Durable superhydrophobic Zn/ZnO/TiO2 surfaces on Ti6Al4V substrate with self-cleaning property and switchable wettability

Durable superhydrophobic (SHP) Zn/ZnO/TiO₂ surfaces with dendritic structures on Ti₆Al₄V substrate were obtained by chemical etching, electrodeposition and following annealing process. The resultant coatings electrodeposited at ?1.5 V for 10 min and annealed at 190 °C for 60 min showed fine superhydrophobicity with a water contact angle of 160° and a rolling angle less than 1°, showing excellent rolling-off and self-cleaning properties. The morphology, chemical components and growth mechanism of samples were investigated by scanning electron microscopy (SEM), X-ray diffraction pattern (XRD), Energy-dispersive spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS). Surface tribological properties were characterized by a universal mechanical tester (UMT). The as-prepared Zn/ZnO/TiO₂ surface still kept excellent SHP stability after exposure to the air, buried in soil and cold storage at 5 °C in the fridge for one year, as well as excellent repellence to some daily-used liquids such as coke, coffee, red wine, milk and tea. The surface can be reversibly switched between superhydrophobicity and superhydrophilicity by alternating UV illumination and dark storage or heating, which offer possibilities to widen future applications.     

A simple method for the fabrication of silica-based superhydrophobic surfaces

The present article reports on a simple and convenient method for the fabrication of superhydrophobic surfaces based on silica particles by spraying the as-prepared silica suspension containing silica sol and silica microspheres on the substrate. The morphologies of the silica particulate coatings could be controlled by varying the silica microsphere concentration. The silica particulate coatings as prepared were exceptionally rough and superhydrophilic, with water contact angles less than 5°. The surface silanol groups of the hydrophilic coatings could be functionalized using 1H,1H,2H,2H-perfluorodecyltriethoxysilane to form hydrophobic groups. The resulting surface showed excellent superhydrophobic property with water contact angle up to 165.6 ± 0.9° and sliding angle of 3.5 ± 0.4°. In addition, the superhydrophobicity of the coating possessed a good stability after 3 months of exposure in air for a wide range of pH values.     

Analysis of structural,morphological alterations,wettability characteristics and adhesion to enamel after various surface conditioning methods

Minimal invasive dental reconstructions and orthodontic appliances are bonded to enamel without removing the enamel with rotating instruments but the top layer of enamel may be partially aprismatic and impair adhesion. The objectives of this study were to investigate the effect of mechanical surface conditioning methods for removing enamel on its structural, morphological alterations, wettability characteristics, and adhesion of resin-based cement to the conditioned surfaces. Maxillary human incisors (N = 40, n_quadrant = 160) were obtained and coronal sections were embedded in acrylic with their labial surfaces exposed. The teeth were randomly divided into four groups and the enamel surface of each tooth was divided into four quadrants. The surfaces were conditioned in a clockwise manner by one of the following methods: (1) Non-conditioned enamel acted as the control group (C); (2) Silicone-coated disk (Sof-Lex disc, Black, 3 M ESPE) (SD); (3) Diamond bur at slow speed (DB) and (4) Airborne particle abrasion (50 μm Al₂O₃, 2 bar, 5 s) (AA). Surface roughness was measured at each quadrant using a non-contact digital profilometer and contact angle measurements were performed using a goniometer. Enamel surfaces were then etched with 37% H₃PO₄ for 60 s and roughness and wettability measurements were repeated. The enamel surfaces in each quadrant received resin composite luting cement (Variolink II, Ivoclar Vivadent) incrementally in a polyethylene mold (diameter: 1 mm²; height: 4 mm) and photopolymerized. The specimens were stored in distilled water for 24 h at 37 °C until the testing procedures and then shear force was applied to the adhesive interface until failure occurred in a Universal Testing Machine (0.5 mm/min). Microshear bond (μSBS) was calculated by dividing the maximum load (N) by the bonding surface area of the resin cement. Representative enamel surfaces were analyzed under the scanning electron microscope (SEM) (x5000) to assess the surface morphology. Failure types were analyzed using optical microscope and SEM. Data (MPa) were analyzed using one-way ANOVA and Tukey`s test for each parameter and Linear model for group comparisons (α = 0.05). Surface conditioning method significantly affected the adhesion results (p < 0.001), surface roughness (p = 0.017), and contact angle (p < 0.001). Interaction terms were significant (p > 0.05). AA (338 ± 182) created significantly higher surface roughness compared to SD (308 ± 180) and DB (242 ± 197) (p < 0.05). After etching with 37% H₃PO₄, DB (307 ± 223) resulted in significantly lower roughness than those of SD (385 ± 173) and AA (414 ± 193) (p < 0.05). AA (40 ± 11) delivered significantly lower contact angle compared to those of SD (61 ± 9) and DB (59 ± 10). After etching with 37% H₃PO₄, AA (42 ± 10) and DB (50 ± 10) presented the lowest contact angle (p < 0.05). Mean μSBS results (MPa) showed significant difference between the experimental groups (p = 0.011) and were in descending order as follows: DB (20 ± 8)^a?a b < C (12 ± 5)^b. Failure types were predominantly mixed failure type between the enamel and the resin cement with more than half of the resin remained on the enamel surface (32 to 33 out of 40) in all groups. Cohesive failure in the enamel was not observed in any of the groups. SEM analysis showed that AA group leaves abundant particles on the enamel surface and after DB and AA, etching could not remove the particles completely and expose the enamel prisms.     

Durable,self-cleaning and superhydrophobic bamboo timber surfaces based on TiO2 films combined with fluoroalkylsilane

Decorative materials, including bamboo timber, have been proposed to exploit their superhydrophobic and self-cleaning properties, but a comprehensive appraisal of their environmental adaptability is still deficient. In this paper, a robust and durable superhydrophobic surface was formed on bamboo timber substrate through a process combining chemical solution deposition and chemical modification. The superhydrophobic surface resulted from micro-nanoscale binary-structured TiO₂ films and the assembly of low-surface-energy fluorinated components, which exhibited a water contact angle of 163±1° and a sliding angle of 3±1°. The surface maintained superhydrophobicity after mechanical abrasion against 1500 mesh SiC sandpaper for 800 mm at the applied pressure of 1.2 kPa, indicating good mechanical stability. Moreover, the superhydrophobic surface exhibited good chemical stability against both acidic and basic aqueous solutions (e.g., simulated acid rain). After exposure to atmosphere for more than 180 days, the obtained surface still maintained a contact angle of 155±2° and a sliding angle of 6±2°, revealing good long-term stability. In addition, the as-prepared superhydrophobic surface exhibited almost complete wet self-cleaning of dirt particles with water droplets. It is believed that the method presented in this study can provide a straightforward and effective route to fabricate a large-area, mechanically robust, anticorrosive and self-cleaning superhydrophobic surface on woody materials for a great number of potential applications.     

The Use of Low-pressure Plasma on Enhancing the Attachment of Al2O3 Nanoparticles to Wood–Plastic Composites

Wood–plastic composites (WPC) are widely used for many purposes due to their interesting properties, but they have poor surface adhesion due to the chemical inertness of the matrix. Thus, in this work, the effect of plasma treatment on the WPC was investigated regarding its influence in the aluminum oxide (Al₂O₃) nanoparticles attachment to the surface. WPC were prepared in a polypropylene (PP) matrix, plasma-treated at 100 W for 600 s, and then covered with Al₂O₃ nanoparticles dispersion. The WPC/Al₂O₃ surfaces have been investigated by means of morphology, surface roughness, chemical structure, wettability, and nanohardness. Plasma treatment improved the attachment of Al₂O₃ onto WPC, which was confirmed by the higher presence of aluminum and oxygen-containing functional groups and the reduction of the intensity of peaks of methylene (CH₂) and methyl (CH₃) groups on the WPC surface. The higher surface reactivity of plasma-treated WPC resulted in a better distribution of the nanoparticles over the entire surface. In addition, plasma treatment avoided the formation of coffee-ring phenomenon but it was able to create cone-like structures on the WPC, increasing the surface roughness due to the etching effect and the attachment of Al₂O₃ nanoparticles. Plasma treatment followed by Al₂O₃ nanoparticles attachment increased the wettability, hardness, and elastic modulus of WPC at nanometric scale.     

Facile fabrication approach for a novel multifunctional superamphiphobic coating based on chemically grafted montmorillonite/Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-polydimethylsiloxane binary nanocomposite

In this paper, a novel multifunctional superamphiphobic coating for anticorrosion was successfully prepared on aluminum substrate via a simple spraying technique. Al₂O₃ nanoparticles were chemically grafted onto montmorillonite (MMT) nanosheets via coupling effect of NH₂-C₃H₆-Si(OC₂H₅)₃ (KH-550) and then modified by low surface energy material polydimethylsiloxane (PDMS). The ethylene tetrafluoroethylene (ETFE) composite coating with 25 wt% MMT/Al₂O₃-PDMS binary nanocomposite exhibited well-designed nano/μ structures and possessed superamphiphobicity with high contact angles towards water (164°), glycerol (158°) and ethylene glycol (155°). This coating demonstrated outstanding self-cleaning ability and strong adhesive ability (Grade 1 according to the GB/T 9286). The superhydrophobicity could be maintained after 8000 times abrasion or annealing treatment for 2 h under 350 °C. The coating still retained high water-repellence after immersion in 1 mol/L HCl (146°), 1 mol/L NaOH (144°) and 3.5 wt% NaCl (151°) solutions for 30 d. It should be noted that this superamphiphobic coating revealed excellent long-term corrosion protection with extremely low corrosion rate (4.3 × 10^?3 μm/year) and high protection performance (99.999%) after 30 d immersion in 3.5 wt% NaCl solutions based on electrochemical corrosion measurements. It is believed that such integrated functional coating could pave new way for self-cleaning and anticorrosion applications under corrosive/abrasive environment.     

Adhesion improvement of electroless copper to PC substrate by a low environmental pollution MnO2–H3PO4–H2SO4–H2O system

A low environmental pollution etching system, MnO₂–H₂SO₄–H₃PO₄–H₂O colloid, was used to investigate surface etching performance of polycarbonate (PC) as a replacement for the chromic acid etching solution. The effects of H₂SO₄ concentrations, H₃PO₄ concentrations and etching times upon the surface topography, surface chemistry and surface roughness were studied. With the appropriate etching treatment, the surface average roughness (R_a) of PC substrates increased from 3 to 177 nm, and the adhesion strength between the electroless copper and PC substrate also reached 1.10 KN m⁻¹. After the etching treatment, the PC surface became hydrophilic and the surface contact angle decreased from 95.2° to 24.8°. The intensity of C–O groups increased and the new functional groups (–COOH) formed on the PC surface with the etching treatment, which improved the adhesion strength between PC substrate and elctroless copper film.     

Stable superhydrophobic surface based on low‐density polyethylene/ethylene‐propylene‐diene terpolymer thermoplastic vulcanizate

Stable superhydrophobic surface based on low‐density polyethylene (LDPE)/ethylene–propylene–diene terpolymer (EPDM) thermoplastic vulcanizate (TPV) was successfully fabricated by using etched aluminum foil as template. The etched aluminum template consisted of micropores and step‐like textures, was obtained by the metallographic sandpaper sanding and the subsequent acid etching. The surface morphology and hydrophobic properties of the series molded TPV surfaces were researched by varying the weight ratio of the LDPE/EPDM TPV. The superhydrophobic LDPE/EPDM TPV surfaces exhibited the microstructures consisting of step‐like textures obtained via molding with etched aluminum template and a large number of fiber‐like structures resulted from the plastic deformation of LDPE matrix. The obtained TPV (LDPE/EPDM weight ratio = 70/30) surface exhibited the remarkable superhydrophobicity, with a contact angle of 152.0° ± 0.7° and a sliding angle of 3.1° ± 0.8°. The molded TPV surface had excellent environmental stability when the pH of water solution was in the range of 1 to 14; moreover, the surface also showed the excellent resistance to various organic solvents. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46241.     

Investigating the effect of water-mixing nitrogen atmospheric pressure plasma jet on polyether-ether-ketone and time stability under different conditions

Possessing excellent properties including good biocompatibility, high strength, and stiffness, polyether-ether-ketone (PEEK) has significant application values in medical and industrial fields. However, the relatively poor wettability and low adhesion limit its further applications. Atmospheric pressure plasma jet (APPJ) has been utilized for adjusting PEEK properties, but better hydrophilization effect and time stability after treatment are still urgently needed. In this paper, we employ a water-mixing nitrogen (N₂ H₂O) APPJ to process PEEK, and surface wettability can be effectively improved (contact angle ~18° within 2 min, distance between sample and nozzle outlet: 10 mm) without inducing obvious microstructure damages. Additionally, after storing for 40 days, the sample treated by N₂ H₂O APPJ also possessed better wettability (~54°) compared with that treated by N₂ APPJ (~65°). On the basis of this low-damage and high-efficient modification method, we perform aging experiments under different conditions (different temperatures 25, −10°C; and low vacuum condition: 50 kPa) to determine a relatively optimum storing condition for this method. The experiment results indicate that low temperature and vacuum are conducive to retaining the plasma-induced wettability (~34°). The treatment method and storing conditions for PEEK presented here may facilitate the application of PEEK in various fields.     

Reversible Photocontrol of Wood-Surface Wettability Between Superhydrophilicity and Superhydrophobicity Based on a TiO2 Film

The reversible photocontrol of wood-surface wettability between superhydrophilicity and superhydrophobicity based on a TiO₂ film modified with octadecyl trichlorosilane (OTS) was achieved via a facile hydrothermal method at low temperature. Under UV illumination, the wood surface became superhydrophilic with a water contact angle (WCA) of approximately 0°. However, when placed in the dark, a superhydrophobic wood surface with a WCA of approximately 152° was achieved. The mechanism of the reversible photocontrol of wood-surface wettability is discussed in this article. This photocontrolled wood surface may have potential for wood self-cleaning or manipulation in response to indoor humidity.     

Micro-structure of ITO ceramics sintered at different temperatures and its effect on the properties of deposited ITO films

Structural characterizations of two ITO ceramics that were respectively sintered at 1560 °C and 1600 °C were focused on and the results indicate that the lower sintering temperature is good for ITO ceramics to have the triangle fine grains, larger elemental concentration gradients of indium and tin and more content of In₄Sn₃O₁₂ phase which displays the stronger grain orientation growth along the crystallographic direction of [0-11]. ITO films with 100 nm thickness deposited at 25 °C–230 °C were used to investigate the effect of micro-structure on the film properties. Grain orientation growth of In₄Sn₃O₁₂ phase is conductive to form ITO films of columnar structure. Otherwise, uniform micro-structure and higher solubility of SnO₂ in In₂O₃ main phase contribute to deposit ITO films of higher sheet resistance, less thickness uniformity and higher transmittance at 25 °C, smaller etching angle and lower etching rate at 230 °C.     

Tunability of the Adhesion of Water Drops on a Superhydrophobic Paper Surface via Selective Plasma Etching

We report the fabrication of a sticky superhydrophobic paper surface with extremely high contact angle hysteresis: advancing contact angle ～150° (superhydrophobic) and receding contact angle ～10° (superhydrophilic). In addition, we report the controlled tunability of the contact angle hysteresis from 149.8 ± 5.8° to 3.5 ± 1.1°, while maintaining superhydrophobicity, as defined through an advancing contact angle above 150°. The hysteresis was tuned through the controlled fabrication of nano-scale features on the paper fibers via selective plasma etching. The variations in contact angle hysteresis are attributed to a transition of the liquid–surface interaction from a Wenzel state to a Cassie state on the nano-scale, while maintaining a Cassie state on the micro-scale. Superhydrophobic cellulosic surfaces with tunable stickiness or adhesion have potential applications in the control of aqueous drop mobility and the transfer of drops on inexpensive, renewable substrates.     

Patterning ZrO2 films surface: Superhydrophilic and superhydrophobic properties

A photosensitive sol-gel method was used to pattern the surface of ZrO₂ film with a groove or a processus mastoideus structure. The surface roughness enhanced by the pattern structure had a strong effect on the ZrO₂ film wettability. Compared to an un-patterned ZrO₂ film, the patterned film showed a smaller static water contact angle (CA) and exhibited superhydrophilicity. Interestingly, the patterned ZrO₂ film did not require the use of UV irradiation to induce the superhydrophilicity and exhibited an excellent anti-fogging behavior. The surface modification with a 1H,1H,2H,2H-perfluorooctyltrichlorosilane (PFOTCS) layer was found to induce the change in the wettability of the patterned ZrO₂ films from superhydrophilicity to hydrophobicity/superhydrophobicity. The PFOTCS-modified ZrO₂ film patterned with the processus mastoideus surface resulted in the highest CA value of 155° and the sliding angle (SA) value of about 7°, and almost did not change under UV irradiation or after being annealed below 350 °C. The surface patterning by using a photosensitive sol-gel method was proved to be a practical approach to fabricate the ZrO₂ film with superhydrophilic/superhydrophobic properties.     

Mangosteen peel and seed as antimicrobial and drug delivery in rubber products

Garcinia mangostana Linn. or mangosteen is a tropical superfruit with an excellent taste. The peel and seed of mangosteen waste can be used in medical, cosmetic, and health-care applications. Both mangosteen peel and seed have outstanding antibiotic properties and are suitable for use as bio-fillers in natural rubber latex products such as medical gloves, rubber transdermal patches, rubber toys, and rubber-health care products. In addition, mangosteen seed composed of griseofulvin polyethylene glycol [(C₂H₄O₂)_n]_1-x (C₁₇H₁₇ClO₆)_x is useful for treating osteoarthritis of the knee, similar to commercial glucosamine (amino sugar). Adding mangosteen peel and mangosteen seed in rubber gloves and rubber patches, respectively, is an alternative form of antimicrobial and drug delivery replacing taking a tablet. This study compared the characteristics and properties of mangosteen peel with silver nitrate (AgNO₃) and compared the characteristics and properties of mangosteen seed with commercial glucosamine using the film casting dipping process. The obtained natural rubber latex gloves with added mangosteen peel powder had a good appearance with a high contact angle (resulting in hydrophobicity and low wettability with water equal to 130.67° ± 2.08°), good mechanical properties (high percentage of elongation at break 815.72 ± 54.67%, high tensile strength 64.59 ± 13.54 MPa, good stiffness 296.50 ± 48.32 N/m, and high Young's modulus 29.65 ± 4.83 MPa), and as it was non-toxic to skin it was suitable for application in medical gloves and transdermal patches. The natural rubber patches added with mangosteen seed had high wettability and good mechanical properties. The Fourier-transform infrared (FTIR) spectra of mangosteen seed were consistent with the FTIR spectra of commercial glucosamine.     

A New Surface Etching Method Using MnO2/H2SO4 Colloid for Adhesion Improvement of Epoxy Polymer

Abstract

A new surface etching method using MnO₂/H₂SO₄ as the etchant to improve the adhesion between an epoxy polymer surface and a metallic layer, was studied. The effects of bath temperature, etching time and H₂SO₄ concentration on the surface topography and chemical properties were investigated. After the etching treatment of the MnO₂–H₂SO₄ colloid, not only did the surface roughness increase remarkably, but also the surface of epoxy became hydrophilic and the contact angle of the epoxy surface was also decreased from 93.5° to about 8.0°. The X-ray photoelectron spectroscopy analysis indicated that as a result of the etching treatment, hydroxyl, carbonyl and carboxylic acid groups formed on the epoxy surface. The adhesion strength was markedly enhanced with the appropriate etching treatment, which was attributed to the improvement of the surface roughness and the increased hydrophilicity.     

Study of an environment-friendly surface pretreatment of ABS-polycarbonate surface for adhesion improvement

In this paper, an environmentally friendly etching system containing MnO₂–H₃PO₄–H₂SO₄ colloid was used to investigate surface etching for ABS- polycarbonate (PC/ABS) as a replacement for conventional chromic acid etching solutions. In order to obtain a good etching performance, a swelling system, containing tetramethylammonium hydroxide (TMAH), and 1-Methyl-2-pyrrolidinone (NMP), was used to investigate the surface swelling for PC/ABS resin. Then the effects of H₂SO₄ concentration, and etching time on the surface topographies and surface contact angle were investigated. After the optimal swelling and etching treatment, the surface contact angle of PC/ABS resin decreased from 95.7° to 28.3°, and the adhesion strength between electroless copper film and PC/ABS resin reached to 1.04 KN m⁻¹. The FT-IR spectra and XPS analyses indicated that hydroxyl and carboxyl groups formed on the PC/ABS surface as a result of the swelling and etching treatment, which improved the adhesion strength between PC/ABS substrate and elctroless copper film.     

Effects of surface modification by Ar+ irradiation on wettability of surfaces of poly(ethylene terephthalate) films

Surfaces of poly(ethylene terephthalate); PET, films were irradiated with Ar⁺ at 1 keV using various ion doses (ID) from 10¹⁴ to 10¹⁷ ions/cm² (isc) with and without an O₂ environment. The wettability of the modified surfaces of PET was determined by measuring the contact angle between water droplets and the modified surfaces. The modified surfaces were also characterized by AFM (atomic force microscopy) and XPS (X-ray photoelectron spectroscopy) for changes in the surface morphology, and the chemical composition and molecular structure, respectively. The contact angle decreased from 70° for unmodified surfaces to 45° for modified surface with ID = 10¹⁴ isc without O₂ and remained relatively constant with higher ID. The contact angle, however, reached a minimum value of 8° for modified surfaces with ID = 10¹⁶ isc with O₂. The improved wettability may be due to a combination of the formation of hydrophilic groups, chemical and molecular structural changes, physical structural or morphological changes, and increased roughness of the surface. The wettability of the modified surfaces also depended on the time of exposure to air. The wettability worsened with exposure time to air, but was revived by immersing the films into water. Possible mechanisms for the change of the wettability of the modified surfaces are given.     

Adhesion of conventional and self-adhesive resin cements to indirect resin composite using different surface conditioning methods

This study evaluated the adhesion of conventional and self-adhesive resin cements to indirect resin composite (IRC) using different surface conditioning methods. Cylindrical IRC specimens (N = 192) were randomly assigned to four surface conditioning methods (n = 8 per group): (a) Control group, (b) Hydrofluoric acid, (c) Tribochemical silica-coating, and (d) 50 μm Al₂O₃ air-abrasion. Specimen surfaces were finished using silicon carbide papers up to 600 grit under water irrigation, rinsed and dried. Direct composite blocks were bonded to IRC specimens using three conventional resin cements (Multilink, Panavia F2.0, and Resicem) and three self-adhesive resin cements (RelyX U100, Gcem, Speed Cem). Specimens were subjected to shear bond strength test in a Universal Testing Machine (0.5 mm/min). Failure types were categorized as mixed, adhesive and cohesive. Data were analyzed using 2-way ANOVA and Tukey’s tests. Two-parameter Weibull modulus, scale (m) and shape (0) were calculated. The bond strength results (MPa) were significantly affected by the surface conditioning method (p < 0.0001) and cement type (p < 0.001). For Panavia F2.0, Resicem, air-abrasion with 50 μm Al₂O₃ significantly increased the results (22.6 ± 6.5, 26.2 ± 6.5, respectively) compared to other conditioning methods (13.6 ± 1.4–21.9 ± 3.1) but for Multilink, hydrofluoric acid etching (20.5 ± 3.5) showed significantly higher results (p < 0.01). For the self-adhesive resin cements, air-abrasion with 50 μm Al₂O₃ significantly increased the results compared to other conditioning methods, except for RelyX U100 (p < 0.05). After air-abrasion with Al₂O₃, Gcem, (11.64), RelyX U100 (9.05), and SpeedCem (8.29) presented higher Weilbul moduli. Exclusively cohesive failure in the IRC was observed with RelyX U100 and Speedcem after Al₂O₃ air-abrasion.     

Could readily silanized silica particles substitute silica coating and silanization in conditioning zirconium dioxide for resin adhesion?

This study investigated the effect of particle types with different morphology and surface properties on the wettability and adhesion of resin cement to zirconia. Zirconia specimens (5 × 5 × 1 mm³) were wet polished. Specimens were randomly assigned to one of the following protocols (N = 36, n = 9 per group): Group CON: Control, no surface conditioning; Group AL: Chairside air-abrasion with aluminium trioxide (50 μm Al₂O₃) + silane; Group SIL: Chairside air-abrasion with alumina particles coated with silica (SIL) (30 μm SiO2, SilJet) + air-drying + silane; Group 4: Chairside air-abrasion with readily silanized silica particles (SILP) (30 μm SiO_2, SilJet Plus). Adhesive resin was applied and resin cement (Variolink II, Ivoclar) was bonded using polyethylene moulds and photo-polymerized and aged (thermocycling, 6.000 cycles, 5–55 °C). Shear bond test was performed using Universal Testing Machine (1 mm/min). Pretest failures were considered 0 MPa. Contact angle measurements were performed (n = 2/group, sessile drop with water). Data (MPa) were analyzed (ANOVA, Tukey’s (α = 0.05). Two-parameter Weibull distribution values including the Weibull modulus, scale (m) and shape (0), values were calculated. Contact angle measurements were in descending order as follows: SIL (74°)^c < CON (60°)^c < AL (51°)^b < SILP (40°)^a. Bond strength (MPa) with SIL (17.2 ± 4)^a and SILP (17.3 ± 1.9)^a demonstrated no significant difference (p > 0.05), being higher than AL (8.4 ± 1.5)^b and CON (0)^c (p < 0.05). Failure types were exclusively adhesive in all groups. Weibull distribution presented the highest shape (0) for SILP (10.8). SILP presented better wettability than AL. SILP provided similar bond strength to SIL. Readily silanized silica particles may substitute for conventional silica coating and silanization.     

Comparison of methanol/hydrochloric,ferric chloride acid versus tribochemical silica coating for adhesion of resin cement to zirconium dioxide

This study compared air-abrasion and etching regimens on adhesion of resin luting agent to zirconium dioxide. Ceramic specimens (LAVA, 3 M ESPE) (N = 16) were embedded in acrylic resin and exposed surfaces were polished. The specimens were randomly assigned into four groups (n = 12, 3 specimens for each disc): SC: Air-borne particle abrasion (30 μm aluminum oxide particles coated with silica, CoJet, 3 M ESPE); MH: Heated chemical solution (Methanol-800 mL; 37% Hydrochloric Acid-200 mL; Ferric Chloride-2 g) at 100 °C for 30 min, MHP: Primer (Metal/Zirconia Primer, Ivoclar Vivadent) + MH, P: Primer only (Metal/Zirconia Primer). Cylindrical molds (internal diameter: 0.7 mm; height: 1.5 mm) were placed on each conditioned specimen, filled with resin cement (Multilink Automix) and photo-polymerized for 60 s. After 24 h, the molds were removed and the specimens were stored in distilled water at 37 °C for six months). Microshear test was performed in a Universal Testing Machine (1 mm/min). Failures types were classified as adhesive, mixed, or cohesive. In another set of specimens (n = 2 per group) contact angle measurements were recorded. Data were analyzed statistically using Kruskal–Wallis and Dunn’s tests (α = 0.05). The surface conditioning method significantly affected the mean bond strength (MPa) (p < 0.0001): SC(18.3 ± 0.3)^a < P(5.00 ± 0.07)^b < MHP(4.7 ± 0.08)^c < MH(0.84 ± 0.01)^c. While Group SC showed mainly adhesive (58%) and mixed (41.7%) failure types, groups MH, MHP, and P presented exclusively adhesive failures. SC, MHP, and P (29–32°) showed lower contact angle than MH (78.9°). Volume loss was the highest with MHP (9.92 μl) followed by SC (9.67 μl).