Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Red Glass Coloration: a Colorimetric and Structural Study
KTH, School of Chemical Science and Engineering (CHE), Chemistry, Inorganic Chemistry.
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: urn:nbn:se:kth:diva-4176ISBN: 91-7178-486-1 (print)OAI: oai:DiVA.org:kth-4176DiVA: diva2:11081
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
List of papers
1. Colour development in copper ruby alkali silicate glasses.: Part 1. The impact of tin(II) oxide, time and temperature
Open this publication in new window or tab >>Colour development in copper ruby alkali silicate glasses.: Part 1. The impact of tin(II) oxide, time and temperature
Show others...
2007 (English)In: GLASS TECHNOLOGY-EUROPEAN JOURNAL OF GLASS SCIENCE AND TECHNOLOGY PART A, ISSN 1753-3546, Vol. 48, no 2, 101-108 p.Article in journal (Refereed) Published
Abstract [en]

The development of the red colour in copper ruby alkali silicate glasses has been studied by means of ultraviolet/visible spectroscopy, TEM and EXAFS. The results show that in both red and slightly overstruck, brownish glasses the colour is due to clusters of metallic copper. Before striking non-coloured glasses contain mainly cuprous ions, Cu+. Tin acts as a reducing agent but also has an accelerating effect on colour development.

Keyword
SMALL METALLIC PARTICLES; SOL-GEL PROCESS; OPTICAL-ABSORPTION; PHOSPHATE-GLASSES; RED COLOR; NANOPARTICLES; NANOCLUSTERS; SPECTROSCOPY; SIZE
National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-24186 (URN)000247317500007 ()2-s2.0-34250881696 (Scopus ID)
Note
QC 20100820Available from: 2010-08-20 Created: 2010-08-20 Last updated: 2010-08-20Bibliographically approved
2. Colour development in copper ruby alkali silicate glasses.: Part 2. The effect of tin (II) oxide and antimony (III) oxide
Open this publication in new window or tab >>Colour development in copper ruby alkali silicate glasses.: Part 2. The effect of tin (II) oxide and antimony (III) oxide
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.

Keyword
optical-absorption, nanoparticles, scattering, particles
National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-16853 (URN)000248619600006 ()2-s2.0-34547638409 (Scopus ID)
Note
QC 20100820Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2010-08-20Bibliographically approved
3. Gold ruby glasses: influence of iron and selenium on their colour
Open this publication in new window or tab >>Gold ruby glasses: influence of iron and selenium on their colour
2006 (English)In: Glass Technology, ISSN 0017-1050, Vol. 47, no 4, 112-120 p.Article in journal (Refereed) Published
Abstract [en]

Colour development of gold ruby alkali silicate glasses, when various elements are added to the batch, has been investigated. Elements used in the study are selenium, iron, tin, lead, antimony, cerium, titanium and bismuth. The colours are presented and compared by their Lab coordinates. Among the elements selenium and iron are found to be important, and the role of these elements in colour development is discussed. Thermodynamic calculations show that important oxidation states are Fe2+ for iron and Se-0 and Se2- for selenium, and that higher melting temperature improves the colour, as it affects the oxidation states of both Fe and Se.

Keyword
X-RAY-SCATTERING; OPTICAL-PROPERTIES; COLLOIDAL GOLD; PARTICLES; NANOPARTICLES; ABSORPTION; SIZE
National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-24188 (URN)000244905100003 ()
Note
QC 20100820Available from: 2010-08-20 Created: 2010-08-20 Last updated: 2017-12-12Bibliographically approved
4. Selenium: molybdenum-based coloration of alkali silicate glasses
Open this publication in new window or tab >>Selenium: molybdenum-based coloration of alkali silicate glasses
2007 (English)In: Glass Technology, ISSN 0017-1050, Glass Technology - European Journal of Glass Science and Technology Part A, Vol. 48, no 5, 213-221 p.Article in journal (Refereed) Published
Abstract [en]

The interaction between selenium and molybdenum in reduced alkali silicate melts, resulting in red glasses has been studied. The oxidation state of Mo is Mo(VI) as evidenced by XANES and ESCA results. Selenium is present in a reduced state, as indicated by ultraviolet/visible spectroscopy and XANES. The colour is described by ultraviolet/visible spectra and CIE colour coordinates. The main absorption peaks are at 450 and 540 nm. Similar bands are reported for MoOSe32−. Several commonly used glass components must be avoided in the batch, as they prevent formation of the red colour.

National Category
Natural Sciences
Identifiers
urn:nbn:se:kth:diva-6384 (URN)
Note
QC 20100820Available from: 2006-11-22 Created: 2006-11-22 Last updated: 2010-08-20Bibliographically approved
5. Potassium sulfate droplets and the origin of turbidity in alabaster glasses
Open this publication in new window or tab >>Potassium sulfate droplets and the origin of turbidity in alabaster glasses
2006 (English)In: Glass Technology, ISSN 0017-1050, Vol. 47, no 1, 15-18 p.Article in journal (Refereed) Published
Abstract [en]

A study of the criteria required to manufacture multicomponent semi-transparent silicate glasses, so called 'alabaster' glasses, has found that the optical effect is caused by noncrystalline potassium sulfate droplets. The droplets were characterised by use of XRD, SEM/EDX and Raman spectroscopy. The size range of the particles is of the order of 5-50 micrometers. It was found that the droplets consisted of potassium sulfate, even if other sulfate compounds were added to the glass. The amount of sulfate compound added, the melting temperature of the furnace and the melting time have significant effects on the optical density of the glass. The optical density of the glass can be correlated to the calculated surface tension of the host glass, suggesting that phase separation of a sulfate enriched liquid phase is part of the mechanism forming the droplets. By adding pigments several different colours can be obtained, but the alabaster effect is not achieved during reducing conditions, thus it seems not possible to produce colours originating from reduced pigments. Pigments tested were Cr, Fe, Co, Cu, Au, Mo/Se, Nd and Ti/Ce/Se.

National Category
Engineering and Technology
Identifiers
urn:nbn:se:kth:diva-16108 (URN)000241757700003 ()2-s2.0-33745453337 (Scopus ID)
Note
QC 20100820Available from: 2010-08-05 Created: 2010-08-05 Last updated: 2017-12-12Bibliographically approved

Open Access in DiVA

fulltext(5636 kB)8904 downloads
File information
File name FULLTEXT01.pdfFile size 5636 kBChecksum MD5
4371550b170ae873d3def096b3954410da323b45b2d570eb8aaa8fa9308b87140fa24600
Type fulltextMimetype application/pdf

Search in DiVA

By author/editor
Bring, Torun
By organisation
Inorganic Chemistry
Organic Chemistry

Search outside of DiVA

GoogleGoogle Scholar
Total: 8904 downloads
The number of downloads is the sum of all downloads of full texts. It may include eg previous versions that are now no longer available

isbn
urn-nbn

Altmetric score

isbn
urn-nbn
Total: 1766 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • harvard1
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf