Numerical simulation of the self‐assembly of a polymer–polymer–solvent ternary system on a heterogeneously functionalized substrate

The spinodal decomposition of a polymer–polymer–solvent ternary blend spin coated on heterogeneously functionalized substrate is studied in a three‐dimensional numerical model. The Cahn‐Hilliard equation was used to describe the free energy profile of the domain. The mechanism of the morphology evolution was studied quantitatively. The well‐established linear relationship of the characteristic length, R(t), with t^1/3 can be observed in the simulation results. The functionalized substrate greatly affected the morphology evolution of blends with different solvent concentrations. The results indicated that a critical time can be observed, at which the evolution rate changes abruptly, also after which the compatibility of the surface morphology to the functionalized substrate pattern increases at a much lower pace in the diluted solution. In the condensed solution, the compatibility actually decreases beyond the critical time. The influence of solvent evaporation is investigated and a sharper interface was observed in the case with solvent evaporation and film thickness reduction. POLYM. ENG. SCI., 2010. © 2010 Society of Plastics Engineers     

A novel mucoadhesive polymer prepared by template polymerization of acrylic acid in the presence of poloxamer

A new mucoadhesive polymer was prepared by template polymerization of acrylic acid using poloxamer as a template polymer. FTIR results showed that the interpolymer complex was formed by hydrogen bonding between the carboxyl group of poly(acrylic acid) (PAA) and the ether group of poloxamer. The extent of hydrogen bonding in the PAA/poloxamer interpolymer complex increased as the ratio of PAA/poloxamer decreased. The T_g of PAA/poloxamer interpolymer complexes was matched well with the T_g calculated by Gordon‐Taylor's equation than that of their blends. This result suggests that the PAA and poloxamer in the interpolymer complexes are more compatible than their blends. The dissolution rate of PAA/poloxamer interpolymer complexes was much slower than that of their blends, and was dependent on the pH of the medium and the ratio of PAA/poloxamer. The adhesive bond strength of PAA/poloxamer interpolymer complexes to a plastic (polypropylene) plate was greater than their blends or a commercial product, Carbopol 971P NF. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1525–1530, 2001     

Preparation method and physical,mechanical, thermal characterization of poly(vinyl alcohol)/poly(acrylic acid) blends

A series of blends of poly(vinyl alcohol)/poly(acrylic acid) (PVA/PAA) were prepared by solution mixing and casting. Glycerol was used as plasticizer. The blends were characterized for their physicochemical and thermo-mechanical properties. The FTIR results revealed the molecular level interaction between PVA and PAA at all blend ratios. The incorporation of PAA significantly reduced the storage modulus of PVA at a given temperature. PVA gradually lost its crystalline character with the increase of PAA and became fully amorphous when the PAA content in the blend exceeded 50 wt%. The kinetic parameters of the semi-crystalline blends were determined using the Avarami–Erofeev model, which showed excellent fitting with the experimental data from DSC. The loss in crystallinity of PVA also contributed to an increase in swelling of the blend when the PAA content is increased. The morphology study by FE-SEM demonstrated that there is no phase separation among the blend components at all blend ratios.     

A study of blending and complexation of poly(acrylic acid)/poly(vinyl pyrrolidone)

Poly(acrylic acid) (PAA) and poly(vinyl pyrrolidone) (PVP) were chosen to prepare polymer complex and blends. The complex was prepared from ethanol solution and the blends were prepared from 1-methyl-2-pyrrolidone solution. DSC results show that the T_gs of the PAA/PVP blends lie between those of the two constituent polymers, whereas T_g of the PAA/PVP complex is higher than both blends and the two constituent polymers. TGA results show that degradation temperature, T_d, of PAA increases upon adding PVP in the blend, but thermal stability of the complex is higher than that of the blends as reflected by the higher T_d. Both FTIR and high-resolution solid state NMR show strong hydrogen bonding between PAA and PVP by showing significant chemical shift. The T_1ρ(H) measurement shows that the homogeneity scale for the blend is at ∼20 Å and that for the complex is ∼15 Å.     

POM匀胶托盘的优化设计

以广泛应用于旋涂功能薄膜工艺中的聚甲醛(POM)匀胶托盘为研究对象,基于数值仿真及实验研究,对现有POM托盘工作中的缺陷进行了分析,结果表明,螺旋托盘基片因发生翘曲形变而易使胶体渗入匀胶机,腔式托盘基片形变量过大。基于分析结果,对现有匀胶托盘进行了优化,提出一种腔式花洒型托盘,其通过过盈配合,在腔式托盘上装配花洒型端盖,数值模拟结果表明,腔式花洒型托盘在保持腔式托盘阻胶结构的基础上,基片最大形变量为2.7μm,与螺旋托盘相比降低了3.9μm左右,且基片边缘处的翘曲形变较小,为0.17μm左右;借助3D打印技术,对优化的托盘进行快速成型制造,并进行了实验分析,实验结果表明,基片形变测量值与数值模拟值变化规律吻合,相同位置的形变值误差最大为9.8%左右,说明仿真结果可靠。     

Absorption of carbon dioxide into aqueous blends of 2-amino-2-methyl-1-propanol and diethanolamine

This work presents an experimental and theoretical investigation of CO₂ absorption into aqueous blends of 2-amino-2-methyl-1-propanol (AMP) and diethanolamine (DEA). The CO₂ absorption into the amine blends is described by a combined mass transfer-reaction kinetics-equilibrium model, developed according to Higbie's penetration theory. The model predictions have been found to be in good agreement with the experimental rates of absorption of CO₂ into (AMP+DEA+H₂O). The good agreement between the model predicted rates and enhancement factors and the experimental results indicate that the combined mass transfer-reaction kinetics-equilibrium model with the appropriate use of model parameters can effectively represent CO₂ mass transfer for the aqueous amine blends AMP/DEA.     

Miscibility and interactions in blends and complexes of poly(4-methyl-5-vinylthiazole) with proton-donating polymers

The miscibility and interactions in blends and complexes of poly(4-methyl-5-vinylthiazole) (PMVT) with poly(p-vinylphenol) (PVPh), poly(acrylic acid) (PAA) and poly(vinylphosphonic acid) (PVPA) were studied. PMVT formed complexes with PVPA but not with PVPh and PAA. Each of the blends of PMVT with PVPh and PAA showed a single glass transition temperature (T_g), indicating miscibility. Fourier-transform infrared spectroscopic and X-ray photoelectron spectroscopic studies provided the existence of interactions in the PMVT blends and complexes. The XPS studies indicated that the thiazole nitrogen atoms are involved in hydrogen-bonding interactions with PVPh and PAA, and ionic interactions with PVPA. The sulfur atoms of PMVT also interact with PVPh, PAA and PVPA.     

The glass transition temperature of nitrated polystyrene/poly(acrylic acid) blends

Low-molecular-weight polystyrene was nitrated to different levels. The nitrated polystyrene was blended with different molecular weights of poly(acrylic acid), PAA. The glass transition temperatures (T_g) for the mixtures were investigated by differential scanning calorimetry. A single T_g was observed for all blends, indicating single-phase blends. In general, it was found that the T_g increases with molecular weight of PAA. The T_g values of the blends showed a positive deviation from the linear average T_g as a result of strong hydrogen bonding between the segments of the component polymers. The observed T_g values were not adequately represented by simple predictive equations or by single-parameter fitting equations. However, two-parameter fitting equations gave a reasonable representation of the data.     

Modelling of a fluidized bed bioreactor for immobilized enzymes (Part 2)

In the first part of this contribution, a mathematical model was presented for a liquid fluidized bed using immobilized enzymes, with reversible Michaelis-Menten kinetics. This part is focused on the experimental results. The reaction kinetics of native and immobilized enzymes was determined in continuous stirred tank reactors under comparable conditions. The influence of external mass transfer was investigated in a fixed bed reactor column. The extend of pore diffusional resistance was examined in a continuous stirred tank reactor and with a numerical simulation. Hydrodynamics was measured in different reactor columns (diameter d_t = 0.052 ? 0.225 m; length L: 1.0–2.0m) and with a static mixer. Further, the concentration profile was determined in a fluidized bed reactor with side stream analysis for different biocatalyst samples, fluid velocities and bed heights. The simulation of experimental results indicates that they are well described by the developed model. Furthermore, the model is well suited to predicting the influence of specific parameters on the effective kinetics of the biocatalyst and the expansion of the fluidized bed.     

Modeling high pressure vapor–liquid equilibrium of ternary systems containing supercritical CO2 and mixed organic solvents using Peng–Robinson equation of state

High pressure vapor–liquid equilibrium (VLE) of CO₂-expanded organic solvents was investigated using Peng–Robinson-LCVM-UNIFAC equation of state. Bubble pressure of several ternary mixtures was predicted using this model and correlations were developed based only on binary experimental data. A sensitivity study of the LCVM parameter numerical value was done by considering the coherence between the mathematical features of the mixing rule and the quality of the simulation. The results provided by PR-LCVM-UNIFAC were compared with those ones given by Peng–Robinson equation of state using the classical quadratic mixing rules (PR-CMR). Despite the use of two adjustable parameters for each binary system, PR-CMR is not able to provide good results when applied to ternary systems. The capability of PR-LCVM-UNIFAC model to predict liquid mixture density for ternary systems using parameters regressed only from bubble pressure experimental data was also investigated. Due to the lack of liquid density experimental data, it was possible to perform only a qualitative assessment of the density curves calculated by this equation of state.     

Prediction of macroscopic effective elastic modulus of micro-nano-composite ceramic tool materials based on microstructure model

In order to investigate the effect of microstructure parameters on the elastic modulus, based on the microstructure model represented by Voronoi tessellation, the reasonable macro-micro connection and boundary conditions were proved through the Hill’s lemma, and the uniaxial tensile process of composite ceramic tool materials was simulated. The influences of grain size, second phase volume fraction and nanoparticle volume fraction on elastic properties were studied through numerical simulation, and the elastic modulus of composite ceramic tool materials was predicted. The results showed the elastic modulus of Al₂O₃-based ceramic tool materials could be increased effectively with the contents of the second phase TiB₂ and nano-particle TiC being 20% and 10%, respectively. The numerical simulation results were in good agreement with the experimental results.     

Molecular weight controlled poly(amic acid) resins end‐capped with phenylethynyl groups for manufacturing advanced polyimide films

To investigate the effect of reactive end‐capping groups on film‐forming quality and processability, a series of molecular weight‐controlled aromatic poly(amic acid) (PAA) resins functionalized with phenylethynyl end groups were prepared via the polycondensation of 3,3′,4,4′‐biphenyltetracarboxylic dianhydride (BPDA), para ‐phenylenediamine (PDA), and 4‐phenylethynyl phthalic anhydride (PEPA) served as molecular‐weight‐controlling and reactive end capping agent. The PAA resins with relatively high concentrations endow enhanced wetting/spreading ability to form PAA gel films by solution‐cast method which were thermally converted to the fully‐cured polyimide (PI) films. The mechanical and thermal properties of PI films were investigated as a function of PAA molecular weights (M_n ) and thermal‐curing parameters. Mechanical property, dimensional stability and heat resistance of the fully‐cured PI films with PAA M_n > 20 ×10³ g mol^?1 are found to be better than that of their unreactive phthalic end‐capped counterparts. The covalent incorporation of chain‐extension structures in the backbones, induced by thermal curing of phenylethynyl groups, might facilitate yielding a higher degree of polymer chain order and consequently improved resistance strength and elongation at break to tensile plastic deformation. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 45168.     

An Investigation of using statistically designed experiments and a computer model

This paper outlines the results of an experimental program aimed at established the best formation parameters for dynamic Zr (IV) — PAA membranes formed on porous ceramic supports. The membrane formation parameters investigated are the pressure, the circulation velocity, the Zr (IV) concentration, and the PAA concentration. The formation pressure was allowed to vary between 200 psig (1.4 MP_a) to 800 psig (5.4 MP_a), the circulation velocity from 6 fps (1.8 m/s) to 24 fps (7.3 m/s), the Zr (IV) concentration from 10^-4M to 9 × 10^-4M, and the PAA concentration from 50 ppm to 250 ppm.Twenty statistically designed experiments were conducted to evaluate the effect of these four parameters on the flux and rejection of the resulting membrane at the end of the formation procedure. The results were used in a multiple linear regression computer program named BMD-PIR which develops the measured values with an accuracy of +_ 2 percent. Using these models, it is possible to form a membrane with a given value of flux or rejection within their ranges.For the range of variables used in this study, the maximum membrane rejection was 91% corresponding to a flux of 10 gpd/ft²(1.7 cm/hr) for 0.05 M NaCl and 800 psi (5.4 MP_a). High rejection was obtained by increasing the membrane formation pressure and by increasing the PAA concentration. High flux can be achieved by increasing the formation pressure, by increasing the Zr (IV) concentration up to 9.0 × 10^-4M -, and by increasing the circulation velocity.     

Modeling and simulation of the formation and utilization of microbial products in aerobic granular sludge

A mathematical model is established to simulate the formation of extracellular polymeric substances (EPS), soluble microbial products (SMP), and internal storage products (X_STO) in aerobic granular sludge. The sensitivity of these microbial products concentrations toward the key model parameters is analyzed. Independent experiments are conducted to find required parameter values and to test its predictive ability. The model is evaluated by using one‐cycle operating experimental results of a lab‐scale aerobic granule‐based sequencing batch reactor (SBR) and batch experimental results. Results show that the model is able to describe the microbial product dynamics in aerobic granules and provide further insights into a granule‐based SBR. The effect of the initial substrate and biomass concentrations on the formation of microbial products in aerobic granular sludge can therefore be analyzed by model simulation. A higher substrate concentration results in a greater concentration of EPS, SMP, and X_STO. An accumulation of biomass in the bioreactor leads to an increased production rate of EPS, SMP, and X_STO. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

The study of poly(styrene‐co‐p‐(hexafluoro‐2‐hydroxylisopropyl)‐α‐methylstyrene)/poly(ethylene oxide) blends

Different hydroxyl content poly(styrene‐co‐p‐(hexafluoro‐2‐hydroxylisopropyl)‐α‐methylstyene) [PS(OH)‐X] copolymers were synthesized and blends with 2,2,6,6‐tetramrthyl‐piperdine‐1‐oxyl end spin‐labeled PEO [SLPEO] were prepared. The miscibility behavior of all the blends was predicted by comparing the critical miscible polymer–polymer interaction parameter (χ_crit) with the polymer–polymer interaction parameter (χ). The micro heterogeneity, chain motion, and hydrogen bonding interaction of the blends were investigated by the ESR spin label method. Two spectral components with different rates of motion were observed in the ESR composite spectra of all the blends, indicating the existence of microheterogeneity at the molecular level. According to the variations of ESR spectral parameters T_a, T_d, ΔT, T_50G and τ_c, with the increasing hydroxyl content in blends, it was shown that the extent of miscibility was progressively enhanced due to the controllable hydrogen bonding interaction between the hydroxyl in PS(OH) and the ether oxygen in PEO. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2312–2317, 2004     

Lattice Boltzmann simulation of alumina-water nanofluid in a square cavity

A lattice Boltzmann model is developed by coupling the density (D2Q9) and the temperature distribution functions with 9-speed to simulate the convection heat transfer utilizing Al₂O₃-water nanofluids in a square cavity. This model is validated by comparing numerical simulation and experimental results over a wide range of Rayleigh numbers. Numerical results show a satisfactory agreement between them. The effects of Rayleigh number and nanoparticle volume fraction on natural convection heat transfer of nanofluid are investigated in this study. Numerical results indicate that the flow and heat transfer characteristics of Al₂O₃-water nanofluid in the square cavity are more sensitive to viscosity than to thermal conductivity.     

建材VOC散发过程模拟与传质参数测定新方法

建材中挥发性有机化合物(VOC)的散发是一个复杂传质过程。为准确把握传质特性,首先建立了一套描述干建材散发行为的显性完全解析模型,适用于模拟对人体最不利的无换气情况;代入有关文献中的传质参数预测了环境舱浓度,与文献中对应的实验数据及数值算法预测值吻合良好。然后基于对模型的分析提出一套简便快捷的实验方法,能够利用不同VOC背景值下干建材在密闭舱中散发的平衡浓度或逐时浓度,求取预测散发过程的4个重要的传质参数:可散发浓度C₀、扩散系数D、分配系数K和对流传质系数h_m;实验部分测算了两类密度板中甲醛散发的C₀、D、K、h_m,代入数值算法预测了密闭舱和直流舱的环境舱浓度,与实验数据吻合良好。该套模型和测定方法能够应用于建材散发的模拟研究。     

Model development,parameter identification,and simulation of SCP production processes in air lift tower reactors with external loop—II: Extended culture modelling and quasi steady state parameter identification

Yeast was cultivated in extended culture in a bench-scale 275 cm high air lift tower reactor 15 cm dia. with an external loop. Longitudinal dissolved oxygen concentration profiles, substrate and cell mass concentrations in the medium, O₂ and CO₂ concentrations in the gas phase, as well as gas flow rates and liquid recirculation rates were measured. A distributed parameter model was used to describe the cultivation process variation along the column, cell mass, substrate and oxygen balances in the medium, O₂ and CO₂ balances in the gas phase, variation of the volumetric mass transfer coefficient along the column due to bubble coalescence, as well as double substrate Monod kinetics. Based on simulation runs it was assumed that under non limited and oxygen transfer limited growth conditions, the cell mass and substrate concentrations are uniform in the reactor. The simulation was carried out by a hybrid computer. The unknown model parameters (volumetric mass transfer coefficient at the gas entrance, k_La^E, and coalescence factor K_ST) and two kinetic parameter R_Omax and K_O were identified by means of experimental results with quasi steady state simulation methods.     

pH响应性PAA/毒死蜱/氨基化介孔硅缓释体系的制备与性能

以共缩聚法合成氨基化介孔硅,采用浸渍法制备毒死蜱/氨基化介孔硅,并以带负电荷的聚丙烯酸（PAA）为功能分子,通过静电吸附作用制备了具有pH响应的PAA/毒死蜱/氨基化介孔硅缓释体系。利用XRD、N₂吸附-脱附、TEM、SEM、TG、Zeta电位和FTIR对PAA/毒死蜱/氨基化介孔硅的结构进行了表征,并探究了其在不同pH和温度下的释药行为。结果表明,PAA通过静电作用包覆于毒死蜱/氨基化介孔硅的表面。缓释体系的药物释放主要受到PAA的阻碍作用,PAA修饰载药氨基化介孔硅显示出明显的pH响应性,当pH≤7时,其药物释放速率随pH减小而增大,而在偏碱性条件下的释药速率稍大于中性环境。同时,载药体系的释药速率还受到温度的影响。其释药行为可用Korsmeryer-Pappas动力学模型来描述。