Investigations of nanoparticle generation during surface decontamination by laser ablation at low fluence

Through laser ablation processes, significant amounts of particles can be generated from a surface of cement, stainless steel, or alumina. The minimal laser fluence (mJ cm^-2), or threshold energy, required to produce a detectable amount of particles (100 particles cm^-3) was investigated experimentally. The threshold energy was wavelength-dependent and was found to be the greatest for a pure material, alumina, then for a complex mixture, cement, and least for a simple mixture, stainless steel. The threshold energy requirement for three tested materials was found to be significantly higher for the IR (1064-nm) laser; it was 2.4–10.1 times higher than for the UV (266-nm) laser and 9.1–15.2 times higher than for the Vis (532-nm) laser. Interestingly, the UV laser has a higher threshold energy (1.5–4.0 times higher) than the Vis does. A log–log linear model was found to correlate particle production with the laser fluence of all three wavelengths. Of the three materials tested, stainless steel produced the most particles at a given fluence while alumina produced the fewest. Hypotheses of the particle generation mechanisms based upon the observations are also given here.     

One-step synthesis of γ-Fe2O3 nanoparticles by laser ablation

A Nd:YAG pulsed laser was used to ablate a 0.5-mm-diameter iron wire in a sealed chamber in a mixed gas flux of N₂ and O₂ to generate pure γ-Fe₂O₃ nanoparticles at atmospheric pressure. Structural characteristics and sizes of the prepared nanoparticles were determined by X-ray diffraction and TEM. The effects of laser power density, total mixed gas pressure and the oxygen ratio on the mean particle size were investigated, respectively. The results showed that the mean particle size decreased with the increase of the laser power density, total gas pressure and the oxygen ratio, respectively. Besides, the nanoparticle formation mechanism by laser ablation of iron wires was also discussed.     

Organic-inorganic composites for novel optical transformation induced by high-energy laser ablation

High-energy continuous-wave (CW) laser has been considered as a significant technology in recent decades. Such laser can destroy conventional materials in an extremely short time, necessitating their protection. In this study, zirconium carbide (ZrC) and silicon carbide (SiC) particle-modified short silicon carbide fiber-reinforced phenolic resin matrix composites (SiC/BPF-ZS) with significant anti-laser performance were designed and prepared. Our results showed that the ceramic particles and SiC fibers rapidly oxidized, leading to the formation of a ceramic coating composed of ZrO₂ and SiO₂. Owing to the formation of the ceramic coating, the reflectivity of the composites improved significantly from 15.8% to 73.2% after ablation at 500 W/cm² for 30 s. Additionally, the SiC fibers played an important role in the formation of a high-reflectivity coating during laser ablation. Contrast experiments indicated that SiC fibers lead to better performance than the carbon fibers. The high reflectivity and low mass ablation rate are demonstrated to be the key factors improving the anti-laser ablation performance of the SiC/BPF-ZS composites.     

The mechanical properties of C/C-ZrC-SiC composites after laser ablation

Considering practical environment, the bending property of C/C-ZrC-SiC, C/C-SiC and C/C composites after ablation was worthily studied. Results revealed that C/C-ZrC-SiC composites had a better laser ablation resistance and higher bending strength retention compared with C/C-SiC and C/C composites. The mass loss rate and ablated depth of C/C-ZrC-SiC composites was − 0.09% and 190.377 μm, respectively. The retention of bending strength of C/C-ZrC-SiC composites was 217.67 ± 44.12 MPa, whose strength decreased by 3.57% compared with that of as-prepared C/C-ZrC-SiC composites. The excellent anti-ablation property and residual bending strength of C/C-ZrC-SiC composites were attributed to the lowest ablative temperature and the effective protection of the ZrO₂ grain and ZrO₂-SiO₂ layer, which were formed by oxidation of ZrC-SiC, evaporation of SiO₂, migration of liquid ZrO₂-SiO₂ and the infiltrated as well as grown ZrO₂. However, the fracture behavior transformation of composites from pseudo-plastic rupture to brittle rupture was induced by the ablation damage.     

Study of cationic UV curing and UV laser ablation behavior of coatings sensitized by novel sensitizers

To improve the laser ablation performance of cycloaliphatic epoxide cationic UV curable coatings, two novel reactive sensitizers were synthesized and characterized and their effect on coating properties examined. The sensitizers were synthesized based on the reaction between naphthalene or anthracene derivatives and monomers or oligomers used in the coating system. HPLC and GC-MS confirmed the formation of the desired products. Three coating systems based on cycloaliphatic epoxide with either oxetane or polycaprolactone polyol were formulated with the reactive sensitizers. The sensitized coatings had higher conversion during UV curing in the oxetane containing formulation and did not deter the curing in the polyol containing formulation. Better UV laser ablation performance was observed in all sensitized coatings compared to the controls. Coatings with the anthracene based sensitizer even had better laser ablation performance than a commercial polyimide. The sensitized coatings had higher hardness, T_g and crosslink density while the adhesion and solvent resistance were not affected. An optimal amount of sensitizer was found for each coating formulation in terms of UV curing behavior. The relationship between coating T_g and laser ablation behavior was investigated and it was found that the higher the T_g and crosslink density, the poorer the laser ablation performance.     

Growth of multi-morphology amorphous silicon oxycarbide nanowires during the laser ablation of polymer-derived silicon carbonitride

Multi-morphology amorphous SiOC nanowires were successfully prepared within the interfacial interstices between the unaffected SiCN ceramic and the bracket during the laser ablation of polymer-derived SiCN ceramic in a low-pressure argon atmosphere. Laser irradiation experiments were performed using a continuous-wave CO₂ laser, and the gas source for the growth of amorphous SiOC nanowires was provided by the laser ablation of the SiCN ceramic. X-ray photoelectron spectroscopy shows that the amorphous SiOC nanowires possess a SiO₂ dominated nanostructure, and the formation of amorphous SiOC nanowires is attributed to the good diffusivity of CO in SiO₂. The morphologies of the amorphous SiOC nanowires include straight nanowires, beaded nanowires, helical nanowires, and branched nanowires, and these are determined by the flowing state of the reactant gases, the laser power, and the surface morphology of the SiCN ceramics. Each amorphous SiOC nanowire with specific morphology can be uniformly distributed in separate regions, which makes it possible to control the growth of amorphous SiOC nanowires in different morphologies.     

Particle surface properties of stainless steel-coated tungsten carbide powders

Tungsten carbide powders sputter-deposited with stainless steel were characterized in order to evaluate the surface properties in air and aqueous environments. The scanning electron microscopy with energy dispersive spectroscopy showed that a very high uniformity of the coating distribution on the WC particles was attained by the sputtering technique, enabling a complete surface coverage for low coating contents (? 1 wt.%).The DTA-TG thermal analysis in air atmosphere revealed that the coating layers increase the oxidation resistance of WC powders, in spite of the coating porosity.The electrophoretic measurements performed in aqueous solution, for different pH at a constant ionic strength (1 mM KCl), showed that the surface charge until pH ? 8 is essentially determined by the stainless steel coating, while for higher pH it becomes closer to that of the WC particles. The coating adhesion measured by a scratch test was found to decrease in the basic pH region. These results were discussed in terms of the effect of the short-range repulsion forces between the coating layer and the particle surface in aqueous suspensions.     

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%.     

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.     

Design and preparation of composite coatings with increased reflectivity under high-energy continuous wave laser ablation

High-energy continuous wave (CW) laser ablation can cause severe damage to structural materials in an extremely short time, which generates considerable concern in terms of material safety. For the purpose of reducing or even eliminating such laser-induced damage, a novel composite coating consisting of a boron-modified phenolic formaldehyde resin incorporating ZrC and SiC has been designed and prepared. The experimental results reveal that ZrC and SiC are rapidly oxidized to ZrO₂ and SiO₂ respectively, leading to the formation of a white ceramic layer consisting of ZrO₂ particles and melted SiO₂. After ablation at 1000 W/cm² for 50 s, elemental analysis indicates that no Si can be found in the central ablation zone because of gasification. A relatively compact ZrO₂ layer is formed through the sintering of adjacent ZrO₂ particles, which effectively improves the reflectivity of the coating from 7.3% (before ablation) to 63.5% (after ablation). The high reflectivity greatly reduces the absorption of laser energy. In addition, no obvious ablation defects are observed in the composite coating. The excellent anti-laser ablation performance of the coating makes it a promising system for protecting a material against the effects of long-term CW laser ablation.     

Research on the ablation mechanism and ablation threshold of CMC-SiCf/SiC by using dual-beam coupling nanosecond laser

Due to the excellent properties of high hardness, oxidation resistance and high temperature resistance, silicon carbide fiber silicon carbide ceramic matrix composite (CMC-SiC_f/SiC) is a typical difficult-to-process material, and is a high-performance advanced material in the aerospace field. In this paper, two groups of ablation experiments (experiment 1 and experiment 2) were performed on CMC-SiC_f/SiC using a dual-beam coupling nanosecond laser, and the ablation morphology was observed by confocal laser microscope. The dual-beam coupling angle of experiment 2 is obtained by experimental method. And through the method of calculation, we get the dual-beam coupling angle of experiment 1 and experiment 2. According to the dual-beam coupling ablation mechanism, based on the theoretical calculation model of non-destructive method D²-lnP₀, combined with the Equivalent Diameter Calculation Method (EDCM) and Equivalent Area Calculation Method (EACM), the laser ablation threshold corresponding to different beam waist size was calculated and compared. The results show that the ablation region of CMC-SiC_f/SiC surface can be divided into three parts: ablation boundary, recast layer area and SiO₂ coverage area. When the pulse energy increases gradually from 300 μJ to 1500 μJ, the variation trend of hole depth is first increase, second decrease, increase again, and finally decrease. The angle between two laser beams affects the waist radius, which in turn affect the laser ablation threshold. The waist of the dual-beam coupling is elliptical, and the orifice of the ablation hole is elliptical. When the waist radius of nanosecond laser is 57 μm, the laser ablation threshold is calculated to be 3.12 J/cm². The main factors affecting the laser ablation threshold are laser pulse repetition frequency (f), beam waist radius (ω₀), laser pulse width (τ), minimum laser power (P_th), and laser wavelength (λ).     

Thermal stability and nanostructure evolution of amorphous SiCN ceramics during laser ablation in an argon atmosphere

The thermal stability and nanostructure evolution of amorphous SiCN ceramics during laser ablation in an argon atmosphere were investigated. Laser irradiation experiments were performed by using a continuous wave CO₂ laser, and a finite element simulation was conducted to quantify the non-uniform temperature field during the laser irradiation. Three regions with different ablation behaviours were identified based on the radial temperature gradient. Cracks extended through these three regions because of the large thermal stress. In the reaction zone, the SiCN ceramic surface was covered by only porous SiC because of the carbothermic reaction. In the transition zone, a weak carbothermic reaction occurred at the surface of the SiCN particles, but the graphitisation of the carbon nanostructure was enhanced dramatically. The heat affected zone showed no change in the microstructure morphology. However, the carbon nanostructure also exhibited higher graphitization.     

Application of laser ablation technique for removal of chemically inert organically modified silicate coatings

Removal of organically modified silicate (Ormosil) coatings from 2024-T3 aluminum alloy substrates has been investigated using a laser ablation technique utilizing a 308 nm excimer laser. Incorporation of UV-absorbing dye molecules containing λ_max in the vicinity of the laser wavelength (butyl-PBD, Furan 2, Morin, HQSA) into the Ormosil thin film was found to facilitate coating removal. Ormosil thin films containing 0.1–0.5 mol% UV-absorbing dye molecules were subjected to laser treatment at various fluences ranging from 0.2 to 0.6 J/cm². The presence of the UV-absorbing dye molecules in the Ormosil thin film was found to facilitate coating removal at a lower fluence as compared to dye-free coatings as determined by scanning electron microscopy. The effectiveness of coating removal was found to depend on several parameters including laser fluence, number of pulses per spot, and dye concentration.     

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。     

The use of laser ablation inductively coupled plasma-mass spectrometry (LA ICP-MS) for the analysis of fly ash

Two methods were used to analyse fly ash for trace elements using laser ablation inductively coupled plasma-mass spectrometry. Individual particles in polished blocks proved difficult to analyse because of the fine grain size of the particles. Identification of particles was one problem and another was loss of sensitivity for key trace elements with a very small diameter (10 μm) laser beam. Analysis using transects covering many particles mounted on slides proved more successful. Statistical analysis of the data using major elements to measure the variation in key components in the ash showed: (1) that the glass is an important location for V, Cr, Cu and Zn; (2) Cr and V are thought to be concentrated in magnetite, although the major source in the ash is the glass; and (3) As, U, Pb, Tl, Mo, Se and probably Ge and Ga to a lesser extent, have a major association with the surfaces of the ash particles.     

Influence of laser surface hardening on the corrosion resistance of martensitic stainless steel

Martensitic high nitrogen stainless steels offer a combination of wear-, corrosion- and fatigue properties. But for some applications a higher surface hardness is required. A laser hardening with rapid heating (without smelting) and cooling (quenching) rates can improve the surface hardness with compressive residual stresses in the near surface layer. Yet, some cases of pitting corrosion in chloride media are reported.In this study, the influence of process parameters, composition of the atmosphere and the overlapping ratio, has been investigated. With complementary surface analytical methods and electrochemical techniques the relation between surface structure and composition and corrosion behavior in chloride media has been studied.It has been shown that, during the laser treatment the surface must be shielded with argon in order to avoid the formation of a porous layer of iron oxides, which is dramatically detrimental to the corrosion resistance.After the laser treatment a mixture of martensite and retained austenite is obtained, depending on the surface temperature and overlapping ratio. With a surface temperature of 1200 °C and a minimal overlapping ratio (10%), a thin surface layer of retained austenite, wherein nitrides are dissolved, improves the corrosion resistance. The hardness increases with the amount of distorted martensite and reaches a maximum at 1000 °C.     

Deep precision machining of SiC ceramics by picosecond laser ablation

Silicon carbide (SiC) ceramic is becoming widely used in multiple industrial applications, owing to its exceptional high-temperature properties. Yet it is still a challenge to machine SiC using traditional means without causing damage due to its high hardness and brittleness. In this study, a subtractive manufacturing technique based on the use of a fiber picosecond laser was employed to remove material from the reaction bonded SiC surface or create micro-patterns with the minimum damage to the surface, maximum surface quality and precision. Multiple laser processing parameters were investigated with the purpose of obtaining deep high-quality cuts with the minimum surface roughness and the minimum amount of the re-deposited material. The heat affected zone was analyzed by grazing angle X-ray diffractometry, cross-sectional scanning electron microscopy, energy dispersive and micro Raman spectroscopy techniques. The cut shape, depth, surface roughness as well as the kerf width and re-deposition height were assessed using a 3D laser scanning microscopy. The optimum values were established for the focal position, the laser power, linear speed, wobble frequency, wobble pattern, and number of passes. This study also identified the processing parameters for shallow and deep high-precision SiC cutting at a material removal rate of ～2 mm³/min. The work demonstrated that the developed laser machining process is an efficient subtractive manufacturing tool that can be integrated into the automated precision cutting systems for machining hard ceramic materials such as SiC and alumina.     

Polymerization of monomers initiated by silyl centers in SiO deposits prepared by pulsed laser ablation

Deposits from silicon monoxide prepared by pulsed laser ablation were allowed to react with acrylic and vinyl monomers—styrene, methyl methacrylate and 1,2 ethylene glycol dimethacrylate. It was revealed by means of FTIR, electron paramagnetic resonance (EPR), and NMR spectroscopies that silyl ?Si· reacts with monomer molecules and initiates the consecutive polymerization. Crosslinking is proved by the occurrence of bending δ(? CH₂) absorption peak at about 750 cm^?1 in FTIR spectra. Because of very low concentration of the propagating radical for styrene we used a radical scavenger N‐phenyl‐t‐butylnitrone for trapping. The measured EPR parameters were compared with the calculated ones. In case of styrene, NMR analysis manifested the presence of Si? C bonds in SiC_xO_y (x + y = 2) units, which can be taken as direct evidence of the reaction between silyl centers and monomer molecules. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4488–4492, 2006