Deflocculation of Concentrated Aqueous Clay Suspensions with

Sodi um Pol ymet hacrylates

Anna Bonamartini Corradi, Tiziano Manfredini, Gian Carlo Pellacani,* and Paolo Pozzi
Dipartimento di Chimica, University of Modena, 41 100 Modena, Italy
The ability of sodium polymethacrylate salts with various
molecular weights (1200 to 30000 g-mol-') to deflocculate
concentrated aqueous suspensions (58 wt %) of two clays,
widely used for stoneware ceramic tile production, was
investigated. Rheological measurements were made in dis-
tilled water or in water containing calcium ions (0 to 6 x
m~l - dm- ~) to evaluate the practical applications of
these salts as deflocculants in the ceramic tile industry. All
slips presented a nowNewtonian behavior. Polymethacry-
lates with low molecular weights were the most efficient
deflocculants for clay suspensions. The salts acted by an
essentially electrosteric stabilization mechanism, in combi-
nation with a high sequestering ability toward flocculating
cations. For their efficient deflocculating capabilities
toward concentrated aqueous clay suspensions, sodium(1)
polymethacrylates may be considered for practical indus-
trial application, in particular for the preparation of liquid
deflocculants.
I. Introduction
N THE ceramic industry, a knowledge of the rheological
I behavior of ceramic slips is fundamental to controlling their
castability, pumpability, and cast strength, to improving the
economics of processes and the quality of end products, and
optimizing energy requirements. The rheology of concentrated
suspensions such as ceramic slips depends on solid-phase con-
centration and on the shape, size, and size distribution of the
disperse phase, as well as its aggregation conditions.' Liquefy-
ing stiff, flocculated clay suspensions thus requires the addition
of chemicals, including inorganic salts, alkalis and organic
compounds.*
In general, suspensions can be dispersed electrostatically (by
generating a common surface charge on the particles), steri-
cally (by causing a polymer, which serves to form protective
colloids, to be adsorbed onto the particles), or electrosterically
(by using both an adsorbed polymer or polyelectrolyte and a
G. L. Messing-contributing editor
2000 I
O f I I I
5 4 5 6 5 8 6 0 6 2 6 4
SOLID CONTENT (WT%)
Fig. 1. Minimumapparent viscosity values (mPas, T =27.9 s - ' )
against solid content for aqueous suspensions of Samone(-) and
Debbia (----) clays (58 wt%) in the presence of sodiumpolymethacry-
lates with various molecular weights (B =0; D =X ).
Table 11. Physico-Chemical Characteristics of the Sodium(1)
Polymethacrylates (pH 7)
Manuscript No. 196730. Received May 23, 199 1; approved December 7, 1992.
Supported by Consiglio Nazionale delle Ricerche (C.N.R.) of Italy.
'Member, American Ceramic Society.
Table I. Cumulative Granulometric Data of the ' h o Clays
(wt% of Particle Undersize)
Water log (avg mol wt) Density CBP*
. (wt%) (gmol -' ) (g.cm- ) (mg.g ' f
Type
A(Soka1an PA 15) 45 3.08 1.32 790
B(Sokalan PA 20) 45 3.39 1.33 762
C(Sokalan PA 30) 45 3.90 1.33 660
D(Sokalan PA 40) 35 4.18 1.25 628
E(Sokalan PA SO) 40 4.48 1.27 610
*Calcium(lI) ion binding power.
~ ~~
Size class Samone Debbia
(pm) (wt%) (wt%)
< I 6.9 6.5
<2 14.1 12.1
<5 29.3 23.1
<10 52.2 35.7
<so 98.1 92.1
<100 100.0 100.0
significant electrical double-layer repulsion).' Industrial experi-
ence shows that, in highly concentrated oxide suspensions,
problems related to high viscosity, aging, and the processing of
multiphase systems, present in electrostatically stabilized sys-
t em~, ~ can be drastically reduced by using polyelectrolytes as
dispersants or deflocculants .'-*
Previous papers deal with the deflocculating ability toward
concentrated aqueous clay suspensions of inorganic monomeric
509
510
700
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*
b
0
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b
z
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a: 400
4
a
a
4
5 300
600
5;
s
500
E
2
200
SAMONE
Journal of the American Ceramic Sociery-Corradi et al.
Vol. 77, No. 2
0
6
s
0
MW 1200 =*
MW 2500 =o
MW 8000 =+
MW 15000 =x
MW 30000 =O
I
0 2 4 6 8
CALCIUM CONTENT ( 1000~ moi/d&
(a)
DEBBIA
6ool
1
500
MW 1200 =*
MW 2500 =o
MW 8000 =+
MW 15000 =x
I MW 30000 =O
400 +: ===: - : , - -
zoo I I I I
0 2 4 6 8
CALCIUM CONTENT (1000 mol/dm3)
(b)
Fig. 2.
Samoneand (b) Debbiaclays (58 wt%) in presenceof sodium polymethacrylates with various molecular weights.
Minimum apparent viscosity values (mPas, T =27.9 s-') against calcium ion concentration (mol-dm-') for aqueous suspensions of (a)
and oligomeric sodium phosphate' and silicate" salts. The pres-
ent work attempts to verify that the advantages of using poly-
electrolytes to stabilize oxide suspensions can be transferred to
highly concentrated aqueous clay suspensions.
A variety of polyelectrolytes are available commercially, but
until now they have found scant use in the ceramic floor-tile
industry, despite their predictably high efficiency as defloccu-
lants.".'* In the present paper, weinvestigate the use of sodium
polymethacrylates with an average molecular weight varying
from 1.200 to 30.000 gmol -' as deflocculants of concentrated
aqueous clay suspensions. The results are compared with those
obtained using inorganic defl occul ant~.~~~~
11. Experimental Procedure
( I ) Materials
The investigated clays (from Modenese Apennines) were
named Debbia and Sumone. Their physicochemical and miner-
alogical properties had been previously reported.'
The sodium polymethacrylates (Sokalan series, BASF, Ger-
many) were reagent-grade, linear chain polymers. The calcium
ion binding power (CBP expressed as milligrams of CaCO,
linked by 1 g of polymer) was determined by titrating aqueous
solutions of sodium polymethacrylates at pH 1 1 with an aque-
ous solution of calcium acetate in the presence of sodium car-
bonate, until incipient precipitation of calcium carbonate.
(2) Preparation of Suspensions
In the sample preparations and in the laboratory tests, experi-
mental industrial conditions were reproduced within certain
limits." Clays, dried in air, were dry-ground in a ball mill with
a 15-L capacity to obtain - 15 kg of powder. The ground pow-
der was put through a 35-mesh ASTM sieve and later used for
slip preparation. The slips, with added weighed amounts of
polymethacrylates, were prepared in a fast ball mill (300-mL
capacity) for 5 min by controlling the solid contents, the num-
ber of grinding media, and the time, to achieve reproducible
experimental conditions. The experiments were also performed
in the presence of 0 to 6 X lo-' m~l - dm- ~ calcium ions.
(3) Physical Measurements
Size analyses were performed with a laser particle size ana-
lyser (Fritsch Model Analysette 22, Idar Oberstein, Germany)
on clays prepared by dispersion for 2 h of -5 g of raw material
in 200 mL of distilled water using 0.36 g of sodium hexameta-
phosphate and 0.08 g of sodium carbonate.
After the slips had stood for 1 min, rheological measure-
ments (Contraves Rheomat Model 1 15, Zurich, Switzerland)
were conducted with a cylindrical coaxial viscometer using the
shear rate sequence 13.6,27.9, 1 17.1, and 492.0 S K I and a DIN
145 measurement system, which gives the best response sensi-
tivity for the measured apparent viscosity. The shear rate was
applied until a steady stress value was obtained. To evaluate the
time-dependent behavior of the slips, a check was performed at
15 min from the end of the experimental measurements, using
the 13.6-s-' shear rate. The results discussed in the present
paper refer to the measurements performed at a shear rate of
27. 9 s- ' , which well represents the industrial conditions as pre-
viously di ~cussed.~~'~
111. Results and Discussion
( I )
Both of the investigated clays are used widely in the factories
of Sassuolo (Italy) in the single-firing technology for producing
highly sintered red floor tiles (known also as red gres or red
Characterization of Clays and Polymers
~
February 1994
Dejlocculution of Concentrated Aqueous Clay Suspensions with Sodium Polyrnethacrylutes
511
SAMONE
-- ~ _ _ ~ ~
MW 1200 =*
MW 2500 =o
MW 8000 =+
MW 15000 =
MW 30000 =O
0
n
0-
0
* - - * -
- - a -
+
-
+
0 2 4 6 8
CALCIUM CONTENT (1000. mol/dm3)
(a)
DEBBIA
- a
a
a a-
/- MW 1200 =.
MW 2500 =o
MW 8000 =+
1 /
MW 15000 =x
MW 30000 =O
0 2 4 6 8
CALCIUM CONTENT (1000. molldm3)
(b)
Fig. 3.
Debbia clays (58 wt%).
Sodium(1) plymethacrylate amounts (wt%) against calciumion concentration (mol.dm ) for aqueous suspensions of (a) Samone and (b)
stoneware). X-ray powder spectra and chemical and thermal
analyses indicate that Debbia contains chloritic and illitic
clays; a large amount of quartz, feldspars, iron oxides, and
kaolinite; and a small amount of montmorillonite. Samone is a
chloritic and illitic clay with kaolinitic minerals, calcite, and a
large amount of quartz, feldspars, and iron oxides. The high
content of clay minerals (-60 wt%) gives these clays great
plasticity.
The particle size dimensions for clays are reported in Table I.
(2) Rheological Measurements
The ground clays, put through a 35-mesh ASTM sieve, were
slowly suspended in distilled water in a fast ball mill (300-mL
capacity) working at slow speed. The pH values of the suspen-
sions were 9.2 for Debbia clay and 9.4 for Samone clay. The
slips, added drop by drop with the calculated amounts of liquid
polymethacrylates, were homogenized at the maximum ball-
mill speed for 5 min. The pH values do not change signifi-
cantly, each being 9.1.
Because all the systems show pseudoplasticity at high con-
centration, the apparent viscosity at 27.9 s- is reported for
composition of the suspension rheology.
( a) Viscosity vs Amount of Clays: The rheological behav-
iors of the aqueous clay suspensions are very similar because
they depend strictly on the type and amount of the polymetha-
crylates, which act as deflocculants. In fact, the apparent vis-
cosities of the slips decrease sharply with increasing amount of
deflocculant. Once minimum viscosity values, which remain
constant for a long interval of deflocculant addition (-0.3 to
0.6 wt%), have been achieved, the overdeflocculation effect
prevails. In particular, the workability range (corresponding to
the concentration range of deflocculant at which the low appar-
ent viscosity values remain constant) increases as the molecular
mass of the deflocculants decreases.
Todetermine the maximum solids content of the slips that is
consistent with good workability and involves only a moderate
increase in thixotropy, the results of numerous experiments
have been summarized in Figs. 1 to 4. The plots, although
unusual, are simple and effective. The minimum apparent vis-
cosity-the lowest value of apparent viscosity of a slip
obtained with the required amount of deflocculant-is plotted
against the amount of clay (wt%) in the presence of two poly-
methacrylates (B and D, see Table I1 and Fig. I ). For good
workability, the minimum apparent viscosity of concentrated
aqueous clay suspensions must be on the order of -500 to 600
mPa.s value, which also enables good instrumental sensitivity
and accurately reproduces industrial conditions. Figure 1 dem-
onstrates that a solids content of 58 wt% for both clays satisfies
the above-mentioned requirement very well. At this concentra-
tion, the slip pH is -9.1 to 9.3.
The Samone clay shows better deflocculating capability
because the Debbia contains more montmorillonitic clay. This
is similar to the behavior observed for inorganic deflocculating
agents, such as sodium phosphates or silicates. These com-
parisons imply that the deflocculating capability of polymetha-
crylates is very similar to that of silicates. The phosphate
salts, in particular the tripolyphosphate, emerge as the most
efficient deflocculants, enabling work at more concentrated
aqueous clay suspensions (>60 wt%).
The stabilization mechanism of the sodium polymethacry-
lates is explained below. The carboxylic acid dissociation and
the charging of the polymer increase as pH increases; at pH
2 8 . 5 the molecules are effectively negative, with 01 (dissocia-
tion degree) approaching 1 , , 13. 14 and form relatively large,
expanded, random coils, as a result of the electrostatic repul-
sion between the negatively charged surface sites.1s At pH -9
all surfaces and edges of three-layer minerals (SiOz) are fully
Journal of the American Ceramic Society-Corradi et al. Vol. 11, No. 2
512
500 -
400 -
300-
~
0
+
X
a
+
0
4
i
200 !
3 4
Log MW
8 0 0 7 0 0 6 0 0
CBP (mg/gr)
(a)
5
700
600
500
400
300
200
3
DEBBIA
a
f
8
t
I
4
Log MW
5
8 0 0 700 6 0 0
CBP (mg/gr)
(b)
Fig. 4.
the log of molecular mass or the sequestering capability (mg-g - ') of the sodium(1) polymethacrylates at various calcium(I1) ion concentrations.
Minimumapparent viscosity values (mPas, 7 =27.9 s-') for aqueous suspensions of (a) Samoneand (b) Debbiaclays (58 wt%) against
negati ~e,~.'~ and therefore repel the anionic moiety, or the ter-
minals of the side branches. This would prevent polymer
adsorption onto the surface and the system would not defloccu-
late. However, the fact that some polyelectrolyte remains
adsorbed at high pH seems to indicate that forces other than
electrostatic are involved in the adsorption process. It has been
suggested that the adsorption of polymers on charged solid sur-
faces may occur by the establishment of hydrogen and hydro-
phobic bonds between small segments of chains and the sur-
faces, while loops and tails protrude into the It is
the combined role of the bonds between segments, the surface
configuration of the adsorbed polymer, particularly the location
of the ionized groups in respect to the solid, and the electro-
static interaction between the polyelectrolyte and the surface
which will determine the amount of deflocculant adsorbed.
(b) Viscosity vs Amount of Polyelectrolytes: Toestablish
the differences in the stabilization efficiencies of various poly-
methacrylates, we investigated the rheological behavior of 58
wt% Debbia and Samone aqueous clay suspensions, in which
calcium ions in the 0 to 6 X mol-dm-' concentration
range, which is known to have a high flocculating ef f e~t,~,~"* ~
was added. These results are relevant to industrial practice,
since the ceramic factories often use recycled waters containing
calcium ions in the concentration range -3 X to 5 X
lo-) m~l - dm- ~.
Changes in the minimum apparent viscosity of the concen-
trated clay suspensions vs the calcium ion content in the water
(Fig. 2) show that both clays are slightly affected by the cal-
cium ion present: the minimum apparent viscosities of the slips
are nearly constant or even decrease. This seems due to the fact
that in the Debbia clay the sodium ions, present in high amount,
are exchanged with the calcium ions, avoiding their flocculat-
ing effects, whereas in the aqueous suspensions of Samone
clay, which contains remarkable amounts of calcite, many more
calcium(I1) ions already exist than those added in the water.
This ion content is also confirmed by the trend of the plots
reporting the amount of deflocculant required to reach the mini-
mum apparent viscosity of the clay slips. The deflocculant, as a
function of the calcium(I1) ion added (Fig. 3), remains nearly
constant or even decreases. Furthermore, Figs. 2 and 3 suggest
that the best deflocculating action is exerted by the polymeth-
acrylates with low molecular weights (1500 to 2500 g.mol-I).
The effect of the polymethacrylate chain length on defloccu-
lating ability is better illustrated in Fig. 4, which reports the
minimum apparent viscosity of the slips at various calcium ion
concentrations vs the logarithm of the molecular weight or the
sequestering ability (CBP) of the polymethacrylates. From Fig.
4 it is predicted that sodium polymethacrylate salts with molec-
ular weight of -4000 g-mol-I and with calcium ion binding
capacities -740 to 750 mgCaCO;g-' present the most effective
deflocculating ability in these types of clays.
Sodium polymethacrylates with medium-low molecular
weights have the best deflocculating capability, suggesting the
important contribution of the electrostatic repulsions to the sta-
bilization mechanism. Their molecules may extend completely,
whereas the long polymethacrylate chains tend to wrap them-
selves up or to be adsorbed onto the clay particles.
February 1994 Dejocculution of Concentrated Aqueous Clay Suspensions with Sodium Polymethacry lates
513
IV. Conclusions
Based on the above results, it is possible to draw the follow-
ing conclusions:
(1) Sodium polymethacrylates are efficient deflocculants of
high-plastic clay suspensions. They combine an electrosteric
stabilization mechanism with a good sequestering action
toward flocculating cations. In particular, polymethacrylates
with low molecular weight (1200 to 2500 g.mol-I) are the best
deflocculants.
The experimental results also demonstrate that sodium
polymethacrylate salts with molecular weight -4000 g.mol-
and CBP values of -740 to 750 mgCaCO;g- would be the most
effective deflocculants.
In ceramic factories, the most widely used deflocculant
is a mixture of sodium tripolyphosphate and metasilicate.*
This system is being completely modified in the Italian ceramic
factories with the introduction of liquid deflocculants based on
a mixture of sodium polymethacrylates and metasilicate. The
substitution of polymethacrylates in place of sodium(1) tripoly-
phosphate is strongly indicated by their similarity in sequester-
ing action toward deflocculating cations. Although economi-
cally unfavorable, this operation is strongly supported, since
with a deflocculant in liquid phase, stabilization of the clay sus-
pensions is better controlled in terms of dosage amount and
time, and thus the detrimental effects of under- and/or over-
deflocculation can be avoided.
( 2)
(3)
Acknowledgment:
plied the sodiumpolymethacrylates.
The authors are grateful to BASF, who kindly sup-
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