The first part of this article reviews the orientation of the surface and the in-bulk microdomain structures of diblock copolymers. Well-defined poly(styrene-b-2-vinylpyridine) diblock copolymers (about 50 wt% polystyrene blocks) formed horizontally oriented lamellar microdomains when these copolymers were cast from a nonselective solvent by means of the air–copolymer and substrate–copolymer interactions. The second section reviews the preparation of semiconducting materials by the exposure of these films to alkyl dihalide vapor. This film had an anisotropic conductivity with about 8 orders of magnitude. The third section reviews the construction of ionic complex phases by an ion-exchange reaction of quaternized poly(2-vinylpyridine) (P2VP) layers with lithium perchlorate. Finally, the introduction of colloidal silver into quaternized P2VP layers by reduction of silver iodide is reported. High electrical anisotropy originated in the orientation of microphase-separated structure of diblock copolymer films. 相似文献
In the first part of this article, the preparation method for core-shell type polymer microspheres from diblock copolymer films is reviewed. The core-shell type polymer microspheres were obtained from the crosslinking reaction in spherical microdomains formed by diblock copolymer film. In the second section, the solution and solid properties of core-shell type microspheres are reviewed. The micelle of core-shell type microsphere moved like pseudolatex. Its solubility depended strongly on that of shell segments. Finally, the miscibility behaviors of binary core-shell type microsphere blends are reported briefly. 相似文献
Films, 2 μm thick, with hexagonally packed and uniformly sized nanochannels with a diameter of ˜17 nm and at a density of ˜5 × 1010 cm–2 were prepared. These channels were partially filled with poly(acrylic acid) (PAA) and the structural change of PAA chains with variations in pH, ionic strength, and ion type caused water permeability to change by several orders of magnitude. These membranes with “chemical valves” should be useful in controlled drug release or chemical sensing. In cyclopentane, the PAA chains probably collapse onto the channel walls and the channel centers should open up. The channels allowed the separation of species according to their difference in size and this property should be useful for future studies of polymer chain reptation through the nanochannels. 相似文献
The thermal conductivity of nanocrystalline ceria films grown by unbalanced magnetron sputtering is determined as a function of temperature using laser‐based modulated thermoreflectance. The films exhibit significantly reduced conductivity compared with stoichiometric bulk CeO2. A variety of microstructure imaging techniques including X‐ray diffraction, scanning and transmission electron microscopy, X‐ray photoelectron analysis, and electron energy loss spectroscopy indicate that the thermal conductivity is influenced by grain boundaries, dislocations, and oxygen vacancies. The temperature dependence of the thermal conductivity is analyzed using an analytical solution of the Boltzmann transport equation. The conclusion of this study is that oxygen vacancies pose a smaller impediment to thermal transport when they segregate along grain boundaries. 相似文献
The thermodynamics of self-assembling systems are discussed in terms of the chemical interactions and the intermolecular forces between species. It is clear that there are both theoretical and practical limitations on the dimensions and the structural regularity of these systems. These considerations are made with reference to the microphase separation that occurs in block copolymer (BCP) systems. BCP systems self-assemble via a thermodynamic driven process where chemical dis-affinity between the blocks driving them part is balanced by a restorative force deriving from the chemical bond between the blocks. These systems are attracting much interest because of their possible role in nanoelectronic fabrication. This form of self-assembly can obtain highly regular nanopatterns in certain circumstances where the orientation and alignment of chemically distinct blocks can be guided through molecular interactions between the polymer and the surrounding interfaces. However, for this to be possible, great care must be taken to properly engineer the interactions between the surfaces and the polymer blocks. The optimum methods of structure directing are chemical pre-patterning (defining regions on the substrate of different chemistry) and graphoepitaxy (topographical alignment) but both centre on generating alignment through favourable chemical interactions. As in all self-assembling systems, the problems of defect formation must be considered and the origin of defects in these systems is explored. It is argued that in these nanostructures equilibrium defects are relatively few and largely originate from kinetic effects arising during film growth. Many defects also arise from the confinement of the systems when they are ‘directed’ by topography. The potential applications of these materials in electronics are discussed. 相似文献
The effects of thermal annealing on the structure of polycrystalline Pb(Zr0.3Ti0.7)O3 (PZT) ferroelectric thin films prepared by chemical solution deposition on Pt/TiO x electrode stacks were studied using scanning electron microscopy, transmission electron microscopy (TEM), and grazing incidence X-ray specular and diffuse reflectivity of synchrotron radiation. The stratified multilayered structure and element diffusions in the sample were characterized by TEM. Global statistical structural parameters including the density, surface or interface roughness and thickness of each layer in the samples were obtained from fitting the X-ray specular reflectivity using a homogeneous stratified multilayer model of PZT/Pt/TiO x /SiO2. The results showed that the PZT surface and PZT/Pt interface roughness changed slightly during thermal annealing in oxygen at 700°C. By contrast, the density increase of the PZT ceramic and density decrease of the Pt-bottom electrode during annealing were observed. A high density value of the PZT ceramic film after the annealing was found, up to 99.8% of the theoretical value of the corresponding bulk ceramics. The density changes of the PZT and Pt layers were further confirmed by X-ray diffuse reflectivity. The influences of the annealing treatment on the density changes of the PZT and Pt layers were attributed to the further densification of the PZT ceramic and incorporation of light elements such as Zr, Ti and O from the neighboring layers into the Pt layer, respectively, as discussed in correlation with the TEM analyses. 相似文献
A water-soluble diblock copolymer, poly[(methacrylic acid)- b -(ethylene oxide)], has been used to formulate alumina slurries that are dispersed over a wide range of pH through a combination of electrostatic and steric repulsion. The anionic poly(methacrylic acid) block, a short chain ( M W∼700 g/mol), interacts with the amphoteric alumina surface at pH 3 and acts as an anchor block. The nonionic poly(ethylene oxide) (PEO) block ( M W= 3000 g/mol) only appears to have a steric functionality. At high pH, the polymer coated surface has a net negative charge due to the excess negative sites associated with the highly dissociated methacrylic acid (MAA) units; this provides electrostatic repulsion at, for example, pH 9, which is the isoelectric point for pure alumina. The PEO chains extend from the surface and stabilize the alumina particles between pH 5 to 9 via an entropy-driven, steric repulsion. The PEO chains provide the dominating dispersive force at low pH, where very little electrostatic repulsion is possible because the positive surface charge of alumina has been neutralized by the negative sites of the adsorbed polyacid. On consolidation through pressure filtration at low pressures (2 to 5 MPa), the saturated, consolidated bodies formulated at pH 5 have a relative density of ∼0.56. These consolidated bodies initially exhibit a flow stress, but then fluidize after an extended strain (up to 0.5). The fluidization phenomenon is believed to be due to the unraveling of the PEO chains that appear to entangle between adjacent particles during consolidation. The unraveling was directly observed with an atomic force microscope between two BaTiO3 surfaces coated with the same diblock copolymer used for the alumina powder. 相似文献
A series of coatings from poly(ethylene-co-vinyl acetate) (EVA) were obtained using the matrix-assisted pulsed laser evaporation (MAPLE) technique. By changing the process parameters, i.e., laser fluence and EVA co-polymer concentration in the target, coatings with various morphologies and topographies were produced. The evaluation of the film structure was based on an analysis of optical and atomic force microscopy and profilometry measurements. A detailed chemical structure investigation, conducted based on Fourier transform infrared (FTIR) and X-ray photoelectron spectroscopy (XPS) spectra, revealed that although the general structure was preserved, some alterations of ethylene (Et) and vinyl acetate (VAc) blocks took place. The most noticeable change was in the ester group that was transformed into ketone and carboxyl groups; nevertheless, some changes in the aliphatic main chain were also present. The chemical structure changes in EVA coatings took place regardless of the process parameters used. The use of chloroform as a solvent to dissolve the EVA copolymer was indicated as a possible reason of the changes as well as the tendency of EVA macromolecules to form clusters. Nevertheless, due to low level of structure alteration, it has been shown that the MAPLE technique can be successfully used to obtain coatings from polymers with more complex structures, which are soluble in a limited number of solvents. 相似文献
The principal axial coefficients of thermal expansion for the (3C), (4H), and (6H) polytypes of SiC are considered to identify the structural role of the stacking layer sequence as it affects the thermal expansion. A general equation based on the fractions of cubic and hexagonal layer stacking is developed that expresses the principal axial thermal expansion coefficients of all of the SiC polytypes. It is then applied to address the thermal expansion anisotropy of the noncubic SiC structures. 相似文献
Chemical and structural evolution of hydroxyapatite thin films produced by sol-gel synthesis is characterized by ion beam analysis, X-ray diffraction, and Fourier transform infrared spectroscopy. Formation of the hydroxyapatite structure began at 500°C; no other phases were observed at higher temperatures. Elimination of residual organics was observed in the form of the disappearance of excess oxygen, hydrogen and carbon. Crystal size increases with increasing anneal temperature; spectroscopy indicates the formation of highly crystalline films. The analytical methods chosen provide insight into subtle chemical and structural changes which occur in films produced by this synthetic route. 相似文献
A novel diblock copolymer with a polyrotaxane block α-cyclodextrins-poly (ε-caprolactone)-b-poly{2,5-bis[(4-methoxypheny)oxycabony]-styrene}
(α-CD-PCL-b-PMPCS) was successfully synthesized by combining ring-opening polymerization (ROP) and
atom transfer radical polymerization (ATRP). The diblock copolymer was confirmed by 1H
NMR, GPC and solid-state 13C CP/MAS NMR spectroscopic analysis. Its phase
structures and phase transitions were investigated by thermogravimetric analyses and wide-angle X-ray
diffraction (WAXD). WAXD and solid-state 13C CP/MAS NMR spectroscopic study
confirmed that inclusion complexes domains of the polyrotaxanes assumed a channel-type structure. 相似文献
An amphiphilic LCBC PEO‐b‐PAz consisting of flexible PEO as a hydrophilic block and poly(methacrylic acid) containing an azobenzene moiety in side chain as a hydrophobic LC segment was synthesized and used to fabricated microporous films by spin‐coating method under a dry environment. With the help of a small amount of water, well‐arranged ellipsoidal micropores embedded in a LC matrix were obtained and the pore size is in the range of several tens µm of water. The influence of water content and rotational speed was studied in detail. It was found that regularly patterned microporous films can be prepared with certain water content, and the pore size can be easily tailored through changing the rotational speed. The obtained microporous structures showed good thermal and photo stability.
Realizing the vast technological potential of patternable block copolymers requires both the precise controlling of the orientation
and long-range ordering, which is still a challenging topic so far. Recently, we have demonstrated that ordered nanoporous
thin film can be fabricated from a simple supramolecular assembly approach. Here we will extend this approach and provide
a general route to fabricate large areas of highly ordered polymeric nanodot and nanowire arrays. We revealed that under a
mixture solvent annealing atmosphere, a near-defect-free nanoporous thin film over large areas can be achieved. Under the
direction of interpolymer hydrogen bonding and capillary action of nanopores, this ordered porous nanotemplate can be properly
filled with phenolic resin precursor, followed by curation and pyrolysis at middle temperature to remove the nanotemplate,
a perfect ordered polymer nanodot arrays replication was obtained. The orientation of the supramolecular assembly thin films
can be readily re-aligned parallel to the substrate upon exposure to chloroform vapor, so this facile nanotemplate replica
method can be further extend to generate large areas of polymeric nanowire arrays. Thus, we achieved a successful sub-30 nm
patterns nanotemplates transfer methodology for fabricating polymeric nanopattern arrays with highly ordered structure and
tunable morphologies. 相似文献
为了获得电化学性能优良的锂离子薄膜电池正极材料,采用快速退火技术制备L iMn2O4薄膜,用X射线衍射、扫描电子显微镜检测和分析了薄膜的物相及表面形貌;用循环伏安、恒流充放电研究了L iMn2O4薄膜的电化学性质。结果表明,制备的L iMn2O4薄膜均匀、致密、无龟裂;在退火温度从700℃升高到850℃的过程中,薄膜容量从34μAh/(cm2.μm)逐步升高到40μAh/(cm2.μm);当退火时间从1 m in延长到4 m in时,薄膜容量由36μAh/(cm2.μm)升高到41μAh/(cm2.μm),但当退火时间进一步延长到8 m in时,薄膜容量下降到39.5μAh/(cm2.μm);对于不同温度退火2 m in制备的薄膜而言,800℃退火得到的L iMn2O4薄膜经100次循环后的每次容量损失为0.021%,循环性能最好;对于750℃不同退火时间制备的L iMn2O4薄膜来说,退火时间为4 m in时得到的薄膜循环性能最好,经100次循环后每次容量损失仅为0.025%,表明快速退火制备的L iMn2O4薄膜具有优良的循环性能。 相似文献