The use of atomic force microscopy in investigating particle caking mechanisms

Spray-dried materials are being used increasingly in industries such as food, detergent and pharmaceutical manufacture. Spray-dried sodium carbonate is an important product that has a great propensity to cake; its moisture-sorption properties are very different to the crystalline and amorphous species, with a great affinity for atmospheric moisture. This work demonstrates how the noncontact surface analysis of individual particles using atomic force microscopy can highlight the possible mechanisms of unwanted agglomeration. The nondestructive nature of this method allows cycling of localised humidity in situ and repeated scanning of the same particle area. The resulting topography and phase scans showed that humidity cycling caused changes in the distribution of material phases that were not solely dependent on topographical changes. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Piezoresponse force microscopy investigations of Aurivillius phase thin films

The sol-gel synthesis and characterization of n≥3n≥3 Aurivillius phase thin filmsdeposited on Pt/Ti/SiO2–SiPt/Ti/SiO2–Si substrates is described. The number of perovskite layers, nn, was increased by inserting BiFeO3BiFeO3 into three layered Aurivillius phase Bi4Ti3O12Bi4Ti3O12 to form compounds such as Bi5FeTi3O15Bi5FeTi3O15 (n=4)(n=4). 30% of the Fe3+Fe3+ ions in Bi5FeTi3O15Bi5FeTi3O15 were substituted with Mn3+Mn3+ ions to form the structureBi5Ti3Fe0.7Mn0.3O15Bi5Ti3Fe0.7Mn0.3O15. The electromechanical responses of the materials were investigated using piezoresponse force microscopy and the results are discussed in relation to the crystallinity of the films as measured by x-ray diffraction.

Relationship between surface topography and energy density distribution of Er, Cr:YSGG beam on irradiated dentin: an atomic force microscopy study

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Unravelling the nanostructure of strawberry fruit pectins by atomic force microscopy

Atomic force microscopy (AFM) allows the analysis of individual polymers at nanostructural level with a minimal sample preparation. This technique has been used to analyse the pectin disassembly process during the ripening and postharvest storage of several fleshy fruits. In general, pectins analysed by AFM are usually visualized as isolated chains, unbranched or with a low number of branchs and, occasionally, as large aggregates. However, the exact nature of these structures is unknown. It has been suggested that pectin aggregates represent a mixture of rhamnonogalacturonan I and homogalacturonan, while isolated chains and their branches are mainly composed by polygalacturonic acid. In order to gain insight into the nature of these structures, sodium carbonate soluble pectins from ripe strawberry (Fragaria x ananassa, Duch.) fruits were subjected to enzymatic digestion with endo-Polygalacturonase M2 from Aspergillus aculeatus, and the samples visualized by AFM at different time intervals. Pectins isolated from control, non-transformed plants, and two transgenic genotypes with low level of expression of ripening-induced pectinase genes encoding a polygalacturonase (APG) or a pectate lyase (APEL) were also included in this study. Before digestion, isolated pectin chains from control were shorter than those from transgenic fruits, showing number-average (LN) contour length values of 73.2 nm vs. 95.9 nm and 91.4 nm in APG and APEL, respectively. The percentage of branched polymers was significantly higher in APG polyuronides than in the remaining genotypes, 33% in APG vs. 6% in control and APEL. As a result of the endo-PG treatment, a gradual decrease in the main backbone length of isolated chains was observed in the three samples. The minimum LN value was reached after 8 h of digestion, being similar in the three genotypes, 22 nm. By contrast, the branches were not visible after 1.5-2 h of digestion. LN values were plotted against digestion time and the data fitted to a first-order exponential decay curve, obtaining R2 values higher than 0.9. The half digestion time calculated with these equations were similar for control and APG pectins, 1.7 h, but significantly higher in APEL, 2.5 h, indicating that these polymer chains were more resistant to endo-PG digestion. Regarding the pectin aggregates, their volumes were estimated and used to calculate LN molecular weights. Before digestion, control and APEL samples showed complexes of similar molecular weights, 1722 kDa, and slightly higher than those observed in APG samples. After endo-PG digestion, size of complexes diminished significantly, reaching similar values in the three pectin samples, around 650 kDa. These results suggest that isolated polymer chains visualized by AFM are formed by a HG domain linked to a shorter polymer resistant to endo-PG digestion, maybe xylogalacturonan or RG-I. The silencing of the pectate lyase gene slightly modified the structure and/or chemical composition of polymer chains making these polyuronides more resistant to enzymatic degradation. Similarly, polygalacturonic acid is one of the main component of the aggregates.

Long-term influence of chitin concentration on the resistance of cement pastes determined by atomic force microscopy

The presence of sulfates potentialize damage on cementbased materials, leading to structural failures. Therefore, structures must be designed to compensate for this effect. The mechanical properties of cement–chitin mixtures are investigated with different percentages of chitin (0.5, 1.3, and 2.1 wt.%) and aging of composite in a joint nanoscopic- and macroscopic-scale by experimental study. The objective is to increase the durability of concrete elements at coastal aquifers where concrete structures are in constant exposure to sulfate ions, chloride ions among others. Tapping mode AFM was used to characterize the surface structure and roughness of the cement pastes. To verify the chitin addition and the formation of sulfate-based aggregates Raman and IR spectra were recorded and are presented in this work. Then, force spectroscopy was used to obtain the nanomechanical properties at three different exposure times (1 day, 6 months, and 1 year) into water or a SO4 2 environment. Macroscopic parameters (e.g., compression strength of cylindrical probes) were assessed for comparison following standard guidelines. The results show a decrease of its mechanical properties as a function of the polymer concentration but more importantly, they correlate the elasticity and adhesion at the nanoscale with the behavior of the bulk material.

Study of heterostructures of Cu3BiS3–buffer layer measured by Kelvin probe force microscopy measurements (KPFM)

The interface formed between Cu3BiS3 thin films and the buffer layer is a potentially limiting factor to the performance of solar cells based on Al/Cu3BiS3/buffer heterojunctions. The buffer layers of ZnS and In2S3 were grown by coevaporation, and tested as an alternative to the traditional CdS deposited by chemical bath deposition. From the Kelvin probe force microscopy measurements, we found the values of the work function of ZnS, In2S3, and CdS, layers deposited into Cu3BiS3. Additionally, different electronic activity was found for different grain boundaries (GBs), from studies under illumination, we also found the net doping concentration and the density of charged GB states for Cu3BiS3 and Cu3BiS3/CdS.

Interstitial Defects Induced Ferroelectricity in Undoped ZnO Nanorods at Room Temperature

A simple approach for obtaining room temperature ferroelectricity in ZnO rod structures at the nanoscale is reported. A systematic comparative study between two kinds of nanorods prepared by different processes reveals the physics behind it. It is observed that ZnO nanorods grown (in-situ) by a sol gel method on platinum substrate show ferroelectric behaviour. On the contrary, ZnO nanorods first grown by a sol gel method and then spin-coated on a platinum substrate (ex-situ) do not demonstrate this kind of feature. X-ray diffraction analysis confirms partially (002) and (100) plane oriented growth of both samples. From photoluminescence (PL) spectral analysis it is interpreted that oxygen vacancies/zinc interstitial defects, which arises from the large lattice mismatch between the Pt substrate and the ZnO nanorods grown thereon, and preferential ZnO growth along 002], can be causes of this type of phenomena. C-V characterization, P-E hysteresis loop along with piezoelectric force microscopy support this observation.

Ferroelectric origin in one-dimensional undoped ZnO towards high electromechanical response

Ferroelectricity in ZnO is an unlikely physical phenomenon. Here, we show ferroelectricity in undoped 001] ZnO nanorods due to zinc vacancies. Generation of ferroelectricity in a ZnO nanorod effectively increases its piezoelectricity and turns the ZnO nanorod into an ultrahigh-piezoelectric material. Here using piezoelectric force microscopy (PFM), it is observed that increasing the frequency of the AC excitation electric field decreases the effective d(33). Subsequently, the existence of a reversible permanent electric dipole is also found from the P-E hysteresis loop of the ZnO nanorods. Under a high resolution transmission electron microscope (HRTEM), we observe a zinc blende stacking in the wurtzite stacking of a single nanorod along the growth axis. The zinc blende nature of this defect is also supported by the X-ray diffraction (XRD) and Raman spectra. The presence of zinc vacancies in this basal stacking fault modulates p-d hybridization of the ZnO nanorod and produces a magnetic moment through the adjacent oxygen ions. This in turn induces a reversible electric dipole in the non-centrosymmetric nanostructure and is responsible for the ultrahigh-piezoelectric response in these undoped ZnO nanorods. We reveal that this defect engineered ZnO can be considered to be in the competitive class of ultrahigh-piezoelectric nanomaterials for energy harvesting and electromechanical device fabrication.

Multiferroic domain dynamics in strained strontium titanate

Multiferroicity can be induced in strontium titanate by applying biaxial strain. Using optical second harmonic generation, we report a transition from 4/mmm to the ferroelectric mm2 phase, followed by a transition to a ferroelastic-ferroelectric mm2 phase in a strontium titanate thin film. Piezoelectric force microscopy is used to study ferroelectric domain switching. Second harmonic generation, combined with phase-field modeling, is used to reveal the mechanism of coupled ferroelectric-ferroelastic domain wall motion. These studies have relevance to multiferroics with coupled polar and axial phenomena.

Epitaxial ferroelectric Pb(Mg1/3Nb2/3)O3-PbTiO3 thin films on La0.7Sr0.3MnO3 bottom electrode

Epitaxial (001)-oriented 0.7Pb(Mg_0.33Nb_0.67)O₃-0.3PbTiO₃ (PMN-PT) thin films were deposited by pulsed laser deposition on vicinal SrTiO₃ (001) substrates using La_0.7Sr_0.3MnO₃ as bottom electrode. Detailed microstructural investigations of these films were carried out using X-ray diffraction (XRD), atomic force microscopy (AFM) and transmission electron microscopy (TEM). Polarization-field hysteresis curves were measured at room temperature. Spontaneous polarization P s , remnant polarization P r and coercive voltage V c were found to be 25 μC/cm², 15 μC/cm² and 0.81 V, respectively. Field dependent dielectric constant measurements exhibited butterfly shaped curves, indicating the true ferroelectric nature of these films at room temperature. The dielectric constant and the dielectric loss at 100 kHz were found to be 238 and 0.14, respectively. The local piezoelectric properties of PMN-PT films were investigated by piezoelectric force microscopy and were found to exhibit a local piezoelectric coefficient of 7.8 pm/V.

Magnetoelectric coefficient in strontium ruthenate buffered lanthanum modified bismuth ferrite thin films grown by chemical method

This paper focuses on the magnetoelectric coupling (ME) at room temperature in lanthanum modified bismuth ferrite thin film (BLFO) deposited on SrRuO 3-buffered Pt/TiO 2/SiO 2/Si(100) substrates by the soft chemical method. BLFO film was coherently grown at a temperature of 500 °C. The magnetoelectric coefficient measurement was performed to evidence magnetoelectric coupling behavior. Room temperature magnetic coercive field indicates that the film is magnetically soft. The maximum magnetoelectric coefficient in the longitudinal direction was close to 12 V/cmOe. Dielectric permittivity and dielectric loss demonstrated only slight dispersion with frequency due the less two-dimensional stress in the plane of the film. Polarization reversal was investigated by applying dc voltage through a conductive tip during the area scanning. We observed that various types of domain behavior such as 71 ° and 180° domain switching, and pinned domain formation occurred. Copyright © 2009 American Scientific Publishers All rights reserved.

Microscopic and dielectric analyses of vanadium and tungsten modified barium zirconium titanate ceramics

Dielectric spectroscopy was used in this study to examine polycrystalline vanadium and tungstendoped BaZr 0.1Ti 0.90O 3 (BZT10:2V and BZT10:2W) ceramics obtained by the mixed oxide method. According to X-ray diffraction analyses, addition of vanadium and tungsten lead to ceramics free of secondary phases. SEM analyses reveal that both dopants result in slower oxygen ion motion and consequently lower grain growth rate. Temperature dependence dielectric study showed normal ferroelectric to paraelectric transition well above the room temperature for the BZT10 and BZT10:2V ceramics. However, BZT10:2W ceramic showed a relaxor-like behavior near phase transition characterized by the empirical parameter γ. Piezoelectric force microscopy images reveals that the piezoelectric coefficient is strongly influenced by type of donor dopant suggesting promising applications for dynamic random access memories and data-storage media. Copyright © 2010 American Scientific Publishers All rights reserved.

Piezoelectric properties of PbTiO(3) thin films characterized with piezoresponse force and high resolution transmission electron microscopy

In this paper we investigate the piezoelectric properties of PbTiO(3) thin films grown by pulsed laser deposition with piezoresponse force microscopy and transmission electron microscopy. The as-grown films exhibit an upward polarization, inhomogeneous distribution of piezoelectric characteristics concerning local coercive fields, and piezoelectric coefficient. In fact, the data obtained reveal imprints during piezoresponse force microscopy measurements, nonlinearity in the piezoelectric deformation, and limited polarization reversal. Moreover, transmission electron microscopy shows the presence of defects near the film/substrate interface, which can be associated with the variations of piezoelectric properties.

AFM cantilever with integrated piezoelectric thin film for micro-actuation

This work presents micro-actuation of atomic force microscopy (AFM) cantilevers using piezoelectric Zinc Oxide (ZnO) thin film. In tapping mode AFM, the cantilever is driven near its resonant frequency by an external oscillator such as piezotube or stack of piezoelectric material. Use of integrated piezoelectric thin film for AFM cantilever eliminates the problems like inaccurate tuning and unwanted vibration modes. In this work, silicon AFM cantilevers were sputter deposited with ZnO piezoelectric film along with top and bottom metallic electrodes. The self-excitation of the ZnO coated AFM cantilever was studied using Laser Doppler Vibrometer (LDV). At its resonant frequency (227.11 kHz), the cantilever displacement varies linearly with applied excitation voltage. We observed an increase in the actuation response (131nm/V) due to improved quality of ZnO films deposited at 200 degrees C.