CN101503186B - Preparing method of precursor water solution for preparing CaCu3Ti4O12 - Google Patents
Preparing method of precursor water solution for preparing CaCu3Ti4O12 Download PDFInfo
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- CN101503186B CN101503186B CN2008100597021A CN200810059702A CN101503186B CN 101503186 B CN101503186 B CN 101503186B CN 2008100597021 A CN2008100597021 A CN 2008100597021A CN 200810059702 A CN200810059702 A CN 200810059702A CN 101503186 B CN101503186 B CN 101503186B
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Abstract
The invention discloses a preparation method of a precursor water solution for preparing calcium copper titanate. The preparation method comprises: providing alkaline calcium compound, alkaline cupric compound, alkoxyl titanium and citric acid water solution, and the ratio between the total mole number of calcium, copper and titanium atoms and the mole number of citrate being more than 0 and less than or equal to 1.5; directly adding the alkaline calcium compound, the alkaline cupric compound and the alkoxyl titanium into the citric acid water solution, continuously stirring during the addition process to ensure undissolved substance to be dissolved in time, and obtaining clear solution which is the precursor water solution of the invention, wherein the alkaline calcium compound is at least one selected from calcium oxide, calcium hydroxide and calcium bicarbonate; the alkaline cupric compound is at leas one selected from basic cupric carbonate and cupric hydroxide. The method has simple preparation technique, simple and available raw materials, low cost and easy industrialization. After the processes such as preburning decomposition, calcination and the like, the precursor water solution can be used for preparing calcium copper titanate powder with regular granule appearance, and the dielectric constant of the calcium copper titanate powder reaches 4*10<5>.
Description
Technical field
The present invention relates to prepare the compound method of the precursor water solution of ceramic powder,, the invention still further relates to the preparation method of calcium copper titanate ceramics powder in particular for the compound method of the precursor water solution of preparation calcium copper titanate ceramics powder.
Background technology
Along with the develop rapidly of semi-conductor industry, the dielectric material that look for novelty must meet the following conditions: high-k, good dielectric and temperature profile, high insulation resistivity, dielectric loss are little, anti-aging etc.People such as Subramanian had found CaCu 3 Ti 4 O (CaCu in 2000
3Ti
4O
12, be called for short CCTO), this material has very high specific inductivity, and (specific inductivity can reach 10 under normal temperature, 1kHz frequency condition
4～10
5), low dielectric loss and higher thermostability.These good comprehensive performances make it might obtain to use in a series of devices such as high density energy storage, thin-film device, high dielectric capacitor, transmitter, and therefore, the preparation of CaCu 3 Ti 4 O has caused people's extensive concern with application.
Existing calcium copper titanate ceramics powder process mainly is a solid-phase synthesis.Solid-phase synthesis mainly is the starting compound powder to be carried out ball milling mix, and then mixed powder is carried out pre-burning, carries out calcination again.Solid-phase synthesis, because its mixing is physical mixed, and in order to obtain more satisfactory mixed effect, the ball milling required time is longer, so the solid-phase synthesis limitation that its inherent arranged, be difficult to overcome.
The preparation of calcium copper titanate ceramics powder can also be used sol-gel method.
A kind of sol-gel method of classics is Pechini Type methods.Pechini Type method is a kind of method of summing up out according to the patent that Pechini delivered in 1967, mainly is to utilize citric acid and ethylene glycol to form netted macromole to come stable metal ion, again this macromole is formed desired product through thermal treatment.Chemical constitution is relevant with the mol ratio of citric acid and metal ion uniformly, and need carefully select employed initial salt, and notes the potential of hydrogen of system.Crystallize out because of supersaturation for fear of metal ion, often utilize the potential of hydrogen of ammoniacal liquor Adjustment System.Do not use the nitric acid dissolve metallic compound in the solution as far as possible, because excessive nitric acid and glycol reaction can generate oxalic acid, and oxalic acid very easily forms the insoluble salt and produces precipitation with metal ion.Therefore, generally can use acetate or carbonate to substitute nitrate as initial reactant.
Open source literature " Synthesis of CaCu
3Ti
4O
12Ceramic via a sol-gel method, Shuhua Jin, Haiping Xia, Yuepin Zhang, Juping Guo, Jun Xu, Materials Letters 61 (2007) 1404-1407 " disclosed the method that a kind of sol-gel method of having used citric acid prepares the calcium copper titanate ceramics powder.Its process is: with Ca (NO
3)
24H
2O, Cu (NO
3)
23H
2O is dissolved in ethanol and makes a solution; Simultaneously, titanium n-butoxide is dissolved in another dehydrated alcohol, adds Glacial acetic acid, nitric acid, deionized water etc. again, make another part solution, stir after 40 minutes; Two parts of solution are mixed; Then, citric acid is joined in the aforesaid mixing solutions, wherein the molar ratio of citrate and metal ion is 1.5: 1, makes transparent blue sol; Through super-dry, the solid matter that drying is obtained carries out just can making the calcium copper titanate ceramics powder after thermal degradation and the calcining again.
Above-mentioned two kinds of technologies, operating process is all more numerous and diverse, and is raw materials used more, need use ethanol etc. as organic solvent, and acetic acid etc. are as stablizer.Particularly in a kind of scheme in back, use HNO
3, Ca (NO
3)
24H
2O, Cu (NO
3)
23H
2Compounds such as O, nitric acid have more intense corrodibility and volatility, Ca (NO
3)
24H
2O, Cu (NO
3)
23H
2O has more intense water-absorbent, and these all can cause the inconvenience of operating.And from the XRD figure that document provides, 900 ℃ of calcining samples still have dephasign to exist.And, inessential ion that a large amount of need remove through aftertreatment, solvent etc. have been introduced according to the final colloidal sol that above-mentioned technology makes.Above-mentioned raw materials technology utilization ratio is low, does not meet the economy requirement.
Prepare in the method for calcium copper titanate ceramics powder by preparing CaCu 3 Ti 4 O precursor water solution method, being formulated in this process of CaCu 3 Ti 4 O solution precursor water solution seems the most key.
Summary of the invention
Technical problem to be solved by this invention is to provide few, even, stable being used to of a kind of inessential component to prepare the compound method of the presoma clear aqueous solution of CaCu 3 Ti 4 O.
Another technical problem to be solved by this invention is to provide a kind of preparation method of calcium copper titanate ceramics powder.
For addressing the above problem, the compound method that is used to prepare the precursor water solution of CaCu 3 Ti 4 O provided by the invention, comprise: provide alkaline calcium compound, alkaline copper compound, titan-alkoxide and aqueous citric acid solution, and the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is greater than 0 and be less than or equal to 1.5; Alkaline calcium compound, alkaline copper compound and titan-alkoxide are directly joined in the aqueous citric acid solution, and constantly stir in the adition process and guarantee that insolubles is in time dissolved, finally obtain the clarifying aqueous solution.
In this patent, as there are not other explanation, " alkaline calcium compound " to be limited at least a in calcium oxide, calcium hydroxide, lime carbonate, the Calcium hydrogen carbonate; " alkaline copper compound " is limited at least a in ventilation breather, the copper hydroxide.
After these compounds join in the aqueous citric acid solution, can with citric acid generation complex reaction, generate the citric acid complex of water miscible calcium, copper, can not produce impurity.And these alkaline calcium compounds, alkaline copper compound, in industrialization, all being easy to obtain, price is also cheaper, and quantitatively, it is more convenient to operate easily.
Citrate of lime, Cuprocitrol all belong to micro-soluble material, if directly use the citrate of lime, the Cuprocitrol hydrate that obtain on the market to be raw material, and to obtain even clarifying clear solution with water as solvent be infeasible.In addition, in appearing in the newspapers, prepare Ca
2+, Cu
2+With the colloidal sol of citrate coexistence, need to add calcium salt, the mantoquita of solubility, and stablizers such as nitric acid or acetic acid are to stop sedimentary generation.
And calcium oxide, calcium hydroxide, lime carbonate, ventilation breather, copper hydroxide all is known indissoluble or slightly soluble material, but in the present invention, as long as determine calcium, the ratio of the mole number of copper and titanium atom total moles and citrate is less than or equal to 1.5, and keep lasting agitation condition, just can be alkaline calcium compound, alkaline copper compound and titan-alkoxide directly join in the aqueous citric acid solution and are mixed with uniform transparent aqueous solution, and do not need prior dissolved oxygen calcium, calcium hydroxide, lime carbonate, ventilation breather and copper hydroxide, and do not want stablizers such as additionally adding nitric acid.The ratio of the mole number of preferred calcium, copper and titanium atom total moles and citrate is 0.5～1.2, more preferably 0.67～1.
Although citric acid and alkaline calcium compound, alkaline copper compound generation complex reaction, generate water miscible calcium, copper citric acid complex, but in this process, for fear of producing citrate of lime, Cuprocitrol precipitation, keep agitation condition constantly, guarantee that it is very necessary that the insolubles that produces in the reinforced process is in time dissolved.Temperature is very unobvious to reinforced process influence, but it should be noted that too high temperature also may cause citrate of lime, Cuprocitrol precipitation, thereby the present invention can't be realized.Therefore the preferred temperature of the present invention is at 5～50 ℃, preferred especially 15～25 ℃.If used alkaline calcium compound is block calcium oxide, so, before reinforced, optimal way is that it is levigate, with the promotion compound dissolution, thereby accelerates follow-up complex reaction speed.
At the process for preparation that is used for preparing the precursor water solution of CaCu 3 Ti 4 O provided by the present invention, used titanium source mostly is common titan-alkoxide, at least a such as in titanium n-butoxide, titanium isopropoxide, positive propoxy titanium, the ethanolato-titanium.Titan-alkoxide has the advantages that to meet water decomposition, in the present invention, be that titan-alkoxide is slowly added in the aqueous citric acid solution of vigorous stirring, because the existence of water, titan-alkoxide is understood hydrolysis equally and is produced insolubles, but by the control feed rate, the insolubles of titan-alkoxide hydrolysis is under intense agitation, stir and slowly to be dissolved through the long time, final transparent homogeneous solution by complexing.For the higher titan-alkoxide of activity,, can under lower temperature, carry out in reinforced process as titanium isopropoxide.
Also it is pointed out that if use the aqueous citric acid solution of low concentration, then in reinforced process, be easy to generate precipitation, and in a single day precipitation produces, just be difficult to dissolving, therefore, need slow down feed rate, still can make the production cycle elongated in order not produce precipitation; And higher aqueous citric acid solution concentration can make feed rate improve, and more promptly obtains homogeneous solution.But if the citric acid consumption is excessive, then can exert an influence to aftertreatment, production cost, excessive citric acid can cause the sample organic substance residues after the pre-burning excessive.In the present invention, the mass percent concentration of aqueous citric acid solution is preferably more than 10%.
When alkaline copper compound, alkaline calcium compound and titan-alkoxide are joined aqueous citric acid solution, alkaline calcium compound and alkaline copper compound can be joined in a aqueous citric acid solution, titan-alkoxide is joined in the aqueous citric acid solution of another part, mix two parts of aqueous citric acid solutions then; Perhaps, also can be that alkaline calcium compound, alkaline copper compound and titan-alkoxide are joined respectively with in a aqueous citric acid solution in batches.
The method for preparing the calcium copper titanate ceramics powder provided by the present invention, comprise: alkaline calcium compound, alkaline copper compound, titan-alkoxide and aqueous citric acid solution are provided, and the ratio of the mole number of definite calcium, copper and titanium atom total moles and citrate is greater than 0 and be less than or equal to 1.5, directly join alkaline calcium compound, alkaline copper compound and titan-alkoxide in the aqueous citric acid solution, adition process guarantees that by continuous stirring insolubles is in time dissolved, and makes the mixing precursor solution; Dry precursor solution obtains pressed powder; Pressed powder makes the calcium copper titanate ceramics powder through pre-burning decomposition and calcination process successively.Wherein, alkaline calcium compound is at least a in calcium oxide, calcium hydroxide, lime carbonate, the Calcium hydrogen carbonate; The alkaline copper compound is at least a in ventilation breather, the copper hydroxide.
The method for preparing the calcium copper titanate ceramics powder provided by the present invention, wherein, titan-alkoxide can be at least a in titanium n-butoxide, titanium isopropoxide, positive propoxy titanium, the ethanolato-titanium.The exsiccant method can be lyophilize, spraying drying or any method in the oven dry in baking oven.What the method that pre-burning is decomposed adopted is thermal degradation or other methods commonly used in 450 ℃ of retort furnaces.The pre-burning decomposition temperature is 300 ℃ to 500 ℃.The incinerating temperature is 700 ℃ to 1200 ℃.
In addition, made by method provided by the invention be used to prepare the precursor water solution of CaCu 3 Ti 4 O after, can also further use other method to make the ceramic powder of CaCu 3 Ti 4 O such as methods such as spray burnings.
The preparation method of CaCu 3 Ti 4 O provided by the present invention is an independently technical scheme, but, therefore possesses unicity with the technical scheme that is used to prepare the precursor water solution of CaCu 3 Ti 4 O disclosed by the invention because adopted the precursor water solution that is used to prepare CaCu 3 Ti 4 O provided by the present invention.
The precursor water solution that is used to prepare CaCu 3 Ti 4 O provided by the present invention, because having only some alcohol, ester, citrate to prepare in the calcium copper titanate ceramics powder process in the later stage needs to remove, the precursor water solution that relatively prior art was mixed with, do not include compositions such as nitrate radical, acetate, therefore also unlikely meeting produces obnoxious flavoures such as oxynitrides in follow-up calcination process because containing nitrate radical.And the precursor water solution among the present invention, be uniform clear aqueous solution, stability is very good, and is at least can 1 week of stable existence under the room temperature above and do not produce precipitation.Above-mentioned precursor water solution not only can be used for preparing the CaCu 3 Ti 4 O powder but also can also be used to preparing CaCu 3 Ti 4 O film etc.
The method of preparation precursor water solution provided by the invention, what adopt from the former preparation of expecting precursor water solution is the technical process of single step, and does not introduce the material beyond the necessary reactant.So the contained inessential ion of final solution, solvent that present method makes are few, and aftertreatment is easy, and process cycle is short, process is simple, raw material availability is high, are fit to suitability for industrialized production.
Equally, the method for preparing CaCu 3 Ti 4 O provided by the invention, raw material is simple and easy to, and preparation process is simple, and preparation cost is cheap, industrialization easily, simultaneously, the CaCu 3 Ti 4 O powder powder of preparation is loose, granule-morphology is regular.
More prepared samples of method that prepare the calcium copper titanate ceramics powder provided by the invention at room temperature record specific inductivity and can reach 4 * 10
5
Description of drawings
Fig. 1 is wherein a kind of operational path of the compound method of the precursor water solution that being used among the present invention prepares CaCu 3 Ti 4 O.Wherein, shown in " alkaline calcium compound " be at least a in calcium oxide, calcium hydroxide, lime carbonate, the Calcium hydrogen carbonate, " alkaline copper compound " is at least a in ventilation breather, the copper hydroxide.
Fig. 2 is the another kind of operational path of the compound method of the precursor water solution that being used among the present invention prepares CaCu 3 Ti 4 O.Wherein, shown in " alkaline calcium compound " be at least a in calcium oxide, calcium hydroxide, lime carbonate, the Calcium hydrogen carbonate, " alkaline copper compound " is at least a in ventilation breather, the copper hydroxide.
Fig. 3 is the SEM figure of the embodiment of the invention 7 prepared calcium copper titanate ceramics powder.
Fig. 4 is the precursor water solution of preparation in the embodiment of the invention 7, decompose through 450 ℃ pre-burning, the XRD figure of the prepared calcium copper titanate ceramics powder of different calcining temperature.
Embodiment
Specific embodiments of the present invention are further described in detail below in conjunction with accompanying drawing.
Embodiment 1
Take by weighing the 12.600g Citric acid monohydrate Food grade, be dissolved in the 60ml deionized water, obtain clear solution.Take by weighing 1.113gCa (OH)
2, keeping under the intense stirring condition, Ca (OH)
2Add in the aqueous citric acid solution that makes, obtain clear solution.
Take by weighing 4.390g Cu (OH)
2, keeping under the intense stirring condition, Cu (OH)
2Slowly add and be dissolved with Ca (OH)
2Aqueous citric acid solution, obtain blue clear solution A1.
Take by weighing the 25.216g Citric acid monohydrate Food grade, be dissolved in the 100ml deionized water, get clear solution.Take by weighing the 20.470g titanium n-butoxide, under the maintenance intense stirring condition, titanium n-butoxide slowly is added drop-wise in the aqueous citric acid solution.After waiting to drip end, continue vigorous stirring, get yellow settled solution B
1
With the A that makes
1Solution and B
1Solution mixes in stirring condition, finally obtains being used to prepare the precursor water solution of CaCu 3 Ti 4 O.
In this embodiment, the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is 0.67.
Embodiment 2
Take by weighing the 12.600g Citric acid monohydrate Food grade, be dissolved in the 60ml deionized water, get clear solution.Take by weighing 0.840g CaO, under keeping intense stirring condition, CaO is added in the aqueous citric acid solution that makes, get clear solution through grinding.
Take by weighing 4.390g Cu (OH)
2, keeping under the intense stirring condition, Cu (OH)
2Slowly add the aqueous citric acid solution that is dissolved with CaO, obtain blue clear solution A
2
Take by weighing the 25.216g Citric acid monohydrate Food grade, be dissolved in the 100ml deionized water, get clear solution.Take by weighing the 20.420g titanium n-butoxide, under the maintenance intense stirring condition, tetrabutyl titanate slowly is added drop-wise in the aqueous citric acid solution.After waiting to drip end, continue vigorous stirring, get yellow settled solution B
2
With the A that makes
2Solution and B
2Solution mixes under stirring condition, finally obtains being used to prepare the precursor water solution of CaCu 3 Ti 4 O.
In this embodiment, the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is 0.67.
Embodiment 3
Take by weighing the 2.102g Citric acid monohydrate Food grade, be dissolved in the 20ml deionized water, get clear solution.Take by weighing 0.371gCa (OH)
2, keeping under the intense stirring condition Ca (OH)
2Add in the aqueous citric acid solution that makes, get clear solution.
Take by weighing 1.463g Cu (OH)
2, keeping under the intense stirring condition, Cu (OH)
2Slowly add and be dissolved with Ca (OH)
2Aqueous citric acid solution, final blue clear solution A3.
Take by weighing the 3.510g Citric acid monohydrate Food grade, be dissolved in the 20ml deionized water, get clear solution.Take by weighing the 6.806g titanium n-butoxide, under the maintenance intense stirring condition, titanium n-butoxide slowly is added drop-wise in the aqueous citric acid solution.After waiting drip to finish, continue vigorous stirring, final yellow settled solution B
3
With the A that makes
3Solution and B
3Solution mixes in stirring condition, finally obtains being used to prepare the precursor water solution of CaCu 3 Ti 4 O.
In this embodiment, the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is 1.5.
Embodiment 4
Take by weighing the 18.900g Citric acid monohydrate Food grade, be dissolved in the 60ml deionized water, get clear solution.Take by weighing 1.113gCa (OH)
2, keeping under the intense stirring condition, Ca (OH)
2Add in the aqueous citric acid solution that makes, get clear solution.
Take by weighing 4.390g Cu (OH)
2, keeping under the intense stirring condition, Cu (OH)
2Slowly add and be dissolved with Ca (OH)
2Aqueous citric acid solution, obtain blue clear solution A
4
Take by weighing the 30.600g Citric acid monohydrate Food grade, be dissolved in the 100ml deionized water, get clear solution.Take by weighing the 20.420g titanium n-butoxide, under the maintenance intense stirring condition, titanium n-butoxide slowly is added drop-wise in the aqueous citric acid solution.After waiting drip to finish, continue vigorous stirring, final yellow settled solution B
4
With the A that makes
4Solution and B
4Solution mixes in stirring condition, finally obtains being used to prepare the precursor water solution of CaCu 3 Ti 4 O.
In this embodiment, the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is 0.5.
Embodiment 5
Take by weighing the 49.500g Citric acid monohydrate Food grade, be dissolved in the 160ml deionized water, get clear solution.Take by weighing 1.113gCa (OH)
2, keeping under the intense stirring condition, Ca (OH)
2Add in the aqueous citric acid solution that makes, get clear solution.
Take by weighing 4.390g Cu (OH)
2, keep vigorous stirring to obtain under the timely dissolved condition, with Cu (OH) with the insolubles of guaranteeing reinforced moment generation
2Slowly add and be dissolved with Ca (OH)
2Aqueous citric acid solution, obtain blue clear solution.
Take by weighing the 20.420g titanium n-butoxide, under intense stirring condition, titanium n-butoxide slowly is added drop-wise in the above-mentioned blue clear solution.After waiting to drip end, continue vigorous stirring, final blue settled solution, i.e. the CaCu 3 Ti 4 O precursor aqueous solution of getting.
In this embodiment, the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is 0.5.
Embodiment 6
Take by weighing the 25.219g Citric acid monohydrate Food grade, be dissolved in the 160ml deionized water, get clear solution.Take by weighing 1.113gCa (OH)
2, keeping under the intense stirring condition, Ca (OH)
2Add in the aqueous citric acid solution that makes, get clear solution.
Take by weighing 4.390g Cu (OH)
2, keep vigorous stirring to obtain under the timely dissolved condition, with Cu (OH) with the insolubles of guaranteeing reinforced moment generation
2Slowly add and be dissolved with Ca (OH)
2Aqueous citric acid solution, obtain blue clear solution.
Take by weighing the 20.420g titanium n-butoxide, under intense stirring condition, titanium n-butoxide slowly is added drop-wise in the above-mentioned blue clear solution.After waiting to drip end, continue vigorous stirring, final blue settled solution, i.e. the CaCu 3 Ti 4 O precursor aqueous solution of getting.
In this embodiment, the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is 1.
Embodiment 7
Take by weighing the 10.507g Citric acid monohydrate Food grade, be dissolved in the 160ml deionized water, get clear solution.Take by weighing 1.113gCa (OH)
2, keeping under the intense stirring condition, Ca (OH)
2Add in the aqueous citric acid solution that makes, get clear solution.
Take by weighing 4.390g Cu (OH)
2, keep vigorous stirring to obtain under the timely dissolved condition, with Cu (OH) with the insolubles of guaranteeing reinforced moment generation
2Slowly add and be dissolved with Ca (OH)
2Aqueous citric acid solution, obtain blue clear solution.
Take by weighing the 20.420g titanium n-butoxide, under intense stirring condition, titanium n-butoxide slowly is added drop-wise in the above-mentioned blue clear solution.After waiting to drip end, continue vigorous stirring, final blue settled solution, i.e. the CaCu 3 Ti 4 O precursor aqueous solution of getting.
In this embodiment, the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is 1.2.
Embodiment 8
Take by weighing the 12.600g Citric acid monohydrate Food grade, be dissolved in the 60ml deionized water, get clear solution.Take by weighing 1.113gCa (OH)
2, keeping under the intense stirring condition, Ca (OH)
2Add in the aqueous citric acid solution that makes, get clear solution.
Take by weighing 4.390g Cu (OH)
2, keeping under the intense stirring condition, Cu (OH)
2Slowly add and be dissolved with Ca (OH)
2Aqueous citric acid solution, obtain blue clear solution A
8
Take by weighing the 25.216g Citric acid monohydrate Food grade, be dissolved in the 100ml deionized water, get clear solution.Take by weighing the 17.052g titanium isopropoxide, under the maintenance intense stirring condition, titanium isopropoxide slowly is added drop-wise in the aqueous citric acid solution.After waiting drip to finish, continue vigorous stirring, final yellow settled solution B
8
With the A that makes
6Solution and B
6Solution mixes under intense stirring condition, finally obtains being used to prepare the precursor water solution of CaCu 3 Ti 4 O.
In this embodiment, the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is 0.67.
Embodiment 9
Take by weighing the 12.600g Citric acid monohydrate Food grade, be dissolved in the 60ml deionized water, get clear solution.Take by weighing 1.113gCa (OH)
2, keeping under the intense stirring condition, Ca (OH)
2Add in the aqueous citric acid solution that makes, get clear solution.
Take by weighing 4.390g Cu (OH)
2, keeping under the intense stirring condition, Cu (OH)
2Slowly add and be dissolved with Ca (OH)
2Aqueous citric acid solution, obtain blue clear solution A
9
Take by weighing the 25.216g Citric acid monohydrate Food grade, be dissolved in the 100ml deionized water, get clear solution.Take by weighing the 20.470g titanium n-butoxide, under the maintenance intense stirring condition, titanium n-butoxide slowly is added drop-wise in the aqueous citric acid solution.After waiting drip to finish, continue vigorous stirring, final yellow settled solution B
9
With the A that makes
7Solution and B
7Solution mixes under intense stirring condition, finally obtains being used to prepare the precursor water solution of CaCu 3 Ti 4 O.Wherein, the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is 0.67.With this precursor solution 180 ℃ of dryings, in retort furnace, decomposed 30 minutes then, after the powder after pre-burning is decomposed grinds in agate grinds, in 850 ℃ of calcinings (heating schedule is 5 ℃/minute) 450 ℃ of pre-burnings, be incubated 10 hours, obtain the calcium copper titanate ceramics powder.Its SEM can observe the calcium copper titanate ceramics powder diameter between 100～300nm as shown in Figure 3 from SEM figure, particle size distribution is even.
Accompanying drawing 4 is to use the method for preparing the calcium copper titanate ceramics powder provided by the invention, in 450 ℃ pre-burnings decomposition, the XRD figure of the prepared calcium copper titanate ceramics powder of different calcining temperature.Through and CCTO standard spectrogram contrast, more than 700 ℃ the time, can observe the diffraction peak of CCTO in calcining temperature significantly.
Taking by weighing the 8.406g citric acid is dissolved in the 40ml deionized water and gets shallow yellow transparent solution under agitation condition;
Take by weighing 0.741g Ca (OH)
2, under stirring condition, slowly add aqueous citric acid solution;
Take by weighing 2.927g Cu (OH)
2, under stirring condition, it is slowly added and is dissolved with Ca (OH)
2Aqueous citric acid solution in, obtain blue clear solution A
10
Take by weighing the 16.812g citric acid and be dissolved in the 60ml deionized water at agitation condition and get shallow yellow transparent solution, take by weighing 13.613gTi (O
nC
4H
9)
4Under intense agitation, slowly add aqueous citric acid solution, get clear solution B
10
Mix A
8, B
8Solution obtains the precursor water solution of CaCu 3 Ti 4 O;
The precursor water solution of CaCu 3 Ti 4 O was got the fluffy pressed powder of black in 12 hours in 180 ℃ of dryings, and pressed powder decomposes in 450 ℃ of pre-burnings after grinding evenly, and heating schedule is: 5 ℃/min, be incubated 3 hours;
Pre-burning gets sample and grinds even back to add concentration be 5% (mass percent) PVB granulation compressing tablet (PVB add-on be about powder weight 5%), every heavy 0.3000-0.3200g, diameter
Pressure 8MPa, 3 minutes hold-times;
Compacting is obtained sheet in 1100 ℃ of sintering, and heating schedule is: 5 ℃/min, be incubated 10 hours.The sample that sintering obtains is coated with conductive silver paste.Be coated with high temperature silver slurry samples in 700 ℃ of calcinings, the test electrical property, its result is as shown in table 1.
The instrument that uses in the present embodiment, model and manufacturer are:
1, Hi-pot Tester; Model: CJ2677F, manufacturer: yangtze river in nanjing radio factory;
2, Precision LCR Meter; Model: E4980A; Manufacturer: Agilent.
Table 1
| The sample sequence number | Cp(nF) | Specific inductivity | Dielectric loss | Compressive strength (kV/mm) |
| A | 182.4 | 619123.68 | 0.87 | 0.043253 |
| B | 122.0 | 425211.79 | 0.78 | 0.042123 |
| C | 133.0 | 450918.17 | 0.66 | 0.04329 |
| D | 164.7 | 563396.66 | 0.83 | 0.042918 |
In these above-mentioned embodiment, violent stirring all is can access dissolving timely in order to ensure the insolubles that reinforced moment produces in the reinforced process, just is difficult to be dissolved fully because in a single day insolubles forms precipitation again.Should be noted that, those skilled in the art are to the simple replacement or the improvement of employed reactant, processing condition or process etc. among the present invention, such as: in the reinforced process in order to ensure the timely dissolving of insolubles, employing is different from other hybrid modes of stirring, but the effect that reaches is identical with mixing effect; Adopted to be different from the titan-alkoxide that uses in the embodiment of the invention, for example titanium n-butoxide, positive propoxy titanium, ethanolato-titanium etc.; Adopt different pre-burning decomposition, calcining manners and other forming material powder method etc., all should be considered to the content that the present invention has disclosed, perhaps should regard as is the replacement that is equal to of technical scheme that the present invention is disclosed.
Claims (12)
1. compound method that is used to prepare the precursor water solution of CaCu 3 Ti 4 O, comprise: provide alkaline calcium compound, alkaline copper compound, titan-alkoxide and aqueous citric acid solution, and the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is greater than 0 and be less than or equal to 1.5; Alkaline calcium compound, alkaline copper compound and titan-alkoxide are directly joined in the aqueous citric acid solution, and constantly stir in the adition process and guarantee that insolubles is in time dissolved, finally obtain the clarifying aqueous solution;
Wherein, alkaline calcium compound is at least a in calcium oxide, calcium hydroxide, lime carbonate, the Calcium hydrogen carbonate;
The alkaline copper compound is at least a in ventilation breather, the copper hydroxide.
2. the compound method that is used to prepare the precursor water solution of CaCu 3 Ti 4 O according to claim 1, wherein, titan-alkoxide is at least a in titanium n-butoxide, titanium isopropoxide, positive propoxy titanium, the ethanolato-titanium.
3. the compound method that is used to prepare the precursor water solution of CaCu 3 Ti 4 O according to claim 1, wherein, the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is 0.5-1.2.
4. the compound method that is used to prepare the precursor water solution of CaCu 3 Ti 4 O according to claim 3, wherein, the ratio of the mole number of calcium, copper and titanium atom total moles and citrate is 0.67-1.
5. the compound method that is used to prepare the precursor water solution of CaCu 3 Ti 4 O according to claim 1, wherein, the mass percent concentration of aqueous citric acid solution is greater than 10%.
6. the compound method that is used to prepare the precursor water solution of CaCu 3 Ti 4 O according to claim 1, wherein, described alkaline calcium compound, alkaline copper compound and titan-alkoxide are joined respectively with making precursor water solution in a aqueous citric acid solution in batches; Perhaps described alkaline calcium compound, alkaline copper compound are added in first part of aqueous citric acid solution, and titan-alkoxide is added in second part of aqueous citric acid solution, then two parts of mixed precursor water solution that get of aqueous citric acid solution.
7. method for preparing the calcium copper titanate ceramics powder, its step comprises: each described precursor water solution that is used to prepare CaCu 3 Ti 4 O of claim 1 to 6 is carried out drying, obtain pressed powder; Pressed powder makes the calcium copper titanate ceramics powder through pre-burning decomposition and calcination process successively.
8. the method for preparing the calcium copper titanate ceramics powder according to claim 7, wherein, the exsiccant method can be lyophilize, spraying drying or any method in the oven dry in baking oven.
9. the method for preparing the calcium copper titanate ceramics powder according to claim 7, wherein, the temperature that pre-burning is decomposed is 300-500 ℃.
10. the method for preparing the calcium copper titanate ceramics powder according to claim 9, wherein, the temperature that pre-burning is decomposed is 450 ℃.
11. the method for preparing the calcium copper titanate ceramics powder according to claim 7, wherein, the incinerating temperature is 700-1200 ℃.
12. the method for preparing the calcium copper titanate ceramics powder according to claim 11, wherein, the incinerating temperature is 850 ℃.
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