KR20110077938A - Method of manufacturing silica hollow microspheres for adiabatic paint - Google Patents
Method of manufacturing silica hollow microspheres for adiabatic paintInfo
- Publication number
- KR20110077938A KR20110077938A KR1020090134627A KR20090134627A KR20110077938A KR 20110077938 A KR20110077938 A KR 20110077938A KR 1020090134627 A KR1020090134627 A KR 1020090134627A KR 20090134627 A KR20090134627 A KR 20090134627A KR 20110077938 A KR20110077938 A KR 20110077938A
- Authority
- KR
- South Korea
- Prior art keywords
- silica
- hollow microspheres
- microspheres
- hollow
- silica hollow
- Prior art date
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/113—Silicon oxides; Hydrates thereof
- C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
- C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
- C01B33/146—After-treatment of sols
- C01B33/148—Concentration; Drying; Dehydration; Stabilisation; Purification
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
Abstract
Description
The present invention relates to a method of manufacturing silica hollow microspheres for thermal insulation coatings, and more particularly, to manufacture hollow hollow microspheres having a predetermined wall thickness so as to effectively use air having low thermal conductivity and to be applied in various environments. It is about a method.
Hollow microspheres are prepared by an emulsion method, a sacrificial core method, a nozzle reaction method, a sol-gel method, and the like.
The emulsion method is characterized by the fact that the particle size of the microspheres produced by the method of making microspheres in the liquid phase using the characteristics of the two phases which do not mix with the surface tension is very small. (Column) Used as a material.
The sacrificial core method is a method in which a polymer resin of a sphere is used as a core and a ceramic layer is coated on its surface to form a membrane layer, followed by melting, volatilizing, and removing the nucleus in the center. Although the particle size can be produced in a variety of micrometers to several tens of micrometers, there is a limiting factor to coat a membrane layer of a specific material for each nucleus that is a polymer resin.
Conventionally, the method of manufacturing the final microsphere is used for insulating paint, which is a building material. Therefore, the wall thickness of the hollow microsphere must be maintained above a certain level so that it can be applied even in a harsh environment. In order for the sphere to be blended into the paint to stably form the coating film on the structure under various conditions, the necessity of maintaining the wall thickness of the silica hollow microspheres to satisfy the bendability, impact resistance, adhesion, and compressive strength has emerged. have.
Accordingly, the present invention has been proposed to solve the above-mentioned conventional problems, and an object of the present invention is to provide a method for producing hollow silica microspheres for use as a heat insulating paint for building materials.
It is another object of the present invention to provide a method for controlling the wall thickness of hollow silica microspheres as needed in order to meet the conditions of bending, impact resistance, adhesion and compressive strength so that they can be applied in various environments. .
In the present invention, a method for preparing hollow microspheres for heat insulating paint is an emulsion step of preparing an emulsion solution by mixing and stirring a hydrophilic silica colloid sol, which is a precursor, and a hydrophobic isooctyl alcohol. The stabilization step of stabilization, the extraction step of dehydrating water from the droplets generated by mixing and stirring the dehydration liquid in the stabilized emulsion solution, the ripening step of determining the shape of the hollow silica microspheres by decelerating the stirring speed and completing the dehydration, It comprises a post-treatment step of filtering and drying the silica hollow microspheres, followed by heating and heat treatment.
The present invention can produce a hollow silica microspheres for insulating paint using air with low thermal conductivity, and to meet the conditions of bending, impact resistance, adhesion and compressive strength to be applied to a variety of environments of silica colloidal sol By controlling the content, particle size and heat treatment temperature, there is an effect that can be produced by adjusting the wall thickness of the hollow silica microspheres according to the required conditions.
Referring to the preferred embodiment of the silica hollow microspheres for heat insulating paint according to the present invention in detail with reference to the accompanying drawings as follows.
In the following description of the present invention, detailed descriptions of well-known functions or configurations will be omitted when it is determined that the detailed description may unnecessarily obscure the subject matter of the present invention. It is to be understood that the following terms are defined in consideration of the functions of the present invention, and may be changed according to the intention of the user, the operator, or the precedent, and the meaning of each term should be interpreted based on the contents will be.
First, the method for preparing hollow microspheres for heat insulating coating of the present invention is (a) an emulsion step of preparing an emulsion solution by mixing and stirring a hydrophilic silica colloid sol as a precursor and a hydrophobic isooctyl alcohol, and (b) generating the step (a). Stabilizing step of stabilizing the emulsion state by adding a catalyst and a surfactant to the prepared emulsion solution, (c) Extraction step of dehydrating water from the resulting droplets by mixing and stirring the dehydration solution to the emulsion solution stabilized in the step (b), (d) decelerating the stirring speed after step (c) to determine the shape of the hollow silica microspheres, and dehydration is completed, (e) filtering the hollow silica microspheres produced in step (d), It comprises a post-treatment step of drying and then heating to heat treatment.
In another embodiment of the present invention, the concentration of the silica colloidal sol in step (a) is 30 to 40% by weight, and the particle size is preferably 20 to 30nm.
In another embodiment of the present invention, the mixing ratio of silica colloid sol and isooctyl alcohol in step (a) is preferably 1: 4.
In another embodiment of the present invention, the stirring speed of the step (a) and the step (c) is 750-2,500rpm, and the stirring speed of the step (d) increases the efficiency of shape determination and dehydration of the silica hollow microspheres. In order to decelerate at a reduction ratio of 15-25 rpm / sec.
In another embodiment of the present invention, the catalyst in step (b) is ammonia water, the surfactant is preferably a nonionic span 80 (Span 80, Sorbitan Monooleate).
In another embodiment of the present invention, the dehydration solution in the step (c) is preferably n-butanol.
In another embodiment of the present invention, the temperature for heating and heat-treating the silica hollow microspheres in the step (d) is preferably 350 to 1,050 ° C.
Hereinafter, a preferred embodiment of the present invention will be described. The following description is only one example and the present invention is not limited thereto.
The present invention comprises an emulsion step, stabilization step, extraction step, aging step and post-treatment step.
The emulsion step is to determine the size of the silica hollow microsphere particles. The process factor in this step is the process factor having the greatest influence on the stirring speed, the particle size of the colloidal sol, and the content ratio of the colloidal sol and the dispersant. Experimentally, the concentration of silica colloidal sol was 30-40 wt%, the silica particle size was 20-30nm, and the mixing ratio of hydrophilic silica colloidal sol and hydrophobic isooctyl alcohol serving as a dispersant was 1: 4 to 750. The emulsion solution is prepared by stirring at ˜2,500 rpm.
The stabilization step stabilizes the emulsion state by introducing Span 80 (Sorbitan Monooleate), a nonionic surfactant as an emulsifier, and ammonia water as a catalyst, to the emulsion solution generated in the emulsion step. Ammonia water acts as a buffer for pH and improves the water solubility of n-butanol, which is used as a dehydrating solution in the next extraction step, to increase the extraction speed due to the concentration gradient and smooth the surface gelation.
In the extraction step, n-butanol, which is a dehydration solution, is added to the emulsion solution stabilized in the stabilization step, and a volume ratio of 4 times that of the emulsion solution is added and stirred at 750-2,500 rpm to extract water from the droplets generated in the emulsion step. In the process of exchanging n-butanol with water contained in the stabilized silica colloid, the silica colloid becomes a membrane forming the outer wall of the droplet and n-butanol is placed in the center of the droplet.
The ripening step is followed immediately by the extraction step, while controlling the agitation speed at a reduction ratio of 15-25 rpm / sec so that the total deceleration agitation time is 0.5-2.7 minutes, thereby increasing the efficiency of shape determination and dewatering of the hollow microspheres and making it stable.
In the post-treatment step, the hollow silica microspheres generated after the aging step are filtered using a filter paper and washed with acetone. Thereafter, the mixture was dried at 30 ° C. for 12 to 24 hours, and heat-treated at 350 ° C. for 1,050 ° C. for 100 minutes at a heating rate of 3 ° C./min using an electric furnace to complete the production of silica hollow microspheres.
The surface area and pore volume of the hollow silica microspheres are determined by the control factors discussed above, such as the stirring speed, the concentration and loading of the silica sol, and the firing temperature. The specific surface area and the pore volume are reduced and the relationship with the composition ratio of the extract to the solution in the emulsion state is very small.
The particle size of the hollow silica microspheres is also affected by various control factors. The particle size decreases with increasing stirring speed in the emulsion stage, but the effect is very small in the extraction stage.
The particle size change of the hollow microspheres with respect to the concentration of silica sol is proportional to each other, but there is a clear threshold of the concentration of silica sol in the reaction characteristics, so increasing the concentration no longer affects the particle size. The closer to the critical concentration where gelation occurs, the less the concentration gradient (driving force of water and alcohol exchange) develops normally, so the dehydration reaction rate is slower, resulting in volume gelation rather than surface gelation, which entangles overall and no longer forms microspheres. .
Here, the wall thickness of the hollow silica microspheres characterized by the present invention is determined by the content of silica sol, particle size and firing temperature of silica sol. The concentration of silica sol has a proportional relationship within a range where volume gelation does not occur. The particle size of silica sol does not have a big influence because the driving force of this reaction is concentration gradient, but as the particle size increases, the thickness tends to be thicker, and the particle wall thickness of the silica hollow microsphere becomes thin as the firing temperature increases. It is considered that the wall thickness becomes relatively thin in the process of thermal expansion of the air inside the hollow during the firing process.
Example 1
In the present embodiment will be described in detail the production example of the silica hollow microspheres for insulating paint through a laboratory scale test example.
Isooctyl alcohol (2-ethyl-1-hexanol) as a dispersant 25 ml of silica sol (Colloidal Silica, pH 9.5, 30 wt%, Sp.G 1.20, S-CHEMTECH) having a particle diameter of 20 to 30 nm and 30 wt% ) Into 100 ml and stirred for 3 minutes at 1,750 rpm to form an emulsion, and stabilize the emulsion state by adding 0.4 ml of a nonionic surfactant (Span 80) and 20 ml of ammonia water with a catalyst.
In the extraction step, 350 ml of n-butanol, a dehydrating agent, is added immediately, followed by stirring at the same speed for 2 minutes and 30 seconds, and then the extraction is finally completed while reducing the stirring speed at a reduction ratio of 15 to 25 rpm / sec. .
In the post-treatment step, the gelled hollow microspheres were filtered through a filter paper, dried at 30 ° C. for 24 hours, and heat-treated at 100 ° C. for 100 minutes at a heating rate of 3 ° C./min using an electric furnace. The yield was obtained by measuring the weight of the final product, and when the hollow silica microspheres were photographed with an electron microscope (SEM, S4700, HITACHI), the average particle size was 21.7 μm and the average wall thickness was 8.3 μm.
[Example 2]
In this embodiment, the change of the silica sol content on the wall thickness of the hollow microspheres will be described.
While the experiment was carried out under the same conditions as in Example 1, only the silica sol content was changed to 15 ml, 25 ml, 35 ml, and 45 ml to form silica hollow microspheres. Measured through and summarized in Table 1.
[Table 1] Wall thickness by content of silica sol
Particle size (㎛)
Wall thickness (㎛)
Example 3
In this example, the change of the particle size of the silica sol on the wall thickness of the hollow microspheres will be described.
The experiment was conducted under the same conditions as in Example 1, but the silica sol size was changed to 10-20 nm, 20-30 nm, 30-40 nm, 40-50 nm to make silica hollow microspheres, and in each case. The wall thickness was measured by SEM photographs every time, and was summarized as shown in Table 2 and FIG.
[Table 2] Wall Thickness by Silica Sol Particle Size
Particle size (nm)
Particle size (㎛)
Wall thickness (㎛)
Example 4
In this embodiment, the effect of the change in the firing temperature on the wall thickness of the hollow microspheres will be described.
The experiment was carried out under the same conditions as in Example 1, but the firing temperature was changed to 350 ° C., 550 ° C., 750 ° C., 950 ° C., and 1050 ° C. when the final product was heat treated. Measured through the photographs are summarized in Table 4.
[Table 4] Wall thickness by firing temperature
Particle size (㎛)
Wall thickness (㎛)
Example 5
In this embodiment, the hollow silica microspheres prepared in Example 1 were bundled with an inorganic binder (40 wt% colloidal silica) and molded into a certain size (300 mm (W) x 300 mm (L) x 40 mm (H)). Then, the thermal conductivity was measured by the plate comparison method (KS L 9016). During molding, the inorganic binder and the hollow microspheres are mixed in small amounts, and then stirred at 350 to 450 rpm using a stirrer to mix uniformly, and the mixture is put into a prefabricated mold and heat-treated at a temperature of 150 to 200 ° C. In this case, in order to compare the thermal conductivity of the hollow silica microspheres, water-soluble epoxy and urethane resins were added in an amount of 5% by weight, 10% by weight, 15% by weight, 20% by weight, and 30% by weight, respectively. Was measured and summarized in Table 5 and FIG.
[Table 5] Thermal conductivity of hollow microspheres
Through the Table 5 and Figure 2 it can be seen that the lower the thermal conductivity, the better the thermal insulation effect.
As described above, the present invention can manufacture hollow microspheres for insulating paints using air having low thermal conductivity, and to meet the conditions of bendability, impact resistance, adhesiveness and compressive strength so that they can be applied to various environments. By controlling the content, particle size and heat treatment temperature of the isidosol, there is an effect that can be produced by adjusting the wall thickness of the hollow silica microspheres according to the required conditions.
Although the present invention has been described with reference to the drawings, the terms or words used in the specification and claims are not to be construed as being limited to the conventional or dictionary meanings, and meanings consistent with the technical spirit of the present invention. It must be interpreted as a concept. Therefore, the embodiments described in the specification and the drawings shown in the drawings are only one embodiment of the present invention and do not represent all of the technical idea of the present invention, various equivalents that may be substituted for them at the time of the present application It should be understood that there may be variations and variations.
1 is a SEM photograph showing the wall thickness according to the particle size of the hollow silica microspheres of the present invention.
Figure 2 is a graph showing the thermal conductivity of the content of the hollow silica microspheres of the present invention.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020090134627A KR20110077938A (en) | 2009-12-30 | 2009-12-30 | Method of manufacturing silica hollow microspheres for adiabatic paint |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020090134627A KR20110077938A (en) | 2009-12-30 | 2009-12-30 | Method of manufacturing silica hollow microspheres for adiabatic paint |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20110077938A true KR20110077938A (en) | 2011-07-07 |
Family
ID=44917465
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020090134627A KR20110077938A (en) | 2009-12-30 | 2009-12-30 | Method of manufacturing silica hollow microspheres for adiabatic paint |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20110077938A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316737A (en) * | 2021-12-28 | 2022-04-12 | 无锡华东锌盾科技有限公司 | Water-based high-performance flexible ceramic coating and preparation method thereof |
-
2009
- 2009-12-30 KR KR1020090134627A patent/KR20110077938A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114316737A (en) * | 2021-12-28 | 2022-04-12 | 无锡华东锌盾科技有限公司 | Water-based high-performance flexible ceramic coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107055556B (en) | A kind of hydrophilic silicon dioxide aerogel microball and preparation method thereof | |
| US20160115079A1 (en) | Self standing nanoparticle networks/scaffolds with controllable void dimensions | |
| CN110002452B (en) | Hollow porous silica microsphere, preparation method and application | |
| US20180305262A1 (en) | Precursor Material for Additive Manufacturing of Low-Density, High-Porosity Ceramic Parts and Methods of Producing the Same | |
| CN111410523B (en) | Ultra-light porous fused quartz foam and preparation method thereof | |
| CN103771863B (en) | Method for solidifying ceramic slurry through controlling high-valent contra-ion by slowly adjusting pH value | |
| CN111116221A (en) | Preparation method of high-temperature-resistant mullite nanofiber aerogel | |
| CN107973592A (en) | A kind of γ-Al of even aperture distribution2O3Ceramic micro filter film and preparation method thereof | |
| KR20150076578A (en) | preparation method for silica particles containing single or multiple functional groups and silica particles prepared thereby | |
| KR20110077938A (en) | Method of manufacturing silica hollow microspheres for adiabatic paint | |
| CN101269975A (en) | Heterogeneous nucleation preparation method for LaPO4 coating alpha-Al2O3 powder body | |
| CN111218024B (en) | Method for continuously preparing core-shell hydrophilic-hydrophobic bipolar composite aerogel powder | |
| US6508082B2 (en) | Method for fabricating high-purity silica glass using sol-gel processing | |
| CN108503360B (en) | Preparation method of LSM bulk material | |
| US20230312355A1 (en) | Hollow inorganic particle and method for producing said hollow inorganic particle | |
| KR101466095B1 (en) | hollow sillica spheres synthetic method using of surfactant | |
| CN100503714C (en) | Method for preparing monodisperse polystyrene/zirconia core-shell glue composite ball particle | |
| CN106477969B (en) | A kind of composition preparing mortar, mortar prepared therefrom, resin paste composition comprising the mortar and preparation method thereof | |
| CN106565268B (en) | Preparation method of low-cost enhanced silicon dioxide aerogel | |
| CN115504479B (en) | SiO (silicon dioxide) 2 Preparation method of microspheres and precursor | |
| KR100974875B1 (en) | Method of Produce of Solution for Thin Flim Coating of Organic/Inorganic hybrid complex and Solution Produced using the Same and Method of Coating Using the Same | |
| JP2023128890A (en) | Hollow inorganic particles, resin composition containing hollow inorganic particles, package for semiconductors in which resin composition is used, and method for producing hollow inorganic particles | |
| CN109306147A (en) | Phenolic resin-silicon dioxide composite aerogel material and preparation method thereof | |
| WO2023128928A1 (en) | Ultra-small nano-porous aerogel and method for synthesizing the same | |
| CN107352997B (en) | A kind of nano ceramic material and preparation method with even crystal grain |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E601 | Decision to refuse application |