CN102515779A - Rare earth oxide composite additive for zinc oxide varistor and preparation method thereof - Google Patents
Rare earth oxide composite additive for zinc oxide varistor and preparation method thereof Download PDFInfo
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- CN102515779A CN102515779A CN2011104045648A CN201110404564A CN102515779A CN 102515779 A CN102515779 A CN 102515779A CN 2011104045648 A CN2011104045648 A CN 2011104045648A CN 201110404564 A CN201110404564 A CN 201110404564A CN 102515779 A CN102515779 A CN 102515779A
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Abstract
The invention relates to a rare earth oxide composite additive for a zinc oxide varistor and a preparation method thereof and belongs to the technical field of varistor material preparation. The preparation method comprises the following steps of: precipitating two or more rare earth element salts, filtering to obtain a precipitate, washing, drying, and calcining to obtain the rare earth oxide composite additive for the zinc oxide varistor. Components of the rare earth oxide composite additive prepared are uniformly mixed. Particle distribution range is narrow. Hydrogen chloride in mother liquor after precipitation can be recovered and reused. There is no discharge of harmful gases such as nitrogen oxide and the like during the calcining process, the whole process is environmentally friendly and has no pollution. In the meanwhile, in comparison with a plurality of rare earth oxide respectively added in a zinc oxide varistor, the rare earth oxide composite additive prepared by the preparation method can be used to make various rare earth elements added to be uniformly distributed, substantially improve the microstructure of the zinc oxide varistor and greatly raise its comprehensive electric properties.
Description
Technical field
The present invention relates to a kind of Zinc-oxide piezoresistor with rare earth oxide complex additive and preparation method thereof, belong to the ceramic material preparing technical field.
Background technology
Zinc-oxide piezoresistor from nineteen sixty-eight by since the PANASONIC exploitation just with the performance of excellence such as with low cost, that preparation is simple, nonlinear factor is big, response is fast, leakage current is little, be widely used in various ultra-high-tension power transmission lines, DC power-supply system and large-scale power grid system.Along with the fast development of above-mentioned various high pressure engineering system, the security and the safety of relevant device are had higher requirement, therefore, electrical property is good, and the exploitation of the pressure-sensitive ceramic material that safety is high gets more and more people's extensive concerning.
Zinc oxide pressure-sensitive ceramic normally adds other an amount of additive metal oxides in zinc oxide matrix material, like bismuthous oxide bismuth trioxide, and Antimony Trioxide: 99.5Min, three powder blues, Manganse Dioxide, chromium trioxides etc. through ball mill mixing, carry out high temperature sintering and form after the moulding.Wherein, doping proper amount of rare-earth oxide compound in zinc oxide pressure-sensitive ceramic can make its anchoring at the crystal boundary place, plays the effect of inhibited oxidation zinc grain growing, can also significantly improve the pressure sensitive voltage of zinc oxide pressure-sensitive ceramic simultaneously.
Patent CN1844044A can make potential gradient bring up to more than the 500V/mm through singly mixing or double rare-earth-mixed oxide compound cerium oxide and oxidation are rolled.
Patent CN101279844A does not mix through interpolation or is mixed with Al
2O
3Sc
2O
3With rare earth oxide Y
2O
3, CeO
2, La
2O
3, Er
2O
3, Nd
2O
3, Dy
2O
3In a kind of, make the potential gradient of zinc oxide pressure-sensitive ceramic bring up to 1300～1600V/mm, nonlinear factor is 30～50, leakage current is 2～20 μ A.
Patent CN101265083A makes the potential gradient of zinc oxide pressure-sensitive ceramic bring up to 1000～1300V/mm through adding the nitrate salt of rare earth element yttrium and praseodymium.
At present existing method is general adopt with the oxide compound of elements such as rare earth oxide and zinc oxide base-material and Bi, Co, Sb, Mn, Cr simultaneously ball mill mixing with the acquisition zinc oxide piezoresistive material; Cause the REE additive of trace to be difficult to be uniformly dispersed on the one hand; Thereby influence uniform microstructure property and the rare earth oxide of voltage-sensitive ceramic anchoring effect, and then influence the potential gradient and the comprehensive electrochemical properties of voltage-sensitive ceramic at the voltage-sensitive ceramic crystal boundary; On the other hand; Through add nitrate of rare earth element then pyrolytic decomposition obtain the method for rare earth oxide additive, though can improve the dispersing uniformity of rare earth oxide additive; Can produce objectionable impuritiess such as oxynitride during high-temperature calcination, environment is caused serious pollution.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide the preparation method of a kind of Zinc-oxide piezoresistor with rare earth oxide complex additive.
The present invention at first prepares two kinds or two or more rare-earth element salt depositions, after calcining, obtains Zinc-oxide piezoresistor then and uses rare earth oxide complex additive.Compare with the addition means of traditional rare earth oxide additive; The interpolation of rare earth oxide complex additive according to the invention can effectively improve the dispersing uniformity of rare earth oxide in zinc oxide pressure-sensitive ceramic; Can effectively improve simultaneously the microstructure of zinc oxide pressure-sensitive ceramic; Improve the anchoring effect of rare earth oxide, improved the comprehensive electrochemical properties of Zinc-oxide piezoresistor at the voltage-sensitive ceramic crystal boundary.
In order to achieve the above object, the present invention has adopted following technical scheme:
Said Zinc-oxide piezoresistor uses the preparation method of rare earth oxide complex additive to be: precipitating rare earth element salt, filter then, and obtain deposition, washing, dry, calcining obtain Zinc-oxide piezoresistor and use rare earth oxide complex additive.Wherein, said REE is selected from two kinds or two or more mixtures among Sc, Y, Pr, Ce, La, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu.Said mixture, for example Sc/Y/Pr, Ce/La, Nd/Pm/Sm/Eu, Ce/La/Nd/Pm, Sm/Eu/Gd/Tb, Tb/Dy/Ho/Er/Tm, Eu/Gd/Tb/Dy/Ho/Er, Sc/Y/Pr/Ce/La/Nd/Pm, Sc/Y/Pr/Ce/La/Nd/Pm, Pr/Ce/La, La/Nd/Pm, Gd/Tb/Dy, Er/Tm/Yb, Y/Pr/Ce/La, Er/Tm, Tm/Yb, Gd/Tb, Sm/Eu, Dy/Ho, Sm/Eu/Gd/Tb/Dy/Ho/Er/Tm/Yb, Sc/Lu, Y/Pr/Lu, Y/Pr/Lu/Gd/Tb, Pr/Lu/Eu/Gd/Tb/Dy, Sm/Eu/Gd/Tb/Lu, Er/Tm/Yb/Lu, Sm/Eu/Gd/Tb/Lu, Sc/Y/Pr/Lu, La/Nd/Lu, Y/Nd/Lu, Lu/Pm/Sm.
Those skilled in the art can be known, and any method that can precipitating rare earth salt all can realize the present invention; As preferred version; The method of precipitating rare earth salt according to the invention is oxalate precipitation method (oxalic acid is precipitation agent), the carbonic acid gas precipitator method (carbonic acid gas is a precipitation agent), ammonium bicarbonate precipitation method (bicarbonate of ammonia is precipitation agent), preferred oxalate precipitation method.
The preferred REE muriate of said rare-earth element salt.
Preferably, the REE chloride soln is mixed with oxalic acid solution, precipitin reaction takes place, filter, obtain the compound oxalate precipitation of REE, dry, calcining obtains Zinc-oxide piezoresistor and uses rare earth oxide complex additive.
Said REE chloride soln middle-weight rare earths volumetric molar concentration is 0.02～2.5mol/L; For example 0.03mol/L, 0.04mol/L, 0.06mol/L, 0.07mol/L, 0.08mol/L, 0.2mol/L, 0.5mol/L, 0.8mol/L, 1.3mol/L, 1.6mol/L, 1.8mol/L, 2.4mol/L, 2.3mol/L, 2.2mol/L; Preferred 0.05～2.0mol/L, further preferred 0.05～1.5mol/L.
In the said rare earth oxide complex additive, the molar percentage of REE is 0.01～99.9%, for example 0.02%, 0.03%, 0.05%, 1.5%, 2.5%, 4.0%, 7.5%, 98.5%, 97%, 95%, 94%, 92%.
The REE chloride soln adds oxalic acid solution, obtains the rare earth oxalate of white crystals.Oxalic acid is as precipitation agent because the solubleness of rare earth oxalate in acid raises with the increase of acidity, and acidity when identical solubleness reduce with the increase of ordination number.Simultaneously, the excessive or too small deposition that all can cause of concentration of oxalic acid is incomplete, therefore; In order to realize the present invention better; As preferred version, the concentration of oxalic acid of said oxalic acid solution is 0.05～4.0mol/L, for example 0.06mol/L, 0.07mol/L, 0.3mol/L, 0.5mol/L, 0.7mol/L, 1.2mol/L, 1.4mol/L, 1.8mol/L, 3.9mol/L, 3.8mol/L; Preferred 0.08～3.0mol/L, further preferred 0.1～2.0mol/L.
Being mixed into of said REE muriate and oxalic acid solution drips REE chloride soln and oxalic acid solution simultaneously, to reach both precipitin reaction takes place better, obtains deposition.
In mixing process; The drop rate of preferred said REE chloride soln is 0.05～80L/min; For example 0.06L/min, 0.07L/min, 0.08L/min, 0.2L/min, 0.3L/min, 0.4L/min, 0.5L/min, 5L/min, 10L/min, 15L/min, 20L/min, 25L/min, 35L/min, 45L/min, 55L/min, 75L/min, 70L/min, preferred 0.1～60L/min.
The drop rate of said oxalic acid solution is 0.1～140L/min; For example 0.11L/min, 0.14L/min, 0.18L/min, 0.5L/min, 10L/min, 20L/min, 25L/min, 30L/min, 40L/min, 50L/min, 60L/min, 80L/min, 110L/min, 115L/min, preferred 0.2～120L/min.
Described mixing, precipitin reaction are all carried out under 20～70 ℃, and for example 21 ℃, 22 ℃, 23 ℃, 24 ℃, 69 ℃, 68 ℃, 67 ℃, 66 ℃, preferably under 35～55 ℃, carry out,
In order to make precipitin reaction abundant, preferred said mixing, precipitin reaction are carried out under agitation condition.
The rotating speed of said stirring is 50～1000 rev/mins; For example 60 rev/mins, 70 rev/mins, 80 rev/mins, 90 rev/mins, 150 rev/mins, 200 rev/mins, 250 rev/mins, 350 rev/mins, 450 rev/mins, 550 rev/mins, 640 rev/mins, 750 rev/mins; 950 rev/mins, 900 rev/mins, preferred 100～800 rev/mins.
Time those skilled in the art of said precipitin reaction can select according to the knowledge of oneself, reach both sedimentary degree that fully react completely and get final product.
Accomplish continued in said precipitin reaction and stir 20～50min, for example 22min, 23min, 24min, 25min, 28min, 35min, 40min, 45min, 49min, 48min, 47min, preferably 30min.
After deposition is accomplished, deposition is washed.Water washing is adopted in said washing, preferably adopts deionized water wash.
Simultaneously, in order to improve washing effect, carry out suction filtration in the time of washing, the present invention of suction filtration number of times is restriction not, reaches washes clean and gets final product.
After washing, deposition is carried out drying.Said drying is selected from a kind of in vacuum-drying, forced air drying, microwave drying, the ultra red ray drying, preferred vacuum-drying, and vacuum drying temperature is 60～100 ℃, for example 70 ℃, 75 ℃, 84 ℃, 91 ℃, 95 ℃.
Dried deposition is calcined, and said incinerating temperature is 500～1200 ℃, for example 510 ℃, 520 ℃, 530 ℃, 540 ℃, 1150 ℃, 1100 ℃, 1050 ℃, and preferred 650～1000 ℃.The incinerating time is 1～4h, for example 1.1h, 1.5h, 1.8h, 2.2h, 3.8h, 3.7h, 3.5h, 3h, preferably 2h.
In sum, Zinc-oxide piezoresistor of the present invention is described below with the preparation method of rare earth oxide complex additive:
(1) preparation REE salts solution: wherein, rare-earth element salt is selected from any two kinds or the two or more mixtures in the described 17 kinds of REEs of aforesaid method of the present invention, preferred REE muriate.REE chloride soln middle-weight rare earths concentration is 0.02～2.5mol/L, preferred 0.05～2.0mol/L, further preferred 0.05～1.5mol/L.
(2) precipitating rare earth element salt: those skilled in the art can select any method that can realize precipitating rare earth element salt in this area, preferably adopt oxalate precipitation method, the carbonic acid gas precipitator method, ammonium bicarbonate precipitation method, the further preferred oxalate precipitation method that adopts.Adopting the oxalate precipitation method is that oxalic acid solution is that precipitation agent precipitates rare-earth element salt.
The preparation oxalic acid solution, the concentration of oxalic acid of oxalic acid solution is 0.05～4.0mol/L, preferred 0.08～3.0mol/L, further preferred 0.1～2.0mol/L.
Drip REE chloride soln and oxalic acid solution simultaneously, wherein, the drop rate of REE chloride soln is 0.05～80L/min, preferred 0.1～60L/min; The drop rate of oxalic acid solution is 0.1～140L/min, preferred 0.2～120L/min.
Both hybrid concurrencies are given birth to precipitin reaction, obtain deposition.Wherein, mixing, precipitin reaction are all carried out under 20～70 ℃, preferably under 35～55 ℃, carry out; Said mixing, precipitin reaction are carried out under agitation condition, and the rotating speed of stirring is 50～1000 rev/mins, preferred 100～800 rev/mins.
After precipitin reaction finishes, continue to stir 20～50min, preferred 30min.
(3) filter: filter mother liquor and precipitate and separate, obtain deposition.
(4) washing: the water washing precipitation, preferably adopt deionized water wash, in order to reach better washing effect, carry out suction filtration in the time of preferred the washing.
(5) drying: the deposition after (4) washing is carried out drying.Can adopt any one method in vacuum-drying, forced air drying, ultra red ray drying, the microwave drying to carry out, preferably adopt vacuum-drying.When vacuum-drying, preferred vacuum drying temperature is 60～100 ℃.
(6) calcining: (5) dried deposition calcined to obtain the finished product Zinc-oxide piezoresistor and use rare earth oxide complex additive.The incinerating temperature is 500～1200 ℃, preferred 650～1000 ℃; The incinerating time is 1～4h, preferred 2h.
In the said rare earth oxide complex additive, the molar percentage of REE is 0.01～99.9%.
Another object of the present invention is to provide a kind of Zinc-oxide piezoresistor that is obtained by method for preparing to use rare earth oxide complex additive, its particle size distribution range is narrow, and size distribution is even.
The rare earth oxide complex additive for preparing through present method has important purposes in Zinc-oxide piezoresistor.It can be used as the rare earth addition of Zinc-oxide piezoresistor, and has effectively improved the dispersiveness of rare earth oxide in Zinc-oxide piezoresistor, has improved the comprehensive electrochemical properties of Zinc-oxide piezoresistor.
Compared with prior art, outstanding advantage of the present invention and positively effect are following:
(1) through preparing the compound oxalate precipitation of REE; After calcining, obtain Zinc-oxide piezoresistor then and use rare earth oxide complex additive; Only produce carbonic acid gas in the calcination process, do not have topsoil deposits yields such as oxynitride, avoided environment is polluted.
(2) compare with the addition means of traditional rare earth oxide additive; The interpolation of this kind rare earth oxide complex additive can effectively improve the dispersing uniformity of rare earth oxide in zinc oxide pressure-sensitive ceramic, can effectively improve the microstructure of zinc oxide pressure-sensitive ceramic simultaneously.
(3) the compound oxalate precipitation of REE directly obtains the rare earth oxide composite additive after calcining, and can improve the anchoring effect of rare earth oxide at the voltage-sensitive ceramic crystal boundary, and then improve the comprehensive electrochemical properties of Zinc-oxide piezoresistor.
(4) preparation technology of the present invention is simple, and is easy to operate.Through the Zinc-oxide piezoresistor that the rare earth oxide complex additive that adds the present invention's preparation obtains, when reducing production costs, effectively improved the potential gradient of Zinc-oxide piezoresistor, reduced the residual voltage ratio of Zinc-oxide piezoresistor, reduced leakage current.
Embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
A kind of Zinc-oxide piezoresistor provided by the invention is said with the summary of the invention part with rare earth oxide complex additive and preparation method thereof.The present invention will further illustrate substantive distinguishing features of the present invention and marked improvement through the description of following embodiment, and still, the present invention only is confined to following embodiment.
Embodiment 1
At ambient temperature Yttrium trichloride and Cerium II Chloride are mixed with the aqueous solution that concentration is 0.05mol/L, wherein, the molar percentage of yttrium and cerium is respectively 70% and 30%; Oxalic acid is added deionized water be mixed with the aqueous solution that concentration is 0.1mol/L, keeping the water temperature of water-bath is 55 ℃, and the rotating speed of magnetic stirring apparatus is 100 rev/mins; Drip Yttrium trichloride and solution of cerium chloride by oxidation and oxalic acid solution simultaneously; Wherein, the drop rate of Yttrium trichloride and solution of cerium chloride by oxidation is 60L/min, and the flow of oxalic acid solution is 120L/min.After adding above-mentioned drips of solution fully, fully precipitate, wait to precipitate complete continued and stir 30min, filter, with deionized water thorough washing repeatedly, suction filtration repeatedly, until washing of precipitate is clean, and in vacuum drying oven 80 ℃ carry out drying.Dried 650 ℃ of calcinings 2 hours that are deposited in obtain the oxide complex additive of required Zinc-oxide piezoresistor with rare-earth element cerium and yttrium.
Oxide complex additive according to oxide powder, above-mentioned rare-earth element cerium and the yttrium of certain ratio weighing ZnO powder, Mn, Co, Bi, Cr and Sb; Carry out high energy wet-milling, drying, calcining, high energy dry grinding, compression moulding, high-temperature calcination, obtain Zinc-oxide piezoresistor.
Comparative Examples 1
Used rare earth oxide additive is respectively cerium oxide and the yttrium oxide that is purchased in this Comparative Examples, and the step of other preparation Zinc-oxide piezoresistors and the content of each material are all said with embodiment 1.
Embodiment 2
At ambient temperature Yttrium trichloride and praseodymium chloride are mixed with the aqueous solution that concentration is 1.5mol/L, wherein, the molar percentage of yttrium and praseodymium is respectively 25% and 75%; Oxalic acid is added deionized water be mixed with the aqueous solution that concentration is 2.0mol/L, keeping the water temperature of water-bath is 35 ℃, and the rotating speed of magnetic stirring apparatus is 800 rev/mins; Drip Yttrium trichloride and praseodymium chloride solution and oxalic acid solution simultaneously; Wherein, the drop rate of Yttrium trichloride and praseodymium chloride solution is 0.1L/min, and the flow of oxalic acid solution is 0.2L/min.After adding above-mentioned drips of solution fully, fully precipitate, wait to precipitate complete continued and stir 30min, filter, with deionized water thorough washing repeatedly, suction filtration repeatedly, until washing of precipitate is clean, and in vacuum drying oven 80 ℃ carry out drying.Dried 900 ℃ of calcinings 2 hours that are deposited in obtain the oxide complex additive of required Zinc-oxide piezoresistor with REE praseodymium and yttrium.
Oxide complex additive according to the oxide powder of certain ratio weighing ZnO powder, Mn, Co, Bi, Cr and Sb, above-mentioned REE praseodymium and yttrium; Carry out high energy wet-milling, drying, calcining, high energy dry grinding, compression moulding, high-temperature calcination, obtain Zinc-oxide piezoresistor.
Comparative Examples 2
Used rare earth oxide additive is respectively Praseodymium trioxide and the yttrium oxide that is purchased in this Comparative Examples, and the step of other preparation Zinc-oxide piezoresistors and the content of each material are all said with embodiment 2.
Embodiment 3
At ambient temperature Yttrium trichloride, praseodymium chloride, Dysprosium trichloride and Erbium trichloride are mixed with the aqueous solution that concentration is 1.0mol/L; Wherein, the molar percentage of rare earth element yttrium, praseodymium, dysprosium and erbium is respectively 35%, 45%, 10% and 10%, oxalic acid is added deionized water be mixed with the aqueous solution that concentration is 1.5mol/L; Keeping the water temperature of water-bath is 45 ℃; The rotating speed of magnetic stirring apparatus is 500 rev/mins, drips Yttrium trichloride, praseodymium chloride, Dysprosium trichloride and Erbium trichloride solution and oxalic acid solution simultaneously, wherein; The drop rate of Yttrium trichloride, praseodymium chloride, Dysprosium trichloride and Erbium trichloride solution is 10L/min, and the flow of oxalic acid solution is 20L/min.After adding above-mentioned drips of solution fully, fully precipitate, wait to precipitate complete continued and stir 30min, filter, with deionized water thorough washing repeatedly, suction filtration repeatedly, until washing of precipitate is clean, and in vacuum drying oven 80 ℃ carry out drying.Dried 1000 ℃ of calcinings 2 hours that are deposited in obtain the oxide complex additive of required Zinc-oxide piezoresistor with REE praseodymium, yttrium, dysprosium and erbium.
Oxide complex additive according to the oxide powder of certain ratio weighing ZnO powder, Mn, Co, Bi, Cr and Sb, above-mentioned REE praseodymium, yttrium, dysprosium and erbium; Carry out high energy wet-milling, drying, calcining, high energy dry grinding, compression moulding, high-temperature calcination, obtain Zinc-oxide piezoresistor.
Comparative Examples 3
Used rare earth oxide additive is respectively Praseodymium trioxide, yttrium oxide, dysprosium oxide and the Erbium trioxide that is purchased in this Comparative Examples, and the step of other preparation Zinc-oxide piezoresistors and the content of each material are all said with embodiment 3.
Embodiment 4
At ambient temperature Lanthanum trichloride, praseodymium chloride, samarium trichloride and Neodymium trichloride are mixed with the aqueous solution that concentration is 0.02mol/L; Wherein, the molar percentage of rare-earth elements of lanthanum, praseodymium, samarium and neodymium is respectively 15%, 45%, 25% and 15%, oxalic acid is added deionized water be mixed with the aqueous solution that concentration is 0.05mol/L; Keeping the water temperature of water-bath is 20 ℃; The rotating speed of magnetic stirring apparatus is 50 rev/mins, drips Lanthanum trichloride, praseodymium chloride, samarium trichloride and neodymium chloride solution and oxalic acid solution simultaneously, wherein; The drop rate of Lanthanum trichloride, praseodymium chloride, samarium trichloride and neodymium chloride solution is 0.05L/min, and the flow of oxalic acid solution is 0.1L/min.After adding above-mentioned drips of solution fully, fully precipitate, wait to precipitate complete continued and stir 20min, filter, with deionized water thorough washing repeatedly, until washing of precipitate is clean, and dry in air dry oven.Dried 500 ℃ of calcinings 1 hour that is deposited in obtains the oxide complex additive of required Zinc-oxide piezoresistor with rare-earth elements of lanthanum, praseodymium, samarium and neodymium.
Oxide complex additive according to oxide powder, above-mentioned rare-earth elements of lanthanum, praseodymium, samarium and the neodymium of certain ratio weighing ZnO powder, Mn, Co, Bi, Cr and Sb; Carry out high energy wet-milling, drying, calcining, high energy dry grinding, compression moulding, high-temperature calcination, obtain Zinc-oxide piezoresistor.
Comparative Examples 4
Used rare earth oxide additive is respectively lanthanum trioxide, Praseodymium trioxide, Samarium trioxide and the Neodymium trioxide that is purchased in this Comparative Examples, and the step of other preparation Zinc-oxide piezoresistors and the content of each material are all said with embodiment 4.
Embodiment 5
At ambient temperature thulium chloride, terbium chloride, cesium chloride and Yttrium trichloride are mixed with the aqueous solution that concentration is 2.5mol/L; Wherein, the molar content of REE thulium, terbium, caesium and yttrium is respectively 10%, 25%, 45% and 20%, oxalic acid is added deionized water be mixed with the aqueous solution that concentration is 4.0mol/L; Keeping the water temperature of water-bath is 70 ℃; The rotating speed of magnetic stirring apparatus is 1000 rev/mins, drips thulium chloride, terbium chloride, cesium chloride and yttrium chloride solution and oxalic acid solution simultaneously, wherein; The drop rate of thulium chloride, terbium chloride, cesium chloride and yttrium chloride solution is 80L/min, and the flow of oxalic acid solution is 140L/min.After adding above-mentioned drips of solution fully, fully precipitate, wait to precipitate complete continued and stir 50min, filter, with deionized water thorough washing repeatedly, until washing of precipitate is clean, and dry in infrared drying oven.Dried 1200 ℃ of calcinings 4 hours that are deposited in obtain the oxide complex additive of required Zinc-oxide piezoresistor with REE thulium, terbium, caesium and yttrium.
Oxide complex additive according to the oxide powder of certain ratio weighing ZnO powder, Mn, Co, Bi, Cr and Sb, above-mentioned REE thulium, terbium, caesium and yttrium; Carry out high energy wet-milling, drying, calcining, high energy dry grinding, compression moulding, high-temperature calcination, obtain Zinc-oxide piezoresistor.
Comparative Examples 5
Used rare earth oxide additive is respectively trioxide, terbium sesquioxide, Cs2O and the yttrium oxide that is purchased in this Comparative Examples, and the step of other preparation Zinc-oxide piezoresistors and the content of each material are all said with embodiment 5.
Embodiment 6
Erbium trichloride, Lanthanum trichloride, cesium chloride, samarium trichloride and Dysprosium trichloride are mixed with the aqueous solution that concentration is 1.8mol/L; Wherein the molar percentage of erbium, lanthanum, caesium, samarium and dysprosium is respectively 10%, 15%, 35%, 20% and 20%; Bicarbonate of ammonia is added deionized water be mixed with the aqueous solution that concentration is 3.0mol/L, keeping the water temperature of water-bath is 50 ℃, and the rotating speed of magnetic stirring apparatus is 700 rev/mins; Drip Erbium trichloride, Lanthanum trichloride, cesium chloride, samarium trichloride and Dysprosium trichloride solution and ammonium bicarbonate soln simultaneously; Wherein, the drop rate of Erbium trichloride, Lanthanum trichloride, cesium chloride, samarium trichloride and Dysprosium trichloride solution is 50L/min, and the flow of ammonium bicarbonate soln is 100L/min.After adding above-mentioned drips of solution fully, fully precipitate, wait to precipitate complete continued and stir 50min, filter, with deionized water thorough washing repeatedly, until washing of precipitate is clean, and dry in microwave drying oven.Dried 800 ℃ of calcinings 3 hours that are deposited in obtain the oxide complex additive of required Zinc-oxide piezoresistor with rare earth element er, lanthanum, caesium, samarium and dysprosium.
Oxide complex additive according to oxide powder, above-mentioned rare earth element er, lanthanum, caesium, samarium and the dysprosium of certain ratio weighing ZnO powder, Mn, Co, Bi, Cr and Sb; Carry out high energy wet-milling, drying, calcining, high energy dry grinding, compression moulding, high-temperature calcination, obtain Zinc-oxide piezoresistor.
Comparative Examples 6
Used rare earth oxide additive is respectively Erbium trioxide, lanthanum trioxide, Cs2O, Samarium trioxide and the dysprosium oxide that is purchased in this Comparative Examples, and the step of other preparation Zinc-oxide piezoresistors and the content of each material are all said with embodiment 6.
Embodiment 7
At ambient temperature Yttrium trichloride and cesium chloride are mixed with the aqueous solution that concentration is 1.8mol/L, wherein, the molar content of yttrium and caesium is respectively 40% and 60%; The rotating speed of magnetic stirring apparatus is 700 rev/mins, in Yttrium trichloride and cesium chloride solution, feeds dioxide gas, fully precipitates; Wait to precipitate complete continued and stir 40min, filter, with deionized water thorough washing repeatedly; Until washing of precipitate is clean, and dry in microwave drying oven.Dried 800 ℃ of calcinings 3 hours that are deposited in obtain the oxide complex additive of required Zinc-oxide piezoresistor with rare earth element yttrium and caesium.
Oxide complex additive according to oxide powder, above-mentioned rare earth element yttrium and the caesium of certain ratio weighing ZnO powder, Mn, Co, Bi, Cr and Sb; Carry out high energy wet-milling, drying, calcining, high energy dry grinding, compression moulding, high-temperature calcination, obtain Zinc-oxide piezoresistor.
Comparative Examples 7
Used rare earth oxide additive is respectively yttrium oxide and the Cs2O that is purchased in this Comparative Examples, and the step of other preparation Zinc-oxide piezoresistors and the content of each material are all said with embodiment 7.
The Zinc-oxide piezoresistor that the foregoing description 1～7 and Comparative Examples 1～7 are obtained carries out performance test, and test result is as shown in table 1:
Table 1:
| Voltage gradient | Leakage current | Limit voltage ratio |
| Embodiment 1: Comparative Examples 1 | 1.5 | 0.4～0.43 | 0.78～0.85 |
| Embodiment 2: Comparative Examples 2 | 1.8 | 0.6～0.65 | 0.80～0.89 |
| Embodiment 3: Comparative Examples 3 | 2.2 | 0.08～0.09 | 0.68～0.72 |
| Embodiment 4: Comparative Examples 4 | 1.7 | 0.4～0.43 | 0.78～0.82 |
| Embodiment 5: Comparative Examples 5 | 1.9 | 0.6～0.65 | 0.75～0.79 |
| Embodiment 6: Comparative Examples 6 | 2.3 | 0.07～0.08 | 0.65～0.73 |
| Embodiment 7: Comparative Examples 7 | 2.1 | 0.3～0.37 | 0.76～0.84 |
Can find out from above-mentioned all embodiment, as long as the proportioning that guarantees various parameters in the preparation process can obtain the high energy ZnO piezoresistive material in the listed scope of claim.
Applicant's statement; The present invention has carried out detailed description through above-mentioned specific embodiment to the present invention; But the present invention is not limited to the foregoing description and implementation method, and in concrete implementation process, those skilled in the art can both carry out concrete enforcement according to the specialized range of each processing parameter; Do not exceed with the given the foregoing description of the present invention; In the scope that does not exceed spirit of the present invention and essence, certain modification and distortion to the present invention makes still can realize result according to the invention.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. a Zinc-oxide piezoresistor is characterized in that said method is: precipitating rare earth element salt with the preparation method of rare earth oxide complex additive; Filter then; Obtain deposition, washing, dry, calcining obtain Zinc-oxide piezoresistor and use rare earth oxide complex additive;
Said REE is selected from two kinds or two or more mixtures among Sc, Y, Pr, Ce, La, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and the Lu.
2. method according to claim 1 is characterized in that, the method for said precipitating rare earth element salt is oxalate precipitation method, the carbonic acid gas precipitator method, ammonium bicarbonate precipitation method, preferred oxalate precipitation method;
Preferably, the preferred REE muriate of said rare-earth element salt.
3. method according to claim 1 and 2 is characterized in that, the REE chloride soln is mixed with oxalic acid solution; Precipitin reaction taking place, filter, obtains the compound oxalate precipitation of REE; Dry, calcining obtain Zinc-oxide piezoresistor and use rare earth oxide complex additive.
4. according to each described method of claim 1-3, it is characterized in that said REE chloride soln middle-weight rare earths volumetric molar concentration is 0.02～2.5mol/L, preferred 0.05～2.0mol/L, further preferred 0.05～1.5mol/L.
5. according to each described method of claim 1-4, it is characterized in that in the said rare earth oxide complex additive, the molar percentage of REE is 0.01～99.9%;
Preferably, the concentration of oxalic acid of said oxalic acid solution is 0.05～4.0mol/L, preferred 0.08～3.0mol/L, further preferred 0.1～2.0mol/L.
6. according to each described method of claim 1-5, it is characterized in that said being mixed into drips REE chloride soln and oxalic acid solution simultaneously;
Preferably, the drop rate of said REE chloride soln is 0.05～80L/min, preferred 0.1～60L/min;
Preferably, the drop rate of said oxalic acid solution is 0.1～140L/min, preferred 0.2～120L/min.
7. according to each described method of claim 1-6, it is characterized in that said mixing, precipitin reaction are all carried out under 20～70 ℃, preferably under 35～55 ℃, carry out;
Preferably, said mixing, precipitin reaction are carried out under agitation condition;
Preferably, the rotating speed of said stirring is 50～1000 rev/mins, preferred 100～800 rev/mins.
8. according to each described method of claim 1-7, it is characterized in that said precipitin reaction continued stirs 20～50min, preferred 30min;
Preferably, water washing is adopted in said washing, preferably adopts deionized water wash;
Preferably, carry out suction filtration said washing the time;
Preferably, said drying is selected from a kind of in vacuum-drying, forced air drying, microwave drying, the ultra red ray drying, preferred vacuum-drying;
Preferably, said vacuum drying temperature is 60～100 ℃;
Preferably, said incinerating temperature is 500～1200 ℃, preferred 650～1000 ℃;
Preferably, the said incinerating time is 1～4h, preferred 2h.
9. a Zinc-oxide piezoresistor that is prepared by each described method of claim 1-8 is used rare earth oxide complex additive, it is characterized in that its particle size distribution range is narrow, and size distribution is even.
10. a Zinc-oxide piezoresistor is with the purposes of rare earth oxide complex additive in Zinc-oxide piezoresistor.
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| CN106316384A (en) * | 2016-08-29 | 2017-01-11 | 张颖 | Piezoresistor material |
| CN109020535A (en) * | 2018-08-29 | 2018-12-18 | 四川大学 | A kind of difunctional titanium dioxide ceramic of pressure-sensitive-capacitor of high dielectric constant and preparation method thereof |
| CN112341186A (en) * | 2020-10-27 | 2021-02-09 | 国网电力科学研究院武汉南瑞有限责任公司 | Preparation method of zinc oxide piezoresistor with rare earth oxide additive subjected to pre-solid solution treatment |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103193489A (en) * | 2013-04-11 | 2013-07-10 | 景德镇陶瓷学院 | Preparation method and using method of additive capable of increasing microwave ceramic Q value |
| CN106316384A (en) * | 2016-08-29 | 2017-01-11 | 张颖 | Piezoresistor material |
| CN106316384B (en) * | 2016-08-29 | 2019-03-12 | 张颖 | A kind of piezoresistive material |
| CN109020535A (en) * | 2018-08-29 | 2018-12-18 | 四川大学 | A kind of difunctional titanium dioxide ceramic of pressure-sensitive-capacitor of high dielectric constant and preparation method thereof |
| CN109020535B (en) * | 2018-08-29 | 2021-03-26 | 四川大学 | High-dielectric-constant pressure-sensitive-capacitor dual-functional titanium dioxide ceramic and preparation method thereof |
| CN112341186A (en) * | 2020-10-27 | 2021-02-09 | 国网电力科学研究院武汉南瑞有限责任公司 | Preparation method of zinc oxide piezoresistor with rare earth oxide additive subjected to pre-solid solution treatment |
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