12 Fire Technology, 51, 503–511, 2015

Ó 2014 Springer Science+Business Media New York. Manufactured in The United States
DOI: 10.1007/s10694-014-0422-5

Application of Green Surfactants

Developing Environment Friendly Foam
Extinguishing Agent

Peng Wang*, The Chinese People’s Armed Police Forces Academy, Langfang
065000 Hebei, China

Received: 2 December 2013/Accepted: 22 June 2014

Abstract. The green surfactants were used to develop environment friendly foam
extinguishing agent instead of fluorocarbon surfactant. The surface tension and foam
property of a variety of green surfactants were studied by orthogonal experiments.
Alkyl glucose amide and organosilicone surfactant were selected. The foam property
of alkyl glucose amide and surface tension of organosilicone surfactant were experi-
mentally studied. And finally, the content of two surfactants were determined by con-
sidering the interaction of orthogonal experiments. The fire extinguishing
performance of 2.5% alkyl glucose amide and 2% organosilicone surfactant contain-
ing foam extinguishing agent met the national standard requirements. Conclusion:
alkyl glucose amide and organosilicone surfactant can replace fluorocarbon surfac-
tant in foam extinguishing agent. This fire extinguishing agent is completely in con-
formity with ‘‘Stockholm Convention’’, and environment friendly foam extinguishing
agent.

Keywords: Green surfactants, Alkyl glucose amides, Organosilicone surfactant, Orthogonal experiment,
Stockholm Convention

1. Introduction
Fluorocarbon surfactant is the key ingredient in aqueous film-forming foam extin-
guishing agent, because of its high surface activity and oleophobicity. However,
Fluorocarbon surfactant has high chemical stability and thermal stability, and is
difficult to degrade in a long-term and pollutes the environment. So, its usage
arouses international attention. Among them, perfluorooctane sulfonate (PFOS),
an internationally recognized POPs, which was included in the ‘‘About the Stock-
holm convention on persistent organic pollutants (pops)’’ [1–3]. The need for envi-
ronmentally acceptable fire fighting foams is very important, with Stockholm
Convention, Fourth Conference of Parties restrictions on perfluorooctanesulfonic
acid (PFOS), its salts and perfluorooctanesulfonyl fluoride (PFOSF) (May 2009).
Other fluorosurfactants have been used to produce effective foam agents, but
restrictions on them will most likely evolve.

* Correspondence should be addressed to: Peng Wang, E-mail: wangpengcapf@139.com

504 Fire Technology 2015

It was Japanese experts who first use green surfactants to develop environment
friendly foam extinguishing agent. Japanese expert Shika Bo has invented a kind
of foam extinguishing agent without fluorocarbon surfactant in 2005 [4], using
betaine typed surfactants. Atsushi Ohya has invented a kind of fire extinguishing
agent which exhibits both high fire extinguishing performance and high safety to
the human body. The fire extinguishing agent is composed of one or more alkali
metal carboxylates selected from potassium acetate, potassium citrate, sodium ace-
tate, and sodium citrate; one or more natural surfactants selected from lecithin,
saponin, and casein; a lower alcohol having four or less carbon atoms which is
designated as a food additive; and water [5]. Izumida Masashi has invented a kind
of fire extinguishing agent which has both high fire-extinguishing performance and
a high level of safety to the environment and the human body. This fire extin-
guishing agent is characterized by containing a biosurfactant [6]. The natural sur-
factants used by Japanese experts: lecithin, saponin; or biosurfactants:
rhamnolipid, surfactin and so on, are very environment friendly, but also very
expensive. The high price of these natural surfactants has prevented their usage in
industrial production of foam fire extinguishing agent. Ted H. Schaefer studied
sealability properties of Fluorine-Free Fire-Fighting Foams (FfreeF) [7]. And Ber-
nard Król studied Biodegradability of Firefighting Foams [8].
This paper finds surfactants which are both biodegradable and cheap, and use
such surfactants instead of fluorocarbon surfactants to develop environment
friendly foam fire extinguishing agent. The Key technology is whether it can find a
surfactant that reduces the surface tension, so that the foam can rapidly spread on
the aliphatic hydrocarbon mixture surface or not.

2. The Choice of Surfactants

The surfactants used to develop foam fire extinguishing agent in this paper should
meet the following conditions: (1) commercially available, such surfactants should
have the chemical production; (2) cheap, the foam extinguishing agent produced
with the surfactant should be able to be used a lot by general fire brigade; (3)
environmental protective, the surfactant should not be water and soil pollution,
thus is recognized as green surfactant. After the author’s detailed research, the fol-
lowing 10 initial choices of surfactants are listed in Table 1.

3. Surfactants Screening Experiment

Ten kinds of the above mentioned surfactants are conducted a 10 factors 2 levels
orthogonal test. Experiments are conducted in accordance with the L12(2 [11])
orthogonal table. 12 Formulations are shown in Table 2.
In Table 2 the number means weight percentage in foam solution and the rest is
water. 10 factors in different formulations are surfactants, which directly effect on
spreading coefficient of the foam solutions and expansion and drainage of foam,
but weakly effect on sediment, viscosity and pH. So the experimental indicators
are surface tension, interfacial tension, expansion and 25% drainage time of
Table 1
Environment Friendly Surfactants

Surfactants Code Property Source

Application of Green Surfactants

1 Soybean lecithin SL Natural China Beijing JingTong LeTai chemical product co., ltd.
2 Organosilicone surfactant OSS Organosilicon China Shanghai LuHong agricultural science and technology co., ltd.
3 Alkyl glycoside APG Nonionic China LinYi LanShan LvSen chemical industry co., ltd.
4 Alkyl glucose amide AGA Nonionic China ShangHai ZhengQi trading co., ltd
5 Methyl ester sulfonate MES Anionic China LinYi LanShan LvSen chemical industry co., ltd.
6 Sodium lauroyl glutamate SLG Amino acid China LinYi LanShan LvSen chemical industry co., ltd.
7 Sodium lauroyl sarcosinate SLS Amino acid China Guangzhou ZhuFeng import and export trade co., ltd.
8 Coconut oil fatty acid glycine potassium GCK-12 K Amino acid Japan Kotobuki Pharmaceutical (bought in China)
9 Cocamidopropyl betaine CAB-35 Betaine China Beijing JingXiFang technology co., ltd.
10 Dodecyl dimethyl betaine BS-12 Betaine China LinYi LanShan LvSen chemical industry co., ltd.
505
506 Fire Technology 2015

Table 2
Formulations of Surfactants Screening Orthogonal Experiment

Formulations SL OSS APG AGA MES SLG SLS GCK-12K CAB-35 BS-12

1 0 0.5 0 0.5 0 0.5 0 0.5 0 0.5

2 0 0.5 0 0.5 0 0 0.5 0 0.5 0
3 0 0.5 0.5 0 0.5 0.5 0 0.5 0.5 0
4 0 0 0 0 0.5 0.5 0.5 0 0 0.5
5 0 0 0.5 0.5 0.5 0 0 0 0 0
6 0 0 0.5 0 0 0 0.5 0.5 0.5 0.5
7 0.5 0.5 0.5 0 0 0.5 0.5 0 0 0
8 0.5 0.5 0.5 0.5 0.5 0 0.5 0.5 0 0.5
9 0.5 0.5 0 0 0.5 0 0 0 0.5 0.5
10 0.5 0 0.5 0.5 0 0.5 0 0 0.5 0.5
11 0.5 0 0 0 0 0 0 0.5 0 0
12 0.5 0 0 0.5 0.5 0.5 0.5 0.5 0.5 0

Table 3
Surfactant Screening Orthogonal Experiment

Surface tension Interfacial tension Drainage

Formulations (mN/m) (mN/m) Expansion time (s)

1 24.7 2.4 6.2 276

2 23.9 2.3 6.2 244
3 24.5 2.5 5.9 253
4 26.9 3.5 6.1 247
5 29.3 2.1 6.5 270
6 28.6 2.5 6.2 285
7 27.6 5.9 6.0 213
8 25.6 3.1 5.9 233
9 25.4 4.7 4.5 139
10 28.0 2.8 6.4 299
11 35.3 9.5 2.0 30
12 28.5 4.1 5.9 275

different formulations. Experimental methods are in the provisions of the

GB15308-2006 ‘‘Foam Extinguishing Agent’’ [9]. GB15308-2006 is a Chinese
national standard, which is written in Chinese. For readers who are lack of famil-
iarity with this standard can look up BS EN 1568-3-2008 [10], which is written in
English. Testing procedures and success criteria in these two standards are exactly
the same. Table 3 shows the experimental data.
The variance analysis of Table 3 data shows that: alkyl glucose amide is very
significantly prolonging drainage time, significantly increasing the expansion ratio,
very significantly reducing the surface tension. Organosilicone surfactant is very
significantly reducing the surface tension. Soybean lecithin is very bad for the
development of foam fire extinguishing agent. Therefore, alkyl glucose amide and
organosilicone surfactant are selected. So Further experiments are needed in the
Application of Green Surfactants 507

6.5 240
expansion
drainage time 220
6.0
200

5.5 180

drainage time (s)

160
expansion

5.0
140
4.5 120

100
4.0
80
3.5
60

3.0 40

20
2.5
0.0 0.5 1.0 1.5 2.0 2.5 3.0
AGA(%)

Figure 1. The influence on foam property with AGA content.

foaming of alkyl glucose amide and reducing the surface tension of organosilicone
surfactant, to determine the content of the two surfactants in the formulation of
fire extinguishing agent.

4. Determining the Content of the Surfactant

4.1. Foam Property Experiment of Alkyl Glucose Amide
Under certain condition of the OSS content (1% in solution), the influence on
drainage time and expansion ratio with different levels of AGA is tested. Experi-
ment is done with the former method. Figure 1 shows the experimental data.
Seen from Figure 1, the foaming expansion ratio and drainage time perfor-
mances are both poor when the AGA is less than 1%; and significantly improved
when the AGA is more than 1% and less than 2%; and very good when the AGA
is more than 2%. So the content of AGA should be more than 2%. P.S. all the
percentages in this paper refer to weight percentage in foam solution and the rest
is water.
The alkyl glucose amide (AGA) is produced from starch or glucose and fatty alco-
hols, organic amines and fatty acids, which is a new kind of green mild surfactant. In
addition to the basic properties of conventional surface active agent, AGA also has
other unique advantages such as moderate to human body, non-toxic, high deter-
gency, rich and stable foam, quickly and completely biodegradable, excellent syner-
gistic effect, and so on. It can satisfy the future need of environment protection.
From the ecology and energy point of view, AGA will be the most promising surfac-
tant in new generation. It can be widely used in daily chemical, pharmaceutical,
508 Fire Technology 2015

27
surface tension

surface tension (mN/m) 26

25

24

23

22

21
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
OSS (%)

Figure 2. Influence of organosilicone surfactant content on surface

tension.

Table 4
Formulations of Orthogonal Experiment Considering the Interaction

Formulations AGA (%) OSS (%)

1 2 1.8
2 2 2
3 2 2.2
4 2.5 1.8
5 2.5 2
6 2.5 2.2
7 3 1.8
8 3 2
9 3 2.2

textile, food, biology, materials, agricultural and industrial separation and other
industries. The new mild green surfactants were developed in 1990s, represented by
AGA and APG (alkyl glucosides), have been gradually commercialized. From the
physical and chemical properties and abroad application point of view, AGA is not
only as good as APG, but also has even more advantages than APG in some
respects [11, 12].

4.2. Influence of Organosilicone Surfactant Content on Surface Tension

Under certain condition of AGA content (3%), the influence of OSS content on
surface tension is tested. The OSS used in experiments is bought from China Shang-
hai LuHong agricultural science and technology co., ltd. And the trade mark is
‘‘LuHong 111’’. Its chemical component is polyethoxylated modified trisiloxane.
Application of Green Surfactants 509

Table 5
The Orthogonal Experiment Considering Interaction of AGA Between
OSS

Formulations Surface tension (mN/m) Interfacial tension (mN/m) Expansion Drainage time (s)

1 21.2 2.0 5.4 215

2 21.0 1.7 5.4 224
3 21.0 1.7 5.3 206
4 20.1 1.6 5.9 232
5 19.7 1.8 5.9 245
6 21.2 1.9 5.9 231
7 21.7 1.8 6.2 234
8 21.8 1.8 6.1 226
9 21.6 1.7 6.0 231

Table 6
The Sequence of Effect of AGA and OSS on Different Experimental
Items

Surface Interfacial Sum of surface and Drainage

Factors tension tension interfacial tension Expansion time

AGA 1 3 1 1 1
OSS 3 2 3 2 2
interaction 2 1 2 3 3

Experiment is done with the former method. The experimental data are shown in
Figure 2.
Seen from Figure 2, as the OSS content is increased, the surface tension decrea-
ses monotonically. According to the equation for calculating the spreading coeffi-
cient in GB15308-2006 [9] or BS EN 1568-3-2008 [10], after experiment, this paper
thinks that: the surface tension of cyclohexane is greater than 24 mN/m, the inter-
facial tension of cyclohexane between foam is less than 2 mN/m. That is to say, as
long as the foam surface tension is less than 22 mN/m, the spreading coefficient
can be guaranteed positive. So the content of OSS should be more than 1.8%.

4.3. The Interaction of AGA Between OSS

The above experiments are single factor and multi-levels, and the interaction of
two factors is not considered. If you want to consider interaction of AGA
between OSS, we must conduct orthogonal experiment. L9(3 [4]) orthogonal table
is taken, 9 formulations are shown in Table 4.
In Table 4 the number means weight percentage in foam solution and the rest is
water. Experimental data are drainage time, expansion ratio, surface tension and
interfacial tension. Experiment with the former method. Experimental data are
shown in Table 5. Table 5 data are analyzed of variance, to determine the
sequence of the effect of various factors on different experimental items. Data
analysis results are shown in Table 6.
510 Fire Technology 2015

Considering the degree of importance of different items and sequence of effect of

different factors on different items, The content of AGA is 2.5% and OSS is 2%.
Organosilicone surfactants (OSS) is a new type of special surfactant, which was
developed after 1960s. It is fluoride free, high surface activity, non-toxic, non-cor-
rosive, cheap, and physiologically inert [13]. OSS compounded with AGA, and the
surface tension can be reduced to less than 20mN/m. It greatly improves the
spreadability of foam. OSS is not persistent organic pollutants and not banned in
Stockholm Convention. It can replace fluorocarbon surfactant. High foam-type
fire extinguishing agents often use anionic or polyether modified organosilicone
surfactant as a stable foam or foaming agent. Such as Germany ‘‘silicone SW-
802’’ foam extinguishing agent is on the basic of anionic OSS [14, 15].

5. Fire Performance Experiment

Based on the above results, the formulation of foam extinguishing agent are AGA
2.5%, OSS 2%, xanthan gum 1& and water. The fire experiment is conducted in
accordance with the national standard GB15308-2006 [9], which is exactly the
same as BS EN 1568-3-2008 [10]. Extinction time is 2.5 min, extinguishing perfor-
mance class achieved class I; burnback time is 6 min, burn-back resistance level
achieved level D. Which meets the low expansion foam extinguishing agent fire
performance requirements of Chinese national standard for water-immiscible
liquid fuel.
The burn-back resistance level of foam extinguishing agent with OSS is only D,
which is much shorter than level B (15 min). I think there are two reasons.

(1) poly- and perfluorinated compounds in foam agents provide a important and
intrinsic property - the oleophobicity, but OSS can’t.
(2) While silicone surfactants may reduce surface tension greatly, some are foam
breakers and not foam formers. Thus, some may be useful for fire fighting
foams, others are not and actually break down foams.

6. Conclusion
Through a large number of orthogonal experiments, it comes to the conclusion
that: alkyl glucose amide (AGA) and organosilicone surfactant (OSS) can replace
fluorocarbon surfactant to prepare foam extinguishing agent. So there isn’t per-
fluorooctane sulfonate and other POPs in the foam extinguishing agent. There-
fore, this foam extinguishing agent is completely in conformity with Stockholm
Convention. It is the first reported OSS based fire fighting foam without fluoro-
carbon surfactant, so far as I know.
Should be dedicated to the development of an organosilicone surfactant used in
foam extinguishing agent. This organosilicon surfactant should have oleophobic-
ity, high surface activity, foamability and environment friendly. This is a new way
to solve the pollution problem of AFFF and the author’s work in the future.
Application of Green Surfactants 511

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