Layer-by-layer deposition of praseodymium oxide on tin-doped indium oxide (ITO) surface

Praseodymium oxide as a thin film of controllable layer is known to display many unique physiochemical properties, which can be useful to ceramic, semiconductive and sensor industries. Here in this short paper, we describe a new chemical method of depositing praseodymium oxide on tin-doped indium oxide (ITO) surface using a layer-by-layer approach. The process is carried out by dipping the ITO in solutions of adsorbable polycationic chitosan and alkaline praseodymium hydroxide Pr(OH)(3) alternatively in order to build up the well-defined multi-layers. XRD suggests that the predominant form of the oxide is Pr6O11, obtained after heat treatment of the deposited ITO in static air at 500 degrees C. Microscopic studies including AFM, TEM and SEM indicate that the deposited oxide particles are uniform in size and shape (cylindrical), mesoporous and the thickness of the film can be controlled. AC impedance measurements of the deposited materials also reveal that the oxide layers display a high electrical conductivity hence suitable for sensor uses. (c) 2006 Elsevier B.V. All rights reserved.

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.

Effect of ceramic surface treatment on the shear bond strength of a resin cement to different ceramic systems

This study evaluated three surface treatments and their effects on the shear bond strength between a resin cement and one of three ceramics. The ceramic surfaces were evaluated with scanning electron microscopy (SEM ) as well. Specimens were treated with 50 μm aluminum oxide airborne particles, 10% hydrofluoric acid etching, or a combination of the two. Using a matrix with a center hole (5.0 mm × 3.0 mm), the ceramic bonding areas were filled with resin cement following treatment. The specimens were submitted to thermal cycling (1,000 cycles) and the shear bond strength was tested (0.5 mm/minute). The failure mode and the effect of surface treatment were analyzed under SEM . Data were submitted to ANOVA and a Tukey test (α = 0.05). Duceram Plus and IPS Empress 2 composite specimens produced similar shear bond strength results (p > 0.05), regardless of the treatment method used. Hydrofluoric acid decreased the shear bond strength of In-Ceram Alumina specimens. For all materials, surface treatments changed the morphological surface. All treatments influenced the shear bond strength and failure mode of the ceramic/resin cement composites.

Bidimensional codes recorded on an oxide glass surface using a continuous wave CO(2) laser

Surface heat treatment in glasses and ceramics, using CO(2) lasers, has attracted the attention of several researchers around the world due to its impact in technological applications, such as lab-on-a-chip devices, diffraction gratings and microlenses. Microlens fabrication on a glass surface has been studied mainly due to its importance in optical devices (fiber coupling, CCD signal enhancement, etc). The goal of this work is to present a systematic study of the conditions for microlens fabrications, along with the viability of using microlens arrays, recorded on the glass surface, as bidimensional codes for product identification. This would allow the production of codes without any residues (like the fine powder generated by laser ablation) and resistance to an aggressive environment, such as sterilization processes. The microlens arrays were fabricated using a continuous wave CO(2) laser, focused on the surface of flat commercial soda-lime silicate glass substrates. The fabrication conditions were studied based on laser power, heating time and microlens profiles. A He-Ne laser was used as a light source in a qualitative experiment to test the viability of using the microlenses as bidimensional codes.

Resin Bonding to a Feldspar Ceramic After Different Ceramic Surface Conditioning Methods: Evaluation of Contact Angle, Surface pH, and Microtensile Bond Strength Durability

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Influence of ceramic surface conditioning and resin cements on microtensile bond strength to a glass ceramic

Statement of problem. It is not clear how different glass ceramic surface pretreatments influence the bonding capacity of various luting agents to these surfaces.Purpose. The purpose of this study was to evaluate the microtensile bond strength (mu TBS) of 3 resin cements to a lithia disilicate-based ceramic submitted to 2 surface conditioning treatments.Material and methods. Eighteen 5 X 6 X 8-mm ceramic (IPS Empress 2) blocks were fabricated according to manufacturer's instructions and duplicated in composite resin (Tetric Ceram). Ceramic blocks were polished and divided into 2 groups (n=9/treatment): no conditioning (no-conditioning/control), or 5% hydrofluoric acid etching for 20 seconds and silanization for 1 minute (HF + SIL). Ceramic blocks were cemented to the composite resin blocks with I self-adhesive universal resin cement (RelyX Unicem) or 1 of 2 resin-based luting agents (Multilink or Panavia F), according to the manufacturer's instructions. The composite resin-ceramic blocks were stored in humidity at 37 degrees C for 7 days and serially sectioned to produce 25 beam specimens per group with a 1.0-mm(2) cross-sectional area. Specimens were thermal cycled (5000 cycles, 5 degrees C-55 degrees C) and tested in tension at 1 mm/min. Microtensile bond strength data (MPa) were analyzed by 2-way analysis of variance and Tukey multiple comparisons tests (alpha=.05). Fractured specimens were examined with a stereomicroscope (X40) and classified as adhesive, mixed, or cohesive.Results. The surface conditioning factor was significant (HF+SIL > no-conditioning) (P<.0001). Considering the unconditioned groups, the mu TBS of RelyX Unicem was significantly higher (9.6 +/- 1.9) than that of Multilink (6.2 +/- 1.2) and Panavia F (7.4 +/- 1.9). Previous etching and silanization yielded statistically higher mu TBS values for RelyX Unicem (18.8 +/- 3.5) and Multilink (17.4 +/- 3.0) when compared to Panavia F (15.7 +/- 3.8). Spontaneous debonding after thermal cycling was detected when luting agents were applied to untreated ceramic surfaces.Conclusion. Etching and silanization treatments appear to be crucial for resin bonding to a lithia disilicate-based ceramic, regardless of the resin cement used.

The effect of ceramic surface treatment on bonding to densely sintered alumina ceramic

Statement of problem. Ceramic surface treatment is crucial for bonding to resin. High crystalline ceramics are poorly conditioned using traditional procedures.Purpose. The purpose of this study was to evaluate the effect of silica coating on a densely sintered alumina ceramic relative to its bond strength to composite, using a resin luting agent.Material and methods. Blocks (6 X 6 X 5 mm) of ceramic and composite were made. The ceramic (Procera AllCeram) surfaces were polished, and the blocks were divided into 3 groups (n = 5): SB, airborne-particle abrasion with 110-mu m Al(2)O(3); RS, silica coating using Rocatec System; and CS, silica coating using CoJet System. The treated ceramic blocks were luted to the composite (W3D Master) blocks using a resin luting agent (Panavia F). Specimens were stored in distilled water at 37 degrees C for 7 days and then Cut in 2 axes, x and y, to obtain specimens with a bonding area of approximately 0.6 mm(2) (n = 30). The specimens were loaded to failure in tension in a universal testing machine, and data were statistically analyzed using a randomized complete block design analysis of variance and Tukey's test (alpha=.05). Fractured surfaces were examined using light microscopy and scanning electron microscopy to determine the type of failure. Energy-dispersive spectroscopy was used for surface compositional analysis.Results. Mean bond strength values (MPa) of Groups RS (17.1 +/- 3.9) (P = .00015) and CS (18.5 +/- 4.7) (P=.00012) were significantly higher than the values of Group SB (12.7 +/- 2.6). There was no statistical difference between Groups RS and CS. All failures occurred at the adhesive zone.Conclusion. Tribochemical silica coating systems increased the tensile bond strength values between Panavia F and Procera AllCeram ceramic.

Evaluation of Chemical Treatment on Zirconia Surface with Two Primer Agents and an Alkaline Solution on Bond Strength

Objectives: This study evaluated the effect of an alkaline solution and two 10-methacryloyloxydecyl dihydrogen phosphate (MDP)-based primer agents on bond strength to zirconia (yttria-stabilized tetragonal zirconium polycrystal [Y-TZP]) through the shear bond strength (SBS) test. Materials and Methods: Sixty square-shaped Y-TZP samples were embedded in an acrylic resin mold, polished, and randomly assigned to one of six groups (n=10) according to treatment surface: group CR, no treatment (control); group NaOH, 0.5 M NaOH; group AP, Alloy Primer; group ZP, Z-Primer Plus; group NaOH-AP, 0.5 M NaOH + Alloy Primer; and group NaOH-ZP, 0.5 M NaOH + Z-Primer Plus. The resin cement (Rely X U100) was applied inside a matrix directly onto the Y-TZP surface, and it was light-cured for 40 seconds. The samples were stored in distilled water at 37 C for 24 hours prior to the test, which was performed in a universal machine at a crosshead-speed of 0.5 mm/min. The data were analyzed by one-way analysis of variance and Tukey tests (p<0.05). Light stereomicroscopy and scanning electron microscopy were used to assess the surface topography and failure mode. Results: The SBS was significantly affected by the chemical treatment (p<0.0001). The AP group displayed the best results, and the use of NaOH did not improve SBS results relative to either AP or ZP. The samples treated with Alloy Primer displayed mainly mixed failures, whereas those conditioned with Z-Primer Plus or with 0.5 M NaOH presented a balanced distribution of adhesive and mixed failure modes. Conclusions: The use of a NaOH solution may have modified the reactivity of the Y-TZP surface, whereas the employment of a MDP/6-4-vinylbenzyl-n-propyl amino-1,3,5-triazine2,4-dithione-based primer enhanced the Y-TZP bond strength.

Development and characterization of non-oxide ceramic composites for mechanical and tribological applications

The main reasons for the attention focused on ceramics as possible structural materials are their wear resistance and the ability to operate with limited oxidation and ablation at temperatures above 2000°C. Hence, this work is devoted to the study of two classes of materials which can satisfy these requirements: silicon carbide -based ceramics (SiC) for wear applications and borides and carbides of transition metals for ultra-high temperatures applications (UHTCs). SiC-based materials: Silicon carbide is a hard ceramic, which finds applications in many industrial sectors, from heat production, to automotive engineering and metals processing. In view of new fields of uses, SiC-based ceramics were produced with addition of 10-30 vol% of MoSi2, in order to obtain electro conductive ceramics. MoSi2, indeed, is an intermetallic compound which possesses high temperature oxidation resistance, high electrical conductivity (21·10-6 Ω·cm), relatively low density (6.31 g/cm3), high melting point (2030°C) and high stiffness (440 GPa). The SiC-based ceramics were hot pressed at 1900°C with addition of Al2O3-Y2O3 or Y2O3-AlN as sintering additives. The microstructure of the composites and of the reference materials, SiC and MoSi2, were studied by means of conventional analytical techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (SEM-EDS). The composites showed a homogeneous microstructure, with good dispersion of the secondary phases and low residual porosity. The following thermo-mechanical properties of the SiC-based materials were measured: Vickers hardness (HV), Young’s modulus (E), fracture toughness (KIc) and room to high temperature flexural strength (σ). The mechanical properties of the composites were compared to those of two monolithic SiC and MoSi2 materials and resulted in a higher stiffness, fracture toughness and slightly higher flexural resistance. Tribological tests were also performed in two configurations disco-on-pin and slideron cylinder, aiming at studying the wear behaviour of SiC-MoSi2 composites with Al2O3 as counterfacing materials. The tests pointed out that the addition of MoSi2 was detrimental owing to a lower hardness in comparison with the pure SiC matrix. On the contrary, electrical measurements revealed that the addition of 30 vol% of MoSi2, rendered the composite electroconductive, lowering the electrical resistance of three orders of magnitude. Ultra High Temperature Ceramics: Carbides, borides and nitrides of transition metals (Ti, Zr, Hf, Ta, Nb, Mo) possess very high melting points and interesting engineering properties, such as high hardness (20-25 GPa), high stiffness (400-500 GPa), flexural strengths which remain unaltered from room temperature to 1500°C and excellent corrosion resistance in aggressive environment. All these properties place the UHTCs as potential candidates for the development of manoeuvrable hypersonic flight vehicles with sharp leading edges. To this scope Zr- and Hf- carbide and boride materials were produced with addition of 5-20 vol% of MoSi2. This secondary phase enabled the achievement of full dense composites at temperature lower than 2000°C and without the application of pressure. Besides the conventional microstructure analyses XRD and SEM-EDS, transmission electron microscopy (TEM) was employed to explore the microstructure on a small length scale to disclose the effective densification mechanisms. A thorough literature analysis revealed that neither detailed TEM work nor reports on densification mechanisms are available for this class of materials, which however are essential to optimize the sintering aids utilized and the processing parameters applied. Microstructural analyses, along with thermodynamics and crystallographic considerations, led to disclose of the effective role of MoSi2 during sintering of Zrand Hf- carbides and borides. Among the investigated mechanical properties (HV, E, KIc, σ from room temperature to 1500°C), the high temperature flexural strength was improved due to the protective and sealing effect of a silica-based glassy phase, especially for the borides. Nanoindentation tests were also performed on HfC-MoSi2 composites in order to extract hardness and elastic modulus of the single phases. Finally, arc jet tests on HfC- and HfB2-based composites confirmed the excellent oxidation behaviour of these materials under temperature exceeding 2000°C; no cracking or spallation occurred and the modified layer was only 80-90 μm thick.

Loading effect in copper(II) oxide cluster-surface-modified titanium(IV) oxide on visible- and UV-light activities

Cu(acac)2 is chemisorbed on TiO2 particles [P-25 (anatase/rutile = 4/1 w/w), Degussa] via coordination by surface Ti–OH groups without elimination of the acac ligand. Post-heating of the Cu(acac)2-adsorbed TiO2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO2). The copper loading amount (Γ/Cu ions nm–2) is controlled in a wide range by the Cu(acac)2 concentration and the chemisorption–calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO2, which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O2. First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO2. These results suggest that visible-light excitation of CuO/TiO2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O2 to achieve the compatibility of high levels of visible and UV-light activities.

The influence of internal surface treatments on tensile bond strength for two ceramic systems

Statement of the Problem: the ceramic composition and surface microstructure of all-ceramic restorations are important components of an effective bonding substrate. Hydrofluoric acid and sandblasting are well-known procedures for surface treatment; however, surface treatment for high alumina-containing and lithium disilicate ceramics have not been fully investigated.Purpose: This in vitro study evaluated the tensile bond strength of resin cement to two types of ceramic systems with different surface treatments.Methods and Materials: Thirty specimens of each ceramic system were made according to the manufacturer's instructions and embedded in polyester resin. Specimens of In-Ceram Alumina [1] and IPS Empress 2 [E] were distributed to three groups with differing surface treatments (n=10): sandblasting with 50 jam aluminum oxide (APA); sandblasting with 110 pm aluminum oxide modified with silica particles (ROCATEC System-RS); a combination of sandblasting with APA and 10% hydrofluoric acid etching (HA) for two minutes on In-Ceram and for 20 seconds for IPS Empress 2. After the respective surface treatments, all the specimens were silanated, and Rely-X resin cement was injected onto the ceramic surface and light polymerized. The specimens were stored in distilled water at 37 degrees C for 24 hours and thermally cycled 1,100 times (5 degrees C/55 degrees C). The tensile bond strength test was performed in a universal testing machine at a 0.5 mm/minute crosshead speed.Results: the mean bond strength values (AWa) for IPS Empress 2 were 12.01 +/- 5.93 (EAPA), 10.34 +/- 1.77 (ERS) and 14.49 +/- 3.04 (EHA). The mean bond strength values for In-Ceram Alumina were 9.87 +/- 2.40 JAPA) and 20.40 +/- 6.27 (IRS). All In-Ceram specimens treated with 10% hydrofluoric acid failed during thermal cycling.Conclusion: the Rocatec system was the most effective surface treatment for In-Ceram Alumina ceramics; whereas, the combination of aluminum oxide sandblasting and hydrofluoric acid etching for 20 seconds worked more effectively for Empress 2 ceramics.

Surface functionalization of alumina ceramic foams with organic ligands.

Different anchoring groups have been studied with the aim of covalently binding organic linkers to the surface of alumina ceramic foams. The results suggested that a higher degree of functionalization was achieved with a pyrogallol derivative - as compared to its catechol analogue - based on the XPS analysis of the ceramic surface. The conjugation of organic ligands to the surface of these alumina materials was corroborated by DNP-MAS NMR measurements.

Bonding of Composite Resin to Alumina and Zirconia Ceramics with Special Emphasis on Surface Conditioning and Use of Coupling Agents

Dental oxide ceramics have been inspired by their biocompability and mechanical properties which have made durable all-ceramic structures possible. Clinical longevity of the prosthetic structures is dependent on effective bonding with luting cements. As the initial shear bond strength values can be comparable with several materials and procedures, long-term durability is affected by ageing. Aims of the current study were: to measure the shear bond strength of resin composite-to-ceramics and to evaluate the longevity of the bond; to analyze factors affecting the bond, with special emphasis on: the form of silicatization of the ceramic surface; form of silanization; type of resin primer and the effect of the type of the resin composite luting cement; the effect of ageing in water was studied regarding its effect to the endurance of the bond. Ceramic substrates were alumina and yttrium stabilized zirconia. Ceramic conditioning methods included tribochemical silicatization and use of two silane couplings agents. A commercial silane primer was used as a control silane. Various combinations of conditioning methods, primers and resin cements were tested. Bond strengths were measured by shear bond strength method. The longevity of the bond was generally studied by thermocycling the materials in water. Additionally, in one of the studies thermal cycling was compared with long-term water storaging. Results were analysed statistically with ANOVA and Weibull analysis. Tribochemical treatment utilizing air pressure of 150 kPa resulted shear bond strengths of 11.2 MPa to 18.4 MPa and air pressure of 450 kPa 18.2 MPa to 30.5 MPa, respectively. Thermocycling of 8000 cycles or four years water storaging both decreased shear bond strength values to a range of 3.8 MPa to 7.2 MPa whereas initial situation varied from 16.8. Mpa to 23.0 MPa. The silane used in studies had no statistical significance. The use of primers without 10-MDP resulted spontaneous debonding during thermocycling or shear bond strengths below 5 MPa. As conclusion, the results showed superior long-term bonding with primers containing 10-MDP. Silicatization with silanizing showed improved initial shear bond strength values which considerably decreased with ageing in water. Thermal cycling and water storing for up to four years played the major role in reduction of bond strength, which could be due to thermal fatigue of the bonding interface and hydrolytic degradation of the silane coupled interface.