2016

CO2 CO2 CO2

2020 50002010 12 17

2600

CO2

20 30 μm1 3 mm

> 15 nm 0.4 nm500 nm

3 nm2 3 μm

70 %30 40

NFC

CNC

CNC

PET

NFC

NFC

NFC

NFC

NFC

NFC

NFC

TEMPO NFC

NFC

NFC

NFC

[NFC]

[CNC]

[MFC]

[CNC]

[ BC]

1990 2000 2010 2011 2012 2013 20140

10000

20000

30000

40000CNT CNF CNC Nanocellulose

CNT

CNT 541,000NFC 42,000CNC 99,200NFC + CNC 142,200

Google Scholar

, 2014

TEMPO

pH 8 10.5TEMPO NaClO NaOH

2

N O

N OH

N O

NaCl NaBrO

NaBrNaClO

OCH2OH

OH

OH

O

OCOOH

OH

OH

OCHO

OH

OH

O

OCOONa

OH

OH

O

NaOH

O

NaClONaBrO

pH 8-10.5

Isogai et al., Nanoscale (2011)

TEMPO

1 g

pH

100 mLTEMPO 0.0125 gNaBr 0.125 g

NaClO 0.4 M NaOH pH 10

TEMPO

TEMPONaClNaBr

pH 6.8

N

O

N

O

Isogai et al., Nanoscale (2011)

3 nm

TOCN

TEMPOpH 10

O

N+

OH

N

TEMPO TOC

100 nmTOCN TEM

TEMPO

TEMPO TOCN

3 nm

TEMPO

COO

Isogai et al., Nanoscale (2011)

20 30 μm1 3 mm

> 15 nm 0.4 nm500 nm

3 nm2 3 μm

70 %30 40

TEMPO

N

O

N

O

TEMPO

20 30 μm1 3 mm

> 15 nm

TEMPO

3 nm2 3 μm

70 %30 40

C6OO Na+

100 101 102 103 104 1051

10

100

1000

TEMPOTOCN

TOCN

nm

CNT

100 nm

TOCN

CNT

woodTOCN

: > 1 mmol/g 1~0.3 mmol/g 0.3~0 mmol/g

Iwamoto et al., Saito et al., Biomacromolecules (2009, 2013)

TEMPO AFMAFM

(nm) (GPa)d (nm)

TOCN272 127 2.6 AFM 3.0

TOCN Kevlar Zylon

AFM 140GPa

145.2 31.3 GPa

[ ] = 0.15 p1.9:

[ ]:p:

p

[]

Tanaka et al., Biomacromolecules (2015)

TOCN

Shimizu et al., Biomacromolecules (2014)

TEMPOCOONa

TEMPOCOOH

TEMPOCOO QA+

TEMPOCOO QA+

TEMPOCOO QA+

QA+OH

QA+OH

pH 2)

Wavelength (nm)

300 400 500 600 700 800

Tran

smitt

ance

(%)

0

20

40

60

80

100

NaNH4

N(Me)4

N(Et)4

N(n-Pr)4

N(n-Bu)4

Time (s)0 2 4 6 8 10

Wat

er c

onta

ct a

ngle

( ° )

0

20

40

60

80

100

120

TOCN-N(n-Bu)4

TOCN-N(n-Pr)4

TOCN-N(Et)4

TOCN-N(Me)4

TOCN-NH4

TOCN-Na

TOCN-RR=

Shimizu et al., Biomacromolecules (2014)

TOCN-QA

TOCN-N(Me)4TOCN-N(n-Bu)4 TOCN-NH4

TOCN-QA

Strain (%)0 3 6 9 12 15 18

Stre

ss (M

Pa)

0

10

20

30

40

Mg2+

Ca2+

Al3+

Fe3+

Wavenumber (cm-1)15001800

TOCN-COOH

H2O

Na+ (original)

Na+

H+

Mg2+

Ca2+

Al3+

Fe3+

–

Counterion

TOCN-COOTOCN-COONa film TOCN-COOM film

aq. HCl or MxCly

Shimizu et al., Journal of Membrane Science (2016)

TOCN Na+ Fe3+ Al3+

TOCN

Wavenumber (cm-1)15001800

TOCN-COOH

H2O

Na+ (original)

Na+

H+

Mg2+

Ca2+

Al3+

Fe3+

–

Counterion

TOCN-COO

RH (%)40 60 80

Oxy

gen

perm

eabi

lity

(mL μm

m-2

kPa

-1 d

ay-1

)

0.01

0.1

1

10

100

1000Na+ (original)H+

Mg2+

Ca2+

Al3+

Fe3+

TOCN-COONa film TOCN-COOM filmaq. HCl or MxCly

TOCNNa+ Ca2+ Al3+

TOCN

Shimizu et al., Journal of Membrane Science (2016)

Filler (%)0 10 20 30 40

E / E

m

1

2

3

4

100 nm1nm 1mm1nm 1mm

f

Fukuzumi et al. Biomacromolecules (2008)

, (10–15 GPa), (200–350 MPa), (6–10 ppm K-1),

TEMPO

40 60 80 1000.000

0.005

0.010

0.015

0.020

0.025

2.7ppm / K

Fukuzumi et al., Biomacromolecules (2009)

TOCN

Fukuzumi et al., Biomacromolecules (2011)

0.0001

0.0010

0.0100

0.1000

1.0000

10.0000

100.0000

1000.0000

PLA TOCNPLA #1

TOCNPLA #2

PEPET

EVOH

EVOH

TOCN (0.8 μm)

PLA (25 μm)

0% RH

0% RH

70% RH

70% RH

TOCN d=0.47nmO2 d=0.34nm

PLA TOCN 0%R.H. 1 500000

(mL μm

/ m

2da

y kP

a)

Kobayashi et a ., Angew. Chem. Int. Ed. (2014)

TOCN / SWCNT

TOCN / SWCNT

TOCN SWCNT

SWCNT Percolation

6% SWCNT/TOCNself-standing filmThickness: ca. 6 μmT600 nm: ca. 30%

Koga et al., Biomacromolecules (2013)

TEMPO

Koga et al., Chem. Commun. (2010)

TEMPOMTM

Wu et al., Biomacromolecules (2012)

TOCN TOCN/MTM-95/5

(g/cm3) 1.5 2.0

(MPa) 210 509

(GPa) 12 18

(%) 3 8

(MJ/m3) 4 26

(mL) 0.03 0.007

TOCN/MTM-95/5

MJ/

m3

TOCN TAC

PEG~3 nm

~25 nm

TOCNTOCN

Soeta et al., ACS Appl. Mat. Interfaces (2015)

TEMPO

Nemoto et al., ACS Appl. Mat. Interfaces (2015)

TOCN dispersionbefore freeze drying

TOCNcontent(g/m2)

Pressure drop (Pa) Particle penetration ratioOriginal base

filterTOCN containing

filter[a]

(10 3%)[b]

(10 3%)[c]

(10 3%)(Reference) 0 305 – 40.1 21.8 6.7Water 0.005 298 298 43.1 19.7 5.0Water 0.015 299 303 36.9 15.4 4.1Water 0.030 299 305 39.6 15.9 4.1Water/TBA [d] 0.005 299 317 9.3 4.5 1.3Water/TBA [d] 0.015 299 329 3.2 1.2 0.3Water/TBA [d] 0.031 300 348 0.4 0.2 0.1

Air filter properties of HEPA-grade base filter and TOCN aerogel-containing filters

TOCN

TOCN

TEMPO

3 nm

TEMPO

3 nm

H+ H2O

Saito et al., Soft Matter (2011), Kobayashi et al., Angew Chem Int Ed. (2014)

- – 80 mV

&

0.4% NaClO, NaBr TEMPO

–COO¯

TEMPO

Isogai et al., Nanoscale (2011)

Sugar composition (%)0 20 40 60 80 100

GlucoseGalactoseMannoseXylose

ArabinoseRhamnoseOthers including uronic acids

TEMPO

Kuramae et al., Reactive & Functional Polymers (2014)

300 400 500 600 700 8000

20

40

60

80

100

B C

TEMPO

nm

%

TEMPO

Tanaka et al., International Journal of Biological Macromolecules (2012)

TEMPO

TEMPO

TEMPO

TEMPO

NO

UTThe University of Tokyo

NEDO

NEDO

(g/m2·24hr at 40°C, 90% RH)0.1 1 10 100 1000

(cc/

m2 ·2

4hr·a

tm a

t 23°

C)

0.01

0.1

1

10

100

1000

10000

OPP LDPE

HDPE

PET

PLA PBS

PHB

EVOH

(g/m2·24hr at 40°C, 90% RH)0.1 1 10 100 1000

(cc/

m2 ·2

4hr·a

tm a

t 23°

C)

0.01

0.1

1

10

100

1000

10000

OPP LDPE

HDPE

PET

PLA PBS

PHB

EVOH

TOCNTOCN

TOCN

100 nm

200 nm

100 nm

MFC

200 kwh / kg

TEMPO

2 kwh / kg

3nm

100 μm

(Gray et al., Cellulose, 1998)

TOCN MFCNCC

Isogai et al., Nanoscale (2011)

NFC CNF

100 μm 100 nm100 nm

50 kwh / kg

TEMPO

TEMPO

CVD

PAN

3 nmμm

10 1000 nm 0.4 70 nm0.5 cm

μm

1.6 g/cm3 1.5 g/cm3 1.4 1.6 g/cm3 1.8 g/cm3

3 GPa 13 150 GPa 2 6 GPa

140 GPa 900 1500 GPa 200 600 GPa

2 kwh/kg 200 400 kwh/kg

60 /kgTOCNXXX / kg

2,000 /kg 10,0003,000,000

/kg

2,000 /kg

3,149

19801991

362,000

1961

2014 6181 70

40

2014 6 2014

2013 100kg TOCNCELLENPIA®

2013 TOCN