XVI ICF TECHNICAL EXCHANGE CONFERENCE 9th-12th October 2004 Karlovy Vary Study of some gilded film/glass interfaces and of one standard type of “liquid gold” Evelyne Darque-Ceretti, Doriane Hélary, Virginie Deram Ecole des Mines de Paris Centre de Mise en Forme des Matériaux UMR CNRS 7635 Sophia-Antipolis France Composition of precious metal preparations precious metals auxiliary materials solvents fixing agents adhesion promoters XIV Technical Exchange Conference Waterford, Ireland October 12 th – 14 th 2002 Annette Lukas/ Ceramic Colour Division Heraeus Germany Introduction Thin gilded films from organo-metallic solutions are used to decorate glass objects Organo-metallic solution = “liquid gold” Objectives: 1. Analysis of interactions after firing between gold and glass, (treated or no) 2. Characterization of another type of “liquid gold” before and during firing Part 1: Gilded film /glass Specimen Characterization methods Surfaces observation Interfacial reactions Conclusions Specimen Substrates soda-lime glass untreated or treated with a Ti oxide film (~ 6 nm thick) or a Sn oxide film (~ 8 nm thick) Gold films - organometallic preparation with 12 % of metallic Au + small metal additions (Rh, Ag, V, Zr …) - deposition on the substrate and firing in air at ~ 600°C during 15 min ~ 0.1-0.2 µm thick Characterisation methods - Why use them ? Scanning Electron Microscope (SEM) morphology (SE mode) and atomic contrast (BSE mode) of the specimen surfaces Secondary Ion Mass Spectrometry (SIMS) Depth distribution of elements (C, Au, Ti, Si, …) with great sensitivity but problems due to charge effects in the glass substrate Glow Discharge Optical Emission Spectrometry (GDOES) with radio frequency Depth distribution for all elements without charge effects SEM surfaces observation Sn treated glass BSE mode For all specimen surfaces : Non continuous gold distribution Formation of an agglomerated structure SE mode Rough surface Ra ~ 0.4 µm Firing temperature 600°C Interfacial reactions SIMS analysis : Sn treated glass In negative secondary mode Charge effects Secondary ion intensity (a.u) 12 C (*1000) 197 Au (*50) 28 Si (*100) 120 Sn (*1000) 107 Ag (*1000) 0 100 200 300 400 500 600 700 800 Time (s) Film ~ 0.2 µm Glass substrate Intermediate zone - Gold diffusion into the substrates - Tin diffusion preferentially into the gilded film - Contamination by hydrocarbons (C) - Silicon diffusion to the surface Distribution of Au diffused into Sn or Ti Interfacial reactions treated or untreated glass at 600°C Fitting by the second Fick’s law : 1 Normalised intensity Au diffusion until Au diffusion until 0.15 µm 0.15 µm 1 Au diffusion until 0.75 µm Normalsed intensity 0 0,00 0,03 0,05 0,08 0,10 0,13 0,15 0,18 0,20 0,23 0,25 0 Distance from interlayer/glass interface (µm) 0 0,25 0,5 0,75 1 1,25 1,5 Distance from gilded film /glass interface (µm ) pre-treated TiTi,Sn Quite the same DAu for Ti or Sn pre-treated glass at 600 °C : D Au treated glass 2.4 10-14 cm2/s DAu untreated glass 4 10-13 cm2/s Gold diffuses faster into untreated glass Intermediate oxide layer = diffusion barrier Interfacial reactions Rf-GDOES analysis : Ti treated glass intensity (a.u) intensity (a.u) Si/2 Au*2 Au*2 Na O*2 Ca/2 H*2 K*2 Ti Ti 0,049 1,049 2,049 3,049 4,049 5,049 Time (s) 0,049 1,049 2,049 3,049 4,049 5,049 Time (s) Film Intermediate Film Intermediate Glass substrate ~ 0.2 µm zone ~ 0.2 µm zone Glass substrate - Migration of alkali constituents of the base glass in the film with segregation at the extreme surface - Gold diffusion into the substrates -Titanium diffusion preferentially into the gilded film - Contamination by hydrocarbons (H) - Oxidation of the gilded layer (due to the thermal treatment in air) Conclusions - For (600°C) faster Au diffusion into untreated glass DAu 4 10-13 cm2/s than pre-treated glass DAu 2.4 10-14 cm2/s Ti and Sn interlayers act as a diffusion barrier - Ti and Sn diffusion into the gold film and into the glass formation of compounds Au-Ti or Au-Sn ? - Diffusion of alkali components from the glass into the gold film formation of compounds ? - Substantial presence of O in the gilded zone formation of a gold oxide ? Part 2: Characterization of a “liquid-gold” Specimen In-situ observations and analyses during the heating process Conclusions Our liquid gold Solid resin in situ analytical methods 500m Optical microscope, X-ray diffraction, and thermal methods (differential scanning calorimeter and gravimetric analysis) Sequential methods Scanning electron microscope, energy dispersive spectrometry FTIR spectroscopy Optical Microscope + Thermo-Gravimetric Analysis 1 mm 1 mm 1 mm 1 mm 1 mm 1 mm 1 mm 1 mm 1 mm 1 mm 25°C 65°C 200°C 350°C 450°C 0 mm 1 mm -10 weight loss (%) -20 600°C Metallic film formation -30 Drying phase smoothing, spreading -40 Evaporation of the solvent mix -50 -60 -70 Thermal decomposition of the resinates -80 0 50 100 150 200 250 300 350 400 450 500 550 600 650 temperature (°C) Reflectance FTIR Transmittance 25°C - 150°C : 630°C 530°C Loss of 430°C 330°C hydrocarbons 280°C 230°C 150°C - 330°C : 180°C 130°C C=O vibration 25°C Decomposition of R-SO2-OR' groups 500 1000 1500 2000 2500 3000 -1 3500 4000 wave number (cm ) Above 350°C : R-SO2-OR' C=O C-H Thin film groups vibration vibration formation X-Ray diffraction 300°C 650°C FWHM Increase of gold crystallite size 300°C Crystalline gold 650°C 600°C Amorphous 650 600 550°C temperature (°C) 550 500°C resins 500 450 400 450°C 350 400°C 300 250 350°C 200 300°C 150 0 10 100 20 30 35 40 45 40 50 50 60 70 2theta (de 80 90 100 0 2 theta (degrees) grees) Complementary analysis : EDS Surface analysis after firing 100 80 Liquid gold after screen-printing C atom (%) O 60 Thickness 50 m S 40 Ag HEATING Au 20 0 100 200 300 400 500 600 temperature ( °C) 600°C : Heterogeneous film Thickness 150 nm Conclusions - Critical temperature 300°C Existence of the first gold crystallites - From 300°C to 600°C, Gold recrystallisation and grain growth Oxidation or decomposition of some componds :V,Rh? Smoothing and spreading of the film Interdiffusion of gold into the glass and alkali elements into the gilded film (part 1) What is the effect on adhesion properties?
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