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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).
"Te tapoitte hänet sen — sen vuoksi?" kysyi Josephine. "Ben tunsi
teidät, hän tiesi, että ette aikonut viedä minua Laskariin.
"Näet siis, että kun en kerran voi ase kädessä saada hänestä
voittoa ja kun vihaan häntä siinä määrin kuin teen, että minun täytyy
käyttää muita keinoja musertaakseni hänet ja saadakseni hänet
harmista vääntelehtimään. Sen vuoksi, että Brannon pitää sinusta —
sen vuoksi vien sinut siis Panya Cacheen. Ja toisena syynä siihen
on se, että minä pidän itse sinusta.
Viimeinen paljastus, tullen heti sen jälkeen kuin hän oli päässyt
selvyyteen Lattimerin todellisesta luonteesta, vei kokonaan hänen
voimansa. Hän tunsi Lattimerin lujat käsivarret ympärillään ja taisteli
häntä vastaan, vaikka tiesi sen toivottomaksi. Hän kuuli hänen
puhuttelevan häntä töykeästi ja tunsi, että häntä kannettiin ja sitten
käyden epätoivon vimmalla satulan nuppiin hän tunsi nousevansa
ylöspäin.
Yhdesneljättä luku.
Musta kiiti alussa tuulena tasangon yli. Sen vauhti hiljeni vähitellen
kun se kierteli muutaman matalan kukkulan juuria, joille alkuvuorista
irtautuneita kallionlohkareita oli vierinyt sen tielle. Se kiipesi
äkkijyrkkää rinnettä taitavasti kuin kissa ja juoksi sitten vuoren
harjannetta pitkän matkaa, syöksyi saccaton-heinää kasvavalle
lakeudelle huimaavaa vauhtia, riensi taasen jyrkkää vuorenkuvetta
ylös ja poikki toisen ruohokentän saman korkean vuorenhuipun
juurella, jolta Josephine edellisenä yönä oli katsellut suureen
laaksoon.
Brannon tunsi siis tien varsin hyvin. Siitäkin huolimatta olisi hänellä
ollut sangen helppo seurata Lattimeria ja Josephineä, sillä heidän
jälkensä näkyivät selvästi matkan pehmeillä osilla.
Kahdesneljättä luku.
Tottumattomana pitkiin ratsastusmatkoihin ja lopen väsyneenä
siitä jännityksestä, minkä matkan vaarat olivat aiheuttaneet, oli
Josephinen pakko jatkaa kulkuaan. Ja ajatellessaan toivotonta
tulevaisuuttaan, itki hän lohduttomasti hevosen laskeutuessa vuoren
syrjännettä heinäiselle tasamaalle.
Ja nyt, kun hän johti hevostaan rinnettä alas, kuoli hänen toivonsa
kokonaan ja hän puhkesi itkuun. Lattimer ratsasti hänen luokseen ja
pani toisen kätensä hänen olkapäälleen.
Se oli Denver. Hän oli ilmestynyt kuin näky. Mutta Josephine tiesi,
että hän olisi saattanut ratsastaa heitä kohti tuntikausia heidän
tietämättään mitään hänestä. Sillä se, joka tahtoi kulkea salassa,
saattoi menestyksellä käyttää hyväkseen niitä kukkuloita, laaksoja,
kallioita ja syvänteitä, joita seutu oli täynnään. Ja hän tiesi myös, että
Denver ei olisi näyttäytynyt jos hän vain oli huomannut heidät,
ennenkuin hän oli varma heidän henkilöllisyydestään. Se kuului
miehen luonteenominaisuuksiin.
"Brannon!"
Kolmasneljättä luku.
Ei ollut muuta kuin yksi keino ja sitä hänen täytyi käyttää. Brannon
oli ollut hänen ystävänsä koko ajan, koettaen turhaan näyttää
hänelle kuinka mielettömät hänen puuhansa olivat ja hän oli
käyttänyt oveluutta, jotta Josephine ei olisi loukkaantunut. Josephine
ei senvuoksi saattanut uhrata Brannonia edes siten pelastuakseen
itse uhkaavasta häpeästä. Koettaen vaientaa sisässään riehuvaa
myrskyä ja epätoivoisesti pyrkien tyyneksi, jotta ei Brannon epäilisi
häntä, onnistui hänen hymyillä hänelle Mustan pysähtyessä hänen
eteensä ja Brannonin hypähtäessä satulasta.
"Oli sitä mieltä, että te teitte väärin!" kertasi Brannon. "Mitä sillä
tarkoitatte?"
Mutta hän näkikin nyt, että hän oli erehtynyt ja että Brannon ei ollut
niinkään altis jättämään häntä. Josephine tunsi, että Brannonin täytyi
epäillä hänen valehtelevan tai että hänellä oli jotakin sanomista
Lattimerille Whitmanin ampumisen johdosta — vaikka, jos kerran
Whitman eli, niin —.
Jos Brannon sen vuoksi aikoi tavata Lattimeriä, niin täytyi hänen
estää se.
"Tuletteko?"