The effect of lignin on the structure and characteristics of composite coatings electrodeposited on titanium

Composite coatings based on lignin, obtained by electrophoretic deposition (EPD) on titanium, were investigated. The aim of this work was to produce hydroxyapatite/lignin (HAP/Lig) coatings on titanium and to investigate the effect of the lignin concentration on microstructure, morphology, phase composition, thermal behavior and cytotoxicity of the HAP/Lig coatings. An organosolv lignin was used for the production of the composite coatings studied in this research. The properties of HAP/Lig coatings were characterized using X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM), thermogravimetric analysis (TGA), attenuated total reflection Fourier transform infrared spectroscopy (ATR-FT-IR) and X-ray photoelectron spectroscopy (XPS), as well as the MTT test of cytotoxicity. The results showed that higher lignin concentrations protected the HAP lattice during sintering, thereby improving the stability of the HAP/Lig coatings. The cell survival of peripheral blood mononuclear cells (PBMC) after proliferation indicates that the HAP/Lig coating with 1 wt% Lig electrodeposited on titanium was non-toxic with significant promise as a potential bone-repair material.     

Ternary hydroxyapatite/chitosan/graphene oxide composite coating on AZ91D magnesium alloy by electrophoretic deposition

In this work, ternary HA/chitosan/graphene oxide (GO) coating was applied via electrophoretic deposition on AZ91D magnesium alloy as bone implants, successfully. Subsequently, phase composition, surface morphology, hardness, corrosion behavior, bioactivity and antibacterial of the composite coatings were studied. Hardness and Young's modulus of the composite coatings increased from 40 ± 1.5 MPa and 3.1 ± 0.42 GPa to 60 ± 3.12 MPa and 8 ± 0.53 GPa for composite coatings with 0 and 2 wt% GO, respectively. The results of the SBF solution soaking of the composites after 24 days, indicated the improvement of HA growth due to the increasing of the GO addition in composite coating. New HA grains with leaf-like morphology grew uniformly at higher amounts of GO (1 and 2 %wt) in a perfectly balanced composition. Rate of the substrate corrosion significantly decreased from 4.3 to 0.2 (mpy), when the amount of GO increased from 0 to 2 wt% due to reduction of the surface cracks at the presence of the GO reinforcement. Also, there was no Escherichia coli and Staphylococcus aureus bacteria growth in broth medium after 24 h and OD₆₀₀ results at 24 h post inoculation for the 2%wt GO addition in coating.     

Hydroxyapatite-carboxymethyl cellulose-graphene composite coating development on AZ31 magnesium alloy: Corrosion behavior and mechanical properties

In this study, hydroxyapatite (HA) coatings containing carboxymethyl cellulose (CMC) and graphene (Gr) were developed on AZ31 magnesium alloy through two-step electrophoretic deposition method. The morphology and chemical bonding of coatings were characterized and also the phase identification was done using scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction, respectively. Moreover, the corrosion behavior of the applied coatings was compared with the bare AZ31 Mg alloy substrate in the simulated body fluid by the means of potentiodynamic polarization test and electrochemical impedance spectroscopy. Obtained results revealed that the novel HA-CMC-Gr coating possesses the highest corrosion resistance compared to the HA, HA-CMC, and HA-Gr coatings due to its uniform and compact structure. To investigate the mechanical properties and to elucidate the effect of CMC on the adhesion of coating-alloy interface, pull-off test was employed, where results demonstrated that the addition of CMC increases the adhesion force from 1.06 MPa to 1.62 MPa. Besides, the modulus of elasticity and the hardness of HA and HA-Gr composite coatings were compared by applying nanoindentation test. Interestingly, it is detected that the presence of Gr has considerably increased the elastic modulus of the coating by approximately 30% in comparison to the pure HA coating.     

Electrodeposition of fluorohydroxyapatite gradient coating on titanium alloy

In order to obtain the apatite implants which can meet the requirements for both bonding strength and bioactivity, the FHA(Ca₁₀(PO₄)₆OH_2−xF_x(x = 0 ~ 2)) gradient coating was prepared by electrophoretic deposition on the surface of titanium alloy (Ti–6Al–4V). The effects of fluorine substitution and gradient structure on the morphology, bonding strength, and bioactivity of the coating were investigated. The gradient coating has the dense inner layer and porous outer layer that were deposited by controlling the suspension concentration and the preparation process. Through controlling of the fluorine substitution gradient, the thermal expansion coefficient gradually changed to improve the bonding strength more than 30 Mpa. The inner layer with high fluorine content can improve the thermal stability of the coating and bonding strength between the coating and the substrate, while the proper content of fluorine in the outer layer improves the bioactivity of the gradient coating.     

Structural characterization of YSZ/Al2O3 nanostructured composite coating fabricated by electrophoretic deposition and reaction bonding

Suspension of YSZ and Al particles in acetone in presence of 1.2 g/l iodine as dispersant was used for electrophoretic deposition of green form YSZ/Al coating. Results revealed that applied voltage of 6 V and deposition time of 3 min were appropriate for deposition of green composite form coating. After deposition, a nanostructured dense YSZ/Al₂O₃ composite coating was fabricated by oxidation of Al particles at 600 °C for 2 h and subsequently sintering heat treatment at 1000 °C for 2 h. Melting and oxidation of Al particles in the green form composite coating not only caused reaction bonding between the particles but also lowered the sintering temperature of the ceramic coating about 200 °C. The EDS maps confirmed that the composition of fabricated coating was uniform and Al₂O₃ particles were dispersed homogenously in YSZ matrix.     

Reinforcing effect of graphene nanoplatelets in the electrochemical behaviour of manganese oxide-based supercapacitors produced by EPD

A simple procedure for the manufacture of metal oxide based supercapacitors consisting on the electrophoretic deposition (EPD) onto graphite paper of well-dispersed aqueous slurries of manganese oxide with graphene nanoplatelets is presented. EPD was performed using optimised slurries and depositing onto graphite paper electrodes. In order to improve manganese oxide conductivity graphene nanoplatelets (GNP) were incorporated in a concentration of 20 wt% over the MnO₂ content. The evaluation of the electrochemical properties of the so prepared deposits demonstrates that the addition of GNP improves both the capacity and specific energy, with values of 158 F g⁻¹ and 4 W h Kg⁻¹ respectively, which represents four times the values reported for the bare manganese oxide.     

Facile solvothermal synthesis of a graphene nanosheet-bismuth oxide composite and its electrochemical characteristics

This work demonstrates a novel and facile route for preparing graphene-based composites comprising of metal oxide nanoparticles and graphene. A graphene nanosheet-bismuth oxide composite as electrode materials of supercapacitors was firstly synthesized by thermally treating the graphene-bismuth composite, which was obtained through simultaneous solvothermal reduction of the colloidal dispersions of negatively charged graphene oxide sheets in N,N-dimethyl formamide (DMF) solution of bismuth cations at 180 °C. The morphology, composition, and microstructure of the composites together with pure graphite oxide, and graphene were characterized using powder X-ray diffraction (XRD), FT-IR, field emission scanning electron microscopy (FESEM), transmission electron microscope (TEM), thermogravimetry and differential thermogravimetry (TG-DTG). The electrochemical behaviors were measured by cyclic voltammogram (CV), galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS). The specific capacitance of 255 F g⁻¹ (based on composite) is obtained at a specific current of 1 A g⁻¹ as compared with 71 F g⁻¹ for pure graphene. The loaded-bismuth oxide achieves a specific capacitance as high as 757 F g⁻¹ even at 10 A g⁻¹. In addition, the graphene nanosheet-bismuth oxide composite electrode exhibits the excellent rate capability and well reversibility.     

钛合金基磷酸钙涂层的制备及机理研究

使用电结晶法在钛合金表面沉积磷酸钙薄膜 ,使复合材料具有更好的韧性、强度和生物相容性。涂层沉积的最佳条件为Ca(NO3 ) 2 0 .1 0mol/L ,(NH4) 2 HPO40 .0 6mol/L ,电压 2 .5V ,电极间距离 2 5cm ,pH值 4 .4 ,温度 2 5℃ ,沉积时间 5h。强调了pH值是特别重要的因素 ,并分析了沉积的电化学反应机理     

Painting method for hydroxyapatite coating on titanium substrate

Coating on prostheses and implantable devices is one of the ways to increase the osseointegration of these products. However, plasma spray techniques, that are normally used, present high complexity and high cost. In this work, a new methodology for coating with nanometric hydroxyapatite is presented, with a low cost and ease of production. The technique proposed involves the formation of a suspension of hydroxyapatite (HAp) and oil of turpentine (OT) and its application, with a paintbrush, on the titanium substrate. In order to qualify the process for medical devices, the properties of the titanium substrate, before and after the coating process, the calcium phosphate phases present and the adhesive bond of the coating were evaluated. The results indicated that thermal treatment does not affect the properties of ASTM F67 titanium in order to compromise the properties and the analyses, by X-ray diffraction and Raman spectroscopy, proved that no formation of second phases of calcium phosphate occurred. The adhesive bond assay showed that the coating behaved according to ISO 13779–2, i.e., it had adhesive bond values higher than 15 MPa. The proposed new coating method proved promising for the titanium coating and is an alternative to the complex and high cost processes normally used in metal implants.     

AC vs. DC electrophoretic deposition of hydroxyapatite on titanium

In this study, electrophoretic deposition (EPD) of hydroxyapatite (HA) powder on titanium plate was performed using butanol as solvent under direct current (DC) and alternating current (AC) fields. The zeta potential of the suspensions was measured to define their stability and the charge on the particles. Coating thickness was varied by adjusting the voltage and time of deposition. Surface morphology and cross section thickness were studied using scanning electron microscopy and image analysis software. Surface crack density was calculated from the micrographs. The results showed that the samples of similar thickness have higher grain density when coated using AC as compared to DC EPD. This facile but novel test proves the capability of AC-EPD to attain denser and uniform HA coatings from non-aqueous medium.     

铝–碳纳米管复合镀层的电沉积

采用有机溶剂体系在紫铜基体上电沉积制备Al–碳纳米管(CNTs)复合镀层。镀液组成为:Li Al H4 10 g/L,四氢呋喃600 m L/L,Al Cl3 100 g/L,甲苯400 m L/L,柠檬酸钠20 g/L,分散剂0.4 g/L,CNTs 1 g/L。研究了电流密度、温度、搅拌速率和电镀时间对电沉积Al–CNTs复合镀层的影响,得到较好的工艺条件为:电流密度6 A/dm2,温度25°C,搅拌速率300 r/min,时间40 min。在该工艺条件下制备的Al–CNTs复合镀层呈较光亮的灰白色,厚度约为30μm,镀层的微观表面凹凸不平,但晶粒比纯Al镀层更为细致。     

Development of a novel smart carrier for drug delivery: Ciprofloxacin loaded vaterite/reduced graphene oxide/PCL composite coating on TiO2 nanotube coated titanium

In the field of orthopaedic implants, post-surgery infections and biocompatibility are the most challenging obstacles. Sustained and controlled antibiotic release is a key factor in novel drug delivery systems. A novel drug delivery system combined with vaterite microsphere, graphite oxide (GO), reduced graphene oxide (rGO) incorporated in a polycaprolactone (PCL) matrix on TiO₂ nanotube coated Ti (TNT-Ti) is established. Anodization was employed to develop TiO₂ nanotubular arrays on Ti. Ciprofloxacin hydrochloride (CPF–HCl) loaded vaterite microspheres were synthesized by in situ precipitation method. Deposition of vaterite/PCL, vaterite-GO/PCL and vaterite-rGO/PCL composite coating on TNT-Ti was carried out by dip coating method. The composite coatings were characterized for their phase content, morphological features and functional groups. Among the three types of composite coatings, vaterite-rGO/PCL composite coating is found to be capable of encapsulating CPF-HCl to a level of 75.14 μg. The drug release profile of CPF-HCl from the vaterite-rGO/PCL composite coating exhibits a controlled release amounting to only 35.02 % of release at the end of 120 h. The vaterite-rGO/PCL composite coating exhibits a low dissolution rate and possesses adequate bioactivity in HBSS and SBF solutions at 37 °C for 14 and 10 days, respectively. The in situ loaded CPF-HCL drug on vaterite microspheres, PCL polymer matrix and GO/rGO nanofillers does not affect the cytocompatibility and all the composite coatings supported cell viability and proliferation. The ability of vaterite-rGO/PCL composite coating to provide a slow and steady release of antibiotics with sufficient bioactivity and biocompatibility at the tissue implant interface makes it a promising for osteomyelitis infection of bone tissue implant materials.     

Multi-walled carbon nanotube/polyimide composite film fabricated through electrophoretic deposition

Multi-walled carbon nanotube (MWCNT)/polyimide composite films were fabricated through electrophoretic deposition (EPD) of MWCNT-polyamic acid colloidal suspension which was derived from carboxylated-MWCNTs and poly(pyromellitic dianhydride-co-4,4′-oxydianiline) (PMDA-ODA). Under electric field, both negatively charged MWCNTs and PMDA-ODA colloid particles migrate onto a positively charged anode simultaneously, and are converted to a coherent MWCNT/polyimide composite film in the ensuing imidization reaction. Uniform dispersion of MWCNTs in the composite film was observed using transmission electron microscopy. The thickness of the prepared composite film can be tuned by varying processing conditions such as deposition time and anode conductivity. The electrical conductivity of the composite film increased with increasing the concentration of MWCNTs in EPD suspension. The mechanical reinforcement of polyimide using MWCNTs was evaluated by tensile testing and nanoindentation testing.     

Fabrication of palladium/graphene oxide composite by plasma reduction at room temperature

ABSTRACT: Pd nanoparticles were fabricated on graphene oxide (GO) using a deposition-precipitation method with a glow discharge plasma reduction at room temperature. Argon was employed as the plasma-generating gas. The novel plasma method selectively reduces the metal ions. The graphene oxide has no change with this plasma reduction according to the Fourier transform infrared analysis. The Pd nanoparticles on the GO were uniformly distributed with an average diameter of 1.6 nm. The functional groups on the GO not only prevent Pd nanoparticles from further aggregation but also provide a strong hydrophilic property to the Pd/GO composite, which can form stable colloidal dispersions in water.     

钛植入合金表面电化学沉积掺镁羟基磷灰石涂层

以Ca(NO3)2、(NH4)2HPO4和Mg(NO3)2为原料,采用电化学沉积法在医用钛合金表面制备了掺镁羟基磷灰石涂层,研究了电沉积工艺条件对掺镁羟基磷灰石涂层表面形貌的影响。结果表明,当电流密度为1.0mA/cm2,温度为65°C,pH为4.5,n(Mg):n(Ca)=1:3,电沉积时间为1300s时,得到了均匀致密的晶须状涂层。X射线衍射分析表明,烧结后的掺镁羟基磷灰石涂层中Mg2+取代了Ca2+,使HA涂层的晶格发生了变化。     

在钛基上电泳沉积羟基磷灰石生物陶瓷涂层的研究

将羟基磷灰石(HAP)电泳沉积在钛基材上，得到了结构稳定的HAP生物陶瓷涂层。研究了电场强度、悬浮液温度、电泳时间、分散介质及HAP浓度对涂层形貌的影响。通过红外光谱仪(FTIR)和X射线衍射仪(XRD)对涂层的组成及结构进行了分析，并采用扫描电镜(SEM)对涂层煅烧前后的微观形貌进行了观察。结果表明：在正丁醇作为分散剂、悬浮液温度30℃、电场强度250V／cm、电泳时间300s以及HAP浓度5．0g／L的条件下可制得形貌较好的HAP生物陶瓷涂层；经二次电泳沉积及煅烧后得到的HAP生物陶瓷涂层均匀致密．     

A calcium phosphate coating improving corrosion resistance of the biodegradable magnesium alloy with graphene oxide modifying the deposition

Biodegradable magnesium alloy is an ideal material for medical implant applications, but its application is limited by its rapid degradation. Therefore, it becomes the main goal to improve corrosion resistance. In this study, a calcium phosphate dihydrate/graphene oxide composite coating was designed on the AZ60 alloy for medical applications. A calcium phosphate dihydrate coating was first prepared by biomimetic deposition on the alkali pretreated magnesium alloy, and graphene oxide was dispersed in the solution to modify the deposition. The results showed that graphene oxide could not only alter the loose striped calcium phosphate coating to the compact flaked composite coating, but also enhance the corrosion resistance with a reduced corrosion current density by 2 orders of magnitude, an increased impedance by 3 orders of magnitude and a corrosion rate down to 7/20. The in vitro biocompatibility of the composite coating was also demonstrated by a series cell experiments, with a cell viability of 120%. The composite coating provides a feasible method to enhance the corrosion resistance and biocompatibility of magnesium alloys.     

Corrosion behaviour of plasma sprayed graphene nanoplatelets reinforced hydroxyapatite composite coatings in simulated body fluid

Hydroxyapatite (HA) coatings, reinforced with varied concentration (0–2 wt%) of Graphene nanoplatelets (GNPs) have been deposited on titanium alloys (Ti–6Al–4V) substrate using atmospheric plasma spraying. Present work studies the effect of GNP concentration on the electrochemical behaviour of the HA coatings in simulated body fluid (SBF). The HA coating exhibited 15% porosity, whereas reinforcement of 1 wt% GNPs in HA (HA-1G) shows 13% porosity, further addition of 2 wt% GNPs in HA reduced the porosity to 10%. Reduction in porosity was achieved as GNPs easily accessed the inter-lamellae to fill the gaps at inter splat region and minimized the occurrence of post-plasma spray defects such as porosity, voids, microcracks etc. These consequences nextward resulted in the significant enhancement in corrosion resistance of the matrix. HA-1G displayed a significant reduction by 67% in the corrosion rate in SBF solution, while this reduction came to 87% for HA-2G coatings. Randomly oriented wrinkles in the GNPs after corrosion process and their hydrophobic nature effectively hindered the SBF infiltration into the coating and resisted their movement towards the underlying substrate. This in turn improved the overall corrosion resistance of the system.     

Synthesis,characterization and in-vitro biocompatibility of electrophoretic deposited europium-doped calcium silicate on titanium substrate

Europium (Eu) has attracted attention to be incorporated as biologically active ions to achieve different biological and functional properties of biomaterials. In this study, calcium silicate (CS) coatings doped with different amount of Eu (up to 10 mol%) were successfully formed on titanium substrates via electrophoretic deposition. A low amount of Eu (2.5 mol%) gave a relatively denser coating and improved coating adhesion strength (～3.3 N). All Eu–CS coatings provided good apatite forming ability, yet lower degradation rate, as compared to CS coating. Moreover, it was observed that the human fetal osteoblast (hFOB) cells could attach and proliferate on all Eu–CS coatings, suggesting their biocompatible nature. Eu2.5CS not only showed comparable cell proliferation with CS, but also enhanced the osteogenic activity of the CS coating. All results suggested that Eu2.5CS coatings are promising coating materials for biomedical implants, particularly bone tissue engineering applications.     

Synthesis of zinc oxide nanostructures on graphene/glass substrate by electrochemical deposition: effects of current density and temperature

The electrochemical growth of zinc oxide (ZnO) nanostructures on graphene on glass using zinc nitrate hexahydrate was studied. The effects of current densities and temperatures on the morphological, structural, and optical properties of the ZnO structures were studied. Vertically aligned nanorods were obtained at a low temperature of 75°C, and the diameters increased with current density. Growth temperature seems to have a strong effect in generating well-defined hexagonal-shape nanorods with a smooth top edge surface. A film-like structure was observed for high current densities above -1.0 mA/cm² and temperatures above 80°C due to the coalescence between the neighboring nanorods with large diameter. The nanorods grown at a temperature of 75°C with a low current density of -0.1 mA/cm² exhibited the highest density of 1.45 × 10⁹ cm^-2. X-ray diffraction measurements revealed that the grown ZnO crystallites were highly oriented along the c-axis. The intensity ratio of the ultraviolet (UV) region emission to the visible region emission, I_UV/I_VIS, showed a decrement with the current densities for all grown samples. The samples grown at the current density below -0.5 mA/cm² showed high I_UV/I_VIS values closer to or higher than 1.0, suggesting their fewer structural defects. For all the ZnO/graphene structures, the high transmittance up to 65% was obtained at the light wavelength of 550 nm. Structural and optical properties of the grown ZnO structures seem to be effectively controlled by the current density rather than the growth temperature. ZnO nanorod/graphene hybrid structure on glass is expected to be a promising structure for solar cell which is a conceivable candidate to address the global need for an inexpensive alternative energy source.