Energetic Effects of Substitution of La–Nd and Si–Ge Oxyapatite‐Type Materials

A series of lanthanide oxyapatites, neodymium silicates (Nd_9.33?xM_3x/2(SiO₄)₆O₂; x = 0.0 and 2.0 and M = Ca, Sr, and Ba), and lanthanum germanate (La₁₀(GeO₄)₆O₃) were prepared by a variety of heat treatments and characterized. High‐temperature oxide melt solution calorimetry in molten 2PbO–B₂O₃ solvent at 1078 K was performed to determine their enthalpies of formation from constituent oxides at room temperature. The energetics of these materials is discussed in terms of the effects of doping on two crystallographic sites, the lanthanide and tetrahedral sites. The enthalpy of formation from oxides becomes less exothermic by substituting La with Nd throughout the whole series, in both doped and undoped compositions, reflecting the smaller radius and lower basicity of Nd compared with La. Cation stoichiometric lanthanum germanate apatite (La₁₀(GeO₄)₆O₃) shows a more endothermic enthalpy of formation than the corresponding silicate, reflecting the larger radius and lower acidity of Ge than Si.     

Structural Investigations on the Compositional Anomalies in Lanthanum Zirconate System Synthesized by Coprecipitation Method

The study set out to investigate the compositional inconsistency in lanthanum zirconate system revealed the presence of nonstoichiometry in lanthanum zirconate powders when synthesized by coprecipitation route. X‐ray diffraction (XRD) and high‐resolution transmission electron microscopy (HRTEM) investigations confirmed the depletion of La³⁺ ions in the system. Analysis using Vegard's law showed the La/Zr mole ratio in the sample to be around 0.45. An extra step of ultrasonication, introduced during the washing stage followed by the coprecipitation reaction, ensured the formation of stoichiometric La₂Zr₂O₇. Noteworthy is also the difference between crystal sizes in the samples prepared by with and without ultrasonication step. This difference has been explained in light of the formation of individual nuclei and their scope of growth within the precipitate core. The differential scanning calorimetry (DSC) analyses revealed that optimum pH for the synthesis of La₂Zr₂O₇ is about 11. The ultrasonication step was pivotal in assuring consistency in mixing and composition for the lanthanum zirconate powders.     

Effects of La content on the densification,microstructure, and conductivity of doped La10−xGe6O26±δ electrolytes

In this study, the influence of La content on the characteristics of Nb‐, Mo‐, and W‐doped La_xGe₆O_26±δ electrolytes was investigated through sintering study, X‐ray diffraction, scanning electron microscopy, and conductivity measurement. The densification of La_xGe_5.5Nb_0.5O_26±δ and La_xGe_5.5W_0.5O_26±δ was retarded as the x reached 9.75, while that of La_xGe_5.5Mo_0.5O_26±δ improved with increasing La content. The average grain size slightly increased and weight loss due to evaporation of GeO₂ significantly reduced with increasing La content, ranging from 1.39% to 0.26%. Among the systems studied, La_9.33Ge_5.5Nb_0.5O_26.245, La_9.33Ge_5.5Mo_0.5O_26.045, and La_9.50Ge_5.5W_0.5O_26.75 electrolytes revealed great potential for use in SOFC applications.     

Raman and X‐ray Studies of Uranium–Lanthanum‐Mixed Oxides Before and After Air Oxidation

UO₂ samples doped with 6, 11, 22 mol% lanthanum were examined before and after air oxidation. To verify the formation of uranium–lanthanum‐mixed oxide solid solutions, powder X‐ray diffraction (XRD) analyses of the crystalline phases in the materials were carried out. The presence of oxygen vacancies in the La‐doped UO₂ samples was identified by Raman spectrometry. It was evidenced by changes induced in the Raman spectra by air oxidation. This latter was carried out either by increasing the Raman laser power or by thermally treating the samples at 500 K for 370 h. In addition, oxidation behavior differences of pure and La‐doped UO₂ samples were reported by comparing XRD and Raman results of the samples before and after air oxidation. It was shown that the concentration of the M₄O₉ (M: U, La) phase increased with increasing content of La, whereas inhibition for the formation of M₃O₈ phase was observed.     

On the influence of silica type on the structural integrity of dense La9.33Si2Ge4O26 electrolytes for SOFCs

Apatite-type rare earth based oxides, such as R-doped lanthanum oxides of general formula La_9.33(RO₄)₆O₂ with R = Ge, Si, exhibit high ionic conductivity and low activation energy at moderate temperatures, when compared to the yttria-stabilized zirconia electrolyte making them potential materials to be used in the range 500–700 °C, for intermediate temperature solid oxide fuel cells (IT-SOFCs). In this study, dense oxyapatite-based La_9.33Si₂Ge₄O₂₆ electrolytes have been successfully prepared either by electrical sintering at 1400 °C or microwave hybrid sintering at 1350 °C for 1 h from La₂O₃, SiO₂ and GeO₂ powders dry milled at 350 rpm for 15 h in a planetary ball mill. The densification behaviour of the apatite-type phase synthesized by mechanical alloying was found to be dependent on the grade of SiO₂ used: either pre-milled quartz powder or amorphous nanosized fumed silica. The influence of the silica type on the La_9.33Si₂Ge₄O₂₆ integrity was assessed by dynamic Young's modulus, microhardness and indentation fracture toughness measurements. A good correlation between the degree of densification (as observed by SEM/EDS) and the resulting mechanical properties could be established. Pre-milling of quartz powder has favoured higher densification rates to be attained suggesting that both Fe content, resulting from the dry milling (as determined by PIXE analyses) and crystallinity of SiO₂ do promote densification of these electrolytes thereby improving their structural integrity.     

Metal-organic chemical vapour deposition of lanthana-doped ceria layers at low temperatures

Non-porous, amorphous and nanocrystalline CeO₂–La₂O₃ layers were synthesized by means of MOCVD using Ce(tmhd)₄ and La(tmhd)₃ as reactants on tubular and planar quartz glass substrates. Different layers were synthesized in the temperature range 500–700 °C using various molar contents of La(tmhd)₃, i.e. 10, 15, 26 and 50%, respectively. A mixture of Ar and air was used as a carrier gas. Air was also an oxygen source necessary for carbon oxidation (a solid by-product of reactant pyrolysis). Therefore, the layers should only contain Ce⁴⁺ ions. When the synthesis process was controlled by the surface reaction rate, there was no correlation between the chemical composition of reactants and that of the layers. Such a dependence was obtained when the synthesis process was controlled by mass diffusion to the substrate. In addition, it was observed that La³⁺ ion segregation can occur during layer synthesis between surface areas with lower and higher amounts of a crystalline phase. The molar percent of La₂O₃ in areas exhibiting less crystallization with smaller grains was higher than in locations with larger grains, because, in this case, intergranular boundary content was lower. X-ray analysis indicates that layers deposited at 500 °C were amorphous, although SEM images show numerous small nuclei of a crystalline phase. It seems that the crystalline phase content was not high enough to be identified by X-ray analysis. Layers deposited at 600 °C consisted of a solid solution of La₂O₃ dissolved in CeO₂. From UV-VIS tests it follows that absorption is very strong up to a wavelength of approximately 320 nm.     

Structural impact of nitrogen incorporation on properties of alkali germanophosphate glasses

The structure, atomic packing density, calorimetric glass transition, and hardness of mixed sodium–lithium germanophosphate oxynitride glasses with varying Ge/P and N/P ratios were investigated. The combined influences of nitridation and mixed network former effect (MNFE) on the glass structure were analyzed using Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and ³¹P nuclear magnetic resonance (NMR) spectroscopy. Evidence for the existence of germanium in a higher coordination state, i.e., five‐ or sixfold coordination, was obtained by performing XPS analysis of the oxide glasses, with indication of conversion to tetrahedral coordination upon nitridation. Raman spectroscopy measurements implied that the germanate network was modified upon nitridation, including the removal of ring‐like germanate structures and P–O–Ge mixed linkages. The partial anionic N‐for‐O substitution gave rise to the linear dependence of the glass transition temperature (T_g) and hardness (H_V) on nitrogen content (expressed as N/P ratio), especially for lower Ge/P ratio. However, nitridation also caused an unexpected increase in liquid fragility and decrease in density. This suggests that the governing structural parameter for property evolution in such LiNaGePON glasses is not only the increased degree of cross‐linking of the phosphate chains, but rather the short‐ and intermediate‐range structural modifications within the germanate component of the oxynitride glasses.     

High Na‐ion conducting Na1+x[SnxGe2−x(PO4)3] glass‐ceramic electrolytes: Structural and electrochemical impedance studies

Na‐ion conducting Na_1+x[Sn_xGe_2?x(PO₄)₃] (x = 0, 0.25, 0.5, and 0.75 mol%) glass samples with NASICON‐type phase were synthesized by the melt quenching method and glass‐ceramics were formed by heat treating the precursor glasses at their crystallization temperatures. XRD traces exhibit formation of most stable crystalline phase NaGe₂(PO₄)₃ (ICSD‐164019) with trigonal structure. Structural illustration of sodium germanium phosphate [NaGe₂(PO₄)₃] displays that each germanium is surrounded by 6 oxygen atom showing octahedral symmetry (GeO₆) and phosphorous with 4 oxygen atoms showing tetrahedral symmetry (PO₄). The highest bulk Na⁺ ion conductivities and lowest activation energy for conduction were achieved to be 8.39 × 10^?05 S/cm and 0.52 eV for the optimum substitution levels (x = 0.5 mol%, Na_1.5[Sn_0.5Ge_1.5(PO₄)₃]) of tetrahedral Ge⁴⁺ ions by Sn⁴⁺ on Na–Ge–P network. CV studies of the best conducting Na_1.5[Sn_0.5Ge_1.5(PO₄)₃] glass‐ceramic electrolyte possesses a wide electrochemical window of 6 V. The structural and EIS studies of these glass‐ceramic electrolyte samples were monitored in light of the substitution of Ge by its larger homologue Sn.     

Effect of La2O3 on the oxidation resistance of SiC ceramic at 1973 K: Experimental and theoretical study

The effect of La₂O₃ on the oxidation resistance of SiC ceramic at 1973 K was investigated using isothermal oxidation test and first-principles calculations. The SiC ceramic with La₂O₃ shows a better oxidation resistance compared with that without La₂O₃ due to the in situ formed La₂Si₂O₇ in SiO₂ glass layer after oxidation at 1973 K. First-principles calculations based on density functional theory were applied to analyze the solution behaviors of La atom in the surface of SiO₂ and La₂Si₂O₇. The solution energy of La atom in SiO₂ (0 1 1) is −19.05 eV, which is far less than −4.19 eV in La₂Si₂O₇ (2 0 1) with a La vacancy, thus resulting in that La atom in La₂Si₂O₇ (2 0 1) diffuses into SiO₂ (0 1 1). The SiO₂ lattice with an interstitial La atom is more stable than that with a substitutional La atom and the interstitial La breaks the nearest Si–O bond to form La–O and La–Si bonds, which is beneficial to improving the high-temperature stability of SiO₂. Experimental and theoretical results indicate that the formation of refractory La₂Si₂O₇ phase enhances the stability of SiO₂ glass layer, so as to protect SiC ceramic from further oxidation at 1973 K.     

Sr2−XLaXMgMoO6 and Sr2−XLaXMgNbO6 for Use as Sulfur‐Tolerant Anodes Without a Buffer Layer

The objective of this effort is to synthesize and characterize a series of lanthanum‐(La) doped Sr₂MgMoO₆ (SMMO) and La‐doped Sr₂MgNbO₆ (SMNO) anode materials which can be used in combination with lanthanum‐containing electrolytes to mitigate the effects of lanthanum poisoning in solid oxide fuel cells (SOFCs). Currently, an La_0.4Ce_0.6O_1.8 (LDC) buffer layer is used with many perovskite‐based anode materials to prevent La diffusion into the anode from the La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8 (LSGM) electrolyte which can create a resistive La species that impedes electrochemical performance. The LDC buffer layer, with diminished electronic conductivity, adds an extra level of complexity in the SOFC manufacturing process. Further, this extraneous layer presents an added experimental challenge when assessing anode material performance. Overall electrochemical performance could be improved if the resistive buffer layer could be removed, thereby allowing the anode material to have direct contact with the electrolyte. To accomplish this, a new class of anode materials was synthesized with the goal of balancing “La” chemical potential between these neighboring materials. La‐doped SMMO and SMNO were prepared and studied. It was hypothesized that by incorporating La into the anode, the gradient of chemical activity between the anode and electrolyte would decrease, which would prevent La diffusion. These anode materials were synthesized via a sol–gel methodology and characterized with X‐ray diffraction to assess phase purity. The conductivity of the materials was analyzed in the presence of both H₂ and 100 ppm H₂S/H₂ to determine the stability and performance of these materials during device operation. The stability experiments demonstrated that 40% La‐doped SMNO is stable in all pertinent environments while not reacting with the LSGM electrolyte.     

Effect of pH on the production of dispersed Bi4Ge3O12 nanoparticles by combustion synthesis

This paper reports the production of bismuth germanate ceramic scintillator (Bi₄Ge₃O₁₂) by combustion synthesis (SHS) method, focusing on the influence of the synthesis parameters on the crystalline phases and agglomeration of the nanoparticles. The synthesis and sintering conditions were investigated through thermal analysis, X-ray diffraction as function of temperature, dilatometry and scanning electron microscopy. Well-dispersed Bi₄Ge₃O₁₂ powder was accomplished by the combustion of the initial solution at pH 9, followed by low temperature calcination and milling. Sintered ceramics presented relative density of 98% and single crystalline Bi₄Ge₃O₁₂ phase. The luminescent properties of the ceramics were investigated by photo- and radio-luminescence measurements and reproduced the typical Bi₄Ge₃O₁₂ single-crystal spectra when excited with UV, β and X-rays. The sintered ceramics presented light output of 4.4 × 10³ photons/MeV.     

Nanocrystalline Rare Earth Phosphates from Glass Dissolution and Precipitation Reactions

A novel method is employed for the formation of rare earth phosphate solid solution compounds with unique mesoscopic structures. Europium‐ and lanthanum‐doped sodium borate glass microspheres and particles, ranging in sizes from 50 to 300 μm, were reacted in 0.25 M K₂HPO₄ solution to form hollow spheres of nanocrystalline rare earth phosphate compounds by dissolution–precipitation reactions. The initially X‐ray amorphous precipitated rare earth phosphate materials were heat‐treated at 700°C for 2 h to form nanocrystalline compounds. Differential thermal analysis (DTA) experiments yield an average activation energy for crystallization of 394 ± 26 kJ/mol. X‐ray diffraction (XRD) data indicate that samples crystallized to the monazite structure (monoclinic P2₁/n) with unit cell volumes ranging from 306.5 Å³ for LaPO₄ to 282.5 Å³ for EuPO₄ and with crystallite grain sizes of 56 ± 14 nm. Compositions containing both rare earth elements formed solid solutions with the composition La_(1?x)Eu_xPO₄. Raman spectroscopy indicates that the P–O symmetric stretching vibrations (ν₁) change systematically from 963 cm^?1 for LaPO₄ to 986 cm^?1 for EuPO₄, consistent with a systematic decrease in average P–O bond length. Photoluminescence measurements show maximum emission intensity for the La_0.65Eu_0.35PO₄ composition.     

Preparation and corrosion resistance of nonstoichiometric lanthanum zirconate coatings

Lanthanum zirconate is a promising thermal barrier coating material owing to its excellent thermophysical properties and La plays the key role in its corrosion resistance. Here, an amorphous precursor is used as raw feedstock material so as to synthesize lanthanum zirconate coatings with tailorable composition by atmospheric plasma spray (APS). Three lanthanum zirconate coatings of La_1.7Zr_2.3O_7.15, La_2.0Zr_2.0O_7.0 and La_2.3Zr_1.7O_6.85 are fabricated. Furthermore, the corrosion resistance of the as-sprayed coatings against CaO-MgO-Al₂O₃-SiO₂ at 1250℃ is investigated. The increased La content promotes the formation of a sealing layer of the crystalline Ca₂La₈(SiO₄)₆O₂ apatite, which slows down the penetration of molten CaO-MgO-Al₂O₃-SiO₂. Therefore, the infiltration rate of the La_2.3Zr_1.7O_6.85 coating decreased up to 42.6 % compared with the other two coatings. This work develops a feasible preparation strategy to control the La composition for the improved corrosion resistance, which is expected to guide the future coating design and synthesis for the materials with big composition changes during the APS process.     

The Effect of La2O3 Addition on Sol–Gel Derived Mullitization

Monophasic gel with stoichiometric 3Al₂O₃·2SiO₂ composition and gels with 0.99, 1.96, and 2.91 mol% La₂O₃ added were sol–gel derived. The crystallization path, structure evolution, microstructure, and morphology of calcined premullite powders and sintered ceramic bodies have been investigated as a function of La₂O₃ content and sintering temperature. In addition to mullite, spinel phase at about 980°C, and α‐alumina at above 1000°C were determined; however, neither La₂O₃ nor La‐related compounds had crystallized. The La₂O₃ predominately incorporated into the glassy phase, enhanced with La₂O₃ level, which affected both mullite structure and composition, as confirmed by electron microscopy, Rietveld structure refinement, determination of unit cell parameters, electron microscopy, and achieved density of the sintered bodies. Increased thermal treatment changes the alumina/silica ratio in mullite (towards 3:2 below 1200°C, and toward 2:1 above), and decreases the mullite/amorphous ratio. Sintered dense ceramic bodies revealed a positive densification effect and increased sinterability as a result of the lanthanum‐induced increase in glassy phase.     

First Identification of Rare‐Earth Oxide Nucleation in Chalcogenide Glasses and Implications for Fabrication of Mid‐Infrared Active Fibers

Gallium (Ga) helps solubilize rare‐earth ions in chalcogenide glasses, but has been found to form the dominant crystallizing selenide phase in bulk glass in our previous work. Here, the crystallization behavior is compared of as‐annealed 0–3000 ppmw Dy³⁺‐doped Ge–As–Ga–Se glasses with different Ga levels: Ge_16.5As_(19?x)Ga_xSe_64.5 (at.%), for x = 3 and 10, named Ga₃ and Ga₁₀ glass series, respectively. X‐ray diffraction and high‐resolution transmission electron microscopy are employed to examine crystals in the bulk of the as‐prepared glasses, and the crystalline phase is proved to be the same: Ge‐modified, face centered cubic α‐Ga₂Se₃. Light scattering of polished glass samples is monitored using Fourier transform spectroscopy. When Ga is decreased from 10 to 3 at.%, the bulk crystallization is dramatically reduced and the optical scattering loss decreases. Surface defects, with a rough topology observed for both series of as‐prepared chalcogenide glasses, are demonstrated to comprise Dy, Si, and [O]. For the first time, evidence for the proposed nucleation agent Dy₂O₃ is found inside the bulk of as‐prepared glass. This is an important result because rare‐earth ions bound in a high phonon–energy oxide local environment are, as a consequence, inactive mid‐infrared fluorophores because they undergo preferential nonradiative decay of excited states.     

Influence of glass composition on photoluminescence from Ge2+ or Ag nano-cluster in germanate glasses for white light-emitting diodes

Germanium glass has attracted much interest because of its potential application as the optical waveguides and communication devices. In this work, germanium glass was prepared, exhibiting the blue luminescence at the 410 nm from the Ge²⁺. The influence of SiO₂ addition in the germanate glass on the 410 nm luminescence of the Ge²⁺ was observed. The SiO₂ addition promoted the formation of Ge²⁺, which is because the Si⁴⁺ ions can deprive the O²⁻ ions from the Ge⁴⁺ ion caused by the lower optical basicity of Si⁴⁺ ions than Ge⁴⁺ ion. The germanium glasses containing the Ag nano-clusters were prepared using ion-exchange method. The influence of SiO₂ concentration on the size of Ag nano-clusters was observed, which stabilize the size distribution and lead to the miniaturization of Ag nano-clusters. The Ag nano-clusters size dependence of their photoluminescence was observed in germanate glasses, and the tunable photoluminescence of Ag nano-clusters was obtained by controlling the size of Ag nano-clusters. It is noticed that the Ag nano-clusters formed in the germanate glass showed the white light emission characteristic excited at the blue chip, exhibiting the practical application as the blue converted white light-emitting diodes.     

Leakage current and dielectric breakdown in lanthanum doped amorphous aluminum oxide films prepared by sol–gel

Dielectric Al_2−2xLa_2xO₃ (x=0.00, 0.005, 0.02, 0.05, and 0.10) thin films were fabricated on Pt/Ti/SiO₂/Si substrates by sol–gel spin coating. The surface morphology of Al_2−2xLa_2xO₃ thin film was observed by field emission scanning electron microscopy. The chemical state of the lanthanum in aluminum oxide films was analyzed using X-ray photoelectron spectroscopy (XPS), indicating that lanthanum reacts with absorbed water to form lanthanum hydroxide. J–E measurements were used to investigate the current conduction mechanism and breakdown behavior. The results show that La doping changes the conduction mechanism and makes influences on leakage current. The dominating conduction process of 10% La doped Al₂O₃ films turns into the space charge limited current (SCLC) mechanism in the field region ranging from 25 to 150 MV/m. The leakage current of the films with 10% La doping decreases by three orders of magnitude from 10⁻⁶ to 10⁻⁹ at the electric field of 25 MV/m. The breakdown strength increases with the increasing content of lanthanum.     

The influence of concentration on the formation of BaTiO3 by direct reaction of TiCl4 with Ba(OH)2 in aqueous solution

The formation of fine BaTiO₃ particles by reaction between liquid TiCl₄ and Ba(OH)₂ in aqueous solution at 85 °C and pH⩾13 has been studied for 0.062⩽[Ba²⁺]⩽0.51 mol l⁻¹. The concentration of Ba²⁺ ions has a strong influence on reaction kinetics, particle size and crystallite size. When [Ba²⁺]>≈0.12 mol l⁻¹, the precipitate consists of nanosized (≈30 nm) to submicron (100–300 nm) particles of crystalline BaTiO₃. At lower concentrations, the final product is a mixture of crystalline BaTiO₃ and a Ti-rich amorphous phase even for very long reaction times. A two-steps precipitation mechanism is proposed. Initially, a Ti-rich amorphous precipitate is rapidly produced. Reaction between the amorphous phase and the Ba²⁺ ions left in solution then leads to crystallisation of BaTiO₃. In addition to nucleation and growth of nanocrystals, the final size and morphology of BaTiO₃ particles obtained at low concentration can be determined by aggregation of nanocrystals and heterogeneous nucleation on existing crystal surfaces.     

Chemical interactions between 3 mol% yttria-zirconia and Sr-doped lanthanum manganite

The chemical interactions between porous (La_0.8Sr_0.2)MnO₃ (LSM) film and 3 mol% yttria tetragonal zirconia (TZ3Y) substrate have been investigated over the temperature range of 1300–1500 °C in air. Two distinct reaction layers of fluorite-type cubic zirconia solid solution c-(Zr,Mn,La,Y)O₂ and lanthanum zirconate pyrochlore (La,Sr)₂(Zr,Y)₂O₇ were observed at the interface of LSM/TZ3Y. It has been found that the diffusion/dissolution of Mn ions in TZ3Y leads to the formation of the fluorite-type cubic zirconia solid solution, while the interaction of lanthanum with TZ3Y results in the formation of the lanthanum zirconate pyrochlore phase. Phase studies in the (ZrY)O₂–La₂O₃–Mn₃O₄ system show that the fluorite-type cubic zirconia solid solution phase c-(Zr,Mn,La,Y)O₂, rather than the tetragonal 3 mol% Y₂O₃–ZrO₂ phase, is in equilibrium with LSM perovskite at high temperatures. A ternary phase diagram of the system at the (ZrY)O₂-rich end at 1400 °C in air was proposed based on the experimental results. It is suggested that the fundamental reason for the beneficial effect of A-site non-stoichiometry or Mn excess of LSM in the inhibiting of the lanthanum zirconate formation is due to the fact that Mn₃O₄ does not equilibrate with lanthanum zirconate at high temperatures.     

Structural origin of the weak germanate anomaly in lead germanate glass properties

Binary PbO–GeO₂ glasses have been studied in detail from 5 to 75 mol% PbO using high-resolution neutron diffraction, high-energy X-ray diffraction, 207-Pb NMR, pycnometry, and thermal analysis. The Ge–O coordination number displays a broad maximum n_GeO = 4.14(3) close to 27 mol% PbO. This is smaller than the maximum n_GeO = 4.3 reported in CaO–GeO₂ glasses but occurs at a similar composition. This structural behavior appears to explain the relatively weak germanate anomaly manifest in lead germanate glasses, for example as a maximum in the measured atom number density and a plateau in the glass transition temperatures. The structural role of Pb(II) is complex. On the one hand, short covalent Pb–O bonds and small Pb–O coordination numbers of ∼3 to 4 indicate glass network former character for Pb(II), associated with a stereochemically active electron lone pair. On the other hand, the presence of some GeO₅ or GeO₆ units, in addition to the majority GeO₄ tetrahedral species, indicates some modifier character of Pb(II) at low PbO contents, giving rise to the observed weak germanate anomaly, as well as elongation and enhanced ionicity of the Pb–O bonds. Overall, the observed structural behavior of Pb(II) in lead germanate glasses appears as intermediate between that observed in lead silicate and lead borate glasses. Despite rapid quenching, at low PbO contents, the glasses studied exhibited nanoscale heterogeneity, evidenced by small-angle X-ray scattering consistent with the early stages of spinodal decomposition.