RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 89 three investigated sites form rather similar pat- Laboratory for Radiological Protection, confirms terns, though their values differ much in some cases the method reliability. like for Sb, Co, Se, Cr and Zn. Some elements like Sb, W, As, Se and Zn are highly concentrated in References APM when compared with their occurrence in the [1]. Boubel R.W., Fox D.L., Turner B.: Fundamentals of Earth’s crust. This shows their anthropogenic oc- Air Pollution. 3rd edition. Academic Press, London currence in APM. Elements like W and Zn are 1994. mainly associated with the steel industry and may [2]. Seinfeld J.H., Pandis S.N.: Atmospheric Chemistry come from Polish as well as from the neighbouring and Physics: From Air Pollution to Climate Change. countries’ sources. The other ones like Sb, As and John Wiley & Sons, 1997. [3]. Environmental Development. IAEA Bull., 38, 2 (1996). Se are mainly associated with coal combustion and [4]. Air Pollution and Its Trends. UNDP/RCA/IAEA motor vehicle exhausts [1,3-5]. Project RAS/97/030/A/01/18, 1997. This could be explained by the fact that over [5]. IAEA/ANL Interregional Training Course on Nuclear 80% of energy production in Poland come from Related Analytical Techniques in Air Pollution Mo- coal burning and that in the neighbourhood of the nitoring and Research. Lectures. Argonne National Polish big cities, power/heating plants are located. Laboratory, Argonne, USA 1993. It is perhaps worth to conclude that high EFs for [6]. Steinnes E., Rambaek J.P., Hanssen J.E.: Chemo- the same elements has also been observed by the sphere, 25, 735 (1992). authors when analyzing fly ashes coming from [7]. Kuik P., Wolterbeek H.Th.: Water, Air, Soil Pollut., Polish power plants [12]. 84, 323 (1995). [8]. Compendium of Methods for Determination of Inor- The method reliability ganic Compounds in Ambient Air. Center for Envi- A significant analytical problem encountered ronmental Research Information, U.S. Environmental in the analysis of APM collected on filters may arise Protection Agency, June 1999. from a blank, i.e. filter itself [5,15,17]. It may con- [9]. Dybczyński R.: Chem. Anal. (Warsaw), 46, 133 (2001). tain some elements at measurable levels (roughly [10]. Barnett V., Turkman K.F.: Statistics for the Environ- from one tenth up to one third) of the content of ment. Vol.3. Pollution Assessment and Control. John these elements in APM. In this work, it was the Wiley & Sons, 1997. case for Yb, Cs, Sc, Sb, Rb, and As. For Br, the [11]. Hopke P.K., Gladney E.S., Gordon G.E., Zoller W.H., relatively high and changeable content of this ele- Jones A.G.: Atmos. Environ., 10, 1015 (1976). ment in filters has made its quantitative determi- [12]. Szopa Z., Dybczyński R., Kulisa K., Sterliński S.: Chem. Anal. (Warsaw), 39, 497 (1994). nation unreliable. [13]. Bysiek M., Biernacka M., Jagielak J.: Zanieczyszczenie Analyzing two CRMs along with the APM promieniotwórcze przyziemnego powietrza atmosfe- analyses has assessed the method reliability. Un- rycznego w Polsce w 1998 roku. Centralne Labora- fortunately, CRMs of the same or similar matrix torium Ochrony Radiologicznej, Warszawa, 2000, like APM have not been available. Therefore, two Raport CLOR Nr 142, in Polish. others, well known CRMs of geological/environ- [14]. Szopa Z., Dybczyński R., Kulisa K., Bysiek M., Bier- mental origination namely SOIL-5 (International nacka M., Sterliński S.: The use of INAA for the evalu- Atomic Energy Agency – IAEA) and CTA-FFA-1 ation of air pollution at three urban sites in Poland. (Institute of Nuclear Chemistry and Technology – Chem. Anal. (Warsaw), 49 (2004), in print INCT) have been analyzed in course of the present [15]. Szopa Z., Dybczyński R.: Simple PC software for rou- tine analysis of gamma-ray specta. In: INCT Annual work. Generally, the results showed a good or at Report 2000. Institute of Nuclear Chemistry and Tech- least satisfactory agreement between them. Addi- nology, Warszawa 2001, p.70. tionally, the agreement of K results, which have [16]. Heide F., Wlotzka F.: Meteorites, Messengers form been obtained on the one hand using INAA at the Space. Springer-Verlag, Berlin 1995. INCT and on the other hand, using the 40K mea- [17]. Bem H., Gallorini M., Rizzio E., Krzemińska M.: surements within ASS-500 network at the Central Environ. Int., 29, 421 (2003).

CENTRAL EUROPEAN CRYSTAL GLASS OF THE FIRST HALF OF THE 18th CENTURY Jerzy Kunicki-Goldfinger, Joachim Kierzek, Piotr Dzierżanowski1/, Aleksandra J. Kasprzak2/ 1/ Faculty of Geology, Warsaw University, Poland 2/ National Museum in Warsaw, Poland Since 1998, a project of investigation into 18th cen- tative chemical analysis of the samples taken from tury central European vessel glass has been under- selected objects. Some preliminary results of the way. Physicochemical analysis has been carried energy dispersive X-ray spectrometry analysis out, as well as stylistic analysis of over 1000 ob- (EDXRF) had been already discussed [2,3]. Here- jects of different provenience. A scheme of the under, some further results in regard to the elec- whole project has been built on three main steps tron probe microanalysis (EPMA) of the selected and had been already discussed in a previous pa- samples will be taken over, and we want to focus per [1]. These steps are historical studies, non-de- on the characteristics of crystal glass which were structive examination of the vessels, and quanti- recognized among the glass manufactured in cer- RADIOCHEMISTRY, STABLE ISOTOPES, 90 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY tain places in central Europe during the first half veloped probably somewhere on the French-Nether- of the 18th century. lands borderlands, chalk glass – credited to Michael In the 17th century, in some centers of northern Müller (1639-1709) in Bohemia, and lead-crystal Europe, new technologies of colourless glass were glass – ascribed traditionally to George Ravenscroft experimented with. It was the consequence of sci- (1618-1681) in England. The first two mentioned ence development of that time, and the migration quickly spread over the continent. But if chalk glass of glassworkers that caused the spread of techno- (later called Bohemian glass, too) became the real- logical innovations. In some glasshouses, new types ly “popular” one; the manufacturing of crystal glass of furnace construction, new kinds of fuel (coal), was characteristic of only a limited number of glass- new raw materials, batches, and so on, appeared. houses that mainly run under royal, ducal or aristo- Many written historical documents may direct our cratic patronage. Michael Vickers writes “No longer attention to certain territories, and information, were kings and princes the arbiters of taste, but revealed in recent years, might lead us to the state- this role was increasingly played by the middle ment that most of the late 17th and early 18th cen- classes of Europe and America. The eighteenth cen- tury luxury colourless glass in almost all of Europe, tury witnessed these important changes” [11]. He including English lead-crystal, could have their tech- writes in relation to the changing role of rock crys- nological roots somewhere on the French and Dutch tal and glass. It also seems true, however, in regard borderland. However, few results of the chemical to the differentiation of crystal glass as a most valu- analyses of these glasses have been known to clearly able metal at this time, and chalk glass as a cheaper support such statement up to now. one; but enough good to fulfil the new baroque The significant changes in the glass technology taste, which expressed itself in frequently dense can be observed already in the earliest 60s in the rich decoration. This decoration occasionally could Netherlands, Netherlands/French borderlands and even be used on metal of imperfect quality. Never- almost immediately on the British islands; in the theless, this simplified history of baroque glass tech- 70s, among other things, also in central Europe nology in northern Europe nowadays seems not [4-6]. Louis le Vasseur d’Ossimont (1629-1689), entirely accurate. Firstly, chalk was already in us- French native, was probably the first and most im- age in western Europe in time of Michael Müller; portant glassworker known to us, who transferred and secondly, lead compounds were used for col- new technology of crystal glass to central Europe. ourless metal in the continent probably indepen- He appeared in Bohemia in Buquoy service in dently of the influence of English technology. Trac- 1673 and established a glasshouse in Nové Hrady ing the succeeding steps of the introduction of the (Gratzen) [7,8]. The lists of raw materials used by new raw materials has, until now, been very puz- him there (which included, among other things, zling. quarz pebbles, saltpeter, arsenic, borax, chalk, wine The terminological context of this crystal glass stone) were characteristic of crystal glass batch. is no less complicated. It is not the intention of the This set of raw materials appeared in Nové Hrady authors to discuss this problem here, but at least at the same time when Johann Kunckel published two of its aspects need be highlighted. The first one crystal glass recipe in “Ars vitraria experimentalis” concerns the differentiation between the original [9]. At present, it is very difficult to state where technological terms and the terms introduced to and when this new batch appeared first in central the professional literature by art historians during Europe. But what is obvious, in the light of docu- the last two centuries. A term Bohemian crystal con- ments as well as of the results of the chemical analy- stitutes one of such examples – whereas crystal glass ses of glasses discussed below, is that these raw was manufactured in Bohemia only in a few glass- materials were characteristic of crystal glass in the houses in the last quarter of the 17th century and last quarter of the 17th century and the 1st half of then probably not before the middle of the 18th the 18th century, as well. This glass formulation century [5]. The second one concerns the different has been practiced in very limited number of glass- semantic connotations of the term crystal glass, houses. One important improvement of this batch, which were sometimes simultaneously used even the addition of lead compounds, was probably of in historical times. The term crystal derives from slightly later origin. Although, what has been al- Greek Krystallo denoting glass that resembles rock ready shown on the example of the 18th century crystal, a material that belonged to one of the most glasses, intentionally introduced lead in central precious ones [12]. Therefore, a quality of metal European glass can already be observed in items constituted an important feature when one used dating around 1700 [10]. This date might well be- the term crystal glass. On the other hand, this high come earlier in the future when more 17th cen- quality glass was used to imitate very expensive, tury crystal glass wares are examined. rare and frequently richly decorated wares made Almost till the end of the 17th century this new of rock crystal [13]. Put simply, glass ware resembled glass formulae competed with Venetian cristallo more expensive rock crystal ware. The type, shape that had been dominant up to that time. This pe- and decoration of the ware was as valuable a fea- riod saw the decline of soda-ash colourless glass ture as the quality of its metal. David Jacoby in his as well as the end of the dominance of façon de article about the raw materials used in Venice and Venice in the market of the luxury tableware. At the Terraferma writes according the term cristallino: turn of the 17th century in Europe, at least three “We may safely assume that once this material [glass] main glass formulae for luxury colourless vessels had been improved, a specific type of vessel was were being developed separately: crystal glass – de- designed to be exclusively made of it so as to high- RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 91 light its particular features. As a result, the term tuted a very important feature. Pyrolusite remain- crsitallino, first applied to the material, was later ed the main decolourizing agent. Beside saltpeter, used to designate the mold and the vessel related there were applied new raw materials: arsenic and to it. There was thus a direct link between the type wine stone. The saltpeter/potash ratio as well as the of material used and the specific shape given to whole batches differentiated each other depend- the finished luxury product. This relationship was ing on the glasshouse and glassmaking tradition. similar, say, to that existing between the particular Crystal glass production required the best qual- features of the glass from which vessels were made ity raw materials, but obviously in this regard, par- and the choice of specific cutting designs and tech- ticular glasshouses differed from one another, too. niques used for their decoration” [14]. Although, The crystal glass batch distinguished itself also in according to Venetian cristallo, W. Patrick McCray certain other qualities. The saltpeter/potash ratio calls our attention towards some statements by the was much higher than in the case of white glass batch Renaissance persons (15th-17th centuries) “regard- or potash could even be completely replaced by salt- ing what was desired in terms of glass quality (the peter. The saltpeter/chalk ratio was also higher than material and not the form)” [15]. The phenomenon for white glass. On the basis of chemical analysis, of understanding the term crystal glass as a certain we are not able to distinguish the fraction of potas- type of vessel or/and certain type of its decoration, sium introduced with saltpeter from the fraction seems to return in the 18th century or even at the introduced with potash and wine stone which also turn of 17th century. It cannot be excluded that this constituted a source of the element. Considering phenomenon was influenced by the change of only dependence of the concentration of alkaline “good taste” in that time, as strongly underlined by and alkaline earths oxides in glass, the differenti- Michael Vickers [11]. Numerous 18th century glass- ating of white and crystal ones is possible in most houses were called crystal glasshouses, and the term cases, but not always. Figure well illustrates the tech- crystal glass was widely applied towards the certain nological relationship between vitrum blanchum types of vessels frequently very rich decorated but and white glass as well as between cristallo and crys- manufactured with the use of cheaper chalk glass. tal glass. Considering vitrum blanchum manufac- The susceptibility of glass for applying fashionable tured in other places than Venice, even in northern decoration constituted more important feature Europe, this scatter plot does not undergo signifi- than quality of the metal. In the discussion below, cant changes. Only for the sum of alkaline oxides the term crystal glass will only concern the special (Na2O + K2O), a contribution of Na2O and K2O kind of metal. According to known sources, in the 1670s in central Europe, crystal glass was manufactured only in a few glasshouses in Bohemia (Buquoy glass) and Brandenburg. At the beginning of the 18th century, crystal glass seemed to survive in central Europe only in some German and Polish glasshouses – on the territories, where luxury glass production was still maintained mainly by the royal and aristoc- racy courts. The Polish-Saxon Union (1697-1763) was of a certain importance in this process, too [16]. In central Europe in the first half of the 18th century, three main types of colourless vessel glass – crystal, white (chalk) and ordinary – were manu- Fig. Scatter plot for Venetian soda-ash glass (vitrum blan- factured. They corresponded to the former Vene- chum, cristallo) [18] and 18th century central European potassium glass (white, crystal) (own results). tian glass types: cristallo, vitrum blanchum and vetro communale [17]. changes respectively to the type of applied ash. Now Vetro communale, as most ordinary glass might we can easily observe that white glass constitute con- be compared with forest glass. Ordinary glass was tinuation of northern vitrum blanchum manufac- their successor. It was melted as a rule with the tured frequently with the use of mixed alkaline ashes use of four basic raw materials (sand, lime, potash or even noticeable potash-ash. The same concerns and pyrolusite) and, excepting of pyrolusite, these crystal glass. In this case, salicornia was replaced raw materials were gained from local, easily ac- mainly by saltpeter and the sodium contribution to cessible sources. We can recognize such glass on this sum of alkaline oxides appears almost insig- the basis of a few qualities. The absence of arsenic nificant. But the overall ratio of alkaline and alka- is the first one, assumed obviously that the element line earths oxides remains the same. Due to the pos- was not introduced with a cullet, and the high con- sible overlapping of regions characteristic of crystal tent of glass contaminations constitutes no less and white glass when the alkaline oxides/alkaline important feature of the metal. earths oxides ratio is considered, the As2O3/CaO White glass might be considered as a successor ratio constitutes a better and more convenient tech- of vitrum blanchum. There were multicomponent nological indicator. Firstly, the proportion of arsenic batches used for its production and the raw mate- is related (in many cases) to the proportion of salt- rials were better selected and purified. Chalk was peter due to the technological requirements. Sec- used in place of lime stone; potash was partly re- ondly, there is easier to estimate arsenic than po- placed by saltpeter; the quality of the sand consti- tassium content in the glassware by the use of RADIOCHEMISTRY, STABLE ISOTOPES, 92 NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY non-destructive methods (like EDXRF). The next taneously working spectrometers (PET, LIF, TAP important feature that discriminates crystal glass crystals and PC2 for boron) at the Electron Micro- is boron presence in the glass. We are not fully con- probe Laboratory (Faculty of Geology, Warsaw vinced whether borax was used exclusively for crys- University). The measurements conditions were as tal glass production. It is difficult to detect boron follows: by the analytical methods commonly applied to ba- - for main constituents: 15 kV, 6 nA, beam diam- roque glass analysis or their detection limits for eter – 20 µm, counting time – 20 s for each ele- boron are not sufficient. But, as till now, both still ment; scarcities of written sources and of the results of - for minor and trace constituents (with fixed con- chemical analyses confirm the boron presence only centration of main constituents): 20 kV, 100 nA, in crystal glass. beam diameter – 80 µm, counting time – 20-60 s; Having distinguished the main glass formula- - for boron (with fixed concentration of main and tions, it is important to underline that among crys- minor constituents): 5 kV, 100 nA, beam diam- tal and white glasses, there were found glasses which eter – 20 µm, counting time – 20 s. contained also lead [10]. For white glass only some Standards were oxides and minerals. Corning C, D of the items examined contained lead and its high- and NIST 610, 612 were used as secondary standards. est concentration reached about 2%wt. It was im- There was good agreement between the EDXRF possible to distinguish white glasses with intention- and EPMA results according to the most of the ally and accidentally (e.g. with cullet) introduced examined elements. For example, the correlation lead. Among crystal glasses, most of them contained coefficient (R) for PbO concentration analysed by lead and it was possible to distinguish unleaded from both the systems amounted to 0.9952 (n=12). Al- leaded items. This is surely influenced by the bet- though some small discrepancies have been also ter technological regime and the greater care taken found. They are discussed in the mentioned above when crystal glass was manufactured. For the lead- forthcoming article. ed crystal glass, the PbO concentration exceeded The authors express their gratitude to the Boards ~0.4%wt. and reached in certain cases almost of Museums who made the vessels available for ex- 13%wt. The overlapping of these PbO concentra- amination: National Museums (Kraków, Poznań, tion ranges (~0.4-~2%) means that knowledge Warszawa, Wrocław), Royal Castle in Warsaw, Wi- about lead concentration does not constitute al- lanów Museum Palace, District Museum in Tarnów, ways a differentiating feature for white and crystal and Historical Museum of Warsaw. formulation. Although, when the PbO content is The research was partly supported by the State really high (much higher than 2%), it may be as- Committee for Scientific Research – grant No. sumed that the examined glass is made of crystal 2 H01E 008 25. metal (although, further results might change these ranges). We have found only one unleaded glass References sample among all crystal glass samples analyzed by [1]. Kunicki-Goldfinger J.J., Kierzek J., Kasprzak A.J., the use of EPMA, but a few more were found by Małożewska-Bućko B.: Analyses of 18th century the use of EDXRF. Supported by these results, we central European colourless glass vessels. In: Annales e want to verify some of our previous conclusions du 15 Congrès de l’Association Internationale pour [1-3] and to state that most of crystal glasses melted l’Histoire du Verre (New York – Corning 2001). AIHV, Nottingham 2003, pp.224-229. in the 1st half of the 18th century in central Europe [2]. Kunicki-Goldfinger J.J., Kierzek J., Kasprzak A.J., contain lead, but some of them do not. Among lead- Małożewska-Bućko B.: X-Ray Spectrom., 29, 310-316 ed crystal glass, the highest PbO concentration was (2000). found in the case of glass medallions on the Dresden [3]. Kunicki-Goldfinger J.J., Kierzek J., Kasprzak A.J., (or Naliboki) goblets (<13%), and in the case of Małożewska-Bućko B.: Non-destructive examination goblets made in Altmünden and Dresden (<11%). of 18th century glass vessels from central Europe. For examined Naliboki and Zechlin glasses, PbO In: Proceedings of the 6th International Conference content did not exceed 6%, and for Potsdam glass on Non-Destructive Testing and Microanalysis for – 3%. It should be emphasized once again, that if the Diagnostics and Conservation of the Cultural and leaded crystal was manufactured for the whole first Environmental Heritage (Rome 1999). Italian Society for Non-destructive Testing Monitoring Diagnostics half of the 18th century, the examined unleaded (Brescia) and Central Institute for Restoration crystal glasses originated only from the beginning (Rome), Rome 1999, Vol.2, pp.1539-1552. of the century. [4]. Francis P.: Apollo, February, 47-53 (2000). The following glasshouses were found to pro- [5]. Buquoy Glass in Bohemia 1620-1851. Buquoyské sklo duce crystal glass (regardless to the lead compounds v Èechách 1620-1851. [Katalog]. Umìleckoprùmyslove usage) in the 1st half of the 18th century: Potsdam Museum v Praze, Prague 2001, in Czech. (since 1737 – Zechlin), Altmünden, Dresden, Nali- [6]. Brain C.: Glass Technol., 43C, 357-360 (2002). boki (since 1722), and Bielany (since ~1710). Till [7]. Drahotová O.: J. Glass Stud., 23, 46-55 (1981). now, for Bielany factory, only certain written sources [8]. Drahotová O.: Vznik buquoyského køišt’álového skla (list of imported raw materials) allow us to include v poslední ètvrtinì 17. století. In: Buquoy Glass in Bohe- mia 1620-1851. Buquoyské sklo v Èechách 1620-1851. it to this register of glasshouses. No glass manu- [Katalog]. Umìleckoprùmyslove Museum v Praze, factured in Bielany has been recognized as till now. Prague 2001, pp.13-16, in Czech. Experimental details: Analyses by wavelength [9]. Kunckel J. [Johannis Kunckelii]: Ars vitraria experi- dispersive spectrometry in the EPMA system were mentalis oder Vollkommene Glasmacher-Kunst. carried out using Cameca SX-100 with three simul- 1679 – 1st edition; 1689 – 2nd edition, in German. RADIOCHEMISTRY, STABLE ISOTOPES, NUCLEAR ANALYTICAL METHODS, GENERAL CHEMISTRY 93

[10]. Kunicki-Goldfinger J.J., Kierzek J., Kasprzak A.J., [15]. McCray W.P.: Glassmaking in Renaissance Venice. Dzierżanowski P., Małożewska-Bućko B.: Lead in The Fragile Craft. Aldershod, Ashgate 1999. central European 18th century colourless vessel glass. [16]. Kunicki-Goldfinger J.J., Kierzek J., Kasprzak A.J.: In: Archäometrie und Denkmalpflege. Kurzberichte Some features of the 18th century glass technology 2003 (Berlin). Berlin 2003, pp.56-58. used in central Europe (Saxony, Brandenburg, Poland). [11]. Vickers M.: Antiquity and utopia: the paradox in glass In: Archäometrie und Denkmalpflege. Kurzberichte studies. In: The Prehistory & History of Glassmaking 2000 (Dresden). Eds. G. Schulze, I. Horn. Mensch & Technology. Ed. P. McCray. The American Ceramic Buch Verlag, Berlin 2000, pp.107-109. Society, Westrville, OH, USA 1998, pp.17-31. Series: [17]. Moretti C., Toninato T.: Rivista della Stazione Speri- Ceramic and Civilization. Vol.VIII. mentale del Vetro, 1, 31-40 (1987), in Italian. [12]. Stern E.M.: J. Roman Archaeol., 10, 192-206 (1997). [18]. Veritá M.: Rivista della Stazione Sperimentale del [13]. Vickers M.: J. Roman Archaeol., 9, 48-65 (1996). Vetro, 1, 17-29 (1985), in Italian. [14]. Jacoby D.: J. Glass Stud., 35, 65-90 (1993).

ELECTRICAL PARAMETERS OF POLYPYRROLE NANOTUBULES DEPOSITED INSIDE TRACK-ETCHED MEMBRANE TEMPLATES Marek Buczkowski, Danuta Wawszczak, Wojciech Starosta

Polypyrrole (PPy) – an electrically conducting poly- 0.1 M pyrrole and 0.3 M FeCl3 (III) as oxidant, have mer seems to be a very interesting material for na- been taken [5,6]. Table. Parameters of membrane templates and nanotubules inside pores.

notechnology [1,2]. In such case, it is necessary to For getting samples without necessity of cutting know its electrical parameters. In the accessible lit- out the prepared membranes, a special matrix has erature there are differences in such data [3,4]. Be- been used. This matrix gave ready disc samples with cause of this the present work was undertaken to measure electrical parameters of PPy nanotubules deposited in track-etched membrane (TM) tem- plates – as resistivity and temperature dependence on resistance. In order to get samples, a synthesis of PPy nano- tubules was carried out in TMs (from the Joint Insti- tute for Nuclear Research – JINR, Dubna, Russia) made of a 10 µm thick poly(ethylene terephthalate) (PET) film. For the synthesis, aqueous solution:

Fig.1. A scheme of measuring set-up for determining nano- tubule resistances in TMs templates: 1 – matching Fig.2. Dependence of resistance of TMs samples with de- resistor, 2 – digital voltmeter, 3 – sample, 4 – mili- posited nanotubules upon outer force applied to the ammeter. sample.