CN110041091A - A kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity - Google Patents
A kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of the heat-insulated microballoon filler of the resistance to ablation of high emissivity, preparation mixing, the preparation of precursor pulp, the preparation of precursor powder, sintering process including powder and etc., the heat-insulated microballoon filler of the resistance to ablation of high emissivity is prepared.Compared with prior art, high production efficiency of the present invention, with short production cycle, equipment is simple, easy to operate, the dusty spray sphericity being prepared is preferable, and there is special pore structure, use the microballoon to have mass ablative rate low as coating prepared by filler, from radiance height, good mechanical property can be effective against 800kW/m2Or more hot-fluid impact, protect matrix not deformed and failed by high temperature erosion.
Description
Technical field
The present invention relates to heat-insulated fields, more particularly, to the preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity.
Background technique
Thermal protection system and thermally protective materials are development and ensure that hypersonic aircraft and Reusable launch vehicles exist
The foundation stone that extreme environment is on active service safely.In order to improve the survival ability of aircraft, " new thermal boundary " problem of thermal protection is broken through, height
Effect thermal protection system and thermally protective materials must improve and resist extreme Service Environment ability, meet the heatproof of aircraft thermal protection system
Property, durability and reliability requirement.In existing thermal protection system, the most mature and heat insulation most preferably heat-insulated system of ablation
System.A variety of objects for absorbing thermal energy such as ablative thermal protection refers in hot-fluid environment, and heat insulation material can decompose, melt, distilling
Physicochemical variation takes away amount of heat by the mass loss consumption of material itself, prevents hot-fluid from being passed to inside configuration to reach
Purpose.But with the development of aerospace flight vehicle, the heat-proof quality and ablation resistance of thermal protection system are proposed more
Big requirement, and traditional ablating heat shield is to sacrifice the effect that the mass loss of heat insulation material exchanges solar heat protection for, for that can weigh
The thermal protection requirement of the space shuttle used again, ablating heat shield are obviously helpless.Therefore a kind of novel resistance to ablation every
Hot filler is just particularly important.
The existing main thinking of repeatable thermal protection system is to brush one layer on the outside of ceramic insulation watt with high-incidence
The coating of rate is penetrated, rigid thermal insulation tile is the thermally protective materials that high-speed aircraft windward side mainly uses, and has porosity height, thermal conductivity
A series of features such as rate is low, and density is low.And outer layer coating is other than having the characteristics that high emissivity, it is also necessary to play waterproof,
Impact resistance, anti-thermal shock effect are to meet the needs of reusing for a long time.Some researches show that when service temperature is (1000 DEG C very high
More than) when, for the transfer mode of heat mainly based on heat radiation, exothermic key lies also in increase radiative thermal protection at this time.Ignore
Disregard the heat flow density of thermal insulation tile surface reflection, can calculate and be transmitted to thermal insulation tile internal structure through coating under hot conditions
In calorie value be about (q- σ ε T4), therefore, the emissivity value ε of increase rate coating can effectively reduce the heat through coating
Amount, to reach heat insulation.
Superhigh temperature ceramics (Ultra-HighTemperatureCeramics, UHTCs) refer in hot environment and reaction
A kind of ceramic material of physics and chemical stability is able to maintain in atmosphere, mainly with the boride of the formation such as Hf, Zr, Mo,
The multiple elements design ceramic material of the transistion metal compounds such as carbide and nitride composition, the fusing point of these compounds is generally all
More than 3000 DEG C, have the characteristics that there is superhigh temperature resistant, high thermal conductivity and high intensity.In addition to this, with HfC and MoSi2For generation
The UHTCs of table have very high radiance, can under the high hot-fluid service condition of superhigh temperature it is as much as possible by heat with hot spoke
Before the form penetrated distributes, and reduces the internal energy preached, therefore it has very high application in repeatable thermal protection field
Scape.But UHTCs is a kind of typical fragile material, is easy to occur under extreme heating environment as a kind of ceramic material
Thermal shock failure, leads to catastrophic failure.Component is shown by the ground and flight test of the crucial hot-end component of UHTCs production
Failure show as mostly thermal shock damage failure, therefore improve UHTCs thermal-shock resistance and damage tolerance it is particularly important.
Summary of the invention
The present invention in order to overcome in above-mentioned UHTCs there are damage tolerance is insufficient and defect, provide it is a kind of prepare high emissivity,
The ceramic microsphere filling method of high damage tolerance and high ablation resistance.This method high production efficiency, with short production cycle, equipment
Simply, easy to operate.The dusty spray sphericity being prepared is preferable, and have special pore structure, use the microballoon as
The coating of filler preparation has mass ablative rate low, and from radiance height, good mechanical property can be effective against 800kW/m2And with
On hot-fluid impact, protect matrix not deformed and failed by high temperature erosion.
The purpose of the present invention can be achieved through the following technical solutions:
A kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity, comprising:
(1) the preparation mixing of powder: using isopropanol or ethyl alcohol as abrasive media, using the method for high-energy ball milling by UHTCs
Constituent element, high emissivity self-healing constituent element and sintering aid are (20~80) in mass ratio: (20~80): (5~10) carry out ball
Mill and mixing, Ball-milling Time are 24~48h, and ball milling speed is 1000~4000r/min, dry obtained slurry after ball milling
It does for 24 hours to constant weight, grinds and be sieved to obtain mixed-powder, the primary particle size of powder should be not more than 200nm after ball milling；
(2) preparation of precursor pulp: being (1~6) by powder obtained in step (1) in mass ratio: (7~12) merging
Be sufficiently stirred and disperse in organic solvent, later be placed in ultrasonic disintegrator in 10~60min of ultrasonic disperse to eliminate nanometer powder
Between physical agglomeration, obtain uniform powder suspension, organic adhesive be added thereto when suspension does not settle and helps
Agent and dispersing agent carry out uniform stirring, mixing time 24 to the mixed liquor by the way of the stirring of oil bath heating comprehensive mechanical
~48h, the revolving speed of stirring rod are 200~700r/min, be added at bottle stopper condensation reflux unit prevent organic solvent volatilize and
Caused by the proportion of precursor pulp change, be cooled to room temperature after being sufficiently stirred spare；
(3) preparation of precursor powder: step (3) obtained slurry is once filtered, filter out it is therein not
Molten impurity carries out slurry before starting to prepare powder to be vacuum-treated the residual air for excluding slurry.Slurry is injected later
Among syringe, syringe is disposed vertically, and is placed below syringe and is filled deionized water (50 of volume greater than slurry total volume
Times) take-up reel, be positive grade with the syringe needle equipped with Vltrasonic device syringe, be cathode application voltage using take-up reel, slurry is in electricity
The droplet of micro-meter scale is separated under acting under the collective effect of field and mechanical wave.After device push to be injected, removal electricity
Field and ultrasound are simultaneously stood, by the solid phase powder sieving in receiving plate and natural air drying, formation precursor powder；
(4) sintering process: by step (3) to precursor powder be laid in crucible, be placed in vacuum tube furnace
Middle carry out high-temperature heat treatment, sieves sintered powder, obtains the heat-insulated microballoon filler of the resistance to ablation of high emissivity high tenacity.
Preferably, UHTC constituent element is Hf (Zr, Ta) C, Hf (Zr, Ta) B in step (1)2、[Hf(Zr,Ta)]3N4、Hf(Zr,
Ta)C-SiC、Hf(Zr,Ta)B2-SiC、[Hf(Zr,Ta)]3N4-SiC、(Zr/Hf/Ta)-Ti-B-C-O、(Zr/Hf/Ta)-Ti-
One kind or combination of the polynary ceramics such as N-C-O, (Zr/Hf/Ta)-Si-B-C-O or (Zr/Hf/Ta)-Si-N-C-O；High emissivity
Self-healing constituent element is platinum black, Si, SiC, SiB4、SiB6、CuO、Si3N4、MoSi2And high emissivity Spinel compound is (such as
MgFe2O4、CuFe2O4、ZnFe2O4、CoFe2O4、NiFe2O4、NiCr2O4、NiAl2O4Deng) one or more of any combination, it burns
Knot auxiliary agent is ZrSi2、TaSi2Etc. transition elements silicide one or more any combination
Preferably, the ratio of grinding media to material in step (1) is 2~5；The mass ratio of abrasive media and material is 1:2~6.
Preferably, the organic solvent in step (2) is n,N-dimethylacetamide, N-Methyl pyrrolidone and dimethyl
Any combination of acetamide one or more, organic binder are polysulfones, poly aromatic amide, polyolefins, poly aromatic chemical combination
Any combination of object one or more, dispersing agent are polyvinylpyrrolidone, polyethylene glycol and octanol it is one or more of
Any combination, dispersing agent additional amount are the 5%~15% of organic solvent quality, organic binder, powder, the quality of organic solvent
Than for (1~2): (2~6): (5~12)；
Preferably, the voltage in step (3) between syringe nozzle and take-up reel is 5~25kV, is surpassed on syringe needle
Frequency of sound wave is 25~100kHz, and syringe nozzle is 6~15cm at a distance from take-up reel, and the fltting speed of syringe is 0.5
~3ml/min will guarantee to insulate, in order to guarantee to starch before syringe starts to promote to all appts surface alcohol wipe
Sufficient mass exchange is carried out between material and water, therefore the time that mixed liquor is stood should be not less than 48h.
Preferably, heat treatment temperature is 1400~1800 DEG C in step (4), and batch-type furnace heating rate is 4~6 DEG C/min,
Cooling rate is 4~6 DEG C/min, and powder thickness should be no more than 10mm in crucible.
This experiment is successfully prepared using the phase conversion method of mechanical wave and electric field-assisted dispersion with special finger-like hole
UHTCs ceramic microsphere, when precursor slurry is entered in water, due to water and organic solvent counterdiffusion act on, it is not soluble in water
Organic binder and ceramic powders inversion of phases mechanism under be frozen into solid powder particle.Sub-micro before entering water, in drop
YSZ particle is random is distributed in PES and NMP organic solution for rice.After entering water, solid phase PES is precipitated, while by submicron order
YSZ particle is bonded together.Since nmp solution is different from the rate of superficial dissolution Yu Shuizhong in drop center portion, presoma drop
Inside forms a series of finger-shaped hole.By sintering processes under the powder metallurgy of EFI, except PES in degranulation etc. is organic
Material obtains the ceramic microsphere of resistance to ablation filler.
The method of be improved material radiance is all so that material system more levels off to ideal black-body model.Classical reason
Think that blackbody model is cavity pin-point model (as shown in Figure 1), when cavity material transmitance be 0 and aperture size it is sufficiently small it
When, it is difficult to project from cavity again into multiple reflections excessively by the light that aperture enters cavity, the radiance of cavity is 1 at this time.
But such aperture cavity is extremely difficult in the actual operation process reaches, but can by improve material own radiation rate and
The complex internal structure of multiple reflections is formed in material internal to increase radiance.There are phases for ceramic microsphere prepared by the present invention
The micron finger-like hole and powder that conversion process is formed stack the other isometric hole of the submicron order to be formed, and have the more of complexity
Layer pore structure, incident electromagnetic wave can pass through multiple reflections inside it, therefore it is with very high absorptivity and emissivity.
Compared with prior art, the present invention carries out structure design using to UHTCs material, is prepared for the specific strength for having high
And the ceramic microsphere of damage tolerance, and the emissivity of material is further increased with Hierarchical porosity gap structure is added, so that it has
There are high emissivity and preferable mechanical performance, has the advantage that
(1) there is complicated multistage pore structure inside ceramic microsphere prepared by the present invention, so that heat radiation electromagnetism wave energy
Enough multiple reflections inside it, in addition to this, powder surface are the spongelike structure of submicron powder accumulation sintering and formation, when
Precursor pulp is into when crossing ultrasonication and electrostatic force and being separated into fine drop and enter in water, due to inside slurry and non-solvent
Concentration gradient is handed over big, it may occur that at this moment quick counterdiffusion process can occur for solvent and non-solvent.Water is entered quickly by surface layer
Inside slurry, hole is formed with exchange of solvent, at this moment counterdiffusion driving force is larger, and the gap of formation has and spread same side
Quick two-phase laminated flow occurs for tropism, precursor pulp surface, forms finger-like pore structure.When diffusion further progress, slurry
The concentration difference of water (NMP) reduces in drop and environment, and driving force weakens, and polymer-poor phase is on polymer-rich phase surface layer at this time
Forming core, and quickly mutually surrounded and separated by the polymer richness of surrounding, form the cell structure of closure.With delaying for diffusion process
Slow-motion row, polymer-poor phase droplet are gradually grown up, some can occur to penetrate through and be merged under the action of surface tension, thus
Surface forms one layer of comparatively dense spongy shell structurre.Sponge pore structure is removed into high temperature sintering, organic matter is crossed, nanometer
Sintering phenomenon occurs between powder, forms comparatively dense sponge shell structurre in outer layer.This is that the microstructure of powder is extra large
Continuous shape shell and the finger-like pore structure at center, submicroscopic structure are the microvoid structure that nanometer powder occurs that sintering is formed,
Therefore there is graded porous structure, compared with traditional ceramic microsphere, specific surface area is bigger, and surface roughness is higher, therefore can
Greatly to promote the emissivity of material.
(2) for ceramic microsphere prepared by the present invention in the state that higher temperature is on active service, ceramic microsphere can keep internal
The integrality of finger-like pore structure, pore scale is smaller, during heat treatment more it is easy gradually aggregation formed macrovoid or from
Surface evolution, the driving force of this process are the diminutions of surface energy.Energy required for finger-like hole generation sinteringization is more, because
This shape structure pore structure integrality that can be kept, to greatly avoid what traditional material hyperthermia radiation rate declined rapidly from showing
As in addition to this thermal structure stability is also beneficial to improve the mechanical behavior under high temperature of microballoon, therefore can be significant as filler
Improve the high temperature emissive rate and ablation resistance of coating.
(3) ablation resistance is good, has flame retardant property.This ceramic microsphere is aided with silicon substrate auxiliary agent, energy using superhigh temperature ceramics
Enough significant high temperature resistants and ablation resistance for improving microballoon, in addition to this, the addition of silicon substrate flame retardant can be in superelevation
The SiO of molten condition is formed under conditions of warm oxidation ablation2, so that material has the performance of self-healing, so that the microballoon filler
Addition can significantly improve the heat resistanceheat resistant vibration of material and ability that violent starting is washed away.
(4) mechanical property is good, and specific strength is high.Compared with the tiny balloon of traditional structure, which has inversion of phases
The finger-like hole and submicron powder of the micro-meter scale of formation stack and the sub-micron porosity of sintering and formation, such classification
Porous structure due to microvoid (crackle) toughening principle enable the ceramic microsphere deform to a greater extent mismatch without
Structure is generated to destroy；In addition to this, mutually divided between hole by radial ceramic wall, when ceramic microsphere is by external force it
When, ceramic wall plays the role of pressure-bearing with very high intensity and specific strength.
(5) preparation process is simple, and operation is simple, particle diameter distribution can by adjust electric field level and mechanical wave frequency rate and
For intensity come the powder good sphericity for controlling, and producing, porosity is high, has very high commercialization value.
Detailed description of the invention
Fig. 1 is ideal black-body model schematic；
Fig. 2 is the ceramic microsphere Cross Section Morphology SEM figure that embodiment 1 is prepared；
Fig. 3 is insulating moulding coating emission spectrum schematic diagram prepared by embodiment 1；
Fig. 4 is the surface microstructure after insulating moulding coating heat flux measurement prepared by embodiment 1.
Specific embodiment
The present invention is described in detail combined with specific embodiments below.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection scope.
Embodiment 1:
The present embodiment is achieved through the following technical solutions above-mentioned performance:
(1) the preparation mixing of powder: using isopropanol or ethyl alcohol as abrasive media, using the method for high-energy ball milling by UHTC group
Member, high emissivity self-healing constituent element and sintering aid are that 50:50:5 carries out ball milling and mixing, Ball-milling Time are in mass ratio
Obtained slurry is dried for 24 hours to constant weight after ball milling, grinds and be sieved and mixed by 36h, ball milling speed 2000r/min
Powder is closed, the primary particle size of powder should be not more than 200nm after ball milling；
(2) preparation of precursor pulp: being in 3:9 merging organic solvent by powder obtained in step (1) in mass ratio
Be sufficiently stirred and disperse, later be placed in ultrasonic disintegrator in ultrasonic disperse 30min to eliminate the physical agglomeration between nanometer powder,
Uniform powder suspension is obtained, organic adhesive auxiliary agent and dispersing agent is added thereto when suspension does not settle, is used
The mode of oil bath heating comprehensive mechanical stirring carries out uniform stirring to the mixed liquor, and the revolving speed of mixing time 48h, stirring rod are
350r/min, be added at the bottle stopper condensation reflux unit prevent organic solvent volatilize and caused by the proportion of precursor pulp occur
Change, is cooled to room temperature after being sufficiently stirred spare；
(3) preparation of precursor powder: step (3) obtained slurry is once filtered, filter out it is therein not
Molten impurity carries out slurry before starting to prepare powder to be vacuum-treated the residual air for excluding slurry.Slurry is injected later
Among syringe, syringe is disposed vertically, and is placed below syringe and is filled deionized water (50 of volume greater than slurry total volume
Times) take-up reel, be positive grade with the syringe needle equipped with Vltrasonic device syringe, be cathode application voltage using take-up reel, slurry is in electricity
The droplet of micro-meter scale is separated under acting under the collective effect of field and mechanical wave.After device push to be injected, removal electricity
Field and ultrasound are simultaneously stood, by the solid phase powder sieving in receiving plate and natural air drying, formation precursor powder；
(4) sintering process: by step (3) to precursor powder be laid in crucible, be placed in vacuum tube furnace
Middle carry out high-temperature heat treatment, sieves sintered powder, obtains the heat-insulated microballoon filler of the resistance to ablation of high emissivity high tenacity.
In above-mentioned preparation process, matrix component is ZrB in step (1)2, silicon source SiB6And MoSi2Mass fraction is 1:1
Combination, sintering aid ZrSi2；
In above-mentioned preparation process, the ratio of grinding media to material in step (1) is 3；The mass ratio of abrasive media and material is 1:3.
In above-mentioned preparation process, the organic solvent in step (2) is N-Methyl pyrrolidone, and organic binder PES divides
Powder is polyvinylpyrrolidone, and dispersing agent additional amount is the 10% of organic solvent quality, organic binder, powder, You Jirong
The mass ratio of agent is 1:3:8；
In above-mentioned preparation process, the voltage in step (3) between syringe nozzle and take-up reel is 5~25kV, syringe
Ultrasonic wave comment is 50kHz on syringe needle, and syringe nozzle is 10cm at a distance from take-up reel, and the fltting speed of syringe is
2.5ml/min will guarantee to insulate, in order to guarantee to starch before syringe starts to promote to all appts surface alcohol wipe
Sufficient mass exchange is carried out between material and water, therefore the time that mixed liquor is stood should be not less than 48h.
In above-mentioned preparation process, heat treatment temperature is 1400 DEG C in step (4), and tube furnace heating rate is 5 DEG C/min, drop
Warm speed is 5 DEG C/min, and powder thickness should be no more than 10mm in crucible.
In the present embodiment, it is that Qingdao Lian Rui precision instrument Co., Ltd produces that high-energy ball milling, which uses,
UNIONPROCESS grinder, model 01-HDDM.
In the present embodiment, ultrasonic cell disruptor is Shanghai reliable industry Development Co., Ltd production only, model JY9Z-
ⅡN
In the present embodiment, high temperature process furnances are the SGL-1400 types of Shanghai Daheng Optical Fine Mechinery Co., Ltd's production
Tube furnace.
In the present embodiment, precise injection pump is that Harvard company in the U.S. produces, model PHDULTRACP.
In the present embodiment, high temperature box furnace is 1700 DEG C of three temperature of Shanghai Ju Jing precision instrument Manufacturing Co., Ltd production
Area's tube furnace, model: SGL-1700- III.
Fig. 2 is the stereoscan photograph of superhigh temperature ceramics microballoon Cross Section Morphology prepared by embodiment 1, and dusty spray is by two
Part forms, and some is center hole area, and the region porosity is larger, up to 40-70%, has special finger-like hole,
The formation of hole is related with counterdiffusion, and one layer of spongy shell is surrounded except finger-like pore region, the region porosity
Only 5%~10%, the formation of hole is related with the removing of organic matter and sintering phenomenon.This outer densification, interior porous knot
Structure has very strong structural stability and specific strength, and classifying porous structure also brings very high strain tolerance and damage to microballoon
Hurt tolerance, as filler, the mechanical property of material can be significantly improved.
Room temperature curing is added into RTV phenyl-containing silicone rubber in the ceramic microsphere and obtains ablative cork coatings.By Wien position
Law and Planck law are moved it is found that in (1800 DEG C or more) military services of superhigh temperature, the heat radiation of object be concentrated mainly on 1 μm~
Between 4 μm, therefore we should pay close attention to the radiance of this section coating.Using UV, visible light near infrared spectrometer (UV-
VIS-NIRspectrophotometer, Lambda950, PerkinElmer) emissivity of the coating 300~2500 is carried out
Characterization is as shown in Figure 3, it can be seen that it is all larger than 0.92 in the emissivity of this wave band, material, it can be effectively by the heat of absorption
Amount distributes, and plays the role of heat radiation screening.
Fig. 4 is surface fiber pattern of the embodiment after superheat flow is impacted, it can be seen that the coating is rushed in superelevation hot-fluid
More complete surface topography is maintained after hitting test, forms one layer of more high-densit oxide layer of hardness on surface, it can be effective
Protect internal base plate not by oxidative attack in ground.Microballoon maintains good knot under the conditions of high heat flux measurement as can be seen from Figure
Looks are configured, and increase the degree of roughness of coating surface, further improve radiance.In addition to this, shape in ablation process
At compact oxidation layer effectively raise the binding force of dope layer in ablation process so that the coating resists external force and vibration
Dynamic ability is stronger；In addition to this radiating layer forms the substance of molten state under service state, and effective Anticrack is filled up
Cracking and defect, enhance the bond strength of coating, there is the good nature of self-healing.Therefore filler is anti-as reusable heat
The high emission filler of resistance to ablation of protecting system has very high application value.
Embodiment 2:
The present invention is achieved through the following technical solutions above-mentioned performance:
(1) the preparation mixing of powder: using isopropanol or ethyl alcohol as abrasive media, using the method for high-energy ball milling by UHTCs
Constituent element, high emissivity self-healing constituent element and sintering aid are that 20:80:10 carries out ball milling and mixing, Ball-milling Time in mass ratio
For for 24 hours, obtained slurry is dried for 24 hours to constant weight after ball milling, grinds and be sieved to obtain by ball milling speed 1000r/min
Mixed-powder, the primary particle size of powder should be not more than 200nm after ball milling；
(2) preparation of precursor pulp: being in 1:7 merging organic solvent by powder obtained in step (1) in mass ratio
Be sufficiently stirred and disperse, later be placed in ultrasonic disintegrator in ultrasonic disperse 10min to eliminate the physical agglomeration between nanometer powder,
Uniform powder suspension is obtained, organic adhesive auxiliary agent and dispersing agent is added thereto when suspension does not settle, is used
The mode of oil bath heating comprehensive mechanical stirring carries out uniform stirring to the mixed liquor, and mixing time is for 24 hours that the revolving speed of stirring rod is
200r/min, be added at the bottle stopper condensation reflux unit prevent organic solvent volatilize and caused by the proportion of precursor pulp occur
Change, is cooled to room temperature after being sufficiently stirred spare；
(3) preparation of precursor powder: step (3) obtained slurry is once filtered, filter out it is therein not
Molten impurity carries out slurry before starting to prepare powder to be vacuum-treated the residual air for excluding slurry.Slurry is injected later
Among syringe, syringe is disposed vertically, and is placed below syringe and is filled deionized water (50 of volume greater than slurry total volume
Times) take-up reel, be positive grade with the syringe needle equipped with Vltrasonic device syringe, be cathode application voltage using take-up reel, slurry is in electricity
The droplet of micro-meter scale is separated under acting under the collective effect of field and mechanical wave.After device push to be injected, removal electricity
Field and ultrasound are simultaneously stood, by the solid phase powder sieving in receiving plate and natural air drying, formation precursor powder；
(4) sintering process: by step (3) to precursor powder be laid in crucible, be placed in vacuum tube furnace
Middle carry out high-temperature heat treatment, sieves sintered powder, obtains the heat-insulated microballoon filler of the resistance to ablation of high emissivity high tenacity.
In above-mentioned preparation process, matrix component is the combination that ZrC and HfC mass fraction is 2:1 in step (1), and silicon source is
Si3N4 and MoSi2Mass fraction is the combination of 3:4, sintering aid ZrSi2And TaSi2Mass fraction is the combination of 1:1.
In above-mentioned preparation process, the ratio of grinding media to material in step (1) is 2；The mass ratio of abrasive media and material is 1:2.
In above-mentioned preparation process, the organic solvent in step (2) is n,N-dimethylacetamide and N-Methyl pyrrolidone
Mass fraction is 2:3 combination, and organic binder is the combination that PES and PC mass fraction is 1:1, and dispersing agent is polyethylene glycol and pungent
Alcohol mass fraction is the combination of 1:2, and dispersing agent additional amount is the 8% of organic solvent quality, organic binder, powder, You Jirong
The mass ratio of agent is 1.5:4:10；
In above-mentioned preparation process, the voltage in step (3) between syringe nozzle and take-up reel is 5kV, syringe needle
Upper ultrasonic wave comment is 25kHz, and syringe nozzle is 6cm at a distance from take-up reel, and the fltting speed of syringe is 0.5ml/
Min will guarantee to insulate, in order to guarantee slurry and water before syringe starts to promote to all appts surface alcohol wipe
Between carry out sufficient mass exchange, therefore the time that mixed liquor is stood should be not less than 48h.
In above-mentioned preparation process, heat treatment temperature is 1400 DEG C in step (4), and batch-type furnace heating rate is 4 DEG C/min, drop
Warm speed is 4 DEG C/min, and powder thickness should be no more than 10mm in crucible.
In the present embodiment, it is that Qingdao Lian Rui precision instrument Co., Ltd produces that high-energy ball milling, which uses,
UNIONPROCESS grinder, model 01-HDDM.
In the present embodiment, ultrasonic cell disruptor is Shanghai reliable industry Development Co., Ltd production only, model JY9Z-
ⅡN
In the present embodiment, high temperature process furnances are the SGL-1400 types of Shanghai Daheng Optical Fine Mechinery Co., Ltd's production
Tube furnace.
In the present embodiment, precise injection pump is that Harvard company in the U.S. produces, model PHDULTRACP.
In the present embodiment, high temperature box furnace is 1700 DEG C of three temperature of Shanghai Ju Jing precision instrument Manufacturing Co., Ltd production
Area's tube furnace, model: SGL-1700- III.
Embodiment 3
The present invention is achieved through the following technical solutions above-mentioned performance:
(1) the preparation mixing of powder: using isopropanol or ethyl alcohol as abrasive media, using the method for high-energy ball milling by UHTCs
Constituent element, high emissivity self-healing constituent element and sintering aid are that 80:80:7 carries out ball milling and mixing, Ball-milling Time are in mass ratio
Obtained slurry is dried for 24 hours to constant weight after ball milling, grinds and be sieved and mixed by 48h, ball milling speed 4000r/min
Powder is closed, the primary particle size of powder should be not more than 200nm after ball milling；
(2) preparation of precursor pulp: being in 6:7 merging organic solvent by powder obtained in step (1) in mass ratio
Be sufficiently stirred and disperse, later be placed in ultrasonic disintegrator in ultrasonic disperse 60min to eliminate the physical agglomeration between nanometer powder,
Uniform powder suspension is obtained, organic adhesive auxiliary agent and dispersing agent is added thereto when suspension does not settle, is used
The mode of oil bath heating comprehensive mechanical stirring carries out uniform stirring to the mixed liquor, and the revolving speed of mixing time 48h, stirring rod are
700r/min, be added at the bottle stopper condensation reflux unit prevent organic solvent volatilize and caused by the proportion of precursor pulp occur
Change, is cooled to room temperature after being sufficiently stirred spare；
(3) preparation of precursor powder: step (3) obtained slurry is once filtered, filter out it is therein not
Molten impurity carries out slurry before starting to prepare powder to be vacuum-treated the residual air for excluding slurry.Slurry is injected later
Among syringe, syringe is disposed vertically, and is placed below syringe and is filled deionized water (50 of volume greater than slurry total volume
Times) take-up reel, be positive grade with the syringe needle equipped with Vltrasonic device syringe, be cathode application voltage using take-up reel, slurry is in electricity
The droplet of micro-meter scale is separated under acting under the collective effect of field and mechanical wave.After device push to be injected, removal electricity
Field and ultrasound are simultaneously stood, by the solid phase powder sieving in receiving plate and natural air drying, formation precursor powder；
(4) sintering process: by step (3) to precursor powder be laid in crucible, be placed in vacuum tube furnace
Middle carry out high-temperature heat treatment, sieves sintered powder, obtains the heat-insulated microballoon filler of the resistance to ablation of high emissivity high tenacity.
In above-mentioned preparation process, matrix component is ZrB in step (1)2、HfB2, (Zr/Hf/Ta)-Ti-N-C-O and (Zr/
Hf/Ta)-Si-B-C-O ceramic mass score is the combination of 2:3:1:1, silicon source CoFe2O4、NiFe2O4And NiCr2O4Quality point
Number is the combination of 1:1:1, sintering aid ZrSi2。
In above-mentioned preparation process, the ratio of grinding media to material in step (1) is 5；The mass ratio of abrasive media and material is 1:6.
In above-mentioned preparation process, organic solvent in step (2) be n,N-dimethylacetamide, N-Methyl pyrrolidone with
And dimethyl acetamide mass fraction be 1:2:3 combination, the combination that organic binder is aramid fiber and PP mass fraction is 1:3,
Dispersing agent is polyvinylpyrrolidone, and the mass fraction of polyethylene glycol and octanol is 1:1:2 combination, and dispersing agent additional amount is organic
The 5% of solvent quality, organic binder, powder, the mass ratio of organic solvent are 1:2:5；
In above-mentioned preparation process, the voltage in step (3) between syringe nozzle and take-up reel is 25kV, syringe needle
Upper ultrasonic wave comment is 100kHz, and syringe nozzle is 15cm at a distance from take-up reel, and the fltting speed of syringe is 3ml/
Min will guarantee to insulate, in order to guarantee slurry and water before syringe starts to promote to all appts surface alcohol wipe
Between carry out sufficient mass exchange, therefore the time that mixed liquor is stood should be not less than 48h.
In above-mentioned preparation process, heat treatment temperature is 1800 DEG C in step (4), and batch-type furnace heating rate is 6 DEG C/min, drop
Warm 6 DEG C/min of speed, powder thickness should be no more than 10mm in crucible.
Embodiment 4
A kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity, using following methods:
(1) the preparation mixing of powder: high using the method for high-energy ball milling by UHTCs constituent element using isopropanol as abrasive media
Emissivity self-healing constituent element and sintering aid are that 20:80:5 carries out ball milling mixing in mass ratio, and the UHTC constituent element used is Hf
(Zr, Ta) C and Hf (Zr, Ta) B2Mixture, high emissivity self-healing constituent element be platinum black, sintering aid ZrSi2, control ball
Time consuming is for 24 hours, ball milling speed 4000r/min, and ratio of grinding media to material when ball milling is 2；The mass ratio of abrasive media and material is 1:
2, obtained slurry is dried for 24 hours to constant weight after ball milling, grinds and be sieved to obtain mixed-powder, powder is primary after ball milling
Partial size should be not more than 200nm；
(2) preparation of precursor pulp: being 1:12 merging organic solvent N by powder obtained in step (1) in mass ratio,
Be sufficiently stirred and disperse in N- dimethyl acetamide, later be placed in ultrasonic disintegrator in ultrasonic disperse 10min to eliminate nano powder
Physical agglomeration between end obtains uniform powder suspension, organic adhesive is added thereto when suspension does not settle
Auxiliary agent poly aromatic amide and polyethylene of dispersing agent pyrrolidones, dispersing agent additional amount are the 12% of organic solvent quality, organic viscous
Tie agent, powder, the mass ratio of organic solvent is 2:5:12, by the way of the stirring of oil bath heating comprehensive mechanical to the mixed liquor into
Row uniform stirring, mixing time are that for 24 hours, the revolving speed of stirring rod is 700r/min, and condensation reflux unit is added at bottle stopper to be prevented
Organic solvent volatilization and caused by the proportion of precursor pulp change, be cooled to room temperature after being sufficiently stirred spare；
(3) preparation of precursor powder: step (3) obtained slurry is once filtered, filter out it is therein not
Molten impurity carries out slurry before starting to prepare powder to be vacuum-treated the residual air for excluding slurry.Slurry is injected later
Among syringe, syringe is disposed vertically, and is placed below syringe and is filled deionized water (50 of volume greater than slurry total volume
Times) take-up reel, be positive grade with the syringe needle equipped with Vltrasonic device syringe, be that cathode applies voltage using take-up reel, control is injected
Voltage between device nozzle and take-up reel is 5kV, and ultrasonic frequency is 25kHz, syringe nozzle and reception on syringe needle
The distance of disk is 6cm, and the fltting speed of syringe is 0.5ml/min, will be to all appts table before syringe starts to promote
For face alcohol wipe to guarantee to insulate, slurry is separated into the small of micro-meter scale under acting under the collective effect of electric field and mechanical wave
Drop.After device push to be injected, removes electric field and ultrasound and stand, in order to guarantee to carry out sufficient object between slurry and water
Mass transter, therefore the time that mixed liquor is stood should be not less than 48h, by the solid phase powder sieving in receiving plate and natural air drying, shape
At precursor powder；
(4) sintering process: by step (3) to precursor powder be laid in crucible, thickness should be no more than 10mm,
It is placed in vacuum tube furnace and carries out high-temperature heat treatment, controlled at 1400 DEG C, batch-type furnace heating rate is 4 DEG C/min, drop
Warm speed is 4 DEG C/min, then sieves to sintered powder, obtains the heat-insulated microballoon of the resistance to ablation of high emissivity high tenacity and fill out
Material.
Embodiment 5
A kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity, using following methods:
(1) the preparation mixing of powder: high-incidence using the method for high-energy ball milling by UHTCs constituent element using ethyl alcohol as abrasive media
Penetrating rate self-healing constituent element and sintering aid in mass ratio is that 80:20:10 carries out ball milling and mixing, wherein the UHTCs group used
Member is (Zr/Hf/Ta)-Si-N-C-O, high emissivity self-healing constituent element is MoSi2, sintering aid TaSi2, Ball-milling Time is
48h, ball milling speed 1000r/min, ratio of grinding media to material 5；The mass ratio of abrasive media and material is 1:6, is incited somebody to action after ball milling
The slurry arrived is dried for 24 hours to constant weight, grinds and be sieved to obtain mixed-powder, the primary particle size of powder should be not more than after ball milling
200nm；
(2) preparation of precursor pulp: being 6:7 merging organic solvent two by powder obtained in step (1) in mass ratio
Be sufficiently stirred and disperse in methylacetamide, later be placed in ultrasonic disintegrator in ultrasonic disperse 60min with eliminate nanometer powder it
Between physical agglomeration, obtain uniform powder suspension, it is organic that polyolefins be added thereto when suspension does not settle
Adhesive aid and dispersing agent octanol, dispersing agent additional amount are the 15% of organic solvent quality, organic binder, powder, You Jirong
The mass ratio of agent is 1:6:5, uniform stirring is carried out to the mixed liquor by the way of the stirring of oil bath heating comprehensive mechanical, when stirring
Between be 48h, the revolving speed of stirring rod is 200r/min, and condensation reflux unit is added at bottle stopper prevents organic solvent from volatilizing and causing
The proportion of precursor pulp change, be cooled to room temperature after being sufficiently stirred spare；
(3) preparation of precursor powder: step (3) obtained slurry is once filtered, filter out it is therein not
Molten impurity carries out slurry before starting to prepare powder to be vacuum-treated the residual air for excluding slurry.Slurry is injected later
Among syringe, syringe is disposed vertically, and is placed below syringe and is filled deionized water (50 of volume greater than slurry total volume
Times) take-up reel, be positive grade with the syringe needle equipped with Vltrasonic device syringe, be that cathode applies voltage using take-up reel, control is injected
Voltage between device nozzle and take-up reel is 25kV, and ultrasonic frequency is 100kHz on syringe needle, syringe nozzle with connect
The distance of closing quotation is 15cm, and the fltting speed of syringe is 3ml/min, will be to all appts table before syringe starts to promote
For face alcohol wipe to guarantee to insulate, slurry is separated into the small of micro-meter scale under acting under the collective effect of electric field and mechanical wave
Drop.After device push to be injected, removes electric field and ultrasound and stand, in order to guarantee to carry out sufficient object between slurry and water
Mass transter, therefore the time that mixed liquor is stood should be not less than 48h, by the solid phase powder sieving in receiving plate and natural air drying, shape
At precursor powder；
(4) sintering process: by step (3) to precursor powder be laid in crucible, thickness should be no more than 10mm,
It is placed in vacuum tube furnace and carries out high-temperature heat treatment, controlled at 1800 DEG C, batch-type furnace heating rate is 6 DEG C/min, drop
Warm speed is 6 DEG C/min, then sieves to sintered powder, obtains the heat-insulated microballoon of the resistance to ablation of high emissivity high tenacity and fill out
Material.
Preferably, heat treatment temperature is 1400~1800 DEG C in step (4), and batch-type furnace heating rate is 4~6 DEG C/min,
Cooling rate is 4~6 DEG C/min, and powder thickness should be no more than 10mm in crucible.
Embodiment 6
Table 1 is the density of three groups of embodiments and blank control group, the contrast table of ablation resistance and emissivity, blank pair
It is the silicon rubber that filler is not added according to group.As can be seen that by the way that filler prepared by the present invention is added, the emissivity of basis material goes out
It now significantly improves, reaches 92% or more；Mass ablative rate is decreased obviously, and wherein embodiment 2 is burnt as the silicon rubber quality of filler
Erosion rate is almost 0, and therefore, the addition of ceramic microsphere can significantly improve the radiance and ablation resistance of coating, in superhigh temperature
Heat-insulated field has very wide application prospect.
The different embodiment emissivity of table 1 and heat resistance comparison sheet
| Sample | Density (g/cm^3) | Emissivity (%) | Mass ablative rate (%) |
| Embodiment 1 | 1.37 | 93.30 | 2.31 |
| Embodiment 2 | 1.42 | 93.43 | 0.97 |
| Embodiment 3 | 1.40 | 92.99 | 1.21 |
| Control group | 0.97 | 46.12 | 9.48 |
In conclusion high emissivity ceramic microsphere prepared by the present invention has special finger-like hole and the porous knot of layering
Structure, it is internal compared with the tiny balloon of traditional structure to have complicated multistage pore structure and powder surface for submicron powder heap
The spongelike structure of product sintering and formation, specific surface area is bigger, and surface roughness is higher, has high emissivity；Silicon substrate
The addition of flame retardant can form the SiO of molten condition under conditions of high temperature is aerobic2, so that material has the property of self-healing
Can, so that the ability that the addition of the microballoon filler can significantly improve the heat resistanceheat resistant vibration of material and violent starting is washed away；And mechanics
Performance and thermal structure excellent in stability are a kind of very ideal heat-insulated resistance to ablation high emissivity self-healing fillers.It is same with this
When, lid ceramic powders are with short production cycle, and equipment cost is low, and powder good sphericity, size tunable, preparation flow is simple, operation letter
It is single, there is very high application value.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity characterized by comprising
The preparation of powder mixes: using isopropanol or ethyl alcohol as abrasive media, by UHTCs constituent element, high emissivity self-healing constituent element and
Sintering aid is (20~80) in mass ratio: (20~80): (5~10) carry out mixing and ball milling as material, and drying obtains powder；
The preparation of precursor pulp: being (1~6) by obtained powder and organic solvent in mass ratio: (7~12) are mixed,
Ultrasonic treatment obtains powder suspension, and organic adhesive auxiliary agent and dispersing agent are added when suspension does not settle, continues to heat
Stirring, is cooled to room temperature；
The preparation of precursor powder: obtained slurry is once filtered, and carries out being vacuum-treated the residual of exclusion slurry to slurry
Remaining air injects slurry among syringe, and syringe is disposed vertically, and the reception that deionized water is housed is placed below syringe
Disk is positive grade with the syringe needle equipped with Vltrasonic device syringe, is cathode application voltage using take-up reel, slurry is in electric field and mechanical wave
Collective effect under act under be separated into the droplet of micro-meter scale, stewing process after device push to be injected, by receiving plate
In solid phase powder sieving and natural air drying, formed precursor powder；
Sintering process: precursor powder is laid in crucible, is placed in vacuum tube furnace and is carried out high-temperature heat treatment, to sintering
Powder afterwards is sieved, and the heat-insulated microballoon filler of the resistance to ablation of high emissivity high tenacity is obtained.
2. a kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity according to claim 1, which is characterized in that
The UHTCs constituent element is Hf (Zr, Ta) C, Hf (Zr, Ta) B2、[Hf(Zr,Ta)]3N4、Hf(Zr,Ta)C-SiC、Hf(Zr,
Ta)B2-SiC、[Hf(Zr,Ta)]3N4-SiC、(Zr/Hf/Ta)-Ti-B-C-O、(Zr/Hf/Ta)-Ti-N-C-O、(Zr/Hf/
Ta) one kind or combination of the more member ceramics of-Si-B-C-O or (Zr/Hf/Ta)-Si-N-C-O,
The high emissivity self-healing constituent element is platinum black, Si, SiC, SiB4、SiB6、CuO、Si3N4、MoSi2Or high emissivity point is brilliant
One or more of any combination in stone phase compound,
Sintering aid is transition elements silicide.
3. a kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity according to claim 2, which is characterized in that
The high emissivity Spinel compound includes MgFe2O4、CuFe2O4、ZnFe2O4、CoFe2O4、NiFe2O4、NiCr2O4
Or NiAl2O4One or more of any combination,
The transition elements silicide includes ZrSi2Or TaSi2One or more of any combination.
4. a kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity according to claim 1, which is characterized in that
It is 2~5 that ratio of grinding media to material is controlled when ball milling；The mass ratio of abrasive media and material is 1:2~6.
5. a kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity according to claim 1, which is characterized in that
Ball-milling Time is 24~48h, and ball milling speed is 1000~4000r/min, and the primary particle size of powder is not more than 200nm after ball milling.
6. a kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity according to claim 1, which is characterized in that
The organic solvent, which is that DMAC N,N' dimethyl acetamide, N-Methyl pyrrolidone or dimethyl acetamide are one or more of, appoints
Meaning combination,
The organic binder is polysulfones, poly aromatic amide, one or more of any of polyolefins or polyaromatic compound
Combination,
The dispersing agent is polyvinylpyrrolidone, one or more of any combination of polyethylene glycol or octanol,
Dispersing agent additional amount is the 5%~15% of organic solvent quality, and the mass ratio of organic binder, powder, organic solvent is
(1~2): (2~6): (5~12).
7. a kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity according to claim 1, which is characterized in that
Heating stirring is carried out to the mixed liquor by the way of the stirring of oil bath heating comprehensive mechanical, mixing time is 24~48h, stirring rod
Revolving speed be 200~700r/min, condensation reflux unit is added when heating stirring on reactor prevents organic solvent from volatilizing.
8. a kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity according to claim 1, which is characterized in that
Voltage between syringe nozzle and take-up reel is 5~25kV, and ultrasonic frequency is 25~100kHz, injection on syringe needle
Device nozzle is 6~15cm at a distance from take-up reel, and the fltting speed of syringe is 0.5~3ml/min.
9. a kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity according to claim 1, which is characterized in that
The time of stewing process is not less than 48h.
10. a kind of preparation method of the heat-insulated microballoon filler of the resistance to ablation of high emissivity according to claim 1, feature exist
In, the temperature of high-temperature heat treatment is 1400~1800 DEG C, and heating rate is 4~6 DEG C/min, and cooling rate is 4~6 DEG C/min,
Precursor powder thickness is no more than 10mm in crucible.
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