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Characterization of Fly-Ash-Based Geopolymeric
Binders Activated with Sodium Aluminate
J. W. Phair, and J. S. J. van Deventer
Ind. Eng. Chem. Res., 2002, 41 (17), 4242-4251 • DOI: 10.1021/ie010937o
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4242 Ind. Eng. Chem. Res. 2002, 41, 4242-4251

Characterization of Fly-Ash-Based Geopolymeric Binders Activated

with Sodium Aluminate
J. W. Phair and J. S. J. van Deventer*
Department of Chemical Engineering, The University of Melbourne, 3010 Victoria, Australia

Properties and characteristics of sodium silicate activated fly-ash-based geopolymers have been
extensively investigated, but the utilization of sodium aluminate activation has received little
attention. The present work, therefore, examines the properties of the starting materials and
sodium aluminate solutions and their effect on the final material properties and microstructure
of fly-ash-based geopolymers. To achieve this, starting sodium aluminate solutions were
characterized with ATR-FTIR and 27Al NMR spectroscopies to determine the coordination state
of aluminum as a function of solution concentration and [OH]/[Al] ratio. Various fly-ash-based
geopolymeric matrixes were synthesized utilizing fly ash, kaolinite, K-feldspar, and slag as the
mineral aluminum sources. The matrixes were activated with alkali silicate or alkali aluminate
solutions as a function of pH, concentration, and alkali ion (Na+ or K+). FTIR and XRD studies
combined with compressive strength tests demonstrated that in certain cases aluminate activated
geopolymers were mechanically superior to traditional silicate activated geopolymers. Of specific
interest was whether the superior properties could be related to a polysialate or calcium-
aluminate-hydrate phase, which both contain 6-coordinate aluminum. A discussion of com-
mercially viable industrial aluminate waste sources as potential large-scale feedstock for
geopolymers was included.

1. Introduction and durability.3 However, the extent to which alterna-

The process design and synthesis of fly-ash-based
geopolymers will continue to undergo intense research
and development until it reaches the stage where it may
be industrially applied. To achieve this, any systematic
method of process and synthesis control that is adopted
must ensure that the output products are competitive
with other materials available on the market.
Motivation for the present work is focused on reducing
the energy costs associated with the mixing and pro-
portioning of fly-ash-based geopolymers, by introducing
an alternative and more cost-effective alkali activator
that reduces the costs for input materials. Given the
projected size and scale at which these materials may
be manufactured and the requirement for large quanti-
ties of ingredients to activate the geopolymerization
reaction, the price of alkali activators will always be at
the forefront of costs to be minimized. The utilization
of inexpensive or waste alkali activators is an effective
approach to ensure the competitiveness of the manu-
facturing process and overall production of fly-ash-based
geopolymers.
Activation of Fly-Ash-Based Geopolymers. The
process of geopolymerization and geopolymers, origi-
nally developed by Joseph Davidovits in the late 1970s
and early 1980s,1,2 involves the addition of sodium
silicate to promote, initiate, or activate the geopolymer-
ization reaction. Recently, interest in geopolymers has
increased because of the potential application of geopoly-
mer technology to a wide variety of industrial aluminum
or silicon-rich waste sources to produce mineral-
polymeric products as construction materials with out-
standing fire resistant properties, compressive strength,
* To whom correspondence should be addressed. Phone:
+61-3-83446620.Fax: +61-3-83444153.E-mail:jannie@unimelb.
edu.au.
10.1021/ie010937o CCC: $22.00 © 2002 American Chemical Society
Published on Web 07/17/2002
tive alkali activators may be utilized to reduce costs and
improve performance of geopolymers has received con-
siderably less attention.
To investigate the effect of novel alkali activators on
geopolymerization, it is impossible to rely on traditional
concepts, methodologies, and models central to the
understanding of calcareous-based cementitious sys-
tems. The purpose of the present research is to therefore
not only further the commercial and economic viability
of geopolymers as an added-value construction material
but to try to develop the means for characterizing fly-
ash-based geopolymers as a function of alkali activator.
An emphasis will be placed on systematically evaluating
experimental data describing both the microstructure
and material properties of fly-ash-based geopolymers.
Efforts will be made to quantify the effects of aluminate
activation on the fundamental polysialate model, es-
tablished by Davidovits to describe the basic chemistry
of geopolymer matrixes.
Microstructure of Fly-Ash-Based Geopolymers
Activated with Sodium Aluminate. The physical
microstructure of fly-ash-based geopolymers activated
with sodium aluminate is not expected to be dramati-
cally different to the microstructure found in conven-
tional sodium silicate activated geopolymers. Chemical
differences in the microstructure, though, are expected
to be significant when comparing aluminate-activated
binders to silicate-activated binders. The basis for
quantifying this chemical difference is to investigate the
manner by which a particular alkali activator may or
may not be incorporated into the polysialate network
of the geopolymer.
It is becoming more and more common for researchers
to utilize the polysialate model of Davidovits,4 to ratio-
nalize and characterize the role of the chemical micro-
structure in determining the various applications and
properties of geopolymeric matrixes. A “sialate” is
 Ind. Eng. Chem. Res., Vol. 41, No. 17, 2002 4243

defined as a silicon-oxo-aluminate repeating unit found Table 1. Composition and Properties of Aluminosilicate
in any polysialate macromolecule and is commonly Source Minerals
denoted by the formula: (-Si-O-Al-O-)n. Poly- chemical composition fly
sialates have an empirical formula of Mn{-(SiO2)z- (weight %) kaolinite K-feldspar slag ash
AlO2}n,wH2O where M is a cation and n is the degree SiO2 52.4 67.1 33.4 42.3
of polycondensation with the most common types being Al2O3 28.6 17.6 14.1 27.1
the following: poly(sialate): Mn-(-Si-O-Al-O-)-n CaO 0.1 0.2 40.7 11.2
[(M)-PS]; poly(sialate-siloxo): Mn-(-Si-O-Al-O-Si- Fe2O3 1.2 0.2 0.3 11.2
O-)-n [(M)-PSS]; and poly(sialate-disiloxo): Mn-(-Si- MgO 0.2 0 6.2 1.4
K2O 0.2 10.6 0.3 0.5
O-Al-O-Si-O-Al-O-)-n [(M)-PSDS]. Na2O 0.1 <0.1 0.2 0.2
The defining properties of polysialates are the IV-fold SO3 0 0 0.02 0.5
aluminum coordination and that they can exist as ring MnO 0.02 <0.01 0.5 0.2
or chain polymers. Compared to alternative approaches P2O5 0.1 0.3 3.3 1.0
of describing geopolymeric matrixes such as phase TiO2 2.8 0.01 0.4 1.6
loss on ignition 14.28 3.88 0.58 2.8
diagrams/compositions,5 ingredient ratios, or dissolution surface area (m2/g) 21.05 3.07 4.02 1.6
properties of the starting materials,6 the polysialate mean particle size (d50, µm) 0.9 5.8 14.1 9.8
model aims to provide a fundamental molecular inter- density (g /m2) 2.65 2.56 2.91 2.33
pretation of the various microscopic, macroscopic, and
physicochemical properties of geopolymeric binders. Table 2. Ingredients and Relative Compositions of
Polysialate chemistry, therefore, serves as a mono- Geopolymeric Mixesa
structural tool in a similar way to which calcium silicate aluminum activator/ M2O/Al2O3/SiO2
hydrates/calcium hydroxide chemistry describes Port- matrix source alkali metal (mol)
land cement-type systems or calcium oxide/aluminum A1 fly ash K-silicate/KOH 1.03/-/0.69
oxide primarily define calcium aluminate cements. The A2 kaolinite K-silicate/KOH 1.03/-/0.69
advantages of such an approach are multiple; namely, A3 K-feldspar K-silicate/KOH 1.03/-/0.69
in defining polysialate chemistry, attention is drawn to A4 slag K-silicate/KOH 1.03/-/0.69
B1 fly ash Na-aluminate 1.48/0.54/-
the molecular and physicochemical features upon which B2 kaolinite Na-aluminate 1.48/0.54/-
material, mechanical, and physical advantages are B3 K-feldspar Na-aluminate 1.48/0.54/-
based. Alternative approaches to date have failed to B4 slag Na-aluminate 1.48/0.54/-
provide such information. For instance, phase diagrams C1 kaolinite Na-aluminate 1.15/0.42/-
assuming either equilibrium or pseudoequilibrium con- C2 kaolinite Na-aluminate 0.87/0.32/-
ditions have yet to include dissolution into compositional C3 kaolinite Na-aluminate 0.57/0.21/-
D1 fly ash Na-Al /K-Si/KOH 1.22/0.08/0.48
predictions. Moreover, consideration of dissolution prop- D2 kaolinite Na-Al /K-Si/KOH 1.22/0.08/0.48
erties of the aluminosilicate starting materials alone has D3 kaolinite Na-Al/Na-Si/NaOH 1.22/0.08/0.48
ignored the final relationship between the geopolymeric D4 K-feldspar Na-Al /K-Si/KOH 1.22/0.08/0.48
phase and the remaining particulates and the conse- D5 slag Na-Al /K-Si/KOH 1.22/0.08/0.48
quences this may have for the physical properties.7 E1 kaolinite Na-Al /K-Si/KOH 1.05/0.02/0.43
E2 kaolinite Na-Al /K-Si/KOH 1.10/0.04/0.43
Polysialate chemistry itself, however, still remains in E3 kaolinite Na-Al /K-Si/KOH 1.30/0.11/0.43
a developmental stage and as a consequence has central E4 kaolinite Na-Al /K-Si/KOH 1.38/0.14/0.43
assumptions requiring clarification before it can be a K-Si is an abbreviation for potassium silicate(K-silicate) and
applied to predict mechanical properties. One such
Na-Al is an abbreviation for sodium aluminate (Na-aluminate).
unclarified assumption of polysialate chemistry is that
chemically bound aluminum is restricted to a tetrahe-
dral (4-fold) coordination environment within the poly- pH electrode calibration were pH 7 and 10. Analytical
sialate macromolecules.3,8 Conversely, the appearance grade reagents (NaOH, KOH, NaNO3, HCl, and CH3-
of 6-coordinate Al in fly-ash-based geopolymers has been COONH4) were obtained from Ajax Chemicals Austra-
well documented.7,10 Substantial research is therefore lia. Polyethylene containers were used throughout to
required to decipher this anomaly and establish the role prevent silicon contamination. Sodium aluminate (Al2O3:
and requirement of 6-coordinate Al in polysialate chem- Na2O ) 0.89, weight % Al2O3 ) 26.5) was obtained from
istry in both purer and more applied geopolymer Aluminates (Tas) Pty. Ltd., Burnie, Tasmania.
systems. It remains to be seen whether the polysialate The fly ash used in the synthesis of all geopolymer
phase can include 6-coordinate Al or whether additional matrixes was of coal origin and obtained from Glad-
phases must exist to permit octahedral Al. stone, Queensland, Australia, through Queensland Ce-
The present work will directly address this issue by ment Limited (QCL). Kembla blast furnace slag was
utilizing a variety of techniques to characterize a series obtained from QCL. Kaolinite (HR1 Grade) and K-Feld-
of solid and liquid aluminum sources with variable Al spar were obtained from Commercial Minerals, Sydney,
coordination for their effect on the process of polysialate Australia. Oxide compositions were determined by fu-
formation and the final chemical and physical properties sion analysis of the starting minerals on a Siemens
of fly-ash-based geopolymeric matrixes. SRS3000 sequential X-ray fluorescence spectrophotom-
eter and are listed in Table 1. Distilled water was used
for all sample preparations, and all other chemical
2. Experimental Section
reagents were of AR(analytical reagent) grade unless
Materials. Sodium silicate (Vitrosol N(N40); weight otherwise stated. Table 2 gives the ingredients and
ratio SiO2:Na2O ) 3.22, weight % SiO2 ) 28.7) and proportions used in the geopolymeric mixes.
potassium silicate (KASIL 2236(K32); weight ratio SiO2: Characterization of Starting Materials. The BET
K2O ) 2.23, weight % SiO2 ) 24.8), were obtained from surface areas of the aluminosilicate mineral sources
P. Q. Australia. All solutions were diluted freshly from were determined by nitrogen sorption on a Micromer-
stock solution using distilled H2O. Standard buffers for itics ASAP 2000 instrument, and the particle size
4244 Ind. Eng. Chem. Res., Vol. 41, No. 17, 2002

Table 3. Solution Equilibrium Concentrations of Starting Aluminum Sources, after Dissolution for 24 Hoursa
sample sol./liq. solid solution Al (mg/L) Si (mg/L) Ca (mg/L) Mg (mg/L)
1A 12 g/25 mL fly ash 1M NaOH 83.0 53.3 9.9 0.1
1B 12 g/25 mL fly ash 1M KOH 19.6 20.4 17.4 0.1
2A 12 g/25 mL fly ash 5M NaOH 1095 1890 4.3 0.1
2B 12 g/25 mL fly ash 5M KOH 776 1095 3.5 0.1
3A 12 g/25 mL fly ash 10M KOH 1050 1820 23.1 3.2
3B 12 g/25 mL kaolinite 10M KOH 814 1200 24.3 3.1
3C 12 g/25 mL slag 10M KOH 599 2410 19.0 2.1
3D 12 g/25 mL K-feldspar 10M KOH 715 2050 22.2 2.0
4A 20 g/25 mL fly ash 10M KOH 1340 2610 8.4 2.2
4B 40 g/25 mL fly ash 10M KOH 1680 3450 17 2
4C 60 g/25 mL fly ash 10M KOH 1860 3820 36.1 5.4
5A 12 g/25 mL fly ash 10M NaOH 2160 2840 18.2 2.3
6A 12 g/25 mL kaolinite 1/1 KOH/H2O* 2720 3050 4.3 2.4
6B 12 g/25 mL kaolinite pH)14 K-Si/KOH 730 61200 28.1 9.6
6C 12 g/25 mL fly ash pH)14 K-Si/KOH 896 50000 2890 134
7A 12 g/25 mL fly ash pH)12 K-Si/KOH 42.4 45600 1340 10.5
7B 12 g/25 mL fly ash pH)13 K-Si/KOH 102 40300 2140 22.1
8A 12 g/25 mL kaolinite 1/4 Na-Al/H2Ob 31000 960 6.4 1.2
8B 12 g/25 mL slag 1/4 Na-Al/H2Ob 26300 4070 0 10.4
8C 12 g/25 mL K-feldspar 1/4 Na-Al/H2Ob 31500 1720 10.3 1.3
8D 12 g/25 mL fly ash 1/4 Na-Al/H2Ob 33100 1640 0 1.4
9A 12 g/25 mL fly ash 1/8 Na-Al/H2Ob 14850 1835 16.5 2.2
9B 12 g/25 mL fly ash 1/16 Na-Al/H2Ob 8080 1815 31.5 2.0
a K-Si is an abbreviation for Potassium Silicate(K-silicate) and Na-Al is an abbreviation for Sodium Aluminate (Na-Aluminate).
b Weight ratio.

distribution was determined by a Coulter LS130 particle
sizer. The BET surface area, mean particle size, and
density of the aluminosilicate sources are given in Table
1.
The solution equilibrium concentrations of dissolved
ions from the aluminosilicate mineral sources were
determined for a range of alkali activators. In most
cases, 12 g of each sample was leached in 25 mL of water
for both 2 and 24 h, and the solution was then analyzed
for Al, Si, Na, K, Ca, and Mg concentrations utilizing
an ICP-OES Perkin-Elmer 3000. The results for samples
leached after 24 h are presented in Table 3. ATR-FTIR
spectra of the various sodium aluminate solutions were
obtained utilizing a Thallium Iodide Bromide crystal
(KRS5) on a Perkin-Elmer Spectrum 2000 FTIR Spec-
trometer with the use of Spectrum v2.0 for Windows.
Selected sodium aluminate solutions and dissolved
aluminum sources were filtered on 36 µm Millipore
filters before freeze-drying and analysis by solid state
27Al MAS NMR. Solution spectra of both dissolved
starting materials and aluminate solutions were ob-
tained on a 300 MHz Inova Varian spectrometer and
referenced against Al(NO3)3.
Synthesis of Geopolymer Samples. The samples
were synthesized as described previously and were cast
into cylinders of height 100 mm and diameter 50 mm.9,10
The mixes consisted mostly of fly ash with kaolinite,
K-feldspar, or slag being added as an extra aluminum
source. The aluminosilicate mineral sources were acti-
vated with either alkali metal silicate or aluminate
activator, or the aluminate was used in a pretreatment
step before the traditional silicate-based mix. The
ingredients and proportions of activator used in geopoly-
meric mixes are presented in Table 2.
All samples were vibrated for 2 min and set at 30 °C
for 24 h before being stored at room temperature.
Geopolymer mixes were activated with either potassium
or sodium hydroxide (Orica Aust. Pty. Ltd.) and/or either
potassium or sodium silicate (PQ Aust. Pty. Ltd),
whereas the SiO2:Al2O3 ratio used in the mixes followed
that of previous work for metakaolin.9 The mixes
comprised a constant % mass of fly ash, a constant %
mass of additional aluminum source, and a constant
amount of alkali activator following proportions used
in previous work.11
Compressive Strength Testing. The mechanical
strength of all samples was tested after 7 days according
to AS 1012.9 using an Amsler FM 2750 compressive
strength measuring apparatus.11 Three cylinders of 100
mm height and 50 mm diameter were tested for each
sample and the results were averaged.
X-ray Diffraction, Infrared, and SEM Analyses.
X-ray powder diffractograms were obtained using a
Phillips PW 1800 diffractometer with Cu KR radiation
generated at 20 mA and 40 kV. Specimens were step
scanned as random powder mounts from 5 to 70° 2θ at
0.02° 2θ steps integrated at the rate of 1.2 s per step.
The infrared spectra of the ground samples were
recorded using the KBr pellet technique (0.5 mg sample
with 250 mg of KBr) on a Bio-Rad FTS 165 FTIR
spectrometer in absorbance mode. Morphological obser-
vations and elemental compositions of the samples were
obtained using a Phillips XL30 scanning electron mi-
croscope (SEM) coupled with an Oxford Instruments
energy dispersive spectrometer (EDS). The instrument
was fitted with an ATW thin window detector for direct
empirical analysis of oxygen. All samples were random
powder mounts and carbon coated before analysis.
Solid State NMR. Solid State MAS NMR 27Al, 29Si,
1H, and 23Na spectra were acquired using a 300 MHz
Inova Varian spectrometer with a 5 mm Doty MAS
probe spinning at 5 kHz. The following experimental
parameters were used: 27Al: 1 µs pulse width, 1 s delay,
referenced to Al(NO3)3; 29Si: 6 µs pulse width, 10 s
delay, referenced to trimethylsilane. In some experi-
ments, high power proton decoupling was used, but it
was not found to substantially contribute to line nar-
rowing.
3. Results
Characterization of Starting Materials. Reported
data for sodium aluminate solutions is less abundant
than data describing sodium silicate solutions despite

27Al
Figure 1. spectrum of S-Grade sodium aluminate.
recent improvements in characterization techniques.
Nominally, the most useful tool for characterizing
sodium silicate solutions at the molecular level is NMR
spectroscopy, despite the low natural abundance of
29Si which significantly reduces the spectral sensitivity
and signal-to-noise ratio.12 The NMR active 27Al nucleus
on the other hand is 100% abundant but is quadrupolar
which significantly broadens the peak width. Figure 1
shows the NMR solution spectrum of S-grade sodium
aluminate to be dominated by one quite broad peak at
around δ ) 80.6 ppm, which is normally due only to
4-coordinate Al sites,13 though in this instance, a small
hump on its shoulder at δ ∼ -3.0 ppm indicates the
presence of some 6-coordinate aluminum sites. Accord-
ingly, solution NMR characterization of raw concen-
trated sodium aluminate solutions is difficult because
of the “missing intensity problem” previously outlined
by Akitt and Gessner14,15 (see Figure 1). Direct evidence
of the coordination state in concentrated aluminum
solution is difficult to obtain, and it is therefore neces-
sary to use a variety of techniques to confirm the nature
and predominance of either 4- or 6-coordinate aluminum
in solution.
One such technique is “attenuated-total-reflectance-
Fourier-transform-infrared spectroscopy” (ATR-FTIR)
which allows direct measurement of concentrated solu-
tions of sodium aluminate. Figure 2 presents the ATR-
FTIR data for a series of aluminate solutions of varying
concentration and [OH]/[Al] ratio. The only significant
peaks were observed in the range <1000 cm-1 and are
associated with the coordination state of the aluminum
present in the system. For a sodium aluminate solution
of high aluminum concentration (labeled line “T” in
Figure 2,) three major peaks at ∼900, 730, and 640 cm-1
are clearly visible and possibly also a shoulder at 540
cm-1. It has previously been reported in the literature
that the IR peak at 728 cm-1 is due to 6-coordinate
aluminum geometry, whereas the peaks at ∼823 and
540 cm-1 are due to 4-coordinate geometry of alumi-
Ind. Eng. Chem. Res., Vol. 41, No. 17, 2002 4245
Figure 2. ATR-FTIR spectra of S-grade sodium aluminate of
variable [OH]/[Al] ratio.
num.16,17 On this basis, it is apparent that at high [Al]
there is a considerable amount of 6-coordinate alumi-
num given that a substantial peak at 730 cm-1 is
observed.
Peaks attributable to 4-coordinate aluminum sites on
the other hand (∼823 and 540 cm-1) are less prominent.
Indeed, the shift of the peak at ∼823 cm-1 at high
aluminum concentration (line “T” in Figure 2) to a
shoulder at ∼900 cm-1 is more indicative of extensive
amounts of 6-coordinate aluminum being present than
4-coordinate aluminum.
Lines U,V, and W represent sodium aluminate solu-
tions that contain the same concentration of aluminum
but vary in their respective [OH]/[Al] ratios. Increasing
the [OH]/[Al] ratio of the solution as shown in Figure 2
has a minimal effect on reducing the proportion of
6-coordinate aluminum or promoting the presence of
4-coordinate aluminum. Any observed decrease in in-
tensity between lines U,V, and W was most likely due
to decreasing aluminum concentration rather than any
increase in 4-coordinate aluminum. Lines X, Y, and Z
represent sodium aluminate solutions of low aluminum
concentration and water for reference and exhibits
peaks of relatively lower intensity. Lines X, Y, and Z
are all dominated by a single and broad peak around
700-750 cm-1 due to octahedral aluminum and water.
A slight anomaly can be observed in the presence of high
[OH] (line Y), as the peak maximum shifts to a lower
wavenumber compared to that expected for water and
octahedral aluminum. The exact cause of this shift
remains unknown at this stage, but it remains evident
that solutions of at least 1 M concentrated are preferred
for meaningful characterization by ATR-FTIR.
An alternative means of quantifying the amount of
either 4- or 6-coordinate aluminum sites in sodium
aluminate is by solid state 27Al MAS NMR analysis of
freeze-dried samples of sodium aluminate. Freeze-
drying of the sample is not considered to greatly alter
the structure of aluminum compared to its structure in
sodium aluminate (Bradley and Hanna19). Figures 3-6
display the 27Al MAS NMR spectra of selected sodium
aluminate solutions of a variable [OH]/[Al]. Generally,
Figures 3-6 indicate the extent of 6-coordinate Al and
4246 Ind. Eng. Chem. Res., Vol. 41, No. 17, 2002
Figure 3. 27Al MAS NMR spectrum of sodium aluminate [OH]/
[Al] ) 4.71.
Figure 4. 27Al MAS NMR spectrum of sodium aluminate [OH]/
[Al] ) 6.67.
4-coordinate Al sites present in the samples of sodium
aluminate as a function of [OH]/[Al]. Once again, it is
shown here that the extent of 6-coordinate Al increases
with increasing [OH] confirming initial results obtained
from ATR-FTIR spectroscopy. The influence of concen-
tration on this effect was negligible.
At lower [OH]/[Al] ratios (e.g., Figure 3, [OH]/[Al] )
4.71), considerable quantities of 4-coordinate aluminum
sites (δ ∼ 78.8 ppm) were present, but only traces of
4-coordinate aluminum were left at [OH]/[Al] ) 6.67 (see
Figure 4). Of considerable interest was the effect which
the nature of the alkali metal had on the dilution of
sodium aluminate at higher [OH]/[Al] ratios. Figure 5
clearly shows that dilution with 10 M NaOH largely
promotes 6-coordinate Al sites (δ ∼ 12.8 ppm). Figure
6, on the other hand, shows that dilution with 10 M
KOH causes significant amounts of 4-coordinate Al sites
(δ ∼ 82.8 ppm) to be stabilized. Reasons for this
observation are largely due to the differing equilibria,
i.e., precipitation/polymerization kinetics and ion-pair
formation which are controlled by the nature of the
alkali metal.5 The phenomenon is akin to the structure-
Figure 5. 27Al MAS NMR spectrum of sodium aluminate [OH]/
[Al] ) 22.35, diluted with 10 M NaOH.
Figure 6. 27Al MAS NMR spectrum of sodium aluminate [OH]/
[Al] ) 22.35, diluted with 10 M KOH.
directing role which alkali ions have in controlling the
relative rates of depolymerization and ionization of
polymeric aqueous silicate.18
Having confirmed the existence of both 6- and 4-co-
ordinate aluminum in our starting sodium aluminate
solutions as a function of [OH]/[Al], it is then necessary
to observe whether the dissolution of solid aluminum
sources in geopolymerization reactions, affects the [OH]/
[Al] ratio and therefore the coordination of aluminum.
Table 3 shows the solution equilibrium concentrations
of ions dissolved from various solid aluminum sources
used in the synthesis of geopolymers, as a function of
alkali activator and concentration of alkali. It has been
previously shown that NaOH dissolves more material
than KOH.5,7
Table 3 is in agreement with earlier results and shows
that, generally, there is more dissolved material after
samples were activated with NaOH rather than KOH
 Ind. Eng. Chem. Res., Vol. 41, No. 17, 2002 4247

Figure 8. 27Al MAS NMR spectrum of aqueous phase leachate

Figure 7. 27Al MAS NMR spectrum of aqueous leachate from from sample 9A (Table 3).
sample 5A (Table 3).

after 24 h. In addition, samples activated with sodium

aluminate were not shown to remove all that much
silicate. Moreover, negligible amounts of calcium and
magnesium were dissolved from the samples, including
slag, except in the presence of excess added silicate. This
would tend to suggest that if calcium is involved in
strength formation reactions, it is more likely to do so
by interfacial-particle reactions with the geopolymeric
phase rather than through the solution phase.
An interesting observation from Table 3 is that fly
ash had the highest concentration of dissolved Al,
whereas slag had the smallest concentration. Slag, in
contrast, provided the highest concentration of dissolved
Si, whereas kaolinite provided the smallest concentra-
tion. The consequence of this is that kaolinite provided
a solution Al/Si ratio equal to 0.68 compared to the 0.25
value provided by slag. Figure 9. 27Al MAS NMR spectrum of aqueous leachate from
Figures 7-9 display the 27Al solid-state NMR of the sample 2B (Table 3.).
filtered and freeze-dried aqueous phase (leachate) after
leaching selected solid aluminum sources with alkali the Al that is leached out produces 4-coordinate alumi-
and the extent that available 6-coordinate aluminum num (δ ∼ 64.3 ppm). This result is highly significant in
varied between samples. Figure 7 shows the nature of that it reaffirms the phenomenon observed in Figures
the aluminum removed from dissolved fly ash (sample 5 and 6 and demonstrates the kinetic effects and
5A) in 10 M NaOH and shows that almost equal structure-directing role of K+ on solution speciation,
proportions of 4 and 6-coordinate Al were present (at δ promoting 4-coordinate Al to a far greater extent than
∼77.2 and -4.82 ppm respectively). The exact structure Na+ can.
of freeze-dried samples and what this fundamentally
Characterization of Geopolymeric Matrixes. The
represents both in terms of phase and solution specia-
tion requires further work, although, it has previously compressive strengths of selected matrixes are pre-
been considered to give a reasonable indication of sented in Table 4. What is clear is that, under certain
solution speciation.19 Furthermore, whether Al is dis- conditions, aluminate activation as a pretreatment stage
solved or reprecipitated as 6-coordinate Al in the pres- is capable of producing geopolymeric matrixes of a
ence of additional species will affect polysialate forma- superior mechanical strength compared to traditional
tion in terms of the Al available for polysialates relative silicate activation alone. For the selected Al2O3/SiO2
to alternative reactions. Figure 8 displays the effect of matrixes presented in Table 4, matrix D5 was stronger
leaching fly ash with sodium aluminate (sample 9A) and than its counterpart A4, whereas the Al2O3/SiO2 ratio
shows that the majority of aluminum remaining in could be adjusted for any of the other matrixes (e.g., E1
solution, which would mostly be attributed to the to E4) to obtain a maximum compressive strength which
sodium aluminate, retains a 6-coordinate geometry (δ is stronger than those of the standard matrixes. Ma-
∼ 9.9 ppm). However, small amounts of 4-coordinate Al trixes activated with sodium aluminate alone were
(δ ∼ 73.6 ppm) are present. For fly ash leached in 5 M generally weaker, although the mix was not optimized
KOH (sample 2B, Figure 9), it is apparent that all of for maximum compressive strength.
4248 Ind. Eng. Chem. Res., Vol. 41, No. 17, 2002

Figure 11. X-ray diffractograms of selected matrixes. Peaks are

identified by their d spacing values (in angstroms).
Figure 10. FTIR spectra of selected matrixes.
Table 5. Infrared Bands of Selected Geopolymeric
Table 4. Seven Day Compressive Strength of Selected Matrixes (cm-1)
Geopolymeric Matrixes
Al-O,Si-O Al-O, Si-O
compress. compress. compress. matrix bending Al-Ooct stretching
strength strength strength
sample (MPa) sample (MPa) sample (MPa) A1 467 725 982
A2 452 693 1008, 1033
B2 26.6 D4 31.8 A4 79.1 A3 449 693 998
B1 17.7 D2 33.9 A2 55.2 A4 451 716 991
B3 4.2 D3 34.8 A3 35.5 B1 467 720 979
B4 10.3 D1 50.6 A1 77 B2 469 697 1007
D5 86.5 B3 461 723 993
C1 9.6 E1 38.2 B4 455 720 996
C2 5 E2 46.9 D1 468 723 999
C3 3.3 E3 26.1 D2 467 745 1007
E4 23 D4 462 722 994
D5 452 716 984
Sodium aluminate activated matrixes exhibited a
different dependence of the mechanical strength on the follows: Al-O/Si-O in-plane bending at ∼460 cm-1,
solid aluminum source compared to the standard ma- octahedral Al ∼730 cm-1, tetrahedral Al-O stretching
trixes. When only sodium aluminate activation was ∼820 cm-1, and asymmetric Al-O/Si-O stretching
used, matrixes containing kaolinite were shown to ∼900-1030 cm-1. These peaks can also be considered
produce the greatest mechanical strength. This is pos- typical of those associated with calcium aluminate
sibly due to the compatibility of the surface of the hydrates.22,23,24
kaolinite to amorphous polysialate structures containing Summaries of the significant T-O bending and
larger amounts of 6-coordinate aluminum. The surface octahedral aluminum infrared active frequencies for
of kaolinite consists of octahedral aluminum sites and selected matrixes are presented in Table 5. According
will far more readily interact with 6-coordinate alumi- to a geopolymeric interpretation of the spectra, the
num than 4-coordinate aluminum to form a more peaks at ∼1000 cm-1 indicate the extent of polysialate
intimate surface precipitate. Despite K-feldspar being formation or aluminum incorporation with a lowering
a tectosilicate and therefore expected to have a high in the energy of the peak. Table 5 provides a consistent
level of microstructural compatibility with polysialate trend between the Si-O bending, Al-O bending, and
species, its influence on the matrix strength was nega- T-O stretching such that the smaller energies can be
tive for the matrixes activated with sodium aluminate. viewed as either a larger extent of aluminum incorpora-
This may not necessarily imply the existence of alterna- tion into the silicate backbone or as a reduction in the
tive chemistry in such systems, although K-feldspar has extent of silicate polymerization within the matrix.
not yet been shown to significantly augment polysialate What can be seen is that matrixes containing fly ash
species formation in more traditional geopolymeric generally contain more polysialate formation given the
matrixes. shifting of the T-O bending peak at smaller energies.
Figures 5 and 6 demonstrate that NaOH promotes The opposite is true for kaolinite based matrixes,
octahedral Al in solution, whereas KOH promotes whereas K-feldspar and slag based matrixes have an
tetrahedral Al in solution. This could explain the intermediate degree of polysialate formation. These
observation that for matrixes D2 and D3 greater strength results, epitomised by matrixes “A”, can be used to
was obtained for NaOH/Na-aluminate solutions than roughly correlate the compressive strength to the degree
KOH/Na-aluminate solutions because of the abundance of polysialate formation. The octahedral peak was
of octahedral Al in the NaOH/Na-aluminate solution. present in most samples particularly preactivated alu-
This also tends to suggest that the presence of octahe- minate samples but was less prolific in the standard
dral Al has a significant effect on the compressive samples. No peaks could be attributed to crystalline
properties of geopolymeric matrixes. Further evidence Al-O or Si-O bonds as observed for hydroxysodalites
for why this may be the case can be obtained through and Na-A and Na-X sodalites.20,25 Nevertheless, it
FTIR and XRD analyses. remains impossible at this stage to ignore the contribu-
Figure 10 displays the FTIR spectra for selected tions of calcium aluminate hydrates to the spectra.
geopolymeric matrixes. The FTIR spectral attributes of Figure 11 displays the XRD patterns for selected
geopolymeric matrixes have been well defined and geopolymeric matrixes. These include a traditional
established.20,21 The main peaks of significance are as silicate activated geopolymeric matrix (A2), a silicate
 Ind. Eng. Chem. Res., Vol. 41, No. 17, 2002 4249

activated matrix with an aluminate pretreatment stage

(D2, D3), and a sodium aluminate activated matrix (B2).
All of these matrixes contain kaolinite as the solid
aluminum source, and the diffractograms display peaks
that are typical of those found in geopolymeric matrixes.
Fly ash consists of both amorphous and crystalline
material with the amorphous material (hump from 20
to 40°2θ) mostly due to silica and the crystalline peaks
attributable to mullite, haematite, and quartz (d spacing
values of 2.77, 3.42, and 4.23/5.38 Å respectively) with
small amounts of ferrite spinel and anhydrite.
Therefore, all fly ash based geopolymeric matrixes
produced an X-ray diffractogram with most basic crys-
talline features attributable to unreacted fly ash or the
aluminum mineral source. For instance, peaks due to
hematite, quartz, and mullite were all regularly ob-
served, as was the hump due to amorphous silica in the
diffractogram. The exact value for the maximum of this
hump is largely controlled by the degree of polymeri-
Figure 12. SEM secondary emission micrograph of preactivated
zation or the M2O:SiO2 ratio26 and the extent of alumi- aluminate fractured matrix D2.
num incorporation.21
No peaks due to ettringite (2.18, 1.93 Å), calcium Table 6. Typical Elemental Compositions (%) of Selected
silicate/spurrite (2.76, 2.18, 1.63 Å), or vaterite (1.64 Å) Geopolymeric Matrixes as Determined by SEM EDS
Analysis
were observed, as had been for lower pH matrixes.21
Furthermore, no peaks which could be attributed to matrix matrix matrix matrix matrix matrix
calcium silica hydrates were observed. The X-ray dif- element (%) D2 D1 B2 B1 A2 A1
fractogram of the standard geopolymeric matrix (A2) O 50.72 48.75 51.75 48 52.82 48.24
consists of 3 major peaks with d spacings of 3.34, 2.96, Na 1.58 1.65 10.46 9.14 0.16 0.14
Al 11.87 10.35 14.91 14.95 9.98 7.86
and 2.52 Å which could mostly be attributed to crystal-
Si 17.14 16.42 14.42 13.59 16.81 14.85
line quartz. For the sodium aluminate activated matrix K 11.14 12.01 0.28 0.41 8.32 15.83
(B2) on the other hand, the X-ray diffractogram exhibits Ca 2.04 3.38 3.62 5.95 6.94 9.4
a series of new peaks at d spacing values around 2.78 Ti 1.04 0.79 0.99 1.03 0.91 0.58
Å which are absent in both standard and preactivated Fe 4.47 6.65 3.57 6.93 4.07 3.09
matrixes.
The potential for calcium aluminate chemistry to material within this interpenetrating paste further
appear in sodium aluminate activated systems, how- highlights its dominating amorphous structure.
ever, is limited because of the low level of calcium Table 6 provides the elemental compositions for a
available from the starting materials (see Tables 1 and series of selected matrixes. Significantly, there was
3), and this was confirmed by the presence of small minor variation in the composition of O, Ca, Ti, and Fe
peaks associated with crystalline aluminum oxides and between samples, and the concentration of alkali was
calcium aluminate hydrates (2.96, 2.52, and 2.11 Å). largely dependent upon the activator used. The overall
Moreover, it is apparent that sodium aluminate activa- Al:Si ratios were shown to vary greatly between ma-
tion or preactivation did not contribute to any substan- trixes, with standard matrixes having Si/Al ∼ 1.79,
tially new crystalline phase formation nor detract from aluminate activated matrixes having Si/Al ∼ 0.94, and
the initial chemical properties observed in the standard aluminate preactivated matrixes having Si/Al ∼ 1.51.
geopolymeric matrixes. Overall, sodium aluminate ac-
tivation shows a high level of compatibility to traditional 4. Discussion
activation techniques and complements geopolymer
Microstructure of Fly-Ash-Based Geopolymers
formation in terms of chemical phase composition and
Activated with Sodium Aluminate. Present defini-
reaction mechanisms.
tions of polysialate species are limited to include hy-
The XRD results demonstrated that no significant drothermal conditions as a prerequisite for polysialate
quantities of hydrates of zeolitic or any other alkali- phase formation.29 This implicitly precludes the pos-
containing crystalline phases are formed in geopoly- sibility of 6-coordinate Al partaking in polysialate
meric matrixes. Furthermore, no crystalline calcium chemistry given the lack of 6-coordinate Al in any
silicate hydrates or calcium hydroxides were observed crystalline synthetic aluminosilicate or zeolitic-type
in slag-containing geopolymeric matrixes, but the exist- structures.30 Modification of this polysialate model to
ence of calcium aluminate hydrates, calcium sulfoalu- include 6-coordinate aluminum as found in more com-
minates,27 and calcium-alumina oxides28 in sodium plex, heterogeneous, and applied systems, therefore,
aluminate activated matrixes could be observed. remains a difficult approach to improving the systematic
The morphological effect of the alkali activator on the description of the microstructure of geopolymers.
starting particles was investigated by scanning electron A strong necessity remains to clarify the limitations
microscopy. Figure 12 provides a secondary emission and assumptions upon which polysialate chemistry can
micrograph of a fractured matrix and clearly shows the describe geopolymers. This will provide a greater basis
“embedding” of the fly ash particles within the hardened for understanding the existence of other chemical
matrix paste and regions where fly ash particles were phases in geopolymers, their contribution to the micro-
previously attached. The visible lack of crystalline structure, and effects on the material properties of
4250 Ind. Eng. Chem. Res., Vol. 41, No. 17, 2002
geopolymers. One such approach, as demonstrated in
the present work, was to consider 6-coordinate Al phases
such as calcium aluminate hydrate and calcium sulfo-
aluminate in combination with the polysialate phase,
to constitute a fly-ash-based geopolymer synthesized at
room temperature.
Potential Industrial Sources of Aluminate Waste.
The commercial production of sodium aluminate in-
volves the dissolution of aluminum hydroxide or metallic
aluminum in liquid caustic under heating. Excess or
waste sodium aluminate can therefore be obtained from
industrial processes that involve alumina in a caustic
environment. Accordingly, the most abundant sources
of solid aluminum-bearing waste in the aluminum
industry are salt cake and spent potliner.31 However,
spent potliner is a hazardous waste due to the presence
of cyanides and fluorides and therefore requires pre-
treatment before obtaining sodium aluminate.32 A more
readily available source of sodium aluminate is alumina-
bearing salt cake which is formed as a byproduct of
aluminum dross formation in the recycling of metallic
aluminum. Processes are already being designed to
obtain either saline-sodium hydroaluminate or saline-
sodium aluminates from the salt-cake recycling process.
However, wastewater from the alumina refinery still
remains as the most readily available source of solubi-
lized sodium aluminate to act as a feedstock for geopo-
lymerization.
The application of geopolymerization to the utilization
of considerable amounts of wet or sludge-type aluminum
wastes such as mentioned above remains a distinct
advantage of the processing flexibility of geopolymer
technology to produce added-value products.
5. Conclusions
Utilization of sodium aluminate-activated fly-ash-
based geopolymeric matrixes remains a commercial
prospect, particularly when sodium aluminate from a
waste source is utilized. 27Al MAS NMR confirmed that
sodium aluminate contained either 4- or 6-coordinate
aluminum depending on the [OH]/[Al] and could react
to form fly-ash-based geopolymers that are equivalent
or greater in strength to those activated with sodium
silicate. Alkaline-dissolved fly ash was shown to promote
soluble 6-coordinate Al, whereas dissolution in the
presence of KOH promoted the existence of tetrahedral
Al in solution to the exclusion of other species. This
observation was repeated for the dilution of concen-
trated sodium aluminate solutions with KOH. Dissolu-
tion in the presence of NaOH, on the other hand,
produced significant amounts of octahedral Al in solu-
tion at high [OH]/[Al] ratio.
Geopolymerization was also confirmed to occur in the
presence of both 4- and 6-coordinate aluminum. Whether
the 6-coordinate aluminum participates in the poly-
sialate phase or in another phase requires further
investigation. XRD and FTIR analyses indicated a
distinct possibility that there are other aluminate
phases present in the system such as calcium aluminate
and calcium sulfo-aluminate, which retain the alumi-
num in 6-fold coordination. Nevertheless, it remains
clear that the presence of sodium aluminate consisting
of predominantly octahedral rather than tetrahedral Al
has a positive effect on the properties of the geopoly-
meric matrixes as observed through compressive strength
testing. This is although the exact microstructural basis
for this feature requires further clarification.
Acknowledgment
The financial support of the University of Melbourne
Scholarships Fund, the Australian Research Council,
and the Particulate Fluids Processing Centre is grate-
fully acknowledged.
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Received for review November 20, 2001
Revised manuscript received May 13, 2002
Accepted June 9, 2002
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