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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


1953, Germany:


1991, Japan:


2004 , England:

Graphene

1985, USA:

Buckyballs

1992, Japan:

Diamond Nanowires

1993, Japan:


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

https://en.wikipedia.org/wiki/File:Diamond_Cubic-F_lattice_animation.gif

https://en.wikipedia.org/wiki/File:Diamond_cubic_animation.gif

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.


● 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




The Discovery Material Properties and PhysicsManufacturing MethodsApplications

Manufacturing

● Physical Vapor

Deposition



● Producing high sp3 ratios, density,

and hardness

● Pulsed laser deposition and

filtered cathodic vacuum arc are

the leading processes

Manufacturing

PLD




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.



● 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


1953, Germany:


1991, Japan:


2004 , England:

Graphene

1985, USA:

Buckyballs

1992, Japan:

Diamond Nanowires

1993, Japan:


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

http://images.google.com/imgres?imgurl=www.orozco.cps.k12.il.us/resources/bwebpagedesignresources/soccer ball 2.jpg&imgrefurl=http://www.orozco.cps.k12.il.us/beginningwebpagedesign/isaias.html&h=200&w=200&sz=13&tbnid=bgu1SY3T114J:&tbnh=99&tbnw=99&prev=/images?q=+soccer+ball&hl=en&lr=&ie=UTF-8&oe=UTF-8&sa=N

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

https://en.wikipedia.org/wiki/Nanometer

https://en.wikipedia.org/wiki/Fullerene

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

https://www.google.com/url?sa=i&rct=j&q=&esrc=s&source=images&cd=&cad=rja&uact=8&ved=0ahUKEwjIyamA85_LAhUCyyYKHcPABQMQjRwIBw&url=https://it.wikipedia.org/wiki/Fullereni&bvm=bv.115339255,d.eWE&psig=AFQjCNE3QuZRcSDa6538vL6nNU16FcTqtw&ust=1456935808039553

Eight selected allotropes of carbon

a) diamondb) graphitec) lonsdaleited) C60 buckminsterfullerene e) C540, Fulleritef) C70 g) amorphous carbonh) single-walled carbon nanotube


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.

https://en.wikipedia.org/wiki/Buckminsterfullerene

https://en.wikipedia.org/wiki/C70_fullerene




https://en.wikipedia.org/wiki/Soot

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]

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


• 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


• 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]

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


1953, Germany:


1991, Japan:

Multi-Wall

Carbon

Nanotubes

2004 , England:

Graphene

1985, USA:

Buckyballs

1992, Japan:

Diamond Nanowires

1993, Japan:


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.

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


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


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.

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



Processes, and ApplicationsPart 4

Terence Kuzma

History


1953, Germany:


1991, Japan:


2004 , England:

Graphene

1985, USA:

Buckyballs

1992, Japan:

Diamond

Nanowires

1993, Japan:


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



Comparison of Thermal

Conductivity of different

types of Wide Band Gap

Materials.


Field Emission Comparison



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.


● 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.


● 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.


● SEM images of vertical

nanowires grown via RIE in

Top-down approach using

nanodiamonds as the mask

for the etching process.


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.



● 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.


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



● SEM images of vertical nanowires grown via CVD in Bottom-up approach.


Manufacturing● Attempt at growing Diamond Nanotubes inside Carbon Nanotubes.

BROWN UNIVERSITY


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.


Processes, and ApplicationsPart 5

Terence Kuzma

History


1953, Germany:


1991, Japan:


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.


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.


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.

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


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).


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

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



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



History


1953, Germany:


1991, Japan:


2004 , England:

Graphene

1985, USA:

Buckyballs

1992, Japan:

Diamond Nanowires

1993, Japan:


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.

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


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.

Allotropes of Carbon, Graphene


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 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

http://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

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

http://ralphgroup.lassp.cornell.edu/projects/graphene_electrochemistry/fig2.jpg

● 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

bottom up manufacturing - unescothe 6:5 bonds (between a hexagon and a pentagon). its average bond...

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