Search Results (15)

This study investigates the formation of by-product species during flame spray synthesis (SFS) of superparamagnetic maghemite (γ-Fe₂O₃) nanoparticles. Four samples are synthesized by utilizing two standardized burner types (SpraySyn1 and SpraySyn2) and varying the iron (III) nonahydrate (INN) concentration (0.1 M and 0.2 M) in the precursor feed while using ethanol and 2-ethylhexanoic acid as solvent. Conducting complementary powder analysis revealed a predominant presence of carboxylates and carbonates as by-product species (~14–18 wt.%), while no strong indications for elemental carbon and precursor/solvent residues can be found. Carbonates/carboxylates are located on particle surfaces, and the particles’ surface loadings by these species are independent of the precursor concentration but depend on burner type, with SpraySyn2 exhibiting lower values, indicating a more complete combustion for this burner. Through time-resolved thermophoretic sampling, we further demonstrate that carbon forms temporally in the visible flame center when using SpraySyn1. Since carbon solely forms momentarily within large flame pulses and decomposes further downstream, its temporal formation is of minor relevance for the final particle purity. However, its local co-existence aside from γ-Fe₂O₃ in the flame has potential to bias in situ diagnostics. Full article

Wettability, typically estimated through the contact angle, is a fundamental property of surfaces with wide-ranging implications in both daily life and industrial processes. Recent scientific interest has been paid to the surfaces exhibiting extreme wettability: superhydrophobic and superhydrophilic surfaces, characterized by high water repellency and exceptional water wetting, respectively. Both chemical composition and morphology play a role in the determination of the wettability “performance” of a surface. To tune surface-wetting properties, we considered coatings of carbon nanoparticles (CNPs) in this study. They are a new class of nanomaterials synthesized in flames whose chemistry, dimension, and shape depend on combustion conditions. For the first time, we systematically studied the wettability of CNP coatings produced in a controlled rich ethylene/air flame stabilized over a McKenna burner. A selected substrate was intermittently inserted in the flame at 15 mm above the burner to form a thin coating thanks to a thermophoretic-driven deposition mechanism. The chemical-physical quality and the deposed quantity of the CNPs were varied by opportunely combing the substrate flame insertion number (from 1 to 256) and the carbon-to-oxygen ratio, C/O (from 0.67 to 0.87). The wettability of the coatings was evaluated by measuring the contact angle, CA, with the sessile drop method. When the C/O = 0.67, the CNPs were nearly spherical, smaller than 8 nm, and always generated hydrophilic coatings (CA < 35°). At higher C/O ratios, the CNPs reached dimensions of 100 nm, and fractal shape aggregates were formed. In this case, either hydrophilic (CA < 76°) or superhydrophobic (CA ~166°) behavior was observed, depending on the number of carbon nanoparticles deposed, i.e., film thickness. It is known that wettability is susceptible to liquid surface tension, and therefore, tests were conducted with different fluids to establish a correlation between the flame conditions and the nanostructure of the film. This method offers a fast and simple approach to determining mesoscale information for coating roughness and topographical homogeneity/inhomogeneity of their surfaces. Full article

Poly (lactic acid) or polylactide (PLA) has gained widespread use in many industries and has become a commodity polymer. Its potential as a perfect replacement for petrochemically made plastics has been constrained by its extreme flammability and propensity to flow in a fire. Traditional flame-retardants (FRs), such as organo-halogen chemicals, can be added to PLA without significantly affecting the material’s mechanical properties. However, the restricted usage of these substances causes them to bioaccumulate and endanger plants and animals. Research on PLA flame-retardants has mostly concentrated on organic and inorganic substances for the past few years. Meanwhile, there has been a significant increase in renewed interest in creating environmentally acceptable flame-retardants for PLA to maintain the integrity of the polymer, which is the current trend. This article reviews recent advancements in novel FRs for PLA. The emphasis is on two-dimensional (2D) nanosystems and the composites made from them that have been used to develop PLA nanocomposite (NCP) systems that are flame retarding. The association between FR loadings and efficiency for different FR-PLA systems is also briefly discussed in the paper, as well as their influence on processing and other material attributes. It is unmistakably established from the literature that adding 2D nanoparticles to PLA matrix systems reduces their flammability by forming an intumescent char/carbonized surface layer. This creates a barrier effect that successfully blocks the filtration of volatiles and oxygen, heat and mass transfer, and the release of combustible gases produced during combustion. Full article

A porous nanostructured film of flame-formed carbon nanoparticles has been produced with a one-step procedure. The morphological and structural characteristics of the film have been characterized by atomic force microscopy and Raman spectroscopy. The electrical resistance as a function of the temperature has been investigated in the range from ambient temperature to 120 °C. A nonmetallic behavior has been observed, with a monotonic decrease of the film resistance as temperature increases. Electrical conduction is explained in terms of charge carriers tunneling and percolation between the carbon grains and is not perfectly described by an Arrhenius behavior. A negative temperature coefficient of resistance (TCR) of the order of −100 × 10⁻⁴ K⁻¹ has been measured. The high absolute TCR value, together with the ease of material microfabrication processing and biocompatibility of the carbon material make this film ideal for temperature sensing in many environments. A functional relationship between resistance and temperature, which is necessary for practical applications, has been finally derived. A very good agreement between experimental data and fit is obtained with a fifth order polynomial. Full article

Carbon-based polymer can catch fire when used as cathode material in batteries and supercapacitors, due to short circuiting. Polyimide is known to exhibit flame retardancy by forming char layer in condensed phase. The high char yield of polyimide is attributed to its aromatic nature and the existence of a donor–acceptor complex in its backbone. Fabrication of hybrid polyimide material can provide better protection against fire based on multiple fire-retardancy mechanisms. Nanocomposites generally show a significant enhancement in mechanical, electrical, and thermal properties. Nanoparticles, such as graphene and carbon nanotubes, can enhance flame retardancy in condensed phase by forming a dense char layer. Silicone-based materials can also provide fire retardancy in condensed phase by a similar mechanism as polyimide. However, some inorganic fire retardants, such as phosphazene, can enhance flame retardancy in gaseous phase by releasing flame inhibiting radicals. The flame inhibiting radicals generated by phosphazene are released into the gaseous phase during combustion. A hybrid system constituted of polyimide, silicone-based additives, and phosphazene would provide significant improvement in flame retardancy in both the condensed phase and gas phase. In this review, several flame-retardant polyimide-based systems are described. This review which focuses on the various combinations of polyimide and other candidate fire-retardant materials would shed light on the nature of an effective multifunctional flame-retardant hybrid materials. Full article

In this study we report the effect of fuel type (biodiesel vs. methane), flame structure and flame height (inner-cone vs. outer-cone), and the percent of oxygen content in the oxidizer stream for the formation of hydrophobic carbon layers using co-flow diffusion flames. It was found that a flame formed using a gaseous fuel (methane) over a vaporized liquid fuel, Canola Methyl Ester (CME), has significant structural differences that enable vastly different deposition behavior of soot layers on the surface of solid substrates. Due to its larger pyrolysis zone (taller inner-cone), the CH₄/air flame has a smaller region that supports uniform soot deposition of hydrophobic carbon layers (C-layers) compared to the CME/air flame. When a solid substrate is placed within the pyrolysis zone (inner-cone) of a flame the resulting layer is non-uniform, hydrophilic, and consists of undeveloped soot. However, when outside the pyrolysis zone, the deposited soot tends to be uniform and mature, ultimately creating a hydrophobic C-layer consisting of the typical microscale interconnected weblike structures formed of spherical soot nanoparticles. The effect of oxygen content (35% and 50% O₂) in the oxidizer stream for the formation of hydrophobic C-layers was also studied in this work. It was found that oxygen enrichment within the CME flame alters the structure of the flame, hence affecting the morphology of the formed C-layer. Under oxygen enrichment the central region of the deposited C-layer is composed of a weblike structure similar to those seen in the air flames; however, this central region is bordered by a region of densely compacted soot that shows signs of significant thermal stress. At 35% O₂ the thermal stress is expressed as multiple microscale cracks while at 50% O₂ this border region shows much larger cracks and macroscale layer peeling. The formed C-layers under the different flame conditions were tested for hydrophobicity by measuring the contact angle of a water droplet. The morphology of the C-layers was analyzed using scanning electron microscopy. Full article

Carbon nano-onions (CNOs) were successfully synthesized by employing the flame pyrolysis (FP) method, using flaxseed oil as a carbon source. The alcohol reduction method was used to prepare Pd/CNOs and Pd-Sn/CNOs electro-catalysts, with ethylene glycol as the solvent and reduction agent. The metal-nanoparticles were supported on the CNO surface without adjusting the pH of the solution. High-resolution transmission electron microscopy (HRTEM) images reveal CNOs with concentric graphite ring morphology, and also PdSn nanoparticles supported on the CNOs. X-ray diffractometry (XRD) patterns confirm that CNOs are amorphous and show the characteristic diffraction peaks of Pd. There is a shifting of Pd diffraction peaks to lower angles upon the addition of Sn compared to Pd/CNOs. X-ray photoelectron spectroscopy (XPS) results also confirm the doping of Pd with Sn to form a PdSn alloy. Fourier transform infrared spectroscopy (FTIR) displays oxygen, hydroxyl, carboxyl, and carbonyl, which facilitates the dispersion of Pd and Sn nanoparticles. Raman spectrum displays two prominent peaks of carbonaceous materials which correspond to the D and G bands. The Pd-Sn/CNOs electro-catalyst demonstrates improved electro-oxidation of methanol and ethanol performance compared to Pd/CNOs and commercial Pd/C electro-catalysts under alkaline conditions. Full article

In this work, an experimental investigation of the nanomechanical properties of flame-formed carbonaceous particle layers has been performed for the first time by means of Atomic Force Microscopy (AFM). To this aim, carbon nanoparticles with different properties and nanostructures were produced in ethylene/air laminar premixed flames at different residence times. Particles were collected on mica substrates by means of a thermophoretic sampling system and then analyzed by AFM. An experimental procedure based on the combination between semi-contact AFM topography imaging, contact AFM topography imaging and AFM force spectroscopy has been implemented. More specifically, a preliminary topological characterization of the samples was first performed operating AFM in semi-contact mode and then tip-sample interaction forces were measured in contact spectroscopy mode. Finally, semi-contact mode was used to image the indented surface of the samples and to retrieve the projected area of indents. The hardness of investigated samples was obtained from the force–distance curves measured in spectroscopy mode and the images of intends acquired in semi-contact mode. Moreover, the Young’s modulus was measured by fitting the linear part of the retraction force curves using a model based on the Hertz theory. The extreme force sensitivity of this technique (down to nNewton) in addition to the small size of the probe makes it extremely suitable for performing investigation of mechanical properties of materials at the nanoscale. The experimental procedure was successfully tested on reference materials characterized by different plastic behavior, e.g., polyethylene naphthalate and highly oriented pyrolytic graphite. Both hardness and Young’s modulus values obtained from AFM measurements for different soot particle films were discussed. Full article

Nanostructured films of carbon and TiO₂ nanoparticles have been produced by means of a simple two-step procedure based on flame synthesis and thermophoretic deposition. At first, a granular carbon film is produced on silicon substrates by the self-assembling of thermophoretically sampled carbon nanoparticles (CNPs) with diameters of the order of 15 nm. Then, the composite film is obtained by the subsequent thermophoretic deposition of smaller TiO₂ nanoparticles (diameters of the order of 2.5 nm), which deposit on the surface and intercalate between the carbon grains by diffusion within the pores. A bipolar resistive switching behavior is observed in the composite film of CNP-TiO₂. A pinched hysteresis loop is measured with SET and RESET between low resistance and high resistance states occurring for the electric field of 1.35 × 10⁴ V/cm and 1.5 × 10⁴ V/cm, respectively. CNP-TiO₂ film produced by flame synthesis is initially in the low resistive state and it does not require an electroforming step. The resistance switching phenomenon is attributed to the formation/rupture of conductive filaments through space charge mechanism in the TiO₂ nanoparticles, which facilitate/hinder the electrical conduction between carbon grains. Our findings demonstrate that films made of flame-formed CNP-TiO₂ nanoparticles are promising candidates for resistive switching components. Full article

A spray-flame reaction step followed by a short 1-h sintering step under O₂ atmosphere was used to synthesize nanocrystalline cubic Al-doped Li₇La₃Zr₂O₁₂ (LLZO). The as-synthesized nanoparticles from spray-flame synthesis consisted of the crystalline La₂Zr₂O₇ (LZO) pyrochlore phase while Li was present on the nanoparticles’ surface as amorphous carbonate. However, a short annealing step was sufficient to obtain phase pure cubic LLZO. To investigate whether the initial mixing of all cations is mandatory for synthesizing nanoparticulate cubic LLZO, we also synthesized Li free LZO and subsequently added different solid Li precursors before the annealing step. The resulting materials were all tetragonal LLZO (I4₁/acd) instead of the intended cubic phase, suggesting that an intimate intermixing of the Li precursor during the spray-flame synthesis is mandatory to form a nanoscale product. Based on these results, we propose a model to describe the spray-flame based synthesis process, considering the precipitation of LZO and the subsequent condensation of lithium carbonate on the particles’ surface. Full article

In this study, flame-formed carbon nanoparticles of different nanostructures have been produced by changing the flame temperature. Raman spectroscopy has been used for the characterization of the carbon nanoparticles, while the particle size has been obtained by online measurements made by electrical mobility analysis. The results show that, in agreement with recent literature data, a large variety of carbon nanoparticles, with a different degree of graphitization, can be produced by changing the flame temperature. This methodology allows for the synthesis of very small carbon nanoparticles with a size of about 3–4 nm and with different graphitic orders. Under the perspective of the material synthesis process, the variable-temperature flame-synthesis of carbon nanoparticles appears as an attractive procedure for a cost-effective and easily scalable production of highly tunable carbon nanoparticles. Full article

Carbon nanotubes (CNTs) are synthesized by the flame fragment deposition (FFD) technique using Iraqi liquefied petroleum gas (LPG) as a source of carbon in a hand-made reactor at a low temperature (160 °C) without using a catalyst. Purification of the multi-walled carbon nanotubes (MWCNTs) is carried out using a two-step process consisting of sonication in 30 wt.% hydrogen peroxide (H₂O₂) solution at room temperature to remove amorphous impurities adhering to the walls of the CNTs and carbon nanoparticles (CNPs), followed by sonication in an acetone bath to remove the polyaromatic hydrocarbons (PAH) formed during the LPG gas burning. Comprehensive characterizations such as X-ray diffraction (XRD), atomic force microscopy (AFM), thermo-gravimetric analysis (TGA), and transmission electron microscopy (TEM) were conducted to verify the efficiency of the purification process. The results clearly demonstrated that this process is promising for the purification of the synthesized CNTs. Full article

Breast cancer is the abnormal, uncontrollable proliferation of cells in the breast. Conventional treatment modalities like chemotherapy induce deteriorating side effects on healthy cells. Non-viral inorganic nanoparticles (NPs) confer exclusive characteristics, such as, stability, controllable shape and size, facile surface modification, and unique magnetic and optical properties which make them attractive drug carriers. Among them, carbonate apatite (CA) particles are pH-responsive in nature, enabling rapid intracellular drug release, but are typically heterogeneous with the tendency to self-aggregate. Here, we modified the nano-carrier by partially substituting Ca²⁺ with Mg²⁺ and Fe³⁺ into a basic lattice structure of CA, forming Fe/Mg-carbonate apatite (Fe/Mg-CA) NPs with the ability to mitigate self-aggregation, form unique protein corona in the presence of serum and efficiently deliver doxorubicin (DOX), an anti-cancer drug into breast cancer cells. Two formulations of Fe/Mg-CA NPs were generated by adding different concentrations of Fe³⁺ and Mg²⁺ along with a fixed amount of Ca²⁺ in bicarbonate buffered DMEM (Dulbecco’s Modified Eagle’s Medium), followed by 30 min incubation at 37 °C. Particles were characterized by turbidity analysis, z-average diameter and zeta potential measurement, optical microscopy, field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), energy dispersive X-ray (EDX), flame atomic absorption spectroscopy (FAAS), pH dissolution, drug binding, cellular uptake, thiazolyl blue tetrazolium bromide (MTT) assay, stability analysis, and protein corona study by LCMS (Liquid chromatography-mass spectrometry). Both formulations of Fe/Mg-CA displayed mostly uniform nano-sized particles with less tendency to aggregate. The EDX and FAAS elemental analysis confirmed the weight (%) of Ca, Fe and Mg, along with their Ca/P ratio in the particles. A constant drug binding efficiency was noticed with 5 μM to 10 μM of initial DOX concentration. A pH dissolution study of Fe/Mg-CA NPs revealed the quick release of DOX in acidic pH. Enhancement of cytotoxicity for the chemotherapy drug was greater for Fe/Mg-CA NPs as compared to CA NPs, which could be explained by an increase in cellular internalization as a result of the small z-average diameter of the former. The protein corona study by LCMS demonstrated that Fe/Mg-CA NPs exhibited the highest affinity towards transport proteins without binding with opsonins. Biodistribution study was performed to study the effect of DOX-loaded Fe/Mg-CA NPs on the tissue distribution of DOX in Balb/c 4T1 tumor-bearing mice. Both formulations of Fe/Mg-CA NPs have significantly increased the accumulation of DOX in tumors. Interestingly, high Fe/Mg-CA NPs exhibited less off-target distribution compared to low Fe/Mg-CA NPs. Furthermore, the blood plasma analysis revealed prolonged blood circulation half-life of DOX-loaded low and high Fe/Mg-CA NPs compared to free DOX solution. Modifying CA NPs with Fe³⁺ and Mg²⁺, thereby, led to the generation of nano-sized particles with less tendency to aggregate, enhancing the drug binding efficiency, cellular uptake, and cytotoxicity without hampering drug release in acidic pH, while improving the circulation half-life and tumor accumulation of DOX. Therefore, Fe/Mg-CA which predominantly forms a transport protein-related protein corona could be a proficient carrier for therapeutic delivery in breast cancer. Full article

The photoreduction of CO₂ is an intriguing process which allows the synthesis of fuels and chemicals. One of the limitations for CO₂ photoreduction in the liquid phase is its low solubility in water. This point has been here addressed by designing a fully innovative pressurized photoreactor, allowing operation up to 20 bar and applied to improve the productivity of this very challenging process. The photoreduction of CO₂ in the liquid phase was performed using commercial TiO₂ (Evonink P25), TiO₂ obtained by flame spray pyrolysis (FSP) and gold doped P25 (0.2 wt% Au-P25) in the presence of Na₂SO₃ as hole scavenger (HS). The different reaction parameters (catalyst concentration, pH and amount of HS) have been addressed. The products in liquid phase were mainly formic acid and formaldehyde. Moreover, for longer reaction time and with total consumption of HS, gas phase products formed (H₂ and CO) after accumulation of significant number of organic compounds in the liquid phase, due to their consecutive photoreforming. Enhanced CO₂ solubility in water was achieved by adding a base (pH = 12–14). In basic environment, CO₂ formed carbonates which further reduced to formaldehyde and formic acid and consequently formed CO/CO₂ + H₂ in the gas phase through photoreforming. The deposition of small Au nanoparticles (3–5 nm) (NPs) onto TiO₂ was found to quantitatively influence the products distribution and increase the selectivity towards gas phase products. Significant energy storage in form of different products has been achieved with respect to literature results. Full article

Because of their extraordinary properties, such as high thermal stability, flame retardant, high chemical resistance and high mechanical strength, thermotropic liquid crystalline polymers (TLCPs) have recently gained more attention while being useful for many applications which require chemical inertness and high strength. Due to the recent advance in nanotechnology, TLCPs are usually compounded with nanoparticles to form particulate composites to enhance their properties, such as barrier properties, electrical properties, mechanical properties and thermal properties. Carbon-based nanofillers such as carbon nanotube (CNT), graphene and graphene oxide are the most common fillers used for the TLCP matrices. In this review, we focus on recent advances in thermotropic main-chain liquid crystalline polymer nanocomposites incorporated with CNTs. However, the biggest challenges in the preparation of CNT/TLCP nanocomposites have been shown to be inherent in the dispersion of CNTs into the TLCP matrix, the alignment and control of CNTs in the TLCP matrix and the load-transfer between the TLCP matrix and CNTs. As a result, this paper reviews recent advances in CNT/TLCP nanocomposites through enhanced dispersion of CNTs in TLCPs as well as their improved interfacial adhesion with the TLCP matrices. Case studies on the important role of chemically modified CNTs in the TLCP/thermoplastic polymer blends are also included. Full article