Synthesis of bis[N,N′-(alkylamideethyl)ethyl] triethylenediamine bromide surfactants and their Oilfield application investigation

Article abstract of DOI:10.1007/s11743-011-1313-0

Bis[N,N′-(alkylamideethyl)ethyl] triethylenedi-amine surfactants are quaternary ammonium salt Gemini surfactants with amide, which are synthesized from fatty acid (dodecanoic, hexadecanoic, tetradecanoic and octa-decanoic) methyl esters, triethylene tetramine and ethyl bromide. The chemical structures of the prepared compounds were characterized by elemental analysis, FTIR and ¹H-NMR spectra, melting point and Krafft point. Several properties of the synthesized surfactants were studied including surface tension, critical micelle concentration, interfacial tension, emulsification power, salt effect, corrosion inhibition efficiency and biological activity. The results show that the surface activity, critical micelle concentration and interfacial activity are correlated to their chemical structures. The emulsification power measurements of these surfactants show their low emulsifying tendency towards Tazhong's crude oil from Tarim Oilfield. The synthesized surfactants also exhibit high biocidal activity towards Gram-positive and Gram-negative bacteria and fungi. This activity increases with the increase of alkyl chain length. The corrosion measurement of these surfactants in acidic media with a weight loss technique show good protection of mild steel alloys against acidic environments. These properties suggest that the synthesized compounds have potential for application in the oilfield area.

Full text of DOI:10.1007/s11743-011-1313-0

J Surfact Deterg (2012) 15:309–315
DOI 10.1007/s11743-011-1313-0
ORIGINAL ARTICLE
Synthesis of Bis[N,N0-(alkylamideethyl)ethyl] Triethylenediamine
Bromide Surfactants and Their Oilfield Application Investigation
•
Ming Zhou Jinzhou Zhao Xingqi Hu
•
Received: 5 November 2010 / Accepted: 21 September 2011 / Published online: 9 December 2011
Ó Crown Copyright as represented by: State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation Engineering
and School of Material Science and engineering /Southwest Petroleum University 2011
Abstract Bis[N,N0-(alkylamideethyl)ethyl] triethylenedi-
amine surfactants are quaternary ammonium salt Gemini
surfactants with amide, which are synthesized from fatty
acid (dodecanoic, hexadecanoic, tetradecanoic and octa-
decanoic) methyl esters, triethylene tetramine and ethyl
bromide. The chemical structures of the prepared com-
pounds were characterized by elemental analysis, FTIR and
1H-NMR spectra, melting point and Krafft point. Several
properties of the synthesized surfactants were studied
including surface tension, critical micelle concentration,
interfacial tension, emulsification power, salt effect, cor-
rosion inhibition efficiency and biological activity. The
results show that the surface activity, critical micelle con-
centration and interfacial activity are correlated to their
chemical structures. The emulsification power measure-
ments of these surfactants show their low emulsifying
tendency towards Tazhong’s crude oil from Tarim Oilfield.
The synthesized surfactants also exhibit high biocidal
activity towards Gram-positive and Gram-negative bacteria
and fungi. This activity increases with the increase of
alkyl chain length. The corrosion measurement of these
surfactants in acidic media with a weight loss technique
show good protection of mild steel alloys against acidic
environments. These properties suggest that the synthe-
sized compounds have potential for application in the
oilfield area.
Keywords Synthesis ꢀ Cationic Gemini surfactant ꢀ
Surface activity ꢀ Interfacial activity ꢀ Corrosion inhibition ꢀ
Biocidal activity
Introduction
Gemini surfactants are a new generation of surfactants
made up of two identical amphiphilic moieties covalently
connected at the level of the head groups by a spacer group.
The separation between the polar head groups within a
Gemini surfactant is strongly decreased when they aggre-
gate and thus the surface activity is greatly enhanced.
On the one hand, compared with conventional surfac-
tants, Gemini surfactants exhibit lower CMC values and
higher surface activity, which make Gemini surfactants
superior to the sole surfactant employed in EOR [1–3]. In
order to improve the ability of oil-displacement agent
reducing the interfacial tension of oil/water and improve
the recovery ratio of crude oil. Gemini surfactants have
application potential in EOR area [4, 5].
M. Zhou ꢀ J. Zhao (&)
State Key Laboratory of Oil and Gas Reservoir Geology
and Exploitation Engineering, 610500 Chengdu, Sichuan, China
e-mail: zhaojz62@163.com
M. Zhou
On the other hand, aggressive acid solutions are widely
used for industrial purposes, and inhibitors are commonly
used to control metal dissolution as well as consumption.
Most acid inhibitors are organic compounds containing
oxygen, nitrogen and/or sulfur [6]. Acid inhibitors have an
important role as a component in pre-treatment composi-
tions, cleaning solutions and in acidization of oil wells.
College of Material Science and Engineering,
Southwest Petroleum University,
610500 Chengdu, Sichuan, China
X. Hu
College of Chemistry and Chemical Engineering,
Southwest Petroleum University,
610500 Chengdu, Sichuan, China
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J Surfact Deterg (2012) 15:309–315
Compounds with functional groups containing heteroat-
oms, which can donate lone pair electrons, are found to be
useful as inhibitors of metal corrosion [7–9]. Meanwhile,
bacteria influence the production process of oil due to their
tendency to degrade crude oil. Also, bacteria have the
capability to reduce sulfur containing crude oil to produce
H2S gas which itself is corrosive. Hence, biocides are
widely used for sewage treatment using recycling in oil-
field applications. The most common biocides in industrial
applications are the quaternary ammonium surfactants. The
integrated consumption of biocides and acid inhibitors
encourages the development of different types of cationic
Gemini surfactants.
The bis(2-alkylamideethyl) ethylene diamine (R =
C11H23, C13H27, C15H31, C17H35) are bis(2-dodecanoyl-
ethyl) ethylene diamine (BDEE), bis(2-hexadecanoylethyl)
ethylene diamine (BHEE), bis(2-tetradecanoylethyl) ethyl-
ene diamine (BTEE) and bis(2-octadecanoylethyl) ethylene
diamine (BOEE), respectively. The yield values of BHEE,
BTEE and BOEE are 70.2, 72.8 and 73.6%, respectively.
Synthesis of the Cationic Gemini Surfactants
A total of 0.02 mol (BDEE 10.21 g, BHEE 10.77 g, BTEE
11.33 g, BOEE 11.89 g) of each of the prepared diamines
was refluxed in the presence of 0.16 mol (17.43 g) of ethyl
bromide and 0.02 mol (2.12 g) of sodium carbonate in
absolute alcohol (100 mL) for 48 h at 90 °C and allowed to
separate overnight. The quaternary ammonium salts were
filtered off in order to remove inorganic salts, then the
solvent and unreacted ethyl bromide were remove by a
rotary evaporation instrument for 8 h; washed twice with
the mixture solution (Vacetone:Vabsolute alcohol = 19:1) and
dried in a vacuum oven at 40 °C [11]. The chemical
structures of the multifuctional cationic Gemini surfactants
(MCGS) are shown in Scheme 2.
In this study, four model quaternary ammonium Gemini
surfactants were prepared from common ingredients, and
their structure characteristics are presented, and its appli-
cation properties in oilfield application areas are evaluated
aiming at providing theory in support of their application
in the oilfield chemistry area. In this paper, four model
quaternary ammonium Gemini surfactants with amide are
referred to below as m–s–m, where m and s stand for the
carbon atom numbers in the alkyl chain and the spacer,
respectively.
Bis[N,N0-(alkylamideethyl)ethyl]
triethylenediamine
bromides were synthesized, namely, 12–2–12, 14–2–14,
16–2–16, 18–2–18 four mode cationic Gemini surfactants
with amide group are synthesized, respectively. The yield
values of 12–2–12, 16–2–16 and 18–2–18 were 61.5, 63.3
and 59.2%, respectively.
Experimental Procedures
Synthesis of Bis(2-alkylamideethyl) Ethylene Diamine
Triethylene tetramine (0.05 mol, 7.31 g) was aminated with
fatty acid (dodecanoic, hexadecanoic, tetradecanoic and
octadecanoic) methyl esters (0.1 mol—21.43, 24.24, 27.05,
29.85 g, respectively) in the presence of xylene (15 mL) as
a solvent and potassium hydroxide (0.0025 mol, 0.14 g) as
a catalyst at 130–140 °C. The reaction lasted for 20 h and
was allowed to cool down to room temperature until a light
yellow solid had separated out. Then, the solvent and
unreacted materials were removed by vacuum distillation
[10], and the solid was recrystallized two times by the
Elemental Analysis
Microelemental analysis of the synthesized surfactants was
performed using a Vario Elementar instrument. The results
are shown in Table 1.
Melting Points and Krafft Points
The melting points (Tm) of the synthesized Gemini sur-
factants were determined using a Bu¨chi melting point
instrument B545. The measurements showed sharp melting
mixture solution (Vabsolute alcohol:Vdiethyl
= 1:1) and
ether
finally filtered and dried in a vacuum oven at 40 °C. The
chemicals were supplied by the Kelong Chemicals Com-
pany and were of analytical purity. The chemical reaction of
the synthesis of bis(2-alkylamideethyl) ethylene diamine is
given in Scheme 1.
Na2CO3
RCOHN(CH2CH2NH)2CH2CH2NHCOR+CH3CH2Br
CH3CH2OH
CH3
CH2
CH3
CH2
Br-
Br-
RCOHNCH2CH2NCH2CH2NCH2CH2NHCOR
KOH
RCOOCH3 + H2N(CH2CH2NH)2CH2CH2NH2
CH3
CH2
CH3
CH2
CH3
RCOHN(CH CH NH) CH CH NHCOR
+ 2CH3OH
R=C 11H23, C13H27, C15H31, C17H35
2
2
2
2
2
Scheme 1 The formula of bis(2-alkylamideethyl) ethylene diamine
Scheme 2 The formula of bis(2-alkylamideethyl) ethylene diamine
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J Surfact Deterg (2012) 15:309–315
311
Table 1 Microelemental analysis of the prepared surfactant
m–s–m
Chemical formula
C (%)
Calc.
H (%)
Calc.
N (%)
Calc.
Br (%)
Calc.
Found
Found
Found
Found
12–2–12
14–2–14
16–2–16
18–2–18
C38H80O2N4Br2
58.36
60.12
61.88
63.41
58.15
59.98
61.59
63.00
10.48
10.75
10.92
11.14
10.27
10.55
10.79
11.00
7.35
6.72
6.41
5.99
7.14
6.66
6.25
5.88
20.48
19.11
18.01
16.89
20.36
19.00
17.81
16.77
C
C
C
42H88O2N4Br2
46H96O2N4Br2
50H104O2N4Br2
1H-NMR Spectra
points for the synthesized surfactants (116, 128, 144 and
162 °C) for dodecanoate, hexadecanoate, tetradecanoate
and octadecanoate derivatives, respectively. With the
increase in the carbon chain length, Tm of surfactant
molecule increased. The results can be seen from Table 2.
The Krafft points (TK) showed low temperature solution
ability of ionic surfactants in distilled water. Electrical
conductivity can be used to determine the TK of the ionic
surfactant using plots of electrical conductivity (K) against
temperature (T). The electric conductivity was measured by
a Model of a DDS-IIA conductometer within the temper-
ature range of 10–80 °C. The results are shown in Table 2.
With the increase in the chain length, the hydrophobicity of
a surfactant molecule increased, leading to an increase in
the TK. For this reason, there was a great difference in the
TK of the m–2–m surfactant. For example, 12–2–12 and
14–2–14 dissolve well enough at 30 °C, however, the TK of
16–2–16 and 18–2–18 was at a temperature of 42.5 °C. For
these reasons, the surfactant and interfacial tension experi-
ments were carried out at a temperature of 45 °C.
NMR spectroscopic analyses of the synthesized Gemini
surfactants were performed using a Bruker model DRX-
300 NMR spectrometer with tetramethylsilane (TMS) as an
1
internal standard. H NMR [D2O, TMS] d: 0.89 (t, 6H,
CH3C– of two long carbon chains), 1.28–1.61 [t, methylene
in alkane, C(CH2)n-3C–], 2.28 [t, 4H,–N(C=O)CH2–], 3.30
[t, 4H, –CH2N (C=O)–], 3.41 [t, 16H, (–CH2)2N?(CH2)2–],
1.41 (t, 12H, CH3C– of four short carbon chains) and
4.28 ppm (s, 2H, –NHCO–). The spectra showed a signal at
2.14 ppm corresponded to a –CONH– group; integration
number of the hydrogen atoms was two. That signal dis-
appeared by addition of D2O. This analysis confirms the
formation of dimeric derivatives with amide only in the
synthesized Gemini surfactants.
Surface Tension Measurements
Surface tension measurements were carried out on freshly
prepared Gemini surfactants solutions within a concentra-
tion range of10-5–10-1mol L-1at 45 °C using a Jzhy1-180
Tensiometer produced by the Chengde Pilot Plant. The
surfactant solutions were prepared in HPLC water [12].
Infrared Spectra
Infrared spectroscopic analysis of the synthesized Gemini
surfactants was performed using a Fourier-transfer infrared
spectrophotometer and showed the following absorption
bands:
Interfacial Tension Measurements
tC–H = 2,950 (CH3–), tC–H = 2,850 cm-1 (–CH2–),
The interfacial tension was measured at 45 °C by the
spinning-drop technique using a JJ2000-B interfacial ten-
siometer produced by the Shanghai Zhongchen Instrument
Company, which has a wide range of measurement,
10-6–10-1 mN m-1. The spinning-drop method is based
on a balance of centrifugal and interfacial tension force [13].
dC–H = 1,470 cm-1(–CH2–),
tN–H,tC=O = 3,285 and
1,660 cm-1, respectively (–CONH–), tC–N = 1,215 cm-1
(–CH2NH–).
Table 2 Melting points and Krafft points of the synthesized Gemini
surfactants
Emulsification Power
m–s–m
Chemical formula
C38H80O2N4Br2
Tm (°C)
TK (°C)
Emulsification power of the synthesized surfactants is
measured by vigorous hand shaking of 10 mL surfactant
solution (1.0 9 10-3 mol L-1) and 10 ml of the same
crude oil described above for 5 min at 45 °C. The emul-
sification power is expressed as the time required for sep-
aration of 9 mL of pure water.
12–2–12
14–2–14
16–2–16
18–2–18
116
128
144
162
22.2
30.0
38.6
42.5
C42H88O2N4Br2
C46H96O2N4Br2
C50H104O2N4Br2
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J Surfact Deterg (2012) 15:309–315
Corrosion Measurements
of the synthesized surfactants decreased the surface tension
considerably due to the hydrophobic effect of the alkyl
chains [16].
A weight-loss technique [14] was used to measure the
inhibiting efficiency to corrosion of the prepared surfac-
tants for mild steel in HCl solutions at 45 °C for 5 days.
The experiments were performed with mild steel speci-
mens having a composition (wt%): 0.22 C, 0.034 Si, 0.55
Mn, 0.78 P, and the remainder Fe. Each specimen was
machined into regular shapes of 4 cm2 cross-sectional area.
The specimens were sequentially abraded with different
emery papers, decreased with acetone, washed with dis-
tilled water and dried. Corrosive solutions of 4 N HCl in
the absence and presence of the inhibitor at a concentration
of 100 mg L-1 were prepared from doubly distilled water.
Critical micelle concentration values were obtained
from the inflection points on the graph. It can be seen from
Fig. 1 that the critical micelle concentrations (CMC) of
12–2–12, 14–2–14, 16–2–16, 18–2–18 were 1.0 9 10-3
,
7.5 9 10-4, 5.0 9 10-4, 5.0 9 10-4 mol L-1, respec-
tively. The critical micelle concentration values show a
consistent decrease with increased alkyl chain length.
Hence, the most effective compound as a surface-active
agent in the synthesized homologue series is the 18–2–18
Gemini surfactant.
Interfacial Activity
Biocidal Activity
The experimental temperature was set at 45 °C and
experiments were carried out with special care to avoid
water evaporation. Also, interfacial tension measurements
were made for surfactant–oil systems at 45 °C. The crude
oil was supplied from the Tarim Oilfield of China and had a
Biocidal activity of the synthesized surfactants was mea-
sured at the Center for Bioengineering and Biotechnology
(CBB, Petroleum University of China (East China)) using
the inhibition zone technique in dimethyl formamide as a
solvent and acetyl trimethyl ammonium chloride as a
reference. The studied microorganisms were isolated using
successive isolation method then identified for each strain
as Gram negative bacteria: Escherichia coli, Gram positive
bacteria: Bacillus subtilis, Staphylococcus aureus. and
fungi: Candida albicans, Aspergillus flavus [15].
density of 0.82 g cm-3
.
The effect of the alkyl chain length on the interfacial
tension between the crude oil and the Gemini surfactant
solution was investigated. The results are shown in Fig. 2.
It can be seen from Fig. 2 that the Gemini surfactants
14–2–14 and 16–2–16 were more effective than 12–2–12
or 18–2–18 in reducing the interfacial tension between the
crude oil and the solution. Both 14–2–14 and 16–2–16
were able to reduce the interfacial tension to an order of
magnitude of 10-3 mN m-1 or less, when the concentra-
tion of the surfactant solution was higher than
5.0 9 10-4 mol L-1 for 14–2–14 or 16–2–16. However,
12–2–12 and 18–2–18 could only reduce the interfacial
Results and Discussion
Surface Activity
Figure 1 represents the variation of surface tension values
(mN m-1) against molar concentration of the synthesized
surfactant solutions at 45 °C. Surface tension values depend
on the alkyl chain length. Increasing the hydrocarbon length
tension to an order of magnitude of 10-2 mN m-1
.
Therefore, the length of alkyl chain has a great effect on the
interfacial tension property of the surfactant.
Emulsification Power
Any chemical in the oilfield application area has to provide
good compatibility with the crude oil without increasing its
emulsification in water. Hence, the emulsification power
of the functional chemicals is a critical factor in their
application. Preferably, corrosion inhibitors, biocides and
oil-displacement agents should produce limited emulsion
formation, which reduces the content of demulsifier and
saves costs.
As shown in Table 3, emulsification and interfacial
tension measurements indicate that the synthesized Gemini
surfactants had a very low emulsification power towards the
Tazhong’s crude oil from the Tarim Oilfield and an order
of magnitude of interfacial tension after emulsification
Fig. 1 Surface tension variation of the synthesized Gemini surfac-
tants with the concentration of surfactants m–2–m at 45 °C, filled
diamonds m = 12; filled squares m = 14; open triangle m = 16;
filled circles m = 18
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J Surfact Deterg (2012) 15:309–315
313
increase the density of the adsorbed surfactant onto the
interface.
Corrosion Inhibition Efficiency
Corrosion of steel alloys is one of the most serious prob-
lems occurring due to the corrosive environments in con-
tact with these alloys. In oil field production, the damage
due to corrosion from SO2, SO3, H2S and NaCl is costly
and causes environmental problems especially with regard
Fig. 2 Interfacial tension variation of the synthesized Gemini
surfactants with the concentration of surfactants m–2–m at 45 °C,
filled diamonds m = 12; filled squares m = 14; filled triangle
m = 16; filled circles m = 18
was not less than that of interfacial tension before
emulsification.
Emulsification power and interfacial tension of the
synthesized molecules are superior to literature values for
other quaternary compounds [17].
Salt Effect
Fig. 3 Variation of the interfacial tension with the concentration of
surfactant at a constant salt concentration at 45 °C: filled diamonds
12–2–12, CNaCl = 0; open diamonds 12–2–12, CNaCl = 0.1 mol L-1
;
It is well known that the addition of salt will alter the
surface activity considerably. In the investigation for this
paper, the effect of salt on the interfacial tension of crude
oil and Gemini surfactant solution was also investigated
with sodium chloride as the exclusive electrolyte. The
results are shown in Fig. 3, in which the interfacial tension
is as a function of the concentration of Gemini surfactants
filled squares 14–2–14, CNaCl = 0; open squares 12–3–12,
CNaCl = 0.1 mol L-1; filled triangles 16–2–16, Cs = 0; open trian-
gles 16–2–16, Cs = 0.1 mol L-1; filled circles 18–2–18, Cs = 0;
open circles 18–2–18, Cs = 0.1 mol L-1
in the condition of a constant salt concentration (CNaCl
=
0.1 mol L-1). It was found that the addition of salt had a
remarkable effect on the interfacial tension between the
crude oil and the surfactant solution, which greatly
decreases the CMC and favors the reduction of interfacial
tension. This indicates that salt has a positive effect on
lowering the tension of the oil–water interface [18]. One
reason is presumably that the addition of salt will modify
the oil–water interface hydrophilic lipophilic balance.
Another reason is the compression of the electrical double
layer of the interface by adding salt, which can decrease
the surface area occupied by one surfactant molecule or
Fig. 4 Corrosion inhibition efficiency of the synthesized cationic
Gemini surfactants at 100 mg L-1 at 45 °C
Table 4 Corrosion inhibition efficiency (versus blank) of the syn-
thesized Gemini surfactants with amide at 100 mg L-1 at 45 °C for
5 days
Table 3 Surface properties of the synthesized multifunctional sur-
factants at 45 °C
m–s–m
Efficiency
(%)
Corrosion rate
(mpy)
m–s–m
Emulsification
power (s)
Interfacial tension
after emulsification (mN L-1
)
Blank
0
65
76
87
90
14
12–2–12
14–2–14
16–2–16
18–2–18
960
670
480
320
1.5 9 10-2
3.1 9 10-2
7.1 9 10-4
1.1 9 10-3
12–2–12
14–2–14
16–2–16
18–2–18
4.223
3.015
0.824
0.212
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J Surfact Deterg (2012) 15:309–315
Table 5 Biocidal activity of the synthesized multifunctional surfactants
m–s–m
Staphylococcus aureus
Bacillus subtilis
Escherichia coli
Candida albicans
Aspergillus flavus
Blank
25
39
40
42
45
30
45
47
49
51
35
41
44
46
47
40
47
46
47
49
0.0
10
12–2–12
14–2–14
16–2–16
18–2–18
12
14
17
Gram-positive strains bacteria: Staphylococcus aureus, Bacillus subtilis; Gram-negative strains bacteria: Escherichia coli; Fungi: Candida
albicans, Aspergillus flavus
to sea and land pollution. Several researchers [19–21] have
dealt with this problem through usage of corrosion inhib-
itors. The research of the corrosion inhibitors were mainly
focused on the surfactants including cationic, anionic, and
nonionic surfactants or combinations thereof.
In the presence of Gemini surfactants, the corrosion rate
varies between 0.212 and 4.223 mpy, while it reach the
maximum in the blank sample (14 mpy). 16–2–16 and
18–2–18 provide the best corrosion inhibition efficiency at
0.212 and 0.824 mpy, respectively.
As shown in Fig. 4, high levels of inhibition efficiency
were obtained from the synthesized surfactants. Also, it is
clear that, with the increase in the alkyl chain length, the
corrosion inhibition efficiency of these inhibitors increased.
The maximum inhibition efficiency was observed
for 16–2–16 and 18–2–18 homologues (87 and 90%,
respectively), while the minimum was obtained with 12–2–
12(65%).
Biocidal Activity
Bacteria, namely sulfate-reducing bacteria (SRB), reduce
sulfur-containing compounds and produce H2S gas. This
increases the acidity of the environment and causes serious
problems for metal pipelines, vessels and oil tubes.
Biocides are widely used in industrial applications to pre-
vent the destructive presence of bacteria, fungi and yeast
[24–26]. These biocides inhibit the growth of the micro-
organisms and decrease their effects on petroleum prod-
ucts, especially crude oil in wells and pipelines.
Cationic surfactants have several characteristics, which
allow them to act as good corrosion inhibitors. They are
quite stable in acidic media and retain their chemical
structure in strong acids, because the concentration of
inhibitors used in the corrosion inhibition measurements
are lower than their CMC values, the inhibiting action is
due to the formation of a tight, well surfactant monolayer at
the metal interface and NOT due to the micelles. This
surfactant monofilm acts as a protective shield, which
protects metal surfaces against the corrosion of the outside
environment [22].
The synthesized cationic surfactants are evaluated for
their biocidal activities against different strains of bacteria
and fungi. As shown in Table 5, all of the synthesized
cationic Gemini surfactants are the high effective biocides
against Gram-positive, Gram-negative bacteria and fungi.
This activity increases with the increase of alkyl chain
length. The action mechanism of these compounds on the
cell membranes is the reduction in their selective perme-
ability. This action is originally due to the adsorbed positive
charges on the cell membrane, then penetrated to the mem-
brane constituents. As a result, disturbance of the biological
processes occur leading to the death of the microorganisms
[27]. The penetration step required homogeneity between
the hydrophobic chains and the membrane constituents.
The reason for the stability of the adsorbed monolayer
on the metal surface is two forces acting on the inhibitor
molecules. One, repulsion occurs between the hydrophobic
chains and their aqueous environment, which direct the
molecules toward the metal interface. In addition, the
attraction force occurring between the positively charged
head groups and the negatively charged metal surface
increases the adsorption strength onto these surfaces [23].
Calculation of the corrosion rate in millimeters per year
(mpy) showed that the rate of corrosion decreased
remarkably in presence of the synthesized Gemini surfac-
tants, in Table 4.
Conclusion
The cationic Gemini surfactants of bis[N,N0-(alkyl-amide-
ethyl)ethyl] triethylene-diamine bromide exhibit high sur-
face activity, high interfacial activity, low CMC, lower
interfacial tension while adding suitable salt, low emulsi-
fying power and high biocidal activity while providing the
desired corrosion inhibition efficiency. These properties
Corrosion rate ðmpyÞ ¼ ðK ꢁ WÞ=ðA ꢁ T ꢁ DÞ
where, K is a constant (8.76 9 104), T is time of exposure
in hours, A is the area in cm2, W is the mass loss (g), D the
density of the steel used (g cm-3).
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315
16. Oda R, Huc I, Candau SJ (1997) Gemini surfactants—the effect
of alkyl chain length and dissymmetry. Chem Commun
21:6382–6389
suggest that the synthesized compounds have application
potential in oilfield areas.
17. Negm NA, Aiad IA (2007) Synthesis and characterization of
multifunctional surfactants in oil-field protection applications.
J Surfactants Deterg 10:87–92
18. Han L, Ye Z, Chen H et al (2009) The interfacial tension between
cationic gemini surfactant solution and crude oil. J Surfactants
Deterg 12:185–190
Acknowledgments This research was supported by the National
Natural Science Foundation of China (Project No. 51074133) and
Major Special Technological Programmes concerning China Petro-
leum (No. 2008ZX05000-049-04-03).
19. Walker ML (2004) Corrosion inhibitor. Canadian Patent CA.
2,482,513
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Author Biographies
Ming Zhou received his B.Sc., M.Sc. and Ph.D. from the Southwest
Petroleum University in Chengdu, PR China, and worked at the
School of Materials Science and Engineering at Southwest Petroleum
University as a research chemist in 2002. He is an associate professor
at the State Key Laboratory of Oil and Gas Reservoir Geology and
Exploitation. His research field is the synthesis and applications of
surfactants and polymers.
Jinzhou Zhao received his master’s degree from Southwest Petro-
leum University in China. He is a professor at the State Key
Laboratory of Oil and Gas Reservoir Geology and Exploitation
(Southwest Petroleum University) with a research field in reservoir
stimulation.
12. Ismail DA, Negm NA (2001) Surface and thermodynamic
properties of sodium alkyl sarcosinate derivatives. J Fac Educ
26:33–45
13. Ismail DA, Negm NA (2001) Surface behaviour of sodium-
N-acyl sarcosinate/sodium dodecyl benzene sulfonate mixed
systems. J Fac Educ 26:47–55
Xingqi Hu received his master’s degree in 1981 from the Sichuan
University in Chengdu, PR China, and in the same year worked at the
School of Chemistry and Chemical Engineering at the Southwest
Petroleum University as a research chemist. His research field is
surfactants and polymers in oilfields.
14. El Achouri M, Kertit S, Gouttaya HM (2001) Prog Org Coatings
43:367–375
15. Hafiz AA, Negm NA, Elawady MY (2005) Influence of structure
on the cationic polytriethanolammonium bromide derivatives III.
Biological activity. Egypt J Chem 48:245–252
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