Investigation of surface and thermogravimetric characteristics of carbon-coated iron nanopowder

Demand for high-density press and sinter components is increasing day by day. Of the different ways to improve the sinter density, the addition of nanopowder to the conventional micrometer-sized metal powder is an effective solution. The present investigation is aimed at studying the surface chemistry of iron nanopowder coated with graphitic carbon, which is intended to be mixed with the conventional iron powder. For this purpose, iron nanopowder in the size range of 30 nm to submicron (less than 1 micron) was investigated using thermogravimetry at different temperatures: 400°C, 600°C, 800°C, 1000°C, and 1350°C. The X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES), and high-resolution scanning electron microscopy (HR-SEM) were used for characterizing the powder as well as samples sintered at different temperatures. The presence of iron, oxygen, carbon, chromium, and zinc were observed on the surface of the nanopowder. Iron was present in oxide state, although a small metallic iron peak at 707 eV was also observed in the XPS spectra obtained from the surface indicating the oxide scale to be maximum of about 5 nm in thickness. For the sample treated at 600°C, presence of manganese was observed on the surface. Thermogravimetry results showed a two-step mass loss with a total mass loss of 4 wt.% when heated to 1350°C where the first step corresponds to the surface oxide reduction.     

Interactive Thermal Effects on Metal–Organic Framework Polymer Composite Membranes

Polymeric membranes are important tools for intensifying separation processes in chemical industries, concerning strategic tasks such as CO₂ sequestration, H₂ production, and water supply and disposal. Mixed‐matrix and supported membranes have been widely developed; recently many of them have been based on metal–organic frameworks (MOFs). However, most of the impacts MOFs have within the polymer matrix have yet to be determined. The effects related to thermal behavior arising from the combination of MOF ZIF‐8 and polysulfone have now been quantified. The catalyzed oxidation of the polymer is strongly affected by the MOF crystal size and distribution inside the membrane. A 16 wt % 140 nm‐sized ZIF‐8 loading causes a 40 % decrease in the observed activation energy of the polysulfone oxidation that takes place at a temperature (545 °C) 80 °C lower than in the raw polymer (625 °C).     

Thermal Decomposition Kinetics of Some Di‐ and Triorganotin(IV) Carboxylates Derived from para‐Nitrophenylethanoic Acid

Thermogravimetric (TG) investigations of organotin(IV) carboxylates with the general formula R_mSnL_4−m (where R=CH₃, C₂H₅, n‐C₄H₉, C₆H₅, cyclo‐C₆H₁₁, n‐C₈H₁₇, m=2, 3, and L=para‐nitrophenylethanoate anion) have been performed. Derivative thermogravimetry (DTG) and differential thermal analysis (DTA) techniques, Horowitz‐Metzger method and the fundamental thermodynamic relations are used to evaluate the thermokinetic parameters of each thermal degradation pattern. Results reveal that the thermal stability is functional to Sn C and Sn O bonds. In the case of R₂SnL₂, activation energy, reaction order and pre‐exponential factor associated with the bulk degradation processes increase as the alkane chain length increases. Hence, Oct₂SnL₂ is thermally more stable than Bu₂SnL₂, which in turn is more resistant to thermal dissociation than Et₂SnL₂. The same phenomenon is not observed for R₃SnL compounds because their degradation is highly irregular. Furthermore, R₂SnL₂ has larger values of kinetic parameters than those of corresponding triorganotin(IV) para‐nitrophenylethanotes. Thermodynamic parameters of these compounds also reinforce the above facts.     

Comparative evolved gas analytical and structural study on trans-diammine-bis(nitrito)-palladium(II) and platinum(II) by TG/DTA–MS, TG–FTIR, and single crystal X-ray diffraction

Detailed study on identification and thermal decomposition of solid title compounds 1 and 2 crystallized from the used aqueous ammonia solutions of Pd(NH₃)₂(NO₂)₂ and Pt(NH₃)₂(NO₂)₂, has been carried out. Beyond the composition of complexes 1 and 2, their trans square planar configuration have already been recognized by reference IR spectra and powder XRD patterns, nevertheless their exact molecular and crystal structure as of trans-Pd(NH₃)₂(NO₂)₂ (1, Pd-NN) and trans-Pt(NH₃)₂(NO₂)₂ (2, Pt-NN) has been determined by single crystal X-ray diffraction (R = 0.0515 and 0.0341), respectively. Despite their compositional and configuration analogy, they crystallize in different crystal systems and space groups. The crystals of 1 (Pd-NN) are triclinic (space group No. 2, P-1, a = 5.003(1) Å, b = 5.419(1) Å, c = 6.317(1) Å, α = 91.34(2)°, β = 111.890(10)°, γ = 100.380(10)°), while those of 2 (Pt-NN) are monoclinic (space group No. 5, C2, a = 7.4235(16) Å, b = 9.130(2) Å, c = 4.4847(10) Å, β = 99.405(7)°).The pyrolytic processes of 1 and 2 (which might be sensitive to shock and heat) have been followed by simultaneous thermogravimetric and differential thermal analysis (TG/DTA), while the evolved gaseous species have been traced in situ by online coupled TG/DTA–EGA–MS and TG–EGA–FTIR instruments in He and air. Pd and Pt powders, forming as final solid products in single step, are captured and checked by TG and XRD. Whilst the unified evolved gas analyses report evolution of N₂, H₂O, NH₃, N₂O, NO, and NO₂ gases as gaseous product components in the exothermic decomposition of both trans-Pd(NH₃)₂(NO₂)₂ (1) and trans-Pt(NH₃)₂(NO₂)₂ (2) starting from ca. 230 and 220 °C, in sealed crucibles with a pinhole on the top, respectively.     

Comparison of isothermal and non-isothermal chemiluminescence and differential scanning calorimetry experiments with benzoyl peroxide

Difference in the kinetics of chemiluminescence (CL) and differential scanning calorimetry records for decomposition of originally solid benzoyl peroxide continuing as a melt reaction was outlined. While the main portion of heat measured by DSC is released in the spontaneous decomposition of benzoyl peroxide starting as a homolytic scission of peroxidic bonds, the CL light emission in oxygen comes presumably from the subsequent disproportionation reaction of polyphenyl peroxyl radicals and monitors the induced decomposition of peroxide. Thermogravimetry revealed that oxygen remains partially bound to the products of benzoyl peroxide decomposition.     

Kinetics of combustion of oil shale with polystyrene

The combustion kinetics of Göynük oil shale, polystyrene and several polystyrene-oil shale blends were investigated by thermogravimetric analysis in the present study. Experiments were conducted at non-isothermal conditions with a heating rate of 5, 10 and 20 K min^?1 in the 298–1173 K temperature interval under an air atmosphere. Differential thermogravimetric data were analyzed by two different models. Effects of blending ratio of oil shale and polystyrene and heating rate on the combustion kinetics were investigated. Kinetic parameters were determined and the results were discussed.     

Thermogravimetric analysis of cellulose insulation and determination of activation energy of its thermo‐oxidation using non‐isothermal,model‐free methods

The aim of the work was to determine the effect of heating rate on initial decomposition temperature and phases of thermal decomposition of cellulose insulation. The activation energy of thermo‐oxidation of insulation was also determined. Individual samples were heated in the air flow in the thermal range of 100°C to 500°C at rates from 1.9°C min^?1 to 20.1°C min^?1. The initial temperatures of thermal decomposition ranged from 220°C to 320°C, depending on the heating rate. Three regions of thermal decomposition were observed. The maximum rates of mass loss were measured at the temperatures between 288°C and 362°C. The activation energies, which achieved average values between 75 and 80.7 kJ mol^?1, were calculated from the obtained results by non‐isothermal, model‐free methods. Copyright © 2014 John Wiley & Sons, Ltd.     

Transformation-Governed Heating Techniques in Thermal Analysis I.

The author gives a detailed survey on thermogravimetric investigations under quasi-isothermal — quasi-isobaric conditions (Q-TG). According to the principle of the technique the heating of the sample is governed by the transformation itself according to the feed-back principle in a way that the transformations should take place at a strictly constant rate, slower by orders of magnitude than in the case of the conventional techniques. Due to this, the transformations take place under ideal conditions, near to physico-chemical requirements.Based on the obtained advantageous results further methods were elaborated, like thermo-dilatometry (Q-TD), evolved gas analysis (Q-EGA) and microdistillation under quasi-isothermal conditions.The second part of the present review deals with DTA and DSC techniques under quasi-isothermal conditions elaborated recentlyThis revised version was published online in November 2005 with corrections to the Cover Date.     

Thermal Decomposition Kinetics of Some Metal Complexes of 2,3-Hydroxyimino-4-phenyl-6-phenyazo-1-thia-4,5-diazacyclohexa-5-diene

The Ni(II), Cu(II) Co(II) and Zn(II) complexes of 2,3‐hydroxyimino‐4‐phenyl‐6‐phenyazo‐1‐thia‐4,5‐diaza‐ cyclohexa‐5‐diene (H₂L) were synthesized. Thermal behavior of these complexes was studied in dynamic nitrogen atmosphere by TA (thermogravimetric analysis), DTA (differential thermal analysis) and DTG (differential thermal gravimetry) techniques. The reaction order, the activation energies, the entropies, the enthalpies, the free energies, and the pre‐exponential factors of the thermal decomposition reactions were calculated from the thermogravimetric curves. The kinetic analysis of the thermogravimetric data was performed by using several methods such as MacCallum‐Tanner (MT), van Krevelen (vK), Madhusudanan‐Krishnan‐Ninan (MKN), Wanjun‐Yuwen‐Hen‐Cunxin (WYHC), Horowitz‐Metzger (HM) and Coats‐Redfern method (CR) based on the single heating rate. Most appropriate methods were determined for each decomposition step according to the least‐square linear regression. The Ni(II), Cu(II) Co(II) and Zn(II) complexes displayed one‐ or two‐stage decomposition pattern when heating in a dynamic nitrogen atmosphere and metal oxides remained as end products of the complexes. The characterization of the end products of the decomposition was performed by X‐ray diffraction.