Photolysis of air-saturated aqueous solutions containing sulphonated poly(ether etherketone) and poly(vinyl alcohol) results in the generation of hydrogen peroxide. Consumption of oxygen and H2O2 formation are initially concurrent processes with a quantum yield of peroxide generation of 0.02 in stirred or unstirred solutions within the range of 7 ≤ pH ≤ 9. The results are rationalized in terms of O2 reduction by photogenerated α-hydroxy radicals of the polymeric ketone in competition with radical-radical processes that consume the macromolecular reducing agents. Generation of H2O2 is controlled by the photochemical transformation that produces the polymer radicals, which is most efficient in neutral and slightly alkaline solutions. Quenching of the excited state of the polyketone by both H3O(+) and OH(-) affect the yields of the reducing macromolecular radicals and of H2O2. Deprotonation of the α-hydroxy polymeric radicals at pH > 9 accelerate their decay and contribute to suppressing the peroxide yields in basic solutions. Maxima in [H2O2] are observed when illuminations are performed with static systems, where O2 reduction is faster than diffusion of oxygen into the solutions. Under such conditions H2O2 can compete with O2 for the reducing radicals resulting in a consumption of the peroxide.

Electrochemical gold plating processes were examined for the metallization of Kevlar yarn. Conventional Sn(2+)/Pd(2+) surface activation coupled with electroless Ni deposition rendered the fibers conductive enough to serve as cathodes for electrochemical plating. The resulting coatings were quantified gravimetrically and characterized via adhesion tests together with XRD, SEM, TEM; the coatings effect on fiber strength was also probed. XRD data showed that metallic Pd formed during surface activation whereas amorphous phases and trace amounts of pure Ni metal were plated via the electroless process. Electrodeposition in a thiosulfate bath was the most efficient Au coating process as compared with the analogous electroless procedure, and with electroplating using a commercial cyanide method. Strongly adhering coatings resulted upon metallization with three consecutive electrodepositions, which produced conductive fibers able to sustain power outputs in the range of 1 W. On the other hand, metallization affected the tensile strength of the fiber and defects present in the metal deposits make questionable the effectiveness of the coatings as protective barriers.

Efficient reduction of CCl took place upon exposure to 350-nm photons of aqueous solutions containing sulfonated poly(ether etherketone) (SPEEK) as a sensitizer and either poly(vinyl alcohol) (PVA) or HCOH/HCO buffer. The photoreaction formed chloride ions whose concentration increased linearly with time in solutions free of O, whereas slower reductions occurred in the presence of air. Utilization of formate buffer as the H-atom donor yielded photoreactions at least 10 times faster than those in the presence of PVA and generated CHCl as another reaction product. The quantum yield of chloride ion formation, ø(Cl), was found to be a function of both the SPEEK concentration and concentration of formate buffer. Whereas the quantum efficiency increased steadily with decreasing solution acidity, a drastic surge in the reaction rate occurred in neutral solutions. ø(Cl) first increased rapidly to a maximum value exceeding 1 at pH 7.3 and then decreased thereafter. The dependence of r(Cl) on (I), where I is the light intensity, and the occurrence of postirradiation formation of Cl through the reduction of CCl in the dark are further evidence that the photoreaction proceeded by a chain process. Several of the kinetic features were rationalized by means of a mechanism involving the α-hydroxy radicals of SPEEK and •CCl as chain carriers.

In the first of a series of papers on the iodine(V) oxide system, the chemical and physical properties associated with iodine(V) oxide in its anhydride (I2O5) and hydrated states (HI3O8 and HIO3) are examined. The three forms of the oxide have been investigated utilizing differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), and powder X‐ray diffraction (PXRD). Furthermore, the hydration rates governing the conversion of the anhydride (I2O5) to the initial hydrate (HI3O8) and later to the final hydrated state (HIO3) are reported and discussed. Results from this study suggest that the hydration mechanism for I2O5→HI3O8 begins with an accelerating period described as a nucleation and growth phase followed by a decelerating period that is diffusion limited. The initial rate of hydration was observed to be governed by a nucleation and growth mechanism, which was inhibited by covering the surface of the particle with an inert metal. Based on this investigation the initial rate of hydration appears to be strongly dependent on the anhydride’s available surface area which facilitates nucleation and growth of HI3O8. The final step, HI3O8→HIO3, proceeds through an initial induction period followed by a continuous acceleratory period unlike the first hydration step.