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NanosturcturesNanosturctures
and Nanomaterialsand Nanomaterials
Lecture 4-5-6
Dr.Jern benchaporn
19/9/2012 – 26/9/2012
What are they?What are they?
 Nano = 10Nano = 10-9-9
or one billionth in sizeor one billionth in size
 Materials with dimensions and tolerances inMaterials with dimensions and tolerances in
the range of 100 nm to 0.1 nmthe range of 100 nm to 0.1 nm
 Metals, ceramics, polymeric materials, orMetals, ceramics, polymeric materials, or
composite materialscomposite materials
 One nanometer spans 3-5 atoms lined up inOne nanometer spans 3-5 atoms lined up in
a rowa row
TermTerm NanomaterialsNanomaterials;;
different classes of materials, including:different classes of materials, including:
1.1. Dry solid nanoparticles and clustersDry solid nanoparticles and clusters
2.2. Dispersions of nanoparticles in liquidsDispersions of nanoparticles in liquids
(nanosuspensions and colloidal solutions)(nanosuspensions and colloidal solutions)
3.3. Nanocrystalline materials held together by glassyNanocrystalline materials held together by glassy
material or embedded in a glassy matrix, such asmaterial or embedded in a glassy matrix, such as
ceramics or glass ceramics with nanosized phaseceramics or glass ceramics with nanosized phase
4.4. Nanocomposite materials including organic as well asNanocomposite materials including organic as well as
inorganic componentsinorganic components
5.5. Stiff macromolecular or supermolecular aggregatesStiff macromolecular or supermolecular aggregates
composed of fullerenes, nanorods, nanotubescomposed of fullerenes, nanorods, nanotubes
TermTerm NanomaterialNanomaterial;;
different classes of materials,different classes of materials,
Nanopolycrystalline materials,Nanopolycrystalline materials,
Partially crystalline polymersPartially crystalline polymers
Emulsions with nanodropletsEmulsions with nanodroplets
Not included:Not included:
04/08/16
Example Nanostructured Materials provided!Example Nanostructured Materials provided!
Carbon Nanotechnologies, Inc.
Hyperion Catalysis International
MicroCoating Technologies
NanoPowder Enterprises, Inc.
Superior MicroPowders
Quantum Polymers
MicroCoating Technologies, Inc
Next Generation Energy Corp.
Millenium Chemicals
Monsanto Company
Nanopowder Enterprises, Inc.
Aerogel Composite, LLC
Applied Nanotechnologies, Inc
NanoMag
NanoPDT
NanoXray
Representative nanoparticle compositions and sizes
Particle compositionParticle composition
MetalsMetals
SemiconductorsSemiconductors
MagneticMagnetic
PolymerPolymer
Available particle size (nm)Available particle size (nm)
 AuAu 2-1502-150
 AgAg 1-1801-180
 PtPt 1-201-20
 CuCu 1-1501-150
 CdX (X = S, Se, Te)CdX (X = S, Se, Te) 1-201-20
 ZnX (X = S, Se, Te)ZnX (X = S, Se, Te) 1-201-20
 PbSPbS 2-182-18
 TiOTiO22 3-503-50
 ZnOZnO 1-301-30
 GaAsGaAs 1-151-15
 GeGe 6-306-30
 FeFe33OO44 6-406-40
 Many compositionsMany compositions 50-100050-1000
Nanocrystals, colloidal and nanotubesNanocrystals, colloidal and nanotubes are some of
the important classes of nanomaterials.
ChemistryChemistry has played a major role in the synthesis
and modification of these nanomaterials.
How to Make NanostructuresHow to Make Nanostructures
Nanometer sizeNanometer size
in one dimensionin one dimension
Nanometer sizeNanometer size
in two dimensionsin two dimensions
Nanometer sizeNanometer size
in three dimensionsin three dimensions
Very thin surface coatings
Nanowires and nanotubes
Nanoparticles
The “bottom-up” or “self-assembly” approach first forms the
nanostructured building blocks and then assembles them into the final
material.
variety of nanostructure synthesis and assembly approaches
The “top-down” approach begins with a suitable starting material and
then “sculpts” the functionality from the material.
Representation of theRepresentation of the
top-down approachtop-down approach
Self-assembly, an exampleSelf-assembly, an example
of the bottom-up approach.of the bottom-up approach.
Classification of nanoscale fabricationClassification of nanoscale fabrication
and synthesesand syntheses
 Top-down approachesTop-down approaches:: Top-down fabrication reduces large
pieces of materials all the way down to the nanoscale, like someone
carving a model airplane out of a block of wood. This approach requires
larger amounts of materials and can lead to waste if excess material is
discarded.
 PaPattern transfer: lithographyttern transfer: lithography
 Nanoscale patterning/writingNanoscale patterning/writing
 Other methods: Irradiation, Mechanical grindingOther methods: Irradiation, Mechanical grinding
Classification of nanoscale fabricationClassification of nanoscale fabrication
and synthesesand syntheses
 Bottom-Bottom-up approaches:up approaches: to nanomanufacturing creates
products by building them up from atomic- and molecular-scale
components, which can be time-consuming. Scientists are exploring the
concept of placing certain molecular-scale components together that
will spontaneously “self-assemble,” from the bottom up into ordered
structures.
 AtomicAtomic manipulationmanipulation
 Gas-pGas-phase syntheseshase syntheses
 ChemicalChemical synthesessyntheses
 Self-assembled systemsSelf-assembled systems
(describes the process in which a group of components
come together to form an ordered structure
without outside direction)
A product of nanomanufacturing: A 16 gauge
wire (above), approximately 1.3 millimeters in
diameter, made from carbon nanotubes that
were spun into thread. And the same wire on a
150 ply spool (below.) Courtesy of Nanocomp.
Top-down approachesTop-down approaches
Nanofabrication:Top-down approachNanofabrication:Top-down approach
It is a SEM micrograph showing part of a gear wheel (micromachine)
made using lithography technology (field of view: 300 micrometers).
MEMSMEMS
Etching
processes
Photolithography
model of photolithographymodel of photolithography
Nanoporous membrane fabricationNanoporous membrane fabrication
Bottom-up approachesBottom-up approaches
Classification of nanoscale fabricationClassification of nanoscale fabrication
and synthesesand syntheses
 Bottom-Bottom-up approaches:up approaches:
 AtomicAtomic manipulationmanipulation
 Gas-pGas-phase syntheseshase syntheses
 ChemicalChemical synthesessyntheses
 Self-assembled systems => biological methodsSelf-assembled systems => biological methods
5 nm
Atomic manipulation with STM
14.3 nm
Quantum Corral
Fe atoms on copper
(M.F Commie, C.P. Lutz and D.M.
Eigler, Science 262, p218 (1993))
Xe atoms on
Ni
(D.M. Eigler& E., Nature 344, p524
(1990))
NOTE: Atomic manipulation is done at 4 K or -270 o
C.
Don Eigler, IBM
Atom Manipulation
หหหห
หห
หหหห
หหหห
STMSTM
Don Eigler, IBM
Atom Manipulation
หหหห
หห
หหหห
หหหห
STMSTM
Don Eigler, IBM
Atom Manipulation
Chemical Syntheses: Au colloids
http://www.mrsec.wisc.edu/Edetc/nanolab
HAuCl4 + trisodium citrate -> Au Note:
Passivated gold
colloid = gold + thiol
(R-SH)
Chemical syntheses:
Functionalization
Fullerene
ModifiedModified
FullereneFullerene
Other methodsOther methods
Chemical Syntheses: coatingChemical Syntheses: coating
Gase-phase syntheses:Gase-phase syntheses:
Chemical Vapour Deposition (CVD)Chemical Vapour Deposition (CVD)
Carbon source
Carbon + metal
catalyst (e.g. Fe)
Atomic deposition
Catalytic properties
M. Valden et. al., Science 281, 1647 (1998)
STM image of Gold nanoparticles
formed by evaporation on TiO2
Cluster size, band gap and catalytic
activity of Au clusters for CO -> CO2
AtomicAtomic deposition: Plasma sputteringdeposition: Plasma sputtering
Self-assembled systems: nanoparticles
Plasma
treatment
Diblock-copolymer micelles
loaded with HAuCl4
Substrate
Substrate
Au nanoparticles
R.E. Palmer, S. Pratontep and H.-G. Boyen, Nature Materials (Review article) 2,
443-448 (2003).
H.G. Boyen et.al. Phys. Rev. B 65, art. no. 075412 (2002).
AFM of Au
clusters on glass
(1 x 1 µm2
)
Self-assembled systems:Self-assembled systems:
Close-packed protein arrayClose-packed protein array
J. Schiener et al., Biochemical and Biophysical Research Communications 328, p477 (2005)
High resolution AFM of GroEL chaperonin on mica
Self-assembled systems :
biomaterial layers
J.-W. Choi et al., Colloids and Surfaces B: Biointerfaces 40, p173 (2005)
Electro-spinning of PVA solution
PVA nanofibers
High voltage
26 Sept26 Sept  TopicTopic
2 Oct2 Oct  5 References5 References
After Midsem examAfter Midsem exam  Discuss the paperDiscuss the paper
27 Nov27 Nov  Slide discussionSlide discussion
4 Dec4 Dec  PresentationPresentation
Nanofabrication
Chemical Syntheses
Fabrication metal nanoparticlesFabrication metal nanoparticles
Fabrication Quantum dotsFabrication Quantum dots
Safety issues with nanoscale powdersSafety issues with nanoscale powders
A well-known application of early
nanotechnology is the ruby red color
that was used for stained glass
windows during the Middle Ages
The color is a result of gold atoms
clustering to form nanoparticles
instead of the more usual solid form.
These small gold particles allow the
long-wave red light to pass through
but block the shorter wavelengths of
blue and yellow light. The color,
therefore, depends both on the
element involved (gold) and on the
particle size; silver nanoparticles, for
example, can give a yellow color.
Gold nanoparticles
Fabrication metal nanoparticlesFabrication metal nanoparticles
1. Small size (1-100 nm) and correspondingly1. Small size (1-100 nm) and correspondingly
large surface-to-volume ratiolarge surface-to-volume ratio
2. Chemically tailorable physical properties,2. Chemically tailorable physical properties,
Which directly relate to size, composition,Which directly relate to size, composition,
and shapeand shape
3. Overall structural robustness3. Overall structural robustness
4. More Catalytic properties etc4. More Catalytic properties etc
Why NANOMATERIALS?Why NANOMATERIALS?
The surface-area-to-volume ratio also called the surface-to-volume
ratio and variously denoted sa/vol or SA:V, is the amount of surface
area per unit volume of an object or collection of objects. The surface
area to volume ratio is measured in units of inverse distance.
Surface areaSurface area
VolumeVolume
LengthLength
00 1 2 3 4 5 6 7 81 2 3 4 5 6 7 8
99
1111
1010
99
88
77
66
55
44
33
22
11
1. Small size (1-100 nm) and correspondingly large surface-to-1. Small size (1-100 nm) and correspondingly large surface-to-
volume ratiovolume ratio
Fabrication metal nanoparticlesFabrication metal nanoparticles
Synthesis of colloidal goldSynthesis of colloidal gold
Au3+
 ions to be reduced to neutral gold atoms
As more and more of these gold atoms form
the solution becomes supersaturated
and gold gradually starts to precipitate in the form of sub-nanometer
particles
The rest of the gold atoms that form stick to the existing particles, and, if
the solution is stirred vigorously enough, the particles will be fairly
uniform in size.
Fabrication metal nanoparticlesFabrication metal nanoparticles
Synthesis of colloidal goldSynthesis of colloidal gold
• Make HAuClMake HAuCl44 solution in water and pour into a beakersolution in water and pour into a beaker
• Heat the solution to boiling on a hot plateHeat the solution to boiling on a hot plate
• Add NaAdd Na33CC66HH55OO77 to Au solution in the beakerto Au solution in the beaker
• Let the solution boil.Let the solution boil.
UV spectra of 13 nm AuNPs. a) 3.5 nM, direct reduction; b) 17 nM,
direct reduction; c) 17 nM, centrifuging (from bottom to top).
520 nm520 nm
3.53.5 nMnM reducingreducing
1717 nMnM reducingreducing
1717 nMnM centrifugingcentrifuging
Gold Particles as a Chemical SensorGold Particles as a Chemical Sensor
•Take a UV-Vis absorbance spectrum of the Au colloid solnTake a UV-Vis absorbance spectrum of the Au colloid soln
•Place Au colloid solution each of three glass vialsPlace Au colloid solution each of three glass vials
•Add water to dilute the colloid solutionAdd water to dilute the colloid solution
•Add 1 M NaCl to the first vial dropwise.Add 1 M NaCl to the first vial dropwise.
•Record what happened.Record what happened.
A layer of absorbed citrate anions on the surface of goldA layer of absorbed citrate anions on the surface of gold
nanoparticles keep the nanoparticles separated (left).nanoparticles keep the nanoparticles separated (left).
Addition of smaller chloride ions (right) allows the particles toAddition of smaller chloride ions (right) allows the particles to
approach more closely and a color change is observed.approach more closely and a color change is observed.
AggregationAggregation
Quantum DotsQuantum Dots
What are Quantum Dots?What are Quantum Dots?
1. Their composition and small size give these dots extraordinary
optical
properties that can be readily customized by changing the size or
composition of the dots.
What are Quantum Dots?What are Quantum Dots?
2. Quantum dots absorb light, then quickly re-emit the light but in a
different color. Although other organic and inorganic materials
exhibit this phenomenon fluorescence—the ideal fluorophores
would be bright and non-photobleaching with narrow, symmetric
emission spectra, and have multiple resolvable colors that can be
excited simultaneously using a single excitation wavelength.
Quantum dots closely fit this ideal.
What are Quantum Dots?What are Quantum Dots?
3. The most striking property is that the color of quantum dots—both in
absorption and emission—can be "tuned" to any chosen
wavelength by simply changing their size.
What are Quantum Dots?What are Quantum Dots?
4. . Quantum dots combine the most sought-after characteristics, such
as multiple colors and brightness, offered by either fluorescent
dyes or semiconductor LEDs (light emitting diodes). In addition,
quantum dot particles have many unique optical properties that
are found only in these materials.
What are Quantum Dots?What are Quantum Dots?
5. The principle behind this unique property is the quantum
confinement effect. This leads to different-sized quantum dots
emitting light of different wavelengths. By using only a small
number of semiconductor materials and an array of different sizes,
one can have quantum dots emit colors that span the spectrum,
from ultraviolet to infrared.
•• Size dependent emission spectraSize dependent emission spectra
•• Single excitationSingle excitation
•• Higher photostabilityHigher photostability
•• Narrow emission peakNarrow emission peak
•• Low toxicity for coated quantum dotsLow toxicity for coated quantum dots
Quantum Dots in BiologyQuantum Dots in Biology
StructureStructure
•• Core quantum dotCore quantum dot
–– CdSe, hydrophobic, not stableCdSe, hydrophobic, not stable
•• Core-shell quantum dotCore-shell quantum dot
–– ZnS/CdSe, hydrophobic, stableZnS/CdSe, hydrophobic, stable
•• Water soluble quantum dotWater soluble quantum dot
–– Hydrophilic polymer coatingHydrophilic polymer coating
•• Quantum dot bioconjugationQuantum dot bioconjugation
–– Bioconjugate to hydrophilic quantum dotBioconjugate to hydrophilic quantum dot
Nanocrystals are zero dimensional nanomaterials, which exhibit
strong quantum confinement in all three dimensions, and thus th
ey are also called “quantum dots”.
• 2 to 10 nm diameter
• under UV light
•under ambient light
smallsmall largelarge
A schematic representation ofA schematic representation of
the band structure in solids:the band structure in solids:
(a) quantum(a) quantum confinement effectconfinement effect
on changing quantum doton changing quantum dot size;size;
(b) surface trap sites with their(b) surface trap sites with their
electronic energy states localizedelectronic energy states localized
within the QDs bandgap;within the QDs bandgap;
(c) the electronic structure of a(c) the electronic structure of a
core–shell quantum dot made ofcore–shell quantum dot made of
two semiconductors forming atwo semiconductors forming a
heterojunction (core surroundedheterojunction (core surrounded
by the shell of a wider bandgap).by the shell of a wider bandgap).
Schematic drawing representingSchematic drawing representing
the changes on opticalthe changes on optical
behavior of nanoparticlesbehavior of nanoparticles
associated with their size.associated with their size.
Top: ElectronicTop: Electronic
structure of QDs with ‘blue shift’ duestructure of QDs with ‘blue shift’ due
to quantum confinement.to quantum confinement.
Typical process used to produce QDs for bioapplications,Typical process used to produce QDs for bioapplications,
considering the major steps:considering the major steps:
(a)(a) Coreshell QDs (CdSe–ZnS);Coreshell QDs (CdSe–ZnS);
organic colloidal stabilizationorganic colloidal stabilization
ligand tri-ligand tri-n-octylphosphinen-octylphosphine oxide (TOPO)oxide (TOPO)
hydrophilic polymer attachment (PEG);hydrophilic polymer attachment (PEG);
Bioconjugated with affinityBioconjugated with affinity
ligands as targeting moleculeligands as targeting molecule
(immunoglobulin-G);(immunoglobulin-G);
Integrated hybrid biocompatibleIntegrated hybrid biocompatible
nanocomposite (‘micellar’ structure).nanocomposite (‘micellar’ structure).
Synthesis of CdSe nanoparticles
Crystal structures of CdSe predicted with theoretical
calculations and found to be physically reasonable.
(A) (CdSe)3 (B) (CdSe)6 (C) (CdSe)13 (D) (CdSe)16
Water soluble CdSe nanoparticles
Quantitative biodistribution of QDs as a function of sizeQuantitative biodistribution of QDs as a function of size
((AA:: 4.4 nm HD, B4.4 nm HD, B:: 6.4 nm HD6.4 nm HD)) using radioactively labeled QDsusing radioactively labeled QDs..
Carbon NanotubesCarbon NanotubesCarbon NanotubesCarbon Nanotubes
Material for the futureMaterial for the future
CNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the future
History of CNTsHistory of CNTs
Japanese scientist, Sumio
Iijima, discoverer of nanotub
es
Multi-wall carbon nanotube
1970 - Discovery of carbon filaments
1985 - Discovery of bucky ball
1991 - Discovery of multi-wall carbon nanotubes
1992 - Conductivity of carbon nanotubes
1993 - Synthesis of single-wall carbon nanotubes
1995 - Nanotube as field emitters
1996 - Ropes of single-wall nanotube
1997 - Hydrogen storage in nanotube
2000 - Thermal conductivity of nanotubes
- Macroscopically aligned nanotubes
2001 - Integration of carbon nanotubes for logic circuit
- Intrinsic superconductivity of carbon
nanotubes………
Types of Carbon Nanotubes:Types of Carbon Nanotubes:
Armchair
Zigzag
Chiral
Single-wall carbon nanotubeSingle-wall carbon nanotube
Double-wallDouble-wall
carbon nanotubecarbon nanotube
Multi-wall carbonMulti-wall carbon
nanotubenanotube
Various forms of carbonVarious forms of carbon
 Arc dischargeArc discharge
 Laser ablationLaser ablation
 Chemical vapor deposition (CVD)Chemical vapor deposition (CVD)
Synthesis :Synthesis :
 etc.etc.
CNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the future
Properties :Properties :
Properties of Carbon nanotubesProperties of Carbon nanotubes::
Recent research has shown that carbon nanotubesRecent research has shown that carbon nanotubes
have promising materials properties for technologicalhave promising materials properties for technological
applications. For examples carbon nanotubes have:applications. For examples carbon nanotubes have:
• the highest elastic module, and mechanical• the highest elastic module, and mechanical
strength that is approximately 200 times strongerstrength that is approximately 200 times stronger
than steelthan steel..
• novel electronic properties.• novel electronic properties.
• high thermal conductivity• high thermal conductivity..
• excellent chemical and thermal stability.• excellent chemical and thermal stability.
• promising electron field emission properties• promising electron field emission properties..
• high chemical (such as lithium) storage capacity.• high chemical (such as lithium) storage capacity.
CNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the future
CNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the future
ApplicationsApplications
scanning probe
microscopy
gate nanotube
transistor logic circuit
CNT-based gas sensors
SWNT FET biosensor with GOx
CNTs composite fiber
woven into fabric for
functional textiles
Energy storage
The winning nanotube-enhanced bike Combat jacket
CNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the future
Applications of Nanotechnology
 Next-generation computer chips
 Ultra-high purity materials, enhanced thermal
conductivity and longer lasting nanocrystalline
materials
 Kinetic Energy penetrators (DoD weapon)
 Nanocrystalline tungsten heavy alloy to replace
radioactive depleted uranium
 Better insulation materials
 Create foam-like structures called ‘aerogels’ from
nanocrystalline materials
 Porous and extremely lightweight, can hold up to 100
times their weight
More applications…
 Improved HDTV and LCD monitors
 Nanocrystalline selenide, zinc sulfide, cadmium
sulfide, and lead telluride to replace current
phosphors
 Cheaper and more durable
 Harder and more durable cutting materials
 Tungsten carbide, tantalum carbide, and titanium
carbide
 Much more wear-resistant and corrosion-resistant
than conventional materials
 Reduces time needed to manufacture parts, cheaper
manufacturing
Even more applications…
 High power magnets
 Nanocrystalline yttrium-samarium-cobalt grains
possess unusually large surface area compared to
traditional magnet materials
 Allows for much higher magnetization values
 Possibility for quieter submarines, ultra-sensitive
analyzing devices, magnetic resonance imaging
(MRI) or automobile alternators to name a few
 Pollution clean up materials
 Engineered to be chemically reactive to carbon
monoxide and nitrous oxide
 More efficient pollution controls and cleanup
Still more applications…
 Greater fuel efficiency for cars
 Improved spark plug materials, ‘railplug’
 Stronger bio-based plastics
 Bio-based plastics made from plant oils lack sufficient
structural strength to be useful
 Merge nanomaterials such as clays, fibers and tubes
with bio-based plastics to enhance strength and
durability
 Allows for stronger, more environment friendly
materials to construct cars, space shuttles and a
myriad of other products
Applications wrapup
 Higher quality medical implants
 Current micro-scale implants aren’t porous enough for tissue to
penetrate and adapt to
 Nano-scale materials not only enhance durability and strength of
implants but also allow tissue cells to adapt more readily
 Home pregnancy tests
 Current tests such as ‘First Response’ use gold nanoparticles in
conjunction with micro-meter sized latex particles
 Derived with antibodies to the human chorionic gonadotrophin
hormone that is released by pregnant women
 The antibodies react with the hormone in urine and clump
together and show up pink due to the nanoparticles’ plamson
resonance absortion qualities
Nanomaterials
conjugation with Bio
QDSQDS
Streptavidin-BiotinStreptavidin-Biotin
Streptavidin-BiotinStreptavidin-Biotin
Streptavidin-BiotinStreptavidin-Biotin
Safety issues with nanoscale powdersSafety issues with nanoscale powders
Many questions need to be addressedMany questions need to be addressed
 How, and in what quantities, will synthetic nanoparticles from nano-How, and in what quantities, will synthetic nanoparticles from nano-
products be released into our environment (soil, air, water)?products be released into our environment (soil, air, water)?
 What level of contamination is to be expected in natural environment (What level of contamination is to be expected in natural environment (
rivers, air, soil samples?rivers, air, soil samples?
 How to control the release of nanoparticles from nano-products toHow to control the release of nanoparticles from nano-products to
environment?environment?
 What analytical methods are appropriate for investigatingWhat analytical methods are appropriate for investigating
environmental samples for nanoparticle concentrations which in manyenvironmental samples for nanoparticle concentrations which in many
cases are expected to be found at low levels?cases are expected to be found at low levels?
 what effects will be found on bacteria, fish, insects, plants and otherwhat effects will be found on bacteria, fish, insects, plants and other
organisms?organisms?
 How to dispose nano-products without releasing of nanoparticles toHow to dispose nano-products without releasing of nanoparticles to
environment?environment?
What are people doing to handle the “nano”What are people doing to handle the “nano”
situation?situation?
NSF and US. EPA announced on SeptNSF and US. EPA announced on Sept .. 17, 08 that they will17, 08 that they will
grant $38 milliongrant $38 million
over five years to establish two new research centers to studyover five years to establish two new research centers to study
the environmentalthe environmental
implications of nanotechnologyimplications of nanotechnology ..
 Center for Environmental Implications of NanotechnologyCenter for Environmental Implications of Nanotechnology
(CEINT, pronounced "saint")(CEINT, pronounced "saint") at Duke Universityat Duke University will focuswill focus
on the fate and transport of natural and manufacturedon the fate and transport of natural and manufactured
nanomaterials in ecosystems.nanomaterials in ecosystems.
 The University of California Center for EnvironmentalThe University of California Center for Environmental
Implications of NanotechnologyImplications of Nanotechnology (( UC CEINUC CEIN )) based in thebased in the
Centre for Nano Safety
http://www.napier.ac.uk/randkt/rktcentres/nanosafety/Pages/CommercialActivites.asp
Activities
Supports industry through the provision of:
Advice based on current knowledge about the risks associated with
various nanomaterials
Writing of reports to summarise current knowledge relating to
nanomaterial risk issues
Testing the biological activity or toxicity of nanomaterials.
The aim of these services are to provide industry with the
information needed to:
Ensure the safe manufacture, handling and use of their nanomaterials
To improve the design of nanomaterials
To allow products to reach their full potential by minimizing risks.
commercial
How to work safely with
nanomaterialsBasic concept is preventing yourself from exposureBasic concept is preventing yourself from exposure
pathways;pathways;
DocumentsDocuments
 Be sure to consider the hazards of precursor materialsBe sure to consider the hazards of precursor materials
in evaluating process hazards.in evaluating process hazards.
 Use good general laboratory safety practices as foundUse good general laboratory safety practices as found
in your chemical hygiene plan. Wear gloves, lab coats,in your chemical hygiene plan. Wear gloves, lab coats,
safety glasses, face shields, closed-toed shoes assafety glasses, face shields, closed-toed shoes as
needed.needed.
 Consideration should be given to the high reactivity ofConsideration should be given to the high reactivity of
some nanopowder (carbonaceous and metal dusts) withsome nanopowder (carbonaceous and metal dusts) with100Adapted from Prof. Peter Lichty of Lawrence Berkeley National Laboratory and web.mit.edu/environment/pdf/Nanomaterial_Toxicity_EHS.pdf
InhalationInhalation
 Synthesis of nanomaterials should be carried outSynthesis of nanomaterials should be carried out
in ventilated fume hoods or glove boxes.in ventilated fume hoods or glove boxes.
 Any experiments should be conducted inAny experiments should be conducted in
enclosed reactors or under vacuum or exhaustenclosed reactors or under vacuum or exhaust
ventilation.ventilation.
 Maintenance on reactor parts that may releaseMaintenance on reactor parts that may release
residual particles in the air should be done inresidual particles in the air should be done in
fume hoods.fume hoods.
 If it is necessary to handle nanoparticle powdersIf it is necessary to handle nanoparticle powders
outside fume hood, wear appropriate respiratoryoutside fume hood, wear appropriate respiratory
protection. The appropriate respirator should beprotection. The appropriate respirator should be
Dermal
 Avoid skin contact with nanoparticles or
nanoparticle-containing solutions by using
appropriate personal protective equipment.
 Do not handle nanoparticles with your bare
skin.
Adapted from Prof. Peter Lichty of Lawrence Berkeley National Laboratory and web.mit.edu/environment/pdf/Nanomaterial_Toxicity_EHS.pdf
Disposal
 Dispose of and transport waste nanoparticles according
to hazardous chemical waste guidelines.
 DO NOT put material from nanomaterial – bearing
waste streams into the regular trash or down the drain.
 All waste materials potentially contaminated with nano
materials should be identified and evaluated or
collected for special waste disposal. On the content
section note that it contains nano sized particles and
indicate what they are.
 CNTs should be treated as potentially toxic fibers and
should be handles with appropriate control.
 Metal based NPs should be treated and handled as toxic
metal
 If large quantities of carbonaceous and metals dusts are
used, safety related to fires and explosions have to beAdapted from Prof. Peter Lichty of Lawrence Berkeley National Laboratory and web.mit.edu/environment/pdf/Nanomaterial_Toxicity_EHS.pdf
““It is a mistake for someone to say nanoparticlesIt is a mistake for someone to say nanoparticles
are safe, and it is a mistake to say nanoparticlesare safe, and it is a mistake to say nanoparticles
are dangerous.are dangerous.
They are probably going to be somewhere in theThey are probably going to be somewhere in the
middle. And it will depend very much on themiddle. And it will depend very much on the
specifics”specifics”
Prof. V. Colvin,
Director of Center for Biological and Environmental Nanotechnology at
Rice University, quouted in Technology Review
105
http://www.tf.uni-kiel.de/matwis/nanochem/nanofabrication.htm
http://www.nature.com/nmat/journal/v10/n7/full/nmat3038.html?WT.ec_id=NMAT-201107
The EndThe End
Group Presentation.Group Presentation.
Paper Selection.Paper Selection.

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Nanotechnology20120918 19-26 lecture 4-5-6 - Nanomaterials

  • 1.
  • 2. NanosturcturesNanosturctures and Nanomaterialsand Nanomaterials Lecture 4-5-6 Dr.Jern benchaporn 19/9/2012 – 26/9/2012
  • 3.
  • 4. What are they?What are they?  Nano = 10Nano = 10-9-9 or one billionth in sizeor one billionth in size  Materials with dimensions and tolerances inMaterials with dimensions and tolerances in the range of 100 nm to 0.1 nmthe range of 100 nm to 0.1 nm  Metals, ceramics, polymeric materials, orMetals, ceramics, polymeric materials, or composite materialscomposite materials  One nanometer spans 3-5 atoms lined up inOne nanometer spans 3-5 atoms lined up in a rowa row
  • 5. TermTerm NanomaterialsNanomaterials;; different classes of materials, including:different classes of materials, including: 1.1. Dry solid nanoparticles and clustersDry solid nanoparticles and clusters 2.2. Dispersions of nanoparticles in liquidsDispersions of nanoparticles in liquids (nanosuspensions and colloidal solutions)(nanosuspensions and colloidal solutions) 3.3. Nanocrystalline materials held together by glassyNanocrystalline materials held together by glassy material or embedded in a glassy matrix, such asmaterial or embedded in a glassy matrix, such as ceramics or glass ceramics with nanosized phaseceramics or glass ceramics with nanosized phase 4.4. Nanocomposite materials including organic as well asNanocomposite materials including organic as well as inorganic componentsinorganic components 5.5. Stiff macromolecular or supermolecular aggregatesStiff macromolecular or supermolecular aggregates composed of fullerenes, nanorods, nanotubescomposed of fullerenes, nanorods, nanotubes
  • 6. TermTerm NanomaterialNanomaterial;; different classes of materials,different classes of materials, Nanopolycrystalline materials,Nanopolycrystalline materials, Partially crystalline polymersPartially crystalline polymers Emulsions with nanodropletsEmulsions with nanodroplets Not included:Not included:
  • 7. 04/08/16 Example Nanostructured Materials provided!Example Nanostructured Materials provided! Carbon Nanotechnologies, Inc. Hyperion Catalysis International MicroCoating Technologies NanoPowder Enterprises, Inc. Superior MicroPowders Quantum Polymers MicroCoating Technologies, Inc Next Generation Energy Corp. Millenium Chemicals Monsanto Company Nanopowder Enterprises, Inc. Aerogel Composite, LLC Applied Nanotechnologies, Inc NanoMag NanoPDT NanoXray
  • 8. Representative nanoparticle compositions and sizes Particle compositionParticle composition MetalsMetals SemiconductorsSemiconductors MagneticMagnetic PolymerPolymer Available particle size (nm)Available particle size (nm)  AuAu 2-1502-150  AgAg 1-1801-180  PtPt 1-201-20  CuCu 1-1501-150  CdX (X = S, Se, Te)CdX (X = S, Se, Te) 1-201-20  ZnX (X = S, Se, Te)ZnX (X = S, Se, Te) 1-201-20  PbSPbS 2-182-18  TiOTiO22 3-503-50  ZnOZnO 1-301-30  GaAsGaAs 1-151-15  GeGe 6-306-30  FeFe33OO44 6-406-40  Many compositionsMany compositions 50-100050-1000
  • 9. Nanocrystals, colloidal and nanotubesNanocrystals, colloidal and nanotubes are some of the important classes of nanomaterials. ChemistryChemistry has played a major role in the synthesis and modification of these nanomaterials.
  • 10. How to Make NanostructuresHow to Make Nanostructures
  • 11. Nanometer sizeNanometer size in one dimensionin one dimension Nanometer sizeNanometer size in two dimensionsin two dimensions Nanometer sizeNanometer size in three dimensionsin three dimensions Very thin surface coatings Nanowires and nanotubes Nanoparticles
  • 12. The “bottom-up” or “self-assembly” approach first forms the nanostructured building blocks and then assembles them into the final material. variety of nanostructure synthesis and assembly approaches The “top-down” approach begins with a suitable starting material and then “sculpts” the functionality from the material.
  • 13. Representation of theRepresentation of the top-down approachtop-down approach Self-assembly, an exampleSelf-assembly, an example of the bottom-up approach.of the bottom-up approach.
  • 14. Classification of nanoscale fabricationClassification of nanoscale fabrication and synthesesand syntheses  Top-down approachesTop-down approaches:: Top-down fabrication reduces large pieces of materials all the way down to the nanoscale, like someone carving a model airplane out of a block of wood. This approach requires larger amounts of materials and can lead to waste if excess material is discarded.  PaPattern transfer: lithographyttern transfer: lithography  Nanoscale patterning/writingNanoscale patterning/writing  Other methods: Irradiation, Mechanical grindingOther methods: Irradiation, Mechanical grinding
  • 15. Classification of nanoscale fabricationClassification of nanoscale fabrication and synthesesand syntheses  Bottom-Bottom-up approaches:up approaches: to nanomanufacturing creates products by building them up from atomic- and molecular-scale components, which can be time-consuming. Scientists are exploring the concept of placing certain molecular-scale components together that will spontaneously “self-assemble,” from the bottom up into ordered structures.  AtomicAtomic manipulationmanipulation  Gas-pGas-phase syntheseshase syntheses  ChemicalChemical synthesessyntheses  Self-assembled systemsSelf-assembled systems (describes the process in which a group of components come together to form an ordered structure without outside direction) A product of nanomanufacturing: A 16 gauge wire (above), approximately 1.3 millimeters in diameter, made from carbon nanotubes that were spun into thread. And the same wire on a 150 ply spool (below.) Courtesy of Nanocomp.
  • 17. Nanofabrication:Top-down approachNanofabrication:Top-down approach It is a SEM micrograph showing part of a gear wheel (micromachine) made using lithography technology (field of view: 300 micrometers). MEMSMEMS
  • 19. model of photolithographymodel of photolithography
  • 22. Classification of nanoscale fabricationClassification of nanoscale fabrication and synthesesand syntheses  Bottom-Bottom-up approaches:up approaches:  AtomicAtomic manipulationmanipulation  Gas-pGas-phase syntheseshase syntheses  ChemicalChemical synthesessyntheses  Self-assembled systems => biological methodsSelf-assembled systems => biological methods
  • 23. 5 nm Atomic manipulation with STM 14.3 nm Quantum Corral Fe atoms on copper (M.F Commie, C.P. Lutz and D.M. Eigler, Science 262, p218 (1993)) Xe atoms on Ni (D.M. Eigler& E., Nature 344, p524 (1990)) NOTE: Atomic manipulation is done at 4 K or -270 o C.
  • 24. Don Eigler, IBM Atom Manipulation
  • 27. Chemical Syntheses: Au colloids http://www.mrsec.wisc.edu/Edetc/nanolab HAuCl4 + trisodium citrate -> Au Note: Passivated gold colloid = gold + thiol (R-SH)
  • 31. Gase-phase syntheses:Gase-phase syntheses: Chemical Vapour Deposition (CVD)Chemical Vapour Deposition (CVD) Carbon source Carbon + metal catalyst (e.g. Fe)
  • 32. Atomic deposition Catalytic properties M. Valden et. al., Science 281, 1647 (1998) STM image of Gold nanoparticles formed by evaporation on TiO2 Cluster size, band gap and catalytic activity of Au clusters for CO -> CO2
  • 33. AtomicAtomic deposition: Plasma sputteringdeposition: Plasma sputtering
  • 34. Self-assembled systems: nanoparticles Plasma treatment Diblock-copolymer micelles loaded with HAuCl4 Substrate Substrate Au nanoparticles R.E. Palmer, S. Pratontep and H.-G. Boyen, Nature Materials (Review article) 2, 443-448 (2003). H.G. Boyen et.al. Phys. Rev. B 65, art. no. 075412 (2002). AFM of Au clusters on glass (1 x 1 µm2 )
  • 35. Self-assembled systems:Self-assembled systems: Close-packed protein arrayClose-packed protein array J. Schiener et al., Biochemical and Biophysical Research Communications 328, p477 (2005) High resolution AFM of GroEL chaperonin on mica
  • 36. Self-assembled systems : biomaterial layers J.-W. Choi et al., Colloids and Surfaces B: Biointerfaces 40, p173 (2005)
  • 37. Electro-spinning of PVA solution PVA nanofibers High voltage
  • 38.
  • 39. 26 Sept26 Sept  TopicTopic 2 Oct2 Oct  5 References5 References After Midsem examAfter Midsem exam  Discuss the paperDiscuss the paper 27 Nov27 Nov  Slide discussionSlide discussion 4 Dec4 Dec  PresentationPresentation
  • 41. Fabrication metal nanoparticlesFabrication metal nanoparticles Fabrication Quantum dotsFabrication Quantum dots Safety issues with nanoscale powdersSafety issues with nanoscale powders
  • 42. A well-known application of early nanotechnology is the ruby red color that was used for stained glass windows during the Middle Ages The color is a result of gold atoms clustering to form nanoparticles instead of the more usual solid form. These small gold particles allow the long-wave red light to pass through but block the shorter wavelengths of blue and yellow light. The color, therefore, depends both on the element involved (gold) and on the particle size; silver nanoparticles, for example, can give a yellow color. Gold nanoparticles
  • 44. 1. Small size (1-100 nm) and correspondingly1. Small size (1-100 nm) and correspondingly large surface-to-volume ratiolarge surface-to-volume ratio 2. Chemically tailorable physical properties,2. Chemically tailorable physical properties, Which directly relate to size, composition,Which directly relate to size, composition, and shapeand shape 3. Overall structural robustness3. Overall structural robustness 4. More Catalytic properties etc4. More Catalytic properties etc Why NANOMATERIALS?Why NANOMATERIALS?
  • 45. The surface-area-to-volume ratio also called the surface-to-volume ratio and variously denoted sa/vol or SA:V, is the amount of surface area per unit volume of an object or collection of objects. The surface area to volume ratio is measured in units of inverse distance. Surface areaSurface area VolumeVolume LengthLength 00 1 2 3 4 5 6 7 81 2 3 4 5 6 7 8 99 1111 1010 99 88 77 66 55 44 33 22 11 1. Small size (1-100 nm) and correspondingly large surface-to-1. Small size (1-100 nm) and correspondingly large surface-to- volume ratiovolume ratio
  • 46.
  • 47.
  • 48. Fabrication metal nanoparticlesFabrication metal nanoparticles Synthesis of colloidal goldSynthesis of colloidal gold Au3+  ions to be reduced to neutral gold atoms As more and more of these gold atoms form the solution becomes supersaturated and gold gradually starts to precipitate in the form of sub-nanometer particles The rest of the gold atoms that form stick to the existing particles, and, if the solution is stirred vigorously enough, the particles will be fairly uniform in size.
  • 49. Fabrication metal nanoparticlesFabrication metal nanoparticles Synthesis of colloidal goldSynthesis of colloidal gold • Make HAuClMake HAuCl44 solution in water and pour into a beakersolution in water and pour into a beaker • Heat the solution to boiling on a hot plateHeat the solution to boiling on a hot plate • Add NaAdd Na33CC66HH55OO77 to Au solution in the beakerto Au solution in the beaker • Let the solution boil.Let the solution boil.
  • 50. UV spectra of 13 nm AuNPs. a) 3.5 nM, direct reduction; b) 17 nM, direct reduction; c) 17 nM, centrifuging (from bottom to top). 520 nm520 nm 3.53.5 nMnM reducingreducing 1717 nMnM reducingreducing 1717 nMnM centrifugingcentrifuging
  • 51. Gold Particles as a Chemical SensorGold Particles as a Chemical Sensor •Take a UV-Vis absorbance spectrum of the Au colloid solnTake a UV-Vis absorbance spectrum of the Au colloid soln •Place Au colloid solution each of three glass vialsPlace Au colloid solution each of three glass vials •Add water to dilute the colloid solutionAdd water to dilute the colloid solution •Add 1 M NaCl to the first vial dropwise.Add 1 M NaCl to the first vial dropwise. •Record what happened.Record what happened.
  • 52. A layer of absorbed citrate anions on the surface of goldA layer of absorbed citrate anions on the surface of gold nanoparticles keep the nanoparticles separated (left).nanoparticles keep the nanoparticles separated (left). Addition of smaller chloride ions (right) allows the particles toAddition of smaller chloride ions (right) allows the particles to approach more closely and a color change is observed.approach more closely and a color change is observed. AggregationAggregation
  • 54. What are Quantum Dots?What are Quantum Dots? 1. Their composition and small size give these dots extraordinary optical properties that can be readily customized by changing the size or composition of the dots.
  • 55. What are Quantum Dots?What are Quantum Dots? 2. Quantum dots absorb light, then quickly re-emit the light but in a different color. Although other organic and inorganic materials exhibit this phenomenon fluorescence—the ideal fluorophores would be bright and non-photobleaching with narrow, symmetric emission spectra, and have multiple resolvable colors that can be excited simultaneously using a single excitation wavelength. Quantum dots closely fit this ideal.
  • 56. What are Quantum Dots?What are Quantum Dots? 3. The most striking property is that the color of quantum dots—both in absorption and emission—can be "tuned" to any chosen wavelength by simply changing their size.
  • 57. What are Quantum Dots?What are Quantum Dots? 4. . Quantum dots combine the most sought-after characteristics, such as multiple colors and brightness, offered by either fluorescent dyes or semiconductor LEDs (light emitting diodes). In addition, quantum dot particles have many unique optical properties that are found only in these materials.
  • 58. What are Quantum Dots?What are Quantum Dots? 5. The principle behind this unique property is the quantum confinement effect. This leads to different-sized quantum dots emitting light of different wavelengths. By using only a small number of semiconductor materials and an array of different sizes, one can have quantum dots emit colors that span the spectrum, from ultraviolet to infrared.
  • 59. •• Size dependent emission spectraSize dependent emission spectra •• Single excitationSingle excitation •• Higher photostabilityHigher photostability •• Narrow emission peakNarrow emission peak •• Low toxicity for coated quantum dotsLow toxicity for coated quantum dots Quantum Dots in BiologyQuantum Dots in Biology
  • 60. StructureStructure •• Core quantum dotCore quantum dot –– CdSe, hydrophobic, not stableCdSe, hydrophobic, not stable •• Core-shell quantum dotCore-shell quantum dot –– ZnS/CdSe, hydrophobic, stableZnS/CdSe, hydrophobic, stable •• Water soluble quantum dotWater soluble quantum dot –– Hydrophilic polymer coatingHydrophilic polymer coating •• Quantum dot bioconjugationQuantum dot bioconjugation –– Bioconjugate to hydrophilic quantum dotBioconjugate to hydrophilic quantum dot
  • 61. Nanocrystals are zero dimensional nanomaterials, which exhibit strong quantum confinement in all three dimensions, and thus th ey are also called “quantum dots”. • 2 to 10 nm diameter • under UV light •under ambient light
  • 63.
  • 64.
  • 65. A schematic representation ofA schematic representation of the band structure in solids:the band structure in solids: (a) quantum(a) quantum confinement effectconfinement effect on changing quantum doton changing quantum dot size;size; (b) surface trap sites with their(b) surface trap sites with their electronic energy states localizedelectronic energy states localized within the QDs bandgap;within the QDs bandgap; (c) the electronic structure of a(c) the electronic structure of a core–shell quantum dot made ofcore–shell quantum dot made of two semiconductors forming atwo semiconductors forming a heterojunction (core surroundedheterojunction (core surrounded by the shell of a wider bandgap).by the shell of a wider bandgap).
  • 66. Schematic drawing representingSchematic drawing representing the changes on opticalthe changes on optical behavior of nanoparticlesbehavior of nanoparticles associated with their size.associated with their size. Top: ElectronicTop: Electronic structure of QDs with ‘blue shift’ duestructure of QDs with ‘blue shift’ due to quantum confinement.to quantum confinement.
  • 67. Typical process used to produce QDs for bioapplications,Typical process used to produce QDs for bioapplications, considering the major steps:considering the major steps: (a)(a) Coreshell QDs (CdSe–ZnS);Coreshell QDs (CdSe–ZnS); organic colloidal stabilizationorganic colloidal stabilization ligand tri-ligand tri-n-octylphosphinen-octylphosphine oxide (TOPO)oxide (TOPO) hydrophilic polymer attachment (PEG);hydrophilic polymer attachment (PEG);
  • 68. Bioconjugated with affinityBioconjugated with affinity ligands as targeting moleculeligands as targeting molecule (immunoglobulin-G);(immunoglobulin-G); Integrated hybrid biocompatibleIntegrated hybrid biocompatible nanocomposite (‘micellar’ structure).nanocomposite (‘micellar’ structure).
  • 69. Synthesis of CdSe nanoparticles
  • 70.
  • 71.
  • 72. Crystal structures of CdSe predicted with theoretical calculations and found to be physically reasonable. (A) (CdSe)3 (B) (CdSe)6 (C) (CdSe)13 (D) (CdSe)16
  • 73. Water soluble CdSe nanoparticles
  • 74.
  • 75. Quantitative biodistribution of QDs as a function of sizeQuantitative biodistribution of QDs as a function of size ((AA:: 4.4 nm HD, B4.4 nm HD, B:: 6.4 nm HD6.4 nm HD)) using radioactively labeled QDsusing radioactively labeled QDs..
  • 76. Carbon NanotubesCarbon NanotubesCarbon NanotubesCarbon Nanotubes Material for the futureMaterial for the future
  • 77. CNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the future History of CNTsHistory of CNTs Japanese scientist, Sumio Iijima, discoverer of nanotub es Multi-wall carbon nanotube 1970 - Discovery of carbon filaments 1985 - Discovery of bucky ball 1991 - Discovery of multi-wall carbon nanotubes 1992 - Conductivity of carbon nanotubes 1993 - Synthesis of single-wall carbon nanotubes 1995 - Nanotube as field emitters 1996 - Ropes of single-wall nanotube 1997 - Hydrogen storage in nanotube 2000 - Thermal conductivity of nanotubes - Macroscopically aligned nanotubes 2001 - Integration of carbon nanotubes for logic circuit - Intrinsic superconductivity of carbon nanotubes………
  • 78. Types of Carbon Nanotubes:Types of Carbon Nanotubes: Armchair Zigzag Chiral Single-wall carbon nanotubeSingle-wall carbon nanotube Double-wallDouble-wall carbon nanotubecarbon nanotube Multi-wall carbonMulti-wall carbon nanotubenanotube
  • 79. Various forms of carbonVarious forms of carbon
  • 80.  Arc dischargeArc discharge  Laser ablationLaser ablation  Chemical vapor deposition (CVD)Chemical vapor deposition (CVD) Synthesis :Synthesis :  etc.etc. CNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the future
  • 81. Properties :Properties : Properties of Carbon nanotubesProperties of Carbon nanotubes:: Recent research has shown that carbon nanotubesRecent research has shown that carbon nanotubes have promising materials properties for technologicalhave promising materials properties for technological applications. For examples carbon nanotubes have:applications. For examples carbon nanotubes have: • the highest elastic module, and mechanical• the highest elastic module, and mechanical strength that is approximately 200 times strongerstrength that is approximately 200 times stronger than steelthan steel.. • novel electronic properties.• novel electronic properties. • high thermal conductivity• high thermal conductivity.. • excellent chemical and thermal stability.• excellent chemical and thermal stability. • promising electron field emission properties• promising electron field emission properties.. • high chemical (such as lithium) storage capacity.• high chemical (such as lithium) storage capacity. CNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the future
  • 82. CNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the future
  • 83. ApplicationsApplications scanning probe microscopy gate nanotube transistor logic circuit CNT-based gas sensors SWNT FET biosensor with GOx CNTs composite fiber woven into fabric for functional textiles Energy storage The winning nanotube-enhanced bike Combat jacket CNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the futureCNT : Materials for the future
  • 84. Applications of Nanotechnology  Next-generation computer chips  Ultra-high purity materials, enhanced thermal conductivity and longer lasting nanocrystalline materials  Kinetic Energy penetrators (DoD weapon)  Nanocrystalline tungsten heavy alloy to replace radioactive depleted uranium  Better insulation materials  Create foam-like structures called ‘aerogels’ from nanocrystalline materials  Porous and extremely lightweight, can hold up to 100 times their weight
  • 85. More applications…  Improved HDTV and LCD monitors  Nanocrystalline selenide, zinc sulfide, cadmium sulfide, and lead telluride to replace current phosphors  Cheaper and more durable  Harder and more durable cutting materials  Tungsten carbide, tantalum carbide, and titanium carbide  Much more wear-resistant and corrosion-resistant than conventional materials  Reduces time needed to manufacture parts, cheaper manufacturing
  • 86. Even more applications…  High power magnets  Nanocrystalline yttrium-samarium-cobalt grains possess unusually large surface area compared to traditional magnet materials  Allows for much higher magnetization values  Possibility for quieter submarines, ultra-sensitive analyzing devices, magnetic resonance imaging (MRI) or automobile alternators to name a few  Pollution clean up materials  Engineered to be chemically reactive to carbon monoxide and nitrous oxide  More efficient pollution controls and cleanup
  • 87. Still more applications…  Greater fuel efficiency for cars  Improved spark plug materials, ‘railplug’  Stronger bio-based plastics  Bio-based plastics made from plant oils lack sufficient structural strength to be useful  Merge nanomaterials such as clays, fibers and tubes with bio-based plastics to enhance strength and durability  Allows for stronger, more environment friendly materials to construct cars, space shuttles and a myriad of other products
  • 88. Applications wrapup  Higher quality medical implants  Current micro-scale implants aren’t porous enough for tissue to penetrate and adapt to  Nano-scale materials not only enhance durability and strength of implants but also allow tissue cells to adapt more readily  Home pregnancy tests  Current tests such as ‘First Response’ use gold nanoparticles in conjunction with micro-meter sized latex particles  Derived with antibodies to the human chorionic gonadotrophin hormone that is released by pregnant women  The antibodies react with the hormone in urine and clump together and show up pink due to the nanoparticles’ plamson resonance absortion qualities
  • 90.
  • 91.
  • 96. Safety issues with nanoscale powdersSafety issues with nanoscale powders
  • 97. Many questions need to be addressedMany questions need to be addressed  How, and in what quantities, will synthetic nanoparticles from nano-How, and in what quantities, will synthetic nanoparticles from nano- products be released into our environment (soil, air, water)?products be released into our environment (soil, air, water)?  What level of contamination is to be expected in natural environment (What level of contamination is to be expected in natural environment ( rivers, air, soil samples?rivers, air, soil samples?  How to control the release of nanoparticles from nano-products toHow to control the release of nanoparticles from nano-products to environment?environment?  What analytical methods are appropriate for investigatingWhat analytical methods are appropriate for investigating environmental samples for nanoparticle concentrations which in manyenvironmental samples for nanoparticle concentrations which in many cases are expected to be found at low levels?cases are expected to be found at low levels?  what effects will be found on bacteria, fish, insects, plants and otherwhat effects will be found on bacteria, fish, insects, plants and other organisms?organisms?  How to dispose nano-products without releasing of nanoparticles toHow to dispose nano-products without releasing of nanoparticles to environment?environment?
  • 98. What are people doing to handle the “nano”What are people doing to handle the “nano” situation?situation? NSF and US. EPA announced on SeptNSF and US. EPA announced on Sept .. 17, 08 that they will17, 08 that they will grant $38 milliongrant $38 million over five years to establish two new research centers to studyover five years to establish two new research centers to study the environmentalthe environmental implications of nanotechnologyimplications of nanotechnology ..  Center for Environmental Implications of NanotechnologyCenter for Environmental Implications of Nanotechnology (CEINT, pronounced "saint")(CEINT, pronounced "saint") at Duke Universityat Duke University will focuswill focus on the fate and transport of natural and manufacturedon the fate and transport of natural and manufactured nanomaterials in ecosystems.nanomaterials in ecosystems.  The University of California Center for EnvironmentalThe University of California Center for Environmental Implications of NanotechnologyImplications of Nanotechnology (( UC CEINUC CEIN )) based in thebased in the
  • 99. Centre for Nano Safety http://www.napier.ac.uk/randkt/rktcentres/nanosafety/Pages/CommercialActivites.asp Activities Supports industry through the provision of: Advice based on current knowledge about the risks associated with various nanomaterials Writing of reports to summarise current knowledge relating to nanomaterial risk issues Testing the biological activity or toxicity of nanomaterials. The aim of these services are to provide industry with the information needed to: Ensure the safe manufacture, handling and use of their nanomaterials To improve the design of nanomaterials To allow products to reach their full potential by minimizing risks. commercial
  • 100. How to work safely with nanomaterialsBasic concept is preventing yourself from exposureBasic concept is preventing yourself from exposure pathways;pathways; DocumentsDocuments  Be sure to consider the hazards of precursor materialsBe sure to consider the hazards of precursor materials in evaluating process hazards.in evaluating process hazards.  Use good general laboratory safety practices as foundUse good general laboratory safety practices as found in your chemical hygiene plan. Wear gloves, lab coats,in your chemical hygiene plan. Wear gloves, lab coats, safety glasses, face shields, closed-toed shoes assafety glasses, face shields, closed-toed shoes as needed.needed.  Consideration should be given to the high reactivity ofConsideration should be given to the high reactivity of some nanopowder (carbonaceous and metal dusts) withsome nanopowder (carbonaceous and metal dusts) with100Adapted from Prof. Peter Lichty of Lawrence Berkeley National Laboratory and web.mit.edu/environment/pdf/Nanomaterial_Toxicity_EHS.pdf
  • 101. InhalationInhalation  Synthesis of nanomaterials should be carried outSynthesis of nanomaterials should be carried out in ventilated fume hoods or glove boxes.in ventilated fume hoods or glove boxes.  Any experiments should be conducted inAny experiments should be conducted in enclosed reactors or under vacuum or exhaustenclosed reactors or under vacuum or exhaust ventilation.ventilation.  Maintenance on reactor parts that may releaseMaintenance on reactor parts that may release residual particles in the air should be done inresidual particles in the air should be done in fume hoods.fume hoods.  If it is necessary to handle nanoparticle powdersIf it is necessary to handle nanoparticle powders outside fume hood, wear appropriate respiratoryoutside fume hood, wear appropriate respiratory protection. The appropriate respirator should beprotection. The appropriate respirator should be
  • 102. Dermal  Avoid skin contact with nanoparticles or nanoparticle-containing solutions by using appropriate personal protective equipment.  Do not handle nanoparticles with your bare skin. Adapted from Prof. Peter Lichty of Lawrence Berkeley National Laboratory and web.mit.edu/environment/pdf/Nanomaterial_Toxicity_EHS.pdf
  • 103. Disposal  Dispose of and transport waste nanoparticles according to hazardous chemical waste guidelines.  DO NOT put material from nanomaterial – bearing waste streams into the regular trash or down the drain.  All waste materials potentially contaminated with nano materials should be identified and evaluated or collected for special waste disposal. On the content section note that it contains nano sized particles and indicate what they are.  CNTs should be treated as potentially toxic fibers and should be handles with appropriate control.  Metal based NPs should be treated and handled as toxic metal  If large quantities of carbonaceous and metals dusts are used, safety related to fires and explosions have to beAdapted from Prof. Peter Lichty of Lawrence Berkeley National Laboratory and web.mit.edu/environment/pdf/Nanomaterial_Toxicity_EHS.pdf
  • 104.
  • 105. ““It is a mistake for someone to say nanoparticlesIt is a mistake for someone to say nanoparticles are safe, and it is a mistake to say nanoparticlesare safe, and it is a mistake to say nanoparticles are dangerous.are dangerous. They are probably going to be somewhere in theThey are probably going to be somewhere in the middle. And it will depend very much on themiddle. And it will depend very much on the specifics”specifics” Prof. V. Colvin, Director of Center for Biological and Environmental Nanotechnology at Rice University, quouted in Technology Review 105
  • 107. The EndThe End Group Presentation.Group Presentation. Paper Selection.Paper Selection.

Editor's Notes

  1. Manufacturing at the nanoscale is known as nanomanufacturing. Nanomanufacturing involves scaled-up, reliable, and cost-effective manufacturing of nanoscale materials, structures, devices, and systems. It also includes research, development, and integration of top-down processes and increasingly complex bottom-up or self-assembly processes. In more simple terms, nanomanufacturing leads to the production of improved materials and new products. As mentioned above, there are two basic approaches to nanomanufacturing, either top-downor bottom-up. Top-down fabrication reduces large pieces of materials all the way down to the nanoscale, like someone carving a model airplane out of a block of wood. This approach requires larger amounts of materials and can lead to waste if excess material is discarded. The bottom-up approach to nanomanufacturing creates products by building them up from atomic- and molecular-scale components, which can be time-consuming. Scientists are exploring the concept of placing certain molecular-scale components together that will spontaneously “self-assemble,” from the bottom up into ordered structures.
  2. M.F. Crommie, C.P. Lutz, D.M. Eigler. Confinement of electrons to quantum corrals on a metal surface. Science 262, 218-220 (1993).
  3. Gold nanoparticles are produced in a liquid by reduction of chloroauric acid (H[AuCl4]), After dissolving H[AuCl4], the solution is rapidly stirred while a reducing agent is added. This causes Au3+ ions to be reduced to neutral gold atoms. As more and more of these gold atoms form, the solution becomes supersaturated, and gold gradually starts to precipitate in the form of sub-nanometer particles. The rest of the gold atoms that form stick to the existing particles, and, if the solution is stirred vigorously enough, the particles will be fairly uniform in size.
  4. By radioactively labeling QD-Cys using Tc99m and quantitatively tracking biodistribution as a function of nanocrystal size, a HD of ~5.5 nm was established as the threshold for renal clearance of QDs (Figure 5).[14] Thus far, few nanometer-sized objects are being actively translated to the clinic. Our study suggests that to satisfy both patient safety and regulatory review, nanoparticle biodistribution and clearance must be carefully considered. This study provides a foundation for the design and development of biologically targeted nanoparticles for biomedical applications.
  5. 1996Ropes of single-wall nanotube 1997Hydrogen storage in nanotube 2000Thermal conductivity of nanotubes Macroscopically aligned nanotubes 2001Integration of carbon nanotubes for logic circuits
  6. Properties of Carbon nanotubes: Recent research has shown that carbon nanotubes have promising materials properties for technological applications. For examples carbon nanotubes have:• the highest elastic module, and mechanical strength that is approximately 200 times stronger than steel. • novel electronic properties. • high thermal conductivity. • excellent chemical and thermal stability. • promising electron field emission properties. • high chemical (such as lithium) storage capacity.
  7. Up to date, many questions need to be addresed. These are lists of research need for nano-ecotoxicology research.
  8. Working safely with nanomaterials involves preventing exposure pathway of nanomaterials to our body such as inhalation, dermal, and ingestion exposure. the synthesis of particles using sol-gel chemistry, should be carried out in ventilated fume hoods or glove boxes. Many nanomaterials are synthesized in enclosed reactors or glove boxes. The enclosures are under vacuum or exhaust ventilation, which prevent exposure during the actual synthesis. Inhalation exposure can occur during additional processing of materials removed from reactors, and this processing should be done in fume hoods. Concerning skin contact, gloves should be worn when handling particulate and solutions containing particles. A glove having good chemical resistance to any solution the particles are suspended in should be used. Two pairs of gloves can be worn if extensive skin contact is anticipated, as well as extended sleeve nitrile gloves, to prevent contamination of lab coats or clothing. One potential safety concern with nanoparticles is fires and explosions if large quantities of dust are generated during reactions or production. Both carbonaceous and metal dusts can burn and explode if an oxidant such as air and an ignition source are present. Consider the hazards of precursor materials in evaluating process hazards. CNTs should be treated as potentially toxic fibers, if capable of being released into the air and not bound up in a substrate, and should be handled with appropriate controls. Metal based NPs should be treated and handled as toxic metal.
  9. Finally, let me make the conclusion of this presentation by show you the view of some researcher in this field.