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Ultrafast laser processing can be used to realize various morphological surface transformations, ranging from direct contour shaping to large-area-surface functionalization via the generation of “self-ordered” micro- and nanostructures as well as their hierarchical hybrids. Irradiation with high-intensity laser pulses excites materials into extreme conditions, which then return to equilibrium through these unique surface transformations. In combination with suitable top-down or bottom-up manufacturing strategies, such laser-tailored surface morphologies open up new avenues toward the control of optical, chemical, and mechanical surface properties, featuring various technical applications especially in the fields of photovoltaics, tribology, and medicine. This article reviews recent efforts in the fundamental understanding of the formation of laser-induced surface micro- and nanostructures and discusses some of their emerging capabilities.
Various methods have been used for introducing fire retardant additives into polymers. Deposition of thick fire retardant coatings directly onto polymer substrates is an alternative technique. An important Advantage of the coating technique is the preservation of the physical and chemical integrity of the polymer material. Moreover, the fire retardancy of the polymer materials can be achieved following their production. Suitable coating materials are inorganics, intumescent, char-forming, oxygendiluting, and cooling or radical quenching layers. The most important problem is to achieve sufficient coating thickness to withstand the direct attack of flame and to protect the polymer bulk from pyrolysis, otherwise blistering of coating, caused by emitted pyrolysis gases, is often observed.
To avoid blistering of coating, the adhesion between polyolefin Substrate and fire retardant coating has to be extraordinarily high.
In order to achieve such a high level of adhesion, the polymer surface has to be modified with adhesion-promoting functional groups. The deposition of thin plasma polymers as adhesion-promoting layers with NH2, OH or COOH groups has been the most suited method. These functional groups are able to form covalent bonds and other interactions between the fire-resistant coating and the plasma-modified polyolefin substrate.
Additionally, the plasma polymer counteracts the strong mechanical stresses in the laminate on exposure to high temperatures by its flexibility. The thick fire retardant coatings were chosen based on “green” ecological aspects to avoid flame-initiated emission of toxic or corrosive gases and remains of toxic char.
A bottom-up approach is presented for the production of arrays of indium islands on a molybdenum layer on glass, which can serve as micro-sized precursors for indium compounds such as copper-indium-gallium-diselenide used in photovoltaics. Femtosecond laser ablation of glass and a subsequent deposition of a molybdenum film or direct laser processing of the molybdenum film both allow the preferential nucleation and growth of indium islands at the predefined locations in a following indium-based physical vapor deposition (PVD) process. A proper choice of laser and deposition parameters ensures the controlled growth of indium islands exclusively at the laser ablated spots. Based on a statistical analysis, these results are compared to the non-structured molybdenum surface, leading to randomly grown indium islands after PVD.
For pulse laser materials processing often optical step index and gradient index multimode fibers with core diameters ranging from 100 to 600 μm are used. The design of a high power fiber transmission system must take into account limitations resulting from both surface and volume damage effects. Especially, breakdown at the fiber end faces and self-focusing in the fiber volume critically influence the fiber performance. At least operation charts are desirable to select the appropriate fiber type for given laser parameters.
In industry-relevant studies the influence of fiber core diameter and end face preparation on laser-induced (surface) damage thresholds (LIDT) was investigated for frequently used all-silica fiber types (manufacturer LEONI). Experiments on preform material (initial fiber material) and compact specimens (models of the cladding and coating material) accompanied the tests performed in accordance with the relevant LIDT standards ISO 11254-1 and ISO 11254-2 for 1-on-1 and S-on-1 illumination conditions, respectively. The relation beam diameter vs. LIDT was investigated for fused silica fibers and preforms. Additionally, the laser-induced (bulk) damage threshold of fused silica preform material F300 (manufacturer Heraeus) in dependence on external mechanical stress simulating fiber bending was measured. All experiments were performed with 10-ns laser pulses at 1064 and 532 nm wavelength with a Gaussian beam profile.
The possibility to excite surface plasmon polaritons (SPPs) at the interface between two media depends on the optical properties of both media and geometrical aspects. Specific conditions allowing the coupling of light with a plasmon-active interface must be satisfied. Plasmonic effects are well described in noble metals where the imaginary part of the dielectric permittivity is often neglected ('perfect medium approximation (PMA)'). However, some systems exist for which such approximation cannot be applied, hence requiring a refinement of the common SPP theory. In this context, several properties of SPPs such as excitation conditions, period of the electromagnetic field modulation and SPP lifetime then may strongly deviate from that of the PMA. In this paper, calculations taking into account the imaginary part of the dielectric permittivities are presented. The model identifies analytical terms which should not be neglected in the mathematical description of SPPs on lossy materials. These calculations are applied to numerous material combinations resulting in a prediction of the corresponding SPP features. A list of plasmon-active interfaces is provided along with a quantification of the above mentioned SPP properties in the regime where the PMA is not applicable.
A great number of Central Asian wall paintings, archeological materials, architectural fragments, and textiles, as well as painting fragments on silk and paper, make up the so called Turfan Collection at the Asian Art Museum in Berlin. The largest part of the collection comes from the Kucha region, a very important cultural center in the third to ninth centuries. Between 1902 and 1914, four German expeditions traveled along the northern Silk Road. During these expeditions, wall paintings were detached from their original settings in Buddhist cave complexes. This paper reports a technical study of a wall painting, existing in eight fragments, from the Buddhist cave no. 40 (Ritterhöhle). Its original painted surface is soot blackened and largely illegible. Grünwedel, leader of the first and third expeditions, described the almost complete destruction of the rediscovered temple complex and evidence of fire damage. The aim of this case study is to identify the materials used for the wall paintings. Furthermore, soot deposits as well as materials from conservation interventions were of interest. Non-invasive analyses were preferred but a limited number of samples were taken to provide more precise information on the painting technique. By employing optical and scanning electron microscopy, energy dispersive X-ray spectroscopy, micro X-ray fluorescence spectroscopy, X-ray diffraction analysis, and Raman spectroscopy, a layer sequence of earthen render, a ground layer made of gypsum, and a paint layer containing a variety of inorganic pigments were identified.
Sub-100-nm laser-induced periodic surface structures (LIPSS) were processed on bulk titanium (Ti) surfaces by femtosecond laser pulse irradiation in air (30 fs pulse duration, 790 nm wavelength). The laser peak fluence, the spatial spot overlap, and the number of overscans were optimized in a sample-scanning geometry in order to obtain large surface areas (5 mm × 5 mm) covered homogeneously by the LIPSS. The laser-processed regions were characterized by optical microscopy (OM), white light interference microscopy (WLIM) and scanning electron microscopy (SEM). The friction coefficient of the nanostructured surfaces was tested during 1000 cycles under reciprocal sliding conditions (1 Hz, 1.0 N normal load) against a 10-mm diameter ball of hardened 100Cr6 steel, both in paraffin oil and in engine oil used as lubricants. Subsequently, the corresponding wear tracks were qualified by OM, SEM, and energy dispersive X-ray analyses (EDX). The results of the tribological tests are discussed and compared to that obtained for near wavelength-sized fs-LIPSS, processed under somewhat different irradiation conditions. Some constraints for a beneficial effect of LIPSS on the tribological performance are provided.
In order to address the dynamics and physical mechanisms of LIPSS formation for three different classes of materials (metals, semiconductors, and dielectrics), two-color double-fs-pulse experiments were performed on Titanium, Silicon and Fused Silica. For that purpose a Mach–Zehnder interferometer generated polarization controlled (parallel or cross-polarized) double-pulse sequences at 400 nm and 800 nm wavelength, with inter-pulse delays up to a few picoseconds. Multiple of these two-color double-pulse sequences were collinearly focused by a spherical mirror to the sample surfaces. The fluence of each individual pulse (400 nm and 800 nm) was always kept below its respective ablation threshold and only the joint action of both pulses lead to the formation of LIPSS. Their resulting characteristics (periods, areas) were analyzed by scanning electron microscopy. The periods along with the LIPSS orientation allow a clear identification of the pulse which dominates the energy coupling to the material. For strong absorbing materials (Silicon, Titanium), a wavelength-dependent plasmonic mechanism can explain the delay-dependence of the LIPSS. In contrast, for dielectrics (Fused Silica) the first pulse always dominates the energy deposition and LIPSS orientation, supporting a non-plasmonic formation scenario. For all materials, these two-color experiments confirm the importance of the ultrafast energy deposition stage for LIPSS formation.
A new technique to fix bioceramic powder on a titanium alloy by using femtosecond laser pulses is presented. It is shown that gentle fixation of a bioactive dielectric material on a metallic model implant is successful. This is potentially a new tool for the improvement of bone prostheses. An advantage of the ultrashort pulses is the very low heat influx into the whole sample. There is only a very thin interaction zone during the fixing, which is the metal surface in contact with the ceramic layer. Neither the fixed ceramic particles nor the major part of the metal suffer any modification. The stability of the model implant (ceramic on metal) is investigated by rotating bending fatigue tests. No indication of a reduction of the mechanical stability compared to untreated metallic reference samples was found.
The adhesion of thick poly(allylamine)-polyphosphate layers (1 µm) deposited by the wet-chemical layer-by-layer technique (LbL) onto polyethylene or polystyrene (each 100 µm) was very low. To promote the adhesion of these LbL layers the polyolefin substrates were oxidized at the surface by short exposure to the oxygen plasma (2 or 5 s) and subsequently coated with an interlayer of plasma-deposited poly(allylamine) or poly(allyl alcohol) (100 nm). The plasma polymer interlayers have improved strongly the adhesion between polyolefin substrates and polyphosphate coatings. Such phosphate coatings are interesting for life sciences (nucleotide formation) but also for fire retardancy in combination with N-rich compounds such as melamine.
The intention was to prefer chemical and hydrogen bonds for adhesion promoting because of their high binding energy. Therefore, the introduced oxygen-containing groups at the polyolefin surface could interact with the OH or NH2 groups of the adhesion-promoting plasma polymer interlayer. These groups were also able to interact strongly with the poly(allylamine)-polyphosphate topcoating.
The coated polyolefins were investigated using Fourier Transform Infrared Spectroscopy in Attenuated Total Reflectance mode (FTIR-ATR), X-ray Photoelectron Spectroscopy (XPS), Thermo-Gravimetric Analyses (TGA) and Atomic Force Spectroscopy (AFM) and 90° peel test.