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 Page 1 of 22 RSC Advances
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DOI: 10.1039/C6RA09769C

1 The equilibrium and dynamic surface tension of polymeric surfactants

2 based on epoxidized soybean oil grafted hydroxyethyl cellulose

3 Xujuan Huang1, 2, He Liu1*, Shibin Shang1*, Zhaosheng Cai2, Jie Song3

4 1.Institute of Chemical Industry of Forestry Products, Chinese Academy of Forestry,

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5 Key Laboratory of Biomass Energy and Material, National Engineering Laboratory
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6 for Biomass Chemical Utilization, Key and Laboratory on Forest Chemical

7 Engineering, State Forestry Administration, Nanjing, Jiangsu Province, 210042 China

8 2. School of Chemical and Biological Engineering, Yancheng Institute of Technology,

9 Yancheng 224051, Jiangsu Province, China

10 3. Department of Chemistry and Biochemistry, University of Michigan-Flint, Flint,

11 Michigan 48502, United States

12 Abstract: Analysis of the equilibrium and dynamic surface tension of epoxidized

13 soybean oil grafted hydroxyethyl cellulose (H–ESO–HEC) surfactants with different

14 molecular weights were carried out at pH values that ranged from 8 to 13. A variation

15 in the surface activity of H–ESO–HEC surfactants was found in the premicellar

16 concentration range because of the formation of surface-active premicellar species,

17 depending on pH and surfactant concentration. The H–ESO–HEC polymeric

18 surfactants displayed excellent surface properties at pH values that ranged from 9 to

19 10, and the critical micelle concentration decreased with increasing molecular weight,

20 as expected. The adsorption behavior of H–ESO–HEC polymeric surfactants at the

21 air/solution interface was analyzed by using the Ward and Tordai equation. The

22 effective diffusion coefficients of H–ESO–HEC polymeric surfactants increased with

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23 pH values, with the exception of pH 13, and also improved with increasing molecular

24 weight. Furthermore, H–ESO–HEC surfactants with higher molecular weight weights

25 had larger micelles.

26 Key words: polymeric surfactant; equilibrium surface tension; dynamic surface

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27 tension; diffusion coefficient
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28 Introduction

29 Polymeric surfactants have received increasing attention in the past decades,

30 particularly for their applications in several fields including emulsion polymerizations,

31 coatings and enhanced oil recovery.1, 2 To study their function mechanism in those

32 applications, various fundamental characteristics of polymeric surfactants, such as

33 equilibrium and dynamic surface tension3, micelles4, aggregation behavior5, 6,

34 interaction mechanisms with micromolecular7 and rheological properties8, 9, must also

35 be examined.

36 The equilibrium and dynamic surface tension at the air–water interface are

37 important properties of polymeric surfactants in some fields, like wetting, foaming

38 and emulsification among others. Dynamic surface tension measurements are often

39 performed to study the adsorption kinetics behavior of surfactants. Furthermore, the

40 adsorption behavior of surfactants in aqueous solutions controls the performance in

41 many practical applications, including household products, such as laundry detergents,

42 as well as crude oil recycling.10 Adsorption kinetics behavior is commonly

43 investigated by creating a freshly exposed surface in contact with the surfactant

44 solution and measuring the temporal dependence of its surface tension.11

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45 A series of theoretical models have been proposed to study the adsorption

46 behavior of surfactants. In 1946，Ward and Tordai pioneered the mathematical

47 description of the relationship between interface and subsurface concentrations.12 The

48 Ward and Tordai equation considered the ideal situations of the surfactant solution

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49 with an infinite diffusion length. Arias presented an axisymmetric model in terms of
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50 both finite and infinite diffusion lengths.13 Yet, it is difficult to improve the accuracy

51 of the mathematical equation because there exist many deviations in several

52 systems.14 Considering the complex species of polymeric surfactants formed in

53 solution, the Ward and Tordai equation, used widely and applicable to the majority of

54 polymeric surfactants, attempts a rigorous mathematical analysis of diffusion in

55 time-effects and indicates the kinetics of adsorption at the interface.15, 16 The effective

56 diffusion coefficients (Deff) and adsorption constants of surfactants or polymeric

57 surfactants calculated by applying the Ward and Tordai equation could be influenced

58 by concentration 17, hydrocarbon chain length7, temperature and pH values18.

59 Nature polymer-derived surfactants were usually prepared by hydroxyethyl or

60 carboxymethyl cellulose19, pullulan20, pectin21, dextran22, chitosan23 and lignin24, 25,

61 which combined both the advantages of natural resources and of polymeric

62 surfactants (e.g., low cost, biodegradation, and emulsification and the ability to

63 thicken in water.26, 27 Hydrophobic units can be introduced through the reaction of the

64 hydroxyl groups with organic halogenide (substitution), epoxides (addition), or esters

65 (transesterification).2 In particular, cellulose-based polymeric surfactants present

66 many novel performances such as associative properties in water as well as

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67 rheological properties and surface-active properties caused by the adsorption

68 behavior in the interface.28 The saponified fatty acid-grafted cellulose surfactants

69 through hydroxyethyl cellulose as backbones were obtained in a previously study.29

70 Those novel polymeric surfactants (H–ESO–HEC) were effective at lowering the

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71 surface tension of water to 26–28 mN/m, and were superior to the fatty acid-esterified
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72 cellulose derivatives that can decrease the surface tension of water from 72.8 to 45

73 mN/m.30 Although the H–ESO–HEC surfactants displayed efficient surface properties

74 in water, the equilibrium and dynamic surface tension of H–ESO–HEC surfactants at

75 different situations were unknown.

76 In this paper, both the dependence of pH values and the molecular weight

77 distribution of H–ESO–HEC on the equilibrium surface tension of H–ESO–HEC

78 surfactants were reported. The influences of the two factors on the dynamic surface

79 tension of H–ESO–HEC polymeric surfactants measured by the pendant drop

80 technique were also discussed. Also, the Deff of the H–ESO–HEC polymeric

81 surfactants were investigated through dynamic surface tension and applying the Ward

82 and Tordai equation. Furthermore, the aggregation behaviors of H–ESO–HEC

83 polymeric surfactants were demonstrated by analyzing the aggregation size.

84 MATERIALS AND METHODS

85 Materials

86 Epoxidized soybean oil (ESO) grafted hydroxyethyl cellulose (HEC) was prepared by

87 ring-opening polymerization, and hydrolysis of ESO grafted HEC (ESO–HEC) was

88 performed with sodium hydroxide to obtain hydrolyzed ESO-HEC (H–ESO–HEC).

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89 Detailed information on the reaction can be found in a previously published paper.29

90 HEC (molecule weight: approximately 228,000 Daltons; viscosity: 80–125 mPa·s,

91 25°C) was purchased from Aladdin Industrial Co., Ltd. Ultrafiltration membranes

92 (Cat. No. PLHK07610; NMWL, 100,000) were obtained from Millipore Reagent Co.,

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93 Ltd. Sodium hydroxide (NaOH) was obtained from Nanjing Chemical Reagent Co.,
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94 Ltd. Deionized water was purified to a conductivity of 18.3 MΩ·cm on a

95 Hitech-Sciencetool Master-Q laboratory water purification system (Shanghai Hetai

96 Reagent Co., Ltd.).

97 Preparation of ESO grafted HEC derivatives

98 ESO grafted HEC polymeric surfactant (H–ESO–HEC) was prepared according to a

99 previously described paper.29 First, ESO grafted HEC derivative (ESO-HEC) was

100 prepared by ring-opening polymerization in dimethyl sulfoxide through the use of

101 SnCl4 as a catalyst. The resulting products were washed sequentially with deionized

102 water. Then, ESO-HEC was added to a flask with 50 mL of 0.6 M NaOH solution.

103 The reactor was heated to 100 °C with agitation for 12 h under a condensing condition.

104 After the reaction, the hydrolysis product (H–ESO–HEC) was obtained through a

105 multistep purification process, including purification through ultrafiltration

106 membranes (NMWL: 100,000) to eliminate the influence of smaller molecules and

107 electrolyte. Finally, H–ESO–HEC was dried by reduced pressure distillation.

108 Equilibrium surface tension

109 The equilibrium surface tension of H–ESO–HEC solution with different pH values

110 was measured at 25°C by using a Wilhelmy plate T107 (width: 19.44 mm; thickness:
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111 0.1 mm; height: 65 mm; circumference: 39.08) on a Sigma 701 Automatic Surface

112 Tensiometer (Biolin Scientific, Sweden). The instrument was calibrated against pure

113 water before measurements were made. The concentrations of H–ESO–HEC

114 polymeric surfactant were increased gradually by dispersing stock solution into the

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115 measurement cell. The software automatically determined the surface tension as a
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116 function of the bulk concentration. Each concentration of aqueous H–ESO–HEC

117 solution was tested in triplicate—this was done automatically by the instrument. All

118 data were obtained from OneAttention software.

119 Dynamic surface tension

120 The dynamic surface tension of the H–ESO–HEC polymeric surfactants in water was

121 measured on a DropMeter A-200 contact angle system (MAIST Vision Inspection &

122 Measurement Co., Ltd., China) by using the pendant drop technique. The DropMeter

123 is equipped with a low-deformation telecentric lens and a high resolution USB 2.0

124 CMOS camera. The instrument squeezes out a drop of water through a needle (1.825

125 mm diameter) and keeps the droplet at the point of the needle. The digital image

126 system produces rapid imaging samples, and the DropMeter system calculates the

127 surface tension from these images in real time. The advantage of pendant drop method,

128 compared with maximum pressure bubble method, is that it is not affected by the

129 viscosity of the system. However, the soonest measuring time (stability time) with the

130 pendant drop method is 1 s. All data were obtained from DropMeter software.

131 Aggregation size

132 The aggregation size of H–ESO–HEC (I–V) polymeric surfactants in aqueous

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133 solution (CMC concentration) was analyzed by using a laser diffraction particle size

134 analyzer (Mastersizer 2000, Malvern Instruments Ltd., UK). Optical properties of the

135 samples were defined as follows: refractive indices of HEC and water were 1.47 and

136 1.33, respectively, and the absorption was assumed to be 0. Aggregation size

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137 distribution was measured on the basis of light-scattering theory.
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138 Statistical analysis.

139 Each concentration of aqueous H–ESO–HEC solution was tested in triplicate. Results

140 are expressed as the mean ± standard deviations. A one-way analysis of variance

141 (ANOVA) was used to establish the significance of differences among the mean

142 values. The standard deviation was calculated with the following equation:

∑(X i − X )2
143 S= i =1
(1)
n −1

144 Here, S is the standard deviation of the sample; X i is the ith value in the sample; X

145 is the average number of the sample, and n is the total number of the sample. The

146 statistical analyses were performed using Origin Pro 9.0.

147 RESULTS AND DISCUSSION

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148

149 Figure 1. Structure of epoxidized soybean oil modified hydroxyethyl cellulose

150 polymeric surfactant.

151 The structure of H–ESO–HEC is shown in Figure 1. Each solution was freshly

152 prepared separately from the cellulose derivatives and dissolved in different pH

153 values of sodium hydroxide aqueous solution by stirring overnight before

154 measurement. This technique eliminated any errors related to solubility

155 time-dependent effects. Surfactant concentrations were expressed in grams per liter

156 (with good precision). Finally, the H–ESO–HEC solution with different pH values

157 was obtained by neutralizing the carboxylic acid of H–ESO–HEC with sodiu

158 hydroxide. Besides, the molecular weights of H–ESO–HEC-(I-V) surfactants were

159 2.71, 3.31, 5.50, 6.61, and 8.28 Daltons, respectively.29

160 Influence of pH values on equilibrium surface tension (γeq)

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161 The γeq experiments of the H–ESO–HEC polymeric surfactant solutions were

162 performed at 25°C. As shown in Figure 2, the surface tensions of H–ESO–HEC in

163 water decreased markedly at low concentrations at first. When the concentration was

164 higher, the surface tension reduced slightly. Finally, the surface tension was held

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165 nearly constant because its concentration was sufficiently high. This is the basic law
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166 of surfactant change in a solution.

167 Table 1 pH dependence on the CAC, CMC and γeq of the H–ESO–HEC–I polymeric

168 surfactant

pH CAC (g/L) CMC (g/L) γeq at CMC (mN/m)

8 0.02–0.04 0.65 29.50±0.26

9 0.02–0.04 1.00 25.87±0.21

10 0.01–0.02 1.06 28.04±0.28

11 0.01–0.02 1.10 31.35±0.13

12 0.01–0.02 1.15 31.30±0.23

13 0.01–0.02 1.15 30.21±0.05

169 The surface tension curves display two distinct characteristic concentrations where the

170 surface tension changes quite sharply (Figure 2). The low-concentration end of the

171 first plateau is usually referred to as the critical aggregation concentration (CAC) of

172 the surfactant, which corresponds to the appearance of low-molecular-weight

173 H–ESO–HEC in a solution.31 The onset of another plateau in the surface tension curve

174 at a high-surfactant concentration corresponds to the critical micelle concentration of

175 the H–ESO–HEC surfactant (CMC).32 The complete CAC, CMC and γeq data of
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176 H–ESO–HEC–I polymeric surfactant from pH 8 to 13 were listed in Table 1 as

177 representative examples. The CMC values were considerably greater than the CAC

178 values. This finding is due, in part, to their polydispersity, both in terms of the length

179 and distribution of hydrophobic groups along the chains.29, 33 Besides, the first plateau

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180 in the curves corresponded to the aggregation of smaller molecular weight products or
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181 the intramolecular aggregation in the solution.

182 As expected, ionic surfactant was sensitive to the pH values of the aqueous solution.

183 As shown in from Figure 2, different efficiencies of these cellulose polymeric

184 surfactants in lowering the surface tensions of water resulted from the existential form

185 of fatty acid in the polymeric surfactants at different pH values. Under the appropriate

186 conditions, the carboxyl in H–ESO–HEC polymeric surfactant could interact to form

187 a range of complexes. This complex species played a significant role in determining

188 surface tension. Because these species have marked differences in surface activity,

189 their functions at lowering the surface tension of water must be dependent on

190 surfactant concentrations and pH values.18 Also, the surface activity differs for the

191 various chemical forms. However, the unknown degree of polymerization of fatty acid

192 on the surface of HEC brought a greater level of complexity to the species in the

193 H–ESO–HEC surfactant solution.

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194

195 Figure 2. Equilibrium surface tension of H–ESO–HEC-(I-V) polymer surfactants with

196 different pH values.

197 The H–ESO–HEC polymeric surfactants displayed excellent surface properties at pH

198 values that ranged from 9 to 10. This condition was feasible because the -COOH in

199 H–ESO–HEC transformed to -COONa gradually with the increasing pH values of the

200 solution. As the ionization degree was enhanced (increasing pH), the effective
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201 hydrophobic content of the polymeric surfactants decreased and thus hydrophobic

202 interactions became weaker.34 Therefore, the decrease in surface tension with the

203 increase in pH was as pronounced at pH values that ranged from 8 to 10. However,

204 the abnormality of H–ESO–HEC–I polymeric surfactant was attributed to the high

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205 hydrophilicity at low ionization degrees because of the lower molecular weight (lower
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206 hydrophobic chain).

207 The influence of molecular weight on γeq

208

209 Figure 3. Equilibrium surface tension of H–ESO–HEC (I–V) polymer surfactants

210 versus concentration at four different pH values.

211 Figure 3 shows some representative examples of γeq versus concentration of the

212 H–ESO–HEC surfactants at different pH values. It was indicated that the CMC values
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213 of H–ESO–HEC polymeric surfactants decreased along with the obviously increasing

214 molecular weight. The amount or density of the hydrophobic groups relatively

215 increases with increasing the molecular weight of H–ESO–HEC.35 In the weakly

216 alkaline pH range (8–9), the γeq decreased along with the increasing molecular weight

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217 of H–ESO–HEC in every different concentration. However, this phenomenon was not
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218 observed under strong base conditions. The relatively high molecular weight of

219 polymeric surfactants, as opposed to the low molecular weight ones, allowed a

220 fine-tuning of the micelle’s properties.

221 Dynamic surface tension (γt)

222 The γt of H–ESO–HEC polymeric surfactant was determined by the variation of

223 surface tension along with times using the pendant drop technique. One advantage of

224 this method is the absence of contact between the air bubble and the solid surfaces,

225 which limits perturbations by contaminants, especially at high dilutions.35

226

227 Figure 4. The γt of H–ESO–HEC–I polymeric surfactant as a function of time

228 measured at a pH of 10: 1) 0.001CMC; 2) 0.01CMC; 3) 0.1CMC; 4) 0.5CMC; and 5)

229 CMC.
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230 Dynamic surface tension measurements were often carried out to study the adsorption

231 behavior of polymeric surfactants. As known, the adsorption process of polymers

232 could be subdivided into three distinct consecutive kinetic regions at a fluid

233 interface.36, 37
These regions, which indicate the existence of the adsorption and

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234 reconfiguration process, are the induction period, the surface coverage, and the
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235 mesophase region. First, the molecules initially are transferred to the subsurface

236 region. Second, adsorption and interfacial unfolding are explained by an increase in

237 the number of adsorbed polymer segments in the interface. This is followed by

238 aggregation within the interfacial layer spreading and unfolding of the polymer chains

239 and multilayer formation.17 Figure 4 shows the dynamic surface tension data of

240 different concentrations of H–ESO–HEC–I polymeric surfactant in the aqueous

241 solution at a pH of 10 as an example. Because of the high efficiency of H–ESO–HEC

242 surfactants and the insensibility of the pendant drop Tensiometer in measuring time

243 (stability time for a drop of water: 1 s), the induction time could not be presented in

244 any of the figures. The γt of 0.001CMC H–ESO–HEC–I polymeric surfactant in

245 aqueous solution has no changes along with the increasing time, which was similar to

246 the surface tension value of the aqueous solution (72.8 mN/m). When the

247 concentration of H–ESO–HEC–I polymeric surfactant ranged from 0.001CMC to

248 CMC, the surface tension decreased up to 30 mN/m. The γt of the H–ESO–HEC–I

249 polymeric surfactant remained constant when the time was sufficient.

250 Analysis of γt over time scales

251 When general polymeric surfactant dissolves in water, it can cause a decrease in the
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252 corresponding surface tension of the water. This condition is normally attributed to a

253 specific orientation of these copolymers at the surface with the hydrophobic block

254 pointing at the air side of the surface. The γt which reflects the change in surface

255 tension along with the time before equilibrium conditions are measured and depends

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256 on the diffusion of the components. The γt data can be described according to the
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257 Ward and Tordai model, as a diffusion-controlled process of adsorption to a clean

258 surface with an infinite diffusion length.38 The process can be analyzed by the integral

259 equation11, 18:

t
D
260 Γ(t ) = 2c0 ( )1 2 ∫ cs (t − τ )dτ 1 2 （2）
π 0

261 Here, Γ (t) is the surface concentration at time t; c0 is the bulk concentration; cs is the

262 subsurface concentration and is a function of time; D is the diffusion coefficient, and

263 τ is a dummy variable of integration. This equation describes the dynamics over the

264 whole timescale and is applicable under ideal conditions.13 In this model, the surface

265 is considered as a two-dimensional monolayer. At the very beginning of the diffusion

266 process, there is little desorption from the surface to the subsurface; and over a longer

267 time period, the subsurface concentration begins to approach bulk concentration.

268 Hence, the equation can be rewritten as follows:

Dt
269 γ (t )t →0 = γ H O − υ RTc0 （3）
2
π

υ RT Γ 2 π
270 γ (t )t →∞ = γ eq + （4）
2c0 2 Dt

271 Here, γ H2O is the surface tension of water. γeq is the equilibrium surface tension of

272 the H–ESO–HEC polymeric surfactant; R is the gas constant; D is the diffusion
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273 coefficient of the H–ESO–HEC polymeric surfactant; C is the concentration of

274 H–ESO–HEC polymeric surfactant in the solution; Γ is the equilibrium surface excess;

275 and υ equals to 1 or 2.35

276 Effect of pH on the γt and effective diffusion coefficient

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277 The dynamic surface tension curves of 0.1CMC H–ESO–HEC–I polymeric surfactant
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278 obtained at pH values that ranged from 8 to 13 are shown in Figure 5(A). Similar

279 characteristic curves were obtained at other concentration (less than CMC

280 concentration). A series of curves of γt versus t-1/2 were shown in Figure 5(B).

281 The γt over a longer period was first decreased when the pH values increased from 8

282 to 10 in Figure 5(A). Then, the γt increased at pH values that ranged from 11 to 13.

283 The curves generally gave reasonable linear behavior corresponding to the longer

284 time scales (low t-1/2) in Figure 5(B). According to Equation 4, if the adsorption

285 process is diffusion-controlled, a plot of γt versus t-1/2 will then be linear, with the

286 slope equal to the effective diffusion coefficient. Therefore, it can be concluded that

287 the adsorption behavior of H–ESO–HEC–I polymeric surfactant was diffusion

288 controlled over long time scales. The Deff of H–ESO–HEC–I polymeric surfactant

289 increased along with the pH values, except for a pH value of 13. At high pH Values,

290 the H–ESO–HEC–I surfactant was more negatively charged due to the complete

291 ionization of COOH. More significantly, these highly negatively charged molecule

292 diffused to the surface of the droplet first prevented the diffusion of other negatively

293 charged molecules to the surface.39 However, over short time scales, it was difficult

294 for the H–ESO–HEC–I polymeric surfactant to establish a linear relationship. Hence,
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295 the adsorption behavior is incompletely diffusion-controlled at the whole process.

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296

297 Figure 5. (A) Dynamic surface tension of H–ESO–HEC -I polymeric surfactant with

298 different pH values in 0.1CMC concentration. (B) Curves of γt vs t-1/2 and linear

299 regression extrapolating the surface tension at long times.

300 Effect of molecular weight on the γt and effective diffusion coefficient

301 In Figure 6(A), representative sets of results are shown for a 0.01CMC H–ESO–HEC

302 polymeric surfactant with different molecular weights at a pH value of 10. As shown

303 in figure 6(A), the surface tension completely decreased along with increasing time.

304 This means that the number of adsorbed polymer segments increased in the interface.

305 In addition, the surface tension changed slowly when the time was sufficient. This

306 fingding represents the third process of the aggregation of the polymer chains and
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307 multilayer formation. The adsorption behavior of H–ESO–HEC polymeric surfactants

308 was diffusion controlled in Figure 6(B). The slopes of the curves increased along with

309 increasing molecule weight. Therefore, the Deff of H–ESO–HEC polymeric surfactant

310 improved along with increasing molecule weight according to Equation 4.

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311

312 Figure 6. (A) The dynamic surface tension of the H–ESO–HEC polymeric surfactant

313 with different molecular weights at a pH value of 10 in 0.01CMC concentrations. (B)

314 Plot of γt vs t−1/2 and linear regression extrapolating the surface tension at long times.

315 Study on the aggregation behavior

316 To study the aggregation behavior, the size distributions of the aggregations formed

317 for the H–ESO–HEC (I–V) polymeric surfactants at CMC concentrations were

318 investigated through size measurements. The chemical structures of the H–ESO–HEC
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319 polymeric surfactant are given in Figure 1. It was considered that the H–ESO–HEC

320 (I–V) polymeric surfactants existed aggregation behavior when the concentrations

321 were in excess of CMC.

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322

323 Figure 7. Measurement of the size distributions of the HEC and H–ESO–HEC (I–V)

324 surfactants in 1.2CMC concentrations at a pH value of 10.

325 As shown in Figure 7, two peaks had an average size of approximately 50 nm, with

326 approximately 300 nm of the raw material-HEC (black curve). Therefore, the average

327 sizes of the H–ESO–HEC polymeric surfactants were also two peaks ( figure 7),

328 which moved towards the higher size regions as the molecular weights increased.

329 In this study, hydroxyl groups of HEC acted as initiators for the ring-opening

330 polymerization of ESO. The fatty acid chains were combined with HEC by ether

331 linkages at the middle site of the fatty acid molecular chain. In this structure, both the

332 hydrophobic alkanes and the hydrophilic carboxyls were introduced into the HEC.

333 The simultaneous introduction of hydrophobic alkanes and hydrophilic carboxyl

334 groups improved the hydrophilic−hydrophobic balance of HEC and provided an

335 opportunity to form micelles in water. It can be concluded that the micelle size of the
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336 H-–ESO-–HEC polymeric surfactants increased with the increasing molecular

337 weights of H–ESO–HEC.

338 CONCLUSION

339 This present work analyzes the equilibrium surface tension and dynamic surface

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340 tension of H–ESO–HEC (I–V) polymeric surfactants at the water–air interface for
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341 several pH values and concentrations. Equilibrium surface tensions of H–ESO–HEC

342 (I–V) polymeric surfactants show a high sensitivity to pH that range from 8 to 13. The

343 CMC values of the H–ESO–HEC (I–V) polymeric surfactants increased along with

344 the pH values. However, the critical micellar concentrations (CMCs) of the

345 H–ESO–HEC (I–V) polymeric surfactants decreased along with the increasing

346 molecular weights of the surfactants. From these experiments, the Deff of the

347 H–ESO–HEC (I–V) polymeric surfactants were determined through the Ward and

348 Tordai diffusion theory. The Deff of the H–ESO–HEC–I polymeric surfactant

349 increased along with the pH values except for the pH value 13. Also, the Deff of the

350 H–ESO–HEC (I–V) polymeric surfactants improved along with the increasing

351 molecular weights under the condition of the same pH values. Furthermore, the size

352 distribution and micelles of the H–ESO–HEC surfactants increased with the higher

353 molecular weights.

354 ACKNOWLEDGEMENTS

355 The authors express their gratitude for the National Natural Science Foundation of

356 China (31200446); Foundation of Jiangsu Province Biomass Energy and Material

357 Laboratory (JSBEM-S-201504); Natural Science Foundation of Jiangsu Province of

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DOI: 10.1039/C6RA09769C

358 China (BK2012063); National Key Technology R&D Program (2015-BAD14B06).

359 References
360 1. J. H. Zhou, L. Wang and J. Z. Ma, Des Monomers Polym, 2009, 12, 19-41.
361 2. P. Raffa, D. A. Z. Wever, F. Picchioni and A. A. Broekhuis, Chem Rev, 2015, 115, 8504-8563.
362 3. L. S. Yang, B. K. Kazmierski, S. D. Hoath, S. Jung, W. K. Hsiao, Y. W. Wang, A. Berson, O. Harlen,
363 N. Kapur and C. D. Bain, Phys Fluids, 2014, 26.
364 4. A. D. Eckard, K. Muthukumarappan and W. Gibbons, Bioenerg Res, 2014, 7, 389-407.
365 5. L. Y. Wang, Y. Zhang, L. M. Ding, J. Liu, B. Zhao, Q. G. Deng and T. Yan, Rsc Adv, 2015, 5,

RSC Advances Accepted Manuscript

366 74764-74773.
367 6. U. Thapa, D. Ray, J. Dey, N. Sultana, V. K. Aswal and K. Ismail, Rsc Adv, 2015, 5, 45956-45964.
Published on 29 June 2016. Downloaded by test 3 on 05/07/2016 09:33:59.

368 7. Y. J. Jiang, T. Geng, Q. X. Li, G. J. Li and H. B. Ju, J Mol Liq, 2015, 204, 126-131.
369 8. S. Nobel, C. Hahn, B. Hitzmann and J. Hinrichs, Int Dairy J, 2014, 39, 157-166.
370 9. C. Oelschlaeger and N. Willenbacher, Colloid Surface A, 2012, 406, 31-37.
371 10. S. N. Moorkanikkara and D. Blankschtein, Langmuir, 2009, 25, 6191-6202.
372 11. H. Ritacco, D. Langevin, H. Diamant and D. Andelman, Langmuir, 2011, 27, 1009-1014.
373 12. A. F. H. Ward and L. Tordai, J Chem Phys, 1946, 14, 453-461.
374 13. S. I. Arias, J. R. Fernandez, L. Garcia-Rio, J. C. Mejuto, M. C. Muniz and C. Nunez, Rsc Adv,
375 2015, 5, 7921-7931.
376 14. B. Nozière, C. Baduel and J.-L. Jaffrezo, Nat Commun, 2014, 5.
377 15. A. F. H. Ward and L. Tordai, Recl Trav Chim Pay B, 1952, 71, 572-584.
378 16. A. F. H. Ward and L. Tordai, Recl Trav Chim Pay B, 1952, 71, 396-408.
379 17. M. Manousakis and A. Avranas, J Colloid Interf Sci, 2013, 402, 237-245.
380 18. K. Theander and R. J. Pugh, J Colloid Interf Sci, 2001, 239, 209-216.
381 19. S. U. Um, E. Poptoshev and R. J. Pugh, J Colloid Interf Sci, 1997, 193, 41-49.
382 20. W. Henni-Silhadi, M. Deyme, M. R. de Hoyos, D. Le Cerf, L. Picton and V. Rosilio, Colloid Polym
383 Sci, 2008, 286, 1299-1305.
384 21. N. Joshi, K. Rawat and H. B. Bohidar, The Journal of Physical Chemistry B, 2016, 120,
385 4249-4257.
386 22. K. Kaewprapan, F. Baros, E. Marie, P. Inprakhon and A. Durand, Carbohyd Polym, 2012, 88,
387 313-320.
388 23. V. G. Babak and J. Desbrieres, Colloid Polym Sci, 2006, 284, 745-754.
389 24. M. Zhou, W. Wang, D. Yang and X. Qiu, Rsc Adv, 2015, 5, 2441-2448.
390 25. C.-Z. Chen, M.-F. Li, Y.-Y. Wu and R.-C. Sun, Rsc Adv, 2014, 4, 16944-16950.
391 26. D. A. Z. Wever, F. Picchioni and A. A. Broekhuis, Prog Polym Sci, 2011, 36, 1558-1628.
392 27. S. De, S. Malik, A. Ghosh, R. Saha and B. Saha, Rsc Adv, 2015, 5, 65757-65767.
393 28. Z. Hu, S. Ballinger, R. Pelton and E. D. Cranston, J Colloid Interf Sci, 2015, 439, 139-148.
394 29. X. J. Huang, H. Liu, S. B. Shang, X. P. Rao and J. Song, J Agr Food Chem, 2015, 63, 9062-9068.
395 30. J. L. Yu, F. Yang, Z. H. Liu, Y. N. Liu and G. Li, J Surfactants Deterg, 2014, 17, 647-653.
396 31. N. Jain, S. Trabelsi, S. Guillot, D. McLouglilin, D. Langevin, P. Letellier and M. Turmine,
397 Langmuir, 2004, 20, 8496-8503.
398 32. Z. S. Liu and G. Biresaw, J Agr Food Chem, 2011, 59, 1909-1917.
399 33. T. Noda, A. Hashidzume and Y. Morishima, Macromolecules, 2001, 34, 1308-1317.
400 34. R. S. Armentrout and C. L. McCormick, Macromolecules, 2000, 33, 2944-2951.
 RSC Advances Page 22 of 22
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DOI: 10.1039/C6RA09769C

401 35. F. Giusti, J. L. Popot and C. Tribet, Langmuir, 2012, 28, 10372-10380.
402 36. I. Nahringbauer, J Colloid Interf Sci, 1995, 176, 318-328.
403 37. I. Nahringbauer, Langmuir, 1997, 13, 2242-2249.
404 38. Y. C. Lee, H. S. Liu and S. Y. Lin, Colloid Surface A, 2003, 212, 123-134.
405 39. Y. Wang, C. Combe and M. M. Clark, J Membrane Sci, 2001, 183, 49-60.
406

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