DFT Studies on Thermal Stabilities,Electronic Structures,and ^(13)C Chemical Shifts of C_(24)O_2 Based on Fullerene C_(24)(D_6)

Quantum chemical calculations on some possible equilibrium geometries of C24O2 isomers derived from C24 （D6） and C24O have been performed using density functional theory （DFT） method. The geometric and electronic structures as well as the relative energies and thermal stabilities of various C24O2 isomers at the ground state have been calculated at the B3LYP/6-31G（d） level of theory. And the 1,4,2,5-C24O2 isomer was found to be the most stable geometry where two oxygen atoms were added to the longest carbon-carbon bonds in the same pentagon from a thermodynamic point of view. Based on the optimized neutral geometries, the vertical ionization potential and vertical electron affinity have been obtained. Meanwhile, the vibrational frequencies, IR spectrum, and 13C chemical shifts of various C24O2 isomers have been calculated and analyzed.

Different Thermal Stabilities of Cation Point Defects in LaAlO_3 Bulk and Films

Using the first-principles method, we investigate the thermal stability of cation point defects in LaAlO3 bulk and films. The calculated densities of states indicate that cation vacancies and antisites act as acceptors. The formation energies show that cation vacancies are energetically favorable in bulk LaAIO3 under O-rich conditions, while the AILa antisites are stable in reducing atmosphere. However, the same behavior does not appear in the case of LaAlO3 films. For LaO-terminated LaAlOa fihns, La or AI vacancies remain energetically favorable under O-rich and O-deficient conditions. For an AlO2-terminated surface, under O-rich condition the La interstitial atom is repelled from the outmost layer after optimization, which releases more stress leading to the decrease of total energy of the system. An AI interstitial atom has a smaller radius so that it can stay in distorted films and becomes more stable under O-deficient conditions, and the Al interstitial atoms can be another possible carrier source contribution to the conductivity of n-type interface under an ultrahigh vacuum. La and Al antisites have similar formation energy regardless of oxygen pressure. The results would be helpful to understand the defect structures of LaAlOa-related materials.

Thermal and hydrothermal stabilities of the alkali-treated HZSM-5 zeolites

HZSM-5 zeolites with the micro-mesopore hierarchical porosity have been prepared by the post-synthesis of alkali-treatment, and their thermal and hydrothermal stabilities were studied using DTA, XRD, and NH3-TPD characterization techniques. Compared to the unmodified zeolite, the thermal and hydrothermal stabilities of the alkali-treated ZSM-5 zeolites were slightly deteriorated because of the introduction of mesopores caused by the desilication. Nevertheless, the alkali-treated zeolite framework could be maintained until the temperature increased to 1175 ℃.

Syntheses,Crystal Structures and Thermal Stabilities of Two New Mixed Ligated Coordination Polymers with Rigid Dicarboxylate and Flexile N-donor Ligands

Two new coordination polymers,[Co（BIPA）（bpp）]（1） and [Zn（BIPA）（bpp）（H2O）]（2）（H2BIPA = 5-bromoisophthalic acid,bpp = 1,3-di（4-pyridyl）propane） have been synthesized via hydrothermal reactions.The two compounds were characterized by elemental analysis,IR spectra,TG analysis and single-crystal X-ray determination.Compound 1 crystallizes in triclinic,space group P1 with a = 9.0316（13）,b = 10.1179（14）,c = 11.8884（17） ,α = 68.022（2）,β = 84.749（2）,γ = 77.791（2）°,V = 984.5（2） 3,Z = 2,C21H17BrN2O4Co,Mr = 500.21,Dc = 1.687 g.cm-3,μ = 2.932 mm-1,S = 0.981,F（000） = 502,R = 0.0440 and wR = 0.1357 for 3773 observed reflections with I 2σ（I）.Compound 2 crystallizes in the monoclinic system,space group P21/c with a = 7.8466（10）,b = 27.483（4）,c = 9.6583（13） ,β = 96.663（3）°,V = 2068.8（5） 3,Z = 4,C21H19BrN2O5Zn,Mr = 524.66,Dc = 1.685 g.cm-3,μ = 3.155 mm-1,S = 0.969,F（000） = 1056,R = 0.0441 and wR = 0.0517 for 4058 observed reflections with I 2σ（I）.The two compounds are constructed from the BIPA2-and bpp ligands but they exhibit different kinds of one-dimensional chain structures.In 1,the chains are composed of the Co（Ⅱ） ions and BIPA2-ligands,and the chains are further extended into a 2D framework structure by π...π interactions of the benzene rings from the BIPA2-ligands between the adjacent chains.In 2,the chains are made up of Zn（Ⅱ） ions and BIPA2-ligands through another fashion,and the chains are further linked via hydrogen bonding interactions to yield a two-dimensional supramolecular layer structure.Furthermore,the bpp ligand features two kinds of different coordination modes in the two compounds.

Linear and Nonlinear QSPR Models for Predicting Thermal Stabilities of Nitroaromatic Compounds

Quantitative structure-property relationships（QSPRs） have been developed to predict the thermal stability for a set of 22 nitroaromatic compounds by means of the theoretical descriptors derived from electrostatic potentials on molecular surface. Several techniques, including partial least squares regression（PLS）, least-squares support vector machine（LSSVM） and Gaussian process（GP） have been utilized to establish the relationships between the structural descriptor and the decomposition enthalpy. The nonlinear LSSVM and GP models have proven to own a better predictive ability than the linear PLS method. Moreover, owing to its ability to handle both linear- and nonlinear-hybrid relationship, GP gives a stronger fitting ability and a better predictive power than LSSVM, and therefore could be well applied to developing QSPR models for the thermal stability of nitroaromatic explosives.

Formation of Natural Melanin/TiO_(2) Nanostructure Hybrids with Enhanced Optical,Thermal and Magnetic Properties as a Soft Material

The natural Melanin/TiO_(2) was synthesized by the use of ultrasonication under UV radiation.The influence of natural melanin on the structural,optical and thermal properties of TiO_(2) nanoparticles was investigated by using Fourier transform infrared spectroscopy,thermogravimetric analysis and UV-Vis spectroscopy.It was observed that incorporating natural melanin on TiO_(2) nanoparticles(TiO_(2)-Mel)occurred at 2.01 eV with a low value of Urbach energy around 100 meV indicating improvement in the crystalline structure.Magnetic measurement at room temperature showed diamagnetic behavior.Furthermore,thermal results showed that TiO_(2)-Mel is stable even at temperatures up to 400℃.According to the results obtained by the thermal stability of melanin with titanium dioxide,it can be a good candidate in many applications such as solar cells and optoelectronics.

Preparation and Thermal Stability of AlMoON Based Solar Selective Absorption Coating

AlMoON based solar selective absorption coatings were deposited on stainless steel substrate by magnetron sputtering.The coatings included infrared reflection layer Mo,absorption layer AlMoN,absorption layer AlMoON and antireflection layer AlMoO from bottom to top.The surface of the deposited coatings is flat without obvious defects.The absorptivity and emissivity are 0.896 and 0.09,respectively,and the quality factor is 9.96.After heat treatment at 500℃-36 h,the surface roughness of the coating increases,a small number of cracks and other defects appear,and the broken part is still attached to the coating surface.A certain degree of element diffusion occurs in the coatings,resulting in the decline of the optical properties of the coatings.The absorptivity and emissivity are 0.883 and 0.131,respectively,the quality factor is 7.06,and the PC value is 0.0335.The coatings do not fail under this condition and have certain thermal stability.

Significantly enhanced thermal stability of HMX by phase-transition lysozyme coating

A new robust bio-inspired route by using lysozyme aqueous solution for surface modification on 1,3,5,7-tetranitro-1,3,5,7-tetrazocane(HMX)was described in this paper.HMX crystals were coated by in situ phase transition of lysozyme(PTL)molecules.The HMX decorated by PTL was characterized by SEM,XRD,FTIR and XPS,demonstrating a dense core-shell coating layer.The coverage of lysozyme on HMX crystal was calculated by the ratio of sulfur content.The surface coverage increased from 60.5% to 93.5% when the content of PTL was changed from 0.5 wt% to 2.0 wt%,indicating efficient coating.The thermal stability of HMX was investigated by in situ XRD and DSC.The thermal phase transition temperature of HMX(β to δ phase)was delayed by 42℃ with 2.0 wt% PTL coating,which prevented HMX from thermal damage and sensitivity by the effect of PTL coating.After heating at 215℃,large cracks appeared in the naked HMX crystal,while the PTL coated HMX still maintained intact,with the impact energy of HMX dropped dramatically from 5 J to 2 J.However,the impact energy of HMX with 1.0 wt% and 2.0 wt% coating content(HMX@PTL-1.0 and HMX@PTL-2.0)was unchanged(5 J).Present results potentially enable large-scale fabrication of polymorphic energetic materials with outstanding thermal stability by novel lysozyme coating.

High-strength and thermally stable TiB_(2)-modified Al-Mn-Mg-Er-Zr alloy fabricated via selective laser melting

To increase the processability and plasticity of the selective laser melting(SLM)fabricated Al-Mn-Mg-Er-Zr alloys,a novel TiB_(2)-modified Al-Mn-Mg-Er-Zr alloy with a mixture of Al-Mn-Mg-Er-Zr and nano-TiB_(2) powders was fabricated by SLM.The pro-cessability,microstructure,and mechanical properties of the alloy were systematically investigated by density measurement,microstruc-ture characterization,and mechanical properties testing.The alloys fabricated at 250 W displayed higher relative densities due to a uni-formly smooth top surface and appropriate laser energy input.The maximum relative density value of the alloy reached(99.7±0.1)%,demonstrating good processability.The alloy exhibited a duplex grain microstructure consisting of columnar regions primarily and equiaxed regions with TiB_(2),Al6Mn,and Al3Er phases distributed along the grain boundaries.After directly aging treatment at a high tem-perature of 400℃,the strength of the SLM-fabricated TiB_(2)/Al-Mn-Mg-Er-Zr alloy increased due to the precipitation of the secondary Al6Mn phases.The maximum yield strength and ultimate tensile strength of the aging alloy were measured to be(374±1)and(512±13)MPa,respectively.The SLM-fabricated TiB_(2)/Al-Mn-Mg-Er-Zr alloy demonstrates exceptional strength and thermal stability due to the synergistic effects of the inhibition of grain growth,the incorporation of TiB_(2) nanoparticles,and the precipitation of secondary Al6Mn nanoparticles.

Construction of core@double-shell structured energetic composites with simultaneously enhanced thermal stability and safety performance

The poor thermal stability and high sensitivity severely hinder the practical application of hexanitrohexaazaisowurtzitane(CL-20).Herein,a kind of novel core@double-shell CL-20 based energetic composites were fabricated to address the above issues.The coordination complexes which consist of natural polyphenol tannic acid(TA) and Fe~Ⅲ were chosen to construct the inner shell,while the graphene sheets were used to build the outer shell.The resulting CL-20/TA-Fe~Ⅲ/graphene composites exhibited simultaneously improved thermal stability and safety performance with only 1 wt% double-shell content,which should be ascribed to the intense physical encapsulation effect from inner shell combined with the desensitization effect of carbon nano-materials from outer shell.The phase transition(ε to γ) temperature increased from 173.70 ℃ of pure CL-20 to 191.87℃ of CL-20/TA-Fe~Ⅲ/graphene composites.Meanwhile,the characteristic drop height(H_(50)) dramatically increased from 14.7 cm of pure CL-20 to112.8 cm of CL-20/TA-Fe~Ⅲ/graphene composites,indicating much superior safety performance after the construction of the double-shell structure.In general,this work has provided an effective and versatile strategy to conquer the thermal stability and safety issues of CL-20 and contributes to the future application of high energy density energetic materials.

Research progress on classification,source,application of phytosterol esters,and their thermal oxidation stability

Phytosterol esters can effectively decrease serum cholesterol concentration in the human body and prevent cardio-cerebrovascular diseases.It was found that phytosterol esters exhibited better solubility and bioavailability than free phytosterols.In recent years,phytosterol esters have attracted increasing attention.However,during food processing,phytosterol esters are susceptible to degradation at high temperatures,resulting in certain losses and formation of potentially harmful substances for humans.This paper reviews the relevant literatures and updates on the thermal oxidation stability of phytosterol esters in recent years from the following aspects:(i)Sources,physiological activities,and applications of phytosterol esters;(ii)Oxidation mechanism of phytosterol esters;(iii)Effects of phytosterols species,the volume of addition,food matrix,heating temperature and time,and antioxidants on the thermal loss and oxidation stability of phytosterol esters.The research progress on the safety of phytosterol esters is also discussed in detail.Additionally,the prospects for future research are highlighted.

Further Analysis of Machine Tool Dimensional Accuracy and Thermal Stability under Varying Floor Temperature

Machining is as old as humanity, and changes in temperature in both the machine’s internal and external environments can be of great concern as they affect the machine’s thermal stability and, thus, the machine’s dimensional accuracy. This paper is a continuation of our earlier work, which aimed to analyze the effect of the internal temperature of a machine tool as the machine is put into operation and vary the external temperature, the machine floor temperature. Some experiments are carried out under controlled conditions to study how machine tool components get heated up and how this heating up affects the machine’s accuracy due to thermally induced deviations. Additionally, another angle is added by varying the machine floor temperature. The parameters mentioned above are explored in line with the overall thermal stability of the machine tool and its dimensional accuracy. A Robodrill CNC machine tool is used. The CNC was first soaked with thermal energy by gradually raising the machine floor temperature to a certain level before putting the machine in operation. The machine was monitored, and analytical methods were deplored to evaluate thermal stability. Secondly, the machine was run idle for some time under raised floor temperature before it was put into operation. Data was also collected and analyzed. It is observed that machine thermal stability can be achieved in several ways depending on how the above parameters are joggled. This paper, in conclusion, reinforces the idea of machine tool warm-up process in conjunction with a carefully analyzed and established machine floor temperature variation for the approximation of the machine tool’s thermally stability to map the long-time behavior of the machine tool.

Development of Morus alba Reinforced Poly-Lactic Acid with Elevated Mechanical and Thermal Properties

This research investigates the mechanical and thermal properties of Morus alba combined with polylactic acid in comparison with other natural fibers. The study uses three different fiber and PLA compositions - 20%, 30%, and 40% respectively - to produce composite materials. In addition, another composite with the same fiber volume is treated with a 4% NaOH solution to improve mechanical properties. The composites are processed by twin-screw extrusion, granulation, and injection molding. Tensile strength measurements of raw fibers and NaOH-treated fibers were carried out using a single-fiber tensile test with a gauge length of 40 mm. It was observed that the NaOH surface treatment increases the resistance against tensile loading and exhibited improved properties for raw fiber strands. The diameter of the fibers was measured using optical microscopy. During this research, flexural tests, impact tests, differential scanning calorimetry (DSC), and heat deflection temperature measurements (HDT) were conducted to evaluate the mechanical and thermal properties of the developed composite samples. The results indicate that the mechanical properties of NaOH-treated Morus alba-reinforced polylactic acid outperform both virgin PLA samples and untreated Morus alba samples.

Effects of γ-Ray Irradiation on the Fatigue Strength, Thermal Conductivities and Thermal Stabilities of the Glass Fibres/Epoxy Resins Composites

Glass fibres/epoxy resins composites have been performed as ideal materials to make support instruments for high-energy and nuclear physics experiments. The effects of the 3,-ray irradiation on the fatigue strength, thermal conductivities and thermal stabilities of the glass fibres/epoxy resins composites were investigated. And a two-parameter fatigue life model was established to predict the fatigue life of the composites. Results revealed that the y-ray irradiation could probably result in the degradation of epoxy resins, but hardly damage to the glass fibres. And the γ-ray irradiation treatment could significantly affect the fatigue strength of the composites at a low-cycle fatigue stage, but seldom influence at a high-cycle fatigue stage. Furthermore, the fabricated glass fibres/epoxy resins composites after the γ-ray irradiation still presented excellent fatigue strength, ideal thermal conductivities, remarkable dimensional and thermal stabilities, which can meet the actual requirements of normal operation for supporting instruments under high-energy and nuclear physics experiments.

Ionic liquid electrolytes for sodium-ion batteries to control thermal runaway

Sodium-ion batteries are expected to be more affordable for stationary applications than lithium-ion batteries,while still offering sufficient energy density and operational capacity to power a significant segment of the battery market.Despite this,thermal runaway explosions associated with organic electrolytes have led to concerns regarding the safety of sodium-ion batteries.Among electrolytes,ionic liquids are promising because they have negligible vapor pressure and show high thermal and electrochemical stability.This review discusses the safety contributions of these electrolyte properties for high-temperature applications.The ionic liquids provide thermal stability while at the same time promoting high-voltage window battery operations.Moreover,apart from cycle stability,there is an additional safety feature attributed to modified ultra-concentrated ionic liquid electrolytes.Concerning these contributions,the following have been discussed,heat sources and thermal runaway mechanisms,thermal stability,the electrochemical decomposition mechanism of stable cations,and the ionic transport mechanism of ultra-concentrated ionic liquid electrolytes.In addition,the contributions of hybrid electrolyte systems consisting of ionic liquids with either organic carbonate or polymers are also discussed.The thermal stability of ionic liquids is found to be the main contributor to cell safety and cycle stability.For high-temperature applications where electrolyte safety,capacity,and cycle stability are important,highly concentrated ionic liquid electrolyte systems are potential solutions for sodium-ion battery applications.

Intrinsic thermal stability of inverted perovskite solar cells based on electrochemical deposited PEDOT

Thermal stability of perovskite materials is an issue impairing the long-term operation of inverted perovskite solar cells(PSCs). Herein, the thermal attenuation mechanism of the MAPb I3films that deposited on two different hole transport layers(HTL), poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate)(PEDOT:PSS) and poly(3,4-ethylenedioxythiophene)(PEDOT), is comprehensively studied by applying a heat treatment at 85℃. The thermal stress causes the mutual ions migration of I, Pb and Ag through the device, which leads to the thermal decomposition of perovskite to form Pb I2. Interestingly, we find that I ions tend to migrate more towards electron transport layer(ETL) during heating, which is different with the observation of I ions migration towards HTL when bias pressure is applied. Moreover, the use of electrochemical deposited PEDOT as HTL significantly decreases the defect density of MAPb I3films as compared to PEDOT:PSS supported one. The electrochemical deposition PEDOT has good carrier mobility and low acidity, which avoids the drawbacks of aqueous PEDOT:PSS. Accordingly, the inverted PSCs based on PEDOT show superior durability than that with PEDOT:PSS. Our results reveal detailed degradation routes of a new kind of inverted PSCs which can contribute to the understanding of the failure of thermal-aged inverted PSCs.

Thermal–moisture dynamics and thermal stability of active layer in response to wet/dry conditions in the central region of the Qinghai–Tibet Plateau,China

The amount of rainfall varies unevenly in different regions of the Qinghai-Tibet Plateau, with some regions becoming wetter and others drier. Precipitation has an important impact on the process of surface energy balance and the energy-water transfer within soils. To clarify the thermal-moisture dynamics and thermal stability of the active layer in permafrost regions under wet/dry conditions, the verified water-vapour-heat coupling model was used. Changes in the surface energy balance, energy-water transfer within the soil, and thickness of the active layer were quantitatively analyzed. The results demonstrate that rainfall changes significantly affect the Bowen ratio, which in turn affects surface energy exchange. Under wet/dry conditions, there is a positive correlation between rainfall and liquid water flux under the hydraulic gradient;water vapour migration is the main form under the temperature gradient, which indicates that the influence of water vapour migration on thermalmoisture dynamics of the active layer cannot be neglected. Concurrently, regardless of wet or dry conditions,disturbance of the heat transport by conduction caused by rainfall is stronger than that of convection by liquid water. In addition, when rainfall decreases by 1.5 times(212 mm) and increases by 1.5 times(477 mm), the thickness of the active layer increases by 0.12 m and decreases by 0.21 m, respectively. The results show that dry conditions are not conducive to the preservation of frozen soil;however, wet conditions are conducive to the preservation of frozen soil, although there is a threshold value. When this threshold value is exceeded, rainfall is unfavourable for the development of frozen soil.

Thermal and ignition properties of hexanitrostilbene(HNS) microspheres prepared by droplet microfluidics

HNS-IV(Hexanitrostilbene-IV) is the main charge of the exploding foil initiators(EFI), and the microstructure of the HNS will directly affect its density, flowability, sensitivity, and stability. HNS microspheres were prepared using droplet microfluidics, and the particle size, morphology, specific surface area, thermal performance, and ignition threshold of the HNS microspheres were characterized and tested. The results shown that the prepared HNS microspheres have high sphericity, with an average particle size of 20.52 μm(coefficient of variation less than 0.2), and a specific surface area of 21.62 m^(2)/g(6.87 m^(2)/g higher than the raw material). Without changing the crystal structure and thermal stability of HNS-IV, this method significantly enhances the sensitivity of HNS-IV to short pulses and reduces the ignition threshold of the slapper detonator to below 1000 V. This will contribute to the miniaturization and low cost of EFI.

Optimizing the morphology of all-polymer solar cells for enhanced photovoltaic performance and thermal stability

Due to the complicated film formation kinetics, morphology control remains a major challenge for the development of efficient and stable all-polymer solar cells(all-PSCs). To overcome this obstacle, the sequential deposition method is used to fabricate the photoactive layers of all-PSCs comprising a polymer donor PTzBI-oF and a polymer acceptor PS1. The film morphology can be manipulated by incorporating amounts of a dibenzyl ether additive into the PS1 layer. Detailed morphology investigations by grazing incidence wide-angle X-ray scattering and a transmission electron microscope reveal that the combination merits of sequential deposition and DBE additive can render favorable crystalline properties as well as phase separation for PTzBI-oF:PS1 blends. Consequently, the optimized all-PSCs delivered an enhanced power conversion efficiency(PCE) of 15.21%along with improved carrier extraction and suppressed charge recombination. More importantly, the optimized all-PSCs remain over 90% of their initial PCEs under continuous thermal stress at 65 °C for over 500 h. This work validates that control over microstructure morphology via a sequential deposition process is a promising strategy for fabricating highly efficient and stable all-PSCs.

17.13% Efficiency and Superior Thermal Stability of Organic Solar Cells Based on a Comb-Shape Active Blend

With rapid progress,organic solar cells(OSCs)are getting closer to the target of real application.However,the stability issue is still one of the biggest challenges that have to be resolved.Especially,the thermal stability of OSCs is far from meeting the requirements of the application.Here,based on the layer-by-layer(LBL)process and by utilizing the dissolubility nature of solvent and materials,binary inverted OSCs(ITO/AZO/PM6/BTP-eC9/MoO3/Ag)with comb shape active morphology are fabricated.High efficiency of 17.13%and simultaneous superior thermal stability(with 93%of initial efficiency retained in~9:00 h under 85℃in N_(2))are demonstrated,showing superior stability to reference cells.The enhancements are attributed to the formed optimal comb shape of the active layer,which could provide a larger D/A interface,thus more charge carriers,render the active blend a more stable morphology,and protect the electrode by impeding ion's migration and corrosion.To the best of our knowledge,this is the best thermal stability of binary OSCs reported in the literature,especially when considering the high efficiency of over 17%.