Showing papers in "Journal of Materials Research in 2000"

Molecular mechanics of binding in carbon-nanotube–polymer composites

Abstract: Nanoscale composites have been a technological dream for many years. Recently, increased interest has arisen in using carbon nanotubes as a filler for polymer composites, owing to their very small diameters on the order of 1 nm, very high aspect ratios of 1000 or more, and exceptional strength with Young’s modulus of approximately 1 TPa. A key issue for realizing these composites is obtaining good interfacial adhesion between the phases. In this work, we used force-field based molecular mechanics calculations to determine binding energies and sliding frictional stresses between pristine carbon nanotubes and a range of polymer substrates, in an effort to understand the factors governing interfacial adhesion. The particular polymers studied were chosen to correspond to reported composites in the literature. We also examined polymer morphologies by performing energy-minimizations in a vacuum. Hydrogen bond interactions with the ∏-bond network of pristine carbon nanotubes were found to bond most strongly to the surface, in the absence of chemically altered nanotubes. Surprisingly, we found that binding energies and frictional forces play only a minor role in determining the strength of the interface, but that helical polymer conformations are essential.

Phase transformation of nanocrystalline anatase-to-rutile via combined interface and surface nucleation

Abstract: The kinetics of phase transformation of nanocrystalline anatase samples was studied using x-ray diffraction at temperatures ranging from 600 to 1150 °C. Kinetic data were analyzed with an interface nucleation model and a newly proposed kinetic model for combined interface and surface nucleation. Results revealed that the activation energy of nucleation is size dependent. In anatase samples with denser particle packing, rutile nucleates primarily at interfaces between contacting anatase particles. In anatase samples with less dense particle packing, rutile nucleates at both interfaces and free surfaces of anatase particles. The predominant nucleation mode may change from interface nucleation at low temperatures to surface nucleation at intermediate temperatures and to bulk nucleation at very high temperatures. Alumina particles dispersed among the anatase particles can effectively reduce the probability of interface nucleation at all temperatures.

A study of microindentation hardness tests by mechanism-based strain gradient plasticity

Abstract: We recently proposed a theory of mechanism-based strain gradient (MSG) plasticity to account for the size dependence of plastic deformation at micron- and submicron-length scales. The MSG plasticity theory connects micron-scale plasticity to dislocation theories via a multiscale, hierarchical framework linking Taylor's dislocation hardening model to strain gradient plasticity. Here we show that the theory of MSG plasticity, when used to study micro-indentation, indeed reproduces the linear dependence observed in experiments, thus providing an important self-consistent check of the theory. The effects of pileup, sink-in, and the radius of indenter tip have been taken into account in the indentation model. In accomplishing this objective, we have generalized the MSG plasticity theory to include the elastic deformation in the hierarchical framework. (c) 2000 Materials Research Society.

Surface stress model for intrinsic stresses in thin films

Abstract: A simple model was presented for intrinsic stress generation in thin films resulting from surface stress effects. This mechanism can explain the origin of compressive stresses often observed during island growth prior to coalescence, as well as intrinsic compressive stresses reported for certain continuous, fully grown films. In some cases, surface stress effects may contribute to a sudden change in the intrinsic stress during island coalescence.

Plasticity contributions to interface adhesion in thin-film interconnect structures

Abstract: The effects of plasticity in thin copper layers on the interface fracture resistance in thin-film interconnect structures were explored using experiments and multiscale simulations. Particular attention was given to the relationship between the intrinsic work of adhesion, Go, and the measured macroscopic fracture energy, Gc. Specifically, the TaN/SiO2 interface fracture energy was measured in thin-film Cu/TaN/SiO2 structures in which the Cu layer was varied over a wide range of thickness. A continuum/FEM model with cohesive surface elements was employed to calculate the macroscopic fracture energy of the layered structure. Published yield properties together with a plastic flow model for the metal layers were used to predict the plasticity contribution to interface fracture resistance where the film thickness (0.25–2.5 μm) dominated deformation behavior. For thicker metal layers, a transition region was identified in which the plastic deformation and associated plastic energy contributions to Gc were no longer dominated by the film thickness. The effects of other salient interface parameters including peak cohesive stress and Go are explored.

Hydrothermal synthesis of multiwall carbon nanotubes

Abstract: Multiwall open-end and closed carbon nanotubes with the wall thickness from several to more than 100 carbon layers were produced by a principally new method— hydrothermal synthesis—using polyethylene/water mixtures in the presence of nickel at 700–800 °C under 60–100 MPa pressure. An important feature of hydrothermal nanotubes is a small wall thickness, which is about 10% of the large inner diameter of 20–800 nm. Closed nanotubes were leak-tight by virtue of holding encapsulated water at high vacuum and can be used as test tubes for in situ experiments in transmission electron microscope (TEM). Raman microspectroscopy analysis of single nanotubes shows a well-ordered graphitic structure, in agreement with high-resolution TEM. The hydrothermal synthesis has the potential for producing multiwall nanotubes for a variety of applications. The fabrication of nanotubes under hydrothermal conditions may explain their presence in coals and carbonaceous rocks and suggests that they should be present in natural graphite deposits formed under hydrothermal conditions.

Novel electrode materials for electrochemical capacitors: Part II. Material characterization of sol-gel-derived and electrodeposited manganese dioxide thin films

Abstract: Material characterization of sol-gel-derived and electrodeposited MnO2 thin films showed that their microstructures are highly porous in nature. While sol-gel-derived films are nanoparticulate, electrodeposited films showed macropores of random and irregular platelike structures, comprising much denser surface layers and highly porous underlying layers. On the basis of calculated and theoretical density values of 1 and 4.99 g/cm3, respectively, the porosity of sol-gel-derived MnO2 films was determined to be as high as 80%, which is substantially higher than electrodeposited films at 67%. Apart from their higher specific capacitance, sol-gel-derived MnO2 films appeared to exhibit higher cycling stability and reversibility than electrodeposited MnO2 films. In the case of sol-gel films, thinner films appeared to exhibit higher cycling stability than thicker films. There was less alteration in surface morphology and microstructure, and the rate of loss in charge-storage capacity upon voltammetric cycling was not as significant for sol-gel MnO2 thin films

Adhesion and reliability of copper interconnects with Ta and TaN barrier layers

Abstract: With the advent of copper metallization in interconnect structures, new barrier layers are required to prevent copper diffusion into adjacent dielectrics and the underlying silicon. The barrier must also provide adequate adhesion to both the dielectric and copper. While Ta and TaN barrier layers have been incorporated for these purposes in copper metallization schemes, little quantitative data exist on their adhesive properties. In this study, the critical interface fracture energy and the subcritical debonding behavior of ion-metal-plasma sputtered Ta and TaN barrier layers in Cu interconnect structures were investigated. Specifically, the effects of interfacial chemistry, Cu layer thickness, and oxide type were examined. Behavior is rationalized in terms of relevant reactions at the barrier/dielectric interface and plasticity in adjacent metal layers.

Nanocrystalline Tungsten Oxide Thin Film: Preparation, Microstructure, and Photochromic Behavior

Abstract: A nanocrystalline tungsten oxide photochromic thin film was prepared by colloid chemistry method. The microstructure, phase transition involved in the solution process, photochromic behavior, and mechanism of the film were investigated by means of transmission electron microscope, x-ray diffraction, ultraviolet-visible absorption spectra, and x-ray photoelectron spectra. It was found that the particle size and crystallinity of the thin film could be easily controlled by adjusting the concentration of oxalic acid in the colloid solution of tungsten oxide hydrate. With the increase of the oxalic acid concentration, the size of nanoparticles in the film decreased sharply, and meanwhile, a blue shift of the absorption peaks caused by the quantum size effect was observed accordingly. With the increase of the pH in the solution, tungsten oxide hydrate was gradually transformed into an oxided 12-tungstate with Keggin structure, which led to the change of photochromic property of the films. The photochromism of the film is believed to be due to the electron transfer between the different valence states of tungsten ions located in adjacent sites.

Cyclic Nanoindentation and Raman Microspectroscopy Study of Phase Transformations in Semiconductors

Abstract: This paper supplies new interpretation of nanoindentation data for silicon, germanium, and gallium arsenide based on Raman microanalysis of indentations. For the first time, Raman microspectroscopy analysis of semiconductors within nanoindentations is reported. The given analysis of the load-displacement curves shows that depth-sensing indentation can be used as a tool for identification of pressure-induced phase transformations. Volume change upon reverse phase transformation of metallic phases results either in a pop-out (or a kink-back) or in a slope change (elbow) of the unloading part of the load-displacement curve. Broad and asymmetric hysteresis loops of changing width, as well as changing slope of the elastic part of the loading curve in cyclic indentation can be used for confirmation of a phase transformation during indentation. Metallization pressure can be determined as average contact pressure (Meyer’s hardness) for the yield point on the loading part of the load-displacement curve. The pressure of the reverse transformation of the metallic phase can be measured from pop-out or elbow on the unloading part of the diagram. For materials with phase transformations less pronounced than in Si, replotting of the loaddisplacement curves as average contact pressure versus relative indentation depth is required to determine the transformation pressures and/or improve the accuracy of data interpretation.

An experimental and modeling investigation of particle production by spray pyrolysis using a laminar flow aerosol reactor

Abstract: The influence of operating parameters on the morphology of particles prepared by spray pyrolysis was investigated using a temperature-graded laminar flow aerosol reactor Experimentally, zirconia particles were prepared by spray pyrolysis using an aqueous solution of zirconyl hydroxide chloride Hollow particles were formed if the reactor temperature was high, the temperature gradient was too large, the flow rate of carrier gas was high, and the initial solute concentration was low A numerical simulation of the pyrolysis process was developed using a combination of two previous models The simulation results compared well with the experimental results

Densification of Al2O3 Powder Using Spark Plasma Sintering

Abstract: Al2O3 powders with four different particle sizes were densified using a spark plasma sintering (SPS) apparatus under three different sintering conditions: holding time, heating rate, and mechanical pressure. The Al2O3 powder compact sintered at a higher heating rate produced a sample with a higher density and a fine-grained microstructure, while abnormal grain growth and a lower density resulted when a lower heating rate was applied, though the sintering temperature and holding time were the same in both cases. This revealed that rapid sintering by SPS was effective for promoting the densification of the powder. However, the powder with a coarse particle size was hard to sinter at a higher heating rate. Microstructural observation revealed that the edge part was denser than the inside of the sample when the holding time was short. Increasing the holding time made it possible for the inside to be sintered almost as dense as the edge part. Mechanical pressure was found to enhance densification of the Al2O3 powder. On the basis of these results, the SPS process is discussed.

Voids in Silicon by He Implantation: From Basic to Applications

Abstract: The mechanism of bubble formation when He is implanted into silicon is described Many experiments are reviewed and several techniques are considered During implantation and subsequent annealing, complex Hen–Vm clusters are formed, trapping vacancies, while Si self-interstitials recombine directly at the surface By increasing temperature He atoms out-diffuse, and the entire process produces a supersaturation of vacancies (void formation) Their evolution is studied during isothermal and isochronal annealing, describing the mechanisms involved; that is, direct coalescence or Ostwald ripening The internal surface is an efficient trap for self-interstitials and for metals The gettering mechanism is governed by a surface adsorption at low impurity concentration while at high value a silicide phase is observed The high getter capability is ensured by the large number of traps introduced (1017–1019 cm−3) Finally, voids introduce mid gap energy levels that act as minority carrier recombination centers, providing a powerful method to control lifetime locally in silicon devices The reviewed results demonstrate that the trap levels are due to the dangling bonds present on the void surface This property can be used in many applications

Fabrication of highly ordered ZnO nanowire arrays in anodic alumina membranes

Abstract: Highly ordered ZnO nanowire arrays were fabricated by oxidizing the metal Zn that was electrodeposited in the pores of anodic alumina membranes (AAMs). The diameters of ZnO nanowires range from 15 to 90 nm. Atomic force microscope, x-ray diffraction, and transmission electron microscopy observations indicate the polycrystalline ZnO nanowires were uniformly assembled into the hexagonally-arranged nanochannels of the AAM. A green emission band caused by the singly ionized oxygen vacancy in the ZnO nanowires was also reported.

Heat Resistance of Sn–9Zn Solder/Cu Interface with or without Coating

Abstract: The potential of the newly developed Sn-9Zn solder paste as a lead-free solder, especially focusing on the stability at high temperature, was examined. The initial interface strength between Sn-9Zn and Cu, about 50 MPa by the tensile test, is higher than other interfaces such as Sn-37Pb/Cu. While the Sn-9Zn/Cu interface maintains the high strength level after heat exposure at 125 °C, the heat exposure at 150 °C degrades strength seriously. The degradation at 150 °C is caused by dissipation and by disruption of the Cu-Zn reaction layer at the interface. Where the Cu-Zn layer is eroded to form a whole, Sn directly reacts with a Cu substrate to form a thick Sn-Cu reaction region. Such an interfacial morphology change causes the serious degradation. With the Ni/Pd/Au coating on a Cu substrate, the interface becomes much stronger than the direct interface. Even after heat exposure at 150 °C, strength degradation is not so significant. Zn segregates into the coating layer. During high-temperature exposure, Ni and Pd diffuse each other. Zn also diffuses into the coating layer to form compounds, and as a result, a depleted zone of Zn is formed in the solder close to the interface.

Lattice parameters and thermal expansion of GaN

Abstract: Neutron powder diffraction methods with Rietveld analysis are utilized to determine GaN lattice parameters from 15 to 298.1 K. Using these measurements and literature data, we calculated the thermal expansion of gallium nitride (GaN) and predicted its higher temperature thermal expansion. The results are compared with available experimental data and earlier work.

Crystallization and nanoindentation behavior of a bulk Zr–Al–Ti–Cu–Ni amorphous alloy

Abstract: The crystallization and nanoindentation behavior of a Zr–10Al–5Ti–17.9Cu–14.6Ni (at.%) bulk amorphous alloy (BAA) were studied. Resulting from the kinetic nature of phase transformation in multicomponent alloys, the crystallization path is complex. Despite the complexity of different crystallization paths, the main final crystallized product in the Zr-based BAA is Zr2Cu. Young’s modulus and hardness of the BAA were found to increase with an increase in annealing temperature. The observed mechanical properties were correlated with the microstructure of the material. Also, in the present paper, both the observed crystallization and nanoindentation behavior are compared with existing data. Zr-based BAAs exhibit a ratio of hardness to Young’s modulus (H/E ratio) of about 1/10, suggesting the interatomic bonding in the alloys is close to being covalent.

Pyrocarbon anisotropy as measured by electron diffraction and polarized light

Abstract: This work deals with the measurement of pyrocarbon anisotropy on very thin fiber coatings used to control the interfacial behavior in carbon/carbon composites. Differentiation of the various pyrocarbons was performed through computerized image analysis of the electron diffraction patterns by measuring the azimuth opening of the carbon 002 diffraction arcs. This orientation angle decreases when the texture switches from rough to smooth laminar. The relationship with the polarized light measurement technique at a lower resolution is discussed.

Microwires coated by glass: A new family of soft and hard magnetic materials

Abstract: The Taylor–Ulitovski technique was employed for fabrication of tiny ferromagnetic amorphous and nanocrystalline metallic wires covered by an insulating glass coating with magnetic properties of great technological interest. A single and large Barkhausen jump was observed for microwires with positive magnetostriction. Negative magnetostriction microwires exhibited almost unhysteretic behavior with an easy axis transverse to the wire axis. Enhanced magnetic softness (initial permeability, μι, up to 14000) and giant magneto impedance (GMI) effect (up to 140% at 10 MHz) was observed in amorphous CoMnSiB microwires with nearly zero magnetostriction after adequate heat treatment. Large sensitivity of GMI and magnetic characteristics on external tensile stresses was observed. Upon heat treatment, FeSiBCuNb amorphous microwires devitrificated into a nanocrystalline structure with enhanced magnetic softness. The magnetic bistability was observed even after the second crystallization process (increase of switching field by more than 2 orders of magnitude up to 5.5 kA/m). Hard magnetic materials were obtained as a result of decomposition of metastable phases in Co–Ni–Cu and Fe–Ni–Cu microwires fabricated by Taylor–Ulitovski technique when the coercivity increased up to 60 kA/m. A magnetic sensor based on the magnetic bistability was designed.

High-tensile ductility in nanocrystalline copper

Abstract: In this work we report a high-tensile ductility in a fully dense bulk nanocrystalline (nc) pure copper sample prepared by electrodeposition A tensile ductility with an elongation to fracture of 30% was obtained in the nc Cu specimen with an average grain size of 27 nm, which is comparable to that for the coarse-grained polycrystalline Cu An enhanced yield stress (119 MPa) and a depressed strain hardening exponent (022) were observed in the nc Cu sample with respect to the conventional polycrystalline Cu The high-tensile ductility was attributed to the minimized artifacts in the nc sample, and the grain-boundary sliding deformation mechanism resulted from the numerous amount small-angle grain boundaries and the low microstrain (dislocation density)

Phase relations and microwave dielectric properties of ZnNb2O6-TiO2

Abstract: The phase relations and microwave dielectric properties of (1−x)ZnNb2O6–xTiO2 were investigated using x-ray powder diffraction and a network analyzer. Four phase regions were studied with increasing TiO2 mol% (x): columbite solid solution, ixiolite (ZnTiNb2O8) solid solution, mixture of ixiolite and rutile solid solutions, and rutile solid solution. It was suggested that the microwave properties depend on crystal structure rather than chemical composition. In the columbite solid solution region, an order–disorder transition was found with an increasing amount of TiO2, and the quality factor decreased sharply. ZnTiNb2O8 (x = 0.5), has a fully disordered structure and possesses a quality factor of 42,500, relative dielectric constant (er) of 34.3, and temperature coefficient of resonant frequency (τf) of −52 ppm/°C. In the mixture region of ixiolite and rutile structure, τf was modified to around 0 ppm/°C.

Ni-based bulk amorphous alloys in the Ni–Ti–Zr–(Si, Sn) system

Abstract: New Ni-based bulk amorphous alloys in the alloy system Ni–Ti–Zr–(Si,Sn) were developed through systematic alloy design based upon the empirical rules for high glass forming alloys. Small additions of Si and/or Sn significantly improved the glass forming ability (GFA) of the alloys Ni57Ti23−xZr20 (Si,Sn)x leading to a Ni-based bulk amorphous alloy. The amorphous ribbons of the alloys Ni57Ti23−xZr20 (Si,Sn)x exhibited very high glass transition temperatures (Tg > 823 K), crystallization temperatures (Tx > 883 K), and large undercooled liquid regions (δTx > 50 K) implying the high GFA of the alloys. Fully amorphous rods with the diameter of up to 2 mm can be fabricated by a copper mold casting method. Development of the new Ni-based bulk amorphous alloys having high Tg,Tx, and δTx expands the practical applications of amorphous alloys as structural materials.

Slow recrystallization in the polymer electrolyte system poly(ethylene oxide)n-LiN(CF3SO2)2

Abstract: Thermal and ion-transport properties of the salt-in-polymer system poly(ethylene oxide)n–LiN(CF3SO2)2 [P(EO)nLiTFSI] were investigated for compositions ranging from n = 5 to n = 50. Particular attention was paid to the region n = 8 to 10 where a crystallinity gap previously had been reported. We concluded that the absence of distinct melting transitions for salt-rich compositions (n = 5 to 12) was attributable to the extremely slow kinetics of recrystallization of this system following a heat treatment. The results further indicated that it was primarily the nucleation process that was inhibited by the [(bis)trifluoromethanesulfonate imide] (TFSI) anion. As a corollary, the ionic conductivity was strongly dependent on the thermal history of samples, and an enhancement of up to 300% was observed in the ambient temperature ionic conductivity for pre-heated salt-rich samples.

The P-h2 relationship in indentation

Abstract: In this paper we derive an analytical expression for the indentation load–depth relation during loading in an indentation experiment, namely $$P = {E_r}{(1/\sqrt {{E_r}/H} + \in \sqrt {\pi /4} \sqrt {H/{E_r}} )^{ - 2}}{(h + \xi )^2}$$ . The advantage over previously used expressions is that no additional empirical constants are necessary. A comparison between the new expression and results from finite element calculations shows excellent agreement.

Liquid metal extraction of Nd from NdFeB magnet scrap

Abstract: This research involves using molten magnesium (Mg) to remove neodymium (Nd) from NdFeB magnet scrap by diffusion. Mg was melted over pieces of NdFeB scrap and held at temperatures in the range 675–705 °C for 2–8 h. The Mg was allowed to solidify, and the castings were then sectioned and characterized using scanning electron microscopy, x-ray diffraction, and chemical analysis. Nd was found to have diffused out of the solid scrap into the molten Mg. The thickness of the diffusion layer was measured, the diffusion of Nd through the NdFeB scrap into liquid Mg was described, and the diffusion coefficient of Nd in liquid Mg was estimated.

RETRACTED – Formation and properties of Zr-based bulk quasicrystalline alloys with high strength and good ductility

Abstract: The crystallization mode of the Zr–Al–Ni–Cu amorphous alloys changed from a single stage to become two stages by the addition of Ag or Pd, and the first-stage exothermic reaction was found to result from the precipitation of nanoscale icosahedral particles with a size of 20 to 50 nm. The precipitation took place by high nucleation and low growth rates in a polymorphous mode for the Ag-containing alloys, and a diffusioncontrolled mode for the Pd-containing alloys. The nanoscale mixed structure alloys exhibited improved strength and ductility as compared with the corresponding amorphous single-phase alloys. The findings of the dispersion strengthening as well as the dispersion ductilization gave a future opportunity to fabricate a new bulk nonequilibrium phase alloy by use of the new phenomenon.

Measurement of the loss tangent of low-density polyethylene with a nanoindentation technique

Abstract: This paper describes experimental measurements of the linear viscoelastic behavior of the surface of low-density (LD) polyethylene in contact with a pyramidal Berkovich diamond indenter. The experiments were carried out at two different temperatures, 15.9 and 27.2 °C, between frequencies of 0.1 and 800 Hz. Using the shift of the loss tangent between the two temperatures at frequencies lower than 20 Hz and an Arrhenius equation, an activation energy of 105 ± 2 kJ/mol was obtained. This value is in good agreement with the bulk value of the a relaxation of LD polyethylene reported in the literature.

Size-dependent phase transformations during point loading of silicon

Abstract: Using a unique combination of in situ electrical and acoustical measurements and ex situ transmission electron microscopy, the phase transformations of silicon during point loading were shown to exhibit a strong dependence on the size of the deformed volume. For nanometer-size volumes of silicon, the final phase was the body centered cubic structure BC8, but for larger volumes it was amorphous. The size dependence was explained by considering how shear stress fields vary with contact size and how interfacial effects between the silicon substrate and the BC8 phase determine its stability. For both small and large contacts the presence of a nonmetallic phase (assumed to be the Rhombohedral structure R8) was observed.

Nano-scratch behavior of a bulk Zr-10Al-5Ti-17.9Cu-14.6Ni amorphous alloy

Abstract: The tribological behavior of a Zr-10Al-5Ti-17.9Cu-14.6Ni (at.%) bulk amorphous alloy, in both the as-cast and annealed states, was investigated using nano-scratch tests, including ramping load scratch and multiple sliding wear techniques. The crystallization sequence of the alloy was also characterized. Mechanical properties, such as Young's modulus, hardness, friction coefficient, and tribological wear were measured. These properties were found to vary with microstructure. In general, an increase in annealing temperature results in an increase in hardness, which in turn produces a decrease in friction coefficient but an increase in wear resistance. Samples having a structure consisting of supercooled liquid matrix with dispersed nanocrystalline particles exhibit the best wear performance. (c) 2000 Materials Research Society.

Materials aspects of the high-temperature superconductors in the system Bi2O3–SrO–CaO–CuO

Abstract: Ten years after the discovery of high-Tc superconductivity in the system Bi-Sr-Ca-Cu-O, the superconducting compounds have been identified, and their structures, crystal chemistry, phase equilibria, and properties have been extensively investigated. In this review, the results of studies of crystal chemistry and phase equilibria are presented to give materials scientists a comprehensive insight into the phase equilibria and crystal chemistry of these challenging materials.