Mousses de verre issues du recyclage : Quelques exemples d’études et applications

1. Mousses de verre issues du recyclage: Quelquesexemplesd’études et applications Ronan LEBULLENGER et al. ronan.lebullenger@univ-rennes1.fr UMR6226 - ISCR – Eq. Verres et Céramiques

2. France ISCR Expertise Conception & Synthesis of Molecules & Materials with Dedicated Properties Chemistry & Engineering for Sustainable Development Molecules &Materials for Optics & Electronics Molecules & Materials for Health Rennes Institut of Chemical Sciences ISCR

3. 3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences

4. 3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences

5. 3R management for glass • 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.

7. By Optimisation of: melting conditions - homogeneity, stone and bubblefreegob, parison viscosity,...) shaping containers process - mould and press conditions) coating - spray in cold section and annealing kiln • better mechanical properties for lighter products

8. Definition of glass from environmental agencies CAS Number for glass: 65997-17-3 Glass, oxide, chemicals CAS Number: 65997-17-3 EPA Registry Name: Glass, oxide, chemicals Molecular Formula: Unspecified

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)

10. Common silicate glass compositions (wt%)

11. European UE28 Glass production (millions tons)

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

13. Infograph on Volunteer contributionsPoints

14. Technology used for glass container wastes sorting

15. Industrial plant for sorting glass container wastes

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

17. The 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 incineration

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

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 elastomercuring in Ballatonibed • Waste 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 ?

21. Waste glass resources Window glass Container glass Televisions - Cathode ray tube Lamp glass

22. 3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences

23. CRT composition

24. CRT glasses compositions

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

26. Foam glass with unleaded glass or panel glasses • Elaboration • Expansion • Heattreatment • Formation of gasbubbles (CO2 or N2) • Glass waste • Foaming agent • + • Glass foam Temperature • Glass waste • CRT: Cathode Ray Tube glass • SLS: Soda-Lime Silicate glass • Operating temperature • Cooling phase Time • Foaming agent • AlN, CaCO3, SiCor C • Temperature ramp Furnace temperature vs. time

27. T = 850°C foaming particles Glass cullet N2, CO2bubbles foaming agent decomposition or reaction Reactiveviscousmolten glass foaming particles

29. Gas production • 2 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 equilibria

30. Tunning open / closed porosity CRT + %x AlN + %y TiO2 @ 850°C Closed porosity (%) Open porosity (%) • Open porosity  Filtration, draining application • Closed porosity  Insulation application

31. Glass foam beads synthesis Granulator: rotary plate

32. granulate of foam glass characteristics * Calculée dcomp=dapp x 0,7 ** Compression sur bloc # Estimée

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

34. 3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences

35. Recycled glass foams for high power microwave terminations • Collaboration with IETR UR1 - UBO • Compare inorganic foam • carbon charged with polymer

36. Recycled glass foams for high power microwave terminations

37. Recycled glass foams for high power microwave terminations

38. 3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences

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

40. Common silicate glasses for catalytic applications • Good impregnation • of NP aggregates (2-5 nm) • without • the use of de g-Al2O3washcoat • as used for ceramic or metal foams • lixiviation test by soxhlet method

41. Common silicate glasses for catalytic applications • Water treatment by advanced oxidation • Coupling with ozone (O3) for aqueous solution • Formation of radicals HO° verypotents at ambiant T and P • Mineralisation of micro-pollutants • Drug residues, endocrine disruptors, pesticides, etc • Potabilization or purification • Air treatment by advanced oxidation • Coupling with ozone (O3) for gaseous solution • Mineralisation of micro-pollutants • Industrial air treatment • Indoor air treatment Half-life time of atrazine / 10 Decomposition of O3 with concomitant degradation of isopropanol and toluene demonstrated

42. 3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences

43. Biomaterials from clear glass cullet 75SiO2 -15Na2O - 10CaO (wt%) for flint glass SLS 46 SiO2 - 24 Na2O - 24 CaO- 6P2O5 (wt%) for 46S6 Hench glass • Compare SLS foam with 46S6 • Check the cytotoxicity of SLS foam • - on bone cells SaOS • - on endothelial cells EAHY926 Figure 5(a) Figure 5(b) SaOS micrograph EAHY 926 micrograph

44. SJ008 SJ010 SJ009 • Raw materials for 46S6 synthesis • SiO2, CaCO3, NaPO3.3H2O, Na2CO3 , CaSiO3 • Raw materials for foam samples • SLS flint glass powder • CaCO3 —> CaO + CO2 • (MAP) 2NH4H2PO4 —> 2NH3 + P2O5 + 3H2O • (DAP) 2(NH4)2HPO4 —> 4NH3 + P2O5 + 3H2O SJ011 SJ001 SJ012 Foamsamples and 46S6 bulksamples

45. MTT test 46S6 best biocompatibility Foam (SLS+CaCO3 ) not so bad... MAP and DAP foams present low biocompatibility, ? The presence of residue of NH4 is may be responsible ? .

46. 3R management for glass wastes • Cathode RayTube (CRT) valorisation (Recyver Project) • Foam glass from CRT for MW applications • Common silicate glasses for catalytic applications • Common silicate glasses for biomaterials • Arts and Sciences

47. Glass recycling: a linkbetween Arts and Sciences • EESAB, École européenne supérieure d'art de Bretagne

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 • All colleagues (Recyver, V&C, ISCR, IPR, ...) Thanks Merci Natural granite from Brittany Or Foam glass ?

49. Q /A