5 - Transparent and Translucent Soaps PDF
5 - Transparent and Translucent Soaps PDF
5 - Transparent and Translucent Soaps PDF
Teanoosh Moaddel
Trumbull, Connecticut, USA
Michael I. Hill
New York, New York, USA
Introduction
Transparent and translucent soaps have a surprisingly long history. It was discovered at
least as far back as 1789 that a transparent soap bar could be made by dissolving soap in
hot ethyl alcohol, pouring the mixture into open molds to solidify, and then allowing the
soap to age (Cristiani, 1881). Well over two centuries later, transparent and translucent
soaps make up a good proportion of soap bars sold in the marketplace. They are sold
in a variety of shapes and degrees of optical clarity, and some are hand-crafted by arti-
sans, whereas others are mass-produced by the large soap manufacturers. However they
are made, these soap bars have much consumer appeal, as clarity in a soap bar connotes
health, purity, mildness, and freshness.
Although transparent soaps have far greater optical clarity than translucent soaps, they
do share some commonalities. All compositions contain mostly tallow and coconut soap,
and they can also include varying levels of soaps made from castor oil, safflower oil, or syn-
thetic detergents. In addition, unlike ordinary soap bars, which are generally exclusively so-
dium soap, transparent and translucent soap bars both typically contain mixtures of sodium,
potassium, and/or triethanolamine soaps. Finally, both transparent and translucent soap bars
generally contain polyols, such as glycerine, propylene glycol, sorbitol, or sucrose.
The manufacturing process for transparent soaps differs from that for translucent
soaps. Translucent soaps are manufactured by energetic working, which easily lends itself
to mass production on a standard soap manufacturing line that has been modified to allow
for this. In contrast, transparent soaps are manufactured by preparing and casting a melt,
followed by cooling and solidification and sometimes by additional aging, a process that
cannot be used in a standard soap finishing line.
In this chapter, we provide a coherent understanding of the relationships and interde-
pendencies between optical clarity, bar composition, processing route, and processing pa-
rameters. First we build on basic concepts of soap phases and structure to identify sources
of light scattering, and we show how molecular interactions amongst the components of a
soap bar are critical to the development of optical clarity. Then we discuss the importance
of the process path and how it affects the efficiency of molecular interactions.
imperfections will cause surface light scattering, decreasing the intensity of transmitted
light. Internal objects that are larger than 200 nm will also scatter light and thereby reduce
the transmitted light intensity. In addition, the presence of any objects that can absorb the
incident light beam will also reduce the transmitted light intensity. These possible sources
of interaction of soap with light are depicted in Figure 5.1.
Applying these general principles of light transmission through soap requires an un-
derstanding of the various phases present in a soap bar. As indicated in Chapter 2 of this
book by Hill and Moaddel (2004), commercial soap bars generally contain multiple com-
ponents divided among multiple phases, and the particulars of the distribution of com-
ponents across the phases depends on the oil blend and the process route that are used to
get to the final structure. In conventional extruded toilet soap, a mixture of two separate
crystal types forms at thermodynamic equilibrium. One crystal type, referred to as delta
phase, is composed of the less soluble saturated long-chain soaps (e.g., C16 and C18 soaps)
and is dispersed in a continuum of another crystal type composed of the more soluble
saturated short-chain soaps and unsaturated soaps (e.g., C12 and C18:1 soaps), referred
to as eta phase. The configuration of less soluble soaps dispersed in a continuum of more
soluble soaps can be compared to bricks and mortar, as depicted in Figure 5.2.
The continuous phase (the mortar), which is composed of the more soluble soaps,
will also contain more water than the dispersed phase (the bricks), which is composed of
the less soluble soaps. Further, because solid soap and water have different refractive indi-
ces (n ≈ 1.5 for solid soap, n = 1.0 for water), these two phases will have different refractive
Continuous phase
(soluble soaps, most
of water/solvents) Dispersed phase
(insoluble soaps)
indices. Thus, incident light can be scattered as it passes through the different phases in
the soap bar. Large dispersed soap crystals, entrapped air, and surface roughness will also
scatter light, and dark objects present in the soap bar will absorb light.
This suggests that to maximize light transmission, the soap formulator should en-
deavor to raise the refractive index of the continuous phase, reduce the size of solid soap
crystals, minimize entrapped air, reduce surface roughness, and keep the color light. The
latter three can be regarded as trivial, and we will not focus on them here. The former two,
however, relate to soap solubilization and soap crystal size. Since a soap bar can consist of
multiple components distributed amongst multiple phases, controlling these two para
meters is nontrivial.
300
250
200
Temperature (°C)
Lα
Neat soap
150 lamellar
liquid L1
crystal
Isotropic liquid
100
H1
Middle
soap
hexagonal
liquid
crystal
50
0
25 50 75 100
% Water
Figure 5.3 Generic binary phase diagram of soap and water. Reprinted from Hill and
Moaddel, 2004.
110 ■ Chapter 5
Short spacing
Long spacing
Figure 5.4 Structure of solid soap crystals.
The structure of solid soap crystals is depicted in Figure 5.4., and it corresponds
to packed bilayers of soap molecules. As Chapter 2 describes in greater detail, the more
common soap phases have been described using two sets of nomenclature; see Table 5.1.
Typical liquid crystal phases encountered in commercial soaps include the lamellar liquid
crystal phase and the hexagonal liquid crystal phase, depicted in Figure 5.5.
The lamellar liquid crystal phase, Lα, is similar to that of solid soap crystal, as both
have soap molecules arranged in planar sheets. However, the hydrocarbon tails in the liq-
uid crystal are in a “fluid” state, whereas the hydrocarbon tails in the solid crystal are in
a “rigid” state. On the other hand, the more viscous hexagonal liquid crystal phase, H1,
consists of close-packed long cylindrical micelles with the soap molecules aligned so that
the hydrophilic heads are on the cylinder surface and the hydrophobic tails point toward
Table 5.1 Common Soap Phases
Omega Kappa Disordered mixed crystal with all chain lengths, saturated
Omega Eta Mixed crystal rich in unsaturated and short chain saturated soap
Beta Zeta Small mixed crystals rich in long chain saturated soap
Delta Delta Large mixed crystals rich in long chain saturated soap
Sources: Buerger et al., 1945; Ferguson et al., 1942; Ferguson, 1944.
Figure 5.5 Photomicrograph of lamellar liquid crystal (A) and hexagonal liquid
crystal (B).
Transparent and Translucent Soaps ■ 111
the center. We refer the reader to Chapter 2 for more details. Optical microscopy with
cross-polarizers, differential scanning calorimetry, small angle X-ray diffraction, and rhe-
ology are typical characterization tools used to investigate the structural nature and flow
behavior of these different phases (Nemeth et al., 1998; Funari et al., 1992; Ahir et al.,
2002; Rosevear, 1968; Borne et al., 2000; Laughlin et al., 1994).
Insoluble
soaps
Soluble
soaps
% Solvent
+ + +
- - -
- - - - - - - -
- - - - - - - - -
+
+ + + +
+ - +
+
+ + + + + + + + + + +
+ +
+ +
+
++ +
+ + + + + + + + + +
- - - - - - - - - - + + + + + +
- - - - - - +
+ +
+
++
- +
+
-
-
-
- - - - - - - - --
- - - - - - - - - - - - -
+ + + + + + + + + +
+ + + + + + + + + + + +
+ + + + + + + + + + + + +
- + + + + - + + + + +
- - - - - - - - - - - - - - - - -
-
- -
requires recrystallization into zeta (beta) phase, and this is facilitated by increasing the
solubility of the continuous phase, translucency should be best at an oleate:laurate molar
ratio of 1:1. This corresponds to a tallow:coconut ratio of between 90–10 and 65–35, re-
spectively, or an IV of between 30 and 50.
Thus, production of translucent soap with excellent optical clarity requires 70–80%
soap with an IV between 30 and 50; 5–12% of a combination of polyols, which can in-
clude select mixtures of glycerine, propylene glycol, and sugars; and 13–20% water, com-
bined with sufficient intensive mixing within the right window of temperature and water
levels (typically 40–50 °C and 13–20% water).
H 2O
0
100
5
95
10
90
15
85
20
80
25
L1 75
30
70
35
65
40
25 °C 60
45
L1
+
55
H1
H1
50
H 50
1
55
45
60
40
65
35
70
30
75
H1 25
80 +
Crystals 20
85
15
90
10
95
5
100
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 0
Na oleate Na laurate
Figure 5.10 Phase diagram of sodium oleate, sodium laurate, and water.
L1—Isotropic micellar phase; H1—Hexagonal liquid crystalline phase. Reprinted from Mongondry
et al. (2006).
114 ■ Chapter 5
1
In the Cavity Transfer Mixer the intensive work occurs between rotor and stator, which provides
for a continuous operation, and it is enclosed and jacketed, which provides good temperature and
moisture control.
2
The L11 phase has been determined to be within 5%. The exact phase boundaries were not ac-
curately determined for the more viscous phases and are only estimates.
Transparent and Translucent Soaps ■ 115
Glycerine
0
100
5
95
10
90
15
85
20
80
25
75
30
70
35
65
40
60
45
55
50
50
55
45
60
L1 1 40
65
35
70
30
75
25
80
20
85
15
90
10
95 H1 1 crystal 5
100 LLαa
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100
H2O 74/26 (w/w) NaOl/NaL
Figure 5.12 Phase diagram of glycerine, water, soluble soap fraction of soap.
L1—Isotropic micellar phase; H1—Hexagonal liquid crystalline phase; Lα—Lamellar liquid crystal-
line phase; NaOl—Sodium oleate; NaL—Sodium laurate.
The final bars were then stamped. The key ingredient helping to render these bars trans-
parent was ethanol, which acts as a hydrotrope. That is, the addition of ethanol increases
the solubility of the soap and prevents the liquid crystal phase from forming when the
soap solution is cooled. In this case, when the soap solution cools, it forms a gel structure
rather than the usual bricks-and-mortar structure. It is still debated whether the struc-
ture of these bars is a gel consisting of a rigid network of small solid crystals with isotro-
pic solution in the interstices, or instead consists of a supercooled solid (a “glassy state”)
with dispersed solid crystals (Wang et al., 2004). Other approaches to making transparent
melt-cast soap bars involve the use of high levels of polyols, such as glycerine, propylene
glycol, various sugars, and triethanolamine, to increase soap solubility and prevent liquid
crystal formation on cooling. In contrast to the methods in which ethanol is used, there
is no need for maturation. The patent literature also shows that highly soluble syndets,
such as sodium lauryl ether sulfate, sorbitan oleate, nonyl phenol ethoxylates, and sodium
cocoyl isethionate, are often used to make transparent soaps. In these cases, however, soap
remains the primary structurant. Transparent soap bars of excellent optical clarity can be
made by combining 35–50% soap (with minimal unsaturation), 30–40% specific blends
of polyols, and 15–25% water. The soap used in these compositions must have a mini-
mum level of unsaturation so as not to promote formation of the liquid crystalline phase
on cooling.
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