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1.
The properties of gel-spun polyethylene fibers hot-drawn to the maximum draw ratio depend on the spinning conditions. Different spinning conditions result in two types of structure in the paraffin oil containing fibers: an isotropic lamellar structure or a shish-kebab structure. Meridional SAXS experiments can identify the structure present. After extraction, these structures are still present but can be detected only in a more indirect way by SAXS experiments because of an excessive contribution of void scattering. During hot-drawing both structures are transformed into a more fibrillar structure. The shish-kebab structures can be drawn only to relatively low hot-draw ratios with an incomplete transformation of the lamellar overgrowth into the fibrils, as demonstrated by the presence of a meridional SAXS maximum/shoulder. This leads to relatively weak fibers. Lamellar structures can be drawn to high draw ratios by chain unfolding. A nearly complete transformation of the lamellae into fibrils is obtained and the fibers have excellent properties. The information about the morphology obtained by SAXS, DSC, WAXS, and SEM can be used to establish a relation between morphology and properties.  相似文献   

2.
The mechanism of the transition from a lamellar phase to a gyroid phase in an aqueous solution of a diblock copolymer has been studied by time-resolved synchrotron small-angle X-ray scattering. The transition occurs via a metastable perforated lamellar structure. The perforations initially have liquidlike ordering before developing hexagonal packing. The transient phase of irregularly perforated layers is revealed by the development of diffuse scattering peaks, just below the Bragg peaks of the lamellar structure. The diffuse scattering is modeled by Monte Carlo simulations of perforated layers. Following the formation of perforations, Bragg peaks characteristic of a hexagonal structure signal an ordering into a hexagonal lattice (with the concomitant loss of diffuse scattering). Computer simulations based on a dynamic density functional model reproduce these features. The hexagonal perforated lamellar phase is rapidly replaced by the gyroid phase. The domain spacing of the gyroid phase is larger than that of the perforated lamellar structure. The perforated lamellar and gyroid phases coexist for a defined period. The reverse transition from gyroid to lamellae occurs directly, with no transient or metastable intermediates.  相似文献   

3.
Polyethylene mats of shish-kebab fibrils were prepared from solution by stirring-induced crystallization, and subjected to deformation. A morphological study by scanning electron microscopy showed that the elementary shish-kebabs are elongated during drawing. For low draw ratios, the average distance between the lamellae on the fibrils increases proportionally to the draw ratio. The invariance of the fibril diameter upon drawing indicates a transformation of lamellar into fibrillar material. The molecular topology which underlies this deformation mode is discussed and related to the crystallization process.  相似文献   

4.
The tensile strength of gel-spun polyethylene fibers obtained after hot-drawing depends on spinning conditions such as spinning speed, spinning temperature, spinline stretching, polymer concentration, and molecular weight/molecular weight distribution. High deformation rates in the spinline result in shish-kebab structures which after hot-drawing lead to fibers with poor properties. This is in contrast to hot-drawn fibers obtained from gel-spun fibers with a lamellar structure. Lamellar or shish-kebab structures in the gel-spun fibers can be distinguished by means of DSC experiments on strained fibers. On the basis of these experiments a qualitative prediction of the final tensile properties can be made. DSC experiments on (un)strained hot-drawn fibers show that in the case of shish-kebab structures an incomplete transformation into a fibrillar structure takes place which partly explains the low tensile strength. Chain slippage which becomes possible after the orthorhombic-hexagonal phase transition is involved in the fracture mechanism. The shift of the orthorhombic-hexagonal phase transition to higher temperatures with increasing tensile strength indicates that the increase in strength corresponds to an increase in length of the crystal blocks. Consequently, creep failure also occurs at higher stresses. The melting behavior of cold-drawn and hot-drawn fibers is qualitatively similar, but the transformation into a fibrillar structure is more complete in the latter case.  相似文献   

5.
6.
The changes in the fibrillar and the lamellar structure in nylon 6 fibers resulting from drawing and annealing were studied by a detailed analysis of their two-dimensional small-angle scattering patterns. The scattering object that gives to rise the diffuse equatorial scattering in the angular range of Q = 0.02 to 0.3 Å−1 is assumed to be a fibril. There are two distinct regimes in the equatorial diffuse scattering. The scattering at Q < 0.1 Å−1 is dominated by scattering due to the longitudinal dimension of the fibril, and that at Q > 0.1 Å−1 to the lateral dimensions/organization of the fibril. The interfibrillar regions, unlike the interlamellar regions that are essentially made of amorphous chain segments, may have microvoids in addition to amorphous chain segments. The intensity distribution within the lamellar reflections was used to obtain the lamellar spacings and the dimension of the lamellar stacks. The length of the fibrils is between 1000 and 3000 Å, the higher values being more prevalent at lower draw ratios. The fibril length is larger than the length of the lamellar stack, and approaches the latter at higher draw ratios. Annealing does not change the lengths of the fibrils, but the length of the lamellar stack increases. The fibrils form crystalline aggregates with a coherence length of ∼200 Å at higher draw ratios. The diameter of the fibrils (50–100 Å) determined from the lamellar reflection using both the Scherrer equation and the Guinier law are consistent with the lateral size of the crystallites derived from wide-angle x-ray diffraction. The longitudinal correlation of the lamellae between the neighboring fibrils improves upon drawing and decreases upon annealing. The degree of fibrillar and lamellar orientation is about the same as the crystalline orientation. Lamellar spacing increases upon drawing (from ∼60 to 95 Å) and annealing (from ∼85 to 100 Å). This is accompanied by an increase in the width of the amorphous domains from 30 to 50 Å in drawn fibers, and from 45 to 55 Å in annealed fibers. The diameter of the fibrils decreases slightly upon drawing and increases considerably upon annealing. © 1996 John Wiley & Sons, Inc.  相似文献   

7.
In this paper, the polyketone (POK) extrusion cast film is manufactured by melt stretching method, and the evolution process of the crystal morphology and mechanical properties with the increase of melt drawing ratio (MDR) are followed. The results show that the melt stretching process produces many micro shish-kebab crystals in the POK. The length of the shish crystal and the thickness of the kebab crystal hardly increase with MDR, but the lateral length of the kebab crystal shows linear growth when MDR exceeds 40. The crystalline morphology of POK is mainly affected by melt relaxation. The molecular chain has sufficient relaxation during cooling at a low MDR (20–40). At this time, micro shish-kebab crystals are mainly randomly arranged. When MDR exceeds 40, the rapid melt stretching shortens the relaxation time of the tie chain between the neighborhood shish crystal, and the atomic force microscopy image shows a typical shish-kebab structure. This experimental result indicates that the formation of the oriented lamella structure may be related to the relaxation of the molecular chains between the micro-shish. When the length of the shish axis and the thickness of the kebab lamellae are similar, it is difficult to distinguish the two.  相似文献   

8.
A set of unimodal and bimodal high density polyethylene (HDPE) pipe resins of different grade were characterized to investigate the relation between branched structure and resistance to SCG. The results showed that the SCB of bimodal PE100RC was more likely to incorporate into long chains and the entanglement of tie molecules was higher, thus making thicker lamellae and more complete lamellae network. The strain hardening (SH) modulus proved bimodal PE100RC had better long term performance compare with unimodal and bimodal PE100. Besides, small-angle/wide-angle X-ray scattering (SAXS/WAXS) presented the lamellae evolution of bimodal PE100RC and PE100 under uniaxial extension. In the transition of shish-kebab to fibrillar crystals, the orientation increased with the rising of strain and presented a two-stage process with the turning point at the strain of about 1.0. And the long period curves exhibited a three-stage process which were yeilding, softening and hardening stage. In the yeilding region, the long period of PE100RC grew at a faster rate compared with PE100 as the amorphous region of PE100RC was easier to stretch. At the end of yield region, the lamellae thickness of PE100 was smaller than before, while that of PE100RC became larger. It can be inferred that in PE100, only fragmentation of lamellae can be observed, while in PE100RC, the recrystallization as well as destruction of lamellae occurred.  相似文献   

9.
We present a neutron scattering study of oriented samples for the lamellar phase of the ternary mixture sodium decyl sulphate/1-decanol/water. Diffuse scatterings are observed, around the Bragg reflections and away from them, which show that the structure of this lamellar phase deviates from the periodic stacking of infinite homogeneous lamellae of water and amphiphilic molecules usually proposed for the structure of lamellar phases. The nature of this deviation evolves with the soap/decanol ratio, according to the location of the sample in the lamellar domain of the phase diagram. In the middle of the domain the deviation relates to the organization of the lamellar stacking, without apparent modification of the structure of the lamellae of amphiphiles. Moving away from the middle, for higher soap/decanol ratios, the structure of the lamellae appears to be randomly perturbed, eventually by the presence of a few water regions piercing them. When the boundary of the lamellar domain is approached, for still higher soap/decanol ratios, the density of these peturbations increases and they start to be correlated over limited distances, within the lamellae and from lamella to lamella. The local symmetry of these short range correlations is such that these perturbations may be seen as structural fluctuations which may be seen as precursors of the transformation of the lamellar phase into a neighbouring phase on the phase diagram. This phenomenon is discussed briefly in relation to the structural fluctuations of the relative concentrations of sodium decyl sulphate and decanol within the aggregates.  相似文献   

10.
Drawing and extrusion of semi-crystalline polymers   总被引:1,自引:0,他引:1  
This review treats mainly the initial transformation of the starting unoriented lamellar material into the final oriented microfibrillar structure and its drawing. If the starting material has partially oriented shish-kebab structure the drawing is a combination of transformation of lamellae into the microfibrils and the drawing of microfibrils. The review article is based on the literature from the last ten years and relys heavily on recent reviewing [1–3]. Older articles are only included if they have contributed to the basic ideas and experiments of drawing.  相似文献   

11.
Studies of lamellar shapes and profiles in linear polyethylene have often been implemented by microscopic examination of appropriately etched random slices through spherulitic specimens. However, since a spherulite crystallized from a bulk specimen is a three-dimensional assembly of radially oriented lamellae with a twisting orientation (except for very high Tcs), it may be difficult to draw appropriate conclusions from a random slice. A technique has been developed that allows one to prepare spherulitic surfaces such that their distance relative to the geometric center can be well characterized. A computer-based graphical representation is also presented which suggests that the projection of lamellae on such surfaces is adequately represented by a radially oriented assembly of helicoidally twisted lamellae. Based on the agreement between the experimental results and the computer model, it is suggested that the C and S shapes previously observed by other researchers are not necessarily intrinsic to the lamellar profile but may arise due to geometrical effects as the lameliae project onto a surface at various angles. From these results it is also evident that in ringed spherulites lamellae undergo continuous twisting rather than successive misalignment of essentially untwisted segments.  相似文献   

12.
Small-angle and wide-angle x-ray scattering measurements, using a position-sensitive detector, were made during melt-crystallization of linear polyethylenes and PEO–PS–PEO triblock copolymer. The scattering measurements indicated that the triblock copolymer grew by the enlargement of regions in which lamellae are regularly stacked. During primary crystallization at higher temperatures similar behavior is observed in two linear polyethylenes. At lower temperatures, changes in the shape of small-angle scattering curves during the primary stage of crystallization indicate that amorphous gaps within the lamellar stacking become filled in. During secondary crystallization at higher temperatures new crystallites appear to grow between those formed in the primary stage. Concurrent decrease of the overall scattered intensity leads to the conclusion that secondary crystallization has two components: crystallization of new lamellae behind the spherulite growth front and the thickening of existing lamellae.  相似文献   

13.
Interaction of slightly crosslinked hydrogels of poly(diallyldimethylammonium chloride) (PDADMACI) and of copolymer DADMACI/acrylamide (AAm) with sodium dodecylsulfate (SDS) and sodium dodecylbenzenesulfate (SDBS) results in significant shrinking of the gels due to the formation of polymer-surfactant complexes. Jump-wise transitions in the collapsed state were observed for the networks with the content of cationic groups 100 and 75 mol %. The structure of complexes was studied by means of X-ray scattering method. The scattering curves for collapsed gels, where most chloride anions were replaced by anions of SDS, show a set of well-pronounced narrow diffraction maxima. Fully charged “wet” complexes studied at the equilibrium swelling conditions exhibit high degree of ordering, which diminishes upon drying with the simultaneous transition from hexagonal to lamellar type of ordering. In contrast to this, for DADMACl/AAm copolymer gels (75 mol % of DADMACl monomers in the initial polymerization mixture) the ordering is less pronounced in the “wet” state and becomes more perfect upon drying. The SDS aqueous solutions of the same concentration in the absence of gel do not show such high degree of ordering, while the system of SDS/neutral AAm gel exhibits lamellar ordering typical for low-temperature phases of SDS solutions. © 1996 John Wiley & Sons, Inc.  相似文献   

14.
Formation of shish-kebab crystals using a bimodal polyethylene system containing high molecular weight(HMW)component with different ethyl branch contents was investigated.In situ small-angle X-ray scattering(SAXS)and wide-angle X-ray diffraction(WAXD)techniques were used to monitor the formation and evolution of shish-kebab structure sheared at low temperature in simple shear mode and low rate.Only the bimodal PE with no branch formed shish-kebab crystals at the shear temperature of 129℃,and the shish length increased with the crystallization time,while bimodal PE with branch has no observable shish under the same conditions.The degree of crystallization for bimodal PE with no branch increased with time up to above 7%,while those with ethyl branch increased continually up to above 23%.Furthermore,bimodal PE's Hermans orientation factor with no branch increased to 0.60,while those with ethyl branch only increased to a value below 0.15.This study indicated that the shish-kebab crystal formed at the low temperature of 129℃is due to the stretch of entangled chains under shear for the bimodal PE with no branch.Only partly oriented lamellar crystals were formed for the bimodal PE with ethyl branch.All the results at the shear temperatures higher,closed to,and lower than the melting point,the modulation of shish crystals formation owing to different mechanisms of the coil-stretch transition and the stretched network by changing shear temperature was achieved in the bimodal PE samples.  相似文献   

15.
The random phase approximation is reformulated to investigate the anisotropic fluctuations about an ordered polymer phase. This very general method is applied to the lamellar phase of block copolymers. The calculated anisotropic scattering intensity captures the main features observed experimentally including the secondary peaks due to fluctuations with hexagonal symmetry. We also determined the limits of metastability of the lamellar phase as well as the bending and elastic moduli of the lamellae.  相似文献   

16.
PBT is a semi-crystalline thermoplastic polymer whose deformation behavior highly depends on processing parameters. This makes it a model polymer for investigating morphological changes caused by deformation on the spherulitic and lamellar level. In the neck region all states of deformation of the spherulites are observed. Even in the fibrillar phase the borders of the spherulites remain visible. The spherulitic structure is not totally destructed in the neck. The lamellar structure of the fibrillar phase significantly differs from that of the spherulitic region. The lamellae are orientated with respect to the direction of deformation and the lamellae heights are reduced distinctly. Scanning electron microscopy of fracture surfaces reveals for some samples a sharp frontier between spherulitic and fibrillar region. This leads to the conclusion that the necking process may be a phase transition between an isotropic and a highly orientated phase, as predicted for a Van der Waals network.  相似文献   

17.
The theory of lamellar superstructures in binary mixtures of AB diblock and linear ABC triblock copolymers under the condition of strong segregation between chemically different blocks is developed. This system is considered using Alexander‐de Gennes (box‐model) and self‐consistent field (SCF) models. The formation of a mixed lamellar superstructure comprising both mixture components is proved. It is shown that a mixed lamella may be the only type of lamellae in the mixture, or it may coexist with pure diblock lamellae, depending on the mixture composition, local characteristics of blocks (thickness and Kuhn segment length), and surface tension coefficients at the A/B and B/C interfaces. Preliminary experimental results provide support of these theoretical estimations. The formation of mixed lamellae in a mixture of linear ABC and branched (AB)2C block copolymers is also considered.  相似文献   

18.
 A separation method by spatial frequency filtering of the diffuse background of small-angle X-ray scattering (SAXS) is transferred to the case of isotropically scattering samples of polymer materials. Analysis of the residual discrete SAXS is demonstrated. Evaluations of model scattering curves from lamellar two-phase systems show that this technique, in general, results in a good separation. If samples with pure particle scattering or such with rough domain surfaces are investigated, the separation of a suitable background is possible, but is prone to some uncertainty which is estimated. In the case of particle scattering from lamellae the problem is solved by fitting a model function considering polydispersity to the Lorentz-corrected scattering intensity. After background correction the residual information on the distorted nanostructure is collected in an interface distribution function, from which topological parameters can be recovered with high accuracy. These parameters comprise average layer thicknesses and parameters of particle polydispersity. Parameter recovery is achieved by nonlinear regression with model functions describing stacking statistics. Automated versions of the technique are suited to process and analyse series of polymers collected in time-resolved synchrotron radiation experiments. Received: 24 July 2001 Accepted: 12 September 2001  相似文献   

19.
We report the synthesis of silver-decanethiolate (AgSC10) lamellar crystals. Nanometer-sized Ag clusters grown on inert substrates react with decanethiol vapor to form multilayer AgSC10 lamellar crystals with both layer-by-layer and in-plane ordering. The crystals have strong (010) texture with the layers parallel to the substrates. The synthesis method allows for a precise control of the number of layers. The thickness of the lamellae can be manipulated and systematically reduced to a single layer by decreasing the amount of Ag and lowering the annealing temperature. The single-layer AgSC10 lamellae are two-dimensional crystals and have uniform thickness and in-plane ordering. These samples were characterized with nanocalorimetry, atomic force microscopy (AFM), transmission electron microscopy (TEM), X-ray diffraction (XRD), X-ray reflectivity (XRR), Fourier transform infrared spectroscopy (FTIR), and Rutherford backscattering spectroscopy (RBS).  相似文献   

20.
In this study, highly oriented shish-kebab structure was achieved via imposing oscillatory shear on the melts of linear low density polyethylene (LLDPE)/high density polyethylene (HDPE) blends during the packing stage of injection molding. To investigate the effect of molecular weight of HDPE on the formation of shish-kebab structure, two kinds HDPE with large melt flow index (low molecular weight) and small melt flow index (high molecular weight) were added into LLDPE matrix. The structural characteristics of LLDPE/HDPE blends were systematically elucidated through two-dimensional wide-angle x-ray scattering, scanning electron microscopy, and differential scanning calorimetry. Interestingly, an unexpected molecular weight dependence of shish-kebab structure of the prepared samples was found that the addition of HDPE with low molecular weight resulted in an higher degree of orientation, better regularity of lamellar arrangement, thicker lamellar size, and higher crystal melting temperature than that adding HDPE with high molecular weight. Correspondingly, the blend containing low molecular weight HDPE had better tensile strength. A possible mechanism was suggested to elucidate the role of HDPE molecular weight on the formation of shish-kebab structure in the oriented blends, considering the change of chain mobility and entanglement density with change of molecular weight.  相似文献   

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