Search Results (43)

The development of 3D printing high-impact denture bases is challenging, as materials exhibiting both high flexural strength/modulus and fracture toughness are required. Nowadays, most of the commercially available 3D printing denture bases contain significant amounts of crosslinking monomers and therefore behave as brittle materials. In this contribution, urethane dimethacrylate DMA1/(octahydro-4,7-methano-1H-indenyl)methyl acrylate (OMIMA) 1/1 (wt/wt) formulations containing a poly(ε-caprolactone)-polydimethylsiloxane-poly(ε-caprolactone) (PCL-PDMS-PCL) triblock copolymer (BCP1) and fumed silica SiO₂-NPs were evaluated for DLP 3D printing of fracture-tough denture bases. The post-curing step was performed at various temperatures (RT, 60 °C, 80 °C, 100 °C and 120 °C). This parameter was shown to strongly influence the T_g and mechanical properties of 3D printed materials. A post-curing temperature of 100 °C was found to be ideal. Under these conditions, 3D printed materials exhibiting excellent mechanical properties were successfully obtained. Furthermore, the amounts of BCP1 and SiO₂-NPs were varied. The formulation containing 8.0 wt% of BCP1 and 10.0 wt% of SiO₂-NPs (FS = 67.5 ± 1.3 MPa, FM = 2450 ± 71 MPa, K_max = 2.11 ± 0.06 MPa m^1/2, W_f = 1109 ± 19 J m⁻²) was able to fulfill the ISO 20795-1:2013 requirements in terms of flexural strength (FS)/modulus (FM) and fracture toughness for denture bases with improved impact resistance (FS > 65 MPa, FM > 2000 MPa, K_max > 1.9 MPa m^1/2, W_f > 900 J m⁻²). This material showed better performance than the commercially available formulations Printodent^® GR-14.2 denture HI (FS = 69.2 ± 1.8 MPa, FM = 2153 ± 76 MPa, K_max = 0.82 ± 0.04 MPa m^1/2, W_f = 79 ± 10 J m⁻²) and Lucitone Digital Print^TM 3D denture base (FS = 56.7 ± 1.9 MPa, FM = 2144 ± 12 MPa, K_max = 1.92 ± 0.09 MPa m^1/2, W_f = 1272 ± 177 J m⁻²). Full article

Smart textiles require conductive materials that maintain electrical stability under repeated mechanical deformation and laundering while preserving textile-like flexibility. In this work, an elastic–rigid copolymer elastomer was designed as a polymer binder for washable conductive pastes used in wearable textile electronics. The copolymer was synthesized using polytetramethylene ether glycol (PTMEG), 3,3′,4,4′-benzophenonetetracarboxylic dianhydride (BTDA), and m-xylylene diisocyanate (XDI), enabling the incorporation of thermally stable imide segments and elastic polyurethane domains within a single polymer framework. By adjusting the molar ratio between rigid and soft segments, the resulting copolymer exhibited balanced tensile strength, Young’s modulus, and elastic recovery, outperforming a commercial thermoplastic polyurethane in mechanical performance. Silver-filled conductive pastes were prepared by dispersing 62 wt% micrometer-sized silver flakes into the copolymer matrix, achieving a bulk resistivity of 3.5 × 10⁻⁵ Ω·cm. The printed conductive films showed stable electrical resistivity under cyclic tensile deformation up to 20% strain. Washing durability was further evaluated following the AATCC 135 top-loading laundering standard. After 50 laundering cycles, the resistance increase remained within 2.8–5.5 Ω for knitted fabrics and 2.0–5.1 Ω for woven fabrics, indicating satisfactory electrical stability and adhesion to textile substrates. These results suggest that elastic–rigid copolymer binders are suitable for the development of wash-durable conductive pastes for wearable textile applications. Full article

The research hypothesis was that adjusting the content of the quaternary ammonium urethane dimethacrylate monomer bearing an N-dodecyl substituent (QAUDMA-12) would yield dental matrices with high antimicrobial activity, good biocompatibility, and favorable physicochemical properties. The research hypothesis was verified for six Bis-GMA, TEGDMA, and UDMA copolymers containing from 2.5 to 40 wt.% QAUDMA-12 by determining their degree of conversion, hardness, flexural properties, water behavior, antimicrobial activity against Staphylococcus aureus, Staphylococcus epidermidis, Escherichia coli, Candida albicans, and cytotoxicity towards L929 mouse fibroblast cells. The research hypothesis was confirmed. Copolymers containing less than 30 wt.% QAUDMA-12 exhibited favorable polymerization efficiency, water sorption and solubility, and mechanical properties comparable to those of conventional Bis-GMA/TEGDMA systems. At the same time, they showed no cytotoxic effects toward mouse fibroblast cells. The results of antimicrobial tests show that the minimum QAUDMA-12 concentration providing sufficient antimicrobial activity was 20 wt.%. Therefore, it can be concluded that the 20 wt.% concentration of QAUDMA-12 makes it possible to obtain dental matrices that are non-toxic, exhibit antimicrobial activity, and possess the desired physico-mechanical performance. Full article

Dental composite reconstructive materials (DCRMs) used in caries treatment possess satisfactory functional properties but lack antimicrobial activity, which may lead to secondary caries. This research aimed to modify the DCRM matrix with urethane-dimethacrylate monomers derived from cycloaliphatic and aromatic diisocyanates bearing quaternary ammonium groups. The diisocyanates used were 1,3-bis(1-isocyanato-1-methylethyl)benzene (TMXDI), isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (CHMDI), and 1,1′-methylenebis(4-isocyanatobenzene) (MDI). As a result, eight modified copolymers were obtained and tested for the surface water contact angle (WCA), water sorption (WS), and water solubility (SL). The WCA results indicated predominantly hydrophilic surfaces, while the WS and SL values were generally satisfactory. Full article

Wearable and skin-mounted electronics demand encapsulation designs that simultaneously provide strong barrier performance, mechanical reliability, and transferability under ultrathin conditions. In this study, a residual stress-balanced transferable encapsulation platform was developed by integrating a urethane-based copolymer superstrate [p(IEM-co-HEMA)] with inorganic thin films. The polymer, deposited via initiated chemical vapor deposition (iCVD), offered over 90% optical transmittance, low RMS roughness (1–3 nm), and excellent solvent resistance, providing a stable base for inorganic barrier integration. An ALD Al₂O₃/ZnO nano-stratified barrier initially delivered effective moisture blocking, but tensile stress accumulation imposed a critical thickness of 30 nm, where the WVTR plateaued at ~2.5 × 10⁻⁴ g/m²/day. To overcome this limitation, a 40 nm e-beam SiO₂ capping layer was added, introducing compressive stress via atomic peening and stabilizing Al₂O₃ interfaces through Si–O–Al bonding. This stress-balanced design doubled the critical thickness to 60 nm and reduced the WVTR to 3.75 × 10⁻⁵ g/m²/day, representing an order-of-magnitude improvement. OLEDs fabricated on this ultrathin platform preserved J–V–L characteristics and efficiency (~4.5–5.0 cd/A) after water-assisted transfer and on-skin deformation, while maintaining LT80 lifetimes of 140–190 h at 400 cd/m² and stable emission for over 20 days in ambient storage. These results demonstrate that the stress-balanced encapsulation platform provides a practical route to meet the durability and reliability requirements of next-generation wearable optoelectronic devices. Full article

The development of high-impact denture base formulations that are suitable for digital light processing (DLP) 3D printing is demanding. Indeed, a combination of high flexural strength/modulus and high fracture toughness is required. In this contribution, eight urethane macromonomers (UMs1-8) were synthesized in a one-pot, two-step procedure. Several rigid diols were first reacted with two equivalents of trimethylhexamethylene diisocyanate. The resulting diisocyanates were subsequently end-capped with a free-radically polymerizable monomer bearing a hydroxy group. UMs1-8 were combined with the monofunctional monomer (octahydro-4,7-methano-1H-indenyl)methyl acrylate and a poly(ε-caprolactone)-polydimethylsiloxane-poly(ε-caprolactone) (PCL-PDMS-PCL) triblock copolymer (BCP1) as a toughening agent. The double-bond conversion, glass transition temperature (T_g), and mechanical properties (flexural strength/modulus, fracture toughness) of corresponding light-cured materials were measured (cured in a mold using a light-curing unit). The results showed that the incorporation of BCP1 was highly efficient at significantly increasing the fracture toughness, as long as the obtained networks exhibited a low crosslink density. The structure of the urethane macromonomer (nature of the rigid group in the spacer; nature and number of polymerizable groups) was demonstrated to be crucial to reach the desired properties (balance between flexural strength/modulus and fracture toughness). Amongst the evaluated macromonomers, UM1 and UM2 were particularly promising. By correctly adjusting the BCP1 content, light-cured formulations based on those two urethane dimethacrylates were able to fulfill ISO20795-1:2013 standard requirements regarding high-impact materials. These formulations are therefore suitable for the development of 3D printable high-impact denture bases. Full article

Six novel urethane-dimethacrylates with quaternary ammonium groups (QAUDMAs) were successfully synthesized from 2-(methacryloyloxy)ethyl-2-hydroxyethylmethylalkylammonium bromide (QAHAMA-n, where n was 8 and 10) and diisocyanate (isophorone diisocyanate (IPDI), 4,4′-methylenedicyclohexyl diisocyanate (CHMDI), and 4,4′-diphenylmethane diisocyanate (MDI)). Their chemical structures were confirmed through nuclear magnetic resonance spectroscopy (NMR) and Fourier transform infrared spectroscopy (FTIR). The refractive index (RI) and density (d_m) were also determined. The novel QAUDMAs were compounded with common dental dimethacrylates and subsequently photopolymerized. The resulting copolymers, comprising QAUDMA 40 wt.%, bisphenol A glycerolate dimethacrylate (Bis-GMA) 40 wt.%, and triethylene glycol dimethacrylate (TEGDMA) 20 wt.%, were tested for water sorption (WS) and solubility (SL). The WS and SL values decreased following these orderings based on the diisocyanate: IPDI > CHMDI > MDI for WS, and MDI > CHMDI > IPDI for SL. The WS values ranged from 11.50 to 13.82 µg/mm³, and were significantly lower than the recommended maximum for dental materials, 40 µg/mm³. The SL values that met the recommended maximum, 7.5 µg/mm³, ranged from 2.67 to 6.75 µg/mm³. Only the copolymer having the QAHAMA-8- and MDI-derived QAUDMA had the SL slightly exceeding 7.5 µg/mm³, at 7.89 µg/mm³. Full article

The paper describes changes in the structure, morphology, mechanical and thermal properties of porous film samples of poly(4,4′-oxidiphenylene)pyromellitimide prepared as a result of selective destruction of urethane blocks in copolymers composed of pyromellitimide blocks and polyurethane blocks. The initial samples of the new composition of statistical copoly(urethane-imide)s (CoPUIs) were prepared via polycondensation methods using pyromellitic dianhydride (PMDA), 4,4′-oxidyaniline (ODA), 2,4-toluylenediisocyanate (TDI), as well as polycaprolactone (PCL) and poly(1,6-hexanediol/neopentylglycol-alt-adipic acid) (ALT) as monomers. The molar ratio of imide and polyurethane blocks in CoPUI was 10:1. The initial films were heated up to 170 °C to complete the polycondensation processes, after which they were subjected to thermolysis and hydrolysis. The thermolysis (thermal degradation) of copolymers was carried out by heating the initial samples to temperatures of 300 °C or 350 °C. Then, the thermolized films were subjected to chemical degradation in hydrolytic baths containing an aqueous solution of potassium hydroxide. As a result, urethane blocks were destroyed and removed from the polymer. The resulting products practically did not contain polyurethane links and, in chemical composition, were practically identical to poly(4,4′-oxidiphenylene)pyromellitimide. NMR and IR spectroscopy, atomic force microscopy, X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry and dynamic mechanical analysis and mechanical properties testing were used to determine the differences in the structure and properties of the initial copolymers and targeted products. The effect of the conditions of destructive processes on the structure, morphology and mechanical properties of the obtained porous polyimide films was determined. From a practical point of view, the final porous films are promising as membranes for filtering aggressive amide solvents at high temperatures. Full article

Background and objectives: The use of polymeric nanoparticles (NPs) in drug delivery systems offers the advantages of enhancing drug efficacy and minimizing side effects; Methods: In this study, L-threonine polyurethane (LTPU) NPs have been fabricated by water-in-oil-in-water emulsion and solvent evaporation using biodegradable and biocompatible LTPU. This polymer was pre-synthesized through the use of an amino acid-based chain extender, desaminotyrosyl L-threonine hexyl ester (DLTHE), where urethane bonds are formed by poly(lactic acid)-poly(ethylene glycol)-poly(lactic acid) (PLA-PEG-PLA) triblock copolymer and 1,6-hexamethylene diisocyanate (HDI). LTPU is designed to be degraded by hydrolysis and enzymatic activity due to the presence of ester bonds and peptide bonds within the polymer backbone. LTPU NPs were fabricated by water-in-oil-in-water double emulsion solvent evaporation methods; Results: The polymerization of LTPU was confirmed by ¹H-NMR, ¹³C-NMR, and FT-IR spectroscopies. The molecular weights and polydispersity, determined with GPC, were 28,800 g/mol and 1.46, respectively. The morphology and size of NPs, characterized by DLS, FE-SEM, TEM, and confocal microscopy, showed smooth and spherical particles with diameters less than 200 nm; Conclusions: In addition, the drug loading, encapsulation efficiency, and drug release profiles, using UV-Vis spectroscopy, showed the highest encapsulation efficiency with 2.5% carboplatin and sustained release profile. Full article

Dental caries are treated using dental composite restorative materials (DCRM). However, commercial DCRMs lack antibacterial activity. This research aimed to analyze the in vitro antibacterial activity of a series of copolymers consisting of a urethane–dimethacrylate monomer (UDMA), bisphenol A glycerolate dimethacrylate (Bis-GMA), triethylene glycol dimethacrylate (TEGDMA) and urethane–dimethacrylate monomer with two quaternary ammonium groups and a 1,3-bis(1-isocyanate-1-methylethyl)benzene core (QAn+TMXDI, where n = 8, 10, or 12 is the number of carbon atoms in the N-alkyl substituent). QAn+TMXDI contents in copolymers were 20 and 40 wt.%. The results of the Staphylococcus aureus and Escherichia coli adhesion test demonstrated that the logCFU/mL decreased as the length of the N-alkyl chain decreased and QAn+TMXDI content increased. The copolymers of QA8+TMXDI 40 wt.%, Bis-GMA 40 wt.%, and TEGDMA 20 wt.% showed the highest antibacterial activity, with a logCFU/mL of 2.39 for S. aureus and no viable E. coli cells. Full article

Polyurethane elastomers are among the most versatile classes of industrial polymers—typically achieved through a two-step synthesis of segmented block copolymers, comprising very long and soft segments that provide elasticity and significantly long and hard segments that provide strength. The present research focused on the design of a single-step synthesis of a new segmented polyurethane consisting of very short soft and hard segments, crosslinked by preferentially side-reacted hierarchical tertiary oligo-uret network structures, thus exhibiting significant strength, elasticity, and toughness. Despite the theoretically linear structure, both FTIR and solid-state ¹³C NMR spectroscopy analyses indicated the quasi-equal presence of urethane groups and tertiary oligo-uret structures in the resulting polymer, indicating a preferential consecutive side reaction mechanism. Thermal analysis indicated the significant crystallization of soft segments consisting of only four ethylene oxide units, which was, hereby, demonstrated to occur via an extended chain mechanism. Tensile mechanical properties included significant strength, elasticity, and toughness. Increasing the soft segment length led to a decreased tertiary oligo-uret secondary crosslinking efficacy. The preferential hierarchical side reaction mechanism was, hereby, further confirmed through the synthesis of a completely new type of hyper-branched polymer via diisocyanate and a mono-hydroxy-terminated reagent. The structure–property relations and reaction mechanisms demonstrated in the present research can facilitate the design of new polyurethanes of enhanced performance and processing efficacy for a variety of novel applications. Full article

In this study, two novel quaternary ammonium urethane-dimethacrylates (QAUDMAs) were designed for potential use as comonomers in antibacterial dental composite restorative materials. QAUDMAs were synthesized via the reaction of 1,3-bis(1-isocyanato-1-methylethyl)benzene with 2-(methacryloyloxy)ethyl-2-decylhydroxyethylmethylammonium bromide (QA10+TMXDI) and 2-(methacryloyloxy)ethyl-2-dodecylhydroxyethylmethylammonium bromide (QA12+TMXDI). Their compositions with common dental dimethacrylates comprising QAUDMA 20 wt.%, urethane-dimethacrylate monomer (UDMA) 20 wt.%, bisphenol A glycerolate dimethacrylate (Bis-GMA) 40 wt.%, and triethylene glycol dimethacrylate (TEGDMA) 20 wt.%, were photocured. The achieved copolymers were characterized for their physicochemical and mechanical properties, including their degree of conversion (DC), glass transition temperature (T_g), polymerization shrinkage (S), water contact angle (WCA), flexural modulus (E), flexural strength (FS), hardness (HB), water sorption (WS), and water leachability (WL). The antibacterial activity of the copolymers was characterized by the minimum bactericidal concentration (MBC) and minimum inhibitory concentration (MIC) against Staphylococcus aureus and Escherichia coli. The achieved results were compared to the properties of a typical dental copolymer comprising UDMA 40 wt.%, Bis-GMA 40 wt.%, and TEGDMA 20 wt.%. The introduction of QAUDMAs did not deteriorate physicochemical and mechanical properties. The WS and WL increased; however, they were still satisfactory. The copolymer comprising QA10+TMXDI showed a higher antibacterial effect than that comprising QA12+TMXDI and that of the reference copolymer. Full article

Using dental composite restorative materials with a copolymeric matrix chemically modified towards bioactive properties can help fight secondary caries. In this study, copolymers of 40 wt.% bisphenol A glycerolate dimethacrylate, 40 wt.% quaternary ammonium urethane-dimethacrylates (QAUDMA-m, where m represents 8, 10, 12, 14, 16 and 18 carbon atoms in the N-alkyl substituent), and 20 wt.% triethylene glycol dimethacrylate (BG:QAm:TEGs) were tested for (i) cytotoxicity on the L929 mouse fibroblast cell line; (ii) fungal adhesion, fungal growth inhibition zone, and fungicidal activity against C. albicans; and (iii) bactericidal activity against S. aureus and E. coli. BG:QAm:TEGs had no cytotoxic effects on L929 mouse fibroblasts because the reduction of cell viability was less than 30% compared to the control. BG:QAm:TEGs also showed antifungal activity. The number of fungal colonies on their surfaces depended on the water contact angle (WCA). The higher the WCA, the greater the scale of fungal adhesion. The fungal growth inhibition zone depended on the concentration of QA groups (x_QA). The lower the x_QA, the lower the inhibition zone. In addition, 25 mg/mL BG:QAm:TEGs suspensions in culture media showed fungicidal and bactericidal effects. In conclusion, BG:QAm:TEGs can be recognized as antimicrobial biomaterials with negligible biological patient risk. Full article

This study aimed to elucidate the physicochemical properties of copolymers comprising 40 wt.% bisphenol A glycerolate dimethacrylate (Bis-GMA), 40 wt.% quaternary ammonium urethane-dimethacrylate analogues (QAUDMA-m, where m corresponds to the number of carbon atoms in the N-alkyl substituent), and 20 wt.% triethylene glycol dimethacrylate (TEGDMA) copolymers (BG:QAm:TEGs). The BG:QAm:TEG liquid monomer compositions and reference compositions (40 wt.% Bis-GMA, 40 wt.% urethane-dimethacrylate (UDMA), 20 wt.% TEGDMA (BG:UD:TEG) and 60 wt.% Bis-GMA, 40 wt.% TEGDMA (BG:TEG)) were characterized in terms of their refractive index (RI) and monomer glass transition temperature (Tg_m) and then photocured. The resulting copolymers were characterized in terms of the polymer glass transition temperature (Tg_p), experimental polymerization shrinkage (S_e), water contact angle (WCA), water sorption (WS), and water solubility (SL). The prepared BG:QAm:TEG liquid monomer compositions had RI in the range 1.4997–1.5129, and Tg_m in the range −52.22 to −42.12 °C. The BG:QAm:TEG copolymers had Tg_p ranging from 42.21 to 50.81 °C, S_e ranging from 5.08 to 6.40%, WCA ranging from 81.41 to 99.53°, WS ranging from 25.94 to 68.27 µg/mm³, and SL ranging from 5.15 to 5.58 µg/mm³. Almost all of the developed BG:QAm:TEGs fulfilled the requirements for dental materials (except BG:QA8:TEG and BG:QA10:TEG, whose WS values exceeded the 40 µg/mm³ limit). Full article

Bone adhesives offer distinct advantages over the use of screws to attached internal fixation plates (IFPs). As the chemical composition of bone is similar to dentine, it is possible that the types of monomers used to make dentine adhesives could be utilised to affix IFPs to bone. The ability to attach a bio-resorbable IFP to porcine bone was assessed for the monomer 10-methacryloyloxydecyl dihydrogen phosphate (MDP), used either as a homopolymer or a copolymer with urethane dimethacrylate (MDP + U). Additionally, the addition of a priming step (MDP + U + P) was evaluated. The chemical interactions of the monomers with bone were assessed using XRD and imaged using TEM, revealing the formation of nano-layered structures with the MDP primer, something we believe has not been reported on bone. In a 6-week artificial aging study both MDP + U and MDP + U + P demonstrated adequate shear bond strength to affix bio-resorbable IFPs. The cytotoxicity profiles of the adhesive formulations were determined using indirect and direct contact with MC3T3 cells, with indirect conditions suggesting the MDP + U + P is as cytocompatible as the resorbable IFP. The findings of this study suggest our newly developed adhesive has the potential to be used as a bone adhesive to affix bioresorbable IFPs. Full article