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

• 1.Study on the penetration of TiO2 nanoparticlesthrough protective clothing and glovesin conditions simulating occupational useLudwig Vinches, Mehdi Ben Salah, Nicolas Testori,Grald Perron, Patricia Dolez*, Kevin J. Wilkinson**, Stphane Hallcole de technologie suprieure *Groupe CTT, Saint-Hyacinthe **Universit de Montral

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 NPsPenetration of NPs when skin is injured by abrasionafter repeated flexionsor even intact Need for dermal protection Precautionary principle : use of protective clothing and gloves against chemicalsAt the best of our knowledge, no study about the penetration of NPsthrough protective clothing and gloves in working conditionsLudwig Vinches et al. Ne3LS 20122 3. MaterialsProtective clothing and gloves / nanoparticles Nitrile rubber (NBR) (t = 100 m)nTiO2 - 15 nm, 99.7% pure anatase powder Pores Anatase TEM SEM x300 Rutile Butyl rubber (IIR) (t = 700 m)3-6% Platelets 50 nm Statistical study on 174 particlesAggregates 80 to 100 nmAgglomerates: up to 1 mSEM 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 20123 4. SetupCylinders DeformationprobeExposurechamber In a glove box SampleSamplingchamber Deformation probesLudwig Vinches et al. Ne3LS 20124 5. Results on NP penetration Sampling protocole Sampling protocoleusing sampling solutions Sampling solution = UHP H2OExposure Centrifugation on mica substrateschambernTiO2 powder or for Atomic Force Microscopy (AFM) colloidal solutionSampling solution = UHP H2O + 1% HNO3 Sample SamplingInductively 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 20125 6. Results on NP penetration through gloves ICP-MS analysis nTiO2 in water 25 20NBR (without nTiO2 in water) Exposure nTiO2 solution NBR (with nTiO2 in water) Ti4+ Concentration (g/L) chamberin water IIR (without nTiO2 in water) 15IIR (with nTiO2 in water)SampleSampling 10chamberSampling solution 5 50% - Biaxial0 deformation01 2 3456 7 8Experiment duration (h)5 minPenetration of nTiO2 in water through nitrile rubber after deformationsStrainNo penetration of nTiO2 in water through butyl rubberTimeLudwig Vinches et al. Ne3LS 20126 7. Elastomer behaviour Effect of nTiO2 liquid carriers and deformations on the sample surface Surface feature identification : SEM 5 kVSurface feature quantification : image processing 80Exposure Unexposedchamber SolventExposed to PG (7h) 70Dynamic biaxial deformation (7h) Dynamic biaxial deformation + PG (7h) Surface feature quantification (%) 60Outer surface 50SampleSamplingchamber40 3050 % - Biaxial 20deformation 10 05 minNitrile rubberButyl rubberStrainSolvent or deformation : Surface damageSolvent + deformation : Lubrication effectTimeLudwig Vinches et al. Ne3LS 2012 7 8. Gravimetric measurements Effect of nTiO2 solutions40 nTiO2 in water Nitrile rubber nTiO2 in PG30Short immersion timeMass gain (%)20 Mass gain after 8h-immersion (%) nTiO2 in water nTiO2 in PG10 35150 Due to the difference in viscosity and polarity 0 100200 300 400 500Immersion time (min) between the two solvents families80Long immersion time70A plateau in the swelling curves is observed60after 40 h of immersion Nitrile rubber(nitrile rubber)Mass gain (%)50 Butyl rubber40No significant mass gain is recorded30 for butyl rubber20nTiO2 in waterMass gain after 40h-immersion (%) in nTiO2 in water10Nitrile rubberButyl rubber 0 010 20 3040 50 60 7080 Immersion time (h) 73 0Ludwig Vinches et al. Ne3LS 2012 8 9. Results on NP penetration through gloves ICP-MS analysis nTiO2 in powder 25NBR (without nTiO2 powder)NBR (with nTiO2 powder)IIR (without nTiO2 powder)Exposure 20IIR (with nTiO2 powder)chambernTiO2 Ti4+ concentration (g/L) powder 15SamplingSample 10chamber Samplingsolution5 50% - biaxial0 deformation0 1 23 4 56 7 8Experiment duration (h)5 minPenetration of nTiO2 in powder through nitrile rubber after deformationsStrainNo penetration of nTiO2 in powderthrough butyl rubberTimeLudwig Vinches et al. Ne3LS 20129 10. Results on NP penetration through glovesAFM analysis nTiO2 in powderMica substrateExposurenTiO2before centrifugationchamber powderSampleSamplingchamber Samplingsolution50% biaxialdeformation Mica substrate 7hafter centrifugation of asampling solution5 min (Nitrile rubber 7h)Penetration of nTiO2 powderStrainthrough nitrile rubber after deformationsConfirmation of ICP-MS analysis TimeNo information on chemical composition of the NPsLudwig Vinches et al. Ne3LS 2012 10 11. Results on NP penetration through glovesnTiO2 in powder nTiO2 in solution80 Unexposed 40 Exposed to PG (7h) nTiO2 in water70 Dynamic biaxial deformation (7h)nTiO2 in PG Dynamic biaxial deformation + PG (7h)Surface feature quantification (%)60 3050 Mass gain (%)40 203020 10100 0 Nitrile rubber Butyl rubber0 100 200300 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 (g/L) Ti4+ Concentration (g/L)IIR (without nTiO2 in water)15 15 IIR (with nTiO2 in water)10 10 55 00 0 1 23 45 6 7 80 1 2 34 5 6 7 8Experiment duration (h) Experiment duration (h)Ludwig Vinches et al. Ne3LS 201211 12. Results on NP penetration through NWC AAS analysis nTiO2 in PG80007000 ExposurenTiO2 solution chamber6000Ti4+ Concentration (mg/L) in PG50004000SampleSampling3000chamber Samplingsolution2000100010% - Biaxial 0deformation0 1 23 4 56 7 8 Experiment duration (h)5 minPenetration of nTiO2 in PGStrain through nonwoven coverall after deformations TimeLudwig Vinches et al. Ne3LS 2012 12 13. Fabrics behaviour Effect of deformations on the water vapor permeability 140000UnexposedDynamic biaxial deformations (5h) 1300001,2-propanediol + deformations (5h) 120000 Outer surface Permeation (g.m/m/day) Solvent 110000 Exposure (PG) chamber 100000 90000 Sample Sampling80000 chamber 70000 6000010 % - Biaxial 50000deformation 050100 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 2500With nTiO2 powderWithout nTiO2 powderExposure 2000chambernTiO2 Ti4+ Concentration (g/L) powder 1500SamplingSample 1000chamber Samplingsolution 500 10% - biaxial0 deformation0 12 3 4 56 7 8Experiment duration (h)5 minPenetration of nTiO2 in powderStrainthrough nonwoven coverallafter deformationsTimeLudwig Vinches et al. Ne3LS 201214 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 effectPenetration 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 Mah, Alice Jambou, Flicien Deltombe,Pierre-Emmanuel Daure-Cagnol, Maud Leblanc (TS) Yves Cloutier, Chantal Dion, Ginette Truchon (IRSST) Gilles lEsprance, Philippe Plamondon (cole Polytechnique de Montral) And the support of the :Research chair in protective materials and equipment for occupational safety and health , TSLudwig Vinches et al. Ne3LS 2012 16 17. Thank you for your attentionLudwig Vinches et al. Ne3LS 2012