CN109776089A - A kind of CaCu 3 Ti 4 O base ceramic material and preparation method thereof - Google Patents
A kind of CaCu 3 Ti 4 O base ceramic material and preparation method thereof Download PDFInfo
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Abstract
A kind of CaCu 3 Ti 4 O base ceramic material and preparation method thereof, belongs to ceramic material and preparation technical field.The chemical composition and crystal phase of the ceramic material are Ca1-xLaxCu3-yCoyTi4O12, wherein 0 ﹤ x≤0.05,0 y≤0.6 ﹤ are prepared ceramic forerunner powder using sol-gel method, are then made through granulation, pre-burning, sintering processes, the crystal phase of material is CaCu Ti4O12Phase has no miscellaneous phase generation, crystal grain homoepitaxial, consistency height.The present invention is maintaining higher dielectric to significantly reduce the loss of material low-frequency dielectric by La and Co codope, and overcoming the conventionally employed high insulating ceramics of doping reduces the deficiency that existing dielectric constant reduces；Preparation method of the present invention makes reactant reach the mixing of molecular level, crystallization temperature is also reduced while improving the doping of conventional solid raw material and there are problems that grain size distribution is unevenly even reunited, and raw material is cheap and easy to get, reacted constituent is controllable, simple process, it is at low cost, solution is provided for production large bulk capacitance component.
Description
Technical field
The invention belongs to ceramic material and preparation technical fields, and in particular to a kind of CaCu 3 Ti 4 O base ceramic material and its system
Preparation Method.
Background technique
Core of the electronic technology as modern technologies, development are ceased with the miniaturization of electronic device, highly integrated process breath
It is related.Bulky capacitor is always a key factor for influencing integrated circuit integrated level, and design or sacrifice for bulky capacitor
Integrated level and use larger area or face dielectric thickness reduce bring electrostatic breakdown problem.Therefore, high dielectric is found
Constant, the dielectric material of high thermal stability are the major issues that electronic component develops urgent need to resolve.CaCu3Ti4O12Ceramic material
Expect (hereinafter referred to as CCTO) because dielectric constant huge (room temperature is up to 105More than), and with fairly good temperature stability and
Frequency stability, while it also shows the same current-voltage nonlinear characteristics of same zinc oxide pressure-sensitive ceramic, is expected to it
It is widely used on Future high-density information storage component, high dielectric capacitor and pressure-sensitive component.But CCTO makes pottery
The huge dielectric constant of porcelain is all lost along with height, and then device heating is caused seriously to influence to use, this is also that current limitation is somebody's turn to do
The main reason for material can not be applied on a large scale.Therefore, under conditions of guaranteeing the high dielectric constant of CCTO ceramic material, how
Reducing its dielectric loss, it is very important.
Researcher speculates that the dielectric properties of CCTO ceramics are influenced by material microstructure, the crystallization degree with material,
Crystal grain arrangement mode and intercrystalline transmission mechanism are closely related.Major part researcher thinks the high dielectric property of CCTO ceramics at present
Matter originates from internal barriers capacity effect (Internal Barrier Layer Capacitance, IBLC), makes pottery in CCTO
Semiconductor grain and insulating crystal boundary inside porcelain form a large amount of barrier-layer capacitys.According to this origin mechanism, CCTO ceramics
The dielectric constant size of low-frequency range is mainly related with ceramic crystalline grain size, and the dielectric loss of the ceramics at low frequency mainly determines
In grain boundary resistance.Therefore the insulating properties for increasing crystal boundary is to reduce the effective way of CCTO ceramic dielectric loss.
CCTO ceramics have perovskite-like structure, are easier to realize ionic compartmentation doping, a large amount of research all collects at this stage
In in the dielectric properties for further improving CCTO ceramics by element doping, to develop the CCTO base with application value
Giant dielectric ceramic material.Such as single element doping Al, Mg and Sr etc., rare earth doped such as La, Nd, Eu and Yb, dual element
Adulterate such as Cr+La and Sm+Mg and CaTiO3、Al2O3、SiO2And the insulating properties such as glass are compound doped.But these doping institutes
The result of acquisition is still ideal not to the utmost, has the following problems not solving still:
(1) grain boundary resistance is increased by adulterating high insulating ceramics, but dielectric constant reduces when the increase of crystal boundary thickness；
(2) element for being doped with Grain Refinement Effect inhibits crystal grain to grow up, but also influences crystal boundary thickness and generate electrostatic
Breakdown.
To sum up, the research in relation to CCTO ceramic dielectric performance needs to develop more efficiently approach, to obtain while have
There is the CCTO dielectric ceramic of high dielectric constant and low-dielectric loss, provides scheme for the application of its industrialization.
Summary of the invention
For doped chemical in the prior art reduce CCTO ceramic dielectric loss while dielectric constant also decrease with
And the problem of breakdown easy to produce static electricity, the present invention provides a kind of to make pottery with the CaCu 3 Ti 4 O base of huge dielectric constant and low-dielectric loss
Ceramic material and preparation method thereof.
To solve the above-mentioned problems, the present invention adopts the following technical scheme:
A kind of CaCu 3 Ti 4 O base ceramic material, which is characterized in that the chemical composition and crystal phase of ceramic material are Ca1- xLaxCu3-yCoyTi4O12, wherein 0 ﹤ x≤0.05,0 y≤0.6 ﹤.
Further, ceramic forerunner powder is prepared using sol-gel method in the ceramic material, then through making
Grain, pre-burning, sintering processes are made.
A kind of preparation method of CaCu 3 Ti 4 O base ceramic material, which comprises the steps of:
Step A: according to Ca1-xLaxCu3-yCoyTi4O12, wherein 0 ﹤ x≤0.05, the stoichiometric ratio ingredient of 0 y≤0.6 ﹤,
Raw material includes: inorganic metal calcium salt, inorganic metal lanthanum salt, inorganic metal mantoquita, inorganic metal cobalt salt and butyl titanate；By nothing
Machine metal calcium salt, inorganic metal lanthanum salt, inorganic metal mantoquita and inorganic metal salt solubility form inorganic metal salt in a solvent
Butyl titanate dissolution is formed solution of tetrabutyl titanate in a solvent, complexing agent dissolution is formed in a solvent by mixed solution
Enveloping agent solution, wherein the mole ratio of metal cation integral molar quantity and complexing agent is 1: 1；Then by solution of tetrabutyl titanate
It is added in enveloping agent solution and obtains mixed solution, then inorganic metal mixed salt solution is added in the mixed solution, mix
It closes uniformly, forms colloidal sol；It handles the drying sol to obtain gel, the gel is fired and pulverizes to obtain
Ceramic forerunner powder；
Step B: the titanium is so far made through granulation, pre-burning, sintering processes in the ceramic forerunner powder that step A is obtained
Sour copper calcium base ceramic material.Further, the solvent is dehydrated alcohol, the inorganic metal calcium salt, inorganic metal lanthanum salt, nothing
Machine copper salt, inorganic metal cobalt salt anion be nitrate anion.
Further, heating water bath is needed when forming colloidal sol, bath temperature is preferably 80 DEG C, guarantees to fill when heating water bath
Reaction is divided to be mixed using agitating mode, mixing time is 2~8 hours.
Further, when forming gel the drying process be specifically dry 6 under the conditions of colloidal sol is placed in 70~100 DEG C~
18 hours.
Further, it is specifically pre- under the conditions of xerogel is placed in 600~900 DEG C for firing when forming ceramic forerunner powder
It burns 2~4 hours.
Further, the granulation processing is specifically to use poly-vinyl alcohol solution, it is preferable that the poly-vinyl alcohol solution
Mass fraction is 5%.
It further, further include compression moulding after sieving before progress pre-burning after the completion of granulation.
Further, the preheating is specifically and is sintered 0.5~2 hour in 500~800 DEG C in air atmosphere.
It further, further include dumping processing, i.e. natural cooling after the completion of pre-burning before being sintered after the completion of pre-burning
To room temperature.
Further, the sintering processes be specifically in air atmosphere in 950~1200 DEG C calcine 6~15 hours, so
Cooled to room temperature afterwards.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention is maintaining higher dielectric to significantly reduce the loss of material low-frequency dielectric, phase by La and Co codope
Insulating ceramics higher than conventionally employed doping is to increase grain boundary resistance and then reduces the means of Frequency Power Loss, Ca proposed by the invention1- xLaxCu3-yCoyTi4O12Due to the interaction of La and Co in (0 ﹤ x≤0.05,0 y≤0.6 ﹤) ceramic systems, overcome due to
Increase the deficiency that the brought dielectric constant of crystal boundary thickness reduces.The crystal phase of ceramic material of the present invention is CaCuTi4O12Phase has no miscellaneous
It mutually generates, crystal grain homoepitaxial, so the dielectric constant of material maintains higher level, while the doping of La can reduce high frequency
Dielectric loss, and the compactness of material is promoted, and the dielectric loss of material integrally decreases.The present invention is production large capacity electricity
Hold component and provides solution.
(2) present invention prepares Ca using sol-gel method1-xLaxCu3-yCoyTi4O12Ceramic material compares conventional solid
Reaction method sol-gel method enables to reactant to reach the mixing of molecular level, obtains the distribution of ceramic forerunner diameter of particle
Uniformly, be on the one hand conducive to the promotion of ceramic dielectric performance；On the other hand improving Solid raw materials doping, there are crystallite dimensions point
The problem of cloth is unevenly even reunited, while the defect for unevenly needing to be sintered under the high temperature conditions due to raw material is also overcomed,
Crystallization temperature is relatively low；In addition, ingredient is controllable in reaction process, be conducive to the generation for avoiding miscellaneous phase, technical process is simple, work
The skill period is short.
(3) calcium nitrate used in present invention ceramics, copper nitrate, the raw material sources such as cobalt nitrate and lanthanum nitrate are abundant, and price is low
It is honest and clean, be conducive to the reduction of production cost.
Detailed description of the invention
Fig. 1 is the XRD diagram that ceramic material is made in embodiment 1 to embodiment 4.
Fig. 2 is that the dielectric constant of ceramic material is made with frequency variation curve in embodiment 1 to embodiment 4.
Fig. 3 is that the dielectric loss of ceramic material is made with frequency variation curve in embodiment 1 to embodiment 4.
Fig. 4 is the SEM figure that ceramic material is made in embodiment 1 and embodiment 5.
Fig. 5 is that the dielectric constant of ceramic material is made with frequency variation curve in embodiment 2 and embodiment 4 to embodiment 6.
Fig. 6 is that the dielectric loss of ceramic material is made with frequency variation curve in embodiment 2 and embodiment 4 to embodiment 6.
Fig. 7 is that the dielectric constant of ceramic material is made with frequency variation curve in embodiment 6 to embodiment 11.
Specific embodiment
In order to enable one of ordinary skill in the art can more understand the present invention program and principle, with reference to the accompanying drawing and have
Body embodiment is described in detail.The contents of the present invention are not limited to any specific embodiment, and also not representing is most preferred embodiment,
General substitution well-known to those skilled in the art is also encompassed within the scope of the invention.
Embodiment:
Embodiment 1:
The present embodiment provides a kind of CaCu3Ti4O12The preparation method of ceramic material, the specific steps are as follows:
Step A: according to CaCu3Ti4O12Stoichiometric ratio accurate weighing calcium nitrate 1.1808g, copper nitrate 3.624g and
Butyl titanate 6.8072g, according still further to citric acid: metal cation=1: 1 molar ratio weighs citric acid 8.4056g, will be above-mentioned
Nitrate, which is completely dissolved in 50ml dehydrated alcohol, forms nitrate mixed solution, while butyl titanate and citric acid being dissolved in
Suspension is formed in 200ml dehydrated alcohol.Nitrate mixed solution is injected in suspension and is slowly stirred to being uniformly mixed, is set
In extremely forming blue sol within stirred in water bath 6 hours at 80 DEG C, blue sol is placed in in 100 DEG C of baking oven dry 12 hours shapes
At blue-green xerogel, by xerogel, with furnace cooled to room temperature, (heating is fast after pre-burning 2 hours at 750 DEG C in Muffle furnace
Degree is 3 DEG C/min) to get the CaCu for arriving black3Ti4O12Ceramic forerunner powder；
Step B: by CaCu3Ti4O12Ceramic forerunner powder is ground uniformly in mortar, and the poly- second of mass fraction 5% is added
Enolate solution continues to grind, and crosses 120 meshes and is granulated, and it is 13mm that diameter is pressed under the pressure of 20MPa, with a thickness of 1.3mm circle
Sheet element embryo.The plain embryo is placed in Muffle furnace, and 600 DEG C of cooled to room temperatures after sintering 1 hour are arranged in air atmosphere
Glue (heating rate be 3 DEG C/min), cooled to room temperature after then calcine 12 hours at 1100 DEG C (heating rate for 5 DEG C/
Min), CaCu is obtained3Ti4O12Ceramics sample.
To CaCu made from the present embodiment3Ti4O12Ceramic disks are polished, and are then respectively coated in upper and lower surface
Silver paste is dried for 200 DEG C in drying box, is then heated up under air atmosphere in Muffle furnace with the speed of 3 DEG C/min for heat preservation 3 minutes
To 580 DEG C, it is sintered at 580 DEG C and cools to room temperature with the furnace after ten minutes to get silver electrode is arrived.Then CaCu is tested3Ti4O12Pottery
The dielectric properties of porcelain, as a result as shown in Fig. 2 to 5.
Embodiment 2:
The present embodiment provides a kind of CaCu2.7Co0.3Ti4O12The preparation method of ceramic material, the specific steps are as follows:
In the present embodiment, CaCu is prepared2.7Co0.3Ti4O12Ceramic forerunner powder needs precise calcium nitrate 1.1808g,
Copper nitrate 3.2616g, butyl titanate 6.8072g and cobalt nitrate 0.4365g, according still further to citric acid: metal cation=1: 1 rubs
You weigh citric acid 8.4056g by ratio, remaining processing step uses processing step same as Example 1, are finally prepared huge
The CaCu of dielectric properties2.4Co0.6Ti4O12Dielectric ceramic material.It is situated between after completing ceramic material preparation using same operation test
Electrical property, as a result as shown in Figures 2 to 5.
Embodiment 3:
The present embodiment provides a kind of Ca0.97La0.03Cu2.7Co0.3Ti4O12The preparation method of ceramic material, specific steps are such as
Under:
In the present embodiment, Ca is prepared0.97La0.03Cu2.7Co0.3Ti4O12Ceramic forerunner powder needs precise calcium nitrate
1.1453g, copper nitrate 3.2616g, butyl titanate 6.8072g, cobalt nitrate 0.4365g and lanthanum nitrate 0.065g, according still further to lemon
Acid: metal cation=1: 1 molar ratio weighs citric acid 8.4056g, remaining processing step uses work same as Example 1
The Ca of giant dielectric performance is finally prepared in skill step0.97La0.03Cu2.7Co0.3Ti4O12Dielectric ceramic material.Complete ceramic material
Dielectric properties are tested using same operation after material preparation, as a result as shown in Figures 2 to 5.
Embodiment 4:
The present embodiment provides a kind of Ca0.95La0.05Cu3Ti4O12The preparation method of ceramic material, the specific steps are as follows:
In the present embodiment, Ca is prepared0.95La0.05Cu3Ti4O12Ceramic forerunner powder needs precise calcium nitrate
1.1217g, copper nitrate 3.624g, butyl titanate 6.8072g and lanthanum nitrate 0.1083g, according still further to citric acid: metal cation=
1: 1 molar ratio weighs citric acid 8.4056g, remaining processing step uses processing step same as Example 1, final to prepare
Obtain the Ca of giant dielectric performance0.95La0.05Cu3Ti4O12Dielectric ceramic material.It is grasped after completing ceramic material preparation using same
Make test dielectric properties, as a result as shown in Figures 2 to 5.
Embodiment 5:
The present embodiment provides a kind of Ca0.95La0.05Cu2.7Co0.3Ti4O12The preparation method of ceramic material, specific steps are such as
Under:
In the present embodiment, Ca is prepared0.95La0.05Cu2.7Co0.3Ti4O12Ceramic forerunner powder needs precise calcium nitrate
1.1217g, copper nitrate 3.2616g, butyl titanate 6.8072g, cobalt nitrate 0.4365g and lanthanum nitrate 0.1083g, according still further to lemon
Acid: metal cation=1: molar ratio weigh citric acid 8.4056g, remaining processing step use work same as Example 1
The Ca of giant dielectric performance is finally prepared in skill step0.95La0.05Cu2.7Co0.3Ti4O12Dielectric ceramic material.Complete ceramic material
Dielectric properties are tested using same operation after material preparation, as a result as shown in Figures 2 to 5.
Embodiment 6:
The present embodiment provides a kind of Ca0.95La0.05Cu2.4Co0.6Ti4O12The preparation method of ceramic material, specific steps are such as
Under:
In the present embodiment, Ca is prepared0.95La0.05Cu2.4Co0.6Ti4O12Ceramic forerunner powder needs precise calcium nitrate
1.1217g, copper nitrate 2.8992g, butyl titanate 6.8072g, cobalt nitrate 0.8731g and lanthanum nitrate 0.1083g, according still further to lemon
Acid: metal cation=1: 1 molar ratio weighs citric acid 8.4056g, remaining processing step uses work same as Example 1
The Ca of giant dielectric performance is finally prepared in skill step0.95La0.05Cu2.4Co0.6Ti4O12Dielectric ceramic material.Complete ceramic material
Dielectric properties are tested using same operation after material preparation, as a result as shown in Figures 2 to 5.
Embodiment 7:
The present embodiment provides a kind of Ca0.95La0.05Cu2.4Co0.6Ti4O12The preparation method of ceramic material, specific steps are such as
Under:
In addition to sintering process becomes cooled to room temperature (heating rate after calcining 12 hours at 950 DEG C in the present embodiment
For 5 DEG C/min), remaining processing step uses processing step same as Example 6, finally obtains CaCu3Ti4O12Ceramic Like
Product.Same operation is used to test dielectric properties after completing ceramic material preparation, as a result as shown in Figure 7.
Embodiment 8:
The present embodiment provides a kind of Ca0.95La0.05Cu2.4Co0.6Ti4O12The preparation method of ceramic material, specific steps are such as
Under:
In addition to sintering process becomes cooled to room temperature (heating rate after calcining 12 hours at 1000 DEG C in the present embodiment
For 5 DEG C/min), remaining processing step uses processing step same as Example 6, finally obtains CaCu3Ti4O12Ceramic Like
Product.Same operation is used to test dielectric properties after completing ceramic material preparation, as a result as shown in Figure 7.
Embodiment 9:
The present embodiment provides a kind of Ca0.95La0.05Cu2.4Co0.6Ti4O12The preparation method of ceramic material, specific steps are such as
Under:
In addition to sintering process becomes cooled to room temperature (heating rate after calcining 12 hours at 1050 DEG C in the present embodiment
For 5 DEG C/min), remaining processing step uses processing step same as Example 6, finally obtains CaCu3Ti4O12Ceramic Like
Product.Same operation is used to test dielectric properties after completing ceramic material preparation, as a result as shown in Figure 7.
Embodiment 10:
The present embodiment provides a kind of Ca0.95La0.05Cu2.4Co0.6Ti4O12The preparation method of ceramic material, specific steps are such as
Under:
In addition to sintering process becomes cooled to room temperature (heating rate after calcining 12 hours at 1150 DEG C in the present embodiment
For 5 DEG C/min), remaining processing step uses processing step same as Example 6, finally obtains CaCu3Ti4O12Ceramic Like
Product.Same operation is used to test dielectric properties after completing ceramic material preparation, as a result as shown in Figure 7.
Embodiment 11:
The present embodiment provides a kind of Ca0.95La0.05Cu2.4Co0.6Ti4O12The preparation method of ceramic material, specific steps are such as
Under:
In addition to sintering process becomes cooled to room temperature (heating rate after calcining 12 hours at 1200 DEG C in the present embodiment
For 5 DEG C/min), remaining processing step uses processing step same as Example 6, finally obtains CaCu3Ti4O12Ceramic Like
Product.Same operation is used to test dielectric properties after completing ceramic material preparation, as a result as shown in Figure 7.
The principle of the invention and effect are described in detail with reference to the accompanying drawing:
It will be seen from figure 1 that CaCu3Ti4O12Ceramics, Ca0.95La0.05Cu3Ti4O12Ceramics, CaCu2.7Co0.3Ti4O12Pottery
Porcelain, Ca0.95La0.05Cu2.7Co0.3Ti4O12Ceramics are respectively formed CCTO crystal phase.In La and Co codope CCTO ceramics, ceramics do not have
Extra miscellaneous phase shows that La and Co ion has been introduced into CCTO crystal phase；In the mono- doping CCTO ceramics of Co, i.e.,
CaCu2.7Co0.3Ti4O12Ceramics, there is also CaTiO other than forming CCTO crystal phase3And Co2TiO4Phase.
From figures 2 and 3, it will be seen that CaCu3Ti4O12Ceramics dielectric constant with higher at low frequency, but its dielectric
The frequency stability of constant is lower, 104Dielectric constant quickly reduces after Hz, this is because sintering temperature is excessively high to lead to CCTO
It mutually liquefies, sample rate declines to a great extent, so the frequency stability of dielectric constant reduces, while dielectric loss also will increase.
CaCu2.7Co0.3Ti4O12Ceramic dielectric constant is minimum, and frequency stability is lower that be also due to its sintering temperature excessively high, so that not
CCTO phase can be formed completely, generate other miscellaneous phases；And the grain boundaries that are entrained in of Co form the CaTiO with high insulating property3With
Co2TiO4Phase makes under its low frequency dielectric loss compared to CaCu3Ti4O12Ceramics are lower, but CaCu in high frequency2.7Co0.3Ti4O12
The dielectric loss highest of ceramics, this is because caused by its grain growth is chaotic.Ca0.97La0.03Cu2.7Co0.3Ti4O12Ceramics and
Ca0.95La0.05Cu2.7Co0.3Ti4O12Ceramics have relatively high dielectric constant and lower dielectric loss, the doping of La so that
Complete, the not extra miscellaneous phase of CCTO crystal phase development, and crystal grain is uniformly grown up, so its dielectric constant increases；Dielectric is damaged
Consumption, due to ceramic crystalline grain Size growth and uniform in size, consistency increase, dielectric loss reduction, while La doping can reduce pottery
The grain boundary resistance of porcelain, and Dielectric Properties loss is related with grain boundary resistance, therefore La doping can reduce the high-frequency dielectric damage of ceramics
Consumption.As can be seen from Figure 2, increase to 0.05at% from 0.03at% with La doping content, the dielectric of La, Co codope ceramics is normal
Number reduces, while dielectric loss also reduces.
From fig. 4, it can be seen that CaCu3Ti4O12The grain boundaries of ceramics (figure a) influence its dielectricity there are impurity and hole
Energy；And Ca0.95La0.05Cu2.7Co0.3Ti4O12The crystal grain of ceramics (figure b) is more uniform and arrangement is close, and crystallite dimension also slightly subtracts
Small, compactness improves, and finds in conjunction with Fig. 2 and Fig. 3, Ca0.95La0.05Cu2.7Co0.3Ti4O12Ceramics dielectric properties also superior to
CaCu3Ti4O12Ceramics.
Fig. 5 and Fig. 6 can be seen that Ca0.95La0.05Cu3Ti4O12The dielectric constant of ceramics is very low, this is because sintering temperature
Height is spent, caused by CCTO phase liquefies, and La doping reduces the grain boundary resistance and grain resistance of ceramics, so that
Ca0.95La0.05Cu3Ti4O12The high-frequency dielectric of ceramics, which is lost, to be reduced.And Co, La codope can be while reducing dielectric loss
Higher dielectric constant is maintained, as Co doping content increases to 0.6at% from 0.3at%, Jie of La, Co codope ceramics
Electric constant also increases.
From figure 7 it can be seen that sintering temperature Ca at 1100 DEG C0.95La0.05Cu2.4Co0.6Ti4O12The dielectric constant of ceramics
Highest, and it is that its dielectric constant is minimum that sintering temperature, which is 950 DEG C, it is seen that Ca0.95La0.05Cu2.4Co0.6Ti4O12Ceramic is best
Sintering temperature is 1100 DEG C.
The embodiment of the present invention is elaborated in conjunction with attached drawing above, but the invention is not limited to above-mentioned
Specific embodiment, above-mentioned specific embodiment is only schematical, rather than restrictive, the ordinary skill people of this field
Member under the inspiration of the present invention, can also make many in the case where not departing from present inventive concept and claimed range
Deformation, these belong to protection of the invention.
Claims (10)
1. a kind of CaCu 3 Ti 4 O base ceramic material, which is characterized in that the chemical composition and crystal phase of ceramic material are Ca1-xLaxCu3- yCoyTi4O12, wherein 0 ﹤ x≤0.05,0 y≤0.6 ﹤.
2. a kind of preparation method of CaCu 3 Ti 4 O base ceramic material, which comprises the steps of:
Step A: according to Ca1-xLaxCu3-yCoyTi4O12, wherein 0 ﹤ x≤0.05, the stoichiometric ratio ingredient of 0 y≤0.6 ﹤, raw material
It include: inorganic metal calcium salt, inorganic metal lanthanum salt, inorganic metal mantoquita, inorganic metal cobalt salt and butyl titanate；By inorganic gold
Belong to calcium salt, inorganic metal lanthanum salt, inorganic metal mantoquita and inorganic metal salt solubility and forms inorganic metal salt mixing in a solvent
Butyl titanate dissolution is formed solution of tetrabutyl titanate in a solvent, complexing agent dissolution is formed in a solvent and is complexed by solution
Agent solution, wherein the mole ratio of metal cation integral molar quantity and complexing agent is 1: 1；Then solution of tetrabutyl titanate is added
Mixed solution is obtained into enveloping agent solution, then inorganic metal mixed salt solution is added in the mixed solution, and mixing is equal
It is even, form colloidal sol；It handles the drying sol to obtain gel, the gel is fired and pulverizes to obtain ceramics
Precursor powder；
Step B: the copper titanate is so far made through granulation, pre-burning, sintering processes in the ceramic forerunner powder that step A is obtained
Calcium base ceramic material.
3. preparation method according to claim 2, which is characterized in that the solvent is dehydrated alcohol, the inorganic gold
Belong to calcium salt, inorganic metal lanthanum salt, inorganic metal mantoquita, inorganic metal cobalt salt anion be nitrate anion.
4. preparation method according to claim 2, which is characterized in that need heating water bath, water-bath temperature when forming colloidal sol
Preferably 80 DEG C of degree, to guarantee that sufficiently reaction is mixed using agitating mode when heating water bath, mixing time is 2~8 hours.
5. preparation method according to claim 2, which is characterized in that form drying process when gel and specifically will
Colloidal sol is 6~18 hours dry under the conditions of being placed in 70~100 DEG C.
6. preparation method according to claim 2, which is characterized in that formed ceramic forerunner powder when fire be specifically
Pre-burning 2~4 hours under the conditions of xerogel is placed in 600~900 DEG C.
7. preparation method according to claim 2, which is characterized in that further included before carrying out pre-burning after the completion of granulation
Compression moulding after sieve.
8. preparation method according to claim 2, which is characterized in that the preheating is specifically in air atmosphere
It is sintered 0.5~2 hour in 500~800 DEG C.
9. preparation method according to claim 2, which is characterized in that further include row before being sintered after the completion of pre-burning
Glue processing, i.e. cooled to room temperature after the completion of pre-burning.
10. preparation method according to claim 2, which is characterized in that the sintering processes are specifically in air atmosphere
Under be sintered 6~15 hours in 950~1200 DEG C, then cooled to room temperature.
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| CN112552039A (en) * | 2020-12-14 | 2021-03-26 | 江西科技学院 | CaCu3Ti4O12Powder preparation and ceramic sintering method |
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| CN111992257B (en) * | 2020-03-25 | 2024-02-13 | 武汉纺织大学 | Modified perovskite hollow porous microsphere for catalytic degradation of antibiotics, and preparation method and application thereof |
| CN112457026A (en) * | 2020-12-14 | 2021-03-09 | 江西科技学院 | Copper calcium titanate ceramic reduction-oxidation atmosphere co-sintering method |
| CN112552039A (en) * | 2020-12-14 | 2021-03-26 | 江西科技学院 | CaCu3Ti4O12Powder preparation and ceramic sintering method |
| CN112661507A (en) * | 2021-01-11 | 2021-04-16 | 湖南省美程陶瓷科技有限公司 | Alumina ceramic material for dual-function pressure sensor and preparation method thereof |
| CN113800901A (en) * | 2021-09-30 | 2021-12-17 | 太原理工大学 | Low-loss copper titanate lanthanum calcium dielectric ceramic material in low-temperature environment and preparation method thereof |
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