Studies of Lead Zirconate Titanate Sol Ageing Part I: Factors Affecting Particle Growth

The formation and growth of polymeric particles during the hydrolysis and condensation of PbZr_0.3Ti_0.7O₃ (PZT 30/70) precursor solutions have been studied as functions of time by using photon correlation spectroscopy (PCS). Particle shape was deduced by measuring the rheological properties of the sols and was found to remain chain-like during sol ageing. Various factors that affect the ageing of PZT sols have been investigated. Ethylene glycol (EG) was found to greatly accelerate the hydrolysis and condensation of the acid-modified Pb-free Zr/Ti solutions but had little effect on the particle growth for the Pb-containing PZT sols. Temperature and H₂O concentration were found to have major effects on the ageing behaviors. The higher the temperature and H₂O concentration, the higher the particle growth rates and the faster the sol gels.     

Simple sound transmission loss measurements using a modified impedance tube technique

A method of comparing the sound transmission characteristics of various materials, and combinations of materials, is presented, using a modified impedance tube technique. The procedure proved to be relatively quick and inexpensive in comparison with standard reverberation suite tests, and is therefore particularly useful for the qualitative ranking of multiple samples.The limitations of the technique are discussed in some detail, and particular emphasis is given to the problems of small sample size and method of mounting in the apparatus.     

Determination of Particle Size and Shape during the Hydrolysis of Pb(Zr0.3Ti0.7)O3 Precursor Solutions

The formation and growth of polymeric particles during the hydrolysis and condensation of PbZr_0.3Ti_0.7 O₃ (PZT 30/70) sol-gel precursor solutions have been investigated by using photon correlation spectroscopy (PCS), small angle X-ray scattering (SAXS) and by measuring their rheological properties. The measurements showed that the growth of the particles in the transition of PZT sol to gel followed a simple polymerisation process. Solution A (containing by-products) and Solution B (by-products removed) displayed a similar plot of logarithmic viscosity against logarithmic time, indicating that the particles in both solutions have similar structures after hydrolysis. The changes in viscosity and particle size with time were described by single logarithmic growth models. However, the increasing rate of logarithmic particle size in Solution B is higher than that in Solution A. A model for the form of the aggregates is discussed which is applicable to PZT organometal-particle aggregation process in systems with acetic acid as a modifier.     

A Comparison of the Nanostructure of Lead Zirconate,Lead Titanate and Lead Zirconate Titanate Sols

Sol-gel processing has been widely used for the fabrication of lead zirconate titanate (PZT) thin films. To successfully and consistently make high quality thin films for different applications, we must develop a fundamental understanding of the structures of the sols. In this study, the characters of lead titanate (PT) and lead zirconate (PZ)sols were studied by measuring the rheological properties and particle sizes in them and comparing their behaviours. The average particle sizes in unhydrolysed PT, PZ and PZT sols are 11.5, 1.0, and 6.0 nm, respectively. PT sol has the highest rate of hydrolysis. It gels at about 24 h after hydrolysis. PZ and PZT sols have a quite similar feature in hydrolysis. The reasons for the differences in the hydrolysis behaviour of the different types of sol are discussed in terms of a model which indicates that the inhomogeneous sols consist of 5 to 6 nm PT particles surrounded by much smaller PZ particles, which tend to dominate the sol behaviour.     

Stereocontrolled synthesis of a d-amicetose functionalised tetrahydroxanthone related to kigamicin A

A glycosylated tetrahydroxanthone mimicking the ABC subunit of kigamicin A is synthesised in five steps by a sequence that exploits a Pd catalysed C–O bond forming reaction to construct the tetrahydroxanthone nucleus; chemo- and enantioselective Ru-catalysed transfer hydrogenation to establish the C-14 hydroxyl stereochemistry in the A-ring; and a trichloroacetimidate activated donor to introduce the β-linked d-amicetose unit in a stereoselective manner.     

Tetrahydroxanthones by sequential Pd-catalyzed C-O and C-C bond construction and use in the identification of the "antiausterity" pharmacophore of the kigamicins

Readily available C-acylated cycloalkanones undergo efficient Pd catalyzed ring closure/cross-coupling providing 7-substituted tetrahydroxanthones in a single operation. One of the synthesized derivatives (depicted) is shown to selectively kill pancreatic cancer (PANC-1) cells under conditions of nutrient deprivation indicating that the tetrahydroxanthone is responsible, in part, for the "antiausterity" effects of the naturally occurring kigamicins.     

Studies of Lead Zirconate Titanate Sol Aging Part II: Particle Growth Mechanisms and Kinetics

The kinetics of particle growth in lead zirconate titanate sol gel precursor solutions has been investigated. It was found that chemical reaction limited aggregation was responsible for most of the sol aging, followed by diffusion limited aggregation in the later stage. At the beginning, particles grow by reaction between initial polymers and particles. As the particle number-density increases, a particle-particle aggregation characterised by an exponential growth law becomes the predominant mechanism. When particles grow larger, towards gel formation, the aggregation changes to diffusion limited. Mathematical models derived according to the above mechanisms agreed well with experimentally measured particle growth profiles.     

Studies toward the synthesis of luminacin D: assembly of simplified analogues devoid of the epoxide displaying antiangiogenic activity

[reaction: see text] A series of structurally simplified luminacin analogues devoid of the epoxide ring are assembled in a stereocontrolled manner from 2,4-dimethoxybenzaldehyde using a syn-selective aldol reaction as the key step. The success of the approach is critically dependent on the nature and extent of the alcohol protecting groups. The synthetic analogues inhibit VEGF-stimulated angiogenesis in an in vitro assay indicating that the epoxide is not essential for biological activity in this compound class.