Chemical Kinetics,Simulation, and Thermodynamics of Glycolytic Depolymerization of Poly(ethylene terephthalate) Waste with Catalyst Optimization for Recycling of Value Added Monomeric Products

Reaction of poly(ethylene terephthalate) (PET) waste powder with ethylene glycol (EG) was carried out in a batch reactor at 1 atm pressure and at various temperatures ranging from 100–220 °C at the intervals of 10 °C. Particle size from 50–512.5 μm, reaction time from 30–150 min, amount of catalyst from 0.001–0.009 mol, and type of catalysts required for glycolysis of PET were optimized. To increase the PET weight (%) loss, various external catalysts were introduced during the reaction at different reaction parameters. Depolymerization of PET was increased with reaction time and temperature. Depolymerization of PET was decreased with increase in the particle size of PET. Reaction rate was found to depend on concentrations of liquid ethylene glycol and ethylene diester groups in the polyester. Analyses of value added monomeric products (DMT and EG) as well as PET were undertaken. Yields of monomers were agreed with PET conversion. A kinetic model was proposed and simulated, and observed consistent with experimental data. Comparisons of effect of various amounts of catalysts and type of catalysts on glycolysis rate were undertaken. Dependence of the rate constant on reaction temperature was correlated by Arrhenius plot, which shows activation energy of 46.2 kJ/mol and Arrhenius constant of 99 783 min^?1.

Arrhenius plot of the rate constant of glycolysis at 1 atm pressure for 127.5 μm PET particle size (KZA = rate constant using zinc acetate as a catalyst, KMA = rate constant using manganese acetate as a catalyst).     

Heat Transfer Studies in an Agitated Vessel During Aqueous Alkaline Depolymerization of Poly(Ethylene Terephthalate) (PET) Waste

Depolymerization reactions of poly(ethylene terephthalate) (PET) waste in aqueous sodium hydroxide solution were carried out in a batch reactor at 150°C at atmospheric pressure. Disodium terephthalate (terephthalic acid salt) and ethylene glycol (EG) remain in the liquid phase. Terephthalic acid (TPA) salt was converted into TPA. The produced monomeric products (TPA and EG) were recovered. Various design parameters were estimated. Design of a batch reactor was undertaken for depolymerization of PET waste in aqueous sodium hydroxide solution. As expected, the Reynolds numbers, Prandtl numbers, Nusselt numbers, coil-side heat transfer coefficients, and overall heat transfer coefficients were consistent with the fluid velocities. It shows excellent potential for commercialization of the depolymerization of PET waste.     

Nonisothermal Crystallization Modeling and Simulation for Polypropylene/Nano CaSO4 Composites with Variations in Nanosizes and Wt.% of Loading

Avrami and Ozawa's combined analysis was employed to study the nonisothermal crystallization kinetics of Polypropylene (PP): CaSO₄ (of 12 and 22 nm) composites using a Differential Scanning Calorimeter (DSC). The parameters, such as Avrami's exponent (n) and growth rate constant (Z_t), that characterized the system of different nanosize composites and virgin PP, were determined. The relative degree of crystallinity as a function of temperature for PP/nano CaSO₄ composites at the same cooling rate and the Sigmoidal shape of curves indicate a strong interaction between PP molecules and the nanolayer, which leads to greater nucleation with a reduction in nanosizes. The theoretical combination of kinetic equations was found to be suitable to describe the physical phenomena of real system. The values of parameters n, Z_t and predicted time t for crystallization at a single cooling rate were obtained from the mathematical model.     

Prediction of back break in blasting using random decision trees

Back break is an unsolicited phenomenon caused due to rock condition, blast geometry, explosive and initiation system in mines. It does not help in creating a smooth high wall and free face for next blasting due to cracks, overhang and under-hang. It can cause rockfall during drilling due to the cracks present in the in situ rock mass at the perimeter. Due to improper free face created from the previous blast and the presence of loose strata in the face increases the overall cost of production. Therefore, predicting and subsequently optimising back break shall reduce their problems to some extent. In this paper, an attempt is made to predict back break using the random forest method. The variables used for the study was such as burden to spacing ratio, stemming to hole-depth ratio, p-wave velocity and the density of explosive. For the random forest model, R² 0.9791 and RMSE 0.87899 and for linear regression was R² was 0.824 and root mean square error (RMSE) 0.72, respectively. From the field trials, it was evident that the use of low-density emulsion can help in reducing the back break and optimise the overall cost of the blasting process. The same results were validated using Random forest method wherein the model R² was 0.9791 and RMSE was 0.8799.

     

Development of an integrated sampler based on direct 222Rn/220Rn progeny sensors in flow-mode for estimating unattached/attached progeny concentration

A flow-mode integrated sampler consisting of a wire-mesh and filter-paper array along with passive solid state nuclear track detectors has been developed for estimating unattached and attached fraction of ²²²Rn/²²⁰Rn progeny concentration. The essential element of this sampler is the direct ²²²Rn/²²⁰Rn progeny sensor (DRPS/DTPS), which is an absorber-mounted-LR115 type nuclear track detector that selectively registers the alpha particles emitted from the progeny deposited on its surface. During sampling at a specified flow-rate, the unattached progeny is captured on the wire-mesh; while the attached progeny gets transmitted and is captured on the filter-paper. The alpha particles emitted by the deposited progeny atoms are registered on the sensors placed at a specified distance facing the wire-mesh and the filter-paper, respectively. The various steps involved in the development of this flow-mode direct progeny sampler such as the optimization of the sampling rate and the distance between the sensor and the deposition substrate are discussed. The sensitivity factor of the DTPS-loaded sampler for ²²⁰Rn progeny deposited on the wire-mesh and filter-paper is found to be 23.77 ± 0.64 (track cm^?2 h^?1) (Bq m^?3)^?1 and 22.30 ± 0.18 (track cm^?2 h^?1) (Bq m^?3)^?1, respectively; while that of DRPS-loaded sampler for ²²²Rn progeny deposition, is 3.03 ± 0.14 (track cm^?2 h^?1) (Bq m^?3)^?1 and 2.08 ± 0.07 (track cm^?2 h^?1) (Bq m^?3)^?1, respectively. The highlight of this flow-mode sampler is its high sensitivity and that it utilizes the passive technique for estimating the unattached and attached progeny concentration, thus doing away with the alpha counting procedures.     

Vortex characteristics due to nozzle clogging in water caster mould: modelling and validation

In continuous slab casting, clogging in the submerged entry nozzle (SEN) ports leads to flow asymmetry and vortex formation in the mould. Knowledge of vortexing and its influence on product quality is fundamental for defect-free production. In this study, the interconnected effects of nozzle clogging and SEN submergence depth, variation on flow asymmetry and vortex characteristics in a 0.4 scale water caster have been characterised by CFD investigation and validated with experimental results from the authors’ previous work. Mean flow velocities at the sub-meniscus and near the port exit predicted by the computational model are compared with the time-averaged values of the impeller probe velocity measurements and found to be in reasonable agreement. Three different clogging conditions (0, 33 and 66% in the left port of the SEN) for SEN submergence depth of 60?mm are studied and the 66% clogging produced vortices having largest diameter, which is consistent with the experimental observations. The effects of SEN submergence depth on flow asymmetry and vortexing are investigated with three different conditions – 40, 60 and 80?mm. It is found that the shallow SEN submergence depth (40?mm) produces vortices of largest diameter and the flow is most stable for a SEN submergence depth of 60?mm among the three cases. Vortex bending towards the SEN as noticed in the experimental observations is also observed in the computational study. This work illustrates the possibility of capturing features of vortexing using validated CFD model.     

Power Performance of AlGaN/GaN HEMTs Grown on SiC by Ammonia-MBE at 4 and 10 GHz

In this letter, we report on the microwave power and efficiency performance of AlGaN/GaN high-electron mobility transistors (HEMTs) grown by ammonia molecular beam epitaxy (ammonia-MBE) on SiC substrates. At 4 GHz, an output power density of 11.1 W/mm with an associated power-added efficiency (PAE) of 63% was measured at V _ds = 48 V on passivated devices. At 10 GHz, an output power density of 11.2 W/mm with a PAE of 58% was achieved for V _ds = 48 V. These results are the highest reported power performance for AlGaN/GaN HEMTs grown by ammonia-MBE and the first reported for ammonia-MBE on SiC substrates.     

High-power polarization-engineered GaN/AlGaN/GaN HEMTs without surface passivation

In this paper, a high-power GaN/AlGaN/GaN high electron mobility transistor (HEMT) has been demonstrated. A thick cap layer has been used to screen surface states and reduce dispersion. A deep gate recess was used to achieve the desired transconductance. A thin SiO/sub 2/ layer was deposited on the drain side of the gate recess in order to reduce gate leakage current and improve breakdown voltage. No surface passivation layer was used. A breakdown voltage of 90 V was achieved. A record output power density of 12 W/mm with an associated power-added efficiency (PAE) of 40.5% was measured at 10 GHz. These results demonstrate the potential of the technique as a controllable and repeatable solution to decrease dispersion and produce power from GaN-based HEMTs without surface passivation.     

Effect of ohmic contacts on buffer leakage of GaN transistors

The effect of ohmic contacts on the buffer leakage of GaN transistors is presented. The buffer leakage for AlGaN/GaN high-electron mobility transistors and GaN MESFETs grown on the same underlying buffer was observed to be different. Controlled experiments show that the increased buffer leakage is due to the nature of the alloyed ohmic contacts and can be minimized if they are screened by the Si doping or by the two-dimensional electron gas.