Case Studies in Construction Materials 11 (2019) e00232

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Case Studies in Construction Materials

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Case study

Effects of chemical and mineral admixtures on the foam

indexes of cement-based materials
Hai Huanga,b , Qiang Yuana,*, Dehua Denga , Jianwei Pengb , Yanling Huanga
a
National Engineering Laboratory for High Speed Railway Construction, School of Civil Engineering, Central South University, Changsha
410075, China
b
Anhui Engineering Material Technology Co. Ltd of CTCE Group, Hefei 230023, China

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

Article history: Air in cement-based materials is one of the important parameters affecting its properties in
Received 30 December 2018 fresh and hardened states. Various types of chemical and mineral admixtures have been
Received in revised form 18 February 2019 combined and used in cement-based materials. This makes the formation and stability of
Accepted 3 March 2019
air bubble in fresh cement-based materials very complicated, and the control of air void in
cement-based materials difficult. In this paper, air-related issues of cement-based
Keywords: materials were evaluated by foam indexes and surface tension test. The effects of mineral
Chemical admixtures
admixtures, including slag, fly ash and silica fume, and chemical admixtures, including
Mineral admixtures
Cement-based materials
superplasticizers, viscosity-modified admixtures and air-entraining admixtures on the
Air foam indexes were studied. Results showed that surface tension is one of the factors
Surface tension affecting foam ability and foam stability, but not decisive one. Foam ability and foam
Foam ability stability of cement-based materials depend on many factors, such as types of chemical
Foam stability admixtures, compatibility of chemical admixtures, fineness and its chemical compositions
of mineral admixtures.
© 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY
license (http://creativecommons.org/licenses/by/4.0/).

1. Introduction

The air in hardened concrete has two different effects on concrete. On one hand, strength decreases with the increase of
air content in concrete. On the other hand, well designed air system in hardened concrete can significantly improve its frost-
resistance performance. The air system in hardened concrete can be modified by air-entraining admixture (AEA). Three
parameters can be used to describe the characteristics of air system in concrete, i.e. total air content, size of air void, and
distance between air voids (i.e. spacing factors). For non-air-entrained concrete, the total air content is often around 3%, and
the spacing factor is usually greater than 700 mm, and the size of air void ranges from 0.5 to 3 mm. For well air-entrained
concrete, the total air content is often around 4–10%, and the spacing factor is usually 100–200 mm, and the size of air void
ranges from 5 to 200 mm [1]. Therefore, AEA is often used to modify the air system of concrete, and thus improve the frost
resistance of concrete in cold regions [2,3]. For example, almost 100% of concrete in Japan and Canada contains an AEA [4].
The air system in hardened concrete depends on the air entrained in fresh concrete and their stability during placing,
transportation and rest. Fresh concrete is a composite consisting of liquid, gas and solid phases. Basically, AEA is a surfactant
which can decrease the surface tension of liquid and facilitate the formation of fine air void in fresh concrete. The use of AEA
can also stabilize air bubble in fresh concrete. This has been explained by two mechanisms [5]: the fixation of the hydrophilic

* Corresponding author.
E-mail address: 209176@csu.edu.cn (Q. Yuan).

https://doi.org/10.1016/j.cscm.2019.e00232
2214-5095/© 2019 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/
4.0/).
2 H. Huang et al. / Case Studies in Construction Materials 11 (2019) e00232

termination of the air entraining molecules on the particle surface and the formation of insoluble hydrophobic membrane at
the water-air interface. Obviously, the formation of air in concrete mainly relates with the surface properties of the liquid of
fresh concrete, which was also greatly affected by the addition of other high molecular polymers in concrete. Apart from AEA,
high range water-reducing admixtures (HRWRA) or superplasticizer (SP) are the most often used chemical admixtures for
concrete. Since some common SPs may increase the air content in concrete [6], it is not easy to obtain low air content for self-
compacting concrete (SCC) [7,8]. It is worth to note that the air voids produced by the SP are usually coarser than those
produced by the AEA [9]. In addition, with the wide application of SCC, viscosity-modified admixtures (VMA) have been used
more and more in the preparation of SCC. Generally, SCC can be divided into three types: powder type (550–650 kg/m3
powder content), VMA type (350–450 kg/m3 powder content and VMA used), mixed type (450–550 kg/m3 powder content
and VMA used) [10]. In the application of SCC, VMA greatly reduces the water sensitivity of concrete which improves the
construction quality [11]. In order to obtain high flowability and stability, concrete often contains a large amount of powder
materials, SP, AEA, and VMA. Furthermore, the possible interactions among chemical admixtures (SP, VMA and AEA) and the
interaction between chemical admixtures and powder materials are very complex [12–14]. This makes the air void
distribution or size of air bubbles in the matrix of cement-based materials very complicated and hard to predict. Air-related
issues of concrete are not only crucial to the frost resistance of concrete, but also important for many engineering
applications. For instance, the air stability in fresh SCC, which is used in a new type of high speed railway track system—CRTS
(China Rail Track System), is also very important [15,16].
Due to economic and ecological benefits, many mineral admixtures have been used in modern cement and concrete
industry, such as fly ash, slag, silica fume, and limestone powder. The synergic effects of cement and mineral admixtures are
also a hot topic in concrete material science [17].
It can be seen that the constituents of modern concrete are quite complicated. Although numerous works have been
carried out on testing and controlling the air characteristics of concrete and some techniques have been proposed to produce
concrete with appropriate air void in concretes, the control of air characteristics is still a difficult topic to deal with [9,18–26].
In order to design concrete with appropriate air system, a series of concrete has to be made, and the air system can be
measured after concrete gets hardened. Instead of measuring the air system of hardened concrete, it is desirable to know the
air system of hardened concrete by measuring the properties of fresh concrete. Under this circumstance, air void analyzer
(AVA) was developed to fulfill this requirement, which measures the air parameters of fresh concrete, and thus the air void
parameters of hardened concrete can be obtained. However, AVA is very sensitive, and the variation of testing results are
quite large [27,8]. In practice, the air content of fresh concrete, instead of air void parameters of hardened concrete, is often
measured as a quality control tool. It is also desirable to obtain the air content by a simple test, instead of batching concrete.
Foam index test or surface tension measurement test are sometimes used to evaluate the effectiveness of air entrainment.
Foam index test was often used to evaluate the degree of fly ash interference with AEA in concrete [28]. In such test, AEA is
added to the suspension with different powders, and the suspension is shaken for a certain time, followed by checking the
volume and stability of bubbles on the surface of suspension. Since this test is operator dependent, a new surface tension test
was proposed to replace the foam test, and found a good relationship between these two methods, but the new surface
tension test needs further improvement [29]. An automated foam index test was proposed to quantify the relationship
between AEA and fly ash-cement suspension [30]. Sahin et al. [25] also proposed to use surface tension measurement as a
tool for the evaluation of air entrainment. Literature [31,32] employed foam ability and foam stability tests and surface
tension measurements to evaluate the effects of SP on the air content in SCC. The authors [31,32] found that foam ability and
foam stability indexes correlated well with air content in SCC, and SP aqueous solution with low surface tension had high
foam ability index and high volume of air-content in SCC. Based on the well-established relationship between foam index or
surface tension measurement and air content, this quick test is potential to evaluate the synergic effect of chemical and
mineral admixtures on the effectiveness of air entrainment of cement-based materials. And, there is few literature focusing
on this topic.
In this paper, foam index test and surface tension measurement were used to evaluate the effects of chemical and mineral
admixtures on the foam indexes of cement-based materials. Chemical admixtures include SP: naphthalene-based
superplasticizer and polycarboxylate-based superplasticizer, VMA: hydroxypropyl methyl cellulose (HPMC) and welan gum
(WG), AEA: two types of alkyl benzene sulfonate with different molecular weights, alcohol benzene sulfonate and rosin.
Mineral admixtures include fly ash, silica fume and slag. The relationship between foam indexes and surface tension were
also evaluated. The abbreviations of the technical terminology are given in Table 1. This study can provide useful information
on the control of the air content of concrete characterized by high contents of powder and chemical admixtures.

2. Experimental program

2.1. Materials

The cement used in this study was P II 52.5R Portland cement complied with Chinese standard GB175-2007. Grade I Fly
ash was used this study, which complied with Chinese standard GB1596-2005. Grade S95 slag was used, which complied
with Chinese standard GBT18046-2008. Silica fume was provided by Aiken Company. The chemical compositions of powders
are given in Table 2. In order to study the coupled effect of SP, VMA and AEA, the chemicals were all provided in solid form,
instead of liquid form, to avoid some unknown chemicals were mixed in liquids, such as de-foamer. PCE and PNS
 H. Huang et al. / Case Studies in Construction Materials 11 (2019) e00232 3

Table 1
Abbreviations of nouns.

Full name Abbreviations

Naphthalene superplasticizer PNS
Polycarboxylate superplasticizer PCE
Hydroxypropyl methyl cellulose HPMC
Welan gum WG
Alkyl benzene sulfonate with high molecular weight air entraining agent No. 1 AEA
Alkyl benzene sulfonate with low molecular weight air entraining agent No. 2 AEA
Alcohol benzene sulfonate air entraining agent No. 3 AEA
Rosin air entraining agent No. 4 AEA
Pure cement PC
20% fly ash + 80% cement 2FA8PC
10% silica fume + 90% cement 1SF9PC
40% slag + 60% cement 4SL6PC

Table 2
Chemical compositions and physical properties of the powders used in this study.

Cement (PC) Silica fume (SF) Ground slag (SL) Fly ash (FA)
CaO (%) 62.80 0.20 41.00 3.70
SiO2 (%) 20.60 93.00 33.10 52.7
Al2O3 (%) 4.13 0.41 15.40 25.8
Fe2O3 (%) 2.99 0.80 0.50 9.70
SO3 (%) 2.56 0.39 1.95 0.20
MgO (%) 2.99 0.60 7.50 1.81
Other minor oxides (%) 3.93 4.60 0.55 6.09
Loss on ignition (%) 0.31 2.01 0.40 1.76
Specific surface area (m2/kg) 353 17800 1287 1633

superplasticizers were provided by BASF company and Japan's Kao company, respectively. Since HPMC and WG are the most
often used VMAs, HPMC and WG in their solid forms were used in this study. The molecular weight of HPMC was 150,000.
Four types of AEAs, which are quite often used in Chinese market, were used, i.e. alkyl benzene sulfonate with high molecular
weight of 348, alkyl benzene sulfonate with low molecular weight of 334, alcohol benzene sulfonate and rosin. Deionized
water with the conductivity of about 10 mS/cm was used.

2.2. Surface tension measurement

The surface tension of the aqueous solution was measured by a commercial automatic surface tension meter based on
Wilhelmy plate method [33]. In this method, the platinum plate was cleaned thoroughly and attached to a balance with a
thin metal wire, and then was oriented perpendicular to the air-liquid interface. The force exerted on the platinum plate was
measured by a tension meter, and used to calculate the surface tension based on the Wilhelmy equation. The surface tension
of deionized water used in this study was determined as 71.150 mN/m, which is very close to the data in textbook. The surface
tension of SP solution with concentrations of 0.2%, 0.5%, 0.8% and 1.2%, and AEA solution with concentrations of 0.01% and
0.02% were measured. According to the testing results of the surface tension, the concentrations of AEA and SP with the
lowest surface tension were used to make complex solutions (0.5% for SP and 0.02% for AEA). The surface tension of solutions
with combined SP, AEA and VMA were also measured. In this study, SP solutions and AEA solution with 30.00% solid content
were prepared by dissolving solids into deionized water. Prior to making complex solution, VMA were first dissolved in water
24 h before use. Since the dissolution of VMA is very slow and its dissolution may affect the viscosity of the solution, the
dissolution of VMA was placed in magnetic stirrer for continuously stirring for 24 h at 25
C. SP solution and VMA solution
were first mixed, followed by adding AEA solution and additional water. These solutions were thoroughly mixed before
measuring surface tension. Three measurements were run on each sample, and the average values were reported. Surface
tension test had very good repeatability. The maximum variation between measurements and the average value was less
than 5%.

2.3. Foam index test

Foam index test (Fig. 1) was usually used to evaluate the effect of fly ash on the foam ability of AEA [29]. In this study, the
similar testing method was used to evaluate the synergic effects of chemical and mineral admixtures on foam indexes.
Powder materials and deionized water were mixed at the mass ratio of 1:5, and 20 ml suspension was poured into a 50 ml
stoppered glass flask. The flask with suspension were manually vigorously shaken for 60 s, and then rested on the table, read
4 H. Huang et al. / Case Studies in Construction Materials 11 (2019) e00232

Fig. 1. Foam ability and foam stability tests.

the foam height after 10 s (Hf). After resting for 3 min, the foam height was read again (Hs). Triplicate tests were run, and the
average values were recorded. The maximum variation between measurements and the average value was less than 15%.
The foam ability index Ff and foam stability index Fs were calculated by the following equations:
F f ¼ 100%  ðHf  20Þ=20 ð1Þ

F s ¼ 100%  ðHs  20Þ=ðHf  20Þ ð2Þ

The tested powder materials were typical binary binders for modern concrete [34], included PC, 4SL6PC,1SF9PC and 2FA8PC,
their chemical compositions are given inTable 2. It is worth to mention that the foam index test is not a standardized method. The
test results are operator dependent. Hence it is difficult to compare results between different operators or laboratories. However,
in the experiment carried out in this study, foam index test has been proved to have good repeatability by the same skilled
operator, and can be a qualified testing method to evaluate the foam ability of cement-based materials.

3. Results and discussion

3.1. Surface tension of solutions with different chemicals

The surface tension of solutions with different combinations of polymer are given in Table 3. It can be seen that the surface
tension of solutions varied from 28 mN/m to70 mN/m, depending on the concentrations and types of chemicals dissolved in
solutions.

Table 3
Surface tension of solution with different chemicals.

Solution with chemicals Surface tension (mN/m) Solution with chemicals Surface tension (mN/m)

AEA (%) SP (%) VMA (%) AEA (%) SP (%) VMA (%)
NO. 1 (0.01) 0 0 31.209 0 PNS (0.2) 0 67.569
NO. 1 (0.02) 0 0 28.188 0 PNS (0.5) 0 70.250
NO. 1 (0.04) 0 0 28.806 0 PNS (0.8) 0 70.333
NO. 2 (0.01) 0 0 39.639 0 PNS (1.2) 0 70.180
NO. 2 (0.02) 0 0 31.958 0 PCE (0.2) 0 42.222
NO. 2 (0.04) 0 0 32.958 0 PCE (0.5) 0 41.333
NO. 3 (0.01) 0 0 31.569 0 PCE (0.8) 0 41.139
NO. 3 (0.02) 0 0 29.069 0 PCE (1.2) 0 40.847
NO. 3 (0.04) 0 0 29.855 NO.1 (0.02) PNS (0.5) 0 38.736
NO. 4 (0.01) 0 0 37.014 NO.2 (0.02) PNS (0.5) 0 51.597
NO. 4 (0.02) 0 0 37.667 NO.3 (0.02) PNS (0.5) 0 41.444
NO. 4 (0.04) 0 0 37.229 NO.4 (0.02) PNS (0.5) 0 43.458
NO. 1 (0.02) PNS (0.5) HPMC (0.08) 35.861 NO.1 (0.02) PCE (0.5) 0 29.014
NO. 2(0.02) PNS (0.5) HPMC (0.08) 44.639 NO.2 (0.02) PCE (0.5) 0 31.639
NO. 3 (0.02) PNS (0.5) HPMC (0.08) 42.403 NO.3 (0.02) PCE (0.5) 0 31.667
NO. 4 (0.02) PNS (0.5) HPMC (0.08) 45.757 NO.4 (0.02) PCE (0.5) 0 35.597
NO. 1 (0.02) PCE (0.5) HPMC (0.08) 28.750 NO.1 (0.02) PCE (0.5) WG(0.08) 41.000
NO. 2 (0.02) PCE (0.5) HPMC (0.08) 29.680 NO.2 (0.02) PNS (0.5) WG(0.08) 52.986
NO. 3 (0.02) PCE (0.5) HPMC (0.08) 31.514 NO.3 (0.02) PNS (0.5) WG(0.08) 41.666
NO. 4 (0.02) PCE (0.5) HPMC (0.08) 35.542 NO.4 (0.02) PNS (0.5) WG(0.08) 43.653
NO. 1 (0.02) PCE (0.5) WG (0.08) 29.306 NO.3 (0.02 PCE (0.5) WG(0.08) 31.917
NO. 2 (0.02) PCE (0.5) WG (0.08) 30.542 NO.4 (0.02) PCE (0.5) WG(0.08) 33.292
 H. Huang et al. / Case Studies in Construction Materials 11 (2019) e00232 5

PCE can effectively reduce the surface tension of the solution from 71.150 mN/m to 40.847 mN/m at the concentration of
0.5%, while PNS had almost no effect on the surface tension of the solution. This is because that PNS molecular is aromatic
sulfonate aldehyde condensation, and a kind of anionic surfactant and non-air entraining superplasticizer. Its molecular
structure is a long chain with functional group. This kind of superplasticizer has little effect on the activity of gas-liquid
interface, therefore, has almost no effect on the surface tension of the solution. The molecular of PCE is comb-like structure.
There are a few strong polar active groups on the main chain and a lot of hydrophilic active groups on the side chain. Because
of strong gas-liquid interface activity, PCE has a significant influence on the surface tension of the solution [35].
Various types of AEA significantly reduced the surface tension of solution. Generally speaking, solutions with No. 4 AEA
(Rosin) had the highest surface tension. Solutions with No. 1 AEA (Alkyl benzene sulfonate with high molecular weight) had
lower surface tension than that of No. 2 (alkyl benzene sulfonate with low molecular weight). The surface tension of AEA
solution did not increase with the increasing of concentration. The lowest surface tensions of solutions with No. 1, No. 2 and
No. 3 AEAs all occurred at the concentration of 0.02% which may be close to their critical micelle concentration (CMC). While
the surface tension of No. 4 AEA had negligible change within the concentrations tested in this study. This indicated that the
CMC of NO. 4 AEA might be lower than 0.01%.
The surface tension of the complex solutions of PCE and AEA were close to that of pure AEA solution, and lower than that
of pure superplasticizer solution. The surface tension of the complex solution of PNS and AEA was lower than that of pure
superplasticizer solution, and higher than that of pure AEA solution. In the presence of PNS, AEA cannot effectively reduce
the surface tension of solution. PNS is condensed polymer, and PCE is a copolymer. The interaction between SP and AEA is
extremely complex, including ionic, polar and hydrophobic interactions. When AEA and SP mix together, they build a new
micro environment [35]. The interaction between PCE and AEA is based on hydrophobic groups, and mainly exhibits
association between hydrophobic groups of superplasticizer and surfactant. This type of interaction is dominant when
electricity is not obvious. The interaction between PNS and AEA is based on electrostatic interaction, which is mainly due to
the interaction between charged naphthalene and anionic surfactants [35].
In comparison with the solutions with SP and AEA, the addition of HPMC or WG had negligible effect on the surface
tension of the complex solutions with SP, AEA and VMA.

3.2. Foam ability and foam stability of suspensions with SP

The foam ability and foam stability of different suspensions with powders and SPs are shown in Fig. 2. As can be seen from
Fig. 2, PCE and PNS had different effects on the foam ability and foam stability of pure solution. Pure PCE solution had much
higher foam ability than that of PNS, and pure PNS solution almost had no foam ability. The suspensions with different
combinations of powders showed the same trend. For the suspensions with PNS, there were a small number of bubbles on
the surface of suspension after shaking, but it was very unstable and disappeared soon. The foam ability and foam stability of
suspensions agreed well with the surface tension of solutions in Table 3. When the surface tension of solution was high, the
foam ability index and foam stability index of suspensions were low.
In comparison with the suspensions with PNS, the foam ability and foam stability indexes of all the suspensions with PCE
were much higher. Although the surface tension of 0.5% PCE solution (41.133 mN/m) was slightly lower than that of 0.2% PCE
solution (42.222 mN/m), the former exhibited lower foam ability than the latter. The critical micelle concentration (CMC) of
superplasticizer molecules might explain this result. The CMC value of PCE might be lower than 0.2%. When the
concentration of solution exceeds the CMC, the excessive superplasticizer molecules have no benefit on the surface tension
and foam ability.

Fig. 2. Effect of SPs on foam ability and foam stability indexes of suspensions.
6 H. Huang et al. / Case Studies in Construction Materials 11 (2019) e00232

For different powder materials, the order of the foam ability index of suspensions with PCE was as follows:
PC > 2FA8PC > 1SF9PC > 4SL6PC. And the order of the foam stability index was as follows: 4SL6PC >1SF9PC > PC > 2FA8PC.
The addition of powder changed the foam indexes of suspensions because of chemical and physical reasons [1]. From the
chemical point of view, different cementitious materials release inorganic ions in different types and quantities (such as Ca2+,
Na+, K+, OH-, SO42) which influence the surface tension of liquid phase. The dissolution rate of FA and SF depends on the
pozzolanic reaction of active Al2O3 and SiO2 with calcium hydroxide. And the hydration rate of SL is much slower than that of
PC. It can be expected that the ionic concentration of the suspension with PC is higher than the others, and the dissolved ions
affect the foam ability of suspensions. It is generally believed that the unburned carbon in fly ash may adsorb the surfactant,
and thus affect the foam ability [28]. From the physical point of view, powder materials with different particle size have
different adsorption behavior at the gas-liquid surface which may affect the bubble formation and stability [1]. For example,
silica fume is a very fine powder and might be adsorbed onto the gas-liquid surface, and thus affect the air bubble formation
and stability.

3.3. Foam ability and foam stability suspensions with AEA

The foam ability and foam stability indexes of suspensions with AEA are shown in Fig. 3. All kinds of pure AEA solution had
good foam ability and foam stability. Although rosin had the highest surface tension, its solution had the best foam ability
and stability. However, the foam ability and foam stability of suspensions with different AEAs and powders were completely
different from that of the pure AEA solution. With the addition of powders, the foam ability and foam stability indexes were
decreased significantly. For all AEAs, suspensions with powders of slag and cement showed high foam ability and foam
stability indexes. Among the four types of AEA, the foam ability and foam stability indexes of suspensions with fatty alcohol
benzene sulfonic acid salts was the worst, while the rosin was the best. Alkyl benzene sulfonate with high molecular weight
had similar foam ability and foam stability as that of alkyl benzene sulfonate with low molecular weight.
Generally, AEA can be divided into ionic, anionic and non-ionic surfactants. Its surface activity stems from the hydrophile-
lipophile molecular structure [1,34]. The balance of the hydrophilic and hydrophobic groups results in the assembly of AEA
molecules in the gas-liquid interface and forming a molecular monolayer. When the interface is saturated with AEA, the

Fig. 3. Effect of AEAs on foam and foam stability indexes of suspensions.

 H. Huang et al. / Case Studies in Construction Materials 11 (2019) e00232 7

residual AEA molecules cannot enter the interface. However, the hydrophobic groups are still struggling to get the surfactant
molecules escape from water, and then the surfactant molecules self-assemble in the solution. In other words, hydrophobic
groups form a core, the hydrophilic groups stay out and contact with water, consequently, the simple micelle is formed.
When the surfactant concentration of solution reaches CMC, the surface tension of the solution reaches the lowest value. If
increasing surfactant concentration, the surface tension of solution does not decrease, but form many micelles and surface
tension may even increase [35]. In addition to the surface tension of solution, the air entraining of AEA also depends on the
input work during mixing. The adsorption of AEA at the gas-liquid interface decreases the surface free enthalpy, and thus air
bubbles can be much easier introduced for the solution with AEA under the same input work.
During the execution of test, it was noticed that fatty alcohol AEA introduced large and unstable bubble in pure solution,
and the addition of powder made the situation worse. Generally speaking, rosin was the best AEA to improve the foam ability
and foam stability of suspensions with different powders.

3.4. Foam ability and foam stability of suspensions with AEA and SP

Fig. 4 gives the foam ability and foam stability indexes of suspensions with SP, AEA and various powders. The foam ability
and foam stability indexes of pure solution with AEA and SP were comparable to that of pure solution with AEA. The addition
of powders significantly decreased the foam ability and foam stability indexes. In PCE-AEA suspension, the foam ability and
foam stability of suspensions with PC, 2FA8PC, and 1SF9PC were similar, while suspension with 4SL6PC had the lowest foam
ability and the best foam stability. For the four types of AEA, No. 3 AEA had the worst foam ability and foam stability, while
No. 4 AEA had the best. From statistical point of view, the average foam ability index of all suspensions with 0.02% AEA was
94.33%, and the average foam stability index was 79.63% (data in Fig. 3). By contrast, the average foam ability index of all
suspensions with AEA and PNS was 83.67%, and the average foam stability was 67.83%; while the average foam ability index
of all suspensions with AEA and PCE was 95%, and the average foam stability index was 81.17% (data in Fig. 4). It can be seen
that PNS decreases while PCE increases the air entraining effect of AEA.

Fig. 4. Effect of combination of 0.02% AEAs and 0.5% SPs on the foam and foam stability indexes of suspensions.
8 H. Huang et al. / Case Studies in Construction Materials 11 (2019) e00232

3.5. Foam ability and foam stability of suspension with SP, AEA and VMA

Fig. 5 gives the foam ability and foam stability indexes of suspensions with WG, SP, and AEA. As can be seen, the
incorporation of WG greatly decreased the foam ability and foam stability of pure solution with AEA and PCE, but slightly
decreased the foam ability and foam stability of pure solution with AEA and PNS. The same trends were observed on the
suspensions with different powders.
Fig. 6 gives the foam ability and foam stability indexes of suspensions with SP, AEA, and HPMC. In the case of pure
solution, the incorporation of HPMC generally had slight effect on the foam ability and foam stability of AEA-SP solution,
except rosin-PCE solution. The effect of HPMC on suspension with PNS-AEA was also more remarkable than that of
suspension with PCE-AEA.
The average foam ability index of all suspensions with AEA and SP was 89.33%, and the average foam stability index was
74.55% (data in Fig. 4). In comparison, the average foam ability of all suspensions with AEA, SP and WG was 28.33%, and the
average foam stability was 66.48% (data in Fig. 5); while the average foam ability of all suspensions with AEA, SP and HPMC
was 66.54%, and the average foam stability was 81.66% (data in Fig. 6). It can be seen that WG significantly decreases and
HPMC to a less extent decreases the air entraining effect of AEA-SP solution.
SP, VMA and AEA are polymers, and all of them have effects on the surface tension, solution viscosity, Gibbs-marangoni
surface elasticity, foam quality, gas solubility and permeability, pressure and bubble size distribution, and surfactant
solubility [35]. Furthermore, very complicated interactions might exist between these polymers. Therefore, the influence of
the combined polymer on the foam ability and foam stability is even more complicated. WG is a polysaccharide produced by
Alcaligenes Sp. (ATCC31555), its structure is like Gellan gum [36]. Literature [37] showed that the skeleton structure of WG
consists of D-glucose, D-glucuronic acid and L-rhamnose, while its side chain is composed of single stranded L-mannose or L-
rhamnose. In aqueous solution, the main force of WG molecules is Van der Waals’ force among intermolecular and hydrogen
bonding interaction between the side chain and backbone. When WG is not fully swelling in water, its molecules are

Fig. 5. Effect of combination of 0.02% AEAs, 0.5% SPs and 0.08% WG on foam ability and foam stability indexes of suspensions.
 H. Huang et al. / Case Studies in Construction Materials 11 (2019) e00232 9

Fig. 6. Effect of combination of 0.02% AEAs, 0.5% SPs and 0.08% HPMC on foam ability and foam stability indexes of suspensions.

dispersed in water in the irregular coil structure. In this case, the intermolecular forces are weak, and the viscosity of its
aqueous solution is low. When fully swelling in water, WG molecules stretch and intermolecular interaction becomes strong,
and thus the viscosity of its aqueous solution increases. When WG combines with PNS and AEA, it has slight effect on the
foam ability and foam stability since PNS and AEA are anionic surfactant. However, WG has significant effect on the comb-
like PCE. HPMC is natural polymer cellulose treated by chemical method. The thickening effect of HPMC is through long chain
expanding in water, and cellulose molecules bond with each other through hydrogen. This increases the volume of the
polymer itself, thereby increasing the viscosity of the system. HPMC is also a kind of cationic surfactant. Similar to WG, HPMC
had more obvious effect on solutions with PCE than that with PNS.

4. Discussion

Since surface tension test is more convenient and highly repeatable, Pederson et al. [28] proposed to use a new surface
tension test to replace foam index test, and good relationship were found on these two methods. The relationship between
surface tension and foam ability and foam stability indexes of suspensions are shown in Fig. 7. If the surface tension of the
solution is low, it is very likely that the foam ability and foam stability indexes of suspensions are high. However, low surface
tension of suspension may also have low foam ability and foam stability indexes. Therefore, surface tension is one of the main
factors influencing the foam ability and foam stability indexes, but the surface tension did not determine the foam ability and
foam stability of suspensions.
The average values of foam ability and foam stability indexes of suspension with various powders are shown in Fig. 8. Note
that all the data appeared in this paper have been used for the statistical analysis. The effect of mineral admixtures on the
foam stability index of suspension was not remarkable. Slag can increase the foam ability of suspension, and fly ash and silica
fume can slightly decrease the foam ability of suspension. Mineral admixtures had slight effect on the foam stability.
10 H. Huang et al. / Case Studies in Construction Materials 11 (2019) e00232

Fig. 7. Average values of foam ability and foam stability of powders.

Fig. 8. Average values of foam ability and foam stability index of suspensions with chemical admixtures.

The average values of foam ability index and foam stability index of suspensions with various chemical admixtures are
shown in Fig. 9. It is surprised to see that PNS was easier to foam than PCE although PNS solution had higher surface tension.
In the case of suspension with SPs and AEAs, suspension with PCE had much higher foam ability and foam stability than
suspension with PNS. VMAs had much more negative effect on the foam ability and foam stability of suspension with PCE
than that with PNS. NO. 1 AEA had the best air entraining effect, and NO. 4 AEA had higher foam stability index. In comparison
with WG, suspensions with HPMC had higher foam ability and foam stability indexes.

Fig. 9. Relationship between surface tension and foam ability and foam stability.
 H. Huang et al. / Case Studies in Construction Materials 11 (2019) e00232 11

5. Conclusions

Based on the experiments, the following conclusions can be drawn:

(1) Surface tension of the solution is one of the main factors influencing the foam ability index and foam stability index, but
not the decisive factor. Low surface tension of suspensions may also lead to high foam ability and foam stability.
(2) The use of PCE in the suspension is much easier to foam than that of PNS when VMA is not used. When VMA is combined
with SP, the opposite phenomenon is observed. This is because VMAs have much more negative effect on the foam ability
and foam stability of suspension with PCE than that with PNS.
(3) The influence of different mineral admixtures on the foam ability and foam stability indexes of suspensions are different,
which depends on powder fineness, particle surface properties, and the concentrations and types of ions released into
water. However, the effect of powder on the foam indexes is much less remarkable than that of chemical admixtures.
(4) In comparison with WG, suspension with HPMC has higher foam ability and foam stability indexes.
(5) Alkyl benzene sulfonate with high molecular weight has good foaming ability, but rosin has good foam stability. The
alcohol benzene sulfonate and alkyl benzene sulfonate with low molecular weight are not suitable for application in
cement-based materials.

Conflict of interest

We declare that we have no financial and personal relationships with other people or organizations that can
inappropriately influence our work.

Acknowledgements

Financial supports by National Key R&D Program of China (contract No. 2017YFB0310100) and National Science
Foundation of China (contract No. 51778629) are greatly appreciated.

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