Dragoslav Stamenković

Relationship between microstructure, cytotoxicity and corrosion properties of a Cu-Al-Ni shape memory alloy.

Cu-Al-Ni shape memory alloys (SMAs) have been investigated as materials for medical devices, but their biomedical application is still limited. The aim of this work was to compare the microstructure, corrosion and cytotoxicity in vitro of a Cu-Al-Ni SMA. Rapidly solidified (RS) thin ribbons, manufactured via melt spinning, were used for the tests. The control alloy was a permanent mould casting of the same composition, but without shape memory effect. The results show that RS ribbons are significantly more resistant to corrosion compared with the control alloy, as judged by the lesser release of Cu and Ni into the conditioning medium. These results correlate with the finding that RS ribbons were not cytotoxic to L929 mouse fibroblasts and rat thymocytes. In addition, the RS ribbon conditioning medium inhibited cellular proliferation and IL-2 production by activated rat splenocytes to a much lesser extent. The inhibitory effects were almost completely abolished by conditioning the RS ribbons in culture medium for 4 weeks. Microstructural analysis showed that RS ribbons are martensitic, with boron particles as a minor phase. In contrast, the control Cu-Al-Ni alloy had a complex multiphase microstructure. Examination of the alloy surfaces after conditioning by energy dispersive X-ray and Auger electron spectroscopy showed the formation of Cu and Al oxide layers and confirmed that the metals in RS ribbons are less susceptible to oxidation and corrosion compared with the control alloy. In conclusion, these results suggest that rapid solidification significantly improves the corrosion stability and biocompatibility in vitro of Cu-Al-Ni SMA ribbons.

The influence of the microstructure of high noble gold-platinum dental alloys on their corrosion and biocompatibility in vitro

The aim of this work was to compare the microstructures of two high noble experimental Au-Pt alloys with similar composition with their corrosion and biocompatibility in vitro. We showed that Au-Pt II alloy, composed of 87.3 wt.% Au, 9.9 wt.% Pt, 1.7 wt.% Zn and 0.5 wt.% Ir + Rh + In, although possessing better mechanical properties than the Au-Pt I alloy (86.9 wt.% Au, 10.4 wt.% Pt, 1.5 wt.% Zn and 0.5 wt.% Ir + Rh + In), exerted higher adverse effects on the viability of L929 cells and the suppression of rat thymocyte functions, such as proliferation activity, the production of Interleukin-2 (IL-2), expression of IL-2 receptor and activation — induced apoptosis after stimulation of the cells with Concanavalin-A. These results correlated with the higher release of Zn ions in the culture medium. As Zn2+, at the concentrations which were detected in the alloy’s culture media, showed a lesser cytotoxic effect than the Au-Pt conditioning media, we concluded that Zn is probably not the only element responsible for alloy cytotoxicity. Microstructural characterization of the alloys, performed by means of scanning electron microscopy in addition to energy dispersive X-ray and X-ray diffraction analyses, showed that Au-Pt I is a two-phase alloy containing a dominant Au-rich α1 phase and a minor Pt-rich α2 phase. On the other hand, the Au-Pt II alloy additionally contained three minor phases: AuZn3, Pt3Zn and Au1.4Zn0.52. The highest content of Zn was identified in the Pt3Zn phase. After conditioning, the Pt3Zn and AuZn3 phases disappeared, suggesting that they are predominantly responsible for Zn loss, lower corrosion stability and subsequent lower biocompatibility of the Au-Pt II alloy.

The Mechanical Properties of a Poly(methyl methacrylate) Denture Base Material Modified with Dimethyl Itaconate and Di-n-butyl Itaconate

This study investigates a wide range of clinically relevant mechanical properties of poly(methyl methacrylate) (PMMA) denture base materials modified with di-methyl itaconate (DMI) and di-n-butyl itaconate (DBI) in order to compare them to a commercial PMMA denture base material. The commercial denture base formulation was modified with DMI and DBI by replacing up to 10 wt% of methyl methacrylate (MMA) monomer. The specimens were prepared by standard bath curing process. The influence of the itaconate content on hardness, impact strength, tensile, and thermal and dynamic mechanical properties was investigated. It is found that the addition of di-n-alkyl itaconates gives homogenous blends that show decreased glass transition temperature, as well as decrease in storage modulus, ultimate tensile strength, and impact fracture resistance with increase in the itaconate content. The mean values of surface hardness show no significant change with the addition of itaconates. The magnitude of the measured values indicates that the poly(methyl methacrylate) (PMMA) denture base material modified with itaconates could be developed into a less toxic, more environmentally and patient friendly product than commercial pure PMMA denture base material.

The effect of the accelerated aging on the mechanical properties of the PMMA denture base materials modified with itaconates

This study evaluated the effect of accelerated ageing on the tensile strength, elongation at break, hardness and Charpy impact strength in commercial PMMA denture base material modified with di-methyl itaconate (DMI) and di-n-butyl itaconate (DBI). The samples were prepared by modifying commercial formulation by addition of itaconates in the amounts of 2.5, 5, 7.5 and 10% by weight. After polymerization samples were characterized by FT-IR and DSC analysis while residual monomer content was determined by HPLC-UV. Accelerated ageing was performed at 70°C in water for periods of 7, 15 and 30 days. Tensile measurements were performed using Instron testing machine while the hardness of the polymerized samples was measured by Shore D method. The addition of itaconate significantly reduces the residual MMA. Even at the small amounts of added itaconates (2.5%) the residual MMA content was reduced by 50%. The increase of itaconate content in the system leads to the decrease of residual MMA. It has been found that the addition of di-n-alkyl itaconates decreases the tensile strength, hardness and Charpy impact strength and increases elongation at break. Samples modified with DMI had higher values of tensile strength, hardness and Charpy impact strength compared to the ones modified with DBI. This is explained by the fact that DBI has longer side chain compared to DMI. After accelerated ageing during a 30 days period the tensile strength decreased for all the investigated samples. The addition of DMI had no effect on the material ageing and the values for the tensile strength of all of the investigated samples decreased around 20%, while for the samples modified with DBI, the increase of the amount of DBI in the polymerized material leads to the higher decrease of the tensile strength after the complete accelerated ageing period od 30 days, aulthough after the first seven days of the accelerated ageing the values of hardness have increased for all of the investigated samples. Such behavior is explained as the result of the polymer chain relaxation. The values of Charpy impact strength decreased after accelerated ageing. The amount of added DMI have no affect on the decrease of Charpy impact strength after accelerated ageing, the decrease was similar as for pure PMMA. The decrease of Charpy impact strength increased as the amount of added DBI increases.

Characterisation of melt spun Ni-Ti shape memory Ribbons’ microstructure

NiTi alloys are the most technologically important medical Shape Memory Alloys in a wide range of applications used in Orthopaedics, Neurology, Cardiology and interventional Radiology as guide-wires, self-expandable stents, stent grafts, inferior vena cava filters and clinical instruments. This paper discusses the use of rapid solidification by the melt spinning method for the preparation of thin NiTi ribbons for medical uses. Generally, the application of rapid solidification via melt-spinning can change the microstructure drastically, which improves ductility and shape memory characteristics and leads to samples with small dimensions. As the increase in the wheel speed led to a reduced ribbon thickness, the cooling rate increased and, therefore, the martensitic substructure became finer. Furthermore, no transition from the crystalline phase to the amorphous phase was obtained by increasing the cooling rate, even at a wheel speed of 30 m/s. Specimens for our metallographic investigation were cut from the longitudinal cross sections of melt-spun ribbons. Conventional TEM studies were carried out with an acceleration voltage of 120 kV. Additionally, the chemical composition of the samples was examined with a TEM equipped with an EDX analyser. The crystallographic structure was determined using Bragg-Brentano x-ray diffraction with Cu-Kα radiation at room temperature.