在低频振动场中注塑成型iPP试样的结构与性能研究

利用自行研制的低频振动注塑成型装置进行等规聚丙烯(iPP)试样的结构与性能研究.实验中对常规注射和振动注射成型的试样力学性能和微观形态进行了对比实验.采用低频振动注塑成型工艺实现了IPP试样的自增强,在190℃下进行注射,强度由常规试样的41.3 MPa最大提高到振动试样的48.4 MPa(振幅PA=59.4 MPa,振频FR=0.7 Hz),强度提高了17.2%;SEM显示常规试样芯层结构主要由球晶构成,振动注射使球晶在流动方向上变形、取向,晶粒尺寸得到细化;DSC表明振动注射促进熔融峰向高温漂移,晶体结晶更加完善,结晶度最大提高了12.1%;WAXD显示低频大振幅振动注塑有利于γ晶型的生成,γ晶型有利于试样实现自增强.     

Studying banded spherulites in HDPE by electron microscopy

HDPE is a semi-crystalline thermoplastic polymer, with remarkable physical properties such as high chemical resistivity, high impact strength, and high modulus. Compared to the other semi-crystalline polymers, HDPE mostly possesses a high crystallinity, due to which, it exhibits a unique combination of mechanical and chemical resistance properties. In the present work, we have characterized the crystalline spherulites of neat and formulated HDPE compositions thoroughly characterized by different electron microscopy techniques such as scanning electron microscopy (SEM) and transmission electron microscopy (TEM). One of the critical steps to obtaining well-resolved SEM images is the sample preparation that typically involves the etching process to elucidate the crystalline spherulites. Though such traditional methodology can effectively be used for neat HDPE, it leads to the creation of undesirable experimental artifacts when used to investigate formulated HDPE compositions. An alternate TEM-based method provides clear images without any artifacts, apart from being a direct and green method and taking relatively a lesser measurement time.     

Morphological development of melt crystallized poly(propylene oxide) by in situ AFM: formation of banded spherulites

The morphology of poly(propylene oxide) (PPO) crystals grown from the melt was investigated. The spherulites of the optically pure S polymers displayed a regular pattern of concentric rings as observed by polarizing optical microscopy, while the stereocopolymer developed irregularly banded, or non-banded spherulites depending on the degree of undercooling. The organization of the lamellar crystals within the spherulites was examined by means of atomic force microscopy (AFM). For all cases, the lamellar structures appeared to adopt an alternating flat or edge-on orientation. Examination of the morphology of single crystals in the melt of the stereocopolymer revealed truncated-lozenge crystals, which were elongated in shape. Results from crystallization kinetics, obtained by in situ AFM observations, showed that the elongated habit is related to differences in the growth rates of the {2 0 0} and {1 1 0} facets. Interestingly, the melt-grown RS-PPO crystals developed a curved asymmetrical three-dimensional shape. Based on these observations it can be proposed that the chiral nature of the chain is transmitted to higher structural levels of ordering in the crystal aggregates.     

Morphological comparison of isotactic polypropylene parts prepared by micro‐injection molding and conventional injection molding

The morphological feature of microparts evolved during micro‐injection molding may differ from that of the macroparts prepared by conventional injection molding, resulting in specific physical properties. In this study, isotactic polypropylene (iPP) microparts with 200 µm thickness and macroparts with 2000 µm thickness were prepared, and their morphological comparison was investigated by means of polarized light microscopy (PLM), scanning electron microscopy (SEM), differential scanning calorimeter (DSC), and wide‐angle X‐ray diffraction (WAXD). The results presented some similarities and differences. PLM observations showed that the through‐the thickness‐morphology of micropart exhibited a similar “skin–core” structure as macropart, but presented a large fraction of shear layer in comparison to the macropart which presented a large fraction of core layer. The SEM observation of shear layer of micropart featured highly oriented shish‐kebab structure. The micropart had a more homogeneous distribution of lamellae thickness. The degree of crystallinity of the micropart was found to be higher than that of the macropart. High content of β‐crystal was found in micropart. The 2D WAXD pattern of the core layer of macropart showed full Debye rings indicating a random orientation, while the arcing of the shear layer indicates a pronounced orientation. The most pronounced arcing of the micropart indicates the most pronounced orientation of iPP chains within lamellae. Copyright © 2011 John Wiley & Sons, Ltd.     

Observation of banded spherulites and lamellar structures by atomic force microscopy

Spherulites are common structures of semi-crystalline polymers. It has been known that semi-crystalline polymers can form spherulites when crystallized from solution or from melt. A dark Maltese cross of a spherulite could be easily observed under the polarized optical microscopy (POM). Moreover, some spherulites show an additional alternating dark and bright concentric ring structure that is attributed to the regular twisting of the radial crystallite ribbons as they grow from the spherulit…     

Morphological changes of BTDA/m‐PDA polyimide banded spherulites: The effect of solvent on banding

BTDA/m‐PDA polyimide banded spherulites with different band spacing were observed in the same sandwiched film. Atom force microscopy (AFM) analysis suggested that the banded structure was caused by periodic twisting of radial grown lamella bundles. Based on polarizing light microscopy (PLM) and AFM observation, it was found that spherulites grown near the center of the film exhibited bigger band spacing and consisted of wider lamellae compared with those grown near the fringe, which was suggested to be caused by different solvent amount during imidization and crystallization: the more solvent existed, the wider the lamella would grow and the bigger the band spacing would be. It was further proved by changing the film thickness and PAA solution concentration. SEM observation showed that when crystallized in the solution, the lamella became ultra thick and straight, and formed small particles. Powder X‐ray diffraction revealed that crystal structures of the banded spherulite and the small particle were identical or at least very similar. Another solvent with lower boiling point was used in sample preparation, however, under the same preparation conditions, the grown features of banded spherulites did not change. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 659–667, 2008     

Molecular orientation induced by cooling stresses. Birefringence in polycarbonate: III. Constrained quench and injection molding

Residual stress and birefringence distributions are determined in polycarbonate samples obtained by quenching in a specially designed apparatus and by injection molding. The molecular orientation is distinguished from the thermally and pressure-induced residual stresses. The birefringence in the quenched samples is found to be positive and almost constant, independent of the quench temperature, but varying strongly with initial quench temperature between 150 and 180°C. The residual stress level, as determined by layer removal and sectioning, is very low. The birefringence distribution is mainly due to a tensile equibiaxial orientation induced by transient cooling stresses built up above T_g. The samples which are injection-molded with a high injection speed and without packing pressure display the same birefringence distribution as the quenched samples, apart from a local maximum beneath the surface due to the shear flow during filling. Apart from the flow during filling and packing, the frozen-in molecular orientation in injection-molded samples is also induced by transient thermal stresses present during vitrification. The birefringence from thermally induced orientation was found to be of comparable magnitude to that from flow-induced orientation. For a correct prediction of molecular orientation the thermal strains above T_g must therefore be included in simulation programs. Because of the low level of thermal stresses, the application of a packing pressure will lead to tensile stresses at the surface in general. © 1994 John Wiley & Sons, Inc.     

Non-destructive measurement of cavity pressure during injection molding process based on ultrasonic technology and Gaussian process

Non-destructive measurement of the cavity pressure is of great importance for monitoring, optimizing and controlling the injection molding process. However, to date, almost all researches have relied on embedded pressure probes, and holes have to be drilled in the molds. In this paper, a non-destructive cavity pressure measurement method is proposed based on ultrasonic technology and a Gaussian process. According to the pressure-volume-temperature profile, the cavity pressure of a given polymer can be treated as a function of the density and the temperature. Moreover, the cavity pressure is significantly affected by injection hydro-cylinder pressure. Ultrasonic technology is employed to detect the variation of polymer density during injection molding. The Gaussian process is adopted to model the functional relationships between the cavity pressure, the ultrasonic signal, the mold temperature and the injection hydro-cylinder pressure. Experimental results show that the proposed Gaussian process regression model has a better modeling performance than that of the neural network regression model, and the proposed measurement method is capable of measuring the cavity pressure at different processing conditions and measurement locations during injection molding. In general, the proposed method offers several advantages: (1) non-destructive, (2) flexible, (3) no wires, (4) low-cost, and (5) health and safety, so it has great application prospects in injection molding.     

Effect of molding parameters on the properties of PP/PP sandwich injection moldings

The basic characteristics of a sandwich injection molded product depend on the properties of the respective resins that comprise the skin and core layers, and the skin/core resin volume ratio. The characteristics of the core layer resin and the skin/core ratio in particular may vary depending on the injection molding conditions. This report considers the influences that the molding conditions such as injection speed, cylinder temperature, and mold temperature confer on the mechanical properties of the sandwich moldings. The study employed, skin/core resin combinations involving similar and dissimilar materials i.e. homopolymer PP/homopolymer PP and homopolymer PP/copolymer PP, respectively. It was demonstrated that core cylinder temperature and mold temperature could be used to adjust the mechanical properties of sandwich injection moldings. In the case of single material sandwich moldings, injection speed seemed to play no significant role, even though it was clearly demonstrated that core volume increases with injection speed. However, core injection speed plays a significant role in the dual material system by lowering or increasing the mechanical strength of moldings as the case may be. Thus, the dormant or active role of injection speed depending on the material system has been highlighted.     

Optimized splitless injection of hydroxylated PCBs by pressure pulse programming

Hydroxylated polychlorobiphenyls (polyhydroxy-PCBs) are subjected to severe discrimination effect when they are introduced into a capillary gas chromatograph by splitless injection. This effect can be considerably reduced by using a pulsed pressure injection to favor sample transfer and by further programming the eluent gas pressure during the GC run. By multistep gas pressure programming, splitless injection provides analytical performances and chromatograms for (poly)hydroxy-PCBs closely resembling those obtained by on-column injection, whose use is generally discouraged with real environmental samples. Among the six model compounds studies, the dihydroxy congeners exhibit the best results.     

Residual stresses and birefringence in injection molding of amorphous polymers: Simulation and comparison with experiment

A physical modeling and a two‐dimensional numerical simulation of the injection‐molding of a disk cavity by using a hybrid finite element method (FEM) and finite difference method (FDM) are presented. Three stages of the injection‐molding cycle––filling, packing, and cooling––are included. The total residual stresses are taken to be a sum of the flow stresses calculated using a compressible nonlinear viscoelastic constitutive equation and the thermal stresses calculated using a linear viscoelastic constitutive equation. The total residual birefringence is taken to be the sum of the flow birefringence related to the flow stresses through the stress–optical rule, and the thermal birefringence related to the thermal stresses through the photoviscoelastic constitutive equation. The Tait equation is used to describe the P‐V‐T relationship. The simulation shows that without packing the birefringence in the surface layer of moldings, with its maximum near the surface, is caused by the frozen‐in flow birefringence (flow stresses) and in the core region by the frozen‐in thermal birefringence (thermal stresses). With packing, a second birefringence maximum appears between the center and the position of the first maximum due to flow in the packing stage. The predicted birefringence profiles and extinction angle profiles are found to be in fair agreement with corresponding measurements in literature for disk moldings. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 622–639, 2006     

Structure and properties of polyethylene prepared via low‐frequency vibration‐assisted injection molding

A self‐made low‐frequency vibration‐assisted injection‐molding (VAIM) device was adopted to explore the relationship between mechanical property and morphology for high‐density polyethylene injected moldings. The main processing variables for the VAIM are vibration frequency and vibration pressure amplitude, and tensile properties and morphology were investigated under different VAIM processing conditions with conventional injection molding for comparison. The moldings prepared by VAIM exhibit a very well defined laminated morphology composed of a layered structure with enhanced crystallinity. Increased with vibration frequency at constant vibration pressure amplitude, the shish‐kebab structure is exhibited in the shear layer of the specimen prepared by VAIM, whereas row nucleation lamella exists in the same layer produced by enhanced vibration pressure amplitude at a constant vibration frequency. These oriented structures and enhanced crystallinity, confirmed by scanning electron microscopy, wide‐angle X‐ray diffraction, and differential scanning calorimetry, serve to obtain stronger injection moldings. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 13–21, 2005     

Reinforcement of solid‐melt interfaces for semicrystalline polymers in a sequential two‐staged injection molding process

The solid‐melt interfaces between polyethylene (PE) and polyamide 6 (PA6) reinforced by in situ reactive compatibilization in a sequential two‐staged injection molding process has been studied in this work. The effects of the maleic anhydride grafted PE content and processing parameters, such as injection pressure, injection speed, melt temperature, and mold temperature, on the interfacial adhesion were investigated experimentally. The results of the interfacial adhesion characterized by lap shear measurement showed that the interfacial temperature and heat transfer between PE and PA6 interfaces play a very significant role in the bonding process. The fracture surfaces of the specimens prepared at different calculated interfacial temperature were investigated by scanning electron microscopy (SEM) and differential scanning calorimetry (DSC), which suggested that the fracture failure changes from adhesive to cohesive failure with increasing interfacial temperature. The contribution of crystalline parts of the in situ formed copolymers to the enhancement in interfacial adhesion also was determined by DSC analysis. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1112–1124, 2009     

Morphology evolution and crystalline structure of controlled‐rheology polypropylene in micro‐injection molding

In this paper, the microstructural evolution of controlled‐rheology polypropylene (CRPP) with different melt viscoelasticities was investigated by polarized optical microscopy, scanning electronic microscopy, differential scanning calorimeter, and wide‐angle X‐ray diffraction. It is found that a typical “skin‐core” structure formed in CRPP microparts and the thickness of oriented layer of CRPP microparts decreases notably with the addition of peroxide. The thickness of oriented layer and the distribution of different layers strongly depend on the melt flow properties and the corresponding relaxation time (λ). Furthermore, the mechanisms of the suppressed formation of oriented layers during the micro‐injection molding process are discussed mainly from the viewpoint of rheology and thermodynamics. It is revealed that the shear‐induced orientation is one of the key factors for the formation of oriented molecular structure (row nuclei). The final thickness of the oriented layer is the result of the competition between the orientation behavior and the disorientation behavior. Copyright © 2015 John Wiley & Sons, Ltd.     

Morphology and mechanical behavior of isotactic polypropylene with different stereo‐defect distribution in injection molding

Large amount of work has been published on the isotacticity–properties relationship of isotactic polypropylene (iPP). However, the stereo‐defect distribution dependence of morphology and mechanical properties of iPP injection molding samples is still not clear. In this study, two different isotactic polypropylene (iPP) resins (PP‐A and PP‐B) with similar average isotacticity but different stereo‐defect distribution were selected to investigate the morphology evolution and mechanical properties (tensile and notching) of their injection molding samples using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), 2D wide angle X‐ray diffraction (2D‐WAXD), and scanning electron microscope (SEM). The results of DMA showed that the molecular movement ability of PP‐A (with less uniform distribution of stereo‐defect) was stronger than that of PP‐B, meanwhile the analysis of DSC and SEM suggested that after injection molding, smaller spherullites, and crystals with higher perfection had formed in the specimens of PP‐A. The resulting of tensile properties of PP‐A were found to be better than that of PP‐B. The results of morphology evolution by SEM observation and 2D‐WAXD showed that PP‐A is more likely to occur interspherulite deformation and can disperse the tensile stress more efficiently, and therefore, its crystal structure can withstand a greater force when tensile stress is applied. On the other hand, PP‐B has larger spherulites and boundaries, and low perfection of lamellaes, and the intraspherulte deformation tend to take place. It is easier for the crystal of PP‐B to be broken up and reoriented along the tensile direction. Copyright © 2014 John Wiley & Sons, Ltd.     

Luminance and brightness field distribution of light guiding plate for backlight panel (BLP) by micro molding

This research investigates the luminance and the brightness field distribution of the microstructure of a light guiding plate (LGP) by micro injection molding (MIM) and micro injection‐compression molding (MICM). The process of manufacturing a LGP includes photo‐etching, MIM, MICM, and optical field measurement. The results show that the luminance of microstructure of LGPs produced using MICM is better than those made using MIM. The results also indicate that the most important processing parameter is the mold temperature for the luminance distribution of the LGP whether made by MIM or MICM. The maximum luminance of the LGP is 80 Nit (cd/m²) on micro molding. The brightness field distribution of the LGP made using MICM is more uniform than those made using MIM for the same processing parameters. MICM is a more suitable process than MIM for the fabrication of a LGP on a backlight panel (BLP). Copyright © 2008 John Wiley & Sons, Ltd.     

Measurement and quantitative analysis of fiber orientation distribution in long fiber reinforced part by injection molding

The fiber orientation distribution is one of the important microstructure variables for thermoplastic composites reinforced with discontinuous fibers. In this paper, the long fibers in the injection molded part are measured in detail by micro X-ray CT. A three dimensional (3D) structure of the sample is built and two dimensional images are generated for image analysis. The orientation tensor of fibers is calculated in the flow plane. It shows a symmetric distribution of fibers through the thickness direction, which consists of outer skin, transition zone and the core. The skin layer is so thin that it has only one layer of highly oriented fibers. The core layer also has highly oriented fibers but the direction of fibers is different from that in the skin layer. Nevertheless, the clustering of the fibers is characterized quantitatively in the core. The transition zone can be divided into two subzones by the principal directions of the tensor.     

聚合物驱弹性效应对注入压力的影响

引人综合粘度度量聚合物溶液的粘弹性,利用无限大地层达西定律,导出了粘弹性流体径向流的压力损失方程。采用数值方法研究了粘弹性流体在变截面孔隙模型中的阻力特性,结合实例分析了粘弹性流体径向流的压力损失随粘弹性的变化规律。研究结果表明,弹性效应是影响注入压力升高的一个重要因素。聚合物溶液的粘弹性越大,其在地层孔隙中的渗流阻力越大,弹性效应在增高注入压力中所占的份额也越大。增加地层渗透率、降低注入排量、减小聚合物溶液的粘弹性均有利于降低注入压力,提高注入能力,改善注入效果。     

Improved hydrostatic pressure sample injection by tilting the microchip towards the disposable miniaturized CE device

A simple method of hydrostatic pressure sample injection towards a disposable microchip CE device was developed. The liquid level in the sample reservoir was higher than that in the sample waste reservoir (SWR) by tilting microchip and hydrostatic pressure was generated, the sample was driven to pass through injection channel into SWR. After sample loading, the microchip was levelled for separation under applied high separation voltage. Effects of tilted angle, initial liquid height and injection duration on electrophoresis were investigated. With enough injection duration, the injection result was little affected by tilted angle and initial liquid heights in the reservoirs. Injection duration for obtaining a stable sample plug was mainly dependent on the tilted angle rather than the initial height of liquid. Experimental results were consistent with theoretical prediction. Fluorescence observation and electrochemical detection of dopamine and catechol were employed to verify the feasibility of tilted microchip hydrostatic pressure injection. Good reproducibility of this injection method was obtained. Because the instrumentation was simplified and no additional hardware was needed in this technology, the proposed method would be potentially useful in disposable devices.     

A study on the micro‐injection molding of multi‐cavity ultra‐thin parts

In this study, we report the micro‐injection molding of ultra‐thin parts (100, 250, and 500 µm). The results show that the flow resistance increases as the cavity becomes thinner. The melt front is not symmetric when filling a four‐cavity ultra‐thin part and filling the eight‐cavity mold under a low temperature. If we increase the mold temperature or cavity thickness, the melt front becomes symmetric. Finally, we construct the operation windows of molding for three kinds of plastics (PS, PMMA, PC) and provide a molding range based on mold temperature and injections speed. Meanwhile, the relationship between the thickness and the operation windows are also investigated. The thinner the cavity is, the smaller the operation window is. We need to increase the injection speed significantly for molding the ultra‐thin parts with micro‐features on both surfaces which are 60 µm in thickness. Furthermore, we succeed in molding 30 µm ultra‐thin parts in this experiment. Copyright © 2009 John Wiley & Sons, Ltd.