Bill M. Culbertson

Mechanical properties and microstructures of glass-ionomer cements

OBJECTIVE The objective of this study was to determine the flexural strength (FS), compressive strength (CS), diametral tensile strength (DTS), Knoop hardness (KHN) and wear resistance of ten commercial glass-ionomer cements (GICs). The fracture surfaces of these cements were examined using scanning electron microscopic (SEM) techniques to ascertain relationships between the mechanical properties and microstructures of these cements. METHODS Specimens were fabricated according to the instructions from each manufacturer. The FS, CS, DTS, KHN and wear rate were measured after conditioning the specimens for 7 d in distilled water at 37 degrees C. One-way analysis of variance with the post hoc Tukey-Kramer multiple range test was used to determine which specimen groups were significantly different for each test. The fracture surface of one representative specimen of each GIC from the FS tests was examined using a scanning electron microscope. RESULTS The resin-modified GICs (RM GICs) exhibited much higher FS and DTS, not generally higher CS, often lower Knoop hardness and generally lower wear resistance, compared to the conventional GICs (C GICs). Vitremer (3M) had the highest values of FS and DTS; Fuji II LC (GC International) and Ketac-Molar (ESPE) had the highest CS; Ketac-Fil (ESPE) had the highest KHN. Ketac-Bond (ESPE) had the lowest FS; alpha-Silver (DMG-Hamburg) had the lowest CS. Four GICs (alpha-Fil (DMG-Hamburg), alpha-Silver, Ketac-Bond and Fuji II) had the lowest values of DTS, which were not significantly different from each other; alpha-Silver and Ketac-Silver had the lowest values of KHN. The highest wear resistance was exhibited by alpha-Silver and Ketac-Fil; F2LC had the lowest wear resistance. The C GICs exhibited brittle behavior, whereas the RM GICs underwent substantial plastic deformation in compression. The more integrated the microstructure, the higher were the FS and DTS. Higher CS was correlated with smaller glass particles, and higher KHN was found where there was a combination of smaller glass particles and lower porosity. Larger glass particle sizes and a more integrated microstructure contributed to a higher wear resistance. SIGNIFICANCE The mechanical properties of GICs were closely related to their microstructures. Factors such as the integrity of the interface between the glass particles and the polymer matrix, the particle size, and the number and size of voids have important roles in determining the mechanical properties.

Glass-ionomer dental restoratives

Abstract The history and chemistry of conventional (chemically cured) and visible light-cured (VLC) glass polyalkeonates (glass-ionomers) is reviewed. The synthesis of new acrylic acid copolymers, containing amino acid residues, derived from amino acid based acrylamides or methacrylmides, and N-vinylpyrrolidone, is described, along with the use of the new polymers to prepare improved restoratives. Supercritical polymerizations for preparing new polyelectrolytes for use in formulating improved glass-ionomers are also described. A completely new method to prepare VLC glass-ionomers, via the use of methacrylate monomers having a cyclic imino ether group, to modify acrylic acid copolymers in aqueous solution, is additionally described.

Differential Scanning Calorimetry (DSC) Analyses Of Superelastic And Nonsuperelastic Nickel-Titanium Orthodontic Wires

The purpose of this study was to determine the transformation temperatures for the austenitic, martensitic, and rhombohedral (R) structure phases in representative as-received commercial nitinol (NiTi) orthodontic wire alloys, to reconcile discrepancies among recent publications. Specimens were examined by differential scanning calorimetry (DSC) over a temperature range from approximately -170 degrees C to 100 degrees C, with a scanning rate of 10 degrees C per minute. Two different pathways, with the intermediate R structure either absent or present, were observed for the transformation from martensitic to austenitic NiTi, whereas the reverse transformation from austenitic to martensitic NiTi always included the R structure. The enthalpy (delta H) for the transformation from martensite to austenite ranged from 0.3 to 3.5 calories per gram. The lowest delta H value for the nonsuperelastic Nitinol wire is consistent with a largely work-hardened, stable, martensitic microstructure in this product. The DSC results indicate that the transformation processes are broadly similar in superelastic, body-temperature shape-memory, and nonsuperelastic NiTi wires. Differences in bending properties for the NiTi orthodontic wires at room temperature and 37 degrees C are due to the relative proportions of the metallurgical phases in the microstructures.

Cyclic imino ethers in step-growth polymerizations

The synthesis of oxazoline and oxazine type monomers is explored, with focus mainly on those methods of most commercial significance. The many varied reactions of cyclic imino ethers with various other functionalities are also discussed, with the main focus being on those reactions most useful to form polymers. The step-growth or polycondensation reaction of cyclic imino ether monomers, oxazoline and oxazine molecules, receives significant attention. For step-growth polymerizations, extensive attention is given to the preparation and reaction of monomers or polymers having ≥2 oxazoline or oxazine residues. Those reactions most useful to prepare thermoplastics or thermosets, which resides in the polycondensation of dicarboxylic acids, dithiols, phenolics, epoxides, etc. with bisoxazolines or bisoxazines receive significant focus. The simultaneous copolymerization of benzoxazines and bisoxazolines with phenolics is also described. Lastly, a variety of oxazoline or oxazine monomers, having acetylacetonate, acetylacetanilide, thiopene, etc. type residues are also described. Clearly, it is shown that there are significant opportunities to use oxazoline or oxazine functionalized monomers, oligomers and polymers to produce new materials for a variety of applications.

Preparation of glass ionomer cement using N-acryloyl-substituted amino acid monomers — Evaluation of physical properties

OBJECTIVES The objectives of this study were (1) to develop polyacid formulations through the incorporation of amino acid-derived monomers with carboxylic acid groups at various distances away from the polymer backbone to allow for greater flexibility, less rigid ionic cluster formation and improved solubility, and (2) to test selected physical and handling properties of experimental ionomers with a conventional glass ionomer as a control. METHODS The polycarboxylic acids prepared and used in glass ionomer formulation in this study included N-acryloylglutamic acid (AGA) and N-acryloyl-6-aminocaproic acid (AACA)- modified acrylic acid- ++itaconic acid copolymers, where the acrylic acid:itaconic acid:amino acid monomers were combined in different proportions. The characterization and purity of the monomers were determined by FTIR and their melting points. The characterization of synthesized polymers included molecular weight and relative viscosity determinations. The compressive strengths, diametral tensile strengths, flexural strengths and fracture toughness of the experimental ionomers and a commercially available ionomer (control) were measured after storage in water, at 37 degrees C for 1 h or 7 d. The working times and setting times of the experimental ionomers were compared to the control specimens. Separate analysis of variance and Tukeys tests were used to study the statistical significance of the physical strength parameters as a function of materials and storage times. RESULTS Significant increases (p< 0.001) in diametral tensile, compressive, flexural strengths and fracture toughness were observed in the AGA co-polymers, while significant increases were observed in diametral and flexural strengths in the AACA co-polymers compared to the control Fuji II. The working and setting times of all except one experimental ionomer studied were comparable to the controls. SIGNIFICANCE The use of amino acid-modified acrylic monomers to produce water soluble copolymers of acrylic-itaconic acid offers a new route of discovery to produce chemical-cured glass ionomers with improved physical properties. The spacer chain length, the hydrophobicity of the chains, the molecular weight and viscosity of the polymer all played important roles in determining the physical properties of the material.

Improved Flexural Strength of N-Vinyl-Pyrrolidone Modified Acrylic Acid Copolymers for Glass-Ionomers

Abstract The flexural strengths of N-vinylpyrrolidone modified glass-ionomer cements were investigated. The optimal molar ratio of the monomers in copolymers, composed of the three components acrylic acid, itaconic acid and N-vinylpyrrolidone, was determined using a SAS statistical program. The copolymers were prepared using a free-radical polymerization process. The viscosities of aqueous solutions of these polymers were determined. Cements were formed by the reaction of these solutions with glass particles. Flexural strength (FS) was used as the basic screening property to find the optimum molar ratio. Statistical models were applied to predict the optimum molar ratios. All strength values were recorded on the specimens conditioned in distilled water at 37°C for 7 days. The optimal molar ratio for these copolymers was 7:1:3 for poly(acrylic acid-co-itaconic acid-co-N-vinylpyrrolidone), based on flexural strength and viscosity. The effect of molecular weight (MW) on FS was also evaluated. Copolymer with ...

METHACRYLOYL DERIVITIZED HYPERBRANCHED POLYESTER. 2. PHOTO-POLYMERIZATION AND PROPERTIES FOR DENTAL RESIN SYSTEMS

The purpose of this research is to demonstrate the usefulness of the synthesized hyperbranched multi-methacrylates (H-MMAs) in dental applications. We synthesized three hyperbranched multi-methacrylate oligomers and evaluated them as modifiers for use in the dental resin system: bisphenol A glycidyl dimethacrylate (BisGMA)/tri(ethylene glycol) dimethacrylate (TEGDMA). Their photo-polymerization activities, viscosity, mechanical properties, such as compression, diametral tensile, and flexural strength, were evaluated. H-MMAs (10%) modified dental resins have lower polymerization shrinkage and about 15% increase in mechanical strength compared to the Bis-BisGMA control. For example, H30-MMA has compressive, diametral tensile, and flexural strength of 576, 47, and 85 MPa, compared with the BisGMA control having 497, 43, and 77 MPa. In addition, hyperbranched polymer modified resins have higher glass transition temperature (Tg) and lower thermal expansion coefficient (α) than the control. This research is significant both for increasing our knowledge about hyperbranched multi-functional polymers as well as leading to new dental resin systems with better performance.

Formulation of Visible Light-Curable Glass-Ionomer Cements Containing N-Vinylpyrrolidone

Abstract The best graft ratio of the light-curable N-vinylpyrrolidone (NVP) modified terpolymers (LC NVPM TPs) with the molar ratio of 8:2:1 (acrylic acid:itaconic acid:NVP) and the optimal formulation for this light-curable glass-ionomer cement, based on the best graft ratio, were determined. Statistical models were utilized to predict the optimal formulations. The terpolymer was prepared using a free-radical polymerization reaction. The LC NVPM TPs were produced by grafting 2-isocyanatoethyl methacrylate (IEM) onto the terpolymer. Cements were formed by both light-curing and the reaction with glass particles. Compressive strength was used as the basic screening property to find the optimal formulation. Diametral tensile and flexural strengths were also used to evaluate the mechanical properties. The strength values were recorded on the specimens conditioned in distilled water at 37&C for 24 hours or 7 days. The best graft ratio for IEM in this system was 15% of the terpolymer by a molar ratio. The optim...

METHACRYLOYL DERIVITIZED HYPERBRANCHED POLYESTER. 1. SYNTHESIS, CHARACTERIZATION, AND COPOLYMERIZATION

Three hyperbranched multi-methacrylates (H20-MMA, H30-MMA and H40-MMA) have been synthesized by reacting Boltorn dendritic polyols with methacrylic anhydride and methacryloyl chloride. Their structures were characterized by FT-IR and NMR (1H and 13C) and molecular weights were measured by GPC. These multi-methacrylates (H-MMAs) mixed well with a variety of monomers such as acrylic acid (AA), methacrylic acid (MA), methyl methacrylate (MMA), 2-hydroxy-ethyl methacrylate (HEMA), tri(ethylene glycol) dimethdimethacrylate (TEGDMA), and bisphenol A glycidyl dimethacrylate (BisGMA). The initial studies on thermal polymerization activities of 10% of H-MMAs with AA, MA, and MMA showed that they gave higher polymerization enthalpy than the corresponding homopolymerization. The resulting materials showed one glass transition temperature, indicating a typical single-phase resin. The H-MMAs can effectively copolymerize with AA, MA, and MMA, with essentially no homopolymers produced, as indicated by acetone extraction studies. This indicated that the hyperbranched multi-methacrylates have the potential to be used as crosslinking agents or modifiers with a number of monomers to produce new thermosets.

Preparation and Evaluation of Visible Light-Cured Multi-Methacrylates for Dental Composites

Abstract To explore new VLC oligomers exhibiting low shrinkage, low water sorption, and improved mechanical properties, a family of multi-methacrylates, based on poly(isopropylidenediphenol) resin (BPA), was synthesized, characterized, and evaluated. The BPA resin, having an average of eight phenolic hydroxyl groups per molecule, was treated with ethylene carbonate and the resultant product esterified at four different grafted levels, using methacryloyl chloride. Structures of these EEBPA oligomers, were confirmed by FT-IR and 13C NMR. The EEBPA oligomer/TEGDMA (50/50, w/w) blends were combined with 0.5 wt% camphoroquinone(CQ) and 1.0 wt% N,N-dimethylaminoethyl methacrylate (DMAEM). The control was BisGMA/TEGDMA (50/50, w/w) blends having the same levels of CQ/DMAEM. Differential photocalorimetry (DPC) and differential scanning calorimetry (DSC) showed the multi-methacrylate/TEGDMA (neat resin) blends have polymerization characteristics comparable to the BisGMA/TEGDMA control. These multi-functional oligo...