CN106747408B - A kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material - Google Patents

A kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material Download PDF

Info

Publication number
CN106747408B
CN106747408B CN201611207278.1A CN201611207278A CN106747408B CN 106747408 B CN106747408 B CN 106747408B CN 201611207278 A CN201611207278 A CN 201611207278A CN 106747408 B CN106747408 B CN 106747408B
Authority
CN
China
Prior art keywords
tio
pressure
sensitive ceramic
voltage
ceramic material
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201611207278.1A
Other languages
Chinese (zh)
Other versions
CN106747408A (en
Inventor
赵敬忠
张成果
胡陈艳
罗磊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xian University of Technology
Original Assignee
Xian University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xian University of Technology filed Critical Xian University of Technology
Priority to CN201611207278.1A priority Critical patent/CN106747408B/en
Publication of CN106747408A publication Critical patent/CN106747408A/en
Application granted granted Critical
Publication of CN106747408B publication Critical patent/CN106747408B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/46—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on titanium oxides or titanates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
    • C04B35/63—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B using additives specially adapted for forming the products, e.g.. binder binders
    • C04B35/632—Organic additives
    • C04B35/634—Polymers
    • C04B35/63404—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C04B35/63416—Polyvinylalcohols [PVA]; Polyvinylacetates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3231—Refractory metal oxides, their mixed metal oxides, or oxide-forming salts thereof
    • C04B2235/3251—Niobium oxides, niobates, tantalum oxides, tantalates, or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3298—Bismuth oxides, bismuthates or oxide forming salts thereof, e.g. zinc bismuthate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
    • C04B2235/54—Particle size related information
    • C04B2235/5418—Particle size related information expressed by the size of the particles or aggregates thereof
    • C04B2235/5445—Particle size related information expressed by the size of the particles or aggregates thereof submicron sized, i.e. from 0,1 to 1 micron
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment
    • C04B2235/6562—Heating rate
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6581—Total pressure below 1 atmosphere, e.g. vacuum
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/658—Atmosphere during thermal treatment
    • C04B2235/6582—Hydrogen containing atmosphere

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)

Abstract

The invention discloses a kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material, by TiO2、Nb2O5And Bi2O3It is put into after mixing in polyester tank, carries out wet ball-milling, then by dry, grinding, obtain mixed powder；Mixed powder is granulated, is then suppressed, biscuit is obtained；Biscuit is sintered after dumping, room temperature is furnace-cooled to, obtains TiO2Voltage-sensitive ceramic；By TiO2Voltage-sensitive ceramic is polished, and is heat-treated to obtain after cleaning, drying.TiO of the present invention2The preparation method of base low-pressure pressure-sensitive ceramic material, with TiO2For raw material, Nb is added2O5And Bi2O3, TiO is prepared using easy preparation process2Voltage-sensitive ceramic, then in H2Or sample is heat-treated in vacuum low oxygen partial pressure atmosphere, TiO can be made2Lattice Oxygen volatilization, oxygen vacancy concentration increase, and the number of semiconducting crystal grain increases, and barrier height reduces and width is thinned, and pressure sensitive voltage significantly reduces.

Description

A kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material
Technical field
The invention belongs to sensitive material preparation technical fields, and in particular to a kind of TiO2The system of base low-pressure pressure-sensitive ceramic material Preparation Method.
Background technique
Voltage-sensitive ceramic refers to that the semiconductive ceramic device of nonlinear change is presented with the variation of voltage for resistance value, microcosmic Structure is usually made of semiconducting crystal grain and insulating crystal boundary, and voltage-sensitive ceramic is protected because of its good nonlinear characteristic as voltage Protective material is widely used among various circuits, wherein what is studied and be most widely used is ZnO varistor, outstanding Advantage is that nonlinear factor is larger, but its pressure sensitive voltage is higher, it is difficult to be applied to the integrated of low pressure as semiconductor components and devices In circuit.
TiO2Base voltage-sensitive ceramic has the performance advantages such as excellent volt-ampere nonlinear characteristic, high dielectric constant, while its Simple production process, TiO similar with ZnO pressure sensitive2Base voltage-sensitive ceramic is also a kind of with the more of typical crystal boundary electrical properties Brilliant ceramic material is expected to realize low pressure to it.
Summary of the invention
The object of the present invention is to provide a kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material, the method achieve TiO2The low pressure of base voltage-sensitive ceramic.
The technical scheme adopted by the invention is that a kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material, including such as Lower step:
Step 1, by TiO2、Nb2O5And Bi2O3Be put into after mixing in polyester tank, carry out wet ball-milling, then by it is dry, Grinding, obtains mixed powder；
Step 2, the mixed powder of step 1 is granulated, is then suppressed, obtain biscuit；
Step 3, biscuit step 2 obtained is sintered after dumping, is furnace-cooled to room temperature, obtains TiO2Voltage-sensitive ceramic；
Step 4, TiO step 3 obtained2Voltage-sensitive ceramic is polished, and is heat-treated after cleaning, drying, and TiO is obtained2 Base low-pressure pressure-sensitive ceramic material.
The features of the present invention also characterized in that
TiO in step 12, Nb2O5, Bi2O3Mass ratio be 120~301:1:1.75~3.5.
TiO in step 12Granularity be 200nm~300nm.
The concrete mode of wet ball-milling is as follows in step 1:
Ratio by mixed raw material and zirconia ball and dehydrated alcohol with mass ratio for 1:1:1.5 is placed in polyester tank, with 8~12h of revolving speed ball milling of 350r/min~450r/min.
Drying is carried out in baking oven in step 1, and drying temperature is 60 DEG C~70 DEG C, and drying time is 10h~14h.
The PVA solution that mass fraction is 5% is added dropwise in step 2 into mixed powder, crosses 20 meshes and is granulated, then use Plastic bag sealing is placed for 24 hours, and re-compacted molding obtains biscuit.
In step 3 dumping be by biscuit in 550 DEG C~600 DEG C of Muffle furnace dumping 1.5h~2h；
Sintering is to be placed in the biscuit after dumping in electric furnace in a manner of burying burning in step 3, with 4 DEG C/min~6 DEG C/min Heating rate be warming up to 1360 DEG C~1410 DEG C, keep the temperature 2.5h~4h.
Heat treatment is in carrying out in vacuum tube furnace, in H in step 42Under atmosphere or vacuum atmosphere environment, with 4 DEG C/ Min~6 DEG C/min heating rate is warming up to 500 DEG C~600 DEG C, keeps the temperature and is cooled to 200 with the rate of 10 DEG C/min after 3h DEG C, then furnace cooling.
When in H2When being handled in atmosphere, partial pressure of oxygen 10-2Pa；When being handled in vacuum atmosphere environment, partial pressure of oxygen It is 10-4Pa。
The invention has the advantages that TiO of the present invention2The preparation method of base low-pressure pressure-sensitive ceramic material, with TiO2For original Material adds Nb2O5And Bi2O3, TiO is prepared using easy preparation process2Voltage-sensitive ceramic, then in H under certain temperature2Or it is true Sample is heat-treated in empty low oxygen partial pressure atmosphere, TiO can be made2Lattice Oxygen volatilization, oxygen vacancy concentration increase, and semiconducting is brilliant The number of grain increases, and barrier height reduces and width is thinned, and pressure sensitive voltage significantly reduces.
Detailed description of the invention
Fig. 1 is TiO of the present invention2The preparation method flow diagram of base low-pressure pressure-sensitive ceramic material；
Fig. 2 is gained TiO after sintering2The XRD spectrum of voltage-sensitive ceramic sample；
Fig. 3 is TiO2Voltage-sensitive ceramic sample before sintering after SEM figure；
Fig. 4 is the TiO being heat-treated under different atmosphere2The I-V curve of voltage-sensitive ceramic.
Specific embodiment
The following describes the present invention in detail with reference to the accompanying drawings and specific embodiments.
TiO of the present invention2The preparation method of base low-pressure pressure-sensitive ceramic material, as shown in Figure 1, including the following steps:
Step 1, according to TiO2, Nb2O5, Bi2O3Mass ratio be 120~301:1:1.75~3.5 weigh TiO respectively2, Nb2O5, Bi2O3, wherein TiO2Granularity be 200nm~300nm；
Step 2, by TiO2、Nb2O5And Bi2O3Mixing after with zirconia ball and dehydrated alcohol with mass ratio be 1:1:1.5 Ratio be placed in polyester tank, with revolving speed 8~12h of ball milling of 350r/min~450r/min, then at 60 DEG C~70 DEG C do Dry 10h~14h, grinding, obtain mixed powder；
Step 3, the PVA solution that mass fraction is 5% is added dropwise into the mixed powder that step 2 obtains, crosses 20 meshes It is granulated, is then placed for 24 hours with plastic bag sealing, re-compacted molding obtains biscuit；
Step 4, biscuit step 3 obtained dumping 1.5h~2h in 550 DEG C~600 DEG C of Muffle furnace, then to bury The mode of burning is placed in electric furnace, is warming up to 1360 DEG C~1410 DEG C with 4 DEG C/min~6 DEG C/min heating rate, is kept the temperature 2.5h ~4h, is furnace-cooled to room temperature, obtains TiO2Voltage-sensitive ceramic；
Step 5, TiO step 4 obtained2Voltage-sensitive ceramic is polished, cleaning, drying, then in vacuum tube furnace, In H2Under atmosphere or vacuum atmosphere environment, 500 DEG C~600 DEG C are warming up to 4 DEG C/min~6 DEG C/min heating rate, 200 DEG C are cooled to 10 DEG C/min rate after heat preservation 3h, then furnace cooling is (when in H2When being handled in atmosphere, partial pressure of oxygen It is 10-2Pa；When being handled in vacuum atmosphere environment, partial pressure of oxygen 10-4Pa), TiO is obtained2Base low-pressure pressure-sensitive ceramic material.
TiO of the present invention2The preparation method of base low-pressure pressure-sensitive ceramic material, with TiO2For raw material, Nb is added2O5And Bi2O3, TiO is prepared using easy preparation process2Voltage-sensitive ceramic, then in H under certain temperature2Or it is right in vacuum low oxygen partial pressure atmosphere Sample is heat-treated, and TiO can be made2Lattice Oxygen volatilization, oxygen vacancy concentration increase, and the number of semiconducting crystal grain increases, potential barrier Height reduces and width is thinned, and pressure sensitive voltage significantly reduces.
Preparation method of the present invention, prepares TiO by doping way first2Voltage-sensitive ceramic, then again to semiconductor grain Heat preservation heat treatment is carried out to realize intra-die semiconductor transformation and influence grain boundary features, finally significantly reduces pressure sensitive voltage.In this way Realization voltage-sensitive ceramic low pressure belong to innovation of the invention, change the mode of traditional pressure sensitive ceramics low pressure, to pressure Quick ceramics low pressure provides another important channel.
Due to Bi2O3Fusing point be 824 DEG C, be far below TiO2Equal high-melting-point substances, so Bi during the sintering process2O3Itself First melting formation liquid phase wraps up TiO2And Nb2O5Equal particles, as sintering temperature increases and progressively reaches sintering temperature, Bi2O3 It will be with TiO2、Nb2O5Deng the physical-chemical reaction that complexity occurs, a certain amount of congruent melting liquid phase is formed.The liquid formed under these high temperature Phase promotes the discharge of gas and the reduction of grain spacing with type of flow mass transfer, accelerates the densification process of sintering, together When promote TiO2Crystal grain is grown up.In this way, when reaching sintering temperature, in TiO2Between particle will filling thickness it is uniform Melt thin layer of liquid.In cooling procedure, Bi2O3It is precipitated from liquid phase and forms the second phase, remaining melting liquid phase component is not analysed Crystalline substance, in the form of glass in the presence of come, form the higher grain boundary layer of resistance value, assign crystal boundary insulation performance, form effective gesture It builds, makes material that there is voltage-sensitive effect.
The present invention mixes Nb2O5Afterwards, the Nb of minor radius5+Easily enter lattice, as donor impurity, Nb5+Part Ti will be replaced4+ And it is solid-solubilized in TiO2In, promote grain semiconducting；On the other hand, Nb is mixed2O5Afterwards in grain boundaries, so that interface state density increases, The increase for being conducive to grain boundary layer resistance value improves the height of boundary barrier potential, influences TiO2The electrical behavior of varistor.Moreover, this Invention is in TiO2Middle donor doping Nb2O5On the basis of, sintered TiO is handled by reducing atmosphere2Voltage-sensitive ceramic, can be into One step promotes its N-shaped semiconducting.For the sample handled under the atmosphere, there is following reaction:
Nb2O5Into lattice:
Lattice Oxygen volatilization:
The low oxygen partial pressure effect formed under hydrogen and high vacuum, can promote Lattice Oxygen to volatilize, balance is made to move right, increase The number of oxygen vacancy concentration and semiconducting crystal grain is added, so that crystal boundary bound charges reduce, pressure sensitive voltage is decreased.
TiO2It is typical non-stoichiometric compound, will form Lacking oxygen in crystal grain in airWith titanous grain SonEtc. point defects.Heat treatment can cause the variation of concentration of oxygen atoms in environment in different atmosphere, thus lead to TiO2Crystal grain Different degrees of diffusion occurs for internal oxygen atom.Crystal boundary is the express passway of Ion transfer, and concentration of oxygen atoms becomes in environment When change, grain boundaries can change therewith.In vacuum, hydrogen, is conducive to oxygen in lattice and volatilizees, intra-die and grain boundaries defect are dense Degree increases, lattice oxygen loss, and the position that trivalent titanium particle occupies tetravalence titanium particle forms defectTi content remains unchanged, therefore The Ti/O value of the sample being heat-treated under high vacuum state and hydrogen atmosphere, intra-die and crystal boundary is larger；Since oxygen atom is in crystalline substance Intragranular portion diffusion velocity is lower than grain boundaries, therefore the oxygen loss amount of grain boundaries is bigger, and Ti/O value is larger.
It is further described combined with specific embodiments below.
Embodiment 1
It is 200nm~300nm, the TiO that purity is 99.5% with granularity2For raw material (Degussa AG), with Nb2O5(AR, And Bi 99.99%)2O3(AR, 99.99%) is additive, TiO used2、 Nb2O5、Bi2O3It is commercial product.According to quality Compare TiO2: Nb2O5: Bi2O3=301:2:5 weighs ingredient, is then with mass ratio with zirconia ball and dehydrated alcohol by batch The ratio of 1:1:1.5 is placed in polyester tank, with the revolving speed ball milling 10h of 400r/min, gained slurry is taken out after the completion of ball milling, then will Slurry dry 12h in 70 DEG C of baking oven excludes dehydrated alcohol, then ground 325 mesh, then into the powder after sieving by It is added dropwise to the PVA solution that appropriate mass fraction is 5% to be uniformly mixed into powder, crosses 20 meshes and be granulated, put with plastic bag sealing It sets for 24 hours；It by powder pressing at diameter is about 15mm under the pressure of 250MPa, the disk that thickness is about 1mm, in 600 DEG C of horse Not dumping 2h in furnace；Biscuit is placed in electric furnace in a manner of burying burning, rises to 1400 DEG C with the heating rate of 5 DEG C/min, heat preservation 4h is furnace-cooled to room temperature and obtains TiO2Voltage-sensitive ceramic sample.Then sample is beaten with the sand paper of 400 mesh and 1500 mesh respectively It grinds, it is spare after cleaning, drying.Above-mentioned sample is placed in H again2Atmosphere processing is carried out under atmosphere, sample is placed in very by when processing In empty tube furnace, control partial pressure of oxygen is 10-2Pa rises to 600 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 3h, after the completion of processing, Furnace atmosphere is kept, 200 DEG C is cooled to according to the 10 DEG C/min of cooling process set, is then shut off system, allows sample with furnace It is cooling, etc. after temperature lower, close breather valve, complete TiO2The preparation of base low-pressure pressure-sensitive ceramic material.
In order to test electric property, to all TiO2Sample disk two sides coats silver electrode, keeps the temperature 30min at 550 DEG C It is allowed to be firmly combined.
In the present embodiment, using Brucker D8X x ray diffractometer x to gained TiO after sintering2Voltage-sensitive ceramic sample into Row material phase analysis, TiO after gained sintering2The XRD spectrum of voltage-sensitive ceramic sample is as shown in Fig. 2.According to Fig.2, it is marked with PDF After quasi- card is compareed, discovery sintering after sample principal crystalline phase be rutile, in addition, 2 θ of the angle of diffraction 33.19 °, 47.25 °, 58.49 ° there are three ebbs be Bi2O3Diffraction maximum, show to be precipitated in the sample being sintered at 1400 DEG C a small amount of Bi2O3。
Using Philip ESEM X30 scanning electron microscope to gained TiO after sintering2Voltage-sensitive ceramic sample carries out microscopic appearance Observation.Simultaneously using after dumping be sintered before biscuit microscopic appearance as compare.Fig. 3 is TiO2Voltage-sensitive ceramic sample is being sintered The SEM of front and back schemes.SEM figure of a of Fig. 3 for the biscuit before sintering after dumping, biscuit Central Plains before being sintered it can be seen from a of Fig. 3 Material particle is ellipsoid, and partial size is between 200nm-300nm, even size distribution, and particle is mutually agglomerated into big a few to tens of The aggregate of micron, contact tightness degree is poor between aggregate, inside aggregate and between there are certain amount scale sizes The scale of different hole, these holes is much larger than feed particles.The b of Fig. 3 is gained TiO after sintering2Voltage-sensitive ceramic sample SEM figure, TiO after being sintered it can be seen from the b of Fig. 32Crystallite dimension is much larger than TiO in 5-18 μ m2Raw material particle size；It is brilliant Interface is clear between grain, is completely embedded, grain boundary layer is relatively thin and thickness is uniform；Hole is uniformly distributed between crystal grain, pore-size Much smaller than crystal grain, shared volume is relatively small.It can also be seen that rutile crystal grain has growed by the b of Fig. 3, grain size Gap is obvious, and little crystal grain is distributed between the crystal boundary of big crystal grain.
In the experimentation of the present embodiment, without any after being sintered using the detection of CJ1001 varistor DC parameter instrument The TiO of heat treatment2The voltage-dependent characteristic of voltage-sensitive ceramic sample (as untreated standard specimen), while detecting through embodiment 1 in H2Atmosphere The TiO being finally prepared is heat-treated under environment2The voltage-dependent characteristic of base low-pressure pressure-sensitive ceramic material.And in other experiment items In the case that part is constant, change after being sintered to TiO2The atmosphere that voltage-sensitive ceramic sample is heat-treated carries out voltage-dependent characteristic The control of detection, specifically, to carry out heat preservation heat treatment, partial pressure of oxygen 10 under oxygen atmosphere environment-2Pa.It is handled under different atmosphere TiO2The results are shown in Table 1 for the pressure-sensitive parameter detecting of voltage-sensitive ceramic.
TiO under 1 different atmosphere of table2The pressure-sensitive parameter of voltage-sensitive ceramic
It can be seen that compared with untreated samples from the detection data of table 1, TiO after being heat-treated in vacuum and hydrogen2Examination The nonlinear factor and pressure sensitive voltage of sample, which have, significantly to be declined, wherein the parameter ratio of heat treatment sample is under hydrogen in a vacuum Range of decrease degree is bigger；And the nonlinear factor of sample and pressure sensitive voltage increase after being heat-treated in oxygen.Under vacuum and hydrogen The voltage-sensitive ceramic leakage current of processing has a degree of reduction compared with untreated sample, illustrates under vacuum and hydrogen The more untreated standard specimen of insulation performance of the voltage-sensitive ceramic sample of processing is good.
In the experimentation of the present embodiment, in order to preferably study atmosphere to TiO2The shadow of voltage-sensitive ceramic electric property It rings, in experimentation of the present invention, TiO obtained by the present embodiment is tested using the comprehensive physical property measuring system of VersLab2Base low-pressure pressure-sensitive Ceramic material is (to sintered TiO2Voltage-sensitive ceramic sample carries out obtained by the heat treatment under hydrogen atmosphere environment) I-V it is bent Line, while in the case where other experiment conditions are constant, change after being sintered to TiO2The gas that voltage-sensitive ceramic sample is heat-treated Atmosphere environment carries out the control of voltage-dependent characteristic detection, specifically, respectively with (partial pressure of oxygen 10 under oxygen atmosphere environment-2Pa), vacuum (partial pressure of oxygen 10 under atmosphere-4Pa heat preservation heat treatment) is carried out.The TiO being heat-treated under different atmosphere2The I-V of voltage-sensitive ceramic is bent Line is as shown in Figure 4.From fig. 4, it can be seen that three groups of VA characteristic curves show nonlinear characteristic.In low current area, curve is oblique Rate be almost greatly very much it is vertical, show what varistor showed almost to insulate.As the increase of voltage enters limited proportionality, electricity Resistance strongly reduces, and electric current increased dramatically, and produces pressure-sensitive character, and at this moment, voltage leads to electric current in a small-scale variation Change across multiple orders of magnitude.Illustrate that crystal boundary is breakdown, crystal boundary becomes electric conductivity good conductor by original insulator, assumes responsibility for Effect in circuit as protection device.As seen in Figure 4, the sample handled by hydrogen and vacuum atmosphere its for Voltage generate jump reaction it is more obvious, and pass through oxygen atmosphere processing sample its be to have one for the reaction of voltage threshold A reaction process, the variation of Cong Tuzhong slope of a curve can be seen that.
Embodiment 2
It is 200nm~300nm, the TiO that purity is 99.5% with granularity2For raw material (Degussa AG), with Nb2O5(AR, And Bi 99.99%)2O3(AR, 99.99%) is additive, TiO used2、 Nb2O5、Bi2O3It is commercial product.According to quality Compare TiO2: Nb2O5: Bi2O3=301:2:5 weighs ingredient, is then with mass ratio with zirconia ball and dehydrated alcohol by batch The ratio of 1:1:1.5 is placed in polyester tank, with the revolving speed ball milling 12h of 350r/min, gained slurry is taken out after the completion of ball milling, then will Slurry dry 14h in 60 DEG C of baking oven excludes dehydrated alcohol, then ground 325 mesh, then into the powder after sieving by It is added dropwise to the PVA solution that appropriate mass fraction is 5% to be uniformly mixed into powder, crosses 20 meshes and be granulated, put with plastic bag sealing It sets for 24 hours；It by powder pressing at diameter is about 15mm under the pressure of 250MPa, the disk that thickness is about 1mm, in 580 DEG C of horse Not dumping 2h in furnace；Biscuit is placed in electric furnace in a manner of burying burning, rises to 1360 DEG C with the heating rate of 5 DEG C/min, heat preservation 4h is furnace-cooled to room temperature and obtains TiO2Voltage-sensitive ceramic sample.Then sample is beaten with the sand paper of 400 mesh and 1500 mesh respectively It grinds, it is spare after cleaning, drying.Above-mentioned sample is placed under vacuum atmosphere environment progress atmosphere processing again, sample is placed in by when processing In vacuum tube furnace, control partial pressure of oxygen is 10-4Pa rises to 600 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 3h, and processing is completed Afterwards, keep furnace atmosphere, be cooled to 200 DEG C according to the 10 DEG C/min of cooling process set, be then shut off system, allow sample with Furnace is cooling, etc. after temperature lower, close breather valve, complete TiO2The preparation of base low-pressure pressure-sensitive ceramic material.
Embodiment 3
It is 200nm~300nm, the TiO that purity is 99.5% with granularity2For raw material (Degussa AG), with Nb2O5(AR, And Bi 99.99%)2O3(AR, 99.99%) is additive, TiO used2、 Nb2O5、Bi2O3It is commercial product.According to quality Compare TiO2: Nb2O5: Bi2O3=601:4:7 weighs ingredient, is then with mass ratio with zirconia ball and dehydrated alcohol by batch The ratio of 1:1:1.5 is placed in polyester tank, with the revolving speed ball milling 10h of 380r/min, gained slurry is taken out after the completion of ball milling, then will Slurry dry 10h in 70 DEG C of baking oven excludes dehydrated alcohol, then ground 325 mesh, then into the powder after sieving by It is added dropwise to the PVA solution that appropriate mass fraction is 5% to be uniformly mixed into powder, crosses 20 meshes and be granulated, put with plastic bag sealing It sets for 24 hours；It by powder pressing at diameter is about 15mm under the pressure of 250MPa, the disk that thickness is about 1mm, in 600 DEG C of horse Not dumping 1.5h in furnace；Biscuit is placed in electric furnace in a manner of burying burning, 1380 DEG C is risen to the heating rate of 5 DEG C/min, protects Warm 3h is furnace-cooled to room temperature and obtains TiO2Voltage-sensitive ceramic sample.Then sample is carried out with the sand paper of 400 mesh and 1500 mesh respectively It polishes, it is spare after cleaning, drying.Above-mentioned sample is placed in H again2Atmosphere processing is carried out under atmosphere, sample is placed in by when processing In vacuum tube furnace, control partial pressure of oxygen is 10-4Pa rises to 500 DEG C with the heating rate of 5 DEG C/min, keeps the temperature 3h, and processing is completed Afterwards, keep furnace atmosphere, be cooled to 200 DEG C according to the 10 DEG C/min of cooling process set, be then shut off system, allow sample with Furnace is cooling, etc. after temperature lower, close breather valve, complete TiO2The preparation of base low-pressure pressure-sensitive ceramic material.
Embodiment 4
It is 200nm~300nm, the TiO that purity is 99.5% with granularity2For raw material (Degussa AG), with Nb2O5(AR, And Bi 99.99%)2O3(AR, 99.99%) is additive, TiO used2、 Nb2O5、Bi2O3It is commercial product.According to quality Compare TiO2: Nb2O5: Bi2O3=240:2:5 weighs ingredient, is then with mass ratio with zirconia ball and dehydrated alcohol by batch The ratio of 1:1:1.5 is placed in polyester tank, with the revolving speed ball milling 11h of 400r/min, gained slurry is taken out after the completion of ball milling, then will Slurry dry 12h in 65 DEG C of baking oven excludes dehydrated alcohol, then ground 325 mesh, then into the powder after sieving by It is added dropwise to the PVA solution that appropriate mass fraction is 5% to be uniformly mixed into powder, crosses 20 meshes and be granulated, put with plastic bag sealing It sets for 24 hours；It by powder pressing at diameter is about 15mm under the pressure of 250MPa, the disk that thickness is about 1mm, in 550 DEG C of horse Not dumping 2h in furnace；Biscuit is placed in electric furnace in a manner of burying burning, rises to 1390 DEG C with the heating rate of 4 DEG C/min, heat preservation 3.5h is furnace-cooled to room temperature and obtains TiO2Voltage-sensitive ceramic sample.Then sample is beaten with the sand paper of 400 mesh and 1500 mesh respectively It grinds, it is spare after cleaning, drying.Above-mentioned sample is placed under vacuum atmosphere environment progress atmosphere processing again, sample is placed in by when processing In vacuum tube furnace, control partial pressure of oxygen is 10-4Pa rises to 580 DEG C with the heating rate of 4 DEG C/min, keeps the temperature 3h, and processing is completed Afterwards, keep furnace atmosphere, be cooled to 200 DEG C according to the 10 DEG C/min of cooling process set, be then shut off system, allow sample with Furnace is cooling, etc. after temperature lower, close breather valve, complete TiO2The preparation of base low-pressure pressure-sensitive ceramic material.
Embodiment 5
It is 200nm~300nm, the TiO that purity is 99.5% with granularity2For raw material (Degussa AG), with Nb2O5(AR, And Bi 99.99%)2O3(AR, 99.99%) is additive, TiO used2、 Nb2O5、Bi2O3It is commercial product.According to quality Compare TiO2: Nb2O5: Bi2O3=602:2:7 weighs ingredient, is then with mass ratio with zirconia ball and dehydrated alcohol by batch The ratio of 1:1:1.5 is placed in polyester tank, with the revolving speed ball milling 8h of 450r/min, gained slurry is taken out after the completion of ball milling, then will Slurry dry 12h in 70 DEG C of baking oven excludes dehydrated alcohol, then ground 325 mesh, then into the powder after sieving by It is added dropwise to the PVA solution that appropriate mass fraction is 5% to be uniformly mixed into powder, crosses 20 meshes and be granulated, put with plastic bag sealing It sets for 24 hours；It by powder pressing at diameter is about 15mm under the pressure of 250MPa, the disk that thickness is about 1mm, in 600 DEG C of horse Not dumping 2h in furnace；Biscuit is placed in electric furnace in a manner of burying burning, rises to 1410 DEG C with the heating rate of 6 DEG C/min, heat preservation 2.5h is furnace-cooled to room temperature and obtains TiO2Voltage-sensitive ceramic sample.Then sample is beaten with the sand paper of 400 mesh and 1500 mesh respectively It grinds, it is spare after cleaning, drying.Above-mentioned sample is placed in H again2Atmosphere processing is carried out under atmosphere, sample is placed in very by when processing In empty tube furnace, control partial pressure of oxygen is 10-4Pa rises to 550 DEG C with the heating rate of 6 DEG C/min, keeps the temperature 3h, after the completion of processing, Furnace atmosphere is kept, 200 DEG C is cooled to according to the 10 DEG C/min of cooling process set, is then shut off system, allows sample with furnace It is cooling, etc. after temperature lower, close breather valve, complete TiO2The preparation of base low-pressure pressure-sensitive ceramic material.

Claims (7)

1. a kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material, which comprises the steps of:
Step 1, by TiO2、Nb2O5And Bi2O3It is put into after mixing in polyester tank, carries out wet ball-milling, then pass through dry, grinding, Obtain mixed powder；
Step 2, the mixed powder of step 1 is granulated, is then suppressed, obtain biscuit；
Step 3, biscuit step 2 obtained is sintered after dumping, is furnace-cooled to room temperature, obtains TiO2Voltage-sensitive ceramic；
In step 3 dumping be by biscuit in 550 DEG C~600 DEG C of Muffle furnace dumping 1.5h~2h；
Sintering is to be placed in the biscuit after dumping in electric furnace in a manner of burying burning in step 3, with 4 DEG C/min~6 DEG C/min liter Warm rate is warming up to 1360 DEG C~1410 DEG C, keeps the temperature 2.5h~4h；
Step 4, TiO step 3 obtained2Voltage-sensitive ceramic is polished, and is heat-treated after cleaning, drying, and TiO is obtained2Base is low Press pressure-sensitive ceramic material；
Heat treatment is in carrying out in vacuum tube furnace, in H in step 42Under atmosphere or vacuum atmosphere environment, with 4 DEG C/min~ The heating rate of 6 DEG C/min is warming up to 500 DEG C~600 DEG C, keeps the temperature and is cooled to 200 DEG C with the rate of 10 DEG C/min after 3h, then Furnace cooling.
2. TiO according to claim 12The preparation method of base low-pressure pressure-sensitive ceramic material, which is characterized in that in step 1 TiO2, Nb2O5, Bi2O3Mass ratio be 120~301:1:1.75~3.5.
3. TiO according to claim 12The preparation method of base low-pressure pressure-sensitive ceramic material, which is characterized in that in step 1 TiO2Granularity be 200nm~300nm.
4. TiO according to claim 12The preparation method of base low-pressure pressure-sensitive ceramic material, which is characterized in that wet in step 1 The concrete mode of formula ball milling is as follows:
Ratio by mixed raw material and zirconia ball and dehydrated alcohol with mass ratio for 1:1:1.5 is placed in polyester tank, with 350r/ 8~12h of revolving speed ball milling of min~450r/min.
5. TiO according to any one of claims 1 to 42The preparation method of base low-pressure pressure-sensitive ceramic material, which is characterized in that step Drying is carried out in baking oven in rapid 1, and drying temperature is 60 DEG C~70 DEG C, and drying time is 10h~14h.
6. TiO according to claim 12The preparation method of base low-pressure pressure-sensitive ceramic material, which is characterized in that in step 2 to The PVA solution that mass fraction is 5% is added dropwise in mixed powder, crosses 20 meshes and is granulated, then placed with plastic bag sealing For 24 hours, re-compacted molding, obtains biscuit.
7. TiO according to claim 12The preparation method of base low-pressure pressure-sensitive ceramic material, which is characterized in that when in H2Gas When being handled in atmosphere environment, partial pressure of oxygen 10-2Pa；When being handled in vacuum atmosphere environment, partial pressure of oxygen 10-4Pa。
CN201611207278.1A 2016-12-23 2016-12-23 A kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material Active CN106747408B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611207278.1A CN106747408B (en) 2016-12-23 2016-12-23 A kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611207278.1A CN106747408B (en) 2016-12-23 2016-12-23 A kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material

Publications (2)

Publication Number Publication Date
CN106747408A CN106747408A (en) 2017-05-31
CN106747408B true CN106747408B (en) 2019-11-22

Family

ID=58919705

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611207278.1A Active CN106747408B (en) 2016-12-23 2016-12-23 A kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material

Country Status (1)

Country Link
CN (1) CN106747408B (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102424577A (en) * 2011-09-20 2012-04-25 桂林电子科技大学 Low voltage varistor ceramic material and preparation method thereof
CN102584210A (en) * 2012-02-07 2012-07-18 上海海事大学 Preparation method for high-voltage TiO2 ring varistor
CN103058648A (en) * 2013-01-04 2013-04-24 河南科技大学 La2O3-SnO2-Zn2SnO4 varistor-capacitor bifunctional ceramic material and preparation method thereof
CN104744029A (en) * 2015-03-10 2015-07-01 河南科技大学 Bi2O3-SnO2-Zn2SnO4 voltage sensitive-capacitance dual-function ceramic material and preparation method thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007223863A (en) * 2006-02-24 2007-09-06 Tdk Corp Dielectric porcelain composition and method of manufacturing the same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102424577A (en) * 2011-09-20 2012-04-25 桂林电子科技大学 Low voltage varistor ceramic material and preparation method thereof
CN102584210A (en) * 2012-02-07 2012-07-18 上海海事大学 Preparation method for high-voltage TiO2 ring varistor
CN103058648A (en) * 2013-01-04 2013-04-24 河南科技大学 La2O3-SnO2-Zn2SnO4 varistor-capacitor bifunctional ceramic material and preparation method thereof
CN104744029A (en) * 2015-03-10 2015-07-01 河南科技大学 Bi2O3-SnO2-Zn2SnO4 voltage sensitive-capacitance dual-function ceramic material and preparation method thereof

Also Published As

Publication number Publication date
CN106747408A (en) 2017-05-31

Similar Documents

Publication Publication Date Title
CN106673642B (en) Giant dielectric low-loss CCTO-based ceramic material and preparation method thereof
Wang et al. Dielectric properties and impedance spectroscopy of MnCO3‐modified (Ba0. 85Ca0. 15)(Zr0. 1Ti0. 9) O3 lead‐free ceramics
Kuo et al. Effect of Ag on the microstructure and electrical properties of ZnO
Liu et al. Structural and electrical properties of ZnO-doped 8 mol% yttria-stabilized zirconia
Xu et al. Microstructure and electrical properties of Sc2O3-doped ZnO–Bi2O3-based varistor ceramics
Anselmi‐Tamburini et al. Nanoscale effects on the ionic conductivity of highly doped bulk nanometric cerium oxide
Zhang et al. Grain boundary conduction of Ce0. 9Gd0. 1O2− δ ceramics derived from oxalate coprecipitation: effects of Fe loading and sintering temperature
US20090211903A1 (en) Indium zinc oxide based sputtering target, method of manufacturing the same, and indium zinc oxide based thin film
Perry et al. Local electrical and dielectric properties of nanocrystalline yttria-stabilized zirconia
Zhao et al. Influence of Ta2O5 doping and microwave sintering on TiO2-based varistor properties
Liang et al. Improved dielectric properties and grain boundary response in neodymium-doped Y2/3Cu3Ti4O12 ceramics
CN106747410A (en) The bias titania-based composite dielectric ceramic material of stable type giant dielectric low-loss
Tian et al. Novel ultrahigh-performance ZnO-based varistor ceramics
Gao et al. Nanocrystalline barium strontium titanate ceramics synthesized via the “organosol” route and spark plasma sintering
Peng et al. Effect of Mg substitution on microstructure and electrical properties of Mn 1.25 Ni 0.75 Co 1.0− x Mg x O 4 (0≤ x≤ 1) NTC ceramics
Hussain et al. Electromechanical properties of lead‐free Nb‐doped 0.95 Bi0. 5Na0. 5TiO3‐0.05 BaZrO3 piezoelectric ceramics
Zhang et al. Effects of the Er2O3 doping on the microstructure and electrical properties of ZnO–Bi2O3 based varistor ceramics
Liu et al. Influence of Co2O3 doping on the microstructure and electrical properties of ZnO–Bi2O3-based varistors
Zhao et al. Ba (Zr0. 3Ti0. 7) O3 doping to enhance the dielectric and energy discharging performances of a 0.65 Bi0. 5Na0. 5TiO3–0.35 Sr0. 7Bi0. 2TiO3 lead-free ceramic
CN106747408B (en) A kind of TiO2The preparation method of base low-pressure pressure-sensitive ceramic material
Sun et al. Effect of dispersant concentration on preparation of an ultrahigh density ZnO–Al2O3 target by slip casting
Aktas et al. Influence of Co3O4 addition on the ionic conductivity and microstructural properties of yttria-stabilized zirconia (8YSZ)
Liu et al. Fabrication, microstructure, dielectric, and ferroelectric properties of (Bi0. 5Na0. 5) 0.94 Ba0. 06TiO3 nanograined ceramics via cold-sintering-assisted sintering
Maglia et al. Transport properties in bulk nanocrystalline Sm-doped ceria with doping content between 2 and 30 at.%
Ramzan et al. Characterization of sub-stoichiometric tungsten trioxide (WO3− X) using impedance spectroscopy

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant