Setting Additives Influence on the

Thermomechanical Properties of
Wet Shotcrete Refractory Castable
REFRACTORY CERAMICS

Matrices
The effect of coagulants and setting admixtures on the thermo-
mechanical properties of wet shotcrete refractory castable
matrices was evaluated and discussed.

Y.A. Marques, R.G. Pileggi, rheometric analyses,2,5 equipment and

F.A.O. Valenzuela, M.A.L. Braulio and additives.2 These developments have led
V.C. Pandolfelli to the introduction of wet shotcrete in
Dept. of Materials Engineering, Federal
University of São Carlos, São Carlos, S.P., Brazil the refractory industry.1

Despite its simple concept, the task of

prayed concretes were preparing refractory shotcrete is com-

S originally developed for

civil construction in the
early 20th century.1 The
advances and benefits that
have been attained since then are
plex. It involves particle-size design, dis-
persion, mixing, pumping, spraying and
setting.2,6–8

responsible for the current widespread Refractory castables can be prepared in

use of this placing technique. High instal- a broad range of particle sizes.5,8 They
lation rates, lower costs, automation consist of a matrix (particle size of <100
capabilities and performances similar to µm, controlled by surface forces and
preshaped refractories are some of the interactions with the aqueous media)
benefits of this technique.1–4 and aggregates (particle size of >100 µm,
controlled by mass forces). For better
Wet shotcrete consists of pumping the sprayability, the pumped castable should
castable suspension out of the mixer and be homogeneous, dispersed and
onto the target surface (Figure 1).1,5 segregation-free (matrix/aggregate
Compressed air is injected into the tip of separation).1,2
the pipeline nozzle to generate the
castable spray that lines the surface. The The design of pumping castables has
sprayed castable is consolidated by an been mastered to a considerable extent.
additive, also injected at the nozzle tip, However, other aspects of wet shotcrete
which causes sudden loss of fluidity in that require research are the generation
the concrete. This technique results in
of spray at the conical nozzle (Figures 1
low rebound and does not require molds.
and 2) and the proper selection and
This process also is characterized by low
quantity of setting additive. The granules
porosity of the placed material because
formed during spraying can become brit-
of the high shearing rates imposed by
the process. tle or plastic during the short trajectory
from the nozzle to the target. These
results depend on the setting additive
Wet shotcrete has evolved as a result of and its interaction with castable
the advances in pumpable castables, constituents.

©The American Ceramic Society American Ceramic Society Bulletin www.ceramicbulletin.org August 2005 9201
Figure 1 Schematic description of the wet shotcrete process,
showing mixing, pumping and spraying stages.5

Figure 2 Schematic illustration of the wet-shotcrete spraying technique of refractory

castables.7

The formation of spray is influenced promotes greater attracting forces recent studies4,5,7 have focused on
by the equipment (pump, pipeline between the particles and, thus, the rheological aspects of wet shot-
and nozzle design), operational pro- directly affects material packing crete applications. Another study
ceedings (compressed air pressure, structure.3,4,9 reports the influence of various
additive injection, placing direction coagulation mechanisms on the per-
and spray opening angle), castable meability and drying behavior of
A novel class of organic viscosity-
rheological behavior and matrix
enhancing admixtures has been refractories.9 However, the impact of
composition. The setting additives developed recently for hydraulically coagulant admixtures on the ther-
directly affect the rheology of the bound materials (cement based).10 momechanical properties of refrac-
material.4 Therefore, spraying and The admixtures in this castable gen- tory castables remains unclear.
consolidation of the castable also erate water-trapping gels that
depend on how the additive inter- increase viscosity of the solution,
acts with the matrix. The major problems involved in
cohesion and material adhesion. studies of the postsetting properties
Nevertheless, these additives may of shotcrete are associated with sam-
Cement accelerators are normally retard the drying of refractory casta- pling. In the field, the panel water-
used in wet shotcrete applications to bles, which extends their processing drilling technique can damage the
make the castable set instantaneous- time. Other admixtures form 3-D net- samples. In the laboratory, the rapid-
ly.1,2,4 Most of these additives are work gels as a result of crosslinked ly decreasing fluidity of the castable
based on alkaline compounds. Their bonds with cement calcium ions.10,11 makes shaping a difficult task. This
performance depends on their This mechanism decreases water inconvenience has been overcome
chemical composition and cement retention, because cohesion also is by pressing the material.
particle-size distribution.3 However, a promoted by the newly generated Nevertheless, the particle-packing
disadvantage of this class of addi- chemical bonds. structure may undergo alterations
tives is that they decrease castable and, therefore, not reproduce the
mechanical strength. Moreover, they Organic polyelectrolytes that have actual process.3,9 Moreover, the vari-
can decrease material refractoriness long polymeric chains also have been ous coagulation mechanisms of
in high-temperature applications. proposed as admixtures for wet shot- additives can directly influence parti-
These effects scale with the amount crete refractory castables.4,9 Although cle packing, which affects material
of additive.2,3 the long polymeric molecule chain microstructure.
establishes bridges between the par-
ticles,12 the steric effect prevents the
To minimize these effects, alkali-free Previous research8 has shown that
particles from approaching each
additives have been developed.2,3 the creep behavior and elastic modu-
other too closely.Therefore, the per-
They also decrease the risks related lus of refractory castables, based on
meability and drying time of the
with the toxic nature of alkaline sub- different Andreasen’s packing coeffi-
castable is not overly affected.9,12
stances. The setting mechanism of cients, are directly related to the
admixtures usually derives from an nature and content of the matrix.
increase in the ionic strength and a Setting additives also can affect Moreover, the maximum deformation
change in suspension pH levels. This other castable properties. Several during the creep test is only slightly

©The American Ceramic Society American Ceramic Society Bulletin www.ceramicbulletin.org August 2005 9202
 setting additives on the thermome- (PAS) (BASF, Germany)); and viscosity-
chanical properties of wet shotcrete enhancing polymer (hydroxyethyl
refractory castable matrices. cellulose QP90 (HEC) (Union Carbide,
Brazil)). Two systems were studied:
0.6 wt% of each of these additives
Design/Evaluation Tests added separately; and combined
Castables for shotcrete applications 0.075 wt% of alginic acid salt (Alg)
are pumped before they are sprayed. (Fluka, Switzerland) and 0.6 wt%
Therefore, a high-alumina, ultra-low- sodium polyacrilate.
cement refractory composition that
had pumpable characteristics was Various additive coagulation mecha-
first formulated (Figure 3(A)).5 It was nisms were chosen to consolidate the
based on the Andreasen model and castables (Figure 4). SS and CC are
had a packing coefficient of q = 0.26. inorganic admixtures commercially
The formulation had an original used. Basically, they increase system
composition of 78.9 wt% white fused ionic strength, alter the potential
alumina (Elfusa, Brazil), 20.6 wt% energy balance, and promote particle
calcined alumina (A1000-SG and attraction and agglomeration.4,9,13
A3000-FL, Almatis, U.S.) and 1 wt%
aluminous cement (CA-14M, Almatis,
U.S.). The castable was reformulated The PAS used in this work is a high-
so that the entire particle-size distri- molecular-weight organic polyelec-
bution was equivalent to that of trolyte (MW = 15,000 g/mol). It floccu-
the castable matrix (<100 µm) lates/coagulates the particles in sus-
(Figure 3(B)). pension by promoting bridging,
depletion and ionic strength
increase.12 However, the steric effect
The matrix formulation also had an
associated with its molecules keeps
Andreasen packing coefficient of q =
the particles apart, which preserves
0.26.The interparticle spacing (IPS)5
was 0.077 µm, similar to that of the their original positions.
castable (0.088 µm).The matrix sus-
pension was prepared with 60 vol% Alg is a high-molecular-weight poly-
of solids and 40 vol% of water.This mer (MW = 48–186 kg/mol) derived
was equivalent to a water content of from brown seaweed.4,9,10 This addi-
18 vol% in the concrete. A polycar- tive gels in water by crosslinking its
boxylate ether (0.15 wt%) (SKW, molecules with the calcium ions in
Germany) was used as the dispersant. the cement. Consolidation promoted
by Alg does not alter particle posi-
The matrix was mixed in a lab mixer tions in the matrix.
(Etica SA, Brazil), and the additive
was incorporated as follows: powder HEC is a water-soluble, nonionic,
Figure 4 Castable coagulation mechanisms: dispersion in water at a constant semisynthetic organic polymer that
(A) castable without additives; mixing speed; injection of setting increases liquid viscosity and yield
(B) agglomeration caused by attraction additive; 20 s of homogenization; stress by generating a thixotropic
forces among the particles; (C) bridging
effect caused by PAS molecules; and
molding of samples for the mechani- lubricant gel. The gel does not affect
(D) bridging effect and gel formation.9 cal strength and creep tests; curing system pH or ionic strength.4,10
in a saturated atmosphere (100% rel-
dependent on the maximum particle ative humidity) at 50°C for 72 h; and
diameter. further drying for another 72 h, Porosity Tests
embedded in silica gel (50°C).
The total matrix porosity of the sam-
The chemical and structural effects ples cured and dried at 50°C and
of the coagulation mechanisms on Additives prefired at 500°C for 5 h was evaluat-
refractory castables can be isolated ed. Kerosene was used as the immer-
by characterizing the fine fraction of Three distinct classes of setting addi- sion liquid (ASTM C 20-87). The mean
the particle-size distribution that cor- tives were used: inorganic (sodium pore-size diameters of these samples
responds to the castable matrix (<100 silicate (SS) (Aldrich, Brazil)); calcium also were evaluated using mercury
µm).Therefore, the main purpose of chloride (CC) (Synth, Brazil); organic porosimetry (Model EUA,
this work is to evaluate the impact of polyelectrolyte (sodium polyacrilate Aminco–Winslow).

©The American Ceramic Society American Ceramic Society Bulletin www.ceramicbulletin.org August 2005 9203
Strength
The splitting strength technique
(ASTM C 496-90) was used to evalu-
ate the mechanical strength of sam-
ples (40 mm in diameter and height).
The splitting strength was evaluated

CPI Hg (%)
for five samples of each experimen-
tal set after they were cured (72 h)
and dried (50°C) or prefired (500°C
for 5 h after they were dried).

Refractoriness under load (RUL) was

evaluated for cylindrical specimens
(50  50 mm) that had a central hole
(12.4 mm in diameter). Tests were
conducted on prefired samples Pore diameter (µm)
(500°C for 5 h) to ensure that all pos-
Figure 6 Influence of shotcrete additives on pore-size distribution of castable matrix after thermal treat-
sible residual hydrates were eliminat- ment at 500°C for 5 h (CPI Hg is cumulative percentage of intruded mercury).
ed. This decreased the likelihood of
explosion. For RUL and creep evalua-
tions, the samples were heated to
1500°C in 5°C/min steps, under a
compressive load of 0.2 MPa (Model
421, Netzsch). For the creep tests, the
load was maintained for 12 h at
1500°C.8,14
σf (MPa)

Shotcrete Additive Selection

Apparent porosity and density
results (Figure 5) showed that these
properties of the castable matrix
were not greatly affected by the set-
ting additives, particularly after they
were prefired at 500°C for 5 h.

Figure 7 Influence of shotcrete additives on mechanical strength of castable matrix.

The total pore volume and pore
mean diameter were similar in all the
mechanical strength of the castable 2CaO·Al2O3·SiO2·8H2O, that prevented
compositions. Therefore, the cumula-
matrix in various ways (Figure 7). The cement hydration.13
tive percentage of intruded mercury
(CPIHg) as a function of the pore influence of organic and inorganic
diameter for the various setting additives is clearly distinguished. The low mechanical strength of the
additives showed no significant castable matrix that contained CC is
influence (Figure 6). Inorganic additives SS and CC attributed to its agglomerating
decreased the mechanical strength effect. CC is a cement hydration
These results are congruent with of the matrix dried at 50°C. The com- accelerator2,3 that promotes a less-
previous research15 that shows these bination of SS and high-alumina packed structure.
characteristics are governed by the cement (HAC) increased the pH level
amount of water in the matrix. of the matrix,4,12 which led to intense The organic additives PAS, HEC and
Therefore, the mechanical strength, particle agglomeration. As a result, the combination of PAS and Alg
RUL and creep values in this study the bonding force of the matrix was increased castable mechanical
are less likely to be influenced by the directly affected, which weakened strength after drying at 50°C. This
apparent porosity of the matrix. the structure of the matrix after dry- effect was caused mainly by the for-
ing at 50°C.4 Furthermore, SS retard- mation of polymeric chains (drying
The present results demonstrate ed HAC setting, which promoted the at 50°C) and gel drying (at 50°C and
that shotcrete admixtures affect the formation of compounds, such as thermal treatment at 500°C). These

©The American Ceramic Society American Ceramic Society Bulletin www.ceramicbulletin.org August 2005 9204
 admixtures. PAS and its combination
with Alg showed a similar behavior
in the RUL and creep tests. Both
additives shifted the onset of defor-
mation to higher temperatures
(Figure 9). Moreover, these organic
admixtures decreased the maximum
creep deformation attained by the
T (°C)

dL/L0 (%)
castable matrix, which improved the
performance of the material.

A comparison of the mechanical

strength of the samples dried at
50°C and the creep results (Figure
10) revealed a definite correlation.

Figure 9 Starting temperature deformation of matrix, T, with various additives, and maximum percentual Particle packing and pore-size dis-
deformation, dL/L0 , attained by matrix during creep test. tribution did not substantially affect
the mechanical strength after drying.
Therefore, the different values
obtained were related to the addi-
tive binding property and the RUL
and creep results to its chemistry.

The amounts of additive in the

matrix can be greater under terms of
dL/L0 (%)

field performance.1,3 Therefore, their

effect on the properties of the
castable can be intensified.
Moreover, a distinct criterion for the
selection of setting additives—
besides rebound loss2–4 and drying
behavior9—should influence the
thermomechanical properties of the
castable matrix.
σf (MPa)

Figure 10 Maximum creep strain, dL/L0 , vs mechanical strength, σf , of unfired castables cured and
dried at 50°C. Admixtures Influence Properties
resulted in a 3-D particle-bound ing deformation temperature (Figure The introduction of coagulant
structure. 9). This result may have been caused admixtures greatly influenced the
by the lower-temperature melting thermomechanical properties of wet
phases in the Na2O–SiO2–Al2O3–CaO shotcrete refractory castable matrix.
The refractoriness under load and Organic additives that contained
system.
creep behavior of the matrix can be sodium PAS and PAS + Alg improved
evaluated by the deformation (dL/L0) matrix performance in all properties
as a function of temperature (up to CC led to greater deformation than evaluated.
1500°C) and time (Figure 8). The did the material without additives.
results indicated that the shotcrete However, its effect was less intense
additives used here influenced these than the SS-containing samples. Commercial inorganic additives
properties significantly. Based on these results, the inorganic that promote particle agglomeration
admixtures yielded the poorest (SS and CC) decreased the mechani-
results in the RUL and creep tests. cal strength of green samples.
The addition of SS resulted in the Moreover, CC and, to a greater
greatest deformation of the castable extent, SS resulted in a higher creep
matrix. Moreover, the SS-containing HEC, a gelling additive, resulted in a and decreased the starting tempera-
samples presented the lowest start- lower creep than the inorganic ture deformation.

©The American Ceramic Society American Ceramic Society Bulletin www.ceramicbulletin.org August 2005 9205
 PAS and PAS + Alg increased the Refract. Appl., 8 [3] 15–20 (2003).
mechanical strength of green and 7D. Vasques Filho, Y.A. Marques, R.G.
prefired matrix samples. These addi- Pileggi and V.C. Pandolfelli,“Influence of
tives also promoted less creep and the Polymeric Fibers on Shotcrete
higher starting deformation temper- Refractory Castables” (in Portuguese),
atures. Additives with these coagu- Ceramica, 50, 69–74 (2004).
lant/flocculation mechanisms should 8R.G. Pileggi, F.T. Ramal Jr., A.E. Paiva and
be taken into greater consideration V.C. Pandolfelli,“High-Performance
for wet shotcreting. ■ Refractory Castables: Particle Size
Design,” Refract. Appl., 8 [5] 17–21 (2003).
9Y.A. Marques, D. Vasques Filho, R.G.
Acknowledgments
Pileggi and V.C. Pandolfelli,“Influence of
The authors are grateful to the Brazilian Additives on the Permeability and Drying
research funding agencies FAPESP and Behavior of Wet Shotcrete Refractory
CNPq. They also are grateful to ALCOA- Castables” (in Portuguese), Ceramica, 50,
Brazil and Magnesita for supporting this 7–11 (2004).
research and to D. Vasques Filho for help-
10K.H. Khayat,“Viscosity-Enhancing
ing on the experimental procedure.
Admixtures for Cement-Based Materials:
An Overview,” Cem. Concr. Res., 20,
References 171–88 (1998).
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Equations
Andreasen Packing Model5,12 Equation
CPFT = 100  (D/DL)q
where CPFT is the cumulative percentage of particles smaller than diameter D, DL
the maximum diameter (CPFT = 100% when D = DL) and q the distribution
coefficient.

Splitting Tensile Strength Equation

σf = 2F/πDh
where σf is the splitting tensile strength, F the maximum force (in newtons) applied,
D the sample diameter and h the sample height.

©The American Ceramic Society American Ceramic Society Bulletin www.ceramicbulletin.org August 2005 9206