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PARTICLES
ON
SURFACES
PARTICLES
ON
SURFACES
Detection, Adhesion, and Removal
edited by
K. L. Mittal
Skill Dynamics, an IBM Company
Thornwood, New York
0 CRC Press
Taylor & Francis Group
Boca Raton London New York
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iii
iv Preface
REFERENCES
1. K. L. Mittal (ed.), Particles on Surfaces 1: Detection, Adhesion and Removal,
Plenum Press, New York (1988).
2. K. L. Mittal (ed.), Particles on Surfaces 2: Detection, Adhesion and Removal,
Plenum Press, New York (1989).
3. K. L. Mittal (ed.), Particles on Surfaces 3: Detection, Adhesion and Removal,
Plenum Press, New York (1991).
Contents
Preface iii
Index 419
Contributors
•current qffiliation: Center for Advanced Materials Processing, Oarkson University, Potsdam,
New York
Contributors xi
1
2 Rimaietal.
INTRODUCTION
The adhesion of small particles to substrates is of great importance to many
teehnological areaa including semiconductor fabrication, paint formulation, xero-
graphic processes, pharmacology, and agriculture. AB is well known, the forces of
adhesion increase with increasing contact area. Moreover, the stresses generated
by the surface forces existing between materials result in a finite contact area
between the materials, thereby increasing the force of adhesion. Thus, adhesion
between particles and substrates is a dynamic problem which depends not only on
the surface energies of the materials, but also on their mechanical response to the
stresses.
Adhesion induced deformations between particles and/or between particles
and substrates were first postulated independently by Bradleyl.2 and by
Derjaguin. 3 Derjaguin attempted to calculate the contact radius by assuming that
the particle could be treated as a Hertzian indentor with the applied load due to van
der Waals forces between the particle and substrate. The deformation would then
be a result of an elastic compression between the two materials.
Specifically, the contact radius, a, for a Hertzian indentor of radius R under
an initial applied load, po, is given by:
[1)
where E and u are the Young's modulus and Poisson ratio of the substrate, respect-
ively. ABsuming that the load is a result of van der Waals interactions, it can be
shown that
po = lim R [2)
87tZ20
where lim is the Hamaker coefficient and zo is the separation distance between the
particle and the substrate (approximately 4 Afor van der Waals bonded crystals).
Therefore, according to the Derjaguin model,
Krupp4 first recognized that the adhesion induced stresses could be large
enough to exceed the elastic limit of at least one of the contacting materials. He
attempted to generalize the Derjaguin model to include plastic flow by postulating
that the contact area could be divided into two coaxial regions of stress. He
assumed that the inner region, being subjected to the greater stress, would deform
plastically. The outer, lower stress, annular region would deform elastically.
Krupp further postulated that the radius of the inner region, a1, and the radius of the
entire contact area, ao, were related to the Young's modulus, E, and a time depen-
dent hardness, H(t) by the equations:
[4)
Adhesion Induced Deformations 3
[5]
Krupp also assumed that H(t) would reach some terminal value, H, within
approximately 30 minutes and that the steady state value of H is of the order of 10·3E.
This allowed for the contact radius reaching a limiting size.
Johnson, Kendall, and Roberts (hereafter referred to as JKR)5 first recognized,
while measuring the contact radii between homogeneous combinations of macro-
scopic rubber and gelatine spheres, that both compressive and tensile interactions
contribute to the size of the contact radius. Approaching the problem thermodynam-
ically and assuming that all interactions occur solely within the contact zone, they
predicted that, for a spherical particle in contact with a planar substrate,
where WA is the work of adhesion and is related to the surface energies 'Yl and 'Y2 of
the two materials and their interfacial energy 'Yl2 by
[7]
[8]
where
k - 1-ur [9]
I- nEI
and E1 and 'Uj are the Young's modulus and Poisson ratio of the ith material, respect-
ively. Implicit in the JKR model is the assumption that the tensile stresses become
infinite at the edge of the contact area.
In the absence of any applied load, Equation (6) reduces to
[10]
Alternatively, the JKR model predicts that, under the influence of a negative
(tensile) load, separation of the particle from the substrate occurs when the contact
radius is reduced to lla - 0.63ao, where ao is the contact radius established with no
applied load. Moreover, the value of this load, P 8 , is given by:
[11]
4 Rimaietal.
As can be seen, the separation force, as predicted by the JKR theory, is indepen-
dent of the moduli of the materials. Johnson et al. recognized that this result was
inconsistent with experimental results for compliant materials and attributed the
discrepancy to difficulties in determining when the particle was in equilibrium
with the substrate under light loads.
An alternative approach to calculating the contact radius was proposed by
Derjaguin, Muller, and Toporov6 (DMT). Following the original approach by
Derjaguin 3 and approaching the problem from a molecular level, they also
assumed that the contact would be Hertzian, thereby ignoring the shape of the zone
outside of the contact region. As a result of the assumption as to the shape of the
contact region, the DMT theory predicts that half of the interaction exists outside of
the contact zone. Moreover, this theory predicts that the elastic flattening has no
effect on the particle adhesion force.
A detailed comparison of the assumptions, predictions, and consequences of
the JKR and DMT theories has been made by Tabor. 7 He showed that the contact
radius as predicted by the DMT model was approximately half of that predicted by
the JKR theory. The reasons for the discrepancy in the predicted contact radius was
further discussed in papers by TaborS and by Derjaguin et al. 9 Finally, Muller,
Yushchenko, and DerjaguinlO,ll (MYD) proposed a model in which they assumed
that the contact potential between a particle and a substrate could be described by a
Lennard-Jones potential. According to Muller et al., both the JKR and DMT
models are limiting cases of the more general MYD theory, with the JKR model
valid for more compliant, higher surface energy materials and the DMT model
valid for more rigid, lower surface energy materials. Moreover, the transition
between the regions of validity of JKR and DMT models is given in terms of a
dimensionless parameter 11. defined as:l2
11
= 32 [2R'!'A
3x xE zg
2
]va [12]
where
[13]
lfll > 1, the JKR model properly describes the interaction, whereas if11 < 1, the
DMT model is valid. Further discussion of the features and limitations of the
various theories of adhesion is presented by Tsai, Pui, and Lui,l3 who also further
generalized the results of Muller et al.lO,ll More recently, Maugis analyzed the
JKR-DMT transition by utilizing fracture mechanics approach based on the
Dugdale model. 14
Maugis and Pollock 16 generalized the JKR model to include nonelastic (i.e.,
plastic) deformation of the contacting materials. They found that if a material
undergoes totally plastic deformation, the contact radius is related to the externally
applied load, P, the work of adhesion, WA, the particle radius, R, and the hardness of
the plastically deforming material, H, by:
H=3Y [15]
EXPERIMENTAL PROCEDURE
RESULTS
As an illustrative example of elastic deformations resulting from the forces of
adhesion, consider glass spheres (obtained from Duke Scientific Corporation) in
contact with an electrically conductive, carbon impregnated polyurethane sub-
strate. The glass spheres had radii ranging between 0.5 J.Un and 100 J.lm.
Typically, glass has a Young's modulus of approximately 7 X 1010 Pa and, being
relatively rigid compared to the polyurethane, would not be expected to deform
significantly. In contrast, the polyurethane had a Young's modulus (as determi-
ned using an Instron tensile tester) of approximately 5 X 106 Pa.
Figures 1A through 1D show typical SEM micrographs of glass particles
having radii of approximately 3.3, 12.5, 22, and 65 J.lm, respectively, on the poly-
urethane substrate. Magnification scales are drawn beneath each image. Figures
2A though 2D show, at increased magnification, the contact region of these ident-
ical particles, respectively. As can be seen, the particles appear to embed deeply
into the substrate and menisci appear around the particle, indicative of tensile
contributions to the size of the contact radius. The contact radius is also seen to
increase with particle radius, but at a sublinear rate. It is interesting to note that,
while the size of the contact radius was fairly reproducible for a given particle
radius, some of the smaller particles exhibited significantly larger than average
meniscus heights. An example of a particle-substrate interface exhibiting a relat-
ively large meniscus, at low and high magnifications, is shown in Figure 3. The
reasons for the variations in meniscus height are not presently known, but may be
related to possible inhomogeneities in the substrate or local substrate surface con-
dition.
Adhesion Induced Deformations 7
1A 18
1C -11"" 10 - - - 1011m
of adhesion, calculated from Equation 10 and assuming that the Poisson ratio
equals 1/3, is found to be 0.17 J/m2.
It is of value now to focus more closely on the response of the system for the case
where the particle radii are less than approximately 5 J.I.III. Following the same
analysis, it is found, from the plot oflog a versus log R, shown in Figure 7 that the
8 Rimaietal.
contact radius varies as the particle radius to the 3/4 power. Moreover, as can be
seen from Figure 8, the least squares fit line of the contact radius, a, as a function
of R to the 3/4 power intersects the origin.
A similar, anomalous dependence of the contact radius on particle radius has
been found for polystyrene particles having radii between approximately 1 J.lm and
6 J.1m in contact with the same substrate. Typical micrographs of the polystyrene
particles in contact with the polyurethane substrate are shown in Figure 9. Figure
10 shows a plot oflog a versus log R. The exponent, determined from the slope of the
curve was found to be 0.77, or close to 3/4. Moreover, from a statistical analysis of
the data (see Appendix A), it was found that the probability of the true exponent being
as small as 2/3 is only 3.3%. A plot of the contact radius versus the particle radius to
the 3/4 power is seen, from Figure 11, to be straight, intersect the origin, and exhibit
little scatter of the data. It is interestin~ to note that Bowden and Tabor report a
similar anomalous dependence of the contact area on applied load for indentation
experiments on viscoelastic materials. 42
Previously reported observations of the relatively short relaxation time of the
surface force induced stresses35 compared to the time scale of the current experi-
ments suggest that 3/4 power law d~:pendence cannot be explained simply by invok-
ing viscoelasticity or relaxation effects. However, it is conceivable that, due
2A 28
- - 2jUII 20 - 1 JUII
2C
- - - - - - 10jUII --IOJlm
Figure 2 Micrographs of the contact region of the exact same particles as shown
in Figure 1, but at increased magnification. Menisci, indicative of
tensile interactions, are clearly visible.
Adhesion Induced Deformations 9
3A 38
1 f.!m
Figure 3 Low (3A) and high (3B) magnification SEMs of a small glass particle
on a polyurethane substrate showing a large meniscus.
20
....
16 ~
e 12 ~
..
.....
~
cu
,.
a~
:
4~.
.t .,.
o'
0 20 40 60 80 100
R (J1111)
Figure 4 A plot of the contact radius as a function of particle radius for glass
spheres on a polyurethane substrate.
10 Rimaietal.
Figure 5 A plot of the log of the contact radius as a function of the log of the particle
radius for R < 60 J.lm. The slope of the least squares fit line is approxi-
mately 213, which is consistent with the predictions of models which
assume elastic response to the adhesion induced stresses.
12.0
..
~ 8.0
E
~
4.0
I
8.0 12.0 16.0
Figure 6 A plot of the contact radius as a function of particle radius to the 2/3
power for glass particles having radii less than 60 J.lm in contact with a
polyurethane substrate. The least squares fit line through the data is
seen to intersect the origin, suggesting the absence of any significant
externally applied load.
Adhesion Induced Deformations 11
to the relatively high stresses generated by the adhesion forces, compared to the
Young's modulus of the substrate, that nonlinear elastic effects may be present.
This hypothesis is consistent with the lack of any distinct break observed in the
curves shown in Figures 5 and 6.
Now consider the glass particles having nominal radii of approximately
103 IJ.IIl. AJ! seen in Figure 4, the contact radius does not increase for these particles
over that measured for the 60 11m radius particles. Moreover, as evident from
Figure 4, there is significantly greater variation in the contact radii associated
with these particles than with the smaller ones. AJ! has been indicated, the plane of
the substrate was perpendicular to the horizontal for all the samples in this study.
Therefore, gravitational forces tend to peel the particles away from the substrate.
For most of the particles used in this study, these forces are small compared to the
surface forces. However, as indicated by the fact that most of the large particles
failed to adhere to the substrate, gravitational forces are not negligible for the
103 11m radius particles. Figure 12 shows a typical electron micrograph of a 103 11m
radius particle in contact with the polyurethane substrate. AJ! can be seen by the
different scales shown in this figure, the magnification was increased just above
the contact region, thereby permitting both an overview of the particle and a high
resolution image of the contact zone in one micrograph. AJ! can be seen, the particle
appears to be pulling the substrate. The sharp contact angle makes the appearance
of distended substrate distinct from the appearance of the menisci observed with the
smaller particles. Similar effects have been reported by Chaudhury.43
The hysteresis associated with the placing and removing of a particle on a
surface can also be observed with an atomic force microscope (AFM). For example,
Schaefer et al. 44 cemented 10 jlm radius silver coated glass and polystyrenespheres
onto the tip of an AFM cantilever and measured the force of adhesion between the
particle and highly oriented pyrolitic graphite, polyurethane, and wax coated laser-
printer paper substrates as a function of particle displacement. A typical result, in
this instance polystyrene spheres on pyrolitic graphite, is shown in Figure 13. AJ!
can be seen, during the loading process, the particle initially experiences little or
no attractive force. Then, at a sufficiently small displacement, which is a function
of the spring constant of the cantilever, the particle jumps to the substrate. This
shows as a small, negative force at zero displacement. Upon further loading, a
positive force is needed to press the particle into the substrate. Upon unloading, the
force initially retraces the loading curve, within the error of the equipment.
However, separation does not occur at zero displacement. Rather, an applied force
must still be applied until, fmally, separation is achieved. Similar observations
have been reported by Mizes et al.45
These results suggest that, in the process of separating a particle from a sub-
strate, energy is put into both propagating a crack in the interfacial zone and into
creating stress distributions in the materials. This further suggests that, due to the
relatively short range nature of surface forces, the placing and removing a particle
from a surface may not be a reversible process, even if the materials respond elasti-
cally to the adhesion induced stresses. In other words, the loading and unloading
process may exhibit a hysteresis effect, even in the absence of plastic or viscoelastic
response.
12 Rimaietal.
Cll
Ol
.3
LogR
Figure 7 The log of the contact radius as a function of the log of the particle radius
for R < 5 IJ.IIl. The observed 314 power law dependence (obtained from the
slope of the curve) is unexplained but is consistent with previously
reported results of indentation experiments on viscoelastic materials
(Ref. 42).
78. Politian was the first that wrote the Latin language
His version of
Herodian. with much elegance; and while every other early
translator from the Greek has incurred more or less of censure at the
hands of judges whom better learning had made fastidious, it is
agreed by them that his Herodian has all the spirit of his original,
and frequently excels it.[409] Thus we perceive that the age of Poggio,
Filelfo, and Valla was already left far behind by a new generation:
these had been well employed as the pioneers of ancient literature;
but for real erudition and taste we must descend to Politian,
Christopher Landino, and Hermolaus Barbarus.[410]
[409] Huet. apud Blount in Politiano.
[410] Meiners, Roscoe, Corniani, Heeren, and Greswell’s Memoirs of early
Italian scholars, are the best authorities to whom the reader can have
recourse for the character of Politian, besides his own works. I think,
however, that Heeren has hardly done justice to Politian’s poetry.
Tiraboschi is unsatisfactory. Blount, as usual, collects the suffrages of
the sixteenth century.
[411] Heeren, 272, Morhof, i. 821, who calls Perotti the first compiler of good
Latin, from whom those who followed have principally borrowed. See
also Baillet and Blount for testimonies to Perotti.
Doctrine of 86. But the Platonism of Ficinus was not wholly that of
Averroes on the master. It was based on the emanation of the
the soul.
human soul from God, and its capacity of reunion by an ascetic and
contemplative life; a theory perpetually reproduced in various
modifications of meaning, and far more of words. The nature and
immortality of the soul, the functions and distinguishing characters
of angels, the being and attributes of God, engaged the thoughtful
mind of Ficinus. In the course of his high speculations he assailed a
doctrine, which, though rejected by Scotus and most of the
schoolmen, had gained much ground among the Aristotelians, as
they deemed themselves, of Italy; a doctrine first held by Averroes;
that there is one common intelligence, active, immortal, indivisible,
unconnected with matter, the soul of human kind, which is not in
any one man, because it has no material form, but which yet assists
in the rational operations of each man’s personal soul, and from
those operations which are all conversant with particulars, derives its
own knowledge of universals. Thus, if I understand what is meant,
which is rather subtle, it might be said, that as in the common
theory particular sensations furnish means to the soul of forming
general ideas, so, in that of Averroes, the ideas and judgments of
separate human souls furnish collectively the means of that
knowledge of universals, which the one great soul of mankind alone
can embrace. This was a theory built, as some have said, on the bad
Arabic version of Aristotle which Averroes used. But, whatever might
have first suggested it to the philosopher of Cordova, it seems little
else than an expansion of the Realist hypothesis, urged to a degree
of apparent paradox. For if the human soul, as an universal, possess
an objective reality, it must surely be intelligent; and, being such, it
may seem no extravagant hypothesis, though one incapable of that
demonstration we now require in philosophy, to suppose that it acts
upon the subordinate intelligences of the same species, and receives
impressions from them. By this also they would reconcile the
knowledge we were supposed to possess of the reality of universals,
with the acknowledged impossibility, at least in many cases, of
representing them to the mind.
Opposed by 87. Ficinus is the more prompt to refute the Averroists,
Ficinus. that they all maintained the mortality of the particular
soul, while it was his endeavour, by every argument that erudition
and ingenuity could supply, to prove the contrary. The whole of his
Platonic Theology appears a beautiful, but too visionary and
hypothetical, system of theism, the groundworks of which lay deep
in the meditations of ancient oriental sages. His own treatise, of
which a very copious account will be found in Buhle, soon fell into
oblivion; but it belongs to a class of literature, which, in all its
extension, has, full as much as any other, engaged the human mind.
Desire of man88. The thirst for hidden knowledge, by which man is
to explore distinguished from brutes, and the superior races of men
mysteries.
from savage tribes, burns generally with more
intenseness in proportion as the subject is less definitely
comprehensible, and the means of certainty less attainable. Even our
own interest in things beyond the sensible world does not appear to
be the primary or chief source of the desire we feel to be acquainted
with them; it is the pleasure of belief itself, of associating the
conviction of reality with ideas not presented by sense; it is
sometimes the necessity of satisfying a restless spirit, that first
excites our endeavour to withdraw the veil that conceals the mystery
of their being. The few great truths in religion that reason discovers,
or that an explicit revelation deigns to communicate, sufficient as
they may be for our practical good, have proved to fall very short of
the ambitious curiosity of man. They leave so much imperfectly
known, so much wholly unexplored, that in all ages he has never
been content without trying some method of filling up the void.
These methods have often led him to folly, and weakness, and
crime. Yet as those who want the human passions, in their excess
the great fountains of evil, seem to us maimed in their nature, so an
indifference to this knowledge of invisible things, or a premature
despair of attaining it, may be accounted an indication of some
moral or intellectual deficiency, some scantness of due proportion in
the mind.
Various 89. The means to which recourse has been had to
methods enlarge the boundaries of human knowledge in matters
employed.
relating to the Deity, or to such of his intelligent creatures as do not
present themselves in ordinary objectiveness to our senses, have
been various, and may be distributed into several classes. Reason
Reason and itself, as the most valuable, though not the most
inspiration. frequent in use, may be reckoned the first. Whatever
deductions have suggested themselves to the acute, or analogies to
the observant mind, whatever has seemed the probable
interpretation of revealed testimony, is the legitimate province of a
sound and rational theology. But so fallible appears the reason of
each man to others, and often so dubious are its inferences to
himself, so limited is the span of our faculties, so incapable are they
of giving more than a vague and conjectural probability, where we
demand most of definiteness and certainty, that few, comparatively
speaking, have been content to acquiesce even in their own
hypothesis upon no other grounds than argument has supplied. The
uneasiness that is apt to attend suspense of belief has required, in
general, a more powerful remedy. Next to those who have solely
employed their rational faculties in theology, we may place those
who have relied on a supernatural illumination. These have
nominally been many; but the imagination, like the reason, bends
under the incomprehensibility of spiritual things; a few excepted,
who have become founders of sects, and lawgivers to the rest, the
mystics fell into a beaten track, and grew mechanical even in their
enthusiasm.
Extended 90. No solitary and unconnected meditations, however,
inferences either of the philosopher or the mystic, could furnish a
from sacred
books. sufficiently extensive stock of theological faith for the
multitude, who, by their temper and capacities, were
more prone to take it at the hands of others than choose any tenets
for themselves. They looked, therefore, for some authority upon
which to repose; and instead of builders, became as it were
occupants of mansions prepared for them by more active minds.
Among those who acknowledged a code of revealed truths, the
Jews, Christians, and Mahometans, this authority has been sought in
largely expansive interpretations of their sacred books; either of
positive obligation, as the decisions of general councils were held to
be, or at least of such weight as a private man’s reason, unless he
were of great name himself, was not permitted to contravene. These
expositions, in the Christian Church, as well as among the Jews,
were frequently allegorical; a hidden stream of esoteric truth was
supposed to flow beneath all the surface of Scripture; and every text
germinated, in the hands of the preacher, into meanings far from
obvious, but which were presumed to be not undesigned. This
scheme of allegorical interpretation began among the earliest
fathers, and spread with perpetual expansion through the middle
ages.[417] The Reformation swept most of it away; but it has
frequently revived in a more partial manner. We mention it here only
as one great means of enabling men to believe more than they had
done, of communicating to them what was to be received as divine
truths, not additional to Scripture, because they were concealed in
it, but such as the church could only have learned through its
teachers.
[417] Fleury (5me discours), xvii. 37. Mosheim, passim.
His literary 96. Picus, about the end of 1486, repaired to Rome, and
performances.with permission of Innocent VIII., propounded his
famous nine hundred theses, or questions, logical, ethical,
mathematical, physical, metaphysical, theological, magical, and
cabbalistical; upon every one of which he offered to dispute with any
opponent. Four hundred of these propositions were from
philosophers of Greece or Arabia, from the schoolmen, or from the
Jewish doctors; the rest were announced as his own opinions,
which, saving the authority of the church, he was willing to defend.
[421] There was some need of this reservation; for several of his
Origin of 103. The less regular, though in their day not less
dramatic interesting, class of scenical stories, commonly called
mysteries.
mysteries, all of which related to religious subjects, were
never in more reputation than at this time. It is impossible to fix
their first appearance at any single æra, and the inquiry into the
origin of dramatic representation must be very limited in its subject,
or perfectly futile in its scope. All nations, probably, have at all times,
to a certain extent, amused themselves both with pantomimic and
oral representation of a feigned story; the sports of children are
seldom without both; and the exclusive employment of the former,
instead of being a first stage of the drama, as has sometimes been
assumed, is rather a variety in the course of its progress.
Their early 104. The Christian drama arose on the ruins of the
stage. heathen theatre: it was a natural substitute of real
sympathies for those which were effaced and condemned. Hence we
find Greek tragedies on sacred subjects almost as early as the
establishment of the church, and we have testimonies to their
representation at Constantinople. Nothing of this kind being proved
with respect to the west of Europe in the dark ages, it has been
conjectured, not improbably, though without necessity, that the
pilgrims, of whom great numbers repaired to the East in the
eleventh century, might have obtained notions of scenical dialogue,
with a succession of characters, and with an ornamental apparatus,
in which theatrical representation properly consists. The earliest
mention of them, it has been said, is in England. Geoffrey,
afterwards abbot of St. Albans, while teaching a school at Dunstable,
caused one of the shows, vulgarly called miracles, on the story of St.
Catherine, to be represented in that town. Such is the account of
Matthew Paris, who mentions the circumstance incidentally, in
consequence of a fire that ensued. This must have been within the
first twenty years of the twelfth century.[441] It is not to be
questioned, that Geoffrey, a native of France, had some earlier
models in his own country. Le Bœuf gives an account of a mystery
written in the middle of the preceding century, wherein Virgil is
introduced among the prophets that come to adore the Saviour;
doubtless in allusion to the fourth eclogue.
[441] Matt. Paris, p. 1007 (edit. 1684). See Warton’s 34th section (iii. 193-
233), for the early drama, and Beauchamps, Hist. du Théâtre Français,
vol. i., or Bouterwek, v. 95-117, for the French in particular; Tiraboschi,
ubi suprà, or Riccoboni, Hist. du Théâtre Italien, for that of Italy.
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