CN105753471B - A kind of preparation method of high electric card effect strontium barium niobate ceramics - Google Patents

A kind of preparation method of high electric card effect strontium barium niobate ceramics Download PDF

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CN105753471B
CN105753471B CN201610041501.3A CN201610041501A CN105753471B CN 105753471 B CN105753471 B CN 105753471B CN 201610041501 A CN201610041501 A CN 201610041501A CN 105753471 B CN105753471 B CN 105753471B
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electric card
sintering
ceramics
strontium barium
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吴淑雅
张志聪
陈湘明
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Zhejiang University ZJU
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Abstract

The invention discloses a kind of preparation methods of high electric card effect strontium barium niobate ceramics, and this method is first by raw material BaCO3, SrCO3And Nb2O5By SrxBa1‑xNb2O6Chemical formula ingredient, wherein x=0.4,0.5 or 0.6, obtains SrxBa1‑xNb2O6Powder.Using discharge plasma sintering system, 1000 DEG C~1050 DEG C sintering in vacuum environment, are prepared ceramic sintered bodies, will finally be heat-treated 3 hours at ceramic sintered bodies in air 965~980 DEG C, high electric card effect strontium barium niobate ceramics is made.The high electric card effect strontium barium niobate ceramics of the method for the present invention preparation, crystallite dimension is small, and consistency is high and improves dielectric breakdown field strength, is expected to be used for solid-state refrigeration system, the destruction due to freon as refrigerant to ozone layer is solved, solves the problems, such as the various climatic environments faced at present.

Description

A kind of preparation method of high electric card effect strontium barium niobate ceramics
Technical field
The present invention relates to solid-state electric card refrigeration and high electric card effect ceramic materials of energy collecting device and preparation method thereof.
Background technique
Electric card effect (Electrocaloric Effect, hereinafter referred to as ECE) refers under adiabatic conditions, to material When applying and removing electric field, the phenomenon that material can generate reversible temperature change, it can effectively realize solid-state refrigeration component Efficiency.It can be achieved without greenhouse gas emission, to solve the problems, such as that freon provides one for environmental disruption brought by refrigerant Effective way.There is the material compared with forceful electric power card effect mainly there are following four classes: one, lead base composite perofskite at present；Two, SrBi2Ta2O9Film；Three, BaTiO3、SrTiO3、Ba(1-x)SrxTiO3Class；Four, (one trifluoro-ethylene of vinylidene fluoride) is base Film.Above-mentioned leaded, secret compound electric card effect is relatively high, but does not meet environmental-friendly requirement, strontium titanates, metatitanic acid The electric card effect of barium system is relatively weak, although organic polymer has stronger electric card effect, its thermal stability is poor. The practical application that these disadvantages limit them is promoted, therefore there is presently no the electric card effects that discovery meets actual operation requirements Material.The existing research for electric card effect material focuses primarily upon film, compares because film has for block High electric card effect.The breakdown strength of ceramic block compares lower (highest bear voltage≤100KV/cm), and film can be with In addition relatively high electric field (~100-2000KV/cm).Although the decline of film single loop temperature is larger in practical applications, by In it is small in size, but its total thermal capacity is small.The volume of ceramic block is bigger, although the decline of single loop temperature is small, It is that its total thermal capacity is big, so the application value of block materials can be higher than thin if the electric card value of two kinds of materials is not much different Membrane material.In addition, the preparation method of ceramics will affect its micro-structure, and the performance micro-structure of ceramics is related.
The compound of tungsten bronze structure is a kind of important dielectric substance for being only second to perovskite structure compound.Tungsten is green Strontium barium niobate (general formula Sr in the relaxation ferroelectric of steel structurexBa1-xNb2O6, solution range 0.32≤x≤0.82 is abbreviated as It SBN), is always domestic and international research group's research because having excellent pyroelectric effect, high photoelectric coefficient and piezoelectric modulus Hot spot.
The strontium barium niobate ceramics for the heterogeneity that the present invention is prepared for discharge plasma sintering.Ceramics are had studied in difference At a temperature of polarization value, find different sintering methods will affect ceramics ferroelectric properties, to influence ferroelectric effect.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to improve a kind of system of high electric card effect strontium barium niobate ceramics Preparation Method, using the maximum electric card effect of strontium barium niobate ceramics of this method preparation up to 0.51 DEG C.
The purpose of the present invention is achieved through the following technical solutions: a kind of system of high electric card effect strontium barium niobate ceramics Preparation Method, comprising the following steps:
(1) by raw material BaCO3, SrCO3And Nb2O5By SrxBa1-xNb2O6Chemical formula ingredient, wherein x=0.4,0.5 or 0.6, it is ground to after partial size is 100nm~400nm and dries, be sieved；
(2) after calcining 1200 DEG C~1300 DEG C of powder made from step (1) 3 hours, Sr is made in sievingxBa1-xNb2O6 Powder；
(3) by Sr made from step (2)xBa1-xNb2O6Powder is packed into the graphite jig of 10mm, is burnt using plasma discharging 1000 DEG C~1050 DEG C sintering under vacuum conditions of clone system, are made ceramic sintered bodies；
(4) under air atmosphere, 960 DEG C~1000 DEG C of ceramic sintered bodies made from step (3) are heat-treated 3 hours, is made The high electric card strontium barium niobate ceramics.
Further, in the step (2), when x=0.4 or 0.5,1200 DEG C are calcined 3 hours；When x=0.6,1300 DEG C Calcining 3 hours.
Further, in the step (3), 1000 DEG C of sintering when x=0.4,1025 DEG C of sintering when x=0.5, when x=0.6 1050 DEG C of sintering.
Further, in the step (4), 980 DEG C of heat treatment when x=0.4,970 DEG C of heat treatments when x=0.5, x=0.6 When 965 DEG C heat treatment.
Further, in step (1), the method for grinding are as follows: raw material is put into ball grinder, zirconia ball and anhydrous second is added Alcohol carries out ball milling.
For the present invention by using discharge plasma sintering method, crystallite dimension is small and uniform, improves consistency and SrNb2 O6 The dielectric breakdown strength of titanate ceramics, to improve the electric card effect of strontium barium niobate ceramics.
Before preparation, raw material needs to be ground to certain fineness, when grinding, raw material can be put into ball grinder, oxidation is added Ball milling is carried out in zirconium ball and dehydrated alcohol.
The beneficial effects of the present invention are: use preparation method of the invention, Sr obtainedxBa1-xNb2O6Ceramics are in room temperature Lower dielectric breakdown field strength reaches 120kV/cm, and uses the Sr of conventional solid-state sintering method preparationxBa1-xNb2O6The dielectric of ceramics Disruptive field intensity is only 50kV/cm, and dielectric breakdown field strength improves 2 times or more；At this point, discharge plasma sintering temperature is 1000 DEG C, and use the Sr of conventional solid-state method method preparationxBa1-xNb2O6Ceramic sintering temperature is 1350 DEG C, and sintering temperature reduces 300 DEG C or more；The electric card value of optimal strontium barium niobate ceramics obtained is 0.51 DEG C, and uses the same of conventional solid-state method method preparation The electric card value of the strontium barium niobate ceramics of ingredient is only 0.15 DEG C or so, and electric card effect improves 3 times or more.Height prepared by the present invention Electric card strontium barium niobate ceramics can be used for the components such as solid-state refrigeration, not need air compressor, volume can be made smaller, Can be the refrigeration such as small-sized electronic product such as CPU, and more efficient, it is important to environmental protection, energy conservation, efficiently, stablize and be easy to small Type.Under the urgent overall background for reducing greenhouse effects and energy shortage at present, refrigeration skill of the electric card refrigeration as green energy conservation Art becomes one of the potential selection of people in the future, is highly desirable to increase it research and development.
Detailed description of the invention
Fig. 1 is the XRD diffracting spectrum of strontium barium niobate ceramics sample: (a) Sr0.4Ba0.6Nb2O6(embodiment 1)；(b) Sr0.5Ba0.5Nb2O6(embodiment 2)；(c)Sr0.6Ba0.4Nb2O6(embodiment 3)；(d) conventional solid-state method prepares Sr0.6Ba0.4Nb2O6 (comparative example 1)；
Fig. 2 is the section SEM photograph of strontium barium niobate ceramics sample: (a) Sr0.4Ba0.6Nb2O6(embodiment 1)；(b) Sr0.5Ba0.5Nb2O6(embodiment 2)；(c)Sr0.6Ba0.4Nb2O6(embodiment 3)；It (d) is conventional solid-state method preparation Sr0.6Ba0.4Nb2O6(comparative example 1)；
Fig. 3 is the dielectric constant and dielectric loss variation with temperature song of strontium barium niobate ceramics sample at different frequencies Line: (a), (b) Sr0.4Ba0.6Nb2O6(embodiment 1)；(c),(d)Sr0.5Ba0.5Nb2O6(embodiment 2)；(e),(f) Sr0.6Ba0.4Nb2O6(embodiment 3)；
Fig. 4 is polarization changing value of the strontium barium niobate ceramics sample under different dielectric field strength: (a) Sr0.4Ba0.6Nb2O6It is (real Apply example 1)；(b)Sr0.5Ba0.5Nb2O6(embodiment 2)；(c)Sr0.6Ba0.4Nb2O6(embodiment 3)；
Fig. 5 is electric card value and isothermal Entropy Changes value of the strontium barium niobate ceramics sample at 10Hz: (a), (b) Sr0.4Ba0.6Nb2O6 (embodiment 1)；(c),(d)Sr0.5Ba0.5Nb2O6(embodiment 2)；；(e),(f)Sr0.6Ba0.4Nb2O6(embodiment 3)；
Fig. 6 is electric card value and isothermal Entropy Changes value of the strontium barium niobate sample at 10Hz of tradition preparation: (a), (b) Sr0.6Ba0.4Nb2O6(comparative example 1).
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
Embodiment 1
(1) by BaCO3, SrCO3And Nb2O5Raw material powder presses Sr respectively0.4Ba0.6Nb2O6Chemical formula weighs ingredient；
(2) step (1) prepared chemical raw material is put into ball grinder, in plastics ball grinder and ZrO is added2Zirconium ball, adds Enter dehydrated alcohol, is placed on ball mill and carries out ball milling 24 hours (partial size is 100nm~400nm), the powder after ball milling is being dried 120 mesh are sieved after drying in case.By powder obtained in 1200 DEG C of 3 hours of calcining, after 2 DEG C/min cools to 1100 DEG C, with Furnace is cooled to room temperature, crosses 120 meshes, and Sr is made0.4Ba0.6Nb2O6Powder；
(3) powder made from step (2) is packed into the graphite jig that diameter is 10mm, is put into discharge plasma sintering system It is sintered under 1000 DEG C and 30MPa mechanical pressure, keeps the temperature 5 minutes, be 100 DEG C/min from room temperature to 900 DEG C of heating rate, DEG C heating rate is 40 DEG C/min from 900 DEG C to 980, and 980 DEG C to 1000 DEG C heating rates are 20 DEG C/min, 1000 DEG C of heat preservations 5min after the completion of sintering, sheds pressure and with being furnace-cooled to 100 DEG C of taking-up samples.
Discharge plasma sintering principle: discharge plasma sintering directly carries out the pressurization burning that is powered using DC pulse current Knot controls heating rate by adjusting the watt level of DC pulse current.Entire sintering process both can be under vacuum conditions It carries out, also to be carried out in protective atmosphere.Pulse current directly acts on sample and mold, fast heating, flash heat transfer, fastly Speed heating, substantially shortens sample sintering time.
(4) ceramics sample made from step (3) is heat-treated 3 at 980 DEG C in air after the graphite paper for grinding off adherency Hour.It is 5 DEG C/min, 980 DEG C of heat preservation 3h from room temperature to 980 DEG C of heating rate, it is cold with furnace after the completion of processing.And in air gas Under atmosphere, it is heat-treated at 980 DEG C and obtains within 3 hours the ceramics with electric card effect higher than Traditional preparation.
Embodiment 2
(1) by BaCO3, SrCO3And Nb2O5Raw material powder presses Sr respectively0.5Ba0.5Nb2O6Chemical formula weighs ingredient；
(2) step (1) prepared chemical raw material is put into ball grinder, in plastics ball grinder and ZrO is added2Zirconium ball, adds Enter dehydrated alcohol, is placed on ball mill and carries out ball milling 24 hours (partial size is 100nm~400nm), the powder after ball milling is being dried 120 mesh are sieved after drying in case.By powder obtained in 1200 DEG C of 3 hours of calcining, after 2 DEG C/min cools to 1100 DEG C, with Furnace is cooled to room temperature, crosses 120 meshes, and Sr is made0.5Ba0.5Nb2O6Powder；
(3) powder made from step (2) is packed into the graphite jig that diameter is 10mm, is put into discharge plasma sintering system It is sintered under 1025 DEG C and 30MPa mechanical pressure, keeps the temperature 5 minutes, be 100 DEG C/min from room temperature to 925 DEG C of heating rate, DEG C heating rate is 40 DEG C/min from 925 DEG C to 1005, and 1005 DEG C to 1025 DEG C heating rates are 20 DEG C/min, 1025 DEG C of heat preservations 5min after the completion of sintering, sheds pressure and with being furnace-cooled to 100 DEG C of taking-up samples.
(4) ceramics sample made from step (3) is heat-treated 3 at 980 DEG C in air after the graphite paper for grinding off adherency Hour.It is 5 DEG C/min, 970 DEG C of heat preservation 3h from room temperature to 970 DEG C of heating rate, it is cold with furnace after the completion of processing.And in air gas Under atmosphere, it is heat-treated at 970 DEG C and obtains within 3 hours the ceramics with electric card effect higher than Traditional preparation.
Embodiment 3
(1) by BaCO3, SrCO3And Nb2O5Raw material powder presses Sr respectively0.6Ba0.4Nb2O6Chemical formula weighs ingredient；
(2) step (1) prepared chemical raw material is put into ball grinder, in plastics ball grinder and ZrO is added2Zirconium ball, adds Enter dehydrated alcohol, is placed on ball mill and carries out ball milling 24 hours (partial size is 100nm~400nm), the powder after ball milling is being dried 120 mesh are sieved after drying in case.By powder obtained in 1300 DEG C of 3 hours of calcining, after 2 DEG C/min cools to 1100 DEG C, with Furnace is cooled to room temperature, crosses 120 meshes, and Sr is made0.6Ba0.4Nb2O6Powder；
(3) powder made from step (2) is packed into the graphite jig that diameter is 10mm, is put into discharge plasma sintering system It is sintered under 1050 DEG C and 30MPa mechanical pressure, keeps the temperature 5 minutes, be 100 DEG C/min from room temperature to 950 DEG C of heating rate, DEG C heating rate is 40 DEG C/min from 950 DEG C to 1030, and 1030 DEG C to 1050 DEG C heating rates are 20 DEG C/min, 1050 DEG C of heat preservations 5min after the completion of sintering, sheds pressure and with being furnace-cooled to 100 DEG C of taking-up samples.
(4) ceramics sample made from step (3) is heat-treated 3 at 965 DEG C in air after the graphite paper for grinding off adherency Hour.It is 5 DEG C/min, 965 DEG C of heat preservation 3h from room temperature to 965 DEG C of heating rate, it is cold with furnace after the completion of processing.And in air gas Under atmosphere, it is heat-treated at 960 DEG C and obtains within 3 hours the ceramics with electric card effect higher than Traditional preparation.
Comparative example 1
Sr is provided0.6Ba0.4Nb2O6The conventional solid-state method preparation process of ceramics:
(1) by BaCO3, SrCO3And Nb2O5Raw material powder presses Sr respectively0.6Ba0.4Nb2O6Chemical formula weighs ingredient；
(2) step (1) prepared chemical raw material is put into ball grinder, in plastics ball grinder and ZrO is added2Zirconium ball, adds Enter dehydrated alcohol, is placed on ball mill and carries out ball milling 24 hours (partial size is 100nm~400nm), the powder after ball milling is being dried 120 mesh are sieved after drying in case.By powder obtained in 1300 DEG C of 3 hours of calcining, after 2 DEG C/min cools to 1100 DEG C, with Furnace is cooled to room temperature, crosses 120 meshes, and Sr is made0.6Ba0.4Nb2O6Powder；
(3) polyvinyl alcohol (PVA) that 8wt% concentration is 5vol% is added in powder made from step (2) and is used as binder After grinding is granulated, 40 meshes are crossed, it is therefore an objective to increase the mobility and plasticity of powder.Then it is made under the single-phase pressure of 98MPa It is the cylindrical idiosome of 12mm, thickness 2mm or so at diameter.
(4) idiosome that step (3) is prepared is put into 600 DEG C of plastic removal 2h of alumina crucible, in order to prevent idiosome and earthenware Crucible reaction, covers powder identical with idiosome, padding more higher than sintering temperature, then in air atmosphere in alumina crucible 1350 DEG C are sintered 3 hours, and after 2 DEG C/min drops to 1100 DEG C, furnace cooling obtains Sr0.6Ba0.4Nb2O6Ceramics.
The cylindrical dielectric ceramics sample abrasive paper for metallograph and polishing machine that Examples 1 to 3 and comparative example 1 are prepared Then sanding and polishing uses sputter to deposit gold thin film as electrode to a thickness of 0.5mm or so in the upper and lower surface of sample.It utilizes Ferroelectricity analyzer measures the ferroelectric hysteresis loop at lower 0 DEG C to 165 DEG C of its 10Hz frequency, calculates its electric card effect using indirect method.
Table 1
From fig. 1, it can be seen that the ceramic sample of two kinds of sintering process preparation is all single-phase.As shown in Figure 2, discharge plasma sintering The crystal grain of the strontium barium niobate ceramics of preparation is small with respect to what conventional solid-state method was sintered, and consistency is high.As can be seen from Figure 3, Jie of sample Electric constant is reduced with the increase of x, is T in the temperature of phase transformation curie pointC, in TCPlace, the dielectric constant of sample are maximum value, Curie temperature TCAlso with x increase and reduce, Sr0.6Ba0.4Nb2O6The Curie temperature of ceramics is close to room temperature.As shown in Figure 4, with The raising of temperature, the polarization value of strontium barium niobate ceramics reduce, reduced near Curie point fastest.It can by Fig. 5,6 Know, the disruptive field intensity and electric card value of the strontium barium niobate ceramics of plasma discharging preparation significantly improve.It is prepared compared to conventional solid The ceramics of method preparation, disruptive field intensity increase to 80kV/cm from 50kV/cm.Therefore its electric card value also correspondinglys increase, in x=0.6 When, Sr0.6Ba0.4Nb2O6The electric card value of ceramics reaches 0.51 DEG C maximum, than improving more than 3 times for conventional solid-state method preparation.
Table 1 shows the Sr being made using preparation method of the inventionxBa1-xNb2O6Ceramics and utilize conventional solid-state method The Sr of sintering method preparation0.6Ba0.4Nb2O6Ceramics are 0 DEG C to 165 DEG C in temperature, dielectric breakdown strength and electricity under 10Hz frequency Calorific power, as shown in Table 1, Sr produced by the present inventionxBa1-xNb2O6The highest electric card value of ceramics is 0.51 DEG C, and utilizes conventional solid The Sr of the identical component of sintering method preparation0.6Ba0.4Nb2O6The electric card value of ceramics is only 0.15 DEG C.

Claims (2)

1. a kind of preparation method of high electric card effect strontium barium niobate ceramics, which comprises the following steps:
(1) by raw material BaCO3, SrCO3And Nb2O5By SrxBa1-xNb2O6Chemical formula ingredient, wherein x=0.4,0.5 or 0.6, grinds It dries, is sieved after being 100nm ~ 400nm to partial size；
(2) by powder 1200 made from step (1)oC~1300oAfter C is calcined 3 hours, Sr is made in sievingxBa1-xNb2O6Powder；
(3) by Sr made from step (2)xBa1-xNb2O6Powder is packed into the graphite jig of 10mm, utilizes discharge plasma sintering system System under vacuum conditions 1000oC ~ 1050 DEG C sintering, is made ceramic sintered bodies；
(4) under air atmosphere, 960 DEG C ~ 1000 DEG C of ceramic sintered bodies made from step (3) is heat-treated 3 hours, the height is made Electric card strontium barium niobate ceramics；
In the step (2), x=0.4 or when 0.5,1200oC is calcined 3 hours；When x=0.6,1300 DEG C are calcined 3 hours；
In the step (3), 1000 when x=0.4oC sintering；1025 DEG C of sintering when x=0.5；1050 DEG C of sintering when x=0.6；
In the step (4), 980 DEG C of heat treatment when x=0.4；970 DEG C of heat treatment when x=0.5；965 DEG C of heat treatment when x=0.6.
2. preparation method as described in claim 1, which is characterized in that in step (1), the method for grinding are as follows: be put into raw material Ball grinder, is added zirconia ball and dehydrated alcohol carries out ball milling.
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