Cement and Concrete Research 106 (2018) 12–22

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Cement and Concrete Research

journal homepage: www.elsevier.com/locate/cemconres

Application of organic- and nanoparticle-modified foams in foamed T

concrete: Reinforcement and stabilization mechanisms
⁎
Wei Shea, , Yi Dua, Changwen Miaoa, Jiaping Liua, Guotang Zhaob, Jinyang Jianga,
Yunsheng Zhanga
a
Jiangsu Key laboratory for Construction Materials, Southeast University, Nanjing 211189, China
b
China Railway Corporation, Beijing 100844, China

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, an ultra-stable foam used for foamed concrete was fabricated by modifying the gas–liquid interface
Foamed concrete by coupling the effects of an organic surfactant and nanoparticles. A serial of techniques was employed to study
Ultra-stable foam the products and microstructure development of foam and foamed concrete, respectively. The results show that
Nanoparticle modification nano-silica and hydroxypropyl methylcellulose can slow the coalescence and disproportionation of the bubbles
Reinforcement
by adsorbing at the air bubble surface and increasing the viscosity of cell wall paste, thus preventing gas transfer
Stabilization mechanism
and hindering physical drainage between the gaseous and liquid phases. Also, a more homogeneous and finer
pore structure is generated with the inclusion of the organic surfactant and nanoparticles. The pozzolanic re-
action between the nano-silica and Ca(OH)2 results in an increased C-S-H content and the densification of the cell
wall structure. In addition, the stability of foamed concrete with modification and relevant stabilization me-
chanisms were also investigated.

1. Introduction
Aqueous foams are widely used in various applications ranging from
food, detergents, cosmetics, fire extinguishers, mineral floatation, to
material production [1,2]. Moreover, foams are commonly used in
engineering as intermediate structures in the preparation of porous
thermally insulating or lightweight materials. Foamed concrete is such
a lightweight porous material, with a porous structure produced by
introducing pre-manufactured aqueous foam into the cement or mortar
paste. The advantages of using foamed concrete in insulation and filling
applications are its low density, self-leveling ability, low cost, low
thermal conductivity, and fire-resistant properties [3–5]. Normal
foamed concrete can be designed to possess a plastic density of
500–1600 kg/m3, and ultra-low density foamed concrete is regarded to
have a plastic density of ≤500 kg/m3. However, a great variety of re-
search and engineering experience has shown that low-density foamed
concretes are more likely to be unstable. Fig. 1 shows an on-site ex-
ample of the instability of foamed concrete happened in the London.
Furthermore, this instability is almost inevitable at very low densities
(≤300 kg/m3) [6–8]. The unstable nature of foamed concrete sig-
nificantly limits its application.
The total porosity of foamed concrete is proportional to the amount
of gas incorporated into the cement-based suspension medium during
the foaming process. The pore size, however, is determined by the
stability of the wet foam before setting takes place. Wet foams are
thermodynamically unstable systems that undergo continuous Ostwald
ripening and coalescence processes, which decrease the overall free
energy of the porous system [2,9]. These destabilization processes
significantly increase the size of the incorporated bubbles, resulting in
large pores in the final cellular microstructure. Therefore, the most
critical issue in direct foaming methods is the approach used to stabilize
the air bubbles incorporated within the initial suspension or liquid
medium. Following previous reports in the literature [10–16], the in-
stability can be partially prevented by using colloidal particles; these
adsorb at the air bubble surface and reduce the interfacial energy
[10,11]. Furthermore, foam formation and stabilization are favored by
increasing the concentration and decreasing the size of the particles in
the initial suspension, which reduce the time required for the particles
to diffuse and adsorb at the air bubble surface [12,13,16].
In this paper, a novel stable aqueous foam was first fabricated by
modifying the gas–liquid interface through coupling the effects of or-
ganic surfactants and nanoparticles. Tests were carried out to study the
preparation and stability of the novel modified foams and resulting
foamed concretes, respectively. Optical microscopy (OM), scanning
electron microscopy (SEM), X-ray diffraction (XRD), and X-ray com-
puted tomography (XCT) were employed to study the composition of

⁎
Corresponding author.
E-mail address: weishe@seu.edu.cn (W. She).

https://doi.org/10.1016/j.cemconres.2018.01.020
Received 5 July 2017; Received in revised form 17 January 2018; Accepted 22 January 2018
Available online 03 February 2018
0008-8846/ © 2018 Elsevier Ltd. All rights reserved.
W. She et al. Cement and Concrete Research 106 (2018) 12–22

Fig. 1. On-site example of the instability of foamed concrete.

Table 1
Molecular parameters of the selected hydroxypropyl methylcellulose. Fig. 3. Close-view photograph of the X-ray computed tomography system.

Admixture Molecular weight/g·mol−1 POOH/% OCH3/%

HPMC 200,000 11.75 26.5 100

Table 2 80
Physical and chemical characteristics of the cementitious materials: Portland cement
(PC), fly ash (FA), and silica fume powder (SF).
Drainage/wt%

Normal foam
60
Property PC FA SF 0%NS/0.5%HPMC
1%NS/0.5%HPMC
Oxide composition/% by mass 40 3%NS/0.5%HPMC
CaO 63.26 7.62 0.88 5%NS/0.5%HPMC
SiO2 19.45 48.3 96.6
Al2O3 4.40 28.7 0.38
Fe2O3 2.73 7.20 0.12 20
MgO 1.28 1.29 0.38
SO3 2.96 0.95 0.12
K2O 0.59 1.47 0.54 0
Na2O 0.13 0.86 0.17 5 10 20 30 60 120 720 14402160
TiO2 0.26 1.46 – Time/min
Physical properties
Median particle size/μm 20 13 0.18 Fig. 4. Drainage of the foams prepared using foaming agents with different nano-silica
Loss on ignition/wt% 1.4 5.0 2.1 (NS) contents (0%, 1%, 3%, and 5%).
Specific gravity/g·cm−3 3.14 2.4 2.2
1080
Foams
100
1060 Surfactant solution

1040
80
1020
the density of normal surfactant
Density/kg· m-3

solution is about 1000kg/m3

Percent Passing/%

1000
60 Cement
Fly Ash
80
Silica Fume
40
70

60 the density of normal foams

20
is about 50kg/m3
50
0 1 3 5

0 Addition of nanosilica/wt%
0.1 1 10 100 1000
Fig. 5. Density of the particle-stabilized foam and surfactant solution.
Particle Size/μm
Fig. 2. Particle size distributions of the cement, fly ash, and silica fume powder.

13
W. She et al. Cement and Concrete Research 106 (2018) 12–22

Fig. 6. Microstructures of the foams at the initial time points (t = 0 min). (a) Normal foam, (b) 0.5% HPMC, (c) 0.5% HPMC/1% NS, (d) 0.5% HPMC/3% NS, and (e) 0.5% HPMC/5% NS.
The scale bar is 200 μm.

Table 3
25 (a) Normal foam Mix designs of the foamed concretes prepared with the various foams.
0%NS/0.5%HPMC
Mix Binder/kg·m−3 Water/ SP/% w/b Foams/kg·m−3
1%NS/0.5%HPMC
kg·m−3
20 3%NS/0.5%HPMC PC FA SF N-Fa HP-Fb HP-NS-Fc
5%NS/0.5%HPMC
– –
Percentage/%

Ref 356 178 59 207 0.45 0.35 28.95

15 N0 356 178 59 207 0.45 0.35 – 37.64 –
N3 356 178 59 207 0.45 0.35 – – 44.00d
N5 356 178 59 207 0.45 0.35 – – 46.32e
10
a
N-F: normal foam.
b
HP-F: HPMC-stabilized foam.
c
HP-NS-F: HPMC-NS-stabilized foam.
5 d
The content of NS was 3%.
e
The content of NS was 5%.

0
8
10 10
20 20
30 0
40 40
50 50
60 60
70 70
80 80
90 -90
0 0
0- 0
0 0
0- 0
0 0
0 0
0- 0
0 0
0 0
0- 0
凰 00
0

Wet density
-3

10 -10
11 -11
12 12
13 -13
14 14
15 -15
16 -16
17 17
18 -18
19 -19

20

7d
0-
-

-
-
-
-
-

14d Normal foamed 800kg/m3

Bubbles diameter/μm concrete at 28d
28d
6
Compressive Strength/MPa

100

(b) 4
80
Cumulative Percentage/%

2
60
D50

40
Normal foam 0
0% 3% 5%
0%NS/0.5%HPMC
1%NS/0.5%HPMC The addition of NS
20
3%NS/0.5%HPMC
Fig. 8. Compressive strengths of foamed concretes prepared with the various foams.
5%NS/0.5%HPMC
0
the hydration products and specimen microstructures. In addition, in
10 0
20 0
30 0
40 0
50 0
60 0
70 0
80 0
90 -90
0 0
0 0
0- 0
0 0
0 0
0 0
0- 0
0 0
0 0
0- 0
凰 00
0

situ XCT was used to monitor the microstructure formation of the

1
-2
-3
-4
-5
-6
-7
-8

10 -10
11 -11
12 -12
13 13
14 -14
15 -15
16 -16
17 17
18 -18
19 -19

20
0-

foamed concretes prepared with and without the modifications.

Bubbles diameter/μm Moreover, the relevant reinforcement and stabilization mechanisms
were investigated.
Fig. 7. Bubble diameter distributions of the various foams immediately after foaming: (a)
frequency distributions and (b) cumulative frequency distributions of the pore sizes.

14
W. She et al. Cement and Concrete Research 106 (2018) 12–22

Fig. 9. Morphology (left) and EDS spectrum (right) of the hydration products of foamed concrete without nano-silica.

Fig. 10. Morphology (left) and EDS spectrum (right) of the hydration products of foamed concrete with 5% nano-silica.

3000 a a-CH b-AFt c-C-S-H N0-28d 2. Experimental

d-SiO2 e-C3S N3-28d
a N5-28d 2.1. Materials
2500
d c a
b e a a 2.1.1. Nano-silica
2000
The nano-silica (NS; HDK® H13L, Wacker) possessed an average
diameter of ~30–40 nm and a specific surface area of 110–140 m2/g, as
Counts

1500 specified by the manufacturer. This NS is a type of hydrophobic

amorphous fume silica that is dimethylsiloxy modified with a residual
1000 silanol content of about 50%. Hydrophobicity is beneficial for the na-
noparticles to adsorb on the surfaces of the gas bubbles and develop a
500 synergistic effect with the surfactant.

0 2.1.2. Surfactant
10 20 30 40 50 60 The betaine-type amphoteric surfactant investigated was cocoami-
2-theta/° dopropyl betaine (C19H38N2O3, Qingdao Usolf Chemical Technology,
China), which is generated by reacting cocoamidopropyl dimethyla-
Fig. 11. XRD patterns of foamed concretes with varied nano-silica contents. mine with sodium chloroacetate. The foaming agent was made up of
water with a solid content of about 35%, comprised of betaine (about

15
W. She et al. Cement and Concrete Research 106 (2018) 12–22

Fig. 12. 2D images of foamed concrete sections obtained by X-ray computed tomography (upper) and these images after binary processing (lower): (a) Ref, (b) N0, (c) N3, and (d) N5.

20 30

Ref N0
25
15
20
Frequency/%

Frequency/%

10 15

10
5
5

0 0
200 400 600 800 1000 1200 1400 1600 1800 2000 200 400 600 800 1000 1200 1400 1600 1800 2000

35 35

30
N3 30
N5
25 25
Frequency/%

Frequency/%

20 20

15 15

10 10

5 5

0 0
200 400 600 800 1000 1200 1400 1600 1800 2000 200 400 600 800 1000 1200 1400 1600 1800 2000

Air void diameter/μm Air void diameter/μm

Fig. 13. Pore size distributions of the foamed concretes with densities of 800 kg/m3.

30%) and sodium chloride (< 5%). cellulose ether (CE) for building materials in China, is a water-soluble
semi-synthetic polymer derived from cellulose. Here, HPMC was used
2.1.3. Organic stabilizer to assist the foam stabilization. HPMC with a molecular weight of
Hydroxypropyl methylcellulose (HPMC; Dingshengfumei Science & 200,000 g/mol was selected; the contents of the methoxyl (OCH3) and
Technology Development Co., Ltd., China), the most widely used hydroxypropyl (denoted POOH) substitution groups are shown in

16
W. She et al. Cement and Concrete Research 106 (2018) 12–22

Table 4 a type of polycarboxylic (Sobute New Materials Co., Ltd., China), with a
Pore structure characterization for the foamed concretes prepared with the various foams. water reducing rate of 40%. The dosage was set at 0.45 wt% of the
binder total.
Mix Wet Dry Porosity/% Average Log–normal curve fitting
density/ density/ diameter/ parameters
kg·m−3 kg·m−3 μm
Mean Standard
2.2. Surfactant solution preparation and foaming process
value deviation
(μ) (σ) Surfactant solutions containing varied NS contents were first pro-
duced. A sodium hydroxide solution with a pH value of 10.5 was used
Ref 820 778 56.8 289 6.008 0.608
N0 815 762 57.6 260 5.799 0.582
as the dispersant. The suspension was prepared by gradually adding the
N3 808 774 57.0 210 5.714 0.543 NS particles to a solution being stirred with a magnetic stirrer. To avoid
N5 823 781 56.6 205 5.672 0.541 the aggregation of the NS particles, an ultrasonic dispersion machine
with a maximum ultrasonic frequency of 40 kHz was then employed.
The ultrasonic treatment time was 20 min, during which the tempera-
1200 ture was kept at 20 °C. Next, 5 wt% betaine was added to the NS sus-
0% B+0% HPMC pension, which was continuously stirred for 3 h. Finally, 0.5 wt% HPMC
1000 5% B+0% HPMC powder was added into the aqueous solution already containing NS and
5% B+0.5% HPMC betaine. As HPMC easily agglomerates, it was added slowly and care-
800
fully.
Viscosity/mPa· s

600 After the surfactant preparation, a high-speed milk mixer was used
for foaming the surfactant solution at its maximum speed for 3 min.
400
1.8
2.3. Foamed concrete specimen preparation
1.6

1.4 Foamed concrete was produced by a mortar mixer. The cementi-

tious materials, made up according to the desired mix proportions, were
1.2
first dry-mixed for 1 min. The water and water reducer agent were then
1.0 added to the premixed powders and mixed for 3 min. Finally, the pre-
0 1 2 3 4 5 formed foam generated with a high-speed milk mixer was added and
NS/wt% mixed for 3 min until the foam was uniformly distributed. The plastic
density of the mix was then measured and values within ± 50 kg/m3 of
Fig. 14. Relationship between the solution viscosity and NS addition under different target density were accepted. If the density was higher than the desired
betaine (B) and HPMC contents.
value, additional foam was incrementally added until the target value
was achieved, followed by further mixing. If the density was lower, the
Table 1. The fraction used was fixed at 0.5 wt% above the total solution mix was rejected and remade. After mixing, the foamed concrete paste
for all NS contents. was cast into molds, which were then covered with cling film to prevent
water evaporation. After 24 h, the specimens were unmolded and stored
2.1.4. Cementitious materials in a standard curing room (20 °C, 100% relative humidity) until testing.
The cementitious materials used in the study were Portland cement
(PC), fly ash (FA), and silica fume powder (SF). Their physical and 2.4. Testing methods
chemical characteristics are given in Table 2, and their particle size
distributions are shown in Fig. 2. The P·II 52.5 cement used conforms to 2.4.1. Foam characterization
the GB Standard for common Portland cement [17], while the grade Ӏ Immediately after foam production, the actual foam density was
FA conforms to the GB Standard for fly ash used for cement and con- measured by filling a pre-weighed standard container of known volume
crete [18]. The mean diameters of the PC, FA, and SF were 20, 13, and with the foam precast and weighing it. The foam stability was evaluated
0.18 μm, respectively. by measuring the mass of liquid that drained from the bottom of the
foam. The weight was recorded at 5, 10, 20, 30, 60, 120, 720, 1440, and
2.1.5. Superplasticizer 2160 min. Also, OM and SEM were used to characterize the micro-
The superplasticizer used in the preparation of the cement paste was structures of the foams.

Fig. 15. Microstructure of the foam produced with both 5% NS and 0.5% HPMC after drying. (a) Optical microscopy image; (b) scanning electron microscopy image; and (c) EDS
spectrum.

17
W. She et al. Cement and Concrete Research 106 (2018) 12–22

Fig. 16. Schematics of the binding forces between the NS, HPMC, and surfactant in the foam system.

height can be drawn and the stability can be judged by the following
1.25 Wet density 800kg/m3 formula:
Ref
N0 ρx
R=
1.20 N3 ρ0
N5 R represents the ratio of the densities, where ρx is the density of the
Ratio of density

1.15
1.10
1.05
1.00
0 200 400 600 800
Distance to the top of the cylinder/mm
Fig. 17. Results of the large-scale stability tests of specimens taken at positions between
the top (0 mm) and bottom (1000 mm) of the foamed concretes.
2.4.2. Viscosity measurements
A digital viscometer (Shanghai Ping Xuan Scientific Instrument Co.)
was used to measure solution viscosity. This was equipped with five
rotors to measure a wide range of viscosities, ~1–1 × 105 mPa·s, with a
measurement accuracy of ± 2%.
2.4.3. Hardened foamed concrete properties
The strengths of the foamed concretes were measured by a sensitive
multifunctional testing system (MTS Systems Corporation) machine
with a 200 KN capacity; the specimens had a dimension of
70.7 × 70.7 × 70.7 mm3. Before the mechanical performance tests,
each specimen was dried in an oven at 60 °C until a constant weight was
reached. XRD and SEM were conducted to observe and characterize the
hydration products of the foamed concretes, and XCT was performed to
observe their microstructures.
2.4.4. Stability of the foamed concrete
Two methods were adopted to characterize the stabilities of the
foamed concretes. For the large-scale tests, the specimens were formed
into cylinders with diameters of 50 mm and heights of 1 m. After 7 days
of casting, the specimens were removed from the molds and cut into
several 30 mm-tall cylinders at intervals of 250 mm. The cut samples
were dried until constant weights were reached; subsequent mass and
volume measurements allowed the densities of the specimens to be
calculated. From this data, a curve of the density variation with casting
specimen at position x and ρ0 is the density at the top of the specimen.
The second method involved using XCT to follow the hardening
process of the foamed concrete (see Fig. 3). Fresh foamed concrete was
cast into a tube with volume of 50 mL and scanned with the XCT Pre-
cision system (YXLON, Germany) at regular intervals. The detector was
a flat-panel type Y.XRD 1620 with an object rotation angle of 360° and
the time of one rotation angle of 360° was 10 min. The voltage of the X-
ray tube was 195 kV.
1000
3. Results and discussion
3.1. Foam stability
The effects of NS and HPMC on the foam stability are shown in
Fig. 4. Within the first 5 min, nearly 80% of the liquid drained from the
normal foam (i.e., that without NS and HPMC) and the foam completely
disappeared after 30 min. However, when the surfactant solution with
NS and HPMC was added, the stability dramatically improved such that
there was no drainage and no foam loss within 30 min. In the case of
using HPMC solely as a stabilizer, the drainage at 120 min was de-
creased by 37.58% as compared to the normal foam, and the foam
disappeared at 720 min. With the addition of NS, the foams are very
stable within 60 min, and the gradual reduction in drainage shows a
positive correlation with the NS content. The drainage at 120 min de-
creased by 73.67%, 86.68%, and 93.7% when the content of NS was
1%, 3%, and 5%, respectively. The foams with both HPMC and NS
stabilizers had higher stabilities; the foams still existed even after
720 min, and remained up to 36 h.
On the other hand, the foam density increased with increasing
amounts of cellulose and NS, which was 20% to 60% higher than that of
the normal foam (Fig. 5). The reason for this increase is the presence of
the particles that increase the density of the surfactant solutions (which
varied between 1.02 and 1.08 g/cm3). However, all the foam densities
were < 85 kg/m3, which is suitable for the preparation of low-density
foamed concrete.
3.2. Foam microstructure
The microstructures of the foams determined by OM at the initial
time points are shown in Fig. 6. The normal foam and those with HPMC

18
W. She et al.
Fig. 18. 2D images (upper) and 3D structures (lower) showing the motion coarsening of normal bubbles in the foamed concrete, obtained with X-ray computed tomography.
and NS had similar structures, with spherical bubbles and concave
triangular Plateau borders between them. The normal foam possessed a
disordered state with a wide bubble size distribution and a thin film
width. The bubbles were tightly packed together and so the Plateau
borders were interconnected with each other, which provided a fast
channel for foam drainage and made the foam extremely unstable [2].
When HPMC was added into the surfactant solution, the size distribu-
tion of the bubbles did not change greatly, but the thickness of the
bubble film slightly increased; the bubbles were better separated, re-
sulting in a lower Plateau border interconnectivity. Fig. 4(c)–(e) pre-
sents the structures of the foams created by adding 1%, 3%, and 5% NS
into the surfactant with 0.5% HPMC. With an increase in the amount of
added NS, the bubble size distribution gradually narrows and the Pla-
teau borders gradually change into nodes. These changes in the chan-
nels hinder foam drainage and greatly improve the stability of the foam.
Fig. 7 shows the bubble size distributions of the various foams,
19
Cement and Concrete Research 106 (2018) 12–22
Fig. 19. 2D schematics of the forces acting on (a) a normal
bubble and (b) a nanoparticle-stabilized bubble when in-
corporated into fresh cement paste.
obtained by analyzing the OM images with Image Pro. The bubble
diameters of the normal foam ranged between 33 and 291 μm, while
those of the foams with added HPMC varied between 32 and 277 μm.
The foams with both HPMC and NS (contents of 1%, 3%, and 5%) had
narrower diameter distributions of 11–255, 3–204, and 2–113 μm, re-
spectively. As shown in Fig. 7(a), the bubble size distributions of the
HPMC-stabilized foams do not show a trend of refinement, though the
stability of the foams with added HPMC will have increased sig-
nificantly. Interestingly, a clear refinement of the bubble sizes was
observed as a function of the amount of added NS. As seen in Fig. 7(b),
the mean bubble sizes of the foams consisting of different NS contents
(1%, 3%, and 5%) are in the ranges of 50–60, 40–50, and 30–40 μm,
respectively, while those of the normal and HPMC-stabilized foams are
in the range of 90–100 μm. Additionally, the majority of the bubbles
produced by the nanoparticle-modified surfactant solutions have dia-
meters smaller than 130 μm, which is 35% lower than for the normal
W. She et al.
Fig. 20. 2D X-ray computed tomography images showing the motion coarsening of the HPMC/NS-stabilized bubbles in the foamed concrete.
foam. The larger the bubble diameter, the higher the probability of
bubble coarsening [2], thus the stability was greatly improved by the
addition of NS.
3.3. Mechanical performance of foamed concrete
To study the effects of the HPMC- and NS-stabilized foams on the
mechanical performance of the resulting foamed concretes, four sets of
foamed concrete specimens were cast: normal foam, HPMC-stabilized
foam, and HPMC/NS-stabilized foams (with 3% and 5% NS). The
casting wet density was 800 kg/m3 and the water-to-binder mass ratio
(w/b) was fixed at 0.35 for all the foams. The mix designs are shown in
Table 3.
The compressive strength test results are shown in Fig. 8. For all
samples, the strength increased with the increase of time. The strengths
at 7 days ranged between 2.98 MPa (0% NS) and 4.21 MPa (5% NS),
which increased to 5.16 and 6.52 MPa, respectively, after 28 days.
Furthermore, a clear increase in compressive strength can be seen as the
NS content increased. When the specimens were prepared with the
normal foam, the strength at 28 days was 3.61 MPa. Compared to this
value, the compressive strengths of the 0% and 5% NS foamed con-
cretes at 28 days were 1.4 and 1.8 times of the Ref samples. This in-
crement of compressive strength is due to the pozzolanic reaction of the
NS with Ca(OH)2. As seen from Fig. 9, significant amounts of Ca(OH)2
formed in the pore walls for foamed concrete without NS. In contrast, a
large number of hydration products existed in the foamed concretes
prepared by the NS-stabilized foams (Fig. 10), which result in the
densification of the cell wall paste structure. The spectra of the che-
mical compositions of the pastes located inside the pores are shown in
Figs. 9 and 10. With the addition of NS, the Ca/Si ratio decreased from
2.27 to 1.92.
3.4. Hydration products of foamed concrete
XRD was used to investigate the hydration products of foamed
concretes, and the results are shown in Fig. 11. With an increasing NS
concentration, the number of Ca(OH)2 in the foamed concrete gradually
decreased. Such silica nanoparticles possess high activities because of
their large specific surface areas [19,20]. When the gas bubbles coated
20
Cement and Concrete Research 106 (2018) 12–22
with NS are added into the foamed concrete mixture, NS reacts with
calcium hydroxide according to the following chemical equation to
generate a layer of hydration products inside each pore, as shown in
Fig. 10.
2SiO2 + 3Ca (OH )2 + mH2 O → 3CaO∙2SiO2 ∙ (m + 3) H2 O
This hydration product layer can fill the pores inside of the cell wall,
increasing the strength of the cell wall and improving the mechanical
properties of the foamed concrete.
3.5. Microstructure of the foamed concrete
XCT was used to detect the pore size distributions of the foamed
concretes prepared either without or with NS; the results are shown in
Fig. 12. Fewer larger pores and a more uniform pore size distribution
become apparent with the addition of HPMC and NS. This is also con-
firmed by Fig. 13, which displays the frequency distributions of the
pore sizes and the fitted log–normal distribution curves. This tendency
towards uniformity is due to the high stabilities of the foams modified
by HPMC and NS. When each foam is coated with a layer of NS parti-
cles, the motion-resistance force of the bubbles in the slurry is greatly
increased. This can restrict the growth, drainage, and coalescence of the
bubbles and thus optimize the size distribution of the foamed concrete.
However, the difference between in the pore size distributions of N3
and N5 in this work is not significant, which means the optimum
content of the NS particles is 3%.
As reported in the literature [21], the pore size distribution of
foamed concrete nearly follows a log–normal distribution. A probability
function denoted by f (x, μ, σ) was used to fit the size distributions, as
follows:
(lnx − μ)2
1
f (x , μ, σ ) = e 2σ 2
xσ 2π
where μ and σ are the mean and standard deviation of the variable's
logarithm. The correlation coefficients of the fitted curves are 0.91,
0.97, 0.90, and 0.91 for the foamed concretes with no NS or HPMC,
with HPMC only, and with HPMC and 3% or 5% NS, respectively. The
corresponding fitted values of μ and σ for the foamed concretes pre-
pared in this study are also summarized in Table 4. The larger the value
W. She et al.
of σ, the wider the pore size distribution of the foamed concrete
[22,23].
4. Stability mechanisms of the foams and foamed concretes
4.1. Foam stability
Due to the non-equilibrium nature of wet foam systems, the struc-
ture and hence performance evolve with time. As demonstrated in the
literature [2], this evolution involves three mechanisms: foam drainage,
film rupture, and bubble coarsening. The three mechanisms are directly
related to the properties of the bubble film and the interactions between
the liquid film and Plateau borders. Foam drainage is the result of
mutual extrusion between the bubbles and the gravity, which mainly
manifests as the loss of liquid from the film. In the case where a sur-
factant is solely used as the stabilizer, foam drainage is very obvious
and the liquid is usually discharged in only a few minutes. Once the
liquid is drained into the Plateau borders, it will enter a free-flowing
state and flow very fast with a speed of about 1 cm/s. If the film does
not rupture, foam drainage will continue until the foam has dis-
appeared completely.
The stabilities of the foams which prepared by using surfactant and
HPMC without NS improved as the viscosity of the surfactant solution
increased. As seen from Fig. 14, when pure water with 5 wt% surfactant
(betaine) was added, the viscosity of the solution increased from 1.15 to
1.18 mPa·s, i.e., only a 2.6% rise. However, when 0.5 wt% HPMC was
also added, the viscosity increased to 406 mPa·s, nearly 353 times more
than that of pure water. The increased viscosity of the surfactant so-
lution makes the bubble film stronger. It has two effects: it increases the
surface strength of the liquid film, and delays the foam drainage. The
improved strength of the film will hinder the diffusion of the internal
gas towards the outside and increase the ability of the bubble to resist
external disturbances. Also, the increased viscosity will increase the
resistance forces when the liquid flows in the Plateau borders, thus
making the foams more stable.
The mechanism of foam stabilization with nanoparticles coupled
with surfactants is well understood. Unlike the stabilization mechanism
of HPMC, nanoparticle stabilization does not depend on the increase of
solution viscosity since no trend is obvious (Fig. 14). The main reason
for stabilization is that the nanoparticles tend to strongly adsorb on the
surfaces of the gas bubbles and a synergistic effect with the surfactant
occurs. Stocco [13] concluded that the particle adsorption free energy is
on the scale of thousands of kBT, while the adsorption free energy of the
surfactant at the gas–water interface is only a few kBT. Thus, the na-
noparticles have a stronger stabilization effect on the gas bubbles than
the surfactant, with a different mechanism than when using the sur-
factant alone. At the same time, with the addition of the nanoparticles,
there exists a three-dimensional network structure between the bubble
and continuous phases; this prevents the coalescence and coarsening of
the gas bubbles and enhances the stability of the foam.
When the NS particles and HPMC are simultaneously added to a wet
foam system, both cooperate with the surfactant to stabilize the foam.
On the one hand, the viscosity of the solution greatly increases when
both HPMC and NS are added, as shown in Fig. 14. Adding NS to a
solution of 0.5 wt% HPMC and 5% betaine dramatically increases the
viscosity of the solution. Also, the growth rate increases with an in-
creasing amount of added NS. When the content of NS was 5%, the
viscosity of the solution reached 1108 mPa·s, about 2.9 times higher
than that of the solution with HPMC only, while this is only 1.6 times
greater when the NS content is 3%. The higher viscosity of the solution
strengthens the bubble film, making film rupture and gas diffusion
more difficult. On the other hand, the NS particles can form a three-
dimensional framework on the bubble surfaces, and the excess particles
can block the Plateau borders, as shown in Fig. 15(a). The enhancement
of these two aspects makes the foam drainage, film rupture, and bubble
coarsening more difficult, and thus the stability of the foam is greatly
21
Cement and Concrete Research 106 (2018) 12–22
improved. Besides the physical enhancements conferred by the surfac-
tant, NS, and HPMC, there exist the binding forces between them.
Fig. 15(b) is a SEM image of a dried foam consisting of NS, HPMC, and
betaine simultaneously. The membrane material was HPMC due to it
being a hydrophilic organic macromolecular substance; this membrane
will give support to the bubble film. The energy-dispersive X-ray
spectroscopy (EDS) spectrum (Fig. 15(c)) shows that the substances
adsorbed on the membrane were silica and sodium chloride, which
indicates some degree of binding between the NS and surfactant with
HPMC.
Betaine is a type of amphoteric surfactant, with hydrophilic groups
bearing both positive and negative ions. When using betaine and NS
particles under an alkaline environment, the hydroxyl groups on the NS
particle surfaces will be hydrolyzed to negative oxygen ions. The po-
sitive ions in the hydrophilic groups of the surfactant can bind with the
oxygen anions through Coulombic forces, as shown in Fig. 16. This
electrostatic force ensures that the NS particles are firmly attached to
the outer surfaces of the bubbles. However, van der Waals forces exist
between the hydrophobic groups of the surfactant and HPMC due to the
absence of free ions. The existence of these two forces ensures the three
components are not fragmented but integrated to jointly stabilize the
foam.
4.2. Stability of foamed concrete
The results of the large-scale stability tests of the foamed concretes
are shown in Fig. 17. The foamed concrete cast with the normal foam is
evidently unstable. The density decreased gradually with an increase of
pouring height; the density at the bottom of the cylinder was the
greatest at 1.25 times that at the top. However, when the HPMC-sta-
bilized and HPMC/NS-stabilized foams were added into the slurry, the
resulting foamed concretes became increasingly stable with maximum
density ratios of 1.12, 1.05, and 1.03 for 0%, 3%, and 5% NS, respec-
tively. This phenomenon is further validated by the XCT tests, which
are shown in Fig. 18.
The images obtained by XCT directly reflect the early collapse be-
havior of the foamed concretes, and their 3D structures can also be
reconstructed from these images; thus, the microstructural evolutions of
the foamed concretes can be obtained. Fig. 18 shows the stratification
of the foamed concrete prepared with the normal foam at the early
stages (within 40 min of casting), which gradually becomes less obvious
with time. Also, as seen in the lower images of Fig. 18, the formation of
the foamed concrete skeleton can also be followed. Due to the low rate
of hydration of the Portland cement, few hydration products were
formed in the first 40 min, and they were separated by a large number
of unhydrated cement particles; thus, there was no overlap between
them. However, bubble formation is a dynamic process once in-
corporated into the base mix. Unlike liquid foams that contain bubbles
interconnected via films, bubbles added to the cementitious matrix are
separated by the paste or mortar paste surrounding them. There are
several types of “forces” acting on the bubbles (Fig. 19(a)) [8]. A stable
bubble equilibrium state is obtained when these forces are balanced:
the bubble confinement force (Fc), drainage force (Fd), internal bubble
pressure (Pi), bubble surface tension due to the effect of the surfactant
(Fst), and the bubble buoyancy force (Fb). The confinement force—a
function of plastic density, water-to-binder ratio, and filler type-
s—decreases at lower densities due to the decrease in yield stress.
Moreover, surface tension is a time-dependent force that reduces gra-
dually with time [2,24]. The drops of Fst and Fc make the bubbles in the
normal foam more unstable, and the bubbles grow easily and float to
the upper region of the slurry under the force of buoyance. The strength
of the foamed concrete at the early stages is not matched with the forces
acting on the bubbles, which results in the limitation of bubble motion
and hence the stratification (Fig. 18) and uneven density (Fig. 17) in the
foamed concrete.
However, different results were observed when the bubble surfaces
W. She et al.
were coated with a layer of NS particles and the films were enhanced
with HPMC. As seen in Fig. 19(b), the NS particles adsorb on the
bubbles and increase the surface roughness, increasing the friction drag
of the bubbles moving in the slurry. In addition, the bubble surface free
energy is absorbed by the NS particles and the strengths of the liquid
films are enhanced by the HPMC. These effects result in the slow re-
duction in surface tension with time. This mechanism can be confirmed
by Fig. 20, which shows that the bubbles do not undergo fusion set-
tlement in the slurry before the final setting time.
5. Conclusions
A novel method for the preparation of highly stable wet foams by
simultaneously using NS particles, HPMC, and a betaine surfactant has
been presented. Foams prepared with the surfactant as well as NS and
HPMC possess longer lifetimes and narrower pore size distributions,
and the effects are more significant at higher NS contents. The foam
stabilization is achieved through the adsorption of NS particles at the
gas–liquid interface and the dissolution of HPMC into the bubble film.
The former can form a three-dimensional network structure between
the bubble and continuous phases, and the latter enhances the strength
of the film. Coulombic forces exist between the NS particles and hy-
drophilic groups of the surfactant, and van der Waals forces link the
HPMC and hydrophobic groups of the surfactant, which interconnect
the three components to jointly stabilize the foams.
The foamed concretes prepared by incorporating nanoparticle-sta-
bilized foams possess higher compressive strengths and narrower pore
size distributions compared to the normal foamed concrete. In addition,
the hydration products can be altered by the reaction between the NS
and Ca(OH)2. Moreover, fresh foamed concrete prepared using NS/
HPMC-stabilized foams is highly stable and does not collapse at the
early stages. This is due to the increased roughness of the NS-coated
bubble surfaces that limits the bubble movement.
Acknowledgements
Authors gratefully acknowledge the financial support from National
Natural Science Foundation of China [5150080804]; 973 Program
[2015CB655100]; National Science & Technology Pillar Program
[2014BAB15B01-02]; Technological Development Projects of China
Railway Engineering Corporation [2015G002-I, 2015G002-K]; State
Key Laboratory of High Performance Civil Engineering Materials
22
Cement and Concrete Research 106 (2018) 12–22
[2016CEM005].
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