United States Patent [191

[11]

4,337,316

Votava

[45]

Jun. 29, 1982

[5

RE

PROCESS OF

[75] Inventor 35mg; Fbxgava Broadvlew

j

g_

[73] Assignee:
'

>

Crystal Particles Uzb. Khim. Zh. 1973(3), pp. 64-67

(Russ.).
'

' '

'
_

501 [lb 501/73:

561/141; 501/142'f501/143

[58] Field of Search ................ .. 106/48, 39.6, 313, 52;

I

'

[56]

501/5, 21, 24, 53, 70, 73

References Cited
-

_ ABSTRACT

sanitary ware. The frit contains. both deflocculent ox

3,319,387 6/1974
3900329 8/1975
--

Primary ExaminerHelen M. McCarthy

Attorney, Agent, or Firm-Milton L. Simmons

the end product are disclosed in which a ?uxing amount

of a glass frit is used in the ceramic slip used to cast the

2:207:911 7/1940 Canno'n _

WollastoniteNew Raw Materials for Ceramics May

27'31 1976

' A process for producing feldspathic sanitary ware and

2,261,884 11/1941 Koenig .............................. .. 106/313

2,621,131 12/1952 Lathe .
3,149,983 9/1964 Maris et a1. .
3 904 423

Berezhnoi, Glass-Ceramics and Photo-Sitalls, Ple

Hum Press, NYC (1970) pp 256_258_

H. G. Kurczyk, Synthetic Diopside and Synthetic

[57]

U.S. PATENT DOCUMENTS

1 855 H 5 4/1932 Peddrick et a1
2O24407 12/1935 was
' '

Yanusov, K. et al. Effect of Boron Oxide on the Prop

erties of Frits of Faience Glazes Opaci?ed by Diopside

[51] int. Cl.3 ........................ .. (5,03%:

52 U S Cl 501/2l_ 1o6/313_
[ 1 '

Maretheu, A. et a1. Utilisation Laitiers Siderurgiques

pourla fabrication de carreaux defaience LIndustrie

' Ceramique, Jun. 1969, No. 619, pp. 405-414.

Ferro Corporation, Cleveland, Ohio

[21] Am N" 188919

[22] Filed: '_ Sep. 19, 1980
1

OTHER PUBLICATIONS

ides and ?occulent alkaline earths which are leachable

_ from the frit when it is placed in the ceramic slip. The
de?occulent oxides counterbalance the effect of the

?occulent alkaline earths to the extent they are respec

tively leached from the frit u on dispersal in a ceramic

9/1975

1-

8 1p an

1'

k b1

malntain t e s 1p at a war a

e vlscoslty.

p011

vgulger

4009015 2/1977 Mcycon'ister

501/5 X
4:102:692 7/1978 Schartau et a1: ".IIIIIIIII "501/70 x

casting and ?ring the slip, the present frit precipitates

?ne crystals of diopside having an average particle size
f1essthah One micm" which are Particularly useful in

4,113,500 9/1973 Ebihara et a1_ .

lowering the ?ring temperature of feldspathic bodies by

4,142,907 3/1979 Maming at a], ,

promoting the required degree of vltri?cation at lower

temperatures than heretofore possible.

FOREIGN PATENT DOCUMENTS

1149840 6/1963 Fed. Rep. of Germany

l06/39.6

4 Claims, N0 Drawings

4,337,316

short time. Also, sintering of the cast ceramic slip leaves

SANITARY WARE AND PROCESS OF
PRODUCTION

a certain amount of unreacted alkaline earth in the sin

tered product. This likewise has an undesirable ?occu

BACKGROUND AND FIELD OF THE ~ -

lating effect on the slip.

The ?eld of this invention deals primarily with the

5.

" i

production of sanitary-ware body additives designed to

lower the production ?ring temperature of a sanitary
'ware body, while at the same time preserving all the
required characteristics of said body in both the slip

The .body is usually formed by the well-known

method of slip casting, carefully and slowly dried,

stage, as well as in the ?nal, ?red product. Further, the

invention includes a counterbalancing of ?occulents

glazed'and ?red to vitri?cation in a tunnel kiln at a

leached by the slip from vfluxing frit and a resulting

maintenance of a workable viscosity of the slip.

INVENTION

'

Sanitary-ware ?xtures, i.e., toilet bowls, lavatories

and the like, particularly the former, are constructed of
a glazed, highly vitri?ed, feld'spathic body.

temperature equivalent of Seger pyrometric cone 9 to

10. The body is normally referred to as feldspathic

The utilization of either wollastonite (CaO.SiO2) or

indicating that a substantial proportion of the mineral 5 diopside (CaO.MgO.2 SiOZ) as an additive for ceramic
content of the slip is feldspar. However, nowadays
bodies is disclosed by H. G. Kurczyk in a paper entitled,

' feldspathic sand or nepheline syenite can be optionally

Synthetic Diopside and Synthetic Wollastonite-New

used as a partial or complete replacement for the feld

Raw Materials for Ceramics, from the Proceedings of

spar without changing this generic description.

the 3rd CIMTEC, 3rd International Meeting on Mod

Ideally, and as will be described in more detail herein 20 ern Ceramics Technologies at Rimini, Italy, May 273 1,

after, the casting slip, as well as the ?nal, ?red,=vitri?ed

1976.

body, must meet certain rigid, rheological and physical

property standards.

'

'

side by any number of means, including synthesis by

For example, the viscosity, speci?cgravity and stabil

ity of the casting slip should ideally remain constant

25

overappreciable periods of time as these factors are'all

critical from the standpoint of casting bodies having

desired wall thicknesses, drying shrinkage, etc.
The ?red body, ideally, will be completely vitri?ed,
have high strength, with minimum, though uniform,
shrinkage on ?ring.

solid-state reaction, crystallization from a molten bath,

sintering, etc. Kurczyks preferred method apparently is

the formation of diopside from dolomite and ground
quartz in the appropriate molecular ratio by hydrother
mal pretreatment and calcination.

However, diopside producedby sintering, from the

standpoint of adaptability to ceramic bodies, has a num
ber of drawbacks. First, the sintering process utilizes a
rotarylkiln operation similar to that used for the manu
facture of portland cement clinker. As is well known, it

In an effort to either, orboth, speed the ?ring opera

tion and to lowerthe ?ring temperature, any number of
body additives have been experimented with. For exam

ple, many ?uxing materials have been tried to speed the

body vitri?cation process, withvarying degrees of suc

35

is exceedingly dif?cult to control the ?ring temperature

in a rotary kiln with any degree of precision, wherein
variations in temperature may promote either a soft
burn, resulting in a high percentage of unreacted mate

cess. However, such ?uxes have generally'c'reated more

problems than they have solved.

That is, speeding up the vitri?cation process poses no
major problem, in and of itself; but slip instability, ex

. ' Kurczyk discloses the possibility of synthesis of diop

rial, or cause a partially molten bath which solidi?es

40

cessive shrinkage or warpage on drying or ?ring, lower

upon discharge from the sintering zone, resulting in the

formation of a non-uniform, heavy, slag-type coating on
the calciner walls with attendant undesirable interrup

strength, short vitri?cation range, etc., have usually

tions in the overall operation.
,
.
accompanied the utilization of conventional body ?uxes
Furthermore, the diopside produced by the method
used heretofore. By way of explanation, short vitri?ca
tion. range refers to the temperature spread, within a 45 disclosed by Kurczyk is relatively large grained (10 to
30 microns) which tends to reduce its, effectiveness in
commercial kiln, over which the required degree of
lowering the ?ring temperature of a sanitary-ware body
vitri?cation will both occur and be sustained without
and, as is well known, the diopside mineral crystal tends
slumping and/or crystallization (devitri?cation). to be extremely hard and tough, thereby making it most
Therefore, while a vitri?cationrange would be of
little or no signi?cance in a small test bar, ?red under 50 dif?cult to mill and grind to a particle size small enough
carefully controlled laboratory conditions, it isvital to , to be effectively dispersed throughout a sanitary-ware

successful manufacture of sanitary-ware products on a

body slip.

commercial scale in a continuous production tunnel

' kiln. Thus, if a sanitary-warebody reaches vitri?cation

It has been found however that, if the molten bath

.which Kurczykfound to be undesirable, is deliberately

atprecisely cone_l0 down, while at, cone 9 it, is not 55 created under controlled conditions, followed by the

vitri?ed, whereas at cone -ll it'hasbegun to slump, the: I e. novel processing steps hereinafter set forth, a more
, production, problems become readily apparent because . economically produced, superior form of diopside is
v.th'ereis no practical way to achieve temperature control achieved, which eliminatesall the disadvantages of
. at precisely cone 10 throughout the cross section ofjthe 1 Kurczyk, while providing a number of additional im
?ring zone of a production kiln.,

' ~

provements ,t-hereover.

' >.

A related problem inqcastingsanitary 'warei from a "

, ceramic, slip in which a glass frit serves asa ?uxiisgthatg '

OBJECTS

- the frit tends to bev somewhat ,soluble. Components, a " 'v-ltisthereforeian object of this invention to provide'a

leached fromthe frit, notably the alkaline earths, act as i

' , gflocculents and can sufficiently raise the viscosity of the

slip to make it unworkableln fact, some slipsmayeven

, lvirtually [solidifyr Moreover, this flocculation to an

unworkable viscositycan oftentake place ina relatively '

new and improved crystalline form of diopside.

- .'It- is anotherobject of this invention to provide a
, relatively'low temperature glass matrix from which ?ne

grained diopside crystals may be formed upon reheating

said glass to its crystallization temperature.

4,337,316

It is yet another object of this invention to provide

diopside precursors in glass solution in a relatively low

-continued

melting temperature glass, which glass may be readily

incorporated into a ceramic body, and which glass,

Additive

5.0 to 20.0

upon ?ring of the body, will precipitate at least some 5 the additive being selected from one or more of the

?ne grained crystalline diopside, uniformly dispersed

following in approximately the percent indicated based

and formed in situ throughout said body.

on the total weight of the glass:

It is yet another object of this invention to provide a

vitreous source of ?ne grained diopside crystals which

can be easily and readily milled to a suf?cient ?neness

for incorporation into a feldspathic ceramic body.

It is another object to achieve a process for manufac

turing the relatively low temperature glass of this inven

tion.

It is a further object to counteract ?occulents leached 15

by a slip from glass and prevent their increasing the

viscosity of the slip to unworkable values.
And ?nally, it is an object to provide a new and im

U20

0 to 5

SrO
ZnO

0 to 5
O to 5

K20
NaZO
A1203
ZrO;
M002

0 t0 5
O to 10
0 to 12
0 to 20
0 to 2

PhD
CeO;

0 to 5
0 to 2

O to 10

proved, sanitary-ware body, as well as provide the pro

20

cess for achieving same.

the ?uorine when present being introduced into the

batch as a ?uoride of at least one metal of the composi
tion.

SUMMARY OF THE INVENTION

The present invention reduces the ?ring temperaturesv
of vitreous and semi-vitreous bodies comprising feld

A more desirable composition comprises in weight

percent about:

spathic materials, while maintaining a suitable ?ring

range and other physical properties of such material. As
a result, there is substantial fuel savings with increased

productivity. By substantially balancing the de?occu

lent oxides and ?occulent alkaline earth extractabilities
from the glass added to a slip, its viscosity can be main 30

CaO

1s m 25

MgO
SiOz

10 to 20
35 to so

Additive

5 to 20

tained within workable limits.

the additive being selected from one or more of the
In one form of the invention, the glass hereof in the
following in approximately the percent indicated based
form of a ?nely ground frit is mixed with the ceramic
on the total weight of the glass:
material to be ?red to form a feldspathic body. The frit
contains in solution quantities of the oxides contained in 35
diopside, namely MgO, CaO, and SiO;, and is so formu
K20
'0 to 3
NagO
0 to 5
lated that when heated above a certain temperature (as
M20
A1203

during the ?ring of the ceramic body) ?ne grained diop

side crystals precipitate out and act as a ?ux, lowering

the ?ring temperature substantially, for example, at least

0 to 3
0 to 10

A preferred compositional range and a preferred

three Seger cones as compared to the ?ring temperature

composition for the glass containing the diopside pre

that would be required without the diopside crystals.

cursors are in weight percent about:

The frit contains leachable de?occulent oxides which
counterbalance any ?occulent alkaline earths leached
therefrom and prevent thickening of the slip to an un 45
Ingredient
Range

workable viscosity.

DESCRIPTION OF THE PREFERRED

EMBODIMENTS
In accordance with the present invention, a glass frit

containing in solution the diopside precursors CaO,

MgO, and SiOZ, is incorporated with a ceramic material
that is shaped into a body and ?red to achieve the de

sired degree of vitri?cation. During the ?ring, diopside

forms from the precursors and precipitates as v?ne crys
tals which serve as a ?ux. The crystalline, ?uxing diop

55

Percentage

CaO
MgO

3.5 to 40.3
2.6 to 26.0

22.1
18.4

SiO;
A1203
K20
NaZO
U20

30.0 to 76.3
5.0 to 12.0
0 to 2.3
0 to 4.6
0 to 0.2

46.0
9.25
1.4
2.5
0.1

It will be appreciated that these compositions consti

tute metal oxide analyses of the smelted glass. The cor
responding batch materials may constitute those materi

als which on smelting and cooling yield the oxide analy

side substantially lowers the ?ring temperature required

sis. For example, the present glasses can be smelted

from dolomite and lithospar in a weight ratio of about
other body. '
60 76:24 to 11:89, respectively. Whiting can be substituted
Considering these components in greater detail, the
for a relatively small portion of the dolomite, and any of
diopside precursors, CaO, MgO, and Si02, should com
the other ingredients optionally included can be added
prise at least 35% by weight of the glass. For example,
to the batch, either in the oxide or salt form or in a form
such a glass may comprise in weight percent about:
of the ceramic material in forming the sanitary-ware or

which reduces to the metal oxide or ?uoride form on

65
C210
MgO
SiOg

35 to 45.0
2.5 to 30.0
30.0 to 78.0

smeltingIFor example, spodumene, lepidolite, and the

like may constitute part of the batch formulation.
Compositions with the ranges disclosed melt at tem
peratures approximating about 2600 F. to about 2750"

4,337,316

6
-continued

F. The melt may be fritted in any convenient manner,

such as bywquenchingthe melt in wateror passing it

Cone 9-10 Body Composition

between fritting rollers. The frit so obtained is conven

tionally ground prior to use. As an example, the frit may
be ground sothat about 95% passes through 325 mesh,
U.S. Standard Sieve. X~ray examination shows that the
frit is totally vitreous or nearly so.

18.0

Feldspar

32.0
100.0

Water

37.5

Na2SiO3

A vglass of the type described, containing the diopside

precursors, is incorporated with suitable ceramic mate

As required

'

The composition of the feldspar was essentially

rial that is adapted to form sanitary ware, and themix

ture is then shaped into a body, as by slip casting. The

KNaO.Al2O3.6SiO2.

The sodium silicate was added as a 50% aqueous

body is then ?redto yield thesanitary ware. As de

solution suf?cient to achieve an initial slip viscosity as

scribed more fully hereinafter, the ,presentglass does

measured on a Brook?eld viscosimete'r on either a #3 or

a #5 spindle at 10 RPM.

not signi?cantly affect the castingproperties of the slip,

and its viscosity'may becontrolled by providing counT

The foregoing sanitary-ware body composition was

teracting or counterbalancing leachable amounts of

cast into test bars having the dimensions one cm. by one
cm. by 10 cm., and measured for ?ring and total shrink
age, absorption and warpage, the results, from cone 8 to
cone ll, tabulated below in Table 1..
TABLE I,

deflocculent. In contrast other commercial glasses can

markedly affect slip properties in a deleterious way.
A preferred'ceramic material used to form the body is
a feldspathic one, that is, bodies in which a substantial
portion of the mineral content is feldspar.

In accordance with the present invention, the temper

Firing

% Firing

ature of ?ring is lower by at least three Seger cones than

would be required, without the presence of the instant
glasses. Any addition of a present.glass effects some

Temperature

Shrinkage

reduction in the ?ring temperature of theceramic body.

Amounts as little as 0.1% by weight oftheabodyvto as
much lasil0%, or more are-useful. 'Howeven'the pre
ferred range of theiglass. is 'about3% tot-about 5% by
weightof the ceramic body.

_ .

Upon ?ring a,__ ceramic body containing a present

,..

_' 1

i % Total '

Cone SD92

9.35%

0.62%

Cone 91710I

. 9.53%

0.03%

Cone 10011l

9.59%

Cone 110121

9.17%

Shrinkage

0.021"
>

11.85%

0.022"

12.03%

0.01%

0.030

12.09%

0.27%

0.033"

11.67%

those which are .reported in the following tables, were

_

Percentage Firing Shrinkage

This was determined as being the difference between
35

of theinstant g1ass_;converts,tocrystalline diopside; the

balance forming a glassy residue.-

Absorption vWarpage

arrived at as follows;

glass, the, described precursors precipitate in situ in the

body as very ?ne crystals of diopside. In one instance, it
was observed that the, glass crystallized at about 1652"

F.. (900 (2.), although thistemperature is notJcritical.

Upon such crystallization, at least about50% by weight

~_

The foregoing physical characteristics, as well as

30

Weight %

Flint (200 Mesh). %

dried length and ?red length, divided by the dried

length and multiplied by 100 to provide the indicated
percentage.

'

In this regard it should be noted that, at least theoreti

cally and predictably, the lower the shrinkage, gener~

ally the better.

The crystals formed are extremely ?ne and this is

believed to. be quite advantageousrA substantial portion
of the crystalline diopside formed has an average parti

However, because existing commercial molds have

been designed to-provide a ?nished article in contem

cle size less than one micron. Diopside formed in accor-.
plation of 10% shrinkage, the body as described below,
dance with the present invention is a better body flux
utilizing the instant invention, has been compounded to
than. synthetic diopside. This is believed to be due at
least in part to the ?ne grained nature of the diopside 45 provide approximately 10% shrinkage to eliminate the
need for extensive commercial moldredesign at this
formed which leads to faster dissolution in the subse

quent ?uxing action. This fluxing action accorded by

time.

the present glasses is so effective that it lowers the re

quired ?ring temperatures at least three Seger pyromet

6, while still retaining a good, suf?ciently wide ?ring

temperature and reducing Warpage.
X-ray diffraction results from ?red mixtures of the
present glasses with feldspathic bodies show that no
newjcompounds are formed other than the diopside
crystals. A progressive glass formation appears to take
place by fusion of the feldspathic matrix and assimila

'

'

'

"

Percentage Absorption ,

test method C373-72.

'

"

"

-'

An absorption of approximately 0.5% or less is gener

ally necessary to assure a suf?ciently vitr'i?ed'body.
Considering the use to 'whichsanitary ware is put, and
. further considering that not every square inch of sur

face exposed to water will be glazed, the need for a high

degree of vitri?cation. will be readily apparent.

,
- Warpage

For purposesof comparing the bene?ts and degree of

utility of the present invention with that which has been
practiced in the past, the following is exemplary of a
conventional cone 9-10 body composition used hereto
fore:

= Percentage absorption was obtained vusing ASTM

ric cones and typically from cone 10 to 12 to cone 5 to

tion of the diopside crystals.

Warpage was measured on test bars supported over a

?ve inch span during ?ring, the measurement, after

cooling to room temperature, taken two andvone half

inches from either support vat the midpoint, using a

depth gauge, the droop being taken as a measure of the

65

Cone 9-10 Body Composition

Plastic Ball Clay

Kaolin

Weight %

34.0
16.0

degree of warpage, reported in inches.

A Warpage of 20 mils, slightly more or less, is consid
ered to be about the norm, and would be expected to

produce commercially acceptable ware. Anything ma

4,337,316

terially beyond 20 mils would likely result in commer

TABLE II-continued

cially unacceptable ?xtures.

Parts Are by Weight

Percent Total Shrinkage

Vitreous Diopside

This ?gure was determined essentially the same as

--

1000
375

1000
375

1000
375

1000
375

30

15

15

1000
375

1000
375

1000
375

?ring shrinkage, except the initial measurement was

made while the test bar was still in the plastic state,

Water

prior to drying.

Referring in more detail to the ?uxes listed in Table

II, Flux A was a high calcium, alumina silicate glass

Modulus of Rupture
Modulus of Rupture was calculated using the stan
dard formula:

having a refractive index of 1.65. Flux B was a glass ?ux

purchased on the open market and is understood to

comprise ground window glass having a coating to

make the glass particles more water resistant. Flux C
was a glass of the present invention and comprised in

weight percent:

where
M=the modulus of rupture in pounds per square

inch;
P=the breaking load, in pounds;

SiOz
A1203

46.0
9.25

l=the distance between the knife edges in inches;

b=the breadth of the bar in inches;
d=the depth of the bar, in inches.

CaO

22.1

MgO
N820
K20
Impurities

18.4
2.5
1.4
0.35

Modulus of rupture of course is a measure of the

strength of the ?red body. Commercial sanitary ware

under our experimental conditions yields modulus of 25
rupture values of about 7000 pounds per square inch,

and this may be compared with experimental body

100.00

The flux indicated as residual glass comprised the

composition just given minus the diopside precipitated

therefrom. That is, the oxides remaining in Flux C after

To comparatively demonstrate the effectiveness of
the combination of some of the MgO, CaO and $0; to
the instant invention in substantially lowering both the 30 give diopside crystals (50% by weight of the ?ux) were
?ring temperature, as well as the time of ?ring of a
used as the constituents of the residual glass ?ux. Body
sanitary-ware body, the following cone 5-6 base body
13 would thus be chemically the same as body 6, though
values shown in Table IV.

composition was used:

Cone 5-6 Base Body Composition

the oxides are combined differently. Bodies 9 and 10

were made to illustrate that the raw materials from
35 which Flux C could be made by melting cannot be used
as such in the casting slip. Vitreous diopside was pre
pared by melting dolomite and quartz in the proportions -

Parts by Weight

Plastic Ball Clay

Kaolin

34.0
16.0

Flint (200 Mesh)

Feldspar

12.5
32.5

184:120 by weight, respectively, to yield a composition

containing MgO, CaO and SiOz in the proportions pres
40 ent in diopside and quenching to form a glass.

95.0

(Na2SiO3 and water as necessary)

It will be seen that, but for a slight reduction in S102,

the above base body composition is essentially the same 45

The following Table III lists the viscosity measure

ments for each body composition set forth in Table II.
TABLE III
Stability of Slips of Table II

as that set forth above for cone 9-10 processing.

Brook?eld Viscosity in Poises

Using the cone 5-6 base body composition as just

given as the feldspathic body, there is tabulated in the
following Table II the components of a series of sani
tary-ware slips which were weighed and mixed with
various auxiliary components added as noted and the

Body
Compo-

Na2SiO3
ml/Kg

Initial

Aged

Aged

Aged

sition

of Slip

Visc.

1 Day

2 Days

3 Days

5
6.5
5.75

19.9
20.4
16.5

10.6
30.0
55.3

9.6
42.2
61.0

9.0
67.5
184.0

1
2
3

viscosity, as with the cone 9 body, adjusted with a 50%

(#5
Spindle)

solution of Na2SiO3.

1 m1

TABLE II
55

Parts Are by Weight

Body Compositions
Base Composition

950

970

985

30

15

Flux A

Flux B

Flux C

970

985

970

30

--

1000
375

1000
375

1000
375

1000
375

Body Compositions

.7

10

11

12

13

Base Composition

970

970

970

970

970

985

970

Synthetic Diopside

30

30

15

--

--

Calcined Dolomite

l2

Lithospar

17.5

Dolomite

--

5.3
5.2
5.0

36.1
29.4
16.0

13.0
10.0
27.8
1 ml

10.3
8.1

9.1
7.2

7.25

Na2SiO3
23.8

15.3
38.3

15.3
31.8

20.2
36.4

5.75

23.9

370.4

'

(#5
Spindle)

1000
375

15

Residual Glass

4
5
6

15

950
375

Water

Na2SiO3

15

8.7

21.3

1.75 ml

NagSiOg
9
10

21.5

9.3

- Addition of calcined dolomite set the slip up and it

could not be de?ccculated.
- After one day slip was too viscous to remove from

container.
11
12

5
5

26.1 - Too viscous to remove from container.

18.0 - Too viscous to remove from container.

4,337,316

10

-9

?ring temperature was effectively reduced from cone

9-10 to cone 56..At the same time, the ?red products
still contained, in addition to relative ease of processing,
those critical characteristics so essential to commercial

TABLE III-continued
Stability of Slips of Table II
Brook?eld Viscosity in Poises
Body

Nazsiog

Composition

ml/ Kg
of Slip

13
l4

5
4

Initial _
. Visc.

Aged
1 Day

Aged
2 Days

success, namely, ?ring shrinkage, absorption, warpage,

Aged
3 Days

and modulus of rupture. These properties are all well

within the values required by the trade. It will also be

16.5 - Too viscous to remove from container.

19.0

12.2
10.9

observed that other additives, even synthetic diopside,

when added to the feldspathic body provided a number
of serious drawbacks. The ?uxing glasses of this inven
tion have excellent properties in all categories needed

Body composition 14 in Tables III and IV represents

the cone 9-10 body composition previously given. The
sodium silicate was added to the slips to de?occulate
the clay. The Brook?eld viscosities were determined
withNo. 3 Spindle at 10 rpm. except for Body Compo

for fluxing action and are not outstanding in just a few

of such categories.
Another aspect of the invention resides in balancing

sitions 3 and 8 where No. 5 Spindle was used with addi 15 the de?occulent oxides and ?occulent alkaline earths
that are gradually leached from the ?uxing glass frit
tional sodium silicate as indicated by a lower entry line
when it is added to the ceramic slip. Such balancing
for late aging periods for those compositions. Similarly,
imparts or improves slip stability, that is, it maintains the
an addedamount of sodium silicate was used for Body

viscosity of the slip at workable viscosity values.

Composition 6 for testing at the aging level of two days

and

more.

'

4 More particularly, as the alkaline earths are leached

from the frit, they tend to raise the viscosity and even
solidify the slip. .But if the de?occulent oxides are

Referring to Table III, Body Compositions 1 and 14

show the normal gradual reduction of viscosity with
age. Body Compositions 2 and 3 with Flux A required
more sodium silicate for initialdeflocculation than did

Body Composition 6 containing a ?ux of the present

invention. Body Compositions containing Flux A also
showed a thickening tendency on aging. Similarly, the

leached along with the ?occulents, the de?occulent

oxides counterbalance or counteract the de?occulents
25

to provide a stable, workable slip viscosity. De?occu

lent oxides include any metal oxide that may be made a
component of the glass frit and which counteracts as

described the ?occulating action of the alkaline earths.

synthetic diopside required more sodium silicate for

Examples of these are the alkali metal oxides such as

tion 6, and the viscosity of the former increased with 30 sodium oxide, potassium oxide, and lithium oxide. After

initial de?occulation than the present Body Composi

leaching from the glass, the de?occulent oxides are

usually present in the slip as silicates such as sodium

age. When calcined dolomite was added, the slip, thick

ened to a thick paste and it was not possible to de?occu

silicate, potassium silicate, and lithium silicate.

late it (Body 7). Body Compositions" 10, ll, '12 and 13 all

The amount of de?occulent oxides needed in the

caused their respective slips to thicken to a stiff paste

after-one day.

'

35 glass frit depends on how much ?occulent alkaline

earths'are leachable from the glass. Normally, however,

Critical data from the standpoint of the ?nished,1?red

piece, are set forth in Table IV. Only Body Composi

at least 5% by weight of the glass frit should be de?oc

tions 2, 4, 6 and 7 even approached vitri?cation at a

culent oxides. The amount leached for both the de?oc

culent oxides and the ?occulent alkaline earths may be

temperature of cone 6; Body Compositions 11, 12 and

13 thickened very rapidly on aging and were impracti
cal for use in a casting slip. Of the remaining composi
tions, only Body Compositions 6 and 7 gave lower
absorptions.

"

1'

'

'

TABLEIV '

in the parts per million range, although substantially

larger concentrations are possible. The absolute
amounts leachable for either thede?occulent oxides or
?occulent alkaline earths are not so critical as is the

Results of Fired Body Compositions

Body Composition 1

6 1

'8

10

ll

12

13

414

9.9
9.9

7.2
7.9

10.0

8.3

%Firing
Shrinkage

Cone 4051
Cone 5061

7.1
8.1

7.1
8.5

6.7
8.8

8.7
9.4

6.7
8.1

9.1
9.9

9.5
9.8

9.4
9.8

7.5
_ 8.4

9.6
10.2

8.8
9.7

Cone 61771

5776

8.9

9.5

8.5

10.1

10.3

9.8

- 8.2

10.4

10.3

'% Absorption

Cone 4151
Cone 5061

Cone 61371

4.8
3.5
2.7

4.0
1.8
0.8

4.1
3.3
.15

Warpage

Cone 4B5l
Cone SD61
Cone 607'
Modulus

of Rupture

061164051
Cone SD61
Cone 6B7I
Specimen cracked

3.5
2.1
0.7

3.7
3.2
2.2
1

2.8
0.8

2.8
0.8

0.3

0.3

2.9
1.0
0.2

g.

-_ 4.9
- 2.9
- 2.2

2.6
0.3

"

0.1

3.01 2.3
1.4
0.4
0.8
0.2

5.3
4.2

3.2

0.012 0.012 0.011 0.016 0.013 0.014 0.018 0.018 - 0.011 0.014 0.014 0.013
0.012 0.014 0.013 0.018 0.015 0.020 0.022 0.020 - 0.016 0.025 0.019 0.027
0.017 0.018 0.019 0.027 0.019 0.021 0.023 0.023 - 0.019 0.024 0.025 0.032

0.008
0.013
0.015

5019 5133 4956 4070 3282 5246 5564 5510 -- 4032

4904 4389 4538 5486 5424 6130 6274 5457 - 5482
4957 5274 3973 5821 5389 7203 7150 6034 - 4932

It will be noted that when using the fritted source of

dissolved diopside in accordance with this invention as
a body additive in the amounts set forth in Table II, the

5073 3407* 5418

5878 5404 5351
5162284595776

circumstance that the two alkaline materials be present

in amounts sufficient to counterbalance or counteract

each other to the extent they are respectively leached

4,337,316

11

from the frit upon its dispersal in a ceramic slip. There

results a buffer or-neutralization-like effect by which the

12

Extraction measurements were carried out on pow

ders of Examples A and B of Table V and, for compari

son purposes, on the synthetic diopside, glass Flux B,
and vitreous diopside of Table II. In each case, one
that it becomes unworkable. The net result is even bet- 5 gram of the ?ux powder having a particle size to pass all

de?occulent oxides successfully prevent the ?occulent

alkaline earth from so changing the viscosity of the slip

ter than adding sodium silicate or the like to the slip

after the frit has been added and undergone some leach~
ing away of its solubilities. The present frit is able to

but 3% on 325 Mesh, US. Standard Sieve, was shaken

with 100 milliliters of distilled water for 24 hours. The

solution was then ?ltered and diluted to 250 ml. The

maintain relatively constant rheological properties for
elements were estimated on the diluted portion by
days following milling, requiring the addition of only 10 atomic absorption. Table VI shows the results.
gziigimal amounts of a deflocculent such as, sodium siliTABLE VI

Considering the previous data more fully from the

standpoint of balancing the deflocculent oxides and

Flux
?occulent alkaline earths, Body Compositions l1, 12 15 Example A
and 13 of Table II use vitreous diopside as a ?ux. The
5x23212363

Na'l'
011
0'10

K+
108
0'02

Ca++
136
0'03

Mg++
101
0'04

PH
109
9'9

vitreous diopside was prepared by melting the oxides in

Dlgopside

0.01

001

0,15

002

ml

correct proportions and roll-quenching to form clear,

Glass Flux B

0.24

0.03

0.04

0.006

8.2

uncrystallized glass having no free (unreacted and un-

vilrequs

dissolved) alkaline earths..As shown by Table III, Body 20 Dwpslde

0'02

om

0'33

0'02

103

Compositions ll, 12 and- 13 within one day were too

viscous to be removed from the container. Referring to

Table IV, it will be noted that the modulus of rupture
for these Body Compositions are extremely poor com-

High _Ca+ + extractions lead to thickening, while

high Na+ leads to thinning of the slip. Example A has
both high Ca++ and reasonably high Nal', so that its

pared, for example, to that value for Body Composition 25 behavior is that of a composite. It does thicken the slip
6 which embodies the present invention. Test bodies
somewhat but nowhere nearly as badly as vitreous diop
were made from these compositions immediately from
side does. Example B contains more NazO than Exam
the slip while initial viscosity was still workable.
ple A to enhance or maintain Na+ extractability. Table
Body Compositions 7 and 8 which comprise synthetic
VI indicates that the Ca+ + extraction from Example B
diopside also contained as a result unreacted alkaline 30 into solution has indeed been drastically reduced, while
earths. Body Compositions 7 and 8 required more sothe Na+ has not been affected.
dium silicate because of the free alkaline earths present,
The glass compositions of Table V are detailed in
but once the effect of the alkaline earths was counterTable VII with respect to extraction and slip stability.

acted, the slip was quite stable as no additional leaching

All casting slips of Table VII have good viscosity
would be expected.
35 stability. The same technique described for Table VI
In contrast, Body Composition 6 representing the
was used in determining the elemental concentrations in
invention required only a normal amount of defloccu-

weight percent. The casting slip used was the same mix

lent for initially making the casting slip and a slight

as in Table II, using a threeweight percent ?ux glass,

addition after 24 hours, after which the slip was stable.

but in addition 1.5 grams of soda ash were added per
The following TableVprovides six additional exam- 40 kilogram of body. All cast bodies using these flux

ples of the present glass composition from which frit

can be made as described.

glasses were ?red to less than 1% porosity at Seger

'

cone 5. There are differences in the physical conditions

TABLE V

of the bodies cast as the glass ?ux is changed. For in

__

stance, the properties may change in hardness to soft

Exemgijrqynffgsjefggfii'"m
Exam p 1 e

Ego

like.. These factors

would be factors
to consider. in se
.
. .

lecting a particular glass composltlon for use with any

"a:

r;

5::

particular industrial body composition mix. The present

U20
CaO
MBO

Q1
23.9
7-3

01
20.5
151

0,]
17.1
12-6

OJ
19.5
14-5

Q1
18.5
13~7

Q1
17.5
13-0

invention does, therefore, provide ?exibility in the glass

50 composition that may be used without losing slip stabil
ity and the usefulness of the composition as a body ?ux.

$10;
P205

47.3
-

47.3
3.5

52.1 '
3.5

47.6
3.5

48.2
3.5

48.4
3.6

A1103

2:1

45 ness, ease of trimming, brittleness to plasticity, and the

6.7

6.7

7.4

6.8

6.8

6.9

TABLE VII
Properties of Glass Fluxes of Table V

Brookfield Viscosity #3 Spindle

Example Na+

Weight Percent
Extractabilities
K+ Ca++ Mgl+

0.11

0.08

0.36

0.01

B
c
D
E
F

0.10
0.07
0.08
0.11
0.10

0.02
0.02
0.02
0.02
0.02

0.03
0.02
0.02
0.05
0.01

0.04
0.04
0.03
0.05
0.04

POISES

P5+
-

0.02
0.01
0.02
0.007
0.03

pI-I
10.9

9.9
9.4
9.8
9.6
9.6

ml Sodium
Ready for
Silicate Used ' Casting
'

4.25
2.15
3.9
2.95
2.5

1 Day 2 Days 5 Days

Condition
of Cast

15.0
12.0
13.0
13.0
12.5

12.0
14.5
13.5
13.5
14.0

13.5
15.0
14.5
14.5
15.5

16.5
22.5
16.5
19.5
220

Brittle
Brittle
Fair
Fair
Best of
Series

4,337,316

14

. 13

While the preferred embodiment hereof is repre

(b) said frit being completely liquid at a smelting

sented by a slip cast sanitary-ware body, as will be un

derstood by those skilled in the art, the bene?ts of the
present invention, though perhaps notas pronounced or
dramatic as they appear in a sanitary-ware body, would
' quite likely be applicable to any ?red, ceramic body;
would de?nitely be applicable to any body which could
be characterized by those skilled in this particular art, as

temperature of about 2600" F. to about 2750 F.

and containing in solution the diopside precursors

CaO, MgO, and SiOg, said frit consisting essentially
of the following:

a feldspathic body.
And, while the preferred embodiment hereof in 10

CaO

15 to 25

MgO
Si02

10 to 20
35 to 50

Additive

5 to 20

volves' slip cast sanitary-ware, other than as slip solubil-

ity bene?ts are a consideration, the method of forming

said additive being selected from one or more of

the body, whether by extrusion, dry pressing, etc.,

the following in approximately the percent indi

would have no bearing on the ?nal results achieved, and 15

cated based on the total weight of the glass:

as such, method of forming really forms no limiting

feature of the invention disclosed herein.

K20
NaZO

The examples hereof amply demonstrate that the

?ne-grained diopside crystals of this invention lower
the ?ring temperature of the feldspathic body disclosed
by at least three Seger cones.

Li20
A1203

0 to 5
Oto l0
0 to 5
0 to 12,

(c) said frit being adapted upon heating to crystallize

Obviously however, an amount of the crystals and/or

frit of this invention which would promote any measur

from solution at least a ?uxing amount of said pre

able reduction in ?ring temperature and/or time of a

cursors in the form of ?ne diopside crystals having

an average particle size less than one micron and

ceramic body would constitute a fluxing amount. 25

Certainly, lowering the required heat treatment even
one Seger cone would involve a fluxing amount of

the diopside crystals and/or glass of this invention.

Although the foregoing describes several embodi

ments of the present invention, it is understood that the 30

invention may be practiced in still other forms within
the scope of the following claims.
I claim:

1. A substantially completely vitreous, smelted, clear

glass frit containing:

35

being substantially free of unreacted alkaline

earths, and
(d) said de?occulent oxides and ?occulent alkaline
earths being leachable from said frit in suf?cient
relative amounts to counterbalance each other and
prevent said thickening of the slip to an unwork

able viscosity.
2. The gl'ass frit of claim 1 in which at least 50% by
weight of said diopside precursors are converted to said

diopside crystals during said heating.

3. The glass frit of claim 1 in which said heating is at
a temperature from about Seger cone ?ve (5) to about
cone six (6).
4. The glass frit of claim 1 containing 0 to 3.6% P205.

(a) leachable amounts of deflocculent oxides and

?occulent alkaline earths and adapted to serve as a

ceramic body flux in a ceramic slip without thick

ening the slip to an unworkable viscosity,

45

50

55

65