CN1221710A - Conductive glass lining composition - Google Patents
Conductive glass lining composition Download PDFInfo
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- CN1221710A CN1221710A CN 97129747 CN97129747A CN1221710A CN 1221710 A CN1221710 A CN 1221710A CN 97129747 CN97129747 CN 97129747 CN 97129747 A CN97129747 A CN 97129747A CN 1221710 A CN1221710 A CN 1221710A
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- glass lining
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- composition
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Abstract
A conductive glass lining composition includes 100 parts by weight of a frit and 0.05 to 1.5 parts by weight of a metal fiber of 0.1 to 30 um in diameter, 1.5 to 10 mm in length and a length-to-diameter ratio of not less than 50.
Description
The present invention relates to a kind of conductive glass lining composition that is used for glass lining equipment, this equipment is made base material with mild steel plate or stainless steel plate, thereby makes them can bear harsh working conditions in the industry such as chemistry, medicine, food.
Thereby conventional glass lining equipment is by the levigate coating glaze that the thickness of roasting on base material such as mild steel plate or stainless steel plate is approximately 0.2-0.4mm levigate coating glaze firmly to be bonded on the base material, and the roasting thickness higher surface layer glaze of erosion resistance that is generally 0.8-2.0mm obtains subsequently.
Because constituting the glass lining material of glass lining equipment is that a kind of volume specific resistance is 1 * 10
13-10
14The insulating material of Ω cm, if glass lining equipment moves and stirs with nonaqueous organic liquid, the quantity of electric charge is just well beyond electrical leakage quantity, thereby produces the static of tens thousand of or hundreds thousand of volts, even glass lining equipment ground, this also can cause glass lining material breaks or blast.
In order to prevent above problem, when glass lining equipment is used to stir non-water-soluble organic liquid, embedding in advance Ta tinsel or twine the Ta wire in the glass lined nexine along surface such as dividing plate.Yet it is difficult that the Ta metal covers whole glass lining surface, does not also obtain the method that static is fully taken precautions against so far.Also have,, replace glass lining equipment with hardware such as stainless steel reckoning with generation under a large amount of electrostatic situations.
Example as glass lining equipment with anti-electrostatic facility, Japanese Utility Model (special permission is open) 7-28834 discloses a kind of glass lining metal tin, ancient piece of jade, round, flat and with a hole in its centre is covered by the bottom glass coating in it, the top glass coating covers on the bottom glass coating simultaneously, wherein the top glass coating has the conductive glass of platinum silk to make by embedding, and this wire links to each other with the base material of metal tin.Yet, do not have the part of embedding platinum silk may not can to make glass lining that too big static resistance is arranged.
Also have, thereby Japanese patent laid-open publication gazette 60-25380 discloses and has a kind ofly joined to have in the foliated glass material that predetermined glass forms and with spray gun or dipping bath and come glazing to make the method for glass lining product by growing inorganic fibre for 0.1-3mm, and wherein the fiber of 2-10% is added in 100% the frit.In this patent, the inorganic fibre that exemplifies is the Fibrotic glass that composition is different from vitreous enamel or industrial glass that comes from; Natural mineral fiber such as ore fiber and kaolinite (Kaowool) cotton; The material of fibers such as Artificial Ceramic fiber or whisker such as zirconium white, aluminum oxide, chromic oxide or whisker.The purpose that adds fiber is in order to reduce the bubble in the enamel product, to prevent to form big bubble and improve anti-color dot, anti-glaze fragility (crack), resistance to heat shocks and anti-mechanical shock.
Japanese patent laid-open publication gazette 4-8390 discloses a kind of glaze compositions that comprises frit, and wherein, said composition comprises that 100 parts of (weight) frits and 20-100 part (weight) diameter are that 0.2-1um, length-to-diameter ratio are not less than 20 inorganic crystal whisker.This whisker is inorganic monocrystalline whisker, and it is selected from titanium oxide, potassium titanate, aluminum oxide, silicon carbide and silicon nitride.The purpose that adds whisker is to give the glass lining cutting processing and improve wear resistance.
Therefore, an object of the present invention is to provide a kind of glass lining composition, it can provide the conductive glass lining with excellent volume specific resistance.
Conductive glass lining composition of the present invention comprises that the diameter of 100 parts of (weight) frits and 0.05-1.5 part (weight) is that 0.1-30 μ m, length are that 1.5-10mm, length-to-diameter ratio are not less than 50 steel fiber.
Fig. 1 is explanation is carried out 3 tests of volume specific resistance to the sample that obtains in embodiment and comparing embodiment a synoptic diagram.
Metallic fiber quantity from join the glass lining composition and composition spray glazing Relation between the energy is wished metal used in conductive glass lining composition of the present invention The diameter of fiber is littler. This diameter is 0.1-30 μ m, be preferably 0.5-10 μ m. If gold Belong to the diameter of fiber less than 0.1 μ m, metallic fiber will be difficult to processing and its cost will hold it back existing Application. If diameter surpasses 30 μ m, the slip-stream viscosity variation of glass lining composition and Spray the glazing performance with obvious step-down. Therefore less than 0.1 μ m with greater than the diameter of 30 μ m be not Preferably. The metallic fiber diameter is more little, and its apparent volume is more big, so, reduce added gold It is possible belonging to fiber number, and considers from the angle of production technology, when the sintered glass lining In the time, be good like this.
The length of metallic fiber is 1.5-10mm, is preferably 1.5-5.0mm, if the metal fibre The length of dimension just is difficult to metallic fiber is cut into shorter less than 1.5mm. If length surpasses 10mm, the slip-stream viscosity of glass lining composition is with regard to variation, and injection glazing performance will be obviously Step-down. Therefore, not preferred less than 1.5mm and the length that surpasses 10mm.
The length-to-diameter ratio of steel fiber should be not less than 50.If the length-to-diameter ratio of steel fiber less than 50, then needs a large amount of steel fibers to improve glass-lined electroconductibility.Therefore, not preferred less than 50 length-to-diameter ratio.
The conductive glass lining composition according to the present invention, the diameter of wherein used steel fiber is in above scope.Yet the size of steel fiber and some positions can be less than above scopes.When the described frit in steel fiber and back mixed mutually, steel fiber was broken and cuts.Thereby make size become littler.When the conductive glass composition by glazing with cover when being coated with, broken and cut after steel fiber can mix mutually with steel fiber with above size.This outer permeation is to the not influence of electroconductibility of the conductive glass lining coating that obtained.
Conductive glass lining composition of the present invention comprises above-mentioned steel fiber.The steel fiber that replaces joining in the frit by adding metal-powder such as platinum powder also can obtain similar advantage.Yet,, require to add metal-powder above 10% in order to obtain and the similar volume specific resistance of glass lining composition that comprises steel fiber.This has just increased cost, so in fact can not use metal-powder.Yet, surpassing 10% metal-powder if add, glass lining is difficult to obtain slick sintered surface, and will produce bubble, thereby, consider that from the angle of quality metal-powder also is unpractical.
Steel fiber is by multiple fibrous, and they are selected from the alloy of stainless steel metal, precious metal family metal, platinum and platinum metals.For stainless steel metal, can use volume specific resistance is 7.4 * 10
-5The SUS-316 fiber of Ω cm, volume specific resistance are 7.2 * 10
-5SUS-304 fiber of Ω cm or the like.Concerning the precious metal fiber, can use volume specific resistance is 1.6 * 10
-6The Ag fiber of Ω cm, volume specific resistance are 2.4 * 10
-6The Au fiber of Ω cm, volume specific resistance are 10.6 * 10
-6Pt fiber of Ω cm or the like.For the alloy fiber of platinum and platinum metals, for example, can use the alloy of Pt and Pd, Ir, Rh, Os and/or Ru.
Conductive glass lining composition of the present invention can be used as bottom or surface layer.Do not require and the firm bonding bottom of matrix metal for requiring the chemically-resistant oxidation, cheap stainless steel metal fibre is preferred.For the surface layer that requires the chemically-resistant oxidation, precious metal fiber, alloy fiber etc. are preferred.
To join 100 parts of steel fiber weight in (weight) frit are 0.05-1.5 parts (weight), be preferably 0.05-1.0 part (weight).If the add-on of steel fiber is less than 0.05 part, electroconductibility does not have too big improvement.If add-on surpasses 1.5 parts (weight), the slip-stream viscosity of glass lining composition is sprayed the glazing performance with obvious step-down with variation.Therefore, not preferred less than 0.05 part (weight) with greater than the add-on of 1.5 parts (weight).The add-on of steel fiber is in above-mentioned scope, and glass lining can obtain the excellent quality that do not have bubble and do not have the irregularity sintered surface.
Frits all in the conductive glass lining composition of the present invention is not particularly limited.Available any general frit.For example, available following frit with (A)-(E) composition.
(A) SiO of 46-67% (weight) (40-75 mole %)
2+ TiO
2+ ZrO
2, SiO wherein
2Be 46-67% (weight) (40-75 mole %), TiO
2Be 0-18% (weight) (0-20 mole %) and ZrO
2Be 0-12% (weight) (0-12 mole %); (A) weight percentage is pressed SiO
2Calculate;
(B) R of 8-22% (weight) (7-22 mole %)
2O, wherein Na
2O is 8-22% (weight) (7-22 mole %), K
2O is 0-16% (weight) (0-15 mole %) and Li
2O is 0-10% (weight) (0-15 mole %); (B) weight percentage is pressed Na
2O calculates;
(C) RO of 0.9-7% (weight) (1-7 mole %), wherein CaO is 0.9-7% (weight) (1-7 mole %), BaO is 0-6% (weight) (0-6 mole %), and ZnO is that 0-6% (weight) (0-6 mole %) and MgO are 0-5% (weight) (0-6 mole %); (C) weight percentage is pressed CaO and is calculated;
(D) B of 0-22% (weight) (0-20 mole %)
2O
3+ Al
2O
3, wherein, B
2O
3Be 0-22% (weight) (0-20 mole %) and Al
2O
3Be 0-6% (weight) (0-10 mole %); (D) weight percentage is pressed B
2O
3Calculate;
(E) CoO+NiO+MnO of 0-5% (weight) (0-4 mole %)
2, wherein CoO is 0-5% (weight) (0-4 mole %), NiO is 0-5% (weight) (0-4 mole %) and MnO
2Be 0-5% (weight) (0-4 mole %); (E) weight percentage is pressed CoO and is calculated.
As colouring component, also can add and be selected from Sb
2O
5, Cr
2O
3, Fe
2O
3And SnO
2In at least a component.Join this component quantity in 100 parts of (weight) glass frit compositions with Fe
2O
3Calculating is not more than 5% (weight) (5 moles of %).In order to make the frit fusing, at SiO
2, CaO or Na
2Can use the fluorochemical that is not more than 5 moles of % among the O.For example, available Na
2SiF
6Come instead of part SiO
2, or Na
2O uses CaF
2Replaced C aO and use Na
3AlF
6Replace Al
2O
3Also have, these components are all used in frit usually.
Glass lining composition of the present invention can for example carry out glazing with ordinary method at conventional base material on mild steel plate and the stainless steel plate etc.Certainly, differing materials can be combined application, and can change the glazing time according to purposes.For example, conventional glass lining composition can be used as bottom, and conductive glass lining composition of the present invention is as surface layer; Conductive glass lining composition of the present invention can be used as bottom, and conventional glass lining composition is as surface layer; Or conductive glass lining composition of the present invention is promptly as bottom, again as surface layer.
The conductive glass lining composition according to the present invention can provide a kind of volume specific resistance lower glass lining.
Embodiment,
Further describe conductive glass lining composition of the present invention below by following work embodiment and comparing embodiment.
Embodiment
Table 1 shows bottom and used ratio of mixture (weight percentage) and the composition (molecular fraction) of investment precoat.
Table 1
The bottom surface layer
Ratio of mixture (weight percentage)
SiO
2+TiO
2+ZrO
2 41 61
R
2O(Na
2CO
3+K
2CO
3+Li
2CO
3) 25 23
RO(CaCO
3+BaCO
3+MgCO
3+ZnCO
3) 11 9
H
3BO
3+Al
2O
3 21 6
CoO+NiO+Mn
2CO
3 2 1
Form (molar percentage)
SiO
2+TiO
2+ZrO
2 55 73
R
2O(Na
2O+K
2O+Li
2O) 21 17
RO(CaO+BaO+MgO+ZnO) 6 5
B
2O
3+Al
2O
3 15.5 4
CoO+NiO+MnO
2 2.5 1
By being ground, the steel fiber of the bottom of 100 parts (weight) or investment precoat and the different umbers (weight) that are shown in Table 2,2 parts of (weight) clays, 0.05 part of (weight) CMC, 0.3 part of (weight) bariumchloride and an amount of water prepare the grinding admixtion.Be that 1.0mm, diameter are this grinding admixtion of glazing on the garden shape mild steel plate of 105mm at thickness under the sintering condition shown in the table 2.Steel fiber is Stainless Steel Fibre and platinum fiber (1) and (2).Stainless Steel Fibre is produced by Nasu Bussan K.K., and diameter is 8 μ m, the long 5mm of being.Platinum fiber (1) is produced by Tanaka Kiknzoku K.K., and diameter is 8 μ m, the long 2mm of being.Platinum fiber (2) is also produced by Tanaka Kikinzoku K.K., and diameter is 0.5 μ m, the long 2mm of being.Platinum powder used in comparing embodiment is produced by KoujnndokagakuKenkyuus K.K, and diameter is 1-10 μ m.
Test the volume of sample resistivity that is obtained with three point methods that are shown among Fig. 1.Its result also is shown in Table 2.
Find out obviously that from table 2 the embodiment 1-3 that wherein steel fiber joined in bottom and the investment precoat and 6-11 and steel fiber wherein do not join bottom and compare with 13 with the comparing embodiment 12 in the investment precoat and obviously have lower volume specific resistance and show electric conductivity preferably.
Wherein not join the volume specific resistance of the embodiment 4 in the base coat be 1.5 * 10 to steel fiber
10Ω cm.Wherein not join the volume specific resistance of the embodiment 5 in the surface layer be 1.3 * 10 to steel fiber
11Ω cm.Although compare with 6-11 with embodiment 1-3, these results obviously do not show lower numerical value, and 12-13 compares with comparing embodiment, and they still have numerical value preferably.Therefore, according to cost and purposes, embodiment 4 and 5 also is enough to satisfy practical application.
The volume specific resistance that wherein adds the comparing embodiment 14 of 5 parts of (weight) platinum powders is 2.5 * 10
14Ω cm.The volume specific resistance that wherein adds the comparing embodiment 15 of 20 parts of (weight) platinum powders is 4.7 * 10
3Ω cm.Clearly adding 20 parts of (weight) platinum powders causes the volume resistance rate score of glass lining composition similar to conductive glass lining composition of the present invention.Yet for the consideration of cost, platinum powder is expensive can not using in glass lining.Table 2 product comparative example of the present invention product
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15+ + Pt 0.05 0.10 0.20 0 0.50 1.0 1.5--5％ 20％850℃ 850℃15 15+Pt ( 2 ) 0.05 0.5 1.0 1.5--850℃15+ + Pt 0.05 0.10-------5％ 20％800℃ 800℃15 15+Pt ( 1 ) --0.20 0.50 0 1.0 1.5--800℃15+Pt ( 2 ) 0.4 0.5 1.0 1.5--800℃15 ( mm ) 0.35 0.37 0.30 0.28 0.30 0.30 0.30 0.30 0.33 0.35 0.35 0.30 0.30 0.32 0.35 ( mm ) 0.95 0.93 0.95 1.10 1.20 1.30 1.10 0.90 0.95 1.00 1.10 1.10 1.00 1.00 1.10 ( mm ) 1.30 1.30 1.25 1.38 1.50 1.60 1.40 1.20 1.28 1.35 1.45 1.40 1.30 1.32 1.45 1.0×9.0×8.0×1.5×1.3×2.0×1.3×1.8×1.3×1.0 ×0.5 ×5.4 ×5.4 ×2.5×10144.7 * 10
4(Ω cm) 10
810
410
310
1010
1110 10
010
710
310
010
010
1310
13Electric conductivity zero ◎ ◎ △ △ ◎ ◎ zero ◎ ◎ ◎ * * * ◎
(explanation) electric conductivity ◎: fine zero: good △: inferior *: bad
Claims (3)
1. conductive glass lining composition, it comprises that the frit of 100 parts (weight) and 0.05-1.5 part (weight) diameter are 0.1-30 μ m, longly are not less than 50 steel fiber for 1.5-10mm and length-to-diameter ratio.
2. the composition of claim 1, wherein steel fiber is one or more steel fibers that are selected from the alloy fiber of Stainless Steel Fibre, precious metal metal fiber, platinum and platinum metals.
3. the composition of claim 1, wherein frit has the composition of following (A)-(E):
(A) SiO of 46-67% (weight)
2+ TiO
2+ ZrO
2, SiO wherein
2Be 46-67% (weight), TiO
2Be 0-18% (weight) and ZrO
2Be 0-12% (weight); (A) weight percentage is pressed SiO
2Calculate;
(B) R of 8-22% (weight)
2O, wherein Na
2O is 8-22% (weight), K
2O is O-16% (weight) and Li
2O is 0-10% (weight); (B) weight percentage is pressed Na
2O calculates;
(C) RO of 0.9-7% (weight), wherein CaO is 0.9-7% (weight), and BaO is 0-6% (weight), and ZnO is that 0-6% (weight) and MgO are 0-5% (weight); (C) weight percentage is pressed CaO and is calculated;
(D) B of 0-22% (weight)
2O
3+ Al
2O
3, B wherein
2O
3Be 0-22% (weight), Al
2O
3Be 0-6% (weight); (D) weight percentage is pressed B
2O
3Calculate;
(E) CoO+NiO+MnO of 0-5% (weight)
2, wherein CoO is 0-5% (weight), and NiO is 0-5% (weight), and NiO is 0-5% (weight) and MnO
2Be 0-5% (weight); (E) weight percentage is pressed CoO and is calculated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97129747 CN1123545C (en) | 1997-12-31 | 1997-12-31 | Conductive glass lining composition |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97129747 CN1123545C (en) | 1997-12-31 | 1997-12-31 | Conductive glass lining composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1221710A true CN1221710A (en) | 1999-07-07 |
| CN1123545C CN1123545C (en) | 2003-10-08 |
Family
ID=5177693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 97129747 Expired - Lifetime CN1123545C (en) | 1997-12-31 | 1997-12-31 | Conductive glass lining composition |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1123545C (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101500957B (en) * | 2006-08-07 | 2012-08-29 | 池袋珐琅工业株式会社 | Glaze composition for glass lining |
| CN102775068A (en) * | 2012-08-03 | 2012-11-14 | 上海锦众信息科技有限公司 | Preparation method for sealing piece of fuel cell |
| CN104402237A (en) * | 2014-11-11 | 2015-03-11 | 中国人民解放军国防科学技术大学 | Low-cost electro-conductive glass and preparation method thereof |
| CN109081584A (en) * | 2018-09-21 | 2018-12-25 | 佛山市禅城区诺高环保科技有限公司 | A kind of heat and corrosion resistant enamel coating |
| CN112154129A (en) * | 2018-05-25 | 2020-12-29 | 尤尼弗瑞克斯 I 有限责任公司 | Inorganic fiber |
-
1997
- 1997-12-31 CN CN 97129747 patent/CN1123545C/en not_active Expired - Lifetime
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101500957B (en) * | 2006-08-07 | 2012-08-29 | 池袋珐琅工业株式会社 | Glaze composition for glass lining |
| CN102775068A (en) * | 2012-08-03 | 2012-11-14 | 上海锦众信息科技有限公司 | Preparation method for sealing piece of fuel cell |
| CN102775068B (en) * | 2012-08-03 | 2016-03-30 | 上海锦众信息科技有限公司 | A kind of preparation method of diaphragm seal of fuel cell |
| CN104402237A (en) * | 2014-11-11 | 2015-03-11 | 中国人民解放军国防科学技术大学 | Low-cost electro-conductive glass and preparation method thereof |
| CN112154129A (en) * | 2018-05-25 | 2020-12-29 | 尤尼弗瑞克斯 I 有限责任公司 | Inorganic fiber |
| CN112154129B (en) * | 2018-05-25 | 2022-10-14 | 尤尼弗瑞克斯 I 有限责任公司 | Inorganic fiber |
| CN109081584A (en) * | 2018-09-21 | 2018-12-25 | 佛山市禅城区诺高环保科技有限公司 | A kind of heat and corrosion resistant enamel coating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1123545C (en) | 2003-10-08 |
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Granted publication date: 20031008 |
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