Filtern
Erscheinungsjahr
Dokumenttyp
- Zeitschriftenartikel (156)
- Vortrag (51)
- Beitrag zu einem Tagungsband (42)
- Beitrag zu einem Sammelband (31)
- Posterpräsentation (13)
- Buchkapitel (12)
Schlagworte
- Femtosecond laser (28)
- Laser-induced periodic surface structures (LIPSS) (26)
- Femtosecond laser ablation (24)
- Laser ablation (23)
- Laser processing (14)
- Radiation protection (12)
- Silicon (11)
- Laser cleaning (10)
- Ablation (9)
- Materialbearbeitung (9)
Organisationseinheit der BAM
- 6 Materialchemie (56)
- 6.2 Material- und Oberflächentechnologien (56)
- 9 Komponentensicherheit (4)
- 9.5 Tribologie und Verschleißschutz (4)
- 6.7 Materialsynthese und Design (3)
- 4 Material und Umwelt (2)
- 4.1 Biologische Materialschädigung und Referenzorganismen (2)
- 6.1 Oberflächen- und Dünnschichtanalyse (2)
- 3 Gefahrgutumschließungen; Energiespeicher (1)
- 3.2 Gefahrguttanks und Unfallmechanik (1)
Paper des Monats
- ja (3)
Characterization of laser-generated microparticles by means of a dust monitor and SEM imaging
(2006)
Nanosecond laser (1064 nm wavelength) cleaning of artificially soiled paper as a model sample simulating a real-world artwork was performed. During the cleaning process, the ejection of particles was monitored in situ by means of a dust monitor (8 size classes, ranging from 0.3 µm to >2 µm) and ex situ using a mini-cascade impactor (MKI, 5 stages). The cleaning result was analyzed by scanning electron microscopy (SEM) considering possible laser-induced damages to the substrate. Size distributions of emitted particles were measured depending on the processing parameters: laser fluence, F, and pulse number per spot, N. High numbers of large (>2 µm) particles were collected by the mini-cascade impactor indicating a gas dynamical liftoff process. Obviously, these particles were not affected by the laser-matter interaction. The different methods (SEM, MKI, and dust monitor) are compared with respect to their usefulness for a proper interpretation of the cleaning results.
Recent publications indicate that the order of electrochemical anodization (before or after the laser processing step) plays an important role for the response of bone-forming osteoblasts—an effect that can be utilized for improving permanent dental or removable bone implants. For exploring these different surface functionalities, multimethod morphological, structural, and chemical characterizations are performed in combination with electrochemical pre- and postanodization for two different characteristic microspikes covered by nanometric laser-induced periodic surface structures on Ti–6Al–4V upon irradiation with near-infrared ps-laser pulses (1030 nm wavelength, ≈1 ps pulse duration, 67 and 80 kHz pulse repetition frequency) at two distinct sets of laser fluence and beam scanning parameters. This work involves morphological and topographical investigations by scanning electron microscopy and white light interference microscopy, structural material examinations via X-ray diffraction, and micro-Raman spectroscopy, as well as near-surface chemical analyses by X-ray photoelectron spectroscopy and hard X-ray photoelectron spectroscopy. The results allow to qualify the mean laser ablation depth, assess the spike geometry and surface roughness parameters, and provide new detailed insights into the near-surface oxidation that may affect the different cell growth behavior for pre- or postanodized medical implants.
Curved substrates can be micro-structured by laser ablation, which is not possible with standard lithographic methods. The novel femtosecond-pulse laser technique allows the production of defined and reproducible micro-perforations of originally analyte-impermeable membranes. The trans-membrane analyte flux can be controlled both by the variation of the laser focus diameter resulting in different areas of single perforations, and the number of perforations in arrays on small membrane areas. This leads to a higher degree of variability as well as reproducibility of the diffusion qualities of sensor membranes, and marks the main innovation with this technique compared to the hand-made mechanical perforation by specially grinded needles used up to now. Touchless micro-perforation of small membrane areas with negligible heat damage of the structures adjacent to the perforation allows the application of analyte door membranes directly onto curved surfaces of miniaturized needle-sensors assigned for in vivo glucose monitoring, for the first time.
The influence of different laser pulse lengths on the removal of a polymer layer from metal substrates was investigated. As model systems, doped poly(methylmetacrylate) (PMMA) on titanium and tungsten substrates were selected.
The ablation threshold and irradiation spot morphology of titanium and tungsten were compared for femtosecond (fs) and nanosecond (ns) laser irradiation and different pulse numbers. Nanosecond laser treatment resulted in a non-homogeneous surface morphology for both titanium and tungsten substrates. Femtosecond irradiation of tungsten revealed a homogeneous ablation spot with little changes in the surface morphology. For titanium, the formation of columnar structures within the irradiation spot was observed.
Two different dopant concentrations were used for PMMA to achieve an equal linear absorption coefficient for the femto- and nanosecond laser wavelengths of 790 and 1064 nm. The best results were achieved for the removal of doped PMMA by femtosecond laser irradiation, where only a minimal modification of the metal surface was detected. In the case of nanosecond laser exposure, a pronounced change of the structure was observed, suggesting that damage-free cleaning of the selected metal may only be possible using femtosecond laser pulses. Different experimental parameters, such as laser fluence, pulse repetition rate and sample speed were also investigated to optimize the cleaning quality of doped PMMA from tungsten substrates with femtosecond laser pulses.
We investigate the periodic structure formation upon intense femtosecond pulsed irradiation of chrome steel (100Cr6) for linearly polarised laser beams. The underlying physical mechanism of the laser-induced periodic structures is explored, their spatial frequency is calculated and theoretical results are compared with experimental observations. The proposed theoretical model comprises estimations of electron excitation, heat transfer, relaxation processes, and hydrodynamics-related mass transport. Simulations describe the sequential formation of sub-wavelength ripples and supra-wavelength grooves. In addition, the influence of the laser wavelength on the periodicity of the structures is discussed. The proposed theoretical investigation offers a systematic methodology towards laser processing of steel surfaces with important applications.
Femtosecond lasers provide a novel method of attaching bioceramic material to a titanium alloy, thereby improving the quality of bone implants. The ultrashort 30 fs laser pulses (790 nm wavelength) penetrate a thin dip-coated layer of fine ceramic powder, while simultaneously melting a surface layer of the underlying metal. The specific adjustment of the laser parameters (pulse energy and number of pulses per spot) avoids unnecessary melting of the bioactive calcium phosphate, and permits a defined thin surface melting of the metal, which in turn is not heated throughout, and therefore maintains its mechanical stability. It is essential to choose laser energy densities that correspond to the interval between the ablation fluences of both materials involved: about 0.1-0.4 J cm-2. In this work, we present the first results of this unusual technique, including laser ablation studies, scanning electron microscopy and optical microscope images, combined with EDX data.
Bone implants made of metal, often titanium or the titanium alloy Ti6Al4V, need to be surface treated to become bioactive. This enables the formation of a firm and durable connection of the prosthesis with the living bone. We present a new method to uniformly cover Ti6Al4V with a thin layer of ceramics that imitates bone material. These calcium alkali phosphates, called GB14 and Ca10, are applied to the metal by dip coating of metal plates into an aqueous slurry containing the fine ceramic powder. The dried samples are illuminated with the 790 nm radiation of a pulsed femtosecond laser. If the laser fluence is set to a value just below the ablation threshold of the ceramic (ca. 0.4 J/cm²) the 30 fs laser pulses penetrate the partly transparent ceramic layer of 20–40 µm thickness. The remaining laser fluence at the ceramic–metal interface is still high enough to generate a thin metal melt layer leading to the ceramic fixation on the metal. The laser processing step is only possible because Ti6Al4V has a lower ablation threshold (between 0.1 and 0.15 J/cm²) than the ceramic material. After laser treatment in a fluence range between 0.1 and 0.4 J/cm², only the particles in contact with the metal withstand a post-laser treatment (ultrasonic cleaning). The non-irradiated rest of the layer is washed off. In this work, we present results of a successful ceramic fixation extending over larger areas. This is fundamental for future applications of arbitrarily shaped implants.
The surface of a titanium alloy (Ti6Al4V) implant material was covered with a bioactive calcium alkali phosphate ceramic with the aim to accelerate the healing and to form a stronger bond to living bone tissue. To fix the ceramic powder we used a femtosecond laser, which causes a thin surface melting of the metal. It is a requirement to prove that the laser irradiation would not reduce the lifetime of implants. Here we present the results of mechanical stability tests, determined by the rotating bending fatigue strength of sample rods. After describing the sample surfaces and their modifications caused by the laser treatment we give evidence for an unchanged mechanical stability. This applies not only to the ceramic fixation but also to a comparatively strong laser ablation.
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 exciting properties of micro- and nano-patterned surfaces found in natural species hide a virtually endless potential of technological ideas, opening new opportunities for innovation and exploitation in materials science and engineering. Due to the diversity of biomimetic surface functionalities, inspirations from natural surfaces are interesting for a broad range of applications in engineering, including phenomena of adhesion, friction, wear, lubrication, wetting phenomena, self-cleaning, antifouling, antibacterial phenomena, thermoregulation and optics. Lasers are increasingly proving to be promising tools for the precise and controlled structuring of materials at micro- and nano-scales. When ultrashort-pulsed lasers are used, the optimal interplay between laser and material parameters enables structuring down to the nanometer scale. Besides this, a unique aspect of laser processing technology is the possibility for material modifications at multiple (hierarchical) length scales, leading to the complex biomimetic micro- and nano-scale patterns, while adding a new dimension to structure optimization. This article reviews the current state of the art of laser processing methodologies, which are being used for the fabrication of bioinspired artificial surfaces to realize extraordinary wetting, optical, mechanical, and biological-active properties for numerous applications. The innovative aspect of laser functionalized biomimetic surfaces for a wide variety of current and future applications is particularly demonstrated and discussed. The article concludes with illustrating the wealth of arising possibilities and the number of new laser micro/nano fabrication approaches for obtaining complex high-resolution features, which prescribe a future where control of structures and subsequent functionalities are beyond our current imagination.
X-ray emission hazards from ultrashort pulsed laser material processing in an industrial setting
(2021)
Interactions between ultrashort laser pulses with intensities larger than 10^13 W/cm^2 and solids during material processing can lead to the emission of X-rays with photon energies above 5 keV, causing radiation hazards to operators. A framework for inspecting X-ray emission hazards during laser material processing has yet to be developed. One requirement for conducting radiation protection inspections is using a reference scenario, i.e., laser settings and process parameters that will lead to an almost constant and high level of X-ray emissions. To study the feasibility of setting up a reference scenario in practice, ambient dose rates and photon energies were measured using traceable measurement equipment in an industrial setting at SCHOTT AG. Ultrashort pulsed (USP) lasers with a maximum average power of 220 W provided the opportunity to measure X-ray emissions at laser peak intensities of up to 3.3 × 10^15 W/cm^2 at pulse durations of ~1 ps. The results indicate that increasing the laser peak intensity is insufficient to generate high dose rates. The investigations were affected by various constraints which prevented measuring high ambient dose rates. In this work, a list of issues which may be encountered when performing measurements at USP-laser machines in industrial settings is identified.
Results of a round-robin experiment in multiple-pulse LIDT measurement with ultrashort pulses
(2004)
Bacterial biofilms pose serious problems in medical and industrial settings. One of the major societal challenges lies in the increasing resistance of bacteria against biocides used in antimicrobial treatments, e.g., via overabundant use in medicine, industry, and agriculture or cleaning and disinfection in private households. Hence, new efficient bacteria-repellent strategies avoiding the use of biocides are strongly desired. One promising route to achieve bacteria-repellent surfaces lies in the contactless and aseptic large-area laser-processing of technical surfaces. Tailored surface textures, enabled by different laser-processing strategies that result in topographic scales ranging from nanometers to micrometers may provide a solution to this challenge. This article presents a current state-of-the-art review of laser-surface subtractive texturing approaches for controlling the biofilm formation for different bacterial strains and in different environments. Based on specific properties of bacteria and laser-processed surfaces, the challenges of anti-microbial surface designs are discussed, and future directions will be outlined.
In this study, femtosecond laser-induced sub-micrometer structures are generated to modify polyethylene (PE) surface topographies. These surfaces were subjected to bacterial colonization studies with Escherichia coli and Staphylococcus aureus as test strains. The results reveal that the nanostructures do not influence S. aureus coverage, while the adhesion of E. coli is reduced.
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.
Many wooden artworks are contaminated by DDT (dichlorodiphenyltrichloroethane) as a result of a surface treatment by means of the liquid preservative Hylotox-59©. It was used until the end of the 1980s. DDT crystal structures are formed on the wood surfaces by the "blooming" of chlorine compounds. In addition to an aesthetic disturbance, it is assumed that DDT represents a health risk. Even decades after applying, the toxins in the wood preservatives are still detectable because they are of low volatility in many wood samples. Contaminated waste wood with natural biocide ageing, gilded and wood carved elements of an old picture frame and wooden samples with paint layers were provided by the Schlossmuseum Sondershausen. Non-contact procedures using laser and plasma appear reasonable to remove the DDT crystals. During the experiments, health and safety issues for the operator have to be taken into account.
The removal of DDT was evaluated employing femtosecond and nanosecond laser radiation and cold atmospheric plasma techniques with different working gases (air, nitrogen, and argon). Before laser application, a chlorine measurement representing the DDT density on the wooden surface is done by X-ray fluorescence (XRF) analysis as reference. After laser processing, the XRF analysis is used again at the same surface position to determine the depletion rate. Additionally, a documentation and characterization of the sample surface is performed before and after laser and plasma treatment using optical microscopy (OM). For plasma processing with various systems a chlorine measurement is done by gas chromatographic-mass spectrometry (GCMS) analysis.
Until the end of the 1980s many wooden artworks underwent surface treatment by liquid preservatives, e.g. Hylotox-59. DDT (dichlorodiphenyltrichloroethane) crystal structures are formed on the wooden surfaces by the "blooming" of chlorine compounds by time. In addition to an aesthetic disturbance, it is assumed that DDT represents a health risk. Therefore, the removal of DDT crystals from the surfaces is requested. Contaminated wood with natural biocide ageing, gilded and wood carved elements and wooden samples with paint layers were provided by the Schlossmuseum Sondershausen, Germany. Laser cleaning on selected surface areas on the objects was done by means of femtosecond and nanosecond laser pulses. For the same object, cleaning results using 30-fs laser pulses at 800 nm wavelength are compared to findings utilizing 10-ns laser pulses at 1064 nm wavelength. Before and after laser treatment, chlorine measurements at the same surface position were done by X-ray fluorescence analysis (XRF) as an indicator for the presence of DDT. In this way, pointwise chlorine depletion rates can be obtained for the different pulse duration regimes and wavelengths. Additionally, the object surfaces were examined using optical microscopy and multi spectral imaging analysis.
Light concentration opens up the path to enhanced material efficiency of solar cells via increased conversion efficiency and decreased material requirement. For true material saving, a fabrication method allowing local growth of high quality absorber material is essential. We present two scalable fs-laser based approaches for bottom-up growth of Cu(In,Ga)Se2 micro islands utilizing either site-controlled assembly of In(,Ga) droplets on laser-patterned substrates during physical vapor deposition, or laser-induced forward transfer of (Cu,In,Ga) layers for local precursor arrangement. The Cu(In,Ga)Se2 absorbers formed after selenization can deliver working solar devices showing efficiency enhancement under light concentration.
Laser ablation with femtosecond pulses (130 fs, wavelength 800 nm, repetition rate 2 Hz) was compared with nanosecond-pulse ablation (10 ns, wavelength 266 nm, repetition rate 2.5 Hz) of bariumalumoborosilicate glass in air using the direct focusing technique. Different ablation thresholds and heat-affected zones were observed. The lateral and vertical machining precision was evaluated. Single nanosecond laser pulses in the far UV resulted in a bubble or a circular hole in the centre of the illuminated spot, depending on the applied fluence. The ablation behaviour in the case of near-IR femtosecond pulses contrasted to this. Bubble formation was not detected. It needed repeated pulses at the same spot to modify the surface until material removal could be observed (incubation). Cavity dimensions of less than the beam diameter were achieved in this case.
Periodic self-organization of matter beyond the diffraction limit is a puzzling phenomenon, typical both for surface and bulk ultrashort laser processing. Here we compare the mechanisms of periodic nanostructure formation on the surface and in the bulk of fused silica. We show that volume nanogratings and surface nanoripples having subwavelength periodicity and oriented perpendicular to the laser polarization share the same electromagnetic origin. The nanostructure orientation is defined by the near-field local enhancement in the vicinity of the inhomogeneous scattering centers. The periodicity is attributed to the coherent superposition of the waves scattered at inhomogeneities. Numerical calculations also support the multipulse accumulation nature of nanogratings formation on the surface and inside fused silica. Laser surface processing by multiple laser pulses promotes the transition from the high spatial frequency perpendicularly oriented nanoripples to the low spatial frequency ripples, parallel or perpendicular to the laser polarization. The latter structures also share the electromagnetic origin, but are related to the incident field interference with the scattered far-field of rough non-metallic or transiently metallic surfaces. The characteristic ripple appearances are predicted by combined electromagnetic and thermo-mechanical approaches and supported by SEM images of the final surface morphology and by time-resolved pump-probe diffraction measurements.
The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of fused silica with multiple irradiation sequences of parallel polarized Ti:sapphire femtosecond laser pulse pairs (160 fs pulse duration, 800 nm central wavelength) was studied experimentally. For that purpose, a Michelson interferometer was used to generate near-equal-energy double-pulse sequences allowing the temporal pulse delay between the parallel-polarized individual fs-laser pulses to be varied between 0 and 40 ps with ~0.2 ps temporal resolution. The surface morphologies of the irradiated surface areas were characterized by means of scanning electron and scanning force microscopy. In the sub-ps delay range a strong decrease of the LIPSS periods and the ablation crater depths with the double-pulse delay was observed indicating the importance of the laser-induced free-electron plasma in the conduction band of the solids for the formation of LIPSS.
Given their unique properties, ultrashort laser pulses with durations in the femtosecond to picosecond range currently open new avenues in the field of laser materials processing, resulting in groundbreaking new applications based on laser-induced surface functionalization. This article reviews the usability of temporally distributed energy deposition via double-pulse irradiation in applications based on laser ablation. This includes simple new techniques for surface nanostructuring and improved sensitivities in spectroscopic material analyses.
The formation of laser-induced periodic surface structures (LIPSS) upon irradiation of fused silica with multiple irradiation sequences consisting of five Ti:sapphire femtosecond (fs) laser pulse pairs (150 fs, 800 nm) is studied experimentally. A Michelson interferometer is used to generate near-equal-energy double-pulse sequences with a temporal pulse delay from -20 to +20 ps between the cross-polarized individual fs-laser pulses (~0.2 ps resolution). The results of multiple double-pulse irradiation sequences are characterized by means of Scanning Electron and Scanning Force Microscopy. Specifically in the sub-ps delay domain striking differences in the surface morphologies can be observed, indicating the importance of the laser-induced free-electron plasma in the conduction band of the solids for the formation of LIPSS.
Indium islands on molybdenum coated glass can be grown in ordered arrays by surface structuring using a femtosecond laser. The effect of varying the molybdenum coated glass substrate temperature and the indium deposition rate on island areal density, volume and geometry is investigated and evaluated in a physical vapor deposition (PVD) process. The joined impact of growth conditions and spacing of the femtosecond laser structured spots on the arrangement and morphology of indium islands is demonstrated. The results yield a deeper understanding of the island growth and its precise adjustment to industrial requirements, which is indispensable for a technological application of such structures at a high throughput, for instance as precursors for the preparation of Cu(In,Ga)Se2 micro concentrator solar cells.
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.
Micro-concentrator solar cells offer an attractive way to further enhance the efficiency of planar-cell technologies while saving absorber material. Here, two laser-based bottom-up processes for the fabrication of regular arrays of CuInSe2 and Cu(In,Ga)Se2 microabsorber islands are presented, namely one approach based on nucleation and one based on laser-induced forward transfer.
Additionally, a procedure for processing these microabsorbers to functioning micro solar cells connected in parallel is demonstrated. The resulting cells show up to 2.9% efficiency and a significant efficiency enhancement under concentrated Illumination.
To save weight and resources lightweight tanks with complex geometries made of glass-fibre reinforced plastics (GFRP) are a promising innovation for the transportation of dangerous goods. To realise the use of polymer tanks for such applications, their fire safety must be guaranteed. This paper presents solutions to protect fibre-reinforced plastic tanks from fire. The fire resistance of six GFRP tanks with different fire protection systems was tested in an outdoor full-scale fire test facility according to the regulation stipulated in the ADR (European agreement concerning the national carriage of dangerous goods by road). All tanks feature a complex geometry and a holding capacity of 1100 litres. The fire protection systems are composed of specialised resins as well as two intumescent coatings. All systems had a protective impact. The best results were achieved by the epoxy based intumescent coating, which was able to prolong the time needed to reach 150 °C inside the tank by 20 min. The emergence of a temperature holding point inside the tank due to condensation effects was observed at temperatures around 100 °C.
Censorship of parts of written text was and is a common practice in totalitarian regimes. It is used to destroy information not approved by the political power. Recovering the censored text is of interest for historical studies of the text. This paper raises the question, whether a censored postcard from 1942 can be made legible by applying multispectral imaging in combination with laser cleaning. In the fields of art conservation (e.g. color measurements), investigation (e.g. Analysis of underdrawings in paintings), and historical document analysis, multispectral imaging techniques have been applied successfully to give visibility to information hidden to the human eye.
The basic principle of laser cleaning is to transfer laser pulse energy to a contamination layer by an absorption process that leads to heating and evaporation of the layer. Partial laser cleaning of postcards is possible; dirt on the surface can be removed and the obscured pictures and writings made visible again. We applied both techniques to the postcard. The text could not be restored since the original ink seems to have suffered severe chemical damage.
Laser cleaning for works of art on paper might be a supplemental, noncontact method to overcome some of the limitations of traditional dry cleaning techniques. Three different types of paper (pure-cellulose filter paper, rag paper, and wood-pulp paper) were mechanically soiled with pulverized charcoal in a standardized procedure to make model samples. These samples were characterized microscopically and by means of lightness measurements using a multi-spectral imaging system. A prototype laser workstation with Laser Class I conditions for the operator was used for the cleaning experiments. For 10-ns laser pulses at a wavelength of 532 nm, a set of laser parameters was established for a successful cleaning of the samples avoiding damage to the paper substrate. Single- and multi-pulse illumination conditions were tested. An extensive microscopic analysis after laser treatment of the cleaned parts of the samples provided insight into the remaining soiling on the surface and in the bulk of the paper material.
Laser cleaning of soiled paper is a challenging task due to the fact that a contamination has to be removed and a fragile organic material has to be preserved. The ejection of particles forms a significant channel for the removal of unwanted surface contaminations and can be exploited for an in-situ monitoring of the cleaning procedure. 532-nm-nanosecond single and multi pulse laser cleaning of artificially soiled Whatman© paper was performed. Particles were registered with a dust monitor. These in-situ experiments were combined with ex-situ investigations of cleaning and substrate damage thresholds by means of light and scanning electron microscopic techniques. The cleaning efficiency measured by a multi-spectral imaging system was compared to the in-situ particle monitoring. Additionally, possible color changes of the paper substrate were evaluated.
The influence of paper type and state of degradation on laser cleaning of artificially soiled paper
(2011)
Lasers can be a supplemental tool for restorers to overcome some of the limitations of traditional dry cleaning techniques for works of art on paper. The laser working range has to be optimized allowing for safe removal of contamination and limitation of damage to the substrate. This paper addresses the influence of paper type and state of degradation on laser working range. Three types of new paper (pure cellulose, bleached pulp paper, rag paper) were degraded and characterized with respect their degree of polymerization. Laser-induced damage thresholds of new and degraded paper were determined using SEM and viscometry. Additionally, artificially soiled model samples were made using two kinds of soiling, namely pulverized charcoal and soot-blackened standard test dust. Cleaning thresholds of soiled paper samples were evaluated. A working range for all combinations of paper and soiling between 0.05 J/cm2 and 0.5 J/cm2 was found for the application of 8-ns laser pulses at 532 nm wavelength.
Cleaning of artificially soiled paper using nanosecond, picosecond and femtosecond laser pulses
(2010)
Cleaning of cultural assets, especially fragile
organic materials like paper, is a part of the conservation
process. Laser radiation as a non-contact tool offers
prospects for that purpose. For the studies presented here,
paper model samples were prepared using three different paper
types (pure cellulose, rag paper, and wood-pulp paper).
Pure cellulose serves as reference material. Rag and woodpulp
paper represent essential characteristics of the basic
materials of real-world artworks. The papers were mechanically
soiled employing pulverized charcoal. Pure and artificially soiled paper samples were treated with laser pulses of
28 fs (800 nm wavelength) and 8–12 ns (532 nm) duration in
a multi pulse approach. Additionally, the cellulose reference
material was processed with 30 ps (532 nm) laser pulses.
Damage and cleaning thresholds of pure and soiled paper
were determined for the different laser regimes. Laser working
ranges allowing for removal of contamination and avoiding
permanent modification to the substrate were found.
The specimens prior and after laser illumination were characterized
by light-optical microscopy (OM) and scanning
electron microscopy (SEM) as well as multi spectral imaging
analysis. The work extends previous nanosecond laser
cleaning investigations on paper into the ultra-short pulse
duration domain.
Paper is one of the most important materials representing and witnessing human culture particularly as a carrier medium for text and image. As soiling hampers the reception of information, paper cleaning techniques are needed. Traditional mechanical and chemical cleaning methods are used by conservator-restorers. In some cases, a classical cleaning procedure of paper objects yields unsatisfactory results or a conventional treatment is even impossible. Especially, fragile paper objects cause problems due to mechanical instabilities. Laser cleaning as a non-contact method might be a way to overcome some of the limitations of classical cleaning techniques. Laser parameters have to be chosen to achieve removal of the soiling without influencing the artwork. Any immediate as well as long-term effects causing an irreversible change of the artwork have to be avoided. At present, most laser applications are found in stone and metal conservation, while laser treatment of complex organic materials like paper is still not fully developed for application in conservators' workshops. This contribution describes recent work of pulsed laser cleaning of soiled model samples. Pure cellulose, rag paper and wood-pulp paper were mechanically soiled with pulverized charcoal in a standardized procedure to make model samples representing essential characteristics of contaminated real-world artworks. Afterwards, model samples were cleaned using short and ultrashort laser pulses in the nanosecond and femtosecond time domain, respectively. An extensive analysis of the model samples after laser treatment using an optical microscope and a multi-spectral imaging system allows a comparison of the cleaning results obtained with both laser sources.
Titanium and its alloys are known to allow the straightforward laser-based manufacturing of ordered surface nanostructures, so-called high spatial frequency laser-induced periodic surface structures (HSFL). These structures exhibit sub-100 nm spatial periods – far below the optical diffraction limit. The resulting surface functionalities are usually enabled by both, topographic and chemical alterations of the nanostructured surfaces. For exploring these effects, multi-method characterizations were performed here for HSFL processed on Ti–6Al–4V alloy upon irradiation with near-infrared ps-laser pulses (1030 nm, ≈1 ps pulse duration, 1–400 kHz) under different laser scan processing conditions, i.e., by systematically varying the pulse repetition frequency and the number of laser irradiation passes. The sample characterization involved morphological and topographical investigations by scanning electron microscopy (SEM), atomic force microscopy (AFM), tactile stylus profilometry, as well as near-surface chemical analyses hard X-ray photoelectron spectroscopy (HAXPES) and depth-profiling time-of-flight secondary ion mass spectrometry (ToF-SIMS). This provides a quantification of the laser ablation depth, the geometrical HSFL characteristics and enables new insights into the depth extent and the nature of the non-ablative laser-induced near-surface oxidation accompanying these nanostructures. This allows to answer the questions how the processing of HSFL can be industrially scaled up, and whether the latter is limited by heat-accumulation effects.
Mixtures of hexamethyldisiloxane (HMDSO) and oxygen have been used for deposition of SiO2-like layers by plasma polymerization under low-pressure conditions onto polyethylene and polystyrene used as basecoat. Water glass was cast onto these 0.5 µm plasma thick siloxane-like layers with a thickness of 5 to 40 µm. The adhesion of these bilayer systems and their flame resistance were tested.
The effect of different plasma parameters such as monomer/gas ratio, pressure and power input into the discharge on the deposition rate and the composition of the formed layers was studied. Characterization and chemical composition of the formed films were performed using infrared, X-ray photoelectron and solid state nuclear magnetic resonance spectroscopy.
Peel strengths of composites were measured and the locus of peel front propagation was detected. Thermal properties of composites were analyzed by thermo-gravimetric analysis. Finally, the fire-retardant properties of thick coated polymers were determined by exposure to flames and the behavior of coatings on the polymers during flaming was observed visually.
Mixtures of hexamethyldisiloxane (HMDSO) and oxygen have been used for deposition of SiO2-like layers by plasma polymerization under low-pressure conditions onto polyethylene and polystyrene used as basecoat. Water glass was cast onto these 0.5 pm plasma thick siloxane-like layers with a thickness of 5 to 40 mu m. The adhesion of these bilayer systems and their flame resistance were tested. The effect of different plasma parameters such as monomer/gas ratio, pressure and power input into the discharge on the deposition rate and the composition of the formed layers was studied. Characterization and chemical composition of the formed films were performed using infrared, X-ray photoelectron and solid state nuclear magnetic resonance spectroscopy. Peel strengths of composites were measured and the locus of peel front propagation was detected. Thermal properties of composites were analyzed by thermo-gravimetric analysis. Finally, the fire-retardant properties of thick coated polymers were determined by exposure to flames and the behavior of coatings on the polymers during flaming was observed visually.
Melamine resins were used as 50-µm-thick fire retardant coatings for polypropylene (PP). Preceding deposition, low-pressure plasma polymer films of allyl alcohol were coated onto PP to improve the adhesion between PP and melamine resin coatings. The efficiency of such fire retardant coatings was confirmed by flame tests. The plasma-deposited polymer and the dip-coated melamine resin films were characterized by Fourier transform infrared-attenuated total reflectance spectroscopy and X-ray photoelectron spectroscopy (XPS). The adhesion of coatings was measured using a 90° peel test with a doubled-faced adhesive tape. To detect the locus of failure, the peeled layer surfaces were inspected using optical microscopy and XPS. Thermal properties of PP thick melamine resin-coated films were analyzed by thermogravimetric analysis.
Melamine and melamine resins are widely used as fire retardants for polymer materials used in pharmaceutical, plastic, textile, rubber, and construction industry. Melamine-based flame retardants act by blowing off intumescent layers, char formation, and emission of quenching ammonia gas and diluent molecular nitrogen. Special advantages are: low cost, low smoke density and toxicity, low corrosive activity, safe handling, and environmental friendliness. Methylated poly(melamine-co-formaldehyde) (mPMF) was used as thick (≥40 µm) fire-retardant coating for plasma pretreated polymers. A combined low-pressure plasma pretreatment consisting of oxygen plasma exposure followed by deposition of thin poly(allylamine) (ppAAm) and poly(allyl alcohol) (ppAAl) plasma polymers as adhesion promoters have improved the adhesion of thick mPMF coatings strongly. Chemical structure and composition of deposited polymer films were characterized by infrared-attenuated total reflectance and X-ray photoelectron spectroscopy (XPS). After peeling, the peeled layer surfaces were also investigated for identification of the locus of failure and their topography using optical microscopy and XPS. Often the adhesion promotion was so efficient that the peeling of coating was not possible. Thermal properties of plasma polymers and dip-coating films were analyzed by thermogravimetric analysis. Significant improvement of fire-retardant properties of coated polymers was confirmed by flame tests.