等温微量量热法研究石油污染对土壤微生物活性的影响

利用TAMⅢ等温微量量热仪研究不同浓度的石油污染对土壤微生物活性的影响。对大港油田不同石油污染程度的土壤样品（3683-5-1、西51-5、西15-14和8-13-6H-1）以及实验室配置的短时间内石油污染土壤（空白、0.5%、1.5%、2.5%和4.0%）进行了微量热检测。含油量升高,总放热量升高,生长速率常数降低,峰值功率先升高后降低,达到最大峰值功率的时间随着含油量的升高而延长。结果表明,石油污染会影响土壤微生物的活性,并且在低浓度时促进微生物的生长,石油浓度高时会抑制土壤中微生物的生长代谢。     

Reactive chemical hazards of diazonium salts

Many diazonium salts are thermally unstable and sensitive to friction and shock. Most diazonium salts are known for their violent decomposition hazard in the solid state. There are many industrial and laboratory incidents caused by this group of chemicals. For safety purposes, the hazards related to the preparation and the handling of diazonium salts are discussed. Twelve cardinal rules are provided:1. Use only a stoichiometric amount of sodium nitrite when generating diazonium salts, avoiding excess sodium nitrite.2. Check for the excess of nitrous acid by starch–potassium iodide papers and neutralize it.3. Minimize the presence of nitrous acid by combining amine and acid first, then subsequently adding the sodium nitrite.4. Keep the temperature below 5 °C.5. Always vent the gases generated.6. Determine the thermal stability of diazonium compounds in your system.7. Understand the explosive properties of diazonium salts. If unknown, always assume they are explosive.8. Never allow the undesired precipitation of diazonium salts out of solution.9. Analyze the residual diazo compounds in the final product, especially for new process conditions.10. Quench the remaining diazonium salts before any further treatments.11. Isolate no more than 0.75 mmol of explosive diazonium salts at one time; also consider the addition of an inert material to stabilize the diazonium salts.12. Use a plastic spatula when handling the solid. The dried powder should not be “scratched” with a metal spatula or ground finely.An example of a testing strategy and data interpretation is provided for a process which has multiple steps and two diazonium compounds. Differential Scanning Calorimetry (DSC) and Heat of Mixing calorimetry (HOM) successfully serve as efficient tests to screen thermal stability and gas generation, identifying the candidates for advanced tests.     

Effects of metal ions on thermal hazard of tert-butyl peroxy-3,5,5-trimethylhexanoate

As a commonly used initiator for polyethylene, tert-butyl peroxide 3,5,5-trimethylhexanoate (TBPTMH), with the molecular formula of C₁₃H₂₆O₃, is more likely to decompose and cause fires and explosions. Understanding the thermal risks of TBPTMH mixed with common metal ions, potentially in containers and pipes, is important. In this work, by using differential scanning calorimetry (DSC) and Phi-Tec adiabatic calorimetry, the effects of CuCl₂, FeCl₃, CuBr_2, and FeBr₃ on the thermal decomposition of TBPTMH were investigated. Adiabatic kinetic analysis was performed and the apparent activation energy (E_a) was calculated by thermodynamic analysis. Time to maximum rise under adiabatic conditions (TMR_ad) and the self-accelerating decomposition temperature (SADT) under different packing qualities were reckoned. It was found that the thermal risk of TBPTMH was increased while mixing these metal ions, especially CuBr₂. To ensure the safety of the substance in process industry, the temperature of TBPTMH in the presence of metal should be governed below 39.48 °C. This work was expected to provide some guidance for improving the process safety of TBPTMH.     

Study of Aging Characteristics of Ternary Blends of Polyethylenes—II

Six film samples of low-density polypropylene (LDPE)/linear LDPE (LLDPE)/high-density polypropylene (HDPE) with varying ratios of LDPE (20–45 ... wt%) and LLDPE (25–50 wt%) having a fixed amount of HDPE at 30 wt% were prepared by blown film extrusion technique. The samples were aged at four different temperatures, 55°, 70°, 85°, and 100°C, for four different time periods in the interval of between 150 hours and up to 600 hours. The change in the structure of various constituents and the formation of various oxygenated (peroxy and hydroperoxy) and unsaturated groups during thermo-oxidative degradation was discussed by infrared spectroscopy. The visiosity-average molecular weight was found to have decreased slowly in the initial aging hours and temperatures, whereas it decreased by 10% with its previous value tensile strength that is, 100°C when aged for 600 hours. The tensile strength of the sample first increased by 67% at 55°C and 89% at 70°C up to 450 hours, whereas the values increased by 52.5% at 85°C and 33.9% at 100°C when aged for 150 hours and then decreased. The percentage elongation at break increased by 2.7% at 55°C and 10.7% at 70°C for 150 and 300 hours of aging, respectively, whereas the percentage decreased when aged at 85°C and 100°C for up to 600 hours of aging. The values of gel content (percent) increased and initial degradation temperature decreased with aging time and temperature.     

陶瓷涂层性能影响因素及工艺优化研究

为了提高Al2O3陶瓷涂层的综合性能,对陶瓷涂层性能影响因素进行了正交试验设计。以磨损量、结合强度和耐腐蚀性为评价指标,得出了在Al2O3陶瓷颗粒粒径为160目,颗粒填入量为125%,涂层厚度为1 mm时,综合性能最好。同时利用差示扫描量热（DSC）技术推算出胶粘剂体系的最佳固化工艺为50℃（1h）→100℃（2 h）→225℃（1h）;采用磷酸阳极化（PAA）方法对铝合金基体表面进行处理,使其与涂层之间获得最好的结合强度。     

基于热爆炸理论的煤燃点确定及动力学分析

为准确判断煤燃点,提高煤自燃灾害防治能力,依据热爆炸理论,结合煤自燃过程放热曲线,将煤自燃升温过程中微分热流曲线上第1处极小值点作为煤的燃点,计算煤着火前后放热过程动力学参数变化.结果表明:随升温速率增加,煤自燃反应放热过程逐渐向高温区域移动,煤燃点逐渐增大,反应的活化能逐渐减小;同一升温速率下燃点之后煤的活化能增大;...     

Experimental hazardous risk investigation of energetic styphnic acid analytical reagent in calorimetric analysis

Analytical reagents identify and manage metal pollution, a major environmental issue. Regrettably, these compounds' safety concerns, especially when heated, have been neglected. This research examines the thermal hazard of the extremely reactive analytical reagent styphnic acid. Differential scanning calorimetry, thermogravimetric analysis, and accelerating rate calorimetry examined styphnic acid's thermodynamics. Thermogravimetric analysis showed weight loss reactions starting at 127 °C and peaking at 208 °C. Differential scanning calorimetry showed an endothermic peak at 176 °C. The accelerating rate calorimetry test showed that styphnic acid self-accelerates at 237 °C after 196.5 °C. Kissinger, Ozawa-Flynn-Wall, and Kissinger-Akahira-Sunose thermokinetic models calculated apparent activation energy from 131.677 to 155.718 kJ/mol. A nonlinear regression analysis showed that styphnic acid undergoes a two-step autocatalytic reaction during heat degradation. Thermal safety was assessed by measuring time to conversion limit, maximum rate, total energy release, self-accelerating decomposition temperature, and adiabatic temperature rise. Styphnic acid is less stable at higher temperatures and its thermal hazards depend on heating rate. The computed SADT was 109.04 °C, with alarm and control temperatures of 104.04 and 99.04 °C, respectively. The risk matrix analysis based on T_ad and TMR_ad suggests reducing thermal instability. This study on styphnic acid's thermal risks and safe storage and transit during analytical applications is beneficial.     

Prediction of the self-ignition temperature in lagging fires by means of isothermal calorimetry

Under certain circumstances, contamination of a porous insulation material by a combustible liquid may result in a lagging/insulation fire. In the current study, a method based on isothermal calorimetry and modelling to estimate the risk of a lagging fire, or a maximum insulation thickness for a certain system temperature, is presented. The studied system was a combination of mineral wool and rapeseed oil. Full-scale tests were performed to determine suitable ignition criteria and to validate the results from the isothermal calorimetry tests and modelling. We contaminated the lagging using two methods – a direct method and a solvent method. These methods were evaluated in the full-scale tests. The solvent method resulted in more repeatable results than the direct method, where the contaminant was poured on the insulation. Using the calorimetric measurements, we estimated the parameters for the kinetic equation. This result was used to estimate the self-ignition temperature of contaminated lagging installed on a pipe. We found that a temperature increase of 40 °C was a reasonable ignition criterion when modelling.