The determination of the lamellar thickness in semi-crystalline polymers by small-angle scattering

Three small-angle scattering methods for determining the thickness of the crystalline lamellae in polymers are described. These are based on 1. observation of the identity period, 2. determination of the specific surface of the phase boundary, and 3. analysis of the shape of the peak at the origin. The conditions for application of these methods and the types of average obtained are discussed, and some results are presented.     

Drawing and extrusion of semi-crystalline polymers

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.     

Quantitative molecular characterization of oriented semi-crystalline polymers

The stress-strain birefringence relations obtained from the hot drawing of poly(ethylene terephthalate) films are analysed within the framework of non-Gaussian models of rubber elasticity. It is found that, in spite of the increasing influence of strain-induced crystallization for higher draw ratios, the proposed treatment of experimental results leads to the definition of the number of statistical links per elastic chain in the amorphous part of the sample for any state of elongation. The results suggest a progressive disentanglement of the physical network structure and make possible an evaluation of the limit of extensibility attainable in cold-drawing.     

Research on viscoelastic behavior of semi-crystalline polymers using instrumented indentation

In this study, the viscoelastic behavior of a polyamide 12 (PA12) polymer was evaluated using instrumented indentation technology based on a rheological model. The creep compliance and retardation spectra were obtained to analyze the viscoelastic response during the holding stage according to the rheological model under different preloading conditions. The results showed that the viscoelastic responses were independent of the indentation depth or load under step loading conditions. However, the creep compliance increases, and the peak intensity of the retardation spectrum decreases with a decrease in the preloading rate owing to the structural relaxation observed during the preloading stage under ramp loading conditions. Furthermore, softening dispersion can be completed during the loading stage under continuous stiffness measurement (CSM) conditions. As the preloading strain rate changes, the peak of the retardation spectrum gradually decreases until it disappears completely. Moreover, studies on indentation creep using the CSM method are challenging because of the complicated viscoelastic response observed during the preloading stage.     

Simulation study of semi-crystalline polymer interphases

The study of structure and properties of semi-crystalline polymer inter-phases is important to explain and extend polymer applications. In this region, polymer chains exist in three distinct populations: tie chains that bridge the two crystals, chain folds and chain ends. The distribution of these populations influences the properties of the interphase. We have developed off-lattice Monte Carlo simulations of constrained interphases of semi-crystalline polymers which utilize robust off-lattice moves. A united atom model with polyethylene-like interactions and with freely rotating bonds is used to mimic the prototypical flexible chain structure. These simulations capture the limiting distributions of tight and loose chain folds and of tie chains within the metastable phase. The dissipation in order and density between the crystal and amorphous regions has been studied, and results for freely rotating chains indicate that the characteristic decay of anisotropy occurs in a length scale of ca. 10 Å. Simulation results for the effect of system size and molecular weight for freely rotating chains have also been investigated.     

The dielectric constant of lamellar semicrystalline polymers

The problem of representing the dielectric constant of semicrystalline polymers in terms of the dielectric constants and volume fractions of the constitutent crystalline and amorphous phases is considered. For locally lamellar morphology, bounds based on uniform electric and displacement fields are derived. The equations also include the degree of crystal orientation as a parameter. For unoriented polymers the bounds are considerably tighter than the Hashin–Shtrikman bounds, the latter being the best possible without knowledge of phase geometries. The bounds presented here are sufficiently tight to represent the dielectric constant with practical accuracy for a number of examples of semicrystalline polymers. A treatment is also given of the dielectric constant where the lamellar morphology is further specified as being organized into spherulite-like structures. These bounds are somewhat tighter than the lamellar bounds.     

The mechanical moduli of lamellar semicrystalline polymers

Bounds on the elastic constants are derived for semicrystalline polymers whose local morphology is lamellar. Local response matrices (stiffness and compliance) are formulated in three dimensions that simultaneously incorporate uniform in-plane strain and additive forces from layer to layer of crystalline and amorphous phases and uniform stress and additive displacements normal to the lamellar surfaces. Spatial averaging of the stiffness and compliance matrices under the assumption of axially symmetric orientation gives the upper and lower bounds on the longitudinal and transverse tensile moduli and the axial and transverse shear moduli as functions of the separate phase elastic constants, the volume percent crystallinity, and the moments of the orientation 〈cos²θ〉 and 〈cos⁴θ〉. The bounds are much tighter than the Voight upper and Reuss lower bounds that do not recognize phase geometry. Using the known crystal elastic constants of polyethylene, sample calculations on isotropic unoriented materials show that the divergence of bounds at high crystallinity necessitated by the extreme crystal anisotropy shows up only at very high crystallinity. At low temperature the bounds are tight enough to specify G₁, the amorphous modulus, from the measured G and the known crystal elastic constants. At higher temperatures and lower G, the bounds are not tight enough for this purpose but the shear modulus versus crystallinity and temperature data are well fitted by the lamellar lower bound using a temperature-dependent, crystallinity-independent G₁.     

Rate sensitivity and deformation mechanism of semi-crystalline polymers during instrumented indentation

Instrumented indentation tests using both constant loading rate (CLR) and continuous stiffness measurement (CSM) operation modes were performed to investigate the deformation mechanism and their sensitivity to the deformation rate in semi-crystalline polymers through the quantitative analysis of load-depth loading and unloading curves. The strain rate was constant during the CSM tests, while the strain rate decreased with the increasing of loading time in CLR tests. The mechanical response mechanism of the semi-crystalline polymers to these tests was very complicated because of the combined effects of strain-hardening in the crystal phase and strain-softening in the amorphous phase. Results show that the loading index m reflects the strain-hardening or strain-softening response during indentation. When m > 2, the mechanical response was due to the strain-hardening, and when m < 2, the response was due to strain-softening. A method based on the measured contact hardness was proposed to obtain the unloading stiffness, and the other mechanical parameters could then be determined according to the unloading stiffness.     

Laser technology application: Deformation and elastic recovery of semi-crystalline polymers

The elastic deformation-recovery and mechanical properties of semi-crystalline polymers (HDPE, LDPE and their blends) were investigated. An optoelectronic technique based on a laser beam was used to analyze the behavior of the samples under radial stress. The laser technology showed that the recovery process develops in two stages. The first one is governed by the elastic component and the second and slower one is controlled by the inelastic component of the material. At low deformation, the overall recovery is attributed to the development of structural micro-domains generated when shearing the amorphous segments of the polymer. The radial Young modulus was also determined and compared to unidirectional measurements. At low deformation both techniques provide very similar values; nevertheless, the radial Young modulus departs significantly from the unidirectional one when increasing the number of cycles of deformation-recovery.     

Quantitative molecular characterization of cold-drawn semi-crystalline polymers. Case of polyethylene terephthalate

The influence of pre-orientation on the natural draw ratio achieved in necking has been studied for poly(ethylene terephthalate). The results are analysed with the aid of the non-Gaussian theory of rubber elasticity assuming that the amorphous phase behaves as a network formed by entanglements of chains. A model for separating the influence of amorphous and strain-induced crystalline regions on deformation is proposed and compared with the pseudo-affine model.     

Tensile properties of semi-crystalline thermoplastic polymers: Effects of temperature and strain rates

This work deals with the study of temperature and time dependency of tensile properties of a PA 12-based polymer. The range of variation of parameters in experiments was linked to in-service conditions of components manufactured with this material (temperature interval from ?25 °C to 50 °C and average strain-rate magnitudes from 0.00028 s^?1 to 9.4 s^?1). For tests with different temperatures and low speed, an electro-mechanical machine, Zwick Z250, equipped with an incremental extensometer was used. To study the effect of strain rate at medium speeds, a servo-hydraulic system, Schenk PC63M, equipped with a strain-gauge extensometer was used, while at high speeds a servo-hydraulic machine, Instron VHS 160/20, equipped with a high-speed camera for strain evaluation by digital image correlation was employed. The changes of the rate of deformation with strain as well as elastic modulus variation with strain were studied. An increase in the elastic modulus and yield strength was observed with a drop in temperature and an increase in the strain-rate, temperature having a stronger influence on the variation of mechanical properties. The collected data was assembled in an elasto-plastic material model for finite-element simulations capable of rendering temperature- and strain-rate-dependency. The model was implemented in the commercial software Abaqus, yielding accurate results for all tests.     

Investigation of structural changes in semi-crystalline polymers during deformation by synchrotron X-ray scattering

The mechanical behavior of polymer materials is strongly dependent on polymer structure and morphology of the material. The latter is determined mainly by processing and thermal history. Temperature-dependent on-line X-ray scattering during deformation enables the investigation of deformation processes, fatigue and failure of polymers. As an example, investigations on polypropylene are presented. By on-line X-ray scattering with synchrotron radiation, a time resolution in the order of seconds and a spatial resolution in the order of microns can be achieved. The characterization of the crystalline and amorphous phases as well as the study of cavitation processes were performed by simultaneous SAXS and WAXS. The results of scattering experiments are complemented by DSC measurements and SEM investigations. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1574–1586, 2010     

Morphology-shrinkage relationships in semi-crystalline polymers. Epitaxy,a way of eliminating amorphous contribution

A new approach for achieving a highly dimensionally stable film of semi-crystalline polymers via blending is demonstrated. To illustrate this approach, a model system, polyethylene-polypropylene is investigated using TEM, TMA, DSC, and DMA. It is shown that epitaxial growth in polymer blends and laminates can induce a cross-hatch morphology which eliminates or reduces the contribution of an oriented amorphous phase. This ultimately leads to greater dimensional stability and synergism in mechanical properties as well. The presence of an appropriate low-melting component can also be used to reduce shrinkage.     

The elastic moduli of anisotropic polymers having a lamellar texture

Summary A model for a semi-crystalline polymer having a welldefined lamellar texture is considered in which the orientation of the lamellar planes, as deduced from lowangle X-ray diffraction studies, is taken into account. The moduli along the crystallographica-,b- andc-axis are calculated on the basis of interlamellar shear mechanism for a 60% crystalline polymer (LDPE) and compared with the experimental values. The broad agreement is shown to be reasonable.

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Zusammenfassung Es wird ein Modell für ein teilkristallines Polymeres mit definierter lamellarer Textur betrachtet, bei dem die Orientierung der Lamellenebenen, wie sie sich aus Kleinwinkelröntgenstreuung ergibt, berücksichtigt wird. Die Moduln längs der kristallographischen Achsena, b, c werden auf der Basis eines interlamellaren Scherungsmechanismus für ein Polymeres von 60% Kristallinität (Niederdruckpolyäthylen) berechnet und mit den experimentellen Werten verglichen. Die Übereinstimmung scheint vernünftig.

     

Initial stages of growth of poly(p-xylylene) coatings: AFM study

The morphology of poly(p-xylylene) ultrathin films prepared by vapor deposition polymerization on the surface of single-crystal silicon (100) and on the cleaved surface of mica at a substrate temperature of 20°C has been studied by atomic force microscopy. At the initial stage, the growth of the poly(p-xylylene) coating follows the island mechanism. Within the framework of pyramidal model of island growth, the mean diffusion length for monomer p-xylylene is calculated: For the single-crystal silicon, this parameter is 15 ± 3 nm; for the cleaved surface of mica, 9 ± 2 nm. The nature of the substrate and defects on its surface show a peculiar effect on the structure of the poly(p-xylylene) coating. Thus, at a low monomer flow, nucleation of polymer islands on the surface of silicon is predominantly homogeneous, whereas on the cleaved surface of mica, it is heterogeneous. A change in the monomer flow significantly affects the rate of nucleation of polymer islands.     

TFC polyamide membranes modified by grafting of hydrophilic polymers: an FT-IR/AFM/TEM study

Surface modification using grafting of a hydrophilic polymer onto the membrane surface is a possible route to improving the fouling properties of polyamide thin-film composite membranes. The structure of nanofiltration (NF) and reverse osmosis (RO) membranes modified using graft polymerization of acrylic (AA) monomers was visualized and analyzed using attenuated total reflection–Fourier transform infrared spectroscopy, atomic force microscopy and transmission electron microscopy. The results show that a layer of AA polymer is indeed formed on the polyamide surface, which could be accompanied by a change of the surface morphology. It was observed that for the NF membranes studied polymerization could also take place inside the pores of the support as a result of penetration of the monomer through the active layer, particularly for high degrees of grafting. It suggests that the modification procedures should be optimized so that the latter effect is minimized.     

A real-time AFM study on crystal nucleation and growth in nanodroplets of isotactic polypropylene

Isotactic polypropylene (iPP) nanodroplets were prepared by using the classical droplet method in this study. The formation of nanodroplets allowed the controlled observation of polymer nucleation as well as access to crystal growth at exceptionally high supercooling in iPP. Three cases including the heterogeneous nucleation and fast crystallization in iPP droplets, the formation of multiple independent homogeneous nuclei within a single droplet and a single nucleus within a single droplet were detected by using atomic force microscopy (AFM) during gradually cooling after remelting the nanodroplets. Moreover, it is found that when the volume of droplet is larger than the value of ca. 130000 nm3, the first case was observed. Otherwise, the latter two cases appeared. The temperature at which the onset of nucleation was observed in individual droplets was found to be mainly dependent on height of the droplets when the size scale of the droplet is comparable to the size of the critical nucleus in at least one dimension, which indicates the nucleation behavior under confinement.     

Construction of lamellar morphology by side-chain crystalline comb-like polymers for gas barrier

A comb-like polymer containing crystallized alkyl side chains and the intermolecular hydrogen bonds between the linking groups was fabricated by grafting long-chain fatty amine onto poly(styrene-co-acrylic acid)_n (P(S-AA)_n, wherein “n” denoted AA feed ratio). The chemical structures and crystallization behaviors of the comb-like polymer P(S-AA)_n-g(p) (wherein “p” denoted the number of side-chain carbon atoms) were analyzed by Fourier transform infrared, gel permeation chromatography, X-ray photoelectron spectroscopy, and X-ray diffractometer, differential scanning calorimetry, atomic force microscopy, respectively. It was found that the lamellar morphology could be generated by controlling the grafting density and side chain length of P(S-AA)_n-g(p). Moreover, it was identified that the hydrogen bonds between amide groups could enhance the crystallinity and then adjust the interlamellar spacing of lamellar phase. As a result, P(S-AA)₇₀-g(18) with the highest degree of crystallinity and closely packed lamellar morphology showed a good gas-barrier performance, and the nitrogen permeability reached 1.78 × 10^?14 cm³·cm/cm²·s·Pa. Furthermore, the permeation switch of the obtained comb-like polymer could reach 500 times traversing the melting point.     

Real-time neutron reflectivity study of the early stages of diffusion into and dissolution of glassy polymers

The early stages of the penetrant behavior of a series of phthalate plasticizers into thin films of glassy, high-molecular-weight deuterated poly(methyl methacrylate) (dPMMA) have been studied with in situ real-time neutron reflectivity. After an initial induction phase, both dioctyl phthalate and diisononyl phthalate penetrate the dPMMA films, as indicated by an increase in the thickness. In both cases, a fast linear rate of swelling of the polymer is followed by another behavior that is much slower. The slowdown in the velocity of the plasticizers at or near the transition point is assumed to occur because of a balancing of the misfit-induced pressure and the osmotic pressure, which is responsible for the initial plasticizer ingress. In contrast, and unexpectedly, lower molecular weight dibutyl phthalate does not swell dPMMA, but after an initial induction period, the polymer film begins to dissolve. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 3267–3281, 2004     

Initial growth process of polystyrene particle investigated by AFM

We carried out molecular-scale and in situ investigations of the initial growth process of polystyrene particles in soap-free polymerization, where a cationic initiator, V-50, was used to make the formed particles transfer onto the mica plate in sampling, using an atomic force microscope. It was found that the particles coagulated soon after the nucleation process. Such coagulation was estimated from a macroscopic research, however; microscopic evidence was not enough. This study verifies it from a microscopic view.