Effect of particle morphology on viscoelastic and flexural properties of epoxy–alumina polymer nanocomposites

Nanocomposites were synthesised by dispersing two different types of alumina nanoparticles in epoxy matrix by ultrasonication. Alumina nanoparticles of two shapes, rod and spherical were selected to investigate the effect of particle morphology on viscoelastic and flexural properties of nanocomposites. Specific surface area of both the selected nanoparticles was kept in the similar range. Good dispersion of nanoparticles was observed through transmission electron microscopy. The addition of nanoparticles in epoxy had significant enhancement in the viscoelastic properties and moderate improvement in flexural properties of composites. Composites having alumina nanorods showed higher improvement both in storage modulus as well as in flexural properties in comparison to composites having spherical alumina nanoparticles. Efficacy of Mori-Tanaka method was explored in modelling storage modulus of nanocomposites. Assorted size of alumina nanorods based on particle size distribution was used to model composites with nanorods to see the effect of size assortment on storage modulus.     

An iterative two‐step sequential phase partition (ITSPP) method for batch process modeling and online monitoring

Operating at different manufacturing steps, multiphase modeling and analysis of the batch process are advantageous to improving monitoring performance and understanding manufacturing processes. Although many phase partition algorithms have been proposed, they have some disadvantages and cause problems: (1) time sequence disorder, which requires elaborate post‐treatments; (2) a lack of quantitative index to indicate transition patterns; and (3) tunable parameters that cannot be quantitatively determined. To effectively overcome these problems, an iterative two‐step sequential phase partition algorithm is proposed in the present work. In the first step, initial phase partition results are obtained by checking changes of the control limit of squared prediction error. Sequentially, the fast search and find of density peaks clustering algorithm is employed to adjust the degradation degree and update the phase partition results. These two steps are iteratively executed until a proper degradation degree is found for the first phase. Then, the remaining phases are processed one by one using the same procedure. Moreover, a statistical index is quantitatively defined based on density and distance analysis to judge whether a process has transitions, and when the transition regions begin and end. In this way, the phases and transition patterns are quantitatively determined without ambiguity from the perspective of monitoring performance. The effectiveness of the proposed method is illustrated by a numerical example and a typical industrial case. Several typical phase partition algorithms are also employed for comprehensive comparisons with the proposed method. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2358–2373, 2016     

Synthesis,characterization, and drug release activity of structurally modified poly(vinyl alcohol)

The main aim of the present investigation is synthesis of drug‐grafted poly(vinyl alcohol) (PVA) for sustainable drug release in order to avoid bulk release and unwanted side effects. Here, the PVA was structurally modified with five different drug molecules in DMSO medium at 85 °C under N₂ atmosphere for 2 h. The structure of modified PVA was confirmed by FTIR and ¹H NMR spectra and further it was characterized by TGA, DSC, and SEM. The tensile strength and % elongation for the structurally modified PVA were determined. The FTIR spectrum showed peaks corresponding to the C?O and C? S stretching due to the grafted drug molecules. The ¹H NMR spectrum showed the acrylic CH₂ proton signal of PVA around 1.6 ppm. The SEM showed different surface morphology for the structurally modified PVA. The mechanical properties of the structurally modified PVA was found to be reduced due to the presence of traces of solvent molecules and the breaking of inter‐ and intramolecular hydrogen bonding. The sustainable drug release through hydrolysis mechanism was tested at the pH of 7.3. Generally, the drug release followed the Korsmeyer–Peppas model with Fickian drug transportation mechanism except Furosemide (Fur)‐grafted PVA system at the pH of 7.3. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46620.     

Emergence of time‐dependent material properties in chain extended polyureas

In this article, we report the emergence of material properties of polyurea over a finite time frame. Due to the rapid isocyanate–amine reaction, polyurea formation occurs practically instantaneously. Despite being an “instant‐curing” system, the material properties of polyurea evolve substantially with time: phenomenon, which warrants a methodical study. The curing process of polyurea formulations, containing both aliphatic and aromatic chain extender, has been studied systematically with an aim to gain insight into the time frame associated with its curing and subsequent stress relaxation. Formulations containing aromatic chain extender mandated relatively lesser time to “gel,” but the complete disappearance of NCO absorbance mandated much longer periods ～7 h. Interestingly, in all the formulations, mechanical properties improved with time and reached their optimal properties over a period of 15 days. This improvement has been attributed to several processes simultaneously occurring within the matrix; the foremost being the relaxation of internal stresses which tend to buildup in the polymer during the spray coating process. In addition, significant changes occur in the internal morphology of segmented polymers, which in turn is a result of H‐bond rearrangement.     

Phase transition of Eu2Ti2O7 under high pressure and a new ferroelectric phase with perovskite‐like layered structure

Ferroelectrics with perovskite‐like layered (PL) structure are well‐known for their high T_c and the application prospect of high‐temperature‐piezoelectric sensing. In this study, the PL‐structure Eu₂Ti₂O₇ was prepared by 1‐step high‐pressure sintering, which show the pyrochlore structure of Eu₂Ti₂O₇ would change into PL structure at 11 GPa, 1300°C. The PL‐structure Eu₂Ti₂O₇ is metastable, which will change back to pyrochlore structure at about 900°C in the air. The PL‐structure Eu₂Ti₂O₇ was confirmed as a high‐temperature ferroelectric material for the first time. The ferroelectric domain switching was directly observed using piezoelectric force microscope. The piezoelectric constant of the PL Eu₂Ti₂O₇ ceramic was measured as 0.7‐0.9 pC/N and its thermal depoling temperature (T_d) was determined as 800°C, which is associated with the PL‐pyrochlore transition.     

Synthesis and characterization of calcium aluminate compounds from gehlenite by high-temperature solid-state reaction

The mineral transition mechanism and self-pulverization property of the sintered products in the Ca₂Al₂SiO₇-CaO system were systematically studied using pre-synthesized gehlenite determined by XRD, SEM, FTIR and particle size analyses. The minerals of Ca₁₂Al₁₄O₃₃, CaAl₂O₄, Ca₃SiO₅ and Ca₂SiO₄ are formed by the direct reactions of Ca₂Al₂SiO₇ with CaO. CaAl₂O₄ reacts with CaO to form Ca₁₂Al₁₄O₃₃ or Ca₃Al₂O₆, while Ca₃SiO₅ reacts with Ca₂Al₂SiO₇ to form Ca₂SiO₄ and calcium aluminate compounds. The sintered products mainly contain CaAl₂O₄, Ca₁₂Al₁₄O₃₃ and Ca₂SiO₄ at 1350?°C or above 1500?°C when the molar ratio of CaO to Al₂O₃ is 1.0. Increasing the sintering duration or the CaO consumption promotes the transition of Ca₂Al₂SiO₇ to Ca₂SiO₄ and calcium aluminate compounds when sintered at 1350?°C, which accordingly improves the self-pulverization property of the sintered products. The formed minerals of Ca₁₂Al₁₄O₃₃, CaAl₂O₄ and Ca₂SiO₄ transform into Ca₂Al₂SiO₇ again when the sintering temperature is between 1400?°C and 1450?°C, and the corresponding self-pulverization property of the sintered products deteriorates sharply.     

Exploration on the origin of enhanced piezoelectric properties in transition-metal ion doped KNN based lead-free ceramics

In this work, we studied effects of Ni₂O₃ and Co₂O₃ doping on crystal structures, microstructures, orthorhombic and tetragonal phase transition temperature (T_o-t), and electrical properties of [Li_0.06(Na_0.57K_0.43)_0.94][Ta_0.05(Sb_0.06Nb_0.94)_0.95]O₃ (LNKTSN) lead-free ceramics. The experimental results showed that the Ni₂O₃ addition with appropriate amount could shift the T_o-t downwards to the room temperature, and thus obviously increasing the room-temperature piezoelectric coefficient (d₃₃), dielectric coefficient (ε_r) and electromechanical coupling coefficient (k_p) of the LNKTSN ceramics. These were consistent with previous experimental results obtained in Fe₂O₃ doped LNKTSN ceramics. On the contrary, Co³⁺ doping shifted continuously the T_o-t upward and deteriorated obviously piezoelectric properties of LNKTSN ceramics. Fe, Co and Ni had similar ion radii and were expected to result in the same (donor or acceptor) doping effects on electrical properties of LNKTSN ceramics. The different doping effects between Co³⁺ (deterioration) and Ni³⁺ or Fe³⁺ (improvement) on the electrical properties of LNKTSN ceramics suggested that the coexistence of orthorhombic and tetragonal phases at room temperature due to downward shift of T_o-t, rather than ion doping (donor or acceptor doping) effects was the main cause for enhanced room-temperature piezoelectric properties. This conclusion can be extended to all KNN-based materials in general, thus offering principle guide for future development of new lead-free materials with good piezoelectric properties.     

Metal recovery from jarosite waste – A resin screening study

Work has been carried out screening hydrometallurgical resins for application in the valorization of industrially produced jarosite. Of the seven resins tested, anion exchange resins performed poorly for valuable metal recovery. Purolite S950+ and S957, along with a strong acid resin, show good extraction properties, but are selective for Fe³⁺ over the other (divalent) metals. Purolite S930+ (iminodiacetic acid-functionalized resin) demonstrates selectivity for Cu²⁺ over Fe³⁺, but poor selectivity for Ni²⁺, Zn²⁺, and Co²⁺. Dowex M4195 (bispicolylamine-functionalized resin) demonstrates promise for extracting metals of value away from a mixed metal pregnant liquor solution (PLS). A three-stage column-based recovery process is proposed for jarosite leachate treatment.     

Monte Carlo modeling of binder‐Less spray agglomeration in fluidized beds

Fluidized bed spray agglomeration is used in the industry to increase the particle size and to improve several properties, for example, bulk density, flowability, and dissolution behavior of particulate products. Usually, a binder liquid is sprayed on a particle bed. If amorphous materials are used, spraying of pure water may cause agglomeration due to glass transition at wet spots on the particle surface. As no process models covering binder‐less spray agglomeration currently exist, a model based on a Monte Carlo method is presented. In this method, the process is described by events and processes on the single particle scale. Additionally, agglomeration experiments in a lab‐scale fluidized bed using three different maltodextrins are presented. For each experiment, a simulation was performed. The simulation results are compared with the obtained experimental data. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3582–3594, 2018     

过渡金属氧化物修饰的金纳米催化剂苯甲醇氧化性能

采用一步法合成介孔二氧化硅负载的金纳米催化剂,以氯化锡为前驱体,通过浸渍法向金纳米催化剂中引入助剂氧化锡,得到过渡金属氧化物修饰的金纳米催化剂。通过N2吸附-脱附、X射线衍射、透射电镜和固体紫外漫反射光谱等对催化剂结构进行表征。将所合成的催化剂用于苯甲醇选择性氧化反应,考察助剂组分对催化剂性能的影响,结果表明,氧化锡的引入改变了金纳米颗粒的表面电子结构,增加了催化剂活性与选择性;但随着氧化锡含量继续增加,催化剂活性降低,这主要是因为金纳米颗粒表面过渡金属氧化物覆盖度增加,减少了催化剂活性组分与苯甲醇的接触。当氧化锡质量分数0.2%时,催化剂效果最佳,在100℃和氧气压力0.2 MPa下反应3 h,苯甲醇转化率25.7%,苯甲醛选择性75.9%,苯甲酸选择性15.8%,苯甲酸苄酯选择性6.3%。