CN105000887A - Method for preparing ZrO2-ZrC composite ceramic microsphere by utilizing sucrose as carbon source - Google Patents
Method for preparing ZrO2-ZrC composite ceramic microsphere by utilizing sucrose as carbon source Download PDFInfo
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- CN105000887A CN105000887A CN201510463391.5A CN201510463391A CN105000887A CN 105000887 A CN105000887 A CN 105000887A CN 201510463391 A CN201510463391 A CN 201510463391A CN 105000887 A CN105000887 A CN 105000887A
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- glue
- gel ball
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- sucrose
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Abstract
The invention provides a method for preparing a ZrO2-ZrC composite ceramic microsphere by utilizing sucrose as a carbon source. The method comprises the steps of preparing of a glue solution, adding of the sucrose, dispersing and seasoning treatment, first washing treatment, hydro-thermal treatment, second washing treatment, drying treatment and sintering treatment. According to the method, the ZrO2-ZrC composite ceramic microsphere can be prepared rapidly and effectively, and the glue solution can be prepared in the normal temperature and can exist stably.
Description
Technical field
The invention belongs to ceramic molding field, be specifically related to the method that interior gelatinizing process prepares ceramic microsphere, more specifically, relate to and prepare ZrO using sucrose as carbon source
2the interior gelation of-ZrC composite ceramics microballoon.
Background technology
Zirconium dioxide (ZrO
2) and zirconium carbide (ZrC) all there is low neutron capture cross section, high fusing point and chemical stability, and under radiation condition the feature such as stable, be all regarded as the inert base of reactor inert base fuel (IMF).Sol-gel technology is adopted to prepare ZrO
2the relevant report of ceramic microsphere is a lot, but adopts sol-gel method preparation substantially not have containing the report of ZrC microballoon.
Interior gelatinizing process is a kind of modern technique preparing ceramic microsphere, is widely used in high temperature gas cooled reactor fuel kernel core as UO
2, PuO
2and the preparation of inert base, and interior gelatinizing process can allow other component Uniform Dopeds to enter in bead, is applicable to non-oxidized substance as the preparation of carbide, nitride-based spheres of ceramic.But, the glue instability of interior gelatinizing process is one of subject matter of gelatinizing process large-scale application in impact always, particularly preparation is containing ZrC microballoon, need in preparation process to add carbon source, the glue stability of its internal gelatinizing process and preparation required highdensity most important containing ZrC ceramic microsphere, but, at present and have no and can be used in the preparation of inner gel technique containing ZrC ceramic microsphere and the relevant report of the comparatively ideal carbon source of performance.
Therefore, still need deeply about the research adopting the preparation of inner gel technique containing ZrC ceramic microsphere.
Summary of the invention
The present invention is intended to solve one of technical problem in correlation technique at least to a certain extent.For this reason, one object of the present invention be to propose a kind of glue at normal temperatures can the preparation ZrC-ZrO of stable existence
2the method of composite ceramics microballoon.
The present invention completes based on the following discovery of contriver:
Contriver finds in research process, ZrO
2thermal conductivity very low, is only 2 ~ 3W/m K and does not substantially change with the change of temperature, and the thermal conductivity of ZrC is 20.52W/m K at 25 DEG C, 38.5 ~ 40.6W/m K can be reached at 1300 ~ 1600 DEG C.At preparation ZrO
2add appropriate carbon source in the glue of microballoon, can obtain the microballoon containing ZrC by carbothermic reduction reaction, ZrC material is incorporated into ZrO by this process simultaneously
2be expected in matrix improve ZrO
2the heat conductivility of material, for reactor inert base fuel provides a kind of ZrC-ZrO of new great potential
2matrix material.
In view of above-mentioned discovery, inventors performed further investigation, result shows, the selection of carbon source is for the glue stability of interior gelatinizing process and the required highdensity ZrC-ZrO of preparation
2composite ceramics microballoon is most important.Because ZrC is directly by ZrO
2be obtained by reacting with the carbon of gel ball inside, if the carbon granule in gel ball is excessive or reunite, hole or unreacted carbon granule can be left at ball interior after carbothermic reduction reaction, obviously this is disadvantageous for the highdensity ceramic microsphere of acquisition, and selected carbon source needs more stable in existing glue system, carry out under making the preparation of glue and being stored in normal temperature (25 degrees centigrade), and chemical reaction do not occur and affect glue stability.
Through a large amount of explorative experiment with repeatedly verify, contriver find carbon dust and sucrose very little for the impact of glue stability as carbon source, but use carbon dust to need to ensure that particle size even less carbon dust that just can make below 5 microns reacts completely and do not leave residual carbon in carbothermic reduction process, even if the carbon powder particle size used can meet the demands, but what be difficult to when carbon dust disperses in glue to avoid there will be reunion (even being also like this when using carbon dust dispersion agent), cause particle to become large, affect the ZrC-ZrO prepared
2the composition profiles of complex microsphere and density.And experiment shows to adopt sucrose as carbon source, substantially can not produce a very large impact the stability of glue under normal temperature (25 degrees centigrade), can ensure that preparation and the storage of glue are carried out at normal temperatures, what is more important sucrose is as carbon source, can ensure carbon in microballoon be uniformly distributed and particle size little, guarantee the ZrC-ZrO prepared
2the high-density of composite ceramics microballoon and uniform composition.
In view of this, in one aspect of the invention, the invention provides one and prepare ZrO
2the method of-ZrC composite ceramics microballoon.According to embodiments of the invention, the method comprises: mixed with the second solution containing hexamethylenetetramine and urea by the first solution containing Zr and Y, and add concentrated nitric acid in obtained mixture, obtain glue; In glue, add sucrose, obtain the glue containing sucrose; Glue containing sucrose is distributed in hot silicone oil, and carries out ripening, obtain gel ball; Gel ball is carried out the first carrying out washing treatment, obtains the gel ball through the first washing; Gel ball through the first washing is carried out hydrothermal treatment consists, obtains the gel ball through hydrothermal treatment consists; Gel ball through hydrothermal treatment consists is carried out the second carrying out washing treatment, obtains the gel ball through the second washing; Gel ball through the second washing is carried out drying treatment, obtains desiccant gel ball; Desiccant gel ball is carried out sintering processes, obtains ZrO
2-ZrC composite ceramics microballoon.
Contriver finds, utilizes the method according to the embodiment of the present invention, can prepare ZrO quickly and efficiently
2-ZrC composite ceramics microballoon, and glue can be prepared and stable existence at normal temperatures, efficiently solve glue in existing inner gel technique unstable, need low temperature environment, the problem of condition harshness, special needs to be pointed out is, in the method, adopt sucrose as carbon source, substantially can not produce a very large impact the stability of glue under normal temperature (25 degrees centigrade), can ensure that preparation and the storage of glue are carried out at normal temperatures, what is more important sucrose is as carbon source, can ensure carbon in microballoon be uniformly distributed and particle size little, the ZrC-ZrO prepared
2composite ceramics microsphere surface is fine and close, inside does not have obvious hole, effectively can guarantee ZrC-ZrO
2the high-density of composite ceramics microballoon and uniform composition.
It will be understood by those skilled in the art that improving glue preparation and the temperature that stores is energy consumption in order to reduce required for cooling glue, the lower glue of temperature more stable (only otherwise freeze just).And according to the preparation ZrO of the embodiment of the present invention
2in the method for-ZrC composite ceramics microballoon, glue, not higher than in the temperature range of 27 degrees Celsius, has satisfactory stability, can meet production requirement.Therefore, described herein normal temperature (25 degrees centigrade) refers to not higher than the temperature range of 27 degrees Celsius.
According to embodiments of the invention, containing ZrO (NO in the first solution
3)
2with Y (NO
3)
3.
According to embodiments of the invention, in the first solution, ZrO (NO
3)
2concentration be 1.6 ~ 1.7 mol/L, Y (NO
3)
3concentration is 0.14 ~ 0.15 mol/L.
According to embodiments of the invention, in the second solution, the concentration of hexamethylenetetramine is 3 ~ 3.2 mol/L, and the concentration of urea is 0.7 ~ 1.1 mol/L.
According to embodiments of the invention, the pH value of glue is 1 ~ 2.
According to embodiments of the invention, containing in the glue of sucrose, the mol ratio of the carbon in sucrose and the zr element in glue is 0.5 ~ 6, preferably 0.5 ~ 4.
According to embodiments of the invention, the temperature of hot silicone oil is 85 ~ 90 degrees Celsius.
According to embodiments of the invention, the time of ripening is 0.5 ~ 1 hour.
According to embodiments of the invention, the first carrying out washing treatment comprises further: utilize trieline detergent gel ball 4 times, and each washing continues at least 20 minutes; Dehydrated alcohol is utilized to rinse the gel ball washed through trieline.
According to embodiments of the invention, hydrothermal treatment consists is washed ball process and is comprised further: the reactor gel ball through the first washing being placed in tetrafluoroethylene take dehydrated alcohol as solvent, reacts 6 hours at 200 degrees celsius.
According to embodiments of the invention, the second washing comprises further: the gel ball of ammonia scrubbing through hydrothermal treatment consists utilizing 0.5mol/L, and the specific conductivity to scrub raffinate is less than 800 μ S/cm; Utilize deionized water wash through the gel ball of ammonia scrubbing, the specific conductivity to scrub raffinate is less than 30 μ S/cm; Utilize propylene glycol monomethyl ether to wash gel ball four times through deionized water wash, each washing continues at least 20 minutes.
According to embodiments of the invention, drying treatment is at room temperature dry 1 ~ 2 hour, and then under 60 ~ 80 degrees Celsius, drying is not less than 12 hours.
According to embodiments of the invention, sintering processes is being calcined 3 ~ 5 hours containing in the argon gas atmosphere of 5% volume fraction C O, under 1500 ~ 1600 degrees celsius.
In another aspect of this invention, the invention provides a kind of inner gel technique that adopts and prepare ZrO
2the method of-ZrC composite ceramics microballoon, in the method, adopts sucrose as carbon source.Contriver is through great many of experiments and repeatedly verify, finds to adopt sucrose as carbon source, can under the prerequisite not affecting interior gelatinization process glue ordinary temperature stability, can ensure carbon in microballoon be uniformly distributed and particle size little, make the ZrC-ZrO prepared
2composite ceramics microsphere surface is fine and close, inside does not have obvious hole, guarantees the ZrC-ZrO prepared
2the high-density of composite ceramics microballoon and uniform composition.
Accompanying drawing explanation
Fig. 1 prepares ZrC-ZrO according to an embodiment of the invention
2the method flow schematic diagram of composite ceramics microballoon.
Fig. 2 is according to an embodiment of the invention containing the viscosity of glue of different carbon source curve over time at 25 DEG C.
Fig. 3 is the viscosity of the glue of different according to an embodiment of the invention sucrose content curve over time at 25 DEG C.
Fig. 4 is the ZrC-ZrO obtained when C/Zr is 1 in carbon source, glue according to an embodiment of the invention with sucrose
2the SEM photo in composite ceramics microsphere surface and cross section.
Fig. 5 is the ZrC-ZrO obtained when C/Zr is 2 in carbon source, glue according to an embodiment of the invention with sucrose
2the SEM photo in composite ceramics microsphere surface and cross section.
Fig. 6 is the ZrC-ZrO obtained when C/Zr is 3 in carbon source, glue according to an embodiment of the invention with sucrose
2the SEM photo in composite ceramics microsphere surface and cross section.
Fig. 7 is the ZrC-ZrO obtained when C/Zr is 0.5 according to an embodiment of the invention using Ts-10 carbon black as carbon source, in glue
2the SEM photo in composite ceramics microballoon cross section.
Embodiment
Embodiments of the invention are described below in detail.Embodiment described below is exemplary, only for explaining the present invention, and can not be interpreted as limitation of the present invention.Unreceipted concrete technology or condition in embodiment, according to the technology described by the document in this area or condition or carry out according to product description.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercial acquisition.
In one aspect of the invention, the invention provides one and prepare ZrO
2the method of-ZrC composite ceramics microballoon.According to embodiments of the invention, with reference to Fig. 1, the method comprises the following steps:
S100: the first solution containing Zr and Y is mixed with the second solution containing hexamethylenetetramine and urea, and add concentrated nitric acid in obtained mixture, obtain glue.
According to embodiments of the invention, containing ZrO (NO in the first solution
3)
2with Y (NO
3)
3.In other words, ZrO (NO can be utilized
3)
2with Y (NO
3)
3be mixed with the first solution.In some embodiments of the invention, in the first solution, ZrO (NO
3)
2concentration be 1.6 ~ 1.7 mol/L, Y (NO
3)
3concentration is 0.14 ~ 0.15 mol/L.Thereby, it is possible to make glue prepare under normal temperature condition, avoid the severe condition of low temperature, its obtained glue can stable existence at normal temperatures, if ZrO is (NO
3)
2with Y (NO
3)
3excessive concentration or too low, all do not reach above-mentioned glue and can prepare at normal temperatures and the effect of stable existence.
According to embodiments of the invention, in the second solution, the concentration of hexamethylenetetramine is 3 ~ 3.2 mol/L, and the concentration of urea is 0.7 ~ 1.1 mol/L.Thus, glue can be made to prepare under normal temperature condition, avoid the severe condition of low temperature, its obtained glue can stable existence at normal temperatures, if the excessive concentration of hexamethylenetetramine and urea or too low, all do not reach above-mentioned glue and can prepare at normal temperatures and the effect of stable existence.
According to embodiments of the invention, the pH value of glue can be 1 ~ 2.Thus, be conducive to improving the stability of glue under normal temperature condition.
Specifically, can comprise in this step: by ZrO (NO
3)
2with Y (NO
3)
3dissolving is mixed with solution, wherein ZrO (NO
3)
2concentration be 1.6 ~ 1.7 mol/L, Y (NO
3)
3concentration is 0.14 ~ 0.15 mol/L, then, hexamethylenetetramine and urea is mixed, and wherein, the concentration of hexamethylenetetramine is 3 ~ 3.2 mol/L, and the concentration of urea is 0.7 ~ 1.1 mol/L.The above-mentioned solution containing hexamethylenetetramine and urea is joined containing ZrO (NO
3)
2, Y (NO
3)
3solution in, stir while adding, simultaneously add appropriate concentrated nitric acid wherein, prepare the glue of clear, the pH value of glue is 1 ~ 2.Preparation and the storage of glue are all carried out under normal temperature condition, and glue has satisfactory stability, can in long-time storage under normal temperature condition.
S200: add sucrose in glue, obtains the glue containing sucrose.
According to embodiments of the invention, containing in the glue of sucrose, the mol ratio of the carbon in sucrose and the zr element in glue is 0.5 ~ 6, under preferable case, and the mol ratio of the carbon in sucrose and the zr element in glue is 0.5 ~ 4.Contriver finds through a large amount of explorative experiment, be surprised to find that the sucrose adopted in this proportional range is as carbon source, can under the condition of ordinary temperature stability not affecting glue, make carbon in microballoon be uniformly distributed and particle size little, the ZrC-ZrO prepared
2composite ceramics microsphere surface is fine and close, inside does not have obvious hole, effectively can guarantee ZrC-ZrO
2the high-density of composite ceramics microballoon and uniform composition.
Specifically, can comprise in this step: in the glue that above-mentioned steps prepares, add appropriate sucrose, stir to clarify, sucrose (C
12h
22o
11) add-on make the molar ratio (hereinafter referred to as C/Zr) of zirconium ion in sucrose institute's carbon content and glue between 0.5 ~ 6, be between 0.5 ~ 4 under preferable case.Sucrose is added in glue as carbon source, does not affect glue stability at normal temperatures, and be conducive to the ZrO that carbon preparing
2be uniformly distributed in-ZrC composite ceramics microballoon and particle size little, make ZrC-ZrO
2composite ceramics microsphere surface is fine and close, inside does not have obvious hole, guarantees the ZrC-ZrO prepared
2the high-density of composite ceramics microballoon and uniform composition.
S300: the glue containing sucrose is distributed in hot silicone oil, and carry out ripening, obtain gel ball.
According to embodiments of the invention, the temperature of hot silicone oil can be 85 ~ 90 degrees Celsius.Thus, be conducive to the dispersing property improving glue, be conducive to the gel ball forming size uniform.
According to embodiments of the invention, the time of ripening is 0.5 ~ 1 hour.Thus, the gel ball that forming property is desirable is conducive to.
S400: gel ball is carried out the first carrying out washing treatment, obtains the gel ball through the first washing.
According to embodiments of the invention, the first carrying out washing treatment can comprise: utilize trieline detergent gel ball 4 times, and each washing continues at least 20 minutes, then utilizes dehydrated alcohol to rinse the gel ball washed through trieline.Thereby, it is possible to effectively remove the residual silicone oil on gel ball surface, in subsequent step, do not introduce impurity, be conducive to the carrying out of subsequent step.
S500: the gel ball through the first washing is carried out hydrothermal treatment consists, obtains the gel ball through hydrothermal treatment consists.
According to embodiments of the invention, hydrothermal treatment process can comprise: the gel ball through the first washing is placed in tetrafluoroethylene reactor (hydro-thermal reaction device, liner is tetrafluoroethylene) in, take dehydrated alcohol as solvent, react 6 hours at 200 degrees celsius.Thereby, it is possible to effectively make the sucrose carbonization in gel ball, and carbon is evenly distributed in gel ball, particle size is little.
S600: the gel ball through carbothermic reduction is carried out the second carrying out washing treatment, obtains the gel ball through the second washing.
According to embodiments of the invention, the second washing may further include: the gel ball of ammonia scrubbing through carbothermic reduction utilizing 0.5mol/L, and the specific conductivity to scrub raffinate is less than 800 μ S/cm; Then utilize deionized water wash through the gel ball of ammonia scrubbing, the specific conductivity to scrub raffinate is less than 30 μ S/cm; Then utilize propylene glycol monomethyl ether to wash gel ball four times through deionized water wash, each washing continues at least 20 minutes.Thereby, it is possible to effectively remove residual reaction solution and other impurity on gel ball surface.
S700: the gel ball through the second washing is carried out drying treatment, obtains desiccant gel ball.
According to embodiments of the invention, drying treatment is at room temperature dry 1 ~ 2 hour, and then under 60 ~ 80 degrees Celsius, drying is not less than 12 hours.
S800: desiccant gel ball is carried out sintering processes, obtains ZrO
2-ZrC composite ceramics microballoon.
According to embodiments of the invention, sintering processes is being calcined 3 ~ 5 hours containing in the argon gas atmosphere of 5% volume CO, under 1500 ~ 1600 degrees celsius.In this step, sintering heating curve can be formulated according to the TG-DSC curve of desiccant gel ball, specifically, and each heat absorption exothermic peak place insulation 0.5 ~ 1 hour on TG-DSC curve.And in order to prevent microballoon from ftractureing in sintering process, sintering process heat-up rate is slow as far as possible, heats up 0.5 degree Celsius, heat up 1 degree Celsius at 600 to 1600 centigrade per minutes at room temperature to 600 centigrade per minute.
Contriver finds, utilizes the method according to the embodiment of the present invention, can prepare ZrO quickly and efficiently
2-ZrC composite ceramics microballoon, and glue can be prepared and stable existence at normal temperatures, efficiently solve glue in existing inner gel technique unstable, need low temperature environment, the problem of severe condition, special needs to be pointed out is, in the method, adopt sucrose as carbon source, substantially can not produce a very large impact the stability of glue under normal temperature (25 degrees centigrade), can ensure that preparation and the storage of glue are carried out at normal temperatures, what is more important sucrose is as carbon source, can ensure carbon in microballoon be uniformly distributed and particle size little, the ZrC-ZrO prepared
2composite ceramics microsphere surface is fine and close, inside does not have obvious hole, effectively can guarantee ZrC-ZrO
2the high-density of composite ceramics microballoon and uniform composition.
In another aspect of this invention, the invention provides a kind of inner gel technique that adopts and prepare ZrO
2the method of-ZrC composite ceramics microballoon, in the method, adopts sucrose as carbon source.Contriver is through great many of experiments and repeatedly verify, finds to adopt sucrose as carbon source, can under the prerequisite not affecting interior gelatinization process glue ordinary temperature stability, can ensure carbon in microballoon be uniformly distributed and particle size little, make the ZrC-ZrO prepared
2composite ceramics microsphere surface is fine and close, inside does not have obvious hole, guarantees the ZrC-ZrO prepared
2the high-density of composite ceramics microballoon and uniform composition.
Embodiments of the invention are described below in detail.
Embodiment 1
By ZrO (NO
3)
2with Y (NO
3)
3dissolving is mixed with solution, wherein, and ZrO (NO
3)
2concentration be 1.6 mol/L, Y (NO
3)
3concentration is 0.14 mol/L.Hexamethylenetetramine and urea are mixed, wherein, the concentration of hexamethylenetetramine is 3 mol/L, and the concentration of urea is 0.7 mol/L.Solution containing hexamethylenetetramine and urea is joined containing ZrO (NO
3)
2, Y (NO
3)
3solution in, stir while adding, simultaneously add appropriate concentrated nitric acid wherein, prepare the glue of clear, the pH value of described glue is 1.35.Then, respectively to adding appropriate polyvinyl alcohol, furfuryl alcohol, Ts-10 carbon black, sucrose, glucose and fructose in glue as carbon source, stir to clarify, wherein, the mol ratio of the carbon in carbon source and the zr element in glue is 0.5, arrange simultaneously do not add carbon source glue in contrast.Next, at 25 DEG C, measure the viscosity curve over time of the glue of the employing different carbon source prepared, the results are shown in Figure 2.
Contriver thinks, when the viscosity of glue is more than 60mPaS, it is shaping that glue is no longer applicable to dispersion, and glue can not stable existence, according to the result of Fig. 2, under 25 degrees Celsius, adopt polyvinyl alcohol, furfuryl alcohol, glucose is as carbon source, glue can only stable existence 2 hours, adopt fructose as carbon source, glue can about 6 hours of stable existence, and adopt Ts-10 carbon black and sucrose as carbon source, glue can stable existence 14 hours, suitable with the stability of the glue not adding carbon source, industrial needs can be met, realize the preparation of glue and store and can carry out under normal temperature condition.
Embodiment 2
According to the method in embodiment 1, prepare respectively not carbonaceous sources, be carbon source with sucrose, and C/Zr is 0.5, take sucrose as carbon source, and C/Zr is 6, take fructose as carbon source, and C/Zr is the glue of 1, at 25 DEG C, measure the viscosity curve over time of the glue prepared, the results are shown in Figure 3.
As shown in Figure 3, employing sucrose is carbon source, and the stability of the stability of glue and the glue of non-carbonaceous sources is suitable, and preparation and the storage that can realize glue are carried out all at normal temperatures.And adopt fructose as carbon source, and little for glue stability influence when fructose content is lower, along with fructose content increases, the stability of glue is sharply declined.
Embodiment 3
In this embodiment, ZrC-ZrO is prepared by following steps
2composite ceramics microballoon:
(1) by ZrO (NO
3)
2with Y (NO
3)
3dissolving is mixed with solution, wherein ZrO (NO
3)
2concentration be 1.6 mol/L, Y (NO
3)
3concentration is 0.14 mol/L.Hexamethylenetetramine and urea are mixed, the concentration of hexamethylenetetramine is 3 mol/L, and the concentration of urea is 0.7 mol/L.Solution containing hexamethylenetetramine and urea is joined containing ZrO (NO
3)
2, Y (NO
3)
3solution in, stir while adding, simultaneously add appropriate concentrated nitric acid wherein, prepare the glue of clear, the pH value of described glue is 1.35.In glue, add appropriate sucrose, stir to clarify.Sucrose (C
12h
22o
11) add-on make the molar ratio (hereinafter referred to as C/Zr) of zirconium ion in sucrose institute's carbon content and glue be 1.
(2) the described glue that step (1) obtains is distributed in the hot silicone oil of 90 degrees Celsius, to make described glue form gel ball in described silicone oil;
(3) the described gel ball that step (2) obtains is carried out ripening in silicone oil, digestion time 0.5 hour;
(4) gel ball with silicone oil step (3) obtained carries out carrying out washing treatment.Adopt trieline to wash 4 times the gel ball obtained after ageing, continue at least 20 minutes at every turn; Then being used by gel ball dehydrated alcohol to rinse is placed in the reactor of tetrafluoroethylene, uses dehydrated alcohol to react the sucrose carbonization made for 6 hours in bead at 200 degrees celsius for solvent; Then bead is through the ammonia scrubbing of 0.5mol/L, and each washing continues at least 20 minutes until the specific conductivity of the waste liquid produced is less than 800 μ S/cm; Then adopt deionized water to continue washing to gel ball, until wash the waste liquid specific conductivity obtained to be less than 30 μ S/cm, finally use propylene glycol monomethyl ether to wash four times to gel ball, continue at least 20 minutes at every turn;
(5) described gel ball step (4) obtained now at room temperature dry 1 hour, then drying treatment more than 12 hours in the loft drier of 60 degrees Celsius; And
(6) gel ball through described drying treatment obtained of step (5) is carried out sintering processes, under containing the argon gas atmosphere of 5%CO, under 1550 degrees Celsius, calcine 4 hours to obtain described ZrC-ZrO
2composite ceramics microballoon, sintering heating curve is formulated according to the TG-DSC curve of xerogel ball, specifically, each heat absorption exothermic peak place insulation 0.5 ~ 1 hour on TG-DSC curve.And in order to prevent microballoon from ftractureing in sintering process, sintering process heat-up rate is slow as far as possible, heats up 0.5 degree Celsius, heat up 1 degree Celsius at 600 to 1550 centigrade per minutes at room temperature to 600 centigrade per minute.
The ZrC-ZrO prepared
2fig. 4 is shown in by the SEM photo in composite ceramics microsphere surface and cross section, and wherein, Fig. 4 (a), Fig. 4 (b) and Fig. 4 (c) are ZrC-ZrO
2the SEM photo of composite ceramics microsphere surface, Fig. 4 (d) is ZrC-ZrO
2the SEM photo in composite ceramics microballoon cross section.The ceramic microsphere good sphericity, size uniformity, the surface compact that prepare can be observed from Fig. 4, internal structure is also dense, and the inner distribution uniform of the ceramic microsphere to obtain using sucrose as carbon source, do not observe obvious hole and macrobead carbon remains.
Embodiment 4
Correlated process in embodiment 4 is identical with embodiment 3 with parameter, and difference is that the add-on of sucrose in step (1) makes the molar ratio (hereinafter referred to as C/Zr) of zirconium ion in institute's carbon content and glue be 3.In other glue layoutprocedures other material concentrations and follow-up dispersion, ageing, washing, drying and heat treatment process identical with embodiment 3.
The ZrC-ZrO prepared
2fig. 5 is shown in by the SEM photo in composite ceramics microsphere surface and cross section, and wherein, Fig. 5 (a), Fig. 5 (b) and Fig. 5 (c) are ZrC-ZrO
2the SEM photo of composite ceramics microsphere surface, Fig. 5 (d) is ZrC-ZrO
2the SEM photo in composite ceramics microballoon cross section.It is complete that Fig. 5 shows the ceramic microsphere good sphericity, size uniformity, the surface that prepare, and internal structure is dense, and the inner distribution uniform of the ceramic microsphere simultaneously obtained using sucrose as carbon source, does not observe obvious hole and macrobead carbon is residual.
Embodiment 5
Correlated process in embodiment 5 is identical with embodiment 3 with parameter, and difference is that the add-on of sucrose in step (1) makes the molar ratio (hereinafter referred to as C/Zr) of zirconium ion in institute's carbon content and glue be 2.In other glue layoutprocedures other material concentrations and follow-up dispersion, ageing, washing, drying and heat treatment process identical with embodiment 3.
The ZrC-ZrO prepared
2fig. 6 is shown in by the SEM photo in composite ceramics microsphere surface and cross section, and wherein, Fig. 6 (a), Fig. 6 (b) and Fig. 6 (c) are ZrC-ZrO
2the SEM photo of composite ceramics microsphere surface, Fig. 6 (d) is ZrC-ZrO
2the SEM photo in composite ceramics microballoon cross section.Also can observe from Fig. 6 the ceramic microsphere good sphericity, size uniformity, the surface that prepare complete, internal structure is dense, and the inner distribution uniform of the ceramic microsphere that obtains using sucrose as carbon source, does not observe obvious hole and macrobead carbon is residual.
Comparative example 1
Correlated process in comparative example 1 is identical with embodiment 3 with parameter, difference is to add Ts-10 carbon black as carbon source in step (1), and in Ts-10 carbon black institute's carbon content and glue, the molar ratio (hereinafter referred to as C/Zr) of zirconium ion is 0.5.In other glue layoutprocedures other material concentrations and follow-up dispersion, ageing, washing, drying and heat treatment process identical with embodiment 3.
The ZrC-ZrO prepared
2fig. 7 is shown in by the SEM photo in composite ceramics microballoon cross section.Can observe from Fig. 7 the ceramic microsphere inside prepared and there is a large amount of black particles and obvious hole, this acquisition for high density ceramic microballoon is disadvantageous.
In the description of this specification sheets, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not must for be identical embodiment or example.And the specific features of description, structure, material or feature can combine in one or more embodiment in office or example in an appropriate manner.In addition, when not conflicting, the feature of the different embodiment described in this specification sheets or example and different embodiment or example can carry out combining and combining by those skilled in the art.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, and those of ordinary skill in the art can change above-described embodiment within the scope of the invention, revises, replace and modification.
Claims (10)
1. prepare ZrO for one kind
2the method of-ZrC composite ceramics microballoon, is characterized in that, comprising:
The first solution containing Zr and Y is mixed with the second solution containing hexamethylenetetramine and urea, and add concentrated nitric acid in obtained mixture, obtain glue;
In described glue, add sucrose, obtain the glue containing sucrose;
The described glue containing sucrose is distributed in hot silicone oil, and carries out ripening, obtain gel ball;
Described gel ball is carried out the first carrying out washing treatment, obtains the gel ball through the first washing;
The described gel ball through the first washing is carried out hydrothermal treatment consists, obtains the gel ball through hydrothermal treatment consists;
The described gel ball through hydrothermal treatment consists is carried out the second carrying out washing treatment, obtains the gel ball through the second washing;
The described gel ball through the second washing is carried out drying treatment, obtains desiccant gel ball;
Described desiccant gel ball is carried out sintering processes, obtains ZrO
2-ZrC composite ceramics microballoon.
2. method according to claim 1, is characterized in that, described first solution contains ZrO (NO
3)
2with Y (NO
3)
3,
Preferably, in described first solution, ZrO (NO
3)
2concentration be 1.6 ~ 1.7 mol/L, Y (NO
3)
3concentration is 0.14 ~ 0.15 mol/L,
Optionally, in the second solution, the concentration of described hexamethylenetetramine is 3 ~ 3.2 mol/L, and the concentration of described urea is 0.7 ~ 1.1 mol/L,
Optionally, the pH value of described glue is 1 ~ 2.
3. method according to claim 1, is characterized in that, in the described glue containing sucrose, the mol ratio of the zr element in the carbon in sucrose and described glue is 0.5 ~ 6, preferably 0.5 ~ 4.
4. method according to claim 1, is characterized in that, the temperature of described hot silicone oil is 85 ~ 90 degrees Celsius, and the time of described ripening is 0.5 ~ 1 hour.
5. method according to claim 1, is characterized in that, described first carrying out washing treatment comprises further:
Utilize trieline to wash described gel ball 4 times, each washing continues at least 20 minutes;
Dehydrated alcohol is utilized to rinse the gel ball washed through trieline.
6. method according to claim 1, is characterized in that, described hydrothermal treatment process comprises further:
The described gel ball through the first washing is placed in tetrafluoroethylene reactor, take dehydrated alcohol as solvent, react 6 hours at 200 degrees celsius.
7. method according to claim 1, is characterized in that, described second washing comprises further:
Through the gel ball of carbothermic reduction described in the ammonia scrubbing utilizing 0.5mol/L, the specific conductivity to scrub raffinate is less than 800 μ S/cm;
Utilize deionized water wash through the gel ball of ammonia scrubbing, the specific conductivity to scrub raffinate is less than 30 μ S/cm;
Utilize propylene glycol monomethyl ether to wash gel ball four times through deionized water wash, each washing continues at least 20 minutes.
8. method according to claim 1, is characterized in that, described drying treatment is at room temperature dry 1 ~ 2 hour, and then under 60 ~ 80 degrees Celsius, drying is not less than 12 hours.
9. method according to claim 1, is characterized in that, described sintering processes is being calcined 3 ~ 5 hours containing in the argon gas atmosphere of 5% volume fraction C O, under 1500 ~ 1600 degrees celsius.
10. one kind adopts inner gel technique to prepare ZrO
2the method of-ZrC composite ceramics microballoon, is characterized in that, adopts sucrose as carbon source.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753487A (en) * | 2016-03-01 | 2016-07-13 | 中钢集团洛阳耐火材料研究院有限公司 | Composite powder for improving scouring resistance of carbon-containing refractory material and preparation method of composite powder |
| CN108840683A (en) * | 2018-07-05 | 2018-11-20 | 清华大学 | It is used to prepare the technique and zirconium nitride ceramic microsphere of zirconium nitride ceramic microsphere |
| CN109824359A (en) * | 2019-04-19 | 2019-05-31 | 中铂传感器(太仓)有限公司 | A kind of Sol-gel Coated modified zirconia ceramic material and preparation method thereof |
| CN111960824A (en) * | 2020-08-11 | 2020-11-20 | 清华大学 | Ceramic microsphere and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003715A (en) * | 2014-05-19 | 2014-08-27 | 清华大学 | ZrC-ZrO2 composite ceramic microsphere and preparation method thereof |
| CN104671797A (en) * | 2015-02-09 | 2015-06-03 | 清华大学 | Internal gelation method for ceramic microspheres capable of keeping gel solution steady at normal temperature |
-
2015
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003715A (en) * | 2014-05-19 | 2014-08-27 | 清华大学 | ZrC-ZrO2 composite ceramic microsphere and preparation method thereof |
| CN104671797A (en) * | 2015-02-09 | 2015-06-03 | 清华大学 | Internal gelation method for ceramic microspheres capable of keeping gel solution steady at normal temperature |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105753487A (en) * | 2016-03-01 | 2016-07-13 | 中钢集团洛阳耐火材料研究院有限公司 | Composite powder for improving scouring resistance of carbon-containing refractory material and preparation method of composite powder |
| CN108840683A (en) * | 2018-07-05 | 2018-11-20 | 清华大学 | It is used to prepare the technique and zirconium nitride ceramic microsphere of zirconium nitride ceramic microsphere |
| CN108840683B (en) * | 2018-07-05 | 2020-07-28 | 清华大学 | Process for preparing zirconium nitride ceramic microspheres and zirconium nitride ceramic microspheres |
| CN109824359A (en) * | 2019-04-19 | 2019-05-31 | 中铂传感器(太仓)有限公司 | A kind of Sol-gel Coated modified zirconia ceramic material and preparation method thereof |
| CN111960824A (en) * | 2020-08-11 | 2020-11-20 | 清华大学 | Ceramic microsphere and preparation method thereof |
| CN111960824B (en) * | 2020-08-11 | 2021-09-24 | 清华大学 | Ceramic microsphere and preparation method thereof |
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