Glass Crystallization Research Articles

Effect of Degradation on the Physicochemical and Mechanical Properties of Extruded Films of Poly(lactic acid) and Chitosan.

This study addresses the fabrication of extruded films using poly(lactic acid) (PLA) and chitosan, with and without maleic anhydride as a compatibilizing agent, for potential applications in disposable food packaging. These films underwent controlled conditions of UV irradiation, water condensation, and temperature variations in an accelerated weathering chamber. The investigation analyzed the effect of different exposure periods on the structural, morphological, mechanical, and thermal properties of the films. It was observed that PLA films exhibited a lower susceptibility to degradation compared to those containing chitosan. Specifically, the pure PLA film showed an increase in elastic modulus and strength during the initial 144 h of exposure, associated with cross-linking induced by UV radiation. On the other hand, film Q2 composed of PLA, chitosan, and maleic anhydride and Q1 without maleic anhydride experienced a tensile strength loss of over 50% after 244 h of exposure. The Q2 film exhibited greater homogeneity, leading to increased resistance to degradation compared to that of Q1. As the degradation time increased, both the Q1 and Q2 films demonstrated a decline in thermal stability. These films also exhibited alterations in crystallinity attributed to the chemo-crystallization process, along with fluctuations in the glass transition temperature and crystallization, particularly at 288 h.

The Substitution of Rare-Earth Gd in BaScCuTe3 Realizing the Band Degeneracy and the Point-Defect Scattering toward Enhanced Thermoelectric Performance.

Zintl compounds have continuously received significant attention, primarily due to their structural characteristics that align with the properties of the electron crystal and phonon glass. In this study, the crystal structure and thermoelectric properties of the quaternary Zintl chalcogenide BaScCuTe3 are investigated. The band structure calculations for BaScCuTe3 reveal a slight energy split of 0.08 eV between the second valence band and the valence band maximum, suggesting the presence of multiband-transport behaviors. Substitution of rare earth Gd for Sc is conducted, which significantly increases the hole concentration from 4.1 × 1019 cm-3 to 8.2 × 1019 cm-3 at room temperature. Meanwhile, the Seebeck coefficient increases because of the participation of the second valence band. A maximum power factor of 6.56 μW/cm·K2 at 773 K is obtained, which is 72% higher than that of the pristine sample. Moreover, the lattice thermal conductivity decreases from 0.57 W/m·K for BaScCuTe3 to 0.48 W/m·K for BaSc0.97Gd0.03CuTe3 at 773 K, owing to the introduction of point-defect scattering. As a result, there is a noteworthy improvement in the thermoelectric figure of merit zT, increasing from 0.44 for the undoped sample to 0.85 for BaSc0.98Gd0.02CuTe3. Considering these findings, BaScCuTe3 exhibits great potential and holds promise for further investigation in the field of thermoelectric materials.

Thermal Effects and Glass Crystallization in Composite Matrices for Immobilization of the Rare-Earth Element–Minor Actinide Fraction of High-Level Radioactive Waste

The current policy of managing high-level waste (HLW) derived in the closed nuclear fuel cycle consists in their vitrification into B-Si or Al-P vitreous forms. These compounds have rather limited capacity with respect to the HLW (5–20 wt%), and their properties change over time due to devitrification of the glasses. Cardinal improvement in the management of HLW can be achieved by their separation onto groups of elements with similar properties, followed by their immobilization in robust waste forms (matrices) and emplacement in deep disposal facilities. One of the possible fractions contains trivalent rare-earth elements (REEs) and minor actinides (MAs = Am and Cm). REEs are the fission products of actinides, which are mainly represented by stable isotopes of elements from La to Gd as well as Y. This group also contains small amounts of short-lived radionuclides with half-lives (T1/2) from 284 days (144Ce) to 90 years (151Sm), including 147Pm (T1/2 = 2.6 years), 154Eu (T1/2 = 8.8 years), and 155Eu (T1/2 = 5 years). However, the main long-term environmental hazard of the REE–MA fraction is associated with Am and Cm, with half-lives from 18 years (244Cm) to 8500 years (245Cm), and their daughter products: 237Np (T1/2 = 2.14 × 106 years), 239Pu (T1/2 = 2.41 × 104 years), 240Pu (T1/2 = 6537 years), and 242Pu (T1/2 = 3.76 × 105 years), which should be immobilized into a durable waste form that prevents their release into the environment. Due to the heat generated by decaying radionuclides, the temperature of matrices with an REE–MA fraction will be increased by hundreds of centigrade above ambient. This process can be utilized by selecting a vitreous waste form that will crystallize to form durable crystalline phases with long-lived radionuclides. We estimated the thermal effects in a potential REE–MA glass composite material based on the size of the block, the content of waste, the time of storage before immobilization and after disposal, and showed that it is possible to select the waste loading, size of blocks, and storage time so that the temperature of the matrix during the first decades will reach 500–700 °C, which corresponds to the optimal range of glass crystallization. As a result, a glass–ceramic composite will be produced that contains monazite ((REE,MA)PO4) in phosphate glasses; britholite (Cax(REE,MA)10-x(SiO4)6O2) or zirconolite ((Ca,REE,MA)(Zr,REE,MA)(Ti,Al,Fe)2O7), in silicate systems. This possibility is confirmed by experimental data on the crystallization of glasses with REEs and actinides (Pu, Am). The prospect for the disposal of glasses with the REE–MA fraction in deep boreholes is briefly considered.

A highly stable and conductive cerium‐doped Li7P3S11 glass‐ceramic electrolyte for solid‐state lithium–sulfur batteries

AbstractIn this report, a facile wet chemical method using acetonitrile combined with thermal annealing was used to prepare Li2S‐P2S5 (LPS) based glass‐ceramic electrolytes with (1 wt%, 3 wt%, and 5 wt% Ce2S3) and without Ce2S3 doping. The crystal structure, ionic conductivity, and chemical stability of Li7P3S11 glass‐ceramic electrolytes were examined at varying temperatures (250–350°C). The results indicated that the highest ionic conductivity of 3.15 × 10−4 S cm−1 for pure Li7P3S11 was observed at a temperature of 325°C. By incorporating 1 wt% Ce2S3 and subjecting it to a heat treatment at 250°C, the glass ceramic electrolyte attained a remarkable ionic conductivity of 7.7 × 10−4 (S cm−1) at 25°C. Furthermore, it exhibited a stable and extensive electrochemical potential range, reaching up to 5 volts when compared to the Li/Li+ reference electrode. By tuning the glass transition and crystallization temperature, cerium doping seems to make Li7P3S11 more chemically stable, compared to its original 70Li2S‐30P2S5 counterpart. According to Raman and X‐ray photoelectron spectroscopy analyses, cerium doping inhibits the decomposition of highly conductive P2S74‐ (pyro‐thiophosphate) to PS43− and P2S64−. Doped LPS has a greater crystallinity and more uniform microstructure than pure LPS, according to XRD, Raman spectroscopy, and scanning electron microscopy analysis. Consequently, Li7P2.9Ce0.1S11 electrolyte shows great potential as a solid‐state electrolyte for constructing high‐performance sulfide‐based all‐solid‐state batteries.

Impact of Shadow Glass Transition on Crystallization in Metallic Glass

Impact of Shadow Glass Transition on Crystallization in Metallic Glass

Study of properties of guar gum and its use in development of packaging film

Discarded plastic materials are now a potential problem throughout the globe; therefore, researchers today attach huge importance and applicability to green chemistry and the sustainable development of biopolymer-based materials that can fulfil the needs of synthetic plastics and polymers and save the biological community of the globe. In this work, a new packaging film was developed by using polyvinyl alcohol (PVA) and guar gum (GG) modified with n-octenyl succinic anhydride (OSA). The objective of the work is to develop a water-resistant film for food packaging applications. In synthesizing the biomaterial film, PVA, glycerol, and guar gum with OSA are used to enhance the capability of water resistance, and the major aim of this study is to improve the hydrophobic nature of guar gum through modification with OSA. The glass transition temperature (Tg = 114.45 °C), crystallization temperature (Tc = 176.85 °C), and melting temperature (Tm = 191.28 °C) of the films indicated better thermal stability. In the characterization study, it was found that 30 % GG/PVA with 5 % OSA provides a better result.

Non-isothermal crystallization kinetics for CaO–SrO–B2O3–Al2O3–Bi2O3–SiO2 glass system with Ta2O5 addition

The effect of Ta2O5 at the rates of 1, 2, 3 and 4 % mol on the CaO–SrO–B2O3–Al2O3–Bi2O3–SiO2 glass system was examined by the melt-quenching at 1400 °C. Non-isothermal crystallization kinetics of the compounds were calculated using Differential Scanning Calorimetry (DSC). The kinetics study revealed activation energy values of 109.4 kJ/mol for the T1 composition, 302.14 kJ/mol for the T2 composition, 471.5 kJ/mol for the T3 composition, and 344.7 kJ/mol for the T4 composition, as determined by applying the Kissinger method. According to the average of Avrami parameters, two-dimensional crystal growth was observed in T1 glass and surface crystallization was observed in all other glass. The glass forming ability (GFA) of the glasses was investigated with the values obtained as a result of HSM analysis. In the XRD analysis performed after heat treatment at 850 °C, crystal phase development was observed in the glasses. As a result of the crystallization process, it was observed that wollastonite, strontium aluminum silicate, strontium aluminum oxide and bismuth oxide phases were formed in T1, T2 and T3 glasses.

Rapid identification of highly glass-forming alloys in Cu–Zr binary system by laser glazing

The high-efficient experimental identification of novel metallic glasses with high glass-forming ability (GFA) is crucial for breaking through the traditional trial-and-error approach, which is time-consuming and costly. A rapid detection method for highly glass-forming alloys using laser glazing was introduced and validated in a classic binary Cu–Zr system with well-known GFA across a wide compositional range. The vitrification degree induced by laser glazing was assessed for each selected alloy and shows a strong correlation with GFA determined by traditional rapid solidification methods. The combination of experimental kinetic analysis and theoretical finite element simulation revealed possible thermodynamic mechanisms of glass formation and crystallization in the heat-affected zone (HAZ) formed by laser glazing. The results offer insights into not only the rapid identification method of highly glass-forming alloys using laser glazing but also the mechanism of glass formation under fast heating and cooling processes, providing guidance on the construction of bulk metallic glasses through laser additive manufacturing.

Crystallization of an undercooled Zn-based glass forming alloy

Zn-based metallic glasses (Zn40Mg11Ca31+xYb18-x, x = 0 - 4) are strong glass forming alloys with low glass transition temperatures. While the crystallization onset temperature is also low, the nucleation behavior has not been examined and analyzed quantitatively. For a Zn40Mg11Ca31Yb18 metallic glass alloy, the crystallization behavior was determined based on the application of the Flash differential scanning calorimetry (DSC) with ultrafast heating and cooling rates. The critical cooling rate range was measured for glass formation at 1.6(±0.2) × 104K/s. A temperature-time-transformation (TTT) diagram for the nucleation onset in an undercooled liquid was obtained by applying a series of isothermal exposures by fast heating from the glass state or fast cooling from the liquid state to the target temperatures. A heterogeneous nucleation analysis model was developed to interpret the experimental TTT diagram, which provided a further understanding of the nucleation in Zn-based metallic glasses.

Impact of impurities on the thermal properties of a Li2S–SiS2–LiPO3 glass

AbstractThe preparation of 0.58 Li2S + 0.315 SiS2 + 0.105 LiPO3 glass, and the impacts of polysulfide and P1P defect structure impurities on the glass transition temperature (Tg), crystallization temperature (Tc), working range (ΔT≡ Tc ‐ Tg), fragility index, and the Raman spectra were evaluated using statistical analysis. In this study, 33 samples of this glass composition were synthesized through melt‐quenching. Thermal analysis was conducted to determine the glass transition temperature, crystallization temperature, working range, and fragility index through differential scanning calorimetry. The quantity of the impurities described above was determined through Raman spectroscopy peak analysis. Elemental sulfur was doped into a glass to quantify the wt% sulfur content in the glasses. Linear regression analysis was conducted to determine the impact of polysulfide impurities and P1P defect impurities on the thermal properties. Polysulfide impurities were found to decrease the Tg at rate of nearly 12°C per 1 wt% increase in sulfur concentration. The sulfur concentration does not have a statistically significant impact on the other properties (α = 0.05). The P1P defect structure appears to decrease the resistance to crystallization of the glass by measurably decreasing the working range of the glasses, but further study is necessary to fully quantify and determine this.

Tunable emission and energy transfer of B2O3–Bi2O3–AlF3 glass system doped with Eu3+/Dy3+

The structure and luminescent properties of the B2O3–Bi2O–AlF3 glass system doped with Eu3+/Dy3+ ions in different molar ratios were studied. A series of glasses were synthesized by the conventional melt quenching technique. Glass transition and crystallization temperatures were examined by Differential Thermal Analysis (DTA) measurements. The amorphous character of the prepared samples was confirmed by the X-ray diffraction (XRD) method. Raman and FTIR spectra were collected and deconvoluted to investigate the glass micro-structure. Luminescence spectra revealed that the added rare-earth ions can be excited by a single wavelength. The emitted color can be tuned by changing the ratios of the Eu3+/Dy3+ ions and the excitation wavelength. Furthermore, the influence of the addition of AlF3 on the luminescence and decay times was investigated. In the glasses with 10 mol% AlF3 an enhancement of the emission and excitation spectra was detected. The energy transfer analysis confirms the energy transfer between Eu3+ and Dy3+ ions in the glass matrix. Additionally, the results of this study indicate that the B2O3–Bi2O–AlF3 glasses doped with Eu3+ and Dy3+ can be used as a color tunable phosphor.

Fabrication and Characterization of Colorant-Doped Glass Produced with Local Sand of Nong Phok Site

It is well-known that silica sand is a special type of quartz sand that is suitable for glass fabrication due to its high silica content and low content of iron oxide. In this work, chemical analysis has been carried out on a sand sample from the Nong Phok site, Roi Et province, northeastern Thailand. The geological resources show that this site possesses a surface-to-near surface sand deposit. The grain of fine white sand consists of clear crystals. The grain shape is mainly angular-to-round. Chemical analysis shows that the sand contains more than 99 wt% silica and small amounts of Al, Ca, Ti, and Zr which is in agreement with international standards for glass production. The sand has been used as raw material for the fabrication of soda-lime, lead crystal, and lead-free high refractive index glasses. The colorless and various colored glass products have been satisfactorily used in domestic art and glass manufacturers which promotes local employment and economics.

Suppression of Surface Crystallization of CaO-Al2O3-SiO2 Glass via Hydrothermal Treatment under Acidic Conditions.

This study demonstrates bulk crystallization of CaO-Al2O3-SiO2 (CAS) glass with suppression of surface crystallization via hydrothermal treatment under acidic conditions. It focuses on CAS glass-ceramics (GCs) with precipitated metastable CaAl2Si2O8, a layered calcium aluminosilicate, because it features a single bulk crystallization phase with a relatively lower volume fraction. After hydrothermal treatment under nitric acid, the resultant glasses possessed silica-rich surface layers. When the obtained glass with the surface layer was heat-treated at 1100 °C for 6 h, the resultant surface layer was easily peeled off by hand, and the cross section of both the edge and interior of the specimen showed precipitation of only metastable CaAl2Si2O8. The volume fraction of this crystalline phase was ∼50%, which was 20% larger than those reported for CAS GCs heat-treated at 1050 °C. By contrast, anorthite, the stable phase of CaAl2Si2O8, grew and invaded from the surface to the interior of the glass specimen heat-treated at 1100 °C for 6 h but not subjected to the hydrothermal treatment. These results indicate that the presence of a silica-rich layer on the glass surface suppressed surface crystallization even at the temperature that promotes surface crystallization, suggesting that the range of heat treatment conditions for glass crystallization can be expanded, enabling microstructural control of CAS GCs.

Bisphosphonium cation based metal halide glass scintillators with tunable melting points.

Organic-inorganic metal halide (OIMH) glass offers the advantages of large-scale production, high transparency, and minimal light scattering. However, undesired crystallization in OIMH glass can occur, leading to deteriorated transparency. Herein, a series of bisphosphonium organic cations were designed to construct Mn-based metal halide crystals with a photoluminescence quantum yield (PLQY) near unity, alongside the development of highly thermally stable OIMH glasses. Two strategies were employed to lower the melting point of OIMH: alkyl chain elongation and fluorine substitution. The (Hex-3,4-2F)MnBr4·MeOH (Hex-3,4-2F = hexane-1,6-diylbis((3,4-difluorobenzyl)diphenylphosphonium)) crystal delivers a glass transition temperature of 100 °C and the highest T g/T m ratio (0.82) among OIMHs. The resulting OIMH glass exhibits a PLQY of 47.6%, achieves an impressive resolution of 25 lp mm-1 in X-ray imaging, and remains transparent even after being heated at 90 °C for six weeks. These bisphosphonium-based OIMH glasses present a feasible design for the practical application of OIMH glasses in radiation detection.

Sb induced effect on glass transition, crystallization kinetics and optical properties of Se96Sn4 alloy

Se96-xSn4Sbx (x = 0, 2, 4, 6, and 8) glassy alloys were prepared using the melt quench technique. Thermal measurements were carried out using differential scanning calorimetry (DSC) in non-isothermal mode. Kissinger and Moynihan methods are used for glass transition kinetics, while Kissinger, Takhor, and Augis-Bennet methods are used to study crystallization kinetics. The inclusion of Sb in the alloy increased the glass transition temperature (Tg), activation energy of the glass transition (Et), and activation energy of crystallisation (Ec). The chemical bond approach has been used to explain the results. The rising trend of Ec is explained by the production of SnSe4/2 structural units with energies greater than those of Se–Se and Se–Sb bonds, increasing the degree of cross-linking. The dimensionality of crystal growth changes from one to two with the addition of Sb to the Se-Sn alloy. The criterion for thermal stability was addressed by using the enthalpy emitted during the crystallization process. In addition, Kubelka-Munk transformation and Tauc plots were used to calculate the band gaps. The energy gap (Eg) decreases from 3.72 to 1.60 eV as the Sb concentration increases from 0 to 8 atm%.

Shape memory hydrogels with remodelable permanent shapes and programmable cold-induced shape recovery behavior.

Most shape memory polymers apply glass transition or crystallization of domains to fix temporary shapes and shape recovery is induced by heating, which hinders their application under heat-intolerant conditions. Moreover, the permanent shapes of polymers normally cannot be altered arbitrarily after fabrication. Herein, we present a novel shape memory hydrogel with a remodelable permanent shape and programmable cold-induced shape recovery behavior. Poly(acrylic acid) (PAA) hydrogel is prepared in the presence of diethylenetriamine (DETA) and subsequently treated with calcium acetate (Ca(Ac)2). The charge-assisted hydrogen bonding between PAA and DETA imparts the hydrogel with remodelability, while the heat-induced hydrophobic aggregation of polymer chains and acetate groups results in shape fixation by heating and shape recovery by cooling. Afterwards, programmable deformable devices are obtained by assembling hydrogel blocks with different concentrations of Ca(Ac)2. This design strategy promotes the development of shape memory polymers with diverse potential applications.

Lithium germanosilicate glass formation, kinetics, stability and crystallization

Lithium disilicate glass (Li2O•2SiO2) was modified using GeO2 resulting in compositions Li2O•2GeO2•2SiO2 (L1G2S2), Li2O•GeO2•SiO2 (L1G1S1), and GeO2•SiO2 (L0G1S1). The glass formation was investigated and confirmed for compositions L1G2S2 and L1G1S1 through differential thermal analysis and X-ray diffraction. Two heat treatments were conducted in order to form a glass-ceramic and a sample with a larger crystalline fraction. The crystalline phase was identified through X-ray diffraction as a Li2(Ge,Si)2O5 solid solution of lithium silicate (PDF 010-70-4856). Raman spectra of all samples were analyzed and discussed. The presence of bands associated with Ge in defect sites in silica glass, and those associated with Si–O-Ge bonds suggest the network is established by both SiO2 and GeO2 and not two separate networks, which is consistent with the formation of a solid solution. The refractive index was measured for the glasses and glass-ceramics samples, revealing a very small dispersion between 0.3 and 0.8 μm.

On the mechanism of helium permeation through silica glass

<abstract> <p>Although the densities of crystal quartz and vitreous silica differ only by about 17% (2.65 and 2.20 g/cm<sup>3</sup>, respectively), the helium permeability of silica glass is six orders more elevated than that of crystal quartz. This vast difference has puzzled researchers for decades considering that silica glass and quartz crystal have the same chemical composition. This work discusses the mechanism of high helium permeation through silica glass. It briefly reviews the experimental data and its contradictions with the continuous random network theory. A recently proposed nanoflake model for silica glass structure is utilized to explain the origin of glass permeation to helium. According to the nanoflake model, the formation of nanoflakes not only brings a one-dimensional medium-range ordering structure into silica glass but simultaneously creates regions where van der Waals bonds replace the oxygen-silicon covalent bonds. It is the weakness of van der Waals bonds that causes the helium mobility in these areas to increase.</p> </abstract>

3D visualization reveals the cooling rate dependent crystallization near a wall in dense microgel systems.

Controlled crystallization, melting and vitrification are important fundamental processes in nature and technology. However, the microscopic details of these fundamental phenomena still lack understanding, in particular how the cooling rate and presence of a wall influence the crystal nucleation and glass formation. Thermoresponsive microgels provide the possibility to study phase transitions at the single-particle level, owing to the ability to tune the particle size with temperature. In this study, we employ composite microgels consisting of a hard core and a crosslinked poly(N-isopropyl acrylamide-co-methacrylic acid) shell to study the crystallization of dense suspensions of soft colloids near a wall using confocal microscopy. We investigate the effect of the cooling rate on the fluid-to-solid transition close to the sample wall. The structures formed during cooling range from glassy in the case of a rapid temperature quench to crystalline when a slow cooling rate is used. Detailed analysis of the final structure reveals that the cooling rate also sets the degree of alignment of the crystal domains with the wall as a result of a balance between homogeneous and heterogeneous crystal nucleation. The results presented here yield valuable insight into the microscopic details of temperature-controlled crystallization near a wall. This understanding will help pave the way towards optimal crystallization conditions for microgel applications.

One-dimensional van der Waals BiSBr: an anisotropic thermoelectric mineral.

The fascinating characteristics of one-dimensional van der Waals crystals (V-VI-VII) enable their wide functionality. In particular, their anisotropic carrier transport and low thermal conductivity are advantageous from a thermoelectric viewpoint. In a quest for the "electron crystal phonon glass" paradigm, the present work investigated the thermoelectric performance of BiSBr. Deep insights were gained into the structural and electronic properties that revealed the synergetic effect of the bonding heterogeneity, lone pair of electrons, and degenerated bands that accelerated favorable transportation. Consequently, a low lattice thermal conductivity (0.225 W m-1 K-1) and considerable power factor (3.471 mW m-1 K-2) and thus a high zT of 2.34 were noted in the x-direction (perpendicular to the chain) at 500 K in the case of the material with 1.5 × 1020 holes per cm3. These observations suggest that BiSBr is a plausible near-room-temperature anisotropic thermoelectric mineral.