CN110467457A - It is a kind of based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process and its preparation and application - Google Patents
It is a kind of based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process and its preparation and application Download PDFInfo
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- CN110467457A CN110467457A CN201910747296.6A CN201910747296A CN110467457A CN 110467457 A CN110467457 A CN 110467457A CN 201910747296 A CN201910747296 A CN 201910747296A CN 110467457 A CN110467457 A CN 110467457A
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- 239000000463 material Substances 0.000 title claims abstract description 104
- CDSUELAXTQWPNC-UHFFFAOYSA-N [Pb].[Hf] Chemical compound [Pb].[Hf] CDSUELAXTQWPNC-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000005096 rolling process Methods 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000012528 membrane Substances 0.000 title claims abstract description 21
- 238000004146 energy storage Methods 0.000 claims abstract description 18
- 239000000853 adhesive Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 13
- 238000012545 processing Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000003990 capacitor Substances 0.000 claims abstract description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 8
- 238000005245 sintering Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims description 36
- 235000015895 biscuits Nutrition 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 14
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 6
- 229910000464 lead oxide Inorganic materials 0.000 claims description 6
- YEXPOXQUZXUXJW-UHFFFAOYSA-N oxolead Chemical compound [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 claims description 6
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 6
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 5
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 5
- 229910001887 tin oxide Inorganic materials 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 239000000919 ceramic Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 4
- 229910052745 lead Inorganic materials 0.000 description 4
- 210000001161 mammalian embryo Anatomy 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- 229910052735 hafnium Inorganic materials 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- KUVFGOLWQIXGBP-UHFFFAOYSA-N hafnium(4+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Hf+4] KUVFGOLWQIXGBP-UHFFFAOYSA-N 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
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- 230000007423 decrease Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(IV) oxide Inorganic materials O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
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- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
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- 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
- C04B35/48—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 zirconium or hafnium oxides, zirconates, zircon or hafnates
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- 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
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- H01G4/00—Fixed capacitors; Processes of their manufacture
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Abstract
The present invention relates to a kind of based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process and its preparation and application, and the chemical general formula of the hafnium lead plumbate based antiferroelectric material is (Pb1‑3z/2Laz)(Hf1‑x‑ySnxTiy)O3, wherein 0 < z≤0.04,0 < x < 1.0,0 < y < 1.0；Preparation method: 1) by respective metal oxide according to (Pb1‑3z/2Laz)(Hf1‑x‑ySnxTiy)O3In corresponding stoichiometric ratio mixed grinding；2) pre-burning is dried；3) secondary grinding drying；4) it mixes, and roughing, finish rolling and cuts with adhesive；5) it carries out arranging at viscous processing and sintering, obtains hafnium lead plumbate based antiferroelectric material；The material can be used for preparing pulse power capacitor device, energy-storage capacitor, energy converter.Compared with prior art, preparation method is simple by the present invention, easy to operate, is suitable for mass production；Sample size adjustable of the present invention, applied widely, resistance to sparking can by force and energy storage density is high, has good application value.
Description
Technical field
The invention belongs to technical field of electronic materials, be related to it is a kind of based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process and
Preparation method and application.
Background technique
In recent years, Pulse Power Techniques are used widely in fields such as health care, laser technology and pollution controls, and
Core component of the energy-storage capacitor as pulse power system is the research emphasis of researcher.It is commonly used in storage
The dielectric material of energy capacitor includes ferroelectric material, antiferroelectric materials and linear dielectric substance.It is situated between with ferroelectric and linear electricity
Material is compared, and antiferroelectric has more excellent energy storage and charge-discharge characteristic due to its distinctive AFE-FE phase transformation, thus
It is considered as excellent energy storage material.
In terms of stored energy application, in order to improve the energy storage density of antiferroelectric materials, there are mainly two types of measures.The first measure
It is that modification is doped to ceramics according to tolerance factor formula, increases switch yard and improve saturated polarization.Second is to mention
Its high disruptive field intensity allows its AFE-FE phase transformation more sufficiently.It is square directly proportional due to energy storage density and breakdown electric field,
The breakdown electric field for improving material is main research direction.Currently, report antiferroelectric ceramics block energy storage density generally compared with
Low, since the ceramic block volume of synthesis in solid state is larger, the probability that defect occurs in inside increases, and it is lower to cause punch through field strength, energy storage
Performance can not improve.Other preparation processes are compared, casting technique and silk-screen printing technique can equally prepare antiferroelectric materials, but
The adhesive of addition is more, and since adhesive volatilization hole is more during burning paper as sacrificial offerings, compactness is poor, and to process environments requirement
It is higher.
Currently, being concentrated mainly on the modified zirconium of the excellent lanthanum of mature preparation process, energy-storage property to the research of antiferroelectric
Lead titanate antiferroelectric materials, but similar hafnium lead plumbate (PbHfO3) energy-storage property of based antiferroelectric material but rarely has report
Road.Although early in nineteen fifty-three PbHfO3It is just confirmed to be antiferroelectric, but about PbHfO3The document report of antiferroelectric is still
Seldom.PbHfO3Ceramics have high AFE-FE phase transformation switch yard (EF > 200kV/cm), higher saturated polarization (PmaxIt is reachable
45μC/cm2), high breakdown field strength (Eb is up to 270kV/cm) and relatively small electric hysteresis (Δ E~46kV/cm), about
PbHfO3Introducing for the preparation process of ceramics is relatively fewer, at present the traditional solid-phase synthesis of most uses, but synthesis in solid state
The energy storage density of the sample of method preparation is lower, limits further applying for antiferroelectric materials.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide one kind to be based on rolling membrane process
Hafnium lead plumbate based antiferroelectric material and the preparation method and application thereof, by a kind of novel technique for preparing hafnium lead plumbate base ceramics,
The uniformity and consistency of ceramics sample are improved, and then improves the disruptive field intensity of sample, the energy storage for being finally reached raising material is close
The purpose of degree, and preparation process is simple, and easy to operate, cost is relatively low, is suitble to industrial production hafnium lead plumbate based antiferroelectric material.
The purpose of the present invention can be achieved through the following technical solutions:
It is a kind of based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process, chemical general formula is (Pb1-3z/2Laz)(Hf1-x- ySnxTiy)O3, wherein the value range of z is 0 < z≤0.04, and the value range of x is 0 < x < 1.0, the value range of y be 0 < y <
1.0, x+y < 1.If x, y, z within the set range, not will be unable to obtain antiferroelectric materials of good performance.
Further, the value range of z is 0.01≤z≤0.04, and the value range of x is 0.18≤x≤0.68, and y's takes
Value range is 0.02≤y≤0.06.
Material is to enter matrix by Partial Elements doping using hafnium titanate system as matrix.
Other metallic elements can also be added as needed in hafnium lead plumbate based antiferroelectric material, such as barium, niobium, strontium, manganese or rare earth
The elements such as metal, to further increase the practical application value of material.
A kind of preparation method based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process, the hafnium lead plumbate based antiferroelectric material
The chemical general formula of material is (Pb1-3z/2Laz)(Hf1-x-ySnxTiy)O3, wherein the value range of z is 0≤z≤0.04, the value of x
Range is 0≤x < 1.0, and the value range of y is 0≤y < 1.0, x+y < 1；
The preparation method the following steps are included:
1) mixed material of metal oxide is subjected to a milled processed.
2) material after a milled processed is dried at 110-130 DEG C, and at 850-900 DEG C constant temperature 2-4h with into
Row preheating；The purpose of pre-burning is to make each raw material that pre-reaction occur by a high temperature action, preliminarily form target product,
To ensure the quality of final products.Temperature is excessively high, and sample loses activity, too low, is unable to pre-reaction and forms target product.
3) material after preheating is subjected to secondary milled processed, is dried at 110-130 DEG C later.
4) material after drying is mixed with adhesive with mass ratio 1:(0.2-0.25), 1-2h is first carried out on roll forming machine
Roughing, then finish rolling cuts later to required size to required thickness, obtains biscuit piece.Roll the organic agent prescription of film
It is as follows: polyvinyl alcohol (20wt%), deionized water (72wt%), dehydrated alcohol (8wt%).It on this basis, can be additional
The glycerol of 12wt% is as plasticizer.If the adhesive being added is too many, excessive organic solvent is remained in follow-up sintering and is easily caused
Hole, compactness decline；But if the adhesive being added is very little, and embryo piece is more dry and cracked, is not easy to roll the embryo piece of large area.Rolling
Successfully element embryo piece should save in the environment of certain humidity as far as possible, prevent dry cracking.
5) biscuit piece is placed in Muffle furnace and is first warming up to the heating rate of 0.5-2 DEG C/min (preferably 1 DEG C/min)
500-700 DEG C (preferably 600 DEG C), and constant temperature 2-5h is to carry out arranging viscous processing, it is therefore intended that embryo is removed with slow heating rate
Moisture and organic bond in body avoid causing hole and defect because heating is too fast in sintering, prevent alice phenomenon；Again
Constant temperature 2-4h obtains hafnium lead plumbate based antiferroelectric material to be sintered at 1200-1300 DEG C.
Further, in step 1), the mixed material of the metal oxide includes lead oxide and hafnium oxide.
Further, in step 1), the mixed material of the metal oxide further includes lanthana, tin oxide or oxidation
One of titanium is a variety of.
Further, a milled processed in step 1) and the secondary milled processed in step 3) are in ball grinder
The ball-milling treatment of progress, the process conditions of the ball-milling treatment are as follows: ball-milling medium is dehydrated alcohol, abrasive body, object to be processed
The mass ratio of material and ball-milling medium is (1.5-3): (0.5-1.5): 1, revolving speed is 300-350 revs/min, Ball-milling Time 12-
24h.The effect of ball milling is that while making raw material particle size thinner, each raw material is uniformly mixed, is made pre- by constantly grinding raw material
It is more abundant to burn reaction progress, the time is unsuitable too short or too long.
After the treating material is the mixed material of metal oxide in step 1) or the preheating in step 3)
Material.
Before material carries out secondary ball milling in step 3) as a preferred technical solution, first passes through mortar and smash.
It is a kind of as described above based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process, the gold-plated electricity of magnetic control sputtering device can be passed through
Pole is heat-treated 20-40min coating silver electrode at 500-600 DEG C, and then is tested for the property or prepares pulse power capacitor
Device, energy-storage capacitor or energy converter.
Compared with prior art, the invention has the characteristics that:
1) present invention prepares hafnium titanate using rolling embrane method, and preparation method is simple, easy to operate, is suitble to big rule
Mould, mass production cut out convenient for later period molding, can be used for industrialized production；
2) sample size adjustable of the present invention rolls the complete material thickness range of film and is generally 0.08-2mm, can meet different realities
Border application needs；
3) present invention is applied widely, can be used for various hafnium lead plumbate based antiferroelectric material prescriptions；
4) present invention compared with other preparation methods compare, since there are huge shearing force and extruding between idler wheel
Power can dramatically increase the consistency of material using technical solution of the present invention, and then improve resistance to sparking energy and energy storage density, breakdown
Field strength is up to 270-350kV/cm, energy storage density 5-7J/cm3, there is good application value.
Detailed description of the invention
Fig. 1 is the PbHfO being prepared in embodiment 13SEM figure；
Fig. 2 is the PbHfO being prepared in embodiment 13Ferroelectric hysteresis loop figure.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention is not limited to
Following embodiments.
Embodiment 1:
It is respectively analytically pure PbO, HfO with purity2, according to PbHfO3In Pb and the stoichiometric ratio of Hf weighed
The material prepared is put into ball grinder by ingredient, and ball material and medium ratio are 2:1:1.Ball-milling Time for 24 hours, takes out drying, In after ball milling
Pre-burning 2h at 850 DEG C, then ball milling 12h again, dries and is sieved.Then 25% adhesive is added, it is anti-first on roll forming machine
The biscuit piece of 10mm*10mm is cut into multiple roughing 1h, last finish rolling to 0.26mm.The finally biscuit piece by row after viscous, is placed in close
In the alumina dry pot closed, and be placed in above sample with thin alumina plate to avoid bending, around sprinkle appropriate lead oxide
Powder, to avoid the loss of lead.The alumina crucible for filling biscuit piece is put into Muffle furnace, viscous 4h, heating speed are arranged at 600 DEG C
1 DEG C of rate per minute, is then gradually heated at 1300 DEG C and keeps the temperature 4h, PbHfO is obtained after the completion of sintering3, carry out surface topography
Analysis plates one layer of gold electrode to sample using magnetic control sputtering device and carries out related ferroelectric properties test.The sample tests of preparation
As illustrated in fig. 1 and 2.Antiferroelectric materials surface manufactured in the present embodiment is clean and tidy, fine and close as seen in Figure 1, crystallite dimension compared with
It is small, material is born compared to the higher breakdown electric field of block materials.PbHfO as can be seen from Figure 23The forward direction of ceramics is opened
Close field EFIt is higher, about 230-240kV/cm, and PbHfO3The saturated polarization of ceramics sample is very big, can reach 45 μ C/
cm2, big EFAnd considerable PmaxValue shows PbHfO3The excellent energy storage potential of ceramics.
Embodiment 2:
It is respectively analytically pure PbO, La with purity2O3、HfO2、SnO2According to (Pb0.97La0.02)(Hf0.45Sn0.55)0.995O3
The stoichiometric ratio of middle Pb, La, Hf, Sn carry out weighing ingredient, and the material prepared is put into ball grinder, and ball material and medium ratio are 2:
1:1.Ball-milling Time for 24 hours, takes out drying, the pre-burning 2h at 850 DEG C, then ball milling 12h again, dries and be sieved after ball milling.So
After 25% adhesive is added, the element of 10mm*10mm is cut into the first repeatedly roughing 1h on roll forming machine, last finish rolling to 0.26mm
Blank.The finally biscuit piece by row after viscous, is placed in closed alumina dry pot, and be placed on sample with thin alumina plate
Side to avoid bending, around sprinkle the raw material of same component, further to avoid the volatilization of lead at high temperature.Biscuit will be filled
The alumina crucible of piece is put into Muffle furnace, and viscous 4h is arranged at 600 DEG C, and 1 DEG C of heating rate per minute, is then gradually heated to 1150
At DEG C and 2.5h is kept the temperature, after the completion of sintering, one layer of gold electrode is plated using magnetic control sputtering device and is tested.
Embodiment 3:
It is a kind of based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process, with (Pb0.04La0.04)(Hf0.26Sn0.68Ti0.06)O3
For matrix, the preparation method is as follows:
1) by lead oxide, hafnium oxide, lanthana, tin oxide and titanium oxide according to (Pb0.04La0.04)
(Hf0.26Sn0.68Ti0.06)O3In the stoichiometric ratio of corresponding Pb, Hf, La, Sn, Ti mixed, obtain mixed material, and
A ball-milling treatment is carried out in ball grinder；
2) material after primary grinding is dried at 130 DEG C, and at 850 DEG C constant temperature 2h to carry out preheating；
3) material after preheating is first passed through mortar to smash, then carries out secondary ball milling processing in ball grinder, and in
It is dried at 130 DEG C；
4) material after drying is mixed with adhesive with mass ratio 0.2:1, the roughing of 1h is first carried out on roll forming machine, then
Finish rolling cuts later to required size to required thickness, obtains biscuit piece；
5) biscuit piece is first warming up to 500 DEG C with the heating rate of 0.5 DEG C/min, and constant temperature 2h to be to carry out arranging viscous processing,
Again at 1200 DEG C constant temperature 2h to be sintered；Obtain hafnium lead plumbate based antiferroelectric material.
The treatment conditions of ball-milling treatment are as follows: ball-milling medium is dehydrated alcohol, abrasive body, treating material and ball-milling medium
Mass ratio is 1.5:0.5:1, and revolving speed is 300 revs/min, Ball-milling Time 12h, and the treating material is in step 1)
The material after preheating in mixed material or step 3).
Hafnium lead plumbate based antiferroelectric material is heat-treated to 30min to be tested for the property to coat silver electrode at 550 DEG C.
Embodiment 4:
It is a kind of based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process, with (Pb0.9854La0.01)(Hf0.8Sn0.18Ti0.02)O3
For matrix, the preparation method is as follows:
1) by lead oxide, hafnium oxide, lanthana, tin oxide and titanium oxide according to (Pb0.9854La0.01)
(Hf0.8Sn0.18Ti0.02)O3In the stoichiometric ratio of corresponding Pb, Hf, La, Sn, Ti mixed, obtain mixed material, and
A ball-milling treatment is carried out in ball grinder；
2) material after primary grinding is dried at 120 DEG C, and at 900 DEG C constant temperature 4h to carry out preheating；
3) material after preheating is first passed through mortar to smash, then carries out secondary ball milling processing in ball grinder, and in
It is dried at 120 DEG C；
4) material after drying is mixed with adhesive with mass ratio 0.25:1, the roughing of 2h is first carried out on roll forming machine,
Finish rolling cuts later to required size to required thickness, obtains biscuit piece again；
5) biscuit piece is first warming up to 700 DEG C with the heating rate of 2 DEG C/min, and constant temperature 5h to be arrange viscous processing, then
Constant temperature 2-4h obtains hafnium lead plumbate based antiferroelectric material to be sintered at 1200-1300 DEG C.
The treatment conditions of ball-milling treatment are as follows: ball-milling medium is dehydrated alcohol, abrasive body, treating material and ball-milling medium
Mass ratio is 3:1.5:1, and revolving speed is 350 revs/min, and Ball-milling Time is that for 24 hours, the treating material is mixed in step 1)
Material after closing the preheating in material or step 3).
Hafnium lead plumbate based antiferroelectric material is heat-treated to 30min to be tested for the property to coat silver electrode at 600 DEG C.
Embodiment 5:
It is a kind of based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process, with (Pb0.97La0.02)(Hf0.76Sn0.2Ti0.04)O3For
Matrix, the preparation method is as follows:
1) by lead oxide, hafnium oxide, lanthana, tin oxide and titanium oxide according to (Pb0.97La0.02)
(Hf0.76Sn0.2Ti0.04)O3In the stoichiometric ratio of corresponding Pb, Hf, La, Sn, Ti mixed, obtain mixed material, and
A ball-milling treatment is carried out in ball grinder；
2) material after primary grinding is dried at 110 DEG C, and at 880 DEG C constant temperature 3h to carry out preheating；
3) material after preheating is first passed through mortar to smash, then carries out secondary ball milling processing in ball grinder, and in
It is dried at 110 DEG C；
4) material after drying is mixed with adhesive with mass ratio 0.2-0.25:1, first carries out 1-2h's on roll forming machine
Roughing, then finish rolling cut later to required size to required thickness, obtain biscuit piece；
5) biscuit piece is first warming up to 600 DEG C with the heating rate of 1 DEG C/min, and constant temperature 4h to be arrange viscous processing, then
Constant temperature 3h obtains hafnium lead plumbate based antiferroelectric material to be sintered at 1250 DEG C.
The treatment conditions of ball-milling treatment are as follows: ball-milling medium is dehydrated alcohol, abrasive body, treating material and ball-milling medium
Mass ratio is 2:1:1, and revolving speed is 320 revs/min, Ball-milling Time 15h, and the treating material is the mixing in step 1)
The material after preheating in material or step 3).
Hafnium lead plumbate based antiferroelectric material is heat-treated to 20min to be tested for the property to coat silver electrode at 560 DEG C.
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process, which is characterized in that the hafnium lead plumbate based antiferroelectric material
Chemical general formula is (Pb1-3z/2Laz)(Hf1-x-ySnxTiy)O3, wherein the value range of z is 0 < z≤0.04, and the value range of x is
The value range of 0 < x < 1.0, y are 0 < y < 1.0.
2. according to claim 1 a kind of based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process, which is characterized in that z's
Value range is 0.01≤z≤0.04, and the value range of x is 0.18≤x≤0.68, the value range of y be 0.02≤y≤
0.06。
3. a kind of preparation method based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process, which is characterized in that the hafnium lead plumbate
The chemical general formula of based antiferroelectric material is (Pb1-3z/2Laz)(Hf1-x-ySnxTiy)O3, wherein the value range of z be 0≤z≤
0.04, x value range is 0≤x < 1.0, and the value range of y is 0≤y < 1.0；
The preparation method the following steps are included:
1) mixed material of metal oxide is subjected to a milled processed；
2) material after a milled processed is dried at 110-130 DEG C, and carries out preheating；
3) material after preheating is subjected to secondary milled processed, is dried at 110-130 DEG C later；
4) material after drying is mixed with adhesive, by roughing, finish rolling and is cut, obtain biscuit piece；
5) biscuit piece is successively carried out arranging viscous processing and sintering processes, obtains hafnium lead plumbate based antiferroelectric material.
4. a kind of preparation method based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process according to claim 3, special
Sign is, in step 1), the mixed material of the metal oxide includes lead oxide and hafnium oxide.
5. a kind of preparation method based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process according to claim 4, special
Sign is that the mixed material of the metal oxide further includes one of lanthana, tin oxide or titanium oxide or a variety of.
6. a kind of preparation method based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process according to claim 3, special
Sign is that the secondary milled processed in step 1) a milled processed and step 3) is the ball milling carried out in ball grinder
Processing, the process conditions of the ball-milling treatment are as follows: ball-milling medium is dehydrated alcohol, and abrasive body, treating material and ball milling are situated between
The mass ratio of matter is (1.5-3): (0.5-1.5): 1, revolving speed is 300-350 revs/min, Ball-milling Time 12-24h.
7. a kind of preparation method based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process according to claim 3, special
Sign is, in step 2), the process conditions of the preheating are as follows: and 850-900 DEG C of temperature, burn-in time 2-4h.
8. a kind of preparation method based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process according to claim 3, special
Sign is, in step 4), the adhesive is 0.2-0.25:1 with the mass ratio of the material after drying.
9. a kind of preparation method based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process according to claim 3, special
Sign is, in step 5), the process conditions of the viscous processing of the row are as follows: 500- is warming up to the heating rate of 0.5-2 DEG C/min
700 DEG C, and constant temperature 2-5h；The process conditions of the sintering processes are as follows: the constant temperature 2-4h at 1200-1300 DEG C.
10. a kind of preparing pulse power based on the hafnium lead plumbate based antiferroelectric material for rolling membrane process as claimed in claim 1 or 2
Application in capacitor, energy-storage capacitor or energy converter.
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| CN113213923A (en) * | 2021-05-07 | 2021-08-06 | 重庆文理学院 | Lead hafnate titanate-based antiferroelectric ceramic material and preparation method thereof |
| CN113213925A (en) * | 2021-05-07 | 2021-08-06 | 重庆文理学院 | Method for preparing hafnium lead titanate-based ceramic material based on hot isostatic pressing method |
| CN115465890A (en) * | 2022-08-29 | 2022-12-13 | 北京科技大学 | Preparation method and application of lanthanum-doped lead hafnate dielectric film |
| CN115465890B (en) * | 2022-08-29 | 2023-08-29 | 北京科技大学 | Preparation method and application of lanthanum-doped lead hafnate dielectric film |
| CN115872735A (en) * | 2022-11-18 | 2023-03-31 | 广东工业大学 | Zirconium tin hafnate lanthanum lead ceramic and preparation method and energy storage application thereof |
| CN115872735B (en) * | 2022-11-18 | 2024-01-16 | 广东工业大学 | Zirconium tin hafnium lanthanum lead acid ceramic, preparation method and energy storage application thereof |
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