CN104867638A - Manufacturing Method Of Zinc Oxide Rheostat - Google Patents
Manufacturing Method Of Zinc Oxide Rheostat Download PDFInfo
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- CN104867638A CN104867638A CN201510087897.0A CN201510087897A CN104867638A CN 104867638 A CN104867638 A CN 104867638A CN 201510087897 A CN201510087897 A CN 201510087897A CN 104867638 A CN104867638 A CN 104867638A
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- 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
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- H—ELECTRICITY
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Abstract
The present invention provides a manufacturing method of a zinc oxide rheostat. A rheostat element is made of the mixed materials formed by mixing a rheostat raw material taking the zinc oxide as a main raw material and adding a first additive in the main raw material, and a glass material as a zinc borosilicate glass and adding a second additive. At the moment, the first additive and the second additive contain the specified common elements added in the rheostat raw material and the glass material, so that the zinc oxide rheostat of excellent electrical characteristics is manufactured by the rheostat element.
Description
Technical field
The present invention relates to the rheostatic manufacture method of Zinc oxide used in the removing of a kind of such as power supply noise, lightning induction noise etc.
Background technology
Along with high frequency, the high capacity of electric/electronic device; as for proterctive equipment circuit in such as mobile phone, the automobile etc. by power supply noise, various surge, pulsive noise, static discharge (ESD) impact or guarantee the countermeasure of stability of work, reply that noise specify, employ and be oxidized zinc-type Stacked rheostat.As its representational application examples, can enumerate: as protection semiconductor by mobile electronic device, vehicle electronic device get rid of that load is surged, surge of lighting a fire, lightning surge, ESD, switching surges the utilization of semiconductor protective elements of impact.
As the basic composition of zinc oxide varistor, add the Bi promoting grain growth
2o
3, suppress the Sb of grain growth
2o
3.In addition, various glass etc. are added as sintering aid.The electrical characteristics that rheostat makes by the combination of additive, its addition to obtain, reliability change significantly.Such as, produce the inhomogeneities (バ ラ つ I) of grain growth when sintering according to the mixed proportion of added raw material, be called as the inhomogeneities of two Schottky barriers of crystal boundary energy level (grain circle Quasi position).Its result, produces large difference in the leakage current when the applying voltage as rheostatic fundamental characteristics, circuit protection ability when representing non linear α value, deboost and apply large surge.
Being explained, about zinc oxide varistor, as seeking the zinc oxide varistor improving the electrical characteristics such as surge tolerance, limit voltage ratio, such as, having bismuth system zinc oxide varistor described in patent documentation 1.
Patent documentation 1: Japanese Unexamined Patent Publication 2006-245111 publication
Summary of the invention
Invent problem to be solved
For the rheostat sintered body being principal component with zinc oxide (ZnO), preferably meet that the space of (1) crystal grain (crystal grain of ZnO) evenly, between (2) crystal grain (ZnO) is few, (3) form crystal boundary energy level (two Schottky barrier) and the important document such as inhomogeneities is little, the ratio resistance of (4) crystal grain (ZnO) is little.But, be difficult at present obtain desirable rheostat, be difficult to obtain all excellent rheostat of rheostatic fundamental characteristics.
The present invention completes in view of above-mentioned problem, its object is to, provide a kind of as the leakage current of rheostatic fundamental characteristics, deboost and pulse tolerance whole in, the rheostatic manufacture method of the Zinc oxide that characteristic is improve.
For solving the scheme of problem
Do for achieving the above object, solve means of above-mentioned problem, the feature of the rheostatic manufacture method of Zinc oxide of the present invention is, possess: prepare in this main material, to add the step of the rheostat raw material of the first additive and the glass material as interpolation second additive of zinc borosilicate system glass using zinc oxide (ZnO) for main material, make the step of the composite material described rheostat raw material and described glass material mixed, with the step being formed the rheostatic varistor element of Zinc oxide (ferritic) by described composite material, described first additive and described second additive contain the common element of the regulation in the both sides making an addition to described rheostat raw material and described glass material.
Such as, it is characterized in that, weigh described glass material in the mode being 0.5 weight portion ~ 2.5 weight portion relative to zinc oxide contained in described rheostat raw material, mix with described rheostat raw material.In addition, such as, it is characterized in that, described common element contains manganese oxide (MnO
2), cobalt oxide (CoO), chromium oxide (Cr
2o
3) in arbitrary transition metal.And then such as, it is characterized in that, described common element contains antimony oxide (Sb
2o
3) or aluminium oxide (Al
2o
3).In addition, such as, it is characterized in that, described glass material contains lead oxide (PbO) or bismuth oxide (Bi
2o
3) as the additive beyond described second additive.
As other the means solving above-mentioned problem, it is characterized in that, Zinc oxide rheostat of the present invention uses the rheostatic manufacture method manufacture of above-mentioned Zinc oxide to form.Such as, it is characterized in that, Zinc oxide rheostatic rheostat raw material packet contains relative to zinc oxide (ZnO) 100mol% in the boron oxide (B of outside percentage (plug-in け)
2o
3) 0.1 ~ 1.0mol%, cobalt oxide (CoO) 0.5 ~ 1.5mol%, manganese oxide (MnO
2) 0.5 ~ 1.5mol%, antimony oxide (Sb
2o
3) 0.1 ~ 1.5mol%, chromium oxide (Cr
2o
3) 0.1 ~ 1.0mol%, boric acid (H
3bO
3) 0.05 ~ 1.0mol% and in relative to zinc oxide (ZnO) contained in described rheostat raw material with the glass material of 0.5 ~ 2.5 weight portion of outside percentage (plug-in け amount).In addition, such as, it is characterized in that, described glass material is borosilicic acid bismuth zinc compound glass.
Invention effect
According to the present invention; can obtain due to while there is excellent characteristic in as the leakage current of rheostatic fundamental characteristics, deboost and pulse tolerance; can the inhomogeneities of suppression characteristic, therefore make the Zinc oxide rheostat that the electrical characteristics as the circuit protection function element of electronic equipment etc. improve significantly.
Accompanying drawing explanation
Fig. 1 is the flow chart of the rheostatic manufacturing process of oxidation zinc-type Stacked that embodiments of the present invention example is shown with time series.
Fig. 2 is the figure of the rheostatic cross-section structure of oxidation zinc-type Stacked that present embodiment example is shown.
Embodiment
Below, with reference to accompanying drawing and table, an embodiment of the invention example is described in detail.First (below, zinc oxide varistor or Zinc oxide rheostat are also only called to the oxidation zinc-type Stacked rheostat forming present embodiment example.) each additive (rheostat raw material) of varistor element be described.
(a) zinc oxide (ZnO)
As the zinc oxide (ZnO) of the main material of the zinc oxide varistor of present embodiment example for there is gap (イ Application タ ー ス テ ィ シ ャ Le) Zn in crystal structure
+n-type semiconductor pottery.As the zinc oxide of rheostat, particle diameter is usually used to be 0.4 ~ 1.5 μm and uniform particle.
(b) bismuth oxide (Bi
2o
3)
Bismuth oxide forms the material of crystal boundary for zinc oxide varistor for bearing.Near 740 DEG C, there is eutectic point, be solid-solution in ZnO, form crystal boundary energy level.The temperature departure due to the catalytic action with other raw material, but form liquid phase from comparatively low temperature, also carry out the transport of additive, oxygen.In addition, the effect promoting grain growth is had.If add excessive bismuth oxide, then unnecessary Bi phase is separated out at element surface, makes electric field become uneven due to this inhomogeneities, the deterioration of deboost, pulse characteristic.In addition, local produces excessive grain growth, the deterioration in characteristics such as deboost.
(c) antimony oxide (Sb
2o
3)
Antimony oxide is for zinc oxide varistor display grain growth inhibition.In the process forming antimony peroxide, pyrochlore, spinelle, suppress grain growth, result can obtain the uniformity of grain growth, the deboost characteristic that the uniformity improving crystal grain is arranged.In addition, if add excessive, then the uneven of electric field is carried out, deboost characteristic, pulse tolerance deterioration in characteristics by the difference band of the ratio resistance in the pyrochlore obtained, spinel crystal portion and crystal boundary portion.On the contrary, if addition is few, then in the inhibition of grain growth, produce inhomogeneities, crystallite dimension produces inhomogeneities, and result, brings the uneven of electric field, deboost characteristic, pulse tolerance deterioration in characteristics.
(d) cobalt oxide, manganese oxide, nickel oxide (CoO, MnO
2, NiO)
The such transition metal of cobalt, manganese, nickel is solid-solution in ZnO to zinc oxide varistor, forms two Schottky barrier.Because respective valence mumber is different, electronic configuration is different, solid solubility temperature is different, ionic radius is different, in order to form stable two Schottky barriers, preferably add more than a kind.Because solid solubility limit neither infinitely solid solution, therefore, rational addition is determined by repeatedly duplicate test.
In addition, if excessively add these transition metals, then because unreacted transition metal works as impurity, there is grain growth inhibition, therefore produce the inhomogeneities of crystal grain, make the deterioration of deboost, pulse tolerance.On the contrary, if addition is few, then owing to cannot form two Schottky barrier fully, therefore electric field concentrates on the defective part of two Schottky barrier, the deterioration of deboost, pulse tolerance.
(e) chromium oxide (Cr
2o
3)
Chromium oxide has the static stabilization of particle and crystal to zinc oxide varistor.If addition is very few, then such stabilization effect is poor, on the contrary, if add excessive, then works as impurity, brings the inhomogeneities of crystal grain, the deterioration of deboost, pulse tolerance.
(f) boric acid, silicon dioxide, germanium oxide (H
3bO
3, SiO
2, GeO
2) and compound glass
For zinc oxide varistor, produce trickle effect change according to the composition of the glass added, but generally speaking, work as sintering aid while contributing to the low temperature of firing temperature, and form Grain-Boundary Phase.If excessively add glass, then separate out in large quantities at crystal boundary and element surface, even if be good result for leakage current characteristic, thermal diffusion efficiency when inputting large pulse reduces, the deterioration of therefore pulse tolerance.
And then due to the exaggerated grain growth of the excessive interpolation generating portion of glass, except pulse tolerance, deboost characteristic is also deteriorated.On the other hand, if the addition of glass is very few, be then difficult to sintering, produce the inhomogeneities of complete characteristic.In addition, firing temperature high temperature, produces Bi
2o
3, Sb
2o
3distillation, the deterioration of rheostatic reliability properties.
G () is for element of volume (Al
2o
3, B
2o
3)
For element of volume for zinc oxide varistor, owing to promoting the low resistance as the ZnO of main material, the effect therefore having the Joule heat produced when large pulse is entered promptly to spread, improves deboost, pulse tolerance.If excessively add for element of volume, then owing to forming spinelle between ZnO, therefore occur that the sintering facilitation effect that exaggerated grain growth is such and grain growth hinder effect, there is the dual character that sintering hinders effect.In a word, deboost, the deterioration of pulse tolerance.On the other hand, if very few for the addition of element of volume, then these effects cannot be manifested.But, because local produces low resistance, therefore, contribute to the inhomogeneities causing characteristic.
Then, the rheostatic manufacture method of oxidation zinc-type Stacked of an embodiment of the invention example is described.Fig. 1 is the flow chart of the rheostatic manufacturing process of oxidation zinc-type Stacked that present embodiment example is shown with time series.In addition, Fig. 2 illustrates an example of the rheostatic cross-section structure of oxidation zinc-type Stacked by the present embodiment example manufactured by the operation shown in Fig. 1.
In the step S11 of Fig. 1, based on the rheostatic material powder of basic composition blending oxidation zinc-type Stacked shown in table 1 grade.At this, such as, the rheostat raw material of intermediate value average grain diameter about 3 μm is weighed.In addition, grain growth inhibiting substances is added according to unit varistor voltage.Be explained, add various glass as sintering aid, but carry out aftermentioned to the composition of this glass material and addition.
In step s 12, the rheostat raw material weighed in above-mentioned step S11 is carried out pulverized particles adjustment.Such as, the alumina medium of 10mm φ is used to pulverize 24 hours, neat particle with ball mill.In following step S13, the above-mentioned material powder through pulverized particles adjustment of false burning.At this, at 900 DEG C, heat-treat adjustment reactivity, particle diameter.Then, in step S14, the material powder after vacation being burnt is pulverized and neat particle with ball mill etc. again.
In step S15, make slurry.Such as, in above-mentioned mixture, add the polyvinyl butyral resin (PVB) of the degree of polymerization 300, phthalic acid ester system plasticizer, polycarboxylic-acid dispersant, the release materials of PEG#600, ethanol/toluene system retarder thinner making slurry.Then, in step s 16, sheet material is made by the slurry made in step S15.At this, with scraper film forming, such as, the green sheet of about 10 ~ 100 μm is made.Be explained, the thickness that can change green sheet makes the rheostat of low pressure, middle pressure, high pressure.
In following step S17, use the electrode paste printing internal electrode patterns such as such as Pt, Pd, Ag/Pd.Such as, as shown in rheostatic cross-section structure and Fig. 2, by overlapping 6 layers of the number of plies of internal electrode 3, carry out thermo-compressed with hot pressing etc., and stacked.Cut in following step S18.As cutting, product size (such as, 3216 sizes) is according to the rules cut stacked green sheet.
In step S19, the duplexer after cutting is kept 10 hours at such as temperature 500 DEG C, carries out unsticking mixture.In step S21 below, at such as 950 ~ 1300 DEG C, burn till 5 hours, in following step S22, at 700 DEG C, annealing in process is carried out to sintered body.And then, in step S23, stick with paste or Ag/Pd paste formation terminal electrode (outer electrode 5a, 5b of Fig. 2) with such as Ag, sinter at the specified temperature.
In step s 24 which, with the order of such as Ni layer, Sn layer, plating is implemented by electrolytic coating to outer electrode 5a, 5b of being formed in step S23.Then, in following step S25, the electrical characteristics such as varistor voltage, leakage current are detected, complete the oxidation zinc-type Stacked rheostat as final products.
Then, the oxidation zinc-type Stacked rheostat of present embodiment example is described in detail.At this, make as the rheostat raw material of the basic composition oxidation zinc-type Stacked rheostatic sample different with its addition, to 3 characteristics (described later leakage current, deboost, pulse tolerance) of this sample determination as rheostatic fundamental characteristics.
Assessment item (varistor properties) and its assay method of the rheostatic each sample made for the rheostatic manufacture method of Zinc oxide by present embodiment example are as described below.
(A) leakage current
So-called leakage current, the electric current that ordinary representation circulates when applying maximum permission circuit voltage.In the evaluation of rheostatic leakage current, under the voltage environment applied serially when rheostat uses, observe and produce how many current losses.Leakage current is more few more preferred, if leakage current is large, then easily produces degradation failure, and therefore, the little rheostat of leakage current is from the viewpoint of long-life such also excellence.
In order to be lower by drain current suppressing, the homogenieity of two Schottky barriers that crystal boundary is formed is very important.If the liquid phase that simultaneously can obtain crystal boundary is brilliant, then high resistance, therefore preferably.In the evaluation of the rheostatic leakage current of oxidation zinc-type Stacked to present embodiment example, by the voltage that the produces during electric current that reads in circulation 1mA, varistor voltage is measured, for leakage current, the current value circulated when applying the voltage of 0.9 times (Hang) of harsh condition and varistor voltage is measured.
(B) deboost
As mentioned above, so-called varistor voltage is the voltage V occurred when circulating the electric current of 1mA
1mA, in contrast, so-called rheostatic deboost, be varistor voltage during larger electric current that circulation about 1A, 2A, 10A are such.Rheostat is in parallel with the part that will protect, and cuts off and protective circuit the high voltage portion of the abnormally high-voltage produced because of some reasons such as ESD.For display in this wise voltage is suppressed be lower function deboost for, its value is lower, and display circuit voltage, the load putting on protection part more reduce.
In order to occur being suppressed by deboost, for lower characteristic, to need the homogenizing of the ZnO crystallite dimension of carrying out sintered body in rheostat.Thus, the electric field of the load voltage applied is dispersed in rheostat entirety, deboost can be suppressed for lower.The rheostatic deboost of oxidation zinc-type Stacked of present embodiment example is the measurement result of the voltage produced when applying the electric current of 2A.Be explained, in evaluation as follows, as the reading and the ratio of varistor voltage, i.e. limit voltage ratio (V that produce voltage
2A/ V
1mA) and show.
(C) pulse tolerance
So-called pulse tolerance, represents tolerance when the such high voltage/heavy current pulse of lightning surge, vehicle-mounted motor surge, igniting surge enters.In order to improve pulse tolerance, need as the correspondence in both grain and grain boundaries of rheostatic basic comprising.First, crystal grain preferably seeks low resistance, this heat that inputted big current becomes Joule heat at crystal boundary is rapidly to bulky single diffusion, prevents the destruction of 1 crystal boundary.
On the other hand, for crystal boundary, make the high uniformity of two Schottky barrier/decentralized, the big current flowed into caused to destroy be important.In order to obtain the zinc oxide varistor with excellent electrical characteristics, need the whole correspondence considering above-mentioned mechanism.In the oxidation zinc-type Stacked rheostat of present embodiment example, as pulse tolerance (2ms waveform), the energy (J) produced when applying the pulse of 2ms waveform is measured.The end-point energy of this display varistor voltage rate of change within ± 10%.
Then, for the rheostatic each sample of oxidation zinc-type Stacked of present embodiment example, the evaluation result etc. of its material composition, characteristic is described particularly.At this, in order to find the material composition of the rheostatic the best of oxidation zinc-type Stacked with excellent electrical characteristics, the effect based on each additive shown in above-mentioned (a) ~ (g) has carried out various experiment.Then, as for oxidation zinc-type Stacked rheostatic evaluation, respectively the effect, the addition of (2) various transition metal and the glass that bring are formed to the addition of (1) various glass and glass and form effect, (3) other additive effect of element of bringing and evaluate.
(1) addition of various glass and glass form the effect and evaluation thereof brought
Due to only cannot varistor properties be obtained with zinc oxide and glass, therefore add various glass material in as the rheostat raw material of basic composition and evaluate.Table 1 illustrates rheostat raw material (element material) as the rheostatic basic composition of oxidation zinc-type Stacked (being called basic composition 1) of present embodiment example and its addition.Be explained, in Table 1, the addition of the element beyond ZnO is the outside percentage addition relative to ZnO 100mol%.
Table 1
Table 2 is for being oxidized the rheostatic glass material of zinc-type Stacked, at this, studies the glass materials (glass A ~ D) of 4 kinds of compositions.Specifically, the glass material of following 4 kinds of compositions is studied:
(i) glass A:SiO
2glass
(ii) glass B: lead borosilicate glass (B
2o
3-SiO
2system)
(iii) glass C: borosilicic acid bismuth glass (B
2o
3-SiO
2-Bi
2o
3system)
(iv) glass D: zinc borosilicate glass (B
2o
3-SiO
2-ZnO is)
Table 2
Table 3 ~ table 6 is the evaluation result of the rheostatic varistor properties assessment item of oxidation zinc-type Stacked of present embodiment example.The addition of the glass shown in each table is the weight ratio relative to ZnO contained in rheostat raw material (basic composition shown in table 1), for having carried out the result of the test of evaluating characteristics project for the addition of 0.3wt% ~ 2.9wt%.
Table 3
Table 4
Table 5
Table 6
From the evaluation result of the varistor properties assessment item shown in table 3 ~ table 6, compared with glass A, B, C, for glass D, in limit voltage ratio, characteristic improves, the result that the project for other also can be balanced.
Add in rheostat raw material glass material be in order to the sintering to the ZnO as rheostatic main material after particle diameter (crystallite dimension) carry out homogenizing.Deboost characteristic, the resistance to flow characteristic of surge can be improved by the homogenizing of particle.And found by above-mentioned experiment, in order to grow with making ZnO uniform crystal particles, the glass (above-mentioned glass D) based on ZnO is applicable.
That is, due to high at middle reactivity degree such as silica glass, therefore, the reaction acceleration of ZnO, makes particle produce inhomogeneities.On the other hand, the glass of zno-based is owing to being rich in ZnO, and the therefore sluggish of ZnO, has the effect of the inhomogeneities suppressing grain growth.In addition, in order to carry out vitrifying to the ZnO of the main material as glass material, add SiO
2, B
2o
3etc. borosilicic acid system glass ingredient.Be explained, Na contained in glass A ~ D
2o, K
2o, CaO add, according to SiO in order to the fusing point reducing glass material
2amount and adjust.At SiO
2amount few when, sometimes do not need yet add.
At this, to research as the additive in glass material, with the relation of contained element in rheostat raw material in be described for improving the result of preferred glass material characteristic further.
< lead oxide, bismuth oxide (PbO, Bi
2o
3) >
As PbO, the Bi of the additive in glass material
2o
3, the crystal boundary constitute as ZnO can be suppressed and the Bi be contained in rheostat raw material
2o
3distribution, concentration difference, make it coexist.In addition, the mobility of these additives to glass impacts.By PbO, Bi
2o
3add in rheostat raw material, also add in glass material simultaneously.In addition, can pass through PbO, Bi
2o
3a part carry out vitrifying after add in rheostat raw material and suppress excessive reaction.Then Bi is selected for unleaded requirement
2o
3.
Be explained, the vitrifying in so-called present embodiment example, refer to by based on material and additive preferably more than the fusing point of glass (such as more than 1000 DEG C) carried out heat treated state.Thus, the reactivity of each additive can be suppressed.
< antimony oxide, aluminium oxide (Sb
2o
3, Al
2o
3) >
As the Sb of the additive in glass material
2o
3, Al
2o
3the grain growth of control ZnO.Added in rheostat raw material, also added to glass material simultaneously.In addition, the Sb making to add in advance in itself and rheostat raw material can be added in rheostat raw material to after vitrifying is carried out to a part
2o
3compatiblely to coexist.Be explained, Sb
2o
3, Al
2o
3be equivalent to the common element recorded in the claim of the application.
< manganese oxide, cobalt oxide, chromium oxide (MnO
2, CoO, Cr
2o
3) >
As the MnO of the additive in glass material
2, CoO, Cr
2o
3for controlling crystal boundary, to the transition metal group of ZnO solid solution, be the particularly preferred element of reactivity.By these additives all or any one add in the both sides of rheostat raw material and glass material.In addition, can by carrying out vitrifying to a part and add in rheostat raw material suppressing excessive reaction, the performance of neat zinc oxide.Be explained, MnO
2, CoO, Cr
2o
3be equivalent to transition metal contained in the common element recorded in the claim of the application.
(2) addition of various transition metal and glass form the effect and evaluation thereof brought
Due to only cannot varistor properties be obtained with zinc oxide and transition metal, therefore add various transition metal in as the rheostat raw material of basic composition and evaluate.Table 7 illustrates rheostat raw material (element material) and its addition as being oxidized the rheostatic basic composition 2 of zinc-type Stacked.Be explained, in table 7, the addition of the element beyond ZnO is the outside percentage addition relative to ZnO 100mol%.
Table 7
At this, in above-mentioned basic composition 2, add following element, carry out effect test.
I () be cobalt oxide (CoO) only
(ii) only manganese oxide (MnO
2)
(iii) cobalt oxide (CoO) and manganese oxide (MnO
2) compound
The result of study of the effect interpolation of above-mentioned transition metal brought is shown in table 8 ~ table 12.Be explained, table 8 ~ table 12 any one in, the addition of transition metal is the outside percentage relative to ZnO 100mol%.
Table 8 illustrates the effect that with the addition of cobalt oxide (CoO) in basic composition 2.Being confirmed by evaluation result, when with the addition of CoO, in limit voltage ratio, pulse tolerance, is particularly the result that can obtain in the scope (in table, the scope of surrounding with two-wire) of 0.5 ~ 1.5mol% at the addition of CoO.
Table 8
Table 9 illustrates and with the addition of manganese oxide (MnO in basic composition 2
2) effect.Confirmed by evaluation result, with the addition of manganese oxide (MnO
2) when, in limit voltage ratio, pulse tolerance, particularly pass through to add MnO in the scope (in table, the scope of surrounding with two-wire) of 0.5 ~ 1.5mol%
2the result that can obtain.
Table 9
Table 10 ~ table 12 illustrates and be mixed with cobalt oxide (CoO) and manganese oxide (MnO in basic composition 2
2) time effect.At this, carry out each evaluation (mensuration of leakage current, deboost, pulse tolerance) according to their addition.That is, table 10 illustrates the result of study about leakage current, and table 11 illustrates the result of study about deboost, and table 12 illustrates the result of study about pulse tolerance.Be explained, table 10 ~ table 12 any one in, cobalt oxide (CoO) and manganese oxide (MnO
2) addition be outside percentage addition relative to ZnO 100mol%.
Table 10 leakage current
Table 11 deboost
Table 12 pulse tolerance
Distinguished by the result shown in table 10 ~ table 12, by cobalt oxide (CoO) 0.5 ~ 1.5mol%, manganese oxide (MnO
2) 0.5 ~ 1.5mol% scope (in table, the scope of surrounding with two-wire) in combination simultaneously add in basic composition 2, excellent characteristic can be obtained in leakage current, deboost, the resistance to flow characteristic of pulse.
(3) additive effect of other element and evaluation thereof
At this, with the addition of crystal boundary formation material (bismuth oxide (Bi in as the rheostat raw material of basic composition
2o
3)), hinder grain growth material (antimony oxide (Sb
2o
3), chromium oxide (Cr
2o
3)), for element of volume (boric acid (H
3bO
3), aluminium oxide (Al
2o
3)) element as other time effect and addition study.
(3-1) bismuth oxide (Bi
2o
3) interpolation and effect
Due to only cannot varistor properties be obtained with zinc oxide and bismuth oxide, therefore, to shown in table 13, with the addition of bismuth oxide element (Bi as in the rheostat raw material (being called basic composition 3) of basic composition
2o
3) time evaluating characteristics project test.Be explained, in table 13, the addition of the element beyond ZnO is the outside percentage addition relative to ZnO 100mol%.
Table 13
Bismuth oxide element (Bi is with the addition of by the basic composition 3 of table 13
2o
3) time evaluating characteristics result be shown in table 14.From evaluation result, by bismuth oxide (Bi
2o
3) 0.1 ~ 1.0mol% scope (in table, with two-wire surround scope) in add, can be balanced and the characteristic of excellence in leakage current, deboost, the resistance to flow characteristic of pulse.
Table 14
(3-2) antimony oxide (Sb
2o
3) and chromium oxide (Cr
2o
3) interpolation and effect
Due to only cannot varistor properties be obtained with zinc oxide and antimony oxide, chromium oxide, therefore, shown in table 15, add antimony oxide (Sb as combination in the rheostat raw material (being called basic composition 4) of basic composition
2o
3) and chromium oxide (Cr
2o
3) as hindering grain growth material, its effect is evaluated.Be explained, in table 15, the addition of the element beyond ZnO is the outside percentage addition relative to ZnO 100mol%.
Table 15
Table 16 ~ table 18 illustrates that antimony oxide (Sb is added in combination in basic composition 4
2o
3) and chromium oxide (Cr
2o
3) time effect.That is, table 16 illustrates the result of study about leakage current, and table 17 illustrates the result of study about deboost, and table 18 illustrates the result of study about pulse tolerance.Be explained, the antimony oxide (Sb in table 16 ~ table 18
2o
3) and chromium oxide (Cr
2o
3) addition is outside percentage addition relative to ZnO 100mol%.
Table 16 leakage current
Table 17 deboost
Table 18 pulse tolerance
From the evaluation result shown in table 16 ~ table 18, what in whole characteristics, show the addition of excellent specific property is combined as antimony oxide (Sb
2o
3) 0.1 ~ 1.5mol%, chromium oxide (Cr
2o
3) scope (in table, the scope of surrounding with two-wire) of 0.1 ~ 1.0mol%, in this range, for leakage current, deboost, pulse tolerance, excellent characteristic can be obtained.
(3-3) for interpolation and the effect thereof of element of volume
Due to only cannot varistor properties be obtained with zinc oxide with for element of volume, therefore, shown in table 19, in as the rheostat raw material (being called basic composition 5) of basic composition, add boric acid (H
3bO
3), aluminium oxide (Al
2o
3) as element of volume, characteristic is evaluated.Be explained, in table 19, the addition of the element beyond ZnO is the outside percentage addition relative to ZnO 100mol%.
Table 19
Table 20 ~ table 22 illustrates and with the addition of boric acid (H in basic composition 5
3bO
3), aluminium oxide (Al
2o
3) time effect.Specifically, table 20 is the result of study about leakage current, and table 21 is the result of study about deboost, and table 22 is the result of study about pulse tolerance.Be explained, the boric acid (H in table 20 ~ table 22
3bO
3), aluminium oxide (Al
2o
3) addition represent outside percentage addition relative to ZnO 100mol%.
Table 20 leakage current
Table 21 deboost
Table 22 pulse tolerance
From the result shown in table 20 ~ table 22, show in whole characteristics the interpolation of excellent specific property be combined as table 20 ~ table 22 with two-wire surround scope in boric acid (H
3bO
3) 0.1 ~ 1.0mol%, aluminium oxide (Al
2o
3) scope of 0.001 ~ 0.005mol%, excellent characteristic can be obtained with the addition of this scope in leakage current, deboost and pulse tolerance.
On the other hand, confirm, add boric acid (H
3bO
3) 0.1 ~ 1.0mol% is aluminium oxide (Al
2o
3) the prerequisite of additive effect.And then, confirm, even if do not add aluminium oxide (Al
2o
3), by adding boric acid (H
3bO
3) 0.1 ~ 1.0mol% also can obtain excellent leakage current and deboost characteristic.
From above research evaluation result, the rheostatic the best composition of oxidation zinc-type Stacked of present embodiment example can be limited.Table 23 is the composition of the rheostatic most preferred rheostat raw material of oxidation zinc-type Stacked of present embodiment example, and 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 illustrates its concrete composition.
Be explained, the addition (not comprising glass material) of the raw material in table 23 is for show relative to the outside percentage mol% of ZnO 100mol%, for the addition of glass material, it is the outside percentage relative to ZnO contained in rheostat raw material.
Table 23
| Masurium | Addition (mol%) |
| ZnO | 100 |
| B 2O 3 | 0.1～1.0 |
| CoO | 0.5～1.5 |
| MnO 2 | 0.5～1.5 |
| Sb 2O 3 | 0.1～1.5 |
| Cr 2O 3 | 0.1～1.0 |
| H 3BO 3 | 0.05～1.0 |
| Glass material | 0.5 ~ 2.5 weight portion/ZnO |
Table 24
| Masurium | Addition (wt%) |
| B 2O 3 | 15～40 |
| SiO 2 | 5～25 |
| ZnO | 50～75 |
| PbO、Bi 2O 3At least any one | 1～10 |
| Sb 2O 3、Al 2O 3At least any one | 0.1～1.5 |
| MnO 2、CoO、Cr 2O 3Any one more than | 1.0 ~ 5.0 are counted with monomer or total |
Thus, make oxidation zinc-type Stacked rheostat by the varistor element employing the material composition shown in table 23 and table 24, the zinc oxide varistor with excellent varistor properties can be obtained thus.More specifically, known to obtain in leakage current 2 (μ A) below, in limit voltage ratio 1.70 (V
2A/ V
1mA) below, in pulse tolerance the varistor properties of more than 1 (J).
As described above, in the rheostatic manufacture method of the Zinc oxide of present embodiment example, by adopting following formation: use the rheostatic varistor element of composite material formation Zinc oxide will mixed with the glass material of the zinc borosilicate system glass that with the addition of the second additive at the rheostat raw material that with the addition of the first additive in the zinc oxide (ZnO) of main material, these first additives and the second additive contain the common element in the both sides making an addition to rheostat raw material and glass material, can obtain thus at the leakage current as rheostatic fundamental characteristics, deboost and pulse tolerance whole in characteristic is improved Zinc oxide rheostat.
Namely; find the common element added in the additive of regulation that adds in the additive of the regulation of adding in rheostat raw material and addition thereof, glass material and the both sides of addition and rheostat raw material and glass material thereof; based on them; limit the composition as the rheostatic the best of Zinc oxide; make varistor element with this material ratio of components, the Zinc oxide rheostat of the electrical characteristics with circuit protection function excellence can be made thus.
Claims (5)
1. the rheostatic manufacture method of Zinc oxide, it is characterized in that, possess: prepare to be main material with zinc oxide (ZnO), in this main material, to add the rheostat raw material of the first additive, and as zinc borosilicate system glass, the step of the glass material that adds the second additive,
Make the step of composite material that described rheostat raw material and described glass material are mixed and
The step of the rheostatic varistor element of Zinc oxide is formed by described composite material,
Described first additive and described second additive contain the common element of the regulation in the both sides making an addition to described rheostat raw material and described glass material.
2. the rheostatic manufacture method of Zinc oxide according to claim 1, it is characterized in that, weigh described glass material in the mode being 0.5 weight portion ~ 2.5 weight portion relative to zinc oxide contained in described rheostat raw material, mix with described rheostat raw material.
3. the rheostatic manufacture method of Zinc oxide according to claim 1 and 2, is characterized in that, described common element contains manganese oxide (MnO
2), cobalt oxide (CoO), chromium oxide (Cr
2o
3) in arbitrary transition metal.
4. the rheostatic manufacture method of Zinc oxide according to claim 1 and 2, is characterized in that, described common element contains antimony oxide (Sb
2o
3) or aluminium oxide (Al
2o
3).
5. the rheostatic manufacture method of Zinc oxide according to claim 1, is characterized in that, described glass material contains lead oxide (PbO) or bismuth oxide (Bi
2o
3) as the additive beyond described second additive.
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| JP2014035311A JP6355360B2 (en) | 2014-02-26 | 2014-02-26 | Manufacturing method of zinc oxide varistor |
| JP2014-035311 | 2014-02-26 |
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| 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 |
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| 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 |
| US5739742A (en) * | 1995-08-31 | 1998-04-14 | Matsushita Electric Industrial Co., Ltd. | Zinc oxide ceramics and method for producing the same and zinc oxide varistors |
| JP2006245111A (en) | 2005-03-01 | 2006-09-14 | Koa Corp | Bismuth-based zinc oxide varistor |
| CN101447265A (en) * | 2007-11-27 | 2009-06-03 | 兴亚株式会社 | Method for fabricating zinc oxide multilayer chip piezoresistor |
| 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 |
| TW201221501A (en) * | 2010-11-26 | 2012-06-01 | Sfi Electronics Technology Inc | Process for producing ZnO varistor particularly having internal electrode composed of pure silver and sintered at a lower sintering temperature |
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