18 TH INTERNATIONAL CONFERENCE ON COMPOSITE MATERIALS RADIOPACITY OF RESTORATIVE COMPOSITES FILLED WITH SiO 2 /ZrO 2 CORE-SHELL PARTICLES M. Kim 1, 5 , M. Lee 1* , W. Seo 1 , M. Oh 2 , W. Kim 2 , N. Oh 3 , Y. Lee 4 , H. Choi 5 1 Green Ceramics Division, Korea Institute of Ceramic Engineering and Technology, 233-5 Gasan-dong, Geumcheon-gu, Seoul 153-801, Korea, 2 R&D center, Vericom CO., LTD, Anyang, Kyeonggi-Do 430-817, Korea, 3 Department of Dentistry, College of Medicine, Inha University, 402-751 Incheon, Korea, 4 Department and Research Institute of Dental Biomaterials and Bioengineering, Yonsei University College of Dentistry, 120-752 Seoul, Korea, 5 Department of Materials Science and Engineering, Yonsei University, 134 Sinchon-dong, Seodaemun-gu, Seoul 120-749, Korea * Corresponding author(mhlee@kicet.re.kr) Keywords : radiopacity; SiO 2 /ZrO 2 ; core-shell; composites; restorative coated with ZrO 2 nanoparticle as a filler to render 1. Introduction proper radiopacity. One of the most desirable properties of any dental restorative materials is radiopacity, a property that both facilitates the radiographic diagnoses adjacent 2. Material and Method to dental composites and enables a practitioner to Radiopaque SiO 2 /ZrO 2 core-shell fillers having a distinguish a restorative material from caries and the controlled shell thickness were obtained using a sol- surrounding tooth structure [1,2]. To render gel process. Commercial silica spheres having a radiopacity, elements having a relatively high atomic mean diameter of 110 nm (Sukgyung AT, Korea) number such as zirconium, barium, strontium or were used as the core particles. To prepare the core- titanium, are often incorporated into SiO 2 -based shell particles, SiO 2 particles (5g) were initially filler particles [3]. Although barium is considered to dispersed in a mixture solution of ethanol (99.5%) be the strongest radiopacifier for the filler phase of and H 2 O using an ultrasonicator. To deposit a composites [4], Smith et al. found that barium ions, uniform ZrO 2 shell on monodispersed silica spheres, once leached out into the oral fluid, are not a mixture solution of zirconium(IV) butoxide biocompatible. Moreover, severe foreign body (TBOZ, 80%, Aldrich, USA) and ethanol was then reactions were noted in the oral soft tissue [5]. In constantly added to the reactor for 2h, and this was contrast, the zirconium is biologically inert in the followed by heating 45˚C for 90min to complete the oral environment [6] and only slightly reduces the sol-gel process. The concentrations of TBOZ were chemical stability of SiO 2 -based fillers [3]. adjusted at 0.015, 0.03, 0.045 and 0.1mol/l so as to Recently, various studies of SiO 2 -ZrO 2 hybrid control the ZrO 2 shell thickness. Finally, the solution fillers utilizing the sol-gel process have been was dried at 100˚C for 24h and pulverized with a observed and discussed. Most of them were focused mortar and pestle. The size, morphology and shell on SiO 2 -ZrO 2 mixed particles [3,7,8,9,10]. There has thickness of the zirconia-coated silica particles were been little research in which a precisely controlled examined using transmission electron microscopy SiO 2 /ZrO 2 core-shell structure prepared by the sol- (JEM 2000EX, Jeol, Japan). gel process for radiopacity has been applied. Core- The visible light-cured composite specimens were shell particles can be tailored according to the fabricated by mixing 50wt% monomer mixture and characteristics of the core and the shell. The mono- 50wt% core-shell fillers. The monomer mixture dispersed SiO 2 as core particles in the resin matrix, consisted of 50wt% bis-GMA (Aldrich, USA), assuming that they have the proper size and a 50wt% TEGDMA (Aldrich, USA) and 0.5wt% CQ spherical shape, enhance the mechanical and optical (λ=468nm, Aldrich, USA). The composite resins properties. The formation of a ZrO 2 shell on silica contained bare SiO 2 particles, and barium silicate spheres differs in terms of radiopacity depending on glasses (Ba Glass, avg. dia. =1.0 µm, Schott, the nanometer scale-shell thickness. This study Germany) were used as a control, respectively. All assesses the possibility of using SiO 2 spherical cores
specimens were manufactured in the form of disks 15 mm in diameter and 1, 2 and 3 mm thick. Nucleation rate = k 2 (2) Each sample was placed on a phosphor plate with an aluminum step-wedge having 20 steps ranging from 1 to 20 mm as a standard to compare the radio- Here, Q is the amount of the dissolved material, S density. The radiographic exposure was done using is the solubility, is the degree of relative super- an x-ray unit (MULTIX-UH, Siemens, Germany), saturation and k 1 and k 2 are constants. When operated for 0.5 s at 70 kV and 5 mA. The film- increasing the concentration of TBOZ, the degree of object distance was 50 cm. The radiographs from the super-saturation is increased. phosphor plates were developed and printed on In the dilute region of solute material, particle medical x-ray film 32 × 39 cm in size. The optical growth is dominant to nucleation because of low density of radiographic film was analyzed with a nucleation rate. The shell thickness of core-shell transmission densitometer (PDA-100, Konica Co., particle was increased linearly up to 0.045M as the Japan). The measured value was converted in terms degree of super-saturation following the linear of the equivalent thickness of aluminum by referring dependence of growth rate in precipitation. Once to the calibration curve for the radiographic density formed, the nuclei grow by aggregation and form the of an aluminum step-wedge. shell where deposit on the SiO 2 core surface. In this region all the materials supplied by hydrolysis and condensation was used for growing and thickening 3. Results and Discussion of zirconia shell. A series of SiO 2 -ZrO 2 core-shell particles were Generally in the high concentration region, prepared via a sol-gel process by varying the nucleation is dominant and the rate follows power reaction conditions. There is a pronounced law dependence as a function of concentration. difference in the shell thickness and morphology However, in the region beyond 0.045M of TBOZ, when adjusting the concentration of the zirconium the shell was thickened in the low rate of linear butoxide (TBOZ). The core-shell particles are shown increase. It is caused by evolution of homo in Figs. 1(a-c), in which ZrO 2 shell appears as a dark aggregate from homogeneous nucleation and growth. ring around the SiO 2 core, showing a uniform shell In this region almost materials supplied by with a smooth surface. In contrast, irregularly coated hydrolysis and condensation was used for homo particles with rough surface were obtained (Fig. aggregate, only small part of materials was used for 1(d)), and self-aggregation of the ZrO 2 particles thickening of zirconia shell. Therefore, the uniform occurred, resulting in homo-aggregates in the core-shell particles for filler of restorative product. composites could be synthesized in the condition of As shown in Fig. 2, the ZrO 2 shell thickness up to 0.045M of TBOZ concentration. increased significantly with the increment of the The amount of the H 2 O is relatively less susceptible TBOZ concentration. The formation of zirconia shell to increase zirconia shell as opposed to the TBOZ is related to the nucleation and growth of the particle. concentration. Fig. 3 shows that the shell thickness The zirconia molecules and nuclei are generated by of the core-shell particles decreased as the H 2 O the hydrolysis and condensation process of concentration increased. The higher the water zirconium alkoxide [11,12]. These nuclei are concentration, the lower concentration of TBOZ in precipitated in a labile super-saturated solution due the reaction solution, and the smaller shell thickness to its low solubility and coalesced fast onto the SiO 2 obtained. Therefore, the shape of core-shell particles core surface. The growth of nuclei take place is directly dictated by the ZrO 2 nano-particle through polycondensation or aggregate with each generation and its deposition and growth on the SiO 2 other. In general, the relationship between core particles. nucleation and the growth rate as a function of the Fig. 4 and Table 1 show the radiopacity values of degree of super-saturation. This is expressed as the experimental composite resins containing follows [13]: prepared SiO 2 /ZrO 2 core-shell fillers, Ba glass and SiO 2 core particles. The samples fabricated with the TBOZ concentrations of 0.015, 0.030, 0.045 and Growth rate = k 1 (1) 0.1M are simply denoted here as Zr-b015, Zr-b030, Zr-b045 and Zr-b100, respectively. There was a
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