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We previously demonstrated that TiOx/Al2O3 nanolaminates (TAO NL) exhibit abnormally high-dielectric constant k (800–1000), due to Maxwell–Wagner polarization, via charge accumulation at insulating Al2O3/semiconducting TiOx interfaces. Here, we report TAO NL dielectric properties related to TiOx phase change in TiOx (0.9 nm)/Al2O3 (0.1 nm) NL. High-resolution transmission electron microscopy shows amorphous TiOx phase change to crystalline anatase TiO2 due to free-energy minimization. The phase change induce reduction in leakage current and dielectric loss (J = 10−2 to 10−4 A/cm2, tan δ = 10 to 10−1), still with k ~ 600 up to MHz, compared to amorphous TAO NLs.
Amorphous polymers are among the most common materials used in adhesives, and a clear understanding of the effects of molecular scale features on macroscopic responses is necessary to design new, better performing adhesives. While many features have been investigated, including effects of molecular weight, inclusion of filler materials, and some effects of crosslinking, much of the understanding of the adhesive response remains empirical. Specifically, choosing the appropriate combination of polymer properties that optimize the work required to debond is still a challenge and the interplay between mechanical and chemical properties of polymers at interfaces is largely unknown. Here, we perform molecular dynamics simulations on a simple coarse-grained polymer model to directly investigate the role of crosslinking in determining the adhesive response of amorphous polymers at the molecular level. We find that crosslinking has a dramatic effect on the mechanical properties even at relatively low crosslink densities, and that crosslinking alone can be effective for optimizing the adhesive response of amorphous polymer adhesives. We observe a clear transition from cohesive to adhesive failure as the crosslink density is increased which coincides with the optimal toughening in the films. Furthermore, we find that our model captures the key molecular scale deformation mechanisms that control the adhesive response. For low crosslink densities, increased crosslinking improves the adhesive response by inhibiting chain sliding and allowing the structures to achieve large deformations, but as the crosslink density is increased further, the adhesive response is diminished due to reduced overall deformability. Our results provide simple but important insights into how crosslinking in amorphous polymer adhesives can be used to tune the mechanical response and ultimately to optimize adhesive performance for various applications.
P-type Cu1.8+xSe (x = 0, 0.16, 0.20) compounds were synthesized by mechanical alloying and spark plasma sintering technique. A 100% enhancement of the Seebeck coefficient was achieved in the whole temperature interval for x = 0.16 and x = 0.20 bulks compared with that of the x = 0 bulk. The thermal conductivity was all below 1.6 W m−1 K−1 in the whole temperature interval for x = 0.16 and x = 0.20 bulks, showing a pronounced reduction compared with that of the x = 0 bulk. The lowest thermal conductivity 0.69 W m−1 K−1 was achieved in the x = 0.16 sample at 773 K, whereby a maximum ZT value of 1.23 was obtained, revealing that optimizing Cu content in Cu1.8+xSe system is an effective method to improve the thermoelectric (TE) merit and indicating a great potential for TE application along with their nontoxicity and low cost.
Self-assembled vertical heteroepitaxial nanostructures (VHN) in the complex oxide field have fascinated scientists for decades because they provide degrees of freedom to explore in condensed matter physics and design-coupled multifunctionlities. Recently, of particular interest is the perovskite-spinel-based VHN, covering a wide spectrum of promising applications. In this review, fabrication of VHN, their growth mechanism, control, and resulting novel multifunctionalities are discussed thoroughly, providing researchers a comprehensive blueprint to construct promising VHN. Following the fabrication section, the state-of-the-art design concepts for multifunctionalities are proposed and reviewed by suitable examples. By summarizing the outlook of this field, we are excitedly expecting this field to rise with significant contributions ranging from scientific value to practical applications in the foreseeable future.
It is widely accepted that oxygen will severely deteriorate the glass-forming ability (GFA) of an alloy. In this work, we report that the GFA of a Fe76Si9B10P5 glassy alloy can be significantly improved (the critical diameter for fully glass formation is increased from 1 to 3 mm) under oxygen casting atmosphere. Furthermore, the pressure of oxygen atmosphere gives an obvious enhancement in the critical diameter of Fe76Si9B10P5 glassy alloy. A dependence of GFA on casting atmosphere species (argon, nitrogen, air, and oxygen) is also observed for this glassy alloy, and its critical diameter is 1, 1.5, 2.5, and 3 mm, respectively. In addition, the Fe-based glassy alloy exhibits excellent soft magnetic properties regardless of the applied casting atmosphere. The mechanism for such an unusual oxygen effect on the GFA of Fe76Si9B10P5 glassy alloy is attributed to the reduced nucleation rate caused by the enhancement of surface tension of the alloy melt.
The structure and phase transition behavior of monoclinic phase of the morphotropic phase boundary composition Pb(Sc1/2Nb1/2)O3]0.58 –[PbTiO3]0.42 (PSN–42PT) in lead scandium niobate–lead titanate (PSN–PT) system have been investigated by in situ high-temperature polarized light microscopy (PLM) and x-ray diffraction (XRD) studies. Temperature-dependent powder XRD studies of PSN–42PT indicated monoclinic structure at 25 °C and cubic structure at 400 °C. It is observed that the room temperature monoclinic structure transforms to cubic structure through an intermediate tetragonal structure. The temperature-induced domain changes at the phase transition are investigated on (001) face of unpoled PSN–42PT crystal while heating as well as cooling the crystal on hot stage of the PLM. Under crossed polar condition, the striplike polar domains observed at lower temperature vanish gradually with increasing temperature. In the vicinity of ferroelectric transition temperature, the mesosize domains that appeared in the variable temperature PLM images are in accordance with the monoclinic–tetragonal–cubic transition sequence concluded by in situ high-temperature XRD studies. The domain rotation corresponding to the structural transformation sequence is concluded for the first time in the PSN–42PT.
A new physical model of plastic deformation in nanocrystalline (NC) materials with finest grains (whose grain size is 2–4 nm) is suggested and theoretically described. The model represents the effect of the finest grains located at triple junctions on the fracture toughness of NC materials in the case that there are multiple dislocations pile-up at grain boundaries (GBs). The maximum number n of the pile-up dislocations is determined by both the capacity of dislocations emitting associated with the crack propagation and the capacity of dislocations pile-up due to the existence of the finest grains. The calculation indicates that the parameter n increases with increment of the grain size and decreases with the finest grain size increasing. The results theoretically reveal that the triple junctions with finest grains can significantly improve the fracture toughness of NC materials compared with the normal triple junctions in wide ranges of their structural parameters.
The present study describes magnetic interactions in (Zn1–xCox)Ga2O4 (x = 0.05, 0.10, and 0.20) particles dependant on Co atoms in both tetrahedral and octahedral sites. The effects of substituted Co atoms to magnetic character are analyzed using Curie–Weiss law. The ferromagnetic character is found dominant in (Zn1–xCox)Ga2O4 semiconductors for x values lower than 0.10; in addition, a specific hysteresis with 139 ± 50 Oe coercivity is observed for 5% Co-doped ZnGa2O4. The high Co amount in tetrahedral site increased the number of antiferromagnetic couplings and the hysteresis at 300 K disappeared for (Zn0.80Co0.20)Ga2O4 particles. Furthermore, the Co+3 ions in the octahedral site decreased µeff values, per Co amounts, in the range of 4.89 ± 0.01 µB/Co to 4.44 ± 0.02 µB/Co, because of enhancing paramagnetic behaviors.
Using detailed information on the spectrum of shear transformation dynamics previously obtained from low-strain, quasi-static anelastic relaxation in a metallic glass, the corresponding response to a cyclic force is calculated, and prevailing analysis approaches are evaluated. It is shown that the time–temperature superposition principle does not resolve the distribution of activation energies for shear transformations. The distribution of shear transformation zone sizes explains the microscopic mechanisms of both slow (α) and fast (β) relaxations, and the fact that the former are irreversible. These results suggest the need to re-evaluate past interpretations of dynamic behavior of glasses.
Nearly dense and almost single-phase bulk (Cr1–xVx)2AlC (x = 0, 0.25, 0.5, 0.75, and 1.0) ceramics were successfully fabricated by in situ hot-pressing method using Cr, V, Al, and C powders as raw materials. A possible synthesis mechanism was proposed to explain the formation of (Cr1–xVx)2AlC solid solutions. The lattice parameters, microstructure, and mechanical properties of the (Cr1–xVx)2AlC ceramics were investigated in detail. The results indicated that the lattice parameters increased with the substitution of Cr by V and the aspect ratio of the grain changed from 1.4 to 3.2. The dependence of the mechanical properties on the V content was a single-peak type. The (Cr0.5V0.5)2AlC ceramic possessed the optimal mechanical performance and its Vickers hardness, flexural strength, and fracture toughness reached the maximum values of 5.18 GPa, 402 MPa, 5.91 MPa m1/2, respectively, due to the solid solution effect. The energy-consuming mechanisms of the material were also discussed.
A novel thermosensitive core/shell microgel with carbon microspheres (CMSs) cores was prepared by three steps. First, oxidized-carbon microspheres were obtained by mixed-acid oxidization. Second, the silane agent of 3-(trimethoxysilyl)-propyl methacrylate was used to functionalize the oxidized-carbon microspheres so as to generate the vinyl groups on the microspheres. Thereafter, the as-synthesized particles were used as seeds in the precipitation polymerization of N-isopropylacrylamide to introduce a thermosensitive polymer microgel shell onto the surfaces of the silanized-CMSs in the presence of an initiator and a crosslinker. The morphology and thermosensitive properties of the composite microspheres were characterized by field emission scanning electron microscopy, transmission electron microscopy, Fourier transformation infrared spectroscopy, thermogravimetry, and dynamic light scattering. Results indicate that the thickness of polymer layer could be adjusted by the crosslinking agent's concentration. The composite microgels had a low critical solution temperature at about 30 °C and exhibited strong thermosensitivity. The controlled release of a drug molecule (a model drug, acetosalicylic acid) was also investigated.
Fe–Mn–Pd alloys are promising candidates as biodegradable material for use in temporary implant applications. In this study, the hardening phase of Fe-rich martensitic alloys containing 1, 3, and 6 wt.% Pd and a fixed Mn content of 10 wt.% was investigated. All of these alloys show considerable age-hardening upon isothermal aging at 500 °C, exhibiting a behavior characteristic of maraging steels. Atom probe tomography (APT) and x-ray diffraction (XRD) measurements were performed to characterize the composition and crystallography of nanometer-sized precipitates forming in the overaged region of the Fe–Mn–Pd alloys. The precipitates consist mainly of Mn and Pd and the peaks of the intermetallic particles observed in the XRD spectra can be ascribed to the face-centered tetragonal β1-MnPd phase. The precipitation sequence for Fe–Mn–Pd is revealed to be similar to that reported for Fe–Mn–Ni and Fe–Mn–Pt maraging steels.
This chapter covers several additional methods used to form micro- and nanofibers. Some of them have already achieved maturity, such as the island-in-the-sea method discussed in Section 6.1, melt fracture in meltblowing processes (Section 6.2) and the flash spinning process (Section 6.3). Some others are still relatively exotic or under development, like the two methods based on Couette shear flow described in Section 6.4, or the centrifugal spinning method in Section 6.5. Nontraditional materials used for nanofiber formation, discussed in Section 6.6, include liquid crystals, conducting polymers, biopolymers and denatured proteins. Finally, Sections 6.7 and 6.8 discuss the specifics of drawing glass optical fibers, and in particular, polarization-maintaining optical fibers with multilobal cladding (Section 6.8).
Island-in-the-sea multicomponent fibers and nanofibers
Microscopic bi- and multicomponent fibers can be formed using melt spinning (Section 1.2 in Chapter 1), meltblowing (Section 4.1 in Chapter 4), or integrated processes such as spunbonding (Section 1.5 in Chapter 1). The additional polymer components are supplied to the main polymer through separate inner spinnerets inserted into the main outer spinneret similarly to formation of core–shell bicomponent fibers in co-electrospinning (Section 5.8 in Chapter 5) and solution blowing (Section 4.8 in Chapter 4). Cross-sections of such bi- and multicomponent fibers are reminiscent of islands in the sea, which explains the name of this technology (Nakajima 2000). In some cases the islands can merge and form winged structures, as seen in Figure 6.1a.
This chapter deals with the mechanisms and electrohydrodynamic modeling of the physical processes resulting in electrospinning of nanofibers with cross-sectional diameters approximately in the range 100 nm to 1 µm. These involve the physical nature of fluids used in electrospinning, leaky dielectrics, discussed in Section 5.2, and the formation of the precursor of electrospun jets, the Taylor cone, described in Section 5.3. Polymer jets in electrospinning possess an initial straight section, which is discussed in Section 5.4. Experimental observations of the key element of the electrospinning process, the electrically driven bending instability, which is similar to the aerodynamically driven jet bending of Chapters 3 and 4, are covered in Section 5.5. Section 5.6 describes the theory of the bending instability in electrospinning. Multiple jet interaction in electrospinning and needleless electrospinning are discussed in Section 5.7. Co-electrospinning and emulsion electrospinning of core–shell fibers (Section 5.8) are based on similar physical principles to electrospinning of monolithic nanofibers. The electrostatic field-assisted assembly techniques developed with the aim of positioning and aligning individual nanofibers in arrays and ropes are discussed in Section 5.9. Melt electrospinning of polymer fibers is briefly outlined in Section 5.10.
Electrospinning of polymer solutions
Electrospinning of polymer solutions, liquid crystals, suspensions of solid particles and emulsions employs an electric field of the strength about 1 kV cm−1. The first US patent on electrospinning was issued to Formhals (1934), but interest in this process was dormant until electrified jets of polymer solutions and melts were investigated as routes to the manufacture of polymer nanofibers (Baumgarten 1971, Larrondo and Manley 1981a–c, Doshi and Reneker 1995, Reneker and Chun 1996). In electrospinning, the electric force results in an electrically charged jet flowing out from a pendant or sessile droplet (see Figure 5.1). After the jet flows away from the droplet in a nearly straight line, it bends into a complex path and other changes in shape occur, during which electrical forces stretch and thin it by very large ratios, quite similar to the effects of the aerodynamic forces in melt- and solution blowing discussed in Chapter 4. After the solvent evaporates, solidified nanofibers are left.
This chapter discusses several post-processing approaches applied to as-spun nanofibers to change their structure and/or enhance certain properties. Section 8.1 describes carbonization, sol-gel transformation and calcination, as well as metal-plating, used to make stiff, hollow or thermally and electrically conducting fibers. Sections 8.2 and 8.3 are devoted to cross-linking of solution-blown soy protein/nylon 6 nanofibers. The collected fiber mats can be bonded both chemically (using aldehydes and ionic cross-linkers, as in Section 8.2), and physically (by means of wet and thermal treatment, as in Section 8.3) to increase the tensile strength and therefore widen the range of applications of these green nonwovens. Chemical cross-linkers bond different amino groups, primary amides and sulfhydryl groups in the protein structure, which is beneficial for the enhancement of tensile strength. It is shown that treatment with ionic cross-linkers results in nanofiber mats with a higher Young’s modulus. Covalent bonds formed by aldehyde groups have a smaller effect on the mat strength. As cross-linked nanofibers are exposed to heat, the bonds formed between amino groups in the fibers are broken and they became less aggregated. In addition, in Section 8.3 it is shown that wet conglutination of soy protein/nylon 6 nanofiber mats leads to partial physical cross-linking of nanofibers and, consequently, to an increase in Young’s modulus. An enhancement of the tensile strength of soy protein nanofiber mats, as well as a slight plasticizing effect, can also result from exposure to water.
This chapter describes the machinery, mechanism and significant experimental and theoretical aspects of melt- and solution blowing. Meltblowing is a popular method of producing polymer micro- and nanofibers en masse in the form of nonwovens via aerodynamic blowing of polymer melt jets (Section 4.1). Its physical aspects were revisited recently. The process involves a complex interplay of the aerodynamics of turbulent gas jets with strong elongational flows of polymer melts, only recently uncovered and explained.
The role of turbulent pulsations (produced by turbulent eddies in the gas jet) in meltblowing is discussed first in Section 4.2 in the framework of a model experimental situation where solid flexible sewing threadlines are used to probe a parallel high-speed gas jet. After that, in Section 4.3, the dynamics of bending and flapping of flexible threadlines in a gas jet is considered. In Section 4.4 the aerodynamically driven stretching of a straight polymer jet is considered. In Section 4.5 it is shown how a severe bending instability leading to strong stretching and thinning of polymer jets can arise. This is done in the framework of a linearized version of the governing equations in the case of small bending perturbations of a single threadline or polymer jet in meltblowing. Then, in Section 4.6 the fully nonlinear case of large-amplitude planar bending perturbations of a single polymer jet is discussed. Both isothermal and non-isothermal cases are considered. In particular, it is shown how the cooling of the surrounding gas jet results in cooling of the polymer jet inside, and in the arrest of the bending perturbation growth due to melt solidification. Section 4.7 is devoted to predictions of three-dimensional configurations of polymer jets in meltblowing from die exit to deposition screen. Not only a single polymer jet, but multiple polymer jets are modeled simultaneously, as well as deposition on a screen moving normally to the principal jet direction being accounted for. The results include prediction of the fiber deposition patterns in lay-down and fiber-size distributions in the resulting nonwovens. The angular distributions in lay-down nonwovens are also predicted. Comparisons with the experimental data suggest that the model captures main trends rather accurately.
The first chapter is devoted to the traditional methods of fiber forming, which are used to produce macroscopic fibers. Since the novel methods used to form micro- and nanofibers described in this monograph have branched from the traditional methods, an introduction into the history of manmade fibers is instructive and fully appropriate (Section 1.1). There is a brief discussion of such traditional extrusion methods of fiber forming as melt spinning (Section 1.2), dry spinning (Section 1.3), wet spinning (Section 1.4) and the integrated process of spunbonding, which is used to form nonwoven fiber webs (Section 1.5). Melt and dry spinning are closely related to the electrospinning used to produce nanofibers, so the discussion of these traditional methods allows a first glimpse of electrospinning, covered in Chapter 5. One of the key elements of spunbonding is pulling polymer filaments by fast co-flowing air, which is known as meltblowing. Meltblowing, and its offshoot solution blowing, are also used to form micro- and nanofibers, as detailed in Chapter 4. In a sense, Section 1.5 serves as an introduction to the nonwoven nanofiber mats discussed later. Section 1.2 also contains some elements of quasi-one-dimensional theory; namely, its application to the draw resonance instability of melt spinning. In its more involved form a similar quasi-one-dimensional approach is applied in Chapters 3–6 to describe processes characteristic of melt- and solution blowing and electrospinning used to form micro- and nanofibers.
History and outlook
The term fiber originates from the French word fibre, from Latin fibra “a fiber, filament,” of uncertain origin, perhaps related to Latin filum “thread,” or from the root findere “to split” (Online Etimology Dictionary 2013). For centuries, the use of fibers was limited to natural materials such as cotton and linen, which had inherent problems with wrinkling. Silk was difficult to produce and was often too delicate. Wool was strong and abundant, but would shrink and was irritating next to the skin, and would not last long, as it was a food source for moths.
Several physical concepts that are of the utmost importance in fiber-forming processes are described in this chapter. The basic physical model of a flexible polymer macromolecule as a random walk is outlined in Section 2.1. The elongational and shear rheometry of polymer solutions and melts, which elucidate the stress relation with strains and strain rate, as well as stress relaxation is described in Section 2.2. The phenomenological rheological constitutive equations appropriate for the description of viscoelastic polymer solutions and melts are introduced in Section 2.3. The micromechanical foundations of the entropic elasticity responsible for viscoelasticity of polymer solutions and melts are sketched out in Section 2.4. Solidification and crystallization are discussed in Sections 2.5 and 2.6, respectively.
A linear polymer macromolecule can be represented as a succession of identical rigid segments connected at arbitrary angles, i.e. freely jointed with each other (Flory 1969, de Gennes 1979, Doi and Edwards (1986). Such a macromolecule is comprised of N segments, each of length b. The total length of a fully stretched macromolecule is then L = Nb. The rigid segments are called Kuhn segments. A real macromolecular chain consisting of n monomers is idealized as a random walk of N Kuhn segments, which are not monomers, nor is N identical to the degree of polymerization n. If the number of Kuhn segments in a macromolecule is not large, i.e. N is close to 1, it is rather inflexible, almost rod-like. On the other hand, if N >> 1, the macromolecule is very flexible, and on length scales that are significant compared to b, but much smaller than L, it can be viewed as a flexible string. Persistence length is another length scale that characterizes the resistance of segments of macromolecular chains to bending. It is of the same order of magnitude as the length of the Kuhn segments.