A New Protocol for Ash Wood Modification: Synthesis of Hydrophobic and Antibacterial Brushes from the Wood Surface

The article presents the modification of ash wood via surface initiated activators regenerated by electron transfer atom transfer radical polymerization mediated by elemental silver (Ag⁰ SI-ARGET ATRP) at a diminished catalyst concentration. Ash wood is functionalized with poly(methyl methacrylate) (PMMA) and poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) to yield wood grafted with PMMA-b-PDMAEMA-Br copolymers with hydrophobic and antibacterial properties. Fourier transform infrared (FT-IR) spectroscopy confirmed the covalent incorporation of functional ATRP initiation sites and polymer chains into the wood structure. The polymerization kinetics was followed by the analysis of the polymer grown in solution from the sacrificial initiator by proton nuclear magnetic resonance (¹H NMR) and gel permeation chromatography (GPC). The polymer layer covalently attached to the wood surface was observed by scanning electron microscopy (SEM). The hydrophobic properties of hybrid materials were confirmed by water contact angle measurements. Water and sodium chloride salt aqueous solution uptake tests confirmed a significant improvement in resistance to the absorption of wood samples after modification with polymers. Antibacterial tests revealed that wood-QPDMAEMA-Br, as well as wood-PMMA-b-QPDMAEMA-Br, exhibited higher antibacterial activity against Gram-positive bacteria (Staphylococcus aureus) in comparison with Gram-negative bacteria (Escherichia coli). The paper presents an economic concept with ecological aspects of improving wood properties, which gives great opportunities to use the proposed approach in the production of functional hybrid materials for industry and high quality sports equipment, and in furniture production.     

Chromatographic chemical characterization of solvent refined coal I and II liquids for toxicological testing

Summary High resolution gas chromatography and gas chromatography/mass spectrometry were employed to determine the components in samples of solvent refined coal (SRC) II naphtha, middle distillate, heavy distillate, and fuel oil blend and SRC-I light oil, wash solvent, and process solvent in concentrations higher than approximately 0.5%. Quantitation was based on the addition of n-alkane internal standards and peak area response of a flame ionization detector with the use of fused silica and glass capillary columns coated with SE-52 and SF-96. The major differences in the SRC-I and II materials were the molecular weight ranges and sizes of the chemical components found in the products, an effect of the differences in the nominal boiling ranges of the materials. Alkanes, alkenes, hydroxylated aromatics, hydrogenated and polycyclic aromatic hydrocarbon ring systems, and alkylated derivatives of the above were found in greatest concentration in the unfractionated materials. Sulfur and nitrogen heteroatomic species were in greates concentration in the higher nominal boiling range materials. A major purpose of these investigations was to develop a method to obtain data on the composition of these complex sample matrices for use in designing studies for toxicological evaluation of these materials.     

Molecular Simulation on Competitive Adsorption Differences of Gas with Different Pore Sizes in Coal

Micropores are the primary sites for methane occurrence in coal. Studying the regularity of methane occurrence in micropores is significant for targeted displacement and other yield-increasing measures in the future. This study used simplified graphene sheets as pore walls to construct coal-structural models with pore sizes of 1 nm, 2 nm, and 4 nm. Based on the Grand Canonical Monte Carlo (GCMC) and molecular dynamics theory, we simulated the adsorption characteristics of methane in pores of different sizes. The results showed that the adsorption capacity was positively correlated with the pore size for pure gas adsorption. The adsorption capacity increased with pressure and pore size for competitive adsorption of binary mixtures in pores. As the average isosteric heat decreased, the interaction between the gas and the pore wall weakened, and the desorption amount of CH₄ decreased. In ultramicropores, the high concentration of CO₂ (50–70%) is more conducive to CH₄ desorption; however, when the CO₂ concentration is greater than 70%, the corresponding CH₄ adsorption amount is meager, and the selected adsorption coefficient S_CO2/CH4 is small. Therefore, to achieve effective desorption of methane in coal micropores, relatively low pressure (4–6 MPa) and a relatively low CO₂ concentration (50–70%) should be selected in the process of increasing methane production by CO₂ injection in later stages. These research results provide theoretical support for gas injection to promote CH₄ desorption in coal pores and to increase yield.     

Electrochemical and Spectroscopic Properties of Fly Ash–Polyaniline Matrix Nanorod Composites

Polyaniline (PANI) nanocomposites were prepared with fly ash (FA) either by aging the starting materials (aniline and FA) before oxidative polymerisation or by including poly(styrene sulphonic acid) (PSSA) eliminating the aging step. The aging procedure formed polymer nanotubes that have cross-sectional diameters of 50–110 nm. The procedure involving PSSA produced nanorods and nanofibres composites that have diameters of 100–500 nm and length of up to 10 μm attributed to the presence of metal oxides and silica in FA. The electrochemical analysis of the PANI–PSSA–FA nanorod composites shows three redox couples with formal potentials, , values of 105 mV, 455 mV and 670 mV, and conductance, C, value of 1.21 × 10⁻² S. The UV-Vis spectroscopy of the polymeric nanorod shows absorption maxima at 340 and 370 nm (due to π–π^* transition of the benzoid rings), and 600–650 nm (due to charge transfer excitons of the quinoid structure), which are characteristic of emeraldine base.     

Microbial liquefaction of lignite pretreated with dilute acid at elevated temperature and pressure

Two microbial cultures—ML-13 (aCandida sp.) and LSC (a fungal isolate from the University of Arkansas)—have been employed in the direct liquefaction of Louisiana lignite. Lignite samples were pretreated with nitric acid and microbial culture broths at elevated temperatures and pressures. Subsequent treatment with active cultures and culture derivatives resulted in significant solubilization of the lignite. Up to 50% liquefaction of pretreated coal (20% HNO₃ at ambient temperature and pressure) was observed in 4 d with ML-13 cultures, whereas almost 80% liquefaction occurred in a similar time period when exposing pretreated lignite to an autoclaved, cell-free culture broth.     

Isotope dilution-thermal ionisation mass spectrometric analysis for tin in a fly ash material

Isotope dilution-thermal ionisation mass spectrometry (ID-TIMS) analysis has been applied to the determination of tin in a fly ash sample supplied by the EC Joint Research Centre (Ispra, Italy). The proposed procedure includes the silica gel/phosphoric acid technique for tin thermal ionisation activation and a strict heating protocol for isotope ratio measurements. Instrumental mass discrimination factor has been previously determined measuring a natural tin standard solution. Spike solution has been prepared from ¹¹²Sn-enriched metal and quantified by reverse isotope dilution analysis. Two sample aliquots were spiked and tin was extracted with 4.5 M HCl during 25 min ultrasound exposure time. Due to the complex matrix of this fly ash material, a two-step purification stage using ion-exchange chromatography was required prior TIMS analysis. Obtained results for the two sample-spike blends (10.11 ± 0.55 and 10.50 ± 0.64 μmol g⁻¹) are comparable, both value and uncertainty. Also a good reproducibility is observed between measurements. The proposed ID-TIMS procedure, as a primary method and due to the lack of fly ash reference materials certified for tin content, can be used to validate more routine methodologies applied to tin determination in this kind of samples.     

几种烟煤及其热处理后的溶胀性能研究

研究了四种不同变质程度烟煤及其二硫化碳/N-甲基-2-吡咯烷酮（CS2/NMP）混合溶剂(1∶1,vol)的抽提物在不同溶剂中的溶胀性能,同时考察了四种煤样不同温度热处理后其溶胀性能的变化。结果表明,煤的溶胀率随煤化度增加而有所降低;变质程度较低的烟煤在极性溶剂中的溶胀率大于非极性溶剂,随着煤化度的增加,两者溶胀度差距减小;四种烟煤经混合溶剂抽提后,其抽余煤的交联密度降低,溶胀率增加。四种煤样150℃热处理后在CS2中的溶胀率均有所增加,表明热处理可以降低煤的交联密度。随着热处理温度提高至240℃,除气煤外,其余三种煤样在NMP和CS2中溶胀率均进一步增大,说明其交联密度进一步降低。这一结果与热处理煤样在混合溶剂中抽提率的变化趋势一致,如240℃热处理后瘦煤的抽提率由原煤的6.9%提高到17.3%。红外光谱研究表明,经过适当温度的热处理,可以脱除煤分子中的羰基和羟基等含氧官能团,破坏煤结构中的氢键,从而降低煤的交联密度,提高煤的溶胀率及其在混合溶剂中的抽提率。     

原位担载Fe_2S_3催化剂煤的热解动力学研究

用加压热天平研究了原位担载纳米级Fe2 S3 催化剂的大柳塔次烟煤的加氢热解动力学 ,考查了 2 0MPa氢气氛或氮气氛下原煤及担载催化剂的煤热解失重过程 ,计算了活化能E和指前因子A等热解动力学参数。结果表明 ,煤原位担载Fe2 S3 催化剂后热失重速率比原煤有较大程度的增加 ,最大热解速率的特征温度也比原煤降低。特别是煤在表面活性剂十六烷基三甲基溴化铵溶液中担载Fe2 S3 催化剂后的热解反应速率高于水溶液中担载同样催化剂的热解反应速度。原位担载Fe2 S3 的煤及原煤的热解反应过程符合一级反应动力学。     

东胜长焰煤热解含氧官能团结构演化的13C-NMR和FT-IR分析

以东胜煤田色拉一号井田2号煤层长焰煤为研究对象,利用浮沉离心法富集其镜质组。基于工业分析、元素分析、¹³C-NMR、FT-IR、谱图分峰拟合技术和化学分析测试,求取镜煤及一系列热解煤含氧官能团结构与含量参数,从不同角度研究了含氧官能团的分布规律与演化特点。镜煤中羧基、羰基含量分别为8.91~10.90 mol/kg、1.61~1.79 mol/kg,随热解温度升高羧基显著减少。热解作用促使以端基形式连接在脂肪链或脂肪环结构氧上的甲基和亚甲基首先脱去,且在温度高于350 ℃后基本稳定。氧在热解过程赋存状态的变化是芳香体系与脂肪体系相互竞争的结果,510 ℃热解煤中芳香类氧和脂肪类氧的含量分别为7.49、3.45 mol/kg。羟基的演化过程与热解过程中氧的赋存状态密切相关。随着热解过程的进行,在热解温度低于440 ℃时,各种羟基含量均减少,热解过程对于大分子网络的破坏干扰了各种氢键作用,而羟基π作用则暂时增强,至510 ℃时各种氢键含量均降为最低。东胜长焰煤中含氧官能团化学活性顺序为:[COOH]>[R-O]>[Ar-O-Ar,Ar-O-C,C-O-C]>[C=O]。镜煤非活性醚键含量为0.68 mol/kg,活性醚键为0.48 mol/kg,主要为非活性醚键。