塑料成型中聚合物的壁面滑移现象

重点阐述了目前3种主要的聚合物壁面滑移机理,介绍了几种常见的壁面滑移模型,并就相关影响因素进行了论述。最后介绍了国内外学者所取得关于壁面滑移的成果,针对壁面滑移的测量、数学建模、仿真等问题,给出了建议。     

Injection Molding Micro‐ and Nanostructures in Thermoplastic Elastomers

Flexible polymers such as poly dimethyl siloxane (PDMS) can be patterned at the micro‐ and nanoscale by casting, for a variety of applications. This replication‐based fabrication process is relatively cheap and fast, yet injection molding offers an even faster and cheaper alternative to PDMS casting, provided thermoplastic polymers with similar mechanical properties can be used. In this paper, a thermoplastic polyurethane is evaluated for its patterning ability with an aim to forming the type of flexible structures used to measure and modulate the contractile forces of cells in tissue engineering experiments. The successful replication of grating structures is demonstrated with feature sizes as low as 100 nm and an analysis of certain processing conditions that facilitate and enhance the accuracy of this replication is presented. The results are benchmarked against an optical storage media grade polycarbonate.

     

Ultrasonic‐assisted dyeing: I. Nylon dyeability with reactive dyes

The use of ultrasonic power (38.5 KHz, 350 W) to assist the dyeability of nylon‐6 fibre with reactive dyes is reported. The effects of the different factors that may affect the dyeability of nylon‐6 fibre with Reactive Red 55 were simultaneously carried out under both ultrasonic power and conventional heating conditions. The colour strength values obtained for the dyed samples using ultrasonic power were higher than those obtained using conventional heating. Also, the effect of alkaline soaping treatment on dye fixation for the dyed fabrics with different reactive dyes, at both acidic and neutral pHs, is generally better with ultrasonic than with conventional heating. The overall results indicate that the enhancing effect is mainly attributed to the de‐aggregation of dye molecules, which leads to better dye diffusion and possible assistance for dye‐fibre covalent‐bond fixation. The results of wet fastness properties of the dyed fabrics reveal improvement using ultrasonic power dyeing relative to the conventional heating method. © 2003 Society of Chemical Industry     

Planar Entry Converging Flow During Extrusion of Polymer Melts

In this article, a planar entry converging flow during die extrusion of polymeric melts was analyzed and a differential equation of entry converging boundary streamline equation with rheological parameters and channel geometry is established. By applying limit theory, the entry converging boundary streamline equation in the case with different non-Newtonian index (n) was discussed, and the corresponding expressions of entry natural convergent half angle and convergent region length were derived. The entrant flow pattern might be described with the half angle of entry natural convergence (α₀) and the convergent region length (L _e ) of the melts, and α₀ and L _e were mainly a function of the entry elastic storage deformation energy (e) and n. The values of α₀ and L _e were calculated by means of these simplified expressions. It was found that the estimations of α₀ decrease nonlinearly white L _e increases linearly with an addition of e. Finally, a preliminary verification of the natural converging half angle equation was made. The results showed that the estimations of 2α₀ based on the experiments of a low-density-polyethylene (LDPE) and a high-density-polyethylene (HDPE) were close to the data reported in reference.     

Extrusion Monitoring of Polymer Melts Using a High‐Temperature Surface‐NMR Probe

Summary: Extrusion is one of the major ways of polymer processing, and extrusion monitoring is important to control or improve the extrusion process and the product quality. Especially methods for in‐line monitoring are desired because those enable the fastest possible response and a localization of chemical reactions in reactive processing. Methods of optical and acoustic spectroscopy have successfully been implemented so far. NMR provides a wealth of information. Surface NMR mostly gives access to molecular mobility via relaxation times. These can be correlated to temperature, composition and homogeneity which are substantial indicators for the product quality. NMR is a non‐destructive method, which does not require direct contact with the sample and it is not restricted to optical transparent materials and is therefore suitable for extrusion monitoring. The problem for the adaptation is the hostile environment in and in front of an extruder for polymer melts. Here, a NMR surface probe is presented sustaining this environment in front of an extruder. First measurements with this device are shown.

High‐temperature surface‐NMR probe.     

壁面滑移对塑料异型材共挤影响的数值模拟研究

在壁面滑移的边界条件下,利用流体有限元分析软件Polyflow,采用Giesekus本构方程,对L型塑料异型材进行了三维等温共挤出数值模拟。分析了滑移系数对共挤出胀大和粘性包围、口模出口面的剪切速率场及共挤出口模压力降的影响。研究表明,随着滑移系数的增大,共挤出胀大和粘性包围、口模出口面的最大剪切速率及口模压力降也逐渐增大,且滑移系数介于105和108之间时增速最大;滑移系数越小,共挤出制品质量越好。     

Micro‐injection molding of CNT nanocomposites obtained via compounding process

Many research efforts have gone in the production of carbon nanotubes (CNT) composites for functional and structural applications and many processing methodologies have been experimented. Twin‐screw extrusion appears to be the most suitable way from the perspective of production scale up and commercialization of these composites. At the same time, micro‐injection molding process is considered as the key manufacturing technology for the mass production of miniaturized components and devices. Despite the massive literature about nanocomposites and microinjection molding process, few articles focus on the interaction between the compounding process and the following micro‐injection molding transformation processes. This article aims at analyzing the influence of the screw configuration used in compounding process on the rheological and technological properties of the resulting nanocomposites. Two different combinations of screw elements have been tested to incorporate CNTs in two different resins: LCP (liquid crystal polymer) and POM (polyoxymethylene) typically used in micro‐injection molding. The effects of the process set up have been observed studying first the rheology and then the moldability of nano‐compounds microinjected ribs with high aspect ratio. The nanofiller dispersion has been evaluated via light and transmission electron microscopy. The results confirm that, the screws show different capacity at promoting the dispersion of the nanofiller, which affects the moldability of micro‐injected CNT nanocomposites. The viscosity of the polymer seems a critical factor as well, because it influences first the dispersion of CNT bundle during extrusion and then the injection moldability of the composites in the micro‐channels. POLYM. COMPOS., 38:349–362, 2017. © 2015 Society of Plastics Engineers     

微注塑充模过程中壁面滑移对熔体流动影响的研究*

针对微型塑料件注塑充模过程中,壁面滑移对流动的影响不可忽略的情况,运用流体分析软件Fluent,以微阶梯圆形截面通道为模型,在考虑和不考虑壁面滑移的情况下,对微注塑充模流动过程中壁面滑移的影响进行了数值模拟。分析了细通道近壁面处熔体的剪切速率和黏度,发现考虑壁面滑移时近壁面处的剪切速率略大,黏度略低。研究了熔体在粗通道和细通道中沿径向的流动速度和温度分布,以及沿微通道流动方向上的压力分布。结果表明,考虑壁面滑移时熔体流动速度较大,与壁面接触的熔体流动速度不再为零,且微通道截面尺寸越小,这种现象越明显;考虑壁面滑移时近壁面处熔体温度略高,并且粗通道中的这种现象更明显一些;壁面滑移对微通道中的压力分布几乎没有影响。总体而言,壁面滑移有利于微注塑充模。     

Ultrasonic‐assisted dyeing: II. Nylon fibre structure and comparative dyeing rate with reactive dyes

Comparative dyeing kinetics of nylon‐6 fibre with different reactive dyes using conventional and ultrasonic conditions are presented. The time/dye‐uptake isotherms are revealing the enhanced dye‐uptake in the second phase of dyeing (diffusion phase). The data of dyeing rate fit well with the integrated form of the first‐order rate equation and values of dyeing rate constant and half‐time of dyeing are discussed. Ultrasonic efficiency in accelerating the dyeing rate relative to conventional heating was examined for all dyes used to show that ultrasonics are most effective for a dyeing system which has difficulty in achieving high dye‐uptake. To clarify the role of fibre fine structure and whether it is affected during dyeing with ultrasonic waves, time‐dependent ultrasonic pre‐treatment of nylon‐6 fibres and its effect on the colour strength obtained is presented. X‐ray diffraction studies on nylon‐6 fibres conventionally and ultrasonically pre‐treated have shown that the percentage of fibre crystallinity has become higher in ultrasonically treated fibre in comparison with that of conventionally treated. Although the increased crystallinity of the fibre, which occurs simultaneously during the ultrasonic dyeing process, would retard dye uptake, it seems that the enhanced effect of power ultrasonic is high enough to overcome this side‐effect on the fibre. © 2003 Society of Chemical Industry     

注射保压过程中O2/N2分子在PMMA熔体内部的扩散行为

研究了注射成型保压过程中,不同工艺条件下O2/N2混合气体在聚甲基丙烯酸甲酯（PMMA）聚合物内部的扩散行为。针对注射成型工艺特点,将注射保压阶段的低分子扩散简化为不同温度条件下的准静态扩散行为;建立了包含O2/N2气体和10条聚合度为10的全同立构PMMA链团的扩散映射模型。经能量最小化及退火算法实现了扩散模型的能量初始化;基于COMPASS力场,实现了O2/N2混合气体在PMMA熔体内部扩散的分子动力学模拟实验。结果表明,O2和N2的扩散系数均随温度的升高而增大,且同一温度下,O2比N2更容易扩散;不同温度下O2和N2的均方位移函数（MSD）对数lg(MSD)与时间对数lg(t)关系曲线的斜率（n）都接近于1,符合Einstein扩散机制。     

Quantitative Characterization of Viscoelastic Properties and their Relationship During Extrusion Flow of Polymer Melts

The viscoelastic behavior, such as end pressure losses, die swell, and normal stress difference, is a very important rheological phenomenon of viscoelastic fluids in channel flow. Therefore, understanding the elastic behavior and the mechanisms is quite necessary and meaningful for polymer rheology. Extrusion is a usual processing way in polymer industry. The viscoelastic behavior and the factors affecting it during die extrusion flow of polymeric melts are discussed, and the relationships among these viscoelastic properties, such as entry pressure drop (ΔP _en), exit pressure drop (ΔP _ex), die-swell ratio (B), and the first normal stress difference (N ₁), are analyzed in this article. The results showed that there are some simple and available expressions for describing the relationships among these viscoelastic property parameters and the values of these parameters can be evaluated. Furthermore, the recent progresses in the quantitative expressions for prediction of these viscoelastic property parameters and their correlations are briefly reviewed.     

Three‐dimensional simulation of multi‐material injection molding: Application to gas‐assisted and co‐injection molding

This paper presents an overview of the results obtained at the Industrial Materials Institute (IMI) on the numerical simulation of the gas‐assisted injection molding and co‐injection molding. For this work, the IMI's three‐dimensional (3D) finite element flow analysis code was used. Non‐Newtonian, non‐isothermal flow solutions are obtained by solving the momentum, mass and energy equations. Two additional transport equations are solved to track polymer/air and skin/core materials interfaces. Solutions are shown for different thin parts and then for thick three‐dimensional geometries. Different operating conditions are considered and the influence of various processing parameters is analyzed.     

Gas‐assisted injection molded polypropylene: The skin‐core structure

In this article, gas penetration‐induced skin‐core structure of isotactic polypropylene(iPP), which is molded by gas‐assisted injection molding at different gas pressures, was investigated. For comparison, the counterpart was also molded by conventional injection molding (CIM) using the same processing parameters but without gas penetration. They were characterized via PLM, DSC, and SEM. And the crystal morphology at different gas pressures was principally concerned. For the GAIM parts, highly oriented structure is formed in the skin zone, and much less oriented structure in the inner zone (near the gas channel surface). Furthermore, it is suggested that the naked shish structure can be developed in the skin zone of GAIM part, which is molded at higher gas pressures, and shish‐kebab structure is mainly formed in the skin zone of that, which is molded at lower gas pressure. However, for the CIM part, from the skin to the core zone, the dominant morphological feature is spherulite. In a word, the presence of gas penetration notably enhances the oriented structure formation and gives rise to the skin‐core structure. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Graphene coating assisted injection molding of ultra‐thin thermoplastics

High strength light weight parts are critical for the development of new technologies, particularly electronic devices, such as laptop computers, smart phones, and tablet devices. Injection molded plastics and composites are excellent choices for mass producing such parts. As the part thickness decreases from traditional injection molding (>2 mm thickness) to thin wall molding (～1 mm thickness), and lastly, to ultra‐thin wall molding (<0.5 mm thickness), avoiding incomplete filling (short shots) becomes more challenging. Even though, methods exist today for molding thin‐wall plastic parts (i.e., fast heating/fast cooling injection molding), they require multiple steps resulting in a noncost efficient process. In this article, we demonstrate the technical feasibility of using graphene coating to facilitate flow, by promoting slip at the mold walls. We evaluate the influence of coated and uncoated mold inserts on fiber orientation. We present experimental results using un‐reinforced polypropylene and a 40% by weight carbon fiber reinforced polycarbonate/acrylonitrile butadiene styrene. POLYM. ENG. SCI., 55:1374–1381, 2015. © 2015 Society of Plastics Engineers     

Residual wall thickness of water‐powered projectile‐assisted injection molding pipes

Water‐powered projectile‐assisted injection molding (W‐PAIM) is an innovative molding process for the production of hollow shaped polymer parts. The W‐PAIM utilizes high pressure water as a power to drive a solid projectile to displace the molten polymer core to form the hollow space. The residual wall thickness (RWT) and its distribution are the important quality criteria. The experimental and numerical investigations were conducted. Experimental specimens showed that the RWT of a W‐PAIM pipe was much thinner than that of a water‐assisted injection molding pipe. The cross‐section size of the projectile defined the basic penetration section size. The software FLUENT was used to obtain the instantaneous distributions of the flow field, which revealed the forming mechanism of the RWT. The experiments indicated that the processing parameters, such as melt temperature, melt injection pressure, mold temperature, and water injection delay time had obvious effects on the RWT, while the water pressure had little effect on it. The RWT of curved pipes was thin at the inner concave side while thick at the outer convex side. The RWTs at the bend portion are influenced by the deflection angle and bending radius, which is due to the pressure difference between the two sides. POLYM. ENG. SCI., 59:295–303, 2019. © 2018 Society of Plastics Engineers     

毛细管动态挤出下聚合物熔体非线性流变行为的研究

采用毛细管动态流变仪,选用PELD、PP、PS和PA等典型物料,研究了毛细管动态挤出下各聚合物熔体的非线性流变行为。结果表明,不同物料的流变行为对振动力场的响应特性有较大差异,只有在一定的振幅和频率下振动力场才能有效降低熔体的黏度。实验首次发现,PP、PS和PA存在窄的振动参数区域,在此区域内,熔体的动态表观黏度值大于相应的稳态值,出现“加振变黏”现象。这一新的发现表明,并非“只要引入振动就一定有利于聚合物材料的成型加工”,必须考虑不同分子结构的聚合物材料对振动的不同响应规律。     

Structuring and Molding of Electrospun Nanofibers: Effect of Electrical and Topographical Local Properties of Micro‐Patterned Collectors

The controlled deposition of electrospun nanofibers at the micro‐scale is studied. Several collectors with microscopic patterns are prepared using photolithography. Nanofiber deposition is influenced by the geometry, the size, and the distance between micro‐patterns. Within certain conditions, membranes with multiple “micro spider‐webs” or perpendicularly interconnected microgrids are obtained. Dielectric micro‐holes having a conductive bottom can be filled by the nanofiber. This kind of micro‐molding is rationalized using simulations that show the influence of the collector relative permittivity on the electric field at the pattern vicinity. “Micro‐woven” membranes of PCL with good mechanical properties can be produced, allowing their use for biomedical applications in tissue engineering.