Do oral biofilms influence the wear and corrosion behavior of titanium?

The main aim of this work was to study the simultaneous wear-corrosion of titanium (Ti) in the presence of biofilms composed of Streptococcus mutans and Candida albicans. Both organisms were separately grown in specific growth media, and then mixed in a medium supplemented with a high sucrose concentration. Corrosion and tribocorrosion tests were performed after 48 h and 216 h of biofilm growth. Electrochemical corrosion tests indicated a decrease in the corrosion resistance of Ti in the presence of the biofilms although the TiO₂ film presented the characteristics of a compact oxide film. While the open circuit potential of Ti indicated a tendency to corrosion in the presence of the biofilms, tribocorrosion tests revealed a low friction on biofilm covered Ti. The properties of the biofilms were similar to those of the lubricant agents used to decrease the wear rate of materials. However, the pH-lowering promoted by microbial species, can lead to corrosion of Ti-based oral rehabilitation systems.     

Tantalum Nitride-Decorated Titanium with Enhanced Resistance to Microbiologically Induced Corrosion and Mechanical Property for Dental Application

Microbiologically induced corrosion (MIC) of metallic devices/implants in the oral region is one major cause of implant failure and metal allergy in patients. Therefore, it is crucial to develop practical approaches which can effectively prevent MIC for broad clinical applications of these materials. In the present work, tantalum nitride (TaN)-decorated titanium with promoted bio-corrosion and mechanical property was firstly developed via depositing TaN layer onto pure Ti using magnetron sputtering. The microstructure and chemical constituent of TaN coatings were characterized, and were found to consist of a hard fcc-TaN outer layer. Besides, the addition of TaN coatings greatly increased the hardness and modulus of pristine Ti from 2.54 ± 0.20 to 29.88 ± 2.59 GPa, and from 107.19 ± 6.98 to 295.46 ± 19.36 GPa, respectively. Potentiodynamic polarization and electrochemical impedance spectroscopy studies indicated that TaN coating exhibited higher MIC resistance in comparison to bare Ti and TiN-coated coating in two bacteria-containing artificial saliva solutions. Moreover, the biofilm experiment showed that the TaN-decorated Ti sample possessed good antibacterial performance. The SEM and XPS results after biofilm removal demonstrated that TaN film remained its integrity and stability, while TiN layer detached from Ti surface in the bio-corrosion tests, demonstrating the anti-MIC behavior and the strong binding property of TaN coating to Ti substrate. Considering all these results, TaN-decorated Ti material exhibits the optimal comprehensive performance and holds great potential as implant material for dental applications.     

Electrochemical prevention of marine biofouling on a novel titanium-nitride-coated plate formed by radio-frequency arc spraying

We have developed a new method for forming titanium-nitride(TiN)-coated plates using radio-frequency arc spraying (RFAS). A TiN coating formed by RFAS has been used for electrochemical prevention of marine biofouling. X-ray diffraction and X-ray photoelectron spectroscopy indicate that a TiN composite film containing Ti was formed on a polyethylene terephthalate plate surface when Ti was sprayed by RFAS under atmospheric pressure. A cyclic voltammogram (scan rate 20 mV/s) of the TiN formed by RFAS revealed no oxidative and reductive peak currents in the range −0.6 V to 1.2 V against a saturated silver/silver chloride (Ag/AgCl) electrode. When a potential of 1.0 V against Ag/AgCl was applied to the electrode in seawater, no dissolved Ti was detected. Changes in pH and the chlorine concentration were not observed in this range. In all, only 4.5% of the Vibrio alginolyticus cells attached to the electrode survived when a potential of 0.8 V against Ag/AgCl was applied in seawater for 30 min. In field experiments, attachment of the organisms to the TiN electrode was inhibited by applying an alternating potential of 1.0 V and −0.6 V against Ag/AgCl. The TiN film can be formed by RFAS on large and intricately shaped surfaces, and it is a practical electrode for the electrochemical prevention of fouling of various marine structures. Received: 17 April 1998 / Received revision: 5 June 1998 / Accepted: 19 June 1998     

Investigation of interfacial capacitance of Pt,Ti and TiN coated electrodes by electrochemical impedance spectroscopy

Electrochemical processes at the electrode-electrolyte (body fluid) interface are of ultimate importance for stimulating/sensing electrode function. A high electrode surface area is desirable for safe stimulation through double-layer charging and discharging. Pt and Pt-Ir alloys have been the most common electrode materials. The use of TiN coating as the surface layer on the electrode has found increasing interest because of its metal-like conductivity, excellent mechanical and chemical properties, and the fact that it can be deposited with a high surface area. In this work, electrochemical impedance spectroscopy (EIS), which is a sensitive and non-destructive technique and widely used for characterization of electrical properties of electrode-electrolyte interfaces, was applied to investigate pure Pt and Ti, and TiN coated electrodes exposed to a phosphate-buffered-saline (PBS) solution. Platinized Pt and Ti were also studied for comparison. The capacitance value of the electrodes in PBS was obtained through quantitative analysis of the EIS spectra. The results reveal that the capacitance of the TiN coated electrodes with a rough surface is several hundreds times higher than that of a smooth Pt surface. Platinization of Ti can also increase the capacitance to the same extent as platina. EIS has been shown to be a powerful technique for characterization of stimulating/sensing electrodes.     

Microstructure analysis and wear behavior of titanium cermet femoral head with hard TiC layer

Titanium cermet was successfully synthesized and formed a thin gradient titanium carbide coating on the surface of Ti6Al4V alloy by using a novel sequential carburization under high temperature, while the titanium cermet femoral head was produced. The titanium cermet phase and surface topography were characterized with X-ray diffraction (XRD) and backscattered electron imaging (BSE). And then the wear behavior of titanium cermet femoral head was investigated by using CUMT II artificial joint hip simulator. The surface characterization indicates that carbon effectively diffused into the titanium alloys and formed a hard TiC layer on the Ti6Al4V alloys surface with a micro-porous structure. The artificial hip joint experimental results show that titanium cermet femoral head could not only improve the wear resistance of artificial femoral head, but also decrease the wear of UHMWPE joint cup. In addition, the carburized titanium alloy femoral head could effectively control the UHMWPE debris distribution, and increase the size of UHMWPE debris. All of the results suggest that titanium cermet is a prospective femoral head material in artificial joint.     

Electrochemical detection of DNA hybridization using a change in flexibility

A novel electrochemical method of detecting DNA hybridization is presented based on the change in flexibility between the single and double stranded DNA. A recognition surface based on gold nanoparticles (GNPs) is firstly modified via mixing self-assembled monolayer of thiolated probe DNA and 1,6-hexanedithiol. The hybridization and electrochemical detection are performed on the surface of probe-modified GNPs and electrode, respectively. Here in our method the charge transfer resistance (R(ct)) signal is enhanced by blocking the surface of electrode with DNA covered GNPs. The GNPs will be able to adsorb on the gold electrode when covered with flexible single stranded DNA (ssDNA). On the contrary, it will be repelled from the electrode, when covered with stiff double stranded DNA (dsDNA). Therefore, different R(ct) signals are observed before and after hybridization. The hybridization events are monitored by electrochemical impedance spectroscopy (EIS) measurement based on the R(ct) signals without any external labels. This method provides an alternative route for expanding the range of detection methods available for DNA hybridization.     

纳米结构Ti/TiN涂层对NiTi合金生物相容性的影响

目的：评价纳米结构Ti/TiN涂层对镍钛形状记忆合金（含镍50.6at%）生物相容性的影响,为生物医用纳米结构Ti/TiN涂层表面改性的NiTi合金材料生物安全性提供依据。方法：不影响基体的形状记忆性或超弹性效应的前提下,采用真空过滤电弧离子镀技术,在NiTi合金表面沉积一层纳米结构Ti/TiN涂层,分别对表面改性前和改性后的NiTi合金样品进行体外细胞毒性实验、溶血实验和血小板粘附实验,探索纳米结构Ti/TiN涂层对NiTi合金生物相容性的影响。结果：表面具有纳米结构Ti/TiN涂层的NiTi合金无细胞毒性,H9C2（2-1）细胞相容性优于涂层前,细胞形态典型,粘附数量明显大于涂层前。纳米结构Ti/TiN涂层有改善NiTi合金的血液相容性作用,其溶血率从2.1%降至涂层改性后的1.2%,同时,血小板黏附量和聚集程度小于处理前的NiTi合金。结论：纳米Ti/TiN涂层能够显著改善NiTi合金的生物相容性。     

Fatigue Performance of Medical Ti6Al4V Alloy after Mechanical Surface Treatments

Mechanical surface treatments have a long history in traditional engineering disciplines, such as the automotive or aerospace industries. Today, they are widely applied to metal components to increase the mechanical performance of these. However, their application in the medical field is rather rare. The present study aims to compare the potential of relevant mechanical surface treatments on the high cycle fatigue (R = 0.1 for a maximum of 10 million cycles) performance of a Ti6Al4V standard alloy for orthopedic, spinal, dental and trauma surgical implants: shot peening, deep rolling, ultrasonic shot peening and laser shock peening. Hour-glass shaped Ti6Al4V specimens were treated and analyzed with regard to the material’s microstructure, microhardness, residual stress depth profiles and the mechanical behavior during fatigue testing. All treatments introduced substantial compressive residual stresses and exhibited considerable potential for increasing fatigue performance from 10% to 17.2% after laser shock peening compared to non-treated samples. It is assumed that final mechanical surface treatments may also increase fretting wear resistance in the modular connection of total hip and knee replacements.     

In situ surface electrochemical characterizations of Ti and Ti-6Al-4V alloy cultured with osteoblast-like cells

The biocompatibility of metal implants is related to their surface electrochemical characterizations. The in situ growing process of osteoblast-like U-2 OS cells on polished Ti and Ti-6Al-4V alloy during 72h incubation was monitored using the electrochemical impedance spectroscopy (EIS) measurement technique. The results showed that the presence of cells on metals led to an increase in the impedance and polarization resistance (R(p)) of metals. The impedance and R(p) increased as the cells grew (i.e., from adhesion, spreading to proliferation period). A trace amount of V element released from Ti-6Al-4V alloy led to a lower R(p) with respect to Ti metal during cell culture. In this study, a satisfactory equivalent circuit simulating the electrochemical characterizations of Ti and Ti-6Al-4V alloy cultured with cells was proposed. The EIS measurement technique was applied successfully to monitor the in situ growing process of U-2 OS cells on Ti and Ti-6Al-4V alloy.     

Optimization of label-free DNA detection with electrochemical impedance spectroscopy using PNA probes

DNA biosensors, especially those based upon detection of the intrinsic negative charge of target DNA, can be greatly improved by the use of uncharged peptide nucleic acid (PNA) probes. Hybridization causes an increased electrostatic barrier for the negatively charged ferri/ferrocyanide redox couple, resulting in an increase in charge transfer resistance R(ct) that is measured using electrochemical impedance spectroscopy. We report on the optimization of PNA probe surface density by the simultaneous co-immobilization of thiol-modified probes and mercaptohexanol, with the PNA surface density controlled by the thiol mole ratio in solution. Maximum R(ct) change upon hybridization is obtained with 10% PNA mole fraction. The effect of the measurement buffer ionic strength is investigated. The electrostatic barrier for charge transfer to the ferri/ferrocyanide redox couple is approximately independent of ionic strength with PNA probes, but greatly increases with decreasing ionic strength, after hybridization with target DNA. This significantly enhances the R(ct) change upon hybridization. The optimization of PNA surface density and measurement buffer ionic strength leads to a 385-fold increase in R(ct) upon hybridization, a factor of 100 larger than previously reported results using either PNA or DNA probes.     

A biocompatible titanium nitride nanorods derived nanostructured electrode for biosensing and bioelectrochemical energy conversion

In this study, a facile method is proposed to fabricate biocompatible TiN nanorod arrays through solvent-thermal synthesis and subsequent nitridation in ammonia atmosphere. The TiN nanorod arrays are potential excellent nanostructured electrodes owing to their good electronic conductivity and large surface area. These nanostructured electrodes not only deliver superior electrocatalytic activity (the limit of detection, LOD is 0.5 μM) and highly selective sensing towards H(2)O(2), but also exhibit excellent biocompatibility with horseradish peroxidase (HRP) in a highly sensitive enzymatic biosensor for H(2)O(2) (the LOD can reach to 0.05 μM). Furthermore, a novel biocatalytic cathode based Li air fuel cell (bio-Li-air fuel cell) is explored based on the combination of TiN nanorod arrays and laccase (LAC) for electrochemical energy conversion. These results demonstrate that TiN nanorod arrays can be served as excellent nanostructured electrodes for multifunctional bioelectrochemical applications.     

Influence of Bio-Lubricants on the Tribological Properties of Ti6Al4V Alloy

Titanium alloy is one of the best materials for biomedical applications due to its superior biocompatibility, outstanding corrosion resistance, and low elastic modulus. However, the friction and wear behaviors of titanium alloys were sensitive to the environment including lubrication. In order to clarify the wear mechanism of titanium alloy under different lubrications including deionized water, physiological saline and bovine serum, the friction and wear tests were performed between Ti6Al4V plates and Si₃N₄ ball on a universal multi-functional tester. The friction and the wear rate of titanium alloy were measured under dry friction and three different lubrication conditions. The worn surfaces were examined by scanning electron microscopy. The results revealed that under the dry friction, the wear resistance of titanium alloy was the worst since the wear mechanism was mainly the combination of abrasive wear and oxidation wear. It was also found that Ti6Al4V alloy had low friction coefficient and wear rate under three lubrication conditions, and its wear mechanism was adhesive wear.     

DNA deposition on carbon electrodes under controlled dc potentials

The native calf-thymus DNA molecule fully dispersed in solution was deposited onto highly oriented pyrolytic graphite, carbon fiber column and disk electrodes under controlled dc potentials. X-ray photoelectron spectroscopy, atomic force microscopy and electrochemical investigations indicated that network structures of DNA could be formed on various carbon electrode surfaces resulting in significant surface enlargement. The conformation, conductivity and stability of the deposited DNA layer largely depended on the concentration of the DNA deposition solution, the applied dc potential and the mode of electric field. The optimal condition for deposition of the DNA on carbon fiber disk electrode was determined as a deposition potential of 1.8 +/- 0.3 V versus 50 mM NaCl-Ag/AgCl and a deposition DNA solution of 0.1 mg ml(-1). Under this condition, the DNA was covalently bonded on the electrode surface forming a three-dimensional modified layer, generating a 500-fold enlarged effective electrode surface area and similarly enlarged current sensitivity for redox species, such as Co(phen)3(3+). A possible mechanism for the formation of DNA networks is proposed.     

Demonstration of biofilm removal from type 304 stainless steel using pulsed-waveform electropolishing

Abstract

This article describes an electrochemical method to remove bacterial biofilm from a stainless steel (SS) surface using a potential pulse/reverse pulse technique. This technique employs a periodic waveform that consists of anodic and cathodic pulses. The pulses can effectively strip a thin layer of metal off the SS surface, along with the adherent biofilm, in a saline solution. Not only can the pulses effectively remove biofilm from the SS surface, but they also regenerate the original mirror-like shiny surface. The importance of this electrochemical biofilm removal method is its wide applicability for any types of biofilms. That is, instead of directly removing the biofilm, it removes a very thin layer of the metal under the biofilm. Thus, the removal process is independent to the nature of the biofilms. Furthermore, this electrochemical biofilm removal method is rapid (less than 30?s of potential pulse time) and does not require hazardous chemicals.     

Electrochemical potential of free and immobilized Cratylia mollis seed lectin

The electrochemical potentials for free or immobilized Cratylia mollis seed lectin (Cra) were obtained through potentiostatic techniques. A saline solution was used as support to control the charge distribution between saturated calomel electrode and platinum electrode (working electrode). The electrochemical potential to free Cra was determined at the following concentrations: 0.6, 0.9 and 1.0 mg/ml in an aerated environment under different temperatures (5, 10 and 20 degrees C). The best electrochemical potential was obtained with 1.0 mg/ml, at 5 and 10 degrees C, 87 and 102 mV, respectively. Electrochemical potential to Cra immobilized on glass beads activated with 3-aminopropyltriethoxysilane described a linear behavior in relation to the increase in glucose concentration. The development of techniques to define interface electrical parameters will be able to give information about charged groups adsorbed to electrode surface revealing interactions particularly in biological systems.     

Comparison of amperometric biosensors fabricated by palladium sputtering, palladium electrodeposition and Nafion/carbon nanotube casting on screen-printed carbon electrodes

Different strategies, including palladium electrodeposition (Pd(CV)), Pd sputtering (Pd(S)) and Nafion-solubilized carbon nanotube casting (Nafion/CNT), were used to modify screen-printed carbon electrodes (SPCEs) for the fabrication of amperometric enzyme biosensors. The electrochemical properties of the bare and modified SPCEs and the optimal conditions for surface modification were determined. The electrochemical response of the bare SPCE to H(2)O(2) under the potential of 0.3 V could be improved about 100-fold by Pd modification by electrodeposition or sputtering. By contrast, the electrochemical response of the bare SPCE was enhanced by only about 11-fold by Nafion/CNT casting. Moreover, the Pd(CV)-SPCEs exhibited better reproducibility of electrochemical response (a relative standard deviation (R.S.D.)<6.0%) than freshly prepared Pd(S)-SPCEs (R.S.D.>10%). The glucose biosensor fabricated from Pd-modified electrodes could be stored for up to 108 days without loosing significant activity. The Pd(CV)-SPCE also showed very reliable signal characteristics upon 50 consecutively repeated measurements of ascorbic acid. The electrocatalytic detection of the Pd-SPCE was combined with additional advantages of resistance to surface fouling and hence good stability. In conclusion, this study demonstrated that deposition of Pd thin film on SPCEs by electrodeposition or sputtering provided superior enhancement of electrochemical properties compared to Nafion/CNT-SPCEs. Despite their high electrochemical response, Pd(S)-SPCEs required an activation process to improve stability and Pd(CV)-SPCEs suffered from poor between electrode reproducibility.     

The effect of mucin,fibrinogen and IgG on the corrosion behaviour of Ni–Ti alloy and stainless steel

In this study, Ni–Ti alloy and stainless steal were exposed to artificial saliva containing fibrinogen, IgG or mucin, and the resultant corrosion behavior was studied. The purpose was to determine the mechanisms by which different types of protein contribute to corrosion. The effect of different proteins on the electrochemical resistance of Ni–Ti and SS was tested by potentiodynamic polarization, and the repair capacity of passivation film was tested by cyclic polarization measurements. The dissolved corrosion products were determined by ICP-OES, and the surface was analyzed by SEM and AFM. The results showed fibrinogen, IgG or mucin could have different influences on the susceptibility to corrosion of the same alloy. Adding protein lead to the decrease of corrosion resistance of SS, whereas protein could slow down the corrosion process of Ni–Ti. For Ni–Ti, adding mucin could enhance the corrosion stability and repair capacity of passivation film. The susceptibility to pitting corrosion of Ni–Ti and stainless steal in fibrinogen AS is not as high as mucin and IgG AS. There are different patterns of deposition formation on the metal surface by different types of protein, which is associated with their effects on the corrosion process of the alloys.     

Wear Behavior of Plasma Oxidized CoCrMo Alloy under Dry and Simulated Body Fluid Conditions

In this study, CoCrMo alloy was oxidized in plasma environment at the temperatures of 600 ℃ to 800 ℃ for 1 h to 5 h with 100% 02 gas and its tribological behavior was investigated. After the plasma oxidizing process, the compound and diffusion layers were formed on the surface. XRD results show that Cr203, a-Co and ε-Co phases diffracted from the modified layers after plasma oxidizing. The untreated and treated CoCrMo samples were subjected to wear tests both in dry and simulated body fluid conditions, and normal loads of 2 N and 10 N were used. For the sliding wear test, alumina balls were used as counter materials. It was observed that the wear resistance of CoCrMo alloy was increased after the plasma oxidizing process. The lowest wear rate was obtained from the samples that were oxidized at 800 ℃ for 5 h. It was detected that both wear environment and load have significant effects on the wear behavior of this alloy, and the wear resistance of oxidized CoCrMo alloy is higher when oxide-based counterface is used. The wear rates of both untreated and plasma oxidized samples increase under high loads.     

Label free novel electrical detection using micromachined PZT monolithic thin film cantilever for the detection of C-reactive protein

In this paper, we report the novel electrical measurement for the label-free detection of C-reactive protein (CRP) using resonant frequency shift in the monolithic thin film cantilever of micromachined Pb(Zr0.52Ti0.48)O3 (PZT) which was fabricated with the composition of SiO2/Ta/Pt/PZT/Pt/SiO2 on silicon nitride (SiNx) supporting layer for the dual purpose of electrical self-excitation and sensing. The specific binding characteristics of CRP antigen to its antibody, which is immobilized with Calixcrown SAMs on Au surface deposited on microcantilever, is determined in high sensitivity to the nanogram level per milliliter by measuring the resonant frequency shift. The nanomechanical PZT cantilever turns out a robust platform for the highly specific antigen-antibody interaction and provides with the novel tool for qualification and quantification of biomolecules without any sample labeling and bulky optical apparatus.     

Impedimetric biosensor based on cell-mediated bioimprinted films for bacterial detection

This work presents the synthesis of bacteria-mediated bioimprinted films for selective bacterial detection. Marine pathogen sulfate-reducing bacteria (SRB) were chosen as the template bacteria. Chitosan (CS) doped with reduced graphene sheets (RGSs) was electrodeposited on an indium tin oxide electrode, and the resulting RGSs-CS hybrid film served as a platform for bacterial attachment. The electrodeposition conditions were optimized to obtain RGSs-CS hybrid films with excellent electrochemical performance. A layer of nonconductive CS film was deposited to embed the pathogen, and acetone was used to wash away the bacterial templates. Electrochemical impedance spectroscopy was performed to characterize the stepwise modification process and monitor the SRB population. Faradic impedance measurements revealed that the charge transfer resistance (R(ct)) increased with increased SRB concentration. A linear relationship between ΔR(ct) and the logarithm of SRB concentration was obtained within the concentration range of 1.0×10(4)cfumL(-1) to 1.0×10(8)cfumL(-1). The impedimetric sensor showed good selectivity towards SRB based on size and shape. Hence, selectivity for bacterial detection can be improved if the bioimprinting technique is combined with other bio-recognition elements.