Electrical Conductivity of Lignocellulose Composites Loaded with Copper powders

Tailoring new composites within a perspective of sustainable development is applied to more and more materials. Ecological concerns have resulted in a renewed interest in natural, renewable resources-based and compostable materials, and therefore issues such as materials elimination and environmental safety are becoming important. For these reasons, material components such as natural fibers, biodegradable polymers obtained from biomass can be considered as interesting environmentally safe alternatives for the development of new biodegradable composites biocomposites!. "iomass is defined as consisting of all plant and plant-derived materials including livestoc# manures. The main classification of biodegradable polymers in different families is$ agro-polymers e.g., polysaccharides! obtained from biomass by fractionation% polyesters, which are obtained by fermentation from biomass or from genetically modified plants e.g., polylactic acid$ '+)!% and polyesters synthesi*ed by petrochemical process e.g., e.g., polyhydro&yal#anoate$ '()!% polymers synthesi*ed from monomers obtained from biomass polycaprolactone$ ',+, polyesteramide$ 'E), aliphatic or aromatic copolyesters!, from fossil resources -./. ) large number of these biodegradable polymers are commercially available. They show a large range of properties and at present, they can compete with non-biodegradable polymers in different industrial fields e.g., pac#aging, agriculture, hygiene, and cutlery! -0/. +ignocellulosic biomass is the nonstarch, fibrous part of plant material and is an attractive resource because it is renewable and abundant -1/. +ignocellulose-based fibers are the most widely used. 2ntrinsically, these fibers have a number of interesting mechanical and physical properties -3-4/. The structural and chemical composition of lignocellulosic feedstoc#s is highly variable because of genetic and environmental influences and their interactions Table .!. Table . lists general characteristics of agriculture-derived biomass, specifically crop residues from corn and small grains and dedicated perennial grasses, and other potential biomass resources -0/. ,hemical composition of lignocellulosic feedstoc#s is a #ey factor affecting properties of this biodegradable polymer and its composites -5, 6/. 7ith their environmentally friendly

character and some techno-economical advantages, these fibres motivate more and more different industrial sectors automotive! to replace common fibreglass, for e&ample. "iocomposites are obtained by the combination of biodegradable polymer as the matri& material and fillers -./. +ignocellulose is the term used to describe the three-dimensional polymeric composites formed by plants as structural material. 2t consists of variable amounts of cellulose, hemicellulose, and lignin -0/. +ignocellulosic feedstoc#s are composed primarily of carbohydrate polymers cellulose and hemicellulose! and phenolic polymers lignin!. +ower concentrations of various other compounds, such as proteins, acids, salts, and minerals, are also present. ,ellulose, the most abundant naturally occurring plant polysaccharide, consists of long chains of anhydro8-9-glu#opyranose units ):;! with each cellulose molecule having three hydro&yl groups per ):;, with the e&ception of the terminal ends, whereas hemicellulose is the second most abundant plant polysaccharide readily available, especially from annual plants and agriculture crop residues such as corn cobs, corn grain, wheat stems, seed coats, and sugar cane stal#s. 'olysaccharides associated with hemicellulose constitute the cell wall of land plants% 9glucoronic acid, +-arabinose, and 9-&ylose are present in the cell wall of corn cobs in the appro&imate ratio of 0$5$.<, respectively -</. +ignin .=0=> of total feedstoc# dry matter! is polyphenolic structural constituent of plants. 2t is the largest non-carbohydrate fraction of lignocellulose. ;nli#e cellulose and hemicellulose, lignin cannot be utili*ed in fermentation processes% however, it may be useful for other purposes. ?ther compounds present in lignocellulosic feedstoc#s are #nown as e&tractives. These include resins, fats and fatty acids, phenolics, phytosterols, salts, minerals, and other compounds -0/. ,ellulose and hemicellulose typically ma#e up two-thirds of cell wall dry matter and can be hydroly*ed to sugars and then fermented to ethanol. )lso, both cellulose and hemicelluloses have properties for potential use in the biomedical area, as they have the ability to pass through the digestive tract unchanged. ?wing to their resistance to digestion, they are eligible as potential e&cipients that could be used in the pharmaceutical industry -.@/. The research effort on electrically conducting polymer composites filled with metallic powders has had a great development in the last two decades. The addition of metals fillers into a polymer matri& allows enables the preservation of the mechanical properties of the polymer while e&ploiting the electrical conduction properties of the metal -../. The conductivity of filled

polymers is usually strongly dependent on the nature of the contact between the conductive filler elements and depends critically on the volume fraction of the conducting filler particles, and is well e&plained by percolation theory -.0-.3/. Table 1: Composition of different natural lignocellulosic feedstocks [2].
Cellulose Crop residues ,orn stover 16 Coybean 11 7heat straw 16 Dye straw 1. "arley straw 30 Warm-season grasses Cwitchgrass 15 "ig bluestem 15 2ndiangrass 1< +ittle bluestem 1= 'rairie 3. cordgrass Aiscanthus 31 Cool-season grasses 2ntermediate 1= wheatgrass Deed 03 canarygrass Cmooth 10 bromegrass Timothyb 06 Tall fescue 0= Other crops )lfalfa 05 Forage sorghum 13 Cweet sorghum 01 'earl millet 0= Cudangrass 11 Hemicellulose Lignin Acid detergent lignin 3 .3 < 1 5 4 4 4 4 4 0 4 = 6 1 6 Crude Protein Ash

04 .3 0< 0= 06 0< 06 0< 1. 11 03 0< 14 14 1@ 0= .0 .5 .3 1= 05

.< .= .< .6 .< .3 .4 .. -

= = 3 1 5 1 4 1 1 1 1 .@ .3 5 .1 .5 .@ .0

4 4 4 4 .. 4 4 6 5 4 0 4 6 6 4 .. < = = < .0

2nformation about numerous e&isting possibilities of polymers containing dispersed conductive fillers and various methods of manufacture of such materials have been reported widely in the literature for the last years -.=00/. Aetal-filled conducting polymer composites have found uses in electromagnetic shielding of computers and electronic eBuipment, as

conducting adhesives in electronics pac#aging, underfill for flip chips, cold solders, switching devices, static charge dissipating materials and devices for surge protection -.., 01-04/. )lso they found numerous technological applications as self regulating heater, photothermal optical recording, direction finding antennas, chemical detecting sensors used in electronic noses, chemical and electrochemical catalysts and adsorbents -05-11/. These polymer-based electrically conducting composites have several advantages over their pure metal counterparts, including lower cost, ease of manufacture, high fle&ibility, reduced weight, mechanical shoc# absorption ability, corrosion resistance, and conductivity control -../. The method most often employed to alter the electrical properties of a polymer is an e&trinsic approach whereby the insulating polymer is combined with a conductive additive. 2t is #nown that, in general, the percolation theory is used to describe the nonlinear electrical conductivity of e&trinsic conductive polymer composites. (ence, the electrical conductivity of polymer composites does not increase continuously with increasing electroconductive filler content. The conducting additive is incorporated into polymers at levels that allow the composite to maintain its electrically insulative Bualities, as well as at higher levels, which allow the composite to become electrically semiconductive. )s the volume fraction of the conducting filler particles increases, the particles come into contact with one another to form the conduction paths through the composite. )s the result there is a critical composition percolation threshold! at which the conductivity increases by some orders of magnitude from the insulating range to values in the semiconductive or metallic range -.0,.1,.4/. For efficiency and in order to decrease the difficulty of the process and economic costs, the amount of the conductive phase for achieving materials with high conductivity should be usually as small as possible. The percolation threshold is typically .=1@ vol.> for dense spherical micron si*e particles -.., .4, 01, 0=/ ) huge number of different models have been proposed for the estimation of the conductivity or inverse resistivity! vs. filler concentration curves -13 - 1</. The aim of this wor# was to investigate electrical properties of copper powder filled lignocellulose matri& composites produced under different pressures, as well to compare the obtained results with previous research in this field and percolation theories.

Materials and methods :iven that one of the most abundant sources of lignocellulose is corn cob, the matri& natural polymer used in e&periments was a commercial grade lignocellulose produced by Aai*e Desearch 2nstitute EFemun 'olGeE -.=/. ,elgranH , fraction was used, with particle si*e below 66 Im. ,hemical composition of ,elgranH , fraction including moistrue, ash, oil, protein and nitrogen free e&tracts content is given in Table 0. ,omposition of lignocellulose comple& of cob fraction is given in Table 1. )ll presented data were statistically analysed using variance analysis +C9! for unifactorial e&periment with randomi*ed bloc# design -.=/. Table 2. Chemical composition of Celgran C fraction -.=/ Fraction Aoisture >! , +C9 @.@. ...0@ @.1.3 )sh >! ..0. @.1.3 ?il >! @.@4 @.1.3 'rotein >! 3.1. @.1.3 JFE >! 4=..@ @.1.3

NFE nitrogen free e!tracts

Table ". #ignocellulose comple! of cob fraction -.=/ Fraction ,ellulose >! , +C9 @.@. 0<.3@ @.333 (emicellulose >! 1<.5@ @.1.3 +ignin >! 4.4@ @.1.3 J9F >! 5<.3 @.=33 )9F >! 1<.5 @.1.3

N$F % neutral detergent fiber &$F % acidic detergent fiber

Table '. (h)sical and chemical properties of Celgran C fraction -.=/

Fraction Colubility - > 7ater Ethanol )cetone Codium hydro&ide )bsorption - > 7ater ?il ?il after water absorption moist sample! ?il after water absorption dry sample!

+C9@.@.

....= =,@@ .@,<< 0=,<4

@.1.3 @,1.3 @,1.3 @,1.3

=6@,.4 .0<,05 03,5< 064,00

03,43 @,401 @,1.3 @,1.3

Thermal stability of the lignocellulose was investigated by thermogravimetry using T) 2nstruments K4@@ thermal analy*er at .@o,Lmin heating rate under dynamic argon atmosphere. ?btained T:) curve, presented on Fig.., illustrates thermal behavior stability! of used lignocellulose and characteristic temperatures of the observed thermal events confirm presence of the main constituents Table 1.!.

Fig. 1. *esults of thermogra+imetric anal)sis of lignocellulose % fraction Celgran, C The mass loss below .@@o, can be attributed to the evaporation of water moisture! originally present in the sample Table 0.!. The mass loss increases with temperature gradually up to appro&imately 0@@o, while in the region between 0@@ and 3@@o, more significant mass loss occurs. ?n the obtained 9T:) curve Fig..! two distinct pea#s can be observed within this temperature interval, suggesting the e&istence of two separate thermal events. )ccording to the literature data -0@-00/, the first event that occurs at 0.@-1@@ o, can be associated with the decomposition of hemicellulose and the slow degradation of lignin, while the second event 05=1=@o,! can be attributed to the degradation of cellulose. 'ossible discrepancies between literature data and the 9T:) results may be associated with the amount of cellulose and lignin in the lignocellulose material Table 1.!, given that Chebani etal. 1 and 9)lmeida et al..3 demonstrated that higher cellulose and lignin content in lignocellulosic materials leads to a greater thermal stability. "a#arni prah #oriMNen #ao ele#tro provodni punioc dobiGen Ge ele#trohemiGs#im putem, programiranim struGno-napons#im reOimom - reversnom struGom -.4,.5/. )mplitudna gustina struGe Ge imala vrednost 14@@ )Lm 0. Preme #atodnog taloOenGa Ge i*nosilo 3@ s, a vreme anodnog rastvaranGa @.0s. Preme narastanGa praha rQ.= min, proto# ele#trolita, KQ@... dm1Lmin, temperatura ele#trolita, tQ =@0!o,, #oncentraciGa ba#ra, , ,uR0! Q .= gLdm1 i #oncentraciGa sumporne #iseline, , (0C?3! Q .3@ gLdm1. "a#arni prah Ge stabili*ovan rastvorom pogodne povrMins#i a#tivne materiGe -.6/. 'article si*e of used lignocellulose and copper powder was analysed using Aalvern 2nstruments laser diffractometer Aastersi*er 0@@@ with the Ccirocco 0@@@ module. ?btained particle si*e distributions are presented on Fig.0. The mean particle si*es of lignocellulose powder and copper powder determined by laser diffractometry are d @.=! Q 4@.=33 Im and d @.=! Q 05.0.< Im, respectively.

a-

bFig 2. (article si.e distribution of used matri! and conducti+e filler po/ders: a- lignocellulose and b- copper Aorphology of matri& lignocellulose! and conductive filler copper! powders was analysed using scanning electron micrscopy CEA!. The si*e and the shape of the matri& and filler particles are illustrated in Fig.1.

a-

bFig. ". 0E1 micrographs of pure matri! and filler po/ders a- lignocellulose and b- copper

2nvestigated lignocellulose and copper powder composites were prepared with filler contents in the range .@ wt.> - <@ wt.> with the .@ wt.> increment, while pure lignocellulose

and copper samples were prepared as reference materials. The samples were produced from thoroughly homogeni*ed powder mi&tures that were pressed into .4 mm diameter tablets at ambient temperature t Q 0=o,! under pressure of .@, 0@ and 05 A'a. Aorphology of the investigated composites was analy*ed using scanning electron microscopy CEA!.

Fig. '.

0E1 micrograph of the obtained lignocellulose%copper po/der composite

Cample thic#nesss necessary for the calculation of porosity and conductivity! was determined using micrometer, to an accuracy of @.@. mm. Ceveral thic#ness measurements were ta#en per sample and then averaged. Theoretical density of composites 2t was calculated according to relation -0,.</$
t = (. 3 f ) m + 3 f f

.!

where 3 is volume fraction, 2 density while f and m inde&es correspond to filler copper powder! and matri& lignocellulose!, respectively. 'orosity of the investigated composites 4 was determined by comparison of e&perimental and theoretical densities of the samples according to relation -.</$
t e = .@@ t

0!

where 2e is e&perimentally obtained value of composite density. Electrical conductivity measurements were carried out by $C 567%characteristic measurements of the samples using 9igital Aultimeter, Aodel 343, Cimpson Elec. ,ompany. :eometry of the instrument contacts rings! used is such that it minimi*es edge effects thus it can be assumed that they do not e&ist. Electrical conductivity was determined according to relation$
=
7 l 5 0

1!

where 8 is electrical conductivity, 7 current through sample, 5 potential difference, l length and 0 cross%sectional area of the sample. (ardness of the samples was determined at ambient temperature t Q 0= o,! using Chore 9 hardness testing method in acordance with )CTA 9 003@-46 standard. Five data points were ta#en for each sample and no difference was found between values obtained for both faces of each sample. esults and discussion The theoretical density of the composite dt! was calculated from the relation .!-pinto, Gahorina, tara/ where 3 is the volume fraction, d is the density, and m and f stand for the matri& and filler, respectively. 'orosity of the investigated composites, 49 was determined by comparison of e&perimental and theoretical densities of the samples according to relation$
0!

where de represents the e&perimental density. Figure 3 represents the porosity rate of different composites as function of the filler volume fraction at various processing pressures. 2t can be seen that, as e&pected, the porosity decreases with the increase of pressure, due to higher pac#aging effect. ?n the other hand, as the volume fraction of the very porous natural matri& decreases, the porosity decreases too. 2n all

cases, the porosity is still rather high around percolation threshold and it is between 03> and 1@>. These results show that although the Buality of the obtained composites was good, some changes in the preparation processes can lead to lover porosity composites.

Figure ': (orosit) of the copper po/der filled lignocellulose matri! composites at +arious pressures. Figure = shows the dependence of hardness measured as shore 9 values, in various composite of lignocelluloses matri& and copper powder filler prepared under various pressures. )s e&pected with pressure molding under low temperatures 0=S,!, the hardness decreases with the increase of the filler fraction and it increases with the increase in processing pressure.

Figure :: ;ardness of lignocelluloses matri! and copper po/der filler composites prepared under +arious pressures. 1easurements are sho/n as 0hore $ +alues. The electrical conductivity of the composites as a function of filler content for the samples was measured as stated in Aaterials section. The conductivity measurements showed typical C-shaped dependency with three regions dielectric, transition, and conductive% Fig. 4!. These measurements were performed on all the samples prepared under three different pressures$ .@ A'a, 0@ A'a and 05 A'a. )s e&pected, samples with low filler content were almost nonconductive. (owever, the electrical conductivity of the composites increased dramatically as the copper content reached the percolation threshold at .3.3> vLv! filler for all the processing pressures. The value of the percolation threshold was obtained from of the ma&imum of the derivative of the conductivity as a function of filler volume fraction Fig. 4!. )ccording to Flandin et al.-3/, values of 0@3@> vLv! are typical for spherical particles of filler. This much lower percolation threshold can be e&plained by much higher specific area of the highly dendritic copper powder particles used as filler. The statistical percolation theory is usually used to relate the electrical conductivity of the composite to the e&istence of clusters of connected particles, which give rise to the so-called conducting infinite cluster above the threshold. 7ith highly porous, highly dendritic particles with high values of specific area, more interparticle connections can be obtained at lower filler content. )bove the percolation threshold, the conductivity of composite increased by much as fourteen orders of magnitude. The increase in

the conductivity is higher than stated by (into et all. due to filler with high specific area. 2t can be seen from the Figure 4 that under investigated range of pressures there is no change in the percolation threshold. (owever, in the conductive region, composites with the same volume fraction of copper powder prepared under higher pressure have higher values of conductivity.

Figure <: 3ariation of electrical conducti+it)9 as a function of filler content9 of lignocellulose composites filled /ith copper po/der under different processing pressures. For percolation theory, the relationship between the electrical conductivity of the mi&ture and the volume fraction of the conductive filler was given by Tir#patric#$ 3! where U is the electrical conductivity of the mi&ture, U @ is the electrical conductivity of the fillers particles, 3f is the volume fraction of the filler, 3fV is the critical volume concentration at the threshold of percolation, and t is an e&ponent that determines the increase in the conductivity above 3fV. This theory provided a good description of the e&perimental results near the transition point. (owever, discrepancies were observed between the critical parameters 3fV, t! resulting from eB. 3! and the e&perimental values, since this theory does not include the shape of the conductive filler and it does not consider several other parameters. )lthough the e&perimental results show that the electrical conductivity depended strongly on the viscosity and the surface tension of the filled polymers, it also depended on the filler particles geometrical parameters and

the filler matri& interactions. These parameters were considered by Aamunya et al.-.=,.4/. ) model they developed consideres specific parameters for each composite and it is given in the basic theory$ =! where Um is the ma&imal conductivity of composites, F is the filler pac#ing density coefficient eBuivalent to the ma&imal value of the filler volume fraction!, and teff is given by the relation 4! where t1 is eBuivalent to the t parameter in the basic eB. 3!. t1 usually has a value around ..5, and t2 depends on the specific composite. Thus, teff could have higher values depending on the filler polymer interactions.

!re"a da resim #ednacinu$ potom da %avrsim posledn#i pasus& EBuation 3! will be used in this study to interpret e&perimental results. The fit, above the percolation threshold, of the electrical conductivity as function of the volume fraction of Fn filled in urea formaldehyde embedded in cellulose powder is given in Figure =. The agreement between the e&periment and the theory was fairly good. The deduced parameters were 3fV W .6.=>, teff W 0.0=, and F W @.3=. The determined pac#ing density coefficient was in good agreement with the prediction of eB. 3!.0= The teff obtained value was close to 0, which represented the accepted theoretical value for three-dimensional lattices.04,05 This theoretical value was independent of the e&act composition of the random composites.04 ?n the other hand, the critical threshold percolation value obtained was in good agreement with that determined by e&perience, 3fV W .6.<>. Elsewhere, this result was also close to the .6> found in Fn-filled nylon 4.00 2ndeed, the random composites electrical conductivity was already shown to depend on several parameters, .601,06,0< such as the viscosity and the polymers surface tension, especially in the case of mi&es in which the conductive powder is dispersed% the si*e, shape, and surface energy of the

filling particles% and the powder dispersion procedure, that is, the type, duration, and strength of shear. 2n this study, the particle si*es and shape of Fn filled in nylon 4 and ureaformaldehyde were the same, and the dispersion procedure was maintained uniformly. ,onseBuently, the small difference in threshold values observed between nylonFn and ureaformaldehydeLFn composites was probably due to the specific matri&filler interaction and viscosity effects.

E'E E(CE) * eference ce "iti us+lad#ene u %avisnosti od casopisa u +o#i se sal#e$ reference samo i% uvoda, -./ +. )verous, F. +e 9igabel in Carboh)drate (ol)mers, --$ ., 36@-3<1, 0@@4! -0/ 9.T. +ee, P.J. ?wens, ). "oe, '. Xeranyama, ,omposition of (erbaceous "iomass Feedstoc#s, Couth 9a#ota Ctate ;niversity, 0@@5! -1/ 'erlac#, D.9., +.+. 7right, ).F. Turhollow, D.+. :raham, ".X. Cotc#s, and 9.,. Erbach. 0@@=. "iomass as feedstoc# for a bioenergy and bioproducts industry$ the technical feasibility of a billion-ton annual supply. 9?EL:?-.@0@@=-0.1=, )pril. ;.C. 9epartment of Energy and ;.C. 9epartment of )griculture. -3/ "led*#i, ). T., Y :assan, X. .<<<!. ,omposites reinforced with cellulosebased fibres. 'rogress in 'olymer Ccience, 03, 00.053. -=/ Aohanty, ). T., Aisra, A., Y (inrichsen, :. 0@@@!. "iofibres, biodegradable polymer and composites$ an overview. Aacromolecular Aaterials and Engineering 054L055!, .03. -4/ Caheb, 9. J., Y Xog, X. '. .<<<!. Jatural fiber polymer composites$ a review. )dvances in 'olymer Technology, .6 3!, 1=.141 -5/ (amelinc#, ,.J., :.P. (ooiGdon#, and ).'. FaaiG. 0@@=. Ethanol from lignocellulosic biomass$ techno-economic performance in short-, middle-, and long-term. "iomass and "ioenergy 06$ 1633.@. -6/ (ames, ".D., C.D. Thomas, ).9. Cluiter, ,.X. Doth, and 9.7. Templeton. 0@@1. Dapid biomass analysis. Jew tools for compositional analysis of corn stover feedstoc#s and process intermediates ethanol production. )pplied "iochemistry and "iotechnology. .@=.@6$ =.4. -</ A. 2oelovich, 2n =io*esources% /*.,, .3@1-.3.6 0@@6! -.@/ A.). (ubbe, ?.X. DoGas, +.). +ucia and. A. Cain, 2n =io*esources% /*/,, <0<-<6@ 0@@6! -../ P.(. 'oblete, A.'. )Z lvare*, P.A. Fuen*alida, '?+[Aer ,?A'?Cites, 1@$106111, 0@@<. -.0/ 9avid C., Ac+achlan. Aichael "las*#iewic*, and Dobert E. Jewnham, X. )m. ,eram. Coc., 51 6!, 0.65 .<<@!. -.1/ Ctauffer, 9ietrich and )harony, )mnon. 2ntroduction To 'ercolation Theory, 0nd ed., Taylor and rancis, +ondon .<<0!. -.3/ +.X. (uiGbregts, 'h.9. thesis ,harge transport and morphology in nanofillers and polymer nanocomposites, Technische ;niversiteit Eindhoven, 0@@6 -.=/ "oGaniN P., ;em. ind. -. 4! =0< 0@.@! -.4/ 'into :., Aaaroufi ).T., >. &ppl. (ol)mer. 0ci.9 0- 0@.. 0@@=! -.5/ Tha#ur A., 1acromolecules9 12 44. .<66!

-.6/ Con (.C., +ee (.X., 'ar# [.X., Tim X.(., (ol)m.7nt.9 .- 1@6 .<<6! -.</ "ouchet X., ,arrot ,., :uillet X., >. (ol)m. Eng. 0ci.9 .3 14 0@@@! -0@/ Flanding +., ,hang )., Ja*aren#o C., (iltner )., "aer E., >. &ppl. (ol)mer. 0ci.9 4- 6<3 0@@@! -0./ Tamel C., E!press (ol)umer #etters9 2 =34 0@@5! -00/ Eduard ). Ctefanescu, ,odrin 9aranga, ,ristina Ctefanescu, 1aterials9 1 0@<= 0@@<! -01/ +. \iangcheng and 9.9.+. ,hung, ,omposites 'art "$ Eng., 1@, 005 .<<<!. -03/ [. \u, 9.9.+. ,hung, and ,. Aro*, ,omposites 'art )$ )ppl. Cci. Aanuf., 10, .53< 0@@.!. -0=/ A.-+. Cham and X.-T. Tim, ,omposites 'art )$ )ppl. Cci. Aanuf., 1=, =15 0@@3!. -04/ C.T. "hattacharya, Ed., Aetal Filled 'olymers$ 'roperties and )pplications, Aarcel 9e##er, Jew [or# .<64!. -05/ 9elmonte X., 2n 1etal6(ol)mer Composites9 Pan Jostrand Deinhold, Jew [or#, .<<@ -06/ +afuente '., Fontecha )., 9ia* X.A., Auno* ).E., *e+. (last. 1od.9 ..4 0=5 .<<1! -0</ :ul P.E., 2n 0tructure and (roperties of Conducting (ol)mer Composites, PC'$ Jew [or#, .<<4. -1@/ [i \.C., 7u :., 'an [., (ol)m. 7nt.9 .. ..5 .<<5! -1./ Auno* ".,., Cteinthal :., Cunshine C., 0ens. *e+.9 20, 1@@ .<<<! -10/ Aottahed ".9., (ol)m. Eng. 0ci.9 .3, 4. 0@@@! -11/ >ignesh et al. E>E&FChe9 ? @1'-9 2AAB. 514/6-14.17 -13/ C. Tir#patric#, *e+. 1od. (h)s., .6, =53 .<51!. -1=/ F. +u&, >. 1ater. 0ci., 18, 06= .<<1!. -14/ \.". ,hen, X. 9evau&, X.'. 2ssi, and 9. "illaud, (ol)m. Eng. 0ci., /6, 415 .<<=!. -15/ E.'. Aamunya, P.P. 9aviden#o, and E.P. +ebedev, Compos. 7nterfaces, ., .4< .<<5!. -16/ E.'. Aamunya, P.P. 9aviden#o, and E.P. +ebedev, (ol)m. Compos., 2-, 1.< .<<=!. -1</ C. 9e "ondt, +. Froyen, and ). 9eruyttere, >. 1ater. 0ci., 14, 1.< .<<=!.