Poly(methyl methacrylate)–TiO2 nanocomposites obtained by non-hydrolytic sol–gel synthesis: the innovative tert-butyl alcohol route

The present article concerns the preparation of poly(methyl methacrylate)/titania nanocomposites by a non-conventional bottom-up approach, as alternative to the conventional mechanical compounding of preformed filler particles. Poly(methyl methacrylate) (PMMA) was modified with in situ generation of titania nanoparticles by means of the so-called non-hydrolytic sol–gel (NHSG) process in the presence of tert-butyl alcohol (tBuOH) as oxygen donor and polymer solvent. The results showed that the synthetic procedure used permitted the preparation of the highly filled PMMA (up to 20 phr of titania in anatase form) with titania actual content values very close to the nominal ones and with enhanced filler dispersion and homogeneous distribution within the polymeric matrix, avoiding the typical rheological problems related to distributive and dispersive mixing of conventional compounding methods. The presence of titania nanoparticles led to increases in glass transition temperature and E′ modulus in the rubbery region for all the prepared samples with respect to the pristine PMMA. Finally, the nanocomposites showed an interesting photo-catalytic activity towards organic molecules. The findings led us to conclude that the NHSG process was successfully employed to produce anatase titania in the presence of tBuOH and PMMA. The proposed process seems to offer a very promising method to produce polymer nanocomposites with good filler dispersion and homogeneous distribution and with interesting functional properties such as photo-catalytic activity.     

Photoluminescence of Eu<Superscript>3+</Superscript> ion in SnO<Subscript>2</Subscript> obtained by sol–gel

Photoluminescence data of Eu-doped SnO₂ xerogels are presented, yielding information on the symmetry of Eu³⁺ luminescent centers, which can be related to their location in the matrix: at lattice sites, substituting to Sn⁴⁺, or segregated at particles surface. Influence of doping concentration and/or particle size on the photoluminescence spectra obtained by energy transfer from the matrix to Eu³⁺ sites is investigated. Results show that a better efficiency in the energy transfer processes is obtained for high symmetry Eu³⁺ sites and low doping levels. Emission intensity from ⁵D₀→⁷F₁ transition increases as the temperature is raised from 10 to 240 K, under excitation at 266 nm laser line, because in this transition the multiphonon emission becomes significant only above 240 K. As an extension of this result, we predict high effectiveness for room temperature operation of Eu-based optical communication devices. X-ray diffraction data show that the impurity excess inhibits particle growth, which may influence the asymmetry ratio of luminescence spectra.     

Crystallographic and magnetic properties of Fe-doped SnO<Subscript>2</Subscript> nanopowders obtained by a sol–gel method

We prepared Sn_1?x Fe _x O₂ (x = 0, 0.03, 0.05, 0.10, and 1.0) nanoparticles by the polymeric precursor method based on the modified Pechini process. Two types of starting reactants for both tin and iron were explored: Sn(II)/Fe(II) and Sn(IV)/Fe(III) precursors. Thermogravimetric analysis revealed that the precursor powders prepared from Sn(IV) have higher excess in ethylene glycol in comparison to precursor samples prepared from Sn(II). XRD patterns for those samples prepared from Sn(IV) and Fe(III) were adequately fitted by introducing only the cassiterite phase of SnO₂. Micro-Raman spectra also support these findings, and additionally it is found that the presence of iron broadened and reduced the intensities of the principal bands. ¹¹⁹Sn Mössbauer spectra indicated only the presence of Sn⁴⁺, whereas RT ⁵⁷Fe Mössbauer spectra suggested the presence of two Fe³⁺ sites located at different distorted sites. On the other hand, micro-Raman and ⁵⁷Mössbauer spectrometry showed the formation of hematite as impurity phase for those samples with iron concentrations above ~5 at.%, prepared from Fe(II) and Sn(II) precursors. In addition, their XRD patterns revealed larger average grain sizes for the cassiterite phase of SnO₂ in comparison to those samples prepared from Sn(IV) and Fe(III).     

Facile synthesis and characterization of CdTiO<Subscript>3</Subscript> nanoparticles by Pechini sol–gel method

In this work, CdTiO₃ nanoparticles were synthesized through reaction between Cd(CH₃COO)₂.2H₂O, Ti(OC₄H₉)₄, trimesic acid as a new chelating agent and ethanol as solvent by Pechini sol–gel method. X-ray diffraction (XRD) patterns showed that CdTiO₃ nanostructures have rhombohedral structure with diameter of about 35.61 nm. The structure, morphology and size of CdTiO₃ nanoparticles were characterized by FT-IR, XRD, SEM and EDAX. The optical properties of the products were studied by DRS. Based on the results of experiments, it was found that temperature and time of calcination, pH and the solvent of reaction are important parameters for formation of CdTiO₃ nanoparticles. Utilizing trimesic acid (benzene-1,3,5-tricarboxylic acid) as a new chelating agent for preparation of CdTiO₃ nanostructures was initiative of this work.     

Nanostructured Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> composite synthesized by sol–gel technique: powder processing and microstructure

Al₂O₃–ZrO₂ composite gel powder was prepared by sol–gel route. The gel precursor compositions were preferred to achieve yield of 5–15 mol% zirconia after calcination of respective powders. The precursor gel was characterized by Differential Thermal Analysis (DTA)/Thermo Gravimetric (TG), IR and X-ray Diffraction study (XRD). The analysis reveal the gel contained pseudoboehmite and amorphous Zr(OH)₄, which was decomposed in three and two stages respectively. The phase transformation of alumina during calcination followed the sequence of pseudoboehmite → bayerite → boehmite → γ-Al₂O₃ → θ-Al₂O₃ → α-Al₂O₃, while that of ZrO₂ follows amorphous ZrO₂ → t-ZrO₂ → (t + m) ZrO₂. Fourier Transform Infrared Spectroscopy (FTIR) studies showed that the number of M–OH and M–O bond increases with zirconia due to a change in the cationic charge of the composite powder. Transmission Electron Microscopy (TEM) photograph of calcined powder exhibited the presence of dispersed as well as agglomerated nano sized spherical particles. SEM and Electron Probe Microscope Analysis (EPMA) confirmed the near uniform distribution of zirconia particles in the alumina matrix.     

Thermal blooming and photoluminescence characterizations of sol–gel CdO–SiO<Subscript>2</Subscript> with different nanocomposite

The CdO NPs was synthesized using the sol–gel method and the nanoparticles were characterized using an UV–Vis spectrophotometer, with shape and size were examined by SEM and XRD. The XRD analysis respects the Bragg’s law and confirmed the crystalline nature of CdO nanoparticles. From the XRD, the average size of CdO NPs was found to be around 41 nm. The photoluminescence spectra of the CdO NPs, as recorded at room temperature, were excited at 300 nm wavelength. The broad emission peaks were between 600 and 650 nm (orange emission). The optical limiting performance of the nanocomposite was described in the sol–gel state. Also, this study has observed and studied the diffraction rings generated in CdO NPs using the same CW laser. The number of rings increases almost exponentially with an increasing volume fraction of SiO₂ in the nanocomposites. The refractive index change, Δn, and effective nonlinear refractive index, n ₂, were found to be 10^?4 and 10^?8 cm²/W, respectively. The effective nonlinear refractive index, n ₂, was determined based on the observed number of rings. The threshold values of the CdO, CdO–2SiO₂ and CdO–5SiO₂ nanocomposites are 7.1, 6.55 and 6.34 mW, respectively. This large nonlinearity is attributed to the thermal effect. The present studies suggest that the nanocomposite is a potential candidate for optical device applications such as the optical limiters. The thermal blooming technique was applied to evaluate the thermo-optic coefficient and thermal diffusivity of the CdO NPs. In the thermal blooming experimental setup a transistor–transistor logic modulated CW laser of wavelength 532 nm was used as the excitation source.     

Photocatalytic degradation of diverse organic dyes by sol–gel synthesized Cd<Subscript>2</Subscript>V<Subscript>2</Subscript>O<Subscript>7</Subscript> nanostructures

Cd₂V₂O₇ nanostructures have been fabricated by Cd(NO₃)₂·4H₂O, NH₄VO₃ as precursor and diverse carboxylic acids as both fuel and capping agent via the simple and novel sol–gel route. Effect of carboxylic acid type and calcination temperature were studied to reach optimum condition. The Cd₂V₂O₇ nanostructures synthesized by citric acid as optimum size and morphology is composed of particles with the diameter in a range of 10–20 nm. The purity, crystalline phase, morphology, and optical properties were characterized by X-ray diffraction (XRD), Fourier transform IR (FT-IR), energy dispersive X-ray microanalysis (EDX), scanning electron microscopy (SEM), transmission electron microscopy (TEM), ultraviolet–visible (UV–Vis) spectroscopy, and Photoluminescence. The photocatalytic property was performed using degradation of Erythrosine, Eriochrome Black T and Eosin Y aqueous solution under UV irradiation. The optimum removal efficiency is 77% in degradation of Eriochrome Black T.     

Piezoelectric BNT-BT<Subscript>0.11</Subscript> thin films processed by sol–gel technique

0.89(Na_0.5Bi_0.5)TiO₃–0.11BaTiO₃, (BNT-BT_0.11) thin film was fabricated by sol–gel/spin coating process, on platinized silicon wafer. Perovskite structure with random orientation of crystallites has been obtained at 700 °C. Piezoelectric activity of BNT-BT_0.11 thin film was detected using piezoresponse force microscopy (PFM). Effective piezoelectric coefficient d _33eff of such film, recorded at 5 V applied dc voltage, was ~29 pm/V, which is similar to other BNT-BT _x thin films. The complex refractive index and dielectric function of BNT-BT_0.11 thin films were also investigated. The high leakage current density significantly influences the dielectric, ferroelectric, and piezoelectric properties of the BNT-BT_0.11 films.     

Synthesis and piezoelectric properties of (Na<Subscript>0.5</Subscript>Bi<Subscript>0.5</Subscript>)<Subscript>0.94</Subscript>Ba<Subscript>0.06</Subscript>TiO<Subscript>3</Subscript> ceramics prepared by sol–gel auto-combustion method

In this study, NaNO₃, Bi(NO₃)₃·5H₂O, Ba(NO₃)₂, Ti(OC₄H₉)₄ and citric acid were successfully introduced to fabricate lead-free piezoelectric (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ [NBBT] nanopartical powders by a novel modified sol–gel auto-combustion method. The resultant products were characterized by the X-ray diffraction analysis and transmission electron microscope method. (Na_0.5Bi_0.5)_0.94Ba_0.06TiO₃ + Mn(NO₃)₂ [NBBTM] can be sintered by the traditional solid-state reaction, and the effects of NBBT doped different amounts of Mn(NO₃)₂ at various sintering temperatures upon phase formation, microstructure as well as piezoelectric properties were further studied. The experimental results show that it was helpful to control their chemical ingredients and microstructure to prepare nanocrystalline single phase NBBT powders. Where is the X-ray diffraction result of the corresponding ceramics to prove the existence of the mixing between rhombohedral and tetragonal phases at the MPB compositions. Doping 0.015 mol% Mn(NO₃)₂ into NBBT at 1,090 °C, piezoelectric constant (d ₃₃) and relative dielectric constant (ε_r) reach the superior value of 159pC/N and 1,304, respectively, and dielectric loss (tan δ) and electromechanical coupling factor (K _t) are 2.5% and 65%, respectively.     

Sol–gel synthesis of Ta<Subscript>2</Subscript>O<Subscript>5</Subscript>–SiO<Subscript>2</Subscript> composites from tantalum(V) chloride and tetraethyl orthosilicate in ethanol

Ta₂O₅–SiO₂ composites containing 10, 50, and 90 wt % SiO₂ have been prepared by a sol–gel process in ethanolic solutions of tantalum(V) chloride with tetraethyl orthosilicate. The physicochemical aspects of their formation have been studied by IR spectroscopy, X-ray diffraction, X-ray microanalysis, and thermal analysis in combination with mass spectrometry. The results demonstrate that the SiO₂ content of the Ta₂O₅–SiO₂ composites influences the uniformity of the tantalum and oxygen distributions on the surface of the materials and that heat-treatment conditions influence their crystallinity.     

Comparative study of multilayered ZnO/TiO<Subscript>2</Subscript>/ZnO and TiO<Subscript>2</Subscript>/ZnO/TiO<Subscript>2</Subscript> thin films prepared by sol–gel dip coating method

The aim of this research work is to represent the comparative study of ZnO/TiO₂/ZnO (ZTZ) and TiO₂/ZnO/TiO₂ (TZT) thin films deposited by sol–gel dip coating on FTO substrates. After deposition, the films were annealed at 500 °C for 1 h. Structural, surface morphology, optical and electrical properties of these films were studied by X-ray diffractrometer (XRD), Raman spectra, atomic force microscope (AFM), photoluminescence spectra (PL) and four point probe technique respectively. XRD and Raman spectra confirmed the anatase, brookite phases of TiO₂ and cubic phase of ZnO. AFM confirmed the formation of nano particles with average sizes of 18.4 and 47.2 nm of TZT and ZTZ films respectively. According to PL spectra, both the multilayer films slowdown the electron hole recombination rate and enhances the optoelectronic properties of the materials. Also it showed the peaks in the visible region of spectrum. The four point probe results showed that the average sheet resistivity of the films is 450 and 120 (ohm-m) respectively.     

Synthesis of CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> powder via PVA assisted sol–gel process

CoFe₂O₄ ferrites were synthesized by sol–gel method, having metal nitrates as precursors and PVA as surfactant, followed by a heat treatment at 960 °C for 2 h. The ultrafine ferrite powders obtained have been characterized by X-ray diffraction, thermal gravimetry, differential scanning calorimetry and room temperature magnetic measurement studies. The morphology of the powder was identified by high resolution-scanning electron microscopy. X-ray diffraction results indicate that the resultant CoFe₂O₄ crystallites consist of spinel phase. Significant differences in magnetic properties of CoFe₂O₄ samples synthesized with various concentrations of PVA were observed. The magnetisation measurements show that when the PVA concentration increased, coercivity initially decreased and then increased where as retentivity and magnetisation decreased. The optimum concentration of PVA for the synthesis of CoFe₂O₄ ferrites is obtained from this investigation. Obviously this material can be used as an efficient candidate for practical recording purpose.     

Synthesis and characterization of Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZrO<Subscript>2</Subscript> nanocomposite powder by sucrose process

Nanocrystalline alumina–zirconia powders were prepared by a modified chemical route using sucrose, polyvinyl alcohol (PVA) and metal nitrates followed by a post calcination process. The process involved dehydration of Al³⁺–Zr⁴⁺ ions-sucrose–PVA solution to a highly viscous liquid which on decomposition process produced a black precursor material. The obtained precursor were then calcined at various temperatures: 1,050, 1,100, 1,150, 1,200 and 1,250 °C for different soaking times (1, 2, 4 h) in air. The formation of a nanocomposite composed of α-alumina (~20 nm) and tetragonal (t) zirconia (~19 nm) crystallites were confirmed for the sample calcined at 1,200 °C for 2 h, based on our XRD and TEM results. However, for the samples calcined below 1,150 °C the composite formed were composed of metastable alumina (γ, δ, θ) as well as t-zirconia phases. Interestingly, the zirconia phase retained its tetragonal structure for all the samples calcined above 1,050 °C. This is possibly related to the “size effect” and reduction of surface enthalpy of the zirconia crystallites surrounded by Al³⁺ cations.     

Cost-effective electrostatic-sprayed SrAl<Subscript>2</Subscript>O<Subscript>4</Subscript>:Eu<Superscript>2 + </Superscript> phosphor coatings by using salted sol–gel derived solution

3 Mol% of europium doped strontium aluminate (SrAl₂O₄:Eu^2 +) coatings on silicon substrates were prepared by electrostatic spray deposition method using a salted sol–gel derived solution as a starting material. As-deposited films at 100°C for 5 h were heated at 1100°C for 2 h under a reducing ambient atmosphere of 95%N₂ + 5%H₂. Nanocrystalline SrAl₂O₄ film was confirmed by surface morphological and crystallographic analyses. Monitored at 520 nm, the excitation spectrum showed a broad band from 300 ~ 500 nm and the emission intensity showed a maximum yellow peak intensity at 512 nm with a broad band from 460 ~ 610 nm.     

The microwave absorbing properties of La<Subscript>0.8</Subscript>K<Subscript>0.2</Subscript>MnO<Subscript>3</Subscript> synthesized by sol–gel method

In this paper, La_0.8K_0.2MnO₃ powder was synthesized by sol–gel method. The phase structure, morphology of the composite have been characterized by X-ray diffraction, field emission scanning electron microscope. Testing of the microwave absorption was carried out by using the network analyzer Agilent HP-8722ES at room temperature. The results show that the La_0.8K_0.2MnO₃ powder has excellent absorbing property. The maximum reflection loss is ?33.51 dB at about 12.22 GHz with a thickness of only 1.25 mm. Moreover, the bandwidth with the reflection loss above 10 dB reaches about 2.1 GHz.     

Dielectric properties of CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> prepared by sol–gel self combustion technique

The preparation of Calcium copper titanate (CCTO) nanopowder was carried out by a sol–gel self combustion method. The X-ray diffraction analysis indicated that the samples calcined at 800 °C were fully crystallized in the CCTO phase. The results of atomic force microscope showed the particles size of CCTO was in the range of 60–80 nm. The absorption bands corresponding to vibrations of Cu–O, Ti–O–Ti and νCa–O were observed at 512, 450 and 562 cm⁻¹ using FTIR. The samples sintered at 950 °C showed the densities as high as 97% of theoretical density. The grain sizes of sintered pellets were determined by HRSEM. The dielectric properties of prepared samples were studied by LCR meter.     

Comparison study on magnetic property of Co<Subscript>0.5</Subscript>Zn<Subscript>0.5</Subscript>Fe<Subscript>2</Subscript>O<Subscript>4</Subscript> powders by template-assisted sol–gel and hydrothermal methods

The nickel cobalt ferrite (Co_0.5Zn_0.5Fe₂O₄) nanopowders were synthesized by a sol–gel method and a hydrothermal method. Polyethylene glycol (PEG-4000) and carboxymethyl cellulose (CMC) were used as the templating agents for controlling the anisotropy and the microstructure of the Co_0.5Zn_0.5Fe₂O₄ nanopowders. The microstructure and magnetic property of the synthesized powders were comparatively studied. The results indicated that the synthesis technique and the template had remarkable dependence on the microstructure and the magnetic property of the nanopowders. The powder synthesized by the sol–gel method without any template had a maximum saturation magnetization of 73.6 emu g⁻¹ closing to the value of the bulk material (80 emu g⁻¹), while the PEG-4000 and CMC decreased the magnetization to 54.0 and 60.9 emu g⁻¹. The three powders showed almost same coercivity (314–343 Oe). However, the PEG-4000 and CMC in the hydrothermal process obviously decreased and increased the coercivity respectively from 1,464 Oe to 5 Oe and 4,304 Oe but had small effect of the magnetization (55.5–59.0 emu g⁻¹).     

Structure and electrical properties of CuAlO<Subscript>2</Subscript> thin films derived by sol–gel processing

CuAlO₂ (CAO) thin films were prepared on quartz glass substrates by sol–gel spin-coating method. The effects of annealing temperatures, concentrations of sols and Al/Cu atomic ratios on structure, morphology and electrical properties have been investigated. It was found that CAO film with an Al/Cu atomic ratio of 0.8 approximately and the total metallic ion concentration of 0.7 M after heat treatment at 750 °C for 3 h in argon gas flow of 450 mL/min exhibited the lowest room temperature resistivity of 13.5 Ωcm.     

Phase formation and dielectric properties of Ba<Subscript>0.5</Subscript>Sr<Subscript>0.5</Subscript>TiO<Subscript>3</Subscript> by slow injection sol–gel technique

A simple sol–gel process incorporating slow precursor injection technique was employed to synthesize homogeneous Ba_0.5Sr_0.5TiO₃ nano powders. The Ba_0.5Sr_0.5TiO₃ samples were subjected to calcination temperatures from 600 to 1,100 °C and sintering temperatures from 1,250 to 1,350 °C for the study of phase formation, crystallite size, particle distribution, and dielectric properties. Single phase Ba_0.5Sr_0.5TiO₃ with a cubic perovskite structure was successfully synthesized after calcination at 800 °C. The average size of the nano particles is 42 nm with a narrow size distribution, and a standard deviation of 10%. The highest values recorded within the investigated range for dielectric constant, and dielectric loss measured at 1 kHz are 1,164 and 0.063, respectively, for Ba_0.5Sr_0.5TiO₃ pellets calcined at 800 °C and sintered at 1,350 °C. Leakage current density measured at 5 V for the Ba_0.5Sr_0.5TiO₃ pellet was found to be 49.4 pA/cm².