CN1320147C - Preparation of nickel-barium titanate high-permittivity composite material using nitrogen protection and preparing process thereof - Google Patents
Preparation of nickel-barium titanate high-permittivity composite material using nitrogen protection and preparing process thereof Download PDFInfo
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- CN1320147C CN1320147C CNB2005100614540A CN200510061454A CN1320147C CN 1320147 C CN1320147 C CN 1320147C CN B2005100614540 A CNB2005100614540 A CN B2005100614540A CN 200510061454 A CN200510061454 A CN 200510061454A CN 1320147 C CN1320147 C CN 1320147C
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- barium titanate
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- nitrogen protection
- sintering
- specific inductivity
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 23
- 229910002113 barium titanate Inorganic materials 0.000 title claims abstract description 21
- 238000000034 method Methods 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 title claims description 18
- 239000002131 composite material Substances 0.000 title abstract description 3
- PXSIFGRGUVISHI-UHFFFAOYSA-N [Ni].[Ba] Chemical compound [Ni].[Ba] PXSIFGRGUVISHI-UHFFFAOYSA-N 0.000 title 1
- 238000005245 sintering Methods 0.000 claims abstract description 23
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 26
- 239000011159 matrix material Substances 0.000 claims description 16
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 12
- 229910052788 barium Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 claims description 9
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 9
- 230000007613 environmental effect Effects 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 238000000748 compression moulding Methods 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910010293 ceramic material Inorganic materials 0.000 abstract description 3
- 239000002360 explosive Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 239000004020 conductor Substances 0.000 description 14
- 239000000919 ceramic Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 238000012423 maintenance Methods 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001757 thermogravimetry curve Methods 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000003985 ceramic capacitor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Inorganic Insulating Materials (AREA)
Abstract
The present invention discloses a high-dielectric Ni-barium titanate composite material and a preparing method thereof under nitrogen protection. The preparing method comprises the following steps: mixing 65% to 99% of barium titanate and 1% to 35% of metal Ni measured by volume percentage content; grinding the mixture for 1 to 5 hours; pressing and shaping the mixture at pressure of 2 to 10MPa; preparing the ceramic material in a Ni environment. The present invention is simple in formula, and the obtained ceramic material has the advantages of high dielectric constant (10000 to 80000 at 1KHz), small grain size of barium titanate, excellent temperature stability, low cost and good market prospect. The change rate (epsilon125 to epsilon25)/epsilon25 of the dielectric constant following a temperature at 30 to 170 DEG C is between 7% and 25%. Additionally, pure N2 gas which is cheap and safe is used as a sintering atmosphere to avoid the possible danger brought by the introduction of explosive gas (H2).
Description
Technical field
The present invention relates to the dielectric ceramic technical field, specially refer to high Jie's matrix material of Ni-Ti acid barium of a kind of nitrogen protection preparation and preparation method thereof.
Background technology
In recent years, developing rapidly of power industry and electronic information industry promotes electronic devices and components to miniaturization, integrated, high reliability and cheaply direction develop.In the ceramic condenser field, miniaturization, heavy body and good temperature stability have become inevitable development trend.As laminated ceramic capacitor (MLCC) is exactly a kind of new texture of realizing the jumbo requirement design of small volume in order to reach.And for further raising capacity with reduce volume, along with preparation technology's development, MLCC is also more towards the number of plies, that medium layer is thinner, and direction develops.Yet, also more and more higher along with the continuous development of science and technology to the requirement of high dielectric constant material, because electric capacity is directly proportional with the specific inductivity of ceramic dielectic, improve heavy body and the miniaturization of specific inductivity with easier realization device.In addition, in order to reach enough good insulating property, with regard to MLCC, the thickness of the ceramic dielectric layer between adjacent two electrodes is at least about 10 times of grain-size, that is the thickness of medium layer can not unlimitedly reduce.In this case, improving the specific inductivity of stupalith, is very necessary.
Seepage theory provides a kind of thinking for the preparation high-k dielectric materials.Usually, in order to obtain high-k, people often adopt the barium titanate based ceramic material, and add Nb, Ta, and Mn, metal oxides such as Mg are properties-correcting agent.Yet the raising to specific inductivity still is not clearly, and technology is comparatively complicated.Seepage theory is then pointed out, in dielectric, add conductor, continuous increase along with the conductor content that is added, compound system turns to conductor from isolator gradually, and this isolator-conductor transformation is a kind of mutation process, the trace that is the volume fraction of conductor increases, and just can make the specific conductivity of compound system that the variation of some orders of magnitude takes place.Usually, the volume fraction of the conductive phase that contained in the system when realizing that isolator-conductor changes of people calls the seepage flow threshold value.When the volume content of conductor was near the seepage flow threshold value, non-linear enhancing also can take place in the specific inductivity of material.Specific inductivity with the variation of conductor volume content can be with the seepage flow formulate: ε=ε
0| f
c-f|
-q, in the formula, f
cBe the seepage flow threshold value of conductor, f is the volume fraction of conductor, ε
0Be the specific inductivity of insulating body, ε is the specific inductivity of compound system, and q then is a critical exponent of seepage flow system.From this formula as seen, as the volume fraction f＜f of conductor
cAnd f → f
cThe time, conductor-isolator compound system just can obtain the specific inductivity than high times of dielectric substrate.Research for this dielectric materials based on seep effect, can be divided into organic radical and ceramic base two big classes: for the organic radical material, the normal dielectric matrix that adopts has PVDF, PTFE etc., its advantage is without sintering, therefore technology is comparatively simple, but shortcoming is the often lower and non-refractory of specific inductivity of organic matrix, thereby the composite diphase material specific inductivity of preparation is low with respect to ceramic based materials such as barium titanates, and can not be applied to hot conditions, application is subject to certain restrictions.For ceramic based material, research is less at present, people such as Carlos Pecharrom á n in calendar year 2001 at Advanced Materials (Carlos Pecharrom á n, F.Esteban-Betegon, et al., Advanced Materials 13 (20) (2001), publish an article on P1541-1544), successfully at reducing atmosphere (90%Ar/10%H
2) (when temperature is lower than 500 ℃) and protective atmosphere (Ar, 500 ℃～1300 ℃) sintering prepared the Ni-BaTiO with ultra-high dielectric coefficient
3Matrix material; People such as Renzheng Chen are at Ceramics International (R.Z.Chen, X.H.Wang, H.Wen, et al., Ceramics International 30 (2004), delivered with nanometer Ni (granularity is about 50nm) and nanometer BaTiO on P1271-1274.)
3(granularity is 100nm) is raw material, and adds MgO and some rare earth oxides, prepared Ni-BaTiO at 1300 ℃ of sintering of reducing atmosphere (90%Ar/10%H2) equally
3Matrix material, but do not obtain ultra-high dielectric coefficient.The characteristics that these materials successfully prepare all are to utilize Ar and H
2As restitutive protection's gas of reaction, solving the metal problem of stable existence at high temperature, yet reducing atmosphere is to BaTiO
3Sintering actual be disadvantageous, cause BaTiO easily
3Semiconductor.Compare with cheap nitrogen, utilize nitrogen will reduce production costs greatly, simultaneously to preventing BaTiO as the inert protective gas of reaction
3It is originally favourable relatively serious semiconductor to occur.
Summary of the invention
The object of the present invention is to provide a kind of high Jie's matrix material of Ni-Ti acid barium in nitrogen protection preparation and preparation method thereof.This material feedstock kind is few, and preparation technology is simple, and is with low cost, and dielectric properties are good, has excellent temperature stability when having ultra-high dielectric coefficient.
The technical solution used in the present invention is as follows:
1, a kind of high Jie's matrix material of Ni-Ti acid barium of nitrogen protection preparation, the composition of this material by volume percentage composition is:
Grain-size is the barium titanate 65%～99% of 100nm～400nm;
Granularity is the metal Ni 1%～35% of 40～200nm;
Represent the volumn concentration of Ni, i.e. 0.01≤f≤0.35 with f.
2, a kind of nitrogen protection prepares the preparation method of the high Jie's matrix material of Ni-Ti acid barium; the step of this method is as follows: with barium titanate and metal Ni is raw material; by volume percentage composition is 65%～99% barium titanate with after 1%～35% metal Ni mixes; ground 1～5 hour; with pressure is 2～10MPa compression moulding, and in nitrogen sintering, sintering range is 1200～1300 ℃; the temperature rise rate span of control is 100～600 ℃/h, and soaking time is controlled at 1～3h.
Adopt nitrogen to carry out sintering for the sintering environmental gas, environmental gas airshed scope is 70～300ml/min.The stupalith for preparing, its barium titanate grain-size is 100nm～1500nm; Thereby cause material to have good temperature stability, between 30～170 ℃, the velocity of variation (ε of dielectric constant with temperature
125-ε
25)/ε
25Between 7%～25%.
The present invention compares the useful effect that has with background technology: stupalith provided by the present invention and preparation method thereof is a kind of novel stupalith system, prescription is simple, the stupalith for preparing has high-k (specific inductivity is 10000 to 80000 during 1KHz), and barium titanate grain-size little (grain-size is less than 1500nm).Undersized barium titanate crystal grain causes material to have good temperature stability, between 30～170 ℃, and the velocity of variation (ε of dielectric constant with temperature
125-ε
25)/ε
25Between 7%～25%.And sintering atmosphere is comparatively cheap and safe pure gas N
2, avoided explosion hazard gas H
2The danger that may bring of introducing, and with low cost, thereby have good market outlook.
Description of drawings
Fig. 1 is the curve of embodiment 1 in the dielectric constant with temperature variation of 1200 ℃ of agglomerating samples;
Fig. 2 is the curve of embodiment 2 in the dielectric constant with temperature variation of 1250 ℃ of agglomerating samples;
Fig. 3 is the curve of embodiment 3 in the dielectric constant with temperature variation of 1300 ℃ of agglomerating samples.
Embodiment
Embodiment 1:
Barium titanate powder and metallic nickel are mixed (the Ni volumn concentration is between 1%～35%) by the different volumes percentage composition; and in mortar, ground 1 hour; under the pressure of 10MPa, be molded into diameter then and be about 10mm; thickness is about the circular green compact of 2mm, carries out sintering in box gas shield resistance furnace.Feed nitrogen in the electric furnace and carry out sintering after 4 hours again, maintenances nitrogen flow is 250ml/min, rise to 550 ℃ with the temperature rise rate of 400 ℃/h after, rise to 1200 ℃ with the temperature rise rate of 150 ℃/h again and be incubated 3 hours, afterwards naturally cooling.The temperature spectrum of relative permittivity, dielectric loss and the specific inductivity of material is tested and calculated to sample behind the sintering 200 ℃ of following burning infiltration silver electrodes, then after surface finish.Test result sees Table 1 and accompanying drawing 1.Table 1 provides that specific inductivity and dielectric loss are with the variation relation (under the room temperature) of metal Ni volume content under the 1KHz, and accompanying drawing 1 is the specific inductivity thermogram (30 ℃～180 ℃) of part high-k sample.From table 1, when Ni volume fraction f was between 0.2～0.25, material obtained bigger specific inductivity, and when f=0.25, specific inductivity is 35000, is about 14 times with the barium titanate matrix material for preparing under the condition; When f=0.26, specific inductivity is 25700, but loss this moment is bigger, is 1.5, and is unavailable; And behind volume fraction f＞0.26 of Ni, material then becomes conductor.Can find out that from accompanying drawing 1 specific inductivity of this material has good temperature stability: when temperature is between 30～170 ℃, (ε
125-ε
25)/ε
25Between 7%～12%.
The dielectric properties of table 1.1200 ℃ agglomerating sample and the relation of metal Ni volume fraction
| Ni | 0 | 0.01 | 0.15 | 0.2 | 0.22 | 0.24 | 0.25 | 0.26 | 0.30 | 0.35 |
| Specific inductivity | 2450 | 1561 | 2856 | 5982 | 10980 | 19800 | 35000 | 25700 | 8300 | 4321 |
| Dielectric loss | 0.042 | 0.057 | 0.051 | 0.063 | 0.17 | 0.21 | 0.43 | 1.5 | 21 | 17 |
Embodiment 2
Barium titanate powder and metallic nickel are mixed (the Ni volumn concentration is between 1%～35%) by the different volumes percentage composition; and in mortar, ground 3 hours; under the pressure of 5MPa, be molded into diameter then and be about 10mm; thickness is about the circular green compact of 2mm, carries out sintering in box gas shield resistance furnace.Feed nitrogen in the electric furnace and carry out sintering after 5 hours again, maintenances nitrogen flow is 170ml/rmin, rise to 400 ℃ with the temperature rise rate of 600 ℃/h after, rise to 1250 ℃ with the temperature rise rate of 200 ℃/h again and be incubated 2 hours, afterwards naturally cooling.The temperature spectrum of relative permittivity, dielectric loss and the specific inductivity of material is tested and calculated to sample behind the sintering 180 ℃ of following burning infiltration silver electrodes, then after surface finish.Test result sees Table 2 and accompanying drawing 2.Table 2 provides that specific inductivity and dielectric loss are with the variation relation (under the room temperature) of metal Ni volume content under the 1KHz, and accompanying drawing 2 is the specific inductivity thermogram (30 ℃～180 ℃) of part high-k sample.From table 2, when Ni volume fraction f was between 0.18～0.23, material obtained bigger specific inductivity, and when f=0.23, specific inductivity is about 25 times with the barium titanate matrix material for preparing under the condition near 80000; When f 〉=0.24, material becomes conductor.Can find out that from accompanying drawing 2 specific inductivity of this high dielectric constant material has good temperature stability: when temperature is between 30～170 ℃, (ε
125-ε
25)/ε
25Between 10%～15%.
The dielectric properties of table 2.1250 ℃ agglomerating sample and the relation of metal Ni volume fraction
| Ni | 0 | 0.10 | 0.15 | 0.18 | 0.20 | 0.21 | 0.22 | 0.23 | 0.24 | 0.30 | 0.35 |
| Specific inductivity | 3133 | 1728 | 2616 | 6842 | 12155 | 37531 | 45412 | 77669 | 56700 | 3200 | 1700 |
| Dielectric loss | 0.034 | 0.047 | 0.034 | 0.037 | 0.026 | 0.028 | 0.032 | 0.38 | 0.13 | 15 | 27 |
Embodiment 3:
Barium titanate powder and metallic nickel are mixed (the Ni volumn concentration is between 1%～35%) by the different volumes percentage composition; and in mortar, ground 5 hours; under the pressure of 2MPa, be molded into diameter then and be about 10mm; thickness is about the circular green compact of 2mm, carries out sintering in box gas shield resistance furnace.Feed nitrogen in the electric furnace and carry out sintering after 7 hours again, maintenances nitrogen flow is 70ml/min, rise to 400 ℃ with the temperature rise rate of 600 ℃/h after, rise to 1300 ℃ with the temperature rise rate of 100 ℃/h again and be incubated 1 hour, afterwards naturally cooling.The temperature spectrum of relative permittivity, dielectric loss and the specific inductivity of material is tested and calculated to sample behind the sintering 230 ℃ of following burning infiltration silver electrodes, then after surface finish.Test result sees Table 3 and accompanying drawing 3.Table 3 provides that specific inductivity and dielectric loss are with the variation relation (under the room temperature) of metal Ni volume content under the 1KHz, and accompanying drawing 3 is the specific inductivity thermogram (30 ℃～180 ℃) of part high-k sample.From table 3, when Ni volume fraction f was between 0.17～0.22, material obtained bigger specific inductivity, and when f=0.22, specific inductivity is 83000, is about 18 times with the barium titanate matrix material for preparing under the condition; When f 〉=0.23, material becomes conductor.Can find out that from accompanying drawing 3 specific inductivity of this material has good temperature stability: when temperature is between 30～170 ℃, (ε
125-ε
25)/ε
25Between 15%～25%.
The dielectric properties of table 3.1300 ℃ agglomerating sample and the relation of metal Ni volume fraction
| Ni | 0 | 0.10 | 0.15 | 0.17 | 0.19 | 0.21 | 0.22 | 0.23 | 0.30 | 0.35 |
| Specific inductivity | 4500 | 3812 | 5421 | 8700 | 24180 | 58690 | 83000 | 68700 | 5420 | 1300 |
| Dielectric loss | 0.03 | 0.04 | 0.052 | 0.035 | 0.09 | 0.11 | 0.32 | 20 | 110 | 87 |
Claims (4)
1, the high Jie's matrix material of Ni-Ti acid barium of a kind of nitrogen protection preparation, the composition that it is characterized in that this material by volume percentage composition is:
Grain-size is the barium titanate 65%～99% of 100nm～400nm;
Granularity is the metal Ni 1%～35% of 40～200nm;
Represent the volumn concentration of Ni, i.e. 0.01≤f≤0.35 with f.
2, a kind of nitrogen protection prepares the preparation method of the high Jie's matrix material of Ni-Ti acid barium; the step that it is characterized in that this method is as follows: with barium titanate and metal Ni is raw material; by volume percentage composition is 65%～99% barium titanate with after 1%～35% metal Ni mixes; ground 1～5 hour; with pressure is 2～10MPa compression moulding, and in nitrogen sintering, sintering range is 1200～1300 ℃; the temperature rise rate span of control is 100～600 ℃/h, and soaking time is controlled at 1～3h.
3, a kind of nitrogen protection according to claim 2 prepares the preparation method of the high Jie's matrix material of Ni-Ti acid barium, it is characterized in that: adopt nitrogen to carry out sintering for the sintering environmental gas, environmental gas airshed scope is 70～300ml/min.
4, a kind of nitrogen protection according to claim 2 prepares the preparation method of the high Jie's matrix material of Ni-Ti acid barium, and it is characterized in that: the stupalith for preparing, its barium titanate grain-size is 100nm～1500nm.
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|---|---|---|---|
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