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Research Paer
!ffect of hi"h#ressure ol$meri%ation on mechanical
roerties of P&&' denture base resin
(atsu)o &ura)ami
a
* (ori$u)i +a)aba$ashi
a*n
* Rie &atsushima
b
*
')io ,ishida
b
* -oshimasa ."arashi
a
a
Removable Partial /enture Prosthodontics* /eartment of &asticator$ 0unction Rehabilitation* /ivision of 1ral 2ealth 3ciences* 4raduate
3chool* 5o)$o &edical and /ental 6niversit$* 1#7#47 -ushima* 8un)$o#)u* 5o)$o 113#8749* 9aan
b
/eartment of &aterial#based &edical !n"ineerin"* /ivision of 8iofunctional Restoration* .nstitute of 8iomaterials and 8ioen"ineerin"*
5o)$o &edical and /ental 6niversit$* 2#3#10 ,anda#3uru"adai* :hi$oda#)u* 5o)$o 101#00;2* 9aan
a r t i c l e i n f o
'rticle histor$<
Received ; /ecember 2012
Received in revised form
2; /ecember 2012
'cceted 30 /ecember 2012
'vailable online 8 9anuar$ 2013
,e$=ords<
2i"h ressure
Pol$meri%ation
Resin
/enture
P&&'
5ou"hness
a b s t r a c t
5he aim of this stud$ =as to assess the effect of hi"h#ressure ol$meri%ation on
mechanical roerties of denture base resin> ' heat#curin" denture base resin and an
e?erimental P&&' =ere ol$meri%ed under 700 &Pa of ressure b$ means of an isostatic
ressuri%ation machine at @0 1: for 24 h to ma)e rectan"ular secimens =hose
dimensions =ere 30 mm 2 mm 2 mm> !ach secimen =as deflected on a three#oint
fle?ural test until either fracture occurred or the samle =as loaded u to 8 mm in
deflection> 5he molecular =ei"ht of the P&&' =ithout filler =as anal$%ed usin" the
hi"h#seed liAuid chromato"rah$ s$stem> .ncreased ductilit$ =ithout fracture =as sho=n
in the secimens subjected to hi"h ressure* =hile most of the control secimens
(ambient ressure) fractured> 5he mean tou"hness of the P&&' secimens
ol$meri%ed under the hi"h ressure =as si"nificantl$ hi"her than the same material
ol$meri%ed under ambient ressure (o0>01)> 5he hi"h ressure "rous of the denture
resin and the P&&' revealed a si"nificantl$ lo=er mean 0>2B $ield stress* fle?ural
stren"th* and elastic modulus than control "rous (o0>01)> 5here =ere certain amounts
of hi"her molecular =ei"ht ol$mers in the hi"h ressure secimens than =ere resent in
the controls> 5he increased tou"hness sho=n in the P&&' ol$meri%ed under the hi"h
ressure =as resumabl$ attributed to the hi"her molecular =ei"ht roduced b$ the
ressure> 5he result su""ests a otential alication of the hi"h#ressure
ol$meri%ation to the develoment of P&&'#based
denture resin =ith imroved fracture resistance>
C 2013 !lsevier Dtd> 'll ri"hts reserved>
1> .ntroduction
5he fracture resistance of acr$lic denture base* =hether for
conventional or imlant#suorted dentures* is one of the
imortant factors in terms of safet$* lon"evit$* and atient
satisfaction =ith removable rosthodontics> 5he most com#
mon material used to fabricate the denture base is an acr$lic
resin made from a mi?ture of meth$l#methacr$late (&&')
n
:orresondin" author> 5el>< E81 3 7803 4937F fa?< E81 3 7803 494;>
!#mail addresses< n > mu ra)ami>r roGtmd>ac>j (( > &ura)ami)* =a) a ba $ ashi>rroGtmd>ac>j (( > + a)ab a $ashi)*
matsushima>mbme G tmd>ac>j (R> &atsushim a )* )ishida>mbm e Gtmd>ac > j ('> ,ishi d a)* i"arashi>r roGtmd>ac>j (- > ."arashi)>
1@71#;1;1HI # see front matter C 2013 !lsevier Dtd> 'll ri"hts reserved>
h t t<HHd?>doi> or"H10>101;Hj>jmbbm>2012>12>011
99 j o u r n a l o f t h e m e c h a n i c a l b e h a v i o r o f b i o m e d i c a l m a t e r i a l s 2 0 ( 2 0 1 3 ) 9 8 1
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and ol$ (meth$l methacr$late) (P&&')> 5his material os#
sesses favorable =or)in" characteristics* olishabilit$* stabi#
lit$ in the oral environment* and e?cellent aesthetic
aearance ((arva et al>* 2007)> 2o=ever* the literature has
reorted that the freAuenc$ of acr$lic fracture is estimated
to be bet=een 7@B and ;4B of all failures of removable
dentures (/arbar et al>* 1994F Jallittu et al>* 1993)> 5he
h$sical roer# ties e?hibited b$ this material are sensitive
to the de"ree of conversion* rocessin" techniAue* and
conditions resented b$ the oral environment> 3tress#
suscetible sites often seen in removable artial dentures
ma$ also have a si"nificant influence on the fracture
initiation in the acr$lic denture base (8ural et al>* 2010F
:arlsson et al>* 19@;F 3himi%u et al>* 2004)> .t is therefore
reco"ni%ed that the material does not meet the mechanical
reAuirements for rostheses that are subjected to hi"h stress
under masticator$ function (,oro"lu et al>* 2009F &emon et
al>* 2001F (arva et al>* 2007)>
2i"h#ressure ol$meri%ation is one of the rocessin"
technolo"ies that have been develoed for the s$nthesis of
hi"h#molecular#=ei"ht ol$mers =ith =ell#defined
structures> 5he effect of ressure has been reorted for
reversible addition fra"mentation (chain) transfer
ol$meri%ation (R'05)* result# in" in hi"her
ol$meri%ation rates and in ol$mers =ith hi"her
molecular =ei"hts and lo=er ol$disersit$ (R%a$ev and
Penelle* 2004)> 2i"h ressures u to ;00 &Pa have been
reorted to enable relativel$ fast s$nthesis of =ell#
defined molecular =ei"ht ol$methacr$lates* even at room
temera# ture (,=iat)o=s)i et al>* 2008)> .t has also been
reorted that ol$meri%ation under ressures u to 700
&Pa at ;0 1: facil# itate atom transfer radical
ol$meri%ation ('5RP) of &&'* resultin" in hi"her
ol$meri%ation rates and in ol$mers =ith hi"her molecular
=ei"hts and lo=er ol$disersit$ ('rita et al>*
2008F R%a$ev and Penelle* 2002)> ' recent reort indicated
that ol$meri%ation under a hi"h ressure of 270 &Pa at a
hi"h temerature of 180 1: increased the fle?ural stren"th
and hardness of commerciall$ available dental resin
comosites (("u$en et al>* 2012)> .n that stud$* a si"nificant
increase of the fracture tou"hness (,
.:
) =ith the hi"h#
ressureHhi"h temera# ture condition =as sho=n in t=o
dental comosite materials out of four> 2o=ever* the effect
of the hi"h ressure ol$mer# i%ation on the mechanical
roerties of the P&&' denture base resin is not )no=n>
.n this stud$* =e utili%ed a hi"h#ressure reaction
s$stem incororatin" a ressure#resistant chamber to
ol$meri%e the
P&&' secimens under ressures u to 980 &Pa> 5he ur#
ose of this stud$ =as to test the h$othesis that al$in"
hi"h ressure durin" ol$meri%ation increases the fracture
resistance of the P&&'#based denture base resin>
2> &aterials and methods
5he materials used in this stud$* =ith their batch numbers*
manufacturers* and o=derHliAuid comositions* are listed
in 5able 1>
2>1> Pac)in" of samles
5he secimens =ere reared usin" a 5eflon
s
late
(P50! 3heet* 0#8037#04* 0lon .ndustr$* 5o)$o* 9aan) =ith
ei"ht rectan"ular mold cavities (30 mm 3 mm 3 mm for
each)> ' commerciall$ available P&&'#based heat#curin"
denture base resin =as mi?ed at a room temerature of
27 1: in accordance =ith the manufacturersK instructions
at the o=derHliAuid ratio of 100 m"H43 mD> +hen the
mi?ture reached the consistenc$ of dou"h* it =as oured
into the mold and covered =ith a ol$vin$l chloride late
sealed =ith a ol$eth$lene film> !ach mold late =as then
ac)ed and sealed in a ol$eth$lene (P!5) container
(3eisannionsha Dtd>* 5o)$o* 9aan)* follo=ed b$
secondar$ ac)in" =ith another P!5 container that =as
filled =ith =ater>
+e reared t=o e?erimental P&&' materials* one =ith
filler material Ldenoted as P&&'H0(E)M and the other =ithout
filler Ldenoted as P&&'H0( )M (5able 1)> .n the reliminar$
molecular =ei"ht measurements* the 'cron and the P&&'H
0(E) did not dissolve in the "el ermeation chromato"rahic
(4P:) solvent* robabl$ due to the inclusion of the cross#
lin)in" ol$mers* thus it =as not ossible to measure the
molecular =ei"ht of these materials accuratel$> 5herefore*
the P&&'H0( ) =as reared secificall$ to ensure the for#
mation of hi"h#molecular#=ei"ht ol$mers> 5he P&&'H0( )
=as reared b$ a mi?ture of &&' and ben%o$l ero?ide
(8P1) as the ol$meri%ation initiator* =ith (*(#dimeth$l##
toluidine (/&P5) as the ol$meri%ation romoter> 5he ac)#
in" of each P&&' secimen =as conducted usin" the same
method as for the 'cron secimens>
5able 1 &aterials used in the stud$>
3amle code :omosition 8atch no> &anufacture
'cron Po=der
a
'cron in) 1012201 4:* 5o)$o* 9aan
DiAuid 'cron 1203121
P&&'H0(E) Po=der< P&&' (/ai$anal 8R88) rccl"18;4#11 &itsubishi Ra$on>* 5o)$o* 9aan
DiAuid
b
&&' /:!2809 +a)o Pure :hemical .ndustries* 1sa)a* 9aan
8P1 101;0333 'lfa 'esar* &'
P&&'H0( ) DiAuid
c
&&' /:!2809 +a)o Pure :hemical .ndustries* 1sa)a* 9aan
8P1 101;0333 'lfa 'esar* &'
/&P5 &R00. 5o)$o :hemical .ndustr$* 5o)$o* 9aan
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a
Po=der contains 8P1 accordin" to the manufacturerKs note>
b
DiAuid contains =ith 8P1 =ith the molar ratio of 180<1 for &&'<8P1>
c
DiAuid contains 8P1 and /&P5 =ith the molar ratio of 180<1<4 for &&'<8P1</&P5>
100 j o u r n a l o f t h e m e c h a n i c a l b e h a v i o r o f b i o m e d i c a l m a t e r i a l s 2 0 ( 2 0 1 3 ) 9 8 1 0 4
2>2> Pol$meri%ation
Pol$meri%ation =as conducted under hi"h ressure* =ith
ambient ressure as the control> 5he hi"h#ressure
ol$mer# i%ation =as erformed b$ usin" an isostatic
ressuri%ation machine (/r> :hef* ,obe 3teel* Dtd>*
2$o"o* 9aan)> 5he samle containers =ere immersed in
transmission fluid in the samle chamber of the machine>
0or the 'cron and the P&&'H0(E) samles* the ressure
=as increased at a rate of
33 &PaHmin at @0 1: until it reached 700 &Pa> 'fter the
ressure =as maintained for 24 h* the chamber =as deres#
suri%ed at a rate of 33 &PaHmin until it reached ambient
ressure> 5he same temerature and ol$meri%ation time
=ere emlo$ed for the control secimens> 0or the P&&'H0(
) samles* one of the hi"h ressure levels of 700 &Pa* 800
&Pa* or 980 &Pa =as used* =ith the temerature
maintained at
27 1: durin" the ol$meri%ation rocess of ;0 min> :ontrol
secimens =ere ol$meri%ed under ambient ressure in a
heat#retention bath> !ach secimen ta)en out from the mold
=as trimmed and finished usin" abrasive aers (270 "rit to
;00 "rit)> 5he avera"e final dimensions of all secimens
measured usin" a di"ital calier =as 30@3 mm 2@0>1 mm
2@0>1 mm in len"th* =idth* and thic)ness* resectivel$>
!i"ht secimens for the hi"h ressure "rou and 1;
secimens for the control "rou =ere reared for the 'cron
and the P&&'H 0(E) and =ere stored in distilled =ater at 3@
1: for 24 h before the fle?ural test>
2>3> 0le?ural test
!ach secimen from the 'cron and the P&&'H0(E) "rous
=as subjected to a three#oint fle?ural test on a h$draulic
servo testin" machine =ith a?ial loadin" units (.nstron 1123*
:anton* &.* 63')> 5he secimens =ere centered on the test
ri" so that the loadin" =ed"e* set to travel at a crosshead
seed of 1 mmH min* en"a"ed the center of the uer
surface of each seci# men* =ith a distance bet=een the
suorts of 20 mm> 5he secimens =ere tested at room
temerature under ambient ressure> !ach secimen =as
deflected =ith a vertical cross# head seed of 1 mmHs until
fracture occurred* or it =as loaded until the loadin" rod
reached a re#set ma?imum vertical drivin" distance of 8
mm> 5he a?ial load and dislacement =ere recorded b$ 7
)( load cells =ith transducers mounted on linear actuators>
5he transverse stren"th (3* (Hmm
2
) =as calculated from
the follo=in" eAuation<
30l
3 N
2bh
2
=here 0 (() is the alied load at the hi"hest oint of
the loaddeflection curve* l is the san len"th* b is the =idth
of the test secimen* and h (mm) is the thic)ness of the
test seci# men> 5he 0>2B $ield stress of each secimen
=as also comuted>
5he modulus of elasticit$ (!* (Hmm
2
) =as comuted from
follo=in" eAuation<
0
1
l
3
! N
4bh
3
d
=here d (mm) is the deflection corresondin" to load 0
1
(() at
a oint in the strai"ht line ortion ta)en from the
loaddeflection curve> 5he oint =as automaticall$
detected b$ the soft=are of the testin" machine>
5ou"hness is the amount of elastic and lastic
deforma# tion ener"$ reAuired to fracture the acr$lic resin
secimens> .t =as measured as the total area under the
loaddeflection curve of the tested secimens> 5he values
for tou"hness (5* ( mm) =ere calculated from follo=in"
eAuation<
5
!ObP
N
lbh
=here !(b) is brea)in" ener"$ calculated from the area
under the loaddeflection curve>
5he mean values for each test "rou =ere calculated
and the non#aired t#test =as used to test the si"nificant
difference bet=een the hi"h ressure and the ambient
ol$meri%ation> 'll statistical anal$ses =ere erformed
usin" 3P33 (17>01* 3P33 .nc>* :hica"o* .D* 63') on a
si"nificance level of 1B>
2>4> &icroscoic
observations
5he fractured and non#fractured secimens after the
load test =ere "old suttered (270 '
Q
thic)ness) and
e?amined b$ a scannin" electron microscoe (3#3400(,*
2itachi* 5o)$o* 9aan) at a 7 )J acceleratin" volta"e> 5he
3!& hotomicro# "rahs =ere ta)en =ith 30 to 70
ma"nifications for visual
observation
s>
5o observe the intermediate la$er bet=een the
P&&' beads and ol$mer matri?* secimens =ere further
olished usin" abrasive aer (800 "rit to 2000 "rit) and
finall$ =ith
0>1 mm alumina articles> 5o e?ose the P&&' beads
b$ sli"htl$ dissolvin" the surface of resin* tetrah$drofuran
(520) =as alied as a solvent for 30 s> 5he observation
usin" the li"ht microscoe ima"es ('R@0 PR1J.3* 1l$mus*
5o)$o* 9aan) =as visuall$ served to evaluate the interfacial
characteri%ation in the surface (,a=a"uchi et al>* 2011a*
2011b)>
2>7> 4el ermeation chromato"rah$
(4P:)
Pol$meri%ed samles from the P&&'H0( ) "rou =ere
ta)en out for 4P: measurement to determine their
molecular =ei"ht and distribution> 5he anal$sis =as
carried out at
40 1: on a hi"h#seed liAuid chromato"rah$ s$stem
(3hode? 4P:#101) eAuied =ith a "uard column (3hode?
4P: D0#4)* t=o 30#cm mi?ed columns (3hode? 4P: D0#804*
e?clusion limit of 2 10
;
)* and a differential refractometer
(3hode? R.#
@13)> (*(#dimeth$l formamide (/&0) containin" 10 m&
Di8r =as used as an eluent at a flo= rate of 0>8 mDHmin>
5he 4P: s$stem =as basicall$ calibrated b$ P&&'
standards S3hode?* 35'(/'R/ &#@7* & N L(2>89 10
3
)(9>;7
10
7
)MT>
3> Results
5he secimens =ere safel$ ol$meri%ed b$ hi"h ressure u
to 980 &Pa* and the e?ternal aearance of the hi"h ressure
secimens =as not distin"uishable from that of the control
secimens> 'll the hi"h ressure secimens =ere loaded u
to a reset ma?imum dislacement of 8 mm =ithout
fracture* e?cet for t=o of the 'cron and one of the
P&&'H0(E) samles* all of =hich fractured into t=o ieces
(0i"s> 1 and 2)> 5he
j o u r n a l o f t h e m e c h a n i c a l b e h a v i o r o f b i o m e d i c a l m a t e r i a l s 2 0 ( 2 0 1 3 ) 9 8 1 0 4 101
0i"> 1 3tressstrain relationshi of the 'cron denture
base resin> 'll hi"h ressure secimens (n N 8) =ere loaded
u to a re#set ma?imum deflection of 8 mm =ithout
fracture* e?cet for t=o secimens that fractured> 'll the
control secimens (n N 1;) e?hibited fractures* e?cet for
t=o that =ere loaded u to the dislacement limit>
0i"> 2 3tressstrain relationshi of the P&&'> 'll hi"h
ressure secimens (n N 8) =ere loaded u to a re#set
ma?imum deflection of 8 mm =ithout fracture* e?cet for
one secimen that fractured> 'll the control secimens
(n N 1;) e?hibited fractures>
stressstrain curve of the hi"h ressure secimens
sho=ed elastic behavior in the earl$ sta"e* a ea) load* and
subseAuent lastic behavior> 'll the ambient control
secimens e?hibited a t$ical stressstrain curve until
reachin" a shar decrease in stress due to fracture* e?cet
for t=o of 'cron samles that =ere loaded u to the
dislacement limit> 5here =as consider# able deviation in
the ma?imum deflection of the fractured secimens in the
control "rou>
5he hi"h ressure "rou of each material e?hibited si"#
nificantl$ lo=er mean values for the 0>2B $ield stress
(o0>01)* fle?ural stren"th (o0>01)* and elastic
modulus (o0>01) in comarison =ith the control "rou of
the corre# sondin" material (5able 2)> 0or each material* no
statisticall$
si"nificant difference bet=een the t=o ressure conditions
=as found in the strain at the ma?imum stress> (o statisti#
call$ si"nificant difference in the tou"hness bet=een the
different ressures =as found in the 'cron* =hereas the hi"h
ressure "rou revealed si"nificantl$ hi"her tou"hness
(o0>01) than the control in the P&&'>
5he 3!& fracture surface microhoto"rahs indicated that
the side surface of all the non#fractured hi"h ressure seci#
mens revealed distributions of cra%in" on the tensile bottom
surface (0i"> 3)> :leava"e#li)e ratchet mar)s =ere evident on
the bottom surface* and the$ created a number of curved
crac) lines that =ere ori"inall$ the strai"ht olishin" mar)s>
.t =as clearl$ indicated in the 'cron and the P&&'H0(E) that
the numbers of the crac)s =ere more for the non#fractured
hi"h ressure secimens (0i"> 3* left) than those for a fe=
non#fractured control secimens (0i"> 3* ri"ht)> 5he crac)s
"enerall$ roa"ated deeer alon" the olishin" mar)s at the
corner of the bottom lane> 5he surface crac)s and the
curved olishin" mar)s =ere not observed on the side and
the bottom surfaces of the fracture secimens (0i"> 3* center)>
5he border bet=een the P&&' beads and the ol$mer matri?
=ere visible in all the hi"h ressure secimens of the 'cron
and the P&&'H0(E) (0i"> 4* uer left)> 5he interenetratin"
ol$mer net=or) (.P() la$er =as also confirmed in the hi"h
ressure "rous after the 520 treatment (0i"> 4* lo=er left)>
+hile* the border of the P&&' articles =as sli"htl$ visible in
the 3!& of the fractured control secimens (0i"> 4* uer
ri"ht) but not detected for the control "rous (0i"> 4* lo=er
ri"ht)>
0i"> 7 sho=s the differential molecular =ei"ht distribution
of the 4P: anal$sis of reresentative secimens for the
P&&'H0( ) that =ere ol$meri%ed under different levels of
hi"h ressure as =ell as under ambient conditions> 5he
control secimen revealed a monohasic =ide distribution*
=hereas all the hi"h ressure secimens rovided a dihasic
distribution* in =hich the number#avera"e molecular =ei"ht
(&n) of the lar"er molecular =ei"ht ea) =as hi"her than
that of the control> 5he differential =ei"ht fraction demon#
strated in the lar"er =ei"ht ea) increased as the ol$mer#
i%ation ressure increased> 1n the other hand* the ea)s for
all the hi"h ressure "rous =ere located above the 10
;
molecular =ei"ht* meanin" that the$ =ere li)el$ close to
the e?clusion limit of the method> 5his indicated that these
hi"h ressure secimens otentiall$ ossessed a hi"her
molecular =ei"ht fraction than those detected =ith the
method used in this stud$>
4> /iscussion
5he h$othesis that the fracture resistance is hi"her =ith
hi"h ressure than it is under ambient ressure =as artiall$
suorted b$ the results* =hich sho=ed si"nificantl$ hi"her
avera"e tou"hness of the P&&' in the hi"h ressure samles
than in the ambient ressure samles> 5he increased tou"h#
ness =as consistent =ith the results reorted in a revious
stud$ for dental comosites that =ere ol$meri%ed under the
hi"h ressure of 270 &Pa (("u$en et al>* 2012)> 5he results of
the =ei"ht measurement of the P&&'H0( ) indicated that
there =ere certain amounts of hi"her molecular =ei"ht
102 j o u r n a l o f t h e m e c h a n i c a l b e h a v i o r o f b i o m e d i c a l m a t e r i a l s 2 0 ( 2 0 1 3 ) 9 8 1 0 4
5able 2 5he mean and the standard deviations of the mechanical roerties for the 'cron denture base resin and
the e?erimental P&&' =ith filler in the three#oint fle?ural load test>
'cron
:ontrol 2i"h ressure
P&&'H0(E)
:ontrol 2i"h ressure
&ean 83>9

;7;>3

87>2

;;>3

0>2B $ield stress (&Pa)
(3>/>) 1>8 1>3 2>; 2>3
&ean 124>0

97>3

128>0

9@>4

0le?ural stren"th (&Pa)
(3>/>) 1@>3 9>9 4>8 2>7
&ean ;>2; 7>81 ;>44 ;>14
3train at the ma?imum stress (B)
(3>/>) 1>@8 1>41 1>1 0>29
&ean 3>3;

2>@7

3>32

2>@9

!lastic modulus (4Pa)
(3>/>) 0>07 0>03 0>10 0>10
&ean 0>94 1>7; 0>@2

1>@;

5ou"hness (( mm)
(3>/>) 0>81 0>33 0>18 0>77
n
'steris) indicates a si"nificant difference bet=een the hi"h ressure and control =ithin the same material "rous (o>01)
0i"> 3 5he 3!& ima"es of reresentative 'cron secimens after the loadin" test> 5he ima"es on the left< a non#fractured
hi"h ressure secimenF center< a fractured control (ambient ressure) secimenF ri"ht< a non#fractured control secimen>
5he ima"es on the uer ro= sho= the side surface ( 30)* =hile the corresondin" secimens on the lo= are vie=ed
from the tensile bottom surface ( 70)> +hite arro=s indicate the cra%in" mar)s on the tensile bottom surface> 3< side
surface* 5<
tensile bottom surface* :< comressive uer surface>
ol$mers in the hi"h ressure ol$meri%ation "rous than
=ere resent in the control "rou> .n addition* the fraction of
the hi"h#molecular#=ei"ht ol$mers increased as the res#
sure level increased> .t =as therefore hi"hl$ li)el$ that the
increased tou"hness of the hi"h ressure secimens =as
attributed to the increased avera"e molecular =ei"ht of the
ol$mer matri?> 5he increased molecular =ei"ht =as con#
sistent =ith revious studies reortin" that the
ol$meri%a# tion under ressure from 300 &Pa (,ojima et
al>* 2002) to
700 &Pa ('rita et al>* 2008) increased the avera"e molecular
=ei"ht and the ol$meri%ation rates of &&'> .n a free
radical ol$meri%ation* it =as e?lained that hi"h ressure
remar)# abl$ increased the ol$meri%ation rate* =ith an
enhanced roa"ation rate constant and a reduced
termination rate constant ('rita et al>* 2008F ,=iat)o=s)i et
al>* 2008)> 'nother otential reason for the increased
tou"hness =as the reduc# tion of the internal voids and
defects (8rosh et al>* 2002F :had=ic) et al>* 1989)* because
the hi"h ressure environment
could reduce the distribution of the voids that =ere
otentiall$ created durin" the ol$meri%ation rocess
(:armai and /unne* 2003F 1nishi and -oshi)a=a* 2002)> .t
=as reorted in a stud$ usin" dental comosites that the
hi"h ressureHhi"h temerature ol$meri%ation resulted
in a reduction in the number and si%e of defects (("u$en
et al>* 2012) that led to the imrovement of the fracture
tou"hness> 5he hi"h#molecular# =ei"ht fraction could
increase rocessin" difficulties because of its enormous
contribution to the melt viscosit$ ('hmed et al>* 2009F
3erlin"* 2001)> 0or these reasons* the lo= end of the
distribution mi"ht be created and act as a lastici%er*
softenin" the material> :ertainl$ it does not contribute
as much to the tensile stren"th ('hmed et al>* 2009F
3erlin"*
2001
)>
5he hi"h ressure of 700 &Pa durin" the
ol$meri%ation rocess decreased the elastic modulus*
the $ield* and the ma?imum fle?ural stren"th of the
P&&'#based heat curin" resin> !mhasis should be
laced on the visible interface
j o u r n a l o f t h e m e c h a n i c a l b e h a v i o r o f b i o m e d i c a l m a t e r i a l s 2 0 ( 2 0 1 3 ) 9 8 1 0 4 103
0i"> 4 5$ical ma"nified ima"es of the fractured surfaces
of the 'cron secimens> 5he 3!& ima"es (uer) and the
li"ht microscoic ima"es follo=in" the 520 treatment
(lo=er)* are sho=n for t$ical hi"h ressure (left) and
control secimens (ri"ht)> 8lac) arro=s indicate the
interface bet=een a P&&' article and the ol$mer
matri?> +hite trian"les indicate the .P( la$er (lo=er left)>
0i"> 7 4P: traces of P&&' ol$meri%ed under ambient
(control) and hi"h ressure (700 &Pa* 800 &Pa* and
980 &Pa)> 5he ?#a?is in the lo"arithmic scale reresents
the molecular =ei"ht and the $#a?is reresents the
differential =ei"ht fraction calculated from the cumulative
=ei"ht ercenta"e> &olecular =ei"hts =ere measured
relative to P&&' standards L(& N (2>89 10
3
)(9>;7 10
7
)M>
bet=een the P&&' articles and the ol$mer matri? in the
hi"h ressure secimens* =hich =as not seen in the control
secimens> .n the heat#ol$meri%ed resin under the ambient
ressure* the P&&' articles =ere li)el$ to s=ell b$ absorb#
in" the monomer* resultin" in the homo"eni%ed aearance
in the micro"rahs (0i">4* ri"ht)> 2o=ever in the hi"h
ressure ol$meri%ation* the interface became visible in
the 3!&* resumabl$ because the hi"h ressure increased
the inter# facial stress bet=een the materials of
dissimilar elastic modulus and coefficient of
comressibilit$ (3asu"a and 5a)ehisa* 19@8)> 3ince the
'cron and the P&&'H0(E) of this stud$ =ere heat#cured
after the dou"h sta"e samles =ere laced in the chamber*
the effect of the comression b$ the
hi"h ressure could la$ a si"nificant role in creatin" the
interfacial stress on the border bet=een the articles and the
matri?> 3uch ne"ative effects of the hi"h ressure ol$mer#
i%ation ma$ artiall$ e?lain the crac) initiation on the
tensile bottom surface of the loaded secimens> 5he distribu#
tions of the cra%in" otentiall$ caused the decrease of some
mechanical roerties and the stren"ths* althou"h the$ =ere
still =ithin the ran"e of the reAuirement secified b$ the .31
standard for the denture base ol$mers and cool$mers (.31
20@97#1<2008)>
.n the hi"h ressure secimens* the cra%es roa"ated
erendicular to the alied tension but =ere arrested b$ the
matri? ol$mer =ithout causin" bul) fracture> 'lthou"h such
cra%in" "enerall$ aears at hi"hl$ stressed re"ions asso#
ciated =ith fla=s* stress concentrations* and molecular inho#
mo"eneities (.shi)a=a and 5a)ahashi* 1991)* the rocess of
cra%e "ro=th rior to crac)in" absorbs fracture ener"$ and
effectivel$ increases the fracture tou"hness of a ol$mer
('t)ins et al>* 19@7F 4reen and Pratt* 19@4)> 5herefore* the
formation of cra%in" on the tensile surfaces =as indicative of
the increased ductilit$ of the P&&' secimens>
/urin" ol$meri%ation* the monomers dissolve and diffuse
to the surface of the P&&' beads> 8$ treatin" the ol$mer
structure =ith a suitable solvent such as 520 used in this
stud$* the .P( la$er can be observed surroundin" P&&'
beads in the microscoe (Jallittu and Ru$ter* 199@F Jallittu
et al>*
199@)> .n the hi"h ressure secimens of this stud$* the
distinctive too"rahical features of the P&&' articles
became visible and the e?istence of the .P( la$er =as also
detected> +hile the thic)ness of the .P( la$er =as deendent
of temerature and the contact =ettin" time of the liAuid
monomers* it has been indicated that the increased thic)ness
of the la$er "ained the cree resistance (1$saed and Ru$ter*
1989) and other mechanical roerties of the autool$meri%#
in" denture base resins (,a=a"uchi et al>* 2011a)> 2o=ever*
the influence of the .P( la$er on the mechanical roerties of
the heat#curin" denture base resins remains to be elucidated>
5he hi"h ressure of 700 &Pa =as emlo$ed for the
fle?ural test secimens* althou"h the hi"hest limit of the
s$stem used =as 980 &Pa> Previous literature indicated that
the alication of hi"h ressure on a monomer mi?ture for
ol$meri%ation decreases the intermolecular distances and
reduces the free volume (&urli and 3on"* 2010)> /ue to
reduced mobile caabilit$ under an e?tremel$ hi"h ressure
(above 1 4Pa)* the monomers are li)el$ to transform into
solids and form monomer cr$stals* thus reducin" the ol$#
meri%ation de"ree (("u$en et al>* 2012F 3chettino et al>* 2008)>
.n fact* =e found that some ilot secimens reared under
the hi"h ressure of 980 &Pa sho=ed lo=er stren"ths than
those made =ith the ressure of 700 &Pa> .t can be secu#
lated that the hi"her ressure more than 700 &Pa further
reduced the interfacial inte"rit$ bet=een the P&&' beads
and the ol$mer matri?> 0urther studies are needed to
otimi%e the ressure level in combination =ith the tem#
erature and rocessin" time for roduction of the P&&'
denture base resin that can stabl$ e?hibit hi"her mechanical
roerties than those sho=n in this stud$> 5he results of this
stud$ ma$ increase the understandin" of the effect of the
hi"h ressure ol$meri%ation on the mechanical roerties
of the P&&'#based heat#curin" denture base resin and lead
104 j o u r n a l o f t h e m e c h a n i c a l b e h a v i o r o f b i o m e d i c a l m a t e r i a l s 2 0 ( 2 0 1 3 ) 9 8 1 0 4
to further develoments of this ol$meri%ation
method> 0uture investi"ations are also encoura"ed to assess
the oten# tial alication of the hi"h ressure
ol$meri%ation in the roduction of the :'/H:'& bloc)s
for the dental rostheses and of the tou"hened P&&'
articles for the conventional heat#activated or chemicall$
activated denture base resins>
7> :onclusions
Pol$meri%ation under a hi"h ressure of 700 &Pa increased
the tou"hness of the e?erimental P&&' =ith filler* =hile
decreasin" the $ield and fle?ural stren"ths and the elastic
modulus> 5he increased tou"hness obtained b$ the hi"h#
ressure ol$meri%ation in the commercial denture base
resin and the e?erimental P&&' resin su""ests otential
develoment of biomedical P&&' materials =ith imroved
fracture resistance>
'c)no=led"ement
5his stud$ =as suorted b$ a 4rant#in#'id (U24792902 to
(>+>) from the 9aan 3ociet$ for Promotion of
3cienceH&!R5>
r e f e r e n c e s
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of lactide isomer> 9ournal of 5hermal 'nal$sis and
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'rita* 5>* ,a$ama* ->* 1hno* ,>* 5sujii* ->* 0u)uda* 5>* 2008>
2i"h# ressure atom transfer radical ol$meri%ation of
meth$l methacr$late for =ell#defined ultrahi"h molecular#
=ei"ht ol$mers> Pol$mer 49* 242;2429>
't)ins* '>4>* Dee* :>3>* :addell* R>&>* 19@7> 5ime#temerature
deendent fracture tou"hness of P&&'> 9ournal of &aterials
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of ol$meri%ation under ressure on indirect tensile
mechanical roerties of li"ht#ol$meri%ed comosites>
9ournal of Prosthetic /entistr$ 88* 38138@>
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ol$merisin" acr$lic resin after =ettin" =ith monomer and
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treatment =ith artial dentures> 'n investi"ation b$
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:armai* 9>* /unne* 0>P>!>* 2003> :onstitutive eAuations
for densification of matri?#coated fibre comosites durin"
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3473;3>
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