Effect of fluence on the discoloration of marble cleaned with UV lasers

The effect of fluence level on the discoloration of marble surfaces after the removal of the encrustation by 355 nm laser pulses is comparatively studied. Considering the thermochemical reaction possibly occurring in the encrustation during laser irradiation, the mechanism responsible for the discoloration of the cleaned marble surface is analyzed. The reduction of iron oxides by graphite plays a key role in determining the final color of the cleaned marble surface. A two-dimensional laser ablative cleaning model including the reaction heat is applied to calculate the temperature distribution during laser heating. The kinetics of the thermochemical reaction is estimated based on the simulated temperature field. The occurrence of the thermochemical reaction is also verified indirectly with experiments. The marble surfaces before and after laser irradiation are characterized in terms of the chemical components through surface enhanced Raman spectroscopy. The surface color is measured with a chromameter using a 1976 CIE L^*a^*b^* color system. The proposed mechanism is also applied to numerically analyze the severe discoloration of marble cleaned with laser pulses at 1064 nm.     

Patterning and morphology of nonlinear optical Gd<Subscript>x</Subscript>Bi<Subscript>1-x</Subscript>BO<Subscript>3</Subscript> crystals in CuO-doped glass by YAG laser irradiation

Dots and lines consisting of nonlinear optical Gd_xBi_1-xBO₃ crystals were patterned on the surface of CuO-doped Gd₂O₃-Bi₂O₃-B₂O₃ glass by heat-assisted (200 °C) Nd:YAG laser irradiations with a wavelength of λ=1064 nm, where the laser energy absorbed by Cu²⁺ is converted to the local heating of the surrounding Cu²⁺. The surface morphology and orientation of crystals in the patterned lines were clarified from confocal scanning laser microscope observations and polarized micro-Raman scattering spectra. Crystal lines with periodic bumps (i.e., ladder-shape like lines) were patterned by laser irradiations with a power of 0.79 W and a scanning speed of 60 μm/s, and the orientation of Gd_xBi_1-xBO₃ crystals in the lines was proposed. The present study demonstrates that the combination of Cu²⁺ and continuous wave Nd:YAG laser with λ=1064 nm is effective in inducting crystallization of oxide glasses. The mechanism of laser-induced crystallization in glass has also been discussed. PACS 61.43.Fs; 42.70.Mp; 68.35.Bs; 78.30.-j; 79.20.Ds     

Current status of astronomical observations on possible cosmological variations of the proton-to-electron mass ratio μ=m<Subscript>p</Subscript>/m<Subscript>e</Subscript>

Astronomical constraints on a possible cosmologicalvariation of the proton-to-electron mass ratio μ=m_p/m_e are discussed. The analysis of H₂ lines observed in thespectra of distant quasars Q 0405-443 (z_em=3.02) andQ 0347-383 (z_em=3.22) is performed [1] using, partly, very precise values of H₂ frequencies from new laboratorymeasurements [2] and sensitivity coefficients from newaccurate calculations [2,3]. A possibleμ-variation of Δμ/ μ= (2.0±0.6)×10^-5over 12 Gyr is not excluded. However, the discussion of systematicerrors show that some may well be underestimated. Thus, the abovevalue should be treated as the most stringent limit the cosmologicalvariation of μ at z≈2.6 - 3.0 (12 Gyr ago).     

Mechanistic comparison of pulse laser induced phase separation of particulates from cellulose paper at 213 nm and 532 nm

The laser-induced phase separation of charcoal particles on additive-free cotton linters cellulose paper was investigated by electron and optical microscopy, colorimetry, and diffuse reflectance FT-IR. The fibre bundles were vaporised in depth of several 10 μm above destruction fluence thresholds using visible 532 nm radiation. This is in contrast to mid-ultraviolet 213 nm radiation, where only the top fibre bundles were modified and partially evaporated. The colorimetric lightness results generally represented the cleaning status, whereas the colorimetric yellowing data represented irreversible chemical and/or photochemical changes. Charcoal-contaminated paper treated with visible and mid-ultraviolet radiation exhibited yellowing, whereas uncontaminated did not. This suggests that the electron-rich plasma generated by the evaporation of the particles heats the adjacent substrate and also excludes oxygen. Mid-ultraviolet, in contrast to visible radiation, shows particle removal always accompanied by paper destruction. IR spectroscopy results suggest cross-linking by ether bonds near the destruction threshold, but do not prove the formation of oxidation products and double bonds as the basis of the yellowing. A “cleaning window” between the cleaning threshold (0.1 J/cm²) and the paper destruction threshold (2.9 J/cm²) with a pulse number of 2 is provided by visible 532 nm laser treatment.     

Cleaning of artificially soiled paper with 532-nm nanosecond laser radiation

Cleaning of paper is a challenging task due to the fact that a contamination should be removed and a fragile organic original material has to be preserved. Pulsed laser cleaning of artificially soiled Whatman© filter paper samples serving as models for historical paper was performed. Different cleaning strategies employing 8-ns laser pulses at 532 nm wavelength were applied to clean paper avoiding undesired effects like discoloration (yellowing) and mechanical deterioration of the substrate. Multi shot experiments with low-energy pulses were compared with single pulse investigations utilizing high pulse energies achieving a constant energy load incident on the samples in both cases. The cleaning efficiency and possible yellowing effects were evaluated by means of a multi spectral imaging system. An extensive microscopic analysis of the cleaned parts of the samples provided insight into the remaining soiling on the surface and in the bulk of the paper material after laser treatment. As a reference, a hard and a soft eraser were used to clean the samples.     

Characterization of channel waveguides in Pr:YLiF<Subscript>4</Subscript> crystals fabricated by direct femtosecond laser writing

Single tracks and pairs of tracks are written in the volume of Pr-doped LiYF₄-crystals using tightly focused femtosecond laser radiation (λ=1045 nm, τ _p=400–500 fs, f=0.1–1 MHz). Waveguiding between the tracks is demonstrated and optimized by varying the distance between the tracks and the laser writing conditions. The stress-induced guiding mechanism is explained based on TEM, interference microscopy, near-field and far-field measurements. It is shown that the single-crystalline material is getting poly-crystalline under femtosecond laser irradiation. By measuring the lifetime of the ³P₁→³H₅ transition and the emission spectrum at excitation with λ=444 nm, no influence on these properties of the guided light is observed. This possibly enables the realization of a channel waveguide laser in the visible spectral range.     

Influence of storage time on laser cleaning of SiO<Subscript>2</Subscript> on Si

The influence of the ‘storage time’ τ_s on the threshold fluence φ_cl and the efficiency in dry laser cleaning is investigated. τ_s denotes the time between the deposition of particles and the cleaning. As a model system we employed silica spheres with diameters of 500 nm and 1500 nm on commercial silicon wafers and single-pulse KrF excimer laser radiation (τ_FWHM=28 ns). For the 1500-nm silica spheres, φ_cl was found to increase from about 65 mJ/cm² to 125 mJ/cm² for storage times of 4 h and 362 h, respectively. For 500-nm silica spheres the increase in the threshold fluence was less than 20% for storage times up to 386 h. Received: 12 July 2002 / Accepted: 12 July 2002 / Published online: 29 January 2003 RID="*" ID="*"Corresponding author. E-mail:dieter.baeurle@jku.at     

Electrical characterization of the [N(CH<Subscript>3</Subscript>)<Subscript>4</Subscript>][N(C<Subscript>2</Subscript>H<Subscript>5</Subscript>)<Subscript>4</Subscript>]ZnCl<Subscript>4</Subscript> compound

The [N(CH₃)₄][N(C₂H₅)₄]ZnCl₄ compound has been synthesized by a solution-based chemical method. The X-ray diffraction study at room temperature revealed an orthorhombic system with P2₁2₁2 space group. The complex impedance has been investigated in the temperature and frequency ranges 420–520 K and 200 Hz–5 MHz, respectively. The grain interior and grain boundary contribution to the electrical response in the material have been identified. Dielectric data were analyzed using the complex electrical modulus M ^* for the sample at various temperature. The modulus plots can be characterized by full width at half height or in terms of a non-exponential decay function ϕ(t) = exp[(−t/τ) ^β ]. The detailed conductivity study indicated that the electrical conduction in the material is a thermally activated process. The variation of the AC conductivity with frequency at different temperatures obeys the Almond and West universal law.     

Optical characterization of pigments by reflectance spectroscopy in support of UV laser cleaning treatments

The study of optical properties of artwork materials is of fundamental importance for laser-based restoration techniques. In this work, reflectance spectroscopic measurements and colorimetric analyses of painted wooden models were performed to discriminate between pigments on the basis of their spectral features. In particular, the spectral reflection factors of different white pigments were recorded with a fibre optics reflectance spectroscopy module, both before and after excimer laser (248 nm) irradiation. Colour data were obtained and monitored with an integrating sphere spectrophotometer and expressed with the CIE L^*a^*b^* colour coordinates. Moreover, the laser-induced morphological changes of the samples were investigated by scanning electron microscopy. PACS  42.62-b; 61.80.Ba; 07.60.Dq     

Initiation of combustion of a methane-air mixture in a supersonic flow behind a shock wave during laser excitation of O<Subscript>2</Subscript> molecules

The possibility of initiating detonation of CH₄ + air in a supersonic flow behind an oblique shock wave under the exposure of the mixture to laser radiation with wavelengths λ_I=1.268 μm and 762 nm is analyzed. It is shown that this irradiation leads to excitation of O₂ molecules to the a ¹Δ_g and b ¹Σ _g ⁺ states, which intensifies the chain mechanism of combustion of CH₄/O₂ (air) mixtures. Even for a small value of the laser radiation energy absorbed by an O₂ molecule (∼0.05–0.1 eV), detonation mode of combustion in a poorly inflammable mixture such as CH₄/air can be realized at a distance of only 1 m from the primary shock wave front for relatively small values of temperature (∼1100 K) behind the front under atmospheric pressure.     

Incubation in the UV irradiation of condensed CHCl<Subscript>3</Subscript> solids

Matrix-Assisted-Pulsed-Laser-Evaporation (MAPLE) has emerged as a very promising technique for the deposition of polymers and biopolymers in intact and functional form. However, our understanding of the mechanism of the procedure is still limited. Here, we examine laser-induced (248 nm) desorption from condensed CHCl₃ solid, which has been employed as a potential matrix in MAPLE. We find that the absorption of the condensed halocarbon increases significantly with successive laser pulses, as a result of the formation and accumulation of strongly absorbing products. This results in a significant increase of the ejection efficiency in the irradiation with successive laser pulses. Thus, in studies employing multi-pulse irradiation protocols, the attained laser-induced temperatures are considerably higher than what is estimated on the basis of the absorption coefficient of CHCl₃. Thus, contrary to previous suggestions, ablation of CHCl₃ frozen solid at 248 nm may be due to explosive boiling. A number of additional implications are also discussed.     

Thermo-optic coefficients of monoclinic KLu(WO<Subscript>4</Subscript>)<Subscript>2</Subscript>

The three thermo-optic coefficients of the biaxial laser host KLu(WO₄)₂ are measured at 633 nm by a deflection method. Their values at 300 K amount to ∂ n _g /∂ T=−7.4×10⁻⁶ K⁻¹; ∂ n _m /∂ T=−1.6×10⁻⁶ K⁻¹ and ∂ n _p /∂ T=−10.8×10⁻⁶ K⁻¹. Nearly athermal propagation directions are found for polarizations along the N _m and N _p dielectric axes.     

Impurity band in SnBi<Subscript>4</Subscript>Se<Subscript>7</Subscript>: thermoelectric power and electrical resistivity measurements

Thermoelectric power and electrical resistivity measurements on polycrystalline samples of Bi₂Se₃ and stoichiometric ternary compound in the quasi-binary system SnSe–Bi₂Se₃ in the temperature range of 90–420 K are presented and explained assuming the existence of an impurity band. The variation of the electron concentration with temperature above 300 K is explained in terms of the thermal activation of a shallow donor, by using a single conduction band model. The density of states effective mass m ^*=0.15m ₀ of the electrons, the activation energy of the donors, their concentration, and the compensation ratio are estimated. The temperature dependence of the electron mobility in conduction band is analyzed by taking into account the scattering of the charge carriers by acoustic phonon, optical phonon, and polar optical phonon as well as by alloy and ionized impurity modes. On the other hand, by considering the two-band model with electrons in both the conduction and impurity bands, the change in the electrical resistivity with temperature between 420 and 90 K is explained.     

Strong decays B<Subscript>s0</Subscript>→B<Subscript>s</Subscript>π and B<Subscript>s1</Subscript>→B<Superscript>*</Superscript><Subscript>s</Subscript>π with light-cone QCD sum rules

In this article, we calculate the strong coupling constants g_Bs0Bsη and g_Bs1B*sη with the light-cone QCD sum rules. Then we take into account the small η–π⁰ transition matrix according to Dashen’s theorem, and we obtain the small decay widths for the isospin violation processes B_s0→B_sη→B_sπ⁰ and B_s1→B_s ^*η→B_s ^*π⁰. We can search the strange-bottomed (0⁺,1⁺) mesons B_s0 and B_s1 in the invariant B_sπ⁰ and B^* _sπ⁰ mass distributions, respectively. PACS  12.38.Lg; 13.25.Hw; 14.40.Nd     

Irradiation of amorphous Ta<Subscript>42</Subscript>Si<Subscript>13</Subscript>N<Subscript>45</Subscript> film with a femtosecond laser pulse

Films of 260 nm thickness, with atomic composition Ta₄₂Si₁₃N₄₅, on 4″ silicon wafers, have been irradiated in air with single laser pulses of 200 femtoseconds duration and 800 nm wave length. As sputter-deposited, the films are structurally amorphous. A laterally truncated Gaussian beam with a near-uniform fluence of ∼0.6 J/cm² incident normally on such a film ablates 23 nm of the film. Cross-sectional transmission electron micrographs show that the surface of the remaining film is smooth and flat on a long-range scale, but contains densely distributed sharp nanoprotrusions that sometimes surpass the height of the original surface. Dark field micrographs of the remaining material show no nanograins. Neither does glancing angle X-ray diffraction with a beam illuminating many diffraction spots. By all evidence, the remaining film remains amorphous after the pulsed femtosecond irradiation.     

Spectroscopic properties of Nd<Superscript>3+</Superscript>:CaNb<Subscript>2</Subscript>O<Subscript>6</Subscript> crystal

The absorption spectra, fluorescence spectrum and fluorescence decay curve of Nd³⁺ ions in CaNb₂O₆ crystal were measured at room temperature. The peak absorption cross section was calculated to be 6.202×10⁻²⁰ cm² with a broad FWHM of 7 nm at 808 nm for E//a light polarization. The spectroscopic parameters of Nd³⁺ ions in CaNb₂O₆ crystal have been investigated based on Judd-Ofelt theory. The parameters of the line strengths Ω _t are Ω ₂=5.321×10⁻²⁰ cm²,Ω ₄=1.734×10⁻²⁰ cm²,Ω ₆=2.889×10⁻²⁰ cm². The radiative lifetime, the fluorescence lifetime and the quantum efficiency are 167 μs, 152 μs and 91%, respectively. The fluorescence branch ratios are calculated to be β ₁=36.03%,β ₂=52.29%,β ₃=11.15%,β ₄=0.533%. The emission cross section at 1062 nm is 9.87×10⁻²⁰ cm².     

Synchrotron and laser excitation of luminescence in PbWO<Subscript>4</Subscript>:Tb crystals at different temperatures

The effect of temperature on the spectral luminescence characteristics of PbWO₄:Tb³⁺ crystals with synchrotron and laser excitation is studied. If PbWO₄:Tb³⁺ is excited by synchrotron radiation with λ = 88 nm at 300 K, a faint recombination luminescence of the impurity terbium is observed against the matrix luminescence. When the temperature is reduced to 8 K, the luminescence intensity of PbWO₄:Tb³⁺ increases by roughly an order of magnitude and the characteristic luminescence of the unactivated crystal is observed. Excitation of PbWO₄:Tb³⁺ by a nitrogen laser at 300 K leads to the appearance of emission from Tb³⁺ ions. At 90 K, a faint matrix luminescence is observed in addition to the activator emission. The formation of the luminescence excitation spectra for wavelengths of 60–320 nm is analyzed and the nature of the emission bands is discussed.     

Diode-pumped Nd:LuVO<Subscript>4</Subscript>-Nd:YVO<Subscript>4</Subscript> laser at 492 nm with intracavity sum-frequency-mixing in LiB<Subscript>3</Subscript>O<Subscript>6</Subscript>

We present for the first time a Nd:YVO₄ laser emitting at 1064 nm intracavity pumped by a 916 nm diode-pumped Nd:LuVO₄ laser. A 809 nm laser diode is used to pump the Nd:LuVO₄ crystal emitting at 916 nm, a Nd:YVO₄ laser crystal was pumped at 916 nm and lased at 1064 nm. Intracavity sum-frequency mixing at 916 and 1064 nm was then realized in a LiB₃O₆ (LBO) crystal to reach the blue range. We obtained a continuous-wave output power of 216 mW at 492 nm under 19.6 W of incident pump power at 809 nm.     

Large optical nonlinearity in CaCu<Subscript>3</Subscript>Ti<Subscript>4</Subscript>O<Subscript>12</Subscript> thin films

CaCu₃Ti₄O₁₂ (CCTO) thin films were successfully prepared on LaAlO₃ substrates by pulsed laser deposition technique. We measured the nonlinear optical susceptibility of the thin films using Z-scan method at a wavelength of 532 nm with pulse durations of 25 ps and 7 ns. The large values of the third-order nonlinear optical susceptibility, χ ⁽³⁾, of the CCTO film were obtained to be 2.79×10⁻⁸ esu and 3.30×10⁻⁶ esu in picosecond and nanosecond time regimes, respectively, which are among the best results of some representative nonlinear optical materials. The origin of optical nonlinearity of CCTO films was discussed. The results indicate that the CCTO films on LaAlO₃ substrates are promising candidate materials for applications in nonlinear optical devices.     

Multiple-wavelength lasing by multiform self-frequency conversion in Nd<Superscript>3+</Superscript>-doped La<Subscript>2</Subscript>CaB<Subscript>10</Subscript>O<Subscript>19</Subscript> crystals

The self-sum-frequency process was firstly demonstrated in Nd³⁺-doped La₂CaB₁₀O₁₉ (LCB) crystal. In addition, simultaneous participation of the fundamental laser in multi-self-frequency conversion including the self-frequency doubling was reported. Emissions at five different wavelengths (525, 529, 533.6, 1050 and 1069 nm) were simultaneously obtained. The output power of the three green visible lasers (525, 529 and 533.6 nm) generated by multi-self-frequency-conversion of the fundamental laser is up to 26.64 mW, and the light-light conversion efficiency is up to 4.85%. The lasers at 525 and 529 nm are very close to the green primary color G (526.3 nm) defined by the 1964CIERGB system, which has potential applications in laser-based high brightness display. The large frequency differences of 4–6 THz between 525 and 529 nm, 529 and 533.6 nm, as well as 1050 and 1069 nm, are also potential useful in generating THz waves by difference frequency generation (DFG) technique in a nonlinear optical (NLO) crystal.