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Titanate structures have been widely investigated as biomedical component surfaces due to their bioactive, osteoinductive and antibacterial properties. However, these surfaces are limited to Ti and its alloys, due to the nature of the chemical conversion employed. The authors present a new method for generating nanoporous titanate structures on alternative biomaterial surfaces, such as other metals/alloys, ceramics and polymers, to produce bioactive and/or antibacterial properties in a simple yet effective way. Wet chemical (NaOH; 5 M; 60 °C; 24 h) conversion of DC magnetron sputtered Ti surfaces on 316L stainless steel were investigated to explore effects of microstructure on sodium titanate conversion. It was found that the more equiaxed thin films (B/300) generated the thickest titanate structures (ca. 1.6 μm), which disagreed with the proposed hypothesis of columnar structures allowing greater NaOH ingress. All film parameters tested ultimately generated titanate structures, as confirmed via EDX, SEM, XPS, XRD, FTIR and Raman analyses. Additionally, the more columnar structures (NB/NH & B/NH) had a greater quantity of Na (ca. 26 at.%) in the top portion of the films, as confirmed via XPS, however, on average the Na content was consistent across the films (ca. 5-9 at.%). Film adhesion for the more columnar structures (ca. 42 MPa), even on polished substrates, were close to that of the FDA requirement for plasma-sprayed HA coatings (ca. 50 MPa). This study demonstrates the potential of these surfaces to be applied onto a wide variety of material types, even polymeric materials, due to the lower processing temperatures utilised, with the vision to generate bioactive and/or antibacterial properties on a plethora of bioinert materials., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Authors. Published by Elsevier Inc. All rights reserved.)

Intravascular stents are being designed which utilise the shape memory properties of NiTi alloy. Despite the clinical advantages afforded by these stents their application has been limited by concerns about the large nickel ion content of the alloy. In this study, the surface chemistry of NiTi alloy was modified by mechanical polishing and oxidising heat treatments and subsequently characterised using X-ray photon spectroscopy (XPS). The effect of these surfaces on monolayer formation and barrier integrity of human umbilical vein endothelial cells (HUVEC) was then assessed by confocal imaging of the adherens junctional molecule VE-cadherin, perijunctional actin and permeability to 42kDa dextrans. Dichlorofluoroscein assays were used to measure oxidative stress in the cells. XPS analysis of NiTi revealed its surface to be dominated by TiO(2). However, where oxidation had occurred after mechanical polishing or post polishing heat treatments at 300 and 400 degrees C in air, a significant amount of metallic nickel or nickel oxide species (10.5 and 18.5 at%) remained on the surface. Exposure of HUVECs to these surfaces resulted in increased oxidative stress within the cells, loss of VE-cadherin and F-actin and significantly increased paracellular permeability. These pathological phenomena were not found in cells grown on NiTi which had undergone heat treatment at 600 degrees C. At this temperature thickening of the TiO(2) layer had occurred due to diffusion of titanium ions from the bulk of the alloy, displacing nickel ions to sub-surface areas. This resulted in a significant reduction in nickel ions detectable on the sample surface (4.8 at%). This study proposes that the integrity of human endothelial monolayers on NiTi is dependent upon the surface chemistry of the alloy and that this can be manipulated, using simple oxidising heat treatments.

The cell-substrate interaction of primary hippocampal neurones with thin films of TiN was studied in vitro. TiN films of different surface chemistries and topographies were deposited by pulsed DC reactive magnetron sputtering and closed field unbalanced magnetron sputter ion plating by Teer Coatings Ltd., Hartlebury, UK to result in TiN films with similar surface chemistries but different topographical features. TiN films were characterised using X-ray diffraction, X-ray photoelectron spectroscopy and atomic force microscopy. The neuron-substrate interaction was examined using environmental scanning electron microscopy (FEG-ESEM) for morphological information. Bromodeoxyuridine and TUNEL assays were used to identify proliferating neurones as well as apoptotic neurones. Fluorescent staining for MAP-2 was used to label neuronal network formation. Primary hippocampal neurones were found to attach and spread to all of the TiN film chemistries and topographies investigated. Neuronal network morphology appeared to be more preferential on the nitrogen rich TiN films and also with reduced nanotopographical features.

The cell-material interaction of 3T3-L1 fibroblasts with TiN films was studied in vitro. TiN films were deposited onto glass substrates to thicknesses of 0.2 and 1.0 microm by pulsed dc reactive magnetron sputtering. For comparison TiN films were deposited by closed field unbalanced magnetron sputter ion plating by Teer Coatings Ltd. (Hartlebury, UK) to result in TiN films with similar surface chemistries but having increased topographical features. TiN films were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, and atomic force microscopy. The cell-material interaction was examined morphologically by monitoring fibroblast attachment and growth and comparing to a control substrate. At early time points increased numbers of 3T3-L1 fibroblasts were found to preferentially attach to TiN films with an increase in the percentage of surface interstitial nitrogen and also with decreased topographical features. At later time points the presence of nanotopography appeared to play a greater role than the effects of surface chemistry and resulted in increased numbers of attached 3T3-L1 fibroblasts. The results show that by changing the deposition route and parameters to produce TiN films, the resultant films can be used to investigate the cellular response to surfaces of differing chemistry and topography., (Copyright 2003 Wiley Periodicals, Inc. J Biomed Mater Res 67A: 138-147, 2003)

Nickel titanium (NiTi) shape memory alloys have been investigated for several years with regard to biomedical applications. However, little is known about the influences of surface modifications on the biocompatibility of these alloys. The effects of a range of surface treatments were investigated. Cytotoxicity and cytocompatibility studies with both fibroblast and endothelial cells showed no differences in the biocompatibility of any of the NiTi surfaces. The cytotoxicity and cytocompatibility of all surfaces were favorable compared to the controls. The hemolysis caused by a range of NiTi surfaces was no different from that caused by polished 316L stainless steel or polished titanium surfaces. The spreading of platelets has been linked to the thrombogenicity of materials. Platelet studies here showed a significant increase in thrombogenicity on polished NiTi surfaces compared to 316L stainless steel and pure titanium surfaces. Heat treatment of NiTi was found to significantly reduce thrombogenicity, to the level of the control. The XPS results showed a significant decrease in the concentration of surface nickel with heat treatment and changes in the surface nickel itself from a metallic to an oxide state. This correlates with the observed reduction in thrombogenicity., (Copyright 2003 Wiley Periodicals, Inc.)

Thin films of TiN were investigated as a candidate microelectrode material for multi-electrode arrays, which are used for recording from electrically active cells in culture. TiN films were deposited onto glass substrates by DC pulsed reactive magnetron sputtering. The structure, phase composition and surface chemistry were studied using X-ray diffraction (XRD), Atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). The biocompatibility of the TiN films was examined morphologically by monitoring neuronal network formation and comparing this to a control substrate. Results indicate that neuronal cell adhesion and growth is influenced by the surface chemistry and associated crystal orientation of the TiN thin films.

Pulsed laser ablation is a new method for deposition of thin layers of hydroxyapatite (HA) on to biomaterial surfaces. In this paper, we report activity and morphology of osteoblasts grown on HA surfaces fabricated using different laser conditions. Two sets of films were deposited from dense HA targets, at three different laser fluences: 3, 6 and 9 Jcm(-2). One set of the surfaces was annealed at 575 degrees C to increase the crystallinity of the deposited films. Primary human osteoblasts were seeded onto the material surfaces and cytoskeletal actin organisation was examined using confocal laser scanning microscopy. The annealed surfaces supported greater cell attachment and more defined cytoskeletal actin organisation. Cell activity, measured using the alamar Blue assay, was also found to be significantly higher on the annealed samples. In addition, our results show distinct trends that correlate with the laser fluence used for deposition. The cell activity increases with increasing fluence. This pattern was repeated for alkaline phosphatase production by the cells. Differences in cell spreading were apparent which were correlated with the fluence used to deposit the HA. The optimum surface for initial attachment and spreading of osteoblasts was one of the HA films deposited using 9 J cm(-2) laser fluence and subsequently annealed at 575 degrees C.

The hemocompatibility of a TiN/TiC/diamond-like carbon (DLC) multilayer structure, deposited on titanium substrates for use as coatings for a heart valve prosthesis, has been studied through the adsorption of blood proteins and the adhesion and attachment of blood platelets. All of the surfaces were characterized by stylus profilometry and water contact angles. The adsorption of albumin and fibrinogen to the surfaces was assessed using the Amido Black assay, whereas platelet attachment was studied by scanning electron microscopy and quantified using stereological techniques. The degree of platelet spreading on the surfaces was seen to correlate with differences in surface energy, indicated from contact angle measurements. The greatest spreading was seen on the more hydrophilic surfaces. When studying protein adsorption to the surfaces, no correlation could be determined between contact angle results and levels of adsorption, although the most hydrophilic surfaces did appear to promote greater amounts of fibrinogen adsorption. Thrombus formation was observed to some degree on all of the surfaces, with the exception of the DLC coating. This coating also promoted less spreading of platelets than the other surfaces. The good hemocompatibility of the DLC coating is attributed to its hydrophobicity and smooth surface, resulting in a higher ratio of albumin to fibrinogen than any of the other surfaces., (Copyright 2000 John Wiley & Sons, Inc.)

The physical, chemical, and biological properties of pulsed laser deposited (PLD) and plasma sputtered (PS) hydroxyapatite (HA) coatings were compared. Human osteoblast-like cell responses to these coatings in vitro were assayed for proliferation and phenotypic expression. PS coatings formed smooth and continuous thin films that followed the contours of the substrate surface. PLD coatings consisted of numerous spheroidal micro- and macroparticles. The crystallinity of all coatings was quantified by comparison with the HA target used for both the PS and PLD processes. The XRD and FTIR results indicated that unannealed PLD coatings deposited at room temperature had X-ray spectra consistent with an amorphous structure and were found to dissolve after only a few hours in saline solution. Annealing at 400 degrees C increased the crystallinity (87-98%), which resulted in improved stability and cell activity. The PS coatings showed greater chemical stability than the unannealed PLD coatings and contained an approximate 15% crystalline phase, increasing to 65% postannealing. Cell proliferation and alkaline phosphatase production were significantly higher on unannealed PS specimens than the other coating treatments. There may be benefits in engineering the presence of a minor percentage of a microcrystalline phase in an amorphous or nanometer scale polycrystalline HA structure., (Copyright 2000 John Wiley & Sons, Inc.)

Plasma-sputtered hydroxyapatite (HA) thin coatings ( approximately 1 microm) were deposited onto uncoated and (TiAlV)N-coated Ti-6Al-4V-alloy substrates at low temperatures. The (TiAlV)N coating interlayer was deposited by reactive sputtering. Depositions were achieved by utilizing unbalanced and balanced magnetrons in a capacitively coupled RF plasma. Characterization of the thermostability, bioerosion resistance, and chemical composition of the coating layer was examined by scanning electron microscopy (SEM), energy-dispersive X-ray analysis (EDX), and Fourier transform infrared spectroscopy (FTIR). The results show that for deposition temperatures as low as 67 degrees C, the crystalline phase of the HA coating still is clearly detectable and that the underlying (TiAlV)N coating can increase the crystallinity and thermostability of the HA coating before and after heat treatment. The thin ( approximately 1 microm) sputtered HA coating shows strong HA characteristic peaks in the FTIR spectra even after a 30-day dissolution test. The experimental results show that a multilayer structure comprised of a bioinert (TiAlV)N and bioactive HA coating has the potential to improve the biocompatibility of implant materials. The bioinert (TiAlV)N coating also may provide a long-term stable interface between bone tissue and an alloy implant after the bioactive HA coating is remodeled by the surrounding tissue., (Copyright 1999 John Wiley & Sons, Inc.)