The kinetics of the gamma-radiolytical or chemical reduction of Au-III Cl-4
(-), or of the combination of both methods, is followed as a function of th
e experimental conditions through the time evolution of the surface plasmon
spectrum of the gold nanoparticles formed or of their sizes as observed by
AFM imaging. It appears from the discussion on the mechanism that even wit
h the strongly reducing radiolytic radicals, the low valency Au-I ions are
somewhat protected by the more concentrated Au-III ions from reduction, up
to a ratio of Au-I/Au-III = 1, and are stabilized for hours, unless cluster
s or 2-propanol (or PVA, but more slowly) catalyze their disproportionation
. The cluster concentration increases correlatively with the dose.
2-Propanol or PVA are mild reducing agents and are unable to reduce Au-III
directly except at the surface of clusters, previously formed, for instance
, by partial radiolytic reduction. In this case, the cluster concentration
remains the same but the size obtained after reduction by the alcohol incre
ases slowly with time up to 100-500 nm, as in a development process. In ord
er to avoid the relative extent of this development, associated with chemic
al reduction and even with the direct gamma-reduction of Au-III, in particu
lar the Au-I disproportionation and reduction steps, high dose rate radioly
sis has been used up to total reduction of the same solutions. The mechanis
m of reduction and growth, step-by-step, is discussed.