US3876455A - Electric insulating porcelain article - Google Patents

Electric insulating porcelain article Download PDF

Info

Publication number
US3876455A
US3876455A US360423A US36042373A US3876455A US 3876455 A US3876455 A US 3876455A US 360423 A US360423 A US 360423A US 36042373 A US36042373 A US 36042373A US 3876455 A US3876455 A US 3876455A
Authority
US
United States
Prior art keywords
porcelain
article
zircon
weight
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US360423A
Inventor
Noboru Higuchi
Yutaka Ogawa
Kyosuke Tunekawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NGK Insulators Ltd
Original Assignee
NGK Insulators Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NGK Insulators Ltd filed Critical NGK Insulators Ltd
Application granted granted Critical
Publication of US3876455A publication Critical patent/US3876455A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/009After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/50Coating 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
    • C04B41/5024Silicates
    • CCHEMISTRY; METALLURGY
    • C04CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04BLIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B41/00After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/80After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
    • C04B41/81Coating or impregnation
    • C04B41/85Coating or impregnation with inorganic materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B19/00Apparatus or processes specially adapted for manufacturing insulators or insulating bodies
    • H01B19/04Treating the surfaces, e.g. applying coatings
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/02Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
    • H01B3/025Other inorganic material
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S174/00Electricity: conductors and insulators
    • Y10S174/01Anti-tracking
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/24Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24802Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.]
    • Y10T428/24926Discontinuous or differential coating, impregnation or bond [e.g., artwork, printing, retouched photograph, etc.] including ceramic, glass, porcelain or quartz layer

Definitions

  • the electric insulating porcelain article whose excellent electrical resistance properties and mechanical strength are not deteriorated even when used in an atmosphere containing the decomposition products obtained with SF gas is subjected to spark discharge.
  • the electric insulating porcelain article comprises an electric porcelain body and a porcelain coating applied to the surface of the porcelain body, the coating containing not less than 50 by weight of zircon and having a thermal expansion coefficient lower than that of the porcelain body.
  • the invention pertains to an electric insulating porcelain article, which is composed of a generally used electric porcelain body and, applied to the surface thereof, a porcelain coating containing not less than 50 by weight of zircon, and hence is not deteriorated in its excellent insulation resistance and mechanical strength even when used in an atmosphere containing decomposed products of SF gas which have been produced due to spark discharge.
  • An electric insulating porcelain article such as electric insulator, bushing or the like, is ordinarily prepared by applying a glaze to a porcelain body containing a crystal phase consisting of 3 to 35 (by weight based on the weight of said porcelain body; the same shall apply hereinafter) of quartz and 6 to 30 of rnullite; to 45 of cristobalite, 2 to 15 of quartz and 15 to 30 of mullite; 15 to 45 ofcristobalite,'2 to 15 of quartz, 15 to 35 of mullite and 3 to 45 of corundum; up to 35 of quartz, 6 to 30 of mullite and l to 45 of corundum; 3 to 35 of quartz, 6 to 30 of mullite and l to 30 of zircon; or up to 35 of quartz, 6 to 30 of mullite, l to 45 of corundum and l to 30 of zircon. Further, such porcelain body contains a glass phase in addition to such crystal phase as mentioned above.
  • the surface of the glaze is too smooth to apply a resincoating which firmly adhere to the porcelain'article.
  • the surface of an unglazed porcelain body is somewhat coarse, an attempt has been made to apply a resin coating to the surface of such unglazed porcelain body so as to firmly adhere the resin-coating tothe porcelain body.
  • the unglazed porcelain body has no such effect of compression glaze as mentioned previously, so thatthere has been such drawback that no desired mechanical strength can be attained unless the porcelain bodyis made large in size.
  • the thermal expansion coefficient of the resin coating is larger than that of the porcelain body, so that there has been suc-hdrawback that the resin coating is peeled off when the porcelain article is used over a long period of time.
  • zircon porcelain article the whole body of which is composed of a zircon article.
  • the zircon porcelain is narrow in firing temperature range and great in firing deformation, so that it is extremely difficult from the technical standpoint to use the zircon porcelain for commercial scale production of large-sized insulators.
  • the zircon porcelain has had such drawback that it is not suitable for commercial scale production of insulating porcelain articles.
  • the present invention is based on the finding that when a porcelain containing not less than 50 by weight of zircon is coated on a generally used electric porcelain body, the resulting porcelain article is not deteriorated in insulation resistance even when used in an atmosphere containing decomposed products of SF, gas which have been produced due to spark discharge, and gives the same effect as the so-called effect of compression glaze, since the porcelain coating formed on the generally used electric porcelain body is smaller in thermal expansion coefficient than the electric porcelain body.
  • the zircon porcelain as a coating is composed of a glass phase and a crystal phase comprising a major proportion of zircon and a minor proportion of mullite, zirconia, quartz and the like crystals.
  • FIG. 1 is a graph showing the variations in insulation resistance of various electric porcelain bodies in SF, gas contaminated due to spark discharge; and
  • FIG. 2 is a graph showing the variations in insulation resistance of zircon porcelain bodies containing varying amounts of zircon in SF gas contaminated due to spark discharge.
  • zircon porcelain according to the present invention is not deteriorated in insulation resistance even when used in an atmosphere containing decomposed products of SF gas which have been produced due to spark discharge, and why this effect is particularly marked in the case of a zircon porcelain containing not less than 50 by weight of zircon, are as follows:
  • test pieces of 10 mm. in diame- 'ter and mm. in length were prepared from such electric porcelain batches (l) to (3) and zircon porcelain batch as shown in Table 2, and the thus prepared test pieces were individually fired in an ordinary kiln for firing of porcelain insulator to obtain samples.
  • Table 2 bonate, zinc white, etc. on an unfired body of a generally used electric porcelain, which, when fired, comes (wt%) to have such crystal phase as mentioned previously, d f r f ch Tt 20 and then firing at a temperature of 1,250 to 1,350C.
  • CaO 0.19 and M 0.08 Same as above Alumina 50 SiO 3l.6l K 0: 2.52 g. not more than 5.0 by weight of at least one oxide 3 1 0? 9 28-113 2 L04 selected from the group consisting of TiO and Fe O ii E the sum of said oxides (d) to (g) being 1.1 to 12 by shred 10 we1ght and the ratio ZrO,/S1O being 0.8 to 2.0.
  • Synthetic zircon may be used in place of the raw ma- Zircon Zircon sand265 510.: 36.87 MgO: 0.61 terial zircon sand. Porcelain This zircon porcelain coating has a thermal expan- 2. $2,32 ,22 Dolomite 3 45 98 Bao 49 s1on coefficient of 3.9 to 4.9 X 10 /C.
  • the porcelain article according to the present invention can be easily obtained by coating to a thickness of about 0.2 to 0.6 mm.
  • a green layer for zircon porcelain coating comprising a mixture of zircon sand, feldspar,
  • the coating is completely vitrified by firing at the aforesaid temperature to show a water absorption ratio of 0 so that the porcelain article is not de-,
  • the zircon porcelain coating according to the present invention may be applied to the whole surface of the porcelain body, but it is preferable that the coating is applied to at least a surface to be brought into contact with SP gas, and a generally used compression glaze is applied to the remaining surface.
  • Test Example 1 A rod-1ike test piece of mm. in diameter and 120 mm. in length was prepared from a green body for porcelain insulator comprising 37 (by weight; the same shall apply hereinafter) of Amakusa pottery stone, 26 of Tsushima feldspar and 37 of Gaerome clay. Subsequently, the test piece was coated with a green layer of about 0.35 mm. in thickness for zircon porcelain coating comprising 70 of zircon sand, 5 of dolomite, 2 of feldspar; 3 of barium carbonate and 20 of clay, and then fired in a firing kiln at a maximum temperature of 1,300C. to'prepare a sample.
  • Test Example 2 A cylindrical test piece of 100 mm. in outer diameter, 60 mm. in inner diameter and 200 mm. in height was prepared from a green body for porcelain insulator comprising 35 of Amakusa pottery stone, 30 of Tsushima feldspar and 35 of Gaerome clay. Subsequently, the test piece was coated on the inner and outer surfaces with a green layer of about 0.3 mm. in thickness for zircon porcelain coating comprising 63 of zircon sand, 4 of dolomite, 2 of feldspar, 6 of alumina, 3 of barium carbonate, 2 of zinc white and 20 of clay, and then fired in a firing kiln at a maximum temperature of l,300C. to prepare a sample.
  • This sample was measured in variation of insulation resistance at the inner surface in the same manner as in Test Example 1 to obtain the results as shown in ing the atmosphereby continuously effecting spark discharge using-spark discharge electrodes (needle and plane plate) under such conditions as a gap between two electrodes of 2 mm., an applied voltage of 15 kv. and a currentof 5 mA. to obtain the results as shown in (1) of Table 3, in which were also shown the results ner as above, except that the coating according to the present invention was replaced by a generally used insulator glaze of the composition 0.20 K 0. 0.10 Na O. 0.30 CaO. 0.40 MgO. 0.70A1 O 7.00 SiO according (l) of Table 4, in which were also shown the results of measurement in inner pressure strength thereof.
  • the electric insulating porcelain article of the present invention is free from the drawbacks of the conventional electric insulating article, such as insulator or insulating bushing, and can be effectively used over a long period of time as an electric insulating article for electric appliances using SF gas as an insulating medium, without any deterioration in insulation resistance and mechanical strength.
  • the industrial value of the present invention is extremely great.
  • a porcelain electric insulating article comprising a porcelain body and a porcelain coating thereon coming into contact with the decomposition products formed when SP gas is subjected to an electrical spark, the improvement wherein the porcelain coating coming into contact with said decomposition products contains not less than 50% by weight of zircon and has a thermal coefficient of expansion lower than the thermal coefficient of expansion of said body.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Insulating Materials (AREA)
  • Glass Compositions (AREA)

Abstract

An electric insulating porcelain article whose excellent electrical resistance properties and mechanical strength are not deteriorated even when used in an atmosphere containing the decomposition products obtained with SF.sub.6 gas is subjected to spark discharge. The electric insulating porcelain article comprises an electric porcelain body and a porcelain coating applied to the surface of the porcelain body, the coating containing not less than 50 % by weight of zircon and having a thermal expansion coefficient lower than that of the porcelain body.

Description

[ 1 Apr. 8, 1975 1 ELECTRIC INSULATING PORCELAIN ARTICLE [75] Inventors: Noboru Higuchi; Yutaka Ogawa,
both of Nagoya; Kyosuke Tunekawa, Aichi, all of Japan [73] Assignee: NGK Insulators, Ltd., Mizuho Nagoya, Japan [22] Filed: May 15, 1973 [2]] Appl. No.: 360,423
[30] Foreign Application Priority Data May 18, 1972 Japan 47-49367 [52] US. Cl. 117/125; 106/396; 106/48; 117/169 A; 174/137 A; 174/209; 174/D1G. l [51] Int. Cl C03c 5/02; B32b 9/00 [58] Field of Search 174/DIG. 1, 137 A, 209; 117/125, 169 A; 200/148 G, 144 C; 106/48, 39.6
[56] References Cited UNITED STATES PATENTS 2,157,100 5/1939 Rowland 117/125 2,170,387 8/1939 Morgan 106/48 2,325,553 7/1943 Schleicher.... 117/125 2,534,327 12/1950 Whitman 117/125 3,024,303 3/1962 Smothers 117/125 3,078,186 2/1963 Trevney.... 106/48 3,166,430 1/1965 Seabright 106/48 FOREIGN PATENTS OR APPLICATIONS 735,243 8/1955 United Kingdom 106/48 1,168,817 4/1964 Germany 106/48 1,091,399 10/1960 Germany 106/48 Primary ExaminerRalph I-Iusack Assistant Examiner-William H. Schmidt Attorney, Agent, or Firm-Craig & Antonelli [57] ABSTRACT An electric insulating porcelain article whose excellent electrical resistance properties and mechanical strength are not deteriorated even when used in an atmosphere containing the decomposition products obtained with SF gas is subjected to spark discharge. The electric insulating porcelain article comprises an electric porcelain body and a porcelain coating applied to the surface of the porcelain body, the coating containing not less than 50 by weight of zircon and having a thermal expansion coefficient lower than that of the porcelain body.
14 Claims, 2 Drawing Figures PATENTEUAPR 8197s 3 876,455
susnzpgz v F G. 2
x i v lNlTlAL VALUES OF EACH ZIRCON PORCELAIN ',-O----0-"" l2 lxl IO VALUES AFTER |oo HOURS OF EACH H ZIRCON PORCELAIN 9 lo I" U) E'z Z o I, 9 I0 I '3; 1 X 3 2 I09 x 0 IO 20 3O 4O 5O 6O 7O 8O AMOUNT OF ZIRCON BY WEIGHT) ELECTRIC INSULATING PORCELAIN ARTICLE BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to an electric insulating porcelain article. More particularly, the invention pertains to an electric insulating porcelain article, which is composed of a generally used electric porcelain body and, applied to the surface thereof, a porcelain coating containing not less than 50 by weight of zircon, and hence is not deteriorated in its excellent insulation resistance and mechanical strength even when used in an atmosphere containing decomposed products of SF gas which have been produced due to spark discharge.
2. Description of the Prior Art An electric insulating porcelain article, such as electric insulator, bushing or the like, is ordinarily prepared by applying a glaze to a porcelain body containing a crystal phase consisting of 3 to 35 (by weight based on the weight of said porcelain body; the same shall apply hereinafter) of quartz and 6 to 30 of rnullite; to 45 of cristobalite, 2 to 15 of quartz and 15 to 30 of mullite; 15 to 45 ofcristobalite,'2 to 15 of quartz, 15 to 35 of mullite and 3 to 45 of corundum; up to 35 of quartz, 6 to 30 of mullite and l to 45 of corundum; 3 to 35 of quartz, 6 to 30 of mullite and l to 30 of zircon; or up to 35 of quartz, 6 to 30 of mullite, l to 45 of corundum and l to 30 of zircon. Further, such porcelain body contains a glass phase in addition to such crystal phase as mentioned above.
It is well known that if, in the above case, the thermal expansion coefficient of the glaze applied to the porcelain body is made smaller than that of the porcelain body, the porcelain article is increased in mechanical strength due to the so-called effect of compression glaze, and hence can be more effectively designed, e.g. made compact in size, etc. (see US. Pat. Nos. 2,157,100 and 3,024,303). However, the use of such a porcelain article in a system employing SF gas as the insulating medium has heretofore yielded the following drawback: Namely, silica components constituting the glaze on the surface of the porcelain article are corroded by the decomposition products obtained when SF gas is subjected to spark discharges, and the fiuorides produced through this corrosion, having a low electric resistance, result in reducing the electric resistance of the porcelain article. In order to overcome the above-mentioned drawback, a required portion of the surface of such porcelain article has sometimes been coated with an epoxy resin containing as'a filler an alumina powder or the like which is not attacked by the decomposed products of SE, gas. However,-the surface of the glaze is too smooth to apply a resincoating which firmly adhere to the porcelain'article. Further, since the surface of an unglazed porcelain bodyis somewhat coarse, an attempt has been made to apply a resin coating to the surface of such unglazed porcelain body so as to firmly adhere the resin-coating tothe porcelain body. However, the unglazed porcelain body has no such effect of compression glaze as mentioned previously, so thatthere has been such drawback that no desired mechanical strength can be attained unless the porcelain bodyis made large in size. Moreover, the thermal expansion coefficient of the resin coating is larger than that of the porcelain body, so that there has been suc-hdrawback that the resin coating is peeled off when the porcelain article is used over a long period of time.
There has been also well known a zircon porcelain article, the whole body of which is composed of a zircon article. However, the zircon porcelain is narrow in firing temperature range and great in firing deformation, so that it is extremely difficult from the technical standpoint to use the zircon porcelain for commercial scale production of large-sized insulators. Even if the zircon porcelain is forcibly used for production of largesized insulators, while overcoming the said difficulty, delicate producton techniques of high degree are required to make the resulting insulators high in cost. Thus, the zircon porcelain has had such drawback that it is not suitable for commercial scale production of insulating porcelain articles.
SUMMARY OF THE INVENTION The present invention is based on the finding that when a porcelain containing not less than 50 by weight of zircon is coated on a generally used electric porcelain body, the resulting porcelain article is not deteriorated in insulation resistance even when used in an atmosphere containing decomposed products of SF, gas which have been produced due to spark discharge, and gives the same effect as the so-called effect of compression glaze, since the porcelain coating formed on the generally used electric porcelain body is smaller in thermal expansion coefficient than the electric porcelain body. In the present invention, the zircon porcelain as a coating is composed of a glass phase and a crystal phase comprising a major proportion of zircon and a minor proportion of mullite, zirconia, quartz and the like crystals.
BRIEF DESCRIPTION OF THE DRAWINGS In the accompanying drawings, FIG. 1 is a graph showing the variations in insulation resistance of various electric porcelain bodies in SF, gas contaminated due to spark discharge; and FIG. 2 is a graph showing the variations in insulation resistance of zircon porcelain bodies containing varying amounts of zircon in SF gas contaminated due to spark discharge.
DETAILED DESCRIPTION OF THE INVENTION The reasons why the zircon porcelain according to the present invention is not deteriorated in insulation resistance even when used in an atmosphere containing decomposed products of SF gas which have been produced due to spark discharge, and why this effect is particularly marked in the case of a zircon porcelain containing not less than 50 by weight of zircon, are as follows:
Using raw materials having the chemical compositions shown in Table 1, test pieces of 10 mm. in diame- 'ter and mm. in length were prepared from such electric porcelain batches (l) to (3) and zircon porcelain batch as shown in Table 2, and the thus prepared test pieces were individually fired in an ordinary kiln for firing of porcelain insulator to obtain samples.
Table 1 Raw material Alumina Silica Feldspar Clay Zircon Dolomite Porcelain sand shred Component lg. loss 0.18 0.20 0.58 13.50 1.05 45.90 510 Trace 99.58 67.95 48.89 32.31 0.38 73.19 66.28 A120,, 99.47 0.02 17.22 33.73 0.12 21.04 Fe o 0.02 0.04 0.14 1.54 0.13 0.23 0.91 Ti Trace Trace Truce 0.98 0.33 0.10 0.05 Trace 0.15 0.33 35.78 0.15 MgO Trace Trace 0.02 0.21 17.35 0.17 K20 0.02 0.02 10.59 0.75 1.66 Na o 0.24 0.02 3.35 0.12 1.95
Table 2 bonate, zinc white, etc. on an unfired body of a generally used electric porcelain, which, when fired, comes (wt%) to have such crystal phase as mentioned previously, d f r f ch Tt 20 and then firing at a temperature of 1,250 to 1,350C.
1n 0 IXllIg ra IO 0 emica composl I OI'I I porcelain raw materials an firing The fired zircon porcelam coating cons1sts of.
a. 37 to 62 by weight of ZrO Generally used Alumina SiO 67.52 K: 2.88 b 18 5 t 465 b i ht f sio electric porcelain Silica :30 A1 0 27.85 Nap. 0.89 5 to 30 y 8 z ar Feldspar: 23 n.0,: 0.65 d. 0.1 to 5.0 by we1ght of at least one oxide se- Clay 37 226 lected from the group consisting of K 0 and Na O,
M 01 107 e. 1.0 to 10.0 b wei ht of at least one oxide ses y Same as above Alumina I 35 S10 41.16 K102 3.07 lected from the group cons st ng of Ca o and S111ca 2 5 A1203: 53.58 Na oz 1.01 f h 07 b ht f t] t peldspar; 25 P6205062 .1101. moret an 0 ywe 1g O 3. eas one OX1 6 Clay :35 'Ti0,: 0.41 selected from the group consisting of ZnO and BaO,
CaO: 0.19 and M 0.08 Same as above Alumina 50 SiO 3l.6l K 0: 2.52 g. not more than 5.0 by weight of at least one oxide 3 1 0? 9 28-113 2 L04 selected from the group consisting of TiO and Fe O ii E the sum of said oxides (d) to (g) being 1.1 to 12 by shred 10 we1ght and the ratio ZrO,/S1O being 0.8 to 2.0.
38 f 86 Synthetic zircon may be used in place of the raw ma- Zircon Zircon sand265 510.: 36.87 MgO: 0.61 terial zircon sand. Porcelain This zircon porcelain coating has a thermal expan- 2. $2,32 ,22 Dolomite 3 45 98 Bao 49 s1on coefficient of 3.9 to 4.9 X 10 /C. (25 to 650C.), coating of Feldspar :2 A1203: 9.34 K20: 0.43 which is identical with that of a generally used com- Barium pression glaze, and hence has the same effect as the socarbonate 3 Fe o z 0.51 Na oz 0.11 called effect of compression glaze on the aforesaid genl :25 erally used electric porcelain body having a thermal ex- Z1nc whlte 2 C210 1.23 o o panslon coefficient of 5.0 to 8.8 X 10 C. (25 to The thus obtained samples were individually placed in SF 8 gas, and were first measured in initial insulation resistance with application of electrodes to both ends of each sample, and then the variations with time in insulation resistance of the samples were measured, while continuously causing spark discharge by use of another sparking means provided in SF gas, to obtain such results as shown in FIG. 1. As is clear from FIG. 1, the zircon porcelain (containing 69 by weight of zircon) is far more excellent in insulation resistance than other 3 kinds of porcelains.
Funt her, 10 kinds of zircon porcelain samples varying in amiaunt of zircon were measured in insulation resistance iii the same manner as above to obtain the results as shown in FIG. 2. As is clear from FIG. 2, the effects of the zircon porcelains containing not less than by weight of zircon are particularly marked.
The porcelain article according to the present invention can be easily obtained by coating to a thickness of about 0.2 to 0.6 mm. a green layer for zircon porcelain coating comprising a mixture of zircon sand, feldspar,
clay, alumina, talc, dolomite, limestone, barium car- Further, the coating is completely vitrified by firing at the aforesaid temperature to show a water absorption ratio of 0 so that the porcelain article is not de-,
teriorated in insulating property.
The zircon porcelain coating according to the present invention may be applied to the whole surface of the porcelain body, but it is preferable that the coating is applied to at least a surface to be brought into contact with SP gas, and a generally used compression glaze is applied to the remaining surface.
It is needless to say that the same effect as above can be attained even when the coating according to the present invention is applied to '"a fired body of an unglazed generally used electric porcelain. In this case, however, it is necessary to carry out the firing two times, i.e., firing of the porcelain body and firing of the coating. It is therefore desirable to obtain the electric insulating porcelain article of the present invention by such one time firing operation that a green layer for zircon porcelain coating according to the present invention is applied to a required surface of an unfired body of generally used electric porcelain, and the resulting coated porcelain is subjected to firing, as mentioned previously.
The present invention is illustrated below with reference to test examples, in which the invention was applied to test pieces.
Test Example 1 A rod-1ike test piece of mm. in diameter and 120 mm. in length was prepared from a green body for porcelain insulator comprising 37 (by weight; the same shall apply hereinafter) of Amakusa pottery stone, 26 of Tsushima feldspar and 37 of Gaerome clay. Subsequently, the test piece was coated with a green layer of about 0.35 mm. in thickness for zircon porcelain coating comprising 70 of zircon sand, 5 of dolomite, 2 of feldspar; 3 of barium carbonate and 20 of clay, and then fired in a firing kiln at a maximum temperature of 1,300C. to'prepare a sample.
This sample was placed in SE gas in a l8-1iter vessel kept under a gas pressure of 1.2 atm., measured in initial insulationresistance with application of electrodes to both ends of the sample, and then measuredin variation of insulation resistance thereof, while contaminatto the Segers formula: and a sample (3) comprising the aforesaid test piece having no coating. From Table 3, it is understood that the sample of the present invention is excellent in properties.
Test Example 2 A cylindrical test piece of 100 mm. in outer diameter, 60 mm. in inner diameter and 200 mm. in height was prepared from a green body for porcelain insulator comprising 35 of Amakusa pottery stone, 30 of Tsushima feldspar and 35 of Gaerome clay. Subsequently, the test piece was coated on the inner and outer surfaces with a green layer of about 0.3 mm. in thickness for zircon porcelain coating comprising 63 of zircon sand, 4 of dolomite, 2 of feldspar, 6 of alumina, 3 of barium carbonate, 2 of zinc white and 20 of clay, and then fired in a firing kiln at a maximum temperature of l,300C. to prepare a sample. This sample was measured in variation of insulation resistance at the inner surface in the same manner as in Test Example 1 to obtain the results as shown in ing the atmosphereby continuously effecting spark discharge using-spark discharge electrodes (needle and plane plate) under such conditions as a gap between two electrodes of 2 mm., an applied voltage of 15 kv. and a currentof 5 mA. to obtain the results as shown in (1) of Table 3, in which were also shown the results ner as above, except that the coating according to the present invention was replaced by a generally used insulator glaze of the composition 0.20 K 0. 0.10 Na O. 0.30 CaO. 0.40 MgO. 0.70A1 O 7.00 SiO according (l) of Table 4, in which were also shown the results of measurement in inner pressure strength thereof. In Table 4, there were also shown, for comparison, the results of measurement in said properties of a sample (2) prepared in the same manner as above, except that the coating according to the present invention was replaced by an insulator glaze of the composition 0.20 K 0. 0.10 Na O. 0.28 CaO. 0.42 MgO. 0.75 A1 0 6.80 Si0 according to the Segers formula; a sample (3) comprising the aforesaid test piece having no coating; and a sample (4) prepared by coating the aforesaid test piece with an epoxy resin containing alumina powder as a filler, and curing theresin at C. for 2 hours and then at 160C. for 2 hours to form a coating of about 0.4 mm. in thickness. From Table 4, it is understood that the sample of the present invention is excellent in properties.
Table 3 Chemical compositionof coating after Amount Insulation resistance (.0) Bending strength Sample firing (wt /z) of (kg/cm) [Chemical composition of porcelain zircon After After After Before After body in the case of the sample (3)] (WV/t lni- 10 30 trcat- 100 tial hrs. hrs. hrs. ment' hrs. 1 1) t it SiO 36.16 A1 0 7.68 TiO 0.21 2.9 3.2 3.2 1.9 Sample of MgO 0.97 Na. 0.10 ZrO :49.68 73 X X X X 1.380 1.360 the present Fe. .O,, 0.43 010: 1.99 K 0: 0.39 10"" 10 10" 10"" invention 8:10 2.49
2) Sample SiO. 76.02 11: 0,; 0.35 CaO: 3.06 4.2 4 2 1.7 9.8 coated with K 0 3.43 A1 O,,:12.9l TiO- 0.17 X X X X 1.350 970 conventional MgO 2.93 Na O: 1.13 10 10' 10 10 glaze 3) Sample SiO. [73.23 'Fe O z 0.83 CaO: 0.17 3 9 9.1 3 3 7 6 having no K 0 2.00 A1 O;,:2l.5l TiO 0.37 X X X X 1,010 980 coating MgO 0.18 Na 1.65 10'' l0" 10" 10 Table 4 Chemical compisition of coating after Amount Insulation resistance (.0) Inner pressure Sample firing (wt /r) of Strength k 1 [Chemical composition of porcelain zircon lnitial After After After Before After body in the case of the sample (3)] (M71) 10 30 100 treat- 100 V hrs. hrs. hrs. ment hrs.
(1) Si0 :33.30 A1 O:,:13.89 TiO-,: 0.21 Sample of MgO: 0.97 ZrO :44. 15 Fe- ,O,-,:0.42 66 3.2 1.9 3.1 2.0 241 235 the present CaO:- 1.98 K 0: 0.38 Na O: 0.11 X 10 X 10 X 10' X 10' invention 3110: 2.46 ZnO: 2.1 1
Table 4 Continued resin Chemical compisition of coating after 7 Amount lnsulation resistance (9) Inner pressure Sample firing(wt/() of strength (kg) [Chemical composition of porcelain zircon lnitial After After After Before After body in the case of the sample (3)] (WW!) 10 30 100 treat- 100 hrs. hrs. hrs. ment hrs.
Sample SiO- :75.08 PC2031 3 CaO: 2.86 6.5 3.3 6.1 7.6 236 169 coated with K 0: 3.45 Al O;,:l3 89 TiO. 0.19 X X 10" X 10 X 10" conventional MgO: 3.08 Na .O: 1.12 glaze Sample 510 :7357 Fe 0 0.87 CaO: 0.19 3.6 1.0 4.9 3.1 173 170 having no K 0: 1.60 A1- O ,:21.06 TiO 0.31 X l0 X 10* X 10" X 10' coating MgO: 0.16 Na ,O: 2.24
Sample 1.1 5.3 6.3 4.2 181 176 coated with X 10" X 10 X 10' X 10' As is clear from the above explanation, the electric insulating porcelain article of the present invention is free from the drawbacks of the conventional electric insulating article, such as insulator or insulating bushing, and can be effectively used over a long period of time as an electric insulating article for electric appliances using SF gas as an insulating medium, without any deterioration in insulation resistance and mechanical strength. Thus, the industrial value of the present invention is extremely great.
What we claim is:
lLln a porcelain electric insulating article comprising a porcelain body and a porcelain coating thereon coming into contact with the decomposition products formed when SP gas is subjected to an electrical spark, the improvement wherein the porcelain coating coming into contact with said decomposition products contains not less than 50% by weight of zircon and has a thermal coefficient of expansion lower than the thermal coefficient of expansion of said body.
2. An electric insulating porcelain article as recited in claim 1, wherein said coating comprises of:
a. 37 to 62 by weight of ZrO b. 18.5 to 46.5 by weight of SiO c. 5 to by weight of A1 0 d. 0.1 to 5.0 by weight of at least one oxide selected from the group consisting of K 0 and Na O,
e. 1.0 to 10.0 by weight of at least one oxide selected from the group consisting of CaO and MgO,
f. not more than 7.0 by weight of at least one oxide selectedfrom the group consisting of ZnO and BaO, and g. not more than 5.0 by weight of at least one oxide selected from the group consisting of TiO and 2 3, the sum of said oxides (d) to (g) being 1.1 to 12 by weight and the weight ratio ZrO /SiO being 0.8 to 2.0. 3. An electric insulating porcelain article as recited in claim 1, wherein said body contains a crystal phase comprising quartz and mullite.
4. An electric insulating procelain article as recited in claim 1, wherein said body contains a crystal phase comprising cristobalite, quartz and mullite.
5. An electric insulating porcelain article as recited in claim 1, wherein said body contains a crystal phase comprising cristobalite, quartz, mullite and corundum.
6. An electric insulating porcelain article as recited in claim 1, wherein said body contains a crystal phase comprising quartz, mullite and corundum.
7. An electric insulating porcelain article as recited in claim 1, wherein said body contains a crystal phase comprising quartz, mullite and zircon.
8. An electric insulating porcelain article as recited in claim 7, wherein said crystal phase further contains corundum.
' 9. The article of claim 1, wherein said coating contains at least about 60% zircon.
10. The article of claim 9, wherein said coating contains about 69% zircon.
13. The article of claim 12, wherein said porcelain body has a thermal expansion coefficient of 5.0 to 8.8
x 10- /C. at 25 to 650C.
14. The article of claim 1, wherein at least a portion of the surfaces of the porcelain body not coming into contact with the decomposition products of SF 6 gas are coated with a compression glaze.

Claims (14)

1. IN A PORCELAIN ELECTRIC INSULATING ARTICLE COMPRISING A PORCELAIN BODY AND A PORCELAIN COATING THEREON COMING INTO CONTACT WITH THE DECOMPOSITION PRODUCTS FORMED WHEN SF6 GAS IS SUBJECTED TO AN ELECTRICAL SPARK, THE IMPROVEMENT WHEREIN THE PROCELAIN COATING COMING INTO CONTACT WITH SAID DECOMPOSITION PRODUCTS CONTAINS NOT LESS THAN 50% BY WEIGHT OF ZIRCON AND HAS A THERMAL COEFFICIENT OF EXPANSION LOWER THAN THE THERMAL COEFFICIENT OF EXPANSION OF SAID BODY.
2. AN ELECTRIC INSULATING PORCELAIN ARTICLE AS RECITED IN CLAIM 1, WHEREIN SAID COATING COMPRISES OF: A. 37 TO 62% BY WEIGHT OF ZRO2, B. 18.5 TO 46.5% BY WEIGHT OF SIO2, C. 5 TO 30% BY WEIGHT OF AL2O3, D. 0.1 TO 5.0% BY WEIGHT OF AT LEAST ONE OXIDE SELECTED FROM THE GROUP CONSISTING OF K2O AND NA2O, E. 1.0 TO 10.0% BY WEIGHT OF AT LEAST ONE OXIDE FROM THE GROUP CONSISTING OF CAO AND MGO, F. NOT MORE THAN 7.0% BY WEIGHT OF AT LEAST ONE OXIDE SELECTED FROM THE GROUP CONSISTING OF ZNO AND BAO, AND G. NOT MORE THAN 5.0% BY WEIGHT OF AT LEAST ONE OXIDE SELECTED FROM THE GROUP CONSISTING TIO2 AND FE2O3, THE SUM OF SAID OXIDES (D) TO (G) BEING 1,1 TO 12% BY WEIGHT AND THE WEIGHT RATIO ZRO2.SIO2 BEING 0.8 TO 2.0.
3. An electric insulating porcelain article as recited in claim 1, wherein said body contains a crystal phase comprising quartz and mullite.
4. An electric insulating procelain article as recited in claim 1, wherein said body contains a crystal phase comprising cristobalite, quartz and mullite.
5. An electric insulating porcelain article as recited in claim 1, wherein said body contains a crystal phase comprising cristobalite, quartz, mullite and corundum.
6. An electric insulating porcelain article as recited in claim 1, wherein said body contains a crystal phase comprising quartz, mullite and corundum.
7. An electric insulating porcelain article as recited in claim 1, wherein said body contains a crystal phase comprising quartz, mullite and zircon.
8. An electric insulating porcelain article as recited in claim 7, wherein said crystal phase further contains corundum.
9. The article of claim 1, wherein said coating contains at least about 60% zircon.
10. The article of claim 9, wherein said coating contains about 69% zircon.
11. The article of claim 1, wherein said coating is composed of a glass phase and a crystal phase comprising a major portion of zircon and a minor portion of mullite, zirconia and quartz.
12. The article of claim 1, wherein said coating has a thermal expansion coefficient of 3.9 to 4.9 .times. 10.sup.-.sup.6 /.degree.C. at 25.degree. to 650.degree.C.
13. The article of claim 12, wherein said porcelain body has a thermal expansion coefficient of 5.0 to 8.8 .times. 10.sup.-.sup.6 /.degree.C. at 25.degree. to 650.degree.C.
14. The article of claim 1, wherein at least a portion of the surfaces of the porcelain body not coming into contact with the decomposition products of SF.sub.6 gas are coated with a compression glaze.
US360423A 1972-05-18 1973-05-15 Electric insulating porcelain article Expired - Lifetime US3876455A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP47049367A JPS5250399B2 (en) 1972-05-18 1972-05-18

Publications (1)

Publication Number Publication Date
US3876455A true US3876455A (en) 1975-04-08

Family

ID=12829035

Family Applications (1)

Application Number Title Priority Date Filing Date
US360423A Expired - Lifetime US3876455A (en) 1972-05-18 1973-05-15 Electric insulating porcelain article

Country Status (6)

Country Link
US (1) US3876455A (en)
JP (1) JPS5250399B2 (en)
CH (1) CH582406A5 (en)
DE (1) DE2325100C3 (en)
FR (1) FR2184991B3 (en)
GB (1) GB1427989A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465900A (en) * 1983-03-16 1984-08-14 Ngk Insulators, Ltd. High voltage glazed porcelain insulators
CN105484551A (en) * 2016-01-24 2016-04-13 常熟市谷雷特机械产品设计有限公司 Iron tower for erecting high voltage transmission line
CN107200568A (en) * 2017-06-01 2017-09-26 合肥尚强电气科技有限公司 Environment-friendly weather-proof high-strength electric power insulator and preparation method thereof

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS51120317U (en) * 1975-03-27 1976-09-29
JPS5221220A (en) * 1975-08-12 1977-02-17 Toyoda Automatic Loom Works Spure serching device of automatic pouring machine for casting
JPS52106329A (en) * 1976-03-05 1977-09-06 Hitachi Ltd Method of detecting gate of mold
JPS5314915U (en) * 1976-07-19 1978-02-07
US4552800A (en) * 1979-03-02 1985-11-12 Blasch Precision Ceramics, Inc. Composite inorganic structures
CA1161238A (en) * 1979-03-02 1984-01-31 Robert Smith-Johannsen Inorganic composite structures
JPS55153664A (en) * 1979-05-15 1980-11-29 Toyota Motor Corp Sprue searching device of automatic pouring machine for casting
DE3444627A1 (en) * 1984-12-07 1986-06-19 Hans Dipl.-Ing. 4030 Ratingen Liebermann High-strength alumina porcelain body for high-tension insulators
DE102004045752B3 (en) * 2004-09-21 2006-05-04 Forschungszentrum Karlsruhe Gmbh Use of a ceramic as a dental ceramic

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2157100A (en) * 1938-12-20 1939-05-09 Locke Insulator Corp Glazed ceramic insulator and the like
US2170387A (en) * 1937-05-25 1939-08-22 Power Patents Co Glaze
US2325553A (en) * 1941-04-14 1943-07-27 Scovill Manufacturing Co Refractory and method of producing the same
US2534327A (en) * 1946-09-06 1950-12-19 Katherine L Whitman Vitrifying refractory composition and product
US3024303A (en) * 1960-03-09 1962-03-06 Ohio Brass Co Glazed insulator which comprises a ceramic body and a primary coat under the glaze which has a lower coefficient of thermal expansion than the ceramic body
US3078186A (en) * 1960-07-26 1963-02-19 Westinghouse Electric Corp Ceramic potting composition and method of encapsulating an electrical article therewith
US3166430A (en) * 1961-12-07 1965-01-19 Harshaw Chem Corp Iron ceramic pigment
US3189475A (en) * 1962-12-20 1965-06-15 Glidden Co Pink ceramic stain and process
US3281270A (en) * 1962-10-22 1966-10-25 Westinghouse Electric Corp Glass composition and thermoelectric element coated therewith
US3528835A (en) * 1964-12-28 1970-09-15 Thann & Mulhouse Preparation of colored ceramic pigments based on synthetic zircon
US3577252A (en) * 1967-09-13 1971-05-04 Goldschmidt Ag Th Process of producing zirconium silicate ceramic coloring substances
US3787218A (en) * 1970-10-27 1974-01-22 Owens Illinois Inc Zircon containing printing paste for overglaze coating of microelectronic circuits on ceramic substrates
US3804666A (en) * 1971-12-13 1974-04-16 Scm Corp Glazed ceramic ware
US3808042A (en) * 1970-06-05 1974-04-30 Owens Illinois Inc Multilayer dielectric
US3826659A (en) * 1971-05-05 1974-07-30 Nat Res Dev High zirconia containing glass ceramics

Patent Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2170387A (en) * 1937-05-25 1939-08-22 Power Patents Co Glaze
US2157100A (en) * 1938-12-20 1939-05-09 Locke Insulator Corp Glazed ceramic insulator and the like
US2325553A (en) * 1941-04-14 1943-07-27 Scovill Manufacturing Co Refractory and method of producing the same
US2534327A (en) * 1946-09-06 1950-12-19 Katherine L Whitman Vitrifying refractory composition and product
US3024303A (en) * 1960-03-09 1962-03-06 Ohio Brass Co Glazed insulator which comprises a ceramic body and a primary coat under the glaze which has a lower coefficient of thermal expansion than the ceramic body
US3078186A (en) * 1960-07-26 1963-02-19 Westinghouse Electric Corp Ceramic potting composition and method of encapsulating an electrical article therewith
US3166430A (en) * 1961-12-07 1965-01-19 Harshaw Chem Corp Iron ceramic pigment
US3281270A (en) * 1962-10-22 1966-10-25 Westinghouse Electric Corp Glass composition and thermoelectric element coated therewith
US3189475A (en) * 1962-12-20 1965-06-15 Glidden Co Pink ceramic stain and process
US3528835A (en) * 1964-12-28 1970-09-15 Thann & Mulhouse Preparation of colored ceramic pigments based on synthetic zircon
US3577252A (en) * 1967-09-13 1971-05-04 Goldschmidt Ag Th Process of producing zirconium silicate ceramic coloring substances
US3808042A (en) * 1970-06-05 1974-04-30 Owens Illinois Inc Multilayer dielectric
US3787218A (en) * 1970-10-27 1974-01-22 Owens Illinois Inc Zircon containing printing paste for overglaze coating of microelectronic circuits on ceramic substrates
US3826659A (en) * 1971-05-05 1974-07-30 Nat Res Dev High zirconia containing glass ceramics
US3804666A (en) * 1971-12-13 1974-04-16 Scm Corp Glazed ceramic ware

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4465900A (en) * 1983-03-16 1984-08-14 Ngk Insulators, Ltd. High voltage glazed porcelain insulators
CN105484551A (en) * 2016-01-24 2016-04-13 常熟市谷雷特机械产品设计有限公司 Iron tower for erecting high voltage transmission line
CN107200568A (en) * 2017-06-01 2017-09-26 合肥尚强电气科技有限公司 Environment-friendly weather-proof high-strength electric power insulator and preparation method thereof

Also Published As

Publication number Publication date
JPS4913699A (en) 1974-02-06
CH582406A5 (en) 1976-11-30
DE2325100A1 (en) 1973-12-06
DE2325100C3 (en) 1975-10-02
JPS5250399B2 (en) 1977-12-23
DE2325100B2 (en) 1975-02-20
FR2184991A1 (en) 1973-12-28
FR2184991B3 (en) 1976-05-14
GB1427989A (en) 1976-03-10

Similar Documents

Publication Publication Date Title
US3876455A (en) Electric insulating porcelain article
KR940005508A (en) Vitreous porcelain, manufacturing method thereof, sanitary ware produced therefrom and glazing thereof
US3380838A (en) Substances for producing crystalline heat-resistant coatings and fused layers
US3499787A (en) Method of manufacturing low thermal-expansion porcelain
US3658583A (en) Method for producing semi-conducting glaze compositions for electric insulators
US3458331A (en) Method of manufacturing relatively high calcia-silica ceramic materials
JPH06172015A (en) Method of preparing silicate bond material
US2859138A (en) Composition and method for coating a ceramic body
US2898217A (en) Ceramic products
US3982048A (en) Method of making an insulator with a non-linear resistivity coating of glass bonded silicon carbide
EP1039485B1 (en) Porcelain insulator and method of manufacturing the same
US3704146A (en) Ceramic whiteware compositions comprising a borate flux
US3860432A (en) Porcelain electric insulator
US2154069A (en) Ceramic body
US3473937A (en) Method of strengthening na2o-al2o3-sio2 glass-ceramics with leaded glazes and product
US3459567A (en) Method for producing porcelain articles
FR2294145A1 (en) Ceramic-glass composites for electrical insulation - made by mixing corundum and glass of controlled particle size, pressing and sintering at low temp
US1631695A (en) Porcelain
US3686007A (en) Aluminous ceramic compositions with tio2+mno2 flux
SU1229192A1 (en) Glaze
GB982600A (en) Improvements in and relating to glazes for ceramic articles
US2424082A (en) Alumina low silica refractory
US2386633A (en) Ceramic material
McCutchen Strontia and its properties in glazes
SU1122634A1 (en) Glaze