A Review of Microwave Synthesis of Zinc Oxide Nanomaterials: Reactants, Process Parameters and Morphoslogies.

Zinc oxide (ZnO) is a multifunctional material due to its exceptional physicochemical properties and broad usefulness. The special properties resulting from the reduction of the material size from the macro scale to the nano scale has made the application of ZnO nanomaterials (ZnO NMs) more popular in numerous consumer products. In recent years, particular attention has been drawn to the development of various methods of ZnO NMs synthesis, which above all meet the requirements of the green chemistry approach. The application of the microwave heating technology when obtaining ZnO NMs enables the development of new methods of syntheses, which are characterised by, among others, the possibility to control the properties, repeatability, reproducibility, short synthesis duration, low price, purity, and fulfilment of the eco-friendly approach criterion. The dynamic development of materials engineering is the reason why it is necessary to obtain ZnO NMs with strictly defined properties. The present review aims to discuss the state of the art regarding the microwave synthesis of undoped and doped ZnO NMs. The first part of the review presents the properties of ZnO and new applications of ZnO NMs. Subsequently, the properties of microwave heating are discussed and compared with conventional heating and areas of application are presented. The final part of the paper presents reactants, parameters of processes, and the morphology of products, with a division of the microwave synthesis of ZnO NMs into three primary groups, namely hydrothermal, solvothermal, and hybrid methods.

In vivo and in vitro study of a novel nanohydroxyapatite sonocoated scaffolds for enhanced bone regeneration.

There still remains a need for new methods of healing large bone defects, i.e., gaps in bone tissue that are too big to naturally heal. Bone regrowth scaffolds can fill the bone gap and enhance the bone regeneration by providing cells with a support to for new tissue formation. Coating of the scaffolds surface with nanocrystalline hydroxyapatite may enhance the osteoinductivity or osteoconductivity of such scaffolds. Here we present the sonocoating method to coat scaffolds with bioactive hydroxyapatite nanoparticles. We show a method, where the material to be coated is immersed in a colloidal suspension of nanoparticles with mean sizes of 10 nm and 43 nm in water, and high-power ultrasound waves are applied to the suspension for 15 min at 30 °C. High power ultrasounds lead to growth of cavitation bubbles in liquid, which implode at a critical size. The implosion energy propels the nanoparticles towards the material surface, causing their attachment to the scaffold. Using this technique, we produced a uniform layer of nanohydroxyapatite particles of thickness in the range 200 to 300 nm on two types of scaffolds: a porous ß-TCP ceramic scaffold and a 3D-printed scaffold made of PCL fibers. In vivo tests in rabbits confirmed that the novel coating strongly stimulated new bone tissue formation, with new bone tissue occupying 33% for the nHAP-coated PCL scaffold and 68% for the nHAP-coated ß-TCP after a 3-month test. The sonocoating method leads to formation of a bioactive layer on the scaffolds at temperature close to room temperature, very short time and in water. It is a green technological process, promising for bone tissue regeneration applications.

Effect of Microwave Radiation Power on the Size of Aggregates of ZnO NPs Prepared Using Microwave Solvothermal Synthesis.

This paper reports the possibility of changing the size of zinc oxide nanoparticles (ZnO NPs) aggregates through a change of synthesis parameters. The effect of the changed power of microwave heating on the properties of ZnO NPs obtained by the microwave solvothermal synthesis from zinc acetate dissolved in ethylene glycol was tested for the first time. It was found that the size of ZnO aggregates ranged from 60 to 120 nm depending on the power of microwave radiation used in the synthesis of ZnO NPs. The increase in the microwave radiation power resulted in the reduction of the total synthesis time with simultaneous preservation of the constant size and shape of single ZnO NPs, which were synthesized at a pressure of 4 bar. All the obtained ZnO NPs samples were composed of homogeneous spherical particles that were single crystals with an average size of 27 ± 3 nm with a developed specific surface area of 40 m²/g and the skeleton density of 5.18 ± 0.03 g/cm³. A model of a mechanism explaining the correlation between the size of aggregates and the power of microwaves was proposed. This method of controlling the average size of ZnO NPs aggregates is presented for the first time and similar investigations are not found in the literature.

Size control mechanism of ZnO nanoparticles obtained in microwave solvothermal synthesis.

The aim of the paper is to explain the mechanism of zinc oxide (ZnO) nanoparticle (NP) size control, which enables the size control of ZnO NPs obtained in microwave solvothermal synthesis (MSS) within the size range between circa 20 and 120 nm through the control of water content in the solution of zinc acetate in ethylene glycol. Heavy water was used in the tests. The mechanism of ZnO NPs size control was explained, discussed and experimentally verified. The discovery and investigation of this mechanism was possible by tracking the fate of water molecules during the whole synthesis process. All the synthesis products were identified. It was indicated that the MSS of ZnO NPs proceeded through the formation and conversion of intermediates such as Zn5(OH)8(CH3COO)2 · xH2O. Esters and H2O were the by-products of the MSS reaction of ZnO NPs. We justified that the esterification reaction is the decisive stage that is a prerequisite of the formation of ZnO NPs. The following parameters of the obtained ZnO NPs and of the intermediate were determined: pycnometric density, specific surface area, phase purity, average particles size, particles size distribution and chemical composition. The ZnO NPs morphology and structure were determined using scanning electron microscopy.

Influence of hydrothermal synthesis parameters on the properties of hydroxyapatite nanoparticles.

Hydroxyapatite (HAp) nanoparticles of tunable diameter were obtained by the precipitation method at room temperature and by microwave hydrothermal synthesis (MHS). The following parameters of the obtained nanostructured HAp were determined: pycnometric density, specific surface area, phase purity, lattice parameters, particle size, particle size distribution, water content, and structure. HAp nanoparticle morphology and structure were determined using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). X-ray diffraction measurements confirmed crystalline HAp was synthesized, which was pure in terms of phase. It was shown that by changing the synthesis parameters, the diameter of HAp nanoparticles could be controlled. The average diameter of the HAp nanoparticles was determined by Scherrer's equation via the Nanopowder XRD Processor Demo web application, which interprets the results of specific surface area and TEM measurements using the dark-field technique. The obtained nanoparticles with average particle diameter ranging from 8-39 nm were characterized by having homogeneous morphology with a needle shape and a narrow particle size distribution. Strong similarities were found when comparing the properties of some types of nanostructured hydroxyapatite with natural occurring apatite found in animal bones and teeth.

Paramagnetism of cobalt-doped ZnO nanoparticles obtained by microwave solvothermal synthesis.

Zinc oxide nanopowders doped with 1-15 mol % cobalt were produced by the microwave solvothermal synthesis (MSS) technique. The obtained nanoparticles were annealed at 800 °C in nitrogen (99.999%) and in synthetic air. The material nanostructure was investigated by means of the following techniques: X-ray diffraction (XRD), helium pycnometry density, specific surface area (SSA), inductively coupled plasma optical emission spectrometry (ICP-OES), extended X-ray absorption fine structure (EXAFS) spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS) and with magnetometry using superconducting quantum interference device (SQUID). Irrespective of the Co content, nanoparticles in their initial state present a similar morphology. They are composed of loosely agglomerated spherical particles with wurtzite-type crystal structure with crystallites of a mean size of 30 nm. Annealing to temperatures of up to 800 °C induced the growth of crystallites up to a maximum of 2 µm in diameter. For samples annealed in high purity nitrogen, the precipitation of metallic α-Co was detected for a Co content of 5 mol % or more. For samples annealed in synthetic air, no change of phase structure was detected, except for precipitation of Co3O4 for a Co content of 15 mol %. The results of the magentometry investigation indicated that all as-synthesized samples displayed paramagnetic properties with a contribution of anti-ferromagnetic coupling of Co-Co pairs. After annealing in synthetic air, the samples remained paramagnetic and samples annealed under nitrogen flow showed a magnetic response under the influences of a magnetic field, likely related to the precipitation of metallic Co in nanoparticles.

Size-dependent density of zirconia nanoparticles.

The correlation between density and specific surface area of ZrO2 nanoparticles (NPs) was studied. The NPs were produced using a hydrothermal process involving microwave heating. The material was annealed at 1100 °C which resulted in an increase in the average grain size of the ZrO2 NPs from 11 to 78 nm and a decrease in the specific surface area from 97 to 15 m(2)/g. At the same time, the density increased from 5.22 g/m(3) to 5.87 g/m(3). This effect was interpreted to be the result of the presence of a hydroxide monolayer on the NP surface. A smaller ZrO2 grain size was correlated with a larger contribution of the low density surface layer to the average density. To prove the existence of such a layer, the material was synthesized using 50% heavy water. Fourier transform infrared spectroscopy (FTIR) permitted the identification of the -OD groups created during synthesis. It was found that the -OD groups persisted on the ZrO2 surface even after annealing at 1100 °C. This hydroxide layer is responsible for the decrease in the average density of the NPs as their size decreases. This study of the correlation between particle size and density may be used to assess the quality of the NPs. In most cases, the technological aim is to avoid an amorphous layer and to obtain fully crystalline nanoparticles with the highest density possible. However, due to the effect of the surface layers, there is a maximum density which can be achieved for a given average NP diameter. The effect of the surface layer on the NP density becomes particularly evident for NPs smaller than 50 nm, and thus, the density of nanoparticles is size dependent.

Highly biocompatible, nanocrystalline hydroxyapatite synthesized in a solvothermal process driven by high energy density microwave radiation.

A microwave, solvothermal synthesis of highly biocompatible hydroxyapatite (HAp) nanopowder was developed. The process was conducted in a microwave radiation field having a high energy density of 5 W/mL and over a time less than 2 minutes. The sample measurements included: powder X-ray diffraction, density, specific surface area, and chemical composition. The morphology and structure were investigated by scanning electron microscopy as well as transmission electron microscopy (TEM). The thermal behavior analysis was conducted using a simultaneous thermal analysis technique coupled with quadruple mass spectrometry. Additionally, Fourier transform infrared spectroscopy tests of heated samples were performed. A degradation test and a biocompatibility study in vitro using human osteoblast cells were also conducted. The developed method enables the synthesis of pure, fully crystalline hexagonal HAp nanopowder with a specific surface area close to 240 m(2)/g and a Ca/P molar ratio equal to 1.57. TEM measurements showed that this method results in particles with an average grain size below 6 nm. A 28-day degradation test conducted according to the ISO standard indicated a 22% loss of initial weight and a calcium ion concentration at 200 µmol/dm(3) in the tris(hydroxymethyl)aminomethane hydrochloride test solution. The cytocompatibility of the obtained material was confirmed in a culture of human bone derived cells, both in an indirect test using the material extract, and in direct contact. A quantitative analysis was based on the 2,3-bis-(2-methoxy-4-nitro-5-sulfophenyl)-2H-tetrazolium-5-carboxanilide. Viability assay as well as on DNA content measurements in the PicoGreen test. Indirect observations were performed at one point in time according to the ISO standard for in vitro cytotoxicity (ie, after 24 hours of cell exposure to the extracts). The direct contact tests were completed at three time points: after 24 hours, on day 7, and on day 14 of a culture in an osteogenic medium. All of the tests revealed good tolerance of cells toward the material; this was also shown by means of live/dead fluorescent staining. Both quantitative results and morphological observations revealed much better cell tolerance toward the obtained HAp compared to commercially available HAp NanoXIM, which was used as a reference material.