J. Cent. South Univ. Technol.

(2009) 16: 09140918

DOI: 10.1007/s117710090152x

Preparation and properties of geopolymer-lightweight
aggregate refractory concrete

HU Shu-guang ()
1
, WU Jing ( )
1
, YANG Wen ( )
2
, HE Yong-jia ()
1
,
WANG Fa-zhou ()
1
, DING Qing-jun ()
1


(1. Key Laboratory for Silicate Materials Science and Engineering, Ministry of Education,
Wuhan University of Technology, Wuhan 430070, China;
2. China Construction Ready Mixed Concrete Co. Ltd., Wuhan 430074, China)


Abstract: Geopolymer-lightweight aggregate refractory concrete (GLARC) was prepared with geopolymer and lightweight
aggregate. The mechanical property and heat-resistance (950 ) of GLARC were investigated. The effects of size of aggregate and
mass ratio of geopolymer to aggregate on mechanical and thermal properties were also studied. The results show that the highest
compressive strength of the heated refractory concrete is 43.3 MPa, and the strength loss is only 42%. The mechanical property and
heat-resistance are influenced by the thickness of geopolymer covered with aggregate, which can be expressed as the quantity of
geopolymer on per surface area of aggregate. In order to show the relationship between the thickness of geopolymer covered with
aggregate and the thermal property of concrete, equal thickness model is presented, which provides a reference for the mix design of
GLARC. For the haydite sand with size of 1.184.75 mm, the best amount of geopolymer per surface area of aggregate should be in
the range of 0.3000.500 mg/mm
2
.

Key words: refractory concrete; geopolymer; lightweight aggregate; thermal property; equal thickness model



1 Introduction

Refractory concrete is suitable for using at high
temperature (200 ) and is composed of refractory
cementing material, heat-resistant aggregate and/or
fillers, which can maintain the necessary physical and
mechanical properties at high temperature for long
term[12]. Refractory concretes, according to different
cementing materials, can be divided into Portland
refractory concrete, aluminate refractory concrete,
phosphate refractory concrete, sulphate refractory
concrete, bauxite refractory concrete, chloride refractory
concrete, sols refractory concrete and organic
refractory concrete[3]. Heat-resistant aggregate can be
divided into broken fire-resistant clay brick, clay, clinker,
broken high-alumina brick, natural light aggregate
(pumice and tuff), industrial wastes (slag, lytag and
gangue), and artificial light aggregate (shale haydite, clay
haydite and expand perlite)[45].
Refractory concrete can be used for the building
engineering with fire incipient fault or in
high-temperature work environment. With the
development of new building structure and new
technology, much better properties of concrete are
demanded. Some concretes of the building structure
should be of high-strength and heat-resistant
characteristics. Many experimental researches on the
mechanical and thermal behavior of concrete at constant
high temperatures have been reported[69].
NEVILLE[10] pointed out that at temperatures
approximately above 430 , concretes with siliceous
aggregate show a significant strength loss compared to
those with lightweight aggregate. At 600 , concrete
can lose half of its strength. Above 800 , loss of the
bound water in the hydrates may cause a strength loss of
80%, which may lead to the failure of a structure.
In Ref.[11], fire resistance of lightweight concretes
having a unit weight of 5001 600 kg/m
3
was inves-
tigated. It was found that an increase in unit weight
resulted in a reduction in the fire resistance of the
concretes.
TURKER et al[4] investigated the micro-structure
and strength of concretes exposed to fire. In their studies,
mortars containing ordinary Portland cement and three
types of aggregates were respectively subjected to 100,
250, 500, 700 and 850 for 4 h. Unlike the mortars
with quartz and limestone, at high temperatures, crack
was observed in the aggregate for the mortars with
pumice instead of crack propagation at the interface.
Therefore, it was concluded that the interface was strong
when pumice was used[12].

Foundation item: Project(2009CB623201) supported by the National Basic Research Program of China; Project(G0510) supported by the Key Laboratory
for Refractories and High-temperature Ceramics of Hubei Province, China
Received date: 20090106; Accepted date: 20090609
Corresponding author: WU Jing, PhD; Tel: +8613476233919; E-mail: wujing313@whut.edu.cn
J. Cent. South Univ. Technol. (2009) 16: 09140918 915

According to KONG et al[12], ABELES and
BARDHAN-ROY[13], concretes containing lightweight
aggregate preserve their strength up to nearly 500 . It
was stated that the residual strength of LWC after fire
decreases linearly from 100% to 40% as a result of
increasing the temperature from 500 to 800 .
Inorganic alkali aluminosilicate polymers,
commonly referred to as geopolymer, are alumino-
silicate materials that exhibit good physical and chemical
properties and a wide range of potential applications,
including precast structures and non-structural elements,
concrete pavements and products, containment and
immobilisation of toxic, hazardous and radioactive
wastes, advanced structural tooling and refractory
ceramics, and fire-resistant composites used in buildings,
aeroplanes, shipbuilding, racing cars, and the nuclear
power industry[1418]. Because of its characteristics of
lightweight, low thermal conductivity and heat-resistance,
lightweight aggregate was widely used in the preparation
of refractory concrete[1920]. Geopolymer and haydite
have good heat-resistance, so they could be compounded
to form a new kind of refractory concrete that should
have excellent mechanical and fire-resistance properties.
However, so far there have been few reports.
In this work, the geopolymer-lightweight aggregate
refractory concrete (GLARC) was prepared using
geopolymer as binding matrix and haydite as aggregate,
and its mechanical performance and resistance to
elevated temperature were investigated. The effects of
aggregate size and the ratio of geopolymer to aggregate
on the performance of the concrete were also discussed.
In order to show the relationship between the thickness
of geopolymer covered with aggregate and the thermal
property of concrete, an equal thickness model was
proposed, which could provide a reference for the mix
design of GLARC.

2 Experimental

2.1 Raw materials
The aluminosilicate mineral used was metakaolin
(MK) clay, which was produced from the decomposition
of kaolinite clay burned at 700 for 6 h. The surface
area of the MK was 2224 m
2
/g. Table 1 lists the
chemical composition of MK. The alkali-activator used
in this work was a mixture of water glass (soluble
sodium silicate), sodium hydroxide (NaOH) and water.
The modulus (m(SiO
2
)/m(Na
2
O)) of water glass was 3.19
and Baume degree was 39.2. Water glass was adjusted to
the required m(SiO
2
)/m(Na
2
O) by adding 98% pure
NaOH pellets and Baume degree by adding distill water.

Table 1 Chemical composition of MK(mass fraction, %)
SiO
2
Al
2
O
3
Fe
2
O
3
CaO MgO TiO
2
Loss
63.06 28.93 2.29 0.37 0.68 0.56 0.135
Lightweight aggregate: the shale haydite was
obtained from the Guangda Haydite Development Ltd,
Hubei province, China. Table 2 lists its main
performance. The shale haydite was broken by the jaw
crusher, and the crushed aggregate was sieved into two
grain size groups of 1.182.36 mm and 2.364.75 mm,
denoted them as S and L respectively. S and L with equal
quantity were mixed to obtain sand M with size of
1.184.75 mm.

Table 2 Parameters of shale haydite
Water-absorbing
capacity/%
Grain
size/
mm
Stacking
density/
(kgm
3
)
Apparent
density/
(kgm
3
0.5 h 1.0 h 24 h
Cylinder-mould
strength/MPa
515 750 1 487 2.6 4.5 5.4 8.8

2.2 Experimental methods
NaOH, sodium silicate solution, and water were
mixed in a beaker to form the alkali-activated solution
(water-glass) with mole ratio of SiO
2
to Na
2
O being 1.2
and the mass fraction of 40%, and cooled down to room
temperature. The alkali activator and MK were combined
to produce a mixture of molasses-like consistency at a
mass ratio of liquid to powder being 0.7 and then beaten
up with the haydite sand and dried at 105 for 24 h
according to the ratios given in Table 3. The admixture
was transferred into 51 mm51 mm51 mm steel
moulds at 5 MPa. After 1 d, the specimens were
demolded and sealed by a plastic bag to prevent water
evaporation, and then cured at a temperature of
(201) for 28 d. Compressive strength was tested by
a hydraulic material testing system (MTS) according to
ASTM C109 80. The cross-head speed was 1.27
mm/min.

2.3 Measurement of heat-resistance property
The specimens were dried at 65 for 24 h in a
vacuum drying oven, and then heated to 950 at a
speed less than 150 /h , holding for 30 min. The power
supply was switched off and the specimens were
naturally cooled to room temperature in the oven. By
comparing the compressive strength of unheated and
heated specimens, the strength loss rate was calculated
according to: =
1
2 1
) (
P
P P
100%[21], where P
1
and P
2

were initial and residual compressive strengths
respectively. From the data obtained, thermal property
and its influencing factors of GLARC were investigated.

3 Results and discussion

As indicated in Table 3, the initial compressive
strength of pure geopolymer is the highest. However, that
of GLARC decreases by the addition of haydite sand.
This can be contributed to the lower strength of haydite
J. Cent. South Univ. Technol. (2009) 16: 09140918 916

Table 3 Mix proportion and test results of specimens
Speciment
No.
Grain size
of haydite sand/mm
Mass ratio of gel
to haydite sand
Initial compressive
strength/MPa
Residual compressive
strength/MPa
Strength loss rate/%
MK 90.1 20.5 77
L1 2.364.75 1.01.5 79.4 29.4 63
L2 2.364.75 1.02.0 73.6 34.7 53
L3 2.364.75 1.02.5 67.9 38.9 43
M1 1.184.75 1.01.5 82.6 33.8 59
M2 1.184.75 1.02.0 75.3 43.3 42
M3 1.184.75 1.02.5 27.4*
S1 1.182.36 1.01.5 85.4 40.1 53
S2 1.182.36 1.02.0 8.7*
S3 1.182.36 1.02.5
Note: * denotes that moulding is difficulty; denotes that moulding is impossible.

sand and the weaker interface transition zone between
gel and aggregate.
After being exposed to 950 , the residual strength
of pure geopolymer is the lowest, only 20.5 MPa, and the
strength loss rate is as high as 77%. On the one hand, the
mechanical syneresis of geopolymer occurs when the
geopolymer is heated, resulting in the decrease of its
strength; on the other hand, the moisture and bound
water in geopolymer transform into vapor when they are
heated, and the vapor pressure destroys the matrix. The
residual strength of specimen M2 is the highest.
Specimens L3, M2 and S1 have better high-temperature
mechanical property. Specimens M3, S2 and S3 cannot
sustain any load at all due to the severe deterioration
when they are heated, because less quantity of gel cannot
strongly bond the aggregate together. Thus, the grain size
of haydite sand and the ratio of gel to haydite sand affect
the mechanical and thermal properties of GLARC (see
Figs.1 and 2).

3.1 Effect of mass ratio of gel to sand on compressive
strength and heat-resistance property
It can be seen from Fig. 1 that, when the size of
sand is kept constant, the original and residual strengths
of GLARC show different development trends: the


Fig.1 Compressive strength and strength loss rate of concrete
with different mass ratios of gel to sand(size of sand is
2.364.75 mm)


Fig.2 Compressive strength and strength loss rate of concrete
with different sizes of sand at mass ratio of gel to sand being
1.01.5

strength of GLARC decreases with the increase of the
aggregate content due to the intrinsic low strength of
haydite sand. But after being heated at 950 , the
residual strength of GLARC increases by reducing the
mass ratio of gel to sand because the moisture and bound
water in geopolymer transform into vapor when the
specimen is heated, and the vapor tries to release[21].
However, there are no channels in the denser geopolymer
paste, water vapor cannot be released and finally the
system is destroyed when the vapor pressure reaches the
limit. This phenomenon is called as vapor effect. The
haydite sand is a porous material that can form a lot
of holes in the matrix, thus providing a room for the
release of vapor pressure. The number of the holes and
channels increase with the content of haydite sand.

3.2 Effect of grain size on compression strength and
thermal property
It can be seen from Fig.2 that, when the mass ratio
of gel to sand is 1.01.5, the initial strength and residual
strengths of GLARC increase with the decrease of sand
size, and the strength loss rate decreases gradually. When
the mass ratio of gel to sand is kept constant, the specific
surface area increases with the decrease of the sand size,
so the thickness of geopolymer per unit surface of
J. Cent. South Univ. Technol. (2009) 16: 09140918 917
aggregate is thinner, and the vapor can be released more
easily. But if the amount of geopolymer is small enough,
it cannot bond the aggregate together firmly.
As a matter of fact, besides the damage from the
vapor effect, the difference in coefficient of thermal
expansion between the geopolymer and shale haydite
results in the crack in the interface zone, so that the
strength declines significantly. This concept is known as
the thermal inconsistency of the ingredients[2223].

3.3 Equal thickness model
In fact, if the mass ratio of gel to sand is too low, or
the grain size of haydite sand is too small, there will not
be enough gel to fill the gap among aggregates.
Consequently, the macroporous three-dimensional
structure of GLARC forms, as shown in Figs.3 and 4.
Just because of the unique porous structure, the
GLARC is of good fire resistant property. When it is
heated, the bound water in geopolymer is converted into
vapor, which is released into the pores of aggregate and
structure, thereby the damage to GLARC is mitigated.
This is the reason why the refractory property of porous
structure GLARC is better than that of the denser system.
The mass of geopolymer covering the surface of the

Fig.3 Porous structure of GLARC

Fig.4 Illustration of test sample with porous structure:
(a) Actual picture; (b) Detail view
aggregate can be expressed as the thickness of
paste.Changing the aggregate size or the mass ratio of
gel to sand is to change the thickness of geopolymer that
covers the surface of aggregate. In order to study the
effect of the thickness of geopolymer on the
heat-resistance property of GLARC, the concept of equal
thickness model is presented, that is, the mortar that
wrapps each sand is of the same thickness, or the mortar
per surface area of aggregate is of the same quantity. And
the samples with the same mortar thickness on the
surface of aggregate are assumed to possess similar
property. The quantity of geopolymer can be expressed
as the quantity of metakaolin. In order to facilitate the
calculation, it is feasible to express the geopolymer
thickness wrapped aggregate by the metakaolin quantity
on per surface area of aggregate.
Equal thickness model is a kind of imaginary
condition, so the following two assumptions are put
forward.
(1) The aggregate is in the form of balls with the
same size, and the average diameter is D.
(2) Sand is located in the 40 mm40 mm40 mm
cube space in accordance with the simple cubic
accumulation, that is, a D-diameter ball is put in a D-D
cube.
So the mass of geopolymer wrapped per surface of
haydite sand can be calculated as follows:
4000 6

4000 6

40 40 40
2
3
2
xD
D
D
x
D
V
x
Ns
x
S
x
h
=

= = =
(1)
where D is the average grain size of aggregate, mm; s
is the average surface area of aggregate, mm
2
; V is the
average volume of aggregate, mm
3
; N is the number of
aggregate in every cube (40 mm40 mm40 mm); S is
the total surface area of all aggregate in every cube; x is
the metakaolin consumption in every cube, g; and h is
the quantity of geopolymer that covers per unit surface of
shale haydite sand, mg/mm
2
.
The quantity of every material is noted accurately
during testing, so the value of x is known, and h can be
calculated by Eq.(1). The results are given in Table 4.
It can be seen from Table 4 that, h values of
specimens L3, M2 and S1 are similar, which are equal to
0.356, 0.334 and 0.351 mg/mm
2
respectively. Obviously,
the thicknesses of geopolymer that wraps aggregate of
these three samples are approximately equal, and the
compressive strength and refractory properties are better
than those of other samples. But when h0.270 mg/mm
2
,
for specimens M3, S2 and S3, compressive strengths are
very low, even losing the sustaining capacity after being
exposed to 950 . When h>0.450 mg/mm
2
, for
specimens L2 and L1, their initial compressive strengths
J. Cent. South Univ. Technol. (2009) 16: 09140918 918
are higher, but the residual strengths are lower and
strength loss rates are higher. So, h has an optimal bound.
When it is in the range of 0.3000.500 mg/mm
2
, the
relevant samples possess better refractory property.

Table 4 Quantity of geopolymer wrapped per unit surface of
shale haydite sand
Specimen
No.
Minimum
grain
size/mm
Maximum
grain
size/mm
D/mm x/g
h/
(mgmm
2
)
L1 2.36 4.75 3.555 39.5 0.699
L2 2.36 4.75 3.555 31.8 0.563
L3 2.36 4.75 3.555 20.1 0.356
M1 1.18 4.75 2.663* 32.7 0.433
M2 1.18 4.75 2.663* 25.2 0.334
M3 1.18 4.75 2.663* 19.3 0.256
S1 1.18 2.36 1.770 40.0 0.351
S2 1.18 2.36 1.770 30.1 0.265
S3 1.18 2.36 1.770 21.0 0.185
Note: * denotes moulding is difficulty; denotes
moulding is impossible.

4 Mix design of GLARC

Compared with ordinary concrete, there is no
recognized mix design method of refractory concrete due
to the uncertainty of raw materials and service
environment. For the GLARC, the mix design can be
based on the equal thickness model, according to the
value of h in Table 4 and the experience accumulated in
the course of experiment. For haydite sand with size of
1.184.75 mm, the optimal quantity of geopolymer on
per surface area of aggregate should be in the range of
0.3000.500 mg/mm
2
, which can be used as a referenced
index of mix design of GLARC. Of course, the
optimized mix design method for GLARC needs to be
more carefully studied in the future experiments.

5 Conclusions

(1) Geopolymer-lightweight aggregate refractory
concrete (GLARC) prepared with geopolymer and
lightweight aggregate possesses excellent heat-resistance
property, and the grain size of haydite sand and the mass
ratio of gel to sand both have an effect on the mechanical
and thermal properties of this composite material.
(2) The thickness of geopolymer that covers the
surface of aggregate is the main factor influencing the
heat-resistance property of GLARC. If it is too thick, the
vapor will destroy the structure when it is released; and if
it is too thin, the gel cannot bond the aggregate together
firmly. In fact, changing the aggregate size and the mass
ratio of gel to sand is to change the thickness of paste.
(3) Equal thickness model presented can be used to
investigate the relationship between the thickness of
geopolymer and the heat-resistance property of GLARC
effectively, and provide a reference for the mix design of
GLARC. For haydite sand with size of 1.184.75 mm,
the optimal quantity of geopolymer on per surface area
of aggregate should be in the range of 0.3000.500
mg/mm
2
.

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