Electrospinning of hydroxyapatite fibrous mats

Polyvinyl alcohol (PVA) with an average molecular weight between 40,500 and 155,000 g/mol was electrospun with a calcium phosphate based sol. The sol was prepared by reacting triethyl phosphite and calcium nitrate and was directly added to an aqueous solution of PVA. This mixture was electrospun at a voltage of 20 kV. The results indicate that the sol was distributed uniformly in the PVA fibers, whose diameter was on the order of 2 μm. This electrospun structure was calcined at 600 °C for 6 h to obtain a residual inorganic, fibrous network, with fiber diameters between 200 and 800 nm. The fibrous structure consists predominantly of hydroxyapatite with an average crystal size of almost 10 to 30 nm. A variety of structures including non-woven mats of solid or micro-porous hydroxyapatite fibers and highly porous scaffolds could be obtained by varying the polymer molecular weight and the sol volume fraction. These structures can have many potential uses in the repair and treatment of bone defects, drug delivery and tissue engineering.     

Ultrafine porous fibers electrospun from cellulose triacetate

Ultrafine porous cellulose triacetate (CTA) fibers were prepared by electrospinning with methylene chloride (MC) and a mixed solvent of MC/ethanol (EtOH) and their intra- and inter-fiber pore structures was investigated. Ultrafine porous CTA fibers electrospun with MC had isolated circular shape pores with a narrow size distribution in the range of 50–100 nm. In the case of ultrafine CTA fibers electrospun with MC/EtOH (90 / 10 v/v), they had interconnected larger pores in the range of 200–500 nm. These porous structures were induced by phase separation resulting from the rapid evaporation of solvent during the electrospinning process. However, non-porous corrugated fibers were obtained from MC/EtOH (85 / 15 v/v) and MC/EtOH (80 / 20 v/v) due to their lower vapor pressure. The pore sizes in ultrafine CTA fibers electrospun with MC showed a bimodal distribution centered at ∼17 and ∼64 nm. CTA fibers electrospun with MC/EtOH (90 / 10 v/v) showed the greatest porosity due to their larger intra-fiber pores and fiber diameter.     

Preparation of poly(vinyl alcohol)/tin glycolate composite fibers by combined sol–gel/electrospinning techniques and their conversion to ultrafine tin oxide fibers

Ultrafine composite fibers made from poly(vinyl alcohol) (PVA)/tin glycolate — a moisture-stable tin oxide containing compound — were prepared by a combined sol–gel processing and electrospinning technique. These fibers were subsequently converted to ultrafine tin oxide fibers by calcination treatment, with the aim of producing tin oxide fiber with a high surface area-to-mass ratio and a high specific conductivity value. The acidity of spinning solution plays an important role to the morphology and size of the obtained fibers. The average diameters of the obtained composite fibers were in the range of 87–166 nm. It was found that the ultrafine tin oxide fiber showed the high conductivity value of 1.59 × 10³ S cm^?1 at calcinations temperature of 600 °C, and the BET surface area was in a range of 71 and 275 m² g^?1. Moreover, the effect of calcinations temperature on the phase and the size of the tin oxide fibers were investigated in this study.     

Down conversion photoluminescence on PVP/Ag-nanoparticles electrospun composite fibers

The influence of Ag nanoparticles (Ag NPs) on the luminescence of electrospun nonwoven mats made of polyvinylpyrrolidone (PVP) has been studied in this work. The PVP fibers incorporating 2.1–4.3 nm size Ag NPs show a significant photoluminescence (PL) band between 580 and 640 nm under 325 nm laser excitation. The down conversion luminescence emission is present even after several hours of laser excitation, which denotes the durability and stability of fibers to consecutive excitations. As so these one-dimensional photonic fibers made using cheap methods is of great importance for organic optoelectronic applications, fluorescent clothing or counterfeiting labels.     

Critical variables in the alignment of electrospun PLLA nanofibers

Electrospun polymer nanofibers show promise as components of scaffolds for tissue engineering because of their ability to orient regenerating cells. Our research focuses on aligned electrospun fiber scaffolds for nerve regeneration. Critical to this are highly aligned fibers, which are frequently difficult to manufacture reproducibly. Here we show that three variables: the distance between the spinneret tip and collector, the addition of DMF to the solvent, and placement of an aluminum sheet on the spinneret together greatly improve the alignment of electrospun poly-L-lactide (PLLA) nanofibers. We identified the most important variable as tip-to-collector distance. Nanofiber alignment was maximal at 30 cm compared to shorter distances. DMF:chloroform (1:9) improved nanofiber uniformity and was integral to maintaining a uniform stream over the 30 cm tip-to-collector distance. Other ratios caused splattering of the solution or flattening or beading of the fibers and non-uniform fiber diameter. The aluminum sheet helped to stabilize the electric field and improve fiber alignment provided that it was placed at 1 cm behind the tip, while other distances destabilized the stream and worsened alignment. This study demonstrates that control of these variables produces dramatic improvement in reproducibly obtaining high alignment and uniform morphology of electrospun PLLA nanofibers.     

Synthesis of organic–inorganic hybrid azobenzene materials for the preparation of nanofibers by electrospinning

The new photochromic hybrid materials containing different mole fractions of highly photoactive 4-[(E)-[4-[ethyl(2-hydroxyethyl)amino]phenyl]azo]-N-(4-methylpyrimidin-2-yl)benzenesulfonamide (SMERe) were prepared by a low temperature sol–gel process. The guest–host systems with triethoxyphenylsilane matrix were obtained. These materials were used to form thin transparent films by a spin-coating technique. Then the ability of thin hybrid films to reversible trans–cis photoisomerization under illumination was investigated using ellipsometry and UV–Vis spectroscopy. The reversible changes of refractive index of the films under illumination were in the range of 0.005–0.056. The maximum absorption of these materials was located at 462–486 nm. Moreover, the organic–inorganic azobenzene materials were used to form nanofibers by electrospinning using various parameters of the process. The microstructure of electrospun fibers depended on sols properties (e.g. concentration and viscosity of the sols) and process conditions (e.g. the applied voltage, temperature or type of the collector) at ambient conditions. The morphology of obtained nanofibers was analyzed by an optical microscopy and scanning electron microscopy. In most instances, the beadless fibers were obtained. The wettability of the surface of electrospun fibers deposited on glass substrates was investigated.     

Improved efficiency of sol–gel synthesized mesoporous anatase nanopowders in photocatalytic degradation of metoprolol

The structural and morphological properties of mesoporous anatase nanopowders, synthesized by sol–gel method, have been modified by varying the duration of calcination, in order to obtain more efficient photocatalyst than Degussa P25 in the degradation of relatively large pollutant molecules (>1 nm in size). According to X-ray diffraction analysis, the crystallite size was increased from 13 to 17.5 nm with the increase of calcination time from 1 to 7 h. The analysis of nitrogen sorption experimental data revealed that all samples were mesoporous, with a mean pore diameters in the range of ∼5–9 nm. The corrugated pore structure model was employed to evaluate pore structure tortuosity. Nanopowder properties have been related to the photocatalytic activity, tested in the degradation of metoprolol tartrate salt, selective β₁-blocker used in a variety of cardiovascular diseases, with molecular size of 0.610 nm × 1.347 nm. The study has demonstrated that samples calcined for 4 and 5 h have displayed higher photocatalytic performance than Degussa P25, whereas the sample calcined for 3 h has shown comparable activity.     

Sol-hydrothermal synthesis and characterization of lead zirconate titanate fine particles

A novel sol-hydrothermal route to prepare lead zirconate titanate (PZT) fine particles is presented, which combined the conventional sol–gel process and the hydrothermal method. The effects of experimental parameters including sol/(sol + water) ratio, reaction temperature and reaction time on the product powders were investigated. The prepared PZT powders were characterized by XRD, SEM/EDS, and Raman techniques. The results indicated that the optimal synthesis conditions were sol/(sol + water) = 20%, 200 °C, 8 h. The obtained powders with an average particle size of 700 nm, were phase pure perovskite PZT with cubic-shaped morphology, and the reaction temperature was as low as 150 °C, which was comparatively lower than that synthesized by the normal sol–gel route. It was supposed that the sol precursor and hydrothermal environment played important roles in the formation of the PZT fine powders at low temperature and low mineralizer concentration.     

Fabrication of WO3 nanofibers by high voltage electrospinning

Mixtures of 0.1, 0.3, and 0.5 mmol ammonium metatungstate hydrate (AMH), and poly (vinyl alcohol) (PVA) were electrospun by a + 20 kV direct voltage to synthesize fibers. Those of 0.5 mmol AMH were further calcined to have PVA removed and crystalline degree improved. At 500 °C and 2 h calcination, WO₃ nanofibers, including two main stretching modes, 3.24 eV direct energy gap, and 378 nm wavelength violet emission were detected. A possible formation mechanism of WO₃ nanofibers was proposed according to the experimental results.     

Characterization of a calcium phosphate–TiO2 nanotube composite layer for biomedical applications

Well-ordered nanotube arrays of titania ~ 0.7 μm high and about 40 or 110 nm in diameter were prepared via electrochemical oxidation at constant voltage (10, 15, 20 or 25 V) in a mixture of 0.86 wt.% of NH₄F, glycerol and deionized water. The effect of annealing the nanotubes at 600 °C on their morphology and structure was examined using SEM and TEM techniques. These substrates are suitable supports for a calcium phosphate coating deposited by a simple immersion in Hank solution.The nucleation and growth of a calcium phosphate (Ca–P) coating deposited on TiO₂ nanotubes (NT) from Hanks' solution was investigated using SEM. XPS and FTIR surface analytical techniques were used to characterize the self-organized porous TiO₂ layers covered with calcium phosphate coatings before and after protein adsorption. Our results confirm that the nanotubular titania layer became stable after annealing at 600 °C, while its internal structure changed from amorphous to crystalline anatase, and eventually, a mixture of anatase and rutile. These thermally stabilized TiO₂ nanotubes significantly enhance apatite formation in Hanks' Balanced Salt Solution as compared to pure Ti covered with a native oxide layer. The Ca–P/TiO₂ NT/Ti surface adsorbs a higher amount of protein (bovine serum albumin, BSA) for a geometric surface area than does the Ti surface. The above difference in protein adsorption suggests a more promising initial cellular response for a Ca–P/TiO₂ NT/Ti composite than for a typical Ti implant surface.     

Development,characterization, and in vitro bioactivity studies of sol–gel bioactive glass/poly(l-lactide) nanocomposite scaffolds

Developing materials combining the advantages of synthetic polymers and bioactive glass nanoparticles can provide an efficient bone engineering scaffold. In this study, sol–gel bioactive glass (SG) nanoparticles were synthesized by quick alkali-mediation; sol–gel derived bioactive glass/poly(l-lactide) nanocomposite scaffolds were then developed. The influence of the glass content on the porosity of nanocomposite scaffolds was evaluated by SEM. The results showed that the neat polymer scaffold (PLA) has a highly interconnected porous structure with a maximum pore size of about 250 μm. For the composite scaffold containing 25 wt.% glass (SGP25), the decrease in the maximum pore size, (to about 200 μm) was not significant while for the SGP50 composite scaffold containing 50 wt.% glass it was a significant decrease (to about 100 μm). The apparent porosity of the scaffolds was 56.56% ± 7.15, 54.14% ± 3.84, and 53.11% ± 3.99 for PLA, SGP25, and, SGP50 respectively. FT-IR, TGA, and XRD results revealed some interaction of the glass filler with the polymeric matrix in the scaffolds. The degradation study showed that, by increasing the glass content in the scaffolds, the water absorption decreased, the weight loss increased, and the cumulative ion concentrations released from them also increased. This indicates the possibility of modulating the degradation rate by varying the glass/polymer ratio. At the end of the incubation period, the weight losses were around 5.44% ± 0.96, 32.50% ± 2.73, and 41.47% ± 3.02 for the PLA, SGP25, and SGP50, respectively. Moreover, the water uptake reached 119.65% ± 18.88 and 93.39% ± 13.01 for SGP25 and SGP50, respectively. The addition of the SG to the scaffolds was found to enhance their in vitro bioactivity. Therefore, these nanocomposite scaffolds have a potential to be applied in bone engineering. All data are expressed as mean ± standard deviation (n = 3).     

Flexible polymer microtubes and microchannels via electrospinning

Here we report an approach to fabricate flexible polymer self standing films embedded with continuous aligned microtubes/microchannels via electrospinning. The scheme is to wash the electrospun fibers selectively to form either microtubes/microchannels. Optical microscope (OM) and Scanning electron microscope images are evident for the well aligned microtubes and microchannels respectively with a diameter of ~ 8 μm and a length of ~ 4 cm. Meniscus of tetrahydrofuran in the microtubes can be observed explicitly in the OM images. Mutually perpendicular microtubes are also fabricated on a polymer film. Angular distribution of aligned microstructures indicates the standard deviation is not more than 1°. These tubes/channels can be potential for tissue engineering as they could provide a directional template for the growth when a biodegradable polymer such as Poly(vinylalcohol) is used.     

Effect of processing methods on physicochemical properties of titania nanoparticles produced from natural rutile sand

Titania (TiO₂) nanoparticles were produced from natural rutile sand using different approaches such as sol–gel, sonication and spray pyrolysis. The inexpensive titanium sulphate precursor was extracted from rutile sand by employing simple chemical method and used for the production of TiO₂ nanoparticles. Particle size, crystalline structure, surface area, morphology and band gap of the produced nanoparticles are discussed and compared with the different production methods such as sol–gel, sonication and spray pyrolysis. Mean size distribution (d₅₀) of obtained particles is 76 ± 3, 68 ± 3 and 38 ± 3 nm, respectively, for sol–gel, sonication and spray pyrolysis techniques. The band gap (3.168 < 3.215 < 3.240 eV) and surface area (36 < 60 < 103 m² g^?1) of particles are increased with decreasing particle size (76 > 68 > 38 nm), when the process methodology is changed from sol–gel to sonication and sonication to the spray pyrolysis. Among the three methods, spray pyrolysis yields high-surface particles with active semiconductor bandgap energy. The effects of concentration of the precursor, pressure and working temperature are less significant for large-scale production of TiO₂ nanoparticles from natural minerals.     

The fabrication of nanocomposites via calcium phosphate formation on gelatin–chitosan network and the gelatin influence on the properties of biphasic composites

A novel biodegradable polymer–ceramic nanocomposite which consisted of gelatin (Gel), chitosan (CS), and calcium phosphate (CaP) nanoparticles was prepared based on in situ preparation method. The fabricated biocomposites were characterized by FTIR, X-ray diffraction (XRD), transmission electron microscopy (TEM) as well as scanning electron microscope with X-ray elemental analysis (SEM-EDX). The characterization results confirmed that the crystalline calcium phosphate nanoparticles were mineralized in polymeric matrix and the interaction between Ca2+ in calcium phosphate and functional groups in polymers molecular chains was formed. XRD result showed that in addition to hydroxyapatite (HA), Brushite (BR) and tricalcium phosphate (β-TCP) particles also were formed due to lack of complete penetration of the basic solution into the polymeric matrix. However, SEM image indicated that the polymeric matrix has the controlling role in the particle size of calcium phosphate. The size of particles in three component composites was about 100 nm while in two component composites proved to be more in μm size. TEM observation supported SEM results and showed that the three component composites have calcium phosphate nanoparticles. The elastic modulus and compressive strength of the composites were also improved by the employment of gelatin and chitosan together, which can make them more beneficial for surgical applications.     

Room temperature synthesis of high temperature stable lanthanum phosphate–yttria nano composite

A facile aqueous sol–gel route involving precipitation–peptization mechanism followed by electrostatic stabilization is used for synthesizing nanocrystalline composite containing lanthanum phosphate and yttria. Lanthanum phosphate (80 wt%)–yttria (20 wt%) nano composite (LaPO₄–20%Y₂O₃), has an average particle size of ～70 nm after heat treatment of precursor at 600 °C. TG–DTA analysis reveals that stable phase of the composite is formed on heating the precursor at 600 °C. The TEM images of the composite show rod shape morphology of LaPO₄ in which yttria is acquiring near spherical shape. Phase identification of the composite as well as the phase stability up to 1300 °C was carried out using X-ray diffraction technique. With the phases being stable at higher temperatures, the composite synthesized should be a potential material for high temperature applications like thermal barrier coatings and metal melting applications.     

Synthesis of nanocomposite powders of γ-alumina-carbon nanotube by sol–gel method

The nanocomposite powders of γ-alumina-carbon nanotube were successfully synthesized by a sol–gel process. The homogeneous mixture of carbon nanotubes and alumina particles was obtained by mixing the carbon nanotubes within alumina solution and followed by heating into gel. The resultant gel was dried and calcined at 200 °C into boehmite-carbon nanotubes composite powders. The mean particle size of synthesized boehmite was of the order of 4 nm. The boehmite-carbon nanotubes composite powders were calcined at different temperatures and XRD investigations revealed that as the amount of carbon nanotube increases, γ- to α-alumina phase transformation is completed at higher temperatures. The specific surface area and mean particle size of resultant nanocomposite powders increased and decreased, respectively by increasing the content of carbon nanotubes.     

Electrospun nanofibers composed of poly(ε-caprolactone) and polyethylenimine for tissue engineering applications

Poly(ε-caprolactone) (PCL) electrospun nanofibers have been reported as a scaffold for tissue engineering application. However, high hydrophobicity of PCL limits use of functional scaffold. In this study, PCL/polyethylenimine (PEI) blend electrospun nanofibers were prepared to overcome the limitation of PCL ones because the PEI as a cationic polymer can increase cell adhesion and can improve the electrospinnability of PCL. The structure, mechanical properties and biological activity of the PCL/PEI electrospun nanofibers were studied. The diameters of the PCL/PEI nanofibers ranged from 150.4 ± 33 to 220.4 ± 32 nm. The PCL/PEI nanofibers showed suitable mechanical properties with adequate porosity and increased hydrophilic behavior. The cell adhesion and cell proliferation of PCL nanofibers were increased by blending with PEI due to the hydrophilic properties of PEI.     

Zero-birefringence optical polymers by nano-birefringent crystals for liquid crystal displays

We report a method for compensating the birefringence of optical polymers by doping them with nanometer-size inorganic birefringent crystals. In this method, an inorganic birefringent crystal is chosen that has the opposite birefringence to the polymer and a rod like shape which is oriented when the polymer chains are oriented. As a result, the birefringence of the polymer is compensated by the opposing birefringence of the crystal. Positive orientational birefringence of poly(methylmethacrylate (MMA)-co-benzylmethacrylate (BzMA)) = 78/22 (wt/wt) was compensated by doping with 0.3 wt.% of the smaller strontium carbonate (SrCO₃) crystals with a length of about 200 nm and a width of about 20 nm. The birefringence of the copolymer containing SrCO₃ was almost zero with any draw ratio between 1.0 and 2.2. The polarization state was almost maintained when it passed through the film. On the other hand, we concluded that the size of the larger crystals (about 3.0 μm × about 300 nm) is too large to form an optically isotropic medium with the polymer. In spite of doping with 0.3 wt.% of the smaller SrCO₃ crystal, the transmittance of the doped film with a thickness of 30 μm was almost the same as the undoped one in the visible region. The increase in haze by doping with 0.3 wt.% of the smaller SrCO₃ crystal was 0.1%. Furthermore, the negative birefringence of PMMA was enhanced by the SrCO₃ crystal.     

Synthesis,characterization and cation adsorption of p-aminobenzoic acid intercalated on calcium phosphate

Crystalline lamellar calcium phosphate retained 4-aminobenzoic acid inside its cavity without leaching. The intense infrared bands in the 1033 and 1010 cm^?1 interval confirmed the presence of the phosphonate groups attached to the inorganic layer, with sharp and intense peaks in X-ray diffraction patterns, which gave basal distances of 712 and 1578 pm for the original and the intercalated compounds, respectively. Solid-state ³¹P nuclear magnetic resonance spectra presented only one peak for the phosphate groups attached to the main inorganic polymeric structure near ?2.4 ppm. The adsorption isotherms from ethanol gave the maximum adsorption capacities of 6.44 and 3.34 mmol g^?1 for nickel and cobalt, respectively, which stability constant and distribution coefficient followed Co > Ni.     

Preparation of silica fibers and non-woven cloth by electrospinning

Silica fibers, which can potentially be used as filters and media for catalysts immobilization, were successfully spun via electrospinning process with precursor prepared through the sol–gel synthesis. Spinnable sols can be obtained only when the molar ratio of water to TEOS is less than 2 which is consistent with the retrospective results derived for other spinning methods. It was confirmed for the first time that the reaction time can be drastically reduced by introducing humidified air, controlled by KCl saturated aqueous solution, during sol–gel process. The size of obtained silica fibers is about 4.5 μm and has a certain degree of flexibility and mechanical strength. Although the specific surface area of as spun fiber was 7.7 m²/g, which is apparently small comparing to generic silica, treatment by boiling water only for 5 min could increase the specific surface area to be about 500 m²/g.