Crystallography: Special Emphasis on Applications in Chemistry. Journal of Chemical and Pharmaceutical Sciences ISSN:

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1 Effet of hydroxylptite nnoprtiles on struturl nd eletril properties of ethylene propylene diene monomer ruer A. Nihmth nd M. T. Rmesn* Deprtment of Chemistry, University of Cliut, Cliut University P.O., Kerl, Indi *Corresponding uthor: E-Mil: ABSTRACT In this rtile, hydroxyptite nnoprtiles (HA) supported on ethylene propylene diene monomer (EPDM) ruer hve een prepred nd hrterized. Nnoomposites of EPDM with HA nnoprtiles were prepred y mehnil mixing in two roll mill in presene of diumyl peroxide (DCP) s rosslinking gent. The struturl reorgniztion of nnoomposite ws studied y FTIR, UV-Visile spetrosopi tehniques nd XRD. Spetrosopi studies reveled tht the inorportion of nnoprtiles into the elstomer leds to n interfil intertion etween the nnoprtiles nd polymer. The XRD nlysis sertined the presene of HA nnoprtiles in the EPDM hin. Optil nd snning eletron mirosopy ws onduted to hrterize the dispersion of nnoprtile inside the mromoleulr hin of EPDM. The hnges in therml ehviour of EPDM ruer ws hrterized y TGA nd DSC. The therml stility nd glss trnsition temperture of nnoomposites were inresed with the inrese in weight perentge of HA nnoprtiles. The AC eletril ondutivity nd dieletri onstnt of nnoomposite were found to e inreses with the inrese in onentrtion of nnoprtiles. KEY WORDS: EPDM, nno-hydroxyptite, nnoomposite, rystllinity, therml properties, eletril properties. 1. INTRODUCTION Ethylene propylene diene monomer (EPDM) ruer is well known generl purpose elstomer hving verstile utiliztion in mteril industry rnging from utomotive to household pplition. Prtiulr ttention hs een foused on EPDM ruer euse of their unique hrteristis suh s outstnding ozone nd het resistne, wethering ility, ging properties et. due to stle sturted hydroron hins with low perentge of olefini side hins (Seo, 211). But the thermodynmi immisiility results high interfil tension due to the lk of polrity, limits its pplition in engineering fields. To overome this diffiulty, reently mny reserh works were rried out on EPDM y mking use of its ility to respond high filler loding due to the presene of high ethylene ontent (Bhdne, 26; El-Wkil, 211). The nnoomposite with lrge interfil re per unit volume shows etter mehnil, eletril, therml performne (Rmesn, 213, Rmesn, 214; Te, 22). EPDM sed nnoomposites hve got gret reserh interest. The nnoomposites of polymer with ermi mteril s filler hve the merits of oth polymer nd ermi. The nno sized hydroxyptite is one of the most studied io ermi mterils whih hve exellent iodegrdility, ioomptiility nd osteoondutive properties (Chen, 22). Polymide /hydroxyptite nnoomposite with greter ioomptiility nd mehnil strength ws prepred y Li (21). Though polypropylene is ioinert polymer, its nnoomposite with HA shows iotive hrteristis, dimensionl stility nd high mehnil strength (Lio, 213). Further, literture reports point out the use of polymeri ermi nnoomposites s energy storge mterils euse of the low temperture proessility of polymer nd high dieletri onstnt of ermis (Siddttuni nd Shumn, 214). The present work report on the preprtion of EPDM/HA nnoomposite with different loding of synthesized hydroxyptite nnoprtiles. The struturl hrteriztion of the prepred nnoomposite ws studied y FTIR nd UV-VIS spetrosopy, XRD, TGA nd DSC. Optil mirosopy nd SEM were used to nlyze the morphologil hrteristis. Furthermore, the AC ondutivity nd the dieletri properties of nnoomposite were lso investigted. 2. MATERIALS AND METHODS EPDM-52 ws otined from Herdilli Unimers Ltd. (Mumi, Indi). The nlytil grde CCl 2, (NH 4) 2HPO 4, NH 4OH were used for the synthesis of nno hydroxyptite. The ross linking gent used ws ommeril grde diumyl peroxide (DCP) otined from lol ruer hemil suppliers Synthesis of Hydroxyptite nnoprtile: Hydroxyptite nnoprtiles were prepred y hemil preipittion method s desried erlier (Png, 23). Typilly, equimolr onentrtion of CCl 2 nd (NH 4) 2HPO 4 were prepred in n queous solution nd these solutions were preheted, mixed under vigorous stirring. NH 4OH ws dded to the retion mixture immeditely fter mixing until the ph rehed to 1. After stirring for 24 hours the preipitte ws filtered, wshed with wter nd dried nd the HA powder ws then sintered t 6 C for 6hrs. JCHPS Speil Issue 1: Jnury Pge 38

2 2.2. Preprtion of EPDM/HA nnoomposite: EPDM/HA nnoomposites were prepred y dding vrious mount of hydroxyptite nnoprtiles in n open two roll mill mixing tehnique. Ruer (1phr) is mixed with uring gent DCP (6phr) nd HA nnoprtiles (5, 1, 15 nd 2 phr). The smples were vulnized to their respetive ure time in hydruli press t 16 C. For omprison lnk ompound ws lso prepred y mixing EPDM nd DCP Chrteriztion: The IR spetr of the omposites were reorded on JASCO (model 41) Fourier trnsform infrred spetrophotometer in the region 5 4 m -1. The UV spetr of smples were otined using Hithi U-3 spetrophotometer. X-ry diffrtion pttern of the smple ws reorded on Philips X-ry diffrtometer using CuKα rdition (λ= A ). The diffrtogrm ws reorded in terms of 2θ in the rnge1 8 o. The optil imges of omposites were tken y using Trinoulr mirosope Model Axio L. A1 tthed Axio Cm ER5s Crl Zeiss Miro imging GmH Anlyzer. The surfe morphology of the ruer ws investigted y using Field Emission Snning Eletron Mirosopy (FESCA)-Hithi, SU 66 (FESEM). Therml deomposition ehviour of the nnoomposite ws investigted y Perkin Elmer thermo grvimetri nlyzer t heting rte of 1 C/min in dry nitrogen tmosphere. DSC nlysis ws rried out y Mettler Toledo DSC 22e t heting rte of 5 C/min (tmosphere N2; flow 4 ml/min). AC resistivity nd Dieletri onstnt of the smples ws mesured y Hewlett Pkrd LCR meter, in frequeny rnge Hz t room temperture. 3. RESULTS AND DISCUSSION 3.1. FT-IR Chrteriztion: Fourier trnsform infrred spetrum is used to determine the omposition of the prepred EPDM/HA nnoomposites. The IR spetr of EPDM with different onentrtion of nnoprtiles re given in Figure 1. The hydroxyptite shows O-H strething virtion t 3573 m -1 nd O-H ending mode t 633 m -1. Also, the IR sorption t 964, 145 m -1 re ssigned to the P-O-strething virtion of (PO 4) 3- group nd the peks otined t 633,62 nd 568 m -1 re orresponding to its ending virtion (Nejti, 29). The pristine EPDM shows sorption peks t 1157 m -1, 1457 m -1 nd 294 m -1 orresponding to C-H strething virtion of polypropylene segment nd the pek t 721 m -1 whih is ttriuted to side ethyl groups of rystlline ethylene loks (Vîlsn, 215). The nnoomposite ontins most of the sorption nds present in the EPDM nd HA long with slight shift in sorption frequeny. The OH strething is shifted from 3573 m -1 to 3568m -1 nd ending virtion is hnged from 633 m -1 to 638 m -1. Furthermore, n sorption nd is present in nnoomposite (t m -1 ) my e due to the omintion of C-H strething virtion of polypropylene in EPDM(1157 m -1 ) nd PO 4 3- entity (145 m -1 ) of HA. These results ssure the inorportion of nno-ha in EPDM ruer UV-VIS Spetrosopy: The diffuse refletne UV-VIS spetr snned t 2-6 nm of EPDM nd EPDM/HA nnoomposite is given in Figure 2. Hydroxyptite nnoprtile shows n sorption mximum t 263 nm nd dip t 421 nm. EPDM shows rod sorption nd with sorption mxim t 347nm. The hromophore responsile for initil UV light sorption is the ron-ron doule ond present in EPDM. It is very ler from the figure tht the nnoomposites lso show mximum sorption of UV light elow 3 nm nd n sorption dip in 3-4 nm rnge whih reflets the suessful introdution of nno-ptite prtiles in to the mtrix. Moreover, the sorption mximum in the nnoomposite shows shift to higher energy region thn tht of EPDM. This hypohromi shift my e due to the interfil intertion of HA nd the hins of EPDM X-Ry Diffrtion Anlysis: The X-ry diffrtion ptterns of EPDM nd EPDM / HA nnoomposite with different onentrtion of nnoprtile is given in Figure 3. Being rystlline ioermi hydroxyptite nnoprtile shows 2θ vlues t 25.7, , 39.7, 46.6,49.5 nd 53.9 orresponding to the rystl plnes 2, 211, 3,22, 31,222, 213, 321 nd 4 (Arsd, 211). EPDM shows n intense rod diffrtion pek t 2θ = 17.8 inditing its morphous nture nd smll pek t 2θ = 28. This smll shrp rystlline pek my e due to the presene of side ethylene of polyethylene lok. From the plots it is very ler tht nnoomposite exhiit very few rystlline peks of HA with derese in intensity. The rystlline pek orresponding to polyethylene segment of EPDM is sent in nnoomposite nd lso new diffrtion pek ppered t 2θ = 31. It is interesting to see tht the morphous region of the omposite is shifted to lower 2θ region with 2 phr HA nnoprtiles. In ddition to this the intensity of morphous nd rystlline peks dereses with inrese in the dosge of nnoprtiles. This proves tht the effiient interfil intertion etween the elstomer nd the ermi ours t lower loding of nnoprtiles. At higher loding of HA, the vrition in morphous nd rystlline region of nnoomposite is ttriuted to the gglomertion of nnoprtiles whih is in good greement with the optil mirogrphs. JCHPS Speil Issue 1: Jnury Pge 39

3 3.4. Morphologil Studies: The distriution of nnoprtile in EPDM mtrix is exmined y SEM nd optil mirosopy. The SEM imge of EPDM with 1 phr HA nnoprtile is presented in Figure 4. It depits the spherilly shped lusters of nno HA in the host ruer. The dispersed prtiles re gglomerted due to the self ggregtion through strong polr ttrtion etween OH groups within nonpolr mromoleulr system. Figure 5 demonstrtes the optil mirogrphs of EPDM nd its nnoomposites with HA. EPDM shows homogenous smooth surfe wheres in nnoomposite t lower onentrtion of nnoprtile (5 phr) shows lmost uniform distriution of filler loding. Thus the mirogrph point out the good dhesion etween nno filler nd the polymer mtrix Thermogrvimetri Anlysis (TGA): Thermogrvimetri nlysis of newly prepred nnoomposite presented in Figure 6 shows single stge deomposition. The degrdtion temperture of EPDM hin is t 434 C wheres the deomposition temperture inreses s the onentrtion of nnoprtile inreses. Tht is EPDM with 5 phr HA shows deomposition t 438 C while EPDM/ 15 phr HA degrdes t 445 C. The elevtion in deomposition temperture lerly indites the improved therml stility of nnoomposite whih is due to the nnoprtile penetrted in to the EPDM redues the diffusion of oxygen in to the long hin of elstomer. Besides, the hr residue otined t 6 C for EPDM is 1.2% wheres the nnoomposites with 5 nd 15 phr HA re out 4.7% nd 9.3 % respetively. The inrese in perentges of finl hr residue with the inrese in filler loding indites tht the nnoprtiles t s het rrier to EPDM nd thus enhnes the flme retrdny of ruer (Nihmth nd Rmesn, 214) Differentil Snning Clorimetry (DSC): DSC nlysis ws performed to determine the glss trnsition temperture (Tg) of frited nnoomposite. The Tg otined s se line shift in thermogrms re shown in Figure 7 for EPDM nd its nnoomposites with HA. The EPDM shows Tg t -53 C, the nnoomposite with 5 nd 15 weight % HA re present t -51 C nd -48 C respetively. The rise in Tg of newly prepred EPDM/HA nnoomposites is ttriuted to the intermoleulr intertion through the enhned interfe of nnoomposite whih restrits the rottionl motion within the hins. Also, the inorportion of HA inreses the omptness of the system s evident from the XRD resulting in the redution of free volume inside the omposite whih in turn suppresses the motion of polymer hins (Rmesn, 214 ) Condutivity Studies AC Condutivity: The AC eletril ondutivity s funtion of frequeny of EPDM nd EPDM with different ontent of HA nnoprtiles re depited in Figure 8. The ondutivity goes on inresing with frequeny whih is due to the hopping of hrge rriers through the onduting networks formed s result of polrity indued y the hydroxyl group of hydroxyptite to the EPDM hins. Further, the eletril ondutivity of nnoomposite is etter thn net EPDM nd the ondutivity inreses proportiontely with inrese in onentrtion of HA. It n e explined on the mirosopi ondutivity rising from the mtrix-filler intertion, polrity nd hin entnglements in the host mtrix (Rmesn, 214 ). As it is reveled from XRD studies the rystllinity of EPDM inreses with the inorportion of nno HA resulting in the improvement of orderness through the interonnetion of dispersed filler nd the ruer mtrix. It n lso e seen from the grph tht the ondutivity of nnoomposite with 2phr HA is less thn tht of nnoomposite with 15phr HA due to ggregtion of nnoprtile t higher loding (Rmesn, 215) Dieletri Constnt: The dieletri onstnts of the omposites re portryed in Figure 9. It n e oserved tht dieletri onstnt shows frequeny independent ehviour t high frequeny nd strong distortion of permittivity t lower frequeny region nd lso the dieletri onstnt inreses with the onentrtion of nno- HA. At lower frequenies the interfil polriztion rised y the introdution of polr filler into the ruer mtrix is the reson for high dieletri onstnt while t higher frequenies the orienttion polriztion plys importnt role (Anil nd Rmesn, 214). Tht is up to out 1 3 Hz the AC urrent is in phse with the pplied potentil wheres ove 1 3 Hz the filler ggregtes do not get enough time for hoping efore the reversl of the field. As the filler onentrtion inreses the eletril polriztion of the elstomer mtrix inreses due to the presene of more numer of polr hydroxyl groups. JCHPS Speil Issue 1: Jnury Pge 4

12 18 16 Trnsmittne 1 HA Trnsmittne 14 12 1 8 EPDM/5 wt % HA 8 6 EPDM 4 1 2 3 4 5 1 15 2 25 3 35 4 Wvenumer(m -1 ) Wvenumer(m -1 ) Figure.1. FTIR spetr of EPDM, HA nd EPDM/5 phr HA 1.3 1.25.1 1.2 Asorne HAp.

4 Trnsmittne 1 HA Trnsmittne EPDM/5 wt % HA 8 6 EPDM Wvenumer(m -1 ) Wvenumer(m -1 ) Figure.1. FTIR spetr of EPDM, HA nd EPDM/5 phr HA Asorne HAp wvenumer (nm) Asorne EPDM. EPDM/5Wt. % HA. EPDM/1Wt. % HA d. EPDM/15Wt. % HA e. EPDM/2Wt. % HA Wvelength (nm) d e Figure.2.UV spetr of HA nd EPDM/HA nnoomposites Intensity (ounts) hydroxyptite Intensity EPDM.EPDM/5 wt % HAp. EPDM/2 wt % HAp thet (degree) Figure.3.XRD pttern of HA, EPDM nd EPDM/HA nnoomposites Figure. 4. SEM imges of EPDM nd EPDM/1phr HA JCHPS Speil Issue 1: Jnury Pge 41

Figure 5. Optil mirogrphs of ) EPDM ) EPDM/5 phr HA ) EPDM/15phr HA 1 8 Weight (%) 6 4 2. EPDM.EPDM/5 wt.

EPDM. EPDM/5 wt.% hydroxy ptite. EPDM/15 wt.

DSC thermogrms of EPDM nd EPDM/HA nnoomposites -6.5 Log (S/m) -7. -7.5-8. -8.5-9.

5 Figure 5. Optil mirogrphs of ) EPDM ) EPDM/5 phr HA ) EPDM/15phr HA 1 8 Weight (%) EPDM.EPDM/5 wt. % hydroxy pptite.epdm/15 wt. % hydroxy pptite Temperture ( o C) Figure.6.TGA thermogrms of EPDM nd EPDM/HA nnoomposites 2 1. EPDM. EPDM/5 wt.% hydroxy ptite. EPDM/15 wt. % hydroxy ptite Het Flow (w/g) Endo Exo Temperture (oc) Figure.7.DSC thermogrms of EPDM nd EPDM/HA nnoomposites -6.5 Log (S/m) EPDM+15 wt % hydroxy ptite EPDM+2 wt % hydroxy ptite EPDM+1 wt % hydroxy ptite EPDM+5 wt % hydroxy ptite EPDM Log F (Hz) Figure.8. AC ondutivity of EPDM nd EPDM/HA nnoomposites JCHPS Speil Issue 1: Jnury Pge 42

6 Dieletri onstnt r EPDM EPDM/5wt.% hydroxy ptite EPDM/1wt.% hydroxy ptite EPDM/15wt.% hydroxy ptite EPDM/2wt.% hydroxy ptite Log F (Hz) Figure.9. Dieletri onstnt of EPDM nd EPDM/HA nnoomposites 4. CONCLUSIONS Hydroxyptite nnoprtiles (HA) ws synthesized y the hemil preipittion etween CCl 2 nd (NH 4) 2HPO 4 in queous solution. EPDM/HA nnoomposite ws prepred y simple two roll mill mixing method in presene of diumyl peroxide s rosslinking gent. The effet of hydroxy ptite nnoprtiles on EPDM ruer ws studied nd hrterized y FTIR, UV, XRD, TGA, DSC nd eletril ondutivity mesurements. FT-IR spetr indited the inorportion of hydroxyptite with the elstomer hin. UV-Visile spetrosopy onfirms the enhned interfil intertion of nnoprtiles nd the elstomeri hin. XRD pttern of omposite showed few diffrtion pek of HA in the polymer mtrix. The interltion nd floultion of inorgni nnoprtiles in orgni mtrix n e reveled from optil mirogrphs nd lso from SEM imges. The therml ehviour of newly prepred nnoomposite inresed with inrese in onentrtion of nnoprtiles. DSC nlysis showed etter the glss trnsition temperture of nnoompoite ws higher thn net EPDM nd the Tg inreses with inrese in ontent of nnoprtiles in the polymer, inditing the interfil intertion etween mtrix nd the nnoprtiles. The EPDM/HA nnoomposite with higher weight perentge of HA nnoprtile shows higher AC ondutivity thn pristine ruer due to the improved interonnetion etween nnoprtile nd polymer tht result in n ordered rrngement of filler inside the mromoleulr hin of EPDM. Dieletri onstnt of nnoomposite exhiit similr ehviour to the pplied frequeny nd ws signifintly inresed with inrese in onentrtion of HA nnoprtiles. 5. ACKNOWLEDGMENTS Authors re thnkful to Dr.P.P.Prdyumnn, Deprtment of Physis, University of Cliut for the ondutivity nd XRD studies. The uthors lso wish to knowledge University Grnts Commission, New Delhi for their finnil ssistne. REFERENCES Anilkumr T, Rmesn MT, Synthesis nd eletril ondutivity studies of metl hloro nd nitroxide group ontining styrene utdiene ruer, Amerin Institute of Physis Conferene Proeedings, 162, 214, Arsd MSM, Lee PM., Hung LK, Synthesis nd hrteriztion of hydroxyptite nnoprtiles nd β-tcp prtiles, 2 nd Interntionl Conferene on Biotehnology nd Food Siene IPCBEE, 7, 211, Bhdne P, Chmpgne M, Huneult M, Tofn F, Fvis B, Continuity development in polymer lends of very low interfil tension, Polymer, 47, 26, Chen F, Wng ZC, Lin CJ, Preprtion nd hrteriztion of nno-sized hydroxyptite prtiles nd hydroxyptite/hitosn nno omposite for use in iomedil mterils, Mteril Letters, 57, 22, El-Wkil AA, Enhnement of dhesion etween EPDM nd polyester fri y using NR modified mlei nhydride, Interntionl Journl of Polymer Siene, 211, 211, 1-4. Li J, Li Y, M S, Go Y, Zuo Y, Hu J, Enhnement of one formtion y BMP-7 trnsdued MSCs on iomimeti nno-hydroxyptite/polymide omposite sffolds in repir of mndiulr defets, Journl of Biomedil Mterils Reserh Prt A, 95, 21, JCHPS Speil Issue 1: Jnury Pge 43

7 Lio CZ, Li K, Wong HM, Tong WY, Yeung KWK, Tjong SC, Novel polypropylene ioomposites reinfored with ron nnotues nd hydroxyptite nnorods for one replements, Mterils Siene nd Engineering: C, 33, 213, Nejti E, Firouzdor V, Eslminejd MB, Bgheri F, Needle-like nno hydroxyptite/poly (L-ltide id) omposite sffold for one tissue engineering pplition, Mterils Siene nd Engineering: C, 29, 29, Nihmth A, Rmesn MT, Development, hrteriztion nd ondutivity studies of hlorinted EPDM, Amerin Institute of Physis Conferene Proeedings, 162, 214, Png YX, Bo X, Influene of temperture, ripening time nd lintion on the morphology nd rystllinity of hydroxyptite nnoprtiles, Journl of the Europen Cermi Soiety, 23, 23, Rmesn MT, Dynmi mehnil properties, mgneti nd eletril ehvior of iron oxide/ ethylene vinyl ette nnoomposites, Polymer Composites, 35, 214, Rmesn MT, Effet of fly sh on therml stility, flmmility, oil resistne nd trnsport properties of hlorinted styrene utdiene ruer omposites, Journl of Elstomers nd Plstis, 46, 214, Rmesn MT, Nihmth A, Frnis J, Preprtion nd hrteriztion of zin sulphide nnoomposites sed on rylonitrile utdiene ruer, Amerin Institute of Physis Conferene Proeedings, 1536, 213, Rmesn MT, Proessing hrteristis nd mehnil nd eletril properties of hlorinted styrene utdiene ruer/ fly sh omposites, Journl of Thermoplsti Composite Mterils, 28, 215, Rmesn MT, Synthesis nd hrteriztion of mgnetoeletri nnomteril omposed of Fe 3O 4 nd polyindole, Advnes in Polymer Tehnolology, 32, 213, Seo YD, Lee HS, Kim YS, Song C, A study on the ging degrdtion of EPDM under lol ondition, Nuler Engineering nd Tehnology, 43, 211, Siddttuni S, Shumn TP, Polymer omposites for energy hrvesting, onversion, nd storge, 1161, ACS Symposium Series, Amerin Chemil Soiety, Wshington DC, 214, Te HK, Lee WJ, Dong CL, Hyoung JC, John MS, Synthesis nd rheology of interlted polystyrene/ N+montmorillonite nnoomposites, Mromoleulr Rpid ommunition, 23 22, Vîlsn MN, Meghe A, Sonmez M, Georgesu M, Dynmilly ured hyrid polymer nnoomposite sed on polypropylene nd EPDM ruer, University Politehni of Buhrest Sientifi Bulletin Series B, 77, 215, JCHPS Speil Issue 1: Jnury Pge 44

Research Article Hydrothermal Synthesis of Ni/Al Layered Double Hydroxide Nanorods

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