A spectroscopic investigation of pigment and ceramic samples from Copán, Honduras

A combination of micro-Raman spectroscopy, micro-infrared spectroscopy and SEM–EDX was employed to characterize decorative pigments on Classic Maya ceramics from Copán, Honduras. Variation in red paint mixtures was correlated with changing ceramic types and improvements in process and firing techniques. We have confirmed the use of specular hematite on Coner ceramics by the difference in intensities of Raman bands. Different compositions of brown paint were correlated with imported and local wares. The carbon-iron composition of the ceramic type, Surlo Brown, was confirmed. By combining micro-Raman analysis with micro-ATR infrared and SEM–EDX, we have achieved a more comprehensive characterization of the paint mixtures. These spectroscopic techniques can be used non-destructively on raw samples as a rapid confirmation of ceramic type.

Sliding wear of YTZP ceramic against steel: observations on ceramic transfer and wear transition

Sliding tests were conducted, in air, of YTZP ceramic pins against steel discs at an applied pressure of 15.5 MPa over a speed range of 0.3 to 4.0 ms(-1). Pin wear was not detectable until 2.0 m s(-1), after which a finite but small wear rate was observed at 3.0 m s(-1), accompanied by a red glow at the contacting surface. A transition in wear behaviour and friction (mu) occurred at 4.0 ms(-1), increasing the former by over two orders of magnitude. Both mu and wear behaviour changed with time at 4.0 m s(-1). During initial periods mu was high and wear rate increased steadily with time accompanied by ceramic transfer onto the disc, which increased with time. When disc coverage exceeds a certain threshold value, mu decreased rapidly and the wear rate stabilized at a very high value. Metal transfer was not observed at any speed. High surface temperatures brought about significant adhesion between TZP and steel and this together with enhanced plastic deformation brought about a transition in wear behaviour.

Intense greeen upconversion luminescence in Er3+: Yb3+ codoped fluorophosphate glass ceramic containing SrTe5O11 nanocrystals

Er3+:Yb3+ codoped tellurite-fluorophosphate (TFP) glass ceramic exhibits much stronger upconversion luminescence. The intensity of the 540 nm green light and 651 nm red light of the TFP glass ceramic is 120 times and 44 times stronger than that of the fluorophospahte (FP) glass, respectively. XRD analysis shows that the nanocrystal in TFP glass ceramic is SrTe5O11. TFP glass ceramic also displays much higher upconversion fluorescence lifetime and crystallization stability. The narrow and strong peak at 540 nm is very ideal for practical upconversion luminescence realization. This work is a new trial for exploring non-PbF2 involved nanocrystal upconversion glass ceramics.

New transparent Er3+-doped oxyfluoride tellurite glass ceramic with improved near infrared and up-conversion fluorescence properties

Transparent glass ceramics have been obtained by nucleation and growth of Y2Te6O15 or Er2Te5O13 cubic phase in a new Er3+-doped oxyfluoride tellurite glass. Effect of beat treatment on absorption spectra, luminescence and up-conversion properties in the oxyfluoride tellurite glass has been investigated. With heat treatment the ultraviolet absorption edge red shifted evidently for the oxyfluoride telluride glass. The near infrared emission that corresponds to Er3+:I-4(13/2)-> I-4(15/2) can be significantly enhanced after heat treatment. Under 980 nm LD pumping, red and green up-conversion intensity of Er3+ in the glass ceramic can be observed much stronger than that in the base glass. (C) 2006 Elsevier B.V. All rights reserved.

In vitro osteogenesis on fluorcanasite glass-ceramic with three different chemical compositions

This study aimed at investigating in vitro osteogenesis on three fluorcanasite glass-ceramic compositions with different solubilities (K3, K5, and K8). Osteoblastic cells were obtained from human alveolar bone fragments and cultured under standard osteogenic condition until subconfluence. First passage cells were cultured on K3, K5, and K8 and on Bioglass (R) 45S5 (45S5-control). Cell adhesion was evaluated at 24 h. For proliferation and viability, cells were cultured for 1, 4, and 10 days. Total protein content and alkaline phosphatase (ALP) activity were measured at 7, 14, and 21 days. Cultures were stained with Alizarin red at 21 days, for detection of mineralized matrix. Data were compared by ANOVA followed by Duncan`s test. Cell adhesion, cell proliferation, viability, total protein content, and ALP activity were not affected by fluorcanasite glass-ceramic composition and solubility. Bone-like formation was similar on all fluorcanasite-glass ceramics and was reduced compared to 45S5. The changes in the chemical composition and consequently solubility of the fluorcanasite glass-ceramics tested here did not significantly alter the in vitro osteogenesis. Further modifications of the chemical composition of the fluorcanasite glass-ceramic would be required to improve bone response, making this biomaterial a good candidate to be employed as a bone substitute.

Vibrational spectroscopy applied to the study of archeological ceramic artifacts from Guarani culture in Brazil

An archeological artifact can be seen as a chronological element, which helps to determine the age of certain society and to understand the thinking, values and the way of life of this society. Thus, the classification of archeological artifacts is one of the approaches used to study the cultural system of antique societies trying to reconstruct their history. The "Centro de Museologia, Antropologia e Argueologia (CEMAARQ)" of the "Unesp Univ Estadual Paulista" in Presidente Prudente, São Paulo state, Brazil, develops projects within this context (identification and preservation). This is the case of the archeological site named "Lagoa São Paulo-02" discovered in 1993 at the margins of the Parana river in the region of Presidente Epitacio city, São Paulo state, Brazil. This site has ceramic fragments of different shapes and sizes that have a strong influence of traces of the Guarani culture, which is one of the Brazilian native populations. These samples were basically characterized via micro-Raman scattering and Fourier transform infrared absorption (FTIR) spectroscopies. The main objective was to identify the pigments used in the manufacture of the ceramic artifacts and to analyze the composition of the ceramic body to understand how the artifacts were made. Three pigments were found: red, black and white. For the red pigment were identified characteristic bands of hematite, an iron oxide found in the red rocks of the river banks that were eroded by water. The black pigment, probably, is due to the use of vegetal charcoal, which is found in nature as the product of burning organic material such as wood. For the white pigment, the FTIR spectra suggested the use of kaolin, either in the ceramic body or in the proper white pigment, due to the presence of the characteristic bands of the kaolinite. Complementary, the additives applied as anti-plastics were identified as charcoal and quartz, being the latter found in the rocks present in the archeological site. (C) 2010 Elsevier B.V. All rights reserved.

Color tunability of intense upconversion emission from Er3+-Yb3+ co-doped SiO2-Ta2O5 glass ceramic planar waveguides

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Multiwavelength visible and white light generation by upconversion emission in Ho/Tm/Yb triply doped fluorogermanate glass-ceramic

Energy transfer excited multiwavelength visible upconversion emission and white light generation is described in a single sample of PbGeO(3)-PbF(2)-CdF(2) glass-ceramic triply doped With Ho/Tm/Yb under single infrared laser excitation. Blue (475 nm), green (540 mn), and red (650 nm), upconversion luminescence signals are generated, and the emissions are assigned, respectively, to thulium ((1)G(4)-(3)H(6)), and holmium ((5)S(2);(5)F(4)) -> (5)I(8), (5)F(5) -> (5)I(8)) ions transitions, both excited via successive energy transfers from ytterbium ions. It is experimentally shown that with a proper combination of the rare earth ions contents, white light may be produced, with the simultaneous generation of fluorescence with controllable intensities at the wavelengths of the three primary colours in a single sample and using a single near-infrared excitation source.

Upconversion luminescence in Ho3+/Yb3+- and Tb3+/Yb3+-codoped fluorogermanate glass and glass ceramic

Energy-transfer excited upconversion luminescence in Ho3+/Yb3+- and Tb3+/Yb3+ -codoped PbGeO3-PbF2-CdF2 glass and glass-ceramic under infrared excitation is investigated. In Ho3+/Yb3+-codoped samples, green (545 nm), red (652 nm), and near-infrared (754 nm) upconversion emission corresponding to the S-5(2) (F-5(4)) -> I-5(8), F-5(5) -> I-5(8), and S-5(2)(F-5(4)) -> I-5(7) transitions, respectively, was observed. Blue (490 nm) emission assigned to the F-5(2,3) -> I-5(8) transition was also detected. In the Tb3+/Yb3+-codoped system, bright UV-visible emission around 384, 415, 438, 473-490, 545, 587, and 623 nm, identified as due to the D-5(3)((5)G(6)) -> F-7(J)(J = 6, 5, 4) and D-5(4) -> F-7(J)(J = 6, 5, 4, 3) transitions, was measured. The comparison of the upconversion process in glass ceramic and its glassy precursor revealed that the former samples present much higher upconversion efficiencies. The dependence of the upconversion emission upon pump power, and doping contents was also examined. The results indicated that successive energy-transfer between ytterbium and holmium ions and cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The viability of using the samples for three-dimensional solid-state color displays is also discussed. (c) 2007 Elsevier B.V. All rights reserved.

Ceramic raw materials from the State of Maranhao, Brazil. Part 1: chemical and mineralogical characterization and technological properties of clays from Sao Luis, Rosario, Pinheiro and Mirinzal

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Optical properties and energy-transfer frequency upconversion of Yb 3+-sensitized Ho3+- And Tb3+-doped lead-cadmium-germanate glass and glass ceramic

In this report we investigate the optical properties and energy-transfer upconversion luminescence of Ho3+- and Tb3+/Yb 3+-codoped PbGeO3-PbF2-CdF2 glass-ceramic under infrared excitation. In Ho3+/Yb 3+-codoped sample, green(545 nm), red(652 nm), and near-infrared(754 nm) upconversion luminescence corresponding to the 4S 2(5F4) → 5I8, 5F5 → 5I8, and 4S2(5F4) → 5I 7, respectively, was readly observed. Blue(490 nm) signals assigned to the 5F2,3 → 5I8 transition was also detected. In the Tb3+/Yb3+ system, bright UV-visible emission around 384, 415, 438, 473-490, 545, 587, and 623 nm, identified as due to the 5D3(5G6) → 7FJ(J=6,5,4) and 5D4→ 7FJ(J=6,5,4,3) transitions, was measured. The comparison of the upconversion process in glass ceramic and its glassy precursor revealed that the former samples present much higher upconversion efficiencies. The dependence of the upconversion emission upon pump power, and doping contents was also examined. The results indicate that successive energy-transfer between ytterbium and holmium ions and cooperative energy-transfer between ytterbium and terbium ions followed by excited-state absorption are the dominant upconversion excitation mechanisms herein involved. The viability of using the samples for three-dimensional solid-state color displays is also discussed.

Upconversion luminescence in Er3+ doped Ga10Ge 25S65 glass and glass-ceramic excited in the near-infrared

The infrared-to-visible frequency upconversion was investigated in Er 3+-doped Ga10Ge25S65 glass and in the transparent glass-ceramic obtained by heat-treatment of the glass above its glass-transition temperature. Continuous-wave and pulsed lasers operating at 980 nm and 1480 nm were used as excitation sources. The green (2H 11/2 → 4I15/2; 4S3/2 → 4I15/2) and red (4F9/2 → 4I15/2) photoluminescence (PL) signals due to the Er3+ ions were characterized. The PL decay times were influenced by energy transfer among Er3+ ions, by cross-relaxation processes and by energy transfer from the Er3+ ions to the host material. The PL from the Er3+ ions hosted in the crystalline phase was distinguished only when the glass-ceramic was excited by the 1480 nm pulsed laser. The excitation pathways responsible for the green and red PL bands are discussed to explain the differences between the spectra observed under continuous-wave and pulsed excitation. © 2013 American Institute of Physics.

The ceramic artifacts in archaeological black earth (terra preta) from Lower Amazon Region, Brazil: chemistry and geochemical evolution

Neste trabalho realizou-se a caracterização química de fragmentos de artefatos cerâmicos encontrados em sítios arqueológicos com terra preta no Baixo Amazonas (Cachoeira-Porteira, Pará, Brasil), representativos da cultura Konduri (de 900 a 400 anos AP). Esses fragmentos são constituídos de SiO₂, Al₂O₃, Fe₂O₃, Na₂O e P₂O₅, sendo que SiO₂ e Al₂O₃, juntos, perfazem mais de 80 % em peso. Os teores de P₂O,₅ são relativamente elevados (2,37 % em média) sob a forma de (Al,Fe)-fosfatos, incomuns em cerâmicas vermelhas primitivas, mas encontrados em algumas cerâmicas arqueológicas egípcias e romanas. As concentrações dos elementos traços são comparáveis ou mesmo inferiores ao nível crustal, embora a composição total seja próxima a mesma. A composição química (exceto P₂O₅) em conjunto com os dados mineralógicos e texturais indicam material saprolítico derivado de rochas ígneas félsicas ou rochas sedimentares como matéria-prima das cerâmicas. Os teores de K, Ca e Na mostram que os feldspatos e fragmentos de rochas foram adicionados ao material argiloso, como sugerido pela mineralogia. Os altos teores de sílica respondem pela presença de cauixi, cariapé e/ou areias quartzosas. Fósforo deve ter sido incorporadoà matriz argilosa da cerâmica, quando do cozimento de alimentos nos vasos cerâmicos, e ainda, em parte, durante a formação do perfil de solo tipo ABE sobre Latossolos Amarelos. A matéria prima e os temperos (cauixi, cariapé, rochas trituradas e fragmentos de vasos cerâmicos descartados) encontram-se disponíveis próximos aos sítios até a atualidade, e, portanto foram a área fonte dos mesmos para a confecção dos artefatos cerâmicos.

Ceramic raw materials from the State of Maranhão, Brazil. Part 1: chemical and mineralogical characterization and technological properties of clays from São Luis, Rosário, Pinheiro and Mirinzal

Nesse trabalho, foram caracterizadas algumas argilas coletadas nos municípios de São Luís, Rosário, Pinheiro e Mirinzal. A caracterização foi realizada através dos ensaios de difração de raios X, massa específica real, capacidade de troca de cátions (CTC), área superficial, distribuição granulométrica, análise química, análise térmica (TG-DTA) e limites de Atterberg. Ensaios tecnológicos de retração linear, antes e após a queima, absorção de água e tensão de ruptura a flexão, em três pontos, foram realizados em corpos de prova prensados uniaxialmente a 20 MPa e tratados termicamente em 850, 950, 1050, 1150 e 1250ºC. Os resultados obtidos permitiram identificar duas argilas de queima branca, constituídas de quartzo, caolim, feldspato e anatásio, com excelentes propriedades para uso em cerâmica branca. As restantes são queima vermelha e possuem composição mineralógica de quartzo, caolim, feldspato, montmorilonita, hematita e goetita. Estas últimas apresentaram valores moderados de plasticidade e são adequadas para aplicações em cerâmica vermelha.

Reassessment of the potential applications of Eu3+-doped Y2O3 photoluminescent material in ceramic powder form

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)