CN116535812A - Composite material based on interface reinforced glass hollow microspheres and preparation method thereof - Google Patents
Composite material based on interface reinforced glass hollow microspheres and preparation method thereof Download PDFInfo
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- CN116535812A CN116535812A CN202210084397.1A CN202210084397A CN116535812A CN 116535812 A CN116535812 A CN 116535812A CN 202210084397 A CN202210084397 A CN 202210084397A CN 116535812 A CN116535812 A CN 116535812A
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- 239000004005 microsphere Substances 0.000 title claims abstract description 154
- 239000002131 composite material Substances 0.000 title claims abstract description 101
- 239000011521 glass Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 27
- 239000011159 matrix material Substances 0.000 claims abstract description 23
- 239000011852 carbon nanoparticle Substances 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 28
- 229910052799 carbon Inorganic materials 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 23
- 238000002386 leaching Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229920002472 Starch Polymers 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 239000008107 starch Substances 0.000 claims description 5
- 235000019698 starch Nutrition 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000009969 flowable effect Effects 0.000 claims description 4
- 238000001179 sorption measurement Methods 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- 239000004793 Polystyrene Substances 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 2
- 229930006000 Sucrose Natural products 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229920000098 polyolefin Polymers 0.000 claims description 2
- 229920002223 polystyrene Polymers 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000005720 sucrose Substances 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims 2
- 239000004593 Epoxy Substances 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 229920002635 polyurethane Polymers 0.000 claims 1
- 239000004814 polyurethane Substances 0.000 claims 1
- 229920006305 unsaturated polyester Polymers 0.000 claims 1
- 230000007547 defect Effects 0.000 abstract description 4
- 230000008439 repair process Effects 0.000 abstract description 3
- 230000002708 enhancing effect Effects 0.000 abstract description 2
- 239000002952 polymeric resin Substances 0.000 abstract description 2
- 229920003002 synthetic resin Polymers 0.000 abstract description 2
- 150000001721 carbon Chemical class 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000006260 foam Substances 0.000 description 7
- 239000000945 filler Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 230000006872 improvement Effects 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- -1 alkali metal alkaline earth metal Chemical class 0.000 description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000007906 compression Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000005188 flotation Methods 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 230000002787 reinforcement Effects 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- VYKXQOYUCMREIS-UHFFFAOYSA-N methylhexahydrophthalic anhydride Chemical compound C1CCCC2C(=O)OC(=O)C21C VYKXQOYUCMREIS-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 230000035899 viability Effects 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- 239000005011 phenolic resin Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920006337 unsaturated polyester resin Polymers 0.000 description 1
Classifications
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
- C03C11/002—Hollow glass particles
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
-
- 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
- C08K7/28—Glass
-
- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Glass Compositions (AREA)
Abstract
The invention discloses a composite material based on interface reinforced glass hollow microspheres and a preparation method thereof, wherein the composite material comprises a glass hollow microsphere, a glass hollow microsphere and a glass hollow microsphere, wherein the glass hollow microsphere is prepared from a glass hollow microsphere materialThe composite material comprises a resin matrix and composite glass hollow microspheres doped in the resin matrix, and the density of the composite material is 0.2-1.0g/cm ‑3 . The composite glass hollow microsphere consists of glass hollow microspheres and carbon nano particles modified on the surfaces of the glass hollow microspheres. In the composite material, the existence of the glass hollow microsphere modified with the carbon nano particles optimizes the hollow surface structure of the microsphere, improves the wettability with a polymer resin matrix, simultaneously repairs the defects on the surface of the microsphere, enhances the strength of the microsphere, and in addition, the carbon nano particles in the composite glass hollow microsphere play a role in enhancing the interface of the microsphere, so that the composite material has better mechanical property and stability.
Description
Technical Field
The invention relates to the technical field of composite materials. More particularly, relates to a composite material based on interface reinforced glass hollow microspheres and a preparation method thereof.
Background
Lightweight is an important application advantage of polymer composites. Hollow microsphere composites (also known as syntactic foams) are a class of closed cell foams obtained by uniformly dispersing a hollow microsphere filler in a matrix resin. The material has the characteristics of light weight and high strength, is an effective scheme for lightening the composite material, can obtain a series of composite materials with different density and strength through formula design and process optimization, and is widely applied to the fields of aerospace and deep sea. In order to reduce the overall density, the volume filling amount of the hollow microspheres in the composite material is larger and can reach more than 60%, and a large amount of interfaces are introduced into a conforming system by increasing the filling amount. The interface is critical to the strength of the composite, and the interface state can affect not only the instant performance of the composite, but also its long-term stability.
The silicate glass hollow microsphere is one of the most commonly used hollow fillers of composite foam, and has the advantages of low cost, high compressive strength, easy dispersion and filling and the like. In the preparation process, alkali metal alkaline earth metal components are added, so that the melting point of silicon dioxide is reduced, and the silicon dioxide is easy to form, but the wettability of the microspheres and resin is weakened, and more importantly, the alkali metal alkaline earth metal components are easy to dissolve out in water environment, so that the interface between the microspheres and a resin matrix is damaged, and the long-term stability of the composite material is reduced. In the Chinese patent application of application number 202010389529.2, the surface acid leaching treatment is carried out on the hollow glass microspheres to remove alkali on the surfaces of the microspheres, and then the heat treatment is carried out, so that the composite material obtained by compositing the microspheres and resin improves the interface and the stability of mechanical properties. However, the instant strength of the composite material obtained in this way is not significantly improved. To improve the instant strength of the composite material, a third phase reinforcement of the resin matrix is an effective method. However, the cavity wall inside the hollow microsphere composite material is a weak area of mechanical properties, and the integral reinforcement of the resin matrix by the third phase filler cannot improve the interface area in a targeted manner. In addition, the third phase filler is generally small in size, and has a problem of difficulty in uniform dispersion; and the density of the filler is usually much higher than that of the conventional resin, so that the overall reinforcement of the resin matrix inevitably requires higher filler usage amount, and the density of the composite material is improved.
Disclosure of Invention
Based on the facts, the invention aims to provide a composite material based on interface reinforced glass hollow microspheres and a preparation method thereof, so as to at least solve the problem that the instant strength of a light composite material based on glass hollow microspheres is not obviously improved.
In one aspect, the invention provides a composite material based on interfacial reinforced glass hollow microspheres, which comprises a resin matrix and composite glass hollow microspheres doped in the resin matrix, wherein the density of the composite material is 0.2-1.0g/cm -3 ；
The composite glass hollow microsphere consists of glass hollow microspheres and carbon nano particles modified on the surfaces of the glass hollow microspheres.
In the technical scheme of the invention, the selection of the glass hollow microspheres has no other requirements, and the glass hollow microspheres can be conventional commercially available glass hollow microspheres or glass hollow microspheres prepared by a method of the existing published literature (for example, the glass hollow microspheres can be prepared by referring to a method disclosed in Chinese patent application No. 201210056295.5).
Further, the glass hollow microsphere comprises alkali metal and/or alkaline earth metal.
Further, the volume content of the composite glass hollow microsphere in the composite material is 0.01-96%, preferably 40-70%.
Further, the particle size of the composite glass hollow microsphere is 10-120 mu m, and the true density is 0.1-0.6g/cm -3 The content of the carbon nano particles is 0.01-1wt%.
In the technical scheme of the invention, the resin matrix is a common resin matrix for preparing the composite material with rigid supporting performance.
Further, the resin matrix is selected from the group consisting of a resin that is in a flowable state prior to curing or is flowable upon dilution with a solvent.
Further, the resin matrix is selected from one of epoxy resin, unsaturated polyester resin, phenolic resin, polyolefin, silicone resin, polyurethane resin or polystyrene.
Further, the composite glass hollow microsphere is prepared by a method comprising the following steps:
and (3) carrying out acid leaching, adsorption of a small molecular carbon source and carbonization treatment on the glass hollow microspheres in sequence to obtain the composite glass hollow microspheres.
Wherein, the acid leaching is to carry out dealkalize treatment on the hollow glass microspheres. Specifically, the pickling may include: the glass hollow microspheres and 1mol/L hydrochloric acid are kept for 60min under mechanical stirring according to the volume ratio of 1:1.5, and then are subjected to suction filtration, drying and sieving to remove agglomerated particles.
Further, the method for adsorbing the small molecular carbon source comprises the following steps: and (3) immersing the acid-leached glass hollow microspheres in an aqueous solution of a small molecular carbon source, filtering, drying and sieving to remove agglomerated particles.
Further, the concentration of the aqueous solution of the small molecular carbon source is 0.01-1g/mL;
the small molecular carbon source is a small molecular organic carbon source and is selected from one or more of starch, sucrose, maltose, glucose or polyvinyl alcohol.
Further, in the dipping treatment process, the volume ratio of the glass hollow microspheres to the aqueous solution of the small molecular carbon source is 1:1-1:10, the process is preferably carried out under the stirring condition, and the stirring time is preferably 5-12h.
Further, the drying temperature is 40-80 ℃ and the drying time is 2-24h. The drying is preferably carried out in a drying oven.
Further, the carbonization treatment is carried out in a nitrogen atmosphere, the temperature of the carbonization treatment is 400-700 ℃, and the time is 1-6h. More specifically, the carbonization treatment process further comprises the steps of removing broken microspheres through floatation after carbonization, drying and sieving.
Wherein, the flotation is preferably to uniformly mix carbonized microspheres with ethanol or water in a volume ratio of 1:1-1:10, stand and layer, take the upper layer floating matter, filter and dry.
Further, the raw materials of the composite material also comprise additives. Exemplary additives include, but are not limited to, one or more selected from the group consisting of curing agents, accelerators, coupling agents, diluents. The choice and amount of each additive can be chosen by the person skilled in the art according to the actual circumstances. Taking a resin matrix as an example of an epoxy resin, suitable curing agents include, but are not limited to, methyl hexahydrophthalic anhydride; suitable accelerators include, but are not limited to, N-dimethylbenzylamine; suitable diluents include, but are not limited to, fatty alcohol diglycidyl ether (V22).
In yet another aspect, the present invention provides a method of preparing a composite material as described above, comprising the steps of:
uniformly mixing raw material components containing a resin matrix;
adding the composite glass hollow microspheres under the stirring condition, uniformly mixing and defoaming;
pouring the materials into a mould, and alternately carrying out vacuum vibration deaeration;
and solidifying the material to obtain the composite material.
The beneficial effects of the invention are as follows:
in the composite material provided by the invention, the existence of the glass hollow microsphere modified with the carbon nano particles optimizes the hollow surface structure of the microsphere, improves the wettability with a polymer resin matrix, simultaneously repairs the defects on the surface of the microsphere, enhances the strength of the microsphere, and in addition, the carbon nano particles in the composite glass hollow microsphere play a role in enhancing the interfaces of the microsphere, so that the composite material has better mechanical property and stability.
In the preparation method of the composite material provided by the invention, the composite glass hollow microspheres with different surface structures and carbon content can be obtained directly through controlling the treatment time, the carbon source type, the carbon source solution concentration and the carbonization treatment. The invention is suitable for different types of glass hollow microspheres, and a series of light high-strength composite materials can be obtained through the regulation and control of the types and the volume fractions of the microspheres. Compared with the blank glass microsphere composite material, the modified glass hollow microsphere can obviously improve the instant mechanical property of the composite material, and the improvement of the interface and the stability of the carbon material improve the long-term stability of the composite material in water environment.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 shows a schematic representation of the surface modification treatment of glass hollow microspheres and the preparation of a composite material in example 1.
Fig. 2 shows SEM images of hollow white glass hollow microspheres, acid-leached glass hollow microspheres, direct modified carbon glass hollow microspheres, acid-leached + modified carbon glass hollow microspheres of example 1.
Fig. 3 shows the contact angle of hollow white glass hollow microspheres of example 1.
Fig. 4 shows the contact angle of the acid leached glass hollow microspheres in example 1.
Fig. 5 shows the contact angle of the acid leaching + modified carbon glass hollow microspheres in example 1.
Fig. 6 shows photographs of composite materials prepared using the hollow white glass hollow microspheres (1), the acid-dipped glass hollow microspheres (2), the direct-modified carbon glass hollow microspheres or the acid-dipped+modified carbon glass hollow microspheres (3) of example 1.
Fig. 7 shows the immediate compression and water environment post-compression strength graphs of the composite material formed by the hollow white glass hollow microspheres, the acid-leached glass hollow microspheres, the direct modified carbon glass hollow microspheres and the acid-leached and modified carbon glass hollow microspheres of example 1.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
The embodiment adopts the method to carry out modification treatment on the self-made glass hollow microspheres, and meanwhile, the treated microspheres are compounded with a resin matrix to form a composite material.
The invention relates to a preparation method of self-made glass hollow microspheres and application thereof, which are realized by referring to application number 201210056295.5' a preparation method of glass hollow microspheres softening theory and the prepared glass hollow microspheres. The density of the glass hollow microspheres in this example was 0.30g/cm 3 Model T30, granularity of 20-80 μm.
Modification of microspheres in this example, the hollow glass microspheres were first subjected to acid leaching and dealkalization, specifically, the microspheres were kept with 1mol/L hydrochloric acid at a volume ratio of 1:1.5 for 60min under mechanical stirring, followed by suction filtration, drying, and sieving to remove agglomerated particles. After that, adsorption treatment, specifically, water-soluble starch was used as a carbon source, and 1g of starch was placed in 40mL of water, and the solution was mechanically stirred until the solution was clear and transparent (the concentration of water-soluble starch was 0.025 g/mL). Controlling the volume ratio of the microspheres to the carbon source solution to be 1:6, mechanically stirring for 5 hours, carrying out suction filtration, drying in a drying oven at 60 ℃ for 2 hours, and sieving to remove agglomerated particles. Then carbonization treatment is carried out, specifically, the microspheres after adsorption treatment are placed in a tube furnace and are placed in N 2 Carbonizing at 600 deg.C for 3h. And finally, carrying out flotation to remove broken microspheres, specifically, selecting a water-ethanol mixed solution with the volume ratio of 1:1 from a flotation solution, controlling the proportion of the microspheres to the ethanol water solution to be 1:3, uniformly mixing, standing and layering to remove sediment, repeating for three times, taking the upper layer of floating material, drying, and sieving to obtain the modified glass hollow microsphere (namely the composite glass hollow microsphere) with unchanged density and modified small amount of carbon. Meanwhile, the blank glass microspheres which are not subjected to acid leaching treatment are directly modified with carbon as a comparison, and the specific carbon modification treatment process is consistent with the above.
The surface morphology of the blank microsphere, the acid-treated microsphere, the direct modified carbon microsphere and the acid-treated and modified carbon microsphere is shown in figure 2, and the surface morphology has no obvious change. However, by carbon sulfur analysis, the direct modified carbon microsphere was indeed modified with 0.18wt% and the acid treated + modified carbon microsphere was modified with 0.15wt% carbon with little effect on density, as shown in table 1. The existence of a small amount of carbon enhances the hydrophobicity as shown in figures 3-5 on one hand, and further improves the wettability of the microsphere and the resin; on the other hand, as shown in table 1, the microspheres after acid leaching have increased defects of the spherical shell due to precipitation of alkali metal ions, resulting in decrease of the strength of the microspheres, and the modified carbon repairs the defects, thereby improving the strength of the microspheres themselves. It is not to be ignored that the carbon material itself has a reinforcing effect.
Finally, preparing a composite material, namely uniformly mixing several reagents of epoxy resin E51, TDE85, methyl hexahydrophthalic anhydride, N-dimethylbenzylamine and KH560 according to the mass ratio of 100:100:228.5:4.3:4.3, respectively adding the blank microsphere, the acid leaching microsphere, the direct carbon-coated microsphere and the acid leaching plus modified carbon microsphere, wherein the adding ratio of the glass hollow microsphere accounts for 58% of the volume of the composite material, and heating and curing for 2 hours, 2 hours and 4 hours at 80 ℃, 120 ℃ and 160 ℃ respectively. After cooling, the corresponding composite material was obtained, respectively, and the result is that the carbon material was reduced in agglomeration with uniform dispersion of the microspheres, as shown in fig. 6. And then respectively carrying out water environment treatment at 100 ℃ on the obtained composite material for 1 day, and measuring the uniaxial compression performance change of the composite material after 12 hours. As shown in fig. 7, the instant compressive strength of the composite material formed by the microspheres after acid leaching is improved by 3.4% compared with that of the blank microspheres, the improvement is not obvious, and the instant compressive strength of the composite foam formed by the directly modified carbon microspheres and the acid leaching and modified carbon microspheres is respectively improved by 10.9% and 11.8%, so that the composite material is obviously improved due to the improvement of the interface, the improvement of the strength of the microspheres and the self-enhancement effect of a small amount of modified carbon. Meanwhile, after the water environment at 100 ℃, the strength of the composite foam formed by the blank microspheres is reduced by 22.3%, the strength of the composite foam formed by the microspheres after acid leaching is reduced by 5.3%, the strength of the composite material formed by the microspheres directly coated with carbon is reduced by 11.3%, and the strength of the composite material formed by the acid leaching and the modified carbon microspheres is reduced by 7.3%. The strength reduction rate of the composite material formed by acid leaching and modifying the carbon microsphere is slightly larger than that of the composite foam of the acid leaching microsphere, and the difference is only 2%, which is probably due to the fact that a small amount of modified carbon introduces a new interface, so that slight performance attenuation is caused; compared with the composite material formed by the blank microspheres, the long-term stability of the composite material is obviously improved, and the reason is that the removal of alkali components and the improvement of interfaces are considered. The strength of the composite material formed by directly modifying the carbon microspheres is reduced to a degree greater than that of the composite material formed by acid leaching and carbon-coated microspheres, and the strength of the composite material is possibly influenced by ion precipitation.
TABLE 1 basic information of microspheres before and after treatment
| Microsphere type | Density/(g/cm) -3 ) | Volume viability/%at 10MPa |
| Blank microsphere | 0.302 | 92.45 |
| Acid leaching microsphere | 0.304 | 90.17 |
| Direct modified carbon microsphere | 0.307 | 96.59 |
| Acid leaching and modified carbon microsphere | 0.304 | 95.81 |
Description: the volume viability test method at 10MPa pressure in Table 1 is referred to GJB 3594-99 "hollow microsphere Performance test method".
The glass hollow microsphere composites of examples 2-13 were prepared similarly to example 1, with specific conditions and performance parameters shown in tables 2-4.
TABLE 2 preparation conditions and Density of glass hollow microsphere composites of examples 2-13
Note that: the preparation of the T20 and T38 glass hollow microspheres is realized by referring to application number 201210056295.5, a glass hollow microsphere softening chemical preparation method and the prepared glass hollow microspheres and application thereof. Wherein the densities of the T20 and T38 glass hollow microspheres are respectively 0.20g/cm 3 And 0.38g/cm 3 。
Table 3: examples 1-13 immediate Strength of glass hollow microsphere composites
Table 4: examples 1-13 strength of glass hollow microsphere composites after hydrothermal treatment
And (3) performing hydrothermal aging treatment: the composite material test standard block is placed in a water environment at 100 ℃ for 1d.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (10)
1. A composite material based on interface reinforced glass hollow microspheres is characterized by comprising a resin matrix and composite glass hollow microspheres doped in the resin matrix, wherein the density of the composite material is 0.2-1.0g/cm -3 ；
The composite glass hollow microsphere consists of glass hollow microspheres and carbon nano particles modified on the surfaces of the glass hollow microspheres.
2. The composite material according to claim 1, wherein the volume content of the composite glass hollow microspheres in the composite material is 0.01-96%, preferably 40-70%.
3. The composite material according to claim 1, wherein the composite glass hollow microspheres have a particle size of 10-120 μm and a true density of 0.1-0.6g/cm -3 The content of the carbon nano particles is 0.01-1wt%.
4. The composite of claim 1, wherein the resin matrix is selected from the group consisting of a resin that is flowable prior to curing or flowable upon dilution with a solvent.
5. The composite material of claim 4, wherein the resin matrix is selected from one of epoxy, unsaturated polyester, phenolic, polyolefin, silicone, polyurethane, or polystyrene.
6. The composite material of claim 1, wherein the composite glass hollow microspheres are prepared by a process comprising the steps of:
and (3) carrying out acid leaching, adsorption of a small molecular carbon source and carbonization treatment on the glass hollow microspheres in sequence to obtain the composite glass hollow microspheres.
7. The composite material according to claim 6, wherein the method for adsorbing the small molecule carbon source comprises the steps of: and (3) immersing the acid-leached glass hollow microspheres in an aqueous solution of a small molecular carbon source, filtering, drying and sieving to remove agglomerated particles.
8. The composite of claim 7, wherein the concentration of the aqueous solution of the small molecule carbon source is 0.01-1g/mL;
the small molecular carbon source is a small molecular organic carbon source and is selected from one or more of starch, sucrose, maltose, glucose or polyvinyl alcohol.
9. The composite material according to claim 6, wherein the carbonization treatment is performed in a nitrogen atmosphere at a temperature of 400-700 ℃ for a time of 1-6 hours.
10. A method of preparing a composite material according to any one of claims 1 to 9, comprising the steps of:
uniformly mixing raw material components containing a resin matrix;
adding the composite glass hollow microspheres under the stirring condition, uniformly mixing and defoaming;
pouring the materials into a mould, and alternately carrying out vacuum vibration deaeration;
and solidifying the material to obtain the composite material.
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