CN105000887B - ZrO is prepared by carbon source of sucrose2The method of ZrC composite ceramics microballoons - Google Patents
ZrO is prepared by carbon source of sucrose2The method of ZrC composite ceramics microballoons Download PDFInfo
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- CN105000887B CN105000887B CN201510463391.5A CN201510463391A CN105000887B CN 105000887 B CN105000887 B CN 105000887B CN 201510463391 A CN201510463391 A CN 201510463391A CN 105000887 B CN105000887 B CN 105000887B
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Abstract
The invention provides prepare ZrO by carbon source of sucrose2The method of ZrC composite ceramics microballoons, this method include：Glue prepares, adds the step of sucrose, scattered and ripening, the first carrying out washing treatment, hydro-thermal process, the second carrying out washing treatment, drying process and sintering processes.Using this method according to embodiments of the present invention, ZrO can be quickly and efficiently prepared2ZrC composite ceramics microballoons, and glue can be prepared and be stabilized at normal temperatures.
Description
Technical field
The invention belongs to ceramic molding field, and in particular to the method that interior gelatinizing process prepares ceramic microsphere, more
Body, it is related to the preparation ZrO using sucrose as carbon source2The interior gelation of-ZrC composite ceramics microballoons.
Background technology
Zirconium dioxide (ZrO2) and zirconium carbide (ZrC) all there is low neutron capture section, high fusing point and chemically stable
Property, and under radiation condition the features such as stabilization, it is considered as the inert base of reactor inert base fuel (IMF).Using
Sol-gel technology prepares ZrO2The relevant report of ceramic microsphere is a lot, but uses sol-gel process to prepare microballoon containing ZrC
Report do not have substantially.
Interior gelatinizing process is a kind of advanced technology for preparing ceramic microsphere, is widely used in HTGR fuel core
Such as UO2、PuO2And the preparation of inert base, and interior gelatinizing process can allow for other components Uniform Doped to enter in bead, fit
Close the preparation of non-oxidized substance such as carbide, nitride-based pottery spheroid.However, it is always shadow that the glue of interior gelatinizing process is unstable
One of subject matter of gelatinizing process large-scale application in sound, microballoon containing ZrC is particularly prepared, need to add carbon in preparation process
Source, highdensity ceramic microsphere containing ZrC needed for the glue stability of its internal gelatinizing process and preparation is most important, however,
At present and have no and can be used in the relevant report that inner gel technique prepares ceramic microsphere containing ZrC and the comparatively ideal carbon source of performance.
Still need to be goed deep into accordingly, with respect to the research using inner gel technique preparation ceramic microsphere containing ZrC.
The content of the invention
It is contemplated that at least solves one of technical problem in correlation technique to a certain extent.Therefore, the present invention
One purpose is the preparation ZrC-ZrO for proposing that a kind of glue can be stabilized at normal temperatures2The method of composite ceramics microballoon.
The present invention is the following discovery based on inventor and completed：
Inventor is in research process discovery, ZrO2Thermal conductivity factor it is very low, only 2~3W/m K and substantially not with temperature
Change and change, and ZrC thermal conductivity factor is 20.52W/m K at 25 DEG C, can reach 38.5 at 1300~1600 DEG C~
40.6W/m K.Preparing ZrO2Appropriate carbon source is added in the glue of microballoon, can be obtained containing ZrC by carbothermic reduction reaction
Microballoon, while ZrC materials are incorporated into ZrO by this process2It is expected to improve ZrO in matrix2The heat conductivility of material, for reaction
Heap inert base fuel provides a kind of ZrC-ZrO of new great potential2Composite.
In view of above-mentioned discovery, inventor have made intensive studies, the results showed that, the selection of carbon source is for interior gelatinizing process
Highdensity ZrC-ZrO needed for glue stability and preparation2Composite ceramics microballoon is most important.Because ZrC is directly by ZrO2
React to obtain with the carbon inside gel ball, if the carbon particle in gel ball is excessive or reunites, after carbothermic reduction reaction
Hole or unreacted carbon particle can be left in ball interior, it is clear that this is unfavorable for obtaining highdensity ceramic microsphere
, and selected carbon source need it is more stable in existing glue system so that the preparation of glue and be stored in normal temperature
Carried out under (25 degrees centigrade), and do not occur to chemically react and influence glue stability.
Verify by a large amount of explorative experiments and repeatedly, inventor has found carbon dust and sucrose as carbon source for glue stability
Influence very little, but use carbon dust to need to ensure that particle size is even more small less than 5 microns could make it that carbon dust is warm in carbon
Reacted completely in reduction process and do not leave residual carbon, even if the carbon powder particle size used can meet to require, but carbon dust exists
What is be difficult to avoid that when disperseing in glue occurs reunion (even in the case of using carbon dust dispersant and such), causes
Particle becomes big, influences the ZrC-ZrO being prepared2The component distributing and density of complex microsphere.And test and show to make using sucrose
For carbon source, the stability of glue will not be produced a very large impact substantially under normal temperature (25 degrees centigrade), glue can be ensured
Prepare and storage is carried out at normal temperatures, what is more important sucrose can ensure carbon being uniformly distributed in microballoon as carbon source
And particle size is small, it is ensured that the ZrC-ZrO being prepared2The high density and composition of composite ceramics microballoon are uniform.
In view of this, in one aspect of the invention, the invention provides one kind to prepare ZrO2- ZrC composite ceramics microballoons
Method.According to an embodiment of the invention, this method includes：By the first solution containing Zr and Y and contain hexamethylenetetramine
Mixed with the second solution of urea, and concentrated nitric acid is added into resulting mixture, obtain glue；Sugarcane is added into glue
Sugar, obtain the glue containing sucrose；Glue containing sucrose is distributed in hot silicone oil, and carries out ripening, obtains gel
Ball；Gel ball is subjected to the first carrying out washing treatment, obtains the gel ball by the first washing；Gel ball by the first washing is entered
Water-filling is heat-treated, and obtains the gel ball by hydro-thermal process；Gel ball Jing Guo hydro-thermal process is subjected to the second carrying out washing treatment, obtained
To the gel ball by the second washing；Processing is dried in gel ball by the second washing, obtains desiccant gel ball；Will be dry
Dry gel ball is sintered, and obtains ZrO2- ZrC composite ceramics microballoons.
Inventor has found, using this method according to embodiments of the present invention, can quickly and efficiently prepare ZrO2-
ZrC composite ceramics microballoons, and glue can be prepared and be stabilized at normal temperatures, efficiently solve glue in existing inner gel technique
Liquid is unstable, it is necessary to low temperature environment, the problem of condition harshness, it is accordingly required in particular to, it is noted that in the method, using sucrose conduct
Carbon source, the stability of glue will not be produced a very large impact substantially under normal temperature (25 degrees centigrade), matching somebody with somebody for glue can be ensured
System and storage are carried out at normal temperatures, what is more important sucrose as carbon source, can ensure carbon in microballoon be uniformly distributed with
And particle size is small, the ZrC-ZrO that is prepared2Composite ceramics microsphere surface is fine and close, internal without obvious hole, Neng Gouyou
Effect ensures ZrC-ZrO2The high density and composition of composite ceramics microballoon are uniform.
It will be understood by those skilled in the art that improving, prepared by glue and the temperature of storage is to reduce cooling glue institute
The energy consumption needed, the lower glue of temperature are more stable (as long as not freezing).And preparation ZrO according to embodiments of the present invention2-
In the method for ZrC composite ceramics microballoons, glue has good stability, energy within the temperature range of not higher than 27 degrees Celsius
Enough meet production requirement.Therefore, normal temperature specifically described herein (25 degrees centigrade) refers to the temperature model not higher than 27 degrees Celsius
Enclose.
According to an embodiment of the invention, ZrO (NO are contained in the first solution3)2With Y (NO3)3。
According to an embodiment of the invention, in the first solution, ZrO (NO3)2Concentration be 1.6~1.7 mol/Ls, Y
(NO3)3Concentration is 0.14~0.15 mol/L.
According to an embodiment of the invention, in the second solution, the concentration of hexamethylenetetramine is 3~3.2 mol/Ls, urine
The concentration of element is 0.7~1.1 mol/L.
According to an embodiment of the invention, the pH value of glue is 1~2.
According to an embodiment of the invention, in the glue containing sucrose, the zr element in carbon and glue in sucrose
Mol ratio be 0.5~6, preferably 0.5~4.
According to an embodiment of the invention, the temperature of hot silicone oil is 85~90 degrees Celsius.
According to an embodiment of the invention, the time of ripening is 0.5~1 hour.
According to an embodiment of the invention, the first carrying out washing treatment further comprises：Using trichloro ethylene detergent gel ball 4 times,
Washing continues at least 20 minutes every time；The gel ball by trichloro ethylene washing is rinsed using absolute ethyl alcohol.
According to an embodiment of the invention, hydro-thermal process is washed ball process and further comprised：By the gel ball by the first washing
It is placed in the reactor of polytetrafluoroethylene (PTFE), using absolute ethyl alcohol as solvent, reacts 6 hours at 200 degrees celsius.
According to an embodiment of the invention, the second washing further comprises：Pass through hydro-thermal using 0.5mol/L ammonia scrubbing
The gel ball of processing, the electrical conductivity to scrub raffinate are less than 800 μ S/cm；Profit is washed with deionized by the solidifying of ammonia scrubbing
Glueballs, the electrical conductivity to scrub raffinate are less than 30 μ S/cm；Utilize gel of the propylene glycol monomethyl ether washing by deionized water washing
Ball four times, every time washing continue at least 20 minutes.
According to an embodiment of the invention, drying process is to be dried at room temperature for 1~2 hour, then at 60~80 degrees Celsius
Lower drying is not less than 12 hours.
According to an embodiment of the invention, sintering processes be in the argon gas atmosphere containing 5% volume fraction C O, 1500~
Calcined 3~5 hours under 1600 degrees celsius.
In another aspect of this invention, ZrO is prepared using inner gel technique the invention provides one kind2- ZrC composite ceramicses
The method of microballoon, in the method, using sucrose as carbon source.Inventor is by many experiments and verifies repeatedly, finds to use
Sucrose can ensure carbon in microballoon as carbon source on the premise of interior gelatinization glue ordinary temperature stability is not influenceed
Be uniformly distributed and particle size is small so that the ZrC-ZrO being prepared2Composite ceramics microsphere surface is fine and close, inside does not have
Obvious hole, it is ensured that the ZrC-ZrO being prepared2The high density and composition of composite ceramics microballoon are uniform.
Brief description of the drawings
Fig. 1 is preparation ZrC-ZrO according to an embodiment of the invention2The method flow schematic diagram of composite ceramics microballoon.
Fig. 2 is that the viscosity of the glue according to an embodiment of the invention containing different carbon source changes with time at 25 DEG C
Curve.
Fig. 3 be the glue of different cane sugar contents according to an embodiment of the invention viscosity at 25 DEG C with the change of time
Change curve.
Fig. 4 be it is according to an embodiment of the invention using sucrose as carbon source, glue in the ZrC-ZrO that obtain when being 1 of C/Zr2
Composite ceramics microsphere surface and the SEM photograph in section.
Fig. 5 be it is according to an embodiment of the invention using sucrose as carbon source, glue in the ZrC-ZrO that obtain when being 2 of C/Zr2
Composite ceramics microsphere surface and the SEM photograph in section.
Fig. 6 be it is according to an embodiment of the invention using sucrose as carbon source, glue in the ZrC-ZrO that obtain when being 3 of C/Zr2
Composite ceramics microsphere surface and the SEM photograph in section.
Fig. 7 be it is according to an embodiment of the invention using Ts-10 carbon blacks as carbon source, in glue C/Zr as 0.5 when obtain
ZrC-ZrO2The SEM photograph in composite ceramics microballoon section.
Embodiment
Embodiments of the invention are described below in detail.The embodiments described below is exemplary, is only used for explaining this hair
It is bright, and be not considered as limiting the invention.Unreceipted particular technique or condition in embodiment, according to text in the art
Offer described technology or condition or carried out according to product description.Agents useful for same or the unreceipted production firm person of instrument,
For the conventional products of acquisition purchased in market can be passed through.
In one aspect of the invention, the invention provides one kind to prepare ZrO2The method of-ZrC composite ceramics microballoons.Root
According to embodiments of the invention, reference picture 1, this method comprises the following steps：
S100：The first solution containing Zr and Y is mixed with the second solution containing hexamethylenetetramine and urea, and to
Concentrated nitric acid is added in resulting mixture, obtains glue.
According to an embodiment of the invention, ZrO (NO are contained in the first solution3)2With Y (NO3)3.In other words, can utilize
ZrO(NO3)2With Y (NO3)3It is configured to the first solution.In some embodiments of the invention, in the first solution, ZrO (NO3)2
Concentration be 1.6~1.7 mol/Ls, Y (NO3)3Concentration is 0.14~0.15 mol/L.Thereby, it is possible to cause glue in normal temperature
Under the conditions of prepare, avoid the harsh conditions of low temperature, its obtained glue can be stabilized at normal temperatures, if ZrO (NO3)2With
Y(NO3)3Excessive concentration or too low, do not reach the effect that above-mentioned glue can be prepared and be stabilized at normal temperatures.
According to an embodiment of the invention, in the second solution, the concentration of hexamethylenetetramine is 3~3.2 mol/Ls, urine
The concentration of element is 0.7~1.1 mol/L.Thereby, it is possible to cause glue to be prepared under normal temperature condition, the harsh bar of low temperature is avoided
Part, its obtained glue can be stabilized at normal temperatures, if the excessive concentration or too low of hexamethylenetetramine and urea,
The effect that above-mentioned glue can be prepared and be stabilized at normal temperatures is not reached.
According to an embodiment of the invention, the pH value of glue can be 1~2.Thus, be advantageous to improve glue in normal temperature condition
Under stability.
Specifically, can include in this step：By ZrO (NO3)2With Y (NO3)3Dissolving is configured to solution, wherein ZrO
(NO3)2Concentration be 1.6~1.7 mol/Ls, Y (NO3)3Concentration is 0.14~0.15 mol/L, then, by six methines four
Amine and urea are mixed, wherein, the concentration of hexamethylenetetramine is 3~3.2 mol/Ls, and the concentration of urea is 0.7~1.1
Mol/L.The above-mentioned solution containing hexamethylenetetramine and urea is added to containing ZrO (NO3)2、Y(NO3)3Solution in, Bian Jia
Enter side stirring, while add appropriate concentrated nitric acid thereto, the glue of clear is prepared, the pH value of glue is 1~2.
The preparation and storage of glue are all carried out under normal temperature condition, and glue has good stability, can be grown under normal temperature condition
Time stores.
S200：Sucrose is added into glue, obtains the glue containing sucrose.
According to an embodiment of the invention, in the glue containing sucrose, the zr element in carbon and glue in sucrose
Mol ratio be 0.5~6, under preferable case, the mol ratio of the zr element in carbon and glue in sucrose is 0.5~4.Hair
A person of good sense has found by substantial amounts of explorative experiment, it has unexpectedly been found that using the sucrose in the proportion as carbon source, Ke Yi
Under conditions of the ordinary temperature stability for not influenceing glue so that carbon being uniformly distributed in microballoon and particle size are small, are prepared into
The ZrC-ZrO arrived2Composite ceramics microsphere surface is fine and close, internal without obvious hole, can effectively ensure ZrC-ZrO2Composite ceramic
The high density and composition of porcelain microballoon are uniform.
Specifically, can include in this step：Appropriate sucrose is added in the glue prepared to above-mentioned steps,
Stir to clarify, sucrose (C12H22O11) addition make it that the molar ratio of zirconium ion in sucrose institute's phosphorus content and glue is (following
Referred to as C/Zr) between 0.5~6, under preferable case be 0.5~4 between.Added sucrose as carbon source in glue, not
The stability of glue at normal temperatures is influenceed, and is advantageous to carbon in the ZrO prepared2It is uniformly distributed in-ZrC composite ceramics microballoons
And particle size is small so that ZrC-ZrO2Composite ceramics microsphere surface is fine and close, internal without obvious hole, it is ensured that is prepared into
The ZrC-ZrO arrived2The high density and composition of composite ceramics microballoon are uniform.
S300：Glue containing sucrose is distributed in hot silicone oil, and carries out ripening, obtains gel ball.
According to an embodiment of the invention, the temperature of hot silicone oil can be 85~90 degrees Celsius.Thus, be advantageous to improve glue
Dispersive property, advantageously form the gel ball of size uniform.
According to an embodiment of the invention, the time of ripening is 0.5~1 hour.Thus, performance ideal is advantageously formed
Gel ball.
S400：Gel ball is subjected to the first carrying out washing treatment, obtains the gel ball by the first washing.
According to an embodiment of the invention, the first carrying out washing treatment can include：Using trichloro ethylene detergent gel ball 4 times, often
Secondary washing continues at least 20 minutes, then rinses the gel ball by trichloro ethylene washing using absolute ethyl alcohol.Thereby, it is possible to have
Effect removes the residual silicone oil of gel ball surface, and impurity is not introduced in subsequent step, is advantageous to the progress of subsequent step.
S500：Gel ball by the first washing is subjected to hydro-thermal process, obtains the gel ball by hydro-thermal process.
According to an embodiment of the invention, hydrothermal treatment process can include：Gel ball by the first washing is placed in poly-
In tetrafluoroethene reactor (hydro-thermal reaction device, liner are polytetrafluoroethylene (PTFE)), using absolute ethyl alcohol as solvent, at 200 degrees Celsius
Lower reaction 6 hours.Thereby, it is possible to effectively cause the sucrose carbonization in gel ball, and carbon is evenly distributed in gel ball,
Particle size is small.
S600：Gel ball Jing Guo carbon thermal reduction is subjected to the second carrying out washing treatment, obtains the gel ball by the second washing.
According to an embodiment of the invention, the second washing may further include：Passed through using 0.5mol/L ammonia scrubbing
The gel ball of carbon thermal reduction, the electrical conductivity to scrub raffinate are less than 800 μ S/cm；Pass through ammoniacal liquor followed by deionized water washing
The gel ball of washing, the electrical conductivity to scrub raffinate are less than 30 μ S/cm；Then deionized water is passed through using propylene glycol monomethyl ether washing
The gel ball of washing four times, every time washing continue at least 20 minutes.Thereby, it is possible to effectively remove the residual reaction of gel ball surface
Liquid and other impurities.
S700：Processing is dried in gel ball by the second washing, obtains desiccant gel ball.
According to an embodiment of the invention, drying process is to be dried at room temperature for 1~2 hour, then at 60~80 degrees Celsius
Lower drying is not less than 12 hours.
S800：Desiccant gel ball is sintered, obtains ZrO2- ZrC composite ceramics microballoons.
According to an embodiment of the invention, sintering processes are in the argon gas atmosphere containing 5% volume CO, 1500~1600 taken the photograph
Calcined 3~5 hours under the conditions of family name's degree.In this step, sintering heating curve can be according to the TG-DSC curve of desiccant gel ball
Formulate, specifically, 0.5~1 hour is incubated at each heat absorption exothermic peak on TG-DSC curves.And in order to prevent microballoon
Ftractureed in sintering process, sintering process programming rate is as slow as possible, Celsius to the heating 0.5 of 600 centigrade per minutes in room temperature
Degree, heated up 1 degree Celsius in 600 to 1600 centigrade per minutes.
Inventor has found, using this method according to embodiments of the present invention, can quickly and efficiently prepare ZrO2-
ZrC composite ceramics microballoons, and glue can be prepared and be stabilized at normal temperatures, efficiently solve glue in existing inner gel technique
Liquid is unstable, it is necessary to low temperature environment, the problem of harsh conditions, it is accordingly required in particular to, it is noted that in the method, using sucrose conduct
Carbon source, the stability of glue will not be produced a very large impact substantially under normal temperature (25 degrees centigrade), matching somebody with somebody for glue can be ensured
System and storage are carried out at normal temperatures, what is more important sucrose as carbon source, can ensure carbon in microballoon be uniformly distributed with
And particle size is small, the ZrC-ZrO that is prepared2Composite ceramics microsphere surface is fine and close, internal without obvious hole, Neng Gouyou
Effect ensures ZrC-ZrO2The high density and composition of composite ceramics microballoon are uniform.
In another aspect of this invention, ZrO is prepared using inner gel technique the invention provides one kind2- ZrC composite ceramics
The method of porcelain microballoon, in the method, using sucrose as carbon source.Inventor is by many experiments and verifies repeatedly, finds to adopt
By the use of sucrose as carbon source, on the premise of interior gelatinization glue ordinary temperature stability is not influenceed carbon can be ensured in microballoon
In be uniformly distributed and particle size is small so that the ZrC-ZrO being prepared2Composite ceramics microsphere surface is fine and close, inside does not have
There is obvious hole, it is ensured that the ZrC-ZrO being prepared2The high density and composition of composite ceramics microballoon are uniform.
Embodiments of the invention are described below in detail.
Embodiment 1
By ZrO (NO3)2With Y (NO3)3Dissolving is configured to solution, wherein, ZrO (NO3)2Concentration be 1.6 mol/Ls, Y
(NO3)3Concentration is 0.14 mol/L.Hexamethylenetetramine and urea are mixed, wherein, the concentration of hexamethylenetetramine is
3 mol/Ls, the concentration of urea is 0.7 mol/L.Solution containing hexamethylenetetramine and urea is added to containing ZrO (NO3)2、
Y(NO3)3Solution in, stir while adding, while add appropriate concentrated nitric acid thereto, the glue of clear be prepared
Liquid, the pH value of the glue is 1.35.Then, appropriate polyvinyl alcohol, furfuryl alcohol, Ts-10 carbon blacks, sugarcane are added into glue respectively
Sugar, glucose and fructose are stirred to clarify as carbon source, wherein, the zr element in carbon and glue in carbon source rubs
You set the glue for being not added with carbon source as control than being 0.5.Next, at 25 DEG C, the use prepared is determined not
With the viscosity versus time curve of the glue of carbon source, Fig. 2 is as a result seen.
It has been recognised by the inventors that when the viscosity of glue is more than 60mPaS, glue is no longer appropriate for scattered shaping, and glue can not be steady
Fixed to exist, it can be seen from Fig. 2 result, under 25 degrees Celsius, using polyvinyl alcohol, furfuryl alcohol, glucose as carbon source, glue is only
It can be stabilized 2 hours or so, using fructose as carbon source, glue can be stabilized about 6 hours, and use Ts-10 charcoals
As carbon source, glue can be stabilized 14 hours or so black and sucrose, suitable with being not added with the stability of glue of carbon source, can
Meet industrial needs, the preparation and storage for realizing glue can be carried out under normal temperature condition.
Embodiment 2
According to the method in embodiment 1, prepare respectively not carbonaceous sources, using sucrose as carbon source, and C/Zr is 0.5, with sucrose
For carbon source, and C/Zr is 6, using fructose as carbon source, and C/Zr is 1 glue, at 25 DEG C, determines the viscous of the glue for preparing
Versus time curve is spent, as a result sees Fig. 3.
From the figure 3, it may be seen that using sucrose, for carbon source, the stability of the stability of glue and the glue of non-carbonaceous sources is suitable, energy
The preparation and storage for enough realizing glue are carried out at normal temperatures.And fructose is used as carbon source, for glue when fructose content is relatively low
Liquid stability influence is little, as fructose content increases so that the stability of glue drastically declines.
Embodiment 3
In this embodiment, ZrC-ZrO is prepared by following steps2Composite ceramics microballoon：
(1) by ZrO (NO3)2With Y (NO3)3Dissolving is configured to solution, wherein ZrO (NO3)2Concentration be 1.6 mol/Ls, Y
(NO3)3Concentration is 0.14 mol/L.Hexamethylenetetramine and urea are mixed, the concentration of hexamethylenetetramine is rubbed for 3
You/liter, the concentration of urea is 0.7 mol/L.Solution containing hexamethylenetetramine and urea is added to containing ZrO (NO3)2、Y
(NO3)3Solution in, stir while adding, while add appropriate concentrated nitric acid thereto, the glue of clear be prepared,
The pH value of the glue is 1.35.Appropriate sucrose is added into glue, is stirred to clarify.Sucrose (C12H22O11) addition
So that the molar ratio (hereinafter referred to as C/Zr) of sucrose institute's phosphorus content and zirconium ion in glue is 1.
(2) glue that step (1) obtains is distributed in 90 degrees Celsius of hot silicone oil, to make the glue in institute
State and gel ball is formed in silicone oil；
(3) gel ball that step (2) obtains is subjected to ripening, digestion time 0.5 hour in silicone oil；
(4) gel ball with silicone oil for obtaining step (3) carries out carrying out washing treatment.The gel ball that will be obtained after ageing
Washed 4 times using trichloro ethylene, continue at least 20 minutes every time；Then poly- four are placed in after gel ball is rinsed using absolute ethyl alcohol
The use of absolute ethyl alcohol is that solvent reacts 6 hours and makes sucrose carbon in bead at 200 degrees celsius in the reactor of PVF
Change；Then bead passes through 0.5mol/L ammonia scrubbing, and washing every time continues at least 20 minutes until the conductance of caused waste liquid
Rate is less than 800 μ S/cm；Then gel ball is continued to wash using deionized water, until the waste liquid electrical conductivity that washing obtains is less than
30 μ S/cm, finally gel ball is washed four times using propylene glycol monomethyl ether, continues at least 20 minutes every time；
(5) gel ball that step (4) obtains now is dried at room temperature for 1 hour, then in 60 degrees Celsius of drying
Drying process more than 12 hours in case；And
(6) the obtained gel ball by the drying process of step (5) is sintered, containing 5%CO's
4 hours are calcined under 1550 degrees Celsius under argon gas atmosphere to obtain the ZrC-ZrO2Composite ceramics microballoon, sintering heating are bent
Line is formulated according to the TG-DSC curves of xerogel ball, specifically, is incubated on TG-DSC curves at each heat absorption exothermic peak
0.5~1 hour.And in order to prevent microballoon from being ftractureed in sintering process, sintering process programming rate is as slow as possible, in room temperature extremely
600 centigrade per minutes heat up 0.5 degree Celsius, are heated up 1 degree Celsius in 600 to 1550 centigrade per minutes.
The ZrC-ZrO prepared2Composite ceramics microsphere surface and the SEM photograph in section are shown in Fig. 4, wherein, Fig. 4 (a), figure
4 (b) and Fig. 4 (c) are ZrC-ZrO2The SEM photograph of composite ceramics microsphere surface, Fig. 4 (d) are ZrC-ZrO2Composite ceramics microballoon is cut
The SEM photograph in face.The ceramic microsphere good sphericity being prepared, size uniformity, surface compact are able to observe that from Fig. 4, it is interior
Portion's structure is also dense, and distribution uniform inside the ceramic microsphere obtained using sucrose as carbon source, is not observed bright
Aobvious hole and bulky grain carbon residual.
Embodiment 4
Correlated process and parameter in embodiment 4 is same as Example 3, difference be sucrose in step (1) plus
Enter amount and make it that the molar ratio (hereinafter referred to as C/Zr) of institute's phosphorus content and zirconium ion in glue is 3.Other glue configuration process
In other material concentrations and follow-up scattered, ageing, washing, dry and heat treatment process is same as Example 3.
The ZrC-ZrO prepared2Composite ceramics microsphere surface and the SEM photograph in section are shown in Fig. 5, wherein, Fig. 5 (a), figure
5 (b) and Fig. 5 (c) are ZrC-ZrO2The SEM photograph of composite ceramics microsphere surface, Fig. 5 (d) are ZrC-ZrO2Composite ceramics microballoon is cut
The SEM photograph in face.Fig. 5 shows that the ceramic microsphere good sphericity being prepared, size uniformity, surface are complete, and internal structure compares
Densification, while distribution uniform inside the ceramic microsphere that is obtained using sucrose as carbon source, obvious hole and big is not observed
Granulated carbon remains.
Embodiment 5
Correlated process and parameter in embodiment 5 is same as Example 3, difference be sucrose in step (1) plus
Enter amount and make it that the molar ratio (hereinafter referred to as C/Zr) of institute's phosphorus content and zirconium ion in glue is 2.Other glue configuration process
In other material concentrations and follow-up scattered, ageing, washing, dry and heat treatment process is same as Example 3.
The ZrC-ZrO prepared2Composite ceramics microsphere surface and the SEM photograph in section are shown in Fig. 6, wherein, Fig. 6 (a), figure
6 (b) and Fig. 6 (c) are ZrC-ZrO2The SEM photograph of composite ceramics microsphere surface, Fig. 6 (d) are ZrC-ZrO2Composite ceramics microballoon is cut
The SEM photograph in face.It can also be observed that the ceramic microsphere good sphericity being prepared, size uniformity, surface are complete from Fig. 6, it is internal
Structure is dense, distribution uniform inside the ceramic microsphere obtained using sucrose as carbon source, obvious hole is not observed
Remained with bulky grain carbon.
Comparative example 1
Correlated process and parameter in comparative example 1 is same as Example 3, and difference is to add Ts-10 in step (1)
Carbon black is as carbon source, and Ts-10 carbon blacks institute's phosphorus content and the molar ratio (hereinafter referred to as C/Zr) of zirconium ion in glue are
0.5.Other material concentrations and follow-up scattered, ageing, washing in other glue configuration process, dry and heat treatment process with
Embodiment 3 is identical.
The ZrC-ZrO prepared2The SEM photograph in composite ceramics microballoon section is shown in Fig. 7.From Fig. 7 it is observed that preparing
Substantial amounts of black particle and obvious hole be present inside obtained ceramic microsphere, this acquisition for high density ceramic microballoon
It is unfavorable.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment or example of the present invention.In this manual, to the schematic representation of above-mentioned term not
Identical embodiment or example must be directed to.Moreover, specific features, structure, material or the feature of description can be with office
Combined in an appropriate manner in one or more embodiments or example.In addition, in the case of not conflicting, the skill of this area
Art personnel can be tied the different embodiments or example and the feature of different embodiments or example described in this specification
Close and combine.
Although embodiments of the invention have been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, one of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changed, replacing and modification.
Claims (10)
1. one kind prepares ZrO2The method of-ZrC composite ceramics microballoons, it is characterised in that including：
The first solution containing Zr and Y is mixed with the second solution containing hexamethylenetetramine and urea, and to resulting
Concentrated nitric acid is added in mixture, obtains glue；
Under 25~27 degrees Celsius, sucrose is added into the glue, obtains the glue containing sucrose；
The glue containing sucrose is distributed in hot silicone oil, and carries out ripening, obtains gel ball；
The gel ball is subjected to the first carrying out washing treatment, obtains the gel ball by the first washing；
The gel ball by the first washing is subjected to hydro-thermal process, obtains the gel ball by hydro-thermal process, wherein, it is described
Hydro-thermal process be using absolute ethyl alcohol as solvent, at 200 degrees celsius react 6 hours；
The gel ball by hydro-thermal process is subjected to the second carrying out washing treatment, obtains the gel ball by the second washing；
Processing is dried in the gel ball by the second washing, obtains desiccant gel ball；
The desiccant gel ball is sintered, obtains ZrO2- ZrC composite ceramics microballoons.
2. according to the method for claim 1, it is characterised in that first solution contains ZrO (NO3)2With Y (NO3)3,
In first solution, ZrO (NO3)2Concentration be 1.6~1.7 mol/Ls, Y (NO3)3Concentration is rubbed for 0.14~0.15
You/liter,
In the second solution, the concentration of the hexamethylenetetramine is 3~3.2 mol/Ls, the concentration of the urea for 0.7~
1.1 mol/Ls,
The pH value of the glue is 1~2.
3. according to the method for claim 1, it is characterised in that in the glue containing sucrose, the carbon member in sucrose
The mol ratio of zr element in plain and described glue is 0.5~6.
4. according to the method for claim 3, it is characterised in that in the glue containing sucrose, the carbon member in sucrose
The mol ratio of zr element in plain and described glue is 0.5~4.
5. according to the method for claim 1, it is characterised in that the temperature of the hot silicone oil is 85~90 degrees Celsius, described
The time of ripening is 0.5~1 hour.
6. according to the method for claim 1, it is characterised in that first carrying out washing treatment further comprises：
The gel ball is washed using trichloro ethylene 4 times, and washing every time continues at least 20 minutes；
The gel ball by trichloro ethylene washing is rinsed using absolute ethyl alcohol.
7. according to the method for claim 1, it is characterised in that the hydrothermal treatment process further comprises：
The gel ball by the first washing is placed in ptfe autoclave.
8. according to the method for claim 1, it is characterised in that second washing further comprises：
Using the gel ball described in 0.5mol/L ammonia scrubbing Jing Guo hydro-thermal process, the electrical conductivity to scrub raffinate is less than 800 μ
S/cm；
The gel ball by ammonia scrubbing is washed with deionized in profit, and the electrical conductivity to scrub raffinate is less than 30 μ S/cm；
Using gel ball four time of the propylene glycol monomethyl ether washing by deionized water washing, washing every time continues at least 20 minutes.
9. according to the method for claim 1, it is characterised in that the drying process is to be dried at room temperature for 1~2 hour,
Then dry and be not less than 12 hours under 60~80 degrees Celsius.
10. according to the method for claim 1, it is characterised in that the sintering processes are containing 5% volume fraction C O
Calcined 3~5 hours in argon gas atmosphere, under 1500~1600 degrees celsius.
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