Glassy Matrix Research Articles

Crystallization processes of rare-earth doped GdF3 nanocrystals in silicate glass matrix: Dimorphism and photoluminescence properties

Rare-earth doped GdF3 nanocrystals embedded in silica glassy matrix have been prepared by controlled crystallization of the xerogel; the influence of rare-earth ion (Pr, Sm, Eu, Tb, Dy, Er, Yb) and additional Li-codopant on structural and optical properties was discussed. The precipitation of RE-doped GdF3 nanocrystalline phase is the result of Gd-trifluoracetate thermolysis revealed as a strong exothermic peak at around 300 °C. Structural analysis of RE-doped SiO2-GdF3 glass-ceramic sample calcined at 525 °C showed the occurrence of GdF3 nanocrystals of about 25 nm size, showing hexagonal or orthorombic structure depending on the RE-ion. Under UV-light excitation at 273 nm of Gd3+ ions (8S7/2 → 6I13/2,15/2 transition), photoluminescence spectra showed characteristic RE3+ luminescence due to the non-radiative energy transfer between the excited Gd3+ and acceptor RE ions; the highest energy transfer (≅ 80 %) was observed for Tb3+ and lowest (≅ 21 %) for Sm3+.

Diffusion Mapping with Diffractive Optical Elements for Periodically Patterned Photobleaching.

Fourier transform-fluorescence recovery after photobleaching (FT-FRAP) using a diffractive optical element (DOE) is shown to support distance-dependent diffusion analysis in biologically relevant media. Integration of DOEs enables patterning of a dot array for parallel acquisition of point-bleach FRAP measurements at multiple locations across the field of view. In homogeneous media, the spatial harmonics of the dot array analyzed in the spatial Fourier transform domain yield diffusion recovery curves evaluated over specific well-defined distances. Relative distances for diffusive recovery in the spatial Fourier transform domain are directly connected to the 2D (h,k) Miller indices of the corresponding lattice lines. The distribution of the photobleach power across the entire field of view using a multidot array pattern greatly increases the overall signal power in the spatial FT-domain for signal-to-noise improvements. Derivations are presented for the mathematical underpinnings of FT-FRAP performed with 2D periodicity in the photobleach patterns. Retrofitting of FT-FRAP into instrumentation for high-throughput FRAP analysis (Formulatrix) supports automated analysis of robotically prepared 96-well plates for precise quantification of molecular mobility. Figures of merit are evaluated for FT-FRAP in analysis for both slow diffusion of fluorescent dyes in glassy polymer matrices spanning several days and model proteins and monoclonal antibodies within aqueous solutions recovering in matters of seconds.

Unlocking the potential of multicomponent mesoporous bioactive glass nanoparticles: An approach to enhanced ion therapy

This work presents the synthesis and characterization of a multicomponent mesoporous bioactive glass (MMBG) derived from the composition of 58S glass modified with copper, zinc, and boron. Morphological data revealed the presence of spherical particles with an average size of 616 nm and a specific surface area of 295 m2·g−1. X-ray diffractogram analysis confirmed the lack of long-range order in the MMBG, indicating the presence of a disordered vitreous structure characteristic of glass. The structural scenario of the bioactive glass MMBG reveals a characteristic configuration of borosilicate glasses, where the [BO4] polyhedra, along with SiO4 tetrahedra, constitute the backbone of the glassy matrix. Concerning zinc and copper ions, they function similarly to calcium in compensating for the remaining negative charges within the borosilicate network, behaving as typical network-modifying ions. The presence of these heavy ions, coupled with the formation of the borosilicate network in MMBG, led to a 20 % increase in density compared to 58S glass. Additionally, alterations in the chemical composition and structure of MMBG resulted in a reduction in molar volume compared to 58S, indicating a decrease in the volume occupied by one mole of oxygen in the glass matrix, thereby increasing the oxygen packing density. The pH studies reveal that changes in the chemical composition of MMBG did not compromise its chemical reactivity in aqueous environments. The capability of MMBG glass to act as a bioactive agent for ion therapy is evidenced by its ability to deliver Zn and Cu ions, as substantiated by the gradual disappearance of absorption in wavenumber range of 690–470 cm−1, attributed to the vibration of Zn-O and Cu-O bonds. Preliminary in vitro assay for bioactivity in SBF revealed that the formation of apatite layer on the surface of MMBG glass was notably thicker and denser compared to 58S glass. This result highlights the superior bioactive response of the MMBG bioactive glass, indicating its potential as an exceptionally favorable material for various biomedical applications.

Mechanistic study of the differences in lactic acid bacteria resistance to freeze- or spray-drying and storage

Lactobacillus delbrueckii subsp. bulgaricus and Lactiplantibacillus plantarum are two lactic acid bacteria (LAB) widely used in the food industry. The objective of this work was to assess the resistance of these bacteria to freeze- and spray-drying and study the mechanisms involved in their loss of activity. The culturability and acidifying activity were measured to determine the specific acidifying activity, while membrane integrity was studied by flow cytometry. The glass transitions temperature and the water activity of the dried bacterial suspensions were also determined. Fourier transform infrared (FTIR) micro-spectroscopy was used to study the biochemical composition of cells in an aqueous environment. All experiments were performed after freezing, drying and storage at 4, 23 and 37 °C. The results showed that Lb. bulgaricus CFL1 was sensitive to osmotic, mechanical, and thermal stresses, while Lpb. plantarum WCFS1 tolerated better the first two types of stress but was more sensitive to thermal stress. Moreover, FTIR results suggested that the sensitivity of Lb. bulgaricus CFL1 to freeze-drying could be attributed to membrane and cell wall degradation, whereas changes in nucleic acids and proteins would be responsible of heat inactivation of both strains associated with spray-drying. According to the activation energy values (47–85 kJ/mol), the functionality loss during storage is a chemically limited reaction. Still, the physical properties of the glassy matrix played a fundamental role in the rates of loss of activity and showed that a glass transition temperature 40 °C above the storage temperature is needed to reach good preservation during storage.Key points• Specific FTIR bands are proposed as markers of osmotic, mechanic and thermal stress• Lb. bulgaricus CFL1 was sensitive to all three stresses, Lpb. plantarum WCFS1 to thermal stress only• Activation energy revealed chemically limited reactions ruled the activity loss in storageGraphical abstract

Voltammetric Sensor Based on Molybdenum-Vanadium-Lithium-Borate Glassy Matrix and Its Application for the Determination of Iron in Fortified Milk Powder

Voltammetric Sensor Based on Molybdenum-Vanadium-Lithium-Borate Glassy Matrix and Its Application for the Determination of Iron in Fortified Milk Powder

A continuous-wave and pulsed X-band electron spin resonance spectrometer operating in ultra-high vacuum for the study of low dimensional spin ensembles.

We report the development of a continuous-wave and pulsed X-band electron spin resonance (ESR) spectrometer for the study of spins on ordered surfaces down to cryogenic temperatures. The spectrometer operates in ultra-high vacuum and utilizes a half-wavelength microstrip line resonator realized using epitaxially grown copper films on single crystal Al2O3 substrates. The one-dimensional microstrip line resonator exhibits a quality factor of more than 200 at room temperature, close to the upper limit determined by radiation losses. The surface characterizations of the copper strip of the resonator by atomic force microscopy, low-energy electron diffraction, and scanning tunneling microscopy show that the surface is atomically clean, flat, and single crystalline. Measuring the ESR spectrum at 15K from a few nm thick molecular film of YPc2, we find a continuous-wave ESR sensitivity of 2.6 × 1011spins/G · Hz1/2, indicating that a signal-to-noise ratio of 3.9G · Hz1/2 is expected from a monolayer of YPc2 molecules. Advanced pulsed ESR experimental capabilities, including dynamical decoupling and electron-nuclear double resonance, are demonstrated using free radicals diluted in a glassy matrix.

Nanomechanical properties of ceramic materials from the SiO2–Al2O3-(Na2O)–K2O–MgO system with an addition of SrO

The ceramic materials studied in this paper consist of finely dispersed crystalline phases embedded in a glassy matrix, which is similar to glass-ceramic materials, porcelain, and VC products. The strength depends then not only on the properties of the individual crystalline phases but also on their interactions and the matrix. Differences in mechanical properties for materials with similar chemical compositions are most likely related to diverging microstructures. Crystal orientation, grain-size distribution and shape, the ratio of the glass matrix to the crystalline phase, and homogeneity control the flexural strength of glass-ceramic materials. The subject of the study is whiteware ceramic materials from the SiO2–Al2O3–Na2O–K2O–MgO–SrO system, fired similarly to the regime used for VC products. The effect of the type of alkali oxide and the share of SrO were tested. This paper presents the results of hot-stage microscopy, X-ray diffraction (XRD), scanning electron microscopy with a micro-analyzer (SEM-EDS) and biaxial flexural strength measurements. Additionally, nanoindentation technique was used to access local mechanical properties.

Effect of Acidic Media on Surface Topography and Color Stability of Two Different Glass Ceramics.

The aim of this study was to determine the effect of two acidic beverages (orange juice and H3PO4-containing fizzy drink) on the surface topography and color stability of two commonly used computer-aided design/computer-aided manufacturing (CAD/CAM) ceramic materials. Sixty samples of two CAD/CAM ceramic materials, lithium disilicate (IPS e-max CAD) and zirconia reinforced lithium silicate (Vita Suprinity), were prepared according to the manufacturer's instructions. The samples were immersed in one of three media (artificial saliva, orange juice and H3PO4-containing fizzy drink) and then stored in an incubator at 37 °C for 24 hours). Before and after immersion in different media, the surface roughness (Ra) of the samples was assessed using profilometer (JITAI8101 Surface Roughness Tester-Beijing Jitai Tech Detection Device Co. Ltd, China) and the color parameters were measured using VITA Easyshade Advance 4.01 (VITA shade, VITA made, VITA). Surface topography was observed using scanning electron microscope (SEM) and surface mineral content was compared before and after immersion. Paired sample t-test was used to determine the change in Ra before and after immersion. Two-way analysis of variance was used to determine the effect of different CAD/CAM materials and immersion media on the mean ∆Ra and mean ∆E of the studied groups. Tukey's honest significant difference posthoc test was used for multiple comparisons at a level of significance (α = 0.05). A significant increase in Ra and a decrease in the color stability of the two investigated ceramic materials were detected after immersion in the acidic media than in artificial saliva. SEM and energy-dispersive X-ray results revealed the dissolution of the glassy matrix and the exposure of silicate crystals. The surface topography and color stability of glass ceramics are affected by the pH of different acidic media.

In-situ crystallization of CoCr2O4 in tellurite glass with enhanced optical nonlinear limiting, photoluminescence, and magnetic properties: Influence of Co content

This article reports the in-situ growth of spinel CoCr2O4 nanocrystals (NC) in tellurite glass through tailoring the Co content by melt-quenching method. The microstructure, optical, and magnetic properties of NC/ glass systems were systematically studied using various techniques. Well-defined 30 nm crystallization of CoCr2O4 (space group of Fd3m) homogeneously distributed in the glassy matrix and the concurrent formation of cubic BiCoO3 (space group of P4mm) when the Co content exceeds 3%. The coexistence of multivalence and coordination states of Co and Cr significantly modified the glass structure with conversion of TeO4→TeO3, BO4→BO3, and CoO4→CoO6 units. Exceptional performance of the glass containing 5% Co-tuned CoCr2O4 was obtained, showcasing the decrease of Eg (2.09 eV), strong ferro-magnetization of 7.04 emu/g, large α3 (4.88×10−10 m/W) and good optical limiting property (threshhold of 1.31×1012 W/m2). Furthermore, the same glass showed excellent red emission between 650 and 800 nm under the excitation of 460 nm, with an increased lifetime (2.648 ms) and good stability of 90.7% within 25–300 °C. The emission mechanism was discussed. EPR analysis confirmed the active role and spin-states of magnetic Cr and Co ions, contributing synergistically to the improved optical and magnetic properties of the glasses.

Finite dimension of the ion pathway networks in conducting glasses

In disordered materials, the ordinary understanding is that charge carriers tend to occupy energetically favorable sites known as ion-conducting channels. Many studies have revealed that the inherent fractal properties of such pathways lead to a sub-diffusive behavior. The linearity or branching of these pathways is crucial for determining how the charge carriers move. It can be thought that as the space dimensionality decreases, the average distance between the highest energy barriers along the conduction paths increases. In this study the finite dimension of those pathways is computed using an extended version of the classical Hausdorff dimension. Also, the Arrhenius behavior of the most mobile lithium ions is proved, confirming that such are responsible for conductivity behavior. The lithium ions mobility behavior in response to temperature changes and the finite dimension allowed to identify the ion diffusion regions fractal features. The reported results demonstrate that as the temperature increases the conducting channels become broadener, facilitating the transfer of electrical charge through the glassy matrix, below the transition temperature. The pathways behavior confirms the increase of the ionic conductivity when the temperature increases as it is experimentally observed.

Element mobility during basalt-water-CO2 interaction: observations in natural systems vs. laboratory experiments and implication for carbon storage

Today, carbon dioxide removal from the atmosphere is the most ambitious challenge to mitigate climate changes. Basalt rocks are abundant on the Earth’s surface (≈ 10%) and very abundant in the ocean floors and subaerial environments. Glassy matrix and minerals constituting these rocks contain metals (Ca2+, Mg2+, Fe2+) that can react with carbonic acid to form metal carbonates (CaCO3, MgO3 and FeCO3). Here, we present a data compilation of the chemical composition of waters circulating in basalt aquifers worldwide and the results of simple basalt-water-CO2 experiments. Induced or naturally occurring weathering of basalts rocks release elements in waters and elemental concentration is closely dependent on water CO2 concentration (and hence on water pH). We also performed two series of experiments where basaltic rock powder interacts with CO2-charged waters for one month at room temperature. Laboratory experiments evidenced that in the first stages of water-rock interaction, the high content of CO2 dissolved in water accelerates the basalt weathering process, releasing in the water not only elements that can form carbonate minerals but also other elements, which depending on their concentration can be essential or toxic for life. Relative mobility of elements such as Fe and Al, together with rare earth elements, increases at low pH conditions, while it decreases notably at neutral pH conditions. The comparison between experimental findings and natural evidence allowed to better understand the geochemical processes in basaltic aquifers hosted in active and inactive volcanic systems and to discuss these findings in light of the potential environmental impact of CO2 storage in mafic and ultramafic rocks.

α-Cleavage of 2,2-Diazido-2,3-dihydroinden-1-one in Solution and Cryogenic Matrices.

The Norrish type I (α-cleavage) reaction is an excellent photochemical method for radical-pair formation in solution. However, in cryogenic matrices, the starting material typically re-forms before the radical pair diffuses apart. This study focused on N2 extrusion from an azido alkyl radical to prevent radical-pair recombination. Irradiation of 2,2-diazido-2,3-dihydroinden-1-one (1) in methanol mainly yielded methyl 2-cyanomethylbenzoate (2) and 2-cyanomethylbenzoic acid (3) via α-cleavage. Laser flash photolysis of 1 in argon-saturated acetonitrile resulted in α-cleavage to form triplet biradical 31Br1 (λmax ∼ 410 nm, τ ∼ 400 ns). In contrast, upon irradiation in glassy 2-methyltetrahydrofuran matrices, triplet alkylnitrene 31N was directly detected using electron spin resonance (D/hc = 1.5646 cm-1, E/hc = 0.00161 cm-1) and absorption spectroscopy (λmax = 276 and 341 nm). Irradiation of 1 in argon matrices generated 31N, benzoyl azide 4, singlet benzoylnitrene 14N, and isocyanide 5, as revealed by IR spectroscopy. The experimental results supported by density functional theory calculations [B3PW91/6-311++G(d,p)] suggest that irradiation of 1 in matrices results in α-cleavage to form biradical 31Br1, which extrudes N2 to yield 31Br2. Rearrangement of 31Br2 into 31N competes with cleavage of a N3 radical to form radical 1Ra3. The N3/1Ra3 radical pair combines to form 4, which upon irradiation yields 14N and 5.

Design and characterization of novel Zr-Al-Fe-Y metallic glasses with nanoscale phase separation

We present a new phase-separated Zr-based metallic glass (MG) composition, free of toxic elements (Ni and Cu) prepared in a glass-forming system by alloying addition. The substitution of Y in Zr70-xAl12.5Fe17.5Yx (x = 0–15 at.%) results in phase separation, giving rise to nano-amorphous domains in a glassy matrix. A homogeneous MG feature is observed for low concentrations of Y up to x = 5. Microstructure and thermal property analysis indicate that the glasses with x = 10 and 15 at.% Y exhibit a typical liquid phase separation-induced two-glassy phase (Zr-rich and Y-rich) with droplet-like microstructures (nano-amorphous domains). With increasing Y addition, the domain size increases. The microstructural evolution arising due to phase separation in these alloys is confirmed by a combination of transmission electron microscopy (TEM) and atom probe tomography (APT) analysis. The formation of nanometer-size Y-enriched clusters is confirmed by APT for x = 15.

Stabilization of an Infectious Enveloped Virus by Spray-Drying and Lyophilization

Enveloped viruses are attractive candidates for use as gene- and immunotherapeutic agents due to their efficacy at infecting host cells and delivering genetic information. They have also been used in vaccines as potent antigens to generate strong immune responses, often requiring fewer doses than other vaccine platforms as well as eliminating the need for adjuvants. However, virus instability in liquid formulations may limit their shelf life and require that these products be transported and stored under stringently controlled temperature conditions, contributing to high cost and limiting patient access. In this work, spray-drying and lyophilization were used to embed an infectious enveloped virus within dry, glassy polysaccharide matrices. No loss of viral titer was observed following either spray-drying (at multiple drying gas temperatures) or lyophilization. Furthermore, viruses embedded in the glassy formulations showed enhanced thermal stability, retaining infectivity after exposure to elevated temperatures as high as 85 °C for up to one hour, and for up to 10 weeks at temperatures as high as 30 °C. In comparison, viruses in liquid formulations lost infectivity within an hour at temperatures above 40 °C, or after incubation at 25 °C for longer periods of time.

Thermal Stability and Crystallization Processes of Pd78Au4Si18 Thin Films Visualized via In Situ TEM.

Amorphous alloys or metallic glasses (MGs) thin films have attracted extensive attention in various fields due to their unique functional properties. Here, we use in situ heating transmission electron microscopy (TEM) to investigate the thermal stability and crystallization behavior of Pd-Au-Si thin films prepared by a pulsed laser deposition (PLD) method. Upon heating treatment inside a TEM, we trace the structural changes in the Pd-Au-Si thin films through directly recording high-resolution images and diffraction patterns at different temperatures. TEM observations reveal that the Pd-Au-Si thin films started to nucleate with small crystalline embryos uniformly distributed in the glassy matrix upon approaching the glass transition temperature Tg=625K, and subsequently, the growth of crystalline nuclei into sub-10 nm Pd-Si nanocrystals commenced. Upon further increasing the temperature to 673K, the thin films transformed to micro-sized patches of stacking-faulty lamellae that further crystallized into Pd9Si2 and Pd3Si intermetallic compounds. Interestingly, with prolonged thermal heating at elevated temperatures, the Pd9Si2 transformed to Pd3Si. Simultaneously, the solute Au atoms initially dissolved in glassy alloys and eventually precipitated out of the Pd9Si2 and Pd3Si intermetallics, forming nearly spherical Au nanocrystals. Our TEM results reveal the unique thermal stability and crystallization processes of the PLD-prepared Pd-Au-Si thin films as well as demonstrate a possibility of producing a large quantity of pure nanocrystals out of amorphous solids for various applications.

Effects of yttrium on microstructures and properties of Cu45.12Zr45.12Al5.76Nb4 bulk metallic glass composites

The effects of yttrium on the microstructures and properties of Cu45.12Zr45.12Al5.76Nb4 bulk metallic glass composites were investigated. It was found that yttrium addition could effectively control the distribution and volume fraction of B2-CuZr precipitated phase in the composites by adjusting the glass-forming ability of the alloys, and suppress the eutectoid decomposition of B2-CuZr.Within 2 at.% yttrium addition, the volume fraction of B2-CuZr precipitation in the glassy matrix decreases significantly with the increase of yttrium content. For more than 2 at.% yttrium addition, the volume fraction of B2-CuZr precipitation increases as yttrium content increases. An optimal amount of yttrium (2–3 at.%) enhances glass-forming ability of the alloy, reduces B2-CuZr precipitation, and obviously improves the agglomeration and distribution uniformity of B2-CuZr in the amorphous matrix. The compressive properties of BMG composites with more than 1 at.% yttrium addition drop considerably, which should be mainly attributed to the abundant and various forms of Y2O3 brittle phase formed in the glassy matrix.

Parameter relationship and product characteristics analysis of heavy-metal hazardous wastes vitrification under the combination of data science and experiment

Heavy-metal hazardous wastes (HMHW) have a large emission, high toxicity and strong resource properties. Its proper disposal and resource utilization is a key challenge. High-temperature melt vitrification technology is an effective solution to realize the detoxification and resource utilization of HMHW. This paper summarizes and analyzes the control parameters of the existing vitrification treatment of HMHW. The phase transformation process of temperature, slag content, and CAS ratio (CaO-Al2O3-SiO2) in the vitrification treatment of zinc leaching residue (ZLR) was investigated around the vitreous content. The common evolution characteristics of the formed vitrification products in infrared spectrum, UV–vis diffuse reflection spectrum, and microstructures were revealed. The idea of using the maximum UV–vis absorption intensity to qualitatively determine the vitreous content of the products is proposed. Moreover, the correlation between experimental parameters and vitreous content was quantified by combining the data science method, and the mapping of the whole process of ZLR vitrification treatment was constructed. This work provides reliable parameter guidance and method induction for the vitrification treatment of HMHW, especially for wastes with less glassy matrix such as Ca and Si.

Exceptionally strong and ductile bulk metallic glass composite with bioinspired architecture mimicking porcupine fish spine

Introducing soft crystalline phases into the glassy matrix to produce bulk metallic glass composites (BMGCs) is an effective way to enhance the ductility of bulk metallic glasses (BMGs). However, the introduction of soft crystalline phases severely sacrifices the strength, resulting in the strength-ductility trade-off. To defeat this dilemma, here, we successfully fabricate a bioinspired BMGC with architecture mimicking a porcupine fish spine. The bioinspired BMGC shows a pronounced yield strength of ∼800 MPa with an excellent fracture strain of ∼35 %. The fabrication of the bioinspired BMGC is achieved through infiltration and vitrification of molten Zr50Ti5Cu27Ni10Al8(Zr50) melt into the crystalline Nb skeleton fabricated by laser additive manufacturing (LAM). Such enhanced strength-ductility synergy is attributed to the asynchronous deformation associated with the delicate bioinspired heterogeneous architecture. The bioinspired structural design motif, enabled by the combination of LAM and infiltration casting technologies, opens a new window to develop high-performance BMGCs on a large scale for structural applications.

Cryogenic thermal cycling induced simultaneous improvement of strength and ductility in a Zr-based bulk metallic glass composite

Preparing bulk metallic glass composites (BMGCs) is an effective way to improve the plasticity of bulk metallic glasses (BMGs). However, the enhancement of plasticity is usually at the cost of deterioration in strength. In this study, a series of BMGCs with the nominal composition of Zr48Cu48Al4 was prepared. Finely dispersed B2 CuZr crystals are embedded in a glassy matrix and subsequently, these composites were cryogenically cycled in liquid nitrogen followed by heating to various temperatures below the glass transition temperature. It was found that the samples after cryogenic thermal cycling (CTC) treated at an intermediate upper temperature shown a simultaneous improvement of yielding strength from 1680 MPa to 1832 MPa and plasticity from 5.6% to 9.1%. The enhancement of yielding strength is ascribed to the existence of the B19′ phase resulted from the partial martensitic transformation during the CTC treatment, while the improvement of plasticity is attributed to the higher free volume content and the larger “blocking effect” from the B19’ after the samples were treated by CTC. The combination of CTC treatment and precipitation of crystals provides a new strategy for improving the mechanical properties of the BMGs.

Hydrogen bonding in glassy trehalose-water system: Insights from density functional theory and molecular dynamics simulations.

We report a detailed density functional theory and molecular dynamics study of hydrogen bonding between trehalose and water, with a special emphasis on interactions in the amorphous solid state. For comparison, water-water interactions in water dimers and tetramers are evaluated using quantum calculations. The results show that the hydrogen bonding energy is dependent not only on the geometry (bond length and angle) but also on the local environment of the hydrogen bond. This is seen in quantum calculations of complexes in vacuum as well as in amorphous solid states with periodic boundary conditions. The temperature-induced glass transition in the trehalose-water system was studied using molecular dynamics simulations with varying cooling and heating rates. The obtained parameters of the glass transition are in good agreement with the experiments. Moreover, the dehydration of trehalose in the glassy state was investigated through a gradual dehydration with multiple small steps under isothermal conditions. From these simulations, the values of water sorption energy at different temperatures were obtained. The partial molar enthalpy of mixing of water value of -18 kJ/mol found in calorimetric experiments was accurately reproduced in these simulations. These findings are discussed in light of the hydrogen bonding data in the system. We conclude that the observed exothermic effect is due to different responses of liquid and glassy matrices to perturbations associated with the addition or removal of water molecules.