Chapter 2.

Principles of Laser Cleaning in Conservation

Salvatore Siano Istituto di Fisica Applicata Nello Carrara, Consiglio Nazionale delle Ricerche, Sesto Fiorentino, Italy

Contents
2.1.1 Introduction 2.1.2 Historical Note 2.1.3 Laser Systems and Parameters 2.1.4 Linear Laser-Material Interaction 2.1.4.1 Absorption and Scattering 2.1.4.2 Laser Heating 2.1.4.3 Photoacoustic Effects 2.1.5 Non-linear Interaction Effects 2.1.6 Note on Laser Induced Plasma 2.1.7 Ablation Channels 2.1.7.1 Ablation Rate 2.1.8 Conclusive Note 2.1.9 References 2.1.10 Contact Information

2.1.1

Introduction

The properties of monochromaticity, collimation, and coherence of laser light and the associated interaction features have favoured the development of a variety of applications in several fields, such as for examples industrial [1-3], biomedical [4-6], and cultural heritage [7-9]. A general distinction between applications not involving relevant and permanent physical changes to the irradiated material and the ones producing irreversible modifications can be done. The former are usually aimed at characterisation purposes, whereas the latter include both diagnostic and processing techniques. Laser ablation is one of the most important irreversible irradiation effect (see for example [10,11], and the other Proceedings of the COLA Conferences), which can be induced on optically absorbing materials or in their close proximity. Laser cleaning is a particular case of laser ablation where a specific material layer or substrate is uncovered through the removal of undesired layers or incoherent particle distributions. Laser cleaning processes are exploited in different fields. Thus for examples, besides the conservation of artworks discussed in the following, it is being used in a number of industrial needs, such as semiconductors cleaning in microelectronics, die cleaning in plastic pressure casting, paint stripping in the aircraft maintenance, and other. Even some laser surgery treatments, such as for example the removal of tattoos, can be classified as a cleaning application. The first observation of the laser ablation and cleaning phenomena dates back to the origins of laser technology [12,16]. Significant advancements on the understanding of the physical mechanisms through systematic phenomenological studies and the diagnostics of the laser-material interaction were achieved starting from beginning eighties. The main results were provided by researches related with medical surgery and microelectronic industry, which resulted of fundamental importance also in other fields of application including the present one. After a short historical note, the following paragraphs report a brief review of the basic mechanisms involved in the laser cleaning process in the restoration of art and historical artefacts. It is based on the suitable framing of the general achievements mentioned above within the present application domain and on the specific insights related with important conservation problems that were approached by laser during the last

decade.

2.1.2

Historical Note

The application of the laser cleaning in the conservation of artworks was proposed by J.F. Asmus since the beginning of seventies [17-19] through a set of practical tests carried out in Venice on encrusted stone artefacts. As reported by the involved conservation scientists and restorers [20-23], the novel approach did not overcome the experimental stage for several years mainly because of the technological limits of the pulsed laser sources available at that time: Ruby and Nd:YAG lasers with low pulse repetition rate, absence of versatile beam delivery systems, very low reliability for long time operations, and high costs. During the eighties the technological level of the laser devices increased significantly but the costs still were out of scale for the specific field of application, even more whether considering the relatively low productivity, as compared with traditional chemical and mechanical cleaning techniques. The surviving of the novel conservation approach for more than a couple of decades, against unfavourable performances along with the caution, scepticism, or indifference of the most of the conservation community, has to be completely attributed to the perseverance of Asmus and his co-workers [24-30]. Mainly thanks to the stimulus provided to the research of innovative technologies dedicated to the study and safeguard of cultural heritage by European Framework Programmes and various National Innovation Programs, the situation drastically changed during the nineties. Several research centres, conservation institutions, and restoration enterprises initiated constructive interactions aimed at developing laser systems and methodologies dedicated to different classes of materials and deterioration problems. Up to 1995 the scientific results were reported in some conservation meetings, disciplinary congresses, and journals without the possibility of real interdisciplinary debates and experience exchanges on the topic [18-49]. The institution of the international conference LACONA (Laser in the Conservation of Artworks) [50] held for first time in Crete (1995) has represented a very important step for consolidating and refining the positive results already achieved on encrusted stone and extending the application to other conservation problems by increasing the scientific level and improving interdisciplinary approach. The conference has become a fundamental reference for the development and dissemination of the laser techniques in the conservation field. Physical investigations on the laser cleaning processes of stones, metals, paintings, paper, parchment etc., and thorough evaluations of the irradiation effects were reported throughout the six editions of the LACONA conference [50-54] held up to now. In recent years, two more congresses were born within the disciplinary context of the applied optics dedicated to the application of laser techniques in conservation (SPIE conference Laser Techniques and Systems in Art Conservation Munich 2001-05 [55-57] CLEO 2005 Symposium on: Laser technology for the preservation of cultural heritage). Furthermore, specific sessions on the topic started to be included in congresses on laser technology and applications (International workshop on: New trends in laser cleaning 2001-05, COLA 2003 [10], and other). Some contributions can be also found in the proceedings of interdisciplinary conferences such as Science and Technology for the Safeguard of the Cultural Heritage in the Mediterranean Basin (since 1995 [58]), International Congress on Deterioration and Conservation of Stone, and other. The gradual acceptance within the scientific and conservation communities of what can be defined as a kind of revolution in the conservation procedures is also documented by the increasing number of studies published in various applied physics, applied chemistry, and interdisciplinary journals. Anyway, as a result of this collective effort, which involved the scientific community of many countries, the most important advancement is represented by the transition of laser techniques from the laboratory experimentation to the everyday practice of important conservation institutions and restoration enterprises. Along the last decade Italy is having a leading role in this acceptance and dissemination process. Laser techniques are being used in the Opificio delle Pietre Dure (OPD), the Istituto Centrale del Restauro (ICR) and other important conservation institutions, as well as in private organisations, and by some tens of restoration enterprises on a large variety of conservation problems. Thus for example, eight different laser systems are presently used in the laboratories of OPD, Florence, where a number of problems encountered in the restoration of Renaissance masterpieces have been solved by optimised laser treatments. From this exploitation standpoint, important results were achieved during the last fifteen years in France, Austria, Spain, and Portugal, for the restoration of stone sculptural elements in historical faades and monuments, in England for museum collections, in Holland for the first applications on paintings, and more recently in Greece on ancient marble masterpieces and wall paintings. Furthermore, promising developments are registered in Croatia and Slovenia where conservation institutions and some restoration enterprises, in

collaboration with research centres, are starting to use laser methodologies in their restoration works. There are no special recipes to speedup the acceptance and dissemination process. The only effective ways are the ones based on rigorous approaches to the material characterisation, physical evaluation, and validation associated with specific conservation objectives, whose definition pass through a strict interaction of the scientific component with the historical, artistic, and management ones. The present section aims at providing a first introductory picture of the main physical phenomena, which should be taken into account for optimising laser cleaning treatments, while the state of the art for the various materials and conservation problems is summarised in some details in the next sessions of this chapter.

2.1.3

Laser Systems and Parameters

Only pulsed lasers are used in the cleaning of art and historical objects. Up to a few year ago, the most employed systems in stone cleaning were based on Q-Switching (QS) Nd:YAG lasers emitting at the fundamental harmonic (1064 nm) pulses of typical duration of 8-20 ns and energies between 0.1-1 J/pulse. Usually, also the Free Running (FR) regime is available on these commercial laser systems providing pulse durations of 200-500 s and higher pulse energies up to 2 J but, as explained in the following, this range of pulsewidth is not effective for the most of the cleaning problems. A novel class of Intermediate Pulse Duration (IPD) Nd:YAG lasers was proposed and commercialised in the last years. These systems are based on Short Free Running (SFR) and Long Q-Switching (LQS) regimes providing pulse duration between 50 ns-3 s and 20-120 s, respectively, with similar energies as FR and QS lasers [59-60]. IPD laser systems are always fibre-coupled (1 mm typical core diameter) and equipped with versatile handpieces providing very homogeneous and a finely controllable irradiation spot. The market also offers QS lasers coupled into relatively thick fibres (1.5 mm core diameter). The output energy from a single fibre is limited to around 200 mJ because of damage risks due to the very high intensity and associated non-linear absorption phenomena (optical breakdown). Only a few of these systems are presently in use, whereas the most of commercialised QS laser systems are coupled in an articulated arm, which allows to propagate higher pulse energies (up to 1 J) but with a low beam quality because of possible hot spots and fringe structures usually associated with Nd:YAG laser beams. The handpieces have a lower spot control and versatility with respect to fibre optical beam deliveries. The success of this class of systems is due to the relatively high cleaning efficiency, which favoured their employ for cleaning intervention on relatively large areas. During the last years the mentioned limits along with the problem of yellow appearance associated with the cleaning of whitish substrates [61-63] have significantly slowed the commercial spread and hence the use of QS systems, which provided room to a relevant penetration of the market by the SFR lasers, which was favoured by a number of basic studies and successful example applications [47,63-71]. Multi-wavelength QS Nd:YAG laser systems were also proposed for overcoming the problem of the yellow appearance and to approach the cleaning of wall paintings. In particular, positive results were documented for the second harmonic (532 nm) [71-74] and the combination of first and third harmonics [75]. Despite the higher technological complexity and costs of the multi-wavelength lasers, which are big obstacle to a wide spread, it is worth nothing that the double wavelength solution was successfully applied to clean sculptural elements of the frieze of the Parthenon [76]. Two more class of lasers were proposed for the cleaning of paintings through extensive laboratory tests and some practical applications. They are KrF excimer laser (248 nm, around 30 ns) and FR Er:YAG (2.94 m, 250 s) [77-80]. Different order of problems, concerning side effects and for the former also costs and lack of portability, are preventing the acceptance and widespread of cleaning treatment based on these laser systems. The present perspective appears hence not so promising. Even less whether considering the positive results recently achieved by Nd:YAG laser systems [74, 81-85] that already dominate the present field of application.

2.1.4

Linear Laser-Material Interaction

Laser ablation of a material stratification is a strongly non-linear process occurring when the irradiation

fluence (pulse energy per unit area: F0 = E/A) or in some cases intensity (peak power per unit area: I0 = P/A) overcomes a critical threshold, which is an intrinsic property of the material structures under irradiation. In the domain of interest fluence and intensity are usually expressed in mJ/cm2 (m=10-3) or J/cm2 and MW/cm2 or GW/cm2 (M = 106, G = 109), respectively. The dynamical development of the laser ablation involves optical, photothermal and photomechanical phenomena depending on the laser parameters and material properties. In order to understand the different ways in which pulsed laser irradiation can produce material removal, it is useful to introduce separately these different phenomena starting from their linear regimes occurring at relatively low fluences, i.e. significantly lower than the critical ones for inducing any irreversible effect to the irradiated material.

2.1.4.1

Absorption and Scattering

The incidence of a laser beam on a material (here and elsewhere if not specified differently the material is assumed to be homogeneous) is accompanied by absorption and scattering phenomena producing attenuation and spatial redistribution (diffusion) of the beam energy. In the case of a layer of dielectric material (as for examples black crust, whitewashes etc.), it is useful distinguishing among back scattered, absorbed, and forward-scattered radiation and to introduce the reflectance (R=Er/E), absorbance (A=Ea/E), and transmittance (T=Et/E) parameters of the material layer (Fig. 2.1.1): (1) When irradiating thick or very absorbing materials T 0, but in practical cases of adjacent material layers, often the transmittance must be taken into account in the energy balance (Fig. 2.1.1c). The flux of energy, which propagates into the material, F, undergoes to a typical exponential attenuation law along the optical axis, z: (2) where Fa=(1-R)F0 and is the effective absorption coefficient, whose reciprocal represents the optical penetration depth = 1 / , also named optical extinction length. It is the length of the optical path along the z-axis, which produces an attenuation of the energy flux at the material surface Fa of a factor 1/e.

For very absorbing material = 1/a, where a is absorption coefficient, whereas at the opposite limit, when the propagation is dominated by the scattering, the diffusion approximation provides the following

expression: (3) where s is the scattering coefficient, g the anisotropy parameter, which represents the integral average of cos on the scattering phase function. These are fundamental parameters of the material depending on its composition and microstructure, as well as on the laser wavelength . The penetration parameter allows estimating the irradiated (or absorption) volume, V=d , where d is the laser spot diameter. For visible and near infrared wavelength the typical values of range from several nanometres of a metal, to 10-100 m of a fairly homogeneous black crust or a brown patination, up to several millimetres of calcite or gypsum. When the thickness of the irradiated material layer, l, is lower than it could be useful to consider = l. Fig. 2.1.1 displays a qualitative representation of the energy re-distribution in homogeneous material layers in the case of absorption (Fig. 2.1.1a) and scattering limits (Fig. 2.1.1b), along with a composite situation of an absorbing layer on a diffusing substrate (Fig. 2.1.1c). Anyway, in cases of practical interest the irradiated material layers are strongly inhomogeneous. Thus besides the mentioned approximation limits also their superposition within the same layer must be taken into account as possible description of the optical propagation regime. Fig. 2.1.2 shows qualitative examples of optical propagation into real stratigraphies where the outer layer is absorbing (Fig. 2.1.2a), diffusing (Fig. 2.1.2b) or both (Fig. 2.1.2c).

Despite the strong variability that can be encountered from zone to zone of the same artefact or also within the depth of a relatively thick stratification and the difficulty to determine the real energy distribution, as well as to measure a, s, and phase function, useful estimations of the irradiation effects can be derived from relatively simple reflectance and transmittance measurements (Fig. 2.1.3). These allow measuring EA, the absorption volume, and hence the energy density inside the material ( = EA /V expressed in J/cm3), which is the fundamental parameter for any irreversible phenomenon associated with the laser irradiation.

Table 2.1.1 reports the results of the reflectance measurements in dry and wet conditions for two stone typologies: white Siena marble and a yellow-brown Pliocene sandstone. The wet condition is of great interest in laser cleaning of art and historical stone artefacts, since for the most of the cases the water assists, usually performed using common atomisers, provides clear advantages in terms of effectiveness and efficiency of the treatment. The two stones are representative of reflective and absorbing stones, respectively. Table 2.1.1: Examples of reflectance measurements of stone quarry samples and fragments from historical facades of Siena: OP334 - Logge del Papa, OP 205 - Baptistery, ER 151 - Palazzo Spannocchi. SAMPLE OP 334, black crust on white Siena marble OP 205, black crust on white Siena marble Quarry sample of Siena marble ER151, black crust on Pliocene sandstone Quarry samples of Pliocene sandstone BLACK CRUST CLEANED SURFACE Rdry, Rwet [%] 11, 8 Ca-oxalates film 48, 29 20, 14 21, 13 Ca-oxalate film 39,32 Sulphated surface: 46, 30 STONE SUBSTRATE Rdry, Rwet [%] 69, 49 69, 49 64, 40 38, 25 40, 27

As it can be seen, the samples from historical faades exhibit a significant increase of reflectance while stepping from the black crust, to the underlying layer (Ca-oxalates film or surface sulphation). This optical feature is very useful in laser cleaning treatments since it favours a self-terminating behaviour of the laser ablation within relatively wide operative fluence ranges. Anyway, as stated above, the most important parameter for any induced effect is energy density realised into the irradiated materials, . Thus, beside high R, the self-termination is also favoured by high . For the white marble of Table 2.1.1 both conditions are realised, being dry = 3.3 0.5 mm and wet = 5.8 0.5 mm, as estimated by calculating a and s from the Kulbelka-Munk parameters and direct measurement of the scattering phase function [66]. Conversely, for Pliocene sandstone direct transmission measurements (Fig. 3c) provided dry=150 m and wet=180 m. Hence, the cleaning of this stone will be relatively more critical, as verified by irradiation tests [65]. As shown by reflectance and penetration measurements, the wetting of the irradiated surface produces and increase of both A and parameters. For the present examples the two effects are balanced, the wetting

does not produces a relevant variation of the energy density within the irradiated volumes (i.e. wet dry). On the other hand water assists plays an important thermal role.

2.1.4.2

Laser Heating

In the most of the cases the absorbed energy Ea is dissipated through the thermal channel, whereas only at high irradiation intensities or short VUV wavelengths also the direct ionisation and molecular photodissociation can play an important role. Hence, the main direct effect of the laser irradiation is a temperature rise within and in proximity of the irradiated volume. Theoretical estimations of the thermal distributions induced in homogeneous materials can be derived through the heat conduction equation [86] under the assumption of constant optical and thermal parameters. This hypothesis holds whenever the temperature peak are lower than the critical ones for any irreversible phenomenon (discoloration, carbonisation, vaporisation etc.). Let us consider a homogeneous laser beam of intensity I(t) incidents on the surface of a semi-infinite conductive material and a surface photothermal conversion of the absorbed energy (=0). The onedimensional solution of the conduction equation allows achieving the temperature rise T induced by the intensity Ia(t)=(1-R)I0(t):

(4) where K and D are the thermal conductivity and diffusivity of the material, respectively. D=K/Cp, with and Cp density and specific heat of the material. Besides the material parameters the use of eq. 4 requires the knowledge of the temporal profile of the laser pulse. As a first approximation it can be often assumed as Gaussian in the nanoseconds range and top-hat for longer pulse durations. For this latter case the expression of the surface temperature assumes the following well-known form:

(5) where is the laser pulse duration (FWHM). As a general behaviour this equation states that the surface temperature increases when the pulse duration decreases, which is particularly important in the cleaning of metal artefacts. As an example Fig. 2.1.4 reports the temperature rise at gold-air interface provided by equations 4 for Gaussian profiles and Fa = 0.15 J/cm2. As it can be seen, the temperature peak decrease from 454 C to 148 C when the pulse duration increases from 6 ns to 100 ns, which corresponds to a scaling law around -0.4, only slightly different from the -1/2 dependence associated with top-hat pulses (eq. 5). The parameter representing the heat propagation into the material is the thermal diffusion length: (6) For top-hat laser pulses, it is the propagation distance of the thermal wave producing an attenuation of the peak temperature to about 0.1 of the maximum surface value. Fig. 2.1.5 displays the thermal diffusion length of copper, sandstone, limestone, and water. Considering for example =200 s (FR lasers) eq. 6 provides zth=305, 38, 30 and 11 m, respectively.

Laser irradiation is indicated as thermally confined whenever zth << , or also << th where:

(7) is thermal relaxation time, representing the transit time of the thermal wave throughout the irradiated volume along the optical axis. In this condition the thermal effects are strictly circumscribed within the irradiated volume. The temperature rise in an absorbing material (s << a) is provided by energy balance:

(8) When considering the ideal case of a homogeneous insulating material, the thermal confinement condition usually represents a good approximation for pulse duration up to the microseconds range, whereas only for a few materials, as for example pure black carbon or graphite, the conduction limit can provide useful estimations. On the other hand, relatively complex features are expected in real stratifications similar to the one of Fig. 2.1.2c because of the superposition of the conduction and confinement regimes described above. Furthermore, also the thermal role of water should be taken into account in water-assisted conditions. In porous materials, such as the one encountered in deterioration stratifications, the wetting produces a relevant reduction of peak temperature within the irradiated volume since the imbibitions improves the thermal conduction and increases the average specific heat. To complete these introductory notes on the photothermal effect it is useful to mention also the possibility of cumulative heating occurring whenever the pulse repetition rate, f, is too high for allowing a complete thermal relaxation within the time interval between two consecutive laser pulses. The saturation temperature rise generated by cumulative heating is proportional to the average power Pav=f E and inversely proportional to the laser spot radius, r:

(9) At the operative fluences of SFR lasers for black crust removal from white marble this contribution could start to be not negligible above 10-20 Hz. Thus for examples direct temperature measurements during 80 s irradiation of aged white marble provided an inferior limit of the saturation temperature of 130 C [8]. In general the cumulative heating should be avoided or at least minimised in order to reduce the risks of thermal side effects such as discoloration, structural damages due to thermal dilatation, and other.

2.1.4.3

Photoacoustic Effects

Pulsed irradiation can generate acoustical transients, which propagates into the irradiated materials structures along distances much larger than and zth. The basic mechanisms can be very different depending on the physical properties and laser parameters. For solid absorbing materials laser intensities of order of 106-108 W/cm2 the photoacoustic effect is usually originated by the thermoelasticity. All the materials in different extents exhibit a volume variation when heated, which is reversible within specific temperature and pressure range, i.e. thermoelasticity domains. The parameter characterising the effect is the thermal expansion coefficient, , representing the relative volume variation produced by unit temperature variation. Laser irradiation with pulse duration short enough to realise the thermal confinement condition ( << th) generates fast thermal transients within the irradiated volume and hence associated pressure rises. This produces a pressure wave, which propagates into the medium with a quasi-sonic speed.

The general problem of the thermoelastic generation in homogeneous absorbing materials can be approached through the classical method of the Green function [87-89]. Two different solutions are determined for rigid (r) and free (f) boundary conditions, respectively:

(10)

(11) where is delayed time, the thermoelastic transfer function, and c the sound speed into the material. These formulas show the strong dependence of the peak pressure on the laser pulse duration, appearing both as inverse proportionality and through the intensity Ia. Fig. 2.1.6 displays qualitatively the development of pressure transients for the two boundary conditions. As described above, the compression phase is generated by thermal expansion whereas the development of a rarefaction phase in free boundary condition is due to the reflection of the compression wave at the solid-air interface. The acoustical reflection coefficient is defined as:

(12) where Zaw = a,m ca,m are the acoustic impedances of air and solid material, respectively. Since it is Zm >> Za eq. 11 provides Ra c -1, that corresponds to a total reflection at the water-air interface, which is accompanied by a phase inversion producing the rarefaction peak described by eq. 11. The transit time along the distance is named elastic relaxation time, el:

(13) If <el, the pressure into the irradiated volume increases along the whole laser pulse duration since the elastic relaxation occurs at longer times. This defines the inertial or pressure confinement condition, which gives rise to a high-pressure gradient at the interface. In principle, this condition can be realised when using short pulse duration (ex. a few nanoseconds) on materials exhibiting relatively large optical penetrations (ex.

several tens of microns).

2.1.5

Non-Linear Laser-Material Interaction

The increase of the laser fluence or intensity produces the transition to non-linear interaction regimes resulting in microscopic and macroscopic irreversible changes to the irradiated material structures, which invalidate the description of the optical, thermal, and mechanical features reported above. The extreme stage is represented by the generation of a multiphase flow including solid particles, vapour, gas, and in some cases also a plasma phase, which characterises the so called ablation plume. Before approaching the description of the different possible ablation channels let us list some of the main non-linear interaction effects, which are involved at sufficiently high fluence or intensity levels. Variation of the macroscopic parameters Discoloration, optical trapping, and atomic scale effects are responsible for significant variations of the optical parameters, For amorphous solids a temperature rise usually produces an increase of K and D, The thermal expansion coefficient depends on the temperature, Porosities, surface roughness, microfractures and other structural features can affect in different extend the description of the laser induced effects based on macroscopic material parameters, Laser induced structural modifications can produce strong non-linear effects, Material removal is an efficient cause of cooling of the material substrate. It produces strong discontinuities in the optical, thermal and mechanical propagation phenomena. Atomic and molecular scale Multiphoton absorption, Saturation of specific absorption bands, Photodissociation, Photoionisation, Plasma formation.

2.1.6

Note on Laser-Induced Plasma

Plasma is a macroscopically neutral gaseous phase where a relevant fraction of particles (of order of 10% or more) is ionised. Laser irradiation of absorbing materials at high intensity (above 108 W/cm2) can induce the onset of plasma in proximity of the surface through the so-called optical breakdown phenomenon [90]. It develops from a number of initial electrons, mostly generated by multiphoton ionisation of atoms and molecules. The energy of these free electrons is increased by absorption of incident photons (inverse bremsstrahlung) up to the ionisation energy levels, thus driving an avalanche multiplication. Depending on the intensity and temporal profile of the laser pulse, after some or several nanoseconds the electron density reaches values of order of 1018-1020 cm-3 and the electron temperatures rises up to 104 K [91]. The plasma plume is very opaque at long wavelength, such as the ones on CO2, Er:YAG and Nd:YAG lasers, being the plasma optical extinction length p (1/)2. Thus for example, if Te=15000 K and ne=1020 cm-3 the analytical estimation at =1064 nm returns p=15 m, against typical plasma sizes 1 mm. Hence dense plasma acts as an effective optical shielding while any further effect to the irradiated material is mostly mediated by the complex fluid dynamic processes associated with the plasma expansion. In the practical cases of laser cleaning, plasma formation can occur when using short QS Nd:YAG lasers (ex. 5 ns) at relatively high fluences and hence intensity (ex. 3 J/cm2, 6 108 W/cm2) to remove hard or weakly absorbing stratifications. Anyway, these operative conditions are often ineffective and harmful for the integrity of the substrate. Whereas, at the typical operative fluences (0.5-1 J/cm2) in water assisted

conditions, the occurrence of a dense plasma phase is unlike, even though some not significant ionisation phenomena, favoured by inhomogeneous beam and strongly absorbing components (hot spots and black carbon particles), could accompany the ablation dynamics [92]. Similarly, no dense plasma is expected for cleaning with LQS and excimer lasers because of the low operative intensities. For example the maximal operative fluence in stone and metal cleaning with LQS Nd:YAG laser pulses of 20-120 ns is around 3 J/cm2, which corresponds to 2.5-15 107 W/cm2, while excimer laser removal of varnishes is carried out around 0.5 J/cm2 (about 1.7 107 W/cm2). SFR lasers at fluences as high as 20-30 J/cm2 can produce the formation of rarefied plasma, which is optically thin and hence does not influence significantly the ablation dynamics driven by direct laser-material interaction [64].

2.1.7

Ablation Channels

A general scheme of the different laser ablation channels is reported in Fig. 2.1.7, for pulse duration ranging between a few nanoseconds up to hundreds of microseconds. Let us distinguish ablation occurring below and above the vaporisation threshold of the irradiated material. At fluences below the minimum one for vaporisation the only possible ablation mechanisms are of photomechanical type, apart from the special case of VUV wavelengths, where the direct molecular bond breaking can provide a relevant contribution. The two main channels are based on pressure confinement (<el), where the impulsive ejection is generated by the high-pressure gradient at the interface, and primary spallation [93-94] occurring when the rarefaction peak exerts a strength larger than the specific breaking load of the material. These two channels are very interesting for laser cleaning applications because they involve moderate temperatures and are very efficient. In real cases of inhomogeneous multilayer stratifications, the mechanisms of the photomechanical ablation gets rather more complex. They include coherent superposition effects of pressure transients generated at the absorption centres, secondary and water mediated spallation. These latter two mechanisms are frequent in cleaning applications. As schematically illustrated in Fig. 2.1.8, in secondary spallation a relevant part of the radiation is absorbed underneath the outer layer of the irradiated stratification, which is removed by interface pressure development in thermoelastic or vaporisation regimes. Instead the concept of water-mediated spallation aims at representing the significant role of water assists in the mechanical coupling and propagation of the pressure wave. Above the vaporisation threshold only fast thermal explosion induced by laser pulses in the nanoseconds range is the most properly called laser ablation, where the thermal confinement is usually assumed as rigorously verified, but in the present concern it is useful to extend the concept to plasma-mediated material removal, of importance in some specific high intensity treatment, and to quasi-continuum vaporisation produced by SFR and FR Nd:YAG lasers. Fast thermal explosion and plasma-mediated ablation are usually characterised by fluid dynamic regimes and strong recoil stresses released to the material surface [95-98]. For pulse duration in the order of microseconds, pure vaporisation and plasma channels do not exhibit strong differences because, as mentioned above, the plasma phase is expected to be very rarefied. For this reason in Fig. 2.1.7 they were merged in a single channel. The front of the ablation plume proceeds with a quasi-sonic speed, so it cannot drive a shock wave and then a significant recoil stress [64]. Finally, not thermally confined (>th) slow vaporisation is the ablation mechanism at pulses duration of 200-500 s, usually provided by commercial Nd:YAG laser systems.

2.1.7.1

Ablation Rate

The ablation rate represents the single pulse efficiency of the laser removal at a given fluence. It is usually measured in g/pulse or m/pulse, while the ablation efficiency in g/Jcm-2/J or g/Jcm-2. The knowledge of the dependence of the ablation rate on laser fluence is of practical importance in order to precisely control the removal of the stratification. The typical behaviour for ablation above the vaporisation threshold is the one reported in Fig. 2.1.9a, where the fluence and rate scales were arbitrarily assumed as the ones of the experimental data of Fig. 2.1.9b.

Laser ablation starts to be observed above the minimum fluence Fth named ablation threshold. Above this value the removal is almost linear up to the saturation fluence Fs, indicating where the efficiency is significantly reduced by dissipative phenomena as in particular ionisation and plasma formation. The maximum efficiency is achieved at the intermediate fluence Fm. The maximum rate in a pure vaporisation regime is equal to the optical penetration depth, . The so-called blow-off model provides a theoretical estimation of the rate curve [99]. It is based on the assumption the material is immediately removed when the laser heating overcomes the critical energy density of the irradiated material, cr, which allows achieving the following estimation of the ablation rate and threshold:

(14) The condition zabl= allows determining the saturation fluence Fs=Fth 3Fth, which can be considered as a limit operative fluence. Equations 13 are derived under the assumption of thermal confinement, i.e. from eq. 2 and eq. 8. It is important to note that in the present approximation Fth does not depend on the laser pulse duration. Conversely, for long pulses > th) eq. 5 (conduction limit) provides the following expression:

(15) which shows a dependence on pulse duration of type . Thus for example if Fth is the ablation threshold at 50 s, the threshold at 500 s will be 3.3 Fth. The strong reduction of efficiency explains why long pulses are rarely used in laser cleaning.
1/2

For real stratifications it is useful to introduce concepts like cleaning fluence of cleaning threshold Fcl, which is the minimum laser fluence providing the desired cleaning result in self-terminated cleaning treatments, since Fth can exhibit strong variations from point to point and within the stratification depth. Anyway, their

fluence and pulse duration dependence are still roughly estimated by eqs. 14 and 15.

2.1.8

Conclusive Note

In this section we provided an introductory description of the main physical concerns involved in the lasers cleaning of artworks. Several insights on the various topics and examples of application aimed at optimising specific laser cleaning treatments can be found in the following sections and in the reported literature. At the same time it is worth noting that further studies are needed in order to provide thorough quantitative descriptions of the interaction dynamics occurring in real inhomogeneous multilayer stratifications.

2.1.9
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2.1.10

Contact information

Istituto di Fisica Applicata Nello Carrara Consiglio Nazionale delle Ricerche Sesto Fiorentino Italy E: s.siano@ifac.cnr.it