HWAHAK KONGHAK Vol. 41, No. 3, June, 2003, pp. 337-342

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* 156-756 221

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(2002' 3( 21) *+, 2003' 3( 20) ,-)

A Study on the Characteristics of Tantalum Condenser over the Pyrolysis Temperature of Manganese nitrate by using a Dry-Radiational Furnace

Jae Kun Kim†, Jee Young Yoo*, Hye Kyong Min and Hee Chan Ko**

Partsnic R&D Center, 543 Dangjeong-dong, Kunpo, Kyonggi 435-030, Korea*Department of Chemical Engineering, Chung-Ang University, 221 Huksuk-dong, Dongjak-gu, Seoul 156-756, Korea

Hanwha Group R&D Center, 6 Shinsung-dong, Yusung-gu, Daejeon 305-345, Korea(Received 21 March 2002; accepted 20 March 2003)

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%&'( )*(MnO2) + ,- ./01. 234( TG/DSC 567 8(dehydration)9:

;< 180-230oC $ MnO2 =->?) @ABC 230-250oC $ MnO2 D@E) FAGH IJK L(MN1.

)O PK 200-300oC QR$ 20oC SJK T 3UV*O WX YZ [1 \'& ]^ _

E` abMG cdJC, 240-260oC QR$ e "#$ f'g h ij' ,-) Z801. 30 wt%K k

5e 8l E$ 3m 9: > ! "#$ n]op h SEM 5 WX 67

- q@% r:e )* +) =-MC s t8u :'v, \'_W, fwxy,

z8 -| ,-) ~EMH I) L(MN1.

Abstract − The characteristics of manganese dioxide(MnO2) layer for the solid electrolyte of tantalum condenser formed in

accordance with its pyrolysis temperature by a dry-radiational pyrolysis instead of a traditional wet-convectional pyrolysis of

manganese nitrate was studied. As a result of TG/DSC analysis, manganese nitrate was started to be pyrolyzed at the temper-

ature range from 180 to 230oC through dehydration process and was transformed into MnO2 single phase at the temperature

range from 230 to 250oC. Tantalum pellets were pyrolyzed at intervals of 20oC from 200 to 300oC in a radiational furnace onthe basis of TG/DSC results and then re-anodized. There were nothing particular physical problems on the dielectric layer after

pyrolysis. The condensers pyrolyzed between 240 and 260oC recorded better properties like as a higher withstanding voltage

and a lower leakage current. According to the impedance and SEM analysis results on the tantalum condenser pyrolytically

decomposed 3 times with 30 wt% manganese nitrate aqueous solution, it was verified that uniform and stable manganese diox-

ide layers were formed by a dry-radiational pyrolysis and its properties like as capacitance, dissipation factor, internal resis-

tance and frequency dependency were improved with the increase of the pyrolysis temperature.

Key words: Manganese Dioxide, Tantalum Condenser, Dry-Radiational Furnace, Pyrolysis, Manganese Nitrate

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30 Vìm aL 9 _-(anodizing)B v

5l Z tu(Ta2O5)1 5IJ[11].

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îäÇ / i40 20 dipping5l qrs 9 3ïP |

pore Ï ð+ / i401 Yñò ó 20 [

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B 30 wt% îä5l 34" Z6 E çh Ì

% µk pore Ï9 ð" 40Yñ 'mE D p8

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: ô1 %5IJ. tU ä1 ~5l _-/,

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vimetry: Sinku-Riko, TGD-9S)Î DSC(differential scanning calorimetry:

Sinku-Riko, DSC-9S)B 345l ä5I*, 3[

.(manganese oxide)9 Da$Í6 XRD(x-ray powder diffraction:

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a5I*, 0.6 A9 aB %5l ÏÞ1 fa5E, faÇ Ï

Þ 5 J 0.6 A9 aB %5l 1 ó9 B

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ä1 v5I*, DMB Fig. 1, 2 ]^ 5IJ.

TG ?9 /B /9 [ Ma 100oCB

ë /(Mn(NO3)2-xH2O)9 Di% <ø76 ri ¤1

ø 180-230oC C MnONO3 MnO29 :ù ¤,

230-250oC Äw MnONO3 MnO29 " B

MnO2 »?9 'm6 9 J» ¤1 øÃ6 1

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¤ ¡êx i nJ[7, 8, 10]. DSC ?6 117oC

ri ¤ 56 [ peak% eö *, 197oCÎ 207oC C

:ù [ ¤ 56 2G9 !" [ peak eö

Fig. 1. Thermogravimetry curve of an aqueous solution of manganesenitrate.

41 3 2003 6

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6 ¢%5IJ. ² TG/DSC DM 7-. 200oC

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20oC ù / i409 [ B 5l

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Mn NO3( )2 MnONO3 NO2+→

MnONO3 MnO2 NO2+→

Mn NO3( ) nH2O⋅ Mn NO3( )2 MnONO3 NnO2→+→

Fig. 2. Differential scanning calorimetry of an aqueous solution of man-ganese nitrate.

Fig. 3. X-ray diffraction pattern of the manganese oxide over the pyrol-ysis temperature in the dry-radiational furnace.

Fig. 4. Voltage versus re-anodized time curves of the pyrolyzed tanta-lum pellets in the dry-radiational furnace.

HWAHAK KONGHAK Vol. 41, No. 3, June, 2003

340

-

~5l 25oC, 2.5 wt% /401 345l wet capacitanceB fa

" DM 100µF1 Ö5IJ.

9 <Í`a h Ta2O5 Z tu Ç qrs

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[56 `a1 3 5l qrs ` ÏÑ

ô1 5 5IJ. = <ÊÇ 9 a4

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o5l _-/,-9 lead »B 5E, ÝB v

5l " B $" ë 101-105 Hz 2­i *~

tU ä1 v5IJ. í¨ [ a49 2

­i9º DMB Fig. 5 ]^, 5IJ. 100 Hz 59 2­i

Äw6 ý, [ 50µF a9 ]F" a41 Æ

8 1 kHz ?9 E2­i ow6 [ % ¢%xiÖ

a4 ?o µkm6 DMB eö(J. + 200oC9 çh

120 Hz ? ù+ a4 56 %g [\" 2­i

1 eö(J. 300oC9 çh6 120 Hz ?9 ý, 2­i ow

4 G ?o ¶5* J Íb ] ?

o µ a4 iÃB ÖY% %g hi" 2­i

1 !H5IJ. E [Ç çh Ç

»?9 % µk;% Î ÃC% ¢%" I

Ç DM 7»ÇJ. 240-280oC [Ç çh iÃ9 ï

6 nm¶ ø9 Z3" ¬?1 eö3% z" 2­i

1 eö(J. 6 TG DSC ä " ÝJ 230-250oC

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7»ÇJ. z" 2­i Äw ~?9 '6 Fig. 6 ]^5IJ

. 200oCÎ 220oC9 çh6 103-105 Hz *~ ~? ø9 '5m

96 ç>1 eö/ 8 % µk/iÖ $ ~?

+ m ¢%5I*, + 103-104 Hz ow G%

¬ L6 _?1 eö(J. 300oC9 çh 103-105Hz ow

%g ¬ %ì° ~? 'B eö3% ô ?o

Table 1. Characteristics of tantalum-condenser over the temperature ofpyrolysis after three times of pyrolysis with 30 wt% manganese-nitrate solution

Pyrolysis temperature (oC)

Capacitance (µF) Dissipation factor (%)

120 Hz 1 kHz 120 Hz 1 kHz

200 49.9 26.9 27.8 54.1220 53.0 34.8 21.5 52.3240 49.3 36.1 18.0 39.3260 52.4 38.1 17.2 40.2280 50.0 37.2 16.0 42.2300 51.3 39.3 14.5 40.9

Table 2. Characteristics of tantalum-condenser over the temperature ofpyrolysis after three times of pyrolysis with 30 wt% manganese-nitrate solution

Pyrolysis temperature (oC)

Withstanding voltage (V)

Leakage current (µA)

200 3.5 250220 3.5 407240 3.5-4.0 300260 3.5-4.0 833280 3.5 1,433300 3.0 2,440

Fig. 5. Frequency dependence of capacitance over the pyrolysis temperature in the dry-radiational furnace.

41 3 2003 6

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%g 5E ÃC5 7-*, ² hi"

ô Ê45E n,1 i nJ. z" 2­i *~ Ï vi

Î Mi9 tUB ]^" nyquist plot Fig. 7 5IJ.

ý, [ b ø9 ¬9 1 eöÏ6

Æk / i40 o" 3 [% P 5 &'¼

*, + qrs Ï9 3ïP $Í9 | ` ? /

,-9 wx1 iy56 MnO2% 7' n,1 i nJ. "

9 Ϩ©1 7»x i n6 1 MHz9 E2­i ow9 v

i ©? ý, 9 100 mΩ 59 B iÃB

ÖY% k9 SEM fa DM 7-. 3 [

9 Ç MnO2 ô ]Ö 30 wt%9 / , [ `a

1 »m 3 5Im¶ ` Ï ]^ 5E ÃC5

7-,1 i nJ. [ = ]^ Æ8 % ¢%xi

Ö Ï¨© ÊkmE, å9 G ¢%56 +aÇ ç>1 e

ö(J. 200oC9 çh %g µ Ϩ©M ¶" Mi ¨©9 ¢

%ç>1 eöÏ6 [\" 1 eö/ 8 300oC9 çh Î

o %g hi" 1 eö(J. 6 a49 2­i9º

ä Ï4M Ã56 DMJ. tU DM õ qrs n

'6 NOU(inductance)Î 0OU(reactance)9 Ä> v/

Ê ; B P<5E v< ¨© Ê456 \%åQ¨©

1 fa5E B Fig. 8 5IJ. AR%m 300oC %g h

i" \%åQ¨© 1 eö(J.

Fig. 6. Phase characteristics of tantalum-condensers over the pyrolysistemperature in the dry-radiational furnace.

Fig. 7. Complex plane impedance diagram for tantalum-condensers overthe pyrolysis temperature in the dry-radiational furnace.

Fig. 8. Frequency dependence of equivalent series resistance over thpyrolysis temperature in the dry-radiational furnace.

Fig. 9. SEM photos of the surface of tantalum-condenser after pyrolysis process in the dry-radiational furnace.

HWAHAK KONGHAK Vol. 41, No. 3, June, 2003

342

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T.,

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MnO2 ô ` ÏÑ ÔS5 7' n6 7-

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[ % µk/iÖ â% Êkm* ô m6

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9 ¨2­ ow 200, 220oC [ b9 a4 E2­

i owM6 E [Ç çhÎ =J ïB Æm 9

6 ]Ö MnO2 â% 5m6 ¥5m¶ ?o È â

?× ` Ï Z tu? ô1 &' ¬7' n ;

ç(path)% ?o ¹5l Ϩ© E E2­i

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; 7' 6 @Y o" -wx1 ð+ iy"I

Ç DM 7»ÇJ. " 7» CH3COO-AgB Z%B

âb9 B Í£Y% â9 Î

9 a4 Zúv9 ?B #$" Gotoh \[8]9 DM

B [jñÇJ.

4.

/ i401 Q-3[ KQ 95l [ =

1 <Í5E B qrs E/ 45l

1 %5IJ. Pÿ" /9 TG/DSC XRD ä

DM 100oCB ë ri ¤ Åy7E 180-230oC C

MnONO3 MnO29 ¤ 'e* 230-250oC9

MnO2 »? &'m6 7-J. " Ç

β-MnO29 Da$ÍB \* [ % µ1iÖ

(intensity)% ¢%5IJ. 3 [ B 200, 220, 240, 260, 280,

300oC 5E 9 30 wt%9 / i401 3

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¨© 56 ç>1 eö(J. 6 [ % µk;

² MnONO39 MnO29 % !mE, D MnO29 »?

o" % µk( ?o " /ô1 ¬" I

" 7»ÇJ. a4, Zúv, ÏÞ, =ã

\9 41 ýÒ E" çh 240oC9 [ %

%g Z" eö J. " 30 wt%9 / i401

3 Q-3 [ " 9 çh º9 Q-o [ 9

10-70 wt%9 J_" 15 ? [B " o

] 50%9 4] 10%o9 Zúv1 ÖY `a »

÷9 %1 5IJ.

² >ë Q-3[ KQ1 4" qrs n'

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o" % #$ cd% Åy7'( x 3"ÇJ.

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41 3 2003 6