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Chapter_04_revised2 (1)

Chapter 4 discusses the Young equation of contact angle, which relates the contact angle between a liquid and a solid to their interfacial tensions. It highlights the complexity of solid surfaces due to factors like roughness and contamination, and introduces the Kelvin equation and Gibbs adsorption equation as important concepts in colloid and surface chemistry. The chapter also covers Langmuir-Blodgett films and their applications in creating organized molecular structures for potential uses in molecular electronics and sensors.

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6 views42 pages

Chapter_04_revised2 (1)

Chapter 4 discusses the Young equation of contact angle, which relates the contact angle between a liquid and a solid to their interfacial tensions. It highlights the complexity of solid surfaces due to factors like roughness and contamination, and introduces the Kelvin equation and Gibbs adsorption equation as important concepts in colloid and surface chemistry. The chapter also covers Langmuir-Blodgett films and their applications in creating organized molecular structures for potential uses in molecular electronics and sensors.

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qkrwogml0918
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We take content rights seriously. If you suspect this is your content, claim it here.
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Colloid and Surface Chemistry

Chapter 4

한경국립대학교 화학공학전공
정 문 근 교수
The Young equation of contact angle

• The component theories (in Chapter 3) are useful for estimating the
interfacial tensions of solid-interfaces (solid–liquid, solid–solid) and for
characterizing solid surfaces using the experimental data for the few
properties that can be measured (liquid–gas surface tension, liquid–liquid
interfacial tension, contact angle).

• Important equations are the Young equation for contact angle and the
work of adhesion (Equations 4.1–4.3).

• Solid surfaces are much more complex than liquids because of roughness,
chemical heterogeneity, impurities and other phenomena and the contact
angle plays an important role in understanding them.
As Figure 4.1 shows, the contact angle is the angle
between the liquid and the solid, a property that
can be measured and is, together with the theories
for interfacial tension.
• When a drop of liquid is placed in contact with a solid, we have three interfaces: the
solid/liquid, solid/vapour and liquid/vapour interfaces.
• Each of these has its own interfacial energy. For a drop that partially wets a solid, the
total interfacial energy is minimal when the horizontal components of the interfacial
tensions are in equilibrium. At this point, the contact angle between liquid and solid
has a value that is determined by the three interfacial energies.
• The relation is known as the Young equation (Equation 4.1). Thus, the Young
equation is derived as a force balance across the x-axis ( ) and
provides the relationship between the contact angle (ϑ) and surface tensions of solid
and liquid (s, l) and the liquid–solid interfacial tension (sl):

• Equation 4.1 is correct if the spreading pressure is zero, which is almost always true for
low energy surfaces like polymers. The spreading pressure ( ) is the
difference between the solid surface tension (in contact with vacuum or air) and the
solid surface tension in presence with vapour coming from the liquid drop.
• Solid surfaces are complex in many ways; they are often heterogeneous (chemically or geometrically)
and rough, they easily become dirty or contaminated (adsorbed liquids or solids, e.g. dust), and their
properties change with time due to chemical or physical adsorption.
• Especially on high energy surfaces, part of the vapour of the liquid will adsorb on the solid. This
lowers the energy of the solid–vapour interface. On a rough solid, the actual interfacial area is larger
than the one that we see: this causes the effective energies of the solid interfaces to be larger than
those of a flat surface.
• If there are contaminants (dirt) in the system, these will adsorb on the solid and lower the effective
interfacial energies of the solid. As a result, simple calculations using “pure” interfacial energies
are often inaccurate.
• Clean metals, metal oxides, glass and ceramics are high energy surfaces, while polymers and fabrics
are low energy surfaces. However, for the high energy surfaces, cleaning of the surface is of
paramount importance. Even the thinnest monolayer of adsorbed oil/grease can dominate the surface
properties. “Clean tin cans” have been reported with surface tensions as low as 31 mN m–1.
• Aging phenomena are also crucial. Even carefully prepared surfaces under vacuum rapidly adsorb
(physically or chemically) material from the environment, e.g. water, hydrocarbons, dirt, etc. For
example, Mica prepared under vacuum has a surface energy of 4500 mN m–1 but the surface energy
decreases to about 300 mN m–1 under normal laboratory conditions, where water can easily adsorb.
Moreover, the way the solid surface is prepared (crystallized in water or air) may have a large effect
on its surface properties.
• Let us look closer now at the well-established phenomenon of “contact angle hysteresis”. As
mentioned, if we have contamination, roughness, significant spreading pressure, heterogeneity or even
when equilibrium is not reached we can experience the phenomenon called “contact angle hysteresis”.

• This means that the contact angle depends on how the


liquid is applied, i.e. whether it is advancing on a dry or
receding from a wet surface.
• The surface has spots with a high effective energy, and
spots with a low effective energy. A liquid advancing along
the surface will be retarded by spots with a low interfacial
energy.
• The Kelvin equation has numerous applications, e.g. in the stability of colloids
(Ostwald ripening, see below), supersaturation of vapours, atmospheric
chemistry (fog and rain droplets in the atmosphere), condensation in
capillaries, foam stability, enhanced oil recovery and in explaining nucleation
phenomena (homo- and heterogeneous).
모세관 내 액체는 열린 공간보다 더 "힘들게" 증발하고 쉽게 응축
•응축은 더 쉬워지고, 증발은 더 어려워지는 경향을 보임
•기공 구조, 토양 수분 이동, 석유 회수 기술, 촉매공학, 기체 흡착 연구 등에 중요한 물리적 현상
• This equation describes the change in solubility of a solid particle in a liquid as the particle
size is reduced. According to this equation, the solubility increases as the size of the
particle is reduced in the same manner as the vapour pressure of the liquid in a drop
increases as the size is reduced.

• This means that larger particles grow by the transference of material from the smaller
particles, the phenomenon we called Ostwald ripening.

• As most suspensions are polydispersed, the Kelvin equation is a crucial indicator of their
stability.

• The smaller particles will have a greater solubility and will tend to dissolve, and the
larger particles will tend to grow at their expense. In a suspension of a highly insoluble
substance, such as silver iodide (AgI) hydrosol, this phenomenon will be of little
consequence, since both large and small particles have extremely little tendency to dissolve.

• In a suspension of more soluble material, such as calcium carbonate (CaCO3) hydrosol,


however, Ostwald ripening occurs to such an extent that it is not possible to prepare a long-
lived dispersion with particles of colloidal dimensions unless a stabilizing agent, such a
gelatin or a surfactant, is incorporated.
• The Gibbs adsorption equation is one of the most important and fundamental equations
in colloid and surface science. An interface in real systems is an area of small but non-
zero thickness (of about 10 molecular diameters).
• The adsorption, as defined in Equation 4.7a, is the number of moles at an interface per
area and has units of concentration (molar) per area. The number of moles at the
interface and thus the adsorption itself can be either positive or negative (for compounds
avoiding the interface).
• Using some algebra and concepts from thermodynamics (see Appendix 4.3), the Gibbs
adsorption equation can be derived:
A special case of adsorption is Liquid films represent an
that related to the behaviour of intermediate stage liquid
monomolecular films (gas, (spreading and gas films.
liquid, solid) (Figure 4.4). There are many experimental
techniques used for studying
In solid films, the molecules are
monolayers, e.g. the
oriented densely close to the
Langmuir trough.
surface, while in the gas films
the molecules are more
independent of each other.
Case study. Langmuir–Blodgett films
• Near the end of the nineteenth century Agnes Pockels (1891), working in the kitchen of her
parents’ home, discovered how to manipulate oil films on water and thus developed the
first surface film balance. Her results led Lord Rayleigh (1899) to suggest that the films
were only one molecule thick, thus providing the foundations for the study of insoluble
monolayers.
• Devaux, Hardy and Langmuir in the following years all contributed a great deal in the study
of such monolayers.If a solid surface is passed vertically through a floating monolayer,
the monolayer may deposit on the solid substrate.
• The process is known as Langmuir–Blodgett or LB deposition after the scientists who
discovered and developed the technique. Repeated passages of the substrate through the
monolayer may lead to the deposition of additional layers on the surface, thus forming
multilayer films.
• However, not all substrates and not all monolayers are suitable. For satisfactory deposition,
the surface pressure should be sufficiently high that the monolayer is in a condensed state.
A surface pressure between 20 and 40 mN m–1 is normally used.
• There are three possible types of deposition. Once the first monolayer has been deposited on the
substrate, subsequent movements in and out of the surface often lead to the deposition of an additional
layer on each passage. This is known as Y-type deposition. Other types of depositions are possible (X
and Z).
• The definitions of these deposition types refer to the behaviour during deposition, not to the structure of
the film that is formed. Much work has been done using monolayers of carboxylic acids and their
salts.
• For good quality films careful preparation of the substrate is essential. Selection of the appropriate pH
and the type and concentration of salt in the subphase affect the type of film that is formed. The highly
ordered layer structure of LB films is a major consideration in potential applications.
• LB film deposition is unique in the control offered for producing highly organized molecular arrays of
controlled, nanometre-scale thickness, and therefore plays a part in the quest towards molecular
electronics (diodes and transistors using the smallest possible elements with single or very few
molecules).
• Great interest has led to the development of Langmuir troughs with various mechanisms for the LB
deposition of, for example, alternate layers of two different amphiphiles. In addition, techniques have
been developed for overcoming problems related to the deposition of a second metal layer on top of a
LB film already deposited on a metal substrate.
• Other applications involve photo-semiconductors, extending the frequency range of laser devices and
chemical and biological sensors.
Thank you

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