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DCIC REPORT 69-2

JUNE, 1363

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DCIC Report 69-2

June, 1969
I
I
I
[

SURFACE ENERGY
OF
CERAMIC MATERIALS

Prepared by

Jules J. Duga

for the

Defense Ceramic Information Center

Battelle Memorial Institute
Columbus Laboratories
505 King Avenue
Columbu3, Ohio 43201
 ABSTRACT

The concepts, experimental techniques, and theoretical analyses of the surface

energy of solid ceramic materials are reviewed with the aim of condensing a large mass
of unrelated data into a concise form for comparison and evaluation. It is shown that
various expeiimental methods can be applied to the measurement of surface energy, but,
that each of these has certain limitations which are often unstated. Furthermore, it is
shown that theoretical analyses and empirical correlations, while sometimes rather
imprecise, can be used to approximate surface energies, particularly as functions of
temperature. While a few materials have been discussed in considerable detail (such
as MgO, AI2O3 and some alkali halides), a review of the literature notes that there is a
great paucity of information on the surface energies of many solids of interest. Improve-
ments and extensions of experimental and empirical techniques are suggested that will
help to fill the voids in the present understanding of ceramic solid surfaces, and specific
analyses of experimental methods are forwarded. It is shown in the report that the
proper use of thermodynamic techniques offers considerable potential for the measure-
ment and interpretation of solid surface energies of a large number of materials that
are poorly understood at present. In addition, the further development of thermody-
namic methods presents an opportunity to investigate solid surface energies of non-
brittle materials, thus overcoming one of the basic limitations of the use of mechanical
methods.

FOREWORD

This special report was prepared for the Defense Ceramic Information Center
(DCIC) by Dr. Jules J. Duga, Associate Adv'sor, Physical Chemistry and Solid State
Materials Division, Department of Chemistry and Chemical Engineering, Columbus
Laboratories, Battelle Memorial Institute.

The author wishes to acknowledge the contributions from the following individuals:
B. R. Emrich of the Air Force Materials Laboratory for his support and encourage-
ment; Prof. J. A. Pask, University of California; Prof. Hayne Palmour, III, North
Carolina State University; Dr. A. R.C. Westwood, Research Institute for Advanced
Studies; and Dr. S. M. Wiederhorn, National Bureau of Standards, for their contribu-
tions to the literature search; and W. H. Duckworth and C. L. Downey of Battelle's
Columbus Laboratories for their advice and editorial comments.

DCIC is operated by Battelle's Columbus Laboratories under U.S. Air Force

Contract No. F336 15-67-C-1472. The program is administered by the Information
Branch (MAAM), Materials Support Division, Air Force Materials Laboratory, Wright-
Patterson Air Force Base, Ohio.
 TABLE OF CONTENTS

I. INTRODUCTION AND SUMMARY 1

II. SCOPE 4

III. THE CONCEPT OF SURFACE ENERGY 6

III-1. Basic Definitions and Distinctions 6

III-2. Factors Affecting the Ideal Surface Energy 6
III-3. Relation of Surface Energy to Other Material Properties .... 7

IV. EXPERIMENTAL TECHNIQUES 12

IV-1. Summary of Experimental Techniques 12

IV-2. Mechanical Methods 15
IV-2. 1, Crack Propagation 15
IV-2. 2. Calculation from Elastic Constants 18
IV-2.3. Strain Energy Release 19
IV-2. 4. Crushing 23
IV-2. 5. Bent-Wafer Techniques 24
IV-2.6. Fiber Stress 25
IV-2.7. Unit-Cell Measurements 27
IV-2. 8. Other Mechanical Techniques 27
IV-3. Thermodynamic Methods 28
IV-3.1. Critical Angle for Wetting 28
IV-3.2. Heat of Immersion 32
IV-3.3. Dissolution and Heat of Solution 34
IV-4. The Interpretation of Experimental Data 35
IV-4. 1. Adsorbate Effects 35
IV-4.2. Liquid-Solid Interfacial Effects 36
iv 4. 3. Particle-Size Effects 38
1V-4.4. Grain-Size Effects 39

V. THEORETICAL CALCULATIONS 41

V-l. The Atomistic Approach 41

V-2. Semi-Quantitative Structural and Thermodynamic Considerations . . 45
V-3. Correlation Techniques 53

VI. SOLID SURFACE ENERGIES 58

VI-1. The Surface Energy of Crystalline Solids 50

VI-2. The Surface Energy of Glasses 72

VII. CONCLUSIONS 75

REFERENCES 77
 TABLE OF CONTENTS
(Continued)

Page

APPENDIX A

APPLICATION OF TECHNIQUES A-l

APPENDIX B

CLASSES OF MATERIALS STUDIED B-l

APPENDIX C

SURFACE TENSION OF SELECTED FUSED SALTS AS A FUNCTION

ut TEMPERATURE C-l

LIST OF FIGURES

Figure 1. Schematic Drawing of the Cleavage of a Crystal 15

Figure 2. Specimen Geometry: Strain-Energy Release 20

Figure 3. A Typical Load/Deflection Curve for Determining Strain-Energy

Release Rates 20

Figure 4. Variation of Crack Depth-to-Thickne 38 Radio Correction Factor,

f(c/t), With Changing Ratio 21

Figure 5. General Form of the Curve of Stiffness, k, versus

Crack Area, A 22

Figure 6. Schematic Load-Time Curves Representing (A) Catastrophic,

(B) SemiPtable, and (C^ Stable Fractures 23

Figure 7. (A) Fiber Elongation and (B) Glass Fiber as a Cylinder of

Viscous Material 25

Figure 8. Surface Tension Versus Silica Contents for Binary Silicate Melts . . 30

Figure 9. Surface Tension Versus SiO£ Contents for FeO-Si02 and

CaO-Si02 Melts 30

Figure 10. Surface Tension in the System FeO-MaO-Si02 at 1400 C 31

Figure 11. Surface Tension in the System FeO-CaO-Si02 at 1400 C . . . . . 31

Figure 12. Structures of Liquids Used for Immersion Studies 37

Figure 13. Calculated Effect of Particle Size on the Surface Tension

of a Liquid 39

ii
 LIST OF FIGURES
(Continued)

Page

Figure 14. Measured Surface Energies as a Function of Grain Size for

AI2O3 and MgO 40

Figure 15. The Positive Quadrant of a Stereographic Projection of a Cubic

Crystal With Some Planes Indicated by Their Miller Indices. ... 49

Figure 16. The Surface Energy Ratios for the Simple Cubic System Plotted
on a Stereographic Projection 49

Figure 17. The Surface-Energy Ratios for the Face-Centered Cubic

System Plotted on a Stereographic Projection 50

Figure 18. The Surface-Energy Ratios for a Body-Centered Cubic

Material (a-Fe) Plotted on a Stereographic Projection ..... 50

Figure 19. Correlation Between Surface Free Energy Density, ^Fg, and the
Cohesive Energy Parameter, 6y, for Various Types of Solids „ 55

Figure 20. Change in Surface Tension of Fused Metal Oxides by Addition of

Various Other Metal Oxides 57

Figure 21. Temperature Coefficient, dT/dT, of the Surface Tension of

Mixtures of Fused Metal Oxides 57

LIST OF TABLES

Table 1. Summary of Principal Experimental Techniques for

Determining Surface Energy 14

Table 2. Partial Surface Energies of Various Solids Immersed in

Different Liquids 36

Table 3. Heats of Immersion of Rutile in Various Liquids 37

Table 4. Theoretical Surface Energies of Alkali Halide Crystals at 0 K . . . 44

Table 5. Surface Tensions (T ) and Energies (7) Calculated for Alkali

Halides at 0 K 45

Table 6. Solid Surface Energies of Ceramic Compounds 60

Table 7. Surface Energies of Various Glasses 74

Table A-l. Primary Experimental Techniques and the Materials Measured

by Them A-l

111
 LIST OF TABLES
(Continued)

Page

Table A-2. Major Theoretical Techniques and Solid Surface Energies

Calculated by Them A-2

Table B-l. Materials Studied by Primary Classes B-2

Table B-2. The Composition of Minerals Listed in the Text, Table 6 B-4
T s k 12
Table C-l. Constants for the Equation 7£, 0 -T/Tc) ' for Various
Fused Salts C-2

IV
 I. INTRODUCTION AND SUMMARY

The surface energy of a solid is an import** t factor in many phases of science and
technology, not only for itself but also through its marked influence on other physical
properties. Since the earliest work of Griffith, in which the now famous "Griffith
criterion" for crack propagation (i.e., for surface formation) was expounded, many
researchers have attempted to use his concepts in describing the nature of fracture in
brittle, semi-brittle or ductile materials. Moreover, numerous modifications to basic
Griffith theory have been developed to account for deviations from the perfect cases,
which are more easily treated.

During the past few years, efforts on the study of solid surface energies have
increased, particularly as a by-product of basic research on fracture. While the pre-
ponderance of recent literature on the subject of solid surface energy is still devoted to
considerations of the fracture process, the study of surface energy is increasingly being
extended to numerous other areas of investigation. One of the most obvious applications
lies in the theory of adhesioi. and the development of adhesive joints, which have tre-
mendous potential, for instance, in airplane and automotive construction, in the fabrica-
tion of habitable dwellings, and in spontaneous cold-welding of components in high vacuum
environments, such as outer space. Surface energy is an important factor in all studies
of friction, lubrication, and wear; of coatings; of glass-to-metal seals; and many other
areas of product development. Similarly, in process development the surface energy of
a material will contribute, in part, to mechanisms of filtering, wetting, catalysis, sin-
tering, epitaxial growth, any kind of joining or bonding, and crystallite and colloid
morphology, including the size and shape cl ultra-fine particles in smokes and other
particulate pollutants. Furthermore, the role of the surface energy is a critical deter-
minant in any surface treatment, such as cleaning, polishing, activation, or the like.
The design of coupling agents for composite structures is an area of particular current
importance in which surface energy is basic.

Inasmuch as the colid surface energy is a significant factor in many different fields
of research and technology, and, in addition, since there is no collected wvrk known to
this writer which organizes the subject in any detail, the present state-of-the-art report
was commissioned.

The concept of surface energy, from its basic definition through a discussion of
general factors that affect measured values, is covered in some detail, and the relations
betv een surface energy and other materials properties are explored.

From an experimental point of view, the report describes various techniques that
have been devised for the determination of surface energy. These may be broadly
classed in two categories: mechanical and thermodynamic. In the former, primary
consideration has been given to the Griffith criterion for -rack propagation and the
extensions ot *his tn Ä multitude of experimental arrangements. The fracture of a ma-
terial is accompanied by the creation of fresh surfaces, and the simplest concepts show
that the energy required to effect fracture is merely the product of the surface energy
and the area of the newly exposed faces. This theory, with inodifications, has been
applied to fhe determination A surface energies in brittle materials, but is seen to be
insufficient in materials with significant plasticity. Techniques based on the Griffith
criterion have included single crystal fracture and crack propagation, determir ation of
total stored elastic energy prior to failure in polycrystalline masses, measurements of
total area created in crushing, the energy to effect drilling, and others.
 Aside from the applications to single-crystal materials, most of these mechanical
methods result in erroneous values of surface energy, generally too large as a result of
not having corrected for plasticity, kinetic energy of resulting particles, friction effects,
and the like.

Other mechanical methods have been devised for specific materials classes, such
as the spontaneous bending of thin wafers of compound semiconductor crystals. In this
case, a lack of inversion symmetry in the (111) direction of the crystal lattice serves to
expose different "compositions" on opposite crystal faces, and a coi responding difference
in surface tension produces a bending moment that may be interpreted in terms of these
tension differences. In addition, analyses of unit cell dimensions of extremely fine
particles provide a measure of the degree to which surface tensions act as body forces
on the bulk of the sample, and the technique is found to apply where there are large sur-
face area/volume ratios. Other determinations of surface energy have been made through
the observation of the stretching of a heated fiber under its own weight or an applied
force. It is presumed that gravitation effects will tend to elongate a fiber while surface
tension forces tend to reduce the length. From the balance of forces that results, an
estimate of the surface tension, as well as the effects of adsorbed impurities, may be
ascertained.

Each technique is des* ribed in sufficient detail to provide familiarity, and each is
criticized for its ranges of applicability and the reliability ^f the results obtained.

The crack propagation experiments are believed to be the most direct method of
determining solid surface energies. Their n.ijor drawback lies in the range of temper-
atures over which thev may be applied. Wherever dislocation maneuverability becomes
appreciable, surface energy measurements are grossly affected, and complicated cor-
rection factors must be applied to the analysis. Hence, additional techniques must be
supplied for the determination of surface energies over a wider temperature range. To
this end, various methods are reviewed that involve the interaction between solids and
liquids, these falling into the general category of thermodynamic techniques. The method
showing the greatest potential for further development involves the determination of the
critical surface tension for wetting of a solid. This method, originally applied to the wet-
ting of low-energy organic materials, has been modified for certain high-energy solids
and suggests that similar critical surface tensions can be measured. There are, how-
ever, two major difficulties in the interpretation of data. First, one must recognize that
the critical tension for wetting is different from the solid surface energy by an amount
equal to the spreading pressure of the candidate liquid on the solid, a term whicli may be
difficult to evaluate. Second, it has been shown by various investigators that thermo-
dynamic technique . will generally provide only a partial answer to the problem, this be-
ing due to the different types of interactions that are possible between dissimilar ma-
terials. In this case, it is necessary to determine critical tensions using various classes
of liquids for a given solid, and the analysis tends to become quite involved.

In spite of these difficulties, thermodynamic techniques (including heats of immer-

sion, heats of solution, solubility rates, and the like) offer considerable promise through
their applicability to materials at elevated temperatures. While the most reliable me-
chanical methods may be applied only to complete brittle materials, the thermody-
namic methods can, in principle, be utilized up to the melting point of the specimen.

The theory of solid surface energies is discussed from essentially two points of
view, with different degrees of sophistication in each. The most detailed work on first-
principles calculations of surface energy is considered, where much of the effort has
 been directed toward materials which crystallize in the simple cubic structure, such as
the alkali halides. Calculations are highlighted in which consideration is given to the
electrostatic forces between ions, the effects of surface relaxation, and deformation of
the lattice due to thermal oscillations. In addition to the detailed formulation given for
the alkali halides, simpler approaches have been used for the estimation of surface
energies of several chalcogenides and oxides.

Various techniques have been proposed for the „dtimation of surface energy of
solids based upon correlations with other physical properties. While one method sug-
gests comparison of surface energies with mechanical properties such as hardness, re-
crystallization temperature, and elastic modulus, to name a few, other methods are
based on the comparison with thermodynamic and structural data, including heats of
formation, critical temperatures, crystal structure, and the like. To make full use of
these correlative approaches, it is necessary to obtain information on the surface ten-
sions of molten ceramics and their temperature dependencies. To this end, the scope of
the report is expanded to include such data on the liquid state, where applicable.

The report includes tabulation of surface energies for many different materials
(with many common minerals), and reports most measured values, with appropriate
comments regarding the reliability of the results. In addition, data on several dif-
ferent types of glasses are combined in separate tables, although no major effort is
expended to evaluate this information.

Finally, recommendations are made regarding the direction in which future re-
search should be directed to the determination of surface energies of ceramic materials.

I
I
I
 II. SCOPE

While the surface energy is an important parameter in a number of different fields

of interest, as indicated in the previous section, certain limitations must be placed on
the scope of materials to be considered in this present review. Firstly, we shall be con-
cerned only with ceramic materials (i.e. , nonmetallic inorganic materials). A number
of research programs have been devoted to the determination of surface energies of
metals, many through the use of scratch-smoothing, grain-boundary grooving, sintering,
and similar techniques. A complete analytical compendium of the solid surface energies
of metals is definitely needed, but this subject is beyond the scope of this report.

Furthermore, much work has been done on organic materials, particularly by

Zisman* ' and his co-workers, but this subject is similarly omitted from this review.
However, some of Zisman's techniques are applicable to ceramic materials and con-
sequently, this report will consider some of the organic materials with which he has been
concerned, but solely for illustration.

Secondly, little space will be given to the discussion of the surface tension of mol-
ten ceramics or glasses. It is well-recognized that the surface tension of glasses and
slags has important technological implications, including the applications to glass mold-
ing, enameling, glass-to-metal seals and other areas; however, the material presently
available is quite voluminous (with many major contributions from the Russian literature)
but so unrelated that no detailed review is possible at the present time. To collect the
data without some semblance of a connecting thread would be inconsistent with the aims
of the present report. Such a compilation will be left to future reviews*.

There are, to be sure, several materials that are expected to fall within the scope
as defined her^ and for which no values of surface energy are available except in the
liquid state (primarily alkali metal compounds). The inclusion of such data here will be
seen to be consistent with the scope of the report when discussions on correlation tech-
niques begin»

There will, in addition, be some reference to the work on selected molten ceramic
systems, particularly where it is believed that the use of critical contact angle data will
provide information relative to the 3urface energy of certain solids. Several glass sys-
tems suggest themselves as being suitable for this application, and mention of these and
their role in the determination of solid surface energies will be made at the appropriate
places.

Two very important aspects of the surface-energy determinations have also been
omitted from this report: namely, surface preparation techniques and surface area
determinations. The first of these constitutes a major report in itself, being comprised
of complicated procedures and analytical techniques. The preparation of a surface for
detailed structural, physical and chemical studies is not necessarily directed toward the
attainment of a clean surface so much as it has the aim of obtaining a characterized
surface. Although clean surfaces are highly desirable in fundamental studies of inter-
face reactions, the characterized surface provides a more direct means of analyzing
effects at real interfaces.

•There are several early reviews on the surface tension of molten glasses, as noted by Parikh(2). The reader is referred
to these <3-4) for general details.
r

Surface area determinations have similarly been omitted from detailed consider-
ation here, although it is necessary to have such information available. This is partic-
ularly true in those cases where fine particle distributions are required in surface
energy measurements, such as by solubility rates and heats of immersion. Quite gen-
erally, the surface area can be measured by adsorption techniques, usually employing
nitrogen gas where interactions other than physical adsorption are generally negligible.
Surface measurement methods have recently been reviewed by Kantro et al. w)
I
6
m. THE CONCEPT OF SURFACE ENERGY

III - 1. Basic Definitions and Distinctions

There are several ways to view the concept of surface energy, depending upon the
degree of detail required and whether interest is theoretical or practical. For a basic
qualitative picture, we may first consider a perfect crystal in an evacuated chamber in
equilibrium with its own vapor. The atoms in the bulk of the crystal are surrounded on
all sides by other bulk atoms and are in an equilibrium configuration that can be readily
determined by well-known x-ray techniques.

At the surface of this perfect crystal, such an arrangement is not generally main-
tained. The surface atoms interact with only half as many atoms as do bulk atoms and,
as a consequence, the surface lattice is somewhat distorted; a certain energy must be
applied if this distortion is to be eliminated. The solid surface energy is the energy
required to restore the bulk lattice configuration at the surface of a perfect crystal. It
is always greater than zero.

A similar concept is surface tension (the force tending to reduce the area of a sur-
face in equilibrium with its vapor), more commonly considered in discussions of the
properties of liquids. Under certain conditions, surface tension and surface energy are
equal, although a rigorous thermodynamic treatment is required to delineate the con-
ditions of equivalence clearly. One of the more important conclusions of such a treat-
ment is that not only can the surface energy and surface tension be different, but the
surface tension can be negative'"' (in anisotropic cases). Specific examples of the dif-
ference between surface energy and surface tension of solids will be given in Section V-l.

The details of the argument regarding the differences between surface energy and
surface tension of solids are not necessary to this revi?w. Perhaps the most critical
review and exposition has been given by Johnson*7', with further discussion by Gregg'8).
In the rest of the text, little distinction will be made between tension and energy. In
general, this decision will not affect the interpretation of experimental techniques and
measurements. Where confusion might arise (for example, in the discussion below
regarding the thermodynamics of surfaces and interfaces), surface tensions will be
denoted by T while surface energies are given as 7. Where the two are equivalent,
particularly with liquids, 7 is used.

III-2. Factors Affecting the Ideal Surface Energy

In the preceeding paragraphs, we considered only the case of nearly perfect crys-
tals that might be studied in the laboratory and neglected the more "practical" types of
morphologies encountered in ceramic technology. The reasons for this are rather
straightforward; it is generally easier to measure, interpret and analyze the experi-
mentally observed behavior of simple, pure structures rather than become involved in
a number of additional variables that are often poorly specified. In fact, throughout
this report major emphasis has been placed on high-quality well-characterized materials
rather than on the so-called "engineering" materials.
 In view of this situation, we should consider, in rather broad terms, the nature of
the differences to be expected between the types of information obtained with pure single
crystals as opposed to polycrystalline masses and other material conditions, particularly
with regard to experimental observation. First, as will be discussed later, the surface
energy of a crystal is not a unique quantity but varies rather widely for different crystal
orientation. Hence, in a polycrystalline material with many different crystal faces ex-
posed, the measured surface energy will be a weighted average of the spectrum of values
realizable for the specific material.

Further complicating the theory of a heterogeneous sample face are the contribu-
tions from exposed grain-boundary traces, where the grain-boundary energy is difficult to
isolate, although it is usually intermediate between the surface energies of the juxtaposed
faces at the boundary; however, exceptions to this are quite important.

Various extrinsic factors also affect the ideal surface energy, the most common of
which is the adsorption of extraneous phases from a surrounding atmosphere. For
example, a freshly cleaved surface will rapidly reduce its surface energy by adsorbing
gaseous species. Such contamination is one of the factors that can prevent easy "repair"
of a fresh break by simply remating the exposed fracture surfaces (surface rearrange-
ment due to surface tension also makes repair difficult).

In addition, "real" materials pose an important impurity problem. In certain sys-

tems, these impurities are surface active, that is, they tend to concentrate at surfaces
and interfaces (grain boundaries) and lower the surface energy. While high-purity ma-
terials maybe available in the laboratory, processing steps can introduce impurities
in the final product, and significant differences in surface energy can result. Further-
more, as mentioned above, in all materials (of both scientific and technological usage)
atmospheric impurities reduce the practical surface energy, not only through adsorption
but often through chemical reaction.

We also note that temperature affects the solid surface energy of any body, both
intrinsically and extrinsically. The intrinsic value of surface energy is temperature
dependent, partly because of configurational changes caused in the crystal lattice.
Secondly, an extrinsic factor arises in consideration of the equilibrium adsorbate pres-
sures, also temperature dependent. As the temperature increases and the degree of
surface coverage decreases, a "cleaner" surface is exposed, which has a higher surface
energy than the "dirty" surface.

III-3. Relation of Surface Energy to Other Material Properties

From purely qualitative reasoning, it appears that the surface energy of a so1 id
could be correlated with other physical properties if we give a more detailed description
of the energy concept. Some of these correlations are introduced below.

Since the analysis of fracture mechanics is important in the measurement of sur-

face energy (as will be discussed in Section IV), it is necessary to consider the condi-
tions necessary for an applied force to propagate a crack. Quite simply, the basic
Griffith criterion for crack propagation stems from an energy-balance relationship in
which the energy required to extend a crack is balanced by the increased energy of the
two fresh surfaces created. Griffith considered the two-dimensional case of an ideal-
ized elliptical crack in an Isotropie elastic material. By calculating the rate of decrease
 8

in strain energy associated with the growth of the crack under stress and equating this
to the rate of increase of surface energy, he derived the relation

»v*s,
where o = minimum applied stress required for crack growth
E = Young's modulus
7 a surface energy
c = length of ideally grown crack

Similar treatments have been given to ellipsoidal cracks, surface cracks, and the dis-
crete nature of the crystal structure. In general, it is found that

o = kVE7/c, (2)
where the geometry factor, k, can vary between 0.8 and 1.3.

A major limitation of such straightforward models is associated with the value

chosen for c, which can be interpreted in different ways. In a review of the brittle
behavior of glasses, MouldO) discussed the effect of stress concentration on the propa-
gation of a crack and showed that for a surface crack of depth, c, and tip radius, p, the
maximum stress, at the tip, is greater than the applied stress by a factor of 2vi . It
follows that the minimum applied stress for growth, a, and the ultimate stress, om, are
related by

^r7amVIö7c" . (3)

This is equivalent to Equation (1) if

ff
mV*
m =v*E.7T
(4)

Several researchers investigating fracture in ceramic materials have concluded

that the definition of the tip radius, p, affects the determination of 7. A major limitation
of fracture energy measurements and their application to surface energy determinations
relates to the uncertainty of assigned values of p, which, in turn, relates to consider-
tions of partial plasticity, effective values of p, and similar perturbations. In a recent
review, Stoke§^0) delved into questions associated with the definition of brittleness,
semibritüeness and ductility, and discussed dislocation mobility and maneuverability in
various crystal systems. Major corrections to the values of p are necessary whenever
a material is sufficiently ductile to result in a plastically deformed sone around the
crack tip. Otherwise, such zones (and the corresponding work to produce these sones)
result in a larger apparent value of the surface energy.

In most materials with a brittle-to-ductile transition, it has been observed that the
transition temperature can depend on the experimental conditions, particularly the mag-
nitude of impulse or strain rate imparted to the specimen. For sufficiently small im-
pulses, a material can behave* in a ductile, plastic manner, while large impulses (at the
same temperature) will produce catastrophic failure. It is therefore important to
 vm+*mm<*rwr ^.*v^«mtmmrlm9*»*W'Wlto*

I
I recognize that fracture-furf ace energy measurements and interpretations must consider

I the relative ductility at particular temperatures. As will be seen in later comparisons

of data, for KC1, for instance, plasticity effects are readily observed in various ma-
terials and these are reflected in the values of surface energy that result.
I At this point, we should also consider the concept of surface energy as it applies
to the thermodynamics of wetting and adhesion, inasmuch as experimental tools related
to these phenomena have been proposed. One of the more complete, yet straight-
forward, descriptions of these interface characteristics has been forwarded by Sharp
andSchonhorn(ll), who use the following approach.

In an equilibrium closed system of a liquid, L^, in contact with a plane surface of

an isotropic solid, Si, (completely insoluble in Lj>) and with the saturated vapor V$ of
the liquid, the Young-Dup re equation may be written as

r
s1vrIwrV2co,e- (5)

where the P's are surface tensions between the phases denoted by the subscripts and 0
is the liquid-solid contact angle. For an equilibrium situation, the surface tensions are
replaced by free energies, which yields:

^vrvr^vr0'0' <6)

where the 7's are the surface free energies.

From purely qualitative considerations, if the new solid surface is completely

devoid of adsorbed species, it follows that the maximum reversible work of adhesion
takes the form

where the first two terms refer to the new surface created by a complete separation of
the interface and the last term represents the work "lost" when the interface is de-
stroyed. Eliminating 'Y&jL? *rom Equations (6) and (7) permits writing the combined
expression

w
.dh=^srv2>+>L2vi(i+c°«9)- <8)

We note here that a smaller work of adhesion, W^^, results if the solid retains
an adsorbed layer of the vapor V2, whence

Käh " 7L2V$ (l + co

« ">• (9)

If, now, one assumes a reversible work of cohesion of the liquid that is merely
the work required to create two new liquid surfaces (without molecular surface re-
arrangement), we have

W = 27
coh L2v2 * (10)
 10

It new follows that for 6 = 0 (that is, complete spreading of a drop on a solid surface),
then Wadk - Wcoij = 7g° - 7s 1V7 and the ^'^ °* *<&««ion it greater than the work of
cohesion of the liquid.

Sharpe and Schonhorn extended the argument to the case in which the liquid of the
.above example is allowed to solidify (without introducing interfacial stresses) and again
concluded that the work of adhesion is always greater than the work of cohesion of the
weaker of the two materials.

The line of reasoning developed here assumes that the conclusions are valid when
solidification occurs after joining the materials. These authors also argue, without
specific substantiation, that the same results will obtain if there is solidification before
joining. In that case many additional parameters must be considered in detail.

From this treatment, it can be deduced that where there is intimate contact be-
tween two dissimilar, distinct and immiscible solid materials, the joint so formed will
always fail cohesively, rather than by a breaking of the interfacial bond. Biker man's
qualitative statistical model^12^, as well as detailed studies on van der Waals forces in
gases tend to support this thermodynamic conclusion. However, the application of this
conclusion to real systems requires that many other factors be included, such as misci-
bility, compound formation, surface texture, interfacial strains, and others.

It has been shown that if the liquid, L2, spreads on a solid, Sj, then the work of
adhesion is greater than the work of cohesion. Conversely, Sharpe and Schonhorn(ll)
point out that if the work of adhesion of L2 to Sj is greater than the work of cohesion of
1*2, then L2must spread on Si. From above we can write

adh coh 'S\ L2V2 S1L2 '

where S shall be considered as the (initial) spreading coefficient.

In the study of the spreading of organic liquids on various substrates, Zismand)

observed that, for a homologous series of liquids, a linear relation could be established
between the contact angle and the liquid surftce tension, such that

cos 9 = a -b7LVo, (12)

provided that 7T yO >yc, a critical surface tension, the significance of which will be
pointed out below. The contact angle vanishes for 7LV° = 7c» anc* wc can then write

cos B = 1 +b(7c -7LV°>- <13>

If the term rs? - rSiV? in

Equation (8) is disregarded, and cos 0 is eliminated between
Equations (8) and (13), a quadratic relation results:

"Uh'^+^LV'-^LV0' (U)
 11

which, following Zisman, »how« a maximum in Wa^ when

i .T

Zisman concluded that experiments on determination of yQt the critical surface tension
for wetting, can be used to determine maximum adherence, even if the solid surface'
energy is not known. The applications of Zisman's techniques and arguments will be
pointed out in the following section.

Before leaving the thermodynamic arguments and definitions, one final point or
critique should be emphasized. Throughout the above discussions, the thermodynamic
relations among the various surface energies and the considerations of different surface
phenomena, including wetting, spreading, contact angles, adhesion, etc., are assumed
to be quite general and applicable to the study of interactions between all different types
of materials. That such may not be the case has been argued quite strongly by Weyl"^)
and Fowkes (**> 15), where they have suggested that the total surface energy should be
divided into various components. Different types of interactions are well known to con-
tribute to the total surface energy of a given material, depending upon the nature of that
material. Van der Waals forces, Coulombic forces, metallic bonding, hydrogen bond-
ing, dispersion forces, and the like can each contribute (to one degree or another) to th«
total surface energy, and similar forces contribute to interfacial interactions between
contiguous dissimilar materials. The basic argument suggests that, in a system where
two materials interact, consideration should only be given to forces common to both
materials. That is to say, for example, that dispersion-force contributions might well
be included in a discussion of the interface between a metal and a polymer, but that the
metallic component of the metal bonding should be disregarded, inasmuch as there is
no counterpart in the other partner. Hence, one should ro-evaluate the conclusions
regarding so-called general rules of wetting and spreading.

As a consequence, some basic questions might arise in the ensuing discussions

of experimental techniques for the determination of the solid surface energy, inasmuch
as some of them use, as a tool, the interaction between two dissimilar materials. It is
possible, of course, to circumvent some of these difficulties or, in fact, to turn them
into advantages by the proper choice of a number of different materials.
 12

IV. EXPERIMENTAL TECHNIQUES

IV-1. Summary of Experiment»! Technique!

In general, the available techniques for measuring solid surface energy are
divided into two broad classes: mechanical and thermodynamic. But it must be pointed
out, as will be shown in the following text, that the vr.lues obtained by different methods
will not necessarily be the same. Moreover, the use of two different thermodynamic
techniques can yield different results. This can be demonstrated by the following
argument.

It was shown earlier that the total surface energy of any material is a result of
partial surface energies arising from different types of interactions. Furthermore,
the available evidence indicates that when two materials interact by surface forces,
only similar components of the surface energy contribute to the total interfacial energy
of the system. These concepts can now be applied to two examples of experimental
methods for determining the surface energy of solids; the extreme mechanical case of
a crack propagated in a completely brittle material, and the thermodynamic case of a
solid brought into contact with a sessile drop of a high-energy (nonspreading) liquid.

In crack propagation, the freshly created surfaces were in contact with each other
in the same material. Since the total surface energy of each of these two surfaces must
be equal, it follows that the surface energy calculated from the experimental data must
represent the total surface energy of the solid.

On the other hand, if the surface energy of the solid is considered as the sum of
individual contributions, say *)5 = *>fc(l) + TgU) + y§{3) + "XS(4), and the surface energy
of the liquid is comprised of only two components, say, 7L * 7L^ + 7L(*)> tnen tne
interfacial energy determined by the sessile drop technique will only be ">§L = "felJ2)
+ "VgiM. This argument shows that the sessile drop or other thermodynamic methods
require not only a detailed study of the solid surfaces in question, but also a detailed
study of the liquids used as the experimental tools.

Returning to the mechanical techniques for surface energy determination, crack

propagation methods have been shown to be most suitable for brittle materials; but
additional terms enter the analysis when ductility becomes significant at elevated tem-
peratures. Part of this difficulty can be overcome by using high strain-rate methods,
although kinetic energy of the separated parts (in a double cantilever experiment) should
be included in the calculations. These comments generally apply to other mechanical
methods.

While the thermodynamic techniques seem to offer the greatest potential for appli-
cation to all types of solids over wide temperature ranges, there are limitations above
and beyond those pointed out immediately above. The proper choice of liquid systems
with which to work (as in sessile drop experiments) is generally difficult, particularly
for high-temperature applications. Even small amounts of impurities (especially the
so-called "surface-active" impurities) must either be avoided or taken into account to
realise the near-equilibrium conditions required. Furthermore, if the substrate dis-
solves or the liquid diffuses into the solid to an appreciable degree, the thermodynamic
analysis will be invalid, at least in the present state of development. Some of these
 w

t^r*-*****mjrnt*mn ->,-.-»-,-~.. mi .»-»»ttitiimi

tm

i 13 I
i restrictions are not quite so severe when solubility and/or heat of solution methods |
are used to assess the solid surface energy.
i Table 1 summarizes the more common experimental techniques for determining
solid surface energy, and points out the areas of applicability and the major difficulties
encountered in using them. As the following discussions will show, each method
suggested for the determination of surface energy has several restrictions that must
[ "• either be eliminated or accounted for in the evaluation of experimental parameters.
J .. Where extraneous factors affect the measured quantities, the necessary correction
factors can be so large they practically swamp the factors sought, and problems inher-
ent in subtracting large numbers to obtain small differences arise.
! ••
One of the better reviews of the early techniques for determining surface ener-
gies was given by Partingtonf1*), where some discussion was directed toward historical
data and the evolution of the significance of the surface energy. Although the data in-
cluded by Partington are not nearly as well defined as those available from later work,
his review provides a reasonable perspective for viewing later results.

More recently, Bikerman*17) investigated the measurement of solid surface ener-

gies and drew the conclusion that nothing provides reliable values of this devious quan-
tity, provided that it does indeed exist. It is of interest here to note two of Bikerman's
quotations. First, it will be shown in the following sections that cleavage techniques
appear to result, when properly interpreted, in values of the surface energy of brit ie
solids that agree reasonably well with theoretical values. Of this, Bikerman notes
that "... it appears that the fracture methods ... not only yield improbable results but
are devoid of any theoretical foundation " Second, after discussing other experi-
mental techniques, Bikerman closes with the comments "... this review does not answer
the question whether surface energy analogous to that existing in liquids exists in solids
but, in the literature, no experiment could be found which would necessitate an affirm-
ative answer. Perhaps the reader of this review will be able to invent such an
experiment...".

In many respects, one has to agree with the attitude taken by Bikerman regard-
ing the state of the art of measurement and interpretation of surface energies of solids.
The techniques described below all leave something to be desired. Moreover, it should
become apparent that the actual experiments depend critically on the definition of sur-
face energy and, therefore, the interpretation of each experiment can be open to
question.

While Benson et al. made their major contributions in the theoretical calculation
of surface energies (particularly of the alkali halides), their recent review articled)
goes to some length in describing various experimental methods that may be used to
determine surface energies.

Techniques have been proposed to measure surface energy other than those dis-
cussed in this review, including adherence tests, which are purported to be reliable.
As a vord of caution, this reviewer points out that extreme care must be used in the
application of adherence tests to the determination of the surface energy, inasmuch as
it is presumed that complete characterisation of the physical and topographical nature
of the pertinent surfaces and interfaces is available. It is the opinion cf this writer
tha. ao simple tests of adhesion have been developed to the point where fundamentally
reliable information can be extracted from the experimental operation.
 14

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 - frH*:-?y- JH» liVün I

15

IV-2. Mechanical Methods

IV-2. 1. Crack Propagation

As discussed in the reference to the Griffith criterion, brittle fracture provides

one of the more popular experimental techniques for determining the surface energy
of solids. While many authors refer to the early work on mica by ObreimovU?), the
more recent developments by GilmanUO) flet the stage for increased activity in solid
surface energy experiments. The method of Gilman will be reviewed, including exten-
sions derived by Westwood et al^l).

The system studied consists of a specimen of cross-section dimensions, w and

2t, with a crack of length, L, as shown in Figure 1. A force, F, is applied to the two
halves of the crystal, which can then be treated as two cantilever beams, and the force
required to propagate the crack is measured. Gilman neglected elastic anisotropy in
the analysis, with the exception of the choice of elastic moduli values.

FIGURE 1. SCHEMATIC DRAWING

OF THE CLEAVAGE
OF A CRYSTAL*2*»

With the physical model described in Figure 1, the cantilever beams have a
moment of inertia I ■ jvt3/12. Applying the force, F, at x = 0 results in a bending
moment M(x) = Fx in each beam and a strain energy, U, in each beam,

F*L3
M2 (x)dx = (16)
»■iH 6EI

Furthermore, the deflection, 6, of the beam (along the line y = 0, the so-called
"neutral" plane in each beam) will be

Fx3 FL2x FL3 Ft2 (L-x)

6 = + (17)
6EI ' 2EI 3EI 8GI

where the first three terms are due to bending and the last is a contribution from shear-
ing. E and G are the Young's and the shear moduli, respectively. Gilman argued
that the contribution from shearing will usually be small enough that the last term of
Equation 17 can be neglected and the deflection curve is taken as
 16

Ö = (x3
6EI *
3L2X+ 2L3
> • <18)

We must now consider the various contributions to the energy of crack propaga-
tion. As a crack propagates under the action of the force, F, the cantilever beams are
put into motion, thus creating a kinetic energy term. The mass of an incremental
volume in one of the cantilevers is pwtdx, where p is the density, and the beam moves
1 7
with velocity dÖ/dt; thus the kinetic energy is dT = - pwtdx(d6/dt) . The total kinetic
energy of the cantilever is
L
T =
T) (Tt) ** ■ tw
0

Now dö/dt = (d6/dL) (dL/dt) = (d6/dL)vc, where vc is the crack velocity. Substitution
and integration yield

T = 12 <vc/v8)2 (L/t)2u , (20)

where vg = (E/p)*'2 _ vei0city of sound. For specimens where L/t is about 10, the
kinetic energy is small compared with the strain energy unless the crack velocity ex-
ceeds about vg/100.

If, now, we turn to the energy balances that obtain during the slow reversible
extension of a crack, the work done (dW) when a crack increases its length (dL) must
be equal to the increase in strain energy (dU) plus the energy of the newly created sur-
faces (dS), i. e., dW = dU + d>. Since dW = Fd60 = (F*L2/EI)dL and dU = (F*L2/
2EI)dL = dW/2, if dS = ->wdL, it follows that

7= 6F2L2/Ew2t3 , (21)

which is the equation derived by Gilman for the measurement of surface energies. This
is expected to be a minimum value, measured under reversible conditions, and should
provide a direct determination of the intrinsic surface energy. When cracking is
accompanied by irreversible phenomena (including plasticity near the crack tip), the
measured value should reflect these additional factors and would be larger.

Gillis(22), and Westwood and Hitch^U discussed the Gilman approach in some
detail, noting that difficulties in interpretation arise for certain values of L/t. In
partially ductile materials, large values of L/t give rise to plastic deformation terms
that increase the apparent surface energy. Furthermore, for small L/t shearing
forces are more pronounced at the crack tip, and erroneous surface energies again
result.

Again assuming the geometry of Figure 1, but now following Westwoou *nd Hitch's
methods, the deflection at the crack opening is taken to be

60 = (FL-J/3EI) + (0FL0t2/4GI) , (22)

 17
5 «»
where the second term (omitted in the preceding discustion) represents the contribution
from shearing forces. Thd factor, a, is a constant determined by the boundary condi-
tions in the vicinity of the crack tip, and, as before, G is the shear modulus. Follow-
* ** ing the same arguments concerning the energy balance at the instant of crack propaga-
I
tion, it follows that

| .. >w = TdT • (23

>
I
i

Taking the derivative of Equation (22) and combining that with Equation (23) yields

Ew2t3 [»♦»(«•] •
or
2£
7= -^-0+C-) , (25)
Ew2t3

where the correction term, Ct, includes contributions from end effects and shearing
forces. For a «0.1 and L > 3t, Cg is «0. 01 and, as in Gilman's report, may be ne-
glected. However, for very short cracks (L < t), C0 becomes quite important in the
analysis. Westwood and Hitch's work on KCl shows that the proper interpretation of
the data requires that C8 be considered.

If, now, one refers to 7A as an "apparent" surface energy (6F2L2/Ew2t3), then

Equation 24 can be rewritten as

Plotting yj^ vs. (t/L)2 should then permit a direct measurement of 7"1 and, from
the slope of the line, the value of a. The value of 7 so calculated is that which would
be expected from elementary beam theory.

In other work, Westwood and Goldheim(23) showed that with long beams, erroneous
values of 7 can be resolved (at least qualitatively) in terms of the plastic relaxation at
the crack tip, even for the reasonably ductile materials they investigated.

A somewhat more detailed calculation of crack velocities and crack accelera-

tions has been given by Berry(24), in which the surface energy may be determined
from the relations:
V.T / L„„\ / 2L„_\l/2
(27)
^('--)('*^)

A2 / L„_\ / 5L2_ L,
(28)

I
I
 18

where

v. = crack velocity

a^ = crack acceleration

vs = velocity of sound in the medium

L = length of crack at time, r

1/2
/E-yw2t3'
Lcr = critical crack length =
"\ 6F2

The other symbols were defined earlier. In an application of these relations,

Wiederhorn(25) has shown that rather precise values of the surface energy may be ob-
tained under a variety of experimental conditions.

In the proceeding discussion, qualitative consideration has been given to the

effect of adsorbed impurities on the measured value of surface energy. That adsorption
should play such a significant role is clearly pointed out for the case of mica
(KgO. 3AI2O3. 6Si02- 2H2O), which was the material originally studied by ObriemovU^).
While investigations of cleavage in vacuum have resulted in surface energies in the
range of 2400 to 5000 dyne per cm(26, 27, 28)^ similar experiments in selected atmo-
spheres^, 29,30) show considerably reduced values of surface energy (180 to 375 dyne
per cm). All of these measurements were performed at 25 C and clearly show the
effects of adsorption on surface energy.

In addition, it should be noted that the values measured in selected atmospheres

vary among themselves, where these differences may be associated with the type of
species adsorbed. As was discussed earlier, the interaction between dissimilar species
will depend upon partial surface energies, and the interaction of mica with water vapor
(yielding a measured surface energy of 180 dyne per cm) is significantly different from
that with hexane vapor (yB - 271 dyne per cm.).

IV-2. 2. Calculation from Elastic Constants

Later discussion will be devoted to the theory of surface energies and various
methods of calculation, but some of the criteria for crack propagation should be con-
sidered here, with the analysis given by Gilman(^I). Gilman's argument rests on
various criteria for predicting cleavage planes in different (metallic and non-metallic)
systems. Some have agreed that the cleavage planes are those with closest packing, or
that bound unit cells, or that cut the fewest chemical bonds; the approach taken here is
that cleavage will occur on planes having minimum surface energy.

In the preceding analysis of cleavage cracks the force necessary for crack propa-
gation depended primarily on two materials constants: the elastic modulus and the sur-
face energy. Attempting to relate these two factors, Gilman assumes that the stress
between two surfaces can be approximated by a sine function
 „, „,w.-v *** -*W WB?^ -' ; *«ti^^*pgffi'-v^w^pi^ yf<

I
19
I 7TW
a(w) = aö iin — , 0 < w < A , (29)

I where A is a "range" or relaxation distance of the attractive forces. Assuming small

displacements (sin TTW/A Z TTW/A) and Hooke's law, we have

- a(w) = E(jL)s(,o!S , (3o,

1 where w0 is the lattice constant perpendicular to the plane.

T Thus,

%-%ro > <31>

and
. , EA 7TW
a(w)=— sinT ,

If we now integrate this stress function over the entire range of application (0 to A), the
resultant surface energy becomes

1/2 A
= I 0
a(w) dw

EA fÄ 7TW
\ sin — dw (32)
27FW

=w
oo U/
Thus, the cleavage planes should be those with minimum elastic stiffness normal to
these planes, maximum separation distance, and minimum relaxation distance for the
attractive forces between them.

In the subsequent tabulation of surface energies, several values will be found

quoted as being "calculated from elastic constants". It is the evaluation of Equation (32)
that results in these entries.

IV-2.3. Strain Energy Release

While cleavage methods as outlined above are reasonably straightforward for

studies on single crystals, the method is difficult to apply to polycrystalline, non-
crystalline, or porous structures.

Davidge and Tapping2) developed methods to determine the surface energies of a

group of different brittle "irregular" materials that require a measure of the total

I
 20

energy released when a pre-notched specimen is completely broken. In essence, the

methods are three separate but related types of measurement with three interpretations.
The specimen geometry for the three methods is shown in Figure 2, where a three-
point bending apparatus with appropriate recording instrumentation is employed. A
typical load/deflection curve is shown in Figure 3.

Deflection ,8

FIGURE 2. SPECIMEN GEOMETRY FIGURE 3. A TYPICAL LOAD/DEFLEC-

STRAIN-ENERGY TION CURVE FOR DETER-
RELEASE MINING STRAIN-ENERGY
RELEASE RATES
I s span; b ■ breadth; c = crack depth;
t * thickness. PF = fracture load; 6F = fracture deflec-
tion; k = specimen stiffness, a-p = fracture
atress; U = strain energy; Yp» = surface
energy.

The strain energy release rate, dU/dA, where A is the new surface area gen-
erated, may be either calculated or determined experimentally. The former involves
the stress distribution computed around the specimen notch while the latter derives
dU/dA directly from load/deflection curves.

Analytical Approach. For small values of c/t (see Figure 2), the effective sur-
face energy, Xi» determined by this method is given by

dU »-^^
(33)
^G = -dA = - 2E
where

v = Poisson's ratio
aF = Fracture stress = 3Fi/2bt2
E = Young's modulus.
 , *«<«\r*|M!f» tfSe&S&tgWß.

21

Aside from specific numerical constants, Equation (33) is essentially the original
Griffith criterion.

For crack depths where c/t >0. 1, various mathematical treatments are avail-
able^) ^ with their form being such that the surface energy may be expressed as

_. (9 (1-v2) F2l2f(c/t)
(34)
>G
8Eb2(t-c)3

where f(c/t) is a dimensionless parameter and is plotted in Figure 4. For this correc-
tion factor to be interpreted properly, the reader should refer to the original publica-
tions, in which the details are explicitly defined.

FIGURE 4. VARIATION OF CRACK DEPTH-TO-

THICKNESS RATIO CORRECTION
FACTOR, f(c/t), WITH CHANGING
RATIO<33>

0 0.1 0.2 0.9 0.4 0.5 0.6

Ratio of Crack Depth to
Thickness (c/t)

Compliance Method. The effective surface energy determined by this method,

7C should be the same as 7Q from above. The load/deflection curve may be rep-
resented as F = kd, where k is the specimen stiffness. The stored energy at the moment
of fracture is then U = F*ö*/2 or k 5*2/2. We now see that, for fracture at a fixed
deflection, we have

7
dU I dk 6*2 o*
(35)
c--SÄ srl0 SA F5A

The specimen stiffness, k, must be measured as a function of the initial crack area,
A = 2bc. For each notch depth, (dk/oA)0 may be obtained from the slope of the crack
area-stiffness curve (Figure 5) at the appropriate value of A. Using these values with
the experimental values of 6* will give a series of 7Q values.

Work of Fracture. For the case of catastrophic failure (which will be better
r defined below), it is desirable to use deeply notched specimens, so that the total stored
* energy in a weakened structure will be small compared with the surface energy. In this
case, controlled fracture proceeds as in Figure 5. The work of fracture is given quite
i simply as
U
'F S 2b(t-c) <36>
 22

FIGURES. GENERAL FORM OF

THE CURVE OF STIFFNESS, k,
VERSUS CRACK AREA, A&V
Solid surface energy can be found
from(äk/oA)6

Crack Area A-2bc

In their studies on alumina and an unspecified glass, Davidge and Tapping*)

have shown that the analytical and compliance approaches provide self-consistent mea-
sures of the surface energy, and are in reasonably good agreement on the value of y^
On the other hand, the surface energy determined from the work of fracture is not as
well-defined, there being a dependence on the ratio c/t.

The needs for techniques which are applicable to "rough11 materials have been
given general consideration by NakayamaO4), who compared various energy conditions
and predicted the nature of failure. Again taking the case of three-point bending of a
specimen of dimension £, w, t, the energies stored at the time of fracture are calculated
to be

IwtS2
w • 18E
4w2t*S2 (37)
(b) Ua =
K42

(c) "o = U + U
. a

where

Ut, Ua = elastic energy stored in specimen and apj ratus, respectively

S = specimen tensile strength
K - apparent spring constant of apparatus
U0 = total stored energy.

For effective fracture energy of 7e£f, the energy required to cause separation in the
test piece (with cross section over A) is U « SA^ff. Now the difference AU = UQ- U^
is an approximate criterion of the mode of iracture. For AU > 0, the failure is
obviously catastrophic since the stress energy must be consumed by other forms, such
as kinetic energy of the fragments. For AU < 0, the stored energy is insufficient to
cause complete fracture, and this is referred to as stable fracture.
 .*,*-m^--*nmym%$*mwm

23

Nakayama showed different modes of failure, illustrated by the three curves of

Figure 6, and discussed the conditions under which these obtain. For completely
catastrophic brittle failure, the load/deflection curves (or, better, the load/time curves
under constant deflection rate) are of the form shown in Curve A of Figure 6. While
the total energy supplied to the system can be calculated, no reliable estimate of 7eff
is possible, because of the kinetic energy of the fragments.

• 1 1(A)
FIGURE 6. SCHEMATIC LOAD-TIME
CURVES REPRESENTING (A) CATA-
STROPHIC, (B) SEMISTABLE, AND
I ^
(C) STABLE FRACTURE^34)

Tims

On the other hand, the introduction of an artificial crack reduces the tensile
strength, S, and thus UQ, and a stable or semi-stable crack can be propagated, as in
Curve8 B and C of Figure 6. Then, the total external work, Uc.

«.-f fdr (38)

can be computed, where v is the speed of the overall deflection, TC the time for frac-
ture completion, and f is the bending force. This method has produced results that are
in essential agreement with the results of other techniques.

IV-2,4. Crushing

While Berdennikov(35) and Kuznetsov06) have considered crushing as away to

determine surface energy, a more nearly complete treatment of the problem has been
forwarded by Johnson et al. (37, 38,39) in which experiments on the crushing of quartz,
rock salt, and a number of minerals and ores was carried out. The results reported
in this latter study seem questionable, but the method itself merits some brief discus-
sion, particularly regarding the difficulties that arise.

In an ideal crushing experiment, a steady force or a sudden impact is applied to

the sample, the heat evolved is measured in a completely adibatic system, and the
total surface area of sample is determined after each step of comminution. Alter-
natively, rather than measure the heat evolved, it is possible, in principal, to deter-
mine the amount of energy dissipated in, say, a falling weight, that effects the crushing
and to translate this energy directly into the surface energy of the resulting fragments.

Either method is grossly oversimplified, since the total energy dissipated in sev-
eral ways, none of which is simple to calculate or account for. For examples, there
are frictional losses in most apparatus used for the transfer of energy to the specimen;

i
 24

in all but the most completely brittle materials, there are energy losses associated
with plastic and elastic deformation of the material, as well as in the apparatus, and
in unconfined systems, there is a contribution from the kinetic energy of the fragments.

The degree to which these uncertainties affect the results can be surmised from
a single comparison of Johnson's data with that reported by other investigators. While
the analysis of data was fairly crude, it can be seen that the surface energy experi-
mentally determined from crushing techniques is approximately 1000 times larger
than the (albeit inaccurate) theoretical figures quoted by Johnson. Clearly, consider-
able development is necessary before this technique can be regarded as a promising
candidate for surface energy determinations.

IV-2. 5. Bent-Wafer Techniques

Certain crystalline materials lack inversion symmetry in particular crystallo-

graphic directions. The most notable of these are the materials with the zincblende
structure, particularly the III-V compound semiconductors such as InSb, GaAs An
examination of the structure of these materials reveals that if these materials were
split along a (111) plane, one resulting face would be all atoms of Group III and the
other would be all atoms of Group V. Hence, a specimen of these materials that is cut
so that it is bounded by (111) planes on opposite faces would show asymmetrical prop-
erties. Some of the earliest experimental evidence of the nonequivalence of the two
faces was the work of Maringert40) on the etching of (111) faces of InSb and on the
resulting dislocation etch pits observed. More detailed observations on the etching
behaviour was documented by Gatos et al. <4l> 42,43) an(j by Faust et al. (**) in several
series of investigations on various materials with the zincblende structure.

A consequence of the dissimilarity in parallel faces is the spontaneous bending

of thin wafers of these compounds. The different chemistry of the parallel surfaces
gives rise to a different surface tension on each face, and the thin specimens will bend
until a balance is achieved between the internal elastic energy and the applied bending
moment; this configuration will be characteristic of the material and its dimensions.
Cahn and Hanneman(45) undertook a detailed study of the surface energy of the III-V
compounds and, with experimental data of Finn and Gatos(*6), compared computed
values of surface energy with the spontaneous bending observed and the resultant sur-
face tension differences. It is expected that similar effects should be found for all ma-
terials which crystallise in the zincblende structure, including the III-V compounds of
indium, aluminum, and gallium with arsenic, antimony, and phosphorus; as well as
compounds from other groups in the periodic table, for example, compounds of beryl-
lium, zinc, cadmium, and mercury with selenium, tellurium, and sulfur in Group VII.

It is interesting that the bent-wafer phenomenon can also be applied to the study of
changes in the surface tension differences caused by adsorption of gases, effects of
bulk impurities (particularly in very thin sections), and the influence of electronic
effects associated with illumination and other excitation mechanisms.

One additional point of clarification should be added regarding the actual quantities
contributing to the spontaneous bending of crystals having this structure. In principle,
the bending is caused by a difference in surface tension rather than surface energy, and
care must be exercised in the design of experiments which study this phenomenon. It
has been demonstrated that, while the absolute surface energy of a material is always
 ■■ r-an :*1*»7 ft TWl^WMt

25

greater than zero, the surface tension can be negative. A better understanding of the
relationships between these two related quantities is required before experimental data
I can be properly interpreted.

IV-2. 6. Fiber Stress

Most mechanical methods apply only to brittle or semi-brittle material. The

fiber-stress technique applies specifically to ductile materials. In this technique for
measuring the surface energy of solids, a fiber to be examined is held in a vertical
T position and a balance of forces is me* in which the downward force (due to the weight
1 of the fiber) is just balanced by the upward force (applied on the periphery) arising
from the surface tension (Figure 7). Early experiments using this method was dis-
cussed by Udin et al.(47), with later contributions from Parikh(2).

T
i
n
(A) (B)

FIGURE 7. (A) FIBER ELONGATION AND (B) GLASS FIBER

AS A CYLINDER OF VISCOUS MATERIAL^2*

According to Parikh's analysis, one considers the fiber stress along the axis of
a cylinder to be given by

xB Znry - w (39)
T* 7ir

where

27Tr"y = upward surface tension force

w & 7Tr2pig = gravitational force, downward.

The radial stresses are taken to be ay = a2 = 2*y/d = >/r. For the case of zero strain,
crx « <Jy a az, and
 26

2 . 22H1ZJ2. (40)
r 2
7Tr

or

w = 7Tr7.

But

w = aQ7Tr2 (41)

where aQ is the stress at zero strain, so that we have

aQ = 7/r. (42)

Fibers of constant radius and different lengths can be suspended in a selected

atmosphere at a given temperature and the length of fibers determined that neither
contracts under the action of surface tension nor elongates under its own weight. If
the radius and density of the material is known, the surface energy can be calculated
directly.

Two limiting situations exist. For long fibers that tend to elongate under their own
weight, the cross section should decrease continuously, increasing stress and finally
causing ductile fracture. On the other hand, the short fibers should react more strongly
to the surface forces that tend to reduce the area of the sample, and a sphere should
result. In most practical cases, the movement is much too slow to be observed in a
reasonable length of time.

As expected, Bikerman^?) takes a somewhat diffeunt view of this method, and

criticizes its use, noting that ". . .there is no reason to suspect that surface properties
of the solid have any influence on the phenomenon studied. " Bikerman has presented
several alternative derivations of the equations necessary to use fiber extension as a
total determination ox surface energy of thin wires and foils. However, he also details
nine different objections to the method, each one of which is supposed to prove that the
technique not only does not work but should nev?r be expected to work. He omitted an
important point from this critique, however, namely, the effects of creep and viscous
flow (also omitted by Parikh). Whatever the relation between the weight of the fiber
and the surface forces, no stable equilibrium is expected; in time, the fibers should
either break under their own weight or reduce to a sphere. But while no stable equilib-
rium can be expected, a kinetic equilibrium might be defined in which the elongation
caused by the weight of the fiber and the contraction associated with the surface energy
are only two of the factors which will be active in the process. In addition to these,
one must include terms associated with the diffusion of vacancies and other imperfec-
tions, dislocation migration, stress-concentration factors, inter- and inter-granular
motion (except in amorphous or single crystal structures), and additional continuously
operating variables that will influence the mass motion of the fiber. A concentrated
effort on the kinetics of this motion should produce, at a fjiven temperature, a more
nearly exact and more rigorously defined value of the surface energy of the specimen.
 27

It should be pointed out, in addition, that while the statement of the problem can
be reasonably concise, it is not suggested that the solution of the problem is simple
and straightforward. Further, and more important, the effective surface energy will
not be constant during the experiment, but will depend, in part, on the composition of
surface and the bulk. It is expected, indeed, that the presence of significant vacancy
concentrations or other physical defects will affect the surface energy, so that second-
order effects will contribute to the dynamic problem. Moreover, the presence of
adsorbed species (where experiments performed in such a manner as to investigate the
effect of such species on the surface energy) will complicate the problem further, in-
asmuch as the density of adsorption sites can be a function of the other variables of the
system.

In summary, the reaction of a fiber to its environment can be used, in principles,

as an experimental tool for determining solid surface energy, but the results must be
analyzed and interpreted very carefully.

IY-2. 7. Unit-Cell Measurements

The determination of unit-cell size by X-ray measurements on fine particles has

been discussed by Nicolson(48) as a tool for the study of surface energies. Simply
stated, it is assumed that the effective unit-cell dimensions are generally affected by
impressed force fields (as observed in high-pressure experiments). For the case con-
sidered here, an increase in surface/volume ratios obtained from specimens with
successively smaller size should manifest itself by an increased effective surface pres-
sure per unit volume and the concomitant change in unit cell dimension would constitute
a direct measure of the surface energy of the material.

It is apparent that the analysis of such an experiment implies that atomic arrange-
ments are independent of position of atoms within a given particle; i. e., the surface
''lattice" is essentially identical to the bulk lattice. That such is the case has been dis-
proved in numerous LEED* studies, particularly of nonmetallic materials. Furthermore,
considerable care must be exercised in making assumptions regarding the uniformity
of the pressure across any crystal face in a fine particle, since it is shown in numerous
examples that the surface energy is strongly orientation dependent. Finally, where
surface tension effects determine the state of strain in fine particles, additional com-
plications arise due to the fact that this term can be negative for selected crystalline
face 8.

At this point, it is not possible to ascertain the degree of reliability of data ob-
tained through the use of this method, since there has not been, to this reviewer's
knowledge, a detailed treatment of the theory of the measurement and its interpretation.

rV-2. 8. Other Mechanical Techniques

Kuznetsov(36) reviewed a number of other techniques forwarded for the deter-

mination of the surface energy of various solids, particularly the alkali halides. Among
these, the major emphasis has been on his own work using mutual grinding, abrading
and drilling methods, as well as on the use of hardness as a correlative function. Much
of this work is devoted to a semi-quantitative analysis of the weight and/or volume
losses of materials that result from the techniques used and, with a few generalities
•Low energy Electron Diffraction.

I
 28

about crystal structure, lattice constants and other parameters, provides a highly
simplified point of view. From a purely qualitative point of view, many of Kuznetsov's
findings suggest areas for fruitful development, but, the analysis of the data (as pre-
sented) leaves much to be desired.

In general, Kuznetsov makes very simple assumptions regarding the products of

the grinding, abrading or drilling methods, with the generalized comment that all con-
tributions to stored and released energy can be associated with the production of new
surfaces of crystallites, which are relatively uniform in size and shape. In some
respects, his arguments resemble Nakayama's(34), described earlier, but lack enough
detail to ascertain the limits of predictability. While Nakayama admits contributions
from elastic and plastic deformation and attempts to correct for them, Kuznetsov ap-
pears to neglect such "spurious" contributions.

For completeness, many of Kuznetsov's results will be included in the tabulation

of surface energy values in Section VI. However, the reader should realize that many
of these are subject to more detailed analysis and might be unreliable (particularly
where no other comparative data are available).

IV-3. Thermo dynamic Methods

IV-3. 1. Critical Angle for Wetting

As mentioned in discussing the thermodynamics of interface phenomena, Zisman(l)

and his co-workers developed the concept of the critical angle for wetting and have used
this to determine wetting conditions and associated phenomena. We shall consider here,
in a little more detail, the nature of the approach and its application to inorganic ma-
terials as more recently pursued by Eberhard57). Using the relation defined in Equa-
tion 13, Zisman used a series of homologous liquid organics to determine the so-called
critical surface tension, 7C, of solid substrates. It is argued that the value of 7C is a
characteristic of the solid surface alone. Zisman considers yc to be an empirical
parameter that varies with the solid surface composition in much the same way as one
would expect for the surface energy 7 2, although no specific claim is made as to the
identity of the two quantities.

More recently, EberhartW) discussed the application of this measurement to

solids with high surface energies (it will be recalled that Zisman confined his consider-
ations to materials with relatively low surface energies), comparing experimental de-
terminations of 7C with other values of 7g. In reviewing the findings of others, Eberhart
noted that the critical surface tension is of the same approximate magnitude as the
solid-vapor interfacial tension, 7g- TT where ^e is the spreading pressure of an ad-
sorbed species. If this is the case, it is then only necessary to determine the spreading
pressure in order to calculate the intrinsic surface energy directly from such contact-
angle measurements.

One immediately encounters certain difficulties in interpretation and translation,

however. The first of these comes from the definition of "homologous series of liquids"
in the sense envisaged by Zisman. To use the technique with any degree of certainty,
 29

the properties of the liquide in a service must be roughly similar or at least must vary
in a well-understood manner. It would seem logical to choose binary or higher order
liquid mixtures with well-behaved surface tensions in the region of miscibility. That
is, the liquids should have a regular (not necessarily linear) variation in surface ten-
sion with composition. Further, no component of the liquid should interact to any mea-
surable extent with the substrate material; obviously, compound formation at the inter-
faces and interdiffusion should be avoided or minimized. These restrictions are
somewhat severe, particularly for measurements at elevated temperatures, and one
cannot expect that the technique will apply readily to a large range of solid materials
until further definitive research has been carried out. Even so, it appears at this writ-
ing that the method has distinct advantages and deserves additional attention.

Examples of the type of binary liquid melts that may be used as homologous series
for the determination of solid surface energies, are shown in Figures 8 and 9. Where
no interactions occur between the melts and the substrates, these curves show that
a wide range of liquid surface tensions can be employed for high-temperature measure-
ments on selected solids. Similarly, Figures 10 and 11 depict the variability in sur-
face tensions available in ternary systems at high temperatures, where these can be
most useful in examining the surface energies of refractory compounds.

Recently, Rhee(5°) used the "homologous series" technique to measure surface

energies of a number of refractory carbides and nitrides using molten metal as the con-
tact liquid, but introduced a simple modification that might be extended to a number of
different systems. Rather than choosing a series of liquid metals or metal alloys,
Rhee elected to use a single metal and vary the temperature over a range where there
is no significant difference in the reactions between liquid and solid surfaces. By plot-
ting the contact angle as a function of temperature, a value is chosen for the critical
angle for wetting (similar to Zisman's and Eberhart's method) as a function of
temperature.

To lend support to Rhee's results, it is necessary to investigate, at least in a

cursory fashion, the theoretical basis for his choice. The most important of Rhee's
basic assumptions relates to the temperature dependence of the various surface energies
and surface tensions that affect the contact angle. The somewhat arbitrary choice of a
linear temperature dependence to all pertinent energies is made and the validity of the
final values rests on this assumption. From the discussion given later regarding the
Bruce technique(53) for estimating surface energies, it is reasonable to assume that the
solid surface energy will be a linear function of temperature. This assumption does
not apply so well to liquids, inasmuch as a 6/5-power dependence can be shown to ob-
tain' 54, 55) However, it is more important to question whether the interfaciai energy
can be assumed to be reasonably linear.

In an attempt to analyse the behaviour of the interfaciai energy of two materials,

each of known surface energy, Berghausen et al. (56) have shown that

^12= f<>l>>^ = "Vl+ ?2" 20

/V>7 (43)

where the y s refer to the two separate materials and the interface, and the function $
depends upon various intrinsic materials parameters. It can be seen here that if both
7, and 72 are approximately linear functions of the temperature (ignoring the 6/5-power
dependence), then 712 wi^ also De a nearly linear function of the temperature, at least

r
i
 30

600

FIGURE 8. SURFACE TENSION VERSUS SILICA CONTENTS FOR

BINARY SILICATE MELTS(51)

600

E
o

c 500

400
8
I
3

300
25 50
SiOjj, m/o

FIGURE 9. SURFACE TENSION VERSUS SiO* CONTENTS FOR

FeO-Sl02 AND CaO-S^ MELTS*51)
I
31
I
I

MnO

FIGURE 10. SURFACE TENSION IN THE SYSTEM FeO-MnO-Si02 AT 1400 C<52)

The surface tension isopleths are in dynes per cm,

Si02

CaO

FIGURE 11. SURFACE TENSION IN THE SYSTEM FeO-CaO-Si02 AT 1400 d52)

The surface tension isopleths are in dynes per cm.

 32

over a small temperature range. It must be emphasized, of course, that Rhee's

method applies strictly only over a small temperature range; for large ranges, reac-
tion kinetics would probably invalidate the basic assumptions of the method.

A major advantage of this and similar techniques lies in the measurement of

solid surface energies at temperatures where mechanical methods no longer apply. In
particular, the fracture techniques required that the specimens fail by completely
brittle fracture; difficulties in interpretation arose when plastic flow occurred in the
vicinity of the crack tip. The present technique precludes such difficulties, and, in
fact, the method is also essentially nondestructive. The only limitations encountered
are those associated with an interpretation of the spreading pressure and the problems
which would arise from high-temperature interactions. Well-defined data on the sur-
face tensions of a number of liquid metals and alloys are available for a wide tempera-
ture range, it appears that this technique, if properly interpreted, provides the most
direct and widely usable method for the determination of surface energies and their
temperature dependence. Further detailed consideration should be given to the theo-
retical and experimental application of this method.

However, at this point, we should again refer to the arguments of Fowkes'1*» **)
and Weyl(13) regarding the interpretation of interface phenomena and the contributions to
total surface tension or energy as represented by the various possible interactions.
Certainly, if these arguments are valid, the critical surface tension experiments out-
lined above would measure only a fraction of the total surface energy of the substrate
material. To avoid this problem and obtain representative values of total surface
energyy it would be necessary to use liquids that would cover the entire range of the
various interactions. Again, it is difficult to determine all the various contributions at
a given temperature. The plater the sirrv'arity between the substrate and the testing
liquid, the greater is their tendency to interact. On the other hand, the more the liquid
and solid are dissimilar, the less likely it is that the total surface energy can be mea-
sured. Obviously, considerable care is necessary in the selection of "tools" and the
interpretation of results. More will be said about this later, when the results of
Eberhart's studies are included in the discussion.

One additional note is of interest here, although it might seldom apply. It may be
expected that, at sufficiently high temperatures, the weight of a sessile drop could de-
form the solid surface elastically. This will change the measured value of the contact
angle slightly [see Lester'5')]. Generally, this effect is probably not significant un-
less a temperature is reached where the solid actually becomes quite viscous, as in a
glass. The correction factor for most cases (particularly since contact-angle tech-
niques do not measure total surface energy) is probably negligible.

IV-3. 2. Heat of Immersion

A series of papers^5**, 59) from the University of Cincinnati (1957-58) considered,

in great detail, the calculation of many factors related to the interaction between dis-
similar phases, with particular emphasis on adhesion, wetting, immersion, adsorp-
tion, and similar phenomena. The basic theory was summarized by Berghausen
et al(*°) and only the general content of these papers will be discussed here.
I
I The general theme of these papers was the application of interaction integrals
I defined by Fowler and Guggenheim(60)? in which the atomic structure of the subject
materials was taken into account and the cohesive and adhesive energies were cal-
culated by integration of the interaction energies over all space. While the form of the
f integral representations sets the stage for detailed calculations, a major drawback is
that the forms of the energies are conXined to only the simplest cases of van der Waals
interactions and the treatment cannot be translated straightforwardly to other types of
i interactions between molecular species.

In addition, Berghausen et al made some extremely simplified assumptions for

the sake of tractability, and thereby sacrificed much of the potential value of their re-
•* suits and methods. Be that as it may, Good et al(58) discussed the use of this theory
in the determination of the surface energies of solids by measurement of the heat of
immersion. Immersion primarily involves the replacement of a solid surface by a
solid-liquid interface. The heat evolved in this process can be measured quite ac-
curately with appropriate calorimeters and, with a knowledge of the surface area in-
volved, the change in energy can be determined. With the use of appropriately defined
functions of the van der Waals constants for the materials being studied, it was shown
that the measured heat of immersion can be related to the surface tension of the liquid
(which is directly measurable) and the surface energy of the solid alone, thereby
eliminating the effect of the solid-liquid interface.

In principle, this technique offers considerable promise for determining surface

energies of solids, rivaling the wetting methods. In fact, it can be shown (through
rather laborious calculations) that there is a distinct relationship between these two
"surface-the rmodynamic" experimental procedures(60, 61). it is anticipated that the
immersion method might even be superior, in that lower-energy liquids can be used
and a more flexible choice of liquids (especially organics) may be available.

There is one particular drawback, however, similar to the limitation imposed in

the earlier discussion of wetting techniques, and this relates to the definition of the
function used to describe interaction phenomena. In general, Berghausen et al(56)
derived this function in terms of the van der Waals constants, which depend on such
factors as polarizabilities, magnetic susceutibilities, interatomic or intermolecular
spacing, crystal structures, and the like. Furthermore, it is assumed throughout
the theory that the two species involved are completely immiscible. In the practical
application of the theory the conditions imposed and the real situation conflict, for it
can be shown that the assumptions necessary to evaluate the function are precisely the
same conditions that lead to a basic breakdown of the theory. Specifically, in most
cases where the function has been evaluated, polarizabilities, lattice constants, force
constants, etc., must be assumed to be roughly equal for the two ''dissimilar" mate-
rials, whereupon they are no longer as dissimilar as the derivation of the theory
demanded. It is in just such cases that compound formation, inter diffusion, and (at
least partial) miscibility are the rule rather than the exception, and the entire appli-
cability of the theory is subject to question.

Moreover, as in wettability studies, there is also the question regarding the

partial surface energies measured and the necessity of delving into several different
materials systems as tools for the determination of the individual components of the
total solid surface energy.

i
 34

The heat of immersion technique also has a few drawbacks that critical wetting
methods don't have. In the first place, fine particle dispersions must be used to take
greatest advantage of the method. With greater area/weight ratios, the heats of immer-
sion are measured more accurately an.1 it would be expected that surface energy would
be determined somewhat more accurately. However, it is also obvious that with
large number of small particles, there are also increased edge and corner effects;
thus the measured heat of immersion represent a more heterogeneous system than does
a critical wetting experiment, and the interpretation of total heat of immersion must
take this into account. While the "effective area" of the edge and corner effects can be
separated by adsorption studies, the heat of immersion is totally integrated, and the
weighting of the different c >mponents could present formidable analytical problems.
Finally, difficulties are expected with the exposure of various crystalline faces, while
the wetting angle experiments can conceivably be performed on selected single-crystal
faces.

This discussion of the limitations of the theory is not meant to completely dis-
courage consideration of the Berghausen technique and calculations, but merely to
point out the immense difficulties to be expected in using heats of immersion as a tool
in the quantitative measure of surface thermodynamic properties.

IV-3. 3. Dissolution and Heat of Solution

Early experiments showed that both the vapor pressure and the dissolution rate of
particles are functions of particle size, with the general result being that in a saturated
solution, large particles tend to grow at the expense of smaller ones. From measure-
ments of particle size and solubility, it is possible to calculate the surface tension (sur-
face tension is one of the driving forces for dissolution and, indeed, is the major driving
force with all other factors, such as composition, being equal). It has been shown^12)
that the surface energy of a material can be determined from the relative rates of solu-
bility for two particle sizes by the Ostwald-Freundlich equation:

where
m
"•'"^

r
l* rZ s
P*rticle radii

S.tS, - solubility rates

R = gas constant

T = temperature (K)

p m density

M = molecular weight.

It should be emphasized here that this relation pertains only to solubility ratios.
A related technique is based on the heat of solution as a function of surface area. There
 35

is a major distinction between the two types of experiments and great care must be
exercised in removing possible confusions. In most heat of solution experiments, the
material under study is immersed in the solvent and is then permitted to dissolve com-
pletely. During the various steps in the heat of solution determination (where it is
assumed that the sample materials are uniform, pure, and homogeneous) the initial
introduction into the solvent results in the destruction of the solid-vacuum (or solid-air)
interface and the creation of a solid-solvent interface. To this point, the experiment it
similar to a normal heat of immersion procedure. However, as dissolution proceeds,
the solid-solvent interface eventually disappears completely and the net result - as
regards the history of the solid - is the complete destruction of both the original solid-
vacuum interface and the intermediate solid-solvent interfaces. With the solvent, the
total history involves the change in the solvent surface tension resulting from the change
in composition. By comparing results of heat of solution determinations that differ
only in the surface area of the initial solid, one may then determine the solid surface
energy from the original solid surface areas, the temperature changes in the solvent,
and the accompanying change in solvent surface tension.

The situation is slightly different in most experimental arrangements employed

for dissolution experiments. Here it is often more convenient to use a saturated solu-
tion of the solid under investigation, to which are added additional solids of known
particle-size distribution. The changes in particle-size distribution (the larger par-
ticles grow at the expense of the smaller) is then used to determine the solid surface
energy. It should be noted, of course, that neither experiment takes specifically into
account the variation in surface energy expected with particle size; such size depend-
ence is averaged out. * Similarly, no account can be made for the presence of surface
inhomogeneities, asperities, and the like.

IV-4. The Interpretation of Experimental Data

In the preceding discussion, various experimental techniques have been described

that are suggested as means to measure the surface energy of ceramic materials.
Whether these do, in fact, result in a true measure of the intrinsic surface energy of
a material will generally depend upon a number of factors, some of which are
environment-controlled and others that are specimen-controlled.

IV-4. 1. Adsorbate Effects

Specifically, it has been shown, in the discussion of the effects of atmosphere

on the measured surface energy of mica, that the presence of various adsorbates will
result in different, though equally reliable, values of surface energy. Where experi-
ments can be performed in selected atmospheres, it is desirable that one choose, a«
an added independent variable, varying pressures of adsorbates. It is then expected
that a plot of measured surface energy as a function of adsorbate pressure should pro-
duce an extrapolated value that is independent of the interaction between the solid
•Balk and Ben$on(63) have shown that (he determination of surface enthalpy of KC1 by dissolution techniques yields values that
are not strongly dependent on original particle size, at least for particles greater than 500 A in diameter. Their experiments
showed that the heat of solution (AH, cal per mole) and the specific area (A. m2 per g), could be related by the simple
equation
AH » 4200 -4.2 A
for 0 < A < 60m2 per g. See also Section tV-4.3.

I
 36

surface and the particular gaseous species. Furthermore, such controlled experi-
ments can provide a measure of the different contributions to the total surface energy
of the subject material.

IV-4. 2. Liquid-Solid Inter facial Effects

As a further example of the effect of various liquids on the measured value of

surface energy, we considered heat of immersion studies of a number of different ma-
terials. The surface energies determined by such methods are assembled in Table 2.

TABLE 2. PARTIAL SURFACE ENERGIES OF VARIOUS SOLIDS

IMMERSED IN DIFFERENT LIQUIDS*61» 64)

Liquid Employed J
Solid Chemical Formula Water Ethanol n-Heptane Benzene
*
a-alumina A1203 693 -- 151 -- *

Amorphous A1203 454 — 85 --

alumina
Kaolinite Al203-2Si02-2H20 292-352 155 52-89 --
1
Pyrophylite Al203-4Si02H20 348 154 97-105 -- !
Barite BaS04 490 -- -- 140
!
Graphite C 48 -- 122.5 225 .<

Calcium —• 226-284 133-150 71-77 --

Montmorillonite <*
Sodium -- 219-296 137 59-76 --
Montmorillonite <
Silica Si02 210 -- -- 218
(amorphous)
Aerosil Si02 165 -- 118 --
ß -quartz sio2 847 -- -- --
Zirconia ZrOz 600 -- -- 190

As is obvious from the Table, the partial surface energy determined by immer-
sion techniques is markedly dependent upon the particular liquid chosen. The ob-
served trends can be understood qualitatively by reference to the chemical structure
of the liquids employed, as shown in Figure 12. It will be recalled from earlier dis-
cussions that the interaction between like species was expected to consist of similar
terms in the expression for the total surface energy or surface tension. Furthermore,
J
37

it is shown in the evaluation of the Guggenheim integrals**6» *8, 60) that the interaction
r between two different materials will increase as they become more nearly alike.
i

H H
a. Water H M b. Ethanol
I I
H— C-C-OH
I I
H H
H
c. Benzene H H d. n-Heptane H H H H K H H
I I I I ! I I
H-C-C-C-C-C-C-C—H
I I I I I I I I I
H H H H H H H
H I H
H

FIGURE 12. STRUCTURES OF LIQUIDS USED FOR IMMERSION STUDIES

Asa further example of the manner in which the heat of immersion is influenced
by the choice of liquid, refer to the data shown in Table 3, where the heats of immer-
sion of rutile (Ti02) are listed for various liquids. The data, taken from
Zettlemoyer^1) have been obtained at 25 C with fine particles (5. 8 m2 per g, or a
particle size of approximately 0. 24 fj). The effect of the liquid molecular structure is
pronounced.

TABLE 3. HEATS OF IMMERSION OF RUTILE IN

VARIOUS LIQUIDS*61*

Heat of Immersion,
Liquid Formula dynes per cm

n - Nitropr opane CH3CH2CH2N02 664

n- Butyl aldehyde CH3CH2CH2CHO 556
Water H20 550
Butyric acid CH3CH2CH2COOH 506
n- Butyl chloride CH3(CH2)2CH2C1 502
n-Amyl alcohol CH3(CH2)3CH2OH 413
n-Butyl alcohol CH3(CH2)2CH2OH 410
Ethyl alcohol CH3CH2OH 397
n-Butyl iodide CH3(CH2)2CH2I 395
n-Butylamine CH3(CH2)2CH2NH2 330
Heptane CH3(CH2)5CH3 144
Octane CH3(CH2)6CH3 140
Hexane CH^CH2)4CH3 135

I
 38

These concepts will help to provide a degree of understanding to the general list of
values of surface energy given in Section VI. In those materials that contain water
molecules in their structure (for example, kaolinite, pyrophylite and the montmoril-
ionites), the interaction with water is considerably greater than that with ethanol or n-
heptane; that is, the use of water appears to measure a greater contribution to the total
surface energy. Similarly, the presence of (OH) groups in ethanol suggests, at least
pictorially chemical similarities and, hence, would measure a greater partial contri-
bution to the total surface energy.

The strong interaction between graphite and benzene (Table 2) is quite obviously
a consequence of the similarity in structure.

In spite of the apparent simplicity of this argument and the qualitative assertions
which can be drawn, particular care must be exercised in attempting to infer too much
from this approach. As the liquids and solids become more similar, there is a greater
tendency for solution, diffusion, compound formation, and the like, and the initial
prerequisites for determining surface energy are sacrificed. Materials which dissolve
in water or show strong tendencies toward hydration would normally be expected to
interact with water to a greater degree and the measured heat of immersion may then
have little relation to the actual surface energy.

IV-4.3 Particle-Size Effects

Throughout much of the discussion, it has been sufficient to consider the surface
energy of semi-infinite materials, recognizing only that difference from bulk structure
which might occur at or near the surface. One should note, however, that the energy of
the surface of a fine particle (which may have a large surface/bulk ratio) is not necessarily|
the same as the semi-infinite surface. DeBruyn(65) discussed the effects of the radius
of curvature on the surface tension of liquids, and Hirschfelder et al. (66) calculated in
detail the variation of liquid surface tension with droplet size. It has been shown that
the surface tension may be expressed as

2*o
oo-

*t--J- k__ 1 dr (45)

1 +
r
I +
^m}
where

7 = surface tension for a semi-infinite specimen

z0 = depth of "surface layer",
ar^ r = radius of curvature.

It is implied that z0 is independent of r in this calculation, which is not necessarily

accurate. Care should be taken in the strict application of Equation (45) at large values
of z0/r. For small z0/r, Equation (45) may be approximated as
 39
2z,
JL.i. (46)

which is sufficiently accurate for qualitative interpretations. Figure 13 shows the

effect of particle drop size on the surface tension of liquids as calculated from Equa-
tion (45).

FIGURE 13. CALCULATED EFFECT OF PARTICLE SIZE ON THE

SURFACE TENSION OF A LIQUID

The relation between liquid drop size and surface tension may be carried to con-
sideration of similar effects in solid particles. Such dependence is inferred in the ex-
periments on solubility of fine particles and also applies to variations in the surface
energies of semi-infinite solids with small, but finite, asperities on the surface. The
small radii of curvature of such asperities provide a locus of different surface energy
on a material prepared by lapping or cutting. Furthermore, the size effect is one of
the major driving forces in scratch-smoothing experiments, which are designed to mea-
sure either the surface energy or surface diffusion coefficients, as well as sintering
rates. Hence, one should be concerned about the effect of particle size in the inter-
pretation of surface energy experiments. It should also be seen that surface texture is
expected to be significant in contact angle observations, a point reviewed by Marian^?).

IV-4.4. Grain-Size Effects

The next point to be considered is the influence of grain size on the measured
value assumed to be the surface energy. The data on grain-size dependence are rather
sparse, with the major effort having been directed toward AI2O3 and MgO, as shown
in Figure 14. For the most part, the data suggest that measured surface energy in-
creases with increasing grain size, although single crystal values are on the order of
1000 to 2000 dynes per cm for both alumina and magnesia. The above emphasis on
 40

"measured" values clearly illustrates the importance of proper interpretation of experi-

mental results. The total energy required to effect fracture is divided among several
simultaneous events including transgranular and intergranular fracture, grain-boundary
sliding, dislocation maneuverability, crack branching, and similar perturbing influ-
ences. It is thus expected that polycrystalline material would show higher apparent
surface energies than single crystal specimens.

20 40 60 SO 100 120 140 160

Grain Size, ft

FIGURE 14. MEASURED SURFACE ENERGIES AS A FUNCTION OF

GRAIN SIZE FOR Al203<68^ and MgO<69>

The explanation of the trends as a function of grain size is not quite so straight-
forward. It is suggested that grain-boundary sliding effects would require less total
energy dissipation in those cases where grain boundary densities are high (small
grain side). Furthermore, more random crystallite distribution would be expected to
provide easier paths for stress relief; hence, less energy is required to propagate a
crack. In view of the complex analysis which is required to resolve the many questions
associated with surface energy determinations on polycrystalline masses, it is sug-
gested that the most meaningful data which is amenable to detailed studies will be ob-
tained on single crystal specimens.
 41

V. THEORETICAL CALCULATIONS

For the most part, earlier attempts to calculate surface energy of solids were
channeled along three approaches. First, several authors went into great detail in the
calculation and summation of the interaction forces between atoms and molecules in
various crystal structures and developed elegant, though complicated, methods to evalu-
ate the lattice sums and integrals involved. Second, there are semiempirical calcula-
tions based upon gross observables, with the inclusion of factors related to general
thermodynamic principles and suitable averages to account for crystalline orientation
effects. And third, there are estimates of surface energy based upon extrapolation and
correlation of various data on other physical properties, such as characteristic tem-
peratures, mechanical properties, diffusion coefficients, and the like. To re-derive the
fundamental relationships that have been proposed in detail would lead us somewhat past
the scope of the report and would require considerable space in background and support-
ing data. It is deemed sufficient, at this point, to bring out some of the highlights of
different treatments and refer the reader to original sources for whatever minutiae of
detail is desired.

For each area, one of the more important contributions to the field will be con-
sidered in order to orient the reader and set the stage for later discussions. It is not
this reviewer's intention to imply that these papers are the most nearly complete,
definitive, or all-inclusive of the many available (some of which are referenced in the
text). Furthermore, it should be understood tlizt heavy reference to any one of these
three does not necessarily "endorse" the methods or conclusions of the individual
authors; the discussion which follows merely illustrates the usage of the different
methods and can provide some clue as to the degree to which such approaches are
profitable.

V-l. The Atomistic Approach

By far the most exhaustive work on the calculation, from first principles, of the
surface energy of solids was carried out by Benson and coworkers in a series of articles
culminating with the definitive review recently publishedUS). For the most part,
Benson's work considered only the solid noble gases and NaCl-type crystals, although
many of the principles evoked concern other systems as well, including the treatments
of defect structures and the effects of impurities, anisotropies, inhomogeneities, physi-
cal defects, nonstoichiometry, and the like. (This is not to infer that the extension to
include these other variables is straightforward and/or easy; the calculations are ex-
ceedingly complex, but the work of Benson sheds considerable light on the use of the
method.) Benson includes, in the review paper, not only a compilation of his own work,
but also a detailed discussion of the contributions made by other researchers, including
the early work of Born and the later computations of Lennard-Jones and Dent*™),
Shuttleworth^«', Huggins and Mayer(7D, and Nicolson(49)t Comparisons of the calcu-
lated results of a number of contributors have been presented in concise form by
Zadumkin and Khulamkhanov^72), with additional discussion by Walton^)

To compute the surface energy of a crystal, it is necessary to define the inter-

action potential between a pair of particles, i and ;, separated by a distance, rj:.
 42

Usually the total interaction must be considered as a sum of contributions from various
types of forces, with the final expression containing characteristic constants that can
be evaluated from other parameters such as compressibility, lattice spacing, etc.

The simplest interaction potential, 0^, used for the rare-gas crystals takes the
Lennard-Jones form:

*ij = *<rij> = c12ri"j12 "V? • (47)

where the c's are adjustable coefficients. Early calculations on the NaCl-type crystals,
recognizing the highly ionic character of the bond, used the coulombic and an unspecified
inverse nth-power to express the potential, yielding:

A.. = e:e. r"1 + br"n , (48)

where the e's represent electrostatic charge and b is an adjustable constant. Refine-
ments were made to account for possible differences in interaction between (+, +), (-, -),
and (+, -) charges on the ions.

A less approximate potential form,

*?j = e'ei ri/ ■ CL6) rÜ6 * cif ri/ + b'i exp ( r /p)
" iJ ' (49)

has been used which includes not only the coulomb and exponential repulsion forces, but
also the interactions due to dipole-dipole and dipole-quadrupole effects^» '*'.

In addition, ions at or near the surface of a crystal are subject to a finite electric
field that arises from the loss of bulk crystal symmetry at the surface. The total
potential energy for surface ions with dipole moments u,{ and ß: will then be a modified
form of Equation (49), namely:

*ij ■ *?j - «i<?ij • M>? + •,<?„ • tyr J-«?„ • Ä» <?ij • ft'? + <S • ftri? ' (50)

Benson also notes that the total interaction energy is found by summing <£- over all pairs
and adding an "elastic energy", jui /?&i, where ai is the ionic polarizability.

The results of Benson, et a)., are found to depend largely upon the values chosen
for various parameters of the bulk materials. In principle, it is possible to compute
the surface energy of a particular material from the above expressions for the potential
and the appropriate lattice sums. In addition, independent expressions containing the
same coefficients may be derived for other characteristic physical properties of the
materials under study. It is thereby possible to use readily measured or derived quan-
tities (such as polar izability, modulus, sound velocity, etc.) to provide numerical values
for the coefficients, and then to determine surface energy, which is not so easily
measured,

A point stressed by Benson that is borne out by recent interpretations of LEED

data^*M), ^8 that the surface structure of a perfect crystal in vacuum is different from
that envisaged on a parallel plane in the bulk of the crystal. The discussion of this point
considers the atomic processes which accompany perfect cleavage along a given plane.
I
I If it is assumed that at the instant of fracture two new surfaces are formed, each having
T the same arrangement as in the bulk, then an amount of energy 7*0 is required. How-
f ever, a spontaneous relaxation occurs on the new surfaces, which contributes to a de-
«ft
crease in the surface energy. The resultant surface energy at absolute zero is then
conveniently expressed as
•y» = 7«0 + A78 j (51)

where the two terms correspond to the two steps outlined. A78 is, of course, a relaxa-
tion term and is negative in value. The Ay8 term is computed much like 7 , taking
into account the different displacements of positive and negative ions at or near the
surface.

One important point regarding surface distortion should be noted here. Benson
assumed that the lattice distorts only in a direction normal to the bulk crystal, that is,
the lateral spacing of the surface layer is no different from that in the bulk and the sur-
face crystal plane has the same configuration as the corresponding bulk plane. Along
the normal to this plane, ions of different sign are in slightly distorted positions, and
the degree of distortion decreases with increasing depth into the bulk. This is essen-
tially the same picture discussed by WeyP '*' in studies of adherence to MgO, where it
is assumed that 0~~ ions protrude further from the nominal (100) plane than do the
Mg++ ions, producing a permanent surface dipole.

On the other hand, Fowkes''"' allowed both normal and lateral displacements
(this has been partially confirmed by LEED studies). However, Fowkes' treatment is
almost entirely confined to a thermodynamic and phenomenological approach, so that
the exact details of surface structure are irrelevant; it is only necessary to state that
the structure is different.

The magnitude and importance of the surface distortion effect can be seen from
the values of 78 7 , and £7*, taken from Benson and Yun's review* *°' and listed for
the (100) and (110) faces of the alkali halides in Table 4.

Benson's steps to include surface distortions are certainly in the right direction.
The numerical calculations suggest that distortion must be considered to arrive at
reasonable values of surface energy. While the treatment is incomplete, the essential
features of the computations appear to suggest additional effort in this area. It is now
necessary to extend the calculations to models which include lateral displacements (that
is, a three-, rather than one-dimensional density change). It is anticipated that the
proper interpretation of LEED data on clean surfaces will provide considerable impetus
to these studies. It is important to note, moreover, that the positioning of stress or
ions on the surface is not the only factor relating to the accuracy of the calculation.
Benson and Yun(18) showed how the particular choice of interaction potential can effect
final results markedly, and the need for a more thorough study of this aspect of the
calculations is certainly indicated.

All of the above discussion centered about the problem of computing the surface
energy at 0 K. For experimental results to compare better with theory, it has been
necessary to extend these studies to finite temperatures. It is generally stated that the
surface energy at any temperature may be expressed as a sum

T<T» " >pot + 7

vib • <">
 44

where the potential energy term, 7pot> depends only on the bulk characteristics and
corresponds to the static lattice energy, while the second term, 7vjk, is an explicitly
temperature-dependent contribution. There is, of course, an implicit dependence of
Tpot on T Decau8e °* tne changing lattice parameter, so that we should write

y'w ■ y8o+ (-dT **+ ^ib^T> (53)

where the lattice parameter is denoted by a and 7« is defined previously [Equation (51)],
Naturally, the contributions from the zero-point energy should be included, although
these were omitted earlier.

TABLE 4. THEORETICAL SURFACE ENERGIES OF ALKALI HALIDE

CRYSTALS AT 0 K

(100) Face (110) Face

-ySO a 7s0 A78
A7 >S ?8
CsBr _- -- -- 234.4 -34.8 200
CsCl -- -- -- 256.6 -37.7 219
CsF 211.2 -63.6 148 436.9 -96.1 341
Csl -- -- -- 207.1 -31.9 175
KbR 159.2 -36.4 123 326.5 -64.8 262
KC1 175.3 -34.0 141 367.3 -69.6 298
KF 225.9 -41.9 184 528.0 -105.2 423
KI 140.8 -27.7 113 279.1 -57.6 222
LiBr 226.2 -140.5 86 515.1 -234.8 280
LiCl 251.4 - 44.7 107 599.2 -259.1 340
LiF 288.7 -146.4 142 962.3 -394.6 568
Lil 199.8 -126.4 73 424.6 -198.3 226
NaBr 192.2 -54.0 138 413.4 -109.2 304
NaCl 210.9 -52.7 158 469.7 -115.6 354
NaF 265.9 -49.5 216 711.7 -156.4 555
Nal 170.5 -52.5 118 348.8 -97.3 252
RbBr 150.5 -28.5 122 300.9 -55.3 246
RbCl 166.0 -28.4 138 337.3 -60.0 277
RbF 213.1 -42.3 171 473.2 -92.9 380
Rbl 133.4 -29.8 104 259.0 -48.9 210

The vibrational energy term can best be computed by considering appropriate inte-
grations or summations over the allowed vibrational states, and the calculations proceed
with appropriate Debye weighting factors. The Benson calculations for some of the
alkali halides and MgO were carried to 298 K for better comparison with experiment.
A few of these results are somewhat tenuous, even allowing for approximation, because
either surface distortion or lattice expansion factors were omitted. This will be dis-
cussed again in Section VI.

Previous discussion has alluded to the difference between surface energy and sur-
face tension. The most detailed calculations of these differences have been reviewed by
Benson and Yun^**). xhe calculations will not be repeated here, but it is worthwhile
f
45
I including, however, a comparison between the estimates given by various authors. As
r in the case of surface energy, there is a "bulk" contribution (T") to surface tension and
i
a correction (AT) due to surface relaxation. The resulting values of fO. AT and
r = rO-ATare compared in Table 5, along with the surface energy 7 g as computed by
Benson and Yun^^

TABLE 5. SURFACE TENSIONS (D AND ENERGIES (7) CALCULATED

FOR ALKALI HALIDES AT 0 K

Shuttleworth(6), Nicolson(48),
(110)face, (100) face (100)face lenson k Yun(18), (100) face
e
r T* Ar f r r° Ar r 7^
CsF 308 497 -126 371 341
KBr 442 341 -842 -501 250 330 -101 229 262
KC1 521 404 -779 -375 310 389 -125 264 298
KF 884 719 -929 -210 549 718 -223 495 423
KI 354 269 -581 -312 172 262 -71 191 222
LiBr .. 827 786 -195 591 280
LiCl -- -- -- -- 1025 948 -324 624 340
LiF -- -- -- -- 2287 1978 -1484 494 568
Lil -- -- -- -- 558 609 -63 546 226
NaBr 646 534 -868 -334 454 499 -113 386 304
NaCl 776 641 -771 -130 562 593 -155 438 354
NaF 1443 1214 -1034 180 1031 1149 -408 741 555
Nal 505 419 -724 -305 303 395 -54 341 252
RbBr -- -- -- -- 204 282 -90 192 246
RbCl -- -- .- -- 248 331 -109 222 277
RbF -- -- -- -- 427 600 -173 427 380
Rbl -- 142 225 -49 176 210

V-2. Semi-Quantitative Structural and Thermodynamic Considerations

The detailed calculations outlined above can provide reasonably good estimates of
the surface energies of a multitude of compounds covering a wide range of variables.
In fact, there appears to be no limit to the extent of applicability of the method; given
sufficient information (from experiments) and time for such calculations, the surface
energies of all materials should be calculable, including ceramics, metals, organic
compounds, etc. The major factor determining the accuracy of the calculations seems
to be in the choice of potential functions and the constants associated with them. As
stressed before, it is reasonable to assume that many different materials parameters
can be computed and their experimental values can be used to adjust the necessary con-
stants, thus giving credence to the computed values of surface energy.

1
 46

While, in principle, the above technique should suffice for all applications, the
calculations are quite time-consuming and a more direct, though perhaps less accurate,
method might be preferred, especially for "quick guesses". There are semi-empirical
methods that provide reasonable values of surface energy but which involve much
simpler calculation. The methods, essentially due to Bruce (53^ circumvent the detail
of Benson but include, practically from the outset, a direct relationship between the
surface energy and the other measurable parameters that are eventually required for
the Benson approach.

The reasoning behind the Bruce approach is not particularly well defined, but many
of the results are sufficiently accurate to merit considerations. At the outset, several
basic definitions and boundary conditions must be stated.

The surface energy, y 8, and surface enthalpy, £8, are usually related through
d-
Y8
e.**y. -T-Jf • <54)

Bruce points out that as T -* 0 K, d7/dT vanishes, so that e- = yat the total surface
energy at 0 K, which can be computed by the methods of Benson. Inasmuch as the sur-
face energy (or surface tension) vanishes at the critical temperature, Tc (where the
liquid-vapor separation is indistinguishable), it then follows that

■w—c--c • (55)

It has also been found that the surface tension of a liquid at a temperature between the
melting point and the critical temperature may be expressed as

1 £ = k(l-T/Tc)n , (56)

with k and n as constants. [Further applications of Equation (56) will be considered

again later. ] If the effect of melting upon the surface energy is known, it should be
possible to compute surface energy and surface tension at all temperatures, from
absolute zero to Tc over both liquid and solid phases.

Bruce takes the point of view that the surface free energy can be described in
terms of the bonding of atoms and that when energy is supplied to effect such breakage
between two atoms, one half goes to each atom. Therefore, the bond energy, ß, is taken
to be

ß = Hf/2cN , (57)

where H8 = molar heat of sublimation (ergs/mole), c is the number of bonds per mole-
cule, and N is Avagadro's number. If b represents the number of bonds per cm2 of the
particular crystal face, then the total surface energy is

7=ßb (58)

b can be determined from inspection of the surface lattice. We note that a perfect sur-
face, similar in configuration to the bulk lattice, is assumed from these estimates. For
the most part, this restriction is no more stringent than the assumptions regarding the
initial calculation of y®.
 ,*3f '- rP..^*v?;-1 #fi«e*"

47

Bruce now takes the point of view that Equations (54), (57), and (58) may be applied
to the estimation of surface energy in the solid and that Equation (56) applies to the
liquid. At the melting point, the latent heat of fusion (Hf) will contribute to a decrease
in surface energy in the amount

-A7 = T)Hf/AN , (59)

where A is the surface area of a molecule and the parameter, 7), is the ratio of free
bonds to normal coordinate bonds in this surface.

It is now possible, in principle, to estimate surface energies over a wide tempera-

ture range, given the appropriate heats of sublimation and fusion. More precisely, the
following "recipes" apply to a given system:

(a) 7° = H8b/2cN T = 0 K

T
(b)
>J=^-ö!) Tm > T > 0

(60
m m
(c) 7g - 7* = - A7 = T)Hf/AN T = Tm

(d) 7L = Ml - T/Tc)n T >T>T

c m

where

b = number of bonds per cm^ of the plane considered

c = number of bonds per molecule
A = surface area of a molecule
7] = ratio of free bonds to normal coordinate bonds
n s adjustable exponent, about 1.2.
i
The constant k can be evaluated by equating Steps (c) and (d) at T = Tm and, using the
definitions of Steps (a) and (b), may be written as:

H.b U-Tm/Tc) - (2T)c/bA)Hf/H8

k =—
2Nc
r (61)
» - Tm/Tc)n

Note that the factor b contains the lattice parameter at T = 0 K, while A contains a
similar contribution from the lattice parameter at T = Tm.

Inasmuch as critical temperatures are unknown for many materials, Bruce pointed
out that the ratio of critical temperature to boiling point, Tc/Tb, is approximately equal
for different classes of oxides: for MO, Tc/Tb s 1. 52; for M02, Tc/Tb * 1. 50; and for
M2O3, Tc/Tb * 1.40. No other such correlations have been noted thus far.

Comparisons of Bruce's data with previous work suggest that while agreements do
I not support the technique without qualification, the order-of-magnitude results indicate
that as a rough approximation, the methods can be applied to a broad range of materials.

I
I
 48

Bruce further considers the effect of crystallographic orientation on the surface

energy of different crystal classes. Quoting Friedel et al.' ''\ the surface energy of a
given (h, k, t) plane is a function of h, k, and i, the bond strength, ß, and lattice
parameter, aQ, such that, for different crystal systems, we have:

7(hk£) = = ^V^'n/i (simple cubic) (62)

a§ (h2 + k2 + iz)llZ

^.i^o\ =
7,hkl) (2h + k) ß (face-centered 63).
4 ö?; k2; fcni «bio <
2[2hj3i + (h + k+ i)ßy]
7(hki)= h
"Vl 2 ,2 1/2 ><k+4>
aQ (h + k + I )
(body-centered ., *
cubic)
2(h + k+ $)(ßiA + M
7<hk£) = —^ / h < (k + I)
a2 (h2 + k2 + I2)1'2

The 7's are surface energies near 0 K, and ßj and ß2 refer to bond strengths between
nearest and next-nearest neighbors, respectively. The equations apply when
h>k>$>0.

It can be readily seen that, for the simple cubic systems, (100) is the lowest sur-
face energy, and we can then define vhe ratio

K{hki} (65)
' 7d00) ~ (h2 + k2 + £2}l/2

which is independent of ß and aQ. It is interesting to note from these expressions that
the surface energy varies around a stereographic projection (lattice projection Figure 15)
in the manner shown in Figure 16, where contours of constant surface enetgy (at 0 K)
are drawn. Thus the surface energies at (Hi), (110), and (100) planes are in the ratio
>fy. *J~2: 1, as expected from the simple bond considerations.

Similarly, stereographic projections can be prepared for other crystal structures,

that for the face-centered cubic being shown in Figure 17. Note that surface energy is
a minimum on the (111) plane, and the indices of Figure 17 refer to the rttio
7(hki)/7UH).

The projections are not quite so simple fot the body-centered cubic structure, the
added complication arising from the different bond strengths needed to describe the
surface energy. Letting ß\l ßz = r, we can rewrite Equation (65) to the form

D/..n (2r + 1) h + k + I . , ^ ,. . tx
R(hkl) = r TTT> *or h > (k + £)
2(h + k2 f l2)l/2(r +1)
2

(66)
R(hkl) = ±llLLL. ior h < (k + I)
Jl (h + k ♦ fi)llZ
2 2
 i
. vrnf»..!!*.-«-!*

I
49
I
I lOlOMiO — N — —
o — — — <\j — IOCM lO^N
o oooo o o o oo
1 I I I I
105
103 tit II
102
203 41« W • tt
» « ll»
>t4
•
,Tl
tS2 .
«At j
101 . . • •«!
BIB 313 tit #
»12

302 614 «•
201 •?3 •♦'«
301
401
701

100

FIGURE 15. THE POSITIVE QUADRANT OF A STEREOGRAPHIC PROJECTION

OF A CUBIC CRYSTAL WITH SOME PLANES INDICATED BY
THEIR MILLER INDICES^53)

? 8

FIGURE 16. THE SURFACE ENERGY RATIOS FOR THK SIMPLE CUBIC
SYSTEM PLOTTED ON A STEREOGRAPHIC
PROJECTION^)
 50

FIGURE 17. THE SURFACIVENERGY RATIOS FOR THE FACE-CENTERED

CUB:C SYSTEM PLOTTED ON ASTEREOGRAPHIC
PROJECTION*53 >

tit

FIGURE 18. THE SURFACE-ENERGY RATIOS FOR A BODY-CENTERED

CUBIC MATERIAL (a-FeJ PLOTTED ON A STEREO-
GRAPHIC PROJECTION*")
 SI

The (110) plane represents the minimum surface energy and all R(hW» are referred to
this plane in the projection of Figure 18. For h > k ♦ ?. R'hk-J :s independent of the
ratio, », and these areas appear in the .hree corners' of the projection. However, the
center portion where h < k ♦ t shows the effects of the differing bond strengths and pro-
duces "saddle lines " in the projection.

It it also expected that the ratios R{hk/) will be time-dependent for T > 0 K, since
a mass arrangement should result from surface diffusion and, in effect, faceting. Such
faceting effects proceed in the direction that produces the greatest density of low-energy
surfaces. It is the very existence of ratios Rlhk/) > 1, that acts as the driving force for
this diffusion. Similarly, differences in surface energy, coupled with 'he high energies
associated with cusps and other surface irregularities, provides the driving force for
sintering or agglommeration.

The nature of the effect of temperature on surface energy cf cations can be esti-
mated is follows. Although surface diffusion and faceting is expected at all tempera-
tures, there is a "threshold" temperature below which such mass motion is essentially
arrested and above which sintering and similar reactions proceed at s measurable rate.
This point is referred to as the "Timmin" temperature, Tj, and, for many oxides, is
reported to range from 0. 5 to 0.6 Tm. This value can vary over relatively wide tem-
perature ranges. The Ty has no theoretical basis, being purely an empirical reference
point, but it i» sufficiently accurate to form the basis of reasonable speculations.

The rate of changt of R(hk/) should be exponential with time for any given tem-
perature, tending to unity in infinite time, so that

sty s 1 ♦ be"** lerTl

where b and ! are merely constants for a particular material. Inasmuch as the rate
should be infinitely slow for T < Ty (for simplicity, • •• assume thai Ry is constant for
T < Tj, so that no significant surface diffusion and faceting -»rcurs below the threshold
temperature) and is infinitely fast at the melting point (where the .*r»sotropies in surface
energy varied), we may then approximate

Since Ry = RQ at t = 0, we may differentiate Equation (66) and substitute from Equa

tion (68) to eliminate the factor b, whence

-k(T-TT)t
ty = 1 ♦ (RQ-l)exp
<R0-r<rm-T>

Assuming a standard diffusion character to the mass motion we may let k Dk r

Dge" ' k '" r . where DQ is the diffusion coefficient; k is a statistics' weight ng
factor £, the activation energy for diffusion, and r, the particle size. Taking reason-
able figures for the . i-ioui factors in Equation (66), Bruce computed the change in the
ratio of surface energy to time for various particle sizes.
 s?

The result« of this < omputation illustrates the nature of the changing dr.vmg
forces for surface reactions and some of the rate-controlling constants that effect
reactions.

Before leaving this section, two points deserve further mention because cf their
potential applicability in studies of surface energies and solid surface cotnpatib;lity.
First, in previous sections we suggested the possible use cf surface-tension versus
contact-&ngle measurements for the determination of critical surface tension? and,
hence, »olid surface energies, following the Ztsrran and Eberhart methods. Then, in
the discussion of Bruce'« work, we have come across the relation between surface
tension of a liquid and its temper «cure dependence, as mentioned in Equation (56). It
is therefore worthwhile a. tuts po<nt to digress to a short testification of the value of
the exponent, n, in that equation.

Mitra and Sanyal'*** showed that the vapor pressure and surface tension of liquids
may be related through

/u\ 2/3
Tl»P=-*7L (^3J ♦* 169»

where p = vapor pressure

*L = surface tens*on
T = absolute te.nperature
D, d = densities of liquid and vapor, respectively
M = molecular weight
a,b = adjustab'; constants

i 78)
It has also been shown1 that the surface tension and density are related by

,L = C(D-d)4 «701

where C is a constant. Using Equrtion 170) to eliminate (D-d) in Equation (t>9) yields

T In p ♦ a,LVb = b (71)

where the factor oi M has been absorbed in the constants. By substituting from the
integrated Clausius -Clapeyron equation

In p = C * d/T , (72»

1 in p ran be dominated, which leaves

>L5/b : A -BT (731

From this, it follow« that elation <56>, with an exponent of 1.2, is based on
better than purely empirical observatu "»•. These relations will be important 'o mea-
surements of critical surface tension over a wide range of temperature«. Further
considerations of the relations among liquid suriu^e tension, heats of vaporization ami
temperature have been forwarded by Bowden'"' and !•»* results can provide good
estimates of this difficultly measured parameter.
 53

The second point which should be mentioned here relate« to the charge ic surface
tension that occurs upon melting or solidification (as well as in other charges of stat«»}.

The Sharpe and Schonho-n*l *' analysis of the thermodynamics of wetting, spread-
ing, and adhesion showed that wetting is not a reciprocal process; that is, if material A
will wet material Ef then B will not wet A, and conversely. For ex mple, to produce
good adhesive bonds between polyethylene at i epoxy resins, it is necessary to set the
epoxy at its curing temperature, and then heat polyethylene to the softening point t;i order
to promote adhesion 4since the liquid epoxy will not wet the solid polyethylene}. In the
Sharpe and Schonhorn analysis, it is implicitly assumed that wetting in any solid-liquid
system could be effected (if necessary) by interchanging the roles of the solid and liquid
at a given temperature, but this is obviously impossible m all but the most specialised
applicatiors. Even given such a situation, their analysis presumes that the surface
energy on curing does not change significantly. The earlier discussion on the contribu-
tion to surface energy made by Jie term at the melting point tends to overrule a strict
application cf the Sharpe and Schonhorn approach, and cautions against the indiscriminate
use of their conclusions. This is particularly important in consideration of the role of
surface energy differences when designing experiments to overcome intrinsic difficulties
in promoting adhesion between dissimilar materials.

These observations are of great importance where attempts to achieve strong

bonds between materials use deposition techniques to effect contact. Here we have a
case where "solidification after contact" is carried out, rather than the mating of two
solid materials. It should be recognized that »he change m surface energ/ of the solidi-
fying material might promote thermodynamic instabilities at the interfaces and the
particular components might net adhere to each other well without the use of an inter-
mediate phase.

V-3. Correlation Techniques

Several authors have attempted to calculate the s ud surface energy of various

solids through the use of correlations with other physical parameters. Quite often,
these aie based more on qualitative observations tnan on fundamental scientific investi-
gations. However, it should he pointed out that this is not a criticism of the use of such
techniques, inasmuch a* the study of solid surface energies needs assistance wherever
it car be found.

Considerable work has been done on the surface tensions of liquid metals and
correlations with other physical observables. wtb perhap: the most nearly complete
work bein* that of Siuta and Balicki,79>. Similarly, Sikorsky* 80- 8l ) and Courtney-
Pratt*8** have studied solid metais, reporting on the relations between physical proper-
ties and a for»n of practical adhesion. Perhaps the most extensive work with ceramic
systems sterns from the work of Livey and Murray .

Livey and Murray considered the qualitative effects oi lattice energy, surface
polarization, molar volume, heat of formation, diffusion, and other properties on the
solid surface energies of a number of oxides, carbides *nd alkali hahdes. They showed
that while ball lattice energy certainly relates to surface energy (particularly 1:1
 54

elemental materials), there may oe some difficulty in associating bulk and surface
energies in compounds, especially where there are the added effects of lattice distortion
&«td surface "non-stoichiometry '. In addition, polarisation effects at the surface add a
new dimension to the computations, as shown earlier by Benson et al.d**; simple
extrapoiatior is not possible.

Furthermore, it is expected that the general rules of correlation should be tem-

pered by the fact that the types of shielding and polarisation effects expected in metal
oxides of the form say, MO, would be different 'rom those found in oxides of the type
MgOj, MO2, etc. Moreover, as one g«>es through a series of "homologous compounds",
intrinsic trends might not be justified as factors of correlation when considered indi-
vidually, and extrapolation must be done carefully within one class of materials.

The results and techniques «f Livey and Murray*®*' are quitv important in that this
is one o the few articles of the correlative type which seems to deal honestly with the
limitations of the empirical methods. Throughout their discussion, it is apparent that
full consideration must be given to the interactions between different types of contribu-
tions to the total surface energy.

Sikorsky ' takes a somewhat different approach in the correlation between

surface energy and mechanical properties of various solids, notably metals. The coef-
ficient of adhesion is taken to be the ratio of the force necessary to pull apart two spec -
mens divided by the force employed in bringing them into intimate contact. In some
cases, it is necessary to effect a twist of the joints in order to break oxide livers,
smooth out asperities, and the like. This coefficient of adhesion is then correlated with
rich factors as hardness, re crystallisation temperature, and associated metallurgical
properties, as well as with liquid surface tensions of the metals. The cross-correlations
then permit the assessment cf surface tension with respect to the mechanical properties
of the solids.

Although such correlations may serve as another method or approach for the esti-
mation of the surface energy of selected solids, it is not felt that there is sufficient
merit in the method to justify extensive use. For example, the use of hardness as an
intrinsic parameter may lead to large discrepancies, since the hardness will depend not
only on the surface characteristics but also on bulk properties of the subject material.
The hardness of a nearly perfect single crysta*. is somewhat different from the hardness
of the same material in the form of a highly worked, polycrystalline mass. Further-
more, the recrystalliaation temperature is expected to be a function of diffutivity,
crystal structure, defect concentration and other intrinsic factors that will also deter-
mine, to a certain extent, the value of surface energy. Consequently, by attempting to
cross-correlate between two uncertain correlations one only multiplies the uncertainty.
(831
Two major factors resulting from researcnes of Bondi should be pointed out
here inasmuch as they contribute to two distinct aspects of the present report the
correlations between surface tension and other physical measurable*, and the use of
"homologous" series of liquids for the determination of solid surface energies. In the
first place, Bondi shows how the surface free-energy density and »he cohesive energy
density may be correlated for a number of different classes of molten specimen!. As
can be seen from Figure 19, the data for these different materials classes is somewhat
incomplete, although more further experiments might extend the range« of applicability
of the Bondi correlation, particularly for the oxides (Class 111). It it most important to
 55

looor

10 >00 ooc
Cohesive Energy Density Porometsi

FIGURE 19. CORRELATION BETWEEN SURFACE FREE ENERGY DENSITY, .Fs, AND
THE COHESIVE ENERGY PARAMETER, lv» FOR VARIOUS TYPES OF
SOLIDS*48*

Surface free energy density is given by Fg - i/vt »

where > it the surface tension and VL it molecular volume.

The cohetive energy density parameter it given by *y = ^vap^VL »

where Evap it the heat of vaporisation

point out, However, that reasonable correlations do indeed exist and even with the limited
data presently available, one may be able to determine order-of-magnitude estimate* of
surface energy for unknown materials.

Secondly, Bonoi collected data on the effects of alloying (in the liquid state) on the
surface tension cf what might be considered a homologous series in the sense defined
earlier. As discussed earlier, it is necessary to establish a series of liquid systems
that do no» interact with a substrate of unknown surface energy in order to define the
critical surface energy for wetting, which is relatable to the solid surface energy. With
such a series, the solid surface energy might be determined under conditions and at
temperatures whs*» mechanical techniques are not valid. Hence, data of the type shown
in Figure 20 can be employed for such determinations.

Naturally, one must be cautious about defining the temperature of the experiments,
for both the «olid surface energy and the surface tension of the liquid mixtures vary with
temperature. Again referring *o Bondi's work, we see. in Figure 2i, the? manner in
which the surface tension can vary with temperature in mixtures. While the form of
the temperature dependence in pu**e liquids has bees« shown to be quite regular (some-
times linear, but believed to be related to the 6/5 power), it is seen from Figure 21 tha*
in mixed systems, the variation can be quite erratic. This is thought to be associated
with eutectic compounds or unique properties cf the selected liquid mixtures. Hence,
one must know in considerate detail the nature of the liquid mixtures before attempting
use them in the deteranitution of solid surface energies. A similar argument must be
*?d in attempting to employ the methods suggested by Rhee*50*, where compound
. r-nation or enhanced diffusion can occur at a particular temperature.
 37

200

0 100 1000
Solute Concentration, m/o

FIGURE 20. CHANGE IN SURFACE TENSION OF FUSED METAL OXIDES BY

ADDITION OF VARIOUS OTHER METAL OXIDES*48*

6
I A 1

i £-2
0 - \

It /
r\,
Curve Symbol System
5 4 m

U
^ \
/ ' ° Bt0s m PbO
SiO, mPtO
/ 2 A
-6 mm
1 / * a ZnO n 8(0) 1

8 1 ^ fiii 1
20 40 60 SO CO Curvet I cmO
10 SO 30 40 Curve 2
Temperature, C

FIGURE Zi. T^MFIRATURE COEFFICIENT, dT/dT, OF THE SURFACE TENSION

OF MIXTURES OF FUSED METAL OXIDES
 Vi. SOLID SURFACE EN£KG!ES

VI- 1. The Surface Energy of Crystalline Solid*

Several aspects of the measurement, interpretation and theory of surface energies

of solid materials have bee'i discussed to provide a framework for understanding the
experimental and theoretical values collected in th« following »Abies. From the outset, it
is well to point out where the major gaps will be encountered, since only relatively fev
materials have been investigated and the understanding of the ptesent data is not uniform.
The following tables list most reported data, including some that mus» obviously be in
error. Erroneous data is included to illustrate the drawbacks of certain experimental
and/or theoretical techniques, but is not meant to be a criticism of the technique as such.
Such an exposition should pro ride a better feel tor the applicability of a given method,
and will suggest areas for more research.

The tables list the values of surface energy (for both liquid and solid, where
applicable i. the temperature of measurement, the method used, the condition of the FT s-
terial, and appropriate remarks. There are a number of gaps in the information, partly
because the description is incomplete in the original source. In many cases, the values
seated by the original authors have not been correlated with other calculat;ons or experi-
ments, and it is difficult to assess the reliability of such results.

The surface energies of most material« have been neither measured, calculated,
nor subjected to much speculation; hence, there is little information on this important
quantity. In addition, while a few techniques have been developed whereby estimates nay
be made by the combination of other physical data, there are two major pitfalls in the
application of such methods: (1) the data for the correlations is not available, or (2) the
correlations are so poorly based that the use of such information can lead to erroneous
results.

Where values of >andd>/dT are available they are included in the table The Bruce1^1
approach has been assumed valid, as w*»il as the relation between surface tensions and
critical temperatures. The critical temperature and multiplicative constant given 4n
Equation (54) have been calculated by the reviewer. It should be noted that the Tc so
determined might not be realistic at all. In many case», it is impossible to measure Tc
or to interpret it in classical terms. For example, where compounds dissociate into
multiple components, the Tc bears little resemblance to the same quantity referred to
with common materials such as water, the noble gases, single-element liquid metals,
etc. Therefore, one should not consider derived vaiues of T as being highly accura:*.
they are included merely for illustration and might bs useful in the determination of a
tew other parameters of the system.

The general character of the tables is such at to present what might at first be con-
sidered a collection cf unrelated data on many difterent substances. In this connection,
it should be pointed out that the purpose of the present report is not only to collect avail-
able data on the surface energies of ceramic son ,s, but also to shea some light on the
relative reliability of different techniques .'bo*' experimental and theoretical) which can be
used in the determination of these values. For many of the materials lisvd in the table,
there is ve y little information to support or refute the quoted values of surface energies;
several individual values must stand alone without benefit of corroboration. l.n other cases
(particularly those of high technical interest, such as alumina, magnesia and th.- like),
 59

* number of investigations have been carried out using a variety of experimental methods
in a variety of materials. It should be obvious, from an inspection of all the data and
the discussion throughout the report, that a large number of vtriioles will contribute to
the measjred values of surfte« energy and that very few research* have been devoted
to a detailed study of these. Lnder these conditions, it woud b* normally expected thit
a variability in results should occur.

For many of the materials reported in the tables, a single value of surface energy
has b-»en singled out as being thought ef as the most reliable available at the present
time. For the most part, however, there is insufficient information available on which
to base such a conclusion, and decisions on "best values" have been postponed until
further significant research has been completed.

L
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 71

root not« »or Tab*- S

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m«thod uttd
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information * «i .(«>•• or wh«f« th« '«««tton to totid turf«ct tn«r fy mifht b« of t«t»cr*t So» #*0 Appondia C.
Tjbtt C 1
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thri fvtffmont hü to* tn« mo»» port. bom mod« by othor mvoitifftorv Th« «btonct of * **»o# to d«t fn#twj #»ou«d
not Off •ntrrpoH«* « moomnf th4t or **t:« ft r«4.*b*«
id) Th« dihodttf «n^ftc m*««ur«mont uv»#My mvoHOS th« fomatry *hr-»n m th« «ccomp«ny»nf f^ur«. m which * from
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not too dnvmiUf from th«t QuObJd m thrt oUtton Of «.our«» tmc« MfO h*i t h.fh«* mottMf point. W mctuwon
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tomp«f«M««
 72

Vi Z. The Surface Energy of GUnci

In the precedi tg tabulation end discussion of the surface energy of solide, we have
purposely omitted ctnside ration of the properties of glasses. At this point, it is well
to coneider some of t>e difficulties that might be expected, not so much in the measure-
ment of surface energy but in the interpretation of experimental results. One basic dif-
ference between glasses and crystalline materials relates m the comparative difficulties
in such measurement and interpretation. For the most part, glasses are elastically
isotropic and, over the temperature range where they are brittle, lend themselves to a
straightforward phenomenological analysis of fracture energies, surface energies, etc.
However, the structure of glass, on an atomic scale, is such that no fundamental calcu-
lations are possible on the basis of atomic arrangements, lattice distortion near the sur-
face, and «kmilar considerations.

On the other hand, while crystalline materials may be investigated rigorously (as
was the case with Benson's theoretical work'181, certain difficulties are encountered in
the analysis of experimental work where crystalline anisotropies must be taken into
account.

Two particular aspects of the surface energies of glasses should be touched upon;
namely, the surface energies of solid glattes and the surface tension of liquid glasses.
The first of these has been covered u» ioi.u detail by the recent work of Wieder horn'
whe included considerable review work alor.g with his recent original findings. This
contribution should be coupled with the paper by Mouldt?), who discussed many details
of the fracture of glass. Inasmuch as these oth* papers are fairly self-contained, we
shall not discuss solid glasses further at this point, but will include, on the following
pages, representative samples of data on various glass systems.

The second point, the surface tensions of liquid glasses, should be mentioned
briefly here, and further reference will be made in the following table. There is a
considerable body of data available on the surface tensions and contact angles of a num-
ber of different glasses, many o- these being mixtures of many (perhaps five or more)
differed compounds, such as SiO^, B2O3, Na£0, P^O^, K^O. In addition, much work
has been done on the surface tension and viscosity of the liquid phases used in enamel-
ing, where these are similarly composed of multiple compounds. Such data can be of
exceeding importance in correlative studies of the surface energies of solids if suffi-
cient «"«liable information is available for these comparisons. One of the mere useful
tools (if it is, indeed, applicable) lies in the use of Bruce's correlations■*** of the
liquid surface tension, the critical temperature, the surface energy at absolute zero and
the temp« iture coefficient of the surface energies of both the liquid and solid state.
The use of this technique depends, of course, on the degree to »hich one can define and
use the critical temperature as a meaningful parameter particularly when applied to a
mixture of liquids and on the availability of reliable da »a on the temperature dependence
of the liquid surface tension

For single liquid oxides, such data can be obtained from the literature (in some
cases) by extrapolation of the results reported for mi*tures, thereby achieving rela-
tively reliable end-point values of surface tensions as a function oc temperature.

The data collected for the surface tensions 01 liquids and their mixtures also has
great applicability in the use of the Z is man- Eber hart technique for determining the
 73

surface energy of selected solids, particularly at temperatures where more "conven-

tion* l" liquids cannot be used.

Table 7 lists the surface energies of various glasses. Surface energy is best
characterised in soda*lime glass, particularly because of the work of Wiederhorn(2S),
who undertook a rather thorough study on the surface energy of it. He investigated, in
some detail, the effects of various atmospheres on crack velocities and acceleration,
using tha relations defined in Equations (27) and (28). The most probable value, as
measured by crack propagation techniques at - i96 C, is given as 3200 dyne per cm, as
measured in a nitrogen atmosphere.
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 7S

VII. CONCLUSIONS

In the text and tablet, we have attempted to summarize t'.ie available information
on the surface energies i>( ceramics, and have found that much research is needed in
order to provide a reasonably defimtve collection of ceramic surface energy dafe

Among the possible routes for advancement in this field, the following are
recom tended:

j\\ Crack propagation experiments. The methods that have been developed and
expanded by Oilman'*01 and Westwood**11 et al. , arc presently applicable to a large
number of materials over a temperature range where th^ specimens are brittle. How-
ever, where a certain degree of plasticity is involved, such as with either mobile or
maneuverable dislocations, the analysis used by these authors breaks down. There are,
quite generally, several different though related factors that must be included in the
interior as to whether brittle fracture occurs, among which one of the more important
is consideration of the dislocation velocity along selected crystallographic planes at a
given temperature. In those cases where the crack tip velocity is much greater than
the dislocation velocity (either «n normal glide or in climb), the material can be con-
sidered brittle and the standard analysis may be used. However, this condition may not
be reached under controlled conditions at higher temperatures. It is then necessary to
either develop inr-owd experimental techniques for effecting high-speed fracture, or
to develop more nearly exact theories of fracture that will accomodate ductile materials.
One must use caution, however, in expending too great an effort at attempting to define
and derive the necessary correction factors, inasmuch as one may rapidly reach the
point where the resultant surface energy is inaccurately determined as a small difference
between large terms.

(2> Thermodynamic interface experiments. It is well to recall the general prob-

lem of the use and interpretation of experiments that rely upon the properties of the solid
surface m question in contact with a different phase or material. Rarlier. the point was
raised that the total surface energy is a summation of contributions from different types
of interactions, i.e., coulombic forces, disp-rsion forces, metallic and ionic bonding,
hydrogen bonding, and the like. Both Weyl and Fowkes have given qualitative arguments
that suggest that, in the interaction between tsj distinct species, each having different
degrees of several of these lomponents. the total interaction «'ill depend only upon the
degree to which similar tompontnts are present. That is to say, if one material has a
surface energy which is totally a result of dispersion and metallic forces and if the other
l» a result of dispersion and ionic forces, then the tofl interaction between these two
v/ould depend *»nly upon *he interaction ef dispersion forces, the remaining contributions
to the surface energy would be unaliected by juxtaposition.

As of the present writing, there has been no di ttnet quantitative argument for-
warded to support this hypothesis. However, one car go somewhat further in the
qualitative analysis by t«insidering a simplified mode* for electronic interactions be-
tween, for example, a metal and a (defect) ceramic. In the case where the metal is
situated in a vacuum, the surface energy will be a total of contributions from dispersion
forces and the metallic bonding forces which Mrt> inherent to the naterial, in addition to
any component deriving from the free (conduction) electrons. The juxtaposition of a
highly insulating material provide» other atoms and'or n>olecules which will interact
via dispersion forces, however, there are no corresponding metallic - for*, e electrons
or conduction electrons «vailable for add:tioi-al interactions and the placement of the
 76

insulator do«« not materially affect the electron cloud distribution» of the metal, the
former being essentially no different from the vacuum state. Hence, one would not
expert significant interaction» between the two materials over those due only to dis-
pers tot. forces.

On the ota. - * hand, as the defect concentration of the insulator increases (toward
the semiconducting state), free electrons are made available in a density corresponding
to the defect concentrator». Fermi levels, temperature, etc., which can interact with
the free electrons of the me» J. Hence, the electronic contribution to inter facial phe-
nomena will increase. (It is noted, of course, that defects in sufficient density will
reduce the dispersion force compone«.? of the total surface energy, so that one can
expect an inflection in a hypothetical plot %.l total interaction energy versus defect con-
i
centration. Similarly, interdiffus ion of components will be a function of the defect con- I
cent ration of the insulate/ material and one should expect a time dependent» for the
total interaction energy. To this author's knowledge, no eWtailed investigation of these
phenomena has been undertaken.)

Generally speaking, the most serious limitation to the uee of thermodyi*_mic

property *•*.** «u re ments for surface energy determinations lies in the paucity of infor-
matirn on the various contributions to the total surfac* »nergy. It is suggested that
selected experiments can be performed where, through appropriate choices of well-
characterised mats rials, one may be able to measure or reduce the individual com-
ponents of the surface energy.

More specifically, the use of "homologous series" of liquids for the performance
of the Ziemen-Eberhart experiments should be evaluated. It is apparent that this -ech-
nique offers considerable promise for the measurement of surface energies provided
that the materials chosen conform rigidly to the constraints that must be imposed.
Since mere is already a vast amount of data available on the surface tensions of binary
and nit&er order liquid mixtures as functions of composition and temperature, it seems
most natural that this would provide an excellent starting point for the determination of
critical surface tensions, and the concomitant derivation of the surface energy of the
substrate, particularly at "high" temperatures. This is especially attractive as a tool
for the further study of surface energies at temperatures where ductility nature of the
material precludes the application of the cleavage technique.

(II Empirical Approaches, Although the semi-empirical techniques, as accred-

ited to Bruce153', are seriously lacking in fundamental justification, it is apparent that
they may be quite useful in estimating surface energies of s number of untested ma-
terials, provided that sufficiently accurate data may be obtained on the physical proper-
ties which enter the snalysis. In addition, there is an obvious need for continuing effort
on the development of meaningful correlation; not only tfcose that seem to give approxi-
mate answers but slso those in which s reasonable phenomenologiral basis for the cor-
relation can be established on theoretical grounds.
 77

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(21 Pariah, N. M. , 'Effect of Atmosphere on the Surface Energy of Glatt", J. Am.

Ceram. Soc. , 4J, IS (1956.,

(3» Moray, G. W. , Proper tie« of Glatt, Second Edition, American Chen.ic el Society
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14» Boni, R. E. and Derge, G. , "Surface Tension of Silicatet", J. Metalt, S, 53

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<«* Kantto, D. L. Bru neuer, S. , and Cope land, L. E. , "BET Surface Areat -
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(6) Shuttlewcrth, R , "The Surface Tension of Solids", Proc. Phyt. Soc. (London»,
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(7| Johnson, R. E. , Jr. , "Conflicts Between Gibbsian Thermodynamics and Recent

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(81 Gregg, S. J., The Surface Energy of Solids, Reinhold Publishing Cc. , New York
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(9) Mould, R. E. , "The Strength of Inorganic Glasses", in Fundamental Phenomena

in the Materials Sciences, Volume IV; Fracture, Edited by L. J. Bonis, J. J.
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(I0> Stokes, R. J., "Fracture €4* Ceramics", in Fundamental Phenor ena in the
Material Sciences, Volume IV: Fracture, Edited by L. J. Bonis, J. J. Duga and
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Mli Sharpe, L. H. , and Schonhorn, H. , "Surface Energetics, Adhesion, and Adhesive

Joints". Advan. Chem. Ser. . 45. 199(1964).

(12) See, for example, Biker men, J. J. , The Science U Adhesive Joints, Academic
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(13) Weyl, W A.. "Partial Surface Energies, the Key to Adhesion", Bull. Am.
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Tensions, Contact Angles, and Heats of Immersion", Advan. Chem. Ser. , 43, 99
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 78

US) Fowkes, F. M. , "Inter mole culsr and interatomic For«;«» at Interfaces", in Sur-
{aces gad Interfaces 1, Edited by J. Jf. Burke, N. L. Rttd and V. Weiss, Syr SCUM
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(16) Parting ton, J. R,, An Advanced Tr«ati»« oc Physical Chemistry, Volums III,
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(19) Obreimoff, J. W., "The Splitting Strength of Mica", Proc. Roy. Sec. (London),
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36, 1374 (1969).

(23) Westwood, A.R.C. and Goldheim, D. L., "Cleavage Surface Energy of (100)
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Science Research, Volume 1U: The Role of Grain Boundaries and Surfaces in
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(26) Orowan, E., "The Tensile Strength of Mica and the Problem of the Technical
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ilh, Gregs s« J- » ',Th# Surface of Solids and its Significance for Industry and in the
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 79

(31) Glimm, J. J., "Cleavage, Ductility, and Tenacity in Cryetals", in Fracture,

£dttc« Vy S. L Ave/bacä, el a!. , Technology Pre««, MIT, and John Wiley a- Son«,
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(32) Davidge, R. W. and Tappin, G., "The effective Surface Energy oi 9Httie Mate-
Halt", J. Mater. Sei., 3. 165 (1968).

(33) Srawley, J. E and Brown, W. F. , "Fracture Toughness Testing and He Applica-

tion", NASA, TMX-S2030 (1*64).

;34) Nakayama, J., "Direct Measurement of Fracture Energies of Brittle Heterogeneous

Materials", J. Am. Ceram. Soc., 48, 583 (1965).

(35) Berdsnnikov, W. P., "Messung der Oberflächenspannung von Festem Korpern",

Soviet Phy«. Z. S., 4, 397 (1933r. Summary by Kusnetsov, Reference (35):
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(36) Kusnetsov, V. D., Surface Energy of Solids, Her Majesty's Stationary Office,
London (1957).

(37) Kvrong, J.N.S., Adams, J. T., Jr., Johnson, J. F., and Piret, E. L., "Energy -
New Surface Relation ir the Crushing of Solids: I. Application of Permeability
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(38) Adams, J. T., Jr.. Johnson, J. F., and Pirct, E. L., "Energy - New Surface
Relation in the C« aihing of Solids: II. Application of Permeability Measure*
ments to an Investigation of the Crush*« f of Halite", ibid. , p 655.

(39) Johnson, J. F., Axe Is on, J., and Piret, Z. L. , 'Energy - New Surface Relation
in the Crushing of Solids: 111. Application of Ga« Adsorption Measurements to an
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(40) Maringer, R. E. , "Etch Pitting on Sing1« Crystal InSb", J. Appl. Phy«. , 29, 12S1
(1958).

(41) Gatos, H. C., Finn. M. C. , and Lavine, M. C , "Antimony Edge Dislocations in

InSb", J. Appl. Phy«., 32, 1174 (1961).

(42) Gatos, H. C., "Dangling Bonds in IU-V Compounds", ibid., p 1232.

(43) Gatos, H. C., Strauss, A. J., Lavine, M. C., and Harmon, T. C. , "Impurity
Striations in Unrotated Crystals of InSb", ibid., p 2057.

«44») Faust, J. W. , Jr., Private Communication.

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(46) Fiun, M. C. and Gatos, H. C. , "Spontaneous Bending of Thin (111) Crystals of

Ili-V Compound«", Surface Sei., K 36k < 19641.
 •0

(4?) Udln, H., Shale r, A. J., and Wulff, J. , "The Surface Ttnilon of Solid Copper",
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(56) Barghansen, P. E., Good, R. J., Kraus, C., PodolsHy, B., and Sollcr, W.,
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 Si

">?; F*«undUch, H., Kepillarchomio, Volume I, Fourth Edition, Akademische

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(66) Hirschfelder, J. O., Curtiss, C. C., and Bird, R. B., Molecular Theory of Gases
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(67) Marian, J. E., "Surface Texture in Relation to Adhesive Bonding", ASTM Mate-
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(68) Gutshall, P. L., and Gross, G. E., "Observations and Mechanisms of Fracture
in Polycrystalline Alumina", in Proceedings of the National Symposium on Fracture
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(69) Clarke, F.J.P. , Tattersall, H. G., aif>"appin, G., "Toughness of Ceramics and
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(70) Lennard-Jones, J, E. and Dent, B. M., "Cohesion at a Crystal Surface", Proc.

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«Til Huggins, M. L. and Mayer, >. E. , "Interatomic Distances in Crystals of the

Alkali Hal ides . J Chem Phys . L 643(1933)

(72) Zadumkin, S. N. and Khulamkhanov, V. Kh. , "A Simp«? Method of Calculating

the Surfec* Energy of Ionic CrysUls", Soviet Ph>*. -Solid State, English Transl. ,
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(73) Walton, A» G., "Calculation of Ionic Crystal Surface Energies From Thermo-
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(74) See, for example, the recent review by Merabito, J. M. ****! 3'.morjai, G. A.,
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<75» See, for example, Weyl, W. A., in Structure and Properties of Solid Surfaces,
Edited by R. Comer, and C. S. Smith, University of Chicago Press, Chicago
(1953), pp 147-184.

(76) Fowkes, F., "Attractive Forces at Interfaces", Ind. Eng. Chem.. 5<M12», 40
(1964).
 82

(77) Fried»!, J. , Cullity, B. D. , tsd Cruiurd, C, 'The Surface Tension of A Grain

Boundary in a Metal as a Function of the Orientation of the Two Grains Which the
Boundary Separates', Acts Met. , 1, 79 (1953).

(78) McLeod, D. B., "On a Relation Between Surface Tension and Density", Tran*.
Faraday Soc., |9, 38 (1<*23).

(79) Siuta, V. p. and Balicki, M. . "Development of a Corrosion Resistant Magnesium

Alloy. i-*rt II. Surface Tension Data of Elements", WADC Technical Report
57-241 (1957).

(•0) Sikor&ki, M C.f "Correlation of the Coefficient of Adhesion With Various Physical
andMechanial Properties of Metals", J Basic Eng., 85, 279(1963).

(81) Sikoreki, M. E. and Courtney Pratt, J. S., "Adhesion of Rare Earth Metil 9'f
Amtr. Sor. Luh. Engrs. Preprint 63 LC-16 (1963).

(82) Uvey, D. T. and Murray, P., 'Surface Energies of Sohd Oxides and Carbides",
J. Am. Ceram. Soc., 39, 363 (1956).

(83) Bondi, A., "The Spreading of Liquid Metals on Solid Surfaces", Chem. Rev., 52
U>, 417 (1953).

(84) Klngery, W. D., "Surface Tension of Liquid Oxides and Their Temperature Co-
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(85) Kiagery, W. D., "Rcle of Surface Energies and Wetting in Motal-Ceramic

Sealing", Bull. Am. Ceram. Soc., 35, 108 (1956).

(§6) Parkins, R. N., Armour Research Foundation (IITRI), Report ASD-TR-61 -628,
Part U (April, 196i).

(87, Klngery, W. D. , "Metal-Ceramic lateracttone: IV. Absolute Measurement of

Metal-Ceramic Inter facial Energy and the Inter facial Adsorption of Silicon From
lro--5il*con Alloys", J. Am. Ceram. Soc, 37, 42 (1954».

(88) Friche, R., "Über die Feinstruktur von Festkörpern mit Bauelementen kolloider
Grosse und Deren Physikalische «tnd Chemische Eigenschaften", Kollc J-Z, 96,
213(1941).

(89) Ryshkewitch, E. , Oxide Ceramics; Physical Chemistry and Technology, Academic

Press, New York (I960), p 169.

(90) Wiederhorn, S. M. (Unpublished».

(91) Petch, N. J., Congleton, J. , Ha r die, D., and Perkins, R. N., "Study of the
*r****e *»haritur of Ceramic Materials: Effect of Surface Energy* , Technical
Documentary Report No. ASD-TR-61 -628, Parts I, 11, and 111 (1961).

i
 83

(921 Robins, D. A., " Bonding in Carbide •, StUcider. and Borides", Pov d*r Met.,
1/2, 172 (1958).

(93) Bronsall, P. C. , Dollimer, D. , and bollimer, J., "T** Selective Effect of

Adsorption on the Strength of Compacts of Various Oxides and Salts', Brit«
Csram. Soc. Proc. , 6, 61 (1966).

(94) Handbook of Chemistry, 10th Edition, Edited by N. A. Lang«, McGraw-Hill

Book Company, New York (1961), p 1648.

(95) Benson, G. C. and CIax ton, T. A., 'Calculation of th« Surface Energy of the
(110) Face of Some Crystals Possessing the Fluorite Structure", Canad. J.
Phys. , 41^, 1287 (1963).

(96) B'.unauer, S., Kantro, D. L., and Weise, C. H. , "The Surface Energies of
Calcium Odde and Calcium Hydroxide", Canad. J. Chem., 34, 729 (19561.

(97) Fricke, R., "Struktur und Verteilungsart Realer Festkörper und Kataylsatoren
Sowie Deren Untersuchungsmethoden', in Handbuch der Katalyse, Volume IV,
Edited by G. M. Schwab, Springer Verlag, Vienna (1943), p 1; also "On the Fine
Structure of Solid Substances With Colloidal-SUed Particles and Their Physical
tsd Chemical PrcpcrtUs", Kail. *., 9*. *** 0*41).

(98) G. E. Boyd, in Surface Chemistry, Echled by F. R. Moulton, Amir. A soc.

Adv. Sei. Publication No. 21 (1943), p 128 ff.

(99) Jaeger, F. M., "Temperatur« Variation of Molar Surface Free Energy J(

Liquids in the Temperature Range 80 to 1650 C", Z. Anorg. Allgem. Chem.,
101, I (1917).

(100) Jaccodine, R. J#f "Surface Energy of Germanium and Silicon", J. Electrochem.

Soc., U0t 524 (1963).

(101) Born, M. and Stern, O. , "The Surface Energy of Crystals and Its Influence on
Crystal Form", SiUber. Preuss. Akad. Witts., 48, 901 (1919).

(102) Lennard-Jonct, J. E. and Taylor. P. A., "Some Theoretical Calculations of

the Physical Properties of Certain Crystal*", Proc. Roy. Soc. (London), A509,
476 (1926).

(103) Dent, B. M. , "The Effect of Boundary Distortion or. the Surface Energy of a
Crystal", Phil. Mag., 8, 533 (1929).

(104) van Zeggeren, F. and Benson, G. C., "Calculation of the Surface Ei*erg*e» of
Alkali Halide Crystals", J. Chem. Phys., 26, 1077 (1957).

<105i van Zeggeren, F. and Benson, G. C. , "The Quantum Mechanical Calculation

of the Surface Energy of Sodium Chloride - A First Approximation", Canad.
J. Phys., 34, 985 (19561.

(106) Benson, G. C., "Recalculation of the Surface Energies of Alkali Halide

Crystals", J. Chem. Phys., 35, 2113 (1961».
 84

(107) Shoe key, D. A. and Grots, G. W., "Effect of Wittr on Toughness of MfO
Crystals", J. Am. Ctrwn. Soc., M, 299 (1968).

(100) GutsheU, P. L. and Gros i, G. C., "Clevage Surface Energies of NaCl and MfO
InVicwim", J. Appl. Phys., 36, 2459 (1965).

(109) Jura, G. and Garland, C. *\ , "The Experimental Determination of the Surface

Energy of Magnesium Onidn", J. Am. Cham. Soc., 74, 6033 (1952).

mm Boyd, G. E., "Some Aspects of the Properties of Solid Surfaces'*, in Surface

Chemistry, Edited by F, R. Moulton, American Adv Sei Pub No 21 (1943),
p tits &
(HI) Benson, G« C., Schreiber, H. P., and van Zeggeren, F., "Experimental
Determination of the Surface Enthalpy of Sodium Chloride", Can**. J. Chem.,
34, 1553 (1956).

(112) Upsitt» A. C, Johnson, F-M.G., and Maas, O., J. Am. Chem. Soc., 49, 1940
(1927); also ibid., 50, 2071 (1928); see also Harlans, W. O., "Energy Relations
of the Surface of Solids. !. Surface Energy of the Diamond", J. Chem« Phys.
10, 269 (1942); Benson, G. C. and Benson, G. W., "Surface Energy of the
Alkali Halides", Canada J. Chem.„ 33, 232 (1955).

(113) Ryasentsev, P. P, ano Shcherhakov, L. M., "The Effect of Comminution on

the Solubility and the Heat of Solution", Kolloid-7., 21, 464 (19591.

(114) Adam roc, A. W., Physical Chemistry of Surfaces, inter science, New York
(1967), p 57. ■.-~-.™=—^—*——~,~

(115) Parikh, N. M,, "Effect of Atmosphere on the Surface Tension of Glass at Low
temperature", 5c. D. Dissertation, Massachusetts Institute of Technology (1953).

(116) Sche!linger, A. K., "Solid Surface Energy acid Colorimetric Determinations of

Surface-Energy Relationships for Some Common Minerals", Mining Eng., 4,
369 (1952).

(117) Wiederhorn, S. M. , "Fracture of Ceramics'% Mechanical and Thermal Properties

of Ceramics, Edited by J. D. Wacbtman, Jr,, Natl. Bur, Std. Special Publication
No. 303 (1969), p2!7.

(1181 Boyd, G. E. and living »ton, H. K., "Adsorption and the Energy Changes at
Crystalline Solid Surfaces", J. Am. Chem. Soc., 64, 2483 (1942).

(119) Basford, P. R, Harkins, W. D. , and Tmii, £• B., "Effect of Temperature

on the Adsorption of n De cane on Iron", J. Phys. Chem., 58, 307 (1954).

(120) Jura, G. and HarKins, W. D., "Surfaces of Solids: XI. Determination of the
Decrease of Free Surface Energy of a Solid by an Adsorbed Film"» J. Am.
Chem. Soc., 66, 1356 Ü944).

(12!) Eberhart, J. G., "The Critical Surface Tension of Uranium Dioxide", J. Nucl.
Mater., 25, 103 Ü968).
 85 and 86

(122) Livey, D. T. and Murray, P., "The Wetting Properties of Solid Oxides and
Carbides by Liquid Metals", in Plan see Proceedings, 1955, Edited by F.
bonesovsky, Pergamon Press, Ltd., London (1956), p 375 ff.

(123) Humenik, M. and Whalen, T. J. , 'Physicochemical Aspects of Cermets", in

Cermets, Edited by J. R. Tinklepaugh. Reinhold Publishing Co , New York (I960),
p 6 ff.

(124) Beimuller, J , Z Physik, 38. 7S9H936)

(125) Glauberman, A. E. , ' Theory of the Surface Energy of Heteropolar Crystals",

Zh T\z. Khim. 23, 124 (1949)
 Al

APPENDIX A

APPLICATION OF TECHNIQUES

Table A-1 lists the various materials measured by the most commonly used ea-
perimental methods lor determining solid surface energy Table A-2 gives a similar
listing for the use of theoretical methods.

TABLE A-l PRIMARY EXPERIMENTAL TECHNIQUES AND THE MATERIALS

MEASURED BY THEM

Technique Material» U««*ured

Maximum bubble pressure and Al203 KB02 NaCl
umiUr experiment« on liquids B203 KBr NaF
BiBr KC1 Nal
B1CI3 KF NaNOj
CdCL» KI NaK>j
CsBr KOH3 Na,S04
CsCl L*2Oj P2CH
CaF L1BO3 RbBr
Csl LiCl RbCl
Cs2S04 Lil RbF
CsNOj LiNOj Rbl
GfO, L.2S04 SnCl2
NaBr
Solubility and heat of solution Af - v- rOA CaS04 2H2C NaCl
Ai/Oj CdO Pbi2
BaS04 CuO I*F2
CaJ2 Fe2<>3 sb2o,
CaO KC1 Si02
CaOH MgO SrS04
Mg<OHi2
Heat of immersion A1203 NaCl
AI2O3 ZSiOz ^H^O Sodium Dlite
AI2O3 4SiO^ H2O Sodium Montmoi lionite
BaS04 SiC»2
C (graphite 1 Sn02
Calcium Illitc T1O2
C«h tun-. Montmo* flomte Zr02
GeO,
Work of fracture. «. leavage Al,03 K O Al203 6S1O2
Alj03 iSiOj 2H20 K2O 3A1203 0S1O2 IHiO
BaF^ LiF
C «graphite' MgO
CaC03 NaCl
CaF> S:
Ge S1O2
KCl ZnO
Conta«. t angle» A1N Sapphire TiC
Al2C3 ThOj TiN
CdO TiB2^ IO2
ZnO
 A-2

TABLE A-2 . MAJOR THEORETICAL TECHNIQUES AND SOLID

SURFACE ENERGIES CALCULATED BY THEM

Technique Mats rials Dstarminad

Atomistic calculation BaF2 KBr NaCl

BaO KC1 NaF
BaS KF Nal
BaSa Kl RbBr
BaTs LiBr RbCl
CaF2 UC1 RbF
CaO UF Rbl
CaS Ul SrF2
CaSs MgS SrS
CaTs MgSa SrSa
CsF NaBr SrTs
Elastic coniUnti AfBr Ga MgO A1203
AgCl InS Mi2Si04
BaS04 KBr NaBr
C {diamond) KC1 NaCl
CaC03 Kl PbS
CaF2 K20 A1203 bSiOt Si
F#203 LiF Ti02
FsS2 MfO ZnS
Sublimation «borgy AlAs Cr203 InP
A1203 F«0 InSb
AIP Fa-03 MgO
AlSb Fa203-CaO MnS
BaS Fa304 NaCl
BaO GaAs PbS
CaC03 Mg COj GaP p-SiC
CaO GaSb TiOz
CaO MfO A1203 St02 InAs
Empirical calculations BaO KBO3 ln02
BaO KG TiC
CaO KF UC
CdO Kl uo2
CsBr MnO VC
CsCl PbO ZnO
CiF SrO ZrC
Csl TaC ZTOI
FeO
 B-l

APPENDIX S

CLASSES OF MATERIALS STUDIED

Sine« it U ^tma of value to study trends within different CUIMI of material*, the
compounds that have boon studiod and roportod in this work are categ• «ised into different
groups It should bo noted that comparisons among different materials within a group
can bo misleading and caution is urgod in attempting to draw correlations between values
of surface energy for various members of the groups. Table B-l lists materials by
class, while Table B-2 provides a minerals cross-reference. It should be pointed out
that the tables of Appendix C list materials by alphabetical order in their chemical
symbols.
 B-2

TABLE B-» MATERIALS STUDIED BY PRIMARY CLASSES

Matarials CUts MatariaU Studiad

Elements C (f raphite)
C (diamond»
Germanium
Silicon

Halid«» AgBr Csl NeF

A«C1 KBr Nal
BaF2 KCt Pbl2
BiBrs KF PbF2
BiCl3 KI RbBr
ceF2 LiBr RbCi
cda2 Lia RbF
CsBr LiF Rbl
CsCl Lil SDC12
CsF NeBr SrF2
N*a
Simple oxides AI2O3 Fs203 Sb203
B2O3 Fe304 SiOz
BaO G«^ SnC^
BeO Le203 SrO
c*o MfO ThC^
CdO MnO TiC^
Cr203 p2o5 UC^
CuO PbO ZnO
FeO ZrOj

Mixed axiom* Af2Cr04 K20 A12G3 i>SiOi

Ai203 2Si02-2H20 K20 3A1203 tSi02 IH20
A1203 4SiOz H20 KP03
CaO MfO A1203 S1O2 UBO3
Calcium Illite Mf O A1203
Calcium Montmoriilonite Mg2Si04
r«203-CaO NaPOj
KB02 Sodium Illite
Sodium Montmoriilonite

Chalcofenides BaS MfS

BaSe MgSe
BeTs MnS
CaS PbS
CaSa SrS
CaTs SrSc
FsS2 SrTt
InS ZnS

lll-V semiconductors AlAi CaP

A1N GaSb
AIP InA»
Al» InP
CaA* InSb
 B-3

TABLE B-1 (Costumed)

Meiertal* CUt* Material« Studied

Carbonates, nitrate», Ba804 C.NO* NeNOj

•ulphatet CaCOj CmH04 Na?S04
CeCOy MgCO3 UNO3 6r804
CaS04 2H20 Li28C4 ZnCOs
MitceUanaott« CaOH TaC liC
Mf(OH)2 TiB2 VC
TiC ZrC
S.3N4 TiN
 i
B-4
!

TABLE B-2 THE COMPOSITION Or MINERALS US TED IN

THE TEXT, TAbLE *<»>

Minaral Comical Formula

Ana tat* Ti02

Apatit« CaF2 3Ca3P208
Barita BaSOa
Caicita CaCOj
Calcium lllita CaCO)
Calcium MontmorUlonita CaCOj
Diamond Carbon
Dolcmita CaCOj MgCOj
For at« ritt Mf2Si04
Catena FfcS
Gaalini*a CaO Mf O A1203 Si02
Graphit« Carbon
HamMita Fa203
Kaolinita Al2Oj 2SiOz 2HaO
Labradorita NaAlSi3Og: CuAi2Si3Og
Mica K20- 3Ai203 bSiOi 2H20
Orthoclaaa K20 Ai203 bSiOi
Ptarl Spar CaCOj MfCO}
Potassium feldspar K20 A1203 bSiOi
Pyrita F9$z
Pyrophylhts A1203 tSiOz H2C
Rutila Ti02
Sapphire A1203
Sphalarita ZnS
Spinal M*0 A1203
Sodium IUito
Sodium MontmorUlonita
Topas (AlFl2Si04 or Al(F2OH;>Si04

{at Far it* num part. missest* «re tfied is the t*bi* of airf«c« eacrgjr (Table 6» uadcf their
chesnicjl fatmul*e There si« however, one misetSU Used by common «scne
 C-1

APPENDIX C

SURFACE TENSION OF SELECTED FUSED SALTS AS

A FUNCTION OF TEMPERATURE

Value* for surface tension of various fuaad salts ovar i broad temperature range
ara available at selected temperatures from The Handbook of Chemistry*?* >. The values
given in the handbook have been approximately fitted here to the general relation
T l 2
> = k (1 - T/T ) , which is used widely. The constants k and Tc were calculated and
L* c
Ubulated in Table C-1. Note that these may be somewhat different from similar calcu-
lations listed under "Remarks" in Table 6; this discrepancy is related to the wider tem-
perature ranges employed bere-

it should be emphasised that the values of Tc are calculated only from experi-
mental data and are not presumed to have intrinsic significance as the critical tempera-
ture (since dissociation and other effects may perturb interpretation)
 c-2

TABLE C-l. CONSTANTS FOR THE EQUATION >* = k (1 -T/Tc)1 2

FOR VARIOUS FUSED SALTS

Critical Temperatur«,
Material k <TC>, k Atmosphere

AgQ 175 2194 Air

B1CI3 112 1161 Nitrogen
CtBr 120 2522 Nitrogen
Cta 13« 2297 Nitrogen
C»F 151 2804 Nitrogen
Cel no 2401 Nitrogen
CtNOj 128 2130 Nitrogen
C 2SO4 163 3576 Nitrogen
KBr 135 2487 Nitrogen
KQ 147 2664 Nitrogen
K2Cr207 1S4 6600 Nitrogen
KF 206 3141 ?. trogen
KI Ho 25CK Nitrogen
KNO3 145 £i*9 Nitrogen
KPO3 220 *43! Nitrogen
K2S04 201 4070 Nitrogen
LiB02 33* 4472 Nitrogen
UCi iol 3178 Nitrogen
UF 340 3686 Nitrogen
UNO* 138 27% Nitrogen
«^^«04 275 5163 Nitrogen
NeBr 159 2683 Nitrogen
NftCl 164 3018 Nitrogen
N*F 290 3539 Nitrogen
N*I 120 2917 Nitrogen
NeN03 145 2*lfc Nitrogen
N»P03 24* 4522 Nitrogen
Ne2S04 2 38 5502 Nitrogen
R>CI2 186 2522 Air
RbBr 134 251* Nitrogen
RbCl i54 2 354 Nitrogen
RbF 191 27rf* Nitrogen
Rbl 124 22*4 Nitrogen
RbNOj 138 ^ 513 Nitrogen
Rb>SCH I"* 44» < Nitrogen
SnClj 132 19*4 Nitrogen
 Mhui
B555fr cotrrtoc DATA . 5T
ITM« ACTIVITY re«*»*
Oef*nsc Ceramic Information Center inOASSIFIED
Battelle Hewrlal Institute I«*
Columbus Laboratories. 505 King Avemr., Cols,. Ohio
» mppmt TtTLf im-
SURFACE ENERGY OF CERAMIC HATERIALS

Social OCIC R^wt

Or. Jules J. üuga, Battelle Memorial Institute, Crlurtous lab*rat**ri»s

CTwrargH
>3 1?5
h— MM
ft* tVTftftftf •« ••*•» «••

F3361S-69-C-H33 OCIC R<wrt <>9-2

t* f*«r**t

It AVAA,AWUrr/UWTAT1OT

Urn-iite« distributiv

it. TA«V MOT<t ( ttUTAAV ACTIVITY

Mr Fnrce Material« labnrafrv
Material* Su^nort Dlvlsio* (MAAN)
Wrloht-Patt^rscr, A1r Fore*? Bate, Ohio *b4|3
•a
The concents, exn*rl-?e«tal techniques, and theoretical analysts of the surface
eneroy of solid ceramic materials are reviewed with the a1~ of condensing a lerne
«ass of unrelated data Into a concise for* f*r ccwoarisnn an* »valuation. It 1s sholn
that vari^u* experimental methods c*i be anolied to the measurement of surface enerq],
but» that each of these has certain limitations which are often unstated. Further
it 1s shown that theoretical analyses and empirical correlations, while sometimes
rather irorecise. can be used to approximate surface enemies, Particularly as functions
cf temperature« While a few materials have been discussed in considerable detail
(such as *jOt AI2O3 and sone alkali halldes), a review of the literature notes the
there 1s a great oauclty of Information on the surface ener*1*»s of many sclids of
interest. Improvements and «x.ensions of exnerlmeiital a <d empirical techniques ere
suggested that will helo to fill the voids In the ^resent understanding of ceramic
snlid surfaces» and soecific analyses of experimental methods *r+ forwarded. It 1
shown in th* r^rt that the nro^r use of thcn»dvna»1c techniques offers onsideralie
»vitentlal for the measurement and Interpretation nf so1 id surface encrnist, of a largl
lumber of naterials that m ooorly understood at nresent. In addition, the further!
development of thermodyruilc nethods -resents an opportunity to investigate solid
surface energies of nonbrittle materiils, thus overcnnlnq nne of tn* basic H^ita-
.I0.1S of th*» use ft! «echanlcal method«.

OD .«1473
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Ceramic materials
ExoerlnenUl lech-ilques
Glass
measurement
Mechanical Piwertles
Physical *ro:*rt1es
Surface tension
Surfaces, ef*rqy
Theoretical calculations

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