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In this work, the galvanic deposition method is used to deposit coatings of brushite/hydroxyapatite/polyvinyl acetate on 304 stainless steel. Coatings are obtained at different temperatures and with different sacrificial anodes, consisting of a mixture of brushite and hydroxyapatite. Samples are aged in a simulated body fluid (SBF), where a complete conversion of brushite into hydroxyapatite with a simultaneous change in morphology and wettability occurred. The corrosion tests show that, compared with bare 304, the coating shifts Ecorr to anodic values and reduces icorr Ecorr, and icorr has different values at different aging times due to chemical interactions at the solid/liquid interface. The best performing deposits are those obtained by using Al as the sacrificial anode. The metal ion release, measured after 21 days of aging, is very low and is attributable to the presence of a coating that slows the steel corrosion. Coating cytotoxicity is investigated through cell viability assays with MC3T3-E1 osteoblastic cells. The results reveal a high cytocompatibility comparable to that of a pure cell culture medium.

Poly-L-Lactic Acid (PLLA) scaffolds for tissue engineering were prepared via thermally induced phase separation of a ternary system PLLA/dioxane/tetrahydrofurane. An extension to solution of a previously developed method for solidification from the melt was adopted, the technique being based on a Continuous Cooling Transformation (CCT) approach, consisting in recording the thermal history of rapidly cooled samples and analysing the resulting morphology. Different foams were produced by changing the thermal history, the dioxane to THF ratio (50/50, 70/30, 90/10 v/v) and the polymer concentration (2, 2.5, 4 ° wt) in the starting ternary solution. Pore size, porosity, melting and crystallization behavior were studied, together with a morphological and kinetic analysis of the foams produced. A large variety of morphologies was achieved, the largest pore size (20 μm) was achieved at the highest polymer concentration (4 ° wt) and the lowest dioxane concentration (50/50 dioxane/THF v/v), whereas the largest porosity (90 °) was attained at the highest dioxane concentration (90/10). The average pore size is related to cooling rate, with a 1/3 power law exponent at low polymer concentrations and low dioxane content for thermal histories driven by low undercoolings. At high undercoolings, the growth of the demixed domains significantly departs from the diffusive-like regime.

Foams with a pore size gradient are promising materials for tissue engineering applications where a complex architecture involving morphological variations in space must be mimicked, e.g. in bone tissue repair. In this paper, a technique to obtain a porous scaffold with a pore size gradient is presented. The preparation procedure is based on Thermally Induced Phase Separation (TIPS), by imposing a different thermal history on the two sides of a polymeric solution. In this way, a gradient in thermal history is produced, which will generate a pore size monotonously varying along scaffold thickness. By controlling some parameters easy to manipulate, such as demixing temperature and/or residence time in the miscibility gap region, the pore size range can be easily tuned.

Adhesion of tissue cells to biomaterials is a prerequisite of paramount importance for the effectiveness of a tissue engineering construct (cell and scaffolds). Functionalization of polymeric scaffolds with organic polymers, such as collagen or proteoglycans, is a promising approach in order to improve the cytocompatibility. As a matter of fact, organic polymers, isolated directly from the extracellular matrix, contain a multitude of surface ligand (fibronectin, laminin, vitronectin) and arginine–glycine–aspartic acid-containing peptides that promote cell adhesion. In tissue engineering, the combination of organic and synthetic polymers gives rise to scaffolds characterized simultaneously by the mechanical strength of synthetic materials and the biocompatibility of natural materials. In this work, porous poly-L-lactide acid scaffolds were functionalized with a synthetic collagen–glycosaminoglycans matrix in order to improve cell adhesion. For this purpose, a protocol for collagen–glycosaminoglycans conjugation into the pores of the scaffolds was set up. Moreover, an innovative protocol for the quantification of the conjugated glycosaminoglycans inside the scaffolds was created and adopted. The results have confirmed the effectiveness of the developed protocol: a collagen–glycosaminoglycans conjugation, with an efficiency of about 21% was obtained inside the scaffold. Moreover, SEM analysis highlighted the presence of the homogeneous synthetic matrix into the bulk of porous scaffolds. Finally, cell culture assays carried out by utilizing mouse embryonic fibroblasts showed that cell proliferation on poly-L-lactide acid-collagen–glycosaminoglycans scaffold is higher than on poly-L-lactide acid collagen scaffold (utilized as control). Therefore, it can be stated that the presence of glycosaminoglycans not only increases the mechanical strength of the matrix, thanks to their cross-linking effect, but also it seems to lead to a more significant cell growth. Overall, it is reasonable to state that the concerned protocol may be proposed as a reliable route to increase the rate of proliferation and in some cases to stimulate the cell differentiation in tissue engineering devices.

Porous biodegradable PLLA membranes, which can be used as supports for perfusion cell culture systems were designed, developed and characterized. PLLA membranes were prepared via diffusion induced phase separation (DIPS). A glass slab was coated with a binary PLLA–dioxane solution (8 wt.% PLLA) via dip coating, then pool immersed in two subsequent coagulation baths, and finally dried in a humidity-controlled environment. Surface and mechanical properties were evaluated by measuring pore size, porosity via scanning electron microscopy, storage modulus, loss modulus and loss angle by using a dynamic mechanical analysis (DMA). Cell adhesion assays on different membrane surfaces were also performed by using a standard count method. Results provide new insights into the foaming methods for producing polymeric membranes and supply indications on how to optimise the fabrication parameters to design membranes for tissue cultures and regeneration.

The phase diagram of the Poly- l -Lactic-Acid (PLLA), dioxane and water system was derived by using the lattice fluid model generalized for specific interactions. A qualitative analysis of Hansen solubility parameters together with empirical observations were adopted to reduce the number of adjustable parameters. The as-selected model parameters were derived by fitting a set of cloud point curves; consequently, the complete phase diagram of the system was computed. The use of specific interactions between species gave out a quantitative agreement with a set of experimental data, whereas changing the polymer polydispersity the agreement is only qualitative. In principle, the presented procedure could be adopted for the calculation of liquid–liquid equilibria in ternary polymer solutions with similar features of PLLA–dioxane–water system.

Liquid–liquid phase separation processes are currently used as a route to prepare polymeric porous structures for various applications (membranes and scaffolds for tissue engineering). In membrane and foam fabrication technologies, binary and mainly ternary polymer solutions are used. Membrane morphology is strongly affected by phase equilibria of processing solution. In order to achieve a better control of membrane morphology and to explore a wide quantity of solvents, a predictive tool addressing experimentals would be strongly advisable. In this paper, group contribution models were chosen to test the applicability on a PLLA–dioxane–water ternary polymer solution, whose experimental data are available. As a general result, the inadequateness of models to predict the phase separation must be highlighted, coupled with a scarce sensitivity to temperature. Moreover, a major task stems about the free volume of water in relation to other components. A brief panoramic of attempts on various models and parameters is presented, underlining the open issues of the group contribution models.

A critical obstacle in tissue engineering is the inability to maintain large masses of living cells upon transfer from the in vitro culture conditions into the host in vivo. Capillaries, and the vascular system, are required to supply essential nutrients, including oxygen, remove waste products and provide a biochemical communication “highway”. Another goal in this research field is the possibility to tune the biodegradability of the scaffold. After implantation, the scaffold has to be gradually replaced by cells and extra cellular matrix and it is crucial that this replacement takes place with an appropriate dynamics. A premature degradation, in fact, could lead to a collapse of the structure as the newly generated tissue could not have reached yet the suitable mechanical properties. Conversely, a long degradation time could brake or completely interrupt the development of the new tissue. In this work PLLA-PLA scaffolds for vascular tissue engineering were produced by dip-coating via Diffusion Induced Phase Separation (DIPS) technique. Pure PLA scaffolds and 75/25 PLA/PLLA scaffolds were obtained and characterized. No homogeneous scaffolds were obtained by using a 50/50 PLLA/PLA blend.

In this study, mouse mesoangioblasts were seeded onto bidimensional matrices within three-dimensional porous scaffolds of poly (L-lactic acid) (PLLA), in the presence or absence of a type I collagen coating. The cells were observed under a scanning electron microscope and tested for their adhesion, survival and proliferation. Immunolocalization of heat shock protein (Hsp) 70, an abundant and ubiquitous intracellular protein in these cells, was also performed in sectioned cell-containing scaffolds under a confocal fluorescence microscope to determine if in situ analysis of intracellular constituents was feasible. The data show that PLLA films allow direct cell adhesion and represent an optimal support for cell growth, and that the internal surfaces of PLLA polymeric sponges can be colonized by mesoangioblasts, which can be submitted for in situ confocal microscopic analyses for possible monitoring of time-dependent expression of differentiation markers.

Scaffolds suitable for tissue engineering applications like dermal reconstruction were prepared by Thermally Induced Phase Separation (TIPS) starting from a ternary solution PLLA/dioxane/water. The experimental protocol consisted of three consecutive steps, a first quench from the homogeneous solution to an appropriate demixing temperature (within the metastable region), a holding stage for a given residence time, and a final quench from the demixing temperature to a low temperature (within the unstable region). A large variety of morphologies, in terms of average pore size and interconnection, were obtained upon modifying the demixing time and temperature, owing to the interplay of nucleation and growth processes during the residence in the metastable state. An interesting combination of micro and macroporosity was observed for long residence times in the metastable state (above 30 min at 35 degrees C). Preliminary degradation tests in a biological mimicking fluid (D-MEM with bovine serum) showed a significant weight loss during the initial stages (ca. 30% in 30 days) related to the degradation of the amorphous part, followed by a negligible weight loss in the next days (few percent from 30 to 60 days).

In a Glass Fiber Reinforced (GFR) polymer, the coefficient of volumetric thermal expansion CVTE (determined as a sum of the coefficients of linear thermal expansion CLTE’s for the three principal directions) is sometimes much smaller than the value predictable on the basis of well acquainted models, such as Chow model, taking into account fibers anisotropy and aspect ratio.

An analysis of the crystallization kinetics of different grades of isotactic polypropylene (iPP) is here presented. To describe the crystallization kinetics as a function of molecular and operating parameters, the methodological path followed was the preparation of quenched samples of known cooling histories, calorimetric crystallization isotherms tests, differential scanning calorimetry cooling ramps, wide angle X-ray diffraction (WAXD) measurements, and density determination. The WAXD analysis performed on the quenched iPP samples confirmed that during the fast cooling at least a crystalline structure and a mesomorphic one form. The diffractograms were analyzed by a deconvolution procedure, to identify the relationship between the cooling history and the distribution of the crystalline phases. The whole body of results (including calorimetric ones) provides a wide basis for the identification of a crystallization model suitable to describe solidification in polymer-processing operations, based on the Kolmogoroff–Avrami–Evans nonisothermal approach. The kinetic parameters, determined for all the materials, are discussed, highlighting the effect of molecular parameters on the crystallization kinetics: molecular mass and distribution, tacticity, nucleating agents, and ethylene units content. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1358–1367, 2007

Polymeric membranes prepared via DIPS (Diffusion Induced Phase Separation) are widely studied and utilized as scaffolds for the regeneration of tissue. In this work, poly (L)-lactide membrane are prepared through a DIPS protocol starting from a ternary solution made of polymer, dioxane (solvent) and water (non-solvent). A three-dimensional, porous and mechanically stable membrane is desirable for ingrowth of human bronchial epithelial cells. Polymeric membranes prepared via DIPS (Diffusion Induced Phase Separation) are widely studied and utilized as scaffolds for the regeneration of tissue. In this work, poly (L)-lactide membrane are prepared through a DIPS protocol starting from a ternary solution made of polymer, dioxane (solvent) and water (non-solvent). A three-dimensional, porous and mechanically stable membrane is desirable for ingrowth of human bronchial epithelial cells.

An inline method for monitoring the solidification process during the injection molding of semicrystalline polymers is demonstrated. The method has been applied to various poly(ethylene terephthalate) (PET) and poly(buthylene terephthalate) (PBT) samples. The technique is based on a simple device by which an additional ejector pin is pushed onto the injection-molded part with a fixed force at different times during the solidification phase while the mold remains closed. The residual deformation (the so-called indentation depth) due to the applied load is measured offline after ejection. By the performance of indentation at different times during the cooling phase, an indentation depth profile, that is, the residual deformation as a function of time, is obtained. With a simplified solid/liquid two-phase model, the evolution of the solidification front in the mold as a function of the cooling time can be determined from the indentation curve. The obtained experimental results agree well with calculations based on the classical theory of heat penetration. Descriptions of several materials (including PET and PBT) with variations in the molecular weight (PET) have been obtained under different operating conditions (various mold temperatures, holding pressures, and indentation pressures). The results show that the indentation test may be regarded as a powerful tool for monitoring the solidification process during injection molding and, therefore, for optimizing injection-molding processing conditions according to material characteristics. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3713–3727, 2003

In this work an innovative apparatus for the characterization of polymer solidification under very high cooling rates (up to thousand of K/s) is described, according to the continuous cooling transformation approach adopted in metallurgy for studying structure development in metals. The proposed model experiment is addressed to design a method for the characterization of non-isothermal solidification behaviour, encompassing typical cooling conditions of polymer processing. Only temperature history determines the structure formed, as melt solidification takes place in quiescent conditions. With respect to the device previously developed by the authors [1, 3] the present equipment presents the following features: - reduced size (30*30*20 cm); - higher heating rates, by using two electrical resistances supported on ceramic plates; - higher cooling rates, carried out through water sprays at very high pressures (120 bar); - thermal insulation of the sample from the sample holder via the application of two wave springs; - automatic control and synchronization of the whole sequence of operations: transfer of the sample from the melting (heating) zone to the cooling (spray) chamber via rotation (it was via sliding in the previous version); - very high heat transfer coefficients, up to 7*10(5) W/m(2)K

Solidification in industrial processes very often involves flow fields, high thermal gradients and high pressures: the development of a model able to describe the polymer behavior becomes complex. Recently a new equipment has been developed and improved to study the crystallization of polymers when quenched under pressure. An experimental apparatus based on a modified, special injection moulding machine has been employed. Polymer samples can be cooled at a known cooling rate up to 100 °C/s and under a constant pressure up to 40 MPa. Density, Micro Hardness (MH), Wide angle X-ray diffraction (WAXD), and annealing measurements were then used to characterize the obtained sample morphology. Results on one iPP sample display a lower density and a lower density dependence on cooling rate for increasing pressure. Micro hardness confirms the same trend. A deconvolution technique of WAXD patterns is used to evaluate the final phase content of samples and to assess a crystallization kinetics behavior. A master curve approach to explain iPP behavior under pressure and high cooling rates was successfully applied on density results. On the basis of this simple model it is possible to predict the final polymer density by superposition of the effect of cooling rate and the effect of pressure in a wide range of experimental conditions.

A temperature-controlled turbidity measurement apparatus for the characterization of polymer solutions has been instrumented and set up. The main features are the coupled temperature-light transmittance measurement and the accurate temperature control, achieved by means of peltier cells. The apparatus allows to measure cloud point temperatures by adopting different cooling protocols: low rate for quasi-equilibrium measurements and high rate for detect kinetic effects. A ternary polymeric solution was adopted as case study system showing that cooling rate affects the measured cloud point temperature.

Porous scaffolds based on blends of high crystalline Poly-L-lactic acid (PLLA) with low crystalline poly-D-L-lactic acid (PLA) were prepared via Ther- mally Induced Phase Separation (TIPS), with the aim of exploring the possibility to control the degradation behaviour of the PLA-based scaffold, simultaneously pre- serving the morphological characteristics required for tissue engineering applica- tions. Porous foams with different PLLA/PLA weight ratios (from 95/5 to 60/40) were produced and characterised in terms of pore size, porosity, and thermal properties. The scaffolds present an open porosity, with average pore sizes ranging from 30 to 70 lm. Results showed that, when dealing with a PLLA/PLA blend, some relevant processing conditions of the preparation process (above all demixing temperature and total polymer concentration) must be carefully tuned, in order to attain suitable structures in term of pore size and porosity. In particular, with increasing amounts of PLA in a PLLA/PLA blend, the demixing temperature must be decreased and the overall polymer concentration decreased. Moreover, a pre- liminary investigation regarding the in vitro biodegradation rate of the blends was attempted, based on the determination of the crystallinity through wide angle X-ray diffractometry.

Vapor mass transfer phenomena in four different membrane distillation (MD) configurations were examined through a self-built laboratory scale experimen- tal apparatus: Air Gap MD, Sweeping Gas MD, Vacuum Sweeping Gas MD and Vacuum MD. Vapor fluxes were measured and compared with those predicted by various models, showing that MD performance under usual processing conditions is severely controlled by the permeate side resistance to mass transfer.

The no‐flow temperature (NFT) is a parameter representing the rheological solidification temperature of a polymer. A polymer, during injection molding filling stage, can stop its flow because of its high viscosity, although it is not yet fully solidified by means of glass transition or crystallization. The NFT is used in most of injection molding simulation packages: with this simple parameter it is possible to reduce the errors deriving from viscosity extrapolation at relatively low temperatures. The viscosity measurements for polymers are usually carried out at high temperatures, and the viscosity models can fail in prediction at temperatures close to the glass transition or crystallization temperature.The NFT is still a parameter not well defined and a standard method to measure it is still lacking. Nevertheless, a simple correlation for NFT estimation, derived from Cross‐WLF equation, is proposed for both amorphous and semicrystalline polymers. The presented correlation takes into account the changes ...

Most injection molding simulation packages use the no-flow temperature (NFT) as a means of determining whether the polymer flows or is solid. The NFT is not well defined, and a standard method for measuring it does not exist. A sensitivity analysis of the filling stage has been carried out with two different packages [VISI Flow (Vero Software Limited, Gloucestershire, UK) and Moldflow (Autodesk, Inc., San Rafael, CA)] to estimate the influence of the NFT on the main processing parameters. The NFT has a large influence on the thickness of the frozen layer, but it does not appreciably affect the filling pressure. Because the NFT affects the frozen layer, an effect on the estimation of shrinkage and warpage is expected. Software packages have also been compared, and similar simulations have been found to produce contrasting results. A simple correlation for NFT estimation, derived from the Cross–Williams–Landel–Ferry equation, is proposed for both amorphous and semicrystalline polymers. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Polymeric membranes are currently adopted in water purification processes, such as reverse osmosis (RO) and membrane distillation (MD). This latter technique is very promising for separation effectiveness and energy savings. A valuable and effective MD unit must be equipped with polymeric membranes that exhibit specific properties, for example, hydrophobicity, a narrow pore size range, a high water penetration pressure, and a large vapor permeability. In this work, we present and examine the main features of membranes for MD processes, with the aim of experimentally evaluating the related performances. Scanning electron microscopy analysis was carried out for a first estimate of the pore size distribution; this showed a discrepancy between the nominal pore size and the actual distribution. Vapor flux under typical water purification conditions was measured for different commercial membranes, and values as high as 35 kg m−2 h−1 were observed. Polytetrafluoroethylene membranes were more permeable for both of the MD configurations tested. The liquid entry pressure (LEP) showed an irreversible decrease in the early operation cycles related to microstructural modifications. A LEP reversible decrease with increasing temperature was observed; this showed that in the membrane selection, the nominal LEP value had to be corrected for the temperature effect for the correct choice. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011

Hydrophobic microporous membranes are utilized in membrane distillation (MD) processes, e.g. seawater desalination at moderate temperatures. The vapour permeability of commercial hydrophobic membranes with different pore sizes (0.2-1 micron) was characterized through a simple apparatus designed-on-purpose. A cylindrical vessel had a face closed by the membrane and the other connected to a thin graduate tube. The water level variation in the tube is recorded and related to the vapour flux across the membrane. Measurements were taken in the temperature range 20-80°C. A fan tangential to membrane surface was employed to maintain a constant driving force for vapour transport. Vapour flux did not depend on pore dimension, but the membrane and support material resulted to influence the mass transfer. Moreover, the results showed that the main resistance for mass transfer is located in the permeate side, thus addressing future works on the set up of a MD pilot unit.

Membrane distillation is an emerging technique for seawater desalination. Hydrophobic polymeric membranes are used to separate the solute‐free water vapour from the hot solution. Vapour fluxes of commercial polymeric membranes were measured in various conditions, i.e. natural and forced convection and vacuum. Vapour fluxes were also predicted with models and compared with experimentals. Higher fluxes were recorded in vacuum conditions.

Scaffolds suitable for tissue engineering applications were prepared by Thermally Induced Phase Separation (TIPS) starting from a ternary solution PLLA/ dioxane/water. The experimental protocol consisted of three consecutive steps, a first quench from the homogeneous solution to an appropriate demixing temperature (within the binodal region), a liquid-liquid demixing stage for a given time and a final quench from the demixing temperature to a low temperature (within the spinodal region). A large variety of morphologies, in terms of average pore size and interconnection were obtained upon modifying the demixing time and temperature, owing to the interplay of nucleation and growth processes during the residence in the metastable state. An interesting combination of micro and macro-porosity was observed for longer demixing times (above 30 min at 35 °C).

PLLA scaffold suitable for dermis regeneration were realized by Thermally Induced Phase Separation (TIPS) starting from a ternary solution PLLA/dioxane/water. The reconstruction of a complex tissues as the dermis implies the use of different cellular types (coculture), with different growth behaviour (2D vs. 3D). The scaffolds present an homogeneous porous surface to allow the keratinocytes 2D growth and a porous internal structure for the fibroblasts 3D growth. Our results show that the porosity of the surface can be tuned by changing the chemical nature of the sample holder (aluminium, teflon, polypropylene). A large variety of morphologies, in terms of average pore size and interconnection were obtained upon modifying the demixing time and temperature. WAXD analysis and DSC scanning tests showed only slight differences among the scaffolds prepared at the various conditions. Finally, a biocompatibility test was carried out by using human fibroblast and keratinocytes, indicating a good proliferation of the cells both on the surface and in the bulk of the scaffold.

An experimental route for investigating polymer crystallization over a wide range of cooling rates (from 0.01 to 1000◦C/s) and pressures (from 0.1 to 40 MPa) is illustrated, using a method that recalls the approach adopted in metallurgy for studying structure development in metals. Two types of experimental setup were used, namely an apparatus for fast cooling of thin films (100–200 μm thick) at various cooling rates under atmospheric pressure and a device (based on a on-purpose modified injection molding machine) for quenching massive samples (about 1–2 cm3) under hydrostatic pressure fields. In both cases, ex situ characterization experiments were carried out to probe the resulting structure, using techniques such as density measurements and wide-angle x-ray diffraction (WAXD) patterns. The cooling mechanism and temperature distribution across the sample thickness were analyzed. Results show that the final structure is determined only by the imposed thermal history and pressure. Experimental results for isotactic polypropylene (iPP), poly(ethylene terephthalate) (PET), polyamide 6 (PA6), and syndiotactic polystyrene (sPS) are reported, showing the reliability of this experimental approach to assess not only quantitative information but also a qualitative description of the crystallization behavior of different classes of semicrystalline polymers. The present study gives an opportunity to evaluate how the combined effect of the cooling rate and pressure influences the crystallization kinetics for various classes of polymer of commercial interest. An increase in the cooling rate translates into a decrease in crystallinity and density, which both experience a sudden drop around the specific “crystallizability” (or “critical cooling rate”) of the material examined. The exception is sPS where competition among the various crystalline modifications determines a minimum in the plot of density vs. cooling rate. As for the effect of pressure, iPP exhibits a “negative dependence” of crystallization kinetics upon pressure, with a decrease of density and degree of crystallinity with increasing pressure, owing to kinetic constraints. PA6 and PET, on the other hand, due to thermodynamic factors resulting in an increase in Tm with pressure, exhibits a “positive dependence” of crystallization kinetics upon pressure. Finally, recent original results concerning sPS have shown that the minimum in the density vs. cooling rate curve shifts toward larger cooling rates upon increasing pressure.

A critical obstacle in tissue engineering is the inability to maintain large masses of living cells upon transfer from the in vitro culture conditions into the host in vivo. Capillaries, and the vascular system, are required to supply essential nutrients, including oxygen, remove waste products and provide a biochemical communication “highway”. For this reason it is mandatory to manufacture an implantable structure where the process of vessel formation – the angiogenesis – can take place. In this work PLLA scaffolds for vascular tissue engineering were produced by dip-coating via Diffusion Induced Phase Separation (DIPS) technique. The scaffolds, with a vessel-like shape, were obtained by performing a DIPS process around a nylon fibre whose diameter was 700 μm. The fibre was first immersed into a 4% PLLA dioxane solution and subsequently immersed into a second bath containing distilled water. The covered fibre was then rinsed in order to remove the excess of dioxane and dried; finally the internal nylon fibre was pulled out so as to obtain a hollow biodegradable PLLA fiber. SEM analysis revealed that the scaffolds have a lumen of ca. 700 μm. The internal surface is homogeneous with micropores 1–2 μm large. Moreover, a cross section analysis showed an open structure across the thickness of the scaffold walls. A cell culture of endothelial cells was carried out into the as-prepared scaffolds. The result showed that cells are able to grow within the scaffolds and after 3 weeks they begin to form a “primordial” vessel-like structure.

Foams for tissue engineering applications were prepared via thermally induced phase separation (TIPS). Poly-L-Lactic Acid (PLLA) and blends of PLLA with PLA in different proportions were used (100/0, 90/10, 75/25, 50/50, 0/100 PLLA/PLA wt/wt) starting from ternary systems where dioxane was the solvent and water the non-solvent. Morphology was evaluated by Scanning Electron Microscopy (average pore size and interconnection) and the void fraction was measured by means of Hg porosimetry. Foams apparent density was also evaluated (porosity ranges from 87% to 92%). Biodegradability was estimated in a body mimicking fluid. Results show that structure and morphology (in terms of average pore size and distribution, interconnectivity and mechanical properties) depend upon the combination of the operating conditions adopted for the process (polymer concentration, solvent/non-solvent ration, demixing temperature and time). Furthermore, by blending PLLA with PLA it is possible to tune the biodegrability of the foam, thus addressing the possible applications in different fields of soft tissue engineering.

Syndiotactic polystyrene (sPS) was solidified from the melt under drastic conditions according to a continuous cooling transformation methodology developed by the authors, which covered a cooling rate range spanning from approximately 0.03 to 3000 °C/s. The samples produced, structurally homogeneous across both their thickness and surface, were analyzed by macroscopic methods, such as density, wide-angle X-ray diffraction (WAXD), and microhardness (MH) measurements. The density was strictly related to the phase content, as confirmed by WAXD deconvolution. The peculiar behavior encountered (the density first decreasing and then increasing with the cooling rate) was attributed to the singularity of the phases formed in sPS; that is, one of the crystalline phases (a) was less dense than the amorphous phase, and the latter, in turn, was less dense than the other crystalline phase (β). With an increasing cooling rate, the thermodynamically stable phase (β) disappeared first, and it was followed by the a phase. On the other hand, the MH values remarkably depended on the amount of the β phase, the α-phase content influencing the mechanical properties only to a minor extent. The behavior of the crystallization kinetics was described through a modified multiphase Kolmogoroff-Avrami-Evans model for nonisothermal crystallization.

Isotactic Poly-propylene samples, previously prepared under known conditions of pressure and cooling rate by means of a special apparatus designed and set-up by the authors, were subjected to several isobaric runs at low cooling and heating rate in a confining fluid dilatometer (by GNOMIX). The effect of the previous thermo-mechanical histories and the effect of pressure in the dilatometry on specific volume of the samples was studied. Results show that the initial specific volume depends upon the previous thermo-mechanical histories, which however cancels out after the first heating run. Moreover the reported dilatometric experimental data support the evidence that an increase of pressure at a constant cooling rate acts as an increase of cooling rate at a constant pressure. © Springer-Verlag 2002.

A new experimental route for investigating polymer crystallization under very high cooling rates (up to 2000°C/s) is described. A complete and exhaustive description of the apparatus employed for preparing thin quenched samples (100– 200 μm thick) is reported, the cooling mechanism and the temperature distribution across sample thickness is also analysed, showing that the final structure is determined only by the thermal history imposed by the fast quench apparatus. Details concerning the characterization techniques used to probe the final structure are reported, including density measurements and wide angle X-ray diffraction patterns. Experimental results concerning isotactic polypropylene, polyethylenetherephthalate and polyamide 6 are reported, showing the reliability of this experimental route to assess not only a quantitative information but also a qualitative description of the crystallization behaviour of different classes of semi-crystalline polymers.

Reliable experimental data for semicrystalline polymers crystallized under pressure are supplied on the basis of a model experiment in which drastic solidification conditions are applied. The influence of the pressure and cooling rate on some properties, such as the density and microhardness, and on the product morphology, as investigated with wide-angle X-ray scattering (WAXS), is stressed. Results for isotactic polypropylene (iPP) samples display a lower density and a lower microhardness with increasing pressure over a wide range of cooling rates (from 0.01 to 20 °C/s). Polyamide-6 (PA6) samples exhibit the opposite behavior, with the density and microhardness increasing at higher pressures over the entire range of cooling rates investigated (from 1 to 200 °C/s). A deconvolution technique applied to iPP and PA6 WAXS patterns has allowed us to evaluate the final phase content and to assess the crystallization kinetics. A negative influence of pressure on the α-crystalline phase crystallization kinetics can be observed for iPP, whereas a slightly positive influence of pressure on the crystallization kinetics of PA6 can be noted. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 40: 153–175, 2002

Among porous materials suitable for Bone Tissue Engineering (BTE) scaffolds, bioactive ceramics (hydroxyapatite, HA) and bioactive glasses (BG) have been used for their excellent biocompatibility, bioactivity and efficient osteointegration (1). However, their major limitations are brittleness, low mechanical stability and low dissolution rate (2). Recent evidences suggest that composite scaffold based on biodegradable polymers (e.g. Poly-lacticacid (PLLA)) simultaneously loaded with HA and BG hold promising potential as efficient osteoconductive implants (3, 4). In this work we investigated the possibility to produce composite PLLA-HA-BG scaffolds via Thermally Induced Phase Separation (TIPS). Morphological investigastions and in-vitro bioactivity tests were performed.

Injuries of tendons and ligaments are common, especially among the young population. Anterior cruciate ligament (ACL) injuries do not heal due to its limited vascularization and hence, surgical intervention is usually required. The ideal scaffold for ligament tissue engineering (TE) should be biocompatible and possess mechanical and functional characteristics comparable to the native ACL. The Diffusion Induced Phase Separation (DIPS) technique allows the preparation of homogenous porous tubular scaffold with micro-pores using a rather simple procedure. Composites based on biodegradable polymers and bioglass have attracted much attention in tissue reconstruction and repair because of their biological and physicochemical advantages. In this work a new approach in ACL TE will be proposed focussing on the development of a suitable technique for in vitro seeding of lapine ACL fibroblasts into tubular-shaped instructive Poly-lactic-acid (PLLA) scaffolds, supplemented or not with bioglass (BG) 1393, produced via DIPS. Tubular composite scaffold (diameters: 1.2 and 2 mm, +/- BG) were obtained through a dip coating around a cylindrical support followed by a DIPS. An 8%wt PLLA/dioxane solution was prepared with 5%wt of BG-1393 as filler. Preliminary in vitro cell culture trials were carried out by seeding lapine ACL fibroblasts inside the scaffolds (2 cm as length) employing different seeding strategies in order to find the best way that allows to obtain a homogeneous fibroblast distribution inside the tubes. (1) First trials consisted in the inoculating of the cell suspension inside the tubes and maintaining them in dynamical culture. (2) The second one was done by suspending the cells in a fibrin gel polymerized within the tubes by using of thrombin. (3) The third approach was carried out by using cell spheroids (three-dimensional self-assembled cell agglomerates). Cell attachment, viability and morphology were examined by live-death and Hematoxylin/Eosin stainings after 1, 7, 14 d and vimentin immunolabelings (7 d). Scanning electron microscopical analysis revealed that the internal surface of the tubes was homogeneously structured with micropores sized around 5 µm and a mean thickness of the wall of 60 µm. The results showed cell adhesion to the wall of the tubes with all seeding techniques applied even though with fibrin gel it was more homogenous. Furthermore, colonized areas expanded with culture time and the majority of cell survived irrespectively of seeding techniques. (1) In inoculation phase, many cells left the scaffold and attached on the plate. Even after the dynamic culture (rotating device) most cells covered only half the tube inner surface. (2) In the second trial, a fibrin gel was used to achieve a homogenous cell distribution during seeding. In the early stage (48 h) cells remained captured inside the fibrin, but after 7 d they become elongated and migrated from the fibrin to the inner tube surface forming a compact cell layer. So, the fibrin appears helpful to achieve an immediate high cell seeding efficiency and an almost homogeneous cell distribution inside the tubes. (3) Although using the spheroid technique the scaffold internal surface was not homogeneously colonized with cells, after 7 d cell migration to the inner scaffold surface from the attaching spheroids could be observed. In longitudinal sections cells were elongated like typical ligament fibroblasts parallel to the longitudinal tube axis. Therefore, it can be affirmed that employment of tubular scaffolds produced by DIPS could be a promising approach of ligament TE. In the future, it would be interesting to evaluate the effectiveness of seeding by combining the spheroids and the fibrin gel.

Among the high‐performance polyesters blends PBT/PET blends are expected to exhibit remarkable properties as far as the crystallization behaviour is concerned. The solidification behaviour of a 60/40 w/w PBT/PET blend was studied in a wide range of cooling conditions, according to a Continuous Cooling Transformation (CCT) procedure developed by the authors, aiming to emulate the typical conditions encountered in polymer processing. A set of several samples characterized by an homogeneous structure was prepared by solidification from the melt through spray cooling, and the resulting structure and properties were evaluated by density, Micro Hardness (MH), Wide Angle X‐ray Diffraction (WAXD) measurements, to describe their dependence upon the imposed thermal history. The resulting solidification behaviour was then compared to that exhibited by the constituents of the blend (PET and PBT).