C. Mohr et al., Formation of silver particles and periodic precipitate layers in silicate glass induced by thermally assisted hydrogen permeation, J PHYS-COND, 13(3), 2001, pp. 525-536
Nanoscale silver particles embedded in sodium silicate glass were produced
by Na/Ag ion exchange and subsequent thermal treatment in a hydrogen atmosp
here. Their structure and spatial distribution were studied by conventional
and high-resolution electron microscopy (HREM). Two different mechanisms o
f particle formation could be identified: (i) reduction of ionic silver by
hydrogen and formation of mostly defective particles (twinned) within a nea
r-surface region; and (ii) formation of single-crystalline particles in the
interior of the glass resulting from reduction by means of polyvalent iron
ions. Electron microscopy investigation revealed the completion of periodi
c layers of silver particles in near-surface regions with high silver conce
ntration induced by thermally assisted hydrogen permeation. The self-organi
zed periodic layer formation may be explained in terms of Ostwald's supersa
turation theory, assuming interdiffusion of two mobile species. Analysis of
lattice plane spacings from HREM images of silver particles revealed the t
ypical size-dependent lattice contraction. The extent of this, however, was
found to be different for particles formed by hydrogen permeation and thos
e formed by interaction with polyvalent iron ions. These differences reflec
t different influences of the surrounding glass matrix, probably originatin
g from the conditions of particle formation (thermal history).