SET-TIME,

TEMPERATURE,
STRENGTH AND
MICROSILICA

Presented at XXXV ALAFAR 2010 at Lima, Perou in December 6-9,

2010.

SET TIME, TEMPERATURE, STRENGTH AND MICROSILICA

Bjrn Myhre,
Elkem Silicon Materials, P.O Box 8126 Vaagsbygd,
4675 Kristiansand, Norway.
bjorn.myhre@elkem.no

ABSTRACT:
The influence of demoulding time on strength of a microsilica containing LCC
system based on white fused alumina has been investigated. Correlations have been
drawn to the setting exotherms of such castables and results show that even though it
is possible to demould very early, around the first exotherm, the strength suffers
significantly, even after firing. The results indicate that the demoulding time should
not be performed earlier than the second (and final) exotherm. Since microsilica
influences the set time, several microsilica qualities with different set times have been
investigated and the results are coherent with the suggestion of demoulding time
given by the exothermic reactions.

INTRODUCTION AND BACKGROUND:

Additionally to the flow, the set time is one of the most important properties
immediately noticed when a castable installation is done. If the set time extends too
long, production may be hampered , if it gets too quick, problems during installation
may occur. These latter problems might be flash setting during mixing, during
pumping or any other unwanted situation. A good control over the setting becomes
particularly important in pre-cast shops where a rapid turnaround may be critical for
the business.
First of all, what shall be defined as set time, when is it appropriate to demould? In
the early days of refractory castables, up to the first half of the 1980ies, the common
way of determining set time of refractory castables was by assessing set with the use
of a Vicat-needle set up. This had a number of difficulties, of which the labour and
lack of precision when used on castable systems was the most important. The Vicat
needle set-up was based on measuring the resistance by the intrusion of a
standardized needle into the hardening mortar. The method could not easily be used
on castables, since if the needle hit an aggregate, the reading would be erroneous.
In 1984, Fentiman, George and Montgomery3, from the cement producer Lafarge
presented an investigation correlating results from Vicat measurements with
temperature development of castables.
Instead of using a Vicat needle (penetration of a needle into fresh mortar) the
temperature of the castable (or mortar) is recorded. Adiabatic calorimetric studies of
aluminous cement (i.e. pure cement) in contact with water have shown that there are

two exotherms. The first occurs immediately and is associated with heat of wetting
and rapid dissolution. A dormant period then follows during which hydrate nuclei
form and develop. Once critical nuclei have been formed, bulk precipitation of
hydrate occurs giving rise to a second exotherm4. This second exothermic reaction
may be used to determine when the setting starts by simply embedding a
thermocouple into a proper amount of fresh castable or mortar. If the thermocouple is
connected to a strip-chart recorder, the exotherm manifests as temperature increase.
The time to initial set may thus be measured. The time to temperature increase
correlates well with data obtained by the Vicat needle. Figure 9 shows a typical
exotherm and the correlation between Vicat and the heat evolution test. The heat
evolution test can, as opposed to the Vicat needle, also give reliable results when
applied on castables.
Time
TTM

TTS

START

Figure 1. Typical Strip-chart print out showing temperature in a microsilica

containing CA-cement based refractory castable.

Figure 2.Correlation between Vicat initial set and results from heat evolution test for
calcium aluminate mortar.

For castables with both microsilica and CA-cement, the castable normally shows two
exotherms, with the first one appearing after an induction period. This induction
period may last a few minutes or several hours, up to several days have been seen.
This first exotherm has been associated with the formation of a layer of CASH
compounds on the surface of the cement particles that dissolves and enables setting to
proceed, giving the final exotherm5. The first exotherm (TTS) is associated with the
end of workability of the castable, and the time to maximum temperature of the
second exotherm (TTM) is traditionally regarded as the time to final set. The
temperature method has been found easy and reliable, but is not suited for castables
with very low cement content due to the limited amount of heat liberated. The
minimum cement content for reliable measurements may be around 3-5% depending
on sample size and apparatus.
The question then arises, what significance have these temperature peaks for the
castable? What correlation between refractory properties and set-exotherms can be
found? Is there anything to gain by waiting until the final exotherm (TTM) or is it ok
to
demould
as
soon
as
it
is
possible?

At UNITECR 2005 in Orlando6, Myhre presented a study showing set time of a standard LC
castable composition, with the microsilica quality as the variable. All microsilica samples
came from the same source and were sampled during February and March 2004 and 2005.
The results shown here in Figure 3 (using the recipe of Table 1), indicates that if microsilica is
taken as a by-product from an uncontrolled source, large variations in set is to be expected,
and that any signs of stability may be regarded as sheer luck.
12:00
36:00
2004
2005

TTS [h:min]

30:00
6:00
24:00
0:00
18:00
12:00
6:00
0:00
24/1

3/2

13/2

23/2
4/3
Sampling date

14/3

24/3

Figure 3. Initial set as a function of production date for microsilica from one silicon furnace
during winter/spring 2004 and 2005.

Table 1 Standard LCC castable composition.

[wt%]
Microsilica
8
CA-14 [wt%]
6
White Fused Alumina. 35mm
10
White Fused Alumina. 0,5-3
mm
32
White Fused Alumina. 00,5mm
16
White Fused Alumina. -74
micron
12
Calcined alumina: CT 9FG
16
Deflocculant:
Castament
FS20
0,05
Water [wt%]
4.15

In 2009 a comprehensive paper on setting of microsilica containing castables was presented

by Parr et al.7 giving more information about this topic. Figure 12, sums Parr et al.s findings
schematically, verifying that TTS indeed can be regarded as initial set. Also TTM can be
regarded as final set according to the ultrasonic speed measurements.

Figure 4. Comparison of ultrasonic, exothermic and conductivity curves for a microsilica

containing LCC mortar at 1.44 water/cement ratio (ref. 5)

After the initial set, strength (ultrasonic speed) develops, but it is not until after the maximum
temperature (TTM) at 8 hours that significant improvement in combined water is found. In
Figure 5, DTA curves of the LCC mortar of Parr et al. is shown for samples stopped at
different curing durations. At 8 hours the maximum temperature was reached, and
interestingly, no more combined water was found than after initial set. It is between 8 and 24
hours that combined water develops giving the hydraulic phases that are responsible for
strength. This is somewhat contradictory to the results from ultrasonic speed measurements
and indicates that a castable must be cured for a duration exceeding the Time To Maximum
temperature in order to obtain full strength.

Figure 5. DTA curves of LCC mortar during the hardening phase (ref. 5)
EXPERIMENTAL RESULTS AND DISCUSSION:
The primary aim for this investigation was to see what correlations that could be found
between setting time as expressed by the exotherms and the resultant strength. Basis was the
LC castable composition of Table 1 and the variables were the demoulding time and the
microsilica used. Different qualities of microsilica were used to influence the TTS and TTM,
and in one instance also citric acid as retarder.
After dry-mixing and 4 minutes wet-mixing, samples 40x40x160mm were cast and placed at
20C at >95%RH for curing. Samples were then demoulded when it was possible, normally
around the TTS, between TTS and TTM, at TTM and after 24 and 48 hours. The demoulded
samples were then immediately placed in a heating cabinet maintained at 110C in order to
both stop further hydration, but primarily to mimic drying of shapes in a precast shop.
Although this represents an approximation of the industrial procedures, it was felt sufficiently
close to disclose relevant information concerning strength development. At IREFCON 2010,

some results were shown. Figure 6 is taken from that presentation8 and shows that unless one
is willing to wait for the required time, the strength of the body may be severely affected. Not
only in the green state, but rather surprisingly, also after firing at 600 or 1000C.
In Figure 6, cold modulus of rupture is shown for two series of LCC castables as a function of
curing time. The resulting strength is here expressed as percentage of the 24 hours strength for
two series of castables based on the recipe of Table 1, One of the two series was retarded with
an addition of 0.02% citric acid. This resulted in an increase of the setting as expressed by
TTS from 2 to 11 hours. The time to TTM also increased to 20 hours. It should be noted
however that the precision of the readings of the retarded castables is not as good as the
reference, primarily because the temperature response on readout becomes diffuse at long set
times. Despite this uncertainty, this might be an indication of a possible influence from citric
acid.

120.00

TTM

100.00

CMOR[ %]

80.00
TTM (citric acid)

60.00

TTS(citric acid)
TTS

110C
600C
1000C
110C (0.02% Citric acid)
600C (0.02% Citric acid)
1000C (0.02% Citric acid)

40.00

20.00

0.00
0

10

15

20

25

30

Time

Figure 6. Strength(C-MOR) of LCC (ref Table 1) as a function of curing time and firing
(12hours at temperature). Samples interrupted after various curing times. Elkem Microsilica
971, lot 3046663. 0.02% citric acid was added as retarder for one serie. TTS and TTM
indicated by ovals.
The impression from Figure 6 is thus that the demoulding time affects strength, not only the
green and dried strength, but also the fired strength up to 1000C. To get maximum strength,
it seems that one should wait until TTM and possibly even longer before demoulding and
drying is performed.
To check these findings, a further test program was therefore performed.
This time both another lot sample of 971 and another microsilica quality was chosen with a
somewhat longer set time (968). The same castable composition was used (Table 1)

968,
968,
968,
971,
971,
971,

40.0

35.0
TTM

968

C-M.O.R. [MPa]

30.0

110C
600C
1000C
110C
600C
1000C

TTS

971

25.0

20.0

15.0

10.0

5.0
0

10

20

30

40

50

60

curing time[h]

Figure 7: Strength as a function of curing time at 20C. LCC with microsilica 968 or 971.
Samples dried at 110C and fired at 600C or 1000C (12 hours).Vertical full drawn lines
indicate the TTS and TTM for 971, dotted vertical lines indicate it for 968.
In Figure 7, the C-M.O.R. of the samples are shown as a function of curing time for samples
dried at 110C and fired at 600C or 1000C. If the results are compared with Figure 6, we
see that the time of demoulding indeed has an influence, but perhaps not as pronounced as
indicated by the results of Figure 6. It does pay off to wait until TTM or longer though,
although the results after firing at 1000C indicates that the effect is less pronounced than
after drying at 110C and firing at 600C. The results for 971 are in good agreement with the
earlier results presented in Figure 6. If 971 is compared to 968, it is seen that the strength
levels are similar but 971 obtains a higher strength than 968 after the 600C firing. Generally
speaking, if the results presented in Figure 6 and 7 are evaluated, they confirm the impression
that waiting until TTM pays off. It may not yield so much to wait longer, but demoulding at
24hours is a good rule if temperatures are not measured and mould turnover is not of big
concern.
CONCLUSION:
If a castable is demoulded at a very early stage of the setting as represented by the TTS,
significantly lower strength (than obtained at a later demoulding) should be expected. In some
instances a 40% reduction of the final strength has been observed by this early demoulding.
Somewhat surprising, the low strength level is mirrored in the fired samples at 600C and
1000C, pinpointing the importance of waiting for the correct time to demould. Demoulding
should according to the present findings not occur before the TTM has been reached.
REFERENCES:

3
4
5
6
7
8

C.H. Fentiman et. al in " Advances in Ceramics vol. 13, New Developments in Monolithic Refractories" ed.
by Robert E. Fisher, The Am. Ceram. Soc. Inc. Columbus, Ohio 1985 p. 131-135
L. S. Wells and E. T. Carlson; J. Res. Natl. Bur. Stand., RP2723, 57, 335 (1956)
Steffen Mhmel: in Die Reaktionen von Calciumaluminaten bei Hydratation und thermischer Belastung
Beitrge zur Chemie der Hochtonerdezemente dr. ing thesis Tech. Univ. Freiberg Germany 2003.
B. Myhre, Microsilica in Refractory Castables - How does Microsilica Quality influence performance? in
proc. UNITECR 2005 Orlando USA Nov. 9, 2005
C. Parr et al. Investigations Into the Interactions of Deflocculated Castables Which Control Placing and
Hardening Properties, Part 1: Placing Properties Ref. Appl. Trans. Vol 4 [2] 2-8, July/August 2009.
B. Myhre Microsilica in Castables Surface properties and Set, in proc. IREFCON 2010, Kolkata, India,
February 4-6, 2010