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.     

Plasticity of Semicrystalline Polymers

Semi-crystalline polymers can be deformed up to a very high strain. The deformation process involves frequently a complete molecular rearrangement of the chain-folded lamellar morphology into a more or less chain-unfolded fibrillar microstructure. This transformation is likely to occur through an intermediate state of high molecular disorder at a local scale. It led to the formulation of a concept of strain-induced melting-recrystallization process as a main mechanism of the structure transformation. In contrast, several structural features occurring at moderate plastic strains are relevant to strictly crystallographic processes. The plastic deformation process of semicrystalline polymers and the micromechanisms involved are discussed. A critical discussion of experimental findings is made to point out the strength or the deficiency of the various argumentations. It is demonstrated that the crystallographic slip mechanisms, including slips: transverse and along the chains are the basic deformation mechanisms in the deformation sequence, active at all strain levels. Direct microscopic evidence of chain slip activity even at well advanced stages of the deformation process is presented. In contrary, the melting-recrystallization seems to be restricted to the high-strain stage accompanied by chain unfolding and perhaps limited to only a small fraction of the crystalline phase. In addition the experimental results demonstrates clearly that the cavitation, necessary in the Peterlin's model, is really unessential in producing high deformation and appearance of the final highly oriented structure. This can be effectively accomplished with only crystallographic mechanisms employed. A very important role in the deformation sequence is played by the partially reversible shear deformation of amorphous interlamellar layers, producing not only high orientation of amorphous component but also influencing deeply the deformation of crystalline phase, since both phases are strongly connected and must deform simultaneously and consistently.     

Crystallinity changes in plastically deformed isotactic polypropylene evaluated by x‐ray diffraction and differential scanning calorimetry methods

The crystallinity of isotactic polypropylene (iPP), when deformed with plastic plane‐strain compression, was studied with wide‐angle X‐ray scattering (WAXS) and differential scanning calorimetry (DSC) techniques. A comparison of the obtained crystallinity data with annealed iPP samples was performed. The material used in this study was commercial iPP (weight‐average molecular weight = 117.400 g/mol; number‐average molecular weight = 17.300 g/mol). A significant decrease in the crystallinity was observed with increasing deformation pressure when the X‐ray method was employed, whereas only a small decrease was registered when the DSC method of crystallinity determination was used. However, the annealed iPP samples demonstrated a slight crystallinity increase when evaluated by both techniques. The reason for the difference between WAXS and DSC crystallinity results is discussed. This study of iPP specimens subjected to large deformation led us to the conclusion that the WAXS method provides accurate crystallinity values for the deformed material, whereas the values obtained by the DSC method do not reproduce the real crystallinity of the deformed material. This is due to the inherent heating process of the method, which causes a relaxation process and a significant change in the crystallinity of the deformed material, providing values nearer to its intrinsic equilibrium state. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 896–903, 2002     

On the plastic deformation of bulk syndiotactic polypropylene

 The plastic deformation of syndiotactic polypropylene (sPP) bulk samples has been investigated. A structural comparison of the initial states before and after plastic deformation by necking is carried out by X-ray diffraction observations. Independent of the initial states (amorphous, semi-crystalline with different crystal phases), only the planar all-trans crystal form of sPP is present in the deformed samples after necking. Form these results, molecular mechanisms of the plastic deformation in the neck zone of semi-crystalline polymers will be discussed. Received: 11 February 1997 Accepted: 15 August 1997     

Structure and mechanical behavior of nylon 6 fibers filled with organic and mineral nanoparticles. II. In situ study of deformation mechanisms

This study reports on the in situ characterization of the deformation mechanisms at room temperature of polyamide 6 (PA6) fibers filled with hyperbranched molecules or montmorillonite (MMT) platelets. A small‐angle X‐ray scattering study shows that the stretching and sliding of the microfibrils takes place concomitantly in the first stage of elastic loading of as‐spun and partially drawn fibers. In the second stage of loading, which is basically plastic, sliding turns out to be the main process of deformation, accompanied by a significant reduction in the microfibril radius. Fibers drawn close to their maximum draw ratio only display the deformation process of microfibril stretching. This in situ study also reveals subtle features of the reversible processes of deformation that could not be detected from ex situ experiments reported previously. A thickening of the crystal blocks in the microfibrils takes place under stress and disappears upon unloading, indicating that some reversible strain‐induced molecular ordering occurs in the amorphous layers close to the crystal surface. The tentative mechanical modeling enabled a characterization of the components of the fibers: the stiffness of the microfibrils appears to be insensitive to the presence of the particles that are excluded in the interfibrillar regions. The presence of HB molecules clearly increases the stiffness of the interfibrillar regions owing to a physical crosslinking effect. Moreover, it seems that the stiffness improvement of the drawn MMT‐PA6 fiber lies in a greater capability of chain unfolding in the interfibrillar amorphous region. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2633–2648, 2004     

Structure and morphology of heavily deformed single crystals of a polydiacetylene. I. Electron microscopy and x-ray diffraction

The structure and morphology of heavily deformed single crystals of a diacetylene polymer have been studied using a combination of x-ray diffraction and electron microscopy. Crystals have been deformed by both rolling and hammering. The crystals remain intact during deformation and can be reduced in thickness by a factor of over 5 in directions perpendicular to their chain axes. It is found that the chain orientation is maintained during both hammering and rolling. A greenish-colored surface skin develops during both types of deformation but the structure of the interior of the crystals depends upon the type of deformation employed. The interior of the hammered crystals consists of crystal blocks ca. 50 μm thick formed by cleavage perpendicular to the chain direction whereas the rolled crystals tend to be fibrous with no evidence of molecular fracture. The possible deformation mechanisms which have given rise to the different structures have been discussed.     

Is a Bent Crystal Still a Single Crystal?

The mention of the word “crystal” invokes images of minerals, gems, and rocks, all of which are inevitably solid, hard, and durable entities with well‐defined smooth faces and straight edges. With the discovery in the first half of the 20th century that many molecular crystals are soft and can be deformed in a similar way as rubber or plastic, this perception is changing, and both the concept and formal definition of what a crystal is may require reinterpretation. The seemingly naïve question posed in the title of this Minireview does not have a simple answer. Here, we discuss how the effects of the elastic and plastic deformation of molecular crystals on the diffraction signature give primary evidence of their degree of crystallinity. In most cases, the definition of a crystal holds for both elastically and plastically deformed crystals and, unless there is significant or complete physical separation of the crystal during the deformation, they can safely be considered (deformed) single crystals with a high concentration of defects.     

Simulation of plastic deformation in glassy polymers: Atomistic and mesoscale approaches

The mechanism of deformation in glasses is very different from that of crystals, even though their general behavior is very similar. In this study, we investigated the deformation of polycarbonate on the atomistic scale with molecular dynamics and on the continuum scale with a new simulation approach. The results indicated that high atomic/segmental mobility and low local density enabled the formation (nucleation) of highly deformed regions that grew to form plastic defects called plastic shear transformations. A continuum-scale simulation was performed with the concept of plastic shear transformations as the basic region of deformation. The continuum simulations were able to predict the primary and secondary creep behavior. The slope of the secondary creep depended on the interactions between the plastic shear transformations. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 994-1004, 2005     

Relevance of cage recombination in the plastic deformation of polymers

For a polymer in which permanent rupture of individual molecules is the rate-limiting process for plastic deformation, the kinetics of chain-end diffusion and secondary radical reactions should be compared with the kinetics of caged radical recombination in the calculation of activation parameters for plastic deformation. If mechanisms of cage escape are slower than those for cage recombination, the activation parameters for plastic deformation will differ from those for the initial bond-breaking process. For the case of polyethylene deformed in the vicinity of 250°K, the critical thermally activated event appears to involve scission of the polymer molecule near the site of an abstracted hydrogen atom. For this system the dominant cage-escape mechanism is diffusion, which is faster than either hydrogen abstraction or unzipping to the monomer. However, at low stresses the rate of cage recombination is expected to be higher than the rate of cage escape, so that the activation parameters for deformation should be the sum of those for chain scission and diffusion. The contribution of diffusion (ca. 15 kcal/mole) to the activation energy for deformation (E^*, extrapolated to zero stress conditions) is relatively modest. However, the calculated molar activation volume for deformation V^* increases by almost an order of magnitude, i.e., from ca. 10 to ca. 76 cm³/mole when diffusion is required. Consideration of experimental values of E^* and V^* for high molecular weight polyethylene indicates that, in the regime examined, chain scission plus chain-end diffusion is required to effect plastic deformation.     

Large Plastic Deformation of Isotactic Poly(propylene) (iPP) Evaluated by WAXD Techniques

Summary: Commercial isotactic poly(propylene) (iPP), obtained in bars, was annealed and submitted to different levels of plastic deformation by uniaxial plane compression using a special device which permits well controlled temperature and strain rate. The evolution of the microstructure was followed at different degrees of deformation by wide angle x-ray diffraction (WAXD) techniques. The spherulite fragmentation process, lamellar orientation and destruction of the crystallites is argued, according to collected analytical data in the flow direction (FD), the loading direction (LD) and the lateral or constrain direction (CD). The evaluation of the WAXD patterns in terms of diffraction line position, intensity and width, permits to affirm that, while the large plastic deformation occurs, the crystalline net suffers anisotropic deformation, the crystallites become preferentially oriented along the flow direction and the crystalline phase diminish in amount indicating lesser and smaller crystallites. The gradual lamellae fragmentation occurs, starting with apparent crystalline size of approximately 30 nm for the non-deformed material and gradually decreasing to approximately 15 nm for the 70% deformed one.     

Molekulare Vorgänge bei der plastischen Verformung von Polymer-Einkristallen

Zusammenfassung Neuere elektronenmikroskopische Beobachtungen über die molekularen Vorgänge bei der plastischen Verformung von Polyäthylen-Einkristallen werden beschrieben. Aus den Ergebnissen dieser Untersuchungen folgt, daß die plastische Verformung (Scherung) von Polyäthylen-Einkristallen parallel zur Molekülrichtung (c-Achse) durch die Bewegung von Schraubenversetzungen mit einem Burgersvektor des Typs 001 erfolgt. Die plastische Verformung senkrecht zur Molekülrichtung scheint bei tiefer Temperatur durch das Auffalten und Abspulen von Molekülen aus dem Kristall zu erfolgen. Bei höherer Temperatur ist diesem Prozeß ein Rekristallisationsvorgang überlagert, der aus dem verformten Gefüge die bekannte Schichtstruktur von gezogenen Fäden entstehen läßt. Der Abspul- und Rekristallisationsvorgang hängt in erster Linie von der molekularen Struktur der amorphen Faltoberfläche ab. Dies wird durch das Verformungsverhalten von bestrahlten und schmelzerstarrten Polyäthylen-Einkristallen gezeigt.

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Summary Observations by means of transmission electron microscopy are reported on the molecular processes occurring during plastic deformation of polyethylene single crystals. The results indicate that plastic shear parallel to the molecules (c-axis) occurs by the movement of screw dislocations the Burgersvector of which is001. Plastic deformation normal to the c-axis involves unfolding of the molecules with a subsequent recrystallization process (at elevated temperatures) resulting in the well established structures of polyethylene fibers. The results of deformation experiments with both irradiated and melt grown single crystals suggest that the molecular mechanism of the unfolding process depends to a considerable extend on the structure of the fold surface of the single crystals.

     

Shear bands in polycarbonate

Lexan polycarbonate specimens in the form of tubes were deformed in torsion. The deformation occurs by the nucleation and growth of discrete shear bands. Shear bands are initially formed at the upper yield point. Development of the bands is accompanied by a drop in the stress to a lower yield point. At the lower yield point the strain inside the bands is approximately 70% and remains constant thereafter. Further deformation occurs by growth of the bands until they cover the entire sample. When the direction of twisting is reversed after the shear bands are formed, the deformed material untwists uniformly, without deformation in the previously undeformed material, and the stress required for untwisting the deformed material is lower than the stress required to propagate the band into undeformed material.     

Plastic deformation of polymer blends with crystallizable components

The application of polymer blends depends mostly on their high ability to plastic deformation. Usually the studies of plastic deformation behavior include only the stress-deformation relationship and investigation of changes of morphology of the blends on the size level of inclusions. The energy absorption is also often considered. The presented, more rigorous, approach to plastic deformation of polymer blends containing a crystallizable component involves the studies of crystal plasticity and associated deformation of the amorphous phase. Plastic deformation of blends containing high-density polyethylene and isotactic poly(propylene) with other components were studied in two modes of deformation: 1. that avoids internal cavitation and 2. in tension with intense voiding. When no internal cavitation was involved, the plastic deformation was crystallographic in nature while the amorphous phase deformed in a manner to accommodate for the rotation and slips of the crystalline phase. Also the plastic deformation associated with intense voiding leads to a preferred orientation of certain crystallographic planes containing macromolecular chains which strongly suggests that the leading mechanisms in plastic deformation of blends are of crystallographic nature. The plastic deformation behavior depends very much on the glass transition of the amorphous component of the blend.     

Crystallite size in highly drawn polyethylene

The size and distortion of crystallites in samples of linear polyethylene were determined before and after plastic deformation. A slowly cooled sample, a quenched sample, and highly drawn films (draw ratio 16) were investigated by different methods. Wide-angle x-ray patterns were analyzed to study the average size of the crystalline mosaic blocks and their distortion. In addition, the longitudinal crystal thickness (in the chain direction) was evaluated by two other approaches, determination of the long period, and the melting temperature of irradiated samples. The results show clearly that the size of the crystalline mosaic blocks changes substantially with drawing of polyethylene. Not only is the lateral crystal thickness affected, but the longitudinal crystal dimensions also change during the drawing process. By the three independent methods we find that the longitudinal crystal thickness after drawing is independent of the value for the undrawn samples, as was reported earlier by Peterlin. The change in crystallite size after drawing is accompanied by a large decrease in crystal volume to about 10% of the value for the undrawn sample. The degree of distortion in the crystals seems not to be affected by the deformation process. These experimental data can be considered evidence for high chain mobility and for the possibility of rearrangement of chain molecules during the process of plastic deformation.     

X-ray photoelectron emission microscopy and time-of-flight secondary ion mass spectrometry analysis of ultrathin fluoropolymer coatings for stent applications

Fluoropolymer plasma coatings have been investigated for application as stent coatings due to their chemical stability, conformability, and hydrophobic properties. The challenge resides in the capacity for these coatings to remain adherent, stable, and cohesive after the in vivo stent expansion, which can generate local plastic deformation of up to 25%. Plasma-coated samples have been prepared by a multistep process on 316L stainless steel substrates, and some coated samples were plastically deformed to mimic a stent expansion. Analyses were then performed by X-ray photoelectron spectroscopy (XPS), X-ray photoelectron emission microscopy (X-PEEM), and time-of-flight secondary ion mass spectrometry (TOF-SIMS) to determine the chemical and physical effects of such a deformation on both the coating and the interfacial region. While XPS analyses always showed a continuous coating with no significant effect of the deformation, TOF-SIMS and near-edge X-ray absorption fine structure (derived from X-PEEM) data indicated the presence of a certain density of porosity and pinholes in all coatings as well as sparse fissures and molecular fragmentation in the deformed ones. The smallness of the area fraction affected by the defects and the subtlety of the chemical changes could only be evidenced through the higher chemical sensitivity of these latter techniques.     

Microdeformation behavior in nanotemplated epoxy thermosets: A study with in situ tensile deformation technique in transmission electron microscopy

Microdeformation behavior in nanostructured block copolymer‐toughened epoxy resins, or templated epoxy thermosets, was studied using an in situ tensile deformation technique performed directly in a transmission electron microscope. The observed microdeformation modes were found to correlate well with the macroscopic mechanical properties of the materials. In the order of decreasing macroscopic fracture toughness, the microdeformation modes were observed to change from large uniform plastic deformation over an extensive area, to localized plastic deformation bands, to little plastic deformation observed in the most brittle material. A similar trend was also observed when samples of the same material were tested at different temperatures, reflecting changes in the deformation mechanism as a function of temperature. Structural defects were observed in nanotoughening phases when plastic deformation was observed. The implication of the observed microdeformation modes to the macroscopic toughening mechanisms is discussed in the context of the micromorphology of the nanometer sized toughening phases and parameters of the epoxy matrix chemistry such as bromination, molecular weight, and interfacial miscibility. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 393–406, 2009     

Thermal processes in succinic acid–aluminum blends subjected to high-pressure plastic deformation

The thermal characteristics of powdered aluminum–succinic acid blends subjected plastic deformation under pressures of 0.5?2.0 GPa have been studied. When heated, deformed samples exhibit exothermal processes, which occur at temperatures below the T _m of the acid and indicate chemical interactions between succinic acid and aluminum induced by the plastic deformation. The values of the thermal effects depend on the degree of deformation and the pressure of the treatment.     

尼龙-6/热塑性聚酰胺系弹性体合金的力学性能和破坏机理

尼龙 ６与在尼龙 ６中分别添加了两种热塑性聚酰胺系弹性体的尼龙 ６合金相比，前者的耐冲击强度低，后者的耐冲击强度高；通过偏光显微镜和扫描电镜的观察，尼龙 ６在Ｕ型缺口前部区域内的塑性约束下，呈脆性破坏；尼龙 ６的合金因塑性区域内的空洞化和空洞的变形及空洞之间区域的颈缩和纤维化，有效的吸收了冲击能量，使塑性约束得到缓解，促进了平面应变状态向平面应力状态转变，最终呈半韧性或韧性破坏．     

Plastic deformation of polypropylene. IV. Wide-angle x-ray scattering in the neck region

Wide-angle x-ray scattering (WAXS) patterns of two polypropylene samples, a quenched sample drawn at 21°C and an annealed sample drawn at 100°C, were investigated in a range of values of draw ratio λ very closely spaced through the neck region. In both cases, a range of small λ where deformation occurred by spherulite deformation was followed by one of higher λ where microfibrils were formed. The contribution to the WAXS pattern of microfibrils could be clearly distinguished from that of deformed spherulites because of the better orientation parallel to the draw direction of the former as compared to the latter. Additionally, for a drawing temperature of 21°C, microfibrils crystallize in the “smectic” phase as compared to the monoclinic phase for the initial sample and deformed spherulites. At this temperature, plastic deformation proceeds through the spherulite deformation mechanism up to λ = 1.4 accompanied by an increase in chain orientation with increasing λ. For λ > 1.4 plastic deformation appears to occur exclusively through microfibril formation. For drawing at 100°C, spherulite deformation is accompanied by very little change in chain orientation up to λ = 2, where microfibril formation begins. For λ > 2 (T_d = 100°C) plastic deformation is accompanied by both microfibril formation and some spherulite deformation as reflected by changes in both orientation and crystallite size. At this temperature the lateral crystallite size in the microfibrils is related to the long period according to the “equilibrium crystallite shape” previously found for annealed polypropylene.     

Analytical method for the representation of atoms-in-molecules densities

We present analytic refinements and applications of the deformed atomic densities method [Fernández Rico, J.; López, R.; Ramírez, G. J Chem Phys 1999, 110, 4213-4220]. In this method the molecular electron density is partitioned into atomic contributions, using a minimal deformation criterion for every two-center distributions, and the atomic contributions are expanded in spherical harmonics times radial factors. Recurrence relations are introduced for the partition of the two-center distributions, and the final radial factors are expressed in terms of exponential functions multiplied by polynomials. Algorithms for the practical implementation are developed and tested, showing excellent performances. The usefulness of the present approach is illustrated by examining its ability to describe the deformation of atoms in different molecular environments and the relationship between these atomic densities and some chemical properties of molecules.