CN112876900B - Method for reducing shrinkage stress of thermal curing coating by using hollow microspheres - Google Patents
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- 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
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- C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
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- C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
Abstract
The invention discloses a method for reducing shrinkage stress of a thermal curing coating by using hollow microspheres, and particularly relates to a method for preparing a coating containing the hollow microspheres by adding the hollow microspheres into the coating, which is used for reducing the curing shrinkage stress of the coating. In the thermosetting coating, the addition amount of the hollow microspheres is 0.5-10 wt% of the thermosetting coating. After the addition of the hollow microspheres, the shrinkage stress of the thermosetting coating is reduced by 25%. The invention tests the normal stress surface of the hollow microsphere through a rheological method, can reduce the shrinkage stress of the cured material and keep the excellent comprehensive performance of the coating.
Description
Technical Field
The invention belongs to the technical field of thermosetting coatings, and particularly relates to a method for reducing the shrinkage stress of a thermosetting coating by using hollow microspheres.
Background
The thermosetting resin has a certain shrinkage problem in the process of curing and forming, and the thermosetting coating is no exception, and the fundamental reason is that the intermolecular force participating in the curing reaction is converted into the covalent bond effect by van der Waals force, so that the intermolecular distance is reduced; in addition, thermal stresses due to temperature changes during thermal curing can also lead to stress buildup of the coating. The coating macroscopically shows that the problems of size shrinkage, deflection and deformation, even stress cracking and the like are generated, the service life of the coating is influenced, and even the safety of life and property is damaged.
At present, the reduction of the shrinkage stress of thermosetting and photocuring coating materials becomes an important problem to be solved urgently in the field of coating industry. In recent years, researchers have addressed this problem by adding inorganic fillers, intumescent monomers, and improved curing processes to the resin formulation. However, these methods have a significant problem in that the inorganic filler is added in a large amount and does not participate in the curing reaction of the thermosetting coating material, which reduces the usability of the thermosetting coating material; the preparation method of the expansion monomer is expensive, the economic practicability is poor, and the popularization and the application in the industrial field are difficult; however, the shrinkage cannot be reduced fundamentally though the improvement of the curing process is frequently used in industry. Therefore, it is necessary to develop a new technology to solve the problem of curing shrinkage of the thermosetting coating.
The hollow microsphere consists of a shell material and an internal cavity, wherein the internal cavity is a hollow cavity, and the mechanical property of the external shell material can be adjusted. The hollow microspheres have hollow cavities, the surface area of the hollow structure is obviously larger than that of the microspheres with the solid structure and the same size and composition, and the density of the hollow structure is lower than that of the microspheres with the solid structure. These unique properties of hollow microspheres greatly facilitate their use in active catalysis and the like. The hollow structure of the microsphere can directly store substances such as gas or small molecules. The difference of refractive index among air, the interface of the hollow microsphere and the air in the microsphere and the special cavity structure of the microsphere enable the covering performance, the anti-reflection performance and the deformability of the hollow microsphere to be excellent, so the hollow microsphere is often used as covering pigment and anti-ultraviolet filler to improve the performance of the thermosetting coating. At present, the application of the hollow microspheres in the market is mainly focused on the industries of coatings, cosmetics, paints, leather and the like, and meanwhile, the hollow microspheres also have good application prospects in the fields of self-repairing materials, heat-insulating materials and the like, and the application range of the hollow microspheres is yet to be further developed and utilized.
However, the problem of shrinkage stress existing in the preparation process of the thermosetting coating is not effectively solved; there is no document in the art that discloses the application of hollow microspheres in the shrinkage stress problem of thermosetting coatings, and further research and development are needed.
Disclosure of Invention
The purpose of the invention is as follows: in order to solve the problems, the mechanical property of the thermosetting coating is kept, and the curing shrinkage stress is reduced at the same time, the invention adds the reactive hollow microspheres with controllable mechanical property into the coating to reduce the shrinkage stress, and the change of the shrinkage stress in the curing process is monitored in real time through rheological test. The stress generated in the curing process is buffered and offset through the elastic deformation of the reactive hollow microsphere, the matching of the mechanical property of the hollow microsphere and the mechanical property of a coating system is a crucial influence factor for reducing the shrinkage stress, and the matching problem is solved, so that the problem of the curing shrinkage stress is fundamentally solved, and the basic mechanical property of the curing material is maintained or improved.
The application of the hollow microspheres in the thermosetting coating is to add the hollow microspheres in the thermosetting coating to prepare the thermosetting coating containing the hollow microspheres and reduce the shrinkage stress of the thermosetting coating.
Further, the shrinkage stress of the thermosetting coating was reduced by 25% after the addition of the hollow microspheres.
Furthermore, in the thermosetting coating, the addition amount of the hollow microspheres is 0.5-10 wt% of the thermosetting coating.
Further, the thermosetting coating is any one or a combination of two or more of glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin and alicyclic epoxy resin.
Further, the method for preparing the thermosetting coating containing the hollow microspheres comprises the following steps: weighing matrix resin and monomer, uniformly mixing, adding hollow microspheres and an auxiliary agent, and stirring a sample for 4-8h at a stirring speed of 200-400rpm under a light-shielding condition; preferably stirring at 300rpm for 6 h; removing air bubbles in the vacuum oven, coating and performing thermocuring to obtain a thermocuring coating; the hollow microsphere has one or more cavities, and the total volume of the cavities accounts for 40-60% of the volume of the hollow microsphere.
Further, in the thermosetting coating, the matrix resin includes, but is not limited to, bisphenol a epoxy resin, bisphenol F epoxy resin, acrylic resin, polyurethane resin; the reactive diluent is any one of monofunctional reactive diluents, difunctional reactive diluents, trifunctional reactive diluents and multifunctional reactive diluents. Preferably, the base resin is EA (bisphenol A type epoxy acrylate) and the reactive diluent is tripropylene glycol diacrylate.
Further, the modulus of the hollow microspheres is 0.1 GPa-8 GPa. The hollow microsphere has close relation with the mechanical property of the coating for reducing the shrinkage of the coating, the ball and the mechanical property of matrix resin, and the smaller the modulus and the hardness of the hollow microsphere and the coating are, the larger the elasticity is, the more beneficial to reducing the curing shrinkage stress is.
Furthermore, the hollow microspheres are formed by mixing a plurality of hollow microsphere individuals with different particle sizes, and the particle size of each hollow microsphere individual is 5-10 μm, or 10-20 μm, or 5-25 μm.
In order to achieve the above object, another object of the present invention is to provide a method for preparing hollow microspheres by using a Pickering emulsion method, wherein the specific preparation scheme is as follows:
(1) firstly, synthesizing silicon dioxide nano particles by a sol-gel method, placing 2.8mL of deionized water, 150mL of absolute ethyl alcohol and 9.7mL of ammonia water in a single-neck flask, heating to 60 ℃, starting magnetic stirring, and stirring at the speed of 300 rmp. 4mL of TEOS (tetraethyl orthosilicate) is slowly added into the mixed solution in a dropwise manner, and SiO is obtained after 6 hours of reaction2And (3) dispersing the mixture.
(2) SiO to the above step (1)2200 mu L of 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane is dripped into the dispersion liquid to react for 19 hours at normal temperature, and the stirring speed is 300 rmp. After the reaction is finished, SiO is obtained2Washing and centrifuging the dispersion liquid of (E) -2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane three times by using ethanol, and then putting the dispersion liquid into a vacuum oven for drying to finally prepare the SiO with double bond modification2And (3) nanoparticles. The addition of 2- (3, 4-epoxycyclohexane) ethyltrimethoxysilane allowed the reaction to proceed on SiO2The surface is grafted with epoxy groups to match the resin system.
(3) Respectively preparing water phase and oil phase. The formula of the oil phase is respectively as follows: 55% by weight of GBL (butyrolactone), 21% by weight of GMA (glycidyl methacrylate), 21% by weight of PUA (urethane acrylate), 3% by weight of 1173 (photoinitiator)And the modified SiO prepared in the step (2)2Nanoparticles in an amount of 5 wt%. The aqueous phase solution consisted of a 1 wt% aqueous solution of polyvinyl alcohol (PVA).
(4) Measuring 1mL of the oil phase in the step (3), and dropwise adding 10mL of the water phase in the step (3). Emulsifying for 2min at a shear rate of 20krmp by a high-speed disperser to prepare the Pickering emulsion.
(5) Immediately illuminating the Pickering emulsion prepared in the step (4) under a 365nm LED lamp, wherein the light intensity is 30mW/cm2The irradiation time was 5 min. And washing and centrifuging by using ethanol, and then drying in a vacuum oven to prepare the porous hollow microspheres. The microspheres have an average particle diameter of 1 to 100. mu.m, preferably 5 to 50 μm, particularly preferably 10 to 30 μm, as measured by laser diffraction.
The invention also aims to provide a preparation method of the thermosetting coating containing the hollow microspheres, wherein the hollow microspheres are added into the thermosetting coating, and the addition amount of the hollow microspheres is 0.5-10 wt% of the thermosetting coating.
Further, the method for preparing the thermosetting coating containing the hollow microspheres specifically comprises the following steps: weighing matrix resin and an active diluent, uniformly mixing, adding hollow microspheres and a curing agent, wherein the hollow microspheres are 0.5-2.5 wt% of the matrix resin and the active diluent, and stirring a sample at the room temperature at the stirring speed of 300rpm for 6 hours; and removing bubbles in a vacuum oven at room temperature, coating the film and performing heat curing to obtain the heat-cured coating. The curing agent includes amine curing agents, acid anhydride curing agents, amide curing agents, and the like.
Further, the hollow microsphere used in the present invention has one or more cavities, and the total volume of the cavities accounts for 10% to 90%, preferably 30% to 70%, more preferably 40% to 60%, and most preferably 50% of the volume of the microsphere.
Furthermore, the shell of the hollow microsphere used in the invention can be a simple polymer shell or a hybrid shell of polymer and inorganic particles.
Generally, the shrinkage stress is reduced after the addition of the inert filler, but the reduction ratio is the same as the ratio of the filler; it is often necessary to add large amounts of inert fillers to completely eliminate shrinkage. In the invention, the shrinkage stress can be greatly reduced by adding a small amount of the hollow microspheres. The hollow microspheres used in the invention have a cavity structure and an elastic shell layer, so that certain deformation can be generated, the shrinkage stress caused by curing shrinkage stress is offset, and the effect of greatly reducing or even eliminating the shrinkage stress is achieved.
The surface of the hollow microsphere used in the invention has decorated active reaction sites (epoxy groups and the like), namely the silica nano-particles with double bonds. The silicon dioxide nano particles with double bonds can increase the compatibility of the hollow microspheres and a resin system on one hand; on the other hand, after the hollow microspheres are successfully prepared, the reaction sites still have activity and can participate in the curing of the thermosetting coating, so that the overall performance of the coating film is not changed/improved. That is, the double-bond modified silica nanoparticles enhance the surface bonding force between the resin and the microspheres, improve the compatibility between the resin phase and the filler phase, and prevent the mechanical properties of the resin matrix from being affected by the gaps generated between the microspheres and the resin. Therefore, the hollow microspheres used in the invention have good compatibility with a coating resin system, and can be blended with the resin system; during the blending process, the shell layer of the microsphere is not damaged. Therefore, the matching of the mechanical properties of the hollow microspheres and the coating system is a crucial influencing factor for reducing the curing shrinkage stress of the system.
Compared with the prior art, the invention has the characteristics and beneficial effects that:
(1) the invention uses the modified silicon dioxide particles as the emulsifier, and improves the compatibility of the hollow microspheres in the thermosetting coating.
(2) The invention utilizes the hollow microspheres to reduce the shrinkage stress of the thermosetting coating, and compared with the prior art, the reaction time can be effectively prolonged and the shrinkage stress of the cured coating film can be greatly reduced only by adding the microspheres with the content of 0.5-10 wt%.
(3) The invention utilizes the hollow microspheres to reduce the shrinkage stress of the thermosetting coating and keep the excellent comprehensive performance of the thermosetting coating.
Drawings
FIG. 1 is a graph of the mechanical properties of hollow microspheres;
FIG. 2 is a graph of curing shrinkage stress in R-50 epoxy coatings and R-80 epoxy coatings with different mechanical properties.
Detailed Description
The invention is further described with reference to the following figures and examples.
The present invention will be better understood from the following examples. However, those skilled in the art will readily appreciate that the specific material ratios, process conditions and results thereof described in the examples are illustrative only and should not be taken as limiting the invention as detailed in the claims.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the following examples are further detailed. It will be appreciated by those skilled in the art that the examples described are only for the purpose of facilitating an understanding of the invention and are not intended to be limiting.
Example 1: influence of addition amount of hollow microspheres on shrinkage stress of thermosetting coating
This example compares the effect of different amounts of hollow microspheres added on the shrinkage stress of a thermosetting coating.
The preparation process comprises the following steps:
1. the bisphenol F epoxy resin 170 and an epoxy reactive diluent XY622 are used as a basic formula according to the mass ratio of 1:1, and 4 wt% (accounting for the percentage content of the basic formula) of dicyandiamide curing agent and 1 wt% (accounting for the percentage content of the basic formula) of imidazole accelerator are added to prepare a coating formula.
2. The hollow microspheres are used as fillers, and the addition amounts of the hollow microspheres are 0wt%, 0.5 wt%, 3 wt% and 8 wt%, respectively.
3. The change of the shrinkage stress in the coating curing process is tested by a Sammer rheometer (MARS 60), a flat plate rotor with the diameter of 20mm is used for the experiment, 0.2mL of sample is dripped on a heating table, the distance (Gap) between the flat plate rotor and a bottom plate is controlled to be 0.5mm in a vibration mode (stress control), and the deformation r is 1%. The shrinkage stress change was tested.
TABLE 1 Effect of different hollow microsphere addition amounts on coating shrinkage stress
As can be seen from table 1, the shrinkage stress of the coating gradually decreased as the amount of the added hollow microspheres increased. Comprehensively considering the influence of the addition of the microspheres on other properties of the coating, the addition of the microspheres is set to be not higher than 10 wt%.
Example 2: influence of hollow microsphere particle size on shrinkage stress of thermosetting coating
This example compares the effect of different particle sizes of the hollow microspheres and different particle size distributions on the shrinkage stress of the thermosetting coating.
The coating preparation method and the test method for the change in the shrinkage stress were the same as in example 1.
In the embodiment, 3 wt% of hollow microspheres are added into the coating as a filler, the particle sizes of the hollow microspheres are respectively 5-10 μm and 20-25 μm, and the influence of the particle size of the hollow microspheres on the shrinkage of the coating is verified; in addition, hollow microspheres which are unevenly distributed within the particle size range of 5-25 mu m are selected, and the influence of the particle size distribution of the hollow microspheres on the shrinkage of the coating is verified.
TABLE 2 influence of the particle size of the hollow microspheres on the shrinkage stress of the coating
As can be seen from table 2, the particle size of the hollow microspheres and the different particle size distributions affect the curing shrinkage stress of the epoxy coating, and the shrinkage stress of the coating decreases with the increase of the particle size of the hollow microspheres, but the change is not obvious; and from different particle size distributions, compared with each particle size distribution section with more uniform particle size distribution, the hollow microspheres with non-uniform particle sizes are more favorable for reducing the shrinkage stress of the coating.
Comparing the data from examples 1 and 2, it can be seen that the widest (5-25 μm) distribution microspheres from example 2 have a shrinkage stress of 178.10 which is greater than the result value of 161.38 at the same 3 wt% addition as in example 1. This is mainly because in example 1, the distribution of particle sizes of the microspheres is more random, and particle sizes ranging from submicron to tens of microns are present. It can therefore be considered that: the wider the particle size distribution of the microspheres, the more beneficial the reduction of shrinkage stress; the narrowly distributed particle size, regardless of size, does not significantly reduce the shrinkage stress.
Example 3: influence of mechanical properties of hollow microspheres on shrinkage stress of thermosetting coating
This example demonstrates the effect of the difference in mechanical properties of hollow microspheres on the shrinkage stress of a thermosetting coating.
The coating preparation method and the test method for the change in the shrinkage stress were the same as in example 1.
First, the mechanical properties of the hollow microspheres were characterized by nanoindentation, and as shown in fig. 1, as the concentration of polyurethane acrylate (PUA) was increased, the elongation at break of the hollow microspheres showed an increasing tendency (fig. 1a), and the elastic modulus and hardness showed a decreasing tendency (fig. 1 b). It is shown that the addition of PUA has a substantial effect on the mechanical properties of the hollow microspheres. Therefore, in this example, PUA is selected as a characterization mode of the mechanical properties of the hollow microsphere, and the influence of the mechanical properties of the hollow microsphere on the shrinkage stress of the coating is explored by changing the addition amount of the PUA.
In this example, 3 wt% of hollow microspheres and commercial hollow microspheres (glass beads) are added to the coating as fillers, and the mass concentrations of polyurethane acrylic resin (PUA) used as a film forming material for the shell layer of the hollow microspheres in the Pickering emulsion oil phase are changed to 10wt%, 20 wt% and 30wt%, respectively, so that the prepared hollow microspheres are PUA-10, PUA-20 and PUA-30 hollow microspheres.
TABLE 3 influence of the differences in mechanical properties of the hollow microspheres on the shrinkage stress of the coating
As can be seen from table 3, the hollow microspheres have different mechanical properties, which significantly affect the shrinkage stress of the epoxy coating, and as the elasticity of the hollow microspheres increases, the shrinkage stress of the coating decreases, which is more advantageous than commercial hollow glass microspheres in reducing the shrinkage of the coating.
Example 4: effect of hollow microspheres on shrinkage stress of thermosetting coatings of different mechanical properties
This example demonstrates the effect of hollow microspheres on the shrinkage stress of thermoset coatings of different mechanical properties.
The coating preparation method and the test method for the change in the shrinkage stress were the same as in example 1.
PUA-30 hollow microspheres are respectively added into the R-80 and R-50 epoxy coatings as fillers,
in this example, the hollow microspheres PUA-30 were added to R-50 epoxy coatings and R-80 epoxy coatings having different mechanical properties to influence the curing shrinkage stress. Compared with a control group without the hollow microspheres, the result shown in fig. 2 shows that the shrinkage stress measured after the matrix resin with different mechanical properties is cured is the same, while the shrinkage stress values measured when the PUA-30 hollow microspheres are added into the epoxy coating with different mechanical properties are greatly different, which indicates that when the resin system has high elasticity and low hardness and modulus, the addition of the PUA-30 hollow microspheres has a good effect of reducing the shrinkage stress. The mechanical property of the microsphere and the mechanical property of the resin have an optimal matching value, but the smaller the hardness and modulus of the hollow microsphere and the epoxy resin are, the larger the elasticity is, the more favorable the curing shrinkage stress is, and the R-50 epoxy coating is preferred.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.
Claims (7)
1. Use of hollow microspheres in a heat-curable coating, characterized in that: adding hollow microspheres into the thermosetting coating to prepare the thermosetting coating containing the hollow microspheres, wherein the hollow microspheres are used for reducing the shrinkage stress of the thermosetting coating;
in the thermosetting coating, the addition amount of the hollow microspheres is 0.5-10 wt% of the thermosetting coating;
the hollow microspheres are formed by mixing a plurality of hollow microsphere individuals with different particle sizes, and the particle sizes of the hollow microsphere individuals are distributed in a multi-particle size range from 5 micrometers to 25 micrometers;
the preparation method of the hollow microspheres by adopting a Pickering emulsion method comprises the following steps:
(1) preparation of modified SiO2Nano-particles:
firstly, synthesizing the silica nanoparticles by a sol-gel method: mixing deionized water, absolute ethyl alcohol and ammonia water, magnetically stirring at 60 ℃, dropwise adding TEOS, and reacting for 6h to obtain SiO2A dispersion liquid; the SiO2Dropwise adding 2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane into the dispersion liquid, reacting for 19 hours at normal temperature, wherein the stirring speed is 300 rmp; after the reaction is finished, SiO is obtained2Washing and drying the (E) -2- (3, 4-epoxycyclohexane) ethyl trimethoxy silane dispersion liquid to obtain the modified SiO with double bond modification2A nanoparticle;
(2) preparing hollow microspheres:
respectively preparing a water phase and an oil phase, wherein the oil phase comprises the following components: butyrolactone, glycidyl methacrylate, urethane acrylate, photoinitiator and modified SiO2Nano particles, wherein the aqueous phase solution is PVA aqueous solution; measuring 1mL of the oil phase, dropwise adding 10mL of the water phase, dispersing and emulsifying to obtain a Pickering emulsion, immediately illuminating under an LED lamp, and washing and drying to obtain the hollow microspheres.
2. Use of hollow microspheres according to claim 1 in a heat curable coating, characterized in that: after the addition of the hollow microspheres, the shrinkage stress of the thermosetting coating is reduced by 25%.
3. Use of hollow microspheres according to claim 1 in a heat curable coating, characterized in that: the method for preparing the thermosetting coating containing the hollow microspheres comprises the following steps: weighing matrix resin and an active diluent, uniformly mixing, adding hollow microspheres and an auxiliary agent, and stirring a sample for 4-8h at the stirring speed of 200-400rpm under the condition of keeping out of the sun; removing air bubbles in the vacuum oven, coating and performing thermocuring to obtain a thermocuring coating; the hollow microspheres have one or more cavities, and the total volume of the cavities accounts for 40-60% of the volume of the hollow microspheres.
4. Use of hollow microspheres according to claim 3 in a heat curable coating, characterized in that: in the thermosetting coating, the matrix resin is any one or more of bisphenol A epoxy resin, bisphenol F epoxy resin, acrylic resin and polyurethane resin; the reactive diluent is any one or more of a monofunctional reactive diluent, a difunctional reactive diluent and a multifunctional reactive diluent.
5. Use of hollow microspheres according to claim 1 in a heat curable coating, characterized in that: the modulus of the hollow microspheres is 0.1 GPa-8 GPa.
6. Use of hollow microspheres according to claim 1 in a heat curable coating, characterized in that: the addition amount of the urethane acrylate in the oil phase is 10-30 wt%.
7. Use of hollow microspheres according to claim 6 in a heat curable coating, characterized in that: the amount of urethane acrylate added in the oil phase was 30 wt%.
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| CN115960483B (en) * | 2023-01-10 | 2023-10-13 | 江南大学 | Method for reducing shrinkage stress of photo-curing coating by using pH responsive cationic microgel |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275576A (en) * | 2013-05-29 | 2013-09-04 | 苏州绿创环保新材料有限公司 | Aqueous environment-friendly heat insulation dope and preparation method thereof |
| CN106634514A (en) * | 2016-12-22 | 2017-05-10 | 西北工业大学 | Preparation method of hollow aluminum oxide ceramic microsphere modified polyurethane coating |
| CN107629411A (en) * | 2017-09-27 | 2018-01-26 | 桂林理工大学 | The preparation method of hollow mesoporous silica microsphere reinforced epoxy composite |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| MX2015002564A (en) * | 2012-08-29 | 2015-10-08 | Hempel As | Anti-corrosive zinc primer coating compositions comprising hollow glass spheres and a conductive pigment. |
| EP3541629A4 (en) * | 2016-11-17 | 2020-05-27 | 3M Innovative Properties Company | Compositions including polymer and hollow ceramic microspheres and method of making a three-dimensional article |
-
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275576A (en) * | 2013-05-29 | 2013-09-04 | 苏州绿创环保新材料有限公司 | Aqueous environment-friendly heat insulation dope and preparation method thereof |
| CN106634514A (en) * | 2016-12-22 | 2017-05-10 | 西北工业大学 | Preparation method of hollow aluminum oxide ceramic microsphere modified polyurethane coating |
| CN107629411A (en) * | 2017-09-27 | 2018-01-26 | 桂林理工大学 | The preparation method of hollow mesoporous silica microsphere reinforced epoxy composite |
Non-Patent Citations (3)
| Title |
|---|
| "Hollow Microcapsules with Controlled Mechanical Properties Templated from Pickering Emulsion Droplets";Wang Xue等;《Macromolecular Chemistry and Physics》;20181231;第220卷(第4期);第1800395页 * |
| "Pickering乳液法制备复合壳层微胶囊及其在涂料中的应用";陈琳琳等;《涂料工业》;20200831;第50卷(第8期);第8-14页 * |
| "Pickering乳液法制备弹性中空微球及其在低收缩涂层中的应用";王雪;《中国优秀博硕士学位论文全文数据库（硕士）工程科技Ⅰ辑》;20191215(第12期);第B020-1页 * |
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