Blends of Bio-Based Poly(Limonene Carbonate) with Commodity Polymers

In this study, blends of the bio-based poly(limonene carbonate) (PLimC) with different commodity polymers are investigated in order to explore the potential of PLimC toward generating more sustainable polymer materials by reducing the amount of petro- or food-based polymers. PLimC is employed as minority component in the blends. Next to the morphology and thermal properties of the blends the impact of PLimC on the mechanical properties of the matrix polymers is studied. The interplay of incompatibility and zero-shear melt viscosity contrast determines the blend morphology, leading for all blends to a dispersed droplet morphology for PLimC. Blends with polymers of similar structure to PLimC (i.e., aliphatic/aromatic polyester) show the best performance with respect to mechanical properties, whereas blends with polystyrene or poly(methyl methacrylate) are too brittle and polyamide 12 blends show very low elongations at break. In blends with Ecoflex (poly(butylene adipate-co-terephthalate)) and Arnitel EM400 (copoly(ether ester)) with poly(butylene terephthalate) hard and polytetrahydrofuran soft segments) a threefold increase in E-modulus can be achieved, while keeping the elongation at break at reasonable high values of ≈200%, making these blends highly interesting for applications.     

Thermal transport and chemical conversion in single reacting sorbent particles

The effects of particle size and carbon dioxide concentration on chemical conversion in engineered spherical particles undergoing calcium oxide looping are investigated. Particles are thermochemically cycled in a furnace under different carbon dioxide concentrations. Changes in composition due to chemical reactions are measured using thermogravimetric analysis. Gas composition at the furnace exit is evaluated with mass spectroscopy. A numerical model of thermal transport phenomena developed previously is adapted to match the physical system investigated in the present study. The model is used to elucidate effects of reacting medium characteristics on particle temperature and reaction extent. Experimental and numerical results show that (1) an increase in particle size results in a decrease in carbonation extent, and (2) the carbonation step consists of fast and slow reaction regimes. The reaction rates in the fast and slow carbonation regimes increase with increasing carbon dioxide concentration. The effect of carbon dioxide concentration and the distinction between the fast and slow regimes become more pronounced with increasing particle size.     

伊拉克A油田Asmari组混积型碳酸盐岩储层隔夹层研究

伊拉克A油田Asmari组为大型混积型碳酸盐岩油藏,发育灰岩、白云岩、砂岩、泥岩和硬石膏等多种岩性,储层复杂、非均质性强,存在多种类型的隔夹层。基于岩心、薄片、测井和分析测试等资料,对研究区隔夹层类型及特征展开综合分析,识别出了泥岩、硬膏岩和泥-微晶碳酸盐岩3类隔夹层。泥岩和硬石膏致密无孔隙、基本不具有渗流能力,对流体流动可以起到阻挡作用;泥-微晶碳酸盐岩属于细粒碳酸盐岩沉积,孔隙度低,但一般裂缝较发育,具有一定渗流能力,不能对流体起到有效的隔挡作用。硬石膏主要在油田中部及北部A段发育,其对油田北部储层纵向连通起到一定隔挡作用,导致纵向压力衰竭不一致。泥岩主要在C段顶部、B4和B1层发育,平面上主要在油田南部较发育。C段顶部发育一套厚度较大、稳定分布的泥岩隔层,将C段和上部B段及A段分隔为两个独立的油水系统,并有效阻挡了C段水层锥进到B段;B4和B1层泥岩较发育,但由于油田南部区域断层和裂缝较发育,导致泥岩隔夹层未能起到有效隔挡作用。搞清研究区隔夹层类型、分布及是否起隔挡作用,对A油田各区域各小层有效动用开发、见水规律研究具有很好的指导意义。     

Nitrate Additives Coordinated with Crown Ether Stabilize Lithium Metal Anodes in Carbonate Electrolyte

Lithium metal anodes (LMAs) are promising for next-generation batteries but have poor compatibility with the widely used carbonate-based electrolytes, which is a major reason for their severe dendrite growth and low Coulombic efficiency (CE). A nitrate additive to the electrolyte is an effective solution, but its low solubility in carbonates is a problem that can be solved using a crown ether, as reported. A rubidium nitrate additive coordinated with 18-crown-6 crown ether stabilizes the LMA in a carbonate electrolyte. The coordination promotes the dissolution of NO₃⁻ ions and helps form a dense solid electrolyte interface that is Li₃N-rich which guides uniform Li deposition. In addition, the Rb (18-crown-6)⁺ complexes are adsorbed on the dendrite tips, shielding them from Li deposition on the dendrite tips. A high CE of 97.1% is achieved with a capacity of 1 mAh cm⁻² in a half cell, much higher than when using the additive-free electrolyte (92.2%). Such an additive is very compatible with a nickel-rich ternary cathode at a high voltage, and the assembled full battery with a cathode material loading up to 10 mg cm⁻² shows an average CE of 99.8% over 200 cycles, indicating a potential for practical use.     

Experimental study on mitigating wind erosion of calcareous desert sand using spray method for microbially induced calcium carbonate precipitation

Wind erosion is one of the significant natural calamities worldwide, which degrades around one-third of global land. The eroded and suspended soil particles in the environment may cause health hazards, i.e. allergies and respiratory diseases, due to the presence of harmful contaminants, bacteria, and pollens. The present study evaluates the feasibility of microbially induced calcium carbonate precipitation (MICP) technique to mitigate wind-induced erosion of calcareous desert sand (Thar desert of Rajasthan province in India). The temperature during biotreatment was kept at 36 °C to stimulate the average temperature of the Thar desert. The spray method was used for bioaugmentation of Sporosarcina (S.) pasteurii and further treatment using chemical solutions. The chemical solution of 0.25 pore volume was sprayed continuously up to 5 d, 10 d, 15 d, and 20 d, using two different concentration ratios of urea and calcium chloride dihydrate viz 2:1 and 1:1. The biotreated samples were subjected to erosion testing (in the wind tunnel) at different wind speeds of 10 m/s, 20 m/s, and 30 m/s. The unconfined compressive strength of the biocemented crust was measured using a pocket penetrometer. The variation in calcite precipitation and microstructure (including the presence of crystalline minerals) of untreated as well as biotreated sand samples were determined through calcimeter, scanning electron microscope (SEM), and energy-dispersive X-ray spectroscope (EDX). The results demonstrated that the erosion of untreated sand increases with an increase in wind speeds. When compared to untreated sand, a lower erosion was observed in all biocemented sand samples, irrespective of treatment condition and wind speed. It was observed that the sample treated with 1:1 cementation solution for up to 5 d, was found to effectively resist erosion at a wind speed of 10 m/s. Moreover, a significant erosion resistance was ascertained in 15 d and 20 d treated samples at higher wind speeds. The calcite content percentage, thickness of crust, bulk density, and surface strength of biocemented sand were enhanced with the increase in treatment duration. The 1:1 concentration ratio of cementation solution was found effective in improving crust thickness and surface strength as compared to 2:1 concentration ratio of cementation solution. The calcite crystals formation was observed in SEM analysis and calcium peaks were observed in EDX analysis for biotreated sand.     

混菌矿化增强再生粗骨料的物理力学性能

为克服单一微生物培养成本高且矿化鲁棒性不足的缺陷，提出了一种混菌矿化增强再生粗骨料物理力学性能的方法.通过筛选矿化效率较高的好氧嗜碱混菌，考察了混菌矿化对再生粗骨料物理力学性能和混凝土抗压强度的影响.结果表明：相同增强时间下，混菌比纯菌呈现出更优异的矿化增强效果；随着混菌矿化增强时间的延长，再生粗骨料吸水率和压碎指标呈现出先减小后增大的趋势，最优增强时间为15 d；采用矿化增强再生粗骨料制备的再生混凝土抗压强度提高幅度达到22.1%.     

Ammonia production using iron nitride and water as hydrogen source under mild temperature and pressure

Ammonia generation was studied in the reaction between water and nitrogen-containing iron at 323 K and atmospheric pressure. Similar to metallic Fe, the interstitial compound Fe₃N reduced water through Fe oxidation to produce hydrogen gas, while the N combined with atomic hydrogen to produce ammonia as a byproduct. The addition of carbon dioxide to this system accelerated the reaction with concomitant consumption of carbon dioxide. The promoted ammonia production upon addition of carbon dioxide can be attributed to the generation of atomic hydrogen from the redox reaction of carbonic acid and Fe, as well as removal of used Fe from the reaction system through the formation of a soluble carbonato complex. When carbonate was added to the reaction system, the production rates of ammonia and hydrogen increased further. The results here confirmed that ammonia can be synthesized from iron nitride under mild conditions by utilizing carbon dioxide.     

Mid-scale biocemented soil columns via enzyme-induced carbonate precipitation (EICP)

Biocemented soil columns were created at a reduced scale (mid-scale) using enzyme-induced carbonate precipitation (EICP) as a prelude to field scale deployment. Approximately 0.3 m diameter × 0.75 m long columns were created using a tube-à-manchette grouting technique in 0.6 m × 0.6 m × 1.2 m boxes filled with a dry washed quarry sand. Treatment solution composition and treatment protocol, including number of cycles of treatment and time interval between cycles, were established based upon laboratory testing. The urease enzyme used in the treatment solution was extracted from jack beans in a just-in-time manner on site. The biocemented soil columns were characterized in situ using shear wave velocity, needle penetrometer and pocket penetrometer testing, dimensional measurements, and by unconfined compression strength (UCS) and carbonate content measurements on specimens recovered from the columns. The in situ measurements indicated the target UCS of 500 kPa was achieved. However, the UCS tests on recovered specimens had inconsistent results, which may be attributed to sample disturbance. Overall, the results demonstrate that EICP is a viable method for creating biocemented soil columns for ground improvement.     

液相沉淀-煅烧法制备大粒径球形四氧化三钴

以硫酸钴为原料,碳酸氢铵为沉淀剂,采用液相沉淀法合成了大粒径球形碳酸钴,考察了不同晶种量、pH和硫酸钴溶液流量对碳酸钴形貌、粒度分布、振实密度和硫元素质量分数的影响,并探究了碳酸钴的生长机理。通过分步煅烧,并设置不同升温时间使碳酸钴热分解,得出优化四氧化三钴理化指标的煅烧条件。结果表明,当晶种量为2 kg,pH在7.2～7.5,硫酸钴溶液流量为500 mL/h时,采用分段式热分解碳酸钴,各温区按统一时间(60 min)升温,所得四氧化三钴形貌为球形,中值粒径为16.52μm,振实密度达2.26 g/cm3。     

THE OLIGOCENE–MIOCENE MENILITE FORMATION IN THE UKRAINIAN CARPATHIANS: A WORLD‐CLASS SOURCE ROCK

This study investigates the hydrocarbon potential of Oligocene–Miocene shales in the Menilite Formation, the main source rock in the Ukrainian Carpathians. The study is based on the analysis of 233 samples collected from outcrops along the Chechva River in western Ukraine in order to analyse bulk parameters (TOC, Rock‐Eval), biomarkers and maceral composition. In Ukraine, the Menilite Formation is conventionally divided into Lower (Lower Oligocene), Middle (Upper Oligocene) and Upper (Lower Miocene) Members. The Early Oligocene and Early Miocene ages of the lower and upper members are confirmed by new nannoplankton data. The Lower Menilite Member is approximately 330 m thick in the study area and contains numerous chert beds and turbidite sandstones in its lower part together with organic‐rich black shales. The shales have a high content of silica which was probably derived from siliceous micro‐organisms. The TOC content of the shales frequently exceeds 20 wt.% and averages 9.76 wt.%. HI values range between 600 and 300 mgHC/gTOC (max. 800 mgHC/gTOC). The Middle Member contains thin black shale intervals but was not studied in detail. The Upper Member is about 1300 m thick in the study area and is composed mainly of organic‐rich shales. Chert layers are present near the base of the Member, and a prominent tuff horizon in the upper part represents a volcanic phase during shale deposition. The member grades into overlying molasse sediments. The average TOC content of the Upper Menilite succession is 5.17 wt.% but exceeds 20 wt.% near its base. Low T_max and vitrinite reflectance measurements for the Lower (419°C and 0.24–0.34 %R_r, respectively) and Upper (425°C and 0.26–0.32 %R_r, respectively) Menilite Member successions indicate thermal immaturity. Biomarker and maceral data suggest a dominantly marine (Type II) organic matter input mixed with varying amounts of land‐plant derived material, and indicate varying redox and salinity conditions during deposition. Determination of the Source Potential Index (SPI) shows that the Menilite Formation in the study area has the potential to generate up to 74.5 tons of hydrocarbons per m². The Chechva River outcrops therefore appear to have a significantly higher generation potential than other source rocks in the Paratethys realm. These very high SPI values for the Menilite Formation may explain why a relatively small area in Ukraine hosts about 70% of the known hydrocarbon reserves in the northern and eastern Carpathian fold‐thrust belt.