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

uvvyvv

0/02030405060708090/00
~ Quartz 7jlpe Material

Fe/dspa?ric Material

US. Patent

Jan. 5, 1988

Sheet 1 of 5

4,717,695

FI .. l
I

I00

8m6=00432

2 345 7 /0

2030405070/00 200

Effective Dbmefer (/um}

Ak/mina Type Mmaia/
0/00

Fl 6.. 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/

US. Patent

Jan. 5, 1988

Sheet 2 of 5

4,717,695

F
///

W
m.
w
w
m
000
m
0
E3$15SmQg m%

2/12043/

// / ,

/ //I6-2/M4/. wmrm/
.

my
07/3
r.m.

23457/0

MW
/

me

m m.1%

20 30 4050 70 I00

Effect/Ye Diameter (,um)

US. Patent

Jan. 5, 1988 ,

Sheet 3 of5

4,717,695

F/G.4
Alumina Type Material
0 I00

\I

= \l

\l

\l

\I

I0 20 30 40 50 60

Quartz 7j/pe Material

\l

70

80 90 I00
Fe/dgoath/c Maten'a/

US. Patent

Jan. 5, 1988

Sheet 4 of5

FY6158

20/um

4,717,695

US. Patent

Jan. 5, 1988 \

Sheet 5 of5

4,717,695

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 ( %)

4,717,695

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.
Accordingly, the particle size of the starting material
is restricted to be larger than a certain value, which
restriction is re?ected in a limitation of the homogeneity
of the porcelain microstructure and a comparatively

1. Field of the Invention

This invention relates to a high strength feldspathic
~ porcelain and a method for producing the same. More

spathic porcelain having a ?ne, homogeneous micro

low mechanical strength of porcelain. For instance, the

three-point bending strength of an unglazed test piece

lators and acid resisting porcelain, and the invention

also relates to a special method for producing such

1,400 kg/cm2 in case of alumina-containing porcelain

porcelain.

containing 20% of corundum. If the particle size of the

starting material is made very ?ne, cracks occur in the

particularly, 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
1,000 kg/cm2 in case of common porcelain and about

2. 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; namely, common porce

duction as pointed out above. Thus, for products which

lain and alumina-containing porcelain. The common

require a high mechanical strength, such as large high

voltage insulators, special measures have been taken, for
example adding a large amount of corundum or by
20 applying static hydraulic pressure onto the body for
quartz-type material, feldspathic material, alumina-type densi?cation followed by carving an insulator out of the
material, and clay-mineral material.
densi?ed body. Such special measures result in an in
FIG. 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.
25

porcelain consists essentially of quartz-type material,

feldspathic material, and clay-mineral material, while
the alumina-containing porcelain consists essentially of

therefor in the case of common porcelain made of

SUMMARY OF THE INVENTION

Therefore, an object of the invention is to obviate the

quartz-type material, feldspathic material, and clay-min

eral material. The ordinate represents unglazed bending
strength of porcelain, 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. As can be seen from 30 ing a more homogeneous microstructure than known

FIG. 7, 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.

Another object of the invention is to provide a

therefor. 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. 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.
On the other hand, it is empirically known in the art
of porcelain production that the ?ner the particle size of
the starting material, the more likely the occurrence of
cracks is in the drying and ?ring processes. In general,
when the content of particles with effective diameters
of not greater than 10 um surpasses 85% by weight (to
be referred to as % hereinafter), the crack tends to

drying and ?ring processes even when the starting ma

terial having a very ?ne particle size is used. The

method of the invention costs less than conventional

porcelain producing methods and does not require a

40

complicated production process.

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. Accordingly, the particle 45 by weight, whereby the unglazed bending strength of
the porcelain is greater than 1,400 kg/cm2 and the por
size of porcelain material has been controlled so that the
celain is free from defects larger than 40 um.
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.

The above cracks occurring in the drying or ?ring 50 following manner. Namely, 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; after being (2) calcined the
expansion and shrinkage between the inside and the
pulverized material is; (3) mixed with clay-mineral ma
surface thereof due to temperature differences therebe
tween during the drying and firing processes. The 55 terial, 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,
ing kneading and extrusion as a result of difference of
dried, 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.
caused during cutting the working of the body. Thus,
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.

In short, the feldspathic porcelain of the prior art has

ventional porcelains of similar types. More particularly,

the three-point bending strength of an unglazed test

a shortcoming in that, when the particle size of the 65 piece with a 12 mm diameter for the porcelain of the
invention is 1,400 kg/cm2 in the case of a common por
starting material is very ?ne, the risk of crack occur
celain composition, 1,800 kg/cm2 in the case of an
rence becomes high, and such risk is further increased

when such porcelain is used in making large high-volt

alumina-containing porcelain composition containing

4,717,695

20% of corundum, 2,100 kg/cm2 in case of an alumina

TABLE l-continued

containing porcelain composition containing 30% of

corundum, and 2,900 lrg/cm2 in case of an alumina-con

taining porcelain composition containing 50% of corun

dum.
The invention will be described in further detail now.

With the invention, the microstructure of porcelain is

made more homogeneous than before so as to improve

the strength thereof. To this end, ?ne materials of por

celain, 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.
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%.
Whereby, although more than 85 % of the starting mate
rials before the calcination are ?ne particles with effec

tive diameters not greater than 10 um, regular porcelain

making steps, such as kneading, extruding, drying and
?ring, can be effected in a manner similar to those of the

Effective
diameter
(pm)
50

Particle size distribution, in percentage

by weight of particles not greater than
designated effective diameter (%)
Coarse side limit
Fine side limit
100

100

In FIG. 1, 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. 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.S. Pat. No.
3,097,101. 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. 22,807/ 1973 which corre

sponds to U.S. Pat. No. 3,674,519. In contrast to such

known particle size distributions, the range between the

curves I1 and I2 represents the particle size distributions

of those quartz type materials, feldspathic material, and

conventional method.
alumina-type materials which are used in the present
The starting materials to be used in the present inven
invention. As can be seen from FIG. 1, the particle size
tion are quartz type materials such as siliceous sand, 25 of the quartz-type materials used in the invention is ?ner
feldspathic materials such as potash feldspar, and alu
than that of conventionally used quartz-type materials.
mina type materials such as (1-Al203. 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, so as to produce a parti
are also ?ner than those of the prior art.
cle size distribution of which 85-95% are particles with 30
FIG. 2 shows the blend composition of material cal
- effective diameters of not greater than 10 pm. The
cined (to be referred to. as calcination material) which
V1 above pulverization can be effected either (i) on each of
consists of quartz-type material, feldspathic material,
' the starting materials followed by mixing of the pulver
and alumina-type material. The shaded portion of FIG.
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, 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, 15-75% of feldspathic material, and not greater

than 85% of alumina type material. The particle size
distribution of a starting material mixture with such
' duction and the manufacturing facilities available.
The particle size in terms of the Stokes diameter, 40 composition is controlled so that 8595% of the parti
cles thereof have effective diameters of not greater than
" ' which is generally referred to as the effective diameter,
10 pm as shown in FIG. 1 and Table l. The starting
is determined by the sedimentation method.
material mixture with the preferred blend composition
FIG. 1 shows the particle size distribution of the
and the proper particle size distribution is calcined at
starting materials used in the invention. For compari
900-1,400 C., so as to provide the calcination material.
son, 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; namely, to
porcelain of the prior art are also depicted therein. In
homogenize the microstructure of the porcelain and to
this ?gure, the abscissa represents the effective diameter
prevent the cracking in later steps of porcelain produc
of particle, 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.
abscissa. 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,
material. 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 I2 of FIG. 1.
'
Namely, (i) to pulverize the calcined material and then
TABLE 1
mix it with clay-mineral material, (ii) to mix the calcined
material with clay-mineral material and then pulverize
Particle size distribution, in percentage
the mixture, 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.
I
0
4O
2
15
49
In a preferred embodiment of the invention, the parti
3
3O
60
cle size of a mixture consisting of 4580% of the cal
5
60
80
65 cined material and 2055% 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.
20
95
100
' tion. 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

4,717,695

made from the thus particle-size-controlled mixture by

proved. Since the starting material of the high strength

following the steps of kneading, extruding, forming,

feldspathic porcelain of the invention are very ?ne par

ticles, i.e., 85-95% thereof having a particle size of not
greater than that 10 pm, a low total degree of crystallin
ity of less than 40% results in a large deformation of the

drying, and ?ring at 1,l00-l,400 C. in a manner simi

lar to the corresponding steps of any suitable conven
tional method.

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, mullite, cristobalite, and quartz. A

preferred crystal composition consists of not greater
than 60%, more preferably 20-60%, of corundum,

porcelain during the ?ring, and stable production of

high-voltage insulators of complicated shapes becomes
difficult. The degree of crystallinity was determined by
the quantitative X-ray diffraction method, and the peak
diffractions for the individual crystals measured were

corundum (113), mullite (220), cristobalite (101), and

550% of mullite, not greater than 40% of cristobalite,

quartz (100).

and not greater than 10% of quartz.

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.

The blend composition of the major ingredients of

the high strength feldspathic porcelain is limited to
22-85% of SiOz, 10-73% of A1203, 1.5-6.5% of K20
and/or NaZO due to the following reasons. Namely, 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. The start

ing materials of the porcelain of the invention are in the
form of very fine particles, i.e., 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, such particles are molten

and reacted during ?ring, so that crystals larger than 20

and to obtain a body which can be easily extruded,
pm hardly remain in the porcelain. The inventors con
molded, and ?red. The performance characteristics
?rmed by an optical microscope and a scanning elec
considered include, in the main, mechanical properties,
thermal properties, and electric properties, such as the 25 tron microscope that the crystals of the porcelain of the
invention were not greater than 20 pm.
bending strength, the coef?cient of thermal expansion,
The defects in the porcelain are restricted to be not
volume resistivity, and the like.
greater than 40 um because defects larger than 40 pm
If the content of SiOZ, which is mainly introduced
reduce the porcelain strength and hamper production of
from the silica type material and the clay-mineral mate
rial, is less than 22% or more than 85%, the body he 30 high strength porcelain. The defects refer to foreign
material and pores in the porcelain. The foreign mate
comes hard to extrude, form, and ?re. If the content of
rial is substance which is different from proper materials
A1203, which is mainly introduced from the clay-min
of the porcelain, and most of such foreign matter enters '
eral material, is less than 10%, the extrusion and form
into the porcelain during body the manufacturing pro
ing become dif?cult, while if it exceeds 73%, the ?ring
temperature becomes too high and the baking process 35 cess. In a preferred method of the invention, the mesh of
the ?nal sieve for the molding slip mixture of the cal
becomes dif?cult. If the content of K20 and/or N820,
cined material and the clay-mineral material is 44 pm,
which are mainly introduced from feldspathic material,
so that foreign material passing the ?nal sieve melt
is less than 1.5%, the ?ring becomes dif?cult, while if it
when the porcelain is tired and the ?red porcelain is free
exceeds 6.5%, content of glass in the porcelain becomes
from residual foreign material larger than 40 pm. The
too high and the porcelain tends to be softened during
magnitude of the pore depends on the method of porce
lain production, and the method according to the inven
tion ensures that the pores in the porcelain produced
thereby are not greater than 40 pm. The inventors con
teristics of the porcelain, 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, mullite, cristobalite, and quartz.
The crystal phase, in terms of percentage by weight,
pm.
The unglazed bending strength of the high strength
is limited to not greater than 60% of corundum, 5-50%
feldspathic porcelain according to the invention is re
of mullite, not greater than 40% of cristobalite, and not
stricted to be more than 1,400 kg/cmz, because when
greater than 10% of quartz due to the following rea
the strength of feldspathic porcelain is improved by
sons. Namely, more than 60% of corundum makes the
restricting the blend composition, the crystal phase, the
?ring difficult. If the content of mullite is less than 5%,

the ?ring, so that stable production of porcelain of com

plicated shapes becomes difficult.
In order to produce the desired performance charac

the strength of the porcelain becomes insufficient, while

if it surpasses 50%, the ?ring becomes dif?cult. If the
content of cristobalite exceeds 40%, the coef?cient of

thermal expansion of the porcelain becomes too large

degree of crystallinity, and the microstructure thereof

in the aforesaid manner, such unglazed bending strength
is achieved. More particularly, an unglazed bending
strength of more than 1,400 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, on the basis of weight, the por
strength of the porcelain is reduced. More than 10% of
quartz makes the strength of the porcelain insuf?cient. 60 celain consists essentially of 22-85% of SiOz, 10-73%
The total degree of crystallinity is restricted to be
of A1203, and l.5-6.5% of K20 and/or NagO; the por
celain has a crystal phase formed of at least one crystal
more than 40% by weight, because if it is less than 40%
by weight, porcelain with excellent mechanical and
phase selected from the group consisting of corundum,
electrical properties cannot be produced. For example,
mullite, cristobalite, and quartz, a total degree of crys
with the increase of the total degree of crystallinity, the 65 tallinity of the crystal phase being more than 40%, 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, 5-50%
the volume resistivity and insulating strength are im
for mullite, not greater than 40% for cristobalite, and

4,717,695

not greater than 10% for quartz, grain size of the crys
tals being smaller than 20 um, and the porcelain being
free from defects larger than 40 pm. 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, the bending test
being carried out by using a loading machine at a cross

head speed of 0.5 mm/min.

High strength feldspathic porcelain with an unglazed

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, while if the content

of feldspathic material exceeds 75%, the porcelain tends
to be softened during the ?ring step and stable produc

tion of large high-voltage insulators is hampered.

As long as proper plasticity of the body is ensured by

bending strength of 1,800 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, clay-mineral mate
rial containing more than 85% of ?ne particles with

of SiOZ, 30-73% of A1203, not greater than 1.5% of

Fe2O3, not greater than 1.5% of TiO;, not greater than

chemical substances may be added to the calcination

effective diameters not greater than 10 pm and other

0.7% of CaO, not greater than 0.5% of MgO, and 5 material, provided that the homogeneity of the porce
l.56.5% of K20 and/or NazO and to contain 20-60%
lain microstructure is not deteriorated thereby. The

of corundum in crystal phase thereof. Such porcelain is

developed for large high-voltage insulators, so that

above-mentioned other chemical substance are, for ex

ample, Ti02, BaO, 21'02, B203, ZnO, etc.

30-60% of SiO; and 30-73% of A1203 are necessary to

The calcining temperature is restricted to be
render a high moldability; not greater than 1.5% of 20 900-1,400 C., because if the calcining temperature is
Fe2O3 is necessary for electric insulation; and not
below 900 C. the sintering effect is insuf?cient for
greater than 1.5 % of TiO;, and not greater than 0.7% of
producing a homogeneous microstructure in the cal
CaO, and not greater than 0.5% of MgO are necessary
cined material, while if it is above 1,400 C. foaming is
to facilitate the fring of large porcelain insulators. The
caused and ?ne homogeneous microstructure is not
reason for the restriction of 1.5-6.5% of K20 and/or
produced in the calcined material.
Na2O is the same as described above. 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 1,800 kg/cm2, while

calcined material, it has been found that a ratio of

strength feldspathic porcelain with an unglazed bending

erable. 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.
20-55% by weight of the clay-mineral material is pref
The inventors have also found that the above high

the clay-mineral material, and if such content is less than

20%
or more than 55%, the plasticity of the body be
blend composition which consists essentially of 30-60%
of SiO;, 30-73% of A1203, not greater than 1.5% of 35 comes insuf?cient and extrusion and forming of the
body become difficult.
Fe2O3, not greater than 1.5% of TiOz, not greater than
The firing temperature of the mixture of the calcined
0.7% of CaO, not greater than 0.5% of MgO, l.56.5%
material
and the clay-mineral material is restricted to be
of K20 and/or NazO, and not greater than 20% of at
l,l00-1,400 C. If the ?ring temperature is below
least one oxide selected from the group consisting of
TiOZ, BaO, ZI02, B203, and ZnO. In addition to the 40 l,100 C. a well sintered porcelain cannot be obtained,
while if it is higher than 1,4000 C. foaming occurs and
:. quartz-type material, feldspathic material, alumina-type
' strength of 1,800 kg/cm2 can be obtained by using a

.. material, and clay-mineral material, if not greater than

20% of at least one ingredient or reagent selected from

stable production of porcelain is hampered.

BRIEF DESCRIPTION OF THE DRAWINGS

For
a better understanding of the invention, reference
45
is made to the accompanying drawings, in which:
FIG. 1 is a graph showing the particle size distribu
ent or reagent is more than 20% the extrusion, forming,
tion of the materials of the porcelain according to the
and ?ring of the porcelain becomes difficult.
invention, 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;, BaO, ZI'OZ, and ZnO is

used, the above unglazed bending strength can be
achieved, but if the content of such additional ingredi

group consisting of quartz-type material, feldspathic

porcelain of the prior art;

material, and alumina-type materials, because such ma~

FIG. 2 is a diagram showing the composition range of

starting materials to be used in the invention, which

terial can produce porcelain having the desired physical

and chemical properties. 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, because if such ?ne particles are not

starting materials include quartz-type material, feld

spathic material, and alumina-type material;

FIG. 3 is a graph showing the particle size distribu

tions of quartz-type material, feldspathic material, and

alumina-type material which were used in the examples

of porcelain of the invention as described hereinafter;
extra pulverizing time is consumed without producing 60 FIG. 4 is a graph showing the quartz-feldspar

greater than 85% the desired strength of the porcelain

cannot be achieved, 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, 15-75% by weight of feldspathic

invention;

material, and not greater than 85% by weight of alumi

na-type material. The dominant reason for selecting

microscope of a penetration type, showing the micro

to be described hereinafter;
FIG. 5A is a photomicrograph, taken by an optical
porcelain according to the invention, the blend compo
sition of the above~mentioned calcination material is
microscope of a penetration type, 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. 5B is a photomicrograph, taken by an optical

4,717,695

10

structure of Reference Sample M of Example 1 pro

duced by a conventional method;

pm. After deferrization by a ferro ?lter, each casting

slip consisting of the mixture of the calcined material

FIG. 6 is a diagrammatic illustration of a solid insulaw

tor with shades; 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, kneaded by a
vacuum kneader, and extruded. 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, dried and ?red at l,300'-1,350 C. in a

porcelain made of quartz-type material, feldspathic

material, and clay-mineral material.
DESCRIPTION OF THE PREFERRED

continuous ?ring furnace. Whereby, ten kinds of porce

lain Samples A through I were produced and Table 3

FIG. 7 is a graph showing the relationship between

shows the properties of such Samples.

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.

but the starting materials and the equipment and condi

EXAMPLE 1

A through I of the invention. Thus, Reference Samples

range of the invention as shown in FIG. 2 and FIG. 4,

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; namely, sili
except the blend composition thereof.
ceous sand as the quartz type material, potash feldspar
Reference Samples L through N of Table 3 were
as the feldspathic material, and a-AlgO; and bauxite as
the alumina type material. Additionally, gaerome clay 20 made by a prior art method. Namely, three ingredients,
was selected as the clay-mineral material. The four
i.e., siliceous sand as the quartz-type material, 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 gaerome clay was elutriated

type material, were mixed at the ratios shown in Table

and 95% of particles thereof had a particle size of not

3, and each of the mixtures was pulverized by a ball mill
greater than 10 um, so that pulverization of this clay 25 through a wet process so as to make particle size of
was not necessary. 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. Gaerome
tion is shown in FIG. 3 and Table 2.
TABLE 2
Effective
diameter

(um)

clay as the clay-mineral material was then added to each

30

Particle size distribution, in percentage

by weight of particles not greater than
design_ated effective diameter (%)
Siliceous
Potash
a-AlzO3
sand
feldspar
alumina
Bauxite

21

' 30

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 casting slip produced
thereby was passed through a ferro ?lter for deferriza
tion. Each casting slip was dehydrated by a ?lter press
using a 88 um mesh sieve, kneaded, and extruded so as

to produce a test piece with a 12 mm diameter. After

35 being dried, each test piece was ?red at l,300'l,350 C.

in a continuous ?ring furnace.

As to the properties listed in Table 3, the degree of

crystallization was measured by the quantitative X-ray
diffraction method, and the blend composition was

determined by wet chemical quantitative analysis. The

sizes of the crystals and defects were determined by
observation through an optical microscope and a scan

ning electron microscope. The bending strength of the

Starting material mixtures for calcination were pre

pared by mixing the quartz-type material, the feld

spathic material, and the alumina-type material by using
nine compositions A through I of FIG. 4. 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 loading speed

being 0.5 mm/min in terms of its crosshead speed. The
coef?cient of thermal expansion was measured by using

mixed by a wet process with a ball mill, 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,l50'-l,300 C. in an ELEMA electric fur 50 principle of optical leverage, and the specimen for this
nace. In FIG. 4, Sample C was made by adding 5% of
measurement was dimensioned 4 mm dia.X50.00 mm.

ZnO into the composition of Sample C by extrapolation

and then calcining.
The clay-mineral material, i.e., gaerome clay in this

Of 'the electric properties, the volume resistivity, the

dielectric constant, and the dielectric loss tangent were

measured by the method of I IS (Japanese Industrial

case, was mixed with the calcined material of each of 55 Standard) C2141; and the insulating strength was mea

the Samples A through I at ratios of Table 3, 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. The acid resistivity was mea
sured by the JIS powder method of JIS R1503.

Sample thereof had particle sizes of not greater than 10

TABLE 3(a)
Composition and
properties

Invention

Reference

K L

73
27

60
30

40
30

40
30

20
5O

20
30

36
l9

27
18

5
30

0
30

20
10

10
80

--

45

55

60

70

70

I0 --

Composition
of calcined

material1%!
Quartz type
Feldspathic
Alumina

4,717,695

11

12

TABLE 3(a)-continued
Composition and
properties

Invention
A

(I-A1203) type
Alumina

Reference

K L

10

30

30

30

50

0 --

1,150 1,200 1,200 1,200 1,200 1,200 1,150 1,200 1,300 1,300 1,200 1,150 - -

(bauxitehypc
ZnO reagent

(extrapolation)
calcining

temperature ('C.)
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

31

30

32

34

30

TABLE 3(b)

Composition and
properties

37

Invention

Reference

79.1
16.8
0.7
0.3
0.1
0.1
2.3
0.6
0.0

72.3
23.1
0.8
0.5
0.1
0.1
2.4
0.7
0.0

60.0
34.9
0.9
0.9
0.1
0.1
2.4
0.7
0.0

58.0
33.7
0.8
0.9
0.1
0.1
2.3
0.6
3.5

56.1
36.8
0.9
0.9
0.1
0.1
3.9
1.2
0.0

47.7
46.8
1.0
1.3
0.1
0.1
2.3
0.7
0.0

51.4 44.6
45.3 52.2
0.5 0.5
0.3 0.3
0.1
0.1
0.1 0.1
1.7
1.6
0.6 0.6
0.0 0.0

35.7
60.1
0.5
0.3
0.1
0.1
2.3
0.9
0.0

33.0
62.8
0.6
0.3
0.1
0.1
2.3
0.8
0.0

35.8
62.0
0.5
0.3
0.1
0.1
0.8
0.4
0.0

62.7
28.7
0.7
0.3
0.2
0.1
5.5
1.8
0.0

76.6
17.9
0.6
0.3
0.1
0.1
3.4
1.0
0.0

67.3
27.8
0.6
0.3
0.1
0.1
2.9
0.9
0.0

53.9
39.9
0.7
0.3
0.1
0.1
3.7
1.2
0.0

14.5
32.1
8.7
0.0
55.3

17.6
25.0
4.0
5.0
51.6

24.0
12.5
1.6
12.8
50.9

35.2
5.1
0.0
8.5
48.8

25.7
0.6
1.0
14.8
42.1

34.6
0.5
0.8
18.8
54.7

12.1 22.1
14.9 4.9
1.4
1.2
32.4 38.2
60.8 66.4

8.4
0.0
0.0
48.0
56.4

8.0
0.0
0.0
49.2
57.2

16.2
3.8
9.1
51.3
80.4

10.5
0.0
0.0
5.6
16.1

13.8
7.6
13.0
0.0
34.4

15.2
1.0
8.0
11.5
35.7

16.0
0.0
1.0
20.8
37.8

Porcelain chemical

comEition%)
SiO-z
A1103
Fe2O3
TD;
CaO
MgO
K20
NaZO
ZnO

Crystals in

@rcelain!%!
Mullite
Cristobalite
Quartz
'
Corundum
Total crystals

TABLE 3(0)
Composition and

Invention

Reference

properties

C'

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 1,120

1,380

0.524 0.467 0.360 0.271 0.326 0.308 0.440 0.345 0.365 0.366 0.398 0.327 0.463 0.415

0.402

0.008 0.008 0.007 0.007 0.006 0.005 0.005 0.005 0.004 0.004 0.250 0.012 0.024 0.022

0.015

Bending strength
of unglazed

1,420 1,570 1,680 1,780 1,750 1,950 2,160 2,400 2,850 2,940

570 1,210

12rnmdia. test

piece (kg/cm2)
Coef?cientot

thermal expansion
(%, at 650 C.)

Acid resistivity

(%)
Volume resistivity

12

11

l5

18

4.1

9.2

25

13

11

8.7

0.015

0.5

0.77

0.89

6.0

6.1

6.1

5.9

6.4

6.6

6.5

6.8

6.9

7.0

5.8

7.5

7.7

8.1

1.5

1.8

1.4

1.0

3.8

1.4

1.2

1.2

1.4

1.5

43

5.8

4.6

4.0

42

43

50

49

41

42

46

48

44

42

15

38

36

27

(x 1013 .(I-cm,
at 25C.)
Dielectric
constants

(50 Hz, at 25 C.)

Dielectric loss

tangenttan?
(x 104, 50111,
at 25' C.)
Insulating

strength (kV/cm)
As can be seen from Table 3, 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, 835% of mullite, not greater than 32% of cristo
26-38 pm. Their blend composition was in a range
balite, and not greater than 9% of quartz, and the total
consisting of 33-80% of SiO;, 16-63% of A1203, and
degree of crystallinity was in a range of 42-66%. Their
2.25.1% of K20 and/or NaZO. The amounts of various
bending strength fell in a range of 1,420-2,940 kg/cm2.

13

4,717,695

More particularly, Sample E containing 18.8% of co

rundum had a bending strength of 1,950 lag/cm2 and
Sample I containing 49.2% of corundum had a bending
strength of 2,940 kg/cmz, 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 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. After deferrization by a ferro ?lter, the

pulverized starting material mixture was passed through

of corundum but was made by a conventional method.

Reference Sample I, 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,

dried by an electric drier. The dried starting material

mixture was crushed by a roll crusher into particles not
greater than 10 mm, and then continuously calcined at
1,150 C. by a rotary hearth kiln for baking tiles. The

i.e., 10% of potash feldspar in the calcination material,

resulted in an insuf?cient amount, i.e., 1.2%, of K20
and NazO. Thus, 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. 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.
15

feldspar in the calcination material resulted in an exces

sive amount, i.e., 7.3%, of K20 and NazO, and its total
degree of crystallinity was 16.1% and its bending

strength was merely 1,210 kg/cml.

In mixing 69% of the calcined material and 31% of

the gaerome clay as shown in Table 3, 15% of the ga
erome clay was at ?rst loaded into a trommel together
with the calcined material. The remaining 16% of the
gaerome clay was pulverized through a wet process in

Reference Samples L through N, which were pre 20 such a manner that when being added to the above
pared by a conventional method, 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, and then such remaining
tallinity in a range of 34-38%, a defect size in range of
gaerome clay was loaded into the trommel and thor
52-86 pm, and their bending strengths were 950-l,380
oughly mixed. After deferrization by a ferro ?lter, the

kg/cmz.

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. The dehy

the quartz type material, the feldspathic material, and

drated slip was extruded by a vacuum extruder so as to

the alumina type material, in order to obtain a high

produce bodies with a diameter of 290-310 mm and an
strength and a low thermal expansion. Such addition of 30 overall length of 1,800 mm. Thirty pieces of the above
ZnO proved to improve the bending strength by 100
solid insulators with shades, thirty rod-like solid insula
kg/cm2 and to reduce the coef?cient of thermal expan
tors of the above ?rst kind, and thirty rod-like solid
sion by about 0.09% at 650' C.
insulators of the above second kind were formed and

Samples A through I of the porcelain of the invention

dried. The dimensions of the solid insulators were all as
proved to have electric properties and acid resistivity 35 mentioned above.
which were better than those of Reference Samples L
After drying, it was con?rmed by inspection of all the
through N made by a conventional method.
FIG. 5A shows a photomicrograph of the micro
structure of Sample F of the porcelain according to the
invention, which photograph was taken by a penetra 40

tion type optical microscope. For reference, FIG. 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. After the inspection, the insulators were
glazed and ?red at l,300-l,350 C. in a continuous
?ring furnace. 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. The drying crack was checked by inspec

5A and FIG. 5B, the porcelain made by the method of 45 tion with the eye, 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.
tration. The sintered conditions were checked by a
method. As can be seen from the comparison of FIG.

EXAMPLE 2

Sample insulators were made by using the porcelain 50

of the invention, 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.

The samples of the large high-voltage insulators of

the invention, i.e., the solid insulator with shades having
a cylindrical portion diameter of 145 mm, rod-like solid

lators. Such sample insulators included solid insulators

insulators with a diameter of 165 mm, and the rod-like

solid insulators with a diameter of 185 mm, were pro
like solid insulators; 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, a shade portion diameter 230 mm, and an overall
cracks and ?ring cracks.
with shades as shown in FIG. 6 and two kinds of rod

length of 1,150 mm, while a ?rst kind of the rod-like

As described in detail in the foregoing, high strength
solid insulator had an overall length of 1,150 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
1,150 mm and a cylindrical portion diameter of 185 mm.
?nely pulverized materials and improve the mechanical

The porcelain of Sample F of Example 1 was used for

strength of porcelain. In a method of the invention, of
the sample insulators. Starting materials were siliceous
various starting materials, the quartz-type material, the
sand as the quartz-type material, potash feldspar as the 65 feldspathic material, and the alumina-type material are
feldspathic material, (It-A1203 as the alumina-type mate
?nely pulverized, mixed and then calcined for provid
rial, and elutriated gaerome clay as the clay-mineral
ing a calcined material with a homogeneous microstruc
material. The siliceous sand, potash feldspar, and a
ture, and then the clay-mineral material is added therein

15

4,717,695

16

phases being not greater than 20 pm, and a size of de

fects in said porcelain being not greater than 40 Jun.

and the particle size distribution of the mixture is con

trolled, so that a suitable moldability is rendered to the
body at each of the steps for kneading, extruding, form

2. High strength feldspathic porcelain as set forth in

claim 1, wherein said unglazed bending strength is at

cracks is effectively prevented in the drying and ?ring 5 least 1,950 kg/cm2, and the amount of Si02 is 30-60%
by weight, and the amount of A1203 is 30-73% by
processes.
weight.
The porcelain and the method of producing the same
3. High strength feldspathic porcelain as set forth in
according to the invention contribute greatly to the art
claim 1, wherein said porcelain is for porcelain insula
of large high-voltage insulators by providing very
tors.
strong and compact insulators with excellent electric
4. High strength feldspathic porcelain as set forth in
properties such as are resistivity. Additionally, the por
claim
1, wherein said porcelain is acid resisting.
celain of the invention has a high chemical resistivity
5. High strength feldspathic porcelain with an un
such as acid resistivity.

ing, drying, and ?ring, whereby the occurrence of

glazed bending strength of greater than 1,800 kg/cmz,

Although the invention has been described with a
the porcelain consisting essentially of:
certain degree of particularity, it is understood that the
30-60% by weight of SiO;, 30-73% by weight of
present disclosure has been made only by way of exam
A1203, not greater than 1.5% by weight of Fe2O3,
ple and that numerous changes in details of construction
not greater than 1.5% by weight of Ti02, not
and the combination and arrangement of ingredients
greater than 0.7 % by weight of CaO, not greater
and steps may be resorted to without departing from the 20
than 0.5% by weight of MgO, l.5-6.5% by weight

scope of the invention as hereinafter claimed.

What is claimed is:

of at least one oxide selected from the group con

sisting of K20 and NazO, and not greater than 20%

vby weight of at least one oxide selected from the
group consisting of TiOz, BaO, ZrOz, B203, and

1. High strength feldspathic porcelain with an un

glazed bending strength of greater than 1,800 kg/cmz,

the porcelain consisting essentially of 22-85% by

ZnO, the porcelain having a ?rst crystal phase

weight of SiO;, 18.8-73% by weight of A1203, not

greater than 1.5% by weight of Fe2O3, not greater than
1.5% by weight of T,O2, not greater than 0.7% by
weight of CaO, not greater than 0.5% by weight of

formed from corundum in an amount of 2060% by

weight and at least one second crystal phase se

MgO and 1.5-6.5% by weight of at least one oxide 30

selected from the group consisting of K20 and NagO;
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, cristo

balite, and quartz, a total degree of crystallinity of

said second crystal phase being greater than 40%

by weight for cristobalite, and not greater than
10% by weight for quartz, a grain size of said crys

tal phases being not greater than 20 um, and a size

of defects in said porcelain being not greater than
sisting of mullite, cristobalite, and quartz, a total degree 35
40 pm.
of crystallinity of said second crystal phase being
6. High strength feldspathic porcelain as set forth in
greater than 40% by weight, a degree of crystallization
claim 5, wherein said porcelain is for porcelain insula
for said at least one second crystal phase being selected
tors.
7. High strength feldspathic porcelain as set forth in
in ranges of 5-50% by weight for mullite, not greater
than 40% by weight of cristobalite, and not greater than 40 claim 5, wherein said procelain is acid resisting.
1!
=8
*
1.!
Ill .
10% by weight for quartz, a grain size of said crystal

45

50

55

65