Collaborators from Chu/Hsiao team: Drs. Y. Su, C. Burger, HY Ma, DF Fang, X Wang, and A. Sato (HS student); Professor BS

HsiaoWork supported by SBU, NSF, NIH, ONR, NSLS

Stony Brook UniversityStony Brook University

Biopolymers-2015Track 6 Biomaterials and Biopolymers

August 11, 2015 14.50-15.10

Structure of Cellulose Nanofibers & its Composite Formation

 

Benjamin Chu1-3 *

Departments of Chemistry1, Materials Science & Engineering2, & Biomedical Engineering3 (affiliated member)

Stony Brook University, Stony Brook, NY 11794-3400 USA

Structure of Cellulose Nanofibers & its Composite Formation

 

Benjamin Chu1-3 *

Departments of Chemistry1, Materials Science & Engineering2, & Biomedical Engineering3 (affiliated member)

Stony Brook University, Stony Brook, NY 11794-3400 USA

Prof. Ben Hsiao

Ying SU

Prof. Christian Burger

Dr. Hongyang Ma

CHU/HSIAO Research Group

Dr. Dufei Fang

Stony Brook UniversityStony Brook University

Xiao Wang

Anna Sato

Message for TodayMessage for Today

1. (a) Take advantage of most abundant sustainable andrenewable materials: Cellulose (crystals) as a basis component.

1. (b) Extraction of Cellulose Nano-fibers & its Characterization

2. (a) Concept 1: Use of Use fibrous format for separation membranes

2. (b) Concept 2: Use nano-fiber/polymer matrix inter-surface as directed water channels for water transport

Long Island Technology Hall of Fame awarded Patent 8,231,013 B2 “Articles Comprising a Fibrous Support” (by Chu, Hsiao, Yoon): the Long Island Patent of the Year Award in the category of Industrial Innovation on March 6, 2013

– one of 3 from 1500 patents

200 nm Fiber

10 m Fiber

Cellulose Fiber (5 nm)

Stony Brook University

Figure courtesy of Dr. Christian Burger.

Plant

Plant cellPlant cell wall

Cellulose fiber

Cellulose microfibril aggregate

Cellulose microfibril/nascent

crystal

Cellulose molecular

chainsWidth 20-30 μmLength 1-3 mm

Width 10-20 nm Width 3-4 nmLength > 2 μm

Hierarchical Structure of Wood BiomassHierarchical Structure of Wood Biomass

Dr. Ying SU

TEMPO-mediated oxidation1,2, pH=10–11TEMPO-mediated oxidation1,2, pH=10–11

Dried pulpDried pulp

Slurry containing oxidized cellulose

fibers

Slurry containing oxidized cellulose

fibers

Cellulose nanofiber suspension

Cellulose nanofiber suspension

Extraction of Cellulose Nanofibers from BiomassSample Description

Biofloc-96Fully bleached sulfite maritime pine wood pulps with

Iα content of 92%

Cotton-7350Dried pulp with viscosity average degree of

polymerization 7350

Bamboo Bleached Kraft-processed bamboo pulp

Jute Vacuum dried bleached jute fibers

TEMALFA-95Fully bleached sulfite spruce wood pulp with Iα

cellulose content of 95%

Cellulose fibril1

Fibril surface

NaClO NaCl

NaBr NaBrO

Centrifugation (2350 g for 10 min) Centrifugation (2350 g for 10 min)

Washing (until pH = 7-8) Washing (until pH = 7-8)

Centrifugation (4700 g for 30 min)Centrifugation (4700 g for 30 min)

Dialysis (6000–8000 MWCO for 192 hours)Dialysis (6000–8000 MWCO for 192 hours)

Sonication (79% outpower (60 Hz, 155 W) for 10 min)Sonication (79% outpower (60 Hz, 155 W) for 10 min)

1 Okita, Saito and A. Isogai, Biomacromolecules, 2010, 11, 1696–17002 Ma, Burger, Hsiao, and B. Chu, Biomacromolecules 2011, 12, 970–976

Solution SAXS/WAXS of Cellulose Nanofibers

Beamline: X9 (NSLS, BNL)Beam wavelength: 0.0885 nmSample-to-detector distance: SAXS: 3.2 m WAXD: 463 mmExposure time: 30 s for each measurement, 3 measurements for each sample

New Collimation New Collimation systemsystem

Advanced Polymers Beam Line, X27C,National Synchrotron Light Source,

Brookhaven National Laboratory, LI, NY

SAXS Characterization of Cellulose Nano-Fibers

Chu, Fang, Mao, Int. J. Mol. Sci. 2015, 16(5), 10016-10037; doi: 10.3390/ijms160510016

Data Correction of SAXS/WAXS patterns

1. Beam center calibration was done using the standard Silver Behenate (d001 = 5.84 nm).

2. Dead pixels and pixels behind the beam stop were blocked off using dark current and mask correction.

3. Water scattering together with capillary scattering were subtracted from the suspension scattering.

Averaged measurement of water

Averaged measurement of suspension

Result after subtraction of water scattering from suspension scattering

s (1/nm)

Inte

nsity

Analysis of SAXS Data – Cylinder Model

Cotton-1320

Cotton-7350

Jute

Biofloc-96

Biofloc-92

Biofloc-920.1 wt%

R0w = 3.6 ± 2.1 nm

Cotton0.1 wt%

R0w = 13.8 ± 8.5 nm

Gaussian distribution

Gaussian distribution

Gamma distribution

SampleWeight

Average (nm)

Biofloc-92 2.2 ± 2

Biofloc-96 3.3 ± 3.2

Cotton-7350 7.9 ± 3.2

Cotton-1320 7.9 ± 3.2

Jute 2.4 ± 2.1

Analysis of SAXS Data – Ribbon Model

Biofloc-96

Weight-average sizes:

aw = 3.2 ± 2.2 nm

bw = 9.5 ± 5.0 nm

aw+ bw = 12.7 ± 5.5 nm

a

ba + b

0.6 wt%

0.3 wt%0.1 wt%

0.05 wt%

Analysis of SAXS Data – Ribbon Model

Cotton-1320

Cotton-7350

Jute

Biofloc-96

Biofloc-92

Ribbon model with Gamma distributions of a and b

Raw Material Size (Weight Average) (nm)

Biofloc-92

aw = 2.2 ± 0.85 nmbw = 6.1 ± 5.3 nm

aw + bw = 8.3 ± 5.4 nm

Biofloc-96

aw= 3.2 ± 2.2 nmbw= 9.5 ± 5.0 nm

aw+ bw= 12.7 ± 5.5 nm

Jute

aw= 2.6 ± 1.6 nmbw= 8.5 ± 4.0 nm

aw+ bw= 11.1 ± 4.3 nm

Cotton-7350

aw= 7.5 ± 4.9 nm bw= 12.9 ± 4.2 nm

aw+ bw= 20.4 ± 6.5 nm

Cotton-1320

aw= 8.6 ± 5.5 nm bw= 12.9 ± 4.2 nm

aw+ bw= 21.5 ± 6.9 nm

a

ba + b

OutlineOutline

1. Structure of Nanofibrous Membrane

Hongyang Ma 2. Microfiltration Membrane

3. Ultrafiltration Membrane

Xiao Wang 4. Nanofiltration Membrane

1. Structure of Nanofibrous Membrane

Hongyang Ma 2. Microfiltration Membrane

3. Ultrafiltration Membrane

Xiao Wang 4. Nanofiltration Membrane

Summary Stony Brook University

Cellulose Nanofiber Coated Ultrafiltration Membrane

Ma, HY.; Burger, C.; Hsiao, BS.; Chu, B. Biomacromolecules, 2011, 12, 970-976.Chu, B.; Hsiao, BS.; and Ma HY. WO 2010/042647; PCT/US09/059884.Ma, HY.; Burger, C.; Hsiao, BS.; Chu, B. Biomacromolecules, 2011, 12, 970-976.Chu, B.; Hsiao, BS.; and Ma HY. WO 2010/042647; PCT/US09/059884.

5 m

500 nm

SEM images of UCN-based UF membrane with barrier layer thickness of ~ 100 nmSEM images of UCN-based UF membrane with barrier layer thickness of ~ 100 nm

Stony Brook University

E-spun Nanofibers

Cellulose Nanofibers

E-spun Nanofibers

Cellulose Nanofibers

Cross-flow Ultrafiltration of Cellulose Nanofiber-based Membrane for Oil/Water Emulsion

Cross-flow Ultrafiltration of Cellulose Nanofiber-based Membrane for Oil/Water Emulsion

Ma, HY.; Burger, C.; Hsiao, BS.; Chu, B. Biomacromolecules, 2011, 12, 970-976.Ma, HY.; Burger, C.; Hsiao, BS.; Chu, B. Biomacromolecules, 2011, 12, 970-976.

0 10 20 30 40 500

100

200

300

400

500

Stony Brook University

Permeation flux of UCN membrane is:11 X higher than that of PAN10 with a comparable rejection ratio, and 2 X higher than that of PAN400 with lower rejection ratio

Permeation flux of UCN membrane is:11 X higher than that of PAN10 with a comparable rejection ratio, and 2 X higher than that of PAN400 with lower rejection ratio

Lower rejection ratioLower rejection ratio

Ultra-fine Cellulose Nanofiber (UCN) Impregnated Microfiltration Membrane

Ultra-fine Cellulose Nanofiber (UCN) Impregnated Microfiltration Membrane

Stony Brook University

500 nm

B. diminata0.3 µm in diameter

0.9 µm long

http://www.hyfluxmembranes.com/http://en.wikipedia.org/wiki/

Microfiltration Membranes for Removal of Bacteria, Viruses and Heavy Metal Ions

SARS100 nmpI = 4.5

Hepatitis A20-30 nmpI = 3 ～ 4

Filtered by Size Exclusion Adsorbed by Charge Interactions

200 nm

200 nm

Most viruses have pI ＜ 7, with negative charges at pH = 7

E. Coli 0.5 µm in diameter

2 µm long2 µm

Most bacteria have sizes over 0.2 µm

As (III), (V)in pesticide and

burning coal

Cr (VI)in dye and paint

Most heavy metal ions have charges and can be interacted via chelating agents

Adsorbed by Charge Interactions &

Chelation

2 µm

Ma, HY.; Burger, C.; Hsiao, BS.; Chu, B. Biomacromolecules, 2012, 13, 180-186.Sato, A.; Wang, R.; Ma, HY.; Hsiao, BS.; Chu, B. J. Electron Microsc., 2011, 60, 201-209.

Ma, HY.; Burger, C.; Hsiao, BS.; Chu, B. Biomacromolecules, 2012, 13, 180-186.Sato, A.; Wang, R.; Ma, HY.; Hsiao, BS.; Chu, B. J. Electron Microsc., 2011, 60, 201-209.

Microfiltration Membrane impregnated with Cellulose Nanofibers

Microfiltration Membrane impregnated with Cellulose Nanofibers

Stony Brook University

E-spun Nanofibers

Cellulose Nanofibers

Sato, A.; Wang, R.; Ma, HY.; Hsiao, BS.; Chu, B. J. Electron Microsc., 2011, 60, 201-209.Sato, A.; Wang, R.; Ma, HY.; Hsiao, BS.; Chu, B. J. Electron Microsc., 2011, 60, 201-209.

Cellulose Nanofibers MF Membrame for Removal of E. Coli by Size Exclusion

Cellulose Nanofibers MF Membrame for Removal of E. Coli by Size Exclusion

E. coli was covered on the surface of microfiltration membrane, and the retention was 99.9999 %.

E. coli was covered on the surface of microfiltration membrane, and the retention was 99.9999 %.

Stony Brook University

Top view after filtrationTop view after filtration

Cross-section view after filtration

Cross-section view after filtration

Ma, HY.; Hsiao, BS.; Chu, B. ACS Macro Lett., 2012, 1, 213-216.Ma, HY.; Hsiao, BS.; Chu, B. ACS Macro Lett., 2012, 1, 213-216.

Cellulose Nanofibers MF Membrame for Removal of Virus and Toxic Metal by Adsorption

Cellulose Nanofibers MF Membrame for Removal of Virus and Toxic Metal by Adsorption

Adsorption capacity of UCN for UO22+ was

167 mg/g;

Adsorption capacity of commercially available activited carbon for UO2

2+ was 57 mg/g.

Adsorption capacity of UCN for UO22+ was

167 mg/g;

Adsorption capacity of commercially available activited carbon for UO2

2+ was 57 mg/g.

UO22+

MS2

Adsorption capacity of UCN MF membrane for MS2 was 99%; 10X

better than Adsorption capacity of commercially available GS9035 for MS2 which

was 90%.

Adsorption capacity of UCN MF membrane for MS2 was 99%; 10X

better than Adsorption capacity of commercially available GS9035 for MS2 which

was 90%.

PSf20 (Sepro), phase-inversioned polysulfone (PSf)

Thin cellulose nanofiber (CN) layer on PAN electro-spun scaffold

Polyacrylonitrile (PAN) electro-spun scaffold

Substrate Ra (nm) Rq (nm) Rmax (nm)

PAN electro-spun 8.93×102 1.18×103 1.19×104

CN 41.6 56.0 5.07×102

PSf 20 6.36 7.87 54.0

Nanofiltration (NF) Membrane Performance as Influenced by Substrates

Nanofiltration (NF) Membrane Performance as Influenced by Substrates

Ra: average roughnessRq: root mean squared roughnessRmax: maximum height of the profile

PA/CN

Electro-spun fibers

TEM image of NF membrane

Schematic of water-channel structure in composite area *

Polyamide

Cellulose nanofibers

* Ma, HY; Burger, C; Hsiao, BS; Chu, B; ACS Macro Lett. 2012, 1, 723−726.

SEM image of NF membrane

Membrane Efficiency Enhanced by Directed Water-Channels

Introduction of directed water channelsIn the barrier layer; CN below the

resolution of SEM.

CN only

CN+PA

PA only

0

20

40

60

80

100

Flux

Rej

ectio

n (%

)

Flux

(LM

H)

80

85

90

95

100

PA(20%BP)/CNPA/CNPA/PSf

Rejection

NF270

10 100 1000

45

50

55

60

65

70

75

80

Flux

Rejc

tion (

%)

Flu

x (L

MH

)

Thinkness of organic phase (m)

90

92

94

96

98

100

Rejection

Membrane Performance Further Enhanced by Slot Die coating

Membrane Performance Further Enhanced by Slot Die coating

Steel plate TrackSlot dieSyringe

pump

bipiperidine (BP)

Membrane Efficiency Enhanced by Slot-Die Coating

Improvement

2004.  

12. Benjamin Chu, Benjamin S. Hsiao and Dufei Fang, “Apparatus and Methods for Electrospinning Polymeric Fibers and Membranes,” issued March 30, 2004, Patent #6,713,011; PCT Int. Appl. WO 0292888.  2008.

17. Benjamin Chu, Benjamin S. Hsiao, Michael Hadjiargyrou, Dufei Fang, Steven Zong and Kwangsok Kim, “Cell Delivery System Comprising a Fibrous Matrix and Cells,” issued January 29, 2008, Patent #7,323,190. 18. Benjamin Chu, Benjamin S. Hsiao, Dufei Fang and Akio Okamoto, “Crosslinking of Hyaluronan Solutions and Nanofibrous Membranes Made Therefrom,” issued January 29, 2008, Patent# 7,323,425.2010.20. Benjamin Chu, Benjamin S. Hsiao, Dufei Fang and Akio Okamoto, “Electro-Blowing Technology for Fabrication of Fibrous Articles and Its Applications of Hyaluronan,” issued February 16, 2010, Patent #7,662,332.2011.

21. Benjamin Chu, Benjamin S. Hsiao and Dufei Fang, “Apparatus for Electro-Blowing or Blowing-Assisted Electro-Spinning Technology and Process for Post Treatment of Electro-spun or Electro-blown Membranes”, US Patent 7,887,311 (2011).22. Benjamin Chu, Benjamin S. Hsiao and Dufei Fang, “Apparatus for Electro-Blowing or Blowing-Assisted Electro-Spinning Technology and Process for Post Treatment of Electro-spun or Electro-blown Membranes”, U.S. Patent 7,934,917 (2011).2012

23-32. Benjamin Chu, Benjamin S. Hsiao, Dufei Fang and Kwang-sok Kim, “High Flux and Low Fouling Filtration Media”, U.S. Provisional Patent Application No. 60/616,592, filed October 6, 2004; PCT Int. Appl. WO 2007001405 (2007), AU 2005333585 (issued by Australia), IN 240572 (issued by India, 2011), - - -, U.S. Patent 8,222,166 (2012).2013

33. Benjamin Chu, Benjamin S. Hsiao and Kyunghwan Yoon “Articles Comprising a Fibrous Support”, filed in SUNY-Stony Brook (R-7925), Docket No. 788-77, U.S. Provisional Application Serial Nos.: 60/872,891 (August 4, 2006) and

60/873,086 (December 06, 2006); or “Articles Comprising a Fibrous Support” U.S. Patent 8,231,013 (2013). Long Island Hall of Fame: Patent of the Year Award in the category of Innovation Industry.

Patents & Patent Applications: 34-58 mostly in separation membranes.

E-Spinning & Membranes: Patents and Patent Applications - ChuE-Spinning & Membranes: Patents and Patent Applications - Chu

$$ $$

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