© 2009 by Taylor & Francis Group, LLC 11 2 Nanoscale Materials Definition and Properties Kathleen Sellers ARCADIS U.S., Inc. This chapter provides a working vocabulary to describe nanoscale materials. It iden- ti es a subset of nanoscale materials that are or will potentially be in most “com- mon” use, and describes those materials as a foundation for understanding their fate andtransportandpossibletoxicologicaleffects. This chapter mentions commercially available products containing nanomateri- alstoillustratevariousaspectsofnanotechnology.Unlessotherwisenoted,product informationinthischapteroriginatedfromtheNanotechnologyConsumerProducts InventorymaintainedbytheWoodrowWilsonInstitute[1]. CONTENTS 2.1 Denitions 12 2.2 Classication of Nanosca le Mater ials 13 2.2.1 Origin 13 2.2.2 Composition and Structure 13 2.2.3 Free versus Fixed Nanoparticles 15 2.3 Properties of Nanoscale Materials 16 2.3.1 Overview 16 2.3.1.1 Effect of Increased Surface Area 16 2.3.1.2 Inuence of Quantum Effects 16 2.3.2 Critical Physical and Chemical Properties 17 2.4 Types of Nanomaterials and Applications 23 2.4.1 Titanium Dioxide 25 2.4.2 Zero -Valent I ron 25 2.4.3 Silver 26 2.4.4 Carbon Black 27 2.4.5 Carbon Nanotubes 28 2.4.6 Fullerenes 29 2.5 Summary 30 References 31 © 2009 by Taylor & Francis Group, LLC 12 Nanotechnology and the Environment 2.1 DEFINITIONS Ananometer(nm)isonebillionthofameter.Thissizescalecanbedifculttograsp and is perhaps best understood by analogy to common materials. A nanometer is about100,000timessmallerthaneitherthediameterofahumanhair(Figure2.1) orthethicknessofasheetofpaper.Aredbloodcellisapproximately5000nmin size.Anotherwaytograsptherelativescaleofnanoparticlesisthis:thediameterof afullerene,whichisasphericalnanoparticle1nmindiametercomprising60carbon atoms, is approximately 10 8 timessmallerthanasoccerball,whichinturnisabout 10 8 smaller than the planet Earth. ASTM International [2] denes nanotechnology as “a term referring to a wide range of technologies that measure, manipulate, or incorporate materials and/or featureswithatleastonedimensionbetweenapproximately1and100nanometers (nm). Such applications exploit the properties, distinct from bulk/macroscopic sys- te ms,ofnanoscalecomponents.”Ananoparticleis“asub-classicationofultrane particle with lengths in two or three dimensions greater than 0.001 micrometer (1 nanometer) and smaller than about 0.1 micrometer (100 nanometers) and which may or may not exhibit a size-related intensive property.” The U.S. Environmental Pro- tection Agency (U.S. EPA) cites a slightly different denition of nanotechnology: “researchandtechnologydevelopmentattheatomic,molecular,ormacromolecular levels using a length scale of approximately one to one hundred nanometers in any dimension;thecreationanduseofstructures,devicesandsystemsthathavenovel properties and functions because of their small size; and the ability to control or manipulate matter on an atomic scale.” [3] These denitions suggest three critical aspectsofnanotechnology:(1)size,(2)functionalityduetothatsize,and(3)inten- ti onal manufacture. As the Nanoforum notes [4], “nanotechnology should not be viewedasasingletechniquethatonlyaffectsspecicareas.Itismoreofa‘catch-all’ termforasciencewhichisbenetingawholearrayofareas,fromtheenvironment, to healthcare, to hundreds of commercial products.” FIGURE 2.1 Micrographofananowirecurledintoaloopinfrontofastrandofhumanhair. (FromMacmillanPublishersLtd.,Tong,L.etal.2003.Subwavelength-diametersilicawires forlow-lossopticalwaveguiding.Nature, 426 (18 December): 816–819. With permission.) © 2009 by Taylor & Francis Group, LLC Nanoscale Materials 13 Thisbookfocusesonasubsetofmaterialsthatareinorhavethepotentialtobe inthewidestuseatthenanoscale: Titaniumdioxide:particlesofTiO 2 at the nanometer scale. Zero-valent iron: particles of Fe 0 . Silver: particles of Ag. Carbon black: particulate form of elemental carbon. Carbon nanotube: hollow tube, commonly made of a single layer of carbon atoms (single-walled carbon nanotube) or multiple layers (multi-walled car - bo n nanotube). Nanotubes also can incorporate materials other than carbon. Fullerene: also known as a “buckminsterfullerene” or “buckyball,” a fuller- en eisahollowsphere.ThetermcommonlyreferstoC60fullerenescom- pr ising60carbonatoms.Otherfullerenestructures,suchasC70andC120, exist. In formationaboutthissubsetofnanomaterialswillprovidethereaderwithan overview of the range of manufacturing processes, physical characteristics, and toxi- co logical effects of nanoscale materials. Table 2.1 summarizes information about thestructureandcompositionofthespeciednanomaterialsandindicatessome of their uses. The focus on these materials continues through subsequent chapters of this book on the manufacture of nanomaterials, fate and transport, and potential toxicological effects. Thesectionsthatfollowprovidemoreinformationabouttheclassication,prop - erties, and uses of common nanomaterials. 2.2 CLASSIFICATION OF NANOSCALE MATERIALS Classication schemes used to describe nanomaterials continue to evolve, but gener- allyrecognizetheoriginofthematerial,whetheritisxedinastructureorfree,its shape, and/or its composition. 2.2.1 ORIGIN Some nanoscale materials occur naturally. Examples include volcanic ash and viruses. Human activities can generate nanoscale materials as incidental byprod- ucts. Diesel exhaust particles and byproducts of welding, for example, can be in the nanoscale range [3, 5]. This book focuses on intentionally manufactured nanoscale materials, however, and not on these naturally occurring or incidental materials. 2.2.2 COMPOSITION AND STRUCTURE Nanoscale materials can be made of elemental carbon, carbon-based compounds, metalsormetaloxides,orceramics.Theycantakemanyshapes.Thesegenerally include the following structures: Particles or crystals Tubes, wires, or rods • • • • • • • • © 2009 by Taylor & Francis Group, LLC 14 Nanotechnology and the Environment TABLE 2.1 Types and Uses of Nanoparticles Composition Carbon Metals Ceramic/Silica Structure Nano- particle Examples of Uses Nano- particle Examples of Uses Nano- particle Examples of Uses Particle Carbon black Pigment; reinforce- ment of rubber products Titanium dioxide (TiO 2 ) Cosmetics; environ- mental remediation Ceramic nano- particles Coating on photo paper Nano-sized wax particles Car wax Zero-valent iron; nano- magnetite (Fe 3 O 4 ) Environ- mental remediation Silver Antibacterial agent in wound care, athletic clothing, washing machines Zinc oxide Cosmetics Cerium oxide Diesel additive to decrease emissions Tube/wire Carbon nanotubes Electronics; sporting goods Nanowire Dendrimer G5 dendrimer Targeted drug delivery Iron sulde clusters immobilized in dendrimers Environ- mental remediation Other Fullerene Cosmetics Quantum dots Semi- conductors Function- alized ceramic nano- porous sorbents Water treatment © 2009 by Taylor & Francis Group, LLC Nanoscale Materials 15 Dendrimers (branched structures) Composites Ot her (e.g., spherical) Some authorities further subdivide these general structural categories. For example,theNationalInstituteforOccupationalSafetyandHealth(NIOSH)denes 11 categories of nanomaterial structure [6]: 1. Agglomerated spheres 2. Colloids 3. Crystalline 4. Films 5. Nanohorns 6. Nanorods 7. Nanotubes 8. Nanowires 9. Quantum dots 10. Spherical 11. Other Others classify nanoparticles by dimension [7–9]. According to this classication scheme, one-dimensional structures include nano lms, two-dimensional nanomate - ri als include nanotubes, and three-dimensional shapes include fullerenes. 2.2.3 FREE VERSUS FIXED NANOPARTICLES Freenanoparticles,asthenameimplies,areinsolutionorsuspension.Asaresult, exposure can occur during manufacture, use, and after disposal. Commercial prod- uct s containing free nanoparticles include: Diesel fuel containing cerium oxide to reduce emissions Certain sunscreens containing titanium dioxide and a face cream contain - in gfullerenes Drugs containing dendrimers for targeted delivery Certain food products, for example vegetable oils, containing nanodrops of components such as vitamins, minerals, and phytochemicals Free nanoparticles are likely to be released into the environment through a vari - et yofpathwaysasmaterialsareusedanddisposed. Alternatively,manufacturingprocessesmayxnanoscaleparticlesintoasolid, as in the following examples: Composite tennis rackets strengthened with carbon nanotubes Rubber products reinforced with carbon black Computer chips containing nanoscale transistors • • • • • • • • • • © 2009 by Taylor & Francis Group, LLC 16 Nanotechnology and the Environment Once in use, these commercial products containing xed nanoparticles are unlikely to release nanomaterials to the environment. Therefore, the potential for humanorecologicalexposuretoxednanoparticlesislimitedaftertheirincorpora- ti on into the nal manufactured materials. 2.3 PROPERTIES OF NANOSCALE MATERIALS 2.3.1 O VERVIEW The properties of nanoscale materials generally differ from those of the same mate- rialsinbulksize.Thiseffectresultsfromtwoaspectsofthesmallsizeofnanopar- ti cles:(1)theincreasedrelativesurfaceareaperunitmass,and(2)theinuenceof quantumeffects.Eachofthesepointsisdiscussedbelow. 2.3.1.1 Effect of Increased Surface Area Reducingthesizeofaparticleincreasestheratioofsurfaceareatomass.Because the reactive portion of the particle is at its surface, increasing the relative surface area will increase reactivity for a given amount of material. To illustrate, consider a spherical particle 0.1 millimeter (mm) in diameter. Its surface area is 3 × 10 −8 m 2 .If technicians mill the same mass of material into 100-nm-sized spheres, then the total surface area increases to 3 × 10 −5 m 2 .Decreasingthediameteroftheparticlebya factor of 1000 increases the surface area by a factor of 1000. If reactive sites cover thesurfaceoftheparticle,then—allelsebeingequal—thisdecreaseinparticle sizewouldincreasereactivitysubstantially.Thiseffectaccountsfortheincreased efciencyofnanoscalecatalystscomparedtotheirbulkcounterparts. 2.3.1.2 Influence of Quantum Effects At the nanoscale, both classical physics and quantum physics can govern the behav - io rofaparticle.Theinuenceofquantumeffectscanchangeessentialmaterial characteristics such as optical, magnetic, and electrical properties. An in-depth explanationoftherelevantphysicsisbeyondthescopeofthisbook,whichfocuses on the implications of nanotechnology for the environment. In lieu of pages of theo - re ticalexplanationandequations,considerthefollowingexamples. Inoureveryday,visibleworld,objectsmoveaccordingtoNewton’smodelsof velocity, acceleration, inertia, and momentum. For example, one can predict the tra - je ctoryofalacrosseballbasedonitsmassandvelocity,thepullofgravity,andthe resistanceoftheair.Ifthelacrosseballsplashesintoapond,itsnaltrajectoryalso willreectthebuoyancyofthewater. Otherfactors,however,caninuencethemovementofamoleculeorcertain nanoparticles. Even nonpolar molecules exhibit slight, transient polarity of charge because of instantaneous shifts in electron density. (Quantum mechanics projects thiselectrondensityprobabilistically.)Aslightnegativechargeonaportionofa moleculeornanoparticleduetothistransientpolaritywillbeattractedtoapositive charge or repelled by a negative charge. These weak and transient intermolecular forces are called Van der Waals forces. For many nanoparticles — unlike the lacrosse © 2009 by Taylor & Francis Group, LLC Nanoscale Materials 17 ball — these slight, transient forces can inuence the movement of a particle through liquid.VanderWaalsforcescancausenanoparticlestoagglomerate,oradsorbto each other via physisorption (physical adsorption). (For further information on the fate and transport of nanoscale materials, see Chapter 6.) Just as Newton’s laws predict the movement of a large solid, Ohm’s Law relates current,voltage,andresistancetomodelthebulkowofelectronsthroughametal - li cwire.Solidcarbonintheformofthegraphiteusedinpencilleaddoesnotconduct electricity well. This property can change when a sheet of graphite one atom thick is wrapped to form a single-walled carbon nanotube. Some carbon nanotube structures canfunctionassemiconductors.Otherscanconductelectricityasifthematerial weremetal,althoughvirtuallywithoutresistanceasaresultofthecoordinatedtrans - fe r of electrons between atoms straight down the length of the nanotube. The ow ofelectricityreectsindividualpacketsofenergyassociatedwiththemovementof individualelectrons,ratherthanthebulkowofelectronsmodeledbyOhm’sLaw. Thenextexampleoftheuniquepropertiesassociatedwithnanoparticlesis,iron - ica lly, centuries old. Medieval glass blowers used nanoscale particles of gold to color stained-glass windows. The optical properties of gold change at nanoscale. As metal particles become smaller, the quanta (or discrete packets) of light energy that can interactwiththemincrease.Dependingontheirsize,nanoscalegoldparticlescan bepurple,green,orange,orred[10].Similarly,zincoxide—notoriousforcoating lifeguards’noseswhiteagenerationago—becomestransparentatthenanoscale. Theseexamplesillustratesomeofthewaysinwhichthesmallsizeofsome nanoparticlescanaffecttheirbehaviorandproperties.Itisthesechangesinproperties relative to those of the corresponding bulk materials that account for many of the usesandmuchoftheexcitementsurroundingnanotechnology. 2.3.2 CRITICAL PHYSICAL AND CHEMICAL PROPERTIES Itisclearthatnanoscalematerialsdonotnecessarilybehaveinwayspredictedfrom thebehavioroftheirtraditionallyscaledcounterparts.Asaresult,thephysicaland chemical properties that scientists usually use to predict environmental fate and transport and the consequences of exposure do not sufce to characterize nanoscale materials. Table 2.2 lists properties that may be relevant to nanotechnology and the environment according to three paradigms: 1. U.S. EPA’s voluntary Nanoscale Materials Stewardship Program (NMSP) under the Toxic Substances Control Act (TSCA) [11]. As described further inChapter4,theU.S.EPAhasproposedthisprogramtogatherinformation aboutnanomaterialstoprovideabasisfordevelopingregulations. 2. The Voluntary Reporting Scheme for engineered nanoscale materials developed by the Department for Environment, Food and Rural Affairs (Defra) in Great Britain [13]. De fraestablishedthisprogramtocollect information needed to assess the extent to which current regulations and controls sufce to control the potential risks from nanomaterials. 3. The Nano-Risk Framework, which the Environmental Defense–DuPont Nano Partnership developed to evaluate the potential risks of nanoscale © 2009 by Taylor & Francis Group, LLC 18 Nanotechnology and the Environment TABLE 2.2 Critical Properties of Nanomaterials Paradigm Property Nanoscale Materials Stewardship Program [11] Voluntary Reporting Scheme [12] Life Cycle Analysis: NanoRisk Framework a [13] 1. Nomenclature: Technical name • • • CAS Registry Number • • • Commercial name/trade name • • • Common name • • • 2. Physical/chemical properties: A. General characteristics: Chemical composition, including surface coating • • • Molecular structure • • b • Crystal structure • • Physical state/form at room temperature and pressure ••• B. Purity of commercial product: Purity (or impurities in commercial product) • • • Byproducts resulting from the manufacture, processing, use, or disposal of the chemical substance •• Stabilizing agent, inhibitor, or other additives • C. General properties: pH (at specied concentration) • Solubility in water • • • Vapor pressure • • • Henry’s Law coefcient • Melting temperature • • Boiling/sublimation temperature • • • Flash point • Self-ignition temperature • Dispersability • Bulk density • • • Dissociation constant • Surface tension • Any unique or enhanced properties that arise from the nanoscale features of the material • © 2009 by Taylor & Francis Group, LLC Nanoscale Materials 19 TABLE 2.2 (CONTINUED) Critical Properties of Nanomaterials Paradigm Property Nanoscale Materials Stewardship Program [11] Voluntary Reporting Scheme [12] Life Cycle Analysis: NanoRisk Framework a [13] D. Particle characteristics: Particle size and size distribution (granulometry) • • • Aspect ratio • Average aerodynamic diameter • Average particle mass • • Particle shape • • • Particle density • • Agglomeration state • • • Deglomeration and disaggregation properties • E. Surface characteristics: Surface area • • • Average particle surface area • Surface charge/zeta potential • • Porosity • • Surface chemical composition • • Surface reactivity • Surface area/volume ratio • 3. Production process: Production type (batch/continuous) and rate • • Brief description of manufacturing process • Source of the material, where the material is not produced by the notier • Intended uses of the material and benets of the uses • Detailed description of production process, including unit operations, chemical conversions, and mass balance (including potential releases to the environment) •• Potential worker exposure • • • Personal protective equipment/engineering controls • • Environmental release and disposal • • • 4. Methods for characterization: Spectra • • Chromatographic data (high-pressure liquid chromatography, gas chromatography) • © 2009 by Taylor & Francis Group, LLC 20 Nanotechnology and the Environment TABLE 2.2 (CONTINUED) Critical Properties of Nanomaterials Paradigm Property Nanoscale Materials Stewardship Program [11] Voluntary Reporting Scheme [12] Life Cycle Analysis: NanoRisk Framework a [13] Methods of detection and determination for the substance and its transformation products after discharge into the environment • 5. Environmental fate and transport c : Diffusion rate • Gravitational settling rate • • Sorption rate • • Deposition rate • • Wet and dry transport • • Adsorption-desorption coefcients • • d • Octanol-water partition coefcient • • Volatilization from water • Volatilization from soil • Distribution among environmental media • Nanomaterial aggregation or disaggregation in exposure medium of concern • Biodegradability (organic nanomaterials only) • • • Bioaccumulation potential • • • Biotransformation • Photodegradability • • Stability in water (hydrolysis) • Inuence of redox reactions • • • Abiotic degradation • 6. Safety hazards: Flammability • • • Explosivity • • • Incompatability • Reactivity • Corrosivity • 7. Human health hazards: Any hazard warning statement, label, material safety data sheet, or other information which will be provided to any person who is reasonably likely to be exposed to this substance •• [...]... Pathways for Synthesis of Titanium Dioxide Nanoparticles In Technical Proceedings of the 20 05 NSTI Nanotechnology Conference and Trade Show, 2: 62 26 © 20 09 by Taylor & Francis Group, LLC 32 Nanotechnology and the Environment 17 Etris, A.F 20 01 Silver and silver alloys In Kirk-Othmer Encyclopedia of Chemical Technology, 4:761–803 New York: John Wiley & Sons, Inc 18 The Silver Institute 20 07 Uses http://www.silverinstitute.org/uses.php... Photocatalytic filter The latter contains nano-sized particles of TiO2 to “get rid of unpleasant smell and smoke.” 2. 4 .2 ZERO-VALENT IRON Engineers use nanoparticles of elemental iron known as nano zero-valent iron (nZVI), as discussed further in Chapter 10, to treat groundwater containing chlorinated © 20 09 by Taylor & Francis Group, LLC 26 Nanotechnology and the Environment solvents, arsenic, and other contaminants... 20 07) 7 Sweet, L and B Strohm 20 06 Nanotechnolgy — Life-cycle risk management Hum Ecolog Risk Assess., 12: 528 –551 8 Environmental Defense and DuPont 20 07 Nano Risk Framework 21 June http:// www.NanoRiskFramework.com (Accessed June 27 , 20 07), 13 9 The Royal Academy of Engineering, the Royal Society 20 04 Nanoscience and Nanotechnologies: Opportunities and Uncertainties, Chapter 3 29 July http://www.royalsoc.ac.uk... 9, 20 07) 19 Baker, M.N 1948 The Quest for Pure Water, 4 New York: The American Water Works Association, Inc 20 Vo-Dinh, T., P Kasili, and M Wabuyele 20 06 Nanoprobes and nanobiosensors for monitoring and imaging individual living cells Nanomed.: Nanotechnol Biol Med., 2: 22 30 21 Oak Ridge National Laboratory 20 04 News Release: ORNL nanoprobe creates a world of new possibilities 14 July 22 Wang, M.-J.,... Nanotechnologies: A Nanotechnology Consumer Products Inventory http://www.nanotechproject.org/ inventories/consumer/ (Accessed June 27 , 20 07) 2 ASTM International 20 06 Designation: E 24 56 – 06 Standard Terminology Relating to Nanotechnology 3 U.S Environmental Protection Agency 20 07 Nanotechnology White Paper EPA/100/ B-07/001 Prepared for the U.S Environmental Protection Agency by members of the Nanotechnology. .. colloid The zeta potential is the charge measured at the outermost portion of the Stern layer As discussed further in Chapter 6, the stability of a nanoparticle suspension relates to its zeta potential The electrostatic repulsion resulting from surface charge can counter the tendency toward agglomeration These properties affect the fate and transport of nanomaterials in the environment, their toxicity, and. .. October):10 http://www particleandfibretoxicology.com/content /2/ 1/10 25 Dresselhaus, M., G Dresselhaus, P Eklund, and R Saito 1998 Carbon nanotubes Physics World (January) http://physicsweb.org/articles/world/11/1/9/1 (Accessed June 22 , 20 07) 26 Helland, A., P Wick, A Koehler, K Schmid, and C Som 20 07 Reviewing the Environmental and Human Health Knowledge Base of Carbon Nanotubes Environmental Health Perspectives... points regarding nanotechnology: 1 Strong attractive forces can cause individual particles to agglomerate readily, changing their characteristics and limiting their transport in the environment (See Chapter 6 for further discussion of the forces that govern the behavior of nanoparticles.) 2 Literature reports on nanotechnology warrant careful reading to ascertain the actual particle size and form under... discussion, and to determine whether experimental conditions correspond accurately to the form of a material that is actually commercially available or used (Chapter 8 discusses some of the techniques used to suspend nanoparticles in solution for © 20 09 by Taylor & Francis Group, LLC 28 Nanotechnology and the Environment toxicity testing, and how those techniques should affect the interpretation of the results.)... and their fate in wastewater treatment, as discussed in subsequent chapters 2. 4 TYPES OF NANOMATERIALS AND APPLICATIONS New applications of nanotechnology appear constantly The Nanotechnology Consumer Products Inventory maintained by the Woodrow Wilson Institute listed over 500 consumer products containing nanomaterials as of June 20 07 [1] The inventory grew from 21 2 to 5 02 products between March 20 06 . 17 2. 4 Types of Nanomaterials and Applications 23 2. 4.1 Titanium Dioxide 25 2. 4 .2 Zero -Valent I ron 25 2. 4.3 Silver 26 2. 4.4 Carbon Black 27 2. 4.5 Carbon Nanotubes 28 2. 4.6 Fullerenes 29 2. 5. nanomateri- alstoillustratevariousaspectsofnanotechnology.Unlessotherwisenoted,product informationinthischapteroriginatedfromtheNanotechnologyConsumerProducts InventorymaintainedbytheWoodrowWilsonInstitute[1]. CONTENTS 2. 1 Denitions 12 2 .2 Classication of Nanosca le Mater ials 13 2. 2.1 Origin 13 2. 2 .2 Composition and Structure 13 2. 2.3 Free versus Fixed. sorption, andisoftenrepresentedbythezetapotential.Apositivechargeonthe surfaceofacolloid(suchasametaloxidenanoparticle)inwaterattracts negativelychargedionsintheuid.Thesenegativelychargedionsform theso-called“Sternlayer”aroundthecolloid.Thezetapotentialisthe chargemeasuredattheoutermostportionoftheSternlayer.Asdiscussed furtherinChapter6,thestabilityofananoparticlesuspensionrelatestoits zeta