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Jeremiah Kelley, Melissa Taylor, Dibyaranjan Mekap, John Simonsen Oregon State University Bruce Arey PNNL
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Stability of cellulose nanocrystal dispersions and aerogels

Feb 14, 2017

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Page 1: Stability of cellulose nanocrystal dispersions and aerogels

Jeremiah Kelley, Melissa Taylor, Dibyaranjan Mekap, John Simonsen

Oregon State University

Bruce AreyPNNL

Page 2: Stability of cellulose nanocrystal dispersions and aerogels

Coming attractions: Preparation of carboxylated cellulose

nanocrystals (C.CNXLs) Preparation of C.CNXL aerogels Stability of aerogels Ester formation Evaluation

SEM FTIR XRD

Page 3: Stability of cellulose nanocrystal dispersions and aerogels

Carboxylated CNC prepcellulose

Reflux2 hr

Dilute, settleand decant

N2 blanketstir

Filter, rinse

TEMPONaOClNaBr1 M NH4OHpH ~10MeOH quench

Filtersolids

Centrifuge,rinse

diafiltrationVacuum filtrationdialysis sonicationC.CNC

suspension

2.4 M HCl

Page 4: Stability of cellulose nanocrystal dispersions and aerogels

Carboxylated CNCsTypical size 7 X 140 nm1.4 mmol CO2H/g CNC~ 2.4 acid groups/nm2

Zeta potential ~ -50Conductivity of 2%

dispersion ~ 1 mS/cm

AFM by A. Mangalam

Page 5: Stability of cellulose nanocrystal dispersions and aerogels
Page 6: Stability of cellulose nanocrystal dispersions and aerogels

~ 7 nm

Page 7: Stability of cellulose nanocrystal dispersions and aerogels

~150 nm

Page 8: Stability of cellulose nanocrystal dispersions and aerogels

Surface charges 1β unit cell has a surface area of 3.32 nm2

neglecting the longitudinal ends and contains two cellulose chains with a cellobiose repeat unit

Thus 1.2 C6 groups/nm2

1.038 nm

0.82 nm

0.778 nm

Not consistent with measured value of 2.4 groups/nm2

Assumes a 7 X 7 nm crystal

Nishiyama, et al, J. AM. CHEM. SOC. 2002, 124, 9074-9082

Page 9: Stability of cellulose nanocrystal dispersions and aerogels
Page 10: Stability of cellulose nanocrystal dispersions and aerogels

Fabrication

Layer acetone over aqueous suspension of C.CNCs

Gel forms in < 1 day Replace the acetone layer at least three

times Dry in supercritical dryer Densities to 30 mg/cm3 have been

achieved

Page 11: Stability of cellulose nanocrystal dispersions and aerogels

http://www.teamonslaught.fsnet.co.uk/co2%20phase%20diagram.GIF

54

5

Supercritical drying

Flush cell to exchange solvent

Page 12: Stability of cellulose nanocrystal dispersions and aerogels

C.CNC aerogels

ORGANOGEL/LYOGEL

Page 13: Stability of cellulose nanocrystal dispersions and aerogels

C.CNC aerogels

AEROGEL

Page 14: Stability of cellulose nanocrystal dispersions and aerogels

C.CNC aerogels

REFLECTED LIGHT TRANSMITTED LIGHT

Page 15: Stability of cellulose nanocrystal dispersions and aerogels
Page 16: Stability of cellulose nanocrystal dispersions and aerogels
Page 17: Stability of cellulose nanocrystal dispersions and aerogels
Page 18: Stability of cellulose nanocrystal dispersions and aerogels
Page 19: Stability of cellulose nanocrystal dispersions and aerogels
Page 20: Stability of cellulose nanocrystal dispersions and aerogels
Page 21: Stability of cellulose nanocrystal dispersions and aerogels
Page 22: Stability of cellulose nanocrystal dispersions and aerogels
Page 23: Stability of cellulose nanocrystal dispersions and aerogels
Page 24: Stability of cellulose nanocrystal dispersions and aerogels

Protocol

Add water

Wait at least one day before next addition

Evaluate visually

Page 25: Stability of cellulose nanocrystal dispersions and aerogels

No addition of water

Page 26: Stability of cellulose nanocrystal dispersions and aerogels

39% H2O

Page 27: Stability of cellulose nanocrystal dispersions and aerogels

47% H2O

Page 28: Stability of cellulose nanocrystal dispersions and aerogels

60% H2O

Page 29: Stability of cellulose nanocrystal dispersions and aerogels

70% H2O

Page 30: Stability of cellulose nanocrystal dispersions and aerogels

80% H2O

Page 31: Stability of cellulose nanocrystal dispersions and aerogels
Page 32: Stability of cellulose nanocrystal dispersions and aerogels

Control ~ 25 nm cross section

Page 33: Stability of cellulose nanocrystal dispersions and aerogels

Heat treated110 °C/~2 hr

~40 nm cross section

Page 34: Stability of cellulose nanocrystal dispersions and aerogels

Butyl ester ~50 nm cross section

Page 35: Stability of cellulose nanocrystal dispersions and aerogels

Butyl ester

Page 36: Stability of cellulose nanocrystal dispersions and aerogels

Reacted aerogel – butyl ester?Starting material

Page 37: Stability of cellulose nanocrystal dispersions and aerogels

Reacted aerogelStarting material

Page 38: Stability of cellulose nanocrystal dispersions and aerogels

Octyl ester

Page 39: Stability of cellulose nanocrystal dispersions and aerogels

Octyl ester

Page 40: Stability of cellulose nanocrystal dispersions and aerogels

Average cross section ~ 80 nmOctyl ester

Page 41: Stability of cellulose nanocrystal dispersions and aerogels

2-3 nm

Octyl ester

Page 42: Stability of cellulose nanocrystal dispersions and aerogels

57 14 nm

Octyl ester dried from hexane

Page 43: Stability of cellulose nanocrystal dispersions and aerogels

Octyl ester dried from hexane

Page 44: Stability of cellulose nanocrystal dispersions and aerogels

Reacted aerogel – octyl ester?Starting material

Page 45: Stability of cellulose nanocrystal dispersions and aerogels

Reacted aerogelStarting material

Page 46: Stability of cellulose nanocrystal dispersions and aerogels

Control Butyl ester

200 nm

Page 47: Stability of cellulose nanocrystal dispersions and aerogels

200 nm

Butyl ester Octyl ester

Page 48: Stability of cellulose nanocrystal dispersions and aerogels

-100

0

100

200

300

400

500

600

700

800

900

1000

5 10 15 20 25 30

Cou

nts

2 theta

Aerogel butyl ester

Controlbutyl ester 1butyl ester 3

Page 49: Stability of cellulose nanocrystal dispersions and aerogels

Octyl ester

-100

0

100

200

300

400

500

600

700

800

900

1000

5 10 15 20 25 30

Cou

nts

2 theta

control

Octyl ester

Octyl ester hexane dried

Page 50: Stability of cellulose nanocrystal dispersions and aerogels

-100

0

100

200

300

400

500

600

700

800

900

1000

5 10 15 20 25 30

Cou

nts

2 theta

control

aerogel HCl

control HAc

Effect of acidification in acetone

Page 51: Stability of cellulose nanocrystal dispersions and aerogels

-100

0

100

200

300

400

500

600

700

5 10 15 20 25 30

Cou

nts

2 theta

control HClButyl esteroctyl ester

Acidification is the problem

Page 52: Stability of cellulose nanocrystal dispersions and aerogels
Page 53: Stability of cellulose nanocrystal dispersions and aerogels

Poly(allyl amine)PAAm

?

Page 54: Stability of cellulose nanocrystal dispersions and aerogels

Acidified cellulose aerogel

Page 55: Stability of cellulose nanocrystal dispersions and aerogels

PAAm

Page 56: Stability of cellulose nanocrystal dispersions and aerogels

Coated (reacted?) aerogel

Page 57: Stability of cellulose nanocrystal dispersions and aerogels

Carbonyl region

Celluloseaerogel

PAAm

combined

Page 58: Stability of cellulose nanocrystal dispersions and aerogels

-100

0

100

200

300

400

500

600

700

800

900

1000

0 5 10 15 20 25 30 35

Cou

nts

2 Theta

Poly(allyl amine)/C.CNXL mixture

Control

PAAm mix

Page 59: Stability of cellulose nanocrystal dispersions and aerogels

controly = 1.3677x - 0.0064

R² = 0.9985

PAAm-1y = 1.5689x - 0.0226

R² = 0.9996PAAm-2

y = 1.5701x - 0.0327R² = 0.9995

0.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

0.00 0.05 0.10 0.15 0.20 0.25 0.30

-str

ess,

Mpa

- strain

control

PAAm-1

PAAm-2

15% increase in bulk modulus

Page 60: Stability of cellulose nanocrystal dispersions and aerogels

Conclusions

CNC aerogels have a different diameter than that observed for dried suspensions using AFM or TEM

The aerogel can be chemically modified Acidification in acetone with

trifluoroacetic acid or HCl can hydrolyze the cellulose crystal

Page 61: Stability of cellulose nanocrystal dispersions and aerogels