Mousses de verre issues du - PowerPoint Presentation

1. Mousses de verre issues du recyclage: Quelques exemples d’études et applicationsRonan LEBULLENGER et al.ronan.lebullenger@univ-rennes1.frUMR6226 - ISCR – Eq. Verres et Céramiques1

2. Rennes Institut of Chemical Sciences ISCR Chemistry &Engineering for Sustainable DevelopmentMolecules &Materials for Optics & ElectronicsMolecules &Materials for HealthISCR ExpertiseConception & Synthesis of Molecules & Materials with Dedicated PropertiesFrance2

3. 3R management for glass wastesCathode Ray Tube (CRT) valorisation (Recyver Project)Foam glass from CRT for MW applicationsCommon silicate glasses for catalytic applicationsCommon silicate glasses for biomaterialsArts and Sciences3

4. 3R management for glass wastesCathode Ray Tube (CRT) valorisation (Recyver Project)Foam glass from CRT for MW applicationsCommon silicate glasses for catalytic applicationsCommon silicate glasses for biomaterialsArts and Sciences4

5. The 3Rs represent a strategy for the management of end-of-life products and the resulting waste:Reduce the amount of products that arrive at the end of life,Reusing products or parts thereof that would otherwise become waste,Recycle raw materials.End-of-life products that can not fit into this scheme are considered ultimate waste, they can only be stored, eventually waiting to find a way to return them to the circuit.3R management for glass5

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7. By Optimisation of:melting conditions - homogeneity, stone and bubble free gob, parison viscosity,...)shaping containers process- mould and press conditions)coating - spray in cold section and annealing kilnbetter mechanical properties for lighter products7

8. CAS Number for glass: 65997-17-3Glass, oxide, chemicalsCAS Number: 65997-17-3EPA Registry Name: Glass, oxide, chemicalsMolecular Formula: UnspecifiedDefinition of glass from environmental agencies8

9. From EPA , United States Environmental Protection Substance Registry Services (SRS).Oxides of the first seven elements listed * comprise more than 95 percent, by weight, of the glass produced: Aluminum*; Boron*; Calcium*; Magnesium*; Potassium*; Silicon*; Sodium*; Antimony; Arsenic; Barium; Bismuth; Cadmium; Carbon; Cerium; Cesium; Chromium; Cobalt; Copper; Germanium; Gold; Holmium; Iron; Lanthanum; Lead; Lithium; Manganese; Molybdenum; Neodymium; Nickel; Niobium; Nitrogen; Phosphorous; Praseodymium; Rubidium; Selenium; Silver; Strontium; Sulfur; Tellurium; Tin; Titanium; Tungsten; Uranium; Vanadium; Zinc; Zirconium RoHS (Register of Hazardous Substance) REACH =Enregistrement, évaluation, autorisation et restriction des substances chimiques en anglais : Registration, Evaluation, Authorization and restriction of CHemicals (REACH) 9

10. Common silicate glass compositions (wt%)10

11. European UE28 Glass production (millions tons)11

12. Glass containers collect(volunteer contribution points)Separated colours(Germany, UK, etc..)Mixed colours(France, ...)12

13. Infograph on Volunteer contributions Points13

14. Technology used for glass container wastes sorting 14

15. Industrial plant for sorting glass container wastes15

16. Specifications for sorted and processed cullet to be accepted for secondary raw materials in glass production16

17. 17The third R step in the 3Rs approach of glass end-consumer life is the recycling. Two ways are possible: the closed-loop recycling where glass waste (cullet or internal cullet) is considered as secondary raw-materials, the open-loop process where glass waste is considered as an additive or a matter to transform before re-using.

18. Benefits of recycling glass (close-loop)Energy savings. An increase of 10% of recycled glass in place of virgin raw materials allows a 3% energy saving, as an example, increasing the cullet % in the batch of an efficient end-port fired regenerative container glass furnace from 65 up to 75 % decreased the specific energy consumption from 3.95 MJ/kg molten glass to 3.8 MJ/kg. The use of cullet also aids in reducing batch-free time by both reducing the amount of refractory material in the batch, and by providing additional liquid throughout the melting process;Limiting the release of CO2. One ton of recycled glass saves more than 500 kg of CO2;Decreasing the removal of natural resources. For each kg of cullet used in replacement of the raw material, is a saving of 1.2 kg for virgin materials;Optimizing logistics and thus minimizing the carbon footprint linked to transportation. Recycled glass comes from local collections, close to the glass production plants;Avoiding landfilling or incineration18

19. Industrial and Academic Research for Glass Recycling (WoS April 2016)19

20. Why recycling cullet and CRT ?Industrial glass wastes (Soda lime silicate SLS):Cullet from container glass or tableware (! colour) Automotive glass Windshield car (! PVB)Lateral windows (! enamels)Glass balls for elastomer curing in Ballatoni bedWaste Electrical and Electronic Equipment - WEEE Microwave furnace glass plate, fridge glass shelf(! heavy metal contain or contamination during dismantling)LCD screen CRT (Pb (funnel), Ba (panel), containing)The glass waste treatments have a cost: Collect, wash and control the cullet composition (metal particle, ceramic stones…) for a re-use in batch melt for container glass (SLS) (100€/ton)Landfilling: 50€/ton for non-hazardous (SLS), more than 150€/ton for hazardous (CRT)What about “alternative” and/or “durable” routes ? 20

21. Waste glass resourcesTelevisions - Cathode ray tubeContainer glassWindow glassLamp glass21

22. 3R management for glass wastesCathode Ray Tube (CRT) valorisation (Recyver Project)Foam glass from CRT for MW applicationsCommon silicate glasses for catalytic applicationsCommon silicate glasses for biomaterialsArts and Sciences22

23. CRT composition23

24. 24CRT glasses compositions

25. 25Mixed crushed panel and funnel CRT glasses+fondant for lowering viscosity (alkaline, earth-alkaline carbonates)+reducing agent (C)=“New” Glass + precipitate Pb° metalLead beads from CRT glassUnleaded Glass[Pb]<0,05 wt%T°, timeLead oxide reduction schema

26. 26Foam glass with unleaded glass or panel glasses Elaboration+Formation of gas bubbles (CO2 or N2)Foaming agentGlass wasteCRT: Cathode Ray Tube glassSLS: Soda-Lime Silicate glass Foaming agent AlN, CaCO3, SiC or C Heat treatmentTemperatureTimeFurnace temperature vs. timeTemperature rampOperating temperatureCooling phaseExpansionGlass waste Glass foam

27. 27foaming particlesGlass culletT = 850°CReactive viscous molten glassfoaming particlesN2, CO2 bubbles foaming agent decomposition or reaction

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29. 292 AlN (s) → Al2O3 (s) + N2 (g) 4 AlN(s) + 3 TiO2 (s) → 2 Al2O3 (s) + 3 TiN (s) + ½ N2 (g)TiN (s) → TiO2 (s) + ½ N2 (g)SiC (s) → SiO2 (s) + CO, CO2 (g)CaCO3 (s) → CaO (s) + CO, CO2 (g)NB: These reactions for gas production are dependent of redox equilibriaGas production

30. 30Tunning open / closed porosityClosed porosity (%)Open porosity (%)Open porosity  Filtration, draining applicationClosed porosity  Insulation applicationCRT + %x AlN + %y TiO2 @ 850°C

31. 31Glass foam beads synthesisGranulator: rotary plate

32. 32Mousses Recyver150 - 170 kg/m3140 - 250 kg/m3 *0,065 – 0,100 W/(m.K)0,055 – 0,090 W/(m.K) #> 1000 kN/m2 **Non mesuréeoui* Calculée dcomp=dapp x 0,7** Compression sur bloc# Estiméegranulate of foam glass characteristics

33. 33Unleaded glass[Pb]<500 ppm Unleaded or panel glasses valorised in foam materials

34. 3R management for glass wastesCathode Ray Tube (CRT) valorisation (Recyver Project)Foam glass from CRT for MW applicationsCommon silicate glasses for catalytic applicationsCommon silicate glasses for biomaterialsArts and Sciences34

35. Recycled glass foams for high power microwave terminationsCollaboration with IETR UR1 - UBO35Compare inorganic foam carbon charged with polymer

36. Recycled glass foams for high power microwave terminations36

37. Recycled glass foams for high power microwave terminations37

38. 3R management for glass wastesCathode Ray Tube (CRT) valorisation (Recyver Project)Foam glass from CRT for MW applicationsCommon silicate glasses for catalytic applicationsCommon silicate glasses for biomaterialsArts and Sciences38

39. 39Common silicate glasses for catalytic applicationsFoam glass as support for metal nanoparticles(Ru, Rh, Pd, Au….)Oxidation catalysis for Volatile Organic Compounds degradation or contaminated water

40. 40Common silicate glasses for catalytic applicationsGood impregnation of NP aggregates (2-5 nm) without the use of de g-Al2O3 washcoatas used for ceramic or metal foamslixiviation test by soxhlet method

41. 41Common silicate glasses for catalytic applicationsWater treatment by advanced oxidation Coupling with ozone (O3) for aqueous solution Formation of radicals HO° very potents at ambiant T and P Mineralisation of micro-pollutantsDrug residues, endocrine disruptors, pesticides, etcPotabilization or purificationAir treatment by advanced oxidation Coupling with ozone (O3) for gaseous solution Mineralisation of micro-pollutantsIndustrial air treatmentIndoor air treatmentHalf-life time of atrazine / 10Decomposition of O3 with concomitant degradation of isopropanol and toluene demonstrated

42. 3R management for glass wastesCathode Ray Tube (CRT) valorisation (Recyver Project)Foam glass from CRT for MW applicationsCommon silicate glasses for catalytic applicationsCommon silicate glasses for biomaterialsArts and Sciences42

43. Biomaterials from clear glass cullet4375SiO2 -15Na2O - 10CaO (wt%) for flint glass SLS46 SiO2 - 24 Na2O - 24 CaO- 6P2O5 (wt%) for 46S6 Hench glassCompare SLS foam with 46S6 Check the cytotoxicity of SLS foam- on bone cells SaOS - on endothelial cells EAHY926 Figure 5(a)SaOS micrograph EAHY 926 micrographFigure 5(b)

44. 44SJ008SJ009SJ010SJ011SJ001SJ012Foam samples and 46S6 bulk samplesRaw materials for foam samplesSLS flint glass powderCaCO3 —> CaO + CO2(MAP) 2NH4H2PO4 —> 2NH3 + P2O5 + 3H2O(DAP) 2(NH4)2HPO4 —> 4NH3 + P2O5 + 3H2ORaw materials for 46S6 synthesisSiO2, CaCO3, NaPO3.3H2O, Na2CO3 , CaSiO3

45. 4546S6 best biocompatibilityFoam (SLS+CaCO3 ) not so bad...MAP and DAP foams present low biocompatibility, ? The presence of residue of NH4 is may be responsible ?.MTT test

46. 3R management for glass wastesCathode Ray Tube (CRT) valorisation (Recyver Project)Foam glass from CRT for MW applicationsCommon silicate glasses for catalytic applicationsCommon silicate glasses for biomaterialsArts and Sciences46

47. Glass recycling: a link between Arts and SciencesEESAB, École européenne supérieure d'art de Bretagne47

48. Undergrate and graduate students who participated Fabien BOIVENT (IUT SGM St Brieuc) - Nicolas FRESLON (IUT Chimie Rennes) , Margot TITOURAIS (IUT Chimie Rennes) , Thibault REYNALDO (L3 Chimie Rennes) , Manu GAUTIER (M1 Chimie) , Laure MOUGENOT (L3 Chimie Rennes) , Alexis MORIN (L3 Chimie Rennes) , Sébastien GENTY (L3 Mag. Matériaux Rennes) , Laure CERCUEIL (IUT Chimie Rennes) , Marc-Antoine THUAL (L3 ESIR1 Rennes) , Clyde MIDELET (L2 Phys Chimie Lorient) , Jade LEMOINE (M1 MEF Rennes) , Pierre ANDORIN (IUT Chimie Rennes) , Youenn POINTEL (ESIR1) , Sébastien GENTY – Ingénieur Etudes R&D (CDD) , Geoffrey LOUVET (IUT Chimie - Prod) , Thibaud BREGENT (L2 PCSTM UR1) , Laure CERCEUIL - Ingénieur Etudes R&D (CDD) , Aymeric HEDREUL - IUT Chimie Rennes , Guillaume LANOE - IUT SGM St Brieuc UR1, Killian DENOUE - L3 Chimie UR1, Valentin AUDEBERT, M2 Quatro – ENSCR, Anthony PIEL - IUT SGM UR1 , Shuyue JI - IUT Chimie ORSAY , Alan MATEU - ESIR1 UR1 , Steven AKOUN, Sarah MONTEUIL et al. EESAB Natural granite from BrittanyOr Foam glass ?Thanks MerciAll colleagues (Recyver, V&C, ISCR, IPR, ...)48

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51. 51Acta Biomater. 2012 Apr;8(4):1597-602. doi: 10.1016/j.actbio.2011.12.036. Epub 2012 Jan 15.A novel dentin bond strength measurement technique using a composite disk in diametral compression.Huang SH1, Lin LS, Rudney J, Jones R, Aparicio C, Lin CP, Fok A.Migliore et Zanotto , Glass technology, 1996

52. 52Foam sampleapparent density (g/cm3)pycnometric density (g/cm3)Open porosity (%)Closed porosity (%)total porosity (%)Average Failure strength (MPa) Weibull 1Weibull 2Foamglas™0,110,2146,7948,8195,60(0,04) --SG 140,332,3185,711,0986,800,829,51-NF 390,332,2485,271,5386,800,556,97-LM 60,432,3181,361,4482,801,078,26-SG 150,462,3480,381,2281,601,28,68-FG 2008-20,51,7371,068,9480,001,585,3267,24AM 030,532,3277,141,6678,801,474,2125,79LM 100,652,3672,501,5074,001,8610,40-NF 020,722,3469,291,9171,201,9713,10-SG14 sample

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54. #dappCompactée à 10%vol 0,31Poudre0,58

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56. #dappLCFG029 - 100g0,28LCFG045 - 500g0,34LCFG054 - 1000g0,47

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58. 58Foam glass properties

59. Glassy foam materials from river vaseCollaboration with COEUR émeraude – Dinan-Léhon59Description de la vaseL’insertion des sédiments doit se faire obligatoirement avec de la poudre de verreLa vase est naturellement carbonatée (DRX, ATG et biblio)Taux d’humidité moyen de 26%Les limites de vase au sein de différents verresLimite 25% de Vase et 75% de verre de bouteille (Verre Vert)Limite 20% de Vase et 80% de St-Gobain, Samin (rebut de verre)Limite 10% de Vase et 90% de verre TRC (Tube à rayons cathodiques)Eviter VOA (rebut de verre : verrerie ouvrière d’Albi) car contient des phases céramiquesCaCO3 : contrôler la porosité, mousse plus homogène, porosité plus fineMnO2 : porosité homogène

60. Glassy foam materials from river vaseCollaboration with COEUR émeraude – Dinan-Léhon60