Quantitative analysis of oxygen-containing surface functional groups on carbon blacks by solid-state NMR method

Shigemi Toda1, Ryusuke Harada1, Shinichi Makino1, Kouji Miura1, Koichiro Hata2, Yuzo Ohata2, Keiko Ideta3, Jin Miyawaki3, Isao Mochida4, Seong-Ho Yoon2,3
Laboratory, Tokai Carbon Co., Ltd. 2 Interdisciplinary Graduate School of Engineering Sciences, Kyushu University 3 Institute for Materials Chemistry and Engineering, Kyushu University 4 Research and Education Center of Carbon Resource, Kyushu University
1 Chita

Aim of this presentation

1. A carbon black is categorized as one of the traditional carbons. 2. However, the interaction mechanism between the carbon black and rubber is not clear yet. 3. One of the factors is that the surface structure of the carbon black has not been clarified. 4. We think that using various types of surface analysis equipment to clarify the mysterious surface structure of the carbon black enables our research to clarify the interaction mechanism with rubber and to develop new types of carbon black.
2011.11.18 Carbon Black 2011 Asia Pacific Conference

Rubber properties of the improved carbon black and the conventional carbon blacks
CB/Silica=50/50 110 improved 100 conventional 90 80 Abrasion resistance

Rolling resistance 60tan

Wet Grip 0tan

Conventional arbon black= N339

The improved carbon black shows the same physicochemical properties as the conventional carbon black, however, the rubber properties do not.
2011.11.18 Carbon Black 2011 Asia Pacific Conference

Various analysis technique of carbon blacks surface

1. We thought that the difference is related to the carbon black surface.
2. We investigated the surface of the improved and conventional carbon blacks by various analysis techniques.

Quantitation of free water for improved and conventional carbon blacks by TGA Qunatitation of adsorbed water and oxygen functional groups by TGA and TPD-Mass Quantitation of bonding state by NMR
2011.11.18 Carbon Black 2011 Asia Pacific Conference

Quantitation of free water for improved and conventional carbon blacks by TGA
Analysis condition:N2 flow(100cc/min), 10/min, 10mg
Conventional
100 99

Improved
500

100 99

TG Te mp.

TG Te mp.

500

Temperature () Temperature () Temperature ()

400 300

400 300 200 100 0

Temperature () Temperature ()

TG (%)

TG (%)

98 97 96 0

200 100 0 50 100 Time (min) 150

98 97 96 0

50 100 Time (min)

150

Weight lossweight reduction by desorption of free water (Conventional:1.29%, Improved:1.02%). Weight lossweight reduction by desorption of adsorbed water in micro pore or by decomposition of the oxygen functional groups
2011.11.18 Carbon Black 2011 Asia Pacific Conference

Quantitation of absorbed water and oxygen functional groups by TGA and TPD-Mass
Analysis condition:He flow(100cc/min), 10/min, 100mg
Conventional
100 99 0 .0 2
100 99 98 97 96 0 100 200 300 400 0 .0 0 500 0 .0 1

Improved
0 .0 2
TG DTG

TG DTG
0 .0 1

D T G (% / )

T G (% )

98 97 96 0 100 200 300 400

0 .0 0 500

T G (% )

DTG %/

T e m p e ra tu re ( )

T e m p e ra tu re ( )

Elimination of adsorbed water (m/z = 17, 18: H 2O) Elimination of functional groups (m/z = 44: CO 2)

Elimination of adsorbed water (m/z = 17, 18: H 2O) Elimination of functional groups (m/z = 44: CO 2)

m/z=18

Intensity (a.u)

Intensity (a.u)

m/z=18 m/z=44

m/z=44

m/z=17
0 100 200 300 400 500

m/z=17
0 100 200 300 400 500

Temperature ()

Temperature ()

The elimination behaviors of CO2m/z=44 was different.

2011.11.18 Carbon Black 2011 Asia Pacific Conference

Model figure of the carbon black surfaces

The surface structure of the improved and conventional carbon blacks are completely different. We wanted to examine the carbon black surface for more detail.

We focused our attention on analyzing the surface by the NMR equipment.

2011.11.18 Carbon Black 2011 Asia Pacific Conference

The characteristics of NMR equipment

The advantage of NMR
Broadly to determine the structure of organic or inorganic compounds to be obtained from the specific local structural information.
1H-NMR

spectrum
3.00

abundance

HOCH2CH3
1.00 2.05

JEOL JNM-ECX-400
5 4 3 2 1 0
2011.11.18 Carbon Black 2011 Asia Pacific Conference

Chemical shift, (ppm)

Result of 1H SS-NMR (as received CB) 400MHz

Sample Conventional Improved weight 17 mg 16 mg

Echo:128 scans TR:4s Pulse:27us

MAS : 5kHz
Adsorbed water
Intensity (Arb. unit)

Conventional Improved Blank

These standardized with sample weight.

50

40

30

20

10

-10

-20

-30

-40

-50

Chemical shift, (ppm)

2011.11.18 Carbon Black 2011 Asia Pacific Conference

Result of 1H SS-NMR (as received CB) 400MHz

Sample Conventional Improved weight 17 mg 16 mg

Echo:128 scans TR:4s Pulse:27us

Adsorbed water

MAS : 10kHz
Intensity (Arb. unit)

Freelike water

Conventional Improved Blank

These standardized with sample weight.

50

40

30

20

10 0 -10 -20 Chemical shift, (ppm)

-30

-40

-50

2011.11.18 Carbon Black 2011 Asia Pacific Conference

Preparation of D2O adsorbed CB

Two kind of carbon blacks Conventional Improved Dried CB under N2 at 100 Exposed D2O vapper, 96 h Inserted into the cylindertype NMR sample cells
1H

N2 Gas

27

D2O CB

or 2H SS-NMR mesurement
2011.11.18 Carbon Black 2011 Asia Pacific Conference

Result of 2H SS-NMR (D2O ad. CB) 800MHz

Sample Conventional Improved weight 17 mg 15 mg

Single pulse:128 scans TR:4s Pulse:27us

MAS : 5kHz
Intensity (Arb. unit)

Spinning side band Conventional Improved

Blank
50 40 30 20

These standardized with sample weight. 10 0 -10 -20 -30 -40 -50 Chemical shift, (ppm)
2011.11.18 Carbon Black 2011 Asia Pacific Conference

Result of 2H SS-NMR (D2O ad. CB) 800MHz

Sample Conventional Improved weight 17 mg 15 mg

Single pulse:128 scans TR:4s Pulse:27us

MAS : 10kHz
Intensity (Arb. unit)

Conventional Improved Blank

These standardized with sample weight. 10 0 -10 -20 -30 -40 -50 Chemical shift, (ppm)
2011.11.18 Carbon Black 2011 Asia Pacific Conference

50

40

30

20

Conclusion Quantitation of free water for improved and conventional carbon blacks by TGA
Weight reduction by desorption of adsorbed water in micro pore or by decomposition of the oxygen functional groups for the improved carbon black is quite different from the conventional carbon black.

Qunatitation of adsorbed water and oxygen functional groups by TGA and TPD-Mass
The behavior of the elimination of oxygen functional groups for the improved carbon black is quite different from the one for the conventional carbon black.

Quantitation of bonding state by NMR

The adsorbed state on the surface of the improved carbon is different from the one for the conventional carbon black.
2011.11.18 Carbon Black 2011 Asia Pacific Conference

Acknowledgment

This study was partially supported by the NEDO project Innovative Zero-emission Coal Gasification Power Generation Project.

2011.11.18 Carbon Black 2011 Asia Pacific Conference

Please contact

If do you have any question, please give me it by e-mail. Because I am not good at English.
TOKAI CARBON CO., LTD.
No.2 Laboratory Chita Laboratory Shigemi Toda E-mail: stoda@tokaicarbon.co,jp TEL. +81-569-73-6871 FAX. +81-569-72-7481
2011.11.18 Carbon Black 2011 Asia Pacific Conference