We modified native wheat starch using 15, 30, and 60 min of acid hydrolysis (AH). The non-modified and AH-modified starches were converted to highly homogeneous thermoplastic starches (TPSs) using our two-step preparation protocol consisting of solution casting and melt mixing. Our main objective was to verify if AH can decrease the processing temperature of TPS. All samples were characterized in detail by microscopic, spectroscopic, diffraction, thermomechanical, rheological, and micromechanical methods, including in situ measurements of torque and temperature during the final melt mixing step. The experimental results showed that (i) AH decreased the average molecular weight preferentially in the amorphous regions, (ii) the lower-viscosity matrix in the AH-treated starches resulted in slightly higher crystallinity, and (iii) all AH-modified TPSs with a less viscous amorphous phase and higher content of crystalline phase exhibited similar properties. The effect of the higher crystallinity predominated at a laboratory temperature and low deformations, resulting in slightly stiffer material. The effect of the lower viscosity dominated during the melt mixing, where the shorter molecules acted as a lubricant and decreased the in situ measured processing temperature. The AH-induced decrease in the processing temperature could be beneficial for energy savings and/or possible temperature-sensitive admixtures for TPS systems.

• Keywords
• low viscosity, melt mixing, processing temperature, thermoplastic starch,
• Publication type
• Journal Article MeSH

The use of electrospun polymeric biodegradable materials for medical applications is becoming increasingly widespread. One of the most important parameters regarding the functionality of nanofiber scaffolds during implantation and the subsequent regeneration of damaged tissues concerns their stability and degradation behavior, both of which are influenced by a wide range of factors (the properties of the polymer and the polymer solution, the technological processing approach, the sterilization method, etc.). This study monitored the degradation of nanofibrous materials fabricated from degradable polyesters as a result of the sterilization method applied (ethylene oxide and gamma irradiation) and the solvent system used to prepare the spun polymer solution. Aliphatic polyesters PCL and PLCL were chosen for this study and selected with respect to the applicability and handling in the surgical setting of these nanofibrous materials for vascular bandaging. The results revealed that the choice of solvent system exerts a significant impact on degradation during sterilization, especially at higher gamma irradiation values. The subsequent enzyme-catalyzed degradation of the materials following sterilization indicated that the choice of the sterilization method influenced the degradation behavior of the materials. Whereas wave-like degradation was evident concerning ethylene oxide sterilization, no such behavior was observed following gamma-irradiation sterilization. With concern for some of the tested materials, the results also indicated the potential for influencing the development of degradation within the bulk versus degradation from the surface of the material. Both the sterilization method and the choice of the spinning solvent system were found to impact degradation, which was observed to be most accelerated in the case of PLCL (L-lactide-co-caprolactone copolymer) electrospun from organic acids and subsequently sterilized using gamma irradiation. Since we planned to use these materials in cardiovascular applications, it was decided that their hemocompatibility would also be tested. The results of these tests revealed that changes in the structures of the materials initiated by sterilization may exert thrombogenic and anticoagulant impacts. Moreover, the microscopic analysis suggested that the solvent system used in the preparation of the materials potentially affects the behavior of erythrocytes; however, no indication of the occurrence of hemolysis was detected.

• Keywords
• biodegradable polyester, electrospun nanofibers, enzymatically catalyzed degradation, ethylene oxide, gamma irradiation, hemocompatibility, sterilization,
• Publication type
• Journal Article MeSH

This contribution lays the foundation for the European database of explanted UHMWPE liners from total joint replacements. Three EU countries (Czech Republic, Italy and Spain) have joined their datasets containing anonymized patient data (such as age and BMI), manufacturer data (such as information on UHMWPE crosslinking, thermal treatment and sterilization), orthopedic evaluation (such as total duration of the implant in vivo and reasons for its revision) and material characterization (such as oxidative degradation and micromechanical properties). The joined database contains more than 500 entries, exhibiting gradual growth, and it is beginning to show interesting trends, which are discussed in our contribution, including (i) strong correlations between UHMWPE oxidative degradation, degree of crystallinity and microhardness; (ii) statistically significant differences between UHMWPE liners with different types of sterilization; (iii) realistic correlations between the extent of oxidative degradation and the observed reasons for total joint replacement failures. Our final objective and task for the future is to continuously expand the database, involving researchers from other European countries, in order to create a robust tool that will contribute to the better understanding of structure-properties-performance relationships in the field of arthroplasty implants.

• Keywords
• European database, UHMWPE, micromechanical properties, oxidative degradation, retrieval study, total joint replacements, ultrahigh molecular weight polyethylene,
• Publication type
• Journal Article MeSH

HDPE-based nanocomposite fibers have been extruded from a melt and drawn up to draw ratio DR = 8. Two kinds of carbon nanodiscs (original ones and those exposed to additional annealing) have been used as fillers. Obtained nanocomposite fibers have been investigated with the help of different experimental methods: rheology, SEM and WAXS. It has been demonstrated that the annealed carbon nanodiscs possess a nucleation ability that finally leads to strong transformation of the material morphology.

• Keywords
• HDPE, SEM, WAXS, carbon nanodiscs, fibers, melt-extrusion, rheology, structure,
• Publication type
• Journal Article MeSH

BACKGROUND: At present time the number of implantations of joint replacements as well as their revisions increases. Higher demands are required on the quality and longevity of implants. The aim of this work was to determine the degree of oxidative degradation and the amount of free/residual radicals in selected ultra-high molecular weight polyethylene (UHMWPE) components of the joint replacements and demonstrate that the measured values are closely connected with quality and lifetime of the polymer components. METHODS: We tested both new (4 samples) and explanted (4 samples) UHMWPE polymers for total joint replacements. The samples were characterized by infrared spectroscopy (IR), electron spin resonance (ESR) and microhardness (MH) test. The IR measurements yielded the values of oxidation index and trans-vinylene index. The ESR measurements gave the free radicals concentration. RESULTS: In the group of new polyethylene components, we found oxidation index values ranging from 0.00-0.03 to 0.24. The trans-vinylene index values ranged from 0.044 to 0.080. The value of free radical concentration was zero in virgin and also in sample of Beznoska Company and non-zero in the other samples. In the group of explanted components, the measured values were associated with their history, micromechanical properties and performance in vivo. CONCLUSIONS: We demonstrated that measuring of oxidative damage may help the orthopaedic surgeon in estimating the quality of UHMWPE replacement component and thus radically to avoid early joint replacement failure due to worse polyethylene quality.

• MeSH
• Biocompatible Materials chemistry   MeSH
• Electron Spin Resonance Spectroscopy MeSH
• Crystallization MeSH
• Hip Prosthesis * MeSH
• Humans MeSH
• Oxidation-Reduction MeSH
• Polyethylenes chemistry   MeSH
• Knee Prosthesis * MeSH
• Reoperation MeSH
• Prosthesis Failure MeSH
• Spectrophotometry, Infrared MeSH
• Materials Testing MeSH
• Hardness MeSH
• Free Radicals analysis   MeSH
• Check Tag
• Humans MeSH
• Publication type
• Journal Article MeSH
• Research Support, Non-U.S. Gov't MeSH
• Comparative Study MeSH
• Names of Substances
• Biocompatible Materials MeSH
• Polyethylenes MeSH
• ultra-high molecular weight polyethylene MeSH Browser
• Free Radicals MeSH