Zn Microparticles Research Articles

Co-occurrence of microplastics and microparticles containing Cu and Zn and other heavy metals in sea-surface microlayer in Osaka Bay, Japan

Antifouling biocides such as Cu, Zn, and organic compounds not only inhibit adhesion of sessile organisms on ship hull but also possess toxicity to non-sessile organisms in marine environment. Thus, we firstly investigated the heavy metals and polymer types of anthropogenic microparticles (MPs) floating in the sea-surface microlayer (S-SML) in Osaka Bay. 7 types of MPs containing different metals (Cu, Cu-Zn, Zn, Ti, Sn, Ba and Fe-Mn-Ni) were found. The polymer type for 97.8 % of Cu and Cu-Zn MPs (41 samples) and 52.6 % of Zn MPs (19 samples) was acrylic resins which are widely used as binders in contemporary antifouling paints for ships; concentrations of 511–54,000 mg/kg for Cu and 95.1–13,200 mg/kg for Zn were found in these MPs. The high metal concentrations found the co-existence of acrylic polymers point towards an origin from antifouling paint particles (APPs). Furthermore, to quantify Cu and Zn concentrations in these MPs based on X-ray fluorescence spectroscopy (μ-XRF), calibration curves obtained from standard paint particles containing different Cu and Zn concentrations and different particle sizes made with similar matrix used in commercial antifouling paint were firstly established, according to which highly reliable Cu and Zn concentrations in MPs were obtained.

Fabrication of RC filters from a single printed Zn layer by reactive inkjet printing

This paper presents the development of planar zinc (Zn) resistor–capacitor (RC) filters from a single printed layer that are both printed and treated at room temperature. The fabrication process involves screen printing the resistor, capacitor and interconnects in a single patterned layer on kraft paper substrates using a Zn microparticle ink. In order to form a distinct resistor and capacitor in the patterned structure, reactive inkjet printing (RIJ) was performed to selectively dispense acetic acid on the RC filter pattern to achieve regions with highly contrasting resistance. The required high degree of spatial contrast was achieved using the positional control of the inkjet printer combined with the number of print passes and drop spacing used to dispense the acetic acid droplets. X-ray diffraction and scanning electron microscopy showed the crystal structure and grain size of Zn microparticles remained unchanged with increasing acetic acid exposure while the prominence of cold-welding increased with increasing exposure. Zn-based RC filters sharing a common set of dimensions but with a wide range of corner frequencies were successfully fabricated using this process. For a fixed filter geometry, the corner frequencies could be tuned from ∼7 kHz to ∼1 MHz as the number of print passes used to form the resistor increased in a stepwise manner. To the best of our knowledge, this is the first room temperature printing process to produce side-by-side resistors and conductors from the same printed layer and the first printing process of any type to produce RC filters with such a wide range of corner frequencies.

Oxidation of Zinc Microparticles by Microwave Plasma to Form Effective Solar-Sensitive Photocatalysts

The presented work studies the processes of synthesis of ZnO microstructures using atmospheric-pressure microwave nitrogen plasma and investigates their photocatalytic activity in the processes of degradation of 2,4-dinitrophenol and the antibiotic ciprofloxacin when irradiated with sunlight. The work proposes an effective method for formation of photosensitive ZnO powders. Due to the features of plasma treatment in the open atmosphere of zinc metal microparticles, ZnO structures are formed with sizes from hundreds of nanometers to several micrometers with various micromorphologies. The lattice parameters of ZnO structures are characteristic of a hexagonal unit with a = 3.258 Å and c = 5.21 Å, volume 47.95 Å3. The size of the crystallites is 48 nm. The plasma treatment was performed by means of a 2.45-GHz plasmatron at a power input of 1 kW in nitrogen flow at a rate of 1–10 L/min. Zn microparticles were injected into the microwave plasma at a mass rate of 20 g/min. High photoactivity was demonstrated (rate constants 0.036 min−1 and 0.051 min−1) of synthesized ZnO structures during photo-degradation of 2,4-dinitrophenol and ciprofloxacin, respectively, when exposed to solar radiation. Photo-active structures of ZnO synthesized using microwave plasma can find application in processes of mineralization of toxic organic compounds. Structures of ZnO synthesized using microwave plasma can find application in processes of mineralization of toxic organic compounds, and also in scintillation detectors, phosphors.

Zinc hybrid sintering for printed transient sensors and wireless electronics

Transient electronics offer a promising solution for reducing electronic waste and for use in implantable bioelectronics, yet their fabrication remains challenging. We report on a scalable method that synergistically combines chemical and photonic mechanisms to sinter printed Zn microparticles. Following reduction of the oxide layer using an acidic solution, zinc particles are agglomerated into a continuous layer using a flash lamp annealing treatment. The resulting sintered Zn patterns exhibit electrical conductivity values as high as 5.62 × 106 S m−1. The electrical conductivity and durability of the printed zinc traces enable the fabrication of biodegradable sensors and LC circuits: temperature, strain, and chipless wireless force sensors, and radio-frequency inductive coils for remote powering. The process allows for reduced photonic energy to be delivered to the substrate and is compatible with temperature-sensitive polymeric and cellulosic substrates, enabling new avenues for the additive manufacturing of biodegradable electronics and transient implants.

The Influence of Supplementation with Zinc in Micro and Nano Forms on the Metabolism of Fatty Acids in Livers of Rats with Breast Cancer.

The aim of this study was to investigate the effect of zinc supplementation (in the form of nano or microparticles) on the profile and metabolism of fatty acids in the liver microsomes of rats with induced breast cancer. The activity of desaturases (Δ5, Δ6, Δ9) and the level of cholesterol and its oxidized derivatives were measured. The aim of this study was also to determine the effect of various forms of zinc supplements on rats that were on 5-, 12- and 15-hydroxyeicosatetraenoic (5-, 12- and 15-HETE) and hydroxyoctadecadienoic (HODE) acids, and the level of prostaglandin E2 (PGE2). Female Spraque-Dawley rats (n = 24) were divided into 2 groups that were supplemented with zinc in the micro form (342 nm) or nano form (99 nm) particles, respectively, and a group with a standard diet (control group). All animals received 7,12-dimethylbenz[a]anthracene twice for the induction of breast cancer. Dietary nano-Zn supplementation increased vaccenic acid content (p = 0.032) and decreased Δ6-desaturase activity (p = 0.006), whereas micro-Zn increased cholesterol (p = 0.006), ∑COPs (total cholesterol-oxidation products) (p = 0.019) and PGE2 (p = 0.028) content. Dietary enrichment with Zn microparticles resulted in lower concentrations of the metabolites 15-, 12- and 5-HETE and HODE. Our study indicates that the effect of zinc supplementation on the metabolism of fatty acids in the liver microsomes under neoplastic conditions depends on the form in which it is administered.

Zinc Affects Cholesterol Oxidation Products and Fatty Acids Composition in Rats' Serum.

The purpose of this work was to evaluate the effect of the nanosized or microsized zinc (Zn) particles on fatty acid profile, enzyme activity and the level of cholesterol, squalene and oxysterols in rats with breast cancer. Rats (female, n = 24) were divided into the following groups: control, and two test groups, whose diets were enriched with either Zn microparticles (342 nm) or Zn nanoparticles (99 nm). All rats were treated twice with the carcinogenic agent; 7,12-dimethylbenz[a]anthracene. In rats whose diet was enriched with zinc (especially in the form of nanoparticles), the number and sizes of tumors were lower. Diet supplementation also significantly reduced the cholesterol (p = 0.027) and COPs (cholesterol oxidation products) levels (p = 0.011) in rats serum. Enriching the diet with Zn microparticles decreased the Δ6-desaturase activity (p < 0.001). Zn influences fatty acids’ profile in rats’ serum as well as inhibiting desaturating enzymes. A reduced amount of pro-inflammatory arachidonic acid derivatives may be the expected effect.

Bubble-Propelled Janus Gallium/Zinc Micromotors for the Active Treatment of Bacterial Infections.

We report a bubble-propelled Janus gallium/zinc (Ga/Zn) micromotor with good biocompatibility and biodegradability for active target treatment of bacteria. The Janus Ga/Zn micromotors are fabricated by asymmetrically coating liquid metal Ga on Zn microparticles and display self-propulsion in simulated gastroenteric acid (pH 0.5) at a speed of up to 383 μm s-1 , propelled by hydrogen bubbles generated by the zinc-acid reaction. This motion of Ga/Zn micromotors is enhanced by the Ga-Zn galvanic effect. The GaIII cations produced from the degradation of Ga/Zn micromotors serve as a built-in antibiotic agent. The movement improves the diffusion of GaIII and results in a significant increase of the antibacterial efficiency against H. pylori, compared with passive Ga microparticles. Such Ga/Zn micromotors combine the self-propulsion, good biocompatibility and biodegradability, and Ga-based antibacterial properties, providing a proof of concept for the active treatment of bacterial infections.

Bubble‐Propelled Janus Gallium/Zinc Micromotors for the Active Treatment of Bacterial Infections

AbstractWe report a bubble‐propelled Janus gallium/zinc (Ga/Zn) micromotor with good biocompatibility and biodegradability for active target treatment of bacteria. The Janus Ga/Zn micromotors are fabricated by asymmetrically coating liquid metal Ga on Zn microparticles and display self‐propulsion in simulated gastroenteric acid (pH 0.5) at a speed of up to 383 μm s−1, propelled by hydrogen bubbles generated by the zinc–acid reaction. This motion of Ga/Zn micromotors is enhanced by the Ga–Zn galvanic effect. The GaIII cations produced from the degradation of Ga/Zn micromotors serve as a built‐in antibiotic agent. The movement improves the diffusion of GaIII and results in a significant increase of the antibacterial efficiency against H. pylori, compared with passive Ga microparticles. Such Ga/Zn micromotors combine the self‐propulsion, good biocompatibility and biodegradability, and Ga‐based antibacterial properties, providing a proof of concept for the active treatment of bacterial infections.

Laser Sintering of Zn Microparticles and Its Application in Printable Biodegradable Electronics

AbstractThe rapid expansion of electronic technology and short lifespan of consumer devices create a huge amount of electronic waste. The disposal of discarded devices represents a serious environmental challenge. Biodegradable devices are able to decompose into benign components after a period of stable operation during its service life, which represents a potential solution to reduce the environmental footprint of electronic technology. The widespread applications of biodegradable electronics are still hampered by the lack of facile manufacturing approach for high quality devices. Here, a laser sintering technique to weld naturally oxidized Zn microparticles into biodegradable conductors is reported. The sintering process is carried out under ambient conditions and compatible with various biodegradable substrates. A low‐cost fabrication procedure involving stencil printing and laser treatment is established to create conductive features with excellent conductivity and mechanical durability. The practical suitability of printed Zn conductor is demonstrated by fabricating near‐field communication tags, which are flexible and fully functional with the transient behavior modulated by the choice of packaging materials. The printed biodegradable conductor may find potential applications in eco‐friendly sensors, transient printed circuit boards, and implantable medical devices.

Room Temperature Electrochemical Sintering of Zn Microparticles and Its Use in Printable Conducting Inks for Bioresorbable Electronics.

This study describes a conductive ink formulation that exploits electrochemical sintering of Zn microparticles in aqueous solutions at room temperature. This material system has relevance to emerging classes of biologically and environmentally degradable electronic devices. The sintering process involves dissolution of a surface passivation layer of zinc oxide in CH3 COOH/H2 O and subsequent self-exchange of Zn and Zn2+ at the Zn/H2 O interface. The chemical specificity associated with the Zn metal and the CH3 COOH/H2 O solution is critically important, as revealed by studies of other material combinations. The resulting electrochemistry establishes the basis for a remarkably simple procedure for printing highly conductive (3 × 105 S m-1 ) features in degradable materials at ambient conditions over large areas, with key advantages over strategies based on liquid phase (fusion) sintering that requires both oxide-free metal surfaces and high temperature conditions. Demonstrations include printed magnetic loop antennas for near-field communication devices.

Chitosan-zein nano-in-microparticles capable of mediating in vivo transgene expression following oral delivery

The oral route is an attractive delivery route for the administration of DNA-based therapeutics, specifically for applications in gene therapy and DNA vaccination. However, oral DNA delivery is complicated by the harsh and variable conditions encountered throughout gastrointestinal (GI) transit, leading to degradation of the delivery vector and DNA cargo, and subsequent inefficient delivery to target cells. In this work, we demonstrate the development and optimization of a hybrid-dual particulate delivery system consisting of two natural biomaterials, zein (ZN) and chitosan (CS), to mediate oral DNA delivery. Chitosan-Zein Nano-in-Microparticles (CS-ZN-NIMs), consisting of core Chitosan/DNA nanoparticles (CS/DNA NPs) prepared by ionic gelation with sodium tripolyphosphate (TPP), further encapsulated in ZN microparticles, were formulated using a water-in-oil emulsion (W/O). The resulting particles exhibited high CS/DNA NP loading and encapsulation within ZN microparticles. DNA release profiles in simulated gastric fluid (SGF) were improved compared to un-encapsulated CS/DNA NPs. Further, site-specific degradation of the outer ZN matrix and release of transfection competent CS/DNA NPs occurred in simulated intestinal conditions with CS/DNA NP cores successfully mediating transfection in vitro. Finally, CS-ZN-NIMs encoding GFP delivered by oral gavage in vivo induced the production of anti-GFP IgA antibodies, demonstrating in vivo transfection and expression. Together, these results demonstrate the successful formulation of CS-ZN-NIMs and their potential to improve oral gene delivery through improved protection and controlled release of DNA cargo.

CORE-SHELL Zn/ZnO STRUCTURES WITH IMPROVED PHOTOCATALYTIC PROPERTIES SYNTHESIZED BY AQUEOUS SOLUTION METHOD

A facile and green method was utilized to synthesize core-shelled Zn / ZnO microspheres by boiling Zn microparticles in water for improving the photocatalytic activity of ZnO . The synthesized Zn / ZnO core-shells were investigated by means of scanning electron microscope, X-ray diffractometer and photoluminescence spectrometer, respectively. The morphology analysis showed that the metallic Zn core was about 6 μm in diameter while the ZnO shell was about 600 nm in thickness. Compared to ZnO nanoparticles, the core-shelled Zn / ZnO microspheres exhibited improved photocatalytic activity in degrading methyl orange in water. Our results suggest that the metal–semiconductor junction formed at the Zn / ZnO interface is responsible for the enhanced photocatalytic activity of ZnO .

Rapid Synthesis of Piezoelectric ZnO-Nanostructures for Micro Power-Generators

In this paper, we report a rapid synthesis of piezoelectric ZnO-nanostructures and fabrication of the nanostructures-based power-generators demonstrating an energy conversion from an environmental mechanical/ultrasonic energy to an electrical energy. The ZnO nanostructures are grown on a silicon wafer by a modified chemical solution method (CSD, chemical-solution-deposition) with a two-step thermal-oxidation approach. The synthesis process can be completed within 1 h. By varying the mixture-ratio of Zn micro-particles in an oxalic acid solution with 0.75 mol/l concentration in the CSD process, the growth mechanism is well-controlled to synthesize three different types of ZnO-nanostructures (i.e., dandelion-like nanostructures, columnar nanostructures, and nanowires). Furthermore, through oxidizing at different temperatures in the thermal-oxidation process, the featured geometry of the nanostructures (e.g., the length and diameter of a nanowire) is modified. The geometry, size, morphology, crystallization, and material phase of the modified nanostructures are characterized by scanning electron microscopy and X-ray diffraction. Finally, the nanostructures are used to fabricate several micro power-generators. Through the piezoelectric effect, a maximum current density output of 0.28 μA cm−2 generated by a power-generator under an ultrasonic wave is observed.

Dusty plasma synthesis of nanostructured Zn/ZnO–carbon nanotube composites by aerosol flow condensation

A new, dusty plasma process for depositing nanoparticles generated by aerosol flow condensation and treated using a 13.56 MHz capacitively-coupled non-thermal glow discharge is described. The use of organometallic compounds as nanoparticle precursors is avoided, thereby allowing for a processing plasma free of contaminating degradation products. Nanostructured composites of zinc and zinc oxide were deposited on carbon nanotubes with complete coverage, and the influences of the argon quench and sheath gas flow rates, and the presence of 0.5 vol.% ethane in the processing plasma on the synthesized composites was investigated by electron microscopy and X-ray diffraction (XRD). In the absence of plasma, ∼1 μm Zn microparticles composed of agglomerated nanoparticles were formed on the carbon nanotube surface. Plasma processing produced coatings of nanoparticles with lognormal size distributions and median diameters of ∼5 nm. At maximum argon flow rates, the distribution was monodisperse, whereas lower flow rates produced bimodal size distributions with the second mode having median values of ∼70 nm.

Thermal evaporation and condensation synthesis of metallic Zn layered polyhedral microparticles

Metallic zinc layered polyhedral microparticles have been fabricated by thermal evaporation and condensation technique using zinc as precursor at 750 °C for 120 min and NH 3 as a carrier gas. The zinc polyhedral microparticles with oblate spherical shape are observed to be 2–9 μm in diameter along major axes and 1–7 μm in thickness along minor axes. The structural, compositional and morphological characterizations were performed by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). A vapour–solid (VS) mechanism based growth model has been proposed for the formation of Zn microparticles. Room temperature photoluminescence (PL) emission spectrum of the product exhibited a strong emission band at 369 nm attributed to the radiative recombination of electrons in the s, p conduction band near Fermi surface and the holes in the d bands generated by the optical excitation.

Evolution of Zn based high purity phases under NH 3 gas atmosphere and their PL properties

We report here the evolution of zinc based high purity phases with novel morphologies such as Zn 3N 2 hollow structures, ZnO nanowires and nanopowders, as well as metallic Zn layered hexagonal microparticles at progressively increased reaction temperature of 600 °C, 700 °C, 800 °C under NH 3 gas atmosphere using Zn powder precursor and keeping all other experimental parameters unchanged. Growth mechanism for Zn 3N 2 obtained by nitridation, ZnO by oxidation and Zn microparticles via thermal evaporation & condensation process are discussed briefly. The as-synthesized products were characterized by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS) and scanning electron microscopy (SEM). Photoluminescence (PL) studies have revealed very interesting and infrequently observed emission bands at 378 and 661 nm for Zn 3N 2, 359 and 396 nm for ZnO as well as 389 nm for Zn polyhedral microparticles.

Catalyst-free combined synthesis of Zn/ZnO core/shell hollow microspheres and metallic Zn microparticles by thermal evaporation and condensation route

Here we report catalyst-free combined synthesis of metal/semiconductor Zn/ZnO core/shell microspheres with hollow interiors on Si substrate and metallic Zn polygonal microparticles on glass substrate in a single experiment via thermal evaporation and condensation technique using nitrogen (N 2) as carrier agent at 800 °C for 120 min. The Zn/ZnO hollow microspheres were observed to have dimensions in the range of 70–80 μm whereas metallic Zn microparticles with polygonal cross section and oblate spherical shape were found to be of 8–10 μm. Some of the Zn/ZnO core/shell hollow spheres were also observed to have single crystalline ZnO pointed rods in extremely low density grown on the outer shell. The structural, compositional and morphological characterization of the products obtained on the substrates were performed by X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and selected area electron diffraction (SAED). A vapor–liquid–solid (VLS) process based growth mechanism was proposed for the formation of Zn/ZnO core/shell microspheres with hollow interior. The optical properties of Zn/ZnO core/shell microspheres were investigated by measuring the photoluminescence (PL) spectra at room temperature (RT). Two very strong emission bands were observed at 373 and 469 nm in the ultraviolet and visible regions respectively under excitation wavelength of 325 nm. Also the effect of the various excitation wavelengths on the PL behaviour was studied at room temperature. PL studies of Zn/ZnO core/shell microspheres show the promise of the material for applications in UV and blue light optical devices.

Synthesis and characterization of ZnO nanostructures by two-step oxidation of Zn nano- and microparticles

H 2O 2 was employed to pre-oxidize the Zn nano- and microparticles and then oxide films with different thickness coated on the surface of the particles were achieved. TG-DSC examinations were carried out for the Zn nano- and microparticles treated with and without H 2O 2 pre-oxidization as well as the SEM technologies for the corresponding morphologies of the thermally oxidized products. There are tremendous differences on the thermal behaviors and the morphologies between the nano- and microparticles, namely, the treatment with H 2O 2 pre-oxidization brought much effect on the Zn nanoparticles but little on the Zn microparticles for the thermal behaviors and resulted in ZnO chestnut bur-like particles, needles, and pellets morphologies for nanoparticles, and only chestnut bur-like particles for microparticles after thermal oxidation. The models for vapor–solid (VS) growth mechanism resulted in ZnO nanostructures growth were presented.

Effect of the polymer layers and bilayers on the corrosion behaviour of mild steel: Comparison with polymers containing Zn microparticles

Electrodeposition methods have been used to obtain polypyrrole and polyaniline polymer layers, bilayers and blends of these polymers on carbon steel by passivation of the steel surface in the electrodeposition solution (oxalic acid and monomer) between −0.5 and 0.3 V versus Ag/AgCl and subsequent electrodeposition using different techniques (potentiodynamic, galvanostatic and potentiostatic). The results obtained indicate that prepassivation gives rise to adherent polymer layers with excellent corrosion resistance. Of all the bilayers obtained, the best results are yielded with those in which polyaniline is deposited as the base for the deposition of polypyrrole. The electrodeposition of Zn microparticles on the previously deposited polymer layers promotes a great improvement in the corrosion current in highly aggressive solutions such as NaCl due to the effect of Zn as an anodic corrosion inhibitor. The drop in the corrosion rate depends on the amount of Zn deposited on the polymer layer, up to a certain point after which the protective effect ceases to be observed.

In Situ Raman Spectroscopy of Single Particle Microelectrodes

An electrochemically sharpened W tip was used as a spear to capture and manipulate single, quasi-spherical particles of metallic Zn a few tens of micrometers in diameter, harvested from the anode of a commercial battery. This tactic made it possible to acquire in situ Raman spectra of Zn passive films formed by potential step techniques on individual Zn microparticles in 1 M KOH aqueous solutions using a shallow electrochemical cell placed directly beneath the objective of the Raman microscope. The results obtained were in good agreement with those reported earlier for Zn disk electrodes, a few millimeters in diameter, in alkaline electrolytes using the same Raman instrument without a microscope. More specifically, films formed by stepping the potential from −1.55 V to either −0.7 or −0.8 V vs. SCE, displayed a largely enhanced feature at ca. 565 cm−1 ascribed to the longitudinal optical (LO) phonon modes of ZnO, an effect associated with the presence of interstitial Zn and oxygen deficiencies in the lattice. In addition, significant amounts of crystalline ZnO could be detected only for passive films formed at the same two potentials after the electrodes had been microroughened by a single passivation-reduction step. © 2003 The Electrochemical Society. All rights reserved.