Synthesis and piezoelectric properties of nanocrystalline PZT-based ceramics prepared by high energy ball milling process

Nanocrystalline powders of a soft FeNbLi-doped PZT material have been prepared by a novel mechanochemical process consisting of mixing the stoichiometric oxides in a planetary ball mill for prolonged times up to 80 h. The constituent oxides were reacted in a tungsten carbide vial with balls of 5, 10 and 20 mm in diameter and a ball/powder ratio of 15/1. The chemical reaction between the component oxides was triggered after 20 h of energetic milling and was completed after 80 h. The XRD of the reacted nanopowder showed the well known perovskite structure. Compacted samples of this powder were sintered between 800-1300°C for 3 h and the main piezoelectric properties were determined. The density of the sintered samples reached nearly 99% of the theoretical density at 1100°C and showed good piezoelectric characteristics: planar coupling factor of 0.66, dielectric displacement constant d ₃₃ of 550 pm/V, mechanical quality factor of 85, and relative dielectric constant of 3800. The possible mechanisms for solid state reaction of mechanically activated nanopowders such as local heating and pressure at collision as well as defects diffusion are discussed.     

Microstructural characterization of amorphous and nanocrystalline boron nitride prepared by high-energy ball milling

Microstructural parameters like crystallite size, lattice strain, stacking faults and dislocation density were evaluated from the X-ray diffraction data of boron nitride (BN) powder milled in a high-energy vibrational ball mill for different length of time (2-120 h), using different model based approaches like Scherrer analysis, integral breadth method, Williamson-Hall technique and modified Rietveld technique. From diffraction line-broadening analysis of the successive patterns of BN with varying milling time, it was observed that overall line broadening was an operative cause for crystallite size reduction at lower milling time (∼5 h), whereas lattice strains were the prominent cause of line broadening at higher milling times (>19 h). For intermediate milling time (7-19 h), both crystallite size and lattice strain influence the profile broadening although their relative contribution vary with milling time. Microstructural information showed that after long time milling (>19 h) BN becomes mixture of nanocrystalline and amorphous BN. The accumulations of defects cause this crystalline to amorphous transition. It has been found that twin fault (β′) and deformation fault (α) significantly contributed to BN powder as synthesized by a high-energy ball-milling technique. Present study consider only three ball-milled (0, 2 and 3 h) BN powder for faults calculation because fault effected reflections (1 0 1, 1 0 2, 1 0 3) disappear with milling time (>3 h). The morphology and particle size of the BN powders before and after ball milling were also observed in a field emission scanning electron microscope (FESEM).     

Solid-state transformation in nanocrystalline Ti induced by ball milling

In the current study, we report for the first time a new Ti rhombohedral (trigonal) structure induced by HEBM and subsequent sintering. During ball milling of Ti powder, solid-state transformation does not only depend on the grain refinement but also on the successful deformation of the nano-sized crystallites due to high energy ball impacts. Thermal stability of Ti-nanocrystalline in FCC allotrope was investigated. Upon sintering, the unstable FCC restored back to the rhombohedral phase rather than to HCP. The appearance of HCP Ti after sintering could suggest that prolonged milling leads to dispersion of hard particles (HCP) into more ductile particles belonging to allotropic phases, and hence possibility of resurfacing on sintering.     

High quality pure ZST ceramics prepared from nanopowders produced by high energy ball milling process

Improved density (>98 %) has been realized in Zr_0.8Sn_0.2TiO₄ (ZST) composition using nano-powder as precursor obtained from high energy milling process. Sintering has been performed at 1,325 °C for 4 h without using any sintering aids. XRD pattern shows single phase formation with orthorhombic structure. The microwave dielectric properties of ZST ceramics derived from precursor nano powder (obtained by high energy milling for 4 h) gives an optimum value of permittivity (ε′ ~ 38) and quality factor (Q × f ~ 1,03,300). However, precursor nanopowder obtained from extended milling (12 h) renders fine particle size (~20 nm) with meager change in permittivity within experimental error, whereas quality factor gets drastically reduced.     

Reactive ball milling to produce nanocrystalline ZnO

Ball milling of zinc powders in oxygen atmosphere leads to nanocrystalline ZnO. The average grain size has a value of 9 nm. The zinc oxidation proceeds gradually. It is compared with the combustion oxidation reactions of metals (Zr, Ti, Fe and Sn) reported previously. We propose a new parameter ΔH/C_p(metal) instead of simplified adiabatic temperature to judge if the mechanochemical oxidation of a particular metal happens via gradual or combustion reaction.     

高能球磨制备钛酸锶铋陶瓷及其介电弛豫研究

采用高能球磨和固相烧结法制备了一系列Sr1-1.5xBixTiO3(SBT)陶瓷.采用XRD和SEM分析了样品的相结构和显微结构.结果表明,高能球磨过后的粉末为具有钙钛矿结构的SBT固溶体,且SBT陶瓷的固溶度有所提高.其介电性能结果表明,SBT的介电常数温度特性具有明显的弛豫现象,并且随Bi含量的增加,相转变温度向高温移动,相变弥散及弛豫程度增强,并对SBT陶瓷的弛豫机制进行了探讨.     

Electrical and magnetic properties of nanocrystalline BiFeO3 prepared by high energy ball milling and microwave sintering

A new synthesis route with high energy ball milling and microwave sintering is used to obtain nanocrystalline BiFeO3 with improved dielectric and magnetic properties. Electrical and magnetic properties are compared with a conventionally sintered microcrystalline BiFeO3. It is found that the dielectric constant is increased more than one order of magnitude, electrical resistivity by six orders of magnitude and remnant polarization value is increased by 4-5 times for nanocrystalline BiFeO3 in comparison to conventionally sintered microcrystalline BiFeO3. Nanocrystalline BiFeO3 is seen to have ferromagnetic behavior whereas microcrystalline BiFeO3 is known to be antiferromagnetic.     

Nanostructure cathode materials prepared by high-energy ball milling method

We prepare Li₂MnO₃ and LiNi_0.5Mn_0.3Co_0.2O₂ as nanostructure cathode materials using a high-energy ball milling method with bulk-type electrodes. The nanostructure electrodes prepared by the ball milling exhibit much smaller particle sizes in diameter than those of bulk-type electrodes. The 1st charge–discharge capacitance and efficiency of the nanostructure cathode materials are superior to those of the bulk-type electrodes.     

Sm-Co hard magnetic nanoparticles prepared by surfactant-assisted ball milling

Hard magnetic nanoparticles based on the Sm(2)Co(17) and SmCo(5) systems have been successfully produced using a surfactant-assisted ball milling technique. A size-selection process has been developed to obtain nanoparticles of different sizes with narrow size distribution. Significant room-temperature coercivity up to 3.1?kOe has been achieved with the Sm(2)Co(17)-based nanoparticles of an average size of 23?nm. It has been found that surfactants play multifold roles in the processing.     

On the nanocrystalline to glass transition during ball milling

Mechanical alloying performed by ball milling metallic powders leads to a nanocrystalline state and metastable phases such as supersaturated solid solutions and amorphous phases. The nanocrystalline state may act as a transition state for the crystal to glass transition. Assuming polymorphic (or partitionless) melting of a nanocrystalline supersaturated solid solution, it is found that a critical nanograin size for amorphization may be defined. This critical size depends on the concentration of the supersaturated solid solution.Application to the Zr based hexagonal solid solution Zr-Ni allows a quantitative evaluation of this effect. It is shown that for nanocrystalline size the classical T₀ curve is significantly lowered in temperature, yielding a polymorphous crystal to glass transition for smaller nickel concentration than for conventional crystalline sizes. Therefore, both supersaturation and grain refining to nanocrystalline dimensions work towards an easier amorphization by ball milling.     

Production of nanocrystalline powders by high-energy ball milling: model and experiment

A model of high-energy ball milling of powders has been proposed. It is demonstrated that part of the energy is consumed for initiation of microstrains ε during milling and, hence, the process of the powder grinding is decelerated. An analytical expression has been deduced describing the size of nanocrystalline powder particles as a function of the milling time. The model and the experiment have been compared, using a powder of tungsten carbide (WC). The average size of the particles and the value of the microstrains in the ball-milled powder were determined by an x-ray method from broadening of diffraction reflections. The size of the particles was also evaluated using scanning electron microscopy and the sedimentation method.     

Incontinuous grain growth in cobalt nanocrystalline powders prepared by high-energy mechanical milling

Cobalt nanocrystalline powders with the average grain size of about 17 nm were prepared by high-energy mechanical milling. Grain growth in highly pure and particle-containing nanocrystalline Co powders were investigated respectively by a series of annealing experiments at different temperatures. The characteristics of incontinuous grain growth were found in both the pure and the particle-containing nanocrystalline powders. It is proposed by the authors that the sharp increase in nanograin size in the transition between the low and high temperature regions is a result of enhanced grain growth promoted by the stored energy as a supplied driving force, based on which rapid grain growth occurs through a particular dominant mechanism of nanograin rotations in the pure nanocrystalline powders, and that through off-pinning of grain boundaries in the particle-containing nanocrystalline powders.     

Microstructure and martensitic transformation in Si-coated TiNi powders prepared by ball milling

Si was coated on the surface of Ti–49Ni (at%) alloy powders by ball milling in order to improve the electrochemical properties of the Si electrodes of secondary Li ion batteries and then the microstructure and martensitic transformation behavior were investigated by means of scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). Ti–Ni powders coated with Si were fabricated successfully by ball milling. As-milled powders consisted of highly deformed Ti–Ni powders with the B2 phase and amorphous Si layers. The thickness of the Si layer coated on the surface of the Ti–Ni powders increased from 3–5 μm to 10–15 μm by extending the milling time from 3 h to 48 h. However, severe contamination from the grinding media, ZrO₂ occurred when the ball milling time was as long as 48 h. By heating as-milled powders to various temperatures in the range of 673–873 K, the highly deformed Ti–Ni powders were recovered and Ti₄Ni₄Si₇ was formed. Two-stage B2–R–B19′ transformation occurred when as-milled Si-coated Ti–49Ni alloy powders were heated to temperatures below 873 K, above this temperature one-stage B2–B19′ transformation occurred.     

Synthesis and structural evolution of tungsten carbide prepared by ball milling

Tungsten carbide has been synthesized directly by ball-milling tungsten powder and activated carbon in vacuum. The structural development of the WC phase with milling times up to 310 h has been followed using X-ray, neutron diffraction and scanning electron microscopy. Subsequent annealing (at 1000 °C for 1 and 20 h) of material milled for 90 h or longer, results in samples comprising almost entirely crystalline WC. The production of WC itself during milling results in enhanced iron contamination from the steel mill and balls on extended milling which were monitored by energy-dispersive X-ray and Mossbauer spectroscopies. This revised version was published online in November 2006 with corrections to the Cover Date.     

Fast amorphization and crystallization in Al-Fe binary system by high-energy ball milling

Large amount of amorphous phase of Al-Fe binary system was obtained by MA of elemental powders using a high-energy ball mill at milling intensity of 150G (G is the gravitational acceleration). XRD, HRTEM and DSC were used to analyze the process of amorphization and crystallization. The time required achieving almost complete amorphous state is only 4.2 ks for Al-25 at.%Fe system and 3 ks for Al-30 at.%Fe system, respectively. The time of amorphous formation is very shorter than that of previous reports on Al-Fe binary system. Further milling causes rapid crystallization of the amorphous phase. By analysis of S(Q), the presence of a strong Al-Fe chemical short-range order in the amorphous matrix is suggested. Moreover, the superstructure of these Al-Fe clusters in the amorphous matrix is similar to the solid structure of Al₅Fe₂, and the clusters transform into the nucleus of Al₅Fe₂ intermetallic compound under the action of milling energy.     

Mechanical behavior of bulk nanocrystalline copper alloys produced by high energy ball milling

Copper alloys with different amounts of zinc were synthesized via high energy ball milling at liquid nitrogen and room temperature. Bulk samples were produced in situ by controlling the milling temperature. It is shown that temperature plays an important role in formation of artifact-free consolidated samples via its effect on defect formation and annihilation during the milling process. The mechanical behavior of Cu–Zn nanocrystalline alloys was examined using Vickers microhardness and tensile tests. The nanostructure of the alloys was investigated by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The hardness results of processed alloys vary as a function of the alloying elements. Considering typical low ductility of nanocrystalline materials, the improved ductility with the high strength observed in these alloys suggests that they are artifact-free and may have several deformation mechanisms, which may include dislocation activity and nano-twinning.     

Thermal analysis on the curie temperature of nanocrystalline Ni produced by ball milling

Ball milling on Ni powder at 2, 4, and 6 h interval resulted in a decrease in crystalline sizes of 35, 17 and 13 nm, respectively. Thermal analysis was carried out on unmilled and milled Ni powders. Differential scanning calorimetry curves of milled powder indicated the shifting of magnetic transition temperature peak to lower values whereas thermo-gavimetric curves revealed higher weight loss during heating which confirmed Ni volume expansion on becoming paramagnetic. However, at high temperature the ferromagnetic suppression induced by mechanical milling is lost, hence the normal Curie temperature is restored due to possible grain growth.