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United States Patent [191

[11]
[45]

Oda
[54]

HIGH STRENGTH FELDSPATHIC

[22] Filed:

Isao Oda, Nagoya, Japan

[57]
ABSTRACI‘
High strength porcelain having an unglazed bending
strength of greater than 1,400 kg/cm2 and consisting
essentially of 22-85% by weight of SiO;, 10-73% by
weight of A1203, and 1.5-6.5% by weight of K20 and

Dec. 30, 1985

Foreign Application Priority Data

Jan. 18, 1985 [JP]

Japan .............................. .. 60-7139

[51]

Int. Cl.‘ ........................................ .. C04B 33/24

[52]

U.S. Cl. . . . . . . . . . . . . . . . . .

[58]

Field of Search .............................. .. 501/143, 153

[56]

. . . ..

Jan. 5, 1988

Assistant Examiner-Karl Group
Attorney, Agent, or Firm-Parkhurst & 01111‘

[73] Assignee: NGK Insulators, Ltd., Japan
[21] Appl. No.: 814,508
[30]

4,717,695

Primary Examiner-Mark L. Bell

PORCELAIN

[75] Inventor:

Patent Number:
Date of Patent:

501/143; 501/153

/or N820. The porcelain has a total degree of crystallin
ity of more than 40% by weight, and a crystalline grain
size of not greater than 20 um, and it is free from defects

of larger than 40 pm. The procelain is produced by
pulverizing a starting material mixture of quartz-feld
spar-alumina system so that 85-95% by weight of parti
cles thereof have a grain size of not greater than 10 um,

References Cited

calcining the mixture, adding clay-mineral material

U.S. PATENT DOCUMENTS

therein, pulverizing so that the clay-mineral-added mix
ture contains less than 85% by weight of particles with

3,097,101

7/1963

Lester ................................ .. 501/ 143

3,431,126

3/1969

Fukui ............ ..

3,674,519 7/1972 Higuchi et a1. ....... ..
3,846,098 11/1974 Nakashima et a1.

.. .. 501/143
...... .. 501/153

a grain size of not greater than 10 pm, forming, drying, '

and thing at 1,100°-1,400° C.

...... .. 501/144

3,860,432 1/1975 Higuchi a a1. ................... .. 501/153

7 Claims, 8 Drawing Figures

Allmina 7j'pe Material
0 I00

00

v

uvvyvv

0

0/02030405060708090/00
~ Quartz 7jlpe Material

Fe/dspa?ric Material

5. l I I00 8m6=00¢432 0 I / 2 345 7 /0 2030405070/00 200 Effective Dbmefer (/um} Ak/mina Type Mm‘aia/ 0/00 Fl 6.US.. 1988 Sheet 1 of 5 4.717.695 FI . Patent Jan. 2 /0 20 30 ' 40 50 60 70 80 90 /00 0 I0 20 30 40 50 60 70 80 90/00 Fe/dspal/ric Material Quartz Type Maferia/ ..

/ //I6-“¢2/M4/.717.1% 20 30 4050 70 I00 Effect/‘Ye Diameter (.m.um) . my 07/3 r.695 F /// W m.US. 1988 Sheet 2 of 5 4. w w m 000 m 0 E3$15SmQg m% 2/12»043/ // / . 23457/0 MW / me m m. 5. wmrm/ . Patent Jan.

717. 1988 .695 F/G. Patent Jan. Sheet 3 of5 4. \l 70 V v 80 90 I00 Fe/dgoath/c Maten'a/ . 5.4 Alumina Type Material 0 I00 / \I 0 = \l \l \l \I I0 20 30 40 50 60 Quartz 7j/pe Material .US.

717.US.695 . 1988 Sheet 4 of5 FY6158 20/um 4. 5. Patent Jan.

Patent Jan.717. 1988 \ Sheet 5 of5 4. 5.US.695 F/Gl? _ {Q8EBN5Q$WD mil-I _ _ _ 65 70 75 80 85 90 95 /00 Percent by We/'ght of Particles Having Effective Diameters of Shorter than l0/um ( %) .

an object of the invention is to obviate the quartz-type material.800 kg/cm2 in the case of an rence becomes high. common porce duction as pointed out above. 7 shows the relationship between porcelain crease in the production cost or a complication of the strength and the grain size of a starting material mixture production process. The above “cracks” occurring in the drying or ?ring 50 following manner. feldspathic material. Namely. Such special measures result in an in FIG. and the invention also relates to a special method for producing such 1. In general. the particle 45 by weight. Field of the Invention This invention relates to a high strength feldspathic ~ porcelain and a method for producing the same. alumina-type densi?cation followed by carving an insulator out of the material. feldspathic material. the strength of porcelain tends to increase with the reduction of the particle size of starting material before so as to improve the strength thereof. the more likely the occurrence of cracks is in the drying and ?ring processes. caused during cutting the working of the body. it is empirically known in the art of porcelain production that the ?ner the particle size of the starting material. and such risk is further increased when such porcelain is used in making large high-volt alumina-containing porcelain composition containing . Another object of the invention is to provide a therefor. (3) mixed with clay-mineral ma surface thereof due to temperature differences therebe tween during the drying and firing processes. a starting material is (l) pulverized so as to produce such particle size distribu tion of which 85-95% by weight has an effective diame strained portions of the porcelain by the difference of ter smaller than 10 um. for example adding a large amount of corundum or by 20 applying static hydraulic pressure onto the body for quartz-type material. ing kneading and extrusion as a result of difference of dried. when the particle size of the 65 piece with a 12 mm diameter for the porcelain of the invention is 1. densi?ed body. such as large high voltage insulators. whereby the unglazed bending strength of the porcelain is greater than 1.717. the three-point bending strength of an unglazed test a shortcoming in that. while the abscissa represents the percentage by weight of particles with an effective above-mentioned shortcomings of the prior art by pro viding a novel high strength feldspathic porcelain hav diameter of not greater than 10 pm. A preferred embodiment of the high strength feld spathic porcelain according to the invention has a crys tal phase whose grain size is smaller than 20 um and whose total degree of crystallization is higher than 40% occur in the above processes. the crack tends to drying and ?ring processes even when the starting ma terial having a very ?ne particle size is used. the mixture is (4) pulverized so that less than 85% of the particles thereof have effective diameters smaller strained portions include both inside strains caused dur than 10 um. and the thus pulverized mixture is formed. when the content of particles with effective diameters of not greater than 10 um surpasses 85% by weight (to be referred to as % hereinafter).400 kg/cm2 in case of alumina-containing porcelain porcelain. the invention relates to high strength feld structure and being suitable for large high-voltage insu 10 with a 12 mm diameter for insulator porcelain is about 1. homogeneous micro low mechanical strength of porcelain. As can be seen from 30 ing a more homogeneous microstructure than known FIG. If the particle size of the starting material is made very ?ne. 25 porcelain consists essentially of quartz-type material. Accordingly. content of particles with effective diameters of not Such high strength feldspathic porcelain can be pro greater than 10 pm is less than 85% in both common duced by a method according to the invention in the porcelain and alumina-containing porcelain.400 kg/cm2 in the case of a common por starting material is very ?ne. The method of the invention costs less than conventional porcelain producing methods and does not require a 40 complicated production process. In short. 1.1 4. More spathic porcelain having a ?ne. which restriction is re?ected in a limitation of the homogeneity of the porcelain microstructure and a comparatively 1. and clay-min eral material. The 55 terial.695 2 HIGH STRENGTH FELDSPATHIC PORCELAIN age insulators or the like in which the temperature dif— ference between the inside and the surface of the porce BACKGROUND OF THE INVENTION lain is large. after being (2) calcined the expansion and shrinkage between the inside and the pulverized material is. cracks occur in the particularly. For instance. The strength of the high strength feldspathic porce the cracks discussed in the description of the invention process refers to those cracks which can be caused at refers to cracks formed in the inside and on the surface lain of the invention is 30-40% higher than that of con of the porcelain during the drying and ?ring processes. the particle size of the starting material is restricted to be larger than a certain value. namely. The ordinate represents unglazed bending strength of porcelain. for products which lain and alumina-containing porcelain. the risk of crack occur celain composition. On the other hand. and clay-mineral material. 35 lain which eliminates the occurrence of cracks in the Such tendency is recognized in both the common por celain and the alumina-containing porcelain. Accordingly. containing 20% of corundum. feldspathic material. Related Art Statement Two kinds of feldspathic porcelain are used in pro drying process and/or ?ring process of porcelain pro ducing high-voltage insulators. The reason for such increase of the porcelain strength is in that the use of ?ner material results in a method for producing high strength feldspathic porce more homogeneous microstructure in the porcelain. the three-point bending strength of an unglazed test piece lators and acid resisting porcelain.000 kg/cm2 in case of common porcelain and about 2. More particularly. Thus. and clay-mineral material. and ?red through similar steps to those of regular particle orientation and density between the inside and porcelain production. The steps (3) and (4) in the afore the surface of body material and the surface strains mentioned process may be interchanged. special measures have been taken. The common require a high mechanical strength. 7. Thus.400 kg/cm2 and the por size of porcelain material has been controlled so that the celain is free from defects larger than 40 um. while the alumina-containing porcelain consists essentially of therefor in the case of common porcelain made of SUMMARY OF THE INVENTION Therefore. the feldspathic porcelain of the prior art has ventional porcelains of similar types.

and alu than that of conventionally used quartz-type materials. and conventional method. Whereby.674. drying and ?ring. alumina-type materials which are used in the present The starting materials to be used in the present inven invention. abscissa. The mixing may be effected by any of the which range corresponds to that between the curves I1 following three methods depending on circumstances. and not greater than 85% of alumina type material.100 kg/cm2 in case of an alumina TABLE l-continued containing porcelain composition containing 30% of corundum. As can be seen from FIG.519. Pat. In contrast to such known particle size distributions. 2. feldspathic material. 1. 25 of the quartz-type materials used in the invention is ?ner feldspathic materials such as potash feldspar.695 3 4 20% of corundum. while the ordinate represents the percentage tion by controlling the particle size of secondary pow by weight of particles whose effective diameters are not der particles to be made by pulverizing the calcined greater than the effective diameters indicated on the material. 2 shows the blend composition of material cal . 1. (i) to pulverize the calcined material and then TABLE 1 mix it with clay-mineral material.717.807/ 1973 which corre sponds to U.S. The invention will be described in further detail now. 1. 22. the microstructure of porcelain is made more homogeneous than before so as to improve the strength thereof. The selection of the pulverization either before or after the above mixing depends on the scale of the pro 30 98 100 A desired high strength feldspathic porcelain can be . The starting mate The particle sizes of those feldspathic materials and rials are pulverized by a conventional pulverizing alumina-type materials which are used in the invention method of porcelain materials. to porcelain of the prior art are also depicted therein.101. The particle size in terms of the Stokes diameter. 40 composition is controlled so that 85—95% of the parti cles thereof have effective diameters of not greater than " ' which is generally referred to as the effective diameter. such as kneading. cle size distribution of which 85-95% are particles with 30 FIG. The range between the curves a1 and a2 indicates that known particle size distribution of the quartz type material which has been disclosed by the U. the particle size distributions of quartz type mate The reason for calcining the ?nely pulverized starting rial in both common porcelain and alumina-containing material in the present invention is two fold. Pat. in percentage the mixture. No. the abscissa represents the effective diameter prevent the cracking in later steps of porcelain produc ‘of particle.097. the particle size tion are quartz type materials such as siliceous sand. extruding. range between the curves S1 and S2 indi cates that particle size distribution of the quartz type material which is generally used in porcelain for insula tors. so as to produce a parti are also ?ner than those of the prior art. I 0 4O 2 15 49 In a preferred embodiment of the invention. ' Namely. The shaded portion of FIG. regular porcelain making steps.900 lrg/cm2 in case of an alumina-con taining porcelain composition containing 50% of corun dum. and 2.. ' the starting materials followed by mixing of the pulver and alumina-type material. 15-75% of feldspathic material. material mixture with the preferred blend composition FIG.400° C.S. The starting ‘ is determined by the sedimentation method. and I2 of FIG.4. or (ii) on a mixture of the starting consists of not greater than 85% of quartz-type mate materials at the predetermined composition for calcina rial. ?ne materials of por celain. the parti 3 3O 60 cle size of a mixture consisting of 45—80% of the cal 5 60 80 65 cined material and 20—55% of the clay-mineral material 7 75 88 is controlled so that not greater than 85% of the parti 10 85 95 cles have effective diameters of not greater than 10 pm. No. 1 shows the particle size distribution of the and the proper particle size distribution is calcined at starting materials used in the invention. as “calcination material”) which V1 above pulverization can be effected either (i) on each of consists of quartz-type material. 1 and Table l. For compari 900°-1. namely. (ii) to mix the calcined material with clay-mineral material and then pulverize Particle size distribution. The particle size distribution of a starting material mixture with such ' duction and the manufacturing facilities available. although more than 85 % of the starting mate rials before the calcination are ?ne particles with effec tive diameters not greater than 10 um. the range between the curves I1 and I2 represents the particle size distributions of those quartz type materials. feldspathic material. ‘ ized materials for producing a predetermind composi 2 represents a preferred composition of the calcination material to be used in the invention which composition tion for calcination. In homogenize the microstructure of the porcelain and to this ?gure. The mixture of calcined material and clay-mineral mate rial is pulverized while controlling its particle size dis tribution so that the content of particles with effective diameters not greater than 10 pm is less than 85%. mina type materials such as (1-Al203. son. can be effected in a manner similar to those of the Effective diameter (pm) 50 Particle size distribution. With the invention. The range between the curves P1 and P2 indicates that known particle size distribution of the quartz-type materials which has been disclosed by Japa nese Patent Publication No. so as to provide the calcination material. material. 20 95 100 ' tion. 3. and (iii) to mix the calcined material with a Effective by weight of particles not greater than diameter designated effective diameter 1%! 60 part of the clay-mineral material for pulverizing the (pm) Coarse side limit Fine side limit mixture and add the remainder of the clay-mineral ma terial into the pulverized mixture. 3. The cined (to be referred to. in percentage by weight of particles not greater than designated effective diameter (%) Coarse side limit Fine side limit 100 100 In FIG.effective diameters of not greater than 10 pm. Table 1 shows the range of particle size distri The calcined material is mixed with clay-mineral butions of the starting materials used in the invention. except clay-mineral materials are pulverized so that more than 85% thereof have effective diameters not greater than 10 pm and then calcined to sinter them. To this end. 10 pm as shown in FIG.

more preferably 20-60%. If the content of cristobalite exceeds 40%. because when greater than 10% of quartz due to the following rea the strength of feldspathic porcelain is improved by sons.. not greater than 40% of cristobalite. i.5% of K20 and/or NaZO due to the following reasons. electrical properties cannot be produced. the body he 30 high strength porcelain. the ?ring becomes dif?cult. 60 celain consists essentially of 22-85% of SiOz. the 65 tallinity of the crystal phase being more than 40%. a low total degree of crystallin ity of less than 40% results in a large deformation of the drying. forming. bending strength. and electric properties. and ?red. and quartz. the ?ring temperature becomes too high and the baking process 35 cess. In a preferred method of the invention.. such as the 25 tron microscope that the crystals of the porcelain of the invention were not greater than 20 pm. the coef?cient of thermal expansion. while if it surpasses 50%. 1. the coef?cient of thermal expansion of the porcelain becomes too large degree of crystallinity. the crystal phase. Namely. i. in the main. the degree of crystallization for the crystals being selected mechanical properties such as the bending strength and the toughness as well as the electrical properties such as in ranges of not greater than 60% for corundum. not greater than 40% for cristobalite. and . The crystal phase. The “defects” refer to foreign material and pores in the porcelain. cristobalite. cristobalite. pm hardly remain in the porcelain. quartz (100). greater than 40 um because defects larger than 40 pm If the content of SiOZ. is less than 10%. The inventors con molded. the por strength of the porcelain is reduced. because if it is less than 40% by weight. the extrusion and form into the porcelain during body the manufacturing pro ing become dif?cult.l00°-l. the above blend composition is selected in order to provide desired performance characteristics of the porcelain 15 produce a homogeneous microstructure and cannot provide the desired high strength porcelain. is less than 22% or more than 85%. and the microstructure thereof in the aforesaid manner. such particles are molten and reacted during ?ring. and quartz.5% of K20 and/or NagO. thermal properties. more than 60% of corundum makes the restricting the blend composition. and quartz. cristobalite (101). not greater than 40% of cristobalite. and the method according to the inven tion ensures that the pores in the porcelain produced thereby are not greater than 40 pm. porcelain with excellent mechanical and phase selected from the group consisting of corundum.400 kg/cmz. The degree of crystallinity was determined by the quantitative X-ray diffraction method. the ?ring. while if it when the porcelain is tired and the ?red porcelain is free exceeds 6. of corundum. and l. Namely.695 6 made from the thus particle-size-controlled mixture by proved. which is mainly introduced from the clay-min of the porcelain. cristobalite. so that stable production of porcelain of com plicated shapes becomes difficult. mechanical properties. mullite. 10-73% The total degree of crystallinity is restricted to be of A1203. The inventors con teristics of the porcelain. and stable production of high-voltage insulators of complicated shapes becomes difficult.5-6. If the content of‘ rial is substance which is different from proper materials A1203.5 4. content of glass in the porcelain becomes from residual foreign material larger than 40 pm. and not greater than 10% of quartz.5%. and ?re. and not stricted to be more than 1. and the like. If the content of mullite is less than 5%. and ?ring at 1. Since the starting material of the high strength following the steps of kneading. an unglazed bending strength of more than 1. The crystal phase of the high strength feldspathic porcelain according to the invention is formed from at least one crystal phase selected from the group consist ing of corundum.400° C. The too high and the porcelain tends to be softened during magnitude of the pore depends on the method of porce lain production. the por celain has a crystal phase formed of at least one crystal more than 40% by weight. A preferred crystal composition consists of not greater than 60%. More particularly. mullite.400 kg/cm2 is obtained when a high strength feldspathic porcelain satis?es the follow resulting in a high inside stress of the porcelain and the ing conditions: namely. cined material and the clay-mineral material is 44 pm. which is mainly introduced reduce the porcelain strength and hamper production of from the silica type material and the clay-mineral mate rial. For example. such unglazed bending strength is achieved. while if it exceeds 73%. and most of such foreign matter enters ' eral material. and the peak diffractions for the individual crystals measured were corundum (113). The performance characteristics ?rmed by an optical microscope and a scanning elec considered include. a total degree of crys with the increase of the total degree of crystallinity.e. so that crystals larger than 20 and to obtain a body which can be easily extruded.717. The start ing materials of the porcelain of the invention are in the form of very fine particles. in terms of percentage by weight. 85-95% thereof having a particle size of not greater than that 10 pm. the mesh of the ?nal sieve for the molding slip mixture of the cal becomes dif?cult. More than 10% of quartz makes the strength of the porcelain insuf?cient. 5-50% the volume resistivity and insulating strength are im for mullite. so that foreign material passing the ?nal sieve melt is less than 1. mullite (220). the ?ring becomes dif?cult. extruding. The blend composition of the major ingredients of the high strength feldspathic porcelain is limited to 22-85% of SiOz. and 5—50% of mullite.e. If the content of K20 and/or N820. In order to produce the desired performance charac the strength of the porcelain becomes insufficient. pm. The unglazed bending strength of the high strength is limited to not greater than 60% of corundum.5-6. The defects in the porcelain are restricted to be not volume resistivity. the ?ring difficult. mullite. The reasons for various limitations of the invention The size of the crystals is restricted to be not greater than 20 am because crystals larger than 20 um cannot will be described now. which are mainly introduced from feldspathic material.5%. porcelain during the ?ring. The foreign mate comes hard to extrude. the crystal phase of the high strength feldspathic porcelain is restricted to at least 45 ?rmed by an optical microscope and a scanning elec tron microscope that the foreign material and pores in one type of crystal selected from the group consisting of the porcelain of the invention were not greater than 40 corundum. with the particle size distribution of 85-95% having an effective diameter of not greater than 10 pm and 5-15% having an effective diameter of larger than 10 pm. form. 10-73% of A1203. on the basis of weight. in a manner simi lar to the corresponding steps of any suitable conven tional method. feldspathic porcelain of the invention are very ?ne par ticles. 5-50% feldspathic porcelain according to the invention is re of mullite.

5% of Fe2O3. not greater than 1.5% of K20 and/or NazO and to contain 20-60% lain microstructure is not deteriorated thereby.5% of K20 and/or produced in the calcined material. Fe2O3. it has been found that a ratio of strength feldspathic porcelain with an unglazed bending erable. foaming occurs and :. and ZnO. forming. and alumina-type material. 1 is a graph showing the particle size distribu ent or reagent is more than 20% the extrusion. High strength feldspathic porcelain with an unglazed 8 such blend composition is the content of the feldspathic material. If the content of feldspathic material is less than 15% a dense structure of porcelain cannot be ob tained even after ?ring a mixture of the calcined mate rial and the clay-mineral material. the bending test being carried out by using a loading machine at a cross head speed of 0. in comparison with those of quartz type ma The starting material of the porcelain of the invention terials for common porcelain and alumina-containing is restricted to be at least one material selected from the the group consisting of TiO. the porcelain tends to be softened during the ?ring step and stable produc tion of large high-voltage insulators is hampered. 30-73% of A1203. because if such ?ne particles are not starting materials include quartz-type material. The starting material is also required to be pulverized so that 85-95% thereof are in the form of particles with effective diameters of not greater than 10 pan. but if the content of such additional ingredi group consisting of quartz-type material. invention.5 % of TiO. 20-55% by weight of the clay-mineral material is pref The inventors have also found that the above high the clay-mineral material. B203. Such porcelain is developed for large high-voltage insulators. As long as proper plasticity of the body is ensured by bending strength of 1. clay-mineral mate rial containing more than 85% of ?ne particles with of SiOZ. and clay-mineral material.5% of TiO. and not greater than 0.. and ZnO is used. if not greater than 20% of at least one ingredient or reagent selected from stable production of porcelain is hampered. and not greater than 20% of at l. not greater than 0. BRIEF DESCRIPTION OF THE DRAWINGS For a better understanding of the invention. not greater than 1. The “unglazed bending strength” as used in the invention refers to that bending strength of an unglazed test piece with a 12 mm diameter at which the test piece is broken in a three point bending test with a 100 mm span. In addition to the 40 l. The caused and ?ne homogeneous microstructure is not reason for the restriction of 1. and not greater than 0.7% of CaO.5% of 20 900‘-1. grain size of the crys tals being smaller than 20 um. the blend compo sition of the above~mentioned calcination material is microscope of a penetration type. while if the content of feldspathic material exceeds 75%. showing the micro to be described hereinafter. 15-75% by weight of feldspathic invention. and if such content is less than 20% or more than 55%. provided that the homogeneity of the porce l. material. The of corundum in crystal phase thereof. ZI‘02.400° C..5% of TiOz. 3 is a graph showing the particle size distribu tions of quartz-type material. not greater than 1.5% of 35 comes insuf?cient and extrusion and forming of the body become difficult. because such ma~ FIG. l. BaO.. When the content of corundum crystals is less than 20% the three-point bending strength of an unglazed test piece with a 12 mm As to the blend composition of the body made by mixing the clay-mineral material with the pulverized diameter becomes not greater than 1. because if the calcining temperature is Fe2O3 is necessary for electric insulation.695 not greater than 10% for quartz. Na2O is the same as described above. taken by an optical porcelain according to the invention. FIG. while if they are more than 95% any improvement in the porcelain strength. In a method for producing high strength feldspathic alumina compositions of Samples used in the examples quartz-type material. 5A is a photomicrograph. the sintering effect is insuf?cient for greater than 1. in which: FIG. the plasticity of the body be blend composition which consists essentially of 30-60% of SiO. so that above-mentioned other chemical substance are. If the ?ring temperature is below least one oxide selected from the group consisting of TiOZ. material.5—6. while if it is above 1. which terial can produce porcelain having the desired physical and chemical properties. 4 is a graph showing the quartz-feldspar greater than 85% the desired strength of the porcelain cannot be achieved. BaO. not greater than 0.100° C. for ex ample.4000 C. tion of the materials of the porcelain according to the and ?ring of the porcelain becomes difficult.800 kg/cm2 is restricted to have a blend composition which consists essentially of 30-60% mixing a suf?cient amount of clay-mineral material with the pulverized calcination material.7% of producing a homogeneous microstructure in the cal CaO. B203.400° C.5% of MgO are necessary cined material. and not greater than 85% by weight of alumi na-type material..400° C. and 5 material. and not below 900‘ C. feldspathic material. a well sintered porcelain cannot be obtained. FIG. 2 is a diagram showing the composition range of starting materials to be used in the invention.5—6. and the porcelain being free from defects larger than 40 pm.l00°-1. alumina-type ' strength of 1. The dominant reason for selecting microscope of a penetration type. quartz-type material. feld spathic material. feldspathic material. while calcined material. reference 45 is made to the accompanying drawings. and alumina-type materials. the above unglazed bending strength can be achieved.5% of MgO.717.. and alumina-type material which were used in the examples of porcelain of the invention as described hereinafter. ZnO. extra pulverizing time is consumed without producing 60 FIG.5-6. not greater than 1. 21'02. 30-60% of SiO.5% of MgO. 5B is a photomicrograph. etc. taken by an optical .. and 30-73% of A1203 are necessary to The calcining temperature is restricted to be render a high moldability. Ti02.7 4. feldspathic porcelain of the prior art. not greater than chemical substances may be added to the calcination effective diameters not greater than 10 pm and other 0. 30-73% of A1203.800 kg/cm2.800 kg/cm2 can be obtained by using a . foaming is to facilitate the fring of large porcelain insulators. showing the rnicro restricted to be not greater than 85% by weight of 65 structure of Sample F of Example 1 according to the FIG.5% material and the clay-mineral material is restricted to be of K20 and/or NazO. The dominant reason for it is in the content of 30 45-80% by weight and the calcined material and if it is more than 60% the ?ring becomes difficult. ZI'OZ. material. not greater than The firing temperature of the mixture of the calcined 0. while if it is higher than 1. BaO. not greater than 1.5 mm/min.7% of CaO.

the loading speed being 0. and a-AlgO.e. 10 Each of Reference Samples J and K of Table 3 had a EMBODIMENTS calcination material composition falling outside of the The invention will be described in further detail by referring to examples. gaerome clay in this Of 'the electric properties. The bending strength of the Starting material mixtures for calcination were pre pared by mixing the quartz-type material. were mixed at the ratios shown in Table and 95% of particles thereof had a particle size of not 3.695 10 structure of Reference Sample M of Example 1 pro duced by a conventional method. each casting slip consisting of the mixture of the calcined material FIG. After deferrization by a ferro ?lter. 4. each of the above mixtures was dried by an electric drier and cal a mirror type thermal expansion meter based on the cined at l... The four i. A test piece with a 12 mm diameter for each sample was molded from the of the starting material thereof in the case of common ' kneaded body.l50'-l. Each casting slip was dehydrated by a ?lter press using a 88 um mesh sieve. and clay-mineral material. Sample thereof had particle sizes of not greater than 10 TABLE 3(a) Composition and properties Invention Reference A B C C‘ D E F G H I J K L M N 73 27 60 30 40 30 40 30 20 5O 20 30 36 l9 27 18 5 30 0 30 20 10 10 — 80 — -—- - 0 0 0 0 0 0 45 55 60 70 70 I0 -- - — Composition of calcined material1%! Quartz type Feldspathic Alumina . The particle size distribution of each 70-80% of particles thereof not greater than 10 am of the above four starting materials after the pulveriza after being further mixed with gaerome clay. so that pulverization of this clay 25 through a wet process so as to make particle size of was not necessary. potash feldspar Reference Samples L through N of Table 3 were as the feldspathic material. pm. The clay-mineral material. The coef?cient of thermal expansion was measured by using mixed by a wet process with a ball mill. ten kinds of porce lain Samples A through I were produced and Table 3 FIG.350° C. namely. Namely. the dielectric constant. each test piece was ?red at l. three ingredients. in a porcelain made of quartz-type material. the feld spathic material.300'-1. Whereby. and the casting slip produced thereby was passed through a ferro ?lter for deferriza tion. and the alumina-type material by using nine compositions A through I of FIG. sili except the blend composition thereof. 7 is a graph showing the relationship between shows the properties of such Samples. feldspathic material.300'—l. After 35 being dried. and the blend composition was determined by wet chemical quantitative analysis.300‘ C. kneaded by a vacuum kneader. and each of the mixtures was pulverized by a ball mill greater than 10 um. Thus. The sizes of the crystals and defects were determined by observation through an optical microscope and a scan ning electron microscope. TABLE 2 Effective diameter (um) clay as the clay-mineral material was then added to each 30 Particle size distribution. tions for production were the same as those for Samples _ J and K were made by the method of the invention Four starting materials were selected. but the starting materials and the equipment and condi EXAMPLE 1 A through I of the invention. and the specimen for this nace. ceous sand as the quartz type material. dried and ?red at l. Gaerome tion is shown in FIG. Reference Samples range of the invention as shown in FIG. i. Additionally. 3 and Table 2.717. 6 is a diagrammatic illustration of a solid insulaw tor with shades. in an ELEMA electric fur 50 principle of optical leverage. Sample C’ was made by adding 5% of measurement was dimensioned 4 mm dia.4. and bauxite as the alumina type material.e. the degree of crystallization was measured by the quantitative X-ray diffraction method. ZnO into the composition of Sample C by extrapolation and then calcining. 4. siliceous sand as the quartz-type material. and the insulating strength was mea the Samples A through I at ratios of Table 3. DESCRIPTION OF THE PREFERRED continuous ?ring furnace. in a continuous ?ring furnace. kneaded. was selected as the clay-mineral material. and each mixture thus produced was pulverized by a wet process with a ball mill so that 80% of the particles in each sured in accordance with VDE (Verband Deutscher Elektrotechniker)-0335. 2 and FIG. As to the properties listed in Table 3. albite as starting materials were individually pulverized in a ball the feldspathic material. and a-AlzO3 as the alumina mill by a wet process. the volume resistivity. The acid resistivity was mea sured by the JIS powder method of JIS R1503. 4. In FIG.00 mm. and extruded. in percentage by weight of particles not greater than design_ated effective diameter (%) Siliceous Potash a-AlzO3 sand feldspar alumina Bauxite l 21 ' 30 5 l7 2 3 5 7 10 20 30 50 36 48 66 79 89 99 100 100 43 54 70 80 89 98 100 1(1) 28 48 76 87 93 98 99 100 32 46 67 82 92 99 100 100 of the pulverized mixture by mixing them in a ball mill through a wet process. and the bending strength of a test piece and the partcle size and the gaerome clay was sifted through a 44 pm mesh sieve for dehydration by a ?lter press.350‘ C. gaerome clay 20 made by a prior art method. and extruded so as to produce a test piece with a 12 mm diameter. was mixed with the calcined material of each of 55 Standard) C2141. and the dielectric loss tangent were measured by the method of I IS (Japanese Industrial case.X50. After being unglazed test piece with a 12 mm diameter was mea 45 sured by the three-point bending method with a 100 mm span while using a loading tester. The gaerome clay was elutriated type material.5 mm/min in terms of its crosshead speed.

9 0.004 0.0 42 43 50 49 41 42 46 48 44 42 — 15 38 36 27 (x 1013 .8 7.210 12rnmdia.7 0.365 0. at 25° C.3 0.3 0. at 25°C.9 0.6 0.1 2.5 0.8 6.1 3.3 0.1% of K20 and/or NaZO.3 0.8 7.1 0.300 1.695 11 12 TABLE 3(a)-continued Composition and properties Invention A (‘I-A1203) type Alumina B C C’ D Reference E F G H I J K L M N _ 0 10 30 30 30 50 0 0 0 0 0 0 — —- — 0 0 0 5 0 0 0 0 0 0 0 0 -- — - 1.5 48.0 14.1 5. The amounts of various bending strength fell in a range of 1.9 7.0 4. CaO MgO K20 NaZO ZnO Crystals in @rcelain!%! Mullite Cristobalite Quartz ' Corundum Total crystals TABLE 3(0) Composition and Invention Reference properties A B C C' D E F G H I J K L M N Crystal size (pm) Defect size (turn) 19 30 l8 38 18 32 17 33 16 31 16 32 16 28 16 29 15 26 15 26 17 55 15 26 50 86 43 77 25 52 950 1.2 0.0 12.5 1.1 0.5 1.8 0.6 0.4 0.7 1.345 0.005 0.3 0.8 0.1 6.9 0.0 11.4 1.7 28.0 67.420-2.8 62. 16-63% of A1203. Their blend composition was in a range balite.6 45.200 1.0 51.3 23.1 9.6 0.2 60.0 60.1 2.6 24.1 2.398 0.5 0.2 3.0 0.750 1.1 22.8 1.250 0.440 0.6 0.0 3. and the total consisting of 33-80% of SiO.308 0. and degree of crystallinity was in a range of 42-66%.6 4.1 2.004 0.9 35. 8—35% of mullite.) Ratio of starting materials!%! Calcined 63 63 63 63 63 63 69 70 68 66 70 63 - -- — 37 30 10 28 24 0 10 37 35 36 32 20 38 material (Quartz type) (Feldspathic) (Alumina type) Clay-mineral material 37 37 37 37 37 I 31 30 32 34 30 G H I J K L M N TABLE 3(b) Composition and properties 37 Invention Reference A B C C‘ D E F 79.1 0.1 0.950 2.0 62.2 0.012 0.7 0.3 0.4 0.8 66.5 32.8 1.007 0.89 6.680 1.008 0.467 0. not greater than 32% of cristo 26-38 pm.0 33.0 49.4 0.463 0.0 34.9 0.008 0.150 1.) Dielectric loss tangenttan? (x 104.7 60.3 27.0 0.0 55.3 0.9 0.6 25.9 0.9 6. .8 0.5 1.8 9.326 0.0 33.7 — 0.8 18.2 16.0 76.0 58.8 42.0 0.2 32.1 8.3 17.360 0.8 50.4 44.2 1.8 25.780 1.0 6.2 1.120 1.1 34.4 8.1 0.400 2.8 0.150 -— —- — (bauxitehypc ZnO reagent (extrapolation) calcining temperature ('C.3 0.7 0.1 51.0 0.7 0.8 0.9 4.9 1.0 14.0 47.9 39.6 17.8 Porcelain chemical comEition§%) SiO-z A1103 Fe2O3 TD.2 5.4 15.7 0.3 0.3 0.7 0.5 56.0 72.2 1.4 10.717.6 0.8 1.6 0.8 0.0 34.6 13.5 0.0 0.022 0.0 0.5 0.0 53.5 0. test piece (kg/cm2) Coef?cientot‘ thermal expansion (%.007 0.005 0.570 1.1 14.9 0.(I-cm.1 0.015 Bending strength of unglazed 1.0 35.850 2.327 0.3 80.3 0.4 1.4 1.9 0.3 0.0 56. and not greater than 9% of quartz.8 0.0 8.0 5.1 0.300 1.1 0.2 25 13 11 8.77 0.524 0.3 0.2 0.8 0.1 0.) Acid resistivity 7 (%) Volume resistivity 12 11 l5 18 4. at 25' C.1 2.8 0.200 1.380 0.2 0.1 3.271 0.6 16.4 8.015 0.402 0.7 1.1 1.1 36.0 0.8 54.2 57.9 0.940 570 1.0 35.4 38.415 0.0 8.0 20.1 0. Samples A to I of the porcelain according to the invention had a crystal size crystals therein were not greater than 50% of corun in a range of 15-18 pm and a defect size in a range of 65 dum.9 1.0 5.0 51.1 0.6 12.0 1.4 1.1 0.0 48.420 1.1 3.1 2.7 16.8 4.0 0.150 1.5 6.1 0.1 13.5 0.3 0..1 16.2—5.5 35.1 0.7 0.6 6.006 0.9 0.1 5.3 52.4 1.7 0.7 8.0 62.0 0.6 1.7 0.3 0.7 0.) Insulating strength (kV/cm) As can be seen from Table 3.4.4 6.) Dielectric constants (50 Hz.005 0.3 0.940 kg/cm2.6 0.1 2.1 0.5 0.160 2.0 1.1 0.1 0. Their 2.024 0. at 650‘ C.200 1.0 — 5.7 12.6 3.5 0.200 1.5 7.6 0.9 0.1 0. 50111.200 1.1 0.8 37.5 — 43 5.1 2.200 1.366 0.7 46.1 1.4 0.200 1.

so that the strength of such Samples proved to be improved by 30-40% as com pared with porcelain which contained a similar amount the Sample F column for composition of calcined mate rial. and an overall cracks and ?ring cracks. the feldspathic material. and the ?ring cracks were checked by the invention has a more homogeneous microstructure both the eye and an inside inspection with X-ray pene than that of conventional porcelain.150 mm. and drated slip was extruded by a vacuum extruder so as to the alumina type material. 5B. and its total degree of crystallinity was 16. had crystals with a mixture more than 80% of the particles have a particle size in a range of 25-50 pm and a total degrees of crys size of not greater than 10 um. Thirty pieces of the above ZnO proved to improve the bending strength by 100 solid insulators with shades. mixed and then calcined for provid rial. FIG. the insulators were glazed and ?red at l. and their bending strengths were 950-l. 25 molding slip prepared by mixing the calcined material Sample C’ of the invention contained 5% of ZnO on the basis of the total of calcination material including with the gaerome clay was passed through a 44 um mesh sieve and dehydrated by a ?lter press. and then such remaining tallinity in a range of 34-38%. The dehy the quartz type material. The drying crack was checked by inspec 5A and FIG.950 lag/cm2 and Sample I containing 49. potash feldspar.150 mm and a cylindrical portion diameter of 185 mm. with shades as shown in FIG. 6 and two kinds of rod length of 1..e.. in order to obtain a high produce bodies with a diameter of 290-310 mm and an strength and a low thermal expansion. 5B shows a similarly taken photograph of the microstruc ' ture of Reference Sample M made by a conventional insulators that no crack occurred at all during the dry ing (drying cracks) at either cylindrical portions or shade portions. which were better than those of Reference Samples L After drying.350° C.300°-l. i.940 kg/cmz. As can be seen from the comparison of FIG. ?nely pulverized materials and improve the mechanical The porcelain of Sample F of Example 1 was used for strength of porcelain. a defect size in range of gaerome clay was loaded into the trommel and thor 52-86 pm. because one of the features of the invention is in its application to large high-voltage insu moisture absorption test on test pieces which were cut out from the central portions of the insulators. For reference. EXAMPLE 2 Sample insulators were made by using the porcelain 50 of the invention. The samples of the large high-voltage insulators of the invention. were pro like solid insulators. of K20 and NazO. the kg/cmz. After deferrization by a ferro ?lter. 7. 10% of potash feldspar in the calcination material.150‘ C.2% of corundum had a bending strength of 2. The sintered conditions were checked by a method.1% and its bending strength was merely 1. a shade portion diameter 230 mm.. and thirty rod-like solid sion by about 0. Sample E containing 18. the dimensions of the solid insulator 55 duced in a manner similar to conventional porcelain with shades were a cylindrical portion diameter of 145 production with a high stability but without any drying mm. in a continuous ?ring furnace.150 mm and a feldspathic porcelain and a method for producing the cylindrical portion diameter of 165 mm and a second 60 same in accordance with the invention facilitate forma kind of rod-like solid insulator had an overall length of tion of homogeneous porcelain microstructure by using 1. rod-like solid lators. i. and the starting material mixture was pulverized through a wet process by using a trommel so as to make the particle size of 90% of particles thereof not greater than 10 pm. by a rotary hearth kiln for baking tiles. and the alumina-type material are feldspathic material. it was con?rmed by inspection of all the through N made by a conventional method.. 5A shows a photomicrograph of the micro structure of Sample F of the porcelain according to the invention. Such addition of 30 overall length of 1. the sand as the quartz-type material.8% of co rundum had a bending strength of 1. thirty rod-like solid insula kg/cm2 and to reduce the coef?cient of thermal expan tors of the above ?rst kind. Reference Sample I was not sintered well and had comparatively large defects in the order of 55 pm and the bending strength thereof was merely 570 kg/cmZ. After the inspection. 15 feldspar in the calcination material resulted in an exces sive amount.e. and elutriated gaerome clay as the clay-mineral ing a calcined material with a homogeneous microstruc material.3%. of K20 and NazO. the solid insulator with shades having a cylindrical portion diameter of 145 mm. which were pre 20 such a manner that when being added to the above pared by a conventional method. The i.695 More particularly. In a method of the invention. Reference Sample K containing 80% of potash 14 A1203 were mixed at the ratio shown in Table 3 under calcined mixture was coarsely crushed by a roll crusher into particles of not greater than 2 mm. dried by an electric drier. It was con?rmed that the ?red solid insulators with shades and rod-like solid insulators were all free from ?ring cracks were and had good sintered conditions. In mixing 69% of the calcined material and 31% of the gaerome clay as shown in Table 3. (It-A1203 as the alumina-type mate ?nely pulverized. FIG. potash feldspar as the 65 feldspathic material.210 kg/cml. and then the clay-mineral material is added therein . After deferrization by a ferro ?lter. insulators of the above second kind were formed and Samples A through I of the porcelain of the invention dried.800 mm. the pulverized starting material mixture was passed through of corundum but was made by a conventional method.13 4.e.2%. Thus. the porcelain made by the method of 45 tion with the eye. tration. resulted in an insuf?cient amount. 1. and a ture. The dimensions of the solid insulators were all as proved to have electric properties and acid resistivity 35 mentioned above. The remaining 16% of the gaerome clay was pulverized through a wet process in Reference Samples L through N. high strength solid insulator had an overall length of 1. while a ?rst kind of the rod-like As described in detail in the foregoing. and the rod-like solid insulators with a diameter of 185 mm. which used a calcination mate a 44 pm mesh sieve and dehydrated by a ?lter press and rial with a composition outside the present invention. The dried starting material mixture was crushed by a roll crusher into particles not greater than 10 mm. the quartz-type material.09% at 650' C. which photograph was taken by a penetra 40 tion type optical microscope.380 oughly mixed. i. Starting materials were siliceous various starting materials. 15% of the ga erome clay was at ?rst loaded into a trommel together with the calcined material. Reference Sample I.e. and then continuously calcined at 1. The siliceous sand. Such sample insulators included solid insulators insulators with a diameter of 165 mm. of the sample insulators.717.

15 4.717. 1! =8 * 1. a grain size of said crystal 45 50 55 65 . What is claimed is: of at least one oxide selected from the group con sisting of K20 and NazO. and 1.5-6.695 16 phases being not greater than 20 pm. a total degree 35 40 pm. 7. BaO. High strength feldspathic porcelain as set forth in according to the invention contribute greatly to the art claim 1. form 2.5% by weight of T.5% by weight scope of the invention as hereinafter claimed. and quartz. not greater than 0. not greater than 40% by weight of cristobalite. the por claim 1. it is understood that the 30-60% by weight of SiO.950 kg/cm2.. Although the invention has been described with a the porcelain consisting essentially of: certain degree of particularity. cristobalite. 10% by weight for quartz. High strength feldspathic porcelain as set forth in claim 1.8-73% by weight of A1203. The porcelain and the method of producing the same 3. not and the combination and arrangement of ingredients greater than 0. and not greater than 40 claim 5. extruding.5% by weight of at least one oxide 30 selected from the group consisting of K20 and NagO. not greater and steps may be resorted to without departing from the 20 than 0. so that a suitable moldability is rendered to the body at each of the steps for kneading. High strength feldspathic porcelain as set forth in greater than 40% by weight.800 kg/cmz. High strength feldspathic porcelain as set forth in properties such as are resistivity. High strength feldspathic porcelain as set forth in in ranges of 5-50% by weight for mullite.7% by weight of CaO. and not greater than 10% by weight for quartz. and the amount of A1203 is 30-73% by processes. wherein said procelain is acid resisting. not greater than 0. a grain size of said crys tal phases being not greater than 20 um. a degree of crystallization claim 5. 18.800 kg/cmz.! Ill . 30-73% by weight of present disclosure has been made only by way of exam A1203. and the particle size distribution of the mixture is con trolled. and ?ring. wherein said porcelain is acid resisting. and not greater than 20% vby weight of at least one oxide selected from the group consisting of TiOz. a total degree of crystallinity of said second crystal phase being greater than 40% by weight for cristobalite.5% by weight of formed from corundum in an amount of 20—60% by weight and at least one second crystal phase se MgO and 1. ZrOz. and a size of de fects in said porcelain being not greater than 40 Jun. not greater than 1. drying.5% by weight of Fe2O3. l. wherein said porcelain is for porcelain insula of large high-voltage insulators by providing very tors. the porcelain consisting essentially of 22-85% by ZnO. and the amount of Si02 is 30-60% by weight.O2. cristo balite. ple and that numerous changes in details of construction not greater than 1.. wherein said porcelain is for porcelain insula for said at least one second crystal phase being selected tors.5-6.5% by weight of Ti02. and a size of defects in said porcelain being not greater than sisting of mullite. weight. Additionally. not greater than 1.5% by weight of Fe2O3. B203. wherein said unglazed bending strength is at cracks is effectively prevented in the drying and ?ring 5 least 1. the porcelain having a ?rst crystal phase weight of SiO. High strength feldspathic porcelain with an un glazed bending strength of greater than 1. ing. whereby the occurrence of glazed bending strength of greater than 1.5% by weight of MgO. High strength feldspathic porcelain with an un such as acid resistivity. celain of the invention has a high chemical resistivity 5. strong and compact insulators with excellent electric 4. and quartz. the porcelain having a crystal phase formed from co rundum in an amount of 20-60% by weight and at least one second crystal phase selected from the group con lected from the group consisting of mullite.7 % by weight of CaO. not greater than 1. of crystallinity of said second crystal phase being 6.