Multiblock poly(ether-b-amide)copolymers comprised of PA1212 and PPO-PEO-PPO with specific moisture-responsive and antistatic properties

Functional multiblock poly(ether-b-amide)(PEBA)copolymers,comprised of PA1212(polyamide 1212)as hard segments and Jeffamine ED-2003 as soft segments,were successfully prepared via two-step melt polycondensation without any amidation catalyst.Here,using diamino-terminated poly(propylene oxide)-poly(ethylene oxide)-poly(propylene oxide)(PPO-PEO-PPO),Jeffamine ED-2003,enhances the compatibility between polyamide oligomer and polyether,which is better than the traditional route using hydroxyl-terminated polyether.The chemical structure of multiblock PEBAs,as well as the microphase separated structure with crystalline phase of polyamide and polyether,were confirmed by heteronuclear multiple-bond correlation spectrum,heteronuclear multiple quantum correlation spectrum,Fourier transform infrared spectroscopy(FT-IR),differential scanning calorimetry and dynamic mechanical analysis.The hydrophilic PEBA copolymers showed water adsorption ranging from 87.3%to 17.1%depending on the polyether content,and specially showed moisture responsive behavior within seconds when exposed to moisture.The corresponding mechanism was studied using time-resolved attenuated total reflectance FT-IR spectroscopy in the molecular level and the water diffusion coefficient was estimated to be 1.07×10^(–8)cm^(2)∙s^(-1).Two-dimensional correlation FT-IR spectra analysis was performed to confirm that the interaction between water and polyether phase was in preference to that between water and polyamide matrix,and water molecule only forms hydrogen bond with the polyether segment.Due to the incorporation of PEO segments,the PEBAs have the surface resistivity varying from 5.6×10^(9)to 6.5×10^(10)Ω,which makes PEBA potential candidate as permanent antistatic agent.

Polyoxometalates-engineered hydrogen generation rate and durability of Pt/CNT catalysts from ammonia borane

Heterogeneously catalyzed hydrolytic dehydrogenation of ammonia borane is a remarkable structure sensitive reaction. In this work, a strategy by using polyoxometalates(POMs) as the ligands is proposed to engineer the surface and electronic properties of Pt/CNT catalysts toward the enhanced hydrogen generation rate and durability. Three kinds of POMs, i.e., silicotungstic acid(STA), phosphotungstic acid(PTA)and molybdophosphoric acid(PMA), are comparatively studied, among which the STA shows positive effects on the catalytic activity and durability. A catalyst structure-performance relationship is established by a combination of kinetic and isotopic analyses with multiple characterization techniques, such as HAADF-STEM, EDS, Raman spectroscopy and XPS. It is shown that the STA compared to the other two POMs can increase the Pt binding energy and thus promote the reaction. The insights demonstrated here could open a new avenue for boosting the reaction by employing the POMs as the ligands to engineer the catalyst electronic properties.

Explosion limits estimation and process optimization of direct propylene epoxidation with H2 and O2

Direct propylene epoxidation with H2 and O2,an attractive process to produce propylene oxide(PO),has a potential explosion danger due to the coexistence of flammable gases(i.e.,C3 H6 and H2)and oxidizer(i.e.,O2).The unknown explosion limits of the multi-component feed gas mixture make it difficult to optimize the reaction process under safe operation conditions.In this work,a distribution method is proposed and verified to be effective by comparing estimated and experimental explosion limits of more than 200 kinds of flammable gas mixture.Then,it is employed to estimate the explosion limits of the feed gas mixture,some results of which are also validated by the classic Le Chatelier’s Rule and flammable resistance method.Based on the estimated explosion limits,process optimization is carried out using commercially high and inherently safe reactant concentrations to enhance reaction performance.The promising results are directly obtained through the interface called gOPT in gPROMS only by using a simple,easy-constructed and mature packed-bed reactor,such as the PO yield of 13.3%,PO selectivity of 85.1%and outlet PO fraction of 1.8%.These results can be rationalized by indepth analyses and discussion about the effects of the decision variables on the operation safety and reaction performance.The insights revealed here could shed new light on the process development of the PO production based on the estimation of the explosion limits of the multi-component feed gas mixture containing flammable gase s,inert gas and O2,followed by process optimization.

Monte Carlo simulation of sequential structure control of AN-MA-IA aqueous copolymerization by different operation modes

The regulation of polyacrylonitrile(PAN)copolymer composition and sequence structure is the precondition for producing high-quality carbon fiber high quality.In this work,the sequential structure control of acrylonitrile(AN),methyl acrylate(MA)and itaconic acid(IA)aqueous copolymerization was investigated by Monte Carlo(MC)simulation.The parameters used in Monte Carlo were optimized via machine learning(ML)and genetic algorithms(GA)using the experimental data from batch copolymerization.The results reveal that it is difficult to control the aqueous copolymerization to obtain PAN copolymer with uniform sequence structure by batch polymerization with one-time feeding.By contrary,it is found that the PAN copolymer with uniform composition and sequence structure can be obtained by adjusting IA feeding quantity in each reactor of a train of five CSTRs.Hopefully,the results obtained in this work can provide valuable information for the understanding and optimization of AN copolymerization process to obtain high-quality PAN copolymer precursor.

Taming Electrons in Pt/C Catalysts to Boost the Mesokinetics of Hydrogen Production

Taming the electron transfer across metal–support interfaces appears to be an attractive yet challenging methodology to boost catalytic properties.Herein,we demonstrate a precise engineering strategy for the carbon surface chemistry of Pt/C catalysts—that is,for the electron-withdrawing/donating oxygencontaining groups on the carbon surface—to fine-tune the electrons of the supported metal nanoparticles.Taking the ammonia borane hydrolysis as an example,a combination of density functional theory(DFT)calculations,advanced characterizations,and kinetics and isotopic analyses reveals quantifiable relationships among the carbon surface chemistry,Pt charge state and binding energy,activation entropy/enthalpy,and resultant catalytic activity.After decoupling the influences of other factors,the Pt charge is unprecedentedly identified as an experimentally measurable descriptor of the Pt active site,contributing to a 15-fold increment in the hydrogen generation rate.Further incorporating the Pt charge with the number of Pt active sites,a mesokinetics model is proposed for the first time that can individually quantify the contributions of the electronic and geometric properties to precisely predict the catalytic performance.Our results demonstrate a potentially groundbreaking methodology to design and manipulate metal–carbon catalysts with desirable properties.

Highly interconnected macroporous MBG/PLGA scaffolds with enhanced mechanical and biological properties via green foaming strategy

In this study,mesoporous bioactive glass particles(MBGs) are incorporated into poly(lactic-co-glycolic acid)(PLGA) to fabricate highly interconnected macroporous composite scaffolds with enhanced mechanical and biological properties via a developed supercritical carbon dioxide(scCO_(2)) foaming method Scaffolds show favorable highly interconnected and macroporous structure through a high foaming pressure and long venting time foaming strategy.Specifically,scaffolds with porosity from 73% to 85%,pore size from 120 μm to 320 μm and interconnectivity of over 95% are controllably fabricated at MBG content from 0 wt% to 20 wt%.In comparison with neat PLGA scaffolds,composite scaffolds perform improved strength(up to 1.5 folds) and Young's modulus(up to 3 folds).The interconnected macroporous structure is beneficial to the ingrowth of cells.More importantly,composite scaffolds also provide a more promising microenvironment for cellular proliferation and adhesion with the release of bioactive ions.Hopefully,MBG/PLGA scaffolds developed by the green foaming strategy in this work show promising morphological,mechanical and biological features for tissue regeneration.

Evaluation of Hepatic Cystic Echinococcosis’ CT image in Xinjiang Uygur Autonomous Region based on Kolmogorov Complexity Model

Designing and developing computer-assisted image processing techniques to help doctors improve their diagnosis has received considerable interests over the past years. In this paper, we used the kolmogorov complexity model to analyze the CT images of the healthy liver and multiple daughter hydatid cysts. Before the complexity characteristic calculating, the image preprocessing methods had been used for image standardization. From the kolmogorov complexity model, complexity characteristic were calculated in order to quantify the complexity, between healthy liver and multiple daughter hydatid cysts. Then we use statistical method to analyze the complexity characteristic of those two types of images. Our preliminary results show that the complexity characteristic has statistically significant (p<0.05) to analyze these two types CT images, between the healthy liver and the multiple daughter hydatid cysts. Furthermore, the result leads us to the conclusion that the kolmogorov complexity model could use for analyze the hydatid disease and will also extend the analysis the other lesions of liver.

Kinetics insights into size effects of carbon nanotubes'growth and their supported platinum catalysts for 4,6-dinitroresorcinol hydrogenation

Size effects are a well-documented phenomenon in heterogeneous catalysis,typically attributed to alterations in geometric and electronic properties.In this study,we investigate the influence of catalyst size in the preparation of carbon nanotube(CNT)and the hydrogenation of 4,6-dinitroresorcinol(DNR)using Fe_(2)O_(3)and Pt catalysts,respectively.Various Fe_(2)O_(3)/Al_(2)O_(3)catalysts were synthesized for CNT growth through catalytic chemical vapor deposition.Our findings reveal a significant influence of Fe_(2)O_(3)nanoparticle size on the structure and yield of CNT.Specifically,CNT produced with Fe_(2)O_(3)/Al_(2)O_(3)containing 28%(mass)Fe loading exhibits abundant surface defects,an increased area for metal-particle immobilization,and a high carbon yield.This makes it a promising candidate for DNR hydrogenation.Utilizing this catalyst support,we further investigate the size effects of Pt nanoparticles on DNR hydrogenation.Larger Pt catalysts demonstrate a preference for 4,6-diaminoresorcinol generation at(100)sites,whereas smaller Pt catalysts are more susceptible to electronic properties.The kinetics insights obtained from this study have the potential to pave the way for the development of more efficient catalysts for both CNT synthesis and DNR hydrogenation.

甲基氯硅烷精馏流程的模拟与优化

采用Aspen plus软件对工业七塔精馏过程进行全流程建模与模拟,优化工艺参数,研究了新的精馏节能工艺。对一甲塔等7个精馏塔采用双因素水平的灵敏度分析,考察了塔釜采出率、回流比、进料位置和塔顶压力对产品浓度和热负荷的影响,确定一甲塔最优的工艺参数:塔釜摩尔采出率为0.92,摩尔回流比为130,塔顶压力为0.18MPa,总理论板数为400,在210块理论板位置进料。在此基础上,针对高能耗的脱高塔/脱低塔,模拟研究了双效精馏新工艺,新工艺可节省39.70%的年总成本;针对一甲塔模拟研究了热泵精馏新工艺,新工艺可降低41.42%的年总成本。

Porous Metal-Organic Framework-Polymer Composites Using High Internal Phase Emulsion Templates: A Review

As promising engineering materials for green and sustainable processes, porous metalorganic framework(MOF)-polymer composites show great potential in applications, including adsorption, separation, catalysis, and bioengineering. Owing to the mild and scalable operation, porous polymeric materials derived from high internal phase emulsion templates(polyHIPE) have received great interests in recent decades. In this contribution, research progress of the preparation of porous MOF@polyHIPE composites and their applications are reviewed, highlighting how can MOF particles be shaped by HIPE templates, in particular the polymerizable ones. Four different emulsion templates stabilized by MOFs and the applications of corresponding MOF@polyHIPE are included. Hopefully,both the state-of-art and future directions present herein can give rise to the development of highperformance porous MOF@polyHIPEs.

Nanomaterials synthesized by gas combustion flames:Morphology and structure

The flame technology has been employed broadly for large-scale manufacture of carbon blacks, fumed silica, pigmentary titania, and also ceramic commodities such as SiO2, Ti02, and A1203. A deeper understanding of the process also made it possible for production of novel nanomaterials with high functionality--various novel nanomaterials such as nanorods, nanowires, nanotubes, nanocoils, and nanocomposites with core/shell, hollow and ball-in-shell structures, have been synthesized recently via gas combustion technology, while the mechanisms of the material formation were investigated based on the nucleation-growth and chemical engineering principles. Studies of the fluid flow and mass mixing, supported by principles of chemical reaction engineering, could provide knowledge for better understanding of the process, and thus make rational manipulation of the products possible.

Catalyst particle shapes and pore structure engineering for hydrodesulfurization and hydrodenitrogenation reactions

Catalyst particle shapes and pore structure engineering are crucial for alleviating internal diffusion limitations in the hydrodesulfiirization(HDS)/hydrodeni-trogenation(HDN)of gas oil.The effects of catalyst particle shapes(sphere,cylinder,trilobe,and tetralobe)and pore structures(pore diameter and porosity)on HDS/HDN performance at the particle scale are investigated via mathematical modeling.The relationship between particle shape and effectiveness factor is first established,and the specific surface areas of different catalyst particles show a positive correlation with the average HDS/HDN reaction rates.The catalyst particle shapes primarily alter the average HDS/HDN reaction rate to adjust the HDS/HDN effectiveness factor.An optimal average HDS/HDN reaction rate exists as the catalyst pore diameter and porosity increase,and this optimum value indicates a tradeoff between diffusion and reaction.In contrast to catalyst particle shapes,the catalyst pore diameter and the porosity of catalyst particles primarily alter the surface HDS/HDN reaction rate to adjust the HDS/HDN effectiveness factor.This study provides insights into the engineering of catalyst particle shapes and pore structures for improving HDS/HDN catalyst particle efficiency.

Solubility of CO_(2) in solid-state PET measured by pressure-decay method

The solubility of CO_(2) in solid-state PET was measured using a pressure-decay method.In order to calculate the solubility of CO_(2) in the amorphous region of PET,the crystallinity of solid state PET dissolved in CO_(2) at different pressures and temperatures was measured by differential scanning calorimetry(DSC).The solubility increases with increasing pressure and it follows a linear relationship and obeys Henry’s law when the pressure is below 8 MPa.The effect of temperature on solubility is weak and the solubilities at different temperatures are almost the same under low pressures.At higher pressure,the solubility decreases with an increase in temperature.The solubility of CO_(2) in the amorphous region of PET at 373.15 K,398.15 K and 423.15 K was correlated with the Sanchez-Lacombe equation of state with a maximal correlation error of 6.69%.