Hydroxyapatite Powder Prepared by Low Temperature Hydrothermal Method from Sea Shells

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1 Hydroxyptite Powder Prepred y Low Temperture Hydrotherml Method from Se Shells Ahmd Fdli *, Fjril Akr, Pnsil Putri, Dewi Indh Prtiwi nd Ikhl Muhr Deprtment of Chemil Engineering, Fulty of Engineering, University of Riu Kmpus Binwidy Jl. HR Surnts Km. 12,5 Peknru Riu Indonesi *Corresponding uthor: fdliunri@yhoo.om Pper History Reeived: 25-Otoer-2014 Aepted: 1Novemer-2014 ABSTRACT Hydroxyptite is ioermis tht widely used in the medil world espeilly for one implnt nd ell ulture. Hydroxyptite ws synthesized y low temperture hydrotherml method whih se shells s derived CO nd (NH 4 ) 2 H with C/P rtio of 0.67, 1.67, 2.67 were heted t 70 C, 80 C, 90 C nd stirred t 300 rpm. The otined pste ws dried nd then the powder lined in the temperture rnge of 700 C C. In order to study the morphology nd struturl hrteristis, XRD nd SEM were used to estimte the prtile size of the powder. FTIR ws used to identify orgni or inorgni hemils for estimting the numer of omponents of n unknown mixture. The rystl dimeter of hydroxyptite inresed with C/P rtio nd retion temperture. Mjority hydroxyptite phse ws otined t C/P rtio of 2.67 nd 90 C retion temperture. KEY WORDS: Hydroxiptite, hydrotherml, powder, hrteriztion 1.0 INTRODUCTION Hydroxyptite (HAP) is the min minerl onstituent of teeth nd ones [1]. Beuse of iomptiility, iotivity, low soluility in wter nd ility to reple toxi ions, HAP (C 10 ( ) 6 (OH) 2 ) re widely used in iomterils [2, 3]. Therefore, multiple tehniques hs een used for preprtion of HAP, inluding preipittion [4], mehnohemil [5, 6], nd hydrotherml [7, 8]. As proposed y Alqp nd Sopyn [9], low temperture hydrotherml method provides dvntges in omprison other methods due the stle phse of HAP. It poses more onvenient method for synthesis HAP with low temperture hydrotherml method thn hydrotherml method euse it hs no need for high tempertures when forming the HAP powder, thus lowering energy osts [10]. It is lso more onvenient thn mehnohemil proedure sine low temperture hydrotherml method presents n queous phse tht is not ville in the mehnohemil method. This queous phse n elerte kineti proesses tht ommonly limit the rte of retion, suh s dissolution, diffusion, dsorption, retion, nd rystlliztion [11]. The low temperture hydrotherml method lso offers vriility in prtile size y hnging the ontrolled vriles suh s temperture, ph, rte of stirring, nd mount of retnts or C/P rtio. 2.0 EXPERIMENTAL 2.1 Mterils Preprtion The strting mterils in this experiment were mmonium dihydrogen phosphte ((NH 4 )H 2 ) (Merk, Germny) nd se shell (Anndr Grnos) from Peknru lol mrket. Initilly, se shell were lened nd dried t mient temperture for 24 hours. Susequently, dried se shell ws rushed nd sieved using 100-mesh sieve. Se shells powder were linted t 1000 C for 24 hours to hnged CCO 3 to CO, y these following retion: CCO 3 CO + CO 2 (1) 2.2 Synthesis of Hydroxyptite Powder For the preprtion of the solution, CO nd ((NH 4 )H 2 ws dropwise in 600 ml distilled wter with C/P rtio of 0.67, 1.67 nd The suspension ws heted t 70 C, 80 C, 90 C while 24 Pulished y Interntionl Soiety of Oen, Mehnil nd Aerospe Sientists nd Engineers

2 stirred t 300 rpm until pste ws otined. Then the pste ws dried t 120 C for 15 hours nd rushed until powder form. The prepred powders were then lined in furne t 900 C. A heting rte of 5 C min -1 ws pplied until the required temperture ws rehed nd then the heting ws ontinued for 1 hour. Vriles in this work were C/P rtio (0.67, 1.67 nd 2.67) nd retion tempertures (70 C, 80 C nd 90 C). pure hydroxyptite. Figure 2 shows the FTIR spetrum of synthesized hydroxyptite with vritions in temperture 70 o C, 80 o C nd 90 o C. The mesurement results of hydroxyptite synthesized using hydrotherml method with temperture t 70 C using FTIR nlysis shown in Figure Chrteriztion The rystl nd phse strutures of the smples were identified using X-ry diffrtometer (XRD) with CuKα (λ = Å) inident rdition over the 2θ rnge of t room temperture. Moreover, the isolte peks ssigned to (002), (112), nd (300) plnes were used to estimte the rystllite size (D) of HAP phses, respetively, using the well-known Sherrer s formul s followed [12]: (2) H 2 O 2- H P 2 O 7 Where k is shpe ftor equl to 0.9, λ is the X-ry wve length, β is the full-width t hlf-mximum (in rdins), nd θ is the diffrtion ngle relted to the diffrtion pek under onsidertion. Fourier trnsform infrred spetrosopy (FTIR) ws used for identifition of funtionl groups present in the HAP powder. The morphology nd size of the nnoprtiles were studied using snning eletron mirosopy (SEM) 3.0 RESULTS AND DISCUSSION 3.1 FTIR Spetr FTIR spetrosopy nlysis ws lso used in this study. FTIR identify the funtionl groups in the smple. Funtionl groups tht re identified in the FTIR nlysis, mong others, OH, H 2- nd CO 3 2- in the rnge 4000 to 600 m-1 s shown in Figure 1. Aording Alqp nd Sopyn [9] group nds pper t wvelengths from 1100 to 1019, 958, 962 nd 605 m -1 in ddition to tht. In 0.67 C/P rtio smple rion ppers t wvelength of 953, 1027, nd 1067 m -1. In 1.67 C/P rtio smple ppers t wvelength of 962, 1087, 1023 m -1, wheres in 2.67 C/P rtio smple t wvelengths of 963, 1024, nd 1086 m -1 s shown in Figure 1. In ddition group, there re ion ppers y FTIR nlysis of the smples. Where ion ours t wvelength of , 630, nd 667 m -1. In 0.67 C/P rtio smple group ppers t wvelength of 683 nd 612 m -1. In 1.67 C/P rtio smple ppers t wvelengths 3572, 3642, 628 m -1, where s in 2.67 C/P rtio smple t wvelength of 3643 nd 630 m - 1. Then there H 2- group ontined t wvelengths 1308 nd 1260 m -1 in 0.67 C/P rtio smple. Figure 1 lso shows lusters t wvelengths 788 nd 710 m -1 whih is sed on reserh Alqp nd Sopyn [9] t the round tht wvelength the funtionl group tht ppers ws group of P 2 O 7. This proves the presene of lium pyrophosphte phse. The results otined spetrum for eh reserher of HAP is different ut still in the djent vlues. The results show tht there is nother group of ompounds tht should not exist in Figure 1 : FTIR spetr of HAP prepred for C/P rtio of () 0.67 () 1.67 nd () 2.67 Phosphte groups ( ) symmetri strething virtion synthesized deteted t wve numer 1019 m -1 whih indites tht the rystls formed in the synthesis results. In ddition, the hydroxyptite visile spetrum hrteristi sorption nd round 2021 m H 2 O -1, 2167 m -1 nd 2182 m -1. An inrese in the intensity of the nd m -1 whih is nd of H 2 O on the surfe euse the surfe sors wter smples HAP. This is possile euse the smple storge tehniques unfvorle sili gel whih does not inlude the storge time or my lso e due to HAP produed from the lintion proess eomes more hygrosopi due to the higher lintion temperture. The mesurement results of hydroxyptite synthesized using low temperture hydrotherml method with 2.67 C/P rtio using FTIR nlysis shown in Figure 2. Phosphte 25 Pulished y Interntionl Soiety of Oen, Mehnil nd Aerospe Sientists nd Engineers

3 groups (PO 4 ) symmetri strething virtion synthesized deteted t wve numer 1024 m -1 nd 1085 m -1 whih indites tht the rystls formed in the synthesis results. In ddition, the hydroxyptite visile spetrum hrteristi of the sorption nd round 3642 m -1. This n hppen euse the HAP powder is hygrosopi, thus preipitting the hydrtion of the ir. group t 3642 m -1 region is lled wter sorption. Rion uptke ronte (CO 2-3 ) synthesis were lso deteted t wve numer 1423 m -1 whih is the symmetri strething virtion sorption nd is wek with no form of symmetry. H 2O sorption nd round 3641 m -1 nd 636 m -1. This n hppen euse the HAP powder is hygrosopi, thus preipitting the hydrtion of the ir. group t 3641 m -1 region is lled wter sorption, wheres the OH groups were deteted round the wve numer of 636 m -1 is n illustrtion of the wter sorption. Cronte sorption nd (CO 2-3 ) synthesis were lso deteted t wve numer 1463 m -1 whih is the symmetri strething virtion sorption nd is wek with no form of symmetry. 3.2 X-ry Anlysis From the results of XRD nlysis, it is found tht hnge in the intensity of the pek from diffrtogrm. The results of XRD nlysis s shown in Figure 3 where for eh smple shows the mjority present of peks re hydroxyptite. Pek of the hydroxyptite 0.67 C/P rtio smple t 2θ , nd with hkl (002), (211) nd (300). In the 1.67 C/P rtio smple t 2θ , , nd with hkl (002), (211) nd (300). And on the 2.67 C/P rtio smple t 2θ , , nd with hkl (002), (211) nd (300). Where in the pek hkl vlues re similr to pttern hrteriztion results of XRD nlysis from JCPDS (Joint Committee on Powder Diffrtion Stndrds) with PDF Crd No In ddition, from the dt se of results otined XRD nlysis of rystl rystl dimeter eh smple sed on the Sherrer eqution, where the rystl dimeter grew long with the inresing rtio of C/P nd temperture is shown in tle 1. Tle 1: The verge rystllite size of the smples C/P rtio Retion temperture ( C) Crystl dimeter (nm) Figure 2 : FTIR spetr of HAP prepred t retion temperture of () 70 C () 80 C nd () 90 C The mesurement results of hydroxyptite synthesized using hydrotherml method with low temperture of 90 o C using FTIR nlysis shown in Figure 2. Phosphte groups (PO 4 ) symmetri strething virtion synthesized deteted t wve numer 1025 m -1 nd 1241 m -1 whih indites tht the rystls formed in the synthesis results. Rion phosphte present in the spetrum of ommeril hydroxyptite s smll nd t wve numer 878 m -1, 961 m -1 nd 981 m -1. In ddition, the hydroxyptite visile spetrum hrteristi of the Bsed on the nlysis of XRD peks n lso e seen other thn hydroxyptite on smples where eh smple ontins phses s shown in Tle 2. In smples with rtio of 0.67 there is phse other thn the phse omposition of hydroxyptite, the lium pyrophosphte. The lium pyrophosphte ompound formed y lium hydroxide derived from the mixing of CO with wter rets with phosphori id, resulting in lium dihydrogen phosphte s the following eqution: C(OH) 2 + 2H 3 C(H 2 ) 2 + 2H 2 O (3) Then lium dihydrogen phosphte rets with mmoni to produe monetite (CHPO4) or dilium phosphte nhydrous (DCPA) s shown in the following retion: C(H 2 ) 2 + NH 3 CH + NH 4 H 2 (4) Tle 2: Phse ontined in different C/P rtio smples C/P rtio 26 Pulished y Interntionl Soiety of Oen, Mehnil nd Aerospe Sientists nd Engineers

4 Minerl phse Hydroxiptite, Clium 0.67 phosphte Hydroxiptite, 1.67 Trilium phosphte Hydroxiptite, Clium 2.67 hydroxide Where monetite (DCPA) is wht uses the formtion of lium pyrophosphte. Monetite (DCPA) deomposes into lium pyrophosphte t temperture of C, this ws lso study done y Alqp nd Sopyn [9]. CP HAP TCP CH C 2 P 2 O 7 + CO C 3 ( ) 2 (5) While the 2.67 C/P smple phse omposition ws onsisting of hydroxyptite nd lium hydroxide. Where lium hydroxide CO derived from mixing with wter following retion: CO + H 2 O C(OH) 2 (6) 3.2 Morphology Smple From the results of SEM morphology ppers ptite rystls tht gther severl ompounds tht pper lrger with smooth nd uniform grin [14]. Smples with higher heting tempertures produe rystls with purity higher thn smples with lower heting tempertures. Beuse of the high temperture heting will mke the proess of etter prtiles growth [15]. HA C(OH) 2 C() 3 Figure 3 : XRD ptterns of HAP t C/P rtio of () 0,67 () 1,67 nd () 2,67 In smples with rtio of 1.67 C/P phse omposition onsisting of hydroxyptite, nd trilium phosphte. The formtion of trilium phosphte in 0.67 C/P smple is influened y the rtio of C/P in whih the rtio of C/P is smller thn trilium phosphte hydroxyptite, it is lso onsistent with studies onduted y Zhng nd Drvell [13] where trilium phosphte formed in the mss rtio of C/P Also ording Alqp nd Sopyn [9] CO were still present in the smple n use the formtion of trilium phosphte nd lium pyrophosphte ret like the following retion: Figure 4 : FTIR spetr of HAP t retion temperture of () 70 C () 80 C nd () 90 C The smple hs monolini nd hexgonl rystlline struture. A monolini rystlline struture tht hs n xis tht is tilted from its three xes. A xis perpendiulr to the xis ; perpendiulr to, ut not -xis perpendiulr to the xis. All three xes re unequl in length, generlly the longest xis nd the shortest xis. While hexgonl rystlline struture tht hs 4 xes of symmetry with the symmetry xis lies in the Pulished y Interntionl Soiety of Oen, Mehnil nd Aerospe Sientists nd Engineers

5 field, whih is horizontl. The third xis of symmetry mkes n ngle of 60 etween the horizontl xis nd the fourth xis is the vertil xis is ut perpendiulr to the xis of symmetry horizontl third. The fourth xis is usully longer thn the third horizontl xis. Results of SEM for the results of the synthesis of hydroxyptite with retion temperture of 70 C, 80 C nd 90 C is shown in Figure 5. Smples with the SEM oservtion results using 7500x mgnifition n e seen in Figure 5. The results of oservtion smples with retion temperture of 70 C, 80 C nd 90 C (Figure 5) looks like group of smll dense prtiles. Grin size of the 90 C retion temperture smple looks smller thn the 70 C nd 80 C smples. This is reinfored y the results of the lultion of the size of the rystls from the XRD pttern. Defined s n individul rystl grins. The size of the rystl smple is nm where s 70 C retion temperture smple, 80 C nd 90 C smples re nm nd nm. The inrese in temperture resulted in n inresed therml virtion energy, whih then elertes the diffusion of toms through the grin oundries, smll droplets into lrger ones. From Figure 5 it n e seen tht the distne etween the prtiles re initilly very tight show tenuous when the heting temperture is lower. d Figure 5 shows the results of the smples with vrition of the rtio C/P.In smple with the C/P rtio of 0.67 is shown in Figure 5 d hs lrger size thn the other smples (1.67 nd 2.67 C/P rtio smples), this is used y the presene of some other ptite ompounds ontined in the smple s hs een seen in the results of XRD nd FTIR nlysis. SEM results lso showed tht the synthesis of the rtio of C/P of 0.67 in oth immture hydroxyptite. SEM result for smple with the rtio C/P of 1.67 is shown in Figure 5 e. From the results of SEM photogrph looks morphology with finer grins. It is lso used y the presene of other ompounds suh s trilium phosphte ptite were lso seen in the results of XRD nlysis. For smple with the rtio C/P of 2.67 is shown in Figure 5 f. From the results of SEM morphology of the grins pper smoother nd more uniform ompre to 0.67 nd 1.67 C/P rtio smples. In ordne with the X-ry diffrtion pttern showed tht the synthesis of the rtio of 2.67 C/P rtio produe hydroxyptite peks more thn 0.67 nd 1.67 C/P rtio smples. 4.0 CONCLUSION Effet of C/P rtio nd retion temperture on hemil properties of hydroxyptite powder from se shell using low temperture hydrotherml method hs een presented the pper. The rystl dimeter of HAP t C/P rtio of 0.67, 1.67 nd 2.67 were 53.38, nd respetively. HAP phse t C/P rtio of 2.67 nd 90 C temperture retion ws found predominnt. ACKNOWLEDGEMENTS The uthors would like to onvey gret ppreition to DIKTI for supporting this reserh through Hih Kompetensi e f Figure 5: SEM results for smple with retion temperture of () 70 C () 80 C, () 90 C nd C/P rtio of () 0,67 (e) 1,67 (f) 2,67 REFERENCE 1. Gosin, A. K., & Persing, J. A. (1999). Biomterils in The Fe: Benefits nd Risks. Journl of Crniofil Surgil 10: Kuo, T. C., Lee B. S., Kng, S. H., Lin, F. H., & Lin, C. P. (2007). Cytotoxiity of DP-ioglss pste used for tretment of dentin hypersensitivity. Journl of Endodontis 33: Henh, L. L. (1991). Bioermis: from onept to lini. Journl of The Amerin Cermi Soiety 74: Mosherpur, I., Heshjin, M. S., Kzemzdeh, A., & Zkeri, M. (2007). Synthesis of nnorystlline hydroxyptite y using preipittion method. Journl of Alloys nd Compounds 430(1-2): Fhmi A., Erhimi-Khrizsngi R., & Nsiri-Trizi, B. (2011). Mehnohemil synthesis of hydroxyptite/titnium nnoomposite. Solid Stte Sienes 13: Rhee, S.-H. (2002). Synthesis of hydroxyptite vi mehnohemil tretment. Biomterils 23(4): Sdt-Shoji, M., Khorsni, M.-T., & Jmshidi, A. (2012). Hydrotherml proessing of hydroxyptite nnoprtiles tguhi experimentl design pproh. Journl of Crystl Growth 361: Zhng, X., & Vehio, K. S. (2006). Cretion of dense 28 Pulished y Interntionl Soiety of Oen, Mehnil nd Aerospe Sientists nd Engineers

6 hydroxyptite (syntheti one) y hydrotherml onversion of seshells. Mterils Siene nd Engineering C 26: Alqp A. S. F., & Sopyn, I. (2009). Low temperture hydrotherml synthesis of lium phosphte ermis: effet of exess C proursor on phse ehviour. Indin Journl of Chemistry 48: Sdt-Shoji, M., Ati, M. & Nodehi, A. (2011). Design of experiments (DOE) for the optimiztion of hydrotherml synthesis of hydroxyptite nnoprtiles. Journl of Brzillin Chemil 22: Zhng, X., Vehio, K. S., Mssie J. B., Wng m., & Kim, C. W. (2007). Conversion of ulk seshells to ioomptile hydroxyptite for one implnts. At Biomterili 3: Sopyn, I., Mel, M., Rmesh, S., & Khlid, K. A. (2007). Porous hydroxyptite for rtifiil one pplitions. Siene nd Tehnology of Advned Mterils 8: Zhng, H., & Drvell, B. W. (2011). Morphology nd struturl hrteristis of hydroxyptite whiskers: effet of the initil C onentrtion, C/P rtio nd ph. At Biomterili 7: Wu, S.-C., Tsou, H.-K., Hsu, H.-C., & Liou, S.-P. (2013). A hydrotherml synthesis of eggshell nd fruit wste extrt to produe nnosized hydroxyptite. Cermis Interntionl 39: Moore, W. R., Grves, S. E. & Bin, G. I Syntheti one grft sustitutes. ANZ Journl of Surgery 71: Pulished y Interntionl Soiety of Oen, Mehnil nd Aerospe Sientists nd Engineers