Kinetic Parameter Estimation from Thermogravimetry and Microscale Combustion Calorimetry

Flammability analysis of extruded polystyrene (XPS) has become crucial due to its utilization as insulation material for energy efficient buildings. Using the Kissinger-Akahira-Sunose and Flynn-Wall-Ozawa methods, the degradation kinetics of two pure XPS from the local market, red and grey ones, were obtained from the results of thermogravity analysis (TG) and microscale combustion calorimetry (MCC) experiments performed under the same heating rates. From the experiments, it was discovered that red XPS released more heat than grey XPS and both materials showed two mass loss stages. Consequently, the kinetic parameters for red XPS were higher than grey XPS. A comparative evaluation of activation energies from MCC and TG showed an insignificant degree of deviation signifying an equivalent apparent activation energy from both methods. However, different activation energy profiles as a result of the different chemical pathways were presented when the dependencies of the activation energies on extent of conversion for TG and MCC were compared.

The Role of Initiator in the Synthesis of Poly(Methyl Methacrylate)-Layered Silicate Nanocomposites through Bulk Polymerization

The structure-property relationship and initiator effect on bulk polymerized poly(methyl methacrylate) (PMMA)–oragnomodified layered silicate nanocomposites was investigated. In this study, we used 2, 2'-azobis (4-methoxy-2,4-dimethyl valeronitrile and benzoyl peroxide initiators for bulk polymerization. The bulk polymerized nanocomposites’ morphology was investigated by X-ray diffraction and transmission electron microscopy. The type of initiator strongly influences the physiochemical properties of the polymer nanocomposite. The thermal degradation of PMMA in the presence of nanofiller was studied. 5 wt% weight loss temperature (T5d) increased as compared to pure PMMA. The peak degradation temperature increased for the nanocomposites. Differential scanning calorimetry and dynamic mechanical analysis were performed to investigate the glass transition temperature and the nature of the constrained region as the reinforcement mechanism respectively. Furthermore, the optical properties such as UV-Vis and Total Luminous Transmission of nanocomposites are examined.

Kinetic Study of Thermal Degradation of a Lignin Nanoparticle-Reinforced Phenolic Foam

In the present study, the kinetics of thermal degradation of a phenolic and lignin reinforced phenolic foams, and the lignin used as reinforcement were studied and the activation energies of their degradation processes were obtained by a DAEM model. The average values for five heating rates of the mean activation energies obtained were: 99.1, 128.2, and 144.0 kJ.mol-1 for the phenolic foam; 109.5, 113.3, and 153.0 kJ.mol-1 for the lignin reinforcement; and 82.1, 106.9, and 124.4 kJ.mol-1 for the lignin reinforced phenolic foam. The standard deviation ranges calculated for each sample were 1.27-8.85, 2.22-12.82, and 3.17-8.11 kJ.mol-1 for the phenolic foam, lignin and the reinforced foam, respectively. The DAEM model showed low mean square errors (

Graft Copolymerization of Methyl Methacrylate onto Cellulose in Homogeneous Medium – Effect of Solvent and Initiator

Homogeneous graft copolymerization of methyl methacrylate (MMA) onto cellulose was carried out in N, N – dimethyl acetamide/LiCl (DMAc/LiCl) and dimethyl sulfoxide/ paraformaldehyde (DMSO/PF) solvent system taking ceric ammonium nitrate (CAN), benzoyl peroxide (BPO) and tin (II)-2-ethyl hexanoate [Sn(Oct)2] as initiators. Different grafting parameters like graft yield (GY), grafting efficiency (GE) and total conversion of monomer to polymer (TC) were evaluated at different reaction conditions of temperature, time, and variation of the amount of monomer and initiator. The viscosity average molecular weight of grafted PMMA and number of grafts per cellulose chain were also calculated. The products were characterized by FT-IR and 1H-NMR analyses and possible reaction mechanisms were deduced. Thermal degradation of the grafted products was also studied by thermo-gravimetric analysis (TG) and differential thermo-gravimetry (DTG).

Rheological and Thermomechanical Properties of Graphene/ABS/PP Nanocomposites

In the present study, the incorporation of graphene into blends of acrylonitrile-butadiene-styrene terpolymer with polypropylene (ABS/PP) was investigated focusing on the improvement of their thermomechanical characteristics and the effect on their rheological behavior. The blends were prepared by melt mixing in a twin-screw extruder and were characterized by measuring the MFI as well as by performing DSC, TGA and mechanical tests. The addition of graphene to ABS/PP blends tends to increase their melt viscosity, due to the confinement of polymer chains motion. Also, graphene causes an increment of the crystallization temperature (Tc), especially in blends with higher PP content, because of the reduction of surface energy of PP nucleation, which is a consequence of the attachment of PP chains to the surface of graphene through the intermolecular CH-π interaction. Moreover, the above nanofiller improves the thermal stability of PP and increases the residue of thermal degradation at all the investigated compositions of blends, due to the thermal isolation effect and the mass transport barrier effect. Regarding the mechanical properties, the addition of graphene improves the elastic modulus, because of its intrinsic mechanical characteristics and its rigidity, and this effect is particularly strong in the case of pure PP.

Kinetics of Polyethylene Terephthalate (PET)and Polystyrene (PS) Dynamic Pyrolysis

Thermo-chemical treatment (TCT) such as pyrolysis is getting recognized as a valid route for (i) materials and valuable products and petrochemicals recovery; (ii) waste recycling; and (iii) elemental characterization. Pyrolysis is also receiving renewed attention for its operational, economical and environmental advantages. In this study, samples of polyethylene terephthalate (PET) and polystyrene (PS) were pyrolysed in a microthermobalance reactor (using a thermogravimetric-TGA setup). Both polymers were prepared and conditioned prior to experimentation. The main objective was to determine the kinetic parameters of the depolymerization reactions that occur within the thermal degradation process. Overall kinetic rate constants (ko) and activation energies (Eo) were determined using the general kinetics theory (GKT) method previously used by a number of authors. Fitted correlations were found and validated using the GKT, errors were within ± 5%. This study represents a fundamental step to pave the way towards the development of scaling relationship for the investigation of larger scale reactors relevant to industry.