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Gojka Pajagič-Bregar, Narodni muzej SlovenijePIXE metoda za analiziranjedrevnog tekstila iz grobnicaZa izložbu «Theatrum vitae et mortis humanae« -Prizorišče človeškega življenja in smrti ( Podobe iz17. stoletja na Slovenskem), koja je održana 2002. godine,u Narodnom muzeju Slovenije 1 konzervirali smo višetekstilnih artefakata, između ostalog i fragmenat takozvaneValvazorove čipke.Čipka (veličine 5,3 – 6 cm x 11,3 cm) pronađena je uArhivu Slovenije, prilikom istraživanja materijala zaimenovanu izložbu, u privatnom arhivu Petra von Radicsa(fascikl 8). On je delovao u 19. stoleću i između ostalogistraživao je Valvazorov život i rad. Čipka je bilaspremljena u plavoj koverti na kojoj je pisalo da se radio čipki iz Valvazorove grobnice, iz dvorca Medije. Prilikomotvaranja grobnice, u 19. stoleću, pronašli su čipkui još neke predmete, koji su se nažalost kasnije izgubili.Radi se o klekanoj čipki.To je tehnika prekrštavanja,sukanja i premetavanja najmanje dve, a po pravilu višeniti, od kojih je svaka namotana na svoj batić/klekalj -posebno oblikovani drveni kalem.Klekana čipka sa cvetnim motivima krizanteme, posvemu sudeći, potiće iz Mechelena, u Belgiji. Čipka je uizuzetno fragilnom stanju. To su uzrokovali ekstremniklimatsko i biološko - hemijski uvjeti u grobnici, teagresivnost železotaninske boje. Mikroskopske analizesu pokazale, da se radi o svilenoj niti. 2 Prilikom posmatranjauzdužnog izgleda vlakna pokazalo se da je vlaknoravno, glatko i bez posebnih odlika, te karakterističnoza svilenu nit.Gojka Pajagič- Bregar, National Museum of SloveniaPIXE method for analyzingancient textile from tombsDa bismo potvrdili rezultate,čipku smo dodatno analizirali naInstitutu za tehnologiju i grafičnu tehnologijui dizajn, koji deluje u okviru Tekstilnog fakulteta uLjubljani, upotrebivši hemijski reagens jod – jodhlor.Mikrohemijska reakcija je rezultirala tako, da su sesvilena vlakna obojila žuto. Analiza je i kod mikroskopiranjarastarskim elektronskim mikroskopom (SEM)potvrdila, da se radi o svilenoj niti. 3 Iz sačuvanog gradiva,a i iz arhiva poznato nam je, da su čipke bile rađenevećinom od lana, i bijele boje, ređe od svile i crneboje, a braon skoro nikako. Valvazor, polihistor i velikium slovenačke istorije, po svom ugledu i društvenom1 Tom prilikom izdali smo knjigu rasprava:Theatrum vitae etmortis humanae –Prizorišče človekovega življenja in smrti i katalogTheatrum vitae et mortis humanae – Prizorišče človeškega življenjain smrti2 Mikroskopsku analizu čipke na optičkom mikroskopu uradilaje mg Gojka Pajagič Bregar, Narodni muzej Slovenija3 Analize su radili dr Urša Stankovič Elesini i inž. JanaRozman, Inštitut za tehnologijo in grafično tehnologijo ter oblikovanje,Oddelek za tekstilstvo, Naravoslovnotehniška fakulteta,Ljubljana146For the purpose of display at the “Theatrum vitae etmortis humanae” –Theatre of Human Life and Death,which took place in the National Museum of Slovenia1 in 2002, we were engaged to conserve several textileartifacts, among other, a fragment of the so-calledValvazor’s lace.The lace (5.3 – 6 cm wide and 11.3 cm long) wasfound in the Archive of Slovenia, while investigatingmaterial for the mentioned exhibition, in the private archiveof Petar von Radics (folder no. 8). He was a 19 thcentury scientist, doing research on Valvazor’s life andwork, among other things. The lace was kept in a blueenvelope, with a note saying it was a lace from Valvazor’stomb, from Media castle. The lace was found in the19 th century, together with other objects when the tombwas opened but unfortunately they were lost afterwards.It is a crocheted lace piece. Various techniques wereapplied in its production, threads transposing, spinningand warping at least of two, but normally of severalthreads wound around crocheting needles, in the formof specially modelled wooden spindles.This pillow lace with bobbins and chrysanthemumdecoration apparently originates from Mechelen, Belgium.The lace is extremely fragile, due to extreme climateand biological-chemical conditionsin the tomb, and the aggressiveness of irontannindye. Microscopic analyses showed that it wasmade of silk thread 2 . The visual investigation of thethread led to a conclusion that the tread is flat, smoothand without special characteristics, which is typical ofa silk thread.In order to confirm the results, the lace was additionallyanalyzed at the Institute of Technology, GraphicalTechnology and Design, which functions as part of theFaculty of Textiles in Ljubljana, using iodine – iodinechlorineas the chemical reaction agent. The micro chemicalresult was yellow colour of the silk threads. TheSEM (Scanning electronic microscope) analysis alsoconfirmed this result 3 .1 On this occasion, a book of papers “Theatrum vitae et mortishumanae – Prizorišče človekovega življenja in smrti», as well as thecatalogue «Theatrum vitae et mortis humanae – Prizoriščečloveškega življenja in smrti» were published.2 The microscopic analysis of the lace by optical microscope wasdone by Gojka Pajagič Bregar, M.A, the National Museum ofSlovenia3 The analyses were carried out by Urša Stankovič Elesini, D.Sc., and Jana Rozman, of the Institute of Technology, GraphicalTechnology and Design, Department of Textile, the Faculty ofScience and Technology in Ljubljana

statusu, i uz činjenicu da je čipka nošena u pijetetnommomentu pokopa, najverovatnije je bio odenut u crnuodoru, a i čipka je, tako samo pretpostavljali bila crneboje. U to vreme su za bojadisanje i pripremanje crneboje, po određenim drevnim recepturama, uz ostalesmese, upotrebljavali železni oksid, te koru drveta, zbogtinina. Da bismo potvrdili tu pretpostavku, odlučili smose za istraživanje Pixe metodom –nedestruktivnomanalizom elemenata. 4 Istraživanja Pixe analizom potvrdilasu našu hipotezu – rezultati su pokazali visokoprisustvo jona železa i tragove tipičnih mikroelemenata.Za bojadisanje svilene niti nedvojbeno su upotrebiliželezov oksid. Železov oksid je agresivan i, koliko namje poznato, njegovo prisustvo u bojama za ukrašavanjeknjižnog gradiva prouzrokovalo je brži raspad pisanoggradiva, a i u našem slučaju prouzrokovalo je veći stupanjdegradacije vlakna svilene niti, od koje je izrađenačipka. Poznato nam je, da je svila kao material inačepodložnija hemiskoj razgradnji. Tome su doprineli iuvjeti grobne atmosfere, te je degradacija boje prouzrokovalapromenu u današnju braon boju. Ovaj rezultatnas je ponukao, da istom metodom provjerimo prisutnostelemenata željeznog oksida i u tekstilnim fragmentimaiz grobnice u Betnavi, kod Maribora i Gradu,kod Slovenj Gradca. 5 Za analizu smo uzeli somotnuplaštanicu, kao i unutrašnju svilenu podlogu uzorkakarakterističnog za 17. stoleće.Pixe postupkom smo analizirali takođe i jednu svilenu,i jednu vunenu čarapu. 6 Svi pomenuti tekstilni artefaktisu vremenom promenili boju i sada su različitihbraon nijansi, te u različitom stupnju degradacije.To su bili tek početni istraživački koraci, koji su seodnosili na problem promene boje na tekstilnim artefaktimaiz grobova. Pitanje ostaje otvoreno za nova istraživanjai radove na tom području, koji će, u svakomslučaju, biti značajan doprinos osvetlenju tog problema.Žiga Šmit, SlovenijaAnaliza fragmenatatkanina metodom PIXEMerenja za fragmente tkanina uradili smo metodomprotonski indukovanih rentgenskih zraka (PIXE) uvazduhu. Za izvor protona upotrebili smo tandemskiakcelerator na Institutu Jožef Stefan. Protoni s energijom3 MeV su prolazili slobodno kroz foliju od tantaladebljine 2 mikrometra. Tako nije bilo potrebno uzimatiuzorke sa delova tkanine, nego smo određena mesta natkanini izložili neposredno protonskim zracima.Za normalizaciju smo upotrebili argonov signal izvazduha i zato smo dužinu vazdušnog otvora između izlaznogprozorčića i uzorka fiksiralimetalnom pregradom. Geometrijske parametre smoodredili na osnovu serije uzoraka čiji sastav je bio poznat.Kao absorber mekih rentgenskih zraka je služio 58mm širok vazdušni otvor između uzorka i detektora. RezolucijaSi (Li) detektora rentgenskih zraka bila je 150eV na 5,9 keV. Program AXIL je korišćen za odvijanjespektra. Proračuni elementarnih koncentracija su sugerisaliceluloznu shemu. Rezultati analize su predstavljeniu tabeli 1.4 Istraživanja je radio dr Miloš Budnar, Inštitut Jožef Štefan,Ljubljana5 Andreja Vrišar, Prispevek k razvoju noše v 17. stoletju naSlovenskem – Grobni najdbi iz Betnave pri Mariboru in Gradu priSlovenjem Gradcu, Kronika,letnik 27, št.2, Ljubljana 19796 Ta istraživanja radio je dr. Žiga Šmit, Inštitut Jožef Štefan,LjubljanaIt is known, from preserved material and archives,that this kind of lace was usually white and made offlax, or, not that often, of silk and in black, but almostnever brown.Valvazor, a polyhistor and a great mind ofthe Slovenian history, having in mind his social statusand the fact that the lace was worn on the occasion ofthe burial, was probably wearing black, so the lace was,as we assumed, dyed black. At the time, iron oxide ortree-bark, because of tannin, were used for dying andpreparation of black dye.To confirm our assumption, wedecided to use PIXE analyzing method – a non-destructiveanalysis of chemical elements 4 . The PIXE analysisconfirmed our hypothesis – the results showed a highquantity of iron ions and traces of typical microelements.Undoubtedly, iron oxide was used for dying thelace. Iron oxide is aggressive and, as far as we know, itspresence in dyes used for decoration of books usuallyaccelerated deterioration of written material, and in ourcase, it caused a higher level of degradation of silk fiber,the material that the lace was made of. It is well knownthat lace is material quite prone to chemical deterioration.The tomb atmospheric conditions contributed tothis process, so deterioration of the dye caused the changeof colour into brown, as it is today. This result encouragedus to use the same method to check the presenceof iron oxide also in textile fragments from the tomb inBetnava, near Maribor and in Grad, near Slovenj Gradec5 .A velvet cloak and an inner silk layer of a sample typicalof 17 th century were chosen for the analysis.The PIXE method was used also for analyzing of asilk and a woolen sock 6 . All these textile artifacts changedtheir colour with time, and now they show differenttones of brown, in different phases of degradation.These analyses were only the beginning, referring tothe problem of colour change on textile artifacts fromtombs. This subject is open for new researches andworks in this field, which would be, nevertheless, a significantcontribution to the interpretation of the issue.Žiga Šmit, SloveniaAnalysis of the textile fragmentsby the PIXE methodMeasuring of the textile fragments was performedby the method of proton-induced X–rays (PIXE) inthe air. As a proton source, the Tandetron accelerator ofthe Jožef Stefan Institute was applied. Protons with anenergy of 3 MeV entered air after passing a 2 micrometertantalum window. The selected points in the textileswere then irradiated directly, thus avoiding sampling.For the spectrum normalization, the argon signal fromthe air was used, so the air gap between the exit windowand target was kept fixed with a metal spacer. The geometricalparameters were calibrated from the measurementof a series of targets with known compositions.The 58 mm wide air gap between target and detector alsoserved as an absorber for soft X-rays. The resolutionof Si(Li) X-ray detector was 150 eV at 5.9 keV. The spectrumde-convolution was performed by the AXIL program.The calculation of elemental concentrations assumeda cellulose matrix. The analytical results are collectedin Table 1.4 The research was conducted by Miloš Budnar, D.Sc., JožefŠtefan Institute, Ljubljana5 Andreja Vrišar, Prispevek k razvoju noše v 17. stoletju naSlovenskem – Grobni najdbi iz Betnave pri Mariboru in Gradu priSlovenjem Gradcu, Kronika, letnik 27, no. 2, Ljubljana 19796 This research was conducted by Žiga Šmit, D.Sc , Jožef ŠtefanInstitute, Ljubljana147

Gojka Pajagič-Bregar, Narodni muzej SlovenijePIXE metoda za analiziranjedrevnog tekstila iz grobnicaZa izložbu «Theatrum vitae et mortis humanae« -Prizorišče človeškega življenja in smrti ( Podobe iz17. stoletja na Slovenskem), koja je održana 2002. godine,u Narodnom muzeju Slovenije 1 konzervirali smo višetekstilnih artefakata, između ostalog i fragmenat takozvaneValvazorove čipke.Čipka (veličine 5,3 – 6 cm x 11,3 cm) pronađena je uArhivu Slovenije, prilikom istraživanja materijala zaimenovanu izložbu, u privatnom arhivu Petra von Radicsa(fascikl 8). On je delovao u 19. stoleću i između ostalogistraživao je Valvazorov život i rad. Čipka je bilaspremljena u plavoj koverti na kojoj je pisalo da se radio čipki iz Valvazorove grobnice, iz dvorca Medije. Prilikomotvaranja grobnice, u 19. stoleću, pronašli su čipkui još neke predmete, koji su se nažalost kasnije izgubili.Radi se o klekanoj čipki.To je tehnika prekrštavanja,sukanja i premetavanja najmanje dve, a po pravilu višeniti, od kojih je svaka namotana na svoj batić/klekalj -posebno oblikovani drveni kalem.Klekana čipka sa cvetnim motivima krizanteme, posvemu sudeći, potiće iz Mechelena, u Belgiji. Čipka je uizuzetno fragilnom stanju. To su uzrokovali ekstremniklimatsko i biološko - hemijski uvjeti u grobnici, teagresivnost železotaninske boje. Mikroskopske analizesu pokazale, da se radi o svilenoj niti. 2 Prilikom posmatranjauzdužnog izgleda vlakna pokazalo se da je vlaknoravno, glatko i bez posebnih odlika, te karakterističnoza svilenu nit.Gojka Pajagič- Bregar, National Museum of SloveniaPIXE method <strong>for</strong> analyzingancient textile from tombsDa bismo potvrdili rezultate,čipku smo dodatno analizirali naInstitutu za tehnologiju i grafičnu tehnologijui dizajn, koji deluje u okviru Tekstilnog fakulteta uLjubljani, upotrebivši hemijski reagens jod – jodhlor.Mikrohemijska reakcija je rezultirala tako, da su sesvilena vlakna obojila žuto. Analiza je i kod mikroskopiranjarastarskim elektronskim mikroskopom (SEM)potvrdila, da se radi o svilenoj niti. 3 Iz sačuvanog gradiva,a i iz arhiva poznato nam je, da su čipke bile rađenevećinom od lana, i bijele boje, ređe od svile i crneboje, a braon skoro nikako. Valvazor, polihistor i velikium slovenačke istorije, po svom ugledu i društvenom1 Tom prilikom izdali smo knjigu rasprava:Theatrum vitae etmortis humanae –Prizorišče človekovega življenja in smrti i katalogTheatrum vitae et mortis humanae – Prizorišče človeškega življenjain smrti2 Mikroskopsku analizu čipke na optičkom mikroskopu uradilaje mg Gojka Pajagič Bregar, Narodni muzej Slovenija3 Analize su radili dr Urša Stankovič Elesini i inž. JanaRozman, Inštitut za tehnologijo in grafično tehnologijo ter oblikovanje,Oddelek za tekstilstvo, Naravoslovnotehniška fakulteta,Ljubljana146For the purpose of display at the “Theatrum vitae etmortis humanae” –Theatre of Human Life and Death,which took place in the National Museum of Slovenia1 in 2002, we were engaged to conserve several textileartifacts, among other, a fragment of the so-calledValvazor’s lace.The lace (5.3 – 6 cm wide and 11.3 cm long) wasfound in the Archive of Slovenia, while investigatingmaterial <strong>for</strong> the mentioned exhibition, in the private archiveof Petar von Radics (folder no. 8). He was a 19 thcentury scientist, doing research on Valvazor’s life andwork, among other things. The lace was kept in a blueenvelope, with a note saying it was a lace from Valvazor’stomb, from Media castle. The lace was found in the19 th century, together with other objects when the tombwas opened but un<strong>for</strong>tunately they were lost afterwards.It is a crocheted lace piece. Various techniques wereapplied in its production, threads transposing, spinningand warping at least of two, but normally of severalthreads wound around crocheting needles, in the <strong>for</strong>mof specially modelled wooden spindles.This pillow lace with bobbins and chrysanthemumdecoration apparently originates from Mechelen, Belgium.The lace is extremely fragile, due to extreme climateand biological-chemical conditionsin the tomb, and the aggressiveness of irontannindye. Microscopic analyses showed that it wasmade of silk thread 2 . The visual investigation of thethread led to a conclusion that the tread is flat, smoothand without special characteristics, which is typical ofa silk thread.In order to confirm the results, the lace was additionallyanalyzed at the Institute of Technology, GraphicalTechnology and Design, which functions as part of theFaculty of Textiles in Ljubljana, using iodine – iodinechlorineas the chemical reaction agent. The micro chemicalresult was yellow colour of the silk threads. TheSEM (Scanning electronic microscope) analysis alsoconfirmed this result 3 .1 On this occasion, a book of papers “Theatrum vitae et mortishumanae – Prizorišče človekovega življenja in smrti», as well as thecatalogue «Theatrum vitae et mortis humanae – Prizoriščečloveškega življenja in smrti» were published.2 The microscopic analysis of the lace by optical microscope wasdone by Gojka Pajagič Bregar, M.A, the National Museum ofSlovenia3 The analyses were carried out by Urša Stankovič Elesini, D.Sc., and Jana Rozman, of the Institute of Technology, GraphicalTechnology and Design, Department of Textile, the Faculty ofScience and Technology in Ljubljana

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