Phase stability,mechanical, and thermal properties of high-entropy transition and rare-earth metal diborides from first-principles calculations

The narrow composition design space of high-entropy transition metal diborides (HE TMB₂) limits their further development. In this study we designed six quaternary and quinary high-entropy transition metal and rare-earth diborides (HE TMREB₂) and investigated their phase stability using the energy distribution of the local mixing enthalpy of all possible configurations. The results show that both quaternary and quinary HE TMREB₂ have higher enthalpic driving forces, which facilitates the formation of single-phase AlB₂-type structures between TMB₂ and REB₂. Calculations of elastic constants show that the TMB₂ component has the greatest effect on the c₄₄ elastic constant and shear modulus G, while REB₂ significantly influences the bulk modulus B. Furthermore, LuB₂ and TmB₂ substantially affect the elastic modulus anisotropy of HE TMB₂. Rare-earth atoms in HE TMREB₂ can enhance the nonharmonic interactions between phonons, which results in a significant hindrance in the thermal transport of low-frequency phonons as well as an increase in the volume thermal expansion coefficients. Thus, the incorporation of REB₂ into HE TMB₂ has a significant impact on the phase stability and properties.     

Polylactide/graphite nanosheets/MWCNTs nanocomposites with enhanced mechanical, thermal and electrical properties

In this study, we have prepared a series of novel biodegradable polymer [polylactide (PLA)]-based nanocomposites using graphite nanosheets (GNs) and multi-walled carbon nanotubes (MWCNTs) by solution-blending technique and investigated their morphologies, structures, thermal stabilities, mechanical and dielectric properties, and electrical and thermal conductivities. Before preparation of the PLA/GNs/MWCNTs nanocomposites, the raw GNs used were endured a rapid expansion by thermal treatment. Temperature of this treatment had some obvious impacts on morphological changes of graphite nanosheets which were verified by means of scanning electron microscope (SEM) and X-ray diffraction (XRD) techniques. Resultant nanocomposites were characterized and evaluated by means of SEM, XRD, thermal conductivity measurements, tensile and impact tests, thermogravimetric analysis and dielectric measurements. Results obtained in this study indicated that thermal-expanded GNs in the presence of MWCNTs facilitate the formation of an appropriate conductive network in PLA matrix which resulted in a relatively low percolation threshold for thermal and electrical conductions of PLA/GNs/MWCNTs nanocomposites. Significant improvements in thermal and electrical conductivities, thermal stability and mechanical properties of PLA/GNs/MWCNTs nanocomposites obtained through the presence of both nanoparticles in PLA matrix were associated with their good co-dispersion and co-reinforcement effects. The macroscopic properties of nanocomposites were found to be strongly dependent on their components, concentrations, dispersion, and the resulted morphological structures.     

Flame retardant performance of a modified aluminum trihydroxide with increased thermal stability

A modified form of aluminum trihydroxide has been synthesized that is thermally stable to approximately 350°C. Flame retardant and smoke generation performance in low melting temperature thermoplastics, such as polyvinyl chloride, polypropylene, and ethylene vinylacetate, are comparable to unmodified ATH. The increased thermal stability also allows this material to be used in thermoplastics with higher melting temperatures, such as polycarbonate, polybutylene terephthalate, and polyphenylene oxide, where ATH cannot be used.     

过渡金属氧化物对苯并恶嗪热稳定性影响研究

将过渡金属氧化物TiO2、MnO2、CuO、Cu2O、ZnO、ZrO2以及Y2O3、CeO2、Sm2O3、Gd2O3分别添加到苯酚/4,4'-二苯甲烷二胺型苯并恶嗪(BB)中间体中,制备了过渡金属氧化物/BB固化物,通过FTIR、TGA和DMA分析研究了过渡金属氧化物对苯并恶嗪热稳定性的影响。结果表明,这些氧化物的添加不改变BB固化物的化学结构;除ZnO外,其他氧化物均使BB的热稳定性和800℃残炭率降低,这是由于过渡金属氧化物与BB中N原子间配位作用的形成削弱了C—N键,使其更易断裂。     

An investigation into the thermal stability of PVC/montmorillonite composites

An effective stabilizing system for poly (vinyl chloride) (PVC)/clay composites was established. Different types of stabilizers, i.e., organotin, calcium/zinc, barium/zinc, and an epoxy costabilizer, were investigated. The combination of the organotin stabilizer and the epoxy costabilizer was the most effective stabilizing system. Different grades of Cloisite nanoclays were investigated. Cloisite Na did not cause premature degradation of PVC. Cloisite 10A strongly accelerated the degradation of PVC because of the presence of excess surfactant, while a PVC/Cloisite 30B system showed much better thermal stability because there was less organic impurity in the Cloisite 30B. Phosphonium‐modified clays were also prepared. They showed better thermal stability than ammonium‐modified clays, but the drying conditions still need to be optimized in order to produce a dispersible clay powder. J. VINYL ADDIT. TECHNOL., 2011. © 2011 Society of Plastics Engineers     

Physical,mechanical, and thermal properties of micronized organo‐montmorillonite suspension modified wood flour/poly(lactic acid) composites

In this study, micronized organo‐montmorillonite (OMMT) suspension was prepared with sodium‐montmorillonite (Na‐MMT), didecyl dimethyl ammonium chloride, and dispersant polyethylene glycol 1000 by a ball‐milling process. Then, wood flours (WFs) were impregnated with prepared OMMT suspension at a concentration of 0.5, 1.0, 2.0, or 4.0%. WFs were characterized by X‐ray diffraction and scanning electron microscopy. The hygroscopicity of WF was investigated by a vapor adsorption method. WFs were, respectively, blended with poly (lactic acid) (PLA) to produce WF/PLA composites. Thereafter, physical, mechanical, and thermal properties of the composites were tested. The results showed that a great amount of OMMT attached on the surface of WF, partly penetrating into the microstructure of WF. Owing to the hydrophobicity of OMMT, the vapor adsorption of OMMT‐modified WF decreased. The composite which was produced by WF treated with 0.5% OMMT suspension, showing an increment in the physical, mechanical, and thermal properties. However, OMMT should not be overloaded. Otherwise, the accumulation of OMMT might cause poor interfacial adhesion between WF and PLA matrix. POLYM. COMPOS., 36:731–738, 2015. © 2014 Society of Plastics Engineers     

Morphology,thermal, and mechanical properties of flame‐retardant silicone rubber/montmorillonite nanocomposites

Flame‐retardant methyl vinyl silicone rubber (MVMQ)/montmorillonite nanocomposites were prepared by solution intercalation method, using magnesium hydroxide (MH) and red phosphorus (RP) as synergistic flame‐retardant additives, and aero silica (SiO₂) as synergistic reinforcement filler. The morphologies of the flame‐retardant MVMQ/montmorillonite nanocomposites were characterized by environmental scanning electron microscopy (ESEM), and the interlayer spacings were determined by small‐angle X‐ray scattering (SAXS). In addition to mechanical measurements and limited oxygen index (LOI) test, thermal properties were tested by thermogravimetric analysis (TGA). The decomposition temperature of the nanocomposite that contained 1 wt % montmorillonite can be higher (129°C) than that of MVMQ as basal polymer matrix when 5% weight loss was selected as measuring point. This kind of silicone rubber nanocomposite is a promising flame‐retardant polymeric material. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3275–3280, 2006     

Improvement of mechanical,thermal and antimicrobial properties of organically modified montmorillonite loaded polycaprolactone for food packaging

The aim of this study is to evaluate the biodegradable packaging materials which will be an alternative to traditional synthetic packaging materials. For this purpose, packaging films containing polycaprolactone (PCL), montmorillonite (MMT), and organically modified montmorillonite (OMMT) were prepared by solution casting method, and the mechanical, physical, structural, antimicrobial, and antifungal properties of these films were examined. Cetyl trimethyl ammonium bromide (CTAB) was used for the modification of montmorillonite. The structural properties of the prepared films were characterized by attenuated total reflection-Fourier transform infrared, X-ray powder diffraction, thermogravimetric analysis, and scanning electron microscopy. The PCL/OMMT structure was found to be thermally more stable than the PCL/MMT structure. The addition of OMMT to PCL improved the thermal and mechanical properties of the films compared with the pure PCL and PCL/MMT films. In addition, adding MMT/OMMT to the PCL caused an increase in the hardness of the films. In the antimicrobial analysis, while no inhibition effect was observed in PCL/MMT films, PCL/OMMT films showed inhibition effect against Staphylococcus aureus. Antifungal tests performed with the prepared films showed that the film-wrapped bread did not deteriorate for 40 days. It is thought that PCL/MMT and PCL/OMMT films prepared in this study will provide an advantage in applications as packaging material.     

Electrocatalysis and detection of nitrite on a polyaniline‐Cu nanocomposite‐modified glassy carbon electrode

A polyaniline (PANI)‐Cu nanocomposite‐modified electrode was fabricated by the electrochemical polymerization of aniline and the electrodeposition of copper under constant potentials on a glassy carbon electrode (GCE), respectively. Scanning electron microscope result shows that the PANI‐Cu composite on the surface of the GCE displays the nanofibers having an average diameter of about 80 nm with lengths varying from 1.1 to 1.2 μm. The electrode exhibits enhanced electrocatalytic behavior to the reduction of nitrite compared to the PANI‐modified GCE. The effects of applied potential, pH value of the detection solution, electropolymerization charge, temperature, and nitrite concentration on the current response of the composite‐modified GCE were investigated and discussed. Under optimal conditions, the PANI‐Cu composite‐modified GCE can be used to determine nitrite concentration in a wide linear range (n = 18) of 0.049 and 70.0 μM and a limit of detection of 0.025 μM. The sensitivity of the electrode was 0.312 μA μM^?1 cm^?2. The PANI‐Cu composite‐modified GCE had the good storage stability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Multiwalled carbon nanotube/montmorillonite hybrid filled ethylene‐co‐vinyl acetate nanocomposites with enhanced mechanical properties,thermal stability,and dielectric response

Homogeneous multiwalled carbon nanotube/montmorillonite hybrid filler (HMM) dispersion was prepared by co‐ultrasonication and was subsequently used to prepare ethylene‐co‐vinyl acetate (EVA) nanocomposites by solution blending method. XRD and TEM analysis of HMM confirm significant interaction between the montmorillonite (MMT) layers and multiwalled carbon nanotubes (MWCNT) in line with previous reports. Analysis of the nanocomposites shows the constituent fillers to be homogeneously dispersed in EVA matrix. Mechanical properties of neat EVA are remarkably improved with HMM content up to 3 wt% followed by reversion. Maximum improvement observed in tensile strength, elongation at break, and toughness are 424%, 109%, and 1122%, respectively. Results show maximum thermal stability at 4 wt% and best dielectric response at 1 wt% HMM content. Exceptional mechanical and dielectric properties of EVA nanocomposites attained may be attributed to homogeneous dispersion of fillers and improved polymer–filler interaction. Comparison shows excellent synergy between MWCNT and MMT towards mechanical reinforcement of EVA. POLYM. ENG. SCI., 58:1155–1165, 2018. © 2017 Society of Plastics Engineers     

FT-IR spectroscopic studies of metal nitrates supported on a modified montmorillonite clay

Diffuse reflectance FT-IR spectra of transition metal nitrates on a modified montmorillonite clay show strong absorptions due to the presence of NO⁺ and NO^– ions. An attempt has been made to explain the mechanism of activation of the metal nitrates by the clay.     

Development of high‐performance epoxy/clay nanocomposites by incorporating novel phosphonium modified montmorillonite

Novel organoclays were synthesized by several kinds of phosphonium cations to improve the dispersibility in matrix resin of composites and accelerate the curing of matrix resin. The possibility of the application for epoxy/clay nanocomposites and the thermal, mechanical, and adhesive properties were investigated. Furthermore, the structures and morphologies of the epoxy/clay nanocomposites were evaluated by transmission electron microscopy. Consequently, the corporation of organoclays with different types of phosphonium cations into the epoxy matrix led to different morphologies of the organoclay particles, and then the distribution changes of silicate layers in the epoxy resin influenced the physical properties of the nanocomposites. When high‐reactive phosphonium cations with epoxy groups were adopted, the clay particles were well exfoliated and dispersed. The epoxy/clay nanocomposite realized the high glass‐transition temperature (T_g) and low coefficient of thermal expansion (CTE) in comparison with those of neat epoxy resin. On the other hand, in the case of low‐reactive phoshonium cations, the dispersion states of clay particles were intercalated but not exfoliated. The intercalated clay did not influence the T_g and CTE of the nanocomposite. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Electrochemical performance and thermal stability of the electrospun PTFE nanofiber separator for lithium‐ion batteries

Separator is a very important set of lithium‐ion batteries. At present, low porosity and poor thermal stability are two major disadvantages of separator. In this work, we first apply electrospinning method to prepare the Polytetrafluoroethylene (PTFE) nanofiber separator, which has the advantages of electrospinning method and PTFE materials. The effect of the PTFE nanofiber separator is investigated by scanning electron microscope, Capillary Flow Porometer, thermogravimetric–differential scanning calorimeter, linear sweep voltammeter, AC impedance, and charge/discharge cycling tests. The results demonstrate that the PTFE nanofiber separator has a special fiber structure made from PTFE particles gathering one by one along the fibers. Moreover, the PTFE nanofiber separator exhibits several advantages, including suitable pore diameter, uniform pore size distribution, high porosity, and electrolyte uptake, which enhance the ionic conductivity. The thermal stability of the PTFE nanofiber separator is much better than that of the conventional polyolefin separator. The Li/LiCoO₂ cell equipped with PTFE nanofiber separator exhibits excellent rate performance and first charge–discharge specific capacity of 142 and 131 mA h g^?1, respectively, accompanied by relatively stable cycle performance at 0.2 C rate. It is supposed to be a candidate for application in lithium‐ion batteries. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46508.     

Effect of oligomeric‐modified montmorillonite on morphology and properties of polycarbonate/montmorillonite nanocomposites

Low‐molecular‐weight copolymers of styrene and vinylbenzyl ammonium salts (oligomeric surfactant) were used to modify montmorillonite (MMT). The oligomeric‐modified MMT showed good thermal stability, which made it suitable to be used for preparing polycarbonate(PC)/MMT nanocomposites at high temperature. A different series of PC/MMT nanocomposites had been prepared by melt processing using a twin screw extruder. The effect of oligomeric surfactant structure and clay loading on the morphology, mechanical property, thermal stability, and color appearance of the nanocomposites were explored. The results of X‐ray diffraction and transmission electron microscopy analyses indicated that the PC/MMT nanocomposites had partially exfoliated structures. The PC/MMT nanocomposites were found to retain light colored, which was important for optical application. Compared to neat PC, the nanocomposites showed better properties of thermal stability and heat insulation. The mechanical properties of the nanocomposites are significantly enhanced by incorporating clay into the PC matrix. The tensile strength of nanocomposites with 2 wt% clay content was up to 55 MPa, which was much higher than that of the neat PC (37 MPa). The maximum tensile modulus value was 19% higher than that of neat PC. POLYM. COMPOS., 2013. © 2013 Society of Plastics Engineers     

Preparation and characterization of phosphonium montmorillonite with enhanced thermal stability

Quaternary phosphonium cations (hexadecyl tributyphosphonium; tetradecyl tributylphosphonium; tetraphenylphosphonium; methyl triphenylphosphonium; ethyl triphenylphosphonium and propyl triphenylphosphonium) were intercalated into montmorillonite (MMT) rich bentonite of Indian origin, by ion exchange reaction. The phosphonium MMT were characterized by Fourier transform infrared spectroscopy (FTIR), powder X-ray diffraction analysis (PXRD), particle size distribution (PSD) and thermogravimetric analysis (TGA). The phosphonium cations significantly influenced the particle size distribution. With longer alkyl chain finer particles were formed. The tetrabutylphosphonium and tetraphenylphosphonium MMT showed enhanced thermal stability (300–400 °C) and may be potentially useful materials for melt processing of polymer/layered silicates nanocomposites.     

Improvement in voltage,thermal, mechanical stability and ion transport properties in polymer‐clay nanocomposites

We report novel results on optimization of intercalated polymer‐clay nanocomposite endowed with desirable properties like, (i) very high ionic conductivity (～ 10^?3 S cm^?1) at room temperature, (ii) substantial improvement in voltage stability (～ 5.6 V), mechanical stability (25 MPa), and thermal stability (250°C) (iii) t_ion ～ 99% and cation transport number (t_Li+) ～ 67%: Intercalation of polymer salt (PAN)₈LiCF₃SO₃ complex into dodecylamine modified montmorillonite clay (DMMT) nanometric channels has been confirmed by X‐ray diffraction and Transmission electron microscopy analysis. Complex impedance spectroscopy suggests bulk electrical conduction in the high frequency region and electrode polarization effect at the low frequencies. The experimental value of conductivity, voltage, and mechanical stability is observed to be invariably higher in polymer nanocomposite film when compared with clay free polymer‐salt complex film. The same is true for cation transport. The optimized polymer film serves dual purpose of electrolyte and separator in energy storage devices. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Thiocarbohydrazide‐modified chitosan as anticorrosion and metal ion adsorbent

To explore the application of chitosan (CS) derivatives in anticorrosion and adsorption, thiocarbohydrazide‐modified chitosan (TCHECS) derivative was synthesized and characterized. The preliminary electrochemical measurements of the behaviors of 304 steel and Cu sheets in 2% HAc (v/v) containing TCHECS, chitosan (CS), and hydrazine cross‐linked epoxy‐N‐phthaloylchitosan (HECS) had been performed. The short‐term electrochemical tests show that the new compound can act as a mixed‐type metal anticorrosion inhibitor; its inhibition efficiency is 88% when the concentration was 30 mg/L. The preliminary adsorption studies for sorbents TCHECS and HECS on a metal ion mixture aqueous solution were also performed. The results show that TCHECS can absorb As (V), Ni (II), Cu (II), Cd (II), and Pb (II) efficiently at pH 9; the removal of the As (V), Ni (II), Cu (II), Cd (II), and Pb (II) are around 55.6–99.9%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40671.     

Enhanced mechanical and thermal properties of polyimide/organically modified montmorillonite hybrid film based on stable poly(amic acid) ammonium salt

In this study, polyimide/organically modified montmorillonite (PI/OMMT) hybrid film was prepared by in situ polymerization from the stable poly(amic acid) ammonium salt/OMMT (PAAS/OMMT) precursor hybrid. PAAS was obtained by incorporating calculated triethylamine into terpolymer poly(amic acid) (PAA), which was synthesized by pyromellitic dianhydride (PMDA), 4,4′‐oxydianiline and p‐phenylenediamine in dimethylacetamide (DMAc). OMMT as a type of layered clays was prepared through surface treatment of montmorillonite (MMT) with 1‐hexadecylamine. Mechanical property measurements of PI/OMMT hybrid film indicated that the addition of 5 wt% of OMMT increased the Young's modulus of PI film up to 11.24 GPa, which is 58% higher than the pristine PI film from PAAS. Besides, the tensile strength increased to 168.36 MPa, which was higher than that of PI film derived from PAA (164.3 MPa) and PI film derived from PAAS (145.2 MPa). Moreover, the thermal stabilities of PI/OMMT hybrid film with appropriate OMMT content were also better than those of original PI films. POLYM. COMPOS., 34:2076–2081, 2013. © 2013 Society of Plastics Engineers     

Preparation and characterization of PVC/montmorillonite nanocomposites—A review

This article presents an overview of the preparation and characterization of poly(vinyl chloride)/montmorillonite (PVC/MMT) nanocomposites. Different methods of PVC/MMT nanocomposite preparation are discussed. The incorporation of MMT into the PVC matrix results in an increase of thermal stability and induces changes in the mechanical properties. However, the properties of PVC/MMT nanocomposites depend strongly on the MMT organic modification procedure that governs the extent of MMT penetration by PVC macrochains and plays an important role with regard to the morphology formation. Flammability as well as other properties—barrier, optical, etc.—of PVC/MMT nanomaterials are also described. Finally, a future outlook is given. J. VINYL ADDIT. TECHNOL., 2009. © 2009 Society of Plastics Engineers     

Experimental investigation of mechanical,thermal, and ablation performance of ZrO2/SiC modified C-Ph composites

In this study, an effort has been made to improve the mechanical, thermal, and ablation performance of carbon-phenolic (C-Ph) composites. The ZrO₂, SiC, and ZrO₂/SiC hybrid fillers were synthesized using sol-gel method followed by individual incorporation into C-Ph composites. The thermal stability and flexural strength of these C-Ph composites were analyzed using thermogravimetry analysis and three-point bending test, respectively. A significant improvement in the flexural strength and modulus of the reinforced C-Ph composites was observed and also exhibited the higher thermal stability. The oxyacetylene flame test was conducted to measure the ablation behavior of these filler reinforced C-Ph composites under a heat flux of 4.0 MW/m² for 60 seconds. ZrO₂/SiC0.5 reinforcement in the C-Ph composite decreased the linear and mass ablation rates by 46% and 22%, respectively when compared with pure C-Ph composite. The surface morphology analysis revealed that the burnt composite covered with the ZrC ceramic phase and SiO₂ bubble-like structure, which could have improved the ablation resistance of composites. These results were found well within the acceptable range when using the surface energy dispersive spectroscopy and X-ray diffraction analysis.