Prediction of fiber orientation in injection molded parts of short-fiber-reinforced thermoplastics

Fiber orientation induced by injection mold filling of short-fiber-reinforced thermoplastics (FRTP) causes anisotropy in material properties and warps molded parts. Predicting fiber orientation is important for part and mold design to produce sound molded parts. A numerical scheme is presented to predict fiber orientation in three-dimensional thin-walled molded parts of FRTP. Folgar and Tucker's orientation equation is used to represent planar orientation behavior of rigid cylindrical fibers in concentrated suspensions. The equation is solved about a distribution function of fiber orientation by using a finite difference method with input of velocity data from a mold filling analysis. The mold filling is assumed to be nonisothermal Hele-Shaw flow of a non-Newtonian fluid and analyzed by using a finite element method. To define a degree of fiber orientation, an orientation parameter is calculated from the distribution function against a typical orientation angle. Computed orientation parameters were compared with measured thermal expansion coefficients for molded square plates of glass-fiber-reinforced polypropylene. A good correlation was found.     

Orientation in amorphous polymers II. Characterization of orientation

A method based on network theory is developed for characterizing molecular orientation in amorphous polymers. The proposed procedure gives not only the orientation distribution function for the chain segments in the polymer network (and hence the average orientation) but also a quantitative measure of how this orientation is distributed among the various types of entanglement junctions. The orientation of chain segments can be characterized by two parameters, one which gives the average orientation and another which reflects how much orientation is concentrated in long time entanglement junctions. The new method of characterizing orientation is used to interpret tensile strength data for both brittle and ductile failures.     

双轴取向聚乙烯薄膜晶体取向的二维X光衍射分析

聚乙烯膜的晶体取向决定着薄膜的多种力学性能和热力学性能。因此,针对薄膜晶体取向的表征显得非常重要,尤其是具有双轴取向的聚乙烯薄膜。通过二维广角衍射研究了单轴和双轴高取向聚乙烯薄膜的取向度。建立表征取向度的三种方法,包括Herman取向分析法、局部积分法和环向积分法。结果发现,上述方法均适用于所有的双轴取向的高分子薄膜,包括非晶态高分子薄膜。Herman取向分析法可以通过取向因子定量计算简单取向材料取向度;局部积分的方法能分析出衍射较弱方向晶体信息,更适用于取向度较复杂的样品;环向积分法能更直观地分析薄膜的取向特点、取向强度。     

Control of molecular orientation

I. Amorphous polymers . The mechanical performance of a glassy amorphous polymer is strongly dependent upon molecular orientation. The pattern of molecular orientation is governed by the kinematics (and temperature) of mechanical forming operations. Three types of controllable orientation are: (a) uniaxial, (b) biaxial, and (c) “crossed.” The optimum pattern of orientation in a part is one which is appropriate for the mechanical stresses encountered in service. For a fiber subjected to tensile and bending loads, uniaxial orientation is appropriate. A shell structure, subjected to multiaxial stresses, requires either biaxial or crossed orientation for maximum performance. As a rule, the maximum achievable multidirectional strength in such a structure is less than the maximum strength of a uniaxially oriented fiber. II. Crystalline polymers . Oriented crystalline polymer structures can be created in two distinct ways. An isotropic polycrystalline polymer can be deformed below the melting point, with extensive reorganization of the crystal morphology, or an oriented amorphous melt can undergo crystallization to yield oriented crystalline polymer. Performance of an oriented semicrystalline polymer depends upon orientation of the amorphous portion as well as orientation of the crystallites. As with amorphous polymers, orientation can be uniaxial, biaxial, or crossed. “Orientation” usually denotes c-axis orientation only, but drawing followed by rolling can result in double orientation—orientation of a-axis, b-axis, and c-axis.     

Prediction of fiber orientation in the thickness plane during flow molding of short fiber composites

Fiber orientations caused by the flow in the thickness plane during injection molding of short fiber reinforced polymer composites has been simulated. The Lagrangian scheme was employed for the finite element analysis. Flow fields were solved by using a penalty method with Uzawa's scheme and orientation fields were also solved by using the second order orientation tensor. A generalized Newtonian fluid whose rheological behavior is independent of fiber orientation was assumed. Automatic mesh generation using an elliptic grid generator was developed for quadrilateral elements. Mold filling and orientation analyses were performed for a cavity of rectangular cross section. To determine the orientation state in other cross-sectional geometries, numerical analyses were also performed for two different typical cross sections. As the result, orientation of short fibers in the flow field was analyzed qualitatively and quantitatively. According to the state of short fiber orientation in the thickness plane, the orientation field can be classified into three regions in the flow direction and three layers in the thickness direction. Orientation of short fibers was mainly influenced by elongational and shear flows. It was observed that critical values are present for upper limits of orientation. Effects of initial orientation at the inlet on the orientation field were examined.     

Numerical prediction of three-dimensional fiber orientation in Hele-Shaw flows

A numerical technique is developed to determine the three-dimensional fiber orientation in complex flows. The fiber orientation state is specified in terms of orientation tensors, which are used in several constitutive models. This method is applied to quasi-steady state Hele-Shaw flows in order to predict the flow-induced fiber orientation during injection molding at zero volume fraction limit. At the inlet, a number of fibers are introduced at a specified rate into the flow and each fiber location is traced during the mold filling. Along these determined paths, the independent components of fourth order orientation tensors are solved, describing the orientation state. The numerical grid generation technique, which is suitable for complex mold shapes, is employed for the flow solution. Orientation ellipsoids are calculated from the second order tensors and are used to present the fiber orientation results. The numerical solutions are obtained for channel and converging flows. Planar, longitudinal, and transverse orientation results are generated from the orthogonal projections of the orientation ellipsoids.     

In-plane orientation and graphitizability of polyimide films: II. Film thickness dependence

The relation between the in-plane orientation of polyimide film and graphitizability was investigated. The degree of in-plane orientation was estimated by means of optical birefringence and ESR technique. The polyimide film was found to have non-uniform orientation in the thickness direction because the thinner the film was, the greater the orientation. The inhomogeneity of orientation caused multiphase graphitization in a film with a composite profile of the X-ray diffraction peak.     

The specification of orientation and its development in polymer processing

A critical review of the specification of orientation and its development in polymer-processing operations is presented. Orientation may in general be specified by orientation distribution functions, but is most conveniently expressed in terms of orientation factors which are second moments of the distribution. The Hermans orientation factor represents polymer-chain orientation for systems with fiber symmetry (uniaxial orientation) and the Hermans-Stein orientation factors express uniaxial orientation for each of the crystallographic axes of crystalline polymers. Biaxial orientation is, however, developed in tubular film extrusion, blowmolding and, indeed, all processing operations other than fiber formation. Orientation factors developed previously by the authors express biaxial orientation in terms of the angles between the machine and transverse directions and the polymer chain axis or crystallographic axes. In flowing polymer melts, the Rheo-Optical Law, which relates birefringence and stress, represents a relationship between polymer-chain orientation and stress. In vitrified polymeric glasses (e.g. polystyrene), the orientation factors are related linearly to the stress field at vitrification. This has been shown experimentally for melt spinning and tubular film extrusion. The results of studies of blowmolding and injection molding are consistent with this. The crystalline orientation factors have also been found to be determined by the stress field at solidification in melt spinning and tubular film extrusion.     

Determination of the orientation of mica in composites

A wide angle x-ray diffraction technique has been used to determine the orientation of mica flakes in composites. The mica used was a fine grade Phlogopite, and the polymers were polystyrene, polycarbonate and poly(vinyl chloride). Composite samples of varying mica contents and orientations were prepared. The x-ray method can give the orientation distribution function of mica flakes across and parallel to the surface of the sample. From this function, an average orientation parameter was calculated. The results show that there is no orientation of mica across the surface of the sample (the x-ray beam is normal to the surface), but that there is a strong orientation in a direction parallel to this surface, the average orientation parameter being strongly dependent upon the particle size of mica and mode of preparation.     

Orientation of poly(vinyl alcohol) nanofiber and crystallites in non-woven electrospun nanofiber mats under uniaxial stretching

The development of macroscopic nanofiber orientation and microscopic crystallite and molecular chain orientation have been investigated during uniaxial stretching of electrospun poly(vinyl alcohol) (PVA) non-woven nanofiber mats. Scanning electron microscopy and stress-strain/small-angle X-ray scattering show that the macroscopic nanofiber orientation significantly increases during the initial stage of deformation, and approaches a plateau on the way of stretching. Detailed analyses of the stress-strain/wide-angle X-ray diffraction measurement and polarized Fourier transform infrared spectroscopy indicate that the microscopic crystallite and molecular chain orientation rapidly increase at the initial stage of stretching due to macroscopic nanofiber orientation. At higher deformation, the microscopic modes of orientation continuously develop as a result of the nanofiber stretching. The complicated deformation process of non-woven nanofiber mats is discussed in terms of macroscopic nanofiber orientation and the microscopic crystallite and molecular chain orientation.     

Specification of biaxial orientation in amorphous and crystalline polymers

The fundamental concepts for specifying orientation in amorphous and crystalline polymers are reviewed. A new set of orientation factors is proposed to represent the second moments of biaxial orientation. The factors are defined both for the chain axis and for three crystallographic axes of an orthorhombic (or pseudo-orthorhombic) crystal structure. The orientation factors are defined in terms of the angles between the crystallographic axes and Cartesian coordinate reference axes defining the machine, transverse and thickness directions of films. This makes the orientation factors symmetric with respect to the machine and transverse directions unlike the Stein-Nomura-Kawai orientation factors which are defined in terms of Euler's angles. A graphical procedure for representing the state of orientation as a point inside an isoceles triangle is described. Methods of measuring the orientation factors are also reviewed. The paper concludes with examples of the application of these concepts to orientation in amorphous polystyrene films fabricated in our laboratories and to crystalline polyethylene samples discussed in the literature.     

A Wide-angle X-ray diffraction method of determining chopped fiber orientation in composites with application to extrusion through dies

A method of determining fiber orientation in composites using wide-angle X-ray diffraction (WAXS) is described. Oriented crystalline fibers are suspended in an amorphous polymer matrix. The WAXS reflects characteristics of the fiber are used to determine the mean orientation and orientation distribution of the crystallographic axes representing the polymer chain relative to preferred axes located in the test specimen. The chain direction crystallographic axis is taken as representing the fiber axis, and the orientation of this axis to represent the orientation of the fibers. Experimental studies were carried out using Kevlar (poly(p-phenylene terephthalamide)) fibers suspended at a 20 volume percent loading in a polymethyl methacrylate matrix. The Kevlar fibers had Hermans orientation factors of 0.92. Specific attention is given to how through circular dies. We have examined both extrudates and the material frozen-in when the composite in the reservoir and die is cooled to room temperature. Fiber orientation factors, corresponding to Hermans orientation factors, 0.3 to 0.38 were obtained for the extrudates. Orientation factors for fibers within the die is about 0.45. Specially prepared completely oriented samples had orientation factors of 0.93, which closely corresponds to the orientation of the fiber.     

Fiber orientation control of short‐fiber reinforced thermoplastics by ram extrusion

In this study we examine the fiber orientation distribution, fiber length and Young's modulus of extruded short‐fiber reinforced thermoplastics such as polypropylene. Axial orientation distributions are presented to illustrate the influence of extrusion ratio on the orientation state of the fibrous phase. Fibers are markedly aligned parallel to the extrusion direction with increasing extrusion ratio. The orientation state of extruded fiber‐reinforced thermoplastics (FRTP) is almost uniform throughout the section. The control of fiber orientation can be easily achieved by means of ram extrusion. Experimental results are also presented for Young's modulus of extruded FRTP in the extrusion direction. Young's modulus follows a linear trend with increasing extrusion ratio because the degree of the molecular orientation and the fiber orientation increases. The model proposed by Cox, and Fukuda and Kawada describes the effect of fiber length and orientation on Young's modulus. The value of the orientation coefficient is calculated by assuming a rectangular orientation distribution and calculating the fiber distribution limit angle given by orientation parameters. By comparing the predicted Young's modulus with experimental results, the validity of the model is elucidated. The mean fiber length linearly decreases with increasing extrusion ratio because of fiber breakage due to plastic deformation. There is a small effect on Young's modulus due to fiber breakage by ram extrusion.     

Influence of orientation on polyester fibres

The technological applications and the associated molecular mechanisms of various levels of orientation in polyester fibres are discussed. The inherent birefringence of these fibres is high and therefore the orientation is easily measurable, while their behaviour is very sensitive to small changes in orientation. In particular, practical properties such as strength, productivity and ease of bulking are very dependent on the spun yarn orientation before the drawing operation takes place, but for completely different reasons. Polyester fibres can be pretreated in terms of orientation in such a way that an extremely high spontaneous extension can be obtained, a property which can be used for bulking. It is shown that variations in low levels of orientation can have profound industrial implications.     

Orientation of carbon nanotubes in polypropylene melt

The correlation between shear stress and the orientation of single‐walled carbon nanotubes (SWCNTs) in an SWCNT/polypropylene composite during the melt process was investigated. Highly oriented composite fibers were produced by extruding the polypropylene melt using a capillary rheometer. The experimental range of shear rates covered those of common polymer melt‐shaping processes. The effect of functionalization of the SWCNTs on orientation was also investigated. Polarized Raman spectroscopy was used to analyze the orientation of the SWCNTs. A high degree of SWCNT orientation was observed under high shear stress, and the functionalized SWCNTs induced a higher degree of orientation than did pristine SWCNTs. The existence of a critical shear stress was observed for the orientation of the SWCNTs, and their orientation was found to occur more efficiently above this critical shear stress. The crystallization temperature and heat of fusion were characterized using a differential scanning calorimeter, and both parameters were observed to increase with the incorporation of SWCNTs. © 2012 Society of Chemical Industry     

The effect of the side chain of acrylate comonomers on the orientation,pore-size distribution,and properties of polyacrylonitrile precursor and resulting carbon fiber

The side-chain size of acrylate comonomer in polyacrylonitrile (PAN) precursor markedly influences the microstructure of PAN fiber and its resulting carbon fiber. In this paper, we propose that the model of the crystal orientation of PAN precursor and its resulting carbon fiber can explain the effect of the side-chain size of acrylate comonomer on the orientation of PAN fiber and carbon fiber. When PAN precursor contains a larger side chain of comonomer, PAN precursor has the preferred crystal orientation and higher crystallinity and the orientation of its resulting carbon fiber unexpectedly decreases. This is because the larger the side chain is, the lower is the orientation of the amorphous region of PAN fiber; as a result, the average orientation after carbonization decreases. In the same mole fraction of comonomer, the carbon fiber based on PAN precursor with a smaller side chain of acrylate comonomer has better mechanical properties and higher yield.     

Characterization of the deformation behavior of dynamic vulcanizates by FTIR spectroscopy

To clarify the deformation mechanisms and to improve the mechanical properties of dynamic vulcanizates, we studied their deformation behavior by Fourier‐transform infrared (FTIR) spectroscopy. It was found that the orientation in the dispersed phase (EPDM phase) is higher than in the matrix (PP phase) upon loading. The orientation of the rubber phase increases continuously. In the thermoplastic phase, a change of the deformation mechanism takes place. With respect to the total strain of the material, the orientation in the thermoplastic phase of the dynamic vulcanizates is lower, and in the elastic phase, it is higher than the corresponding orientation of the pure components. During stress relaxation, there is an increase of the orientation in the crystalline PP phase. Simultaneously, a decrease of the orientation in the EPDM phase is observed. Upon unloading, the orientation recovery in the EPDM phase is always complete, while the orientation recovery in the PP phase is reversible only at low strains. The critical point, where the elastic deformation gets lost, corresponds to the minimum in the orientation function curve. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 148–158, 2001     

Ultrasonic measurement of orientation in HDPE/iPP blends obtained by dynamic packing injection molding

The orientation of polymer chain has a great effect on its mechanical properties, therefore, it is always an important issue on how to characterize, accurately and quickly, the orientation of polymer chain during processing. In this article, according to the property that ultrasound travels in different velocities in anisotropic media, normal incident shear wave was utilized to explore the orientation structure of HDPE/iPP blends obtained by dynamic packing injection molding. The ultrasonic technique is consistent with the 2D-WAXS in charactering the orientation degree of polymer chains, although ultrasonic technique focuses on the overall orientation of polymer blends while the 2D-WAXS reveals the crystalline orientation of each component. Our work demonstrates that ultrasonic technique might be a reliable, fast and easy way to characterize the orientation structure of crystalline polymer blends. The ultrasonic measurements were performed off-line, but the achievement provides the possibility for on-line detection of orientation structure in injection molding by using ultrasonic technique.