+"

!\

>

Lecture notes on Unit No.8 on'Nanomateriofs ond trlonotechnology' of B. E. I Materials Science SYllobus
By

Prof- P- B. "'oshi Dept. of Metollurgicol and l,loteriois Engineering. Focul4'of Tech. ond Engg., M. 5. UniversitY of Bcrodo. Earodo

Definition and Introduction:

]'{anotechnology is at the forefront of various research and development progralmnes urdertaken globaUy si;e the end of the 20e century'. it is a universal technology capable ol influencing tevelopments not only in science and technology but in eve$ rvalk of life. M4prials irl r*g*.ter regime exhibit novel ph1'sical, chemical and biological propelti:t T .;!q$I rc. .treir Uutt state- By taki"g the advantage of this exctic nature of nano-sizrd maleriats, marvelous materials, devices and systems with many new features can be fabricated. in the liglrt of above, a new field termed as 'Nanotechnology' has emeiged. The fust mention about-nanotechnology was made in a taik given by physicist Richard feln-ma$ nThere,s Hgyggflo,oi gi the Bottom-." at Americar Ph;'sicdl Society rneeti-r.rg at entitled Ciliecltb; DecdmGi z\ tg sg.

. ,/a ,'/ t J

Nanotechnology is the science of very small things. It is rnainly concerned with the crcation of nanosized materials, devices and s7stems with unique characteristics. A nanonr.eter is one biilionth of a meter _(! qqr:lQ-'meter) ant *lu-s nanotechnologv is the . seience of constniitidn od'...he'seXdl'-of-; biltionth of a meter. A nanometer is 1i80,0-QQ dianreter cf a hunan haii or approximately i0 hydrogen atoms frd-e-. Albert Franks di'finecl ir"tr as. 'Thd area'df sciance'and-techirology where dimensi..'rrs anC toierancrs in the r.trige c,f. O 1 fv nrn to i00 nm play a critical role'. Nanotechnology deais with the creatiott of usefi,rl mate;iais,{ devices and systems through control of matter on the naltometer length scale and expioitrtion I of novel phenomena and properties (physical, chemical, biological) at that length

/ lii. y ./

scale. J

Nanomaterials fall benveeq the sizr range of conventional macro materials on one end wherein the properties are govemed by'the collective behaviour of a very large nurnber of groups of atoms, & the'pieco level materia! on the other end comprising atoms and rnolec.ules whose properties are govemed by the laws of quanlqn mechanics. $44omgterials nanometer. In nano forrn, the crystallographic, have at least one dimension of less Lhan 100-opticul anii theffiil-pro.perties pf the materials tifec-tro*i; magt"di, Aotraniqal, electni{ ur. r*tri different frd;ii-tliEii ed,ne'spondirig .c-oiivn!iol9J.&tq:-

A unique aspect of nanotechnology is the significantly

i*t"gf4 *tio of surlbi:r? r.r&

i
I j

to volume present in many nanoscale material which opens new possibilities in surface-based science, such as catalysis. A number of physical phenomena become noticeably proncunced as the size of the System decreases to nano level. These include statistical mechanical effects, as well as quanhrm mechanical effects, for example the "guanfum size effect" where the
t

I f
ii
;l
lj !t
6:

*'
fr

s
m

H r g

Ii

/ .A,lectonic Droperties of solids i;;;-pluy uy going from macrolo micro dimensions' Ho'*'ever' it becomes ;;;;;;-.;;;
dominant onir u-hen the nanometer size range i1 rery!9d-'

are altered with great reductions in particle size. This effect

rsold); Flylq!gfs*becgl]9-!94419!9rs Hrcti X-@;Wn-cnftremically 11e.ft,utno.."al size scales, can serye as emit tiSnt Uyt.when ip;i;;i .iremr.-afc6ia'1,"1 at nanoscales. Likewis., lulk {-!ic-o1-{-9es.not properties of silicon it is nade ....., ,*ull. i, emits llght. This funcarrrental change in the occlrs ri.hen it reaches ?-l * iri size. Much of the fascination with nanotechnology stems from these unique quantum and surface'phenomena that matter exhibits at the nanoscale.

different In other *-ords. materials rl,hen reduced to the nancscale suddenly show very appiications' For properties compared to n'hat they exhibit on a macroscale. enabling unique ; inert m_aterial-s-become --cat3lJr.Lts opaque s ub stanc es beco@ i n r*... -

tpir,i""r'I, -("rlfi.onifttatJdils

toii;;f;

oftopics.Thef.ieldoinanoscien.eandnanotechrblogyis@nnatureto

the extent that the material scientisfs, mechanical and glectroniqs-gng.ia99rs,-*uedical

chemistry, applied Nanotec6.,rologl.cuts across many disciplines, including colloidal science, ph1,ri.r, materlals science, and even mechanical and electrical engineering. This hasresulted J in ar enormou number of applications of nanotechnology ranging from various fields of I engineering to. automation and cybernation; defense and spa?e gloflaTl.nes; ,nuciear ll programmes, ele-ctronics and infonnati6n tecirnologf; sensors and robotics; bigechnology -l me<licine, K*g"ry anO fr'eatttr care and many more' '

researchesinteract@iogistilp6yiicistsandchemisj91lnissuespertaining -tlsi$r, developmfri & - applic'atiofr-ofl ridiro mite.iali, devices and systems. ro

*ai.rli.s;

A ferv irnportart renns frequently used in nanotechnology may be defined

as

follows:

-.Ncnocrystai -Asolid particie that is a single crystal in ttre nanometer range i.e. < 100nm {iu.rtei or ne-irociuster - A collection of units (atoms or reactive molecules) of up to about 50 units. Nanoclusters are mesoscopic particles ranging from several atoms to thousands of atoms in size. Colloids - A stable liquid phase containing particles in the 1-1000 nm range. A colloidal particle is one-suctr 1-1000 nm particie ,' Nanoparticle or nanopowder - A solid ilarticle in the 1-100 nm range that could be air aggregate of crystallites or noncrystalline in nature. Nanoparticles are constituted of several tens or hundreds of atoms or moleiules and can have a variety of sizes and morphologies (amorphous, crystalline, spherical, needles, etc.). ^ Nanoporous materials - have specifically a high surface to volume ratio, with a high surface area and large porosity, with unifunn pore structure Fullerenes - The fullerenes can be considered, after graphite and diarnond, to be the third well-defined allotrope of carbon. It is a hollow, pure carbon moleculd in which the atoms lie'at the vertices of a polyhedron with 12 pentagonal faces and any number (other than one) of hexagonal faces. The

nroleculewasnamedafterR.BuckminsterFuller,theinventorofgeodesic
sheet consists of either one cylindrical graphite .u,carhon nanotuurs _ c*bon nanotubes domes'

(singlew.allnanotuuesrttlT)orofseveralnestedcylinderswithan M\&NT). swNT i*"iruy., ,pu"ing or o.:+ - 0.36nm (multiwall nanotubes

areusuallyclosedutuott'endsbyFullerenelikehalfspheres.Carbon them potentiall,v u-seful in a rvide nanotubes ha'e novel proftrri.r thaimake optics' materials applications' variety of applications'(eg.. nano-electronics, and unique electrical properties' etc.). They exhibit .*r*o?dinurl' strength

*i*"

efiicient conductors oiheat'

Classifi cation of Nanomaterials

the nanotechnogy that are used to synthesize Following are the main building blocks of
various nanomaterialssitf (.tPlttt,-{-, | - ionm
rdianr.)
.l

I<rlctitls
ic
al at eri:rl

N'rntr-r)'slals and c ltt:{c'rs

(

\'l <ta ls- 5arn il1-l}JtlL-t(rrs- rn'rgnt't

qtl.at.tttlllr dt\ls)
na nofal rt

)tlr('r

icl!'s

I - lot) rrm (diant.)

t

(-r:ramic trxidc:

\31pr* irr=

- tfil

nin (dianr- l i

\1pt11t}.i
Narxr!'rvttts sr'lids
r-L) arral's
S,.* f:x_r=, .i1t-l-

I - tfi) nin ldiam.)

rrr r:i drts' s u l ii tl's l s - i' n l LI rll t lc* nitritl.'s CartDn. la1'er"'d nrelrl chalcolcnitl=
\'t t' ta
i r i

'

O.5- lOnfir{PtYr'
diarn)
S<'rr'ru1

Z!\) I i tl's - Ji t t>*grlr.rtr-r r'tc'

nanoparticl*s)

nnt' -

1t,t.t:

\'lr'lals- s{'nlicr)rhjtlL.ttrr\ nu!:ndic mat'{'

and lilin l-itrns

{

I - l0OO nnt tthickrxro)

)

A
\.t

vari<'t1' ol- rnrlq-rials

l)

:t rttc.l ttrcs

sltF'rlall il\\

S<'r c'ral

nm in tlts'

*lals. s:-nliL-f'ftliicl()ri rTnln.'tic nint,:rilrls

thr!'!'dilrr!'nsions

' Classification of Nanofflaterials

,1

Synthesis of Nanomaterials

'bcttrom-up' approach. The top-do\\n approach to nanotechnology involves reduction in the size of the things that already exist on the micrometer scales, firther down to nano level. This is ensureci using subtractive techniques such as milling, micro machining. lithoglaphl' and etching. On the other hand nanostructures ma!'also be built from the fundamental entities of matter viz. atoms and molecules using bottom-up approach. The bottom-up or molecuiar nanotechnoiogy deals with the building up of organic and inorganic structues atom-by-atom, cr rnolecuie-b1,-molecule. The mechanosl'nthesis or chemosynthesis techniques are used for nanornaterial s1-nthesis b1' the bonom-up approach. The nanotechnology with botton-: uP approach is therefore identified as the pr.ocess of handTfi!-individual atoms and 9f buil{iag nutos.ale s),stems fiom scratch, 'atom bj'atom' by using process kttouqn as'self-asserrr[11"

Trvo Flndamentally diflerent approaches that are used for the fabrication of nanomaterials using diflbrent techniques of nano fabrication are named as 'top-dov'n' and

or'self-replication'.

i
;

Already kno*n techniques doun approach are mechanical attrition, crystallization from amorphous state, and those based on bottom-up approach include synthesis frori atomic and molecular precursors (using
methods like PVD, CVD, gas-condensation, chemical precipitation, etc.)

for s5rnthes*i?*" nanostructured materials ,rritg 6p-

-. Various methods of synthesis of nanomaterials:

Starting
Phase

Techniques of Synthesis

Nature of, Product

3D 1D

..Vapour

. 1,/ ' ' -.s' .

t I

lnert gas condesation Vttysical vapour deposition andsputtering Plasma processiltg Chemical vapour depcsition Chernical reactions

3D,2D
3D

i..Liquid

Rapid solidification " Electrodeposition 1/ Chemical reactions

3D

ID,3D

( Solid

t./

Mechanical atfrition or Higb-energy milting

3D
3D

Devihification

A representatir.e iechnique from each ctne of the atrove groups has been discusseci here beiou'.

Phvsical Vapo.r Deposition Technieue

(PW :

The nanograined materials can be produced b1' metalorganic and chemical vapour depcsition routes as well as physical vapour deposition (PVD) roi,rtes. lhe PVD technique, also knonn as the vacuum evaporation. is emplol'ed to develop 2D fiims/coatings froin a monolayer to several micrometer in thickness from naterials iike metals, alloys and compounds. The properties of films deposited using these techniques viz. the structure, density or electrical conductivit)' can be precisel,r' monitored by means of the process parameters such as the evaporation rate, substrate temperature. degree of vacuunt. etc. I'he follo\a'ing figure sho'*s the schematic vie*'of a tvpical vacuurn evaporation setup. It consists ola highly evacuated glass or a metal belljar closed at the top and sealed ar its base. The vacuum of the order of lOa Pa or even better is normally attained using a combination of mechanical pump as roughing pump and oil-diffusion pump as hish-vacuum pump. The- qrateri4l 1o be dgpogited as film. is usually vaporized from a source b1. suppll ing the energy for its vaporization by resistive heating. inductive heating, electron bam or laser heating. Af,er placing the evaporation source in the sourc heater, the belljar is lowered and sealed rviih the help of sealing gasket. The primary' \'acuum is obtained by means of the roughing pump and -hen at an appropriate stage the bell jar charnber is exposed to highvacuum system and the required level of vacuum is attained. The source heater and the heater for the substrate are switched on and the vaporization of the material to be deposited is
ensured.

por.i
Vacuun't

u; Y'tf

chamber

3Scil \n.l

((/"rtuht

c11o I r'=Z; A
"*t

gaLsbat-e- !-tc'^f
Ccmf

(c'-yqdc-)
(w;1afu*1'

-ts_ to ic"( (

PUInP

Figure: Physical Vapor Deposition (PVD) Unit

",fu.

tr -u

::.

Egpid solidification
the_crystallisatign and er.en belon. the crystallisation temperatuie T, in a short time 99ch that crosslng is a'oided. then the liquid retains its state :n the form of underQooled liquid. U-pg4 these the gla-ss transition temperature (T,) the liqurrl.frezgs iltg u metallicglass. However, under certain metastable rnetaliic glasses mall .lndergo partial or cornpfe-tE Crystallization devitrification conditions to producJ stable crjstalline ph^.t. This phenomena is knorm as are often of and can be achie'ed by thermai ag.ing. The grains obtained after devitrification nanometric dimensionIn ,h. *gl_lpil+!qgg44. the most relevanl of the rapid solidification techniques,

During rapid solidit-rcatiol.

if the liquid is undercoole! belo-w- the melting point T'

ajeto|-olt"@er-cooledcopperrvheel,whichisrotatingatahighspeed.

are thrown off The liquid solidifies at a cooling rate of up to 10" K/s and fine,. brittle ribbons the uheel. The melt undergoes rapid quenching. Depending on wheel speed, ejection .onaiiio,-,, and melting tempelature. iubstantial undercooling belorv the equilibrium freezing achieved' The temprature and. .onrlqu.*ly, a ven'' high frequency of crystal nucleation are grain size of rJer.iirification,/ amealing of the ,.ruit*iu*orphous phase leads to the ultrafine tlpicalll'20-50 nm.

Mechanical attiition or hish-enersv milling: \4echanical anritio4_or high-e4ergy__bal!_ ryilling plgcers iq qs-qd-&-r ploducing used for elemental or nanoc-omposG po*aeis with co4!io-!!ed microgtrugture. The equipment gbe o{tti-gh-g!9!gy-m1U;-;ucllas a producing such nanopowders consiits ono of several horizon.ral ball mill, ilanetary ball mill, stirred ba-ll miil or an attrior, shaker mill, vibratory mill. etc. Duiing high-energ,r' milling the metal porvder particles are. repeatedly flaff,e,ned, phase fractured and rewelded regu{!ng-14-eq- %g.9491y-qn9 and uniform dispersiol-of second final-parliclelize at the end of f*i.t.r in the mltrix p.o_4ug,l_qg "i"g"_ryp_"jl,gL Though the milling may or *uy no1#il;a"d r.nba,'iUe erain size /crystallite-size reaches a nanomeqlg level. Euik solids produced from such materials are termed as nanostructured materials. The follou,ing figure gi.,,,., a schematic representation of the changes in the morphology of pouder particles duing milling.

Striirgpowdc

o o
N.
p

.N -?^<\

.*s
lvCdrlprcdonrinacc
Steadl'xtete

Prticlcfattairyr

@
,,

T.t**

m*

le

fornahou

Rmdour s'dtlilS oncillatioo

Properties anci Appl ications o f Nanomaterial

Categories of Nanomaterials:

s:

t
I
l

- .-Main categories of Nanomaterials from applications point of view are: '/ . Carbon based nanomaterials . Metais and alloys . Nanoceramics . Nanocomposites . Nano-glasses i.e. nano amorphous materials . Nano-polymers . Biologicalnanomaterials ! I Nanopowders of metallic, ceramip and composite materials ic ?
$

,-.,

Improvements in Material Propertieslat Nano Level ma1'be summarized as follows: i i Increased hardness & strength of metals ar,d allovs at nano level. Light u,eighti r) high strength metals & alloysof Al, Mg and Ti xith improved mechanical l
1

properties

,v

Nano-nano and nano-micro composites befrveen metal & metai or metal & ceramic phases such as TD- N, SAP, UO2-S.S., WC- Co, TiC- Ni, SiC- Al, TiN-AlN, MgO-SiC, Al2O3-SiC composites Carbon nanotube dispersed cqmposites for high strength or high electrical / thermal conductivity related applications .:,, Coatings with radically improved tribological properties, high v,'ear resistence, -/ reduced friction, improved corrosion resistance, etc. ' Enhanced ductility, toughnesd'& formability of ceramics. Nanocrystalline cera:nics may be ductile, as opposed to traditional ceramics. A significant increase in the elongation of a material with incieasing temperature without necking or fracfure is attributed to superplasticity iir ceramics in nanometric regffii i_'o Enhanced electrical conductivity in ceramics & magnetic nanocomposires. B, Bi, Cu, Co or Sn dcped naoncrysthllin" ZnO for applications as varistor , Hydrogen storage materials such as Mg2Ni, LaNi5, Ti3Al. Zr7NilO, etc. and a.,. metal matrix intermeial I ic dispersed compos ites Higher electrical resistivity in metal a superiorsoft magnetic properties (low coercivity & high permeability) a Giant magnetoresistance (GMR) - drastic decrease in electrical resistivity of materials on exposure to magnetic field. GMR materials for magnetic record.ing heads. GMR comprise of small ferromagnetic single- domain particles with randomly oriented magnetic axes in a nonmagnetic matrix .G,r Higher chemical activity in materials due to very high surface to volume ratio a Enhanced dittrsivity & improved sinterability due to short circuit diffusion paths

T;-pical Bulk Nanostructured Materials:

l{anostrtrcturecl Bulk Jv{aterials include : I .Any material with nanoskuctured grain sizes ' AtnorPhous / glassl'materials " \lultila)"er nanoscale thin f-rinls ' E NanoPorous materials

'Nanocompositeshar,ingnanoparticiesenibededinamatrix
polr-cn'stalline Solids lbrnred are cn'stalline' amorphous or

rtaaaa. ttaacl ata.tlo la.*ata

rltol'tloa

fr:iii
1 . 1...t '.al a.li'r aa -.1t
art l'a

t.t

ta

ir.a.

llt.-

a.

materials Ceveloped are: A representative list of bulk metallic nanostruciured . Titanium

. ' . ' " . ' .

Ti-Al

alloYs

Ti- transition metal alloYs Mg-Ni alloYs Fe-Cu-Nb-Si-Ballol's Fe- transition metal alloys (Co' Ni, Cr, Cu, Zr:) Al- transition metal alloys (Fe, IIi, Ti' Zr) Al. Mg, Al'Mg {Ftt

t.

a.