Ronald E. Kerby

Synthesis and evaluation of modified urethane dimethacrylate resins with reduced water sorption and solubility

OBJECTIVES New aliphatic and aromatic urethane dimethacrylate monomers containing pendant phenyl methoxy or ethyl substituents were synthesized in order to reduce the water sorption and solubility of urethane dimethacrylate systems. Selected properties including flexural strength, flexural modulus, water sorption and solubility, and water contact angle were evaluated. Hoys solubility parameters were also calculated to rank copolymer hydrophilicity. METHODS Filled (20%) composite resins were formulated with each of the newly synthesized dimethacrylates as well as the commercially available urethane dimethacrylate monomer, UDMA. Flexural strength, flexural modulus, water sorption and solubility of the urethane composites were evaluated after light-cured specimens were immersed in water for seven days. Water contact angles were measured on the surface of each material. Data were analyzed using ANOVA and Ryan-Einot-Gabriel-Welsch multiple range tests (alpha=0.05). RESULTS A significant reduction of nearly 30% and 40% in water uptake was observed with composite polymers containing pendant ethyl and phenyl methoxy groups, respectively, compared to UDMA (p<0.05). Urethane copolymers containing pendant ethyl groups also showed a significant reduction in water solubility (p<0.05). A positive correlation was found between contact angle and water sorption as well as Hoys delta(h) for hydrogen bonding forces. SIGNIFICANCE The results of this study indicate that the incorporation of pendant hydrophobic substituents within the monomer backbone may be an effective method in reducing the water sorption and water solubility of urethane based dimethacrylate systems. The use of Hoys solubility parameters to determine the relative hydrophilicity of a polymer may be limited by its three-dimensional chemical structure.

Fracture toughness of resin-based luting cements

STATEMENT OF PROBLEM The introduction of resin-modified glass ionomer cements has expanded the choices of luting cements available to the clinician; however, few independent studies are available on the fracture toughness of the currently available resin-modified glass ionomer luting agents compared with the composite cements. PURPOSE This investigation evaluated the relative fracture toughness (K(IC)) of 3 composite luting cements (Panavia 21, Enforce, and C&B Metabond), 3 resin-modified glass ionomer luting cements (Advance, Vitremer Luting, and Fuji Duet), and a conventional glass ionomer luting cement (Ketac-Cem) at 24-hour and 7-day storage times. MATERIAL AND METHODS K(IC) was determined by preparing minicompact test specimens (n = 8) with introduced precracks. Specimens were stored in distilled water at 37 degrees C + 2 degrees C until testing. Testing was performed on an Instron testing machine at a displacement rate of 0.5 mm/min. RESULTS ANOVA (P <.001) and REGW Multiple Range Test (P <.05) demonstrated significant differences among several of the cements tested. The mean fracture toughness values of C&B Metabond at 24 hours and Enforce at both 24 hours and 7 days were significantly greater than use any of the other cements tested. CONCLUSION The resin-modified glass ionomer cements exhibited improved fracture toughness when compared with the conventional glass ionomer; however, they were still inferior to Enforce and C&B Metabond composite cements.

Mechanical properties of urethane and bis-acryl interim resin materials

STATEMENT OF PROBLEM The fracture or dislodgement of an interim prosthesis may result in additional appointments and could negatively affect the outcome of a fixed prosthodontic procedure. PURPOSE The purpose of this study was to evaluate the flexural strength (FS), flexural modulus (FM), work-of-fracture (WOF), and Weibull parameters of 4 bis-acryl (Protemp Plus, Integrity, Turbo Temp 2, Temphase Fast-set) and 2 urethane (NuForm and Tuff-Temp) interim resins after being stored in distilled water for 1 hour and 24 hours. MATERIAL AND METHODS Rectangular beam specimens (25 × 2 × 2 mm) of each resin (n=23) were prepared and stored in distilled water at 37°C. Then 3-point bending tests were performed on 1-hour and 24-hour (wet) and 24-hour (dry and wet) specimens in a universal testing machine at a cross-head speed of 1.0 mm/min. Stress/strain curves were generated and flexural strength, flexural modulus, and WOF values were calculated. Data were subjected to 3-way ANOVA and the Tukey-Kramer pairwise comparison test (α=.05). FS data were also subjected to a 2-parameter Weibull analysis. RESULTS The 24-hour (wet) mean flexural strength and flexural modulus values were significantly higher than 1-hour values. The urethane Tuff-Temp, chemically and dual-polymerized, showed significantly higher (P<.05) 1-hour FS and FM, while the bis-acryl Protemp Plus showed significantly greater flexural strength and work-of-fracture than the other resins after 24 hours of wet storage. Protemp Plus, NuForm, and Turbo Temp 2 did not decrease in flexural strength and flexural modulus after 24 hours in dry and wet storage conditions. The Weibull modulus values of the flexural strengths of the interim resins at 1 hour and 24 hours ranged from 8.4 to 26.8. CONCLUSIONS Postgelation polymerization plays an important role in the substantial increase in the flexural strength and flexural moduli of the interim resins between 1 and 24 hours. A wide variation in the mechanical properties of the interim resin materials was noted but was, for the most part, not category specific.

Relative fracture toughness of bis-acryl interim resin materials

STATEMENT OF PROBLEM Fracture of the interim partial denture may cause patient discomfort and result in unplanned appointments and expense. At present, limited information is available concerning the fracture toughness of bis-acryl interim resins, especially immediately following fabrication. PURPOSE The purpose of this investigation was to evaluate the relative fracture toughness and Weibull parameters of 4 commercial chemically polymerized (Protemp Garant 3, Perfectemp II, Integrity, Temphase) and 1 dual polymerizing (Luxatemp Solar) bis-acryl interim resin materials with various filler loading after 1 hour and 24 hours. MATERIAL AND METHODS Disk-shaped, mini-compact test specimens (8.20 × 1.85 mm thick, n=18) with introduced pre-cracks were prepared in a pre-heated split-mold and maintained at 37°C for 5 minutes during polymerization to simulate clinical conditions. Polymerization temperature was measured using an infrared digital thermometer. Specimens were stored in distilled water at 37°C after which the peak load to fracture was recorded at 1 and 24 hours and the fracture toughness (K(1c)) was calculated. An overall Weibull analysis of the fracture toughness was performed incorporating the fracture toughness data with factors polymerization method, time of testing and filler load of the resin. Weibull analysis was performed at (α =.05). Fracture surfaces of representative specimens were examined using scanning electron microscopy. RESULTS The overall Weibull analysis results showed significant differences (P<.001) in fracture toughness between the times of testing (1 and 24 hours), polymerization method, and as a function of filler loading. The results of the individual Weibull survival analyses showed a significant increase in Weibull Characteristic Strength (σo) values between 1 and 24 hours for all materials. The Weibull moduli (m) for the interim resins ranged between 5.8 and 10.3. SEM analysis of fractured surfaces revealed that crack propagation occurred primarily through the resin matrix between filler particles. CONCLUSIONS Post-gelation polymerization has an important role in determining the fracture properties of both chemical and dual-polymerized bis-acryl interim materials within the first 24 hours. For the materials tested, the higher the filler load, the lower the fracture toughness.

Effect of mixing methods on the physical properties of dental stones

OBJECTIVES This in vitro comparative study evaluated the effect of different stone mixing methods on material properties of four dental stones. Two ADA type IV stones (Silky-Rock and Snap-Stone), one type V high expansion stone (Die Keen), and one recently introduced type V specialty stone (HandiMix) were chosen for this study. METHODS Forty cylindrical specimens (25 mm x 12.5 mm) were cast for each of the nine stone sub-groups and bench dried at 23+/-2 degrees C for 1 and 24h. Specimens were then tested in an Instron in tensile and compression modes at crosshead speeds of 0.5 and 1.0 mm/min, respectively. Four rectangular-shaped specimens (30 mm x 15 mm x 15 mm) of each stone type were cast and bench dried for 48 h. Knoop microhardness measurements were obtained from defined areas on each specimen for surface hardness testing using 200 g load and 20s dwell time. A 12.6 mm(2) area was then delimited in the center of two sides of each specimen and photographed under low power magnification (40x). The average pore number per area was then determined for each specimen for surface porosity testing. The setting time and setting expansion for each stone type was recorded as well. RESULTS ANOVA (P<0.001) and Ryan-Einot-Gabriel-Welsh test (P<0.05) showed significant differences between diametral tensile strengths and pore numbers for both stone types and mixing methods. CONCLUSION Within the limitations of this study, the newly introduced mixing method did not appear to have an effect on the physical properties of HandiMix stone.

EVALUATION OF TERTIARY AMINE CO-INTIATORS USING DIFFERENTIAL SCANNING PHOTOCALORIMETRY

The purpose of this investigation was to compare the degree of photo- and thermal-polymerization obtained using various tertiary amine co-initiators of differing reactivities and molar concentrations, utilizing differential scanning photocalorimetry (DPC) and DSC. Amines tested were 2-(dimethylamino)ethyl methacrylate (A), triethanolamine (B), N,N,3,5-tetramethyl-aniline (C), ethyl 4-dimethylaminobenzoate (D), 0.95 (A) and 0.05 (D) in combined mixture (E), 4-N,N-(dimethylamino)phe-nylacetic acid (F) and a newly-synthesized tertiary aromatic amine methacryloxyethyl substituted 4-N,N-(dimethyla-mino)phenylacetamide (G). The monomer system consisted of Bis-GMA and triethylene glycol dimethacrylate neat resins, and 0.5% camphoroquinone for all groups tested. Samples of the blended monomers with 0.5–4.0 mol/eq (co-initiator to initiator) were irradiated with visible light under N2. The heat of reaction (ΔH) was calculated for each run in order to determine the degree of polymerization (DP). D resulted in a sig...