Biomimetic fabrication of mulberry-like nano-hydroxyapatite with high specific surface area templated by dual-hydrophilic block copolymer

Novel porous and mulberry-like hydroxyapatite (HAp) nanoparticles with three-dimensionally hierarchical microstructures were developed by using the dual-hydrophilic block copolymer poly(methacrylate acid)-b-poly[N-(2-methacryloylxyethyl) pyrrolidone] (PMAA-b-PNMP) as the template. It was found that the morphology and Ca/P ratio of synthesized HAp was highly related to the concentration of block copolymer and solution pH, respectively. The morphological evolution of HAp nanoparticles in different conditions was investigated systematically by scanning electron microscopy (SEM), transmission electron microscope (TEM), high-resolution transmission electron microscope (HRTEM), powder X-ray diffraction (XRD), and Fourier transform infrared spectroscopy (FTIR). The possible mechanism of PMAA-b-PNMP assisted mulberry-like HAp formation was also proposed based on the time-dependent TEM results. Attributing to the high specific surface area (SSA) of 119 m² g⁻¹, these mulberry-like HAp nanoparticles exhibited excellent adsorption ability for Congo Red (CR). The maximum adsorption capacity was 467 mg g⁻¹ according to the Langmuir monolayer adsorption model.     

Synthesis of flower-like 3D ZnO microstructures and their size-dependent ethanol sensing properties

Flower-like 3D ZnO microstructures constructed from nanorods of different sizes were prepared by a microwave hydrothermal (MH) process in the presence of o-, m- and p-nitrobenzoic acid, respectively. Well-crystallized flower-like ZnO microstructures were obtained after 10 min MH treatment. The X-ray powder diffraction (XRD) test indicated that all the products were consistent with the hexagonal ZnO phase, and scanning electron microscopy (SEM) investigation revealed that the flower-like 3D ZnO microstructures were built with sword-like nanorods 60-100 nm in width and several micrometers in length. The formation mechanism of these flower-like 3D ZnO microstructures is discussed briefly. The gas sensitivity of the as-prepared ZnO microstructures to ethanol at different operation temperatures and concentrations was also studied. The results indicated that the gas sensitivity of the ZnO microstructures was influenced by the particle size and microcosmic configuration, the larger particles with crowded nanorods having higher gas sensitivity.     

DC-field-induced synthesis of ZnO nanowhiskers in water-in-oil microemulsions

ZnO nanowhiskers were successfully fabricated using DC-field induced water-in-oil microemulsions method. Phase structure, morphology and microstructure of the product were investigated by X-ray diffraction and transmission electron microscopy. Parameters in preparation process such as electric field intensity and surfactant were discussed and the product formation mechanism was studied. XRD and TEM results showed that the obtained ZnO particle was hexagonal wurtzite-type with 1-3 nm in diameter and 20-70 nm in length, and morphology of the particles was shown to be correlated not only with the electric field intensity but also with the surfactant. There was a threshold when the electric field intensity was 80 V/mm. The morphology of the particles was basically spherical before the threshold, while L/D increased with the raise of electric field intensity. ZnO nanowhiskers were obtained under mixed surfactants but spherical particles were got with a single surfactant.     

Solvothermal synthesis of microsphere ZnO nanostructures in DEA media

Microsphere ZnO nanostructures (ZnO-MNs) were synthesized via solvothermal method in diethanolamine (DEA) media. DEA was utilized to terminate the growth of ZnO nanoparticles which forms the ZnO-MNs. The ZnO-MNs were characterized by a number of techniques, including X-ray diffraction analysis (XRD) and field emission scanning electron microscopy (SEM). The ZnO-MNs prepared by solvothermal process at the temperature of 150 °C for 6, 12, 18, and 24 h exhibited a hexagonal (wurtzite) structure with sizes ranging from 2 to 4 μm. The growth mechanism and morphology of the ZnO-MNs were also investigated, and it was found that the ZnO-MNs were formed by ZnO nanoparticles with average particle size of 25 ± 5 nm. To show role of DEA in the formation of Zn-MNs, effect of MEA (monoethanolamine) and TEA (triethanolamine) on morphology of the final product are also investigated. The results showed that DEA is a good polymerization agent that can be used as a stabilizer in the solvothermal technique for preparing fine ZnO powder.     

The Effect of Sodium Dodecyl Sulfate (SDS) and Cetyltrimethylammonium Bromide (CTAB) on the Properties of ZnO Synthesized by Hydrothermal Method

ZnO nanostructures were synthesized by hydrothermal method using different molar ratios of cetyltrimethylammonium bromide (CTAB) and Sodium dodecyl sulfate (SDS) as structure directing agents. The effect of surfactants on the morphology of the ZnO crystals was investigated by field emission scanning electron microscopy (FESEM) and transmission electron microscopy (TEM) techniques. The results indicate that the mixture of cationic-anionic surfactants can significantly modify the shape and size of ZnO particles. Various structures such as flakes, sheets, rods, spheres, flowers and triangular-like particles sized from micro to nano were obtained. In order to examine the possible changes in other properties of ZnO, characterizations like powder X-ray diffraction (PXRD), thermogravimetric and differential thermogravimetric analysis (TGA-DTG), FTIR, surface area and porosity and UV-visible spectroscopy analysis were also studied and discussed.     

Application of impregnation combustion method for fabrication of nanostructure CuO/ZnO composite oxide: XRD,FESEM, DRS and FTIR study

Nanostructured CuO/ZnO composite oxide was prepared by a novel impregnation combustion method using copper nitrate and zinc oxide tetrapod. The X-ray diffraction patterns revealed that CuO/ZnO composite oxide was formed. The effects of different impregnation combustion parameters on the properties of composite were studied by field-emission scanning electron microscope (FESEM), powder X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR) and UV–vis diffuse reflectance spectrum (DRS). The synthesis of ZnO–CuO nanocomposites through impregnation of a zinc oxide tetrapod with copper nitrate aqueous sodium carbonate solutions is reported. During thermal treatment the samples evolve toward the formation of nanocrystalline ZnO particles (zincite phase) dispersed onto tenorite, CuO annealed at 450 °C. XRD patterns of the precursors calcined at 450 °C showed the formation of the zincite–tenorite phases. Field emission scanning electron microscopy (FESEM) exhibited loosely agglomerated hexagonal particles with uniform morphology having a size around 50 nm.     

Synthesis and characterization of self-crosslinkable zinc polyacrylate latices at room temperature

The zinc ion self-crosslinkable polyacrylate latexes (PAs) cured at room temperature were synthesized by seeded semi-continuous emulsion polymerization with zinc oxide (ZnO) as crosslinker. The ZnO and methacrylic acid (MAA) mass contents, method of ZnO introduction in relation to the degree of crosslinking, and the properties of self-crosslinkable latices are examined and discussed. The characterization techniques such as Fourier transform infrared spectroscopy (FTIR), differential scanning calorimeter (DSC), transmission electron microscopy (TEM), and thermal gravimetric analysis (TGA) have been used to determine the structure and properties of PAs. The experimental results show that in a certain range, the average particle size decreases with an increase in the content of MAA, while the latex stability is undoubtedly improved. The optimum mass content of MAA is 12?% of the total monomers. The optimum amount of ZnO needed is 25?% (mole fraction) of MAA, and the optimum temperature of ZnO introduction is 60?°C. TEM analyses show that the latex particles are coarse spherical particles with surface enriched with comprising abundant carboxyl groups, and zinc ions are dissociated as zinc ammine complex in the aqueous phase. FTIR analyses confirm that the chelate crosslinking occurs between zinc ions and carboxylic acid during the film-forming process. The DSC results indicate that the glass transition temperature (T _g) of PAs increases as a function of the formation of a coordinate structure, and the obtained film exhibits excellent initial hardness and sandability. TGA analyses demonstrate that the introduction of ZnO evidently enhances the thermal stability of self-crosslinkable PAs.     

Characterization of the fracture behavior and viscoelastic properties of epoxy-polyamide coating reinforced with nanometer and micrometer sized ZnO particles

The mechanical and viscoelastic properties of an epoxy-polyamide coating containing nano and micro sized ZnO particles were studied. The nanocomposites were prepared at different loadings of the nano sized ZnO particles. The composites were also prepared using micro sized ZnO particles at different lambdas (lambda (λ) = PVC/CPVC). The optical properties of each nanocomposite were studied by UV–vis technique. Dynamic mechanical thermal analysis (DMTA) and micro-Vickers were used to investigate the mechanical properties of the composites. The viscoelastic properties of the composites were studied by a tensile test. The fracture morphologies of the composites were studied by a scanning electron microscope (SEM). An increase in Tg together with a decrease in cross-linking density of the composites was obtained when the coating was reinforced with the micro sized ZnO particles. On the other hand, the Tg and cross-linking density of the composites were decreased using nano sized ZnO particles. It was also found that, the Young's modulus and the fracture energy of the coating were decreased using micro and nano sized ZnO particles. The greater toughness as well as fracture energy of the composite was obtained when it was reinforced with the nano sized ZnO particles. The curing behavior of the epoxy coating was affected in the presence of the micro and nano sized ZnO particles.     

In situ preparation of nano ZnO/hyperbranched polyimide hybrid film and their optical properties

Novel hybrid films of fluorinated hyperbranched polyimide (HBPI) and zinc oxide (ZnO) were prepared via the in situ sol-gel polymerization technique, in which mono-ethanolamine (MEA) was used as the coupling agent between the termini of HBPI and the precursor of ZnO. The hybrid films were characterized by transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) absorption, ultraviolet-visible (UV-vis) absorption, and fluorescent excitation/emission spectroscopy. The films, which originated from the colourless fluorinated HBPI structure and homogeneously dispersed ZnO nanoparticles, exhibited good optical transparency. Furthermore, two kinds of model compounds with and without ZnO and a HBPI film blended with ZnO microparticles were prepared to clarify the fluorescence mechanism in the pristine HBPI and in situ hybrid films. Efficient energy transfer from the ZnO nanoparticles to the aromatic HBPI main chains was observed in the in situ hybrid films, whereas energy transfer occurred only from the locally excited (LE) states to the charge-transfer (CT) state in the HBPI film. These facts demonstrate that the peripheral termini of HBPI are covalently bonded to ZnO particles via the MEA function, which operates as an effective pathway for energy transfer to give intense fluorescent emission.     

Shape and Structure of Zinc Oxide Particles Prepared by Vapor-Phase Oxidation of Zinc Vapor

The shape and structure of granular and tetrapod-like ZnO particles prepared by a vapor-phase method were analyzed by electron microscopy, and the growth mechanism is discussed. Only the wurtzite structure exists in ultrafine particles less than 50 nm, indicating that the ZnO particles have the wurtzite structure from the early stages of growth. The legs of the tetrapod-like particles are hexagonal prisms grown along the <001> direction. With regard to the geometrical orientation relationship between any two of the four legs, it was found that the (1¯0) planes of the two legs are parallel to each other.     

A green and facile one-pot synthesis of Ag–ZnO/RGO nanocomposite with effective photocatalytic activity for removal of organic pollutants

In this study, Ag–ZnO/reduced graphene oxide (Ag–ZnO/RGO) composite was synthesized by a green and facile one-step hydrothermal process. Aqueous suspension containing Ag and ZnO precursors with graphene oxide (GO) sheets was heated at 140 °C for 2 h. The morphology and structure of as-synthesized particles were characterized by field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, and Photoluminescence (PL) spectroscopy which revealed the formation of composite of metal, metal oxide and RGO. It was observed that the presence of Ag precursor and GO sheets in the hydrothermal solution could sufficiently decrease the size of ZnO flowers. The hybrid nanostructure, with unique morphology, obtained from this convenient method (low temperature, less time, and less number of reagents) was found to have good photocatalytic and antibacterial activity. The perfect recovery of catalyst after reaction and its unchanged efficiency for cyclic use showed that it will be an economically and environmentally friendly photocatalyst.     

Continuous synthesis of surface-modified zinc oxide nanoparticles in supercritical methanol

Continuous synthesis of surface-modified zinc oxide (ZnO) nanoparticles was examined using surface modifiers (oleic acid and decanoic acid) in supercritical methanol at 400 °C, 30 MPa and a residence time of ∼40 s. Wide angle X-ray diffraction (WAXD) analysis revealed that the surface-modified nanoparticles retained ZnO crystalline structure. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) showed that the surface modifiers changed drastically the size and morphology of the ZnO nanoparticles. When the molar ratio of oleic acid to Zn precursor ratio was 30, 10 nm size particles with low degree of aggregation were produced. The surface-modified ZnO nanoparticles had higher BET surface areas (29-36 m²/g) compared to unmodified ZnO particles synthesized in supercritical water (0.7 m²/g). Fourier transform infrared (FT-IR) and thermogravimetric analysis (TGA) indicated that aliphatic, carboxylate and hydroxyl groups were chemically attached on the surface of ZnO nanoparticles. Long-term (80 days) dispersion test using ultraviolet transmittance showed that the surface-modified ZnO particles had enhanced dispersion stability in ethylene glycol.     

TEA协助层状LZH到ZnO纳米材料控制生长机制研究

三乙醇胺(TEA)协助下类水滑石氢氧化物碱式硝酸锌(LZH)结构到二维层状氧化锌纳米片(ZnO)转变及其性能研究相对较少。以Zn(NO3)2为锌源,借助于三乙醇胺/水体系,研究制备LZH和二维氧化锌纳米片工艺条件及影响合成层状LZH和氧化锌纳米材料的各种因素。利用X-射线粉末衍射(PXRD)、扫描电镜(SEM)、红外光谱(FT-IR)、荧光光谱(PL)等技术手段对其进行解析和表征,探讨层状碱式硝酸锌和氧化锌纳米材料之间的转变机制。结果表明:在研究范围内,温度和反应时间的改变不会影响产物的组成和结构,TEA用量直接影响到合成的目标产物。首先生成Zn(OH)2,其次转化为Zn5(OH)8(NO3)2·2H2O,过渡生成[Zn5(OH)10-x·2H2O]x+,最终自组装形成层状ZnO二维纳米材料,从而实现无需焙烧,通过控制TEA用量制备ZnO二维纳米材料的方法。     

Morphological exploration of chemical vapor–deposited P-doped ZnO nanorods for efficient photoelectrochemical water splitting

Photoelectrochemical (PEC) water splitting is beneficial and has received attractive attention due to a greater potential to generate hydrogen and oxygen from water by using plentiful solar light to solve the problem of energy crisis. Various active semiconductor materials are used in PEC water splitting applications. Nevertheless, in past decades, most of the researchers suggested that titanium oxide (TiO₂) is the best photoanode for this type of applications. Now, Zinc oxide (ZnO) is considered a perfect substitution to TiO₂ due to its comparable energy band structure and superior photogenerated electron transfer rate. In this study, bare and phosphorous-doped ZnO nanorods were successfully developed on fluorine-doped tin oxide-coated glass (FTO) substrate by chemical vapor deposition. X-ray diffraction (XRD) pattern authenticated hexagonal structure formation with strong diffraction peak of (101), which showed that ZnO nanorods were perfectly developed along c axis. The optical and morphological properties were analyzed by UV–Vis and scanning electron microscopy images. The energy-dispersive X-ray spectra demonstrated that doping agent phosphorous was present in ZnO nanorods. The PEC properties of the developed ZnO nanorods were further investigated and obtained results suggested that a small amount of phosphorous-doped ZnO nanorods enhances their PEC performance.     

Novel synthesis of ZnO nanoparticles and their enhanced anticancer activity: Role of ZnO as a drug carrier

In this work, a simple and versatile technique was developed to prepare highly crystalline ZnO nanoparticles (ZnO NPs) by organic precursor method using 5, 6 dimethyl benzimidazole and Zn(CH₃COO)₂·2H₂O followed by calcination. These synthesized ZnO NPs were used as a drug carrier to form 5-Fluorouracil (5 Fu) encapsulated ZnO NPs by varying the molar ratio (100–300:1) of ZnO NPs to 5-Fu. X-ray diffraction (XRD) results indicated that the ZnO NPs had single phase nature with the wurtzite structure. Field emission scanning electron microscopy (FESEM) and Transmission electron microscopy (TEM) results showed nanometer dimension of the NPs. FTIR analysis further reaffirmed the formation/encapsulation of ZnO NPs. UV–vis spectroscopy determined the encapsulation efficiency (EE) and loading capacity (LC) of 5-Fu drug on ZnO NPs. HPLC analysis of encapsulated NPs indicated release of 5-Fu was higher at tumor cell pH (pH 6.0) than physiological pH. Moreover, the anti-tumor activity of ZnO NPs and 5-Fu-encapsulated ZnO NPs investigated using flow cytometry demonstrated that 5-Fu encapsulated ZnO NPs have more anti-tumor activities than 5-Fu itself toward MCF-7 (Breast cancer) cell line. Also, cytotoxicity of MCF-7 increased with the increase of ZnO NPs: 5-Fu ratio. This research will introduce a new concept to synthesize 5-fluorouracil encapsulated ZnO NPs and its application towards the cancer cell line. Thus, the ZnO NPs could not only apply as the drug carrier to deliver 5-Fluorouracil into the cancer cells, but also enhances anti-tumor activity.     

Synthesis of ZnO Microtubes by a Facile Aqueous Solution Process

Zinc oxide (ZnO) microtubes 1.0–2.5 μm in length, 300–500 nm in outer diameter, and 50–80 nm in wall thickness have been synthesized by a facile aqueous solution process, by simply dropping ammonia water into zinc chloride aqueous solution. This new method shows some advantages, such as synthesis under atmospheric pressure at a glass flask, low cost and easy control. The growth mechanism of ZnO microtubes is discussed in this paper. The different growth rates of ZnO crystal facets create the different crystallographic facets of hexagonal microtubes. And the polar structure results in the formation of ZnO microtubes for minimizing the spontaneous polarization energy. The dependence of morphologies of ZnO particles on the reaction temperature is also investigated. The scanning electron microscopy results show that the reaction temperature plays an important role in the morphologies of ZnO particles.     

Stability scheme of ZnO-thin film resistive switching memory: influence of defects by controllable oxygen pressure ratio

We report a stability scheme of resistive switching devices based on ZnO films deposited by radio frequency (RF) sputtering process at different oxygen pressure ratios. I-V measurements and statistical results indicate that the operating stability of ZnO resistive random access memory (ReRAM) devices is highly dependent on oxygen conditions. Data indicates that the ZnO film ReRAM device fabricated at 10% O₂ pressure ratio exhibits the best performance. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) of ZnO at different O₂ pressure ratios were investigated to reflect influence of structure to the stable switching behaviors. In addition, PL and XPS results were measured to investigate the different charge states triggered in ZnO by oxygen vacancies, which affect the stability of the switching behavior.     

CdS quantum dots sensitized ZnO spheres via ZnS overlayer to improve efficiency for quantum dots sensitized solar cells

This paper reports the preparation of three-dimensional ZnO spheres by using a hydrothermal method and their application to quantum dots sensitized solar cells (QDSSCs). After achieving the desired thickness of sensitized CdS quantum dots (QDs) for ZnO spheres, ZnS overlayer was deposited on the surface of CdS/ZnO photo-anodes to further improve the photoelectric properties. CdS QDs and ZnS overlayer were deposited by successive ionic layer adsorption and reaction (SILAR) method. The surface morphology and crystal structure of the samples were verified by field-emission scanning electron microscopy (FE-SEM), Transmission electron microscopy (TEM) and X-ray diffraction (XRD). The CdS QDs sensitized solar cells were ameliorated via using ZnS as a protection-layer between quantum dots and electrolyte. As a result, the power conversion efficiency (η) has been increased from 0.60 to 1.43% after being treated by ZnS overlayer for CdS/ZnO photo-anodes.     

Tailoring the properties of cerium doped zinc oxide/reduced graphene oxide composite: Characterization,photoluminescence study,antibacterial activity

Ce doped ZnO/rGO composite materials were prepared by a one-pot hydrothermal process without any surfactant. The size, crystallography and morphology of the composite were investigated in detail by X- ray diffraction (XRD) studies, Raman spectroscopy, scanning electron microscopic (SEM), transmission electron microscopic (TEM) studies, UV–Vis spectroscopic analysis and X-ray photoelectron spectroscopic (XPS) analysis. The XRD pattern substantiates the formation of Ce doped ZnO/rGO composite revealing the wurtzite structure of ZnO. The SEM micrograph illustrates flower-like morphology for ZnO/rGO composite which coalesced further after cerium incorporation. Additionally, TEM image illustrated that ZnO hexagons were disoriented from its flower structure in Ce/ZnO/rGO composite. The XPS spectra further reaffirm the formation of cerium doped ZnO/rGO composite. The photoluminescence (PL) spectra confirms that emission occurs in the UV and visible region and several active sub-levels were observed in visible region on deconvolution, due to the incorporation of cerium. Antibacterial activity towards B. subtills and V. harveyi affirmed that the incorporation of Ce in ZnO/rGO composite leads to an improved antibacterial activity.     

Influence of zinc oxide on thermoplastic elastomer‐based composites: Synthesis,processing, structural,and thermal characterization

It was aimed to investigate how thermal conductivity and stability properties of synthesized thermoplastic elastomers were influenced by zinc oxide (ZnO) additives which differed in size and surface treatment. ZnO particles were prepared by the homogeneous precipitation method by mixing aqueous solutions of hexamethylenetetramine (HMT) and zinc nitrate. The obtained particles were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Poly(vinyl pyrrolidone) (PVP) was used as a modifier to reduce aggregation among the ZnO particles. The composites, prepared by melt compounding method, were characterized in terms of their morphology and thermal properties. Uniformly distributed surface treated particles caused an enhancement in thermal conductivity properties. At 10 wt% ZnO concentration the thermal conductivity of composite reached 1.7 W/mK compared with 0.3 W/mK for the neat polymer. At the same filler loading, ZnO nanoparticles exhibited a greater effect on thermal conductivity compared with submicron sized particles. It was found that the coefficient of thermal expansion of composites decreased at low temperature (55°C) with increasing ZnO content. Thermal gravimetric analysis (TGA) showed that the neat polymer and the composites were resistant up to 340°C without significant mass loss. POLYM. COMPOS., 37:2369–2376, 2016. © 2015 Society of Plastics Engineers