Hamaker Constants of Inorganic Materials

ELSEVIER
Advancesin Colloid and Interface Science 70(1997) 125-169
ADVANCESIN COLLOID AND INTERFACE SCIENCE
Hamaker constants of inorganic materials

Lennart Bergstr6m
Institute for Surface Chemistry, P.O. Box 5607, S-114 86 Stockholm, Sweden
Abstract
Calculations of H a m a k e r constants using Lifshitz t h e o r y require the a v a i l a b i l i t y of a c c u r a t e dielectric data, especially in the ultraviolet spectral region, a n d the use of a convenient a n d a p p r o p r i a t e m a t h e m a t i c a l representation. In this review, a m u l t i p l e oscillator model - - t h e so-called N i n h a m - P a r s e g i a n ( N - P ) r e p r e s e n t a t i o n - - h a s been used a n d spectral p a r a m e t e r s for 31 different inorganic m a t e r i a l s (including diamond) h a v e been g e n e r a t e d from critically e v a l u a t e d optical d a t a or collected from the literature. F o r m o s t m a t e r i a l s , a two-oscillator model (one UV a n d one IR t e r m ) was used b u t more d e t a i l e d r e p r e s e n t a t i o n s were included when available. The spectral p a r a m e t e r s p r e s e n t e d h e r e can be combined with previous data, m a i n l y focused on hydrocarbon a n d organic systems, to yield a n extensive spectral d a t a b a s e for both solids a n d liquids e n a b l i n g Lifshitz calculations of H a m a k e r constants for m a n y m a t e r i a l s combinations. N o n - r e t a r d e d H a m a k e r constants for s y m m e t r i c m a t e r i a l combinations across vacu u m (Alvl) a n d w a t e r (Alwl) have been calculated for the different m a t e r i a l s ; these calculations were p e r f o r m e d using t h e full Lifshitz theory. A s y m m e t r i c combinations, A lv3 a n d A lw3, a g a i n s t four commonly used m a t e r i a l s in atomic force microscopy studies: silica, a m o r p h o u s silicon nitride, s a p p h i r e , a n d muscovite mica, have also been covered. The use of a new dielectric r e p r e s e n t a t i o n for w a t e r r e s u l t e d in significantly lower values of A l w l c o m p a r e d to previous calculations. Analytical a p p r o x i m a t i o n s to the full Lifshitz t h e o r y were e v a l u a t e d a n d found to give s u r p r i s i n g l y accurate r e s u l t s (the T a b o r - W i n t e r t o n a p p r o x i m a t i o n ) for A l v l when t h e IR contribution is of m i n o r importance. An a t t e m p t to m a k e t h e TW a p p r o x i m a t i o n more general by e s t a b l i s h i n g some scaling r e l a t i o n s h i p b e t w e e n no and couv was m e t with little success; only t h e UV spectral p a r a m e t e r s of the covalent oxides, sulphides and n i t r i d e s m a y be fitted to a simple power law relation. The Lifshitz calculations in this s t u d y were compared with an a l t e r n a t i v e m e t h o d w h e r e a more d e t a i l e d dielectric r e p r e s e n t a t i o n in the visible-ultraviolet spectral r a n g e w a s o b t a i n e d t h r o u g h K r a m e r s - K r o n i g ( K - K ) t r a n s f o r m a t i o n of reflectivity d a t a over a broad frequency range. Despite the difference in dielectric information, the two 0001-8686/97/$32.00 1997 - - Elsevier Science B.V. All rights reserved.
PII: S0001-8686(97)00003-1
126
L. BergstrSm /Adv. Colloid Interface Sci. 70 (1997) 125-169
m e t h o d s g e n e r a l l y yield n o n - r e t a r d e d H a m a k e r constants which do not differ significantly. This is not t r u e for all m a t e r i a l s , e.g. water, w h e r e a more d e t a i l e d r e p r e s e n t a t i o n using e i t h e r an N - P r e p r e s e n t a t i o n with several oscillators or the K - K r e p r e s e n t a t i o n m u s t be used. It was shown t h a t the omission of the static and low frequency contribution in the l a t t e r m e t h o d m a y r e s u l t in a significant u n d e r e s t i m a t i o n of the value for Alwl w h e n the dispersive contribution becomes v e r y small. Keywords: H a m a k e r constant, v a n der W a a l s interaction, inorganic m a t e r i a l s , i n t e r p a r ticle forces, A F M
Contents
Introduction .................................... Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IIA. Dielectric response . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IIB. Calculation of n o n - r e t a r d e d H a m a k e r constants . . . . . . . . . . . . III. Dielectric r e p r e s e n t a t i o n . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IIIA. Dielectric d a t a of m a t e r i a l s . . . . . . . . . . . . . . . . . . . . . . . . IIIB. D e t e r m i n a t i o n of spectral p a r a m e t e r s . . . . . . . . . . . . . . . . . . IV. S p e c t r a l p a r a m e t e r s of m a t e r i a l s . . . . . . . . . . . . . . . . . . . . . . . . IVA. A m o r p h o u s m a t e r i a l s . . . . . . . . . . . . . . . . . . . . . . . . . . . IVB. Cubic h a l i d e s . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . IVC. Cubic covalent m a t e r i a l s . . . . . . . . . . . . . . . . . . . . . . . . . IVD. Hexagonal, t e t r a g o n a l and trigonal m a t e r i a l s . . . . . . . . . . . . . . IVE. Birefringent m a t e r i a l s . . . . . . . . . . . . . . . . . . . . . . . . . . . V. C a l c u l a t e d H a m a k e r constants . . . . . . . . . . . . . . . . . . . . . . . . . VA. I m p o r t a n c e of the IR r a n g e . . . . . . . . . . . . . . . . . . . . . . . . VB. Full Lifshitz calculations a n d analytical a p p r o x i m a t i o n s . . . . . . . . VC. H a m a k e r constants for use in A F M studies . . . . . . . . . . . . . . . VD. S p e c t r a l p a r a m e t e r scalings . . . . . . . . . . . . . . . . . . . . . . . . VE. C o m p a r i s o n w i t h a K r a m e r s - K r o n i g dielectric r e p r e s e n t a t i o n . . . . . VI. S u m m a r y and conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . I. II. 126 129 129 134 137 137 139 142 142 143 145 147 149 150 150 154 155 159 162 165 167
I. I n t r o d u c t i o n
The surface forces between two bodies in close proximity play an important role in many scientific and technical areas, e.g. adhesion, wetting, adsorption, colloidal phase equilibrium, flocculation rates, rheologic a l p r o p e r t i e s a n d o t h e r c o l l o i d a n d i n t e r f a c e p h e n o m e n a [1,2]. I n p h e n o m ena involving inorganic materials, examples include the important role of interparticle forces in determining the rheological behaviour of the ceramic suspensions in the powder preparation and consolidation step [2-4], and
L. Bergstr6m/Adv. Colloid Interface Sci. 70 (1997) 125-169
127
the suggestion t h a t a surface force balance controls the thickness of t h i n i n t e r g r a n u l a r glass films in polycrystalline ceramics [5]. A m o n g the m a n y contributions to the interaction between surfaces, e.g. double layer, structural, steric, depletion, h y d r a t i o n and hydrophobic forces, t h e r e is one type of interaction which is always present, the van der Waals interaction. This ubiquitous interaction m a y be of v a r y i n g importance depending on the system. The H a m a k e r constant represents a conventional and convenient way of assessing the m a g n i t u d e of this interaction. Recent work has shown t h a t m a n y inorganic systems are characterised by relatively high H a m a k e r constants [6,7], hence m a k i n g this interaction of significant importance. It is obvious t h a t accurate estimations of the H a m a k e r constants is necessary for a quantitative u n d e r s t a n d i n g of the effect of interparticle forces on various phenomena. The van der Waals force has an electrodynamic origin as it arises from the interactions between atomic or molecular oscillating or rotating electrical dipoles within the i n t e r a c t i n g media. There are t h r e e types of interactions w h i c h contribute to the van der Waals force: (i) The Keesom force which is the interaction between two p e r m a n e n t dipoles. (ii) The Debye force which is the interaction b e t w e e n one p e r m a n e n t dipole a n d one induced dipole. (iii) The London or dispersion force which is the interaction between two induced dipoles. B e t w e e n molecules, each of these contributions has an interaction free e n e r g y w h i c h varies w i t h the inverse sixth power of the distance at small and intermediate distances of separation (from 1-2 .~ to several nm). H a m a k e r [8] calculated the distance dependence of the free e n e r g y of macroscopic bodies by performing a pair-wise s u m m a t i o n over all the atoms in the bodies. For example, the van der Waals interaction free energy, VvdW, per u n i t area, between semi-infinite parallel plates at separation, L, can be expressed as
Vvd w -
A 12xL 2
(1)
w h e r e A is the H a m a k e r constant. As seen in Eq. (1), t h e r e is a direct proportionality b e t w e e n the m a g n i t u d e of the van der Waals interaction and the H a m a k e r constant. The H a m a k e r constant is a m a t e r i a l s c o n s t a n t t h a t depends on the properties of the two m a t e r i a l s and the i n t e r v e n i n g media. The distance d e p e n d e n c e of the van der Waals e n e r g y depends essentially on the geometry of the two i n t e r a c t i n g bodies
128
being proportional to L -2 for parallel plates and scale to L -1 for two spherical particles at short separation distances where retardation can be ignored. In the original treatment, also called the microscopic approach, the H a m a k e r constant was calculated from the polarizabilities and number densities of the atoms in the two interacting bodies [8]. Lifshitz presented an alternative, more rigorous approach where each body is treated as a continuum with certain dielectric properties [9]. This approach automatically incorporates many-body effects which is neglected in the microscopic approach. In the Lifshitz treatment, the van der Waals interaction is the result of fluctuations in the electromagnetic field between two macroscopic bodies, modified by the separating media, where the interaction can be referred to the standing waves which only occur at certain frequencies. Hence, the van der Waals interaction, and thus the associated H a m a k e r constants, can be estimated from a knowledge of the frequency dependent dielectric properties of the interacting materials together with the intervening medium, and the geometry of the bodies. The accuracy of the estimated H a m a k e r constants are directly related to the precision and accuracy of the dielectric spectra and the mathematical representation of this data. The main focus of this review is to provide a collection of dielectric representations for a range of inorganic materials presented in a condensed but appropriate manner, suitable for calculations of accurate H a m a k e r constants. The dielectric representation follows the form presented by Hough and White [10] in their collection of spectral parameters and H a m a k e r constants for a number of materials, focusing mainly on liquids and organic solids. Since their work was published, collections of accurate dielectric data for many inorganic materials have become easily available [11,12] which makes the determination of the necessary spectral parameters an easy task. The two handbooks of Optical Constants of Solids I and II [11,12] will constitute the main source of dielectric spectral information but previously published data will also be included. In the next, theoretical section, the basis of the dielectric response representation and an outline of the Lifshitz theory for van der Waals forces together with a description of simplifying assumptions made to facilitate calculations will be described. It should be noted that no theoretical advances are being presented here; the theoretical section completely relies on previously published material and merely forms a basis for the estimations of spectral parameters and calculations of
129
H a m a k e r constants. This is followed by a presentation of dielectric data and discussion how the spectral parameters in the ultraviolet (UV) and the infrared (IR) frequency range can be determined. The spectral parameters for 31 different inorganic materials (including diamond) are either taken directly from the literature or estimated from data on the static dielectric constant, ~(0), the frequency dependence of the refractive index, n(o~), in the UV frequency range, and the frequency of the strongest IR-absorption band. Non-retarded Hamaker constants for the inorganic materials across vacuum and water was calculated using the full Lifshitz theory. In addition, Hamaker constants for systems important in atomic force microscopy (AFM) studies have also been calculated. A recently published improved spectral parametric representation of water [13] has been used for these calculations which resulted in some significant changes compared to previous estimates. The full Lifshitz calculations have been compared with various analytical simplifications and a surprisingly good agreement was found for the Hamaker constants with vacuum as the intervening medium. The importance of the IR range for the calculation of H a m a k e r constants was evaluated. In the final section, the H a m a k e r constants obtained in this study were compared with calculations based on an alternative dielectric representation using K r a m e r s Kronig relations.
II. Theory
IIA. Dielectric response
The dielectric properties of a material are commonly represented by the frequency dependent dielectric response function, e(co) c(o) = c'(co) + ic"(co) (2)
which is a complex function where e'(co) is the real part, and e"(co) the imaginary part. This function is intimately related to the transmission (c'(co)) and absorption (e"(o~)) of the applied electromagnetic radiation. In frequency regions where e"(o) is zero, the material is transparent and the real part of the dielectric response is directly related to the refractive index, n(co) through c(co) = c'(9) = n2(~o) (3)
130
For a static applied field (co = 0), non-conductor m a t e r i a l s are characterised by e"(co) ~- 0, h e n c e ~'(0) = a(0) which is the static dielectric constant. As a completely equivalent a l t e r n a t i v e to the dielectric response function, e(o~), can the complex refractive i n d e x , N(c0), be used
N(o~) = n(co) - i k ( o )
(4)
w h i c h m i g h t be more familiar to some readers. The real part, n(o2), r e p r e s e n t s the refractive index and k(o3) is the extinction coefficient. R e m e m b e r i n g the transmission and absorption d e p e n d e n c e of the complex dielectric function, the m a t h e m a t i c a l connection between a(co) and N(o~) can be expressed as:
~(o~) = N2(co)
(5) (6) (7) (8)
N2(co) = (n(co) - ik(o))2 e'(co) = n2(o)) - k2(o) e"(o) = 2n(co)k(o)
Dielectric d a t a can be obtained with a n u m b e r of methods including capacitance bridge, optical reflectance and ellipsometric techniques, and electron loss spectroscopy. Most of these techniques yield only one of the components of the complex dielectric response function w h i c h often necessitate the t r a n s f o r m a t i o n from the real to the i m a g i n a r y c o m p o n e n t or v i c e v e r s a . Such a t r a n s f o r m a t i o n can be performed using the K r a m e r s - K r o n i g (K-K) relations, one of t h e m defined as a'(co) = 1 + 2 i ~ _ - ~ 2 dx
0
xe"(o))
(9)
w h e r e x r e p r e s e n t s real values of the frequency. The K - K relation in Eq. (9) shows t h a t if e"(o~) (i.e. the absorption spectrum) is k n o w n in the entire frequency range, 0 < co < ~, t h e n e'(o~) can be fully defined. Similar K - K relations can be defined for other dielectric properties such as the f r e q u e n c y d e p e n d e n t i n t e r b a n d transition s t r e n g t h [7]. N i n h a m a n d P a r s e g i a n [14,15] showed t h a t by constructing an imagin a r y dielectric response function, e(i~m), a m u c h simpler dielectric r e p r e s e n t a t i o n could be used for the purpose of calculating H a m a k e r constants. H o u g h and White [10] have given a t h o r o u g h analysis of this representation. The reason for using this i m a g i n a r y r e p r e s e n t a t i o n is
L. Bergstr~m /Adv. Colloid Interface Sci. 70 (1997) 125-169
131
completely m a t h e m a t i c a l , the i m a g i n a r y p a r t of the frequency has no physical significance t h a t refers to the m a t e r i a l s behaviour. The complex i m a g i n a r y function decreases monotonically from ~0 w h e n ~ = 0, a n d goes to 1 as ~ approaches infinity. The final form of the Lifshitz expression for calculation of H a m a k e r constants (see next section) shows t h a t i m a g i n a r y dielectric function only has to be e v a l u a t e d at discrete, equally spaced i m a g i n a r y frequencies, i~m, w i t h
~m = rn( 4~2kB T/h )
(10)
w h e r e h is Planck's constant, k B represents Boltzmann's constant, m is an integer; m = 0,1,2,3,4.., and T is the t e m p e r a t u r e in Kelvin. The i m a g i n a r y dielectric response function, e(i~m), can be obtained from g'(co) using a n o t h e r K r a m e r s - K r o n i g relation [10]:
oo
~(i~) = 1 + ~ ~ x2 + ~2 dx
0
_2f
(11)
The K - K relation in Eq. (10) has been used in several studies to construct the n e c e s s a r y a(i~m) function [7,16,17] for estimations of H a m a k e r constants. However, since the K - K relation is formally correct only w h e n ~"(co) is k n o w n in the entire frequency range, 0 < 0`) < ~, this p r o c e d u r e is prone to n u m e r i c a l error since approximations for parts of the absorption s p e c t r u m invariably has to be used due to lack of spectral information. With limited dielectric data available, the function s(i~m) is usually represented by a model based on a damped oscillator. The so-called N i n h a m - P a r s e g i a n (N-P) representation of ~(i~) can be given as [14,15, 18,191
N
~(i~m) = 1 + 1 + ~----~ + y=" 1 + (~

j=l
/coj)2 + gj~ /0.)2
Cj
(12)
w h e r e the first t e r m after u n i t y represents the contribution from the orientation of p e r m a n e n t dipoles (present in polar liquids like water), a n d t h e final s u m m a t i o n relates to the absorption peaks in the infrared and ultraviolet range. B and gj are related to the oscillator s t r e n g t h in the microwave r a n g e and d a m p i n g coefficient of the oscillator, respectively, and Cj is r e p r e s e n t e d by
cj-
2 fj
(13)
132
where fj is the oscillator strength and coj is the relaxation frequency (in the unit rad/s) of the absorption band. The N-P representation simplifies the construction of the required function e(i~m) since the frequencies and relative strengths of the peaks in the absorption spectrum can be used. With a well-characterised absorption spectrum over a relatively wide frequency range, many spectral parameters can be defined. Water is such a material and spectral parameters in the ultraviolet, infrared as well as the microwave range have been determined [13,20]. Roth and Lenhoff [13] have recently published an improved UV representation of water based on previously published reflectivity data [21]. Figure 1 shows that the real and imaginary dielectric data in the important frequency range can be closely fitted by using the summation in Eq. (12) and six [IV terms including band widths. The full spectral representation of water including one microwave term and five infrared terms from Parsegian [20] and the six UV terms from Roth and Lenhoff [13] are collected in Table 1. The accuracy of Hamaker constants calculated from Lifshitz theory relies on the quality of the experimental dielectric data and the accuracy of the spectral representation. With dielectric data over a wide frequency range, the two alternative methods: K-K transformation using Eq. (11), or the N - P representation, Eq. (12), should yield a similar result. If the dielectric data is limited, both approaches may result in inaccurate representations. The K-K transformation is sensitive to the
Table 1 Spectral parameters* for water**
eli V
O~uvx 1016 (rad/s)

1.25 1.52 1.73 2.07 2.70 3.83
guv 1015 (tad/s)

0.957 1.28 3.11 5.92 11.1 8.11
CIR
C 0 1 RX 1014 (rad/s)
0.314 1.05 1.40 3.06 6.46
gIR 1013 (rad/s)

2.29 5.78 4.22 3.81 8.54
0.0484 0.0387 0.0923 0.344 0.360 0.0383
1.46 0.737 0.152 0.0136 0.0751
B = 76.8 a n d 1/TMW = 1.08 x 1011 rad/s. * C m a n d Cuv are the absorption strengths, and com and a)uv r e p r e s e n t the characteristic absorption frequencies in the IR and UV range, respectively. The d a m p i n g t e r m s are denoted by gia a n d guy. ** UV r e p r e s e n t a t i o n from Roth and Lenhoff [13], and IR a n d microwave r e p r e s e n t a t i o n from P a r s e g i a n [20].
L. BergstrSm/Adv. Colloid Interface Sci. 70 (1997) 125-169
133
(a)
... Roth and L e n h o f f [13] 2.5 - - P a r s e g l a n [14] - - Data [21._._~_~] m
1.5
LL
0.5
0 0
10
15
Frequency (eV)
20
25
30
(b)
1.8 1.6 1.4
1.2
/',~
~"
.,. Roth and L e n h o f f [13] . - P a r s e g l a n [14]

~ uuta L~:lj
0.8 0.6
0.4 0.2 0
! I i i i
10
15 Frequency (eV)
20
25
30
Fig. 1. Comparison of experimental dielectric data (solid line) for water of the real (a) and imaginary (b) component [21], and two different mathematical representations (broken lines) from Parsegian [14] and Roth and Lenhoff [13]. Each representation uses six oscillators including band widths. From Roth and Lenhoff [13].
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L. Bergstr6rn/Adv. ColloidInterface Sci. 70 (1997) 125-169
approximations outside the available spectral data, and the N - P representation, using a limited n u m b e r of oscillators, m a y be of poor quality for m a t e r i a l s w i t h complicated spectral features. However, t h e r e is some evidence t h a t m a n y m a t e r i a l s w i t h "simpler" spectral f e a t u r e s can be reasonably well described by less complicated N - P r e p r e s e n t a t i o n s [10]. At room t e m p e r a t u r e , ~m are sampled at i n t e g r a l multiples of 2.4 1014 rad/s w h i c h corresponds to one static term, only a few t e r m s in the infrared and m a n y in the visible-ultraviolet region. Hence, since the dielectric response in the visible-UV r a n g e completely d o m i n a t e s the v a n der Waals interaction for most systems, it is of outmost importance to have access to accurate spectral d a t a in this frequency range. In this study, E(i~m) for most of the inorganic m a t e r i a l s will be r e p r e s e n t e d by one UV and one IR relaxation e(i~m) = 1 +
CIR CUV + l+(~/com) 2 l+(~/O)uv) 2
(14)
w h e r e each m a t e r i a l is characterised by four parameters; CIR and Cvv are t h e absorption s t r e n g t h s in the IR and UV range, respectively, a n d 0)IR a n d a)vv r e p r e s e n t the characteristic absorption frequencies in the IR a n d UV range, respectively. The d a m p i n g t e r m s are omitted. In some cases w h e n a more detailed r e p r e s e n t a t i o n has already been presented, this d a t a will be included. The limitations and accuracy of this dielectric r e p r e s e n t a t i o n will be discussed in more detail later.
IIB. Calculation of non-retarded Hamaker constants

The interaction free e n e r g y per u n i t area, E132, b e t w e e n two halfspaces of m a t e r i a l 1 and m a t e r i a l 2 interacting over m e d i a 3, can in the n o n - r e t a r d e d approximation (small separation distance, L) be w r i t t e n as [9,10,18]
E132- ~
kBT
2" I m--0 0
ydy ln(1 - A13A23 e -2yL)
(15)
w i t h the differences in dielectric response, Akl, defined as
ak(i~m ) -- ez(i{m )
Akl- ek(i~m ) + e/(i~ m)
(16)
135
where ek(i~m) and el(i~m) are the dielectric response function of material k and l, respectively, evaluated at the imaginary frequency, i~ n according to Eq. (10). The prime on the first summation in Eq. (15) indicates that the m = 0 term (the static contribution) is given half weight. By a change of variables (x = 2yL), it is possible to define El32 according to Eq. (1), A132 El3 2 = - 12EL 2 (17)
thus identifyingthe non-retarded Hamaker constantA132 which is given

as
A132 -
3kBT 2 ~'
f dxx ln(1 - A13A23e -x)
(18)
m=O 0
This integral can be performed analytically to yield
3kBT
A1322 ~'~
rn=0 s = l
(A13A23)s s3
(19)
A detailed account of how this double summation equation (Eq. (19)) is derived directly from the original expression given by Lifshitz [9] can be found in previous work [18]. The frequency sum can be replaced by an integral to yield
A132:
3h
f at E
0 s=l
(A13A23)s
s3
(20)
which is correct only in the limit, T --->0, where the distance between the sampled frequencies (Eq. (10)) tend to zero [9,18]. This transformation is equivalent to omitting the static term (m = 0, ~ = 0) in the frequency summation (Eq. (19)). The temperature independent dispersive part of the non-retarded Hamaker constant, represented by the summation m > 1, however, is not affected by the transformation. Hence, when the static contribution to the non-retarded Hamaker constant is negligible, the error of using Eq. (20) will be minor. However, when water or another material characterised by a high static dielectric constant is one part of the system, the static contribution may be significant thus restricting the use of the integral equation (Eq. (20)).
136
T h i s will be i l l u s t r a t e d in m o r e d e p t h later. Also, at e l e v a t e d t e m p e r a t u r e s , t h e static c o n t r i b u t i o n to t h e H a m a k e r c o n s t a n t m a y be large. Simplified a p p r o x i m a t i o n s for less a c c u r a t e e s t i m a t i o n s of non-ret a r d e d H a m a k e r c o n s t a n t s h a v e been derived for a n u m b e r of cases by only r e t a i n i n g a single UV r e l a x a t i o n to r e p r e s e n t t h e dielectric r e s p o n s e of each m a t e r i a l . T h e s e simplifications h a v e b e e n m o t i v a t e d by t h e pivotal role of t h e u l t r a v i o l e t r e l a x a t i o n s on t h e m a g n i t u d e of t h e d i s p e r s i v e interactions. W i t h s u c h a simple dielectric r e p r e s e n t a t i o n , e a c h m a t e r i a l is fully described by t h r e e p a r a m e t e r s , e(0), t h e characteristic f r e q u e n c y in t h e ultraviolet, otr, a n d t h e low-frequency limit of t h e refractive i n d e x in t h e v i s i b l e - U V r a n g e , n o (since Cuv = n2s - 1). F o r e x a m p l e , t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t for two identical m a t e r i a l s 1, i n t e r a c t i n g across a m e d i u m 3 w a s calculated by u s i n g Eq. (19), n e g l e c t i n g all s u m m a t i o n t e r m s s > 1, c o n v e r t i n g t h e s u m m a t i o n over n to an i n t e g r a l for m > 1, a n d finally s e t t i n g (01 -- 033 ~ 03. This r e s u l t s in [1] 3he0 (n 2 -- n2) 2 3 k T tel(0) _ e3(0)~2 A131 = T el(0 ) + ~ !) + 3 2 ~ / 2 n21 + n32)3/2
(21)
w h e r e t h e first t e r m on t h e r i g h t h a n d side r e p r e s e n t s t h e static c o n t r i b u t i o n a n d t h e second t e r m r e p r e s e n t s t h e dispersive c o n t r i b u t i o n a n d n I a n d n 3 is t h e refractive index in t h e visible of t h e m a t e r i a l a n d m e d i u m , respectively. If t h e m e d i u m is v a c u u m a n d t h e static contribution is ignored, Eq. (21) r e d u c e s to t h e so called T a b o r - W i n t e r t o n (TW) r e p r e s e n t a t i o n [22]. A m o r e complicated expression for t h e dispersive c o n t r i b u t i o n is o b t a i n e d if t h e i n t e r a c t i n g m a t e r i a l a n d t h e m e d i u m are allowed to h a v e different a b s o r p t i o n frequencies 031 (03 [23]. Adisp,131 = 3h ~ (X2 ~ + 2XAe a 1/2 + Ae2(3 + 211)) 1 2 8 / ~ 7'4 [ ( y _ h/~-~-i-)1/2 + (Y + a ] - ~ _ lil/213
(22)
where = 0.5(nl 2 + n32) AE = n 2 - n 2

X = - - ( n 2 - i ) - - - (n~- 1) (01 (03-
)1
(03
L. BergstriJm/Adv. Colloid Interface Sci. 70 (1997) 125-169
137
Y = 4_~1/---~
(n 2 + 1) + - - (n 2 + 1)
COl
It m a y be shown t h a t Eq. (22) will be identical to the dispersive p a r t of Eq. (21) if 31 and (03 are replaced with co. These approximations of the n o n - r e t a r d e d H a m a k e r constant and others r e p r e s e n t i n g dissimilar m a t e r i a l s across a dielectric and interactions b e t w e e n coated m a t e r i a l s have been presented in a condensed form by Prieve and Russel [19]. In this study, the appropriateness of the different approximations for inorganic materials will be evaluated and the importance of the IR-range and the static contribution to the m a g n i t u d e of the H a m a k e r constant will be evaluated. For the full Lifshitz calculations using Eq. (19), a s u m m a t i o n over s = 1 to 4 and the first 3000 t e r m s of m w h e r e employed.
III. Dielectric r e p r e s e n t a t i o n
IIIA. Dielectric data of materials The dielectric response can be directly referred to the electronic and vibrational states of a material. In the infrared region, lattice vibrations d o m i n a t e while in the ultraviolet-visible frequency range, electronic or i n t e r b a n d transitions d o m i n a t e for a non-conducting solid. T h e r e is a w e a l t h of d a t a on the frequency dependence of the optical properties of solid inorganic m a t e r i a l s available in the literature. M a n y inorganic m a t e r i a l s h a v e been critically s u m m a r i s e d in the two H a n d b o o k s of Optical C o n s t a n t s of Solids [11,12] which constitute an excellent source of d a t a for the p r e s e n t t a s k of elucidating spectral p a r a m e t e r s for inorganic materials. Some recently published optical d a t a on ceramic m a t e r i a l s [6] illust r a t e the typical features of the optical characteristics in the i m p o r t a n t UV-visible range. Figure 2 shows a plot of the refractive index, n(c0), a n d extinction coefficient, k(co) (ZnO only), as a function of photon e n e r g y for the polycrystalline materials: 6H-SiC, tetragonal ZrO2, a-A1203, a n d ZnO based on spectroscopic ellipsometry m e a s u r e m e n t s . Three of these materials: SiC, ZrO 2 and A1203, display the n o r m a l dispersive b e h a v i o u r of a t r a n s p a r e n t material; the refractive index increases w i t h an increase in photon e n e r g y (frequency). This is related to a low photon absorption w i t h the extinction coefficient, k(co), close to zero and always below 0.1 (not shown). ZnO on the other hand, shows a distinct p e a k in the refractive index and a s h a r p increase in the extinction coefficient at
138
L. Bergstr6mlAdv. Colloid Interface Sci. 70 (1997) 125-169
(a)
3.5
3.0
C
.E
2.5 "5
O iv-
J
AI203
i i ,
2,0
1.5
P h o t o n e n e r g y (eV)
(b)
2.8 ZnO
1.0
2.6!
0.8
~'2.4
.E
,> 2.2
2.0
j
2 3
e,-
L_.
' 4
0.6 "~
0 0
0.4.
o
c x
0.2 I,U
1.8
0.0
P h o t o n e n e r g y (eV)
Fig. 2. Optical characteristics versus photon energy from ellipsometry measurements for (a) 6H-SiC, tetragonal, partially stabilized ZrO2, and a-A1203; and (b) ZnO. Taken from Ref. [6]. a critical p h o t o n e n e r g y . A t p h o t o n e n e r g i e s b e l o w 3.2 eV, t h e e x t i n c t i o n coefficient is close to zero (k < 0.05). H o w e v e r , a b o v e 3.3 eV, k s u d d e n l y i n c r e a s e s to k > 0.5. H e n c e t h e m a t e r i a l c e a s e s to b e t r a n s p a r e n t in t h e h i g h p h o t o n e n e r g y range. This t r a n s i t i o n is a s s o c i a t e d w i t h a n electronic e x c i t a t i o n since Z n O is a s e m i c o n d u c t o r w i t h a b a n d g a p a t 3.3 eV [24].
139
For the simplified spectral r e p r e s e n t a t i o n used in this study, optical d a t a over a relatively n a r r o w frequency range (as shown in Fig. 2) suffices for the elucidation of the UV term. However, if a more detailed spectral r e p r e s e n t a t i o n of the ultraviolet spectral region is to be constructed, dielectric d a t a over a wider frequency r a n g e is needed, as i l l u s t r a t e d for w a t e r in Fig. 1. Anisotropic m a t e r i a l s can display different dielectric responses in different crystal orientations. This can be r e p r e s e n t e d by a dielectric response function in tensorial form w h e r e the n u m b e r of i n d e p e n d e n t components depends on the crystal symmetry. Cubic systems only h a v e one component, i.e. display no anisometry, while tetragonal, hexagonal and trigonal systems have two components, r e s u l t i n g in optical birefringence. More complicated crystal forms such as orthorhombic, monoclinic a n d triclinic systems display a h i g h e r n u m b e r of components. In a birefringent material, the following n o m e n c l a t u r e is often used: no, n = o r d i n a r y ray, E p e r p e n d i c u l a r to the optical axis neo, n//= e x t r a o r d i n a r y ray, E parallel to the optical axis w h e r e E denotes the electric field. The s e p a r a t e components can only be d e t e r m i n e d for single crystals while polycrystalline m a t e r i a l s yields an a v e r a g e due to the r a n d o m orientation of the grains.
IIIB. Determination of spectral parameters

In the simplified r e p r e s e n t a t i o n of the ~(i~m) function used in this study, the ultraviolet frequency region is r e p r e s e n t e d by only one oscillator w h i c h can be w r i t t e n as ~(i~m) = 1 + Cuv 1 + (~ / tour) 2 (23)
valid at frequencies below the band gap and m u c h above the i n f r a r e d absorption band. For m a t e r i a l s t h a t do not absorb in the visible and UV range, the dielectric s p e c t r u m is simplified according to Eq. (3). H o u g h and W h i t e [10] utilised a simple graphic m e t h o d of obtaining Ouv and Cuv from the frequency d e p e n d e n c e of the refractive index, n(c0); the so-called "Cauchy equation" n2(co) - 1 = (n2(co) - 1) )2 + Cuv (24)
which should result in a linear plot of [(n2(o~) - 1)] versus [(n2(co) - 1) (o2].
140
L. B e r g s t r f m / A d v . Colloid Interface Sci. 70 (1997) 1 2 5 - 1 6 9
"C
~c
I I I
o. t":, ~.. o. ~. ~. ~. m. q. ~
O. ~.. ~. m. ~. e,!. ~
~. ~
g~
ea~
.~-~- F
~.~
L. Bergstr6m /Adv. Colloid Interlace Sci. 70 (1997) 125-169
141
~0
~D
~D
~ ~ ~ o ~ o ~ ~
a3
~9 9
~ ~ ~ o~ ~ o o ~ .o ~
~9 O 0 4.z
142
L. BergstrSm /Adv, Colloid Interface Sci. 70 (1997) 125-169
Figures 3-6 show "Cauchy" plots based on optical data from the literature [11,12] for a number of inorganic materials. The data was selected from the frequency range where the materials display negligible extinction coefficients (below the band gap) and sufficiently above the IR absorption range. More details of the spectral data is given below for each of the materials. The slope and intercept of the straight lines were determined by least square regression, which yields Cu r and tour. The UV-visible optical data for all the materials in this review can be well fitted to this type of single oscillator model. Materials where the optical data was too sparse or the Cauchy fit too poor, have not been included here. The values of the spectral parameters are collected in Table 2. A simplified infrared representation was used since the infrared and microwave contribution to the ~(i~m) function usually is of minor importance. This is due to the sparse sampling which is related to the large spacing of the sampling frequencies, ~m is about 2.5 1014 rad/s at room t e m p e r a t u r e (see Eq. (10)). The spectral constant CIR is given by
CIR -- E(O) -- C U V 1
(25)
and the characteristic absorption frequency, C0iR,will be defined as the frequency of the major absorption peak in the IR spectrum. The values of static dielectric constants for the different materials and the IR data were obtained from two major sources [12,25]. More details of the infrared data are given below for each material.
IV. Spectral p a r a m e t e r s of materials

The values of both the IR and UV spectral parameters for the 31 inorganic materials (including diamond) are summarised in Table 2. The dielectric data or representation of each material is briefly described below. All the spectral data represents room-temperature values.
IVA. Amorphous materials

Two amorphous materials were included in Table 2: silicon nitride (Si3N 4) and silica (SiO2). Senden and Drummond [26] have published a thorough analysis of the spectral parameters of these materials in both the UV-visible and infrared spectral region, included in Table 2.
L. Bergstri~m/Adv. Colloid Interface Sci. 70 (1997) 125-169
143
IVB. Cubic halides
All of the spectral parameters for the halides have been obtained from Cauchy plots (UV-visible spectral range), and infrared absorption peaks (IR spectral range) from the literature. Figure 3 shows that all of the cubic halides display a similar behaviour, well described by the single oscillator expression in the UV-visible range.
1. CaF2 Bezuidenhout [27] has compiled the data for calcium fluoride which is a highly ionic compound having a cubic fluorite crystal structure. The data of Malitson [28] on the refractive index values in the ultravioletvisible frequency range was used in the Cauchy plot (Fig. 3). The infrared absorption data from Kaiser et al. [29] was used to determine the frequency of the main absorption peak.
r , , ' J = ! I i , , , , i i , ,
I A
I "
c~
r-
.I
1 10 32
2 10 32
(o2(n2(oj)-1) [(rad/s) 2]
Fig. 3. Cauchy plots for the cubic ionic halide materials; (a) CsI, (b) KBr, (c) NaC], (d) KC1, (e) CaF2, (f) LiF, (g) NaF.
144
2. CsI Cesium iodide which has a cubic CsC1 structure does also display a very wide transmission band making it a common window material in infrared spectroscopy. Eldridge [30] has compiled the dielectric data and the ultraviolet-visible data used in the Cauchy plot (Fig. 3) were based on the tabulated values by Li [31]. The very low frequency of the infrared absorption peak was determined by Beairsto and Eldridge [32] using transmission measurements. 3. K B r The spectral data of potassium bromide having a cubic rock salt crystal structure has been compiled by Palik [33]. The collection and analysis of refractive index data by Li [34] was used for the Cauchy plot in Fig. 3. Infrared data from Johnson and Bell [35] was used for absorption peak determination. 4. K C l Palik [36] has also collected the spectral data of potassium chloride having a cubic rock salt crystal structure. The ultraviolet-visible data used in the Cauchy plot (Fig. 3) was based on refractive index data tabulated by Li [31]. The infrared absorption peak was identified with the transverse phonon frequency, also from Li [31]. 5. L i F Lithium fluoride also display the cubic rock salt crystal structure. The dielectric data has been compiled by Palik and H u n t e r [37], and the Cauchy plot in Fig. 3 is based on tabulated refractive index data by Li [38]. The identification of the main absorption peak in the infrared was based on the data by Kachare et al. [39]. 6. N a C l The refractive index data of sodium chloride used in the Cauchy plot in Fig. 3 was taken from Li [31] again, compiled by Eldridge and Palik [40]. The infrared data are from Eldridge and Staal [41]. 7. N a F The dielectric data of sodium fluoride, having a cubic rock salt crystal structure, was compiled by Ohlidal and Navratil [42]. The refractive index data in the ultraviolet-visible range was obtained from Harting [43], while the infrared data originates from Pai et al. [44].
145
IVC. Cubic covalent materials
The spectral parameters of two of the cubic, covalent materials, magnesium oxide (MgO) having a periclase structure and magnesium aluminate (MgA1204) having a spinel structure, were collected from a previous study using literature optical data [6].
1. C (diamond type IIa)
Although diamond (cubic carbon) cannot be classified as an inorganic solid, it was included in this review due to the general interest in this material. Diamond is classified into four types depending on its optical and electrical properties. Edwards and Philipp [45] have compiled spectral data for the natural types Ia and IIa and they concluded that the difference of the refractive index in the visible range is very small (less than 1%) between these types. In the Cauchy plot (Fig. 4), the
i ! = = i : i i i i , i | ! j = = : i i = r i i i i = : =
|St
.........
i .........
171
I 16
~
S
I3
CM
7 o 6 S rTiO a ~ ~ C (diamond II) 5 1030 1 SiC
I=
1 10 32
2 10 32
3 10 32
0)2(n2(~o)-1) [(radls) 2]
Fig. 4. Cauchy plots for the cubic materials: p-SiC, C (diamond type II), SrTiO3, ZnS, and PbS (insert).
146
L. BergstrOm/Adv. Colloid Interface Sci. 70 (1997) 125-169
sparse refractive index data from Peter [46] was used. The infrared absorption is of minor importance since the absorption, and thus the CIR value, is so low (Table 2). However, the value of the phonon frequency [47] was used for the characteristic frequency in the infrared.
2. PbS Lead sulphide is a semiconductor having a cubic rock salt crystal structure. Guizzetti and Borghesi [48] have compiled the dielectric data, generally focusing on materials with low free carrier concentrations. Since lead sulphide displays significant absorption in the ultraviolet-visible frequency range, the Cauchy plot in Fig. 4 rests on some sparse data in the near-infrared, originating from Zemel et al. [49]. Fortunately, the infrared absorption band occurs at very low frequencies [50], leaving a sufficiently broad transparent frequency region for Cauchy treatment. 3. p-SiC The spectroscopic ellipsometry data on cubic p-silicon carbide reported by Alterovitz and Woollam [51] was used in the Cauchy plot (Fig. 4). The spectral data of this material, which is of the zincblende structure, agree very well with reported values of n o for hexagonal 6H-silicon carbide [52]. The infrared absorption data are from Spitzer et al. [53]. 4. SrTi03 Dielectric data on undoped strontium titanate single crystals of the cubic perovskite structure have been collected by Gervais [54]. The n(o) data plotted in the Cauchy plot (Fig. 4) were taken from reflectivity measurements by Cardona [55]. The infrared absorption data are from Spitzer et al. [56]. 5. Z n S The natural crystal modifications of zinc sulphide include the cubic, zincblende, and the hexagonal, wurtsite type. Zinc sulphide minerals usually contain substantial amounts of impurities with iron being the principal one. These impurities affect the colour of the minerals with the purest minerals having a light yellow body colour [57]. Palik and Addamiano [57] have collected the dielectric data of both of the zinc sulphide forms, focusing on synthetic materials or pure minerals. The calculated refractive index values presented by Pikhtin and Yaskov [58] in the ultraviolet-visible frequency range for the cubic modification were used for the Cauchy plot in Fig. 4. Infrared data was taken from Deutsch [59].
147
IVD. Tetragonal, hexagonal and trigonal materials

In this section, the spectral parameters of tetragonal, hexagonal or trigonal materials with negligible or undetermined birefringence are reported. The spectral parameters of several polycrystalline ceramic materials were recently reported by BergstrSm et al. [6]. They used spectroscopic ellipsometry to determine n(o) in the ultraviolet-visible spectral range and calculated the oscillator parameters from Cauchy plots (UV range). The spectral constant CIR was determined from the static dielectric constant using Eq. (25). Their spectral parameters for polycrystalline hexagonal 6H-SiC and ~-Si3N4, and tetragonal, partially stabilised ZRO2(3% Y) are included in Table 2 with some slight modifications. The number of valid figures has been increased and a slightly lower value of e(0) for polycrystalline, hexagonal {~-A1203- - which is the average value of~(0) for the ordinary and extraordinary ray - - w a s used in this study. The spectral parameters of hexagonal yttrium oxide (Y203) were also collected from the study by BergstrSm et al. [6] using optical data from the literature. Crystalline quartz (SiO 2) of the trigonal crystal structure displays a small birefringence, as analysed by Hough and White [10]. Only the average values are reported in Table 2. Senden and Drummond [26] have performed a thorough analysis of the dielectric data of muscovite mica which is a potassium aluminosilicate (KA]2Si3AIO10(OH)2)belonging to the monoclinic crystal class. They concluded that the spectral parameters in different crystallographic directions affect the calculated by no more than +1%; hence, only the average values are reported in Table 2.
1. CdS The semiconducting compound cadmium sulphide (CdS) is normally of the hexagonal close-packed (wurtzite) crystal structure but a cubic form may occur. Here, only the hexagonal form will be treated, summarised by Ward [60]. Data for both the ordinary and extraordinary rays are available but since the difference in dielectric response is negligible, data for polycrystalline CdS [61] in the ultraviolet-visible range was used for the Cauchy plot in Fig. 5. The infrared data was from Manabe et al. [62]. 2. MgF2 Magnesium fluoride (MgF 2) is an ionic, tetragonal material with rutile crystal structure. The dielectric data of this slightly birefringent material has been compiled by Cotter et al. [63]. Refractive index data
148
L. BergstrSm/Adu. Colloid Interface Sci. 70 (1997) 125-169
'
'
'
'
"
'
'
'
'
CdS
ZnS
Zl'~O
I
i # l l g l l l i l l l l l l l U i l
ii
ill_l!
i-I
I!!-!
I-!
e-
MgF 2
0 O----e 0 0
1 103t
2 103~
310 ~t [(rad/s) 2]
41031
51031
(o2(n2(o~)-1)
Fig. 5. Cauchy plots for tetragonal and hexagonal materials with negligible birefringence; CdS, MgFe, ZnO, ZnS.
for the ordinary ray, presented in a fitted form by Dodge [64] was used for the Cauchy plot in Fig. 5. The infrared data was from Barker's compilation of IR modes [65].
3. Z n O
The optical data in the ultraviolet-visual range for polycrystalline, hexagonal zinc oxide (ZnO) was taken from the Fig. 2, previously reported by BergstrSm et al. [6]. Only the data in the transparent region, thus sufficiently below the band gap energy, was used for the Cauchy plot in Fig. 5. The infrared data was from Farmer [66].
4. Z n S
The optical data in the ultraviolet-visual spectral range for the hexagonal modification of zinc sulphide was taken from Bienewski and Czyzak [67]. The material only displays a minor birefringence in this transparent spectral region so only the ordinary ray data was used for the Cauchy plot (Fig. 5). The infrared data was from Manabe et al. [62]. Comparison of the spectral parameters for cubic and hexagonal zinc
L. Bergstr6m /Adv. Colloid Interface Sci. 70 (1997) 125-169
149
sulphide show relatively small differences; hence, it is not critical to know the exact composition when estimating the Hamaker constant for a phase mixture, e.g. the commercially available IRTRAN 2 material. IVE. Birefringent materials Previous analysis of the dielectric data in different crystallographic orientations has shown that the trigonal material calcite (CaCO 3) and the tetragonal material rutile (TiO 2) display significant birefringence. The data for calcite from Hough and White [10] and the spectral parameters for rutile, recently reported by Buscall [68], are shown in Table 2. 1. BaTi03 The Cauchy plot for tetragonal BaTiO 3 having a perovskite crystal structure, is shown in Fig. 6. Spectral data have been collected by Wong
2,2
. . . . . . . ' . . . .
Be5
BaTiO 3
O
EO
2
1,8 . . . . . . . 0
I ........ 4 1031
A
8 10 31
5
c
4
0 5 1 0 31 1 1 0 32
0)2(n2(~)-1)
[(rad/s) 2]
Fig. 6. Cauchy plots for the birefringent materials; tetragonal BaTiO3, and inserted; hexagonal BeO. The ordinary (O) and extraordinary (EO) rays represent the refractive indices perpendicular and parallel to the optical axis, respectively. The averaged representation (A) can be obtained by n a = (1/3)neo + (2/3)n o.
150
L. Bergstrbm/Adv. Colloid Interface Sci. 70 (1997) 125-169
et al. [69] and the optical properties of melt-grown single crystal BaTiO 3 [70] w a s used in the C a u c h y plot. It can be seen t h a t the optical anisotropy for this m a t e r i a l is quite significant; the curves for the o r d i n a r y a n d e x t r a o r d i n a r y rays are well s e p a r a t e d and t h e r e is a 4-6% difference in obtained spectral p a r a m e t e r s for the two crystallographic orientations. The average r e p r e s e n t a t i o n for the ultraviolet-visible spectral r a n g e was obtained by adding one third of the c-axis (extraordinary) contribution and two thirds of the a-axis (ordinary) contribution following r a t i o n a l e above. The infrared and static spectral p a r a m e t e r s will be discussed in detail later.
2. BeO The relatively sparse optical d a t a for hexagonal beryllium oxide (BeO) h a v e been collected by E d w a r d s and White [71]. The d a t a from N e w k i r k et al. [72] was used for the C a u c h y plot (insert in Fig. 6). The optical a n i s o m e t r y is quite significant also for this material, in particular r e g a r d i n g the (Ouv w h e r e a 20% difference b e t w e e n the two crystallographic orientations was found. The infrared d a t a was from Loh [73].
V. C a l c u l a t e d H a m a k e r c o n s t a n t s
VA. Importance of the IR range.

The i m p o r t a n c e of the IR r a n g e for the calculation of H a m a k e r c o n s t a n t s was tested for two materials: BaTiO 3 which is c h a r a c t e r i s e d by a v e r y h i g h e(0), and t h u s a high Cm, and SiO 2 which h a s a low e(0). Full Lifshitz calculations, using Eq. (19), were performed across t h r e e different media: v a c u u m , w a t e r and n-dodecane; investigating the effect of the i n f r a r e d contribution. The calculated values collected in Table 3 show t h a t the IR contribution to the H a m a k e r constant is significant for BaTiO 3 in all media; for SiO 2 the IR contribution is negligible except in t h e case of n-dodecane w h e r e the Cuv and O~v of the m e d i u m and the m a t e r i a l are very similar resulting in a very low UV contribution to the n o n - r e t a r d e d H a m a k e r constant. Hence, for a m a t e r i a l characterised by a relatively low value of CIR , like most ceramic materials, the IR contribution to the H a m a k e r constant is very small, typically only a few percent, except in the case w h e n the i n t e r v e n i n g m e d i u m has a similar dielectric response function in the UV r a n g e as the material. In the case of a m a t e r i a l characterised by a high Ciz and sufficiently h i g h OiR, e.g. BaTiO 3, the IR contribution is significant irrespective of
L. Bergstr6m/Adv. Colloid Interface Sci, 70 (1997) 125-169

Table 3
151
N o n - r e t a r d e d H a m a k e r constants for t e t r a g o n a l BaTiO 3 and silica i n t e r a c t i n g across v a c u u m , w a t e r and n-dodecane at room t e m p e r a t u r e (298 K) Material Medium Vacuum B aT i O 3 com (1014 rad/s) 0.7 1.0 SiOe ~o m (10 TM rad/s) See Table 2 (3 IR contributions) 6.35 6.50 14.1 17.6 19.3 Water n-dodecane
H a m a k e r constant (10 .2o J) 4.45 7.91 9.49 3.77 7.44 8.99
H a m a k e r constant (10 .2o J) 0.48 0.46 0.097 0.14
t h e dielectric properties of the m e d i u m . With w a t e r or n-dodecane as t h e i n t e r v e n i n g media, t h e IR contribution a t t r i b u t e s for m o r e t h a n 50% of t h e total v a l u e of the n o n - r e t a r d e d H a m a k e r constant, t h u s m a k i n g an a c c u r a t e dielectric r e p r e s e n t a t i o n of the i n f r a r e d r a n g e i m p o r t a n t . In t h e case of BaTiO 3, Wemple et al. [70] r e p o r t e d room t e m p e r a t u r e dielectric c o n s t a n t s m e a s u r e d at 100 kHz of: Ea = 3600, ec = 150. The a v e r a g e static dielectric c o n s t a n t was e s t i m a t e d as eaver = 2400. Busca et al. [74] h a v e studied the IR characteristics of a t e t r a g o n a l BaTiO 3 powder. T h e y found t h a t t h e IR s p e c t r u m h a s two d o m i n a n t complex absorptions: one in the region 600-500 cm -1 a n d the o t h e r in the region 450-350 cm -1. T h e s e absorptions correspond to (~IR at 1.0 10 -14 a n d 0.7 10 -14 rad/s, respectively. With t h e u n c e r t a i n t y in the IR absorption frequency, t h e e r r o r in t h e H a m a k e r c o n s t a n t becomes relatively large. A r e a s o n a b l e e s t i m a t e of t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t for t e t r a g o n a l BaTiO 3 in v a c u u m is 18 + 1.5 10 -20 J, across w a t e r Alw I = 8 _+ 1.5 10 -20 J, a n d across n-dodecane A = 7.5 + 1.5 10 -20 J. Hence, for such a m a t e r i a l w i t h a significant IR contribution, the e r r o r in the H a m a k e r c o n s t a n t calculation becomes relatively large (10-20%) using t h e p r e s e n t r e p r e s e n t a t i o n . The a c c u r a c y of the calculations m a y be i m p r o v e d using a m o r e detailed IR r e p r e s e n t a t i o n .
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L. BergstrOm/Adv. Colloid Interface Sci. 70 (1997) 125-169
v$
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L. BergstrSm /Adv. Colloid Interface Sci, 70 (1997) 125-169
VB. Full Lifshitz calculations and analytical approximations

N o n - r e t a r d e d H a m a k e r c o n s t a n t s w e r e calculated for all t h e s y m m e t ric s y s t e m s , m a t e r i a l 1 i n t e r a c t i n g across a m e d i u m 3, u s i n g full Lifshitz c a l c u l a t i o n s , Eq. (19), a c r o s s v a c u u m a n d w a t e r . N o n - r e t a r d e d H a m a k e r c o n s t a n t s w e r e also e s t i m a t e d u s i n g two different a p p r o x i m a tions, Eq. (21) for t h e H a m a k e r c o n s t a n t in v a c u u m ( T a b o r - W i n t e r t o n e q u a t i o n i n c l u d i n g t h e static c o n t r i b u t i o n (TWS)), a n d Eq. (22) t o g e t h e r w i t h t h e static t e r m in Eq. (21) ( H o r n - I s r a e l a c h v i l i (HIS) e q u a t i o n ) for t h e H a m a k e r c o n s t a n t across water. T h e calculated v a l u e s are collected in Table 4. T h e n o n - r e t a r d e d H a m a k e r c o n s t a n t s in v a c u u m , Alvl, v a r y b e t w e e n 296 zJ (1 zJ = 10 -21 J) for d i a m o n d down to 40.5 zJ for N a F . Most of t h e h a l i d e s h a v e relatively low n o n - r e t a r d e d H a m a k e r c o n s t a n t s while t h e m o r e covalently b o n d e d oxides, carbides a n d n i t r i d e s h a v e significantly h i g h e r values. T h e TWS a p p r o x i m a t i o n gave a s u r p r i s i n g l y good c o r r e s p o n d e n c e to t h e full Lifshitz calculations. It s h o u l d be obs e r v e d t h a t for t h e s e calculations, t h e a p p r o p r i a t e O>~v a n d n o for e a c h m a t e r i a l (from Table 2) w e r e used. T h e a v e r a g e error for t h e 31 i n o r g a n i c m a t e r i a l s w e r e only =3%, except for BaTiO 3 w h e r e t h e TWS a p p r o x i m a tion p r e d i c t s a v a l u e 23% too low. T h e m a i n difference b e t w e e n t h e TWS a p p r o x i m a t i o n a n d t h e full Lifshitz calculation is t h a t t h e TWS approxim a t i o n only considers t h e c o n t r i b u t i o n from t h e UV-vis region, h e n c e i g n o r i n g t h e IR c o n t r i b u t i o n to e(i~), a n d t h a t t h e double s u m m a t i o n in Eq. (19) is a p p r o x i m a t e d w i t h an analytical expression. T h e good agreem e n t b e t w e e n t h e full Lifshitz a n d t h e TWS a p p r o x i m a t i o n s u p p o r t s t h e p r e v i o u s s t a t e m e n t t h a t t h e IR c o n t r i b u t i o n to t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t is negligible for m o s t ceramic m a t e r i a l s in v a c u u m or air. This is a n e n c o u r a g i n g r e s u l t since it w a s difficult to obtain d e t a i l e d i n f o r m a t i o n of t h e IR absorption b e h a v i o u r for s o m e of t h e m a t e r i a l s . A s m a l l e r error in O~IR a n d C m s h o u l d n o t r e s u l t in a n y s i g n i f i c a n t c h a n g e in t h e e s t i m a t e d v a l u e of A i r 1. W i t h w a t e r as t h e i n t e r v e n i n g m e d i u m , t h e r e is a m u c h l a r g e r s p r e a d in t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t s , Alwl; from 3.1 zJ for N a F to 138 zJ for d i a m o n d . All t h e s e calculation w e r e p e r f o r m e d u s i n g t h e n e w s p e c t r a l r e p r e s e n t a t i o n of w a t e r [13], see Table 1. In general, t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t s p r e s e n t e d h e r e are significantly lower t h a n e a r l i e r e s t i m a t e s u s i n g t h e p r e v i o u s , less exact, U V r e p r e s e n t a t i o n s of w a t e r . For example, t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t s across w a t e r H o u g h a n d W h i t e [10] calculated for silica (8.49 zJ), calcite (22.3 zJ), c a l c i u m fluoride (10.4 zJ) a n d s a p p h i r e (53.2 zJ) are u p to two
155
times larger t h a n the values calculated in this study. Similarly, the n o n - r e t a r d e d H a m a k e r constants across w a t e r p r e s e n t e d by BergstrSm et al. [6] for nine different inorganic m a t e r i a l s are significantly larger t h a n the p r e s e n t values. One m a t e r i a l w h e r e the m a g n i t u d e of the vdW interaction is of special importance is muscovite mica; an extensively used m a t e r i a l in direct surface force m e a s u r e m e n t s [1,22,75]. Comm o n l y used values for Alwl(mica) = 20 + 2 zJ [1,26] are almost 50% h i g h e r compared to the p r e s e n t value OfAlwl(mica) = 13.4 zJ. A lowering of the H a m a k e r c o n s t a n t for this system m a y have i m p o r t a n t implications r e g a r d i n g the i n t e r p r e t a t i o n of the obtained force curves. T h e r e is a relatively poor correspondence between the full Lifshitz calculations and the HIS approximation across water. The HIS approximation, w h i c h utilises only one value for COuvand Cuv for the m a t e r i a l and the m e d i u m , respectively, appears to overestimate the H a m a k e r c o n s t a n t across w a t e r for almost all the m a t e r i a l s while the TWS a p p r o x i m a t i o n u n d e r e s t i m a t e s the n o n - r e t a r d e d H a m a k e r constant in v a c u u m . Note t h a t the TWS approximation can not be used for calculations w i t h an i n t e r v e n i n g m e d i u m since the i n h e r e n t a s s u m p t i o n of a c o m m o n ekyv for the m a t e r i a l and the m e d i u m n e v e r holds. D e p e n d i n g on the spectral p a r a m e t e r s of the materials, the HIS approximation o v e r e s t i m a t e s the n o n - r e t a r d e d H a m a k e r constant w i t h almost a factor of two. While the u n d e r e s t i m a t i o n in the TWS case can be explained by t h e absence of the IR r a n g e contribution, the overestimation using the HIS approximation across w a t e r is probably due to the poor spectral r e p r e s e n t a t i o n of w a t e r using only one UV oscillation. For m e d i a with simpler spectral features, e.g. dodecane, a very good correspondence b e t w e e n the full Lifshitz calculations and the HIS approximation is obtained (not shown).
VC. H a m a k e r constants for use in A F M studies
The use of atomic force microscopy (AFM) to probe the distance d e p e n d e n t forces between various m a t e r i a l s s e p a r a t e d by air, v a c u u m or liquids h a v e recently gained m u c h interest. Initially, the forces b e t w e e n the cantilever tip - - typically m a d e of silicon nitride - - and a substrate, commonly mica, was monitored and m a n i p u l a t e d [75-79]. This w o r k has been extended by m e a s u r i n g the force curves between silicon nitride tips and s u b s t r a t e in liquids at different conditions [26,80,81], a n d a t t a c h i n g colloidal spheres of different m a t e r i a l s to the AFM cantilevers [82-85]. These developments have made AFM a versatile
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L. Bergstriirn /Adv. Colloid Interface Sci. 70 (1997) 125-169
tool for studying the complex interactions between surfaces of different materials. To assist the interpretation of AFM force measurements, the non-retarded Hamaker constants of materials interacting across vacuum (air) and water against four materials: silica, amorphous silicon nitride, s a p p h i r e (a-A1203), a n d m u s c o v i t e m i c a h a v e b e e n c a l c u l a t e d ( T a b l e 5). These materials are commonly used either as cantilever tips (silicon n i t r i d e ) , c o l l o i d a l p r o b e s ( s i l i c a ) or i n o r g a n i c s u b s t r a t e s ( s a p p h i r e , m i c a ) in AFM studies. In general, the magnitude of the Hamaker constants follows the expected trends with a large value for high refractive index
Table 5 Non-retarded H a m a k e r constants in vacuum and across water (vacuum/water) of inorganic materials interacting against four materials at room temperature H a m a k e r constant (10 -2oJ) Material BaTiO 3 BeO C (diamond) CaCO 3 CaF 2 CdS KC1 MgA1204 MgF 2 MgO Mica NaC1 PbS 6H-SiC ~-Si~N 4 SiO 2 (quartz) SrTiO~ TiO 2 Y20:~ ZnO ZnS (cubic) 3Y-ZrO 2 Silica 10.1/0.62 9.67/0.95 13.7/1.71 8.07/0.69 6.70/0.45 8.03/0.72 5.94/0.37 9.05/0.85 6.15/0,36 8.84/0.81 8.01/0.69 6.45/0.44 5.37/-0.08 12.6/1.52 10.8/1.17 7.59/0.63 9.44/0.57 9.46/0.69 9.24/0.89 7.38/0.58 9.69/1.02 11.4/1.25 Silicon nitride 16.5/4.84 15.4/3.87 22.0/7.94 12.9/2.53 10.6/1.17 13.1/3.12 9.53/0.73 14.5/3.39 9.74/0.66 14.2/3.26 12.8/2.45 10.3/1.17 8.88/0.64 20.3/7.22 17.3/5.13 12.112.07 15.4/4.02 15.4/4.26 14.9/3.80 12.0/2.30 15.7/4.56 18.4/5.89 Alumina 15.2/3.55 14.8/3.50 21.117.05 12.3/2.17 10.3/1.10 12.0/2.15 9.00/0.51 13.8/2.97 9.42/0.69 13.5/2.79 12.2/2.15 9.77/0.88 7.90/-0.20 19.2/6.05 16.5/4.43 11.6/1.83 14.2/2.98 14.2/3.11 14.0/3.11 11.111.58 14.6/3.55 17.4/4.95 Mica 12.4/1.98 1L9/2.06 17.0/4.03 9.94/1.35 8.26/0.73 9.86/1.43 7.3110.46 11.2/1.79 7.57/0.50 10.9/1.69 9.86/1.34 7.93/0.66 6.57/-0.03 15.5/3.54 13.3/2.61 9.35/1.16 11.6/1.69 11.6/1.83 11.4/1.89 9.06/1.08 11.9/2.19 14.112.89
157
m a t e r i a l like silicon nitride and a lower value for a low refractive index m a t e r i a l like silica. In vacuum, the n o n - r e t a r d e d H a m a k e r constants span is relatively narrow: from 53.7 zJ (PbS against silica) to 220 zJ ( d i a m o n d a g a i n s t silicon nitride). With w a t e r as the i n t e r v e n i n g medium, the m a g n i t u d e of the v a n der Waals attraction is of course r e d u c e d and also b r o a d e n e d d e p e n d i n g on the material: from 3.7 zJ (KC1 a g a i n s t silica) to 79.4 zJ (diamond against silicon nitride). In fact, negative n o n - r e t a r d e d H a m a k e r constants, indicating a repulsive v a n der Waals interaction, w e r e calculated for several m a t e r i a l combinations involving PbS across water. A negative H a m a k e r c o n s t a n t r e p r e s e n t s a destructive electrodynamic interaction between the materials and it is only recently t h a t direct m e a s u r e m e n t s of repulsive van der Waals forces w e r e d e m o n s t r a t e d [86,87]. In general, repulsive van der W a a l s forces are predicted for systems w h e r e the m a g n i t u d e of the dielectric response of the m e d i u m is i n t e r m e d i a t e to the m a g n i t u d e of t h e dielectric response of the two different i n t e r a c t i n g materials. For PbS, h a v i n g the spectral characteristics of a very high e(0), e x t r e m e l y h i g h n o (or Cur), and a very low muv, the calculations against t h e four m a t e r i a l s across w a t e r (Table 5) display several i n t e r e s t i n g features. The static contribution (m = 0) is negative (repulsive) for all these m a t e r i a l combinations since ~(0) of the m e d i u m (water) is i n t e r m e d i a t e to ~(0) for PbS and the materials. Since the static contribution u s u a l l y is of m i n o r importance, it is of interest to analyse the dispersive contribution in some detail. However, it should be noted t h a t the spectral p a r a m e t e r s in the UV-visible spectral r a n g e for PbS relies on relatively sparse data, t h u s m a k i n g the spectral r e p r e s e n t a t i o n less accurate. As i l l u s t r a t e d in Fig. 7 for two of the m a t e r i a l s combinations: PbS against silica, a n d PbS a g a i n s t silicon nitride, the dispersive contribution changes sign from positive to negative above a critical frequency. Hence, in the i n f r a r e d and visible p a r t of the s p e c t r u m (m < 25), the interaction is c o n s t r u c t i v e while t h e contribution from the ultraviolet region (m > 25) is destructive. In the system silica against PbS, this balance is v e r y delicate r e s u l t i n g in a v e r y small, positive dispersive contribution (0.2 zJ) to the n o n - r e t a r d e d H a m a k e r constant w h e n the contributions from all the frequencies h a v e been s u m m a t e d . Since t h e static contribution (-1.0 zJ) d o m i n a t e s the total van der Waals interaction for this system, the calculations suggests t h a t screening this interaction, e.g. by addition of salt [2J, would result in a system with a negligible vdW attraction.
158

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159
VD. Spectral parameter scalings

With the absence of detailed spectroscopic data, we are limited to t h e simplified expressions for calculating n o n - r e t a r d e d H a m a k e r constants. The TWS a n d HIS approximations are examples of such simplifications. However, even for t h e simple TWS approximation of the n o n - r e t a r d e d H a m a k e r c o n s t a n t in v a c u u m , we h a v e to know t h r e e p a r a m e t e r s : okrv, n 0, a n d e(0). Usually, values of the refractive index in the visible a n d the static dielectric c o n s t a n t can be found for most m a t e r i a l s b u t O)uv is u s u a l l y not t a b u l a t e d a n d h a s to be e x t r a c t e d from d a t a of t h e f r e q u e n c y d e p e n d e n c e of t h e refractive index which m a y be h a r d to find. W i t h o u t such data, t h e a s s u m p t i o n originating from Tabor and W i n t e r t o n [22] of a common value of Ouv = 2 x 10 i6 rad/s for all materials is frequently used. F i g u r e 8 illustrates how a common value ofa)cv = 2 x 1016 rad/s results in a s y s t e m a t i c o v e r e s t i m a t i o n of t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t s for m a n y of t h e inorganic materials. For simplicity, the original T a b o r W i n t e r t o n (TW) a p p r o x i m a t i o n was used, t h u s not including t h e static contribution w h i c h is negligible for vdW interactions across v a c u u m . The deviation of t h e Lifshitz value for A i r i from this simplified TW
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160
a p p r o x i m a t i o n i n c r e a s e s w i t h i n c r e a s i n g refractive index. This agrees w i t h previous s t u d i e s [7,88] w h i c h concluded t h a t t h e T W a p p r o x i m a tion r e s u l t s in poor c o r r e s p o n d e n c e to full Lifshitz calculations for h i g h refractive index m a t e r i a l s . However, this does n o t reflect a n y significant i n h e r e n t errors in t h e TWS a p p r o x i m a t i o n s ; it m e r e l y r e l a t e s to a poor choice of Ouv. If t h e a p p r o p r i a t e v a l u e s of t h e spectral p a r a m e t e r s , in p a r t i c u l a r Ouv, are used, t h e r e s u l t s in Table 4 clearly show t h a t t h e TWS a p p r o x i m a t i o n gives quite a c c u r a t e r e s u l t s w h e n c o m p a r e d to full Lifshitz calculations for m o s t m a t e r i a l s . T h e r e l a t i o n b e t w e e n t h e refractive index, no, a n d Ovv is s h o w n in Fig. 9. All t h e m a t e r i a l s display a d e c r e a s i n g mvv w i t h an i n c r e a s i n g refractive i n d e x w h i c h can explain t h e i n c r e a s i n g d e v i a t i o n in t h e v a l u e ofAlv 1 b e t w e e n t h e full Lifshitz calculations a n d t h e TW a p p r o x i m a t i o n u s i n g a c o n s t a n t v a l u e of O)uv. An a t t e m p t w a s m a d e to e s t a b l i s h a g e n e r a l scaling relation for all t h e s e m a t e r i a l s . D u e to t h e large s c a t t e r of t h e d a t a in Fig. 9a, however, it w a s n o t possible to describe all t h e d i f f e r e n t m a t e r i a l s w i t h s u c h a scaling relation. If we s o m e w h a t arbit r a r i l y limit t h e d a t a to covalent oxides, s u l p h i d e s a n d nitrides, t h u s e x c l u d i n g t h e ionic halides, a n d SiC a n d d i a m o n d , a s i m p l e scaling r e l a t i o n at h i g h e r refractive indices, following t h e power law 8.8 1016 n2.S
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(26)
m a y be e s t a b l i s h e d , a l t h o u g h a significant scatter of t h e d a t a still r e m a i n s (Fig. 9b). F i g u r e 9b indicates t h a t for covalent m a t e r i a l s w i t h a low refractive i n d e x (n o < 1.7), O)cv a p p e a r s to be i n d e p e n d e n t o f n 0. A s i m p l e scaling b e t w e e n t h e refractive index in t h e visible a n d t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t h a s been i l l u s t r a t e d previously by Buscall [68] for m a t e r i a l s such as polymers, h y d r o c a r b o n s , q u a r t z a n d calcite. T h e success of this scaling can be referred to t h e n e a r l y identical Ouv of t h e s e low refractive index m a t e r i a l s . Buscall also concluded t h a t s u c h a correlation is n o t applicable w h e n Ovv deviates s u b s t a n t i a l l y f r o m this c o m m o n value, as observed w i t h rutile, a h i g h refractive index Fig. 9. Relation between the characteristic frequency in the UV range, Otrv, and the refractive index in the visible, no: (a) all the inorganic materials, (b) only the covalent materials thus excluding the halides. The high refractive index materials, diamond and silicon carbide have also been excluded in (b) where the full line represents the power law fit according to Eq. (26).
Opposite:
161
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162
material (n = 2.46). In this work, however, no attempt to implement the scaling in Eq. (26) in the TWS approximation was made due to the large scatter of the data.
VE. Comparison with a Kramers-Kronig dielectric representation

French and co-workers [7,88] have recently published several papers where the non-retarded H a m a k e r constants of ceramic materials have been calculated using a slightly different scheme applying the integral form of the H a m a k e r constant expression (Eq. (20)). The imaginary dielectric representation, ~(i~), of the materials were obtained through K r a m e r s - K r o n i g transformations of experimentally determined interband transition strengths over a relatively wide photon energy range (0.46 to 44 eV) from optical reflectivity spectra. Non-retarded H a m a k e r constants for different combinations were calculated using a commercially available collection of the necessary programs and a spectral data base of m a n y materials. As previously stated, the accuracy of H a m a k e r constants calculated from Lifshitz theory relies on the quality of the experimental dielectric data and the accuracy of the spectral representation. Since French and co-workers [7,88] use dielectric data over a wide frequency range, their method has the potential of obtaining a very detailed spectral representation in the important frequency range. In principle, the N - P representation has the same potential if a sufficient n u m b e r of relaxations is introduced. Of course, accurate dielectric representations can only be obtained from accurate dielectric data. Ackler et al. [88] recently presented data on non-retarded H a m a k e r constants calculated by the method described above, using the integral equation and Kramers-Kronig relations (IKK method), and compared their values with previously published values where the method in this study, the summation equation (Eq. (19)) with an N - P dielectric representation (SNP method) was used. Also, other simplified models were used for 5 different materials: muscovite mica, A1203, SiO2, Si3N4, and rutile TiO2, separated by vacuum and water. In the IKK calculations [88], the dielectric representation for the inorganic materials was obtained from VUV reflectivity data as described above while the a(i~) function for water was determined from literature data [12] and K - K transformed to be incorporated in the data base. Here, their values for the non-retarded H a m a k e r constants using the IKK method are compared with values using the SNP method (Table 6) in an attempt to assess the accuracy of representing the materials with
163
Table 6 C o m p a r i s o n of calculated n o n - r e t a r d e d H a m a k e r c o n s t a n t s using two different methods: the integral Kramers-Kronig (IKK) method and the summation Ninham-
Parsegian (SNP) method

Material H a m a k e r constant (10 -20 J) Vacuum I K K [881 Mica A1203 SiO 2 Si3N 4 TiO 2 r u t i l e 6.96 14.5 6.60 17.4 17.3 SNP 9.86 15.2 6.50 18.0 15.3 Water I K K [88] 0.29 2.75 0.16 4.6 6.0 SNP 1.34 3.67 0.46 5.47 5.35 SNP-UV* 1.08 3.48 0.17 5.22 5.02
* S N P - U V calculations were performed using Eq. (19) including only the UV contribution of the ~(i~m) function of both the m a t e r i a l s a n d water.
t h e simplified, two oscillator, N - P r e p r e s e n t a t i o n . Observe t h a t t h e v a l u e s for t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t s u s i n g t h e S N P m e t h o d differs in this s t u d y a n d in Ackler et al. [32] since a n e w w a t e r repres e n t a t i o n is u s e d here. W i t h v a c u u m as t h e i n t e r v e n i n g m e d i a , t h e r e is a v e r y good c o r r e s p o n d e n c e of t h e calculated v a l u e s ofAlv I for t h r e e of t h e m a t e r i a l s : a l u m i n a , silica, a n d silicon nitride, w i t h an a v e r a g e difference of only 3%. For mica, t h e I K K m e t h o d yields a significantly lower v a l u e while t h e IKK m e t h o d yields a 12% h i g h e r v a l u e of t h e H a m a k e r c o n s t a n t for rutile. T h e difference in t h e c a l c u l a t e d v a l u e s b e t w e e n t h e two m e t h o d s is i n c r e a s e d significantly for t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t s across water. T h e r e a r e two m a i n differences b e t w e e n t h e I K K a n d t h e S N P m e t h o d s . In t h e I K K m e t h o d , t h e i n t e g r a l e q u a t i o n for t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t is u s e d (Eq. (20)) w h i c h ignores t h e static contribution. T h e S N P m e t h o d uses t h e double s u m m a t i o n e q u a t i o n w h i c h i n c l u d e s this c o n t r i b u t i o n , r e f e r r i n g to t h e first s u m m a t i o n (m = 0) in Eq. (19). T h e I K K m e t h o d typically h a s an i m a g i n a r y dielectric repres e n t a t i o n over a significantly b r o a d e r f r e q u e n c y r a n g e , in p a r t i c u l a r t h e h i g h f r e q u e n c y r a n g e , c o m p a r e d to t h e simplified N - P r e p r e s e n t a t i o n u s i n g only one UV a n d possibly a few IR t e r m s (Eq. (14)). T h e I K K
164
method, however, also ignores the IR contribution at p r e s e n t [7]. It is of i n t e r e s t to e v a l u a t e the effect and m a g n i t u d e of these two differences b e t w e e n the I K K and SNP method. Unfortunately, such a comparison is complicated by the fact t h a t dielectric d a t a of different origin was used for most materials. Hence, the difference in the calculated values of the n o n - r e t a r d e d H a m a k e r constants can be caused by either the difference in m a t h e m a t i c a l t r e a t m e n t (integral and summation), the accuracy of the original dielectric d a t a (frequency d e p e n d e n c e of the refractive index or i n t e r b a n d transition strengths) and using an appropriate i m a g i n a r y dielectric representation. I g n o r i n g the static and low frequency contribution of the a(i~) repres e n t a t i o n will only have a m a r g i n a l effect on the n o n - r e t a r d e d H a m a k e r c o n s t a n t for m a t e r i a l s i n t e r a c t i n g across v a c u u m since the dispersive p a r t completely d o m i n a t e s the value of Air 1. The static contribution is u s u a l l y of m i n o r importance in all systems since its m a x i m u m v a l u e is 0.75 k T (4.1 zJ at room t e m p e r a t u r e ) but it can h a v e a significant influence at high t e m p e r a t u r e s or w h e n the dispersive p a r t of the H a m a k e r c o n s t a n t is very small. The significance of the IR contribution was discussed previously and no major influence is expected except for m a t e r i a l s w i t h very high values of the static dielectric constant. Hence, since no major differences are expected using the integral or the summ a t i o n equations (Eqs. (20) and (19), respectively) for low a(0) m a t e r i a l s in v a c u u m , the n e a r l y identical values of A i r 1 for A1203, SiO 2 and Si3N 4 suggests t h a t the dielectric r e p r e s e n t a t i o n s are similar in the two studies. This is supported by the close correspondence of the index of refraction (An < 0.05) for these m a t e r i a l s in Ackler et al. [32] and in this work. For rutile, the h i g h e r A l v 1 using the I K K m e t h o d m a y be explained by a difference in the original dielectric data, Ackler et al. [32] reporting n = 2.6 while this study uses n = 2.46 based on d a t a from Buscall [68]. For mica, a similar explanation m a y apply, or the significantly lower Alv 1 v a l u e using the I K K m e t h o d m a y be related to the fine details of t h e a(i~) r e p r e s e n t a t i o n over a wider frequency range. T u r n i n g to the n o n - r e t a r d e d H a m a k e r constants across w a t e r , t h e r e is a significant difference in Alw 1 b e t w e e n the two m e t h o d s for all materials. The I K K m e t h o d always yields lower values compared to the S N P method. In water, the dispersive contribution becomes very small for some materials, t h u s m a k i n g the static and low frequency contribution i m p o r t a n t . For silica, the result in Table 6 shows t h a t the difference b e t w e e n t h e two methods can be fully related to the omission of this contribution in the I K K method. For all the other materials, except mica,
165
the difference between the IKK and SNP-UV (omitting static and IR contribution) was less than 30%. The large difference in Alw I for mica, almost a factor of four, must be related to major differences in the imaginary dielectric representation, either due to major differences in the original dielectric data or to the capability of the IKK method to yield a detailed e(i~) representation over a wide frequency range. In summary, a comparison of these two methods suggests that the simplified N - P representation over a limited frequency range in general yields non-retarded H a m a k e r constants which do not differ significantly from calculations using a more detailed representation over a broader frequency range. This is not true for all materials, e.g. water, where a more detailed representation using either an N - P representation with several oscillators or the K - K representation. It is possible that mica also is such a material.
V/. S u m m a r y a n d c o n c l u s i o n s
Calculation of non-retarded H a m a k e r constants from Lifshitz theory relies on the accuracy of the dielectric spectral representation and the quality of the experimental dielectric data of the materials and media. In this review, spectral parameters for 31 different inorganic materials (including diamond) have been generated from critically evaluated optical data [11,12] or collected from different sources. The spectral parameters: the oscillator strengths and characteristic frequencies in the UV and IR range; Cur, tour, and Cm, ~ a , respectively, and the static dielectric constant, a(0), for the different inorganic materials generated here can be combined with previous data, mainly focused on hydrocarbon and organic systems [10], to yield an extensive spectral data base for both solids and liquids. Non-retarded H a m a k e r constants across vacuum and water have been calculated using Lifshitz theory for the different inorganic materials (including diamond). All the symmetric combinations (material 1 against material 1) have been treated and the asymmetric combinations with most of the materials against silica, silicon nitride, alumina and mica. These calculations were performed using the full Lifshitz theory utilising the N i n h a m - P a r s e g i a n representation of the imaginary dielectric response function for the materials and medium. A recently reported improved spectral parametric representation of water [13] was used for these calculations which resulted in some significant changes in the value for Alvd, e.g. for mica, compared to previous studies.
166
T h e full Lifshitz calculations were c o m p a r e d w i t h v a r i o u s analytical simplifications a n d a n a l t e r n a t i v e Lifshitz m e t h o d . W h e n t h e appropria t e v a l u e s of o~y a n d n o w e r e used, a s u r p r i s i n g l y good a g r e e m e n t w a s f o u n d - - w i t h v a c u u m as t h e i n t e r v e n i n g m e d i u m - - b e t w e e n t h e full t r e a t m e n t a n d t h e T a b o r - W i n t e r t o n (TWS) approximation. The correspondence between t h e full Lifshitz t r e a t m e n t a n d the TWS approximation s u g g e s t e d t h a t t h e IR frequency range of t h e dielectric r e p r e s e n t a t i o n is of m i n o r i m p o r t a n c e for m o s t m a t e r i a l s . This w a s c o r r o b o r a t e d by a s e p a r a t e e v a l u a t i o n s h o w i n g t h a t t h e IR c o n t r i b u t i o n to t h e non-ret a r d e d H a m a k e r c o n s t a n t is significant only for m a t e r i a l s , like BaTiO3, w h i c h are c h a r a c t e r i s e d by a v e r y h i g h static dielectric c o n s t a n t . T h e calculations in this s t u d y utilising t h e N i n h a m - P a r s e g i a n repr e s e n t a t i o n of t h e dielectric d a t a (SNP m e t h o d ) w e r e c o m p a r e d w i t h a n a l t e r n a t i v e m e t h o d i g n o r i n g t h e static a n d low f r e q u e n c y c o n t r i b u t i o n a n d u s i n g t h e K r a m e r s - K r o n i g t r a n s f o r m a t i o n for t h e v i s i b l e - U V r a n g e (IKK method). In general, t h e S N P m e t h o d u s i n g a simplified N - P r e p r e s e n t a t i o n yields n o n - r e t a r d e d H a m a k e r c o n s t a n t s w h i c h do n o t differ significantly from calculations u s i n g t h e I K K m e t h o d c o n t a i n i n g a m o r e d e t a i l e d dielectric r e p r e s e n t a t i o n over a b r o a d e r f r e q u e n c y r a n g e . However, this is n o t t r u e for all m a t e r i a l s , e.g. w a t e r , w h e r e a m o r e d e t a i l e d r e p r e s e n t a t i o n u s i n g e i t h e r an N - P r e p r e s e n t a t i o n w i t h s e v e r a l r e l a x a t i o n s or t h e K - K r e p r e s e n t a t i o n m u s t be used. It is possible t h a t mica is also s u c h a m a t e r i a l w h i c h implies t h a t t h e m o r e d e t a i l e d dielectric r e p r e s e n t a t i o n of t h e IKK m e t h o d s h o u l d yield a m o r e a c c u r a t e v a l u e of t h e n o n - r e t a r d e d H a m a k e r c o n s t a n t for t h i s m a t e r i a l . It s h o u l d be n o t e d t h a t t h e v a l u e s for Alw I calculated for mica u s i n g t h e S N P (13.4 zJ) a n d t h e I K K m e t h o d (2.9 zJ) are significantly lower t h a n e x p e r i m e n t a l l y d e t e r m i n e d v a l u e s u s i n g t h e surface force a p p a r a t u s (22 zJ). U s i n g silica as a n example, it w a s s h o w n t h a t t h e omission of t h e static a n d low f r e q u e n c y c o n t r i b u t i o n in t h e I K K m e t h o d m a y r e s u l t in a significant u n d e r e s t i m a t i o n of t h e v a l u e for Alw I w h e n t h e dispersive c o n t r i b u t i o n becomes v e r y small.
Acknowledgements
T h e a u t h o r g r a t e f u l l y a c k n o w l e d g e s t h e S w e d i s h N a t i o n a l B o a r d for I n d u s t r i a l a n d T e c h n i c a l D e v e l o p m e n t (NUTEK) for financial support. A n d e r s M e u r k is t h a n k e d for s t i m u l a t i n g discussions.
167
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Hamaker Constants of Inorganic Materials

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ELSEVIER

Advancesin Colloid and Interface Science 70(1997) 125-169

ADVANCESIN COLLOID AND INTERFACE SCIENCE

Hamaker constants of inorganic materials

L. BergstrSm /Adv. Colloid Interface Sci. 70 (1997) 125-169

L. Bergstr6m/Adv. Colloid Interface Sci. 70 (1997) 125-169

L. BergstrSm /Adv. Colloid Interface Sci. 70 (1997) 125-169

L. Bergstr6m/Adv. Colloid Interface Sci. 70 (1997) 125-169

L. Bergstr6m/Adv. Colloid Interface Sci. 70 (1997) 125-169

(5) (6) (7) (8)

N2(co) = (n(co) - ik(o))2 e'(co) = n2(o)) - k2(o) e"(o) = 2n(co)k(o)

L. Bergstr~m /Adv. Colloid Interface Sci. 70 (1997) 125-169

~m = rn( 4~2kB T/h )

~(i~m) = 1 + 1 + ~----~ + y=" 1 + (~

/coj)2 + gj~ /0.)2

L. Bergstr6m/Adv. Colloid Interface Sci. 70 (1997) 125-169

O~uvx 1016 (rad/s)

guv 1015 (tad/s)

gIR 1013 (rad/s)

0.0484 0.0387 0.0923 0.344 0.360 0.0383

1.46 0.737 0.152 0.0136 0.0751

L. BergstrSm/Adv. Colloid Interface Sci. 70 (1997) 125-169

.,. Roth and L e n h o f f [13] . - P a r s e g l a n [14]

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IIB. Calculation of non-retarded Hamaker constants

ydy ln(1 - A13A23 e -2yL)

w i t h the differences in dielectric response, Akl, defined as

Akl- ek(i~m ) + e/(i~ m)

L. Bergstr6m/Adv. Colloid Interface Sci. 70 (1997) 125-169

thus identifyingthe non-retarded Hamaker constantA132 which is given

f dxx ln(1 - A13A23e -x)

This integral can be performed analytically to yield

L. Bergstr6m/Adv. Colloid Interface Sci. 70 (1997) 125-169

where = 0.5(nl 2 + n32) AE = n 2 - n 2

L. BergstriJm/Adv. Colloid Interface Sci. 70 (1997) 125-169

L. Bergstr6mlAdv. Colloid Interface Sci. 70 (1997) 125-169

L. BergstrSm/Adv. Colloid Interface Sci. 70 (1997) 125-169

IIIB. Determination of spectral parameters

L. B e r g s t r f m / A d v . Colloid Interface Sci. 70 (1997) 1 2 5 - 1 6 9

L. Bergstr6m /Adv. Colloid Interlace Sci. 70 (1997) 125-169

L. BergstrSm /Adv, Colloid Interface Sci. 70 (1997) 125-169

IV. Spectral p a r a m e t e r s of materials

IVA. Amorphous materials

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IVB. Cubic halides

L. Bergstr6m/Adv. Colloid Interface Sci. 70 (1997) 125-169

L. BergstrSm/Adv. Colloid Interface Sci. 70 (1997) 125-169

IVC. Cubic covalent materials

7 o 6 S rTiO a ~ ~ C (diamond II) 5 1030 1 SiC

L. BergstrOm/Adv. Colloid Interface Sci. 70 (1997) 125-169

L. BergstrSm/Adv. Colloid Interface Sci. 70 (1997) 125-169

IVD. Tetragonal, hexagonal and trigonal materials

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VA. Importance of the IR range.

L. Bergstr6m/Adv. Colloid Interface Sci, 70 (1997) 125-169

H a m a k e r constant (10 .2o J) 4.45 7.91 9.49 3.77 7.44 8.99

H a m a k e r constant (10 .2o J) 0.48 0.46 0.097 0.14

L. BergstrOm/Adv. Colloid Interface Sci. 70 (1997) 125-169

L. BergstrSm/Adv. Colloid Interface Sci. 70 (1997) 125-169

L. BergstrSm /Adv. Colloid Interface Sci, 70 (1997) 125-169

VB. Full Lifshitz calculations and analytical approximations

L. BergstrSm /Adv. Colloid Interface Sci. 70 (1997) 125-169