Herman's Orientation Parameter Research Articles

Coaxial Wet Spinning of Boron Nitride Nanosheet-Based Composite Fibers with Enhanced Thermal Conductivity and Mechanical Strength

HighlightsA core-sheath structured coaxial composite fiber with highly aligned and densely stacked boron nitride nanosheets arrangements in the sheath was successfully fabricated.The coaxial fibers have an ultrahigh axial Herman orientation parameter of 0.81, thermal conductivity of 17.2 W m−1 K−1, and tensile strength of 192.5 MPa.The coaxial fibers exhibit intensively potential applications in the wearable thermal management textile.

Degree of Orientation in Liquid Crystalline Elastomers Defines the Magnitude and Rate of Actuation

The anisotropy of liquid crystalline elastomers (LCEs) is derived from the interaction-facilitated orientation of the molecular constituents. Here, we correlate the thermomechanical response of a series of LCEs subjected to mechanical alignment to measurements of the Hermans orientation parameter. The LCEs were systematically prepared with varying concentrations of liquid crystalline mesogens, which affects the relative degree of achievable order. These compositions were subject to varying degrees of mechanical alignment to prepare LCEs with orientations that span a wide range of orientation parameters. The stimuli-response of the LCEs indicates that the liquid crystalline content defines the temperature of actuation, whereas the orientation parameter of the LCE is intricately correlated to both the total actuation strain of the LCE as well as the rate of thermomechanical response.

Improved alignment and stress transfer in CNT fibre fabrics studied by in situ X-ray and Raman during wet-drawing

Translating the superlative mechanical properties of nanocarbons to the scale of structural components requires assembling them into highly aligned networks with uniform internal stress transfer. Continuous, non-woven fabrics are produced by winding multiple filaments of carbon nanotube fibres (CNTF) directly spun from the gas phase. The CNTF fabrics are drawn by stretching in regular solvents, which increases specific tensile strength to 1.2 GPa/SG and modulus to 44 GPa/SG, reaching ∼70% the strength and ∼50% modulus of the single filament. Tensile measurements of misaligned CNTF fabrics soaked in solvents show an increased strain-to-break, a large drop in tensile force, and shear-induced local deformation, analogous to a polymer wet-drawing process. In-situ small-angle X-ray scattering during wet-drawing shows a progressive and transient increase in porosity, attributed to the separation of adjacent bundles “wedged” by the ingress of solvent when the fabric is under load. Wet-drawing increases degree of alignment, reaching Herman's orientation parameter values <P2> = 0.54 and a narrower distribution of local alignment. Maps of the downshift of 2D Raman band during tensile deformation confirm a more homogeneous spatial distribution of local moduli after wet-drawing CNTF fabrics, evidencing more cooperative loading and stress transfer. Tensile mechanical properties of fabrics aligned after wet-drawing can be successfully described by the uniform stress transfer model.

Ultraflexible polyamide-imide films with simultaneously improved thermal conductive and mechanical properties: Design of assembled well-oriented boron nitride nanosheets

The highly thermally conductive yet electrically insulating polymeric materials are exhibiting tremendous potential for thermal management materials. However, the practical application of these materials is restrained by the limited thermal conductivity (TC) and deterioration of mechanical properties. In this work, an ultraflexible polyamide-imide (PAI) film with a sandwich-like structure composed with assembled well-oriented functionalized boron nitride nanosheets (FBN) by facile layer-by-layer solution-coating strategy is constructed. The design of the layered structure and highly oriented arrangement of interconnected FBN (Herman's orientation parameter ƒ up to 0.847) endows the obtained PAI composite film with super-flexibility, ultrahigh in-plane thermal conductivity (λ//), superior thermal transfer capability (ΔTmax = 24.4 °C) and excellent electrical insulation performance. The PBP composite film reaches an ultrahigh λ//of 45.7 W m−1 K−1 with only 23 wt% FBN loading and exhibits a remarkable TC enhancement factor over 23 because of the more continuous phonon transfer networks that constructed by interconnected well-oriented FBN which could effectively suppress the phonon scattering. Furthermore, the mechanical properties of the layered composite film (PB4P) exhibit noteworthy enhancement compared with uniform PBN composite film, in which the tensile strength is increased by 110% and toughness enhancement is 329%. Meaningfully, our fabrication strategy has the advantage of simplicity and adaptability for commercial amplification. The composite film developed in this work provides a promising prospect for the thermal management system of modern power electronic devices.

Orientation-Dependent Host-Dopant Interactions for Manipulating Charge Transport in Conjugated Polymers.

Molecular orientation plays a critical role in controlling carrier transport in organic semiconductors (OSCs). However, this aspect has not been explored for surface doping of OSC thin films. The challenge lies in lack of methods to precisely modulate relative molecular orientation between the dopant and the OSC host. Here, the impact of molecular orientation on dopant-host electronic interactions by large modulation of conjugated polymer orientation via solution coating is reported. Combining synchrotron-radiation X-ray measurements with spectroscopic and electrical characterizations, a quantitative correlation between doping-enhanced charge carrier mobility and the Herman's orientation parameter is presented. This direct correlation can be attributed to enhanced charge-transfer interactions at host/dopant interface with increasing face-on orientation of the polymer. These results demonstrate that the surface doping effect can be fundamentally manipulated by controlling the molecular orientation of the OSC layer, enabling optimization of carrier transport.

Absorbent Filaments from Cellulose Nanofibril Hydrogels through Continuous Coaxial Wet Spinning.

A continuous and scalable method for the wet spinning of cellulose nanofibrils (CNFs) is introduced in a core/shell configuration. Control on the interfacial interactions was possible by the choice of the shell material and coagulant, as demonstrated here with guar gum (GG) and cellulose acetate (CA). Upon coagulation in acetone, ethanol, or water, GG and CA formed supporting polymer shells that interacted to different degrees with the CNF core. Coagulation rate was shown to markedly influence the CNF orientation in the filament and, as a result, its mechanical strength. The fastest coagulation noted for the CNF/GG core/shell system in acetone led to an orientation index of ∼0.55 (Herman’s orientation parameter of 0.40), Young’s modulus of ∼2.1 GPa, a tensile strength of ∼70 MPa, and a tenacity of ∼8 cN/tex. The system that underwent the slowest coagulation rate (CNF/GG in ethanol) displayed a limited CNF orientation but achieved an intermediate level of mechanical resistance, owing to the strong core/shell interfacial affinity. By using CA as the supporting shell, it was possible to spin CNF into filaments with high water absorption capacity (43 g water/g dry filament). This was explained by the fact that water (used as the coagulant for CA) limited the densification of the CNF core structure, yielding filaments with high accessible area and pore density.

Phase Separation and Stack Alignment in Aqueous Cellulose Nanocrystal Suspension under Weak Magnetic Field.

Isotropic-nematic (I-N) transitions in cellulose nanocrystal (CNC) suspension and self-assembled structures in the isotropic and nematic phases were investigated using scattering and microscopy methods. A CNC suspension with a mass fraction of 7.4% spontaneously phase separated into an isotropic phase of 6.9% in the top layer and a nematic phase of 7.9% in the bottom layer. In both the phases, the CNC particles formed stacks with an interparticle distance being of ≈37 nm. One-dimensional small-angle neutron scattering (SANS) profiles due to both phases could be fitted using a stacking model considering finite particle sizes. SANS and atomic force microscopy studies indicate that the nematic phase in the bottom layer contains more populations of larger particles. A weak magnetic field of ≈0.5 T was able to induce a preferred orientation of CNC stacks in the nematic phase, with the stack normals being aligned with the field (perpendicular to the long axis of CNC particles). The Hermans orientation parameter, ⟨ P2⟩, was ≈0.5 for the nematic phase; it remained unchanged during the relaxation process of ≈10 h. The fraction of oriented CNC populations decreased during the relaxation; dramatic decrease occurred in the first 3 h. The top layer remained isotropic in the weak field. Polarized microscopy studies revealed that the nematic phase was chiral. Adjacent particles in a stack form a twisting angle of ≈0.6 °, resulting in a helix pitch distance of ≈22 μm.

Hierarchical structure of MWCNT reinforced semicrystalline HDPE composites: A contrast matching study by neutron and X-ray scattering

Combining neutron and X-ray scattering (SANS, SAXS, and WAXD) as the contrast matching probes, the hierarchical structures of the multi-wall carbon nanotubes/high density polyethylene (MWCNTs/HDPE) composites (0.1–2.0 wt%) have been studied. SANS measurement avoided the correlation peak associated to the semicrystalline nature of HDPE from SAXS, and the passible scattering from the stretch induced voids. Benefitting from SANS data, the power law (α) taking the flexible cylinder suggested that whole MWCNTs in the unstretched composites follow a self-avoiding random walk (α ≈ 1.67). SANS data suggest a hollow flexible cylinder structure with outer and inner diameters (core-shell-like cross section) of the scatterers as ca. 12.6 nm and 4.1 nm, while the Kuhn length is about 43.0 nm. Tensile test displayed improved mechanical properties. Interestingly, the Hermans orientation parameter (f) of HDPE crystals (fc) in the stretched composites are around a plateau ca. 0.96 initially, while decreased remarkably to 0.776 when the fraction is further increased to 2.0 wt%. f obtained by SANS showed a similar tendency (decreased from 0.756 to 0.572). Combining all the results along with differential scanning calorimetry (DSC) measurement, a mechanism of adhered crystals on the surface of MWCNTs and a reinforcement model are proposed.

Large-scale parallel alignment of platelet-shaped particles through gravitational sedimentation.

Parallel and concentric alignment of microscopic building blocks into several orders of magnitude larger structures is commonly observed in nature. However, if similarly aligned structures are artificially produced their thickness is generally limited to just about one or two orders of magnitude more than the dimensions of the smallest element. We show that sedimentation provides a promising approach to manufacture solid materials consisting of well-aligned platelet-shaped particles while being more than 30 000 times thicker than the individual particle. Such sediments contain up to 28 vol% of particles without any further treatment and can be densified to 67 vol% particle fraction by subsequent unidirectional pressing. The degree of orientation of the platelet-shaped particles within the sediments was tracked by high-energy X-ray diffraction measurements. The Hermans orientation parameter, a statistical measure of the quality of alignment, was determined to be 0.63 ± 0.03 already for as-sedimented samples while the standard deviation of the orientation distribution of particles, another measure of average misalignment, was found to be (21.5 ± 1.4)°. After pressing, these values further improved to (0.81 ± 0.01) and (14.6 ± 0.4)°, respectively. Such quality of alignment competes with, if not even exceeds, values reported in the literature.

Effects of glow-discharge nitrogen-plasma on the linear birefringence of polyester sheets

A simple white light interferometric method is used to study the effects of plasma on the steady-state linear birefringence of polyester sheet films. Glow-discharge nitrogen-plasma of power 13 W with nine different exposure times from 0 to 25 min is applied to films of 0.22 mm thickness. The relationship between the linear birefringence and some atomic parameters is derived theoretically and tested experimentally. Effects on the linear birefringence, the linear retardance and Herman's orientation parameter are investigated. The increase of plasma exposure time produces an increase in the linear birefringence and Herman's orientation parameter. Characterization of plasma-treated and plasma-untreated polyester samples have been thoroughly examined using Fourier transform infrared (FTIR) spectroscopy. It is noted that no new bands have appeared after treatment for all the tested samples at different time intervals. There is an increase in intensity and band definition, and a shift of some bands that were already present in the spectrum of the untreated sample, assigned to the trans conformer.

The Effect of Nanotube Content and Orientation on the Mechanical Properties of Polymer-Nanotube Composite Fibers: Separating Intrinsic Reinforcement from Orientational Effects

We have measured the mechanical properties of coagulation-spun polymer–nanotube composite fibers. Both the fiber modulus, Y, and strength, σB, scale linearly with volume fraction, Vf, up to Vf ∼10%, after which these properties remain constant. We measured dY/dVf = 254 GPa and dσB/dVf = 2.8 GPa in the linear region. By drawing fibers with Vf < 10% to a draw ratio of ∼60%, we can increase these values to dY/dVf = 600 GPa and dσB/dVf = 7 GPa. Raman measurements show the Herman's orientation parameter, S, to increase with drawing, indicating that significant nanotube alignment occurs. Raman spectroscopy also shows that the nanotube effective modulus, YEff, also increases with drawing. We have calculated an empirical relationship between the nanotube orientation efficiency factor, ηo, and S. This allows us to fit the data for YEff versus ηo, showing that the fiber modulus scales linearly with ηo, as predicted theoretically by Krenchel. From the fit, we estimate the nanotube modulus to be; YNT = 480 GPa. Finally, we show that the fiber strength also scales linearly with ηo, giving an effective interfacial stress transfer of τ = 40 MPa and a nanotube critical length of lc=1250 nm. This work demonstrates the validity of the Cox-Krenchel rule of mixtures and shows that continuum theory still applies at the near-molecular level.

Morphological evolution and orientation development of stretched iPP films: Influence of draw ratio

AbstractVarying the processing conditions of semicrystalline polymers can produce different morphologies of crystallization, which leads to different properties. There have been extensive studies of flow‐induced crystallization on isotactic polypropylene (iPP) using predominantly shear flow. A stretching method, deduced from extrusion, was introduced to study the morphological evolution of elongation‐induced shish‐kebab crystallization. Different morphologies of the resultant samples with different draw ratios (DRs) were carefully investigated and characterized via differential scanning calorimetry, polarizing light microscopy, scanning electron microscopy, atomic force microscopy, and 2D small‐angle X‐ray scattering. In addition, the degree of orientation of the samples with different DRs was also investigated using the 2D wide‐angle X‐ray scattering technique. The results indicate that the elongation‐induced morphology is strongly dependent on the effective stretching flow expressed in terms of the DR, which is defined as the ratio of rates between take‐up and the extrusion. The spherulite is dominant at low DRs, but it starts to deform along the stretching direction with increasing DR. The shish‐kebab structure in the stretched film, composed of stretched chains (shish) and layered crystalline lamellae (kebabs), increases gradually with an increase in the DR, whereas the spherulites gradually decreased. Furthermore, the overall orientation of α‐phase crystals, expressed by the Hermans orientation parameter, is also found to increase dramatically with the DR, and the rate of increase strongly depends on the DR. The different crystal morphologies are attributed to crystallization induced by different elongations of the stretched iPP films. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1223–1234, 2010

Microstructure of carbon nanofiber/thermotropic liquid crystalline polymer composites

AbstractThe properties and microstructure of a thermotropic liquid crystalline polymer (TLCP, Vectran V400P) were investigated in the presence of carbon nanofibers (CNF). The electrical conductivity of TLCP increased with an addition of CNFs. The thermal analysis of pure TLCP and its composites revealed that a glass transition at ∼ 110°C did not change significantly. However, a decrease of tensile modulus and strength was observed with the addition of CNFs. WAXD studies showed a decrease of Herman's orientation parameter, indicating reduction of anisotropy of TLCP. Further, the disruption of molecular orientation of TLCPs was inferred by SEM and TEM analysis. SEM micrographs revealed a fibrillar structure for pure TLCPs at a macro‐scale (2–5 μm). However, this structure was not observed in composites at the same scale even though micro‐size fibrils (0.05 μm) were found with the addition of CNFs. TEM micrographs displayed banded structures of pure TLCPs, but these structures were not significant in the vicinity of CNFs. These observations confirmed that a decrease of molecular alignment and disruption of fibrillar structure of TLCP, in the presence of nanofibers, are attributed to a significant decrease in tensile modulus and strength. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Optically transparent self-reinforced poly(ethylene terephthalate) composites: molecular orientation and mechanical properties

Self-reinforced composites have been fabricated by compaction of oriented polyethylene terephthalate (PET) fibers under pressure at temperatures near, but below, their melting point. The originally white fiber bundles, which were about 40% crystalline, show increased crystallinity (55%) but optical translucency after processing. Differential scanning calorimetry (DSC) and wide-angle X-ray diffraction (WAXD) were used to study the crystallization and orientation of the fibers, revealing that the degree of crystallinity was somewhat insensitive to compaction conditions while the melting point increased substantially with increasing compaction temperature. Crystalline orientation, gauged using the Hermans orientation parameter from WAXD data, indicated that no significant loss in orientation of the crystalline fraction occurs due to compaction. Mechanical characterization revealed a stepwise decrease in flexural modulus (9.4–8.1GPa) and concomitant increase in transverse modulus and strength on increasing the compaction temperature from 255 to 259°C. This transition in behavior was accompanied by a loss of optical transparency and a change in the distribution of amorphous fraction from fine intrafibrillar domains to coarse interfibrillar domains as seen with electron microscopy. We argue then that the mechanical properties of PET compactions are influenced more by orientation of the amorphous phase than that of the crystalline phase. The impact properties of compacted materials, characterized using an unnotched Charpy test method, showed remarkable impact resistance after compaction, with impact toughness decreasing as compaction temperature was increased.

Thermal and mechanical properties of injection molded liquid crystalline polymer/amorphous polymer blends

AbstractInjection molded samples of binary blends of Vectra (LCP) and the three amorphous polymers polyethersulfone (PES), polycarbonate (PC), and aromatic poly(ester carbonate) (APEC) have been subjected to morphological and rheological characterization, and coefficients of linear thermal expansion and Young's moduli have been determined. The Young's modulus of the PES/LCP blends exhibited a near lower‐bound behavior that could be predicted by the one‐adjustable‐parameter equations of Halpin‐Tsai (ζ = 0.18) and Takayanaga (b = 0.23), whereas the coefficients of linear thermal expansion followed the Takayanaga equation with a value of b = 0.50. The chain orientation of the LCP component was essentially constant in all PES/LCP blends with a Herman's orientation parameter of 0.39 ± 0.03. Transesterification reactions led to randomization of the constituents of the PC/LCP and APEC/LCP blends. The effect was more pronounced in the PC/LCP blends. The introduction of the LCP into the PC/LCP blends led to no reduction in melt viscosity and no self‐reinforcement. APEC/LCP exhibited self‐reinforcement in blends with a content greater than 27 vol% LCP, and especially the blend with 67 vol% LCP. The self‐reinforcement was caused by the presence of an oriented LCP phase, confirmed by X‐ray diffraction, and by improved interfacial bonding, presumably resulting from the transesterification reactions occurring at the phase boundaries.

Brillouin scattering studies of poly(vinylidene fluoride) films subject to uniaxial stretching

AbstractBrillouin scattering spectra of poly(vinylidene fluoride) films subject to stretching have been studied as a function of draw (stretch) ratios. The longitudinal sound velocity is found to be isotropic for the unoriented film, but as the film is stretched, the velocity along the direction of stretch becomes higher than that perpendicular to it. The increase in the sound velocity is due to the induced orientation of the chains in the amorphous and the crystalline regions. The Hermans orientation parameter has been determined as a function of stretch from the velocity data. The result indicates the occurrence of recrystallization and reorganization as a result of transformation to form I crystallites from the amorphous phase as the film is stretched.