PEO Surface Research Articles

Modification of Ti13Nb13Zr Alloy Surface via Plasma Electrolytic Oxidation and Silver Nanoparticles Decorating.

The dynamically developing field of implantology requires researchers to search for new materials and solutions. In this study, TiNbZr samples were investigated as an alternative for popular, but potentially hazardous TiAl6V4. Samples were etched, sandblasted, subjected to PEO, and covered in AgNP suspension. Simultaneously, SEM images were taken, and the wettability and roughness of the surface were measured. Samples covered in AgNPs were subjected to biological trials. A six-day measurement of human fibroblast proliferation was conducted to assess biocompatibility, and the population of E. coli and S. aureus was measured over eight hours. Results showed that the TiNbZr PEO surface is biocompatible with human fibroblast cells and promotes growth. However, deposited AgNPs exhibited only slight effectiveness in decreasing bacterial growth over the first two hours. The results suggest that the method of surface preparation is sufficient and might promote osseointegration. On the other hand, more efficient and reliable methods of application of AgNPs should be researched.

Effects of polyimide on corrosion and wear resistance of PEO composite coating on AZ91 Mg alloy

The accelerated deterioration resulting from microscopic defects in Mg alloy PEO coatings is a notable issue. This study introduced a PEO/PI composite coating on the surface of AZ91 Mg alloy PEO coating through coating method, aiming to enhance its corrosion resistance and wear resistance. The findings indicated that as the coating time increases, the surface micropores sealed and filled by the PI coating. This led to a positive shift in the corrosion potential of the composite coating, a significant decrease in corrosion current density by three orders of magnitude, and a marked improvement in corrosion resistance. The strong adhesion of the PI coating to the PEO surface acted as a lubricant, making the composite coating self-lubricating. Additionally, PI's excellent high temperature resistance ensured that surface wear was not induced by elevated temperatures resulting from localized friction.

Cytocompatibility, cell-material interaction, and osteogenic differentiation of MC3T3-E1 pre-osteoblasts in contact with engineered Mg/PLA composites.

Bioabsorbable Mg wire-reinforced poly-lactic acid (PLA) matrix composites are potential candidate for load-bearing orthopedic implants offering tailorable mechanical and degradation properties by stacking sequence, volume fraction and surface modification of Mg wires. In this study, we investigated the cytocompatibility, cell-material interaction, and bone differentiation behavior of MC3T3-E1 pre-osteoblast cells for medical-grade PLA, Mg/PLA, and PEO-Mg/PLA (having PEO surface modification on Mg wires) composites. MTT and live/dead assay showed excellent biocompatibility of both composites while cell-material interaction analysis revealed that cells were able to adhere and proliferate on the surface of composites. Cells on the longitudinal surface of composites showed a high and uniform cell density while those on transversal surfaces initially avoided Mg regions but later migrated back after the formation of the passivation layer. Bone differentiation tests showed that cells in extracts of PLA and composites were able to initiate the differentiation process as osteogenesis-related gene expressions, alkaline phosphatase protein quantity, and calcium mineralization increased after 7 and 14 days of culture. Interestingly, the bone differentiation response of PEO-Mg/PLA composite was found to be similar to medical-grade PLA, proving its superiority over Mg/PLA composite.

Characterization and In Vitro Behavior of PEO Coated Mg Modified with Antibacterial Ag(I) and Cu(II) Complexes.

The use of Mg-based biomaterials with a number of their advantageous properties are overshadowed by uncontrollable metal corrosion. Moreover, the use of implants goes alongside with the threat of pathogens-associated complications. In this study, PEO coated Mg biomaterial loaded with antibacterial Ag(I) and Cu(II) complexes is produced and tested to meet both appropriate protective characteristics as well as sufficient level of antibacterial activity. To achieve a suitable level of anticorrosion protection phosphate and fluoride-phosphate electrolytes are used in the PEO process. Investigation of the surface thickness and morphology done by means of cross-section analysis and scanning electron microscopy (SEM), as well as electrochemical impedance spectroscopy (EIS) assay show precedence of the fluoride containing PEO coating and make it the material of choice for further modification with Ag(I) and Cu(II) complexes. The presence of the complexes on the PEO surface is confirmed by energy dispersive X-ray spectroscopy (EDX). X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM) and glow discharge optical emission spectroscopy (GDOES) are used to estimate the complexes' chemical state and depth of penetration in the coating surface. Based on the results of antibacterial assay, the modified coatings are found to be active against both Gram-positive and Gram-negative bacteria.

Unknown tribological possibilities - Wear resistance for light metals by PEO, hybrid, and laser functionalized surface solutions

Facing today's demands on components in general industry, aerospace, automotive, machinery or medical industry, lightweight and a tailored surface might be the right answer to reduce waste in terms of wear or frictional energy losses. PEO, plasma-electrolytical oxidation, remains as an unknown or at least niche surface technology, giving lightweight metals a hard and robust protection shell. Expiring an increasing interest in the research society in the last decade, it is supposed to be a promising candidate for increasing lightweight potential but being not ready for wide industrial applications by being too expensive or applicable only on small parts or series. The CERANOD® PEO surfaces are on the market for over 20 years, applied under different harsh conditions. The CERANOD® -surfaces can withstand high loading by vibrations giving lightweight alloys like Aluminum or Magnesium a very high corrosion and wear protection.Combining the high wear resistance of the PEO surfaces with polymers like doped PEEK, we can achieve low friction and wear in tribological applications without additional lubricants, leading to sustainable systems. Further improvement can be done using laser radiation for patterning and selective laser sintering of the polymer top coating.This work reports on laboratory tribological and wear test results accompanied by SEM and EDS findings for different CERANOD® surface solutions. These findings can be correlated with some different application cases of clients, who utilize these solutions on their end products to enable the usage of lightweight metals under harsh tribological, vibrating and/or corrosive environments, and, thus, saving a lot of energy and resources.

Incorporating Binary Metal Oxides in Poly(ethylene oxide)-Based Solid Electrolytes by Vapor Phase Infiltration

Vapor phase infiltration (VPI) derived from atomic layer deposition (ALD) enables inorganic materials to nucleate and grow within the free volume of polymers, which has shown promising prospects in the field of composite solid polymer electrolytes (CSPEs). However, there are only a few types of metal oxides that can be incorporated into the polymer matrix by VPI, let alone binary metal oxides, due to the limited knowledge of the VPI synthesis process. To combine the merits of different metal oxides, we investigate the VPI method to prepare ZnO-Al2O3 composites in poly(ethylene oxide) (PEO). When the introducing order is Al2O3/ZnO (AZO), due to the extremely high reactivity of trimethyl aluminum (TMA) with PEO, VPI-Al2O3 will accumulate near the surface of PEO. The surface Al2O3 layer inhibits the further diffusion of the diethyl zinc (DEZ) into the PEO matrix, leading to weak polymer-filler interactions and limited improvement of the Li+ conduction. In the incorporation order of ZnO/Al2O3 (ZAO), the moderate reactivity of DEZ renders the uniform distribution of VPI-ZnO within PEO, and the following TMA can both react with PEO and VPI-ZnO particles near the surface of PEO, which not only preserves the interactions between VPI-ZnO and PEO but also better inhibits the growth of lithium dendrites. The incorporation order plays a crucial role in the morphology and composition of binary metal oxides synthesized by VPI.

Mapping Bone Marrow Cell Response from Senile Female Rats on Ca-P-Doped Titanium Coating.

Chemical and topographical surface modifications on dental implants aim to increase the bone surface contact area of the implant and improve osseointegration. This study analyzed the cellular response of undifferentiated mesenchymal stem cells (MSC), derived from senile rats’ femoral bone marrow, when cultured on a bioactive coating (by plasma electrolytic oxidation, PEO, with Ca2+ and P5+ ions), a sandblasting followed by acid-etching (SLA) surface, and a machined surface (MSU). A total of 102 Ti-6Al-4V discs were divided into three groups (n = 34). The surface chemistry was analyzed by energy dispersive spectroscopy (EDS). Cell viability assay, gene expression of osteoblastic markers, and mineralized matrix formation were investigated. The cell growth and viability results were higher for PEO vs. MSU surface (p = 0.001). An increase in cell proliferation from 3 to 7 days (p < 0.05) and from 7 to 10 days (p < 0.05) was noted for PEO and SLA surfaces. Gene expression for OSX, ALP, BSP, and OPN showed a statistical significance (p = 0.001) among groups. In addition, the PEO surface showed a higher mineralized matrix bone formation (p = 0.003). In conclusion, MSC from senile female rats cultured on SLA and PEO surfaces showed similar cellular responses and should be considered for future clinical investigations.

Formation of plasma electrolytic oxidation coatings on pure niobium in different electrolytes

The development of PEO surface treatments for Nb (niobium) provides a possibility to produce functionalized coatings with a combination of new compositions and phases. In the frame of this work, PEO coatings on pure Nb are produced in three electrolytes containing aluminate, phosphate and silicate. Furthermore, the influence of the electrolyte composition on the PEO process and the microstructure, composition and properties of the coatings were studied. It was observed that most of the coating forming species did not participate in the plasma reactions directly, while the chemical-, electrochemical- and thermal stimulated reactions are dominating the coating formation. The results show that all the coatings are mainly composed of the Nb2O5 phase. An additional mixture of oxides (Al2O3 and AlNbO4) is found in the coating formed in aluminate-containing electrolyte, and the coating formed in phosphate-containing electrolyte contains a small amount of Nb2(PO4)3 and amorphous phosphate. No additional crystalline phase other than the amorphous silica phase is detected in the coating formed in silicate-containing electrolyte. Additionally, different morphology of the coatings is revealed and the most uniform coating is produced in silicate-containing electrolyte, which further improves its corrosion resistance. This coating also shows the highest photocatalytic activity due to the combination of Nb2O5 and silica. Since all PEO coatings on pure Nb show superior corrosion resistance and photocatalytic activity, they might be interesting for a wide range of applications ranging from transportation, biomedical implants to environmental protection.

Polyoxyethylene (PEO)|PEO-Perovskite|PEO Composite Electrolyte for All-Solid-State Lithium Metal Batteries.

Composite solid electrolytes (CSEs) are regarded as one of the most promising candidates for all-solid-state lithium metal batteries (ASSLMBs) due to inherited desirable features from both ceramic and polymer materials. However, poor interfacial contact/compatibility between the electrodes and solid electrolytes remains a critical challenge. In this work, we prepare a flexible CSE composed of polyoxyethylene (PEO)-perovskite composite with a layer of PEO on either side. This PEO|PEO-perovskite|PEO structure prevents direct contact between theperovskite and lithium metal at the anode side, avoiding the undesired reaction between the two materials (Ti4+ + Li → Ti3+ + Li+). Moreover, the design incorporating the PEO surface on either side enables superb contact between the electrolyte and the electrodes and buffers the change in electrolyte volume from the cathode and lithium metal during repeated cycling, resulting in low interfacial resistances and excellent cycling stability. Meanwhile, perovskite inorganic electrolyte Li0.33La0.557TiO3 (LLTO) 3D nanofiber networks formed by electrospinning enable the CSE to achieve enhanced mechanical strength and high ionic conductivity of 0.16 mS cm-1 at 24 °C. As a result, a Li|PEO-LiTFSI-LLTO|Li symmetric cell remains stable after 400 h of operation without short-circuiting. Most notably, a Li|PEO-LiTFSI-LLTO|LiFePO4 full battery is capable of delivering a high capacity of 135.0 mAh g-1 even at 2 C with a retention rate of 79.0% after 300 cycles at 60 °C. These results demonstrate that the integrated sandwich structure proposed in this work is effective in developing high-performance composite solid electrolytes for ASSLMBs.

New protein-resistant surfaces of amphiphilic graft copolymers containing hydrophilic poly(ethylene glycol) and low surface energy fluorosiloxane side-chains

Methacryloyl-terminated poly[methyl(3,3,3-trifluoropropyl)siloxane] (PMTFPS-MA) macro-monomers with controlled segment length were designed and synthesized by anionic ring-opening polymerization of 1,3,5-trimethyl-1,3,5-tri(3′,3′,3′-trifluoropropyl)cyclotrisiloxane (F3). Then, a series of novel amphiphilic fluorosiloxane-containing graft copolymers were prepared using PMTFPS-MA, poly(ethylene glycol) methyl ether methacrylate (PEG-MA) and methyl methacrylate (MMA) as the co-monomers, and their surface properties and protein-resistant performance were investigated. It was found that the composition of amphiphilic graft copolymers would play an important role in the protein-resistant properties. When the copolymers contain 65.5 wt% PEO segments and 6.4 wt% PMTFPS segments, the coating surface exhibits strong protein-resistant property and shows almost no protein adsorption on it. Based on the surface analysis of amphiphilic graft copolymer films both in dry and wet conditions, the protein-resistant property of amphiphilic copolymers can be owing to the transition from a hydrophobic surface to hydrophilic surface with highly efficient water-driven PEO surface migration. The PEO segments are utilized to prevent protein adsorption whereas the low surface energy PMTFPS segments are utilized to drive away the adsorbed proteins.

Impact of Bioactive Peptide Motifs on Molecular Structure, Charging, and Nonfouling Properties of Poly(ethylene oxide) Brushes

Polymer layers capable of suppressing protein adsorption from biological media while presenting extracellular matrix-derived peptide motifs offer valuable new options for biomimetic surface engineering. Herein, we provide detailed insights into physicochemical changes induced in a nonfouling poly(ethylene oxide) (PEO) brush/polydopamine (PDA) system by incorporation of adhesion ligand (RGD) peptides. Brushes with high surface chain densities (σ ≥ 0.5 chains·nm-2) and pronounced hydrophilicity (water contact angles ≤ 10°) were prepared by end-tethering of heterobifunctional PEOs ( Mn ≈ 20 000 g·mol-1) to PDA-modified surfaces from a reactive melt. Using alkyne distal end group on the PEO chains, azidopentanoic-bearing peptides were coupled through a copper-catalyzed Huisgen azide-alkyne "click" cycloaddition reaction. The surface concentration of RGD was tuned from complete saturation of the PEO surface with peptides (1.7 × 105 fmol·cm-2) to values which may induce distinct differences in cell adhesion (<6.0 × 102 fmol·cm-2). Infrared reflection-absorption and X-ray photoelectron spectroscopies proved the PDA-PEO layers covalent structure and the immobilization of RGD peptides. The complete reconstruction of experimental electrohydrodynamics data utilizing mean-field theory predictions further verified the attained brush structure of the end-tethered PEO chains which provided hydrodynamic screening of the PDA anchor. Increasing the surface concentration of immobilized RGD peptides led to increased interfacial charging. Supported by simulations, this observation was attributed to the ionization of functional groups in the amino acid sequence and to the pH-dependent adsorption of water ions (OH- > H3O+) from the electrolyte. Despite the distinct differences observed in the electrokinetic analysis of the surfaces bearing different amounts of RGD, it was found that the peptide presence on PEO(20 000)-PDA layers does not have a significant effect on the nonfouling properties of the system. Notably, the presented PEO(20 000)-PDA layers bearing RGD peptides in the surface concentration range 5.9 to 1.7 × 105 fmol·cm-2 reduced the protein adsorption from fetal bovine serum to less than 30 ng·cm-2, that is, values comparable to the ones obtained for pristine PEO(20 000)-PDA layers.

Reversible Protein Adsorption on Mixed PEO/PAA Polymer Brushes: Role of Ionic Strength and PEO Content.

Proteins at interfaces are a key for many applications in the biomedical field, in biotechnologies, in biocatalysis, in food industry, etc. The development of surface layers that allow to control and manipulate proteins is thus highly desired. In previous works, we have shown that mixed polymer brushes combining the protein-repellent properties of poly(ethylene oxide) (PEO) and the stimuli-responsive adsorption behavior of poly(acrylic acid) (PAA) could be synthesized and used to achieve switchable protein adsorption. With the present work, we bring more insight into the rational design of such smart thin films by unravelling the role of PEO on the adsorption/desorption of proteins. The PEO content of the mixed PEO/PAA brushes was regulated, on the one hand, by using PEO with different molar masses and, on the other hand, by varying the ratio of PEO and PAA in the solutions used to synthesize the brushes. The influence of ionic strength on the protein adsorption behavior was also further examined. The behavior of three proteins-human serum albumin, lysozyme, and human fibrinogen, which have very different size, shape, and isoelectric point-was investigated. X-ray photoelectron spectroscopy, quartz crystal microbalance, atomic force microscopy, and streaming potential measurements were used to characterize the mixed polymer brushes and, in particular, to estimate the fraction of each polymer within the brushes. Protein adsorption and desorption conditions were selected based on previous studies. While brushes with a lower PEO content allowed the higher protein adsorption to occur, fully reversible adsorption could only be achieved when the PEO surface density was at least 25 PEO units per nm2. Taken together, the results increase the ability to finely tune protein adsorption, especially with temporal control. This opens up possibilities of applications in biosensor design, separation technologies, nanotransport, etc.

The study of Design Surface Treatment Obtained Metal Color in Magnesium Alloy

The shape of the reflection spectrum is complex and appears to overlap with several signals, because the surface state is uneven due to the natural oxide film, so that the spectrum becomes a complicated signal shape divided into regions 1 and 2 due to diffuse reflection. On the other hand, it is seen that the reflection spectrum after PEO surface treatment is overlapped with several signals. In addition, the reflectance of the energy band varies from 1.32 to 1.46 eV. Usually, the MgO-type oxide film was observed at an energy band of ~4.2 eV. The thickness of the oxide film was increased as the DC voltage was increased by the thin film thickness meter (QuaNix; 7500M) after Plasma Electrolytic Oxidation (; PEO) surface treatment. This is because the higher the DC voltage, the easier the binding of the OH- ions in the solution solution and the Mg+ ions of the magnesium alloy. An important part of the bonding of ordinary ions is the energy source (plasma) which can promote bonding. However, when a certain threshold voltage or more is applied, the material is adversely affected. The oxide film of the surface may be destroyed without increasing the thickness of the oxide film, that is, whitening of the material may occur.

Electrochemical rutile and anatase formation on PEO surfaces

A highly porous surface with a high crystalline content and resultant photocatalytic activity is ensured through the process of plasma electrolytic oxidation on pure titanium. In the present study the morphology, crystallinity and photocatalytic activity of plasma electrolytic oxidized TiO2-surfaces were investigated. The surfaces were prepared in acidic and alkaline electrolytes over an applied voltage range between 50V and 300V to optimize the crystalline and photocatalytic properties. Scanning electron microscopy (SEM) and X-ray powder diffraction (XRD) were selected to determine the morphologies which differ according to the type of electrolyte as well as the crystal structures of anatase and rutile on the surface material, which increase with the applied voltage. The oxide surfaces did not show morphological differences compared to typical PEO surfaces with the exception of oxide films obtained in H2SO4-solution which also exhibited an astounding amount of rutile even with low applied voltages. The increased parts of anatase and rutile on the surfaces resulted in photocatalytic activity, which was investigated under UV-light using methylene blue, while the PEO surfaces showed degradation activity. There is an indication that a high proportion of anatase and small amounts of rutile in the PEO layers positively influence photocatalytic activity.

Crystallization and Rheology of Poly(ethylene oxide) in Imidazolium Ionic Liquids

Polymer and ionic liquid (IL) mixtures have attracted an increasing amount of attention due to their unique properties and potential applications. The interactions between poly(ethylene oxide) (PEO) and imidazolium ILs of different cation alkyl lengths and anion structures have been investigated by measuring melting points (Tm), contact angles, and rheological properties. Tm of crystalline PEO dramatically decreased when it was blended with ILs. Similarly, the contact angles of different ILs on a PEO surface proportionally decreased. The interaction energy, as calculated from melting point depression using the Flory equation, increased with the length of imidazolium alkyl cations and the size of anions. The different anionic structures had a more significant influence on the interaction energy than the alkyl chain lengths of cations. These trends accorded with the solubility obtained by high-energy X-ray diffraction and swelling ratio measurements of PEO in different ILs [Asai Macromolecules 2013, 46, 236...

Force-pad made from contact-electrification poly(ethylene oxide)/InSb field-effect transistor

A contact electrification field-effect transistor (CE-FET) is first made from poly(ethylene oxide)/InSb/PET(polyethylene terephthalate) on the flexible force-pad application. The CE-FET operates on a unique principle that relies on the triboelectric potential difference that is established between the two tribo-surfaces, to induce an inner electrical signal by utilizing the external frictional force. Such a signal is able to modulate the carrier transport characteristics in the FET and is self-generated to have the same effect as applying a gate signal. The traditional gate electrode in the FET is replaced by an individually mobile aluminum and a polytetrafluoroethene (PTFE) electrode to serve as a positive and negative gate voltage, respectively. The n-type rich indium (In) InSb thin film is then used as a conduction channel in the CE-FET. When the PTFE film acted as a mobile gate electrode to progressively contact the PEO surface, the drain current was increased from 6 to 12μA by increasing the distance (d) between the PEO and the PTFE surfaces in the range from 0 to 80μm. In contrast, when the Al film was used as a mobile electrode to gradually contact the PEO surface, the corresponding drain current decreases from 7μA to 1.5μA, while increasing the corresponding distance from 0 to 80μm, respectively. Thus, the characteristic of the CE-FET has established an enhancement and depletion mode in the InSb conduction channel when the mobile electrodes of the PTFE and aluminum films were mechanically attached to the PEO surface, respectively. The CE-FET InSb is highly reliable and sensitive, which thereby opens up a new research field on the applications of the force pads.

Interactions of Apolipoproteins AI, AII, B and HDL, LDL, VLDL with Polyurethane and Polyurethane-PEO Surfaces.

The lipoproteins (HDL, LDL, VLDL) are important components of blood present in high concentration. Surprisingly, their role in blood-biomaterial interactions has been largely ignored. In previous work apolipoprotein AI (the main protein component of HDL) was identified as a major constituent of protein layers adsorbed from plasma to biomaterials having a wide range of surface properties, and quantitative data on the adsorption of apo AI to a biomedical grade polyurethane were reported. In the present communication quantitative data on the adsorption of apo AI, apo AII and apoB (the latter being a constituent of LDL and VLDL), as well as the lipoprotein particles themselves (HDL, LDL, VLDL), to a biomedical segmented polyurethane (PU) with and without an additive containing poly(ethylene oxide) (material referred to as PEO) are reported. Using radiolabeled apo AI, apo AII, and apoB, adsorption levels on PU from buffer at a protein concentration of 50 μg/mL were found to be 0.34, 0.40, and 0.14 μg/cm(2) (12, 23, and 0.25 nmol/cm(2)) respectively. Adsorption to the PEO surface was <0.02 μg/cm(2) for all three apolipoproteins demonstrating the strong protein resistance of this material. In contrast to the apolipoproteins, significant amounts of the lipoproteins were found to adsorb to the PEO as well as to the PU surface. X-ray photoelectron spectra, following exposure of the surfaces to the lipoproteins, showed a strong phosphorus signal, confirming that adsorption had occurred. It therefore appears that a PEO-containing surface that is resistant to apolipoproteins may be less resistant to the corresponding lipoproteins.

Cell adhesion and growth enabled by biomimetic oligopeptide modification of a polydopamine-poly(ethylene oxide) protein repulsive surface.

Protein-repulsive surfaces modified with ligands for cell adhesion receptors have been widely developed for controlling the cell adhesion and growth in tissue engineering. However, the question of matrix production and deposition by cells on these surfaces has rarely been addressed. In this study, protein-repulsive polydopamine–poly(ethylene oxide) (PDA–PEO) surfaces were functionalized with an RGD-containing peptide (RGD), with a collagen-derived peptide binding fibronectin (Col), or by a combination of these peptides (RGD + Col, ratio 1:1) in concentrations of 90 fmol/cm2 and 700 fmol/cm2 for each peptide type. When seeded with vascular endothelial CPAE cells, the PDA–PEO surfaces proved to be completely non-adhesive for cells. On surfaces with lower peptide concentrations and from days 1 to 3 after seeding, cell adhesion and growth was restored practically only on the RGD-modified surface. However, from days 3 to 7, cell adhesion and growth was improved on surfaces modified with Col and with RGD + Col. At higher peptide concentrations, the cell adhesion and growth was markedly improved on all peptide-modified surfaces in both culture intervals. However, the collagen-derived peptide did not increase the expression of fibronectin in the cells. The deposition of fibronectin on the material surface was generally very low and similar on all peptide-modified surfaces. Nevertheless, the RGD + Col surfaces exhibited the highest cell adhesion stability under a dynamic load, which correlated with the highest expression of talin and vinculin in the cells on these surfaces. A combination of RGD + Col therefore seems to be the most promising for surface modification of biomaterials, e.g. vascular prostheses.Electronic supplementary materialThe online version of this article (doi:10.1007/s10856-015-5583-3) contains supplementary material, which is available to authorized users.

Bioactive coatings on Ti6Al4V alloy formed by plasma electrolytic oxidation

Abstract In this study, coatings, consisting of hydroxyapatite and titanium oxide bioceramic phases, were produced on Ti6Al4V alloy by plasma electrolytic oxidation for different times in a solution containing calcium acetate and β-calcium glycerophosphate. The phases of anatase, rutile, TCP (Ca3(PO4)2), perovskite-CaTiO3 and hydroxyapatite (HAp, Ca10(PO4)6(OH)2) were detected in the PEO coatings. The crystallinity of these phases was enhanced with increasing treatment time. The friction and wear resistance properties of the PEO coatings in simulated body fluid (SBF) were substantially improved compared to Ti6Al4V alloy. The corrosion resistance of the PEO samples in SBF was determined by an electrochemical method, and found to be significantly improved compared to Ti6Al4V alloy due to the existence of titanium oxide and the calcium phosphate-based phases. The amount of apatite induced at the PEO surface increased with increasing immersion time in SBF at 36.5 °C. According to the SEM images and FTIR results, after soaking in SBF for 14 days, the amount of secondary apatite formed in the coating electrolytically oxidized for 90 min was maximized due to high surface area and high amount of TiO2 and HAp in the coating structure.

Effect of peptide secondary structure on adsorption and adsorbed film properties on end-grafted polyethylene oxide layers

Poly-l-lysine (PLL), in α-helix or β-sheet configuration, was used as a model peptide for investigating the effect of secondary structures on adsorption events to poly(ethylene oxide) (PEO) modified surfaces formed using θ solvents. Circular dichroism results showed that the secondary structure of PLL persisted upon adsorption to Au and PEO modified Au surfaces. Quartz crystal microbalance with dissipation (QCM-D) was used to characterize the chemisorbed PEO layer in different solvents (θ and good solvents), as well as the sequential adsorption of PLL in different secondary structures (α-helix or β-sheet). QCM-D results suggest that chemisorption of PEO 750 and 2000 from θ solutions led to brushes 3.8±0.1 and 4.5±0.1nm thick with layer viscosities of 9.2±0.8 and 4.8±0.5cP, respectively. The average number of H2O per ethylene oxides, while in θ solvent, was determined as ∼0.9 and ∼1.2 for the PEO 750 and 2000 layers, respectively. Upon immersion in good solvent (as used for PLL adsorption experiments), the number of H2O per ethylene oxides increased to ∼1.5 and ∼2.0 for PEO 750 and 2000 films, respectively. PLL adsorbed masses for α-helix and β-sheet on Au sensors was 231±5 and 1087±14ngcm−2, with layer viscosities of 2.3±0.1 and 1.2±0.1cP, respectively; suggesting that the α-helix layer was more rigid, despite a smaller adsorbed mass, than that of β-sheet layers. The PEO 750 layer reduced PLL adsorbed amounts to ∼10 and 12% of that on Au for α-helices and β-sheets respectively. The PLL adsorbed mass to PEO 2000 layers dropped to ∼12% and 4% of that on Au, for α-helix and β-sheet respectively. No significant differences existed for the viscosities of adsorbed α-helix and β-sheet PLL on PEO surfaces. These results provide new insights into the fundamental understanding of the effects of secondary structures of peptides and proteins on their surface adsorption.