file - CarbonInspired
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file - CarbonInspired
CarbonInspired Workshop Internacional: Aplicación de Nanomateriales en la Industria Madrid, 21 de Noviembre de 2012 CarbonInspired es una red de transferencia de conocimiento orientada a la aplicación de materiales de alto valor añadido basados en nanopartículas carbonosas, con especial interés en los sectores de automoción y construcción. Programa 09:00-09:15 REGISTRO 09:15-09:30 Apertura & bienvenida Raquel Nieto Resp. de Comunicación y Capitalización - STC SUDOE 09:30-10:00 CarbonInspired: red de transferencia de conocimiento en nanomateriales Alberto Tielas Responsable del Grupo I+D New Materials - CTAG 10:00-10:30 Nanoestructuras de Carbono: logros & retos Miren Blanco Investigadora - IK4-TEKNIKER 10:30-11:00 Orientado a investigadores, emprendedores, ingenieros, directores técnicos, directores de proyecto, responsables de producto, gerentes y profesionales de cualquier sector industrial. Nanopartículas en el sector de automoción Mario Ordóñez Responsable de la Ud. Materiales - MAIER 11:00-11:30 PAUSA CAFÉ La inscripción es gratuita. Solo tiene que seguir dos pasos: 11:30-12:00 Sectores de Automoción y Construcción: papel presente y futuro de los composites nanocarbonosos Olivia Menes Investigadora - AIMPLAS 12:00-12:30 Diseño y desarrollo de nuevos nanocomposites de carbono por fuerzas electrohidrodinámicas para aplicaciones en el sector aeroespacial Pablo Ballorca Ingeniero de I+D - YFLOW 12:30-13:00 Comercializando nanotubos de carbono Alexander Korzhenko Ingeniero de I+D en el Dpto. NTC - ARKEMA 13:00-13:30 Nanofibras de plata para tintas conductoras y adhesivos flexibles conductores Carlos Vázquez Co-fundador de NANOGAP - Profesor en la Universidad de Santiago de Compostela 13:30-14:30 PAUSA COMIDA 14:30 15:00 Compounding industrial de elastomeros y nanocargas Maxime Charman Director de I+D - EMAC 15:00-15:30 Aspectos de seguridad: ¿cuál es la realidad de las nanotecnologías? Marilys Blanchy Ingeniera de I+D - Asociación ADERA / RESCOLL 15:30-16:00 Films de Nanodiamante: carbono para aplicaciones tribológicas Victor Neto Investigador - Universidad de Aveiro 16:00-16:30 Nanomateriales en la industria de la construcción José Vera-Agullo Resp. Grupo de Materiales Tradicionales - ACCIONA 16:30-17:00 Ruegos y preguntas. Clausura de la jornada El principal objetivo de la red CarbonInspired es transferir el conocimiento existente a las empresas, permiténdoles transformar este conocimiento en valor real dentro del mercado. Participe en este workshop gratuita y aproveche la oportunidad para compartir conocimientos y experiencias, conocer posibles socios e intercambiar información de interés. Inscripción 1. Registro en la platforma virtual www.carboninspired.com para obtener su código de usuario y contraseña. 2. Cumplimentar el formulario adjunto y enviarlo por e-mail a la siguiente dirección: [email protected]. Por favor, un formulario por asistente. Plazo máximo de registro: martes 13 de noviembre de 2012 Aforo limitado. Plazas asignadas por orden de solicitud. El registro en la plataforma virtual es imprescindible Lugar de celebración Hotel Santo Domingo Mercure C/ San Bernardo 1 28013 - Madrid GPS: N40º 25' 14.13'' W03º 42' 30.15'' Sponsors www.carboninspired.com 9 COMPOUNDING INDUSTRIAL DE ELASTÓMEROS Y NANOCARGAS MAXIME CHARMAN DIRECTOR I+D EMAC Industrial compounding of elastomers with nanofillers M. Charman EMAC élastomères industriels, Mauléon (64) CarbonInspired International Workshop « Application of Nanomaterials in Industry » Madrid, November 21st 2012 1 EMAC introduction • • • Set up in 1950 Staff : 70 Turnover 2011 : 12.5 M € • • French Leader for technical rubber and polymer compounds 6000 tons produced in 2011 : – 4000 tons of black compounds – 2000 tons of coloured compounds CarbonInspired International Workshop Madrid, November 21st 2012 2 The elastomers compounded • NR / SBR • EPDM • CR > NBR/IIR • « Special » elastomers (ACM, ECO, FKM, HNBR,CSM…) Special Elast om er s 13% IIR 4% NBR 4% NR 27% CR 9% SBR 16% EPDM 27% CarbonInspired International Workshop Madrid, November 21st 2012 3 Markets Aeronautics 5% Adhesives 5% Wires 5% Extruders 8% Automotive 49% Moulding 10% Railways 8% Building 10% CarbonInspired International Workshop Madrid, November 21st 2012 4 Emac in the nanoworld First trials EMAC/Arkema 2005 2006 Industrial mixer securisation Start of PhD thesis between EMAC / UPPA 2007 2008 2009 2010 2011 Lab mixer securisation First industrial trials with CNTs 2013 2012 End of Nacomat Project Start of Nacomat Project End of PhD thesis between EMAC / UPPA CarbonInspired International Workshop Madrid, November 21st 2012 5 Agenda 1.HSE issue 2.CNT EPDM formulation 3.Rubber‐Nanoclays formulation 4.Conclusions CarbonInspired International Workshop Madrid, November 21st 2012 6 HSE issue CarbonInspired International Workshop Madrid, November 21st 2012 7 Mixing securisation Main potential expositions : inhalation, ingestion, eye and skin contacts. INRS1 recommandations : •Isolate and mechanize the process ; •Work with continous process and use of masterbatches ; •Avoid weighing and transfering of powder form; •Capture locally the free powder nanofiller residue ; •Filter the polluted air : HEPA filter (quality > H13) •Wear a personal protective equipment : FFP3 mask, gloves, glasses, Dust‐proof clothes (type 5) •Clean the work environment ; •Collect and treat the waste ; HEPA filter •Train and inform the exposed workers. CarbonInspired International Workshop Madrid, November 21st 2012 1 M. Ricaud, et al., ND 2286, INRS, (2008) 8 Mixing securisation Lab mixer (1,5 L) Using of CNTs pre‐weighed bags from Arkema Ventilation by air extraction and filtration (HEPA H14 filters) Using of PPE Industrial mixer (17 L) CarbonInspired International Workshop Madrid, November 21st 2012 9 CNT EPDM formulation CarbonInspired International Workshop Madrid, November 21st 2012 10 CNT Physical structure : ‐ High aspect ratio (L/D = 1000) ‐ Very good electrical1 and mechanical2 properties 1 Hamada, N. et al., 2 Phys. Rev. Lett. 1992; 68:1579‐1581 Treacy, M.M.J. et al., Nature 1996; 381 : 678‐680 Potential Applications in Rubber domain: ‐ Electrostatic charge dissipation (ESD) ‐ Wire and automotive industries Many problems ‐ Difficulties to obtain a good dispersion of CNTs in polymer matrixes 3 techniques : ‐ Solvent mixing ‐ “In‐situ” polymerization ‐ Melt mixing ‐ Lack of affinity between CNTs and various polymers Æ Functionalization 3 techniques : ‐ Chemical modification of CNTs surface3 ‐ Polymer grafting onto CNTs surface4 ‐ Polymer adsorption5 3 Courbaron , AC, et al. Adv. Mat. Res. 2010;112:29‐36 4 Datsyuk, V. et al. Carbon 5 2005; 43:873‐76 Bhattacharyya, A.R. et al. Chem. Phys. Lett. 2004; 392, 28–33 CarbonInspired International Workshop Madrid, November 21st 2012 11 Improvement of the filler‐matrix affinity Copolymer adsorption onto CNTs surface by melt mixing S. Peeterbroeck et al. Comp. Sci. Tech. 2007; 67 :1659–1665 Better CNTs dispersion when the matrix polarity is improved EVA (12%VA, MFI=0.5g/10min) +3%NTC EVA (19%VA, MFI=0.65g/10min) +3%NTC EVA (27%VA, MFI=3g/10min) +3%NTC PVac (100%VA, 3%NTC Hypothesis EPM EVA ‐ Association between EPM and EVA being very current in the rubber industry ‐ Affinity between CNTs and EVA and between EPM and EVA VA CarbonInspired International Workshop Madrid, November 21st 2012 E EPM 12 Rheological properties Influence of the matrix viscosity on the CNTs dispersion (1wt%) Master curves at Tref=120°C (100‐120‐140‐160) dmax = 40 à 50 µm dmax = 15 à 20 µm More important increase in viscosity and non‐newtonian behavior for EPM 2 Æ Better dispersion of CNTs Correlation between dispersion and rheological behavior CarbonInspired International Workshop Madrid, November 21st 2012 13 Electrical properties Electrical conductivity vs CNT wt% for EPM2/EVA Electrical conductivity is modeled with a power law equation for φ>φc: σ ∝ (φ − φc )t φc : percolation threshold concentration φc = 2,93wt% t = 2,20 1D. Stauffer, Introduction to percolation theory, Taylor & Francis, London (1985) CarbonInspired International Workshop Madrid, November 21st 2012 14 Rheological properties Mooney Viscosimeter MV2000 100°C – 4 min – 1s‐1 Viscosity level is too important = impossibility to process this blend Important increase of the viscosity by addition of CNTs and conductive carbon black The viscosity remains constant when CNTs come from Master Batches The effect of CNTs on the viscosity level was cancelled by EPM‐EVA phase CarbonInspired International Workshop Madrid, November 21st 2012 15 Rheological properties RDA2 Rheometer ‐60 à 120°C – 2°C/min – 1rad/s Better reinforcement with CNT than conductive carbon black Better reinforcement with an association of conductive carbon black and CNTs Synergistic effect between the fillers1,2 1Bokobza, L. et al., J. Polym. Sci.: Part B: Polym. Phys., 46, 1939‐1951, (2008) 2Yan, N. et al., Plast. Rubb. Comp., 38, 290‐296, (2009) CarbonInspired International Workshop Madrid, November 21st 2012 16 Electrical Properties Keithley 6430 Surface conductivity on film (thickness = 200µm) Low increase of electrical conductivity for blends which associate fillers Low interactions between fillers No synergistic effect on electrical properties Results in contradiction with the literature1 for rubbers obtain by solvent mixing 1Bokobza, L. et al., J. Polym. Sci.: Part B: Polym. Phys., 46, 1939‐1951, (2008) CarbonInspired International Workshop Madrid, November 21st 2012 17 Rubber‐Nanoclays formulation CarbonInspired International Workshop Madrid, November 21st 2012 18 Nanoclays The nanoclays more used belong to the phyllosilicates familly. Hydrophilic material Æ chemical treatment (organo modification) Montmorillonite Fibrous clays China Clay Hydrated sodium calcium aluminium magnesium silicate hydroxide Formula : (Na,Ca)0,3(Al,Mg)2Si4O10(OH)2∙nH2O Sepiolite : hydrated magnesium natural silicate Hydrated aluminium silicate Formula : Al2Si2O5(OH)4 Formula : Mg4Si6O15(OH)2 6(H2O) Application fields : Fire resistance, gas permeability CarbonInspired International Workshop Madrid, November 21st 2012 19 Nanoclays in EPDM Dispersion limited over 15 phr with twin‐screw extruder Æ LCPO laboratory ¾ Using of organo‐modified nanoclays (Pangel B20®) ¾ Better dispersion after encapsulation by PE‐g‐MAH (Orevac®) or EVA‐g‐MAH (Fusabond®) 1μ 100nm 20nm CarbonInspired International Workshop Madrid, November 21st 2012 20 Encapsulation of nanoclays in Fusabond (50/50) Ko‐Buss kneader (100°C, 110tr/min, 30 ‐ 40s‐1). Kneader pins Single‐screw extruder at low shear rate Distributive and dispersive mixing through the screw CarbonInspired International Workshop Madrid, November 21st 2012 21 Formulation of nanoclay MB Twin‐screw encapsulation (LCPO) Ko‐Buss kneader encapsulation (EMAC) Dispersion state and mechanical properties equivalent (10 phr of MB) Strain at break : 2.4 MPa vs 2.5 Mpa Elongation at break : 257% vs 253% Young modulus : 2.7 MPa vs 2.6 MPa A trial has been done up to 27,5 phr of Sepiolite (55 phr of MB) CarbonInspired International Workshop Madrid, November 21st 2012 22 Comparison between CNT / Nanoclay / silica Final SPS application : improve ablation resistance (EPDM material) 3 compounds are compared: ‐Silica ‐ CNT ‐ Nanoclay allumeur structure PTI Chargement Tuyère Results (torch fire) : v(ablation mm/s) = f(density) Butée Divergent Nanoclay (B20, 27,5 phr) : decrease of density (8%) compared to silica for the same level of ablation speed. Good level of dispersion. CNT (pure) : decrease of density (16%) compared to silica for the same ablation speed. Bad level of dispersion. CarbonInspired International Workshop Madrid, November 21st 2012 23 Nanoclays in NBR Gaz Permeability for seal applications Introduction in the blends :‐ natural montmorillonite ‐ organo‐modified talc ‐ organo‐modified montmorillonite Increase of imperméability by 25% with organo‐modified nanoclays ESD coloured rubber Introduction in the blends : ‐ SiO2 functionalized nanoparticles ‐ ester of polyethylene glycol modified with nanoparticles Resistivity = 2.106 Ω/m CarbonInspired International Workshop Madrid, November 21st 2012 24 Conclusion HSE has to be considered as a priority before any industrial nanofiller compounding. Typical rubber techniques are applicable to disperse nanofillers if an encapsulation is prior considered. CNT composite has shown really interesting conductivity properties. Nanoclay seems a potential candidate for ablation application but must be tried at a higher level to assess any better properties. CNT is also an option to consider for ablation resistance because shows a significant weight advantage despite the bad level of dispersion. Nanoclay seems a potential candidate for improve gas impermeability of for rubber seal applications CarbonInspired International Workshop Madrid, November 21st 2012 25 Perspective Colaborative R&D project on nanomaterials NAWHICEL Development of elastomers compounds filled with cellulose nanofibers or nanowhiskers Potential markets : Automobile and transport, adhesive, … PENELOPE Development of elastomers filled with nanoclays Æ Improvement of fluid and gas permeability Potential markets : Pomp seal CarbonInspired International Workshop Madrid, November 21st 2012 26 Thanks for your attention CarbonInspired International Workshop Madrid, November 21st 2012 27 10 ASPECTOS DE SEGURIDAD: ¿CUÁL ES LA REALIDAD DE LAS NANOTECNOLOGÍAS? MARILYS BLANCHY INGENIERA I+D ADERA / RESCOLL Nanotechnologies : What the reality of safety issue? Marilys Blanchy- ADERA International Workshop, Madrid 21st of September Index Some european definition and regulations Safety Risk presented by nanotechonologies Management of the risk Environmental issue Nanomaterials : an European definition Definition of nanomaterial from the European Commission : “Nanomaterial means a natural, incidental or manufactured material containing particles, in an unbound state or as aggregate or as an agglomerate and where, for 50% or more of the particles in the number size distribution, one or more external dimensions is in the size range 1nm-100nm”. This definition does not take into account toxicity and reactivity of the materials Nanomaterials : an European definition Nanotechnologies : an European definition Two standard ISO for nanomaterials ISO/TS 27687 : 2008 : Nanotechnologies – Terminology and definition of nano-objects – Nanoparticles, nanofibers and nanoplates. ISO/TR 13121: 2011 (October 2011) gives a guideline for the assessment of risks associated to nanomaterials. REACH So far nanoparticles and nanomaterials were not included into REACH Regulation. This is going to be revised to include nanomaterials Nanomaterials still need more general framework rules : depending on their chemistry, size, shape, adequat low limit of exposure… Occupational exposure One of the main fields involved in nanotechnologies in Europe is the automotive field with more than 40% of SMEs in Europe More 1200 SMEs are involved in developing nanotechnologies Today more than 400 consumers product include nanoparticles Occupational exposure Some example of activities including nanotechnology Construction – For the improvment of wear resistance, rigidity, more efficient insulation materials Health Care – engineering,… New drug and active agent, drug delivery system, tissue Energy conversion and use – Increasing efficiency of energy conversionand low wastage storage of energy Automobile and aerospace industry – Reinforced and stronger material, sensors Chemical industry Electronics and communication – components Occupational exposure optical and optoelectronic Occupational exposure It exists several pathways to be exposed to materials in general Inhalation Cutaneous contact Ingestion And several methods to evaluate the potential impact on the organism Occupational exposure Inhalation The main risk of exposure Nanoparticles are difficult to eliminate from the organism Today there is no low limit of observable effect Capacity to reach deap respiratory area Occupational exposure Cutaneous contact Dermal contact Eye contact Ingestion If rules of good pratice implemented Æ low risk of exposure The issue with nanoparticle is its possible reactivity compared to the same particles at a larger scale Occupational exposure There are 4 differents methods to evaluate health effect of a material Epidemiology/occupational studies No studies had been carried on for carbon nanoparticles yet In Vivo studies on animals Inhalation exposure is the main concern Question about the extrapolation of the route of exposure and the relationship between animals and humans However dose dependance, accumulated dose have to be considered In vitro studies on cells In vitro study allow to study inflamatory, cytotoxicty, gentoxicity However a better model to predict real effect on human body need to be validated Occupational exposure Physico-chemical properties Size Shape Porosity Chemical composition Reactivity Solubility, aggregat statut Means of detection are limited and still on development They are based on measuring : Size Number Specific surface Occupational exposure Why assessing risk exposure to nanomaterials ? Because some nanoparticles show some potential toxicity to human being Because of the lack of knowledge about the toxicity and the impact on health and environment of nanomaterials Workplace exposure management In the absence of specific regulations of nanoparticles and in view of the potential toxicity of nanomaterials it is important to avoid any risk of exposure. Several steps of the risk assessement can be conducted : Collecting information Characterization of scenariis of exposure Characterization of risk Plan for Management of risk Evaluation of the plan Workplace exposure management Collecting information Characterization of scenariis of exposure Characterizing nanotechnology and nanoparticles properties Characterizing workplace, equipment, quantity of materials, level of exposure Characterization of risk Identification of every steps of the process Identification of potential risk Evaluating potential risk and its gravity Workplace exposure management Plan for Risk Management Substitution : Avoid using volatil material, if possible use of masterbatch Technical Measure : Confinment of the place of work and/or Confinment of the equipment Control quantity in and out , Air extraction (local and general ) with High performance filter (HEPA 14) as closest as possible from the source Workplace exposure management Organisational Measure : General information : proper training of workers General procedure : cleaning of the equipment, generak rules to Access to the workplace respect, Individual Protection : Choose the appropriate equipment for the individual protection Proper Mask following the lenght of exposure and the toxictyof the particles – Type FFP3 or P3 filter for short exposure. Autonomous Gloves (doubles pairs if necessary) Safe glass ware Protection clothes of at least class 5 ( EN ISO 13982) apparatus in case of longer operation Workplace exposure management End of production cycle Cleaning : Equipement, machine and laboratories should be cleaned with vaccum cleaner equipped with a high efficiency filter Transfer Storage Disposal Waste and not used material should be well labelled and keep in a ventilated closed area Waste should be considered as dangerous substance and treated like this Environmental exposure Environmental exposure Three main way of environmental exposure Rejection in water Several factors impact the release and its importance of nanoparticles into air Solubility in water Reactivity of nanoparticles in a chemical environment Interaction with some biologic processus Rejection in air Several factor affect the release of nanoparticle in air Time during which particles remain airborne Interaction with other particles Distance particles can travel in air Rejection in ground Environmental exposure Rejection in ground Depend on the physical and chemical properties of nanoparticles Mobility of particles into the ground Reactivity with the media Properties o the ground (porosity, size of the grain, electrical charge) Disposal of nanoparticle Today there is no specific regulation for nanomaterial A general rule is to consider nanoparticle as a dangerous substance and treat like it is Thank you for your attention ! 11 FILMS DE NANODIAMANTE: CARBONO PARA APLICACIONES TRIBOLÓGICAS VICTOR NETO INVESTIGADOR UNIVERSIDAD DE AVEIRO Nanodiamond films: carbon for tribological applications Victor Neto Universidade de Aveiro Universidade de Aveiro 16 Departments 4 Polytechnical schools (Environment and Planning; Biology; Materials and Ceramic Engineering; Economics, Management and Industrial Engineering; Mathematics; Social, Political and Territorial Sciences; Physics; Chemistry; Geosciences; Education; Communication and Art; Mechanical Engineering; Civil Engineering; Languages and Cultures; Electronics, Telecommunications and Informatics; Health sciences) 4 Associated Laboratories a 12 Research Units About 15000 students More than 1000 employees (Professors, researchers, Staff) Department of Mechanical Engineering People Teaching people: PhD: 29 No PhD: 6 Researchers: 73 Secretariat and technicians: 7 Department of Mechanical Engineering Graduation and Post-graduation Teaching Integrated Master (1st and 2nd cycle) Mechanical Engineering Masters (MSc) - 2nd cycle Industrial Automation Engineering Sustainable Energy Systems Product Design and Engineering Graduation and Post-graduation Teaching Adv. Specialisation Programme Energy Efficiency and Renewable Energies Doctoral Programme Mechanical Engineering Energy Systems and Climate Change Nanosciences and Nanotechnology Research, Development and Innovation Research Unit TEMA - Centre for Mechanical Technology and Automation Advanced Mechanical Engineering and Fracture Mechanics Group (GAME) Applied Energy Group (AE) Biomechanics Research Group (GIBUA) Nanotechnology Research Group (NRD) R&D Group on Transportation Technology (TT) Simulation Software Research and Development Group (GRIDS) Cooperation with industry DIAMOND COATINGS Chronology of diamond utilization Date 340 BC 1000s 1400s 1500s 1600s 1700s 1800s Event Aristotle describes the use of diamond tipped drills in Greece. Pliny describes the use of diamond splinters in handles of iron to form an engraving tool in Italy. Reports describe the use of a diamond engraving tool called jade cutter knife in China. Crushed diamond powder used for polishing diamond. Leonardo da Vinci reports the use of diamond tools for glass cutting. Report on the first diamond drilling tool. Ramsden reports the first single diamond turning tool for application in metal working. Smith-Tennant reports diamond to be composed solely of carbon. Diamond grinding wheels are being used by Pritchard in England to shape lenses. France grants a patent for a diamond core drill for use in the French stone industry. Use of diamond as a wire drawing die. Diamond drills for dentistry are introduced in the USA by Desau. Chronology of diamond utilization Date 1900s Event Wheel for glass grinding developed by Carl Zeiss Jena. First description of grinding tungsten carbide with diamond. First successful diamond synthesis via High Pressure, High Temperature by ASEA, Sweden (February 16th, 1953). Shockwave sintering of diamond reported. Natural diamond used as heat spreaders for semiconductors. First large synthetic diamond crystals grown up to 0.25 cts in weight. Polycrystalline diamond launched commercially. Growth of diamond crystals via low pressure CVD on non-diamond substrates announced in the Soviet Union. 2000s Sales by volume of synthetic diamond products exceeds natural diamond for the first time. Development of high quality single crystal CVD diamond for electronic applications. Polycrystalline CVD diamond dome used as tweeter in loudspeaker application. © Diamond At Work Spears, K.E. and J.P. Dismukes, eds. Synthetic diamond: emerging CVD science and technology. The Electrochemical Society. 1994, Wiley Inter-Science: New York. 688. Use of diamond in insdustry Diamond properties Property Comments Vicker’s hardness (kgmm−2) 12000-15000 As hard as bulk diamond Possible application Friction coefficient ~0,1 (in air) Depends on the grain size Young’s modulus (Nm−2) 1.2 × 1012 Twice the value of alumina, high mechanical strength Stiff membrane for lithography masks, tweeter components, micromechanical oscillators Sound propagation velocity (km s−1) 18.2 1.6× the value of alumina SAW filters Property Comments Possible application Chemical inertness Inert At room temperature resistant to all acids bases and solvents Coating for reactor vessels, diamond containers, diamond electrodes Range of high transmittance (μm) 0.22–0.25 and >6 In the IR orders of magnitude lower than other materials; Refractive index 2.41 1.6× the value of silica UV–VIS–IR windows and coatings, microwave windows, optical filters, optical wave guides Band gap (eV) 5.47 1.1 for Si; 1.43 for GaAs; 3 for B-SiC Electron/hole mobility (cm2 V−1s−1) 2400/2100 1500/600 for Si 8500/400 for GaAs Dielectric constant 5.5 11 for Si 12.5 for GaAs Drill bits, polishing materials, cutting tools, sintered or brazed diamond compacts, wear resistant coatings on windows and molds and bearing under vacuum Gracio et al, J. Phys. D: Appl. Phys. 43 (2010) 374017 CVD diamond films High power electronics, high frequency devices, high temperature devices, solid-state detectors Gracio et al, J. Phys. D: Appl. Phys. 43 (2010) 374017 CVD diamond films Property Comments Possible application Thermal conductivity (W cm−1 K−1) 20 ∼4× the value of Cu or Ag Heat sinks for electronic devices, heat spreading films on RF devices, laser packages Thermal expansion coefficient (K−1) 0.8 × 10−6 At room temperature close to silica value of 0.57 × 10−6 Thermal stable substrates, e.g. for x-ray lithography masks Work function Negative The vacuum level lies below the conduction band Light emitters, displays CVD diamond growth Typical polycrystalline diamond growth by CVD Temprature 700 – 1000 ºC Pressure 30 Torr (~4000 Pa) Gas precursors CH4 0.5 – 2% H2 balanced Gracio et al, J. Phys. D: Appl. Phys. 43 (2010) 374017 CVD diamond films CVD diamond growth CVD diamond growth Hot Filament CVD systems Main advantage: easily scalable Main disadvantage: low growth rate CVD diamond growth Microwave-plasma CVD Main advantage: high growth rate; purity of film. Main disadvantage: Low area deposition. Combustion-flame-assisted CVD Main advantage: Large area deposition. Main disadvantage: Very poor purity. Other CVD systems: DC-plasma, RF-plasma, etc. Controlling the film characteristics Film characteristics can be tuned: Film thickness Crystal size Crystal orientation Surface roughness … By controlling the deposition conditions Deposition time Gas mixture composition Substrate temperature Reactor pressure … Controlling the film characteristics Deposition time Raman spectroscopy Controlling the film characteristics Gas composition: CH4 concentration CH4/H2: 1% 2% 3% 4% Controlling the film characteristics Gas composition: Addition of Ar Argon (Ar): 0% 50% Crystals size: 1,5 μm Ra: 70,0 nm Rms: 85,6 nm 100nm 17,6 nm 22,0 nm 90% <10nm 11,1 nm 14,1 nm May et al., Diamond & Related Materials 15 (2006) 345 Controlling the film characteristics Gas composition DIAMOND COATINGS @ TEMA Diamond Coatings @ TEMA First research paper Since 2001 Main research topics Development and application of diamond coatings onto cutting tools to machine electrodes for mold industry Performance (Coated WC-Co bits for the tooling of EDM graphite electrodes and/or aluminum alloys) CVD Diamond coated tools Commercial PCD inserts Main research topics Diamond coating of injection molding tools for the production of polymeric micro-components Micro-injection molding machine Injection molding tools Molding insert Polymeric micro-component Main research topics Diamond coating of injection molding tools for the production of polymeric micro-components Coated Polymer flow Dimensional stability - Polymer part surface depend strongly on the diamond crystal size. Not coated Part number Not coated Coated Work still in progress! Main research topics Nanodiamond coated mechanical seals (Mechanical seals are used in rotary equipment, pumps, agitators, compressors) Work still in progress! Material: Wc-Ni Dimensions: Øe = 30 mm / Øi = 18 mm Main research topics Nanodiamond coated Bragg gratings for sensing applications a) Uncoated optical fiber; b) Diamond coated FBG (D-FBG); c) D-RFBG. Work still in progress! OTHER CARBON RELATED RESEARCH @ TEMA Other carbon related research @ TEMA Nanocomposite of graphene-zeolite with nickel for hydrogen storage; Polymer reinforcement with carbon nanotubes for biomechanical applications; Shape memory polymers reinforced with carbon nanotubes; Thermal properties of carbon nanotubes in a fluidic medium; Large-Area epitaxial growth of graphene thin films by CVD for micro-electronics; Graphene based nanocomposites as probes for biodetection by SERS; … Thank you Victor Neto e-mail: [email protected] MSN ID: [email protected] Skype ID: vfsneto Linkedin: linkedin.com/in/victorneto 12 NANOMATERIALES EN LA INDUSTRIA DE CONSTRUCCIÓN JOSÉ VERA‐AGULLO RESP. GRUPO MATERIALES TRADICIONALES ACCIONA INFRAESTRUCTURAS Acciona R&D: On vanguard of sustainable development. Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. BUSINESS MAIN LINES Urban and Environmental Services Infraestructures Facility Management Construction Hospital Services Engineering Waste Treatment Concesions Logistics and Transport Real State Airports Heritage Transmediterránea & Others Promotion Water Energy Treatment Reverse Osmosis Desalination Eolic Other Businesses Other renewables Bestinver Hijos de Antonio Barceló GPD Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. OUR INTERNATIONAL PRESENCE Canada Poland U.S.A. Italy India Mexico Chile U.A.E. Brazil Australia Infraestructures Real State Energy Water Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. INNOVATIVE ACTIVITY. ORGANIZATION STRUCTURE INFRAESTRUCTURES REAL STATE LOGISTICS Technological Center MADRID URBAN SERVICES WATER Technological Center BARCELONA ENERGY Technological Center PAMPLONA Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. INVESTMENT EFFORT R&D Project Investment R&D Investment Distribution WATER ENERGY INFRAESTRUCTURES Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. IMPROVEMENT HUMAN R&D STAFF R&D Employees R&D Percentages EMPLOYEES WATER ENERGY INFRAESTRUCTURES Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. Nanomaterials in the construction industry International Workshop: Application of Nanomaterials in Industry Jose Vera-Agullo, PhD, Head of the Traditionals Materials Group [email protected] Madrid 21/11/2012 Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. INDEX NANOTECHNOLOGY IMPLEMENTATION IN ACCIONA: ¾ PHOTOCATALYTIC BUILDINGS AND TO THE NANOTECHNOLOGY APPLIED INFRASTRUCTURE: CONSTRUCTION SECTOR - Photocatalytic Island. R&D facilities building University Carlos III, Getafe Bus station, Ávila Pavement of two city-center streets, Madrid ¾NANOSÍLICA - Dome of liquified gas tank, Cartagena Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. NANOTECHNOLOGY APPLIED TO THE CONSTRUCTION SECTOR PHOTOCATALYTIC BUILDINGS AND INFRASTRUCTURE Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. OBJECTIVE To confer to the construction materials new added value functionalities: selfcleaning, air depollution and biocide effects. The final applications could be: façades, pavements (asphalt or precast bricks), concrete urban furniture, network of sanitary and storm drains, hospitals, etc. NEEDS To reduce the final cost of the photocatalytic materials. To increase their activity. We have developed our own additive with an improved performance with respect to the commercial available products. Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. PHOTOCATALYTIC BUILDINGS AND INFRASTRUCTURE Photocatalytic Island. R&D facilities building Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. REAL IMPLEMENTATION 1/4: Photocatalytic island. R&D Building PHOTOCATALYTIC PAVING STONE Double layer paving stone. Upper side with photocatalytic additive. 1cm 7cm MONOLAYER MORTAR ASPHALT PAVIMENT WITH PHOTOCATALYTIC SLURRY Conventional Monolayer mortar Monolayer mortar With photocatalytic additive Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. REAL IMPLEMENTATION 1/4: Photocatalytic island. R&D Building PRODUCTION OF BRICKS Liquid additive Solid additive PHOTOCATALYTIC PAVING STONE INSTALLATION OF 250 m2 of BRICKS Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. REAL IMPLEMENTATION 1/4: Photocatalytic island. R&D Building 450 m2 of ASPHALT PAVIMENT WITH PHOTOCATALYTIC SLURRY Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. PHOTOCATALYTIC BUILDINGS AND INFRASTRUCTURE University Carlos III, Getafe Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. REAL IMPLEMENTATION 2/4: Carlos III University Campus 1 h. 10 h. 12 h. Without additive With additive Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. 24 h. >2000 h. REAL IMPLEMENTATION 2/4: Carlos III University Campus PRODUCTION of 7,5 KM of FAÇADE PANELS Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. PHOTOCATALYTIC BUILDINGS AND INFRASTRUCTURE Bus station, Ávila Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. REAL IMPLEMENTATION 3/4: Bus station concrete slab, Ávila 2000 m2 of PHOTOCATALITIC SLAB Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. REAL IMPLEMENTATION 3/4: Bus station concrete slab, Ávila EXECUTION OF THE ADDITIVATED CONCRETE FOR THE SLAB Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. PHOTOCATALYTIC BUILDINGS AND INFRASTRUCTURE Pavement of two city-center streets, Madrid Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. REAL IMPLEMENTATION 4/4: Pavement of two city-center streets, Madrid Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. REAL IMPLEMENTATION 4/4: Pavement of two city-center streets, Madrid • Análisis descontaminación NOx en probetas-testigo de implantación ejecutada en obra ayuntamiento de Madrid. • Aditivo descontaminante percolado sobre mezcla asfáltica M10. • Eliminación de 60% de Dióxido de Nitrógeno en pruebas realizadas en laboratorio certificado UPVCSIC. Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. NANOTECHNOLOGY APPLIED TO THE CONSTRUCTION SECTOR EFFECTS OF NANOSILICA IN CONCRETE Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. CONCRETES WITH NANOSILICA Î ADDED VALUE Î SOLUTIONS NANO-SILICA High purity spherical particles, with an ideal size distribution. Applied to the mixture in the propper proportion conferes to the mix improved rheological and mechanical properties. – TEM micrograph (TEM) of nanosilica (scale bar: 100 nm). Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. • Effect in concrete – Chemical effect: more CSH gel production. Puzzolanic effect. Portlandite Ca(OH)2 Gel C‐S‐H Nanosílice Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. – Hydratation rate increase, tested by Termogravimery analysis. Cement paste specimens TGA equipment Thermogravimetric Analysis 7 days 28 days Samples Reference NS Nano Silica Content, % 0% 1% 70 82 76 91 % hydrated cement Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. Physical effect: – Increase the size of the chains of silicates, refilling holes and increasing the mechanical properties of the mortar or concrete. – This effect is greater at early ages due to the fact that the reaction is more energetic because there is more portlandite at the beginning. Gel CSH Structure Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. – High Strenght concrete with less than 350Kg of cement per m3 Material with NS Reference material 9 More homogeneous mixture 9 Increase the viscosity of the cement paste without losing workability Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. – Hight strength concrete: (> 50MPa) – Same amount of cement as a conventional concrete. – Use less than 1% of nanosilica. • 50Mpa is obtained at 3 days. • Cost reduction of around 1€/m3 related to conventional mixture. Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. Finish of the specimens Material with nanosilica Reference material Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. NANOTECHNOLOGY APPLIED TO THE CONSTRUCTION SECTOR DOME OF A LIQUEFIED GAS TANK (Cartagena, Spain) From small things to huge ones… Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. CONCRETE FOR THE DOME OF THE LIQUEFIED GAS TANK: • Problems – requirements for the Concrete for the Gas Tank Dome: – Absence of shrinkage and cracks BUT high strength mechanical properties (¿high cement content?). – Sloping structure of 30°: Low consistency to avoid segregation and concrete losses in the perimeter of the dome BUT good workability to fill the steel rebar. – Good superficial finish. • Solutions proposed from ACCIONA R&D: – To reduce the cement quantity to diminish the possible appearance of cracks due to the plastic retraction. – Use of nanosilica to compensate the minor quantity of cement, and to improve the rheology and docility of the concrete with low consistency. Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. • Initial tests: ideal workability in the mock-up sloping structure. Prototype. Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. • After 24h, there was analyzed the visual finish and the possible appearance of cracks. • Nanosilica improves the rheology of the low consistency concrete. • No fissures. • Good finish. Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. • Mechanical properties: test sample extraction of concrete: 9 With regard to the compression tests, porosity and determination of the depth of water penetration under pressure, they reach the general specifications of project. Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. Liquefied gas tank Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. Inside the tank Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. CONCRETE FOR THE DOME OF THE LIQUEFIED GAS TANK: • Problems – requirements for the Concrete for the Gas Tank Dome: – Absence of shrinkage and cracks BUT high strength mechanical properties (¿high cement content?). – Sloping structure of 30°: Low consistency to avoid segregation and concrete losses in the perimeter of the dome BUT good workability to fill the steel rebar. – Good superficial finish. • Solutions obtained with the use of nanosilica: – – – – – – Low consistency : 6cm with good rheology and workability at the same time. Absence of cracks in the surface. Very low permeability. High resistances. 25MPa in only 12 hours. 2 days: 40 Mpa - 7 days: 50 Mpa - 28 days: 60 Mpa Cost reduction of 12% in materials. Economical benefit due reduction in time in the construction site. Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. CONCLUSIONS • Construction sector is highly traditional and a low tech oriented sector. • Internal investment in R&D is low to adapt the processes to the addition of nanomaterials. • There use to be low qualified workers manipulating the nano-based materials. This fact could affect to their correct use/application increasing the health and safety risks. • Only large construction companies will reach the nanotechnology market and adapt their proceses to manage it properly. R&D requires expensive equipment and skilled people and SME can not invest, specially taking into account that R&D is not very used in the construction sector. •There are uncertainty with respect to health and safety risk of nanoproducts. Lack of standarized methods to determine occupational health hazards. • IT IS DESIRABLE TO SOLVE THE NANOTECH H&S ISSUES BEFORE REACHING THE CONSTRUCTION SECTOR by means of using peletized nanomaterials or nanomaterials dispersed in water instead of bulk nanomaterials, etc. Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados. Nanomaterials in the construction industry International Workshop: Application of Nanomaterials in Industry Jose Vera-Agullo, PhD, Head of the Traditionals Materials Group [email protected] Madrid 21/11/2012 Centro Tecnológico de I+D+i © 2012. ACCIONA Infraestructuras. I+D+i. Todos los derechos reservados.