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Open Physics
|
2007
|
vol. 5
|
issue 1
83-90
EN
Experimental results on the current-voltage characteristics of polydiacetylene (PDA) single crystals reported by Aleshin et al [Phys. Rev. Vol. B 69, (2004) art. 214203] are reinterpreted in terms of the phonon-assisted electron tunnelling model. It is shown that the experimental results, measured in the temperature range from 1.8 K to 300 K are consistent with the tunnelling rate dependence on field strength, computed for the same range of temperatures. An advantage of this model over that of Aleshin et al, using the variable range hopping (VRH) model, is the possibility of describing the behaviour of I - V data measured at both high and low temperatures with the same set of parameters characterizing this material. This assertion is confirmed by comparison of the temperature-dependent current-voltage data extracted from Aleshin et al’s work with tunnelling rate dependence on temperature, computed using two different expressions of the phonon-assisted tunnelling theory. The temperature dependence of the conductivity of an ion implanted PDA crystals [B. S. Elman et al, Appl. Phys. Lett., Vol. 46, (1985) p. 100] and polypyrrole [P. Dutta et al, Synth. Met., Vol. 139 (2003) p. 201] are also explained on the basis of this model.
EN
Free volume size V_{f} and proton conductivity σ of a novel polymer electrolyte membrane were investigated as a function of temperature and relative humidity up to 140°C and 80%, respectively. The free volume size V_{f} for Nafion® HP JP reflect the α-transition temperature at about 98°C. In addition the free volume size V_{f} for Nafion® HP JP is smaller than that for Nafion® NRE212 membrane which leads to lower methanol permeability of the former membrane. The proton conductivity σ for Nafion® HP JP decreases with increase of temperature up to transition temperature due to free and bound water loss, then it starts to increase due to dynamic segmental motion. It increases for Nafion® HP JP with the increase of the relative humidity. A good correlation between V_{f} and σ was successfully established for both membranes which indicates that σ is governed by the free volume. In conclusion, Nafion® HP JP is a suitable membrane for a proton exchange membrane fuel cell application.
EN
The proton conductivity mechanism in per-fluorinated sulfonic acid/PTFE copolymer Fumapem® membranes for polymer electrolyte membranes has been investigated. Three samples of Fumapem® F-950, F-1050 and F-14100 membranes with different ion exchange capacity 1.05, 0.95, and 0.71 meq/g, respectively, were used in this study after drying. The o-Ps hole volume size (V_{FV,Ps}) was quantified using the positron annihilation lifetime technique while the proton conductivities (σ ) were measured using LCR Bridge as function of temperature. It was found that as the ion exchange capacity increases, the proton conductivity increases and the free volume expands. Temperature dependences of proton conductivity and the o-Ps hole volume size (V_{FV,Ps}) reflect the glass transition temperature of the membrane. A good linear correlation between the reciprocal of the o-Ps hole volume size (1/V_{FV,Ps}) and log(σ)+Δ E_a/2.303k_{B}T, (where ΔE_a is the activation energy, T is the absolute temperature and k_{B} is the Boltzmann constant) at different temperatures indicate that the ionic motion in dry Fumapem® is governed by the free volume. A linear relationship between the critical hole size γ V*_{i} and the ion exchange capacity was also achieved.
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