Mechanical and adhesion properties of polymer-modified cement mortars in relation with their microstructure

In this study, cement mortars were modified with a commercial polymer admixture. The aim of this study is to investigate the influence of the polymer content on the mechanical and adhesion properties of the mortars and to relate these properties with mortars’ microstructure. A series of mortars were produced with various polymer/cement/water/aggregate ratios. The adhesion properties of the mortars to clay bricks were tested with a simplified tensile testing measurement. The microstructure of mortars, as well as interfaces, were evaluated by Scanning Electron Microscopy (SEM). It was found that with high polymer content, large size hardened particles are formed, reducing the compressive strength of the mortars. Polymer addition enhances the adhesion between the mortar and brick. The mortar microstructure at the interface affects the adhesion properties and the mode of failure.     

Examining chemical structure at the interface between a polymer binder and a pharmaceutical crystal with neutron reflectometry

The mechanical properties of many composites are determined in part by the chemical structure and bonding at the interface between constituents in the microstructure. The study of these interfaces in molecular crystal - polymer composites is difficult using traditional techniques such as electron microscopy or X-ray scattering because of weak or detrimental interactions between the probe and materials. Here, the interface between acetaminophen and a poly(ester urethane) copolymer is analyzed using ellipsometry, infrared spectroscopy, and neutron reflectometry. These materials were chosen for their relevance to pharmaceutical tablets and plastic-bonded explosives. The acetaminophen was shown to dissolve into the polymer coating and creates an interphase region between the two materials; this mixing is almost certainly produced by typical formulation conditions, and likely affects mechanical response of the composite. Additionally, reflectometry shows that plasticizing the polymer alters this interphase region. These techniques can be applied to similar composites to reveal the relation between formulation conditions, constituent interface microstructure characteristics, and bulk mechanical response.     

Orientation‐dependent mechanical and thermal properties of plasma‐sprayed ceramics

Due to droplet‐based assembly, microstructure anisotropy is expected in atmospheric plasma‐sprayed coatings (APS), with lamellar separations and interfaces having critical effects on properties. Quantitative determination of these anisotropic properties is difficult due to geometric test constraints. This has been overcome in the literature through a variety of indirect, local, or modeled evaluation, however direct measurement on like‐dimensioned coatings is not available. In this work, 25‐mm thick ceramic coating variants, deposited at two different feed rates, were obtained from industry and macroscopic mechanical and thermal properties were evaluated in both in‐plane and out‐of‐plane orientations using identical specimen geometries. As expected, and confirming select past work, coating anisotropy has a direct influence on measured properties. The response of each property is microstructure‐dependent, highlighting the specific interaction: for instance, the fracture toughness is 120% higher in the through‐thickness orientation versus in‐plane after thermal aging, while the thermal conductivity was 24% lower in the through‐thickness. The former benefits from the lamellar interfaces that provide obstacles to crack propagation while the latter sees these interfaces as efficient phonon scatters. The results provide insights for design through robust property measurements and into operational mechanisms in this class of highly defected ceramics.     

Preferred orientation of chopped fibers in polymer-based composites processed by selective laser sintering and fused deposition modeling: Effects on mechanical properties

The orientation of reinforcing fibers in polymer-based composites greatly affects their mechanical features. It is known that different orientations of continuous fibers in the stacked layers of a laminate play a crucial role in providing an isotropic mechanical behavior, while the alignment of chopped fibers in injection molding of composites results in a degree of anisotropy. Recent additive manufacturing techniques have offered a way of controlling the fiber orientation. This article aims to investigate the effect of fiber orientation on the mechanical properties of polyamide/carbon fiber composites processed by fused deposition modeling and selective laser sintering. Tensile samples which had different fibers and layer interface with respect to the sample axis (and therefore to the tensile load) were produced. Tensile tests were performed at different strain rates; the tensile properties and the fracture surface morphology were correlated with the processing method and the sample microstructure. The best strength and stiffness were observed when the fibers and the layer interfaces were parallel to the sample axis.     

Elastic moduli of particulate composites with graded filler‐matrix interfaces

The elastic response of plane‐array models of composites reinforced by particles or aligned fibers having graded interfaces with the matrix is analyzed. Such microstructure is representative of a new class of polymer matrix composite materials in which the filler is nanometer‐sized. In such materials, the polymer chains in the matrix are preferentially oriented close to the interface with the relatively rigid fillers, this leading to a graded interfacial layer about each inclusion. The composite elastic moduli are determined based on the properties and geometry of the interfacial graded layer as well as on the moduli of the filler and the matrix, and the volume fraction of filler. Conversion curves are constructed allowing for an equivalence to be established between the present case and that of similar composites without graded interfaces. Based on these conversion curves, standard homogenization algorithms can be applied to determine the overall elastic properties of such composite. The fillers are considered to be stiffer than the matrix, both rigid and of finite stiffness. Results for both sliding and bonded interfaces are presented. The effect of anisotropic material properties in the graded region on the composite moduli is also investigated. The results of the model are compared with published experimental data.     

炼焦煤镜质组反射率分布对焦炭显微结构和热性能的影响

对近年来武钢炼焦单种煤和配合煤进行镜质组反射率分布分析,并对相应焦炭进行显微结构和热性能测试。实验发现,炼焦煤镜质组反射率分布的变化,引起焦炭显微结构的变化,而焦炭显微结构的变化最终影响焦炭的热性能;要使含碱大型高炉用焦炭的热性能保持良好,焦炭显微结构中的各显微组分要有合理的比例,细粒结构不能过高,其他各向异性结构也不能过高。     

Combined effects of nanotube aspect ratio and shear rate on the carbon nanotube/polymer composites

We use fiber-level simulations to investigate the combined effects of carbon nanotube (CNT) aspect ratio and shear rate on the microstructure and electrical properties of CNT/polymer composites. In our previous studies, we studied the effects of aspect ratio at a constant shear rate as well as the effects of shear rate for a constant aspect ratio. In this study electrical properties and microstructure changes (e.g. agglomeration/deagglomeration, network strength, nanotube orientation) of CNT/polymer composites are investigated for varying aspect ratios at different shear rates. When shear rate is increased, we observe a decrease in the electrical conductivity and an increase in the anisotropy factor due to the deagglomeration and flow induced orientation. Increasing aspect ratio shifts the conductivity vs. shear rate curve to larger values and anisotropy vs. shear rate curve to lower values showing that there is a tendency for tube agglomeration when high aspect ratio nanotubes are used. On the other hand when low aspect ratio nanotubes are used, conductive networks can be more easily destroyed by the shear forces because networks formed by low aspect ratio nanotubes have lower strength than those formed by high aspect ratio nanotubes. Our results show that electrical conductivity is anisotropic with a larger component in the flow direction. The critical shear rate defined as the shear rate where the conductive network is destroyed and all components of the composite conductivity decrease to the matrix conductivity, shifts to higher values when the aspect ratio is increased. Reduced alignment and increased entanglement are the reasons of this decrease.     

Microstructural investigation of diamond-SiC composites produced by pressureless silicon infiltration

Superhard silicon carbide-bonded diamond materials were synthesized by liquid silicon infiltration of diamond-containing preforms. The properties of the materials were strongly influenced by the strength of the interfaces between the diamond and the silicon carbide. Interface formation was investigated through local analysis of the microstructure in the interface regions using field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and electron backscatter diffraction (EBSD) as well as X-ray diffraction (XRD). The results of these experiments revealed a pronounced orientation relationship between SiC and diamond at their interfaces and, as a result, strong bonding of the diamond particles to the ceramic matrix. There was also an orientation relationship between the nano-sized SiC grains, which were embedded in residual silicon near the diamond interfaces, and diamond. Additionally, the different morphologies and phenomena occurring in the microstructures of the diamond-SiC composites and their dependence on the infiltration temperature were studied.     

Design of Janus particles based on silica@polystyrene and their compatibilization on poly(p-dioxanone)/poly(lactic acid) composites

The compatibility of poly(p-dioxanone) (PPDO) and poly(lactic acid) (PLA) is very important when they are blended. Herein, three kinds of snowman-like Janus particles (JPs) with different hydrophilic–lipophilic balance (HLB) were prepared by one-pot method by adjusting the surficial functional groups of polystyrene (PS) side and used as the compatibilizer of PPDO/PLA composites. JPs self-assemble at the cell-structure PPDO/PLA interface, which provides channels for the migration of PPDO. The silica (SiO₂) side forms hydrogen bond with PLA, and the PS side forms hydrophobic action with PPDO. Therefore, JPs improve interfacial adhesion and suppress phase separation. Among the three JPs, silica@polystyrene-graft-polymethylmethacrylate (SiO₂@PS-PMMA) possesses the most excellent interfacial behavior because its HLB value is similar to that of PPDO/PLA composites. Tensile strength was increased from the original 14.59 MPa to the maximum 24.18 MPa at 1.5 phr of SiO₂@PS-PMMA JPs, and the elongation at break increased from 39% to 203%.     

Dilational viscoelastic properties of fluid interfaces—I

The rheological properties of interfaces play a significant role in many engineering and scientific applications where an interfacial motion is involve The present study focuses on the dilational rheological properties of liquid-gas interfaces. The study of dilational interfacial properties presents so inherent difficulties, because ddational strains are accompanied by a mass exchange between the interface and the adjoining bulk, as also by a mass tra on the interface itself. These mass transfer interactions manifest themselves as additional “compositional” viscoelastic resistance to dilational d and thereby make the analysis and interpretation of measured quantities difficult. This difficulty has been overcome in the present work by a suitable of “net” viscoelastic properties which combine the contributions of the “intrinsic” viscoelastic properties of an interface and the composition properties.A longitudinal wave technique combined with tracer particle measurements, which o offers a promising method for the measurement of dilational viscoelas fluid interfaces, has been developed. In this technique, a longitudinal wave disturbance is imparted to an interface by means of a sinusoidally oscilla the resulting response of the interface is measured in terms of amplitude and time-lag of the tracer particle motion relative to the original disturban of the hydrodynamics and mass transfer interactions for liquid-gas interfaces is presented.     

Effect of powder,binder and process parameters on anisotropic shrinkage in tape cast ceramic products

The effect of powder, binder and process parameters on the properties of cast alumina tapes and their anisotropic shrinkage were investigated. Three alumina powders with different particle shapes (platelets, spherical, standard) and three PVB binders with different chain lengths were used. In addition, casting velocity and blade gap height were varied. The orientation of the particles in the tape was detected quantitatively by image analysis of micrographs. The shrinkage anisotropy is more than 12% for the platelet shaped powder and 8% for the standard powder, whereas the spherical particles lead to almost isotropic shrinkage. The influence of the organic binder chain length proved to be minor compared to the influence of the particle morphology. The variation of casting speed and blade gap height has no effect on anisotropic shrinkage in the investigated parameter range. This is explained by theoretical considerations of particle rotation in a sheared fluid.     

Carbonization and liquid-crystal (mesophase) development. 6. Effect of pre-oxidation of vitrinites upon coking properties

The effects of atmospheric oxidation at 378 K upon the carbonization of a coking and a caking vitrinite have been examined in terms of the origins and extents of development of anisotropic material. The vitrinites, oxidized from 1 to 40 days, were carbonized to temperatures between 618 and 878 K, in open boats under nitrogen at atmospheric pressure, and in sealed gold tubes at maximum pressures of 140 to 310 MPa. Optical microscopy was used to observe, qualitatively, changes in reflectance and in shape and size of the anisotropic material of the carbonized product; morphological changes were monitored by scanning electron microscopy. For both vitrinites, whereas one day of oxidation destroyed coking properties and almost all of the anisotropic development in the open-boat carbonizations, the pressure carbonizations were not significantly affected until after five days of oxidation. Anisotropy still developed by mesophase growth from the plastic phase of carbonization, to produce the shaped, botryoidal material characteristic of pressure carbonizations. Thereafter, although in the pressure carbonizations the particles of coking vitrinite only fused slightly at interfaces to form a coherent product, marked increases occurred in reflectance and in observed anisotropy, showing maxima at nine days of oxidation. Results are interpreted on the assumption that oxidation cross-links the macromolecular structure of the vitrinite substance. The effect of high pressure during carbonization after five days of oxidation is to preserve and perfect the original basic anisotropy of the vitrinites initially stabilized by the cross-linkage of oxygen atoms.     

Effect of pore orientation on anisotropic shrinkage in tape-cast products

During tape casting, an anisotropic shrinkage can be observed, which is attributed to particle alignment during the casting process. The understanding of the relationship between green body microstructure and shrinkage anisotropy is of great importance for further miniaturization of multilayer ceramics. In the current study, four alumina powders with different particle shape (spherical, standard, plate-like and extreme plate-like) were used to cast green tapes. The sintering shrinkage behavior and the microstructure were analyzed. In particular, the pore orientation was determined quantitatively by using a modified linear intercept method. The relationship between pore alignment and anisotropic sintering shrinkage of cast green tapes is discussed in all three spatial directions. The shrinkage anisotropy could be correlated quantitatively with the pore anisotropy. Furthermore, this correlation was verified by mathematical modeling based on elongated particles and pores.     

Vibrational spectroscopy of water at interfaces

Understanding liquid water's behavior at the molecular level is essential to progress in fields as disparate as biology and atmospheric sciences. Moreover, the properties of water in bulk and water at interfaces can be very different, making the study of the hydrogen-bonding networks therein very important. With recent experimental advances in vibrational spectroscopy, such as ultrafast pulses and heterodyne detection, it is now possible to probe the structure and dynamics of bulk and interfacial water in unprecedented detail. We consider here three aqueous interfaces: the water liquid-vapor interface, the interface between water and the surfactant headgroups of reverse micelles, and the interface between water and the lipid headgroups of aligned multi-bilayers. In the first case, sum-frequency spectroscopy is used to probe the interface. In the second and third cases, the confined water pools are sufficiently small that techniques of bulk spectroscopy (such as FTIR, pump-probe, two-dimensional IR, and the like) can be used to probe the interfacial water. In this Account, we discuss our attempts to model these three systems and interpret the existing experiments. For the water liquid-vapor interface, we find that three-body interactions are essential for reproducing the experimental sum-frequency spectrum, and presumably for the structure of the interface as well. The observed spectrum is interpreted as arising from overlapping and canceling positive and negative contributions from molecules in different hydrogen-bonding environments. For the reverse micelles, our theoretical models confirm that the experimentally observed blue shift of the water OD stretch (for dilute HOD in H(2)O) arises from weaker hydrogen bonding to sulfonate oxygens. We interpret the observed slow-down in water rotational dynamics as arising from curvature-induced frustration. For the water confined between lipid bilayers, our theoretical models confirm that the experimentally observed red shift of the water OD stretch arises from stronger hydrogen bonding to phosphate oxygens. We develop a model for heterogeneous vibrational lifetime distributions, and we implement the model to calculate isotropic and anisotropic pump-probe decays. We then compare these results with experimental data. Clearly, recent experimental advances in vibrational spectroscopy have led to beautiful new results, providing information about the structure and dynamics of water at interfaces. These experimental and concomitant theoretical advances (particularly the unified theoretical framework of non-linear response functions) have greatly contributed to our understanding of this unique and important substance.     

Anisotropic strength and fracture resistance of epoxy-ceramic composite materials produced by ultrasound freeze-casting

The anisotropic mechanical properties of ultrasound freeze cast epoxy-ceramic composite materials were studied by measuring flexural strength and fracture resistance curves (R-curves) using both unnotched and notched three-point beam bending experiments, respectively, cut in three different orientations relative to the directional freezing axis. Three ultrasound frequencies of 0.699, 1.39 and 2.097 MHz were used in order to introduce different length scales into the microstructure, with 0 MHz used as the control samples. For all cases, the composites showed higher strength and fracture resistance when the crack plane cut across the direction of ice growth (denoted as the YX orientation). The anisotropic properties were more evident for the material produced without ultrasound (0 MHz) where the flexural strength was approximately 160% higher for the YX orientation compared to two orthogonal orientations. Most of the fracture resistance increase was found to occur within a crack extension, Δa, of ～0.5 mm. Comparing the fracture resistance at Δa = 0.5 mm for the highly anisotropic 0 MHz samples showed that the YX orientation was approximately 86% tougher than the two orthogonal orientations. When the ultrasound operation frequencies of 0.699, 1.39 and 2.097 MHz were applied, the amount of anisotropy in the strength and fracture resistance gradually decreased as the operating frequency increased. The high strength and fracture resistance for the YX orientation was attributed to the alignment of the ceramic particles along the freeze front direction creating a barrier for crack propagation. Ultrasound modifies the material microstructure, introducing relatively dense ceramic layers perpendicular to the freezing front direction that act as an additional, orthogonal barrier to crack propagation. The addition of the denser layers acts to improve the mechanical properties in the weaker orientations and reduce the overall anisotropy.     

ORDERING TRANSITIONS IN LIQUID CRYSTALS PERMIT IMAGING OF SPATIAL AND TEMPORAL PATTERNS FORMED BY PROTEINS PENETRATING INTO LIPID-LADEN INTERFACES

Recent studies have reported that full monolayers of L-α-dilaurylphosphatidylcholine (L-DLPC) and D-α-dipalmitoylphosphatidylcholine (D-DPPC) formed at interfaces between thermotropic liquid crystals (LCs) and aqueous phases lead to homeotropic (perpendicular) orientations of nematic LCs and that specific binding of proteins to these interfaces (such as phospholipase A ₂ binding to D-DPPC) can trigger orientational ordering transitions in the liquid crystals. We report on the nonspecific interactions of proteins with aqueous-LC interfaces decorated with partial monolayer coverage of L-DLPC. Whereas nonspecific interactions of four proteins (cytochrome c, bovine serum albumin, immunoglobulins, and neutravidin) do not perturb the ordering of the LC when a full monolayer of L-DLPC is assembled at the aqueous-LC interface, we observe patterned orientational transitions in the LC that reflect penetration of proteins into the interface of the LC with partial monolayer coverage of L-DLPC. The spatial patterns formed by the proteins and lipids at the interface are surprisingly complex, and in some cases the protein domains are found to compartmentalize lipid within the interfaces. These results suggest that phospholipid-decorated interfaces between thermotropic liquid crystals and aqueous phases offer the basis of a simple and versatile tool to study the spatial organization and dynamics of protein networks formed at mobile, lipid-decorated interfaces.     

Plant Surface Properties in Chemical Ecology

The surface of the primary aerial parts of terrestrial plants is covered by a cuticle, which has crucial autecological functions, but also serves as an important interface in trophic interactions. The chemical and physical properties of this layer contribute to these functions. The cuticle is composed of the cuticular layer and the cuticle proper, which is covered by epicuticular waxes. Whereas the cutin fraction is a polyester-type biopolymer composed of hydroxyl and hydroxyepoxy fatty acids, the cuticular waxes are a complex mixture of long-chain aliphatic and cyclic compounds. These highly lipophilic compounds determine the hydrophobic quality of the plant surface and, together with the microstructure of the waxes, vary in a species-specific manner. The physicochemical characteristics contribute to certain optical features, limit transpiration, and influence adhesion of particles and organisms. In chemical ecology, where interactions between organisms and the underlying (allelo-) chemical principles are studied, it is important to determine what is present at this interface between the plant and the environment. Several useful equations can allow estimation of the dissolution of a given organic molecule in the cuticle and its transport properties. The implementation of these equations is exemplified by examining glucosinolates, which play an important role in interactions of plants with other organisms. An accurate characterization of physicochemical properties of the plant surface is needed to understand its ecological significance. Here, we summarize current knowledge about the physical and chemical properties of plant cuticles and their role in interactions with microorganisms, phytophagous insects, and their antagonists.     

Interfacial phenomena between conjugated organic molecules and noble metals

Understanding interfacial interaction between conjugated organic molecules and noble metals is important not only for surface science, but also in relation to organic epitaxy, the architecture of intermolecular networks or nanostructures, and organic electronics. Particularly, properties of interfacial geometric and electronic structures and their related phenomena have attracted much interest for their potential in various electronic and optoelectronic applications, and thus extensive efforts have been devoted to understand and control organic/metal interfaces. We provide an overview of interfacial phenomena between conjugated organic molecules and noble metals via various interactions at the organic/metal interfaces such as surface-molecule and intermolecular interactions, as well as recent progress achieved in this area.     

复合微粒高性能混凝土的二级界面显微结构及耐久性研究

将天然纳米纤维材料及活性球形掺合料复合应用于高性能混凝土中,用以改善高性能混凝土的二级界面,探讨胶凝材料的颗粒紧密堆积及显微结构。对混凝土力学性能的研究表明:改善混凝土的二级界面,可以大幅度提高其抗弯强度和弹性模量;对耐久性的研究表明,由于加入了纳米纤维材料,改善了体系颗粒级配及二级界面显微结构,增加了体系密实度,是提高混凝土抗冻性、抗渗性的有效途径。因而,研究高性能混凝土的二级界面显微结构,对于提高高性能混凝土的宏观物理力学性能及耐久性存在巨大潜能。     

Three dimensional discrete element modeling of granular media under cyclic constant volume loading: A micromechanical perspective

Discrete element modeling is employed to investigate the micromechanics of two granular assemblies subjected to constant-volume cyclic loading. For this purpose, two assemblies of spherical particles are modeled at the same confining pressure but with two different void ratios. The cyclic behaviors of the assemblies are inspected and the micromechanical parameters and their variations during cyclic loading are carefully observed and analyzed. The evolution of contact force networks with the progression of the loading cycles confirms that the contact force networks are hysteretic and their formation depends on the previous strain conditions of the assemblies. The distributions of the contact normals and their normal forces are also investigated to obtain a quantitative insight of the changes in the contact force networks. The probability distributions of the normal and tangential forces during cyclic loading are similar to the results of previous experimental studies that were conducted on two-dimensional specimens of granular materials. In addition, variations of the fabric tensors, which were calculated for strong contacts, are studied to trace the changes of the structural anisotropy of the specimens. The results suggest that the structural anisotropy of the specimens increases dramatically when they approach the state of liquefaction and that the degree of anisotropy is more profound in the strong contacts. Finally, the displacements of the particles during specific loading cycles are calculated to determine the relation between the movements of the particles and the changes in the macro-scale behavior of the two assemblies. The results of this study elaborate the origin of liquefaction phenomena with respect to the microstructure of the granular soils, showing the role of different mode of contacts failure in micro-scale (sliding and rolling) on the overall observed behavior of granular soils with two different relative densities, moreover the importance of strong and weak contacts in cyclic constant-volume loading of the media. It also emphasizes on the variation of structural anisotropy in undrained cyclic loading of granular media and its relationship with common soil behavior in macro-scale during liquefaction failure.