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Journal of Colloid and Interface Science 383 (2012) 49–54

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Journal of Colloid and Interface Science


www.elsevier.com/locate/jcis

Investigation of colloidal properties of modified silicone polymers emulsified


by non-ionic surfactants
Parag S. Purohit a, Ravi Kulkarni b, P. Somasundaran a,⇑
a
NSF Industry/University Cooperative Research Center for Advanced Studies in Novel Surfactants, Columbia University, New York, NY 10027, USA
b
Elkay Chemical, Pune 411 026, India

a r t i c l e i n f o a b s t r a c t

Article history: Functionalized silicones are a unique class of hybrid materials due to their simultaneous hydrophobic–
Received 25 February 2012 oleophobic properties, which results in applications in a variety of surface modification techniques. Prior
Accepted 9 June 2012 research has shown that changes in surface charge and turbidity of modified silicone emulsions as a func-
Available online 18 June 2012
tion of pH have a marked effect on their performance in coating applications. The emulsion droplet size is
also believed to play significant role in such coating applications. In this work, modified silicone polymer
Keywords: emulsions stabilized by non-ionic surfactants were studied using dynamic light scattering (dilute) and
Silicone polymer
electroacoustic (concentrated) spectroscopy to monitor the emulsion droplet size. The dilute and concen-
Emulsion
Droplet size
trated regime studies showed the emulsion droplet to be in nanometer range with no appreciable change
Stability in size as a function of pH. Electroacoustic studies showed a small fraction of droplets to be present in the
Pyrene fluorescence micron size range. The emulsions were examined using Cryo-TEM technique, and the effect of pH and
dilution on hydrophobicity of nanodomains was studied by employing fluorescence spectroscopy. It is
shown from pyrene excimer behavior that both the dilution and pH have an effect on emulsion stability
with a presence of critical surfactant concentration after which the emulsion was destabilized. It is pro-
posed that the emulsion stability characteristics and the particle size distribution both play a significant
role in their ability to impart desired macro and nano surface properties to treated substrates through
electrostatic interactions and selective binding.
Ó 2012 Elsevier Inc. All rights reserved.

1. Introduction are qualitative in nature, they form critical part of assessing the ef-
fects of silicone formulations on treated fabrics.
Silicone polymers constitute an important class of high perfor- Amino silicones are by far the most extensively used functional
mance materials, since they derive their uniqueness from being or- silicones [8–11] for imparting desired surface properties to various
ganic/inorganic hybrid polymers. Silicone polymers differ substrates. They are commonly used in micro-emulsion form, typ-
markedly from their organic counterparts such as paraffin waxes ically as is or as partially quaternized by reagents such as di-alkyl
and fatty acid derivatives due to their weak intermolecular attrac- sulfate. Silicone formulations are applied to the fabric surface
tive forces. Earlier studies [1] have shown that silicones have spe- through either exhaust or padding process. It is believed that the
cial physical and chemical properties such as good thermal and silicone droplet size, surface charge, molecular conformation, bath
oxidative stability, relatively low dependence of physical proper- pH, and temperature play a major role in imparting desired prop-
ties on temperature, chemical inertness, and low surface energy. erties. The emulsions exhibit positive surface charge in a certain
Since the discovery of straight chain and cross-linked silicone poly- pH range and are shown to impart smoothness and uniformity to
mers, a variety of modifications designed for specific applications, cotton fibers [12].
which include pharmaceuticals [2], cosmetics and personal care The silicone polymer literature, which is extensively available in
[3], antifoaming [4], coatings [5], delivery [6], and paints and inks the form of patents [13–17], generally focuses on: optimization of
[7], have been envisaged. One of the important applications of sil- primary and secondary emulsion technologies, defining molecular
icones is to impart better properties such as softness, bounciness, weight of polymers, creating additional functionalities, and optimi-
feel to substrates (fabric, hair, skin). Although these properties zation of ratios of individual compounds. Surface chemical under-
standing, which could provide a good approach through the
selection of specific polymers and, their effect on emulsion stabil-
⇑ Corresponding author. Address: 911 S.W Mudd MC#4711, Columbia University,
ity, nano-droplet selective adsorption, is generally lacking. Re-
New York, NY 10027, USA. Fax: +1 212 854 8362. cently, some novel emulsification phenomena have been
E-mail address: ps24@columbia.edu (P. Somasundaran). reported in the presence of silica particles [18] and hydroxypropyl

0021-9797/$ - see front matter Ó 2012 Elsevier Inc. All rights reserved.
http://dx.doi.org/10.1016/j.jcis.2012.06.019
50 P.S. Purohit et al. / Journal of Colloid and Interface Science 383 (2012) 49–54

methyl cellulose polymer [19]. Our earlier work describes the elec- teem 27AJ), consisting of 2.5, 6, and 10 mol of ethoxylate mixed
trokinetic and turbidimetric properties of silicone emulsions used in proportion to result in 11.9 HLB. Actual emulsions were made
for surface treatment [12]. These studies show the possibility of using a high shear mixer, at room temperature by sequence addi-
emulsion destabilization in the alkaline pH range, as well as bene- tion method.
ficial effects on the treated fibers using Atomic Force Microscopy. The nature and composition (i.e., surfactant content and degree
Current study is an attempt to understand droplet size and their of quaternization of amino silicone) of these emulsions are given in
solution behavior, which needs to be correlated with their impact Table 1. The nomenclature of these emulsions reflects the compo-
on textile fabric surface modification or surface feel. Textile fabric sition, for example LK-L0-2080 refers to the name of the company
represents a complex microstructure involving nano size to micron (LK) followed by non-ionic surfactant type (L for lauryl ethoxy-
size voids and spaces as well as similar size surface textures that lates), degree of quaternization (0 for 0%), and surfactant content
control the touch and feel sensation, which can be modified by (20%) and total content of silicone oil and water (80%). The total sil-
appropriate treatment. The emulsion droplet size is believed to icone oil content in the emulsion is 20%. For easier understanding,
play significant role in such coating applications. In the current the emulsions are distinguished by the amount of quaternization
work, we analyze the stability of these emulsions using light scat- in the subsequent discussion. The basic structure of diamino sili-
tering and acoustic techniques to monitor the dilute as well as con- cone used for the study is given in Fig. 1.
centrated regime of silicone emulsions. The emulsions are studied The pH of the solutions was adjusted using Fisher standard
using a Cryo-Transmission Electron Microscopy technique and the hydrochloric acid and sodium hydroxide solutions. Reagent grade
effect on hydrophobicity of nanodomains is studied by employing potassium chloride from Sigma-Aldrich was used to adjust the io-
pyrene fluorescence technique. It is shown that both the dilution nic strength of the solutions. Triple distilled water (TDW) was used
and pH have an effect on the emulsion stability with the presence for the dilution purposes. Pyrene, purchased from Sigma-Aldrich,
of a critical dilution of emulsions. Studies of emulsions in the high was used as probe for fluorescence studies.
concentration range show a bimodal distribution with majority as
nano-droplets by weight. A core shell model calculation for emul- 3. Methods
sion (oil phase) showed qualitative agreement with the observed
emulsion droplet size. The emulsion droplet size and stability were studied using vari-
ety of light scattering as well as spectroscopic techniques to probe
2. Materials the dilute as well as concentrated regimes. The droplet size data
from dilute and concentrated regimes were correlated with Cryo-
The silicone emulsions were donated by Elkay Chemicals, India, TEM imaging of emulsions.
and used as received. These emulsions were prepared from amino The silicone emulsion was diluted to the desired amount using
modified silicone shown in the Fig. 1. It is a poly-di-methyl-silox- triple distilled water, and the pH was adjusted using HCl or NaOH.
ane modified by partial substitution of methyl group by a di-amino The solutions were magnetically stirred overnight and ultrasoni-
group such as aminoethyl amino propyl group. Specific parameters cated for 15 min before the experiment. For the acoustic studies,
would be m = 7 and m + n = 400, with resulting viscosity of the emulsions were diluted to 5% polymer content (i.e., a 4
1050 cps at 25 C. The said amino modified silicone was then quart- dilution).
ernized through a stoichiometric reaction with dimethyl sulfate, at
25 C leading to 0%, 15%, 35%, and 70% quaternization. These were 3.1. Dynamic light scattering
represented in the current study as LK-L0, LK-L15, LK-L35, and
LK-L70, corresponding to 0%, 15%, 35%, and 70% quaternization. The droplet size of silicone emulsions in dilute phase (200
These amino fluids are then emulsified using a blend of three Lau- dilution with TDW) was measured using a Brookhaven system con-
ryl ethoxylate (Trade name, Esteem 27AC, Esteem 27AF and Es- sisting of BI-900 AT correlator and BI-200SM goniometer. In order
to minimize the dust effect encountered frequently in light scatter-
ing measurement, the sample solutions were filtered through a 0.5
CH 3 CH 3 CH 3 CH 3 lm Nalgene membrane prior to use. All of the measurements were
H3 C Si O Si O Si O Si O CH 3 taken in the dynamic mode (at 90° detection), that is, the instru-
n m
ment measures the diffusion coefficient of the molecules and back
CH 3 CH 3 CH 2 CH 3
calculates the effective diameter assuming spherical shape and re-
CH 2 quires at least 30 min to equilibrate the system. The autocorrela-
CH 2 tion function was transformed into the size distribution using
NH cumulant analysis, and the hydrodynamic diameter was calculated
according to the Stokes–Einstein equation.
CH 2
CH 2 3.2. Acoustic spectroscopy
NH 2
The properties of emulsions vary markedly when in concen-
Fig. 1. Basic structure of diamino silicone used for emulsion formulation. trated form, and most techniques are incapable of studying the

Table 1
Composition of amino silicone-based emulsions.

Surfactant Polymer Degree of quaternization of amino polymer


(%) (%) (amine value 25)
0% 15% 35% 70%
20 20 LK-L0-2080 LK-L15 2080 LK-L35 2080 LK-L70 2080
25 20 LK-L0-2575 LK-L15-2575 LK-L35 2575 LK-L70 2575
P.S. Purohit et al. / Journal of Colloid and Interface Science 383 (2012) 49–54 51

concentrated systems. Acoustic spectroscopy has been employed over, the droplet size seems to remain constant over a wide pH
[20,21] to monitor the silicone emulsion droplets at high concen- range (4–10). The earlier reported zeta potential studies had limi-
trations. Acoustic spectroscopy measures the attenuation and tation of 1 lm droplet size (Zeta Meter System 3.0 + with Zeiss DR
speed of ultrasound pulses as they pass through systems. The microscope), and hence, the droplet reported here by dynamic light
measurements were taken over a range of frequencies (1 MHz to scattering is different from those investigated in earlier zeta meter
100 MHz) and the resulting spectra are used to calculate the drop- studies (12).
let size distribution. The raw attenuation spectra were treated with It is considered important to examine the behavior of emulsions
a model designed to select the best droplet size distribution that in native, highly concentrated form by employing methods, which
generates the theoretical attenuation spectra fitting the experi- do not involve dilution. Acoustic spectroscopy is one such
mental data with the least error [20,21]. technique, as it can give information on droplet size in highly

3.3. Cryo-TEM
14
For the Cryo-TEM studies, the samples were pre-filtered
through 0.5 lm filter. A drop of the sample was deposited on Cu 12
TEM grid and blotted to remove excess fluid. The resulting thin film
10
of solution was vitrified by rapid plunging into liquid ethane. The

% fraction
measurements were performed below 170 C. The images are 8 0 % quaternized
recorded on a high-resolution cooled CCD camera at magnifica- 15 % quaternized
35 % quaternized
tions of up to 50,000. 6 70 % quaternized

4
3.4. Steady state fluorescence
2
To obtain quantitative information about the hydrophobic
microdomains, fluorescence spectroscopy was performed using a 0
SPEX FluorMax 2 spectrofluorometer with pyrene as the probe at 0.001 0.01 0.1 1
a concentration of 106 M. Fluorescence spectrum was obtained size (micron)
at the excitation wavelength of 335 nm within the scanning span
Fig. 3. Unimodal distribution of emulsion droplets measured by electroacoustic
of 350–600 nm [22–24]. technique (4 dilution).

4. Results and discussion


25
4.1. Emulsion droplet size
20
Dynamic light scattering (DLS) was used to measure the droplet
size of silicone emulsions in dilute phase. The results of the 0% Quaternized
15 15% Quaternized
dynamic light scattering study are summarized in the Fig. 2. It
% fraction

35% quaternized
shows the average droplet size remained fairly constant in the 70% Quaternized
10
experimental pH range for a given quaternization. This result
was unexpected, since earlier reported zeta potential and turbidi-
metric studies [12] had shown that there is a sudden change in 5
the charge and the turbidity around pH 8–10. The turbidity in-
crease [12] indicated a change in the emulsion particle size, which 0
0.001 0.01 0.1 1 10 100
is not observed by DLS.
Fig. 2 shows a systematic trend of lowering of droplet size with -5
Size (micron)
increasing quaternization, from a mean value of 115 nm with 0%
quaternization to a value of 70 nm with 70% quaternization. More- Fig. 4. Bimodal distribution of emulsion droplet measured by Electroacoustic
technique (4 dilution).

130
120 1
0.9 Attenuation
110
0.8 Attenuation of best fit unimodal
100
Attenuation

0.7
Size (nm)

Attenuation of best fit bimodal


90 0.6
0 % quaternized 0.5
80
0.4
70 15 % quaternized
0.3
60 35 % quaternized 0.2
70% quaternized 0.1
50
0
40 1 10 100
2 4 6 8 10 12 frequency mHZ
pH
Fig. 5. Attenuation and fitting (unimodal and bimodal) function for 70% quatern-
Fig. 2. Emulsion droplet size as a function of pH measured by dynamic light ized emulsion, electroacoustic measurements. 4% error observed for bimodal, 15%
scattering technique (200 dilutions). for unimodal fitting.
52 P.S. Purohit et al. / Journal of Colloid and Interface Science 383 (2012) 49–54

concentrated systems. The emulsion droplet size obtained from 115 nm size silicone droplets. With 20% total surfactant concen-
eletro-acoustic measurements is given in Fig. 3 (uni-modal distri- tration, one would expect 50% surfactant in the solution phase
bution) and Fig. 4 (bimodal distribution). As it can be seen, the gen- and remaining at the interface. Similarly, for 70 nm size droplet,
eral droplet size as measured by this technique is in the same the surfactant distribution would be 15% at the interface and 5%
range as that by DLS. It, however, gives additional information on in solution. As one dilutes these emulsions, at some critical level
the nature of distribution being narrow for higher degree of quat- of dilution, a significant migration of surfactant from surface to
ernization. More importantly, it can be seen from Fig. 5 that the bulk would commence, leading to increase in interfacial tension
attenuation function shows better fit for bimodal distribution as and hence the instability.
compared to unimodal distribution (calculated errors: 4% fitting
error for bimodal compared to 15% for unimodal distribution). 4.2. Cryo-TEM investigation-visual comparison of emulsion size
Thus, the bimodal distribution with the presence of a small per-
centage of micron size droplets and a larger fraction of nano-drop- Cryo-TEM was performed on 70% quaternized emulsions for a
lets is a better representation of the concentrated emulsion. We comparison with the light scattering and electroacoustic size mea-
believe that these micron sized emulsion droplets were studied surements. Fig. 6 shows the 70% quaternized emulsion studied at
in earlier zeta potential measurements [12]. Also, the DLS studies different magnification using cryo-TEM. Although the cryo-TEM
discussed above may not have detected this small fraction of images indicate a number distribution of the emulsion droplet,
micron droplets due to the filtering prior to measurement. they are used as visual comparison with the light scattering and
The process of emulsification is in essence the process of creat- acoustic-based studies. Cryo-TEM investigation showed the pres-
ing new surface. Energy required to create these new surfaces is ence of typical supramolecular assemblies in an emulsion, that is,
equal or more than the total surface energy of the new surfaces the emulsion droplets and the micellar structures. It can be seen
created. Thus, the two key parameters for the creation of emulsion from Fig. 6 that the droplet size was indeed in nanometer range
are surface energy and shear energy used to create the emulsion. (25–80 nm) with emulsion droplets of micron size not visible
Silicone fluids are known to exhibit high interfacial energy due a limitation of the film thickness [26–27]. The droplet size
(44 mN/m) with respect to water [25]. Assuming 1000 cps viscos- was in good agreement with the DLS and electroacoustic measured
ity, it would require a shear rate of over 700/s to allow droplet size values of 40–110 nm.
of 0.4 lm. Such shear rates through homogenizer, having orifice A core–shell model can be employed to describe the emulsion
size of 1 mm would not be possible. Experimental practice in- (polymer) droplets stabilized by the non-ionic surfactant systems
volves use surfactants, which would lower surface energies to (an oil-in-water emulsion system). A micellar shell encloses the
acceptable levels such as 3 mN/m. Since the emulsions prepared functionalized silicone polymer in such a way that the polar groups
for this study have used the same protocol including the same of surfactants are in contact with aqueous phase. For the current
homogenizer and same pressure difference, one can assume that system, it is the ethoxylated group of surfactants which are water
the change in droplet size must have been due to change in inter- solvated. The dimension of oil droplet can then be calculated using
facial energies rather than process parameters such as shear rates oil–surfactant ratio.
or velocity profiles across homogenizer orifice. Sample LK-L0 The volume of oil core is given by
2080, which has 0% quaternization, shows the highest droplet size,
4 3
in the range of 115 nm, while the one with 70% quaternization Vc ¼ pr ;
3
(LK-L70-2080) shows the smallest droplet size of 70 nm. It thus
could be assumed that the process of quaternization would lower where r is the radius of core.
surface energy by similar magnitude. Since the droplet size distri- The volume of surfactant shell is given by
bution is narrow, one can approximate the mean diameter to rep-
Vs ¼ 4pr2 d;
resent realistic volume as well as surface area. Thus, with
spherical geometry and droplet size of 115 nm, one would expect where d is the thickness of surfactant palisade layer.
droplet surface area to be 56 m2/gm, while that of 70 nm droplet Ratio of oil to surfactant volume is given by,
to be 88 m2/gm. One can thus postulate that 70% quaternization
Vc 4p r 3 r
would lower interfacial energy by a factor (88  56)/88 = 37%. It ¼ ¼
also appears logical that quaternization would create charge on Vs 3  4pr 2 d 3d
the surface, which in turn would reduce interfacial energy be- For Vc/Vs = 2.63 (using polymer density to be 0.76 g/cm3 and
tween silicone and aqueous solution. Lowering of surface energy 2:1 oil-to-surfactant ratio) and d  20 Å or 2 nm,
would be related to adsorption and ordering of surfactants at
r ¼ 2:63  3  d  16 nm
the silicone oil aqueous interface. Surfactant total concentration
can be represented as; C = Cf + Cb, where Cf is the surfactant at Hence, the estimated diameter of emulsion droplet from above
the interface, Cb is the surfactant in the solution phase, and C rep- is given by
resents total concentration. With small droplet size in the range of
Dcal ¼ 2r þ 2d  36 nm
70–115 nm size would consume sizable amount of surfactant at
the interface. As one dilutes emulsion using triple distilled water, It can be seen from Fig. 6 that the calculated diameter is in
part of the surfactants would desorb from the interface and would agreement with the lower end of emulsion droplets observed by
transfer itself to the bulk solution, to maintain its concentration. cryo-TEM studies (25–80 nm).
Such desorption process would lower surface concentration of
surfactant, thereby increasing its interfacial tension. Theoretical 4.3. Pyrene fluorescence investigation of polymer nanodomains
limits would be an infinite dilution where droplet would be left
with no surfactant and thus would be expected to exhibit interfa- The formation of hydrophobic nanodomains in the emulsions
cial tension of pure fluid with respect to water, which would be in was investigated using fluorescence technique with pyrene as a
the range of 45 mN/m. Simple calculation, with assumption that probe. The vibrational fine structure of pyrene fluorescence de-
the surfactant lauryl ethoxylate is 5 nm long and that the stabil- pends on the polarity of its environment. The ratio between the
ization process requires a fully packed layer of surfactant with intensities of the third (I3) and the first (I1) fluorescence peaks of
70% packing, there is 10% surfactant requirement to cover pyrene is commonly used as a polarity parameter [22–23]. The
P.S. Purohit et al. / Journal of Colloid and Interface Science 383 (2012) 49–54 53

Fig. 6. Cryo-TEM images for 70% quaternized silicone emulsion.

1.2 parameter but from the excimer formation. Ie/Im, the excimer-to-
Amino Silicone
Polarity parameter I 3 /I1

1.15 10X dilution monomer intensity ratio represents the probability of excimer for-
1.1 200X dilution mation for pyrene molecules [28]. Excimer formation takes place
1.05 500X dilution when two pyrene probe molecules reside in close proximity, either
1 in micellar species or the hydrophobic polymer domains. Interest-
0.95 ingly, as can be seen in Fig. 8, excimer formation is observed as
0.9 the emulsion is diluted. Clearly as a function of dilution, the number
0.85
of surfactant micellar species in the emulsion is reduced, and hence,
0.8
we conclude that the pyrene excimer is reporting from the polymer
0.75
microdomains as opposed to the surfactant micelles. Although
0.7
3 4 5 6 7 8 9 10 11 qualitatively the excimer formation increased with the amount of
pH dilution (as seen in Fig. 8), calculated values of Ie/Im indicate that
there is maximum of excimer ratio at 200 times dilution, that is,
Fig. 7. Fluorescence spectroscopy: Pyrene polarity parameter (I3/I1 ratio) for pure polymer concentration of 0.1% v/v for emulsion at pH 7.2 and pH
aminosilicone polymer and 70% quaternized silicone emulsion at various dilutions. 9.9 (Fig. 9). At pH 5.0, Ie/Im ratio follows a linear relationship with
the dilution of emulsion. This shows the presence of a critical dilu-
tion at which emulsion destabilization may occur above neutral pH.
I3/I1 ratio of pyrene in water is 0.56 and increases with a decrease
in the polarity of the medium (e.g., 1.4 in hexane).
As seen in Fig. 7, the I3/I1 ratio for pure amine silicone is 1.1, indi-
5. Summary
cating the presence of relatively hydrophobic environments. The
fluorescence studies at various dilutions show a reduction in I3/I1
The silicone emulsions droplet size was studied in both dilute
from pure aminosilicone polymer (I3/I1 = 1.1) to 200 diluted emul-
and concentrated regime by using complimentary techniques
sion (I3/I1  0.75) as seen in Fig. 7. This is expected, since the
(DLS and Electroacoustic). The combined results show that the sil-
intensity of the peaks is an average value over the period of mea-
icone emulsions consist predominantly of submicron droplets with
surement and with dilution of the system fewer micellar/hydro-
a small fraction of micron. We believe that these micron sized
phobic domains are present along with water in the emulsion. In
emulsion droplets were studied in earlier zeta potential and tur-
addition, the decrease in I3/I1 ratio, with dilution, indicates that
bidity measurements [12]. The predominance of nano-droplets
the pyrene molecules are in contact with polar water molecules
was confirmed by cryo-TEM studies and supported by core–shell
as observed elsewhere [24]. It is expected that the decrease in sur-
model calculation. The formation of hydrophobic nanodomains in
factant micellar species on dilution will lead to emulsion destabili-
the emulsions was investigated using pyrene fluorescence mea-
zation, which in turn will lead to the presence of globules or
surements. The fluorescence studies showed that the polarity
networks of free polymer where the pyrene can reside. Such a
parameter (I3/I1 ratio) of the emulsion approaches that of water
presence of free polymer can be detected not through polarity
Excimer/monomer ratio Ie/Im

3.5
7.00E+06
pH 7.2
500X dilution 3
6.00E+06
pH 5.0
200X Dilution 2.5
5.00E+06
Intensity

10X Dilution pH 9.9


4.00E+06 2

3.00E+06 1.5
2.00E+06 1
1.00E+06 0.5
0.00E+00 0
350 400 450 500 550 600 0.01 0.1 1 10
Wavelength (nm) Conc (%)

Fig. 8. Fluorescence spectroscopy: pyrene fluorescence spectra for 70% quaternized Fig. 9. Excimer-to-monomer intensity ratios (Ie/Im) for 70% quaternized emulsion as
emulsion as function of polymer concentration, data for pH 7.2. a function of polymer concentration.
54 P.S. Purohit et al. / Journal of Colloid and Interface Science 383 (2012) 49–54

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