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Aging Behavior of Deflocculated Low Cement Castable -Influence of

Deflocculant, Microsilica Quality and Aggregate Base

Conference Paper · August 2020

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 Aging Behavior of Deflocculated Low Cement Castable – Influence of Deflocculant, Microsilica Quality and
Aggregate Base

C. J. Dileep Kumar, Gaurav Sinha, Shushavon Sarkar, Suparna Basu, Sumit Samanta, Saumen Sinha, Santanu Basak and
Indra Nath Chakraborty

Calderys India Refractories Limited, Nagpur India

Abstract

Low Cement Castables (LCC) are vulnerable to aging owing to the presence of Calcium Aluminate Cement (CAC),
deflocculant and microsilica. All these constituents individually are known to change their characteristics with time. These
changes are primarily due to the interaction of these constituents with atmospheric moisture. Impact of these aspects on
the flow, setting and strength characteristics of low cement castable has been evaluated. This work has revealed that in
addition to the aforementioned constituents of LCC, nature of the aggregate also has significant bearing on LCC
aging. For specified level of water used for casting, no significant change in setting behaviour observed with changes in pH
of deflocculant and microsilica. Whereas with aging castable setting time of Silicon Carbide containing castable increases,
whereas setting time goes through maxima for alumina based castable. Strength of castables, both Cold Crushing and
Modulus of rupture, shows decreasing trend with aging of castable for all permutation of variables studied during this work.

Introduction

Monolithic refractories, compared to pre-shaped items like brick, can be considered to be a semi – finished product since its
shaping is done during the installation. Owing to this reason the material behaviour as well as adherence to specified
parameters, during installation, is a major determinant of the final monolithic quality. It is well known that conceptually
refractory castables are similar to civil concrete but the type of cement used in these 2 formulations differs. Cement used in
castable refractory formulations is Calcium Aluminate (CAC), whereas it is calcium silicate (CS) in normal concrete. Affinity
as well as reaction rate of CAC is many folds higher than those of CS. Owing to this reason degradation of CAC based
concrete formulations is significantly faster than those based on CS, in case they are exposed to atmospheric moisture.
Even with best of methods adopted for prevention of atmospheric moisture attack, interaction of CAC with atmospheric
moisture can truly not be prevented, and hence, castable degradation is inevitable.
Apart from the vulnerability of CAC in refractory castable formulations, there are other aspects also cause its degradation by
aging. Today it is no secret that ultrafine material like microsilica and dispersants are unavoidable constituents of low
cement castable formulations. These constituents of castable formulations also have significant impact on its aging
characteristics.
In one of our earlier work impact of ambient temperature as well as aging on the castable installation characteristics, viz.
Flow, setting time, have been evaluated1. In this work the impact of deflocculant, microsilca and aggregate quality on the
aging of Low cement castables has been evaluated.

Experimental
Castables were produced and packed in HDPE bags, as is done for normal industrial castable production condition.
Subsequently the bags were stored in normal industrial storage conditions for 6 months. Table I reports the formulations
evaluated during this work. In this castable formulations were prepared by using:

- Microsilica of 2 different pH
- Phosphate deflocculant with different pH
- Different aggregate, viz. calcined bauxite and fused Mullite

In one of the trials, where microsilica pH was varied, Silicon Carbide was one of the aggregates in the formulation. It also is
evident from the Table that a formulation based on fused Mullite was prepared for studying the impact of aggregate quality
on the castable installation features.

For the measurement flow, setting time and strength requisite quantity of castable was drawn from freshly opened bags,
which were stored in normal ambient condition. During this work no special effort was made for maintaining the castable –
water mix temperature at the constant level while measuring the flow and setting characteristics at different stages of aging.
Castable – water mix temperature, thus, primarily depended on the ambient temperature. Experiment was designed in this
fashion since in India; ambient temperature shows a variation of > 40 0C during one year. Such experiment design, thus,
would combine the effect castable aging as well as mix temperature variation simultaneously on castable installation
parameters and reproduce the actual site condition.

Castable mix consistency, during this work, was determined as per EN ISO 1927 – 4. Water requirement, for flow of 100 –
115% for each castable, was determined for all the castables on Day zero of measurement. Subsequent work, with the
aged castables, was done with the addition of the same water percentage and corresponding flow was measured. Setting
time of castable was measured by checking the compressibility of the cast material. Strength measurement was done as
per IS 10570.

Table I Formulations of the Castables Studied during this work

Impact of
Phosphate
Nomenclature used in the Text Microsilica Aggregate
Deflocculant
Fused Mullite Calcined Bauxite
pH 7 pH Acidic pH 8.3 pH 9.6
(ACCMON 70 M) (ACCMON 90)
Constituents
Calcined Bauxite √ √ √ √ – √
Calcined Clay √ √ – – – –
Fused Mullite – – – – √ –
Silicon Carbide √ √ – – – –
Phosphate Deflocculant pH 9.6 √ √ – √ √ √
Phosphate Deflocculant pH 8.3 √ – – –
Microsilica pH 7.1 √ – √ √ √ √
Microsilica pH 3.8 – √ – – – –
Other Additive and Constituents
√ √ √ √ √ √
of Low Cement Castables

Results and Discussion

A) Impact of Microsilica pH
The results reported in Figure 1 are for a Silicon Carbide containing formulation, where phosphate deflocculant of pH 9.6
has been used. Apart from Silicon Carbide, the other aggregates in this castable were Calcined Bauxite and calcined Clay.
To study the impact of microsilica pH on castable aging behavior, neutral microsilica (pH ~ 7) and acidic microsilica (pH ~ 4)
were used. Water for casting for pH ~7 and pH ~ 4 microsilica, for all the castings, were 5.5. and 5.2 % respectively. It has
been observed that, for same level of flow, acidic microsilica requires lesser water compared to the one based on neutral
(pH ~7) microsilica.

450 40
Setting Time, Minutes / Flow, %

400 35
350
Mix Temperature, C

Setting Time, Minutes 30

300
25
250 Flow, %
20
200 Mix Temperature, C
15
150
100 10
50 5
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Day Day
Microsilica pH 7 Month Acidic Microsilica
 Figure 1 Impact of Microsilica pH on the Flow and Setting Time of Silicon Carbide containing Aged Low Cement Castable

Even with lesser water used for casting on Day 0, i. e. measurement done on the day of production, castable based on
microsilica with pH of 4 had slightly higher flow, compared to that based on microsilica of pH 7. Setting time of the former
castable, on the other hand, was distinctly higher. During the course of the experiment the castable – water mix
temperature decreased for both the castables.

Lowering of mix temperature did not affect the flow characteristic of castables a great degree but had distinct impact on the
castable setting time. With aging the setting time of both the castable increased, which for Microsilica pH 4 based castable
was distinctly higher compared to that based on Microsilica pH 7. The increase in setting time could be attributed to
both lowering of Castable – water mix temperature and the pH effect of microsilica. It is evident from the plot that for
a given mix temperature setting time of Microsilica pH 4 based castable is longer with a lesser aging time, compared to that
of the one based on Microsilica pH 7. This observation implies that the aging of Microsilca 4 based castable is faster
compared to the other under consideration. It also can be seen from the plot that the setting time, at initial stage of
aging, increases at a much faster rate compared to the one based on Microsilca pH 7.

Figure 2 illustrates the variation of Modulus of Rupture (MOR) with aging. During this work focus has been more on
MOR since it is an indicator of bond strength. MOR, thus, is likely to indicate the bond strength, which is expected
to get affected due to aging since matrix constituents are significantly more vulnerable. Based on the results it can
be stated that MOR for both the castables, in general, reduces with aging. Similar to the observations made for setting time
variation, reduction of MOR in the early stage of aging, for acidic Microsilica based castable, is much faster compared to the
one based on neutral microsilica. Additionally, subsequent to aging of castable for 6 months the MOR of acidic microsilica
based castable is lower. This implies that the castable bond is adversely affected to a greater degree, with aging, when it is
based on acidic microsilica.

180
160
140
MOR, kgs / cm2

120
100
80
60
Dried
40
1100 C / 3 hrs
20
0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Day Day
Moicrosilica pH 7 Months Acidic Microsilica

Figure 2 Impact of Microsilica pH on the Modulus of Rupture (MOR) of Silicon Carbide containing Aged Low Cement
Castable

B) Impact of Deflocculant pH

Figure 3 illustrates the effect of phosphate based deflocculant of different pH on the installation characteristics of castables
based on calcined bauxite and Microsilica of pH ~7. The pH of the deflocculant used during this work was 9.6 and 8.3 and
water used for the casting these castables was 4.5 and 4.3%, respectively for achieving similar flow. It, thus, can be stated
that water required for casting increases with increase of deflocculant pH. Flow characteristic of castables do not show any
significant variations, with aging when same level of water was used for casting.

Setting time of both the castables do not show significant variation, for up to 3 months, while the castable – water mix
temperature increased. Increased mix temperature is expected to decrease the castable setting time. It may be
hypothesized that initial stage of aging increase of setting time due to aging is being compensated by increase of
temperature. After 3 months of aging, however, setting times of both the castables increase in spite of increase in mix
temperature. At this stage impervious layer on the cement surface is a predominant mechanism for delaying the cement
hydration compared to its enhancement due to temperature rise.

Beyond 4 months of aging, setting time of both the castables decreases in spite of decrease of mix temperature. It is
hypothesized that at this stage of aging, interaction of cement with moisture yields calcium aluminate hydrated phases,
which act as an accelerator for setting and over rides the impact of lower mix temperature

The impact of deflocculant, with pH in the range of 8.3 and 9.6, on setting time shows similar trend. Deflocculant of higher
pH, however, yields lower setting time at early stage of aging. Additionally, setting time variation with aging, for the same
castable, however, is lower.

250 39
Setting Time, Minutes
Flow, % / Setting Time, Minutes

Flow, % 38
200

Mix Temperature, C
Mix Temperature, C 37
150 36

100 35
34
50
33
0 32
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Day Day
Phosphate (pH 9.6) Month Phosphate (pH 8.3)

Figure 3 Impact of Deflocculant pH on Setting Time and Flow of Calcined Bauxite based Aged Low Cement Castable

Figure 4 illustrates effect of castable aging on dried MOR. For identical formulation deflocculant with lower pH yields higher
MOR, compared to the one based on higher pH. Both the castables, which are based on phosphate deflocculant of different
pH, show similar trend on aging. At the initial stage of aging MOR increases which probably is attributable to completion of
hydration reactions in the castable. Beyond 1 month the MOR of both the castables decreases. In this context it is
important to note that the degradation for castable based on deflocculant with higher pH commences early. Also, MOR of
this castable is significantly lower compared to the one based on low pH deflocculant. Lower pH deflocculant, hence, is a
better option in castable formulation for achieving higher strength.

350
Dried
300 1100 C / 3 hrs
250 1550 C / 3 hrs
MOR, kgs / cm2

200

150

100

50

0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Day Day
Phosphate (pH 9.6) Months Phosphate (pH 8.3)
 Figure 4 Impact of Deflocculant pH on Modulus of Rupture (MOR) of Calcined Bauxite based Aged Low Cement Castable

C) Type of Aggregate Impact on higher pH Microsilica as well as deflocculant based ACCMON(LC Castable)

Two formulations, one based on calcined bauxite and the other on fused Mullite, viz. ACCMON 90 and ACCMON 70 M,
respectively, were chosen for evaluation of aggregate impact on aging of low cement castable. Higher pH Microsilica as
well as high pH deflocculant were used for these 2 formulations. Water percentage used for casting ACCMON 90 was
4.5%, whereas the same for ACCMON 70 M was 4.7%. This observation is expected since the density of ACCMON 90
castable was higher.

Castable – water mix temperature during casting remained in a narrow range and hence, the differences in the installation
characteristics as well as physical properties of the castable with aging, are attributable to changes in the castables
occurred during their aging. Flow characteristic of castables virtually did not vary at all due to aging. ACCMON 90 setting
time remained at the same level till the material was aged for 3 months. On the other hand, setting time of ACCMON 70 M
increased significantly after a month’s aging. Beyond 3 months setting time of ACCMON 90 increases and then reduces.
This phenomenon has been explained in the literature by formation of impervious layer on the cement surface and formation
of hydrated phases, respectively. It appears rate of impervious layer formation on the cement surface, for ACCMON 90, is
lower compared to that of ACCMON 70 M. Increase in setting time, however, is significantly higher for Mullite based
ACCMON 70 M. In other words, aggregate type also contributes to setting characteristics of castable during aging.

450 40
Flow, % / Setting Time, Minutes

400 35
350 30
Setting Time, Minutes

Temperature, C
300
Flow, % 25
250
20
200 Mix Temperature, C
15
150
100 10
50 5
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Day Day
ACCMON 90 Months ACCMON 70 M

Figure 5 Impact of Aggregate base on Flow and Setting Time of aged Low Cement Castable

Figure 6 illustrates the MOR of both ACCMON 90 as well as ACCMON 70 M castables dried at 110 0C for 24 hours. MOR
of both the castables reduces with aging. MOR reduction of ACCMON 90 is in expected line, i. e. initially it increases, which
is probably due to completion of hydration reaction and subsequently reduces.

Reduction in MOR for ACCMON 70 M, on the other hand, starts early and the reduction continues with aging. Though
ACCMON 70 M has higher initial MOR, compared to ACCMON 90, but its magnitude of reduction after 6 months aging is
higher. This aspect implies that matrix degradation of castable, which determines the MOR, also depends on the castable
aggregate base.
 200

Dried MOR, kgs / cm2

150

100

50

0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
Day Day
ACCMON 70 M ACCMON 90
Months

Figure 6 Impact of Aggregate base on Modulus of Rupture (MOR) of aged Low Cement Castable

Conclusion

Aging of low cement castable affects installation features, i. e. flow and setting time, as well as strength characteristics.
Deflocculating system, microsilica as well as aggregate characteristics of the product formulation alters the castable aging.
Both acidic and neutral microsilica in Silicon Carbide containing LCC formulation delays the setting with aging but the delay
with acidic microsilica is significantly higher. Silicon Carbide free LCC, however, shows a different trend of setting time with
aging. For such formulations setting time increases up to ~ 4 months and then decreases. Decrease in setting time can be
attributed to formation Calcium Aluminate hydrate phases. Delay in setting time is higher for formulations based on lower
pH deflocculant. Setting time variation with aging, for LCC based on higher alumina aggregate is lower. Wider setting time
variation is observed for mullitic aggregate based formulations.

Bonding strength of castable reduces with aging beyond certain period, which is reflected by the MOR data generated
during this work. Increase of MOR, during the early period of aging, is attributable to completion of hydration reaction. This
observation is true for formulations based on all variances of aggregate, microsilica and deflocculant used during this work.
Strength reduction for acidic microsilica based formulation, due to aging, is higher. Opposite is the effect of deflocculant.
LCC based on lower pH deflocculant has higher strength, compared to that based on higher pH. Additionally, overall
reduction in strength due to aging also is lower for LCC based on lower pH deflocculant. Aging pattern of Calcined bauxite
and fused mullite based LCC formulations is similar. Though as expected the strength of calcined based formulation is
higher. For both these formulations, strength rises during the early stage of aging but reduces during prolonged aging.
Overall reduction of strength due to aging is almost same for both the formulations.

References:

References

1. Mathieu, A., Bayoux, J.P., Vialle, M., Ageing of Aluminous Cement in LCC. Conference Proceedings of UNITECR 1995,
Kyoto (Japan) 1995
2. H. Fryda, J. Mariaoui, and C. Parr, The determination of the shelf life of refractory castables through accelerated ageing
tests, Interceram Refractories Manual (2010).
3. C. J. Dileep Kumar, G. Sinha, S. Sarkar, S. Basu, S. Sinha, S. Basak, I. N. Chakraborty, Aging Behaviour of
Deflocculated Low Cement and Self-flow Castables – Influence of Materials, Additives and Atmospheric Conditions,
Conference Proceedings of UNITECR 2019, Yokohama (Japan) 2019
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