Crystallization of short aliphatic polymer chains. I. General chain-folding behavior

Short aliphatic polymer chains of different lengths were prepared by degrading polyethylene samples of appropriately chosen initial fold lengths to the chain lengths which correspond to a single chain traverse through the lamella. The resulting dicarboxylic acids were either used as such for further crystallization experiments or were first converted into diiodides to remove polar endgroups. The resulting short polymers all crystallized by chain folding even if the chains (peak of distribution) were only 1.5–4 times the length of a traverse through the lamella. In the diiodides the fold length varied continuously with crystallization temperature, as is usual in high molecular weight material, but with the dicarboxylic acids such variation, while observable, was only small. The effect of the molecular weight on the fold length due to its influence on supercooling at a given crystallization temperature has become apparent. Renewed degradation with nitric acid and subsequent GPC analysis of the degradation products confirmed the folded nature of the chains in the above crystals. This analysis combined with experiments on the reactivity of chain ends has led to the picture that each chain folds completely, once, twice etc. so that both folds and ends are in the surface zone but are located at varying heights, as appropriate to the overall layer thickness for the molecular weight distribution in question. This picture is consistent with other concurrent work.     

Crystallization of short aliphatic chains. II. Example of even fold surface with adjacent fold reentry and of a transition to chain extension

As a continuation of the preceding study on the folding behavior of short polymer chains, an iodine-terminated paraffin having 156 Å peak molecular length and a sharp molecular weight distribution was prepared. The paraffin could be crystallized in lamellae of two different thicknesses: (A) thickness close to half the chain length (the most readily obtained); (B) thickness intermediate between half chain length and fully extended chain. Case A corresponds to each chain folding once with equal stems and with ends at the surface. Degradation behavior revealed that the folds must be of closely equal length giving rise to an even fold surface. In case B the situation is more involved: here the chain ends must turn into the lattice. Adjacent reentry is a necessity throughout. In both cases the lamellar thickness could be increased by annealing up to complete chain extension.     

Bond rupture in highly oriented crystalline polymers

The strength-limiting process in the fracture of semicrystalline fibers and highly oriented films is the rupture of tie molecules connecting the folded chain lamellae in the machine direction. This view is supported by the data on stress and temperature dependence of lifetime of fibers under load and on radical formation during the fracture experiment. The observed tensile strength, however, is about 10 times smaller and the number of fractured chains between 100 and 1000 times larger than expected on the basis of the known number of tie molecules in the fracture plane. This discrepancy is a consequence of the inhomogeneity of the micromorphology of fiber structure, which causes a much larger stress concentration on the most unfavorably located tie molecules than the average value one would expect in the case of perfectly uniform stress distribution on identical tie molecules. The fluctuation of amorphous layer thickness, of number and length of tie molecules, produces such a high stress concentration on some tie molecules throughout the sample that they rupture long before the average stress concentration is sufficient for chain fracture. By accumulation of damage caused by gradual chain rupture the weakening of the sample locally proceeds so far that at the maximum damage concentration, microcracks start to form, and the fiber breaks.     

High speed injection molding of high density polyethylene �� Effects of injection speed on structure and properties

Thin wall samples of high density polyethylene (HDPE) were prepared via injection molding with different injection speeds ranging from 100 mm/s to 1200 mm/s. A significant decrease in the tensile strength and Young??s modulus was observed with increasing injection speed. In order to investigate the mechanism behind this decrease, the orientation, molecular weight, molecular weight distribution, melt flow rate, crystallinity and crystal morphology of HDPE were characterized using two-dimensional wide-angle X-ray diffraction (2D-WAXD), gel permeation chromatography (GPC), capillary rheometry and differential scanning calorimetry (DSC), respectively. It is demonstrated that the orientation, molecular weight, molecular weight distribution, melt flow rate and crystallinity have no obvious change with increasing injection speed. Nevertheless, the content of extended chain crystals or large folded chain crystals was found to decrease with increasing injection speed. Therefore, it is concluded that the decrease in tensile properties is mainly contributed by the reduced content of extended chain crystals or large folded chain crystals. This study provides industry with valuable information for the application of high speed injection molding.     

Conformational behaviour of laterally dialkoxy branched mesogens. Part one

The crystal structures of two mesogenic compounds having two neighbouring lateral alkoxy chains in the central part of the molecules have been solved. In both structures, the common four ring central core is extended and quite rigid with a total length close to 28.5 Å. All the molecules are strictly parallel because of the P1 space group; the molecular arrangement is characteristic of a nematogenic system. In these structures, the lateral alkoxy chains are folded back to the core; they exhibit slightly different conformations and are quite disordered. The ¹³C chemical shift of the first -OCH₂- within the lateral chains can probe the mean conformation of the chain in the nematic phase. This chemical shift is independent of the compound. Nevertheless, in the solid phase, this chemical shift is dependent on small geometrical changes due to the influence of the oxygen in the neighbouring lateral chain. In addition, temperature cycling of the sample leads to different crystalline solid forms as evidenced by DSC and NMR studies.     

A biocompatible surfactant with folded hydrophilic head group: enhancing the stability of self-inclusion complexes of ferrocenyl in a beta-cyclodextrin unit by bond rigidity

This work reports a new biocompatible surfactant structure, of which the hydrophilic head group is composed of a folded, stable self-inclusion complex of a ferrocenyl substituted beta-cyclodextrin (betaCD). While multiple intra- or intermolecular complexes can exist for this amphiphile, the molecule folds into a unique intramolecular complex with well-defined conformation, in which part of the aliphatic chain and the ferrocene group are both included in the annular cavity of betaCD. Study of different isosteric covalent linkages indicates that this folded structure is stable against displacement by the presence of other small guest molecules. Furthermore, in contrast to ferrocene-CD conjugates that are without the aliphatic chain, the presence of small guest molecules in solution does not influence at all the induced circular dichroism signal of this amphiphile, indicating a sterically congested, but stable, folded conformation of the inclusion complex. This new amphiphile is surface active and, more importantly, does not denature the membrane protein bacteriorhodopsin. Finally, because this surfactant forms self-assembled aggregates, this work introduces a folded structure into soft matters formed by amphiphiles in water.     

DNA conformation in nanochannels: Monte Carlo simulation studies using a primitive DNA model

We have performed canonical ensemble Monte Carlo simulations of a primitive DNA model to study the conformation of 2.56 ~ 21.8 μm long DNA molecules confined in nanochannels at various ionic concentrations with the comparison of our previous experimental findings. In the model, the DNA molecule is represented as a chain of charged hard spheres connected by fixed bond length and the nanochannels as planar hard walls. System potentials consist of explicit electrostatic potential along with short-ranged hard-sphere and angle potentials. Our primitive model system provides valuable insight into the DNA conformation, which cannot be easily obtained from experiments or theories. First, the visualization and statistical analysis of DNA molecules in various channel dimensions and ionic strengths verified the formation of locally coiled structures such as backfolding or hairpin and their significance even in highly stretched states. Although the folding events mostly occur within the region of ~0.5 μm from both chain ends, significant portion of the events still take place in the middle region. Second, our study also showed that two controlling factors such as channel dimension and ionic strength widely used in stretching DNA molecules have different influence on the local DNA structure. Ionic strength changes local correlation between neighboring monomers by controlling the strength of electrostatic interaction (and thus the persistence length of DNA), which leads to more coiled local conformation. On the other hand, channel dimension controls the overall stretch by applying the geometric constraint to the non-local DNA conformation instead of directly affecting local correlation. Third, the molecular weight dependence of DNA stretch was observed especially in low stretch regime, which is mainly due to the fact that low stretch modes observed in short DNA molecules are not readily accessible to much longer DNA molecules, resulting in the increase in the stretch of longer DNA molecules.     

Thermal fractionation of vinyl acetate-vinyl alcohol copolymers

Thermal fractionation via the method of successive self-nucleation and annealing was used for the first time to study the crystallinity of vinyl acetate-vinyl alcohol copolymers with different random distributions of chain units. The lamella-thickness distribution was calculated through the Gibbs-Thomson equation. It was shown that, for all samples, the minimum lamella thickness is the same and corresponds to a block of no less than 15 vinyl alcohol units. On the basis of these data and with the use of the computer simulation of the polymer-analogous reaction via the Monte Carlo method, the block-length distribution in the crystalline phase was found. It was shown through a comparison of the lamella-thickness and block-length distributions that the maximum lamella thickness increases with the block length and vinyl alcohol content in the copolymer. In crystallites, blocks with lengths exceeding the maximum lamella thickness comprise a significant fraction. Thus, it is probable that these blocks form folds. The dependences of melting temperatures of crystalline lamellas on their thicknesses, as well as the dependences of the melting temperatures of copolymers not subjected to thermal fractionation on the chain-structure parameters, are adequately described by the Flory crystallization theory.     

On the location of chain-ends in rapidly crystallized poly(ethylene terephthalate)

Phenylmercurated poly(ethylene terephthalate) (PET) chain-ends are obtainable through the transesterification of PET by phenylmercury hydroxide or acetate in solution in nitrobenzene at 165 ± 10°C. The reaction results in an average of one mercury atom per chain. The phenylmercuration may be followed by infrared or x-ray fluorescence. Reaction with concentrated HCI Affords the elucidation of some structural parameters of the resultant partially crystalline tagged PET, through analyses of changes in viscosity and molecular weight, in percent crystallinity, and in the amount of mercury in the system. The chain-ends are almost completely excluded from the stem region of the PET crystal with no more than 2% remaining. The chain-ends are distributed unevenly throughout the amorphous phase. This is corroborated by sharp decreases in scattered intensity of small-angle x-ray measurements. Two models for the distribution of chain-ends in the amorphous phase are considered. The one in which the ends are pushed farthest from the crystal surface and concentrate halfway between crystallites is tentatively adopted. Analysis of the HCI hydrolysis kinetics and products leads to the following picture concerning the fold tightness and position. About one out of five folds extends significantly into the amorphous matter where it is mingled with cilia, tie molecules, and unattached molecules. Random scission throughout such an amorphous mass should lead to a preponderance of cleaved molecules whose length should be four to five times the lenght of the crystalline stem region, as is indeed observed.     

Accordion-type laser-Raman scattering by drawn linear polyethylene

One can reproduce the observed accordion-type laser-Raman (ALR) scattering of highly drawn linear polyethylene if one assums that any gauche defect in the crystal lattice which interrupts the all-trans conformation sequence of the molecular chain completely decouples the accordion-type longitudinal oscillations of the two sections on both sides of the defect. Each oscillates independently of the rest. The length of the section, smaller than the full length of the straight chain between the crystal surfaces, determines the frequency of the ALR absorption. One such defect per five chain stems of the ideal crystal yields a straight-length distribution which agrees sufficiently well with that derived from the ALR spectrum. Small-angle x-ray scattering very generally registers the resulting decrease of the electron density of the crystalline component without yielding more detailed information about the location and frequency of such gauche defects.     

Molecular dynamics simulations of end-to-end contact formation in hydrocarbon chains in water and aqueous urea solution

We probe the urea-denaturation mechanism using molecular dynamics simulations of an elementary "folding" event, namely, the formation of end-to-end contact in the linear hydrocarbon chain (HC) CH(3)(CH(2))(18)CH(3). Electrostatic effects are examined using a model HC in which one end of the chain is positively charged (+0.2e) and the other contains a negative charge (-0.2e). For these systems multiple transitions between "folded" (conformations in which the chain ends are in contact) and "unfolded" (end-to-end contact is broken) can be observed during 4 ns molecular dynamics simulations. In water and 6 M aqueous urea solution HC and the charged HC fluctuate between collapsed globular conformations and a set of expanded structures. The collapsed conformation adopted by the HC in water is slightly destablized in 6 M urea. In contrast, the end-to-end contact is disrupted in the charged HC only in aqueous urea solution. Despite the presence of a large hydrophobic patch, on length scales on the order of approximately 8-10 A "denaturation" (transition to the expanded unfolded state) occurs by a direct interaction of urea with charges on the chain ends. The contiguous patch of hydrophobic moieties leads to "mild dewetting", which becomes more pronounced in the charged HC in 6 M aqueous urea solution. Our simulations establish that the urea denaturation mechanism is most likely electrostatic in origin.     

Crystal structures of n-alkanes with branches of different size in the middle

We synthesized four branched n-alkane samples C35-C1, C35-C4, C35-C6, and C35-C4Ph with the same number of carbons as the main chain, n = 35, to which the methyl, butyl, hexyl, and butyl phenyl groups were respectively attached at the middle, and also the corresponding linear homologue of C35, and studied their crystalline structures from DSC, IR, and Raman spectroscopy, X-ray diffraction measurement, and computer simulation. Solid-solid phase transitions characteristic of linear alkane C35 are not observed for any branched alkanes, and their melting temperatures Tm are lowered to 325.2, 318.5, 314.3, and 314.1K, respectively. Main chains of branched alkane molecules are not folded, irrespective of length and chemical structure of branches, but are extended to take the planar zigzag form in the solid state. The branches of C35-C4 and C35-C6 are also aligned inside the crystal in the extended form. Data analyses on solution-grown crystallized samples reveal that, with increasing the branch length, their crystal structures transform from polymorphic forms of the orthorhombic (P2(1)2(1)2(1)) and the triclinic (P) for C35-C1 and C35-C4 to the unique triclinic form for C35-C6 and C35-C4Ph, so as to minimize extra surface energy invoked by introduction of long branches.     

纤维素Ⅱ和碱纤维素Ⅱ单结晶的研究

本文用电子显微镜和电子衍射技术研究苎麻的纤维素Ⅱ和碱纤维素Ⅱ单晶。纤维素Ⅱ单晶成长条状,长约2μ,宽约0.4～0.6μ,电子衍射技术表明长条状单晶长的方向是纤维分子链的方向,故分子链不应该是折叠链结构。碱纤维Ⅱ单晶是不规则的多边形,单晶的大小为0.3～4μ,碱纤维素Ⅱ孪晶是由两块单晶重叠并错开约2.6°角度而构成的,孪晶面为(001)面。     

Studies of the morphology of emulsion-grade polytetrafluoroethylene

Two types of emulsion-grade polytetrafluoroethylene particles have been studied. We refer to these as ribbons and rods. The ribbons consist of very thin ribbons or lamellae folded upon themselves a number of times. In typical emulsion-grade material prepared at Allied Chemical, the unraveled ribbon measures about 3.25 μ in length, 0.25 μ in width, and 60Å in thickness. The folded ribbons, which form the particles, are about 0.5 μ long and 0.25 μ wide. Electron diffraction shows that the ribbons are single crystals with the chain axis parallel to the long axis of the ribbons thus forming extended chain crystals. This extended-chain packing is consistent with the observed cleavage or fibrillation of the ribbons and with the molecular weight. The rods are formed in low–yield polymerizations. Electron diffraction also shows that the rods are single crystals with the chain axis parallel to the long axis of the rods. Striations parallel to the long axis are believed to result from stacking of parallel segments. Considerable bending of the long axis of rods is observed.     

The AFM observation of linear chain and crystalline conformations of ultrahigh molecular weight polyethylene molecules on mica and graphite

Atomic force microscopy (AFM) has been applied to visualize expanded linear chain and compact crystalline conformations of ultrahigh molecular weight polyethylene (PE) molecules deposited on mica and graphite from diluted solutions at elevated temperatures. Isolated PE chains are visualized on mica with the apparent negative AFM height and the contour length much shorter than the molecular length. The chain conformations have both the kinked random‐coil sites and the sites of the unexpectedly large two‐dimensional expansion. The crystalline conformations on mica are small single‐molecule rod‐like nanocrystallites and the isolated block‐type “edge‐on” nanolamellae comprising several PE molecules. Noticeable fluctuations of the fold length in the range of approximately 10–20 nm around the averaged value of about 15 nm are observed for nanocrystallites and on tips of some nanolamellae. The explanation of the experimentally observed features of chain surface conformations on mica is proposed. It implies the immobilization of PE molecules in the nm‐thickness salt layer formed on mica surface at ambient conditions after PE deposition and the presence along the chain of multiple expanded chain folds. Only isolated lamellae and lamellar domains of a monolayer height are observed on graphite samples. The substrate/polymer epitaxial incommensurability important for the observation of the PE linear chain surface conformations is discussed from the comparison of the results obtained for mica and graphite, the coil‐to‐crystal intramolecular transformation is assumed to be inhibited on mica surface. The slow disintegration of the original gel structure of PE stock‐solution used for the high‐temperature depositions was found to result in the characteristic large‐scale morphological heterogeneity of the samples. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 766–777, 2010     

Elastic properties of poly(hydroxybutyrate) molecules

Elasticity of various poly(hydroxybutyrate) (PHB) molecules of regular and irregular conformational structure was examined by the molecular mechanics (MM) calculations. Force - distance functions and the Young's moduli E were computed by stretching of PHB molecules. Unwinding of the 2(1) helical conformation H is characterized at small deformations by the Young's modulus E = 1.8 GPa. The H form is transformed on stretching into the highly extended twisted form E, similar to the beta-structure observed earlier by X-ray fiber diffraction. The computations revealed that in contrast to paraffins, the planar all-trans structure of undeformed PHB is bent. Hence, a PHB molecule attains the maximum contour length in highly straightened, but slightly twisted conformations. A dependence of the single-chain moduli of regular and disordered conformations on the chain extension ratio x was found. The computed data were used to analyze elastic response of tie (bridging) molecules in the interlamellar (IL) region of a semi-crystalline PHB. A modification of the chain length distribution function of tie molecules tau(N) due to secondary crystallization of PHB was conjectured. The resulting narrow distribution tau(N) comprises the taut tie molecules of higher chain moduli prone to overstressing. The molecular model outlined is in line with the macroscopically observed increase in the modulus and brittleness of PHB with storage time.     

Gel permeation chromatographic studies of the degradation of polyethylene with fuming nitric acid. I. Single crystals

This paper describes the application of gel permeation chromatography to the morphology of polymer single crystals. Various types of single crystals of polyethylene were etched with fuming nitric acid, and the molecular weight distributions of the degraded fragments determined. The crystal preparations studied were monolayer crystals grown from xylene solution at 85°C and multilayer crystals grown at 84°C and 70°C. In all cases peaks in the molecular weight distribution were observed corresponding to single and double transverses of the molecular chains through the lamellae. By using the chromatograph calibration described in a previous paper, the position of these peaks were compared and correlated with previous estimates of lamellar thickness from low-angle x-ray measurements. The relative positions of the peaks provide information regarding the nature of the fold surface. The results are found to be consistent with a model in which the majority of the molecules are tightly folded.     

Molecular imaging of monodendron jacketed linear polymers by scanning force microscopy

Polystyrene and polymethacrylate with 3,4,5-tris[4-(tetradecyloxy)benzyloxy]benzoic acid and 3,4,5-tris[3,4,5-tris(dodecyloxy)benzyloxy]benzyl alcohol side groups, respectively, were visualized by scanning force microscopy (SFM). The cylindrical molecules did not interpenetrate and their chain ends could be resolved in the images allowing quantitative evaluation of their length distribution. Whereas the polymethacrylate with the sterically most demanding side groups demonstrated a fairly good agreement between the SFM length and the calculated contour length, the polystyrene with the less branched substituent appeared to be at least two times shorter. The reduced length of the polymer chains was attributed to a disordered helixlike conformation.     

Crystallite structure of cellulose

The crystallite structure of cellulose has been elucidated through analyses of the degradations of model compounds by gel-permeation chromatography. These compounds include single crystals of cellulose triacetate, regenerated cellulose from single crystals, precipitated celluloses from solutions, and commercial regenerated cellulose. The corresponding distribution profiles are found to follow the Keller transformation, which is a characteristic behavior of the folded crystals of synthetic polymers. It is also found that the leveling-off DP of cellulose is a first-order approximation of the corresponding fold length. A detailed folding chain model for the regenerated cellulose was constructed, and the various aspects of the structure are discussed. The kinetic data and the degradation products of native celluloses were also analyzed and found to obey the ruling of the chain fold model but not the conventional fringe-micellar model. In addition, an iodine-staining experiment pinpoints a minimum of 1.5% of true amorphous material; this is in quantitative agreement with the conformation analysis for the six-fold helical β-loop bonds. It is therefore suggested that the same chain-fold conformation is applicable to the native polymer. The hydrolysis of cellulose is found to be composed of a triple mode of degradation, i.e., a first-order random scission at the folds, a zero-order peeling reaction at the ends of the crystallites, and a first-order random scission on the lateral surfaces of the cellulose.     

Termination rate constant in free-radical polymerization

The specific rate constant for the termination reaction between two flexible polymer molecules with active chain ends has been considered in relation to the segmental diffusion of chain ends in solution. The probability of reaction between two chain ends per unit time when the centers of gravity of two polymer molecules are at a distance of separation has been calculated by using the Smoluchowski equation and a Gaussian distribution of chain ends. The time during which two polymer molecules are in contact has also been calculated by using the diffusion equation and the potential energy function for intermolecular interaction. The rate constant may then be completely expressed as a complex function of the intramolecular linear expansion factor, molecular weight, and the frictional properties of the reacting polymers' segment. This expression predicts that the rate constant is inversely proportional to solvent viscosity, decreasing with increasing molecular weight to some extent, and is affected by the excluded volume effect and chain flexibility. The complete expression for the rate constant has been simplified and the result compared with experimental data. Close agreement is found between the calculated rate constants and those experimentally obtained.