Fixation of bioactive calcium alkali phosphate on Ti6Al4V implant material with femtosecond laser pulses

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.     

Laser ablation of polysulfone films: a laser ionization TOF mass spectrometric study

2 . Major peaks were assigned to direct fragments and recombination products ejected from the PS surface. The arrival profiles of these ablation products varied from product to product and were fitted by using a shifted Maxwell–Boltzmann distribution with a center-of-mass flight velocity [(1.4-5.6) ×10⁵ cm/s] and a Knudsen layer temperature (350–3810 K). Two types of ablation products, whose velocities and temperatures showed different dependences on laser fluence, were found to exist. Dynamical aspects in the decomposition of the polymer chain, the ejection of various fragments, and their expansion are discussed on the basis of a photothermal ablation model, where a heated surface layer with a temperature gradient along its depth plays an important role. Received: 11 August 1998/Accepted: 12 August 1998     

Time-resolved plasma diagnostics and mass removal during single-pulse laser ablation

Laser ablation processes occurring over several orders of magnitude in time were investigated by using time-resolved spectroscopy, shadowgraphs and interferograms. A picosecond ablation plasma was measured with an electron density on the order of 10²⁰ cm^-3 originating from the breakdown of air. The longitudinal expansion of this plasma was suppressed due to the development of a strong space-charge field. At post-pulse times, the lateral (radial) expansion of the plasma was found to follow the relation, r~t^1/2, consistent with the expansion from an instantaneous line source of energy. The electron number density and temperature were deduced by measuring spectroscopic emission-line broadening during the early phase (30-300 ns) of a mass (atomic/ionic) plasma. These properties were measured as a function of the delay time and irradiance. Possible mechanisms such as inverse bremsstrahlung and self-regulation were used to describe the data before an explosion threshold of 20 GW/cm². The laser self-focusing and critical temperature are discussed to explain dramatic changes in these properties after the irradiance threshold. On the microsecond time scale, the surface explodes and large (>7m) particles are ejected. Mass removed from single-crystal silicon by high power (10⁹-10¹¹ W/cm²) single-pulse laser ablation is studied by measuring the crater morphology. Time-resolved shadowgraph images show that the rapid increase in the crater depth at the threshold corresponds to large-size droplets leaving the surface. This rapid growth of the crater volume is attributed to explosive boiling.     

Dynamics of femtosecond-laser-ablated liquid-aluminum nanoparticles probed by means of spatiotemporally resolved X-ray absorption spectroscopy

We investigated spatiotemporal evolution of expanding ablation plume of aluminum created by a 100-fs, 10¹⁴–10¹⁵-W/cm² laser pulse. For diagnosing dynamic behavior of ablation plume, we employed the spatiotemporally resolved X-ray absorption spectroscopy (XAS) system that consists of a femtosecond-laser-plasma soft X-ray source and a Kirkpatrick–Baez (K–B) microscope. We successfully assigned the ejected particles by analyzing structure of absorption spectra near the L _II,III absorption edge of Al, and we clarified the spatial distribution of Al⁺ ions, Al atoms, and liquid droplets of Al in the plume. We found that the ejected particles strongly depend the irradiated laser intensity. The spatial distribution of atomic density and the expansion velocity of each type of particle were estimated from the spatiotemporal evolution of ablation particles. We also investigated a temperature of the aluminum fine particles in liquid phase during the plume expansion by analyzing the slope of the L _II,III absorption edge in case of 10¹⁴-W/cm² laser irradiation where the nanoparticles are most efficiently produced. The result suggests that the ejected particles travel in a vacuum as a liquid phase with a temperature of about 2500 to 4200 K in the early stage of plume expansion.     

Analysis of surface and material modifications caused by laser drilling of AlN ceramics

For the laser drilling of aluminum nitride ceramic the processing results and the effects related to pulsed irradiation were investigated. Images of the drilled surface revealed regular, cylindrically shaped holes of about 100 μm in diameter independently of the laser wavelength (1064/532/355 or 266 nm). The holes were surrounded by circular heat-affected zones of larger diameter. A comparison of the elemental compositions of the original material and the processed one indicated a decrease of the nitrogen concentration in the affected area. The spectral analysis of the ablated material composition revealed the presence of ions and neutrals in dependence on the laser intensity applied. It was found that at intensity values close to the ablation threshold the ejected material consisted mainly of neutrals, while doubling of the intensity resulted in appearance of single-ionized Al species, which were also observed together with Al clusters in the mass spectra of the UV-excited plasma. Their prevailing content was revealed for drilling at higher intensities around 15 GW/cm² at 532 nm. Results of model calculations indicated, in agreement with the experiment, that at the threshold the ceramic decomposes into gaseous nitrogen and solid Al particulates, while at a higher fluence the material particles vaporize and influence the quality of drilling.     

Considerations on the determining factors of the angular distribution of emitted particles in laser ablation

Simulations of particles which are emitted in laser ablation have been performed by the method of Direct Simulation Monte Carlo to investigate the deposition profiles of the emitted particles. The influences of the temperature, pressure and stream velocity of the initial evaporated layer formed during laser ablation process on the profile of the deposited film have been examined. It is found that the temperature gives a minor influence on the deposition profile, whereas the stream velocity and the pressure of the initial evaporated layer have a greater impact on the deposition profile. The energy in the direction of surface normal (E_⊥) and that in the parallel direction of the surface (E_||) are shown to increase and decrease, respectively after the laser irradiation due to collisions between the emitted particles, and this trend is magnified as the pressure increases. As a consequence, the stream velocity in the direction of surface normal increases with the increase in the pressure. A mechanism of the phenomenon that a metal with a lower sublimation energy shows a broader angular distribution of emitted particles is presented. It is suggested that low density of evaporated layer of a metal with a low sublimation energy at its melting point decreases the number of collisions in the layer, leading to the low stream velocity in the direction of surface normal, which results in the broader deposition profile of the emitted particles.     

Aluminum thin film enhanced IR nanosecond laser-induced frontside etching of transparent materials

Laser processing of glass is of significant commercial interest for microfabrication of precision optical engineering devices. In this work, a laser ablation enhancement mechanism for microstructuring of glass materials is presented. The method consists of depositing a thin film of aluminum on the front surface of the glass material to be etched. The laser beam modifies the glass material by being incident on this front-side. The influence of ablation fluence in the nanosecond regime, in combination with the deposition of the aluminum layer of various thicknesses, is investigated by determining the ablation threshold for different glass materials including soda-lime, borosilicate, fused silica and sapphire. Experiments are performed using single laser pulse per shot in an air environment. The best enhancement in terms of threshold fluence reduction is obtained for a 16 nm thick aluminum layer where a reduction of two orders of magnitude in the ablation threshold fluence is observed for all the glass samples investigated in this work.     

等离子屏蔽效应下飞秒激光照射金箔的分子动力学模拟

采用耦合了双温度模型的分子动力学方法对飞秒激光烧蚀金箔的传热过程进行了模拟研究,考虑了非傅里叶效应,探究了不同激光能流密度下等离子体羽流的屏蔽作用.根据密度分布将激光烧蚀过程中的金箔划分为过热液体层、熔融液体层和固体层,并比较了不同激光能量密度下过热液体层表面发生的相爆炸沸腾现象以及表面温度的变化情况.结果表明,随着激光能量密度的增大,等离子体的屏蔽比例几乎呈线性增大.在激光的烧蚀过程中,金箔的上表面最先经历液体层以及过热液体层,并且随着时间的推移,液体层和过热液体层逐渐向金箔底部移动.过热液体层发生体积移除的相爆炸沸腾是金箔烧蚀的主要方式,随着激光能量的增大,爆炸沸腾发生的时间提前,并且结束的时间相应延后,持续时间变长.     

Plasma-mediated ablation of biofilm contamination

Ultra-short pulsed laser removal of thin biofilm contamination on different substrates has been conducted via the use of plasma-mediated ablation. The biofilms were formed using sheep whole blood. The ablation was generated using a 1.2 ps ultra-short pulsed laser with wavelength centered at 1552 nm. The blood contamination was transformed into plasma and collected with a vacuum system. The single line ablation features have been measured. The ablation thresholds of blood contamination and bare substrates were determined. It is found that the ablation threshold of the blood contamination is lower than those of the beneath substrates including the glass slide, PDMS, and human dermal tissues. The ablation effects of different laser parameters (pulse overlap rate and pulse energy) were studied and ablation efficiency was measured. Proper ablation parameters were found to efficiently remove contamination with maximum efficiency and without damage to the substrate surface for the current laser system. Complete removal of blood contaminant from the glass substrate surface and freeze-dried dermis tissue surface was demonstrated by the USP laser ablation with repeated area scanning. No obvious thermal damage was found in the decontaminated glass and tissue samples.     

Non-contact subsurface temperature measurements following mid-infrared laser irradiation

A difficult challenge in laser processing at nanosecond time scales is monitoring substrate temperature in the laser focal volume, particularly for mid-infrared laser irradiation where the absorption depth is relatively large and the attained temperatures are often relatively low. Here, we describe time-dependent measurements of the subsurface temperature of a target material following absorption of pulsed mid-infrared (MIR) laser irradiation, by detecting the luminescence from micron-size ceramic phosphor particles (Gd-doped YAG:Ce) embedded in the target material at a concentration of up to 10 %. Temperature calibrations were obtained by measuring the luminescence decay of the probe particles in an oil-bath heater. A silica-nanoparticle film was irradiated by an Er:YAG laser operating in a free-running mode over a fluence range up to but below the ablation threshold, while the third harmonic of the Nd:YAG laser excited the luminescence of the probe particles. From the temperature calibrations, it was possible to infer the thermal history of the target as a function of time delay between the Er:YAG and Nd:YAG laser pulses.     

Silicon cluster formation in the laser ablation of SiO at 308 nm

Neutral silicon cluster formation in the laser (308 nm) ablation of silicon monoxide was investigated through the analysis of composition and dynamics of the ablation plume under different laser fluence conditions. The neutral species were ionized by a second laser (193 nm) and the positionized species detected by TOF-MS (time-of-flight mass spectrometry). At low laser fluences, plume composition is dominated by SiO; above 0.6 J/cm² Si, SiO and Si₂ have comparable intensity and Si_n (n≤7) clusters are observed. Flow velocities and temperatures of the ejected species are nearly mass-independent, indicating that the plume dynamics are close to the strong expansion limit, implying a collisional regime. Through the relation between the estimated values of terminal flow velocity and surface temperature, u_T²∝T_S, it is found that, at low laser fluences, the surface temperature increases linearly with laser fluence, whereas, at the laser fluence at which Si_n clusters are observed, the increase of temperature is below the linear dependence. The population distribution of the ejected Si_n provides some indication of a formation mechanism based on condensation. Analogies between the ablation behavior of silicon monoxide and silicon targets are considered. PACS 82.30.Nr; 81.05.Gc; 78.70.-g     

Formation of silver nanoparticles with dielectric shell on the silver-containing glass during laser evaporation and ablation

We demonstrate a new method of silver nanoparticles formation on a silver-containing glass surface due to its irradiation by a pulsed CO₂ and YAG:Nd lasers. The particles are formed as a result of reduction of silver ions from the glass at the edges of a laser torch emerging during evaporation and ablation. The settled particles are then fixed on sample surface by a shell of glass dielectric components. The method allows creating plasmonic nanostructures on the glass surface for sensing applications.     

The influence of substrate temperature on femtosecond laser micro-processing of silicon,stainless steel and glass

We report the influence of substrate temperature on femtosecond laser ablation of silicon, stainless steel, and glass. Remarkable decrease in surface roughness was observed under high substrate temperature for silicon and stainless steel. While the ablation efficiency of glass as a typical wide band-gap material is scarcely altered at 900 K, the efficiency for stainless steel as a conductor apparently increased about 20% accompanied to the elevation of substrate temperature from 300 to 900 K. Silicon wafer results in slight increase of the ablation efficiency with decreasing the ablation threshold. Considering that the melting temperature of glass is much lower than those of silicon and steel, the observations from this work suggests that the material ablation caused by the ultrafast laser irradiation could not be explained in term of only laser-induced thermal excitation.     

Laser opto-acoustic study of phase transitions in metals confined by transparent dielectric

First-order phase transitions in metal induced by nanosecond laser pulse are studied here. The metal surface is irradiated through a layer of transparent dielectric??an optical glass. Such confinement considerably increases the efficiency of pressure generation at the metal surface. This technique allows to obtain near-critical states of metals??with temperatures ??10⁴ K and pressures ??10⁴ atm with table-top equipment. At the same time the glass prevents the ablation plume formation??so the surface temperature can be measured using thermal radiation data. An experimental setup for simultaneous measurements of pressure, temperature and reflectivity was assembled based on the elaborated method of experimental research. The processes of melting of lead and boiling of mercury were studied. The onset of the phase transition process led to a considerable tightening of the pressure pulse. A substantial drop of surface reflectivity due to increase of temperature and decrease of density was observed.     

Nanospallation induced by an ultrashort laser pulse

A femtosecond laser pulse with power density of 10¹³ to 10¹⁴ W/cm² incident on a metal target causes ablation and ejection of the surface layer. The ejected laser plume has a complicated structure. At the leading front of the plume, there is a spall layer where the material is in a molten state. The spall layer is a remarkable part of the plume in that the liquid-phase density does not decrease with time elapsed. This paper reports theoretical and experimental studies of the formation, structure, and ejection of the laser plume. The results of molecular dynamics simulations and a theoretical survey of plume structure based on these results are presented. It is shown that the plume has no spall layer when the pulse fluence exceeds an evaporation threshold F _ev. As the fluence increases from the ablation threshold F _a to F _ev, the spall-layer thickness for gold decreases from 100 nm to a few lattice constants. Experimental results support theoretical calculations. Microinterferometry combined with a pump-probe technique is used to obtain new quantitative data on spallation dynamics for gold. The ablation threshold is evaluated, the characteristic crater shape and depth are determined, and the evaporation threshold is estimated.     

Phase explosion and recoil-induced ejection in resonant-infrared laser ablation of polystyrene

We investigate the phenomenon of resonant-infrared laser ablation of polymers using polystyrene as a model material. Ablation is carried out using various mid-IR laser wavelengths that are resonant with vibrational modes of a polystyrene target. Time-resolved plume imaging coupled with etch-depth measurements and thermal calculations indicate that ablation begins after a superheated surface layer reaches a temperature of ∼1000°C and undergoes spinodal decomposition. The majority of the ablated material is then expelled by way of recoil-induced ejection as the pressure of the expanding vapor plume compresses a laser-melted area.     

Large area laser surface micro/nanopatterning by contact microsphere lens arrays

Laser surface micro/nanopatterning by particle lens arrays is a well-known technique. Enhanced optical fields can be achieved on a substrate when a laser beam passes through a self-assembled monolayer of silica microspheres placed on the substrate. This enhanced optical field is responsible for ablative material removal from the substrate resulting in a patterned surface. Because of the laser ablation, the microspheres are often ejected from the substrate during laser irradiation. This is a major issue impeding this technique to be used for large area texturing. We explored the possibility to retain the spheres on the substrate surface during laser irradiation. A picosecond laser system (wavelength of 515 nm, pulse duration 6.7 ps, repetition rate 400 kHz) was employed to write patterns through the lens array on a silicon substrate. In this experimental study, the pulse energy was found to be a key factor to realize surface patterning and retain the spheres during the process. When the laser pulse energy is set within the process window, the microspheres stay on the substrate during and after laser irradiation. Periodic patterns of nanoholes can be textured on the substrate surface. The spacing between the nanoholes is determined by the diameter of the microspheres. The depth of the nanoholes varies, depending on the number of laser pulses applied and pulse energy. Large area texturing can be made using overlapping pulses obtained through laser beam scanning.     

Pulse laser ablation at water–air interface

We studied a new pulse laser ablation phenomenon on a liquid surface layer, which is caused by the difference between the refractive indices of the two materials involved. The present study was motivated by our previous study, which showed that laser ablation can occur at the interface between a transparent material and a gas or liquid medium when the laser pulse is focused through the transparent material. In this case, the ablation threshold fluence is reduced remarkably. In the present study, experiments were conducted in water and air in order to confirm this phenomenon for a combination of two fluid media with different refractive indices. This phenomenon was observed in detail by pulse laser shadowgraphy. A high-resolution film was used to record the phenomenon with a Nd:YAG pulse laser with 10-ns duration as a light source. The laser ablation phenomenon on the liquid surface layer caused by a focused Nd:YAG laser pulse with 1064-nm wavelength was found to be followed by the splashing of the liquid surface, inducing a liquid jet with many ligaments. The liquid jet extension velocity was around 1000 m/s in a typical case. The liquid jet decelerated drastically due to rapid atomization at the tips of the ligaments. The liquid jet phenomenon was found to depend on the pulse laser parameters such as the laser fluence on the liquid surface, laser energy, and laser beam pattern. The threshold laser fluence for the generation of a liquid jet was 20 J/cm². By increasing the incident laser energy with a fixed laser fluence, the laser focused area increased, which eventually led to an increase in the size of the plasma column. The larger the laser energy, the larger the jet size and the longer the temporal behavior. The laser beam pattern was found to have significant effects on the liquid jet’s velocity, shape, and history.     

Laser fluence, repetition rate and pulse duration effects on paint ablation

The efficiency (mm³/(J pulse)) of laser ablation of paint was investigated with nanosecond pulsed Nd:YAG lasers (λ = 532 nm) as a function of the following laser beam parameters: pulse repetition rate (1-10,000 Hz), laser fluence (0.1-5 J/cm²) and pulse duration (5 ns and 100 ns). In our study, the best ablation efficiency (η ≅ 0.3 mm³/J) was obtained with the highest repetition rate (10 kHz) at the fluence F = 1.5 J/cm². This ablation efficiency can be associated with heat accumulation at high repetition rate, which leads to the ablation threshold decrease. Despite the low thermal diffusivity and the low optical absorption of the paint (thermal confinement regime), the ablation threshold fluence was found to depend on the pulse duration. At high laser fluence, the ablation efficiency was lower for 5 ns pulse duration than for the one of 100 ns. This difference in efficiency is probably due to a high absorption of the laser beam by the ejected matter or the plasma at high laser intensity. Accumulation of particles at high repetition rate laser ablation and surface shielding was studied by high speed imaging.     

Chromium carbide thin films deposited by ultra-short pulse laser deposition

Pulsed laser deposition performed by a laser with a pulse duration of 250 fs has been used to deposit films from a Cr₃C₂ target. Due to the different processes involved in the laser ablation when it is performed by an ultra-short pulse source instead of a conventional short pulse one, it has been possible to obtain in vacuum films containing only one type of carbide, Cr₃C₂, as shown by X-ray photoelectron spectroscopy. On the other hand, Cr₃C₂ is not the only component of the films, since a large amount of amorphous carbon is also present. The films, deposited at room temperature, are amorphous and seem to be formed by the coalescence of a large number of particles with nanometric size. The film composition can be explained in terms of thermal evaporation from particles ejected from the target.