New Thermal l y Remendabl e Hi ghl y Cross-Li nked Pol ymeri c Materi al s

Xiangxu Chen,

Fred Wudl,*
,
Ajit K. Mal,

Hongbin Shen,

and Steven R. Nutt

Department of Chemistry and Biochemistry and Exotic Materials I nstituteand Department of

Mechanical and AerospaceEngineering, University of California, Los Angeles, California 90095, and
Department of Materials Science, University of Southern California, Los Angeles, California 90089
Received J uly 8, 2002; Revised Manuscript Received December 19, 2002
ABSTRACT: Two new remendabl e hi ghl y cross-l i nked pol ymers, 2ME4F and 2MEP4F, were prepared
wi thout sol vent. Sol i d-state NMR (nucl ear magneti c resonance) was used to study the thermal reversi bi l i ty
of Di el s-Al der (DA) cross-l i nki ng, and i t was found that DA connecti ons and di sconnecti ons of both
pol ymers are thermal l y reversi bl e. Di fferenti al scanni ng cal ori meter and dynami cal mechani cal anal ysi s
were appl i ed to study thermal and mechani cal properti es of these materi al s, and i t i s found that the
gl ass transi ti on temperature (T
g) of 2ME4F i s about 30-40 C and that of 2MEP4F i s about 80 C. A
qual i tati ve study of the heal i ng effi ci ency of 2MEP4F showed that cracks can be heal ed effecti vel y wi th
a si mpl e thermal heal i ng procedure. Thi s process can be repeated to heal cracks mul ti pl e ti mes.
Introduction
Duri ng past decades, hi ghl y cross-l i nked pol ymers
have been wi del y studi ed as matri ces for composi tes,
foamed structures, structural adhesi ves, i nsul ators for
electronic packaging, and other applications.
1
The densely
cross-l i nked structures are the basi s of superi or me-
chani cal properti es such as hi gh modul us, hi gh fracture
strength, and sol vent resi stance. Though these are
commendabl e properti es, hi ghl y cross-l i nked pol ymeri c
engi neeri ng materi al s are al so notori ous for thei r bri ttl e-
ness and propensi ty to crack. The ul ti mate cause of
fai l ure of al l structural materi al s i s due to i ni ti ati on and
growth of cracks, often hi dden wi thi n the bul k and
ul ti matel y l eadi ng to thei r catastrophi c fai l ure.
2
A substanti al effort has been spent to fi nd effecti ve
ways for crack-heal i ng of pol ymeri c materi al s duri ng the
past decades.
3
Based on the mechani sm of l i near
pol ymer chai n i nterpenetrati on at i nterfaces, techni ques
of crack-heal i ng of l i near pol ymers have been wel l
establ i shed, such as hot pl ate wel di ng and smal l mol -
ecul e i nduced crack-heal i ng.
4
However, crack-heal i ng of
cross-l i nked pol ymers i s sti l l a fai rl y new research fi el d.
Crack-heal i ng of a composi te of l i near pol ymer and
thermoset was reported.
5
However, onl y 1.7% of the
fracture energy was recovered after anneal i ng of frac-
tured sol i d i nterfaces wi thout any surface treatment or
new monomers. Several years ago, the concept of sel f-
repai r was i ntroduced to heal cracks by embeddi ng
hol l ow fi bers that can rel ease repai r chemi cal s when a
crack propagates.
6
I n 2001, the crack sel f-heal i ng abi l i ty
of an epoxy resi n composi te was reported by Whi te et
al ., consi sti ng of a cl ever use of a catal yti c network
formati on of an encapsul ated add-monomer, whi ch i s
hel d wi thi n a capsul e embedded i n the epoxy matri x.
7
However, i t was not cl ear how effi ci ent mul ti pl e sel f-
heal i ng was.
Retro-Di el s-Al der cycl oaddi ti ons have been studi ed
for decades.
8
Si nce the earl y days of the appl i cati on of
the Di el s-Al der (DA) cycl oaddi ti on to the synthesi s of
thermal l y reversi bl e cross-l i nked pol ymers,
9
many stud-
i es have been reported i n thi s area.
10,11
Reversi bl y cross-l i nked pol ymers usi ng the retro-DA
reacti on have been reported by Smal l , Loy, and thei r
col l eagues.
11
For thei r appl i cati on of debondi ng adhe-
si ves, l i qui d monomers were requi red, and Si -O-C
bonds are essenti al to achi eve l i qui ds at room temper-
ature. However, i t i s wel l -known that Si -O-C bonds
are suscepti bl e to aci d- or base-catal yzed hydrol ysi s,
13
and potenti al l y bi odegradabl e pol ymers have been
reported recentl y based on thi s feature of Si -O-C
bonds.
14
Furthermore, onl y soft materi al s, wi th Youngs
modul us of 29-36 MPa and compressi ve strength of l ess
than 1 MPa,
11c
were reported, whi ch are not sui tabl e
for engi neeri ng materi al s.
I n our previ ous work,
12
the concept of debondabl e
adhesi ves
11
was taken one step further, and a remend-
abl e pl asti c was reported. I t was found that the energy
to break DA adducts i s much l ower than that to break
al l the other coval ent bonds, and the retro-DA reacti on
was found responsi bl e for crack propagati on. When the
sampl e was reheated, the furan and mal ei mi de moi eti es
were found to reconnect agai n and the cracks heal ed or
fractures mended. On the basi s of thi s concept, a
transparent organi c pol ymeri c materi al was devel oped
that coul d repeatedl y mend or remend i tsel f under
mi l d condi ti ons. The i ntermonomer l i nkages were
formed by DA cycl oaddi ti ons that di sconnected upon
heati ng to 120 C and above and reconnected upon
cool i ng. I t was found that thi s process was ful l y revers-
i bl e and coul d be used to restore a fractured part
mul ti pl e ti mes, and i t di d not requi re addi ti onal i ngre-
di ents such as a catal yst, addi ti onal monomer, or speci al
surface treatment of the fractured i nterface. At the end
of that paper, we suggested that a col orl ess mal ei mi de
monomer and a process to make pol ymeri c materi al s
wi thout sol vent (the methyl ene chl ori de) woul d be
essenti al features of the next generati on of thi s type of
pol ymeri c materi al .
I n thi s work, we report two remendabl e cross-l i nked
pol ymeri c materi al s based on thermal l y reversi bl e DA
cycl oaddi ti on. These materi al s are hard, colorless, and
transparent at room temperature and do not requi re
sol vent for the pol ymeri zati on processes.

Department of Chemi stry and Bi ochemi stry and Exoti c Ma-

teri al s I nsti tute, UCLA.

Department of Mechani cal and Aerospace Engi neeri ng, UCLA.

Uni versi ty of Southern Cal i forni a.

* To whom correspondence shoul d be addressed.
1802 Macromolecules 2003, 36, 1802-1807
10.1021/ma0210675 CCC: $25.00 2003 Ameri can Chemi cal Soci ety
Publ i shed on Web 02/15/2003
Experimental Section
Furan monomer (4F) was synthesi zed as descri bed i n the
Supporti ng I nformati on of our previ ous work.
12
Monomer 1,8-
bi s(mal ei mi do)-3,6-di oxaoctane (2ME) was synthesi zed ac-
cordi ng to the l i terature.
15
Al l other reagents, exo-3,6-epoxy-
1,2,3,6-tetr ahydr ophthal i c anhydr i de, di methyl for mami de
(DMF), Ac
2O, Et3N, Ni (OAc)24H2O, SOCl 2, CH2Cl 2, tol uene,
pyri di ne, and furfuryl al cohol , were purchased from Al dri ch,
Fi sher, or Acros and used wi thout puri fi cati on.
El emental anal ysi s was provi ded by Desert Anal yti cs (Tuc-
son, AZ). Sol uti on NMR spectra were obtai ned on a Bruker
400 MHz NMR i nstrument. The sol i d-state NMR spectrum
was obtai ned on a Bruker Avance 300 NMR i nstrument.
Di fferenti al scanni ng cal ori meter (DSC) data were obtai ned
on a Thermal Anal ysi s MDSC 2920 wi th scan rate of 10 C/
mi n. Dynami c mechani cal anal ysi s (DMA) data were obtai ned
on a TA I nstrument DMA 2980 wi th scan rate of 1 C/mi n
and frequency of 1 Hz. The ul trasoni c testi ng was performed
i n accordance wi th ASTM E494-95 at a frequency of 5 MHz
wi th a Compuscope 8012 12 bi t A-D 100 Megasampl e/second
two-channel card wi th a Matek I nstruments TB-1000 Gated
Ampl i fi er Toneburst card. Compressi on testi ng was performed
accordi ng to the ASTM D695 protocol on an I nstron Fl oor
Model (TT). A Hopki nson bar test was al so conducted to obtai n
compressi on data accordi ng to the condi ti ons and procedures
descri bed i n the l i terature
17
wi th 0.5 i n. di ameter bars
(desi gned and bui l t at the Uni versi ty of Cal i forni a, San Di ego,
by Prof. Nemat-Nasser and J. I saacs) and a Ni col et 4094B data
acqui si ti on system. Compact tensi on speci mens wi th a dri l l ed
hol e were used to obtai n cri ti cal l oad data. Testi ng was
performed on an I nstron model 5544 usi ng a crosshead speed
of 0.1 mm/mi n, and speci mens were hel d i n pl ace by C-cl amps
duri ng testi ng. Al l mechani cal tests were performed at 24 ( 1
C. Duri ng crack-heal i ng, speci mens were hel d i n pl ace wi th
a 1-i n. hose cl amp. The cl amp pressure was i nsi gni fi cant,
suffi ci ent onl y to prevent l ateral di spl acement of the fracture
surfaces.
Synthesis of 1,8-Bis(maleimido)-1-ethylpropane
(2MEP). To a sol uti on of 36 g (0.37 mol ) of mal ei c anhydri de
and 70 mL of N,N-di methyl formami de (DMF) i n a 500 mL
three-neck round-bottom fl ask wi th magneti c sti rri ng, 20 mL
(0.17 mol ) of Dytek-EP (Al dri ch) was added dropwi se. The
temperature of the sol uti on was kept bel ow 85 C. Sti rri ng
was conti nued for 2 h after addi ti on at 75 C. Then, 64 mL of
aceti c anhydri de, 8 mL of tri ethyl ami ne, and 0.4 g of ni ckel
acetate tetrahydrate were added i n one porti on to the sol uti on.
Sti rri ng was conti nued for about 2 h at 80 C. Water (100 mL)
was added, and the sol vent was di sti l l ed under vacuum at 60
C. The resi due was redi ssol ved i n 500 mL of CH
2Cl 2 and
washed wi th H2O (3 300 mL). The organi c l ayer was
col l ected and shaken wi th about 200 g of si l i ca gel . The sol vent
from the fi l tered sol uti on was evaporated, and the resi due was
puri fi ed by chromatography on a short si l i ca gel col umn usi ng
ethyl acetate as sol vent. The sol vent was removed on a rotary
evaporator, and crystal l i zati on from 50% ethyl acetate and
50% hexane was carri ed out to afford whi te crystal s (21 g,
42%); mp 82-84 C.
1
H NMR (CDCl 3): 6.61 (4H, s); 3.76-3.3
(3H, 3m); 2.19-1.56 (4H, 4m); 0.70 (3H, t).
13
C NMR (CDCl 3):
171.09; 170.59; 134.08; 133.85; 50.32; 34.88; 29.97; 25.58;
10.78. FT-I R: 3102; 1705; 1407; 1189 cm
-1
. UV-vi s: 237; 296
nm. El emental anal ysi s: Cal cd: C, 59.52; H, 5.38; N, 10.6.
Found: C, 59.68; H, 5.38; N, 10.38.
Synthesis of Polymer 2ME4F. A typi cal procedure i s as
fol l ows: 1.004 g (1.35 mmol ) of monomer 4F and 0.831 g (2.76
mmol ) of monomer 2ME (powder) were mi xed together i n a
gl ass test tube. Ai r trapped i nsi de was removed by vacuum.
The mi xture was then heated to 125 C on a si l i con oi l bath
for about 20 mi n. The sol i d di ssol ved i nto the l i qui d i n about
5 mi n. The resul ti ng gel was then cool ed to about 40 C i n 12
h to obtai n a col orl ess, transparent materi al .
Synthesis of Polymer 2MEP4F. A typi cal procedure i s
as fol l ows: 7.154 g (9.61 mmol ) of monomer 4F and 5.038 g
(19.21 mmol ) of monomer 2MEP (powder) were mi xed together
i n a gl ass test tube. Ai r trapped i nsi de was removed by
vacuum. The mi xture was then heated to 115 C i n a si l i cone
oi l bath for about 20 mi n. The sol i d di ssol ved i nto the l i qui d
i n about 3 mi n. The resul ti ng gel was cool ed to about 40 C i n
12 h to obtai n a transparent, col orl ess materi al .
Results and Discussion
Chart 1 depi cts three monomers used i n thi s and
previ ous work. Mal ei mi de monomer 3M and furan
monomer 4F were used to make pol ymer 3M4F i n our
previ ous work.
12
Mal ei mi de compounds usual l y have
hi gh mel ti ng poi nts. The tri s(mal ei mi de) reported i n our
previ ous work,
12
3M, has a mel ti ng poi nt of 113 C.
Because of thei r hi gh mel ti ng poi nts, mal ei mi de mono-
mers are di ffi cul t to di ssol ve i n furan monomers. I n our
previ ous work,
12
the mal ei mi de monomer was di ssol ved
i n methyl ene chl ori de fi rst, and the sol vent was evacu-
ated after mi xi ng wi th the furan monomer. However,
pol ymeri zati on starts as soon as sol vent i s bei ng re-
moved, and resi dual sol vent i n the materi al makes the
processi ng procedure di ffi cul t. To avoi d the necessi ty of
di l uents, l ow mel ti ng poi nt mal ei mi de deri vati ves were
requi red. Even though Si -O bonds were previ ousl y used
to obtai n l ow mel ti ng mal ei mi de compounds,
11,13
as
menti oned i n the I ntroducti on, the hydrol yti c stabi l i ty
i s margi nal , and the sti ffness of the resul ti ng materi al
fal l s short of common engi neeri ng pol ymeri c materi al s.
Several mal ei mi de compounds have been reported i n
the l i terature.
15
I n thi s work, mal ei mi de monomer 2ME
and 4F were used to make pol ymer 2ME4F and
mal ei mi de monomer 2MEP (shown i n Scheme 1) and
4F were used to synthesi ze 2MEP4F. Wi th ethyl ene-
di oxy uni ts, compound 2ME has a mel ti ng poi nt of 92
C, whi ch i s much l ower than that of the tri s(mal ei mi de)
3M (mp 113-114 C). As shown i n Scheme 1, a bi s-
(mal ei mi de) wi th a branch and potenti al chi ral center,
2MEP, was synthesi zed, and the mel ti ng poi nt was
found to be as l ow as 82 C, even though there are onl y
three bri dge carbons. Both of these two bi s(mal ei mi de)
compounds were mi xed wi th l i qui d furan monomer (4F)
and heated to about 20-30 C above thei r mel ti ng
poi nts. Both materi al s can be processed i n the pregel
as wel l as i n the gel state, and hard pol ymers are formed
upon cool i ng.
Sol i d-state
13
C NMR spectra of pol ymer 2ME4F and
2MEP4F, as a functi on of thermal cycl i ng, are shown
i n Fi gures 1 and 2. I n our previ ous work,
12
i t was shown
that unreacted or di sconnected furan uni ts have
13
C
NMR peaks at chemi cal shi fts of ca. 111 and 150 ppm
whi ch shi ft to l ower val ues upon cycl oaddi ti on. These
resul ts are of di agnosti c val ue to moni tor the change of
Chart 1
Scheme 1. (i) DMF; (ii) DMF, Acetic Anhydride,
Triethylamine, Nickel Acetate Tetrahydrate
Macromolecules, Vol. 36, No. 6, 2003 Cross-Li nked Pol ymeri c Materi al s 1803
cross-l i nki ng. As shown i n Fi gures 1a and 2a, there are
two smal l peaks at ca. 111 and 150 ppm resonances on
both spectra, whi ch means that most furan uni tes have
reacted i n the current pol ymeri zati on process for both
2ME4F and 2MEP4F. The reason for the resi due of
furan uni ts mi ght be that DA cycl oaddi ti on happens as
soon as mal ei mi de compounds di ssol ve i n the furan
compound, and the mi xture i s not as homogeneous as
the one formed wi th the hel p of a sol vent. The revers-
i bi l i ty of both pol ymers was al so studi ed by sol i d-state
13
C NMR. For 2ME4F, the pol ymer was heated to 130
C for 25 mi n, fol l owed by quenchi ng i n l i qui d ni trogen
to produce a materi al wi th the sol i d-state
13
C NMR
spectrum shown i n Fi gure 1b. Pol ymer 2MEP4F was
heated to 140 C for 25 mi n, fol l owed by quenchi ng i n
l i qui d ni trogen, and the sol i d-state
13
C NMR spectrum
of the product i s shown i n Fi gure 2b. I t i s cl ear that i n
both Fi gure 1b and Fi gure 2b the i ntensi ty of the ca.
111 and ca. 150 ppm resonances are now much hi gher,
i ndi cati ng more of unreacted furan moi eti es. Further-
more, the i ntensi ty of the two peaks for mal ei mi de
carbonyl groups changes. After heati ng and quenchi ng,
the peak at hi gher fi el d, 172 ppm, whi ch bel ongs to
unreacted mal ei mi de carbonyl s,
12
i ncreases. Thi s i ndi -
cates that there are many more unreacted mal ei mi de
moi eti es. The same sampl es were heated to 90 C and
cool ed to 30 C i n 6 h to repol ymeri ze. Thei r sol i d-state
13
C NMR spectra are shown i n Fi gures 1c and 2c. Si nce
the l atter are essenti al l y i denti cal to the spectra i n
Fi gures 1a and 2a, respecti vel y, the si mpl est i nterpreta-
ti on demands that di sconnected l i nkages had recon-
nected, whi ch was al so observed i n our previ ous work.
12
Mechani cal properti es of these two pol ymers have
been tested at room temperature and are shown i n
Tabl e 1, together wi th data for pol ymer 3M4F.
12
For
al l three pol ymers, the densi ti es are between 1.31 and
1.37 g/cm
3
, and Poi sson rati os are al so very si mi l ar, from
0.32 to 0.37. The mechani cal properti es of 2MEP4F are
l ower than, but cl ose to, those of 3M4F. Youngs
modul us of 2MEP4F i s as hi gh as 4.41 GPa, and the
speci fi c strength i s as hi gh as 180 MPa. Both of these
are si mi l ar to, or hi gher than, those of wi del y used epoxy
resi ns and unsaturated pol yesters
12
whose typi cal
Youngs modul us are i n the range of 2-4 GPa and
compressi on stresses are 80-200 MPa. However, the
mechani cal properti es of 2ME4F are weaker than those
of 3M4F and 2MEP4F. A reasonabl e conjecture for thi s
resul t i s the presence of the ethyl enedi oxy soft uni t i n
monomer 2ME. The Youngs modul us and compressi ve
strength of 2ME4F and 2MEP4F are about 2 orders of
magni tude hi gher than those reported i n si l i con-based
DA pol ymers.
11c
The speci fi c modul us (modul us di vi ded
by densi ty) of 2ME4F and 2MEP4F (3.40 and 3.16
GPa/(g cm
3
), respecti vel y) are about 15 ti mes hi gher
Figure1. Sol i d-state
13
C NMR of 2ME4F: (a) ful l y pol ymeri zed; (b) sampl e of (a) heated to 130 C and then quenched i n l i qui d
ni trogen; (c) sampl es of (b) heated to 80 C and then cool ed to room temperature.
Table 1. Mechanical Testing of Polymer 2MEP4F and
3M4F
3M4F 2MEP4F 2ME4F
ul trasoni c densi ty (g/cm
3
) 1.34 1.31 1.33
testi ng Poi sson rati o 0.32 0.36 0.37
Youngs modul us (GPa) 4.70 4.41 3.6
compressi on Youngs modul us (GPa) 4.55
a
4.14
a
3.4
b
testi ng speci fi c modul us
(GPa/(g cm
3
))
3.40 3.16
ul ti mate tensi l e (MPa) 241
a
234
a
strai n to fai l ure (%) 25
a
24
a
strength at yi el d (MPa) 121
b
116
b
a
Hopki nson bar testi ng.
b
ASTM D695.
1804 Chen et al . Macromolecules, Vol. 36, No. 6, 2003
thanthe materi al s reported i n ref 11c (ca. 0.22 GPa/
(g cm
3
)).
To test the thermal properti es of both pol ymers,
di fferenti al scanni ng cal ori metry (DSC) and dynami c
mechani cal anal ysi s (DMA) were carri ed out. The DSC
resul ts of 2ME4F and 2MEP4F are shown i n Fi gure
3. I t can be seen that the DSC curve of pol ymer 2ME4F
has three transi ti ons that start at 21, 93, and 120 C.
The l ower transi ti on at 21 C mi ght be due to the
movement of ethyl enedi oxy segments. Al so as shown i n
Fi gure 3 are onl y two transi ti ons at about 86 and 120
C for pol ymer 2MEP4F. The transi ti ons that start at
110-120 C have al ready been assi gned to be the retro-
DA cycl oaddi ti ons.
12
DMA resul ts are shown i n Fi gure 4. I n Fi gure 4a, i t
can be seen that even though the storage modul us of
2ME4F at 30 C i s as hi gh as 2.87 GPa, i t starts
droppi ng at that temperature, i ndi cati ng that the mate-
ri al starts softeni ng and the tan peak shows at 59 C.
Thi s resul t matches previ ous DSC data, whi ch al so show
a transi ti on at around 20-30 C. From Fi gure 2b, i t can
be seen that storage modul us of 2MEP4F starts at 4.46
GPa. The onset poi nt of gl ass transi ti on i s at about 78
C and the peak of tan shows at 95 C, whi ch al so
matches previ ous DSC data, wi th a transi ti on at about
86 C. For compari son, DMA resul ts of 3M4F are shown
i n Fi gure 2c. I t can be seen that the transi ti on al so
starts at about 84 C, and the peak of tan appears at
100 C.
Regardi ng the heal i ng/mendi ng effi ci ency of both
pol ymers, pol ymer 2ME4F softens and can be remol ded
at 160 C, whi l e pol ymer 2MEP4F exhi bi ts the same
behavi or at a temperature above 180 C. However, the
quanti tati ve study of heal i ng effi ci ency of pol ymer
2ME4F was not successful because the shape of the
speci mens changed before i t reached the heal i ng tem-
perature. To determi ne the fracture-mendi ng effi ci ency
of pol ymer 2MEP4F, tests were performed usi ng com-
pact tensi on test speci mens.
16
I n our previ ous work,
12
speci mens fractured (fai l ed) i nto two pi eces. The resul t-
i ng pi eces were hel d together wi th a si mpl e hose cl amp
to heal /mend the crack. However, i t was essenti al l y
i mpossi bl e to perfectl y match the two hal ves, and
heal i ng/mendi ng effi ci enci es were thereafter affected.
To overcome thi s probl em, compact tensi on speci mens
i n thi s work were machi ned as shown i n the di agram
i n Fi gure 5, i n whi ch a hol e was dri l l ed i n the mi ddl e of
the speci mens to stop crack-propagati on.
A sharp precrack was created i n the tapered sampl es
by gentl y tappi ng a fresh razor bl ade i nto a machi ned
starter notch. Appl i cati on of a l oad i n the di recti on
perpendi cul ar to the precrack to the poi nt at whi ch the
fracture toughness l i mi t was exceeded beyond the
Figure2. Sol i d-state
13
C NMR of 2MEP4F: (a) ful l y pol ymeri zed; (b)sampl e of (a) heated to 150 C and then quenched i n l i qui d
ni trogen; (c) sampl es of (b) heated to 90 C and then cool ed to room temperature.
Figure3. Resul ts of DSC obtai ned on 2ME4F and 2MEP4F.
Macromolecules, Vol. 36, No. 6, 2003 Cross-Li nked Pol ymeri c Materi al s 1805
cri ti cal l oad, whi ch i s about 62 N, the speci men frac-
tured and the crack was stopped by the hol e. Load vs
di spl acement resul ts are shown i n Fi gure 6. Because
the dri l l ed hol e mi ght l i e wi thi n the vol ume associ ated
wi th the stress concentrati on i ntroduced by the notch,
the cri ti cal l oad val ue shoul d be consi dered as an
esti mati on of fracture toughness. Addi ti onal studi es are
requi red to resol ve thi s i ssue.
After fai l ure, the speci men was hel d by a cl amp and
pl aced i n a thermal chamber at 115 C for 30 mi n to
heal the crack. The ti me for the speci men to reach
thermal equi l i bri um wi th the chamber was ca. 15 mi n.
The speci men was then cool ed i n the chamber to 40 C
i n 6 h to ful l y repol ymeri ze the materi al . Mi ni mal
pressure was provi ded by the cl amp, al though some
pressure arose from the thermal expansi on of the
pol ymer. Duri ng thi s treatment, onl y the cracks were
mendedsthe starter notches were not affected. The
same fracture tests were al so carri ed out i n an effort to
study the heal i ng effi ci ency. Representati ve l oad-
di spl acement curves for a pol ymer speci men are pl otted
i n Fi gure 6, showi ng recovery of about 81% of the
ori gi nal fracture l oad, and an average of 80% was
achi eved from three i ndependent speci mens (83%, 81%,
and 76%). Usual l y, the second crack propagated al ong
the ori gi nal crack pl ane. An i denti cal heati ng/cool i ng
procedure was appl i ed to heal the second crack. The
average of second mendi ng effi ci ency achi eved was 78%
of the ori gi nal l oad, as determi ned from three i ndepen-
dent speci mens (79%, 79%, and 76%). Thi s resul t
i ndi cates that the materi al can be heal ed effi ci entl y
mul ti pl e ti mes. Because the parameter of cri ti cal l oad
Figure4. Resul ts of DMA obtai ned on pol ymers (a) 2ME4F,
(b) 2MEP4F, and (c) 3M4F.
Figure 5. Di agram of compact tensi on speci mens (thi ck-
ness: 6 mm).
Figure6. A typi cal l oad vs di spl acement di agram of fracture
toughness testi ng of compact tensi on test speci mens of pol ymer
2MEP4F. The ori gi nal and heal ed fracture toughness were
determi ned by the propagati on of the starter crack al ong the
mi ddl e pl ane of the speci men at the cri ti cal l oad.
1806 Chen et al . Macromolecules, Vol. 36, No. 6, 2003
can be i nfl uenced by several factors, such as crack
l ength and crack bl untness, the heal i ng effi ci ency
reported here shoul d be regarded as an esti mate. More
quanti tati ve experi ments wi l l be undertaken i n future
work.
Conclusion
Two new thermal l y remendabl e hi ghl y cross-l i nked
pol ymers, 2ME4F and 2MEP4F, were synthesi zed i n
neat form. Pol ymer 2ME4F wi th soft ethyl enedi oxy
chai ns exhi bi ts a T
g
of about 30-40 C, whi l e the T
g
of
2MEP4F i s about 80 C. I t was found that the DA cross-
l i nks of both pol ymers are thermal l y reversi bl e and can
be used to remend fractured parts. The prel i mi nary
study of the heal i ng/mendi ng effi ci ency of 2MEP4F
shows that, qual i tati vel y, cracks i n thi s materi al can
be recovered effecti vel y after a si mpl e thermal heal i ng
procedure, and thi s process can be repeated.
Acknowledgment. We thank NSF for support
through a grant (DMR 9796302, DMR 0209651). We
al so thank Dr. Si avouche Nemat-Nasser, Mr. Thomas
Pl ai sted, and Dr. Kanji Ono for mechani cal testi ng.
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Macromolecules, Vol. 36, No. 6, 2003 Cross-Li nked Pol ymeri c Materi al s 1807