Crystallization kinetics of iPP. Model and experiments

Summary The model proposed by Ziabicki [1] [2] for non-isothermal crystallization kinetics was adopted in this work, to describe the crystallization kinetics of a commercial iPP under a very wide range of conditions (i.e. isothermal, slow-cooling rate and high-cooling rate (up to 200 °C/s) from the melt). A modification of the model was required in order to achieve a good agreement between model predictions and the whole set of experimental data. Received: 22 December 2000/Accepted: 30 January 2001     

Morphology,structure, and kinetic analysis of nonisothermal cold‐ and melt‐crystallization of syndiotactic polystyrene

Nonisothermal cold‐ and melt‐crystallization of syndiotactic polystyrene (sPS) were carefully carried out by Perkin–Elmer Diamond differential scanning calorimetry, polarized optical microcopy (POM), and wide angle X‐ray diffraction. The experimental data subjected to the two types of processing were thoroughly analyzed on the basis of Avrami, Tobin, Ziabicki, and combination of Avrami and Ozawa models. Avrami, Tobin, and Ziabicki analyses indicate that nonisothermal cold‐crystallization (A) characterizes smaller Avami and Tobin exponent and larger Ziabicki kinetic crystallizability index G than those obtained from nonisothermal melt‐crystallization (B) possibly due to the existence of partially ordered structures in the quenched samples. Kissinger and the differential isoconversional method (DICM) of Friedman's were utilized to obtain effective energy barrier of A, in good agreement with that obtained by using Arrhenius equation to analyze the isothermal cold‐crystallization, indicating that Kissinger and Friedman equations can be applied to obtain activation energy from A of sPS. X‐ray diffraction analysis indicates that cold‐crystallization mainly produces α‐type crystal but for melt‐crystallization the contents of α‐type and β‐type crystals depend on the cooling rates. The POM also indicates the difference of end morphology of the sample between A and B. At the same time, the DICM of Friedman's was applied to analyze experimental data of B, which were divided into two groups with 20 K/min as the threshold, and it was found that the formation of β‐type crystal possesses larger absolute value of effective activation barrier than the formation of α‐type crystal. © 2006Wiley Periodicals, Inc. J Appl Polym Sci 103: 1311–1324, 2007     

Nanofibers from gas-assisted polymer melt electrospinning

The concept of a gas-assisted polymer melt electrospinning process is presented. This technique allows for reduced quenching of the melt jet in the spinning region, and thus increasing the jet attenuation rate and resulting in production of sub-micron scale fibers. A comprehensive melt electrospinning model was used to analyze the effects of the heated air stream on the polymer jet. It was found that under the investigated conditions in electrospinning of polylactic acid (PLA) melt, air drag produced an additional 10% thinning compared to the un-assisted melt electrospinning process, and the heating provided by the air stream resulted in an additional 20-fold jet thinning.     

熔喷工艺参数和喷嘴设计参数对纤维直径的影响

引　言熔喷法是 2 0世纪 5 0年代发展起来的一种制备超细纤维非织造布的方法 ,其纤维直径仅 1～10 μm.熔喷非织造布是高效精细过滤材料 ,过滤效率可达 99 9%以上 ,广泛用于医疗和环保等领域 .熔喷是依靠高速高温气流喷吹聚合物熔体使其迅速拉伸而形成超细纤维的 .数学模型对于     

Transient flow-induced crystallization of a polyethylene melt

Extensional, flow-induced crystallization (FIC) of a high-density polyethylene (HDPE) melt has been studied using a four-roll mill flow cell. Simultaneous measurement of the birefringence and scattering dichroism are used to quantify the crystallization process during and following transient flow deformation in planar extensional flow. Suspension of the HDPE phase as a droplet in a linear low-density polyethylene carrier phase prevents die blockage on crystallization and allows measurement of the flow kinematics. Initial crystallization rates following a transient flow deformation show a stress-strain dependence. Crystallization induction times during flow correlate with the extension rate during the transient flow deformation. Measurement of the HDPE melt steady and oscillatory flow rheological properties, along with measurements of time constants following step-shear and extensional strains, allow determination of the viscoelastic properties which enhance FIC. Parameters obtained from these experiments are used in a phenomenological model for FIC which allows qualitative and semiquantitative analysis of the data trends, particularly the relaxation behavior of the birefringence during flow cessation/crystallization. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 2165–2176, 1997     

Modeling of flow‐induced crystallization in blends of isotactic polypropylene and poly(ethylene‐co‐octene)

Poly(ethylene‐co‐octene) (PEOc) has been shown to provide a high toughening contribution to isotactic polypropylene (iPP). The theoretical modeling of flow‐induced crystallization (FIC) of blends of iPP and PEOc is not much reported in the literature. The aim of the present work is to clarify the FIC of iPP upon addition of PEOc in terms of theoretical modeling. The crystallization of iPP and PEOc blends in flow is simulated by a modified FIC model based on the conformation tensor theory. Two kinds of flow fields, shear flow and elongational flow, are considered in the prediction to analyze the influence of flow field on the crystallization kinetics of the polymer. The simulation results show that the elongation flow is much more effective than shear flow in reducing the dimensionless induction time of polymer crystallization. In addition, the induction time of crystallization in the blends is sensitive to the change of shear rate. In comparison with experimental data, the modified model shows its validity for the prediction of the induction time of crystallization of iPP in the blends. Moreover, the simulated relaxation time for the blends becomes longer with increasing percentage of PEOc in the blends. Copyright © 2012 Society of Chemical Industry     

Wire Melt Electrospinning of Thin Polymeric Fibers via Strong Electrostatic Field Gradients

Here, a novel melt electrospinning method to produce few‐micron and nanometer thick fibers is presented, in which a polymer‐coated wire with a sharp tip is used as the polymer source. The polymer coating is melted via Joule heating of the source wire and extracted toward the target via electrostatic forces. The high viscosity and low charge density of polymer melts lower their stretchability in melt. The method relies on confining the Taylor cone and reducing initial jet diameter via concentrated electrostatic fields as a means to reduce the diameter of fibers. As a result, the initial jet diameter and the final fiber diameter are reduced by an order of magnitude of three to ten times, respectively, using wire melt electrospinning compared to syringe‐ and edge‐based electrospinning. The fiber diameter melt electrospun via this novel method is 1.0 ± 0.9 µm, considerably thinner than conventional melt electrospinning techniques. The generation of thin fibers are explained in terms of the electrostatic field around the wire tip, as obtained from finite element analysis (FEA), which controls the size and shape of the melt electrospun jet.     

尼龙66纤维高速纺丝研究(Ⅱ)——数学模型的发展

本文以前文报道的尼龙66高速纺丝的在线直径、温度和双折射的测定结果为依据,对Zieminski提出的结晶高聚物熔融纺丝的数学模型进行了验证,进而对尼龙66高速纺丝的有关表观拉伸粘度、传热系数等材料函数以及结晶特性进行了有益的探讨。结果表明,纺线上实测的直径和温度数据与数学模型预期的结果有很好的相似性,实验中测定的拉伸粘度及热传导系数能更有效地改善数学模型对直径和温度分布预测的准确性。模型预期的双折射数值与纺线上实测的结果有较大的偏差,表明取向情况下结晶动力学的关系式有待于发展和完善。     

Crystallization of running filament in melt spinning of polypropylene

The crystallization kinetics of the running filament in melt spinning have been studied for three cases: isothermal crystallization of an isotropic melt, non-isothermal crystallization of an isotropic melt, and non-isothermal crystallization of a non-isotropic melt. Both the temperature and the orientation dependences of nucleation rate and growth rate are estimated for polypropylene. Calculated curves for non-isothermal crystallization of a non-isotropic melt with partial high orientation closely approximate the experimental data. In particular, the experimental data are best explained by crystallization with two-dimensional growth. The crystallization processes in melt spinning may be governed by localized molecular orientation of the supercooled melt in the initial stage.     

Orthogonal design study on factors effecting on fibers diameter of melt electrospinning

Melt electrospinning is a much more simple and safe method to produce ultra fine fibers than solution electrospinning. The diameters of melt electrospinning fibers are thicker. To find the factors that affect the fibers diameter in melt electrospinning, orthogonal design was used to examine melt temperature, spinning voltage, spinning distance, and melt flow rate (MFR) of polymer. Results showed that MFR at present three levels has the most important impact both on the average diameters and standard deviations of fiber diameters. The scanning electron microscopy pictures show that all the fibers have smooth surface, which means the melt electrospinning fibers have good mechanical properties. POLYM. ENG. SCI., 50:2074–2078, 2010. © 2010 Society of Plastics Engineers     

New approach to develop a 3D non-isothermal computational framework for injection molding process based on level set method

The simulation of three-dimensional (3D) non-isothermal, non-Newtonian fluid filling process is an extremely difficult task and remains a challenging problem, which includes polymer melt flow with free surface coupled with transient heat transfer. This paper presents a full 3D non-isothermal two-phase flow model to predict the complex flowinmelt filling process,where the Cross-WLFmodel is applied to characterize the rheological behavior of polymer melt. The governing equations are solved using finite volume method with SIMPLEC algorithm on collocated grids and the melt front is accurately captured by a high resolution level set method. A domain extension technique is adopted to dealwith the complex cavities, which greatly reduces the computational burden. To verify the validity of the developed 3D approach, the melts filling processes in two thin rectangular cavities (one of them with a cylindrical insert) are simulated. The predicted melt front interfaces are in good agreement with the experiment and commercial software prediction. For a case with a rather complex cavity, the dynamic filling process in a hemispherical shell is successfully simulated. All of the numerical results show that the developed numerical procedure can provide a reasonable prediction for injection molding process.     

Non-Isothermal crystallization of isotactic polypropylene in dotriacontane. I: Effects of dilution,cooling rate,and nucleating agent addition on overall crystallization kinetics

The overall non-isothermal crystallization kinetics for nucleated and non-nucleated isotactic polypropylene (iPP) in dotriacontane systems was investigated. Adipic acid was used as the nucleating agent. Crystallization peak temperature was determined via differential scanning calorimetry as a function of the experimentally controlled variables iPP concentration, cooling rate, and nucleating agent concentration. The influence of these variables on crystallization mechanism and spherulitic structure as implied by the Ozawa and Ziabicki analyses was determined. The non-isothermal crystallization kinetics presented here are the first for iPP-diluent systems with and without nucleating agent.     

Continuous electrospinning of polymer nanofibers of Nylon-6 using an atomic force microscope tip

An atomic force microscopy (AFM) probe is successfully utilized as an electrospinning tip for fabricating Nylon-6 nanofibers. The nanometre-size tip enabled controlled deposition of uniform polymeric nanofibers within a 1 cm diameter area. Nylon-6 nanofibers were continuously electrospun at a solution concentration as low as 1 wt% Nylon-6 in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP). Wide-angle X-ray diffraction (WAXD) and differential scanning calorimetry (DSC) results of the AFM electrospun fibers indicated that the nanofibers predominantly display the meta-stable γ crystalline form suggesting rapid crystallization rate during the process. In addition to precise control over fiber deposition and diameter, some of the drawbacks of conventional electrospinning such as large volume of solutions and clogging of needles can be overcome using this AFM based electrospinning technique. Lastly, a comparison of electrospun fibers from syringe-needle based electrospinning and AFM probe-tip based electrospinning indicated significant morphological and microstructural differences in the case of AFM based electrospinning.     

Preparation of poly(ether sulfone) nanofibers by gas‐jet/electrospinning

Poly(ether sulfone) (PES) nanofibers were prepared by the gas‐jet/electrospinning of its solutions in N,N‐dimethylformamide (DMF). The gas used in this gas‐jet/electrospinning process was nitrogen. The morphology of the PES nanofibers was investigated with scanning electron microscopy. The process parameters studied in this work included the concentration of the polymer solution, the applied voltage, the tip–collector distance (TCD), the inner diameter of the needle, and the gas flow rate. It was found from experimental results that the average diameter of the electrospun PES fibers depended strongly on these process parameters. A decrease in the polymer concentration in the spinning solutions resulted in the formation of nanofibers with a smaller diameter. The use of an 18 wt % polymer solution yielded PES nanofibers with an average diameter of about 80 nm. However, a morphology of mixed bead fibers was formed when the concentration of PES in DMF was below 20 wt % during gas‐jet/electrospinning. Uniform PES nanofibers with an average diameter of about 200 nm were prepared by this electrospinning with the following optimal process parameters: the concentration of PES in DMF was 25 wt %, the applied voltage was 28.8 kV, the gas flow was 10.0 L/min, the inner diameter of the needle was 0.24 mm, the TCD was 20 cm, and the flow rate was 6.0 mL/h. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Behavior of melt electrospinning/blowing for polypropylene fiber fabrication

The fabrication process of polymer fibers has been analyzed in various ways, and several studies have been conducted to develop new processes and optimize existing ones. Several studies have been conducted on the electrospinning process, which can easily fabricate nanofibers, and the development of materials manufactured through electrospinning has also been investigated. However, research on the nanofiber fabrication and processing of thermoplastic polymers, such as polypropylene (PP), polyethylene and polyethylene terephthalate, is relatively lacking. Therefore, research on nanofiber fabrication is essential. In this study, PP fibers were successfully manufactured through a melt electrospinning/blowing process, which combined melt blowing and electrospinning. To analyze the melt electrospinning/blowing process, the dynamic behavior of the spinning process was observed using a charge-coupled device camera in real time, and the effects of the different spinning conditions were compared and analyzed. As the hot air or high voltage was increased, the spinning jet area tended to increase. In addition, the average diameter of the fabricated fibers tended to decrease as a high voltage was applied at a hot air pressure of 0.01 MPa; conversely, the average diameter tended to increase at a hot air pressure of 0.03 MPa. A similar trend was observed for the tensile stresses in the PP web fabrics. The polymer fibers produced by this melt electrospinning/blowing process can be applied as a production process for nanomembranes, filters and battery separators. © 2022 Society of Industrial Chemistry.     

Electrospinning of polymer nanofibers with specific surface chemistry

Electrospinning is a process by which sub-micron polymer fibers can be produced using an electrostatically driven jet of polymer solution (or polymer melt). Electrospun textiles are of interest in a wide variety of applications including semi-permeable membranes, filters, composite applications, and as scaffolding for tissue engineering. The goal of the research presented here is to demonstrate that it is possible to produce sub-micron fibers with a specific surface chemistry through electrospinning. This has been accomplished by electrospinning a series of random copolymers of PMMA-r-TAN from a mixed solvent of toluene and dimethyl formamide. X-ray Photoelectron Spectroscopy (XPS) analysis shows that the atomic percentage of fluorine in the near surface region of the electrospun fibers is about double the atomic percentage of fluorine found in a bulk sample of the random copolymer, as determined by elemental analysis. These results are in good agreement with XPS and water contact angle results obtained from thin films of the same copolymer materials.     

KINETICS OF MELT CRYSTALLIZATION IN FALLING FILMS

An analysis of the solidification rates of binary mixture melts flowing as a thin film on a cold surface, useful in the separation or purification of eutectic mixtures, is presented. The analysis which incorporates the hydrodynamics of the falling film and the convective heat transfer at the melt/crystal interface was used to determine the average crystallization velocity. The effect of parameters such as Stefan number (subcooling), initial superheat and the melt loading rate on the average crystallization velocity was examined. Experiments were performed using three different binary organic mixtures at subeutectic compositions. The results of the theoretical and experimental studies showed good agreement validating the model.     

Computational fluid dynamics simulation and theoretical study the air jet flow field of a wide slot positive pressure drawing assembly in the spunbonding nonwoven process

The polymer air‐drawing model of polyethylene terephthalate spunbonding nonwovens and the air jet flow field model in wide slot positive pressure spunbonding process have been established. The influence of the density and the specific heat capacity of polymer melt at constant pressure changing with polymer temperature on the fiber diameter have been studied, which is solved by introducing the numerical computation results of the air jet flow field of attenuator. It is simulated by means of the finite difference method. The predicted fiber diameter agrees with the experimental data. The effects of the processing parameters on the fiber diameter with the help of the image analysis method have been investigated. A higher inlet pressure, smaller slot width, and smaller jet angle will all cause higher z‐axis position of air velocity and air pressure, which are beneficial to the air drawing of the polymer melt and thus to reducing the fiber diameter. The experimental results show that the agreement between the results and experimental data is better, which verifies the reliability of these models. The results present great prospects for this research in the field of computer assisted design of spunbonding process, technology, and equipment. POLYM. ENG. SCI., 55:231–242, 2015. © 2014 Society of Plastics Engineers     

Experimental study and numerical simulation the air jet flow field of a dual slot sharp blunt die in the melt blowing nonwoven process

In this work, the physical model of a polymer in a melt blowing process is established and solved by introducing the numerical computation results of the air jet flow field of the dual slot sharp inset die. The influence of the melt blowing processing parameters and the die design parameters on the fiber diameter is also studied. A lower polymer throughput rate, higher polymer melt initial temperature, higher air initial temperature, higher air initial velocity, smaller angle between slot and axis of the spinneret, smaller width of the die head, and larger width of the slot can all produce finer fibers. At the same time, the air jet flow field model of the dual slot sharp inset die of polypropylene polymer nonwovens fabrics in melt blowing process was also established. The air jet flow field model was solved by using the finite difference method. The computational simulation results of the distributions of the z‐components of air temperature and air velocity along the spinline during melt blowing process are in accordance with the experimental data. The air drawing model of melt blowing process was simulated by means of the numerical simulation results of the air jet flow field. The predicted fiber diameter agree with the experimental data. The effects of the air initial velocity and air initial temperature on the fiber diameter were studied and discussed. The results demonstrate that a higher air initial velocity and a higher air initial temperature are beneficial to the air drawing of the polymer melt and thus to reduced fiber diameter. The results show the great potential of this research for computer assisted design in melt blowing nonwoven process and technology. POLYM. ENG. SCI., 57:417–423, 2017. © 2016 Society of Plastics Engineers     

Numerical modeling,simulation, and experimental validation of predicting fiber diameter in wide‐slot positive‐pressure spunbonding process

An air‐drawing model of polypropylene (PP) polymer and an air jet flow field model in wide‐slot positive‐pressure spunbonding process are established. The influences of the density and the specific heat capacity of polymer melt at constant pressure changing with polymer temperature on the fiber diameter have been studied. The predicted fiber diameter agrees with the experimental data as well. The effects of the processing parameters on the fiber diameter have been investigated. The air jet flow field model is solved by means of the finite difference method. The numerical simulation computation results of distribution of the fiber diameter match quite well with the experimental data. The air‐drawing model of polymers is solved with the help of the distributions of the air velocity. It can be concluded that the higher air velocity and air temperature can yield the finer fibers diameter. The higher inlet pressure, longer drawing segment length, smaller air knife edge, longer exit length, smaller slot width, and smaller jet angle can all cause higher air velocity and air pressure along z‐axis position, which are beneficial to the air drawing of the polymer melt and thus to reduce the fiber diameter. The experimental results show that the agreement between the predicted results and the experimental measured data is very better, which verifies the reliability of these models. Also, they reveal great prospects for this work in the field of computer‐assisted design (CAD) of spunbonding process. POLYM. ENG. SCI., 58:1371–1380, 2018. © 2017 Society of Plastics Engineers