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To cite this article: Maria‐Teresa Celis & Luis H. Garcia‐Rubio (2008) Characterization of
Emulsions: A Systematic Spectroscopy Study, Journal of Dispersion Science and Technology,
29:1, 20-26, DOI: 10.1080/01932690701686775
Download by: [Australian Catholic University] Date: 09 October 2017, At: 04:55
Journal of Dispersion Science and Technology, 29:20–26, 2008
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print/1532-2351 online
DOI: 10.1080/01932690701686775
Emulsification processes results in the generation of droplets populations produced from the
dynamic equilibrium between the breakup and coalescence phenomena determined primarily
by the formulation and composition variables, mixing characteristics and emulsion prep-
aration. The information contained in the UV-vis spectrum on the absorption and scattering
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properties of the emulsions lead to the interpretation of the spectra in terms of the particle
size distribution, the particle shape, and the chemical composition of the oil and emulsifier.
This article reports analysis of emulsions on transmission spectrum as function of the oil con-
centration and physicochemical variables. The quantitative interpretation of the transmission
spectrum is performed in the portion where no absorption is present (300 – 820 nm) leading to
reliable estimated of droplet size populations in the range of 1 to 20 mm. The possibility of
obtaining information from a single multiwavelength measurement makes UV-vis spec-
troscopy a powerful tool for characterization of dispersed systems.
scattered light measured at one or several observation angles. In the Qext(m(l0), D) corresponds to the Mie extinction coefficient, and
diluted regime, Mie theory can be used for the interpretation of Np is the number of particles per unit volume.
transmission and angular scattering data. This theory describes The theoretical basis for the analysis is Equation (1) from
the absorption and scattering behavior of spherical particles of which it can be inferred that the shape of the spectra as
any size and refractive index and it has shown to be very successful function of wavelength depends on the kernel of the integral
in a large variety of applications.[2,18,19] Techniques for the esti- and of the number of particles. To be able to compare the
mation of particle size distribution from multiwavelength shape of the spectra as function of wavelength it is necessary
spectral data have been reported in the literature.[19 – 21] to eliminate the effect of the number of particles. It is
However, most of these techniques require that the shape of the apparent from Equation (1) that if the optical density
PSD be known, or rely on the advantages inherent in the mathemat- measured at every wavelength is divided by the integral of
ical properties of particle size distributions such as the Lognormal, the optical density as function of wavelength, the number of
Gaussian, etc. In addition, most measurement techniques rely on a particles is canceled. It is given by:
limited number of wavelengths and do not address issues related to " #
differences in chemical composition.[21,22] The spectroscopy tech- t0 ðlÞ
t ðlÞ ¼ Ð lf ½2
nique applied herein utilizes a broad wavelength range (190–
li t0 ðlÞd l
820 nm), which make possible particles population analysis with
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sizes ranging from nanometric to micrometer range.[13 – 17,23,24] where t̄ (l) is the normalized spectrum transmission, li and lf
In addition to the dynamic range for scattering the absorption com- are the wavelengths (nm) over which the discrete optical den-
ponent, due to the presence of chromophores, provides quantitative sities as function of the wavelength t0(l) are measured.
information for chemical composition of the labeled mol-
ecules.[15,16,25] The technique applied herein is based on the regu- Quantitative Interpretation
larized solution to the inverse scattering problem posed by the
The interpretation of the spectra can be done in terms of the
multiwavelength turbidity equation. As such, it does not require
particle size distribution, the particle shape and the chemical
prior assumptions regarding to the shape of the particle size distri-
composition of the oil and emulsifier. Equation (1) can be
bution.[13,26,27] Spectroscopy study over range of wavelength
written in matrix form by discretizing the integral with an
(190–820 nm) and analysis of emulsions, in terms, of droplet
appropriate quadrature approximation:[13,31]
size distribution in the spectral region (300–820 nm) have been
successfully applied to the continuous estimation of the droplet t ¼ A f þ 1
size distribution (DSD) and to the assessment of stability of
emulsions.[8,12,17,28] In addition, monomer emulsions have been where A represents the discretized kernel, f̄ is the discrete rep-
characterized on the implementation of the multiwavelength spec- resentation of the particle size distribution, and 1̄ represents
troscopy technique and its verification with osmium tetroxide/ experimental errors, the errors associated with the adequacy
electron microscope technique.[29] This article reports a qualitative of the model, and the errors resulting from the discretization
spectroscopy study of saturated hydrocarbon emulsions over a procedure.[13] The regularized solution a Equation (3) is
broad wavelength range (190–820 nm), and a quantitative given by:[13,26,27,31]
interpretation in the wavelength range of 300 to 820 nm, in
^f ðgÞ ¼ ðAT A þ gHÞ1 AT t ½4
terms, of spectral differences as function of physicochemical vari-
ables and of the oil concentration. In the framework of this paper,
where H is a covariance matrix that essentially filters the exper-
the terms PSD and DSD will be used interchangeably.
imental errors, and the errors arising from the model adequacy
and the approximations required for its numerical implemen-
INTERPRETATION OF THE TRANSMISSION SPECTRUM tation (1); g is the regularization parameter estimated using
the Generalized Cross-Validation technique.[27] The General-
Qualitative Interpretation ized Cross Validation technique requires the minimization of
The UV-vis spectra of particle suspensions are known to the following objective function with respect to g.[13,26,27,30,31]
contain information on the absorption and scattering properties
of the particles.[20] For spherical particles, Mie theory relates the j½I AðAT A þ gHÞ1 AT tj2
VðgÞ ¼ m1 ½5
transmission t (l0) measured at a given wavelength l0 and the nor- ½trace½I AðAT A þ gHÞ1 AT 2
malized particle size distribution f(D) through the following
equation.[18,20,30] m1, represents the number of discrete turbidity measurements.
Simultaneous application of Equations (4) and (5) to the turbid-
p ð 1 ity spectra yields the discretized droplet size distribution.[13,30]
t ðl0 Þ ¼ lNp Qext ðmðl0 Þ; DÞD2 f ðDÞdD ½1 The range of integration and the width of the discretization
4 0
elements are algorithmically selected to achieve an optimal
where l is the cell path length, D is the particle diameter, solution for a desired number of discretization elements.
22 M.-T. CELIS AND L. H. GARCIA-RUBIO
Equation (1) can be explicitly expressed in terms of the from the liquid-liquid dispersions are recorded using a diode
absorption and scattering components: array spectrometer (HP 8452 Hewlett-Packard, USA) having
p ð 1 an acceptance angle smaller than 2 degrees, and a thermoelec-
t ðl0 Þ ¼ lNp Qsca ðmðl0 Þ; DÞD2 fDÞdD tric cell holder with a temperature controller with temperature
4 0 programming capabilities. Prior to recording the spectrum of
p ð 1 ½6
2 each sample the spectrometer is zeroed to account for any
þ lNp Qabs ðmðl0 Þ; DÞD f ðDÞdD
4 0 stray light. To avoid the effect of inhomogeneities in the sus-
pending medium, the background spectrum is taken using the
where, Qabs and Qsca represents the absorption and scattering respective suspending media from the batch utilized in the
efficiencies respectively. Upon convergence, Equation (6) preparation of the original sample (sterilized de-ionized
can be useful to evaluate the contribution of chromophoric water) to the operation temperature. Equation (1) requires as
groups present in the emulsion, typically, the emulsifier. input the optical properties of the components of the
Equations (1) and (3) – (5) can be utilized to obtain the emulsion which are represented through the complex relative
droplet size distribution from continuous spectroscopy refractive index (m(l0)):
measurements of the emulsions as functions of time and of
dilution ratio.[12] nðl0 Þ þ ikðl0 Þ
mðl0 Þ ¼ ½7
n0 ðl0 Þ
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EXPERIMENTAL SECTION where n(l0) corresponds to the real component of the refractive
index of the droplets, and n0(l0) corresponds to the refractive
Materials index the suspending medium. The imaginary part of the
The ionic emulsifier, sodium dodecyl benzene sulfonate complex refractive index is represented by absorption coeffi-
(SDBS) is obtained from Polysciences Inc. The absence of the cient (k(l0)). Saturated hydrocarbons are known to have negli-
characteristic dip prior to the critical micellar concentration gible absorption in the UV-vis portion of the spectrum. The real
(cmc) in the surface tension versus emulsifier concentration part of the complex refractive index as a function of wave-
curve indicates the purity of this material. The cmc is length is calculated, using a modification of Sellmeier-Drude
1.4 g/L + 0.1. Saturated hydrocarbons obtained from correlation.[17] The refractive index of water n0(l0) in
(Aldrich Chemical Company (USA) with a purity of 99%) are Equation (7) as a function of wavelength is calculated from
free of impurities and used without purification. The purity of the correlation reported in Elicabe and Garcia-Rubio.[13,31]
these oils is verified spectroscopically. Sterilized de-ionized The Mie scattering coefficients in Equation (1) are calcu-
water is used in emulsion preparation. The equipment utilized lated with a computer program, which includes multiwave-
for the preparation of the emulsions consists of a 100 ml glass length spectral calculations and has been adapted to calculate
reactor, an electric stirrer and a temperature controller. distributions of particle sizes.[13,26,27,30,31]
concentration.
Figure 12 shows the variation of the droplet size of decane/
SDBS/H2O emulsions with the oil concentration for different
Figure 7 shows the variation of the droplet size distribution emulsifier concentration. As suggested, from spectra in
with the alkane chain length at (Co ¼ 1e-4 g/mL), and Figure 5, the emulsion droplet size undergoes changes with
Figure 8 summarizes the changes of droplet average diameter the emulsifier concentration. An increase in emulsifier concen-
with the oil concentration as a function of alkane chain tration generally tends to speed up the emulsifier adsorption,
length. Both plots confirm what is suggested by Figure 3, the which is associated with interfacial tension decreasing and
droplet size decreases and the breadth of the distribution droplet breaking. All of these effects promote the formation
change as the alkane chain length increase. As expected, of smaller droplets.
from Figure 3, the variance of the distribution increase for As it is noted, there is a relation between the spectral changes
shorter oil chain length (Figure 9). and droplet size distribution of emulsion populations in the
Figures 10 and 11 show the quantitative spectral interpret- macroemulsion range as function of the oil concentration.
ation of heptadecane/SDBS/H2O emulsions as function of Therefore, the spectra can be used to obtain quantitatively
the temperature. Figure 10 shows the variation of the droplet measurements of emulsion droplet size and its distribution as
size distribution for different temperatures (T ¼ 308C, function of physicochemical variables. Additional spectroscopy
T ¼ 458C, and T ¼ 558C). The close match of the normalized studies of labeled emulsifiers are necessary to interpret the wave-
transmission spectra in the region between 300 and 820 nm length portion of the spectrum (240–300 nm). These studies are
shown in Figure 4 lead to unimportant changes in the breadth ongoing in order to assess the distribution of emulsifier among
of the distribution observed in Figure 10, and similar the phases present and the quantification of droplet population
emulsion droplet size (Figure 11). in the nanoemulsion range.
FIG. 10. Number based particle size distribution of heptadecane/SDBS/ FIG. 12. Variation of the droplet size of decane/SDBS/H2O emulsions
H2O emulsions as function of temperature at Co ¼ 1e-3 g/mL. with the oil concentration for different emulsifier concentrations.
26 M.-T. CELIS AND L. H. GARCIA-RUBIO
CONCLUSION [12] Celis, M.-T. and Garcia-Rubio, L.H. (2002) J. Dispersion Sci.
A systematic study of emulsions as function of the oil con- Technol., 23 (1– 3): 293– 299.
centration and physicochemical variables over the entire wave- [13] Elicabe, G. and Garcia-Rubio, L.H. (1990) In Polymer Charac-
terization, Advances in Chemistry Series 227; Craver, C. and
length (190 –820 nm) has been shown using multiwalength
Provder, T. (eds.); American Chemical Society: Washington,
ultraviolet/visible (UV-vis) spectroscopy. The changes of
DC, pp. 83 – 104.
absorption bands in the different spectral regions are related [14] Brandolin, A., Garcia-Rubio, L.H., Provder, T., Koehler, M.E.,
with the size and distribution of droplet populations and and Kuo, C. (1991) ACS Symposium Series American
found to be in agreement with process conditions. Droplet Chemical Society, Washington, DC, pp. 20 – 33.
populations in the range of 1 to 20 mm have been measured [15] Mattley, Y. (2000) An investigation of the spectroscopy proper-
from the quantitative interpretation of spectra in the wave- ties of platelet during activation of storage: implementation of
length range (300 – 820 nm), and experimental results may be the new interpretation model. Ph.D. Dissertation, University of
indicative of the existence of nanodroplet populations in the South Florida: Tampa, Florida, USA.
spectral region (240 –300 nm) where chromophoric groups of [16] Bacon, C.P. (1999) Simultaneous characterization of particles
emulsifier are present. The potential to extract large amounts properties (size, shape and composition) for the development
of information from a single multiwavelength measurement of multiangle-multiwavelength spectrometer system. Ph.D.
Dissertation, University of South Florida: Tampa, Florida, USA.
makes UV-vis spectroscopy a powerful tool in the area of
[17] Celis, M.-T. (2000) Studies of the initial conditions in emulsion
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colloids, and it provide the essential information for continuing polymerization reactors. Ph.D. Dissertation, University of South
studies on the evaluation of the distribution of emulsifier in the Florida: Tampa, Florida, USA.
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nanoemulsion range as function of the oil concentration and Williams, J.C. (ed.); Chapman and Hall: New York,
operation conditions. pp. 314– 327.
[19] van de Hulst, H.C. (1981) In Light Scattering by Small Particles;
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