CN1027634C - Producing method for porcelain very-fine powder of thermal-sensitive resistor with positive temp. coefficient - Google Patents
Producing method for porcelain very-fine powder of thermal-sensitive resistor with positive temp. coefficient Download PDFInfo
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- CN1027634C CN1027634C CN 91111035 CN91111035A CN1027634C CN 1027634 C CN1027634 C CN 1027634C CN 91111035 CN91111035 CN 91111035 CN 91111035 A CN91111035 A CN 91111035A CN 1027634 C CN1027634 C CN 1027634C
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- 239000000843 powder Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910052573 porcelain Inorganic materials 0.000 title description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000919 ceramic Substances 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000010936 titanium Substances 0.000 claims abstract description 15
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 10
- 239000002184 metal Substances 0.000 claims abstract description 10
- 159000000009 barium salts Chemical class 0.000 claims abstract description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 7
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 7
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 7
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 7
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 7
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 6
- 159000000008 strontium salts Chemical class 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000004519 manufacturing process Methods 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 11
- 238000000354 decomposition reaction Methods 0.000 claims description 7
- 239000002019 doping agent Substances 0.000 claims description 7
- 150000001298 alcohols Chemical class 0.000 claims description 6
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical group [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 2
- 229910001864 baryta Inorganic materials 0.000 claims description 2
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical group [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 abstract description 7
- 238000001914 filtration Methods 0.000 abstract description 2
- 230000007062 hydrolysis Effects 0.000 abstract description 2
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 2
- 239000007853 buffer solution Substances 0.000 abstract 1
- JBFIKAWSLUUIRM-UHFFFAOYSA-N diazanium;oxalate;dihydrate Chemical compound [NH4+].[NH4+].O.O.[O-]C(=O)C([O-])=O JBFIKAWSLUUIRM-UHFFFAOYSA-N 0.000 abstract 1
- 150000001455 metallic ions Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 44
- 239000000126 substance Substances 0.000 description 30
- 239000007864 aqueous solution Substances 0.000 description 24
- 238000004448 titration Methods 0.000 description 23
- 239000002585 base Substances 0.000 description 21
- 238000000975 co-precipitation Methods 0.000 description 19
- 239000012530 fluid Substances 0.000 description 19
- 238000000967 suction filtration Methods 0.000 description 16
- 238000001035 drying Methods 0.000 description 15
- 239000007788 liquid Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 238000002441 X-ray diffraction Methods 0.000 description 13
- 238000002156 mixing Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 7
- 229910002367 SrTiO Inorganic materials 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 101100496858 Mus musculus Colec12 gene Proteins 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001012 protector Effects 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000003746 solid phase reaction Methods 0.000 description 2
- 238000010671 solid-state reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229940045511 barium chloride Drugs 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- GXUARMXARIJAFV-UHFFFAOYSA-L barium oxalate Chemical compound [Ba+2].[O-]C(=O)C([O-])=O GXUARMXARIJAFV-UHFFFAOYSA-L 0.000 description 1
- 229940094800 barium oxalate Drugs 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- KQAGKTURZUKUCH-UHFFFAOYSA-L strontium oxalate Chemical compound [Sr+2].[O-]C(=O)C([O-])=O KQAGKTURZUKUCH-UHFFFAOYSA-L 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
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Abstract
The present invention relates to a producing method for ceramic superfine powder of a positive temperature coefficient thermal-sensitive resistor, and belongs to the technical field of functional ceramics. A titanium tetrachloride alcohol stable product or a hydrolysis object is deposited and reacts with water solubility barium salt, water solubility strontium salt or water solubility lead salt, water solubility trivalent metal salt and a water solubility pentavalency metal salt in a buffer solution which is composed of ammonium hydroxide-ammonium oxalate monohydrate and normal butyl alcohol, the ceram ultrafine powder is obtained by filtering, baking and pre-burning, the ceram ultrafine powder comprises the formula: (Ba<1-x-y>Sr<x>M<y>)(Ti<1-z>M'<z>)O'3 or (Ba<1-x'-y'>Pb<x'>M<y'>)(Ti<1-z'>M'<z'>)O3, (wherein x and x'=0 to 100 mol%, y and y'=0 to 0.5 mol% and z and z'=0 to 0.5 mol%; the M is a trivalent metal ion of La, Y, Nd, etc., and the M' is a pentavalency metallic ion of Nb, Ta, etc.).
Description
The invention relates to the manufacture method of posistor (PTCR) ceramic ultrafine powder, belong to the function ceramics field.
The PTCR pottery is that a class is with BaTiO
3For base by partly leading the semiconductive ceramic that mixes and to form, it is to pass through BaTiO
3And with BaTiO
3For solid solution in the sosoloid of base is mixed a certain amount of donor impurity, the material that sintering forms in oxidizing atmosphere.When being lower than material Curie temperature or phase transition temperature, it presents n N-type semiconductorN feature, and along with the rising of temperature, in Curie temperature or more than the phase transition temperature, resistivity sharply increases, and its increasing degree can reach several magnitude, presents so-called PTCR effect.Utilize resistivity-temperature characteristic, voltage-current characteristic (static characteristic), the current-time characteristic (dynamic characteristic) of this material can make temperature sensor, overheat protector, controlled heating element, overcurrent protector, delay device and demagnetizer, have at aspects such as electronic industry, automotive industry, chemical, health care, industrial automation and household electrical appliance widely and use.
In recent years,, need high pure and ultra-fine PTCR ceramic powder, to satisfy the needs of low-resistivity, high withstand voltage, high curie point, big electric current, High-Power PTC R device along with the widespread use of PTCR material.In addition, along with electronic equipment to light, thin, short, littleization development, the PTCR components and parts are the same with other electronic devices and components, require miniaturization, lightweight, therefore correspondingly require big electric currentization, the high withstand voltage of PTCR material, and this also requires to make high-purity, superfine PTCR powder.Moreover, high-temp PTC R material, because contain lead, if the sintering temperature height causes the plumbous volatilization of part to cause material structure inhomogeneous, unstable properties, and the PTCR superfine powder can reduce firing temperature greatly, suppresses plumbous volatilization.
In addition, multilayer PTCR element is to realize small-sized, light weight, big electric fluidizing novel texture element, and ultrafine powder PTCR raw material also is the key that improves its characteristic.In sum, the manufacturing of high-purity, ultra-fine, uniform PTCR powder is the ten minutes needs.
But the technology in past is to adopt solid state reaction manufactured PTCR powder, is about to BaCO
3, SrCO
3Or Pb
3O
4With TiO
2Partly lead doping agent and mix, carry out solid state reaction at 1000～1200 ℃, through mechanical disintegration, sieve and obtain the PTCR powder, so grain-size is big and inhomogeneous.In crushing process, tend to again bring detrimental impurity into and reduce its performance.Trace doped because mechanically mixing is inhomogeneous, also must cause the inconsistent and yield rate of PTCR material property to reduce.
The somebody uses metal alkoxide manufactured BaTiO
3And BaTiO
3The matrix composite ultrafine powder, the production cost height is difficult to practicability, and particle diameter is 500
Go up and wait flat dawn the people on the clear 59-45926 of Japanese Patent, clear 59-45927, clear 59-45928, to disclose another kind of synthetic BaTiO
3, CaTiO
3, SrTiO
3The method of ultrafine powder, this resultant and water-soluble metal barium salt, calcium salt, strontium salt that is the compound that will contain Ti adds water decomposition reacts generation in strong alkali aqueous solution.The weak point of this technology is: it requires precipitin reaction to carry out in greater than 13 strong alkali aqueous solution in the pH value, the mobility scale of pH value is bigger in the reaction process, make that reaction conditions is inconsistent in the whole precipitin reaction process, thereby influence the homogeneity and the consistence of made powder particles and composition; And this method also is difficult to once the synthetic complex body PTCR ceramic ultrafine powder material that contains multiple metal ion.
The object of the present invention is to provide the method for a kind of economy and the large-duty PTCR of preparation ceramic ultrafine powder, the mobility scale that overcomes pH value in the above-mentioned synthetic method is bigger, and be difficult to once the synthetic defective that contains the complex body PTCR superfine powder of multiple metal ion, so that once synthesize high-purity, ultra-fine, the uniform PTCR ceramic powder that contains multiple metal ion.
A kind of general formula of the present invention is (Ba
1-x-ySr
xM
y) (Ti
1-xM '
x) O
3(wherein: x=0～100mol%; Y=0～0.5mol%; Z=0～0.5mol%; M is a kind of in the trivalent metal ions such as La, Y, Na; M ' is a kind of in the pentavalent metal ions such as Nb, Ta.) the manufacture method of posistor ceramic ultrafine powder, it is characterized in that with titanium tetrachloride (TiCl
4) alcohols stablize resultant or add the water decomposition resultant and water soluble barium salt, water-soluble strontium salt and introduce a kind of water-soluble trivalent metal salt or a kind of water-soluble pentavalent metal-salt of partly leading dopant ion, in the buffered soln of ammoniacal liquor-ammonium oxalate and organic alcohol formation, carry out precipitin reaction, the gained throw out is filtered (can wash if desired), oven dry (105～110 ℃), pre-burning (600～850 ℃), constant temperature (30min.～3hr).
Another kind of general formula of the present invention is (Ba
1-x '-y 'Pb
X 'M
Y ') (Ti
1-x 'M
X ') O
3(wherein: x '=0～100mol%; Y '=0～0.5mol%; Z '=0～0.5mol%; M is a kind of in the trivalent ions such as La, Y, Nd; M ' is a kind of in the pentavalent metal ions such as Nb, Ta.) the manufacture method of posistor ceramic ultrafine powder, it is characterized in that with titanium tetrachloride (TiCl
4) the alcohols resultant or add the water decomposition resultant and water soluble barium salt, introduce a kind of water-soluble trivalent metal salt and a kind of water-soluble pentavalent metal-salt partly lead dopant ion, be mixed with second titrating solution, be mixed with first titrating solution with water-soluble lead salt, successively first titrating solution and second titrating solution are added respectively in the buffered soln that ammoniacal liquor-ammonium oxalate and organic alcohol constitutes and carry out precipitin reaction, with the gained throw out filter, oven dry (105～110 ℃), pre-burning (600～850 ℃), constant temperature (30min～3hr).
Have now the present invention is discussed in detail.
In preparation process, the introducing of Ti element can be used TiCl
4Alcohols stablize resultant or add water decomposition resultant, wherein TiCl
4Alcohols stablize resultant and can use TiCl
4With the alcohols prepared in reaction; The introducing of Ba element can be selected nitrate of baryta Ba(NO for use
3)
2, bariumchloride BaCl
2, barium oxalate Ba(CH
3COO)
2; The introducing of Sr element can be selected strontium nitrate Sr(NO for use
3)
2, strontium chloride SrCl
2, strontium oxalate Sr(CH
3COO)
2; The introducing of Pb element can be selected lead nitrate Pb(NO for use
3)
2; The introducing of trace doped element can be selected its corresponding water miscible salt for use; As the buffered soln of titration base fluid,, can select ammoniacal liquor-ammonium oxalate (NH according to the requirement of required pH value scope
3H
2O-(NH
4)
2C
2O
4) system, and add an amount of organic reagent therein, as propyl carbinol etc.
According to stoichiometric ratio, with above-mentioned salts solution with contain Ti solution and mix and be made into the mixing titrating solution; But for containing Pb series, the Pb salts solution should be made into first titrating solution separately, and other component is made into second titrating solution.With the slow titration of above-mentioned titrating solution or be sprayed in the above-mentioned buffered soln as the titration base fluid, stir fast simultaneously, carry out chemical coprecipitation.
After the chemical coprecipitation, carry out suction filtration or press filtration; If desired, can wash; Then carry out drying treatment; Under certain pre-burning system, the throw out after the above-mentioned processing is carried out pre-burning again, synthetic crystalline state superfine powder.
Fig. 1 is NH
3H
2O-(NH
4)
2C
2O
4The buffer curve of buffered soln (C wherein
SConcentration for ammonium oxalate solution).
Fig. 2, Fig. 4, Fig. 6 are the XRD figure of powder after the pre-burning.
Fig. 3, Fig. 5, Fig. 7 are the TEM images of powder after the pre-burning.
Hereinafter elaborate the present invention with several embodiment.
With Sr(NO
3)
2The aqueous solution and certain density TiCl
4Pure stable liquid be made into the mixing titrating solution by stoichiometric ratio, and the titration base fluid is selected NH for use
3H
2O-(NH
4)
2C
2O
4Buffered soln adds an amount of organic reagents such as propyl carbinol.Fig. 1 is NH
3H
2O-(NH
4)
2C
2O
4The buffer curve of buffered soln.As can be seen from Figure 1, this buffered soln is between 8.5～10.0 the time in the pH value, curve is quite mild, utilizes this buffered soln to make that as the titration base fluid rangeability of the pH value of system is quite little in the precipitation process, thereby is guaranteed throw out chemical ingredients and particle diameter uniformity.Get most an amount of NH
3H
2O-(NH
4)
2C
2O
4With organic reagents such as propyl carbinols, make pH value 〉=9.2 of this buffered soln.At room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr. ", synthetic SrTiO
3The crystalline state superfine powder.Fig. 2 is the XRD figure of powder after the pre-burning, according to powder method, selects Cu target, Ni filter plate for use.Fig. 3 is SrTiO
3The TEM image, the particle diameter of this sample is 100～200
, particle diameter is homogeneous very.
Respectively with SrCl
2, Sr(CH
3COO)
2The aqueous solution and certain density TiCl
4Pure stable liquid be made into the mixing titrating solution by stoichiometric ratio, and the titration base fluid is selected the NH that adds organic reagents such as an amount of propyl carbinol for use
3H
2O-(NH
4)
2C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr. ", synthetic SrTiO
3The crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, its XRD figure is similar to Fig. 2, and the observations of TEM is with shown in Figure 3.
Embodiment 3
With Ba(NO
3)
2The aqueous solution and certain density TiCl
4Pure stable liquid be made into the mixing titrating solution by stoichiometric ratio, and the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr ", synthetic BaTiO
3The crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, its XRD figure is similar to Fig. 2, and the observations of TEM is similar in appearance to Fig. 3.
According to chemical formula Ba
0.7968Sr
0.2Y
0.0032TiO
3Press stoichiometric ratio with Ba(NO
3)
2, Sr(NO
3)
2, Y(NO
3)
3The aqueous solution and TiCl
4Pure stable liquid be made into the mixing titrating solution, the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2) C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr " obtains the crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, the result as shown in Figure 4.Fig. 5 is its TEM photo, and the particle diameter of this sample is 100～200
, and particle diameter homogeneous very.
Embodiment 5
According to chemical formula Ba
0.5968Sr
0.4Y
0.0032TiO
3Press stoichiometric ratio with Ba(NO
3)
2, Sr(NO
3)
2, Y(NO
3)
3The aqueous solution and TiCl
4Pure stable liquid be made into the mixing titrating solution, the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2) C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr " obtains the crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, the result is the same substantially with Fig. 4.The tem observation result is with shown in Figure 5.
Embodiment 6
According to chemical formula Ba
0.5968Sr
0.4Y
0.0032TiO
3Press stoichiometric ratio with Ba(NO
3)
2, Sr(NO
3)
2, Y(NO
3)
3The aqueous solution and TiCl
4Pure stable liquid be made into the mixing titrating solution, the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2) C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 600 ℃ * 3hr ", " 850 ℃ * 30min " obtains the crystalline state superfine powder respectively.Powder is carried out XRD analysis under above-mentioned identical condition, the result is the same substantially with Fig. 4.The tem observation result is with shown in Figure 5.
Embodiment 7
According to chemical formula Ba
0.7968Sr
0.2Y
0.0032TiO
3Press stoichiometric ratio with Ba(NO
3)
2, Sr(NO
3)
2, Y(NO
3)
3The aqueous solution and TiCl
4The resultant that adds water decomposition is made into the mixing titrating solution, and the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr " obtains the crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, the result is similar with Fig. 4.The same Fig. 5 of its tem observation result.
Embodiment 8
According to chemical formula Ba
0.7968Pb
0.2Y
0.0032TiO
3Press stoichiometric ratio with Pb(NO
3)
2The aqueous solution is made into first titrating solution separately, with Ba(NO
3)
2, Y(NO
3)
3The aqueous solution and TiCl
4Pure stable liquid be made into second titrating solution, the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, first in order titration first titrating solution, titration second titrating solution perhaps carries out titration respectively simultaneously again.Then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr " obtains the crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, its result such as Fig. 6.The observations of its TEM is shown in Fig. 7, and its particle diameter is 100～200
, and the suitable homogeneous of particle diameter.
Embodiment 9
According to chemical formula Ba
0.5968Pb
0.4Y
0.0032TiO
3Press stoichiometric ratio with Pb(NO
3)
2The aqueous solution is made into first titrating solution separately, with Ba(NO
3)
2, Y(NO
3)
3The aqueous solution and TiCl
4Pure stable liquid be made into second titrating solution, the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr " obtains the crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, its result is similar to Fig. 6.The tem observation result of powder is with shown in Figure 7.
Embodiment 10
According to chemical formula Ba
0.5968Pb
0.4La
0.0032TiO
3Press stoichiometric ratio with Pb(NO
3)
2The aqueous solution is made into first titrating solution separately, with Ba(NO
3)
2, LaCl
3The aqueous solution and TiCl
4Pure stable liquid be made into second titrating solution, the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr " obtains the crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, its result is similar to Fig. 6.The tem observation result of powder is with shown in Figure 7.
Embodiment 11
According to chemical formula Ba
0.5968Pb
0.4Nd
0.0032TiO
3Press stoichiometric ratio with Pb(NO
3)
2The aqueous solution is made into first titrating solution separately, with Ba(NO
3)
2, NdCl
3The aqueous solution and TiCl
4Pure stable liquid be made into second titrating solution, the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr " obtains the crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, its result is similar to Fig. 6.The tem observation result of powder is with shown in Figure 7.
Embodiment 12
According to chemical formula Ba
0.8Pb
0.2Ti
0.998Nb
0.002O
3Press stoichiometric ratio with Pb(NO
3)
2The aqueous solution is made into first titrating solution separately, with Ba(NO
3)
2, NbCl
5The aqueous solution and TiCl
4Pure stable liquid be made into second titrating solution, the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr " obtains the crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, its result is similar to Fig. 6.The tem observation result of powder is with shown in Figure 7.
Embodiment 13
According to chemical formula Ba
0.8Pb
0.2Ti
0.998Ta
0.002O
3Press stoichiometric ratio with Pb(NO
3)
2The aqueous solution is made into first titrating solution separately, with Ba(NO
3)
2, TaCl
5The aqueous solution and TiCl
4Pure stable liquid be made into second titrating solution, the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, at room temperature carry out chemical coprecipitation, then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr " obtains the crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, its result is similar to Fig. 6.The tem observation result of powder is with shown in Figure 7.
Embodiment 14
In this embodiment, inquire into the influence of co-precipitation temperature to synthetic crystalline state powder.
According to chemical formula Ba
0.7968Pb
0.2Y
0.0032TiO
3Press stoichiometric ratio with Pb(NO
3)
2The aqueous solution is made into first titrating solution separately, with Ba(NO
3)
2, Y(NO
3)
3The aqueous solution and TiCl
4Pure stable liquid be made into second titrating solution, the titration base fluid is selected above-mentioned NH for use
3H
2O-(NH
4)
2C
2O
4Buffered soln.Make pH value 〉=9.2 of this buffered soln, under the temperature of 15 ℃, 30 ℃, 45 ℃, 60 ℃ and 75 ℃, carry out chemical coprecipitation respectively.Then carry out suction filtration, washing, drying treatment, pre-burning under the processing condition of " 800 ℃ * 2hr " obtains the crystalline state superfine powder.Powder is carried out XRD analysis under above-mentioned identical condition, its result is all similar to Fig. 6.The observations of TEM shows that the variation of co-precipitation temperature is very little to synthetic crystalline state superfine powder influence, and its TEM image is all very close with Fig. 7.
In the present invention, as the selection and the preparation of the buffered soln of titration base fluid, be important means and method.In the precipitation pulverizing process, require component evenly, as one man be precipitated out, guarantee the relatively stable of pH value of solution value in the reaction process, thereby the consistence that guarantees the precipitation process reaction conditions is extremely important.For this reason, selecting suitable buffered soln for use is the key that addresses the above problem as precipitation agent (titration base fluid).In addition, because the experimental raw of selecting for use, as corresponding nitrate such as Ba, Sr, Pb, its aqueous solution is because of effects such as hydrolysis, present acidity to a certain degree, and the alcohols stable liquid of aforementioned Ti has extremely strong acidity, and this just certainly will make the pH value of solution in the reaction process change a lot, and this also is to select buffered soln as one of precipitation agent important reason.In buffered soln, add in right amount as organic reagents such as propyl carbinols, can reduce the surface tension of solution greatly, prevent that throw out from assembling in the chemical coprecipitation process.In addition,, and there is the organic reagent of a great deal of to be suspended in the water surface, can plays the volatilization that stops ammonia in the buffered soln because the dissolving of these organic reagents in water is limited, favourable to stablizing of pH value in the reaction process.
For containing Pb series, the Pb salts solution is made into first titrating solution separately, and other component is made into second titrating solution.This is because if these two kinds of titrating solutions also are made into mixing titrating solution, Pb
2+With the Cl that contains in the Ti solution
-Can form PbCl
2Precipitation is stopped up dropper mouth or nozzle, also can be because of PbCl
2Sedimentary losing and cause proportioning to depart from.
Wash during suction filtration, can remove Cl
-With other water-soluble impurity.
Adopt above-mentioned technology of the present invention, both can synthesize single titanate superfine powder, as BaTiO
3, SrTiO
3Deng, also can synthesize such as Ba
0.5968Sr
0.4Y
0.0032TiO
3Deng complex body PTCR superfine powder.The primary particle size of gained powder is 100～200
Between, and particle diameter is even, narrow distribution range.Because temperature is not obvious to the influence of precipitation process, make the precipitation pulverizing process be easy to control.In addition, this method provided by the invention does not need the operation through mechanical disintegration, thereby can avoid mixing of tramp material.Generally speaking, utilize method provided by the invention once to synthesize to contain high-purity, ultra-fine, uniform PTCR ceramic powder of multiple metal ion.
Claims (7)
1, a kind of general formula is (Ba
1-x-ySr
xM
y) (Ti
1-zM
' z) O
3(wherein: x=0～100mol%; Y=0～0.5mol%; Z=0～0.5mol%; M is a kind of in the trivalent metal ions such as La, Y, Nd; M
'The manufacture method of posistor ceramic ultrafine powder a kind of in the pentavalent metal ions such as Nb, Ta) is characterized in that with titanium tetrachloride (TiCl
4) alcohols stablize resultant and water soluble barium salt, water-soluble strontium salt and introduce a kind of water-soluble trivalent metal salt or a kind of water-soluble pentavalent metal-salt of partly leading dopant ion, in the buffered soln of ammoniacal liquor-ammonium oxalate and organic alcohol formation, carry out precipitin reaction, the gained throw out is filtered (can wash if desired), oven dry (105～110 ℃), pre-burning (600～850 ℃), constant temperature (30min～3hr).
2, a kind of general formula is (Ba
1-x-ySr
xM
y) (Ti
1-zM
z') O
3(wherein: x=0～100mol%; Y=0～0.5mol%; Z=0～0.5mol%; M is a kind of in the trivalent metal ions such as La, Y, Nd; M ' is a kind of in the pentavalent metal ions such as Nb, Ta) the manufacture method of posistor ceramic ultrafine powder, it is characterized in that with titanium tetrachloride (TiCl
4) add water decomposition resultant and water soluble barium salt, water-soluble strontium salt and introduce a kind of water-soluble trivalent metal salt or a kind of water-soluble pentavalent metal-salt of partly leading dopant ion, in the buffered soln of ammoniacal liquor-ammonium oxalate and organic alcohol formation, carry out precipitin reaction, the gained throw out is filtered (can wash if desired), oven dry (105～110 ℃), pre-burning (600～850 ℃), constant temperature (30min～3hr).
3, a kind of general formula is (Ba
1-x '-y 'Pb
X 'M
Y ') (Ti
1-z 'M
Z '') O
3(wherein: x '=0～100mol%; Y '=0～0.5mol%; Z '=0～0.5mol%; M is a kind of in the trivalent ions such as La, Y, Nd; M ' is a kind of in the pentavalent ions such as Nb, Ta) the manufacture method of posistor ceramic ultrafine powder, it is characterized in that with titanium tetrachloride (TiCl
4) alcohols resultant and water soluble barium salt, introduce a kind of water-soluble trivalent metal salt and a kind of water-soluble pentavalent metal-salt partly lead dopant ion, be mixed with second titrating solution, be mixed with first titrating solution with water-soluble lead salt, successively first titrating solution and second titrating solution are added respectively in the buffered soln that ammoniacal liquor-ammonium oxalate and organic alcohol constitutes and carry out precipitin reaction, the gained throw out is filtered, and oven dry (105～110 ℃), pre-burning (600～850 ℃), constant temperature (30min～3hr).
4, a kind of general formula is (Ba
1-x '-y 'Pb
X 'M
Y ') (Ti
1-z 'M
Z '') O
3(wherein: x '=0～100mol%; Y '=0～0.5mol%; Z '=0～0.5mol%; M is a kind of in the trivalent ions such as La, Y, Nd; M ' is a kind of in the pentavalent ions such as Nb, Ta) the manufacture method of posistor ceramic ultrafine powder, it is characterized in that with titanium tetrachloride (TiCl
4) add water decomposition resultant and water soluble barium salt, introduce a kind of water-soluble trivalent metal salt and a kind of water-soluble pentavalent metal-salt of partly leading dopant ion, be mixed with second titrating solution, be mixed with first titrating solution with water-soluble lead salt, successively first titrating solution and second titrating solution are added respectively in the buffered soln that ammoniacal liquor one ammonium oxalate and organic alcohol constitutes and carry out precipitin reaction, the gained throw out is filtered, and oven dry (105～110 ℃), pre-burning (600～850 ℃), constant temperature (30min～3hr).
5,, it is characterized in that said water soluble barium salt is nitrate of baryta (Ba(NO according to the manufacture method of claim 1,2,3 and 4 said posistor ceramic ultrafine powders
3)
2).
6,, it is characterized in that said water-soluble strontium salt is strontium nitrate (Sr(NO according to the manufacture method of claim 1 and 2 said posistor ceramic ultrafine powders
3)
2).
7,, it is characterized in that said water-soluble lead salt is lead nitrate (Pb(NO according to the manufacture method of claim 3 and 4 said posistor ceramic ultrafine powders
3)
2).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91111035 CN1027634C (en) | 1991-11-28 | 1991-11-28 | Producing method for porcelain very-fine powder of thermal-sensitive resistor with positive temp. coefficient |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 91111035 CN1027634C (en) | 1991-11-28 | 1991-11-28 | Producing method for porcelain very-fine powder of thermal-sensitive resistor with positive temp. coefficient |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1072658A CN1072658A (en) | 1993-06-02 |
| CN1027634C true CN1027634C (en) | 1995-02-15 |
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|---|---|---|---|
| CN 91111035 Expired - Fee Related CN1027634C (en) | 1991-11-28 | 1991-11-28 | Producing method for porcelain very-fine powder of thermal-sensitive resistor with positive temp. coefficient |
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|---|---|
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| CN1036190C (en) * | 1994-04-28 | 1997-10-22 | 西北大学 | High pureness super fined titanate and its sosoloid synthetic process |
| CN105006317A (en) * | 2015-08-03 | 2015-10-28 | 成都顺康电子有限责任公司 | Glass-encapsulated PTC thermistor and manufacturing method thereof |
| CN110776310B (en) * | 2019-11-06 | 2021-09-28 | 常州大学 | Method for preparing perovskite type composite oxide high-entropy ceramic powder by coprecipitation of ion compensation mixture |
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1991
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