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.     

Mason: morphological simplification

The traditional rounding and filleting morphological filters are biased. Hence, as r grows, the rounding R_r (S) of S shrinks and the filleting F_r (S) grows. A shape S is r-regular when R_r (S) = F_r (S) = S. The combinations F_r (R_r (S)) and R_r (F_r (S)) produce nearly r-regular shapes, but retain a bias: F_r (R_r (S)) is usually smaller than S and R_r (F_r (S)) is larger. To overcome this bias, we propose a new filter, called Mason. The r-mortar M_r (S) of S is F_r (S)–R_r (S), and the stability of a point P with respect to S is the smallest value of r for which P belongs to M_r (S). Stability provides important information about the shape’s imbedding that cannot be obtained through traditional topological or differential analysis tools. F_r (R_r (S)) and R_r (F_r (S)) only affect space in M_r (S). For each maximally connected component of M_r (S), Mason performs either F_r (R_r (S)) or R_r (F_r (S)), choosing the combination that alters the smallest portion of that component. Hence, Mason acts symmetrically on the shape and on its complement. Its output is guaranteed to have a smaller symmetric difference with the original shape than that of either combination F_r (R_r (S)) or R_r (F_r (S)). Many previously proposed shape simplification algorithms were focused on reducing the combinatorial storage or processing costs of a shape at the expense of the smoothness and regularity or altered the shape in regular portions that did not exhibit any high frequency complexity. Mason is the first shape simplification operator that is independent of the particular representation and offers the advantage of preserving portions of the boundary of S that are regular at the desired scale.     

Taylor approximation for hybrid systems

We propose a new approximation technique for Hybrid Automata. Given any Hybrid Automaton H, we call Approx(H, k) the Polynomial Hybrid Automaton obtained by approximating each formula ϕ in H with the formulae ϕ_k obtained by replacing the functions in ϕ with their Taylor polynomial of degree k. We prove that Approx(H, k) is an over-approximation of H. We study the conditions ensuring that, given any ϵ > 0, some k₀ exists such that, for all k > k₀, the “distance” between any vector satisfying ϕ_k and at least one vector satisfying ϕ is less than ϵ. We study also conditions ensuring that, given any ϵ > 0, some k₀ exists such that, for all k > k₀, the “distance” between any configuration reached by Approx(H, k) in n steps and at least one configuration reached by H in n steps is less than ϵ.     

Development of wireless compressive/relaxation-stress measurement system integrated with pressure-sensitive carbon black-filled silicone rubber-based sensors

In order to detect the installation compressive stress and monitor the stress relaxation between two bending surfaces on a defensive furnishment, a wireless compressive-stress/relaxation-stress measurement system based on pressure-sensitive sensors is developed. The flexible pressure-sensitive stress sensor array is fabricated by using carbon black-filled silicone rubber-based composite. The wireless stress measurement system integrated with this sensor array is tested with compressive stress in the range from 0 MPa to 3 MPa for performance evaluation. Experimental results indicate that the fractional change in electrical resistance of the pressure-sensitive stress sensor changes linearly and reversibly with the compressive stress, and its fractional change goes up to 355% under uniaxial compression; the change rate of the electrical resistance can track the relaxation stress and give out a credible measurement in the process of stress relaxation. The relationship between input (compressive stress) and output (the fractional change in electrical resistance) of the pressure-sensitive sensor is ΔR/R₀ = σ × 1.2 MPa^?1. The wireless compressive stress measurement system can be used to achieve sensitivity of 1.33 V/MPa to the stress at stress resolution of 920.3 Pa. The newly developed wireless stress measurement system integrated with pressure-sensitive carbon black-filled silicone rubber-based sensors has advantages such as high sensitivity to stress, high stress resolution, simple circuit and low energy consumption.     

Design,simulation and validation of a novel uncooled infrared focal plane array

This paper describes a novel single-layer bi-material cantilever microstructure without silicon (Si) substrate for focal plane array (FPA) application in uncooled optomechanical infrared imaging system (UOIIS). The UOIIS, responding to the radiate infrared (IR) source with spectral range from 8 to 14 μm, may receive an IR image through visible optical readout method. The temperature distribution of the IR source could be obtained by measuring the thermal–mechanical rotation angle distribution of every pixel in the cantilever array, which is consisted of two materials with mismatching thermal expansion coefficients. In order to obtain a high detection to the IR object, gold (Au) film is coated alternately on silicon nitride (SiN_x) film in the flection beams of the cantilevers. And a thermal–mechanical model for such cantilever microstructure is proposed. The thermal and thermal–mechanical coupling field characteristics of the cantilever array structure are optimized through numerical analysis method and simulated by using the finite element simulation method. The thermal–mechanical rotation angle simulated and thermal–mechanical sensitivity tested in the experiment are 2.459 × 10⁻³ and 3.322 × 10⁻⁴ rad/K, respectively, generally in good agreement with what the thermal–mechanical model and numerical analysis forecast, which offers an effective reference for FPA structure parameters design in UOIIS.     

Evaluation of response characteristics of resistive oxygen sensors based on porous cerium oxide thick film using pressure modulation method

In order to reduce the response time of resistive oxygen sensors using porous cerium oxide thick film, it is important to ascertain the factors controlling response. Pressure modulation method (PMM) was used to find the rate-limiting step of sensor response. This useful method measures the amplitude of sensor output (H(f)) for the sine wave modulation of oxygen partial pressure at constant frequency (f). In PMM, “break” response time, which is minimum period in which the sensor responds precisely, can be measured. Three points were examined: (1) simulated calculations of PMM were carried out using a model of porous thick film in which spherical particles are connected in a three-dimensional network; (2) sensor response speed was experimentally measured using PMM; and (3) the diffusion coefficient and surface reaction coefficient were estimated by comparison between experiment and calculation. The plot of log f versus log H(f) in the high f region was found to have a slope of approximately −0.5 for both porous thick film and non-porous thin film, when the rate-limiting step was diffusion. Calculations showed the response time of porous thick film was 1/20 that of non-porous thin film when the grain diameter of the porous thick film was the same as the thickness of non-porous thin film. At 973 K, “break” response time (t_b) of the resistive oxygen sensor was found by experiment to be 109 ms. It was concluded that the response of the resistive oxygen sensor prepared in this study was strongly controlled by diffusion at 923–1023 K, since the experiment revealed that the slope of plot of log f versus log H(f) in the high f region was approximately −0.5. At 923–1023 K, the diffusion coefficient of oxygen vacancy in porous ceria (D_V) was expressed as follows: D_V (m²s⁻¹) = 5.78 × 10⁻⁴ exp(−1.94 eV/kT). At 1023 K, the surface reaction coefficient (K) was found to exceed 10⁻⁴ m/s.     

A simple semi-analytical model for remote estimation of chlorophyll-a in turbid waters: Validation

Accurate assessment of phytoplankton chlorophyll-a (chla) concentrations in turbid waters by means of remote sensing is challenging due to the optical complexity of case 2 waters. We have applied a recently developed model of the form [R_rs^? 1(λ₁) ? R_rs^? 1(λ₂)] × R_rs(λ₃) where R_rs(λ_i) is the remote-sensing reflectance at the wavelength λ_i, for the estimation of chla concentrations in turbid waters. The objectives of this paper are (a) to validate the three-band model as well as its special case, the two-band model R_rs^? 1(λ₁) × R_rs(λ₃), using datasets collected over a considerable range of optical properties, trophic status, and geographical locations in turbid lakes, reservoirs, estuaries, and coastal waters, and (b) to evaluate the extent to which the three-band model could be applied to the Medium Resolution Imaging Spectrometer (MERIS) and two-band model could be applied to the Moderate Resolution Imaging Spectroradiometer (MODIS) to estimate chla in turbid waters.The three-band model was calibrated and validated using three MERIS spectral bands (660–670 nm, 703.75–713.75 nm, and 750?757.5 nm), and the 2-band model was tested using two MODIS spectral bands (λ₁ = 662–672, λ₃ = 743–753 nm). We assessed the accuracy of chla prediction in four independent datasets without re-parameterization (adjustment of the coefficients) after initial calibration elsewhere. Although the validation data set contained widely variable chla (1.2 to 236 mg m^? 3), Secchi disk depth (0.18 to 4.1 m), and turbidity (1.3 to 78 NTU), chla predicted by the three-band algorithm was strongly correlated with observed chla (r² > 0.96), with a precision of 32% and average bias across data sets of ? 4.9% to 11%. Chla predicted by the two-band algorithm was also closely correlated with observed chla (r² > 0.92); however, the precision declined to 57%, and average bias across the data sets was 18% to 50.3%. These findings imply that, provided that an atmospheric correction scheme for the red and NIR bands is available, the extensive database of MERIS and MODIS imagery could be used for quantitative monitoring of chla in turbid waters.     

An uncooled optically readable infrared imaging detector

This paper presents a design and fabrication of bi-material micro-cantilever array (focal plane array, FPA) made of silicon nitride (SiN_x) and gold (Au) for uncooled optical readout infrared (IR) imaging system, in which silicon (Si) substrate is removed. Compared with the conventional thermal imaging detectors where the FPA must be put in high vacuum, IR thermal images can be obtained even though the cantilever array is placed in the atmosphere. The reason is the elimination of air gap (∼2 μm) between the cantilever beam and substrate, which introduces the air conduction of high temperature gradient. The preliminary experimental results with the micro-cantilever array of 140 × 98 elements and a 12-bit charge-coupled device (CCD) indicate that objects at temperature of higher than 120 °C can be detected and the noise-equivalent temperature difference (NETD) is ∼7 K. Also, the experimental results are well accordant with the thermomechanical analysis of designed micro-cantilever array.     

Humidity-insensitive and low oxygen dependence tungsten oxide gas sensors

Gas sensing characteristics of WO₃ powder and its physical properties under different heat treatment conditions have been investigated. The WO₃ powder was synthesized by wet process from ammonium tungstate parapentahydrate and nitric solution. The precipitated product was then calcined at 300–800 °C for 2–12 h. The physical properties of the products were characterized by using X-ray diffractometer (XRD), scanning electron microscope (SEM), and BET method. It was found that the crystallite size, particle size and surface area of the WO₃ powders were in the range of 30–45 nm, 0.1–3.0 μm and 1.2–3.7 m²/g, respectively. Calcination at higher temperature and longer time led to the increase of particle size by more than 300%, and reduction in specific surface area by more than 60%. However, the crystallite size was found to increase only by ∼30% under identical heat treatment. These results inferred that such heat treatment had more profound effect on crystallite aggregation than on crystallite growth. Gas sensing measurement showed that the largest change of output voltage to both ethyl alcohol and ammonia was obtained from the sensor calcined at 600 °C for 2 h, which had the highest surface area. However, the highest sensitivity which is defined as the ratio of sensor's resistance in air to that in the sample gas, R_air/R_gas, was obtained from the sensor calcined at 600 °C for 6 h due to its highest background resistance in air. Moreover, it was also found that the sensors were less sensitive to the oxygen content in the carrier gas and did not sensitive at all to water vapor.     

Mechanistic and kinetic study on the reaction of methylperoxy radical with atomic iodine

Singlet and triplet potential energy surfaces for the CH₃O₂ with I reaction have been investigated computationally to propose the reaction mechanisms and possible products. Multichannel RRKM theory and transition-state theory have been used to compute the overall and individual rate constants at 200–3000 K and 10⁻¹⁴–10¹⁴ Torr. On the singlet PES, addition-elimination, substitution and H-abstraction mechanisms are located, and the addition-elimination mechanism is dominant. At 70 Torr with N₂ as bath gas, IM1(CH₃OOI) formed by collisional stabilization is dominated at 200–300 K, whereas CH₂O and HIO are the major products at the temperatures between 350 and 3000 K; The title reaction exhibits the typical falloff behavior. The results show that temperature and pressure affect the yield of products.Furthermore, the predicted rate constants at 298 K 70 Torr of N₂ agree well with the available experimental values. On the triplet PES, the most favorable product should be CH₃I + O₂(³Σ) at atmospheric condition. Other two pathways on the triplet PES will not compete with the pathways on the singlet PES in kinetically and thermodynamically.     

Evaluation of a non-point source pollution model,AnnAGNPS, in a tropical watershed

Impaired water quality caused by human activity and the spread of invasive plant and animal species has been identified as a major factor of degradation of coastal ecosystems in the tropics. The main goal of this study was to evaluate the performance of AnnAGNPS (Annualized Non-Point Source Pollution Model), in simulating runoff and soil erosion in a 48 km² watershed located on the Island of Kauai, Hawaii. The model was calibrated and validated using 2 years of observed stream flow and sediment load data. Alternative scenarios of spatial rainfall distribution and canopy interception were evaluated. Monthly runoff volumes predicted by AnnAGNPS compared well with the measured data (R² = 0.90, P < 0.05); however, up to 60% difference between the actual and simulated runoff were observed during the driest months (May and July). Prediction of daily runoff was less accurate (R² = 0.55, P < 0.05). Predicted and observed sediment yield on a daily basis was poorly correlated (R² = 0.5, P < 0.05). For the events of small magnitude, the model generally overestimated sediment yield, while the opposite was true for larger events. Total monthly sediment yield varied within 50% of the observed values, except for May 2004. Among the input parameters the model was most sensitive to the values of ground residue cover and canopy cover. It was found that approximately one third of the watershed area had low sediment yield (0–1 t ha⁻¹ y⁻¹), and presented limited erosion threat. However, 5% of the area had sediment yields in excess of 5 t ha⁻¹ y⁻¹. Overall, the model performed reasonably well, and it can be used as a management tool on tropical watersheds to estimate and compare sediment loads, and identify “hot spots” on the landscape.     

Critical pressure for capillary valves in a Lab-on-a-Disk: CFD and flow visualization

Capillary valves are used as pressure barriers to control flow sequencing in microfluidic devices. Influence of valves height on liquid flow pattern and critical pressure are studied through flow visualization and CFD predictions (Gambit® 2.2.30 and FLUENT® 6.2.16). Both hydrophilic and hydrophobic walls are studied. Results show that the surface tension plays a major role in the liquid progress through the microchannel/valve and also in the valve filling process. Critical pressure varies linearly with the valve hydraulic diameter in the range 0.91 < D_h < 3.5 [mm] according to: P = 14.14 · D_h + 47.42 [Pa].     

Performance analysis of networks of queues under active queue management scheme

Analysis of networks of queues under repetitive service blocking mechanism has been presented in this paper. Nodes are connected according to an arbitrary configuration and each node in the networks employs an active queue management (AQM) based queueing policy to guarantee certain quality of service for multiple class external traffic. This buffer management scheme has been implemented using queue thresholds. The use of queue thresholds is a well known technique for network traffic congestion control. The analysis is based on a queue-by-queue decomposition technique where each queue is modelled as a GE/GE/1/N queue with single server, R (R ⩾ 2) distinct traffic classes and {N = N₁, N₂, … , N_R} buffer threshold values per class under first-come-first-serve (FCFS) service rule. The external traffic is modelled using the generalised exponential (GE) distribution which can capture the bursty property of network traffic. The analytical solution is obtained using the maximum entropy (ME) principle. The forms of the state and blocking probabilities are analytically established at equilibrium via appropriate mean value constraints. The initial numerical results demonstrate the credibility of the proposed analytical solution.     

Dielectric and piezoelectric properties of [0 0 1] and [0 1 1]-poled relaxor ferroelectric PZN–PT and PMN–PT single crystals

The properties of PZN–PT and PMN–PT single crystals of varying compositions and orientations have been investigated. Among the various compositions studied, [0 0 1]-optimally poled PZN-(6–7)%PT and PMN-30%PT exhibit superior dielectric and piezoelectric properties, with K^T ≈ 6800–8000, d₃₃ ≈ 2800 pC/N, d₃₁ ≈ −(1200–1800) pC/N for PZN-(6–7)%PT; and K^T = 7500–9000, d₃₃ = 2200–2500 pC/N and d₃₁ = −(1100–1400) pC/N for PMN-30%PT. These two compositions are also fairly resistant to over-poling. The [0 0 1]-poled electromechanical coupling factors (k₃₃, k₃₁ and k_t) are relatively insensitive to crystal composition. [0 1 1]-optimally poled PZN-7%PT single crystal also exhibits extremely high d₃₁ values of up to −4000 pC/N with k₃₁ ≈ 0.90–0.96. While [0 1 1]-poled PZN-7%PT single crystal becomes over-poled with much degraded properties when poled at and above 0.6 kV/mm, PZN-6%PT crystal shows no signs of over-poling even when poled to 2.0 kV/mm. The presence of a certain amount (i.e., 10–15%) of orthorhombic phase in a rhombohedral matrix has been found to be responsible for the superior transverse piezoelectric properties of [0 1 1]-optimally poled PZN-(6–7)%PT. The present work shows that flux-grown PZN–PT crystals exhibit superior and consistent properties and improved over-poling resistance to flux-grown PMN–PT crystals and that, for or a given crystal composition, flux-grown PMN–PT crystals exhibit superior over-poling resistance to their melt-grown counterparts.     

Piezoresistive TiB2/silicone rubber composites for circuit breakers

Piezoresistive composites with high hardness and conductivity are required for circuit breakers for multi-cycle operation under large current flow. Based on the simulation results for the mechanical behavior of piezoresistive composites, we developed piezoresistive composites with conductive TiB₂ ceramic materials and silicone rubber. TiB₂ up to 70 vol.% was embedded into the polymer matrix without any mechanical deterioration while the electrical resistance was decreased with increasing TiB₂ content. Piezoresistive composites with 70 vol.% TiB₂ particles exhibited a resistance of 1.7 Ω at a pressure of 1.1 MPa. A circuit breaker with the fabricated piezoresistive composites acted as a switch with a response time of around 2 ms.     

Hands-free administration of subjective workload scales: Acceptability in a surgical training environment

IntroductionSubjective workload measures are usually administered in a visual–manual format, either electronically or by paper and pencil. However, vocal responses to spoken queries may sometimes be preferable, for example when experimental manipulations require continuous manual responding or when participants have certain sensory/motor impairments. In the present study, we evaluated the acceptability of the hands-free administration of two subjective workload questionnaires – the NASA Task Load Index (NASA-TLX) and the Multiple Resources Questionnaire (MRQ) – in a surgical training environment where manual responding is often constrained.MethodSixty-four undergraduates performed fifteen 90-s trials of laparoscopic training tasks (five replications of 3 tasks – cannulation, ring transfer, and rope manipulation). Half of the participants provided workload ratings using a traditional paper-and-pencil version of the NASA-TLX and MRQ; the remainder used a vocal (hands-free) version of the questionnaires. A follow-up experiment extended the evaluation of the hands-free version to actual medical students in a Minimally Invasive Surgery (MIS) training facility.ResultsThe NASA-TLX was scored in 2 ways – (1) the traditional procedure using participant-specific weights to combine its 6 subscales, and (2) a simplified procedure – the NASA Raw Task Load Index (NASA-RTLX) – using the unweighted mean of the subscale scores. Comparison of the scores obtained from the hands-free and written administration conditions yielded coefficients of equivalence of r = 0.85 (NASA-TLX) and r = 0.81 (NASA-RTLX). Equivalence estimates for the individual subscales ranged from r = 0.78 (“mental demand”) to r = 0.31 (“effort”). Both administration formats and scoring methods were equally sensitive to task and repetition effects. For the MRQ, the coefficient of equivalence for the hands-free and written versions was r = 0.96 when tested on undergraduates. However, the sensitivity of the hands-free MRQ to task demands (η_partial² = 0.138) was substantially less than that for the written version (η_partial² = 0.252). This potential shortcoming of the hands-free MRQ did not seem to generalize to medical students who showed robust task effects when using the hands-free MRQ (η_partial² = 0.396). A detailed analysis of the MRQ subscales also revealed differences that may be attributable to a “spillover” effect in which participants’ judgments about the demands of completing the questionnaires contaminated their judgments about the primary surgical training tasks.ConclusionVocal versions of the NASA-TLX are acceptable alternatives to standard written formats when researchers wish to obtain global workload estimates. However, care should be used when interpreting the individual subscales if the object is to make comparisons between studies or conditions that use different administration modalities. For the MRQ, the vocal version was less sensitive to experimental manipulations than its written counterpart; however, when medical students rather than undergraduates used the vocal version, the instrument’s sensitivity increased well beyond that obtained with any other combination of administration modality and instrument in this study. Thus, the vocal version of the MRQ may be an acceptable workload assessment technique for selected populations, and it may even be a suitable substitute for the NASA-TLX.     

A new metric based on extended spatial frequency and its application to DWT based fusion algorithms

A new quantitative metric is proposed to objectively evaluate the quality of fused imagery. The measured value of the proposed metric is used as feedback to a fusion algorithm such that the image quality of the fused image can potentially be improved. This new metric, called the ratio of spatial frequency error (rSFe), is derived from the definition of a previous measure termed “spatial frequency” (SF) that reflects local intensity variation. In this work, (1) the concept of SF is first extended by adding two diagonal SFs, then, (2) a reference SF (SF_R) is computed from the input images, and finally, (3) the error SF (SF_E) (subtracting the fusion SF from the reference SF), or the ratio of SF error (rSFe = SF_E/SF_R), is used as a fusion quality metric. The rSFe (which can be positive or negative) indicates the direction of fusion error—over-fused (if rSFe > 0) or under-fused (if rSFe < 0). Thus, the rSFe value can be back propagated to the fusion algorithm (BP fusion), thereby directing further parameter adjustments in order to achieve a better-fused image. The accuracy of the rSFe is verified with other quantitative measurements such as the root mean square error (RMSE) and the image quality index (IQI), as well as with a qualitative perceptual evaluation based on a standard psychophysical paradigm. An advanced wavelet transform (aDWT) method that incorporates principal component analysis (PCA) and morphological processing into a regular DWT fusion algorithm is implemented with two adjustable parameters—the number of levels of DWT decompositions and the length of the selected wavelet. Results with aDWT were compared to those with a regular DWT and with a Laplacian pyramid. After analyzing several inhomogeneous image groups, experimental results showed that the proposed metric, rSFe, is consistent with RMSE and IQI, and is especially powerful and efficient for realizing the iterative BP fusion in order to achieve a better image quality. Human perceptual assessment was measured and found to strongly support the assertion that the aDWT offers a significant improvement over the DWT and pyramid methods.