Emissions from melted glass: experimental and theoretical approaches MAKAROV Pavel 2 st year master student MSU Trainee in SGR: 18/03/2013 – 31/07/2013 Supervisors: BLAHUTA Samuel CONDOLF Cyril

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. INTRODUCTION 2

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. Key questions What gaseous species are the most stable during volatilization of glass in Na-B-Si-O(-H) system according to literature data? What thermochemical databases do we have? Are current databases convenient for simulation of experimental processes? 3

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. Literature survey on the most stable gaseous species in high temperature (1700 – 1800 K) region; Volatilization experiments (binary, ternary glasses); Thermodynamic simulation (FactSage) of the experiments; Comparison of experimental results to FactSage simulation; General conclusions; Perspectives. Summary of presentation 4 NaBO 2, HBO 2 (+NaOH)

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. 5 Poor agreement of FactPS and experimental data In high temperature region Data for NaBO 2 (g) were modified (based on FactPS data);Data for NaBO 2 (g) were modified (based on FactPS data); New database FactTEST was created;New database FactTEST was created; NaBO 2 (g) partial pressure (log) 1000/T, K -1 (1) NaBO 2 (g) : literature data, comparison to FactSage Cole et al., 1935 Cable et al., 1987 Gorokhov et al., 1971 Nalini et al., 2008 Ivanov, 2002

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (1) How to build new database? NaBO 2 (l) ↔ NaBO 2 (g) 6 ∆G = G(NaBO 2(g) ) – G(NaBO 2(l) ) = - RT lnK eq K eq = P(NaBO 2(g) )/a(NaBO 2(l) ) a(NaBO 2(l) )=1 _____________________________________ ∆G = G(NaBO 2(g) ) – G(NaBO 2(l) )= - RT lnP(NaBO 2(g) ) 1) Thermodynamic description 2) Experimental description lg P = A + B/T Literature data FactSage (SLAGA) ?

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (1) NaBO 2 (g) : literature data, comparison to FactSage 7 FactTEST is also efficient for Na 2 O/B 2 O 3 system with different compositions NaBO 2 (g) partial pressure (log) 1000/T, K -1 2 B 2 O 3 + Na 2 O Cole et al., 1935

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (1) HBO 2 (g) : literature data, comparison to FactSage 8 FactPS: Good agreement to Knudsen effusion mass- spectrometric method data; HBO 2 (g) partial pressure (log) 1000/T, K -1 B 2 O 3(s) + H 2 O (g) : 1960

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (1) HBO 2 (g) : literature data, comparison to FactSage 9 FactPS: Good agreement for values obtained from transpiration method; Equilibrium constant (log) T, K B 2 O 3 (l) + H 2 O (g) = 2 HBO 2 (g)

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (1) HBO 2 (g) : literature data, comparison to FactSage 10 FactPS calculation results in agreement with experimental (Knudsen effusion method) at different T; 0.5 H 2 O (g) B 2 O 3 (l or s) = HBO 2 (g) y = x

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (1) Conclusions on thermodynamic databases?  new database (FactTEST); thermodynamic functions for NaBO 2 (g) modified;  new database (FactTEST);  still using FactPS. thermodynamic functions for HBO 2 (g) – no change;  still using FactPS. 11

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. Literature survey on the most stable gaseous species in high temperature (1700 – 1800 K) region; Volatilization experiments (binary, ternary glasses); Thermodynamic simulation (FactSage) of the experiments; Comparison of experimental results to FactSage simulation; General conclusions; Perspectives. Summary of presentation

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (2) Experimental set-up Conditions: T = 1475 °C, P(H 2 O) = 0,19 & 0,65 bar; Glass: 1) binary (26 wt. % Na 2 O, 74 wt. % SiO 2 ); 2) ternary (26 wt. % Na 2 O, 5 wt. % B 2 O 3, 69 wt. % SiO 2 ); 13 Flacons with deionized water Quartz fiber filter

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (2) What changes during the experiment? 14 Initial composition of glass Composition of glass changes during the experiment 5 series of solutions for each hour was analyzed with ICP

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (2) Analyses used, sample preparation ICP (for all solutions); pH – measurments; μprobe analyses; SEM/EDS (additional); 15 C i in each solution Final glass composition, concentration profiles Verification of ICP & μprobe Verification μprobe Gas / melt composition on each step

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. Literature survey on the most stable gaseous species in high temperature (1700 – 1800 K) region; Volatilization experiments (binary, ternary glasses); Thermodynamic simulation (FactSage) of the experiments; Comparson of experimental results to FactSage simulation; General conclusions; Perspectives. Summary of presentation

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (3) Thermodynamic simulation (FactSage) of volatilization experiments 17 ICP - output FactSage simulation comparison Q i = ΣQ (i elem) Input for FactSage

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (3) Ternary glass: working assumption 18 ICP result recalculation: Main assumption - NaOH amount is negligible NaB NaBO 2 HBO 2 ICP: C i in each solution P j we want to calculate

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. Literature survey on the most stable gaseous species in high temperature (1700 – 1800 K) region; Volatilization experiments (binary, ternary glasses); Thermodynamic simulation (FactSage) of the experiments; Comparison of experimental results to FactSage simulation; General conclusions; Perspectives. Summary of presentation 19 4

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (4) Binary glass: experiment vs FactSage 20 0,19 bar 0,65 bar Time ↑ NaOH (g) partial pressure (log) Time ↑ NaOH (g) partial pressure (log) FactSage simulation results are close to experimental points Na, Si

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. 21 P (H 2 O) SiO 2, wt. % Na 2 O, wt. % 0.19 bar bar μprobe SiO 2 Na 2 O (4) Binary glass: experiment vs FactSage Na, Si ICP µprobe 1)Flat profiles (µprobe) → it’s possible to recalculate melt composition from ICP results; 2)Differs between w(Na 2 O) for ICP and for µprobe.

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (4) Binary glass: experiment vs FactSage 22 ? EDS 1)Precipitation during cooling of melt; 2)Precipitate absorbs Na from glass matrix. Na, Si Black particles Si O Na Glass matrix

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (4) Ternary glass: experiment vs FactSage 23 Na, Si, B T = 1475 °C

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (4) Ternary glass: experiment vs FactSage 24 ICP analysis FactTEST is not suitable because of problems with mass balance at phase equilibrium calculation (reason – G(T) for NaBO 2 (g) in FactTEST) Na, Si, B

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (4) Ternary glass: experiment vs FactSage 25 Cross section plotting Na, Si, B

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (4) Ternary glass: experiment vs FactSage 26 NaBO 2 HBO 2 1)FactPS results are in agreement with ICP for NaBO 2 (g) ; 2)Differs for HBO 2 (g) at 0,65 bar: Possible reasons: - not all condensate was collected in experiments; Possible reasons: - not all condensate was collected in experiments; - deffects of thermodynamic glass model in FactSage. - deffects of thermodynamic glass model in FactSage. Na, Si, B

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. 27 μprobe SiO 2 Na 2 O (4) Ternary glass: experiment vs FactSage ICP µprobe 1)Flat profiles (µprobe); 2)Differs (less than for binary glass) between w(Na 2 O) for ICP and for µprobe. Na, Si, B P (H 2 O) SiO 2, wt. % B 2 O 3, wt. % Na 2 O, wt. % 0.19 bar 72,9 1,6 19, bar 73,2 1,6 20,9 B2O3B2O3B2O3B2O3

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (4) Ternary glass: experiment vs FactSage 28 EDS 1)Precipitation during cooling of melt; 2)Precipitate absorbs Na from glass matrix. Na, Si, B Black particles O Si Na Glass matrix

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (4) Industrial glass (SGR, 2009) Insulation glass (wt. %): SiO 2 = 65.6 Al 2 O 3 = 2 B 2 O 3 =4.3 CaO=8 MgO=2.7 Na 2 O (+K 2 O)=17.0 (K 2 O=0.6 put as Na 2 O) T = 1475 °C, P(H 2 O) = 0,19 bar 29

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (4) Industrial glass (SGR, 2009) 30 1) FactPS can be approached for experiment simulation; 2) FactTEST is not suitable.

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. (4) Industrial glass (SGR, 2009) 31 NaBO 2 HBO 2 The same magnitudes for P i like in our experiments → Differs for HBO 2 (g) for ternary glass at 0,65 bar could be explained by problems of theoretical glass model in FactSage;

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. Literature survey on the most stable gaseous species in high temperature (1700 – 1800 K) region; Volatilization experiments (binary, ternary glasses); Thermodynamic simulation (FactSage) of the experiments; Comparison of experimental results to FactSage simulation; General conclusions; Perspectives. Summary of presentation 32

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. General conclusions According to literature analysis: - Thermodynamic properties of NaBO 2 (g) in FactPS were modified; - New FactTEST database was created; - Properties of HBO 2 (g) are in good agreement with literature data; Volatilization experiments were carried out; FactTESTcan not be used FactTEST can not be used for real experiment simulation; FactPSrecommended to be used Initial database FactPS was recommended to be used for experiment optimizing. 33

CONFIDENTIAL - Disclosure or reproduction without prior written permission of Saint-Gobain Recherche is prohibited. PERSPECTIVES Verification of T boiling of pure NaBO 2 (g) (literature – 1434°C, FactPS – 1757°C); Check SLAG database on data correctness, creating new database/ new solution model for glass melt in Na 2 O-B 2 O 3 -SiO 2 system; 34 NaBO 2 (g) partial pressure (log) 1000/T, K °C 1434°C