Multiscale ablation mechanism and performance of 2.5D Si3N4 f/SiBN-CMCs under continuous-wave laser irradiation

The multiscale laser ablation mechanism and performance of 2.5D Si₃N_4 f/SiBN-CMCs were investigated experimentally. The results show that the ablation process has obvious multiscale characteristics. The morphology of the ablation zone was determined by the temperature distribution, 2.5D microstructure, and location of the laser spot. The difference in thermal conductivity of the fiber and matrix induced a discrepancy in the cooling rate at the mesoscale, resulting in a regular distribution of the white powder of SiO₂ on the matrix-rich zones in the ablation pit. The extremely high-temperature anaerobic environment caused by laser irradiation made the Si₃N_4 f/SiBN-CMCs undergo a violent decomposition reaction to generate liquid silicon. When the irradiation power density is constant, the ablation center and transition area diameters are all proportional to the laser energy. The linear ablation rate increases with increasing laser power but decreases with prolonged irradiation time. The ablation resistance of this composite is hampered by the absence of a continuous molten layer during exposure to the laser.     

Laser Direct Writing of Dual-Scale 3D Structures for Cell Repelling at High Cellular Density

The fabrication of complex, reproducible, and accurate micro-and nanostructured interfaces that impede the interaction between material’s surface and different cell types represents an important objective in the development of medical devices. This can be achieved by topographical means such as dual-scale structures, mainly represented by microstructures with surface nanopatterning. Fabrication via laser irradiation of materials seems promising. However, laser-assisted fabrication of dual-scale structures, i.e., ripples relies on stochastic processes deriving from laser–matter interaction, limiting the control over the structures’ topography. In this paper, we report on laser fabrication of cell-repellent dual-scale 3D structures with fully reproducible and high spatial accuracy topographies. Structures were designed as micrometric “mushrooms” decorated with fingerprint-like nanometric features with heights and periodicities close to those of the calamistrum, i.e., 200–300 nm. They were fabricated by Laser Direct Writing via Two-Photon Polymerization of IP-Dip photoresist. Design and laser writing parameters were optimized for conferring cell-repellent properties to the structures, even for high cellular densities in the culture medium. The structures were most efficient in repelling the cells when the fingerprint-like features had periodicities and heights of ≅200 nm, fairly close to the repellent surfaces of the calamistrum. Laser power was the most important parameter for the optimization protocol.     

Femtosecond laser microstructuring in the bulk of diamond

In this paper we report the fabrication of graphitic microstructures in the bulk of diamond using 120-fs-laser pulses at 800 nm wavelength. Polished plates of single crystal diamond and optical quality polycrystalline CVD diamond were used as samples for 3D microstructuring. Under low fluence conditions and focusing a laser beam into the bulk of diamond plates, multipulse irradiation was found to result in the appearance and continuous growth of a laser-modified (graphitized) region from the focal plane towards the laser beam. Controlling the laser fluence and sample translation velocity (scanning beam velocity) allowed high-aspect-ratio ‘graphitic wires’ – microstructures of a few microns in diameter and several hundred micrometers in length – to be fabricated in the bulk of diamond. Physical processes responsible for the continuous growth of microscopic graphitic regions towards a laser beam are discussed. Results of comparative investigations of graphitic microstructures produced by laser pulses of different durations (120 fs and 300 ps) are presented to show the advantages of ultrashort laser pulses in 3D microstructuring of diamond.     

Effects of pulse duration in laser processing of diamond-like carbon films

Experimental studies of the interaction between amorphous hydrogenated carbon (a-C:H) film and short and ultrashort laser pulses in the near-infrared and visible spectral ranges (150 ns and 1064 nm, 10 ns and 1078 nm, 300 ps and 1078 nm, 220 ps and 539 nm, 100 fs and 800 nm.) are reported. The influence of the irradiation conditions (pulse duration, wavelength, laser intensity and the number of laser shots) on the structure and thickness of the laser-induced graphitized layer has been investigated. The effects of heat dissipation on the annealing duration and on the graphitized layer thickness are discussed for the case of laser processing with short pulses. It was found that the resulting morphology of the irradiated a-C:H film surface was determined by the concurrence of three processes: change of the mass density induced by structural transformations, multiple spallations of thin layers, and material evaporation. The laser-induced spallation is asserted to be the main factor limiting the laser microprocessing reproducibility for the examined a-C:H film; its effects were found to increase dramatically for longer (150 ns) laser pulses. The ablation (evaporation) rates of the a-C:H films and glassy carbon were revealed to be similar for femtosecond and picosecond pulses, but they essentially differed for nanosecond pulses. The ablation process demonstrated the same main features for both materials: (i) increase of the ablation rate with the pulse duration, and (ii) saturation of the ablation rate with fluence for picosecond and nanosecond pulses.     

Fine-grained 3C-SiC thick films prepared via hybrid laser chemical vapor deposition

An ultraviolet laser (λ = 266 nm) operated in pulsed mode and a diode laser (λ = 1060 nm) operated in continuous mode were simultaneously applied to create a hybrid laser chemical vapor deposition (CVD) approach. Fine-grained 3C-SiC thick films were prepared via hybrid laser CVD by using SiCl₄, CH₄ and H₂ as precursors. The effects of the ultraviolet laser on the preferred orientations, microstructures, microhardness values and deposition rates of 3C-SiC thick films were investigated. The 3C-SiC thick films that were prepared at 4 kPa via diode laser CVD exhibited <110>-orientations and 5-100 µm grain sizes, whereas those prepared via hybrid laser CVD were randomly oriented with 0.5-5 µm grain sizes. Compared to diode laser CVD, the additional irradiation of the ultraviolet laser in the hybrid laser CVD improved the Vickers microhardness values of the 3C-SiC thick films from 30 to 35 GPa, and the maximum deposition rate was also increased from 935 to 1230 µm/h.     

Growth and Microstructure‐Dependent Hardness of Directionally Solidified WC–W2C Eutectoid Ceramics

Directionally solidified WC–W₂C ceramics containing 40 at% carbon, corresponding to the WC–W₂C eutectoid composition, were produced by laser surface melt processing. The resulting microstructures showed a lamellar‐type eutectic/eutectoid microstructure with the WC minor phase embedded in the W₂C matrix phase. The interlamellar spacing (λ) in the eutectoid regions followed the relationship Vλ^3.8 = constant, with the smallest spacing of 331 ± 36 nm achieved in the 3.24 mm/s processed sample. The indentation hardness increased with decreasing interlamellar spacing, and a Vickers indentation hardness of 28.5 GPa was achieved in the sample with the smallest interlamellar spacing. The directionally solidified WC–W₂C materials show enhanced indentation mechanical properties in comparison to previously reported WC–Co composites and WC‐based materials.     

UV curing and matting of acrylate nanocomposite coatings by 172 nm excimer irradiation

For UV-curable acrylate coatings reinforced by silica nanoparticles, the effect of 172 nm excimer irradiation on the surface roughness has been studied. A dual UV lamp set-up consisting of a 172 nm excimer lamp and a mercury arc lamp allowed obtaining gloss levels down to 0.5 units (at 60°) depending on the acrylate formulation and curing conditions. Moreover, UV matt-finished sample showed enhanced surface hardness and increased chemical resistance. It is assumed that 172 nm excimer irradiation resulted in a higher network density via additional cross-linking reactions.To study the depth profile of acrylate conversion for coatings cured by the combination of a 172 nm excimer lamp (accountable for surface curing) and a mercury arc lamp (responsible for through curing), FTIR microscopy as well as (Ge)ATR-FTIR having an IR penetration depth of less than 0.5 μm have been applied. Providing the presence of a photoinitiator as well as the absence of oxygen inhibition, similar degrees of double bond conversion of about 90% were observed on the entire area of the cross-section of the coating, i.e. the wavelength of UV irradiation was found to have no significant impact on acrylate conversion.     

Porous Mullite Ceramics Formed by Direct Consolidation Using Native and Granular Cold‐Water‐Soluble Starches

In this article, the processing and microstructures of porous mullite bodies prepared by modifying the conventional route of the starch consolidation casting method were studied. The proposed route, called the “soluble route”, involves the use of native starches (i.e., potato, cassava, and corn starches) and a synthesized granular cold‐water‐soluble (GCWS) starch. Stable aqueous mullite‐starch suspensions (0.25 starch volume fraction of 40 vol% total solids) were prepared by mixing. The total starch content was a mixture of ungelatinized native starch and GCWS starch with a 1:10 ratio of GCWS starch to total starch. Steady‐state shear flow properties of the suspensions were analyzed by measuring viscosity. The addition of CGWS starch increased the starting suspension viscosity and thus prevented the particle segregation. Porous mullite bodies were obtained by heating (80°C, 2 h) the suspensions in metallic molds and by drying (40°C, 24 h) and sintering (1650°C, 2 h) the green disks after burning out the starch (650°C, 2 h). Green bodies obtained before and after the burning‐out process, and the sintered disks were characterized with density and porosity measurements (Archimedes method) and microstructural analysis by scanning electron microscopy. The phases generated after the sintering process were determined by X‐ray diffraction analysis, and pore size distributions were studied by Hg‐porosimetry. The obtained results showed that the use of the GCWS starch made the shaping of homogeneous mullite bodies without cracks or deformations possible along with the development of controlled porous microstructures.     

Incubation phenomena during UV‐pulse excimer laser processing of silicone elastomers

Observations of the interaction of poly(dimethylsiloxane) (PDMS) sheet (210 μm thick) with KrF excimer laser irradiation (λ = 248 nm), with low energy of 50 mJ/pulse are presented. The negative ablation or swelling of the material caused by low frequency pulse irradiation is characterized by optical microscopy, μ‐Raman spectrometry and X‐ray micro‐tomography. The appearance of defected areas in the form of cones inside the sheet and changes of material chemistry are discussed. These phenomena are considered as a precursor of the ablation occurring after passing a threshold of absorbed laser irradiation energy. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44541.     

Oberflächenstrukturierung polymerer Fasern durch UV-Laserbestrahlung, 15. Beschreibung des Temperaturfeldes in PETP-Polymeren während und nach der Laserbestrahlung mit einem gepulsten UV-Laser

For understanding the generation of UV laser induced surface structures of PETP polymers the temperature field within the irradiated surface is calculated in dependence on the laser irradiation wavelength (193 nm, 248 nm, 308 nm), pulse time, pulse form, the irradiation intensity and depth, using temperature-independent material data of PETP polymers known from literature. For this purpose the solution function of the one-dimensional heat differential equation is used. Depending on the order of magnitude of the absorption coefficient of the polymer for UV light of different wavelengths, surface temperatures of approx. 16 000°C (193 nm), 11 000°C (248 nm) and 500°C (308 nm) are calculated at the end of the laser pulse. The temperature input within the polymer layer is limited to only a very small penetration depth. For the irradiation with the two laser wavelengths of 193 nm and 248 nm this is less then 0.4 μm. The cooling process is considerably slower, reaching the initial temperature after approx. 4 μs.     

Near‐Net‐Shaped Porous Ceramics for Potential Sound Absorption Applications at High Temperatures

We present an interesting processing route for obtaining alumina/mullite‐based ceramics with controlled porosity and airflow resistance leading to promising microstructures for application as sound absorbers. The use of ceramic materials aims for potential applications where high temperatures or corrosive atmospheres are predominant, e.g., in combustion chambers of gas turbines. For the production of the porous ceramics we combined freeze gelation and sacrificial templating processes to produce near‐net‐shaped parts with low shrinkage (<3%) based on environmental‐friendly and low cost conditions. The obtained microstructure presents a bimodal pore size distribution, with small pores derived from the freeze gelation process (~30 μm) connecting large pores (2–5 mm diameter) originated from the expanded polystyrene template particles. These connections, called “windows” in this study, show a significant impact on the sound absorption properties, allowing the pressure diffusion effect to take place, resulting in a significant improvement of the sound absorption coefficient. By varying the template particle content and the slurry solid content, it is possible to control the sound absorption behavior at different frequencies of the open‐celled ceramics. These ceramics feature a high open porosity, from 77% to 82%, combined with sufficient compressive strength ranging from 0.27 to 0.68 MPa and sound absorption coefficients of 0.30–0.99, representing a highly promising combination of properties for noise control and reduction at corrosive environments and high temperatures.     

Comprehensive study of polymer fiber surface modifications Part 1: high‐fluence UV‐excimer‐laser‐induced structures

Recently, there has been great interest in physico‐chemical surface treatments for modifying polymer surfaces. Ultraviolet (UV)‐excimer‐laser irradiation of polymers is of particular interest. In this study, polyamide was irradiated by a 193 nm excimer laser with a fluence above its ablation threshold (high‐fluence). Morphological changes of the resulting samples were characterized by scanning electron microscopy (SEM) and tapping mode atomic force microscopy (TM‐AFM). Chemical modifications by laser treatment were studied by X‐ray photoelectron spectroscopy (XPS), time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) and chemical force microscopy (CFM). Topographical results indicated that ‘ripple‐like’ structures of micrometer size were formed after laser irradiation. XPS and Tof‐SIMS results showed that bond scission occurred on the polymer surface under the action of high‐fluence. Changes in surface chemical properties of the laser‐irradiated polyamide were supported by CFM experiments. Copyright © 2004 Society of Chemical Industry     

One-step preparation of amorphous iron nanoparticles by laser ablation

Amorphous Fe nanoparticles are always difficult to prepare by physical gas-phase methods though rapid cooling rates are applied. Here we report a physical preparation of pure amorphous Fe nanoparticles by laser ablation of a 0.5-mm-diameter Fe wire and the investigation of their formation mechanism. Amorphous Fe nanoparticles with a shell of γ-Fe₂O₃ and the sizes of 1–3 nm are obtained at the laser power densities above the ablation threshold. Finally, the as-prepared nanoparticles are characterized by XRD, TEM, XPS and VSM to discover the structure, morphology, surface composition, crystallization and magnetic property in detail. We find that the holistic explosive evaporation induced by the small-size target not by the processing parameters determines the nature of the amorphous Fe nanoparticles. The as-prepared amorphous Fe nanoparticles are crystallized at 400 °C with an increase of particle size to about 10 nm.     

Optical thermometry of Sm3+ on laser‐induced local heating for precipitation of PbS quantum dots in glasses

Fluorescence intensity ratios (FIRs) of the 640 nm and 602 nm emissions from Sm³⁺ were recorded at various temperatures T to identify the temperature increases ΔT associated with laser‐induced local heating of Ag nanoparticles. The FIRs increased as intensities of the excitation beam from a 532‐nm continuous‐wave laser increased. Estimated T of the irradiated region increased to as high as 586°C when at laser irradiation of 1.5 W on the surface containing Ag nanoparticles. Local heating due to the surface plasmon resonance of Ag nanoparticles is a main reason for the ΔT that eventually leads to precipitation of PbS quantum dots in glasses.     

Diketopyrrolopyrrole dyes: Structure/reactivity/efficiency relationship in photoinitiating systems upon visible lights

Several diketopyrrolopyrrole derivative based dyes (DPP), combined with an iodonium salt or an amine (and optionally an additive), are studied as photoinitiating systems for the cationic polymerization CP of epoxides or the free radical polymerization FRP of acrylates under different irradiation sources i.e. a very soft halogen lamp as well as laser diodes at 473 nm (blue light) and 532 nm (green light). The diketopyrrolopyrrole-furan derivative (FuDPP) is very efficient in CP. The structure/reactivity/efficiency relationships in this series of DPP derivatives are investigated. A comparison with a well known reference for visible light photoinitiating system (i.e. camphorquinone based photoinitiating system) is also provided showing the better efficiency of the new proposed structures. The photochemical mechanisms are studied by steady state photolysis, fluorescence, cyclic voltammetry, laser flash photolysis and electron spin resonance spin-trapping techniques.     

Simultaneously achieving high strength,thermal resistance and high self‐healing efficiency for polyacrylate coating by constructing a Diels–Alder reversible covalent structure with multi‐maleimide terminated hyperbranched polysiloxane

It is difficult for the self‐healing polyacrylate coatings reported so far to simultaneously achieve high mechanical strength and high self‐healing efficiency within a short healing time. Herein, derived from multi‐maleimide terminated hyperbranched polysiloxane, linear polyacrylate with furan‐containing side chain and polydopamine particles (photothermal conversion agent), a new kind of polyacrylate coating (HPA) with a strong and flexible crosslinking network was developed, which simultaneously shows high mechanical strength and high self‐healing efficiency within a short time. With 0.3 wt% polydopamine particles in HPA, the resulting coating (HPA3) has the highest toughness (2.63 ± 0.10 MPa) with 12.9 ± 0.7 MPa tensile strength and 23.9% ± 1.6% elongation at break; in addition, the self‐healing efficiency of HPA3 is over 87.6% after only 2.5 min of near‐infrared laser irradiation, overcoming intractable problems in developing self‐healing polyacrylate coatings. A study of the mechanism behind these outstanding performances of the HPA system reveals that the reversible covalent crosslinking formed by multi‐maleimide terminated hyperbranched polysiloxane is the necessary and crucial factor for simultaneously achieving high mechanical strength and high self‐healing efficiency in a short time. © 2019 Society of Chemical Industry     

Effects of intermediate energy heavy‐ion irradiation on the microstructure of rutile TiO2 single crystal

This study reports the microstructure evolution of single crystal rutile TiO₂ under 3 MeV Nb⁺ ion irradiation, with the irradiating ions incident on the {100} plane. A complex, multi‐layered microstructure evolution is observed with 4 distinct regions: (i) short‐range disorder in the first 60 nm below the specimen surface, (ii) dislocation loops oriented parallel to the incident ion beam direction, located along the increasing slope of the irradiation damage profile at ~60‐650 nm from the surface, (iii) loops oriented perpendicular to the incident ion beam direction, at depths encompassing the ion implantation and irradiation damage peaks ~650‐1250 nm, and (iv) a high density of nano‐scale atomic rearrangements with long‐range order, located at depths ~1250‐1750 nm. These results present evidence that multiple defect mechanisms occur during irradiation including ion channeling, nuclear stopping, and electronic stopping interactions as a function of depth and disorder accumulation.     

In‐Situ Reactor Radiation‐Induced Attenuation in Sapphire Optical Fibers

The purpose of this work was to determine the suitability of using instrumentation utilizing sapphire optical fibers in a nuclear reactor environment. In this work, the broadband (500–2200 nm, or 0.56–2.48 eV) optical transmission in commercially available sapphire optical fibers was monitored in‐situ prior to and during reactor irradiation. The sapphire fibers were irradiated at a neutron flux of 1.5 × 10¹² n/(cm²·s) and a gamma dose rate of 75 kGy/h (dose in sapphire) to a total neutron fluence of 1.1 × 10¹⁷ n/cm² and total gamma dose of on the order of 1.5 MGy. Consistent with previous gamma irradiation experiments, an absorption band centered below 500 nm (the minimum measurable wavelength using the measurement system described in this work) and extending as far as ~1000 nm reached saturation during irradiation in the gamma shut‐down field (the gamma‐ray radiation field that is present in the reactor post‐operation, as a consequence of the decay of radioisotopes that were produced during reactor operation) of the reactor prior to reactor irradiation. Beginning reactor irradiation and increasing the reactor power caused rapid increases in attenuation, followed by a linear increase with irradiation time at constant reactor power. Shutting down the reactor caused a decrease in the added attenuation; however, restarting the reactor caused the added attenuation to rapidly return to values almost identical to those observed at the end of the previous irradiation. The decrease in attenuation that was observed after the reactor was shut down shows the importance of the in‐situ nature of the measurements made in this work (previous ex‐situ attenuation measurements could not have captured this effect). A model is proposed for the experimentally obtained values of the radiation‐induced attenuation that involves three previously identified color centers including a composite V‐center, a center, and a center. The model accounts for gamma radiation‐induced ionization of pre‐existing defects, generation of new defects via displacement damage, and conversion between defect centers via ionization and charge recombination.     

Lateral Conduction Switching in Sputtered Ni‐rich NiO Thin Films for Write‐Once‐Read‐Many‐Times Memory Applications

Magnetron sputtering has been used to deposit Ni‐rich nickel oxide thin films. Based on the switching of lateral current conduction in the nickel oxide thin film between two in‐plane electrodes, a planar write‐once‐read‐many‐times memory device has been demonstrated. The switching from a low‐conductance state (i.e., the OFF state) to a high‐conductance state (i.e., the ON state) is induced by a writing voltage, and it is irreversible due to the formation of tilted conductive filaments that are hard to be dissolved by the Joule heating effect. For 80 devices under test, the writing voltage is in a narrow range of 2.0?3.5 V and the ON/OFF resistance ratio is larger than 10⁵ at the reading voltage of 0.3 V. An excellent reading endurance (10⁶ readings) for both ON and OFF states is demonstrated. The device is promising in low‐power applications as it can operate at ultra‐low voltages (e.g., the reading voltage can be below 100 mV).     

Influence of the degree of exfoliation of an organoclay on the flame‐retardant properties of cross‐linked ethylene‐co‐Propylene‐co‐diene monomer‐g‐Maleic anhydride‐based composites

Layered montmorillonite was synthesized by hydrothermal method, progressively modified by an alkylammonium and thoroughly characterized by elemental, thermal, and X‐ray diffraction (XRD) analysis. Pristine and modified clays were introduced in maleic anhydride‐modified ethylene‐co‐propylene‐co‐diene monomer matrix. XRD and transmission electron microscopy investigations showed microcomposite as well as intercalated or exfoliated nanocomposites morphologies depending on the organic content of the clay. The inhibitor character of the pristine clay on peroxides as crosslinking agent for rubbers was then demonstrated and overcome by using electron beam irradiation for specimens containing unmodified clay. Dynamic mechanical analyses and swelling measurements showed that it is possible to obtain the same degree of crosslinking of the polymer matrix by electron beam irradiation of the composites based on pristine clay specimens and conventional peroxide curing of modified‐clay‐based ones. Finally, flame‐retardant properties of different clays‐based composites showed a direct dependence on the degree of exfoliation. It was observed that the better the exfoliation, the higher is the flame retardancy. POLYM. COMPOS., 38:966–973, 2017. © 2015 Society of Plastics Engineers