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In this work, glass-ceramics in the xBeO–20Fe2O3–(80-x)TeO2 system with x = 0–25 mol% were synthesized by the traditional melt quenching route and studied by inductively coupled plasma optical emission spectroscopy, X-ray diffraction, confocal microscopy, infrared and Raman spectroscopy. BeO addition was found to support the crystallization process of Fe2O3 during melting, and an increased BeO content was associated with an increased fraction of the crystalline Fe2O3 phase and an increased size of these crystallites. Furthermore, samples doped with BeO exhibit an increasing polymerization of the residual tellurite glass network compared to the undoped sample. The magnetic properties and specific heat of all synthesized materials were measured, and the results show that all studied samples behave as spin-glasses. Also, the Morin transition of hematite was observed at 260 K with intensity depending on the material content in Fe2O3 crystalline phase, the formation of which correlates with the amount of added BeO.

A systematic investigation of the luminescence properties of Dy3+ doped alkali-alkaline earth orthoborates of the stoichiometric composition XZBO3 with X = Li, Na, K and Z = Mg, Ca, Ba was conducted. XRD diffractograms show that the compounds LiMgBO3, LiCaBO3, LiBaBO3, NaMgBO3, NaCaBO3, NaBaBO3, and KMgBO3 could be produced in high purity. Relatively intense luminescence was observed only for the phases LiCaBO3, NaMgBO3, NaCaBO3 and NaBaBO3. Micro Raman investigations show that the Dy3+ luminesence mainly originates from the orthoborate phase in these samples. Photo-luminescence spectroscopy of LiCaBO3, NaCaBO3 and NaBaBO3 shows the typical Dy3+ emission with the prominent emission peak in the yellow spectral range around 575 nm. A second, but much less intense peak is observed at around 485 nm (cyan). The luminescence emission spectrum of Dy3+:NaMgBO3 is much different: here, the highest emission intensity is observed at about 485 nm. It is proposed that the Dy3+ ions occupy the Na positions in this crystal phase which has a much higher symmetry than the alkaline earth positions in the other examined crystal phases. This is supported by broadened and more split up peaks in the excitation and emission spectra of Dy3+:NaMgBO3 suggesting a much stronger local crystal field at the rare earth position in this compound. The results are additionally compared to spectroscopic data of different well known Dy3+ doped crystalline compounds and Dy3+ and Eu3+ doped alkali-alkaline earth orthoborates from other publications, which offer further insight into the relation between the crystallographic sites of the doped rare earth ions and their luminescence.

Glass formation and structure-property relations were explored in highly modified borate glasses containing high loads of rare-earth elements, whose crystalline analogues display a trigonal to tetrahedral borate phase transition (BO33− → BO2O23−, where O and O− indicate bridging and non-bridging oxygen atoms). The resulting borate networks are completely depolymerized, where borate anions are crosslinked to rare-earth and modifier cations via ionic bonds. The borate structure was found to be based on a single structural unit, BO33− triangles, whose fundamental vibrations are all active in both the Raman and infrared. The local environment of the rare-earth ions in orthoborate glasses was studied with far infrared spectroscopy and, in some cases, by using terbium as a probe ion. A linear correlation was obtained between the effective force constant in the far infrared and the field strength of the rare-earth cation.

Opaque mosaic glass tesserae containing calcium antimonates from Ancient Messene, Greece (1st–4th century CE) were investigated by scanning electron microscopy, Raman spectroscopy and X-ray diffraction. Both trigonal CaSb2O6 and cubic Ca2Sb2O7, with crystallite diameters below 1 μm, were identified as opacifying agents. To better understand ancient technologies, we prepared model glasses that were opacified by crystallisation via a secondary heat treatment, by direct crystallisation during the melting process, or by the addition of pre-reacted calcium antimonate to a base glass. We found that direct crystallisation replicated the antique glass artefacts most accurately. We demonstrated that 0.2 wt% of nucleating agents like TiO2 and SnO2 already exert significant influence on the crystallisation behaviour of calcium antimonates. Secondary scattering centres such as silica and carbonates contribute to the optical appearance. Concurrently, we reproduced opaque white glass ceramics in a reconstructed, wood-fired, Roman-type glass furnace built by Wiesenberg (2014).

Sodium-calcium-phosphate glasses doped with SiO2 or Si3N4 having similar sodium ion concentrations were prepared by melt quenching. The conductivity was measured by impedance spectroscopy under nitrogen atmosphere in a wide frequency range (10 mHz–1 MHz) and wide temperature range (153–473 K). At 36.6 °C, DC conductivities of all glasses vary between 1.1 ∗ 10−12 and 8.9 ∗ 10−12 S cm−1 and have similar activation energies (between 0.87 and 0.91 eV), which are characteristic for an ionic conduction mechanism. The analysis of AC conductivities showed that the spectra are governed by one dynamic process – hopping of the mobile charge carriers - which may be described i.e., by the ‘concept of mismatch and relaxation’ or by the ‘random barrier’ model. The obtained results confirmed a higher influence of nitrogen incorporation on the various glass conductivity parameters than shown for silicon doping alone. However, the influence of fundamental structural changes on the glass conductivity is less relevant as is the overall sodium ion concentration, which remains the decisive factor for a high ion conduction.

Laser-induced defects in glasses are of considerable interest for many applications from optics to photonics. The importance of low-level impurities of polyvalent ions in aiding defect formation has been identified early on. (Fluoride-)phosphate glasses are used today as laser materials, waveguides, amplifiers and luminescing materials, all sensitive to a change of the materials transmission by the interaction with light during application. To better understand the processes of defect generation and recovery, a systematic comparison of defect formation in various glasses and for various radiation sources and dopants has been conducted over the last decades. Here we will focus on (fluoride-) phosphate glasses doped with 50 to 5000 ppm of the 4d and 5d ions Zr, Nb, Ta, Mo and W. Glasses were melted under air or under reducing conditions in order to shift the redox equilibrium of the dopants before irradiation with either the 193 nm or 248 nm excimer laser. Only for W, Mo and Nb reduced ion species were confirmed by optical and/or ESR spectroscopy in the pre-irradiated glasses. However, irradiation showed for all metaphosphates the presence of reduced dopant species (W5+, Mo5+, Ta4+, Nb4+, Zr3+), acting as extrinsic hole centers (HC) after being photo-oxidized by laser irradiation to the fully oxidized d0 ions (Mn+)+–HC. Only for Ta5+ with its (Ta5+)− -electron center (EC), photo-reduction to the tetravalent ion was observed. Defect recovery was followed up to 16 years after the irradiation experiments, showing that most (Mn+)+–HC were very stable, while intrinsic HC either recombined with EC or converted into extrinsic (Mn+)+–HC. Due to ubiquitous iron impurities, even these high purity glasses with iron levels of 5–10 ppm or less, showed the formation of (Fe2+)+-HC.

Oxynitride phosphate glasses and glass-ceramics were prepared using new synthesis routes for phosphate glasses. Materials were melted from pre-prepared glass samples in the system Na-Ca-P-O with addition of Mg and/or Si3N4 powders under different preparation conditions. The melting process was conducted at 1000–1500 °C either under air or nitrogen atmosphere to obtain materials with different nitrogen content. Their topography and structure were characterized by Confocal Microscopy, Scanning Electron Microscopy, X-ray powder diffraction and Raman and infrared spectroscopy techniques, while their chemical compositions were examined by Energy Dispersive X-ray spectroscopy (EDS). All materials prepared under nitrogen atmosphere were found to contain a relative low quantity of nitrogen and high amount of Nb leached from the crucible. The reaction with the Nb crucible was not previously observed for silicon-based oxynitride glasses. The synthesized materials form two groups: glasses and glass-ceramics. The first ones, were prepared under air and nitrogen atmospheres at temperatures up to 1400 °C, and were found to be amorphous and homogeneous. Raman and infrared spectroscopy measurements confirm the presence of amorphous phosphates in the synthesized materials. The samples of the second group were prepared at temperatures above 1400 °C and were found to be translucent and partially crystallized. They contain nanocrystallites of calcium and sodium phosphates including hydroxyapatite (HAp). The thermal properties of samples were studied by Differential Scanning Calorimetry (DSC). The obtained glass transition temperatures range from about 360 °C to 640 °C and exhibit high values for glass-ceramic materials. Stability is improved in the studied glass-ceramics because of the increased degree of network polymerization of the remaining glassy matrix. The approximate fragility index decreases two times for oxynitride materials compared to the primary glass. The synthesized new materials may be competitive to well-known bioactive phosphate glasses thanks to their improved stability by Mg, Si, N and Nb doping.

Red opaque glasses of two different sites in central Germany, a medieval glassworks in Glashutten, Taunus Mountains, and an early modern glassworks in Wieda, Harz Mountains, were analysed with regard to their optical appearance. By scanning electron microscopy and X-ray diffraction, metallic copper nanoparticles were identified as a conspicuous constituent in these glasses. In addition, similar opaque red glasses were reproduced in the laboratory in order to better understand the manufacturing process. Detailed analysis of the optical scattering was conducted in order to evaluate the role of Cu0 nanoparticles in the colouring mechanism relative to other possible reasons of colouration. We find clear differences between the possible contributions of Cu2O (cuprite) particles and metallic copper (Cu0) nanoparticles. Through simulated backscattering spectra we were able to calculate an average copper particle radius in the archaeological glass samples resulting in a value of up to 95 nm, which matches well the results of SEM investigation (minimum 65 nm). Using the methods we applied in this study, it becomes possible to reconstruct various processing conditions as they were applied in medieval manufacture of these particular materials.

Alkali germanotellurite glasses of composition 0.3M2O–0.7[(1-x)GeO2–xTeO2], M=Li, Na and 0 ≤ x ≤ 1, were investigated by Raman and infrared vibrational spectroscopic techniques to search for the origins of the alkali ion-dependent network former mixing (NFM) effect in these ion-conducting glasses. The vibrational spectra measured on mixed network-former glasses, and the spectral comparison between equimolar-mixed glasses (x = 0.5) and pellet-mixtures of the endmember glasses, 0.3M2O–0.7GeO2 and 0.3M2O–0.7TeO2, provided evidence for the formation of hetero-atomic Ge–O–Te linkages and structural rearrangements in the germanate and tellurite components of the glass. The mixing-induced structural rearrangements were expressed in terms of chemical equilibria between the network-building units and were used to make qualitative predictions for changes in the network cross-linking density and the related network-strain energy, as well as in the binding energy part of the activation energy for ion conduction. Thus, it is proposed that the mixing-induced structural modifications in the germanate and tellurite parts of glass cause the cancelation of changes in the binding energy and the network-strain energy contributions to the activation energy for ion transport. These qualitative predictions were discussed in the context of the previously found absence of an NFM effect in ionic conductivity for M=Na and the presence of a weak positive NFM effect for M=Li.

Thermal poling, i.e., exposure of a glass to a DC electrical field at moderate temperature, enables the generation of an anisotropic surface layer. Cation motion on the anode side results in the formation of an internal gradient in the electrical potential which can be frozen-in upon cooling. This is accompanied with a change in the polarity of the anode surface and, hence, a change in surface wettability. In this article, we study the effect of thermal poling on the wettability of soda-lime silicate glasses. We confirm a poling-induced increase in surface hydrophobicity on the air-side of commercial float glass, with a water wetting angle increase of around 20° for poling at 210 °C and 1.5 kV. The effect is persistent after storage for three months under ambient conditions. Significant variation between air and tin-side of the float glass indicates strong compositional dependence and offers a route for tailoring the surface chemical properties of functional glass substrates.

Modifier-mixing provides a well-established tool for generating non-linear trends in physical properties of multi-component glasses. While typically, mixtures of alkali or alkaline earth ions are considered, here, we report on the structural incorporation of Co 2 + and Mn 2 + , respectively, in strontium metaphosphate glasses, and on the associated Co-Sr/Mn-Sr mixed-modifier effect. Structural variations in the short and intermediate range were investigated with vibrational spectroscopy and synchrotron X-ray diffraction, elucidating the coordination states of the two transition metals as a function of mixing ratio. For the join of Co-Sr, we find that the octahedral coordination dominates for lower contents of cobalt, whereas the tetrahedral state is predominantly found at higher cobalt concentration. The analogue decrease in the coordination number is weaker when mixing manganese and strontium ions. Coordination numbers are shown to correlate clearly with vibrational spectroscopic data and macroscopic physical properties.

Undoped, singly Sm doped, Ce doped, and Sm/Ce co-doped lithium alumino-phosphate glasses with different alkaline earth modifiers were prepared by melt quenching. The structure of the prepared glasses was investigated by FT-IR and Raman, as well as by optical spectroscopy. The effect of the optical basicity of the host glass matrix on the added active dopants was studied, as was the effect doping had on the phosphate structural units. The optical edge shifts toward higher wavelengths with an increase in the optical basicity due to the increased polarizability of the glass matrix, but also with increasing CeO2 concentration as a result of Ce3+/Ce4+ inter valence charge transfer (IV-CT) absorption. The optical band gap for direct and indirect allowed transitions was calculated for the undoped glasses. The glass sample containing Mg2+ modifier ions is found to have the highest value (4.16 eV) for the optical band gap while Ba2+ has the lowest value (3.61 eV). The change in the optical band gap arises from the structural changes and the overall polarizability (optical basicity). Refractive index, molar refractivity Rm and molar polarizability αm values increase with increasing optical basicity of the glasses. The characteristic absorption peaks of Sm3+ were also investigated. For Sm/Ce co-doped glasses, especially at high concentration of CeO2, the absorption of Ce3+ hinders the high energy absorption of Sm3+ and this effect becomes more obvious with increasing optical basicity.

The effect of alkaline earth ions on the structure and properties of borate glasses near the metaborate composition was studied for two glass series, 30MO-10Li2O-10Al2O3-50B2O3 with M=Mg, Ca, Sr or Ba and xMgO-(30-x)BaO-10Li2O-10Al2O3-50B2O3 series, for undoped and doped (0.5 mol% MnO or CuO) glasses. Thermal and optical properties, including the optical basicity, were correlated with structural variations. IR and Raman spectra showed the highest N4 fraction for the high basicity glasses, decreasing for higher field strength ions (Ba>Sr>Ca>Mg). As determined from far IR bands the mixing of dissimilar cations affects M-O interactions. The glass transition temperature Tg correlates well to the average bond strength of the compared alkaline earth ions. The redox ratio of Mn2+/Mn3+ or Cu2+/Cu+ shifted to lower valences in low basicity glasses. The optical basicity probe ion Mn2+ gives consistently higher values compared to the average optical basicity, suggesting that Mn2+ ions seek out high basicity ligands.

Fluoride–phosphate (FP) glasses have been developed (in terms of glass forming ability) as a more stable alternative to fluoride glasses. Benefitting from the low polarizability of the fluoride anion, high electronic band-gap and low phonon energy, they present one of the most important host species for the inclusion of rare-earth and other optically active dopants into fiber and bulk glass. A major limitation, however, has been the mechanical performance of these glasses and their susceptibility to damage and fracture. Here, we provide comprehensive data on elasticity, plasticity and fracture of a series of mixed fluoride–phosphate glasses with strongly ionic bonding character, spanning the compositional join of strontium metaphosphate and alkaline earth aluminum fluoride. Simplistic models such as that of Makishima and Mackenzie can reproduce the mechanical properties of these glasses within a limited compositional range. This break-down is explained in the context of glass structure, in particular, the role of intermediate VIAl3 + species which act as bridges between the fluoride and the phosphate sub-networks. A simple binominal model is implemented to estimate the atomic fractions of aluminum as well as of magnesium cations, which are linked to two or more phosphate units, and used as an indicator for the connectivity between the anion sub-networks. Such adjustment of the Makishima–Mackenzie model provides an unambiguous rational for the elastic properties, but also for the susceptibility to inelastic deformation and fracture of FP glasses.

Plastic deformation, densification, and cracking of sodium borosilicate (NBS) glasses were examined during indentation with a three-sided pyramidal indenter. Compositions of 74.0SiO 2 –10.0B 2 O 3 –16.0Na 2 O (NBS1), and 74.0SiO 2 –20.7B 2 O 3 –4.3Na 2 O–1.0Al 2 O 3 (NBS2) (mol%) were investigated. The effect of thermal history was additionally considered for the NBS2 composition, which lies near the boron anomaly line. Hardness, elastic modulus, and fracture toughness were estimated with instrumented indentation techniques. Atomic force microscopy (AFM), Raman micro-spectroscopy, and post-indent annealing experiments were used to analyze surface topographies, densification, and recovery of deformed material. The results indicate that NBS1 exhibits a greater hardness and elastic modulus, and undergoes less densification than the NBS2 glasses. Different casting conditions influenced the plastic deformation and onset of crack initiation in NBS2. Interpretation of fracture toughness measured by indentation is complicated by residual stresses, densification during contact, and model assumptions. However, distinct differences in elastic modulus, plastic deformation and cracking between the glasses were noticeable. Such results and observations are discussed in terms of structural changes in the glass.

We report on the deformation behavior of a series of glasses in the ternary alkali-borosilicate system. Vickers indentation was applied to different samples and structural changes were studied by micro-Raman spectroscopy. Selected sodium- and potassium-borosilicate glasses, a soda-lime silicate glass and pure vitreous SiO 2 were chosen as models for technical glasses, as their varying content of non-bridging oxygen atoms affects the connectivity of the silicate and borate sub-networks. Indentation experiments were performed with different loads and two different load times in order to analyze the response of the two sub-networks in the studied glasses. The measured Raman spectra show distinct indentation-induced changes in the glass structure. These changes depend not only on the borate concentration, but also on the silicate sub-network's connectivity and reflect anomalous (densification-driven) and normal (shear-driven) deformation mechanisms. Using vitreous SiO 2 as reference material, indentation-induced structural changes were also correlated to hydrostatic compression experiments from the literature in order to develop a more detailed picture of the apparent evolution of the local compaction in and around the indent.

We report on the effect of micro-indentation on the local structure of glasses in the ternary borosilicate glass system Na2O–B2O3–SiO2. Indentation experiments were performed with loads ranging from 0.49 to 4.91 N and for loading times of 10–30 s in order to analyze the impact on the silicate and borate sub-networks in glasses ranging from pure SiO2 to binary Na2O–4B2O3, with a ratio of R = Na2O/B2O3

A collection of Roman glass samples from Ancient Messene, Greece, was analysed non-destructively for colouring elements and non-colouring additives such as fining agents, opacifiers and decolourizers, by comparing the chemical composition with the observed optical spectra. The resulting information on ion speciation is important for the discussion of technological parameters such as the applied melting temperatures or the prevalent redox conditions. Speciation also helps to distinguish intentionally added dopants from impurities. This knowledge might be used in provenancing the raw materials. The Roman assemblage under study included purple coloured Mn 3+ -containing glasses, but also samples with high levels of colourless Mn 2+ . Manganese ions can either be considered a residue of recycling, or are indicative of an intentional addition, either as a fining or as a decolouring agent. Antimony oxide was either added as a fining agent, resulting in good quality transparent glasses, or as crystalline antimonates which act in glass mosaic tesserae as opacifiers. The much weaker molar extinction coefficient and the partial reduction of blue Cu 2+ to colourless Cu + explain why CuO is a weaker colouring agent than CoO. The colours of iron-bearing glasses range from light blue to green and from yellow to dark brown, reflecting a complex interplay between redox conditions and the presence of sulphur in the glass melt. Quantitative speciation of dopants will be reviewed on the basis of the ligand field theory. The different transition probabilities will be demonstrated on differently doped soda lime silicate glasses which were prepared for this purpose in the laboratory.

X-ray-induced defects in undoped and Ag-doped sulfophosphate glasses were studied by optical and electron paramagnetic resonance (EPR) spectroscopy. Besides intrinsic phosphate-related positively charged hole centers (HC) and negatively charged electron centers (EC), also oxygen hole centers (OHC), sulfate-related electron centers (SEC) and zinc centers (Zn*-HC) were identified. The formation of three different Ag-related defects was evident in the Ag+-doped glasses: (Ag+)− and (Ag+)2−-EC, as well as (Ag+)+-HC. Undoped glasses recover at room temperature within two weeks. In contrast, other defects are stabilized when Ag+ is present in the glasses, as some intrinsic defects transform over time at room temperature into more stable Ag-related defects.

Be-Na-(Li)-Si oxide glasses containing up to 15 mol% of BeO were prepared. Their structure was characterized by X-ray powder diffraction and Raman as well as infrared spectroscopic techniques, while their chemical compositions were examined by Inductively Coupled Plasma Optical Emission Spectrometry. All materials were found to be amorphous and contain Al contaminations from minor dissolution of the alumina crucibles. The results of Raman and IR spectroscopies showed that BeO addition to Na-(Li)-Si glass systems resulted in the formation of [BeO4/2]2− tetrahedra which are inserted into the silicate glass network, demonstrating the intermediate glass-forming role of BeO. In parallel, the effective destruction of Si-O-Si bridges was observed by vibrational spectroscopy. The glass transition temperature was studied by Differential Thermal Analysis and found to range from about 431 °C to 551 °C. A significant increase in Tg by 70 °C was found as SiO2 was substituted by up to 15 mol% BeO.

Two oxynitride glass series with the composition of 35Na2O-5BeO-(60-x)SiO2-xSi3N4 and 9Li2O- 27Na2O-5BeO-(59-x)SiO2-xSi3N4, were prepared. The glasses' topography and structure were studied by Scanning Electron Microscopy and Raman spectroscopy. The composition was analyzed by Inductively Coupled Plasma Optical Emission Spectrometer, SEM-EDS and nitrogen and oxygen elemental analyzer. Na-(Li)-Be-silicate glasses were found to contain up to approximately 3.4 (or 5.2 for EDS measurements) at.% of N, respectively. The samples were homogenous in their topography and composition s of their cross-sections. The presence of three-fold coordinated nitrogen atoms in Na-Be-Si-O-N glasses results in higher degree of polymerization as was observed by Raman spectroscopy. The spectrum of analogous glasses with lithium did not show a significant decrease in Q2 units but exhibit the presence of Q4 units which also indicates a polymerization of the network. The incorporation of nitrogen in these glasses leads to the increase of the glass transition temperature and thermal stability.

We report on photoluminescence down-shifting and near-IR emission from Nd 3 + centers in 50P 2 O 5 –(50- x )SrO– x MnO metaphosphate glasses. In those glasses, manganese exists predominantly in its divalent state with a Mn 3 + fraction of less than 0.1 % of total Mn. The Mn 2 + ions are octahedrally coordinated so that a broad red emission band is observed after blue excitation. The emission peak red-shifts from 680 to 743 nm, the lifetime decreases from 14.5 to 1.7 ms and the internal quantum efficiency decreases from 36.5% to 2.5% with increasing Mn 2 + concentration due to concentration quenching, but luminescence activity can still be observed in the pure manganese metaphosphate. The absorption bands of Mn 2 + cover the broad region from 300 to 550 nm, which allows for the sensitization of Nd 3 + . Energy transfer from Mn 2 + to Nd 3 + occurs through a multi-phonon assisted non-radiative down-shifting energy transfer process. A decrease of the emission intensity and lifetime for VI Mn 2 + is observed after doping with Nd 3 + giving evidence for the energy transfer. A value of 89% is estimated for the maximum energy transfer efficiency.

Highly modified borate glasses with the composition (1 − 2x)MnO–x(SrO–B2O3) (x = 0.46, 0.42, 0.36, 0.25, and 0.20) were prepared and investigated by Raman, infrared (IR), and electron paramagnetic resonance (EPR) spectroscopy. Optical properties were studied in regard to photoluminescence, optical absorption, and refractive index. The Mn2 +/Mn3 + equilibrium was shifted towards the divalent manganese ion as a result of the strongly reducing melting conditions employed in this work, which facilitate the preparation of transparent glasses with up to 80 mol% total SrO and MnO content. Changes in the optical and physical properties within this glass series were related to structural variations. The structure of glasses with relatively low MnO content was found to involve mainly trigonal [BO2O]− and tetrahedral [BO4]− metaborate groups, which are replaced progressively by pyroborate [B2O5]4 − and orthoborate [BO3]3 − triangular units upon increasing MnO content. At the highest modification level (x = 0.20) the structure is built of orthoborate isomeric species in triangular [BO3]3 − and tetrahedral [BO2O2]3 − configuration. The latter species form [B3O9]9 − rings, which reestablish some degree of network connectivity, as they involve three bridging and six non-bridging oxygen atoms, and this is reflected by the increase of the glass transition temperature for x = 0.25 over x = 0.20. Micro-Raman measurements showed structural inhomogeneities in these glasses due to chemical isomerization processes involving short- and medium-range order structures. Also, increasing MnO content was shown to cause MnO-clustering in the glasses as revealed by luminescence and EPR measurements.

Controlled collapse of a silicoaluminophosphate molecular sieve CHA-type SAPO-34 by thermal aging was studied in a multi-method approach. Structural changes and the mechanism of order–disorder–order transitions during collapse were followed for varying annealing conditions between 1000 and 1100 °C. Collapse of SAPO-34 occurs via the formation of an intermediate amorphous state by the loss of long-range order but preservation to a high degree of short-range order and macroscopic morphology. This intermediate amorphous state with low entropy may be classified as a “perfect glass”. Prolonged aging in the collapse regime results in the precipitation of crystalline AlPO 4 while the SiO 2 species initially remain in an amorphous phase. Further increasing the aging temperature leads to virtually complete recrystallization and, ultimately, melting.

Electron paramagnetic resonance (EPR) and fluorescence spectroscopy are sensitive and selective methods for probing coordination and bonding of Mn2+ ions in glasses. Both methods provide additional information on Mn–Mn ion interactions and cluster formation. Mn2+ was found to be tetrahedrally coordinated in boro-silicate glasses of high optical basicity, and octahedrally coordinated in low alkaline boro-silicate glasses (duran-type) as in fluoride-phosphate glasses. Broad emission bands and multicomponent fluorescence decay curves in duran glasses indicate very strong Mn–Mn ion interactions and the presence of multiple Mn2+ sites. Site distribution is more homogenous in metaphosphate glasses, though concentration quenching is apparent at high Mn-levels. As the Mn-content increases the EPR spectra show exchange narrowing due to a decrease in the Mn–Mn distances in the duran series, but show extreme linewidth broadening due to increased cluster sizes at constant Mn–Mn distances for metaphosphate glasses. For the fluoride-phosphate and boro-silicate systems investigated, fluorescence lifetimes are found to decrease as the wavelength of the emission maximum increases and with increasing g-values of the sextet at g = 2. For octahedral coordination of Mn2+ ions the EPR hyperfine splitting constant decreases linearly with increasing optical basicity, as a result of an increasing covalent character of the Mn2+–ligand bond.

Corona poling of two different methacrylate-type co-polymers with the chromophore Disperse Red 1 methacrylate (MDR1) results in the orientation of molecular dipoles and gives a nonlinear optical response in the form of second harmonic generation (SHG). The intensity of the SHG signal was used to measure the effectiveness of poling-induced alignments, which depend also on fundamental order phenomena in the co-polymers. The two matrix polymers varied in length and polarity of their side chains, which affect strongly side chain tacticity and chromophore aggregation. In situ SHG measurements during and after poling showed that the relaxation rate in methacrylic acid (MAA) co-polymers could be lowered by heat-induced cross-linking of the polymer chains. Order parameters derived from SHG measurements were found to be greater than 4, even when no changes were recorded in the optical spectra after poling. When changes were observed in the optical spectra, it was found that these were due to a decrease in the molar extinction coefficient for hydroxy-propyl-methacrylate (HPMA) based co-polymers, and solely due to the poling-induced decrease in film thickness in methacrylic acid based co-polymers (MAA).

The effectiveness of chromophore alignment in polymer films following corona poling can be assessed by the generated second harmonic signal. Optimization of the stability and strength of this nonlinear optical response may improve with a better understanding of the underlying principal order phenomena. Structural analysis by vibrational, optical, and 1H NMR spectroscopy reveals side chain tacticity, aggregation effects, and changes in orientation as a function of temperature. Co-polymers with the functionalized chromophore Disperse Red 1 methacrylate (MDR1) were prepared for three different methacrylate types. High side chain polarity and short side chain length increase generally chromophore aggregation in films, whereas the very long poly-ether side chains in PMEO based co-polymers are wrapped separately around the DR1 entities. Side chain tacticity depends on space requirements, but also on the capacity of side groups to form OH-bridges. Side chain tacticity might present an additional parameter for the assessment of chromophore aggregation and poling induced alignments. Stepwise heating of co-polymer films causes an increase in the number of random over ordered side chain arrangements. Cross-linking by anhydride formation is observed after heating the methacrylic acid based co-polymer.

(Fluoride)phosphate and borosilicate glasses of high intrinsic transparency in the deep ultraviolet (UV), were doped with 50–5000 ppm of the 4d- and 5d-ions Zr, Nb, Ta, Mo, or W. All of these ions absorb strongly in the UV. Samples plates were irradiated by UV lasers and the as a consequence generated various extrinsic and intrinsic defects were characterized by optical and EPR spectroscopy. The laser induced transmission changes depend not only on the glass matrix, but also on the valence of the dopants. Only fully oxidized d0-ions are observed in fluoroaluminate glasses. Laser irradiation photoreduces the d0-ions to extrinsic electron-centers (EC). Laser induced transmission changes extend from the UV up to 600 nm in the visible. The dopants are easily reduced to lower valences in metaphosphate glasses. Extrinsic hole centers (HC) replace intrinsic HC in samples containing the reduced transition metal ions. The strong transmission changes seen below 300 nm arise from intrinsic EC and extrinsic HC. The few remaining intrinsic HC (300–600 nm) recombine rapidly with EC or transform into more stable extrinsic HC. Borosilicate glasses show the formation of intrinsic boron oxygen hole center in the EPR spectra and of intrinsic HC and EC in the optical spectra. The d1-ion Mo5+ is the only identified reduced dopant species in the borosilicate glasses. The band intensity of intrinsic EC in relation to intrinsic HC is correspondingly highest for the Mo-doped samples, in which extrinsic HC are generated.

The extent of solarization is strongly influenced by many factors such as glass matrix, dopants, or irradiation source. Typical irradiation induced effects are illustrated in a series of glasses doped with a selection of polyvalent ions. Intrinsic and extrinsic defects, consisting of electron and hole centers, are characterized with optical and EPR spectroscopy. Used in combination, both spectroscopic methods allow to detect a wide range of defects. UV-lamp irradiation causes in fluoride-phosphate glasses the photoreduction of Ni 2þ ,P b 2þ and Ag þ while Co 2þ ,C e 3þ ,F e 2þ and Mn 2þ are photooxidized. The influence of the glass matrix is evident for Ni 2þ which is photooxidized in borosilicate, but reduced in fluoride-phosphate glasses. Iron ions also show different redox reactions depending on the glass matrix, as well as on the melting conditions, which will be shown for low alkaline borosilicate glasses doped with iron or tin. Changes in the nature and the rate of defect formation could be observed within the irradiation process of a fluoride-phosphate glass co-doped with Mn 2þ and Fe 2þ and during thermal annealing of a lamp irradiated phosphate glass containing Co 2þ . The series Mn 2þ ,F e 2þ ,C o 2þ and Ni 2þ shows a trend of increased photooxidation with increasing electro-negativity or