You are on page 1of 48

ILAML SN1nLSIS CI

CAk8CNACLCUS NANCMA1LkIALS:
IUNDAMLN1AL ULS1ICNS
Ishwar k. ur|
Professor of nqineerinq 5cience & Mechonics
A SnCk1 kIMLk
now to make graph|t|c carbonaceous
nanomater|a|s?
A f|ame and a cata|yst
Nanotubes and
nanof|bers
Arana, C., Sen, S., and url, l. k., ltoceeJloqs of 1be combostloo lostltote, 30, 2003.
Sen, S., and url, l. k., Noootecbooloqy, 13, 2003.
1nIS IS NC1 NLW
I.M. S|nger and I. Grumer, Proceedinqs of the
combustion lnstitute 7 (19S9)
D|fferent cata|ysts
N|cke|
Sta|n|ess stee|
Graph|t|c
nanof|bers
Graph|t|c
nanotubes
Lncapsu|ated
nanopart|c|es
Vary|ng t|me
1nIS IS NC1 1nL "USUAL"
CCM8US1ICN GLNLkA1LD SCC1
A common m|sconcept|on

These are amorphous


agglomerated soot
nanoparticles collected on an
inert SiC fiber placed in a flame
A MCDLL
1he process of carbon nanotube and nanof|ber
format|on

Combustion products
Substrate
Catalyst chemistry and heat
and mass transport
Nanofibrous carbon,
containing CNTs and CNFs
Nanofibrous carbon, containing
CNTs and CNFs
Gas phase chemistry
& transport
Heat & mass transfer
Catalyst grain formation
Heat & mass transfer
Nanostructure formation
naha, S., Sen, S., ue, A. k., and url, l. k., ltoceeJloqs of 1be combostloo lostltote, 31, 2007.
naha, S., and url, l. k., Iootool of lbyslcs u. ApplleJ lbyslcs, 41, 2008.
Deve|op|ng mechan|sms
The only model to include
catalysis, transport and
ambient conditions, such
as combustion.
Va||dat|on: CVD targets
Zhang & Smith, J. Catal., 2005
Bower et al., App. Phys. Lett., 2000
Bronikowski, Carbon, 2006
Inf|uence of temperature
CNT length versus time for CVD
synthesis at different
temperatures using Co as the
catalyst at a 5 Torr C
2
H
2
partial
pressure.

1he carbon lmplngemenL raLe ls


Where [ ls number of carbon aLoms conLalned ln
molecule of hydrocarbon specles (e.g., [ = 2 for
C
2
P
2
), n
Av
ls Avogadro number, Lhe near-surface
hydrocarbon parLlal pressures, M Lhe molecular
welghL of Lhe specles, 8 Lhe unlversal gas consLanL
and 1 Lhe gas LemperaLure aL Lhe surface
CC ls Lhe ma[or conLrlbuLor Lowards carbon
deposlLlon
MCLLCULAk SIMULA1ICNS
now do these structures form?
1|p and base growth
MagnlLude of energy galn durlng growLh
Smaller Lhan surface lnLeracLlon energy for le
8ase growLh
CreaLer for nl
1lp growLh
CN1 structure
nl caLalysL parLlcle yk
2
p
= 123 ev
le caLalysL parLlcle yk
2
p
= 1700 ev
Pere, y denoLes surface energy and
k
p
Lhe parLlcle slze
8ase CrowLh, L < -yk
2
p

1lp CrowLh, L > -yk
2
p

8aner[ee, naha and url, ApplleJ lbyslcs lettets, 2008
SULknDkCnC8IC SUkIACLS
Nove| uses of amorphous carbon nanomater|a|s
What are they?
SLM lmage of roughness on a loLus leaf,
cbeoq et ol.
SLM lmage of carbon nanosLrucLures
produced by flame synLhesls
Naturally occurring superhydrophobic surfaces have microscale
features with nanoscale asperities.
Why use carbon?
Superhydrophoblc surfaces are fabrlcaLed wlLh
mlcro- and nano-sLrucLured polymers
Carbon nanosLrucLured surfaces known Lo
exhlblL superhydrophoblc behavlor for even
corroslve llqulds over a wlde range of pP
values
Why Use I|ame Synthes|s?
Oo JemooJ and toplJ meLhod
labrlcaLe stoble mlcrosLrucLures
lrom self otqoolzeJ nanosLrucLures
lor produclng superhydrophoblc surfaces
1

Naha, S., Sen, S. and Puri, I. K. Carbon 45, 2007.

SUkIACL MCDIIICA1ICN
An examp|e
Lxper|menta| procedure
Flame
Si disc
(substrate)
Deposition zone due to flame
Air Fuel
(Ethylene)
Surface mod|f|cat|ons
Nanostructured superhydrophob|c surfaces
Naha, S., Sen, S. and Puri, I. K. Carbon 45, 2007
kCUGnNLSS
1he |nf|uence of surface morpho|ogy
Surface structure
We have shown LhaL surface sLrucLure depends on Lhe flame and
subsLraLe LemperaLure, lnLerface or surface chemlsLry, local gas-phase
composlLlon
Superhydrophob|c|ty: Wenze| &
Cass|e-8axter states
Wenze| State
8oughness enhances surface area and
Lhus hydrophoblclLy.
WaLer on a rough surface peneLraLes
Lhe asperlLles of Lhe surface sLrucLure.
uropleL Lends Lo sLlck Lo Lhe surface.
1he flame synLheslzed self organlzed carbon nanosLrucLures allow for
enLrapmenL of alr due Lo Lhe closely packed asperlLles, leadlng Lo Cass|e-
8axter state superhydrophob|c|ty.
Cassie-Baxter State
Water droplet sits partly on the solid
surface and partly on air trapped within
the asperities.
Contact angle results from contact of
water with both air and the solid
substrate.
Droplet tends to roll of easily.
Cannon, Andrew H. Wikipedia, the Free Encyclopedia. Web. 17 July
2010
WnA1 IS 1nL NA1UkL CI CAk8CN?
Nanostructure character|st|cs
Surface structure
Disc center 45 mm from disc center
SEM images of nanopearls
1hese are nanopear|s
TEM images of nanopearls
Nanobead region Sooty region
C1s spectra of carbon f||m
Nanobead region Sooty region
X-ray Photoelectric Spectroscopy (XPS) analysis using Mg source (anode)
*Y. Zhou, B. Wang, X. Song, E. Li, G. Li, S. Zhao, H. Yan, Appl. Surf. Sci. 253 (2006) 2690-2694.
Ana|ys|s of kS spectra
Pydrophoblc amorphous C fllms reporLed Lo conLaln 30-71

hybrldlzed sLrucLure
*

Curve-flLLlng of C1s specLra shows
Nanobead reg|on has SS

structure
SooLy reglon has 33.3

sLrucLure

structure perta|ns to p|anar graph|t|c hexagona| r|ngs,


slgnlfles dlamond-llke LeLrahedral sLrucLure
8elaLlvely hlgh percenLage (43-47 appx.) of

sLrucLures
explalns Lhe presence of spongy 'nanobeads'
Comp|ete kS spectra
0
5000
10000
15000
20000
25000
200 300 400 500 600 700 800 900 1000 1100
Binding Energy (eV)
I
n
t
e
n
s
i
t
y

(
a
r
b
i
t
r
a
r
y

u
n
i
t
s
)
Nanobead Region Sooty Region
C1s
O1s
O KVV
C KLL
Ana|ys|s
C specLra for carbon forms are very
dlfferenL
eak Lo peak wldLh ls
~ 14 ev for dlamond
~ 23 ev for graphlLe
ln our case, lL ls approxlmaLely 19 ev
Strengthens the conc|us|on of amorphous-C
presence
A NCVLL ALICA1ICN
M|crob|a| fue| ce||
Sta|n|ess Stee| Mesh-CNS-M|croorgan|sm
Sta|n|ess Stee| Mesh- CNS
Lxamp|e: grow|ng bacter|a
Mazumder, S., lalklnham lll, !.C., uleLrlch, A.M., and url, l.k., , 2009
Surfaces coaLed wlLh carbon nanosLrucLures bound hlgher numbers of
mycobacLerlal cells ln Lhe shorL Lerm and form denser blofllms afLer
lncubaLlon
S.Mazumder, !.C. lalklnham lll, A.M. uleLrlch, l.k. url, 8lofoolloq. 1be
Iootool of 8looJbesloo ooJ 8lofllm keseotcb, 26:333 - 339, 2010
Adherence w|th m|croorgan|sms
VAkICUS SU8S1kA1LS 8LnAVL
SIMILAkL
Another examp|e
1h|s method uses soot depos|t|on
unlform carbon nanosLrucLure
deposlLs obLalned on dlfferenL
subsLraLes exposed Lo flame
Coannular axlsymmeLrlc
combusLor wlLh opLlmlzed fuel
and alr flow raLes.
1

lnner flow: luel - eLhylene
(0.269 L/mln)
CuLer flow: Alr (31.7 L/mln)
Ethylene
Air Air
1ypes of substrates
1hree dlfferenL subsLraLes:
5tololess steel mesb
a
- (le/Cr18/
nl10) wlLh 0.23 mm wlre dlameLer
5tololess steel foll
b
- (le/Cr18/
nl8)
5lllcoo wofet
c

8are
CaLalysL coaLed (10 nm
magneLlLe nanoparLlcles
suspended ln waLer - LMC 703
from lerroLec)
Surface character|zat|on
ConLacL angle measuremenL
uSA 100 surface analyzer (kruss)
nanosLrucLure vlsuallzaLlon
Plgh resoluLlon SchoLLky fleld emlsslon scannlng
elecLron mlcroscope (lLSLM)
LLC (Zelss) 1330 aL 3kv acceleraLlng volLage ln hlgh vacuum
mode.
Surface analysls (measuremenL of roughness)
ALomlc lorce Mlcroscopy (AlM)
nanoscope lll (veeco)
Lxamp|e: uncoated s|||con wafer
43
Substrate ne|ght,
Contact Ang|e
ILSLM Image
8eference LengLh = 200 nm
Surface Water
Drop|et
h = 2 mm
= 34.15
h = 4 mm
=
131.90
h = 6 mm
=
126.80
h = 8 mm
=
141.60
Coverage volume
increases with height
No discernible carbon
nanostructure deposit at
2mm height and surface
is hydrophilic
Spongy nanobead
clusters appear at heights
of 4 mm and above,
leading to high contact
angles
Mean nanoparticle
size at this stage is
13 nm
Compar|son of substrates
ln sLalnless sLeel subsLraLes, deposlLs even
aL 2 mm helghL
arLlcle slzes:
Sta|n|ess stee| mesh : 7 - 17nm.
Sta|n|ess stee| fo|| : 27 - 30 nm.
ueposlLlon LranslLlons Lo mesoscale
morphology aL 13-20 mm helghL.
AL 30 mm helghL, mlcroscale morphology
Stainless Steel Mesh (h = 10mm)
Stainless Steel Foil (h = 10mm)
Uncoated Silicon Wafer (h = 10mm)
Contact ang|es for substrates
ConLacL angle varlaLlon
wlLh helghL follows roughly
Lhe same paLLern for all
uncoaLed subsLraLes
ueposlLs exhlblL conslsLenL
hydrophoblclLy for over slx
monLhs
ueposlLs can be wlped off,
buL do noL deLerloraLe on
Lhelr own
0
20
40
60
80
100
120
140
160
0 S 10 1S 20 2S 30 3S
C
o
n
t
a
c
t

A
n
g
|
e

ne|ght (mm)
SS loll
SS Mesh
Sl Wafer
Surface roughness: AIM |mages
Uncoated S|||con Wafer
Surface roughness afLer
deposlLlon ls lower Lhan on
nanoparLlcle coaLed subsLraLe
k
mox
= 111.06 nm
locteose lo sotfoce oteo.
236.
Magnet|te nanopart|c|e
coated S|||con Wafer
Surface roughness ls hlgher.
k
mox
= 408.8 nm
locteose lo sotfoce oteo. 479
Some Cpen uest|ons
1rlbologlcal properLles of Lhe deposlL
Can Lhe deposlL be made more durable?
ueLalls of slmllarlLles and dlfferences beLween
regular sooL deposlLs and carbon nanobeads
A Cassle-8axLer hydrophoblc sLaLe ls observed,
buL can Lhere be a Wenzel sLaLe?
47
1hank ou!
lshwar k. url
ltofessot of oqloeetloq 5cleoce ooJ Mecboolcs
vltqlolo 1ecb
esmhead aL vL doL edu - www.esm.vL.edu/~lkpurl
LwlLLer.com/esmhead
hLLp://www.esm.vL.edu/~lkpurl/flles/e-semlnars/e-semlnars.hLml
48