Custom-Made Poly(urethane) Coatings Improve the Mechanical Properties of Bioactive Glass Scaffolds Designed for Bone Tissue Engineering

The replication method is a widely used technique to produce bioactive glass (BG) scaffolds mimicking trabecular bone. However, these scaffolds usually exhibit poor mechanical reliability and fast degradation, which can be improved by coating them with a polymer. In this work, we proposed the use of custom-made poly(urethane)s (PURs) as coating materials for 45S5 Bioglass®-based scaffolds. In detail, BG scaffolds were dip-coated with two PURs differing in their soft segment (poly(ε-caprolactone) or poly(ε-caprolactone)/poly(ethylene glycol) 70/30 w/w) (PCL-PUR and PCL/PEG-PUR) or PCL (control). PUR-coated scaffolds exhibited biocompatibility, high porosity (ca. 91%), and improved mechanical properties compared to BG scaffolds (2–3 fold higher compressive strength). Interestingly, in the case of PCL-PUR, compressive strength significantly increased by coating BG scaffolds with an amount of polymer approx. 40% lower compared to PCL/PEG-PUR- and PCL-coated scaffolds. On the other hand, PEG presence within PCL/PEG-PUR resulted in a fast decrease in mechanical reliability in an aqueous environment. PURs represent promising coating materials for BG scaffolds, with the additional pros of being ad-hoc customized in their physico-chemical properties. Moreover, PUR-based coatings exhibited high adherence to the BG surface, probably because of the formation of hydrogen bonds between PUR N-H groups and BG surface functionalities, which were not formed when PCL was used.

Influence of Soft Segment Molecular Structure on Physicochemical Properties of Cellulose Nanocrystals based Polyurethane

SPUs are commonly used in clinic due to their good biocompatibility and can respond to different external stimuli. Among them, introducing CNCs into PUs to prepare water-driven PUs had attracted increasing attention. Herein, we report two new types of CNCs based PU nanocomposites by chemically cross-linking CNCs and PDLLA soft segment with flexible PEG chain or rigid piperazine ring structures. Specifically, the prepared nanocomposites were characterized by their morphology, chemical structure, thermal property, hydrophilicity as well as crystallinity, and the results showed that regardless of the molecular structure of the PDLLA, chemically cross-linking CNCs and PDLLA could significantly improve their compatibility. In addition, when the soft segment contains hydrophilic flexible sections, ie, PEG 200, the compatibility of CNCs with PU and crystallinity of obtained materials were better, and when the PDLLA contains a rigid cyclic structure, the thermal stability of obtained CNCs based PU would be more excellent. These results suggest that we can design the soft segment molecular structure of CNCs based PU to meet the performance requirements of different biomedical applications.

Transition Metal-Ions Incorporated PEG300 and TDI Based Hydroxy-Terminated Polyurethanes

Present work reports the synthesis of polyethylene glycol, PEG 300 (soft segment) and toluene 2,4-diisocyanate, TDI (hard segment) based hydroxy-terminated polyurethane ligands (HTPU300) for the first time to the best of our knowledge. The effect of 3d transition metal ions with different 3d electrons within HTPU (M(II)-HTPU300, M= Mn, Co, Ni, and Zn) was evaluated by their physical and antibacterial studies of the final complex polymeric unit. M(II) HTPU300 and was conveniently synthesized in appreciable yields following a facile and one-pot addition polymerization reaction scheme. Foremost the thermal stability of all the M(II)-HTPU300 polymeric materials were evaluated using TGA, DSC, and IPDT calculations. FTIR technique was used to ascertain the structure of M(II)-HTPU300, while SEM/EDX and XRD techniques were used to study their morphology, elemental analysis, and crystalline nature of the material, respectively. Further, the in-vitro antimicrobial activity of the PU was investigated against gram-positive (Staphylococcus aureus, Bacillus subtilis) and gram-negative (Escherichia coli and Pseudomonas aeruginosa) bacterial strains. The comparatively moderate efficacy against bacterial stain supports the possible application of such PU as thermally stable bacterial resistant materials constructed out of degradable PEG.

Crystallization and degradation behaviour of multiblock copolyester blends in Langmuir monolayers

Supporting the wound healing of soft tissues requires fixation devices becoming more elastic while degrading. To address this unmet need, we designed a blend of degradable multiblock copolymers, which is cross-linked by PLA stereocomplexation combining two soft segments differing substantially in their hydrolytic degradation rate. The degradation path and concomitant structural changes are predicted by Langmuir monolayer technique. The fast hydrolysis of one soft segment leads to a decrease of the total polymer mass at constant physical cross-linking density. The corresponding increase of the average spacing between the network nodes suggests the targeted increase of the blend’s flexibility. Graphic abstract

The Crystallisation, Microphase Separation and Mechanical Properties of the Mixture of Ether-Based TPU with Different Ester-Based TPUs

The difference in compatibility at the molecular level can lead to a change of microphase separation structure of thermoplastic polyurethanes blend systems, which will improve their thermal and mechanical properties. In this study, TDI-polyester based TPU was blended with MDI-polyether-based TPU and MDI-polyester based TPU, with different ratios. In the blend system, the obvious reduction of the melting temperature of the high-temperature TDI-polyester based TPU component indicates its hard segments can be mutually integrated with the other component. For TDI-polyester based TPU/MDI-polyether based TPU blends, their similar hard segment ratio and similar chemical structure of the soft segment give the molecular chains of the two components better compatibility. The aggregation structure of the two kinds of chains can rearrange at the molecular level which makes the hard domains mutually integrate to form a new phase separation structure with larger phase region distance. As a result, the yield strength of this blend increased by almost 143% when the elongation at break was only reduced by 12%. In contrast, the other group of blends still partly maintain their respective micro domains, forming a weak interface and leading to a decreased of elongation at break.

Investigating Physio-Thermo-Mechanical Properties of Polyurethane and Thermoplastics Nanocomposite in Various Applications

The effect of the soft and hard polyurethane (PU) segments caused by the hydrogen link in phase-separation kinetics was studied to investigate the morphological annealing of PU and thermoplastic polyurethane (TPU). The significance of the segmented PUs is to achieve enough stability for further applications in biomedical and environmental fields. In addition, other research focuses on widening the plastic features and adjusting the PU–polyimide ratio to create elastomer of the poly(urethane-imide). Regarding TPU- and PU-nanocomposite, numerous studies investigated the incorporation of inorganic nanofillers such as carbon or clay to incorporating TPU-nanocomposite in several applications. Additionally, the complete exfoliation was observed up to 5% and 3% of TPU–clay modified with 12 amino lauric acid and benzidine, respectively. PU-nanocomposite of 5 wt.% Cloisite®30B showed an increase in modulus and tensile strength by 110% and 160%, respectively. However, the nanocomposite PU-0.5 wt.% Carbone Nanotubes (CNTs) show an increase in the tensile modulus by 30% to 90% for blown and flat films, respectively. Coating PU influences stress-strain behavior because of the interaction between the soft segment and physical crosslinkers. The thermophysical properties of the TPU matrix have shown two glass transition temperatures (Tg’s) corresponding to the soft and the hard segment. Adding a small amount of tethered clay shifts Tg for both segments by 44 °C and 13 °C, respectively, while adding clay from 1 to 5 wt.% results in increasing the thermal stability of TPU composite from 12 to 34 °C, respectively. The differential scanning calorimetry (DSC) was used to investigate the phase structure of PU dispersion, showing an increase in thermal stability, solubility, and flexibility. Regarding the electrical properties, the maximum piezoresistivity (10 S/m) of 7.4 wt.% MWCNT was enhanced by 92.92%. The chemical structure of the PU–CNT composite has shown a degree of agglomeration under disruption of the sp2 carbon structure. However, with extended graphene loading to 5.7 wt.%, piezoresistivity could hit 10-1 S/m, less than 100 times that of PU. In addition to electrical properties, the acoustic behavior of MWCNT (0.35 wt.%)/SiO2 (0.2 wt.%)/PU has shown sound absorption of 80 dB compared to the PU foam sample. Other nanofillers, such as SiO2, TiO2, ZnO, Al2O3, were studied showing an improvement in the thermal stability of the polymer and enhancing scratch and abrasion resistance.

Impact of Macrodiols on the Morphological Behavior of H12MDI/HDO-Based Polyurethane Elastomer

In this study, we evaluated the morphological behavior of polyurethane elastomers (PUEs) by modifying the soft segment chain length. This was achieved by increasing the soft segment molecular weight (Mn = 400–4000 gmol−1). In this regard, polycaprolactone diol (PCL) was selected as the soft segment, and 4,4′-cyclohexamethylene diisocyanate (H12MDI) and 1,6-hexanediol (HDO) were chosen as the hard segments. The films were prepared by curing polymer on Teflon surfaces. Fourier transform infrared spectroscopy (FTIR) was utilized for functional group identification in the prepared elastomers. FTIR peaks indicated the disappearance of −NCO and −OH groups and the formation of urethane (NHCOO) groups. The morphological behavior of the synthesized polymer samples was also elucidated using scanning electron microscopy (SEM) and atomic force microscopy (AFM) techniques. The AFM and SEM results indicated that the extent of microphase separation was enhanced by an increase in the molecular weight of PCL. The phase separation and degree of crystallinity of the soft and hard segments were described using X-ray diffraction (XRD). It was observed that the degree of crystallinity of the synthesized polymers increased with an increase in the soft segment’s chain length. To evaluate hydrophilicity/hydrophobicity, the contact angle was measured. A gradual increase in the contact angle with distilled water and diiodomethane (38.6°–54.9°) test liquids was observed. Moreover, the decrease in surface energy (46.95–24.45 mN/m) was also found to be inconsistent by increasing the molecular weight of polyols.