Quantitative characterization of deformation in polypropylene fibers

A modus operandi is developed for characterizing, in quantitative morphological terms, the structural changes occurring during the preparation (spinning, drawing, and heat setting) and testing (tensile modulus) of isotactic polypropylene fiber. This involves the application of the following eight different physical techniques: wide-angle x-ray diffraction, birefringence, density, sonic modulus, small-angle x-ray diffraction, dark-field microscopy, small-angle light scattering, and tensile modulus. Structural changes on several organizational levels, the spherulitic, the interlamellar, and the molecular, are determined in this manner and related to the processes involved.     

Morphology of drawn syndiotactic polypropylene films

Morphological studies were conducted to investigate the drawability of melt-quenched (MQ) and slowly cooled (MSC) films of syndiotactic polypropylene (sPP) with a high syndiotactic pentad fraction. Transmission electron microscopy (TEM) using the ruthenium tetraoxide staining and ultrathin sectioning method revealed that amorphous chains as the matrix of MQ film played a role in drawability of the film by their alignment to machine direction (MD) and partial crystallizations into nanofibrils. On the other hand, the initial strain induced, rotations of clusters of long lamellar crystals as the major entity of MSC film accompanying breaks of long lamellae and formation of crazes and microvoids at the cluster boundary. Compared with a homogeneous thinning of MQ film by drawing, ca. 100 nm-thick layer slips along MD and parallel to the film surface took place in MSC film. This gave rise to the formation of V-shaped bent lamellar morphology and their further break into a smaller cluster of stacked lamellae which were aligned oblique by ca. 35° from MD. With elongation, some nanofibrils formed from chains generated by the partial breaks of lamellae are aligned perpendicular to the remained oblique lamellae and others parallel to MD in region where lamellar morphology almost disappeared. No chain slips in the nanofibrils can be related to a low elongation at break, i.e. a low ductility of sPP films. The lower elongation at break for MSC film than for MQ one can be interpreted by microvoids initially formed in the neck region and later moved to the fully drawn part, the microvoids initiating the break of the drawn film.     

Plastic deformation of highly drawn polypropylene monofilaments

The tensile properties of highly oriented polypropylene (PP) filaments are markedly dependent on their fabrication drawn history. Highly oriented filaments prepared by drawing at <100°C were capable of appreciable plastic deformation after passing through a marked yield point. This deformation process was very rate dependent, transforming to essentially brittle behavior at deformation rates >500%/min. Filaments produced by drawing at a higher temperature, or by annealing above 100°C of those produced at 100°C, had a slightly lower modulus, greatly reduced residual elongation to break, and showed no yield point. A model for the plastic deformation is proposed involving localized fibrillation to produce craze-like structures. This model is consistent with the observed filament susceptibility to chromic acid etching. Electron micrographs of highly drawn then etched samples show that just prior to fracture only small plastes of the acid resistant (presumably original, unvoided) structure remain.     

Electron microscopy of drawn polypropylene

Extremely thin polypropylene films formed by evaporation of dilute solutions floating on water, thin films deposited on Mylar or on carbon-coated Mylar, and bulk samples were deformed; after etching with aqua regia or chromic acid, the surfaces were studied by electron microscopy of surface replicas. At small draw ratio, microfibrils with lateral dimensions of about 200 Å, originating in micronecks at crack boundaries of the original crystal lamellae, were obtained in isolated areas exhibiting maximum local strain separated by large regions of much less deformed material. With increasing draw ratio the necked regions grow, the old structure gradually being reduced to smaller and smaller islands until it disappears completely. The inhomogeneity of strain in adjacent bundles of microfibrils creates a great many longitudinal voids with more or less disoriented microfibrils bridging the gaps. The regular arrangement of crystalline blocks of rather uniform length and width can be occasionally seen on surface replicas of drawn samples, and much better on dark-field electron micrographs of drawn and annealed thin membranes. In the latter case the blocks are very uniform and have similar dimensions along and perpendicular to the axis of the microfibril. The evidence from the electron micrographs, together with previous small-angle x-ray scattering data, supports Peterlin's molecular model for plastic deformation of crystalline polymers.     

Melting behavior of drawn polypropylene

The melting behavior of drawn, compression-molded isotactic polypropylene has been ex-amined in terms of the infuence of drawing conditions on the observed properties. Two endothermic peaks were observed on differential scanning calorimetry (DSC) for samples when high draw ratios and high heating rates were used during DSC tests. The peak at lower temperature is influenced by draw ratio, temperature, and rate, and exhibits a strong superheating effect. The species associated with this peak can partially recrystallize into another species associated with the peak at higher temprature during DSC measurements. The position of the peak at higher temperature depends only on draw ratio. It is proposed that the doubel-melting peaks at lower and higher temperature result from extremely thin quasi-amorphous or crystalline layers between microfibrils and the lamellar crystals within microfibrils, repectively. © 1993 John Wiley & Sons, Inc.     

Crystallite size in drawn and then annealed polypropylene

Crystallite sizes have been obtained from the breadth of equatorial x-ray reflections from polypropylene samples subjected to a draw ratio of 6 at 21°C and then annealed at 155°C, 140°C, and 120°C, respectively. For all samples it was found that the ratio of the dimension of the crystallite perpendicular to the {110} planes to that perpendicular to the (040) plane is a constant. The ratio of the lateral crystallite size to the meridional long period was also found to be constant, independent of annealing temperature. In contrast, the thickness of the crystallites in the direction parallel to the draw direction, as calculated from the meridonal long period and density data, was not proportional to the lateral crystallite size.     

Mechanical anisotropy of a monoaxially drawn polypropylene film

The tensile strength values, tensile moduli (measured with an Instron dynamometer) and sonic moduli of a monoaxially oriented polypropylene film were determined. Anisotropy was defined by the ratio between the tensile strength or modulus values in the direction of drawing and in the perpendicular direction. The difference amounting to an order of magnitude between the anisotropy of tensile strength and of the sonic modulus is explained by the existence of cracks between bundles of microfibrils. Anisotropy of the modulus determined with the instron dynamometer is lower than that of tensile strength, but higher than that of the sonic modulus. This is a consequence of the failure of the system which occurs in the transverse direction already at low deformations.     

Quantitative structural characterization of the melting behavior of isotactic polypropylene

The melting behavior of restrained isotactic polypropylene fibers is examined quantitatively in terms of the influence the anisotropic structural state of the polymer has on the observed properties. Two endotherm peaks are observed to occur in some of the samples. The formation and location of the multiple peaks are determined by the orientation of the noncrystalline chains, and is independent of the fabrication path used to achieve that orientation. Above a certain minimum orientation of the noncrystalline chains, multiple endotherm peak formation occurs. The high-temperature endotherm (T_2M) extrapolates to an ultimate melting point for fully oriented noncrystalline chains of 220°C, while the lower-temperature endotherm (T_1M) extrapolates to an ultimate melting point of 185°C. Noncrystalline chain orientation influences the endotherm temperature through its changing configurational entropy. It is shown quantitatively that the noncrystalline polymer must be considered as plastically deformed, since rubber elasticity theory is not followed as predicted. The melting behavior of isothermally crystallized samples are also reported to further elucidate the nature of the observed endotherms.     

Aging phenomena in isotactic polypropylene drawn at different temperatures

Fibers of isotactic polypropylene drawn at different temperatures show aging phenomena after drawing. In particular a modulus stiffening is observed at room temperature where the modulus increases with the aging time. In the same time scale the birefringence is constant, while drastic effects on the transport properties are observed. The aging phenomenon can be explained in terms of two mechanisms: a secondary crystallization and/or a densification of the amorphous component.     

Birefringence study of drawn Nafion films

Nafion films are birefringent. This optical property has been studied as a function of the draw ratio to obtain insight into the film morphology. At small draw ratios, the structure shows biaxial behavior. At higher draw ratios (>150%), Nafion can be considered to have a uniaxial symmetry. The influence on the birefringence of three different counterions (hydrogen, lithium, and tetramethylammonium) is negligible. Undrawn Nafion shows preorientation, which can be eliminated with drawing in the proper direction. X‐ray experiments suggest that the physical origin of the birefringence in Nafion is mainly due to the orientation of the polymer chains and not due to deformation or form birefringence. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2857–2870, 2004     

Mechanical and transport properties of highly drawn isotactic polypropylene

Quenched films of isotactic polypropylene were drawn at 110°C up to draw ratio λ = 18. The axial elastic modulus was measured as function of λ up to the highest achieved λ. The sorption and diffusion of CH₂Cl₂ at 25°C in the undrawn and drawn samples were studied. Exclusively transparent samples were used for the measurement of the density and transport properties. This reduces the maximum usable draw ratio to 15. The drawing process is inhomogeneous with neck propagation. In the neck the draw ratio increases by about 6. As a consequence of the increasing fraction of taut tie molecules the axial elastic modulus increases faster than the draw ratio. The transport parameters D, S, and λ indicate that the original lamellar morphology is completely transformed into the microfibrillar structure.     

Diffusion of camphorquinone in uniaxially drawn polycarbonate films

Employing the laser-induced holographic grating relaxation technique, we have measured tracer diffusion coefficients of a phtochromous dye, camphorquinone, in uniaxially drawn polycarbonate films as a function of stretch ratio. Anisotropy in the tracer diffusion coefficient has been observed with D_∥ greater than D_⟂ by at least a factor of 4 for the film stretched to the stretch ratio δ = 2.3. The diffusion coefficient along the direction of stretch D_∥ increases significantly with increasing δ, whereas D_⟂ decreases slightly with increasing δ. The stretch ratio dependence of D_∥ and D_⟂ is interpreted according to a modified free volume theory. The strain rate and stretch temperature dependence of the anisotropic tracer diffusion coefficient has also been investigated. © 1992 John Wiley & Sons, Inc.     

Quantitative characterization of optical anisotropy in high refractive index films

Waveguide coupling measurements of polymers have largely concentrated on the application of mode analysis to the study of thin supported films (such as spin coatings). The use of prism coupling to study thick, freestanding polymer films, however, has not been reported. In this paper, the ability of prism coupling to characterize the three-dimensional optical properties of thick, freestanding polymer films and sheets is demonstrated. A modified prism coupling procedure is described that allows the determination of all three principal refractive indices in thick, three-dimensionally anisotropic freestanding films. A Metricon prism coupler is used in a manner similar to an Abbé refractometer for the measurement of isotactic polypropylene, poly(ethylene terephthalate), PMDA-ODA polyimide, and poly(phenylene sulfide). Three series of PMDA-ODA films are also investigated in this study. The first series has been drawn to different extensions from three-dimensionally random films. The second series has random orientation in the plane of the film but different degrees of planarity with respect to the through direction. The third series are commercial films of varying thickness. These three series of films are compared as to the optical an-isotropy that is developed from the three different fabrication processes. © 1993 John Wiley & Sons, Inc.     

Crystallite sizes and paracrystalline lattice distortions in drawn hard elastic polypropylene

Summary The paracrystalline lattice distortions and the mosaic crystallite sizeD ₀₀₁ are constant at all draw ratios ( =1 ... 2,3) of a hard elastic polypropylene foil. The lateral crystallite sizes decrease sharply (but not much) at a small draw ratio and slow to higher .

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Zusammenfassung Beim Verstrecken einer hartelastischen Polypropylen-Folie (Verstreckgrade =1 ... 2,3) bleiben die parakristallinen Gitterstörungen und die MosaikkristallitgrößeD ₀₀₁ konstant. Die lateralen Kristallitgrößen nehmen bei kleinem A steil, aber wenig, ab und verringern sich dann langsam weiter mit wachsendem .

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Quantitative characterization of DNA films by X-ray photoelectron spectroscopy

We describe the use of self-assembled films of thiolated (dT)25 single-stranded DNA (ssDNA) on gold as a model system for quantitative characterization of DNA films by X-ray photoelectron spectroscopy (XPS). We evaluate the applicability of a uniform and homogeneous overlayer-substrate model for data analysis, examine model parameters used to describe DNA films (e.g., density and electron attenuation length), and validate the results. The model is used to obtain quantitative composition and coverage information as a function of immobilization time. We find that when the electron attenuation effects are properly included in the XPS data analysis, excellent agreement is obtained with Fourier transform infrared (FTIR) measurements for relative values of the DNA coverage, and the calculated absolute coverage is consistent with a previous radiolabeling study. Based on the effectiveness of the analysis procedure for model (dT)25 ssDNA films, it should be generally valid for direct quantitative comparison of DNA films prepared under widely varying conditions.     

Optical properties and structure of drawn polyethyleneterephtalate-polyethylene films

Films made by coextrusion of polyethyleneterephtalate and low density polyethylene exhibit specular reflection of light when stretched. Unlike the behaviour of films made of pure PET, where specular reflection is rare and does occur at extremely high stretching rates only, PET/LDPE films show specular reflection independent of the stretching rate.A film, containing 70% PET and 30% LDPE, prepared by coextrusion of the two components, has been investigated by scanning electron microscopy, light microscopy and by measuring the optical properties with a spectrophotometer. The (unstretched) as prepared sample has been compared with a sample stretched to =4.The optical measurements show as a result of the stretching a strong decrease of the transmittance and an increase of the remittance. While there is no drastic change of the dispersion (which is only slight), the increase of the refractive index indicates some straininduced crystallization.The scanning electron micrographs show long, needlelike voids and indicate a fractionation of the two components as a result of the stretching. This fractionation has been investigated by heating the samples up under the light microscope: while the stretched sample shows a separation of the components, the unstretched sample does not.Dedicated to Prof. Dr. F. H. Müller.     

Non-isothermal crystallization kinetics of hot drawn polyester films

The non-isothermal crystallization kinetics of hot drawn poly(ethylene terephthalate) films were studied using the Kissinger and Ozawa equations. The influence of the initial drawing on the crystallization kinetics was investigated. The values of the apparent activation energy and of the Avrami exponent indicates that the nucleation and growth of crystallites depend greatly on the stress submitted to the samples.     

Drawing behavior and characteristics of laser‐drawn polypropylene fibers

Drawing behavior, flow drawing, and neck drawing, was studied for isotacticpolypropylene fibers in CO₂ laser drawing system, and the fiber structure and the mechanical properties of drawn fibers were analyzed. For a certain laser power, flow drawing of polypropylene (PP) was possible up to draw ratio (DR) 19.5. Though the drawing stress was very low, the flow‐drawn PP fiber exhibited oriented crystal structure and improved mechanical properties. On the other hand, neck‐drawing was accomplished from DR 4 to 12, with significant increase in drawing stress that enhanced the development of fiber structure and mechanical properties. Unlike PET, the drawing stress depends not only on the DR, but on irradiated laser power also. The 10–12 times neck‐drawn fibers were highly fibrillated. The fibers having tensile strength 910 MPa, initial modulus 11 GPa, and dynamic modulus 14 GPa were obtained by single‐step laser drawing system. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 398–408, 2006     

Melting behavior of drawn films from polyethylene single-crystal mats

Drawing of mats of linear polyethylene single crystals prepared from dilute solution is possible at temperatures above about 90°C. The structure and properties of the drawn specimens are much different from those ordinary drawn bulk polymer. Drawn mats have been investigated by differential scanning calorimetry. The characteristic experimental results are: (a) a broad melting curve, (b) considerable superheating depending on the rate of heating, (c) constancy of the melting point and the heat of fusion with annealing, (d) deviation from the relation between the heat of fusion and the density obtained for the drawn bulk specimens, (e) appearance of two melting peaks in samples annealed at temperatures above about 130°C. These results imply that the structure of the drawn mat is characterized by a larger number of the tie chains connecting the neighboring crystals (the structure postulated in earlier papers) than is the case in ordinary drawn bulk polymer. It can be concluded that the transformation of a fringed micellar type of structure to the folded lamellar structure may be difficult during annealing unless crystals melt and then recrystallize during cooling.