying oven with the temperature of 60 ℃. And (4) after demolding treatment, naturally curing for 7 days at room temperature to obtain the product.
Comparative example six
The geopolymer material comprises 50 parts of metakaolin, 15 parts of fly ash, 10 parts of silica fume, 18 parts of sodium hydroxide solid, 48 parts of sodium silicate solution, 15 parts of deionized water, 2.5 parts of polydimethylsiloxane, 5 parts of methyl hydrogen silicone oil, 0.15 part of silane coupling agent, 1 part of calcium lignosulfonate and 1 part of grinding aid.
SiO in sodium silicate solution2With Na2The molar mass ratio of O is 3; the polydimethylsiloxane viscosity was 50 stokes.
The preparation method of the geopolymer material comprises the following steps:
1) preparation of alkali activator: mixing 18 parts of sodium hydroxide solid, 48 parts of sodium silicate solution and 15 parts of deionized water, stirring until the mixture is uniform and clear, pouring the mixture into a plastic container, and sealing and storing for 12 hours to obtain an alkali activator;
2) preparation of siloxane-base activator solution: mixing 2.5 parts of polydimethylsiloxane, 0.15 part of silane coupling agent and the alkali activator in the step 1), and performing 50 Hz ultrasonic dispersion for 60 minutes to obtain a siloxane-alkali activator solution;
3) preparation of solid raw materials: mixing 50 parts of metakaolin, 15 parts of fly ash, 10 parts of silica fume, 1 part of calcium lignosulfonate and 1 part of grinding aid in proportion, stirring and grinding for 60 minutes to obtain a solid raw material;
4) preparing a nylon net with hydrogen-containing silicone oil: soaking a 600-mesh nylon net in methyl hydrogen-containing silicone oil for 24 hours, wiping the nylon net with a paper towel before preparation test until the surface is dry, and then placing the nylon net at the bottom of a mold;
5) preparation of geopolymer slurry: mixing the siloxane-fiber-alkali activator solution obtained in the step 2) with the solid raw material obtained in the step 3), and mechanically stirring at the rotating speed of 1200 revolutions per minute for 30 minutes to obtain geopolymer slurry;
6) preparing a sample: pouring the geopolymer slurry obtained in the step 5) into a mold with the bottom padded with the hydrogen-containing silicone oil nylon net obtained in the step 4) for curing, and firstly maintaining for 36 hours in an oven or a vacuum drying oven at the temperature of 60 ℃ in a water-retaining manner. And (4) after demolding and nylon net removal treatment, naturally curing for 7 days at room temperature to obtain the product.
In order to verify the mechanical property and the hydrophobic property of the super-hydrophobic geopolymer anticorrosive material, a compressive strength test, a flexural strength test and a contact angle test, the specific method and the result are as follows:
(1) and (3) strength test: the foamed geopolymer materials obtained in examples and comparative examples were used as test specimens for testing the compressive strength and the flexural strength in accordance with GB/T17671-1999 Cement mortar Strength test method (ISO method).
(2) Contact angle test: the foamed geopolymer materials prepared in examples and comparative examples were used as test samples, dried naturally and cut to measure the surface and internal hydrophobic contact angles, respectively.
Table 1: test results of super-hydrophobic geopolymer anticorrosive material
Figure BDA0002610685430000101
The test results of examples one, two and three show that the siloxane modified super-hydrophobic polymer anticorrosion material has the compressive strength of more than 55MPa and the breaking strength of more than 20 MPa. The material has higher mechanical strength under the combined action of the compound raw materials, the nano-particle material and the short fiber, and is far higher than the organic hydrophobic material. The surface of the material is super-hydrophobic, the contact angle is larger than 155 degrees, the interior of the material also has good hydrophobic performance, and the contact angle is larger than 140 degrees. The material is proved to have achieved good hydrophobic modification from the substrate under the action of the nano-particle material and the short fiber. The surface of the material has better hydrophobic property than the interior due to further hydrophobic modification of methyl hydrogen-containing silicone oil and roughness modification of a nylon net.
The test results of comparative example four show that the surface and internal hydrophobic angles of the geopolymer material, which is surface-treated without the addition of polydimethylsiloxane and the silane coupling agent and without the nylon mesh and the methyl hydrogen-containing silicone oil, are less than 10 °. The polymer material itself is illustrated as being strongly hydrophilic and the siloxane is significantly effective in its hydrophobic modification. However, silicone hydrophobing agents have a certain weakening effect on the strength of the material, but have limited weakening under the action of fillers and short fibres.
The test result of the fifth comparative example shows that the mechanical strength and the internal contact angle of the geopolymer material without surface hydrophobic modification (without the nylon net and the methyl hydrogen-containing silicone oil) are similar to those of the example, but the surface contact angle is reduced by about 20 degrees, which indicates that the nylon net and the methyl hydrogen-containing silicone oil have obvious effect on the hydrophobic modification of the material surface. The nylon net can create a micron-scale rough structure on the surface of the geopolymer, the methyl hydrogen-containing silicone oil enables the geopolymer to have a hydrophobic effect on the chemical structure, and the combination effect of the methyl hydrogen-containing silicone oil and the methyl hydrogen-containing silicone oil enables the surface hydrophobic effect to be better.
The test results of comparative example six show that for geopolymer materials without the addition of nano-particulate material and short fibers, the mechanical strength is reduced by about 25% and the contact angle is reduced by about 15%. The nano particle material and the short fiber can fill up the gaps of the matrix to increase the compactness and promote the improvement of the mechanical strength, and can also create the surface roughness and promote the improvement of the hydrophobic property.
The foregoing detailed description is intended to illustrate and not limit the invention, which is intended to be within the spirit and scope of the appended claims, and any changes and modifications that fall within the true spirit and scope of the invention are intended to be covered by the following claims.

Claims (7)

1. The siloxane modified super-hydrophobic geopolymer anticorrosive material is characterized by comprising the following raw materials in parts by weight: 70-90 parts of a silicon-aluminum mineral raw material, 75-100 parts of an alkali activator, 2-3 parts of polydimethylsiloxane, 4-5 parts of methyl hydrogen-containing silicone oil, 0.1-0.2 part of a silane coupling agent, 4-6 parts of nano magnesium hydroxide powder, 7-10 parts of nano silicon dioxide powder, 3-5 parts of short fibers, 1-2 parts of calcium lignosulfonate and 1-1.5 parts of a grinding aid;
the alkali activator is a compound material and comprises 15-20 parts of sodium hydroxide solid, 45-55 parts of sodium silicate solution and 15-25 parts of deionized water, wherein the total water content is 40-50%;
the short fiber is one or the combination of more than two of silicon carbide fiber, basalt fiber and carbon fiber, the average diameter is 20-50 microns, and the length is 2-6 mm;
the preparation method comprises the following steps:
1) preparation of alkali activator: mixing 15-20 parts of sodium hydroxide solid, 45-55 parts of sodium silicate solution and 15-25 parts of deionized water, stirring until the mixture is uniform and clear, pouring the mixture into a plastic container, and sealing and storing for 12-24 hours to obtain an alkali activator;
2) preparation of the siloxane-fiber-alkali activator solution: mixing 2-3 parts of polydimethylsiloxane, 0.1-0.2 part of silane coupling agent, 3-5 parts of short fiber and the alkali activator obtained in the step 1), and performing ultrasonic dispersion for 60-90 minutes at 50-60 Hz to obtain a siloxane-fiber-alkali activator solution;
3) preparation of solid raw materials: mixing 70-90 parts of a silicon-aluminum mineral raw material, 4-6 parts of nano magnesium hydroxide powder, 7-10 parts of nano silicon dioxide powder, 1-2 parts of calcium lignosulphonate and 1-1.5 parts of a grinding aid in proportion, stirring and grinding for 40-60 minutes to obtain a solid raw material;
4) preparing a nylon net with hydrogen-containing silicone oil: soaking a 400-mesh nylon net with 1000 meshes in methyl hydrogen-containing silicone oil for 12-24 hours, wiping the nylon net with a paper towel until the surface is dry before the preparation test, and then placing the nylon net at the bottom of a mold;
5) preparation of geopolymer slurry: mixing the siloxane-fiber-alkali activator solution obtained in the step 2) with the solid raw material obtained in the step 3), and mechanically stirring at the rotating speed of 800-;
6) pouring the geopolymer slurry obtained in the step 5) into a mold with the bottom padded with the hydrogen-containing silicone oil nylon net obtained in the step 4) for curing, firstly, maintaining in a drying oven or a vacuum drying oven at 40-65 ℃ for 24-48 hours in a water-retaining manner, demolding, removing the nylon net, and then naturally curing at room temperature for 3-14 days to obtain the geopolymer composite material.
2. The siloxane-modified superhydrophobic polymeric anticorrosion material of claim 1, wherein: the silicon-aluminum mineral raw material is a compound material and comprises 45-55 parts of metakaolin, 15-20 parts of fly ash and 10-15 parts of silica fume.
3. The siloxane-modified superhydrophobic polymeric anticorrosion material of claim 1, wherein: the sodium silicate solution is a mixed solution of sodium silicate and deionized water, wherein SiO is2With Na2The molar mass ratio of O is 3-4.
4. The siloxane-modified superhydrophobic polymeric anticorrosion material of claim 1, wherein: the viscosity of the polydimethylsiloxane is 50-200 stokes; the main component of the methyl hydrogen-containing silicone oil is polymethylhydrosiloxane, and the effective component is more than 95%; the effective component of the silane coupling agent is more than 95 percent.
5. The siloxane-modified superhydrophobic polymeric anticorrosion material of claim 1, wherein: the particle size of the nano magnesium hydroxide powder is 20-100 nanometers, and the purity is more than 99 percent.
6. The siloxane-modified superhydrophobic polymeric anticorrosion material of claim 1, wherein: the particle size of the nano silicon dioxide powder is 10-30 nanometers, and the purity is more than 99 percent.
7. The siloxane-modified superhydrophobic polymeric anticorrosion material of claim 1, wherein: the purity of the calcium lignosulphonate is more than 95%.
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