elko ep branches over the worlds exporting countries 13 70 12 000 000 manufactured products 10 000 inels installation 330 employees 2nd position in europe
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Atmospheric corrosion of ferrous alloys and deterioration of pro - tective coatings is a serious problem for the safeguard of cultural heritage exposed to the action of natural weathering and urban pollution. Metal corrosion occurs at the surface/moisture film in-terface and air pollutants and particulate matter, which partially
Archaeological and historical artefactsteenth century Over centuries other materials were also used destructive tool for studying the electrochemical reaction on thesuch as concrete for street lamps and stone for balconies and metal surface and for identifying cracks and or porosity on thegrids Nevertheless cast iron alloys brought street furniture to a surface layersmassive diffusion 3 In the last three decades EIS has been successfully used for theAtmospheric corrosion of ferrous alloys and deterioration of pro evaluation of the protective efficiency of organic coatings andtective coatings is a serious problem for the safeguard of cultural its change during exposure to corrosive environments 13 byheritage exposed to the action of natural weathering and urban specially designed monitoring probes during laboratory tests aspollution Metal corrosion occurs at the surface moisture film in well as field trials 14 16 Letardi et al performed in situ EISterface and air pollutants and particulate matter which partially measurements with a special contact probe to determine thedissolve and ionize in the moisture film can accelerate it Solid effectiveness of some protective coatings applied on artificiallyand or gaseous pollutants such as SO2 NOx and CO2 under the patinated coupons and real monuments 17 18 The same probeeffects of O2 temperature humidity and sunlight may also react arrangement is adopted by Balbo et al to monitor the corrosionto form new secondary pollutants 4 rate in the presence of synthetic rainwater of bronze and gildedCast irons have good resistance to atmospheric corrosion thanks bronze coupons produced with the ancient techniques employedto more or less corrosion resistant phases graphite phospho during the Renaissance period 19 More recently solid staterous eutectic and to a lesser extent carbides and carbide eutec probes are designed and used in EIS measurements to evaluatetic that are largely or completely absent from steel 5 The rate the level of corrosion protection afforded by the paint coatingof atmospheric corrosion of cast iron is lower than that of steel on a steel sculpture Toku sculpture Canberra Nara Peace Parkespecially in the presence of high concentrations of pollutants Canberra Australia 206 At relative humidity RH lower than 65 atmospheric Our study evaluates the state of conservation of four painted andcorrosion rates are usually relatively low However at RH above partially corroded post mounted luminaries in cast irons dating70 unalloyed cast irons suffer of generalized corrosion in back to the nineteenth and the twentieth centuries and comvolving the formation of mixtures of oxides and hydrated oxides ing from foundries located in Italy and France The results of thesimilar to those in steel In polluted atmospheres the corrosion investigations on the cast irons microstructure are presented Milayer also contains sulfates chlorides and nitrates These corro crostructural features are used for evaluating manufacturing prosion rates tend to decrease with increasing exposure duration cedures The study of the corrosion attack morphology the patinadue to the formation of an adherent and highly protective layer stratification and the main corrosion products is also performedof corrosion products 5 The historical street furniture composed to elucidate the corrosion process Finally the electrochemicalof cast irons was usually exposed to the atmosphere for fifty or characterization is carried out for estimating the protectivenesseven one hundred and more years but for the majority of its of paints applied on the surface of the examined artefactsexposure the surfaces were protected by paints with active pigments able to provide cathodic protection or anodic passivation MATERIALS AND METHODS7 Corroded surfaces of cast irons tend to crumble and flake In order to preserve the objects from further damage most of thethis phenomenon is more evident under the paint layers investigations were carried out on fragments collected from theThe electrochemical impedance spectroscopy EIS is proven to artefacts A summary of characteristics of the studied fragmentsbe a useful technique for estimating the rate of atmospheric i e the origin the year of manufacturing the nationality of thecorrosion of metals 8 12 It has a great advantage as a non foundries together with the performed experimental procedureconventional non destructive in situ are listed in Tab 1Tab 1 Summary of the studied fragments with information on year of manufacturing nationality of the foundries and performed experimental analyses conventional non destructive in situ Elenco dei frammenti analizzati con indicazione dell anno di produzionedella nazionalit della fonderia di provenienza e della tipologia di tecnica utilizzata su ciascun frammentoInvestigationsNationality ofFragment Year Conventional Non destructive In situthe foundryMetallography SEM EDS XRD FT IR EIS1 Enna 1880 1890 Italy x x x x2 Bergamo 1900 n r x x x x x3 Imola 1929 Italy x x x4 Nice 1930 France x x x xn r non reported6 La Metallurgia Italiana n 4 2018Storia della metallurgia e beni culturaliThe microstructural characterization was performed on some performed with a 0 02 step size and a 10 s dwell timerepresentative fragments obtained from the longitudinal sec The protectiveness of paints of the samples 1 Enna andtion sample observed in the direction of the metal surface 2 Bergamo was evaluated by electrochemical impedanceand from the cross section sample observed across the thick spectroscopy EIS In order to check the reliability of theness of the metal The fragments were embedded in cold technique EIS measurements were also performed on sammounting resin polished and analyzed by conventional me ples in modern gray cast iron plates 5 5 x 10 cm in sizetallographic techniques The analyses of the cast irons micro approximately subjected to the current standard paintingstructure before chemical etching were carried out by a Leica cycle thickness about 200 m of Neri S p A Longiano FCMEF4M optical microscope OM Leica Wetzlar Germany Italy The modern gray cast iron samples were monitored byto determine the form distribution and size of graphite in collecting EIS spectra during exposure to neutral salt sprayaccordance with the standard EN ISO 945 1 2008 The mi test 5 sodium chloride dissolved in deionized water aftercrostructure was analyzed after chemical etching with Nital 15 42 and 83 days corresponding to 360 1000 and 20004 4 nitric acid in ethanol by both optical microscopy and hours The tests were performed by using an EIS probe forscanning electron microscopy The scanning electron micro in situ electrochemical characterization of coatings on outscope was a Zeiss EVO MA 15 Zeiss Oberkochen Germany door real components and structures similar to that alreadyequipped with an energy dispersive microprobe EDS operat used in 19 that was placed in contact with the samples bying in variable pressure conditions VPSEM interposing a cloth soaked with a natural mineral water havThe patina stratigraphy was investigated on the cross sec ing constant conductivity 222 S cm 1 at 20 C The spectrations in non etched conditions by VPSEM EDS The coating were recorded after about 20 min monitoring of the openthickness was non uniform and difficult to be correctly es circuit potential EOCP when the EOCP variations were lowertimated due to the degradation conditions It resulted to be than 2 mV 10 min For these tests a PAR EG G 273A poaround 200 m in all cases with the exception of 2 Bergamo tentiostat Princeton Applied Research Princeton USA wassample which was thinner about 100 m Both paints and used coupled with a FRA Solartron 1260 frequency responsecorrosion products collected from the fragments were ana analyzer Ametek Berwyn USA under the following experilyzed by diffuse reflectance FT IR DRIFT spectroscopy with mental conditions 10 mV rms alternating potential signala Thermo Scientific Nicolet iS50 spectrometer Thermo Fisher 1MHz 1 mHz frequency rangeScientific Waltham USA The spectrometer was purged withdry CO2 free air generated with a Balston 75 52 unit and RESULTSa deuterated triglycine sulfate DTGS detector was used to Microstructural characterizationinvestigate the region from 4000 400 cm 1 with a resolu The optical micrographs of the microstructure observed ontion of 4 cm 1 Paint samples were obtained by abrading the the cross sections of cast irons before chemical etching arepainted post surfaces with a SiC abrasive sampling stick and shown in Fig 1 In accordance with the standard EN ISO 945the scrapings were analyzed on SiC substrate The samples 1 2008 samples 1 Enna Fig 1a 2 Bergamo Fig 1b andof corrosion products were directly collected from post sur 3 Imola Fig 1c were characterized by lamellar graphite offaces and before the analysis were ground and mixed with Type B rosette grouping with random orientation For sampotassium bromide In addition the samples collected from ples 1 Enna and 2 Bergamo the graphite lamellae were bethe surfaces of the fragments were analyzed by X ray diffrac tween 0 12 and 0 25 mm in length while on sample 3 Imolation XRD technique The XRD spectra were acquired by a lamellae lengths in the range of 0 06 and 0 12 mm wereBruker D8 diffractometer Bruker Billerica USA using a Cu measured The sample 4 Nice Fig 1d showed Type D lamelKa radiation source with a 40 kV accelerating voltage and a lar graphite fine randomly oriented graphite flakes in the40 mA filament current 2 scans from 6 to 130 were interdendritic position with length shorter than 0 015 mmLa Metallurgia Italiana n 4 2018 7Archaeological and historical artefactsFig 1 Optical micrographs of the microstructure observed on the cross sections of cast irons before chemical etching a sample1 Enna b sample 2 Bergamo c sample 3 Imola d sample 4 Nice Micrografie ottiche rappresentative della microstruttura delleghise in sezione trasversale ed in assenza di attacco metallografico a campione 1 Enna b campione 2 Bergamo c campione3 Imola d campione 4 NiceFig 2 Optical micrographs of the microstructure observed on the cross sections of sample 1 Enna a b and sample 2 Bergamo cd after chemical etching Micrografie ottiche rappresentative della microstruttura dei campioni 1 Enna a b e 2 Bergamo c d insezione trasversale e dopo attacco metallografico8 La Metallurgia Italiana n 4 2018Storia della metallurgia e beni culturaliFig 3 VPSEM backscattered electron images of the cross section of the corrosion patina observed on the surface of the sample2 Bergamo a overview of the patina b detail of the inner layer Micrografie VPSEM in modalit elettroni retrodiffusi rappresentative della patina di corrosione osservata sulla superficie del campione 2 Bergamo a visione generale della patina di corrosione bdettaglio dello strato interno di corrosioneFig 2 shows the optical micrographs of 1 Enna and 2 Bergamo ticles were higher than in the metal matrix In the 2 Bergamocross sections after chemical etching In the first case Fig 2a sample Fig 2c and d characterized by a pearlitic microstructureand b the microstructure was characterized by the presence with uniformly distributed steadite a higher amount of impuriof pearlite ferrite close to the graphite rosettes white areas in ties than that observed on the cross section of the sample 1Fig 2a steadite eutectic of iron phosphide Fe3P and iron Fig Enna was detected The microstructures of the cross sections of2b and impurities in the form of polygonal shape particles The samples 3 Imola and 4 Nice were similar to that of the samplesemi quantitative EDS analyses highlighted that the amounts of 2 Bergamo but with very few impuritiessulfur and manganese detected in these polygonal shape parLa Metallurgia Italiana n 4 2018 9Archaeological and historical artefactsFig 4 VPSEM backscattered electron images upper left corner layered image of X ray maps upper center and maps of elementaldistribution in the cross section of the sample 3 Imola Micrografia VPSEM in modalit elettroni retrodiffusi in alto a sinistra sovrapposizione di mappe di raggi X in alto al centro e mappe rappresentative della distribuzione degli elementi chimici nella sezionetrasversale del campione 3 Imola10 La Metallurgia Italiana n 4 2018Storia della metallurgia e beni culturaliCharacterization of the corrosion phenomena cles likely BaSO4 were detected whereas Zn rich particles wereAn example of the stratigraphy of the corrosion patina observed identified in the paint layer of the sample 4 Niceon 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 Thebackscattered electron images of Fig 3 Two distinct layers of paints spectra were complicated by the presence of additionalcorrosion products were recognizable an inner layer indicated components in the paint formulation such as the pigments exby letter A in Fig 3a characterized by non uniform penetration tenders and dryers that exhibited their specific absorption peaksinside the less noble alloy phase Fig 3b and an external one on making the identification of the paints a complex task In allthe top indicated by letter B in Fig 3a spectra the typical vibration of aliphatic functional groups wasThe VPSEM EDS mapping of the corrosion patina and paint on present related to symmetric and asymmetric C H stretching andthe cross section of the sample 3 Imola is reported in Fig 4 The C H deformation bands occurring respectively at 2926 cm 1 andEDS maps measured on the inner layer of corrosion suggested 2856 cm 1 and at 1452 1413 cm 1 and a large band centeredthat the selective attack of the matrix essentially produced iron around 3400 cm 1 related to OH stretching The samples 1 Ennacorrosion products Inside the outer corrosion layer iron oxides and 2 Bergamo showed a strong and intense peak at 1733 cm 1were visible admixed with elements from the corrosive environ related to the stretching of the carbonyl group In addition toment e g K and Al from particulate matter The EDS maps also a strong band present in the region 1285 1175 cm 1 involvinghighlighted that the corrosion patina was overlain by a multilayer the stretching of the carboxylic group bonds a further IR bandpaint Beginning from the outer corrosion layer the paint was near 1030 cm 1 related to the stretching of O C bond in thecomposed of a Pb rich layer a S and Ba rich layer and a Ti rich O CH2 group was observed These findings suggested that theselayer The VPSEM EDS mapping performed on the sample 2 Ber coatings were alkyd resins The sample 2 Bergamo Red Layergamo showed that the stratification of the corrosion products collected from the layer beneath the paint showed in the lowand paint was similar to that observed on sample 3 Imola In energy portion of the spectrum three peaks at 550 529 and 429the 1 Enna and 4 Nice samples the EDS maps on the layers of cm 1 related to the presence of minium Pb3O4corrosion products were similar to those in Fig 4 However inthe paint layer of 1 Enna sample only Ba S and O rich partiFig 5 FT IR spectra of a paints and b corrosion products collected on post mounted luminaries exposed outdoor Spettri FT IRrelativi alle vernici a e ai prodotti di corrosione b visibili sulla superfice dei lampioni oggetto di studioLa Metallurgia Italiana n 4 2018 11Archaeological and historical artefactsIn Fig 5b the FT IR spectra collected on the corrosion products Bergamo and 4 Nice could be related to the presence of miniumscraped from the post surfaces are reported All the spectra ap but the XRD spectra highlighted the presence of the crystallinepeared quite similar the peak at 1022 cm 1 and the shoulder at form of this compound together with anatase TiO2 only in the1127 cm 1 were related to the in plane Fe O H bending while samples 2 Bergamo and 3 Imola The spectra also indicated thethe peaks at 760 and 476 cm 1 were related to the out of plane presence of some organic compounds band at 2800 3000 cm 1Fe O H bending All these characteristic peaks indicated the pres and peaks around at 1480 and 1380 cm 1 probably due to theence of lepidocrocite FeOOH 21 22 in all the samples The deposition of organic substances or to the residues of the origipeaks at 884 and 623 cm 1 also suggested the occurrence of nal painta small amount of goethite FeOOH 21 22 The large band In all samples the VPSEM EDS observations highlighted the presin the range 3100 3600 cm 1 was related to OH stretching of ence of both flower like pattern and the foam like morphologyhydroxyl groups of both goethite and lepidocrocite but it was of the lepidocrocite Fig 6a and the cloudy or cotton ball likealso probably related to the vibration of water in crystal struc microstructure associated to the goethite Fig 6bture as confirmed by the presence of a shoulder at 1650 cm 1The shoulder detected at 529 cm 1 on the samples 1 Enna 2Fig 6 VPSEM images of the corrosion products observed on the surface of the examined samples a detail of lepidocrocite b detailof goethite Micrografie VPSEM rappresentative dei prodotti di corrosione osservati sulla superfice dei campioni indagati a dettagliodella lepidocrocite b dettaglio della goethiteElectrochemical characterization at frequencies lower than 1 Hz for the ancient samples or 10 1Fig 7 shows the EIS spectra in Nyquist format recorded on 1 Hz for the modern one For a defective organic coating 23 24Enna and 2 Bergamo samples carrying the original paint layers the HF time constant is linked to the porous coating propertiesFig 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 coatstandard 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 time83 days of exposure to the salt spray test constant was detectable at intermediate frequencies around 102The EIS spectra mainly showed two time constants the high Hz which could be related to the dielectric properties of the corfrequency HF one corresponds to the semicircle at frequencies rosion product layer formed underneath the protective coatinghigher than 103 Hz for the ancient samples or 101 Hz for the 25 26 The shape of the spectrum of 1 Enna sample did notmodern one and the low frequency LF one is related to the arc exclude that this time constant was also present but overlappedto the LF one12 La Metallurgia Italiana n 4 2018Storia della metallurgia e beni culturaliThe HF range of the EIS spectra related to the coating dielectric to 0 Rp is known to be inversely proportional to the corrosionproperties were analyzed by using a simple parallel R C circuit rate 25 All the obtained parameters are reported in Table 2to evaluate the coating pore resistance Rpore and the coating ca For the modern gray cast iron sample exposed to the salt spraypacitance Cc 25 The corrosion behavior of the metal substrate test for 15 days the second semicircle in the Nyquist plot waswas evaluated by estimating the polarization resistance value Rp characterized by too few scattered data thus the Rp value wasas the limit of the LF capacitive semicircle for frequency tending not evaluatedFig 7 EIS spectra in Nyquist format recorded on a 1 Enna and 2 Bergamo samples and on the plates in modern gray cast iron bSpettri EIS sotto forma di diagrammi di Nyquist registrati a sui campioni 1 Enna e 2 Bergamo e sulle lastrine in ghisa grigiaTab 2 Values of Rpore cm2 Cc F cm 2 and Rp cm2 obtained from EIS fitting with the adopted equivalent circuit Valori di Rporecm2 Cc F cm 2 e Rp cm2 ottenuti dopo fitting dei dati EIS mediante il circuito equivalente adottatoSample Rpore cm2 Cc F cm 2 Rp cm2Modern gray cast iron after 3 9 107 1 7 10 1015 days in salt spray testModern gray cast iron after 2 1 107 2 0 10 10 9 8 10783 days in salt spray test1 Enna 6 3 104 7 0 10 11 2 4 1062 Bergamo 4 0 104 1 7 10 10 2 6 106La Metallurgia Italiana n 4 2018 13Archaeological and historical artefactsRpore values of the coating on the modern gray cast iron remained weakening This phenomenon is referred to in the literature ashigher than107 cm2 until the end of the exposure to the salt graphitization graphitic or spongy corrosion 5 7 28spray test The corresponding Cc values only slightly increased The examinations of paints applied on the surfaces of cast ironsduring the test indicating that it offered a high barrier effect indicate the use of pigments TiO2 and likely BaSO4 alkyd resagainst water absorption 27 Rpore values of the ancient paints ins and minium as a passivating primer layer According to thewere more than two orders of magnitude lower than those of literature the most common coating system detected on historithe modern one suggesting that they were affected by many cal ironworks was a traditional oil paint composed of turpentinepores and cracks The Cc value of 1 Enna sample was smaller solvent linseed oil binder pigments and additives mainly driersthan those measured on the modern paint while that of 2 Ber These were usually applied over a primer containing pigmentsgamo was equal Capacitances are proportional to the dielectric red ochre with a small proportion of white lead in the sevenconstant of the coatings and inversely proportional to their teenth and early eighteenth centuries and red lead minium inthickness Dry conditions are present in both ancient paints due linseed oil primers in the late eighteenth and nineteenth centuto their persistence in indoor conditions for many years and due ries Red lead formed lead soaps with linseed oil which becameto the short measurement time in contact with mineral water an elastic and tough film impervious to water At least two slowThese conditions induce low coating values and justify the drying linseed oil based finish layers were applied over a red leadlow Cc value measured on 1 Enna sample as this ancient and primer 7 From the 1930s on the most common replacementthe modern coatings have comparable thickness In the case of for traditional oil paints was the painting with alkyd resins These2 Bergamo Cc is comparable to those measured on the modern materials provided the advantage of a higher layer thicknesspaint and this could be connected to the lower coating thickness from one application and faster drying than the traditional oilsThe estimated Rp values of the ancient samples were more than 4one order of magnitude lower than that on modern gray cast The electrochemical characterization of paints further confirmediron at the end of salt spray test exposure evidencing the higher the capability of EIS technique in evaluating the conservationcorrosion rates of the underlying metal due to the scarce residual state of ancient painted artefacts 9 11 12 and the barrier propprotectiveness of the ancient coatings erty variations in modern coatings even when not detectable byvisual observation 29DISCUSSIONThis work evaluates the conservation state of European street CONCLUSIONSfurniture in painted and partially corroded cast iron artefacts All Our study investigates the state of conservation of four paintedexamined cast irons can be classified as gray cast irons The dis and partially corroded post mounted luminaries dating back totribution of the lamellar graphite of Type B in samples 1 Enna the nineteenth and the twentieth centuries and coming from2 Bergamo and 3 Imola is frequently encountered on alloys so foundries located in Italy and France The microstructure of thelidified with an intermediate degree of undercooling whereas cast irons was consistent with the procedures employed forthe distribution of type D and the very fine graphite lamellae of manufacturing complex shape casting with variable wall thickthe sample 4 Nice forms typically under a relatively high degree ness The Italian castings were composed of lamellar graphite ofof undercooling 28 All metalworks show microstructures with Type B and with lamellae between 0 06 and 0 25 mm in lengthhigh steadite contents It is known that the presence of steadite For the samples 2 Bergamo and 3 Imola the microstructureis due to the addition of phosphorus This element lowers the was pearlitic with a high amount of steadite and manganesemelting point and improves the fluidity of cast iron alloys thus sulfides The microstructure of the sample 1 Enna was similarfavoring the manufacturing of complex shape castings with thin but with ferrite close to the graphite rosettes The French castwall thickness e g castings for European street furniture 28 ing had lamellar graphite of Type B with lamellae length shorterThe study of the patina stratification the main corrosion products than 0 015 mm and a microstructure similar to that of samplesand corrosion attack morphology suggests that a specific corro 2 Bergamo and 3 Imolasion phenomenon occurred In an outdoor environment where The study of the patina stratification the main corrosion productspaints are partially removed and or damaged acidic rainwater and corrosion attack morphology indicated the graphitization ofstarts to corrode cast iron alloys As the ferrous matrix corrodes cast irons This phenomenon was accompanied by the depositionthe more noble graphite further promotes the attack of the sur of thick layers of corrosion containing lepidocrocite goethiterounding metal by the galvanic coupling effect The graphitic cor and impurities from the corrosive environmentrosion residue is impregnated with corrosion products of iron On the examined fragments no historical paints were detectedlepidocrocite characterized by a flower like pattern and a foam suggesting the removal of the deteriorated paint layers from thelike morphology and goethite with a cloudy or cotton ball like surfaces before the application of modern paint systems Finallymicrostructure as identified by FT IR and VPSEM EDS The af the electrochemical characterization established the poor protecfected surfaces show a compact layer of graphite rust and impu tiveness offered by the paints on the post mounted luminariesrities as confirmed by the scanning electron microscope observations that may inhibit further damage The cast iron elementsretain their appearance and shape but undergo a mechanical14 La Metallurgia Italiana n 4 2018Storia della metallurgia e beni culturaliACKNOWLEDGEMENTSDr Raffaella Bassi Neri and Dr Antonio Neri NERI Foundation The Italian Museum of Cast Iron Longiano FC Italy are gratefullyacknowledged for providing the cast iron artefacts investigated in the present workREFERENCES1 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 castiron in the 19th and 20th centuries R Bassi C Biasini Selvaggi M G Massafra Eds Barbieri Selvaggi Editori Manduria 20112 R Bassi Neri La ghisa quando il gusto incontro l arte industriale Arredo Citta 2 2011 53 J Gay Cast iron Architecture and ornament Function and Fantasy John Murray Publishers Ltd London 19854 S Godfrain R Pender B Martin English Heritage Practical building conservation Metals Ashgate Publishing Limited Farnham5 A Reynaud Corrosion of cast irons in Sheir s Corrosion Corrosion and degradation of engineering materials vol 3 B Cottis MGraham R Lindsay S Lyon T Richardson D Scantlebury H Stott Eds Elsevier Ltd Amsterdam 2010 p 1737 17886 P Dillmann D Watkinson E Angelini A Adriaens Corrosion and conservation of cultural heritage metallic artefacts WoodheadPublishing Cambridge 20137 K Kreislova D Knotkova H Geiplova Atmospheric corrosion of historical industrial structures in Corrosion and conservation ofcultural heritage metallic artefacts P Dillmann D Watkinson E Angelini A Adriaens Eds Woodhead Publishing Cambridge2013 p 311 3438 X X Fu J H Dong E H Han W Ke A new experimental method for in situ corrosion monitoring under alternate wet dry conditions Sensors 9 2009 10400 104109 C Li Y Ma Y Li F Wang EIS monitoring study of atmospheric corrosion under variable relative humidity Corros Sci 52 201010 C Thee L Hao J Dong X Mu X Wei X Li W Ke Atmospheric corrosion monitoring of a weathering steel under an electrolytefilm in cyclic wet dry condition Corros Sci 78 2014 130 13711 E Angelini D Assante S Grassini M Parvis EIS measurements for the assessment of the conservation state of metallic works ofart Int J Circ Syst Signal Process 8 2014 240 24512 S Grassini S Corbellini M Parvis E Angelini F Zucchi A simple Arduino based EIS system for in situ corrosion monitoring ofmetallic works of art Measurement 114 2018 508 51413 F Mansfeld Use of electrochemical impedance spectroscopy for the study of corrosion products protection by polymer coatings JAppl Electrochem 25 1995 187 20214 A Nishikata Y Ichihara T Tsuru An application of electrochemical impedance spectroscopy to atmospheric corrosion study Corros Sci 37 1995 897 91115 A Nishikata Y Yamashita H Isatayama T Tsuru A Usami K Tanabe H Mabuchi An electrochemical impedance study on atmospheric corrosion of steels in a cyclic wet dry condition Corros Sci 37 1995 2059 206916 A Nishikata F Suzuki T Tsuru Corrosion monitoring of nickel containing steels in marine atmospheric environment Corros Sci47 2005 2578 258817 P Letardi Use of electrochemical impedance spectroscopy on outdoor bronze monuments CSA EAS06 13 14 November 2006Somerset USA18 P Letardi Laboratory and field tests on patinas and protective coating systems for outdoor bronze monuments Proceedings ofMetal 2004 4 8 October 2004 National Museum of Australia Canberra ACT Australia p 379 38719 A Balbo M Abbottoni A Frignani C Chiavari C Martini E Bernardi C Monticelli In situ EIS characterization of outdoor corrosion behaviour of bronze and gilded bronze EUROCORR 2014 European Federation of Corrosion Event No 364 8 12 September2014 Pisa Italy Paper 7259 p 1 920 S S Jamali Y Zhao Z Gao H Li A C Hee In situ evaluation of corrosion damage using non destructive electrochemical measurements A case study J Ind Eng Chem 43 2016 36 4321 S Rahimi R M Moattari L Rajabi A Ashraf Derakhshan M Keyhani Iron oxide hydroxide FeOOH nanoparticles as highpotential adsorbents for lead removal from polluted aquatic media J Ind Eng Chem 23 2015 33 4322 T Ishikawa Y Kondo A Yasukawa K Kandori Formation of magnetite in the presence of ferric oxyhydroxides Corros Sci 401998 1239 125123 J N Murray Electrochemical test methods for evaluating organic coatings on metals an update Part III Multiple test parametermeasurements Prog Org Coat 31 1997 375 391La Metallurgia Italiana n 4 2018 15Archaeological and historical artefacts24 A Lasia Electrochemical impedance spectroscopy and its application Springer Science Business Media New York 201425 G Trabanelli C Monticelli V Grassi A Frignani Electrochemical study on inhibitors of rebar corrosionin carbonated concrete Cement Concrete Res 35 2005 1804 181326 C Zhang J Zhao Effects of pre corrosion on the corrosion inhibition performance of three inhibitors on Q235 steel in CO2 H2Ssaturated brine solution Int J Electrochem Sci 12 2017 9161 917927 J Gonzalez Guzman J J Santana S Gonzalez R M Souto Resistance of metallic substrates protected by organic coating containing glass flakes Prog Org Coat 68 2010 240 24328 ASM Specialty Handbook Cast Irons ASM International Materials Park Ohio 199629 F Deflorian S Rossi L Fedrizzi P L Bonora Testing of protective organic coatings on metals comparison of salt spray and electrochemical impedance spectroscopy J Test Eval 31 2 2003 91 9716 La Metallurgia Italiana n 4 2018
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elko ep branches over the worlds exporting countries 13 70 12 000 000 manufactured products 10 000 inels installation 330 employees 2nd position in europe
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