Introduction to Soft Matter

Soft Matter
As its name implies, soft matter deals with
materials that are easily deformed. These
materials, which include polymers, gels,
colloids, emulsions, foams, surfactant
assemblies, liquid crystals, granular materials,
and many biological materials, have in common
that they are organized on mesoscopic length
scales, with structural features that are much
larger than an atom, but much smaller than
the overall size of the material.

The large size of the basic structural units and

the relatively weak interactions that hold them
together are responsible for the characteristic
softness of these materials, but they also lead
to many distinct features of soft materials, such
as sensitivity toward thermal fluctuations and
external stimuli and a slow response with long
relaxation times, often resulting in complex
flow and arrest in non-equilibrium states.
These features make soft matter problems
challenging.
Soft Matter
In hard condensed matter physics, it is
possible to predict material properties based
on the interactions between the individual
atoms, which are organized on a regular
crystalline lattice. For soft matter systems,
with their intrinsically heterogeneous
structure, complex interactions across
different length scales, and slow dynamics,
this is much more difficult.

The subtle interplay between interactions

and thermal fluctuations can lead to
complex emergent behavior, such as
spontaneous pattern formation, self-
assembly, and a large response to small
external forces.

The realization that liquid crystals and

polymers exhibit symmetry breaking and
many fluctuating degrees of freedom has
revived classical fields of physics such
as elasticity and fluids, including non-
Newtonian, and helped to establish the field
of soft condensed matter Physics (de
Gennes, Nobel Prize 1991).
Building blocks and
interactions
Atoms and small molecules, in Nature or synthesized
in the laboratory, on the (sub)nanometer scale are
the building blocks of solid state Physics.

Colloids, polymers and other macromolecules, the

size of which lies between 5 nanometers and 5
micrometers, may be considered the building blocks
of soft matter.

The interactions between nanometer and micrometer

sized particles are radically different, both in nature
and strength. While at the nanoscale the interactions
are mostly electronic (order of eV) and quantum
mechanics rules, on larger length scales the
interactions between the particles are much weaker.
They are effective interactions obtained from the free
energy of the (two) particle system. They are often
entropy driven and are of the order of the room
temperature thermal energy (order of kT, where k is
the Boltzmann constant or 1/40 eV at room
temperature).
Building blocks and
interactions
Colloidal particles are particles typically between 1
and a 1000 nm that can be dispersed (suspended) in
fluids and for which Brownian forces are usually
stronger than gravitation − the particles do not
(usually) precipitate. Model colloidal particles are
made of monodisperse spheres (polystyrene, silica ...)

In suspension, the particles are attracted by London

dispersion or van der Waals forces. In water, the
colloidal particles can have like charges, for example,
through attaching ionisable acid groups on the
surface. These like charges repel, but the repulsion is
usually screened. DLVO theory (Deryaguin-Landau-
Verwey- Overbeek) puts together the attractive
London part and the screened Coulomb repulsion,
and the potential takes the form depicted by the
green curve in Figure on the bottom.
 The weak interactions between
particles may be used as the
defining characteristic of soft
matter.

Soft matter comprises a

Defining variety of states, best
distinguished as being

characteristics dominated by energies of the

order of room temperature
thermal energy.

At these temperatures,
quantum aspects are generally
unimportant.
 While at the nanometer scale the shape of the
particles is fixed, at the micrometer scale the
particles may be shaped and sculpted in
almost any way. It is not only the sizes of the
particles that differ but the blocks can be made
to take a much wider range of forms.

It is if the LEGO blocks could be molded to take

arbitrary shapes.

More on the
building blocks
 Soft materials

Soft materials are important in a wide

range of technological applications. They
appear as packaging materials, foams and
adhesives, detergents and cosmetics,
paints, food additives, lubricants, rubber,
etc.

In addition, a number of biological

materials (blood, muscle, milk, yogurt,
jello) are classifiable as soft matter.

Liquid crystals, another category of soft

matter, exhibit a responsivity to electric
fields that makes them very important as
materials in display devices (LCDs).
 Soft materials

In spite of the various forms of these

materials, many of their properties
have common origins:

• a large number of degrees of

freedom,

• weak interactions between the

structural elements,

• a balance between entropic and

enthalpic contributions to the free
energy.
 The macroscopic properties of soft matter depend on its
structure at the mesoscale and the challenge is to
Challenge understand this mesoscale structure and how it determines
the material properties.
Bridging the scales

• Computer simulations &

theoretical concepts and a
range of experimental tools are
required to investigate these
systems and to bridge the
length and time scales.
• Clearly, the interaction between
colloidal particles with billions
of atoms cannot be calculated
from first principles, i.e., by
solving Schrodinger’s equation.
• Effective interaction potentials,
coarse-grained dynamics and
collective Monte Carlo moves
are needed.
 Examples

Most soft materials are made of linear or

branched polymers, amphiphilic
(macro)molecules, colloids, granular matter and
liquid crystals.

In some cases the building blocks are not very

large but they self-assemble into units or phases
that respond to external forces and move
collectively (amphiphiles and liquid crystals).

In others, the building blocks contain millions or

billions of atoms (polymers, colloids and
granular matter).

In all cases the response of the system is large

and the dynamics slow, leading to non-
equilibrium and non-linear response, which
make the properties of soft materials
challenging and unique.
Polymers A polymer is a substance consisting of very large molecules, or macromolecules, also
called polymers. The defining feature of polymer macromolecules is their chain-like
structure, made up of repeating monomers. The number of monomers in a polymer
is typically thousands but can be as large as tens of millions.

The structure of a polymeric material can be described at different length scales,

from the sub-nm length scale up to the macroscopic one. At the sub-nm scale the
structure of a polymer is that of its constituent monomers.
Polymers

Next, the structure

essentially describes the
arrangement of these
monomers within the
polymer at the scale of a
single chain, which may be
linear or branched.

Crosslinked or networked
structures are also possible.
Left: Appearance of real linear polymer chains as recorded using an atomic force
microscope on a surface, under liquid medium. Chain contour length is
approximately 204 nm; thickness is approximately 0.4 nm. Right: Microstructure of
part of a DNA double helix biopolymer
In his book Scaling Concepts in
Polymer Physics, Pierre-Gilles de
Gennes describes three
developments that have been
essential for advances in the study
of large-scale conformations and
motions of flexible polymers in
solutions and melts.
They are neutron-scattering
experiments on selectively
deuterated molecules; inelastic
scattering of laser light, which allows
the study of cooperative motions of
the chains; and the discovery of an
important relationship between
polymer statistics and critical
phenomena, leading to many simple
scaling laws, for which de Gennes
was awarded the Nobel prize.
Polymer structure
The microstructure determines the possibility for
the polymer to form phases with different
arrangements, through crystallization, the glass
transition or microphase separation. Polymer
crystallization is a hard problem both
theoretically and experimentally.

These phases play a major role in determining the

physical properties of a polymer.

Polymers are indispensable materials in modern

technology; they are used as plastics, rubbers,
films, and textiles.

Polymers are also the basic molecules of life as

proteins (machinery of biological functions) or
DNA (genetic information).
Amphiphiles
Amphiphile is a
molecule possessing
both hydrophilic
(water-loving) and
hydrophobic (water-
hating) properties.

Typical amphiphiles
are: sodium dodecyl
sulfate (anionic),
benzalkonium chloride
(cationic) and 1-octanol
(long-chain alcohol,
non-ionic).
Surfactants
An important class of
amphiphiles are
surfactants, or surface
active agents,
responsible for the
reduction of the
interfacial tension
between two
immiscible phases.

The relation that links

the surface tension
and the surface excess
is the Gibbs isotherm.
 Surfactant self-
assemby
Surfactants exhibit
spontaneous formation of
mesoscopic structures from
smaller building blocks, by
self-assembly.

The simplest example of self-

assembly is into micelles or
vesicles in water.

Much more intricate

examples can be found in
biology, where self-assembly
leads to complex structures,
such as viruses and
hierarchically organized
collagen fibers.
When in a two-phase
system the surfactant self-
assembles to partition the
two immiscible phases.
The extent of the
hydrophobic and
hydrophilic portions and
the concentrations
determine the
partitioning and the
structure of the resulting
phases.

Phase diagram of water-

oil-surfactant mixtures,
exhibiting emulsion,
microemulsion and liquid
crystalline phases. On the
left the system is water-
rich, on the right oil-rich
and in the middle water-
oil balanced. The
surfactant composition
increases from bottom to
top.
Colloids
A colloid is a phase separated
mixture in which one
substance of microscopically
dispersed particles (A) is
suspended throughout
another substance (B).

Sometimes the dispersed

substance alone is called the
colloid; the term colloidal
suspension refers
unambiguously to the overall
mixture.

Unlike a solution, whose

solute and solvent constitute
only one phase, a colloid has
a dispersed phase (the
suspended particles, A) and a
continuous phase (the
medium of suspension, B).
 Left: Freshly whipped (A, B) and aged (C, D)
cream. A and C are unstabilized, while B and D
Microstructure are stabilized. Bar 150 𝜇m.
Right: milk (oil droplets in water)
 Typically, colloids do not completely settle or
Colloidal sizes take a long time to settle. The dispersed-phase
particles have a size between 5 nanometers and
5 micrometers.
 Colloids as atoms

A dissolved body differs from a

suspended one solely by its
dimensions and
N suspended particles produce
the same osmotic pressure as N
molecules.

Ann. d. Physik, 17, 549 (1905)

Colloidal shapes
Many of the forces that govern the
structure and behavior of matter, such as
excluded volume interactions or
electrostatic forces, govern the structure
and behavior of colloidal suspensions. For
example, the same techniques used to
model ideal gases can be applied to model
the behavior of a hard sphere colloidal
suspension.

Colloidal particles can be synthesized in

many sizes and shapes, and the interactions
between them can be finely tuned, by
varying the surface charge, by changing the
pH, by adding polymeric depletants, or by
decorating the particles surfaces with
complementary DNA strands.

This can lead to self-organization into a

large variety of structures and phases, such
as colloidal liquids, crystals, liquid crystals,
and glasses, mimicking and going beyond
the assembly of atoms.
 A strategy to control material properties from the bottom
up, is by starting with colloidal building blocks.
Bottom-up
Carefully designed colloidal building blocks may become
strategy the “atoms” and “molecules” of future materials, with
potentially very interesting optical and mechanical
properties.
 Since colloids are big and slow enough to
be followed individually using an optical
microscope, they can be used to study
fundamental physics problems at the
single particle level, such as nucleation,
melting, and crystal defects.
Confocal
microscopy Non-equilibrium states are more
prominent for colloids than for molecules.
For example, gelation of particles can
arrest the particles in a non-equilibrium
aggregated state, completely suppressing
crystallization.
 Granular matter is defined as a collection of
particles that are large enough that thermal
motion ceases to be important, and
dissipation upon collisions of particles
dominates the dynamics.

Granular The grains may be solid particles (as in sand),

liquid droplets (as in emulsions), or gas
matter bubbles (as in foams). The lower size limit for
grains in granular matter is a few μm. On the
upper size limit, the physics of granular matter
may be applied to asteroid belts of the Solar
System with individual grains being asteroids,
with sizes of several metres.
Characterization
The most important parameter characterizing
the behaviour of a granular system is its
density.

Loose granular matter can flow like a fluid,

while dense granular packings behave like a
solid. Both cases have their own physics. At
intermediate densities the granular material
can switch from fluid to solid, as in avalanches.
Granular gases, granular fluids, and granular
packings are discussed within the framework of
statistical physics of disordered media, carried
from equilibrium into out-of-equilibrium.

There is at present no microscopic model that

explains the rich flow behavior of granular
suspensions and emulsions.
 Liquid crystals (LCs) are a state of matter which
has properties between those of conventional
liquids and those of solid crystals. For instance,
a liquid crystal may flow like a liquid, but its
molecules may be oriented in a crystal-like
way.

Liquid crystals If a material is made of rod-like molecules, in

the crystalline state the molecules are
regularly placed on lattice sites and are also
aligned. There is order in position and in
orientation. In the liquid state, the position
and orientation of the molecules are both
random. In the liquid crystalline state,
molecules have orientational order and lack
full positional order.
 LC phases
In nematics the molecules
retain the orientational
order, while there is no
positional order, a).

In smectics, in addition to the

orientational order, there is
partial positional order: the
molecules are regularly
placed along one direction,
but are random on the plane
perpendicular to it. If the
direction of the positional
and the orientational order is
the same the phase is called
semectic A, b), while if these
directions do not coincide
the phase is a smectic C, c).

In the cholesteric the

direction of the orientational
order twists with a
characteristic period, d).
Textures &
Applications

LC phases, are distinguished by their

different optical properties (such as
textures). The contrasting areas in the
textures correspond to domains where
the LC molecules are oriented in
different directions. Within a domain
the molecules are ordered.

Examples of liquid crystals can be found

both in the natural world and in
technological applications. Widespread
LC displays (LCD) use liquid crystals,
since their optical properties are easily
controlled by electric fields.
Lyotropic LC phases are abundant in
living systems. For example, many
proteins and cell membranes are LCs.
Active matter

Systems intrinsically out of

equilibrium, as the particles
continuously consume
energy to propel active
motion or to exert
mechanical forces.

The interplay between a

large number of these
active particles can lead to
very complex patterns of
collective motion and self-
organized structures.
• A common thread in soft matter
physics is to find microscopic models
for macroscopically observed behavior.
The inverse problem—designing a
material with a specific property—is
much more difficult. Yet, it is certainly
one major goal. With the increase in
computer power, the development of
novel experimental tools, and new
algorithms for analyzing large data sets,
this goal may be within reach.

• Despite the differences among the

various soft matter systems
mechanistic insight and modelling may
start by using standard tools such as
Landau theory.

OUTLOOK
 Compreensão das propriedades de agregados
macroscópicos de micropartículas. Estes
componentes, à escala do mícron, agregam-se
em materiais com um comportamento por
vezes inesperado.

Muitos são utilizados na vida quotidiana e têm

um número crescente de aplicações
Objetivos tecnológicas. Exemplos destes materiais
incluem cristais líquidos, polímeros, colóides e
matéria granular.

As descrições teóricas atuais da matéria mole

são baseadas nas ferramentas da mecânica
estatística clássica de equilíbrio e de
nãoequilíbrio, na quebra espontânea de
simetria e na física de muitos corpos.
 1. Introdução
1.1 O que é matéria mole ?
1.2. Polímeros, Colóides, Surfactantes e Cristais Líquidos.
1.3. O que é comum em matéria mole ?
2. Soluções de matéria mole
2.1. Termodinâmica de soluções
2.2. Separação de fases

Programa 2.3. Modelo de rede

2.4. Soluções de polímeros
Margarida Telo da Gama
2.5. Soluções coloidais
2.6. Soluções multi-componentes
3. Superfícies e surfactantes
3.1. Tensão superficial
3.2. Wetting
3.3. Surfactantes
3.4. Potenciais interfaciais
 4. Cristais Líquidos
4.1. Cristais líquidos nemáticos
4.2. Teoria de campo médio para a transição isótropo-
Programa nemático
4.3. Teoria de Landau-de Gennes
Mykola Tasinkevych
4.4. Efeitos de um gradiente espacial na ordem nemática
4.5. Teoria de Onsager para a transição isótropo-nemático
de soluções coloidais
 5. Movimento Browniano, flutuações térmicas e partículas
ativas
5.1. Movimento Browniano de uma partícula esférica:
aproximação de Langevin, funções de correlação e movimento
num potencial
5.2. Movimento Browniano de uma partícula com forma
generalizada
5.3. Flutuação-dissipação
5.4. Movimento de uma partícula ativa
Programa 6. Princípio variacional em matéria mole:
6.1. Princípio variacional para a dinâmica de sistemas
Nuno Araújo partícula-fluído
6.2. Princípio de Onsager
6.3. Difusão em soluções diluídas e concentradas
7. Difusão e permeabilidade
7.1. Correlações espaciais
7.2. Sedimentação de partículas
7.3. Cinética de separação de fases
 Bibliografia
Principal
Soft Matter Physics: Masao Doi 2013 Masao Doi, Soft Matter Physics, Oxford
University Press, 2013
Secundária
Soft Condensed Matter: R. A. L. Jones 2002 R. A. L. Jones, Soft Condensed Matter,
https://videoconf- (Oxford Master Series in Physics) 2002.

colibri.zoom.us/j/85130
Avaliação
949185?pwd=SGorSXl2
50%: 5 conjuntos de exercícios (Termodinâmica de soluções, Superfícies e
OW84R2J1aGkvWk1oS surfactantes, Cristais Líquidos, Princípio variacional, Difusão e permeabilidade).
UhoUT09 A ser submetidos até 2 semanas depois da data a que forem propostos.
Os exercícios devem ser discutidos com o docente (numa TP).
Para cada conjunto de exercícios a avaliação tem em conta a resposta
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