Constant rate thermal analysis for thermal stability studies of polymers

This paper explores the relationship between the shapes of temperature-time curves obtained from experimental data recorded by means of constant rate thermal analysis (CRTA) and the kinetic model followed by the thermal degradation reaction. A detailed shape analysis of CRTA curves has been performed as a function of the most common kinetic models. The analysis has been validated with simulated data, and with experimental data recorded from the thermal degradation of polytetrafluoroethylene (PTFE), poly(1,4-butylene terephthalate) (PBT), polyethylene (PE) and poly(vinyl chloride) (PVC). The resulting temperature-time profiles indicate that the studied polymers decompose through phase boundary, random scission, diffusion and nucleation mechanisms respectively. The results here presented demonstrate that the strong dependence of the temperature-time profile on the reaction mechanism would allow the real kinetic model obeyed by a reaction to be discerned from a single CRTA curve.     

Oxyreactive thermal analysis

The paper presents the applicability of Oxyreactive Thermal Analysis (OTA) for the investigation of different kinds of carbon matter. For comparative reasons and more precise interpretation, along with OTA some physico-chemical properties of analyzed materials were used as the methods commonly applied for the investigations. The carbon materials of both natural (anthracites, graphite and diamonds) and synthetic origin (active carbon, glass carbon, expanded graphite, soot and synthetic diamonds) were investigated. It was stated that there is close relationship between structure parameters and physico-chemical properties and the thermal reactivity within the investigated groups of carbon matters. The results show that OTA can be accepted as a good investigative way for such materials. This revised version was published online in July 2006 with corrections to the Cover Date.     

Controlled-rate thermal analysis

Controlled-rate thermal analysis (CRTA) and differential scanning calorimetry (DSC) were used to investigate the adsorbed water layers and the surface properties of different commercial activated carbons. A simple method is proposed to obtain information on the properties of the adsorbed water film and the surface heterogeneity of the materials studied. This method utilizes TG mass loss and the first derivative of the DTG mass loss curves with respect to temperature and time, obtained during programmed liquid thermodesorption. The obtained TG mass loss curves, which reflect the energetic heterogeneity, consisted of steps and inflections which were associated with the mechanism of wetting of the solid surfaces. The heights of these steps and inflections depend on the adsorption capacity, the adsorption potential and the nature and number of the active centers of the carbon samples studied. The values of the total porosity and the surface phase capacity obtained by this method are in good agreement with those estimated on the basis of independent methods. The behaviour of water/carbon samples was studied by means of DSC at subambient and elevated temperatures. The experimental results provided novel data on the structural heterogeneity, the thermal stability of the water/carbon interface and its phase and structural transitions.Support from the Research Council of Kent State University (Ohio, USA) is acknowledged. The author is pleased to thank Drs M. Jaroniec, R. K. Gilpin, J. Choma and R. Dobrowolski for fruitful discussions and the active carbon samples.     

Unimolecular thermal fragmentation of ortho-benzyne

The ortho-benzyne diradical, o-C(6)H(4) has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments: o-C(6)H(4)+Delta--> products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix-isolation Fourier transform infrared absorption spectroscopy, and (iii) chemical ionization mass spectrometry. At the threshold dissociation temperature, o-benzyne cleanly decomposes into acetylene and diacetylene via an apparent retro-Diels-Alder process: o-C(6)H(4)+Delta-->HC triple bond CH+HC triple bond C-C triple bond CH. The experimental Delta(rxn)H(298)(o-C(6)H(4)-->HC triple bond CH+HC triple bond C-C triple bond CH) is found to be 57+/-3 kcal mol(-1). Further experiments with the substituted benzyne, 3,6-(CH(3))(2)-o-C(6)H(2), are consistent with a retro-Diels-Alder fragmentation. But at higher nozzle temperatures, the cracking pattern becomes more complicated. To interpret these experiments, the retro-Diels-Alder fragmentation of o-benzyne has been investigated by rigorous ab initio electronic structure computations. These calculations used basis sets as large as [C(7s6p5d4f3g2h1i)H(6s5p4d3f2g1h)] (cc-pV6Z) and electron correlation treatments as extensive as full coupled cluster through triple excitations (CCSDT), in cases with a perturbative term for connected quadruples [CCSDT(Q)]. Focal point extrapolations of the computational data yield a 0 K barrier for the concerted, C(2v)-symmetric decomposition of o-benzyne, E(b)(o-C(6)H(4)-->HC triple bond CH+HC triple bond C-C triple bond CH)=88.0+/-0.5 kcal mol(-1). A barrier of this magnitude is consistent with the experimental results. A careful assessment of the thermochemistry for the high temperature fragmentation of benzene is presented: C(6)H(6)-->H+[C(6)H(5)]-->H+[o-C(6)H(4)]-->HC triple bond CH+HC triple bond C-C triple bond CH. Benzyne may be an important intermediate in the thermal decomposition of many alkylbenzenes (arenes). High engine temperatures above 1500 K may crack these alkylbenzenes to a mixture of alkyl radicals and phenyl radicals. The phenyl radicals will then dissociate first to benzyne and then to acetylene and diacetylene.     

Emanation thermal analysis

A high pressure differential thermal analysis (DTA) apparatus is described which is capable of operation in the pressure range up to 500 MPa and at temperatures from 25 to 300°C. The requirements for quantitative DTA are examined. The apparatus enables the determination of heat of transition under high pressure by using small samples.     

Mechanism of thermal dehydrochlorination

Co(II), Ni(II), Cu(II) and Zn(II) complexes ofo-hydroxyacetophenone Girard-P hydrazone were prepared by using the organic ligand and the corresponding transition metal chlorides. The protonation and formation constants were evaluated for the organic ligando-hydroxyacetophe-none Girard-P hydrazone and its transition metal complexes, respectively. The thermal behaviour of the test materials was established by means of DTA. Their semiconducting parameters were evaluated through DC-conductivity measurements, and their thermodynamic parameters were evaluated, assigned and interpreted. The mechanism of thermal dehydrochlorination of the metal chloride complexes was proposed.     

A contribution to Semenov's general theory of thermal ignition regarding thermal analysis

The general theory of thermal ignition under the conditions of thermal analysis of flammable substances is discussed. For a linear heating rate of the specimen the ignition temperature is obtained from the relationship $$(dT/dt)_b - \frac{q}{{(dT/dt)_b }} = \frac{E}{{RT_b^2 }}(T_b - T_c^\prime )$$ whereT′_c is the temperature of the reactor wall (heated at the rateq) at the starting moment of the development of the thermal explosion.     

The application of thermal and mass chromatography to thermal oxidative degradation of polymers

A modification of a relatively new technique (thermal and mass chromatography) is used to study the volatile products evolved in the thermal oxidative degradation of isotactic poly(1-pentene) at 115° C under 100% oxygen. This new technique allows certain data to be obtained much more easily and more reliably than before.     

Determination of thermal parameters of one-dimensional nanostructures through a thermal transient method

We present an improved methodology for a thermal transient method enabling simultaneous measurement of thermal conductivity and specific heat of nanoscale structures with one-dimensional heat flow. The temporal response of a sample to finite duration heat pulse inputs for both short (1 ns) and long (5 μs) pulses is analyzed and exploited to deduce the thermal properties. Excellent agreement has been obtained between the recovered physical parameters and computational simulations through choosing an optimized pulse width.     

Intercomparison of thermal conductivity and thermal diffusivity methods for plastics

An intercomparison of measurements of the thermal conductivity and thermal diffusivity of two poly(methyl methacrylates) is reported. A wide variety of methods were used: temperature wave analysis, laser flash, transient plane source (Hot Disk^®), transient line-source probe, and heat flux meter methods. Very good agreement of thermal conductivity results and, separately, of thermal diffusivity results was obtained. Similarly, good agreement between thermal conductivity and thermal diffusivity results, when converted using specific heat capacity and density values, was also obtained. Typically, the values were within a range of approximately ±10%. Considering the significant differences between the methods and the requirements on specimen dimensions, the level of agreement between results was considered to be good.     

Particle behavior in thermal plasmas

In this overview, effects exerted on the motion and on heat and mass transfer of particulates injected into a thermal plasma are discussed, including an assessment of their relative importance in the context of thermal plasma processing of materials. Results of computer experiments are shown for particle sizes ranging from 5–50 μm, and for alumina and tungsten as sample materials. The results indicate that (i) the correction terms required for the viscous drag and the convective heat transfer due to strongly varying properties are the most important factors; (ii) noncontinuum effects are important for particle sizes <10 μm at atmospheric pressure, and these effects will be enhanced for smaller particles and/or reduced pressures; (iii) the Basset history term is negligible, unless relatively large and light particles are considered over long processing distances; (iv) thermophoresis is not crucial for the injection of particles into thermal plasmas; (v) turbulent dispersion becomes important for particle <10 μm in diameter; and (vi) vaporization describes a different particle heating history than that of the evaporation process which, however, is not a critical control mechanism for interphase mass transfer of particles injected into thermal plasmas.     

Effect oftrans-polyoctenamer on thermal stability of rubbers determined by thermal analysis

An effect of a cyclic low molecular-weight polymertrans-polyoctenamer rubber (TOR) on the thermal stability of diene rubbers and their vulcanizates was investigated. The investigation was carried out in the air and nitrogen atmospheres using thermogravimetry, DSC and simultaneous thermoanalytical methods. The thermal stability indexes:T ₅,T _max and activation energy of degradation (E), as well asT _g andT _m values, have been determined.It was found thattrans-polyoctenamer (TOR) increases of the thermal stability indices of raw diene rubbers and their vulcanizates. The results show that the thermal degradation of diene rubbers occurred at higher temperature if they were blended with TOR. In our opinion, intermolecular structures formed between the cyclic low-molecular weight polymer and some linear rubber molecules may be the reason for the higher thermal stability of these rubber blends.The work was supported by State Committee for Research, Poland. Grant No. 7.T08 E 032-08.     

A nonequilibrium molecular dynamics method for thermal conductivities based on thermal noise

We developed a nonequilibrium molecular dynamics (NEMD) method for calculating thermal conductivities. In contrast to other NEMD algorithms, here only the heat sink is localized, whereas the heat source can be uniformly distributed throughout the system. The noise due to cutting off the pair forces or to integration errors is such a uniform heat source. In traditional NEMD methods it is normally considered a nuisance factor. The new algorithm accounts for it and uses it. The algorithm is easy to derive, analyse and implement. Moreover, it circumvents the need to calculate energy fluxes. It is tested on the enhanced simple-point charge model for liquid water and reproduces the known thermal conductivity of this model liquid of 0.81 W m(-1) K(-1). It can be generalized to situations, where the thermal noise is replaced by another uniform heat source, or to the inverse situation, where the heat source is localized but the heat sink extends over the entire system.     

Characterization of groundwater contaminants using dynamic thermal stripping and adsorption/thermal desorption-GC-MS

Summary Alternate methods to the time consuming solvent extraction technique used in the characterization of groundwater contaminants were sought to reduce the analysis time and allow for automation. By adsorbing (ADS) groundwater samples on a quartz tube filled with graphitized charcoal (Carbotrap, Carbotrap C) and thermally desorbing it in a Envirochem Unacon 810 unit directly interfaced with a GC-MSD, it was possible to detect the major groundwater contaminants originating from several types of industrial landfills. Compounds such as aniline, dioxane, and phenols were measured simultaneously with minimal sample preparation. The results were compared to those obtained by dynamic thermal stripping (DTS) followed by GC-MS. These methods are much more cost effective than solvent extraction since they require only a few minutes of the analyst's time for the introduction of the sample. ADS was superior to DTS and solvent extraction for the analysis of water soluble compounds which are poorly extracted into solvents. DTS provided cleaner chromatograms and allowed for lower detection limit than ADS. The two techniques are therefore complementary.     

Use of emanation thermal analysis in the study of thermal behaviour of inorganic materials

Emanation thermal analysis [1, 2] (ETA) is based on the measurement of the inert gas release from samples previously labelled. The high detection sensitivity of radioactive nuclides used for the measurement makes it possible to use very low concentrations of the inert gases (10^–14 at %) so that no influence of the inert gases on the properties of the solids can be supposed.

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Zusammenfassung Emanations — Thermoanalyse [1, 2] (ETA) basiert auf der Messung von freigesetztem inerten Gas aus zufor markierten Proben. Die große Nachweisempfindlichkeit der bei der Messung verwendeten radioaktiven Nuklide ermöglicht die Anwendung sehr niedriger konzentrationen (10^–14 Atom%) für das inerte Gas. Somit kann angenommen werden, daß die Eigenscahften des Feststoffes durch das inerte Gas nicht beeinflußt werden.

     

Determination of calibration function in thermal field flow fractionation under thermal field programming

A new procedure for determining the calibration function able to relate retention and operative parameters to molecular weight of the species in thermal field flow (ThFFF) under thermal field programming (TFP) conditions is presented. The procedure involves determining the average values of retention parameters under TFP and determining a numerical function related to the temperature variations that occur during TFP. The calibration parameters are obtained by a procedure fitting the retention and operative parameters that hold true at the beginning of the TFP. The procedure is closely related to the one previously developed to calibrate the retention time axis under TFP ThFFF and, together, they constitute a full calibration procedure. Experimental validation was performed with reference to polystyrene (PS)-decalin and PS-THF systems. The calibration functions here obtained were compared to those derived by the classical procedure at constant thermal field ThFFF to obtain the calibration function at variable cold wall temperatures. Excellent agreement was found in all cases proving "universality" of the ThFFF calibration concept, i.e. it is independent of the particular system on which it was determined and can thus be extended to ThFFF operating under TFP. The new procedure is simpler than the classical one since it requires less precision in setting the instrumentation and can be obtained with fewer experiments. The potential applications for the method are discussed.     

Theory of multichannel thermal unimolecular reactions. 2. Application to the thermal dissociation of formaldehyde

The thermal dissociation of formaldehyde proceeds on three channels, the molecular-elimination channel H2CO --> H2 + CO (1), the radical-forming bond-fission channel H2CO --> H + HCO (2), and the bond-fission-initiated, intramolecular-hydrogen-abstraction channel H2CO --> H...HCO --> H2 + CO (3) which also forms molecular products. The kinetics of this system in the low-pressure range of the unimolecular reaction is shown to be governed by a subtle superposition of collisional channel coupling to be treated by solving a master equation, of rotational channel switching accessible through ab initio calculations of the potential as well as spectroscopic and photophysical determinations of the threshold energies and channel branching above the threshold energy for radical formation which can be characterized through formaldehyde photolysis quantum yields as well as classical trajectory calculations. On the basis of the available information, the rate coefficients for the formation of molecular and radical fragments are analyzed and extrapolated over wide ranges of conditions. The modeled rate coefficients in the low-pressure range of the reaction (neglecting tunneling) over the range 1400-3200 K in the bath-gas Ar in this way are represented by k0,Mol/[Ar] approximately 9.4 x 10(-9) exp(-33,140 K/T) cm3 molecule(-1) s(-1) and k0,Rad/[Ar] approximately 6.2 x 10(-9) exp(-36,980 K/T) cm3 molecule(-1) s(-1). The corresponding values for the bath-gas Kr, on which the analysis relies in particular, are k0,Mol/[Kr] approximately 7.7 x 10(-9) exp(-33,110 K/T) and k0,Rad/[Kr] approximately 4.1 x 10(-9) exp(-36 910 K/T) cm3 molecule(-1) s(-1). While the threshold energy E0,2 for channels 2 and 3 is taken from spectroscopic measurements, the threshold energy E0,1 for channel 1 is fitted on the basis of experimental ratios k0,Rad/k0,Mol in combination with photolysis quantum yields. The derived value of E0,1(1) = 81.2 (+/-0.9) kcal mol(-1) is in good agreement with results from recent ab initio calculations, 81.9 (+/-0.3) kcal mol(-1), but is higher than earlier results derived from photophysical experiments, 79.2 (+/-0.8) kcal mol(-1). Rate coefficients for the high-pressure limit of the reaction are also modeled. The results of the present work markedly depend on the branching ratio between channels 2 and 3. Expressions of this branching ratio from classical trajectory calculations and from photolysis quantum yield measurements were tested. At the same time, a modeling of the photolysis quantum yields was performed. The formaldehyde system so far presents the best characterized multichannel dissociation reaction. It may serve as a prototype for other multichannel dissociation reactions.     

Influence of thermal transport properties of NEPCM for cool thermal energy storage system

Journal of Thermal Analysis and Calorimetry - The present work deals with thermal energy storage behavior of the nano-enhanced phase change materials (NEPCMs) for building space cooling...