Theoretical and Experimental Investigation of 3D-Printed Polylactide Laminate Composites' Mechanical Properties.

The purpose of this work is to theoretically and experimentally investigate the applicability of the Tsai-Hill failure criterion and classical laminate theory for predicting the strength and stiffness of 3D-printed polylactide laminate composites with various raster angles in mechanical tests for uniaxial tension and compression. According to the results of tensile and compression tests, the stiffness matrix components of the orthotropic individual lamina and strength were determined. The Poisson's ratio was determined using the digital image correlation method. It was found that the Tsai-Hill criterion is applicable for predicting the tensile strength and yield strength of laminate polymer composite materials manufactured via fused deposition modeling 3D printing. The calculated values of the elastic moduli for specimens with various raster angles correlate well with the values obtained experimentally. In tensile tests, the error for the laminate with a constant raster angle was 3.3%, for a composite laminate it was 4.4, in compression tests it was 11.9% and 9%, respectively.

Highly Stable Docetaxel-Loaded Nanoparticles Based on Poly(D,L-lactide)-b-Poly(ethylene glycol) for Cancer Treatment: Preparation, Characterization, and In Vitro Cytotoxicity Studies.

Stability and narrow size distribution are among the main requirements that apply to drug formulations based on polymeric nanoparticles. In this study, we obtained a series of particles based on biodegradable poly(D,L-lactide)-b-poly(ethylene glycol) (P(D,L)LAn-b-PEG113) copolymers with varied hydrophobic P(D,L)LA block length n from 50 to 1230 monomer units stabilized by poly(vinyl alcohol) (PVA) by a simple "oil-in-water" emulsion method. We found that nanoparticles of P(D,L)LAn-b-PEG113 copolymers with relatively short P(D,L)LA block (n ≤ 180) are prone to aggregate in water. P(D,L)LAn-b-PEG113 copolymers with n ≥ 680 can form spherical unimodal particles with values of hydrodynamic diameter less than 250 nm and polydispersity less than 0.2. The aggregation behavior of P(D,L)LAn-b-PEG113 particles was elucidated in terms of tethering density and conformation of PEG chains at the P(D,L)LA core. Docetaxel (DTX) loaded nanoparticles based on P(D,L)LA680-b-PEG113 and P(D,L)LA1230-b-PEG113 copolymers were formulated and studied. It was observed that DTX-loaded P(D,L)LAn-b-PEG113 (n = 680, 1230) particles are characterized by high thermodynamic and kinetic stability in aqueous medium. The cumulative release of DTX from the P(D,L)LAn-b-PEG113 (n = 680, 1230) particles is sustained. An increase in P(D,L)LA block length results in a decrease in DTX release rate. The in vitro antiproliferative activity and selectivity studies revealed that DTX-loaded P(D,L)LA1230-b-PEG113 nanoparticles demonstrate better anticancer performance than free DTX. Favorable freeze-drying conditions for DTX nanoformulation based on P(D,L)LA1230-b-PEG113 particles were also established.

Poly(Ethylene Glycol)-b-Poly(D,L-Lactide) Nanoparticles as Potential Carriers for Anticancer Drug Oxaliplatin.

Nanoparticles based on biocompatible methoxy poly(ethylene glycol)-b-poly(D,L-lactide) (mPEG113-b-P(D,L)LAn) copolymers as potential vehicles for the anticancer agent oxaliplatin were prepared by a nanoprecipitation technique. It was demonstrated that an increase in the hydrophobic PLA block length from 62 to 173 monomer units leads to an increase of the size of nanoparticles from 32 to 56 nm. Small-angle X-ray scattering studies confirmed the "core-corona" structure of mPEG113-b-P(D,L)LAn nanoparticles and oxaliplatin loading. It was suggested that hydrophilic oxaliplatin is adsorbed on the core-corona interface of the nanoparticles during the nanoprecipitation process. The oxaliplatin loading content decreased from 3.8 to 1.5% wt./wt. (with initial loading of 5% wt./wt.) with increasing PLA block length. Thus, the highest loading content of the anticancer drug oxaliplatin with its encapsulation efficiency of 76% in mPEG113-b-P(D,L)LAn nanoparticles can be achieved for block copolymer with short hydrophobic block.

Kinetics of D,L-Lactide Polymerization Initiated with Zirconium Acetylacetonate.

The kinetic of D,L-lactide polymerization in presence of biocompatible zirconium acetylacetonate initiator was studied by differential scanning calorimetry in isothermal mode at various temperatures and initiator concentrations. The enthalpy of D,L-lactide polymerization measured directly in DSC cell was found to be ΔH=-17.8±1.4 kJ mol-1. Kinetic curves of D,L-lactide polymerization and propagation rate constants were determined for polymerization with zirconium acetylacetonate at concentrations of 250-1000 ppm and temperature of 160-220 °C. Using model or reversible polymerization the following kinetic and thermodynamic parameters were calculated: activation energy Ea =44.51±5.35 kJ mol-1, preexponential constant lnA=15.47±1.38, entropy of polymerization ΔS=-25.14 J mol-1 K-1. The effect of reaction conditions on the molecular weight of poly(D,L-lactide) was shown.

Biodegradable poly(l-lactide)/calcium phosphate composites with improved properties for orthopedics: Effect of filler and polymer crystallinity.

Biodegradable poly(l-lactide)/calcium phosphate composites are promising materials for fabrication of bone fixation implants with improved properties. Multistage compounding was proposed as an efficient method for the preparation of biodegradable poly(l-lactide)/calcium phosphate composites with submicron filler dispersion and mechanical characteristics similar to native bone. The improvement of the characteristics is caused both by the filler itself and by the increase of polymer crystallinity due to the nucleation effect. The technique allows to fabricate biodegradable composites with controlled properties by varying concentration and type of the filler as well as degree of PLLA matrix crystallinity. Animal studies revealed that all the composites were biocompatible and non-toxic.

Noninvasive high-frequency acoustic microscopy for 3D visualization of microstructure and estimation of elastic properties during hydrolytic degradation of lactide and ε-caprolactone polymers.

The monitoring of degradation processes' kinetics in polymers is one of the attractive possibilities of ultrasound technique applications that provide non-destructive imaging of polymers' internal microstructure and measurements of elastic properties. In this work, biodegradable polymers and copolymers based on L,L-lactide, D,L-lactide and ε-caprolactone have been studied at different stages of hydrolysis at 37 °C by high-frequency (100 and 200 MHz) ultrasound. The acoustic microscopy technique has been developed to reveal changes in the internal microstructure and bulk sound speed in polymer samples over a hydrolysis period of 25 weeks. Ultrasound imaging provides visualization of amorphous and crystalline phases, internal imperfections, variation in packing density, and other microstructural features. Acoustic images demonstrate nucleation, growth, and the changes in internal inhomogeneities in polymers during degradation accompanied by a decrease in the polymers' molecular weight. We associate the changes in the elastic properties (the speed of a longitudinal wave) with crystallinity variations in polymers during hydrothermal aging. The results of the ultrasound investigations are supplemented by gel permeation chromatography, differential scanning calorimetry, and wide-angle X-ray spectroscopy. STATEMENT OF SIGNIFICANCE: Monitoring the kinetics of degradation processes in polymers is one of the attractive possibilities of applying ultrasound techniques that provide non-destructive imaging of the polymers' internal microstructure and measurements of elastic properties. In this work, visualization of nucleation, growth, and evolution of internal inhomogeneities in the volume of polymers and variation of values of speed of longitudinal and transverse sound waves during hydrolysis are compared with measurements of molecular weight, density, data of DSC curves, and X-ray scattering analysis. We discuss several common phenomena that occur in the volume of poly(L-lactide) and poly(D,L-lactide) over the degradation process as well as improvement of elastic properties of the poly(ε -caprolactone) and poly(L-lactide-co-caprolactone) during hydrothermal aging.

Cold Crystallization of Glassy Polylactide during Solvent Crazing.

Uniaxial tension accompanied by the orientation and crystallization of polymer chains is one of the powerful methods for the improvement of mechanical properties. Crystallization of amorphous isotropic polylactide (PLA) at room temperature is studied for the first time during the drawing of films in the presence of liquid adsorption-active media (ethanol, water-ethanol mixtures, and n-heptane) by the solvent crazing mechanism. The crystalline structure arises only under simultaneous actions of a liquid medium and a tensile stress and does not depend on the nature of the environment. The degree of polymer crystallinity increases nearly linearly with the growth in the fraction of the fibrillar material and reaches a maximum value of 42-45%. It has been stated that polymer crystallization happens in crazes involving nanofibrils with a diameter of about 10-20 nm without affecting the bulk polymer parts. Wide-angle X-ray scattering has been used to confirm that the crazing-induced crystallization is accompanied by the formation of the α'-crystalline phase with crystallite sizes (X-ray coherent scattering region) of 3-5 nm, depending on the nature of the liquid medium. After stretching in liquid media to a high tensile strain, the strength of a PLA film has increased to 200 MPa.