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Ludwig Vinches et al._Study on the penetration of ti o2 nanoparticles through protective clothing and gloves in conditions simulating occupational use
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Ludwig Vinches et al._Study on the penetration of ti o2 nanoparticles through protective clothing and gloves in conditions simulating occupational use

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  • 1. Study on the penetration of TiO2 nanoparticles through protective clothing and gloves in conditions simulating occupational use Ludwig Vinches, Mehdi Ben Salah, Nicolas Testori,Gérald Perron, Patricia Dolez*, Kevin J. Wilkinson**, Stéphane Hallé École de technologie supérieure *Groupe CTT, Saint-Hyacinthe **Université de Montréal
  • 2. Context• Increasing number of people (6 millions in 2020) exposed to nanoparticles (NPs) Scientists in laboratories Workers in companies• Increasing evidence that skin is not an impervious membrane for NPs Penetration of NPs when skin is injured by abrasion after repeated flexions or even intact Need for dermal protection Precautionary principle : use of protective clothing and gloves against chemicals At the best of our knowledge, no study about the penetration of NPs through protective clothing and gloves in working conditionsLudwig Vinches et al. – Ne3LS 2012 2
  • 3. Materials Protective clothing and gloves / nanoparticles Nitrile rubber (NBR) (t = 100 µm) nTiO2 - 15 nm, 99.7% pure anatase powder Pores Anatase TEM SEM x300 Rutile Butyl rubber (IIR) (t = 700 µm) 3-6% Platelets 50 nm Statistical study on 174 particles Aggregates ≈ 80 to 100 nm Agglomerates: up to 1 µm SEM x300 Nonwoven coverall material (NWC) in polyolefin Commercial nTiO2 solutions  15 nm, anatase, 20 wt% in 1,2-propanediol (PG) Pores  15 nm, anatase, 15 wt% in water Mass fractions and sizes of nanoparticles similar to manufacturer data (TGA & FCS) SEM x300Ludwig Vinches et al. – Ne3LS 2012 3
  • 4. SetupCylinders Deformation probe Exposure chamber In a glove box Sample Sampling chamber Deformation probesLudwig Vinches et al. – Ne3LS 2012 4
  • 5. Results on NP penetration Sampling protocole Sampling protocole using sampling solutions Sampling solution = UHP H2O Exposure Centrifugation on mica substrates chamber nTiO2 powder or for Atomic Force Microscopy (AFM) colloidal solution Sampling solution = UHP H2O + 1% HNO3 Sample Sampling Inductively Coupled Plasma – Mass chamber Sampling solution Spectroscopy (ICP-MS) Atomic Absorption Spectroscopy (AAS)• No contact with the sample during the test• Used to rinse the chamber walls after thetestLudwig Vinches et al. – Ne3LS 2012 5
  • 6. Results on NP penetration through gloves ICP-MS analysis – nTiO2 in water 25 20 NBR (without nTiO2 in water) Exposure nTiO2 solution NBR (with nTiO2 in water) Ti4+ Concentration (µg/L) chamber in water IIR (without nTiO2 in water) 15 IIR (with nTiO2 in water) SampleSampling 10chamber Sampling solution 5 50% - Biaxial 0 deformation 0 1 2 3 4 5 6 7 8 Experiment duration (h) 5 min Penetration of nTiO2 in water through nitrile rubber after deformationsStrain No penetration of nTiO2 in water through butyl rubber TimeLudwig Vinches et al. – Ne3LS 2012 6
  • 7. Elastomer behaviour Effect of nTiO2 liquid carriers and deformations on the sample surface Surface feature identification : SEM – 5 kV Surface feature quantification : image processing 80 Exposure Unexposed chamber Solvent Exposed to PG (7h) 70 Dynamic biaxial deformation (7h) Dynamic biaxial deformation + PG (7h) Surface feature quantification (%) 60 Outer surface 50 Sample Sampling chamber 40 30 50 % - Biaxial 20 deformation 10 0 5 min Nitrile rubber Butyl rubber Strain Solvent or deformation : Surface damage Solvent + deformation : Lubrication effect TimeLudwig Vinches et al. – Ne3LS 2012 7
  • 8. Gravimetric measurements Effect of nTiO2 solutions 40 nTiO2 in water Nitrile rubber nTiO2 in PG 30 Short immersion timeMass gain (%) 20 Mass gain after 8h-immersion (%) nTiO2 in water nTiO2 in PG 10 35 15 0 Due to the difference in viscosity and polarity 0 100 200 300 400 500 Immersion time (min) between the two solvents families 80 Long immersion time 70 A plateau in the swelling curves is observed 60 after 40 h of immersion Nitrile rubber (nitrile rubber) Mass gain (%) 50 Butyl rubber 40 No significant mass gain is recorded 30 for butyl rubber 20 nTiO2 in water Mass gain after 40h-immersion (%) in nTiO2 in water 10 Nitrile rubber Butyl rubber 0 0 10 20 30 40 50 60 70 80 Immersion time (h) 73 0Ludwig Vinches et al. – Ne3LS 2012 8
  • 9. Results on NP penetration through gloves ICP-MS analysis – nTiO2 in powder 25 NBR (without nTiO2 powder) NBR (with nTiO2 powder) IIR (without nTiO2 powder) Exposure 20 IIR (with nTiO2 powder) chamber nTiO2 Ti4+ concentration (µg/L) powder 15 Sampling Sample 10 chamber Sampling solution 5 50% - biaxial 0 deformation 0 1 2 3 4 5 6 7 8 Experiment duration (h) 5 min Penetration of nTiO2 in powder through nitrile rubber after deformations Strain No penetration of nTiO2 in powder through butyl rubber TimeLudwig Vinches et al. – Ne3LS 2012 9
  • 10. Results on NP penetration through gloves AFM analysis – nTiO2 in powder Mica substrate Exposure nTiO2 before centrifugation chamber powder Sample Sampling chamber Sampling solution 50% – biaxial deformation – Mica substrate 7h after centrifugation of a sampling solution 5 min (Nitrile rubber – 7h) Penetration of nTiO2 powder Strain through nitrile rubber after deformations Confirmation of ICP-MS analysis Time No information on chemical composition of the NPsLudwig Vinches et al. – Ne3LS 2012 10
  • 11. Results on NP penetration through gloves nTiO2 in powder nTiO2 in solution 80 Unexposed 40 Exposed to PG (7h) nTiO2 in water 70 Dynamic biaxial deformation (7h) nTiO2 in PG Dynamic biaxial deformation + PG (7h)Surface feature quantification (%) 60 30 50 Mass gain (%) 40 20 30 20 10 10 0 0 Nitrile rubber Butyl rubber 0 100 200 300 400 500 Immersion time (min) 25 25 NBR (without nTiO2 powder) NBR (with nTiO2 powder) 20 IIR (without nTiO2 powder) 20 NBR (without nTiO2 in water) IIR (with nTiO2 powder) NBR (with nTiO2 in water) Ti4+ concentration (µg/L) Ti4+ Concentration (µg/L) IIR (without nTiO2 in water) 15 15 IIR (with nTiO2 in water) 10 10 5 5 0 0 0 1 2 3 4 5 6 7 8 0 1 2 3 4 5 6 7 8 Experiment duration (h) Experiment duration (h) Ludwig Vinches et al. – Ne3LS 2012 11
  • 12. Results on NP penetration through NWC AAS analysis – nTiO2 in PG 8000 7000 Exposure nTiO2 solution chamber 6000 Ti4+ Concentration (mg/L) in PG 5000 4000 Sample Sampling 3000 chamber Sampling solution 2000 1000 10% - Biaxial 0 deformation 0 1 2 3 4 5 6 7 8 Experiment duration (h) 5 min Penetration of nTiO2 in PG Strain through nonwoven coverall after deformations TimeLudwig Vinches et al. – Ne3LS 2012 12
  • 13. Fabrics behaviour Effect of deformations on the water vapor permeability 140000 Unexposed Dynamic biaxial deformations (5h) 130000 1,2-propanediol + deformations (5h) 120000 Outer surface Permeation (g.m/m²/day) Solvent 110000 Exposure (PG) chamber 100000 90000 Sample Sampling 80000 chamber 70000 60000 10 % - Biaxial 50000 deformation 0 50 100 150 200 250 300 350 Time (min) 5 min Deformation : • A significant decrease in water vapor permeability • Reduction of the pores size Strain Deformation + solvent : • Lubrication effect TimeLudwig Vinches et al. – Ne3LS 2012 13
  • 14. Results on NP penetration through NWC AAS analysis – nTiO2 powder 2500 With nTiO2 powder Without nTiO2 powder Exposure 2000 chamber nTiO2 Ti4+ Concentration (µg/L) powder 1500 Sampling Sample 1000 chamber Sampling solution 500 10% - biaxial 0 deformation 0 1 2 3 4 5 6 7 8 Experiment duration (h) 5 min Penetration of nTiO2 in powder Strain through nonwoven coverall after deformations TimeLudwig Vinches et al. – Ne3LS 2012 14
  • 15. Conclusions Development of a test method for protective clothing and gloves against NPs inconditions simulating occupational use • Experimental setup + NP detection techniques • NPs: powder and in colloidal solutions • Mechanical deformations / glove microclimate Glove material behaviour after mechanical deformations • Surface damage / Lubrication effect • Swelling effect Nonwoven coverall material behaviour after mechanical deformations • Water vapor permeability decrease • Lubrication effect Penetration of TiO2 nanoparticles (in powder and solutions) through nitrile rubber protective gloves and nonwoven coverall after deformations Need for further investigationsLudwig Vinches et al. – Ne3LS 2012 15
  • 16. With the collaboration of : Swann Mahé, Alice Jambou, Félicien Deltombe, Pierre-Emmanuel Daure-Cagnol, Maud Leblanc (ÉTS) Yves Cloutier, Chantal Dion, Ginette Truchon (IRSST) Gilles l’Espérance, Philippe Plamondon (École Polytechnique de Montréal) And the support of the : Research chair in protective materials and equipment for occupational safety and health , ÉTSLudwig Vinches et al. – Ne3LS 2012 16
  • 17. Thank you for your attentionLudwig Vinches et al. – Ne3LS 2012