Crystal growth of polyethylene from dilute solution: Growth kinetics of {110} twins and diffusion-limited growth of single crystals

We have studied the growth kinetics of {110} twins and single crystals of polyethylene in dilute solution of tetrachlorethylene. In terms of {110} twins, we succeeded in obtaining twins without {100} sectors, using a relatively high molecular weight fraction M_w > 10⁴. It is confirmed that the growth is enhanced at the reentrant corner of the twins, and the enhanced growth face inclines to the {110} face because of consecutive generation of steps at the corner. These facts are strong evidence for nucleation-controlled growth of single crystals. The growth rates and obliquity are measured at various supercoolings and concentrations. From consideration of kinetics of steps on the growth face, the following rates and velocity are independently determined from the experimental data: nucleation rate on a flat face, velocity of step propagation, and generation rate of steps at the reentrant corner. The supercooling dependence strongly supports regime II growth. The results on concentration dependence show that the velocity of steps is proportional to concentration over the whole range examined, and the nucleation rate is independent of it in the usual range and becomes proportional to it in the lower range. This concentration dependence of nucleation rate is attributed to the density of adsorbed polymer on the growth face. From this evidence, it is suggested that the rate of travel of steps is limited by volume diffusion of solute polymer, whereas the growth face is saturated with adsorbed polymer at ordinary concentrations. This contradictory situation could be explained by the hypotheses that the saturation density is rather low and that surface diffusion of adsorbed polymer is much slower than volume diffusion of solute polymer. The lower limit of the rate of folding is also determined for the first time from the velocity of step propagation. As regards the single crystals, it is found that the habit maintains a lozenge shape with sharpened points, even at very high supercooling (δT < 50°C) if the concentration is very dilute. Diffusion-limited growth is verified for the first time at the higher supercoolings, where the growth rate is almost independent of supercooling. The growth rate becomes almost equivalent to the velocity of steps determined in the experiments with twins, and this fact will support the accuracy of the evaluation of the step velocity. The order of magnitude of the growth rate obtained agrees with the value which is calculated from the balance between the flux of solute polymer to the growth face and the rate of growth of single crystals.     

Nucleation-controlled growth in polyethylene single crystals: Growth and shape of {100} sectors

The nucleation rate and propagation rate of steps on the {100} faces of polyethylene crystals have been determined. For single crystals, under conditions where the width of the {100} sectors remains constant during growth, it is confirmed that the growth is in regime I or the crossover region between regime I and II. In {110} twinned crystals, the {100} sectors are well developed and the width increases linearly with time; therefore, the growth in the twins must be in regime II. It is shown that the differing growth regimes of {100} faces in single crystals and twins allow the independent determination of the nucleation rate and the propagation rate of steps. The nucleation rate and propagation rate of steps on the {100} faces were determined from measurements of the constant width of the {100} faces in single crystals and the growth rate of the {100} faces in single crystals and twins. The observed rates show abnormal dependence on supercooling and concentration. The results are attributed to a weaker dependence of the constant width of {100} sectors on supercooling and concentration than predicted.     

Growth of polyethylene single crystals from the melt: Morphology

Three-dimensional shape of polyethylene single crystals grown from the melt has been studied. Two distinct types of lateral habit have been obtained: lenticular shape (type A) and truncated lozenge (type B) in the range of regime I and II. Electron microscopy has revealed chair-like shape of type B crystal and reconfirmed the planar shape of type A crystal. In the type B crystal, spiral growth has occurred frequently in the {110} sectors and the sense of the handedness of spiral terraces has been maintained. It has been, suggested that the frequens occurrence of spiral growth is responsible for a morphological change (axialite-spherulite) accompanying the regime I–II transition. The origin of the chair-like crystals has been discussed and, a possible mechanism has been suggested for the formation of spiral terraces; the mechanism is based on a distortion caused by the three-dimensional shape of chair-like crystals. It has been found that the chair-like crystals are curved in the opposite way to S-shaped lamellae observed by Bassett and Hodge in banded spherulites. In fact, the present work has led to the recognition of further classes of crystal with curving cross-sections and of distinctions between them. In final analysis, a unifying thread has been identified between lateral habits, growth kinetics and three-dimensional shape of lamellae, in turn, leading to some rationalization of multilayer developments including twisting in banded spherulites, the latter based on existing suggestions in the literature.     

Poly(decamethylene oxide) single crystals from dilute solution

Summary A preliminary study on the morphology and chain orientation of four low molecular weight poly(decamethylene oxide) fractions crystallized from ethyl alcohol diluted solution is reported. The single crystals predominantly show the polyethylene orthorhombic unit cell projection although some also present the polytetrahydrofuran structure. The characteristic X-ray long periods obtained are indicative in all cases of a chain folded crystal surface.

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Zusammenfassung Eine vorläufige Studie der Morphologie und der Kettenorientierung von vier Polydecamethylenoxyd-Fraktionen niederen Molekulargewichtes, die aus verdünnter Methylalkohol-Lösung kristallisiert wurden, wird wiedergegeben.Die Einzelkristalle zeigen bevorzugt die orthorhombische Projektion der Einheitszelle, obgleich einige auch die Polytetrahydrofuranstruktur präsentieren. Die charakteristischen Röntgenstrahllangperioden deuten in allen Fällen auf eine kettengefaltete Kristalloberfläche hin.

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With 5 figures

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Thanks are due to Mr.J. Tinas Gálvez for the kind supply of the samples.     

Terephthalamide-nylon single crystals isolated from dilute solutions of hexafluoro-2,2-propandiol

Terephthalamide nylons with two to five carbon atoms in the aliphatic portion of the chain have been crystallized from aqueous solutions of hexafluoro-2,2-propandiol. The 3T and 4T nylons in particular form rodlike crystals. Indications are that these are bundles of cylindrical structures about 50 nm in diameter. Electron diffraction shows the symmetry to be C_2v. Films of the nylons were drawn with great difficulty. The x-ray diffraction on the films is consistent with a monoclinic structure, though the crystal structure could not be positively established. There is some evidence for a polymer chain alignment perpendicular to the long axis of the rods.     

Growth of polyethylene single crystals from the melt: change in lateral habit and regime I–II transition

Using the technique of extraction, single crystals have been obtained from polyethylene fractions isothermally crystallized from the melt at atmospheric pressure. It has been found that the lateral habit of single crystals changes in the vicinity of the transition temperature of growth regime (regime I–II): lenticular shape elongated in the direction of theb axis (type A) in the range of regime I and truncated lozenge with curved edges of {200} and {110} growth faces (type B) in that of regime II. The transition of lateral habit causes a drastic change in the width of {110} growth faces; {110} growth faces are well developed in type B crystals while they cannot be observed and must be very small in type-A crystals. It has been shown that the growth regime of the small {110} growth face of type-A crystals must be in regime I; hence the regime I–II transition can be explained as the result of this change in lateral habit (width of the {110} growth face).     

Growth kinetics of single copper crystals: the concentration dependence

The growth of single copper crystals electrodeposited on a tungsten electrode is studied at different concentrations of copper ions in the electrolyte solution. Information is obtained on the diffusion coefficient of copper ions, the exchange current density at the crystal-solution phase boundary and the charge transfer coefficient at a constant temperature.     

Adsorption dynamics of water on Pt{110}-(1 x 2)

The dynamics of H(2)O adsorption on Pt{110}-(1 x 2) is studied using supersonic molecular beam and temperature programed desorption techniques. The sticking probabilities are measured using the King and Wells method at a surface temperature of 165 K. The absolute initial sticking probability s(0) of H(2)O is 0.54+/-0.03 for an incident kinetic energy of 27 kJmol. However, an unusual molecular beam flux dependence on s(0) is also found. At low water coverage (theta<1), the sticking probability is independent of coverage due either to diffusion in an extrinsic precursor state formed above bilayer islands or to incorporation into the islands. We define theta=1 as the water coverage when the dissociative sticking probability of D(2) on a surface predosed with water has dropped to zero. The slow falling H(2)O sticking probability at theta>1 results from compression of the bilayer and the formation of multilayers. Temperature programed desorption of water shows fractional order kinetics consistent with hydrogen-bonded islands on the surface. A remarkable dependence of the initial sticking probability on the translational (1-27 kJ/mol) and internal energies of water is observed: s(0) is found to be essentially a step function of translational energy, increasing fivefold at a threshold energy of 5 kJ/mol. The threshold migrates to higher energies with increasing nozzle temperature (300-700 K). We conclude that both rotational state and rotational alignment of the water molecules in the seeded supersonic expansion are implicated in dictating the adsorption process.     

Separation of Co(II) from dilute aqueous solutions by precipitate and adsorbing colloid flotation

Ion, precipitate and adsorbing colloid flotation of cobalt(II) have been investigated at different pH values, using N-dodecylpyridinium chloride (DPCl), A strong cationic surfactant, and sodium lauryl sulfate (NaLS), a strong anionic surfactant, as collectors. In case of adsorbing colloid flotation, hydrous manganese dioxide was used as an adsorbent. The precipitate flotation curves experimentally obtained with the two tested collectors were compared with the corresponding theoretical one calculated from the data published for Co(II) hydrolysis. The effects of the collector concentration, ageing of the water-MnO₂–Co(II) system, bubbling time period, cobalt(II) concentration and foreign salts on the percent removal of Co(II) by adsorbing colloid flotation using DPCl as collector were determined. Removals approaching 100% could be achieved under the optimum conditions.     

Copper(II) and nickel(II) complexes of pyruvaldehyde bis{N(3)-substituted thiosemicarbazones}

Copper(II) and nickel(II) complexes of pyruvaldehyde bis{N(3)-methyl-, bis{N(3)-ethyl-, bis{N(3)-dimethyl- and bis{piperidylthiosemicarbazone} have been prepared and studied spectroscopically. The four thiosemicarbazones have been characterized by their melting points, as well as i.r., electronic and n.m.r. (1H,13C) spectra. The four coordinate copper(II) complexes have been studied by e.s.r. spectroscopy, and the copper(II) and nickel(II) complexes by several of the spectroscopic techniques mentioned above. Upon formation of these complexes, loss of protons from each thiosemicarbazone moiety occurs, and the bis(thiosemicarbazones) coordinate to the metal centres as dianionic, tetradentate N2S2 ligands.     

Copper(II) and nickel(II) complexes of glyoxaldehyde bis{N(3)-substituted thiosemicarbazones}

Copper(II) and nickel(II) complexes of glyoxaldehyde bis{N(3)-methyl-, bis{N(3)-ethyl-, bis{N(3)-dimethyl-, bis{piperidyl- and bis{hexamethyleneiminylthiosemicarbazone} have been prepared and studied spectroscopically. The five bis(thiosemicarbazones) have been characterized by their melting points, as well as i.r., electronic and 1H-n.m.r. spectra. The four-coordinate copper(II) complexes have been studied by e.s.r. spectroscopy, and the copper(II) and nickel(II) complexes by a number of the spectroscopic techniques mentioned above. Upon formation of these complexes, loss of protons from each thiosemicarbazone moiety occurs, and the bis(thiosemicarbazones) coordinate to the metal centres as dianionic, tetradentate N2S2 ligands. This revised version was published online in June 2006 with corrections to the Cover Date.     

Syntheses and characterization of μ-Bis{N-(oxopropyl)-glycinamidato}-dicopper(II) and μ-Bis{n-(oxopropyl)-DL-alaninamidato}-dicopper(II)

Two new complexes, [Cu(OP-gld)]₂ and [Cu(OP-alad)]₂ (shown in Fig. 2) with a subnormal magnetic moment have been synthesized and characterized by means of analyses, magnetic susceptibility measurements, IR-, and electronic spectra, and conductivity measurement.     

Removal of Zn(II) from dilute aqueous solutions and radioactive process wastewater by foam separation

Ion, precipitate and adsorbing colloid flotations of zinc(II) from dilute aqueous solutions have been investigated over a wide pH range using the anionic surfactant Aerosol OT or the cationic collector cetyl pyridinium chloride. In case of adsorbing colloid flotation (ACF) iron oxyhydroxide and aluminium hydroxide were used, either separately or together, as coprecipitants. The precipitate flotation curves were compared with the corresponding theoretical one calculated from the data published for Zn(II) hydrolysis. In addition to the effect of pH on the percent removal the effects of collector concentration, ionic strength, bubbling time and metal ion concentration were investigated and the optimum conditions were established. High removals could be achieved especially with ACF. The results obtained are discussed with respect to the chemical state of zinc, the ionization behaviour of the collectors and properties of the coprecipitants. The developed ACF process was applied to the removal of⁶⁵Zn from radioactive process wastewater.     

AFM investigation of the {101} surface morphology of l-arginine trifluoroacetate (LATF) crystals

The {101} surface of l-arginine trifluoroacetate (LATF) crystals has been investigated by ex situ atomic force microscopy (AFM). The main step sources were observed in the form of growth spirals. The growth spirals are rounded and highly anisotropic. Microcrystals transferred from aggregates deposit at the step-edged on the facets. It is suggested that the microcrystals may lead to the formation of macrodefects during growth. Etching experiments reveal circular hollow cores, indicative of both screw dislocation growth, and negative crystals generated by further crystallization in the entrapped liquid inclusions are investigated.     

Electron spin-lattice relaxation of Cu(II) in Zn(II)-bis(diethyl-diselenocarbamate) single crystals

Using the pulse saturation method the spin-lattice relaxation rate T₁⁻¹ for Cu(II) in Zn(II)-bis(diethyl-diselenocarbamate) was measured in the temperature range 1.5 < T < 33 K. From the T-dependence of T₁⁻¹ the Debye temperature of the host crystal was obtained. The angular dependence of T₁⁻¹ as well as the influence of the hyperfine interaction on T₁⁻¹ are discussed.     

The role of210Pb in evaluating container adsorption of Pb(II) from dilute aqueous solutions

Solutions of Pb²⁺ at ppb to ppm levels were tagged with²¹⁰Pb and then counted from time to time over a period of one year to measure the extent of container adsorption. All count rates for samples which were acidified with HNO₃ were at least 90% of their initial values, even after one year of storage. Amber glass containers proved to be superior to polypropylene for 0.1 and 1.0 ppm Pb²⁺ solutions; but below 0.1 ppm, polypropylene was superior. For non-acidified samples, the count rate dropped rapidly within the first two months, and then declined more gradually thereafter, with polypropylene generally superior.     

Longitudinal growth of polymer crystals from flowing solutions V.: Structure and morphology of fibrillar polyethylene crystals

Summary Longitudinal fibrillar polyethylene crystals grown from xylene solutions subjected to simple shear flow have been investigated by various X-ray diffraction and electron microscopic techniques. The macrofibers with diameters in the micron range are composed of elementary fibrils of two basically different types. They may consist of either striated fibrils of the shishkebab type or smooth fibrils. The latter morphologies were obtained when the crystallization was carried out at temperatures above approximately 114 °C and the fibrillar crystals were allowed to grow longitudinally at the surface of the rotor of a Couette type instrument at a sufficiently high speed.The average spacings between the lamellae of the shish-kebabs as derived from the maximum in the small-angle X-ray scattering curve correspond remarkably well to the values obtained from transmission electron micrographs. The lateral dimensions of the elementary fibrils were acquired from equatorial line-broadening analysis of electron diffraction spots, wide-angle X-ray diffractograms, dark-field images and Guinier plots.They varied from 260 Å for fibrillar polyethylene crystals grown at 103 °C to approximately 150 Å for fibers formed at 118 °C The lateral crystallite size was also found to diminish at higher growth rates. Under the latter conditions the growth is accompanied by an extensive coil deformation as reflected by the presence of a considerable amount of the triclinic crystal modification.Dark-field electron microscopy indicates that the lengths of the crystallite blocks are of the order of 250–350 Å for fibers grown at 103 °C and 450 Å and longer for fibers formed at 118 °C. These values are in agreement with those obtained from the broadening of the (002) electron diffraction spots.

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Zusammenfassung Dieser Bericht befaßt sich mit der Untersuchung von longitudinalen Polyäthylen-Faserkristallen, gewachsen aus Xylollösungen in einer Scherströmung, mit Hilfe verschiedener Röntgen-Diffraktions- und elektronenmikroskopischer Techniken. Die Makrofasern mit Durchmessern von einigen Mikron enthalten Elementar-Fibrillen von 2 grundsätzlilch verschiedenen Typen. Sie enthalten entweder gestreifte Fibrillen, die wie Schaschlik-Strukturen erscheinen, oder glatte Fibrillen.Die letztgenannten glatten Fibrillen wurden erhalten, wenn die Kristallisation bei Temperaturen oberhalb ungefahr 114 °C ausgeführt wurde und die Faserkristalle die Möglichkeit hatten, longitudinal an der Oberfläche des Rotors eines Apparates vom Couette-Typ zu wachsen, wobei der Rotor genügend rasch rotierte.Der mittlere Abstand zwischen den Lamellen der Schaschlik-Struktur, berechnet aus dem Maximum der Weitwinkel-Streuungskurve, stand in sehr guter Übereinstimmung mit den Werten der elektronenmikroskopischen Beobachtungen im Durchlicht. Die lateralen Dimensionen wurden aus der Verbreiterung der Reflexe erhalten, aus Weitwinkel-Aufnahmen Bowie aus Dunkelfeld- und Guinier-Aufnahmen.Die Abstände waren 260 Å für Polyäthylen-Faserkristalle, gewachsen bei einer Temperatur von 103 °C, und ungefähr 150 Å für Fasern entstanden bei 118 °C. Die laterale Kristallitgröße verringerte sich bei höheren Wachstumsgeschwindigkeiten. Unter den letztgenannten Verhältnissen ist das Wachstum verbunden mit größerer Knäuelverformung, was sich durch die Anwesenheit eines erheblichen Anteils von trikliner Kristallmodifikation bemerkbar macht.Dunkelfeld-elektronenmikroskopische Untersuchung hat gezeigt, daß die Länge der Kristallanteile von einer Größenordnung von 250–350 Å für Fasern, gewachsen bei 103 °C, and 450 Å und länger für Fasern entstanden bei 118 °C ist. Diese Werte stehen in guter Übereinstimmung mit den Werten, erhalten aus Verbreiterung der (002) Elektronen-Beugungsbilder.

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With 13 figures and 2 tables     

Morphology and structure of nylon‐2,14 single crystals from dilute solution

A perfect single crystal of nylon‐2,14 was prepared from 0.02% (w/v) 1,4‐butanediol solution by a “self‐seeding” technique and isothermal crystallization at 120 and 145 °C. The morphology and structure features were examined by transmission electron microscopy with both image and diffraction modes, atomic force microscopy, and wide‐angle X‐ray diffraction (WAXD). The nylon‐2,14 single crystal grown from 1,4‐butanediol at 145 °C inhabited a lathlike shape with a lamellar thickness of about 9 nm. Electron diffraction and WAXD data indicated that nylon‐2,14 crystallized in a triclinic system with lattice dimensions a = 0.49 nm, b = 0.51 nm, c = 2.23 nm, α = 60.4°, β = 77°, and γ = 59°. The crystal structure is different from that of nylon‐6,6 but similar to that of other members of nylon‐2Y. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1913–1918, 2002     

Reactivity and spectroscopy of the {Ru(DMAP)5} fragment: an {Ru(NH3)5} analogue

Reaction of trans-Ru(DMSO)4Cl2 with DMAP (DMAP = 4-dimethylaminopyridine) yields the yellow [Ru(DMAP)6](2+) cation in good yield. The crystal and molecular structure of [Ru(DMAP)6]Cl2.6CH3CH2OH was determined by X-ray diffraction methods. The complex crystallizes in the trigonal R3 space group with a = b = 16.373(1), c = 20.311(1) A, gamma = 120 degrees , and Z = 3 molecules per unit cell. The reaction of [Ru(DMAP)6](2+) in aerobic water gives the red [Ru(III)(DMAP)5(OH)](2+) cation. This complex shows a chemical behavior similar to [Ru(III)(NH3)5Cl](2+) and allows the preparation of a family of [Ru(DMAP)5L](n+) complexes. Their electronic properties indicate that the {Ru(II)(DMAP)5} fragment is a weaker pi-donor than {Ru(II)(NH 3)5}. Our density functional theory (DFT) calculations show that in {Ru(II)(DMAP)5} the DMAP ligands can compete for the pi electron density of the ruthenium making the fragment a weaker pi-donor.     

Molecular ordering and adsorbate induced faceting in the Ag{110}-(S)-glutamic acid system

The adsorption of the amino acid, (S)-glutamic acid, was investigated on Ag{110} as a function of coverage and adsorption temperature using the techniques of scanning tunneling microscopy, low energy electron diffraction, and reflection absorption infrared spectroscopy. In the monolayer, (S)-glutamic acid was found to adsorb predominantly in the anionic glutamate form. Several discrete ordered adlayer structures were observed depending on preparation conditions. In addition, (S)-glutamic acid was found to induce both one- and two-dimensional faceting of the Ag{110} surface. In some cases, evidence was found that the 2-D faceting involved the creation of a chiral facet distribution. A comparison is made of the Ag/(S)-glutamic acid system with analogous studies of amino acids on Cu.