Journal of Energy Technologies and Policy www.iiste.

org
ISSN 2224-3232 (Paer! ISSN 222"-#"$3 (%nline!
&ol.4' No.3' 2#(4

(
Influence of Low Temperature on Heat Transfer in Epoxide
NanoComposites

)r.*++as *lwi Sa,hir *+ed

-ni.ersity of *l-/adissiya-0ollege of Engineering-I1*/
a++asa+ed"23g4ail.co4

Abstract
The rocess of heat transfer in oly4er syste4s and co4osites due to the .ariety of factors deter4ining their
roerties is e5tre4ely co4le5 and has +een oorly studied ractically. 6eat transfer in unfilled oly4ers
largely deends on oly4er structure in general' on the degree of order of structural ele4ents within one.
Infusion of nanofillers into a oly4er syste4 leads to significant changes of 4echanical' ther4al' electrical' and
other roerties. *t infusion of fillers' the heterogeneity of a oly4er syste4 at a 4acroscoic le.el also
increases.
Keywords:-nanofillers oly4er heterogeneity intra4olecular nanoco4osites

Introduction
Nowadays a lot of 4aterials a+out research and co4ilation of 4echanical and ther4al roerties of
con.entional filled oly4ers ha.e +een accu4ulated. 7or oly4ers filled +y nanoarticles' there is only
frag4entary infor4ation' often contradictory' 4ainly in.estigating 4echanical roerties of 4aterials.
8echanis4s of the interaction +etween oly4er and filler for crystalli9ing a4orhous oly4ers ha.e a different
character. 7illed to crystalline oly4er solid articles can +e laced in the 4iddle of sura4olecular structures
and ser.e as a +asis for growth of conglo4erates or to +e dislaced in the regions +etween structural ele4ents.
*t filling of a4orhous oly4ers' with the surface of filler +oth indi.idual 4acro4olecules and sura4olecular
structures interact.
It has +een found that the 4ain feature in the influential 4echanis4 of fillers on roerties of oly4ers is the
nature of the rocesses at sura4olecular le.els. The order of sura4olecular structure of oly4er co.ers 4ore
outlying fro4 filler surface areas than it leads fro4 ther4odyna4ic concets. Therefore' as a result of the
interaction +etween oly4er and filler' rigid structural ele4ents for4' er4eating the entire .olu4e of oly4er
and ha.ing a significant effect on its 4echanical roerties. In nanoco4osites the entire oly4er 4atri5
transfor4s to the state of an interfacial layer with different fro4 oly4er in .olu4e roerties. These rocesses
are illustrated +y figures (figure (!' 4ade +y scanning electron 4icroscoe 0arl :eiss Sura
T8
"" for eo5ide
nanoco4osites.
Thus' in co4osites heat transfer rocesses are caused +oth +y conducti.ity of indi.idual co4onents and
significantly +y a +oundary layer filler ; fi5ant' its structure and hysical ;4echanical changes deending on
e5ternal influences are still oorly researched.
Therefore' e5eri4ental data is of articular .alue for the creation and oeration of de.ices fro4 co4osite
4aterials.
7ro4 a wide .ariety of oly4ers' ther4oset fi5ants ha.e +een chosen ; na4ely eo5ide ; as the 4ost widely
used in .arious structural and electroinsulating 4aterials in aeronautics' auto4oti.e and electronics industries.
Ther4osetting eo5ides are widely used due to the fact that they co4+ine high strength roerties' e5cellent
di4ensional sta+ility' heat resistance and resistance to .arious e5ternal en.iron4ental influences. 6owe.er'
these highly crosslin,ed ther4oset oly4ers ha.e inherent fragility' which increases with increasing of
crosslin,ing density. So they are filled +y different 4ineral fillers to eli4inate this disad.antage.
Nanoco4osites +ased on oly4eric fi5ants are ro4ising 4aterials fro4 the .iewoint of reinforce4ent of
oly4ers and i4arting the4 i4ro.ed roerties +y infusion of nanoarticles of different 4aterials into a
oly4er 4atri5.
<ith decreasing of article si9e' secific surface area of filler' length of the interfaces and +oundary layer
roortion increase. =oundary layer >uantity at the article si9e of #." ; " 4icrons increases u to "#?' and its
influence on roerties of co4osite 4aterial increases. *t the article si9e of (# ; (## n4' co4osite 4aterial
can +e called nanoco4osite. In such 4aterials e.en with the roortion of filler on the order of arts of a
ercent' ractically the entire oly4er transfor4s into the +oundary layer state @(A.
8any of ro4ising directions in 4aterial sciences' nanotechnology' nanoelectronics and alied che4istry are
associated recently with nanotu+es and other si4ilar nanostructures which can +e called +y a general ter4 ;
car+on s,eletal structures. )ue to different roerties of nanoarticles' such as e5tended surface' di4ensional
and >uantu4 effects of nanoeo5ide co4osites e5hi+it i4ro.ed 4echanical and ther4al roerties.
=ut' desite the fact that car+on nanotu+es can +e considered as heat suerconductors (the highest .alues of
ther4al conducti.ity of car+on nanotu+es are 4ore than 3### <B(4CD! @2A!' it does not 4ean that they can ha.e
Journal of Energy Technologies and Policy www.iiste.org
ISSN 2224-3232 (Paer! ISSN 222"-#"$3 (%nline!
&ol.4' No.3' 2#(4

2
the sa4e high le.el of conducti.ity' +eing integrated into other 4aterials. *s oscillation fre>uency of ato4s
for4ing car+on nanotu+es is 4uch higher than of surrounding 4aterial ato4s' it results large ther4al resistance
at the interface +etween nanotu+es and other 4aterial co4onents. Therefore ther4al conducti.ity of oly4ers
with nanotu+es as filler is 4any ti4es lower than it was e5ected. 6owe.er' there is still the +elief that it is
ossi+le to increase ther4al conducti.ity of oly4ers in 2 ; 3 ti4es +y a s4all a4ount of added nanofiller (u to
(?!. The ro+le4 is in the difficulty of disergation' disersion of nanoarticles in a oly4er 4atri5 without
adhesion' without for4ation of conglo4erates' +ecause secial roerties of car+on nanotu+es are +etter
o+ser.ed when they are in the isolated state. In this case' a oly4eric 4atri5 turns into the state of a +oundary
layer with roerties which are different fro4 .olu4e oly4er sa4les.
Physical roerties of car+on nanotu+es and oly4er co4osites ha.e +een widely studied in recent years.
Nu4erous wor,s are de.oted to 4athe4atic 4odeling rocesses' occurring in car+on nanotu+es and to the
calculation of transfer coefficients' while there is li4itation of e5eri4ental wor,s. 8any articles are de.oted to
the study of 4echanical and electrical roerties of car+on nanotu+es. *s for ther4al hysical roerties such as
secific heat caacity' heat and ther4al conducti.ity' such wor,s are not enough. 8oreo.er' the u+lished
results show a large scatter of characteristics.
The authors @3A +y three different 4ethods were 4easured ther4al conducti.ity and secific heat caacity of
single ; walled car+on nanotu+es in a te4erature range fro4 ; 2#
o
0 u to E $#
o
0. 0lean single ; walled car+on
nanotu+es 4odified +y thionyl chloride were in.estigated as well as grahite owder (for co4arison!. The
calculation of heat conducti.ity coefficient +ased on the 4easured .alues of ther4al conducti.ity coefficient and
secific heat caacity showed that clean nanotu+es ha.e heat conducti.ity #.(F <B(4CD!' 4odified ; #.3
<B(4CD!' that is 4uch less than the .alues shown +y other authors @4-FA.
%nly a few aers are de.oted to heat conducti.ity of eo5ide nanoco4osites. The authors @$A studied heat
conducti.ity of co4osite +ased on eo5ide' where rando4ly oriented single ; walled car+on nanotu+es are
unifor4ly disersed on the 4icro4eter le.el. E.en a s4all >uantity of nanotu+es introduced into an eo5ide
4atri5 significantly i4ro.ed its ther4al roerties. So' addition of ( 4ass? of uncleaned nanotu+es led to the
increase of heat condacti.ity +y $# ? at 4# D and +y (2"? at roo4 te4erature. The influence of the sa4e
additi.es of car+on fi+ers ha.ing 4uch larger dia4eter (G 2## n4! is three ti4es lower. The 4easured .alues
were lower than it leads fro4 the esti4ated .alues @HA.
The authors @2A in.estigated rheological' 4echanical' electric and ther4al roerties of eo5ide nanoco4osites
containing car+on nano4aterials' deending on filler concentration. In articular' for heat conducti.ity it was
shown that the 4a5i4u4 .alue #.2" <B(4CD! was o+ser.ed at (." 4ass? of car+on nanotu+es. 6owe.er' the
.alue of heat conducti.ity of ure eo5ide #.(2 <B(4CD! is surrising due to it is usually fro4 #.(H u to #.2(
<B(4CD!.

Experimental part
! "aterials and preparation of samples of nanocomposites
*s the studied o+Iects' oly4eric co4osite 4aterials +ased on eo5ide' filled +y nanostructured owders were
chosen. *s nanofillers car+on nanotu+es and aerosil were selected with sufficiently s4all concentrations fro4
#.#" 4ass? u to 3.# 4ass?' due to definitely s4all concentrations of nanofillers roduce the 4ost significant
effect at filling of oly4er co4osites @((-(2A. <ith the urose of chec,ing the influence of low concentrations
of 4icrofillers on heat conducti.ity of co4osite 4aterials' eo5ide co4osites with concentration of talc and
acti.ated car+on #.( 4ass? were studied.
Jar+on nanoowders used as fillers in oly4er nanoco4osites were reared at KI68 N*S in las4a of a
high ; .oltage discharge at at4osheric ressure @(3A. *s raw 4aterial' a 4i5ture of 4ethane and air was used.
These nano4aterials include +esides car+on nanotu+es a4orhous car+on additi.es' grahite nanoarticles and
4etal catalyst nanoarticles. So' their cleaning fro4 additi.es to get nanotu+es with 4a5i4u4 urity is a .ery
i4ortant ste in the roduction of car+on nanotu+es. *ll nanofillers were introduced as owders which had
+een cleaned +efore (heating in the air' treat4ent with hydrochloric or nitric acid with following heat treat4ent!.
6owe.er' density' and therefore orosity' .aried. So' 4ulti ; walled car+on nanotu+es had density 2F# ,gB4
3
'
and nanoowders containing car+on nanotu+es ; (## ,gB4
3
. The differences in density ro.ide e.idence of
different orosity as well as significant differences in secific surface of the o+tained nano4aterials.
The 4ain ro+le4 during creating of nanoco4osites is the rocess of unifor4ly disersing of nanofillers in a
oly4er 4atri5 due to ultradiserse articles are at to aggregate. * re.iew of e5isting 4ethods of eo5ide
nanoco4osites 4anufacturing showed that there are so4e general rinciles of for4ing of such 4aterials.
7irstly' eo5ide at roo4 te4erature has high .iscosity. Therefore' usually to reduce its .iscosity it is heated u
to "#
o
0 or is diluted +y .arious diluents' for e5a4le' +y acetone. Secondly' hardener is not inIected into eo5ide
i44ediately' +ut firstly nanoarticles are added and 4echanical 4i5ing of co4onents is roduced. =esides
4echanical 4i5ing' different e5ternal ower influences are used such as ultrasound' 4agnetic and electric fields
for 4ore unifor4 disersion of nanoarticles in a oly4er 4atri5. Thirdly' hardening is carried out in stagesL
Journal of Energy Technologies and Policy www.iiste.org
ISSN 2224-3232 (Paer! ISSN 222"-#"$3 (%nline!
&ol.4' No.3' 2#(4

3
first at roo4 te4erature and then at ele.ated te4eratures.
*s a +ase eo5ide was used' which is a art of uni.ersal eo5ide glue. *cetone was a diluent. 8echanical and
ultrasonic 4i5ing rocedures of the co4onents were used. 6ardener was olyethyleneolya4ine (PEP*!.
Te4eratures and hardening ti4es were .aried. 6owe.er' the +est results were o+tained with the following
sche4e of ther4al treat4entL (F hours at roo4 te4erature' then 3 hours at F#M0 and 3 hours at (3#
o
0.
)ensity of all the in.estigated nanoco4osites was a+out the sa4e ((((# ,gB4
3
!' due to the concentration of
filler is too s4all to ha.e a significant effect on density.
# Heat conducti$ity measurement
6eat conducti.ity 4easure4ents were carried out using de.ice IT ; N ; 4## +y the 4onotonous heating 4ethod
@(4A in a range of te4eratures fro4 ; ("#
o
0 u to ("#
o
0 with an error "?. 7irstly a sa4le was cooled until
li>uid nitrogen te4erature and then was heated adia+atically with .elocity F DB4in u to ("#
o
0.

%esults and discussion
%n figure 2 te4erature deendences of heat conducti.ity coefficient of owders of car+on 4aterials are shown'
used as filler in eo5ide nanoco4osites.
In site of nanosi9e character of the owders' heat conducti.ity of the owders on 4acroscoic scale in the state
of free filling is 4any orders less than calculated and e5ected heat conducti.ity of a searate nanotu+e. It is
connected with the fact that nanotu+es in the owder locate chaotically and their ac,age is >uite er4ea+le. The
sa4les are o+tained with high orosity that decreases heat conducti.ity coefficient. 6eat conducti.ity
coefficient of the owder of single ; walled car+on nanotu+es is less than of the owder of 4ulti ; walled car+on
nanotu+es due to its density is less.
%n figure 3 te4erature differences of heat conducti.ity coefficient of eo5ide nanoco4osites with different
fillers at the sa4e concentration are shown.
The 4ost significant increase of heat conducti.ity coefficient is o+ser.ed during filling of eo5ide +y
nano4aterials' containing 4ulti ; walled and single ; walled tu+es. -sage of acti.ated coal as filler looses the
structure that leads to decrease of heat conducti.ity of co4osite in co4arison with clean eo5ide at ele.ated
te4eratures. S4all >uantities of aerosil also increase heat conducti.ity of eo5ide' although not with the sa4e
rate as car+on nano4aterials. Since the a.erage si9e of aerosil articles is fro4 $ ; 2" n4 and aerosil has
de.eloed surface (secific surface is fro4 ((" u to 3H# 4
2
Bg! @("A so it can +e considered as nanofiller. - to
the te4erature of "#
o
0 heat conducti.ity coefficient can +e aro5i4ated +y linear deendence. The
te4erature at the +end 9one oint characteri9es the transition to the glass for4ation 9one.
To co4are te4erature deendences of all sa4les' their .alues can +e nor4ali9ed using their heat
conducti.ity coefficient at roo4 te4erature (2"
o
0!. Such nor4ali9ed te4erature deendencies are shown on
figure 4.
*ll the 4aterials ha.e al4ost linear deendence' although sloe of these deendences is different. It is esecially
significant at low te4eratures. So it is ossi+le to esti4ate heat conducti.ity of any nanoco4osite at any
te4erature in a range fro4 ; ("#
o
0 u to 2"
o
0' assessing its heat conducti.ity Iust at roo4 te4erature. The
te4erature deendence of nanoco4osites can +e descri+ed +y >uasilinear deendenceL


and te4erature deendence of eo5ide and co4osite with filling +y acti.ated coalL



where N(T! ; heat conducti.ity coefficient at the te4erature of t
o
0' N(T! ; heat conducti.ity coefficient at the
te4erature of 2"
o
0' T ; te4erature in 0elsius degrees.
The research of the influence of the concentration of car+on filler on heat conducti.ity of eo5ide
nanoco4osite was carried out using the 4aterial of eo5ide E 4ulti ; walled car+on nanotu+es at the
concentrations of #.#?' #.#" 4ass?' #.( 4ass?' #.3 4ass?' #." 4ass?' #.$ 4ass?' (.# 4ass?' 3.# 4ass?. %n
figure " the concentration deendence of heat conducti.ity coefficient of this 4aterial at roo4 te4erature is
shown.
It is o+ser.ed that e.en such s4all concentration of 4ulti ; walled car+on nanotu+es as #.#" 4ass? increases
heat conducti.ity coefficient. The 4a5i4u4 increase is o+ser.ed not at a certain concentration' +ut in a range of
concentrations fro4 #.( 4ass? u to (.# 4ass?. The decrease of heat conducti.ity coefficient at the increase of
concentration is due to the technological features.
Kow te4eratures influence on the structure of co4osites. )ue to the differences in heat e5ansion coefficients
Journal of Energy Technologies and Policy www.iiste.org
ISSN 2224-3232 (Paer! ISSN 222"-#"$3 (%nline!
&ol.4' No.3' 2#(4

4
of filler and fi5ant during cooling' the rocess of crac,ing with for4ation of 4icro and 4acroorosity can occur.
*s a result heat conducti.ity of the 4aterial decreases. %n figure F te4erature characteristics of heat
conducti.ity coefficient of nanoco4osite Oeo5ide E 4icro ; walled car+on nanotu+esP with different
concentration of filler are shown.
The 4ost significant increase of heat conducti.ity in the whole te4erature range is referred to nanoco4osite
with #.( 4ass? of 4ulti ; walled car+on nanotu+es. It see4s as this concentration is oti4al for this 4aterial.
7or 4ore co4lete reali9ation of roerties of different nanotu+es it is necessary to diserse the4 carefully in a
oly4er 4atri5 with the a+sence of agglo4erates fro4 the strands of nanotu+es due to e5actly the interfaces of
nanotu+es contri+ute to ther4al resistance of heat trans4ission in the 4aterial. )uring the increase of filling rate'
the increase of contact surface of nanotu+es and' corresondingly' of ther4al resistance' occurs.
Therefore it is necessary to gain different disergation 4ethods' including ultrasound' and also to use electric
and 4agnetic fields for lining of nanotu+es and their unifor4 disersion in a oly4er 4atri5. In recent ti4es
close attention is aid to functioning' to acti.ating of nanotu+esQ surface to searate the4 +etter and to increasing
of adhesion' due to 4aIority of researchers refer less .alues of roerties of oly4er nanoco4osites with
car+on filler in co4arison with the redicted theoretical .alues to inert nature of grahene structure and' as a
result' to di4inished interface interaction @(F' HA.



7IR. 2. Te4erature deendencies of heat conducti.ity coefficient of car+on nanofillers.


( + !
Journal of Energy Technologies and Policy www.iiste.org
ISSN 2224-3232 (Paer! ISSN 222"-#"$3 (%nline!
&ol.4' No.3' 2#(4

"

7IR. 3. Te4erature deendencies of heat conducti.ity coefficient of eo5ide co4osites with the concentration
of filler #.( 4ass?.


7IR. 4. 6eat conducti.ity coefficient nor4ali9ed to the .alue at 2"
o
0.


7IR. ". )eendence of heat conducti.ity coefficient fro4 the concentration of 4ulti ; walled car+on nanotu+es.
( ; heat conducti.ity coefficient' <B(4CD!S c ; the concentration of filler' 4ass?.
Journal of Energy Technologies and Policy www.iiste.org
ISSN 2224-3232 (Paer! ISSN 222"-#"$3 (%nline!
&ol.4' No.3' 2#(4

F

7IR. F. Te4erature deendences of heat conducti.ity coefficient of eo5ide co4osite with different
concentrations of 4ulti ; walled car+on nanotu+es.

%eferences
(. &aia 1.*.' <agner 6.). 7ra4ewor, for nanoco4osites. 8aterials today' 2##4' No.e4+er' . 32 ; 3$.
2.IiIi4a S. 6elical 4icrotu+ules of grahitic car+on. Nature. (22(. &ol. 3"4' . "F ; "H.
3.&retenar &.' S,a,alo.a &.' Du+icar K.' 1oth S. Ther4ohysical roerties of single wall car+on nanotu+es.
Euro8at ; 2##3' Kausanne' Swit9erland' Set. ( ; "' 2##3. -2 ; ("F#.
4.6one J.' <hitney 8.' Pis,oti 0.' :ettl *. Ther4al conducti.ity of single ; walled car+on nanotu+es. Physical
re.iew =. (222. &ol. "2' No. 4' 12"(4 ; 2"(F.
". 6one J.' Klaguno 8.0.' Ne4es N.8.' Johnson *.T.' 7ischer J.E.' <alters ).*.' 0asa.ant 8.J.' Sch4idt J.'
S4alley 1.E. Electrical and ther4al transort roerties of 4agnetically aligned single wall car+on nanotu+e
fil4s. *lied Physics Ketters. 2###. &ol. $$' No. "' . FFF ; FFH.
F.7ischer J.E.' :how <.' &a.ro J.' Klaguno 8.0.' Ruthy 0.' 6aggen4ueller 1.' 0asa.ant 8.J.' <alters ).E. and
S4alley 1.E. 8agnetically aligned single wall car+on nanotu+e fil4sL Preferred orientation and anisotroic
transort roerties. Journal of *lied Physics. 2##3. &ol. 23' No. 4' . 2("$
$. =iercu, 8.J.' Klaguno 8.0.' 1adosa.lIe.ic' 6yun D.J.' Johnson *.T. and 7ischer J.E. 0ar+on nanotu+e
co4osites for ther4al 4anage4ent. *l. Phys. Ketters. 2##2. &ol. H#' . 2$F$ ; 2$F2.
H.Nan 0. ; <.' Shi :.' Kin T. * si4le 4odel for ther4al conducti.ity of car+on nanotu+e ; +ased co4osites.
0he4. Phys. Ketters. 2##3. &ol. 3$"' . FFF.
2.Song T.S.' Toun J.1.' Proerties of eo5y nanoco4osites filled with car+on nano4aterials. (2
th
P%KT06*1
<orld 7oru4 on *d.anced 8aterials. Portugal' Jan. F ; 2' 2##4.
(#.Schadler K.S.' Riannaris S.0.' *Iayan P.8. Single ; walled car+on nanotu+e ; oly4er co4ositesL strength
and wea,ness. *d.anced 8atter. 2###. &ol. (2' No. (#' . $"# ; $"3.
((.*llaoui *.' =ai S.' 0heng 6.8.' =ai J.=. 8echanical and electrical roerties of a 8<NTBeo5y co4osite.
0o4os. Sci. Tech. 2##2. &ol. F2' . (223 ; (22H.
(2.Kau D.T.' Shi S./.' 0heng 6.8. 8icro ; 4echanical roerties and 4orhological o+ser.ation on fracture
surface of car+on nanotu+e co4osites re ; treated at different te4eratures. 0o4. Sci. Tech. 2##3' &ol. F3' .
((F( ; ((F4.
(3.:hdano, S.*.' =uya,o. I.7.' 0hernu,ho *.P.' Drau,lis *.&.' Solntse. *.P.' Shash,o. *.E. 0ar+on
nanotu+es synthesis under none>uili+riu4 conditions. Nanotechnology in Physics' 0he4istry and =iotechnology'
St ; Peters+urg. 2##2.
(4.Platuno. E.S. Ther4ohysical analysis under 4onotonous 4ode. 8.L Energiya' (2$2.
(".8aligin *.*. Surface che4istry and nanotechnologyL interaction and rosects. Soroso. scientific Iournal.
2##4. &ol. H' No. (' . 32 ; 3H.
(F.<eisen+erger 8.0.' Rrul,e E.*.' Jas>ues ).' 1antell T.' *ndrews 1. Enhanced 4echanical roerties of
olyacrylonitrile. J. Nanosci. Nanotech. 2##3. &ol. 3' . "3" ; "32.