CN104867638B - The rheostatic manufacturing method of Zinc oxide - Google Patents
The rheostatic manufacturing method of Zinc oxide Download PDFInfo
- Publication number
- CN104867638B CN104867638B CN201510087897.0A CN201510087897A CN104867638B CN 104867638 B CN104867638 B CN 104867638B CN 201510087897 A CN201510087897 A CN 201510087897A CN 104867638 B CN104867638 B CN 104867638B
- Authority
- CN
- China
- Prior art keywords
- oxide
- rheostat
- zinc oxide
- rheostatic
- glass
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/10—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material voltage responsive, i.e. varistors
- H01C7/105—Varistor cores
- H01C7/108—Metal oxide
- H01C7/112—ZnO type
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Compositions Of Oxide Ceramics (AREA)
- Thermistors And Varistors (AREA)
- Apparatuses And Processes For Manufacturing Resistors (AREA)
Abstract
The present invention provides a kind of rheostatic manufacturing method of Zinc oxide.By will be added to rheostat raw material made of the first additive using zinc oxide as main material, in the main material, and as zinc borosilicate system glass, be added to the mixing material that glass material mixes made of the second additive and form varistor element.At this point, the first additive and the second additive contain the defined common element in the both sides for making an addition to rheostat raw material and glass material, thus by the excellent Zinc oxide rheostat of varistor element manufacture electrical characteristics.
Description
Technical field
The present invention relates to the Zinc oxide variable resistances used in a kind of removing such as power supply noise, lightning induction noise
The manufacturing method of device.
Background technology
With the high frequency of electric/electronic device, high capacity, as being protected in such as mobile phone, automobile etc.
Circuitry is not influenced or is ensured the steady of work by power supply noise, various surges, pulsive noise, static discharge (ESD)
Qualitative countermeasure, for being coped with as defined in noise, used oxidation zinc-type Stacked rheostat.As its representative application
Example, can enumerate：As protect semiconductor not by mobile electronic device, vehicle electronic device got rid of load surge, surge of lighting a fire,
The utilization of the semiconductor protective elements of the influence of lightning surge, ESD, switching surges.
As the basic composition of zinc oxide varistor, addition promotes the Bi of grain growth2O3, inhibit grain growth
Sb2O3.In addition, adding various glass etc. is used as sintering aid.Rheostat by additive, its additive amount combination by make to obtain
Electrical characteristics, reliability significantly changes.For example, generating grain growth when sintering according to the mixed proportion of the raw material added
Inhomogeneities (バ ラ つ I), be referred to as crystal boundary energy level (grain circle Quasi) double Schottky barriers inhomogeneities.As a result,
In leakage current when applying voltage, the non linear α values of expression, limitation voltage, the Yi Jishi as rheostatic fundamental characteristics
Big difference is generated in circuit protection ability when increasing surge.
It is explained, about zinc oxide varistor, as the oxygen for seeking the electrical characteristics such as raising surge tolerance, limit voltage ratio
Change zinc rheostat, such as has bismuth system zinc oxide varistor recorded in patent document 1.
Patent document 1：Japanese Unexamined Patent Publication 2006-245111 bulletins
Invention content
Problems to be solved by the invention
For with the rheostat sintered body that zinc oxide (ZnO) is principal component, it is equal to preferably satisfy (1) crystal grain (crystal grain of ZnO)
Gap even, between (2) crystal grain (ZnO) is few, (3) formation crystal boundary energy level (double Schottky barriers) and inhomogeneities are small, (4) crystal grain
(ZnO) the small equal important documents of specific resistance.However, being difficult to obtain ideal rheostat at present, it is difficult to obtain rheostatic fundamental characteristics
All excellent rheostats.
The present invention is completed in view of above-mentioned project, it is intended that providing a kind of as rheostatic basic
In the whole of the leakage current of characteristic, limitation voltage and pulse tolerance, make the rheostatic manufacturer of the Zinc oxide that characteristic improves
Method.
Solution for solving the problem
Make to achieve the above object, solve above-mentioned project a means, the rheostatic system of Zinc oxide of the invention
The method of making is characterized in that having：Prepare to add for main material and in the main material the first additive with zinc oxide (ZnO) and
At rheostat raw material and the second additive of addition as zinc borosilicate system glass made of glass material the step of, make will
The step of mixing material that the rheostat raw material and the glass material mix and oxidation is formed by the mixing material
The step of zinc system rheostatic varistor element (ferritic), first additive and second additive, which contain, makes an addition to institute
State the defined common element in the both sides of rheostat raw material and the glass material.
Such as, which is characterized in that with relative to zinc oxide contained in the rheostat raw material be 0.5 parts by weight~2.5
The mode of parts by weight weighs the glass material, is mixed with the rheostat raw material.In addition, for example, which is characterized in that described total
Contain manganese oxide (MnO with element2), cobalt oxide (CoO), chromium oxide (Cr2O3) in any transition metal.In turn, for example, its
It is characterized in that, the common element contains antimony oxide (Sb2O3) or aluminium oxide (Al2O3).In addition, for example, which is characterized in that institute
It states glass material and contains lead oxide (PbO) or bismuth oxide (Bi2O3) as the additive other than second additive.
As the other means for solving above-mentioned project, which is characterized in that Zinc oxide rheostat of the invention uses
The rheostatic manufacturing method of above-mentioned Zinc oxide is fabricated.Such as, which is characterized in that the rheostatic rheostat of Zinc oxide
Raw material includes the boron oxide (B relative to zinc oxide (ZnO) 100mol% in terms of external percentage (plug-in け)2O3) 0.1~
1.0mol%, cobalt oxide (CoO) 0.5~1.5mol%, manganese oxide (MnO2) 0.5~1.5mol%, antimony oxide (Sb2O3) 0.1~
1.5mol%, chromium oxide (Cr2O3) 0.1~1.0mol%, boric acid (H3BO3) 0.05~1.0mol% and with relative to the change
Hinder the glass material of 0.5~2.5 parts by weight of the zinc oxide (ZnO) in terms of external percentage (plug-in け amounts) contained in device raw material
Material.In addition, for example, which is characterized in that the glass material is borosilicic acid bismuth zinc compound glass.
Invention effect
According to the present invention it is possible to obtain due in leakage current, limitation voltage and the pulse as rheostatic fundamental characteristics
, can be with the inhomogeneities of rejection characteristic while there is excellent characteristic in tolerance, therefore make the circuit as electronic equipment etc.
The Zinc oxide rheostat that the electrical characteristics of defencive function element have been significantly increased.
Description of the drawings
Fig. 1 is the rheostatic manufacture work of oxidation zinc-type Stacked that embodiments of the present invention example is shown with time series
The flow chart of sequence.
Fig. 2 is the figure for the rheostatic cross-section structure of oxidation zinc-type Stacked for showing present embodiment example.
Specific implementation mode
In the following, being described in detail to an embodiment of the invention example with reference to attached drawing and table.First to forming this
The oxidation zinc-type Stacked rheostat of embodiment example is (hereinafter, be also only called zinc oxide varistor or Zinc oxide variable resistance
Device.) each additive (rheostat raw material) of varistor element illustrate.
(a) zinc oxide (ZnO)
The zinc oxide (ZnO) of the main material of zinc oxide varistor as present embodiment example is between existing in crystal structure
Gap (イ ン タ ー ス テ ィ シ ャ Le) Zn+N-type semiconductor ceramics.As the zinc oxide of rheostat, it is usually using grain size
0.4~1.5 μm and uniform particle.
(b) bismuth oxide (Bi2O3)
Bismuth oxide undertakes the substance to form crystal boundary for zinc oxide varistor.Nearby there is eutectic point at 740 DEG C, Gu
It is dissolved in ZnO, forms crystal boundary energy level.The temperature departure due to the catalytic action with other raw materials, but liquid phase is formed from compared with low temperature,
It is added the transport of object, oxygen.In addition, there is the effect for promoting grain growth.If the bismuth oxide of excessive addition, extra Bi phases
It is precipitated in element surface, so that electric field is become uneven due to the inhomogeneities, limitation voltage, pulse characteristic deterioration.In addition, office
Portion generates excessive grain growth, the deterioration in characteristics such as limitation voltage.
(c) antimony oxide (Sb2O3)
Antimony oxide shows grain growth inhibition for zinc oxide varistor.Forming antimony peroxide, pyrochlore, point
Inhibit grain growth during spar, the uniformity of grain growth as a result can be obtained, improves what the uniformity of crystal grain was dominated
Limit voltage characteristic.If in addition, excessive addition, by the specific resistance of obtained pyrochlore, spinel crystal portion and crystal boundary portion
Difference band comes the uneven of electric field, limitation voltage characteristic, pulse tolerance deterioration in characteristics.On the contrary, if additive amount is few, in grain growth
Inhibition in generate inhomogeneities, crystallite dimension generates inhomogeneities, as a result, brings the uneven of electric field, limits voltage
Characteristic, pulse tolerance deterioration in characteristics.
(d) cobalt oxide, manganese oxide, nickel oxide (CoO, MnO2、NiO)
Cobalt, manganese, transition metal element as nickel are solid-solution in ZnO for zinc oxide varistor, form double Schottky gesture
It builds.Since respective valence mumber is different, electronic configuration is different, solid solubility temperature is different, ionic radius is different, in order to form stable double Xiao
Special base potential barrier preferably adds a kind or more.Due to solid solubility limit nor unlimited be dissolved, rational additive amount can be by more
It is secondary to repeat experiment to determine.
If in addition, excessively add these transition metal elements, since unreacted transition metal works as impurity,
There is grain growth inhibition, therefore generate the inhomogeneities of crystal grain, makes limitation voltage, the deterioration of pulse tolerance.If on the contrary, adding
Dosage is few, then due to that can not form adequately double Schottky barriers, electric field concentrates on the defective part of double Schottky barriers, limit
Voltage processed, the deterioration of pulse tolerance.
(e) chromium oxide (Cr2O3)
Chromium oxide has the static stabilization of particle and crystal for zinc oxide varistor.If additive amount is very few, in this way
Stabilization effect it is poor, if on the contrary, excessive addition, works as impurity, bring the inhomogeneities of crystal grain, limitation voltage,
Pulse tolerance deteriorates.
(f) boric acid, silica, germanium oxide (H3BO3、SiO2、GeO2) and compound glass
For zinc oxide varistor, generate subtle effect variation according to the composition of the glass of addition, but it is total for
It, works while the low temperature for contributing to firing temperature as sintering aid, and forms Grain-Boundary Phase.If excessively adding
Glass is then precipitated in large quantities in crystal boundary and element surface, even if being good for leakage current characteristic as a result, the big arteries and veins of input
Thermal diffusion efficiency when rushing reduces, therefore pulse tolerance deteriorates.
In turn, since the abnormal grain growth for generating part that is excessively added of glass limits voltage in addition to pulse tolerance
Characteristic also deteriorates.On the other hand, it if the additive amount of glass is very few, is difficult to be sintered, generates the inhomogeneities of complete characteristic.Separately
Outside, firing temperature high temperature generates Bi2O3、Sb2O3Distillation, the deterioration of rheostatic reliability properties.
(g) for element of volume (Al2O3、B2O3)
For element of volume for zinc oxide varistor, due to promoting the low resistance of the ZnO as main material, having makes
The effect that the Joule heat of big pulse into fashionable generation is promptly spread improves limitation voltage, pulse tolerance.If excessively adding
For element of volume, then due to forming spinelle between ZnO, occur the such sintering facilitation effect of abnormal grain growth and
Grain growth hinders effect, and there is sintering to hinder the dual character of effect.In short, limitation voltage, the deterioration of pulse tolerance.Another party
Face can not show these effects if the additive amount for element of volume is very few.But since part generates low resistance,
Contribute to the inhomogeneities for leading to characteristic.
Then, the rheostatic manufacturing method of oxidation zinc-type Stacked of an embodiment of the invention example is said
It is bright.Fig. 1 is the flow chart for the rheostatic manufacturing process of oxidation zinc-type Stacked that present embodiment example is shown with time series.
In addition, cuing open Fig. 2 shows the oxidation zinc-type Stacked by the present embodiment example manufactured by process shown in FIG. 1 is rheostatic
One example of face structure.
In the step S11 of Fig. 1, based on table 1 it is equal shown in composition blending oxidation zinc-type Stacked substantially it is rheostatic
Raw material powder.Here, for example, weighing the rheostat raw material of 3 μm or so of intermediate value average grain diameter.In addition, according to unit rheostat electricity
Pressure addition grain growth inhibiting substances.It is explained, adds various glass as sintering aid, but to the composition of the glass material
It is carried out with additive amount aftermentioned.
In step s 12, the rheostat raw material weighed in above-mentioned step S11 is crushed into particle adjustment.For example,
It is crushed 24 hours using the alumina medium of 10mm φ with ball mill, neat particle.In following step S13, in vacation burning
State the raw material powder adjusted through pulverized particles.Here, carrying out heat treatment adjustment reactivity, grain size at 900 DEG C.Then, exist
In step S14, by the raw material powder after false burn again with ball mill etc. crushes and neat particle.
In step S15, slurry is made.For example, the polyvinyl alcohol contracting fourth of the degree of polymerization 300 is added in above-mentioned mixture
Aldehyde (PVB), phthalic acid ester system plasticizer, polycarboxylic-acid dispersant, the release materials of PEG#600, the dilution of ethanol/toluene system
Solvent makes slurry.Then, in step s 16, sheet material is made by the slurry made in step S15.Here, formed a film with scraper,
For example, making 10~100 μm or so of green sheet.It is explained, thus it is possible to vary the thickness of green sheet makes low pressure, middle pressure, height
The rheostat of pressure.
In following step S17, internal electrode pattern is printed using electrode pastes such as such as Pt, Pd, Ag/Pd.For example,
As shown in rheostatic cross-section structure, that is, Fig. 2, the number of plies of internal electrode 3 is overlapped 6 layers, is thermally compressed with hot pressing etc., and layer
It is folded.It is cut in following step S18.As cutting, according to the product size (such as 3216 sizes) of regulation to layer
Storied sheet material is cut.
In step S19, the laminated body after cutting is kept for 10 hours etc. at such as 500 DEG C of temperature, carries out debinding
Agent.In step S21 below, it is burnt into 5 hours at such as 950~1300 DEG C, in following step S22, at 700 DEG C
Under sintered body is made annealing treatment.In turn, it in step S23, pastes to form terminal electrode (figure with such as Ag pastes or Ag/Pd
2 external electrode 5a, 5b), it is sintered at the specified temperature.
In step s 24, to external electrode 5a, 5b formed in step S23 by electrolytic coating with such as Ni layers, Sn
The sequence of layer implements plating.Then, in following step S25, the electrical characteristics such as varistor voltage, leakage current are examined
It surveys, completes the oxidation zinc-type Stacked rheostat as final products.
Then, the oxidation zinc-type Stacked rheostat of present embodiment example is described in detail.Make here, making
For the rheostat raw material formed substantially the oxidation zinc-type Stacked rheostatic sample different with its additive amount, which is surveyed
It is set for 3 characteristics (aftermentioned leakage current, limitation voltage, pulse tolerance) for rheostatic fundamental characteristics.
The rheostatic each sample made for the rheostatic manufacturing method of Zinc oxide by present embodiment example
Assessment item (varistor properties) and its assay method are as described below.
(A) leakage current
So-called leakage current is generally represented in the electric current for applying and circulating when maximum allowable circuit voltage.In rheostatic electric leakage
In the evaluation of stream, rheostat using when the voltage environment that can be applied continuously under, observation generates how many current loss.Leakage current
It is more few the more preferred, if leakage current is big, degradation failure is easy tod produce, therefore, the small rheostat of leakage current is as the long-life
From the aspect of it is also excellent.
In order to be relatively low by drain current suppressing, the homogenieity that double Schottky barriers are formed by crystal boundary is critically important.Simultaneously
If the liquid phase that crystal boundary can be obtained is brilliant, high resistance, therefore it is preferred that.In the oxidation zinc-type Stacked variable resistance to present embodiment example
In the evaluation of the leakage current of device, by read circulate 1mA electric current when generate voltage by varistor voltage is measured,
For leakage current, the current value to circulate when applying the voltage of 0.9 times (Hang) of harsh condition, that is, varistor voltage is carried out
It measures.
(B) voltage is limited
As described above, so-called varistor voltage, for the voltage V occurred in the electric current for the 1mA that circulates1mA, in contrast, institute
Rheostatic limitation voltage is called, for varistor voltage when electric current larger as 1A, 2A, 10A or so that circulates.Rheostat with
Part to be protected is in parallel, and the high voltage portion of the abnormally high-voltage to being generated by certain reasons such as ESD protects electricity due to cut-out
Road.For voltage is suppressed to the limitation voltage of lower function by display in this wise, value is lower, display circuit voltage,
The load for being applied to protection part is more reduced.
In order to occur limitation voltage being suppressed to lower characteristic in rheostat, the ZnO crystal grain for being sintered body is needed
The homogenization of size.The electric field of the load voltage applied as a result, is dispersed in rheostat entirety, can be suppressed to limitation voltage
It is relatively low.The rheostatic limitation voltage of oxidation zinc-type Stacked of present embodiment example is the electricity generated when applying the electric current of 2A
The measurement result of pressure.Be explained, in evaluation as follows, as generate voltage reading and varistor voltage ratio,
That is limit voltage ratio (V2A/V1mA) and shown.
(C) pulse tolerance
So-called pulse tolerance indicates lightning surge, vehicle-mounted motor surge, high voltage/heavy current pulse as surge of lighting a fire
Into fashionable tolerance.In order to improve pulse tolerance, need as pair in both the rheostatic crystal grain constituted substantially and crystal boundary
It answers.First, crystal grain preferably seeks low resistance, and the high current inputted is become the heat of Joule heat rapidly to volume in crystal boundary
Whole diffusion, prevents the destruction of 1 crystal boundary.
On the other hand, for crystal boundary, make the high uniformity of double Schottky barriers/decentralized, not for inflow
High current is incurred destruction and is important.Zinc oxide varistor with excellent electrical characteristics in order to obtain, needs to consider above-mentioned
Mechanism whole correspondences.In the oxidation zinc-type Stacked rheostat of present embodiment example, as pulse tolerance (2ms
Waveform), the energy (J) generated when applying the pulse of 2ms waveforms is measured.This display varistor voltage change rate ±
End-point energy within 10%.
Then, for the rheostatic each sample of oxidation zinc-type Stacked of present embodiment example, to its material composition, spy
The evaluation result etc. of property is concretely demonstrated.Here, in order to be found that the oxidation zinc-type laminates with excellent electrical characteristics
The rheostatic best material composition of formula, the effect based on each additive shown in above-mentioned (a)~(g) have carried out various experiments.
Then, as the oxidation rheostatic evaluation of zinc-type Stacked, the additive amount to (1) various glass and glass form respectively
Effect that additive amount and the glass composition of the effect, (2) various transition metal elements brought are brought, (3) other elements add
Effect is added to be evaluated.
(1) effect and its evaluation that the additive amount of various glass and glass composition are brought
Due to being only unable to get varistor properties with zinc oxide and glass, as the rheostat raw material formed substantially
The middle various glass materials of addition are evaluated.Table 1 is shown as the oxidation zinc-type Stacked rheostat of present embodiment example
Basic composition (being known as basic composition 1) rheostat raw material (element material) and its additive amount.It is explained, in table 1,
The additive amount of element other than ZnO is the external percentage additive amount relative to ZnO 100mol%.
Table 1
Table 2 is for aoxidizing the rheostatic glass material of zinc-type Stacked, here, the glass material of 4 kinds of compositions of research
(glass A~D).Specifically, the glass material formed to 4 kinds below is studied：
(i) glass A：SiO2Glass
(ii) glass B：Lead borosilicate glass (B2O3-SiO2System)
(iii) glass C：Borosilicic acid bismuth glass (B2O3-SiO2-Bi2O3System)
(iv) glass D：Zinc borosilicate glass (B2O3-SiO2- ZnO systems)
Table 2
3~table of table 6 is the rheostatic varistor properties assessment item of oxidation zinc-type Stacked of present embodiment example
Evaluation result.The additive amount of glass shown in each table is relative to contained in rheostat raw material (being formed substantially shown in table 1)
The weight ratio of ZnO is the result for the experiment that evaluating characteristics project has been carried out for the additive amount of 0.3wt%~2.9wt%.
Table 3
Table 4
Table 5
Table 6
The evaluation result of the varistor properties assessment item shown in 3~table of table 6 it is found that compared with glass A, B, C, for
Glass D, in limit voltage ratio, characteristic improves, and other projects can also be obtained with the result balanced.
It is for the sintered grain to the ZnO as rheostatic main material that glass material is added in rheostat raw material
Diameter (crystallite dimension) is homogenized.Limitation voltage characteristic, the resistance to flow characteristic of surge can be improved by the homogenization of particle.And
And be found that by above-mentioned experiment, in order to make ZnO crystal grain equably grow, the glass (above-mentioned glass D) based on ZnO is
Suitable.
That is, due to the reactivity degree height in silica glass etc., the reaction of ZnO accelerates, and particle is made to produce
Raw inhomogeneities.On the other hand, for the glass of zno-based due to being rich in ZnO, the reaction of ZnO is slow, has and inhibits grain growth
The effect of inhomogeneities.In addition, in order to carry out vitrifying to the ZnO of the main material as glass material, SiO is added2、B2O3Deng
Borosilicic acid system glass ingredient.It is explained, Na contained in glass A~D2O、K2O, CaO is to reduce the fusing point of glass material
And add, according to SiO2Amount and adjust.In SiO2Amount it is few in the case of, need not also add sometimes.
Here, to study as in glass material additive, in the relationship of element contained in rheostat raw material
Result for further increasing preferred glass material for characteristic is illustrated.
<Lead oxide, bismuth oxide (PbO, Bi2O3)>
PbO, Bi as the additive in glass material2O3, the crystal boundary as ZnO can be inhibited to constitute substance and include
Bi in rheostat raw material2O3Distribution, concentration difference, so that it is coexisted.In addition, these additives cause the mobility of glass
It influences.By PbO, Bi2O3It is added in rheostat raw material, while is also added in glass material.Furthermore it is possible to by PbO,
Bi2O3A part carry out vitrifying after be added to and inhibit excessive reaction in rheostat raw material.It is then selected for unleaded requirement
Select Bi2O3。
It is explained, the vitrifying in so-called present embodiment example, refers to that material by based on and additive are preferred
The state that (such as 1000 DEG C or more) are heat-treated more than the fusing point of glass.Thus, it is possible to inhibit the anti-of each additive
Ying Xing.
<Antimony oxide, aluminium oxide (Sb2O3、Al2O3)>
Sb as the additive in glass material2O3、Al2O3Control the grain growth of ZnO.It is added to rheostat
In raw material, while being also added to glass material.Furthermore it is possible to by being added to rheostat raw material after carrying out vitrifying to a part
In make it and the pre-added Sb of institute in rheostat raw material2O3It is compatible to coexist.It is explained, Sb2O3、Al2O3It is equivalent to this Shen
The common element described in claim please.
<Manganese oxide, cobalt oxide, chromium oxide (MnO2、CoO、Cr2O3)>
MnO as the additive in glass material2、CoO、Cr2O3Crystal boundary in order to control, the transition metal being dissolved to ZnO
Group, for the particularly preferred element of reactivity.All or any one is added to rheostat raw material and glass material by these additives
In both sides.Furthermore it is possible to by the way that a part is carried out vitrifying and is added to inhibit excessive reaction in rheostat raw material, together
The performance of whole zinc oxide.It is explained, MnO2、CoO、Cr2O3It is equivalent in the common element described in claims hereof
Contained transition metal.
(2) effect and its evaluation that the additive amount of various transition metal elements and glass composition are brought
Due to being only unable to get varistor properties with zinc oxide and transition metal, as the rheostat formed substantially
Various transition metal elements are added in raw material and are evaluated.Table 7 is shown as the oxidation rheostatic base of zinc-type Stacked
The rheostat raw material (element material) of this composition 2 and its additive amount.It is explained, in table 7, element other than ZnO adds
Dosage is the external percentage additive amount relative to ZnO 100mol%.
Table 7
Here, adding element below in above-mentioned basic composition 2, effect test is carried out.
(i) only cobalt oxide (CoO)
(ii) only manganese oxide (MnO2)
(iii) cobalt oxide (CoO) and manganese oxide (MnO2) it is compound
The result of study for the effect that the addition of above-mentioned transition metal element is brought is shown in 8~table of table 12.It is explained,
In any one of 8~table of table 12, the additive amount of transition metal element is the external percentage relative to ZnO 100mol%.
Table 8 shows the effect that cobalt oxide (CoO) is added in basic composition 2.It is confirmed, is being added to by evaluation result
In the case of CoO, in limit voltage ratio, pulse tolerance, especially in the range that the additive amount of CoO is 0.5~1.5mol%
The result that can be got well in (in table, with the range of two-wire encirclement).
Table 8
Table 9 shows to be added to manganese oxide (MnO in basic composition 22) effect.It is confirmed, is being added by evaluation result
Manganese oxide (MnO2) in the case of, in limit voltage ratio, pulse tolerance, especially in the range (table of 0.5~1.5mol%
In, with two-wire surround range) in pass through add MnO2The result that can be got well.
Table 9
10~table of table 12 shows to be mixed with cobalt oxide (CoO) and manganese oxide (MnO in basic composition 22) when effect.
This, according to their additive amount carried out each evaluation (leakage current, limitation voltage, pulse tolerance measurement).That is, table 10 shows to close
In the result of study of leakage current, table 11 shows the result of study about limitation voltage, and table 12 is shown about pulse tolerance
Result of study.It is explained, in any one of 10~table of table 12, cobalt oxide (CoO) and manganese oxide (MnO2) additive amount it is equal
For the external percentage additive amount relative to ZnO 100mol%.
10 leakage current of table
Table 11 limits voltage
12 pulse tolerance of table
Result is distinguished shown in 10~table of table 12, by cobalt oxide (CoO) 0.5~1.5mol%, manganese oxide
(MnO2) 0.5~1.5mol% range (in table, surrounded with two-wire range) in during combination is added to and forms 2 substantially simultaneously,
Excellent characteristic can be obtained in leakage current, limitation voltage, the resistance to flow characteristic of pulse.
(3) additive effect of other elements and its evaluation
Here, to being added to crystal boundary forming material (bismuth oxide (Bi in as the rheostat raw material formed substantially2O3))、
Hinder grain growth substance (antimony oxide (Sb2O3), chromium oxide (Cr2O3)), for element of volume (boric acid (H3BO3), aluminium oxide
(Al2O3)) as other elements when effect and its additive amount studied.
(3-1) bismuth oxide (Bi2O3) addition and its effect
Due to being only unable to get varistor properties with zinc oxide and bismuth oxide, to shown in table 13, as basic
It is added to oxidation bismuth element (Bi in the rheostat raw material (being known as basic composition 3) of composition2O3) when evaluating characteristics project carry out
Experiment.It is explained, in table 13, the additive amount of the element other than ZnO is the external percentage relative to ZnO 100mol%
Additive amount.
Table 13
Oxidation bismuth element (Bi will be added in the basic composition 3 of table 132O3) when evaluating characteristics result shown in table 14.
By evaluation result it is found that by bismuth oxide (Bi2O3) 0.1~1.0mol% range (in table, with two-wire surround range) in
It is added, the good and excellent characteristic of balance can be obtained in leakage current, limitation voltage, the resistance to flow characteristic of pulse.
Table 14
(3-2) antimony oxide (Sb2O3) and chromium oxide (Cr2O3) addition and its effect
Due to being only unable to get varistor properties with zinc oxide and antimony oxide, chromium oxide, shown in table 15, make
For the middle combination addition antimony oxide (Sb of rheostat raw material (being known as basic composition 4) formed substantially2O3) and chromium oxide (Cr2O3) make
To hinder grain growth substance, its effect is evaluated.It is explained, in table 15, the additive amount of the element other than ZnO is
External percentage additive amount relative to ZnO 100mol%.
Table 15
16~table of table 18 shows the combination addition antimony oxide (Sb in basic composition 42O3) and chromium oxide (Cr2O3) when effect
Fruit.That is, table 16 shows the result of study about leakage current, table 17 shows the result of study about limitation voltage, and table 18 shows
Go out the result of study about pulse tolerance.It is explained, the antimony oxide (Sb in 16~table of table 182O3) and chromium oxide (Cr2O3) add
Dosage is the external percentage additive amount relative to ZnO 100mol%.
16 leakage current of table
Table 17 limits voltage
18 pulse tolerance of table
The evaluation result shown in 16~table of table 18 in whole characteristics it is found that show the group of the additive amount of excellent specific property
It is combined into antimony oxide (Sb2O3) 0.1~1.5mol%, chromium oxide (Cr2O3) 0.1~1.0mol% range (in table, with two-wire packet
The range enclosed), in this range, for leakage current, limitation voltage, pulse tolerance, excellent characteristic can be obtained.
The addition and its effect of (3-3) for element of volume
Due to only with zinc oxide and being unable to get varistor properties for element of volume, as shown in table 19, as basic
Addition boric acid (H in the rheostat raw material (being known as basic composition 5) of composition3BO3), aluminium oxide (Al2O3) be used as element of volume, it is right
Characteristic is evaluated.It is explained, in table 19, the additive amount of the element other than ZnO is relative to ZnO 100mol%'s
External percentage additive amount.
Table 19
20~table of table 22 shows to be added to boric acid (H in basic composition 53BO3), aluminium oxide (Al2O3) when effect.Tool
For body, table 20 is the result of study about leakage current, and table 21 is the result of study about limitation voltage, and table 22 is about pulse
The result of study of tolerance.It is explained, the boric acid (H in 20~table of table 223BO3), aluminium oxide (Al2O3) additive amount indicate phase
For the external percentage additive amount of ZnO 100mol%.
20 leakage current of table
Table 21 limits voltage
22 pulse tolerance of table
The result shown in 20~table of table 22 is it is found that show the addition of excellent specific property in whole characteristics is combined as table
Boric acid (H in the range of 20~table 22 surrounded with two-wire3BO3) 0.1~1.0mol%, aluminium oxide (Al2O3) 0.001~
Excellent spy can be obtained in leakage current, limitation voltage and pulse tolerance with the additive amount of the range in the range of 0.005mol%
Property.
On the other hand, it confirms, addition boric acid (H3BO3) 0.1~1.0mol% be aluminium oxide (Al2O3) additive effect
Premise.In turn, it confirms, even if not adding aluminium oxide (Al2O3), by adding boric acid (H3BO3) 0.1~1.0mol%
Excellent leakage current and limitation voltage characteristic can be obtained.
By above research evaluation result it is found that the oxidation zinc-type Stacked rheostat of present embodiment example can be limited
Best composition.Table 23 is the group of the rheostatic most preferred rheostat raw material of oxidation zinc-type Stacked of present embodiment example
At table 24 is the composition of best glass material.Glass material in table 23 is preferably borosilicic acid bismuth zinc compound glass, and table 24 shows
Go out its specific composition.
It is explained, the additive amount (not including glass material) of the raw material in table 23 is relative to the outer of ZnO 100mol%
Portion percentage mol% is shown, for the additive amount of glass material, for the outside hundred relative to ZnO contained in rheostat raw material
Divide proportion.
Table 23
| Masurium | Additive amount (mol%) |
| ZnO | 100 |
| B2O3 | 0.1~1.0 |
| CoO | 0.5~1.5 |
| MnO2 | 0.5~1.5 |
| Sb2O3 | 0.1~1.5 |
| Cr2O3 | 0.1~1.0 |
| H3BO3 | 0.05~1.0 |
| Glass material | 0.5~2.5 parts by weight/ZnO |
Table 24
| Masurium | Additive amount (wt%) |
| B2O3 | 15~40 |
| SiO2 | 5~25 |
| ZnO | 50~75 |
| PbO、Bi2O3At least either | 1~10 |
| Sb2O3、Al2O3At least either | 0.1~1.5 |
| MnO2、CoO、Cr2O3It is any more than | With monomer or it is calculated as 1.0~5.0 |
Oxidation zinc-type laminates are made by using the varistor element that material shown in table 23 and table 24 forms as a result,
Formula rheostat, it is hereby achieved that the zinc oxide varistor with excellent varistor properties.More specifically, it is known that available
2 in leakage current (μ A) below, in limit voltage ratio 1.70 (V2A/V1mA) variable resistance following, 1 in pulse tolerance more than (J)
Device characteristic.
As described above, in the rheostatic manufacturing method of Zinc oxide of present embodiment example, by using following structure
At：It rheostat raw material made of the first additive and is added to using will be added in the zinc oxide (ZnO) as main material
The mixing material that the glass material of zinc borosilicate system glass mixes made of second additive forms Zinc oxide rheostat
Varistor element, these first additives and the second additive, which contain, to be made an addition in the both sides of rheostat raw material and glass material
Common element, it is hereby achieved that as rheostatic fundamental characteristics leakage current, limitation voltage and pulse tolerance it is complete
The Zinc oxide rheostat for improving characteristic in portion.
I.e., it was found that the rule added in the defined additive and its additive amount that are added in rheostat raw material, glass material
The common element added in fixed additive and its additive amount and the both sides of rheostat raw material and glass material is with them
Basis, limits as the rheostatic best composition of Zinc oxide, and varistor element is made with the material ratio of components, it is possible thereby to
The Zinc oxide rheostat with the excellent electrical characteristics of circuit protection function is made.
Claims (5)
1. a kind of rheostatic manufacturing method of Zinc oxide, which is characterized in that have：Prepare with zinc oxide (ZnO) be main material,
Add rheostat raw material made of the first additive in the main material, and as zinc borosilicate system glass, addition second adds
The step of adding glass material made of object,
Make the rheostat raw material and the glass material are mixed mixing material the step of and
The step of rheostatic varistor element of Zinc oxide is formed by the mixing material,
First additive and second additive contain pair for making an addition to the rheostat raw material and the glass material
Defined common element in side,
The common element is manganese oxide (MnO2), cobalt oxide (CoO), chromium oxide (Cr2O3) in any.
2. the rheostatic manufacturing method of Zinc oxide according to claim 1, which is characterized in that with relative to the variable resistance
Zinc oxide contained in device raw material is that the mode of the parts by weight of 0.5 parts by weight~2.5 weighs the glass material, with the rheostat
Raw material mixes.
3. the rheostatic manufacturing method of Zinc oxide according to claim 1 or 2, which is characterized in that the common element
Additive amount in the glass material is 1.0~5.0wt%.
4. the rheostatic manufacturing method of Zinc oxide according to claim 1 or 2, which is characterized in that the common element
Contain antimony oxide (Sb2O3) or aluminium oxide (Al2O3)。
5. the rheostatic manufacturing method of Zinc oxide according to claim 1, which is characterized in that the glass material contains
Lead oxide (PbO) or bismuth oxide (Bi2O3) as the additive other than second additive.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014035311A JP6355360B2 (en) | 2014-02-26 | 2014-02-26 | Manufacturing method of zinc oxide varistor |
| JP2014-035311 | 2014-02-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104867638A CN104867638A (en) | 2015-08-26 |
| CN104867638B true CN104867638B (en) | 2018-09-14 |
Family
ID=53913416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510087897.0A Active CN104867638B (en) | 2014-02-26 | 2015-02-26 | The rheostatic manufacturing method of Zinc oxide |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6355360B2 (en) |
| KR (2) | KR101817831B1 (en) |
| CN (1) | CN104867638B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI820611B (en) * | 2022-02-23 | 2023-11-01 | 國立成功大學 | Zno-based varistor material, the manufacturing method of the same, and the zno-based varistor applying the same |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165125A (en) * | 1995-08-31 | 1997-11-19 | 松下电器产业株式会社 | Zinc oxide ceramics composition and its manufacture method and zinc oxide nonlinear resistance |
| CN101447265A (en) * | 2007-11-27 | 2009-06-03 | 兴亚株式会社 | Method for fabricating zinc oxide multilayer chip piezoresistor |
| EP2458597A1 (en) * | 2010-11-26 | 2012-05-30 | SFI Electronics Technology Inc. | Process for producing multilayer chip zinc oxide varistor containing pure silver internal electrodes and firing at ultralow temperature |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5512624U (en) * | 1978-07-07 | 1980-01-26 | ||
| JPS57159001A (en) * | 1981-03-26 | 1982-10-01 | Meidensha Electric Mfg Co Ltd | Voltage nonlinear resistor |
| JPS57166007A (en) * | 1981-04-06 | 1982-10-13 | Meidensha Electric Mfg Co Ltd | Voltage nonlinear resistor |
| JPS5994401A (en) * | 1982-11-19 | 1984-05-31 | 松下電器産業株式会社 | Method of producing voltage nonlinear resistor |
| JPS60170208A (en) * | 1984-02-15 | 1985-09-03 | 株式会社明電舎 | Voltage nonlinear resistor |
| JP3039224B2 (en) * | 1993-09-29 | 2000-05-08 | 松下電器産業株式会社 | Varistor manufacturing method |
| JPH07220906A (en) * | 1994-02-02 | 1995-08-18 | Murata Mfg Co Ltd | Multifunction element |
| JP2006245111A (en) | 2005-03-01 | 2006-09-14 | Koa Corp | Bismuth-based zinc oxide varistor |
| KR20120057533A (en) * | 2010-11-26 | 2012-06-05 | 에스에프아이 일렉트로닉스 테크날러지 인코어퍼레이티드 | Process for producing multilayer chip zinc oxide varistor containing pure silver internal electrodes and firing at ultralow temperature |
-
2014
- 2014-02-26 JP JP2014035311A patent/JP6355360B2/en active Active
-
2015
- 2015-02-25 KR KR1020150026775A patent/KR101817831B1/en active IP Right Grant
- 2015-02-26 CN CN201510087897.0A patent/CN104867638B/en active Active
-
2018
- 2018-01-04 KR KR1020180001112A patent/KR101889678B1/en active IP Right Grant
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1165125A (en) * | 1995-08-31 | 1997-11-19 | 松下电器产业株式会社 | Zinc oxide ceramics composition and its manufacture method and zinc oxide nonlinear resistance |
| CN101447265A (en) * | 2007-11-27 | 2009-06-03 | 兴亚株式会社 | Method for fabricating zinc oxide multilayer chip piezoresistor |
| EP2458597A1 (en) * | 2010-11-26 | 2012-05-30 | SFI Electronics Technology Inc. | Process for producing multilayer chip zinc oxide varistor containing pure silver internal electrodes and firing at ultralow temperature |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20150101425A (en) | 2015-09-03 |
| JP6355360B2 (en) | 2018-07-11 |
| JP2015162499A (en) | 2015-09-07 |
| KR20180006624A (en) | 2018-01-18 |
| CN104867638A (en) | 2015-08-26 |
| KR101817831B1 (en) | 2018-01-11 |
| KR101889678B1 (en) | 2018-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8217751B2 (en) | Electronic device and method | |
| EP2426678B1 (en) | Zinc-oxide surge arrester for high-temperature operation | |
| CN104867638B (en) | The rheostatic manufacturing method of Zinc oxide | |
| CN101447265A (en) | Method for fabricating zinc oxide multilayer chip piezoresistor | |
| JP4690123B2 (en) | Method for producing zinc oxide laminated varistor | |
| US9601244B2 (en) | Zinc oxide based varistor and fabrication method | |
| EP0098993A1 (en) | Low voltage ceramic varistor | |
| JP6387969B2 (en) | Sintered body for varistor, multilayer substrate using the same, and manufacturing method thereof | |
| WO2019204430A1 (en) | Varistor for high temperature applications | |
| JP4184172B2 (en) | Voltage nonlinear resistor ceramic composition, electronic component and multilayer chip varistor | |
| JP2008100856A (en) | Method for producing zinc oxide laminated chip varistor | |
| JP5301853B2 (en) | Zinc oxide chip varistor | |
| JP5282332B2 (en) | Manufacturing method of zinc oxide laminated chip varistor | |
| JP5674317B2 (en) | Zinc oxide varistor and method for producing the same | |
| KR102666011B1 (en) | ZnO-BASED VARISTOR COMPOSITION AND MANUFACTURING METHOD AND VARISTOR THEREOF | |
| JP2006245111A (en) | Bismuth-based zinc oxide varistor | |
| KR102615494B1 (en) | ZnO-BASED VARISTOR COMPOSITION AND VARISTOR INCLUDING THE SAME AND MANUFACTURING METHOD THEREOF | |
| TWI447750B (en) | Chip varistor containing rare-earth oxide sintered at lower temperature and method of making the same | |
| JP2546726B2 (en) | Voltage nonlinear resistor | |
| JP2625178B2 (en) | Varistor manufacturing method | |
| TW201813943A (en) | Antimony-free varistor composition and laminated varistor having excellent varistor characteristics and low manufacturing costs | |
| KR20160022668A (en) | Zinc oxide baristor for overvoltage protection and manufacturing method the same | |
| JP2628389B2 (en) | Voltage non-linear resistor | |
| KR100676724B1 (en) | Zinc oxide composition for arrester of power transmission and power transformation | |
| JPS6115303A (en) | Method of producing oxide voltage nonlinear resistor |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information |
Inventor after: Gomi Yoji Inventor after: God also Qi Inventor before: Gomi Yoji |
|
| COR | Change of bibliographic data | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |