脉冲激光轰击法连续制备纳米铜研究

采用脉冲激光轰击法连续制备了纳米铜及表面活性剂原位修饰的油溶性纳米铜,用UV-Vis研究了不同表面活性剂不同浓度对纳米铜／乙醇溶胶的紫外-可见光谱的影响,从而确定各表面活性剂的最佳浓度,用TEM研究了不同表面活性剂对纳米铜溶胶分散稳定性的影响,确定了最佳表面活性剂为平平加O,傅立叶红外光谱发现纳米铜／乙醇溶胶中乙醇分子基团振动波长受纳米铜颗粒的影响而出现红移现象,分散性实验表明：平平加O表面修饰纳米铜具有良好的油溶性。     

Fracture toughness of zirconia from a shallow notch produced by ultra-short pulsed laser ablation

Fracture toughness of submicron grain size tetragonal zirconia polycrystals doped with 3 mol% yttria (3Y-TZP) is measured by the single edge V-notch beam (SEVNB) method from a shallow sharp notch produced by ultra-short pulsed femtolaser ablation (UPLA) on the surface of a bending bar. It is shown that the radius of the notch tip achieved is in the submicron range and the damaged volume in front of the notch tip is characterized by using focus ion beam milling and scanning electron microscopy. It consists of a narrow fully microcracked region less than ∼4 μm wide and ∼15 μm deep in front of the notch. If the extension of this region and the length of the notch are used in the determination of the fracture toughness (K_Ic) in the four bending test, the values obtained for submicron grain size 3Y-TZP are in agreement those obtained by using very sharp cracks. It is concluded that the SEVNB testing method with a sharp notch induced by UPLA may be used for K_Ic testing of submicron grain size ceramics.     

Designing zinc oxide nanostructures (nanoworms,nanoflowers, nanowalls,and nanorods) by pulsed laser ablation technique for gas-sensing application

In this study, pulsed laser ablation technique, also known as pulsed laser deposition (PLD), is used to design and grow zinc oxide (ZnO) nanostructures (nanoworms, nanowalls, and nanorods) by template/seeding approach for gas-sensing applications. Conventionally, ZnO nanostructures used for gas-sensing have been usually prepared via chemical route, where the 3D/2D nanostructures are chemically synthesized and subsequently plated on an appropriate substrate. However, using pulsed laser ablation technique, the ZnO nanostructures are structurally designed and grown directly on a substrate using a two-step temperature-pressure seeding approach. This approach has been optimized to design various ZnO nanostructures by understanding the effect of substrate temperature in the 300-750°C range under O₂ gas pressure from 10-mTorr to 10 Torr. Using a thin ZnO seed layer as template that is deposited first at substrate temperature of ~300°C at background oxygen pressure of 10 mTorr on Si(100), ZnO nanostructures, such as nanoworms, nanowalls, and nanorods (with secondary flower-like growth) were grown at substrate temperatures and oxygen background pressures of (550°C and 2 Torr), (550°C and 0.5 Torr), and (650°C and 2 Torr), respectively. The morphology and the optical properties of ZnO nanostructures were examined by Scanning Electron Microscope (SEM-EDX), X-ray Diffraction (XRD), and photoluminescence (PL). The PLD-grown ZnO nanostructures are single-crystals and are highly oriented in the c-axis. The vapor-solid (VS) model is proposed to be responsible for the growth of ZnO nanostructures by PLD process. Furthermore, the ZnO nanowall structure is a very promising nanostructure due to its very high surface-to-volume ratio. Although ZnO nanowalls have been grown by other methods for sensor application, to this date, only a very few ZnO nanowalls have been grown by PLD for this purpose. In this regard, ZnO nanowall structures are deposited by PLD on an Al₂O₃ test sensor and assessed for their responses to CO and ethanol gases at 50 ppm, where good responses were observed at 350 and 400°C, respectively. The PLD-grown ZnO nanostructures are very excellent materials for potential applications such as in dye-sensitized solar cells, perovskite solar cells and biological and gas sensors.     

A comparative investigation on micro-channel by using direct laser ablation and liquid-assisted laser ablation on zirconia

In this work, direct laser ablation (DLA), liquid-assisted laser ablation in water (LALA-W) and in ethanol (LALA-E) is applied to fabricate single micro-channels on the zirconia ceramic by using a picosecond laser. To assess the machining ability of them, micro-channels fabricated are characterized and compared the differences in morphology, geometric profile, chemical and phase composition. The morphological results indicate that both LALA-E and DLA can fabricate microchannel with obvious recast layer and cracks, and LALA-W can fabricate microchannel with a porous surface, and almost no recast layer and cracks. The results of geometric characteristics show that LALA-W can fabricated micro-channels with “U” shape profile with 52.74% enhancement in depth compared to that “V” shape by DLA and LALA-E. The XPS results demonstrate that LALA-W can exhibit the smallest oxygen vacancies with 50.01% than that of LDA 53.81% and LALA-E 54.56%. For XRD results, after machining by all three processes, the zirconia ceramic undergoes the tetragonal→monoclinic phase transformation, resulting in an increase in monoclinic phase. While LALA-W exhibits the smallest increase in monoclinic phase from 9.9% to 12.7%, and has the most tetragonal phase content of 58.8%.     

The formed surface characteristics of SiCf/SiC composite in the nanosecond pulsed laser ablation

For the advantages of high-temperature resistance, corrosion resistance and ultra-high hardness, SiC_f/SiC composite is becoming a preferred material for manufacturing aero-engine parts. However, the anisotropy and heterogeneity bring great challenges to the processing technology. In this study, a nanosecond pulsed laser is applied to process SiC_f/SiC composite, where the influence of the scanning speed and laser scanning direction to the SiC fibers on the morphology of ablated grooves is investigated. The surface characteristics after ablation and the involved chemical reaction of SiC_f/SiC are explored. The results show that the increased laser scanning speed, accompanied by the decreasing spot overlap rate, leads to the less accumulation of energy on the material surface, so the ablation effect drops. In addition, for the anisotropy of the SiC_f/SiC material, the obtained surface characteristics are closely dependent on the laser scanning direction to the SiC fibers, resulting in different groove morphology. The element composition and phase analysis of the machined surface indicate that the main deposited product is SiO₂ and the carbon substance. The results can provide preliminary technical support for controlling the machining quality of ceramic matrix composites.     

Effect of temperature on sulfur-doped diamond-like carbon films deposited by pulsed laser ablation

In this study, S-DLC films were deposited using pulsed laser ablation of a novel sulfur-graphite (SG) mixture target using an ArF excimer laser (193 nm). The SG targets were made by mixing sulfur and graphite powders at different sulfur molar percentages from 0% to 25%. The S-DLC films were deposited at room temperature, 150 °C and 250 °C. The optical and electronic properties of the doped films were studied. Laser Raman spectroscopy indicated increased graphitic behavior with temperature but decreased with higher sulfur content. Spectroscopic ellipsometry analyses found that the optical band-gap energy, extinction coefficient and reflective index, clearly depended on deposition temperature and sulfur content. Hall Effect measurements indicated n-type carrier with concentration in the range of 1 × 10¹⁴ to 2 × 10¹⁷ cm^− 3, strongly depended upon the deposition temperature and amount of sulfur.     

Temperature dependent upconversion properties of Yb3+:Ho3+ co-doped Gd2O3 nanoparticles prepared by pulsed laser ablation in water

Yb³⁺:Ho³⁺ co-doped Gd₂O₃ nanoparticles were successfully synthesized by pulsed laser ablation in water under different laser energy. The phase structure, morphology, crystallization and upconversion photoluminescence properties of obtained samples were investigated using X-Ray diffraction (XRD), transmission electron microscopy (TEM), selected area electron diffraction (SAED) and photoluminescence spectra. The mechanism of the upconversion process was discussed based on the energy level diagram and power dependent upconversion emission. Upconversion mechanisms and thermal effects caused by absorption of excitation laser were discussed. Temperature dependent green and red emissions of Yb³⁺:Ho³⁺ co-doped Gd₂O₃ nanoparticles under the excitation of 980 nm were investigated in the low temperature range of 130 K–280 K. Non-radiative decay rate theory was used to explain the difference of quenching rates of green and red emissions. A further study on temperature sensing properties based on fluorescence intensity ratio (FIR) of green and red emissions was carried out. The FIR as a function of temperature can be well fitted by the model based on the thermal quenching theory. The relative sensitivity reaches its maximum value of 0.804% K⁻¹ at 216 K.     

Fabrication of micro-scale textured grooves on green ZrO2 ceramics by pulsed laser ablation

The green ZrO₂ ceramics were fabricated by cold isostatic pressing. Pulsed laser ablation with a wavelength of 1064 nm was performed to fabricate micro-scale textured grooves on the surface of green ZrO₂ ceramics. The influence of laser parameters on surface quality was studied. The heat-affected zone around the machined grooves and micromorphology of laser-irradiated surface were investigated. Results showed that micro-scale textured grooves with a width of 30–50 µm and a depth of 15–50 µm on the green ZrO₂ ceramic surfaces were successfully fabricated by pulsed laser ablation. The laser parameters had a profound influence on the surface quality of micro-scale textured grooves. Better surface quality could be obtained with frequency below 40 Hz, power below 6 W, and scanning velocity above 200 mm/s. A sintering layer was found on the laser-irradiated surfaces when frequency was above 60 Hz, power was above 10 W, and scanning velocity was below 150 mm/s. Analysis of this sintering layer revealed clear melting and resolidification of ZrO₂ particles.     

Transformation of CeO2 into a mixed phase CeO2/Ce2O3 nanohybrid by liquid phase pulsed laser ablation for enhanced photocatalytic activity through Z-scheme pattern

Cerium-based nanohybrids have attracted considerable attention in photocatalytic research owing to their remarkable potential in the photodegradation of environmental pollutants. However, the process of nanohybrid formation suffers from complex operations with specialized equipment, extreme conditions, long durations, and low yields, making it infeasible for efficient utilization. Considering the above obstacles, we herein describe the first pulsed laser ablation (PLA) for the synthesis of oxygen vacancy affluent CeO₂/Ce₂O₃ nanohybrids, as an alternative to hydrothermal and calcination methods. The microstructures and optical properties of the nanocomposites are characterized by TEM, XRD, XPS, and DRS analysis. The photocatalytic activity of the CeO₂/Ce₂O₃ nanohybrid showed an MB dye degradation rate superior to that of bare CeO₂ nanostructures. The enhanced performance of CeO₂/Ce₂O₃ was attributed to an oxygen-vacancy-driven Z-scheme mechanism, where efficient separation of the photogenerated charge carriers significantly contributed to photocatalytic enhancement. This was further evidenced by both PL and scavenger experiment results. Moreover, the synthesized CeO₂/Ce₂O₃ nanocomposites exhibit a strong blue emission, which could have potential applications in LED manufacturing.     

Kinetic study on free radical polymerization of alkyl acylamidoacrylates by pulsed laser polymerization using nitrogen laser

Radical polymerization of captodatively substituted alkyl acylamidoacrylates was studied by pulsed laser polymerization using a N₂ laser. Propagation rate coefficient of the acrylates was varied with solvents used in spite of a radical mechanism, but little varied with methyl, n-propyl, and isopropyl substituents on the acrylates. Arrhenius parameters for the propagation indicated that a solvent affected mostly on a frequency factor rather than a activation energy. In addition, it was suggested that these captodatively substituted propagating radicals were thermodynamically persistent but kinetically active in propagation, which resulted in rather smooth propagation in spite of bulky 1,1-disubstituted olefins. The mechanism of the polymerizations was discussed in detail on the basis of the kinetic studies and ESR spectroscopy.     

Controllable ZnO nanostructures evolution via synergistic pulsed laser ablation and hydrothermal methods

We report the morphology-controlled ZnO nanostructures (ZNSs) evolution synthesized via a novel and facile technique at different growth times, where the pulse laser ablation in liquid (PLAL) is creatively combined with hydrothermal (H) method (hereafter called PLAL-H technique). Four types of ZNSs with varying sizes and shapes such as tapers, multipods, flowers, and hollow flowers are produced on Si substrate via PLAL-H technique. Furthermore, multipod- and flower-like ZNSs are grown using direct hydrothermal method to compare them with the one obtained via synergistic effects of PLAL-H method. This catalyst-free fabrication method is not only cost-effective but greatly useful for the rapid production of different quality of ZNSs at low temperature. ZNSs synthesized under prolonged growth time (60 min) exhibited structural deformation. Growth technique and time dependent morphology, structure, composition, and optical properties of these as-grown ZNSs are characterized using FESEM, X-ray diffraction, FTIR, photoluminescence, and UV–vis measurements. Synthesized ZNSs revealed excellent crystallinity and growth process dependent variation in the physical and optical features. The ZNSs growth mechanism is understood. Excellent features of the results demonstrate that this synergized new growth technique may constitute a basis for modifying the morphology, sizes, and optical properties of ZNSs in a controllable manner useful for diverse applications.     

在位分散聚合制备聚甲基丙烯酸甲酯/二氧化硅复合材料研究

采用在位分散聚合方法制备聚甲基丙烯酸甲酯 /二氧化硅微米级复合材料 ,讨论了不同表面性质的二氧化硅对材料拉伸性能、热性能、耐溶剂性能的影响 ,并用SEM、TG等手段研究了材料性能。结果表明 :由WD -70硅烷偶联剂处理过的二氧化硅微粒子填充的材料的各方面性能较好 ,由WD -10硅烷偶联剂处理过的二氧化硅填充的材料的拉伸性能次之 ,未经表面处理二氧化硅填充的材料的拉伸性能最差 ,后两者的热性能以及耐溶剂性能无明显差异     

钛合金表面止焊剂脉冲式激光清洗工艺

采用脉冲式激光清洗钛合金表面的止焊剂。先通过调节功率和频率得到合适的单脉冲能量为2.0～5.0 mJ。再对比了不同单脉冲能量和光斑搭接率组合下的清洗效果,得到较优的激光清洗参数为:光斑搭接率0%～40%,功率120～200 W,频率40～50 kHz。经过较佳工艺激光清洗并酸洗后,钛合金表面品质、力学性能、显微组织及氢、氧含量均符合要求。     

Polymerization of vinyl monomers initiated by zwitterionic polymer in aqueous solution

The polymerization of vinyl monomers, mainly styrene and methyl methacrylate, initiated by zwitterionic poly[3-dimethyl(methacryloyloxy-ethyl)ammonium propane sulfonate], [poly(DMAPS)], in aqueous solution was studied under vacuum at 85°C. An initiation mechanism involving hydrogen atom transfer is proposed. The effects of the efficiency of grafting. pH, water content and betaine polymer content on the polymerization were investigated. The conversion of vinyl monomers in poly(DMAPS) is lower than that in poly [3-dimethyl(acryloyloxyethyl)ammonium propane sulfonate], which may be due to steric hindrance of the methyl group on the α-carbon of the former.     

Polymerization of epoxy resins initiated by metal complexes

BACKGROUND: Processing parameters and material properties of epoxy resins can be vastly influenced by choice of curing agent. In this work, metal complexes were investigated as initiators for anionic and cationic epoxide polymerization. Systems for thermally induced and electron beam‐induced curing are described. RESULTS: Zinc or cobalt imidazole complexes of the type [M(imidazole)₂(anion)₂] are efficient initiators for anionic polymerization of glycidyl‐based epoxy resins. The complexes can be employed to prepare tailored resin systems ranging from fast curing systems at slightly elevated temperatures to systems with very high thermal latencies curable at temperatures far above 150 °C. Silver complexes [Ag(L)_n]SbF₆ (L = crown ether or alkene) are highly efficient initiators for cationic curing and low initiator contents of around 1% are sufficient to reach high degrees of crosslinking. The complexes are excellent initiators for both thermally induced and electron beam‐induced polymerizations. CONCLUSION: Metal complexes are powerful initiators for the homopolymerization of epoxy resins and can be designed not only for anionic and cationic polymerization but also for thermal and radiation curing. Based on this study and additional work, a library can be compiled which allows retrieval of optimized metal–ligand–anion combinations and adjustment of the initiators to the respective processing and material demands. Copyright © 2009 Society of Chemical Industry     

Polymerization of N-vinylcarbazole initiated by UV-radiation

The solid-state polymerization of N-vinylcarbazole initiated by UV-radiation at 25, 32.5, and 45°C was studied. The rate of polymerization increased with increase in temperature. The limiting conversion at all temperatures is 56%. The molecular weight, determined by viscosity measurements, first increased, reached a maximum, then decreased. The molecular weight distribution, studied by GPC, was broad with a shoulder on the low molecular weight side. The morphology of partially polymerized single crystals was studied by electron scanning microscopy to determine the propagation mode of polymerization with respect to the monomer structure. The high activation energy of 71-9kJ/mol and ESR spectrum suggest a radical mechanism of polymerization.     

Improving the composition and multifunctional properties of amorphous boron nitride films prepared by post-annealing assisted femtosecond pulsed laser deposition method

Amorphous boron nitride (aBN) materials have similar density to crystalline phases and retain many unique electronic properties, valuable chemical inertness and high thermal stability characteristics. However, the current research on aBN materials has mainly focused on the synthesis and electrical properties of ultrathin aBN films. In this study, we developed a post-annealing assisted femtosecond laser deposition route towards stoichiometric, continuous, and multifunctional aBN films with thickness values of ∼1 μm. A series of boron nitride films were deposited on silicon wafers using a 1030 nm, 300 fs laser with a pulse energy of ∼1 mJ and a high repetition rate of 2 kHz to ablate a hexagonal boron nitride target. The deposited films were then annealed at 900 °C in a nitrogen atmosphere. The structures and chemical compositions of these obtained films were analysed by X-ray diffraction and X-ray photoelectron spectroscopy. Fourier transform infrared and nano-scratch tests were performed to measure the infrared optical and frictional properties of the adhered films. An infrared thermal imager was used to investigate the heat-dissipation performance of these films. The results indicate the components of the aBN film are further purified, the number of large heterogeneous particles is effectively reduced, and the surface becomes smooth after post-annealing treatment. This improvement promotes the transfer of heat flux and increases the transmittance in the mid-infrared light band. The significant effect mechanisms of the post-annealing treatment on the enhancement of the composition and multifunctional properties of aBN films prepared by the femtosecond pulsed laser were provided. The uniform coverage of the aBN films on the substrates, as well as the mid-infrared optical transparency and the protective performance are highly valuable and practical for infrared window protection applications.     

Effect of annealing on SiC thin films prepared by pulsed laser deposition

Crystalline cubic SiC thin films were successfully fabricated on Si(100) substrates by using laser deposition combined with a vacuum annealing process. The effect of annealing conditions on the structure of the thin films was investigated by X-ray diffraction and Fourier transform infrared spectroscopy. It was demonstrated that amorphous SiC films deposited at 800°C could be transformed into crystalline phase after being annealed in a vacuum and that the annealing temperature played an important role in this transformation, with an optimum annealing temperature of 980°C. Results of X-ray photoelectron spectroscopy revealed the approximate stoichiometry of the SiC films. The characteristic microstructure displayed in a scanning electron microscope image of the films was indicative of epitaxial growth along the (100) plane.     

Fabrication of silver nanoparticles dispersed in palm oil using laser ablation

In this study we used a laser ablation technique for preparation of silver nanoparticles. The fabrication process was carried out by ablation of a silver plate immersed in palm oil. A pulsed Nd:YAG laser at a wavelength of 1064 nm was used for ablation of the plate at different times. The palm coconut oil allowed formation of nanoparticles with very small and uniform particle size, which are dispersed very homogeneously within the solution. The obtained particle sizes for 15 and 30 minute ablation times were 2.5 and 2 nm, respectively. Stability study shows that all of the samples remained stable for a reasonable period of time.     

Femtosecond pulsed laser deposition of silicon thin films

Optimisation of femtosecond pulsed laser deposition parameters for the fabrication of silicon thin films is discussed. Substrate temperature, gas pressure and gas type are used to better understand the deposition process and optimise it for the fabrication of high-quality thin films designed for optical and optoelectronic applications.