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VOl. 10 April, 1927 No. 4

ORIGINAL PAPERS
THE EFFECT O F VARIOUS SODIUM SILICATES
AND OTHER ELECTROLYTES ON CLAY SLIPS
BY SAMUELJ. MCDOWELLZ

ABSTKACT

Attention is drawn to the fact that different brands of sodium silicate vary 250% in
their soda t o silica ratio. Four silicates with ratios from 1:1.8to 1:4 were added on a basis
of per cent NazO to slips of six clays commonly used in the whiteware industry. Rate of
flow, hydrogen-ion concentration, and settling behavior were studied. Maximum rate of
flow was produced in each case while the slip was acid. Those silicates high in silica were
the most potent in their effect on rate of flow for a given amount of NarO. The effect
was also more pronounced than that of NaOH, Na2COa, or silica sol which were used
as comparisons. Possible explanations of the mechanism of deflocculation are discussed
to explain the results.
Introduction
Sodium silicate as it is used in the ceramic industry is a more or
less thick syrupy liquid. I t is made b y fusing proper proportions
r?f soda ash (Na2C03) an d sand (SiOz) and dissolving the resulting
glass in water. Soda ash and silica in all proportions where silica is
present in greater amounts than the 1 : 1 molecular ratio will form
glasses. Figure 1 shows the melting point diagram of this part of the
Published by permission of the Director, Bureau of Standards. Presented a t
the Annual 'Meeting, AMERICAN CERAMIC SOCIETY, Detroit, Mich., February, 1927.
(White Wares Division.) Received November 15, 1926.
Superintendent, Columbus Branch, Bureau of Standards.
226 MCDOWELL-THE EFFECT op VARIOUS SODIUN SILICATES

system NazO-Si02.1 The approximate composition range for com-

mercial sodium silicate glasses is also shown. Melting may start a t as
low as 790°C and, in a majority of cases, will be complete under 1000°C.
As the silica content is raised above 77% by weight, (Fig. 1),2 the
temperature required to melt the glass goes up rapidly, and the solu-
bility of the resulting glass in water is decreased. This fact places the
high silica ratio a t about 1 Na2O : 4 SiOz for the commercial solutions,
while the lower limit is determined at about 1 NazO : 1.5 SO2 by the
tendency for sodium metasilicate (NazO Si02 NH20) to crystallize.
6

The term sodium silicate then does

-
‘700
not mean one definite chemical com-
pound. I t rather applies to a series
1500.-
of solutions one of which may have
two and one-half times as much silica
as another for a given soda content.
The water contents of these solutions
are also variable depending on the
solubility of the glass: each ratio of
soda to silica in the glass produces
a silicate solution which has its own
peculiar physical properties and re-
sulting uses which vary considerably.
A solution high in silica loses its
water with comparative ease but can
‘‘I NO, 0 S;02 ‘.* Na20;2SiO,
sioz only be concentrated to a point
NOz 0 h;o* Quartz where it contains about 30% solids
FIG.1.-Melting point diagram of without gelling.3 The gelled mass has
the system NazO * SiOz-SiO*. Compo- a conchoidal fracture and bounces
sition is expressed as weight Per cent like rubber. It flows under moderate
SO,.
pressure, however, and the flow-
pressure curve passes through the origin. A solution high in soda
loses its water slowly, but may be concentrated to a point where over
60% solids are present and still be handled and pulled into long threads.
Upon further concentration the stiffness increases until the material is
practically a solid but it will again become somewhat pliable under
pressure.*
1 G. W. Morey and N. L. Bowen, “Binary System Na20 .SiOrSiOa”, Joxr. Pllys.

Chem., 28, 1167 (1924).

* Since the molecular weights of NazO and SiOl are nearly the same (approximately
62 and 60, respectively) the ratios “by weight” and “molecularly” can be used inter-
changeably for practical purposes.
* W. D. Bancroft, Applied Colloid Chemistry, McGraw-Hill Book Co.
4 J. G. Vail, “Silicate Solutions and Some Siliceous Gels,” SOC.Chem. Ind., 44,
214 (1925).
 AND OTHER ELECTROLYTES ON CLAY SLIPS 227

the ratio of soda

to silica.
Although sodi-
um silicate is not
usually used
alone t o defloc-
culate clays it is,
according to Ble-
ininger3 a n d
S ~ h u r e c h ta, ~po-
tent material for
this purpose. T h e
silicate which
Bleininger used
228 MCDOWELL-THE EFFECT OF VARIOUS SODIUM SILICATES

T h e present investigation was undertaken to ascertain the defloccu-

lating effect of sodium silicates of various ratios and the four whose
compositions are given in Table I1 are probably representative of those
used in the industry. I t was also later found desirable t o include
the effect of other electrolytes for comparison.
Procedure
Each clay (Table I) was crushed through an 8-mesh
Preparation
screen and approximately four pounds were dried for 24
Of ‘lay ’lips
hours at 70°C. T h e temperature was not carried to
110°C as i t was feared th at this might injure the plasticity to be ob-
tained when the clay was mixed with water. Fourteen hundred grams
were weighed u p with 2800 grams of distilled water. This water was
not absolutely constant in its hydrogen-ion concentration, the p~
TABLE I
CHEMICAL
COMPOSITIONS
OF CLAYS
USED
Loss on
ignition SiOs Aln01 FerOa CaO MgO KtO NatO Ti08
M. W. M. Eng.
china clay 13.14 45.75 38.96 .61 1.18 .29 .04
Tenn. ball
clay No. 7 12.81 45.60 38.70 1.00 .12 .20 .25 .42 1.04
Georgia (Albion)
china clay 13.10 45.25 38.7 .58 .21 .09 .51 .49 1.17
Florida pIastic
kaolin 13.46 48.82 36.78 .80 .40 .41 .14
N. Carolina
kaolin 13.42 44.72 39.66 .50 .07 .01 .94 .17
Kentucky ball
clay No. 4 12.40 49.32 32.64 1.44 .34 1.03 .29 1.00
M. W. M. English china clay is a washed secondary clay and is about average for
this type.
Tennessee ball clay No. 7 is a light colored, rather plastic ball clay.
Albion (Georgia) china clay is an unwashed secondary china clay of the soft variety.
Florida plastic kaolin is a washed clay of secondary origin. I t is quite plastic.
North Carolina kaolin is a washed primary kaolin and is low in plasticity.
Kentucky ball clay No. 4 is a medium dark, rather plastic ball clay.
TABLE I1
CHEMICAL
COMPOSITION
OF THE SODIUM
SILICATES
USED~
Silicate No. 1 No. 1 No. 3 No. 4
% % % %
NazO 6.34 9.12 13.63 19.32
SO2 24.47 29.37 33.17 33.87
HZO by difference 69.19 61.51 53.20 46.81
Molecular ratio NazO t o SiOz 1: 4 1: 3.33 1: 2.52 1: 1.81
’Analyses obtained through the courtesy of the Philadelphia Quartz Company.
value varying from 6.0 to 6.5. T h e batch was mixed in a ball mill for
one hour t o bring the clay into suspension with a minimum of grinding.
T h e slip was screened through a 65-mesh screen and placed in sealed
jars; no water was added an d none allowed to evaporate so t h a t the
ratio of water to clay (by weight) was as 2 : 1. T h e specific gravity
of the slip was 1.25 k .01.
 AND OTHER ELECTROLYTES ON CLAY SLIPS 229

Three hundred and sixty grams of slip (con-

Preparation of
taining 120 grams of d r y clay) were taken for
each determination and sodium silicate was
added in increments of .00570 Nan0 (per cent based on weight of
clay in the slip). This is comparable t o additions of approximately
0.1 of 1% of No. 1 silicate. However, since the other silicates (Table 11)
contained a greater percentage of N a 2 0 than did No. 1, less than 0.1%
of silicate was added in their cases for each increment. This method
of addition was thought t o be the most logical since the presence of
the sodium ions, with the consequent presence of hydroxyl ions, is
thought t o be the activating agent in deflocculation phenomena when
sodium salts a r e used. T h e addition of electrolyte t o the slip was
based on the d r y clay content rather than the water content because
Schurecht’ has shown the clay phase to be the more important. T h e
$H values of the silicate
solutions used were as
foIlows :
1 = 10.25
2 = 10.50
3 = 10.75
4=11.55
O n e or
Determina-
more in-
tion of Rate c r e m e n t s
Of of sodium
silicate solution were
added t o 360 grains of
each slip, together with
sufficient distilled water
to total 400 grams. T h e
treated slip was thor-
oughly shaken in a
graduated cylinder and
allowed to flow through
a n “efflux viscosimeter”
Additions o f odium Silicate
of the Mariott tube type in Increments &o Percent NazO
(similar t o t h a t de- FIG.3.-English h i n a clay.
scribed by B1eininger)Z
- ,

with an opening of 3~inch. T h e time required for 200 cc to flow was

measured with a stop-watch and checked until two readings were
H. G. Schurecht, loc. cit.
A. V. Bleininger, “Use of Sodium Salts in the Purification of Clays and in the
Casting Process,” Bur. Stand., Tech. Paper, No. 51. Also, by T. G. McDougal, Bur.
Mines, Tech. Paper, No. 126.
230 MCDOWELL-THE EFFECT OF VARIOUS SODIUM SILICATES

obtained to within $ of a second. The average of these two was taken

as the time required, and was compared with the time required for
the flow of 200 cc of water at the same temperature. (The temperature
varied only 5 3 ° C and no correction was made for it.) T h e density
of the water and slip being known, the quantity used as ordinates for
Figs. 3 to 14 was calculated from the following formula which is the
one used with the Oswald viscosimeter :
Relative time of flow
7 ._
,
- (corrected for difference in
(c
v) density) =ax/wt
6;
where a=density of liquid
- w =density of water
9 x = time of discharge
5 1 of liquid
a
t =time of discharge
4 of same amount
of water

The potenti-
Hydro- ometer method
gen-Ion
was used to de-
Deter-
termine the
mination
value as it could
be done directly on the
slip itself, thus making i t
unnecessary to filter the
material and test the fil-
trate as must be done in
the colorimetric method.
000 '.005 ,010 .Ol5 .020 .025 .030 ,035 .040 045
I
A Leeds and Northrup po-
Additions o f Sodium Silicate tentiometer, and a calomel
in Increments of.005 Percent Na,O
electrode with a porous
FIG.4.-Tennessee ball clay.
cup in which was placed
an excess of KCI so t h a t there was at all times a saturated solution,
were used. T h e hydrogen electrode consisted of a piece of platinized
platinum wire around which bubbled hydrogen which was procured
in purified form in tanks. This apparatus is similar t o that described
by Randolph and D0nnenwirth.l T h e equipment used is shown in
Fig. 2.
After the determination of relative time of flow
Settling Behavior
and hydrogen-ion concentration, 200 cc of the
D. W. Randolph and A. L. Donnenwirth, "Hydrogen-Ion Measurements on Clay
Slips", Jour. Amer. Cernm. Soc., 9, 541-47 (1926).
 AND OTHER ELECTROLYTES ON CLAY SLIPS 231

slip were placed in graduated stoppered bottles and the per cent of
settling for a period of sixteen hours determined. T h e tests on the
ball clay and plastic kaolin were unsatisfactory due to the thickness
of the slip and the inability to measure accurately the small per cent
of settling.
Results
Figures 3, 4,5 , 6 , 7, and 8 show graphically the effect of the various
sodium silicates on the rate of flow of the different slips. T h e corre-
sponding PH values an d the settling behavior, when i t could be ascer-
tained, are also shown. s"
T he rate of flow, $H
value, and settling be- 2
25
havior for each batch of un- .$ 20
treated slip varied slightly; z,5
for this reason a compari- 2
son of values resulting from z ' O
additions of each incre- 2 5
ment of electrolyte is diffi-
cult. However, the addi-
tion which causes the 1.7

curve t o flatten out, th at ~

is, attain minimum time e1.6

of flow-can be deter- bo
mined rather closely in .-g1.5
each case. I t will be noted I-
9
t h a t this condition is pro- 21.4
-
duced by a smaller per- 8
centage of NazO when 1.3
No. 1 silicate is used than .OOO ,005 .O/O ,015 .020 .025 .030 .035 .040 .045
Additions o f Sodium Silicate
is the case with any of the in Increments of.005 Percent Na,O
others, although the effects FIG.S.-Georgia china clay.
of No. 2 are similar and,
in some cases, equal. T h e case of English china clay is typical, for
which the following percentages of NazO are necessary to attain
minimum time of flow:
Per cent
For No. 1 silicate .015
" No.2 " .015
No. 3 .025
I' No.4 " .030

With some clays the difference is more marked than with others,
bu t t he order of effect is the same in each case.
232 MCDOWELL-THE EFFECT O F VARIOUS SODIUM SILICATES

One thing which was unexpected was the p~ values which corre-
sponded t o the minimum time of flow figures. There was no one value
where minimum time of Bow occurred nor was there a break in the
curve of $11 values a t t h a t point. Th e value varied with each clay
and each silicate and ranged from 4.3 to 6.9 occurring in each case
while the slip was acid.
- This is different from
.a
6; the conditions which a re
- thought to prevail when
53 a clay reaches minimum
time of flow. Neither
does i t bear o u t the find-
26 ings of Scripture and
Schramm’ who found th a t,
2.4 with china clays, the @H
8G varied from 7 to 11.7
bo 2.2 where a 5 ratio of Q was
? used and NaOH used as
5>
2.0 the electrolyte. Hall also
P found, using a $ ratio of
-
$ 1.8 M, and testing for maxi-
mum deflocculation b y the
46 settling method, t h a t the
point of maximum defloc-
1.4 culation was reached at a
,000 ,005 .OJO .0/$ ,020 ,025 030 ,035 .040 045 PH value between 10 and
Additions of Sodium Silicate
in Increments of.005 Percent No,O 12 where NaOH was
FIG.6.-Florida kaolin. used.2
I t was therefore thought
desirable t o use NaOH and Na2 C0 3solutions as electrolytes and deter-
mine their behavior when added to this group of clays. T h e solutions
were made up as before, based on the ratio of N a 2 0 to dry clay, except
t h a t each increment consisted of .02% NazO instead of .OOS%. T h e
*H values of the solution as used were:

NaOH 13.15
Na2C03 11 .o
T h e results obtained using NaOH closely checked those of Scripture
and Schramm and also those of Hall. Figures 9, 10, 11, 12, 13, and 14
show the relations between the effects of No. 1 sodium silicate, NaOH,
“Deflocculation of Clay Slips and Related Properties”, Jour. Amer. Ceram. SOC..
9 [4], 175 (1926).
* F. P. Hall, “Effect of Hydrogen-Ion Concentration upon Clay Suspensions,”
Jour. Arne*. Ceram. SOC.,9,989 (1923).
 AND OTHER ELECTROLYTES O N CLAY SLIPS 233

Na2C03and silica sol.’ The latter was used in an attempt to explain

why the effect of sodium silicate was so much more pronounced than
that of either sodium hydroxide or sodium carbonate. Assuming that
silicates contain colloidal silica, it was thought that perhaps colloidal
silica alone might be a deflocculating agent. I t was added to various
clays and the effect on rate of flow, #H values, and settling noted as
before. Unfortunately
there was sufficient solu- a,
tion available to test only 3;
three china clays and one 22
ss
ball clay. As will be noted, p
additions of silica sol alone
had little or no effect on
either rate of flow, #H
value, or settling behavior.
An interpretation of the
relation between
6
the G f . 4 ~
settling behavior and the \
other properties is diffi- E
cult due to the somewhat Z f 4 O
erratic results obtained in 5
some cases. There is ap- s,,
parently not sufficient evi-
Additions o f Sodium Silicate
dence on which to base in increments of.005Percent No,O
any conclusions in regard FIG.7.-North Carolina kaolin.
to this property. The
variation in results may have been due to the absorption in some cases
of some KCl solution through the porous cup of the calomel electrode
and its effect on the settling behavior of the slip.

Discussion of Results
The mechanism of the dispersion of clay slips by the addition of
salts is generally agreed to be connected with the presence of the
hydroxyl ion. The exact r6le of this ion, however, is the subject of
Through the courtesy of Richard Bradfield of the College of Agriculture, Univer-
sity of Missouri, a small amount of silica sol was obtained which had been prepared by
him by adding dilute HCI to dilute sodium silicate and centrifuging. (Richard Brad-
field, “A Centrifugal Method of Preparing Colloidal Ferric Hydroxide, Aluminum
Hydroxide and Silicic Acid,” Jour. Amer. Chem. SOC., 44, No. 5 ) . I t had been further
purified by electro dialysis which was continued until the cathode solution no longer
reacted pink to phenolphthalein. I t may therefore be assumed that only SiOn was
present. The solution as received contained 1.21 % SiOz and had stood three years with-
out any apparent tendency to gel. It was made into a solution which contained the same
amount of SiOl as the solution of No. 1 silicate used; the pHvalue was 5.2.
234 MCDOWELL-THE EFFECT OF VARIOUS SODIUM SILICATES

some discussion, Bleiningerl says, that the negatively charged OH

ions repel the similarly charged clay particles electrostatically. Span-
genberg2 claims that the OH ion is adsorbed by the clay particle
and the so charged particles repel each other. Bole3 suggests that
the OH ion may form a
hydroxyl-ion colloid ab-
sorption complex with the
positively charged surface
coating on the clay par-
ticle and that the then
negatively charged clay
particles repel each other.
Mattson4 found that the
negative charge on the
clay particle reached a
maximum in the region of
000 005 010 0/5 .OZO ,025 .030 .035 .040 .a6 maximum deflocculation
Additions o f Sodium Silicate
in Increments of.005 Percent Na,O
but that the actual value
FIG.8.-Kentucky ball clay. of this charge varied for
each solution.
I t would seem, if dis-
persion were due merely
to the repelling effect of
the OH ions and clay
particles as noted by I2 &
In
Bleininger, that a given 10 %

amount of NazO in the 3 :-

form of sodium carbon- 6 9
ate (or particularly sodi- 4 %
um hydroxide which is
highly ionized) should
produce just as great or
greater dispersion as
does sodium silicate and
a t the same PH value,
but this is not the case. 00 .02 04 .06 .03 O./O 0.12 0.14 0.16 0./8
Percent Additions o f Na,O
If, according to Span-
FIG.9.-English china clay.
genberg, the OH ion is
1 Bur. Stand., Tech. Paper, No. 51, p. 7.
* A. Spangenberg, Zin Evkenntnis des Tongreszens ihren Einflusz auf die Tonver-
flussigung Dissertation Darmstadt 1910;J. K. Neubat, DieTonverflussigungdurch alkali.
G. A. Bole, “Mechanism of Plasticity from Colloid Standpoint”, Jour. Amer.
Ceram. SOC.,5 , 469 (1922).
‘ “Die Beziehungen zwischen Ausflockung, Adsorption und Teilchenladung mit
besonderer BerUcksightigung der Hydroxyleionen”, Kolloidchem. Beihefle, 14 (9-12) 227.
 AND OTHER ELECTROLYTES ON CLAY SLIPS 235
adsorbed by the clay particle, which seems unlikely as both have a
negative charge, NaOH again should produce dispersion just as quickly
as sodium silicate and at the
same f i H value.
Acombination of the theories
of Bole and Mattson seems to
most nearly explain the results
obtained in this investigation.
I t seems probable that hy- 3.6
droxyl-ion colloid absorption 3.
complexes are formed as has
been suggested. When sodium 63.0
hydroxide or carbonate is used,
the hydroxyl ions attract the
positively charged particles
and ions from the surface of
the clay particles until the
particles of clay have de- /.8
veloped maximum charge for
that solution and we have
maximum dispersion. With
sodium silicates colloidal FIG.10.-Tennessee ball clay.
silica is present which is
negatively charged. This
tends to adsorb Na+ ions
and disturb the equilib-
rium so that the OH-ions
are more active in their
formation of the hydroxyl
ion absorption complexes.
Y
The clay particle therefore
attains maximum charge
for that solution sooner
and maximum dispersion
results.
For this reason there is
a,
'3 a different PH value for
9, 1.4
LL
each clay and each electro-
lyte where maximum
charge on the particles is
Percent Additions of No,O attained and with the use
FIG.11.-Georgia china-clay. of sodium Silicates, particu-
larly those high in silica, the action i s more pronounced for a given
236 MCDOWELL-THE EFFECT OF VARIOUS SODIUM SILICATES

lo01
82 &
.”?
6ro
4a

00 02 04 06 08 010 012 0 1 4 0/6 018

Percent Additions o f No,O
FIG 12.-Florida kaolin.

0.0 .02 .04 .06 .08 0.10 0.12 0.14 0.f6 0.18
Percent Additions o f M , O
FIG. 13.-North Carolina kaolin,
 AND OTHER ELECTROLYTES O N CLAY SLIPS 237

amount of N a 2 0 . There is not, however, a break in the P H curve at

7 as predicted by Bole b u t in view of Mattson’s work this does not
seem probable.
I t has been noted by shop men th at sodium silicate used alone
produces “stringy” slip while sodium carbonate produces slip with a
high surface tension if both are brought to minimum time of flow.
This would be expected from the curves in Figs. 9, 10, 11, 12, 13, and
14, which show t h at a slip treated with sodium silicate has a much lower
time of flow than the same slip
treated with sodium carbonate.
I t will be noted also th at much
more NazO is required in the
case of the carbonate.

Conclusions
b G
16

(c

1. Sodium Silicates low in

soda and high in silica between l5

the ratios 1 : 3.33 to 1 : 4 are the

most effective deflocculating 42 14
agents for a given NazO con-
tent. I t must be remembered Percent Additions o f N a p
tha t these silicates contain a FIG.14.-Kentucky ball clay.
large amount of water and
therefore i t may be necessary to add more of this type of silicate
solution than of the other solutions to introduce the same amount
of NazO.
2. T h e PH value at which clay particles attain maximum charge is
lower for sodium silicate solutions than for NaOH or NazC03 solutions.
Th e probable reason th at sodium silicate is a more potent deflocculat-
ing agent is due to the presence of colloidal silica which adsorbs
the Na+ ions thus disturbing their equilibrium with the OH- ions
and allowing the latter to become more active in forming hydroxyl-
ion complexes with the positive charged particles and ions on the
clay particles and allowing the clay particles to reach maximum charge .
for that particular solution. I t is therefore necessary to specify the
agent used when giving the PITvalue at which a clay reaches minimum
time of flow.
3. For the clays of this investigation, and when sodium silicate
was used, minimum time of flow occurred while the slip was acid
(@H value < 7).
4. Silica sol ( S O z )used alone is not a deflocculating agent.
5. T h e use of high silica sodium silicate rather than sodium carbon-
ate would seem desirable especially where soda blisters are a difficulty.
BRANCH
COLUMBUS
BURXAUor STANDARDS
COLUlaSVS, OHIO