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
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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:
[email protected]. 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 history, continue to surprise us with hitherto-unknown novel self-
viscoplastic rheological behavior. In this article, we intend assembled structures and how the area is still an open arena for
to illustrate the role played by typical phases exhibited by research.
soap molecules and their supra-assemblies in the above
categories of products, while “structuring” them to control 2. Polymorphic Forms of Soap Molecules and Their
their form, appearance, and other physical, mechanical, and Aggregates in Aqueous Systems
sensory properties.
For nearly a century, soap molecules have been the subject
In section 2, we briefly introduce commonly encountered of a large number of scientific studies because of their ready
primary phases and forms exhibited by soap molecules in aqueous availability and commercial importance. Driven by the need to
environments and their dominant rheological behaviors. In sections shield their solvophobic part in a particular environment, soaps,
3 and 4, we highlight, through examples, the role of processing on like other amphiphilic molecules, organize themselves into a
the micromechanical superstructures formed by these phases and range of micellar, liquid-crystalline, and crystalline forms. Phase
their influence on the end properties of finished products. Finally, diagrams depicting these different transitions as functions of
we illustrate how soap molecules, despite centuries of technological temperature, concentrations, presence of electrolytes, cosolvents,
 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008 6349

Figure 4. Effect of flash drying and shear working (below TK) on the mixed soap microstructure.

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,
Figure 5. (a) Flow-direction-dependent transient behavior of platelike mica
ribbons, twisted fibers, rods, and flat platelets (Figure 2),
particles suspended in 5% sodium carboxymethyl cellulose (SCMC) solution depending on the type and mixture of soap molecules involved,
with 20 wt % particle loading. Shear rate ) 1 s-1. The flow direction was as well as the crystallization conditions. The presence of nonsoap
reversed every 300 s. (b) Schematic depicting the effect of reversing the inclusions (cosurfactants, electrolytes, solvents, and so on) can
direction of shear on the suspension viscosity with anisotropic particles. modify the phase behavior, even at very low concentration
and so on have been determined for a large number of soap levels. For instance, hydrotropes such as ethanol solubilize the
species and their mixtures.5–21 The typical phase diagram of a liquid-crystalline phases, increasing the micellar solution region
soap species, in the presence of a solvent system, has the general in the phase diagram. Minor levels of electrolytes can have a
form depicted schematically in Figure 1. The diagram is strong influence on both the CMC and the Krafft temperature
characterized by the TK line corresponds to the Krafft boundary, through the common-ion effect, or they can produce insoluble
which essentially gives the temperature above which the soap soap salts.19
molecules exist in a molten but aggregated form. The Krafft The rheological behavior of aqueous soap solutions is
point is defined as the point of intersection on the temperature dependent on the nature of aggregation and the phases formed
axis between the curve of molecular solubility for the solid soap, by the soap species.21,22 Whereas dilute spherical micellar
depicted by the dashed-line extrapolation, and the curve of the solutions can exhibit Newtonian rheology, the rheological
critical micelle concentration (CMC), depicted by the dotted behaviors of solutions containing concentrated spherical
line. As the soap molecules are introduced into water, at very micelles or anisotropic rodlike or disklike micelles are more
low concentration (to the left of the dotted line), they exist as complex. These micelles rotate in shear flow. The viscosity
individual molecules in solution, exhibiting preferential adsorp- of solution increases sharply with increasing concentration
tion at surfaces or excess concentrations in the interfacial of soap, when the rotating rods/disks start to overlap with
regions. They thus serve to stabilize interfaces by lowering the each other, forming transient networks. The liquid-crystalline
total free energy associated with maintaining a phase boundary. phases formed at higher concentrations exhibit even more
Upon an increase in concentration beyond the CMC curve, the complex nonideal rheological behaviors, as well as mani-
molecules start forming aggregates, shielding their hydrophobic festations such as thixotropy, dilatency/pseudoplaticity, and
tails from the aqueous surroundings, thereby resulting in the shear banding. Peculiarly, the hexagonal and cubic phases
formation of spherical micelles. With a further increase in 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.

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
Figure 7. Current yield stress versus concentration behavior for the solid about 60% of the phase volume, are composed of solid
structurant and the desired behavior through hierarchical structures.
crystallites of long-chain insoluble soaps (e.g., sodium stearate,
lamellar phases, whose bilayers can slide more readily over sodium palmitate) that serve the role of structurants, whereas
one another. Most liquid-crystalline phases also exhibit a the mortar consists of a mix of liquid-crystalline (LC) phases
yield stress, with the cubic and hexagonal phases exhibiting (30%) and isotropic liquid (10%) of short-chain and unsaturated
pure elastic behavior under low deformation and at high soluble soaps (e.g., sodium laurate, sodium oleate) that provide
oscillatory frequencies. Because of difficulties in obtaining the function of lathering and cleaning. In the initial stages of
single soap crystals of sufficiently large sizes, however, the soap preparation, the neutralization of the fatty acids with caustic
mechanical properties of solid crystalline phases are not very soda results in a soap mass with about 30-40% water in which
well studied and reported in the open literature. 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%.
3. Soap as a “Material”
This rapid drying operation, which takes place on a time scale
One of the most common items of our daily use that consists on the order of milliseconds, congeals the mixed lamellar phase
almost entirely of soap molecules (as high as 85%) is a bar of into a nonequilibrium supersaturated state with the soluble and
soap. In this section, we use various case studies to illustrate insoluble soap molecules trapped into a congealed mixed-
how it is not the chemical composition alone but the nature crystalline phase called the kappa phase (cf. Figure 4) character-
and hierarchical superassembly of the coexisting phases that ized by a unique X-ray pattern with peaks at 4.05, 3.20, and
dictates the material properties of bar of soap. 2.97 Å, with the latter being used to characterize the phase.
In the first case study, we discuss a historically well-known The trapped soluble soap is thus no longer readily available for
bar soap, namely, Pears. During the manufacturing process, it providing rapid lathering or cleaning functions, and the resultant
is cast as an approximately 60% solution of soap species in bar of soap has the structure of a bar but does not display the
aqueous denatured spirit into molds and allowed to solidify as most desirable in-use characteristics of a bar soap. It lathers
unmatured “green” Pears bars. At room temperature, these green slowly and forms slimy mush in contact with a water layer.
Pears bars contain only about 20% solids as determined using The bar, therefore, has to be shear-worked with the temperature
low-field NMR techniques, with the remaining 80% being in maintained below the Krafft boundary to restore the equilibrium
liquid state. Yet, a green Pears bar exhibits a solidlike rheology phase structure. The shear working is required to overcome the
(cf. Figure 3). However, if the bar is subjected to shear, it breaks activation energy barrier for getting the soluble soap out of the
down to form a flowable slurry. This is very similar to the nonequilibrium mixed soap crystals into the mortar phase. When
rheological characteristics exhibited by fruits such as apples, the soluble soaps are extracted into the mortar phase, the long-
which can be sheared to obtain a “juice”. The Pears slurry has chain crystals left behind recrystallize into a new form called
the functionality of a bar of soap but lacks the structure, just as the zeta phase (characteristic X-ray peaks at 4.05, 3.50, and
the crushed apple has the same taste but lacks the rigidity of a 2.75 Å). Another effect that has been observed after shear
fruit. Analogously to the unique arrangement of lignocellulosic working of a bar of soap is a higher optical transparency for
networks of turgid cells in fruits forming closed foam sample- some specialty formulations. This is caused by a reduction of
spanning structures, resulting in their rigidity, the green Pears the crystal size (because of particle breakdown during shearing
formulation is also rendered into a rigid bar through the unique and recrystallization of the zeta phase, which is characterized
microstructural morphology of its solid crystallites, which form by smaller crystallite sizes) and better refractive index matching
a sample-spanning load-bearing network. The commonality lies between the solid and mortar phases because of the higher
in the inability of both of the sample-spanning networks to extents of soap solubilization in the mortar. The relative impact
withstand steady shear or large deformation. The desired of both on the scattering behavior of the composite bar can be
morphology of the Pears bar, which is a nonequilibrium assessed by the Raleigh-Gans equation. Thus, in this case, in
arrangement, is achieved through appropriate processing routes contrast to the case of a Pears bar, the nonequilibrium structure
 Ind. Eng. Chem. Res., Vol. 47, No. 17, 2008 6351

Figure 8. Different hierarchical structures observed in bar soaps.

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

Figure 9. Transition from (a) equilibrium platelike crystals to (b) straight
fibers, (c) branched fibers, and (d) glassy/amorphous structures with The ∼60% solid crytallites present in a typical milled and
increasing cooling rate.
extruded bar of soap, which represents the majority of bar soaps
is detrimental to the functioning of the bar soap. It is the produced today, are present only to give the bar its structural
restoration of a near-equilibrium structure that helps achieve rigidity and do not contribute to its functionality in any way.
the desired structure, function, and appearance of the bar. The solid crystals are washed down the drain as the bar wears
Whereas the applied shear provides the necessary energy input down during use and are a huge load on the environment. A
into the bar soap to bring about the phase transformations, it challenge faced by the soap industry is, therefore, to reduce the
also interacts physically with the soap mix at various levels. level of structurants required in a bar to the minimum possible.
Both the LC phases in the mortar and the solid platelike A typical yield stress versus structurant concentration relation-
crystallites of soap are known to align along flow lines, leading ship for a milled and extruded brick-and-mortar bar of soap is
to complex rheological behaviors that can pose significant shown in Figure 7. The question is: Can the shape of this curve
challenges during processing. In Figure 5, we show results from be altered to achieve the same yield stress at much lower
transient viscosity measurements that were carried out employ- concentration of structurant? It is likely that multiscale hierar-
ing a model suspension of mica platelets suspended in a 5% chical structures as seen in nature (e.g., bone) and as employed
sodium carboxymethyl cellulose (SCMC) solution. This was by man to create built environment (e.g., Eiffel tower) can also
used as a model system to obtain a qualitative understanding be deployed in soap to obtain rigidity at lower concentrations
of the motion of the anisotropic platelike soap particles under of structurant materials.24 We have made attempts to build these
shear, as similar studies with a fully formulated opaque soap hierarchical structures inside a bar of soap through appropriate
system would not be feasible. The measurements were carried processing routes25 to achieve the required yield stress with a
out on a CarriMed CSL 500 controlled-stress rheometer (TA lower usage of insoluble soaps. Figure 8 shows some of the
Instruments, West Sussex, U.K.) using a parallel-plate geometry. hierarchical structures achieved inside different soap systems
It was observed that the suspension retained a memory of its obtained by casting, through appropriate manipulation of the
past shear history. When the shearing was stopped and restarted processing conditions. The microstructures of these hierarchical
in the opposite direction, the measured shear stress showed a structures can be controlled through variations in formulation,
sudden increase before falling off to the steady-state value. rates of cooling, solvent systems, supersaturation, electrolytes,
Alternatively, when the shearing was restarted in the same and so on. Changing the rate of cooling and hence modifying
direction, there was no change in the measured shear stress. the relative rates of nucleation vs crystal growth can result in
These measurements provide insight into the microstructural very different structures from equilibrium platelets to straight
rearrangements taking place in the suspension of flat platelets fibers and branched fibers as illustrated in Figure 9. The
of soap under shear flow. The shear flows thus result in product mechanical properties of these structures are also very different.
microstructures that have inherently anisotropic properties. It
is well-known that the microstructural arrangement of the 5. Soap as a Source of Surprises and Inspiration in
crystallites inside a bar of soap is anisotropic as a result of its Materials Science
flow history through the extruders, noodler plates, and dies. A
typical bar of soap is thus more likely to crack along the length Control of the cooling rate during the casting of soap systems
because the defect lines run in the direction of extrusion. The 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 surprises in the form of hitherto unseen, aesthetically charming,
of these fascinating structures formed by self-organization of and entirely novel supra-structures such as micropottery. These
sodium myristate (NaMy) soap crystallites at the air-liquor bulk and surface structures bear testimony to the fact that
interface.26 The surface structures constitute planar spiral the soap molecules still afford an extensive arena for research.
assemblies of soap fibers, as well as 3D “micropottery” We hope that the examples and challenges provided in this
structures emerging from the solidifying surface. Attempts were article more than justify its title. The polymorphic forms
made to observe the actual dynamics of ring/structure formation exhibited by simple soap molecules and the myriad of roles
through video microscopy. However, the dynamics of ring/ they play in a range of products are indeed no less bewildering
structure formation could not be resolved because the evolution/ than those of a mythological genie.
development of the spiral structures was frozen into a latent
pattern long before the filament thickness grew large enough
Acknowledgment
for visibility. This indicates that the assembly process is initiated
when the fibers are at an incipient stage in the crystallization. The authors acknowledge Dr. Hari Koduvely from Unilever
While the formation of the surface assemblies is broadly Research India for useful discussions on crystal growth and the
attributed to the Marangoni effect, i.e., motion and deformation morphology of soap molecules.
of the crystallizing fiber owing to interfacial tension gradients
in its vicinity;26 the exact origin of these fascinating assemblies
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