Measurement Challenges for Carbon Nanotube Material

Edward Sosa1, Sivaram Arepalli1, Pasha Nikolaev1, Olga Gorelik1 and Leonard Yowell2

1 ERC Inc. / NASA - Johnson Space Center, Houston, TX 2 NASA - Johnson Space Center, Houston, TX

Abstract

The advances in large scale applications of carbon nanotubes demand a reliable supply of raw and processed materials. It is imperative to have a consistent quality control of these nanomaterials to distinguish material inconsistency from the modifications induced by processing of nanotubes for any application. NASA Johnson Space Center realized this need five years back and started a program to standardize the characterization methods. The JSC team conducted two workshops (2003 and 2005) in collaboration with NIST focusing on purity and dispersion measurement issues of carbon nanotubes [1]. In 2004, the NASA-JSC protocol was developed by combining analytical techniques of SEM, TEM, UV-VIS-NIR absorption, Raman, and TGA [2]. This protocol is routinely used by several researchers across the world as a first step in characterizing raw and purified carbon nanotubes. A suggested practice guide consisting of detailed chapters on TGA, Raman, electron microscopy and NIR absorption is in the final stages and is undergoing revisions with input from the nanotube community [3]. The possible addition of other techniques such as XPS, and ICP to the existing protocol will be presented. Recent activities at ANSI and ISO towards implementing these protocols as nanotube characterization standards will be discussed. Ref.: 1) http://mmptdpublic.jsc.nasa.gov/jscnano/

2) Arepalli S., Nikolaev P., Gorelik O., Hadjiev V. G., Holmes W. A., Files B. S., and Yowell L., “Protocol for the Characterization of Single-Wall Carbon Nanotube Material Quality”, Carbon, Vol. 42, pp. 1783-1791 (2004). 3) http://www.msel.nist.gov/Nanotube2/Carbon_Nanotubes_Guide.htm

https://ntrs.nasa.gov/search.jsp?R=20070001007 2018-07-26T00:28:34+00:00Z

Mea

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QU

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o W

e W

an

t to

Kn

ow

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no

tub

e P

uri

ty?

•Over the years, various manufacturers claimed purity

anywhere from 50 to 90%. Do we trust these numbers?

What are we buying?

•How consistent is NT material produced by the same

manufacturer in different batches?

•What are implications of nanotube purity in applications?

•How does the purity affect stress transfer in composites,

electrical and thermal conductivity, surface area, sidewall

chemistry, dispersion properties, etc.?

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600

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(cm

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1000

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1500

0

2000

0

2500

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3000

0

3500

0

4000

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0 1000

1100

1200

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Ram

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r

colla

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n

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1000

2000

3000

4000

5000

6000

100

120

140

160

180

200

220

240

260

280

300

Ram

an S

hift (c

m-1)

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inne

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ve

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0.0

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0.0

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L

PROPERTIESRe

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l M

as

s

Th

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al

Sta

bilit

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pe

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n

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tio

s

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d

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sit

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all D

iam

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r %

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r M

ate

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ecti

on

Va

riab

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y S

um

ma

ry

La

ser

Ma

teri

al

Va

ria

bil

ity

: C

on

clu

sio

ns

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ow

nst

ream

SW

CN

T m

ater

ial

tends

to h

ave

low

er

ther

mal

sta

bil

ity

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GA

sp

ectr

al s

hap

e si

mil

ar f

or

mai

n a

nd f

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r S

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NT

mat

eria

l. I

nner

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mat

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hal

f th

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ass

com

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ed t

o o

ther

mat

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ow

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mat

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s cr

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(?)

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(T

GA

an

d U

V-V

is-N

IR)

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pec

tral

fea

ture

s in

UV

-Vis

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dat

a is

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pro

po

rtio

nal

to

dis

tance

fro

m t

arget

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nt

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sorp

tion c

han

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fro

m t

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dep

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and c

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100

500

900

1300

1700

2100

2500

2900

Ra

ma

n S

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100

150

200

250

300

350

400

Ram

an

Sh

ift

(cm

-1)

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Ca

tho

de

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ll D

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sit

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teri

al:

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man

Sp

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a (

con

td.)

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m

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m

(9,4

)

1.4

7n

m

(8,4

)

1.3

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m

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)

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7n

m ?

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)

Ma

teri

al d

ep

osite

d fu

rth

er

aw

ay fro

m e

lectr

od

es h

ave

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er

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ntr

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f la

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r d

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r tu

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wall

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col>

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ilit

y S

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mp

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n o

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rc M

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rial

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zed

)

0

0.2

0.4

0.6

0.81

1.2

1.4

1.6

130

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0140

014

50

15

00

15

50

16

00

1650

1700

1750

1800

Ra

ma

n S

hif

t (c

m-1

)

Scattering Intensity

Ca

tho

de

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bbs

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ll D

epo

sit

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d a

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es w

ith

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ter

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ctio

ns –

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bs

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d w

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posit h

ave

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r fr

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n o

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dy

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rifie

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stin

g S

tud

y, 3

0 m

in. S

on

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Cha

ng

e A

fter

1 H

our

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9 32

552

572

592

511

2513

25

Wav

elen

gth(

nm)

Absorption (arb. Units)

JSC

-A72

.3_1

: 700

-100

0nm

Are

a 73

.75

JSC

-A72

.3_2

: 700

-100

0nm

Are

a 72

.82

Ha

rves

ted

Arc

Ma

teri

al:

UV

-Vis

-NIR

Sp

ectr

aU

V-V

IS D

isp

ersi

on

Stu

dy

: JS

C-A

72.1

Arc

un

pu

rifie

d, 1

5min

So

nic

atio

n, 1

.595

% C

han

ge

Aft

er 1

Ho

ur

0

0.050.1

0.150.2

0.250.3

0.350.4 32

552

572

592

511

2513

25

Wav

elen

gth

(nm

)

Absorption

JSC

-A72

_1:

700-

1000

nm A

rea

49.6

5

JSC

-A72

_2:

700-

1000

nm A

rea

48.8

6

UV

-VIS

Dis

per

sio

n S

tud

y :

JSC

-A72

.2

JSC

Arc

un

pu

rifie

d-H

arve

stin

g S

tud

y, 1

20 m

in. S

on

icat

ion

, 0.6

665%

Ch

ang

e A

fter

1 H

ou

r

0

0.1

0.2

0.3

0.4

0.5

0.6 32

552

572

592

511

2513

25

Wav

ele

ng

th(n

m)

Absorption (arb. Units)

JSC

-A72

.2_1

: 70

0-10

00nm

Are

a 60

.55

JSC

-A72

.2_2

: 70

0-10

00nm

Are

a 60

.15

UV

-VIS

Dis

pers

ion

Stu

dy :

JSC

-A72

.4

JSC

Arc

unp

urifi

ed-H

arve

stin

g S

tudy

, 30

min

. Son

icat

ion,

0.1

114%

Cha

nge

Afte

r 1 H

our

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8 32

552

572

592

511

2513

25

Wav

elen

gth(

nm)

Absorption (arb. Units)

JSC

-A72

.4_1

: 700

-100

0nm

Are

a 73

.44

JSC

-A72

.4_2

: 700

-100

0nm

Are

a 73

.36

Ca

tho

de

Co

lla

rett

e

We

bs

Wa

ll D

ep

osit

Need

to

fo

cu

s i

n o

n t

hese r

eg

ion

s

Arc

Ma

teri

al

Co

llec

tion

Va

ria

bil

ity

Su

mm

ary

Arc

Ma

teri

al

Va

ria

bil

ity

: C

on

clu

sio

ns

TG

A:

Lo

wer

oxid

ation tem

ps for

mate

rial fu

rther

from

ele

ctr

odes m

ore

lik

ely

due t

o s

om

e d

egre

e o

f over-

coating.

Lo

wer

meta

l conte

nt observ

ed in

vers

ely

to d

ista

nce fro

m e

lectr

odes.

Ram

an

:

D-b

an

d d

oes n

ot support

TG

A c

arb

on im

purity

specula

tion

.

RB

M s

ugg

ests

sm

alle

r dia

mete

rs m

ore

pre

vale

nt in

cath

ode m

ate

ria

ls.

G-b

and m

ay s

ho

w m

ore

meta

llic featu

res in c

ath

ode m

ate

ria

l, w

hile

more

SC

featu

res in w

all

dep

osit.

UV

-Vis

:

Su

ppre

ssed o

ptica

l fe

atu

res s

upport

over-

coating o

f tu

bes.

Str

onger

S22 tra

nsitio

n in a

gre

em

ent w

ith R

am

an r

esults.

HiP

co M

ate

ria

l V

ari

ab

ilit

y S

tud

y -

TG

A

Fro

nt

En

d C

olle

cti

on

-0.4

-0.2

0.0

0.2

0.4

0.6

Deriv. Weight (%/°C)

20

40

60

80

100

120

Weight (%)

0200

400

600

800

1000

Tem

pera

ture

(°C

)

Siz

e:

2.9

339 m

g

Ru

n #

1

357.9

5ºC

419.8

5ºC

554.7

6ºC

B-

28.3

5%

T

-30.6

1%

-0.2

0.0

0.2

0.4

0.6

Deriv. Weight (%/°C)

20

40

60

80

100

120

Weight (%)

0200

400

600

800

1000

Tem

pera

ture

(°C

)

Siz

e:

3.0

069 m

g

Ru

n #

2

364.3

0ºC

418.2

6ºC

551.5

8ºC

B-

30.3

8%

T

-31.1

7%

-0.2

0.0

0.2

0.4

0.6

Deriv. Weight (%/°C)

20

40

60

80

100

120

Weight (%)

0200

400

600

800

1000

Tem

pera

ture

(°C

)

Siz

e: 2.9

74

1 m

g

Ru

n #

3

B-

29.0

5%

T

-30.2

6%

361.1

3ºC

418.2

6ºC

554.7

6ºC

Ba

ck

En

d C

oll

ec

tio

n

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

Deriv. Weight (%/°C)

0

20

40

60

80

100

120

Weight (%)

0200

400

600

800

1000

Tem

pera

ture

(°C

)

Siz

e: 2.9

42

7 m

g

367.4

8ºC

B-

20.4

2%

T

-19.7

4%

389.7

0ºC

-0.5

0.0

0.5

1.0

1.5

2.0

2.5

Deriv. Weight (%/°C)

0

20

40

60

80

100

120

Weight (%)

0200

400

600

800

1000

Tem

pera

ture

(°C

)

Siz

e: 2.9

695 m

g

367.4

8ºC

388.1

1ºC

B-

20.1

1%

T

-19.6

4%

-10123

Deriv. Weight (%/°C)

0

20

40

60

80

100

120

Weight (%)

0200

400

600

800

1000

Tem

pera

ture

(°C

)

Siz

e: 2.8

543 m

g

366.0

8ºC

389.9

3ºC

B-

21.6

5%

T

-19.0

5%

Re

su

lts:

1. B

oth

Ma

teri

als

sh

ow

go

od h

om

oge

ne

ity fro

m c

on

sis

tent T

GA

sp

ectr

a

2. B

ack e

nd

ma

teri

al d

isp

lays c

om

bu

stive

be

ha

vio

r

3

. B

ack e

nd

ma

teri

al h

as ~

33

% le

ss n

on

-ca

rbo

n im

pu

ritie

s

HiP

co M

ate

rial

Vari

ab

ilit

y S

tud

y:

UV

-Vis

-NIR

HiP

co

Va

ria

bilit

y S

tud

y -

Ba

ck

En

d M

ate

ria

l

0.1

5

0.2

5

0.3

5

0.4

5

0.5

5

0.6

5

0.7

5

30

05

00

70

09

00

11

00

13

00

15

00

Wav

ele

ng

th (

nm

)

Absorption

Perc

ent A

bsorp

tion C

hang

e: 18.3

5%

HiP

co

Va

ria

bilit

y S

tud

y -

Fro

nt

En

d M

ate

ria

l

0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

300

500

700

900

1100

1300

1500

Wav

ele

ng

th (

nm

)

Absorption

Perc

ent A

bsorp

tion C

hang

e: 1.9

3%

SW

CN

T M

easu

rem

ent

Ch

all

enges

Cu

rren

t st

ate

of

reli

ab

ilit

y a

nd

un

cert

ain

ty

NA

SA

-JS

C p

roto

col

for

pu

rity

an

d d

isp

ersi

on

Stu

dy

of

fin

e va

ria

tio

ns

in h

arv

este

d m

ate

ria

l

-Lase

r, a

rc a

nd

CV

D p

rod

uct

ion

ch

am

ber

s

Ad

dit

ion

s to

NA

SA

-JS

C p

roto

col

-“N

on

-na

no

tub

e”ca

rbon

an

d n

an

od

isp

ersi

on

Na

no

tub

e ch

ara

cter

iza

tio

n s

tan

da

rds

Fu

ture

Wo

rk

8000

10000

12000

8000

10000

12000

8000

10000

12000

0.0

0.2

0.4

0.0

0.1

= 0

.095

A(T

,S1)

A(S

22,S

1)

S1

A(S

22,S

1)

(b)

A(T

,S1) S

WN

Ts:

67%

CA

RB

ON

AC

EO

US

IM

PU

RIT

IES

: 33%

Wavenum

ber

(cm

-1)

(c)

A(T

,S2)

SW

NT

s:

40%

CA

RB

ON

AC

EO

US

IM

PU

RIT

IES

: 60%

Wavenum

ber

(cm

-1)

= 0

.057

A(T

,S2)

A(S

22,S

2)

A(S

22,S

2)

S2

(a)

RE

FE

RE

NC

E (

R2)

A(T

,R2)

Absorbance

Wavenum

ber

(cm

-1)

= 0

.141

A(T

,R2)

A(S

22,R

2)

A(S

22,R

2)

R2

No

n-n

an

otu

be

Ca

rbo

n b

y N

IR A

bso

rpti

on

M.

E.

Itk

is,

et a

l. N

ano

Let

t, 3

, 3

09

(2

003

)

50

00

10

00

01

50

00

0.0

0

0.0

5

0.1

0

0.1

5

0.0

0.1

0.2

0.3

S22

S11

CA

RB

ON

BLA

CK

PU

RIF

IED

SW

NT

S

AN

NE

AL

ED

PU

RIF

IED

SW

NT

s

(a)

Absorbance

Wa

ve

nu

mb

ers

(cm

-1)

M11

AP

SW

NT

s

(b)

HiP

co

Vari

ab

ilit

y S

tud

y -

Back E

nd

Mate

rial

0.1

5

0.2

5

0.3

5

0.4

5

0.5

5

0.6

5

0.7

5 300

500

700

900

1100

1300

1500

Wa

ve

len

gth

(n

m)

Absorption

Pe

rce

nt

Ab

so

rptio

n C

ha

nge

: 1

8.3

5%

-101

M11

meta

llic

DO

S

energy (eV)

-101

sem

ico

nd

uctin

g

DO

S

S22

S11

energy (eV)

2000

1000

6

66

M 1

1

S 2

2S

11

Wav

elen

gth

(nm

)

How

do

We

Per

form

Ch

ara

cter

iza

tio

n?

Nan

osc

op

ic

•T

ran

smis

sion

Ele

ctro

n M

icro

scop

y

(TE

M)

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tom

ic F

orc

e

Mic

rosc

opy (

AF

M)

•S

cannin

g T

unnel

ing

Mic

rosc

opy (

ST

M)

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rosc

op

ic

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can

nin

g E

lect

ron

M

icro

scop

y (

SE

M)

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ner

gy D

isp

ersi

ve

X-r

ay A

naly

sis

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X)

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am

an

Sp

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osc

op

y

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-ray

Photo

elec

tron

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tro

scopy (

XP

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osc

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her

mal

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vim

etri

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naly

sis

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A)

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V-V

isib

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ear

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IR)

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sorp

tion

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IR F

luore

scen

ce

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duct

ivel

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ou

ple

d

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(IC

P)

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pti

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ynam

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tter

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DL

S)

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-ray

Dif

frac

tio

n

(XR

D),

SA

XS

, S

AN

S

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tiv

ity

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urf

ace

Are

a(B

ET

)

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tren

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her

mal

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an

od

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tica

l D

isp

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aly

sis

Pro

toco

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Gu

idel

ines

for

a q

ua

nti

tati

ve

rep

rod

uci

ble

pro

toco

l:

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oll

ow

guid

elin

es f

or

UV

-Vis

pro

toco

l an

d e

stab

lish

dis

per

sio

n g

rad

e (A

, B

, o

r C

).

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nce

dis

per

sio

n g

rade

has

bee

n a

ssig

ned

, so

nic

ate

sam

ple

(0

.1 m

g/

mL

) fo

r 1

h.

•A

fter

1 h

of

sonic

atio

n, al

low

sam

ple

to

res

t at

ro

om

te

mp

erat

ure

fo

r 1

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tir

sam

ple

tho

rou

ghly

an

d r

emo

ve

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liqu

ot

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vo

lum

e o

f 17

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und

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r fu

ll

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rag

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sli

de

cove

r. T

his

volu

me

min

imiz

ed

the

form

ati

on

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vacu

ole

s w

ith

out

exce

ss s

pil

lag

e o

uts

ide

22

mm

x 2

2m

m a

rea

.

•U

se t

he

Op

tica

l C

om

par

ito

r at

10

0x

mag

nif

icat

ion

eq

uip

ped

wit

h a

gri

d t

o c

ou

nt

the

par

ticl

e dis

trib

uti

ons

wit

hin

an a

rea.

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ou

nt

an a

rea

that

rep

rese

nts

th

e hig

hes

t co

nce

ntr

atio

n o

f p

arti

cles

in

th

e sa

mple

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se t

he

OD

A P

roto

col

Tab

le t

o d

eter

min

e th

e dis

per

sio

n g

rad

e.

Nik

on V

12A

Com

par

ator 0.0

2”

100X

Alc

ohol

CV

D

HiP

co

NIR

Flu

ore

scen

ce f

or

Na

no

dis

per

sio

n

Ch

irali

ty D

eter

min

ati

on

-101

sem

ico

nd

uctin

g

DO

S

S22

S11

energy (eV)

Po

ssib

le A

dd

itio

ns

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SC

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toco

l

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Ab

sorp

tion

fo

r P

uri

ty A

sses

smen

t

OD

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and

NIR

Flu

ore

scen

ce f

or

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per

sion

AF

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or

Len

gth

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eter

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frac

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, S

TM

fo

r C

hir

alit

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cal

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or

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CN

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easu

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all

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ab

ilit

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cert

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n s

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esp

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ilit

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ty

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roto

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