MICROFABRICATION METHODS FOR MICROCHANNEL REACTORS AND SEPARATIONS SYSTEMS

The fabrication of a microchannel chemical solvent separation unit and a microchannel chemical reactor is described. The performance of the solvent separation unit was enhanced by improved kinetic effects resulting from short liquid/liquid contact times in the device. These effects were exploited to allow preferential extraction of solute species from a fluid waste stream. The completed unit consisted of a series of microchannels separated by micromachined metal or polyimide membranes. Channel and membrane layers were produced from individual layers of type 304 stainless steel shim. Laser micromachining, photochemical machining, and photolithographic patterning were used to fabricate the individual layers. Flow channel width, height and length was 100 μm, 1 cm, and 8 cm respectively. The channels had an aspect ratio of 1000. The separation membranes consisted of an array of 5- μm to 30- μm-diameter micropores laser micromachined in polyimide or 130 μm diameter micropores machined through the stainless steel shim using photochemical etching

Microscale catalytic and mass transfer reactions were employed by the chemical reactor to achieve high efficiency partial oxidation reactions and conversion of methane to syngas. The chemical reactor was fabricated from laminated stainless steel, and consisted of four micro-channel chambers with a combustion section. The reactor successfully operated at temperatures near 900°C.     

Size dependency of citric acid monohydrate growth kinetics

An experimental study concerned with the growth kinetics of citric acid monohydrate crystals is presented. Due to the properties of the system, which is very soluble, with low solid-liquid density difference and high liquid viscosity, two different techniques were used: large crystals (710-850 μm) were growtn in a fluidized bed crystallizer; small crystals, belonging to three size ranges from 90 to 355 μm, were grown in the cell of a laser light diffraction granulometer. A first order growth kinetics resulted in both cases; a comparative analysis of both the present data and those reported in the literature relevant to larger or smaller crystals, indicates that the system exhibits size-dependent growth, which increases linearly with the crystal size.     

Excimer Laser Induced Removal of Particles from Hydrophilic Silicon Surfaces

A pulsed KrF excimer laser was used to remove several types of submicron-sized particles from silicon surfaces. Polystyrene latex particles, 0.1 μm and larger, were removed from silicon surfaces by dry laser cleaning (no water layer condensed on the surface) but SiO₂ particles could not be so removed. However, during steam laser cleaning, in which a thin film of water is deposited on the surface as both an energy transfer medium and an adhesion force reduction agent, these 0.1-0.2 μm SiO₂ particles were almost entirely removed. Calculations of the various forces contributing to adhesion indicate that hydrogen bonds are the major contributor to the adhesion of inorganic particles to substrate surfaces. Photoacoustic detection, using piezoelectric transducers, monitored the surface vibrations induced by the laser pulses.     

Sequential multiple-laser-assisted polishing of free-standing CVD diamond substrates

Diamond, the best thermal conductor known, is the ultimate choice as a substrate material for the fabrication of denser, smaller and faster electronic packages. Consequently, in recent years, worldwide efforts have focused on the design of manufacturing transparent technologies for post-synthesis processing (polishing, planarization, metallization, die attach,, etc.) of diamond substrates In this study, a manufacturing-transparent, cost-effective, non-vacuum, laser-assisted coarse polishing technique for thick free-standing CVD diamond substrates was investigated [2]. The thickness of the substrates varied from 700 to 1000 μm, with the average grain size ranging from 150 to 200 μm. The average surface roughness (R_a) of the substrates, measured using contact surface profilometry, was between 20 and 30 μm. The substrates were initially irradiated with a Nd-YAG laser (λ = 532 nm) for coarse material removal, followed by an ArF excimer laser (λ = 193 nm) for finer surface finishing. Under optimized conditions, the average surface roughness (R_rma) was reduced from 25 to 5 μm with the Nd-YAG laser, and further to less than or equal to 1 μm with the excimer laser. The technique, which is the fastest processing technique known to the authors, is capable of polishing a 1 cm × 1 cm × 0.07 cm substrate in 50 s.     

Effect of Microstructure on Ferroelectric and Piezoelectric Properties of A-Site and B-Site Modified PLZT

Ba modified (Pb,La,Ag)(Zr,Ti)O₃ ceramics synthesized by conventional mixed-oxide method with chemical formula [Pb_{0.983 - z}La_0.012Ag_0.005Ba_z] [(Zr_0.52Ti_0.48)_0.99825]O₃ were investigated for ferroelectric and piezoelectric properties. XRD studies indicate that increment of Ba concentration resulted in strong tetragonality in the ceramics. Grain growth (3.08 μ m) inhibited and apparent density (7.54 gm/cm³) enhanced up to 1.5 mole% Ba respectively. As Ba content increased dielectric properties showed maximum values (ε_RT = 2347, ε_Tc = 23449) while T_c constantly decreased. The remanent (P_r = 34.72 μ C/cm²) and spontaneous polarization (P_s = 41.84 μ C/cm²) were optimum in 1 mole% Ba respectively while E_c showed increasing trend throughout the series. Piezoelectric properties attained maximum values of d₃₃ = 438 pC/N in 1.5 mole% Ba while k_p = 0.533 and k_t = 0.412 in 1 mole% Ba doped (Pb,La,Ag)(Zr,Ti)O₃ ceramics respectively.     

Graphite-to-diamond transformation induced by ultrasound cavitation

Diamond microcrystals have been synthesized using ultrasonic cavitation of a suspension of hexagonal graphite in various organic liquid media, at an average bulk temperature of the liquid up to 120°C and at atmospheric pressure. The yield of diamond is up to 10% by mass. The diamonds were characterized by scanning electron microscopy, X-ray diffraction and laser Raman spectroscopy. Analysis of the crystallite size distribution showed that the diamonds were nearly mono-dispersed, having a size 6 or 9μm ± 0.5μm, with cubic, crystalline morphology.     

Pretreatment of substrate surface for improved adhesion of diamond films on hard metal cutting tools

The d.c. plasma jet CVD process is one of the most promising coating processes used for the production of polycrystalline diamond films. In comparison with other CVD processes, its obtainable linear growth rates, in the range of 100 μm/h, are much higher than growth rates of microwave or hot filament CVD (1–10 μm/h).

One interesting application is the diamond coating of cutting tools. The main problem here is the poor adhesion of the films. Therefore, a mechanical or chemical pretreatment or intermediate layers are used to improve the adhesion.

In these investigations the influence of mechanical pretreatment by grinding and polishing with diamond powder of different grain sizes as well as chemical etching are examined on WC-Co hardmetals. Sputtered metallic interlayers of different thicknesses and arc-ion plated amorphous carbon films are deposited on these substrates, and diamond films were synthesized on these pretreated cutting tools by d.c. plasma jet CVD.

Adhesion and wear resistance of the diamond films have been examined by dry turning tests on very abrasive metal-matrix composites. Distinct improvement in adhesion of diamond coatings on hard metal substrates was achieved by two methods of substrate surface pretreatment: etching with Murakami's solution and following ultrasonically seeding with diamond particles or using an amorphous carbon film as intermediate layer.     

Crystallisation of Wild-Type and Variant Forms of a Recombinant Plant Enzyme ��-d-Glucan Glucohydrolase from Barley (Hordeum vulgare L.) and Preliminary X-ray Analysis

Wild-type and variant crystals of a recombinant enzyme β-d-glucan glucohydrolase from barley (Hordeum vulgare L.) were obtained by macroseeding and cross-seeding with microcrystals obtained from native plant protein. Crystals grew to dimensions of up to 500 × 250 × 375 μm at 277 K in the hanging-drops by vapour-diffusion. Further, the conditions are described that yielded the wild-type crystals with dimensions of 80 × 40 × 60 μm by self-nucleation vapour-diffusion in sitting-drops at 281 K. The wild-type and recombinant crystals prepared by seeding techniques achived full size within 5–14 days, while the wild-type crystals grown by self-nucleation appeared after 30 days and reached their maximum size after another two months. Both the wild-type and recombinant variant crystals, the latter altered in the key catalytic and substrate-binding residues Glu220, Trp434 and Arg158/Glu161 belonged to the P4₃2₁2 tetragonal space group, i.e., the space group of the native microcrystals was retained in the newly grown recombinant crystals. The crystals diffracted beyond 1.57–1.95 Å and the cell dimensions were between a = b = 99.2–100.8 Å and c = 183.2–183.6 Å. With one molecule in the asymmetric unit, the calculated Matthews coefficients were between 3.4–3.5 ų·Da⁻¹ and the solvent contents varied between 63.4% and 64.5%. The macroseeding and cross-seeding techniques are advantageous, where a limited amount of variant proteins precludes screening of crystallisation conditions, or where variant proteins could not be crystallized.     

Dielectric, Ferroelectric and Piezoelectric Studies of PMN Modified PLZT Ceramics

Dielectric, ferroelectric and piezoelectric properties of xPb(Mg_1/3Nb_2/3)O₃-(1-x)(Pb_0.988 La_0.012)(Zr_0.535Ti_0.465)O₃ ceramic system synthesized through columbite precursor method are investigated. X-ray diffraction patterns of ceramics indicated pseudocubic phase formation with pyrochlore phase. Grain growth (4.47 μ m) and apparent density (7.68 gm/cm³) enhanced remarkably in 0.8PMN-0.2PLZT composition, respectively. Increasing PMN content remarkably increased both room temperature dielectric permittivity (ε_RT = 2316) and dielectric maximum (ε_Tc = 24747) in 0.6PMN-0.4PLZT composition, respectively. PMN substitution in PLZT system enhanced the ferroelectric remanent (P_r = 28.4 μ C/cm²) and spontaneous (P_s = 31.2 μ C/cm²) polarization while coercive field (E_c) continuously decreased in xPMN-(1-x)PLZT system. PMN modification in PLZT system influenced piezoelectric properties (d₃₃, k_p and k_t) throughout the PMN-PLZT system.     

Modelling the ignition of brown-coal particles

The unsteady-state mass and energy equations have been set up for the case of a single particle of brown coal plunged into a hot gas stream. These equations have been solved, with the aid of a digital computer, to give temperature histories for particles 20, 100 and 1000 μm in diameter. Analysis of these histories reveals that although ignition sometimes occurs with an abrupt temperature-jump, it can also occur without it; the last may possibly be associated with ignition instability. Reduction of particle size and of oxygen partial pressure both render temperature-jump ignition less likely. Gas temperatures required for ignition of brown-coal particles are only 600–800 K, the larger particles igniting at lower temperatures; ignition times are typically 5 ms for a 20 μm particle and 50 ms for a 100 μm particle, and are more affected by gas temperature than by oxygen concentration. It is unlikely that radiation plays a major part in the ignition of pulverized brown coal; recirculation of hot combustion products probably dominates. It is concluded that the ignition stability of burners fired with pulverized brown coal could be improved by avoiding the dilution of the coal stream with water vapour or inert drying gas, and by promoting the recirculation of hot gases back to the burner inlets. While the methods used are general and applicable (with appropriate reaction rate data) to other materials, the results here given depend heavily on the high chemical reaction rates between brown coal and oxygen at relatively low temperatures and are specific.     

Counting efficiencies of six commercial particle counters

Counting efficiencies of a condensation nuclei counter (TSI 3020), a white-light optical particle counter (Climet CI-8060) and four laser instruments (PMS LAS-X, LAS-250X, LPC 525 and HP-LAS) were determined relative to the LAS-X.

Measurements were made in the geometric diameter range of 0.1–4 μm using latex spheres as well as monodisperse organic and inorganic particles produced by a vibrating orifice generator.

The high-pressure in-line counter (HP-LAS) shows a nonlinear response to gas velocity which can be taken into account by a calibration. The lower detection limits (50% points) of the conventional laser counters (LAS-X and LAS-250X) agree within 0.05 μm with their nominal specifications; for the white-light counter (CI-8060) the actual lower limit is at about 0.4 μm. For all counters, the degree of inlet losses for larger particles varies greatly with inlet design and flow velocity of each counter.     

A polarised μ-FTIR study on a model system for nylon 6 6: implications for the nylon Brill structure

Polarised transmission FTIR microscopy studies (μ-FTIR) have been performed on a monodisperse 3-amide oligomer. The oligomer is a model compound for nylon 6 6; it has essentially the same room temperature crystal structure, and it undergoes the same high temperature transition, the Brill transition, prior to melting. However, the oligoamide forms extended chain, rather than chain-folded, crystals, and so crystals are produced that are essentially 100% crystalline, and of μm–mm size. Consequently, this material is ideally suited for polarised μ-FTIR single crystal studies. The thermal polarised FTIR behaviour of this material provides definitive proof that the Brill transition does not involve major rearrangement of hydrogen bonds, since the strong parallel polarisation of both the NH stretch and amide I bands are retained right up to melting. Quantitative infrared dichroism measurements indicate that a maximum of 5° rotation of the N–H bonds about the extended chain axis occurs prior to melting. These results strongly suggests that the equivalent Brill transition in nylon 6 6 also proceeds without significant hydrogen bond rearrangement. In addition we have investigated the behaviour of designated ‘Brill’, ‘crystalline’, ‘amorphous’ and ‘fold’ bands that are present in our spectra.     

Enhancement of NaA zeolite membrane properties through organic cation addition

Thin NaA zeolite membranes, with uniform and small crystals, were prepared on the tubular -Al₂O₃ support by adding a small amount of tetramethylammonium hydroxide (TMAOH) in the clear synthesis solution. The as-synthesized NaA zeolite membranes were characterized by XRD and SEM. The permeation properties of the membranes were evaluated by pervaporation and gas permeation. The effects of TMAOH amount on membrane formation and permeation properties were investigated. By addition of suitable amount of TMAOH in the clear synthesis solution, the crystals size of NaA zeolite could be remarkably reduced from about 10 μm to 3–4 μm, and the membrane thickness correspondingly reduced from about 16 μm to 5 μm. The thinner membrane prepared by adding TMAOH in the clear synthesis solution, with uniform and small crystal, displayed higher perm-selective properties than that without adding TMAOH. For the as-synthesized NaA zeolite membrane prepared with adding suitable amount of TMAOH (x = 1), the separation factor (water/isopropanol) was 4700 and the flux was 1.67 kg/(m² h), which were higher than that without adding TMAOH of 339 and 1.08 kg/(m² h), respectively. The ideal separation factor of H₂/N₂ was 6.60, higher than that without adding TMAOH of 3.41.     

Electrical and mechanical properties of ferroelectric lead zirconate titanate/tungsten oxide ceramics

Ferroelectric PZT/xWO₃ ceramics (when x = 0, 0.5, 1, 3 and 5 vol%) were fabricated from PZT and nano-sized WO₃ powders by a solid-state mixed-oxide method. Phase characterization suggested that the reaction between PZT and WO₃ occurred during the sintering. This reaction seemed more pronounced with increasing the content of WO₃. The maximum density at approximately 97% of the theoretical value was achieved at 1 vol% of WO₃ addition. The grain size was reduced with an addition of WO₃ particles from 7.8 μm for PZT to 1.8 μm for 0.5 vol% WO₃ and 0.8 μm for 1–5 vol% WO₃. Mechanical properties of PZT could be improved with an addition of WO₃ nano-particulates. The addition of 0.5 vol% WO₃ could maintain good electrical properties while increasing WO₃ significantly reduced dielectric and piezoelectric constants of the PZT.     

Effect of sintering aid and repeated sol infiltrations on the dielectric and piezoelectric properties of a PZT composite thick film

Thick PZT films have been produced using a combination of spin coating of a composite slurry and subsequent infiltration of PZT producing sol. The effect of adding a Cu₂O–PbO sintering aid and repeated sol infiltrations have been studied with the aim of producing dense PZT films. Relative permittivity has been shown to increase with the addition of sintering aid and increased levels of sol infiltration. Measurements of piezoelectric properties indicate that sol infiltrations have no effect on d₃₃ once a critical density has been exceeded. A sample with approximately 10% closed porosity was obtained following the incorporation of sintering aid and four infiltration steps per layer. This resulted in a mean relative permittivity of approximately 700 and a d₃₃ of 62 pC/N (poling conditions: 8 V/μm for 5 min at 200 °C).     

Field emission of polycrystalline diamond films grown by microwave-plasma chemical vapor deposition. I. Effects of surface morphology of diamond

The effects of surface morphology on the field emission of non-doped polycrystalline diamond films with thicknesses ranging from 5 to 55 μm were studied. Diamond films grown by a microwave-plasma chemical vapor deposition technique had both the diamond and non-diamond components with pyramidal and angular crystalline structures. Although the average crystallite size increased with increasing the film thickness (d), the volume fraction of the non-diamond components in the films was insensitive to the film thickness. However, the turn-on electric field, F_T, (defined as the low-end electric field to emit electrons) showed a U-shape dependence on the film thickness. This U-shape dependence was explained by a model in which the emission current was controlled by Fowler–Norheim tunneling of electrons at surface of the pyramids when d was thinner than 20 μm and by carrier transport in the polycrystalline diamond film when d was thicker than 20 μm. The lowest field of 4 V/μm was obtained in the film with 20 μm thick.     

Studies on simultaneous crystallization of polypropylene/nylon 12 blends

The effect of the morphology of polypropylene (PP)/nylon 12 (PA12) blends on their crystallization behaviour is studied using differential scanning calorimetry and scanning electron microscopy. In PP/ maleated polypropylene (PP-MA)/PA12=65/10/25 blend, simultaneous phase (PA12) is smaller than 0.5 μm, PP crystallizes first and its crystals induce the crystallization of PA12. When some of the PA12 particles are larger than 0.5 μm, this part of PA12 crystallizes first. Then this part of the PA12 crystals induces the crystallization of PP, and PP crystals induced the crystallization of PA12 fine droplets in turn.     

A novel TGS/70:30 VDF:TrFE copolymer composite material for pyroelectric sensors

A novel thin composite film has been fabricated in which both phases are electroactive. Triglycine sulphate crystals (5μm in size), grown by rapid quenching and freeze drying of an aqueous solution, were mixed (10% w/w) with 70:30 vinylidene fluoride:trifluoroethylene copolymer in butanone. When spin cast, the material possessed a pyroelectric coefficient of (60±2)μCm^-2K^-1 and a figure of merit (pyroelectnc coefficient/√(relative permittivity x dielectric loss)) of 150μCm^-2K^-1, some 18% and 35% larger, respectively, than that of the pure copolymer.     

MEASUREMENTS OF THE NEAR INFRARED OPTICAL PROPERTIES OF COAL SLAGS

The spectral complex refractive index has been measured over the wavelength range of 1 μm to 12 μm for three coal ash samples. The measurements were conducted by making spectral transmittance and near-normal reflectance measurements on thin, homogeneous slag wafers prepared from the ash samples. The imaginary part of the refractive index k exhibits a large peak near 9 μm, attributable to Si-O vibrational absorption. Three smaller peaks in the k spectra were observed at 1·2μm, 1·8 μm, and 2·8 μm, which have been identified as due to absorption by the ferrous iron ion Fe²⁺ and the hydroxyl group OH. The dependence of the ash optical properties on ferrous iron content in the wavelength range of 1 μm to 5 μm suggests that both the total iron content of the ash and the ash oxidation state may affect the contribution of ash to radiative heat transfer in coal combustion systems.     

Dielectric and pyroelectric properties of triglycine sulphate-polystyrene composites

A composite of Triglycine sulphate (TGS) and polystyrene has been fabricated by mixing different particle size TGS powders (75 μm to 400 μm) and polystyrene solution. The dielectric constant has been measured in the frequency range 0.1 to 100 KHz, and the pyroelectric current measurements were made by the Byer and Roundy direct method. Specific heat of the composite was determined by the differential them analysis (DTA) technique.

Particle size dependance of dielectric constant, pyroelectric coefficient and responsivity have been studied. Anomalies in ε' and P_y were observed even in the composite with the lowest particle size of TGS (75 μm). The surface effects have much greater influence on electrical properties but thermal properties are, not affected. This is indicated by a decrease in ε' and P^y with decreasing particle size of TGS, while specific heat of composite is almost independent of particle size.