Effects of surface mechanical attrition treatment (SMAT) on a rough surface of AISI 316L stainless steel

Surface mechanical attrition treatment (SMAT) improves mechanical properties of metallic materials through the formation of nanocrystallites at their surface layer. It also modifies the morphology and roughness of the work surface. Surface roughening by the SMAT has been reported previously in a smooth specimen, however in this study the starting point was a rough surface and a smoothening phenomenon is observed. In this paper, the mechanisms involved in the surface smoothening of AISI 316L stainless steel during the SMAT are elucidated. The SMAT was conducted on a specimen with a roughness of R_a = 3.98 μm for 0–20 min. The size of milling balls used in the SMAT was varied from 3.18 mm to 6.35 mm. The modification of subsurface microhardness, surface morphology, roughness and mass reduction of the specimen due to the SMAT were studied. The result shows the increasing microhardness of the surface and subsurface of the steel due to the SMAT. The impacts of milling balls deform the surface and produce a flat-like structure at this layer. Surface roughness decreases until its saturation is achieved in the SMAT. The mass reduction of the specimens is also detected and may indicate material removal or surface erosion by the SMAT. The size of milling ball is found to be the important feature determining the pattern of roughness evolution and material removal during the SMAT. From this study, two principal mechanisms in the evolution of surface morphology and roughness during the SMAT are proposed, i.e. indentation and surface erosion by the multiple impacts of milling balls. A comparative study with the results of the previous experiment indicates that the initial surface roughness has no influence in the work hardening by the SMAT but it does slightly on the saturated roughness value obtained by this treatment.     

Peri-implant osteogenesis in health and osteoporosis

Long-term clinical success of endosseous dental implants is critically related to a wide bone-to-implant direct contact. This condition is called osseointegration and is achieved ensuring a mechanical primary stability to the implant immediately after implantation. Both primary stability and osseointegration are favoured by micro-rough implant surfaces which are obtained by different techniques from titanium implants or coating the titanium with different materials. Host bone drilled cavity is comparable to a common bone wound. In the early bone response to the implant, the first tissue which comes into contact with the implant surface is the blood clot, with particular attention to platelets and fibrin. Peri-implant tissue healing starts with an inflammatory response as the implant is inserted in the bone cavity, but an early afibrillar calcified layer comparable to the lamina limitans or incremental lines in bone is just observable at the implant surface both in vitro than in vivo conditions. Just within the first day from implantation, mesenchymal cells, pre-osteoblasts and osteoblasts adhere to the implant surface covered by the afibrillar calcified layer to produce collagen fibrils of osteoid tissue. Within few days from implantation a woven bone and then a reparative trabecular bone with bone trabeculae delimiting large marrow spaces rich in blood vessels and mesenchymal cells are present at the gap between the implant and the host bone. The peri-implant osteogenesis can proceed from the host bone to the implant surface (distant osteogenesis) and from the implant surface to the host bone (contact osteogenesis) in the so called de novo bone formation. This early bone response to the implant gradually develops into a biological fixation of the device and consists in an early deposition of a newly formed reparative bone just in direct contact with the implant surface. Nowadays, senile and post-menopausal osteoporosis are extremely diffuse in the population and have important consequences on the clinical success of endosseous dental implants. In particular the systemic methabolic and site morphological conditions are not favorable to primary stability, biological fixation and final osseointegration.

An early good biological fixation may allow the shortening of time before loading the implant, favouring the clinical procedure of early or immediate implant loading. Trabecular bone in implant biological fixation is gradually substituted by a mature lamellar bone which characterizes the implant ossoeintegration. As a final consideration, the mature lamellar bone observed in osseointegrated implants is not always the same as a biological turnover occurs in the peri-implant bone up to 1 mm from the implant surface, with both osteogenesis and bone reabsorption processes.     

In vitro evaluation of osteoblast‐like cells on hydroxyapatite‐coated porous stainless steel implants by synchrotron radiation x‐ray fluorescence

The successful application of artificial implants requires osseointegration in the implanted structures. To stimulate bone growth, synthetic hydroxyapatite obtained by the coprecipitation process was coated onto porous stainless steel substrates in order to enhance the biocompatibility and, consequently, mineralization. The substrate of choice was porous 316L stainless steel for its high resistance, mechanical strength and low density due to its foam structure. The aim of the present study was to investigate the biological response of the fabricated implants cultured with MC3T3‐E1 mouse osteoblast‐like cells by analyzing the variation in the elemental concentration, mainly calcium, along with the cellular differentiation and mineralization. By employing synchrotron radiation x‐ray fluorescence spectroscopy (SRXRF), intracellular elemental distribution and concentration could be determined, revealing a clear increase in the total calcium content. This preliminary data suggests that synthetic hydroxyapatite on porous stainless steel substrates might be successfully used for biocompatible medical implants. Copyright © 2009 John Wiley & Sons, Ltd.     

Bio-activated titanium surface utilizable for mimetic bone implantation in dentistry—Part III: Surface characteristics and bone–implant contact formation

This study was carried out to quantify the effect of an alkali-modified surface on the bone–implant interface formation during healing using an animal model. A total of 24 screw-shaped, self-tapping, (c.p.) titanium dental implants, divided into test group B—implants with alkali-modified surface (Bio surface) and control group M—implants with turned, machined surface, were inserted without pre-tapping in the tibiae of three beagle dogs. The animals were sacrificed after 2, 5 and 12 weeks and the bone–implant contact (BIC%) was evaluated histometrically. The surface characteristics that differed between the implant surfaces, i.e. specific surface area, contact angle, may represent factors that influence the rate of osseointegration and the secondary implant stability. The alkali-treated surface enhances the BIC formation during the first 2–5 weeks of healing compared to the turned, machined surface.     

Surface modification of Ti dental implants by Nd:YVO4 laser irradiation

Surface modifications have been applied in endosteal bone devices in order to improve the osseointegration through direct contact between neoformed bone and the implant without an intervening soft tissue layer. Surface characteristics of titanium implants have been modified by addictive methods, such as metallic titanium, titanium oxide and hydroxyapatite powder plasma spray, as well as by subtractive methods, such as acid etching, acid etching associated with sandblasting by either AlO₂ or TiO₂, and recently by laser ablation. Surface modification for dental and medical implants can be obtained by using laser irradiation technique where its parameters like repetition rate, pulse energy, scanning speed and fluency must be taken into accounting to the appropriate surface topography. Surfaces of commercially pure Ti (cpTi) were modified by laser Nd:YVO₄ in nine different parameters configurations, all under normal atmosphere. The samples were characterized by SEM and XRD refined by Rietveld method. The crystalline phases αTi, βTi, Ti₆O, Ti₃O and TiO were formed by the melting and fast cooling processes during irradiation. The resulting phases on the irradiated surface were correlated with the laser beam parameters. The aim of the present work was to control titanium oxides formations in order to improve implants osseointegration by using a laser irradiation technique which is of great importance to biomaterial devices due to being a clean and reproducible process.     

Effect of two-step functionalization of Ti by chemical processes on protein adsorption

Titanium and its alloys are widely used for orthopedic and dental implants because of their superior mechanical properties, low modulus, excellent corrosion resistance and good biocompatibility. However, it takes several months for titanium implants and bone tissue to reach integration. Hence, there is growing interest in shortening the process of osseointegration and thereby reducing surgical restrictions. Various surface modifications have been applied to form a bioactive titanium oxide layer on the metal surface, which is known to accelerate osseointegration.The present work shows that titanium dioxide (TiO₂) layers formed on titanium substrates by etching in a solution of sodium hydroxide (NaOH) or hydrogen peroxide/phosphoric acid (H₃PO₄/H₂O₂, with a volume ratio of 1:1) are highly suitable pre-treatments for apatite-like coating deposition. Using a two-step procedure (etching in an alkaline or acidic solution followed by soaking in Hanks’ medium), biomimetic calcium phosphate coatings were deposited on porous TiO₂ layers. The combined effects of surface topography and chemistry on the formation of the calcium phosphate layer are presented. The topography of the TiO₂ layers was characterized using HR-SEM and AFM techniques. The nucleation and growth of calcium phosphate (Ca-P) coatings deposited on TiO₂ porous layers from Hanks’ solution was investigated using HR-SEM microscopy. AES, XPS and FTIR surface analytical techniques were used to characterize the titanium dioxide layers before and after deposition of the calcium phosphate coatings, as well as after the process of protein adsorption. To evaluate the potential use of such materials for biomedical applications, the adsorption of serum albumin, the most abundant protein in the blood, was studied on such surfaces.     

Composite coating of 58S bioglass and hydroxyapatite on a poly (ethylene terepthalate) artificial ligament graft for the graft osseointegration in a bone tunnel

The purpose of this study was to determine the effect of the combination of hydroxyapatite (HA) and bioglass (BG) on polyethylene terephthalate (PET) artificial ligament graft osseointegration within the bone tunnel. The results of in vitro culturing of MC3T3-E1 mouse osteoblastic cells proved that this HA/BG composite coating can promote the cell compatibility of grafts. A rabbit extraarticular tendon-to-bone healing model was used to evaluate the effect of this composite coating on PET artificial ligaments in vivo. The final results demonstrated that HA/BG coating improved new bone formation at the graft-bone interface and increased the load-to-failure property of graft in bone tunnel compared to the control group at early time. The study has shown that HA/BG composite coating on the PET artificial ligament surface has a positive effect in the induction of artificial ligament osseointegration within the bone tunnel.     

The effect of surface nanocrystallization on plasma nitriding behaviour of AISI 4140 steel

A plastic deformation surface layer with nanocrystalline grains was produced on AISI 4140 steel by means of surface mechanical attrition treatment (SMAT). Plasma nitriding of SMAT and un-SMAT AISI 4140 steel was carried out by a low-frequency pulse excited plasma unit. A series of nitriding experiments has been conducted at temperatures ranging from 380 to 500 °C for 8 h in an NH₃ gas. The samples were characterized using X-ray diffraction, scanning electron microscopy, optical microscopy and Vickers microhardness tester. The results showed that a much thicker compound layer with higher hardness was obtained for the SMAT samples when compared with un-SMAT samples after nitriding at the low temperature. In particular, plasma nitriding SMAT AISI 4140 steel at 380 °C for 8 h can produced a compound layer of 2.5 μm thickness with very high hardness on the surface, which is similar to un-SMAT samples were plasma nitrided at approximately 430 °C within the same time.     

Adsorption of Metformin on Graphene Nanoribbons and Application in Treatment of Oral Cancer Using Photothermal Energy

Graphene nanoribbons are thin sheets of graphene showing exclusive characteristics such as better drug-loading capacity, adsorption on mammalian cells, greater surface area, and light-absorbing ability. The current research work is to develop metformin-adsorbed carboxyl-functionalized oxidized graphene nanoribbons and utilize drug repurposing for the treatment of oral cancer by activating photo-thermal radiation therapy. The nanoribbons are formulated by Hummer's method and evaluated for several characterization parameters like ATR- Fourier Transform Infrared (FTIR), Differential scanning calorimetry (DSC), topology, in vitro efficacy, ex vivo and in vitro cell line studies. The ATR-FTIR spectrum of formulated nanoribbons shows distinctive peak at 3370 cm⁻¹ ( N H group) of metformin. The DSC specifies the incidence of steep endothermic crests at 235 °C ( C NH₃). The in vitro and ex vivo drug release studies show enhanced drug release in acidic pH (6.4) than physiological pH (7.4) with photothermal radiation. The in vitro cell line studies are processed via two-way ANOVA that exhibits 67.74 ± 0.03% of % inhibition in presence of photothermal radiation. The study demonstrates higher inhibition of cancerous cells at lower concentration of drug and photothermal therapy in comparison to plain drug. The characteristic feature of graphene is used to develop targeted drug delivery system against the oral cancerous cells.     

The effect of nanostructured surface layer on the fatigue behaviors of a carbon steel

A nanostructured surface layer was formed on a carbon steel by means of surface mechanical attrition treatment (SMAT). The microstructure of the surface layer of the SMATed sample was characterized by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Microhardness and residual stress distribution along the depth from the SMATed surface layer were measured at the same time. Fatigue behaviors of the carbon steel subjected to the SMAT process were investigated. A nanostructured layer with average grains size of ∼12.7 nm was formed, of which microhardness is more than twice as high as that in matrix and residual compressive stress can reach about −400 MPa with maximum depth of ∼600 μm. The fatigue strength of as-received sample is 267 MPa and that of SMATed sample is 302 MPa based on fatigue life 5 × 10⁶ cycles. The SMAT process has improved the fatigue strength by as much as 13.1% for the carbon steel. It is shown that the SMAT is an effective method to render the material with the features, such as a nanostructured and work-hardened surface layer as well as compressive residual stresses, which can pronouncedly improve the fatigue strength of the carbon steel.     

One way of surface alloying treatment on iron surface based on surface mechanical attrition treatment and heat treatment

A method of surface alloying treatment has been developed: Ni powders were welded into the surface of iron plates by Surface Mechanical Attrition Treatment (SMAT), followed by annealing at certain temperature for 30 min. A Ni-Fe alloy layer with thickness about 100 μm in the sample surface was fabricated on pure iron plate. Scanning electron microscope (SEM), glow discharge spectrum (GDS), and X-ray diffraction (XRD) methods were used to analyze the microstructure, the composition and the phases of the alloy layer. Studies on the interface microstructure indicated that there was significant atomic diffusion and formation of multilayer of intermetallic compound and solid solution in SMAT process. Subsequent annealing accelerates the alloying process. The corrosion test shows the sample by SMAT treated with Ni powders exhibit the best corrosion resistance.     

Surface bioactivity modification of titanium by CO2 plasma treatment and induction of hydroxyapatite: In vitro and in vivo studies

Since metallic biomaterials used for orthopedic and dental implants possess a paucity of reactive functional groups, bioactivity modification of these materials is challenging. In the present work, the titanium discs and rods were treated with carbon dioxide plasma and then incubated in a modified simulated body fluid 1.5SBF to obtain a hydroxyapatite layer. Surface hydrophilicity of samples, changes of surface chemistry, surface morphologies of samples, and structural analysis of formed hydroxyapatite were investigated by contact angle to water, X-ray photoelectron spectrometer (XPS), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and X-ray diffraction (XRD). The results demonstrated that hydrophilicity of titanium surface was improved and hydroxyl groups increased after modification with carbon dioxide plasma treatment. The hydroxyl groups on the surface of titanium were the richest after carbon dioxide plasma treatment under the condition of 20 W for less than 30 s. The hydroxyapatite formability of titanium surface was enhanced by carbon dioxide plasma pretreatment, which was attributed to the surface chemistry. MC3T3-E1 cell as a model cell was cultured on the Ti, CPT-Ti and CPT/SBF-Ti discs in vitro, and the results of the morphology and differentiation of the cell showed that CPT/SBF-Ti was the highest bioactive. The relative parameters of the new bone around the Ti and CPT/SBF-Ti rods including bone mineral density (BMD), a ratio of bone volume to total volume (BV/TV), trabecular thickness (Tb.Th.) and trabecular number (Tb.N.) were analyzed by a micro-computed tomography (micro-CT) after 4-, 8- and 12-week implantation periods in vivo. The results indicated that the CPT/SBF-Ti was more advantageous for new bone formation.     

Bone regeneration based on nano-hydroxyapatite and hydroxyapatite/chitosan nanocomposites: an in vitro and in vivo comparative study

Surface morphology, surface wettability, and size distribution of biomaterials affect their in vitro and in vivo bone regeneration potential. Since nano-hydroxyapatite has a great chemical and structural similarity to natural bone and dental tissues, incorporated biomaterial of such products could improve bioactivity and bone bonding ability. In this research, nano-hydroxyapatite (23 ± 0.09 nm) and its composites with variety of chitosan content [2, 4, and 6 g (45 ± 0.19, 32 ± 0.12, and 28 ± 0.12 nm, respectively)] were prepared via an in situ hybridization route. Size distribution of the particles, protein adsorption, and calcium deposition of powders by the osteoblast cells, gene expression and percentage of new bone formation area were investigated. The highest degree of bone regeneration potential was observed in nano-hydroxyapatite powder, while the bone regeneration was lowest in nano-hydroxyapatite with 6 g of chitosan. Regarding these data, suitable size distribution next to size distribution of hydroxyapatite in bone, smaller size, higher wettability, lower surface roughness of the nano-hydroxyapatite particles and homogeneity in surface resulted in higher protein adsorption, cell differentiation and percentage of bone formation area. Results obtained from in vivo and in vitro tests confirmed the role of surface morphology, surface wettability, mean size and size distribution of biomaterial besides surface chemistry as a temporary bone substitute.     

Interaction of biological and nonbiological surfaces. New opportunities for research and technologies using synchrotron radiation

The applicability of synchrotron radiation to implementation of medical ideas associated with introduction of nonbiological objects into a human body—implants, drug nanocapsules, and X-ray therapeutic means (metal nanoparticles and nanocrystalline phosphors and scintillators)—is considered. Synchrotron radiation presents new possibilities of analyzing the surface with a resolution comparable to the sizes of biological nanostructures involved in interactions such as chemical and biochemical modification of implant surfaces in vitro; activation of implant surface integration with biological tissue in a tissue culture (in vitro) and in vivo; biochemical modification of therapeutic nanoparticle surface in vitro; immunocamouflage by host proteins; attachment of “molecular targets”, i.e., antibodies, to target tissue to provide targeted delivery vehicles; and local activation of X-ray therapeutic drugs and drug nanocapsules in biological tissues. A functional block diagram of a medical technological station is given.     

Enhanced electroluminescence of ZnO nanocrystalline annealing from mesoporous precursors

An improved sol-gel method was used to prepare ZnO nanoparticles. EL results showed that slowing the addition of LiOH solution and heating in vacuum to obtain gel precipitation made the final ZnO samples’ emission peak blue shift to 520 nm. Simultaneously, the peak value of the sample processed with no templates was enhanced 4.68 times and that of the sample processed with ODA was enhanced 0.71 times. Two copolymers Pluronic P123 (P123) and Pluronic F-127 (F-127) were adopted respectively as template reagents. The obtained mesoporous ZnO precursors exhibited a surface area of 69.21 m²/g and 103.57 m²/g and an average pore size of 6.61 nm and 5.70 nm, respectively. After calcining in a muffle furnace in air, the obtained ZnO nanocrystalline samples from these precursors revealed stronger green emission than the samples dealt with ODA. Compared to the magnification multiple of 0.89 times of the sample processed with ODA, the peak intensity of the sample processed with P123 was 2.03 times higher than that of the sample processed with no template reagents, and the intensity of the sample processed with F-127 was 3.3 times higher. This may be due to the larger surface area of samples from the longer molecule chains of the two template reagents.     

Advances in the ultrastructural study of the implant-bone interface by backscattered electron imaging

The biocompatibility of titanium implants in bone depends on the response shown by cells in contact with the implant surface. Several developments have been targeted at achieving successful implant treatment. The aim of this study was to develop a novel preparation procedure to evaluate the bone cell response produced at the bone–implant interface using the technique scanning electron microscopy with backscattered electron imaging (SEM-BSE). Dental prostheses with an SLA-modified or TOP-modified surface were implanted in a toothless part of the mandibula in female pigs. The animals were sacrificed 12 weeks after surgery, at which time block specimens containing the implants were obtained. These specimens were then processed for SEM-BSE by optimizing a protocol involving chemical fixation and heavy metal staining. In addition, element distribution maps for the implant–bone tissue interface were obtained using a microanalytical system based on energy-dispersive X-ray spectrometry (EDS). This novel visualisation approach enabled a comprehensive study of the extracellular matrix and cell components of the host tissues neoformed around the implant. SEM-BSE images also provided ultrastructural details of the bone cells. This technique appears to be an effective and very promising tool for detailed studies on the implant–bone tissue interface and the host response to the bone incorporation process.     

Improved biological performance of low modulus Ti-24Nb-4Zr-7.9Sn implants due to surface modification by anodic oxidation

Dental implants are usually made from commercially pure titanium or titanium alloys. The purpose of this study was to evaluate the influence of surface treatment to low modulus Ti-24Nb-4Zr-7.9Sn (TNZS) on cell and bone responses. The TNZS alloy samples were modified using anodic oxidation (AD). Surface oxide properties were characterized by using various surface analytic techniques, involving scanning electron microscopy (SEM) equipped with energy dispersive spectrometer (EDS), X-ray diffractometry (XRD) and surface profilometer. During the AD treatment, porous titanium oxide layer was formed and Ca ions were incorporated into the oxide layer. The viability and morphology of osteoblasts on Ca-incorporated TNZS were studied. The bone responses of Ca-incorporated TNZS were evaluated by pull-out tests and morphological analysis after implantation in rabbit tibiae. The non-treated Ti and TNZS samples were used as the control. Significant increases in cell viability and pull-out forces (p < 0.05) were observed for Ca-incorporated TNZS implants compared with those for the control groups. Porous structures supplied positive guidance cues for osteoblasts to attach. The enhanced cell and bone responses to Ca-incorporated TNZS implants could be explained by the surface chemistry and microtopography.     

Nanostructured β-type titanium alloy fabricated by ultrasonic nanocrystal surface modification

The surface of β-type Ti-Nb-Ta-Zr (TNTZ) alloy, which is a promising material for biomedical applications, was treated with the ultrasonic nanocrystal surface modification (UNSM) technique to enhance its hardness. As a result, a gradient nanostructured (GNS) layer was generated in the surface; the microstructure of the top surface layer consisted of nanoscale lamellae with a width of about 60–200 nm. In addition, there were lamellar grains consisting of nanostructured subgrains having unclear and wavy boundaries. The treated surface exhibited a hardness value of ∼385 HV compared to 190 HV for the untreated alloy. It was further determined that highly dense deformation twins were generated at a depth of ∼40–150 µm below the UNSM-treated surface. These deformation twins led to a significant work hardening effect which aided in enhancing the mechanical properties. It was also found that UNSM treatment resulted in the formation of micropatterns on the surface, which would be beneficial for high bioactivity and bone regeneration performance of TNTZ implants.     

Surface evolution of a gradient structured Ti in hydrogen peroxide solution

In this work, the interaction between hydrogen peroxide (H₂O₂) and a gradient structured Ti was investigated extensively. The gradient structured Ti (SMAT Ti) was produced by surface mechanical attrition treatment (SMAT), and then it was immersed in H₂O₂ solution for different time until 48 h at room temperature (25 °C). The structure and surface morphology evolution were examined by Raman spectra and scanning electron microscopy (SEM). The formation mechanism of nanoporous titania was discussed based on above results.     

Influence of ion implantation on titanium surfaces for medical applications

The implantation of ions into the near surface layer is a new approach to improve the osseointegration of metallic biomaterials like titanium. Meanwhile it is well known that surface topography and surface physico-chemistry as well as visco-elastic properties influence the cell response after implantation of implants into the human body. To optimize the cell response of titanium, ion implantation techniques have been used to integrate calcium and phosphorus, both elements present in the inorganic bone phase. In this context, the concentration profile of the detected elements and their chemical state have been investigated using X-ray photoelectron spectroscopy and Auger electron spectroscopy depth profiling. Ion implantation leads to strong changes of the chemical composition of the near surface region, which are expected to modify the biofunctionality as observed in previous experiments on the cell response. The co-implantation of calcium and phosphorus samples, which showed best results in the performed tests (biological and physical), leads to a strong modification of the chemical surface composition.