Thermoanalytical Measurements Research Articles

Antitumor neodymium(III) complex with 1,10-phenanthroline and nitrate ligands: A comprehensive experimental-theoretical study, in silico pharmacokinetic and cytotoxic properties

Here we report the crystallization of the tris(nitrate-O,O')-bis(1,10-phenanthroline-N,N')-neodymium(III) complex by the slow solvent evaporation method. Structural, electronic, thermal, and vibrational properties have been explored and discussed. Additionally, all vibrational modes were carefully assigned, and geometric parameters and chemical reactivity indices were obtained from the results of density functional theory (DFT) calculations including solvation effects in dimethylformamide and water, as well as in vacuum. Moreover, a computational study using Hirshfeld surfaces identified and quantified the intermolecular interactions that stabilize the crystal lattice. X-ray powder diffraction results showed that the system has monoclinic symmetry with C2/c-space group and four monomers per unit cell (Z = 4). The thermoanalytical measurements revealed that the material has high thermal stability (≈ 300°C) and the experimental Raman and FT-IR spectroscopic data showed good correlation with the spectra calculated via DFT, where it was confirmed the influence of the solvents on the structure of the complex. Finally, cell viability assays showed that the neodymium(III) complex has cytotoxic activity and selectivity against MCF-7 (breast) and SiHa (cervical) cancer cells, with a potent biological effect. Complementary, a computational study of the pharmacokinetic profile was performed to support the experimental biological data via absorption, distribution, metabolism and elimination (ADME), and druglikeness.

3D Printed Concrete: Fresh and Hardened Properties

3D concrete printing (3D CP) is an advanced form of additive manufacturing (AM), that allows for the creation of complex geometrical structures using concrete. This technology has the potential to reduce construction time and labour costs while minimizing material waste. However, there are also challenges related to material properties, structural integrity, and standardization of construction practices. The primary challenge in developing 3D printable cementitious materials lies in engineering specific fresh properties that enable extrusion-based printing. Unlike cast concrete, where formwork provides dimensional stability during the printing process, the absence of formwork in 3D printing necessitates fresh mixtures with low-slump and high-thixotropy to be suitable for concrete 3D printing. Additionally, the orthotropic nature of the resulting 3D printed object due to the extrusion process impacts its mechanical properties. Therefore, this research aims to study the effect of water content and loading directions on 3D printed concrete. A pre-mix material from Sika was used in this study. Three mixes were prepared by using three different water to dry material (w/d) ratios, 0.140 l/kg, 0.145 l/kg and 0.150 l/kg. The experiments focused on analysing flowability, green strength, mechanical properties (compressive strength, flexural strength, and modulus of elasticity), water absorption, porosity, and chemical transformations at high temperatures through thermoanalytical measurement. The results showed that the mixture containing 0.145 l/kg (w/d) exhibited satisfactory 3D printability, optimal mechanical performance, lower porosities compared with mixtures 0.140 and 0.150, and same total porosity compared with cast specimen.

THERMAL PROPERTIES OF CROSS-LINKED POLYMERS BASED ON CHITOSAN AND POLYACRYLAMIDE

The thermal properties of cross-linked polymers based on chitosan and polyacrylamide were studied. Samples of the resulting network polymers, which included chains of polyacrylamide and chitosan, were obtained as hydrogel materials by radical polymerization of acrylamide in the presence of chitosan using the redox system of cerium (IV) ammonium nitrate as an initiator and N,N’-methylene-bis-acrylamide as a crosslinker. The structure of the obtained polymers was confirmed by comparing their IR spectra with the spectra of chitosan and polyacrylamide. It was shown that in the IR spectrum of the chitosan-containing sample, the peak at 2932 cm -1 indicates the presence of CH2 groups in the polymer chains and the formation of cross-links. Deformation and valence vibrations of the amide group in polyacrylamide are observed at 1600–1660 cm -1, and the band at 1633 and 1411 cm -1, which appears when the amide bond of polyacrylamide is formed, corresponds to C-N vibrations in the graft copolymer. These characteristic bands confirm the possibility of graft copolymerization of acrylamide on chitosan. The influence of the mass ratio of chitosan and polyacrylamide on the thermal properties of polymer systems was investigated by the method of thermogravimetric and differential thermogravimetric analysis. Atmospheric gas (1 bar, 40 % relative humidity) was used in all thermoanalytical measurements. The samples were examined after vacuum drying at 4 × 10-7 bar and 60 °C using Concentrator Plus. TGA and DTG curves were obtained in the temperature range from 30 to 500 °C with a scanning speed of 5 °C/min using 40 μl aluminum oxide crucibles. It was established that increasing the concentration of chitosan during synthesis reduces the amount of bound water in the obtained samples. Analysis of thermal destruction at the final stages of heating indicates that the presence of chitosan in samples of cross-linked polymers increases their heat resistance by 10–15 °C. The obtained regularities can be used in the creation of composite materials for hydrogel wound dressings and covering medical agents for external use.

Imipramine-imprinted polymer: Designing by theoretical and empirical studies

In this study the model drug imipramine was used to elaborate a theoretical protocol for the evaluation of the selectivity of molecularly imprinted polymer (MIP) system towards the drug and its main metabolite, viz. imipramine and desipramine for the bioanalytical purpose. The MIP1 prepared from 4-vinylbenzoic acid disclosed the highest binding capacity (8.3 ± 1.6 µg g−1) and the lowest ΔEB (–200.88 kcal mol−1) among all tested MIP systems together with the highest specificity with imprinting factor close to 16. The morphological and thermoanalytical measurements confirmed differences between MIP1 and NIP1 with the total specific surface areas equal to 147.2 m2 g−1 and 129.4 m2 g−1, respectively. The selectivity study revealed the highest binding capacities for imipramine and its close structural analogs, viz. maprotyline and protriptyline. The optimized experimental molecularly imprinted solid phase extraction protocol for MIP1 allowed for the recovery of imipramine and its main metabolite, desipramine from spiked human plasma samples with 108% and 69%, respectively, verifying positively the elaborated theoretical model.

Removal of Methylene Blue from Aqueous Solution by Mixture of Reused Silica Gel Desiccant and Natural Sand or Eggshell Waste

The purpose of this work was to develop, characterize and test new low-cost materials suitable for removing methylene blue dye from water and wastewater by adsorption. The solid materials consisted of silica gel powder (SG), silica gel mixed with eggshell powder (SG-ES) and a mixture of silica gel with sand from the western Iraqi desert (SG-SI). The samples were milled by using an electrical mixer and a ball mill, followed by a drying step. In addition, desert sand was acid-treated in order to remove impurities. The structure and chemical composition of the samples were investigated by X-ray diffraction (XRD), a scanning electron microscopy technique equipped with an energy-dispersive X-ray spectrometer (SEM-EDX), a low-temperature nitrogen adsorption (BET) technique, thermo-analytical (TG/TGA) measurements and Fourier-transformed infrared spectroscopy (FTIR). The previously mentioned materials were tested to remove methylene blue from an aqueous solution. The adsorption experiments were monitored by ultraviolet-visible (UV-Vis) spectrophotometry and showed that SG and SG-ES gave promising results for the methylene blue removal from water. After 40 min of treatment of the aqueous solution containing 10 mg/L of MB at room temperature, the tested SG, SG-ES and SG-SI materials were found to have 86%, 80% and 57% dye adsorption efficiency, respectively. Taking into consideration not only the adsorption activity of the studied material but their availability, cost and concepts of cleaner production and waste minimization, the developed silica gel with eggshell can be considered as a good, cost-effective alternative to commercially available activated-carbon-based adsorbents. Different kinetic and isotherm models were fitted to the experimental results. A pseudo-second-kinetics-order model revealed high correlation fitting, while the Freundlich model was found to appropriately describe the adsorption isotherm. The thermal stability during the possible regeneration process of the SG-ES adsorbent mixture and its interaction mechanism with cationic dye was discussed.

Synthesis, crystal structure and magnetic properties of coordination compounds of Mn(NCS)2 with the 3-bromopyridine ligand

Abstract Reactions of Mn(NCS)2 with 3-bromopyridine in acetonitrile lead to the formation of Mn(NCS)2(3-bromopyridine)4 (1) and Mn(NCS)2(3-bromopyridine)2(MeCN)2 (2) that were characterized by single crystal X-ray diffraction. Compounds 1 and 2 consist of discrete complexes, in which the Mn(II) cations are octahedrally coordinated by two trans-N-bonding thiocyanate anions and four pyridine (1) or two pyridine and two acetonitrile ligands (2). Thermoanalytical measurements on 1 and 2 have shown that upon heating half of the 3-bromopyridine co-ligands from 1 or both acetonitrile ligands from 2 are removed leading to a crystalline phase with the composition [Mn(NCS)2(3-bromopyridine)2] n (3-II). From dry n-butanol a phase with the same composition was obtained (3-I) that corresponds to a polymorphic or isomeric form of 3-II. Crystal structure analysis of 3-I shows that in this form the Mn cations are linked by pairs of anionic ligands into linear chains. The results of magnetic measurements on 3-I show antiferromagnetic interactions along the chains and the analysis of the magnetic susceptibility using the Fisher model for chains gave a J value of −5.76(5) K.

Physiological and molecular aspects of seed longevity: exploring intra-species variation in eight Pisum sativum L. accessions.

Conservation of plant genetic diversity is fundamental for crop improvement, increasing agricultural production and sustainability, especially in the face of climatic changes. Although seed longevity is essential for the management of seed banks, few studies have, so far, addressed differences in this trait among the accessions of a single species. Eight Pisum sativum L. (pea) accessions were investigated to study the impact of long‐term (approximately 20 years) storage, aiming to reveal contrasting seed longevity and clarify the causes for these differences. The outstanding seed longevity observed in the G4 accession provided a unique experimental system. To characterize the biochemical and physical status of stored seeds, reactive oxygen species, lipid peroxidation, tocopherols, free proline and reducing sugars were measured. Thermoanalytical measurements (thermogravimetry and differential scanning calorimetry) and transmission electron microscopy combined with immunohistochemical analysis were performed. The long‐lived G4 seeds neither consumed tocopherols during storage nor showed free proline accumulation, as a deterioration hallmark, whereas reducing sugars were not affected. Thermal decomposition suggested a biomass composition compatible with the presence of low molecular weight molecules. Expansion of heterochromatic areas and reduced occurrence of γH2AX foci were highlighted in the nucleus of G4 seeds. The longevity of G4 seeds correlates with the occurrence of a reducing cellular environment and a nuclear ultrastructure favourable to genome stability. This work brings novelty to the study of within‐species variations in seed longevity, underlining the relevance of multidisciplinary approaches in seed longevity research.

Synthesis, Crystal Structure and Properties of a new Hydrate of Manganese Thiocyanate with the Composition Mn(NCS)2(H2O)2

AbstractThe reaction of Mn(NCS)2 with 3‐cyanopyridine in water accidentally leads to the formation of single crystals of Mn(NCS)2(H2O)2 (1). If the synthesis is performed without 3‐cyanopyridine, the known tetrahydrate Mn(NCS)2(H2O)4 is formed. In the crystal structure of the new hydrate, the Mn2+ cations are linked by pairs of μ‐1,3‐bridging anionic ligands to chains, which are further connected via Mn(NCS)2(H2O)4 units into layers, that are additionally stabilized by intralayer hydrogen bonding. These layers are linked by interlayer hydrogen bonding into a 3D network. The structure of 1 shows strong similarities to that of both the tetrahydrate and of Mn(NCS)2. The synthesis from water always leads to the tetrahydrate, which is also obtained, when Mn(NCS)2 is stored in a humid atmosphere. Thermoanalytical measurements on the tetrahydrate show a more complicated behavior, which includes melting at about 46 °C and on cooling sometimes the dihydrate is observed. If the tetrahydrate is stored in vacuum at room temperature, the dihydrate forms before the transformation to the anhydrate is observed. Isothermic water sorption measurements prove, that at low humidity the dihydrate is obtained, which transforms into the tetrahydrate at higher humidities.

Synthesis, Physicochemical, Thermal and Antioxidative Properties of Zn(II) Coordination Compounds with Pyrazole-Type Ligand

The reactions of pyrazole derivative, i.e., ethyl-5-amino-1-methyl-1H-pyrazole-4-carboxylate (L) with zinc halogenides in methanolic solution and zinc nitrate and zinc acetate in acetonic solution are described. The formulae of synthesized compounds are ZnL2Cl2 (1), [ZnL2Br2] (2), ZnL2I2·0.5MeOH (3), [Zn(L)2(H2O)4](NO3)2 (4), and {ZnL(OAc)2}2 (5). Two complexes are obtained in form of single crystals: [ZnL2Br2] (2) and [Zn(L)2(H2O)4](NO3)2 (4). Their crystal and molecular structure were determined by single-crystal X-ray structure analysis. The FTIR spectra of compounds prove the complex formation with all five zinc salts. The complexes are characterized by conductometric and thermoanalytical measurements, and their antioxidative activity was also tested by the scavenging effect on the DPPH radical. Conductometric results, solvolytic stability, and antioxidative activity of the compounds are in correlation.

Thermodynamic investigation of Co–Cr alloys, III: Thermo-analytical measurements using DSC and DTA techniques

Abstract Several Co–Cr alloys have been investigated by Differential Scanning Calorimetry (DSC) as well as by Differential Thermal Analysis (DTA) in the temperature range 298 – 1823 K. The compositional range investigated was from 0 to 87 wt.% Cr with special attention given to alloys with low Cr contents, i. e. 0 to 10 wt.% Cr. From the DSC measurements molar heat capacity values, phase transformation temperatures, enthalpies of transformation and Curie transition temperatures were derived. From the DTA measurements, the melting temperatures and melting enthalpies were evaluated. The trends obtained were compared with the results for pure Co as well as the proposed phase diagram reported in literature.

Co-ordination behaviour of hydrazine and isomers of acetoxy benzoic acids with transition metal ions

ABSTRACT. New hydrazine complexes of some divalent transition metal ions of formulae, [M{(2-ab)2(N2H4)}].3H2O, [M{(3-ab)2(N2H4)}].3H2O and [M{(4-ab)2(N2H4)2}].2H2O where M = Co, Ni, Zn and Cd; 2-abH = 2-acetoxy benzoic acid, 3-abH = 3-acetoxy benzoic acid and 4-abH = 4-acetoxy benzoic acid were prepared using their respective metal nitrates and hydrazine hydrate at pH 6 and 5, respectively, and characterized by elemental analysis, IR and UV-reflectance spectroscopic techniques, thermo analytical technique, powder XRD, SEM-EDX and magnetic susceptibility measurements. All the transition metal complexes were sparingly soluble in water. The IR spectra of complexes showed N-N absorptions of hydrazine in the range of 964-988 cm-1 substantiating the bidentate bridging coordination of hydrazine. They showed endothermic decomposition in the range of 67-100 °C, exothermic dehydrazination in the range, 210-281 °C and an oxidative decomposition between 350 and 490 °C to form their respective metal oxides. The electronic spectral and magnetic susceptibility data could substantiate the distorted octahedral geometry of nickel and cobalt complexes and the XRD pattern indicates the existence of isomorphism. Crystals of [Cd(H2O)3((C6H4(4-OH)(COO))2].H2O obtained as by-product, was also characterized using single crystal XRD, IR and thermal studies.
 
 KEY WORDS: Acetoxy benzoic acids, Hydrazine, Thermal analysis, Single crystal XRD
 
 Bull. Chem. Soc. Ethiop. 2021, 35(2), 337-350. 
 DOI: https://dx.doi.org/10.4314/bcse.v35i2.9

Integrating Thermal Analysis and Reaction Modeling for Rational Design of Pyrolytic Processes to Remediate Soils Contaminated with Heavy Crude Oil.

We developed a novel methodology that combines thermo-analytical measurements and mathematical methods to inform the reliable pyrolytic treatment of specific soil/contaminant systems. Our approach improves upon current "black-box" design methods that may overestimate the required treatment intensity and hinder cost efficacy. We used thermogravimetry and evolved gas analysis to characterize the complex network of soil mineral transformations, contaminant desorption, and pyrolytic reactions occurring when contaminated soils are heated in an anoxic atmosphere. The kinetics of these reactions were quantified using a distributed activation energy (DAE) approach with six pseudocomponents and used in a mathematical model for continuous-flow reactors to predict the removal of hydrocarbon contaminants without other fitting parameters. This model was tested with pilot-scale data from pyrolytic treatment of soils contaminated with crude oil and found to be a good predictor of the total petroleum hydrocarbon (TPH) removal for temperatures between 370 and 470 °C and residence times from 15 to 60 min. The light hydrocarbon fraction desorbed quickly, and over 99.7% removal was achieved at 420 °C and 15 min residence time. However, 95% removal of the heavy hydrocarbon fraction, which is a good proxy for polyaromatic hydrocarbons (PAHs), required 470 °C with 15 min residence time. This model can be employed to select operating conditions (e.g., reactor size, treatment time, and temperature) to reliably achieve remediation objectives for specific hydrocarbon/soil mixtures without inflating energy requirements, which would lower operating costs and decrease the process carbon footprint on a system-specific basis.

Surface Properties of 1DTiO2 Microrods Modified with Copper (Cu) and Nanocavities.

This work deals with Cu-modified 1DTiO2 microrods (MRs) and their surface properties. The pristine lyophilized precursor Cu_1DTiO2, prepared by an environmentally friendly cryo-lyophilization method, was further annealed in the temperature interval from 500 to 950 °C. The microstructure of all samples was characterized by electron microscopy (SEM/EDS and HRTEM/SAED), X-ray powder diffraction (XRD), infrared spectroscopy, simultaneous DTA/TGA thermoanalytical measurement, and mass spectroscopy (MS). Special attention was paid to the surface structure and porosity. The 1D morphology of all annealed samples was preserved, but their surface roughness varied due to anatase-rutile phase transformation and the change of the nanocrystals habits due to nanocavities formation after releasing of confined ice-water. The introduction of 2 wt.% Cu as electronically active second species significantly reduced the direct bandgap of 1DTiO2 in comparison with undoped TiO2 and the standard Degussa TiO2_P25. All samples were tested for their UV absorption properties and H2 generation by PEC water splitting. We presented a detailed study on the surface characteristics of Cu doped 1DTiO2 MRs due to gain a better idea of their photocatalytic activity.

Preparation and Characterization of Silicon-Metal Fluoride Reactive Composites.

Fuel-rich composite powders combining elemental Si with the metal fluoride oxidizers BiF3 and CoF2 were prepared by arrested reactive milling. Reactivity of the composite powders was assessed using thermoanalytical measurements in both inert (Ar) and oxidizing (Ar/O2) environments. Powders were ignited using an electrically heated filament; particle combustion experiments were performed in room air using a CO2 laser as an ignition source. Both composites showed accelerated oxidation of Si when heated in oxidizing environments and ignited readily using the heated filament. Elemental Si, used as a reference, did not exhibit appreciable oxidation when heated under the same conditions and could not be ignited using either a heated filament or laser. Lower-temperature Si fluoride formation and oxidation were observed for the composites with BiF3; respectively, the ignition temperature for these composite powders was also lower. Particle combustion experiments were successful with the Si/BiF3 composite. The statistical distribution of the measured particle burn times was correlated with the measured particle size distribution to establish the effect of particle sizes on their burn times. The measured burn times were close to those measured for similar composites with Al and B serving as fuels.

Series of Near-IR-Absorbing Transition Metal Complexes with Redox Active Ligands.

New soluble and intensely near-IR-absorbing transition metal (Ti, Zr, V, Ni) complexes were synthesized using a redox non-innocent N,N’-bis(3,5-di-tertbutyl-2-hydroxy-phenyl) -1,2-phenylenediamine (H4L) as a ligand precursor. In all the complexes, ([Ti(Lox)2, [Zr(Lox)2], [V(Lsq1)(HLox)] and [Ni(HLox)2], two organic molecules coordinate to the metal center as tri- or tetradentate ligands. The solid-state structures of the complexes were determined using single crystal XRD, and the compounds were further characterized with Electrospray Ionisation Mass Spectrometry (ESI-MS). Thermoanalytical measurements indicated the thermal stabilities of the complexes. All compounds absorb strongly in the near-IR region and show very interesting magnetic and electrochemical properties. Moreover, it was shown that the V and Ni complexes can also convert absorbed near-IR photons to (un)paired electrons, which indicates great promise in photovoltaic applications.

La3 B6 O13 (OH): The First Acentric High-Pressure Borate Displaying Edge-Sharing BO4 Tetrahedra.

La3B6O13(OH) was obtained by a high‐pressure/high‐temperature experiment at 6 GPa and 1673 K. The compound crystallizes in the space group P21 (no. 4) with the lattice parameters a=4.785(2), b=12.880(4), c=7.433(3) Å, and β=90.36(10)°, and is built up of corner‐ as well as edge‐sharing BO4 tetrahedra. It represents the first acentric high‐pressure borate containing these B2O6 entities. The compound develops borate layers of „sechser“‐rings with the La3+ cations positioned between the layers. Single‐crystal and powder X‐ray diffraction, vibrational and MAS NMR spectroscopy, second‐harmonic generation (SHG) and thermoanalytical measurements, as well as computational methods were used to affirm the proposed structure and the B2O6 entities.

Estimating errors in the determination of activation energy by advanced nonlinear isoconversional method applied for thermoanalytical measurements performed under arbitrary temperature programs

In a previous paper (Thermochim. Acta 670 (2018) 1–6) it was shown that the estimation of errors (ΔE) in the determination of apparent activation energies (E) determined by a nonlinear isoconversional method applied for thermoanalytical measurements performed under constant heating rates involves the following successive steps: (1) the determination of Fisher confidence interval (ΔFE) for confidence level of 95 % by applying the procedure suggested by Vyazovkin and Wight, and (2) the application of the relation: ΔE=0.2447×ΔFE+0.00037×ΔFE2. The check of this procedure when using advanced nonlinear incremental isoconversional method (A-NL method) suggested by Vyazovkin is applied for thermoanalytical data under arbitrary temperature programs has been performed for: simulated sinusoidal modulated data, thermogravimetric (TG) data for thermal decomposition of a sort of high density polyethylene (HDPE) under quasi-isothermal conditions, and TG data corresponding to thermal decomposition of a sort of low density polyethylene under arbitrary temperature programs. It has been concluded that the suggested procedure for estimating the error in E evaluation based on above relationship is also applicable when A-NL method is used for kinetic analysis of thermoanalytical data recorded under arbitrary temperature programs.

Design and Optimization of Nanostructured Lipid Carrier Containing Dexamethasone for Ophthalmic Use.

The aim of this study was to perform a preformulation study of dexamethasone (DXM)-loaded nanostructured lipid carriers (NLCs) for ocular use. Lipid screening was applied to find the most suitable solid and liquid lipids and surfactant for the NLC formulation. The visual observation was proved with XRD measurements for the establishment of the soluble state of DXM. Thermoanalytical measurements indicated that the most relevant depression of the crystallinity index could be ensured when using a 7:3 solid lipid:oil ratio. In order to optimize the NLC composition, a 23 full factorial experimental design was used. It was established that each independent factor (lipid, DXM, and surfactant concentration) had a significant effect on the particle size while in the case of entrapment efficiency, the DXM and surfactant concentrations were significant. Lower surfactant and lipid concentrations could be beneficial because the stability and the entrapment efficacy of NLCs were more favorable. The toxicity tests on human cornea cells indicated good ophthalmic tolerability of NLCs. The in vitro drug release study predicted a higher concentration of the solute DXM on the eye surface while the Raman mapping penetration study on the porcine cornea showed a high concentration of nanocarriers in the hydrophylic stroma layer.

Single Crystal Growth of FeGa3 and FeGa3−xGex from High‐Temperature Solution Using the Czochralski Method

AbstractSingle crystal growth and characterization of the binary semiconducting compound FeGa3 and its Ge‐substitute FeGa3–xGex are reported. Whereas there have been several investigations on the thermoelectric properties based on small samples grown by the flux method, this study is the first approach using the Czochralski growth technique from well‐oriented single‐crystalline seeds. Problems and solutions of the growth of cm3‐size single crystals are discussed in detail. Ge segregation in FeGa3–xGex is described by a segregation coefficient lower than unity which leads to an axially increasing Ge content along the pulling direction. Consequences with respect to lattice parameter changes and thermoanalytic measurements are reported.

Improvement of intrinsic plasticity and strength of Zr55Cu30Ni5Al10 metallic glass by tuning the glass transition temperature

We report the tuning of the glass transition temperature (Tg) in Zr55Cu30Ni5Al10 metallic glass by rolling at room temperature. The precise thermo-analytical measurements using step-scan modulated temperature differential scanning calorimeter (MTDSC) revealed a decrease of Tg by 16.9 K in ribbons and 7.1 K in bulk glassy plates upon 40% and 70% thickness reduction, respectively. The cold rolled plates exhibit higher yield strength up to σy = 1.66 GPa and larger plastic strain (εp = 8.0%) before failure than that of as-cast plates (σy = 1.45 GPa). Transmission electron microscopy and DSC studies suggest that a relaxed structure has evolved due to the deformation induced structural change upon rolling, which reduces the activation energy of the shear transformation zone and improves the inherent plasticity of the glassy phase.