Yongfeng Men

Nanostructured Hybrid Organic–Inorganic Lanthanide Complex Films Produced In Situ via a Sol‐Gel Approach

Communication: Nanostructural hybrid organic-inorganic lanthanide complex films were prepared in situ by use of a novel sol-gel precursor containing pendant triethoxy-silyl and carboxyl groups (see Figure). The resulting transparent and crack-free films gave rise to strong red or green emission, even at low lanthanide ion concentration. Phase separation and lanthanide ion aggregation were controlled at the nanoscale.

CRITICAL STRAINS DETERMINING THE YIELD BEHAVIOR OF s-PP*

Video-controlled tensile deformation experiments giving true stressstrain curves were carried out on samples of s-PP. Dividing the total tensile deformation into elastic and plastic parts shows three critical strains (A, B, C) for which the differential compliance and the recovery properties change. It was found that all critical strains remain constant on varying the crystallite thickness or the testing temperature. Point A marks the end of the linearelastic range. The yield point, as given by the maximum on the engineering stress-strain curve for a necking sample, essentially corresponds to the second critical point, although the yield point is shifted relative to B to higher strains and varies with temperature. It is associated with the collective onset of inter- and intralamellar slip processes. At the third critical strain (C), the lamellae become destroyed, and fibrils are formed. The texture changes accompanying the drawing determined by a simultaneous measurement of wide-angle X-ray scattering (WAXS) patterns indicate a common activity of intra- and interlamellar slip processes setting in at A and a dominance of intralamellar block slips at moderate deformations above B. The Youngs modulus and the yield stress show a large decrease with temperature, whereas there are only minor changes in the crystallinity. We understand it as resulting from a change of coupling, both between the crystalline lamellae and of the blocks within the lamellae. *Dedicated to Prof. Francisco J. Baltá Calleja on the occasion of his 65th birthday.

Understanding of the tensile deformation in HDPE/LDPE blends based on their crystal structure and phase morphology

The mechanisms of tensile deformation in high density polyethylene/low density polyethylene (HDPE/LDPE) blends were studied by a video-controlled tensile set-up, combined with dynamic mechanical analysis and small angle X-ray scattering. When quenching from the melt to room temperature, HDPE forms well-organized spherulits with high crystallinity and rigid amorphous layers between lamellae, and LDPE forms irregular aggregates with low crystallinity and mobile amorphous layers between lamellae. A separate lamellar stack-like structure is formed in HDPE/LDPE blends during the quenching. The deformation is affected by both the crystal structure and the phase morphology. Because the semi-crystalline polymers are made up of two interpenetrating networks, one is built up by the entangled fluid part and the other by the crystallites, at low deformations the coupling and coarse slips of the crystalline blocks dominate the mechanical properties, which allows the system to maintain a homogeneous strain distribution in the sample. The assumption of a homogeneous strain distribution can now be further proved by the tensile deformation in HDPE/LDPE blends, which shows two-step processes, with HDPE crystallites being broken down first at imposed strain of 0.4 and then LDPE crystallites being broken later, at an imposed strain of 0.6.

Lamellar Thickness and Stretching Temperature Dependency of Cavitation in Semicrystalline Polymers

Polybutene-1 (PB-1), a typical semicrystalline polymer, in its stable form I shows a peculiar temperature dependent strain-whitening behavior when being stretched at temperatures in between room temperature and melting temperature of the crystallites where the extent of strain-whitening weakens with the increasing of stretching temperature reaching a minima value followed by an increase at higher stretching temperatures. Correspondingly, a stronger strain-hardening phenomenon was observed at higher temperatures. The strain-whitening phenomenon in semicrystalline polymers has its origin of cavitation process during stretching. In this work, the effect of crystalline lamellar thickness and stretching temperature on the cavitation process in PB-1 has been investigated by means of combined synchrotron ultrasmall-angle and wide-angle X-ray scattering techniques. Three modes of cavitation during the stretching process can be identified, namely “no cavitation” for the quenched sample with the thinnest lamellae where only shear yielding occurred, “cavitation with reorientation” for the samples stretched at lower temperatures and samples with thicker lamellae, and “cavitation without reorientation” for samples with thinner lamellae stretched at higher temperatures. The mode “cavitation with reorientation” occurs before yield point where the plate-like cavities start to be generated within the lamellar stacks with normal perpendicular to the stretching direction due to the blocky substructure of the crystalline lamellae and reorient gradually to the stretching direction after strain-hardening. The mode of “cavitation without reorientation” appears after yield point where ellipsoidal shaped cavities are generated in those lamellae stacks with normal parallel to the stretching direction followed by an improvement of their orientation at larger strains. X-ray diffraction results reveal a much improved crystalline orientation for samples with thinner lamellae stretched at higher temperatures. The observed behavior of microscopic structural evolution in PB-1 stretched at different temperatures explains above mentioned changes in macroscopic strain-whitening phenomenon with increasing in stretching temperature and stress-strain curves.

Film Thickness Dependence of Phase Separation and Dewetting Behaviors in PMMA/SAN Blend Films

Film thickness dependence of complex behaviors coupled by phase separation and dewetting in blend [poly(methyl methacrylate) (PMMA) and poly(styrene-ran-acrylonitrile) (SAN)] films on silicon oxide substrate at 175 °C was investigated by grazing incidence ultrasmall-angle X-ray scattering (GIUSAX) and in situ atomic force microscopy (AFM). It was found that the dewetting pathway was under the control of the parameter U(q0)/E, which described the initial amplitude of the surface undulation and original thickness of film, respectively. Furthermore, our results showed that interplay between phase separation and dewetting depended crucially on film thickness. Three mechanisms including dewetting-phase separation/wetting, dewetting/wetting-phase separation, and phase separation/wetting-pseudodewetting were discussed in detail. In conclusion, it is relative rates of phase separation and dewetting that dominate the interplay between them.

Temperature and Relative Humidity Dependency of Film Formation of Polymeric Latex Dispersions

Thermogravimetric analysis and a synchrotron small-angle X-ray scattering technique were employed to characterize the structural evolution of a polymeric latex dispersion during the first three stages of film formation at different temperatures and relative humidities. Three intermediate stages were identified: (1) stage I*, (2) stage I**, and (3) stage II*. Stage I* is intermediate to the conventionally defined stages I and II, where latex particles began to crystallization. The change of drying temperature affects the location of the onset of ordering, whereas relative humidity does not. Stage I** is where the latex particles with their diffuse shell of counterions in the fcc structure are in contact with each other. The overlapping of these layers results in an acceleration of the lattice shrinkage due to a decrease of effective charges. Stage II* is where the latex particles, dried well above their T(g), are deformed and packed only partially during film formation due to incomplete evaporation of water in the latex film. This is because of a rapid deformation of the soft latex particles at the liquid/air interface so that a certain amount of water is unable to evaporate from the latex film effectively. For a latex dispersion dried at a temperature close to its minimum film formation temperature, the transition between stages II and III can be continuous because the latex particles deform at a much slower rate, providing sufficient surface area for water evaporation.

Confined crystallization and phase transition in semi-rigid chitosan containing long chain alkyl groups

We report on the confined crystallization and polymorphism behavior of a series of comb-like polymers (CS(n)Cs), which were prepared via an N-alkylation reaction between chitosan and n-alkyl bromides (n = 14–20). Analysis by temperature-dependent synchrotron X-ray scattering, Fourier transform infrared spectroscopy (FTIR), solid-state nuclear magnetic resonance spectroscopy (NMR) and differential scanning calorimetry (DSC) revealed that the phase transition and crystalline structure were sensitively controlled by the length scale and the confinement state of alkyl groups, which could induce different packing structures and conformational variation behavior. Remarkably, phase transition from orthorhombic-hexagonal to monoclinic structure was observed for these side-chain polymers, demonstrating that the length scales of alkyl groups and the microstructure of polymeric backbones play an important role in the evolution of packing mode of nano-crystallites.

Properties, Morphology and Structure of BPDA/PPD/TFMB Polyimide Fibers

Abstract A family of random co-poly(amic acid)s containing 4,4′-oxydianiline (ODA) moiety were synthesised in N,N′-dimethylacetamide. The co-poly(amic acid) solutions were used as spinning dope for dry jet wet spinning process into as spun poly(amic acid) (PAA) fibres. The polyimide (PI) fibres were obtained from PAA fibres after being imidised and drawn in furnace. The processability and mechanical properties of the fibres were notably improved by incorporating ODA into 3,3′,4,4′-biphenyltetracarboxylic dianhydride/p-phenylenediamine (BPDA/PPD) backbone. The best strength and modulus of BPDA/PPD/ODA PI fibre (diamine mole ratio of PPD/ODA = 85∶15) attained 2·25 and 96·5 GPa respectively, which were approximately three times the tenacity of the BPDA/PPD PI fibre. The SEM image showed that the cross-section of each stage fibres was round and void free. In addition, ‘skin–core’ and microfibrillar structure were not observed. The thermal properties of PI fibres were also investigated. The results showed that the PI fibres have excellent thermal stability; moreover, the dimensional stability and structural homogeneity of the fibres were significantly improved by heat drawn stage. Tg was found to be ∼290°C by thermomechanical and dynamic mechanical analyses. The X-ray (wide angle X-ray diffraction and small angle X-ray scattering) experiments indicated that the ordering degree of longitudinal and lateral stacks, as well as the molecular orientation of PI fibre, was improved in the preparation process of fibres. Furthermore, the mechanical properties of fibres are profoundly affected by the heat drawn conditions.

Microstructure and Deformation Behavior of Polyethylene/Montmorillonite Nanocomposites with Strong Interfacial Interaction

Deformation behavior of polyethylene/modified montmorillonites with polymerizable surfactant (PE/P-MMT) nanocomposite with strong interfacial interaction was studied by means of morphology observation and X-ray scattering measurements. The orientation of PE chains was accompanied by the orientation of well-dispersed MMT platelets due to the presence of strong interfacial interaction, and both of the orientations were parallel to the deformation direction. The high degree of orientation of MMT platelets and PE chains resulted from the synergistic movement of PE matrix and MMTs, which originated from the presence of a network-like structure. Meanwhile, the existence of MMT platelets with good mobility during deformation and strong interfacial interaction with PE matrix could further improve the break energy of material by restraining the initiation and growth of cavities during deformation. In contrast, PE/MMT nanocomposite with no strong interfacial interaction and poor dispersed state of MMT sheets showed the weaker orientation of both PE chains and MMT platelets, and a strong cavitation during deformation.

Study of temperature dependence of crystallisation transitions of a symmetric PEO-PCL diblock copolymer using simultaneous SAXS and WAXS measurements with synchrotron radiation

The reversible transitions of the lamellae of a crystalline-crystalline diblock copolymer from the melt to crystallites were studied using simultaneous small-angle X-ray scattering (SAXS) and wide-angle X-ray scattering (WAXS) measurements with synchrotron radiation. A symmetric poly(ethylene oxide)-poly(