Effects of flow history on oil entrapment in porous media: An experimental study

The effect of flow history on fluid phase entrapment during immiscible two‐phase flow in Hele‐Shaw cells packed with spherical and crushed glass beads is investigated. The wetting fluid is injected into an initially oil saturated cell at a well‐defined capillary number. It is observed that the size and shape of the trapped clusters strongly depend on the history of flooding such that less oil was trapped in the medium when the injecting capillary number gradually increased to the final maximum capillary number compared to the case when the injection was started and maintained constant at the maximum capillary number. In addition, a comprehensive series of experiments were conducted to delineate the effects of the capillary number on the phase entrapment. Contrary to previously published data, our experimental data reveal that the residual oil saturation depends on capillary number nonmonotonically. A physically based relationship to scale the capillary desaturation curve is proposed. © 2014 American Institute of Chemical Engineers AIChE J, 61: 1385–1390, 2015     

A unified polymer reaction engineering methodology for catalytic olefin polymerization: From reaction conditions and catalyst reaction performance to molecular and rheological properties for forward,reverse engineering and deconvolution applications

This work presents a unified polymer reaction engineering methodology for the catalytic olefin polymerization process. The proposed modelling approach offers a modelling pathway from the polymerization recipe to production rate and polymer microstructure, and finally to rheological properties. Furthermore, this work introduces for the first time the constraint of the actual reaction performance of the polymerization catalyst in the inverse rheology and microstructural deconvolution problem, limiting the solution only to the most realistic potential molecular weight distributions (MWDs) that a specific catalyst can produce. This approach can be applied for both single- and multi-site catalysts, providing not a potential MWD but the unique one that the selected catalyst can offer under given polymerization conditions. Depending on the available catalyst reaction performance insight, the constraint can vary and include from the number of active sites in use to the exact kinetic parameters of each site type. The potential of the proposed methodology is highlighted within a series of indicative examples, including forward, reverse engineering and deconvolution applications.     

黏弹性聚合物熔体多相成型界面不稳定的机理分析

基于动网格法和EVSS/SU等混合有限元技术,建立了黏弹性聚合物多相成型界面不稳定的数值模拟系统,模拟结果与Matsunaga的理论研究和Yamaguchi的实验研究结论相符合。通过研究流率、黏度和松弛时间（弹性）对界面不稳定的影响规律,发现在相应条件下流率、黏度和松弛时间都能使界面变得不稳定,而界面两侧第一法向应力差的阶跃是导致黏弹性界面不稳定的根本原因,进而揭示了黏弹性界面不稳定的机理,并对生产实践提出了若干指导原则。     

Tuning gradient microstructures in immiscible polymer blends by viscosity ratio

Bioinspired gradient microstructures provide an attractive template for functional materials with tailored properties. In this study, filaments with gradient microstructures are developed by melt-spinning of immiscible polymer blends. The distribution of the gradient morphology is shown to be controlled by the viscosity ratio of polymers as well as the geometry of the capillary die. Distinct microstructure gradients with long thin fibrils near the surface region and short large droplets near the center region of the filament, as well as the inverse pattern, are formed in systems with different viscosity ratios. The shear flow field in the capillary can elucidate the formation mechanisms of gradient morphologies during processing. The results demonstrate how the features of a gradient microstructure can be tailored by the design of capillary geometry and processing conditions. The viscosity ratio is then introduced as an adjusting tool to control the gradient morphology in a given processing setup. In consequence, this study provides novel design routes for achieving gradient morphologies in immiscible polymers. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48165.     

Microfluidic synthesis of elastomeric microparticles: A case study in catalysis of palladium‐mediated cross‐coupling

Palladium (Pd)‐loaded poly‐hydromethylsiloxane (PHMS) microparticles of tunable size and elasticity are prepared in a capillary‐based coaxial flow‐focusing microfluidic device constructed using off‐the‐shelf components. Simultaneous droplet formation and chemical cross‐linking processes are performed by tuning the dilution of the cross‐linking catalyst in the annular flow of the microreactor, resulting in PHMS microparticles synthesized in a single step. The size of the elastomeric microparticles can be tuned by adjusting the flow rate ratio of the polymer and cross‐linker mixture to water, while the elasticity can be tuned by the polymer to cross‐linker ratio as well as the flow rate ratio of the polymer mixture to cross‐linking catalyst mixture. Microparticle elasticity is characterized by the degree of solvent uptake. Application of the synthesized PHMS microparticles in organic synthesis is demonstrated by producing monodispersed Pd‐loaded microparticles and utilizing them as microreaction vessels for continuous Suzuki‐Miyaura cross‐coupling in a Pd‐loaded microparticle‐packed bed reactor. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3188–3197, 2018     

The viscosity of immiscible polymer blends: influences of the interphase and deformability

The viscosity of immiscible polymer blends has been studied via application of certain aspects of rheology. A symmetric mixture rule was derived, and the deviations from the ‘additivity rule’ have been associated, essentially, with the properties of the interphase, with its influence on the effective volumes of the two polymers constituting the blend and with the deformability of both the interphase and the disperse phase. The rule predicts a positive deviation for a mixture with a disperse-phase viscosity (η_d) greater than that (η_m) of the continuous medium, and a much higher-viscosity interphase, i.e. η_i å η_d ≥ η_m. Negative deviation is to be expected when the interphase has a much lower viscosity than those of the two pure polymers (η_d, η_m å η_i) in the blend. The viscosity and strength of the interphase depend mostly on the specific thermodynamic interactions that led to its creation.     

Grafting of polymer chains on the surface of carbon nanotubes via nitroxide radical coupling reaction

Poly(butylene succinate) (PBS) was grafted on the surface of TEMPO (2,2,6,6‐tetramethyl‐1‐piperidinyloxy) modified multi‐walled carbon nanotubes (MWCNTs) via a nitroxide radical coupling reaction. TEMPO functionalized MWCNTs (MWCNTs‐g‐TEMPO) were synthesized using the Cu(I)‐catalyzed azide/alkyne click chemistry approach and the covalent bond of the nitroxide moieties onto the MWCNTs was confirmed via electron paramagnetic resonance (EPR) spectroscopy. The PBS grafting on the sidewalls of MWCNTs was carried out in solution via peroxide‐induced formation of macroradicals and it was confirmed by EPR and attenuated total reflectance Fourier transform infrared analysis. Preliminary rheological and calorimetric analyses revealed that the grafting improves both the quality of stress transfer across the polymer ? nanotube interface and the degree of dispersion of the filler, which also exhibited a moderate nucleating action on the PBS. Overall, our results demonstrate that nitroxide radical coupling is an efficient and feasible ‘grafting to’ method to covalently bond polymer chains on MWCNTs with possible advantages in the final properties of the polymer nanocomposites. © 2015 Society of Chemical Industry     

Membrane reactor immobilized with palladium‐loaded polymer nanogel for continuous‐flow Suzuki coupling reaction

A catalytic membrane reactor, which was immobilized with palladium‐loaded nanogel particles (NPs), was developed for continuous‐flow Suzuki coupling reaction. Palladium‐loaded membranes were prepared by immobilization of NPs, adsorption of palladium ions, and reduction into palladium(0). The presence of palladium in the membrane was confirmed by the scanning electron microscopy; palladium aggregation was not observed. The catalytic activity of the membrane reactor in continuous‐flow Suzuki coupling reaction was approximately double that of a comparable reactor in which palladium ions were directly adsorbed onto an aminated membrane. This was attributed to the formation of small palladium particles. The reusability in the continuous‐flow system was higher than that in a batch system, and the palladium‐loaded membrane reactor had high long‐term stability. © 2014 American Institute of Chemical Engineers AIChE J, 61: 582–589, 2015     

Drag reduction in turbulent pipeline flow of mixed nonionic polymer and cationic surfactant systems

Turbulent drag reduction behaviour of a mixed nonionic polymer/cationic surfactant system was studied in a pipeline flow loop to explore the synergistic effects of polymeric and surfactant drag reducing additives. The nonionic polymer used was polyethylene oxide (PEO) at three different concentrations (500, 1000, and 2000 ppm). The surfactant used was cationic octadecyltrimethylammonium chloride (OTAC) at concentration levels of 1000 and 2500 ppm. Sodium salicylate (NaSal) was used as a counter‐ion for the surfactant at a molar ratio of 2 (MR = Salt/OTAC = 2). Relative viscosity and surface tension were measured for different combinations of PEO and OTAC. While the relative viscosities demonstrated a week interaction between the polymer and the surfactant, the surface tension measurements exhibited negligible interaction. The pipeline results show a considerable synergistic effect, that is, the mixed polymer–surfactant system gives a significantly higher drag reduction (lower friction factors) as compared with pure polymer or pure surfactant. The addition of surfactant to the polymer always enhances drag reduction. However, the synergistic effect in mixed system is stronger at low polymer concentrations and high surfactant concentrations. © 2011 Canadian Society for Chemical Engineering     

Transient and steady-state deformations and breakup of dispersed-phase droplets of immiscible polymer blends in steady shear flow

Transient and steady-state deformations and breakup of viscoelastic polystyrene droplets dispersed in viscoelastic high-density polyethylene matrices were observed in a simple steady shear flow between two transparent parallel disks. By separately varying the elasticities of the individual blend components, the matrix shear viscosity, and the viscosity ratio, their effects on the transient deformation, steady-state droplet size, and the breakup sequence were determined. After the startup of a steady shear flow, the viscoelastic droplet initially exhibits oscillations of its length in the flow direction, but eventually stretches preferentially in the vorticity direction. We find that at fixed capillary number, the oscillation amplitude decreases with increasing droplet elasticity, while the oscillation period depends primarily on, and increases with, the viscosity ratio. At steady-state, the droplet length along the vorticity direction increases with increasing capillary number, viscosity ratio, and droplet elasticity. Remarkably, at a viscosity ratio of unity, the droplets remain in a nearly undeformed state as the capillary number is varied between 2 and 8, apparently because under these conditions a tendency for the droplets to widen in the vorticity direction counteracts their tendency to stretch in the flow direction. When a critical capillary number, Ca_c, is exceeded, the droplet finally stretches in the vorticity direction and forms a string which becomes thinner and finally breaks up, provided that the droplet elasticity is sufficiently high. For a fixed matrix shear stress and droplet elasticity, the steady-state deformation along the vorticity direction and the critical capillary number for breakup both increase with increasing viscosity ratio.     

Effects of excluded volume and hydrodynamic interactions on the behavior of isolated bead‐rod polymer chains in shearing flow

A detailed study of the effects of hydrodynamic interaction (HI) and excluded volume (EV), on isolated bead‐rod chains in shear flows, where the “rods” are mimicked by stiff Fraenkel springs is presented. It is observed that the deformation behavior at weak and intermediate shear rates is qualitatively similar to that observed for polymer chains in the absence of EV and HI, while that at high‐shear rates is sensitive to modeling details and chain resolution. Our simulations with varying degrees of resolution reveal universality in chain behavior in the presence of EV (without HI), while the onset of the transition to a compressed chain in the presence of HI (without EV) shifts to higher shear rates with increasing chain resolution. The results also highlight the success of the bead‐spring models in predicting the chain behavior in shear flows in the presence of HI, when the HI parameter is appropriately chosen. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1400–1412, 2014     

The kinetics of polyurethane structural foam formation: Foaming and polymerization

Kinetic models have been developed to understand the manufacturing of polymeric foams, which evolve from low viscosity Newtonian liquids, to bubbly liquids, finally producing solid foam. Closed‐form kinetics are formulated and parameterized for PMDI‐10, a fast curing polyurethane, including polymerization and foaming. PMDI‐10 is chemically blown, where water and isocyanate react to form carbon dioxide. The isocyanate reacts with polyol in a competing reaction, producing polymer. Our approach is unique, although it builds on our previous work and the polymerization literature. This kinetic model follows a simplified mathematical formalism that decouples foaming and curing, including an evolving glass transition temperature to represent vitrification. This approach is based on IR, DSC, and volume evolution data, where we observed that the isocyanate is always in excess and does not affect the kinetics. The kinetics are suitable for implementation into a computational fluid dynamics framework, which will be explored in subsequent articles. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2945–2957, 2017     

Flow accelerates adhesion between functional polyethylene and polyurethane

Polyethylene (PE) has relatively poor adhesion with polar polymeric materials. In an effort to improve the adhesion between PE and thermoplastic polyurethane (TPU), maleic anhydride (MA), hydroxyl (OH), and secondary amine (NHR) functionalized PEs were blended into nonmodified PE. These functional groups will react with urethane linkages in TPU at the temperature of melt processing. We bonded these PEs to TPU via lamination and coextrusion. To compare the two processes, we determined the interfacial copolymer density Σ considering both advection and interfacial area generation. We found that the development of adhesion in coextrusion was much faster in comparison with lamination at the same temperature. This difference was attributed to the extensional and compressive flow in coextrusion overcoming the diffusion barrier at the interface and forcing reactive species to penetrate the interface. The effects of functional group reactivity and processing variables on adhesion were correlated with interfacial copolymer coverage. Amine functionalized PE showed dramatic adhesion improvement even at 1 wt %. © 2011 American Institute of Chemical Engineers AIChE J, 2011     

Hydrogel–hydrogel composites: The interfacial structure and interaction between water and polymer chains

This work examines the interfacial structure and interaction between water and polymer chains in the hydrogel–hydrogel composites with the goal of establishing foundations for further investigation of drug diffusion from one hydrogel to another in the soft contact lens. This is based on the ability of the hydrogel–hydrogel composites to release ophthalmic drugs in a sustained manner. The hydrogel–hydrogel composites were synthesized by immersing the glycerol-swollen particles of crosslinked N-vinyl-2-pyrrolidone (NVP) into the monomer of hydroxyethylmethacrylate (HEMA) containing initiator benzoylperoxide (BPO) that polymerizes to form a matrix in the presence of the first networks. The hydrogel–hydrogel composites were characterized by UV/Vis spectrophotometer, scanning electronic micrography (SEM), and differential scanning calorimetry (DSC). The results showed that the samples of hydrogel–hydrogel composites of the particles of crosslinked NVP and poly-HEMA were transparent and glassy and suitable for soft contact lens. Three types of the interfacial structure, no interpenetrating interface, partly interpenetrating interface, and fully interpenetrating interface, of the hydrogel–hydrogel composites existed, and the type of the interfacial structure was determined by the degree to which the monomer of HEMA penetrated into the first networks before formation of the matrix. Different from poly-HEMA hydrogels, the peaks near 0°C on DSC curves of the hydrogel–hydrogel composites did not split while they were kept acute, and the amount of freezable-bound water was less. This shows that the water incorporated in the hydrogel–hydrogel composites does not strongly interact with polymer matrix, so the hydrogel–hydrogel composites cannot keep their shape during the phase transition of water. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

FCC反应过程的CFD模拟进展

流化催化裂化（fluid catalytic cracking,FCC）工艺是石油炼制中的重要转化工艺,用于生产汽油、柴油、轻质烯烃等重要化工原料。FCC反应过程的CFD模拟有助于理解FCC反应器中流动和反应行为,辅助设计和优化FCC工艺设备,最终指导工业生产和实现虚拟调控和放大。从与FCC反应模拟相关的多相流动模型、反应动力学模型以及流动与反应之间耦合等方面做了回顾和总结。在流动与反应耦合研究方面,从湍流模型的使用、流动结构的影响、精细化模型的发展以及原油汽化模型的重要性这4个角度做了分析比较及总结。基于已有的研究工作,认为虽然很多研究表明CFD模拟能较好地揭示工业FCC提升管反应器内的流动和反应行为,但缺乏采用同一方法实现从小试到工业反应器模拟放大的实例,从侧面反映了当前的FCC理论模型和模拟技术还远未达到可以代替实验的水平。展望未来的FCC反应模拟,建议从模型精细度和计算效率上加强研发,并在此两方面寻求平衡,最终实现虚拟调控。     

Polymer reaction engineering: From reaction kinetics to polymer reactor control

Polymer reaction engineering is a relatively “young”, very broad, multidisciplinary, rapidly developing field. It is the combination of polymer science, chemistry and technology with process engineering principles. The outcome of this high degree of synergism has evolved over the last fifteen or so years towards an area that includes any or all of the following: polymerization and post-polymerization (chemical modification) reaction kinetics; mathematical modelling and process simulation; polymer reactor design and scale-up; sensor development and process monitoring; and polymer reactor optimization, state estimation and computer control. This article will attempt to give an overview of the results obtained in our laboratory over the last seven years from systematic studies of polymer reaction engineering and polymer production technology problems. These problems cover all aspects of polymer reaction engineering mentioned above. Going from fundamentals to practice, the basic premise of the article is that only by adopting a holistic approach can one devise effective strategies in order to achieve the final objective of more efficient polymer reactor design and control, and hence improved production systems of polymeric materials.     

Experimental research on drag reduction by polymer additives in a turbulent pipe flow

In order to investigate the effects of injection position on drag reduction as well as further the effects of polymer additives on turbulent structures, LDA measurements of turbulent pipe flows were conducted. The results show that the amount of drag reduction grows with the increase of the Reynolds number, and injecting the polymer at the centre of pipe is more effective than at the wall. Due to the addition of polymer solution, the axial, radial r.m.s. velocity fluctuations and Reynolds stress decrease over the entire pipe cross‐section, the time auto‐correlation coefficients of axial and radial velocity fluctuation at the centre of pipe decay more slowly, the number of spectrum peaks is decreased, and the peak shifts towards lower wave numbers. The results also reveal that, due to the addition of polymer solution, the large‐scale vortices are enhanced and small‐scale vortices are suppressed.     

一种提高聚合物挤出流量在线测量精度的方法

针对聚合物挤出加工过程挤出流量间接测量的特点,提出了介于静态数字滤波与动态数字滤波之间的转静态数字滤波方法,将具有动态测量特点的直接测量变量转化为相对稳定的具有静态测量特点的间接测量变量。在此基础上,将限幅滤波和递推平均滤波应用于挤出流量在线测量的数据处理,以克服挤出过程中随机干扰和周期干扰对挤出流量测量精度的影响。通过实验选取最佳的滤波参数——滤波采样周期T及递推平均次数N,结果证明,转静态数字滤波输出值与挤出流量真值吻合度很好,符合对挤出流通量在线测量精度的要求。     

Effect of solvent quality on Poiseuille flow of polymer solutions in microchannels: A dissipative particle dynamics study

The Poiseuille flows of polymer solutions for varying quality solvents in microchannels have been simulated using dissipative particle dynamics. In particular, the velocity distributions and the polymer migration across the channel have been investigated for good, athermal, and poor solvents. The velocity profiles for all three kinds of solvent deviate from the parabolic profile, and the velocity profile of the athermal solvent falls in between the good solvent and the poor solvent. For the athermal solvent, a migration away from the wall due to the hydrodynamic interactions between the chains and the wall is observed, and a migration away from the channel center due to the different chain Brownian diffusivities is also observed. For the good solvent, because of the more stretched polymer chains, the migration away from the wall is stronger than that for the athermal solvent. However, the migration away from the channel center is not observed for good solvents. For the poor solvent, the hydrodynamic interaction within the chains is screened, and the polymer chains migrate toward the wall and appear to be absorbed by the wall. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47345.