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Senior Participants: Ashcroft (Phys), Ast (MS&E), Baker (MS&E), Blakely (MS&E),
Dieckmann (MS&E), J. Silcox (A&EP) Umbach (MS&E), Zehnder (T&AM). 3 Graduate Students, 1
Research Associate.
This IRG is concerned with the structure and properties of glass, particularly at and near surfaces and
interfaces. IRG-C uses a broad range of approaches and tools to explore the complexity of useful
engineered glass systems and to develop fundamental insights into these materials. To this end, we
are focusing on a set of calcium aluminosilicate (formed from mixtures of SiO2, Al2O3 and CaO)
glasses around the anorthite ([Ca0.5AlO2] 0.5 - [SiO2] 0.5) composition. They are of interest both
because they are good model glassesthe simplest glasses that have the physical attributes of
complex technological glassesand because they are closely related to the advanced glasses used in,
for example, computer displays. Surprisingly, given their technological utility, much of the fundamental surface behavior of these glasses is either not understood or not yet explored. When the ratio
of Al2O3 to CaO is maintained at 1:1, a fully linked network structure like that of SiO2 is obtained;
this network is preserved even when the SiO2 content is systematically varied over a wide range. An
important collaboration with scientists at Cornings R&D laboratories has been developed and they
have prepared high purity samples of calcium aluminosilicates for IRG-C research. IRG-Cs recent
efforts have been focussed on studies of these
model glasses and the initial results suggest that this
will be an incredibly rich area in which to work.
Recent Accomplishments
Tracer diffusion studies: In Dieckmanns previous IRG-C work with other glasses,1,2 exposure
of the glass surface to moist air at elevated
temperatures results in a near-surface zone tens of
microns thick that is likely due to water-induced
structural relaxations. In the calcium
aluminosilicates, Dieckmann has now seen that
the rate of formation of this zone depends strongly on composition and on temperature. The diffusivity of 22Na- decreases sharply with decreasing
50 nm
SiO2 content, both in the modified zone and in the
bulk, possibly because AlO2 acts as a deep trap
for Na+, with the trapping increasing as the glass
Fig. 1: Non-contact AFM image of structure relaxes.
fracture surface of anorthite glass. Inset
AFM on fracture surfaces: Umbach and Blakely
shows typical nanometer scale features.
have used non-contact AFM to study the
nanoscale surface structure of calcium aluminosilicate glasses fractured in ultra-high vacuum.
These surfaces are free of mechanical damage from polishing and free from extrinsic
contaminants. Fig. 1 shows a typical fracture surface for anorthite glass. There appear to be
characteristic structures at several length scales. Hillocks of width 15 to 20 nm contain distinct
features with a lateral length scale of 5 nm (see the inset of Fig. 1). Similar characteristic length
scales are observed in commercial display glasses. The origin of these features may be associated
with the fracture process or may reflect some underlying structural unit of the glass itself.
effects of interface chemistry on metal film adhesion as a function of glass composition will be
studied. With the acquisition of a new FTIR microscope, IRG-C will be able to characterize all
the glasses it studies for water content and structural relaxations. This new capability will be
particularly useful for the diffusion experiments, where the width of the modified zone can be
determined directly by cross-sectional IR microscopy.
Theory: Glass formation: Application by Ashcroft of a variational approach (via the GibbsBogolyubov inequality) to the Helmhotz energies of systems with more realistic interactions will
allow a better understanding of those fluid mixtures which form glasses and those which do not.
Adhesion: As an alternative to previous first-principles calculations of metal-glass interactions
where the metal and glass were both in solid form, Ashcroft intends to study the wetting
properties of a multicomponent glass forming liquid in the presence of a substrate whose
interactions with the constituents of the liquid are known.
References for IRG-C
1. L. Tian, R. Dieckmann, C.-Y. Hui, Y.-Y. Lin, and J. G. Couillard, Effect of water
incorporation on the diffusion of sodium in Type I silica glass, J. Non-Cryst. Sol. (submitted
for publication).
2. L. Tian, R. Dieckmann, C.-Y. Hui, and J. G. Couillard, Effect of water incorporation on the
diffusion of sodium in an alkaline-earth boroaluminosilicate glass, J. Non-Cryst. Sol.
(submitted for publication).
3. N.Jiang, J.Qiu and J.Silcox, Precipitation of nanometer scale Zn crystalline particles in ZnOB2O3-SiO2 glass during electron irradiation, Appl. Phys. Lett 77 3956-3958 (2000).
4. N. Jiang and J. Silcox, Electron radiation damage in multi-component glasses J.Appl. Phys.,
submitted for publication.
5. J. Liu, N. Nemchuk, D. G.Ast, J. G. Couillard, Etch rate and surface morphology of plasma
etched glass substrates, to be published in the Proceedings of MRS 2000 Fall Meeting,
Boston, Mass.
6. A. Koenig and N. W. Ashcroft, Structure and effective interactions in three-component hard sphere
fluids, Physical Review E (submitted for publication).