Patentamt

Office
J E u r o p European
a i s c h e Patent
s

Publication number:

EUROPEAN

048

5 2 6

A2

Office europeen des brevets

PATENT A P P L I C A T I O N

Application number: 81201048.6

Int. CI.3: C 03 C 9 / 0 0

@ Date of filing: 18.09.81

Priority: 19.09.80 US 188919

Date of publication of application:
31.03.82 Bulletin 82/13
Designated Contracting States:
AT BE CH DE IT LI LU NL SE

54) Vitreous frit and fired sanitary-ware body.

A process for producing feldspathic sanitary ware and
the end product are disclosed in which a fluxing amount of a
glass frit is used in the ceramic slip used to cast the sanitary
ware. The frit contains both deflocculent oxides and flocculent alkaline earths which are leachable from the frit when it
is placed in the ceramic slip. The deflocculent oxides
counterbalance the effect of the flocculent alkaline earths to
the extent they are respectively leached from the frit upon
dispersal in a ceramic slip and maintain the slip at a workable
viscosity. Upon casting and firing the slip, the present frit
precipitates fine crystals of diopside having an average
particle size of less than one micron which are particularly
useful in lowering the firing temperature of feldspathic
bodies by promoting the required degree of vitrification at
lower temperatures than heretofore possible.

Applicant: FERRO CORPORATION

One Erieview Plaza
Cleveland Ohio 441 14(US)
Inventor: Votava, Werner Friedrich
4092 Diana Drive
Broadview Heights Ohio 44147(US)
@ Representative: Kooy, Leendert Willem et al,
Octrooibureau Vriesendorp & Gaade Dr. Kuyperstraat 6
NL-2514 BB The Hague(NL)

like,

the

particularly

vitrified,

feldspathic

The body is u s u a l l y
tunnel

kiln

former,

are

dried,

slip

is

nepheline
d

casting

for

the

slip,

meet c e r t a i n

rigid,

For example,

the

slip

periods

of time

point

of c a s t i n g

shrinkage,

as the

ideally

bodies
c

as a

having
.

constant

are

all

hereinafter,

property

body,

the

must

standards.
of t h e

and stability

over a p p r e c i a b l e

critical

desired wall

or c o m p l e t e

generic

vitrified

fired,

of

more d e t a i l

specific gravity

factors

cone

content

partial

and p h y s i c a l

remain

in a

sand o r

feldspathic

changing this

final,

rheological

as these
t

casting,

to vitrification

of the mineral

used

be d e s c r i b e d i n

viscosity,

should

casting

highly

to as " f e l d s p a t h i c "

nowadays

without

feldspar

as well

a glazed,

of Seger p y r o m e t r i c

proportion

However,

as will

Ideally, and

referred

can be o p t i o n n a l l y

syenite

and t h e

method of s l i p

and f i r e d

equivalent

a substantial

feldspar.

replacement

constructed of

glazed

at a t e m p e r a t u r e
that

indicating

lavatories

bowls,

b o d y .

10. The body is normally

9 to
the

toilet

formed by t h e w e l l - k n o w n

and slowly

carefully

i.e.,

fixtures,

Sanitary-ware

from the

thicknesses,

stand-

drying

The f i r e d

body,

strength,

with minimum,

In an e f f o r t
the

lower

firing

been

tried

with.

vitrification

but

of c o n v e n t i o n a l

body f l u x e s

"short

vitrification

within

a commercial

vitrification

will

kiln,

slip

sanitary-ware
vitrification

test

fired

bar,

on a commercial

kiln.

Thus,

at p r e c i s e l y

if

cone
11 i t

way to achieve

A related
which

problem

a glass

somewhat

frit

soluble.

spread,
of

degree

without

slumping

in c a s t i n g
serves

of the

Components

leached

is

that

of

body r e a c h e s

at cone
slump,

because

9 it

is

there

at p r e c i s e l y

is

no

cone

zone of a p r o d u c t i o n

the

from the

frit tends

frit,

not

the

ware from a ceramic

sanitary

as a flux

manufacture

in a c o n t i n u o u s

control
firing

or no
controlled

carefully

while

apparent

temperature

section

scale

has begun to

problems become r e a d i l y

at cone

cross

required

under

10 down,

production

the

temperature

a sanitary-ware

whereas

throughout

utilization

By way of e x p l a n a t i o n ,

to s u c c e s s f u l

vitrified,
practical

the

would be of l i t t l e

range

is v i t a l

it

products

tunnel

production

to the

short

strenght,

accompanied

and be s u s t a i n e d

a vitrification

conditions,

laboratory

lower

which the

over

excessive

(devitrification).

in a small

significance

created

no m a j o r

poses

instability,

or f i r i n g ,

refers

both occur

crystallization
while

have

with v a r y i n g

have g e n e r a l l y

used h e r e t o f o r e .

range"

have

materials

process,

process

have u s u a l l y

etc.,

range,

and t o

operation

solved.

or warpage on drying

Therefore,

firing

many f l u x i n g

such f l u x e s

However,

in and of i t s e l f ;

shrinkage

and/or

For example,

up the v i t r i f i c a t i o n

speeding

on f i r i n g .

any number of body a d d i t i v e s

than they have

more problems

problem,

the

speed

have h i g h

vitrified,

shrinkage

to speed the body v i t r i f i c a t i o n

of success.

is,

uniform,

or both,

temperature,

experimented

That

be c o m p l e t e l y

though

to e i t h e r ,

been

degrees

will

ideally,

slip
to b e

notably

the

10
kiln.
in

alkaline
the

earths,

of the

visocity

to make it

slip

may even v i r t u a l l y

slips

an unworkable
time.

short

Also,

of t h i s

The f i e l d

invention

all

the

slip

the

invention

by the

the r e q u i r e d
as well

stage,
slip

workable

includes

The u t i l i z a t i o n
Kurczyk

Synthetic
Ceramics

in a paper

Kurczyk d i s c l o s e s
crystallization
preferred
dolomite

at

pretreatment
produced

to ceramic

same t i m e
Further,

of f l o c c u l e n t s
maintance

leached
of a

or diopside

(Ca0.Si02)

ceramic

bodies

"Synthetic

Italy,

bath,

is

the

in the

is

disclosed

Diopside

and

for Ceramics",
Meeting

May 27-31,

of s y n t h e s i s

synthesis

from a molten

and ground q u a r t z

adaptability

slip.

body in b o t h

product.

3rd I n t e r n a t i o n a l

Rimini,

including

diopside

the

at

of said

fired

New Raw M a t e r i a l s

method a p p a r e n t l y

hydrothermal
However,

entitled,

the p o s s i b i l i t y

number of means,

while

body,

final,

for

3rd CIMTEC,

Technologies

product.

on the

effect

and a r e s u l t i n g

as an a d d i t i v e

of the

sintered

to lower the p r o d u c t i o n

designed

wollastonite

Wollastonite -

Proceedings

slip.

of e i t h e r

(CaO.MgO.2 SiO )
by H.G.

of the

to

with the p r o d u c t i o n

characteristics

frit

leaves

slip

in the

a counterbalancing

from fluxing

viscosity

ceramic

earth

flocculation

in a r e l a t i v e l y

flocculating

as in the

In f a c t ,

this

place

cast

of a s a n i t a r y - w a r e

temperature

preserving

some

deals primarily

body a d d i t i v e s

of s a n i t a r y - w a r e

unworkable.

alkaline

has an u n d e s i r a b l e

likewise

firing

of the

sintering

raise

take

can o f t e n

viscosity

and can s u f f i c i e n t l y
Moreover,

solidify.

amount of u n r e a c t e d

certain
This

as f l o c c u l e n t s

act

from t h e
on Modern

1976.

of d i o p s i d e

by any

by s o l i d - s t a t e

reaction,

etc.

Kurczyk's

sintering,
formation

of d i o p s i d e

from

appropriate

molecular

ration

by

and c a l c i n a t i o n .
by s i n t e r i n g ,

bodies,

from the

standpoint

has a number of drawbacks.

of

First,

the

sintering
for

that

used

well

known,

utilizes

process

the manufacture
is

it

kiln

in t e m p e r a t u r e

variations

with

in a high p e r c e n t a g e

partially

molten

sintering

zone,

slag-type

coating

the

Furthermore,
is

relatively
its

to reduce

tends

crystal

to mill

to be e f f e c t i v e l y
It

has been

dispersed

to

heavy,

undesirable

the

all

providing

a number of a d d i t i o n a l

temperature

and tough,

thereby
size

a particle

molten

under

steps

enough

body s l i p .

controlled

hereinafter

form of d i o p s i d e
of Kurczyk,

disadvantages

improvements

mineral

bath which Kurczyk

created

superior

of

making i t

small

a sanitary-ware

processing

the

which

firing

by

which t e n d s

the d i o p s i d e

produced,

achieved,

30 microns)

known,

the

if

by the novel

eliminates

attendant

method d i s c l o s e d

(10 to

is d e l i b e r a t e l y

a more economically

forth,

of a n o n - u n i f o r m ,

with

throughout

found however t h a t ,
followed

conditions,

hard

and grind

found to be u n d e s i r a b l e ,

from t h e

in l o w e r i n g

to be extremely

most d i f f i c u l t

upon d i s c h a r g e

by the

as is well

body and,

a sanitary-ware

burn",

operation.

grained

effectiveness

wherein

or cause

walls

produced

large

firing

material,

formation

calciner

diopside

a "soft

of u n r e a c t e d

in the

resulting
on the

either

solidifies

in the o v e r a l l

interruptions

Kurczyk

which

the

to

As i s

of p r e c i s i o n ,

any degree

may promote

resulting

bath

to c o n t r o l

difficult

similar

operation

cement c l i n k e r .

of p o r t l a n d

exceedingly

in a r o t a r y

temperature

kiln

a rotary

set
is

while

thereover.

OBJECTS
It

is

therefore

improved
It

is

an o b j e c t

crystalline

another

temperature

object

glass

of t h i s

invention

to provide

a new and

form of d i o p s i d e .
of t h i s

matrix

invention

from which

may be formed upon r e h e a t i n g

said

to provide

fine

glass

grained
to

its

a relatively
diopside

low

crystals

crystallization

temperature.
It

is yet

another

in g l a s s

precursors

and which g l a s s ,
some fine
formed
It

is yet

of fine

readily

milled

will

a ceramic

body,

at

least

precipitate

uniformly

invention

and

dispersed

fineness

a vitreous

to provide

can be e a s i l y

diopside crystals which

to a c h i e v e a

object

low t e m p e r a t u r e

is a f u r t h e r

from glass

of t h i s

to a s u f f i c i e n t

is a n o t h e r

relatively

into

temperature

said b o d y .

throughout

grained

low melting

incorporated

diopside,

diopside

for

and

into

incorporation

ceramic b o d y .

feldspathic

It

crystalline

object

to provide

of the body,

upon f i r i n g

another

source

It

may be r e a d i l y

grained

in s i t u

invention

in a r e l a t i v e l y

solution

which g l a s s

glass,

of this

object

object

of t h i s

glass

to c o u n t e r a c t

invention.

flocculents

leached by a s l i p

their

increasing

the

an o b j e c t

to provide

a new and i m p r o v e d ,

and p r e v e n t

of the

viscosity

slip

values.

to unworkable
And f i n a l l y ,

for m a n u f a c t u r i n g t h e

process

it

is

body,

sanitary-ware

as w e l l a s

the

provide

for

process

achieving

same.
SUMMARY OF THE INVENTION
The p r e s e n t

invention

and s e m i - v i t r e o u s
maintaining

increased

deflocculent

bodies

a suitable

of such m a t e r i a l .
with

reduces
firing

productivity.

range
there

glass

of v i t r e o u s

temperatures

feldspathic
is

substantial

alkaline

while

materials,

and o t h e r p h y s i c a l

By s u b s t a n t i a l l y

and f l o c c u l e n t

from the

firing

comprising

As a r e s u l t ,

oxides

extractabilities

the

properties

fuel

balancing

savings
the

earth

added to a s l i p ,

its

visocity

can

within

be m a i n t a i n e d

In one form of the

finely

(as during

temperature
diopside
firing

crystals

oxides

deflocculent
earths

the

without

leached

unworkable

for

diopside

therefrom

above a c e r t a i n

ceramic
at

firing

temperature

crystals.

The f r i t

and p r e v e n t

fine

body)

as a flux,

example,

which c o u n t e r b a l a n c e

to be f i r e d

namely MgO, CaO,

when heated

and act

substantially,

form of a

in s o l u t i o n

in d i o p s i d e ,
of the

out

as compared to the

Seger cones

contains

that

firing

precipitate

temperature

required

the

in the

ceramic m a t e r i a l

the

contained

so f o r m u l a t e d

and is

hereof

glass

The f r i t

body.

oxides

of the

and Si02,

the

is mexed with

to form a f e l d s p a t h i c
quantities

limits.

invention,

frit

ground

workable

lowering

least
that

the

three
would b e

contains

any f l o c c u l e n t
of the

thickening

grained

leachable

alkaline
to a n

slip

visocity.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

the

in s o l u t i o n

to achieve

and f i r e d
the
fine

firing,

diopside
the

the

which

desired

serve

as a f l u x .
the

lowers

material

in forming

these

precursors,

CaO, MgO, and Si02,

of the

weight p e r c e n t

frit

containing

components

glass.
about;

of v i t r i f i c a t i o n .

firing

the

For example,

temperature

sanitary-ware

should

detail,
comprise

such a glass

During

and p r e c i p i t a t e s

The c r y s t a l l i n e ,

in g r e a t e r

Considering
weight

degree

from the p r e c u r s o r s

substantially

ceramic

a glass

precursors

forms

diopside

crystals

invention,

CaO, MgO, and SiO2, i n

a ceramic m a t e r i a l t h a t is shaped into a b o d y

diopside

with

incorporated

the p r e s e n t

with

In accordance

as

fluxing
required

or o t h e r

of

body.

the d i o p s i d e
at l e a s t

35% b y

may comprise

in

the additive

in a p p r o x i m a t e l y
of the

a fluoride

percent

when p r e s e n t
of at

A more d e s i r a b l e

additive

least

indicated

being

based

introduced

one metal

composition

being

approximately
the

the

on the

following
total

weight

glass:

the f l u o r i n e

the

from one or more of the

selected

being

selected

the p e r c e n t

into

the batch

as

of the c o m p o s i t i o n .

comprises

in weight

percent

from one or more of the

indicated

based on the

about:

in

following

total

weight

of

glass:

A preferred
the glass
about:

compositional
containing

the

range

and a p r e f e r r e d

diopside

precursors

are

composition
in weight

for
percent

be a p p r e c i a t e d

It will
oxide

of the

analyses

the

yield

can be smelted
about

76:24

ingredients
oxide

11:89,

or s a l t

or f l u o r i d e

lepidolite,

included

Whiting

the p r e s e n t

glasses

can be added to the batch,

reduces

For example,

may c o n s t i t u t e

of

can be s u b s t i t u t e d

form or in a form which

like

and

for

and any of the o t h e r

dolomite,

form on s m e l t i n g .

and the

bath

in a weight r a t i o

and l i t h o s p a r

of the

metal

which on smelting

For example,

respectively.

optionally

The c o r r e s p o n d i n g

materials

analysis.

small p o r t i o n

oxide

in the

oxide

constitute

compositions

glass.

those

from dolomite

to

a relatively

these

smelted

may c o n s t i t u t e

materials
cooling

that

to the m e t a l

spodumene,

of the

part

either

batch

formulation.
Compositions

with

approximating

is

about
it

or p a s s i n g

conventionally

may be ground
Sieve.

vitreous

or n e a r l y

A glass

of the

incorporated

manner,

ground p r i o r
about

temperatures

The melt may b e

rollers.

to use.

95% p a s s e s

examination

X-ray

at

the melt

such as by quenching

between f r i t t i n g

so t h a t

Standard

is

ranges d i s c l o s e d melt
2600F to about 2750F.

in any c o n v e n i e n t

fritted
water

the

The f r i t

As an example,
through

shows t h a t

so o b t a i n e d
the

325 mesh,

the

frit

in

frit
U.S.

is t o t a l l y

so.

type d e s c r i b e d ,
with

suitable

containing
ceramic

the

materials

diopside
that

precursors,
is

adapted

to form s a n i t a r y

As d e s c r i b e d

ware.

the

is

then

fired

casting

may be c o n t r o l l e d

by p r o v i d i n g

balancing

leachable

of d e f l o c c u l e n t .

amounts

commercial

glasses

deleterious

way.

A preferred

ceramic

that

one,

is

content

with

is lower by at
without

the

present

glass

the

body.

Amounts

instant

precipitate

other
in a

properties

a feldspathic

of the m i n e r a l

portion

in s i t u

In one i n s t a n c e ,

crystallized

at about

not c r i t i c a l .
of the

Upon such
instant

forming

The c r y s t a l s

advantageous.

are

in a c c o r d a n c e

a present

preferred

the

this

at l e a s t

crystals
glass

temperature

about

to c r y s t a l l i n e

body.

the d e s c r i b e d

fine

that

range

ceramic

glass,

although

converts

of the body

of the

was observed

extremely

A substantial

an average

the

5% by weight

of

temperature

is

50% by

diopside,

the

residue.

a glassy

formed

firing

However,

(9000C),

of a

Any a d d i t i o n

as 0.1% by weight

crystallization,

glass

of f i r i n g

temperature

in the body as very

it

16520F

the

in the

body c o n t a i n i n g

of d i o p s i d e .

formed

In c o n t r a s t

glasses.

as l i t t l e

3% to about

about

precursors

formed has

or c o u n t e r -

cones than would be r e q u i r e d

some r e d u c t i o n

a ceramic

quite

and i t s

counteracting

invention,

Seger

of the

Upon f i r i n g

balance

slip,

slip

10% or more a r e u s e f u l .
is

glass

present

three

least
effects

to as much as

weight

of the

in which a s u b s t a n t i a l

presence

ceramic

of the

does

feldspar.

In accordance

the

sanitary
glass

used to form the body is

material

bodies

is,

affect

can markedly

the

a body,

the p r e s e n t

properties

viscosity

into

shaped

to y i e l d

hereinafter,

more f u l l y
affect

not s i g n i f i c a n t l y

then

The body is

casting.

as by s l i p

and the mixture

ware,

particle
with

fine

and t h i s

portion of

size

less

the p r e s e n t

than

the

is b e l i e v e d

crystalline diopside

one micron.

invention

to b e

is a

Diopside

better

body

than

flux

in part

to the

fluxing

lowers

the

of the

dissolution

in the

subsequent

required

still

retaining

and reducing

by the p r e s e n t
firing

a'good,

results

with

bodies

feldspathic
the

than

appears

from cone

10 to

diopside

to take

place

from f i r e d

This

so e f f e c t i v e
three

that

Seger

12 to cone 5 to 6 ,

wide

show t h a t
crystals.

by f u s i o n

mixtures

firing

temperature

A progressive
of the

For purposes

of comparing the b e n e f i t s

invention

following

is

diopside

with

that

exemplary

of the p r e s e n t

no new compounds

of the

the

is
least

at

assimilation

present

action.

fluxing

glasses

sufficiently

formed which

warpage.

X-ray d i f f r a c t i o n
other

to be due at l e a s t

diopside

temperatures

and t y p i c a l l y

cones

pyrometric
while

nature

accorded

action

is b e l i e v e d

This

diopside.
grained

fine

to f a s t e r

leads
it

synthetic

are

formed

formation

glass

feldspathic

glasses

matrix

and

crystals.
and degree

of u t i l i t y

which has been p r a c t i c e d

of a c o n v e n t i o n a l

of t h e

in the p a s t ,

cone 9-10 body

used h e r e t o f o r e :

composition

The composition

of the

feldspar

KNaO . A l 2 O 3 .

was e s s e n t i a l l y

6SiO2.
The sodium s i l i c a t e
to achieve

was added as a 50% aqueous

an i n i t i a l

viscosimeter

on e i t h e r

slip

viscosity

solution

as measured

a 3 or a 5 s p i n d l e

sufficient

on a B r o o k f i e l d
at

10 RPM.

The f o r e g o i n g
bars
the

for

in the

reported

Firing

Percentage
This

physical

the

In t h i s

it

regard

the

predictably,

provide

because

following

as being

need for

the

by the

indicated

lower

the

existing
article
below,

compounded to provide
the

in Table

below

as well

as those

were a r r i v e d

tables,

difference
dried

at

1.

which

as f o l l o w s :

extensive

Percentage

Absorption:

Percentage

absorption

between

length

dried

length

and m u l t i p l i e d

by

percentage.

should be noted

a finished

body as d e s c r i b e d

tabulated

11,

and

and w a r p a g e ,

adsorption

characteristics,

divided

length,

100 to p r o v i d e

However,

shrinkage,

test

Shrinkage:

was determined

and f i r e d

into

one cm. by one cm. by 10 cm.,

from cone 8 to cone

results,

was c a s t

body composition

and t o t a l

firing

The f o r e g o i n g
are

dimensions

the

having

measured

sanitary-ware

at l e a s t

that,

shrinkage,
commercial

generally

the

approximately
commercial

was o b t a i n e d

of 10% s h r i n k a g e ,

instant

invention,

10% shrinkage

mold r e d e s i g n

using

and

the b e t t e r .

molds have been d e s i g n e d

in c o n t e m p l a t i o n
utilizing

theoretically

the

has been

to e l i m i n a t e

at t h i s

ASTM t e s t

to

time.

method C373-72.

of a p p r o x i m a t e l y

An a b s o r p t i o n
to a s s u r e

inch

square
for

vitrified

a sufficiently

which s a n i t a r y
a high

is put,

ware

of s u r f a c e

0.5% or less
body.

and f u r t h e r

exposed

will

generally

considering

use

to

that

not

every

the

be g l a z e d ,

be r e a d i l y

necessary

the

Considering

to water will

of v i t r i f i c a t i o n

degree

is

need

apparent.

Warpage:
Warpage was measured
the

firing,

during

two and one h a l f

using

a depth

of warpage,

A warpage
acceptable

Percent

Total

figure
the

except

at the

midpoint,
of t h e

as a measure

in i n c h e s .

slightly

is

more or l e s s ,

and would be expected

unacceptable

considered

to produce

to b e

commercially

beyond 20 mils

Anything m a t e r i a l l y

ware.

would l i k e l y

fixtures.

Shrinkage:

was d e t e r m i n e d
initial

essentially

the

same as f i r i n g

measurement was made while

in the p l a s t i c

state,

the

test

shrinkage,

bar was

to d r y i n g .

prior

Modulus of R u p t u r e :
Modulus of Rupture

wherein

span

to room t e m p e r a t u r e ,

support

taken

inch

a five

over

cooling

from e i t h e r

droop being

reported

in c o m m e r c i a l l y

result

still

the

of 20 m i l s ,

the norm,

about

This

gauge,

inches

supported

after

measurement,

taken
degree

bars

on t e s t

was c a l c u l a t e d

M = the modulus

of r u p t u r e
load,

1 = the d i s t a n c e

between

breadth

d = the

depth

standard

in pounds per

the knife

of the bar

of the

the

formula:

square

inch;

in p o u n d s ;

P = the b r e a k i n g
b = the

using

bar,

edges

in i n c h e s ;
in i n c h e s .

in i n c h e s ;

Modulus
the

of r u p t u r e

fired

per

Commercial

body.

conditions

and t h i s

inch,

shown in Table

values

in

following

cone

be seen

It w i l l

above base
forth

Using the

cone

feldspathic
the

for

the

both

body

of the

the

firing

but for
is

a slight

instant

temperature,
the

body,

was u s e d :

reduction
the

essentially

in Si02,

the

same as t h a t

set

cone 9-10 p r o c e s s i n g .
5-6 base body c o m p o s i t i o n
there

is t a b u l a t e d

of a s e r i e s

of s a n i t a r y - w a r e

and mixed with v a r i o u s

auxiliary

and the

viscosity,

cone

as with the

of Na2SiO3.

as t h e

as j u s t g i v e n

in the

weighed
solution

7000 p o u n d s

experimental

of a s a n i t a r y - w a r e

5-6 base body c o m p o s i t i o n

that,

our e x p e r i m e n t a l

of about

effectiveness

lowering

time of f i r i n g

body,

components

values

of

strength

IV.

body composition

above

ware under

may be compared with

substantially

as the

as well

of the

a measure

sanitary

demonstrate

To c o m p a r a t i v e l y
invention

is

modulus of r u p t u r e

yields

square

of course

following

slips which

components

9 body,

Table

adjusted

II

were

added as n o t e d
with a 50%

in more d e t a i l

Referring
was a high
index
and is

of

glass

fluxes

silicate

Flux B was a g l a s s

understood

to make the

alumina

calcium,

1.65.

to the

glass

to

comprise

particles

of the p r e s e n t

listed

glass

in Table

having

flux p u r c h a s e d

ground window g l a s s

more water r e s i s t a n t .

invention

and comprised

II,

Flux A

a refractive
on the
having

open m a r k e t
a coating

Flux C was a

in weight p e r c e n t :

The f l u x
given
oxi'es

as r e s i d u a l

indicated

minus

the

diopside

glass

precipitated

in Flux C a f t e r

remaining

the

MgO, CaO and SiO2 to give d i o p s i d e

flux)

were used as the

Body 13 would thus

oxides

are

combined d i f f e r e n t l y .

illustrate

that

by m e l t i n g

cannot

diopside

proportions
containing

184:120 by weight,
MgO, CaO and Si02

to form a g l a s s .

The f o l l o w i n g

Table

III

each body composition

lists

set

residual

dolomite

casting

though

the

II.

be made

Vitreous

slip.

to y i e l d

proportions

in Table

of t h e
flux.

glass

and q u a r t z

the v i s c o s i t y

forth

of some of t h e

9 and 10 were made t o

in the

in the

just

the

is,

(50% by weight

respectively,

and quenching

That

from which Flux C could

be used as such
by m e l t i n g

composition

same as body 6,

Bodies

the raw m a t e r i a l s

was p r e p a r e d

combination
of the

the

the

therefrom.

crystals

constituents

be c h e m i c a l l y

comprised

in t h e
a composition

present

measurements

in d i o p s i d e

for

Body c o m p o s i t i o n

14 in Tables

body c o m p o s i t i o n

previously

to the

slips

to d e f l o c c u l a t e

were d e t e r m i n e d

with No.

III

given.
the

3 Spindle

and IV r e p r e s e n t s

the

The sodium s i l i c a t e
clay.
at

The B r o o k f i e l d
10 rpm.

except

cone

9-10

was a d d e d
viscosities
for

Body

3 and 8 where No.

Compositions

sodium s i l i c a t e
silicate

sodium
aging

those

for

periods

as i n d i c a t e d

level

gradual

was used for

reduction

a thickening
present

thickened

to a t h i c k

are

set

age.

When c a l c i n e d
and i t

slips

to t h i c k e n

10,

from the

standpoint

forth

in Table

IV.

11,

impractical

compositions,

initial

the

Flux A also
synthetic

of the

was added,

was not p o s s i b l e
paste

after

finished,

Only Body Compositions

vitrification

at a t e m p e r a t u r e

12 and 13 t h i c k e n e d
for use in a c a s t i n g

only Body Compositions

very
slip.

of t h e
showed

diopside
than

the

former
the

slip,

to d e f l o c c u l a t e

12 and 13 a l l

of the

a flux

deflocculation

dolomite

to a s t i f f

data

Compositions

6 containing

containing

11,

2 and 3

initial

and the v i s c o s i t y

6,

paste

for

Simflarly,
for

Body Compositions

even approached
were

on aging.

Body Composition
with

Critical

the

at

testing

Body Compositions

age.

Body Compositions

more sodium s i l i c a t e

respective

aging

1 and 14 show the n o r m a l

more sodium s i l i c a t e

tendency

(Body 7).

with

did Body Composition

increased
it

6 for

Body Composition

of v i s c o s i t y

invention.

required

late

for

an added amount o f

Similarly,

Body Compositions

III,

than

deflocculation
present

line

entry

additional

of two days and m o r e .

Flux A r e q u i r e d

with

by a lower

compositions.

to Table

Referring

was used with

5 Spindle

caused t h e i r

one d a y .
fired
2,

4,

piece,
6 and 7

of cone 6. Body

rapidly
Of the

on aging

and

remaining

6 and 7 gave lower

absorptions.

It

will

be noted

in accordance

diopside
the

amounts

reduced

effectively
the

fired

those

processing,

additives,

even

synthetic

invention

needed for

have

5-6.

also

same t i m e ,

to r e l a t i v e

well

and modulus

warpage,

within

the v a l u e s

be observed

other

that

when added to the

feldspathic

The f l u x i n g
in a l l

properties

of

ease

to c o m m e r c i a l

so e s s e n t i a l

drawbacks.

serious

excellent

At the

in

was

temperature

absorption,

diopside,

action

fluxing

firing

in a d d i t i o n

all

are

will

It

a number of

body provided

as a body a d d i t i v e

9-10 to cone

shrinkage,

of d i s s o l v e d

source

characteristics

critical

by the t r a d e .

required

the

II,

contained,

These p r o p e r t i e s

of r u p t u r e .

of t h i s

still

firing

namely,

success,

in t a b l e

from cone

products

fritted

invention

this

with

forth

set

the

when using

that

glasses

categories

and are not o u t s t a n d i n g

in j u s t

a few o f

such c a t e g o r i e s .
Another a s p e c t
deflocculent

that

ceramic

slip.

it

is,

from the

Such b a l a n c i n g

as the

More p a r t i c u l a r l y ,
the

tend to r e a i s e
deflocculent

deflocculent
to provide
include
frit
the

the

maintains

the

oxides

oxides

that

when i t

or improves

of the

viscosity

any metal

such as sodium oxide,

that

are

is

added t o

slip

stability,

at w o r k a b l e

slip

slip

slip

as s i l i c a t e s

along

such

leached

the

solidify
with the

But i f

slip.

the

deflocculents

Deflocculent

viscosity.

frit,

flocculents,

the

or c o u n t e r a c t

from the

oxides

may be made a component of the g l a s s

of these

potassium
the

are

and even

as d e s c r i b e d

Examples

glass,

earths

leached

are

workable

oxide

earths.

from the

alkaline

counterbalance

a stable,

alkaline

in the

earths

firt

glass

imparts

viscosity

and which c o u n t e r a c t s

leaching

alkaline

fluxing

the

in b a l a n c i n g

values.

viscosity

they

resides

invention

and f l o c c u l e n t

oxides

leached

gradually
the

of the

oxide,

the
are

flocculating
the

alkali

and l i t h i u m

deflocculent

action

metal

oxide.

of

oxides

After

oxides

are u s u a l l y

as sodium s i l i c a t e ,

potassium

present

and l i t h i u m

silicate,

silicate.

The amount of d e f l o c c u l e n t
on how much f l o c c u l e n t

oxides

concentrations
not

deflocculent

the

so c r i t i c a l

in amounts
to the

each o t h e r

counteract
from the

frit

a buffer

or n e u t r a l i z a t i o n - l i k e

oxides

successfully
is

net r e s u l t
slip

even b e t t e r
the

after

leaching

away of i t s

maintain

relatively

following

of a d e f l o c c u l e n t
Considering
balancing

the

oxides

having

silicate
frit

properties

or the

The
like

some

is able

to

for d a y s

of only minimal

from the

and f l o c c u l e n t

amounts

was p r e p a r e d
(unreacted
III,

one day were too v i s c o u s

it

standpoint
alkaline

II use v i t r e o u s

earths,
the

to form c l e a r ,
and u n d i s s o l v e d )

Body Compositions

11,

to be removed from t h e

will

of

diopside

by melting

and r o l l - q u e n c h i n g

IV,

from s o

silicate.

no free

to Table

leached

earth

added and undergone

addition

As shown by Table

Referring

or

There r e s u l t s

slip.

The p r e s e n t

oxides

proportions

are

becomes unworkable.

sodium

data more f u l l y

diopside

earths

respectively

alkaline

it

12 and 13 of Table

11,

glass

earths.

and 13 within
container.

such as sodium

The v i t r e o u s

uncrystallized

the

for

by which the d e f l o c c u l e n t

rheological

requiring

deflocculent

in c o r r e c t

alkaline

has been

solubilities.

the p r e v i o u s

Body Compositions
as a flux.

frit

are

that

adding

larger

to c o u n t e r b a l a n c e

flocculent

slip

than

constant

milling,

effect

the

of the

they

may be i n

alkaline

in a ceramic

dispersal

prevent

the v i s c o s i t y

changing
to the

upon i t s

earths

the two a l k a l i n e

that

sufficient

extent

should

amounts l e a c h a b l e

or f l o c c u l e n t

circumstance

frit

glass.

for both t h e

substantially

The a b s o l u t e

oxides

is the

as

be p r e s e n t

materials

although

range,

depends

from the

of the glass

alkaline

flocculent

frit

glass

leachable

are

leached

The amount

possible.

are

earths

in the

5% by weight

and the

per m i l l i o n

the p a r t s
either

least

oxides.

be d e f l o c c u l e n t
deflocculent

alkaline

at

however,

Normally,

needed

oxides

be noted t h a t

the

12

of r u p t u r e

modulus

for

compared,
embodies
was s t i l l

these

Body Compositions
value

to t h a t

example,

the p r e s e n t

compositions

from the

are

extremely

for Body Composition

Test bodies

invention.

immediately

6 which

were made from t h e s e

while

slip

poor

initial

viscosity

workable.
7 and 8 which

Body Compositions
contained

as a r e s u l t

7 and 8 r e q u i r e d
earths

for

present,

counteracted,

unreacted

comprise

synthetic

alkaline

earths.

more sodium s i l i c a t e
but

the

once the

slip

effect

was q u i t e

because
of the

stable

diopside

also

Body C o m p o s i t i o n s

of the

alkaline

free

alkaline

earths

as no a d d i t i o n a l

was
leaching

would be e x p e c t e d .
In c o n t r a s t ,
only

6 representing

a normal amount of d e f l o c c u l e n t

casting
the

Body Composition

slip

slip

addition

invention

required

for

initially

making t h e

after

24 hours,

after

which

was s t a b l e .

The following
present

and a s l i g h t

the

glass

described.

Table

V provides

composition

six

additional

from which f r i t

examples

of t h e

can be made a s

Extraction

measurements

and B of Table
diopside,
case,
all

glass

diluted

comparison p u r p o s e s ,

and d i l u t e d

diopside

flux powder having

U.S.

of d i s t i l l e d

portion

out on powders

Flux B, and v i t r e o u s

3% on 325 Mesh,

milliliters
filtered

for

V, and,

one gram of the

but

were c a r r i e d

Standard

water

to 250 ml.

by atomic

for

24 hours.

The elements

absorption.

Table

on the s y n t h e t i c
of Table

a particle

Sieve,

of Examples

In e a c h

II.

size

to p a s s

was shaken with

The s o l u t i o n

was t h e n

were e s t i m a t e d
VI shows the

100
on t h e

results.

High Ca++ e x t r a c t i o n s

lead

t h i n n i n g of the s l i p .
+
high Na , so t h a t i t s

Example A has both

the

thicken

that

is

of a composite.
as badly

does

It

as v i t r e o u s

Example B c o n t a i n s

or m a i n t a i n

enhance

behavior

somewhat but nowhere n e a r l y

slip

does.

diopside

high N a leads t o
high Ca++ and r e a s o n a b l e
while

to t h i c k e n i n g ,

more Na20 than Example A t o

e x t r a c t a b i l i t y . Tabel VI i n d i c a t e s t h a t

Na

the Ca++ e x t r a c t i o n

from Example B into s o l u t i o n has indeed b e e n

r e d u c e d , while the N a has not been a f f e c t e d .

drastically
The g l a s s

to e x t r a c t i o n

respect

All c a s t i n g

described

glass,

of body.

fired

less

to

differences
glass

flux

All

than

in the
is
to

plasticity,

and the

consider

in

therefore,

physical

composition

like.

the
used

slip

provide

conditions

ease

of the

bodies

the p r o p e r t i e s

factors

losing

slip

cast

composition

in the

stability

mix.

as t h e

may c h a n g e

brittleness

body c o m p o s i t i o n
flexibility

are

to

would be f a c t o r s

glass

were

glasses

5. There

of trimming,

These

flux

to

for use w i t h

The p r e s e n t

glass

invention

composition

and the u s e f u l n e s s

as a body f l u x .

sanitary-ware

flux

cent

weight per

cone

at Seger

a particular

industrial

While the p r e f e r r e d
cast

The c a s t i n g

these

using

For i n s t a n c e ,

softness,

may be used w i t h o u t

in d e t e r m i n i n g

a three

using

bodies

1% p o r o s i t y

selecting

any p a r t i c u l a r
does,

cast

changed.

in h a r d n e s s

II,

cent.

The

stability.

1.5 grams of soda ash were added p e r

in a d d i t i o n

kilogram

in weight per

in Table

same mix as
but

stability.

for Table VI was used

concentrations

elemental
was the

and s l i p

in Table VII w i t h

of Table VII have good v i s c o s i t y

slips

same t e c h n i q u e

detailed

of Table V are

compositions

embodiment hereof
body,

as will

is

represented

be u n d e r s t o o d

by

by a s l i p

that
of t h e

those

skilled

in the

though perhaps

not

as pronounced

sanitary-ware

body,

would q u i t e

ceramic

would d e f i n i t e l y

body;

could be c h a r a c t e r i z e d
a "feldspathic"
And, while

or d r a m a t i c

be a p p l i c a b l e

embodiment h e r e o f

than

consideration,

the method of forming

etc.

of t h i s

as s l i p

lower the
by at

crystals

Although

the

invention,
still

other

time

and/or

foregoing

it

is

understood

forms w i t h i n

the

that

the

and/or

frit

of t h i s
in f i r i n g

heat

amount"

treatment

of t h e

invention.

several
the

cones.

reduction

diopside

of t h e

Seger

required

a "fluxing

of t h i s

describes

fine-grained

body would c o n s t i t u t e

lowering

glass

three

any m e a s u r a b l e

involve

results

temperature

crystals

of a ceramic

Certainly,

the

firing

least

an amount of the

cone would

diopside

whether by e x t r u s i o n ,

body,

that

amply d e m o n s t r a t e

which would promote

even one Seger

the

are a

herein.

disclosed

invention

amount".

benefits

solubility

cast

slip

forms no l i m i t i n g

invention

and/or

involves

really

however,

"fluxing

as

method of forming

Obviously

temperature

art,

final

body d i s c l o s e d

feldspathic

particlar

on the

invention

The examples h e r e o f
crystals

to any f i r e d ,

would have no b e a r i n g

and as such,
of the

in a

appear

body.

other

feature

invention,

to any body which

in t h i s

skilled

sanitary-ware,

achieved,

as they

be a p p l i c a b l e

likely

by those

the p r e f e r r e d

dry p r e s s i n g ,

of the p r e s e n t

the b e n e f i t s

art,

embodiments

invention

scope of the

of the p r e s e n t

may be p r a c t i s e d

following

claims.

in

1. A s u b s t a n t i a l l y
frit

completely

clear

smelted,

glass

containing:
(a)

leachable

amounts

alkaline

earths

(b)

body flux

in a ceramic

said

frit

(c)

frit

(d)

least

size

a fluxing
diopside

less

than

said

deflocculent

oxides

being

leachable

from said

amounts to

counterbalance

thickening

of the

said

of claim

precursors

heating.

slip

earths,

having

frit

from

substantially

alkaline

in s u f f i c i e n t

least
said

earths

relative

and p r e v e n t

to an unworkable

to

in

and

each o t h e r

converted

of

an a v e r a g e

and being

and f l o c c u l e n t

1 in which at

are

to c r y s t a l l i z e

amount of said p r e c u r s o r s

one micron

alkaline

frit

slip

frit,

crystals

of u n r e a c t e d

diopside

during

at

of the

free

2. The g l a s s

the

thickening

adapted upon h e a t i n g

form of fine

particle

body

CaO, MgO, and SiO2 in ananount

precursors

being

solution
the

without

as a ceramic

viscosity,

35% by weight

least

said

serve

c o m p l e t e l y l i q u i d at a s m e l t i n g
of about 26000F and c o n t a i n i n g in s o l u t i o n

diopside

at

slip

to

and f l o c c u l e n t

oxides

being

temperature
the

of d e f l o c c u l e n t
and adapted

to an unworkable

said

vitreous,

said

viscosity.

50% by weight
diopside

of

crystals

3. The g l a s s

frit

from about

temperature
4. The g l a s s
in weight

said

frit

percent

additive

said

Seger

cone

said

five

1 in which

(5)
said

is at

heating
to about

cone

composition

a
six

(6).

comprises

about:

selected

the p e r c e n t

from one or more of the

indicated

based

on the

following
total

weight

glass:

fluorine

a fluoride

in weight

when p r e s e n t

of at

5. The g l a s s

said

1 in which

of claim

being

in a p p r o x i m e t a l y
of the

of claim

frit

percent

additive

least

being

one metal

of claim

introduced
of the

1 in which

into

the batch

as

composition.

said

composition

comprises

about:

being

selected

from one or more of the

following

of the

frit

dolomite

76:24

11:89,

to

7. A f i r e d

and l i t h o s p a r

the

form of a c l e a r ,

with

a substantial
size

particles

of both

fritted

less

than

crystalline

extent

frit

effect

precipitated

diopside

vitrified

composition

smelt.
amount o f
insitu

during

vitrified
having
frit

leached

substantially

alkaline

alkaline

thereof,

an a v e r a g e

being

in a q u a n t i t y

of f l o c c u l e n t

solution

earths

sufficient
earths

to

present

upon d i s p e r s a l

of

body of claim
comprise

7 in which s a i d
from about

0.1% to a b o u t

of said b o d y .

diopside

frit

oxides

crystals

sanitary-ware

precipitated

the

slip.

sanitary-ware

5.0% by weight

of a b o u t

formed

and u n r e a c t e d

they are r e s p e c t i v e l y

in a ceramic

The f i r e d

completely

phases

8. The f i r e d

9.

into

said

the

by

CaO, MgO and Si02, s a i d

said body p r i o r to f i r i n g i n

one micron,

counterbalance

ration

chemically

crystals

deflocculent

said

weight

attained

a fluxing

of said

portion

and c o n t a i n i n g
to the

total

precursors

introduced

initially

precursors

is

fritting

body c o n t a i n i n g

from the d i o p s i d e

firing

frit

in a weight

of d i o p s i d e

crystals

said

and then

respectively,

sanitary-ware

precipitated

1 in which

of claim

smelting

free

on the

glass:

6. The g l a s s

said

based

indicated

the p e r c e n t

in a p p r o x i m a t e l y

crystals

of claim

prior

body of claim

7,

to said

said

are
frit

firing:

formed

7 in which
from the

having

the

said
completely

following

said

additive

in a p p r o x i m a t e l y
of the

said

indicated

the p e r c e n t

when p r e s e n t

fluorine
of at

The f i r e d

vitrified

frit

composition

least

based

prior

additive
glass:

of the

on the

following
total

weight

are

said

frit

into

the batch

as a

composition.

body of claim

crystals

to said

being

in a p p r o x i m a t e l y
of the

one metal

of claim 8,

introduced

being

sanitary-ware
diopside

precipitated

said

from one or more of the

glass:

fluoride
10.

selected

being

formed

7 in which
from the

having

the

said

completely

following

firing:

selected

the p e r c e n t

from one or more of the

indicated

based

following

on the t o t a l

weight