Near-grazing Incidence Angle Research Articles

EMP Coupling to a Straight Conductor Above Ground: Transmission Line Formulation Based on Electromagnetic Reciprocity

A simple model for coupling of an electromagnetic plane wave incident on a conductor above ground has been developed using reciprocity theory, providing some advantages as compared to the conventional transmission line approach. The model is developed using a semi-infinitely long single conductor above a lossy ground plane and connected by an arbitrary load impedance to a vertical grounding conductor. This configuration corresponds to the worst-case wave coupling, because it leads to a line induced current larger than in the cases of finite and multiconductor lines. A frequency-domain Thevenin equivalent model is developed to relate the incident wave amplitude to the voltage across a generic load, connected at any point on the vertical conductor. The application to the threat analysis of a high-altitude electromagnetic pulse impact on a power transmission line is discussed by considering the time-domain solution (via inverse Fourier transform) for an incident EMP fast-rise transient (E1) waveshape, following the standard IEC specifications. For typical high-voltage power line load impedances, it is shown that voltage magnitudes in the MV range can be induced across the line termination, in the case of a wave with a near-grazing incidence angle and with wave vector aligned along the horizontal conductor.

Comparison of electrochromic properties of Ni1−xO in lithium and lithium-free aprotic electrolytes: From Ni1−xO pigment coatings to flexible electrochromic devices

Electrochromic nickel oxide (Ni1−xO) pigment powder which was made from nickel acetate reacting with H2O2/urea solution followed by heat treatment of xerogels at 400°C (24h) was milled with zirconia beads in pure water or water with added nickel oxyhydroxy precipitate acting simultaneously as the dispersant and the coating binder. The corresponding pigment particle suspensions were spin coated on FTO glass and flexible ITO-PET foils, respectively, and cured at 150°C. The optical properties of the deposited pigment coatings on FTO glass substrates were determined with an UV VIS spectrometer, providing total direct transmittance (TT), total diffuse transmittance (DT) and haze (in %). Haze increased with the coating thickness but did not exceed 4%. SEM micrographs of the deposited pigment coatings revealed that they consisted of agglomerated Ni1−xO pigment with voids.Potential cycling of Ni1−xO pigment coatings and Ni1−xO thin films was performed in 1M LiClO4/PC and 0.1M TBA+ triflate/PC electrolytes, revealing that the pigment coatings exhibited electrochemical and electrochromic activity also in lithium free (aprotic) electrolyte, while variations of the oxidation and reduction reaction peaks at various scan rates confirmed the presence of surface electrochemical reactions. The near-grazing incidence angle reflection–absorption spectroscopic technique (IR RA) was employed for identifying surface and inner-grain Ni–O stretching modes, the former being responsible for observed electrochemical properties, which was also demonstrated from the ex situ IR RA measurements performed for coatings charged/discharged in 1M LiClO4/PC and 0.1M TBA+ triflate/PC electrolytes. The results disclosed in this study suggest that the electrochromic effect was not in direct correlation with the de-insertion/insertion of small ions into the NiO (bunsenite) grains but rather the pigment coatings behave similarly to nickel oxide electrochemical capacitors. The electrochromic response of a flexible EC devices made either of PEDOT (self-standing foil) or WO3 and Ni1−xO pigment coatings glued with PMMA based electrolytes without and with lithium salt were recorded for the demonstration of the possible practical application of wet deposited Ni1−xO pigment coatings made as “electrochromic” paints.

The coloration and degradation mechanisms of electrochromic nickel oxide

Nickel oxide (NiO) is the most common low-cost high-performance anodic electrochromic material that is widely used in the applications for smart windows. The coloration mechanism is, however, still not well understood and we show that this is due to the evolving chemical nature of the film during the electrochromic process. Chemical bath deposited (CBD) NiO was studied using the near-grazing incidence angle Fourier transform infrared spectroscopy (NGIA FTIR) and endurance potential cycling. We will show that the initial hydration of NiO films toward Ni(OH)2 proceeds gradually through a combination of coloration from hydroxyl (OH−) ions and bleaching through H+ ions. This process increases the optical modulation of the deposited film. However, when the OH− ion diffusion is significantly enhanced, OH− ion incorporation during coloration will lead to water incorporation. The extensive intercalated networks can then isolate NiOOH grains that results in irreversible coloration and this is commonly reported as degradation. We will propose a model to show that an isolation process can explain this degradation and can be easily reversible by annealing. This understanding of the coloration and degradation mechanisms suggests that an optimum control of hydroxyl ions is critical for both efficiency and durability of NiO electrochromic devices.

Effect of sample rotation on surface roughness with keV C 60 bombardment in secondary ion mass spectrometry (SIMS) experiments

The simplicity of interpreting depth profiling in SIMS experiments is often limited by sample damage and surface roughness that accompany the ion bombardment process. Molecular dynamics simulations are implemented to obtain mechanistic insight into the improvement of depth profiles due to sample rotation during keV C 60 bombardment of solids. The simulations show that sample rotation decreases the RMS roughness of the sample compared to a single azimuthal angle of incidence, as observed by experiment. The improvement is most noticeable for near-grazing angles of incidence. Bombardment of the sample at these angles builds up an anisotropic topology which sample rotation at least partially removes.

Effect of adsorbates on the formation of doubly excited He atoms during impact of He 2+ ions on a Ni(1 1 0) surface

The formation of doubly excited states of He atoms during impact of He 2+ ions with projectile energies of 60–1000 eV under near-grazing angles of incidence of 5°–20° on clean and adsorbate-covered Ni(1 1 0) surfaces is studied by means of Auger electron spectroscopy. Pronounced dependencies of electron spectra from autoionization of atoms in doubly excited 2 s 2, 2 s2 p and 2 p 2 configurations on the coverage of the target surface with adsorbates are observed. These are directly related to work function changes, which are studied for the controlled adsorption of oxygen. Changes of the electron spectra on the target temperature are found for adsorbate-covered surfaces only, which puts into question recent interpretations of similar electron spectra in terms of a high local electron spin polarization of Ni(1 1 0) by an alternative interpretation based on thermal desorption or dissolution into bulk of surface contaminations. The formation of doubly excited states is studied for the oxygen p(2 × l) and p(3 × l) superstructures on Ni(1 1 0) in order to provide well-defined experimental data for theoretical investigations.

Thermochromic properties of vanadium oxide films prepared by dc reactive magnetron sputtering

A transparent vanadium oxide film has been one of the most studied electrochromic (EC) and Thermochromic (TC) materials. Vanadium oxide films were deposited at different substrate temperatures up to 400 °C and different ratios of the oxygen partial pressure (PO2). SEM, AFM and X-ray diffraction's results show detail structure data of the films. IR mode assignments of the films measured by IR reflection–absorbance in NGIA (near grazing incidence angle) are given. It is found that the film has V2O5 and VO2 combined structures. The films exhibit clear changes in transmittance when the environment temperature (Te) is varied, especially in the 3600–4000 cm−1 range. Applying a Te that is higher than a critical temperature (Tc) to the samples, the as-RT (room temperature) deposited film with 9% PO2 has a transmittance variation of 30%, but the films that were deposited on a heated substrate of 400 °C have little variation. There is tendency of bigger variation in transmittance for the sample deposited at a larger PO2, when it is applied by 200 °C Te.

Ship detection and characterization using polarimetric SAR

Polarimetric information is investigated for ship detection and characterization at operational satellite synthetic aperture radar (SAR) incidence angles (20°‐60°). It is shown that among the conventional single-channel polarizations (HH, VV, or HV), HV provides the best ship‐sea contrast at incidence angles smaller than 50°. Furthermore, HH polarization permits the best ship‐sea contrast at near-grazing incidence angles. The wave polarization anisotropy is used for optimal information extraction from polarimetric SAR data. It is shown that fully polarimetric information permits a significant improvement in the ship‐sea contrast for relatively calm wind conditions, in comparison with conventional (i.e., scalar) single-channel polarizations (i.e., HH, VV, or HV). For rougher sea conditions, the effectiveness of polarimetric tools may be significantly degraded. Ship characterization is also investigated using the symmetric scattering characterization method (SSCM). Identification of ship targets with significant symmetric scattering can provide a useful ship pitch angle estimate under certain conditions.

Solar absorber coatings based on CoCuMnOx spinels prepared via the sol–gel process: structural and optical properties

Abstract Titanium-doped and undoped CuCoMnOx spinel films were deposited on Al substrates from sols which were made from the following: Co-acetate, Cu-chloride and Mn-acetate (Ti:CoCuMnOx-I); and Co-acetate, Cu-nitrate and Mn-acetate (CoCuMnOx-II). The precursors’ ratio Co:Cu:Mn was equal to 1:3:3. The solar absorptance (αs) and the thermal emittance (eT) of the films, which were annealed at 450°C for 15 or 30 min, were determined from the corresponding diffuse reflectance spectra in the 0.32–20 μm range. The results show that the CoCuMnOx-II films with SiOx protective over-coatings exhibited values of αs=0.85–0.91 and eT below 0.036 after just a single dipping/annealing cycle. The structure of the films was studied with X-ray diffraction (XRD), infrared (IR) absorbance and near-grazing incidence angle (NGIA) reflection-absorption spectroscopy. Our results suggested that the films have a spinel structure with the composition CoCuMnOx. The stability of the films was tested by soaking them in boiling water for 2 h. NGIA IR spectra of the treated films confirmed the formation of the hydrated mixed oxide (Mn-, Co-, Cu-) phases. To improve the stability of the films two kinds of protective over-coatings were tested: one over-coating was based on polysiloxane resin and the other on high-density silica (T-resin). Films that were resistant to boiling water were obtained by applying the high-density silica protective over-coating, which was cured at 140°C for 30 min.

Characterization of vanadium oxide and new v/ce oxide films prepared by sol-gel process

The preparation of vanadium oxide and new mixed V/Ce oxide thin films as intercalation compound for lithium ions (at 55 and 38 at. % of V) started from aqueous inorganic precursors. Thin films were prepared via the sol-gel process by dip-coating only once. Glass slides covered with SnO 2:F were used as substrates. The influence of added cerium precursors on the electrochemical optical and structural properties of thin films was studied by cycling voltammetry (CV), in-situ ultraviolet and visible (UV-VIS) spectroscopy, atomic force microscopy (AFM) and IR spectroscopy. The addition of CeO 2 improved the poor stability of vanadium oxide films and enhanced their ion-charge capacity up to 30 mC/cm 2. In all films the process of intercalation of lithium ions was followed by in-situ UV-VIS spectroscopy and ex-situ FT-IR spectroscopy performed at near-grazing incidence angle. The intercalation of Li + ions was confirmed trough shifting of the absorbance edge in UV-VIS spectra and by the observed shifts of V-O v vibrations in the IR spectra. The surface of the films was also characterized by AFM imaging before and after cycling in 1M LiClO 4 in propylene carbonate electrolyte.

Ex situ and In situ Infrared Spectroelectrochemical Investigations of V 2 O 5 Crystalline Films

Vanadium oxide films were prepared by dip‐coating from V‐oxoisoproxide sols and heating at 300°C for 1 h. Transmission electron microscopy combined with electron and X‐ray diffraction revealed that the films consist of disordered grains with an orthorombic structure . Electromotor force (emf), cyclic voltammetric (CV), and chronocoulometric measurements, combined with in situ ultraviolet‐visible (UV‐vis) spectroelectrochemical measurements, revealed similar electrochromic and electrochemical properties with other sputtered and sol‐gel derived films. IR absorbance and reflection‐absorption spectra, performed at near‐grazing incidence angle (NGIA) conditions (80°, P‐polarized), allowed us to compare the observed transverse optical (TO) and longitudinal optical (LO) frequencies obtained from the dispersion analyses of crystalline reflection IR spectra. TO and LO spectra of charged films show that interactions modify the terminal (vanadyl), bridging , and edge‐sharing stretching frequencies, suggesting that these interactions take place between the oxygens bordering the cavities in which ions are accomodated during charging. The red‐frequency shift of the stretching and disappearance of the bridging stretching mode can be used as a diagnostic tool to differentiate between films cycled in the safe and unsafe potential regions. A polaron absorption was observed above in the ex situ TO and in situ NGIA reflection‐absorption (LO) spectra of films charged in the safe potential region. © 1999 The Electrochemical Society. All rights reserved.

New counter electrode prepared as vanadium oxide and V/Ce oxide films: preparation and characterization

Vanadium oxide and mixed V/Ce-oxide films at 78, 55, 38, 32 atomic % of V were prepared via the sol-gel route from an aqueous colloidal solution of inorganic precursors. The influence of the added cerium precursor on their electrochemical, optical and structural properties was investigated by cyclic voltammetry (CV), X-ray analysis, IR spectroscopy and UV-VIS techniques. The electrochemical stability of films was tested by CV measurements in 1 M LiClO 4 in propylene carbonate electrolyte. The addition of CeO 2 improved the poor stability of vanadium oxide films and enhanced their ion-charge capacity up to 30 mC/cm 2 for thicknesses about 300 nm. The intercalation of Li + ions in vanadium oxide and V/Ce-oxide films was followed by FT-IR spectroscopy performed at near-grazing incidence angle (NGIA) conditions in combination with CV measurements at potentials of −1.5 V and +2.0 V (vs. Ag/AgCl). The observed shift of V–O v vibrations in the IR spectra confirmed the intercalation of Li + ions.

In situ UV-Vis and ex situ IR spectroelectrochemical investigations of amorphous and crystalline electrochromic Nb 2 O 5 films in charged/discharged states

Niobium oxide (Nb2O5) films and powders have been obtained via the sol-gel route from an NbCl5 precursor. XRD spectra revealed that films with pseudohexagonal (TT-phase) and orthorhombic (T-phase) structure were formed at 500 °C and 800 °C, respectively, while at 300 °C films were amorphous. Infrared (IR) and Raman spectra of powders and films of Nb2O5 in different polymorphic forms were detected, and vibrational band assignments were made. Electrochromic properties of amorphous films and films with the TT-phase were established from in situ ultraviolet visible (UV-Vis) spectroelectrochemical measurements and correlated with ex situ IR transmission spectra of charged films. Ex situ IR spectra revealed that charging of amorphous films is accompanied by variations of the Nb-O stretching mode intensity, while, for films with the TT- and T-phase, splitting of the Nb3-O stretching modes and the appearance of polaron absorption were noted with Li+ ion insertion. Ex situ X-ray diffraction (XRD) spectra of charged films with the TT-phase showed changes of the unit cell dimensions with charging. The influence of the polaron absorption on the ex situ near-grazing incidence angle (NGIA) IR reflection-absorption spectra of charged/discharged films is discussed in detail.

Characterisation of redox states of Ni(La)-hydroxide films prepared via the sol-gel route by ex situ IR spectroscopy

Ni(La)-hydroxide films were prepared from aqueous colloidal solutions containing nickel sulfate and lanthanum acetate in the molar ratio 10:1. Two types of film were made by heating for 15 and 60 min at 300 °C. Thermogravimetry (TG) and X-ray diffraction (XRD) reveal that both films consist of NiO (bunsenite 40%) nanoparticles (particle size ∼30 A), the remainder being amorphous. IR spectroscopy showed that the amorphous phase comprised the α(II)-Ni(OH)2 phase incorporating SO42−, carboxylate and water species. Cyclic voltammetry (CV) in a 0.1 M LiOH electrolyte combined with in situ UV-VIS spectroscopy revealed that the colouring/bleaching changes, as a function of applied potential, differed considerably for the two types of film. Ex situ IR spectroelectrochemical measurements at near-grazing incidence angle conditions using P-polarised light (NGIA IR) were performed for films heated for 60 min in 0.1 M LiOH and 0.1 M tetramethylammonium hydroxide (TMAH) electrolytes and cycled 1402 and 1802 times. During the oxidation/reduction cycles the α(II)-Ni(OH)2 phase transforms to the γ(III)-NiOOH phase, while the β(II)-Ni(OH)2 did not develop. This explains the high cycling stability of Ni(La)-hydroxide films. The incorporation of TMA+ ions was observed from the ν(CH3) stretching band intensities in the IR spectra of cycled films.

FT- IR Spectroscopy as a Method for the Study of the Different Crystallization Forms of CaCo<sub>3</sub>

The phenomenon of softening water by magnetic field has been known for several years. It was established that nucleation and crystallization of calcium carbonate in hard water can be influenced by the magnetic field and since that time it is no longer necessary to look always for chemical means to prevent accumulation of calcium carbonate on surfaces exposed to hard water. This is also of essential importance in diminishing the chemical pollution of the environment. Our interest was to search for an explanation of changes in crystallization of calcium carbonate (crystals grown from the hard water) with the presence of magnetic field. The water used for the expenmental work was a model system based on the ultraclean water with resistivity R = 18 MΩ, and 0.035 M solutions of Na 2 CO 3 and CaCl 2 in such amounts that their concentrations in the resulting solutin were 0.008 M. Those solutions were added to water as precursors for obtaining calcium carbonate. The concentration of Ca 2+ was 350 ppm. Magnetically treated and non-treated water samples were dried under controlled conditions (a temperature of 70°C and 40% humidity). Treated water was exposed to magnetic field of 200 - 280 mT during drying. The crystals obtained by the evaporation of water were analysed by different methods: scanning electron microscopy (SEM), FT - IR spectroscopy and magnetic measurements with a susceptometer - magnetometer. The present contribution is focused on FT - IR (Fourier Transformed Infra Red) spectroscopy as a new method for characterizing thin films of crystallization products formed under the influence of a magnetic field. In order to overcome the problems encountered with thin films (50 - 100 μm), NGIA (Near Grazing Incidence Angle) FT - IR reflection absorption spectroscopy in combination with P - porarized IR light have been used. We used polished platelets of different metals (5 x 2.5 cm) as substrates for NGIA FT - IR thin films analyses to study the influence of impurity ions on the crystallization of calcium carbonate under an applied magnetic field.. The platelets were of Fe, Cu and Zn, as well as glass substrates covered by a thin layer of SnO 2 :F. Platelets were covered with thin films of the tested solutions and the samples were dried afterwards under the same conditions as mentioned above. A Perkin Elmer Spectrometer Model 2000 equipped with Spectra Tech NGIA, wich enables measurements at 80° with P - polarized radiation was used to characterize the thin films of deposited material. Figure 1 shows the comparison of spectra (magnetically treated and nontreated sample) obtained on thin films of calcium carbonate grown from hard water deposited on the Fe substrate.

Electrochemical and structural characterisation of dip-coated Fe/Ti oxide films prepared by the sol-gel route

Thin solid films of mixed Fe/Ti oxide composition (Fe/Ti molar ratios: 0.5∶1, 1∶1, 1.5∶1) have been made from Fe(NO3)3 alcoholic solution to which Ti(OiPr)4 was added. Films have been deposited by the dip-coating technique and heat-treated at 300°C and 500°C. Powders of Fe/Ti oxide heat-treated at 300°C are amorphous, while powders annealed at 500°C for 40 hours transformed to mixed rutile, pseudobrookite and hematite phases. The structure of the XRD amorphous films was identified with the help of near-normal reflection absorption (6°) (IRRA) and near-grazing incidence angle (NGIA) spectroscopy. NGIA FT-IR spectra of films are characterised with a single phonon mode appearing in the spectral range 600–950 cm−1 which shifts with increasing Ti concentration from 675 cm−1 (Fe2O3) to 904 cm−1 (TiO2) thus exhibiting one-mode behavior.

Sol-gel derived hydrated nickel oxide electrochromic films: Optical, spectroelectrochemical and structural properties

Electrochromic hydrated Ni-oxide films were prepared using a dip-coating technique from a nickel sulphate heptahydrate precursor in combination with glycerol, formamide and polyvinyalcohol. In-situ monochromatic (λ=400 nm) spectroelectrochemical measurements using a potential of −0.4 V to 0.8 V in 0.1M LiOH electrolyte revealed that the electrochromic efficiency was 23.5 cm2/C. The observed colouring/bleaching transmittance of a 100 nm thick film changed during potential cycling (20 cycles) by 45%. Ex-situ FT-IR absorption/reflection measurements performed at near-grazing incidence angle conditions (80°) confirmed transformation of as-deposited α-Ni(OH)2 phase to β-Ni(OH)2 at cathodic (bleached state) and β-NiOOH at anodic (coloured state) potentials during extended cycling (200 cycles). Clear evidence of the OH− ions insertion and release of SO 4 2− ions from the as-deposited films when soaked (0.5 hour) in 0.1M LiOH are given. These processes are accompanied by the transformation of the residual COO− groups originating from the peptisation with glacial acetic acid into CO 3 2− species residing in the films during extensive potential cycling.

Spectroelectrochemical and structural properties of electrochromic Co(Al) -oxide and Co(Al,Si) -oxide films prepared by the sol-gel route

New electrochromic spinel-type Co(Al)-oxide and Co(Al,Si)-oxide films exhibiting coloring/bleaching changes Δ T= T colored− T bleached = 75% − 25% = 50% (where T is transmittance) with a coloring efficiency of 22cm 2 C −1 were deposited by a dip-coating method from aqueous colloidal solutions made by thermal hydrolysis of Co(II)-acetate, Al(III)-sulphate, citric acid and 3-aminopropyltriethoxysilane precursors. The nanocomposite spinel structure of the films and powders was determined using X-ray diffraction, thermogravimetry, visible and infrared transmission and reflection-absorption spectroscopy performed at near-grazing incidence angle conditions (80°) using p-polarized light. The existence of spinel lattice modes in the IR spectra of cycled films proved that the spinel structure of Co(Al,Si)-oxide films is preserved at least on the scale of short-range interactions detected with IR spectroscopy. In addition to this, sulphate (SO 4 2−) ions are retained in the structure of cycled films heat-treated at 500 °C. The role of order-disorder transitions of sulphate ions present in cycled films is discussed with respect to their influence in enhancing the speed and degree of coloring/bleaching changes of electrochromic Co(Al,Si)-oxide spinel films.

Optical, spectroelectrochemical and structural properties of sol-gel derived Ni-oxide electrochromic film

Ni-oxide films prepared using the sol-gel route and dip-coating method have been investigated by X-ray diffraction, scanning electron microscopy, FT-IR spectroscopy, cyclic voltammetry and in situ UVVIS spectroelectrochemical methods. The sols were prepared from a nickel sulphate hexahydrate precursor with formamide and polyvinylalcohol added to improve the abrasive resistance of films and to increase the yield from dip-coating deposition method (100–120 μm per dipping cycle). The films consisted of 40% NiO crystalline phase with an average grain size of 10 to 30 Å. The crystallites were incorporated into the amorphous phase which was found to resemble the α(II)-Ni(OH) 2 phase. A pronounced electrochromic effect ( ΔT ≈ 60%) was found by cycling the films in a 0.1 M LiOH electrolyte. This produced a maximum colouration efficiency ( λ = 450 nm) of 35–40 cm 2 C −1. Longitudinal optical (LO) mode of films potentially cycled up to 200 times have been detected by near-grazing incidence angle (NGIA) FT-IR reflection-absorption spectroscopy. The results revealed that the as-deposited films are progressively transformed to the β(II)-Ni(OH) 2 phase which is then converted to the β(III)-NiOOH phase during further potential cycling. The influence of foreign ions (SO 2− 4, CO 2− 3, OH −) on the development of persistent electrochromism and stability of films was established and discussed in detail.

Analysis of scattering from rough surfaces at large incidence angles using a periodic-surface moment method

The moment method is used to calculate electromagnetic backscattering from one-dimensionally rough surfaces at near-grazing incidence (angles of incidence up to 89/spl deg/). A periodic representation of the scattering surface is used to prevent edge effects in the calculated scattering without the use of an artificial illumination weighting function. A set of universal series common to all elements of the moment interaction matrix are derived that allow the efficient application of the moment method to the periodic surface. Comparison with other moment method implementations demonstrates the efficiency of this approach. The scattering from surfaces with Gaussian roughness spectra is calculated at both horizontal and vertical polarizations, and the results are compared with the theoretical predictions of the small-perturbation method (SPM) and Kirchhoff approximation (KA). SPM shows the expected loss of accuracy in predicting the vertically polarized backscattering from small-roughness, short-correlation-length surfaces at large incidence angles. SPM accurately predicts the backscattering from the same type of surface at incidence up to 89/spl deg/ at horizontal polarization, KA provides accurate estimates of the scattering from long correlation-length surfaces as long as the incidence angle is small enough that surface self-shadowing does not occur. When shadowing occurs, KA severely underpredicts vertically polarized backscattering and less severely overpredicts backscattering at horizontal polarization. >

Mixed phosphotungstic acid/titanium oxide gels and thin solid xerogel films with electrochromic-ionic conductive properties

Electrochromic-ion conductive gels (σ = 1.7 × 10−4 S/cm) and thin solid films composed of phosphotungstic acid (PWA) incorporated in titanium oxide xerogel (PWA:Ti = 0.07) were made via the sol-gel route by the dip-coating technique. The electrochromism of the as-deposited films was studied with the help of cyclic voltammetric (CV) measurements in HClO4 electrolyte, in situ ultraviolet-visible spectroelectrochemical measurements and ex situ near-grazing incidence angle (NGIA) reflection spectroscopy. It was demonstrated that the colour change from transparent to blue is about 40% efficient and is accompanied by effective inserted charges up to 35 mC/cm2, giving rise to HxPW12y+O403− species with x = 4.7 and y = 5.6. Ex situ NGIA Fourier transform infrared reflection measurements revealed that proton injection decreases the intensity of the longitudinal optical (LO) modes corresponding to the intra νW-Oc-W and inter νW-Ob-W vibrations of the Keggin's ions, while the νW-Od modes remain unaffected. An intensity decrease of the LO modes of TiO vibrations was also detected in the ex situ NGIA reflection spectra of cathodically coloured pure Ti xerogel films. It was found that the proton insertion process is accompanied by the hydroxylation of titanate ions, while no such effect was noted for PWA/Ti and Ti xerogel films aged in water and the corresponding electrolytes without the applied potential. The electrochromic-ionic conductive properties of mixed PWA/Ti gels were demonstrated in a semi-liquid electrochromic cell.