CN109686520A - The preparation of high throughflow ZnO varistor special utility side high-resistance layer - Google Patents
The preparation of high throughflow ZnO varistor special utility side high-resistance layer Download PDFInfo
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- CN109686520A CN109686520A CN201811434753.8A CN201811434753A CN109686520A CN 109686520 A CN109686520 A CN 109686520A CN 201811434753 A CN201811434753 A CN 201811434753A CN 109686520 A CN109686520 A CN 109686520A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/06—Apparatus or processes specially adapted for manufacturing resistors adapted for coating resistive material on a base
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C17/00—Apparatus or processes specially adapted for manufacturing resistors
- H01C17/30—Apparatus or processes specially adapted for manufacturing resistors adapted for baking
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Abstract
A kind of preparation of high throughflow ZnO varistor special utility side high-resistance layer, the raw material prepared is mixed and dissolved by heating, uniform solution is made, and the side of resistor disc is applied directly to after resistance sheetmolding, it is characterized in that, including raw material preparation steps, ball milling mixing step, spray drying step, compression moulding step, sintering step, coating step, step in blocks, the raw material preparation steps, ball milling mixing step, spray drying step, compression moulding step, sintering step, coating step are successively carried out.The beneficial effect is that: selection upper resistive formation after shaping reduces originally because of the fluctuation of the inconsistent bring glazed thickness of pre-burning shrinking percentage, more stable in technique.
Description
Technical field
The present invention relates to resistor disc preparation process field, resistive formation in especially a kind of non-linear resistor manufacturing process
New method.
Background technique
Permittivity of zinc is the core component of ZnO arrester, thus is the key component for determining arrester performance superiority and inferiority.?
It is respectively the ability of its 4/10 μ s heavy current impact of the arrester of 5kA and 10kA tolerance twice to nominal discharge current in national standard,
It requires to reach 65kA and 100kA respectively.SiO has been selected in foreign patent research2Fe2O3The formula of system, but D3, D4 resistor disc are resistance to
It is only capable of respectively reaching 60kA and 80kA or so by the ability of heavy current impact, reaches 65kA and 100kA Shang Youyi away from requirement respectively
Set a distance.The common difficulty of permittivity of zinc high current ability domestic pharmaceutical industry is improved, technical difficulty is various, because it
Not only it is decided by the dielectric level of resistive formation itself, but also further depends on the associativity of resistive formation and resistor disc ontology, thermal expansion
The matching of the performances such as coefficient, elasticity and tensile strength.Because inorganic high resistant series of strata are sintered in the thickness of this body side surface of resistor disc
The only thin layer of 0.1-0.12mm, when being burnt at high temperature, complicated physical-chemical reaction will occur for the two, in the contact of the two
Place forms boundary's transition zone between the two ingredient, and thickness, compactness of the transition zone etc. both had with the composition of the two, coating layer thickness
It closes, it is also related with firing temperature.So it is extremely difficult for developing with Ontology Matching is appropriate, sintering range is wide resistive formation
's.
It is analyzed for information about both at home and abroad from what is be collected into, for the permittivity of zinc of arrester, improves its high current to understand
Tolerance, majority are taken on the basis of this burning inorganic resistive formation, and the measure of cryogenic glass glaze or various organic coatings is applied.
There are following several situations:
(1) cryogenic glass glaze is applied after the inorganic resistive formation of this burning.Certain producers are shown using the actual conditions of this technique
In the case that glass glaze formulation selection is appropriate, thickness is relatively thick, deposition temperature schedule is suitable for, it can achieve and improve high current energy
The sample of the effect of power, some producers has passed through the type approval test of national inspection centers.But from the test of mass production random sampling
As a result it sees, is extremely difficult to standard requirements.The reason is that glazed thickness is difficult to control in heat-treatment furnace in addition usually in mass production
The fluctuation of the glaze melting temperature temperature difference is allowed to inconsistent with the associativity quality of ontology, and the appearance luster of glaze is also different: especially
Glaze is difficult to match with the thermal expansion coefficient of ontology, so being difficult to achieve the effect that stablize to improve high current.In addition glaze spraying technique
Production efficiency is low, and production cost is also high, and quality is difficult to ensure, so these, which become it, is difficult to the determinant promoted and applied.
(2) add on the basis of this burning inorganic resistive formation and apply organic insulator.As Tu Naire (200 °C or so) Polyester Paint,
High temperature epoxy resins etc., some also add inorganic insulation powder, such as titanium oxide or aluminium oxide wherein.This be China use compared with
To be universal, measure not only convenient but also economic in technique.
(3) inorganic resistive formation is not applied, in the resistor disc porcelain body side direct spraying fluid silicone rubber of sintering.Due to silicon rubber
Coupling agent in conjunction with ontology, thus have the shortcomings that combine loosely, mechanical strength it is low.But since silicon rubber is a kind of elasticity
Plastic body good, dielectric strength is high, so having good tolerance heavy current impact.Below U1m electric potential gradient 200V/mm
In the case where, D25 and D4 can respectively reach 65KA and 100KA.But since production efficiency is low, material cost is high, Er Qieyou
In in packed and transported process, coating is easy clashing and breaking, abrasion, thus resistor disc cannot function as commodity selling, so the producer is not
It uses again, but as the successful techniques measure for improving resistor disc high-rate performance, it should say a kind of thinking for original creation of can yet be regarded as.
Based on the above situation, the good resistive formation of tolerance heavy current impact, it is necessary to have following properties and characteristics:
(1) it is prone to react and the influence degree of the electric property to ontology from resistive formation and resistor disc ontology in sintering process
Consider, should select identical as ZnO ceramic segment ingredient in high resistant layer formula or play the similar ingredient of product insulating effect, in this way
It can not only be easy to happen with ontology in sintering process and diffuse into one another permeable reactive, generate suitable thickness, compact structure, in conjunction with jail
Gu, the high resistive formation of insulating properties, and with the surface layer far from ontology even if cannot react with ontology itself and also can generate knot
The resistive formation that structure is fine and close, insulating properties is high.The main object of its product should be mutually zinc silicate, antimony gahnite and a small amount of solid solution
Or devitrified glass.
Both (2) thermal expansion coefficient of resistive formation and ontology must match, i.e., thermal expansion coefficient should approach or most
It is that the former is 06-15 × 10C smaller than the latter well, forms compression stress, raising resistor disc to ensure to be burnt into cooling procedure resistive formation
Mechanical strength and cold and hot performance, thus improve its resist high current surge withstanding capability.
The manufacturing method of existing zinc oxide resistance sheet, because of its process stabilizing, product qualification rate is high and is preferably answered
With.But there is also following disadvantages for it:
Disadvantage one: resistive formation complex manufacturing technology, glaze slip stability are poor；
Disadvantage two: glaze layer uniformity is poor, and glazed thickness is affected by percent of firing shrinkage；
Disadvantage three: the pressure ratio of resistor disc is poor, and the through-current capability of resistor disc is restricted.
With the continuous improvement of product technology grade, the requirement to properties of product is also higher and higher, original pressure ratio performance
Requirement is had been unable to meet, the resistor disc of exploitation low-pressure ratio, high throughflow is badly in need of.
Summary of the invention
The technical problem to be solved in the invention: it in million volts of resistance slice prescriptions, is adjusted by high resistant layer formula, Yi Jigong
The control of skill has both solved the problems, such as the side insulation of resistor disc, simultaneously so that the ontology of resistor disc is matched with the shrinking percentage of glaze layer
Improve the square wave discharge capacity of resistor disc.
Technology path of the invention: pass through the variation of the introducing form to elements such as antimony, iron in high resistant layer formula, Yi Jiliang
Adjustment so that resistor disc is well combined between ontology and glaze layer after sintering, and shrinking percentage is close, so that resistor disc is passing through
When large capacity electric current, resistor disc is not cracked.
The purpose of the present invention is to solve the above problems, devise a kind of high throughflow ZnO varistor special utility side
The preparation of face resistive formation.Specific design scheme are as follows:
A kind of preparation of high throughflow ZnO varistor special utility side high-resistance layer, the raw material prepared is mixed and is heated molten
Solution, is made uniform solution, and the side of resistor disc, including raw material preparation steps, ball are applied directly to after resistance sheetmolding
Mixing step, spray drying step, compression moulding step, sintering step, coating step, step in blocks are ground, the raw material is prepared
Step, ball milling mixing step, spray drying step, compression moulding step, sintering step, coating step successively carry out.
In the raw material configuration step, composition of raw materials zinc oxide ZnO, bismuth oxide Bi2O3, antimony oxide Sb2O3, manganese oxide
MnO2, stannic oxide SnO2, chromium oxide Cr2O3, polyvinyl alcohol C2H4O, deionized water.
In the sintering step,
With high-temperature electric resistance furnace, sintered body, actual temp and control time are as follows in closed atmosphere:
From room temperature to 400 DEG C, heating-up time 10-15h；
In 280 DEG C of holding low temperature dumping 5h；
It is cooled to room temperature, cooling rate is 15 DEG C/h.
In the coating step,
Coating method includes spray, roller coating, directly brushes,
Form resistive formation after coat, the resistive formation with a thickness of 0.1-0.15mm.
In the step in blocks,
From room temperature to 900 DEG C, heating-up time 9h, average heating speed is 100 DEG C/h；
From 900 DEG C to 1250 DEG C, heating-up time 5h, average heating speed is 100 DEG C/h；
In 1250 DEG C of heat preservation 2-4h；
Temperature fall, average cooling rate are 100 DEG C/h.
The mass percent of each ingredient in the composition of raw materials are as follows: zinc oxide ZnO:30-50%, bismuth oxide Bi2O3: 10-
25%, antimony oxide Sb2O3: 5-15%, manganese oxide MnO2: 2-5%, stannic oxide SnO2: 1-5%, chromium oxide Cr2O3: 0.1-0.5% gathers
Vinyl alcohol C2H4O:2.5-5%, deionized water: 35-50%.
The system for the high throughflow ZnO varistor special utility side high-resistance layer that above-mentioned technical proposal through the invention obtains
It is standby, the beneficial effect is that:
Upper resistive formation after shaping is selected, is reduced originally because of the fluctuation of the inconsistent bring glazed thickness of pre-burning shrinking percentage, work
It is more stable in skill.
Detailed description of the invention
Fig. 1 is 2 ms square wave the selection result of resistance slice prescription resistive formation valve block；
Fig. 2 is 4/10 μ s heavy current impact experimental results of resistance slice prescription resistive formation.
Specific embodiment
The present invention is specifically described with reference to the accompanying drawing.
Embodiment 1:
D5 specific resistance piece is selected, and matches resistive formation: zinc oxide 35%, bismuth oxide 15%, antimony oxide 6% in the following way, oxidation
Manganese 4%, boron oxide 0.3%, PVA(polyvinyl alcohol) 3.5%, deionized water 36.2%.The raw material prepared is mixed and is dissolved by heating, system
At uniform solution, and it is applied directly to after resistance sheetmolding the side of resistor disc.
The following are specific formula grade technological process of production detailed descriptions.
Zinc oxide valve plate is after raw material preparation, ball milling mixing, spray drying, compression moulding:
1) it is sintered
With high-temperature electric resistance furnace, sintered body, actual temp and control time are as follows in closed atmosphere:
From room temperature to 400 DEG C, the heating-up time 10 ~ 15 hours；
280 DEG C holding low temperature dumping 5 hours；
It is cooled to room temperature (15 ° per hour)
2) coat resistive formation (each resistor disc coats 2g, resistive formation coating thickness 0.1mm)；
3) from room temperature to 900 DEG C, heating-up time 9(100 degree is per hour) hour；
From 900 DEG C to 1250 DEG C, heating-up time 5(70 degree is per hour) hour；
2 ~ 4 hours are kept the temperature at 1250 DEG C；
Temperature fall (100 degree per hour).
Then resistor disc such as is normally ground, is aluminium-plated at the subsequent manufacturing processes, is then tested, as a result as shown in Figure 1, Figure 2
Shown, raw material use various soluble-salts, simplify the manufacture craft of resistive formation, and to be easier to control using upper in technique
System；The various reasonable introduction volumes of raw material, can attain the results expected.
Above-mentioned technical proposal only embodies the optimal technical scheme of technical solution of the present invention, those skilled in the art
The principle of the present invention is embodied to some variations that some of them part may be made, belongs to the scope of protection of the present invention it
It is interior.
Claims (5)
1. a kind of preparation of high throughflow ZnO varistor special utility side high-resistance layer, the raw material prepared is mixed and is heated
Dissolution, is made uniform solution, and the side of resistor disc is applied directly to after resistance sheetmolding, which is characterized in that including original
Expect preparation steps, ball milling mixing step, spray drying step, compression moulding step, sintering step, coating step, step in blocks,
The raw material preparation steps, ball milling mixing step, spray drying step, compression moulding step, sintering step, coating step are successively
It carries out,
In the raw material configuration step, composition of raw materials includes zinc oxide ZnO, bismuth oxide Bi2O3, antimony oxide Sb2O3, manganese oxide
MnO2, stannic oxide SnO2, chromium oxide Cr2O3, polyvinyl alcohol C2H4O, deionized water.
2. the preparation of high throughflow ZnO varistor special utility side high-resistance layer according to claim 1, feature exist
In, in the sintering step,
With high-temperature electric resistance furnace, sintered body, actual temp and control time are as follows in closed atmosphere:
From room temperature to 400 DEG C, heating-up time 10-15h；
In 280 DEG C of holding low temperature dumping 5h；
It is cooled to room temperature, cooling rate is 15 DEG C/h.
3. the preparation of high throughflow ZnO varistor special utility side high-resistance layer according to claim 1, feature exist
In, in the coating step,
Coating method includes spray, roller coating, directly brushes,
Form resistive formation after coat, the resistive formation with a thickness of 0.1-0.15mm.
4. the preparation of high throughflow ZnO varistor special utility side high-resistance layer according to claim 1, feature exist
In, in the step in blocks,
From room temperature to 900 DEG C, heating-up time 9h, average heating speed is 100 DEG C/h；
From 900 DEG C to 1250 DEG C, heating-up time 5h, average heating speed is 100 DEG C/h；
In 1250 DEG C of heat preservation 2-4h；
Temperature fall, average cooling rate are 100 DEG C/h.
5. the preparation of high throughflow ZnO varistor special utility side high-resistance layer according to claim 1, feature exist
In the mass percent of each ingredient in the composition of raw materials are as follows: zinc oxide ZnO:30-50%, bismuth oxide Bi2O3: 10-25%, oxidation
Antimony Sb2O3: 5-15%, manganese oxide MnO2: 2-5%, stannic oxide SnO2: 1-5%, chromium oxide Cr2O3: 0.1-0.5%, polyvinyl alcohol
C2H4O:2.5-5%, deionized water: 35-50%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922182A (en) * | 2019-11-28 | 2020-03-27 | 新疆大学 | Preparation method of high-gradient low-leakage-current ceramic |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59191303A (en) * | 1983-04-14 | 1984-10-30 | 株式会社明電舎 | Nonlinear resistor |
| CN101700976A (en) * | 2009-11-20 | 2010-05-05 | 中国西电电气股份有限公司 | Formula of non-linear resistor for high voltage surge arrester and manufacturing method thereof |
| CN103325512A (en) * | 2013-06-28 | 2013-09-25 | 清华大学 | Preparation method of lateral insulating layer of high-gradient zinc oxide voltage-sensitive valve plate |
| CN103646738A (en) * | 2013-12-13 | 2014-03-19 | 中国西电电气股份有限公司 | Preparation method of high-resistance layer for side surface of zinc oxide resistor disc |
-
2018
- 2018-11-28 CN CN201811434753.8A patent/CN109686520A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59191303A (en) * | 1983-04-14 | 1984-10-30 | 株式会社明電舎 | Nonlinear resistor |
| CN101700976A (en) * | 2009-11-20 | 2010-05-05 | 中国西电电气股份有限公司 | Formula of non-linear resistor for high voltage surge arrester and manufacturing method thereof |
| CN103325512A (en) * | 2013-06-28 | 2013-09-25 | 清华大学 | Preparation method of lateral insulating layer of high-gradient zinc oxide voltage-sensitive valve plate |
| CN103646738A (en) * | 2013-12-13 | 2014-03-19 | 中国西电电气股份有限公司 | Preparation method of high-resistance layer for side surface of zinc oxide resistor disc |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110922182A (en) * | 2019-11-28 | 2020-03-27 | 新疆大学 | Preparation method of high-gradient low-leakage-current ceramic |
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Application publication date: 20190426 |
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