Simulation of solid thermal explosion and liquid thermal explosion of dicumyl peroxide using calorimetric technique

Dicumyl peroxide (DCPO), is produced by cumene hydroperoxide (CHP) process, is utilized as an initiator for polymerization, a prevailing source of free radicals, a hardener, and a linking agent. DCPO has caused several thermal explosion and runaway reaction accidents in reaction and storage zone in Taiwan because of its unstable reactive property. Differential scanning calorimetry (DSC) was used to determine thermokinetic parameters including 700 J g^–1 of heat of decomposition (ΔH_d), 110 °C of exothermic onset temperature (T₀), 130 kJ mol^–1 of activation energy (E_a), etc., and to analyze the runaway behavior of DCPO in a reaction and storage zone. To evaluate thermal explosion of DCPO with storage equipment, solid thermal explosion (STE) and liquid thermal explosion (LTE) of thermal safety software (TSS) were applied to simulate storage tank under various environmental temperatures (T_e). T_e exceeding the T₀ of DCPO can be discovered as a liquid thermal explosion situation. DCPO was stored under room temperature without sunshine and was prohibited exceeding 67 °C of self-accelerating decomposition temperature (SADT) for a tank (radius = 1 m and height = 2 m). SADT of DCPO in a box (width, length and height = 1 m, respectively) was determined to be 60 °C. The TSS was employed to simulate the fundamental thermal explosion behavior in a large tank or a drum. Results from curve fitting demonstrated that, even at the earlier stage of the reaction in the experiments, ambient temperature could elicit exothermic reactions of DCPO. To curtail the extent of the risk, relevant hazard information is quite significant and must be provided in the manufacturing process.     

Theoretical and experimental characterization of wettability of various nanolens arrayed polymer surfaces replicated with nanodimpled aluminum mold insert

Various types of polymer surfaces with a nanolens array, which has an entrant shape with a low aspect ratio, were fabricated and the wettability of the fabricated surfaces was evaluated in both theoretical and experimental ways. The nanolens array was replicated on three different polymer surfaces of polydimethylsiloxane (PDMS), cyclic olefin copolymer (COC), and polymethylmethacrylate (PMMA) by means of replica molding and hot embossing with a nanodimpled aluminum mold that was manufactured by a chemical oxidation process. From the theoretical and experimental evaluations of the wettability it was found that the measured contact angles were very similar with the theoretically estimated ones and also the hydrophilicity and hydrophobicity of the hydrophilic PMMA and hydrophobic PDMS, respectively, surfaces were reinforced by the nanolens array within the Wenzel wetting state.     

Fabrication of dense Ce0.9Mg0.1P2O7-PmOn composites by microwave heating for application as electrolyte in intermediate-temperature fuel cells

In the present work, we report a method of fabrication of dense 10 mol% Mg²⁺-doped cerium pyrophosphate-phosphate (Ce_0.9Mg_0.1P₂O₇-P_mO_n; CMP-P) composites by microwave heat-treatment of the preformed Ce_0.9Mg_0.1P₂O₇ substrates in the presence of phosphoric acid. The composite was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). The microwave heating at 375 °C for 5 min resulted in the formation of dense CMP-P composites which retained most of the pyrophosphate phase. The electrical conductivity was extracted from the EIS data and for the CMP-P composite prepared by H₃PO₄ loading for 10 h and microwave heat-treatment for 5 min it was found to be >10^?2 S m^?1 in 100–250 °C range with a maximum of 0.062 S cm^?1 at 190 °C, which was significant for its application as electrolyte in intermediate temperature fuel cells.     

Computational Analysis of Oxide Ion Conduction in Orthorhombic Perovskite Structured La0.9A0.1InO2.95 (A = Ca,Sr and Ba)

Oxide ion conduction in orthorhombic perovskite structured oxides, La_0.9A_0.1InO_2.95 (A = Ca, Sr and Ba) is analyzed using molecular dynamics simulation. Factors influencing oxide ion conductivity of the compositions considered are analyzed using radial distribution function, bond energies between dopant and oxide ions, and the diffusion path. It is known that perovskite oxides with smaller ion size mismatch between host and dopant ions have higher electrical conductivities. However, exceptions exist, such as a La_0.9A_0.1InO_2.95 (A = Ca, Sr and Ba) system, where high electrical conductivities occur with large ion size mismatches. Based on this study, a dopant with smaller ion than host ion results in the formation of strong ionic bonds with oxide ions, suggesting that the A‐site dopant should be larger than the host ion for forming weaker O–A bonds. Consequently, the trade‐off between ion size mismatch and O–A bond needs to be considered for enhancing oxide ion conductivity of perovskite oxides.     

Study of electrochemical hydrogen charge/discharge properties of FePO4 for application as negative electrodes in hydrogen batteries

We report the electrochemical hydrogen charge/discharge properties of electrodes containing crystalline and amorphous FePO₄ as active material in KOH electrolyte. Crystalline and amorphous FePO₄ were synthesized by an alcohol-assisted precipitation method, and the powders obtained were characterized by X-ray diffraction. X-ray photoelectron spectroscopy is used to investigate the mechanism of hydrogen charge/discharge behavior of FePO₄. The electrochemical hydrogen charge/discharge properties of electrodes containing crystalline and amorphous FePO₄ were investigated for potential application as negative electrodes in rechargeable hydrogen batteries. In galvanostatic discharge/charge mode at 25 °C, the crystalline FePO₄ showed a maximum discharge capacity of 109 mA h g⁻¹, while the amorphous FePO₄ showed a maximum discharge capacity of 81.4 mA h g⁻¹. The electrochemical kinetic properties, exchange current density, and proton diffusivity were calculated using linear polarization measurement and the potential-step method.     

Development of an auto-welding system for CRD nozzle repair welds using a 3D laser vision sensor

A control rod device (CRD) nozzle attaches to the hemispherical surface of a reactor head with J-groove welding. Primary water stress corrosion cracking (PWSCC) causes degradation in these welds, which requires that these defect areas be repaired. To perform this repair welding automatically on a complicated weld groove shape, an auto-welding system was developed incorporating a laser vision sensor that measures the 3-dimensional (3D) shape of the groove and a weld-path creation program that calculates the weld-path parameters. Welding trials with a J-groove workpiece were performed to establish a basis for developing this auto-welding system. Because the reactor head is placed on a lay down support, the outer-most region of the CRD nozzle has restricted access. Due to this tight space, several parameters of the design, such as size, weight and movement of the auto-welding system, had to be carefully considered. The cross section of the J-groove weld is basically an oval shape where the included angle of the J-groove ranges from 0 to 57 degrees. To measure the complex shape, we used double lasers coupled to a single charge coupled device (CCD) camera. We then developed a program to generate the weld-path parameters using the measured 3D shape as a basis. The program has the ability to determine the first and final welding positions and to calculate all weld-path parameters. An optimized image-processing algorithm was applied to resolve noise interference and diffused reflection of the joint surfaces. The auto-welding system is composed of a 4-axis manipulator, gas tungsten arc welding (GTAW) power supply, an optimized designed and manufactured GTAW torch and a 3D laser vision sensor. Through welding trials with 0 and 38-degree included-angle workpieces with both J-groove and U-groove weld, the performance of this auto-welding system was qualified for field application.     

Removal of PM2.5 entering through the ventilation duct in an automobile using a carbon fiber ionizer-assisted cabin air filter

This study evaluated the charging characteristics of a carbon fiber ionizer for PM2.5 and carried out particle capture laboratory tests after an ionizer was installed upstream of the media of an electret cabin air filter. When the ion concentration per particle (N_i) of the carbon fiber charger was 10⁶ ions/cm³, the average charge numbers for each particle were 1.54, 0.88, and 0.49 at 0.6, 1.2, and 1.8 m/s of face velocity, respectively (the particle charging times, τ, were 167, 83, and 56 ms, respectively). For these face velocities, the PM2.5 removal efficiencies of the filter media were 69.3%, 65.2% and 62.2%, respectively, but increased to 80.4%, 71.2% and 65.5%, respectively, when the ionizer was turned on. The carbon fiber ionizer was then installed in front of an electret cabin filter in the air conditioning system of an automobile, after which field tests were performed at a roadside area. For the same N_iτ used in the lab-scale tests, the effects of the carbon fiber ionizer on increasing PM2.5 %Reduction were mild as 9.4%, 4.0%, and 2.8% when the flow rates were at the second, fourth, and sixth levels, respectively (the face velocities were 0.6, 1.2, and 1.8 m/s, respectively). The PM2.5 %Reduction can be substantially increased by 20–21%, for a higher value of N_iτ (=1.0×10⁸ ions s/cm³), which is realized by increasing the power consumption of the carbon fiber ionizer.     

Surface Modification of Exfoliated Layered Gadolinium Hydroxide for the Development of Multimodal Contrast Agents for MRI and Fluorescence Imaging

A novel method for modifying the surface of magnetic‐resonance‐contrasting layered gadolinium hydroxide (LGdH) is developed providing them with water‐ and bio‐compatibility and acid‐resistance, all of which are essential for medical applications. A stable colloid of exfoliated layers is synthesized by exchanging interlayer anions of LGdH with oleate ions. The delaminated layers are successively coated with phospholipids with poly(ethylene glycol) tail groups, and their effectiveness as a contrast agent for magnetic resonance imaging (MRI) is demonstrated. The adaptability of this surface modification approach for incorporating functional molecules and fabricating a fluorescent colloid of LGdH, which has the potential utility as a multimodal probe, is also demonstrated. This result provides a novel approach for expanding the applications of layered inorganic materials and developing a new class of MRI contrast agents.