The Use of Electrochemical Impedance Spectroscopy in the Evaluation of Coatings for Outdoor Bronze L.A. Ellingson,TJ. Shedlosky, G.P.

Bierwagen, E.R. de la Rie and L.B. Brostoff Electrochemical impedance spectroscopy (EIS) is a technique that quantitatively measures the amount of corrosion protection provided by a coating to a metal sub strate. This article illustrates the theory of EIS along with its potential for application in the evaluation of protective coatings for outdoor bronze sculptur e and ornamentation. Three coating systems were evaluated on a monumental cast b ronze: a microcrystalline wax; the methyl methacrylate copolymer sold under the trade name Incralac; and an acrylic/acrylic methane topcoat. Each coating system was aged using accelerated weathering and evaluated via EIS. This information wa s then used to calculate the impedance modulus of the samples, which is displaye d in Bode plots and interpreted in terms of coating performance. INTRODUCTION Continuing efforts to protect bronze works of art from the hazards of the outdoo r environment are vital endeavors in the fields of conservation and conservation science [110]. The use of clear coatings is an important option in the protectio n of bronze. Although protective coatings delay the onset of corrosion, their ef fectiveness varies greatly. An effective method to evaluate and compare the degr ee of corrosion protection afforded by different coatings is electrochemical imp edance spectroscopy (EIS). Electrochemical techniques for the quantitative evaluation of coatings on metall ic substrates have been in use for many years [1114]. EIS has been used extensive ly in corrosion research throughout the past two decades, and is a valuable tech nique for monitoring the performance of various coatings on bronze [15, 16]. Rec ently, Carullo et al. described the potential for use of an in situ EIS instrume nt that would allow corrosion monitoring of works of art [17]. In anticipation o f such a tool, EIS is shown in this paper to aid in the evaluation of the coatin g performance of model samples of coated bronze subjected to accelerated weather ing in simulated laboratory conditions. The following discussion encompasses a d etailed introduction to the theory of EIS, as well the interpretation of EIS dat a gathered from select samples that were created at the National Gallery of Art in Washington DC as part of a broader research study into new protective coating s for bronze [24]. ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY Theory Electrochemical impedance spectroscopy is a technique that determines a numerica l value for the degree of corrosion protection provided by a coating to a metal substrate. This numerical value is called the impedance of the coating and is de fined as the ability of the coating to resist or oppose corrosion through a comb ination of barrier and adhesive properties. The more the coating protects the un derlying metal, the higher the impedance value. Impedance values typically range from 1 x 10 ohms to as low as 100 ohms. The lower limit is defined as the imp edance, or resistance, of the metal substrate and is dependent on the chosen mat erial. Thus the impedance of bronze is not comparable to the impedance of aluminum. The substrate impedance can be determined by simply testing an uncoate d sample. This value is then defined as the failure point for any coated samples . The impedance data are usually not illustrated in the form of a bar graph but, for explanation purposes, Figure 1 displays the information that impedanc e spectroscopy provides. The impedance of a sample can be explained through the concepts of current and v oltage. Webster's Dictionary defines current as a 'moving stream of electricity' , but more specifically it is the rate of flow of positive charge. Current (1) p

asses through an object as shown in Figure 2; current is expressed in amperes. Voltage (E) is defined as the potential difference (AE) between two points and i s expressed in units of volts. The potential can be described as the driving for ce for the electrochemical reactions. Electrochemical reactions will occur more readily as the potential gradient becomes greater. Figure 3 illustrates the pote ntial difference that exists between two planes within an object where a current , I, is flowing [18]. Both current and voltage are used to determine the impedance of an electrochemic al cell. EIS data are collected using a three-electrode cell that consists of a reference, counter, and working electrode. The working electrode is the sample o f interest being studied, while the reference electrode may be, for example, a s aturated calomel electrode, as used in this study. No current, or electricity, f lows through the reference electrode. Instead it only serves as a reference with a known and constant potential. The third element in the electrochemical cell is the counter electrode, to which the current is allowed to flow. Initially the open circuit potential is determined and is defined as the voltage between the reference electrode and the working electrode. A sinusoidal voltage with an amplitude of 110 mV is then applied to the electrochemical cell with resp ect to the open circuit potential; this results in a sinusoidal current response . Whatever current is necessary to maintain the potential difference will flow t hrough the electrochemical cell between the working electrode and counter electr ode. The sinusoidal current that flows through the cell is out of phase with the sinusoidal potential. In-phase behavior only occurs in a pure resistor. A 90 lag ging of the current only occurs for a pure capacitor. A capacitor is an electron ic circuit element that has the ability to store charge. Because a coated sample contains both resistive and

Figure 1 Bar graph illustrating information determined by electrochemical im pedance spectroscopy (EIS).

Figure 2

Illustration of current flow.

Figure 3

Illustration of voltage.

capacitive elements, the phase shift of the current and the potential will resid e between 0 and 90. This sinusoidal behavior is illustrated in Figure 5. The impedance of a sample is determined from information provided by these two s inusoidal curves. The sample is scanned over a range of frequencies () and over a period of time (t). The impedance (denoted as Z) can be determined according to equation 1, shown below:

where |E0| and |I0| are the amplitudes of the AC voltage and current respectivel y, ft) is the angular frequency, and v and 1 are the phase angles of the voltage a nd current respectively. The impedance modulus (denoted as | Z |) is equal to the following:

The impedance modulus, | Z |, incorporates both in-phase and out-or-phase impeda nce information. | Z | is defined by using the imaginary forms of impedance as s een in equation 3.

where i = -l and = the phase angle between the real and imaginary axis. Impedance data are normally illustrated in Bode plots, with log impedance modulu s (| Z |) shown versus log frequency (CO) of the imposed sinusoidal signal. Bode plots are one way of graphing EIS data to interpret the data further. Experimental conditions The samples used in this work were designed and coated at the National Gallery o f Art, as part of a broader research project [24]. The elemental composition of t he cast, polished, monumental bronze was 85% copper, 5% lead, 5% zinc and 5% tin . This bronze alloy was chosen because it is generally representative of metals that have been used in outdoor bronzes [4]. The substrate was coated in a cleane d, degreased state. Once received at North Dakota State University, initial impe dance measurements were taken, and samples were subsequently cycled weekly betwe en an ultraviolet weathering chamber and a fog/humidity chamber in accordance wi th ASTM D 5894-96 Standard Practice for Cyclic Salt Fog/UV Exposure of Painted M etal (Alternating Exposures in a Fog/Dry Cabinet and a UV/Condensation Cabinet). The ultraviolet weathering chamber (QUV) consisted of four hours of exposure to 340 nm UV-A light at 60C. alternated with four hours of condensation at 50C. The use of accelerated weathering chambers has been debated in numerous publicat ions, but currently this method has been found to correlate fairly well to typic al outdoor exposure [19]. It was shown in a previous study that the cyclic Prohe sion corrosion testing correlates well with real-world testing [2()|. There are a number of advantages to accelerated weathering versus outdoor exposure. The fi rst obvious advantage is that the experimental time is drastically reduced. The second is that the weathering scheme can be reproduced. As pointed out by Jacque s, no period of natural weathering can be reproduced precisely to provide equiva lent weathering conditions for samples tested at different time periods [21]. On e disadvantage of accelerated aging is that many replicate specimens are needed to construct a representative data set. Because of variations in sample preparat ion, multiple samples should be considered mandatory. A second weakness is that the corrosion process is only representative of what occurs naturally. Accelerat ed aging will not produce all of the same corrosion products found in natural ex posures nor can it reproduce all of the variations of outdoor weathering. The ma jor goal of accelerated weathering is to reproduce and increase those stresses w hich have been

Figure 4

Schematic diagram of electrochemical cell used in EIS.

shown to cause most failures in outdoor exposure. Accelerated weathering usually will tell whether a coating will provide object protection for some finite, but often uncertain, period of time in outdoor weathering. The following week, samp les underwent exposure in the fog/humidity chamber (called a Prohesion chamber) to an environment that cycled between one hour of salt fog at 25C and one hour of no fog at 35C. The salt fog used for weathering was dilute Harrison solution (0. 35 wt% (NH4)2SO4 and 0.05 wt% NaCl in H2O). This solution has been shown to emul ate acid rain exposure [18]. EIS analysis of the protective coatings on the monumental bronze samples was de termined through application of an alternating voltage of 5 mV. The electrochemical cell consiste d of a saturated calomel reference electrode and a platinum mesh counter electro de that were immersed in dilute Harrison solution. The electrolyte was kept in c ontact with the working electrode sample by using an O-ring clamp with an area o f 7.0 cm2. A Gamry PC3 potentiostat with CMS 100 software was used to collect th e data over the frequency range of 0.1 to 5000 Hz. Impedance measurements were m ade at regular intervals during the weathering regime. The results of the impeda

nce measurements that are reported in this paper were taken from a single sample . Subsequent work has verified these results with multiple samples [5].

Figure 5 Sinusoidal potential and current behavior for EIS Impedance plots A portion of the data that were collected in this study is exhibited here as an illustration of how EIS can be effectively used in evaluating various coating sy stems. The Bode plot in Figure 6 shows the impedance of the uncoated bronze, whi ch maintains its value of ~300 ohms at low frequency over the period of 14 days of accelerated weathering exposure. This value thus represents true failure of a coating over bronze, i.e., the point at which a coating no longer provides corr osion protection. Higher impedance values of a coated sample would imply that th e coating system provides protection to the metal substrate. However, if corrosi on forms underneath the coating, a higher impedance value will result, as the co rrosion acts as an additional barrier layer. Hence the development of corrosion needs to be monitored as well as the impedance. Coatings for the protection of bronze are currently in use throughout the world. Two of the most popular types of coatings used in the United States are waxes a nd the methyl methacrylate copolymer coating sold under the name Incralac [2-10] . The latter coating is sometimes applied with an additional wax topcoat. Waxes are considered to be high-maintenance coatings, since they should be reapplied o r renewed at least once a year [24-26]. Figure 7 shows a Bode plot of impedance data from a monumental bronze plaque pretreated with the corrosion inhibitor ben zotriazole (BTA) (1.5% in ethanol), rinsed, and brush-coated with a blend of 75% Bareco Victory Wax (a microcrystalline, synthetic, low melting point wax), plus Bareco Polywax 2000 and 500 (both polyethylene microcrystalline waxes), and Pet ronauba C (an oxidized polyethene wax) [24]. Two coats of the wax mixture were ap plied by brush, followed by light buffing. The measured coating thickness was le ss than 50 m [2, 3|. The data indicate that the coating system initially showed s ome corrosion resistance but, after only 14 days of accelerated exposure conditi ons, the impedance of the coated sample was approximately the same value as the uncoated bronze. This value was assigned as the point of failure for this system . The rise in impedance after the first day of exposure is probably due to the f act that the system was not in the steady state at that time, but came to local equilibrium with the immersion solution by the second day. The Bode plot in Figure 8 displays impedance data for a bronze sample coated wit h Incralac and a topcoat of wax, the same wax mixture as used previously. The In cralac was prepared as a 60 wt% solution in xylene and sprayed onto the panels a s recommended by the manufacturer. The thickness of the Incralac plus wax topcoa t was measured to be 15 x 2.5 m [2, 3]. The data show that the impedance of this coating was initially much higher than that of the BTA-pretreated, wax-coated sa mple, and remained so over a period of about 112 days of accelerated weathering. Ultimate failure was approached at 140 days, and is seen as a gradual drop in t he impedance modulus. This drop, which commenced

Figure 6

EIS Bode plot of uncoated bronze sample.

Figure 7

Bode plot of benzotriazole pretreatment + wax over bronze.

after about eight days, corresponds to a gradual decrease in the protective prop erties of the coating. Incralac coatings, as typically applied to bronze in cons ervation treatments, are generally considered to provide adequate protection for

about three to five years [6, 10, 27]. Therefore, the 140-day period of acceler ated weathering may correlate roughly to this time-frame in natural outdoor expo sure. Although this coating may not be thought of as a high-performance coating, the impedance data show that the Incralac coating greatly outperforms the wax coating as applied and weathered in this study. In order for a coating to be categorized as 'high performance' it should maintai n high impedance values for a longer duration of time than seen with the Incrala c on bronze samples. Data for one coating that fulfilled this requirement are sh own in Figure 9. This novel coating is a three-part system: Nikolas acrylic 115 65,

Figure 8

Bode plot of Incralac + wax coating over bronze.

Figure 9 Bode plot of Nikolas acrylic 11565 + Nikolas acrylic urethane 9778 + wax coating over bronze. followed by Nikolas acrylic urethane 9778, and top-coated with a wax [24]. This h igher performance coating was chosen because of its chemistry and potential for a longer lifetime and better protection. The un-thinned acrylic was sprayed onto the surface in a single coat, on top of which a 50% solution of the acrylic ure thane in a recommended thinner was then spray-applied. The resultant coating thi ckness was measured to be 40 x 7.5 u.m [2, 3]. Failure of this coating did not a ppear to commence until about 98 days of exposure. Corrosion was evident after t hat period and is shown by the gradual decrease in the impedance modulus to fail ure approached at about 252 days of accelerated exposure. The low frequency impedance values shown in Figures 69 are also plotted in a bar graph format (Figure 10) in order more easily to compare the overall behavior of the three coatings on bronze as studied by EIS. This figure shows that the Incr alac and acrylic/ acrylic urethane coatings initially showed good barrier

Figure 10

Bar graph illustrating impedance variations between samples.

properties, whereas the wax coating initially provided only limited resistance. The bar graph also indicates that the overall time to ultimate failure for the t hree coatings was significantly different: the durability of the acrylic/acrylic urethane coating was almost double that of the Incralac coating, and almost 20 times greater than the wax coating. This indicates that the Acrylic/ acrylic ure thane coating, as applied in this study, provided the greatest corrosion prote ction of the coatings studied by EIS. EIS is thus shown to be an enormously usef ul tool in the ranking, as well as in the relative service-life prediction, of c oatings on a metallic substrate. CONCLUSIONS Electrochemical impedance spectroscopy is a valuable method for quantitatively d etermining the overall protective ability of various coating systems. Three coat ings on bronze, as analyzed by EIS and the resulting Bode plots, show various de grees of progressive failure as the impedance values approached that of an uncoa ted substrate over different periods of time. The quantitative information obtai ned from these plots illustrates a significant difference in protection provided by wax, Incralac + wax, and an acrylic/acrylic urethane coating on monumental b ronze. Quantitative information such as this can be used to aid in the investiga tion of new protective coatings for outdoor bronze, as well as to aid decisions

about existing coating options in outdoor bronze conservation. The value of this application could furthermore be greatly enhanced in the future by the developm ent of commercially available, in situ electrochemical impedance spectrosco py instruments for use in the field. ACKNOWLEDGEMENTS This work was made possible by funding from the National Center for Preservation Technology and Training fund MT-2210-9-NC-20. MATERIAL SUPPLIES [ncralac was obtained from StanChem, Inc., 401 Berlin Street, East Berlin, CT 06 023, USA. Nikolas Acrylic 11565 and Nikolas acrylic urethane 9778 is produced by G.J. Niko las & Co.. Inc., 2800 Washington Blvd. Bellwood, IL 60104, USA. The wax used in this study is a typical recipe blend used by American conservators. REFERENCES 1 Van Zelst, L., and Lachevre, }., 'Outdoor bronze sculpture: problems and proce dures of protective treatment', Technology and Conservation 8 (1983) 18-24. 2 Brostoff, L., and de la Rie, R., 'Research into protective coating systems for outdoor bronze sculpture and ornamentation. Phase IV, PTT Publications No. 199923, National Center tor Preservation Technology and Training, Natchitoches, Loui siana (1999). 3 Brostoff, L., Shedlosky, T., and de la Rie, R., 'Research into protective coat ing systems for outdoor bronze sculpture and ornamentation. Phase III', PTT Publ ications No. 2000-05, National Outer for Preservation Technology and Training, N atchitoches, Louisiana (2000). 4 BrostofF, L.B., and de la Rie, E.R., 'Research into protective coating system s for outdoor bronze sculpture and ornamentation' in 1.0. MacLeod, S.L. Pennec an d L. Robbiola (eds), Metal 95, James & James, London (1995) 242-244. 5 Bierwagen, G.P., Ellingson, L., and Shedlosky, T., "Development and testing of organic coatings for the preservation of outdoor bronze sculpture from air-poll utant enhanced corrosion', PTT Publications No. 2001-08, National Center for Pre servation Technology and Training, Natchitoches, Louisiana (2001). 6 Scott, D., Copper and Bronze in Art Corrosion, Colorants, Conservation, G etty Publications, Los Angeles (2002). 7 Montagna, D., 'Caring for outdoor bronze sculpture', Cultural Resources Manag ement 18 (1995) 26-28. 8 Riss, LX, 'Managing the care of outdoor metal monuments by the National Park Service: Some past experience and future direction' in V.N. Naude (ed.). Sculp tural Monuments in an Outdoor Environment, Pennsylvania Academy of the Fine Arts . Philadelphia (1983) 29-38. 9 Kipper. P.V., The Care of Bronze Sculpture, 2nd edn, Path Publications and Rodgers & Nelsen, Loveland (1998). 10 Weil, P.0., 'The conserva tion of outdoor bronze sculpture: a review of modern theory and practice' in Pre prints of Papers Presented at the Eighth Annual Meeting, San Francisco, 1980, Am erican Institute for Conservation of Historic and Artistic Works, Washington DC (1980) 129-140. 1 I Bierwagen, G.P., Jeffcoate, C, Li, J., Balbyshev, S., Tallman, D.T., and Mil ls, D.J., 'The use of electrochemical noise methods (ENM) to study thick, high i mpedance coatings', Progress in Organic Coatings 29 (1996) 21-29. 12 Bierwagen, G.P., Tallman, D.E., Li, J., Balbyshev, S., and Zidoune, M., 'El ectrochemical noise studies of aircraft coatings Over A12024-T3 in accelerated e xposure testing' in Corrosion 2000, NACE International, Houston (2000) paper 427 . 13 Hunter, C.N., Osborne, J.H., and Taylor, S.R., 'Electrochemical screening tes t for corrosion protective aerospace coatings for A12024-T3', Corrosion 56 (2000

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North Dakota State University. Address: Department of Polymers & Coatings, North Dakota State University, 1735 NDSU Research Park Drive, Fargo, ND 58105-5376, U SA. Email: tara,shcdlosky@ndsu.nodak.edu GORDON P. BIERWAGEN received his BS in chemistry and mathematics from Valparaiso University and his PhD in physical chemistry from Iowa State University. After post-doctoral work in chemical engineering at the University of Minnesota, he wo rked in the paint and coatings industry until 1989, when he joined the Departmen t of Polymers & Coatings at North Dakota State University in Fargo, as professor . His research interests have been in the physical chemistry of coatings and coa ting materials, pigment dispersion and dispersion stability, pigment particle pa cking in coating films, corrosion control by coatings, and coating lifetime pred iction and its testing. Since 1999 he has been Chair of Polymers & Coatings, and editor-m-chief of Progress in Organic Coatings since 1995. Address as for Shedl osky. Entail: gordon.bierwagen@ndsu.nodak.edu E. RENE HE LA RIE received MS and PhD degrees in chemistry from the University o f Amsterdam, The Netherlands. He has been head of the scientific research depart ment at the National Gallery of Art in Washington DC since 1989, where artists' methods and materials as well as materials used in the treatment of works of art are being studied. Before coming to the National Gallery of Art, he held positi ons at the Metropolitan Museum of Art, New York, and at the Training Program for Conservators and the Central Research Laboratory for Objects of Art and Science , both in Amsterdam. He has held adjunct positions at the University of New York and the University of Amsterdam. He has been an editor for Studies in Conservat ion since 1994. Address: Scientific Research Department, National Gallery of Art , 6th and Constitution Avenue NW, Washington, DC 20565, USA. Email: rdelarie@fs i.com LYNN B. BROSTOFF received her Ali from Vassar College, MA in art history and Cer tificate of Con-servation from the Institute of Fine Arts at New York University , MS in polymer materials science from the University of Cincinnati, and PhD in chemistry (conservation science) from the University of Amsterdam, The Netherlands. After leaving the scientific research department at the National Gallery of Art in Washington, DC in 1998, she held a position as se nior staff scientist at the Research Center on the Materials of the Artist and C onservator (Carnegie Mellon University), and is currently a staff scientist at t he Smithsonian Center for Materials Research and Education. Address; SCMRE, 4210 Silver Hill Road, Suitland, MD 20746, USA. Email: brostoffl@scmre.si.edu

Rsum La spectroscopic d'impdance lcctrochimiquc (SIE) est une technique qui mesure q uantitativement le niveau de protection contre la corrosion d'un substrat mtalliq ue fourni par un revtement. L'article illustre la thorie de la SIE et dcrit son app lication pour valuer les revtements protecteurs des sculptures et ornements en bro nze exposs l'extrieur. Trois types de revtements ont t tudis sur un bronze coul mon al : une cire microcristalline, un copolymre de mthacrylate de mthyle vendu sous le nom commercial de lncralac, et un revtement de surface base d'acrylique/ mthane a crylique. Chaque type de revtement a t soumis un vieillissement acclr et valu par S 'information a ensuite t utilise pour calculer le module d'impdance des chantillons, reprsent dans des diagrammes de Bode et interprt en termes de performance protectric e. Zusammenfassung Mit Hilfe der Elektrochemischen Impedanz Spektroskopie (EIS) kan n man den Korrosionsschutz durch ein berzugsmaterial auf einem Metall quantitativ bestimmen. In dieser Arbeit wird einerseits die Methode theoretisch beschrieben , andererseits werden die Mglichkeiten von EIS anhand von Schutzberzgen auf Auenbron zen und Ornamenten ausgelotet. Drei Schutzberzge wurden evaluiert: ein Mikrokrista llines Wachs, ein Acryl/Methacrylat Copolymer, das unter dem Namen Incar/ack geh andelt wird, sowie ein Acryl/Acrylurethanberzug. Jedes Schutzsystem ivurde durch beschleunigte Bewitterung gealtert und mit Hilfe von EIS bewertet. Diese Informa tion ivurde zur Bestimmung des Impedanzmoduls der Proben genutzt. Das lmpcdanzmo duls wurde in Bode Diagrammen aufgetragen und hinsichtlich der Schutzwirkung int erpretiert.

Resumen La espectroscopia electroqumica de impedancia (EIS) es una tcnica que mide cuantitativamente el nivel de proteccin contra la corrosin que suministra una cap a de recubrimiento a un substrato metlico. Este artculo ilustra primeramente los a spectos tericos de la EIS, se evala adems su potencial para evaluar la efectividad de las capas de proteccin en esculturas y ornamentaciones de bronce en exteriores . Se evaluaron tres sistemas de recubrimiento en un bronce monumental: una cera microcristalina, un copolmero de metilmetacrilato vendido bajo el nombre de lncra lac y un acabado acrilico/acrlico de metano. Cada sistema de recubrimiento fue en vejecido aceleradamente de modo artificial y evaluado mediante EIS. La informacin obtenida fue despus usada para calcular los mdulos de impedancia de las muestras, los cuales se representan en grficos Bode y se interpretan en trminos del desempeo de los recubrimientos.