We present a systematic study of isolated hydrogen in diverse forms of ZrO 2 (zirconia), both undoped and stabilized in the cubic phase by additions of transition-metal oxides (Y 2 O 3 , Sc 2 O 3 , MgO, CaO). Hydrogen is modeled by using muonium as a pseudoisotope in muon-spin spectroscopy experiments. The muon study is also supplemented with first-principles calculations of the hydrogen states in scandia-stabilized zirconia by conventional density-functional theory (DFT) as well as a hybrid-functional approach which admixes a portion of exact exchange to the semilocal DFT exchange. The experimentally observable metastable states accessible by means of the muon implantation allowed us to probe two distinct hydrogen configurations predicted theoretically: an oxygen-bound configuration and a quasiatomic interstitial one with a large isotropic hyperfine constant. The neutral-oxygen-bound configuration is characterized by an electron spreading over the neighboring zirconium cations, forming a polaronic state with a vanishingly small hyperfine interaction at the muon. The atom-like interstitial muonium is observed also in all samples but with different fractions. The hyperfine interaction is isotropic in calcia-doped zirconia [A iso = 3.02(8) GHz], but slightly anisotropic in the nanograin yttria-doped zirconia [A iso = 2.1(1) GHz, D = 0.13(2) GHz] probably due to muons stopping close to the interface regions between the nanograins in the latter case.

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Positron annihilation techniques are used for the structural investigation of solids but the interpretation of results in grainy and porous media is still unclear. A unique picture can be obtained assuming that the dominant process is Ps trapping in competing "extended free volume" sites. In samples with a large amount of free volumes near-saturation Ps trapping will rule the lifetime pattern, and very long lifetimes of over 100 ns might arise from o-Ps trapped in mesopores. It is shown that lifetime parameters must be corrected for the 3γ/2γ counting efficiency ratio. The results demonstrate the high sensitivity of Ps to mesopores in zeolites but also that Ps-trapping poses limitations on the applicability of lifetime to structural investigation in porous systems. The evolution of the lifetime spectra upon changes in the sample and measuring conditions should be considered in a complex way, observing not only changes in some selected components but in the whole lifetime pattern simultaneously.

The free-volume parameters in various urethane/urea membranes obtained by varying the ratio of the structural constituents, polypropylene oxide and polybutadiene, were studied by positron lifetime and Doppler broadening measurements. On bi-soft segment membranes, a correlation was found between the composition of membranes, the normalized free volume, the radii of the holes and gas permeability. However, the correlation is not clear when PU data are also considered, indicating that other features must also play an important role in the permeation mechanism.