CN106699143B - A kind of nucleocapsid ceramic microsphere and preparation method thereof - Google Patents
A kind of nucleocapsid ceramic microsphere and preparation method thereof Download PDFInfo
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Abstract
The present invention discloses a kind of nucleocapsid ceramic microsphere and preparation method thereof, belongs to ceramic microsphere technical field, combines method using emulsion technology and precursor pyrolysis and hot pressing and prepared.Surface is carried out to silica with silane coupling agent first to be modified, it, will modified SiO using emulsion method2It is dispersed in aqueous phase system, oily phase ceramics precursor polysilazane is added dropwise, ultrasonic disperse obtains uniform lotion, and hydro-thermal reaction obtains SiO in autoclave2/ PSN microballoon.Microballoon is sintered in vacuum drying oven again, polysilazane forms SiCN ceramics through Pintsch process, obtains SiO2/ SiCN nucleocapsid ceramic microsphere.Preparation process of the present invention is simple, has excellent performance, and coats one layer of non-oxide SiCN shell on silicon dioxide microsphere surface, the high temperature insulating performance of titanium dioxide silicon substrate core-shell structure microballoon can be improved.
Description
Technical field
The invention belongs to ceramic microsphere technical fields, more particularly to a kind of SiO2/ SiCN nucleocapsid ceramic microsphere and its system
Preparation Method.
Background technique
Silica has the characteristics that low purity is high, density, large specific surface area, dispersion performance are good and superior hot steady
Qualitative, chemical inertness and optics and mechanical performance are widely used in ceramics, rubber, plastics, coating, catalyst carrier and heat-insulated
Equal fields.But as high temperature insulating material, under the conditions of temperature is more than 800 DEG C, SiO2Particle is infrared to 0.75~8 mu m waveband
Heat radiation be almost it is transparent, make it difficult to prevent this heat transfer mode of heat radiation, limit answering in its hot environment
With.
To improve its high temperature insulating performance, in recent years, titanium dioxide silicon substrate Core-shell structure material is constantly developed.But
It is that it is with ZrO that research is mostly at present2And TiO2Equal oxides coated Si O2Based on, using precursor pyrolysis and hot pressing in SiO2Surface cladding
Non-oxide ceramics, the research for forming core-shell structure ceramic microsphere but have not been reported.Compared with oxide ceramics, silicon substrate is non-oxide
Object ceramics have the performances such as excellent high-temperature stability, creep resistant, counter infrared ray radiation, using it as core-shell structure microballoon shell,
The high temperature insulating performance of titanium dioxide silicon substrate core-shell structure microballoon is improved, so as to make core-shell particles stable application in all kinds of superelevation
In warm environment.
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide a kind of SiO2/SiCN nucleocapsid ceramic microsphere and its
Preparation method.It is combined using emulsion method with ceramic precursor conversion method, surface is carried out to silica with silane coupling agent and is changed
Property, one layer of non-oxidized substance SiCN shell is deposited on the surface SiO2 and obtains core-shell structure ceramic microsphere, and titanium dioxide silicon substrate core can be improved
The radiation resistance of shell structure microballoon in the high temperature environment.
The technical purpose of the present invention certainly is achieved by following technical proposals:
A kind of nucleocapsid ceramic microsphere and preparation method thereof, it is equal using the inorganic matter that SiCN is formed as shell using silica as core
The even surface for being coated on the silicon dioxide microsphere as core is carried out as steps described below with forming the ceramic microsphere of core-shell structure
Preparation:
Step 1, silicon dioxide microsphere surface is modified using silane coupling agent, silica is dispersed in nothing
In water-ethanol, silane coupling agent is added thereto, is reacted 20-24 hours under 40-50 degrees Celsius of water-bath, silane coupling agent
It is 1:1 with the mass ratio of silicon dioxide microsphere, the mass ratio of silane coupling agent and dehydrated alcohol is 1:(10-20)；
In the step 1, dispersed using ultrasound, and silane coupling agent is added under ultrasonic disperse state and carries out two
The surface of silicon oxide microsphere is modified；After the completion of reaction, it carries out eccentric cleaning and places into 50 DEG C of drying box drying.
In the step 1, the silicon dioxide microsphere diameter used is at 1-5 microns.
In the step 1, the silane coupling agent is 3- (methacryloxypropyl) propyl trimethoxy silicane (MPS).
In the step 1, the mass ratio of the silane coupling agent and dehydrated alcohol is 1:(12-15).
Step 2, the silicon dioxide microsphere modified using ceramic precursor clad surface, by step 1 surface modified two
Silicon oxide microsphere ultrasonic disperse is in the aqueous phase system that emulsifier and mixed solvent form and is uniformly dispersed, and disperses in continual ultrasonic
In the case where, ceramic precursor is added drop-wise in above-mentioned aqueous phase system to obtain lotion, then by lotion at 150-250 degrees Celsius
Lower carry out crosslinking curing, crosslinking curing time are 3-6 hours, obtain the core-shell particles of ceramic precursor coated silica；?
After crosslinking curing, core-shell particles are filtered and are cleaned and dried by selection；
The mixed solvent is made of the deionized water and acetonitrile of volume ratio 1:1, and the emulsifier is alkyl phenol polyoxy second
Alkene ether (OP-10), molecular formula C8H17C6H4O(CH2CH2O)10H, the ceramic precursor are polymer poly silazane (PSN),
Molecular formula is [- (H) Si (CH3)NH-]x-[(CH3) Si (CH=CH2)NH-]y-[NHSi(CH3)2] z-, molal weight is
500g/mol, molecular structural formula is as follows, and polysilazane is linear structure.
In the step 2, emulsifier quality is 5%-the 10% of ceramic setter weight；Mixed solvent and ceramics are first
The mass ratio for driving body is (10-20): 1, preferably (12-15): 1；The modified silicon dioxide microsphere in step 1 surface and ceramics are first
The mass ratio for driving body is 0.5:(1-5), preferably 0.5:(1-2).
In the step 2, lotion carries out crosslinking curing under 180-240 degrees Celsius, and the crosslinking curing time is 4-6 small
When.
In the step 2, ceramic precursor is added drop-wise in aqueous phase system, rate of addition is per minute 0.01-
0.05ml。
Step 3, nucleocapsid ceramic microsphere is prepared, the core-shell particles for the ceramic precursor coated silica that step 2 is obtained
It is sintered so that ceramic precursor is converted into ceramics (i.e. SiC and the Si being made of silicon carbide and silicon nitride3N4, SiCN pottery
Porcelain), it is sintered in vacuum furnace chamber and is warming up to 2-5 degrees Celsius per minute of speed since 20-25 degrees Celsius of room temperature
Then 20-25 degrees Celsius of room temperature are cooled to the furnace and can be obtained by silicon carbide for 1000-1600 degrees Celsius and heat preservation 1-5 hours
With the nucleocapsid ceramic microsphere of the ceramic coatings silica of silicon nitride composition；
In the step 3, the air atmosphere of an atmospheric pressure is selected to be sintered or vacuum item in vacuum furnace chamber
Part (i.e. 10-3—10-5Atmospheric pressure) it is sintered.
In the step 3,2-4 hours are kept the temperature under 1200-1400 degrees Celsius.
Morphology characterization is carried out to ceramic microsphere using surface sweeping Electronic Speculum and transmission electron microscope, nucleocapsid is presented in ceramic microsphere of the invention
Structure is evenly coated at by shell of the inorganic matter that SiCN is formed that is, using silica as core as the silicon dioxide microsphere of core
Surface.Using 380 type Fourier infrared spectrograph (FTIR) of Thermo company, U.S. Nicolet to the chemical structure of sample into
Row analysis.Fig. 3 is for silica and through the modified silica dioxide granule infrared spectrum of silane coupling agent MPS.It can be with from figure
Find out, in pure SiO2In infrared spectrum, it is located at 958cm-1It is the characteristic peak of Si-OH, 1117cm-1And 810cm-1Place is Si-O-Si
The characteristic peak of key.SiO after modified2In infrared spectrum, in 2960cm-1Nearby there is the methyl of MPS, the feature of methylene
Peak, 1720cm-1And 1638cm-1There is the stretching vibration peak of C=O and C=C respectively in place.Compared to pure SiO2, modified to be located at
958cm-1The Si-OH absorption peak at place obviously weakens, and-OH the content of silica surface reduces, this is because SiO2With silane idol
Connection agent occurs condensation reaction and has consumed part of hydroxyl.Fig. 4 is SiO2The FT-IR spectrogram of/PSN microballoon.With silane coupling agent MPS
Modified SiO2Infrared spectrum (MPS-SiO in figure2) compare, SiO2/ PSN core-shell particles (SiO2@PSN) FT-IR spectrogram in
There is the characteristic peak of PSN: 3400cm-1The N-H stretching vibration peak at place, 3047cm-1Locate unsaturation C-H (- CH=CH2) flexible vibration
Dynamic peak, 2960cm-1And 2894cm-1The saturation C-H stretching vibration peak at place, 1406cm-1And 1600cm-1The C=C stretching vibration at place
Peak, 1260cm-1Locate Si-CH3Vibration peak and 904cm-1Place belongs to the stretching vibration of Si-N-Si.Meanwhile SiO2/ PSN nucleocapsid
In the FT-IR spectrogram of microballoon, in 1720cm-1Place belongs to the C=O and 1638cm of MPS-1The stretching vibration peak of C=C disappears out.
Illustrate PSN by with modified SiO2The C=C on surface occurs addition reaction and is bonded in SiO2Surface forms SiO2/ PSN nucleocapsid is micro-
Ball.
Using Rigaku company D/max-2500 type X-ray diffractometer (XRD) measurement pyrolysis product object phase, Cu target,
10-80 ° of measurement angle range, as shown in attached drawing 5-7.When starting, when such as 1200 DEG C, XRD spectra only occurs at 2 θ=23 °
One broad peak, belongs to unformed SiO2Characteristic peak, show after microballoon pyrolysis that thermal decomposition product is amorphous Si O in amorphous state2/
SiCN nucleocapsid ceramic microsphere.SiO when pyrolysis temperature is 1300 DEG C, at 2 θ=22.79 °2Characteristic peak is sharpened, SiO2By nothing
Sizing state is changed into crystalline state；When calcinations and sintering is increased to 1400 DEG C, XRD spectra 2 θ=35.82 °, 60.23 ° and
There is β-SiC diffraction maximum in 71.98 ° of positions, Si occur in 2 θ=26.5 ° positions3N4Peak crystallization occurs in 2 θ=22.79 °
SiO2Diffraction maximum.1400 DEG C of thermal decomposition products of microballoon crystallize, and generate SiO2, SiC and Si3N4Crystal phase.In sintering of the invention
In temperature range, the PSN ceramic precursor layer on silicon dioxide microsphere surface is crystallized, and generates SiC and Si3N4Crystal phase.In dioxy
The inorganic matter being made of SiCN that SiClx surface is formed is SiCN amorphous inorganic object with calcinations and sintering temperature change, and with forging
There is SiC and Si in the rising for burning sintering temperature3N4When crystal phase, i.e. calcinations and sintering temperature are lower than 1400 DEG C, in silicon dioxide microsphere table
What face was formed is SiCN amorphous inorganic object, when calcinations and sintering temperature is more than or equal to 1400 DEG C, on silicon dioxide microsphere surface
There is SiC and Si in the SiCN inorganic matter of formation3N4Crystal phase, i.e. SiCN amorphous inorganic object crystallize.
Using the infrared of 380 FT-IR Fourier infrared spectrograph device test sample of Thermo company, U.S. Nicolet
Rate is crossed, according to obtained infrared transmittivity as a result, effective extinction coefficient (e*) is calculated using extinction coefficient formula, is effectively disappeared
Spectrum numerical value is bigger, and sample is stronger to the screening capacity of infra-red radiation.The related derivation formula of effective extinction coefficient (e*) is as follows:Wherein, I is to project infrared luminous intensity, I0For directs luminous intensity, for print thickness in test, ρ
For test sample density (J.P.Feng, D.P.Chen, W.Ni, S.Q.Yang, Z.J.Hu, Study of IR absorption
properties of fumed silica-opacifier composites,Journal of Non-Crystalline
Solids 356(2010)480-483)。
Effective extinction coefficient (e*) of the simple silica sample within the scope of 2.5-7 mu m waveband is 2.9-9.7m2/
Kg illustrates that nano-silicon dioxide particle can be passed freely through in 2.5-7 mu m waveband radiant heat flux, substantially rises not to infra-red radiation
To effect.Using the core-shell particles of technical solution of the present invention, due to forming the shell knot of SiCN on the surface of silicon dioxide microsphere
Structure, the effective extinction coefficient (e*) within the scope of 2.5-7 mu m waveband are average up to 16-20m2/ kg, along with the growth of crystal form
So that effective extinction coefficient (e*) is average up to 25-30m2/kg。
Compared with prior art, core-shell structure ceramic microsphere of the present invention is that have superior heat steady using silica as core
Qualitative, chemical inertness and optics and mechanical performance, and silica source is extensive, it is cheap.Compared with oxide ceramics, silicon
Base non-oxide ceramics have the performances such as excellent high-temperature stability, creep resistant, counter infrared ray radiation, core-shell structure ceramics of the present invention
The high temperature counter infrared ray radiativity of titanium dioxide silicon substrate core-shell structure microballoon can be improved using non-oxidized substance SiCN as shell in microballoon
Energy.Obtained core-shell structure ceramic microsphere regular shape, rough surface.Preparation process is simple to operation, experiment condition requirement
It is low.
Detailed description of the invention
Fig. 1 is SiO prepared by the present invention2/ SiCN nucleocapsid ceramic microsphere scanning electron microscope (SEM) photo.
Fig. 2 is SiO prepared by the present invention2/ SiCN nucleocapsid ceramic microsphere transmission electron microscope (TEM) photo.
Fig. 3 is the infrared spectrum for the silica that silica and MPS are modified.
Fig. 4 is the modified silica and SiO of MPS2The infared spectrum of/PSN core-shell particles.
Fig. 5 is SiO prepared by the present invention2The XRD spectrum (1) of/SiCN nucleocapsid ceramic microsphere.
Fig. 6 is SiO prepared by the present invention2The XRD spectrum (2) of/SiCN nucleocapsid ceramic microsphere
Fig. 7 is SiO prepared by the present invention2The XRD spectrum (3) of/SiCN nucleocapsid ceramic microsphere.
Specific embodiment
Technical solution of the present invention is further illustrated combined with specific embodiments below.Emulsifier op-10 alkyl phenol polyoxy second
Alkene ether, chemistry is pure, is purchased from the chemical inc Tianjin Bo Di；Preceramic Polymers polysilazane (PSN), molecular formula
For [- (H) Si (CH3)NH-]x-[(CH3) Si (CH=CH2)NH-]y-[NHSi(CH3)2] z-, molal weight is 500g/mol.
Embodiment 1
Silica 0.5g and dehydrated alcohol 5mL is added in there-necked flask, is put into the abundant ultrasonic disperse 15min of Ultrasound Instrument.
Silane coupling agent MPS 0.5mL is added, is reacted for 24 hours at 40 DEG C of water-bath.Centrifuge washing, drying.By modified silica
Be dispersed in containing emulsifier op-10 0.1g and deionized water 7.5g, acetonitrile 7.5g aqueous phase system in, 1g polysilazane is added dropwise
Into above-mentioned aqueous phase system, rate of addition is 0.01ml per minute, and ultrasonic disperse obtains uniform lotion, 160 DEG C in autoclave
Crosslinking curing 4h after reacting three times by its centrifuge washing after drying at 80 DEG C, is placed it in vacuum drying oven and is sintered,
1000 degrees Celsius are warming up to 5 degrees Celsius of speed per minute since 20 degrees Celsius of room temperature and to keep the temperature 5 hours then cold with furnace
But to 20 degrees Celsius of room temperature.
Embodiment 2
Silica 0.5g and dehydrated alcohol 5mL is added in there-necked flask, is put into the abundant ultrasonic disperse 15min of Ultrasound Instrument.
Silane coupling agent MPS 0.5mL is added, is reacted for 24 hours at 40 DEG C of water-bath.Centrifuge washing, drying.By modified silica
Be dispersed in containing emulsifier op-10 0.2g and deionized water 15g, acetonitrile 15g aqueous phase system in, 2g polysilazane is added drop-wise to
In above-mentioned aqueous phase system, rate of addition is 0.05ml per minute, and ultrasonic disperse obtains uniform lotion, 200 DEG C of friendships in autoclave
Connection solidification 4h after reacting three times by its centrifuge washing after drying at 80 DEG C, is placed it in vacuum drying oven and is sintered, from
25 degrees Celsius of room temperature are started to be warming up to 1600 degrees Celsius with 2 degrees Celsius of speed per minute and keep the temperature 1 hour and then furnace cooling
To 25 degrees Celsius of room temperature.
Embodiment 3
Silica 0.5g and dehydrated alcohol 5mL is added in there-necked flask, is put into the abundant ultrasonic disperse 15min of Ultrasound Instrument.
Silane coupling agent MPS 0.5mL is added, is reacted for 24 hours at 40 DEG C of water-bath.Centrifuge washing, drying.By modified silica
Be dispersed in containing emulsifier op-10 0.2g and deionized water 15g, acetonitrile 15g aqueous phase system in, 2g polysilazane is added dropwise
Into above-mentioned aqueous phase system, rate of addition is 0.03ml per minute, and ultrasonic disperse obtains uniform lotion, 200 DEG C in autoclave
Crosslinking curing 6h after reacting three times by its centrifuge washing after drying at 80 DEG C, is placed it in vacuum drying oven and is sintered,
1200 degrees Celsius are warming up to 4 degrees Celsius of speed per minute since 20 degrees Celsius of room temperature and to keep the temperature 3 hours then cold with furnace
But to 25 degrees Celsius of room temperature
Embodiment 4
Silica 0.5g and dehydrated alcohol 5mL is added in there-necked flask, is put into the abundant ultrasonic disperse 15min of Ultrasound Instrument.
Silane coupling agent MPS0.5mL is added, is reacted for 24 hours at 40 DEG C of water-bath.Centrifuge washing, drying.By modified silica point
Be dispersed in containing emulsifier op-10 0.3g and deionized water 22.5g, acetonitrile 22.5g aqueous phase system in, 1g polysilazane is dripped
It is added in above-mentioned aqueous phase system, rate of addition is 0.04ml per minute, and ultrasonic disperse obtains uniform lotion, 240 in autoclave
DEG C crosslinking curing 4h after reacting three times by its centrifuge washing after drying at 80 DEG C, is placed it in vacuum drying oven and is burnt
Knot is started to be warming up to 1400 degrees Celsius with 3 degrees Celsius of speed per minute since 25 degrees Celsius of room temperature and keeps the temperature 2 hours and then with furnace
It is cooled to room temperature 20 degrees Celsius.
Ceramic microsphere of the invention can be prepared by being adjusted according to the preparation technology parameter that summary of the invention is recorded, and be showed
Essentially identical property out forms the ceramic surface of silicon carbide and silicon nitride on the surface of silicon dioxide microsphere, in 2.5-7 μm of wave
Effective extinction coefficient (e*) in segment limit is average up to 25-30m2/ kg, ceramic microsphere of the invention are being built as filler
Application in material, effective lift pins promote the thermal insulation of construction material to the effective extinction coefficient within the scope of 2.5-7 mu m waveband
Energy.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (10)
1. a kind of nucleocapsid ceramic microsphere, which is characterized in that using silica as core, uniformly wrapped by shell of the inorganic matter that SiCN is formed
The surface of the silicon dioxide microsphere as core is overlayed on, to form the ceramic microsphere of core-shell structure, is prepared as steps described below:
Step 1, silicon dioxide microsphere surface is modified using silane coupling agent, silica is dispersed in anhydrous second
In alcohol, silane coupling agent is added thereto, is reacted 20-24 hours under 40-50 degrees Celsius of water-bath, silane coupling agent and dioxy
The mass ratio of SiClx microballoon is 1:1, and the mass ratio of silane coupling agent and dehydrated alcohol is 1:(10-20)；The silane coupling agent
For 3- (methacryloxypropyl) propyl trimethoxy silicane；
Step 2, the silicon dioxide microsphere modified using ceramic precursor clad surface, by the modified titanium dioxide in step 1 surface
Silicon microballoon ultrasonic disperse is in the aqueous phase system that emulsifier and mixed solvent form and is uniformly dispersed, in the feelings of continual ultrasonic dispersion
Under condition, ceramic precursor is added drop-wise in above-mentioned aqueous phase system to obtain lotion, then by lotion under 150-250 degrees Celsius into
Row crosslinking curing, crosslinking curing time are 3-6 hours, obtain the core-shell particles of ceramic precursor coated silica；It is described mixed
Bonding solvent is made of the deionized water and acetonitrile of volume ratio 1:1, and the emulsifier is alkyl phenol polyoxyethylene ether, and the ceramics are first
Drive body is polymer poly silazane, and molal weight is 500g/mol；In the step 2, emulsifier quality is ceramic precursor
5%-the 10% of quality；The mass ratio of mixed solvent and ceramic precursor is (10-20): 1；Step 1 surface modified two
The mass ratio of silicon oxide microsphere and ceramic precursor is 0.5:(1-5)；
Step 3, nucleocapsid ceramic microsphere is prepared, the core-shell particles for the ceramic precursor coated silica that step 2 is obtained carry out
Be sintered so that ceramic precursor is converted into SiCN ceramics, be sintered in vacuum furnace chamber since 20-25 degrees Celsius of room temperature with
2-5 degrees Celsius per minute of speed is warming up to 1000-1600 degrees Celsius and keeps the temperature 1-5 hours and then cool to room temperature with the furnace
20-25 degrees Celsius of nucleocapsid ceramic microspheres that can be obtained the ceramic coatings silica being made of silicon carbide and silicon nitride.
2. a kind of nucleocapsid ceramic microsphere according to claim 1, which is characterized in that in step 2, mixed solvent and ceramics
The mass ratio of precursor is (12-15): 1；The mass ratio of step 1 surface modified silicon dioxide microsphere and ceramic precursor
For 0.5:(1-2).
3. a kind of nucleocapsid ceramic microsphere according to claim 1, which is characterized in that in the step 1, the dioxy that uses
SiClx microsphere diameter is at 1-5 microns；Dispersed using ultrasound, and silane coupling agent is added under ultrasonic disperse state and carries out two
The surface of silicon oxide microsphere is modified；After the completion of reaction, it carries out eccentric cleaning and places into 50 DEG C of drying box drying；In the step
In 1, the mass ratio of the silane coupling agent and dehydrated alcohol is 1:(12-15).
4. a kind of nucleocapsid ceramic microsphere according to claim 1, which is characterized in that in the step 2, by ceramic setter
Body is added drop-wise in aqueous phase system, and rate of addition is 0.01-0.05ml per minute；In the step 2, lotion is 180-240
Crosslinking curing is carried out under degree Celsius, the crosslinking curing time is 4-6 hours.
5. a kind of nucleocapsid ceramic microsphere according to claim 1, which is characterized in that in the step 3, in vacuum furnace chamber
The air atmosphere of one atmospheric pressure of middle selection is sintered or vacuum condition is sintered；In the step 3,
2-4 hours are kept the temperature under 1200-1400 degrees Celsius.
6. a kind of preparation method of nucleocapsid ceramic microsphere, which is characterized in that prepared as steps described below:
Step 1, silicon dioxide microsphere surface is modified using silane coupling agent, silica is dispersed in anhydrous second
In alcohol, silane coupling agent is added thereto, is reacted 20-24 hours under 40-50 degrees Celsius of water-bath, silane coupling agent and dioxy
The mass ratio of SiClx microballoon is 1:1, and the mass ratio of silane coupling agent and dehydrated alcohol is 1:(10-20)；The silane coupling agent
For 3- (methacryloxypropyl) propyl trimethoxy silicane；
Step 2, the silicon dioxide microsphere modified using ceramic precursor clad surface, by the modified titanium dioxide in step 1 surface
Silicon microballoon ultrasonic disperse is in the aqueous phase system that emulsifier and mixed solvent form and is uniformly dispersed, in the feelings of continual ultrasonic dispersion
Under condition, ceramic precursor is added drop-wise in above-mentioned aqueous phase system to obtain lotion, then by lotion under 150-250 degrees Celsius into
Row crosslinking curing, crosslinking curing time are 3-6 hours, obtain the core-shell particles of ceramic precursor coated silica；It is described mixed
Bonding solvent is made of the deionized water and acetonitrile of volume ratio 1:1, and the emulsifier is alkyl phenol polyoxyethylene ether, and the ceramics are first
Drive body is polymer poly silazane, and molal weight is 500g/mol；In the step 2, emulsifier quality is ceramic precursor
5%-the 10% of quality；The mass ratio of mixed solvent and ceramic precursor is (10-20): 1；Step 1 surface modified two
The mass ratio of silicon oxide microsphere and ceramic precursor is 0.5:(1-5)；
Step 3, nucleocapsid ceramic microsphere is prepared, the core-shell particles for the ceramic precursor coated silica that step 2 is obtained carry out
Be sintered so that ceramic precursor is converted into SiCN ceramics, be sintered in vacuum furnace chamber since 20-25 degrees Celsius of room temperature with
2-5 degrees Celsius per minute of speed is warming up to 1000-1600 degrees Celsius and keeps the temperature 1-5 hours and then cool to room temperature with the furnace
20-25 degrees Celsius of nucleocapsid ceramic microspheres that can be obtained the ceramic coatings silica being made of silicon carbide and silicon nitride.
7. a kind of preparation method of nucleocapsid ceramic microsphere according to claim 6, which is characterized in that in the step 1,
The silicon dioxide microsphere diameter used is at 1-5 microns；Dispersed using ultrasound, and silane idol is added under ultrasonic disperse state
The surface for joining agent progress silicon dioxide microsphere is modified；After the completion of reaction, it carries out eccentric cleaning and places into 50 DEG C of drying box drying.
8. a kind of preparation method of nucleocapsid ceramic microsphere according to claim 6, which is characterized in that in the step 1,
The mass ratio of the silane coupling agent and dehydrated alcohol is 1:(12-15).
9. a kind of preparation method of nucleocapsid ceramic microsphere according to claim 6, which is characterized in that in the step 2,
Ceramic precursor is added drop-wise in aqueous phase system, rate of addition is 0.01-0.05ml per minute；Lotion is Celsius 180-240
Degree is lower to carry out crosslinking curing, and the crosslinking curing time is 4-6 hours；The mass ratio of mixed solvent and ceramic precursor is (12-
15): 1；The mass ratio of the modified silicon dioxide microsphere in step 1 surface and ceramic precursor is 0.5:(1-2).
10. a kind of preparation method of nucleocapsid ceramic microsphere according to claim 6, which is characterized in that in the step 3
In, the air atmosphere of one atmospheric pressure of selection is sintered in vacuum furnace chamber or vacuum condition is sintered；In the step
In rapid 3,2-4 hours are kept the temperature under 1200-1400 degrees Celsius.
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| CN103351156B (en) * | 2013-07-05 | 2014-07-16 | 陕西师范大学 | Silicon dioxide-based composite ceramic with near-zero resonance frequency temperature coefficient and preparation method thereof |
| CN105036733B (en) * | 2014-01-17 | 2017-03-01 | 天津城建大学 | Infrared high shielding nucleocapsid structure opacifier and its preparation method and application |
| CN103979965B (en) * | 2014-05-12 | 2016-02-24 | 西北工业大学 | A kind of method preparing Si-C-N based ceramic microsphere |
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