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A Comprehensive Framework For Surfactant Selection and Design For Emulsion Based Chemical Product Design PDF
A Comprehensive Framework For Surfactant Selection and Design For Emulsion Based Chemical Product Design PDF
a r t i c l e
i n f o
Article history:
Received 23 July 2013
Received in revised form 11 October 2013
Accepted 16 October 2013
Available online 25 October 2013
Keywords:
Product design
Emulsions
Property prediction
Cloud point
a b s t r a c t
The manufacture of emulsied products is of increasing interest in the consumer oriented chemical industry. Several cosmetic, house-hold and pharmaceutical products are in the emulsied form when sold
and/or they are expected to form an emulsion when used. Therefore, there is a need for the development
of a methodology and relevant tools in order to spare time and resources in the design of emulsionbased chemical products, so that the products can reach the market faster and at a reduced cost. The
understanding and modeling of the characteristic behavior of emulsions and their peculiar ingredients
is consequently necessary to tackle this problem with computer-aided methods and tools. A comprehensive framework for the selection and design of surfactants, the main responsible for the formation
and the stability of emulsions, is presented here together with the modeling of the cloud point, a keyproperty of nonionic surfactants, with a group-contribution model. The mathematical formulation of a
standard product design problem is presented, together with the list of both the pure component properties (related to nonionic surfactants) and the mixture properties (relevant to the overall products as
an emulsion) needed for the solution of the design algorithm. These models are then applied together
with established predictive models for pure component properties of ionic surfactants and for standard
mixture properties such as the density, the viscosity, the surface and the interfacial tension, but also the
type of emulsion expected (through the hydrophiliclipophilic balance), and its stability (through the
hydrophiliclipophilic deviation), forming a robust chemical product design tool. The application of this
framework is highlighted for the design of some emulsion based chemical products.
2013 Elsevier B.V. All rights reserved.
289
Formulations can also have other physical forms [11]: suspensions containing insoluble chemicals dispersed in the liquid
with the help of a dispersant; emulsions where solid constituents
have been emulsied through selected emulsiers together with
solvents and additives; solid products such as pharmaceutical
tablets or soap bars. In chemical product design, Cussler and Moggridge [2] distinguish between commodities, chemical devices,
molecular products and microstructured products, where the term
microstructure refers to a chemical organization on the scale of
micrometers, belonging to the colloidal domain and incorporating
polymer solutions, foams, gels and emulsions. The performances of
such products are related not only to the presence of active ingredients and additives in the formulation, but also to the products
structural and material properties [12]. Among the microstructured
products, emulsied products are the most relevant, particularly in the food and cosmetic industries. Emulsions are dened
as mixtures of two normally immiscible liquids, kinetically stabilized by emulsiers (most often surface active agents, better
known as surfactants) that lie on the interface between the two
phases. Active ingredients and additives are usually dissolved in
the continuous and/or dispersed phases, according to the needs
of the products. Bernardo and Saraiva [13] proposed a simultaneous approach to address product and process design, with
special attention to cosmetic emulsions, while Bagajewicz et al. [14]
extended a generic approach [15] to consider price-competitive
markets. Recently, a systematic procedure, which is applicable to
the design of emulsied formulated products, has been proposed
by Mattei et al. [16] and it is further extended in this work (see
Fig. 2).
For emulsion-based chemical product design, the solvent(s)
design task (Task 3a) provides as output two non-miscible liquid
phases and an additional task (Task 3b: Surfactant(s) design) is
needed. Necessarily, some of the models applied for the denition
of the target properties might differ when considering an emulsied product, rather than a homogeneous formulation. In particular,
surfactants are key chemicals in most emulsied formulations and
a wide range of peculiar properties need to be considered when
designing or selecting chemicals such as surfactants [17].
290
Fig. 2. Work-ow diagram for the computer-aided stage of the formulation design methodology.
form of hi (x), gi (x) and FOBJ is different and the property models
needed are also different in each case.
(1)
hi (x) = 0
(2)
h2 (x) = 0
(3)
h3 (x) = 0
(4)
l1 g1 (x) u1
(5)
l2 g2 (x) u2
(6)
l3 By + Cx u3
(7)
Ni Ci +
Mj Di +
Ok Ek
(8)
xi i
(9)
291
292
100
W + L1
Temperature [C]
80
60
L
40
L1
20
V1
H1
S
0
0
10
20
30
40
50
60
70
80
90
100
Surfactant weight %
Fig. 3. Phase diagram of an aqueous mixture of a polyoxyethylene-based nonionic surfactant over the temperature range 0100 C Data are relative to the system between
water and dodecyl-esaethylene oxide.
Source: Data are taken from [34].
i
Ni Ci +
j
Mj Dj +
Ok Ek
(10)
groups and 1 second order group are needed, according to the original set of parameters by Marrero and Gani [18]. The results of
the parameter estimation step performed through the step-wise
regression method are illustrated in the parity plot of Fig. 4.
The results in Fig. 4 indicate that the accuracy of the Marrero and
Gani GC-methods using only rst and second order groups is not
satisfactory, as quantied in Table S4 in Supplementary material.
In particular, the maximum absolute errors (column AADmax )
are too high for many categories of surfactants considered to consider the model reliable enough to be implemented in the product
design methodology. It is therefore considered necessary to include
new third order groups in the set of parameters, in order to improve
the performances of the method, as described in [24,39], in particular relation to those compounds for which the correlation indices
were poor: branched alkyl ethoxylates and carbohydrate-derivate
ethoxylates primarily. According to Marrero and Gani [18], in fact,
the second order groups are strictly dened and one cannot arbitrarily add new second order groups as one can do with third
order groups, instead. A step-by-step systematical data-error analysis as in [24] has been performed, generating 5 new third order
groups taking care of complex structures peculiar of the available
120
100
80
60
40
20
0
0
20
40
60
80
100
120
293
Table 1
List of the original data-set of experimental cloud point (in C) of nonionic surfactants (1% weight percentage). Distinction in classes is based only on the molecular structure,
each of which is described. Compounds highlighted in gray have been excluded from the parameter regression step.
Code
CPexp ( C)
Code
CPexp ( C)
Code
CPexp ( C)
44.5
36
0
40.5
63.8
75
83
27.6
7
38.5
58.6
72.5
96
100
106
32
55
75
19.7
41.6
60.3
75
84.5
95
10.5
37
57.5
82
6
28.9
51
64.7
77.9
87.8
C12E10
C12E11
C13E5
C13E6
C13E8
C14E5
C14E6
C14E7
C14E8
C15E6
C15E8
C16E6
C16E7
C16E8
C16E9
C16E10
C16E12
95.5
100.3
27
42
72.5
20
42.3
57.6
70.5
37.5
66
35.5
54
65
75
66
92
TCnEm
IC6E6
IC10E6
78
27
TC13E9
TC16E12
34
48
64.3
22
54
75
89
C12PE9
C12PE11
C12PE15
33
50
90
C12E5P4
29.8
C11COOE8
53
C12SE3
44
AGM-13(3)
29
34
56
75
87
89
Carbohydrate-derivate ethoxylates
CnCOOEmC
CnCOOEm
C9COOE7C
44
65
C9COOE10C
Ethoxylated amides
CnGEm
CnAEm
CnSEm
C12GE2
C12GE3
78
46
34
74
54
30
absolute values of the third order contribution might be comparable or even exceed those of the rst and second order groups.
It has to be noted that the only second-order group used in this
work, AROMRINGs1 s4 , has a zero contribution since the regression performed with the simultaneous method did not nd any
non-zero value for it. Fig. S3 in Supplementary material highlights
the effect of the addition of dedicated third-order groups in the
reduction of the absolute error of the model. In particular, it can
be noticed that only 2 calculated values clearly differ of more than
10 K after the introduction of the third order groups, while in the
regression with only rst and second order groups 11 correlations
show high absolute errors.
By comparing the results before and after the addition of the new
dedicated third order groups, it can be seen that evident improvements have been achieved. In particular, after the addition of the
third order groups, linear and branched alkyl ethoxylates show
294
Table 2
Marrero and Gani group denition and contributions after the regression based on 72 experimental data of cloud point.
1st order group (i)
Ci (K2 )
6.4351e+04
2.2149e+03
6.5736e+04
1.4320e+05
5.8171e+03
0
3.0249e+03
2.7706e+03
3.7198e+04
8.9104e+03
0
0
3.3508e+04
CH3
CH2
CH
C
aCH
aC-CH2
OH
CH2 COO
CH3 O
CH2 O
aC-O
CH2 NH
OCH2 CH2 OH
AROMRINGs s
Dj (K2 )
Ek (K2 )
1.1108e+04
6.7595e+03
2.1595e+04
6.0521e+03
2.4357e+04
Table 3
Statistical indices of performances relative to the correlation of 72 data-points regarding the cloud point of nonionic surfactants using Marrero and Gani method before and
after the addition of 3rd order groups, compared with 3 different QSPR models [3537].
Model
SD
AAD
AADmax
73
73
81
68
78
8.91
5.65
9.31
5.89
7.46
7.65
4.62
7.09
4.69
3.13
25.90
15.83
50.2
17.98
52.8
100
80
60
40
20
40
60
80
100
120
As seen from Fig. 2, in the step-by-step methodology for emulsied product design, the surfactant system is designed after the
active ingredients and both the continuous and the dispersed
phases have been selected. Table S6 in Supplementary material provides the output of steps 2 and 3a, that is the chemicals chosen as
active ingredients and continuous and dispersed solvents, together
with consumer assessments and the target properties responsible
295
Table 4
List of the surfactant property applied in the case studies reported together with the model used and statistical indices.
Surfactant property
Model used
Coefcient of determination
Cloud point
Critical micelle concentration
Hansen solubility parameters
Hydrophiliclipophilic balance
Hydrophiliclipophilic deviation
Krafft temperature
Open cup ash point
Surface tension reduction
Toxicity parameter
R2 > 0.94
R2 > 0.99
R2 > 0.78
a
a
R2 > 0.94
R2 > 0.96
R2 > 0.99
R2 > 0.77
Statistical indices for hydrophiliclipophilic balance and hydrophiliclipophilic deviation cannot be provided since relative experimental values cannot be found.
precisely, the lower the surface tension, the higher the foam-ability,
and the lower the critical micelle concentration, the higher the
foam-ability. The non-irritability of the skin, on the other hand, is
estimated through Hansen solubility parameters [31]. If the Hansen
solubility parameters of the designed ingredient are compatible
with the parameters characterizing the proteins of the skin, then
that ingredient is likely to partly dissolve the protein layer, consequently irritating the skin. Therefore, proper boundaries on the
Hansen solubility parameters are set in order to qualitatively satisfy
the constraint of non-irritability. Given the above, the foam-ability
is usually related to the presence of ionic surfactants (since ionic
surfactants are characterized by low surface tension as well as low
critical micelle concentration), while the skin-care is usually connected to the use of nonionic surfactants, due to the values of their
solubility parameters, usually far from those of the proteins of the
skin. Therefore, a mixture of ionic and nonionic surfactants is usually chosen, the stability of which needs to be checked once the
other ingredients of the formulation have been chosen. Numerical constraints on the properties, as reported in Table 6, are applied
and through a CAMD techniques a restrict number of candidates are
generated. Between these, octyl esaethylene oxide is designed as
the most advantageous nonionic surfactant to be used as a nonionic
surfactant, while Sodium Laureth Sulfate is selected with rulebased selection criteria as the most advantageous ionic surfactant
to be chosen. Calculated values for the key-properties considered
in the case-study are reported in Table 6.
The stability of the two surfactants in the formulation, though,
needs to be ensured after all the other ingredients have been
selected and the most advantageous overall composition of the
product has been chosen. Table S7 in Supplementary material lists
the ingredients chosen, together with the relative consumer assessments and target properties to be satised.
The overall composition of the formulation is needed in order to
qualitatively estimate the stability of the emulsion by calculating
the HLD-value of each of the two active-ingredients selected at the
second step of the procedure, that are expected to form a stable
emulsion.
5. Future perspectives: surfactant-related phase behaviors
The description of binary (water-surfactant and oil-surfactant)
and ternary (wateroil-surfactant) phase behaviors with a
Table 5
Target properties, relative physico-chemical properties and models needed, constraints and modeled value for surfactant design for an emulsied UV sunscreen.
Target properties
Constraints
Modeled value
HLB > 12
CP > 55 C
Tf > 55 C
log(LC50 ) > 3.16 mol/m3
HLD =
/ 0
13.4
73 C
341 C
3.97 mol/m3
0.7
0.009 mol/L
296
Table 6
Target properties, relative physico-chemical properties and models needed, constraints and modeled value for surfactant design for an emulsied hand-wash.
Target properties
Constraints
Calculated
value nonionic
surfactant
Calculated
value ionic
surfactant
Foam-ability
< 33 mN/m
CMC < 0.01 mol/L
31 mN/m
0.009 mol/L
27.8 mN/m
0.008 mol/L
Non-irritability
D =
/ 22.4 1.5 Mpa0.5
P =
/ 9.8 1.5 Mpa0.5
H =
/ 11.9 1.5 Mpa0.5
16.9
9.2
13.7
a
a
a
Cleaning performances
31 mN/m
13.4
27.8 mN/m
40
Safety
Tf > 55 C
341 C
94 C
Non-toxicity
3.97 mol/m3
LD50 = 5 g/kgb
Thermal stability
CP > 55 C
TK < 20 C
73 C
16 C
Stability as an emulsion
HLD =
/ 0
0.9
1.5
Hansen solubility parameters are not available, but the surfactant (Sodium Laureth Sulfate) is known to be soluble in water, so it is unlikely to dissolve the proteins of
the skin, given their Hansen solubility parameters.
b
LC50 is not available, so a value for LD50 , another toxicity parameter, has been provided instead.
360
6. Conclusion
2 - W/O
350
Temperature [K]
297
340
330
320
310
300
2 - O/W
290
0%
20%
40%
60%
80%
Surfactant weight %
Fig. 6. Calculated sh-diagram of the system water-tetradecane-2-butoxyethanol;
wateroil ratio: 7.03.
Source: Data taken from [44].
the possibilities for the formation of each of them are easily identied, given the temperature and the composition of the formulation.
An example of such as sh-type phase diagram for the system
water-tetradecane-2-butoxyethanol is shown in Fig. 6.
In Fig. 6 different areas are can be identied: the region dened
with the symbol 1 represents the area where a micro-emulsion
can be formed, the region dened with the symbol 2 (both 2
W/O and 2 O/W) is the area where an emulsied product can be
formulated, while the region identied by the symbol 3 is a hybrid
domain, where an emulsion and a microemulsion may coexist. The
emulsion domain (2) consists of two areas: one above the hybrid
domain, described by the symbol 2 W/O, where a water-in-oil
emulsion can be formed and another below the hybrid domain,
described by the symbol 2 O/W, where an oil-in-water emulsion
is favored instead. Consequently, the region of the emulsion domain
located at intermediate temperatures between the two abovementioned areas represents an unstable region where it is not
recommended to design an emulsied product, since its life time
is expected to be limited. As a part of an emulsion-based chemical
product design procedure, then, it is necessary to make sure that the
designed formulation lies in the 2 W/O area when a water-in-oil
emulsion is desired and in the 2 O/W if an oil-in-water emulsion is wanted. This type of diagrams can be used both during the
design of the surfactant and during the verication of the designed
product. The authors are not aware of any reliable model for the
prediction of such phase equilibria, and therefore this analysis can
be performed up to now only when experimental data are available.
When predictions are necessary, the hydrophiliclipophilic deviation (HLD) approach [32] is applied instead. This method consists
of the application of an experimental-based correlation for each
of the surfactant in the formulation, considering several variables
such as the presence of electrolytes, the nature of the oil as well
as of the water phases, the temperature, and the molecular structures of the surfactant. If the calculated HLD-value is zero, then
the formulation is located in the 3 domain of Fig. 6 and therefore
an unstable system is expected. On the other hand, if a positive
value is obtained, then a water-in-oil emulsion is favored, while if
a surfactant is characterized by a negative value of its HLD, then
an oil-in-water emulsion may be formed. The higher the absolute
value of the HLD of the surfactant is, the more stable the emulsion formed is expected to be, since it is located further away from
the unstable region identied by the hybrid domain. This method
does not have the thermodynamic basis of the representation of the
ternary phase diagram, but it can be used as a qualitative predictive
model when the needed experimental data are not available.
Acknowledgments
Financial support from the Technical University of Denmark is
greatly acknowledged.
Advice given by Professor Michael Hill, from the Department
of Chemical Engineering of Columbia University, New York, in the
development of one of the case studies is greatly appreciated.
Appendix.
Appendix B. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.uid.2013.10.030.
298
Table A1
Calculation of the cloud point of Nonyl phenyl octaethylene oxide after the introduction of new third order groups. Calculated value is compared with experimental value
and with the calculations with the GC-model without 3rd order groups and three QSPR models.
Nonyl phenyl octaethylene glycol Molecular structure
O
HO
O
O
O
O
O
O
Occurrences
CH3
CH2
aCH
aC-CH2
CH2 O
aC-O
OCH2 CHOH
1
16
4
1
7
1
1
6.4351e+04
2.2149e+03
5.8171e+03
0
8.9104e+03
0
3.3508e+04
Occurrences
Group contribution
AROMRINGs1 s4
Occurrences
Group contribution
(CH2 )m
6.0521e+03
(CP )calc =
C6 H4
i
(OCH2 CH2 ) (m = 8)
Ni Ci +
j
Mj Dj +
Ok Ek = 107576.3 K , (CP)calc = 327.99 K GC-model without 3rd order groups: (CP)calc = 322.04 K, QSPR models from Table 8:
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