CN110317072A - A kind of preparation method and application method of magnetism anti-bacteria ceramic polymer precursor - Google Patents

A kind of preparation method and application method of magnetism anti-bacteria ceramic polymer precursor Download PDF

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CN110317072A
CN110317072A CN201910449712.4A CN201910449712A CN110317072A CN 110317072 A CN110317072 A CN 110317072A CN 201910449712 A CN201910449712 A CN 201910449712A CN 110317072 A CN110317072 A CN 110317072A
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magnetic
mixed
polymer precursor
ferrocene
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余国海
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Fuyang Chuangqi Crafts Co Ltd
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Fuyang Chuangqi Crafts Co Ltd
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Abstract

The invention discloses the preparation methods and application method of a kind of magnetic anti-bacteria ceramic polymer precursor, the present invention is using ferrocene and the complex reaction of siloxanyl monomers elder generation, it is re-introduced into silane, borine monomer, polymerization reaction forms ferrocene performed polymer containing borosilicate, it is being that activity processing component surface handles silica template microballoon with this performed polymer, pass through the dispersion of performed polymer and package template microsphere effect again, the carbon containing borosilicate magnetic ceramics polymer of template microsphere is enclosed in hydrothermal condition controlled syntheses, template is etched, form microcosmic core-shell structure toughening, magnetic ceramics polymer precursor disclosed by the invention is obtained through high-temperature process in nitrogen again and assigns its good absorbing property, and it discloses by the method for its microwave low-temperature sintered ceramics, obtain the ceramic material with excellent heatproof antioxygenic property and high intensity of polynary composition, operation Simply, raw material sources are extensive, increase substantially magnetism, provide conveniently for the magnetic ceramics preparation of diversified shape.

Description

A kind of preparation method and application method of magnetism anti-bacteria ceramic polymer precursor
Technical field
The present invention relates to ceramic technology field, in particular to a kind of preparation method of magnetic anti-bacteria ceramic polymer precursor With application method.
Background technique
Magnetic material typically refers to directly or indirectly generate magnetism by transition elements iron, cobalt, nickel and its alloy etc. Substance is a kind of functional material that purposes is very extensive.Modem magnetic materials have been widely used among our life, example Such as, permanent-magnet material is used as motor, the core material applied in transformer, the magneto-optic disk, the Yi Jiji that use as memory Calculation machine magnetic recording floppy disk etc., and with informationization, automation, electromechanical integration, national defence, the close phase of the every aspect of national economy It closes.Magnetic material can be divided into soft magnetic material and retentive material by the complexity of degaussing after magnetization, be easy to remove after magnetization Magnetic substance is soft magnetic material, conversely, being not easy to demagnetize after magnetization, can retaining magnetic is then retentive material, generally For soft magnetic material remanent magnetism it is smaller, retentive material remanent magnetism is larger.Hard magnetic material is also known as permanent-magnet material or permanent magnetic material, this Kind material property is preferable, and cost is relatively low, can be used not only as the magnetic of the telecommunications devices such as phonographic recorder, telephone set and various instrument Iron, and medicine, biology and in terms of be also widely applied.In hard magnetic material, Hard Magnetic metal material Be widely used because magnetic property is good, but the shortcomings that material be in high frequency energy loss it is serious, and exist easy The problems such as oxidation.Especially with ferrite hard magnetic material as main component, have eddy current loss small, and abundant raw material, magnetism The excellent advantage of energy, in high frequency and microwave regime, such as communication, computer etc. are still preferred material.Typical hard magnetic material Representative has barium ferrite, strontium ferrite, lead ferrite and their complex.But such material coercivity (Hc) is smaller, magnetic Level density ((BH) max) is lower and molding is more difficult, and high temperature is oxidizable, easy to reunite, and processing difficulties cause actual There are still very big problem in terms of engineer application, simple mixing addition magnetic material can not achieve ceramics and have good magnetism Energy.Therefore, how to control the molding diversification of magnetic ceramic material, customize, automation, and improve the magnetism of ceramic material Can, it is the widely applied key problem in technology of this kind of material.Currently, the molding mode of the magnetic materials such as ferrite mainly includes pouring into Type method, injection molding method, compression molding method and hot pressing sintering method.Studies have shown that although these methods are available certain The magnetic material of shape, but it is only limitted to the ceramic material of simple shape.And it is excellent to have conventional ceramic and special cermacis Different magnetism is even more the problem of field of ceramic preparation technology.And as modern device is intended to high-performance, miniaturization, customization Direction is developed, and traditional handicraft has been unable to meet the demand of ceramic material personalization.Generally for obtaining custom-shaped and size Ceramic material generally requires expensive mold or pressing element, and some then must be further by the way of machine cuts.But It is that not only production technology is complicated, production cost is higher for such forming method, but also also causes the waste of material, seriously limits The diversification and customization production of ceramic material shape.Polymer precursor is converting to have prepared inorganic ceramic technology increasingly Maturation, but rarely having magnetic polymer ceramic forerunner Polymer ceramic precursor itself at present is high temperature of the organic matter in experience After cracking, inorganic ceramic resistant to high temperature can be transformed into, have both the processability and inorganic material heat-resisting quantity of organic material Advantage, using it as ceramics etc., the bridging agent of materials can not only meet requirement resistant to high temperature, and due to polymer precursor Usually liquid or slurry, sizing is convenient, good manufacturability, is conducive to prepare complicated shape and high-performance pottery using Organic adhesive The Polymer ceramic precursor of effect realizes that presoma can at a certain temperature to after the connection of base material for polymer precursor Cracking is converted into the bridge joint that amorphous ceramics play the role of similar inorganic adhesive.Connection is directly with chemical bonds. CN101830559A discloses " water process magnetic porous environmental-conscious ceramic filter material and preparation method thereof ", but its is made Standby ceramic material magnetism is weak." a kind of magnetic ceramic material and preparation method thereof " disclosed in CN104609857A, it is still unresolved For Fe 3 O 4 magnetic additive in problem of oxidation under the conditions of 1350 ~ 1380 DEG C of equal high temperature, ceramic material magnetism is weak.At present Not being magnetic also in the market, strong, preparation method is simple, easily molded, the convenient ceramics polymer presoma of plasticity, art technology Personnel urgently develop novel ceramics polymer precursor preparation method, to meet higher use demand.
Summary of the invention
The purpose of the present invention is being directed to existing problem, a kind of preparation of magnetic anti-bacteria ceramic polymer precursor is provided Method and application method.
A kind of preparation method of magnetism anti-bacteria ceramic polymer precursor includes the following steps: one, in nitrogen protection and stirs It mixes down, n-BuLi hexane solution is added drop-wise in the evenly dispersed n-hexane for having ferrocene, tetramethyl second two is then added Amine, mixture are stirred to react, 10 ~ 12h, are filtered under oxygen-free atmosphere, are washed with n-hexane, and revolving removes n-hexane solvent, vacuum Dry ferrocene complex compound；Two, under nitrogen protection, then by ferrocene complex compound, the uniform stirring in -5 ~ 0 DEG C of ice-water bath While be added dimethyldichlorosilane, phenyl dichloro boron, then with oil bath heating to 80 ~ 90 DEG C start be added dropwise 0.5 ~ lh of dimethylamine It drips off, 105 ~ 110 DEG C is warming up to after 1 ~ 2h of insulation reaction, reaction to system pH is 6.7 ~ 7.5, is cooled to 60 ~ 70 DEG C, adds Styrene, polyethylene glycol, and drop evenly catalyst, are warming up to 100 ~ 110 DEG C and are stirred to react 1 ~ 2h and drop evenly dipropyl again Silicon diol is stirred to react 1 ~ 2h to get the modified poly- boron silane pre-polymer of ferrocene；Three, uniformly divided using sol-gal process preparation Ethyl orthosilicate, dehydrated alcohol, formamide, water are specially mixed, are made adjustments with dilute hydrochloric acid by scattered silica template microballoon Agent adjusts pH3 ~ 4, then 60 DEG C of heated at constant temperature 1 ~ 2h of reflux adjust pH6 ~ 7 with ammonium hydroxide and obtain template microsphere, then use dehydrated alcohol 1 ~ 3h of silica template microballoon is impregnated, 1 ~ 2h of ageing in the ethanol solution of ethyl orthosilicate is placed into, is obtained in step 2 The modified poly- boron silane pre-polymer of the ferrocene arrived carries out the modified 1 ~ 2h in surface, i.e., silica mould after being aged to product after ageing Plate microballoon is distributed in the modified poly- boron silane pre-polymer of ferrocene, is added acetone, is stirred by ultrasonic and is uniformly mixed 30 ~ 40min, so Hydrogenperoxide steam generator is added slowly in above-mentioned mixed solution afterwards, 30 ~ 40min of magnetic agitation keeps mixed liquor evenly dispersed, then In the stainless steel reaction under high pressure gold that mixed liquor is gone to, sustained response 20 ~ for 24 hours is kept the temperature after being heated to 180 ~ 200 DEG C, reaction terminates Room temperature is naturally rung to later, sediment is cleaned multiple times with acetone, Magnetic Isolation, finally obtains black magnetic product and in vacuum tube After 350 ~ 400 DEG C of nitrogen atmospheres are dry in formula furnace, grey black magnetic product is obtained；Four, it will be ground in grey black magnetic product Subcommittee-to alms bowl It is broken, it is mixed with appropriate abrasive media dehydrated alcohol and zirconium oxide balls, 1 ~ 2h of ball milling, 600 ~ 800 turns per minute of revolving speed, it is rear to dry Dry, sieving is mixed with terpene-phenolic resin, carries out thermoforming, molding using product of the add in-place piezoresistance heating metal die to black Method is to take that powder filling hot pressing die need to be formed, and pressurize 100 ~ 200MPa when being warming up to 200 ~ 340 DEG C, heat-insulation pressure keeping 10 ~ 30min, cooling release demoulding are chosen fine and close flawless molding blank and are put into Si-Mo rod high temperature furnace, with one in nitrogen atmosphere Determine heating rate and be warming up to 700 ~ 900 DEG C of heating rates, 10 DEG C/min, 700 ~ 900 DEG C of 5 ~ 35min pyrolysis keep the temperature 1 ~ 1.5h, i.e., , a kind of magnetism anti-bacteria ceramic polymer precursor, the raw material proportioning are as follows: 30 ~ 40 parts of ferrocene, 100 ~ 200 parts of n-hexane, 150 ~ 160 parts of n-BuLi hexane solution, 2 ~ 5 parts of tetramethylethylenediamine, 10 ~ 15 parts of ethyl orthosilicate, dehydrated alcohol 20 ~ 30 Part, 0.5 ~ 2.3 part of formamide, 0.2 ~ 0.5 part of polyethylene glycol, 0.2 ~ 0.3 part of catalyst, 10 ~ 22 parts of styrene, acetone 20 ~ 34 Part, 15 ~ 36 parts of hydrogenperoxide steam generator, 0.2 ~ 0.5 part of terpene-phenolic resin.
A kind of magnetism anti-bacteria ceramic polymer precursor application method are as follows: (1) by magnetic anti-bacteria ceramic polymer precursor 17 ~ 23 parts, 3.9 ~ 4.2 parts of calcite, 2.6 ~ 3.0 parts of nepheline, 2.8 ~ 5.0 parts of calcinated talc powder, calcining zinc oxide 2.6 ~ 4.8 Part, 3.3 ~ 5.0 parts of spodumene of calcining, 2.5 ~ 3.8 parts of kaolin, 1.2 ~ 2.3 parts of barium monoxide, 1.1 ~ 3.3 parts of boron oxide, oxidation are dilute 2.5 ~ 3.0 parts of soil, 1.2 ~ 1.8 parts of basalt fibre, 3 ~ 10 parts of modified meerschaum, 2.2 ~ 4.8 parts of zirconium silicate weigh, and will be described Potassium feldspar, calcite, nepheline, calcinated talc powder, calcining zinc oxide, calcining spodumene, kaolin, barium monoxide and boron oxide, fill Divide and be uniformly mixed, obtains mixed material, carboxymethyl cellulose and water is added in Xiang Suoshu mixed material, is sufficiently mixed uniformly, obtains To mixed slurry；The carboxymethyl cellulose accounts for the 0.1 ~ 0.2% of the mixed material quality, and the amount for adding water accounts for the mixing The 20 ~ 25% of quality of material；(2) rare earth oxide is added in Xiang Suoshu mixed slurry, is sieved after 1 ~ 1.5h of wet-milling, to strained pulp Middle addition basalt fibre is sieved after 1 ~ 1.5h of wet-milling, modified meerschaum, mistake after 1 ~ 1.5h of wet-milling is added into strained pulp Sieve, zirconium silicate is added into strained pulp, is sieved after 1 ~ 1.5h of wet-milling, obtains ceramic mixture；(3) ceramic mixture is consolidated Change processing, solidification temperature are re-fed into microwave agglomerating furnace progress, sintering temperature 700 at 120 ~ 250 DEG C, 0.5 ~ 10h of soaking time ~ 1050 DEG C of low-temperature sintering process, the frequency of low-temperature sintered microwave are 2450 ~ 2600MHz, 400 ~ 1000W of power；Microwave sintering Stove heating uses temperature controlling mode, first with 800 ~ 1000W microwave irradiation 5 ~ 15 minutes, then irradiates 10 ~ 30 points using 400 ~ 800W Clock, and in 700 ~ 1050 DEG C of 65 ~ 90min of calcining, room temperature is cooled to according still further to 15 ~ 50 DEG C/min of cooling velocities, after cooling Up to the ceramics for using precursor preparation.
Further, the modified meerschaum powder the preparation method comprises the following steps: sepiolite powder is put into double-[γ-(triethoxy Silicon) propyl] in tetrasulfide alcohol dispersion liquid solution, the sepiolite powder and double-[γ-(triethoxysilicane) propyl] four vulcanize The volume ratio of object alcohol dispersion liquid solution is 1:12.5, is impregnated 1 hour, and double-[γ-(triethoxysilicane) propyl] four is then removed Sulfide alcohol dispersion liquid solution, 45 DEG C of modified meerschaum powder obtained by drying.
Further, the n-BuLi hexane solution is 1.3 ~ 1.6M, the matter of hydrogen peroxide in hydrogenperoxide steam generator Measuring score is 20% ~ 35%, and ammonia concn is 0.1 ~ 1.5mol/L, and dilute hydrochloric acid concentration is 0.1 ~ 1mol/L.
Further, the catalyst is RuCl3、H2PtCl6、H2IrCl6。
Further, the mixed oxidization that the rare earth oxide is yttrium oxide and ceria mass ratio is 2:1 ~ 2.75:1 is dilute Soil.
Further, the terpene-phenolic resin be softening point be 65 ~ 71 DEG C, hydroxy radical content be 5.5 ~ 6.3%, bromine number be 175 ~ The terpene-phenolic resin of 180mg/100g resin.
Further, the potassium feldspar is powder head, canescence；Ferric oxide content is less than 1% in the nepheline.
Further, calcium oxide content >=53.5% in the calcite；The calcining zinc oxide be it is powdered, it is slightly yellow It adjusts, content of magnesia >=36.5% in the calcinated talc powder.
Beneficial effects of the present invention:
The conjugated system conductive structure that the pi-electron of luxuriant ring and transition metal d orbital electron participate in ferrocene, and core-shell structure It is formed not only due to and in practice process, be found surprisingly that because its ferroso-ferric oxide is that ceramics provide the source of magnetism, Contain nucleocapsid meso-hole structure in component, the toughener of ceramic material can be formed, this is not available for general solid magnetic material Outstanding properties, do not have to additional addition toughener, and because performed polymer itself because of the long last chain of silane molecule, naturally to have table The generation of the phenomenon that active dispersion in face, magnetisable material is uniformly dispersed, does not have reunion, and performed polymer sheet is by ferrocene group Divide and constitute, the template magnetic carbon sphere of package silica is generated by hydro-thermal reaction, and performed polymer is in the process because of its tool Some Natural surfactants can be surface-treated silica again, keep silica evenly dispersed, and pass through etching off two Silica makes polymer precursor have mesoporous carbon-coating, forms the suction that the bent duct returned of microwave turnover further increases presoma Wave performance, and carbon-coating can be ferroso-ferric oxide, provide oxidation resistant protection shell, reduce the possibility of its oxidation, and preceding It in the application process for driving body preparation ceramics, is found surprisingly that, microwave low temperature is passed through using the magnetic polymer presoma of preparation Sintering temperature, festival energy, the ceramics of the complicated pattern of more controllable preparation, requirements at the higher level can be significantly reduced in sintering.And pass through By rare earth modified synergetic antibacterial effect can occur for the magnetic ceramics of this precursor preparation.
The present invention has the advantage that compared with prior art
Present invention employs the poly- ceramics polymer presomas of magnetism of preparation to have the characteristic inhaled wave component and turn round micropore, significantly Sintering temperature is reduced, compared with conventional sintering, cooling extent maximum is up to 300 ~ 500 DEG C.It is energy-efficient, than conventional sintering energy conservation 70%~90%.Since the time of microwave sintering greatly shortens, the utilization efficiency of the energy is substantially increased；Safety non-pollution makes It obtains the usage amount during the sintering process as the gas of sintering atmosphere to substantially reduce, this not only lowers costs, also make sintered Exhaust gas in journey, waste heat discharge amount be reduced；Improve the performance of material under the conditions of being rapidly heated.It is quickly risen using microwave sintering Mild densification can inhibit grain structure to grow up, to prepare nanometer powder, ultra-fine or nano bulk material.It improves fine and close Degree increases grain uniformity.Particle kinetic energy, the diffusion of effective accelerated particle can be improved in microwave radiation, so microwave sintering facilitates Material density is improved, grain uniformity is increased.
Specific embodiment
Illustrate the present invention with specific embodiment below, but is not limitation of the present invention.
Embodiment 1
A kind of preparation method of magnetism anti-bacteria ceramic polymer precursor, includes the following steps: one, in nitrogen protection and stirring Under, n-BuLi hexane solution is added drop-wise in the evenly dispersed n-hexane for having ferrocene, tetramethylethylenediamine is then added, Mixture is stirred to react, 12h, is filtered under oxygen-free atmosphere, is washed with n-hexane, and revolving removes n-hexane solvent, is dried in vacuo Ferrocene complex compound；Two, under nitrogen protection, then by ferrocene complex compound, in -5 ~ 0 DEG C of ice-water bath while uniform stirring Dimethyldichlorosilane, phenyl dichloro boron is added, then starts dropwise addition dimethylamine lh to 90 DEG C with oil bath heating and drips off, insulation reaction 110 DEG C are warming up to after 2h, reaction to system pH is 7.5, is cooled to 70 DEG C, adds styrene, polyethylene glycol, and drop evenly Catalyst, is warming up to 110 DEG C and is stirred to react 1h and drop evenly dipropyl silicon diol again, is stirred to react 1 ~ 2h and changes to get ferrocene The poly- boron silane pre-polymer of property；Three, evenly dispersed silica template microballoon is prepared using sol-gal process, specially by positive silicon Acetoacetic ester, dehydrated alcohol, formamide, water mixing make adjustments agent with dilute hydrochloric acid and adjust pH4,60 DEG C of heated at constant temperature reflux 2h, then PH7 is adjusted with ammonium hydroxide and obtains template microsphere, is then used soaked in absolute ethyl alcohol silica template 1 ~ 3h of microballoon, is placed into positive silicic acid second Be aged 2h in the ethanol solution of ester, the modified poly- boron silane pre-polymer of ferrocene obtained in step 2 to product after ageing into Row surface is modified 2h, i.e., silica template microballoon after ageing is distributed in the modified poly- boron silane pre-polymer of ferrocene, then plus Enter acetone, is stirred by ultrasonic and is uniformly mixed 30 ~ 40min, then hydrogenperoxide steam generator is added slowly in above-mentioned mixed solution, magnetic force Stirring 40min keeps mixed liquor evenly dispersed, in the stainless steel reaction under high pressure gold for then going to mixed liquor, after being heated to 200 DEG C Keep the temperature sustained response for 24 hours, reaction naturally rings to room temperature after terminating, and sediment is cleaned multiple times with acetone, Magnetic Isolation, finally It obtains black magnetic product and in vacuum tube furnace after 350 ~ 400 DEG C of nitrogen atmospheres dryings, obtains grey black magnetic product；Four, will It grinds, is mixed with appropriate abrasive media dehydrated alcohol and zirconium oxide balls, ball milling 2h in grey black magnetic product Subcommittee-to alms bowl, turned 800 turns per minute of speed, rear drying, sieving are mixed with terpene-phenolic resin, using add in-place piezoresistance heating metal die to black Product carries out thermoforming, and forming method is to take that powder filling hot pressing die need to be formed, and pressurize 200MPa when being warming up to 340 DEG C, protects Warm pressure maintaining 30min, cooling release demoulding are chosen fine and close flawless molding blank and are put into Si-Mo rod high temperature furnace, in nitrogen atmosphere In 900 DEG C of heating rates, 10 DEG C/min is warming up to certain heating rate, 900 DEG C of 5 ~ 35min pyrolysis keep the temperature 1h to get a kind of Magnetic anti-bacteria ceramic polymer precursor, the raw material proportioning are as follows: 30 parts of ferrocene, 100 parts of n-hexane, n-BuLi n-hexane 150 parts of solution, 2 parts of tetramethylethylenediamine, 10 parts of ethyl orthosilicate, 20 parts of dehydrated alcohol, 0.5 part of formamide, polyethylene glycol 0.2 Part, 0.2 part of catalyst, 10 parts of styrene, 5 parts of ammonium hydroxide, 20 parts of acetone, 15 parts of hydrogenperoxide steam generator, 0.2 part of terpene-phenolic resin.
A kind of magnetism anti-bacteria ceramic polymer precursor application method are as follows: by magnetic anti-bacteria ceramic polymer precursor 23 Part, 4.2 parts of calcite, 3.0 parts of nepheline, 5.0 parts of calcinated talc powder, 4.8 parts of calcining zinc oxide, calcining 5.0 parts of spodumene, kaolinite Soil 3.8 parts, 2.3 parts of barium monoxide, 3.3 parts of boron oxide, 3.0 parts of rare earth oxide, 1.8 parts of basalt fibre, 10 parts of modified meerschaum, 4.8 parts of zirconium silicate weigh, and by the potassium feldspar, calcite, nepheline, calcinated talc powder, calcining zinc oxide, calcining spodumene, Kaolin, barium monoxide and boron oxide are sufficiently mixed uniformly, obtain mixed material, and it is fine that carboxymethyl is added in Xiang Suoshu mixed material Dimension element and water, are sufficiently mixed uniformly, obtain mixed slurry；The carboxymethyl cellulose accounts for the 0.2% of the mixed material quality, The amount of addition water accounts for the 25% of the mixed material quality；(2) rare earth oxide is added in Xiang Suoshu mixed slurry, after wet-milling 1.5h Sieving, basalt fibre is added into strained pulp, is sieved after wet-milling 1.5h, modified meerschaum is added into strained pulp, wet It is sieved after mill 1.5h, zirconium silicate is added into strained pulp, is sieved after wet-milling 1.5h, obtains ceramic mixture；(3) ceramics are mixed Object carries out curing process, and solidification temperature is re-fed into microwave agglomerating furnace progress, sintering temperature 700 at 250 DEG C, soaking time 10h ~ 1050 DEG C of low-temperature sintering process, the frequency of low-temperature sintered microwave are 2450 ~ 2600MHz, 400 ~ 1000W of power；Microwave sintering Stove heating uses temperature controlling mode, first uses 800W microwave irradiation 15 minutes, is then irradiated 30 minutes using 400W, and at 1050 DEG C 65min is calcined, room temperature is cooled to according still further to 50 DEG C/min of cooling velocities, uses the ceramics of precursor preparation after cooling to obtain the final product.
Further, the modified meerschaum powder the preparation method comprises the following steps: sepiolite powder is put into double-[γ-(triethoxy Silicon) propyl] in tetrasulfide alcohol dispersion liquid solution, the sepiolite powder and double-[γ-(triethoxysilicane) propyl] four vulcanize The volume ratio of object alcohol dispersion liquid solution is 1:12.5, is impregnated 1 hour, and double-[γ-(triethoxysilicane) propyl] four is then removed Sulfide alcohol dispersion liquid solution, 45 DEG C of modified meerschaum powder obtained by drying.
Further, the n-BuLi hexane solution is 1.3M, the quality point of hydrogen peroxide in hydrogenperoxide steam generator Number is 20%, ammonia concn 0.5mol/L, and dilute hydrochloric acid concentration is 0.5mol/L.
Further, the catalyst is RuCl3、H2PtCl6、H2IrCl6。
Further, the mixed rare earth oxide that the rare earth oxide is yttrium oxide and ceria mass ratio is 2:1.
Further, the terpene-phenolic resin be softening point be 65 ~ 71 DEG C, hydroxy radical content be 5.5 ~ 6.3%, bromine number be 175 ~ The terpene-phenolic resin of 180mg/100g resin.
Further, the potassium feldspar is powder head, canescence；Ferric oxide content is less than 1% in the nepheline.
Further, calcium oxide content >=53.5% in the calcite；The calcining zinc oxide be it is powdered, it is slightly yellow It adjusts, content of magnesia >=36.5% in the calcinated talc powder.
Embodiment 2
A kind of preparation method of magnetism anti-bacteria ceramic polymer precursor, includes the following steps: one, in nitrogen protection and stirring Under, n-BuLi hexane solution is added drop-wise in the evenly dispersed n-hexane for having ferrocene, tetramethylethylenediamine is then added, Mixture is stirred to react, 10h, is filtered under oxygen-free atmosphere, is washed with n-hexane, and revolving removes n-hexane solvent, is dried in vacuo Ferrocene complex compound；Two, under nitrogen protection, then by ferrocene complex compound, in -5 ~ 0 DEG C of ice-water bath while uniform stirring Dimethyldichlorosilane, phenyl dichloro boron is added, then starts dropwise addition dimethylamine lh to 90 DEG C with oil bath heating and drips off, insulation reaction 110 DEG C are warming up to after 2h, reaction to system pH is 7.5, is cooled to 70 DEG C, adds styrene, polyethylene glycol, and drop evenly Catalyst, is warming up to 110 DEG C and is stirred to react 1 ~ 2h and drop evenly dipropyl silicon diol again, is stirred to react 2h and changes to get ferrocene The poly- boron silane pre-polymer of property；Three, evenly dispersed silica template microballoon is prepared using sol-gal process, specially by positive silicon Acetoacetic ester, dehydrated alcohol, formamide, water mixing make adjustments agent with dilute hydrochloric acid and adjust pH3 ~ 4,60 DEG C of heated at constant temperature reflux 2h, so PH7 is adjusted with ammonium hydroxide afterwards and obtains template microsphere, is then used soaked in absolute ethyl alcohol silica template microballoon 3h, is placed into positive silicic acid second Be aged 2h in the ethanol solution of ester, the modified poly- boron silane pre-polymer of ferrocene obtained in step 2 to product after ageing into Row surface is modified 2h, i.e., silica template microballoon after ageing is distributed in the modified poly- boron silane pre-polymer of ferrocene, then plus Enter acetone, is stirred by ultrasonic and is uniformly mixed 40min, then hydrogenperoxide steam generator is added slowly in above-mentioned mixed solution, magnetic force stirs Mixing 40min keeps mixed liquor evenly dispersed, in the stainless steel reaction under high pressure gold for then going to mixed liquor, protects after being heated to 200 DEG C For 24 hours, reaction naturally rings to room temperature after terminating to warm sustained response, sediment is cleaned multiple times with acetone, Magnetic Isolation, finally Black magnetic product simultaneously after 400 DEG C of nitrogen atmospheres dryings, obtains grey black magnetic product in vacuum tube furnace；Four, by grey black It grinds, is mixed with appropriate abrasive media dehydrated alcohol and zirconium oxide balls, ball milling 2h, every point of revolving speed in magnetic product Subcommittee-to alms bowl 800 turns of clock, rear drying, sieving are mixed with terpene-phenolic resin, using add in-place piezoresistance heat metal die to the product of black into Row thermoforming, forming method are to take that powder filling hot pressing die need to be formed, and pressurize 200MPa when being warming up to 200 DEG C, heat-insulation pressure keeping 30min, cooling release demoulding are chosen fine and close flawless molding blank and are put into Si-Mo rod high temperature furnace, with one in nitrogen atmosphere Determine heating rate and be warming up to 900 DEG C of heating rates, 10 DEG C/min, 900 DEG C of 35min pyrolysis keep the temperature 1.5h to get a kind of magnetic anti- Bacterium ceramics polymer presoma, the raw material proportioning are as follows: 40 parts of ferrocene, 200 parts of n-hexane, n-BuLi hexane solution 160 parts, 5 parts of tetramethylethylenediamine, 15 parts of ethyl orthosilicate, 20 ~ 30 parts of dehydrated alcohol, 2.3 parts of formamide, polyethylene glycol 0.5 Part, 0.3 part of catalyst, 22 parts of styrene, 8 parts of ammonium hydroxide, 34 parts of acetone, 36 parts of hydrogenperoxide steam generator, 0.5 part of terpene-phenolic resin.
A kind of magnetism anti-bacteria ceramic polymer precursor application method are as follows: (1) by magnetic anti-bacteria ceramic polymer precursor 17 parts, 3.9 parts of calcite, 2.6 parts of nepheline, 2.8 parts of calcinated talc powder, 2.6 parts of calcining zinc oxide, 3.3 parts of spodumene of calcining, height Ridge soil 2.5 parts, 1.2 parts of barium monoxide, 1.1 parts of boron oxide, 2.5 parts of rare earth oxide, 1.2 parts of basalt fibre, modified meerschaum 3 Part, 2.2 parts of zirconium silicate weigh, and by the potassium feldspar, calcite, nepheline, calcinated talc powder, calcining zinc oxide, calcining lithium brightness Stone, kaolin, barium monoxide and boron oxide are sufficiently mixed uniformly, obtain mixed material, carboxymethyl is added in Xiang Suoshu mixed material Cellulose and water are sufficiently mixed uniformly, obtain mixed slurry；The carboxymethyl cellulose accounts for the mixed material quality 0.2%, the amount for adding water accounts for the 25% of the mixed material quality；(2) rare earth oxide, wet-milling is added in Xiang Suoshu mixed slurry It is sieved after 1h, basalt fibre is added into strained pulp, is sieved after wet-milling 1h, modified meerschaum is added into strained pulp, It is sieved after wet-milling 1h, zirconium silicate is added into strained pulp, is sieved after wet-milling 1.5h, obtains ceramic mixture；(3) ceramics are mixed Object carries out curing process, 250 DEG C of solidification temperature, soaking time 10h, is re-fed into microwave agglomerating furnace progress, sintering temperature 1050 DEG C low-temperature sintering process, the frequency of low-temperature sintered microwave is 2600MHz, 400 ~ 1000W of power；Microwave sintering stove heating uses Temperature controlling mode is first used 800W microwave irradiation 15 minutes, is then irradiated 30 minutes using 800W, and in 1050 DEG C of calcining 90min, Room temperature is cooled to according still further to 15 DEG C/min of cooling velocities, uses the ceramics of precursor preparation after cooling to obtain the final product.
Further, the modified meerschaum powder the preparation method comprises the following steps: sepiolite powder is put into double-[γ-(triethoxy Silicon) propyl] in tetrasulfide alcohol dispersion liquid solution, the sepiolite powder and double-[γ-(triethoxysilicane) propyl] four vulcanize The volume ratio of object alcohol dispersion liquid solution is 1:12.5, is impregnated 1 hour, and double-[γ-(triethoxysilicane) propyl] four is then removed Sulfide alcohol dispersion liquid solution, 45 DEG C of modified meerschaum powder obtained by drying.
Further, the n-BuLi hexane solution is 1.3M, the quality point of hydrogen peroxide in hydrogenperoxide steam generator Number is 20%, ammonia concn 0.1mol/L, and dilute hydrochloric acid concentration is 0.1mol/L.
Further, the catalyst is RuCl3、H2PtCl6、H2IrCl6。
Further, the mixed oxidization that the rare earth oxide is yttrium oxide and ceria mass ratio is 2:1 ~ 2.75:1 is dilute Soil.
Further, the terpene-phenolic resin be softening point be 65 ~ 71 DEG C, hydroxy radical content be 5.5 ~ 6.3%, bromine number be 175 ~ The terpene-phenolic resin of 180mg/100g resin.
Further, the potassium feldspar is powder head, canescence；Ferric oxide content is less than 1% in the nepheline.
Further, calcium oxide content >=53.5% in the calcite；The calcining zinc oxide be it is powdered, it is slightly yellow It adjusts, content of magnesia >=36.5% in the calcinated talc powder.
Comparative example 1
This comparative example compared with Example 2, weighs in step in raw material, saves modified meerschaum ingredient, method step in addition to this It is rapid all the same.
Comparative example 2
This comparative example compared with Example 2, weighs in step in raw material, saves terpene-phenolic resin ingredient, method and step in addition to this It is all the same.
Comparative example 3
This comparative example compared with Example 2, weighs in step in raw material, saves phenyl dichloro boron component, method step in addition to this It is rapid all the same.
Comparative example 4
This comparative example compared with Example 2, weighs in step in raw material, saves ferrocene ingredient, and method and step in addition to this is equal It is identical.
Comparative example 5
This comparative example compared with Example 2, during precursor preparation ceramics, saves microwave treatment, i.e. removal microwave, removes this Outer method and step is all the same.
Comparative example 6
This comparative example compared with Example 2, weighs in step in raw material, saves rare earth oxide ingredient, method and step in addition to this It is all the same.
Ceramic the performance test results prepared by 1 embodiment and comparative example magnetic ceramics prepolymer presoma of table
Note: anti-microbial property is that 50mm × 50mm (scale error is in 5mm) test piece is intercepted from product exemplary operation face, by GB/ Method as defined in 28116-2011 appendix A is detected；GB/T 3217-2013 magnetic test method for permanent magnetic (hard magnetic) material； GBT6569 fine ceramics bending strength test method；GBT13841 electronic ceramics part surface roughness；GBT16534 fine ceramics Room temperature hardness test method；GBT16535 fine ceramics coefficient of linear thermal expansion test method mandril method；GBT25995 fine ceramics Density and apparent porosity test method；GJB1201.1 solid material high temperature thermal diffusivity test method laser pulse method；ASTM The test method of E1269 differential scanning calorimetric determination specific heat capacity；Chemical-resistant reagent corrosive nature unit is annual corrosion Rate mg/cm2Year, 100 DEG C.
It can be seen that magnetic ceramics magnetism obtained is good, there is good anti-microbial property corrosion resistance and good, intensity is high, and reduces Sintering temperature.
The performance test results of 2 embodiment and comparative example magnetic ceramics polymer precursor of table
With reference to EPA6010C-2007 indutively coupled plasma atomic emission spectrometry (ICP-AES)；Shanghai precision scientific instrument Co., Ltd WRS-2A tests oil site and the test method with reference to described in its specification；IS021068-3:2008 silicon carbide-containing is former The chemical analysis of material and refractory product；
As it can be seen that the application has synthesized boracic by ferrocene etc., the presoma of silicon drives body, heat resistance is good, and molecular weight is high.

Claims (9)

1. a kind of preparation method of magnetism anti-bacteria ceramic polymer precursor, which comprises the steps of: one, in nitrogen Under gas shielded and stirring, n-BuLi hexane solution is added drop-wise in the evenly dispersed n-hexane for having ferrocene, is then added Tetramethylethylenediamine, mixture are stirred to react, 10 ~ 12h, are filtered under oxygen-free atmosphere, are washed with n-hexane, and revolving removes n-hexane Solvent is dried in vacuo to obtain ferrocene complex compound；Two, under nitrogen protection, then by ferrocene complex compound, in -5 ~ 0 DEG C of ice-water bath Dimethyldichlorosilane, phenyl dichloro boron are added while uniform stirring, then is started that diformazan is added dropwise to 80 ~ 90 DEG C with oil bath heating 0.5 ~ lh of amine is dripped off, and 105 ~ 110 DEG C are warming up to after 1 ~ 2h of insulation reaction, and reaction to system pH is 6.7 ~ 7.5, is cooled to 60 ~ 70 DEG C, styrene, polyethylene glycol are added, and drop evenly catalyst, is warming up to 100 ~ 110 DEG C and is stirred to react 1 ~ 2h and uniformly drip again Add dipropyl silicon diol, is stirred to react 1 ~ 2h to get the modified poly- boron silane pre-polymer of ferrocene；Three, using collosol and gel legal system Standby evenly dispersed silica template microballoon specially mixes ethyl orthosilicate, dehydrated alcohol, formamide, water, with dilute salt Acid makes adjustments agent and adjusts pH3 ~ 4, then 60 DEG C of heated at constant temperature 1 ~ 2h of reflux adjust pH6 ~ 7 with ammonium hydroxide and obtain template microsphere, then use Soaked in absolute ethyl alcohol silica template 1 ~ 3h of microballoon is placed into ethyl orthosilicate after being aged 1 ~ 2h and is filtered, obtains in step 2 The modified poly- boron silane pre-polymer of the ferrocene arrived carries out the modified 1 ~ 2h in surface, i.e., silica mould after being aged to product after ageing Plate microballoon is distributed in the modified poly- boron silane pre-polymer of ferrocene, is added acetone, is stirred by ultrasonic and is uniformly mixed 30 ~ 40min, so Hydrogenperoxide steam generator is added slowly in above-mentioned mixed solution afterwards, 30 ~ 40min of magnetic agitation keeps mixed liquor evenly dispersed, then In the stainless steel reaction under high pressure gold that mixed liquor is gone to, sustained response 20 ~ for 24 hours is kept the temperature after being heated to 180 ~ 200 DEG C, reaction terminates Room temperature is naturally rung to later, sediment hydrofluoric acid, acetone are cleaned multiple times, Magnetic Isolation, finally obtains black magnetic product simultaneously After 350 ~ 400 DEG C of nitrogen atmospheres are dry in vacuum tube furnace, grey black magnetic product is obtained；Four, grey black magnetic product is existed It grinds, is mixed with appropriate abrasive media dehydrated alcohol and zirconium oxide balls, 1 ~ 2h of ball milling in Subcommittee-to alms bowl, revolving speed per minute 600 ~ 800 turns, rear drying, sieving are mixed with terpene-phenolic resin, are carried out using product of the add in-place piezoresistance heating metal die to black Thermoforming, forming method are to take that powder filling hot pressing die need to be formed, and pressurize 100 ~ 200MPa when being warming up to 200 ~ 340 DEG C, protects Warm 10 ~ 30min of pressure maintaining, cooling release demoulding are chosen fine and close flawless molding blank and are put into Si-Mo rod high temperature furnace, in nitrogen gas 700 ~ 900 DEG C of heating rates, 10 DEG C/min is warming up to certain heating rate in atmosphere, 700 ~ 900 DEG C of 5 ~ 35min are pyrolyzed, heat preservation 1 ~ 1.5h is to get a kind of, magnetism anti-bacteria ceramic polymer precursor, the raw material proportioning are as follows: 30 ~ 40 parts of ferrocene, n-hexane 100 ~ 200 parts, 150 ~ 160 parts of n-BuLi hexane solution, 2 ~ 5 parts of tetramethylethylenediamine, 10 ~ 15 parts of ethyl orthosilicate, anhydrous second 20 ~ 30 parts of alcohol, 0.5 ~ 2.3 part of formamide, 0.2 ~ 0.5 part of polyethylene glycol, 0.2 ~ 0.3 part of catalyst, 10 ~ 22 parts of styrene, third 20 ~ 34 parts of ketone, 15 ~ 36 parts of hydrogenperoxide steam generator, 0.2 ~ 0.5 part of terpene-phenolic resin.
2. a kind of magnetic anti-bacteria ceramic polymer precursor application method according to claim 1, which is characterized in that including Following steps: (1) by 17 ~ 23 parts of magnetic anti-bacteria ceramic polymer precursor, 3.9 ~ 4.2 parts of calcite, 2.6 ~ 3.0 parts of nepheline, 2.8 ~ 5.0 parts of calcinated talc powder, 2.6 ~ 4.8 parts of calcining zinc oxide, calcining 3.3 ~ 5.0 parts of spodumene, 2.5 ~ 3.8 parts of kaolin, 1.2 ~ 2.3 parts of barium monoxide, 1.1 ~ 3.3 parts of boron oxide, 2.5 ~ 3.0 parts of rare earth oxide, 1.2 ~ 1.8 parts of basalt fibre, modified sea 3 ~ 10 parts of afrodite, 2.2 ~ 4.8 parts of zirconium silicate weigh, and by the potassium feldspar, calcite, nepheline, calcinated talc powder, calcined oxide Zinc, calcining spodumene, kaolin, barium monoxide and boron oxide, are sufficiently mixed uniformly, obtain mixed material, Xiang Suoshu mixed material Middle addition carboxymethyl cellulose and water are sufficiently mixed uniformly, obtain mixed slurry；The carboxymethyl cellulose accounts for the mixture Expect the 0.1 ~ 0.2% of quality, the amount for adding water accounts for the 20 ~ 25% of the mixed material quality；(2) add in Xiang Suoshu mixed slurry Enter rare earth oxide, be sieved after 1 ~ 1.5h of wet-milling, basalt fibre is added into strained pulp, is sieved after 1 ~ 1.5h of wet-milling, to sieve Modified meerschaum is added in slurry afterwards, is sieved after 1 ~ 1.5h of wet-milling, zirconium silicate, mistake after 1 ~ 1.5h of wet-milling are added into strained pulp Sieve, obtains ceramic mixture；(3) curing process is carried out to ceramic mixture, solidification temperature at 120 ~ 250 DEG C, soaking time 0.5 ~ 10h is re-fed into microwave agglomerating furnace progress, the low-temperature sintering process that sintering temperature is 700 ~ 1050 DEG C, the frequency of low-temperature sintered microwave Rate is 2450 ~ 2600MHz, 400 ~ 1000W of power；Microwave sintering stove heating uses temperature controlling mode, first with 800 ~ 1000W microwave spoke According to 5 ~ 15 minutes, then irradiated 10 ~ 30 minutes using 400 ~ 800W, and in 700 ~ 1050 DEG C of 65 ~ 90min of calcining, according still further to 15 ~ 50 DEG C/min of cooling velocity cools to room temperature, uses the ceramics of precursor preparation after cooling to obtain the final product.
3. a kind of preparation method of magnetic anti-bacteria ceramic polymer precursor according to claim 1, which is characterized in that institute State modified meerschaum powder the preparation method comprises the following steps: be put into double-[γ-(triethoxysilicane) propyl] tetrasulfide ethyl alcohol for sepiolite powder Disperse in liquor, the body of the sepiolite powder and double-[γ-(triethoxysilicane) propyl] tetrasulfide alcohol dispersion liquid solution Product impregnates 1 hour than being 1:12.5, then goes double-[γ-(triethoxysilicane) propyl] tetrasulfide alcohol dispersion liquid molten Liquid, 45 DEG C of modified meerschaum powder obtained by drying.
4. a kind of preparation method of magnetic anti-bacteria ceramic polymer precursor according to claim 1, which is characterized in that institute Stating n-BuLi hexane solution is 1.3 ~ 1.6M, and the mass fraction of hydrogen peroxide is 20% ~ 35% in hydrogenperoxide steam generator, ammonium hydroxide Concentration is 0.1 ~ 1.5mol/L, and dilute hydrochloric acid concentration is 0.1 ~ 1mol/L.
5. a kind of preparation method of magnetic anti-bacteria ceramic polymer precursor according to claim 1, which is characterized in that institute Stating catalyst is RuCl3、H2PtCl6、H2IrCl6。
6. a kind of magnetic anti-bacteria ceramic polymer precursor application method according to claim 2, which is characterized in that described The mixed rare earth oxide that rare earth oxide is yttrium oxide and ceria mass ratio is 2:1 ~ 2.75:1.
7. a kind of preparation method of magnetic anti-bacteria ceramic polymer precursor according to claim 1, which is characterized in that institute State terpene-phenolic resin be softening point be 65 ~ 71 DEG C, hydroxy radical content is terpene phenol that 5.5 ~ 6.3%, bromine number is 175 ~ 180mg/100g resin Resin.
8. a kind of magnetic anti-bacteria ceramic polymer precursor application method according to claim 2, which is characterized in that described Potassium feldspar is powder head, canescence；Ferric oxide content is less than 1% in the nepheline.
9. a kind of magnetic anti-bacteria ceramic polymer precursor application method according to claim 2, which is characterized in that described Calcium oxide content >=53.5% in calcite；The calcining zinc oxide is powdered, slightly yellow to adjust, oxygen in the calcinated talc powder Change content of magnesium >=36.5%.
CN201910449712.4A 2019-05-28 2019-05-28 A kind of preparation method and application method of magnetism anti-bacteria ceramic polymer precursor Withdrawn CN110317072A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112768633A (en) * 2021-01-26 2021-05-07 蒋央芳 Preparation method of silicon-carbon cathode
CN115246745A (en) * 2022-07-14 2022-10-28 航天特种材料及工艺技术研究所 High-temperature-resistant composite component aerogel material and preparation method thereof
CN117030043A (en) * 2023-08-08 2023-11-10 岭南师范学院 Curved polymer precursor ceramic film temperature sensor and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112768633A (en) * 2021-01-26 2021-05-07 蒋央芳 Preparation method of silicon-carbon cathode
CN115246745A (en) * 2022-07-14 2022-10-28 航天特种材料及工艺技术研究所 High-temperature-resistant composite component aerogel material and preparation method thereof
CN115246745B (en) * 2022-07-14 2023-04-11 航天特种材料及工艺技术研究所 High-temperature-resistant composite component aerogel material and preparation method thereof
CN117030043A (en) * 2023-08-08 2023-11-10 岭南师范学院 Curved polymer precursor ceramic film temperature sensor and preparation method thereof
CN117030043B (en) * 2023-08-08 2024-03-19 岭南师范学院 Curved polymer precursor ceramic film temperature sensor and preparation method thereof

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