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Colour development in copper ruby alkali silicate glasses.: Part 2. The effect of tin (II) oxide and antimony (III) oxide
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Inorganic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Inorganic Chemistry.
KTH, School of Chemical Science and Engineering (CHE), Chemistry.ORCID iD: 0000-0001-6737-8233
2007 (English)In: GLASS TECHNOLOGY-EUROPEAN JOURNAL OF GLASS SCIENCE AND TECHNOLOGY PART A, ISSN 1753-3546, Vol. 48, no 3, 142-148 p.Article in journal (Refereed) Published
Abstract [en]

The effect of Sb3+ and Sn2+ during the heat treatment of copper ruby alkali silicate glasses is investigated. The reducing power of SnO and Sb2O3 with respect to Cu is investigated and it is concluded that SnO has the strongest reducing capability. When Cu2O and SnO concentrations are low, minor additions of Sb2O3 have an observable impact on colour development and absorbance, as thin pieces of glass develop a bluish tint and a larger shift towards longer wavelengths is observed in UV/vis spectra. The differences in colour and spectra are suggested to be caused by differences in size of the colour forming agent, Cu metal particles.

Place, publisher, year, edition, pages
2007. Vol. 48, no 3, 142-148 p.
Keyword [en]
optical-absorption, nanoparticles, scattering, particles
National Category
Engineering and Technology
Identifiers
URN: urn:nbn:se:kth:diva-16853ISI: 000248619600006Scopus ID: 2-s2.0-34547638409OAI: oai:DiVA.org:kth-16853DiVA: diva2:334896
Note
QC 20100820Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2010-08-20Bibliographically approved
In thesis
1. Red Glass Coloration: a Colorimetric and Structural Study
Open this publication in new window or tab >>Red Glass Coloration: a Colorimetric and Structural Study
2006 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [sv]

Syftet med detta arbete har varit att försöka hitta alternativ till det kadmiumbase¬rade röda pigment som används idag. Detta har gjorts genom att delvis under¬söka kombinationer av grundämnen som i litteraturen finns omnämnda som röda glaspigment, delvis genom att försöka förbättra och underlätta produktionen av redan kända, men problematiska pigment.

Det har konstaterats att det går att framställa ett rött glas när man smälter soda¬kalkglas med en kombination av molybden och selen, under reducerande beting¬elser. Rött glas med denna kombination har inte rapporterats tidigare. Pigmentet är känsligt för vilken glassammansättning man använder och flera vanliga glas¬komponenter måste undvikas. För att utvärdera färgen hos glasen användes UV/vis-spektroskopi och färgkoordinater i CIE-systemet. Både ESCA- och XANES-analyser visar att molybden finns i glaset som Mo6+joner. Färgen upp¬kommer troligtvis genom en interaktion mellan molybdenjonerna och selen i reducerad form. UV/Vis- och XANES spektra visar att selen finns i glaset i redu¬cerad form.

Färgutvecklingen hos kopparrubinglas studerades med UV/vis-spektroskopi. Detta pigment behöver värmebehandlas för att färgen skall bildas. När låga vär¬mebehandlingstemperaturer och låga halter av de färgande komponenterna an¬vänds, är pigmentet stabilt under lång tid. Experimentella resultat från EXAFS- och TEM-analyser visar tydligt att färgkällan är metalliska kopparpartiklar i na¬nostorlek.

Inverkan av olika reduktionsmedel på guld- och kopparrubinpigmenten har un¬dersökts. Det konstaterades att SnO är mer reducerande gentemot koppar än Sb2O3 i sodakalkglas. Kopparrubinglas kan framställas med bara endera av dessa reduktionsmedel, men SnO ger bättre resultat. Skift i absorbanstoppens läge och provets färg har observerats hos både guld- och kopparrubiner. Det största skiftet finns hos glas där en blåaktig ton erhållits. Skiftet beror troligtvis på att större partik¬lar bildats.

Möjligheterna att kombinera röd färg med halvtransparenta alabasterglas har undersökts. Det konstaterades dock att alabastereffekten inte går att kombinera med pigment som kräver starkt reducerande miljöer.

Både guld- och kopparrubiner är miljövänligare än det kadmiumbaserade pig¬mentet, och måste anses som möjliga alternativ. Mo/Se-pigmentet kan också vara ett alternativ.

Abstract [en]

The aim of this thesis has been to find alternatives in the alkali silicate glass system to the most commonly used red glass pigment today, which is based on Cd(S, Se). The overall strategy has been to facilitate the use of already existing, well known but complicated and control-demanding pigments. Also the possi¬bilities to obtain red glass by combining elements as briefly reported in litera¬ture as possible red glass pigments, has been investigated.

It has been found that by combining molybdenum and selenium in alkali-lime-silica glass under reducing conditions, a red pigment can be obtained. Red glass originating from this combination has not been reported earlier. The pigment is sensitive to batch composition and some glass components must be avoided. UV/vis spec¬troscopy and CIE colour coordinates were used when colour of samples was evaluated. Both ESCA and XANES give evidence that molybde¬num is present as Mo6+ ions. The colour is caused by an interaction between the molybdenum ions and selenium under reducing conditions. The presence of se¬lenium in a reduced state is evidenced by UV/vis spectroscopy and XANES analysis.

The colour development in copper ruby glasses was studied by UV/vis spectros¬copy. It was observed that when low concentrations of colouring components were used, the pigment is stable regarding colour over long periods of time. Ex¬peri¬mental results from TEM and EXAFS provided good evidence that the col¬our origi¬nates from nanoparticles of metallic copper. This is in analogy with the gold ruby pigment.

The impact of different reducing agents on the copper and gold ruby pigments was examined. It was concluded that SnO has a stronger reducing capacity to¬wards copper than Sb2O3 in alkali silicate glasses. The copper ruby colour can be obtained by the use of one of these reducing agents solely. Shifts in absorbance peak position as well as in colour hues are observed in both pigments and the largest shifts in absorption are observed in blue or bluish glasses, probably caused by larger particles.

The possibility to combine red colour and semi-transparent alabaster glasses was studied. The studies however, indicated that the alabaster effect is not compati¬ble with pigments requiring strongly reducing conditions.

Both gold and copper rubies are more environmentally friendly than the cad¬mium based Cd(S, Se) pigment, and must be regarded as possible alternatives. The Mo/Se pigment can also be an alternative.

Place, publisher, year, edition, pages
Stockholm: KTH, 2006
Series
Trita-OOK, ISSN 0348-825X ; 1083
National Category
Organic Chemistry
Identifiers
urn:nbn:se:kth:diva-4176 (URN)91-7178-486-1 (ISBN)
Public defence
2006-12-01, Sal F3, KTH, Lindstedtsvägen 26, Stockholm, 13:00
Opponent
Supervisors
Note
QC 20100820Available from: 2006-11-22 Created: 2006-11-22 Last updated: 2010-08-20Bibliographically approved

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