CN111635635A - Fly ash-based ceramic silicone rubber composite material and preparation method thereof - Google Patents
Fly ash-based ceramic silicone rubber composite material and preparation method thereof Download PDFInfo
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- CN111635635A CN111635635A CN202010597546.5A CN202010597546A CN111635635A CN 111635635 A CN111635635 A CN 111635635A CN 202010597546 A CN202010597546 A CN 202010597546A CN 111635635 A CN111635635 A CN 111635635A
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- fly ash
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- 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
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- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention provides a fly ash-based porcelain silicone rubber composite material and a preparation method thereof, wherein the material comprises the following components in parts by mass: 100 parts of a silicon rubber substrate, 20-40 parts of white carbon black, 5-15 parts of an activating agent, 2-10 parts of hydroxyl silicone oil, 15-40 parts of modified fly ash, 6-16 parts of modified short fibers, 15-30 parts of a structure control agent and 2-4 parts of a vulcanizing agent. According to the invention, by adding a proper inorganic filler and a low-melting-point structure control agent, the silicon rubber material is subjected to ceramic sintering reaction in a high-temperature environment to form a compact ceramic body, so that the ablation resistance of the silicon rubber is obviously improved; in addition, the fly ash plays a role of an inorganic reinforcing filler in the silicone rubber composite material and simultaneously participates in the ceramic process of the material, so that the ceramic material layer after ceramic is more compact; the fly ash is waste of coal-fired power plants, has wide sources and low cost, can save carbon black and recycle the waste when being applied, and improves the application value of the fly ash.
Description
Technical Field
The invention belongs to the field of preparation of high polymer materials, and particularly relates to a fly ash-based ceramic silicone rubber composite material and a preparation method thereof.
Background
Along with the improvement of social production efficiency, the application of the conveying belt in the material transportation industry is more and more extensive, and the production and transportation efficiency is greatly improved. According to the difference of transported substance temperature, select for use different types of conveyer belt, when carrying high temperature material, need use special high temperature resistant conveyer belt. The high-temperature resistant conveying belt generally has short service life due to the severe operation environment. The heat resistance of the covering rubber is a main factor for determining the performance of the high-temperature resistant conveying belt. Therefore, the improvement of the high temperature resistance and the extension of the service life of the high temperature resistant conveyor belt become a hot problem in the following research.
In recent years, researchers are dedicated to research on flame-retardant and high-temperature-resistant materials to solve the problem, and the ceramifiable rubber is a high-temperature-resistant material with good performance. The ceramifiable silicone rubber has good elasticity and mechanical property at normal temperature, and can quickly form a hard protective layer at high temperature, so that the normal operation of the conveyer belt can be ensured under the high-temperature condition.
According to the excellent characteristics of the ceramifiable silicone rubber, people are devoted to research the ceramifiable silicone rubber composite material with lower cost, good mechanical property, excellent sintering characteristic and strong flame retardant capability. Chinese patent CN1040772996A discloses a burning-resistant conveyer belt covering rubber, which is prepared by taking silicon sulfide rubber as a matrix, adding an active agent, a vulcanizing agent, a plasticizer, an anti-aging agent and the like, and mixing. The covering rubber material can be used for a long time in an environment of 250-400 ℃, the service life of the conveying belt in a high-temperature environment is prolonged, and good economic benefits are achieved.
In recent years, a plurality of patents in China disclose silicon rubber ceramic composite materials, for example, Chinese patent CN106349698A discloses a ceramic fireproof silicon rubber ceramic composite belt which has high puncture resistance, fireproof performance and fireproof performance. The invention is formed by vulcanizing and compounding silicon rubber and polyimide adhesive tape, and magnesium oxide, silane coupling agent modifier and the like are added, but the invention has the advantages of large dosage, complex process and high cost, and is difficult to realize industrial production.
The silicon rubber has excellent performance, high temperature resistance and low temperature resistance, the using temperature range is the widest in general rubber, and the silicon rubber can be used in the temperature range of-200 to 400 ℃; the paint has oil resistance, solvent resistance and weather resistance, is not easy to age, and is suitable for outdoor use; electrical insulation properties; the special surface property and physiological inertia, the specific surface energy of the silicon rubber is small, the silicon rubber has hydrophobicity, good ageing resistance and flame retardance, and no smoke or toxic gas is discharged during combustion. Therefore, the ceramic silicon rubber composite material has low smoke, no toxicity and no melting and dripping under the condition of flame ablation, generates silicon dioxide and refractory filler by combustion, generates a high-temperature resistant ceramic layer by eutectic reaction of the silicon dioxide and the refractory filler under the help of the bonding and combustion assisting action of glass flow, keeps the original shape and size unchanged, and the self-supporting ceramic body with a complete structure can effectively block the transfer of heat and fuel substances.
The ceramifiable silicone rubber is prepared by adding several auxiliary agents such as: the porcelain-forming filler, the cross-linking agent, the fluxing agent and the like are prepared by utilizing silicon rubber. The fluxing agent is an inorganic filler with a very low melting point, and when the ceramifiable silicon rubber meets a high-temperature environment, the fluxing agent is melted to generate a liquid phase, and a ceramic body with certain strength is generated through reaction. The fluxing agents used are glass powder, boron oxide, zinc borate, etc. The ceramic filler is basically silicate inorganic powder with a higher melting point, and can be used as a support framework raw material after silicon rubber decomposition while improving the thermal stability of the ceramic silicon rubber, and the ceramic filler needs enough strength.
More ablation-resistant particles can be added to the silicone rubber, mica, kaolin,High-temperature resistant inorganic fibers such as calcium carbonate, carbon fibers, high silica, SiC fibers and the like, and organic fibers such as PPTA, PSA and the like are researched. Different fillers have a greater impact on ablation rate and char layer structure. At present, researchers at home and abroad mainly study the influence of silicate fillers, fillers containing crystal water, metal oxides and functional powder fillers on the ablation rate and the carbonization layer structure of the silicon rubber, the silicate fillers, the metal oxides and the metal soaps can better improve the ablation performance, and the carbonization layer structure becomes loose after the crystal water and the fillers capable of sublimating or decomposing to generate volatile gases are added. Usually, silicate minerals such as mica, kaolin, wollastonite and montmorillonite are added, and the mineral fillers show a crystal structure at room temperature, have the characteristics of high melting point and high sintering degree, can generate phase change conversion at high temperature to absorb heat, and are in contact with SiO2Eutectic reaction is generated to form a liquid phase.
Chinese patent CN103923465A discloses an environment-friendly ablation-resistant ceramic silicone rubber composite material, which is prepared by mixing and vulcanizing silicone rubber, white carbon black, a coupling agent, ceramic powder, a melting auxiliary agent and the like. The invention greatly improves the ceramic property of the material while ensuring the mechanical property.
The fibers and the filler can fill the holes formed after the pyrolysis of the matrix and participate in the ceramic reaction in the carbonization layer. However, in order to obtain a ceramic-like carbonized layer with a dense and hard structure, a large amount of inorganic filler or reactive precursor needs to be added into the system.
Chinese patent CN102800404A discloses a burning-resistant conveyer belt, which adopts butylbenzene material as burning-resistant layer, and adds glass fiber in the heat-insulating layer, the produced conveyer belt has excellent burning-resistant performance, can be used for conveying high-temperature material with temperature of 200-600 ℃, the service life can reach five months under normal condition, and under the same service environment, the service life is 2-3 times of that of common high-temperature-resistant conveyer belt.
The inorganic filler has good high temperature resistance, but has larger relative density, so the addition of a large amount of the inorganic filler can cause the remarkable increase of the density and the reduction of the mechanical property, while the addition of the precursor can not remarkably increase the density, but usually causes the sharp reduction of the elongation at break, thereby having adverse effect on the complex mechanical environment coping capability in the transportation, the storage and the work of an engine. The silicone rubber ablation material with excellent performance is obtained, and on the premise of ensuring ablation resistance, a small amount of proper inorganic filler is added, so that the silicone rubber composite material keeps higher mechanical strength and elongation at break at room temperature.
The fly ash is industrial solid waste generated by a thermal power plant, is low-cost inorganic powder, is precious aluminosilicate mineral, has the characteristics of a pore structure, low density, high surface activity, large specific surface area and the like, and has wide application prospect. In recent years, a great deal of research has been conducted on the performance of fly ash for filling polymer materials. Research shows that SiO in the fly ash2Has the function of increment reinforcement in rubber and can partially replace clay, white carbon black and Al2O3And CaCO3Plays an incremental role in rubber; the unburned combustible material has a reinforcing effect similar to carbon black, has obvious technical advantages and economic advantages when applied to high polymer materials and composite materials, and is beneficial to solving the problem of environmental hazard caused by the mass accumulation of the fly ash.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a fly ash-based ceramic composite material and a preparation method thereof, wherein the adopted inorganic filler is cheap and easy to obtain, the mechanical property and the ablation resistance of the material can be taken into consideration while the material cost is remarkably reduced, and the purpose is to enable silicon rubber to form a ceramic structure on the surface of a carbonized layer in the ablation process and increase the strength and the density of the carbonized layer, so that the ablation resistance and the oxidation resistance of the material are enhanced, and the requirements of high temperature resistance and ablation resistance of a conveyer belt covering rubber or the use in a specific high-temperature environment can be met.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a composite ceramic silicon rubber material based on flyash is prepared from flyash (SiO)2,Al2O3Etc. capable of ceramicizing under flux while simultaneously pulverizing pulverized coalThe surface modification is carried out on the ash, so that the ash has good compatibility with a silicon rubber matrix, and the effect of improving the mechanical property of the composite material can be achieved after the ash is filled.
The fly ash-based ceramic silicone rubber composite material comprises the following components in parts by mass:
silicon rubber: 100, respectively;
white carbon black: 20-40 parts of;
activating agent: 5-15;
hydroxyl silicone oil: 2-10;
modified fly ash: 15-40;
modified short fiber: 6-16;
a structure control agent: 15-30;
vulcanizing agent: 2 to 4.
The silicone rubber is methyl vinyl silicone rubber and/or methyl phenyl vinyl silicone rubber, preferably methyl vinyl silicone rubber with the molecular weight of 45-80 ten thousand and the vinyl molar percentage of 1.8-5.0%.
The white carbon black is one or two of fumed silica and precipitated silica, and the fumed silica is preferred.
The activating agent is zinc oxide or a compound of magnesium oxide and stearic acid in a mass ratio of 1/1-3/1; or a compound of zinc oxide or magnesium oxide and zinc stearate or magnesium stearate in a mass ratio of 1/1-1/3; preferably a mixture of zinc stearate and zinc oxide in a mass ratio of 1/2.
The viscosity of the hydroxyl silicone oil is less than or equal to 2000 mPa.s.
The fly ash raw material used by the modified fly ash is a product obtained by ultrafine grinding of fly ash of a coal-fired power plant, and the fineness of the fly ash is 1000-2500 meshes; the modified fly ash is prepared by a dry modification process and a macromolecular modifier, and is prepared by the following steps:
weighing fly ash with the fineness of 1000-2500 meshes, adding the fly ash into a high-speed stirrer, and stirring at a high speed for 15-20 min to activate the fly ash;
(2) mixing a macromolecular modifier accounting for 3-10% of the mass of the fly ash with xylene according to the mass ratio of 1:1-2 to prepare a xylene solution of the macromolecular modifier;
(3) adjusting the rotating speed of the high-speed stirrer to be 300 revolutions per hour (100 ℃), adding 1/3 xylene solution of the macromolecular modifier, adjusting the rotating speed to be 2000 revolutions per hour (1500 ℃), stirring for 5-10 min, and controlling the temperature to be lower than 130 ℃; then the rotating speed is adjusted to be 100-300 turns, 1/3 of the xylene solution of the macromolecular modifier is added, the rotating speed is adjusted to be 1500-2000 turns, the stirring is carried out for 5-10 min, and the temperature is controlled to be lower than 130 ℃; then the rotating speed is adjusted to be 300 turns at 100-; finally, the modified fly ash is prepared.
The macromolecular modifier is prepared by adopting the following method:
adding low molecular weight polybutadiene (LMPB) and xylene with the mass of 3-5 times that of the LMPB into a reaction kettle which is heated by an oil bath, can be sealed and is provided with a condensing tube and a dropping funnel, fully dissolving, and preparing into a solution;
dissolving gamma-methacryloxypropyltrimethoxysilane (KH570) with the mass of 1/10-1/4% of LMPB and dibenzoyl peroxide (BPO) with the mass of 1-3% of LMPB in xylene with the mass of 3-5 times that of LMPB to prepare a mixed solution, adding the mixed solution into a constant-pressure dropping funnel, and adding the constant-pressure dropping funnel onto a reaction kettle; pumping air in the reaction kettle, and introducing high-purity nitrogen for protection;
raising the temperature of the oil bath to 85-90 ℃, opening a valve of a dropping funnel under stirring, slowly dropping a xylene mixed solution of KH570 and BPO, finishing dropping within 30-60min, raising the temperature to 95-100 ℃, stopping heating after reacting for 4-8 hours, and cooling to room temperature;
pouring the reaction solution into a separating funnel, and adding methanol with the same volume as that of the xylene to precipitate and separate the macromolecular modifier; the precipitate was washed 2 times with equal amounts of methanol; and (3) carrying out rotary evaporation and drying at the temperature of 60-80 ℃ to obtain the macromolecular modifier.
The macromolecular modifier can also be replaced by one or more of small molecular silane coupling agents of gamma-aminopropyl triethoxysilane (KH550), gamma-glycidoxypropyl trimethoxysilane (KH560), gamma-methacryloxypropyl trimethoxysilane (KH570), vinyl triethoxysilane (silane coupling agent YDH-151) and the like.
The modified short fiber is prepared by the following method: the high-speed stirrer is preheated to 50-70 ℃, 40 parts by mass of short fibers, 5-15 parts by mass of paraffin oil, 5-10 parts by mass of hydroxyl-terminated polybutadiene with the molecular weight of 1000-2000 and 5-10 parts by mass of stearic acid are added to be stirred at a low speed for 30s, and then the mixture is stirred at a high speed for 6-15 min; and stopping the machine once every 3-5min to clean the materials attached to the stirrer cover and uniformly mix the materials with the rest materials to finally prepare the modified short fibers.
The short fiber raw material used by the modified short fiber can be one or more of aramid chopped fiber, aramid pulp fiber, polyimide chopped fiber, cellulose chopped fiber, acrylic chopped fiber, polypropylene chopped fiber, polyester chopped fiber, chopped carbon fiber, high silica glass fiber and basalt fiber, and is preferably polyimide chopped fiber (3-7 mm).
The hydroxyl-terminated polybutadiene with the molecular weight of 1000-2000 can also be polyisobutylene with the molecular weight of 1000-2000.
The structure control agent is a mixture of low-melting-point glass micro powder and metal oxide in a mass ratio of 1/1-3/1; the metal oxide is one or a mixture of more than two of aluminum oxide, calcium oxide, zirconium oxide, magnesium oxide, titanium oxide, boron oxide and zinc oxide, and is preferably boron oxide; the melting point of the low-melting-point glass micro powder is 350-800 ℃, and the fineness is 1000-3000 meshes.
The vulcanizing agent is one or more than two of benzoyl peroxide, dicumyl peroxide, di-tert-butyl peroxide, 2, 4-dichloroperoxybenzoyl (bis-di-tetra) and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane (bis-di-penta), and preferably is a bis-penta vulcanizing agent.
A preparation method of a fly ash-based ceramic silicone rubber composite material comprises the following steps:
uniformly mixing silicon rubber on a double-roller open mill, wrapping the silicon rubber on a roller, adding a required activating agent, and uniformly mixing rubber; then adding the reinforcing agent white carbon black, and performing thin pass for several times to mix uniformly, so as to improve the strength of the silicone rubber; adding hydroxymethyl silicone oil, uniformly mixing, adding the modified fly ash, the structure control agent and the modified short fiber into a double-roll open mill, and mixing at the mixing temperature of 20-50 ℃; finally, adding a vulcanizing agent, performing thin pass for more than 5-10 times in a triangular bag forming mode at the temperature of not higher than 50 ℃ to achieve a uniform state, adjusting the roller distance to 2mm, and uniformly discharging to obtain mixed silicon rubber; after the sheet is taken out, curing the silicon rubber composite material at room temperature for 16-48 h; putting the rubber compound into a mold, and vulcanizing by using a flat vulcanizing machine, wherein the vulcanizing temperature is 150-180 ℃, and the vulcanizing time is 10-30 min, so as to finally obtain the fly ash-based ceramic silicone rubber composite material;
or,
adding silicon rubber, an activating agent, hydroxyl silicone oil, white carbon black, modified fly ash, a structure control agent and modified short fibers into an internal mixer according to the proportion for internal mixing, wherein the temperature is not higher than 80 ℃, the internal mixing is carried out until the torque of the internal mixer tends to be stable, discharging is carried out, and the temperature is reduced to room temperature; opening the rubber material placed to room temperature on an open mill, uniformly wrapping rollers, adding a vulcanizing agent, allowing the temperature to be lower than 50 ℃, performing thin pass for more than 5-10 times in a triangular wrapping mode to achieve a uniform state, adjusting the roller distance to 2mm, and uniformly discharging to obtain mixed silicon rubber; after the sheet is taken out, curing the silicon rubber compound for 16-48 hours at room temperature; and putting the rubber compound into a mold, and vulcanizing by using a flat vulcanizing machine at the vulcanization temperature of 150-180 ℃ for 10-30 min to finally obtain the fly ash-based ceramic silicone rubber composite material.
The design idea of the invention is as follows:
(1) the ablation resistance and the mechanical property of the silicon rubber heat insulating layer are two aspects of a problem, the two aspects are mutually connected and restricted, the selection of the filler which can improve the two properties is a research hotspot of the material of the silicon rubber heat insulating layer, the fly ash has the characteristics of wide raw material source, low price, small density, small permanent deformation, large surface area and the like, the compatibility of the fly ash with a rubber matrix can be enhanced through surface organic function modification, and the fly ash has the enhancement effect on the aspects of dispersion property, filling reinforcement effect and the like. Meanwhile, SiO contained in the fly ash2,Al2O3The main components can be easily vitrified under the fluxing agent, so that the composite material can easily form a vitrified layer when being subjected to external high heat, and the vitrified layer plays a role in protecting the material.
(2) The low-melting-point glass material, boron oxide and the like are added into the silicon rubber base material to serve as a fluxing agent, the vitrification temperature is reduced, the strength of a vitrified object is improved, a ceramic layer structure is formed on the surface of the carbonization layer, and a firmer compact heat insulation layer structure is formed in the heating or combustion process of the carbonization layer, so that the ceramic layer and the base layer are combined more tightly, the ceramic layer and the base layer are less prone to being washed away under the action of gas flow and particle washing, and the ablation rate of the material is reduced.
(3) The fly ash is inorganic powder, the rubber is an organic polymer material, the two materials are completely different in property, a certain degree of incompatibility exists between the two materials, and the performance of a composite material product depends on the transmission of stress on an interface between two phases of a filler and a base material. If stress concentration is generated on the interface of the filler and the matrix material, the interface becomes a weak link of the composite material. Therefore, it is critical to improve the strength of the composite material to take appropriate measures to improve the adhesive strength property of the interface. The surface modification of the fly ash can improve the compatibility and the dispersibility of the fly ash in a high polymer material. The invention adopts dry modification, the coal ash is modified by adding macromolecular modifier and mixing at high speed, polar group at one end of the modifier is connected with the surface of the coal ash by physical adsorption or chemical reaction, organic group is grafted on the surface of the coal ash, lipophilic group at the other end is physically wound or chemically reacted with the rubber matrix, the modifier plays a role of molecular bridge between the coal ash and macromolecules, and the interaction between the coal ash and the rubber matrix is enhanced.
Compared with the prior art, the invention has the beneficial effects that:
according to the invention, the modified ultrafine fly ash is added into the silicone rubber, so that the strength of the silicone rubber is greatly improved, the fly ash is a product of combustion in a thermal power plant at a high temperature, and has excellent flame retardant property, and meanwhile, the fly ash participates in ceramization in the presence of a fluxing agent and a structure control agent, namely low-melting-point glass micropowder, so that the composite material has good heat resistance of the silicone rubber and also has excellent mechanical properties. Compared with other inorganic fillers, the high-temperature-resistant composite material has low cost and better high-temperature resistance. The modified fly ash is modified by a dry method, and the low-cost modification mode is selected to be beneficial to realizing industrial application. The composite material is prepared by adopting a room temperature mixing method, the operation is simple, the cost is low, the control is easy, and the realization of industrial production is convenient.
Drawings
FIG. 1 is a flow chart of a preparation process of the fly ash-based ceramic silicone rubber composite material
FIG. 2 is an infrared spectrum of KH570, LMPB and macromolecular modifier (LMPB-g-KH570)
FIG. 3 is an infrared spectrum of fly ash before and after modification with a macromolecular modifier
FIG. 4 thermogravimetric plot of fly ash before and after modification with macromolecular modifier
FIG. 5 comparison of the appearance of the fly ash-based ceramic silicone rubber before and after ceramic
Detailed Description
The technical solution of the present invention is further described in detail below with reference to the examples and the drawings, but the technical solution is not limited thereto.
TABLE 1 raw material types and manufacturers used in the examples
TABLE 2 raw materials and amounts (unit: g) used in the examples
The macromolecular modifier for the modified fly ash is prepared by the following method:
in a reaction kettle which is heated by oil bath, can be sealed and is provided with a condenser tube and a dropping funnel, 400g of low molecular weight polybutadiene (LMPB) and 2000ml of dimethylbenzene are added and fully dissolved to prepare a solution.
A solution of 240g KH570 and 8g BPO in 2000ml xylene was added to the storage tank. Pumping air in the reaction kettle, and introducing high-purity nitrogen for protection.
Raising the temperature of the oil bath to 90 ℃, slowly adding a xylene mixed solution of KH570 and BPO by using an infusion pump under stirring, and adding all the solutions within 45 min; then the temperature of the reaction kettle is raised to 100 ℃, after 6 hours of reaction, the heating is stopped, and the reaction kettle is cooled to the room temperature. The reaction solution was poured into a separatory funnel in portions, and 200ml of methanol was added to precipitate the macromolecular modifying agent for separation. The precipitate was washed 2 times with equal amounts of methanol. The mixture was rotary-evaporated and dried at 80 ℃ to give 456g of a colorless viscous macromolecular modifier.
The macromolecular modifier was characterized by infrared spectroscopy as shown in FIG. 2.
FIG. 2 is an IR spectrum of KH570, LMPB and synthetic macromolecular modifier (LMPB-g-KH 570). According to the infrared spectrums of KH570 and LMPB, whether the silane coupling agents KH570 and LMPB are grafted successfully can be seen. As can be seen from the figure, the length of the groove is 1650cm-1The part is a stretching vibration peak of a C ═ C double bond, the strength of the C ═ C double bond of the LMPB-g-KH570 is increased, and the fact that the C ═ C double bond in the LMPB hardly participates in the reaction process is shown; at 3000--1In the range of 740cm-1The positions are respectively a C-H stretching vibration peak and an out-of-plane bending vibration peak on a benzene ring in LMPB; 1730cm in the figure-1，1170cm-1The infrared spectrum of LMPB has no characteristic absorption peak, and the grafted polymer macromolecular modifier (LMPB-g-KH570) has strong characteristic absorption peaks at the two positions, namely C-O stretching vibration and C-O-C stretching vibration in-COO-of the silane coupling agent KH570, and at the same time, the peak value is 1090cm-1The LMPB-g-KH570 also shows a characteristic absorption peak of Si-O-C bonds in KH570 molecules, and the infrared analysis results show that the macromolecular modifier (LMPB-g-KH570) is successfully synthesized.
The modified fly ash used in the following examples was prepared by the following method:
preheating a high-speed stirrer to 110 ℃, weighing 4000g of fly ash, adding into the high-speed stirrer, and stirring at high speed for 15-20 min to activate the fly ash. 120g of the macromolecular modifier prepared above was mixed with 200ml of xylene to prepare a xylene solution. Adjusting the rotating speed of a high-speed stirrer to about 100 revolutions, adding 1/3 containing a xylene solution of a macromolecular modifier, adjusting the rotating speed to 1700 revolutions, stirring at a high speed for 5-10 min, and controlling the temperature to be not higher than 130 ℃. And adjusting the rotating speed to 100 revolutions, adding 1/3 xylene solution containing the macromolecular modifier, adjusting the rotating speed to 1700 revolutions, stirring at a high speed for 5-10 min, and controlling the temperature to be not higher than 130 ℃. And adjusting the rotating speed to 100 revolutions, adding the rest dimethylbenzene solution containing the macromolecular modifier, adjusting the rotating speed to 1700 revolutions, stirring at a high speed for 5-10 min, and controlling the temperature to be not higher than 130 ℃. The modifier and the fly ash are fully and uniformly mixed to finally prepare the macromolecular modified fly ash.
The infrared spectrum characterization and the thermal weight loss analysis are carried out on the modified fly ash, and the results are shown in the attached figures 3 and 4.
As can be seen from the attached FIG. 3, the mass spectrum of 2940cm on LMPB-g-KH570-F is compared with that of pure fly ash-1And 2840cm-1Respectively appear as-CH3and-CH2Middle C-H stretching vibration at 1720cm-1Stretching vibration of carbonyl (C ═ O) appeared nearby at 1640cm-1Characteristic absorption peaks of deformation vibration of C ═ C double bonds appear, and the characteristic absorption peaks are new characteristic absorption peaks appearing on a spectrogram of the macromolecular modifier. This shows that the LMPB-g-KH570 macromolecular modifier successfully realizes grafting or adsorption on the surface of the fly ash.
FIG. 3 is a thermal weight loss curve of a fly ash raw material, KH570 modified fly ash and LMPB-g-KH570 modified fly ash. As can be seen from the figure, the original fly ash raw material only has a rapid thermal weight loss within the temperature range of 600-650 ℃, and the weight loss part is caused by the combustion of residual carbon in the fly ash and is about 2.5 percent. KH570-g-FA has two rapid thermal weight losses at 200-250 ℃ and 600-650 ℃, namely the thermal decomposition of KH570 and the combustion of residual carbon. The LMPB-g-KH570 modified fly ash has only one obvious rapid thermal weight loss, and the temperature span is very large from 400 ℃ to 700 ℃, which shows that the macromolecular modifier fully covers the surface of the fly ash and is fully integrated with the fly ash, and the weight loss amount reaches 6%.
The modified polyimide chopped fibers used in the following examples were prepared by the following method:
the high-speed stirrer is preheated to 70 ℃, 1200g of polyimide chopped fiber with the length of 3mm, 300g of paraffin oil, 300g of hydroxyl-terminated polybutadiene and 300g of stearic acid are added to be stirred at a low speed for 30s, then stirring is carried out for 15min every 1500 revolutions per minute, the materials attached to the stirring cover are cleaned off every 5min and are uniformly mixed with the rest materials, and finally the modified polyimide chopped fiber is prepared.
Example 1
Compounding according to the ingredients listed in table 2; uniformly mixing 100g of silicon rubber on a double-roll open mill, wrapping the silicon rubber on a roll, adding 2g of zinc stearate and 2g of zinc oxide, and uniformly mixing the silicon rubber with rubber tapping; then 20g of white carbon black is added and then the mixture is subjected to thin pass for several times and is mixed evenly; adding 6g of hydroxyl silicone oil, uniformly mixing, adding 20g of modified fly ash, uniformly mixing, adding the rest 6g of hydroxyl silicone oil, adding 8g of modified polyimide chopped fiber, 15g of low-melting-point glass powder and 5g of boron trioxide micropowder in batches, and mixing for 5 times; finally, 4g of a bis-di-penta vulcanizing agent is added, the temperature is not higher than 50 ℃, the roll spacing is adjusted to 2mm after the thin passing is carried out for 10 times in a triangular packaging mode, and the sheets are uniformly discharged from a packaging roll to obtain the mixed silicon rubber; after the sheet is taken out, the silicon rubber composite material is cured for 24 hours at room temperature; and putting the rubber compound into a mold, and vulcanizing and tabletting by using a flat vulcanizing machine, wherein the vulcanizing temperature is 160 ℃, and the vulcanizing time is 21min, so as to finally obtain the fly ash-based ceramic silicone rubber composite material.
Example 2
Compounding according to the ingredients listed in table 2; uniformly mixing 100g of silicon rubber on a double-roll open mill, wrapping the silicon rubber on a roll, adding 2g of zinc stearate and 2g of zinc oxide, and uniformly mixing the silicon rubber with rubber tapping; then 20g of white carbon black is added and then the mixture is subjected to thin pass for several times and is mixed evenly; adding 6g of hydroxyl silicone oil, uniformly mixing, adding 30g of modified fly ash, uniformly mixing, adding the rest 6g of hydroxyl silicone oil, adding 8g of modified polyimide chopped fiber, 15g of low-melting-point glass powder and 5g of boron trioxide micropowder in batches, and mixing for 5 times; finally, 4g of a bis-di-penta vulcanizing agent is added, the temperature is not higher than 50 ℃, the roll spacing is adjusted to 2mm after the thin passing is carried out for 10 times in a triangular packaging mode, and the sheets are uniformly discharged from a packaging roll to obtain the mixed silicon rubber; after the sheet is taken out, the silicon rubber composite material is cured for 24 hours at room temperature; and putting the rubber compound into a mold, and vulcanizing and tabletting by using a flat vulcanizing machine, wherein the vulcanizing temperature is 160 ℃, and the vulcanizing time is 25min, so as to finally obtain the fly ash-based ceramic silicone rubber composite material.
Example 3
Compounding according to the ingredients listed in table 2; uniformly mixing 100g of silicon rubber on a double-roll open mill, wrapping the silicon rubber on a roll, adding 2g of zinc stearate and 2g of zinc oxide, and uniformly mixing the silicon rubber with rubber tapping; then 20g of white carbon black is added and then the mixture is subjected to thin pass for several times and is mixed evenly; adding 6g of hydroxyl silicone oil, uniformly mixing, adding 40g of modified fly ash, uniformly mixing, adding the rest 6g of hydroxyl silicone oil, adding 8g of modified polyimide chopped fiber, 15g of low-melting-point glass powder and 5g of boron trioxide micropowder in batches, and mixing for 5 times; finally, 4g of a bis-di-penta vulcanizing agent is added, the temperature is not higher than 50 ℃, the roll spacing is adjusted to 2mm after the thin passing is carried out for 10 times in a triangular packaging mode, and the sheets are uniformly discharged from a packaging roll to obtain the mixed silicon rubber; after the sheet is taken out, the silicon rubber composite material is cured for 24 hours at room temperature; and putting the rubber compound into a mold, and vulcanizing and tabletting by using a flat vulcanizing machine, wherein the vulcanizing temperature is 160 ℃, and the vulcanizing time is 30min, so as to finally obtain the fly ash-based ceramic silicone rubber composite material.
Example 4
Compounding according to the ingredients listed in table 2; uniformly mixing 100g of silicon rubber on a double-roll open mill, wrapping the silicon rubber on a roll, adding 2g of zinc stearate and 2g of zinc oxide, and uniformly mixing the silicon rubber with rubber tapping; then 20g of white carbon black is added and then the mixture is subjected to thin pass for several times and is mixed evenly; adding 6g of hydroxyl silicone oil, uniformly mixing, adding 30g of modified fly ash, uniformly mixing, adding the rest 6g of hydroxyl silicone oil, adding 8g of modified polyimide chopped fiber, 20g of low-melting-point glass powder and 10g of boron trioxide micropowder in batches, and mixing for 5 times; finally, 4g of a bis-di-penta vulcanizing agent is added, the temperature is not higher than 50 ℃, the roll spacing is adjusted to 2mm after the thin passing is carried out for 10 times in a triangular packaging mode, and the sheets are uniformly discharged from a packaging roll to obtain the mixed silicon rubber; after the sheet is taken out, the silicon rubber composite material is cured for 24 hours at room temperature; and putting the rubber compound into a mold, and vulcanizing and tabletting by using a flat vulcanizing machine, wherein the vulcanizing temperature is 160 ℃, and the vulcanizing time is 26min, so as to finally obtain the fly ash-based ceramic silicone rubber composite material.
Example 5
Compounding according to the ingredients listed in table 2; uniformly mixing 100g of silicon rubber on a double-roll open mill, wrapping the silicon rubber on a roll, adding 2g of zinc stearate and 2g of zinc oxide, and uniformly mixing the silicon rubber with rubber tapping; then 20g of white carbon black is added and then the mixture is subjected to thin pass for several times and is mixed evenly; adding 6g of hydroxyl silicone oil, uniformly mixing, adding 30g of modified fly ash, uniformly mixing, adding the rest 6g of hydroxyl silicone oil, adding 8g of modified polyimide chopped fiber, 10g of low-melting-point glass powder and 10g of boron trioxide micropowder in batches, and mixing for 5 times; finally, 4g of a bis-di-penta vulcanizing agent is added, the temperature is not higher than 50 ℃, the roll spacing is adjusted to 2mm after the thin passing is carried out for 10 times in a triangular packaging mode, and the sheets are uniformly discharged from a packaging roll to obtain the mixed silicon rubber; after the sheet is taken out, the silicon rubber composite material is cured for 24 hours at room temperature; and putting the rubber compound into a mold, and vulcanizing and tabletting by using a flat vulcanizing machine, wherein the vulcanizing temperature is 160 ℃, and the vulcanizing time is 26min, so as to finally obtain the fly ash-based ceramic silicone rubber composite material.
Comparative example 1
Compounding according to the ingredients listed in table 2; uniformly mixing 100g of silicon rubber on a double-roll open mill, wrapping the silicon rubber on a roll, adding 2g of zinc stearate and 2g of zinc oxide, and uniformly mixing the silicon rubber with rubber tapping; then 20g of white carbon black is added and then the mixture is subjected to thin pass for several times and is mixed evenly; adding 6g of hydroxyl silicone oil, uniformly mixing, then adding 8g of modified polyimide chopped fibers in batches, uniformly mixing, adding the remaining 6g of hydroxyl silicone oil, and mixing for 5 times; finally, 4g of a bis-di-penta vulcanizing agent is added, the temperature is not higher than 50 ℃, the roll spacing is adjusted to 2mm after the thin passing is carried out for 10 times in a triangular packaging mode, and the sheets are uniformly discharged from a packaging roll to obtain the mixed silicon rubber; after the sheet is taken out, the silicon rubber composite material is cured for 24 hours at room temperature; and putting the rubber compound into a mold, and vulcanizing and tabletting by using a flat vulcanizing machine, wherein the vulcanizing temperature is 160 ℃, and the vulcanizing time is 23min, so as to finally obtain the fly ash-based ceramic silicone rubber composite material.
Examples performance testing of comparative examples:
the mechanical property test of the material samples obtained in the 5 embodiments adopts the GB/T528-2009 standard, the test samples are I-type dumbbell type, the stretching speed is 500mm/min, and the average value of the 5 test samples is taken. The Shore hardness is subjected to sample preparation and test according to GB/T531.1-2008, the test instrument is a hardness tester, each group of samples is tested at least for 5 points, and the obtained results are shown in Table 3.
The ablation experiment is carried out according to GJB 323A-96 standard, the sample is a small cylinder with the thickness of 10mm and the diameter of 30mm, the oxyacetylene flame is vertically rushed to the sample during the test, the diameter of the nozzle is 2mm, the distance between the nozzle and the sample is 10mm, the ablation time is 20s, the oxygen flow rate is 1512L/h, the acetylene flow rate is 1116L/h, and the obtained result is shown in Table 3.
And (3) performing a steel ball firing depth test, namely heating a steel ball with the diameter of 30mm to 800 +/-50 ℃, placing the steel ball on the surface of an upper covering layer of a sample for 5min, taking the steel ball away, cooling for 1h, cleaning a firing position by using a brush, measuring the thickness of a residual fired belt by using a micrometer, and selecting the full thickness of a 3-point measuring belt within the range of 20-30 mm away from the firing position. The results are shown in Table 3.
The ceramic forming performance test is carried out according to the standard sample size required by GB/T3810.4-2006 ceramic tile test method, and the calcination is carried out in a box-type resistance furnace under the set temperature condition of 800 ℃ for 0.5 h. The porcelain forming performance of the porcelain forming object is tested after standing and cooling, and the obtained results are shown in table 3.
TABLE 3 Performance data Table
The results of the examples show that the addition of the modified fly ash significantly improves various mechanical properties of the silicone rubber composite material, and the material can be well ceramized at high temperature in the presence of the modified fly ash to generate a high-strength and ignition-resistant ceramic layer. FIG. 5 is a photograph showing the appearance of the fly ash-based ceramic silicone rubber before and after being ceramized. It can be seen from the photo that the silicone rubber sheet cut into two pieces is well fused with the rubber of the bottom layer into a hard and firm whole after being sintered.
Claims (9)
1. The fly ash-based ceramic silicone rubber composite material is characterized by comprising the following components in parts by mass:
silicon rubber: 100, respectively;
white carbon black: 20-40 parts of;
activating agent: 5-15;
hydroxyl silicone oil: 2-10;
modified fly ash: 15-40;
modified short fiber: 6-16;
a structure control agent: 15-30;
vulcanizing agent: 2 to 4.
2. The fly ash-based ceramicized silicone rubber composite according to claim 1, wherein the silicone rubber is methyl vinyl silicone rubber and/or methyl phenyl vinyl silicone rubber.
3. The fly ash-based ceramic silicone rubber composite material as claimed in claim 1, wherein the activating agent is zinc oxide or a composite of magnesium oxide and stearic acid in a mass ratio of 1/1-3/1; or zinc oxide or magnesium oxide and zinc stearate or magnesium stearate in a mass ratio of 1/1-1/3.
4. The fly ash-based ceramicized silicone rubber composite according to claim 1, wherein the hydroxyl silicone oil has a viscosity of less than 2000 mpa.s.
5. The fly ash-based ceramic silicone rubber composite material according to claim 1, wherein the modified fly ash is prepared by the following method:
(1) firstly, preheating a high-speed stirrer to 90-110 ℃, weighing fly ash with the fineness of 1000-2500 meshes, adding the fly ash into the high-speed stirrer, and stirring at a high speed for 15-20 min to activate the fly ash;
(2) mixing a macromolecular modifier accounting for 3-10% of the mass of the fly ash with xylene according to the mass ratio of 1:1-2 to prepare a xylene solution of the macromolecular modifier;
(3) adjusting the rotating speed of the high-speed stirrer to be 300 revolutions per hour (100 ℃), adding 1/3 xylene solution of the macromolecular modifier, adjusting the rotating speed to be 2000 revolutions per hour (1500 ℃), stirring for 5-10 min, and controlling the temperature to be lower than 130 ℃; then the rotating speed is adjusted to be 100-300 turns, 1/3 of the xylene solution of the macromolecular modifier is added, the rotating speed is adjusted to be 1500-2000 turns, the stirring is carried out for 5-10 min, and the temperature is controlled to be lower than 130 ℃; and then regulating the rotating speed to 100-300 turns, adding the remaining xylene solution of the macromolecular modifier, regulating the rotating speed to 1500-2000 turns, stirring for 5-10 min, and controlling the temperature to be lower than 130 ℃ to finally prepare the modified fly ash.
The macromolecular modifier is prepared by adopting the following method:
adding low molecular weight polybutadiene (LMPB) and xylene with the mass of 3-5 times that of the LMPB into a reaction kettle which is heated by an oil bath, can be sealed and is provided with a condensing tube and a dropping funnel, fully dissolving, and preparing into a solution;
dissolving gamma-methacryloxypropyltrimethoxysilane (KH570) with the mass of 1/10-1/4% of LMPB and dibenzoyl peroxide (BPO) with the mass of 1-3% of LMPB in xylene with the mass of 3-5 times that of LMPB to prepare a mixed solution, adding the mixed solution into a constant-pressure dropping funnel, and adding the constant-pressure dropping funnel onto a reaction kettle; pumping air in the reaction kettle, and introducing high-purity nitrogen for protection;
raising the temperature of the oil bath to 85-90 ℃, opening a valve of a dropping funnel under stirring, slowly dropping a xylene mixed solution of KH570 and BPO, finishing dropping within 30-60min, raising the temperature to 95-100 ℃, stopping heating after reacting for 4-8 hours, and cooling to room temperature;
pouring the reaction solution into a separating funnel, and adding methanol with the same volume as that of the xylene to precipitate and separate the macromolecular modifier; the precipitate was washed 2 times with equal amounts of methanol; and (3) carrying out rotary evaporation and drying at the temperature of 60-80 ℃ to obtain the macromolecular modifier.
6. The fly ash-based ceramic silicone rubber composite material according to claim 1, wherein the modified short fiber is prepared by the following method:
the high-speed stirrer is preheated to 50-70 ℃, 40 parts by mass of short fibers, 5-15 parts by mass of paraffin oil, 5-10 parts by mass of hydroxyl-terminated polybutadiene with the molecular weight of 1000-2000 and 5-10 parts by mass of stearic acid are added to be stirred at a low speed for 30s, and then the mixture is stirred at a high speed for 6-15 min; then stopping the machine once every 3-5min to clean the materials attached to the stirrer cover and uniformly mix the materials with the rest materials to finally prepare modified short fibers;
the short fiber raw material can be one or more of aramid chopped fiber, aramid pulp fiber, polyimide chopped fiber, cellulose chopped fiber, acrylic chopped fiber, polypropylene chopped fiber, polyester chopped fiber, chopped carbon fiber, high silica glass fiber and basalt fiber.
7. The fly ash-based ceramic silicone rubber composite material as claimed in claim 1, wherein the structure control agent is a mixture of low-melting-point glass micropowder and metal oxide in a mass ratio of 1/1-3/1; the metal oxide is one or a mixture of more than two of aluminum oxide, calcium oxide, zirconium oxide, magnesium oxide, titanium oxide, boron oxide and zinc oxide.
8. The fly ash-based ceramicized silicone rubber composite according to claim 1, wherein the vulcanizing agent is one or a mixture of two or more of Benzoyl Peroxide (BPO), dicumyl peroxide (DCP), di-tert-butyl peroxide (DTBP), 2, 4-dichloroperoxybenzoyl (bis-di-tetra) and 2, 5-dimethyl-2, 5-bis (tert-butylperoxy) hexane.
9. The preparation method of the fly ash-based ceramic silicone rubber composite material according to claim 1, comprising the steps of:
uniformly mixing silicon rubber on a double-roller open mill, wrapping the silicon rubber on a roller, adding a required activating agent, and uniformly mixing rubber; then adding the reinforcing agent white carbon black, and performing thin pass for several times to mix uniformly, so as to improve the strength of the silicone rubber; adding hydroxyl silicone oil, uniformly mixing, adding the modified fly ash, the structure control agent and the modified short fibers into a double-roll open mill, and mixing at the mixing temperature of 20-50 ℃; finally, adding a vulcanizing agent, performing thin pass for more than 5-10 times in a triangular bag forming mode at the temperature of not higher than 50 ℃ to achieve a uniform state, adjusting the roller distance to 2mm, and uniformly discharging to obtain mixed silicon rubber; after the sheet is taken out, curing the silicon rubber composite material at room temperature for 16-48 h; putting the rubber compound into a mold, and vulcanizing by using a flat vulcanizing machine, wherein the vulcanizing temperature is 150-180 ℃, and the vulcanizing time is 10-30 min, so as to finally obtain the fly ash-based ceramic silicone rubber composite material;
or,
adding silicon rubber, an activating agent, hydroxyl silicone oil, white carbon black, modified fly ash, a structure control agent and modified short fibers into an internal mixer according to the proportion for internal mixing, wherein the temperature is not higher than 80 ℃, the internal mixing is carried out until the torque of the internal mixer tends to be stable, discharging is carried out, and the temperature is reduced to room temperature; opening the rubber material placed to room temperature on an open mill, uniformly wrapping rollers, adding a vulcanizing agent, allowing the temperature to be lower than 50 ℃, performing thin pass for more than 5-10 times in a triangular wrapping mode to achieve a uniform state, adjusting the roller distance to 2mm, and uniformly discharging to obtain mixed silicon rubber; after the sheet is taken out, curing the silicon rubber compound for 16-48 hours at room temperature; and putting the rubber compound into a mold, and vulcanizing by using a flat vulcanizing machine at the vulcanization temperature of 150-180 ℃ for 10-30 min to finally obtain the fly ash-based ceramic silicone rubber composite material.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113248244A (en) * | 2021-05-18 | 2021-08-13 | 国网重庆市电力公司电力科学研究院 | Low-temperature ceramic insulating material suitable for complex insulating structure and preparation method thereof |
| CN113308120A (en) * | 2021-06-30 | 2021-08-27 | 华南理工大学 | Light ceramizable silicone rubber and preparation method thereof |
| CN113539585A (en) * | 2021-06-28 | 2021-10-22 | 安徽正豪电缆有限公司 | Production process of flexible fireproof cable |
| WO2022099650A1 (en) * | 2020-11-13 | 2022-05-19 | 金序能 | High-strength composite material and application thereof |
| CN115386140A (en) * | 2022-09-01 | 2022-11-25 | 江西广源化工有限责任公司 | Nano flaky kaolin-wollastonite-hydroxy silicone oil ternary composite powder and preparation method and application thereof |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050247469A1 (en) * | 2004-05-10 | 2005-11-10 | Wacker-Chemie Gmbh | Cable components of silicone comprising glass fibers |
| CN101735620A (en) * | 2009-12-27 | 2010-06-16 | 周忠坤 | High-temperature resisting methyl vinyl silicone rubber |
| CN104629374A (en) * | 2015-01-22 | 2015-05-20 | 东北大学 | Silicone rubber based ablation-resisting heat insulation composite material and preparation method thereof |
| CN104927358A (en) * | 2015-06-16 | 2015-09-23 | 安徽天元电缆有限公司 | High-strength flame-retardant cable material for power cables and preparation method thereof |
| CN105860536A (en) * | 2016-04-13 | 2016-08-17 | 山东兆圭高分子材料科技有限公司 | Flame-retardant and fire-resistant ceramic silicone rubber and preparation method thereof |
| CN107325561A (en) * | 2017-07-11 | 2017-11-07 | 芜湖市宝艺游乐科技设备有限公司 | It is a kind of can porcelain polyimide fiber silicon rubber composite material and preparation method thereof |
| CN107400257A (en) * | 2017-09-14 | 2017-11-28 | 苏州盱酋汽车科技有限公司 | A kind of automobile engine cover carbon fiber reinforced polymer composite and preparation method thereof |
| CN108948743A (en) * | 2018-05-14 | 2018-12-07 | 倍仕得电气科技（杭州）股份有限公司 | A kind of waterproof anti-aging Ceramic silicon rubber material, preparation method and applications |
-
2020
- 2020-06-28 CN CN202010597546.5A patent/CN111635635A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050247469A1 (en) * | 2004-05-10 | 2005-11-10 | Wacker-Chemie Gmbh | Cable components of silicone comprising glass fibers |
| CN101735620A (en) * | 2009-12-27 | 2010-06-16 | 周忠坤 | High-temperature resisting methyl vinyl silicone rubber |
| CN104629374A (en) * | 2015-01-22 | 2015-05-20 | 东北大学 | Silicone rubber based ablation-resisting heat insulation composite material and preparation method thereof |
| CN104927358A (en) * | 2015-06-16 | 2015-09-23 | 安徽天元电缆有限公司 | High-strength flame-retardant cable material for power cables and preparation method thereof |
| CN105860536A (en) * | 2016-04-13 | 2016-08-17 | 山东兆圭高分子材料科技有限公司 | Flame-retardant and fire-resistant ceramic silicone rubber and preparation method thereof |
| CN107325561A (en) * | 2017-07-11 | 2017-11-07 | 芜湖市宝艺游乐科技设备有限公司 | It is a kind of can porcelain polyimide fiber silicon rubber composite material and preparation method thereof |
| CN107400257A (en) * | 2017-09-14 | 2017-11-28 | 苏州盱酋汽车科技有限公司 | A kind of automobile engine cover carbon fiber reinforced polymer composite and preparation method thereof |
| CN108948743A (en) * | 2018-05-14 | 2018-12-07 | 倍仕得电气科技（杭州）股份有限公司 | A kind of waterproof anti-aging Ceramic silicon rubber material, preparation method and applications |
Non-Patent Citations (4)
| Title |
|---|
| 乔昭毓: "粉煤灰表面改性及其在聚氨酯弹性体中的应用", 《中国优秀硕士学位论文全文数据库工程科技I辑》 * |
| 刘英俊等: "《改性塑料行业指南：塑料改性理论与实践及企事业名录》", 30 September 2000 * |
| 周安宁等: "《洁净煤技术》", 28 February 2018 * |
| 橡胶工业原材料与装备简明手册编审委员会: "《橡胶工业原材料与装备简明手册，原材料与工艺耗材分册》", 31 January 2019 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022099650A1 (en) * | 2020-11-13 | 2022-05-19 | 金序能 | High-strength composite material and application thereof |
| CN113248244A (en) * | 2021-05-18 | 2021-08-13 | 国网重庆市电力公司电力科学研究院 | Low-temperature ceramic insulating material suitable for complex insulating structure and preparation method thereof |
| CN113248244B (en) * | 2021-05-18 | 2023-01-20 | 国网重庆市电力公司电力科学研究院 | Low-temperature ceramic insulating material suitable for complex insulating structure and preparation method thereof |
| CN113539585A (en) * | 2021-06-28 | 2021-10-22 | 安徽正豪电缆有限公司 | Production process of flexible fireproof cable |
| CN115537137A (en) * | 2021-06-29 | 2022-12-30 | 中国科学院化学研究所 | Ceramizable silicone rubber compound, ceramizable silicone rubber, and preparation method and application thereof |
| CN115537137B (en) * | 2021-06-29 | 2023-09-12 | 中国科学院化学研究所 | Ceramic silicon rubber compound, ceramic silicon rubber and preparation method and application thereof |
| CN113308120A (en) * | 2021-06-30 | 2021-08-27 | 华南理工大学 | Light ceramizable silicone rubber and preparation method thereof |
| CN115386140A (en) * | 2022-09-01 | 2022-11-25 | 江西广源化工有限责任公司 | Nano flaky kaolin-wollastonite-hydroxy silicone oil ternary composite powder and preparation method and application thereof |
| CN115386140B (en) * | 2022-09-01 | 2023-08-25 | 江西广源化工有限责任公司 | Nanometer flaky kaolin-wollastonite-hydroxyl silicone oil ternary composite powder and preparation method and application thereof |
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