以机油为分散剂高温热解人发合成新型碳点及其生物效应研究

目的以机油为分散剂高温热解人发后发现新型纳米碳点,通过动物实验评价了该碳点的生物效应。方法利用高温热解法对人发和机油进行炭化,对炭化产物进行萃取、过滤分离和透析得到一种具有水溶性的新型物质碳点,并命名为JYRF-CDs。利用透射电子显微镜(TEM)、高分辨透射电子显微镜(HR-TEM)、紫外-可见分光光谱、傅里叶变换红外光谱、荧光光谱、X射线光电子能谱分析(XPS)等多种方法对JYRF-CDs进行表征,利用小鼠单核巨噬细胞RAW264.7细胞进行CCK-8毒性实验来评价JYRF-CDs的安全性,并通过小鼠耳肿胀实验和小鼠醋酸扭体实验对JYRF-CDs的生物效应进行评价。结果 JYRF-CDs外形为类球形,粒径均匀分布在1.8～3.6 nm,晶格间距为0.219 7 nm。细胞毒性实验结果显示,JYRF-CDs具有低毒性,动物实验结果表明JYRF-CDs具有良好的抗炎和镇痛作用。结论首次以机油为分散剂高温热解人发后发现一种全新的碳点JYRF-CDs,以JYRF-CDs为突破口,更加明确阐释以机油为分散剂高温热解人发后炭化产物具有生物效应的物质基础,为纳米类成分的研究提供了一种新方法。     

赤石脂和禹余粮作为灶心土替代品的分析

目的:通过比较灶心土、赤石脂和禹余粮的热解特性及红外光谱相似度来探讨赤石脂、禹余粮替代灶心土的可行性。方法:热解特性研究采用热重差热综合热分析仪,取试样量(30±5)mg置于坩锅中,以10℃·min~(-1)的升温速率、流量60 m L·min~(-1)的恒定流速通入模拟空气[N_2-O_2(4∶1)],从室温升至900℃。红外光谱试验采用溴化钾压片法,光谱分辨率4 cm~(-1),测量范围4 000~500 cm-1,扫描信号累加32次,所得数据经Omnic软件进行自动基线校正、平滑及纵坐标归一化。数据处理及图表绘制采用Origin 8.0软件和Omnic软件完成。结果:比较热解特性发现灶心土、赤石脂、禹余粮的热解特性均在400~600℃处出现一段失重台阶;但整体而言,赤石脂与禹余粮热解特性没有体现出灶心土热解特性的复杂性;通过红外光谱相似度数值得出,以灶心土作为对照,赤石脂与灶心土相似度数值较偏低,禹余粮与与灶心土相似度数值处于中等水平。结论:就热解特性及红外光谱相似度而言,禹余粮与灶心土相似性较好,可能较赤石脂更适用作灶心土的替代品,为相关中药炮制辅料的研究提供参考。     

大黄、地榆、牡丹皮炒炭过程中热解反应机制的分析

目的:推断并验证大黄、地榆、牡丹皮3味中药炒炭的热解反应机制,进一步完善这3味中药炒炭研究的理论。方法:采用模式函数法中的单个扫描速率的不定温法(Coats-Redfern模型与Achar模型)推断大黄、地榆、牡丹皮3味中药炒炭过程中热解反应的机理函数,通过比较转化率(α)理论值、实验值与1/T的热分析曲线对机理函数进行验证。结果:积分形式表达式能更较好地描述大黄、地榆、牡丹皮3味中药炒炭热解的反应机制,三者的炒炭热解机理函数分别为9号机理函数积分形式g(α)=[(1-α)-1/3-1]2,2号机理函数积分形式g(α)=α+(1-α)ln(1-α),9号机理函数积分形式g(α)=[(1-α)-1/3-1]2。结论:3味中药炒炭的热解反应机制均属于反应扩散,转化率理论值与实验值存在一定的差异,运用热分析动力学方法只是尽可能地模拟这3味中药的炒炭热解反应过程。     

Control of Porous Layer Thickness in Thermophoretic Deposition of Nanoparticles

The film thickness plays an important role in the performance of materials applicable to different technologies including chemical sensors, catalysis and/or energy materials. The relationship between the surface and volume of the functional layers is key to high performance evaluations. Here we demonstrate the thermophoretic deposition of different thicknesses of the functional layers designed using flame combustion of tin 2-ethylhexanoate dissolved in xylene, and measurement of thickness by scanning electron microscopy and focused ion beam. The parameters such as spray fluid concentration (differing Sn²⁺ content), substrate-nozzle distance and time of the spray were considered to investigate the layer growth. The results showed ≈ 23, 124 and 161 μm thickness of the SnO₂ layer after flame spray of 0.1, 0.5 M and 1.0 M tin 2-EHA-Xylene solutions for 1200 s. While Sn²⁺ concentration was 0.5 M for all the flame sprays, the substrates placed at 250, 220 and 200 mm from the flame nozzle had layer thicknesses of 113, 116 and 132 µm, respectively. Spray time dependent thickness growth showed a linear increase from 8.5 to 152.1 µm when the substrates were flame sprayed for 30 s to 1200 s using 0.5 M tin 2-EHA-Xylene solutions. Changing the dispersion oxygen flow (3–7 L/min) had almost no effect on layer thickness. Layers fabricated were compared to a model found in literature, which seems to describe the thickness well in the domain of varied parameters. It turned out that primary particle size deposited on the substrate can be tuned without altering the layer thickness and with little effect on porosity. Applications depending on porosity, such as catalysis or gas sensing, can benefit from tuning the layer thickness and primary particle size.     

Pyrolysis Kinetic Properties of Thermal Insulation Waste Extruded Polystyrene by Multiple Thermal Analysis Methods

Extruded polystyrene (XPS) is a thermal insulation material extensively applied in building systems. It has attracted much attention because of outstanding thermal insulation performance, obvious flammability shortcoming and potential energy utilization. To establish the reaction mechanism of XPS’s pyrolysis, thermogravimetric experiments were performed at different heating rates in nitrogen, and multiple methods were employed to analyze the major kinetics of pyrolysis. More accurate kinetic parameters of XPS were estimated by four common model-free methods. Then, three model-fitting methods (including the Coats-Redfern, the iterative procedure and masterplots method) were used to establish the kinetic model. Since the kinetic models established by the above three model-fitting methods were not completely consistent based on different approximations, considering the effect of different approximates on the model, the reaction mechanism was further established by comparing the conversion rate based on the model-fitting methods corresponding to the possible reaction mechanisms. Finally, the accuracy of the above model-fitting methods and Particle Swarm Optimization (PSO) algorithm were compared. Results showed that the reaction function g(α) = (1 − α)⁻¹ − 1 might be the most suitable to characterize the pyrolysis of XPS. The conversion rate calculated by masterplots and PSO methods could provide the best agreement with the experimental data.     

Amorphous Silicon Oxynitride-Based Powders Produced by Spray Pyrolysis from Liquid Organosilicon Compounds

Silicon oxynitrides (SiO_xN_y) have many advantageous properties for modern ceramic applications that justify a development of their new and efficient preparation methods. In the paper, we show the possibility of preparing amorphous SiO_xN_y-based materials from selected liquid organosilicon compounds, methyltrimethoxysilane CH₃Si(OCH₃)₃ and methyltriethoxysilane CH₃Si(OC₂H₅)₃, by a convenient spray pyrolysis method. The precursor mist is transported with an inert gas or a mixture of reactive gases through a preheated tube reactor to undergo complex decomposition changes, and the resulting powders are collected in the exhaust filter. The powders are produced in the tube at temperatures of 1200, 1400, and 1600 °C under various gas atmosphere conditions. In the first option, argon Ar gas is used for mist transportation and ammonia NH₃ gas serves as a reactive medium, while in the second option nitrogen N₂ is exclusively applied. Powder X-Ray Diffraction (XRD) results confirm the highly amorphous nature of all products except those made at 1600 °C in nitrogen. SEM examination shows the spheroidal particle morphology of powders, which is typical for this method. Fourier Transform Infrared (FT-IR) spectroscopy reveals the presence of Si–N and Si–O bonds in the powders prepared under Ar/NH₃, whereas those produced under N₂ additionally contain Si–C bonds. Raman spectroscopy measurements also support some turbostratic free carbon C in the products prepared under nitrogen. The directly determined O- and N-contents provide additional data linking the process conditions with specific powder composition, especially from the point of view of oxygen replacement in the Si–O moieties formed upon initial precursor decomposition reactions by nitrogen (from NH₃ or N₂) or carbon (from the carbonization of the organic groups).     

Weakly Hydrated Anion Exchangers Doped with Cu2O and Cu0 Particles—Thermogravimetric Studies

Hybrid ion exchangers (HIXs) containing fine Cu₂O and Cu⁰ particles were subjected to thermal analysis in order to determine their hygroscopic water content (with regard to their anomalously low porosity) and to determine the effect of the oxidation state of the copper atom in the deposit on the thermal properties of composite materials. Commercially available anion exchangers, Amberlite IRA 900Cl (macroreticular, M) and Amberlite IRA 402OH (gel-like, G), were used as supporting materials. M/Cu₂O, G/Cu₂O, M/Cu and G/Cu, containing 4.3–8.4 wt% Cu, were subjected to thermal analysis under respectively air and N₂. TG/DTG curves revealed that dry M/Cu and G/Cu contained as little as 7.2% and 4.3% hygroscopic water, while M/Cu₂O and G/Cu₂O contained respectively 10.6% and 9.4% (Cu⁰ was a stronger water repellent than Cu₂O). The oxidation state of the copper atom in the deposit was found to affect the amount of the forming char, and also Cu⁰ was found to contribute to the formation of more char than in the pyrolysis of the pure resin (the anion exchanger with no copper deposit). Under air the two kinds of particles transformed into CuO, while under N₂ metallic copper and char (from the resin phase) made up the solid residue. This means that in the pyrolysis of the HIXs the inorganic phase participated in char formation and it also transformed itself (undergoing reduction when possible). The above findings provide a basis for in-depth research aimed at the innovative use of copper-containing HIXs and at obtaining usable composite materials with a designed (organic-inorganic) composition.     

Formation of polycyclic aromatic hydrocarbons from tobacco: the link between low temperature residual solid (char) and PAH formation.

The formation of condensed ring polycyclic aromatic hydrocarbons (PAHs) from the pyrolysis of ground tobacco in helium over the temperature range of 350-600 degrees C was investigated. PAH yields in the ng/g range were detected and the maximum yields of all PAHs studied including benzo[a]pyrene (B[a]P) and benzo[a]anthracene (B[a]A) occurred between 500 and 550 degrees C. The pathway to PAH formation in the 350-600 degrees C temperature range is believed to proceed via a carbonization process where the residual solid (char) undergoes a chemical transformation and rearrangement to give a more condensed polycyclic aromatic structure that upon further heating evolves PAH moieties. Extraction of tobacco with water led to a two fold increase in the yields of most PAHs studied. The extraction process removed low temperature non-PAH-forming components, such as alkaloids, organic acids and inorganic salts, and concentrated instead (on a per unit weight basis) tobacco components such as cell wall bio-polymers and lipids. Hexane extraction of the tobacco removed lipophilic components, previously identified as the main source of PAH precursors, but no change in PAH yields was observed from the hexane-extracted tobacco. Tobacco cell wall components such as cellulose, hemicellulose, and lignin are identified as major low temperature PAH precursors. A link between the formation of a low temperature char that evolves PAHs upon heating is established and the observed ng/g yields of PAHs from tobacco highlights a low temperature solid phase formation mechanism that may be operable in a burning cigarette.     

加压快速热解液相炭化焦的物理性质及CO2气化活性

以一种液相炭化焦(石油焦)为原料,在快速升温和热解压力为常压至3 MPa下制备了热解焦,主要考察了热解停留时间和热解压力对其失重、BET表面积和CO2气化活性的影响。结果表明：在加压快速热解条件下,随热解停留时间增加,液相炭化焦的失重率增加,BET表面积呈下降趋势,气化活性略微减小;随热解压力增加,液相炭化焦的失重率增加,BET表面积先增加后下降,气化活性略微变化,甚至基本不变;常压条件下液相炭化焦的气化活性明显高于加压条件下的气化活性。