RESUMO
The purpose of this study was to investigate the synthesis of iron oxide nanoparticles under two different conditions, namely high and low gas flow rates, using laser pyrolysis and to examine the influence of laser power. The attained nanoparticles have been characterised regarding their stability and hydrodynamic dimensions by dispersive light scattering analysis (DLS), structure-X-ray diffraction (XRD), elemental composition-energy-dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS), and morpho-structural characterisation achieved by transmission electron microscopy (TEM) and selected-area electron diffraction (SAED). For a better understanding of the laser power influence, the residence time was also calculated.
RESUMO
The carbonization of polyacrylonitrile (PAN) by direct laser writing to produce microsupercapacitors directly on-chip is reported. The process is demonstrated by producing interdigitated carbon finger electrodes directly on a printed circuit board (PCB), which is then employed to characterize the supercapacitor electrodes. By varying the laser power, the process can be tuned from carbonization to material ablation. This allows to not only convert pristine PAN films into carbon electrodes, but also to pattern and cut away non-carbonized material to produce completely freestanding carbon electrodes. While the carbon electrodes adhere well to the printed circuit board, non-carbonized PAN is peeled off the substrate. Specific capacities as high as 260 µF cmâ»2 are achieved in a supercapacitor with 16 fingers.
Assuntos
Carbono , Lasers , Resinas Acrílicas , Carbono/química , Eletrodos , RedaçãoRESUMO
TiO2 nanoparticles were synthesized by laser pyrolysis from TiCl4 vapor in air in the presence of ethylene as sensitizer at different working pressures (250-850 mbar) with and without further calcination at 450 °C. The obtained powders were analyzed by energy-dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, X-ray diffractometry, and transmission electron microscopy. Also, specific surface area and photoluminescence with optical absorbance were evaluated. By varying the synthesis parameters (especially the working pressure), different TiO2 nanopowders were obtained, whose photodegradation properties were tested compared to a commercial Degussa P25 sample. Two series of samples were obtained. Series "a" includes thermally treated TiO2 nanoparticles (to remove impurities) that have different proportions of the anatase phase (41.12-90.74%) mixed with rutile and small crystallite sizes of 11-22 nm. Series "b" series represents nanoparticles with high purity, which did not require thermal treatment after synthesis (ca. 1 atom % of impurities). These nanoparticles show an increased anatase phase content (77.33-87.42%) and crystallite sizes of 23-45 nm. The TEM images showed that in both series small crystallites form spheroidal nanoparticles with dimensions of 40-80 nm, whose number increases with increasing the working pressure. The photocatalytic properties have been investigated regarding the photodegradation of ethanol vapors in Ar with 0.3% O2 using P25 powder as reference under simulated solar light. During the irradiation H2 gas production has been detected for the samples from series "b", whereas the CO2 evolution was observed for all samples from series "a".
RESUMO
The concentration of environmental pollutants needs to be monitored constantly by reliable analytical methods since they pose a public health risk. Developing simple and affordable sensors for such pollutants can allow for large-scale monitoring economically. Here, we develop a simple electrochemical sensor for sulfanilamide (SFD) quantification using a phenolic resin substrate and a CO2 laser to pyrolyze the sensor geometry over the substrate. The sensors are modified with carbon nanotubes via a simple drop-casting procedure. The carbon nanotube loading effect the electrochemical performance toward a redox probe and analytical performance for SFD detection is investigated, showing no net benefit beyond 1 mg L-1 of carbon nanotubes. The effects of the modification on the SFD oxidation are shown to be more than just an electrode area effect and possibly attributed to the fast electron transfer kinetics of the carbon nanotubes. SFD detection is performed at small solution volumes under static (800 µL) and hydrodynamic conditions (3 mL) in a fully integrated, miniaturized batch-injection analyses cell. Both methods have a similar linear range from 10.0 to 115.0 µmol L-1 and high selectivity for SFD determination. Both systems are used to quantify SFD in real samples as a proof of concept, showcasing the proposed device's applicability as a sensor for environmental and public health monitoring of SFD.
RESUMO
The fabrication of flexible pressure sensors with low cost, high scalability, and easy fabrication is an essential driving force in developing flexible electronics, especially for high-performance sensors that require precise surface microstructures. However, optimizing complex fabrication processes and expensive microfabrication methods remains a significant challenge. In this study, we introduce a laser pyrolysis direct writing technology that enables rapid and efficient fabrication of high-performance flexible pressure sensors with a micro-truncated pyramid array. The pressure sensor demonstrates exceptional sensitivities, with the values of 3132.0, 322.5, and 27.8 kPa-1 in the pressure ranges of 0-0.5, 0.5-3.5, and 3.5-10 kPa, respectively. Furthermore, the sensor exhibits rapid response times (loading: 22 ms, unloading: 18 ms) and exceptional reliability, enduring over 3000 pressure loading and unloading cycles. Moreover, the pressure sensor can be easily integrated into a sensor array for spatial pressure distribution detection. The laser pyrolysis direct writing technology introduced in this study presents a highly efficient and promising approach to designing and fabricating high-performance flexible pressure sensors utilizing micro-structured polymer substrates.
RESUMO
Polymer-derived ceramic (PDC)-based high-temperature thin-film sensors (HTTFSs) exhibit promising applications in the condition monitoring of critical components in aerospace. However, fabricating PDC-based HTTFS integrated with high-efficiency, high-temperature anti-oxidation, and customized patterns remains challenging. In this work, we introduce a rapid and flexible selecting laser pyrolysis combined with a direct ink writing process to print double-layer high-temperature antioxidant PDC composite thin-film thermistors under ambient conditions. The sensitive layer (SL) was directly written on an insulating substrate with excellent conductivity by laser-induced graphitization. Then, the antioxidant layer (AOL) was written on the surface of the SL to realize the integrated manufacturing of double-functional layers. Through characterization analysis, it was shown that B2O3 and SiO2 glass phases generated by the PDC composite AOL could effectively prevent oxygen intrusion. Therefore, the fabricated PDC composite thermistors exhibited a negative temperature coefficient in the temperature range from 100 to 1100 °C and high repeatability below 800 °C. Meanwhile, it has excellent high-temperature stability at 800 °C with a resistance change of only 2.4% in 2 h. Furthermore, the high-temperature electrical behavior of the thermistor was analyzed. The temperature dependence of the conductivity for this thermistor has shown an agreement with the Mott's variable range hopping mechanism. Additionally, the thermistor was fabricated on the surface of an aero-engine blade to verify its feasibility below 800 °C, showing the great potential of this work for state sensing on the surface of high-temperature components, especially for customized requirements.
RESUMO
Laser-induced graphene (LIG) has shown great potential for controllable and scalable realization of microsupercapacitors (MSCs). However, as is well-known, LIG electrodes suffer from low charge storage capacity and conductance. In this paper, a lasing-centric method is presented for defect control and morphological enhancement in LIG electrodes through unique dual laser pyrolysis. This method encompasses dual lasing pyrolysis, one for the synthesis of defocused LIG, and another for the decoration of Ru nanoparticles to enhance electrochemical performance. Fundamentally, the investigation simultaneously optimizes for defocused lasing distance and lasing speed, which to the best of the author's knowledge, has not been previously reported. The defocused LIG electrode exhibits a remarkably improved electrochemical capacitance of over 25 times (114 mF cm-2 ) compared to the one based on focused laser-induced graphene (FLIG). As a device demonstration, a flexible and self-healable MSC has been fabricated based on DFLIG/Ru-PEDOT/Au electrodes, exhibiting a high areal specific capacitance (25.7 mF cm-2 ), excellent electrochemical stability (91% retention of specific capacitance after 8000 cycles), and good self-healing performance (85.6% retention of specific capacitance after two cut-heal cycles). By enhancing material properties via dual defocused laser pyrolysis, this work presents a strategy for highly controllable and scalable realization of electrodes in micro-energy storage devices.
RESUMO
Polymer-derived ceramic (PDC) is considered an excellent sensing material for harsh environments such as aero-engines and nuclear reactors. However, there are many inherent limitations not only in pure PDC but also in its common fabrication method by furnace thermolysis. Therefore, this study proposes a novel method of rapid in situ fabrication of PDC composite thin-film sensors by laser pyrolysis. Using this method with different fillers, a sensitive PDC composite film layer with high-quality graphite can be obtained quickly, which is more flexible and efficient compared to the traditional furnace thermolysis. Furthermore, this study analyzes the reaction differences between laser pyrolysis and furnace thermolysis. The laser pyrolysis method principally produces ß-SiC and enhances the graphitization of amorphous carbon, while the degree of graphitization by furnace thermolysis is low. In addition, it is capable of rapidly preparing an insulating PDC composite film, which still has a resistance of 5 MΩ at 600 °C. As a proof of this method, the PDC composite thin-film strain sensors are fabricated in situ on nickel alloys and aluminum oxide substrates, respectively. The sensor fabricated on the nickel alloy with a high gauge factor of over 100 can be used in high-temperature environments below 350 °C without the protection of an oxidation-resistant coating. In this way, the approach pioneers the in situ laser fabrication of functional PDC films for sensors, and it has great potential for the in situ sensing of complex curved surfaces in harsh environments.
RESUMO
Pyrolytic carbon microelectrodes (PCMEs) are a promising alternative to their conventional metallic counterparts for various applications. Thus, methods for the simple and inexpensive patterning of PCMEs are highly sought after. Here, we demonstrate the fabrication of PCMEs through the selective pyrolysis of SU-8 photoresist by irradiation with a low-power, 806 nm, continuous wave, semiconductor-diode laser. The SU-8 was modified by adding Pro-Jet 800NP (FujiFilm) in order to ensure absorbance in the 800 nm range. The SU-8 precursor with absorber was successfully converted into pyrolytic carbon upon laser irradiation, which was not possible without an absorber. We demonstrated that the local laser pyrolysis (LLP) process in an inert nitrogen atmosphere with higher laser power and lower scan speed resulted in higher electrical conductance. The maximum conductivity achieved for a laser-pyrolyzed line was 14.2 ± 3.3 S/cm, with a line width and thickness of 28.3 ± 2.9 µm and 6.0 ± 1.0 µm, respectively, while the narrowest conductive line was just 13.5 ± 0.4 µm wide and 4.9 ± 0.5 µm thick. The LLP process seemed to be self-limiting, as multiple repetitive laser scans did not alter the properties of the carbonized lines. The direct laser writing of adjacent lines with an insulating gap down to ≤5 µm was achieved. Finally, multiple lines were seamlessly joined and intersected, enabling the writing of more complex designs with branching electrodes and the porosity of the carbon lines could be controlled by the scan speed.
RESUMO
Silicon is a promising material for high-energy anode materials for the next generation of lithium-ion batteries. The gain in specific capacity depends highly on the quality of the Si dispersion and on the size and shape of the nano-silicon. The aim of this study is to investigate the impact of the size/shape of Si on the electrochemical performance of conventional Li-ion batteries. The scalable synthesis processes of both nanoparticles and nanowires in the 10-100 nm size range are discussed. In cycling lithium batteries, the initial specific capacity is significantly higher for nanoparticles than for nanowires. We demonstrate a linear correlation of the first Coulombic efficiency with the specific area of the Si materials. In long-term cycling tests, the electrochemical performance of the nanoparticles fades faster due to an increased internal resistance, whereas the smallest nanowires show an impressive cycling stability. Finally, the reversibility of the electrochemical processes is found to be highly dependent on the size/shape of the Si particles and its impact on lithiation depth, formation of crystalline Li15Si4 in cycling, and Li transport pathways.
RESUMO
The design or dimension of micro-supercapacitor electrodes is an important factor that determines their performance. In this study, a microsupercapacitor was precisely fabricated on a silicon substrate by irradiating an imprinted furan micropattern with a CO2 laser beam under ambient conditions. Since furan is a carbon-abundant polymer, electrically conductive and porous carbon structures were produced by laser-induced pyrolysis. While the pyrolysis of a furan film in a general electric furnace resulted in severe cracks and delamination, the laser pyrolysis method proposed herein yielded porous carbon films without cracks or delamination. Moreover, as the imprinting process already designated the furan area for laser pyrolysis, high-precision patterning was achieved in the subsequent laser pyrolysis step. This two-step process exploited the superior resolution of imprinting for the fabrication of a laser-pyrolyzed carbon micropattern. As a result, the technical limitations of conventional laser direct writing could be overcome. The laser-pyrolyzed carbon structure was employed for microsupercapacitor electrodes. The microsupercapacitor showed a specific capacitance of 0.92 mF/cm2 at 1 mA/cm2 with a PVA-H2SO4 gel electrolyte, and retained an up to 88% capacitance after 10,000 charging/discharging cycles.
RESUMO
Zn/F co-doped SnO2 nanoparticles with a mean diameter of less than 15 nm and a narrow size distribution were synthesized by a one-step laser pyrolysis technique using a reactive mixture containing tetramethyltin (SnMe4) and diethylzinc (ZnEt2) vapors, diluted Ar, O2 and SF6. Their structural, morphological, optical and electrical properties are reported in this work. The X-ray diffraction (XRD) analysis shows that the nanoparticles possess a tetragonal SnO2 crystalline structure. The main diffraction patterns of stannous fluoride (SnF2) were also identified and a reduction in intensity with increasing Zn percentage was evidenced. For the elemental composition estimation, energy dispersion X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) measurements were performed. In general, both analyses showed that the Zn percentage increases with increasing ZnEt2 flow, accompanied at the same time by a decrease in the amount of F in the nanopowders when the same SF6 flow was employed. The Raman spectra of the nanoparticles show the influence of both Zn and F content and crystallite size. The fluorine presence is due to the catalytic partial decomposition of the SF6 laser energy transfer agent. In direct correlation with the increase in the Zn doping level, the bandgap of co-doped nanoparticles shifts to lower energy (from 3.55 to 2.88 eV for the highest Zn dopant concentration).
RESUMO
Laser synthesis was used for one-step synthesis of titania/graphene composites (G-TiO2 (C)) from a suspension of 0.04 wt% commercial reduced graphene oxide (rGO) dispersed in liquid titanium tetraisopropoxide (TTIP). Reference titania sample (TiO2(C)) was prepared by the same method without graphene addition. Both samples and commercial titania P25 were characterized by various methods and tested under UV/vis irradiation for oxidative decomposition of acetic acid and dehydrogenation of methanol (with and without Pt co-catalyst addition), and under vis irradiation for phenol degradation and inactivation of Escherichia coli. It was found that both samples (TiO2(C) and G-TiO2(C)) contained carbon resulting from TTIP and C2H4 (used as a synthesis sensitizer), which activated titania towards vis activity. The photocatalytic activity under UV/vis irradiation was like that by P25. The highest activity of TiO2(C) sample for acetic acid oxidation was probably caused by its surface enrichment with hydroxyl groups. G-TiO2(C) was the most active for methanol dehydrogenation in the absence of platinum (ca. five times higher activity than that by TiO2(C) and P25), suggesting that graphene works as a co-catalyst for hydrogen evolution. High activity under both UV and vis irradiation for decomposition of organic compounds, hydrogen evolution and inactivation of bacteria suggests that laser synthesis allows preparation of cheap (carbon-modified) and efficient photocatalysts for broad environmental applications.
RESUMO
This review describes promising laser-based approaches to produce silicon nanostructures, including laser ablation of solid Si targets in residual gases and liquids and laser pyrolysis of silane. These methods are different from, and complementary to, widely used porous silicon technology and alternative synthesis routes. One can use these methods to make stable colloidal dispersions of silicon nanoparticles in both organic and aqueous media, which are suitable for a multitude of applications across the important fields of energy and healthcare. Size tailoring allows production of Si quantum dots with efficient photoluminescence that can be tuned across a broad spectral range from the visible to near-IR by varying particle size and surface functionalization. These nanoparticles can also be integrated with other nanomaterials to make multifunctional composites incorporating magnetic and/or plasmonic components. In the energy domain, this review highlights applications to photovoltaics and photodetectors, nanostructured silicon anodes for lithium ion batteries, and hydrogen generation from water. Application to nanobiophotonics and nanomedicine profits from the excellent biocompatibility and biodegradability of nanosilicon. These applications encompass several types of bioimaging and various therapies, including photodynamic therapy, RF thermal therapy, and radiotherapy. The review concludes with a discussion of challenges and opportunities in the applications of laser-processed nanosilicon.
Assuntos
Atenção à Saúde , Lasers , Nanoestruturas/química , Silício/química , Animais , Técnicas Biossensoriais , Humanos , Imagem Multimodal , Nanoestruturas/ultraestruturaRESUMO
The pyrolysis of the lignocellulosic biomass is a promising process to produce biofuels or green chemicals. Specific analytical methods have to be developed in order to better understand the composition of biomass and of its pyrolysis products and therefore to optimize the design of pyrolysis processes. For this purpose, different biomasses (Douglas and Miscanthus) and one biochar were analyzed by laser desorption/ionization Fourier transform ion cyclotron resonance mass spectrometry (LDI FT-ICR MS). This method allowed the biomass and biochar to be analyzed without any sample preparation and with a spatial resolution of about 100 µm. The influence of LDI conditions (laser wavelength and laser irradiance) and the nature of the biomass and biochar on the obtained mass spectrum were investigated. The nature and origin of the observed ions highly depended on LDI conditions. In the softest laser-biomass interaction conditions (low laser irradiance), the detected ions were related to the nature of the investigated biomass. Indeed, the main part of the detected species came from the different biomass subunits and was produced by photolysis of covalent bonds. When more severe laser irradiation conditions were used, the obtained mass spectra gathered the ions relative to (i) the chemical components of the investigated samples, (ii) the recombination products of these species in the gas phase after their ejection from the sample surface, and (iii) the compounds produced by laser pyrolysis of the sample. This was expected to be useful to mimic thermal pyrolysis. Graphical Abstract.
RESUMO
C-encapsulated highly pure PtxCoy alloy nanoparticles have been synthesized by an innovative one-step in-situ laser pyrolysis. The obtained X-ray diffraction pattern and transmission electron microscopy images correspond to PtxCoy alloy nanoparticles with average diameters of 2.4 nm and well-established crystalline structure. The synthesized PtxCoy/C catalyst containing 1.5 wt% of PtxCoy nanoparticles can achieve complete CO conversion in the temperature range 125-175°C working at weight hourly space velocities (WHSV) of 30 L h-1g-1. This study shows the first example of bimetallic nanoalloys synthesized by laser pyrolysis and paves the way for a wide variety of potential applications and metal combinations.
RESUMO
Magnetic nanoparticles offer multiple utilization possibilities in biomedicine. In this context, the interaction with cellular structures and their biological effects need to be understood and controlled for clinical safety. New magnetic nanoparticles containing metallic/carbidic iron and elemental silicon phases were synthesized by laser pyrolysis using Fe(CO)5 vapors and SiH4 gas as Fe and Si precursors, then passivated and coated with biocompatible agents, such as l-3,4-dihydroxyphenylalanine (l-DOPA) and sodium carboxymethyl cellulose (CMC-Na). The resulting magnetic nanoparticles were characterized by XRD, EDS, and TEM techniques. To evaluate their biocompatibility, doses ranging from 0â»200 µg/mL hybrid Fe-Si nanoparticles were exposed to Caco2 cells for 24 and 72 h. Doses below 50 μg/mL of both l-DOPA and CMC-Na-coated Fe-Si nanoparticles induced no significant changes of cellular viability or membrane integrity. The cellular internalization of nanoparticles was dependent on their dispersion in culture medium and caused some changes of F-actin filaments organization after 72 h. However, reactive oxygen species were generated after exposure to 25 and 50 μg/mL of both Fe-Si nanoparticles types, inducing the increase of intracellular glutathione level and activation of transcription factor Nrf2. At nanoparticles doses below 50 μg/mL, Caco2 cells were able to counteract the oxidative stress by activating the cellular protection mechanisms. We concluded that in vitro biological responses to coated hybrid Fe-Si nanoparticles depended on particle synthesis conditions, surface coating, doses and incubation time.
RESUMO
Laser pyrolyzed SnO2 nanoparticles with an option of nitrogen (N) doping are prepared using a cost-effective method. The electrochemical performance of N-doped samples is tested for the first time in Li-ion batteries where the sample with 3% of N-dopant exhibits optimum performance with a capacity of 522 mAh gactive material-1 that can be obtained at 10 A g-1 (6.7C).
RESUMO
Flame-retarded bioepoxy resins were prepared with the application of commercially available sorbitol polyglycidyl ether (SPE). The additive-type flame retardancy of the cycloaliphatic amine-cured SPE was investigated. Three-percent phosphorus (P)-containing samples were prepared with the application of the liquid resorcinol bis(diphenyl phosphate) (RDP), the solid ammonium polyphosphate (APP), and by combining them. Synergistic effect was found between the inorganic APP and the organophosphorus RDP, when applied in combination: formulations applying RDP or APP alone showed increased limiting oxygen index (LOI) values, however, their UL-94 standard ratings remained HB. When the same amount of P originated from the two additives, V-0, self-extinguishing rating and LOI value of 34% (v/v) was reached. By the combined approach the heat release rate of SPE could be lowered by approximately 60%. The assumed balanced solid and gas phase mechanism was confirmed by thermogravimetric analysis, Fourier transform infrared spectrometry (FTIR) analysis (of the gases formed during laser pyrolysis), attenuated total reflection-infrared spectrometry (ATR-IR) analysis (of the charred residues), as well as by mechanical testing (of the char obtained after combustion).
RESUMO
Carbon-covered silicon nanoparticles (Si@C) were synthesized for the first time by a one-step continuous process in a novel two stages laser pyrolysis reactor. Crystallized silicon cores formed in a first stage were covered in the second stage by a continuous shell mainly consisting in low organized sp(2) carbon. At the Si/C interface silicon carbide is absent. Moreover, the presence of silicon oxide is reduced compared to materials synthesized in several steps, allowing the use of such material as promising anode material in lithium-ion batteries (LIB). Auger Electron Spectroscopy (AES) analysis of the samples at both SiKLL and SiLVV edges proved the uniformity of the carbon coating. Cyclic voltammetry was used to compare the stability of Si and Si@C active materials. In half-cell configuration, Si@C exhibits a high and stable capacity of 2400 mAh g(-1) at C/10 and up to 500 mAh g(-1) over 500 cycles at 2C. The retention of the capacity is attributed to the protective effect of the carbon shell, which avoids direct contact between the silicon surface and the electrolyte.