Thermal Stability of Z-Type Perfluoro Poly Ether Lubricant Polymers: A Combined Thermogravimetric and Temperature Programmed Desorption Study

Author(s):  
Paul M. Jones ◽  
Lei Li ◽  
Yiao-Tee Hsia

The thermal stability of Zdol 4000, 7800 and Ztetraol perfluoropolyethers (PFPE) have been studied in both the bulk with thermogravimetric analysis (TGA) and in thin film form with temperature programmed desorption spectroscopy (TPD). The TGA results have been interpreted to yield an evaporation activation energy for both Zdol 4000 (13 kcal/mole) and Zdol 7800 (19 kcal/mole). A larger activation energy is also found for all three samples investigated that is consistent with polymer decomposition (22, 27 and 21 kcal/mole respectively). The TPD threshold has been found to be approximately similar all three samples (∼500 K). The temperature of decomposition was also found to be similar for all three samples and was dominated by the CF2O+ mass fragment at ∼660 K. Two desorption maximums were observed for both Zdol 4000 and Ztetraol indicating the similarity in their decomposition chemistry. In contrast only one desorption peak was observed from Zdol 7800 (675 K). A CF3+ fragment was not observed in any of the TPD spectra indicating the absence an acidic decomposition path for all of the Fomblin Z polymers studied.

2021 ◽  
Author(s):  
Zuzanna Kabacińska ◽  
Alida Timar-Gabor ◽  
Benny Guralnik

<p>Thermally activated processes can be described mathematically by the Arrhenius equation. The Meyer-Neldel Rule (MNR), or compensation law, linearly relates the pre-exponent term to the logarithm of the excitation enthalpy for processes that are thermally driven in an Arrhenian manner. This empirical rule was observed in many areas of materials science, in physics, chemistry, and biology. In geosciences it was found to uphold in hydrogen diffusion (Jones 2014a) and proton conduction (Jones 2014b) in minerals.</p><p>Trapped charge dating methods that use electron spin resonance (ESR) or optically or thermally stimulated luminescence (OSL and TL) are based on the dose-dependent accumulation of defects in minerals such as quartz and feldspar. The thermal stability of these defects in the age range investigated is a major prerequisite for accurate dating, while the accurate determination of the values of the trap depths and frequency factors play a major role in thermochronometry applications. </p><p>The correlation of kinetic parameters for diffusion has been very recently established for irradiated oxides (Kotomin et al. 2018). A correlation between the activation energy and the frequency factor that satisfied the Meyer–Neldel rule was reported when the thermal stability of [AlO<sub>4</sub>/h<sup>+</sup>]<sup>0</sup> and [TiO<sub>4</sub>/M<sup>+</sup>]<sup>0</sup> ESR signals in quartz was studied as function of dose (Benzid and Timar-Gabor 2020). Here we compiled the optically stimulated luminescence (OSL) data published so far in this regard, and investigated experimentally the thermal stability of OSL signals for doses ranging from 10 to 10000 Gy in sedimentary quartz samples. We report a linear relationship between the natural logarithm of the preexponent term (the frequency factor) and the activation energy E, corresponding to a Meyer-Neldel energy of 45 meV, and a deviation from first order kinetics in the high dose range accompanied by an apparent decrease in thermal stability. The implications of these observations and the atomic and physical mechanisms are currently studied.</p><p> </p><p><strong>References</strong></p><p>Benzid, K., Timar Gabor, A. 2020. The compensation effect (Meyer–Neldel rule) on [AlO<sub>4</sub>/h<sup>+</sup>]<sup>0</sup> and [TiO<sub>4</sub>/M<sup>+</sup>]<sup>0</sup> paramagnetic centers in irradiated sedimentary quartz. <em>AIP Advance</em>s 10, 075114.</p><p>Kotomin, E., Kuzovkov, V., Popov, A. I., Maier, J., and Vila, R. 2018. Anomalous kinetics of diffusion-controlled defect annealing in irradiated ionic solids. <em>J. Phys. Chem. A</em> 122(1), 28–32</p><p>Jones, A. G. (2014a), Compensation of the Meyer-Neldel Compensation Law for H diffusion in minerals, <em>Geochem. Geophys. Geosyst.</em>, 15, 2616–2631</p><p>Jones, A. G. (2014b), Reconciling different equations for proton conduction using the Meyer-Neldel compensation rule, <em>Geochem. Geophys. Geosyst</em>., 15, 337–349</p>


2021 ◽  
Vol 1016 ◽  
pp. 338-344
Author(s):  
Wan Ji Chen ◽  
Jie Xu ◽  
De Tong Liu ◽  
De Bin Shan ◽  
Bin Guo ◽  
...  

High-pressure torsion (HPT) was conducted under 6.0 GPa on commercial purity titanium up to 10 turns. An ultrafine-grained (UFG) pure Ti with an average grain size of ~96 nm was obtained. The thermal properties of these samples were studied by using differential scanning calorimeter (DSC) which allowed the quantitative determination of the evolution of stored energy, the recrystallization temperatures, the activation energy involved in the recrystallization of the material and the evolution of the recrystallized fraction with temperature. The results show that the stored energy increases, beyond which the stored energy seems to level off to a saturated value with increase of HPT up to 5 turns. An average activation energy of about 101 kJ/mol for the recrystallization of 5 turns samples was determined. Also, the thermal stability of the grains of the 5 turns samples with subsequent heat treatments were investigated by microstructural analysis and Vickers microhardness measurements. It is shown that the average grain size remains below 246 nm when the annealing temperature is below 500 °C, and the size of the grains increases significantly for samples at the annealing temperature of 600 °C.


1999 ◽  
Vol 14 (5) ◽  
pp. 1760-1770 ◽  
Author(s):  
H. G. Jiang ◽  
H. M. Hu ◽  
E. J. Lavernia

The synthesis of nanocrystalline Fe, Fe–4 wt% Al, and Fe–10 wt% Al solid solutions by SPEX ball milling has been studied. The microstructural evolution during ball milling, as well as subsequent heat treatment, has been characterized. The results demonstrate that ball milling promotes the formation of αFe–4 wt% Al and αFe–10 wt% Al solid solutions by reducing the activation energy of these alloys and generating thermal energy during this process. For Fe–10 wt% Al powders milled for various time intervals up to approximately 20 min, the FeAl intermetallic compound is formed. For alloys annealed at temperatures ranging from 600 to 1000 °C, the addition of 10 wt% Al to Fe significantly enhances the thermal stability of the nanocrystalline Fe–Al alloys. Interestingly, the addition of Al within the range of 4–10 wt% seems to have little effect on the thermal stability of these alloys annealed under the same conditions. Also, the thermal stability improves for alloys milled in air as opposed to those processed using Ar.


2011 ◽  
Vol 415-417 ◽  
pp. 261-264
Author(s):  
Yuan Ren ◽  
Zheng Xi ◽  
Wen Jun Gan ◽  
Liang Zhang ◽  
Jing Zhang ◽  
...  

A siloxane-containing dianhydride, succinic anhydride terminated polydimethylsiloxane (DMS-Z21) was selected to cure diglycidyl ether of bisphenol-A based epoxy resin (DGEBA). The cure kinetics and thermal properties were investigated by nonisothermal and isothermal differential scanning calorimetry (DSC) and thermogravimetric analyses (TGA), respectively. The activation energy (Ea) of the curing reaction was obtained based on the methods of Kissinger and isothermal measurements. The results of the thermogravimetric analyses of the DGEBA/DMS-Z21 system showed that the thermal stability of the DGEBA/DMS-Z21 system was slightly higher than the DGEBA/MeTHPA system.


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