Corrosion Resistance of Titanium Dental Implant Abutments: Comparative Analysis and Surface Characterization.

Metals subjected to the oral environment are prone to corrosion over time and this can be harmful. Metallic restoration components such as dental subgingival implant abutments are exposed to pH changes and different ions while in contact with saliva. The aim of the study was to evaluate the corrosion resistance of titanium dental implant abutments and to compare and contrast the surface characteristics of these alloys before and after corrosion. The corrosion examination (Ecorr, jcorr, OCP, polarization curve) of two implant abutments (TiDesign EV, Astra Tech, Dentsply, York, PA, USA; Individual Titanium Abutment, Apollo Implants Components, Pabianice, Poland) was performed in 0.9% NaCl and 5% HCl. Moreover, specimens were investigated using SEM-EDS before and after the corrosion test. The value of jcorr in NaCl was higher for Astra (34.2 × 10-8 ± 2.5 × 10-8 A/cm2) than for Apollo (8.8 × 10-8 ± 2.5 × 10-8 A/cm2). Whereas, in HCl, the opposite relationship was observed (Astra 2.9 × 10-4 ± 0.8 × 10-4 A/cm2 and Apollo 62.7 × 10-4 ± 9.3 × 10-4 A/cm2). An average reactive anodic current density in NaCl for Astra amounted up to ~0.2 × 10-5-1.5 × 10-5 A/cm2, while for Apollo-up to ~3.3-9.7 × 10-7 A/cm2. The composition of both alloys after corrosion in NaCl demonstrated some changes: a decrease in the Ti, and Al and an increase in oxygen content. Hence, both alloys after corrosion in HCl demonstrated some minor changes in the elemental composition. Based on the results it can be concluded that: 1. Astra and Apollo abutments revealed good corrosion resistance and a passivation layer on the surface. 2. Apollo abutments exhibited better corrosion resistance in a neutral environment, suggesting that Astra abutments were found to be more resistant to corrosion in an acidic medium.

A Devonian crinoid with a diamond microlattice.

Owing to their remarkable physical properties, cellular structures, such as triply periodic minimal surfaces (TPMS), have multidisciplinary and multifunctional applications. Although these structures are observed in nature, examples of TPMS with large length scales in living organisms are exceedingly rare. Recently, microstructure reminiscent of the diamond-type TPMS was documented in the skeleton of the modern knobby starfish Protoreaster nodosus. Here we report a similar microlattice in a 385 Myr old crinoid Haplocrinites, which pushes back the origins of this highly ordered microstructure in echinoderms into the Devonian. Despite the low Mg2+/Ca2+ ratio of the 'calcite' Devonian sea, the skeleton of these crinoids has high-Mg content, which indicates strong biological control over biomineralogy. We suggest that such an optimization of trabecular arrangement additionally enriched in magnesium, which enhances the mechanical properties, might have evolved in these crinoids in response to increased predation pressure during the Middle Palaeozoic Marine Revolution. This discovery illustrates the remarkable ability of echinoderms, through the process of evolutionary optimization, to form a lightweight, stiff and damage-tolerant skeleton, which serves as an inspiration for biomimetic materials.

Earthworm granules: A model of non-classical biogenic calcium carbonate phase transformations.

Different non-classical crystallization mechanisms have been invoked to explain structural and compositional properties of biocrystals. The identification of precursor amorphous nanoparticle aggregation as an onset process in the formation of numerous biominerals (crystallization via particle attachment) constituted a most important breakthrough for understanding biologically mediated mineralization. A comprehensive understanding about how the attached amorphous particles transform into more stable, crystalline grains has yet to be elucidated. Here, we document structural, biogeochemical, and crystallographic aspects of the formation as well as the further phase transformations of the amorphous calcium carbonate particles formed by cultured specimens of earthworm Lumbricus terrestris. In-situ observations evidence the formation of proto-vaterite after dehydration of earthworm-produced ACC, which is subsequently followed by proto-vaterite transformation into calcite through nanoparticle attachment within the organic framework. In culture medium spiked with trace amounts of Mn2+, the cauliflower-like proto-vaterite structures become longer-lived than in the absence of Mn2+. We propose that the formation of calcite crystals takes place through a non-classical recrystallization path that involves migration of proto-vaterite nanoparticles to the crystallization site, and then, their transformation into calcite via a dissolution-recrystallization reaction. The latter is complemented by ion-by-ion crystal growth and associated with impurity release. These observations are integrated into a new model of the biocrystallization of earthworm-produced carbonate granules which highlights the sensibility of this process to environmental chemical changes, its potential impact on the bioavailability of contaminants as well as the threat that chemical pollution poses to the normal development of its early stages. STATEMENT OF SIGNIFICANCE: Understanding the mechanisms of nucleation, stabilization and aggregation of amorphous calcium carbonate (ACC) and factors controlling its further transformation into crystalline phases is fundamental for elucidation of biogenic mineralization. Some species of earthworms are natural workbench to understand the biogenic ACC, stabilization and the transformation mechanisms, because they create millimeter-sized calcareous granules from amorphous calcium carbonate, which crystallize to a more stable mineral phase (mostly calcite). This study undergoes into the mechanisms of ACC stabilization by the incorporation of trace elements, as manganese, and the ulterior precipitation of calcareous granules by a coupled process of amorphous particle attachment and ion-by-ion growth. The study points to sensibility of this process to environmental chemical changes.

Refinement of the Magnesium-Aluminium Alloy Microstructure with Zirconium.

The magnesium-aluminium alloy AZ91 was inoculated with zirconium to refine the microstructure. Six different concentrations of zirconium content were tested, ranging from 0.1 to 0.6 wt %, and compared to the baseline AZ91 alloy without modification. Melted metal was poured into a preheated ceramic mould and the temperature was measured and recorded during the solidification. The derivative and thermal analysis (DTA) was performed to compare the crystallisation dynamics. Formed microstructure was analysed using an optical microscope, scanning electron microscopy (SEM-EDX) and energy dispersive X-ray spectrometry (XRD). The chemical composition was measured using an arc spectrometer. The time of solidification was shortened for the samples with a concentration of zirconium 0.3 wt % and the microstructure was refined. The level of grain refinement remained below 10% and the grain shape was changed to more spherical shapes. Both the primary magnesium and eutectic phases were modified. However, at a low concentration of zirconium (0.1 and 0.2 wt %), the primary grain size was increased. Therefore, the optimal zirconium concentration was 0.3 wt %. Larger concentrations (0.4 to 0.6 wt %) did not provide any additional benefit. Theoretical analysis showed that some Al3Zr intermetallic phases can form, which was confirmed on the derivate curve of the thermal analysis, and SEM-EDS and XRD analyses.

Influence of Abrasive Treatment on a Transformation of Zirconium Oxide Used in Dental Prosthetics.

Zirconium oxide is a ceramic most often used in the field of dentistry for permanently cementing the substructures of prosthetic restorations in patients. The surface of zirconium oxide should be prepared properly because in the next stage it must be covered with porcelain. The success of prosthetics treatment depends on various factors, but it has been reported that the transformation of zirconium oxide plays a key role. The purpose of the research was to investigate the effect of abrasive blasting on the transformation of zirconium oxide. The research has shown that this type of surface treatment causes the transformation of the tetragonal phase into a monoclinic one. The samples were examined using X-ray diffraction (XRD). The study confirmed the assumption.

The Influence of the Depth of Grinding on the Condition of the Surface Layer of 20MnCr5 Steel Ground with the Minimum Quantity Lubrication (MQL) Method.

This paper describes the research on abrasive machining conditions and their influence on microhardness and residual stresses distribution in the technological surface layer of 20MnCr5 steel. The roughness of ground samples was also measured. Samples underwent a vacuum carburizing process (LPC) followed by high-pressure gas quenching (HPGQ) in a 4D quenching chamber. Processes were realized with a single-piece flow method. Then, the flat surfaces of samples were ground with a Vortex type IPA60EH20VTX alumina grinding wheel using a flat-surface grinder. The samples were ground to three depths of grinding (ae = 0.01; 0.02; 0.03 mm) with grinding fluid supply using either flood method (WET) or minimum quantity lubrication (MQL) method. The condition of the technological surface layer was described using microhardness and residual stresses, as well as some selected parameters of surface roughness. The results obtained revealed that changes in microhardness as compared to microhardness of the material before grinding were lower in samples ground with grinding fluid supplied with MQL method. At the same time, the values of residual stresses were also better for samples ground using MQL method. Furthermore, the use of grinding fluid fed with MQL method produced lower values of surface roughness compared to the parameters obtained with WET method. It was concluded that for the tested scope of machining conditions, the MQL method can be a favourable alternative to the flood method of supplying grinding fluid into the grinding zone.

Impact of a Graphene Oxide Reducing Agent on a Semi-Permeable Graphene/Reduced Graphene Oxide Forward Osmosis Membrane Filtration Efficiency.

Graphene has been considered as a material that may overcome the limitations of polymer semi-permeable membranes in water treatment technology. However, monolayer graphene still suffers from defects that cause leakage. Here, we report a method of sealing defects in graphene transferred onto porous polymer substrate via reduced graphene oxide (rGO). The influence of various reducing agents (e.g., vitamin C, hydrazine) on the properties of rGO was investigated by SEM, Raman, FTIR, and XRD. Subsequently, membranes based on graphene/reduced graphene oxide were tested in a forward osmosis system using sodium chloride (NaCl). The effect of the effectiveness of the reduction of graphene oxide, the type and number of attached groups, the change in the distance between the rGO flakes, and the structure of this material were examined in terms of filtration efficiency. As a result, semi-permeable centimetre-scale membranes with ion blocking efficiency of up to 90% and water flux of 20 mL h-1 m-2 bar-1 were proposed.

Analysis of the Surface Condition and Changes in Crystallographic Structure of Zirconium Oxide Affected by Mechanical Processing.

Zirconium oxide is a material commonly used in dental prosthetics for making cups of permanent prosthetic restorations. In order to properly prepare the surface of zirconium oxide for prosthetic treatment, it must be veneered with ceramics. The quality of cup-veneered ceramics is dependent on many factors, including the surface free energy (SFE) and transformation of zirconium oxide. The aim of the study was to investigate the type of phase transition and the value of free energy of the surface subjected to machining (wet and dry grinding, polishing). Quantitative and qualitative phase identification measurements showed that mechanical treatment causes transformation of the tetragonal phase into a monoclinic phase in the zirconium oxide surface. Prepared samples were analyzed by means of X-ray diffraction (XRD), which confirmed the phenomenon of transition. Measurements of the wetting angle and the calculated values of the surface free energy (SFE) showed no significant differences between the samples subjected to each treatment.

Perovskite versus ZnCuInS/ZnS Luminescent Nanoparticles in Wavelength-Shifting Layers for Sensor Applications.

In this work, the application of quantum dots is evaluated in order to sensitize the commercially popular Si detectors in the UV range. The wavelength-shifting properties of two types of all-inorganic halide perovskite quantum dots as well as ZnCuInS/ZnS quantum dots are determined in order to assess their potential in the effective enhancement of the sensors' detection range. In a further part of the study, the wavelength-shifting layers are formed by embedding the quantum dots in two kinds of polymers: PMMA or Cyclic Olefin Polymer. The performance of the layers is evaluated by transmission and PLE measurement. Incorporating the nanoparticles seemingly increases the transmittance in the UV range by several percent. The observed phenomenon is proportional to the quantum dots to polymer concentration, which indicates the successful conversion action of the luminescent agents.

Comparison of Different Thermo-Chemical Treatments Methods of Ti-6Al-4V Alloy in Terms of Tribological and Corrosion Properties.

Titanium and its alloys are characterized by high mechanical strength, good corrosion resistance, high biocompatibility and relatively low Young's modulus. For many years, one of the most commonly used and described titanium alloys has been Ti-6Al-4V. The great interest in this two-phase titanium alloy is due to the broad possibilities of shaping its mechanical and physico-chemical properties using modern surface engineering techniques. The high coefficient of friction and tendency to galling are the most important drawbacks limiting the application of this material in many areas. In this regard, such methods as carburizing, nitriding, oxidation, and the synthesis of thin films using physical vapor deposition (PVD) and chemical vapor deposition (CVD) methods may significantly improve the tribological properties of titanium alloys. The influence of thermo-chemical treatment (oxidation, carburizing and nitriding) on tribological properties and corrosion resistance of Ti-6Al-4V alloy is presented in this paper. The results include metallographic studies, analysis of tribological and mechanical properties and corrosion resistance as well. They indicate significant improvements in mechanical properties manifested by a twofold increase in hardness and improved corrosion resistance for the oxidation process. The carburizing was most important for reducing the coefficient of friction and wear rate. The nitriding process had the least effect on the properties of Ti-6Al-4V alloy.

Frictional Behaviour of Composite Anodized Layers on Aluminium Alloys.

Three variants of the micro arc oxidation (MAO) technique have been used to treat a 2017A alloy surface. The first variant was a pure anodized layer, the second an anodized layer with SiC embedded nanoparticles and the third an anodized layer with Si3N4 nanoparticles. Tribological tests were performed for all variants, on three samples for every case. Friction coefficients and wear rates were calculated on the basis of experiments. The pure anodized layer manifested friction coefficient values within the range of 0.48 ÷ 0.52 and a wear rate in the range ~10-15 m3N-1m-1. SiC nanoparticles improved the tribological properties of the layer, as indicated by a reduction of the friction coefficient values to the range of 0.20 ÷ 0.26 with preserved very high resistance against wear (wear rate ~10-15 m3N-1m-1). Si3N4 particles embedded in anodized layer deteriorated the tribological properties, with a reduction in the resistance against fatigue and wear, intensification of friction forces and a change in the nature of friction contact behavior to more abrasive-like nature (friction coefficients ranging from 0.4 to 0.6 and wear rates ~10-14 m3N-1m-1).

Production of Methane, Hydrogen and Ethanol from Secale cereale L. Straw Pretreated with Sulfuric Acid.

The study describes sulfuric acid pretreatment of straw from Secale cereale L. (rye straw) to evaluate the effect of acid concentration and treatment time on the efficiency of biofuel production. The highest ethanol yield occurred after the enzyme treatment at a dose of 15 filter paper unit (FPU) per gram of rye straw (subjected to chemical hydrolysis with 2% sulfuric acid (SA) at 121 °C for 1 h) during 120 h. Anaerobic digestion of rye straw treated with 10% SA at 121 °C during 1 h allowed to obtain 347.42 L methane/kg volatile solids (VS). Most hydrogen was released during dark fermentation of rye straw after pretreatment of 2% SA, 121 °C, 1 h and 1% SA, 121 °C, 2 h-131.99 and 134.71 L hydrogen/kg VS, respectively. If the rye straw produced in the European Union were processed into methane, hydrogen, ethanol, the annual electricity production in 2018 could reach 9.87 TWh (terawatt-hours), 1.16 TWh, and 0.60 TWh, respectively.

Degradation of ozonized tire rubber by aniline - Degrading Candida methanosorbosa BP6 strain.

Aniline-degrading yeast strain - Candida methanosorbosa BP-6 was tested for its ability to degrade ground tire rubber, treated and non-treated with ozone. The protein content, respiratory activity, critical oxygen concentration (COC) and emulsifying activity of the yeast strain were monitored during 21 day degradation process. The effects of biodegradation were evaluated using aldehyde detection, Scanning Electrone Microscope (SEM) and Fourier-transform infrared spectroscopy (FTIR) analysis. Pre-treatment of ground tire rubber with ozone resulted in lower microbial growth. However, metabolic condition of the C. methanosorbosa BP-6 yeast strain was higher in sample with ozonized tire rubber. Furthermore, the COC values in the last days of the process were about 30% lower regarding non-ozonized polymer. Also, the ozonization of tire rubber resulted in higher biosurfactant production of the yeast strain. The roughness and visible gaps in rubber matrix (SEM analysis) confirmed the ability of Candida methanosorbosa BP-6 yeast strain for tire rubber biodegradation.

Ozonolysis of straw from Secale cereale L. for anaerobic digestion.

The effect of different ozonation conditions on straw from Secale cereale (rye straw) pretreatment has been investigated. Using the Taguchi method, this study analyzed the optimum conditions for pretreatment of rye straw by ozonation. After 60min of rye straw ozonation the concentration of reducing sugars (RS) and volatile fatty acid (VFA), chemical oxygen demand (COD) were 7.4, 32.3 and 11.7 times higher, respectively compared to samples raw rye straw. The most effective rye straw ozonation occurred while using the highest amount of the rye straw (15g) treated with lower ozone dose (100gO3/m3) in the longest period of time (60min). For this variant of experiment the increment of methane production was 291.71dm3CH4/kgVS. Moreover, co-digestion of sewage sludge with addition of 20% ozonated rye straw allowed to obtain 269.1dm3CH4/kgVS. The positive effect of ozone on changes in the rye straw structure has been confirmed by SEM and FTIR analysis.