research article novel polyvinyl alcohol/styrene butadiene...

Hindawi Publishing CorporationJournal of NanomaterialsVolume 2013 Article ID 542421 8 pageshttpdxdoiorg1011552013542421

Research ArticleNovel Polyvinyl AlcoholStyrene Butadiene RubberLatexCarboxymethyl Cellulose Nanocomposites Reinforced withModified Halloysite Nanotubes

Yanjun Tang12 Dingding Zhou1 and Junhua Zhang3

1 Key Laboratory of Advanced Textile Materials and Manufacturing Technology Ministry of Education Zhejiang Sci-Tech UniversityHangzhou 310018 China

2 Tianjin Key Laboratory of Pulp amp Paper Tianjin University of Science amp Technology Tianjin 300457 China3 Engineering Research Center for Eco-Dyeing amp Finishing of Textiles Ministry of Education Zhejiang Sci-Tech UniversityHangzhou 310018 China

Correspondence should be addressed to Yanjun Tang tangyjzstueducn

Received 13 May 2013 Accepted 24 September 2013

Academic Editor John Zhanhu Guo

Copyright copy 2013 Yanjun Tang et al This is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Novel polyvinyl alcohol (PVA)styrene butadiene rubber (SBR) latexcarboxymethyl cellulose (CMC)halloysite nanotubes (HNTs)nanocomposites were successfully prepared through physical blending The as-obtained PVASBRCMCHNTs nanocompositeswere coated on the surface of old corrugated container (OCC)-based paper in an effort to improve the mechanical propertiesof paper To improve the dispersion of HNTs and enhance the compatibility between HNTs and polymer matrix HNTs weremodified with titanate coupling agent (TCA) FT-IR together with TGA confirmed that TCA was grafted onto the surface ofHNTs successfully XRDdemonstrated that the crystal structures ofHNTs remained almost unchanged TEM showed thatmodifiedHNTs exhibited good dispersion and possessed nanotubular structures with an outer diameter of around 50 nm and an innerdiameter of about 20 nm SEM gave an indication that modified HNTs were dispersed more uniformly than unmodified HNTswithin PVASBRCMC matrix Rheological measurement exhibited that surface modification process enhanced the compatibilitybetween HNTs and polymer matrix thus resulting in the decreased viscosity of nanocomposites In comparison with unmodifiedHNTs modified HNTs were found to contribute more to the enhancement in mechanical properties which might be attributed tothe better dispersion and compatibility of modified HNTs evidenced by TEM SEM and rheological measurement

1 Introduction

HNTs derived from mineral resources deposited in suchcountries as China America New Zealand France andBelgium [1 2] are naturally occurring aluminosilicate min-erals with molecular formula of Al

2Si2O5(OH)4sdotnH2O [3] In

general HNTs exhibiting multiwalled nanotube structures[4] which essentially belong to kaolin varieties with thelengths of 300ndash1500 nm internal diameters of 15ndash100 nmand external diameters of 40ndash120 nm [5 6] However HNTsare to some extent different from kaolin [7] HNTs possesstwo-layered aluminosilicate mineral structures where thealuminol (AlndashOH) groups dominate the internal surface and

siloxane (SindashOndashSi) groups take up the outer surface [8ndash11]Furthermore as an alternative for carbon nanotubes HNTshave their outstanding advantages of abundantly availableresource and low cost [12ndash15] As a consequence HNTs havereceived much attention over the past decade in such fields asbiomaterials [16] and nanocomposites [17] There are manystudies regarding the application of HNTs in improving thematerial properties in the previous literature Ismail et al [18]studied the morphological characteristics and mechanicalproperties of ethylene-propylene-diene monomer (EPDM)composites filled with HNTs and found that the tensilestrength stiffness and ductility of EPDMHNTs nanocom-posites were simultaneously enhanced with the added HNTs

2 Journal of Nanomaterials

particularly at a high HNTs loading Schmitt et al [19] usedboth modified and unmodified HNTs as nanofillers to plasti-cized starch polymericmatrix and investigated the structuralmorphological thermal and mechanical properties of plasti-cized starchHNTs nanocomposites Rybinski et al [20] andDu et al [21] studied the thermal properties and flammabilityof different nanocomposites based on HNTs respectivelyand proposed that the nanofillers can increase the thermalstability and decrease the flammability of nanocomposites

However much like other nanofillers the main difficultyin utilization of HNTs in nanocomposites arises from theagglomeration ofHNTs and the poor interfacial compatibilitybetween HNTs and polymer matrix [22] To overcome thesedisadvantages many efforts have been made to disperseHNTs uniformly in polymer matrix and to improve the inter-facial compatibility between HNTs and polymer matrix Jiaet al [23] used complex of resorcinol and hexamethylenete-tramine (RH) to modify HNTs and found that RH can notonly facilitate the dispersion and orientation of HNTs in SBRmatrix at nanometer scale but also enhance the interfacialcombination between HNTs and rubber matrix Joo et al[24] modified the functional groups of HNTs from hydroxylgroups (HNTs-OH) to carboxylic acids (HNTs-COOH) toimprove the dispersion of HNTs in acidic basic and neutralsolutions Prashantha et al [25] conducted the modificationof HNTs with quaternary ammonium salt and concluded thatmodifiedHNTs can lead to better performances than unmod-ified HNTs due to strong interfacial interaction between thepolymer matrix and the nanotubes

Paper quality is strongly dependent on the structuraland chemical properties of paper surface which is not onlyassociated with the fibrous matrix but also related to the finalsurface treatment [26] Surface treatments such as coatingand sizing are widely applied in papermaking industry toimprove surface strength Conventional polymer compositessuch as PVA copolymers of styrene and maleic anhydride(SMA) SBR polyurethane (PU) and polyacrylamide (PAM)are often employed to improve the properties of paperby forming a layer of polymer film on the whole papersheet [27] However there are limited studies regarding thenanocomposites containing HNTs for the surface coating ofpaper in the previous publications In the present work novelnanocomposites were designed using a blend of PVA SBRand CMC especially the incorporation of modified HNTsTo achieve desired dispersion of HNTs nanofillers and toyield a good compatibility between HNTs and the polymermatrix HNTs were modified first by TCA SubsequentlyPVASBRCMCHNTs nanocomposites were successfullyprepared through physical blending In addition the effectsof unmodified and modified HNTs on the nanocompositeproperties and the subsequent paper properties were alsostudied

2 Experimental

21 Materials HNTs used in this study were mined fromHubei Province China TCA possessing a decompositiontemperature of 210∘C a density of 1095 gcm3 and a refrac-tive index of 1446 was purchased from Hangzhou Jessica

Chemical Co Ltd SBR-latex with a solid content of 50was supplied by BASF CMC was provided by ShanghaiSinopharm Chemical Reagent Co Ltd PVA was supportedby a paper mill in Hangzhou City of China Anhydrousethanol serving as the dissolvent in the modification processof HNTs was purchased from Hangzhou Gaojing FineChemical Industry Co LtdThe commercial base paper witha basic weight of about 130 gm2 was provided by a paper millin Zhenjiang Province of China It was derived from OCCpulp a cheap and low-grade raw material

22 Surface Modification of HNTs Initially 2 g of HNTs weredispersed in 40mL of anhydrous ethanol upon ultrasonictreatment for 5min TCA was dissolved in 10mL of anhy-drous ethanol at the ratio (TCAHNTs) of 375 75 and15 respectively and then was added into the solution ofHNTs The mixture was reacted at a constant temperatureof 80∘C for 6 h under the mechanical stirring (550 rpm) ina three-necked round-bottomed flask Finally the reactionmixture was filtered and washed with anhydrous ethanol forseveral times prior to the drying process in an oven at 60∘Cfor 24 h

23 Preparation of PVASBRCMCHNTs NanocompositesIn this process the PVASBRCMCHNTs nanocompositeswith a solid content of 10were madeThe added proportionof PVA SBR was 3 1 and the weight ratio of CMCHNTswas 2 1 Initially 6375 g of PVA was added into distilledwater and heated to 90ndash95∘C until PVA was completelydissolved Subsequently specified amount of SBR was slowlyadded into the resulting PVA solution followed by theaddition of 10 g of CMC Lastly HNTs (unmodified sampleor modified sample treated with 375 TCA) were gradu-ally added into the PVASBRCMC nanocomposites As aresult PVASBRCMCHNTs and PVASBRCMCMHNTsnanocomposites were obtained

24 Preparation of Coated Paper OCC-based paper wasselected as the base paper for surface coating process Thesurface coating process was completed on a laboratory scaleZAA 2300 multicoater (Zehntner Switzerland) About 10mLof obtained nanocomposites were loaded on the base paperand then spread over with the aid of a round steel bar Thecoated paper was initially dried at ambient temperature andthen dried at 100∘C for 20min The coat weight of the papersamples was about 3 gm2

25 Characterization Fourier transformed infrared (FT-IR)spectra of HNTs were conducted on Nicolet 5700 spectrome-ter (Thermo Fisher Scientific USA)The thermal behavior ofmodified and unmodified HNTs was determined with PyrislTGA (PerKin Elmer USA) under nitrogen atmosphere at aheating rate of 20∘Cmin X-ray diffraction (XRD) was per-formed on a diffractometer (X1015840TRA-055 ARL Switzerland)with a nickel-filter Cu K120572 (120582 = 0154 nm) The morphologyanalysis was carried out by transmission electronmicroscopy(TEM) on a JSM-2100 electron microscope (JEOL Japan)at an accelerating voltage of 200KV The morphology of

Journal of Nanomaterials 3

4000 3500 3000 2500 2000 1500 1000 500

3697

3619

34492929 2854 1629

2929

2861

(a)

(b)

(c)

(TCA)

1069

912

1030

Wavenumber (cmminus1)

Figure 1 FT-IR spectra of pure TCA and HNTs modified with (a)375 (b) 75 and (c) 15 of TCA

the sized paper was observed by a ULTRA-55 field emissionscanning electron microscope (JEOL Japan) Rheologicalbehavior of the PVASBRCMCHNTs nanocomposites wasdetermined by an advanced cylinder rotary rheometer Phys-ica MCR301 (Anton Paar Austria) at 25∘C The mechanicalstrength of the paper coated with PVASBRCMCHNTsnanocomposites including tensile strength tear strength andburst strength was measured according to Chinese NationalStandards

3 Results and Discussion

31 FT-IR Spectra The FT-IR spectra of modified HNTstreated with various percentages of TCA were investigatedand the results are shown in Figure 1 For the sake ofcomparison the spectrum of pure TCA is also presentedFrom the FT-IR spectra of modified HNTs (Figures 1(a) 1(b)and 1(c)) the absorbances at 3697 3619 and 1629 cmminus1 areassociated with pure HNTs mainly due to OndashH stretchingof inner surface hydroxyl groups OndashH stretching of innerhydroxyl groups and decomposition of water respectively[28] Similarly a very strong adsorption at 1030 cmminus1 possiblyoriginates from the asymmetric flexible vibration of OndashSidue to the plenty of OndashSindashO groups on the outer surfaceThese characteristic absorption peaks mentioned above areclose to the results reported in previous literature [29] forthe same HNTs materials In addition it should be notedthat the spectra of modified HNTs samples provide evidenceof surface modification by the occurrence of the absorbanceat 2929 cmminus1 and 2854 cmminus1 These bands are indicative ofthe stretching vibrations of CndashH bonds of TCA which canbe observed in the spectra of TCA shown in Figure 1 Thesechanges in FT-IR spectra demonstrate that TCA is tightlyabsorbed on the surface of HNTs by chemisorptions which isstill existed on the surface of the modified particles even afterbeing fully washed by anhydrous ethanol [30]

100 200 300 400 500 600 70075

80

85

90

95

100

(c) (d)

(b)

200 250 300 350 400 450

85

90

95

100

Wei

ght (

)

(a)

Temperature (∘C)

Figure 2 TGA curves of (a) unmodified HNTs and HNTsmodifiedwith (b) 375 (c) 75 (d) 15 of TCA

15 20 25 30 35 40 45 50

(a)

(b)

(c)

(d)

2120579 (deg)

Figure 3 XRD patterns of (a) unmodified HNTs and HNTsmodified with (b) 375 (c) 75 and (d) 15 of TCA

32Thermal Analysis To figure out the TCA amount graftedonto the surface of HNTs the unmodified and modifiedHNTs are characterized by TGA technique Figure 2 showsthe TGA curves of unmodified HNTs and modified HNTswith different percentages of TCA As shown in Figure 2the weight loss of unmodified HNTs is about 18 when it isheated from room temperature to 700∘C (Figure 2(a)) whichis probably attributed to the weight loss of hydroxyl groupsand adsorbed matters on HNTs The results are in goodagreementwith those of Zhangrsquos investigation [31]where boththe pure HNTs and PANIHNTs nanocomposites exhibiteda similar weight-loss trend and the weight loss was lessthan 20 Moreover the vast majority of the weight lossoccurred in the range of 200ndash475∘C which can make upthe total weight above 60 In comparison with unmodifiedHNTs the TGA curves (Figures 2(b) 2(c) and 2(d)) ofmodified HNTs with different percentages of TCA show


(a) (b)

(c) (d)

Figure 4 TEM images of (a) (b) unmodified HNTs and (c) (d) modified HNTs

1 10 100 1000

01

1

10

100

Shea

r stre

ss (P

a)

A1

A2

Shear rate (sminus1)

(a)

001

01

1

A1

A2

1 10 100 1000Shear rate (sminus1)

Visc

osity

(Pamiddot

s)

(b)

Figure 5 Shear stress (a) and shear viscosity (b) as a function of the shear rate for PVASBRCMC nanocomposites with (A1) modified HNTsand (A2) unmodified HNTs

a high decomposition rate with the ascent of temperaturefrom 200 to 450∘C due to the TCA grafting on HNTs Inaddition it can be derived from Figure 2 that the total weightloss of each modified HNTs is essentially consistent with thepercentage of TCA used in surface modification The biggerthe TCA percentage used in surface modification the higherthe total weight loss of the modified HNTsTherefore similarto the results of FT-IR spectra TGA also confirms that TCA is

really anchored or grafted on the surface of HNTs regardlessof the various grafting ratio

33 X-Ray Diffraction Analysis To survey the influence ofsurfacemodification on the crystal structures of HNTs X-raydiffraction patterns of the unmodified and modified HNTswere conducted and the results are given in Figure 3 It isapparent that the X-ray diffraction peaks of the modified


(a) (b)

(c) (d)

Figure 6 SEM images of (a) base paper paper coated with (b) PVASBR composites (c) PVASBRCMCHNTs nanocomposites and (d)PVASBRCMCMHNTs nanocomposites

HNTs samples nearly remain consistent with the unmodifiedHNTs After surface modification there is no indication ofthe significant change in X-ray diffraction peaks (Figure 3)implying that the crystal structures of HNTs are not signifi-cantly altered regardless of the surface modification

34 TEM Analysis TEM images of the unmodified andmodified HNTs are illustrated in Figure 4 In order toobtain detailed morphological information of the specimensdifferent magnifications of various samples are presentedIn Figures 4(a) and 4(b) an obvious agglomeration canbe observed indicating that the unmodified HNTs exhibitlow polydispersity which is certainly unfavorable to theirreinforcement capability However in Figures 4(c) and 4(d)it can be observed that the modified HNTs are well separatedand exhibit almost ideal nanotubular structures with anouter diameter of around 50 nm an inner diameter of about20 nm and a length of about 1000 nm One can draw aconclusion that surface modification of HNTs nanofillerswith TCA can effectively prevent their agglomeration andgreatly improve the dispersion properties The improvementin HNTs dispersion properties might be explained thatTCA imparts nonpolar functional groups to HNTs thusleading to the significant decrease in surface energy ofHNTs

35 Rheological Behavior of PVASBRCMCHNTs Nanocom-posites Rheological measurement is generally recognizedas an indirect method to describe the dispersion stateof particles in polymer matrix [32] To investigate thecompatibility between HNTs and the polymer matrix therheological behavior of PVASBRCMCHNTs nanocom-posites was measured and the rheological behavior curvesare presented in Figures 5(a) and 5(b) As can be seenthe nanocomposites exhibit a nonlinear flow curve withshear-thinning behavior providing direct evidence thatPVASBRCMCHNTs nanocomposites are characteristics ofa typical nonNewtonian fluid [33] It is apparent in Figure 5(a)that the shear stress increases with increasing the shear rateshowing a behavior close to Bingham pseudoplastic fluidsIn Figure 5(b) it can also be observed that the viscositydecreases as the shear rate increases which may be due tothe presence of random-oriented and highly entangled stateof the PVASBRCMC polymer chains under high shear rate[32] More importantly compared to PVASBRCMCHNTsnanocomposites PVASBRCMCMHNTs nanocompositesare found to exhibit a marked decline in viscosity at the sameshear rate This finding could possibly be explained by virtueof the fact that TCA can react with hydroxyl groups at theHNTs surface which facilitates the formation ofmonomolec-ular layer on the HNTs Thus the formed monomolecular


Table 1 Effect of PVASBRCMCHNTs nanocomposites on the mechanical properties of paper

Sample Tensile index(Nsdotmsdotgminus1)

Tear index(mNsdotm2

sdotgminus1)Burst index(KPasdotm2

sdotgminus1)Base paper 2223 497 169Coated paper with PVASBRCMCHNTs nanocomposites 2353 523 195Coated paper with PVASBRCMCMHNTs nanocomposites 2526 571 208

layer may increase the compatibility and reduce the flowresistance between HNTs and PVASBRCMC composites[34]

36 Microstructure of Paper Coated with PVASBRCMCHNTs Nanocomposites It is well known that uniform disper-sion of nanofillers in polymer matrix is a key factor affectingthe improvement of the mechanical properties of polymermaterials [35] SEM images were employed to investigatethe interaction between HNTs and polymer composites onthe base paper Figure 6(a) shows the SEM image of basepaper surface It can be perceived that the base papercontains interlaced cellulose fibrils and appears to have roughsurfacesThemicrostructure of sized paperwith conventionalPVASBR composites can be observed in Figure 6(b) Itpresents that the base paper is covered with polymer filmexcept some uneven spacing Moreover the SEM images ofpaper sized with HNTs-polymer nanocomposites are shownin Figures 6(c) and 6(d) In comparison with Figure 6(c)Figure 6(d) reveals that the majority of modified HNTs areembedded and uniformly dispersed in the polymer matrixcoated on the base paper which is likely due to the increasedsurface hydrophobicity and decreased surface free energy[33] In addition the interface between modified HNTs andPVASBRCMC matrix is blurry and hardly debonded sug-gesting the very strong interfacial bonding between modifiedHNTs and PVASBRCMC matrix [29] Similar dispersionbehavior of HNTs in specific polymer matrix was reported inprevious publications [36 37] All of the above results furthersupport that surface modification of HNTs with TCA has animportant impact on the dispersion properties in polymermatrix which would subsequently facilitate the potentialapplication in surface coating of paper

37 Mechanical Properties of Paper Coated with PVASBRCMCHNTs Nanocomposites The mechanical properties ofbase paper as well as the paper coated with PVASBRCMCHNTs nanocomposites and PVASBRCMCMHNTsnanocomposites are illustrated in Table 1 The tensileindex tear index and burst index of the base paperare 2223Nsdotmsdotgminus1 497mNsdotm2sdotgminus1 and 169KPasdotm2sdotgminus1respectively As expected the incorporation of HNTs innanocomposites indeed exerts an important impact on themechanical strength of sized paper which can be attributedto the nanotubular structure of HNTs with high surfacearea More importantly it can be derived that the appli-cation effect of HNTs in PVASBRCMC nanocompositesis strongly associated with their surface chemistry andstructure derived from surface modification process As

shown in Table 1 compared with PVASBRCMCHNTsnanocomposites PVASBRCMCMHNTs nanocompositesare found to make the coated paper remarkably increasedby 735 918 and 667 in tensile index tear index andburst index respectively The significant reinforcing effectsof PVASBRCMCMHNTs nanocomposites might be dueto the uniform dispersion of modified HNTs and stronginterfacial interaction assigned to hydrogen bonding betweenHNTs and the polymermatrix [34] Consequently all of thesefurther indicate that surfacemodification of theHNTs is a keyfactor affecting the further application of HNTs in polymermatrix

4 Conclusions

In this work novel PVASBRCMCHNTs nanocompositeswere prepared for the potential application in surface coatingof paper To enhance the application effect of HNTs inpolymer composites the surface of HNTs was modified withTCA The results showed that modified HNTs exhibitedgood dispersion and displayed an ideal interfacial com-patibility within PVASBRCMC composites Compared tounmodified HNTs the incorporation of modified HNTs inPVASBRCMC nanocomposites showed more significantimprovement in tensile index tear index and burst index ofcoated paper which ismainly due to the better dispersion andinterfacial compatibility

Acknowledgments

The research is grateful for the financial support from theNational Natural Science Foundation of China (Grant no31100442) Foundation (no 201108) of Tianjin Key Labo-ratory of Pulp amp Paper (Tianjin University of Science ampTechnology China) the Science and Technology Program ofZhejiang Environmental Protection Bureau of China (Grantno 2012B008) and 521 Talent Cultivation Program of Zhe-jiang Sci-Tech University (Grant no 11110132521310)

References

[1] B Lecouvet J G Gutierrez M Sclavons and C BaillyldquoStructure-property relationships in polyamide 12halloysitenanotube nanocompositesrdquo Polymer Degradation and Stabilityvol 96 no 2 pp 226ndash235 2011

[2] M Zhao and P Liu ldquoAdsorption behavior of methylene blue onhalloysite nanotubesrdquo Microporous and Mesoporous Materialsvol 112 no 1ndash3 pp 419ndash424 2008

[3] X M Sun Y Zhang H B Shen and N Q Jia ldquoDirectelectrochemistry and electrocatalysis of horseradish peroxidase


based on halloysite nanotubeschitosan nanocomposite filmrdquoElectrochimica Acta vol 56 no 2 pp 700ndash705 2010

[4] Y Lin K M Ng C-M Chan G Sun and J Wu ldquoHigh-impactpolystyrenehalloysite nanocomposites prepared by emulsionpolymerization using sodium dodecyl sulfate as surfactantrdquoJournal of Colloid and Interface Science vol 358 no 2 pp 423ndash429 2011

[5] M X Liu B C Guo M L Du F Chen and D M JialdquoHalloysite nanotubes as a novel120573-nucleating agent for isotacticpolypropylenerdquo Polymer vol 50 no 13 pp 3022ndash3030 2009

[6] K Prashantha H Schmitt M F Lacrampe and P KrawczakldquoMechanical behaviour and essential work of fracture of hal-loysite nanotubes filled polyamide 6 nanocompositesrdquoCompos-ites Science and Technology vol 71 no 16 pp 1859ndash1866 2011

[7] E E Ibrahim D M Chipara R Thapa K Lozano andM Chipara ldquoRaman spectroscopy of isotactic polypropylene-halloysite nanocompositesrdquo Journal of Nanomaterials vol 2012Article ID 793084 8 pages 2012

[8] S A Hashemifard A F Ismail and T Matsuura ldquoMixedmatrix membrane incorporated with large pore size halloysitenanotubes (HNTs) as filler for gas separation morphologicaldiagramrdquo Chemical Engineering Journal vol 172 no 1 pp 581ndash590 2011

[9] W N Xing L Ni P W Huo et al ldquoPreparation highphotocatalytic activity of CdShalloysite nanotubes (HNTs)nanocomposites with hydrothermal methodrdquo Applied SurfaceScience vol 259 pp 698ndash704 2012

[10] E Tierrablanca J Romero-Garcıa P Roman and R Cruz-Silva ldquoBiomimetic polymerization of aniline using hematinsupported on halloysite nanotubesrdquo Applied Catalysis A vol381 no 1-2 pp 267ndash273 2010

[11] M X Liu W D Li J H Rong and C R Zhou ldquoNovel polymernanocomposite hydrogel with natural clay nanotubesrdquo Colloidand Polymer Science vol 290 no 10 pp 895ndash905 2012

[12] R C Liu B Zhang D D Mei H Q Zhang and J DLiu ldquoAdsorption of methyl violet from aqueous solution byhalloysite nanotubesrdquoDesalination vol 268 no 1ndash3 pp 111ndash1162011

[13] P Luo Y Zhao B Zhang J Liu Y Yang and J Liu ldquoStudyon the adsorption of Neutral Red from aqueous solution ontohalloysite nanotubesrdquo Water Research vol 44 no 5 pp 1489ndash1497 2010

[14] S Q Deng J N Zhang and L Ye ldquoHalloysite-epoxy nanocom-posites with improved particle dispersion through ball millhomogenisation and chemical treatmentsrdquo Composites Scienceand Technology vol 69 no 14 pp 2497ndash2505 2009

[15] B C Guo F Chen Y D Lei X L Liu J J Wan and D M JialdquoStyrene-butadiene rubberhalloysite nanotubes nanocompos-ites modified by sorbic acidrdquo Applied Surface Science vol 255no 16 pp 7329ndash7336 2009

[16] M X Liu Y Zhang C C Wu S Xiong and C R ZhouldquoChitosanhalloysite nanotubes bionanocomposites structuremechanical properties and biocompatibilityrdquo International Jour-nal of Biological Macromolecules vol 51 no 4 pp 566ndash5752012

[17] J M Duan R C Liu T Chen B Zhang and J D LiuldquoHalloysite nanotube-Fe

3O4composite for removal of methyl

violet from aqueous solutionsrdquo Desalination vol 293 pp 46ndash52 2012

[18] H Ismail P Pasbakhsh M N A Fauzi and A Abu BakarldquoMorphological thermal and tensile properties of halloysite

nanotubes filled ethylene propylene diene monomer (EPDM)nanocompositesrdquo Polymer Testing vol 27 no 7 pp 841ndash8502008

[19] H Schmitt K Prashantha J Soulestin M F Lacrampe and PKrawczak ldquoPreparation and properties of novel melt-blendedhalloysite nanotubeswheat starch nanocompositesrdquo Carbohy-drate Polymers vol 89 no 3 pp 920ndash927 2012

[20] P Rybinski and G Janowska ldquoThermal properties and flamma-bility of nanocomposites based on nitrile rubbers and activatedhalloysite nanotubes and carbon nanofibersrdquo ThermochimicaActa vol 549 pp 6ndash12 2012

[21] M Du B Guo and D Jia ldquoThermal stability and flameretardant effects of halloysite nanotubes on poly(propylene)rdquoEuropean Polymer Journal vol 42 no 6 pp 1362ndash1369 2006

[22] L C Tan YW ChenWH Zhou and SW Ye ldquoCrystallizationbehavior and mechanical strength of poly (butylene succinate-co-ethylene glycol)-based nanocomposites using functional-ized multiwalled carbon nanotubesrdquo Polymer Engineering andScience vol 52 no 12 pp 2506ndash2517 2012

[23] Z-X Jia Y-F Luo S-Y Yang B-C Guo M-L Du andD-M Jia ldquoMorphology interfacial interaction and proper-ties of styrene-butadiene RubberModified halloysite nanotubenanocompositesrdquoChinese Journal of Polymer Science vol 27 no6 pp 857ndash864 2009

[24] Y Joo Y Jeon S U Lee et al ldquoAggregation and stabilizationof carboxylic acid functionalized halloysite nanotubes (HNT-COOH)rdquo Journal of Physical Chemistry C vol 116 no 34 pp18230ndash18235 2012

[25] K Prashantha M F Lacrampe and P Krawczak ldquoProcessingand characterization of halloysite nanotubes filled polypropy-lene nanocomposites based on a masterbatch route effect ofhalloysites treatment on structural and mechanical propertiesrdquoExpress Polymer Letters vol 5 no 4 pp 295ndash307 2011

[26] T Enomae N Yamaguchi and F Onabe ldquoInfluence of coatingproperties on paper-to-paper friction of coated paperrdquo Journalof Wood Science vol 52 no 6 pp 509ndash513 2006

[27] A Ashori W D Raverty and J Harun ldquoEffect of chitosan addi-tion on the surface properties of kenaf (Hibiscus cannabinus)paperrdquo Fibers and Polymers vol 6 no 2 pp 174ndash179 2005

[28] M Du B Guo M Liu X Cai and D Jia ldquoReinforcingthermoplastics with hydrogen bonding bridged inorganicsrdquoPhysica B vol 405 no 2 pp 655ndash662 2010

[29] M L Du B C Guo Y D Lei M X Liu and D M JialdquoCarboxylated butadiene-styrene rubberhalloysite nanotubenanocomposites interfacial interaction and performancerdquoPolymer vol 49 no 22 pp 4871ndash4876 2008

[30] Y L Tai J S Qian Y C Zhang and J D Huang ldquoStudy of sur-face modification of nano-SiO

2with macromolecular coupling

agent (LMPB-g-MAH)rdquo Chemical Engineering Journal vol 141no 1ndash3 pp 354ndash361 2008

[31] W L Zhang and H J Choi ldquoFabrication of semiconductingpolyaniline-wrapped halloysite nanotube composite and itselectrorheologyrdquo Colloid and Polymer Science vol 290 no 17pp 1743ndash1748 2012

[32] C Y Tang T M Yue D Z Chen and C P Tsui ldquoEffect ofsurface coating on the rheological properties of a highly opaquenano-TiO

2HIPS compositerdquo Materials Letters vol 61 no 23-

24 pp 4618ndash4621 2007[33] Z Y Yang Y J Tang and J H Zhang ldquoSurface modification of

CaCO3nanoparticles with silane coupling agent for improve-

ment of the interfacial compatibility with styrene-butadiene


rubber(SBR) latexrdquo Chalcogenide Letters vol 10 no 4 pp 131ndash141 2013

[34] C Ai Wah L Yub Choong and G Seng Neon ldquoEffectsof titanate coupling agent on rheological behaviour disper-sion characteristics and mechanical properties of talc filledpolypropylenerdquo European Polymer Journal vol 36 no 4 pp789ndash801 2000

[35] J H Gou S OrsquoBraint H Gu and G Song ldquoDamping aug-mentation of nanocomposites using carbon nanofiber paperrdquoJournal of Nanomaterials vol 2006 Article ID 32803 7 pages2006

[36] N-Y Ning Q-J Yin F Luo Q Zhang R Du and QFu ldquoCrystallization behavior and mechanical properties ofpolypropylenehalloysite compositesrdquo Polymer vol 48 no 25pp 7374ndash7384 2007

[37] S Rooj ADas VThakur RNMahaling A K Bhowmick andG Heinrich ldquoPreparation and properties of natural nanocom-posites based on natural rubber and naturally occurring hal-loysite nanotubesrdquoMaterials and Design vol 31 no 4 pp 2151ndash2156 2010

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Journal ofNanomaterials


particularly at a high HNTs loading Schmitt et al [19] usedboth modified and unmodified HNTs as nanofillers to plasti-cized starch polymericmatrix and investigated the structuralmorphological thermal and mechanical properties of plasti-cized starchHNTs nanocomposites Rybinski et al [20] andDu et al [21] studied the thermal properties and flammabilityof different nanocomposites based on HNTs respectivelyand proposed that the nanofillers can increase the thermalstability and decrease the flammability of nanocomposites

However much like other nanofillers the main difficultyin utilization of HNTs in nanocomposites arises from theagglomeration ofHNTs and the poor interfacial compatibilitybetween HNTs and polymer matrix [22] To overcome thesedisadvantages many efforts have been made to disperseHNTs uniformly in polymer matrix and to improve the inter-facial compatibility between HNTs and polymer matrix Jiaet al [23] used complex of resorcinol and hexamethylenete-tramine (RH) to modify HNTs and found that RH can notonly facilitate the dispersion and orientation of HNTs in SBRmatrix at nanometer scale but also enhance the interfacialcombination between HNTs and rubber matrix Joo et al[24] modified the functional groups of HNTs from hydroxylgroups (HNTs-OH) to carboxylic acids (HNTs-COOH) toimprove the dispersion of HNTs in acidic basic and neutralsolutions Prashantha et al [25] conducted the modificationof HNTs with quaternary ammonium salt and concluded thatmodifiedHNTs can lead to better performances than unmod-ified HNTs due to strong interfacial interaction between thepolymer matrix and the nanotubes

Paper quality is strongly dependent on the structuraland chemical properties of paper surface which is not onlyassociated with the fibrous matrix but also related to the finalsurface treatment [26] Surface treatments such as coatingand sizing are widely applied in papermaking industry toimprove surface strength Conventional polymer compositessuch as PVA copolymers of styrene and maleic anhydride(SMA) SBR polyurethane (PU) and polyacrylamide (PAM)are often employed to improve the properties of paperby forming a layer of polymer film on the whole papersheet [27] However there are limited studies regarding thenanocomposites containing HNTs for the surface coating ofpaper in the previous publications In the present work novelnanocomposites were designed using a blend of PVA SBRand CMC especially the incorporation of modified HNTsTo achieve desired dispersion of HNTs nanofillers and toyield a good compatibility between HNTs and the polymermatrix HNTs were modified first by TCA SubsequentlyPVASBRCMCHNTs nanocomposites were successfullyprepared through physical blending In addition the effectsof unmodified and modified HNTs on the nanocompositeproperties and the subsequent paper properties were alsostudied

2 Experimental

21 Materials HNTs used in this study were mined fromHubei Province China TCA possessing a decompositiontemperature of 210∘C a density of 1095 gcm3 and a refrac-tive index of 1446 was purchased from Hangzhou Jessica

Chemical Co Ltd SBR-latex with a solid content of 50was supplied by BASF CMC was provided by ShanghaiSinopharm Chemical Reagent Co Ltd PVA was supportedby a paper mill in Hangzhou City of China Anhydrousethanol serving as the dissolvent in the modification processof HNTs was purchased from Hangzhou Gaojing FineChemical Industry Co LtdThe commercial base paper witha basic weight of about 130 gm2 was provided by a paper millin Zhenjiang Province of China It was derived from OCCpulp a cheap and low-grade raw material

22 Surface Modification of HNTs Initially 2 g of HNTs weredispersed in 40mL of anhydrous ethanol upon ultrasonictreatment for 5min TCA was dissolved in 10mL of anhy-drous ethanol at the ratio (TCAHNTs) of 375 75 and15 respectively and then was added into the solution ofHNTs The mixture was reacted at a constant temperatureof 80∘C for 6 h under the mechanical stirring (550 rpm) ina three-necked round-bottomed flask Finally the reactionmixture was filtered and washed with anhydrous ethanol forseveral times prior to the drying process in an oven at 60∘Cfor 24 h

23 Preparation of PVASBRCMCHNTs NanocompositesIn this process the PVASBRCMCHNTs nanocompositeswith a solid content of 10were madeThe added proportionof PVA SBR was 3 1 and the weight ratio of CMCHNTswas 2 1 Initially 6375 g of PVA was added into distilledwater and heated to 90ndash95∘C until PVA was completelydissolved Subsequently specified amount of SBR was slowlyadded into the resulting PVA solution followed by theaddition of 10 g of CMC Lastly HNTs (unmodified sampleor modified sample treated with 375 TCA) were gradu-ally added into the PVASBRCMC nanocomposites As aresult PVASBRCMCHNTs and PVASBRCMCMHNTsnanocomposites were obtained

24 Preparation of Coated Paper OCC-based paper wasselected as the base paper for surface coating process Thesurface coating process was completed on a laboratory scaleZAA 2300 multicoater (Zehntner Switzerland) About 10mLof obtained nanocomposites were loaded on the base paperand then spread over with the aid of a round steel bar Thecoated paper was initially dried at ambient temperature andthen dried at 100∘C for 20min The coat weight of the papersamples was about 3 gm2

25 Characterization Fourier transformed infrared (FT-IR)spectra of HNTs were conducted on Nicolet 5700 spectrome-ter (Thermo Fisher Scientific USA)The thermal behavior ofmodified and unmodified HNTs was determined with PyrislTGA (PerKin Elmer USA) under nitrogen atmosphere at aheating rate of 20∘Cmin X-ray diffraction (XRD) was per-formed on a diffractometer (X1015840TRA-055 ARL Switzerland)with a nickel-filter Cu K120572 (120582 = 0154 nm) The morphologyanalysis was carried out by transmission electronmicroscopy(TEM) on a JSM-2100 electron microscope (JEOL Japan)at an accelerating voltage of 200KV The morphology of


4000 3500 3000 2500 2000 1500 1000 500

3697

3619

34492929 2854 1629

2929

2861

(a)

(b)

(c)

(TCA)

1069

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1030






100 200 300 400 500 600 70075

80

85

90

95

100

(c) (d)

(b)

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85

90

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4 Conclusions


Acknowledgments


References

























































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




4000 3500 3000 2500 2000 1500 1000 500

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(a)

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Temperature (∘C)


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4 Conclusions


Acknowledgments


References

























































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(a) (b)

(c) (d)


1 10 100 1000

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Acknowledgments


References

























































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials




(a) (b)

(c) (d)








Tear index(mNsdotm2







4 Conclusions


Acknowledgments


References

























































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials






Tear index(mNsdotm2







4 Conclusions


Acknowledgments


References

























































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials
























































CeramicsJournal of







Biomaterials




Journal of


Journal of





CoatingsJournal of

Advances in








MaterialsJournal of


Nano

materials



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