Bottom Up Manufacturing - UNESCOthe 6:5 bonds (between a hexagon and a pentagon). Its average bond...
Transcript of Bottom Up Manufacturing - UNESCOthe 6:5 bonds (between a hexagon and a pentagon). Its average bond...
Bottom Up Manufacturing
Carbon Allotropes,
Processes, and Applications
Terence Kuzma
Carbon Physical Properties• Comes from the Latin word carbonem meaning“charcoal”.• Well-known forms of carbon include diamond, coal
and graphite. Naturally these are made of carbon exclusively, but offer unique functionality
• Carbon likes to bond to carbon, and many other elements, individual C atoms can covalently bond to other C atoms
• Covalent bonds and the molecules shape provide superb stability and resistance to stress
• By careful processing, the carbon can be shaped into rods, tubes, balls, and sheets.
• Unique materials from one inexpensive element offers a wide array of applications.
Physical Properties• Carbon, forms to many other elements. Our
discussion will focus on carbon to carbon materials
https://en.wikipedia.org/wiki/Carbon
Physical Properties• Carbon is the 4th most abundant chemical element
in the universe by mass after hydrogen, helium, and oxygen.
• Carbon has the ability to form very long chains of interconnecting C-C bonds
• There are more known carbon-containing compounds than all the compounds of the other chemical elements combined except those of hydrogen
• Carbon has 4 valence electrons and these are available to make covalent bonds.
• Each of these electrons can pair with an electron from another atom to form a strong covalent bond, making materials like graphene very strong.
Physical Properties• Carbon has 4 valence electrons and these are
available to make covalent bonds.C nucleus
electron
A single pair of electrons is shared Single (covalent) bond
C CH
H
H
H
H
HDouble bond
C C
Triple bond
C C
• Each of these electrons can pair with an electron from another atom to form a strong covalent bond, making materials like graphenevery strong. http://archive.cnx.org/contents/b01d9904-ce2f-4153-b956-
36e68700e63f@2/graphene-ic-part-2-graphene-ic-graphene-allotropes
Physical Properties• Carbon can be the basis for the entire range of
intrinsic nanometer scaled structures– Fullerene, zero dimensional nanoparticle– Nanotube, one dimensional nanowire– Graphite, two dimensional layered anisotropic
material– Fullerene solids, three dimensional bulk material
using the fullerene as a fundamental building block• Fulerenes can have multiple configurations such
as C70, C76, C78, C80, and higher order variations
Eight selected allotropes of carbon
a) diamondb) graphitec) lonsdaleited) C60 buckminsterfullerene e) C540, Fulleritef) C70 g) amorphous carbonh) single-walled carbon nanotube
https://en.wikipedia.org/wiki/Allotropes_of_carbon
Physical Properties• Synthetic Carbon Allotropes (SCA), are carefully
crafted that can be manufactured in as topologically confined objects in zero, one, and two dimensions as shown previously.
Topics by History
Future of Carbon Allotropes
1953, Germany:
Diamond-like Coatings
1991, Japan:
Multi-Wall Carbon Nanotubes
2004 , England:
Graphene
1985, USA:
Buckyballs
1992, Japan:
Diamond Nanowires
1993, Japan:
Single-Wall Carbon Nanotubes
Examining Unique Carbon Materials
• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
History line
Future of Carbon Allotropes
1953, Germany:
Diamond-like Coatings
1991, Japan:
Multi-Wall Carbon Nanotubes
2004 , England:
Graphene
1985, USA:
Buckyballs
1992, Japan:
Diamond Nanowires
1993, Japan:
Single-Wall Carbon Nanotubes
Diamond-Like Material• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Diamond-Like Discovery● 1953 - Heinz
Schmellenmeier’s
discovery○ C
2H
2 gas in glow-
discharge plasma
○ 1970s - Eisenberg and
Chabot○ Negatively biased metallic
substrate through ion
beam deposition
○ High dielectric constant, a
high index of refraction,
optically transparent, and
highly resistant to
corrosion in acidic
solutions. https://de.wikipedia.org/wiki/Heinz_Schmellenmeier
Diamond-Like Discovery● Mid 1970’s - DLCs first
made from hydrocarbon sources by glow-discharge plasma.
● 1985 - DLCs used for recording media
● 2000s - Articles start research around the topic, focusing on the properties of thematerial.
Donnet, Christophe, Ali Erdemir, and John Robertson. Tribology of Diamond-like Carbon Films
Fundamentals and Applications. New York: Springer, 2010. Print.
Diamond-Like Material
• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Physical Properties• Diamond and Diamond Like Films• Each carbon atom in a diamond is covalently
bonded to four other carbons in a tetrahedron. • These tetrahedrons together form a 3-
dimensional network of six-membered carbon rings (similar to cyclohexane),
• This stable network of covalent bonds and hexagonal rings, is the reason that diamond is so strong.
http://www.bbc.co.uk/education/guides/zjgmn39/revision
Physical Properties
https://en.wikipedia.org/wiki/Diamond_cubic
Diamond cubic structure
Physical Properties• Diamond is one well known allotrope of carbon• Diamond is the hardest known natural mineral • Industrial diamonds are valued mostly for their
hardness and heat conductivity• Diamonds are embedded in drill tips or saw
blades, or ground into a powder for use in grinding and polishing applications
http://wanlonggroup.en.made-in-china.com/product/XMWQRreBnbfy/China-300mm-General-Edge-Cutting-Saw-Blade-Diamond-Edge-Cutting-Segment-for-Granite-Stone.htmlhttp://shopidc.com/diamond-jewelry-atlanta.html
Physical Properties• 400 million carats (80 tons) of synthetic
diamonds are produced annually for industrial use which is nearly four times the mass of mined natural diamonds
• Diamond is often used as a heat sink in electronics
• Diamond like coatings are popular in optics to retard lens abrasion.
Properties / Physics
● Thin film material made up of an
amorphous carbon, a-C, or a hydrogenated
amorphous carbon, a-C:H
● Only material that can provide both high
hardness and low friction under dry sliding
conditions
● Sp3 carbon bonding
● C-C sp3 molecules are responsible for
Young’s modulus, hardness, and
diamond-like quality
Hybridization in Covalent Bonds. Web. 25 July2017.
Properties / Physics
● graphitic C: a glassy carbon, but it not a DLC
● sputtered a-C(:H): Unbalanced magnetron
sputtering is commonly used to create DLCs
with large sp3 contents
● ta-C: tetrahedral amorphous carbon and is
made from ion or plasma beams
● no films: hydrogen is so great that a
material with a fully connected system is
unable to form
● HC polymer region: not of DLCquality
Donnet, Christophe, Ali Erdemir, and John Robertson. Tribology of Diamond-like Carbon Films
Fundamentals and Applications. New York: Springer, 2010. Print.
Diamond-Like Material
The Discovery Material Properties and PhysicsManufacturing MethodsApplications
Manufacturing
● Physical Vapor
Deposition
Donnet, Christophe, Ali Erdemir, and John Robertson. Tribology of Diamond-like Carbon Films
Fundamentals and Applications. New York: Springer, 2010. Print.
● Producing high sp3 ratios, density,
and hardness
● Pulsed laser deposition and
filtered cathodic vacuum arc are
the leading processes
Manufacturing
PLD
Donnet, Christophe, Ali Erdemir, and John Robertson. Tribology of Diamond-like Carbon Films
Fundamentals and Applications. New York: Springer, 2010. Print.
Diamond-Like Material
The Discovery Material Properties and PhysicsManufacturing MethodsApplications
Applications
● Tribological applications.
● Protect structures from potentially destructive contact.
● Reduces the likelihood of hard particles penetrating into tools or parts.
● Protect moving parts from abrasion, preserving smooth movement.
● Low coefficient of friction.
■ Reduction in friction reduces the need for lubrication.
● Chemical inertness a high resistivity against oxidation and corrosion.
● Must be able to tolerate internal stress and resist delamination.
● Due to their high film stresses, DLCs had poor adhesion.
● Resolved by using multilayer stacks that included an adhesion layer.
● These stacks also reduces film stress, allowing for thicker coatings.
● Thicker coatings generate exceptional properties such as extremely high
microhardness, low coefficients of friction, and slower rates of wear.
Applications
Applications
● Perfect for mold materials and automotive wear parts.
● Often used to coat cutting tools used in both lubricated and dry environments.
● Torque needed to insert and remove stainless steel bone screws has reduce by 5 0 % by
coating them with DLCs.
Donnet, Christophe, Ali Erdemir, and John Robertson. Tribology of Diamond-like Carbon Films
Fundamentals and Applications. New York: Springer, 2010. Print.
● Decorative aspects
● Provides durability and wear
resistance
● Gives the watches a shiny and
black appearance
Applications
"Ashford Luxury Watches." Luxury Watch Movado, Ebel, Tag Heuer, Concord, Bulova, Breitling, Seiko, ESQ, Cartier, Corum, Kenneth Cole, Citizen, Bulgari, Chopard - Ashford.com. Web. 23 July 2017.
Bottom Up ManufacturingCarbon Allotropes,
Processes, and ApplicationsPart2
Terence Kuzma
History
Future of Carbon Allotropes
1953, Germany:
Diamond-like Coatings
1991, Japan:
Multi-Wall Carbon Nanotubes
2004 , England:
Graphene
1985, USA:
Buckyballs
1992, Japan:
Diamond Nanowires
1993, Japan:
Single-Wall Carbon Nanotubes
Buckyballs / Fullerene• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Fullerene Discovery● 1985 Smalley, Kroto, and
Curl at Rice University.● 1990 Larger Quantity
Synthesis.● 1996 Nobel Prize
The Fullerene Discovery Team in front of the Space Science Building at Rice University. Shown from left to right: Sean O'Brien,
Richard Smalley, Robert Curl, Harry Kroto, and James Heath [Buckminsterfullerene discovery team at RiceUniversity]
Fullerene• Discovered and documented in 1985 by Kroto• A fullerene is a molecule of carbon that may
include many shapes. The molecule based solely on carbon may be a sphere, tube, ellipsoid, or a combination of other shapes.
• Historically the fullerine was the first widely studied synthetic carbon allotrope
• A Buckyball is a special subset of the fullerene family.
• Buckyballs are comprised of 60 covalently bonded carbon atoms
Fullerene• Characteristic soccer ball shape • Self assembling structure • Discovered in 1985 by Smalley, Kroto and Curl
at Rice University, awarded the 1996 Nobel Prize in Chemistry
• (C60) named it after Richard Buckminster Fuller, who was a architectural designer that popularized the geodesic dome
• Sometimes called the “third allotrope” of carbon
Fullerene• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
PHYSICS AND GEOMETRY:
● 6 0 atoms hexagons cannot form a sphere.
● Party line.
● Pentagon road.
● Poly-cyclic ring elimination.
Properties
A visual representation of the collapse of polycyclic rings into spherical fullerenes
[Baggott]
Fullerene/BuckyballsThe C60 Buckyball
C60 Fullerene• Also known as the C60 molecule or
the more popular “buckyball”• 32 sided structure comprised of 12
pentagons and 20 hexagons• Each carbon atom in C60 is trigonally
bonded to other carbon atoms• There are 20 hexagonal faces and 12
additional pentagonal faces in each c60 molecule
C60 Fullerene• The C60 molecule has two bond lengths. The 6:6
ring bonds (between two hexagons) can be considered double bonds and are shorter than the 6:5 bonds (between a hexagon and a pentagon). Its average bond length is 1.4 angstroms. This is the same bond length as graphite
• The nucleus to nucleus diameter of a C60molecule is about 0.71 nm.
• C60 molecule is about 1.1 (nm).
C60 Fullerene• C60 molecule is about 1.1 nanometers (nm).[26] The
nucleus to nucleus diameter of a C60 molecule is about 0.71 nm.
• Solutions of pure buckminsterfullerene have a deep purple color.
By Alpha six from Germany - C60-Fulleren 2Uploaded by Diaa_abdelmoneim, CC BY-SA 2.0, https://commons.wikimedia.org/w/index.php?curid=6632211
Other Fullerenes• Other fullerenes are
formed geometrically by adding hexagonal faces
• Euler’s theorem states that a closed surface consisting of hexagons and pentagons has exactly 12 pentagons and an arbitrary number of hexagons
It.wikipedia.org
Eight selected allotropes of carbon
a) diamondb) graphitec) lonsdaleited) C60 buckminsterfullerene e) C540, Fulleritef) C70 g) amorphous carbonh) single-walled carbon nanotube
https://en.wikipedia.org/wiki/Allotropes_of_carbon
Fullerenes• Fullerenes are similar in structure to graphite,
which is composed of stacked graphene sheets of linked hexagonal rings
• Fullerenes are found in nature and have been detected in outer space.
• Fullerenes, in the form of C60, C70, C76, C82 and C84 molecules, are produced in nature, hidden in soot and formed by lightning discharges in the atmosphere.
Fullerene Properties • High electrical conductivity due to a free electron
on every carbon atom• Becomes super conductive when doped with
potassium at –255 C • Metallic conductor at room temperature• Three dimensional conductor that conducts
equally well in all directions • May become an ideal material for making super
conducting wires
Fullerene Properties • Can withstand very high temperatures and
pressures.• Ability to trap other molecules in its cage
structure.• It exhibits ferromagnetic properties.• Thermal conductivity is as good as those of
diamonds.• It is twice as hard as diamond when compressed
to 70% of its original size.• It has a blackbody radiation property. It absorbs
and re-emits all radiation landing on it.
Fullerene Properties • Thermal conductivity is as good as those of
diamonds.• It is twice as hard as diamond when compressed to
70% of its original size.• It has a blackbody radiation property. It absorbs and
re-emits all radiation landing on it.
Fullerene Properties • Chemically fullerenes are soluble in many organic
solvents• Functionalization can further control and enhance the
solubility• Fullerenes in organic solvents exhibit 5 stages of
reversible oxidation/reduction• Redox is (short for reduction–oxidation reaction) is a
chemical reaction in which the oxidation states of atoms are changed. – Oxidation is the loss of electrons or an increase in
oxidation state by a molecule, atom, or ion.– Reduction is the gain of electrons or a decrease in
oxidation state by a molecule, atom, or ion.
PHYSICAL PROPERTIES:
● Highly symmetrical: 4 peaks
● Resists deformation
● 0.7 nm diameter
Properties
IR Spectra of a coating 2 microns thick on a silicon substrate with nominal peaks, showing the 4 strong
peaks expected because of the very symmetrical nature of the molecules[Krätschmer]
Fullerene• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
NOBEL PRIZE SYNTHESIS:
● 1985 Rice University
● High energy laser
● Graphite disk
● Cooled
● Inert He ~100 mTorr
● TOF mass spectrometer
● New method in 1990 University
of Arizona
Manufacturing
Block Diagram of Fullerene Discovery[Farnsworth]
Fullerene FabricationArc Discharge Method
• Fullerenes are generated by the vaporization of a pure graphite source (anode) at a pressure of 500 Torr
• Vaporized graphite collects as a soot on the graphite cathode
• Carbon atoms begin to self assemble forming C60 molecule
• Fullerenes removed from the carbon soot using AFM and specialized techniques
Fullerene FabricationArc Discharge Method
• The process was first established by Kratschmer in 1990
• The process chamber consists of a pure graphite anode and cathode
• A 50-100 A dc arc (20 V) discharge at about 200 Torr is struck between the electrodes using helium gas
• The carbon atoms in the anode are vaporized and deposited on the cathode and water cooled walls of the reactor
Fullerene FabricationArc Discharge Method
• This discharge can contain up to 15% fullerenes, with C60 at 13%, and C70 about 2%
• The fullerenes are separated by chromatography using solvents such as toluene.
• Low yield and laborious process• Troublesome by products
common to carbon processing
Carbon Nanotube-Based Polymer Composites: Synthesis, Properties and Applications
By Waseem Khan, Rahul Sharma and Parveen Saini
MODERN
SYNTHESIS:
Manufacturing
Figure 10 Comparison of total energy embodiment in 4 popular
methods of fullerene synthesis[Anctil]
Fullerene• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
MEDICAL APPLICATIONS:
● Caged medicine.
● Caged contrast agents.
● Free radical reduction.
Applications
Figure 11 Radiation protection of zebrafish at various levels of radiation. Reduction of the
phenotype seen in radiation damage (curled up spine) is comparable to the well-known
protectiveAmifostine.[Partha]
TECHNOLOGICAL
APPLICATIONS:
● STM tip
● Lubricants
● Organic heterojunction solar
cells
Applications
Figure 12 Shows the use for functionalized fullerenes in solar cells
[Anctil]
History
Future of Carbon Allotropes
1953, Germany:
Diamond-like Coatings
1991, Japan:
Multi-Wall
Carbon
Nanotubes
2004 , England:
Graphene
1985, USA:
Buckyballs
1992, Japan:
Diamond Nanowires
1993, Japan:
Single-Wall Carbon Nanotubes
MWCNT• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
MWCNT Discovery● 1991 – Sumio Iijima
discovers multi-walled carbon nanotubes (MWCNTs).
● Iijima’s discovery is seen worldwide, bringing about further development of nanotubes.
MWCNT Discovery● 1952 - Soviet
researchers publish images that closely resemble carbon nanotubes.
● The images go largely unnoticed due to theCold War
Monthioux, Marc, and Vladimir L. Kuznetsov. "Who should be given the credit for
the discovery of carbon nanotubes?." Carbon 44.9 (2006):1621-1623.
Carbon Nanotubes• Carbon nanotubes were observed over the
years, but not seriously examined • Appreciated, or “discovered” in 1991 by Sumio
Iijima while working at NEC in Tokyo• A carbon nanotubes is a highly ordered sheet of
carbon atoms rolled into a tube• The carbon nanotube is a subset of the
fullerene family• Comes in two forms single-walled nanotubes
(SWNTs)and multiwalled nanotubes (MWNTs)• Diameter as small as 1nm
http://oer.physics.manchester.ac.
Veena Choudhary1 and Anju Gupta
Carbon Nanotubes (CNTs)
MWNT• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Physical Properties• Nanotubes consist of carbon atoms covalently
bonded in a repeating hexagonal pattern• This highly ordered pattern gives the nanotube
exceptional mechanical flexibility and strength• A single perfect nanotube is 50 times stronger
than steel at a sixth of the weight
Physical Properties• Large surface area on which to form bonds and
doping• SWNTs have diameters from 1- 10 nm• MWNTs can have many layers of tubes with an
overall diameter of up to 20 nm• Thermal conductance as high as diamond• Gases and other molecules can be stored within
its cylindrical structure
MWNT• MWCNTs consist of multiple layered,
needle-like tubes, all arranged helically about a needle axis.
– H – Top portion
– V – Side portions
– C – Layer number
Iijima, Sumio. "Helical microtubules of graphitic carbon." nature 354.6348 (1991): 56.
Properties ELECTRICAL CONDUCTIVITY:
● Percolation threshold – critical
concentration of MWCNTs
● If an insulating polymer has a MWCNT
concentration below the percolation
threshold, the nanotubes will not strongly
affect the conductivity
● If the MWCNT concentration exceeds the
percolation threshold, the conductivity
increases by orders of magnitude. Moisala, A., et al. "Thermal and electrical conductivity of single-and multi-walled carbon nanotube-epoxy composites." Composites science
and technology 66.10 (2006): 1285-1288.
MECHANICAL STRENGTH:
● High aspect ratio & high dispersion of
MWCNTs will reinforce a polymer’s
mechanical strength.
● MWCNTs make the stress distribution
more uniform.
● High level of order – greater strength and
stiffness, less flexibility.
MWCNT Properties
Montazeri, Arash, et al. "Mechanical properties of multi-walled carbon nanotube/epoxy composites." Materials & Design 31.9 (2010): 4202-4208.
MWNT Properties• High aspect ratio &
high dispersion of MWCNTs will reinforce a polymer’s mechanical strength.
• MWCNTs make the stress distribution more uniform. High level of order – greater strength and stiffness, less flexibility.
MWNT• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Manufacturing • CATALYTIC CHEMICAL VAPOR DEPOSITION:
– VLS growth – an Ni-Cu-Al catalyst is used
– Uses tube furnace
– Two-hour deoxidization of catalyst at 973 K
– Reaction at 1023 K – can use carrier gas
Zhao, Naiqin, et al. "Fabrication and growth mechanism of carbon nanotubes by catalytic chemical vapor deposition." Materials
Letters 60.2 (2006):159-163.
Chemical Vapor Deposition• Iron nanoparticles are deposited in a porous silica
substrate• Catalyzed iron particles are heated in a tube furnace• Hydrocarbon gas is flowed over the pores in the
substrate• Nanotubes begin to grow on the iron catalyst• Tube shape and growth controlled by the pore
shape• CVD can grow both MWNTs and SWNTs• SWNTs grown in CO at a temperature of 800-
1400C• MWNTs grown in acetylene at a range of 600-800C
An example: Carbon Nanotubes (CNTs) Grown From Methane Gas Decomposition
at Iron Nanoparticle Catalysts
www.helixmaterial.com
High Pressure CO Process
• Relatively new process for producing SWNTs• Carbon Monoxide (CO) is the source gas• Catalytic iron particles are heated in the HipCO
reactor up to 1200C• Process utilizes high pressure to facilitate
growth (10’s Torr)• Many of the process methods can produce ant
SCA, but parameters are selected to provide the highest yield for a particular SCA
• Mo:Fe:Al Alloy catalysts are deposited via Sol Gel, onto a porous substrate and heated in a tube furnace to anneal them to the substrate.
• Hydrocarbon gas is flowed over the pores in the substrate and nucleate at the catalyst.
• Nanotube growth occurs at the site of the catalysts.• Base growth and Tip Growth are possible.
• CVD can grow both MWNTs and SWNTs.• SWNTs can be grown from hydrocarbon gas feeds at a
temperature range of 800 – 1400C.• MWNTs can be grown from hydrocarbon gas feeds at a
range of 600 – 800C.
LPCVD Growth of Carbon Nanotubes
Ming Su, Bo Zheng, Jie Liu. A scalable CVD method for the synthesis of single-walled carbonnanotubes with high catalyst productivity. Chemical Physics Letters 3222000.321–326
LPCVD Growth of Carbon Nanotubes
Mo:Fe:Al - Alloy catalysts deposited via Sol Gel
Heat is applied for catalysts to anneal to substrate in tube furnace
Flow hydrocarbon gas for nucleation at catalysis
Nanotube growth occurs at catalysts
Photos created by CNEU
• Synthesized SWNTs using the following CVD parameters:– 50mg Fe/Mo catalyst supported on Al2O3
aerogel• The aerogel is a ultra-low density, highly
porous material.• Fe/Mo has a proven track record of being a
nucleation site for CNTs.– A furnace was heated to 100oC. From
850 – 1000oC, 100 sccm Ar was flown to purge the system.
Ming Su, Bo Zheng, Jie Liu. A scalable CVD method for the synthesis of single-walled carbonnanotubes with high catalyst productivity. Chemical Physics Letters 3222000.321–326
LPCVD Growth of Carbon Nanotubes
Carbon Nanotube FabricationArc Discharge Method
• Same process used to generate fullerenes
• Nanotube yield controlled by:- Stability of the arc- Pressure of the gas in the
chamber - Number of nanoparticles
in the carbon soot (1/3)
Carbon Nanotube FabricationArc Discharge Method
• Two graphite rods (anode and cathode) in an open vessel with deionizedwater
• Supply DC power for less than a minute – 100-200 A, 20-30 V
• The anode sublimates and the soot containing nanotubes is deposited on the cathode
Sharma, Ritu, Anup Kumar Sharma, and Varshali Sharma. "Synthesis of carbon nanotubes by arc-discharge and chemical vapor deposition method with analysis of itsmorphology, dispersion and functionalization characteristics." Cogent Engineering 2.1 (2015): 1094017.
MWNT• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Applications• DUCTILE FIBERS
– MWCNTs can be made into fibers that are highly ductile but alsostrong.
Naraghi, Mohammad, et al. "A multiscale study of high performance double-walled nanotube− polymer fibers." ACS
nano 4.11 (2010): 6463-6476.
Directed assembly of organized, multiwalled carbon-nanotube structures grown by chemical-vapourdeposition. a, Image obtained by scanning electron microscopy of three blocks of cylindrical pillars (about 10µm in diameter) of aligned carbon-nanotube arrays. Each pillar consists of several tens of nanotubes grown in vertical alignment and in a normal direction to Si02 patterns on the Si/Si02 template. No growth occurs on the Si parts of the template. The separation (d in diagram, top right) between pillars in the three blocks is indicated. B, Vertical and horizontal growth of aligned nanotubes (CNTs), viewed in a cross-section of a patterned Si/Si02 substrate. Scale bars, 100µm.
B.Q. Wei, R. Vajtai, Y. Jung, J. Ward, R. Zhang, G. Ramanath, P.M. Ajayan,
Department of Materials Science and Engineering, Nature, Vol. 416, April 2002, page 495-496
LPCVD Growth of Carbon Nanotubes
Bottom Up ManufacturingCarbon Allotropes,
Processes, and ApplicationsPart 4
Terence Kuzma
History
Future of Carbon Allotropes
1953, Germany:
Diamond-like Coatings
1991, Japan:
Multi-Wall Carbon Nanotubes
2004 , England:
Graphene
1985, USA:
Buckyballs
1992, Japan:
Diamond
Nanowires
1993, Japan:
Single-Wall Carbon Nanotubes
Diamond Nanowires• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Diamond Nanowires Discovery
● After Iijima’sdiscovery, it took a year of research until Diamond coatings were obtained, in 1992.
Hsu, Chih-Hsun, et al. "Synthesis of diamond nanowires using atmospheric-pressure chemical vapor deposition." Nano letters 10.9 (2010): 3272-3276.
Diamond Nanowires Discovery
Hsu, Chih-Hsun, et al. "Synthesis of diamond nanowires using atmospheric-pressure chemical vapor deposition." Nano letters 10.9 (2010): 3272-3276.
Diamond Nanowires• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Properties / Physics
Comparison of Thermal
Conductivity of different
types of Wide Band Gap
Materials.
Hsu, Chih-Hsun, et al. "Synthesis of diamond nanowires using atmospheric-pressure chemical vapor deposition." Nano letters 10.9 (2010): 3272-3276.
Field Emission Comparison
Properties / Physics
Hsu, Chih-Hsun, et al. "Synthesis of diamond nanowires using atmospheric-pressure chemical vapor deposition." Nano letters 10.9 (2010): 3272-3276.
Diamond Nanowires• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
ManufacturingTOP DOWN APPROACH
● A diamond film is applied to the surface of a substrate.
● An aluminum coating is deposited on top of the diamond film.
Drawn by Alix Joy, Summer2017.
ManufacturingTOP DOWN APPROACH
● Nanoparticles are scattered onto the top of this substrate and used as a mask during the
etching process.
● The substrate is then placed into the RIE system and etched.
Szunerits, Sabine, Yannick Coffinier, and Rabah Boukherroub. "Diamond nanowires: a novel platform for electrochemistry and matrix-free mass spectrometry." Sensors 15.6
(2015):12573-12593.
ManufacturingTOP DOWN APPROACH
● SEM image of diamond
nanowires grown vertically
upward in a top-down approach
in the RIE. This method tends to
form the diamond nanowires in
peak shapes.
Szunerits, Sabine, Yannick Coffinier, and Rabah Boukherroub. "Diamond nanowires: a novel platform for electrochemistry and matrix-free mass spectrometry." Sensors 15.6 (2015): 12573-12593.
ManufacturingTOP DOWN APPROACH
● SEM images of vertical
nanowires grown via RIE in
Top-down approach using
nanodiamonds as the mask
for the etching process.
Szunerits, Sabine, Yannick Coffinier, and Rabah Boukherroub. "Diamond nanowires: a novel platform for electrochemistry and matrix-free mass spectrometry." Sensors 15.6 (2015): 12573-12593.
ManufacturingBOTTOM UP APPROACH
● Catalysts are used as seeds in
this type of diamond nanowire
synthesis.
● A solution of catalysts are
mixed with a sol gel and this
gelatin mixture is spin coated
onto a substrate.
Hsu, Chih-Hsun, et al. "Synthesis of diamond nanowires using atmospheric-pressure chemical vapor deposition." Nano letters 10.9 (2010): 3272-3276.
ManufacturingBOTTOM UP APPROACH
● The gelatin substrate is then placed into the CVD furnace and heated to approximately
700⁰C under atmospheric pressure.
● Carbon based gas is flown into the chamber and deposition of carbon atoms occurs on
the catalyst suspended within the gelatin.
Hsu, Chih-Hsun, et al. "Synthesis of diamond nanowires using atmospheric-pressure chemical vapor deposition." Nano letters 10.9 (2010): 3272-3276.
Manufacturing
● Plasma enhanced CVD is a similar process to the
CVD system.
● Catalyst seeds are used as a foundation of growth
in this method, however the plasma is used in this
deposition process.
BOTTOM UP APPROACH
Szunerits, Sabine, Yannick Coffinier, and Rabah Boukherroub. "Diamond nanowires: a novel platform for electrochemistry and matrix-free mass spectrometry." Sensors 15.6 (2015): 12573-12593.
ManufacturingBOTTOM UP APPROACH
● SEM images of vertical nanowires grown via CVD in Bottom-up approach.
Szunerits, Sabine, Yannick Coffinier, and Rabah Boukherroub. "Diamond nanowires: a novel platform for electrochemistry and matrix-free mass spectrometry." Sensors 15.6 (2015): 12573-12593.
Manufacturing● Attempt at growing Diamond Nanotubes inside Carbon Nanotubes.
BROWN UNIVERSITY
Hsu, Chih-Hsun, et al. "Synthesis of diamond nanowires using atmospheric-pressure chemical vapor deposition." Nano letters 10.9 (2010): 3272-3276.
Diamond Nanowires• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Applications● Diamond Nanowires in the Top Down approach are
mostly used in biosensor systems.● Ridged peaks and high conductivity of the diamond
nanowires lends itself to a very efficient material to be used in sensor systems.
● Diamond Nanowires in the Bottom-up approach are being studied for UV detector systems.
● High conductivity and the ability to isolate more straight and single diamond nanowires allows for it to be arranged in precise patterns in the UV detectorsystems.
Bottom Up ManufacturingCarbon Allotropes,
Processes, and ApplicationsPart 5
Terence Kuzma
History
Future of Carbon Allotropes
1953, Germany:
Diamond-like Coatings
1991, Japan:
Multi-Wall Carbon Nanotubes
2004 , England:
Graphene
1985, USA:
Buckyballs
1992, Japan:
Diamond Nanowires
1993, Japan:
Single-Wall
Carbon
Nanotubes
SWCNT• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
SWNT Discovery● After 1991, the first
confirmed single-wall carbon nanotubes were synthesized in 1993. However, research in thetopic can be traced back to1952.
Kuznetsov, Vladimir, and Marc Monthioux. "Who Should Be Credited for the Discovery of Carbon Nanotubes?" CARBON 43rd ser. 44.1621 (2006): 342-349. ResearchGate. Web. 27 July 2017.
SWNT Discovery● Since 2006,
annual production has increased 10 fold.
SWCNT• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Properties / Physics
Ong, Yit Thai, Ahmad, Abdul Latif, Zein, Sharif Hussein Sharif, & Tan, Soon Huat. (2010). A review on carbon nanotubes in an environmental protection and green engineering perspective. Brazilian
Journal of Chemical Engineering, 27(2),227-242.
STRUCTURE:
● Responsible for varying tensile strength, higher resistance, etc.
Properties / Physics
Monthioux, Marc, Philippe Serp, Emmanuel Flahaut, Manitra Razafinimanana, Christophe Laurent, Alain Peigney, Wolfgang Bacsa, and Jean-Marc Broto. "Introduction to Carbon Nanotubes." Springer
Handbook of Nanotechnology 2nd ser. 8.39 (2007): 43-112. ResearchGate. Web. 17 July 2017.
SWCNT• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
PRIMARY SYNTHESIS METHODS:
● Electric Arc Discharge
● Laser Ablation
● Gas-Phase Catalytic Growth
● Chemical Vapor Depositions
Minimize impurities and subsequent processes, maximize yield.
Manufacturing
● Used for Iijima’s discovery.
● Two high purity graphite rods,
the cathode and the anode.
● Cathode doped with catalytic
particles.
● Helium atmosphere
● High voltage until stable arc is
formed.
● Anode consumes, and deposits
on cathode.
Manufacturing
Thostenson, Erik, Zhifeng Ren, and Tsu-Wei Chou. "Advances in the Science and Technology of Carbon Nanotubes and Their Composites: A Review." Composites Science and Technology 61(2001):1899-912. Elsevier. Web. 17 July2017.
● Initially used for fabrication of
Fullerenes.
● Laser vaporizes graphite target
in vacuum.
● High temperatures around
1200० C.
● Graphite doped with cobalt and
nickel catalysts.
● Material condenses on cool
target.
Manufacturing
Thostenson, Erik, Zhifeng Ren, and Tsu-Wei Chou. "Advances in the Science and Technology of Carbon Nanotubes and Their Composites: A Review." Composites Science and Technology 61(2001):1899-912. Elsevier. Web. 17 July2017.
Manufacturing
● Solves yield issue, and provides more purity. Thus reducing filtering steps
● Decomposition of gas containing carbon.
● Excellent uniformity (diameter, length, straightness, and site density).
Thostenson, Erik, Zhifeng Ren, and Tsu-Wei Chou. "Advances in the Science and Technology of Carbon Nanotubes and Their Composites: A Review." Composites Science and Technology 61(2001):1899-912. Elsevier. Web. 17 July2017.
Pulsed Laser Vaporization• Process for producing SWNTs• A laser pulse is used to ablate a graphite
electrode• The electrode contains up to 1% of Co-Ni• Vaporization occurs in a tube furnace at 1200C• Vaporized material carried downstream by an
inert gas where it is collected outside of the furnace
• Produces reasonable quantities of pure SWNTs having good uniformity
SWCNT• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
COMPOSITE MATERIAL
● Electrically conductive filler, creating clear
polymers with electrical conductivity properties.
● Carbon nanotubes powders mixed with polymers or
precursor resins can increase stiffness, strength,
and toughness. These enhancements depend on
carbon nanotubes diameter, aspect ratio,
alignment, and dispersion.
Applications
Xie, Sishen, Wenzhi Li, Zhengwei Pan, Baohe Chang, and Lianfeng Sun. "Mechanical and Physical Properties on Carbon Nanotube." Journal of Physics and Chemistry of Solids 61.7 (2000): 1153-158.
ResearchGate. Web. 17 July2017.
MICROELECTRONICS
● Attractive for transistors because of their low
electron scattering and their band gap.
● high-k dielectrics
The International Technology Roadmap for the
replacement of Cu in microelectronic interconnects:
● Low scattering
● High current-carrying capacity
● Resistance to electromigration.
Applications
Xie, Sishen, Wenzhi Li, Zhengwei Pan, Baohe Chang, and Lianfeng Sun. "Mechanical and Physical Properties on Carbon Nanotube." Journal of Physics and Chemistry of Solids 61.7 (2000): 1153-158.
ResearchGate. Web. 17 July2017.
BIOTECHNOLOGY
● Dimensional and chemical compatibility of
carbon nanotubes with biomolecules, such as
DNA and proteins, make it suitable for medical
devices.
● Can be internalized by cells, thus used for cancer
treatment.
● More effective that liposomes.
● Cargo release can be triggered by using
near-infrared radiation.
Applications
Xie, Sishen, Wenzhi Li, Zhengwei Pan, Baohe Chang, and Lianfeng Sun. "Mechanical and Physical Properties on Carbon Nanotube." Journal of Physics and Chemistry of Solids 61.7 (2000): 1153-158.
ResearchGate. Web. 17 July2017.
History
Future of Carbon Allotropes
1953, Germany:
Diamond-like Coatings
1991, Japan:
Multi-Wall Carbon Nanotubes
2004 , England:
Graphene
1985, USA:
Buckyballs
1992, Japan:
Diamond Nanowires
1993, Japan:
Single-Wall Carbon Nanotubes
Graphene• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Graphene• The existence of graphene has been noted for over
100 years, but the material was not fully appreciated• Graphene is the basic structural element of other
allotropes, including graphite, charcoal, carbon nanotubes and fullerenes
• Graphene was later “rediscovered”, isolated and characterized in 2004 by Andre Geim and Konstantin Novoselov at the University of Manchester.
• This work resulted in the two winning the Nobel Prize in Physics in 2010 "for groundbreaking experiments regarding the two-dimensional material graphene”.
• The global market for graphene is reported to have reached $9 million by 2014
Graphene Discovery● Professor Andre Geim and
Professor Kostya Novoselov, University of Manchester.
● Nobel Prize in Physics 2010.
Hildebrand, Gabriel. Discovery of Graphene. Digital image.
Wikipedia. Nobelmuseet, 2011. Web. 23 July2017.
Graphene• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
WHAT IS GRAPHENE?
● Conductive - > Zero-band gap semiconductor.
● Strong - > 200x stronger than steel.
● Flexible - > Stretch 25% its length.
● Ultrathin - > 1 atom thick.
● Transparent - > 2 % absorbed light.
● Selectivity permeable - > H2O only.
Properties
Properties / Physics
CONDUCTIVITY:
● Carbon has 4 valence electrons.
● Zero-band gap semiconductor.
● Dirac points and Fermions.
● Electron mobility at room temperature.
○ 15,000 cm2 * V-1 * s -1.
Warner, Jamie H., Fransizka Schaffel, Mark Rummeli, and Alicja Bachmatiuk. Graphene: Fundamentals to Applications. Kidlington, Oxford: Elsevier, 2013. Print.
Properties / Physics
Allotropes of Carbon, Graphene
https://en.wikipedia.org/wiki/Allotropes_of_carbon
Graphene• A single layer of graphite is
called graphene and has extraordinary electrical, thermal, and physical properties.
• The graphene image derived from an AFM is shown to the right
• Graphene is a form of a two-dimensional, atomic-scale, honey-comb lattice in which one atom forms each vertex.
https://www.flickr.com/photos/armymaterielcommand/6795812766
Graphene
1.42 Å
•Crystalline allotrope of carbon
•Light weight
•100x stronger than steel
•Perfect thermal conductor
•Bond length of 1.42 Å Diamond has a bond length of 1.54 Å!
Graphene Properties• Graphene has many extraordinary properties. It
is about 100 times stronger than the strongest steel with a hypothetical thickness of 3.35Å which is equal to the thickness of the graphene sheet
• It conducts heat and electricity efficiently and is nearly transparent
• The global market for graphene is reported to have reached $9 million by 2014 with most sales in the semiconductor, electronics, battery energy and composites industries.
Properties / PhysicsSTRENGTH
● Tensile strength - > 130GPa
● Hooke’s Law - > 39 N/m - 39 x10 - 6 N/m
○ K: spring constant
○ X: displacement
● Young’s Modulus - > 1Tpa
○ Tensile Stress: σ=F/A
○ F: tension, A: area
○ Extensional Strain: ε=ΔL/L0
○ ΔL: change in length, L0 : original length
"Young's Modulus." Wikipedia. Wikimedia Foundation, 13 July 2017. Web. 23 July 2017.
Graphene• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
Graphene Production• There are two main types of manufacturing
process’s when it comes to isolating graphene.• Graphene manufacturing processes include two
separate types; mechanical cleaving, and chemical methods
• The least expensive process is mechanical in nature and uses what is known as mechanical cleaving to separate the carbon monolayers from an original graphite crystal.
Graphene• Mechanical exfoliation (repeated peeling) from
graphite• It can be produced by epitaxy on an insulating or
conducting substrate • Applications may include replacing silicon in
high-performance electronic devices.
Graphene• Mechanical cleaving is very favorable when it
comes to obtained large (~100 μm) and very pure monolayers of graphene
• This cleaving method was used by Geim and Novoselov in their Nobel Prize winning research.
• Describe method…………………..• The disadvantage of mechanical cleaving is that
large scale production is very hard to perform.• It is difficult to be consistent in the exact amount
of layers that are removed during cleaving
Graphene Production• Chemical exfoliation process utilizes common
chemicals such as potassium permanganate or sulfuric acid to strip away thin layers of graphene
• Although there are several different types of chemical exfoliation methods the highest yielding one is the unzipping of carbon nanotubes along with a methane plasma defect repair process
Manufacturing
SEM images of
Graphene
Oxide Layers.
https://www.intechopen.com/books/syntheses-and-applications-of-carbon-nanotubes-and-their-composites/carbon-nanotubes-for-energy-applications
Manufacturing
TEM images of
Few Layer
Graphene (FLG).
http://www.nature.com/nature/journal/v446/n7131/fig_tab/nature05545_F4.html
Manufacturing
Raman
Spectra of
Graphene.
http://ralphgroup.lassp.cornell.edu/projects/graphene_electrochemistry/fig2.jpg
Graphene• The Discovery • Material Properties and Physics• Manufacturing Methods• Applications
● CONDUCTIVITY - > Solar Panel Coatings.
● STRENGTH - > Damascus Blades.
● FILTRATION - > Salt Water Filter.
Applications
Graphene-Coated Solar Panels
● Ocean University in China
● Ions in rain form pseudocapacitor○ Na+, Ca+, NH3+
● Prototype generates 6.35%○ Compared to 18%
Applications
Wolf, E. L. Applications of Graphene: An Overview. Cham: Springer, 2014. Print.
ApplicationsDAMASCUS BLADES:
● South Central India - 4 0 0 B.C.
● Bloomery iron and carbon in
crucible for days.
● 1 - 2 % carbon is strength and
durable for Middle East weapons.
● Strength from CNT and graphene.
Hirst, Kris K. "Wootz Steel - Raw Material for Damascus Steel Blades." ThoughtCo. ThoughtCo, 24 Aug. 2016. Web. 23 July 2017.
SALTWATER FILTER:
● 2.5% of Earth’s water is freshwater.
● Graphene is permeable only to H2O.
● Graphene Oxide.
● 500 times thinner = 100 times less pressure.
Applications