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This study details the design, fabrication, clinical trials’ evaluation, and analysis after the clinical application of 3D-printed bone reconstruction implants made of nHAp@PLDLLA [nanohydroxyapatite@poly(l-lactide-co-d,l-lactide)] biomaterial. The 3D-printed formulations have been tested as bone reconstruction Cranioimplantsin 3 different medical cases, including frontal lobe, mandibular bone, and cleft palate reconstructions. Replacing one of the implants after 6 months provided a unique opportunity to evaluate the post-surgical implant obtained from a human patient. This allowed us to quantify physicochemical changes and develop a spatial map of osseointegration and material degradation kinetics as a function of specific locations. To the best of our knowledge, hydrolytic degradation and variability in the physicochemical and mechanical properties of the biomimetic, 3D-printed implants have not been quantified in the literature after permanent placement in the human body. Such analysis has revealed the constantly changing properties of the implant, which should be considered to optimize the design of patient-specific bone substitutes. Moreover, it has been proven that the obtained composition can produce biomimetic, bioresorbable and bone-forming alloplastic substitutes tailored to each patient, allowing for shorter surgery times and faster patient recovery than currently available methods.

The semicrystalline state of polymers implies the formation of a noncrystalline interphase beside lamellar crystals known as the rigid amorphous fraction (RAF). This devitrifies on heating at temperatures much higher than the one typical of the bulk-amorphous fraction. Its glass transition and physical aging in the glassy state have thus far remained elusive. Here, we study the RAF glassy dynamics in poly(l-lactic acid) (PLLA) applying recently developed aging thermal protocols based on fast scanning calorimetry (FSC). Specifically, semicrystalline samples are aged in different conditions between the glass transition of mobile amorphous fraction and the crystals’ melting temperature (TM). A distinct endothermic peak at temperatures above that of aging develops with time. We provide compelling evidence that in the initial part of aging the origin of this peak is due to the enthalpy recovery of glassy RAF. At longer aging times, the aging peak is at least partly associated with secondary crystallization. Isochronous experiments at different aging temperatures enable to obtain a fair estimate of the RAF glass transition temperature, whose upper limit is about 135 °C. The proposed method holds the promise of gaining new insights into the elusive glassy dynamics of the RAF of semicrystalline polymers.

AbstractCompatible blends of isotactic polypropylene (iPP)/low-density polyethylene (LDPE)/ethylene-propylene-diene monomer (EPDM) were prepared by reactive blending in the presence of dicumyl peroxide (DCP). The blends were characterized using different techniques: dynamical rheological analysis (DRA), differential scanning calorimetry (DSC), optical microscopy (OM) and scanning electron microscopy (SEM), dynamical mechanical thermal analysis (DMTA), viscosity and impact strength, to evaluate their properties. Results revealed that the presence of the peroxide in LDPE/EPDM blends gives rise to crosslinking reactions, as is the case in iPP/LDPE/EPDM blends. However, in the latter case, scission reactions of the iPP component also take place. As a consequence of the whole process, morphological changes arise mainly in the amorphous regions, without affecting the degree of crystallinity of the components. The mechanical properties of the blends are consequently improved, due to the crosslinked network thus formed in the blends.

This article details a study of irregularly shaped DSC exotherms of poly(3-hydroxybutyrate) (PHB) developed during isothermal and non-isothermal crystallization. Due to the extreme purity of the polymer, PHB crystallization is mainly initiated by homogeneous nucleation, with the formation of very large spherulites, especially under slow nucleation conditions. When the number of growing spherulites is low, the evolution of latent heat is very sensitive to every act of nucleation as well as to the space limitations in the process of growth, resulting in non-monotonous development of latent heat, with sudden increases and decreases in crystallization rates. This results in non conventional DSC exotherms, under given crystallization conditions, characterized by spikes or shoulders associated to nucleation of new spherulites. This article details a study of irregularly shaped DSC exotherms of poly(3-hydroxybutyrate) (PHB) developed during isothermal and non-isothermal crystallization. Due to the extreme purity of the polymer, PHB crystallization is mainly initiated by homogeneous nucleation, with the formation of very large spherulites, especially under slow nucleation conditions. When the number of growing spherulites is low, the evolution of latent heat is very sensitive to every act of nucleation as well as to the space limitations in the process of growth, resulting in non-monotonous development of latent heat, with sudden increases and decreases in crystallization rates. This results in non conventional DSC exotherms, under given crystallization conditions, characterized by spikes or shoulders associated to nucleation of new spherulites.

This article contains a detailed calorimetric analysis of the multiple melting behavior of poly(L‐lactic acid) (PLLA) in dependence of crystallization conditions. PLLA crystals formed upon primary crystallization have a greater tendency to reorganize into more stable structures during the heating scan that leads to fusion. Depending on crystallization temperature, one or multiple melting endotherms and/or reorganization exotherms can be evidenced. This complex melting behavior arises from the fusion of a certain amount of the original crystals (already partially perfected during the heating scan), followed by recrystallization and final melting of more perfect crystals, partly grown during primary crystallization, and partly formed through the reorganization processes occurring during the heating scan. A detailed map of the melting behavior of PLLA is described in this contribution. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3145–3151, 2006

A throughout investigation of crystallization and melting behavior of poly(L‐lactic acid) is detailed in this contribution. Crystallization analyses, conducted in both isothermal and non‐isothermal conditions, revealed the occurrence of a sudden acceleration in phase transition rate in the temperature range between 100 and 118 °C. This unusual increase, due to very high rates of spherulite growth, seems not related to morphological changes of PLLA spherulites, nor to unexpected variations in nucleation rate. DSC analyses disclosed multiple melting behavior of PLLA, depending on crystallization temperature. At low temperatures the very high crystallization rates lead to the achievement of low values of crystalline degree, with formation of small and/or defective crystals, which have a large tendency to reorganize into more stable structures during the heating scan that leads to complete fusion. The multiple melting process of PLLA was also analyzed at different heating rates.

A detailed morphological analysis of the melting process of poly(butylene terephthalate) (PBT) is presented. Investigations were conducted by polarizing optical microscopy, coupling the measurement of depolarized light intensity with examination of morphology of PBT spherulites during their fusion. These analyses allowed to prove that the spherulitic superstructure of PBT developed upon isothermal crystallization from the melt does not vary with temperature until complete melting takes place, despite the large reorganization involved in the fusion process. It is thus shown that the double melting behavior commonly observed in PBT does not arise from the presence of various spherulitic morphologies with different thermal stabilities, and the structural changes caused by the reorganization processes do not involve variations in the spherulitic morphology. The recrystallization of PBT above the apparent melting point was also analyzed, and the role of memory effects of crystalline precursors remaining in the melt was discussed.