Tuning the acidic properties of aluminas via sol-gel synthesis: New findings on the active site of alumina-catalyzed epoxidation with hydrogen peroxide

This study answers several pending questions about alumina-catalyzed epoxidation with aqueous 70 wt% H2O2. To evaluate the effect of the water-to-aluminum tri-sec-butoxide molar ratio, this was systematically changed from 1 to 24. The xerogels were calcined at 450 degrees C and gave different gamma-Al2O3's with distinct textural and acidic properties. A combination of Al-27 MAS NMR and TPD-NH3 results of calcined aluminas allowed us to assign the type la. Al-OH sites as the catalytic sites for epoxidation. The type Ib Al-OH sites have no function in catalytic epoxidation, because ethyl acetate poisons these sites. The strong acid sites of types IIa, IIb, and III Al-OH groups are responsible for the undesired H2O2 decomposition and decreased oxidant selectivity. (c) 2006 Elsevier B.V. All rights reserved.

Alumina/zirconia composite coated by biomimetic method

In this study, a bioactive zirconia-toughened alumina (ZTA) composite was developed for orthopedic applications. This composite was obtained by slip casting of suspension powder mixtures.Biomimetic processes were used to grow a bone-like apatite layer on composite substrates using sodium silicate solution as a nucleating agent and simulated body fluids. The composites, with or without coating, were characterized by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy and scanning electron microscopy (SEM) with energy dispersion spectroscopy (EDS), and their apparent density was determined by the Archimedes method. The composites obtained by this process possessed the expected stiffness and dimensions and their density values were similar to those of the composite's theoretical density (98.8%TD). The morphology of the hydroxyapatite formed on the composite surface was homogeneous and composed of small globules, characterizing a carbonated hydroxyapatite. The results of the tests indicated that the method employed to produce the composite and its coating was efficient under the conditions of this study. (c) 2006 Elsevier B.V. All rights reserved.

The effectiveness of alumina powder on carious dentin removal

This study determined the size of aluminum oxide particles used in an air abrasion system that is able to remove carious dentin tissue with maximum preservation of sound structure. Thirty extracted and carious-free third molars were used in this study. The dentin sample was obtained by sectioning the middle of the crown longitudinal to the long axis of the tooth in a mesio-distal direction. One half of the crown corresponded to the sound dentin group (SD), while the other half was used to develop artificial caries, constituting the, carious dentin group (CD). The specimens were air abraded for 15 seconds. The SD and CD groups were each randomly divided into three subgroups (N=10) according to the particle diameter employed (27, 50 and 125 pm). The prepared cavity was perpendicularly cut in half, and the profiles of all hemi-fragments were observed using SEM microscopy. The cavity measurements were made using a modified cephalometric analysis. The 27, 50 and 125 pun aluminum oxide particles did not present selectivity in the removal of carious dentin. However, when using the air abrasive technique for carious dentin treatment, the use of 27 and 50 pun aluminum oxide particles is recommended, due to their capacity to remove less sound tissue than the 125 pun particles.

Highly selective nickel ethylene oligomerization catalysts based on sterically hindered tris(pyrazolyl)borate ligands

The reaction of TlTp' (Tp' = HB(3-mesitylpyrazolyl)(3)(-) (Tp(Ms)), HB(3-mesitylpyrazolyl)(2)(5-mesitylpyrazolyl)(-) (Tp(Ms)*)) with NiCl(2).6H(2)O affords Tp(Ms)NiCl (1) and Tp(Ms)*NiCl (2) in good yield. The compound 2 undergoes an isomerization process to form [{Tp(Ms)**}NiCl](2) (3) (Tp(Ms)** = HB(5-mesitylpyrazolyl)(2)(3-mesitylpyrazolyl)(-)) in 68% yield. Treatment of the tris(pyrazolyl)-borate nickel compounds 1 and 2 with alkylaluminum cocatalysts such as methylalumoxane (MAO) and trimethylaluminum (TMA) in toluene generates active catalysts for ethylene oligomerization. The compound 1 shows turnover frequencies in the range of (2.2-43.1) x 10(3) h(-1). Oligomerization reaction conditions can be adjusted that lead to selectivities as high as 81% for butene-1.

Niobium to alcohol mol ratio control of the concurring esterification and etherification reactions promoted by NbCl5 and Al2O3 catalysts under microwave irradiation

Alcohols and acids can be switched to produce ethers or esters by varying the alcohol to catalyst mol ratio, in a new etherification and esterification method using NbCl5/Al2O3 catalyst under "solvent free" conditions and promoted by MW (microwave) irradiation. A "two sites" mechanism for the reaction is proposed, in an attempt to clarify the tendency of the catalyst to be dependent on the alcohol alone during the esterification process. (c) 2008 Elsevier B.V. All rights reserved.

Key features of alumina/magnesia/graphite refractories for steel ladle lining

The corrosion resistance of resin bonded alumina/magnesia/graphite refractories containing different kinds of aggregates were investigated when submitted to the action of slags of several CaO/SiO2 ratios. The laboratory testing was performed by means of the rotary slag attack test. Specifically evaluated was the influence of alumina/carbon ratio and magnesia and silica contents on the refractories corrosion resistance. It was found that this property could be improved by increasing the refractory Al2O3/SiO2 ratio as well as by choosing the appropriate Al2O3/C ratio. © 2000 Elsevier Science Ltd.

Effect of ceramic surface treatment on the microtensile bond strength between a resin cement and an alumina-based ceramic

Purpose: The objective of this study was to test the following hypothesis: the silica coating on ceramic surface increases the bond strength of resin cement to a ceramic. Materials and Methods: In-Ceram Alumina blocks were made and the ceramic surface was treated: G1 - sandblasting with 110-μm aluminum oxide particles; G2 - Rocatec System: tribochemicai silica coating (Rocatec-Pre powder + Rocatec-Plus powder + Rocatec-Sil); G3 - CoJet System: silica coating (CoJet-Sand) + ESPE-Sil. The ceramic blocks were cemented to composite blocks with Panavia F resin cement (under a load of 750 g/1 min). The cemented blocks were stored in distilled water at 37°C for 7 days and sectioned along the x and y axes with a diamond disk. Samples with an adhesive area of ca 0.8 mm 2 (n = 45) were obtained. The samples were attached to an adapted device for the microtensile test, which was performed in a universal testing machine (EMIC) at a crosshead speed of 1 mm/min. Results: The obtained results were submitted to ANOVA and Tukey's test. Mean values of tensile strength (MPa) and standard deviation values were: (G1) 16.8 ± 3.2; (G2) 30.6 ± 4.5; (G3) 33.0 ± 5.0. G2 and 63 presented greater tensile strength than G1. There was no significant difference between G2 and G3. All the failures took place at the ceramic/resin cement interface. Conclusion: The silica coating (Rocatec or CoJet systems) of the ceramic surface increased the bond strength between the Panavia F resin cement and alumina-based ceramic.

On the specific filtration mechanism of a mesoporous silica membrane, prepared with non-connecting parallel pores

We report the singular filtration properties of an ultrafiltration membrane made with mesoporous silica that exhibits cylindrical pores aligned mostly normal to the support. This membrane supported on tubular commercial macroporous alumina supports was prepared by the interfacial growth mechanism between stable silica-surfactant hybrid micelles made of the association of silica oligomers with polyethyleneoxide-based (PEO) surfactants and sodium fluoride, a well-known silica condensation catalyst [Boissière et al., An ultrafiltration membrane made with mesoporous MSU-X silica, Chem. Mater. 15 (2003) 460-463]. It appears that the combined effect of the silica nature of the membrane, whose surface charge can be easily adjusted by changing the pH and the non-connected cylindrical shape of the pores provides a new behavior in the retention properties, as proved by the filtration of polyoxyethylene polymers (PEO) with different molecular weights. Depending on the filtration conditions, a rejection rate of 80% and a steep cut-off at 2000 Da can be obtained or, on the reverse, polymers three times bigger than the pore diameter can diffuse through the membrane. This new filtration mechanism, which opens up new modes of separation modes, is explained in the light of both topology of the porous network and pH-dependent interactions between PEO polymers and silica porous media. © 2004 Elsevier B.V. All rights reserved.

Fatigue resistance of the bond of a glass-infiltrated alumina ceramic to human dentin

Purpose: To evaluate the fatigue resistance of the bond between dentin and glass-infiltrated alumina ceramic, using different luting protocols. Materials and Methods: The null hypothesis is that the fatigue resistance varies with the luting strategy. Forty blocks of In-Ceram Alumina were prepared, and one surface of each block was abraded with 110-μm aluminum oxide particles. Then, the blocks were luted to flat dentin surfaces of 40 human third molars, using 4 different luting strategies (luting system [LS]/ceramic surface conditioning [CSC]) (n=10): (G1) [LS] RelyX-Unicem/[CSC] airborne abrasion with 110-μm Al2O3 particles; (G2) [LS] One-Step + Duo-Link (bis-GMA-based resin)/[CSC] etching with 4% hydrofluoric acid + silane agent; (G3) [LS] ED-Primer + Panavia F (MDP-based resin)/[CSC] Al2O 3; (G4) [LS] Scotchbond1+RelyX-ARC (bis-GMA-based resin)/[CSC] chairside tribochemical silica coating (air abrasion with 30-μm SiO x particles + silane). After 24 h of water storage at 37°C, the specimens were subjected to 106 fatigue cycles in shear with a sinusoidal load (0 to 21 N, 8 Hz frequency, 37°C water). A fatigue survivor score was given, considering the number of the fatigue cycles until fracture. The failure modes of failed specimens were observed in a SEM. Results: G3 (score = 5.9, 1 failure) and G4 (score = 6, no failures) were statistically similar (p = 0.33) and had significantly higher fatigue resistance than G1 (score = 3.9, 5 failures) and G2 (score = 3.7, 6 failures) (p < 0.03). SEM analysis of fractured specimens of G1 and G2 showed that almost all the failures were between ceramic and cement. Conclusion: The MDP-based resin cement + sandblasting with Al2O3 particles (G3) and bis-GMA-based resin cement + tribochemical silica coating (G4), both using the respective dentin bonding systems, were the best luting protocols for the alumina ceramic. The null hypothesis was confirmed.

Bond strength of a resin cement to high-alumina and zirconia-reinforced ceramics: The effect of surface conditioning

Purpose: The aim of this study was to evaluate the effect of two surface conditioning methods on the microtensile bond strength of a resin cement to three high-strength core ceramics: high alumina-based (In-Ceram Alumina, Procera AllCeram) and zirconia-reinforced alumina-based (In-Ceram Zirconia) ceramics. Materials and Methods: Ten blocks (5 ×6 × 8 mm) of In-Ceram Alumina (AL), In-Ceram Zirconia (ZR), and Procera (PR) ceramics were fabricated according to each manufacturer's instructions and duplicated in composite. The specimens were assigned to one of the two following treatment conditions: (1) airborne particle abrasion with 110-μm Al2O3 particles + silanization, (2) silica coating with 30 μm SiOx particles (CoJet, 3M ESPE) + silanization. Each ceramic block was duplicated in composite resin (W3D-Master, Wilcos, Petrópolis, RJ, Brazil) using a mold made out of silicon impression material. Composite resin layers were incrementally condensed into the mold to fill up the mold and each layer was light polymerized for 40 s. The composite blocks were bonded to the surface-conditioned ceramic blocks using a resin cement system (Panavia F, Kuraray, Okayama, Japan). One composite resin block was fabricated for each ceramic block. The ceramic-composite was stored at 37°C in distilled water for 7 days prior to bond tests. The blocks were cut under water cooling to produce bar specimens (n = 30) with a bonding area of approximately 0.6 mm2. The bond strength tests were performed in a universal testing machine (crosshead speed: 1 mm/min). Bond strength values were statistically analyzed using two-way ANOVA and Tukey's test (≤ 0.05). Results: Silica coating with silanization increased the bond strength significantly for all three high-strength ceramics (18.5 to 31.2 MPa) compared to that of airborne particle abrasion with 110-μm Al2O3 (12.7-17.3 MPa) (ANOVA, p < 0.05). PR exhibited the lowest bond strengths after both Al2O3 and silica coating (12.7 and 18.5 MPa, respectively). Conclusion: Conditioning the high-strength ceramic surfaces with silica coating and silanization provided higher bond strengths of the resin cement than with airborne particle abrasion with 110-μm Al2O3 and silanization.

Polishing methods of an alumina-reinforced feldspar ceramic

The purpose of this study was to test the hypothesis that mechanical polishing methods of ceramic surfaces allow similar superficial roughness to that of glazed surfaces. Twenty-five Vitadur Alpha ceramic discs (5 mm x 2 mm) were prepared according to the manufacturer's specifications. All specimens were glazed and randomly assigned to 5 groups (n=5), according to finishing and polishing protocols: G1: glazed (control); G2: diamond bur finishing; G3: G2 + silicon rubber tip polishing; G4: G3 + felt disc/diamond polishing paste; G5: G3 + felt disc impregnated with fine-particle diamond paste. Next, surface roughness means (Ra - μm) were calculated. Qualitative analysis was made by scanning electron microscopy. Surface roughness data were submitted to ANOVA and Tukey's test at 5% significance level. G1 and G4 were statistically similar (p>0.05). G2 presented the highest roughness means (p<0.05) followed by groups G3, G5, G4 and G1 in a decreasing order. The hypothesis was partially confirmed as only the mechanical polishing (G4) produced similar superficial roughness to that of surface glazing, although finishing and polishing are technically critical procedures.

Durability of feldspathic veneering ceramic on glass-infiltrated alumina ceramics after long-term thermocycling.

This study compared the bond strength durability of a feldspathic veneering ceramic to glass-infiltrated reinforced ceramics in dry and aged conditions. Disc shaped (thickness: 4 mm, diameter: 4 mm) of glass-infiltrated alumina (In-Ceram Alumina) and glass-infiltrated alumina reinforced by zirconia (In-Ceram Zirconia) core ceramic specimens (N=48, N=12 per groups) were constructed according to the manufacturers' recommendations. Veneering ceramic (VITA VM7) was fired onto the core ceramics using a mold. The core-veneering ceramic assemblies were randomly divided into two conditions and tested either immediately after specimen preparation (Dry) or following 30000 thermocycling (5-55 oC±1; dwell time: 30 seconds). Shear bond strength test was performed in a universal testing machine (cross-head speed: 1 mm/min). Failure modes were analyzed using optical microscope (x20). The bond strength data (MPa) were analyzed using ANOVA (α=0.05). Thermocycling did not decrease the bond strength results for both In-Ceram Alumina (30.6±8.2 MPa; P=0.2053) and In-Ceram zirconia (32.6±9 MPa; P=0.3987) core ceramic-feldspathic veneering ceramic combinations when compared to non-aged conditions (28.1±6.4 MPa, 29.7±7.3 MPa, respectively). There were also no significant differences between adhesion of the veneering ceramic to either In-Ceram Alumina or In-Ceram Zirconia ceramics (P=0.3289). Failure types were predominantly a mixture of adhesive failure between the veneering and the core ceramic together with cohesive fracture of the veneering ceramic. Long-term thermocycling aging conditions did not impair the adhesion of the veneering ceramic to the glass-infiltrated alumina core ceramics tested.

Use of high energy ball milling on the sintering optimization of alumina ceramics

In this work, the effect of the milling time on the densification of the alumina ceramics with or without 5wt.%Y 2O 3, is evaluated, using high-energy ball milling. The milling was performed with different times of 0, 2, 5 or 10 hours. All powders, milled at different times, were characterized by X-Ray Diffraction presenting a reduction of the crystalline degree and crystallite size as function of the milling time increasing. The powders were compacted by cold uniaxial pressing and sintered at 1550°C-60min. Green density of the compacts presented an increasing as function of the milling time and sintered samples presented evolution on the densification as function of the reduction of the crystallite size of the milled powders. © (2010) Trans Tech Publications.