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Reference : TP-GB-RE-LAF-028
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* Kerneos
100 Ohio Street
Chesapeake, VA 23324 - USA
** National Refractories & Minerals Corporation 1852 Rutan Drive
Livermore, CA 94550 - USA
***Kerneos France
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Abstract
stiffness of the castable in a flexible container
As castable placement technology advances, (e.g. cup). Once this reaction has occurred, it is
often referred to as “set” or “initial set” or
further information is needed to assess the
“gelled”. After this reaction, a castable does not
rheological properties. Flowability, set time and
necessarily have sufficient mechanical strength
st ren gt h g ai n m easur em ent s h av e been
to survive significant handling. Measured
successfully used to assess rheology, however a
compressive strength numbers may only be on
growing number of laboratories are supplementing
these measurements with an Exothermic Profile the order of about 1.5 MPa (220 psi). When this
measurement of the castable and also the raw reaction is related to the initial dissolution of
materials used to formulate the castable. CAC, it can release a small amount of heat,
which may be measured by a thermocouple.
The heat of hydration of Portland cement and
Calcium Aluminate Cement are on the same order The second reaction is the hydration of the
at about 500 kJ/kg. Because Calcium Aluminate cement with water. During this reaction,
Cement releases this energy over a much shorter hydrates are formed through precipitation from
period of time, this reaction is easy to measure, solution. These hydrates grow in the liquid
even when the cement contents are low. portion of the castable, converting liquid to solid
and binding other materials in the castable
Certain deflocculated castables also exhibit a heat together. This causes the castable to gain
rise during initial flocculation, well bef ore mechanical strength.
hydration, marking the end of working time.
Because these measurements can be automated For this second reaction to begin, germination
of nuclei from the saturated solution must occur
with a thermocouple and a PC, the test is easy to
within the castable. After these nuclei are
set up and run.
formed, the hydration reaction begins and
Creating an exothermic profile on a neat cement proceeds as described by Le Chatelier’s cycle
paste gives information about the composition and (figure I).
reactivity of that cement and may be useful for QA
purposes.This paper will present practical olution olution saturated
saturate
Solution Solution
examples of the above-mentioned topics and unersaturateiwith
undersaturated
p
respect tocement
ceent
th with
with
respecttotohydrates
hrates
res ect to respect
attempt to explain the reason for the occurrences.
Re sul t s a nd di sc u ssi on conc erni ng t he
repeatability and reproducibility of these tests will Wa ter
Sol i d hy dr at es
also be presented.
Pr ec ip i ta ti o n
Dissolution
of h ydra tes
1 Introduction
C ement
Nucleation
Both complex and simple castables utilizing
calcium aluminate cements (CAC) as the binder olution
Solution olution saturated
Solution saturate
undergo two visible reactions after water has been unersaturate with
undersaturated
p
respect tocement
ceent
ith
respect
ith
with
to hrates
res ect to respect to hydrates
added. The first reaction is a flocculation reaction
and is noted by a lack of mobility of the castable
(end of working time) and/or a set by Vicat needle.
Fig I. The Le Chatelier cycle
This type of reaction can also be measured by the
Technical Paper
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2 Practice
Fig II. Exothermic heat profile for a 70% Alumina
Le Chatelier’s principle as applied to simple cement
calcium aluminate cement mortars produces
3:
hydration reactions with the following equations
Technical Paper
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Both the slope of the temperature profile and the Figure III shows no thermal activity (hydration)
derivative of that profile with respect to time can until about 11 hours, with a peak temperature
note these three regions. Not only can we confirm occurring at about 13 hours. In contrast, the
the onset of hydration and therefore strength gain, mortar peak temperature occurred at 5 1/2 hours.
but we can also derive some information about The reason for this slow activity in the neat
the hydrate phases that are being formed by the paste is the lack of germination sites for the
temperature inside the castable. nuclei to start the hydration reaction. Without
the heterogeneous nucleation sites provided by
2.2. Exothermic Profile of Neat Paste the normally present “other” castable raw
materials, like aggregates, fines, etc., the
It is interesting to now compare this mortar profile reaction must start from precipitates only.
to an exothermic profile generated with the same
70% alumina cement in a neat paste formulation.
Neat paste is a formulation of only cement and
water. In this case the water is added at 25% of
the weight of the cement.
Technical Paper
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28
27 0 2 4 6 8 10 12 14 16
26
Time (hours)
Temp (C)
25
24
23 43,0
22
21
0% 0,01%
0,02% 0,06%
20
41,0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24
0,1
Time (h)
Fig. 5
39,0
Time (Hours)
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3 Conclusion 4 References
1. H. Fentiman, C. M. George, and R. G. J.
Exothermic profiling of hydraulic minerals and the Montgomery, “The Heat Evolution Test for
castable systems created from them can reveal Setting Time of Cements and
useful information about the reactions present in Castables”, New Developments in
these systems. In the laboratory, this method is Monolithic Refractories in Advances in
normally automated and if the environment is Ceramics 13 131-35 (1984).
stable, can produce results not generally subject 2. N. E. Bunt, Advanced Techniques for
to operator and equipment error. Only the Measuring Rheology of Cement-Based
thermocouples need to be calibrated. th
Refractories, 29 Annual Symposium on
Refracotires, St. Louis Missouri, March
This technique can be used as a research and 1993.
development tool to generate profiles of castables 3. K. L. Scriv ener, A. Capm as, Cal ci um
being optimized for admixture interaction. The Aluminate Cements; Chapter 13 in Lea’s
addition of an accelerator or retarder can effect Chemistry of Cement and Concrete, 4 ed.
th
significant changes in the exothermic peak times Edited by Peter C. Hewlett, John Wiley &
and temperatures. As the castable can easily be Sons, New York, NY, 1998.
stored in environments of different temperatures, 4. Hervé Fryda, Karen Scrivener, Gilles
studies could also be done on the effect of Chanvillard, Célinine Féron, Relevance of
temperature on the system under investigation. Laboratory Tests to Field Applications of
Calcium Aluminate Cement Concretes,
When designing experiments, one should keep in International Conference on Calcium
mind that the following variables can significantly Aluminate Cements, Edinburgh, Scotland,
affect the results of the profile: Size and shape of 2001.
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starting temperature of the mix, temperature of the “Fume Silica and cement interactions parts
surroundings and the thermal conductivity of the 1-3”, Unitecr 89, Anaheim, CA, USA, 1989.
surrounding medium. 6. K. Jono, E. Maeda, K. Sorimochi, “Reaction
between Alumina cement and phosphate”,
Exothermic profiling could also be used as a Vol 50 No. 4, Taikatbutsu, Japan, 1998.
quality control tool to verify the setting time of 7. E. Maeda, K. Jono, “Adsorption of silica
manufactured castable, troubleshoot problem ont o t h e cem ent part i cl e surf ace i n
castables and to screen reactive raw materials for castables”, Vol 52 No. 3, Taikabutsu,
use in these systems. Japan, 2000.