WASTE

MANAGEMENT

PERGAMON Waste Management 18 (1998) 17-24

Behaviour of ordinary Portland cement during the stabilization/

solidification of synthetic heavy metal sludge: macroscopic and
microscopic aspects
J.-N. Diet at*, P. Moszkowicz a, D. Sorrentino b
aLaboratoire d’ Analyse Environnementale des Pro&d& et des Systemes Industriels (LAEPSI) - Institut National des Sciences Appliqukes de Lyon,
Bdtiment 404,20 avenue Albert Einstein, 69621 Villeurbanne Ceakx. France
bLafarge Laboratoire Central de Recherche, B.P. 15, 95 rue du Montmurier, 38291 St-Quentin Fallavier Cedex, France

Received 12 May 1997; accepted 16 January 1998

Abstract

Chromium and/or zinc hydroxide sludges were mixed at variable proportions with OPC, in order to evaluate the macroscopic
and microscopic effects caused by the waste on the cement hydration process. Initial setting time, heat production during hydration,
leaching characteristics and microstructure of the samples were investigated using varied techniques. For zinc hydroxide sludge,
hydration was stopped after a few minutes, because of the precipitation of a solid hydrated phase. Since the sludge:cement ratio
remains under 2-3:1, chromium hydroxide sludge accelerated the cement hydration. For higher ratios, hydration was hindered.
Some microstructural modificatiops have been detected, such as the possible formation of a U-phase analog, related to the presence
of chromate ions in the sludge. The influence of the oxidation degree of chromium on its fixation in the matrix is discussed. 0 1998
Elsevier Science Ltd. All rights reserved.

1. Introduction the annual hazardous waste production of the French

Stabilization/solidification (S/S) technologies have
first been developed to reduce waste handling and/or
disposal problems (liquid, muddy or pulverulent waste,
mostly composed of soluble species) by their encapsula-
tion into a solid matrix as physically and/or chemically
stable as possible [1,2]. Research programs have often
been conducted in order to evaluate the mechanical and
leaching properties of S/S products [3-51, but the
understanding of physical and chemical mechanisms
involved in, e.g. cement-based processes is of more
recent interest for researchers [6-91. For instance, the
ability of cement to hydrate normally and form a solid
and impermeable block when mixed with waste is of
great importance for S/S process design.
In this study, we investigated the behaviour of OPC
during the S/S of heavy metal hydroxide sludge (MHS),
composed of water (65-95% w/w) and precipitated
heavy metal hydroxides (Fe, Zn, Cr, Ni, Cu, Cd, Al).
Heavy metal hydroxide sludges represent about 20% of
* Corresponding author. Tel.: + 33-4-72-43-88-41;
43-87-1 7; e-mail: jean-noel.diet@insa-lyon.fr.
industry of mechanics (-175,000 tons), and about 1 mil-
lion tons for the European Union [lO,l 11. According to
the recent French regulation for waste management
[12,13], heavy metal hydroxide sludges will have to be
treated by some S/S process before disposal after the 30
March, 1998.
2. Materials
A MHS is an extremely complex system (one of our
recent determinations of the elementary composition of
a MHS sample showed at least 20 components) with
large variation in composition depending on where and
when it has been produced [ll]. For that reason we
chose to use a laboratory-prepared synthetic sludge,
with a simple and well-known composition. Three
different types of sludge were prepared based on chro-
mium hydroxide, zinc hydroxide and iron, zinc and
chromium hydroxide, using analytical grade reagents.
The chromium hydroxide sludges were obtained by
dissolving 200g of potassium dichromate in a sulfuric
Fax: + 33-4-72- acid solution prepared with 16Og of 98% H$04 and
500 mL of deionized water. Dichromate ions were totally

0956-053X/98/$19.00 0 1998 Elsevier Science Ltd. All rights reserved

PII: SO956-053X(98)00003-8
18 J.-N. Diet et al.1Waste Management 18 (1998) 17-24

or partially reduced into Cr3+ ions by the addition of
610m1, (CO), 500ml (ClO) or 280mL, (CSO) of a 50%
sodium hydrogen sulphite solution. Deionized water
was then added until the total volume reached 2.5 L.
The pH of the solution was raised to 8.5 with a 2OOg/L
solution of soda in order to precipitate chromium
hydroxide. The water content was finally reduced by
vacuum filtration.
For the zinc hydroxide sludge, 1OOg of zinc chloride
was dissolved in a hydrochloric acid solution prepared
by mixing 100 g of 35.5% HCl and 500 mL, of deionized
water. The pH of the solution was raised to 9 with 200
g/L soda, and the result was vacuum filtered.
The iron, zinc and chromium sludges were prepared
from two solutions. The first one contained 17 g of zinc
dissolved in a nitric acid solution (110 g of 51% HN03
with 200 mL of deionized water) and 35 g of orthopho-
spheric acid 84%. The second one was made of iron
chloride (150 g FeC13.6H20) and 9 g of potassium
dichromate dissolved in a sulfuric acid solution (90g of
98% H2S04 in 500 mL of deionized water). The resulting
solution was dechromated with 18g of 50% HNaS03.
The pH was raised to 8.5 with a lOOg/L suspension of
lime and the solution was vacuum filtered.
Sludge compositions are shown in Table 1. Only the
chromium hydroxide sludges have been used in all
tests, so that they can be considered as the core of this
study.
Two different type l-Ordinary Portland Cements,
compositions of which are shown in Table 2, were mixed
with the sludges, without any water or sand addition.
The pastes were placed into closed cylindrical plastic
molds, and cured without any supplementary precau-
tions for samples 1-12, or moist cured at room tem-
perature for samples OA, OB and 13 to 34, for at least 28
days. The nature of the mixes is shown in Table 3.
3. Experimental
Two parameters were selected in order to follow the
hydration progress of the samples: the initial setting time
and the heat flow during cement hydration. Initial setting
times were measured using a Vicat apparatus as described
in CEN 196-3 European standard, on mixes of sludge
and cement placed in cylindrical plastic molds (diameter:
Table 1
Sludges composition (wt%)
Sludge Na K Cr Fe
5cm, height: 5cm). Heat flow measurements were
conducted according to the NF P15-436 French standard.
An adiabatic calorimeter was specifically designed fol-
lowing the recommendations of this standard, but
adapted to small samples of sludge and cement mixes
(-30 g)*
The microstructure of solidified samples was studied
with a JEOL Scanning Electron Microscope coupled
with an EDAX system. Diffractograms have been made
on a Siemens 5000 Diffractometer.
Finally, a semi-dynamic leaching test was carried out on
samples that were placed in closed plastic vessels contain-
ing de-ionized water, without agitation, at a water:solid
ratio of 5:l by weight. Eight static extractions were
taken by replacing leachate with new de-ionized water
after 3, 6.5, 17, 33, 46, 68, 94 and 122h.
Metal, calcium and alkali concentrations in the lea-
chates were determined by flame atomic absorption
spectroscopy using a Perkin-Elmer 3110 Atomic
Absorption Spectrometer, and sulfate and chromate
contents by ion chromatography with a Dionex 2OOOi/
SP and an AS4A SC anion column.
4. Results
4.1. Initial setting time
Table 4 shows the initial setting times determined for
different samples. Results depend on the nature of the
treated sludge. The chromium hydroxide sludge tends to
accelerate cement setting. This can be partly associated
with the high sulfate content of the sludge.
The zinc hydroxide sludge has two opposite effects:
cement B is largely accelerated, while for cement A
no setting had been detected after 80 days. As the
main difference between the two cements is their C3A
content, it is possible that zinc accelerates the cal-
cium aluminate hydration, while it has a harmful
effect on silicate hydration, as was suggested by
Arliguie [14].
The effect of the mixed hydroxides sludges (FCZl,
FCZ2 and FCZ3) depends on the sludge cement ratio
(Fig. 1). Below a ratio of 1:l by weight, the cement set-
ting time was slightly reduced. On the other hand,
beyond this value, setting was greatly delayed.
-
Zn Ca SO4 Cl HP04 NO3 Hz0

FCZl 0.04 0.04 0.06 0.82 0.46 2.14 1.72 0.54 0.57 1.08 88.10
FCZ2 0.04 0.03 0.09 1.45 0.75 2.62 4.91 6.06 _ 1.05 77.50
FCZ3 0.03 0.03 0.15 2.23 1.24 3.92 6.05 1.29 1.98 0.81 71.90
co 3.55 1.42 6.68 - - - 6.89 _ _ - 70.50
c50 2.37 1.42 5.82 _ _ - 5.54 - 76.10
Z 3.91 - - _ 9.78 - _ 6.12 _ _ 74.80
 J.-N. Diet et al./Waste Management 18 (1998) 17-24 19

Table 2
Cements composition

Composition (wt%) Phase composition (wt%)

Cement SiOz AllO3 FezOx CaO MgO K20 NazO SO3 Ti02 Cr203 1.o.i C3S C$S C,A CdAF KzSOI Na#04 CaS04 free CaO

A 24.0 2.7 2.3 67.6 0.8 0.1 0.1 1.7 0.2 0.0 1.0 68.6 17.1 3.0 7.0 0.3 0.2 2.5 0.3
B 20.7 5.5 2.4 63.0 2.1 0.6 0.1 3.3 0.3 0.0 2.5 54.8 17.9 10.4 7.3 1.2 0.2 4.5 0.5

Table 3 Table 4
Samples composition Initial setting times

Sample Cement Sludge Sample # Cement Sludge Initial setting time (h)

# Type wt% wt% 1 A FCZ 1 1.3

2 A FCZ 1 5
OA A 71.4% H20 28.6% 3 A FCZ 1 11
OB B 71.4% H20 28.6% 4 A FCZ 1 65
1 A 64.1% FCZ 1 35.9% 5 A FCZ 2 6
2 A 47.1% FCZ 1 52.9% 6 A FCZ 2 10
3 A 30.8% FCZ 1 69.2% 7 A FCZ 2 20
4 A 22.9% FCZ 1 77.1% 8 A FCZ 2 40
5 A 61.5% FCZ 2 38.5% 9 A FCZ 3 4.5
6 A 44.4% FCZ 2 55.6% 10 A FCZ 3 18.5
7 A 28.6% FCZ 2 71.4% 11 A FCZ 3 22.7
8 A 21.1% FCZ 2 78.9% 12 A FCZ 3 24
9 A 59.0% FCZ 3 41 .O% 13 A Z > 80 days
10 A 41.9% FCZ 3 58.1% 14 B 2 1.4
11 A 26.5% FCZ 3 73.5% 16 A co 1.2
12 A 19.4% FCZ 3 80.6% 19 B co 1.5
13 A 66.7% Z 33.3% 28 A c 50 1.8
14 B 66.7% Z 33.3% 31 B c 50 1.8
15 A 66.7% co 33.3%
16 A 50.0% co 50.0%
17 A 33.3% co 66.7%
18 A 20.0% co 80.0%
to sample OA which was taken as a reference. A high
19 B 66.7% co 33.3%
20 B 50.0% co 50.0% peak was observed immediately after mixing, but no
21 B 33.3% co 66.7% exothermic reaction was detected after that. This
22 B 20.0% co 80.0% indicates an inhibition of the cement hydration, which
23 A 66.7% c IO 33.3% can be associated with the absence of setting observed
24 A 50.0% c 10 50.0%
for this sample. This result may be explained by an
25 A 33.3% c 10 66.7%
26 B 66.7% c 10 33.3% initial precipitation (responsible for the initial peak) of a
27 B 50.0% c 10 50.0% solid phase that could hinder further hydration. The
28 B 33.3% c 10 66.7% rapid setting observed with sample 14 (same sludge,
29 A 66.7% c 50 33.3% cement B) may be the consequence of the same kind of
30 A 50.0% c 50 50.0%
precipitation.
31 A 33.3% c 50 66.7%
32 B 66.7% c 50 33.3% The influence of sludge CO on hydration depends on
33 B 50.0% c 50 50.0% the sludge:cement ratio (Fig. 3). For low sludge con-
34 B 33.3% c 50 66.7% tents, cement hydration was weakly disturbed (samples
-
15), even if the main peak was accelerated. When the
sludge:cement ratio increased (samples 16-18), the
initial peak was enhanced and the main peak decreased
4.2. Heat of hydration until it disappeared. When the sludge:cement ratio was
greater than 2, normal hydration did not appear to take
place.
This part of the study was conducted on samples OA,
13 and 15 to 18, prepared by mixing the sludges Z and 4.3. Leaching tests
CO with the cement A.
Fig. 2 shows the heat flow during cement hydration Samples 1-12 (mixed hydroxides sludge and cement
for the sample 13 (sludge Z). The thin line corresponds A) showed a good retention of metals, since the
20 J.-N. Die1 et al./ Waste Management 18 (1998) 17-24

??
4

??
8

??
6
??
2
I

50% 60% 70% 80% 90%

sludge content (Wt %)

Fig. 1. Initial setting times for samples 1-12.

80

60

0 5 10 15 20 25
time (h)

Fig. 2. Rate of heat for zinc hydroxide sludge sample.

cumulative mass of metal extracted after 10 extractions
was never more than 7% of the total content. However,
leaching tests were only applied to samples 15-34, pre-
pared with chromium hydroxide sludges.
The study of the leaching kinetics of the ions con-
tained in the solidified matrices can be summarized:
Non-polluted samples (OA and OB) showed an ion
leaching behaviour controlled by the flow of calcium
hydroxide through the sample surface. Alkali ions had
only a small influence on final pH of the leachate.
Chromium concentration in the leachates of samples
OA and OB was near or below the detection limit (about
0.1 ppm), and will be neglected hereafter.
When sludge is added, the flow of alkali ions was
enhanced, whereas the calcium ions flow was reduced.
When the sludge:cement ratio was high (2:1), the pH of
leachates was elevated (0.6 or 0.7 pH units), as shown in
Fig. 4. The pH seemed to be controlled by the leaching
of sodium and potassium hydroxides. Chromium was
mostly at the oxidation state +VI in the leachates,
whatever the kind of sludge we used.
Table 5 gives the cumulative mass of different ions,
for samples OA, OB and 15-34, extracted after 10
renewings of the leaching solution, given in percent of
the total content before leaching. Since the leaching
behaviour of most of the studied species seems not to be
only controlled by diffusion phenomena, we have cho-
sen not to calculate effective diffusion coefficients [ 151.It
shows two ‘very different leaching characteristics whe-
ther samples contained low (33.3%) or high (66.6%)
levels of sludge. Indeed, the cumulative extracted mass
was proportionally much more important for the latter
than for the former, particularly for CrOd’-, K+, Na+
and SOd2- ions. Several explanations can be found: the
 J.-N. Diet et al./ Waste Management 18 11998) 17-24 21

60 ~~~ OA
----- ,5
--_----I6
-___,7
- 18

0 5 10 15 20 25
time (h)

Fig. 3. Rate of heat for chromium hydroxide sludges samples.

12,5
Samples 17,21,25,28, 31,34

E 11,5
Samples OA,OB, 15, 19,23,26,29,32

10,5
0 50 100 150 200 250 300 350 400
Cumulative leaching time (hours)

Fig. 4. pH of the leachates versus leaching time.

sludge content influenced the physical characteristics of
the material; these species may be involved in two or
more solid phases, with different solubilities; the solid
phase(s) which contained these species were more solu-
ble (or unstable) when pH increased (e.g. amphoteric
metals).
4.4. A4icrostructure
SEM observations of samples l-12 have shown typi-
cal cement solid structures, as C-S-H gel, hexagonal
plates of portlandite or AFt-like hexagonal needles,
which contain variable amounts of the anions of the
sludge. In particular, the C-S-H network often con-
tained a few percent of chloride or phosphate ions. The
nature of the needle-like phases frequently observed in
these samples is quite uncertain. However, diffracto-
grams (Fig. 5) indicated the presence of ettringite, but
no (or very little) aluminum was detected by EDAX
analysis of these needles (Fig. 6 ). The presence of sili-
con indicated that this phase could be thaumasite crys-
tals, Ca3Si(OH)6(S04)(C03). 12H20, which has an XRD
pattern similar to ettringite. This result fits with the
characteristics of cement A, which was formulated to
produce very little ettringite, and confirms the partial
carbonation of the samples. Since the samples have been
cured in closed plastic molds, the most likely source of
carbonate ions is the sludge itself, which contains high
levels of calcium hydroxide that may have turned to
calcium carbonate between the time the sludge was pre-
pared and the time it was mixed with cement. This is
partially confirmed by another observation: the higher
22 J.-N. Diet et al.1 Waste Management 18 (1998) 17-24

the sludge:cement ratio, the greater the amount of The diffractograms of the samples containing the
“thaumasite” detected by XRD. chromium hydroxide sludge (samples 15-34) are given in
We also noticed that many samples presented Fig. 7. All samples contained ettringite, even though
numerous microcracks which were probably due to cement A does not form ettringite when mixed with
drying during sample preparation for SEM, or to an water. On the other hand, the formation of portlandite
expansive growth of thaumasite. We also noticed that was reduced, despite the dissolution of the anhydrous
portlandite formation after 28 days of curing was low- calcium silicates. Finally, other work [ 16,171 suggests
ered when sludge was present. that the peaks labelled “U-phase” in these diffractograms
Finally, we did not find any solid phase with a high
level of metal. This is in accordance with a homo-
geneous distribution of metallic species in the matrix.
The crystallographic data from samples 13 and 14,
made with the zinc hydroxide sludge, have revealed the
absence of hydration products after one month of cur-
ing, except for ettringite, which is present in small
quantities especially for the cement A. This confirmed
that the setting of sample 14 was not due to a normal
hydration of cement.

Table 5
Leaching results

% leached

Sample # Cement Sludge Slu./cem Ca Cr04 K Na SO4 (a)

_
(w/w)
_ 1.26 1 25.9 26.5 3.5
I
I
c
A
OA A
15 A co 0.5 0.7 1.5 28.3 22.5 2.3
23 A c 10 0.5 0.76 0.9 29.3 28.1 2.1
29 A c 50 0.5 0.73 1.2 29.7 23.1 1.5
17 A co 2 1.52 3.1 92.8 26.6 22.2
25 A Cl0 2 1.19 9.5 92.1 41.2 12.7
31 A c50 2 1.01 14.3 100.8 41 11.3
OB B _ _ 1.13 0.9 23.3 24.4 1.3
19 B co 0.5 0.63 1.4 22.1 17.5 1.3 c E F
E
z
R w
26 B c 10 0.5 0.67 0.4 22.9 20.6 1.3
0.000 VFS I 512 10240
32 B c 50 0.5 0.65 1.3 25.7 21 1.5
21 B co 2 0.79 2.8 89.8 27.8 14.4
28 B Cl0 2 0.68 10.5 88 41.4 13.3 04
34 B c50 2 0.68 14 96.5 41.7 12.1
Fig. 6. (a) SEM Micrograph of sample 11 (b) EDAX analysis of point 1.

Fig. 5. Diffractograms for samples OA, 5, 6, 7 and 8. P = Portlandite; A = Anhydrous Silicates; T = Thaumasite.
 J.-N. Diet et al.1Waste Management 18 (1998) 17-24
Fig. 7. Diffractograms for samples OA, 16 and 30. P = Portlandite,
may be due to a complex hydrated sulfate phase, similar
to the “U-phase” (3Ca0.A120s.CaS0~.0,5Na2S04.
15H20) first described by Doch and zur Strassen in
1967 [ 181.Its formation here seemed to increase with the
chromate ion content of the sludge, but it disappeared
during leaching, whilst ettringite content was enhanced.
However, no real evidence that could confirm the
latter results have been found by SEM observation.
EDAX analysis showed a rather homogeneous
distribution of chromium within the samples. Yet, three
kinds of structures contained no chromium: the
anhydrous grains of cement, the few portlandite plates
and the C-S-H hydrates that form a ring around the
cement grains, and which Bonen calls “inner hydration
products” [19].
5. Discussion
Notable modifications of the cement hydration pro-
cess when mixed with sludge, were shown in the first
part of this work, especially the precipitation of one or
more solid phases during the first moments. However,
this precipitation hindered further hydration, as shown
for the zinc hydroxide samples, even for low sludge
content (33%), or, for the other samples, when the
sludge content became too high. This last result can be
related to those of Hills [6,20,21] who established that
cement hydration is poisoned by industrial hydroxide
sludge when the waste:cement ratio is over a certain
limit. This threshold depends on the nature of the sludge
and, for our chromium hydroxide sludge, corresponded
to a value of 2:l (w/w).
The microstructural study has established that the
solidified wastes remained largely composed of the usual
cement hydration products, that can include small
amounts of the sludges components, especially anions.
Since the cement grains seemed to be well hydrated, the
23
16
-
S = anhydrous Silicates, LJ = U-phase.
systematic decrease in portlandite formation indicated
that calcium was consumed by some other mechanism.
Indeed, ettringite production was generally enhanced,
even though it was not formed during normal cement
hydration (cement A). The formation of a U-phase
analog was also detected in the chromium containing
samples. Li et al. [2,22] have shown that the formation
of this phase is possible in cement-based solidified
wastes containing high levels of alkali. Nevertheless, we
have found that as more chromate ions were present in
the sludge, more U-phase analog was produced, indi-
cating a possible substitution of sulfate ions by chro-
mate ions, as has been demonstrated for ettringite
elsewhere [24-291.
Besides, Li et al. [22,23] have proved that U-phase
may revert into ettringite in the presence of water and
sulfate and calcium ions, releasing alkalis that increase
the pH of the solution. This would explain the dis-
appearance of the U-phase during leach testing, and the
development of ettringite and corresponding increase of
the pH of the leachate. The chromium retention cap-
ability of the matrix may be affected by this variation of
pH. According to the electrochemical equilibrium dia-
grams [30,31] based on chromium hydroxide, a pH
increase may Iead to the oxidation of Cr+“’ into Cr+V1.
Since the solubility of Cr+V’ is much higher than for
Cr’“’ in high pH conditions, such an oxidation could
explain the increase of chromium release in the leachates.
Finally, the distribution of chromium in samples indi-
cated that this element was fixed during the early hydra-
tion of silicates that leads to the setting of the paste.
6. Conclusion
Two major conclusions result from this work:
Metal hydroxide sludges affect cement hydration, in
ways that depend on the nature and the amount of
24 J.-N. Diet et al.1 Waste Management 18 (1998) 17-24
treated sludge. For instance, sludge can lead to a very
rapid setting (flash set) or to the complete inhibition of
the hydration. The fixation of chromium by OPC
depends on its oxidation state: Crfvl is harder to retain
than Crfm. A too high sludge:cement ratio causes an
increase of the pH of the leachates, that can induce an
oxidation of chromium.
In any case, it can be seen that S/S processes applied
to metal hydroxide sludges need the use of a minimal
quantity of cement, in order to improve, from one hand,
the formation of a solid material, and from the other
hand, an efficient retention of pollutants. Even though
our results do not allow us to define precisely the fixa-
tion mechanisms that take place in the matrix, some
hypothesis may be formulated, that imply both physical
and chemical immobilization, involving: calcium alumi-
nate hydrates such as ettringite and/or U-phase that
may contain chromate ions; calcium silicate hydrates:
physical entrapping of waste components during early
hydration.
Acknowledgements
This study is a part of a Ph.D. thesis that received the
scientific and financial support of Ademe (French
agency for the environment and the energy control) and
Lafarge Central Research Laboratory.
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