Reactivity in the solid-state between ZnWO<Subscript>4</Subscript> and some rare-earth metal molybdates RE<Subscript>2</Subscript>MoO<Subscript>6</Subscript> (<Emphasis Type="Italic">RE</Emphasis>=Y,Sm, Eu,Gd, Dy,Ho, Er and Lu)

Organic peroxides (OPs) have caused many momentous explosions and runaway reactions, resulting from thermal instability, chemical pollutants, and even mechanical shock. In Taiwan, dicumyl peroxide (DCPO), due to its unstable reactive nature, has caused two thermal explosions and runaway reaction incidents in the manufacturing process. To evaluate thermal hazards of DCPO in a batch reactor, we studied thermokinetic parameters, such as heat of decomposition (†H _d), exothermic onset temperature (T ₀), maximum temperature rise ((dT/dt)_max), maximum pressure rise ((dP/dt)_max), self-heating rate (dT/dt), etc., via differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2).     

Large-Scale Molecular Dynamics Simulations of Energetic Ni Nanocluster Impact onto the Surface

On the atomic scale, Molecular Dynamics (MD) Simulation of Nano Ni cluster impact on Ni (100) substrate surface have been carried out for energies of E _a = 1–5 eV/atom and total energy of E _T = 195 eV (the total energy of cluster is E _T = nE _a, n is the number of cluster atoms) to understand quantitatively the interaction mechanisms between the cluster atoms and the substrate atoms. The many-body Embedded Atom Method (EAM) was used in this simulation. We investigated the maximum substrate temperature T _max and the time t _max within which this temperature is reached as a function of cluster sizes and the total energy E _T. The temperature T _max is linearly proportional to total cluster energy. For the constant energy per atom and for the cluster size increase, the correlated collisions rapidly transfers energy to the substrate, and the time t _max approached a constant value. For constant total energy the temperature T _max and the time t _max versus different cluster sizes was studied. We showed that the cluster implantation and sputtering atoms from the surface are affected by the cluster size and total kinetic energy of the clusters. Finally time dependence of the number N _dis of disordered atoms in the substrate was observed.     

A new spectral memory of filled rubbers

We recently discovered that shearing particle‐reinforced rubbers in oscillation at a frequency f_a at a small strain γ_a (e.g., ～1% strain) for time t_a can often produce a spectrum hole or drop in the strain‐dependent dissipation spectra of the materials. The location of the hole (or localized perturbation in the loss modulus or loss tangent) depends on the aging strain amplitude γ_a. The depth of this hole is influenced by both the oscillatory aging frequency f_a and the aging duration t_a, and follows a simple power relationship of the product of f_a and t_a. The exponent for the power relationship is a function of filler concentration. These attributes of the spectral hole in filled rubbers are not sensitive to the frequency used to postanalyze the hole. This new memory effect occurs at very small strains and involves material stiffening during the strain aging, and both of those features are quite different from the Mullins effect in filled elastomers. We interpret this newly discovered memory character of filled rubbers from a much broader concept of structure pinning in a condensed frustrated system and consider that the agglomeration of filler particles in rubber matrix shares common physics with granular materials and glass‐forming materials. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 859–869, 2010     

Effects of cumene hydroperoxide on phenol and acetone manufacturing by DSC and VSP2

Cumene hydroperoxide (CHP) being catalyzed by acid is one of the crucial processes for producing phenol and acetone globally. However, it is thermally unstable to the runaway reaction readily. In this study, various concentrations of phenol and acetone were added into CHP for determination of thermal hazards. Differential scanning calorimetry (DSC) tests were used to obtain the parameters of exothermic behaviors under dynamic screening. The parameters included exothermic onset temperature (T ₀), heat of decomposition (ΔH _d), and exothermic peak temperature (T _p). Vent sizing package 2 (VSP2) was employed to receive the maximum pressure (P _max), the maximum temperature (T _max), the self-heating rate (dT/dt), maximum pressure rise rate ((dP/dt)_max), and adiabatic time to maximum rate ((TMR)_ad) under the worst case. Finally, a procedure for predicting thermal hazard data was developed. The results revealed that phenol and acetone sharply caused a exothermic reaction of CHP. As a result, phenol and acetone are important indicators that may cause a thermal hazard in the manufacturing process.     

Isothermal crystallization of concentrated amorphous starch systems measured by modulated differential scanning calorimetry

The slow isothermal crystallization of concentrated amorphous starch systems is measured by Modulated Differential Scanning Calorimetry (MDSC). It can be followed continuously by the evolution (stepwise decrease) of the MDSC heat capacity signal (Cp), as confirmed with data from X-ray diffractometry, Dynamic Mechanical Analysis, Raman spectroscopy, and conventional Differential Scanning Calorimetry. Isothermal MDSC measurements enable a systematic study of the slow crystallization process of a concentrated starch system, such as a pregelatinized waxy corn starch with 24 wt % water and 76 wt % starch. After isothermal crystallization, a broad melting endotherm with a bimodal distribution is observed, starting about 10°C beyond the crystallization temperature. The bulk glass transition temperature (T_g) decreases about 15°C during crystallization. The isothermal crystallization rate goes through a maximum as a function of crystallization time. The maximum rate is characterized by the time at the local extreme in the derivative of Cp (t_max), or by the time to reach half the decrease in Cp (t_1/2). Both t_max and t_1/2 show a bell-shaped curve as a function of crystallization temperature. The temperature of maximum crystallization rate, for the system studied, lies as high as 75°C. This is approximately 65°C above the initial value of T_g. Normalized Cp curves indicate the temperature dependence of the starch crystallization mechanism. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2881–2892, 1999     

Explosion evaluation and safety storage analyses of cumene hydroperoxide using various calorimeters

Plenty of thermal explosions and runaway reactions of cumene hydroperoxide (CHP) were described from 1981 to 2010 in Taiwan. Therefore, a thermal explosion accident of CHP in oxidation tower in 2010 in Taiwan was investigated because of piping breakage. In general, high concentration of CHP for thermal analysis using the calorimeter is dangerous. Therefore, a simulation method and a kinetic parameter were used to simulate thermal hazard of high concentrations of CHP only by the researcher. This study was applied to evaluate thermal hazard and to analyze storage parameters of 80 and 88 mass% CHP using three calorimeters for the oxidation tower, transportation, and 50-gallon drum. Differential scanning calorimetry (DSC) (a non-isothermal calorimeter), thermal activity monitor III (TAM III) (an isothermal calorimeter), and vent sizing package 2 (VSP2) (an adiabatic calorimeter) were employed to detect the exothermic behavior and runaway reaction model of 80 and 88 mass% CHP. Exothermic onset temperature (T ₀), heat of decomposition (ΔH _d), maximum temperature (T _max), time to maximum rate under isothermal condition (TMR_iso) (as an emergency response time), maximum pressure (P _max), maximum of self-heating rate ((dT/dt)_max), maximum of pressure rise rate ((dP/dt)_max), half-life time (t _1/2), reaction order (n), activation energy (E _a), frequency factor (A), etc., of 80 and 88 mass% CHP were applied to prevent thermal explosion and runaway reaction accident and to calculate the critical temperature (T _c). Experimental results displayed that the n of 80 and 88 mass% CHP was determined to be 0.5 and the E _a of 80 and 88 mass% CHP were evaluated to be 132 and 134 kJ mol^?1, respectively.     

Study on curing reaction of epoxy resin modified with prepolymers containing spiro orthocarbonate

Prepolymers were prepared by the reaction of 3,9-dihydroxyethyl-3′9′-dibenzyl-1,5,7,11-tetraoxaspiro(5,5)undecane with 4,4′-diphenylmethane diisocyanate (MDI) and 1,6-hexa-methylene diisocyanate (HDI). The number-average molecular weights of the prepolymers can be controlled by changing the mole ratios of spiro compound and diisocyanates. Kinetic studies of the cure reaction for the epoxy resin system modified with or without prepolymers were followed by a HLX-1 dynamic torsional vibration apparatus. The results indicated that gel time (t_g) and activation energy (E_a) increased as the content of prepolymers in the epoxy resin system increased. A difference with the cure reaction of the pure epoxy resin, the second-order reaction for the epoxy resin modified with the prepolymers, was obtained. Rate constants (k) of the cure reaction are 0.231 min^?1 for the epoxy resin, and 0.312 min^?1 for the modified epoxy resin. The mechanism of the cure reaction was discussed. © 1995 John Wiley & Sons, Inc.     

Microcalorimetric investigation of water vapor adsorption on silica gel

In this study, the activities of four ginsenosides Rc, Re, Rd, and Rf on splenic lymphocytes growth were studied by microcalorimetry. Some qualitative and quantitative information, such as the metabolic power–time curves, growth rate constant k, maximum heat-output power of the exponential phase P _max and the corresponding appearance peak time t _max, total heat output Q _t, and promotion rate R _p of splenic lymphocytes growth affected by the four ginsenosides were calculated. In accordance with thermo-kinetic model, the corresponding quantitative relationships of k, P _max, t _max, Q _t, R _p, and c were established, . Also, the median effective concentration (EC₅₀) was obtained by quantitative analysis. Based on both the quantitative quantity–activity relationships (QQAR) and EC₅₀, the sequence of promotion activity was Rc > Re > Rd > Rf. The analysis of structure–activity relationships showed that the number, type, and position of sugar moieties on the gonane steroid nucleus had important influences on the promotion activity of Rc, Re, Rd, and Rf on splenic lymphocytes growth. Microcalorimetry can be used as a useful tool for determining the activity and studying the quantity–activity relationship of drugs on cell.     

Thermal hazard evaluation for methyl ethyl ketone peroxide mixedwith inorganic acids

Methyl ethyl ketone peroxide (MEKPO) possesses complex structures which have caused many incidents involving fires or explosions by mixing with incompatible substances, external fires, and others. In this study, reactivities or incompatibilities of MEKPO with inorganic acids (HCl, HNO₃, H₃PO₄ and H₂SO₄) were assessed by differential scanning calorimetry (DSC) and vent sizing package 2 (VSP2). Parameters obtained by the above-mentioned devices could be readily employed to discuss the runaway reaction, such as onset temperature (T ₀), heat of reaction (ΔH _d), time to maximum rate (TMR), maximum self heat rate (dT/dt)_max, adiabatic temperature rise (ΔT _ad), maximum pressure of decomposition (P _max) and so on. Mixing MEKPO with hydrochloric acid resulted in the lowest T ₀ among inorganic acids. Nitric acid not only lowered the T ₀ but also delivered the highest heat releasing rate or self heat rate (dT/dt), which was concluded to be the worst case in terms of contamination hazards during storage or transportation of MEKPO.     

Microcalorimetric investigation of the effect of berberine alkaloids from <Emphasis Type="Italic">Coptis chinensis</Emphasis> Franch on <Emphasis Type="Italic">Staphylococcus aureus</Emphasis> growth

The inhibitory effects of three berberine alkaloids (BAs) from rhizome of Coptis chinensis Franch, a traditional Chinese medicinal (TCM) herb, on Staphylococcus aureus growth were investigated by microcalorimetry. The power-time curves of S. aureus with and without BAs were acquired; meanwhile the extent and duration of inhibitory effects on the metabolism were evaluated by studying the growth rate constant (k), half inhibitory ratio (IC₅₀), maximum heat-output power (P _max), peak time of maximum heat-output power (t _p) and total heat production (Q _t). The value of k of S. aureus in the presence of the three BAs decreased with the increasing concentrations of BAs. Moreover, P _max was reduced and the value of t _p increased with increasing concentrations of the three drugs. The inhibitory activity varied with different drugs. The values of IC₅₀ of the three BAs are respectively, 101.4 μg/mL for berberine, 241.0 μg/mL for palmatine and 792.3 μg/mL for jateorrhizine. The sequence of antimicrobial activity of the three BAs is: berberine > palmatine > jateorrhizine. It is suggested that the functional group methylenedioxy or methoxyl at C2 on the phenyl ring could possibly improve antimicrobial activity more strongly than hydroxyl at C2 on the phenyl ring. Supported by the National Natural Science Foundation of China (Grant No. 30625042)     

Evaluation of adiabatic runaway reaction of methyl ethyl ketone peroxide by DSC and VSP2

Methyl ethyl ketone peroxide (MEKPO) is generally applied to manufacturing in the polymerization processes. Due to thermal instability and high exothermic behaviors of MEKPO, if any operation is undertaken recklessly or some environmental effect is produced suddenly during the processes, fires and explosions may inevitably occur. In this study, thermal analysis was evaluated for MEKPO by differential scanning calorimetry (DSC) test. Vent sizing package 2 (VSP2) was used to analyze the thermal hazard of MEKPO under various stirring rates in a batch reactor. Thermokinetic and safety parameters, including exothermic onset temperature (T ₀), maximum temperature (T _max), maximum pressure (P _max), self-heating rate (dT dt ⁻¹), pressure rise rate (dP dt ⁻¹), and so on, were discovered to identify the safe handling situation. The stirring rates of reactor were confirmed to affect runaway and thermal hazard characteristics in the batch reactor. If the stirring rate was out of control, it could soon cause a thermal hazard in the reactor.     

On the origin of the multiple melting behavior in poly(ethylene naphthalene‐2,6‐dicarboxylate): Microstructural study as revealed by differential scanning calorimetry and X‐ray scattering

In this article a study on the melting behavior and microstructure of semicrystalline poly(ethylene naphthalene‐2,6‐dicarboxylate) (PEN) prepared by crystallization from the glass under different annealing conditions is presented. The influence of the annealing temperature (T_a), annealing time (t_a), and the heating rate (R_h) at which T_a is reached on the endothermic behavior of the samples was investigated by means of differential scanning calorimetry (DSC). A dual melting behavior appeared for low R_h values (2 deg · min⁻¹) within the range of 145 °C < T_a < 250 °C and 1 min ≤ t_a. ≤ 16 h. Samples subjected to fast heating rates (R_h = 200 deg · min⁻¹) to reach a T_a ≥ 230 °C showed DSC traces in which a transition is observed from three peaks to a single melting peak when t_a increases in the 30–240 min range. On the basis of the DSC results, PEN samples were prepared displaying single or dual endothermic behavior. The microstructure of these samples was studied by wide (WAXS) and small‐angle X‐Ray scattering (SAXS) techniques. The SAXS data were analyzed using the correlation function and interface distribution function formalisms, respectively. In samples with a single melting behavior, microstructural parameters such as the long spacing, the amorphous and the crystalline phase thicknesses are consistent with a lamellar stacking model in which the thickness distributions of both phases are almost the same. For samples exhibiting two melting endotherms, a dual lamellar model, which is in agreement with the experimental results is proposed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1167–1182, 2000     

Electrochemical nucleation of lead and copper on indium-tin oxide electrodes

The nucleation process of Pb and Cu onto indium-tin oxide electrodes was studied by single potentiostatic steps using 0.1×10^–4 mol L^–1 Cu(NO₃)₂ and 2×10^–2 mol L^–1 Pb(NO₃)₂ solutions in aqueous 1.0 mol L^–1 NaNO₃. The current, I_max, and the time, t_max, corresponding to the maximum, were evaluated by 3D nucleation with a diffusion-controlled growth model for instantaneous and progressive nucleation. The non-dimensional plots of (I/I_max)² vs. t/t_max showed that Cu and Pb nucleation closely followed the response predicted for instantaneous nucleation. Other parameters, such as I vs. t^1/2 and I²_maxt_max, as well as nuclei micrographs, were analyzed, corroborating the results obtained.     

Electron paramagnetic resonance spectroscopic studies of thermally generated free radicals in PMR-15 polyimide resins

PMR-15 is a high-performance thermoset polyimide resin that is used in many high-temperature applications. Postcured PMR-15 produces room-temperature electron paramagnetic resonance (EPR) spectra from stable freeradical species that are formed during the postcuring stages. The variable-temperature EPR spectral intensities show a minimum at T_min in the range ?60 to ?40°C, and a maximum at T_max in the range 80–120°C. The EPR intensities follow the inverse temperature dependence of Curie's law below T_min and are due to a stable free radical. The intensities then increase with increasing temperature between T_min and T_max. The free radical with such temperature dependence is not present below T_min and is undetectable by EPR at temperatures above T_max. These free radicals are generated during the postcuring process at elevated temperature above 310°C. The thermo-oxidative degradation involves free radicals generated during the postcuring process in the presence of oxygen gas. © 1993 John Wiley & Sons, Inc.     

Incident investigation on thermal instability of an intermediate using adiabatic calorimeter

Thermal instability is a loss of thermal control which liberates high amount of energy and pressure. An incident took place during drying of an intermediate having amino alcohol functional group in agitated nutsche filter dryer at plant scale. During our investigation using advanced reactive system screening tool (ARSST), thermal decomposition was observed. Onset temperature of decomposition (T _o) is at 85 °C, adiabatic temperature rise due to decomposition (ΔT _ad) is 215 °C, maximum temperature attained due to decomposition (T _max) is 300 °C, maximum self-heat rate (dT/dt)_max is 6,215 °C min^?1, and maximum rate of pressure rise (dP/dt)_max is 1,442 psi min^?1 obtained from ARSST experiments. T _D24 value is 75 °C which was estimated experimentally. The correlations of these results were utilized to identify the root cause of this incident and necessary control measures were taken accordingly.     

Effect of finite extensibility on the viscoelastic properties of a styrene–butadiene rubber vulcanizate in simple tensile deformations up to rupture

Stress–strain and rupture data were determined on an unfilled styrene–butadiene vulcanizate at temperatures from ?45 to 35°C and at extension rates from 0.0096 to 9.6 min^?1. The data were represented by four functions: (1) the well-known temperature function (shift factor) a_T; (2) the constant strain rate modulus, F(t,T), reduced to temperature T₀ and time t/a_T, i.e., T₀F(t/a_T)/T; (3) the time-dependent maximum extensibility, λ_m(t/a_T); and (4) a function Ω(χ) where χ = (λ ? 1)λ_m⁰/λ_m, in which λ is the extension ratio and λ_m⁰ is the maximum extensibility under equilibrium conditions. The constant strain rate modulus characterizes the stress–time response to a constant extension rate at small strains, within the range of linear response; λ_m is a material parameter needed to represent the response at large λ; and Ω(χ) represents the stress–strain curve of the material in a reference state of unit modulus and λ_m = λ_m. The shift factor a_T was found to be sensibly independent of extension. At all values of t/a_T for which the maximum extensibility is time-independent, the relaxation rate was also found to be independent of λ. These observations indicate that the monomeric friction coefficient is strain-independent over the ranges of T and λ covered in the present study. It was found that λ_m⁰ = 8.6 and that the largest extension ratio at break, (λ_b)_max, is 7.3. Thus, rupture always occurs before the network is fully extended.     

Zymomonas mobilis as catalyst for the biotechnological production of sorbitol and gluconic acid

The conversion of glucose and fructose into gluconic acid (GA) and sorbitol (SOR) was conducted in a batch reactor with free (CTAB-treated or not) or immobilized cells of Zymomonas mobilis. High yields (more than 90%) of gluconic acid and sorbitol were attained at initial substrate concentration of 600 g/L (glucose plus fructose at 1:1 ratio), using cells with glucose-fructose-oxidoreductase activity of 75 U/L. The concentration of the products varied hyperbolically with time according to the equations (GA)=t(GA)_max/(W_GA +t), (SOR)=t (SOR)_max/(W_Sor+t), v_GA=[W_GA (GA)_max]/(W_GA+t)² and V_SOR=[W_SOR (SOR)_max]/(W_SOR+t)². Taking the test carried out with free CTAB-treated cells as an example, the constant parameters were (GA)_max= 541 g/L, (SOR)_max=552 g/L, W_GA=4.8h, W_SOR=4.9h, υ_GA=112.7 g/L· and υ_SOR=112.7 g/L·.     

Thermal conductivity measurement of liquids by means of a microcalorimeter

A study has been carried out of calorimetric cells based on the coaxial cylinder method suitable for the thermal conductivity measurements in a C80D micro-calorimeter from Setaram (France). On the hypothesis of a pure conductive process, it has been possible to obtain the equation expressing the thermal conductivity k of a liquid sample in function of the heat flow measured by the calorimeter, and the relative thermal conductivity uncertainty has been analysed. To justify the hypothesis of practical absence of convection and negligible temperature differences during experimentation, a CFD (Computational Fluid Dynamics) study has been performed. With a view to testing our equipment and calibration method, the thermal conductivities of some pure liquids (toluene, n-decane) and systems (water + ethanol and nanofluid water/Al₂O₃), which cover a wide range, have been measured.     

Self-reactive rating of thermal runaway hazards on 18650 lithium-ion batteries

Vent sizing package 2 (VSP2) was used to measure the thermal hazard and runaway characteristics of 18650 lithium-ion batteries, which were manufactured by Sanyo Electric Co., Ltd. Runaway reaction behaviors of these batteries were obtained: 50% state of charge (SOC), and 100% SOC. The tests evaluated the thermal hazard characteristics, such as initial exothermic temperature (T ₀), self-heating rate (dT?dt ^?1), pressure-rise rate (dP?dt ^?1), pressure temperature profiles, maximum temperature, and pressure which were observed by adiabatic calorimetric methodology via VSP2 using customized test cells. The safety assessment of lithium-ion cells proved to be an important subject. The maximum self-heating rate (dT?dt ^?1)_max and the largest pressure-rise rate (dP?dt ^?1)_max of Sanyo 18650 lithium-ion battery of 100% SOC were measured to be 37,468.8???C?min^?1 and 10,845.6?psi?min^?1, respectively, and the maximum temperature was 733.1???C. Therefore, a runaway reaction is extremely serious when a lithium-ion battery is exothermic at 100% SOC. This result also demonstrated that the thermal VSP2 is an alternative method of thermal hazard assessment for battery safety research. Finally, self-reactive ratings on thermal hazards of 18650 lithium-ion batteries were studied and elucidated to a deeper extent.     

Evaluation of thermal hazard for lauroyl peroxide by VSP2 and TAM III

When above certain temperature limits, lauroyl peroxide is an unstable material. If the thermal source cannot be properly governed during any stage in the preparation, manufacturing process, storage or transport, runaway reactions may inevitably be induced immediately. In this study, the influence of runaway reactions on its basic thermal characteristic was assessed by evaluating thermokinetic parameters, such as activation energy (E _a) and frequency factor (A) by thermal activity monitor III (TAM III). This was achieved under five isothermal conditions of 50, 60, 70, 80, and 90?°C. Vent sizing package 2 (VSP2) was employed to determine the maximum pressure (P _max), maximum temperature (T _max ), maximum self-heating rate ((dT?dt ^?1)_max), maximum pressure rise rate ((dP?dt ^?1)_max), and isothermal time to maximum rate ((TMR)_iso) under the worst case. Results of this study will be provided to relevant plants for adopting best practices in emergency response or accident control.