Construction and Building Materials 59 (2014) 188–194

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Construction and Building Materials

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Geopolymer prepared with high-magnesium nickel slag:

Characterization of properties and microstructure
Tao Yang a, Xiao Yao a,⇑, Zuhua Zhang b,⇑⇑
a
Faculty of Materials Science and Engineering, Nanjing University of Technology, Nanjing, Jiangsu 210009, China
b
Faculty of Engineering and Surveying, University of Southern Queensland, Toowoomba, QLD 4350, Australia

h i g h l i g h t s

 We investigate the feasibility of using nickel slag to synthesize geopolymers.

 The performance of fly ash-nickel slag blended geopolymers was studied.
 20% nickel slag substitution favors the compressive strength development.

a r t i c l e i n f o a b s t r a c t

Article history: High-magnesium nickel slag (HMNS) is a hazardous waste that is generated in nickel pyrometallurgical
Received 21 October 2013 production. The present work investigates the feasibility of using this slag in geopolymer manufacturing.
Received in revised form 3 January 2014 The effects of HMNS addition on the reaction, mechanical properties and microstructure of fly ash-based
Accepted 6 January 2014
geopolymers are studied through isothermal conduction calorimetry (ICC), compressive strength testing,
Available online 20 March 2014
mercury intrusion porosimetry (MIP), scanning electron microscopy (SEM), X-ray diffractometry (XRD)
and drying shrinkage testing. The results showed that the major phase in fly ash-HMNS geopolymers
Keywords:
was a type of sodium magnesium aluminosilicate gel (N–M–A–S) with amorphous features. The Si/Al
Geopolymer
Nickel slag
ratio of the gel phase increased with HMNS content due to the high silica supplied by HMNS. In terms
Fly ash of compressive strength, the maximal strength of fly ash-based geopolymers was achieved by 20% HMNS
Alkaline activation substitution. At this optimal content, the sample possessed a refiner pore structure and lower linear
Drying shrinkage drying shrinkage compared with the other samples containing 0%, 40% and 60% HMNS contents. This
study shows the potential of incorporating HMNS as value source material for geopolymer production.
Ó 2014 Published by Elsevier Ltd.

1. Introduction to be hazardous or at least harmful to ground and underground

Nickel production from high-magnesium nickel oxide ore fol-
lows a pyrometallurgical process including pre-reduction, smelting
in a blast furnace and nickel enrichment-refining [1]. During the
smelting stage, besides the nickel alloy, high-magnesium nickel
slag (HMNS) with a range of oxides is produced. The HMNS is
recycled back into the process until its nickel concentration is
low to a level of quenching and grinding, and then is disposed of
in piles on site [2]. In China, the annual generation of nickel slag
is about 800,000 tonnes, only 8% of which is utilized in Portland
cement production, harbor and road construction [2–5]. The rest
is disposed of on site or by land filling, which is often considered
⇑ Corresponding author. Tel.: +86 25 83587253.
⇑⇑ Co-corresponding author.
E-mail addresses: htmpaper@sina.com (X. Yao), Zuhua.Zhang@usq.edu.au
(Z. Zhang).
water [2]. This industry requires low cost technologies to treat or
use the waste in economical and sustainable models.
Geopolymers, also known as inorganic polymers, are a class of
alkali aluminosilicate materials synthesized through the reaction
of solid aluminosilcate precursors with highly concentrated aque-
ous alkali hydroxide and/or silicate solutions [6]. They are consid-
ered as the analogues of certain zeolites but have an amorphous to
semi-crystalline three-dimensional molecular structure [7,8]. The
formula to describe the chemical composition of the materials is
Mn{(SiO2)zAlO2}nwH2O, where M is alkali cations (K+ or Na+),
n is usually called degree of polymerization, and z is Si/Al ratio
[9]. Depending on the raw material selection and processing condi-
tions, geopolymer binders exhibit a variety of performances,
including quick compressive strength development, low perme-
ability, resistance to acid attack and fire [10].
A number of raw precursors have been extensively investigated
in geopolymer production, including natural minerals (e.g.,

http://dx.doi.org/10.1016/j.conbuildmat.2014.01.038
0950-0618/Ó 2014 Published by Elsevier Ltd.
 T. Yang et al. / Construction and Building Materials 59 (2014) 188–194 189

kaolinite, either kaolin clay or heated power) and industrial wastes

(e.g., fly ash, slag) [11–15]. This technology is highly valued for the
(a)
capacity of turning waste materials into profitable products
[16–21]. Many researchers have made efforts to prepare geopoly-
mer binders with proper performances by incorporating a series
of industrial wastes, such as lead slag [22], ferronickel slag
[23–25] and red mud [26], and agriculture wastes, such as rice
husk ash [27]. HMNS provides an potential in geopolymer produc-
tion in respect of its high silica content and major amorphous
phase formed during quenching process [1,2]; however, the
feasibility has not been reported in open literature.
The aim of present work is to explore the feasibility of using
HMNS in geopolymer production. The hydration evolution heat,
compressive strength, porosity and shrinkage behavior are the 10µm
concerned subjects. The microstructure of geopolymer binders
are analyzed using SEM-EDS and XRD techniques.
(b)
2. Experimental part

2.1. Materials

The fly ash (FA) obtained from Xuzhou Guohua power station (Jiangsu, China)
can be classified as type F as per ASTM-618 [28]. The HMNS obtained from Nanjing,
China, is derived from nickel production with garnierite ore following metallurgy
process. It is a siliceous material rich in SiO2 and MgO, whereas the concentrations
of Al2O3 and CaO are much less than normal granulated blast furnace slag (GBFS)
[29]. Table 1 gives the chemical compositions of the fly ash and HMNS, as
determined by X-ray fluorescence (XRF) method. The concentrations of Cr and other
heavy metals are higher than normal slag [29], even the lead slag and ferronickel
slag [22–25].
The SEM images (Fig. 1) show the morphology of fly ash and HMNS particles. 30µm
The particle geometric properties were analyzed using a laser particle size analyzer,
as shown in Fig. 2. The mean particle sizes (d50) of the fly ash and HMNS are
14.74 lm and 21.59 lm respectively. The mineral components were investigated Fig. 1. SEM micrograph of FA (a) and HMNS (b).
using X-ray diffractograms (XRD). It can be seen from Fig. 3, the fly ash and HMNS
are basically amorphous, as reflected by the broad peaks among the range of
2h = 20–35° and 25–40°, respectively. A small amount of crystalline phases, such
as mullite (Al2.4Si0.6O4.8) and quartz (SiO2) in fly ash and forsterite ferroan (Mg1.824-
100
Percent finer by weight (%)

Fe0.176SiO4) and traces of quartz and calcium silicate (Ca2SiO4) in HMNS are fly ash
observed. HMNS
80
The alkali silicate activators were mixtures by dissolving sodium hydroxide pel-
lets (P96% purity) and a sodium silicate solution (Huaian, China, with an original
modulus Ms = 2.44) into distilled water in certain ratios to achieve Ms = 1.2–2.0 60
at constant concentration of 30 wt.% (the solid content of Na2OnSiO2, n = 1.2–
2.0). The mixtures were allowed to cool at room temperature for 24 h prior to use.
40
2.2. Synthesis of geopolymer binders
20
The fly ash and HMNS blends were dry-mixed for 5 min and then mixed with
alkali silicate activators to form geopolymer binders. The liquid/solid ratio was kept
at 0.42. This ratio gave a suitable workability. The binders were casted in two 0
moulds, with sizes of £25.4  25.4 mm and 20  20  80 mm, to measure the com- 0.1 1 10 100 1000
pressive strength and drying shrinkage, respectively. The binders were cured at
20 °C and RH > 95% in an air-conditioned fog room. As the setting times of mixtures
Particle size, D (µm)
were different, the samples were de-moulded after curing for 72 h to obtain initial
Fig. 2. Particle size distribution of fly ash and HMNS.
strengths, and continually cured to 28 days until testing. The samples with 80% and
100% HMNS were not strong enough to handle, even after 7 days of curing, so only
the mixtures with 0–60% HMNS were studied in the following sections.
condition. Once activator was injected, and mixed with the powder, the heat flow
was recorded immediately at 30 s intervals. Mercury intrusion porosimetry (MIP)
2.3. Analytical methods
was performed using a Poremaster GT-60 (Quantachrome, USA). Before testing,
the samples were crushed into small pieces. The specimens were stored in ethanol
The geopolymer binders were analyzed using a 3114/3236 TAM 83 Air isother-
for 24 h to extract free water, and then dried at 60 °C for 4 h. This relatively low
mal conduction calorimeter (Thermometric AB, Sweden) at 20 °C for 7 days by an
temperature is believed to have little effects on the pore structure. The compressive
internal mixing procedure. The solid precursor was placed in an ampoule, and
strength testing of the cylindrical samples was conducted on a WHY-200 Auto Test
activator was held separately in an injector. Both of the ampoule and injector were
Compression Machine. Drying shrinkage was tested using the cuboid specimens.
maintained in the calorimeter at the reaction temperature to a thermal balance

Table 1
Chemical compositions of fly ash and HMNS, wt.%. LOI is loss on ignition.

Oxide SiO2 Al2O3 MgO CaO Fe2O3 K2O TiO2 Na2O Cr Ni Zn LOI
Fly ash 53.00 30.58 1.25 4.57 3.81 1.43 1.08 0.52 n.d. n.d. n.d. 2.29
HMNS 52.27 6.19 26.93 8.77 4.20 0.16 0.10 0.11 0.37 0.03 0.02 n.d.
190 T. Yang et al. / Construction and Building Materials 59 (2014) 188–194

the system using 100% fly ash. However, the cumulative heat

release does not increase at a fixed rate of HMNS content. This
♥ ♥♠ ♥
♥♥ can be accounted for by the complexity of the interaction between
♠ ♥ ♣
HMNS the heat release of dissolution stage and that of polymerization
stage in the systems.
♦ mullite
♦ ♠ quartz
♥ forsterite ferroan 3.2. Compressive strength
♣calcium silicate
♠ ♦♦ ♦
♦ Fig. 6 shows the compressive strength of fly ash-HMNS geopoly-
♦
mer binders with the activator solutions in the range of Ms = 1.2–
FA 2.0. The compressive strength increases as the Ms. is increased
from 1.2 to 1.4, while further increase up to 2.0 results in decreas-
10 20 30 40 50 60 70 80 ing in compressive strength. Similar results were reported by
2-theta Maragkos et al. [23] in the synthesis of ferronickel slag-based
geopolymers. The decrease of molar ratios promotes the dissolu-
Fig. 3. X-ray diffractograms for fly ash and HMNS. Mullite (Al2.4Si0.6O4.8), PDF No.
tion of solid precursors in the aqueous phase with high alkalinity,
73-1389; quartz (SiO2), PDF No. 83-539; forsterite ferroan (Mg1.824Fe0.176SiO4), PDF
No. 88-1991; calcium silicate (Ca2SiO4), PDF No. 36-0642. and consequently the formation of polymeric binder is increased,
which make a great contribution to the increase of compressive
strength [23]. However, an excessive amount of NaOH in the
The testing age was prolonged to 120 days to obtain relatively long term data. A lowest Ms. studied here seems to inhibit the formation of
length comparator was used to measure the linear variation of the samples, along
polymeric binder, which is also reported in alkali activation of
the longitudinal axis. Linear drying shrinkage of geopolymers was calculated by
Eq. (1): ferronickel slag [23].
The 20% HMNS substitution leads to increase in the compres-
Linear drying shrinkage ¼ ðLin  Lfi Þ=75 ð1Þ sive strength by 20–40%, with the optimal one activated with
where Lin (mm): de-moulded length of each binder after curing for 72 h, Lfi (mm): Ms = 1.4. More HMNS (40% and 60%) results in a decrease. It means
measured length of each binder at different ages, 75 (mm): the effective length of that the extent of geopolymerization, either in the stage of dissolu-
each sample as casted. tion or polymerization, is not the only factor of determining the
Powder samples were prepared for XRD analysis by grinding the geopolymer
mechanical properties of geopolymers. The benefits brought by
binders followed by oven-drying at 105 °C for 6 h. The XRD analysis was conducted
on a Thermo ARL’tra machine with Cu Ka radiation at a scanning rate of 10°/min 20% HMNS should be considered in two perspectives: in geometry,
from 10° to 80° (2-theta). A ZEISS EVO MA18 scanning electron microscope (SEM) the irregular polyhedron HMNS particles which do not react com-
was used to analyze the fracture surface of samples, and to conduct elemental com- pletely will work as micro-aggregates in the fly ash-based system,
position analysis, using an equipped energy dispersive spectroscopy (EDS). Samples benefiting their strength increase or maintenance; in terms of pore
were coated with gold.
structure, a more refined structure leads to a more uniform stress
distribution under loading, and increases the compressive strength
3. Results and discussion of the samples [32]. The two perspectives will be studied in more
detail in the following sections.
3.1. ICC testing It was observed that the samples with 80% and 100% HMNS
were not able to set within 24 h and were too weak to handle after
Fig. 4 shows the heat evolution rates of geopolymer binders one week of curing. The reason is due to the extremely low reactiv-
with different HMNS contents at 20 °C in the first 168 h of reaction. ity of HMNS, although which is highly amorphous in nature. How-
In each of the curves, a sharp peak appears immediately after mix- ever, as observed in ICC data, the cumulative heat is higher in
ing, and the heat evolution rate reaches a maximum at the same HMNS-containing systems than in the 100% fly ash system. This
point of time around 30 min. This peak corresponds to a combina- is believed due to continuous activation of fly ash at these
tion of particle wetting and dissolution of solid precursors into HMNS-containing systems, in which activator is relatively exces-
silica and alumina monomers [30,31]. The maximal heat release sive. It does not exclude the possibility of different exothermic
rate of this peak decreases monotonically as HMNS content in- properties of the formation of Mg-containing gels. The chemical
creases. It implies that the HMNS particles may have lower solubil- compositions in HMNS are dominant of Si and Mg, while Al and
ity under the current activation conditions, compared with the FA Ca are not as high as normal slag. The lack of Al and Ca affects
particles, probably due to the lack of Al species in HMNS particles,
which are more readily to be dissolved than Si species [7]. After the
first dominant peak, a period of sustainable heat interchange is ob- 1.00 2.0
Peak1 0%
served, which is related to the polymerization and condensation of 0%
Heat evolution (mw/g)
Heat evolution (mW/g)

20% 20%
silica and alumina monomers into aluminosilicate oligomers [30]. 1.5
40%
0.75 40%
In contrast with the curves in the dissolution stage, the heat release 60%
1.0 60%
rate during this stage is usually higher in the systems with more
HMNS contents. There is a broad shoulder in the 20% and 40% 0.5

HMNS samples, and even a broad peak with a maximum heat re- 0.50
lease rate at the point of time around 16 h in the 60% sample. This 0.0
0 1 2 3 4 5
reveals that the HMNS particles participate in the geopolymeriza- Peak2 Reaction time (h)
0.25 40%
tion, and probably enhance the extent of polymerization. Further 20% 60%
discussion on this point combined with other measurements will
be presented later in this paper. 0%
0.00
The heat release during the polymerization stage exhibits a 0 42 84 126 168
desired trend as reflected by the cumulative heat release of geopo- Reaction time (h)
lymerization in the first 168 h, as shown in Fig. 5. The HMNS
substitution leads to a higher total heat release, compared with Fig. 4. Effects of HMNS content on heat evolution rate of geopolymerization.
 T. Yang et al. / Construction and Building Materials 59 (2014) 188–194
50
60%
40
Heat release (J/g)
20%
40%
30
0%
20
10
0
0 30 60 90 120
Reaction time (h)
Fig. 5. Effects of HMNS content on cumulative heat release of geopolymerization.
80
Compressive strength (MPa)
60
40
20
0 angular HMNS particles are surrounded and bonded with the gel
0 20% 40%
Slag (wt.%)
Fig. 6. Compressive strength (±5%) for geopolymer binders.
the geopolymerization of Si to form aluminosilicate gels and cal-
cium silicate hydrates, which are two major contributors of
strength development [7]. In order to utilize HMNS more effec-
tively and produce FA-HMNS geopolymers with high compressive
strength, further research is recommended to produce geopoly-
mers by mixing HMNS with other aluminosilicate solid precursors,
such as high calcium fly ash. The high calcium fly ash will lead to
higher dissolution of precursor, more rapid hardening process,
and usually higher compressive strength than low calcium fly
ash [15,35].
3.3. Pore size distribution
Fig. 7 shows the pore size distribution and porosity of geopoly-
mer binders activated with Ms = 1.4. The curve of 100% fly ash bin-
der presents dominant pore diameters between 10 nm and
100 nm. Its maximal distribution at diameters of around 27 nm
and the pores in the mesopores interval 10–50 nm account for
80% frequency of total porosity. This curve is different from the
bimodal profile of the pore size distribution as observed in alkali
activated fly ash cured for 28 days, where pores are respectively
located at 100 and 1000 nm [21,33]. It indicates that the large
capillary pores (around 100–1000 nm) are space-filled by the
aluminosilicate gels, and thus there is only one peak in the binders
with a denser pore structure developed.
All of the curves of the alkali-activated fly ash-HMNS blends
present unimodal profiles with pore sizes range from 10 to
300 nm. The diameters of distribution-maximal pores increase
from 24 to 64 nm as HMNS content increases, meanwhile the total
porosity decreases. It means that when more HMNS is used, the to-
191
tal volume of pores in the geopolymer binders turns to be lower,
while more macropores (>50 nm) are formed. This is different from
the effects of granulated blast furnace slag on the pore structure of
fly ash-based geopolymer. Provis et al. [34] found that the high-cal-
cium slag addition could not only provide an overall porosity
reduction but also a pore refinement effect. The presence of more
bound water within the C–(A)–S–H gel predominantly formed in
the slag-rich geopolymer systems would lead to more pore-filling
capacity for the pore structure of binders. However, in this work
HMNS particles will supply silica during the dissolution stage for
the reaction system. The silicate ingredients appear to be helpful
of forming more aluminosilicate gels with lower bond water con-
150 180 tent in the geopolymers. The connectivity degree of the binders
is supposed to be improved [35], and some mesopores will be filled
with these reaction products, resulting in a decrease of porosity for
the binders. Nevertheless, the reaction will compensate the pore
solution bonded with the aluminosilicate gels.
It is interesting to note that the amount of maximum pores and
total porosity of 20% HMNS geopolymer binders are a bit lower
than those of the 100% fly ash binders (Fig. 7). HMNS particles work
as micro-aggregate in the fly ash-based system, resulting in a
refinement for the pore structures of the samples and the positive
1.4 influences on their mechanical properties. This is consists with the
1.2 compressive strength testing results.
1.6 3.4. Microstructure
The microstructure of the geopolymer binders activated with
2.0 Ms = 1.4 are presented in Fig. 8. The residue fly ash particles and
60% phase. Microcracks and pores due to ash hollows are observed,
but none of the crystalline phases is identified. It is evident that
the microstructure of 20% HMNS geopolymer is more compact
than the one only with fly ash.
The Si/Al ratio of gel phases, as determined by SEM-EDS tech-
nique, increases from 1.34 to 3.50 as HMNS content increases from
0% to 60%, shown in Table 2. This suggests that quantities of silicate
species supplied by HMNS will participate in the geopolymeriza-
tion to influence the component and microstructure of the gel
phase in reaction products, resulting in the decrease of porosity
and presence of more large gel pores in the binders.
3.5. XRD analysis
Fig. 9 plots the XRD patterns of 60 days-aged geopolymer bind-
ers activated with activator Ms = 1.4. In the 100% fly ash binder, the
major X-ray crystalline phases are mullite and quartz contributed
by the unreacted fly ash. Minor calcite is also detected, due to
the carbonation on the surface of the products under atmospheric
conditions. The broad peak from 20° to 35° 2h in fly ash is broad-
ened to 40° after sodium silicate activation, with the intensity
shifting to higher angel. This is well known as an indication due
to the formation of geopolymeric gels [7,36].
The intensity of the peaks for forsterite ferroan, which is con-
tributed by the unreacted HMNS, presence in the fly ash-HMNS
geopolymers increases as the HMNS substitution increases. It indi-
cates that the crystalline phase is relatively stable during the geo-
polymerization process, unlike the iron-containing phases in
ferronickel slags [25]. Meanwhile, the intensity of the peaks related
to mullite and quartz due to uncreated fly ash decreases with the
incorporation of HMNS. The peaks of trace calcium silicate inden-
tified in HMNS disappear after geopolymerization. This suggests
the dissolution of this crystalline phase under highly alkaline
conditions. Semi-crystalline to crystalline zeolitic phases, which
are detectable in the geopolymerization system of a class of low
calcium ferronickel slags [23,25], have not been detected in the
192 T. Yang et al. / Construction and Building Materials 59 (2014) 188–194

(a) 0.3 Mesopores Macropores (b) 20

-dV/d(logD) (×10-3 cm3· μm-1 )

Macropores
27 nm Large mesopores
16
0

Porosity (%)
0.2 20%
40% 12
24 nm
42 nm 60%
8
0.1
64 nm
4

0.0 0
10 100 1000 0 20% 40% 60%
Pore size-diameter (nm) Slag (wt.%)

Fig. 7. Pore size (a) and porosity distribution (b) of geopolymer binders using different HMNS contents and Ms = 1.4.

Table 2
(a) Si/Al molar ratios of gel phase in the binders. (The values are obtained through
averaging molar ratios of Si and Al in gel phase within two areas for each binder).

F Slag contents (%) Samples Si Al Si/Al Average value

0 1 17.36 19.93 0.87 1.34
2 26.53 14.53 1.81
20 1 25.02 11.37 2.20 2.07
2 24.56 12.66 1.94
40 1 22.37 7.82 2.86 3.34
2 26.94 7.04 3.81
60 1 15.72 4.21 3.73 3.50
G 2 22.76 6.96 3.27

10 µm
♠ ♦mullite ◊ calcite
♠quartz ♥forsterite ferroan
(b) ♦
♠♥♥ ♦ ♦♦♥ ♦ ♦ ♦
60%

F
40%
H

20% ♠
G ♦
♦ ♠ ◊ ♦ ♦♦ ♦
0% ♦ ♦

10 20 30 40 50 60 70 80
2-theta
10 µm
Fig. 9. X-ray diffractograms for geopolymer binders with different HMNS contents.
Mullite (Al2.4Si0.6O4.8), PDF No. 73-1389; quartz (SiO2), PDF No. 83-539; calcite
Fig. 8. SEM image for fracture section of geopolymer binders with different HMNS (CaCo3) PDF No. 05-0586; forsterite ferroan (Mg1.824Fe0.176SiO4), PDF No. 88-1991.
contents: (a) 0% and (b) 20%. (F-fly ash particles, H-HMNS particles, G-gel phase
formed.)

required [25]. In addition, Mg(OH)2 crystalline products, which will

FA-HMNS binders. This is probably due to the room temperature
curing – hydrothermal curing is beneficial to obtaining crystalline
phases [15]. The major products formed in alkali-activated fly
ash-HMNS are a type of amorphous gel phase, also inferred by
the broad peak of 2h = 20–40°. In conjunction with the SEM-EDS
analysis, the gel phase is sodium magnesium aluminosilicate gel
(N–(M)–A–S), which is different from the products formed in
alkali-activated a single fly ash [9,17], or single GBFS [14,31,32].
In order to identify the influence of HMNS addition on the specific
molecular structures of geopolymers, mainly the Si–O–Si(Al) bonds
that reflect the extent of polymerization, further infrared spectros-
copy (IR) study and nuclear magnetic resonance (NMR) are
cause undesired expansion to the structure [37], is not detected in
the binders. This means that the HMNS may not be able to provide
enough reactivity to generate expansion in geopolymerization.
3.6. Drying shrinkage
Fig. 10 plots the linear drying shrinkage of geopolymer binders
cured at 20 °C and 90% RH. The drying shrinkage behavior takes
place mainly in the early ages (before 28 days). The increase of
SiO2/Na2O ratio from 1.2 to 2.0 in the activators results in a 2–4
times higher drying shrinkage, due to the large shrinkage nature
of silica gels of the sodium silicate solutions [38].
 T. Yang et al. / Construction and Building Materials 59 (2014) 188–194 193

1.6

Drying shrinkage mm/mm (10-3 )

Drying shrinkage mm/mm (10-3 )
1.6
(a) Ms=1.2 (b) Ms=1.4

1.2 1.2

0.8 0.8

0
20%
0.4 0 0.4 40%
20%
60%
40%
60%
0.0 0.0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Age (days) Age (days)

2.4 8
Drying shrinkage mm/mm (10-3 )

Drying shrinkage mm/mm (10-3 )

(c) Ms=1.6 (d) Ms=2.0

1.8 6 0
20%
40%
60%
1.2 4

0
0.6 20% 2
40%
60%
0.0 0
0 20 40 60 80 100 120 0 20 40 60 80 100 120
Age (days) Age (days)
Fig. 10. Linear drying shrinkage of geopolymers: (a)–(d) present the effects of HMNS contents on drying shrinkage of the samples prepared with different activators, Ms = 1.2,
1.4, 1.6 and 2.0.

The linear drying shrinkage of 120-day cured geopolymer bind- explained in other perspectives. The HMNS has processed
ers activated with Ms = 1.2, is in the range of 0.7–1.5  103 mm/ 1400 °C calcination, so the large amount of magnesium in HMNS
mm, which is much lower than 1–9  103 mm for alkali activated cannot work as an MgO-based expansive agent. This is confirmed
granulated blast furnace slag binders under similar reaction condi- by the XRD analysis. As shown in SEM images, the residual HMNS
tions [32,38]. It is probably attributed to two reasons: (1) lower particles work as micro-aggregates to fill into the macropores, and
degree of polymerization for high-calcium slag [39]; and (2) the the shrinkage of geopolymer binders will be restricted with HMNS
difference between the shrinkage natures of geopolymeric substitution. However, when too much HMNS is used, the shrink-
products for two systems. The alkali-activated GBFS is well known ing nature of high Si/Al gels overcomes the beneficial influence of
to produce C–S–H gels [14,31,32], while the products here are micro-aggregate effect.
N–(M)–A–H gels with frame structure.
It is interesting to note that only 20% HMNS addition leads to a 4. Conclusions
decrease in drying shrinkage for the fly ash-based geopolymer
binders, prepared with different activators Ms = 1.2–2.0. This is in An industrial solid waste HMNS generated by pyrometallurgical
consistent with the variation tendency in pore structures of the production of nickel is attempted in the manufacture of fly
geopolymer binders activated with Ms = 1.4. The drying shrinkage ash-based geopolymers through geopolymerization technique.
of geopolymers takes place and relates to the evaporation of free The major products formed in the binders are a class of sodium
water from macropores and mesopores [38]. The 20% HMNS magnesium aluminosilicate gels (N–(M)–A–S). The HMNS substi-
geopolymer binders possess a refiner porous structure and lower tution can provide a large number of silicate ingredient for the
total porosity, compared with the matrix of 100% fly ash geopoly- fly ash-based geopolymer, and thus the Si/Al ratio of the gel phase
mer. When the 20% samples are exposed to drying environment, increases with HMNS content. HMNS particles can work as mico-
the evaporation rate of water from their mesopores and macrop- aggregates in geopolymer binders. The total volume of pores in
ores is slower. This is helpful of keeping a relative higher humidity the geopolymer binders turns to be lower and more macropores
of the pores in the matrix, and lower capillary tension and contrac- are formed as the content of HMNS increases. When the molar
tion force in the pores [38]. In the 40% and 60% HMNS binders, a ratio of activator solutions is in the range of 1.2–2.0, the optimal
large number of macropores are formed, even though the total vol- dosage of HMNS is 20%, resulting in the highest compressive
ume of pores in the binders is small. The evaporation of free water strength and the lowest linear drying shrinkage. These perfor-
from numerous macropores causes an increase drying shrinkage. mances correlate well with the most refined pore sizes and more
The effects of pore structure on the shrinkage behavior of alkali compact microstructure in geopolymer binders compared to non-
activated fly ash-HMNS blends show significant similarity to those and more HMNS systems. Because of the high temperature of pyro-
in activated GBFS cement system [32,38]. metallurgical process, the HMNS is much less active than normal
Despite the role of the pore structure, the influence of HMNS MgO-based expansive agent, thus will not trigger the volume
addition on the shrinkage behavior of geopolymers can be stability problem of fly ash-based geopolymers.
194 T. Yang et al. / Construction and Building Materials 59 (2014) 188–194
Acknowledgements
The authors acknowledge the financial support of the Jiangsu
Higher Education Institutions for a project PAPD (Priority
Academic Program Development). Program for Changjiang Schol-
ars and Innovative Research Team in University (PCSIRT,
IRT1146) and Graduate Education Innovation Project in Jiangsu
Province (CXLX13_409) are also appreciated. The work by Zhang
is supported by University of Southern Queensland and an
ARC-linkage project.
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