Two‐step cavitation in semi‐crystalline polymer during stretching at temperature below glass transition

Cavitation behavior in poly(4‐methyl‐1‐pentene) upon stretching below glass transition temperature was investigated by in situ ultra‐small angle X‐ray scattering technique. Strong stress‐whitening was observed indicating an extensive occurrence of cavitation in the material during tensile deformation below Tg. The X‐ray scattering patterns suggest oriented disc‐shaped cavities with normal mostly parallel to the stretching direction occurred. Structural parameters of such cavities such as thickness, radius, and tilting angle of the normal of the disc with respect to the stretching direction have been successfully calculated using a model fitting procedure. The results exhibited a two‐step process of cavitation that small amount of large cavities appeared first and then small cavities were triggered extensively in the samples at larger strains. This two‐step cavitation phenomenon can be weakened after the quenched sample was annealed or the sample was prepared by slow cooling. This peculiar two‐step cavitation process can be understood as a result of high frozen in internal stress in quenched sample that led to local failure of the materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 2007–2014     

The free volume of poly(vinyl methylether) as computed in a wide temperature range and at length scales up to the nanoregion

In the present work, we focus on the free volume evaluations from different points of view, including the aspect of probe sizes, temperature, and cavity threshold. The free volume structure is analyzed on structures of poly(vinyl methylether) prepared by fully atomistic molecular dynamics. At first, the temperature behavior of an overall free volume and a free volume separated into individual cavities is shown. The origin of large free volume cavities is explained. A complex view on the cavity number is provided, while a complicated behavior previously observed is now explained. The number of large cavities remained almost constant with the temperature. Oppositely, the number of small cavities related to the atomic packing changes with temperature in a distinct way for glassy and supercooled regions. The cavity number maxima determine a percolation threshold according to percolation theory. The change in polymer properties with temperature can be related to a percolation of the free volume according to the free volume theory, when proper probe radii ～0.8 A? are used for its observation. A construction of probabilistic distribution of free volume sizes is suggested. The free volume distributions reported here are bimodal. The bimodal character is explained by two different packings--atomic and segmental--forming a prepeak and a main peak on the distribution. Further attention is dedicated to comparisons of the computed free volume sizes and the ortho-positronium (o-Ps) lifetimes. The prepeak of the free volume distribution is probably unseen by o-Ps because of a cavity threshold limit. The effect of the shape factor on the computed o-Ps lifetimes is tested. The quasicavities obtained by redistributing the free volume maintain the ratio of the main dimensions with temperature. Finally, novel data on the cavity environment are provided, while it is suggested how these can be useful with the recent developments in the positron annihilation methods. The coordination number of large cavities with the polymer segments is around 1, as predicted in the free volume theory. Similarly to the percolation and the cavity number, the coordination number exhibits a change when explored by a suitable probe radius ～0.8 A?. The insightful visualizations showed properties of interest investigated within the actual work.     

Impact testing of polymeric foam using Hopkinson bars and digital image analysis

The present investigation aims at testing polymeric foam under impact loading using large diameter nylon Hopkinson bars and optical field measurements. Accurate average stress-strain relations can be obtained when soft large diameter polymeric pressure bars and the appropriate data processing are used. However, as there are generally no homogeneous strain and stress fields for polymeric foams, an optical field observation is needed. In contrast to quasi-static tests where the digital image correlation (DIC) measurement is commonly used, technical difficulties still remain for the reliable use of DIC under impact conditions. In this paper, an accurate synchronization method based on the displacement measurement of the end of pressure bars (calculated by a robust DIC algorithm) is preferred to conventional MCDL box time synchronization. Also, the bar end displacement measurement offers a complementary calibration method for the tension/strain conversion coefficient. Strain fields are obtained for tests on foam sample at impact velocities up to 20 m/s. The localized strain fields permit better understanding of the observed stress plateau from SHPB results. The relevance of the present method for establishing mechanical response of polymeric foam is then demonstrated.     

Scaled particle theory study of the length scale dependence of cavity thermodynamics in different liquids

It has been noted that the work of cavity creation in water exhibits a crossover behavior, in that its cavity size dependence changes from volume dependence for small cavities to area dependence for larger cavities [Lum, K.; Chandler, D.; Weeks, J. D. J. Phys. Chem. B 1999, 103, 4570]. It is shown here that this behavior can be reproduced using the scaled particle theory in a straightforward manner for six different liquids (water, methanol, ethanol, benzene, cyclohexane, and carbon tetrachloride). It has also been suggested that the crossover is due to a change in the physical mechanism of the process, from one entropy-dominated to another enthalpy-dominated. However, the crossover behavior can be produced using the scaled particle theory without invoking any change in any physical mechanism. Also, the crossover occurs at a length scale of the size of the liquid molecules, as has been pointed out by others. This is the length regime where the work of cavity creation bears little relation to the bulk liquid surface tension. In addition, it is pointed out that cavity creation can always be considered as a purely entropy-driven process, which is usually accompanied by another process with compensating enthalpy and entropy changes.     

Physical state of the amorphous phase of polypropylene‐influence on free volume and cavitation phenomenon

Model polypropylene and polypropylene/low molecular weight modifier systems with identical crystalline structure but of different physical state of noncrystalline regions were analyzed. The deformation of reference material was accompanied by a cavitation phenomenon while the deformation of the polypropylene/modifier systems occurred in non‐cavitating manner. Based on X‐ray and PALS measurements the observed change of the intensity of the cavitation phenomenon during the deformation of the analyzed systems was explained. Additionally, the change of interlamellar distance (induced by introducing the modifier molecules and uniaxial stretching) was correlated with the change of average size of the free volume pores of the amorphous phase—this analysis was performed based on experimental data and theoretical estimations. It was proven that the presence of modifier reduce significantly the average size of free volume pores in relation to the system with similar interlamellar distance. Finally, the method enabling specifying the effective content of the modifier in interlamellar regions based on PALS measurements and the observed change of the value of long period was presented. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 531–543     

Morphological characterization during deformation of a poly(ether ester) thermoplastic elastomer by small-angle x-ray scattering

The scattering behavior of pre-drawn and annealed bristles of a highly deformable poly(ether ester) themoplastic elastomer based on poly(butylene terephthalate) as hard segments and poly(ethylene glycol) as soft segments in a ratio of 57/43 wt.-% is studied. Small-angle x-ray seattering measurements with an area detector are carried out on bristles with and without application of stress up to 195% relative deformation. Two-dimensional scattering patterns are used for morphological characterization of the sample.At small deformations one morphology peak is found, corresponding to a periodicity that changes affinely with deformation. The morphology of the smaple represents assemblies of mutually parallel crystalline lamellae, positioned perpendicular to the stretching direction both under and without stress. When macrodeformation increases a second peak appears, and a four-point pattern is observed in the relaxed state. In this intermediate deformation range coexisting morphologies contribute to the scattering. Additional contributions arise from lamellae, which are inclined to the stretching direction, as well as from lamellae, which are again perpendicular to the stretching direction, as a result of microfibril relaxation and loss of interfibrillar contacts. At large deformations the latter morphology dominates and the 2D-scattering pattern again shows a two-point character. A morphological model for this behaviour is discussed, where the break of interfibrillar contacts during deformation and the inhomogeneous stress field in the sample play an important role.Dedicated to the 65th birthday of Prof. E.W. Fischer Prof. Fischer was always a quide and patient teacher to us, he inspired our work with his intense interest and many valuable suggestions. We want to congratulate and thank him sincerely and extend our best wishes for the future.     

3D aluminum/silver hierarchical nanostructure with large areas of dense hot spots for surface‐enhanced raman scattering

Plasmonic nanomaterials possessing large‐volume, high‐density hot spots with high field enhancement are highly desirable for ultrasensitive surface‐enhanced Raman scattering (SERS) sensing. However, many as‐prepared plasmonic nanomaterials are limited in available dense hot spots and in sample size, which greatly hinder their wide applications in SERS devices. Here, we develop a two‐step physical deposition protocol and successfully fabricate 3D hierarchical nanostructures with highly dense hot spots across a large scale (6 × 6 cm²). The nanopatterned aluminum film was first prepared by thermal evaporation process, which can provide 3D quasi‐periodic cloud‐like nanostructure arrays suitable for noble metal deposition; then a large number of silver nanoparticles with controllable shape and size were decorated onto the alumina layer surfaces by laser molecular beam epitaxy, which can realize large‐area accessible dense hot spots. The optimized 3D‐structured SERS substrate exhibits high‐quality detection performance with excellent reproducibility (13.1 and 17.1%), whose LOD of rhodamine 6G molecules was 10^?9 M. Furthermore, the as‐prepared 3D aluminum/silver SERS substrate was applied in detection of melamine with the concentration down to 10^?7 M and direct detection of melamine in infant formula solution with the concentration as low 10 mg/L. Such method to realize large‐area hierarchical nanostructures can greatly simplify the fabrication procedure for 3D SERS platforms, and should be of technological significance in mass production of SERS‐based sensors.     

A Single‐Step Synthesis of Electroactive Mesoporous ProDOT‐Silica Structures

The single‐step preparation of highly ordered mesoporous silica hybrid nanocomposites with conjugated polymers was explored using a novel cationic 3,4‐propylenedioxythiophene (ProDOT) surfactant (PrS). The method does not require high‐temperature calcination or a washing procedure. The combination of self‐assembly of the silica surfactant and in situ polymerization of the ProDOT tail is responsible for creation of the mesoporosity with ultralarge pores, large pore volume, and electroactivity. As this novel material exhibits excellent textural parameters together with electrical conductivity, we believe that this could find potential applications in various fields. This novel concept of creating mesoporosity without a calcination process is a significant breakthrough in the field of mesoporous materials and the method can be further generalized as a rational preparation of various mesoporous hybrid materials having different structures and pore diameters.     

Mechanochromic Photonic‐Crystal Fibers Based on Continuous Sheets of Aligned Carbon Nanotubes

A new family of mechanochromic photonic‐crystal fibers exhibits tunable structural colors under stretching. This novel mechanochromic fiber is prepared by depositing polymer microspheres onto a continuous aligned‐carbon‐nanotube sheet that has been wound on an elastic poly(dimethylsiloxane) fiber, followed by further embedding in poly(dimethylsiloxane). The color of the fiber can be tuned by varying the size and the center‐to‐center distance of the polymer spheres. It further experiences reversible and rapid multicolor changes during the stretch and release processes, for example, between red, green, and blue. Both the high sensitivity and stability were maintained after 1000 deformation cycles. These elastic photonic‐crystal fibers were woven into patterns and smart fabrics for various display and sensing applications.     

Influence of oriented β‐lamellae on deformation and pore formation in β‐nucleated polypropylene

Four β‐nucleated polypropylene samples with increasing die draw ratio (DDR) were prepared to modify lamellae arrangement. The DSC, SEM, and 2D‐XRD results show that all four cast films had similar crystallinity, high contents of β‐crystal but lowering stability of β‐lamellae with ascending DDR. Meanwhile, the anisotropy of β‐lamellae distribution strengthens gently and the stacked lamellae structure perpendicular to the machine direction (MD) predominates dramatically. Tensile testing at 25 °C and 90 °C were conducted along MD and transverse direction (TD), respectively. The markedly expanding difference of deformation indicates the anisotropy highlighted significantly. Additionally, when the samples stretched along MD, a more homogeneous deformation occurs with ascending anisotropy, which is completely opposite to the β‐lamellae stability. But samples deformed more heterogeneous when stretched along TD. The characterization of morphological evolutions during stretching shows that the stacked lamellae debonds uniformly and abundant microvoids formed when the sample stretched along MD with higher anisotropy, resulting in evenly dispersion of stress, consequently making a more uniform distribution of defects and a better isotropic deformation. Moreover, the microfibrils and defects distributed uniformly within higher orientation sample after longitudinal stretching stretched along MD, leading to the dramatic improvement of pore size distribution of the membrane after biaxial stretching. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1745–1759     

Non-affine structural evolution of soft colloidal crystalline latex films under stretching as observed via synchrotron X-ray scattering

A polymer dispersion consisting of soft latex spheres with a diameter of 135 nm was used to produce a crystalline film with face-centered cubic (fcc) packing of the spheres. Different from conventional small-molecule and hard-sphere colloidal crystals, the crystalline latex film in the present case is soft (i.e., easily deformable). The structural evolution of this soft colloidal latex film under stretching was investigated by in-situ synchrotron ultra-small-angle X-ray scattering. The film exhibits polycrystalline scattering behavior corresponding to fcc structure. Stretching results not only in a large deformation of the crystallographic structure but also in considerable nonaffine deformation at high draw ratios. The unexpected nonaffine deformation was attributed to slippage between rows of particles and crystalline grain boundaries. The crystalline structure remains intact even at high deformation, suggesting that directional anisotropic colloidal crystallites can be easily produced.     

Initiation,Development and Stabilization of Cavities during Tensile Deformation of Semicrystalline Polymers

By using polybutene-1 as a typical example, we illustrate the initiation, development and stabilization of cavities in the sample during tensile deformation. Samples with the same crystallinity, long spacing and crystalline lamellar thickness but very different sizes of spherulites were prepared via changing the melt history. Dimension of cavities during stretching the samples was determined by in situ ultra small angle X-ray scattering techniques. It turned out that the size of the cavities was bigger in the sample with larger spherulites than the one with smaller spherulites. The results show clear evidence of initiating cavities within crystalline phase at the grain-boundary of crystalline blocks, growing of cavities passing through parallel stacked lamellar crystals and amorphous layers and finally stablized by tilted lamellae at both ends of the plate-like cavities within the spherulites.     

A study of the deformation‐induced whitening phenomenon for cavitating and non‐cavitating semicrystalline polymers

In this work, we used two techniques to study the deformation‐induced whitening phenomenon that occurs when certain semicrystalline polymers (SCPs) are subjected to tensile drawing: (1) IPLST (Incoherent Polarized Steady Light Transport) was used for characterizing the light scatterers and in particular for determining their size. (2) SRXTM (Synchrotron Radiation X‐Ray Tomographic Microscopy) was used to visualize the internal structure of the deformed SCPs. In particular, with this technique the possible presence of micrometric cavities can be detected. In the early whitening stage of a cavitating polypropylene (PP), the IPLST technique was found to show that the size of the light scatterers is larger than 1 μm. At the same time, the SRXTM measurements showed that no void larger than 1 μm was present in the material. The micrometric light scatterers responsible for the whitening phenomenon may thus not be simple cavities. In fact, this experimental study suggests that they correspond to areas where smaller objects (possibly nanovoids) are highly confined. At the scale of visible wavelengths, these regions could scatter visible light like individual entities of micrometric size. The study also showed that the size of cavities observable using SRXTM for a very deformed PP is dependent on the initial dimensions of the spherulites. Results previously obtained for a non‐cavitating high density polyethylene are also briefly presented in this article to confirm the theory that deformation‐induced‐whitening phenomenon may have various origins for such complex microstructuring. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys., 2013     

The use of synchrotron radiation for study of structural changes in polymers during phase transition and deformation

An experimental method using monochromatized synchrotron radiation for a wide-angle x-ray scattering study of polymers during phase transition and deformation is described. Results obtained on low-density and high-density polyethylenes and on polypropylene are given. Melting processes could be studied conveniently by making exposures during a temperature scan; a few seconds were found sufficient to obtain a diffraction spectrum. This way relatively fast crystallization processes and the structural change accompanying stress relaxation could be followed easily. The crystalline-amorphous ratio was found to decrease continuously much below the melting temperature measured dilatometrically and by DSC, implying that in the α_c-relaxation transition region of polyethylene and polypropylene a structural change takes place. At the initial state of crystallization the 040 reflection in polypropylene was found to be stronger than the 110 one, while after crystallization has been completed this ratio was inverted. Equatorial spectra made after rapid uniaxial stretching of polypropylene sheet were found to exhibit a slight time dependence demonstrating that orientation went on after stretching had been stopped.     

A Light‐Responsive Metal–Organic Framework Hybrid Membrane with High On/Off Photoswitchable Proton Conductivity

Mimicking biological proton pumps to achieve stimuli‐responsive protonic solids has long been of great interest for their diverse applications in fuel cells, chemical sensors, and bio‐electronic devices. Now, dynamic light‐responsive metal–organic framework hybrid membranes can be obtained by in situ encapsulation of photoactive molecules (sulfonated spiropyran, SSP), as the molecular valve, into the cavities of the host ZIF‐8. The configuration of SSP can be changed and switched reversibly in response to light, generating different mobile acidic protons and thus high on/off photoswitchable proton conductivity in the hybrid membranes and device. This device exhibits a high proton conductivity, fast response time, and extremely large on/off ratio upon visible‐light irradiation. This approach might provide a platform for creating emerging smart protonic solids with potential applications in the remote‐controllable chemical sensors or proton‐conducting field‐effect transistors.     

Modulation of Prins Cyclization by Vibrational Strong Coupling

Light‐molecule strong coupling has emerged within the last decade as a new method to control chemical reactions. A few years ago it was discovered that chemical reactivity could be altered by vibrational strong coupling (VSC). Only a limited number of reactions have been investigated under VSC to date, including solvolysis and deprotection reactions. Here the effect of VSC on a series of aldehydes and ketones undergoing Prins cyclization, an important synthetic step in pharmaceutical chemistry, is investigated. A decrease of the second‐order rate constant with VSC of the reactant carbonyl stretching groups is observed. We also observe an increased activation energy due to VSC, but proportional changes in activation enthalpy and entropy, suggesting no substantive change in reaction pathway. The addition of common cycloaddition reactions to the stable of VSC‐modified chemical reactions is another step towards establishing VSC as a genuine tool for synthetic chemistry.     

Capillary electrophoresis of small solutes in linear polymer solutions: relation between ionic mobility, diffusion coefficient and viscosity

Electrophoretic mobilities, mu, and diffusion coefficients, D, of a small ion (molecular weight 579) were determined in dependence on the viscosity, eta, of aqueous buffer solutions containing ethylene glycol, or polyethylene glycol (PEG) with average molecular weights of 400, 20000, 100000 or 2000000, respectively, as additives. The values for mu and D are inversely proportional to the viscosity for the solutions with small-sized additives (ethylene glycol and PEG400), in accordance to Walden's rule. In contrast, for the longest polymers the mobilities and the diffusion coefficients approximate the values observed for pure water, and are nearly independent of the viscosity. This result agrees with the model of fractional free volume and the obstruction theory. For solutions with equal viscosity, three ranges can be differentiated for mu and D in relation to the size of the additive: for small additives, on the one hand, and the long-chained polymers, on the other hand, the values for mu and D are nearly independent of the size of the additive. In contrast, a pronounced increase of mu and D is found with increasing polymer size in the molecular weight range between 20000 and 100000. The ratio mu/D, occurring in a number of expressions for the plate height contributions, exhibits a remarkably small change over the entire polymer size and viscosity range (between 1 and 7 cP) under consideration. Consequently, the separation efficiency, expressed by the plate number, is found to be nearly constant, and is independent of viscosity.     

A Generalized Strategy for the Synthesis of Large‐Size Ultrathin Two‐Dimensional Metal Oxide Nanosheets

Two‐dimensional (2D) nanomaterials show unique electrical, mechanical, and catalytic performance owing to their ultrahigh surface‐to‐volume ratio and quantum confinement effects. However, ways to simply synthesize 2D metal oxide nanosheets through a general and facile method is still a big challenge. Herein, we report a generalized and facile strategy to synthesize large‐size ultrathin 2D metal oxide nanosheets by using graphene oxide (GO) as a template in a wet‐chemical system. Notably, the novel strategy mainly relies on accurately controlling the balance between heterogeneous growth and nucleation of metal oxides on the surface of GO, which is independent on the individual character of the metal elements. Therefore, ultrathin nanosheets of various metal oxides, including those from both main‐group and transition elements, can be synthesized with large size. The ultrathin 2D metal oxide nanosheets also show controllable thickness and unique surface chemical state.     

Preparation and characterization of double metal-silica sorbent for gas filtration

This paper presents the preparation of a porous (Mg, Ca) silicate structure, which could be employed as sorbent filter media. The sorbents have been prepared using sodium silicate precipitated with various ratios of magnesium and calcium salts. The sorbents obtained were characterized using scanning electron microscope (SEM), X-ray diffraction (XRD) and nitrogen physisorption isotherm. Further, the applicability and performance of the sorbent impregnate with potassium hydroxide for removal of sulphur dioxide (SO₂) has been demonstrated. From the isotherms, specific surface area, pore diameter and volume of pores were estimated. Results show that the chemical composition and textural properties of the resultant sorbents were highly dependent on Mg/Ca molar ratio. It was found that sorbents made with 68 mol% Mg and 32 mol% Ca (PSS-MgCa-68/32); and 75 mol% Mg and 25 mol% Ca (PSS-MgCa-75/25) exhibited even higher specific surface area and pore volume than the sorbents containing a single metal. The Mg/Ca-silica sorbents obtained contains interconnected bimodal porosity with large portions being mesopores of varied sizes. The pore size distribution (PSD) results further indicate that PSS-MgCa-68/32 sorbent exhibits wide PSD of interconnected pores in the size range of 1 to 32 nm while PSS-MgCa-50/50 and PSS-MgCa-75/25 exhibits narrow PSD of 1 to 5 nm. Using SO₂ as model contaminate gas, it was shown that the dynamic adsorption performance of the PSS-MgCa-sorbents impregnated with 8 wt% KOH exhibits SO₂ uptake, with impregnated PSS-MgCa-68/32 showing better performance. This shows that the materials prepared can be used as adsorbent for gas filtration.     

Stable Diindeno‐Fused Corannulene Regioisomers with Open‐Shell Singlet Ground States and Large Diradical Characters

The synthesis of open‐shell polycyclic hydrocarbons with large diradical characters is challenging because of their high reactivities. Herein, two diindeno‐fused corannulene regioisomers DIC‐1 and DIC‐2 , curved fragments of fullerene C₁₀₄, were synthesized that exhibit open‐shell singlet ground states. The incorporation of the curved and non‐alternant corannulene moiety within diradical systems leads to significant diradical characters as high as 0.98 for DIC‐1 and 0.89 for DIC‐2 . Such high diradical characters can presumably be ascribed to the re‐aromatization of the corannulene π system. Although the DIC compounds have large diradical characters, they display excellent stability under ambient conditions. The half‐lives are 37 days for DIC‐1 and 6.6 days for DIC‐2 in solution. This work offers a new design strategy towards diradicaloids with large diradical characters yet maintain high stability.