CN104030678B - A kind of BaTiO 3base unleaded relaxation type ceramic dielectric material and preparation method thereof - Google Patents
A kind of BaTiO 3base unleaded relaxation type ceramic dielectric material and preparation method thereof Download PDFInfo
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- CN104030678B CN104030678B CN201410299999.4A CN201410299999A CN104030678B CN 104030678 B CN104030678 B CN 104030678B CN 201410299999 A CN201410299999 A CN 201410299999A CN 104030678 B CN104030678 B CN 104030678B
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- 239000000919 ceramic Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000003989 dielectric material Substances 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 98
- 238000005469 granulation Methods 0.000 claims abstract description 42
- 230000003179 granulation Effects 0.000 claims abstract description 42
- 239000000843 powder Substances 0.000 claims abstract description 35
- 238000000498 ball milling Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 23
- 238000009413 insulation Methods 0.000 claims abstract description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002003 electrode paste Substances 0.000 claims abstract description 12
- 229910052709 silver Inorganic materials 0.000 claims abstract description 12
- 239000004332 silver Substances 0.000 claims abstract description 12
- 238000007873 sieving Methods 0.000 claims abstract description 3
- 239000004615 ingredient Substances 0.000 claims description 40
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 33
- 239000000853 adhesive Substances 0.000 claims description 33
- 230000001070 adhesive effect Effects 0.000 claims description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000002156 mixing Methods 0.000 claims description 29
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 22
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 238000010792 warming Methods 0.000 claims description 22
- 229910052726 zirconium Inorganic materials 0.000 claims description 22
- 229910010293 ceramic material Inorganic materials 0.000 claims description 15
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 11
- 229910052797 bismuth Inorganic materials 0.000 claims description 11
- 238000004140 cleaning Methods 0.000 claims description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 11
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 3
- 230000007704 transition Effects 0.000 abstract description 8
- 238000005516 engineering process Methods 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000003836 solid-state method Methods 0.000 abstract description 2
- 230000008859 change Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000005498 polishing Methods 0.000 description 9
- 239000006185 dispersion Substances 0.000 description 4
- 239000003985 ceramic capacitor Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000005343 Curie-Weiss law Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 230000027311 M phase Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- -1 compound ion Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910002112 ferroelectric ceramic material Inorganic materials 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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Abstract
A kind of BaTiO
3base unleaded relaxation type ceramic dielectric material and preparation method thereof, takes BaCO
3and TiO
2be mixed to form mixture; After mixture is carried out ball milling, oven dry, briquetting, be placed in box type furnace in insulation, form the BaTiO of pure phase
3powder; By Bi
2o
3and Al
2o
3be added into the BaTiO of pure phase
3in powder, formed and entirely prepare burden, carrying out ball milling, oven dry, granulation by entirely preparing burden, sieving, form granulation material; Granulation material is made sample, then sinters, then sinter after applying silver electrode paste.Prepared by employing conventional solid-state method, technical maturity, is applicable to industrialization and produces.Adopt Bi
2o
3and Al
2o
3carry out codope, realize valence compensation and be conducive to realizing BaTiO
3the Diffuse phase transition of pottery.Preparation technology is simple, and the cost of material is low and environmental protection, and the unleaded relaxation type ceramic dielectric material of preparation has higher dielectric constant, low dielectric loss.
Description
Technical field
The invention belongs to ceramic dielectric material field, particularly a kind of BaTiO
3base unleaded relaxation type ceramic dielectric material and preparation method thereof.
Background technology
Perovskite structure ferroelectric studies a class ferroelectric the most widely at present, and its skeleton symbol is ABO
3.Because the distinctive geometry laxity of perovskite structure can hold the Doped ions of different size, so different A position or B position and A position and B position recombination energy access much complex perovskite structure solid solution and compound, this compounds becomes the object that many scholars competitively study naturally.Wherein, the former Russian scholar etc. synthesize the New Wave that the lead magnesio-niobate with Relaxivity has started relaxation ferroelectric research first.Be different from independent relaxation phenomena and ferroelectricity, traditional sense is thought that both break mutual unrelated saying by unique relaxation behavior, and both perfect adaptations are called Relaxation Ferroelectrics by people together.Compared with common ferroelectric, topmost two the feature Diffuse phase transition in relaxation ferroelectric dielectric property aspect and frequency dispersion.
At present, many scholars have been had to BaTiO
3the unleaded relaxation ferroelectric ceramic material of base conducts extensive research.Henan ferroelectric not only has high dielectric property, relatively low firing temperature, also has the low temperature coefficient of capacitance caused by " Diffuse phase transition ".No matter be therefore preparation technology aspect or aspect with low cost, be all considered to the only choosing of alternative multilayer ceramic capacitor.
Summary of the invention
The object of the present invention is to provide a kind of BaTiO
3base lead-free ceramics dielectric substance and preparation method thereof, not only preparation technology is simple, and the cost of material is low, and have higher dielectric constant, low dielectric loss.
For achieving the above object, the present invention takes following technical scheme:
A kind of BaTiO
3the preparation method of base unleaded relaxation type ceramic dielectric material, comprises the following steps:
Step one: preparation BaTiO
3for subsequent use: to take BaCO according to mol ratio 1:1
3and TiO
2be mixed to form mixture;
Step 2: after mixture is carried out ball milling, oven dry, briquetting, is placed in box type furnace in 1130-1170 DEG C of insulation 2-3 hour, forms the BaTiO of pure phase
3powder;
Step 3: with the BaTiO of pure phase
3powder is 1mol meter, takes 0.5mol%Bi respectively according to molar content
2o
3and xmol%Al
2o
3be added into the BaTiO of pure phase
3in powder, formed and entirely prepare burden, carrying out ball milling, oven dry, granulation by entirely preparing burden, sieving, form granulation material; Wherein, x=0.00 ~ 3.00;
Step 4: granulation material is made sample, then be placed in zirconia be backing plate the inherent high temperature box furnace of aluminium oxide saggar in, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, 2-3 hour is incubated when being warming up to 1230 ~ 1290 DEG C with 5 DEG C/min, afterwards, after being cooled to 500 DEG C with 5 DEG C/min, cool to room temperature with the furnace, obtain the sample sintered;
Step 5: after the sample sintered being carried out polish, cleaning, evenly apply silver electrode paste at sample tow sides, in 600 DEG C of sintering 20-30 minute, obtain BaTiO
3base unleaded relaxation type ceramic dielectric material.
In described step 3, ball milling specifically will be prepared burden and zirconium ballstone, deionized water entirely, be carry out after 1:1:1 mixes according to mass ratio.
In described step 3, Ball-milling Time is 3-4 hour.
In described step 3, formed after full batching, zirconium ballstone and deionized water mixing, ball milling, oven dry and dry material, adhesive is added into dry in material and carries out granulation, then cross 40 orders and 80 mesh sieves respectively and get and middlely to expect, obtain granulation material; Wherein, adhesive accounts for and dries 8 ~ 10% of material quality.
Described adhesive to be mass concentration be 4 ~ 6% polyvinyl alcohol water solution.
In described step 3, x is 0,0.25,0.75,1.00,2.00 or 3.00.
In described step 4, granulation material makes sample under the pressure of 120MPa.
The BaTiO obtained by said method
3base lead-free ceramics dielectric substance, described BaTiO
3the major ingredient of base lead-free ceramics dielectric substance is BaCO
3and TiO
2, its mol ratio is 1:1, and auxiliary material is Bi
2o
3and Al
2o
3; According to molar percent, Bi
2o
3account for the 0.5mol% of major ingredient, Al
2o
3account for the xmol% of major ingredient, wherein, x=0.00 ~ 3.00.
According to molar percent, described x is 0,0.25,0.75,1.00,2.00 or 3.00.
Compared with prior art, the beneficial effect that has of the present invention: doping Bi
3+replace Ba
2+the relaxation behavior that can strengthen, at BaTiO
3b position doped with Al
3+t can be reduced
m.At BaTiO
3a position doping Bi
3+not mating of ionic radius can be caused, the Al of B position doping
3+valence fluctuation and local heterogeneity can be caused.In order to obtain relaxation behavior when low temperature, the present invention is at BaTiO
3a position doping Bi
3+, simultaneously in B position doped with Al
3+.By to obtained ceramic dielectric performance evaluation, digital proof its there is relaxation phenomena, meet topmost two the feature Diffuse phase transition characteristic sum frequency dispersion characteristics in relaxation ferroelectric dielectric property aspect, alternative non-plumbum ferroelectric body in actual applications.The present invention also has the following advantages: 1. adopt conventional solid-state method preparation, technical maturity, is applicable to industrialization and produces.2. adopt Bi
2o
3and Al
2o
3carry out codope, realize valence compensation and be conducive to realizing BaTiO
3the Diffuse phase transition of pottery.3. not only preparation technology is simple for method of the present invention, the cost of material is low and environmental protection, and the unleaded relaxation type ceramic dielectric material of preparation has higher dielectric constant, low dielectric loss, multilayer ceramic capacitor important candidate material double excellent is technically and economically become to alternative lead base ceramic material.
Accompanying drawing explanation
Fig. 1 (a) is the characteristic curve of the dielectric constant with temperature change of embodiment 1 sample, and Fig. 1 (b) is for embodiment 1 sample is at the inverse dielectric constant with temperature change curve for pottery under 1kHz;
Fig. 2 (a) is the temperature variant characteristic curve of temperature coefficient of capacitance of embodiment 2 sample, and Fig. 2 (b) is for embodiment 2 sample is at the inverse dielectric constant with temperature change curve for pottery under 1kHz;
Fig. 3 (a) is the characteristic curve of the dielectric constant with temperature change of embodiment 3 sample, and Fig. 3 (b) is for embodiment 3 sample is at the inverse dielectric constant with temperature change curve for pottery under 1kHz;
Fig. 4 (a) is the temperature variant characteristic curve of temperature coefficient of capacitance of embodiment 4 sample, and Fig. 4 (b) is for embodiment 4 sample is at the inverse dielectric constant with temperature change curve for pottery under 1kHz;
Fig. 5 (a) is the characteristic curve of the dielectric constant with temperature change of embodiment 5 sample, and Fig. 5 (b) is for embodiment 5 sample is at the inverse dielectric constant with temperature change curve for pottery under 1kHz;
Fig. 6 (a) is the temperature variant characteristic curve of temperature coefficient of capacitance of embodiment 6 sample, and Fig. 6 (b) is for embodiment 6 sample is at the inverse dielectric constant with temperature change curve for pottery under 1kHz;
Fig. 7 is ln (1/ ε-1/ ε of embodiment 1 ~ 6 sample
m) ~ ln (T-T
m) curve;
Fig. 8 is the lnf ~ T of embodiment 6 sample
mcurve.
Embodiment
Below in conjunction with accompanying drawing, by embodiment, the present invention is described in detail.
Embodiment 1
BaTiO of the present invention
3base unleaded relaxation type ceramic dielectric material, comprises major ingredient and auxiliary material, and major ingredient is BaCO
3and TiO
2, its mol ratio is 1:1, and auxiliary material is Bi
2o
3, Bi
2o
3account for the 0.5mol% of major ingredient.
Above-mentioned BaTiO
3the preparation method of base unleaded relaxation type ceramic dielectric material is as follows:
Step one: preparation BaTiO
3for subsequent use: to take BaCO according to mol ratio 1:1
3and TiO
2be mixed to form mixture.
Step 2: get mixture and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixing after, be placed in box type furnace respectively at 1150 DEG C of insulations 2 hours, form the BaTiO of pure phase
3powder, for subsequent use;
Step 3: with pure phase BaTiO
3powder is 1mol meter, takes 0.5mol%Bi respectively according to molar content
2o
3add the BaTiO of pure phase to
3in powder, after mixing, form full batching;
Entirely will prepare burden and zirconium ballstone and deionized water, and be carry out ball milling 4h successively after 1:1:1 mixing according to mass ratio, then dry to be formed and dry material, adhesive is added into dry in material and carries out granulation, then cross 40 orders and 80 mesh sieves respectively and get middle material, obtain granulation material; Wherein, adhesive accounts for dries 8% of material quality, adhesive to be mass concentration be 4% polyvinyl alcohol water solution.
Step 4: granulation material is made sample under the pressure of 120MPa, then, be placed in zirconia be backing plate the inherent high temperature box furnace of aluminium oxide saggar in, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, 3 hours are incubated, afterwards, after being cooled to 500 DEG C with 5 DEG C/min when being warming up to 1290 DEG C with 5 DEG C/min, cool to room temperature with the furnace, obtain the sample sintered;
Step 5: after the sample that polishing, cleaning sinter, evenly apply silver electrode paste at sample tow sides, sinter 20 minutes in 600 DEG C, obtain BaTiO
3base unleaded relaxation type ceramic material.
Embodiment 2
BaTiO of the present invention
3basic ring protects relaxation type ceramic dielectric material, and comprise major ingredient and auxiliary material, major ingredient is BaCO
3and TiO
2, its mol ratio is 1:1, and auxiliary material is Bi
2o
3and Al
2o
3, according to molar percent, Bi
2o
3account for the 0.5mol% of major ingredient, Al
2o
3account for the 0.25mol% of major ingredient.
BaTiO
3the preparation method of base unleaded relaxation type ceramic dielectric material, comprises the following steps:
Step one: preparation BaTiO
3for subsequent use: to take BaCO according to mol ratio 1:1
3and TiO
2be mixed to form mixture.
Step 2: get mixture and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixing after, be placed in box type furnace respectively at 1150 DEG C of insulations 2 hours, form the BaTiO of pure phase
3powder, for subsequent use;
Step 3: with pure phase BaTiO
3powder is 1mol meter, takes 0.5mol%Bi respectively according to molar content
2o
3, 0.25mol%Al
2o
3add the BaTiO of pure phase to
3in powder, full batching is formed after mixing, to entirely prepare burden and zirconium ballstone and deionized water, according to mass ratio be 1:1:1 mixing after carry out ball milling 4h successively, then dry to be formed and dry material, adhesive is added into dry in material and carries out granulation, then cross 40 orders and 80 mesh sieves respectively and get middle material, obtain granulation material; Wherein, adhesive accounts for dries 9% of material quality, adhesive to be mass concentration be 6% polyvinyl alcohol water solution.
Step 4: granulation material is made sample under the pressure of 120MPa, then, be placed in zirconia be backing plate the inherent high temperature box furnace of aluminium oxide saggar in, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, 3 hours are incubated, afterwards, after being cooled to 500 DEG C with 5 DEG C/min when being warming up to 1270 DEG C with 5 DEG C/min, cool to room temperature with the furnace, obtain the sample sintered;
Step 5: after the sample that polishing, cleaning sinter, evenly apply silver electrode paste at sample tow sides, sinter 20 minutes in 600 DEG C, obtain BaTiO
3base unleaded relaxation type ceramic material.
Embodiment 3
BaTiO of the present invention
3base unleaded relaxation type ceramic dielectric material, comprises major ingredient and auxiliary material, and major ingredient is BaCO
3and TiO
2, its mol ratio is 1:1, and auxiliary material is Bi
2o
3and Al
2o
3, according to molar percent, Bi
2o
3account for the 0.5mol% of major ingredient, Al
2o
3account for the 0.75mol% of major ingredient.
BaTiO
3the preparation method of base unleaded relaxation type ceramic dielectric material, comprises the following steps:
Step one: preparation BaTiO
3, for subsequent use: to take BaCO according to mol ratio 1:1
3and TiO
2be mixed to form mixture.
Step 2: get mixture and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixing after, be placed in box type furnace respectively at 1150 DEG C of insulations 2 hours, form the BaTiO of pure phase
3powder, for subsequent use;
Step 3: with pure phase BaTiO
3powder is 1mol meter, takes 0.5mol%Bi respectively according to molar content
2o
3, 0.75mol%Al
2o
3add the BaTiO of pure phase to
3in powder, full batching is formed after mixing, to entirely prepare burden and zirconium ballstone and deionized water, according to mass ratio be 1:1:1 mixing after carry out ball milling 4h successively, then dry to be formed and dry material, adhesive is added into dry in material and carries out granulation, then cross 40 orders and 80 mesh sieves respectively and get middle material, obtain granulation material; Wherein, adhesive accounts for dries 10% of material quality, adhesive to be mass concentration be 5% polyvinyl alcohol water solution.
Step 4: granulation material is made sample under the pressure of 120MPa, then, be placed in zirconia be backing plate the inherent high temperature box furnace of aluminium oxide saggar in, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, 3 hours are incubated, afterwards, after being cooled to 500 DEG C with 5 DEG C/min when being warming up to 1250 DEG C with 5 DEG C/min, cool to room temperature with the furnace, obtain the sample sintered;
Step 5: after the sample that polishing, cleaning sinter, evenly apply silver electrode paste at sample tow sides, sinter 20 minutes in 600 DEG C, obtain BaTiO
3base unleaded relaxation type ceramic material.
Embodiment 4
BaTiO of the present invention
3base unleaded relaxation type ceramic dielectric material, comprises major ingredient and auxiliary material, and major ingredient is BaCO
3and TiO
2, its mol ratio is 1:1, and auxiliary material is Bi
2o
3and Al
2o
3, according to molar percent, Bi
2o
3account for the 0.5mol% of major ingredient, Al
2o
3account for the 1.00mol% of major ingredient.
BaTiO
3the preparation method of base unleaded relaxation type ceramic dielectric material, comprises the following steps:
Step one: preparation BaTiO
3for subsequent use: to take BaCO according to mol ratio 1:1
3and TiO
2be mixed to form mixture.
Step 2: get mixture and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixing after, be placed in box type furnace respectively at 1150 DEG C of insulations 2 hours, form the BaTiO of pure phase
3powder, for subsequent use;
Step 3: with pure phase BaTiO
3powder is 1mol meter, takes 0.5mol%Bi respectively according to molar content
2o
3, 1.00mol%Al
2o
3add the BaTiO of pure phase to
3in powder, full batching is formed after mixing, to entirely prepare burden and zirconium ballstone and deionized water, according to mass ratio be 1:1:1 mixing after carry out ball milling 4h successively, then dry to be formed and dry material, adhesive is added into dry in material and carries out granulation, then cross 40 orders and 80 mesh sieves respectively and get middle material, obtain granulation material; Wherein, adhesive accounts for dries 9% of material quality, adhesive to be mass concentration be 6% polyvinyl alcohol water solution.
Step 4: granulation material is made sample under the pressure of 120MPa, then, be placed in zirconia be backing plate the inherent high temperature box furnace of aluminium oxide saggar in, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, 3 hours are incubated, afterwards, after being cooled to 500 DEG C with 5 DEG C/min when being warming up to 1250 DEG C with 5 DEG C/min, cool to room temperature with the furnace, obtain the sample sintered;
Step 5: after the sample that polishing, cleaning sinter, evenly apply silver electrode paste at sample tow sides, sinter 20 minutes in 600 DEG C, obtain BaTiO
3base unleaded relaxation type ceramic material.
Embodiment 5
BaTiO of the present invention
3base unleaded relaxation type ceramic dielectric material, comprises major ingredient and auxiliary material, and major ingredient is BaCO
3and TiO
2, its mol ratio is 1:1, and auxiliary material is Bi
2o
3and Al
2o
3, according to molar percent, Bi
2o
3account for the 0.5mol% of major ingredient, Al
2o
3account for the 2.00mol% of major ingredient.
BaTiO
3the preparation method of base unleaded relaxation type ceramic dielectric material, comprises the following steps:
Step one: preparation BaTiO
3for subsequent use: to take BaCO according to mol ratio 1:1
3and TiO
2be mixed to form mixture.
Step 2: get mixture and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixing after, be placed in box type furnace respectively at 1150 DEG C of insulations 2 hours, form the BaTiO of pure phase
3powder, for subsequent use;
Step 3: with pure phase BaTiO
3powder is 1mol meter, takes 0.5mol%Bi respectively according to molar content
2o
3, 2.00mol%Al
2o
3add the BaTiO of pure phase to
3in powder, full batching is formed after mixing, to entirely prepare burden and zirconium ballstone and deionized water, according to mass ratio be 1:1:1 mixing after carry out ball milling 4h successively, then dry to be formed and dry material, adhesive is added into dry in material and carries out granulation, then cross 40 orders and 80 mesh sieves respectively and get middle material, obtain granulation material; Wherein, adhesive accounts for dries 9% of material quality, adhesive to be mass concentration be 4% polyvinyl alcohol water solution.
Step 4: granulation material is made sample under the pressure of 120MPa, then, be placed in zirconia be backing plate the inherent high temperature box furnace of aluminium oxide saggar in, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, 3 hours are incubated, afterwards, after being cooled to 500 DEG C with 5 DEG C/min when being warming up to 1230 DEG C with 5 DEG C/min, cool to room temperature with the furnace, obtain the sample sintered;
Step 5: after the sample that polishing, cleaning step five sinter, evenly apply silver electrode paste at sample tow sides, sinter 20 minutes in 600 DEG C, obtain BaTiO
3base unleaded relaxation type ceramic material.
Embodiment 6
BaTiO of the present invention
3base unleaded relaxation type ceramic dielectric material, comprises major ingredient and auxiliary material, and major ingredient is BaCO
3and TiO
2, its mol ratio is 1:1, and auxiliary material is Bi
2o
3and Al
2o
3, according to molar percent, Bi
2o
3account for the 0.5mol% of major ingredient, Al
2o
3account for the 3.00mol% of major ingredient.
BaTiO
3the preparation method of base unleaded relaxation type ceramic dielectric material, comprises the following steps:
Step one: preparation BaTiO
3for subsequent use: to take BaCO according to mol ratio 1:1
3and TiO
2be mixed to form mixture.
Step 2: get mixture and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixing after, be placed in box type furnace respectively at 1150 DEG C of insulations 2 hours, form the BaTiO of pure phase
3powder, for subsequent use;
Step 3: with pure phase BaTiO
3powder is 1mol meter, takes 0.5mol%Bi respectively according to molar content
2o
3, 3.00mol%Al
2o
3add the BaTiO of pure phase to
3in powder, full batching is formed after mixing, to entirely prepare burden and zirconium ballstone and deionized water, according to mass ratio be 1:1:1 mixing after carry out ball milling 4h successively, then dry to be formed and dry material, adhesive is added into dry in material and carries out granulation, then cross 40 orders and 80 mesh sieves respectively and get middle material, obtain granulation material; Wherein, adhesive accounts for dries 8% of material quality, adhesive to be mass concentration be 5% polyvinyl alcohol water solution.
Step 4: granulation material is made sample under the pressure of 120MPa, then, be placed in zirconia be backing plate the inherent high temperature box furnace of aluminium oxide saggar in, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, 3 hours are incubated, afterwards, after being cooled to 500 DEG C with 5 DEG C/min when being warming up to 1230 DEG C with 5 DEG C/min, cool to room temperature with the furnace, obtain the sample sintered;
Step 5: after the sample that polishing, cleaning sinter, evenly apply silver electrode paste at sample tow sides, sinter 20 minutes in 600 DEG C, obtain BaTiO
3base unleaded relaxation type ceramic material.
Refer to shown in Fig. 1 to Fig. 8, dielectric property test shows: the ceramic medium material prepared by embodiment 1 to embodiment 6 all meets Relaxation Ferroelectrics, and concrete parameters is as shown in table 1.
The T of the ceramic material obtained by table 1 embodiment 1-6
m, T
c, T
cw, △ T
m, ε
m, γ, △ T
difwith △ T
relax
In table, T
mit is dielectric constant maximum corresponding temperature; T
cit is Curie-point temperature; T
cwit is the temperature that change in dielectric constant starts to follow corresponding to Curie-Weiss law; △ T
m=T
cw-T
m; ε
m-dielectric constant maximum; γ is disperse index; △ T
difthe parameter △ T of exosyndrome material Phase Transformation Diffusion degree
difbe defined as T
dif1kHz=T
0.9 ε m1kHz-T
ε m1kHz; △ T
relaxbe the parameter describing frequency dispersion degree under 1kHz ~ 1000kHz, be defined as T
relax=T
m1000kHz-T
m1kHz.
As can be seen from Figure 7, ferroelectric-para-electric phase transformation diffusion parameter deviate from concrete Curie-Weiss law, but still follows general Curie-weiss relational expression:
In formula: ε
m-dielectric constant maximum, ε-dielectric constant, T
m-phase transition temperature, C-Curie-Weiss constant, γ-disperse index, by carrying out matching with formula, the straight slope obtained is γ.
Fig. 8 is 1000/T
m~ lnf curve and formula (1-2) matched curve, carry out matching by experiment the data obtained and Vogel-Fulcher equation, by calculating the E of obtained ceramic material
afor 0.0678eV, T
ffor 382.28K, f
0be 1.76 × 1018Hz.From Fig. 8, also can find out that experiment the data obtained conforms to substantially with Vogel-Fulcher matched curve, the process of ceramic material frequency of occurrences dispersion meets glassy state model.
Vogel-Fulcher equation is:
In formula: f
0-pre-exponential factor, E
a-activation energy, k
b-Boltzmann constant, T
f-solidification point.
As can be seen from the above table by doping Bi
2o
3and Al
2o
3, and and BaTiO
3form solid solution, effectively can improve Curie point, Curie peak be moved to high temperature direction, can also sintering temperature be reduced; Along with Al
2o
3the increase of content, can make grain refinement.Meanwhile, form the fluctuating of micro components, composition fluctuation theory proposes based on compound ion random distribution phenomenon.Think that different ions such as to occupy at random at the isomorphous position, produce microscopic concentration and the different microcell of integral macroscopic concentration, form different microcell and there is slightly different Curie temperature, macroscopically produce the transition temperature area of broadening, even if the average component of microcell is identical, also may form the different microcell of structure due to cell configuration difference, thus produce Diffuse phase transition.By adulterating or changing the physical dimension of crystal grain, the Curie temperature of ferroelectric ceramic can be made to change, the dielectric constant of peak value both sides rises, namely the warm curve that is situated between becomes more extensive, smooth, this by adulterating or changing the effect that grainiess size improves the temperature stability of ceramic dielectric constant, be called broadening effect.BaTiO prepared by the present invention
3base unleaded relaxation type ceramic dielectric material, not only preparation technology is simple, the cost of material is low, and have higher dielectric constant, low dielectric loss, and being expected to alternative lead base ceramic material becomes one of multilayer ceramic capacitor important candidate material double excellent technically and economically.
Embodiment 7
BaTiO of the present invention
3base unleaded relaxation type ceramic dielectric material, comprises major ingredient and auxiliary material, and major ingredient is BaCO
3and TiO
2, its mol ratio is 1:1, and auxiliary material is Bi
2o
3, Bi
2o
3account for the 0.5mol% of major ingredient.
Above-mentioned BaTiO
3the preparation method of base unleaded relaxation type ceramic dielectric material is as follows:
Step one: preparation BaTiO
3for subsequent use: to take BaCO according to mol ratio 1:1
3and TiO
2be mixed to form mixture.
Step 2: get mixture and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixing after, be placed in box type furnace respectively at 1130 DEG C of insulations 2 hours, form the BaTiO of pure phase
3powder, for subsequent use;
Step 3: with pure phase BaTiO
3powder is 1mol meter, takes 0.5mol%Bi respectively according to molar content
2o
3add the BaTiO of pure phase to
3in powder, after mixing, form full batching;
Entirely will prepare burden and zirconium ballstone and deionized water, and be carry out ball milling 3h successively after 1:1:1 mixing according to mass ratio, then dry to be formed and dry material, adhesive is added into dry in material and carries out granulation, then cross 40 orders and 80 mesh sieves respectively and get middle material, obtain granulation material; Wherein, adhesive accounts for dries 8% of material quality, adhesive to be mass concentration be 6% polyvinyl alcohol water solution.
Step 4: granulation material is made sample under the pressure of 120MPa, then, be placed in zirconia be backing plate the inherent high temperature box furnace of aluminium oxide saggar in, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, 3 hours are incubated, afterwards, after being cooled to 500 DEG C with 5 DEG C/min when being warming up to 1240 DEG C with 5 DEG C/min, cool to room temperature with the furnace, obtain the sample sintered;
Step 5: after the sample that polishing, cleaning sinter, evenly apply silver electrode paste at sample tow sides, sinter 30 minutes in 600 DEG C, obtain BaTiO
3base unleaded relaxation type ceramic material.
Embodiment 8
BaTiO of the present invention
3base unleaded relaxation type ceramic dielectric material, comprises major ingredient and auxiliary material, and major ingredient is BaCO
3and TiO
2, its mol ratio is 1:1, and auxiliary material is Bi
2o
3, Bi
2o
3account for the 0.5mol% of major ingredient, Al
2o
3account for the 2.5mol% of major ingredient.
Above-mentioned BaTiO
3the preparation method of base unleaded relaxation type ceramic dielectric material is as follows:
Step one: preparation BaTiO
3for subsequent use: to take BaCO according to mol ratio 1:1
3and TiO
2be mixed to form mixture.
Step 2: get mixture and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixing after, be placed in box type furnace respectively at 1170 DEG C of insulations 2.5 hours, form the BaTiO of pure phase
3powder, for subsequent use;
Step 3: with pure phase BaTiO
3powder is 1mol meter, takes 0.5mol%Bi respectively according to molar content
2o
3, 2.5mol%Al
2o
3add the BaTiO of pure phase to
3in powder, after mixing, form full batching;
To entirely prepare burden and zirconium ballstone and deionized water, according to mass ratio be 1:1:1 mixing after carry out ball milling 3.5h successively, then dry formed dry material, adhesive is added into dry material in carry out granulation, then 40 orders and 80 mesh sieves get middle material excessively respectively, obtain granulation material; Wherein, adhesive accounts for dries 9% of material quality, adhesive to be mass concentration be 5% polyvinyl alcohol water solution.
Step 4: granulation material is made sample under the pressure of 120MPa, then, be placed in zirconia be backing plate the inherent high temperature box furnace of aluminium oxide saggar in, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, 2.5 hours are incubated, afterwards, after being cooled to 500 DEG C with 5 DEG C/min when being warming up to 1280 DEG C with 5 DEG C/min, cool to room temperature with the furnace, obtain the sample sintered;
Step 5: after the sample that polishing, cleaning sinter, evenly apply silver electrode paste at sample tow sides, sinter 25 minutes in 600 DEG C, obtain BaTiO
3base unleaded relaxation type ceramic material.
Embodiment 9
BaTiO of the present invention
3base unleaded relaxation type ceramic dielectric material, comprises major ingredient and auxiliary material, and major ingredient is BaCO
3and TiO
2, its mol ratio is 1:1, and auxiliary material is Bi
2o
3, Bi
2o
3account for the 0.5mol% of major ingredient, Al
2o
3account for the 1.5mol% of major ingredient.
Above-mentioned BaTiO
3the preparation method of base unleaded relaxation type ceramic dielectric material is as follows:
Step one: preparation BaTiO
3for subsequent use: to take BaCO according to mol ratio 1:1
3and TiO
2be mixed to form mixture.
Step 2: get mixture and zirconium ballstone and deionized water, according to mass ratio be carry out ball milling, oven dry, briquetting successively after 1:1:1 mixing after, be placed in box type furnace respectively at 1160 DEG C of insulations 3 hours, form the BaTiO of pure phase
3powder, for subsequent use;
Step 3: with pure phase BaTiO
3powder is 1mol meter, takes 0.5mol%Bi respectively according to molar content
2o
3, 1.5mol%Al
2o
3add the BaTiO of pure phase to
3in powder, after mixing, form full batching;
Entirely will prepare burden and zirconium ballstone and deionized water, and be carry out ball milling 4h successively after 1:1:1 mixing according to mass ratio, then dry to be formed and dry material, adhesive is added into dry in material and carries out granulation, then cross 40 orders and 80 mesh sieves respectively and get middle material, obtain granulation material; Wherein, adhesive accounts for dries 10% of material quality, adhesive to be mass concentration be 4% polyvinyl alcohol water solution.
Step 4: granulation material is made sample under the pressure of 120MPa, then, be placed in zirconia be backing plate the inherent high temperature box furnace of aluminium oxide saggar in, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, 2 hours are incubated, afterwards, after being cooled to 500 DEG C with 5 DEG C/min when being warming up to 1260 DEG C with 5 DEG C/min, cool to room temperature with the furnace, obtain the sample sintered;
Step 5: after the sample that polishing, cleaning sinter, evenly apply silver electrode paste at sample tow sides, sinter 20 minutes in 600 DEG C, obtain BaTiO
3base unleaded relaxation type ceramic material.
Claims (5)
1. a BaTiO
3the preparation method of base unleaded relaxation type ceramic dielectric material, is characterized in that: comprise the steps:
Step one: preparation BaTiO
3for subsequent use: to take BaCO according to mol ratio 1:1
3and TiO
2be mixed to form mixture;
Step 2: after mixture is carried out ball milling, oven dry, briquetting, is placed in box type furnace in 1130-1170 DEG C of insulation 2-3 hour, forms the BaTiO of pure phase
3powder;
Step 3: with the BaTiO of pure phase
3powder is 1mol meter, takes 0.5mol%Bi respectively according to molar content
2o
3and xmol%Al
2o
3be added into the BaTiO of pure phase
3in powder, formed and entirely prepare burden, carrying out ball milling, oven dry, granulation by entirely preparing burden, sieving, form granulation material; Wherein, x=0.00 ~ 3.00;
Step 4: granulation material is made sample, then be placed in zirconia be backing plate the inherent high temperature box furnace of aluminium oxide saggar in, 500 DEG C of insulation 60min are warming up to 2 DEG C/min, 2-3 hour is incubated when being warming up to 1230 ~ 1290 DEG C with 5 DEG C/min, afterwards, after being cooled to 500 DEG C with 5 DEG C/min, cool to room temperature with the furnace, obtain the sample sintered;
Step 5: after the sample sintered being carried out polish, cleaning, evenly apply silver electrode paste at sample tow sides, in 600 DEG C of sintering 20-30 minute, obtain BaTiO
3base unleaded relaxation type ceramic dielectric material; The E of obtained ceramic material
afor 0.0678eV, T
ffor 382.28K, f
0be 1.76 × 1018Hz;
In described step 3, Ball-milling Time is 3-4 hour;
In described step 4, granulation material makes sample under the pressure of 120MPa;
In described step 3, formed after full batching, zirconium ballstone and deionized water mixing, ball milling, oven dry and dry material, adhesive is added into dry in material and carries out granulation, then cross 40 orders and 80 mesh sieves respectively and get and middlely to expect, obtain granulation material; Wherein, adhesive accounts for and dries 8 ~ 10% of material quality;
Described adhesive to be mass concentration be 4 ~ 6% polyvinyl alcohol water solution.
2. a kind of BaTiO as claimed in claim 1
3the preparation method of base unleaded relaxation type ceramic dielectric material, is characterized in that: in described step 3, ball milling specifically will be prepared burden and zirconium ballstone, deionized water entirely, is carry out after 1:1:1 mixes according to mass ratio.
3. a kind of BaTiO as claimed in claim 1
3the preparation method of base unleaded relaxation type ceramic dielectric material, is characterized in that: in described step 3, x is 0,0.25,0.75,1.00,2.00 or 3.00.
4. according to the BaTiO that the preparation method described in any one in claims 1 to 3 prepares
3base lead-free ceramics dielectric substance, is characterized in that: described BaTiO
3the major ingredient of base lead-free ceramics dielectric substance is BaCO
3and TiO
2, its mol ratio is 1:1, and auxiliary material is Bi
2o
3and Al
2o
3; According to molar percent, Bi
2o
3account for the 0.5mol% of major ingredient, Al
2o
3account for the xmol% of major ingredient, wherein, x=0.00 ~ 3.00.
5. according to the BaTiO that preparation method according to claim 4 prepares
3base lead-free ceramics dielectric substance, is characterized in that: according to molar percent, and described x is 0,0.25,0.75,1.00,2.00 or 3.00.
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