Thermal Degradation Kinetics of N,N'-Di(diethoxythiophosphoryl)-1,4-phenylenediamine

The non-isothermal degradation kinetics of N,N＇-di（diethoxythiophosphoryl）-1,4-phenylenediamine in N2 was studied by TG-DTG techniques.The kinetic parameters,including the activation energy and pre-exponential factor of the degradation process for the title compound were calculated by means of the Kissinger and Flynn-Wall-Ozawa（FWO）method and the thermal degradation mechanism of the title compound was also studied with the Satava-Sestak methods.The results indicate that the activation energy and pre-exponential factor are 152.61 kJ/mol and 9.06×101 4s -1with the Kissinger method and 154.08 kJ/mol with the Flynn-Wall-Ozawa method,respectively.It has been shown that the degradation of the title compound follows a kinetic model of one-dimensional diffusion or parabolic law,the kinetic function is G（α）=α2and the reaction order is n=2.

Thermal degradation kinetics and lifetime estimation for polycarbonate/polymethylphenylsilsesquioxane composite

The thermal degradation behaviors of poly-carbonate/polymethylphenylsilsesquioxane(FRPC)com-posites were investigated by thermogravimetric analysis(TGA)under isothermal conditions in nitrogen atmo-sphere.The isothermal kinetics equation was used to describe the thermal degradation process.The results showed that activation energy(E),in the case of isothermal degradation,was a quick increasing function of conversion(α)for polycarbonate(PC)but was a strong and decreasing function of conversion for FRPC.Under the isothermal condition,the addition of polymethylphenylsilsesquioxane(PMPSQ)retardanted the thermal degradation and enhanced the thermal stability of PC during the early and middle stages of thermal degradation.It also indicated a possible existence of a difference in nucleation,nuclei growth,and gas diffusion mechanism in the thermal degradation process between PC and FRPC.Meanwhile,the addition of PMPSQ influenced the lifetime of PC,but the composite still met the demand in manufacturing and application.

Kinetics and mechanism of thermal degradation of vegetable-tanned leather fiber

Thermal degradation of vegetable-tanned leather fiber(VLF)was investigated by thermogravimetric analysis aiming to know the exact kinetics and degradation mechanism.The thermogravimetric(TG)and differential thermogravimetric(DTG)curves showed that decomposition of the VLF occurs mainly in the range of 150-600℃,and the latter exhibits asymmetrical peak with a pronounced shoulder.The decomposition process was first analyzed by deconvolution of the experimental DTG curves,followed by reconstruction of the weight loss profiles of two individual processes.Several common isoconversional approaches were applied to calculate the activation energy over a wide range of conversion for the sample,including modified Kissinger-Akahira-Sunose(MKAS),Friedman,and Flynn-Wall-Ozawa.The average activation energy of vegetable-tanned leather fiber was found to be 241.9 kJ mol^(−1) by MKAS method.The activation energy values obtained for the pseudocomponents representing highly-crosslinked and low-crosslinked collagen in VLF were given as 190.6 and 124.8 kJ mol^(−1),respectively.Generalized master plots results suggested that the reaction mechanism for highly-crosslinked collagen follows the random nucleation and growth process at conversion values lower than 0.5.When the conversion is higher than 0.5,the mechanism tends to random scission model.For low-crosslinked collagen,the degradation is mainly governed by random nucleation and nuclei growth.The gaseous products of VLF thermal degradation were analyzed with an online-coupled TG-Fourier transform infrared spectroscopy system.

Effect of DOPO-containing Flame Retardants on Poly（lactic acid）： Non-flammability, Mechanical Properties and Thermal Behaviors

The flame retardancies of three kinds of 9,10-dihydro-9-oxa-10-phosphaphenan-threne 10-oxide（DOPO）- containing flame retardant（A1, A2, A3）/poly（lactic acid）（PLA） composites[PA-n/（Ax-y）, n= 1--12; x= l, 2, 3, denoting three kinds of flame retardants; y= 10%, 20%, 30%, 40%, denoting the mass fraction of Ax] were greatly enhanced by melt blending of flame retardant Ax with PLA, including twin-screw extrusion and injection-molding processes. With only 10%（mass fraction） of Ax added to PLA, good flame retardancy with limiting oxygen index（LOI） values of more than 33% was achieved. As the Ax mass fraction was further increased to 20%, PA-n/（Ax-20%） composites showed much better flame retardancy（LOI~〉35% and UL-94 V-0 rating）. Moreover, the thermal degradation behaviors and mechanical properties of PA-n/（Ax-y） composites were investigated via thermogravimetric analysis（TGA）, differen- tial thermal analysis（DTA）, tensile testing, notched impact-bar testing, and dynamic mechanical analysis（DMA）. TGA results show that PA-n/（Ax-y） composites have slower rate of mass loss and much higher char yield, compared to neat PLA. With the addition of Ax to PLA, the DTA and DMA results indicate slight variations in glass transition tcmpe- ratures（Tg） of PA-n/（Ax-y） composites. Based on TGA results under nonisothermal conditions, the thermal degrada- tion kinetics of PA-n/（Ax-y） composites were studied by KAssinger＇s and Ozawa＇s methods. These thermal degrada- tion dynamic analyses show lower activation energies（EK or Eo） for PA-n/（Ax-y） composites, corresponding to higher mass fractions of Ax（from 10% to 40%）. The PA-n/（Ax-y） composites with good flame retardancy and good mecha- nical properties obtained in this study could be potential candidates for fire- and heat-resistant applications in auto- motive engineering and building fields with more safety and excellent performance.

Thermal decomposition of poly(ethylene terephthalate)/mesoporous molecular sieve composites

The nonisothermal and isothermal degradation processes of poly(ethylene terephthalate)/mesoporous molecular sieve(PET/MMS)composites synthesized by in-situ polymerization were studied by using thermogravimetric analysis in nitrogen.The nonisothermal degradation of the composite is found to be the first-order reaction.An iso-conversional procedure developed by Ozawa is used to calcu-late the apparent activation energy(E),which is an average value of about 260 kJ/mol with the weight conversion from 0%to 30%,and is higher than that of neat PET.Isothermal degradation results are confirmed with the nonisothermal process,in which PET/MMS showed higher thermal stability than neat PET.The polymer in mesoporous channels has more stability due to the protection of the inorganic pore-wall.These results indicate that mesoporous MMS in PET/MMS composites improve the stability of the polymer.