Shigemi Toda (a) 111117 Action PPT (Rev.4)Tokaicarbon Toda
Transcript of 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.
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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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Chemical shift, (ppm)
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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Chemical shift, (ppm)
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
Conventional 17 mgImproved 16 mg
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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Chemical shift, (ppm)
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
Conventional 17 mgImproved 15 mg
MAS : 5kHz
Spinning side band
Conventional
Improved
BlankThese standardized with sample weight.
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Chemical shift, (ppm)
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
Conventional 17 mgImproved 15 mg
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
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mailto:[email protected],jpmailto:[email protected],jp