Deformation morphology of polyester single crystals

Truncated, six-sided single crystals of a 10–16 linear polyester were grown from dilute solution in hexanol, deposited onto Mylar film, and uniaxially deformed at room temperature. For elongations below 10%, the crystals deform uniformly; however, above 20% elongation many cracks spanned by fibrils of 300 Å diameter develop approximately normal to the applied stress direction. Depending on the position of the crystal relative to the draw direction, lateral buckling pleats and cleavage cracks can also occur. Collapse of the nonplanar crystals onto the substrate with a resulting nonuniform adherence of the crystal influences the deformation. The deformation morphology is compared to that of truncated sixfold sector polyethylene crystals. Most notably, in contrast to polyethylene, {010} fold sectors do not deform differently from {110} fold sectors and phase boundaries between {110} and {010} fold sectors do not fracture easily.     

Polymer deformation. XI. Biaxial deformation of polyethylene single crystals

Uniaxial deformation of polyethylene single crystals has been reported in the previous papers of this series. This paper presents an extension of this study to the simultaneous biaxial deformation of polyethylene single crystals. Diamond-shaped crystals containing {110} fold domains and truncated crystals containing in addition {100} domains were used in these experiments. The results show that these crystals fail at deformations as low as 6%, giving rise to cracks predominantly in the a direction. Electron diffraction patterns suggest that {310} twinning is more favorable than {110} twinning at the lower degrees of deformation. No phase change from orthorhombic to monoclinic unit cell is observed.     

Texture development in polyethylene II. Unidirectional rolling

The effect of degree of strain on texture development in high-density polyethylene has been studied by pole figure analysis for unidirectional rolling. The crystallite orientation distribution in rolling textures has been quantified with an efficient technique which fits three-parameter, two-dimensional Gaussian-type distributions to pole figure intensity data around ideal single crystal orientations. During flat rolling of polyethylene a texture consisting of a strong (100) [001] component and a weak (110) [001] component develops continuously from the lowest true strain of 0.24 (21% reduction) up to the highest true strain of 1.36 (74% reduction). The peak intensity of the Gaussian distributions of both (100) [001] and (110) [001] components increase continuously to the highest strain. The maximum angular breadth of both component distributions, which are roughly perpendicular to the strain direction, remains constant with increasing strain. The minimum angular breadth of both component distributions, which are roughly parallel to the strain direction, decreases continuously owing to gradual alignment of the covalently bonded chain backbone parallel to the strain direction. The development of the (100) [001] component is explained by slip on (100) planes while the weak (110) [001] component is explained by slip on (110) planes. Although the latter component was previously attributed to (110) or (310) relaxation twinning, this seems unlikely because of the lateral constraint during plane strain deformation conditions used in this study.     

Orientation in nylon 6 films as determined by the three-dimensional polarized infrared technique

A three-dimensional polarized infrared technique was used to obtain information about molecular orientation in both uniaxially and biaxially drawn nylon 6 films. The 835 and 930 cm^?1 bands were used to describe the orientation of the A (extended chain) conformation while absorptions at 1175 cm^?1, and 1120 cm^?1 and 1075 cm^?1 were used to give some information about orientation of the B (twisted chain) conformation. On the basis of the 835 and 930 cm^?1 bands, it was shown that the hydrogen-bonded sheets made up of chains in the A conformation are parallel to the film surface in the biaxially drawn film. Uniaxially drawn films obtained by drawing both at 100 and 150°C showed a high degree of chain alignment in the draw direction for the A conformation at draw ratios greater than 2.5. Some planar orientation was also observed in these uniaxially drawn films for both the A and B conformations at high draw ratios.     

Single-crystal-like orientation of ultrahigh-molecular-weight polyethylene by uniaxial stretching

Dried gel film of ultrahigh-molecular-weight polyethylene (UHMW PE) can be drawn to 370 times its original length at 135°C. Single-crystal mats and dried gel film of UHMW PE develop double orientation despite uniaxial stretching. This is unique for preferentially oriented UHMW PE systems. To elucidate the origin of this single-crystal-like orientation, precursors with different aspect ratios were prepared and drawn uniaxially. The degree of double orientation was measured by infrared spectroscopy. The origin of single-crystal-like orientation seems to reside in the necking region. The stacked lamellar structure is transformed into a fibrillar structure in a two-dimensional fashion. This condition is easily provided when UHMW PE single-crystal mat or dried gel film is drawn uniaxially. A draw ratio of 40 and aspect ratio of 40 are the optimal conditions to obtain a doubly oriented structure from UHMW PE single-crystal mat or gel film at 135°C.     

冲击载荷下TATB晶体滑移和各向异性的分子动力学研究

采用ReaxFF反应力场和分子动力学方法,研究了1,3,5-三氨基-2,4,6-三硝基苯(TATB)炸药晶体在沿不同方向冲击载荷下的滑移和各向异性。冲击方向分别垂直于(101)、(111)、(011)、(110)、(010)、(100)和(001)晶面,冲击强度为10 GPa。研究结果表明,各冲击方向下可能被激发的滑移系均在{001}面,而其它滑移系均因很大的剪切阻力不容易被激发,这与TATB晶体沿c轴的层状结构和平面分子结构相符。预测了七个冲击方向下最容易被激发的滑移系,分别为(101)/{001}100、(111)/{001}010、(011)/{001}010、(110)/{001}010、(010)/{001}110、(100)/{001}120和(001)/{001}010。TATB晶体的冲击响应具有各向异性,动力学过程中体系的应力、能量、温度和化学反应都依赖于冲击方向。对垂直于(100)和(001)晶面的冲击,体系在滑移过程中遭遇的剪切阻力较高、持续时间较长,使得能量和温度较快升高,化学反应较容易发生;对垂直于(101)和(111)晶面的冲击,体系在滑移过程中遭遇的阻力较小且出现次数少,使得能量和温度缓慢升高,化学反应不易发生;对其余冲击方向,体系的响应居中。据此评价了7个冲击方向的相对敏感程度:(101)、(111)(011)、(110)、(010)(100)、(001)。本研究有助于在微观层次深入认识动载荷下TATB的响应机制、结构与性能的关系,为高能低感炸药的设计和研制提供理论参考。     

Thermal diffusivity of polymer films by pulsed photothermal radiometry

We have developed a pulsed photothermal radiometry technique for determining the thermal diffusivity parallel to the surface of a polymer film that involves flashing a line-shaped laser beam on the surface of the sample at right angle to its length, and monitoring the temperature change with time at a distance from the line source using an infrared detector. Combining this with our previous laser-flash radiometry method for thermal diffusivity measurement perpendicular to the film surface, we can now measure the thermal diffusivity of a polymer film along all directions. These two techniques have been used to study uniaxially and biaxially oriented poly(ethylene terephalate) and uniaxially drawn ultrahigh molecular weight polyethylene films. For uniaxially oriented poly(ethylene terephalate), the thermal diffusivity along the draw direction is substantially higher than that in the transverse direction, which in turn, is slightly higher than that in the thickness direction. For a polyethylene film with a draw ratio of 200, the axial thermal diffusivity is extremely high, being about five times that of stainless steel. The anisotropy of the thermal diffusivity of this film exceeds 90. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1621–1631, 1997     

Coextrusion drawing of reactor powder of ultrahigh molecular weight polyethylene

Certain nascent polymers have been shown to have unusual thermal and morphological properties that are irretrievably lost once the polymer has been melted or otherwise reduced to the isotropic state. We show further that nascent ultrahigh molecular weight polyethylene “reactor powder” exhibits a remarkable ductility when uniaxially drawn by coextrusion techniques after initial compaction in film form at 100°C. When drawn at a temperature of 110°C, draw ratios of 56 have been obtained, resulting in an enhanced tensile modulus of 58 GPa. Thermal analyses and dynamic mechanical measurements were also made towards understanding the initial and final morphologies.     

Evolution of crystalline orientation and texture during solid phase die‐drawing of PP‐Talc composites

The objective of the present work was to examine the development of crystalline orientation and texture in the polypropylene matrix of talc‐filled i‐PP and in unfilled i‐PP with increasing draw ratio during solid‐phase die‐drawing at high strain rates (～1 s^?1) and a die temperature of 145 °C. After drawing, the entire billet was cooled rapidly “under tension” to room temperature before releasing the billet and cutting specimens from different axial locations for analysis. Orientation distributions of the three crystal axes for increasing axial strains have been presented as pole figures in the MD‐TD plane with the direction of draw (MD) as the reference direction. While disruption of spherulites was noticed within the die for neat PP at a draw ratio of 1.5, transcrystalline domains within the composite persisted even at a draw ratio of 3.5 in the free draw region outside the die. The transformation to fibrillar crystal morphology was complete in both materials at a draw ratio of 4.5 but the texture continued to develop beyond this stage. While the (110)[001] texture component was found to be dominant at all draw ratios for neat PP, the (010)[001] texture component was dominant at the higher draw ratios in the drawn composite. This may be attributed to the (010)[001] slip system being more active as the transverse spacing between elongated voids encasing the particles was decreased. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1528–1538     

New Orientation Formation During Recrystallization of Cold Deformed, High Symmetry Aluminium Bicrystals

The crystallography of recrystallization nucleation has been investigated in channel-die deformed pure Al bicrystals with {100}〈011〉/{110}〈001〉, {100}〈001〉/{110}〈011〉 and {100}〈001〉/{110}〈001〉 orientations. The new grain orientations and misorientations were followed by systematic local orientation measurements using SEM and semi-automatic measurements in TEM. The bicrystals were cold deformed by channel-die compression up to true strains of 1.5. During recrystallization annealing, the deformation bands of unstable orientations are the privileged sites for the formation of new grains. These nuclei were misoriented with respect to the orientations identified within the neighbouring deformed areas by α(〈111〉, 〈112〉 or 〈100〉) relations. Grain boundary migration and ‘consumption’ of the as-deformed areas was always favoured along directions parallel to the traces of the {111} slip planes that had been most active during deformation as shown in the stable and structurally homogeneous Goss {110}〈001〉 oriented grains. At logarithmic strains below 1–1.5 the grain boundary does not seem to be a specific nucleation site of new grains.     

Texture development in polyethylene. I. Uniaxial extension and uniaxial compression

Texture development of high-density polyethylene has been studied by x-ray diffraction at various strains for uniaxial extension, as achieved by uniaxial tension and extrusion, and for uniaxial compression. Pole distributions were measured for the (100), (200), (020), and (011) reflections. Textures were described by ideal single-crystal orientations with inverse pole figures. In uniaxial extension, samples were deformed up to true strains of 1.83 (reductions of up to 84%). After a strain of 0.55, the c axis oriented at 35° from the extension axis and with increasing strain approached the extension axis. This was attributed to initial (110) or (310) twinning in combination with (100) slip, followed subsequently by [001] slip. In compression, samples were deformed up to true strains of 1.83 (reductions up to 84%). The texture consisted of strong components of the compression axis near (100) and weaker components near (110). At higher strains the intensity of the near-(100) components decreased, whereas the near-(110) components became more intense. The near-(100) components are explained by slip on (100) planes. The growth of the near-(110) components at the expense of the near-(100) components can be explained by relaxation twinning of the near-(100) components.     

Planar deformation of amorphous poly(ethylene terephthalate) by stretching and forging

The planar deformation of amorphous poly(ethylene terephthalate) (PET) was performed by stretching and by forging under comparable conditions at a series of constant temperatures, 80, 90, 100, and 110°C. The highest planar draw ratios of 4.5 × 4.5 and 3.5 × 3.5 were obtained by forging and stretching, respectively. Samples were studied before and after deformation by wide angle x-ray scattering (WAXS), differential scanning calorimetry (DSC), density measurements, and elastic recovery at 100°C. A distinct difference in efficiency of draw between these two techniques is found, as judged mainly by the straininduced crystallization. The forging is more effective than stretching in achieving stabilized planar draw under comparable process conditions.     

Three-dimensional crystallographic determination of the body-centered-cubic morphologies of shear-aligned block copolymer systems

The texture of ordered phases of block copolymer melts and gels is highly sensitive to shear. In the body-centered-cubic phase of a block copolymer system [polystyrene–poly(ethylene butylene)–polystyrene] mixed with oil, we show how a given textures can be controlled with the application of a specific shear rate and amplitude. The low-amplitude shear texture is dominated by {001} planes perpendicular to the shear gradient and by the [110] axis parallel to the flow direction, that is, the {001}/[110] slip system. Detailed crystallographic studies show that both intermediate-amplitude oscillatory shear and large-amplitude oscillatory shear lead to twin structures with {112} planes sharing neighboring twins and [111] axes parallel to the shear flow. At an intermediate shear amplitude, the ve shear plane, defined by the shear flow direction (v) and shear vorticity direction (e), is parallel to the {112} twin planes. At a high shear amplitude, the orientation is rotated 90°, and this makes the ve shear plane parallel to the {110} crystallographic planes. The crystalline slip system is accordingly ({112 }/[111] + {11 2}/[111]) under intermediate-amplitude shear and ({11 0}/[111] + {1 10}/[111]) under large-amplitude shear. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3095–3101, 2004     

Structural Changes in Drawn Poly(L-lactide)/Clay Hybrid Films

The films composed of poly(L-lactide)(PLLA)/organoclay hybrids (PLACHs) have been prepared via a melt-compounding process, in which the organoclay paticles are uniformly dispersed in the PLLA matrix. The changes in PLLA crystal orientation for the uniaxially drawn films were studied by differential scanning calorimetry, X-ray diffractometry and transmission electron microscopy. Additionally, temperature dependence of the mechanical properties for these drawn films were examined by a dynamic viscoelastometer. After drawing the quenched PLACHs film at 90 °C, the orientation and crystallinity of PLLA crystal increased rapidly with increasing drawing ratio (λ) in the range more than 3 times. At the higher λ, the organoclay platelet particles in the PLACHs became parallel to the draw direction. The mechanical properties of drawn PLACHs were strongly dependent on both clay concentration and λ.     

Plastic deformation behavior of β phase isotactic polypropylene in plane‐strain compression at elevated temperatures

Isotactic polypropylene (iPP) rich in β crystal modification was deformed by plane‐strain compression at T = 55–100 °C. The evolution of phase structure, morphology, and orientation were studied by DSC, X‐Ray, and SEM. The most important deformation mechanisms found were interlamellar slip operating in the amorphous layers, resulting in numerous fine deformation bands and the crystallographic slip systems, including the (110)[001]_β chain slip and (110)[ ]_β transverse slip. Shear within deformation bands leads to β→α solid state phase transformation in contrast to β→smectic transformation observed at room temperature. Newly formed α crystallites deform with an advancing strain by crystallographic slip mechanism, primarily the (010)[001]_α chain slip. As a result of deformation and phase transformation within deformation bands β lamellae are locally destroyed and fragmented into smaller crystals. Deformation to high strains, above e = 1, brings further heavy fragmentation of lamellae, followed by fast rotation of crystallites with chain axis towards the direction of flow FD. This process, together with still active crystallographic slip, leads to the final texture with molecular axis of both crystalline β and α phase oriented along FD. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 92–108, 2008     

Determination of orientation of the crystalline and amorphous phases in polyethylene by X-ray diffraction

For polyethylene fibers, orientation parameters of the form 〈cos² ?〉 were calculated from traces obtained with an x-ray diffractometer equipped with an orientation integrator. The angle ? is that which a crystal or molecular axis makes with the fiber axis. Traces over a continuous range of diffraction angle were obtained for (2/π)I_av, and also the weighted averages (2/π)I_av 〈cos²?〉 and (2/π)I_av 〈sin²?〉, where I_av is the intensity averaged over all orientations. The orientation for the crystal a, b, and c axes were determined from area measurements of the {110} and {200} lines, and the orientation parameter for the molecular axis in the amorphous phase was determined from area measurements of the amorphous halos. An undrawn fiber showed a slight a and c axis orientation along the fiber axis, and a slight transverse orientation of the b axis and the molecular axis. For a highly drawn fiber the orientation parameter for the c axis was 0.98 and for the molecular axis 0.65. The degree of crystallinity, measured from the (2/π)I_av versus 2θ traces, were 66.1% and 73.3% for the undrawn and drawn fiber, respectively.     

Rheo-optical Fourier-transform infrared spectroscopy of polymers. VII. Uniaxial deformation of heat-set poly-(ethylene terephthalate) film

Poly(ethylene terephthalate) (PET) film was uniaxially stretched to a draw ratio of 2.5. Two samples were prepared from this oriented film by heat-setting it at 493 K while free to relax and when held at constant length. The structural changes occurring during uniaxial elongation up to fracture of these two oriented crystalline samples and their stress–strain characteristics were simultaneously monitored by rapid-scanning Fourier-transform infrared (FTIR) spectroscopy. In the free-annealed sample, the orientation of the molecules in the amorphous phase shows a gradual improvement throughout the test, while chain unfolding occurs above 20% strain. This indicates that the predominant mechanism of deformation in this sample could be chain uncoiling in the amorphous phase followed by longitudinal slip processes within the sample. In the taut-annealed sample, chain unfolding occurs at low strains accompanied by slight improvements in amorphous and crystalline orientation. Thus, in this sample longitudinal slip would appear to be the main deformation mechanism. The results of the FTIR measurements are discussed with reference to the dependence of the deformation mechanisms on the initial structure of the samples.     

Morphological evolution of Cu2O nanocrystals in an acid solution: stability of different crystal planes

The morphological evolution of uniform Cu(2)O nanocrystals with different morphologies in a weak acetic acid solution (pH = 3.5) has been studied for cubic, octahedral, rhombic dodecahedral, {100} truncated octahedral, and {110} truncated octahedral nanocrystals. Cu(2)O nanocrystals undergo oxidative dissolution in weak acid solution, but their morphological changes depend on the exposed crystal planes. We found that the stability of Cu(2)O crystal planes in weak acid solution follows the order of {100} ? {111} > {110} and determines how the morphology of Cu(2)O nanocrystals evolves. The stable {100} crystal planes remain, and new {100} facets form at the expense of the less stable {111} and {110} crystal planes on the surface of Cu(2)O nanocrystals. Density functional theory calculations reveal that the Cu-O bond on Cu(2)O(100) surface has the shortest bond length. These results clearly exemplify that the morphology of inorganic crystals will evolve with the change of local chemical environment, shedding light on fundamentally understanding the morphological evolution of natural minerals and providing novel insights into the geomimetic synthesis of inorganic materials in the laboratory.     

Drawing of single-crystal mats of linear polyethylene

Drawing of single-crystal mats of linear polyethylene has been investigated. Drawing is possible at temperatures higher than about 90°C. The drawing is accompanied by distinct necking, with a large decrease in the thickness of the mat and a very high maximum draw ratio, sometimes over 30. The maximum draw ratio is approximately proportional to the thickness of the lamellae. This behavior strongly suggests the unfolding of chains during drawing. A change of orientation of crystal axes occurs before necking without change of lamellar orientation. The a axis orients in the drawing direction; the b axis orients perpendicular to the direction of drawing; and the chain axis tilts away from the thickness direction of the mat. The structure of films drawn from mats is characterized by a distinct double orientation of crystals. This biaxial orientation in the drawn films has a high degree of correlation with the orientation of crystal axes observed before necking, and suggests that necking takes place in such a way that the chain tilts gradually about the b axis and ultimately unfolds. The postulate of formation of transitory two-dimensional crystals in necking seems useful in explaining the double orientation in the drawn film. The orientation behavior of crystal axes observed before necking is not always similar to that observed in the deformation of a single crystal. The difference is thought to be due to the effect of forces induced by drawing that act in the direction normal to the lamellae within a mat.     

Molecular orientation of rigid‐rod polyimide films characterized by polarized attenuated total reflection/fourier transform infrared spectroscopy

The variations in the molecular orientation of uniaxially drawn rigid‐rod polyimide films were systematically characterized in all three dimensions with polarized attenuated total reflection/Fourier transform infrared spectroscopy. The second‐order orientation coefficients were directly deduced from the anisotropy in IR absorptions of particular bands. With the draw ratio increasing, the state of the molecular orientation changed from being nearly planar to completely uniaxial via biaxial orientation, and the degree of orientation was much larger than that of a semirigid polyimide having an ether linkage at the same draw ratio, which originated from the rigid‐rod structure. In addition, the imide planes were rotationally oriented to the out‐of‐plane direction of the film geometry. Furthermore, the relationship between the molecular chain orientation and the in‐plane birefringence in the biaxial orientation state was examined. The intrinsic birefringence was estimated from biaxial orientation films to be 0.33 at a wavelength of 1307 nm. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 418–428, 2003