Lamellar Growth Research Articles

Interphase anisotropy effects on lamellar eutectics: a numerical study.

In directional solidification of binary eutectics, it is often observed that two-phase lamellar growth patterns grow tilted with respect to the direction z of the imposed temperature gradient. This crystallographic effect depends on the orientation of the two crystal phases α and β with respect to z. Recently, an approximate theory was formulated that predicts the lamellar tilt angle as a function of the anisotropy of the free energy of the solid(α)-solid(β) interphase boundary. We use two different numerical methods-phase field (PF) and dynamic boundary integral (BI)-to simulate the growth of steady periodic patterns in two dimensions as a function of the angle θ(R) between z and a reference crystallographic axis for a fixed relative orientation of α and β crystals, that is, for a given anisotropy function (Wulff plot) of the interphase boundary. For Wulff plots without unstable interphase-boundary orientations, the two simulation methods are in excellent agreement with each other and confirm the general validity of the previously proposed theory. In addition, a crystallographic "locking" of the lamellae onto a facet plane is well reproduced in the simulations. When unstable orientations are present in the Wulff plot, it is expected that two distinct values of the tilt angle can appear for the same crystal orientation over a finite θ(R) range. This bistable behavior, which has been observed experimentally, is well reproduced by BI simulations but not by the PF model. Possible reasons for this discrepancy are discussed.

Eutectic Structures Competition in the Stripes Strengthening the (Zn) – Single Crystal

Abstract Some eutectic stripes have been generated in a hexagonal (Zn) - single crystal. The stripes are situated periodically with the constant interstripes spacing. The eutectic structure in the stripes consists of strengthening inter-metallic compound, Zn16Ti, and (Zn) - solid solution. The rod-like irregular eutectic structure (with branches) appears at low growth rates. The regular lamellar eutectic structure is observed at middle growth rates. The regular rod-like eutectic structure exists exclusively in the stripes at some elevated growth rates. A new thermodynamic criterion is recommended. It suggests that this eutectic regular structure is the winner in a morphological competition for which the minimum entropy production is lower. A competition between the regular rod-like and the regular lamellar eutectic growth is described by means of the proposed criterion. The formation of branches within irregular eutectic structure is referred to the state of marginal stability. A continuous transitions from the marginal stability to the stationary state are confirmed by the continuous transformations of the irregular eutectic structure into the regular one.

Molecular self-assembly of nylon-12 nanorods cylindrically confined to nanoporous alumina.

Molecular self-assembly of nylon-12 rods in self-organized nanoporous alumina cylinders with two different diameters (65 and 300 nm) is studied with transmission electron microscopy (TEM) and wide-angle X-ray diffraction (WAXD) in symmetrical reflection mode. In a rod with a 300 nm diameter, the tendency of the hydrogen-bonding direction of a γ-form crystal parallel to the long axis of the rod is not clear because of weak two-dimensional confinement. In a rod with a diameter of 65 nm, the tendency of the hydrogen-bonding direction of a γ-form crystal parallel to the long axis of the rod is more distinct because of strong two-dimensional confinement. For the first time, selected-area electron diffraction (SAED) is applied in a transmission electron microscope to a polymer nanorod in order to determine the hydrogen-bond sheet and lamellar orientations. Results of TEM-SAED and WAXD showed that the crystals within the rod possess the γ-form of nylon-12 and that the b axis (stem axis) of the γ-form crystals is perpendicular to the long axis of the rod. These results revealed that only lamellae with 〈h0l〉 directions are able to grow inside the nanopores and the growth of lamellae with 〈hkl〉 (k ≠ 0) directions is stopped owing to impingements against the cylinder walls. The dominant crystal growth direction of the 65 nm rod in stronger two-dimensional confinement is in between the [-201] and [001] directions due to the development of a hydrogen-bonded sheet restricted along the long axis of the rod.

Acquired heterotopic ossification in hips and knees following encephalitis: case report and literature review

BackgroundHeterotopic ossification (HO) is a rare and potentially detrimental complication of soft-tissue trauma, amputations, central nervous system injury (traumatic brain injuries, spinal cord lesions, tumors, encephalitis), vasculopathies, arthroplasties and burn injury, characterized by lamellar bone growth in non-osseous tissues such as the muscle and the joint capsule. Heterotopic ossification associated with encephalitis is rare and the occurrence of excessive, symptomatic heterotopic ossification around bilateral hips and bilateral knees is rarely described in the literature.Case presentationWe present a 47-year-old man with heterotopic ossification in the bilateral hips and bilateral knees that prevented him from walking after being attacked by encephalitis as the case study. He developed severe pain and significantly impaired range of motion of bilateral hips and bilateral knees. Research so far revealed that the management of heterotopic ossification is controversial. After requiring revision surgery resection of heterotopic ossification, reconstruction of the medial collateral ligament and adjunctive pharmacotherapy of 200 mg Celecoxib for 8 weeks after operation, he regained mobility of his joints. On review of X-ray, there was no recurrence of HO and no loosening of rivets which were used in the reconstruction of medial collateral ligament.ConclusionHeterotopic ossification in the bilateral hip joints and bilateral knee joints associated with encephalitis have never been reported previously. Daily functions of heterotopic ossification patients can be hampered by pain, inflammation, reduced mobility, the loss of normal posture and other complications. Further studies of presumptive root causes, the early diagnosis, preventability and optimal therapeutic measures for heterotopic ossification following encephalitis are required. Different patient should be managed with different appropriated protocol based on the risk of individual patient and the institutional experience.

New insight into lamellar branching of β-nucleated isotactic polypropylene upon melt-stretching: WAXD and SAXS study

Polymer processing generally plays a crucial role in determining the development of microstructure in the fabricated product. In this paper, isotactic polypropylene (iPP) containing 0.1 wt% β-nucleating agent was extruded via a slit die and immediately melt-stretched upon various stretching rates (SR) at the die exit. The microstructure of β-nucleated iPP samples was investigated using two-dimensional wide-angle X-ray diffraction and small-angle X-ray scatterings (2D-WAXD/SAXS) measurements. It is observed that, no matter what SR is, lamellar branching of β-form crystal is formed in melt-stretched samples, which is scarcely reported in open literatures. A method is proposed to calculate the crystallinity of daughter lamellae in β-crystal (X β−D). It is found that X β−D decreases with increasing SR, indicating that lamellar branching of β-form crystal is restrained by higher SR. Such case should be attributed to the denser-oriented structures (e.g., shish) induced by higher SR, leaving a confined space between adjacent-oriented structures for the growth of daughter lamellae.

Kinetics of triple-junctions in eutectic solidification: a sharp interface model

The kinetics of triple-junctions (TJs) in eutectic solidification is modeled by the thermodynamic extremum principle (TEP). It consists of two parts. First, TJs as the interaction of interfaces follow the interface kinetics according to which the temperature and concentration at the TJs are determined. This interface part of TJ kinetics is closely related to the eutectic point in the kinetic phase diagram. Second, TJs have their specific kinetics according to which their morphology (e.g., the contact angles in two dimensions) is determined. Using a new solution of solute diffusion in liquid, the TJ kinetics is incorporated into the current lamellar eutectic growth model. The model is applicable to the concentrated alloy systems and can be extended to any kind of eutectics. Simulation results of the rapid solidification of a lamellar Ni5Si2–Ni2Si (γ–δ) eutectic show that both parts of TJ kinetics can play important roles in eutectic solidification and need to be considered to improve the current eutectic theory.

Uniform to accelerated crystal twisting transition in deuterate polyethylene/poly(ethylene-alt-propylene) blend films

A uniform to accelerated crystal twisting transition is observed in deuterate polyethylene/poly(ethylene-altpropylene) (d-PE/PEP) blend films. And the band period is a function of initial d-PE concentration, quench depth and annealing time of phase separation. As Keith and Padden suggested, twisting of lamella is due to the unbalanced stress on its both sides, which can supply a satisfying explanation to banded spherulites formed in homogeneous systems. When it comes to d-PE/PEP blend system, in homogeneous 99% d-PE/PEP (weight fraction of d-PE) blend film, the formation of banded spherulite is observed as a result of uniform twisting of ribbon like d-PE lamellae along the radial direction. With the amorphous PEP piling up, it transfers into accelerated edge-on to flat-on twisting due to crystallization assisted phase separation. The mechanism can be interpreted as following: d-PE molecules must inter-diffuse to the twisting growth front to continue the secondary nucleation and growth process. Meanwhile, the amorphous PEP molecules are rejected and accumulated at the twisting growth front. Once the d-PE lamella begins to twist because of unbalanced stress on both sides, the accumulated rubber phase at the growth front strengthens the unbalance and accelerates the edge-on to flat-on twisting. The concentration wave propagates further away with constant speed, and leads to concentric ring pattern with periodic nonuniform twisting along the radial direction. Since this is a kinetic effect, the band period can be controlled through initial d-PE concentration, quench depth and annealing time of phase separation. Our result shows that crystallization assisted phase separation can modify lamella growth kinetic pathway, thereby assisting concentric ring pattern formation.

Interconnection of thermal parameters, microstructure, macrosegregation and microhardness of unidirectionally solidified Zn-rich Zn–Ag peritectic alloys

In this work, the microstructural evolution of Zn–3.2wt%Ag (hypoperitectic) and Zn–8wt%Ag (hyperperitectic) alloys during transient unidirectional solidification is investigated. The experimental results include solidification thermal parameters such as the growth rate (VL), thermal gradient (GL) and tip cooling rate (Ṫ), which are related to the microstructural interphase spacing (λ) by proposed experimental growth laws. It is shown that, the classical lamellar eutectic growth law λ2V=constant, applies to the growth of the peritectic Zn–Ag alloys examined, despite the different values of the constant associated with each alloy composition. In contrast, it is shown that identical functions of the form λ=constant (GL)−14 (VL)−1/8, and λ=constant (Ṫ-1/3) can be applied to both alloys examined. Positive solute macrosegregation was observed in regions close to the bottom of the castings. The dependence of microhardness (HV) on the length scale of the microstructures (including that of a single phase Zn 0.8wt%Ag alloy: λC− cellular spacing) is examined. An experimental Hall–Petch type power law is proposed relating the resulting microhardness to λC for the single phase alloy, and despite the segregation profiles and the alloying differences of the hypoperitectic and hyperperitectic alloys, the average microhardnesses of these alloys is shown to be essentially constant and similar along the castings lengths.

“Raft” Formation by Two‐Dimensional Self‐Assembly of Block Copolymer Rod Micelles in Aqueous Solution

Block copolymers can form a broad range of self-assembled aggregates. In solution, planar assemblies usually form closed structures such as vesicles; thus, free-standing sheet formation can be challenging. While most polymer single crystals are planar, their growth usually occurs by uptake of individual chains. Here we report a novel lamella formation mechanism: core-crystalline spherical micelles link up to form rods in solution, which then associate to yield planar arrays. For the system of poly(ethylene oxide)-block-polycaprolactone in water, co-assembly with homopolycaprolactone can induce a series of morphological changes that yield either rods or lamellae. The underlying lamella formation mechanism was elucidated by electron microscopy, while light scattering was used to probe the kinetics. The hierarchical growth of lamellae from one-dimensional rod subunits, which had been formed from spherical assemblies, is novel and controllable in terms of product size and aspect ratio.

“Raft” Formation by Two‐Dimensional Self‐Assembly of Block Copolymer Rod Micelles in Aqueous Solution

AbstractBlock copolymers can form a broad range of self‐assembled aggregates. In solution, planar assemblies usually form closed structures such as vesicles; thus, free‐standing sheet formation can be challenging. While most polymer single crystals are planar, their growth usually occurs by uptake of individual chains. Here we report a novel lamella formation mechanism: core‐crystalline spherical micelles link up to form rods in solution, which then associate to yield planar arrays. For the system of poly(ethylene oxide)‐block‐polycaprolactone in water, co‐assembly with homopolycaprolactone can induce a series of morphological changes that yield either rods or lamellae. The underlying lamella formation mechanism was elucidated by electron microscopy, while light scattering was used to probe the kinetics. The hierarchical growth of lamellae from one‐dimensional rod subunits, which had been formed from spherical assemblies, is novel and controllable in terms of product size and aspect ratio.

Morphology and formation mechanism of pyrite induced by the anaerobic oxidation of methane from the continental slope of the NE South China Sea

In order to understand the response of authigenic pyrite to gas hydrate geo-systems, pyrite tubes or rods at the sulfate–methane transition (SMT) zone of core GC10 from the northern continental slope of the South China Sea (SCS) were investigated. In situ X-ray diffraction (XRD) results show that the pyrite tube consists of pyrite micro-crystals with trace amount of graphite in the inner tube. Scanning electron microscope (SEM) observations of pyrite tubes indicate various aggregations in the form of framboidal, euhedral, and colloidal pyrite microcrystals. Typical framboidal pyrite is considered as packing of octahedral microcrystals. Interestingly, many framboids in the tubes consist of round or irregular microcrystals and have an outer crust that consists of secondary pyrite. The size of the framboids in the inner wall of the tube is larger than that in the middle wall or foraminifer-filled pyrite. High-resolution transmission electron microscopic (HRTEM) images show marcasite lamellae defects in the spherulitic pyrite crystals, which reveal different solution conditions during the pyrite precipitation. Nano-foil-like graphitic carbon was observed to be closely associated with the pyrite spherules. The occurrence of both marcasite layers and nano-foil-like graphitic carbon suggest that the migration of methane from deep sediment. It is suggested that the formation of pyrite serves as a catalyst during the reaction from methane to elemental carbon under the anaerobic oxidation of methane. Meanwhile, this reaction results in local acidification of the solution inside the pyrite tubes, which favors marcasite lamellae growth on the host pyrite substrate.

Ultrasonic decrosslinking of crosslinked high‐density polyethylene: Effect of screw design

ABSTRACTThe effect of screw design on decrosslinking of the crosslinked high‐density polyethylene (XHDPE) by means of ultrasonic twin‐screw extruder with two screw configurations is investigated. Die pressure and ultrasonic power consumption during extrusion are recorded. Swelling characteristics, rheological properties, thermal analysis, scanning electron microscopy, and tensile properties are used to investigate the structure–property relationship of decrosslinked XHDPE. It is found that the screw configuration with conveying elements and reverse conveying elements (decrosslinking screws) is an effective means to reduce the gel fraction and crosslink density of decrosslinked XHDPE and significantly improve its processibility. Rheological properties of decrosslinked XHDPE are correlated with structural changes occurring during ultrasonic decrosslinking. The presence of the highly branched sol in decrosslinked XHDPE is revealed through measurements of the activation energy for flow. Comparison of morphologies of the lamellar structure of HDPE, XHDPE, and decrosslinked XHDPE reveals that the presence of the crosslink network inhibits the lamella growth. Significant improvements in the mechanical performance of decrosslinked XHDPE are obtained by using decrosslinking screws. The molecular structure and morphology of the lamellar structure of decrosslinked XHDPE are used to explain the processing–solid‐state property relationship. The measured results on the gel fraction and crosslink density are compared with those of numerical simulations. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 40680.

Global instabilities of lamellar eutectic growth in directional solidification

The present paper is concerned with the global instability mechanisms for the basic steady state of lamellar eutectic growth with curved and tilted interface affected by the triple point. We solve the related linear eigenvalue problem (EVP) by using the analytical approach for the case that the Peclet number is small and the segregation coefficient parameter κ is close to the unit. It is found that the system involves two types of global instability mechanisms: the ‘exchange of stability’ invoked by the non-oscillatory, unstable modes and the global wave instabilities invoked by four types of oscillatory unstable modes, namely (AA)-, (SS)-, (AS)- and (SA)-mode. The quantization conditions for these modes are derived, the neutral curves for these global instabilities on the parameters plane are calculated. The stability criterion yields the range of the interlamellar spacing and explains the interfacial pattern transitions observed in the experiments.

Solvent micro-evaporation and concentration gradient synergistically induced crystallization of poly(l-lactide) and ring banded supra-structures with radial periodic variation of thickness

The crystalline morphology and structure of poly(L-lactide) (PLLA) in a PLLA film–chloroform system were investigated by means of wide angle X-ray diffraction (WAXD), polarized optical microscopy (POM) and atomic force microscopy (AFM). Birefringent and nonbirefringent ring banded supra-structures with radial periodic variation of thickness were obtained, which were induced by micro-evaporation of solvents and concentration gradient of PLLA. The ring banded morphologies consisted of multilayer lamellar crystals, which is a manifestation of alternating ridge and valley bands of periodic variation of thicknesses along the radial direction. The formation of the ring banded supra-structures is associated with diffusion and crystal growth induced periodic variation of concentration gradient, which is attributed to diffusion-related rhythmic growth and the competition between diffusion of polymer segments and growth of crystal lamellae. The mechanism of such banded-ring formation was explored on the basis of rhythmic growth resulting from non-linear diffusion.

Lamellar to Rod Eutectic Transition in the Hypereutectic Nickel-aluminum Alloy

Directional solidification experiments were carried out on the hypereutectic Ni-25 at.% Al alloy to examine the effect of growth velocity on the eutectic microstructure. The growth velocity was varied from 1 to 20μm/s at a constant temperature gradient of 10.0K/mm. The microstructural observations of unidirectionally solidified samples show that the lamellar eutectic growth was observed in the sample solidified at a constant velocity of 1μm/s and the rod eutectic growth at velocities higher than 10μm/s. A microstructural transition from lamellar to rod eutectics was achieved at the intermediate velocity. The lamellar to rod eutectic transition was shown to result from the compositional change due to the presence of strong convection in the melt. The undercooling-spacing curves showed that the average eutectic spacings for the lamellar and the rod structures were 1.6 times larger than that in the minimum undercooling for a given velocity.

Global steady state solutions for lamellar eutectic growth in directional solidification

The present paper investigates steady eutectic growth with the isotropic surface tension by using the analytical approach. We consider the case that Peclet number ϵ is small and the segregation coefficient κ is close to the unit, and obtain a family of the global steady state solutions with two free parameters: the Peclet number ϵ and tilt angle φ, which may describe the basic states of both tilted and non-tilted eutectic growth. It is found that due to the singularity of the triple point in the system, there is a thin boundary layer in the vicinity of the triple point, where the curvature and the temperature of interface vary drastically. The quantitative comparisons between the theoretical predictions with recent available experimental data are made with no adjustable parameter. The agreements are very good.

Effect of processing parameters on the morphology development during extrusion of polyethylene tape: An in-line small-angle X-ray scattering (SAXS) study

The in-line development of crystalline morphology and orientation during melt extrusion of low density polyethylene (LDPE) tape at nil and low haul-off speeds has been investigated using Small-Angle X-Ray Scattering (SAXS). The processing parameters, namely haul-off speed and distance down the tape-line have been varied and the resulting crystalline morphology is described from detailed analysis of the SAXS data. Increasing haul-off speed increased orientation in the polymer tape and the resulting morphology could be described in terms of regular lamellar stacking perpendicular to the elongation direction. In contrast, under nil haul-off conditions the tape still showed some orientation down the tape-line, but a shish-kebab structure prevails. The final lamellae thickness ( ∼50 Å) and bulk crystallinity (∼20%), were low at, for all processing conditions investigated, which is attributed to the significant short-chain branching in the polymer acting as point defects limiting lamellae crystal growth.

Lamellar coupled growth in the neopentylglycol-(D)camphor eutectic

Lamellar eutectic growth was investigated in the transparent organic alloy neopentylglycol-(D)camphor of eutectic composition (NPG-45.3wt% DC) using bulk (3D) and thin (2D) samples. Two types of eutectic grains were observed in the polycrystalline samples, either with lamellae well aligned to the direction of solidification or inclined at an angle of 21.5±1.5°. The well aligned grains were used for determining lamellar spacing as function of growth velocity V and temperature gradient G. Based on these data the Jackson–Hunt constant was evaluated to be KJH=1.60±0.15μm3s−1. For low growth velocity experiments the contact angles for (DC) and (NPG) lamellae at eutectic triple junctions were also evaluated, being θ(DC)=50.9±4.1° and θ(NPG)=41.8±4.7°, respectively. Using these values, as well as phase diagram data and the Gibbs–Thomson coefficients, the chemical coefficient of diffusion of (D)camphor in the eutectic liquid at eutectic temperature 53°C was estimated to be DL=97±15µm2s−1.

Molecular dynamics and crystallization precursors in polylactide and poly(lactide)/CNT biocomposites in the insulating state

The early stages of the cold crystallization process and the formation of a rigid amorphous phase as seen by the dielectric response of polylactide, PLA, and composites polylactide/carbon nanotubes, PLA/CNT, are studied here by broadband dielectric spectroscopy for CNT concentrations below percolation. The presence of precursors during the nucleation and crystallization process is demonstrated by the existence of a time shift between the decline in the number of mobile segments and the growth of a 3D ordered phase as seen by variable temperature wide angle X-ray scattering measurements. Also, the loss of the mobile amorphous phase is not justified by the slow lamellar growth in identical conditions. The variation of the molecular dynamics, either for short range reorientations or cooperative motions, is followed in both amorphous and semicrystalline states. The changes observed in the composites PLA/CNT show a moderate heterogeneous nucleating effect of the nanofiller and a sensitivity of the three subglass transitions to the chain ordering. The relaxation parameters of the segmental relaxation are not very sensitive to the presence either of lamellae or of the nanofiller.

First carbon ring closures started by the combustive radical addition of propargyl to butadiyne. A theoretical study

Formation of the first ring structure from small aliphatic molecules is often regarded as the rate-determining step (and in any case as a step of paramount importance) in the combustive growth of larger aromatic systems and soot lamellae. Among possible reactions able to start off this process, the radical addition of the propargyl radical to butadiyne (diacetylene) has been recently studied theoretically [G. da Silva, A. Trevitt, Phys. Chem. Chem. Phys. 13 (2011) 8940] and shown to lead preferentially to a 5-membered ring intermediate. The same reaction is here addressed focusing instead on the possible formation of 6-membered rings. The large variety of partially intertwined reaction pathways is the basis for a subsequent RRKM study (carried out at different combustion temperatures). It confirms, on one hand, the favored formation of fulvenallenyl radical indicated by da Silva and Trevitt, but also indicates the possible formation of six-membered cyclic systems as minor products. In particular, at high pressure, six-membered ring system yields are very low, but at lower pressures a more significant yield of six-membered ring product is predicted.