Whisker-reinforced bioactive composites containing calcium phosphate cement fillers: effects of filler ratio and surface treatments on mechanical properties

Calcium phosphate cement (CPC) sets to form microporous solid hydroxyapatite with excellent osteoconductivity, but its brittleness and low strength prohibit use in stress-bearing locations. The aim of this study was to incorporate prehardened CPC particles and ceramic whiskers in a resin matrix to improve the strength and fracture resistance, and to investigate the effects of key microstructural variables on composite mechanical properties. Two types of whiskers were used: silicon nitride, and silicon carbide. The whiskers were surface-treated by fusing with silica and by silanization. The CPC particle fillers were either silanized or not silanized. Seven mass ratios of whisker-silica/CPC were mixed: 0:1 (no whisker-silica), 1:5, 1:2, 1:1, 2:1, 5:1, and 1:0 (no CPC). Each powder was blended with a bisphenol-a-glycidyl methacrylate-based resin to harden in 2 x 2 x 25 mm molds by two-part chemical curing. The specimens were tested in three-point flexure to measure strength, work-of-fracture (toughness), and elastic modulus. Two-way analysis of variance was used to analyze the data, and scanning electron microscopy was used to examine specimen fracture surfaces. The whisker-silica/CPC ratio had significant effects on composite properties (p < 0.001). When this ratio was increased from 0:1 to 1:0, the strength was increased by about three times, work-of-fracture by five times, and modulus by two times. Whisker surface treatments and CPC filler silanization also had significant effects (p < 0.001) on composite properties. Scanning electron microscopy revealed rough fracture surfaces for the whisker composites with steps and whisker pullout. Resin remnants were observed on the surfaces of the pulled-out whiskers, indicating strong whisker-matrix bonding. In conclusion, incorporating highly osteoconductive CPC fillers and ceramic whiskers yielded composites with substantially improved mechanical properties compared with composites filled with CPC particles without whiskers. The composite properties were determined by whisker-to-CPC ratio and filler surface treatments.     

Dental resin composites containing silica-fused whiskers--effects of whisker-to-silica ratio on fracture toughness and indentation properties.

Dental resin composites need to be strengthened in order to improve their performance in large stress-bearing applications such as crowns and multiple-unit restorations. Recently, silica-fused ceramic whiskers were used to reinforce dental composites, and the whisker-to-silica ratio was found to be a key microstructural parameter that determined the composite strength. The aim of this study was to further investigate the effects of whisker-to-silica ratio on the fracture toughness, elastic modulus, hardness and brittleness of the composite. Silica particles and silicon carbide whiskers were mixed at whisker:silica mass ratios of 0:1, 1:5. 1:2, 1:1, 2:1, 5:1, and 1:0. Each mixture was thermally fused, silanized and combined with a dental resin at a filler mass percentage of 60%. Fracture toughness was measured with a single-edge notched beam method. Elastic modulus and hardness were measured with a nano-indentation system. Whisker:silica ratio had significant effects on composite properties. The composite toughness (mean+/-SD; n = 9) at whisker:silica = 2:1 was (2.47+/-0.28) MPa m(1/2), significantly higher than (1.02+/-0.23) at whisker:silica = 0:1, (1.13+/-0.19) of a prosthetic composite control, and (0.95+/-0.11) of an inlay/onlay composite control (Tukey's at family confidence coefficient = 0.95). Elastic modulus increased monotonically and hardness plateaued with increasing the whisker:silica ratio. Increasing the whisker:silica ratio also decreased the composite brittleness, which became about 1/3 of that of the inlay:onlay control. Electron microscopy revealed relatively flat fracture surfaces for the controls, but much rougher ones for the whisker composites, with fracture steps and whisker pullout contributing to toughness. The whiskers appeared to be well-bonded with the matrix, probably due to the fused silica producing rough whisker surfaces. Reinforcement with silica-fused whiskers resulted in novel dental composites that possessed fracture toughness two times higher than, and brittleness less than half of current dental composites.     

Whisker-reinforced dental core buildup composites: effect of filler level on mechanical properties

The strength and toughness of dental core buildup composites in large stress-bearing restorations need to be improved to reduce the incidence of fracture due to stresses from chewing and clenching. The aims of the present study were to develop novel core buildup composites reinforced with ceramic whiskers, to examine the effect of filler level, and to investigate the reinforcement mechanisms. Silica particles were fused onto the whiskers to facilitate silanization and to roughen the whisker surface for improved retention in the matrix. Filler level was varied from 0 to 70%. Flexural strength, compressive strength, and fracture toughness of the composites were measured. A nano-indentation system was used to measure elastic modulus and hardness. Scanning electron microscopy (SEM) was used to examine the fracture surfaces of specimens. Whisker filler level had significant effects on composite properties. The flexural strength in MPa (mean +/- SD; n = 6) increased from (95+/-15) for the unfilled resin to (193+/- 8) for the composite with 50% filler level, then slightly decreased to (176+/-12) at 70% filler level. The compressive strength increased from (149+/-33) for the unfilled resin to (282+/-48) at 10% filler level, and remained equivalent from 10 to 70% filler level. Both the modulus and hardness increased monotonically with filler level. In conclusion, silica particle-fused ceramic single-crystalline whiskers significantly reinforced dental core buildup composites. The reinforcement mechanisms appeared to be crack deflection and bridging by the whiskers. Whisker filler level had significant effects on the flexural strength, compressive strength, elastic modulus, and hardness of composites.     

Strong and bioactive composites containing nano-silica-fused whiskers for bone repair

Self-hardening calcium phosphate cement (CPC) sets to form hydroxyapatite with high osteoconductivity, but its brittleness and low strength limit its use to only non-stress bearing locations. Previous studies developed bioactive composites containing hydroxyapatite fillers in Bis-GMA-based composites for bone repair applications, and they possessed higher strength values. However, these strengths were still lower than the strength of cortical bone. The aim of this study was to develop strong and bioactive composites by combining CPC fillers with nano-silica-fused whiskers in a resin matrix, and to characterize the mechanical properties and cell response. Silica particles were fused to silicon carbide whiskers to roughen the whisker surfaces for enhanced retention in the matrix. Mass ratios of whisker:CPC of 1:2, 1:1 and 2:1 were incorporated into a Bis-GMA-based resin and hardened by two-part chemical curing. Composite with only CPC fillers without whiskers served as a control. The specimens were tested using three-point flexure and nano-indentation. Composites with whisker:CPC ratios of 2:1 and 1:1 had flexural strengths (mean+/-SD; n=9) of (164+/-14) MPa and (139+/-22) MPa, respectively, nearly 3 times higher than (54+/-5) MPa of the control containing only CPC fillers (p<0.05). The strength of the new whisker-CPC composites was 3 times higher than the strength achieved in previous studies for conventional bioactive composites containing hydroxyapatite particles in Bis-GMA-based resins. The mechanical properties of the CPC-whisker composites nearly matched those of cortical bone and trabecular bone. Osteoblast-like cell adhesion, proliferation and viability were equivalent on the non-whisker control containing only CPC fillers, on the whisker composite at whisker:CPC of 1:1, and on the tissue culture polystyrene control, suggesting that the new CPC-whisker composite was non-cytotoxic.     

Effects of incorporating nanosized calcium phosphate particles on properties of whisker-reinforced dental composites

Clinical data indicate that secondary caries and restoration fracture are the most common problems facing tooth restorations. Our ultimate goal was to develop mechanically-strong and caries-inhibiting dental composites. The specific goal of this pilot study was to understand the relationships between composite properties and the ratio of reinforcement filler/releasing filler. Nanoparticles of monocalcium phosphate monohydrate (MCPM) were synthesized and incorporated into a dental resin for the first time. Silicon carbide whiskers were fused with silica nanoparticles and mixed with the MCPM particles at MCPM/whisker mass ratios of 1:0, 2:1, 1:1, 1:2, and 0:1. The composites were immersed for 1-56 days to measure Ca and PO4 release. When the MCPM/whisker ratio was changed from 0:1 to 1:2, the composite flexural strength (mean +/- SD; n = 5) decreased from 174 +/- 26 MPa to 138 +/- 9 MPa (p < 0.05). A commercial nonreleasing composite had a strength of 112 +/- 14 MPa. When the MCPM/whisker ratio was changed from 1:2 to 1:1, the Ca concentration at 56 days increased from 0.77 +/- 0.04 mmol/L to 1.74 +/- 0.06 mmol/L (p < 0.05). The corresponding PO4 concentration increased from 3.88 +/- 0.21 mmol/L to 9.95 +/- 0.69 mmol/L (p < 0.05). Relationships were established between the amount of release and the MCPM volume fraction v(MCPM) in the resin: [Ca]= 42.9 v(MCPM) (2.7), and [PO4] = 48.7 v(MCPM) (1.4). In summary, the method of combining nanosized releasing fillers with reinforcing fillers yielded Ca- and PO4-releasing composites with mechanical properties matching or exceeding a commercial stress-bearing, nonreleasing composite. This method may be applicable to the use of other Ca-PO4 fillers in developing composites with high stress-bearing and caries-preventing capabilities, a combination not yet available in any dental materials.     

Strength and fluoride release characteristics of a calcium fluoride based dental nanocomposite

Secondary caries and restoration fracture remain the two most common problems in restorative dentistry. Release of fluoride ions (F) could be a substantial benefit because F could enrich neighboring enamel or dentin to combat caries. The objective of this study was to incorporate novel CaF(2) nanoparticles into dental resin to develop stress-bearing, F-releasing nanocomposite. CaF(2) nanoparticles, prepared in our laboratories for the first time, were combined with reinforcing whisker fillers in a resin. Flexural strength (mean+/-sd; n=6) was 110+/-11MPa for the composite containing 30% CaF(2) and 35% whiskers by mass. It matched the 108+/-19MPa of a stress-bearing, non-releasing commercial composite (Tukey's at 0.05). The composite containing 20% CaF(2) had a cumulative F release of 2.34+/-0.26mmol/L at 10weeks. The initial F release rate was 2mug/(hcm(2)), and the sustained release rate after 10weeks was 0.29mug/(hcm(2)). These values exceeded the reported releases of traditional and resin-modified glass ionomer materials. In summary, nanocomposites were developed with relatively high strength as well as sustained release of fluoride ions, a combination not available in current materials. These strong and F-releasing composites may yield restorations that can reduce the occurrence of both secondary caries and restoration fracture.     

三种方法对硼酸铝晶须表面改性作用及其对复合树脂性能的影响

分别采用三种不同方法对硼酸铝晶须(AlBw)进行表面改性。方法一:将AlBw与商品纳米二氧化硅(SiO2)在一定工艺下直接高温熔附;方法二:将正硅酸乙酯(TEOS)用溶胶-凝胶法水解形成Si-O网络结构的膜,同时包裹于AlBw表面,进一步与商品纳米SiO2高温熔附;方法三:用溶胶-凝胶法在一定工艺条件下使TEOS水解得到纳米SiO2,同时沉积于AlBw表面,然后高温熔附。透射电镜(TEM)和扫描电镜(SEM)观察不同方法改性AlBw后其表面形态的变化。按一定质量比加入树脂基质中,测试树脂弯曲性能,SEM观察断口形貌。结果表明:晶须改性后可以提高复合树脂的弯曲性能,不同改性方法作用不同;商品SiO2纳米颗粒直接熔附于AlBw进行表面改性,复合树脂的弯曲强度达(95.28±4.53)MPa,但AlBw、纳米SiO2间团聚明显;采用TEOS溶胶-凝胶法对AlBw进行表面处理后与商品SiO2纳米颗粒混合,团聚有改善,但分布不均匀;采用TEOS溶胶-凝胶法直接生成纳米SiO2改性AlBw,是一种理想的改性方法,经此法改性的AlBw-SiO2复合体可以显著提高复合树脂的弯曲性能,复合树脂的弯曲强度达(130.29±8.38)MPa,SiO2粒径分布均匀,AlBw表面有分布较均匀的、分散的SiO2纳米颗粒熔附,团聚程度降低。     

CaSO4和MgSO4晶须填料对牙科复合树脂抗弯强度的影响

目的 观察CaSO4晶须和MgSO4晶须对复合树脂的抗弯强度的影响.方法 制备CaSO4晶须和MgSO4晶须,以硬脂酸钠改性剂表面改性,随后分别按质量分数为1%、10%、20%、30%混合添加到复合树脂中,固化后评价其三点抗弯强度,扫描电镜观察断面形态.结果 添加2种晶须的质量分数在10%及以下时,复合树脂的三点抗弯强度均下降,质量分数为20%和30%时,MgsO4晶须组的三点抗弯强度增加.结论 添加适当比例的MgSO4晶须可以提高复合树脂的三点抗弯强度.     

Reinforcement of a self-setting calcium phosphate cement with different fibers

A water-based calcium phosphate cement (CPC) has been used in a number of medical and dental procedures due to its excellent osteoconductivity and bone replacement capability. However, the low tensile strength of CPC prohibits its use in many unsupported defects and stress-bearing locations. Little investigation has been carried out on the fiber reinforcement of CPC. The aims of the present study, therefore, were to examine whether fibers would strengthen CPC, and to investigate the effects of fiber type, fiber length, and volume fraction. Four different fibers were used: aramid, carbon, E-glass, and polyglactin. Fiber length ranged from 3-200 mm, and fiber volume fraction ranged from 1.9-9.5%. The fibers were mixed with CPC paste and placed into molds of 3 x 4 x 25 mm. A flexural test was used to fracture the set specimens and to measure the ultimate strength, work-of-fracture, and elastic modulus. Scanning electron microscopy was used to examine specimen fracture surfaces. Fiber type had significant effects on composite properties. The composite ultimate strength in MPa (mean +/- SD; n = 6) was (62+/-16) for aramid, (59+/-11) for carbon, (29+/-8) for E-glass, and (24+/-4) for polyglactin, with 5.7% volume fraction and 75 mm fiber length. In comparison, the strength of unreinforced CPC was (13+/-3). Fiber length also played an important role. For composites containing 5.7% aramid fibers, the ultimate strength was (24+/-3) for 3 mm fibers, (36+/-13) for 8 mm fibers, (48 +/-14) for 25 mm fibers, and (62+/-16) for 75 mm fibers. At 25 mm fiber length, the ultimate strength of CPC composite was found to be linearly proportional to fiber strength. In conclusion, a self-setting calcium phosphate cement was substantially strengthened via fiber reinforcement. Fiber length, fiber volume fraction, and fiber strength were found to be key microstructural parameters that controlled the mechanical properties of CPC composites.     

Self-hardening calcium phosphate cement-mesh composite: reinforcement, macropores, and cell response

Calcium phosphate cement (CPC) self-hardens to form hydroxyapatite, has excellent osteoconductivity and bone-replacement ability, and is promising for craniofacial and orthopedic repair. However, its low strength limits CPC to only nonstress repairs. This study aimed to reinforce CPC with meshes to increase strength, and to form macropores in CPC for bone ingrowth after mesh dissolution. A related aim was to evaluate the biocompatibility of the new CPC-mesh composite. Absorbable polyglactin meshes, a copolymer of poly(glycolic) and poly(lactic) acids, were incorporated into CPC to provide strength and then form interconnected cylindrical macropores suitable for vascular ingrowth. The composite flexural strength, work-of-fracture, and elastic modulus were measured as a function of the number of mesh sheets in CPC ranging from 1 (a mesh on the tensile side of the specimen) up to 13 (mesh sheets throughout the entire specimen), and as a function of immersion time in a physiological solution from 1 to 84 days. Cell culture was performed with osteoblast-like cells and the cell viability was quantified using an enzymatic assay. The strengths (mean +/- SD; n = 6) of CPC containing 13 or 6 meshes were 24.5 +/- 7.8 and 19.7 +/- 4.3 MPa, respectively, not significantly different from each other; both were significantly higher than 8.8 +/- 1.9 MPa of CPC without mesh (Tukey's at 0.95). The work-of-fracture of CPC with 13 or 6 meshes was 3.35 +/- 0.80 and 2.95 +/- 0.58 kJ/m(2), respectively, two orders of magnitude higher than 0.021 +/- 0.006 kJ/m(2) of CPC without mesh. Interconnected macropores were formed in CPC at 84 days' immersion. The new CPC-mesh formulation supported the adhesion, spreading, proliferation, and viability of osteoblast-like cells in vitro. In conclusion, absorbable meshes in CPC increased the implant strength by three-fold and work-of-fracture by 150 times; interconnected macropores suitable for bone ingrowth were created in CPC after mesh dissolution. The higher strength may help extend the use of CPC to larger stress-bearing repairs, and the macropores may facilitate tissue ingrowth and integration of CPC with adjacent bone.     

Effects of filler composition and surface treatment on the characteristics of opaque resin composites

The effects of filler composition and surface treatment of titanium dioxide (TiO2) on the shear bond strength to noble metal and mechanical properties of opaque dental resin composites were assessed. A series of fillers for resin composites were prepared with untreated TiO2 or treated silica/alumina-coated TiO2 with silane coupling agent; these fillers were replaced with silanized SiO2 in increasing amounts. Each of various powder compositions were mixed with the liquid and applied to the surface of a silver-palladium-copper-gold (Ag-Pd-Cu-Au) alloy and light cured. A light-activated resin-veneering composite material was placed on top with the use of a brass ring mold and light cured. Specimens were stored at 37 degrees C in water for a period of 24 h. Additionally some specimens were thermocycled at 4 degrees C and 60 degrees C in water baths for 1 min each for 5000 cycles before shear mode testing was performed. Light-activated opaque resin composites containing filler with specific filler compositions of 50 wt% of untreated TiO2-50 wt% of silanized SiO2 (untreated TiO2(50)) and 40 wt% of untreated TiO2-60 wt% of silanized SiO2 (untreated TiO2(40)) showed higher shear bond strengths to the Ag-Pd-Cu-Au alloy than any other specific compositions when no thermocycling was involved. Surface treatment of TiO2 filler and TiO2(50)- and TiO2(40)-opaque resin composites prepared thereof showed significantly higher shear bond strengths than untreated TiO2(50)- and TiO2(40)-opaque resin composites when subjected to thermocycling. Surface-treated opaque resin composite had significantly higher compressive and flexural strength than untreated opaque resin composite after immersion in water for 1 month. Scanning electron microscopy of the fractured opaque resin composite surface showed an interface failure between TiO2 and the matrix resin for untreated composite, and cohesive failure within the resin for surface-treated composite. Surface-treated TiO2(50) and TiO2(40) may be clinically useful as the filler for light-activated opaque dental resin composites.     

Synergistic reinforcement of in situ hardening calcium phosphate composite scaffold for bone tissue engineering

Calcium phosphate cement (CPC) hardens in situ to form solid hydroxyapatite, can conform to complex cavity shapes without machining, has excellent osteoconductivity, and is able to be resorbed and replaced by new bone. Therefore, CPC is promising for use in craniofacial and orthopaedic repairs. However, the low strength and lack of macroporosity of CPC limit its use. The aim of the present study was to increase the strength and toughness of CPC while creating macropores suitable for cell infiltration and bone ingrowth, and to investigate the effects of chitosan and mesh reinforcement on the composite properties. Specimens were self-hardened in 3 mm x 4 mm x 25 mm molds, immersed in a physiological solution for 1-84 d, and tested in three-point flexure. After 1d, the unreinforced CPC control had a flexural strength (mean+/-s.d.; n=6) of (3.3+/-0.4)MPa. The incorporation of chitosan or mesh into CPC increased the strength to (11.9+/-0.8) and (21.3+/-2.7)MPa, respectively. The incorporation of both chitosan and mesh synergistically into CPC dramatically increased the strength to (43.2+/-4.1)MPa. The work-of-fracture (WOF) (toughness) was also increased by two orders of magnitude. After 84 d immersion in a simulated physiological solution, the meshes in CPC dissolved and formed interconnected cylindrical macropores. The novel CPC scaffold had a flexural strength 39% higher, and WOF 256% higher than the conventional CPC without macropores. The new composite had an elastic modulus within the range for cortical bone and cancellous bone, and a flexural strength higher than those for cancellous bone and sintered porous hydroxyapatite implants. In conclusion, combining two different reinforcing agents together in self-hardening CPC resulted in superior synergistic strengthening compared to the traditional use of a single reinforcing agent. The strong and macroprous CPC scaffold may be useful in stress-bearing craniofacial and orthopaedic repairs.     

Effects of filler composition on flexibility of microfilled resin composite

The effects of the filler composition on physical and mechanical properties of microfilled composites was investigated by measuring water absorption, solubility, compressive, flexural, and impact strength. A series of experimental composites, consisting of UDMA/TEGDMA comonomer matrix and prepolymerized fillers, was fabricated. The prepolymerized fillers were composed of hydrophobic colloidal silica and two monomers in varying ratios, trimethylolpropanetrimethacrylate (TMPT), and polyesterdiacrylate (PEDA). TMPT/PEDA ratios were 100:0, 64:36, 46:54, 18:82, and 0:100%. There were no significant differences in water sorption and solubility, regardless of the amount of PEDA monomer. Young's modulus and modulus of resilience increased with decreasing PEDA ratio. Fracture energy exhibited drastic changes (30.1 x 10(-5) J to 93.4 x 10(-5) J). The highest value of flexural strength (96.0 +/- 3.5 MPa) was obtained when the TMPT-PEDA filler was 46:54. The impact strengths of composites fabricated with TMPT-PEDA filler of 46:54 (11.2 +/- 1.4 kJ/m(2)), 18:82 (10.6 +/- 3.2 kJ/m(2)), and 0:100 (13.1 +/- 3.8 kJ/m(2)) were significantly higher than those with 100:0 (6.0 +/- 1.8 kJ/m(2)) or 64:36 (7.1 +/- 2.4 kJ/m(2)). Based upon the results, it was concluded that the mechanical properties of microfilled composites were improved by the modification of prepolymerized filler composition.     

Fast-setting calcium phosphate scaffolds with tailored macropore formation rates for bone regeneration

Calcium phosphate cement (CPC) is highly promising for craniofacial and orthopedic repair because of its ability to self-harden in situ to form hydroxyapatite with excellent osteoconductivity. However, its low strength, long hardening time, and lack of macroporosity limit its use. This study aimed to develop fast-setting and antiwashout CPC scaffolds with high strength and tailored macropore formation rates. Chitosan, sodium phosphate, and hydroxypropyl methylcellulose (HPMC) were used to render CPC fast-setting and resistant to washout. Absorbable fibers and mannitol porogen were incorporated into CPC for strength and macropores for bone ingrowth. Flexural strength, work-of-fracture, and elastic modulus were measured vs. immersion time in a physiological solution. Hardening time (mean +/- SD; n = 6) was 69.5 +/- 2.1 min for CPC-control, 9.3 +/- 2.8 min for CPC-HPMC-mannitol, 8.2 +/- 1.5 min for CPC-chitosan-mannitol, and 6.7 +/- 1.6 min for CPC-chitosan-mannitol-fiber. The latter three compositions were resistant to washout, whereas the CPC-control paste showed washout in a physiological solution. Immersion for 1 day dissolved mannitol and created macropores in CPC. CPC-chitosan-mannitol-fiber scaffold had a strength of 4.6 +/- 1.4 MPa, significantly higher than 1.2 +/- 0.1 MPa of CPC-chitosan-mannitol scaffold and 0.3 +/- 0.2 MPa of CPC-HPMC-mannitol scaffold (Tukey's). The strength of CPC-chitosan-mannitol-fiber scaffold was maintained up to 42 days and then decreased because of fiber degradation. Work-of-fracture and elastic modulus showed similar trends. Long cylindrical macropore channels were formed in CPC after fiber dissolution. The resorbable, fast-setting, anti-washout and strong CPC scaffold should be useful in craniofacial and orthopedic repairs. The novel method of combining fast- and slow-dissolution porogens/fibers to produce scaffolds with high strength and tailored macropore formation rates to match bone healing rates may have wide applicability to other biomaterials.     

Effects of resin formulation and nanofiller surface treatment on the properties of experimental hybrid resin composite

This study evaluated the effects of nanofiller surface treatment and resin viscosity on the early and long-term properties of experimental hybrid composites. Three resin formulations (low, medium and high viscosity) were prepared by varying the ratio of TEGDMA:UDMA:bis-GMA (47:33:16 wt%; 30:33:33 wt%; 12:33:51 wt%). Composites contained 71.3 wt% silanated strontium glass (1-3 microm) and 12.6 wt% of either silanated or unsilanated silica (OX-50; 0.04 microm). Specimens (n=10) for flexural strength, flexural modulus, fracture toughness and Knoop hardness were tested after 24 h, 1 and 6 months exposure to water at 37 degrees C. Degree of conversion (DC) was determined 24 h after photoinitiation using FTIR. Resin viscosity only had a marginal influence on the mechanical response of composites but it can be adjusted to achieve a balance between DC and mechanical properties. Adding non-bonded nanofiller to hybrid composites had no systematic effect on DC. Non-bonded nanofillers had no significant effect on the long-term properties of hybrid composites.     

Novel nano-particles as fillers for an experimental resin-based restorative material

The purpose of this study is to compare the properties of two experimental materials, nano-material (Nano) and Microhybrid, and two trade products, Clearfil AP-X and Filtek Supreme XT. The flexural strength and modulus after 24h water storage and 5000 thermocycles, water sorption, solubility and X-ray opacity were determined according to ISO 4049. The volumetric behavior (DeltaV) after curing and after water storage was investigated with the Archimedes principle. ANOVA was calculated with p<0.05. Clearfil AP-X showed the highest flexural strength (154+/-14 MPa) and flexural modulus (11,600+/-550 MPa) prior to and after thermocycling (117+/-14 MPa and 13,000+/-300 MPa). The flexural strength of all materials decreased after thermocycling, but the flexural modulus decreased only for Filtek Supreme XT. After thermocycling, there were no significant differences in flexural strength and modulus between Filtek Supreme XT, Microhybrid and Nano. Clearfil AP-X had the lowest water sorption (22+/-1.1 microg mm(-3)) and Nano had the highest water sorption (82+/-2.6 microg mm(-3)) and solubility (27+/-2.9 microg mm(-3)) of all the materials. No significant differences occurred between the solubility of Clearfil AP-X, Filtek Supreme XT and Microhybrid. Microhybrid and Nano provided the highest X-ray opacity. Owing to the lower filler content, Nano showed higher shrinkage than the commercial materials. Nano had the highest expansion after water storage. After thermocycling, Nano performed as well as Filtek Supreme XT for flexural strength, even better for X-ray opacity but significantly worse for flexural modulus, water sorption and solubility. The performances of microhybrids were superior to those of the nano-materials.     

Calcium-deficient hydroxyapatite-PLGA composites: mechanical and microstructural investigation

The microstructural and mechanical properties of composites composed of calcium deficient hydroxyapatite (CDHAp) and poly(lactide-co-glycolide) (PLGA) have been investigated. The composites were formed by hydrolysis of alpha-tricalcium phosphate (alpha-TCP) to CDHAp in pressed precomposite compacts of alpha-TCP-PLGA-NaCl. The differences in hydrolysis of alpha-TCP-PLGA-NaCl for two compositions of 80:10:10 wt % and 60:20:20 wt %. were monitored by isothermal calorimetry and X-ray diffraction. The microstructural evolution and variance in final composite microstructure after hydrolysis at 37 degrees C, 45 degrees C, and 56 degrees C were examined by scanning electron microscopy. HAp-PLGA composite formed from the alpha-TCP-PLGA-NaCl (80:10:10) precomposites at 37 degrees C developed a tensile strength of 13.3 +/- 0.9 MPa, a flexural strength of 24.8 +/- 1.7 MPa, and Young's modulus of 2.8 +/- 0.3 GPa. These values were 12.00 +/- 0.2 MPa, 36.1 +/- 2.1 MPa, and 5.5 +/- 0.8 GPa for the precomposite composition 60:20:20. All these mechanical properties showed a variation with hydrolysis temperature and composition. The differences in mechanical properties were related to the final microstructures of the composites, which are governed by the morphological changes in the polymer structure at its glass transition temperature and the extent of cement-type formation of CDHAp by hydrolysis of alpha-TCP.     

Processing and tensile properties of hydroxyapatite-whisker-reinforced polyetheretherketone

Polyetheretherketone (PEEK) was reinforced with 0-50 vol% hydroxyapatite (HA) whiskers using a novel powder processing and compression molding technique which enabled uniform mixing at high whisker content. Texture analysis showed that viscous flow during compression molding produced a preferred orientation of whiskers along the specimen tensile axis. Consequently, the elastic modulus or ultimate tensile strength of HA-whisker-reinforced PEEK was able to be tailored to mimic human cortical bone. PEEK reinforced with 40 and 50 vol% HA whiskers exhibited elastic moduli of 17 and 23 GPa, respectively. Elastic constants were measured using ultrasonic wave propagation and revealed an orthotropic anisotropy also similar to that measured in human cortical bone. PEEK reinforced with 10 and 20 vol% HA whiskers exhibited an ultimate tensile strength of 90 and 75 MPa, respectively. Tensile specimen fracture surfaces showed evidence of brittle failure in both reinforced and un-reinforced PEEK. Whisker pullout was observed with PEEK adhered to HA whiskers, suggesting a relatively strong interface between the PEEK matrix and HA whisker reinforcements.     

Self-setting collagen-calcium phosphate bone cement: mechanical and cellular properties

Calcium phosphate cement (CPC) can conform to complex bone cavities and set in-situ to form bioresorbable hydroxyapatite. The aim of this study was to develop a CPC-collagen composite with improved fracture resistance, and to investigate the effects of collagen on mechanical and cellular properties. A type-I bovine-collagen was incorporated into CPC. MC3T3-E1 osteoblasts were cultured. At CPC powder/liquid mass ratio of 3, the work-of-fracture (mean +/- sd; n = 6) was increased from (22 +/- 4) J/m(2) at 0% collagen, to (381 +/- 119) J/m(2) at 5% collagen (p < or = 0.05). At 2.5-5% of collagen, the flexural strength at powder/liquid ratios of 3 and 3.5 was 8-10 MPa. They matched the previously reported 2-11 MPa of sintered porous hydroxyapatite implants. SEM revealed that the collagen fibers were covered with nano-apatite crystals and bonded to the CPC matrix. Higher collagen content increased the osteoblast cell attachment (p < or = 0.05). The number of live cells per specimen area was (382 +/- 99) cells/mm(2) on CPC containing 5% collagen, higher than (173 +/- 42) cells/mm(2) at 0% collagen (p < or = 0.05). The cytoplasmic extensions of the cells anchored to the nano-apatite crystals of the CPC matrix. In summary, collagen was incorporated into in situ-setting, nano-apatitic CPC, achieving a 10-fold increase in work-of-fracture (toughness) and two-fold increase in osteoblast cell attachment. This moldable/injectable, mechanically strong, nano-apatite-collagen composite may enhance bone regeneration in moderate stress-bearing applications.     

An in vitro investigation of the effect of the addition of untreated and surface treated silica on the transverse and impact strength of poly(methyl methacrylate) acrylic resin

Silica is a commonly used filler in dental materials and as a reinforcing agent in industry. The aim of this study was to further investigate the effect of the addition of untreated and a novel surface treated silica on the transverse bend and impact strength of acrylic resin denture base material. It was hypothesized that the silica/resin composite materials would have an improved flexural and impact strength than the conventional heat-cured acrylic resin. Three types of untreated and two of treated silica powder were used in this study. The range of percentages used were 1%, 0.5%, 0.2%, 0.1%. The treated particles were coated with hexamethyldisilazane or dimethyldichloridesilazane. Conventional heat cured acrylic resin was used as a control. The modulus of rupture for all groups of acrylic resin containing silica was significantly lower than for the control. The modulus of elasticity was not significantly greater than the control group. For the impact strength statistical analysis revealed a significant difference between the groups. There was a nonsignificant increase in the impact strength for specimens compared to the control. In conclusion the addition of silica to poly(methyl methacrylate) denture base materials did not produce a significant improvement in the transverse bend or impact strength compared to conventional heat-cured acrylic resin. The incorporation of untreated and surface treated silica cannot be recommended as a method of reinforcement.