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WilliamAndrewisanimprintofElsevier LinacreHouse,JordanHill,OxfordOX28DP,UK 30CorporateDrive,Suite400,Burlington,MA01803,USA Firstedition2009 Copyright©2009,JeremyR.Ramsden.PublishedbyElsevierInc.Allrightsreserved TherightofJeremyR.Ramsdentobeidentifiedastheauthorofthisworkhasbeenassertedwiththe Copyright,DesignsandPatentsAct1988. Nopartofthispublicationmaybereproduced,storedinaretrievalsystemortransmittedinanyformor byanymeanselectronic,mechanical,photocopying,recordingorotherwisewithoutthepriorwritten permissionofthepublisher. PermissionsmaybesoughtdirectlyfromElsevier’sScience&TechnologyRightsDepartmentinOxford, UK:phone:(+44)(0)1865843830;fax:(+44)(0)1865853333;email:permissionselsevier.com. AlternativelyvisittheScienceandTechnologywebsiteatwww.elsevierdirect.com/rightsforfurther information. 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IMRE MADÁCH Series Editor’s Preface The possibility of modifying materials using electrical discharges has fasci- natedmankindeversinceheobservedtheresultsoflightningstrikingobjects innature.Wedonot,ofcourse,knowwhenthefirstobservationtookplace, but we may be reasonably sure that it was a sufficiently long time ago that manymillenniahadtopassbeforeelectricitywas“tamed,”andsubsequently puttoworkmodifyingmaterialsinasystematic,“scientific”way—asexem- plified by Humphry Davy’s electrolysing common salt to produce metallic sodiumattheRoyalInstitutioninLondon. Buttheseareessentiallyfaradaicprocesses(namedafterDavy’serstwhile assistantMichaelFaraday),andsuchprocessesarealsousedextensivelytoday for (micro)machining, as exemplified by electrochemical machining (ECM). Theyarerelativelywellknown,andareapplicabletoconductingworkpieces. Far less well known is the technology of what is now called spark-assisted chemical engraving (SACE), in which the workpiece is merely placed in the closevicinityofthepointedworkingelectrode,andiserodedbysparksjump- ing across the gas bubbles that develop around the electrode to reach the electrolyte in which everything is immersed, the circuit being completed by thepresenceofalargecounter-electrode. This technology can therefore be equally well used for workpieces madefromnon-conductingmaterialssuchasglass,traditionallydifficultto machine,especiallyatthemicrolevelprecisionneededforsuchapplications asmicrofluidicmixersandreactors.Thedevelopmentofattractivemachin- ingtechnologiessuchasSACEisinitselflikelytoplayadecisivepartinthe growth of microfluidics-based methods in chemical proccssing and medical diagnostics,tonamejusttwoimportantareasofapplication. Since, as the author very correctly points out, knowledge about non- faradaicECMmethodsispresentlyremarkablyscantywithinthemicrosys- temscommunity,thisbookisconceivedasacomprehensivetreatise,covering theentirefield,startingwithalucidexplanationofthephysicochemicalfun- damentals,continuingwithathoroughdiscussionofthepracticalquestions likelytobeasked,andendingwithanauthoritativeexpositionofthemeans totheirresolution. xi xii Series Editor’s Preface I therefore anticipate that this book will significantly contribute to enabling the rapid growth of micromachining of non-conducting materials, forwhichthereistremendoushithertounexploitedpotential. JeremyJ.Ramsden CranfieldUniversity,UnitedKingdom December2008 Preface This is as much a book about ideas as about facts. It begins (Chapter 1) byexplaining—yetagain!—whatnanotechnologyis.Forthosewhofeelthat this is needless repetition of a well-worn theme, may I at least enter a plea that as more and more people and organizations (latterly the International StandardsOrganization)engagethemselveswiththequestion,thedefinition is steadily becoming better refined and less ambiguous, and account needs tobetakenofthesedevelopments. Thefocusofthisbookisnanotechnologyincommerce,henceinthefirst part dealing with basics, Chapter 2 delves into the fascinating relationship betweenwealth,technologyandscience.Whereasformillenniawehavebeen accustomedtotechnologyemergingfromwealth,andscienceemergingfrom technology,nanotechnologyexemplifiesanewparadigminwhichscienceis inthevanofwealthgeneration. Theemergenceofnanotechnologyproductsfromunderlyingscienceand technology is an instantiation of the process called innovation. The process is important for any high technology; given that nanotechnology not onlyexemplifiesbutreallyepitomizeshightechnology,therelationbetween nanotechnology and innovation is of central importance. Its consideration (Chapter3)fusestechnology,economicsandsocialaspects. Chapter4addressesthequestion“Whymightonewishtointroducenan- otechnology?”Nanotechnologyproductsmaybediscontinuouswithrespect to existing ones in the sense that they are really new, instantiating things that simply did not exist, or were only dreamt about, before the advent of nanotechnology. They may also be a result of nanification, decreasing the size of an existing device, or a component of the device, down to the nanoscale.Noteverymanufacturedartefactcanbeadvantageouslynanified; thischaptertacklesthecrucialaspectsofwhenitistechnically,andwhenit iscommerciallyadvantageous. These first four chapters cover Part 1 of this book. Part 2 looks at actual nanotechnologyproducts—ineffect,definingnanotechnologyostensively.It is divided into four chapters, the first one (Chapter 5) giving an overview of the entire market. Chapters 7 and 8 deal with, respectively, information xiii xiv Preface technology and healthcare, which are the biggest sectors with strong nano- technologyassociations;allotherapplications,includingcoatingsofvarious kinds,compositematerials,energy,agriculture,andsoforth,areincludedin Chapter6. Part 3 deals with more specifically commercial, especially financial aspects, and comprises three chapters. The first one (Chapter 9) is devoted to business models for nanotechnology enterprises. Particular emphasis is placed on the spin-off company, and the role of government in promot- ing nanotechnology is discussed in some detail. Chapter 10 deals with how demandfornanoproductscanbeassessed.Thethirdchapter(11)dealswith specialproblemsofdesigningnanoproducts. The final part of the book takes a look toward the future. Chapter 12 essentially deals with productive nanosystems; that is, what may happen whenmolecularmanufacturingplaysasignificantroleinindustrialproduc- tion. The implications of this future state are so profoundly different from what we have been used to during the past few centuries that it is worth discussing, even though its advent must be considered a possibility rather thanacertainty.Thereisalsoadiscussionaboutthelikelihoodofbottom-up nanofacture (self-assembly) becoming established as an industrial method. Chapter13askshownanotechnologycancontributetothegrandchallenges currentlyfacinghumanity.Itisperhapsunfortunatethatinsofarasfailureto solvethesechallengeslooksasthoughitwilljeopardizetheverysurvivalof humanity,theymustbeconsideredasthreatsratherthanopportunities,with thecorollarythatifnanotechnologycannotcontributetosolvingtheseprob- lems,thenhumanitycannotaffordtheluxuryofdivertingresourcesintoit. ThefinalChapter14isdevotedtoethicalissues.Whetherornotoneaccepts the existence of a special branch of ethics that may be called “nanoethics”, undoubtedlynanotechnologyraisesahostofissuesaffectingthelivesofevery oneofus,bothindividuallyandcollectively,andwhichcannotbeignoredby eventhemostdispassionatebusinessperson. In summary, this book tries to take as complete an overview as possi- ble, not only of the technology itself, but also of its commercial and social context.Thisviewiscommensuratewiththeall-pervasivenessofnanotech- nology, and hopefully brings the reader some way toward answering the three questions: What can I know about nanotechnology? What should I do with nanotechnology (how should I deal with it)? What can I hope forfromnanotechnology? Nanotechnologyhasbeenandstillisassociatedwithafairshareofhyper- bole,whichsometimesattractscriticism,especiallyfromsoberopen-minded scientists.Butisthishyperboleanydifferentfromtheexuberancewithwhich Isambard Brunel presented his new Great Western Railway as the first link Preface xv in a route from London to New York, or Sir Edward Watkin his new Great Central Railway as a route from Manchester to Paris? Moreover, apart from thetechnology,thenanoviewpointisalsoanadvanceinthewayoflooking attheworldwhichisaworthysuccessortothepreviousadvancesofknowl- edge that have taken place over the past millennium. And especially now, whenhumanityisfacingexceptionalthreats,anexceptionalviewpointcou- pled with an exceptional technology might offer the only practical hope for survival. Ishouldliketoespeciallyrecordmythankstothemembersofmyresearch groupatCranfieldUniversity,withwhomourweeklydiscussionsaboutthese issues helped to hone my ideas, my colleagues at Cranfield for many stim- ulating exchanges about nanotechnology, and to Dr Graham Holt for his invaluablehelpinhuntingoutcommercialdata.Itisalsoapleasuretothank EnzaGiaracuniforhavingpreparedthedrawings. JeremyJ.Ramsden CranfieldUniversity January2009 CHAPTER 1 What is Nanotechnology? CHAPTER CONTENTS 1.1 Nanotechnology as Process 4 1.2 Nanotechnology as Materials 7 1.3 Nanotechnology as Materials, Devices and Systems 8 1.4 Direct, Indirect and Conceptual Nanotechnology 9 1.5 Nanobiotechnology and Bionanotechnology 10 1.6 Nanotechnology—Toward a Definition 10 1.7 The Nanoscale 11 1.8 Nanoscience 11 Further Reading 12 Intheheadydaysofanynew,emergingtechnology,definitionstendtoabound andarefirstdocumentedinreportsandjournalpublications,thenslowlyget into books and are finally taken up by dictionaries, which do not prescribe, however,butmerelyrecordusage.Ultimatelythetechnologywillattractthe attention of the International Standards Organization (ISO), which may in duecourseissueatechnicalspecification(TS)prescribinginanunambiguous mannertheterminologyofthefield,whichisclearlyanessentialprerequisite fortheformulationofmanufacturingstandards. Inthisregard,nanotechnologyisnodifferent,exceptthatnanotechnology seems to be arriving rather faster than the technologies we might be famil- iar with from the past, such as steam engines and digital computers. As a reflectionoftherapidityofthisarrival,theISOhasalreadysetupaTechnical AppliedNanotechnology:TheConversionofResearchResultstoProducts,ISBN9780815520238 3 Copyright©2009,JeremyJ.Ramsden.PublishedbyElsevierInc.Allrightsreserved. 4 CHAPTER 1: What is Nanotechnology? Committee (TC 229) devoted to nanotechnologies. Thus, unprecedentedly in the history of the ISO, we shall have technical specifications in advance ofasignificantindustrialsector. TheworkofTC229isnotyetcomplete,however,henceweshallhaveto makeourownattempttofindaconsensusdefinition.Asastart,letuslookat therootsofthetechnology.TheyarewidelyattributedtoRichardFeynman, who in a now famous lecture at Caltech in 1959 advocated manufacturing thingsatthesmallestpossiblescale,namelyatombyatom—hencetheprefix “nano”,atomstypicallybeingafewtenthsofananometre(10−9m)insize. Hewasclearlyenvisagingamanufacturingtechnology,butfromthelecture wealsohaveglimpsesofanovelviewpoint,namelythatoflookingatthings at the atomic scale—not only artefacts fashioned by human ingenuity, but alsotheminutemolecularmachinesgrowninsidelivingcells. 1.1 NANOTECHNOLOGY AS PROCESS Weseenanotechnologyaslookingatthings—measuring,describing,charac- terizingandquantifyingthem,andultimatelyreachingadeeperassessment of their place in the universe. It is also making things. Manufacturing was evidently very much in the mind of the actual inventor of the term “nanotechnology”,NorioTaniguchifromtheUniversityofTokyo,whoconsidered itastheinevitableconsequenceofsteadilyimprovingengineeringprecision (Figure1.1).1 Clearly,thesurfacefinishofaworkpieceachievedbygrinding cannotbelessroughthanatomicroughness,hencenanotechnologymustbe theendpointofultraprecisionengineering. At the same time, improvements in metrology had reached the point whereindividualatomsatthesurfaceofapieceofmaterialcouldbeimaged, hencevisualizedonascreen.Thepossibilitywasofcoursealreadyinherent in electron microscopy, which was invented in the 1930s, but numerous incremental technical improvements were needed before atomic resolu- tion became attainable. Another development was the invention of the “Topografiner” by scientists at the US National Standards Institute.2 This instrumentproducedamapoftopographyatthenanoscalebyrasterscanning a needle over the surface of the sample. A few years later, it was developed 1N.Taniguchi,Onthebasicconceptofnano-technology.Proc.IntlConf.Prod.EngngTokyo, PartII(Jap.Soc.PrecisionEngng). 2R.Youngetal.,TheTopografiner:aninstrumentformeasuringsurfacemicrotopography. Rev.Sci.Instrum.43(1972)999–1011.