RESUMEN

Processing and properties of biodegradable load-bearing nanocomposite Fe-Ag scaffolds for bone ingrowth are reported. Fe-Ag nanocomposites were prepared employing high energy attrition milling of powders. Scaffolds with regular interconnected 300-400 µm pores and 60-75% porosity were prepared by cold sintering/high pressure consolidation of nanocomposite Fe-Ag granules, blended with porogen - highly water soluble sugar particles. The scaffolds' strength and permeability were found to be inversely related and to be strongly dependent on porosity. Presence of galvanic nanocouples in Fe5Ag and Fe10Ag resulted in desirable increase of degradation rate in saline solution as compared to pure Fe. The 70% and 75% macroporous Fe-Ag scaffolds possess high compressive strength (9.1-14.9 MPa) and permeability (1.0-3.5·10-10 m2) being in the range of trabecular/spongy bone. Method of estimation surface area of metal based macroporous scaffolds was proposed and successfully used.

Asunto(s)

RESUMEN

An original fabrication route of high-strength bulk Fe-5Ag and Fe-10Ag nanocomposites with enhanced degradation rate is reported. Near fully dense materials with fine nanostructures and uniform distribution of Ag nanoparticles were obtained employing high energy attrition milling of Fe-Ag2O powder blends followed by cold sintering - high pressure consolidation at ambient temperature that allowed the retention of the nanoscale structure. Annealing in hydrogen flow at 550 °C resulted in enhanced ductility without coarsening the nanostructure. The strength in compression of Fe5Ag and Fe10Ag nanocomposites was several-fold higher than the values reported for similar composites with micrometer grain size. The galvanic action of finely dispersed Ag nanoparticles greatly increased the corrosion rate and degradation kinetics of iron. Following four weeks immersion of Fe-Ag nanocomposites in saline solution, a more than 10% weight loss accompanied by less than 25% decrease in bending strength were measured. The interconnected nanoporosity of cold sintered Fe-Ag nanocomposites was utilized for incorporation of vancomycin that was gradually released upon immersion. In cell culture experiments, the Fe-Ag nanocomposites supported the attachment of osteoblast cells and exhibited no signs of cytotoxicity. The results suggest that the proposed Fe-Ag nanocomposites could be developed into attractive biodegradable load-bearing implant materials with drug delivery capability.

Asunto(s)

RESUMEN

In this paper, the processing and properties of iron-toughened bioresorbable ß-tricalcium phosphate (ß-TCP) nanocomposites are reported. ß-TCP is chemically similar to bone mineral and thus a good candidate material for bioresorbable bone healing devices; however intrinsic brittleness and low bending strength make it unsuitable for use in load-bearing sites. Near fully dense ß-TCP-matrix nanocomposites containing 30vol% Fe, with and without addition of silver, were produced employing high energy attrition milling of powders followed by high pressure consolidation/cold sintering at 2.5GPa. In order to increase pure iron's corrosion rate, 10 to 30vol% silver were added to the metal phase. The degradation behavior of the developed composite materials was studied by immersion in Ringer's and saline solutions for up to 1month. The mechanical properties, before and after immersion, were tested in compression and bending. All the compositions exhibited high mechanical strength, the strength in bending being several fold higher than that of polymer toughened ß-TCP-30PLA nanocomposites prepared by the similar procedure of attrition milling and cold sintering, and of pure high-temperature sintered ß-TCP. Partial substitution of iron with silver led to an increase in both strength and ductility. Furthermore, the galvanic action of silver particles dispersed in the iron phase significantly accelerated in vitro degradation of ß-TCP-30(Fe-Ag) nanocomposites. After 1month immersion, the composites retained about 50% of their initial bending strength. In cell culture experiments, ß-TCP-27Fe3Ag nanocomposites exhibited no signs of cytotoxicity towards human osteoblasts suggesting that they can be used as an implant material.

Asunto(s)

RESUMEN

A novel route for the synthesis of boehmite nanospheres with a hollow core and the shell composed of highly crumpled AlOOH nanosheets by oxidizing Al nanopowder in pure water under mild processing conditions is described. The stepwise events of Al transformation into boehmite are followed by monitoring the pH in the reaction medium. A mechanism of formation of hollow AlOOH nanospheres with a well-defined shape and crystallinity is proposed which includes the hydration of the Al oxide passivation layer, local corrosion of metallic Al accompanied by hydrogen evolution, the rupture of the protective layer, the dissolution of Al from the particle interior and the deposition of AlOOH nanosheets on the outer surface. In contrast to previously reported methods of boehmite nanoparticle synthesis, the proposed method is simple, and environmentally friendly and allows the generation of hydrogen gas as a by-product. Due to their high surface area and high, slit-shaped nanoporosity, the synthesized AlOOH nanostructures hold promise for the development of more effective catalysts, adsorbents, vaccines and drug carriers.

Asunto(s)

RESUMEN

In this work, osteoconductive composite materials comprising a large volume fraction of a bioresorbable calcium phosphate ceramic (CaP) and a smaller amount of a polycaprolactone polymer (PCL) were studied as a degradable antibiotic carrier material for treatment of osteomyelitis. Beads loaded with 1 and 4wt.% vancomycin were prepared by admixing dissolved drug to an in situ synthesized dicalcium phosphate (DCP)-PCL or solution-mixed beta-tricalcium phosphate (ßTCP)-PCL composite powder followed by high pressure consolidation of the blend at room temperature. Vancomycin release was measured in phosphate-buffered saline (PBS) at 37°C. All the beads gradually released the drug over the period of 4-11weeks, depending on the composite matrix homogeneity and porosity. Mathematical modeling using the Peppas equation showed that vancomycin elution was diffusion controlled. The stability of the antibiotic after high pressure application at room temperature was demonstrated by high-performance liquid chromatography-mass spectrometry (HPLC-MS) studies and MIC testing. The preservation of the structure and activity of vancomycin during the processing of composite beads and its sustained in vitro release profile suggest that high pressure consolidated CaP-PCL beads may be useful in the treatment of chronic bone infections as resorbable delivery vehicles of vancomycin and even of thermally unstable drug substances.

Asunto(s)

RESUMEN

Release of antimicrobial agents from bone healing devices can dramatically reduce the risk of implant-associated infection. Here we report the fabrication and antimicrobial activity of a multifunctional load-bearing bioresorbable material that can provide mechanical support to the healing bone all while slowly releasing an antibiotic drug. Dense beta-tricalcium phosphate (ß-TCP)-40 vol% polylactic acid (PLA) nanocomposite containing 1 wt% vancomycin (VH) was high pressure consolidated at 2.5 GPa, at room temperature, or at 120 °C. Over the course of 5 weeks in TRIS solution, the ß-TCP-PLA-VH nanocomposite released approximately 90 % of its drug load. Specimens consolidated at 120 °C had the highest initial mechanical properties and maintained 85 % of their compressive strength and 30 % of their bending strength after 5 weeks release. In vitro growth inhibition study showed significant antimicrobial efficacy of VH-impregnated ß-TCP-PLA against methicillin-resistant Staphylococcus aureus when exposed to both high (2 × 10(5) CFU/mL) and very high (1 × 10(8) CFU/mL) bacterial concentrations. After 1 week, total eradication of the microorganisms was achieved. The results suggest that the developed high-strength antibiotic-eluting ß-TCP-PLA nanocomposite can be a promising material for orthopedic surgical devices.

Asunto(s)

RESUMEN

Biodegradable calcium phosphate-PCL nanocomposite powders with unusually high ceramic volume fractions (80-95%) and uniform PCL distribution were synthesized by a non-aqueous chemical reaction in the presence of the dissolved polymer. No visible polymer separation occurred during processing. Depending on the reagents combination, either dicalcium phosphate (DCP) or Ca-deficient HA (CDHA) was obtained. CDHA-PCL composite powders were high pressure consolidated at room temperature yielding dense materials with high compressive strengths. Such densification route provides the possibility of incorporating drug and proteins without damaging their biological activity. The CDHA-PCL composites were tested in osteoblastic and endothelial cell line cultures and were found to support the attachment and proliferation of both cell types.

Asunto(s)

RESUMEN

Calcium phosphate (CaP) ceramics are widely used in bone tissue engineering due to their good osteoconductivity. The mechanical properties of CaP can be modified by the addition of small volume fractions of biodegradable polymers such as polycaprolactone (PCL). Nevertheless, it is also important to evaluate how the polymer content influences cell-material or cell-cell interactions because of potential consequences for bone regeneration and vascularization. In this study we assessed the general biocompatibilty of Ca-deficient hydroxyapatite (CDHA)-PCL disks containing nominally 11 and 24% polycaprolactone using human umbilical vein endothelial cells and human primary osteoblasts. Confocal microscopy showed that both CDHA-PCL variants supported the growth of both cell types. In terms of the endothelial cells grown on CDHA-PCL nanocomposites with 24% PCL, an increased expression of the endothelial marker vWF compared to CDHA-PCL with 11% PCL was observed in real-time polymerase chain reaction analysis. In addition to monocultures, co-cultures of outgrowth endothelial cells, derived from peripheral blood, and primary osteoblasts were assessed as an example of a more complex test system for bone regeneration and vascularization. Constructs based on CDHA with different PCL contents were investigated with regard to the formation of microvessel-like structures induced by the co-culture process using confocal microscopy and quantitative image analysis. Furthermore, the osteogenic differentiation of the co-culture was assessed. As a result, more pre-vascular structures were observed after 1 week on the CDHA-PCL disks with 24% PCL, whereas after 4 weeks of culture the extent of microvessel-like structure formation was slightly higher on the CDHA with 11% PCL. In contrast to this, variation of PCL content had no effect on the osteogenic differentiation in the co-culture.

Asunto(s)

RESUMEN

A new low modulus beta Ti-Nb alloy with low elastic modulus and excellent corrosion resistance is currently under consideration as a surgical implant material. The usefulness of such materials can be dramatically enhanced if their surface structure and surface chemistry can be controlled. This control is achieved by attaching a self assembled monolayer (SAM) based on 11-chloroacetyl-1-undecylphosphonic acid, CAUDPA, to the surface and immobilization of a peptide to the monolayer. The SAM is characterized by Fourier Transform Infrared Spectroscopy (FTIR) and X-ray Photoelectron Spectroscopy (XPS) at two different takeoff angles. The CAUDPA molecules were covalently bonded on the substrate in a configuration in which the phosphonic group turns toward the Ti45Nb while the acetyl chloride end group tail turns to the topmost surface. In such configuration sequential in situ reaction is possible by exchange between the chloride and a biological molecule. Such biological molecule is the arginine-glycine-aspartic acid-cysteine, RGDC, small amino acid sequence present in many molecules of the extracellular matrix. Preliminary cell culture in-vitro result shows an improvement of the response of osteoblast cells to Ti45Nb after the peptide immobilization.

Asunto(s)

RESUMEN

The corrosion and electrochemical behavior of a low stiffness beta -Ti-45wt.%Nb (Ti45Nb) was studied in solutions that resemble body environment, as compared to Ti6Al4V and Ti-55wt.%Ni (Ti55Ni, Nitinol) alloys currently used in surgical implants. In Ringers' solution, Ti45Nb alloy exhibited an excellent corrosion resistance, comparable to that of Ti6Al4V and much better than that of Nitinol. In acidic environments, beta -Ti45Nb remained passive under conditions where active dissolution was observed for both Ti6Al4V and Nitinol alloys. The results warrant further corrosion and biocompatibility studies of beta -Ti45Nb alloy to establish its suitability as implant material.

Asunto(s)

RESUMEN

Wear behaviour of TiN(titanium nitride)-coated Ti and Ti-6AI-4V alloy against UHMW polyethylene was studied in hip simulation test. Ti alloys possess an excellent combination of mechanical properties and biocompatibility, however, they suffer from inadequate wear resistance. Thus, their use as articulating components of total joint replacements requires surface hardening, e.g. by TiN. Thirty-two millimetre diameter cp-Ti and Ti-6AI-4V femoral heads were coated with several micrometre thick TiN layers employing an original PIRAC nitriding method based on interaction of Ti alloy substrate with highly reactive monatomic nitrogen. The heads were tested against UHMWPE cups at 37 degrees C in Ringer's solution or in distilled water. Simulator tests were performed at peak pressures of 1.5 and 2.0 MPa in a constant rotation mode at the frequency of 1.5 Hz. The wear of UHMWPE was estimated by weight loss, and the worn metallic and polyethylene surfaces were examined in SEM. The wear rate of UHMWPE cups articulating against PIRAC coated Ti and Ti-6AI-4V after up to 4 x 10(6) cycles was significantly lower than that of UHMWPE articulating against 316L stainless steel. No delamination of TiN coatings was observed after 4 x 10(6) cycles. These results suggest that TiN PIRAC coating on Ti-6AI-4V heads could minimise the wear of total hip replacements without compromising the mechanical properties of the femoral component.

Asunto(s)

RESUMEN

Nickel-titanium (NiTi, nitinol) shape memory alloy was nitrided using an original powder immersion reaction assisted coating (PIRAC) method in order to modify its surface properties. PIRAC nitriding method is based on annealing the samples in the atmosphere of highly reactive nitrogen supplied by decomposition of unstable nitride powders or, alternatively, by selective diffusion of the atmospheric nitrogen to the sample surface. Being a non-line-of-sight process, PIRAC nitriding allows uniform treatment of complex shape surgical implants. Hard two-layer titanium nitride (TiN)/Ti2, Ni coatings were obtained on NiTi surface after PIRAC anneals at 900 and 1000 degrees C. PIRAC coating procedure was found to considerably improve the corrosion behavior of NiTi alloy in Ringer's solution. In contrast to untreated nitinol, no pitting was observed in the samples PIRAC nitrided at 1000 degrees C, 1 h up to 1.1 V. The coated samples were also characterized by very low anodic currents in the passive region and by an exceedingly low metal ion release rate. The research results suggest that PIRAC nitriding procedure could improve the in vivo performance of NiTi alloys implanted into the human body.

Asunto(s)

RESUMEN

Hard titanium nitride (TiN) coatings were obtained on the surface of Ti-6Al-4V alloy using an original PIRAC nitriding method, based on annealing the samples under a low pressure of monatomic nitrogen created by selective diffusion of N from the atmosphere. PIRAC nitrided samples exhibited excellent corrosion resistance in Ringer's solution in both potentiodynamic and potentiostatic tests. The anodic current and metal ion release rate of PIRAC nitrided Ti-6Al-4V at the typical corrosion potential values were significantly lower than those of the untreated alloy. This, together with the excellent adhesion and high wear resistance of the TiN coatings, makes PIRAC nitriding an attractive surface treatment for Ti-6Al-4V alloy surgical implants.

RESUMEN

Coating titanium alloy implants with titanium nitride (TiN) by the method of Powder Immersion Reaction Assisted Coating (PIRAC) produces a stable layer on their surface. We have examined the ability of the new TiN coating to undergo osseointegration. We implanted TiN-coated and uncoated Ti6Al4V alloy pins into the femora of six-month-old female Wistar rats. SEM after two months showed a bone collar around both TiN-coated and uncoated implants. Morphometrical analysis revealed no significant differences between the percentage of the implant-bone contact and the area and volume of the bone around TiN-coated compared with uncoated implants. Electron-probe microanalysis indicated the presence of calcium and phosphorus at the implant-bone interface. Mineralisation around the implants was also confirmed by labelling with oxytetracycline. Strong activity of alkaline phosphatase and weak activity of tartrate-resistant acid phosphatase were shown histochemically. Very few macrophages were detected by the non-specific esterase reaction at the site of implantation. Our findings indicate good biocompatibility and bone-bonding properties of the new PIRAC TiN coatings which are comparable to those of uncoated Ti6Al4V alloy implants.

Asunto(s)

RESUMEN

The performance of any material in the human body is controlled by two sets of characteristics: biofunctionality and biocompatibility. With the wide range of materials available in the mid-1990s, it is relatively easy to satisfy the requirements for mechanical and physical functionality of implantable devices. Therefore, the selection of materials for medical applications is usually based on considerations of biocompatibility. When metals and alloys are considered, the susceptibility of the material to corrosion and the effect the corrosion has on the tissue are the central aspects of biocompatibility. Corrosion resistance of the currently used 316L stainless steel, cobalt-chromium, and titanium-based implant alloys relies on their passivation by a thin surface layer of oxide. Stainless steel is the least corrosion resistant, and it is used for temporary implants only. The titanium and Co-Cr alloys do not corrode in the body; however, metal ions slowly diffuse through the oxide layer and accumulate in the tissue. When a metal implant is placed in the human body, it becomes surrounded by a layer of fibrous tissue of a thickness that is proportional to the amount and toxicity of the dissolution products and to the amount of motion between the implant and the adjacent tissues. Pure titanium may elicit a minimal fibrous encapsulation under some conditions, whereas the proliferation of a fibrous layer as much as 2 mm thick is encountered with the use of stainless steel implants. Superior fracture and fatigue resistance have made metals the materials of choice for traditional load-bearing applications. In this review, the functionality of currently used metals and alloys is discussed with respect to stenting applications. In addition, the "shape memory" and "pseudo-elasticity" properties of Nitinol-an alloy that is being considered for the manufacturing of urologic stents-are described.

Asunto(s)