CN106630634B - High-voltage ceramic semi-conducting glaze - Google Patents
High-voltage ceramic semi-conducting glaze Download PDFInfo
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- CN106630634B CN106630634B CN201710002735.1A CN201710002735A CN106630634B CN 106630634 B CN106630634 B CN 106630634B CN 201710002735 A CN201710002735 A CN 201710002735A CN 106630634 B CN106630634 B CN 106630634B
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C1/00—Ingredients generally applicable to manufacture of glasses, glazes, or vitreous enamels
- C03C1/04—Opacifiers, e.g. fluorides or phosphates; Pigments
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5022—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with vitreous materials
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
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- Organic Chemistry (AREA)
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Abstract
The present invention relates to semi-conducting glaze technical fields, more particularly to High-voltage ceramic semi-conducting glaze, semi-conducting glaze contains the component of following quality proportioning: high potassium is 25~35 parts of iron feldspar, 8~14 parts of base mud low, 4~10 parts of east victory soil, 1~4 part of talcum, 20~30 parts of silica flour, 2~4 parts of barium carbonate of forging, 12~18 parts of iron oxide red, 1~3 part of chrome oxide green, 9~12 parts of titanium dioxide, 1~2 part of spodumene.The structural stability of semi-conducting glaze of the present invention is high, and surface is fine and smooth, and surface is glossy, and reduces eutectic point, improves and melts efficiency；Meanwhile the binding ability using east victory soil and base mud, after improving the glazing of semiconductor glaze slip.
Description
Technical field
The present invention relates to semi-conducting glaze technical fields, especially High-voltage ceramic semi-conducting glaze.
Background technique
Semi-conducting glaze be it is a kind of for high-voltage electromagnetic and with property glaze, surface resistivity between insulator with
Between conductor.Semi-conducting glaze is usually that a certain amount of conductive metal oxide or compound structure are added in common glaze for electric porcelain
At.The microstructure of formation is different from common glaze, in semi-conducting glaze other than containing a large amount of glass phase and a small amount of bubble, also
Conductive crystallization or solid solution containing various forms, these conductive phases are through between glass matrix, constituting continual conduction
Network.
The electric conductivity of semi-conducting glaze depends primarily on the conductive characteristic of semiconductor crystal phase in glaze, and semiconductor die compares height
When, the gloss on glaze surface and the chemical stability of glaze are deteriorated, and the gloomy tarnish in glaze surface has harsh feeling, since crystal phase is more, lead to
Normal thermal expansion coefficient is also higher, it is difficult to prepare compression glaze, cannot match well with porcelain body, be the pass of semi-conducting glaze material development
Key.
For this purpose, Chinese patent notification number is a kind of low partial discharge porcelain shell for transformer semiconductor of large distance of CN102531705B
It discloses, several metal oxide semiconductors is added in parent glaze according to a certain percentage, specifically in glaze and its glazing process
For the formula of TiO 23-5%, Fe2O3 18-20%, Cr2O3 2-4%.By the addition of three kinds of above-mentioned oxides, improve
The electric conductivity of glaze improves the melting property of glaze, reduces thermal expansion coefficient and matches with common glaze, reaches raising mechanical strength
Purpose, while glaze is bright and clean, has the features such as ageing resistance, long service life.
However, the program has the following problems: 1, in the formula di-iron trioxide too high levels, will lead to be formed half
The content structure of conductor glaze is loose, and structural stability is not high, and the finish of semi-conducting glaze is inadequate, dimer, semi-conducting glaze
Surface is relatively rough；2, general using containing original of the compound of potassium perhaps sodium ion as flux due to potassium or sodium element
Son amount is smaller, and chemical property is more active, and stability is poor；3, three kinds of oxides of the formula are added in parent glaze, congruent melting
Point is higher, causes to melt efficiency reduction；4, mostly use Zuoyun native now, the glazing binding ability of semi-conducting glaze is poor.
Summary of the invention
The purpose of the present invention is to provide High-voltage ceramic semi-conducting glazes, so that the structural stability of semi-conducting glaze is high, table
Face is fine and smooth, and surface is glossy, and reduces eutectic point, improves and melts efficiency；Meanwhile using east victory soil and base mud, semiconductor is improved
Binding ability after the glazing of glaze slip.
In order to achieve the above objectives, the technical scheme is that High-voltage ceramic semi-conducting glaze, semi-conducting glaze include according to
The following component of mass fraction: high potassium is 25~35 parts of iron feldspar low, and 8~14 parts of base mud, 4~10 parts of east victory soil forges talcum 1~4
Part, 20~30 parts of silica flour, 2~4 parts of barium carbonate, 12~18 parts of iron oxide red, 1~3 part of chrome oxide green, titanium dioxide 9~12
Part, 1~2 part of spodumene.
The utility model has the advantages that
1. increasing the content of titanium dioxide in the present invention, titanium dioxide and ferrous oxide are reacted, and are formed stable
Iron-titanium crystal structure, reduces the content of di-iron trioxide, so that the internal structure of semi-conducting glaze is more stable, semiconductive
Can more preferably, with the increase for using the time, the semiconducting behavior variation of semi-conducting glaze is small；Meanwhile the semi-conducting glaze of formation is by passing
The black rough surface of system becomes smooth surface russet, and the glossiness of semi-conducting glaze is fine, and surface texture is fine and smooth；
The content for increasing titanium dioxide, can be improved the corrosion resistance of semi-conducting glaze, and the scope of application is wider, in particular for acid or
The adverse circumstances such as alkalinity.
2. the present invention joined barium carbonate in three traditional oxides, barium carbonate can be used as flux, due to barium element
Atomic weight it is big, compared with traditional potassium or sodium element, barium element is more stable, for this purpose, its electrical property is more stable, especially
Be anti-breakdown performance more preferably；Meanwhile being added after barium carbonate, it can make with metal oxides such as potassium, sodium, iron, titanium, lithium, calcium, magnesium
With formation eutectic point accelerates its high-temperature fusion, accelerates melting efficiency, and makes the surface of glaze more smooth.
3. the binding force of traditional Zuoyun soil is 3.0MPa, and native binding force is won for 5.0MPa in the east that the present invention uses, and ties
Resultant force degree improves, and semi-conducting glaze formula is made to have preferable glaze slip suspendability；And base mud is a part of original blank, is used for
Semiconductor glaze slip and blank are combined, base mud can reduce the mismatch problems of glazing as a changeover portion, while using east
Victory soil and base mud, the binding ability after improving the glazing of semiconductor glaze slip.
4. improve glazing intensity to enable semi-conducting glaze formula preferably to match blank formulation, increase silica flour and
Forge talcum dosage.
5. in order to make semi-conducting glaze formula that there is preferable temperature flowing, using the low iron feldspar of high potassium.
To the preferred embodiment 1 that the improvement of base case obtains, semi-conducting glaze includes the component of following mass fraction: high potassium is low
27 parts of iron feldspar, 10 parts of base mud, 6 parts of east victory soil, 2 parts of talcum of forging, 25 parts of silica flour, 3 parts of barium carbonate, 14 parts of iron oxide red, oxygen
Change 2 parts of chrome green, 9 parts of titanium dioxide, 2 parts of spodumene.The semi-conducting glaze structural stability of the mass fraction is high, and surface is fine and smooth, table
Face is glossy, and eutectic point is low, and combines dynamics good.
To the preferred embodiment 2 that the improvement of base case obtains, semi-conducting glaze includes the component of following mass fraction: high potassium is low
25 parts of iron feldspar, 8 parts of base mud, 4 parts of east victory soil is forged 1 part of talcum, 20 parts of silica flour, 2 parts of barium carbonate, 12 parts of iron oxide red, is aoxidized
1 part of chrome green, 9 parts of titanium dioxide, 1 part of spodumene.The semi-conducting glaze structural stability of the mass fraction is high, and surface is fine and smooth, surface
Glossy, eutectic point is low, and combines dynamics good.
To the preferred embodiment 3 that the improvement of base case obtains, semi-conducting glaze includes the component of following mass fraction: high potassium is low
35 parts of iron feldspar, 14 parts of base mud, 10 parts of east victory soil, 4 parts of talcum of forging, 30 parts of silica flour, 4 parts of barium carbonate, 18 parts of iron oxide red, oxygen
Change 3 parts of chrome green, 12 parts of titanium dioxide, 1.5 parts of spodumene.The semi-conducting glaze structural stability of the mass fraction is high, and surface is fine and smooth,
Surface is glossy, and eutectic point is low, and combines dynamics good.
Specific embodiment
One, the physicochemical property of raw material
High-voltage ceramic semi-conducting glaze uses the low iron feldspar of high potassium, silica flour, forging talcum, base mud, barium carbonate, east victory
Ten kinds of soil, iron oxide red, chrome oxide green, titanium dioxide and spodumene raw materials are formulated, and specific raw material physicochemical property is as follows:
1. the low iron feldspar of high potassium: using Fujian feldspar, originate in three mineral products processing factory of Shaowu, Fujian Province.
(1) presentation quality
Before burning: being in yellow or slight yellow powdery material.
After burning: white frit shape, mellow and full smooth, section relatively light is evenly distributed with a small amount of stain.
(2) chemical analysis
| SiO2 | AI2O3 | Fe2O3 | TiO2 | CaO | MgO | K2O | Na2O | LL |
| % | % | % | % | % | % | % | % | % |
| 66.2 | 16.0 | 0.2 | / | 0.7 | 0.5 | 11.5 | 3.0 | 0.1 |
(3) fineness
Fujian feldspar feldspar powder is a kind of processing material, the particle of≤0.063mm about 70% or so.
(4) mechanical iron content
Raw material after Fujian feldspar feldspar powder is processed, therefore its machinery iron is 0.01% or so.
2. silica flour: Yichuan silica flour originates in Yichuan Yin Feng mining industry Co., Ltd.
(1) presentation quality
Before burning: being in dark brown or lark powder.
After burning: white or yellow-white powder contains a small amount of black impurity.
(2) chemical analysis
| SiO2 | AI2O3 | Fe2O3 | TiO2 | CaO | MgO | K2O | Na2O | LL |
| % | % | % | % | % | % | % | % | % |
| 98.90 | / | 0.10 | / | / | / | 0.15 | / | / |
(3) fineness
Yichuan silica flour is a kind of natural superfine powdery material, the particle of >=0.063mm only 3% or so.
(4) mechanical iron content
Yichuan silica flour is the raw material that a kind of fineness does not have to processing, therefore its machinery iron is very low, 0.001% or so.
3. base mud: workshop
(1) presentation quality
Before burning: being in canescence fine-powdered material.
After burning: being in pale yellow piece, be sintered.
(2) chemical analysis
(3) fineness
320 mesh screen residues are 0.12%.
4. east victory soil: originating in Ordos City, Inner Mongolia Autonomous Region Jungar Banner
(1) presentation quality
Before burning: gray/grey black is blocky, and blocky containing a small amount of yellow/carbonarius, matter is soft, fine and smooth, there is sliding sense.
After burning: blocky in ash/canescence, there is a small amount of yellow black spot on surface, and section is in grey black/grey/greyish white color lump
Shape simultaneously has a small amount of yellow black patches, un-sintered.
(2) chemical analysis
(3) aquation rate
East victory soil is a kind of clay of high aquation rate, is summarized by test over the years, and average water rate is on 96% left side
The right side, aquation rate are the smallest also 94% or more.
(4) binding force
East victory soil is high plasticity clay, and binding force is strong to the dry bending for improving green body averagely in 5.0MPa or so
Degree plays a decisive role, and adhesion degree is strong.
5. forging talcum: originating in Guangxi
(1) presentation quality
Before burning: white bulk.
After burning: white bulk.
(2) chemical analysis
6. iron oxide red: being purchased from the chemical plant Ba Yu
(1) presentation quality
Before burning: being in peony powder-material.
After burning: melting block in dark brown.
(2) chemical analysis
7. chrome oxide green: being purchased from the chemical plant Ba Yu
(1) presentation quality
Before burning: dark green powder-material.
After burning: dark green powder-material.
(2) chemical analysis
8. titanium dioxide: being purchased from the chemical plant Ba Yu
(1) presentation quality
Before burning: white powder-material.
After burning: being in ivory buff powder-material.
(2) chemical analysis
9. spodumene: being purchased from the chemical plant Ba Yu
(1) presentation quality
Before burning: in light yellow or shallow white particle.
After burning: white or shallow white molten particle.
(2) chemical analysis
10. barium carbonate: being purchased from the chemical plant Ba Yu
(1) presentation quality
Before burning: white powder.After burning: white powder.
(2) fineness
Barium carbonate is a kind of superfine powder, and >=63 microns of particle is 0.
(3) purity: BaCO3 >=95%
Two, formula design and test
1. formula design and test:
According to function caused by the different performance of raw material, successively devises several formulas and carry out Physicochemical test, test
Method is carried out by Xian Electrical Ceramics Research Institute " the electroceramics inspection of raw and process materials and technology controlling and process test method ".By being comprehensively compared, select
Cost performance relatively best semi-conducting glaze formula.Formula and physicochemical property are as follows:
(1) semi-conducting glaze formula:
(2) semi-conducting glaze is formulated ball-milling technology
The production of semi-conducting glaze: by formula using once feeding intake, expect: ball: water=1:2:1.2, the control of ball milling fineness are 360
Mesh sieve margin (>=0.045mm) is 0.1~0.3%.
(3) semi-conducting glaze chemical component
(4) semi-conducting glaze glaze slip performance
(5) semi-conducting glaze high-temperature behavior
(6) porcelain performance
(7) semiconducting behavior
The glazed thickness of the semi-conducting glaze is 0.35~0.42mm, and surface resistivity is 6.6~9.8 × 107 Ω cm.
Electroceramics is set thus to generate a certain amount of resistance heat, surface voltage is evenly distributed.
Three, it discusses
It is proved by a series of experiments, semi-conducting glaze formula has the following characteristics that
(1) east victory soil and base mud, the binding ability after improving the glazing of semiconductor glaze slip are used.
(2) barium carbonate, iron oxide red, chrome oxide green, titanium oxide are used, makes semi-conducting glaze formula that there is stable resistance
Rate.
(3) base glaze matches very much, and glazing bending strength is made to improve 20% or more.
The semi-conducting glaze glaze slip mobility and temperature flowing performance reach production requirement, are convenient for green body glazing, product can
Well in conjunction with production base, after porcelain, 20% or more intensity is improved；The presentation quality for improving high pressure porcelain, makes insulator glaze colours
Exquisiteness is in bronzing.
What has been described above is only an embodiment of the present invention, and the common sense such as well known characteristic do not describe excessively herein in scheme.
It should be pointed out that for those skilled in the art, without departing from the inventive concept of the premise, several changes can also be made
Shape and improvement, these also should be considered as protection scope of the present invention, these all will not influence the effect and patent that the present invention is implemented
Practicability.The scope of protection required by this application should be based on the content of the claims, the specific embodiment party in specification
The records such as formula can be used for explaining the content of claim.
Claims (4)
1. High-voltage ceramic semi-conducting glaze, which is characterized in that the semi-conducting glaze includes the component of following mass fraction: high potassium is low
25~35 parts of iron feldspar, 8~14 parts of base mud, 4~10 parts of east victory soil, 1~4 part of talcum of forging, 20~30 parts of silica flour, barium carbonate 2
~4 parts, 12~18 parts of iron oxide red, 1~3 part of chrome oxide green, 9~12 parts of titanium dioxide, 1~2 part of spodumene.
2. High-voltage ceramic semi-conducting glaze according to claim 1, it is characterised in that: the semi-conducting glaze includes following matter
Measure the component of number: high potassium is 27 parts of iron feldspar low, and 10 parts of base mud, 6 parts of east victory soil, 2 parts of talcum of forging, 25 parts of silica flour, barium carbonate 3
Part, 14 parts of iron oxide red, 2 parts of chrome oxide green, 9 parts of titanium dioxide, 2 parts of spodumene.
3. High-voltage ceramic semi-conducting glaze according to claim 1, it is characterised in that: the semi-conducting glaze includes following matter
Measure the component of number: high potassium is 25 parts of iron feldspar low, and 8 parts of base mud, 4 parts of east victory soil, 1 part of talcum of forging, 20 parts of silica flour, barium carbonate 2
Part, 12 parts of iron oxide red, 1 part of chrome oxide green, 9 parts of titanium dioxide, 1 part of spodumene.
4. High-voltage ceramic semi-conducting glaze according to claim 1, it is characterised in that: the semi-conducting glaze includes following matter
Measure the component of number: high potassium is 35 parts of iron feldspar low, and 14 parts of base mud, 10 parts of east victory soil, 4 parts of talcum of forging, 30 parts of silica flour, barium carbonate
4 parts, 18 parts of iron oxide red, 3 parts of chrome oxide green, 12 parts of titanium dioxide, 1.5 parts of spodumene.
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| CN111995434B (en) * | 2020-09-11 | 2022-04-08 | 重庆鸽牌电瓷有限公司 | Green electroceramic glaze and preparation method thereof |
| CN113416057B (en) * | 2021-07-08 | 2022-05-31 | 萍乡强盛电瓷制造有限公司 | Production raw material of disc-shaped insulator with good insulating property and preparation method |
| CN116003162B (en) * | 2022-12-14 | 2023-08-08 | 萍乡学院 | Electroceramics semiconductor glaze and preparation method thereof |
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|---|---|---|---|---|
| CN101172879A (en) * | 2007-10-30 | 2008-05-07 | 西安电力机械制造公司 | Inorganic bonding glaze and porcelain bushing bonding method for high-pressure porcelain sleeve |
| CN102557735A (en) * | 2011-12-13 | 2012-07-11 | 重庆鸽牌电瓷有限公司 | Formula of high-voltage insulation white glaze |
| CN102838383A (en) * | 2012-09-27 | 2012-12-26 | 重庆鸽牌电瓷有限公司 | High-voltage insulation sky blue glaze formula |
| CN102838384A (en) * | 2012-09-27 | 2012-12-26 | 重庆鸽牌电瓷有限公司 | High-voltage insulation ceramic ash glaze formula |
| CN103497004A (en) * | 2013-09-18 | 2014-01-08 | 重庆鸽牌电瓷有限公司 | High-voltage ceramic insulated dark blue glaze |
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2017
- 2017-01-03 CN CN201710002735.1A patent/CN106630634B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101172879A (en) * | 2007-10-30 | 2008-05-07 | 西安电力机械制造公司 | Inorganic bonding glaze and porcelain bushing bonding method for high-pressure porcelain sleeve |
| CN102557735A (en) * | 2011-12-13 | 2012-07-11 | 重庆鸽牌电瓷有限公司 | Formula of high-voltage insulation white glaze |
| CN102838383A (en) * | 2012-09-27 | 2012-12-26 | 重庆鸽牌电瓷有限公司 | High-voltage insulation sky blue glaze formula |
| CN102838384A (en) * | 2012-09-27 | 2012-12-26 | 重庆鸽牌电瓷有限公司 | High-voltage insulation ceramic ash glaze formula |
| CN103497004A (en) * | 2013-09-18 | 2014-01-08 | 重庆鸽牌电瓷有限公司 | High-voltage ceramic insulated dark blue glaze |
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