Institute of Fundamental Technological Research

The development of bone tissue engineering, a field with significant potential, requires a biomaterial with high bioactivity. The aim of this manuscript was to fabricate a nanofibrous poly(L-lactide) (PLLA) scaffold containing nano-hydroxyapatite (nHA) to investigate PLLA/nHA composites, particularly the effect of fiber arrangement and the addition of nHA on the piezoelectric phases and piezoelectricity of PLLA samples. In this study, we evaluated the effect of nHA particles on a PLLA-based electrospun scaffold with random and aligned fiber orientations. The addition of nHA increased the surface free energy of PLLA/nHA (42.9 mN/m) compared to PLLA (33.1 mN/m) in the case of aligned fibers. WAXS results indicated that at room temperature, all the fibers are in an amorphous state indicated by a lack of diffraction peaks and amorphous halo. DSC analysis showed that all samples located in the amorphous/disordered alpha' phase crystallize intensively at temperatures just above the Tg and recrystallize on further heating, achieving significantly higher crystallinity for pure PLLA than for doped nHA, 70 % vs 40 %, respectively. Additionally, PLLA/nHA fibers show a lower heat capacity for PLLA in the amorphous state, indicating that nHA reduces the molecular mobility of PLLA. Moreover, piezoelectric constant d33 was found to increase with the addition of nHA and for the aligned orientation of the fibers. In vitro tests confirmed that the addition of nHA and the aligned orientation of nanofibers increased osteoblast proliferation.

Scaffolds, Tissue engineering, Bone tissue engineering, Smart medicine, Biodegradable polymers, Regenerative medicine

Nanofibrous materials generated through electrospinning have gained significant attention in tissue regeneration, particularly in the domain of bone reconstruction. There is high interest in designing a material resembling bone tissue, and many scientists are trying to create materials applicable to bone tissue engineering with piezoelectricity similar to bone. One of the prospective candidates is highly piezoelectric poly(vinylidene fluoride) (PVDF), which was used for fibrous scaffold formation by electrospinning. In this study, we focused on the effect of PVDF molecular weight (180,000 g/mol and 530,000 g/mol) and process parameters, such as the rotational speed of the collector, applied voltage, and solution flow rate on the properties of the final scaffold. Fourier Transform Infrared Spectroscopy allows for determining the effect of molecular weight and processing parameters on the content of the electroactive phases. It can be concluded that the higher molecular weight of the PVDF and higher collector rotational speed increase nanofibers’ diameter, electroactive phase content, and piezoelectric coefficient. Various electrospinning parameters showed changes in electroactive phase content with the maximum at the applied voltage of 22 kV and flow rate of 0.8 mL/h. Moreover, the cytocompatibility of the scaffolds was confirmed in the culture of human adipose-derived stromal cells with known potential for osteogenic differentiation. Based on the results obtained, it can be concluded that PVDF scaffolds may be taken into account as a tool in bone tissue engineering and are worth further investigation.

scaffolds,polymers,piezoelectricity,bone tissue engineering,nanofibers,regenerative medicine

The study explores the in vitro biocompatibility and osteoconductivity of poly(methyl methacrylate)/nano-hydroxyapatite (PMMA/nHA) composite nanofibrous scaffolds for bone tissue engineering (BTE). Electrospun scaffolds, exhibiting both low and high fiber orientation, were investigated. The inclusion of hydroxyapatite nanoparticles enhances the osteoconductivity of the scaffolds while maintaining the ease of fabrication through electrospinning. SEM analysis confirms the high-quality morphology of the scaffolds, with successful incorporation of nHA evidenced by SEM-EDS and FTIR methods. DSC analysis indicates that nHA addition increases the PMMA glass transition temperature (Tg) and reduces stress relaxation during electrospinning. Furthermore, higher fiber orientation affects PMMA Tg and stress relaxation differently. Biological studies demonstrate the composite material’s non-toxicity, excellent osteoblast viability, attachment, spreading, and proliferation. Overall, PMMA/nHA composite scaffolds show promise for BTE applications.

biomaterials, nanofibrous scaffolds, bone tissue engineering

Thermoresponsive shape memory polymers (SMPs) have garnered increasing interest for their exceptional ability to retain a temporary shape and recover the original configuration through temperature changes, making them promising in various applications. The SMP shape change and recovery that happen due to a combination of mechanical loading and appropriate temperatures are related to its particular microstructure. The deformation process leads to the formation and growth of micro-cracks in the SMP structure, whereas the subsequent heating over its glass transition temperature Tg leads to the recovery of its original shape and properties. These processes also affect the SMP microstructure. In addition to the observed macroscopic shape recovery, the healing of micro-crazes and micro-cracks that have nucleated and developed during the loading occurs. Therefore, our study delves into the microscopic aspect, specifically addressing the healing of micro-cracks in the cyclic loading process. The proposed research concerns a thermoplastic polyurethane shape memory polymer (PU-SMP) MM4520 with a Tg of 45 °C. The objective of the study is to investigate the effect of the number of tensile loading-unloading cycles and thermal shape recovery on the evolution of the PU-SMP microstructure. To this end, comprehensive research starting from structural characterization of the initial state and at various stages of the PU-SMP mechanical loading was conducted. Dynamic mechanical analysis (DMA), differential scanning calorimetry (DSC), wide-angle X-ray scattering (WAXS) and scanning electron microscopy (SEM) were used. Moreover, the shape memory behavior in the thermomechanical loading program was investigated. The obtained average shape fixity value was 99%, while the shape recovery was 92%, which confirmed good shape memory properties of the PU-SMP. Our findings reveal that even during a single loading-unloading tension cycle, crazes and cracks nucleate on the surface of the PU-SMP specimen, whereas the subsequent temperature-induced shape recovery process carried out at the temperature above Tg enables the healing of micro-cracks. Interestingly, the surface of the specimen after three and five loading-unloading cycles did not exhibit crazes and cracks, although some traces of cracks were visible. The traces disappeared after exposing the material to heating at Tg + 20 °C (65 °C) for 30 min. The crack closure phenomenon during deformation, even without heating over Tg, occurred within three and five subsequent cycles of loading-unloading. Notably, in the case of eight loading-unloading cycles, cracks appeared on the surface of the PU-SMP and were healed only after thermal recovery at the particular temperature over Tg. Upon reaching a critical number of cycles, the proper amount of energy required for crack propagation was attained, resulting in wide-open cracks on the material’s surface. It is worth noting that WAXS analysis did not indicate strong signs of typical highly ordered structures in the PU-SMP specimens in their initial state and after the loading history; however, some orientation after the cyclic deformation was observed.

polyurethane shape memory polymer, glass transition temperature, tensile loading cycles, structure analysis, micro-cracks, healing

Bone repair and regeneration require physiological cues, including mechanical, electrical, and biochemical activity. Many biomaterials have been investigated as bioactive scaffolds with excellent electrical properties. Amongst biomaterials, piezoelectric materials (PMs) are gaining attention in biomedicine, power harvesting, biomedical devices, and structural health monitoring. PMs have unique properties, such as the ability to affect physiological movements and deliver electrical stimuli to damaged bone or cells without an external power source. The crucial bone property is its piezoelectricity. Bones can generate electrical charges and potential in response to mechanical stimuli, as they influence bone growth and regeneration. Piezoelectric materials respond to human microenvironment stimuli and are an important factor in bone regeneration and repair. This manuscript is an overview of the fundamentals of the materials generating the piezoelectric effect and their influence on bone repair and regeneration. This paper focuses on the state of the art of piezoelectric materials, such as polymers, ceramics, and composites, and their application in bone tissue engineering. We present important information from the point of view of bone tissue engineering. We highlight promising upcoming approaches and new generations of piezoelectric materials.

piezoelectricity, scaffolds, smart scaffolds, PVDF, PLLA, PVDF-TRFE, collagen, keratin, tissue engineering, bone tissue engineering, smart medicine, regenerative medicine

Thermomechanical behaviour of Gum Metal (Ti–23Nb–0.7Ta–2.0Zr–1.2O, at.%) under cyclic tension was experimentally investigated using infrared thermography and digital image correlation. The thermomechanical characteristics of particular stages of the subsequent loading-unloading cycles of Gum Metal were identified, i.e. (I) the linear, elastic loading accompanied by the temperature drop, (II) the nonlinear super-elastic loading related to the temperature growth, (III) the transient stage (at which both the superelastic-like behaviour and the plastic one are present simultaneously) and the temperature starts growing fast, (IV) the plastic deformation with a significant growth of temperature, (V) the superelastic-like unloading accompanied by a fast drop in temperature, (VI) the transient unloading with a slower decrease in temperature and (VII) the elastic unloading, with a slight increase in temperature. Thermoelastic effect in Gum Metal during both loading and unloading was analysed in each tensile cycle. Finally, the evolution of strain and temperature fields just before unloading in each cycle was discussed and a comparison of the fields at selected stages of cycles 12 and 24 was presented. The results of this work enabled us to identify the non-dissipative processes of elastic and superelastic-like deformations as well as the dissipative process of plastic deformation.

Gum Metal,β-Ti alloy,cyclic tension,superelasticity,thermoelastic effect,infrared thermography,digital image correlation

Local bacterial infections lead to delayed wound healing and in extreme cases, such as diabetic foot ulcers, to non-healing due to the impaired cellular function in such wounds. Thus, many scientists have focused on developing advanced therapeutic platforms to treat infections and promote cellular proliferation and angiogenesis. This study presents a facile approach for designing nanofibrous scaffolds in three dimensions (3D) with enhanced antibacterial activity to meet the need of treating chronic diabetic wounds. Being a cationic surfactant as well as an antimicrobial agent, octenidine (OCT) makes a 2D membrane hydrophilic, enabling it to be modified into a 3D scaffold in a “one stone, two birds” manner. Aqueous sodium borohydride (NaBH4) solution plays a dual role in the fabrication process, functioning as both a reducing agent for the in situ synthesis of silver nanoparticles (Ag NPs) anchored on the nanofiber surface and a hydrogen gas producer for expanding the 2D membranes into fully formed 3D nanofiber scaffolds, as demonstrated by morphological analyses. Various techniques were used to characterize the developed scaffold (e.g., SEM, XRD, DSC, FTIR, and surface wettability), demonstrating a multilayered porous structure and superhydrophilic properties besides showing sustained and prolonged release of OCT (61% ± 1.97 in 144 h). Thanks to the synergistic effect of OCT and Ag NPs, the antibacterial performance of the 3D scaffold was significantly higher than that of the 2D membrane. Moreover, cell viability was studied in vitro on mouse fibroblasts L929, and the noncytotoxic character of the 3D scaffold was confirmed. Overall, it is shown that the obtained multifunctional 3D scaffold is an excellent candidate for diabetic wound healing and skin repair.

Shape memory polymers (SMP) are new multifunctional materials that are of increasing interest in various functional applications. Among them, polyurethane shape memory polymers (PU-SMP) are particularly attractive due to their combination of shape memory, high strength and biocompatible properties. Developing new applications for PU-SMP requires comprehensive research on their characteristics. This work involved investigating the structure and mechanical behaviour and characterizing the energy storage and dissipation of a thermoplastic PU-SMP with a glass transition temperature (Tg) of 25 °C during tensile loading-unloading. The process of energy storage and dissipation in the PU-SMP was investigated based on the stress-strain curves recorded by a quasi-static testing machine and the temperature changes, accompanying the deformation process, obtained by using a fast and sensitive infrared camera. The results showed that the thermomechanical behaviour of the examined PU-SMP depends significantly on the strain rate. At a higher strain rate, there are higher stress and related temperature changes, which lead to greater energy dissipation. However, the energy storage values estimated during the deformation process turned out to be not significant, indicating that the work supplied to the PU-SMP structure during loading is mainly converted into heat. It should also be noted that the structural investigation revealed no crystalline phase in the investigated PU-SMP

shape memory polymer,infrared camera,thermomechanical couplings,energy storage and dissipation,tension test

Cross-linking of poly(vinyl alcohol) (PVA) creates a three-dimensional network by bonding adjacent polymer chains. The cross-linked structure, upon immersion in water, turns into a hydrogel, which exhibits unique absorption properties due to the presence of hydrophilic groups within the PVA polymer chains and, simultaneously, ceases to be soluble in water. The properties of PVA can be adjusted by chemical modification or blending with other substances, such as polymers, e.g., conductive poly[3-(potassium-5-butanoate)thiophene-2,5-diyl] (P3KBT). In this work, PVA-based conductive semi-interpenetrating polymer networks (semi-IPNs) are successfully fabricated. The systems are obtained as a result of electrospinning of PVA/P3KBT precursor solutions with different polymer concentrations and then cross-linking using “green”, environmentally safe methods. One approach consists of thermal treatment (H), while the second approach combines stabilization with ethanol and heating (E). The comprehensive characterization allows to evaluate the correlation between the cross-linking methods and properties of nanofibrous hydrogels. While both methods are successful, the cross-linking density is higher in the thermally cross-linked samples, resulting in lower conductivity and swelling ratio compared to the E-treated samples. Moreover, the H-cross-linked systems have better mechanical properties─lower stiffness and greater tensile strength. All the tested systems are biocompatible, and interestingly, due to the presence of P3KBT, they show photoresponsivity to solar radiation generated by the simulator. The results indicate that both methods of PVA cross-linking are highly effective and can be applied to a specific system depending on the target, e.g., biomedical or electronic applications.

poly(vinyl alcohol),poly[3-(potassium-5-butanoate)thiophene-2.5-diyl],electrospun nanofibers,cross-linking,fibrous hydrogel,semi-IPN

In situ crosslinked materials are the main interests of both scientific and industrial research. Methylcellulose (MC) aqueous solution is one of the representatives that belongs to this family of thermosensitive materials. At room temperature, MC is a liquid whereupon during temperature increase up to 37 °C, it crosslinks physically and turns into a hydrogel. This feature makes it unique, especially for tissue engineering applications. However, the crosslinking rate of MC alone is relatively slow considering tissue engineering expectations. According to these expectations, the crosslinking should take place slowly enough to allow for complete injection and fill the injury avoiding clogging in the needle, and simultanously, it should be sufficiently fast to prevent it from relocation from the lesion. One of the methods to overcome this problem is MC blending with another substance that increases the crosslinking rate of MC. In these studies, we used agarose (AGR). These studies aim to investigate the effect of different AGR amounts on MC crosslinking kinetics, and thermal, viscoelastic, and biological properties. Differential Scanning Calorimetry (DSC) and dynamic mechanical analysis (DMA) measurements proved that AGR addition accelerates the beginning of MC crosslinking. This phenomenon resulted from AGR's greater affinity to water, which is crucial in this particular crosslinking part. In vitro tests, carried out using the L929 fibroblast line and mesenchymal stem cells (MSCs), confirmed that most of the hydrogel samples were non-cytotoxic in contact with extracts and directly with cells. Not only does this type of thermosensitive hydrogel system provide excellent mechanical and biological cues but also its stimuli-responsive character provides more novel functionalities for designing innovative scaffold/cell delivery systems for tissue engineering applications.

A methylcellulose (MC) is one of the materials representatives performing unique thermal-responsive properties. While reaching a critical temperature upon heating MC undergoes a physical sol-gel transition and consequently becomes a gel. The MC has been studied for many years and researchers agree that the MC gelation is related to the lower critical solution temperature (LCST). Nevertheless, a precise description of the MC gelation mechanism remains under discussion. In this study, we explained the MC gelation mechanism through examination of a wide range of MC concentrations via differential scanning calorimetry (DSC). The results evidenced that MC gelation is a multistep thermoreversible process, manifested by three and two endotherms depending on MC concentration. The occurrence of the three endotherms for low MC concentrations during heating has not been reported in the literature before. We justify this phenomenon by manifestation of three various transitions. The first one manifests water–water interactions, i.e., spanning water network breakdown into small water clusters. It is clearly evidenced by additional normalization to the water content. The second effect corresponds to polymer–water interactions, i.e., breakdown of water cages surrounded methoxy groups of MC. The last one is related to the polymer–polymer interactions, i.e., fibril hydrophobic domain formation. Not only did these results clarify the MC crosslinking mechanism, but also in the future will help to assess MC relevance for various potential application fields.

methylcellulose, thermosensitive hydrogel, crosslinking, DSC

Tissue engineering (TE) scaffolds have enormous significance for the possibility of regeneration of complex tissue structures or even whole organs. Three-dimensional (3D) printing techniques allow fabricating TE scaffolds, having an extremely complex structure, in a repeatable and precise manner. Moreover, they enable the easy application of computer-assisted methods to TE scaffold design. The latest additive manufacturing techniques open up opportunities not otherwise available. This study aimed to summarize the state-of-art field of 3D printing techniques in applications for tissue engineering with a focus on the latest advancements. The following topics are discussed: systematics of the available 3D printing techniques applied for TE scaffold fabrication; overview of 3D printable biomaterials and advancements in 3D-printing-assisted tissue engineering.

tissue engineering, 3D printing, biomaterials

Piezoelectric polymers are promising energy materials for wearable and implantable applications for replacing bulky batteries in small and flexible electronics. Therefore, many research studies are focused on understanding the behavior of polymers at a molecular level and designing new polymer-based generators using polyvinylidene fluoride (PVDF). In this work, we investigated the influence of voltage polarity and ambient relative humidity in electrospinning of PVDF for energy-harvesting applications. A multitechnique approach combining microscopy and spectroscopy was used to study the content of the β-phase and piezoelectric properties of PVDF fibers. We shed new light on β-phase crystallization in electrospun PVDF and showed the enhanced piezoelectric response of the PVDF fiber-based generator produced with the negative voltage polarity at a relative humidity of 60%. Above all, we proved that not only crystallinity but also surface chemistry is crucial for improving piezoelectric performance in PVDF fibers. Controlling relative humidity and voltage polarity increased the d33 piezoelectric coefficient for PVDF fibers by more than three times and allowed us to generate a power density of 0.6 μW·cm^–2 from PVDF membranes. This study showed that the electrospinning technique can be used as a single-step process for obtaining a vast spectrum of PVDF fibers exhibiting different physicochemical properties with β-phase crystallinity reaching up to 74%. The humidity and voltage polarity are critical factors in respect of chemistry of the material on piezoelectricity of PVDF fibers, which establishes a novel route to engineer materials for energy-harvesting and sensing applications.

PVDF, polymer crystallinity, electrospinning, piezoelectricity, voltage polarity

Electric field strength and polarity in electrospinning processes and their effect on process dynamics and the physical properties of as-spun fibers is studied. Using a solution of the neutral polymer such as poly(methyl methacrylate) (PMMA) we explored the electrospun jet motion issued from a Taylor cone. We focused on the straight jet section up to the incipient stage of the bending instability and on the radius of the disk of the fibers deposited on the collecting electrode. A new correlation formula using dimensionless parameters was found, characterizing the effect of the electric field on the length of the straight jet, L˜E~E˜0.55. This correlation was found to be valid when the spinneret was either negatively or positively charged and the electrode grounded. The fiber deposition radius was found to be independent of the electric field strength and polarity. When the spinneret was negatively charged, L˜E was longer, the as-spun fibers were wider. The positively charged setup resulted in fibers with enhanced mechanical properties and higher crystallinity. This work demonstrates that often-overlooked electrical polarity and field strength parameters influence the dynamics of fiber electrospinning, which is crucial for designing polymer fiber properties and optimizing their collection.

fibers, electrical polarity, charges, electrospinning, PMMA, mechanical properties

Injury to the central or peripheral nervous systems leads to the loss of cognitive and/or sensorimotor capabilities, which still lacks an effective treatment. Tissue engineering in the post-injury brain represents a promising option for cellular replacement and rescue, providing a cell scaffold for either transplanted or resident cells. Tissue engineering relies on scaffolds for supporting cell differentiation and growth with recent emphasis on stimuli responsive scaffolds, sometimes called smart scaffolds. One of the representatives of this material group is piezoelectric scaffolds, being able to generate electrical charges under mechanical stimulation, which creates a real prospect for using such scaffolds in non-invasive therapy of neural tissue. This paper summarizes the recent knowledge on piezoelectric materials used for tissue engineering, especially neural tissue engineering. The most used materials for tissue engineering strategies are reported together with the main achievements, challenges, and future needs for research and actual therapies. This review provides thus a compilation of the most relevant results and strategies and serves as a starting point for novel research pathways in the most relevant and challenging open questions.

neural tissue engineering, piezoelectric scaffolds, smart materials, polymers

Electrospun polymer nanofibers have received much attention in tissue engineering due to their valuable properties such as biocompatibility, biodegradation ability, appropriate mechanical properties, and, most importantly, fibrous structure, which resembles the morphology of extracellular matrix (ECM) proteins. However, they are usually hydrophobic and suffer from a lack of bioactive molecules, which provide good cell adhesion to the scaffold surface. Post-electrospinning surface functionalization allows overcoming these limitations through polar groups covalent incorporation to the fibers surface, with subsequent functionalization with biologically active molecules or direct deposition of the biomolecule solution. Hydrophilic surface functionalization methods are classified into chemical approaches, including wet chemical functionalization and covalent grafting, a physiochemical approach with the use of a plasma treatment, and a physical approach that might be divided into physical adsorption and layer-by-layer assembly. This review discusses the state-of-the-art of hydrophilic surface functionalization strategies of electrospun nanofibers for tissue engineering applications. We highlighted the major advantages and drawbacks of each method, at the same time, pointing out future perspectives and solutions in the hydrophilic functionalization strategies.

surface functionalization, electrospinning, polymers, nanofiber, immobilization, tissue engineering

Smart piezoelectric materials are of great interest due to their unique properties. Piezoelectric materials can transform mechanical energy into electricity and vice versa. There are mono and polycrystals (piezoceramics), polymers, and composites in the group of piezoelectric materials. Recent years show progress in the applications of piezoelectric materials in biomedical devices due to their biocompatibility and biodegradability. Medical devices such as actuators and sensors, energy harvesting devices, and active scaffolds for neural tissue engineering are continually explored. Sensors and actuators from piezoelectric materials can convert flow rate, pressure, etc., to generate energy or consume it. This paper consists of using smart materials to design medical devices and provide a greater understanding of the piezoelectric effect in the medical industry presently. A greater understanding of piezoelectricity is necessary regarding the future development and industry challenges.

polymers, smart materials, piezoelectric materials, inorganic materials, organic materials, biomedical devices

Polyvinylidene fluoride (PVDF) is one of the most important piezoelectric polymers. Piezoelectricity in PVDF appears in polar β and ɣ phases. Piezoelectric fibers obtained by means of electrospinning may be used in tissue engineering (TE) as a smart analogue of the natural extracellular matrix (ECM). We present results showing the effect of rotational speed of the collecting drum on morphology, phase content and in vitro biological properties of PVDF nonwovens. Morphology and phase composition were analyzed using scanning electron microscopy (SEM) and Fourier-transform infrared spectroscopy (FTIR), respectively. It was shown that increasing rotational speed of the collector leads to an increase in fiber orientation, reduction in fiber diameter and considerable increase of polar phase content, both b and g. In vitro cell culture experiments, carried out with the use of ultrasounds in order to generate electrical potential via piezoelectricity, indicate a positive effect of polar phases on fibroblasts. Our preliminary results demonstrate that piezoelectric PVDF scaffolds are promising materials for tissue engineering applications, particularly for neural tissue regeneration, where the electric potential is crucial.

scaffolds, electrospinning, polyvinylidene fluoride, tissue engineering

Thermosensitive, physically crosslinked injectable hydrogels are in the area of interests of various scientific fields. One of the representatives of this materials group is an aqueous solution of methylcellulose. At ambient conditions, methylcellulose (MC) is a sol while on heating up to 37 °C, MC undergoes physical crosslinking and transforms into a gel. Injectability at room temperature, and crosslinkability during subsequent heating to physiological temperature raises hopes, especially for tissue engineering applications. This research work aimed at studying crosslinking kinetics, thermal, viscoelastic, and biological properties of MC aqueous solution in a broad range of MC concentrations. It was evidenced by Differential Scanning Calorimetry (DSC) that crosslinking of MC is a reversible two-stage process, manifested by the appearance of two endothermic effects, related to the destruction of water cages around methoxy groups, followed by crosslinking via the formation of hydrophobic interactions between methoxy groups in the polymeric chains. The DSC results also allowed the determination of MC crosslinking kinetics. Complementary measurements of MC crosslinking kinetics performed by dynamic mechanical analysis (DMA) provided information on the final storage modulus, which was important from the perspective of tissue engineering applications. Cytotoxicity tests were performed using mouse fibroblasts and showed that MC at low concentration did not cause cytotoxicity. All these efforts allowed to assess MC hydrogel relevance for tissue engineering applications.

methylcellulose, thermosensitive hydrogel, crosslinking kinetics, DSC, DMA, cellular tests

The degradation in vivo and its effect on the supermolecular structure of poly(caprolactone) was examined. Poly(caprolactone) (PCL) samples were prepared in the form of porous scaffolds implanted into rat calvarial defects. The degradation was investigated by means of gel permeation chromatography, wide angle X-ray scattering (WAXS), scanning electron microscopy (SEM) and differential scanning calorimetry (DSC). The study showed that the observed decrease of PCL crystallinity during degradation is accompanied by reduction of crystal size and/or perfection. The observed phenomenon could be explained by the presence of the high content of the low mobile fraction of investigated polymer, consisting not only almost 50% of crystal fraction but also most probably relatively high fraction of s.c. rigid amorphous fraction (RAF). Considering the type of structure characterized by the dominance of low mobile fraction, it is expected that the degradation will mainly concern these fractions, which in turn will lead to a decrease in the degree of crystallinity as well as crystal size and/or perfection.

PCL degradation, In-vivo conditions, Crystallinity, Rigid amorphous fraction

Calorimetric studies on poly(ethylene glycol) Mn = 400 g/mol, encapsulated in polystyrene fibers show non-trivial crystallization behavior. Analysis, assuming constant Avrami exponent n, is unsuitable. Approach allowing for changes in the exponent n, requires assumption of the crystallization rate function, derived from the nucleation theory. Changes in Avrami exponent n, follow the changes in geometry of crystal growth and in nucleation mechanisms. Crystallization in micrometer fibers starts from heterogeneous nucleation with three-dimensional crystal growth e as in bulk e but changes to two and one-dimensional, terminated by homogeneous nucleation. For bulk and in 1 and 0.6 micron thick fibers, the approach evidences similar thermodynamic parameters. In 0.6 micron thick fibers, crystallization rate is lower due to higher energy barrier for diffusion, ED = 10 kJ/mol versus 8.7 kJ/mol for bulk and 1 micron thick fibers. Additionally, fiber thickness depends not only on parameters of the electrospinning process but also on the thermal history.

core-shell fibers, confinement effects, crystallization kinetics, DSC, polyethylene glycol

Crystallization from melt of poly(vinylidene fluoride) was studied by thin film chip calorimetry at cooling rates from 500 to 100,000 Ks−1 and isothermally down to 76°C. At ca. 70°C, for cooling rates higher than 2000 Ks−1, there appears a change in crystallization from high temperature α phase to low temperature β phase. The amorphous state is preserved at cooling rate 100,000 Ks−1. Analysis of the crystallization kinetics with Ziabicki model reveals maximum of the steady-state crystallization rate of β phase as 2200 s−1 at 22°C, and the highest crystallization rate of α phase as 200 s−1 at 70°C. Approximation of the temperature dependent steady-state crystallization rate with the Turnbull and Fisher nucleation model results in the equilibrium melting temperatures 227 and 173°C for the α and β phase, respectively, and in the energy barrier for short-distance transport, ED, as 70–80 kJ mol−1 at high supercooling.

Poly(vinylidene fluoride), Ultra-fast calorimetry, Crystallization kinetics

The Ni/Al multilayer coating of λ ≈100 nm was deposited onto (001)-oriented monocrystalline silicon substrate using double target magnetron sputtering system equipped with rotating sample holder. The thicknesses of alternating layers were adjusted in the way to preserve the chemical composition ratio close to 50%Al:50%Ni (at.%). The in situ X-ray diffraction and in situ transmission electron microscopy heating experiments were carried out at relatively low heating rates (20°C/min) in order to study the phase transformation sequence. The investigations revealed that the reaction between Ni and Al multilayers starts at ≈200°C with precipitation of Al₃Ni phase, while above 300°C dominates precipitation of Ni₃Al and NiAl intermetallic phases. Both the X-ray and electron diffractions acquired at 450°C confirmed presence of the Ni₃Al and NiAl intermetallics, but the former pointed at still lasting traces of Ni(Al) solid solution.

transmission electron microscopy, multilayers

In this paper extensive research on the polyurethane shape memory polymer (PU-SMP) is reported, including its structure analysis, our experimental investigation of its thermomechanical properties and its modelling. The influence of the effects of thermomechanical couplings on the SMP behaviour during tension at room temperature is studied using a fast and sensitive infrared camera. It is shown that the thermomechanical behaviour of the SMP significantly depends on the strain rate: at a higher strain rate higher stress and temperature values are obtained. This indicates that an increase of the strain rate leads to activation of different deformation mechanisms at the micro-scale, along with reorientation and alignment of the molecular chains. Furthermore, influence of temperature on the SMP's mechanical behaviour is studied. It is observed during the loading in a thermal chamber that at the temperature 20°C below the glass transition temperature (Tg) the PU-SMP strengthens about six times compared to the material above Tg but does not exhibit the shape recovery. A finite-strain constitutive model is formulated, where the SMP is described as a two-phase material composed of a hyperelastic rubbery phase and elastic-viscoplastic glassy phase. The volume content of phases is governed by the current temperature. Finally, model predictions are compared with the experimental results.

shape memory polyurethane, thermomechanical couplings, infrared camera, temperature change, dynamic mechanical analysis, strain rate, constitutive model

Fibers were electrospun from a solution comprised of oppositely charged polyelectrolytes, in efforts to achieve highly confined macromolecular packaging. A stoichiometric ratio of poly(allylamine hydrochloride) and poly(acrylic acid) solution was mixed in an ethanol–water co-solvent. Differential scanning calorimetry (DSC) analysis of electrospun fibers demonstrated no indication of glass transition, Tg. Infrared spectroscopy (FTIR) analysis of the fibers as a function of temperature, demonstrated an amidation process at lower temperature compared to cast film. Polarized FTIR indicated a preference of the functional groups to be perpendicular to the fiber axis. These results imply formation of mixed phase fibers with enhanced conditions for intermolecular interactions, due to the highly aligned and confined assembly of the macromolecules. The tunable intermolecular interactions between the functional groups of the polyelectrolytes, impact pH-driven, reversible swelling–deswelling of the fibers. The degree of ionization of PAA at pH 5.5 and pH 1.8 varied from 85% to 18%, correspondingly, causing transformation of ionic interactions to hydrogen bonding between the functional groups. The chemical change led to a massive water diffusion of 500% by weight and to a marked increase of 400% in fiber diameter, at a rate of 0.50 μm s−1. These results allow for manipulation and tailoring of key fiber properties for tissue engineering, membranes, and artificial muscle applications.

polyelectrolytes, electrospinning, pH responsive fibers

Wide Angle X-ray Scattering (WAXS), Differential Scanning Calorimetry (DSC) and Fourier Transform Infrared spectroscopy (FTIR) analyses of phase composition and of thermal properties of PVDF samples, crystallized at temperatures 27 - 155°C by casting from N,N-dimethyl formamide (DMF) solution, are reported. Samples obtained at 27°C contain only β crystal phase and with increase of casting temperature content of β phase decreases in favor of α phase. Evaluation of combined: phase content (WAXS) and melting heat (DSC), leads to two fold higher than for 100 % α phase value of 100% β melting enthalpy, ΔHβ0= 219.7 J.g-1, which may be justified by strong polar interactions in β phase TTT conformation. The relation ΔHβ0 > ΔHα0 leads either to the thermodynamic stability of β phase in whole temperature range (if Tmβ0 ≥ Tmα0) or to the limited temperature range of thermodynamic stability of α phase (if Tmβ0 < Tmα0).

pvdf, WAXS, FTIR, DSC, crystallinity, polymorphism

Analysis of the thermo-mechanical behavior of electrospun thermoplastic polyurethane (TPU) block co-polymer nanofibers (glass transition temperature ∼−50°C) is presented. Upon heating, nanofibers began to massively contract, at ∼70°C, whereas TPU cast films started to expand. Radial wide-angle X-ray scattering (WAXS) profiles of the nanofibers and the films showed no diffraction peaks related to crystals, whereas their amorphous halo had an asymmetric shape, which can be approximated by two components, associated with hard and soft segments. During heating, noticeable changes in the contribution of these components were only observed in nanofibers. These changes, which were accompanied with an endothermic DSC peak, coinciding with the start of the nanofibers contraction, can be attributed to relaxation of an oriented stretched amorphous phase created during electrospinning. Such structure relaxation becomes possible when a portion of the hard segment clusters, forming an effective physical network, is destroyed upon heating.

Block-copolymer, Electrospinning, Nanofibers, Thermo-mechanical properties

The estimation of compostability of different polyurethanes under natural weather depending conditions in compost with active sludge at waste treatment plant was the subject of this study. The incubation of polymer samples took place for a period up to 24 months. The characteristic parameters of compost: temperature, pH, moisture content and activity of dehydrogenases were monitored and their influence on degradation of polyurethanes was discussed. The proper compoststability of polyurethanes was investigated by changes of weight, tensile strength and morphology of polyurethane samples after incubation in environment. The degradation study revealed that the degree of degradation of polyurethanes in the natural environment, like compost, is dependent on their chemical and structural composition.

polyurethanes, degradation, compost

The kinetics of isothermal crystallization of various polymers was investigated by light depolarization technique (LDT) using the new setup with direct registration of depolarization ratio. Experimental data were analyzed using new method proposed by Ziabicki who shown that degree of crystallinity is a non-linear function of degree of depolarization, crystal thickness, and its birefringence. Other experimental methods were involved providing supplementary information on crystal thickness (SAXS) and allowing comparison of crystallization kinetics (WAXS, DSC). The advantage of LDT relies on high sampling rate allowing on-line measurements and lack of inertia effects that exist in other methods like calorimetry. The limitations of the applicability of the method are discussed. The method needs supplementary information not only on crystal thickness but also on variable optical birefringence of real crystals. Our results show that LDT can be used in a simple way for investigation of crystallization kinetics at relatively high temperatures, providing large and perfect crystals. In such a case it is sufficient to use crystal intrinsic birefringence and final crystal thickness typical at particular temperature of crystallization. On the other hand, depolarization ratio combined with measurements by other methods (crystallinity and crystal thickness) can be used for estimation of crystal birefringence.

Polymer, Crystallization kinetics, Light depolarization, Crystal birefringence

Phase transitions in isotactic polypropylene were investigated during isothermal crystallization and heating after isothermal crystallization using various experimental techniques. The results obtained by wide angle x-ray scattering (WAXS), light depolarization technique (LDT), differential scanning calorimetry (DSC) and optical microscopy show that crystallization of isotactic polypropylene can result in simultaneous formation of two crystal modifications, alpha and beta. There is clear experimental evidence that beta phase tends to convert into alpha modification during crystallization as well as during subsequent heating. Experimental results are compared with numerical simulation performed according to the model of nucleation-controlled phase transitions in multiphase systems. The results of simulation show that beta phase is not thermodynamically stable in any temperature range. The reason for the appearance of beta phase is related to low interfacial tension of melt vs. beta. It has been also shown that maximum crystallinity reached in experiments does not exceed 40–50% in agreement with the concept of constrained amorphous phase.

polypropylene, polymorphism, metastability, crystallization

A new setup for light depolarization measurements was designed. Two innovative elements have been introduced. The first is an electronic system which enables depolarization ratio to be registered directly. The second is a system of temperature control allowing effective implementation of a temperature–time program according to the particular requirements. Direct registration of depolarization ratio instead of intensity of depolarized light for individual components (parallel and perpendicular), as is performed in the usual apparatus, allows elimination of light scattering effects because of the insensitivity of depolarization ratio to the scattering level. Application of the new setup was shown for crystallization and melting of isotactic polypropylene (i-PP). Comparison of phase transitions in i-PP, as registered by light depolarization and DSC, indicates some differences. Possible sources of the observed differences are discussed.

Light depolarization, Polymers, Crystallization, Melting, Kinetics of phase transitions

Studies of kinetics of polymer crystallization are generally performed by heating the material above the melting point, in order to erase previous thermal and mechanical history, followed by rapid cooling to the desired crystallization temperature or by cooling at a constant rate. For poly(3-hydroxybutyrate) this procedure implies some degradation of the polymer chain, which starts below the onset of melting. In this article the effects of melting conditions on the subsequent crystallization kinetics are discussed. It is shown that in order to sufficiently cancel memories of previous crystalline order of the analyzed PHB, it is necessary to bring the material at a temperature higher than 192 °C. Thermal treatments conducted at lower temperatures are not sufficient to destroy all solid aggregates, and crystallization of PHB has an anticipated onset of crystallization due to nucleation occurring via self-seeding. The chain degradation attained upon exposure at high temperatures has much lesser influence on crystallization kinetics than incomplete melting, with some effects detectable on the spherulitic morphology and on the final degree of crystallinity.

PHB, thermal history, crystallization, degradation

The time dependence of nucleation rate in isothermal crystallization of poly(3-hydroxybutyrate) was experimentally shown, both in heterogeneous and homogeneous nucleation. The time dependence of nucleation rate is one of the important limitations for the applicability of the simplified form of Kolmogoroff- Avrami-Evans model with time independent kinetic characteristics. The presented results are interpreted in terms of non-steady-state cluster size distribution underlying transient nature of nucleation. The relaxation time needed for reaching a steady-state cluster size distribution and thus steady-state nucleation rate is relatively long, exceeding the time of exhaustion of heterogeneities. The relaxation time estimated from homogeneous process was tens of seconds in the temperature range between 83 and 120 oC. Application of Arrhenius law allows estimation of relaxation time in broader temperature range, showing an increase of relaxation time with decreasing temperature.

PHB, isothermal crystallization, nucleation rate

Melt-crystallization of polyvinylidene fluoride (PVDF) was investigated in non-isothermal mode at ultra-high cooling rates ranging between 30–3000 K/s as well as at constant temperatures after quenching at 6000 K/s. An increase of the cooling rate above 150 K/s leads to the formation of betaphase manifested by a low temperature shoulder of crystallization exotherm in addition to the alphamodification. At the cooling rates above 2000 K/s there is only low temperature exothermic peak that is attributed to the crystallization of pure betamodification. Isothermal crystallization was possible to realize at 110 oC as the lowest, resulting in form. Much higher crystallization rate in submicrogram samples, as compared to standard DSC experiments, is also reported.

Polyvinylidene fluoride, Crystallization, Ultra-fast calorimetry, Polymorphism

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.

PHB, crystallization, nucleation, DSC

The analysis of WAXS profiles for various polyethylenes indicates that the proper description of a structure needs the introduction of a kind of ‘third phase’ in addition to the classical crystalline and amorphous phases. The structure of the additional phase is intermediate between that of the amorphous and crystalline phase. With increasing branch content and molecular weight the intermediate phase becomes more similar to the structure of amorphous phase. The experimental evidence for the intermediate phase is derived not only from the crude approximation of WAXS profiles based on the two phase model but also from the unexpected behavior of the parameters of amorphous halo during crystallization. When crystallization is started, an analysis based upon two-phase model results in an apparent increase of the diffraction angle and width of amorphous halo with time above the values anticipated from the range before the start of crystallization. This is caused by the fact that the amorphous fitting function tries to cover a peak of the intermediate component that appears between morphous halo and (110) reflection of crystalline phase. The conventionally applied two-phase model leads to several serious errors in determination of structural parameters of both phases. The analysis of crystallization kinetics using three-phase model provides additional information on the nature of crystallization itself.

Polyethylene, Crystallization, Intermediate phase

Crystallization of polypropylene (PP) can result in formation of different crystal modifications depending on external conditions. The mechanisms of formation of various crystal modifications in polypropylene are still under discussion.We have investigated non-isothermal melt crystallization of isotactic polypropylene at cooling rates ranging from 1 up to 180,000 K/min using two types of differential scanning calorimeters-standard device Perkin–Elmer DSC Pyris-1 and ultra-fast calorimeter. Additional results were obtained by means of wide angle X-ray scattering and optical microscopy. At cooling rates below 6000 K/min there is only one exothermic peak corresponding to simultaneous crystallization ofalpha andbeta modifications. At cooling rates higher than 6000 K/min there is additional low temperature DSC peak corresponding to formation of mesomorphic phase. At the rates higher than 36,000 K/min there is no trace of formation of any ordered phase. In our opinion this complex behavior observed during crystallization of polypropylene can be explained using the concept of metastable phases. An increase ofbeta content in samples with quinacridone pigment has been observed only at very low cooling rates, corresponding to high temperatures of crystallization and low homogeneous nucleation rate.

Polypropylene, Crystallization, Utra-fast calorimetry, Crystallographic modifications, Metastable phases

Piezo-nerve, scaffold, nanofibers, tissue engineering, stem cells

scaffolds, electrospinning, polyvinylidene fluoride, tissue engineering