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Archaeological and historical artefacts, teenth century Over centuries other materials were also used destructive tool for studying the electrochemical reaction on the. such as concrete for street lamps and stone for balconies and metal surface and for identifying cracks and or porosity on the. grids Nevertheless cast iron alloys brought street furniture to a surface layers. massive diffusion 3 In the last three decades EIS has been successfully used for the. Atmospheric corrosion of ferrous alloys and deterioration of pro evaluation of the protective efficiency of organic coatings and. tective coatings is a serious problem for the safeguard of cultural its change during exposure to corrosive environments 13 by. heritage exposed to the action of natural weathering and urban specially designed monitoring probes during laboratory tests as. pollution Metal corrosion occurs at the surface moisture film in well as field trials 14 16 Letardi et al performed in situ EIS. terface and air pollutants and particulate matter which partially measurements with a special contact probe to determine the. dissolve and ionize in the moisture film can accelerate it Solid effectiveness of some protective coatings applied on artificially. and or gaseous pollutants such as SO2 NOx and CO2 under the patinated coupons and real monuments 17 18 The same probe. effects of O2 temperature humidity and sunlight may also react arrangement is adopted by Balbo et al to monitor the corrosion. to form new secondary pollutants 4 rate in the presence of synthetic rainwater of bronze and gilded. Cast irons have good resistance to atmospheric corrosion thanks bronze coupons produced with the ancient techniques employed. to more or less corrosion resistant phases graphite phospho during the Renaissance period 19 More recently solid state. rous eutectic and to a lesser extent carbides and carbide eutec probes are designed and used in EIS measurements to evaluate. tic that are largely or completely absent from steel 5 The rate the level of corrosion protection afforded by the paint coating. of atmospheric corrosion of cast iron is lower than that of steel on a steel sculpture Toku sculpture Canberra Nara Peace Park. especially in the presence of high concentrations of pollutants Canberra Australia 20. 6 At relative humidity RH lower than 65 atmospheric Our study evaluates the state of conservation of four painted and. corrosion rates are usually relatively low However at RH above partially corroded post mounted luminaries in cast irons dating. 70 unalloyed cast irons suffer of generalized corrosion in back to the nineteenth and the twentieth centuries and com. volving the formation of mixtures of oxides and hydrated oxides ing from foundries located in Italy and France The results of the. similar to those in steel In polluted atmospheres the corrosion investigations on the cast irons microstructure are presented Mi. layer also contains sulfates chlorides and nitrates These corro crostructural features are used for evaluating manufacturing pro. sion rates tend to decrease with increasing exposure duration cedures The study of the corrosion attack morphology the patina. due to the formation of an adherent and highly protective layer stratification and the main corrosion products is also performed. of corrosion products 5 The historical street furniture composed to elucidate the corrosion process Finally the electrochemical. of cast irons was usually exposed to the atmosphere for fifty or characterization is carried out for estimating the protectiveness. even one hundred and more years but for the majority of its of paints applied on the surface of the examined artefacts. exposure the surfaces were protected by paints with active pig. ments able to provide cathodic protection or anodic passivation MATERIALS AND METHODS. 7 Corroded surfaces of cast irons tend to crumble and flake In order to preserve the objects from further damage most of the. this phenomenon is more evident under the paint layers investigations were carried out on fragments collected from the. The electrochemical impedance spectroscopy EIS is proven to artefacts A summary of characteristics of the studied fragments. be a useful technique for estimating the rate of atmospheric i e the origin the year of manufacturing the nationality of the. corrosion of metals 8 12 It has a great advantage as a non foundries together with the performed experimental procedure. conventional non destructive in situ are listed in Tab 1. Tab 1 Summary of the studied fragments with information on year of manufacturing nationality of the foundries and performed ex. perimental analyses conventional non destructive in situ Elenco dei frammenti analizzati con indicazione dell anno di produzione. della nazionalit della fonderia di provenienza e della tipologia di tecnica utilizzata su ciascun frammento. Investigations,Nationality of, Fragment Year Conventional Non destructive In situ. the foundry,Metallography SEM EDS XRD FT IR EIS,1 Enna 1880 1890 Italy x x x x. 2 Bergamo 1900 n r x x x x x,3 Imola 1929 Italy x x x. 4 Nice 1930 France x x x x,n r non reported,6 La Metallurgia Italiana n 4 2018.
Storia della metallurgia e beni culturali, The microstructural characterization was performed on some performed with a 0 02 step size and a 10 s dwell time. representative fragments obtained from the longitudinal sec The protectiveness of paints of the samples 1 Enna and. tion sample observed in the direction of the metal surface 2 Bergamo was evaluated by electrochemical impedance. and from the cross section sample observed across the thick spectroscopy EIS In order to check the reliability of the. ness of the metal The fragments were embedded in cold technique EIS measurements were also performed on sam. mounting resin polished and analyzed by conventional me ples in modern gray cast iron plates 5 5 x 10 cm in size. tallographic techniques The analyses of the cast irons micro approximately subjected to the current standard painting. structure before chemical etching were carried out by a Leica cycle thickness about 200 m of Neri S p A Longiano FC. MEF4M optical microscope OM Leica Wetzlar Germany Italy The modern gray cast iron samples were monitored by. to determine the form distribution and size of graphite in collecting EIS spectra during exposure to neutral salt spray. accordance with the standard EN ISO 945 1 2008 The mi test 5 sodium chloride dissolved in deionized water after. crostructure was analyzed after chemical etching with Nital 15 42 and 83 days corresponding to 360 1000 and 2000. 4 4 nitric acid in ethanol by both optical microscopy and hours The tests were performed by using an EIS probe for. scanning electron microscopy The scanning electron micro in situ electrochemical characterization of coatings on out. scope was a Zeiss EVO MA 15 Zeiss Oberkochen Germany door real components and structures similar to that already. equipped with an energy dispersive microprobe EDS operat used in 19 that was placed in contact with the samples by. ing in variable pressure conditions VPSEM interposing a cloth soaked with a natural mineral water hav. The patina stratigraphy was investigated on the cross sec ing constant conductivity 222 S cm 1 at 20 C The spectra. tions in non etched conditions by VPSEM EDS The coating were recorded after about 20 min monitoring of the open. thickness was non uniform and difficult to be correctly es circuit potential EOCP when the EOCP variations were lower. timated due to the degradation conditions It resulted to be than 2 mV 10 min For these tests a PAR EG G 273A po. around 200 m in all cases with the exception of 2 Bergamo tentiostat Princeton Applied Research Princeton USA was. sample which was thinner about 100 m Both paints and used coupled with a FRA Solartron 1260 frequency response. corrosion products collected from the fragments were ana analyzer Ametek Berwyn USA under the following experi. lyzed by diffuse reflectance FT IR DRIFT spectroscopy with mental conditions 10 mV rms alternating potential signal. a Thermo Scientific Nicolet iS50 spectrometer Thermo Fisher 1MHz 1 mHz frequency range. Scientific Waltham USA The spectrometer was purged with. dry CO2 free air generated with a Balston 75 52 unit and RESULTS. a deuterated triglycine sulfate DTGS detector was used to Microstructural characterization. investigate the region from 4000 400 cm 1 with a resolu The optical micrographs of the microstructure observed on. tion of 4 cm 1 Paint samples were obtained by abrading the the cross sections of cast irons before chemical etching are. painted post surfaces with a SiC abrasive sampling stick and shown in Fig 1 In accordance with the standard EN ISO 945. the scrapings were analyzed on SiC substrate The samples 1 2008 samples 1 Enna Fig 1a 2 Bergamo Fig 1b and. of corrosion products were directly collected from post sur 3 Imola Fig 1c were characterized by lamellar graphite of. faces and before the analysis were ground and mixed with Type B rosette grouping with random orientation For sam. potassium bromide In addition the samples collected from ples 1 Enna and 2 Bergamo the graphite lamellae were be. the surfaces of the fragments were analyzed by X ray diffrac tween 0 12 and 0 25 mm in length while on sample 3 Imola. tion XRD technique The XRD spectra were acquired by a lamellae lengths in the range of 0 06 and 0 12 mm were. Bruker D8 diffractometer Bruker Billerica USA using a Cu measured The sample 4 Nice Fig 1d showed Type D lamel. Ka radiation source with a 40 kV accelerating voltage and a lar graphite fine randomly oriented graphite flakes in the. 40 mA filament current 2 scans from 6 to 130 were interdendritic position with length shorter than 0 015 mm. La Metallurgia Italiana n 4 2018 7,Archaeological and historical artefacts. Fig 1 Optical micrographs of the microstructure observed on the cross sections of cast irons before chemical etching a sample. 1 Enna b sample 2 Bergamo c sample 3 Imola d sample 4 Nice Micrografie ottiche rappresentative della microstruttura delle. ghise in sezione trasversale ed in assenza di attacco metallografico a campione 1 Enna b campione 2 Bergamo c campione. 3 Imola d campione 4 Nice, Fig 2 Optical micrographs of the microstructure observed on the cross sections of sample 1 Enna a b and sample 2 Bergamo c. d after chemical etching Micrografie ottiche rappresentative della microstruttura dei campioni 1 Enna a b e 2 Bergamo c d in. sezione trasversale e dopo attacco metallografico,8 La Metallurgia Italiana n 4 2018. Storia della metallurgia e beni culturali, Fig 3 VPSEM backscattered electron images of the cross section of the corrosion patina observed on the surface of the sample.
2 Bergamo a overview of the patina b detail of the inner layer Micrografie VPSEM in modalit elettroni retrodiffusi rappresenta. tive della patina di corrosione osservata sulla superficie del campione 2 Bergamo a visione generale della patina di corrosione b. dettaglio dello strato interno di corrosione, Fig 2 shows the optical micrographs of 1 Enna and 2 Bergamo ticles were higher than in the metal matrix In the 2 Bergamo. cross sections after chemical etching In the first case Fig 2a sample Fig 2c and d characterized by a pearlitic microstructure. and b the microstructure was characterized by the presence with uniformly distributed steadite a higher amount of impuri. of pearlite ferrite close to the graphite rosettes white areas in ties than that observed on the cross section of the sample 1. Fig 2a steadite eutectic of iron phosphide Fe3P and iron Fig Enna was detected The microstructures of the cross sections of. 2b and impurities in the form of polygonal shape particles The samples 3 Imola and 4 Nice were similar to that of the sample. semi quantitative EDS analyses highlighted that the amounts of 2 Bergamo but with very few impurities. sulfur and manganese detected in these polygonal shape par. La Metallurgia Italiana n 4 2018 9,Archaeological and historical artefacts. Fig 4 VPSEM backscattered electron images upper left corner layered image of X ray maps upper center and maps of elemental. distribution in the cross section of the sample 3 Imola Micrografia VPSEM in modalit elettroni retrodiffusi in alto a sinistra so. vrapposizione di mappe di raggi X in alto al centro e mappe rappresentative della distribuzione degli elementi chimici nella sezione. trasversale del campione 3 Imola,10 La Metallurgia Italiana n 4 2018. Storia della metallurgia e beni culturali, Characterization of the corrosion phenomena cles likely BaSO4 were detected whereas Zn rich particles were. An example of the stratigraphy of the corrosion patina observed identified in the paint layer of the sample 4 Nice. on the surfaces of the examined cast irons is shown in the VPSEM The FT IR spectra of the paint samples are showed in Fig 5a The. backscattered electron images of Fig 3 Two distinct layers of paints spectra were complicated by the presence of additional. corrosion products were recognizable an inner layer indicated components in the paint formulation such as the pigments ex. by letter A in Fig 3a characterized by non uniform penetration tenders and dryers that exhibited their specific absorption peaks. inside the less noble alloy phase Fig 3b and an external one on making the identification of the paints a complex task In all. the top indicated by letter B in Fig 3a spectra the typical vibration of aliphatic functional groups was. The VPSEM EDS mapping of the corrosion patina and paint on present related to symmetric and asymmetric C H stretching and. the cross section of the sample 3 Imola is reported in Fig 4 The C H deformation bands occurring respectively at 2926 cm 1 and. EDS maps measured on the inner layer of corrosion suggested 2856 cm 1 and at 1452 1413 cm 1 and a large band centered. that the selective attack of the matrix essentially produced iron around 3400 cm 1 related to OH stretching The samples 1 Enna. corrosion products Inside the outer corrosion layer iron oxides and 2 Bergamo showed a strong and intense peak at 1733 cm 1. were visible admixed with elements from the corrosive environ related to the stretching of the carbonyl group In addition to. ment e g K and Al from particulate matter The EDS maps also a strong band present in the region 1285 1175 cm 1 involving. highlighted that the corrosion patina was overlain by a multilayer the stretching of the carboxylic group bonds a further IR band. paint Beginning from the outer corrosion layer the paint was near 1030 cm 1 related to the stretching of O C bond in the. composed of a Pb rich layer a S and Ba rich layer and a Ti rich O CH2 group was observed These findings suggested that these. layer The VPSEM EDS mapping performed on the sample 2 Ber coatings were alkyd resins The sample 2 Bergamo Red Layer. gamo showed that the stratification of the corrosion products collected from the layer beneath the paint showed in the low. and paint was similar to that observed on sample 3 Imola In energy portion of the spectrum three peaks at 550 529 and 429. the 1 Enna and 4 Nice samples the EDS maps on the layers of cm 1 related to the presence of minium Pb3O4. corrosion products were similar to those in Fig 4 However in. the paint layer of 1 Enna sample only Ba S and O rich parti. Fig 5 FT IR spectra of a paints and b corrosion products collected on post mounted luminaries exposed outdoor Spettri FT IR. relativi alle vernici a e ai prodotti di corrosione b visibili sulla superfice dei lampioni oggetto di studio. La Metallurgia Italiana n 4 2018 11,Archaeological and historical artefacts.
In Fig 5b the FT IR spectra collected on the corrosion products Bergamo and 4 Nice could be related to the presence of minium. scraped from the post surfaces are reported All the spectra ap but the XRD spectra highlighted the presence of the crystalline. peared quite similar the peak at 1022 cm 1 and the shoulder at form of this compound together with anatase TiO2 only in the. 1127 cm 1 were related to the in plane Fe O H bending while samples 2 Bergamo and 3 Imola The spectra also indicated the. the peaks at 760 and 476 cm 1 were related to the out of plane presence of some organic compounds band at 2800 3000 cm 1. Fe O H bending All these characteristic peaks indicated the pres and peaks around at 1480 and 1380 cm 1 probably due to the. ence of lepidocrocite FeOOH 21 22 in all the samples The deposition of organic substances or to the residues of the origi. peaks at 884 and 623 cm 1 also suggested the occurrence of nal paint. a small amount of goethite FeOOH 21 22 The large band In all samples the VPSEM EDS observations highlighted the pres. in the range 3100 3600 cm 1 was related to OH stretching of ence of both flower like pattern and the foam like morphology. hydroxyl groups of both goethite and lepidocrocite but it was of the lepidocrocite Fig 6a and the cloudy or cotton ball like. also probably related to the vibration of water in crystal struc microstructure associated to the goethite Fig 6b. ture as confirmed by the presence of a shoulder at 1650 cm 1. The shoulder detected at 529 cm 1 on the samples 1 Enna 2. Fig 6 VPSEM images of the corrosion products observed on the surface of the examined samples a detail of lepidocrocite b detail. of goethite Micrografie VPSEM rappresentative dei prodotti di corrosione osservati sulla superfice dei campioni indagati a dettaglio. della lepidocrocite b dettaglio della goethite, Electrochemical characterization at frequencies lower than 1 Hz for the ancient samples or 10 1. Fig 7 shows the EIS spectra in Nyquist format recorded on 1 Hz for the modern one For a defective organic coating 23 24. Enna and 2 Bergamo samples carrying the original paint layers the HF time constant is linked to the porous coating properties. Fig 7a and on the plates in modern gray cast iron with the while the LF one to the charge transfer at the bottom of the coat. standard Neri S p A coating Fig 7b the latter after 15 42 and ing pores In the case of the sample 2 Bergamo also a third time. 83 days of exposure to the salt spray test constant was detectable at intermediate frequencies around 102. The EIS spectra mainly showed two time constants the high Hz which could be related to the dielectric properties of the cor. frequency HF one corresponds to the semicircle at frequencies rosion product layer formed underneath the protective coating. higher than 103 Hz for the ancient samples or 101 Hz for the 25 26 The shape of the spectrum of 1 Enna sample did not. modern one and the low frequency LF one is related to the arc exclude that this time constant was also present but overlapped. to the LF one,12 La Metallurgia Italiana n 4 2018,Storia della metallurgia e beni culturali. The HF range of the EIS spectra related to the coating dielectric to 0 Rp is known to be inversely proportional to the corrosion. properties were analyzed by using a simple parallel R C circuit rate 25 All the obtained parameters are reported in Table 2. to evaluate the coating pore resistance Rpore and the coating ca For the modern gray cast iron sample exposed to the salt spray. pacitance Cc 25 The corrosion behavior of the metal substrate test for 15 days the second semicircle in the Nyquist plot was. was evaluated by estimating the polarization resistance value Rp characterized by too few scattered data thus the Rp value was. as the limit of the LF capacitive semicircle for frequency tending not evaluated. Fig 7 EIS spectra in Nyquist format recorded on a 1 Enna and 2 Bergamo samples and on the plates in modern gray cast iron b. Spettri EIS sotto forma di diagrammi di Nyquist registrati a sui campioni 1 Enna e 2 Bergamo e sulle lastrine in ghisa grigia. Tab 2 Values of Rpore cm2 Cc F cm 2 and Rp cm2 obtained from EIS fitting with the adopted equivalent circuit Valori di Rpore. cm2 Cc F cm 2 e Rp cm2 ottenuti dopo fitting dei dati EIS mediante il circuito equivalente adottato. Sample Rpore cm2 Cc F cm 2 Rp cm2,Modern gray cast iron after 3 9 107 1 7 10 10. 15 days in salt spray test, Modern gray cast iron after 2 1 107 2 0 10 10 9 8 107. 83 days in salt spray test,1 Enna 6 3 104 7 0 10 11 2 4 106.
2 Bergamo 4 0 104 1 7 10 10 2 6 106,La Metallurgia Italiana n 4 2018 13. Archaeological and historical artefacts, Rpore values of the coating on the modern gray cast iron remained weakening This phenomenon is referred to in the literature as. higher than107 cm2 until the end of the exposure to the salt graphitization graphitic or spongy corrosion 5 7 28. spray test The corresponding Cc values only slightly increased The examinations of paints applied on the surfaces of cast irons. during the test indicating that it offered a high barrier effect indicate the use of pigments TiO2 and likely BaSO4 alkyd res. against water absorption 27 Rpore values of the ancient paints ins and minium as a passivating primer layer According to the. were more than two orders of magnitude lower than those of literature the most common coating system detected on histori. the modern one suggesting that they were affected by many cal ironworks was a traditional oil paint composed of turpentine. pores and cracks The Cc value of 1 Enna sample was smaller solvent linseed oil binder pigments and additives mainly driers. than those measured on the modern paint while that of 2 Ber These were usually applied over a primer containing pigments. gamo was equal Capacitances are proportional to the dielectric red ochre with a small proportion of white lead in the seven. constant of the coatings and inversely proportional to their teenth and early eighteenth centuries and red lead minium in. thickness Dry conditions are present in both ancient paints due linseed oil primers in the late eighteenth and nineteenth centu. to their persistence in indoor conditions for many years and due ries Red lead formed lead soaps with linseed oil which became. to the short measurement time in contact with mineral water an elastic and tough film impervious to water At least two slow. These conditions induce low coating values and justify the drying linseed oil based finish layers were applied over a red lead. low Cc value measured on 1 Enna sample as this ancient and primer 7 From the 1930s on the most common replacement. the modern coatings have comparable thickness In the case of for traditional oil paints was the painting with alkyd resins These. 2 Bergamo Cc is comparable to those measured on the modern materials provided the advantage of a higher layer thickness. paint and this could be connected to the lower coating thickness from one application and faster drying than the traditional oils. The estimated Rp values of the ancient samples were more than 4. one order of magnitude lower than that on modern gray cast The electrochemical characterization of paints further confirmed. iron at the end of salt spray test exposure evidencing the higher the capability of EIS technique in evaluating the conservation. corrosion rates of the underlying metal due to the scarce residual state of ancient painted artefacts 9 11 12 and the barrier prop. protectiveness of the ancient coatings erty variations in modern coatings even when not detectable by. visual observation 29,DISCUSSION, This work evaluates the conservation state of European street CONCLUSIONS. furniture in painted and partially corroded cast iron artefacts All Our study investigates the state of conservation of four painted. examined cast irons can be classified as gray cast irons The dis and partially corroded post mounted luminaries dating back to. tribution of the lamellar graphite of Type B in samples 1 Enna the nineteenth and the twentieth centuries and coming from. 2 Bergamo and 3 Imola is frequently encountered on alloys so foundries located in Italy and France The microstructure of the. lidified with an intermediate degree of undercooling whereas cast irons was consistent with the procedures employed for. the distribution of type D and the very fine graphite lamellae of manufacturing complex shape casting with variable wall thick. the sample 4 Nice forms typically under a relatively high degree ness The Italian castings were composed of lamellar graphite of. of undercooling 28 All metalworks show microstructures with Type B and with lamellae between 0 06 and 0 25 mm in length. high steadite contents It is known that the presence of steadite For the samples 2 Bergamo and 3 Imola the microstructure. is due to the addition of phosphorus This element lowers the was pearlitic with a high amount of steadite and manganese. melting point and improves the fluidity of cast iron alloys thus sulfides The microstructure of the sample 1 Enna was similar. favoring the manufacturing of complex shape castings with thin but with ferrite close to the graphite rosettes The French cast. wall thickness e g castings for European street furniture 28 ing had lamellar graphite of Type B with lamellae length shorter. The study of the patina stratification the main corrosion products than 0 015 mm and a microstructure similar to that of samples. and corrosion attack morphology suggests that a specific corro 2 Bergamo and 3 Imola. sion phenomenon occurred In an outdoor environment where The study of the patina stratification the main corrosion products. paints are partially removed and or damaged acidic rainwater and corrosion attack morphology indicated the graphitization of. starts to corrode cast iron alloys As the ferrous matrix corrodes cast irons This phenomenon was accompanied by the deposition. the more noble graphite further promotes the attack of the sur of thick layers of corrosion containing lepidocrocite goethite. rounding metal by the galvanic coupling effect The graphitic cor and impurities from the corrosive environment. rosion residue is impregnated with corrosion products of iron On the examined fragments no historical paints were detected. lepidocrocite characterized by a flower like pattern and a foam suggesting the removal of the deteriorated paint layers from the. like morphology and goethite with a cloudy or cotton ball like surfaces before the application of modern paint systems Finally. microstructure as identified by FT IR and VPSEM EDS The af the electrochemical characterization established the poor protec. fected surfaces show a compact layer of graphite rust and impu tiveness offered by the paints on the post mounted luminaries. rities as confirmed by the scanning electron microscope obser. vations that may inhibit further damage The cast iron elements. retain their appearance and shape but undergo a mechanical. 14 La Metallurgia Italiana n 4 2018,Storia della metallurgia e beni culturali. ACKNOWLEDGEMENTS, Dr Raffaella Bassi Neri and Dr Antonio Neri NERI Foundation The Italian Museum of Cast Iron Longiano FC Italy are gratefully.
acknowledged for providing the cast iron artefacts investigated in the present work. REFERENCES, 1 R Bassi L Bazzocchi Cast iron artefacts for city d cor a list of the principal typologies in So light and yet a metal The art of cast. iron in the 19th and 20th centuries R Bassi C Biasini Selvaggi M G Massafra Eds Barbieri Selvaggi Editori Manduria 2011. 2 R Bassi Neri La ghisa quando il gusto incontro l arte industriale Arredo Citta 2 2011 5. 3 J Gay Cast iron Architecture and ornament Function and Fantasy John Murray Publishers Ltd London 1985. 4 S Godfrain R Pender B Martin English Heritage Practical building conservation Metals Ashgate Publishing Limited Farnham. 5 A Reynaud Corrosion of cast irons in Sheir s Corrosion Corrosion and degradation of engineering materials vol 3 B Cottis M. Graham R Lindsay S Lyon T Richardson D Scantlebury H Stott Eds Elsevier Ltd Amsterdam 2010 p 1737 1788. 6 P Dillmann D Watkinson E Angelini A Adriaens Corrosion and conservation of cultural heritage metallic artefacts Woodhead. Publishing Cambridge 2013, 7 K Kreislova D Knotkova H Geiplova Atmospheric corrosion of historical industrial structures in Corrosion and conservation of. cultural heritage metallic artefacts P Dillmann D Watkinson E Angelini A Adriaens Eds Woodhead Publishing Cambridge. 2013 p 311 343, 8 X X Fu J H Dong E H Han W Ke A new experimental method for in situ corrosion monitoring under alternate wet dry condi. tions Sensors 9 2009 10400 10410, 9 C Li Y Ma Y Li F Wang EIS monitoring study of atmospheric corrosion under variable relative humidity Corros Sci 52 2010. 10 C Thee L Hao J Dong X Mu X Wei X Li W Ke Atmospheric corrosion monitoring of a weathering steel under an electrolyte. film in cyclic wet dry condition Corros Sci 78 2014 130 137. 11 E Angelini D Assante S Grassini M Parvis EIS measurements for the assessment of the conservation state of metallic works of. art Int J Circ Syst Signal Process 8 2014 240 245, 12 S Grassini S Corbellini M Parvis E Angelini F Zucchi A simple Arduino based EIS system for in situ corrosion monitoring of.
metallic works of art Measurement 114 2018 508 514. 13 F Mansfeld Use of electrochemical impedance spectroscopy for the study of corrosion products protection by polymer coatings J. Appl Electrochem 25 1995 187 202, 14 A Nishikata Y Ichihara T Tsuru An application of electrochemical impedance spectroscopy to atmospheric corrosion study Cor. ros Sci 37 1995 897 911, 15 A Nishikata Y Yamashita H Isatayama T Tsuru A Usami K Tanabe H Mabuchi An electrochemical impedance study on atmo. spheric corrosion of steels in a cyclic wet dry condition Corros Sci 37 1995 2059 2069. 16 A Nishikata F Suzuki T Tsuru Corrosion monitoring of nickel containing steels in marine atmospheric environment Corros Sci. 47 2005 2578 2588, 17 P Letardi Use of electrochemical impedance spectroscopy on outdoor bronze monuments CSA EAS06 13 14 November 2006. Somerset USA, 18 P Letardi Laboratory and field tests on patinas and protective coating systems for outdoor bronze monuments Proceedings of. Metal 2004 4 8 October 2004 National Museum of Australia Canberra ACT Australia p 379 387. 19 A Balbo M Abbottoni A Frignani C Chiavari C Martini E Bernardi C Monticelli In situ EIS characterization of outdoor corro. sion behaviour of bronze and gilded bronze EUROCORR 2014 European Federation of Corrosion Event No 364 8 12 September. 2014 Pisa Italy Paper 7259 p 1 9, 20 S S Jamali Y Zhao Z Gao H Li A C Hee In situ evaluation of corrosion damage using non destructive electrochemical measure.
ments A case study J Ind Eng Chem 43 2016 36 43, 21 S Rahimi R M Moattari L Rajabi A Ashraf Derakhshan M Keyhani Iron oxide hydroxide FeOOH nanoparticles as high. potential adsorbents for lead removal from polluted aquatic media J Ind Eng Chem 23 2015 33 43. 22 T Ishikawa Y Kondo A Yasukawa K Kandori Formation of magnetite in the presence of ferric oxyhydroxides Corros Sci 40. 1998 1239 1251, 23 J N Murray Electrochemical test methods for evaluating organic coatings on metals an update Part III Multiple test parameter. measurements Prog Org Coat 31 1997 375 391,La Metallurgia Italiana n 4 2018 15. Archaeological and historical artefacts, 24 A Lasia Electrochemical impedance spectroscopy and its application Springer Science Business Media New York 2014. 25 G Trabanelli C Monticelli V Grassi A Frignani Electrochemical study on inhibitors of rebar corrosion. in carbonated concrete Cement Concrete Res 35 2005 1804 1813. 26 C Zhang J Zhao Effects of pre corrosion on the corrosion inhibition performance of three inhibitors on Q235 steel in CO2 H2S. saturated brine solution Int J Electrochem Sci 12 2017 9161 9179. 27 J Gonzalez Guzman J J Santana S Gonzalez R M Souto Resistance of metallic substrates protected by organic coating contain. ing glass flakes Prog Org Coat 68 2010 240 243, 28 ASM Specialty Handbook Cast Irons ASM International Materials Park Ohio 1996.
29 F Deflorian S Rossi L Fedrizzi P L Bonora Testing of protective organic coatings on metals comparison of salt spray and electro. chemical impedance spectroscopy J Test Eval 31 2 2003 91 97.

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