We report measurements of the kinetics of polymer diffusion in latex f
ilms prepared from two pairs of poly(butyl methacrylate) (PBMA) latex
particles. One set contains only a small amount of sulfate groups at t
he surface; the other contains a significant amount of carboxylic acid
groups at the surface. Neutralization of these acid groups with ammon
ium, sodium, and barium hydroxide retards the interdiffusion rate at 1
00-degrees-C but does not suppress it. In these experiments, we employ
pairs of particles identical in size, with very similar molecular wei
ghts, molecular weight distributions, and surface charge densities, th
at differ only in the fluorescent chromophore [phenanthrene (Phe) or a
nthracene (An)] used to label the polymer. Each pair of latex allows u
s to use direct nonradiative transfer (DET) experiments to follow poly
mer interdiffusion in films prepared from their dispersions. Acid grou
p neutralization in the latex converts an acid-rich phase at the inter
particle boundary in the film into an ionomer phase. Ba2+ salts are mo
re effective than Na+ at slowing down the polymer diffusion rate, and
both metal ions are much more effective than NH4+. In the case of the
carboxylated latex, this may point to loss of NH3 during film annealin
g, regenerating free COOH groups.