Lecture #2.

Contact between solids. Solid surfaces. Roughness of surfaces. Characterization of

Adhesion and Cohesion Properties of Solids: Adsorption to Solids

Aggregates, clumps, or groups of atoms are all generally attracted toward each other just as the planets
and stars are. Bonding between atoms may be described in terms of their electron structure. In the current
shell theory of electrons it would appear that the number of electrons with negative charge would balance
the positive charge on the nucleus and there would be no net electrostatic attraction between atoms.
However, within clusters of atoms the valence electrons (those in the outer shells) take on two different
duties. In the covalent bond, for example, a pair of electrons orbit around two adjacent atoms and constitute
the "s" bond. The remaining electrons in nonconductors, and all valence electrons in metal, become
"delocalized," setting up standing waves among a wide group of nuclei, forming the к bond. The average
energy state of these delocalized electrons is lower than the energy state of valence electrons in single atoms,
and this is the energy of bonding between atoms. These energy states can be detected most readily by
spectroscopic measurements.

ATOMIC (COHESIVE) BONDING SYSTEMS

There are four atomic bonding systems in nature: the metallic bond, the ionic bond, the covalent bond,
and the van der Waals bond systems. These are often referred to as cohesive bonding systems.
The Metallic (or Electronic) Bond-.
Metallic bonding is a type of chemical bonding that arises from the electrostatic attractive force
between conduction electrons (in the form of an electron cloud of delocalized electrons) and positively
charged metal ions. It may be described as the sharing of free electrons among a lattice of positively
charged ions (cations). Metallic bonding accounts for many physical properties of metals, such
as strength, ductility, thermal and electrical resistivity and conductivity, opacity, and luster.
Metallic bonding is not the only type of chemical bonding a metal can exhibit, even as a pure
substance. For example, elemental gallium consists of covalently-bound pairs of atoms in both liquid
and solid state—these pairs form a crystal lattice with metallic bonding between them. Another example
of a metal–metal covalent bond is mercurous ion .

Those elements that readily conduct heat and electricity are referred to as metals. The valence electrons
of metallic elements are not bound to specific nuclei as they are in ceramic and polymeric materials.
Coincidentally, the variation in bonding energy, as a single atom moves along a "flat" array of other atoms,
is small. The atoms are therefore not highly constrained to specific locations or bond angles relative to other
atoms.
The Covalent Bond:
A covalent bond, also called a molecular bond, is a chemical bond that involves the sharing
of electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs,
and the stable balance of attractive and repulsive forces between atoms, when they share electrons, is
known as covalent bonding. For many molecules, the sharing of electrons allows each atom to attain
the equivalent of a full outer shell, corresponding to a stable electronic configuration.
When two or more atoms (ions of the same charge) share a pair of electrons such that they constitute a
stable octet, they are referred to as covalently bonded atoms. For example, a hydrogen atom can bond to one
other hydrogen or fluorine or chlorine (etc.) atom because all of these have the same number of valence
electrons (+ or -). Some single atoms will have enough electrons to share with two or more other atoms and
form a group of strongly attached atoms. Oxygen and sulfur have two covalent bonds, nitrogen has three,
carbon and silicon may have four. To dislodge covalently bonded atoms from their normal sites requires
considerable energy, almost enough to separate (evaporate) the atoms completely. The bond angles are very
specific in covalent solids.
 The carbon-carbon bond, as one covalent material, may produce a three- dimensional array. In this array
the bonds are very specific as to angle and length. This is why diamond is so hard and brittle.
When a single atom is brought down to a plane containing covalently bonded atoms, the single atom may
receive either very little attention, or considerable attention depending on the exact site upon which it lands.
Two planes of three- dimensional covalently bonded atoms will adhere very strongly if the atoms in the two
surfaces happen to line up perfectly, but if each surface is a different lattice plane or if identical lattice
planes are rotated slightly, the adhesion will be considerably reduced, to as low as 3% of the maximum.
The Ionic Bond:
Some materials are held together by electrostatic attraction between positive and negative ions. Where
the valence of the positive and negative ions is the same, there will be equal numbers of these bonded ions.
Where, for example, the positive ion has a larger charge than do surrounding negative ions, several negative
ions will surround the positive ion, consistent with available space between the ions. (Recall that the positive
ion will usually be smaller than the negative ion.) Actually, the ion pairs or clusters do not become isolated
units. Rather, all valence electrons are n electrons, that is, the valence electrons vibrate in synchronization
with those in adjacent electrons, binding the atoms together.
Ionic bonds are very strong. They can accommodate only a little more linear and angular displacement
than can the covalent bonds. Again, two surfaces of ionic materials may adhere with high strength, or a
lower strength depending on the lattice alignment.
The van der Waals Bonds:

Attractive forces of atoms extend a distance of 3 or 4 times the radius of an atom, though the forces at
this distance are weak. When atoms are assembled as molecules these forces are enhanced in proportion to
the size of molecules, and enhanced further by any polarity that exists in some molecules. In large molecular
structures such as the polymers, these forces bind the molecules together and constitute a major part of the
strength of the polymer material. The strength is much less than that of the ionic, covalent, and metallic
bonds however.

ADHESION

Adhesion is the tendency of dissimilar particles or surfaces to cling to one another

Bonding Between Dissimilar Materials Within the Same Bond Classification: The discussions on atomic
bonding often focus on simple systems. In engineering practice, parts sliding against each other are often
dissimilar. A brass sliding on steel, with no adsorbed layers present, might be expected to bond according to
the rales of the metallic bond system, and similarly with the covalent, ionic, and van der Waals systems. All
cleaned metals that have been contacted together in vacuum have bonded together with very high strength. It
is possible that solubility of one metal in the other may enhance adhesion and thereby influence friction (and
wear) but not significantly at temperatures below two thirds of the MP in absolute units.
Adhesion experiments with ceramic materials have not yielded high bond strength, probably because of
the difficulty in matching lattices as perfectly as required. However, when two different ceramic materials
are rubbed together, there is an increased probability that some fortuitous and adequate alignment of lattices
occurs to form strong bonds. Debris is also formed and these particles also bond to one or another of the
sliding surfaces. Layers of debris sometimes form such compact films as to reduce the wear rate.
Disparate Bonds: The term "disparate" bonds is an unofficial classification, used here to refer to the
bonding that takes place between a covalent system and an ionic system, or between an ionic and metallic
system, etc. For example, the bond strength between a layer of A1 203 "grown on" aluminum is very high
though A1203 is an ionic ceramic material and aluminum is a metal. Again, when polyethylene is rubbed
against clean glass or metal, a film of the polymer is left behind, indicating that the (adhesive) bond between
the polymer film and glass or metal is about as strong as the (cohesive) bonds within the polymer. In general
some disparate systems might be expected to bond well because the surfaces of all materials have different
structures and energy states than do the interiors. Where there is reasonable lattice matching there could then
be high bond strength. This is the subject of current research in materials science, and few guidelines are yet
available.

Solid Surfaces

TECHNOLOGICAL SURFACE MAKING

Surfaces are produced in a wide variety of ways, and each process produces its peculiar roughness,
subsurface damage, and residual stress. Several processes will be described.

Cutting: One of the more common surface making processes is done with a hard tool on metals (which are
usually softer than 40 Rc) in lathes, milling machines, and drilling machines. (Steels as hard as 60 Rc can be
cut with very hard tools such as cubic boron nitride.) Material removal in a lathe is done by a tool moving
(usually) from right to left while a cylinder rotates. The finished surface is somewhat like a very shallow
screw thread, depending on the rate of tool motion and the shape at the end of the tool. For some uses,
this roughness of the cylinder along its length, i.e., across the screw threads or feed marks, adequately
characterizes the surface. For many uses, however, the roughness in the direction of cutting is more
important, particularly when using tools designed to minimize the feed marks.

The mechanics of cutting is usually represented as being done with a perfectly sharp tool edge. Such tools
are difficult to make as is seen in the difficulty in getting very sharp points for use in scanning tunnel
microscopes or field ion microscopes. Rather, practical tool "edges" can best be represented as being
rounded, with radii, R, in the range of 2 to 40 (xm. These dimensions are equivalent to 7000 to 60,000
atoms.

The cutting action of conventional tools can best be visualized by observing the cutting of fairly brittle metal
such as molybdenum. Figure 4.1 is a sketch of a cutting process.

As the tool advances against the material to be removed it exerts a stress upon the material ahead of it. In
a brittle material a crack initiates at some point where the strength of the material is first reached and
propagates along pathway "a." As the tool advances it imposes a changing stress field upon the material
ahead of it until crack "a" has insufficient tensile stress to advance further. With further movement of the
tool, the chip bends, exerting a tensile stress such that crack "b" initiates and propagates downward. This
crack also moves into a diminishing stress field and stops. The stress field changes such that a new crack,
"c," begins and propagates as shown. (Figure 4.1 shows a stationary tool but an advancing sequence of
cracks.) The region below the cracks shows the shape of surface left by the crack sequences, which the heel
of the tool alters further.
The sliding of the heel of the tool over a newly formed metal is a particularly severe form of sliding,
producing very high friction. The tool burnishes the surface, pushing high regions downward, which causes
valleys to rise by plastic flow. It shears the high regions so that tongues of metal become laps and folds
lying over the lower regions. The result is a very severely deformed surface region that is particularly
vulnerable to corrosion. This severe deformation extends about 5R to 10R into the surface. The surface is
rough, but the laps and folds are relatively easily removed by later sliding. This is one reason why new
surfaces wear faster during first use and why surfaces need to be broken in.

The above illustration uses brittle properties of material initially to explain how cracks propagate ahead of
the tool but suggests plastic behavior under the heel of the tool. The latter is reasonable in brittle material
because the material under the tool has large compressive stress components imposed.

Initially ductile material does not fracture in the manner shown in Figure 4.1, but a wandering pattern of
shear is seen, followed by a finer pattern of ductile fracture planes. Fracture is likely to follow the interfaces
between two phases so that the resulting surface topography will be affected by the sizes of grain and
phase regions. Burnishing by the heel of the tool produces the same effect as described above.

The burnishing action is severe, resulting in a hardening of the surface layer. Strains of e=3 (and as high as
£=10) can be inferred from hardness measurements. (An e=2 can be achieved by stretching a mm-gage
length of a tensile specimen to 14.8 mm and an £=10 by stretching to 22 m.)

Rolling: Rolled sheet, plate, bar, et al„ may be processed hot or cold. Hot rolling of metal is done at
temperatures well above the recrystallization temperature and usually results in a surface covered by oxide
and pock marks where oxides had been pressed into the metal and then fallen off. Cold rolling is usually
done after thick scales of oxides are pickled off in an acid. It produces a smoother surface. There is some
slip between rollers and sheet, which roughens the sheet surface, but this effect can be reduced by good
lubrication.

Extrusion and Drawing: These processes can also be done hot or cold. The effect of oxides is the same as in
rolling although the billets for extrusion and drawing are often heated in nonoxidizing atmospheres to
reduce these effects. In any case, sliding of the deforming metal, polymer, and unsintered ceramic mate-
rials against hard dies (usually steel) will produce very rough surfaces unless the process is well lubricated.

Most cold-forming processes leave the surface of the processed part strained more (in shear) than the
substrate has been strained. This produces surface hardening, but more important it produces compressive
residual stresses in the surface with tensile residual stresses in the deeper substrate.

Electrospark Erosion: This process (applicable mostly to metals) melts a small region of the surface and
washes some molten metal away. The final surface roughness depends on the size of the "sparks" and the
spacing between sparks if the electrode is moving. Just below the melt region the metal goes through a
cycle of heating and cooling, leaving that region in a state of tensile residual stress.
Grinding and Other Abrasive Operations: Removal of material by abrasive operations involves the same
mechanics as in cutting with a hard tool. The major difference is the scale (size) of damage and plastic
working. The abrasive particles (grit) in grinding wheels, hones, and abrasive paper are small but rounded
primarily, and they produce grooves on surfaces. The abrasive particles cut (remove) very little material but
they plastically deform the surface severely, as may be seen by the fact that abrasive operations require
between 5 and 10 times more energy to remove a unit of material than do operations using a hard tool.
Abrasive operations leave surfaces somewhat rough and severely cold-worked with residual stresses. Cold
operations produce compressive residual stresses, but high severity grinding can produce tensile residual
stresses.

Surface Topography

Surface imperfections at an atomic level are matched by macroscopic deviations from flatness.
Almost every known surfaces, apart from the cleaved faces of mica, [8] are rough. Roughness
means that most parts of a surface are not flat but form either a peak or a valley. The typical
amplitude between the peaks and valleys for engineering surfaces is well bellow one micrometre.
The profile of a rough surface is almost always random unless some regular features have been
deliberately introduced. The random components of the surface profiles look very much the same
whatever their source, irrespectively of the absolute scale of size involved [9]. This is illustrated in
Figure 10.2 where the series of surface roughness profiles extracted from machined surfaces and
from the surface of the earth and the moon (on a large scale) are shown.
Another unique property of surface roughness is that, if repeatedly magnified, increasing details
of surface features are observed down to the nanoscales.
It has been observed that surface roughness profiles resemble electrical recordings of white noise
and therefore similar statistical methods have been employed in their analysis. The introduction
of statistical methods to the analysis of surface topography was probably due to Abbott and
Firestone in 1933 [11] when they proposed a bearing area curve as a means of profile
representation [9]. This curve representing the real contact area, also known as the Abbott curve,
is obtained from the surface profile. It is compiled by considering the fraction of surface
intersected by an infinitesimally thin plane positioned above a datum plane. The intersect length
with material along the plane is measured, summed together and plotted as a proportion of the
total length. The procedure is repeated through a number of slices. The proportion of this sum to
the total length of bearing line is considered to represent the proportion of the true area to the
nominal area [9]. Although it can be disputed that this procedure gives the bearing length along a
profile, it has been shown that for a random surface the bearing length and bearing area fractions
are identical [12,9]. The obtained curve is in fact an integral of the height probability density
function 'p(z)' and if the height distribution is Gaussian then this curve is nothing else than the
cumulative probability function 'P(z)' of classical statistics. The height distribution is constructed
by plotting the number or proportion of surface heights lying between two specific heights as a
function of the height [9]. It is a means of representing all surface heights. The method of
obtaining the bearing area curve is illustrated schematically in Figure 10.4.
FIGURE 10.2 Similarities between random profiles of rough surfaces whether natural or artificial
(adapted from [9].

FIGURE 10.4 Determination of a bearing area curve of a rough surface; z is the distance perpendicular to
the plane of the surface, Az is the interval between two heights, h is the mean plane separation, p(z) is
the height probability density function, P(z) is the cumulative probability function [9].

ROUGHNESS OF SURFACES
 5 5 5 n
1 1 1
. R z=
10 ( 1 1
)
∑|y imax|+ ∑ |y imin| , R z= ∑ | y i| , Ra = ∑ | y i|
n 1 n 1
The roughness of surfaces is expressed as the height of the small irregularities or asperities on the surfaces.
The practical range of roughness of commercial surfaces is given in Table 4.1.
It is obvious that all of the roughnesses described above are large compared with nm units (atoms are of
the order of 0.3 nm apart). Atomic models lose their significance in the face of such great roughnesses.
However, since the majority of surfaces that come into contact with each other have relatively rough
surfaces, we shall spend most of our time with such surfaces. (The Appendix to Chapter 12 contains a
section on Surface Roughness Measurement.)

Ra -nın qiyməti Rz - ə çevirmək üçün aşağıdakı asılılıqdan istifadə etmək olar:

Rz KRa ,

burada Ra .2,5 mkm olarsa, K 4 ; Ra 25... 0,02 olarsa, K 5 qəbul olunur.
FINAL CONCLUSIONS ON SURFACE LAYERS

Surfaces are quite complicated. From various sources we may estimate the thickness of various layers on a
tool-cut surface that has been exposed to atmosphere for a day or two. (Iron oxide becomes = 25A thick in
10 minutes in a pressure of 80 x 10-5 Torr or = 0.1 Pa. This indicates the early growth rate of oxides. In
contrast, Figure 4.3 shows oxide thickness in the 3 to 15 nm range, which takes hours to days.)

Figure 4.3 Sketch of the condition of surfaces cut with hard tools in air.

In grinding, the highly strained solid layers may be one tenth as thick as those shown in Figure 4.3, and in
fine polishing these layers may be even thinner.

Measuring the roughness of surfaces

Koster, W.P., International Conference on Surface Technology, May 1973, Carnegie Mellon University,
Society of Manufacturing Engineers, Dearborn, MI, 1973.

Bowden F.P. and Tabor, D., Friction and Lubrication of Solids, Oxford University Press, Oxford, U.K., 1954.