Shigemi Toda (a) 111117 Action PPT (Rev.4)Tokaicarbon Toda

8/3/2019 Shigemi Toda (a) 111117 Action PPT (Rev.4)Tokaicarbon Toda

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Quantitative analysis of oxygen-containing

surface functional groups on carbon blacksby 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

1

Chita Laboratory, Tokai Carbon Co., Ltd.2 Interdisciplinary Graduate School of Engineering Sciences, Kyushu University3 Institute for Materials Chemistry and Engineering, Kyushu University

4 Research and Education Center of Carbon Resource, Kyushu University


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Aim of this presentation

1. A carbon black is categorized as one of thetraditional carbons.

2. However, the interaction mechanism between thecarbon black and rubber is not clear yet.

3. One of the factors is that the surface structure ofthe carbon black has not been clarified.

4. We think that using various types of surface

analysis equipment to clarify the mysterioussurface structure of the carbon black enables ourresearch to clarify the interaction mechanism withrubber and to develop new types of carbon black.

2011.11.18 Carbon Black 2011 Asia Pacific Conference


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Rubber properties of the improved carbon black

and the conventional carbon blacks

The improved carbon black shows the same physico-chemical properties as the conventional carbon black,

however, the rubber properties do not.

Conventional arbon black= N339



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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 andconventional carbon blacks by TGA

Qunatitation of adsorbed water and oxygenfunctional groups by TGA and TPD-Mass

Quantitation of bonding state by NMR



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Quantitation of free water for improved and

conventional carbon blacks by TGA

Weight loss weight reduction by desorption of free water(Conventional:1.29%, Improved:1.02%).

Weight loss weight reduction by desorption of adsorbed water inmicro pore or by decomposition of the oxygen functional groups

Analysis condition:N2 flow(100cc/min), 10 /min, 10mg

TG

Temp.

TG

Temp.

TG

Temp.

TG

Temp.

TG

Temp.



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Quantitation of absorbed water and oxygen functional

groups by TGA and TPD-MassAnalysis condition:He flow(100cc/min), 10 /min, 100mg

T G

D T GT G

D T G

The elimination behaviors of CO2 m/z=44 was different.2011.11.18 Carbon Black 2011 Asia Pacific Conference


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Model figure of the carbon black surfaces

The surface structure of the improved and conventional carbonblacks 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


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The characteristics of NMR equipment

JEOL JNM-ECX-400

3.

00

2.

05

1.

00

Chemical shift, (ppm)

abundance

012345

HO CH2 CH3

1H-NMR spectrum

The advantage of NMR

Broadly to determine the structure oforganic or inorganic compounds to be

obtained from the specific local structural

information.



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Intensity(Arb.unit)

-50-40-30-20-1001020304050

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

MAS : 5kHz

Echo:128 scans

TR:4sPulse:27us

Sample weight

Conventional 17 mgImproved 16 mg

Adsorbed water

Conventional

Improved

Blank

These standardized with sample weight.



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Inte

nsity(Arb.unit)

-50-40-30-20-1001020304050

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

Echo:128 scans

TR:4sPulse:27us

Sample weight


MAS : 10kHz

Adsorbed water

Freelike water

Conventional

Improved

Blank

These standardized with sample weight.



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Preparation of D2O adsorbed CB

Two kind of carbon blacks

ConventionalImproved

Exposed D2Ovapper, 96 h

Inserted into the cylinder-type NMR sample cells

1H or 2H SS-NMR mesurement

D2O CB

27

N2 GasDried CB under

N2 at 100



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Intensity(Arb.unit)

-50-40-30-20-1001020304050

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

Single pulse:128 scans

TR:4sPulse:27us

Sample weight


MAS : 5kHz

Spinning side band

Conventional

Improved

BlankThese standardized with sample weight.



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Inten

sity(Arb.unit)

-50-40-30-20-1001020304050

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

Single pulse:128 scans

TR:4sPulse:27us

Sample weight


MAS : 10kHz

Conventional

Improved

BlankThese standardized with sample weight.



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Conclusion

Quantitation of free water for improved and

conventional carbon blacks by TGAWeight reduction by desorption of adsorbed water in micropore or by decomposition of the oxygen functional groupsfor the improved carbon black is quite different from theconventional carbon black.

Qunatitation of adsorbed water and oxygenfunctional groups by TGA and TPD-MassThe behavior of the elimination of oxygen functionalgroups for the improved carbon black is quite different

from the one for the conventional carbon black.

Quantitation of bonding state by NMRThe adsorbed state on the surface of the improved carbonis different from the one for the conventional carbon black.



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Acknowledgment

This study was partially supported

by the NEDO project InnovativeZero-emission Coal Gasification

Power Generation Project.



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Please contact

If do you have any question, pleasegive 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: [email protected],jp

TEL. +81-569-73-6871

FAX. +81-569-72-7481

mailto:[email protected],jpmailto:[email protected],jp

Shigemi Toda (a) 111117 Action PPT (Rev.4)Tokaicarbon Toda

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