CN112777599B - Preparation method and application of waxberry-shaped nano silicon particles - Google Patents
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Abstract
The invention relates to a preparation method and application of waxberry-shaped nano silicon particles, and belongs to the technical field of building materials. The invention solves the technical problems that the existing concrete sealing curing agent is easy to whiten and has limited strength improvement. The invention takes waxberry-shaped nano silicon particles with ultra-high specific surface area and the like as raw materials, and prepares the concrete sealing curing agent through one-step mixing. The curing agent effectively utilizes the characteristics of the ultrahigh specific surface area and microstructure of the waxberry-shaped nano silicon particles, provides more reactive sites for free calcium ions in the nano silicon particles and concrete, and further improves the curing strength by taking the curing agent as a physical anchor point while forming stable and firm C-S-H permanent gel. Through even infiltration, the curing agent can form a compact and firm protective layer with a hydrophobic effect, so that the compactness of the concrete is effectively enhanced, and the firmness, wear resistance, impermeability and alkali efflorescence resistance of the concrete are greatly improved.
Description
Technical Field
The invention relates to a preparation method and application of waxberry-shaped nano silicon particles, and belongs to the technical field of building materials.
Background
Modern buildings have increasingly high requirements on the strength and structural durability of concrete floors, and concrete surface protection and treatment technologies are particularly important. The concrete sealing curing agent is a preferable technical means for the surface treatment of the concrete terrace because of the advantages of hardness, wear resistance, compression resistance, durability, environmental protection, attractive appearance and the like. The sealing and curing agent for concrete is used as a good additive for protecting concrete structures and prolonging the service life of concrete, and is invented by American in the seventies of the last century and is widely applied to the building decoration industry.
Currently, the market mainly has four generations of products: the first generation is magnesium-based curing agent, which can improve the hardness and strength of the ground to a limited extent, but is toxic, and has poor environmental friendliness and timeliness; the second generation is a sodium-based curing agent, which can provide higher curing strength and durability, but has the problem of surface whitening due to the introduction of new metal salts; the third generation is a lithium-based curing agent, which provides a higher curing effect and solves the problem of whitening the ground of the second generation, but has high cost; the fourth generation is a silica gel type high-performance concrete sealing curing agent which has the advantages of strong curing timeliness, environmental friendliness, no whitening and the like, but has low curing strength due to fewer reactive sites caused by the lower specific surface area, so that the large-scale application of the silica gel type high-performance concrete sealing curing agent in the domestic building market is limited.
Therefore, based on the problems of limited strength improvement, easy whitening and the like of the existing concrete sealing curing agent, the concrete sealing curing agent with better performance and the preparation method thereof are very necessary.
Disclosure of Invention
The invention provides a preparation method of waxberry-shaped nano silicon particles and a preparation method of the waxberry-shaped nano silicon particles by using the waxberry-shaped nano silicon particles, aiming at solving the technical problems that the existing concrete sealing curing agent has limited strength improvement and is easy to whiten.
The technical scheme of the invention is as follows:
a preparation method of waxberry-shaped nano silicon particles comprises the following specific operation processes:
Still further, the silane includes, but is not limited to, ethyl orthosilicate, tetrapropoxy silane, tetrabutoxy silane, methyltriethoxy silane, dimethyldiethoxy silane, or ethyl polysilicate.
Still further, the micelles include, but are not limited to, cetyltrimethylammonium bromide, sodium dodecyl sulfate or cetyltrimethylammonium tosylate.
Still further, amine mineralizers include, but are not limited to, aqueous ammonia, triethanolamine, ethylamino, propylamino, butylamino, diethylamine, diethylamino, or triethylamino.
Further, the method comprises the following specific operation processes:
firstly, 2.87g of cetyltrimethylammonium bromide and 35.27g of triethanolamine are dissolved in 100mL of deionized water, transferred into a 250mL three-neck flask, and after the reagent is uniformly dispersed, the three-neck flask is placed in a constant temperature water bath kettle at 80 ℃ and mechanically stirred for 10.0h at the speed of 800rpm by using a cantilever stirrer;
then, 8.9mL of tetraethoxysilane is added, stirring is continued, and the reaction is carried out for 20.0h;
and finally, concentrating the reaction liquid by a rotary evaporation method to obtain stable nano silicon particle dispersion liquid, and drying to obtain the waxberry-shaped nano silicon particles with ultrahigh specific surface area.
The concrete sealing curing agent of the waxberry-shaped nano silicon particles prepared by the method comprises the following raw materials in percentage by mass: 10 to 50 percent of waxberry-shaped nano silicon particles, 0.2 to 0.4 percent of catalyst, 0.2 to 1 percent of complexing agent, 0.03 to 0.05 percent of surfactant, 0.02 to 0.1 percent of wetting agent, 1 to 8 percent of water repellent and the balance of deionized water.
Further, the curing agent comprises the following raw materials in percentage by mass: 20 to 40 percent of waxberry-shaped nano silicon particles, 0.2 to 0.4 percent of catalyst, 0.4 to 1 percent of complexing agent, 0.03 to 0.05 percent of surfactant, 0.04 to 0.08 percent of wetting agent, 2 to 6 percent of water repellent and the balance of deionized water.
Further, the catalyst is one or more of sodium metaaluminate, potassium metaaluminate, sodium fluosilicate, potassium fluosilicate and sodium bicarbonate which are mixed according to any proportion.
Further, the complexing agent is a mixture of disodium ethylenediamine tetraacetate and sodium hydroxide.
Further, the surfactant is one or two of fluorocarbon surfactant and siloxane surfactant, which are mixed in any proportion.
Further, the wetting agent is an organosilicon wetting agent.
Further, the water repellent is one or more of sodium methyl siliconate, potassium methyl siliconate, sodium methyl silicate and potassium methyl silicate which are mixed according to any proportion.
The preparation method of the concrete sealing curing agent comprises the steps of weighing all raw materials according to mass ratio, mixing at normal temperature and normal pressure, uniformly stirring and reacting to obtain the concrete sealing curing agent.
Further, the method comprises the following operation processes: and uniformly mixing a catalyst, a complexing agent, a surfactant, a wetting agent and a water repellent at normal temperature and normal pressure, putting into nano silicon particles, uniformly stirring and reacting to obtain the concrete sealing curing agent, wherein the pH value is 8.0-12.0.
The invention has the following beneficial effects: the invention takes waxberry-shaped nano silicon particles with ultra-high specific surface area and the like as raw materials, and prepares the concrete sealing curing agent through one-step mixing. The concrete sealing curing agent provided by the invention also has the following advantages:
(1) The invention effectively utilizes the characteristics of the ultra-high specific surface area and the microstructure of the waxberry-shaped nano silicon particles, the waxberry-shaped microstructure enables the surface of the nano silicon particles to have a complex and dense pore structure, not only provides the ultra-high specific surface area for the nano silicon particles, but also provides more reactive sites for free calcium ions in the nano silicon particles and concrete, and can effectively improve the curing strength by taking the adhesive as a physical anchor point while forming stable and firm C-S-H permanent gel.
(2) The nano silicon particles used in the invention are prepared by adopting
The purity produced by the method is more than 99 percent, the average grain diameter is 70-130 nm, and the specific surface area is 600-1000 m 2 ·g -1 Waxberry-like nano silicon particles with ultra-high specific surface area, which are the most important matters for producing secondary chemical reaction of concreteThe waxberry-shaped microstructure of the material can effectively penetrate the interior of the concrete, more reactive sites are provided for nano silicon particles and the concrete through the structural advantage of high specific surface area, hydration reaction is carried out with free active calcium ions, new calcium silicate is generated, and carbonate ions and precipitated Ca (OH) in the interior of the concrete are filled in the pores 2 Substitution reaction occurs; the advantage of the waxberry-shaped dense pore structure not only can ensure that the nano silicon particles are firmly combined with concrete, but also can further effectively improve the curing strength by bearing the action of physical anchor points relative to the whole curing plate, so that the curing agent is more uniformly permeated, a compact and firm protective layer with a hydrophobic effect is formed, the compactness of the concrete is effectively enhanced, and the firmness, wear resistance, impermeability and anti-whiskering performance of the concrete are greatly improved.
(3) Because the aluminum hydroxide gel is easily formed by the metaaluminate alone to influence the catalytic effect, the catalyst for preparing the curing agent is a mixture of the metaaluminate, fluorosilicate and bicarbonate.
(4) The complexing agent mainly has the function of complexing calcium ions in concrete, so that the curing reaction is slowed down to achieve the effect of deep penetration; the surfactant is fluorocarbon surfactant or siloxane surfactant, so that the surface tension of the curing agent can be effectively reduced, and the deep penetration effect is achieved; the hydrophobic agent is used for penetrating into the concrete to capture free carbonate ions, generating substitution reaction, generating micro-expansion in capillary pores of the concrete, and further enhancing the waterproof and impervious functions of the concrete;
(5) The curing agent prepared by the method has the silicon dioxide content of 10-40%, the solid content of more than 16%, the wear resistance ratio of more than 87% and the compressive strength of more than 69MPa, and has excellent mechanical properties;
(6) The curing agent provided by the invention also has the characteristics of simple and convenient preparation method, simple production, environmental protection and convenient construction.
Drawings
FIG. 1A is a scanning electron microscope picture of waxberry-like nano-silicon particles with ultra-high specific surface area at a magnification of 10 ten thousand times;
FIG. 1B is a scanning electron microscope picture of waxberry-like nano-silicon particles with ultra-high specific surface area at a magnification of 30 ten thousand times;
FIG. 2A is a transmission electron microscope picture of waxberry-like nano-silicon particles with ultra-high specific surface area at a magnification of 10 ten thousand times;
FIG. 2B is a transmission electron microscope picture of the ultra-high specific surface area waxberry-like nano-silicon particles at a magnification of 30 ten thousand times;
FIG. 3 is a graph showing nitrogen adsorption and desorption curves of waxberry-shaped nano-silicon particles with ultra-high specific surface areas;
FIG. 4A is a graph of nitrogen adsorption and desorption for a conventional silica sol;
FIG. 4B is a graph of nitrogen adsorption and desorption for ultra-high specific surface area dendritic nano-silicon particles;
FIG. 5 is a scanning electron microscope image of a cross section of the cured concrete of example 4;
FIG. 6 is a scanning electron microscope image of the surface of the concrete after curing in example 4.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The raw materials used in the following examples are all commercial products except for the ultra-high specific surface area Yang Meizhuang nano silicon particles.
Preparing waxberry-shaped nano silicon particles with ultra-high specific surface area:
2.87g of cetyltrimethylammonium bromide and 35.27g of triethanolamine are accurately weighed by an electronic analytical balance, 100mL of deionized water is taken from a dosage cylinder, the cetyltrimethylammonium bromide and the triethanolamine are all dissolved in distilled water and transferred into a 250mL three-neck flask, after the reagents are uniformly dispersed, the three-neck flask is placed in a constant temperature water bath kettle at 80 ℃ and mechanically stirred for 10.0h at the speed of 800rpm by a cantilever stirrer. Then, 8.9mL of ethyl orthosilicate is accurately weighed by a pipette, added into a three-necked flask and stirred, and the reaction time is 20.0h. And concentrating the nano silicon particle solution by a rotary evaporation method to obtain stable nano silicon particle dispersion liquid, and drying to obtain the waxberry-shaped nano silicon particles with the ultrahigh specific surface area.
The scanning electron microscope pictures of the obtained waxberry-shaped nano silicon particles with ultra-high specific surface area are shown in fig. 1A and 1B, and as can be seen from fig. 1A and 1B, micelle automatically formed by a surfactant and a mineralizer in deionized water is taken as a template, and the method adopts
The waxberry-shaped nano silicon particles prepared by the method have uniform particle size distribution and certain monodispersity, the average particle size of the nano particles is 100+/-30 nm, the surface of the waxberry-shaped nano silicon particles is rough, and the waxberry-shaped nano silicon particles have a dense micropore structure, which is the result generated after micelle templates are removed, and also means that the nano silicon particles have extremely high surface area. The transmission electron microscope pictures of the obtained waxberry-shaped nano silicon particles with the ultra-high specific surface area are shown in fig. 2A and 2B, and as can be seen from fig. 2A and 2B, under the condition of higher magnification, the interior of the Yang Meizhuang nanometer silicon particles still has obvious micropores and waxberry-shaped structures, and the dense micropores and waxberry structures enable the nano particles to have more active reaction sites to be in contact with concrete.
The nitrogen adsorption and desorption curves of the obtained waxberry-shaped nano silicon particles with the ultra-high specific surface area and the common silica sol are respectively shown in fig. 3 and fig. 4A.
Specific surface area and pore volume of the common silica sol and the ultra-high specific surface area waxberry-shaped nano silicon particles are compared, and the following table shows:
| sample of | Specific surface area (BET)/m 2 ·g -1 | Pore volume (BJH)/cm 3 ·g -1 |
| Waxberry-shaped nano silicon particles | 857.30 | 0.44 |
| Ordinary silica sol | 164.81 | 0.76 |
And preparing the concrete sealing curing agent by using the prepared waxberry-shaped nano silicon particles with the ultra-high specific surface area.
Example 1
(1) The concrete sealing curing agent comprises the following raw materials in percentage by mass:
20% of waxberry-shaped nano silicon particles with ultra-high specific surface area, 0.6% of catalyst, 0.8% of complexing agent, 0.03% of surfactant, 0.07% of wetting agent, 5% of water repellent and 73.5% of deionized water.
Wherein the water repellent is sodium methyl silanol; the complexing agent is a mixture of disodium ethylenediamine tetraacetate and sodium hydroxide, wherein the mass ratio of the disodium ethylenediamine tetraacetate to the sodium hydroxide is 1:4; the catalyst is a mixture of sodium bicarbonate, magnesium fluosilicate and sodium metaaluminate, wherein the mass ratio of the sodium bicarbonate to the magnesium fluosilicate to the sodium metaaluminate is 1:2:1; the surfactant is a siloxane surfactant; the wetting agent is an organosilicon wetting agent.
(2) Preparing a concrete sealing curing agent:
weighing all the raw materials according to the mass ratio, mixing at normal temperature and normal pressure, uniformly mixing a catalyst, a complexing agent, a wetting agent, a surfactant and a water repellent, putting nano silicon particles into the mixture, uniformly stirring and reacting, and obtaining the concrete sealing curing agent in a clear and transparent state.
Example 2
This embodiment differs from embodiment 1 in that: the concrete sealing curing agent of the embodiment comprises the following raw materials in percentage by mass: 30% of waxberry-shaped nano silicon particles with ultra-high specific surface area, 0.6% of catalyst, 1.2% of complexing agent, 0.04% of surfactant, 0.06% of wetting agent, 7% of water repellent and 61.1% of deionized water.
Wherein the water repellent is sodium methyl silanol; the complexing agent is a mixture of disodium ethylenediamine tetraacetate and sodium hydroxide, wherein the mass ratio of the disodium ethylenediamine tetraacetate to the sodium hydroxide is 1:5; the catalyst is a mixture of sodium bicarbonate, magnesium fluosilicate and sodium metaaluminate, wherein the mass ratio of the sodium bicarbonate to the magnesium fluosilicate to the sodium metaaluminate is 2:1:1; the surfactant is fluorocarbon surfactant; the wetting agent is an organosilicon wetting agent.
The concrete sealing curing agent was prepared in exactly the same manner as in example 1.
Example 3
This embodiment differs from embodiment 1 in that: the concrete sealing curing agent comprises the following raw materials in percentage by mass: 40% of waxberry-shaped nano silicon particles with ultra-high specific surface area, 0.6% of catalyst, 0.5% of complexing agent, 0.03% of surfactant, 0.07% of wetting agent, 6% of water repellent and 52.8% of deionized water.
Wherein the water repellent is sodium methyl silanol; the complexing agent is a mixture of disodium ethylenediamine tetraacetate and sodium hydroxide, wherein the mass ratio of the disodium ethylenediamine tetraacetate to the sodium hydroxide is 1:3; the catalyst is a mixture of sodium bicarbonate, magnesium fluosilicate and sodium metaaluminate, wherein the mass ratio of the sodium bicarbonate to the magnesium fluosilicate to the sodium metaaluminate is 1:1:1; the surfactant is fluorocarbon surfactant; the wetting agent is an organosilicon wetting agent.
The concrete sealing curing agent was prepared in exactly the same manner as in example 1.
Example 4
This embodiment differs from embodiment 1 in that: the concrete sealing curing agent comprises the following raw materials in percentage by mass: 40% of waxberry-shaped nano silicon particles with ultra-high specific surface area, 0.4% of catalyst, 1% of complexing agent, 0.03% of surfactant, 0.07% of wetting agent, 5% of water repellent and 53.5% of deionized water.
Wherein the water repellent is methyl potassium silicate; the complexing agent is a mixture of disodium ethylenediamine tetraacetate and sodium hydroxide, wherein the mass ratio of the disodium ethylenediamine tetraacetate to the sodium hydroxide is 1:2; the catalyst is a mixture of sodium bicarbonate, magnesium fluosilicate and sodium metaaluminate, wherein the mass ratio of the sodium bicarbonate to the magnesium fluosilicate to the sodium metaaluminate is 1:2:1; the surfactant is a siloxane surfactant; the wetting agent is an organosilicon wetting agent.
The concrete sealing curing agent was prepared in exactly the same manner as in example 1.
Comparative example 1:
preparation of ultra-high specific surface area dendritic nano silicon particles:
3.52g of cetyltrimethylammonium bromide, 2.38g of sodium dodecyl sulfate and 5.27g of triethanolamine are accurately weighed by an electronic analytical balance, 100mL of deionized water is taken from a dosage cylinder, the cetyltrimethylammonium bromide, the sodium dodecyl sulfate and the triethanolamine are all dissolved in distilled water and transferred into a 250mL three-neck flask, after the reagents are uniformly dispersed, the three-neck flask is placed in a constant temperature water bath kettle at 80 ℃ and mechanically stirred for 10.0h at 800rpm by a cantilever stirrer. Then, accurately weighing 5.6mL of ethyl orthosilicate by a pipette, adding the ethyl orthosilicate into a three-necked flask, and stirring, wherein the reaction time is 20.0h. Then concentrating the nano silicon particle solution by a rotary evaporation method to obtain stable nano silicon particle dispersion liquid, and drying to obtain dendritic nano silicon particles with ultrahigh specific surface area, wherein the average particle size is 100+/-30 nm.
The nitrogen adsorption and desorption curves of the obtained ultra-high specific surface area dendritic nano-silicon particles are shown in fig. 4B.
Specific surface area and pore volume contrast of ultra-high specific surface area dendritic nano-silicon particles are shown in the following table:
| sample of | Specific surface areaProduct (BET)/m 2 ·g -1 | Pore volume (BJH)/cm 3 ·g -1 |
| Dendritic nano silicon particles with ultrahigh specific surface area | 554.03 | 1.93 |
And preparing the concrete sealing curing agent by using the prepared waxberry-shaped nano silicon particles with the ultra-high specific surface area.
This comparative example differs from example 4 in that: this comparative example uses ultra-high specific surface area dendritic silicon nanoparticles instead of ultra-high specific surface area waxberry-like silicon nanoparticles of example 4.
Comparative example 2
This comparative example differs from example 4 in that: this comparative example uses a common silica sol to replace the ultra-high specific surface area waxberry-like nano-silicon particles of example 4.
Comparative example 3
This comparative example differs from example 4 in that: no catalyst was added in this comparative example.
The properties of the concrete sealing curatives obtained in the examples and comparative examples above can be characterized:
the test method comprises the following steps: the curing agents obtained in examples 1 to 4 and comparative examples 1 and 2 were applied to the surface of a concrete block of 10X 10cm with a brush, and the application was repeated once after one hour, while the application was repeated with the brush until the curing agent became viscous, and finally the superfluous curing agent on the surface was removed with deionized water, and after drying, the surface was polished with polishing plates 400#, 800#, 1500# and 3000# respectively. The solid content of the curing agent and the water absorption capacity, the wear resistance ratio, the hardness and the compressive strength of the surface of the cured concrete for 24 hours are compared.
The test results are shown in the following table:
as can be seen from the above table, the curing agent of the present invention has a solid content of 16% or more, a wear resistance ratio of more than 87%, a compressive strength of more than 69MPa, and the 24-hour surface water absorption, wear resistance ratio and compressive strength of comparative examples 1, 2 and 3 are not the same as those of the curing agents of examples 1 to 4 of the present invention.
The scanning electron microscope pictures of the cross section and the surface of the concrete cured by the concrete sealing curing agent obtained in the example 4 are shown in fig. 5 and 6 respectively, the circles in the figures are ultra-high specific surface area waxberry-shaped nano silicon particles, and the concrete sealing curing agent obtained in the example 4 can be completely permeated on the observable nano scale, and the permeation depth is 5-8 mm.
Claims (7)
1. The concrete sealing curing agent of the waxberry-shaped nano silicon particles is characterized by comprising the following raw materials in percentage by mass: 10 to 50 percent of waxberry-shaped nano silicon particles, 0.2 to 0.4 percent of catalyst, 0.2 to 1 percent of complexing agent, 0.03 to 0.05 percent of surfactant, 0.02 to 0.1 percent of wetting agent, 1 to 8 percent of water repellent and the balance of deionized water;
the preparation method of the waxberry-shaped nano silicon particles comprises the following steps:
firstly, 2.87g of cetyltrimethylammonium bromide and 35.27g of triethanolamine are dissolved in 100mL of deionized water, transferred into a 250mL three-neck flask, and after the reagent is uniformly dispersed, the three-neck flask is placed in a constant temperature water bath kettle at 80 ℃ and mechanically stirred for 10.0h at the speed of 800rpm by using a cantilever stirrer;
then, 8.9mL of tetraethoxysilane is added, stirring is continued, and the reaction is carried out for 20.0h;
finally, concentrating the reaction solution by a rotary evaporation method to obtain stable nano silicon particle dispersion liquid, drying to obtain the silicon nanoparticle silicon particle dispersion liquid with the purity of more than 99 percent, the average particle diameter of 70-130 nm and the specific surface area of 600-1000 m 2 ·g -1 Waxberry-shaped nano silicon particles with ultrahigh specific surface area;
the catalyst is a mixture of sodium bicarbonate, magnesium fluosilicate and sodium metaaluminate.
2. The concrete sealing curing agent according to claim 1, wherein the curing agent comprises the following raw materials in percentage by mass: 20 to 40 percent of nano silicon particles, 0.2 to 0.4 percent of catalyst, 0.4 to 1 percent of complexing agent, 0.03 to 0.05 percent of surfactant, 0.04 to 0.08 percent of wetting agent, 2 to 6 percent of water repellent and the balance of deionized water.
3. The concrete sealing curing agent according to claim 1, wherein the complexing agent is a mixture of disodium edetate and sodium hydroxide.
4. The concrete sealing curing agent according to claim 1, wherein the surfactant is one or two of fluorocarbon surfactant and siloxane surfactant mixed in any ratio.
5. The concrete sealing curing agent according to claim 1, wherein the wetting agent is an organosilicon wetting agent.
6. The concrete sealing curing agent according to claim 1, wherein the water repellent is one or more of sodium methyl siliconate, potassium methyl siliconate, sodium methyl silicate and potassium methyl silicate mixed in any proportion.
7. A method for preparing the concrete sealing curing agent as claimed in claim 1, which is characterized by comprising the following operation processes: and uniformly mixing a water repellent, a complexing agent, a catalyst, a wetting agent and a surfactant at normal temperature and normal pressure, putting nano silicon particles into the mixture, uniformly mixing the mixture again, adding the wetting agent into the mixture, uniformly stirring the mixture, and reacting the mixture to obtain the concrete sealing curing agent.
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| CN202110026578.4A CN112777599B (en) | 2021-01-08 | 2021-01-08 | Preparation method and application of waxberry-shaped nano silicon particles |
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