Surface Chemistry

By
Dinda Bazliah

School of Materials and Science

Department of Chemical Engineering
Nanjing Normal University
Nanjing, China
2022
 Surface Chemistry
Surfaces and interfaces define a boundary between a material and its surrounding
environment and influence interactions with that environment. At the molecular level, the
surface atoms have a different chemical environment, that is, fewer nearest neighbors, from
that in the bulk. Consequently, these surface atoms with changed atomic and electronic
structures exhibit high chemical reactivity. This property makes surfaces and interfaces a
favored medium for chemical and biological processes in nature and in technological
applications (1).
Modern surface chemistry is about molecular-level understanding and the control of
surface chemical reactions. Over the past decades, various surface science techniques have
been developed and a vast amount of knowledge about surface chemistry has been
accumulated (1–6). The fundamental knowledge that is accumulated provides a foundation
for the development of many industrial technologies that produce items including chemicals
and fuels (7), semiconductor devices (8), and biomedical devices (9). Technological
advances, in turn, necessitate the further development of new surface characterization
techniques with higher spatial, temporal, and energy resolution.
This perspective begins with an overview of several applications of surface chemistry
that have an enormous economic impact on our society. Advances in the fundamental
understanding of molecular processes on surfaces over the past decades are then reviewed
with an emphasis on the development of the molecular-level surface techniques. We highlight
new scientific insights provided by in situ experimental and theoretical techniques capable of
characterizing surfaces and interfaces under working conditions.

Colloid Effect in Surface Chemistry

Colloid is the particle dimension - not the chemical composition (organic or

inorganic), sources of the sample (e.g., biological or mineralogical), or physical state (e.g.,
one or two phases)-that consigns it to our attention. Based on that determination, colloid
science is the science of both large molecules and finely subdivided multiphase systems. The
word surface is thus used in the chemical sense of a phase boundary rather than in a strictly
geometrical sense. Geometrically, a surface has area but not thickness. Chemically, however,
it is a region in which the properties vary from those of one phase to those of the adjoining
phase. This transition occurs over distances of molecular dimensions at least. For us,
therefore, a surface has a thickness that we may imagine as shrinking to zero when we desire
a purely geometric description
Impact of Colloid and Surface Chemistry in Science, Engineering, and Technology. It
should be evident from the partial list of examples summarized in Table 1.1 how many
materials or phenomena of current scientific or everyday interest touch on colloid and surface
science to some extent. Many of these areas, of course, have enormous technological and/or
theoretical facets that are totally outside our perspective. Nevertheless, all share a common
interest in small particles and/or large molecules. 
Two of the important consequences of the size range of colloids are (a) colloidal
materials have enormous surface areas and “surface energies,” and (b) the properties of
colloidal “particles” are not always those of the corresponding bulk matter or those of the
corresponding atoms or molecule.
Colloids are also often classified on the basis of the affinity of the surfaces of the
particles to the continuous phase. The terms used to distinguish colloidal “particles” on the
basis of their affinity to the fluid in which they are dispersed are lyophilic and lyophobic.
These terms mean, literally, “solvent loving” and “solvent fearing,” respectively. When water
is the medium or solvent, the terms hydrophilic or hydrophobic are often used. The classical
use of the term lyophilic colloids refers to soluble macromolecular materials in which the
individual particles (macromolecules such as synthetic polymer chains or proteins) are of
colloidal dimensions. However, there are macromolecules of colloidal dimensions containing
both lyophobic and lyophilic components (e.g., proteins with hydrocarbon [ hydrophobic]
portions and hydrophilic [peptide and carboxyl groups] portions. The onset of micellization
occurs at a well-defined concentration - known as the critical Richelle concentration - which
makes micelle formation very much like a phase separation. However, the individual small
molecules retain their identity in the micelles, which are not covalent entities like polymers,
so their surface is problematic. Above we used the words continuous phase and dispersed
phase to refer to the medium and to the particles, respectively, in the colloidal size range. It
should be understood that these are solvent and solute in lyophilic systems. In micellar
systems, the micelles are dispersed in an aqueous continuous phase, Furthermore, the system
as a whole is generally called a dispersion when we wish to emphasize the colloidal nature of
the dispersed particles. This terminology is by no means universal. Lyophilic dispersions are
true solutions and may be called such, although this term ignores the colloidal size of the
solute molecules. Lyophobic colloids are known by a variety of terms, depending on the
nature phases involved. 
 Likewise, many colloidal dispersions have kinetic stability, even though they are
unstable thermodynamically. The coarsening process of a thermodynamically unstable
dispersion is called coalescence or aggregation. It is important that we differentiate between
coalescence and aggregation. By coalescence we mean a process by which two (or more)
small particles fuse together to form a single larger particle. The central feature of
coalescence is thLe fact that total surface area is reduced. Aggregation is the process by
which small particles clump together like a bunch of grapes (an aggregate), but do not fuse
into a new particle. In aggregation there is no reduction of surface, although certain surface
sites may be blocked at the points at which the smaller particles touch. The term coagulation
is also used to describe the process of aggregation. A colloid that is stable against coalescence
or aggregation is called kinetically stable. 
Incidentally, when small particles coalesce all evidence of the smaller particles is
erased. Only the new, larger particle remains. With aggregation, however, the small particles
retain their identity; only their kinetic independence is lost. The aggregate moves as a single
unit. Likewise, the clusters that form as the products of the process may be called aggregates.
In contrast to the above-described kinetic stability, colloids may also be
thermodynamically stable. A stable macromolecular solution is an example we have already
discussed. Formation of micelles beyond the critical micelle concentration is another example
of the formation of a thermodynamically stable colloidal phase. However, when the
concentration of the (say, initially spherical) micelles increases with addition of surfactants to
the system, the spherical micelles may become thermodynamically unstable and may form
other forms of (thermodynamically stable) surfactant assemblies of more complex shapes
(such as cylindrical micelles, liquid-crystalline phases, bilayers, etc.). 
Similarly, charged solid particles (such as latex spheres) - kinetically stable lyophobic
colloids - may exist in colloidal crystalline phases (with body-centred or face-centred cubic
structures) as a consequence of thermodynamically favoured reduction in free energies.
Clearly, uniform-size particles of spherical geometry are the easiest to deal with in
this respect, but colloidal particles come in all sizes and shapes. Even in the case of spherical
particles of uniform size, other physical and chemical properties (e.g., surface charge) may
not be uniform due to surface heterogeneities at the molecular scale (10). 

Corrosion Inhibitors
Corrosion is a natural, spontaneous and thermodynamically favoured process. There are
several methods by which corrosion can be controlled; one such method is the use of
corrosion inhibitors. Corrosion inhibitors are chemical compounds which, when added in
small quantities, reduce or completely prevent the corrosion process. They may be anodic,
cathodic or mixed type depending upon whether they control the anodic reaction, the cathodic
reaction or both anodic and cathodic reactions. A good inhibitor is expected to have the
following characteristics:
• Water solubility (but not too much).
• Hydrophobicity (to displace water from metal surface).
• Reactivity with metal or high adsorption strength.
• A good delivery mechanism (11).
Surface chemistry research is an interdisciplinary area on the frontiers of physical
chemistry and nanoscience. Residual unbalanced forces exist on the surface of a solid. As a
result of these residual forces, the surface of a solid has a tendency to attract and retain
molecules of other species with which it is brought into contact.
Nanoparticles can be better inhibitors, because, as the size of the particle decreases,
the surface area for a given mass and hence the number of active centres increases. This
ultimately leads to efficient physisorption/chemisorption of nanosized inhibitors on corroding
metal surfaces. Hence better corrosion inhibition efficiency can be realized when
nanoparticles are used as corrosion inhibitors (12).
To increase the longevity of the corrosion inhibitors it is necessary to hold the
corrosion inhibitors in a non-leachable form until the onset of metal corrosion triggers the
release of the corrosion inhibitor. One approach would be to incorporate into the corrosion-
inhibiting material a labile bond that can be disrupted by products released from the corrosion
process. For most coated metals in air/water vapour environments, the galvanic corrosion cell
consists of the oxidation of the metal (anode) and reduction of oxygen (in the presence of
water) to form hydroxide anions (cathode). Thus, the design of carriers that protect the
reactive groups of the corrosion inhibitors while the coating is curing before releasing the
corrosion inhibitors in the presence of hydroxyl groups would be an attractive corrosion-
inhibiting system (13).
Surface-modified nanoparticles are good candidates for corrosion-inhibiting additives.
Nanoparticles have high surface areas (high loadings of organic corrosion inhibitors) and
novel surface chemistries (enhanced chemical reactivity) and offer multiple property
enhancements without trade-offs. However, there are also some practical limitations to the
use of nanoparticles as corrosion inhibitors. These include cost (paints are a commodity
product), accessible surface chemistry (one needs to tether the corrosion inhibitor to the
nanoparticle surface) and a release mechanism (14).
A material known as boehmite (AlOOH) fulfils the needs of a carrier for organic
corrosion inhibitors. Commercially available boehmite has a high surface area (250 fm 2/g).
Furthermore, commercial boehmite can easily be converted from its delivered form (30–50
micron agglomerates) to individual (40–70 nm) nanoparticle crystallites in water.
Nanoparticle boehmite also has a rich and readily accessible surface chemistry (15). Finally,
the bond between a carboxylate and the boehmite particle surface is cleavable by hydroxide
anions. Thus, boehmite particles that are surface-modified with carboxylic acids can serve as
on-demand releasable carriers for corrosion inhibitors if the inhibitor is bound to the
boehmite surface through a pH-cleavable carboxylate bond (16). Recent modelling studies
have found that the pH dependence of the inhibitor release is a critical factor in optimizing
the effectiveness and service life of a functional coating (17). This type of corrosion-
inhibiting mechanism prevents premature depletion of the inhibitor reservoir of the coating
(18).

Functionalized nanoparticles and nanostructures as carriers

Nanostructured carriers improve the efficiency of corrosion inhibitors/biocides. The
advantages are:
• Nanoparticles and nanostructures can serve as excellent carriers for inhibitors.
• Organic inhibitor, inorganic inhibitor and mixed inhibitor carriers are possible.
• Controlled and triggered release of inhibitors can be built in (19).
As an example, noteworthy properties of nanostructured boehmite 1 to function as effective
carriers are:
• Pores are accessible to water without organic burnout.
• Surface area of 260 m2/g.
• Tuneable hydrophobicity.
• Nonporous carriers can be prepared without corrosion inhibitors and then be filled
with inhibitors later.
• ‘Burned-out’ nanostructures can also be filled with corrosion inhibitors.
• Release rate controlled by pore size and pore hydrophobicity (20).
Figure 1. Types of nanostructured carriers: (a) supported polyelectrolytes; (b) surface-
modified nanoparticles; (c) layered clays; (d) sol–gel encapsulants; (e) boehmite
nanoparticle carriers; (f) nanostructured boehmite carriers (21).
Carboxyl groups can be anchored on boehmite particles and they may be
released on demand by change in pH, especially by hydroxide anions generated
during the corrosion process. The anchored inhibitors can also be released by change
 in pore size which can be achieved by variation in temperature. Thus, the inhibitors
remain in the coating until needed and when corrosion occurs they release, migrate to
the metal surface and arrest corrosion. Current inhibitors are selected to be slightly
soluble in water, and slowly but continually leach out of the coating. In contrast, the
new corrosion inhibitor additives are released only when needed to arrest corrosion.
This smart release-on-demand mechanism extends the life of the coating, since the
inhibitors are not being continually lost (22).

Figure 2, Corrosion arrested by release of corrosion inhibitor.

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