Page 1
HWAHAK KONGHAK Vol. 41, No. 4, August, 2003, pp. 479-484
rea
��������/�� � ��� ���� � ����� ��������� ��� �
���†� ���� ��*
������� �����305-600 �� ��� �� 100
*����� ������561-756 �� �� ��� ��� 1� 664-14(2003� 1� 15� !, 2003� 3� 25� "#)
Effect of Poly(phenylene oxide) on Cure Behavior and Fracture Toughness of Poly(phenylene oxide)/Epoxy Blends
Soo-Jin Park†, Hyo-Jin Jeong and Changwoon Nah*
Advanced Materials Division, Korea Research Institute of Chemical Technology, 100 Jang-dong, Yuseong-gu, Daejeon 305-600, Ko*Department of Polymer Science and Engineering, Chonbuk National University,
664-14 1ga Duckjin-dong, Duckjin-gu, Jeonju, Jeonbuk 561-756, Korea(Received 15 January 2003; accepted 25 March 2003)
� �
� ����� 4�� �� � (4EP)� Poly (phenylene oxide) (PPO) ���� ����, � �� ��� ���
� !" #$%&'. PPO� ()� 0, 5, 10, 15, 20 phr* +,'. 4EP/PPO ���-� ����. /�01 234
5 �678�9�: ;< �=+,�, � ��. �2< >�?@(IDT), ��� AB ��� �2 �2< CD?@(IPDT)
� �< �=+,'. �E� ��� � !" �=+� F<� GHA ��" �D+,�, �E� GHI " 78JB
KL�M* 2N+,'. � ��O5, J�P. 5 phr�� Q. R" STUV�, �� W� �X (Ea)� 5 phr�� PPO
� �< ��Y YZ�[\ ]^[� �_" STUV'. ���. 2BU PPO� `a�b� cd* A< PPO� e9f
gYe� hi gY+,'. jk GHA AB(KIC, GIC)� 5 phr�� �2B 8l 2B8f� � Omn� _oM* A
< Yp Q. R" STUV'.
Abstract − In this work, the effect of poly (phenylene oxide) (PPO) in tetrafunctional epoxy resin (4EP) was investigated in
terms of cure kinetics, thermal properties, and mechanical interfacial properties of the blends. The content of PPO was varied
within 0, 5, 10, 15, and 20 phr to neat 4EP. The cure kinetics of 4EP/PPO blend system are examined by near-IR and DSCmeasurements. And the thermal stabilities were determined by initial decomposed temperature (IDT), thermal stability factors,
and integral procedural decomposition temperature (IPDT) of the blends. For the mechanical interfacial properties of the casting
specimens, the fracture toughness test was performed, and their fractured surfaces were examined by SEM. As a result, the con-
version (α) is indicated in high value at 5 phr of PPO and, the cure activation energy (Ea) is decreased at 5 phr PPO, due to the
plasticized PPO polymer molecule in epoxy resins. The thermal stabilities were increased, which can be explained by the presence
of phenyl group of PPO in intermolecular chains. Also the fracture toughness parameters (KIC, GIC) show high values at 5 phr
PPO. This result is interpreted in the development of interfacial adhesion force between intermolecules of the polymer chains.
Key words: Tetrafunctional Epoxy Resin, Poly (Phenylene Oxide), Cure Behavior, Mechanical Interfacial Properties
1. � �
�� ��� ��� � �� ��, ��� ��, �� ���,
���, ��� ��� �� ��� � � !"#, � $� ��%&
�� ��� ��� '(�") *+ ,�-. /� 0 12-� ��
3 45 6��7 � 8 9: ;�<")= > �?� @A�") B
.%� �2� CD8 EF-� !G[1, 2]. > H 3IJ � K�
L�� MN 9O2P� 3QR� SO2P7 T�%U -� VW�@
XK�� )=, 1940YV OZ�� [ \ ]^_, ��� `�, a
���, ��, aX�, a6b� �� %� cdT� �"# K
�efJ 6'`� g�- h�G� i$") @N ]^B, ����,
†To whom correspondence should be addressed.E-mail: [email protected]
479
Page 2
480 ���� ���� ��
jk, lm�� �� Gn� �o3 f�-� !� > pqr s� Y
20%t u�%� !� �(�") H1� Av7 Q %� !� `?�
G[3-5].
we�") 3IJ H �i *+ ,�-� !� xy �z{�
@ diglycidyl ether of bisphenol-A (DGEBA)@|, � DGEBA�
� �}~�� �� ��3=� ��� �? � X��� �� �
. � ��3 ��� �2��y �z{� �G �}� �y �
}~�� � X� ·��� �?� � ,z{� 3IJ @
tetraglycidyl diamine diphenyl methane (TGDDM)� ��{ lm��
� ���� ) ,�%� !G[6-8]. % � ��� � `�3
� �2%� TGDDM�� �y �}~�) @N= ���@ ��3 �
��%� ��/�� ��(hot/wet property)� � �� �$� �
� !. �7 �9%� A� ¡") �@�B7 ,�N= K�J¢
� ¡� £1%G� ¤¥¦ !G.
3IJ 7 �@� J¢� ¡")� 2Q �OO� �§%�
¡� !�| ,�%� `?3 45 �¨[9, 10], ̈ �K? §�[11], X
�p� [12] �") ©ª !G. �i we�@ ¡y «�¬(
) ef� �¨)7 3 ;�%� x@| > L�� ®¯�° ef�
�¨� 3IJ � SO2Pa) �.� K�[ a3= O�+
� w.©U -. B2�'O� T�%U -�| �L�") 3IJ S
O2Pa3 �'-. !� «� ±²� ³´� EF� N%� ²µ
� %U -. 3IJ � �@�� ¶OJ¢U [G. % � �� �
}~�7 ·%J¸ ��� ��� aX�� ·%-� �L� ©¹© �
�{ lm�� ��� B�$") º�%� !G[9, 10]. s� ¨�K?
§�� K �@� »L� � � h"© ��� `�, aX�� ·%
� ¼� i$� � � !. �2� -./G[11]. % � 3IJ� ¨
�K? §�� ½ ~�Q� ��3 ��O .¥¾� !� ¿$� �
� !G[13].
�� �. ÀÀ� XK�� ��� ����3 ��� !� X�p�
�� �'JÁ") �@� »L7 ©¹a� ¡� �2� E
F H@| ��{ à Ä.Å X�p� Æ+Ç@ polysulfone (PSF) [14],
poly (ether sulfone) (PES) [15], poly (ether imide) (PEI) [16], polyimide
(PI) [17]� ,�-� !G. �@� »L7 AN X�p� 7 ÈÉ
Ê µ K �¨© ¨�K? §�3= �ËÌ ¿$� Íl%� �@�
� ¶O JÎ !.= ÏÐ� !�|, > H poly (phenylene oxide)
(PPO)� �Ñ$�� ³� ��3 �T��� �Ò¦ ���y � �
210oC� �y �+����� ��� ��, a���� �� ºy Ó
ÔL ��� �?� %& 3IJ� �@�� ¶OJÎ !�
�Õ� � � !G.
45= Ö �23=� aX�� �y PPO7 ,z{� 3IJ3 <r
×) ÈÉØ%& K�JÙ� � 0 ÈÉØ`� K� ÚÛ � X�Ü�
�� �°��3 PPO� Ýv� ±¶3 VN P,N �ÞG.
2. ���� �
2-1. ��
Ö �23=� ����) tetraglycidyl-4,4'-diamino diphenylmethane
(TGDDM)�� ,z{� 3IJ @ LG��()� LER-430 (E.E.W=
110-130 g/eq, $� 14,000 cps, ~� 1.17 g/cm3)� ,�%�, �@�
B) ,�� X�p� ß5�à@ poly (phenylene oxide) (PPO)� GE
Plastics Korea()3= B�ÐÞG. K�B)� wÖ ÛK�� BZ@
4,4'-diaminodiphenylmethane (DDM, Ñ$=89-91oC, C� p ár
=49.5)� ,�%� PPO� ��)� tetrahydrofuran (THF)� ,�%
ËG. ,�[ TGDDML PPO >+� DDM� ��2P7 Fig. 13 ©
¹aâG.
2-2. ��� ��
Ö lm��� TGDDM� <r� 100") w�%U � � \, PPO
� <r� TGDDM3 V%& 00 0, 5, 10, 15 >+� 20 phr) d�
J¸ ��@ THF3 ã�8 ä@ \ TGDDML K�B7 åm%ËG.
�7 �á� ��3= }eJæ \ � 80oC) � -� E�çè é3
= êë, ì�J¸ íî%� �� �� � �ï �� BÚJÙG. � 3
IJ ÈÉØ`� Airtec, �TB@ Release #19) ð+� \ 80oC)
ñXJæ ò+ó �¨� �+ô") 2�-. !� �T� õØ3 =
=8 ö÷ \ çè3= 150oC(1 h), 180oC(1 h), 200oC(2 h)� K�
,�ø) Jù� K�Jæ Gú 0 �û3 ,�%ËG.
2-3. �� � �
BP� lm��� XK� ��� �û%� A%& JQ,Xr�
(Perkin Elmer DSC-6, DSC)7 ,�%ËG. � 10 mg� J�7 stainless
sample pan3 ü� ~ý%& DSC cell a63 AvJæ \ w�þK %
3= òÿ� EFJ¢� A%& òÿ� EF-� Û� DSC cell a6
) ?p��7 30 ml/min� é�) ��%ËG. Û� DSC òÿy 30
-350oC ���A3= 5, 10, 15, >+� 20oC/min� �Xé�) òÿ
%ËG.
2-4. ��� �
K� ef3 �N g�[ g�`� ̀ +� ��� ��y K���3
�N �� . � ��3 K� ��� �û%� �¡� � H1%
G[18]. 45= Ö K�J��3=� �J�9L H���9 ±²(400-
1,400 cm−1) ,�3= ©¹©� Ó�Ø7 ��%� ���9 ��¡
(near-infrared spectroscopy, NIRS)� MN K�ef� Û_�� ��%
ËG. �3 ,�[ ��� Perstorp Analytical NIR system 6,500�# �
�� �) NIR ���57 ,�%& �û%ËG.
2-5. ��� ��
lm��� X���� ��%� AN= XHr �û�(du Pont,
TGA2950)7 ,�%& ?p �A� %3= 30oC6� 850oC 10oC/
min� ��é�7 � %°= ��O�3 4� Hr� êp7 �û%
ËG.
2-6. ��� ���� � ��� ��
BP[ lm��� ��� �°��� ¤Ò�� AN= ��@� @
Fig. 1. Chemical structures of TGDDM, PPO, and DDM.
���� �41� �4� 2003� 8�
Page 3
PPO/Epoxy �� � � ���� 481
�@ ��f_ ��@�(critical stress intensity factor, KIC)� �� d
T3� �é�(critical strain energy release rate, GIC)7 ��%ËG.
PPO <r×) Jù� 00 BP� \ diamond saw7 ��N= ASTM
D5045-91a3 �%� 52�10�5 mm3� v) Jù� ¿%& 4��
single edge notched bending (SENB) Jù") ��%ËG. V�
Ú+� Jù ���� �(span-to-depth ratio)� 4:1) ��%� cross-
head speed� 1 mm/min") � � ö �{Jÿ ���(#1125, Lloyd
LR 5k, UTM)� ,�%& ��%ËG. ��@� �� \ Jù� �¿
°� z�%� A%& ,���ÝK(JEOL Model 840A, SEM)� ,
�%& �¿ ��� P,%ËG.
3. � ��
3-1. �� � �
K�ef Û_�� �û%� ¡")� IR, UV spectroscopy �
chromatography �� ,�%& �¿�7 ��<") q�Ç ��7
�] ��%� ¡L efrL < z�� !� `+� �?� ��
%& �]�") �û%� ¡� !G[19, 20]. � � ��-� `+�
�?)� �d�, �����, DSC � DTA3 �� DXr� � !
�|, �H DSC� Od� �� `� d� � w� s� � w� �
� ef� Û_�� �2%�| !1%U ,�-. /G. we�")
DSC� Û� K� Û_� �û3� ¿w Û� òÿ[21]L GH Û� ò
ÿ[22-24] � � ¡� !�|, � H3= Û� DSC)6� 2NE
"³� �V ef é�J #.E x�5� �� %3= ��[ Kissinger
b�[23] Û� Û_� @��� ��µ � $� ,�%# by nQ e
f �%Ä&� 4'� �T� �Nb3= ��[ x")= �(�")
b (1)L )� ©¹*G.
(1)
� b3= φ� ��é�, Tm� �V DX ��, A� é� O, Ry
�¬ O >+� Ea� K� C�� 3� 7 ©¹*G. Tmy 0� G
� ��é�3= Û� X�û��)6� �] #� !"#, K� C
�� 3� (Ea)� ln[φ/Tm2] 1/Tm >+,� �-�)6� 2µ !G.
Table 1y ln[φ/Tm2 ]L 1/Tm >+,� �-�� �./")6� K�
C�� 3� � O/� 2%& ©¹* x�G. K� C�� 3�
� TGDDM ¿w P��G PPO7 5 phr ;�%Ë� K C�� 3�
� êp%� K¶� ©¹aâG� PPO� <r� u�<3 45 K
� C�� 3� � GJ u�%� K¶� ©¹aâG. �� K� C�
� 3� � K� efé�3 ³U �0%� ��3 pr� PPO� e
f� 1EJ¸ K� C�� 3� � êp%� x") ô¿-#, > \
PPO� åm") @� �}�3 ±¶� . K� efé�� �-�
ef`� $�� u�%& 10, 15, 20 phr3=� C�� 3� � GJ
u�%� x") z�-. EG.
3-2. ��� ��
���9 ��¡(NIRS)� ��%& K�ef3 �� z{�� d�
7 2@%Ë�, �x")6� K�ef� ��Ô� �û%ËG. 3IJ
� �Õ �@ "³)� � ��� 2P� z�[ ��7 � � !
� 4,000-4,900 cm−1� finger print ±², �<r ��3 ,�-� "³
� K�ef3 3&% h� �� "³� 0�%� 5,000-6,000 cm−1 ±
² >+� '�� ±²@ 7,000 cm−1� !� x") ¤¥¦ !G[18].
�x� �Ö") Ö �23=� PPO <r3 4� lm��� K�
� ·\� ���9 ���û �L7 Fig. 2� 33 ©¹aâ"#, ���
9 �� �û3= ©¹©� �� "³7 Table 23 ©¹aâG.
Fig. 2� TGDDM/PPO ÈÉØ�� K� � ���9 ���4�
©¹* x")= >53= �� 6� )� 3I,�Ø "³�
4,530 cm−1 ±²3= 2@-â"#, � 3I,�Ø�� �JB� e
f%& �þ-. '�7 g�<")= 3QR SO2P7 T�%U
-� x") ¤¥¦ !G[18]. 45= K� \� "³@ Fig. 33=
©¹* 6� )� K�� EF78 � "³� 9:�") êp%U
-�| � ;.Ø� 3I,�Ø °� d�7 �ûN �( ��Ô�
2µ !G. 3I,�Ø °� d�3 �� �( ��Ôy b (2)�
,�%& 2%ËG.
Conversion(α)(%)= �100 (2)
&�= α� ��Ô, Acure� K�[ <ß� 3I,�Ø °� >+�
Auncure� K�� <ß� 3I,�Ø °��G.
φTm
2------ln AR
Ea
--------lnEa
R----- 1
Tm
------⋅–=
1A cure
Auncure
----------------–
Table 1. Cure activation energies (Ea) of TGDDM/PPO blend system
CompositionsKineticfactor
Heating rate (oC/min) Ea
(kJ/mol)5 10 15 20
Pure 4EP 1/Tm (×103) 1-2.34 1-2.25 1-2.19 1-2.15 52.8ln[Φ/Tm
2] −10.49 −9.88 −9.53 −9.28PPO 5 phr 1/Tm (×103) 1-2.38 1-2.26 1-2.21 1-2.16 45.9
ln[Φ/Tm2] −10.47 −9.87 −9.51 −9.27
PPO 10 phr 1/Tm( ×103) 1-2.35 1-2.25 1-2.20 1-2.15 51.5ln[Φ/Tm
2] −10.49 −9.88 −9.52 −9.27PPO 15 phr 1/Tm (×103) 1-2.33 1-2.26 1-2.22 1-2.15 58.2
ln[Φ/Tm2] −10.51 −9.87 −9.50 −9.27
PPO 20 phr 1/Tm (×103) 1-2.35 1-2.29 1-2.23 1-2.18 59.6ln[Φ/Tm
2] −10.49 −9.84 −9.50 −9.25
Fig. 2. Near-IR spectrum of TGDDM/PPO blend system before curing.
HWAHAK KONGHAK Vol. 41, No. 4, August, 2003
Page 4
482 ���� ���� ��
Table 3y b (2)7 ,�N= PPO <r3 4� ��Ô� ©¹* x�
G. �( ��Ôy PPO7 5 phr ;�%Ë� K TGDDM ¿w P�
�G �y 92%� ��Ô� ©¹aG� PPO� <r� u�%° 89%,
87.7%, 87.1%) ��Ôy GJ êp%%� K¶� ©¹=G. �� 3
IJ� �å��@ PPO7 pr ;�%Ë� K �}�3 ±¶� Ð
Ò 3IJ� PPO� ef%& semi-IPN 2P7 T�%U -. > ��
Ô� O�-� x") ô¿[G. % � > �O") ;�%U -°
PPO >2P �3 !� phenyl�) @N ,?�� ÷Û�� ·%J¢
U -� �� �Û�� êp%& ef`� $�� u�%U [G[25].
�L�") 5 phr�O� PPO� K�ef� N%& ��Ô� êpJ
¢� x") z�-. EG.
3-3. �� �
XHr�û(thermogravimetric analysis, TGA)y P�� �û, �Hm
`� �û, X��� �� ��µ !� ¡@|, �8 X�N �J
��(initial decomposition temperature, IDT), �� X�N �� (integral
procedural decomposition temperature, IPDT)� X��� ��3 �
��� �r�@ �û �@�G. � H3= �� X�N ��� �r�
@ X���3 VN= A�%� A%& Doyle3 �N B�[ ��)=
TGA3 �N= #.E 0 °��)6� ©¹a� �r�@ /�� �
�3 X���3 VN � ��� !� ��� ��7 B�N �G�
¤¥¦ !G[26, 27].
IPDT(oC)=A*·K*(T f − Ti)+Ti (3)
&�= A*� TGA� �¬ °�3 V� B9� °����, K*� A*
� �, Ti� C� òÿ���� Tf� �( òÿ��7 ©¹a� x�G.
Fig. 4� TGDDM/PPO ÈÉØ�� TGA B9� ©¹* x�#, �)
6� X�N �J��(IDT), X��� (A*·K*) >+� �� X�
N EF ��(IPDT)7 2%& Table 43 ©¹aâG[27]. Fig. 4� �L
PPO� <r� u�<3 45 TGDDM/PPO ÈÉØ`� X�N í0r
y u�<� 2@µ !â"#, Table 43= �� 6� )� PPO�
<r� u�<3 45 IDT� �,� e° A*·K*� IPDT �� X �
�� @��y u�<� ¤ !âG. �� aromatic ring� �E
TGDDML PPO ��a 0�%� DE>F �� 2P�@ ���L �
�� � aX��")@N ÈÉØ�� a6) �§-� X� Ó
%� X�G 2'� B�%& X���� u�-� x") ô¿[G.
3-4. ��� ����
TGDDM/PPO� P�× Jù3 V� ��� �°��� ¤Ò�� A
N= ³´�i ·H(crack growth resistance)� ©¹a� ��f_��
@�(critical stress intensity factor, KIC)� �� dT3� �é�
(critical strain energy release rate, GIC)7 M%& ¤Ò�ÞG. ��f_
�� @�(KIC)� Jù� TI, ³´� TI >+� ��[ %H/3 4
� ³´ J 6�� f_� OI) =@-� �@� @� H� %©)Â, G
Fig. 3. Near-IR spectrum of TGDDM/PPO after curing.
Table 2. Band assignment for chemical groups from NIR absorptionspectra of cure system
Wavenumber (cm−1) Chemical group
7,000 -OH overtone and combination bands6,067 Firsts overtone of terminal (methylene)
-CH fundamental strtching vibration5,990 Phenyl C-H stretching overtone band5,890 Aromatic CH band5,240 CH2, -CH combination band
Combination band of the conjugated4,682-4,619 C=C stretching with the aromatic
-CH fundamental stretching4,530 Conjugated epoxy CH2 deformation band4,530 Amine group NH2
Table 3. Conversion ratio of TGDDM/PPO blend system
Composites Conversion ratio (%)
0 phr 89.35 phr 92.010 phr 89.015 phr 87.720 phr 87.1
Fig. 4. TGA thermograms of TGDDM/PPO blend system.
Table 4. Thermal stabilities of TGDDM/PPO blend system
Content of PPO IDT [oC]* Tmax [oC] A*·K IPDT [oC] Residual weight [%]
0 phr 375 404.0 0.686 558.7 10.95 phr 378 403.2 0.707 577.7 12.010 phr 378 403.9 0.730 595.1 12.815 phr 376 404.0 0.755 614.8 13.920 phr 376 404.2 0.760 618.4 14.3
���� �41� �4� 2003� 8�
Page 5
PPO/Epoxy �� � � ���� 483
ú b (4))6� > /� 2µ !G[28, 29].
(4)
&�= P� %H, Sy span�� Ú+, B� Jù� ��, w� Jù�
��7 ©¹*G. s� Y� ³´� K�, ³´� Av, %H ¡3 �
0%� geometric factor�# Gú b (5)� )� ©¹L !G.
(5)
&�= a� ³´� K�7 ©¹*G.
s� GIC� «�3� 3�N ³´")6� M)÷ �¿°� T�7
� ³´� �i�+)6� �G-� ¿AK�3 4� 3� 7 �Ý%#
KIC� ~]� z�� !�| � GIC� Gú b (6)� M%& 2µ !G.
(6)
&�= υ� Poisson’s ratio(υN0.35) >+� E� ��@� �� PO
3=� tensile modulus7 ©¹*G.
Fig. 5� TGDDM/PPO ÈÉØ`� 0 P�× Jù3 V� KIC/�
©¹* x�� Fig. 6y GIC �L7 ©¹* x�G. > �L PPO� <
r� 5 phrw �� �°��� �i �y x") ©¹=G. ��[ 6
3 4'° KIC� GIC� �L� ��Ô3 �0��5� ��-. !G
[30]. 45= � �L� P= K�ÚÛ3= Q�� 6� )� PPO7 5
phr ;�%� K 3IJ� PPO ��� ef%& semi-IPN 2P7
T�N DG[ �}2P7 T�%U R3 45 ��� ,? ��,�
� �° �m_� ¶O-U -. ��� �°��� u�-� x")
z�-. EG. % � > �O") ;�7 J3� KIC, GIC /� êp
-� x� z�-â�| �� O�+ �O") @N= ��� �°�
�� ·%-� x") ô¿[G.
3-5. !"#$%� ��&'
TGDDM/PPO ÈÉ�� ��@� Jÿ \ g�[ �¿°� ,��
�ÝK") z�� \ Fig. 73= ©¹aâG. � 3IJ� ��¿°
� ©¹* Fig. 7(a)� K7 �° �S�÷ W°� ©¹a� ³´�
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Fig. 5. Critical stress intensity of TGDDM/PPO blend system. Fig. 6. Critical strain energy release rate of TGDDM/PPO blend system.
Fig. 7. SEM micrograph of TGDDM/PPO blend (a) 0 phr (b) 5 phr (c) 10 phr (d) 20 phr.
HWAHAK KONGHAK Vol. 41, No. 4, August, 2003
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