Ind. Eng. Chem. Res.

2008, 47, 6347–6353 6347

Soap: The Polymorphic Genie of Hierarchically Structured Soft

Condensed-Matter Products
Janhavi S. Raut* and Vijay M. Naik†
Hindustan UnileVer Limited, Research Centre, 64 Main Road, Whitefield, Bangalore
560 066, Karnataka, India

Siddhant Singhal‡ and Vinay A. Juvekar‡

Indian Institute of Technology Bombay, Powai, Mumbai, 400 076 Maharashtra, India

More than 5 million tonnes of metal salts of fatty acids are manufactured and used worldwide every year, to create
a range of soft condensed-matter products such as bar soaps, stick deodorants, personal care creams, toothpastes,
and lubricant greases. These molecules, popularly known as soaps, are capable of forming a plethora of states and
self-assembled aggregates such as micelles, liquid crystals, solid crystals, and gels, whose characteristic sizes or
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domain sizes can span from nanometers to centimeters. The type and mix of the phases formed, their morphologies,
and their states of dispersion or the nature of their further supra-assemblies dictate the underlying micromechanical
Downloaded via COLGATE-PALMOLIVE CO on June 22, 2021 at 21:47:23 (UTC).

structures of products, which, in turn, are responsible for their optical, structural, and rheological properties.
Developing processing guidelines to manipulate characteristic micromechanical structures is therefore key to obtaining
the desired look, touch, feel, and function of these products. The article discusses a few illustrative examples of
these structure-property relationships demonstrated by multiscale soap assemblies. Observations of some novel
tertiary structures formed by crystallizing soap fibers at the air-water interface, serendipitously discovered by us
in the recent past, are also discussed, to illustrate the richness and mysteries of the well-studied and so-called
mature subject of soaps.

1. Introduction bar of soap or a transparent bar of soap. Alternatively, by

obtaining the right crystal morphology and state of dispersion,
The term “soap” includes all compounds formed by one can produce an extrudable/thermoplastic bar of soap at
reaction of either an inorganic or organic base with an organic less than 15% water content or a rigid framework-structured
fatty acid.1 An important subgroup of soaps is a class of nonextrudable bar containing as much as 90% water. This
molecules that are metal salts of linear fatty acids. These very ability of soap molecules to form self-assembled
simple metal alkyl carboxylates are some of the oldest structures even in hydrophobic liquids makes them suitable
surfactants known. Today, more than 5 million tonnes of these for use as so-called low-molecular-mass organic gelators
molecules annually find their way into various products that (LMOGs)2,3 in a diverse range of products. For example,
fall in the class of soft condensed-matter composites. A bulk lithium salts of 12-hydroxy stearic acid are employed4 to
of these soap molecules are used in consumer goods such as structure free-flowing lubricant liquids into viscous, gellike
bar soaps, liquid washes, personal care creams, and tooth- lubricant greases. Aluminum salts of naphthenic and palmitic
pastes. In almost all of these products, the soap molecules acids can be used to structure free-flowing inflammable
play the familiar role of a surface-active agent to deliver a liquids, typically gasoline, to create the notorious flammable
variety of functions such as lather and emulsion stabilization, liquid napalm. Even simple products such as plasticine are
detergency, and surface wetting. What is relatively less
appreciated is the ability of the soap molecules to self-
assemble in numerous ways and form aggregates to reduce
the system free energy, resulting in a range of different phases
with unique molecular arrangements and physical character-
istics. These aggregates and phases can, in turn, be engineered
to take varied shapes and assemble into different tertiary
structures through judicious use of field variables and
processing conditions. The different equilibrium and non-
equilibrium micromechanical structures thus produced can
be employed to obtain a extensive spectrum of variations in
physical properties and in-use characteristics of products, with
minor changes in their mean bulk compositions. For example,
by adjusting the size of soap crystallites and the refractive
indices of various phases, one can produce an opaque white
* To whom correspondence should be addressed. E-mail:
janhavi.raut@unilever.com. Figure 1. Simplified schematic T-x phase diagram of the aqueous soap
†
Current address: Indian Institute of Technology Bombay, Powai, system. L1, micellar solution; H1, hexagonal phase; LR, lamellar phase; S,
Mumbai, 400 076 Maharashtra, India. solid phase; TK, Krafft boundary; dotted line, CMC curve; dashed line,
‡
Indian Institute of Technology Bombay. molecular solubility curve for solid phase.

10.1021/ie0714753 CCC: $40.75  2008 American Chemical Society

Published on Web 07/02/2008
6348 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008

Figure 2. Polymorphism exhibited by soap molecules below the Krafft boundary: (a) plates, (b) rods, (c) ribbons, (d) twisted fibers, (e) C12 soap gel, and
(f) C16/C18 soap gel formed in the presence of solvents such as mono-/dipropylene glycol (MPG/DPG). Plate b for 1% sodium myristate (NaMy) in water
is from ref 17. Plates e and f are from ref 29.

Figure 3. (a) Phase composition of fresh-cast Pears soap as a function of temperature determined using wide-line NMR spectroscopy. (b) Small deformation
oscillatory compression measurements as a function of temperature. Frequency ) 1 Hz. (c) Small deformation oscillatory shear measurements as a function
of angular velocity. Amplitude of strain controlled at 0.05%.

formulated by employing suitable soaps to obtain their desired
viscoplastic rheological behavior. In this article, we intend
to illustrate the role played by typical phases exhibited by
soap molecules and their supra-assemblies in the above
categories of products, while “structuring” them to control
their form, appearance, and other physical, mechanical, and
sensory properties.
In section 2, we briefly introduce commonly encountered
primary phases and forms exhibited by soap molecules in aqueous
environments and their dominant rheological behaviors. In sections
3 and 4, we highlight, through examples, the role of processing on
the micromechanical superstructures formed by these phases and
their influence on the end properties of finished products. Finally,
we illustrate how soap molecules, despite centuries of technological
history, continue to surprise us with hitherto-unknown novel self-
assembled structures and how the area is still an open arena for
research.
2. Polymorphic Forms of Soap Molecules and Their
Aggregates in Aqueous Systems
For nearly a century, soap molecules have been the subject
of a large number of scientific studies because of their ready
availability and commercial importance. Driven by the need to
shield their solvophobic part in a particular environment, soaps,
like other amphiphilic molecules, organize themselves into a
range of micellar, liquid-crystalline, and crystalline forms. Phase
diagrams depicting these different transitions as functions of
temperature, concentrations, presence of electrolytes, cosolvents,

Figure 4. Effect of flash drying and shear working (below TK) on the mixed soap microstructure.
Figure 5. (a) Flow-direction-dependent transient behavior of platelike mica
particles suspended in 5% sodium carboxymethyl cellulose (SCMC) solution
with 20 wt % particle loading. Shear rate ) 1 s-1. The flow direction was
reversed every 300 s. (b) Schematic depicting the effect of reversing the
direction of shear on the suspension viscosity with anisotropic particles.
and so on have been determined for a large number of soap
species and their mixtures.5–21 The typical phase diagram of a
soap species, in the presence of a solvent system, has the general
form depicted schematically in Figure 1. The diagram is
characterized by the TK line corresponds to the Krafft boundary,
which essentially gives the temperature above which the soap
molecules exist in a molten but aggregated form. The Krafft
point is defined as the point of intersection on the temperature
axis between the curve of molecular solubility for the solid soap,
depicted by the dashed-line extrapolation, and the curve of the
critical micelle concentration (CMC), depicted by the dotted
line. As the soap molecules are introduced into water, at very
low concentration (to the left of the dotted line), they exist as
individual molecules in solution, exhibiting preferential adsorp-
tion at surfaces or excess concentrations in the interfacial
regions. They thus serve to stabilize interfaces by lowering the
total free energy associated with maintaining a phase boundary.
Upon an increase in concentration beyond the CMC curve, the
molecules start forming aggregates, shielding their hydrophobic
tails from the aqueous surroundings, thereby resulting in the
formation of spherical micelles. With a further increase in
Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008 6349
concentration, the spherical micelles deform to form rod-/
wormlike or disklike micelles. The individual micelles start
packing together as the charge repulsion diminishes in the
presence of higher counterion concentrations. This leads to the
formation of liquid-crystalline phases in the molten state.
Hexagonal phases (H1) are composed of rodlike micelles packed
together side by side in a hexagonal pattern, whereas maximum
packing of the molecules is achieved through the formation of
lamellar structures (LR), wherein flattened disk micelles come
together and form large stacks of double-layered sheets, as
shown in Figure 1. Bicontinuous cubic phases (V1) having an
aggregate curvature between those of rods and disks can also
be present between the H1 and La phases. Below, the Krafft
boundary, the soap molecules can form chain-frozen solid
crystals, or gel phases, which consist of rigid lamellae of soap
double layers with a disordered liquid solution sandwiched
between them. It is well-documented that the chain-frozen solid
soap crystals exhibit a number of forms such as fine fibers,
ribbons, twisted fibers, rods, and flat platelets (Figure 2),
depending on the type and mixture of soap molecules involved,
as well as the crystallization conditions. The presence of nonsoap
inclusions (cosurfactants, electrolytes, solvents, and so on) can
modify the phase behavior, even at very low concentration
levels. For instance, hydrotropes such as ethanol solubilize the
liquid-crystalline phases, increasing the micellar solution region
in the phase diagram. Minor levels of electrolytes can have a
strong influence on both the CMC and the Krafft temperature
through the common-ion effect, or they can produce insoluble
soap salts.19
The rheological behavior of aqueous soap solutions is
dependent on the nature of aggregation and the phases formed
by the soap species.21,22 Whereas dilute spherical micellar
solutions can exhibit Newtonian rheology, the rheological
behaviors of solutions containing concentrated spherical
micelles or anisotropic rodlike or disklike micelles are more
complex. These micelles rotate in shear flow. The viscosity
of solution increases sharply with increasing concentration
of soap, when the rotating rods/disks start to overlap with
each other, forming transient networks. The liquid-crystalline
phases formed at higher concentrations exhibit even more
complex nonideal rheological behaviors, as well as mani-
festations such as thixotropy, dilatency/pseudoplaticity, and
shear banding. Peculiarly, the hexagonal and cubic phases
have much higher viscosities than the more concentrated
6350 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008
Figure 6. Stacking of (a) stearic acid platelets in a pearlescent skin cream and (b) aragonite platelets in a sea abalone shell.
Figure 7. Current yield stress versus concentration behavior for the solid
structurant and the desired behavior through hierarchical structures.
lamellar phases, whose bilayers can slide more readily over
one another. Most liquid-crystalline phases also exhibit a
yield stress, with the cubic and hexagonal phases exhibiting
pure elastic behavior under low deformation and at high
oscillatory frequencies. Because of difficulties in obtaining
single soap crystals of sufficiently large sizes, however, the
mechanical properties of solid crystalline phases are not very
well studied and reported in the open literature.
3. Soap as a “Material”
One of the most common items of our daily use that consists
almost entirely of soap molecules (as high as 85%) is a bar of
soap. In this section, we use various case studies to illustrate
how it is not the chemical composition alone but the nature
and hierarchical superassembly of the coexisting phases that
dictates the material properties of bar of soap.
In the first case study, we discuss a historically well-known
bar soap, namely, Pears. During the manufacturing process, it
is cast as an approximately 60% solution of soap species in
aqueous denatured spirit into molds and allowed to solidify as
unmatured “green” Pears bars. At room temperature, these green
Pears bars contain only about 20% solids as determined using
low-field NMR techniques, with the remaining 80% being in
liquid state. Yet, a green Pears bar exhibits a solidlike rheology
(cf. Figure 3). However, if the bar is subjected to shear, it breaks
down to form a flowable slurry. This is very similar to the
rheological characteristics exhibited by fruits such as apples,
which can be sheared to obtain a “juice”. The Pears slurry has
the functionality of a bar of soap but lacks the structure, just as
the crushed apple has the same taste but lacks the rigidity of a
fruit. Analogously to the unique arrangement of lignocellulosic
networks of turgid cells in fruits forming closed foam sample-
spanning structures, resulting in their rigidity, the green Pears
formulation is also rendered into a rigid bar through the unique
microstructural morphology of its solid crystallites, which form
a sample-spanning load-bearing network. The commonality lies
in the inability of both of the sample-spanning networks to
withstand steady shear or large deformation. The desired
morphology of the Pears bar, which is a nonequilibrium
arrangement, is achieved through appropriate processing routes
and provides an excellent example of structure-property
behavior manipulation through processing.
However, the same is not true of all bar soaps, and a
nonequilibrium structure is not always preferred. For a more
conventional bar of soap (e.g., Lux), which is our next case
study, the rules are completely different. These soaps, which
contain approximately 85 wt % various soap species and
12-15% water, are processed via a high-shear milling and
extrusion forming route, and their formulations are very different
from that of a Pears bar. The structure of these soaps is described
by the “brick-and-mortar” model. The bricks, which occupy
about 60% of the phase volume, are composed of solid
crystallites of long-chain insoluble soaps (e.g., sodium stearate,
sodium palmitate) that serve the role of structurants, whereas
the mortar consists of a mix of liquid-crystalline (LC) phases
(30%) and isotropic liquid (10%) of short-chain and unsaturated
soluble soaps (e.g., sodium laurate, sodium oleate) that provide
the function of lathering and cleaning. In the initial stages of
soap preparation, the neutralization of the fatty acids with caustic
soda results in a soap mass with about 30-40% water in which
both the insoluble and soluble soaps are held in a mixed lamellar
phase. Downstream, this soap mass is subjected to flash drying
to reduce the water content to the desired level of 12-15%.
This rapid drying operation, which takes place on a time scale
on the order of milliseconds, congeals the mixed lamellar phase
into a nonequilibrium supersaturated state with the soluble and
insoluble soap molecules trapped into a congealed mixed-
crystalline phase called the kappa phase (cf. Figure 4) character-
ized by a unique X-ray pattern with peaks at 4.05, 3.20, and
2.97 Å, with the latter being used to characterize the phase.
The trapped soluble soap is thus no longer readily available for
providing rapid lathering or cleaning functions, and the resultant
bar of soap has the structure of a bar but does not display the
most desirable in-use characteristics of a bar soap. It lathers
slowly and forms slimy mush in contact with a water layer.
The bar, therefore, has to be shear-worked with the temperature
maintained below the Krafft boundary to restore the equilibrium
phase structure. The shear working is required to overcome the
activation energy barrier for getting the soluble soap out of the
nonequilibrium mixed soap crystals into the mortar phase. When
the soluble soaps are extracted into the mortar phase, the long-
chain crystals left behind recrystallize into a new form called
the zeta phase (characteristic X-ray peaks at 4.05, 3.50, and
2.75 Å). Another effect that has been observed after shear
working of a bar of soap is a higher optical transparency for
some specialty formulations. This is caused by a reduction of
the crystal size (because of particle breakdown during shearing
and recrystallization of the zeta phase, which is characterized
by smaller crystallite sizes) and better refractive index matching
between the solid and mortar phases because of the higher
extents of soap solubilization in the mortar. The relative impact
of both on the scattering behavior of the composite bar can be
assessed by the Raleigh-Gans equation. Thus, in this case, in
contrast to the case of a Pears bar, the nonequilibrium structure

Figure 8. Different hierarchical structures observed in bar soaps.
Figure 9. Transition from (a) equilibrium platelike crystals to (b) straight
fibers, (c) branched fibers, and (d) glassy/amorphous structures with
increasing cooling rate.
is detrimental to the functioning of the bar soap. It is the
restoration of a near-equilibrium structure that helps achieve
the desired structure, function, and appearance of the bar.
Whereas the applied shear provides the necessary energy input
into the bar soap to bring about the phase transformations, it
also interacts physically with the soap mix at various levels.
Both the LC phases in the mortar and the solid platelike
crystallites of soap are known to align along flow lines, leading
to complex rheological behaviors that can pose significant
challenges during processing. In Figure 5, we show results from
transient viscosity measurements that were carried out employ-
ing a model suspension of mica platelets suspended in a 5%
sodium carboxymethyl cellulose (SCMC) solution. This was
used as a model system to obtain a qualitative understanding
of the motion of the anisotropic platelike soap particles under
shear, as similar studies with a fully formulated opaque soap
system would not be feasible. The measurements were carried
out on a CarriMed CSL 500 controlled-stress rheometer (TA
Instruments, West Sussex, U.K.) using a parallel-plate geometry.
It was observed that the suspension retained a memory of its
past shear history. When the shearing was stopped and restarted
in the opposite direction, the measured shear stress showed a
sudden increase before falling off to the steady-state value.
Alternatively, when the shearing was restarted in the same
direction, there was no change in the measured shear stress.
These measurements provide insight into the microstructural
rearrangements taking place in the suspension of flat platelets
of soap under shear flow. The shear flows thus result in product
microstructures that have inherently anisotropic properties. It
is well-known that the microstructural arrangement of the
crystallites inside a bar of soap is anisotropic as a result of its
flow history through the extruders, noodler plates, and dies. A
typical bar of soap is thus more likely to crack along the length
because the defect lines run in the direction of extrusion. The
Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008 6351
formation of mush, which is associated with water ingress and
subsequent swelling of the soap at the interface, is more
predominant along the straight edges as compared to the ends,
because of the alignment of the crystallites during extrusion.
Additionally, controlled alignment can be exploited to create
desirable optical effects in a bar of soap, such as color striping
and pearlescence. The origin of soap pearlesence is similar to
that observed, for instance, in a sea abalone shell (Figure 6),
which occurs as a result of the interference of light reflected
from the multilayer stacks of crystalline platelets of aragonite
having a characteristic nanoscale thickness. Apart from a bar
of soap, pearlesence can be seen in other soap-rich products
such as liquid soaps or skin creams, wherein the crystallites of
both sodium soaps and fatty acids (which are “protonated”
soaps) are deployed to obtain the desired optical effects.23
4. Materials Science Challenges to Soap Technologists
The ∼60% solid crytallites present in a typical milled and
extruded bar of soap, which represents the majority of bar soaps
produced today, are present only to give the bar its structural
rigidity and do not contribute to its functionality in any way.
The solid crystals are washed down the drain as the bar wears
down during use and are a huge load on the environment. A
challenge faced by the soap industry is, therefore, to reduce the
level of structurants required in a bar to the minimum possible.
A typical yield stress versus structurant concentration relation-
ship for a milled and extruded brick-and-mortar bar of soap is
shown in Figure 7. The question is: Can the shape of this curve
be altered to achieve the same yield stress at much lower
concentration of structurant? It is likely that multiscale hierar-
chical structures as seen in nature (e.g., bone) and as employed
by man to create built environment (e.g., Eiffel tower) can also
be deployed in soap to obtain rigidity at lower concentrations
of structurant materials.24 We have made attempts to build these
hierarchical structures inside a bar of soap through appropriate
processing routes25 to achieve the required yield stress with a
lower usage of insoluble soaps. Figure 8 shows some of the
hierarchical structures achieved inside different soap systems
obtained by casting, through appropriate manipulation of the
processing conditions. The microstructures of these hierarchical
structures can be controlled through variations in formulation,
rates of cooling, solvent systems, supersaturation, electrolytes,
and so on. Changing the rate of cooling and hence modifying
the relative rates of nucleation vs crystal growth can result in
very different structures from equilibrium platelets to straight
fibers and branched fibers as illustrated in Figure 9. The
mechanical properties of these structures are also very different.
5. Soap as a Source of Surprises and Inspiration in
Materials Science
Control of the cooling rate during the casting of soap systems
also results in some very dramatic structure formation at the
6352 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008
Figure 10. Spiral coiling of sodium myristate (NaMy) fibers and formation of 3D micropottery structures at the surface of the soap mass.
surface of the crystallizing soap mass. Figure 10 presents some
of these fascinating structures formed by self-organization of
sodium myristate (NaMy) soap crystallites at the air-liquor
interface.26 The surface structures constitute planar spiral
assemblies of soap fibers, as well as 3D “micropottery”
structures emerging from the solidifying surface. Attempts were
made to observe the actual dynamics of ring/structure formation
through video microscopy. However, the dynamics of ring/
structure formation could not be resolved because the evolution/
development of the spiral structures was frozen into a latent
pattern long before the filament thickness grew large enough
for visibility. This indicates that the assembly process is initiated
when the fibers are at an incipient stage in the crystallization.
While the formation of the surface assemblies is broadly
attributed to the Marangoni effect, i.e., motion and deformation
of the crystallizing fiber owing to interfacial tension gradients
in its vicinity;26 the exact origin of these fascinating assemblies
is still unknown. Drawing from similar pattern formation in
nature, we have multiple hypothesis ranging from (i) transient
heat and mass fluxes at the interface leading to alternating
depletion and restoration zones resulting in these patterns of
nucleation and fiber growth; (ii) formation of precursor rings
as a result of the bending of flexible filaments under the stress
imposed by surface pressure gradients,16 followed by continual
drawing of filaments from the crystallizing soup as a result of
the cohesive forces between the loose filament and the filament
bobbins, analogous to the coiling rope phenomenon described
by Mahadevan et al.;27,28 and (iii) precursor rings causing flow
patterns with roll cells normal to the interface, resulting in
alignment of the nucleating fibers along the flow lines before
they grow large enough to entangle. However, all of these
hypotheses currently remain unsubstantiated, and further ex-
perimental and theoretical probing is warranted.
6. Concluding Remarks
More than two centuries have elapsed since we first under-
stood the molecular nature of soap. Nearly a century of research
has been spent on understanding the intriguing phase behavior
of soaps and the physical properties of individual phases. As
this article illustrates, however, the consumer-relevant properties
of most consumer goods containing soap as a functional or
structuring ingredient are dependent on the mesoscopic and
microscopic tertiary supra-structure formed by soap molecules
in these products. What is fascinating is the myriad of different
supra-structures formed by simple soap molecules to impart a
range of desirable properties to the end products. What is
bewildering is the ability of simple soap molecules to spring
surprises in the form of hitherto unseen, aesthetically charming,
and entirely novel supra-structures such as micropottery. These
bulk and surface structures bear testimony to the fact that
the soap molecules still afford an extensive arena for research.
We hope that the examples and challenges provided in this
article more than justify its title. The polymorphic forms
exhibited by simple soap molecules and the myriad of roles
they play in a range of products are indeed no less bewildering
than those of a mythological genie.
Acknowledgment
The authors acknowledge Dr. Hari Koduvely from Unilever
Research India for useful discussions on crystal growth and the
morphology of soap molecules.
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ReceiVed for reView October 31, 2007
ReVised manuscript receiVed May 6, 2008
Accepted May 16, 2008
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