Biosurfactant-Assisted Cu Doping of Brushite Coatings: Enhancing Structural, Electrochemical, and Biofunctional Properties.

Stainless steel (316L SS) has been widely used in orthopedic, cardiovascular stents, and other biomedical implant applications due to its strength, corrosion resistance, and biocompatibility. To address the weak interaction between steel implants and tissues, it is a widely adopted strategy to enhance implant performance through the application of bioactive coatings. In this study, Cu-doped brushite coatings were deposited successfully through pulse electrodeposition on steel substrates facilitated with a biosurfactant (BS) (i.e., surfactin). Further, the combined effect of various concentrations of Cu ions and BS on the structural, electrochemical, and biological properties was studied. The X-ray diffraction (XRD) confirms brushite composition with Cu substitution causing lattice contraction and a reduced crystallite size. The scanning electron microscopy (SEM) and energy-dispersive spectroscopy (EDS) studies reveal the morphological changes of the coatings with the incorporation of Cu, which is confirmed by X-ray photoelectron spectroscopy (XPS) and elemental mapping. The Fourier transform infrared (FTIR) and Raman spectroscopy confirm the brushite and Cu doping in the coatings, respectively. Increased surface roughness and mechanical properties of Cu-doped coatings were analyzed by using atomic force microscopic (AFM) and nanohardness tests, respectively. Electrochemical assessments demonstrate corrosion resistance enhancement in Cu-doped coatings, which is further improved with the addition of biosurfactants. In vitro biomineralization studies show the Cu-doped coating's potential for osseointegration, with added stability. The cytocompatibility of the coatings was analyzed using live/dead and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide (MTT) assays; cell adhesion, proliferation, and migration studies were evaluated using SEM. Antibacterial assays highlight significant improvement in the antibacterial properties of Cu-doped coatings with BS. Thus, the developed Cu-doped brushite coatings with BS demonstrate their potential in the realm of biomedical implant technologies, paving the way for further exploration.

Development of Zn-2Cu-xMn/Mg Alloys for Orthopedic Applications: Mechanical Performance to In Vitro Degradation under Different Physiological Environments.

Zinc (Zn) and its alloys are considered futuristic biodegradable materials for their acceptable mechanical properties, suitable corrosion rate, and good biocompatibility. In this study, we report newly developed biodegradable Zn-2Cu-xMn/Mg (x = 0, 0.1, and 0.5) alloys, aiming to achieve good mechanical strength with excellent elongation, desirable wear resistance, and suitable corrosion rate. The effect of Mn/Mg addition on the structural, mechanical, wear, and degradation behaviors of the Zn-2Cu-xMn/Mg alloys was thoroughly investigated. Degradation and tribological behaviors of the alloys were explored in the presence of simulated body fluid (SBF), Dulbecco's modified Eagle medium (DMEM), and DMEM with a 10% fetal bovine serum (FBS) solution. Alloy elements and hot rolling improve their mechanical properties significantly due to precipitation hardening, grain refinement, and solid solution strengthening owing to the formation of MnZn13 and Mg2Zn11 phases. Among all the alloys, the Zn-2Cu-0.5Mn alloy achieved the highest ultimate tensile strength (UTS) of ∼405 MPa and yield strength (YS) of ∼293 MPa with an excellent elongation of ∼51%. The corrosion behavior of the alloys as determined by a potentiodynamic polarization study under different solutions follows the sequence Zn-2Cu < Zn-2Cu-0.5Mn < Zn-2Cu-0.1Mn < Zn-2Cu-0.1Mg < Zn-2Cu-0.5Mg. The corrosion rate by immersion testing for 30 and 90 days also follows the same sequence. The corrosion rate in different solutions follows the order SBF > DMEM + 10%FBS > DMEM. The addition of Mn/Mg also improves the wear resistance and slows the wear rate under wet conditions. The bending test results also indicate the highest bending strength of ∼375 MPa for the Zn-2Cu-0.5Mn alloy, among all the alloys. The bending and tensile strengths deteriorate continuously after the immersion for 30 and 90 days in the solution of SBF, DMEM, and DMEM + 10%FBS. Therefore, the Zn-2Cu-xMn/Mg (x = 0.1 and 0.5) alloys can be considered potential biodegradable implant materials.

Influence of Copper on the Microstructural, Mechanical, and Biological Properties of Commercially Pure Zn-Based Alloys for a Potential Biodegradable Implant.

Three Zn-based alloys (Zn1Cu, Zn2Cu, and Zn3Cu) were developed by the addition of Cu (1, 2, and 3 wt %) into commercially pure Zn. This report systematically investigates the potential for these newly developed Zn-based alloys as biodegradable materials. Microstructural studies reveal the presence of spherical-shaped nanosized precipitates of ε-CuZn4 in the Zn1Cu alloy, whereas Zn2Cu and Zn3Cu alloys exhibit the presence of both micron- and nanosized precipitates of ε-CuZn4. The mechanical properties such as hardness, tensile and compressive strengths improve significantly with an increase in the amount of Cu in the alloy. The Zn3Cu alloy exhibits the highest yield strength (225 ± 9 MPa) and ultimate tensile strength (330 ± 12 MPa) among all of the alloys, which are ∼2.7 and 2 times higher than those of pure Zn. In vitro degradation behavior is evaluated by the potentiodynamic polarization study and immersion testing in Hank's solution for 20 and 75 days. The corrosion rate after both polarization and immersion testing follows the order of pure Zn < Zn1Cu < Zn3Cu < Zn2Cu. An electrochemical impedance spectroscopy (EIS) study also concludes that Zn2Cu shows the lowest corrosion resistance. The % cell viability values of 3T3 fibroblasts cells after 5 days of culture in a 50% diluted extract of pure Zn, Zn2Cu, and Zn3Cu alloys are 76 ± 0.024, 86.18 ± 0.033, and 92.9 ± 0.026%, respectively, establishing the improved cytocompatibility of the alloys as compared to pure Zn. Furthermore, an antibacterial study also reveals that the Zn3Cu alloy exhibits 80, 67, and 100% increases in the zone of inhibition (ZOI) for Escherichia coli, Bacillus subtilis, and Pseudomonas aeruginosa bacteria, respectively, as compared to that of pure Zn.

Electrodeposited functionally graded coating inhibits Gram-positive and Gram-negative bacteria by a lipid peroxidation mediated membrane damage mechanism.

The current work deals with a time-dependent study to track the antibacterial action of electrodeposited Cu, Cu-SiC functionally graded coating (FGC) against Escherichia coli NCIM 2931 (Gram-negative) and Bacillus subtilis NCIM 2063 (Gram-positive). After 24 h of incubation, the Cu, Cu-SiC FGC causes 7 Escherichia coli NCIM 2931 and 10 Bacillus subtilis NCIM 2063 log reduction of planktonic cells. The outer membrane permeabilization experiment proves that the intake of excessive Cu ions leads to the damage of bacterial cell membrane followed by lipid degradation. The thiobarbituric acid reactive substances assay reveals that Cu ions released from the surface of Cu, Cu-SiC FGC triggers the oxidative degeneration of phospholipids (most abundant constituent of bacterial cell membrane). This was further cross-verified using atomic absorption spectroscopy. From 0 to 24 h, the bacterial morphology is characterized using transmission electron microscope and scanning electron microscope which shows the cytoplasmic leakage and cell death. The Cu, Cu-SiC FGC also exhibits hydrophobic surface (contact angle of 144°) which prevents the bacterial adherence to the surface and thus, inhibits them to penetrate into its bulk. The observed results of antibacterial and anti-adhesion properties of Cu, Cu-SiC FGC are compared with single-layered metallic Cu and Cu-SiC nanocomposite coatings. Hence, the electrodeposited Cu, Cu-SiC FGC has the potential to serve as an inexpensive touch surface alternative for the healthcare industries.

Synthesis of calcium hydrogen phosphate and hydroxyapatite coating on SS316 substrate through pulsed electrodeposition.

The orthopaedic implants for human body are generally made of different biomaterials like stainless steels or Ti based alloys. However, it has been found that from surface properties point of view, none of these materials is attractive for fast tissue or cell growth on the surface of implant. This is one of the most important criteria to assure quick bonding between implant and body tissues vis-à-vis minimum recovery time for the patient. Keeping in view of the above facts, this work involves the pulsed electro-deposition coating of biocompatible hydroxyapatite and its group compounds from a diluted bath of calcium and phosphate salt at various current densities over the biomaterial sheet of SS316. SEM study confirms different morphologies of the coatings at different current densities. Characterization techniques like X-ray diffraction, SEM with EDX and FTIR have been used to confirm the phase and percentage quantity of hydroxyapatite compound in the depositions. This coating can serve as a medium for faster tissue growth over the metallic implants.

Influence of sodium saccharin on the microstructure of pulse electrodeposited Ni-CeO2 nanocomposite coating.

In the present study the Ni-CeO2 nanocomposite coating has been pulse electrodeposited from a watt's type bath containing 30 g/l CeO2 nanoparticles and varying amount of sodium saccharin (SS). Experimental results show that both the amount of codeposited CeO2 particle and crystallite size of Ni in the composite coating decrease with an increase in the SS concentration of the electrolyte. The microhardness increases up to 0.50 g/l SS concentration in the electrolyte; beyond it there is no further increase in the microhardness.

Effect of current density on the microstructure and hardness of Ni-CeO2 nanocomposite coating synthesized by pulse electrodeposition technique.

The Ni-CeO2 nanocomposite coatings have been synthesized by pulse electrodeposition technique with different current densities (0.10, 0.30, 0.40, 0.50, 0.70 and 0.90 A/cm2) from a Watts-type electrolyte containing nano-sized ceria particles. The Ni-CeO2 coatings produced with different current densities have been characterized by X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM) and scanning electron microscopy (SEM) coupled with an energy dispersive spectrometer (EDS). The hardness of the coatings has been measured by Vickers microhardness tester (VMHT). It has been found that the crystallite size decreases and hardness increases with the increasing current density. However, the co-deposition of ceria in the nickel matrix increases up to the current density of 0.5 A/cm2, beyond which it decreases.

Synthesis and characterization of pulse co-electrodeposited nickel/ceria nanocomposites.

Nanocrystalline nickel matrix composites reinforced with the nanosized ceria particles have been synthesized by cathodic pulsed electrodeposition. The reinforcement is synthesized by the high energy ball milling (HEBM) technique. Both the reinforcement and composites have been characterized by XRD, TEM and SEM coupled with EDS. The microhardness of the composites containing different volume fractions of ceria have been evaluated and compared with that of pure nanocrystalline nickel deposited under the same conditions. The results show that the hardness of the composite is significantly higher than that of the nanocrystalline pure nickel.

Pulsed co-electrodeposition and characterization of Ni-based nanocomposites reinforced with combustion-synthesized, undoped, tetragonal-ZrO(2) particulates.

Nanostructured nickel matrix composites reinforced with nanosized, undoped, tetragonal zirconia has been synthesized by cathodic pulsed electrodeposition. The reinforcement is synthesized by the aqueous combustion synthesis route with glycine as the fuel and zirconyl nitrate as the oxidizer. The reinforcement and composite have been characterized by XRD, TEM and SEM coupled with EDS. The microhardness and thermal stability (Kissinger method) of the composite are evaluated. These values are compared with those of pure nickel deposited under the same conditions. The results show that the microhardness of the nickel matrix is enhanced by the presence of the reinforcement from 450 to 575 VHN. Also the strengthening due to grain size effects and dispersion strengthening effect are evaluated individually and the interparticle separation is estimated to be around 85 nm. The volume fraction of the reinforcement is estimated to be 12-15% and the particles are uniformly distributed and monodispersed in the nickel matrix. The thermal stability of the composite is better than that of pure nickel in contrast to some of the reported literature.

Synthesis and characterization of Al-Zn/Al2O3 nano-powder composites.

Composites consisting of Al-Zn/Al2O3 have been synthesized using high energy mechanical milling. High energy ball milling increases the sintering rate of the composite powder due to increased diffusion rate. Owing to the finer microstructure, the hardness of the sintered composite produced by using the mechanically milled nanocomposite powder is significantly higher than that of the sintered composite produced by using the as-mixed powder. The mean crystallite size of the matrix has been determined to be 27 nm by Scherrer equation using X-ray diffraction data. The powders have been characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), and differential thermal analysis (DTA). The effect of high-energy ball milling and subsequent annealing on a mixture of Al and ZnO has also been investigated. DTA result show that the reaction temperature of Al-ZnO decreases with the increase in the ball milling time.