From Femtosecond to Nanosecond Laser Microstructuring of Conical Aluminum Surfaces by Reactive Gas Assisted Laser Ablation

A conical microstructure is one of the most versatile surface textures obtained by ultrashort laser micromachining. Besides an increased surface area, unique surface properties such as superhydrophilicity, increased absorptivity; and thermal emissivity can be tailored. On metals, usually ultrashort laser pulses in the femtosecond to low picosecond range are used to obtain these surface structures, whereas nanosecond laser pulses favor melting processes. Herein, we report on an investigation of reactive gas atmospheres such as oxygen, steam, and halogens during laser micromachining of aluminum with 6 ns laser pulses. At a reduced pressure of 20 hPa (air) with additional iodine vapor as reactive species, we found a perfectly microconical structured surface to be formed with nanosecond laser pulses. The resulting surface structures were proven to be free of residual halogens. The application of nanosecond instead of femtosecond laser pulses for the surface structuring process allows to apply significantly less complex laser sources.     

Local damage of HT-materials by laser irradiation in the SEM

By using a pulsed Nd:YAG laser the high temperature materials zirconium oxide, fine grain graphite and silicon nitride were rapidly irradiated (heating thermal shock) and their damage behavior was investigated. The laser beam parameters at sample surface were detected by a laser beam analyzing system and correlated with the local damage mechanisms of the materials as erosion, crack formation and solid-solid phase transformation. For the investigations image analysis, localized x-ray analysis, and the ion beam slope cutting technique were applied. The temperature field in the material was simulated by using temperature dependent material parameters for different laser beam parameters. The results illustrate both the strong influence of the temporal and spatial laser energy profile and the materials properties to the material damage.Dedicated to Professor Dr. rer. nat. Dr. h.c. Hubertus Nickel on the occasion of his 65th birthday     

The microstructural characterization of PA6/PA12 blend specimens fabricated by selective laser sintering

This study investigates the processing of blends of polyamide 6 (PA6) and polyamide 12 (PA12) by selective laser sintering (SLS) using a CO₂ laser. Powder properties of undiluted polymers, mixture composition, and processing parameters, as well as their influence on the microstructure of the specimens manufactured, were evaluated. Polyamides showed higher absorption of laser energy during the sintering of blend specimens, with subsequent thermal energy transfer to the melting of the polymeric phases. The structure of parts obtained by SLS is dependent on the process parameters and the characteristics of the powder material to be processed. The microstructures of PA6/PA12 blend specimens were heterogeneous, with co-continuous and disperse phases depending on the quantity of PA12. The porosity and crystallinity also changed as a function of the component proportions. The use of polymeric blends can increase the range of structures and properties of SLS parts.     

利用H3PO4液层侧面红外热像研究YBCO高温超导薄膜的激光辅助刻蚀特性

利用红外热像实时监测系统,获取钇钡铜氧激光辅助化学刻蚀中H₃PO₄液层的侧面红外热像,研究了其溶液温度分布与热对流特性,并对红外监测数据与钇钡铜氧薄膜激光化学刻蚀特性的关系进行了分析.主要实验结论包括:红外灰度图可真实反映溶液的温度分布和热对流情况,为激光化学刻蚀的热环境分析提供有价值的红外监测数据;通过任意时刻钇钡铜氧表面生成热流所到达高度的分布情况和该时刻的红外灰度图,分析出钇钡铜氧薄膜表面各区域的腐蚀启动先后和刻蚀程度差异等重要信息,为钇钡铜氧及其它材料的激光化学刻蚀特性的实时监测提供了一种新的技术手段.     

Corrélation entre les conditions de traitement thermique par laser co2 de puissance et les modifications structurales de surface d'alliage de titane TA6V

The transfer of electromagnetic wave energy to the metallic material is done by an exchange between the laser photons and the lattice electrons via the inverse bremstrahlung. This process induces the passage of an electron from the valence to the conduction band in which it becomes free and energetic and it provokes, by collision with others electrons of the crystal lattice, the heating of the sample surfaces. The laser energy is then transformed, at the surface, into thermal energy (heat) which diffuses into the sample.For the same kind of materials with surfaces prepared in the same conditions, only laser beam parameters vary, following the relation: Qs = P τ / S, where Qs is the specific energy at the lighted surface, P the power of the laser, τ the interaction time and S the surface lighted by the laser beam. This factor indicates if the laser treatments are done without microstructural modification of the samples or with melting of the material surface.The martensitic phase α' obtained after the laser treatment is metastable, with a small grain size compared to those obtained with the classical thermal treatments. The size of α' grains depends on the energy density (Qs = P τ / S ) received by the specimen from the laser wave.     

Thermal waves scattering by a subsurface sphere in a semi-infinite exponentially graded material using non-Fourier's model

In this study, the multiple scattering of thermal waves and temperature distribution resulting from a subsurface sphere in a semi-infinite exponentially graded material are investigated, and the analytical expression of the temperature at the surface of the graded material is obtained. Non-Fourier heat conduction equation is applied to solve the temperature at the surface, and the image method is used to satisfy the semi-infinite boundary condition of graded material. The thermal wave fields are expressed using wave function expansion method, and the expanded mode coefficients are determined by satisfying the boundary condition of the sphere. According to the wave equation of heat conduction, a general solution of scattered thermal waves is presented for the first time. The temperature distribution and phase difference at the surface of the semi-infinite material with different parameters are graphically presented. Analyses show that the hyperbolic heat conduction equation cannot be regarded as a continuation of the parabolic heat conduction equation at very short time scale. The effects of the incident wave number, the structural and physical parameters on the distribution of temperature and phase difference in the semi-infinite material are also examined.     

Simulation of the densification of semicrystalline polymer powders during the selective laser sintering process: Application to Nylon 12

The processes of heating and densification of semicrystalline polymer powders during the selective laser sintering process are simulated using the finite element method. Based on a previously developed three-dimensional approach for the sintering of amorphous polymer powders, the modeling methodology is extended to semicrystalline polymers by taking into account the effects of latent heat during melting. In these simulations, the temperature-dependent thermal conductivity, the specific heat, the density, and the effect of latent heat are computed and then used as material constants for the integration of the heat equation. Results for the temperature and density distribution using Nylon-12 powder are presented and discussed. The effects of processing parameters on the density distribution are also presented. Published in Russian in Vysokomolekulyarnye Soedineniya, Ser. A, 2008, Vol. 50, No. 6, pp. 1067–1073. This article was submitted by the authors in English.     

Measurement of thermal diffusivity and specific heat capacity of polymers by laser flash method

We measured thermal diffusivity and heat capacity of polymers by laser flash method, and the effects of measurement condition and sample size on the accuracy of the measurement are discussed. Thermal diffusivities of PTFE films with thickness 200–500 μm were the same as those data that have been reported. But, the data for film thickness less than 200 μm have to be corrected by an equation to cancel thermal resistance between sample film and graphite layers for receiving light and detecting temperature. Thermal diffusivity was almost unaffected by the size of area vertical to the direction of laser pulse, because heat flow for the direction could be negligible. Specific heat capacity of polymer film was exactly measured at room temperature, provided that low absorbed energy (< 0.3 J) and enough sample mass (> 25 mg) were satisfied as measuring conditions. Thermal diffusivity curve of PS or PC versus temperature had a terrace around T_g, whereas that of PE decreased monotonously with increasing in temperature until T_m. Further, we estimated relative specific heat capacity (RC_p) by calculating ratios of heat capacities at various temperatures to the one at 299 K. RC_p for PS obtained by laser flash method was larger than that obtained by DSC method, whereas the RC_ps for PE obtained by the both methods agreed with one another until T_m (305 K). RC_p for PS decreased linearly, with increase in temperature after it increased linearly until T_g (389 K), showing similarity to temperature dependency of thermal conductivity. RC_p for PE also decreased until T_m, similar to thermal conductivity. ©1995 John Wiley & Sons, Inc.     

Sensitivity analysis of a predictive model for the fire behaviour of a sandwich panel

A sensitivity analysis to assumptions and input variables is carried out for a predictive model previously developed [1] for the fire response of a glass-fibre/polyester panel and a glass-fibre/polyester-Vermiculux sandwich. It is an unsteady, one-dimensional model using the porous medium approximation and a constant gas pressure with two-step, finite rate kinetics for the thermal decomposition and combustion of the polymeric resin, moisture evaporation described by an Arrhenius rate law, heat and mass transfer by convection, heat conduction and radiation described by effective thermal conductivities, variation of the volumetric fractions of the polymeric resin and the moisture with the conversion degree, effective specific heats, external heat transfer resistances and surface ablation. The strongest impact on the model predictions is exerted by the imposed external heat flux with variations on the characteristic process times between 49 and 774%. An important role in sample heating/conversion is also played by surface ablation and/or external heat transfer resistance with variations up to 30-72% or, when ablation is disregarded, with temperatures along the core layer well below those of the degrading skin. These are also significantly affected by surface heat losses, with the assumption of adiabatic bottom surface leading to heterogeneous ignition of the lower skin, and evaporation of moisture with variations in the characteristic times up to 35%. The model for the effective thermal conductivity of the fibre-reinforced skin (the Parallel, the Maxwell-Eucken and the Effective Medium Theory models versus the Series model) is also important resulting in characteristic time variations up to 35%. The absence of local thermal equilibrium between the condensed and the gas/vapour phase and the kinetic details of the polymer reactions are comparatively less important (maximum diminution in the characteristic times of 16%). Moreover, although over-pressures, modelled by the Darcy law, become quite high especially during the moisture evaporation stage (up to ten times the atmospheric value), their effects on the thermal response of the structure are completely negligible when structural changes are not modelled. Finally, a sensitivity analysis is also carried out to input parameters.     

镍表面三维微图形的复制加工

运用约束刻蚀剂层技术(CELT)在金属镍(Ni)表面实现三维微图形加工,以规整的三维齿状微结构作模板,获得可有效CELT加工的化学刻蚀和捕捉体系,在Ni表面得到了与齿状结构互补的三维微结构并应用扫描电子显微镜(SEM)和原子力显微镜(AFM)表征刻蚀图案,证实CELT可用于金属表面Ni的三维微图形刻蚀加工．     

The role of physical and chemical properties of Pd nanostructured materials immobilized on inorganic carriers on ion formation in atmospheric pressure laser desorption/ionization mass spectrometry

Fundamental parameters influencing the ion‐producing efficiency of palladium nanostructures (nanoparticles [Pd‐NP], nanoflowers, nanofilms) during laser irradiation were studied in this paper. The nanostructures were immobilized on the surface of different solid inorganic carrier materials (porous and mono‐crystalline silicon, anodic porous aluminum oxide, glass and polished steel) by using classical galvanic deposition, electroless local deposition and sputtering. It was the goal of this study to investigate the influence of both the nanoparticular layer as well as the carrier material on ion production for selected analyte molecules. Our experiments demonstrated that the dimensions of the synthesized nanostructures, the thickness of the active layers, surface disorders, thermal conductivity and physically or chemically adsorbed water influenced signal intensities of analyte ions during surface‐assisted laser desorption/ionization (SALDI) while no effects such as plasmon resonance, photoelectric effect or catalytic activity were expected to occur. Excellent LDI abilities were seen for Pd‐NPs immobilized on steel, while Pd nanoflowers on porous silicon exhibited several disadvantages; viz, strong memory effects, dependency of the analytical signal on amount of physically and chemically adsorbed water inside porous carrier, reduced SALDI activity from unstable connections between Pd and semiconductor material, decrease of the melting point of pure silicon after Pd immobilization and resulting strong laser ablation of metal/semiconductor complex, as well as significantly changed surface morphology after laser irradiation. The analytical performance of Pd‐NP/steel was further improved by applying a hydrophobic coating to the steel surface before galvanic deposition. This procedure increased the distance between Pd‐NPs, thus reducing thermal stress upon LDI; it simultaneously decreased spot sizes of deposited sample solutions. Copyright © 2014 John Wiley & Sons, Ltd.     

Influence of thermophysical properties on burning behavior of intumescent fire-retardant materials

Thermophysical properties of intumescent fire-retardant (IFR) materials are important parameters as input data in modeling the combustion process of IFR materials in a fire. In this paper, the influences of several thermophysical properties on burning behavior of IFR materials are simulated based on a combustion model of IFR materials. Thermophysical properties selected here are thermal conductivity of virgin material and char layer, specific heat capacity of virgin material, density of virgin material, surface emissivity of virgin material and char layer, heat of decomposition, heat of combustion, and intumescent temperature. Predicted heat release rates curves for the IFR material at an incident heat flux of 50 kW m^?2 are shown for the varied thermophysical parameters’ values. The results show that these varied parameter values can affect the burning behavior of materials remarkably. A comparison with experimental results demonstrates that the predictions of heat release rates are in reasonably good agreement with the experiment.     

Cell adhesion and locomotion on microwell-structured glass substrates

The purpose of this study was to investigate the effect of microstructured material surface on cell adhesion and locomotion in real-time. ArF excimer laser direct-writing ablation was used to fabricate microwell patterns with precise control of size and spacing on glass. The influence of the ablation process parameters (laser fluence, pulse number and repetition rate) on the micromachining quality (depth, width, aspect ratio and edge effects) of the microwells was established. Human fibroblast cells, as an example of anchorage-dependent cells, were seeded onto the microstructured glass substrate and time-lapse microscopy was used to study cell adhesion and locomotion. The interaction with microstructured materials resulted in fibroblast cell repulsion and the cells exhibited a higher locomotion speed (75.77±3.36 μm/h) on the structures in comparison with plane glass control (54.01±15.53 μm/h). Further studies are needed to firmly establish the potential of microstructuring, for example, in elongating the life spans of implantable devices.     

Noncontact measurement of thermal and optical parameters of biological tissues and materials using IR laser radiometry

A technique for simultaneous measurements of the thermal diffusivity, specific heat, and effective absorbtion coefficient was developed. The technique is based on local heating of a sample by laser radiation and thermal imager measurement of the temperature field dynamics in the surface layer in both the heating and cooling stages. The technique includes a program for calculating the laser-induced temperature field in the sample volume and the determination of three parameters by the Levenberg-Marquardt algorithm to provide the best fit of calculations to experimental results. The statistical error of thermal diffusivity, specific heat, and effective absorbtion coefficient measurements was 5–6%. The technique efficiency was demonstrated by the example of the development of a thermal and optical equivalent of cartilage tissue, based on polyacrylamide hydrogel.     

Thermo-kinetics study of laser-induced desorption of self-assembled monolayers from gold: case of laser micropatterning

Laser-induced desorption of self-assembled monolayers (SAMs) from gold surfaces within context of the direct laser patterning methodology was investigated through combining results of a heat diffusion thermal model with desorption kinetics of alkanethiol SAMs. It was found that contrast plots of experimental scanning electron microscopy (SEM) images, which are correlated to surface coverage of SAMs desorbed after laser irradiation, agreed with the theoretically predicted surface composition of SAMs. The surface composition of SAM was then interpreted in terms of the wetting property of the resulting surface. The effect of incident laser beam power and size on the final spatial coverage of SAMs on the surface and feature sizes was investigated both experimentally and by modeling. Theoretical modeling and experimental evidence showed that the resulting feature sizes are wider when the surface is heated by a laser of higher power. Increasing the laser beam size results in broadening of feature sizes. Considering the correlation of the theoretical and experimental results, we concluded that the feature sizes are controllable in a predictable way (using the presented thermal-kinetics model) through varying laser beam power and beam size.     

Novel polyphenylene oxide microcapsules filled with epoxy resins

Novel polyphenylene oxide (PPO) microcapsules filled with epoxy resins (PPOMCs) were synthesized by in situ polymerization technology with 2, 6‐dimethy phenol as shell materials and diglycidyl ether of bisphenol A epoxy resins as core materials. The structures and morphologies of PPOMCs were characterized using Fourier‐transform infrared spectroscopy, micro‐confocal Raman microscope, laser scanning confocal microscopy, scanning electron microscopy and optical microscopy, respectively. The thermal properties of PPOMCs were investigated using differential scanning calorimetry and thermogravimetric analysis. The influences of different processing parameters such as the weight ratio of shell material to core material, kind of surfactant and reaction temperature on the morphologies and sizes of PPOMCs were investigated. Preliminary investigation on application of PPOMCs to thermosetting resins 4,4′‐bismaleimidodiphenylmethane/O,O′‐diallylbisphenol A (BMI/BA) system was conducted. Results indicate that PPOMCs can be synthesized successfully. The sizes and surface morphologies of PPOMCs may be significantly affected by different processing parameters. PPOMCs can be well prepared at about 30°C, and they depend strongly on the kind of surfactant and the weight ratio of shell material to core material. PPOMCs basically exhibit high thermal stability when the temperature is below 258°C. The addition of PPOMCs can improve the mechanical properties and maintain the thermal properties of BMI/BA system. The released core materials from PPOMCs may repair the matrix cracks through the polymerization of epoxy resins initiated by curing agent. Copyright © 2012 John Wiley & Sons, Ltd.     

General bottom-up construction of spherical particles by pulsed laser irradiation of colloidal nanoparticles: a case study on CuO

The development of a general method to fabricate spherical semiconductor and metal particles advances their promising electrical, optical, magnetic, plasmonic, thermoelectric, and optoelectric applications. Herein, by using CuO as an example, we systematically demonstrate a general bottom-up laser processing technique for the synthesis of submicrometer semiconductor and metal colloidal spheres, in which the unique selective pulsed heating assures the formation of spherical particles. Importantly, we can easily control the size and phase of resultant colloidal spheres by simply tuning the input laser fluence. The heating-melting-fusion mechanism is proposed to be responsible for the size evolution of the spherical particles. We have systematically investigated the influence of experimental parameters, including laser fluence, laser wavelength, laser irradiation time, dispersing liquid, and starting material concentration on the formation of colloidal spheres. We believe that this facile laser irradiation approach represents a major step not only for the fabrication of colloidal spheres but also in the practical application of laser processing for micro- and nanomaterial synthesis.     

Thermal analysis of oxide-isolated stripe diode lasers

The finite-element thermal model of the oxide-isolated stripe geometry diode laser is presented in this work. The calculation procedure was carried out with a standard IBM PC/AT microcomputer. The ohmic contact heat generation and the thickness d_ox of the SiO₂ layer, as two parameters of OIS lasers crucial from a thermal aspect, were taken into account. The system of isotherms obtained for this laser allowed a discussion of the heat spreading process within the laser structure and a comparison of the relative contributions of all heat sources.This work was carried out in program CFRN 117/90 of the Polish Ministry of Education Research project P/04/142/90-2.     

Rotational averaging and optimization of laser-induced population transfer in molecules

The dynamics of a molecule subject to a short laser pulse is investigated, with focus on the averaging over initial rotational states and on the optimization of laser parameters for the efficient population transfer between vibrational and electronic states. A relation is established between final-state populations obtained with a fixed orientation and those based on a full treatment of the rotational degrees of freedom. In the short-pulse approximation, rotational averaging amounts to integrating the fixed molecule results over all orientations. The theory is applied to a variety of model systems and verified with numerical calculations using Gaussian pulses. We calculate target state populations with three procedures, optimizing the laser pulse for a fixed orientation without orientational averaging, averaging without changing the laser parameters, and reoptimizing the parameters after averaging. The analysis of the two-level system provides a reference for the order of magnitude of the effects of averaging. The three-level system brings out the relevant role of the geometry of polarization vectors and transition dipoles. The multiphoton excitation of a Morse oscillator shows the importance of taking into account the dependence of resonance frequencies on the laser intensity. Within a proton transfer model we discuss the results obtained with and without chirping and we show that "optimizing after averaging" can be as effective as choosing a more refined pulse shape.