Crystallographic Texture Evolution in 3D Printed Polyethylene Reactor Blends.

In this work, crystallographic texture evolution in 3D printed trimodal polyethylene (PE) blends and high-density PE (HDPE) benchmark material were investigated to quantify the resulting material anisotropy, and the results were compared to materials made from conventional injection molded (IM) samples. Trimodal PE reactor blends consisting of HDPE, ultrahigh molecular weight PE (UHMWPE), and HDPE_wax have been used for 3D printing and injection molding. Changes in the preferred orientation and distribution of crystallites, i.e., texture evolution, were quantified utilizing the wide angle X-ray diffraction through pole figures and orientation distribution functions (ODFs) for 3D printed and IM samples. Since the change in weight-average molecular weight (Mw) of the blend was expected to significantly affect the resulting crystallinity and orientation, the overall Mw of the trimodal PE blend was varied while keeping the UHMWPE component weight fraction to 10% in the blend. The resulting texture was analyzed by varying the overall Mw of the trimodal blend and the process parameters in 3D printing and compared to the texture of conventional IM samples. The printing speed and orientation (defined with respect to the axis along the length of the samples) were used as the variable process parameters for 3D printing. The degree of anisotropy increases with an increase in the nonuniform distribution of intensities in pole figures and ODFs. All the highest intensity major texture components in IM and 3D printed samples (0° printing orientation) of reactor blends are observed to have crystals oriented in [001] or [001̅]. Overall, for the same throughput, 3D printed samples in the 0° orientation showed greater texture evolution and higher anisotropy compared to IM samples. Most notably, an increase in 3D printing speed increased the crystalline distribution closer to the 0° direction, increasing the anisotropy, while deviation from this printing orientation reduced crystalline distribution closer to the 0° direction, thus increasing isotropy. This demonstrates that tailoring material properties in specific directions can be achieved more effectively with 3D printing than with the injection molding process. Change in the overall Mw of the trimodal PE blend changed the preferential orientation distribution of the crystal planes to some degree. However, the degree of anisotropy remained the same in almost all cases, indicating that the effect of molecular weight distribution is not as significant as the printing speed and printing orientation in tailoring the resulting properties. The 3D printing process parameters (speed and orientation) were shown to have more influence on the texture than the material parameters associated with the blend.

Dimensional accuracy and simulation-based optimization of polyolefins and biocopolyesters for extrusion-based additive manufacturing and steam sterilization.

Polyolefins exhibit robust mechanical and chemical properties and can be applied in the medical field, e.g. for the manufacturing of dentures. Despite their wide range of applications, they are rarely used in extrusion-based printing due to their warpage tendency. The aim of this study was to investigate and reduce the warpage of polyolefins compared to commonly used filaments after additive manufacturing (AM) and sterilization using finite element simulation. Three types of filaments were investigated: a medical-grade polypropylene (PP), a glass-fiber reinforced polypropylene (PP-GF), and a biocopolyester (BE) filament, and they were compared to an acrylic resin (AR) for material jetting. Square specimens, standardized samples prone to warpage, and denture bases (n = 10 of each group), as clinically relevant and anatomically shaped reference, were digitized after AM and steam sterilization (134 °C). To determine warpage, the volume underneath the square specimens was calculated, while the deviations of the denture bases from the printing file were measured using root mean square (RMS) values. To reduce the warpage of the PP denture base, a simulation of the printing file based on thermomechanical calculations was performed. Statistical analysis was conducted using the Kruskal-Wallis test, followed by Dunn's test for multiple comparisons. The results showed that PP exhibited the greatest warpage of the square specimens after AM, while PP-GF, BE, and AR showed minimal warpage before sterilization. However, warpage increased for PP-GF, BE and AR during sterilization, whereas PP remained more stable. After AM, denture bases made of PP showed the highest warpage. Through simulation-based optimization, warpage of the PP denture base was successfully reduced by 25%. In contrast to the reference materials, PP demonstrated greater dimensional stability during sterilization, making it a potential alternative for medical applications. Nevertheless, reducing warpage during the cooling process after AM remains necessary, and simulation-based optimization holds promise in addressing this issue.

Influence of Graphene Type and Content on Friction and Wear of Silicon Carbide/Graphene Nanocomposites in Aqueous Environment.

Two different types of graphene materials were used as functional nanofillers for the mechanical and tribological improvement of silicon carbide/graphene nanocomposites. On the one hand is thermally reduced graphite oxide (TRGO) reduced at three different temperatures, and on the other hand is graphene made of three different organic precursors, which were directly coated on silicon carbide (SiC) platelets (GSiC). Additionally, benchmark materials were also used as carbon fillers. The SiC/graphene nanocomposites with 2 wt% filler content were manufactured by pressureless sintering (PLS). Some composites were produced with higher graphene contents of 4% and 8% and sintered by spark plasma sintering (SPS). Microstructural analyses were conducted using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Underwater lubrication, the SP sintered TRGO and GSiC materials with high graphene content have shown the most promising tribological performance. Furthermore, the reduced size of the homogeneously distributed nanoparticles promotes the formation of surface states, which improve the friction and wear properties.

Laser Ablation on Isostatic Graphite-A New Way to Create Exfoliated Graphite.

In search of a new way to fabricate graphene-like materials, isostatic graphite targets were ablated using high peak power with a nanosecond-pulsed infrared laser. We conducted dry ablations in an argon atmosphere and liquid-phase ablations in the presence of a liquid medium (water or toluene). After the dry ablation, the SEM images of the target showed carbon in the form of a volcano-like grain structure, which seemed to be the result of liquid carbon ejected from the ablation center. No graphite exfoliation could be achieved using dry ablation. When using liquid phase ablation with water or toluene as a liquid medium, no traces of the formation of liquid carbon were found, but cleaner and deeper craters were observed. In particular, when using toluene as a liquid medium, typical graphite exfoliation was found. We believe that due to the extremely high pressure and high temperature induced by the laser pulses, toluene was able to intercalate into the graphite layers. Between the laser pulses, the intercalated toluene was able to flash evaporate and blow-up the graphite, which resulted in exfoliated graphite. Exfoliated graphite was found on the ablated graphite surface, as well as in the toluene medium. The ablation experiments with toluene undertaken in this study demonstrated an effective method of producing micrometer-sized graphene material. When using water as a liquid medium, no massive graphite exfoliation was observed. This meant that under the used laser conditions, toluene was a better intercalant for graphite exfoliation than water.

Closing the Carbon Loop in the Circular Plastics Economy.

Today, plastics are ubiquitous in everyday life, problem solvers of modern technologies, and crucial for sustainable development. Yet the surge in global demand for plastics of the growing world population has triggered a tidal wave of plastic debris in the environment. Moving from a linear to a zero-waste and carbon-neutral circular plastic economy is vital for the future of the planet. Taming the plastic waste flood requires closing the carbon loop through plastic reuse, mechanical and molecular recycling, carbon capture, and use of the greenhouse gas carbon dioxide. In the quest for eco-friendly products, plastics do not need to be reinvented but tuned for reuse and recycling. Their full potential must be exploited regarding energy, resource, and eco-efficiency, waste prevention, circular economy, climate change mitigation, and lowering environmental pollution. Biodegradation holds promise for composting and bio-feedstock recovery, but it is neither the Holy Grail of circular plastics economy nor a panacea for plastic littering. As an alternative to mechanical downcycling, molecular recycling enables both closed-loop recovery of virgin plastics and open-loop valorization, producing hydrogen, fuels, refinery feeds, lubricants, chemicals, and carbonaceous materials. Closing the carbon loop does not create a Perpetuum Mobile and requires renewable energy to achieve sustainability.

Small-Molecule Investigation of Diels-Alder Complexes for Thermoreversible Crosslinking in Polymeric Applications.

Combinations of dienes and dienophiles were examined in order to elicit possible combinations for thermoreversible crosslinking units. Comparison of experimental results and quantum calculations indicated that reaction kinetics and activation energy were much better prediction factors than change in enthalpy for the prediction of successful cycloaddition. Further testing on diene-dienophile pairs that underwent successful cycloaddition determined the feasibility of thermoreversibility/retro-reaction of each of the Diels-Alder compounds. Heating and testing of the compounds in the presence of a trapping agent allowed for experimental determination of reverse kinetics and activation energy for the retro-reaction. The experimental values were in good agreement with quantum calculations. The combination of chemical calculations with experimental results provided a strong insight into the structure-property relationships and how quantum calculations can be used to examine the feasibility of the thermoreversibility of new Diels-Alder complexes in potential polymer systems or to fine-tune thermoreversible Diels-Alder systems already in use.

Nickel nanoparticle-decorated reduced graphene oxide/WO3 nanocomposite - a promising candidate for gas sensing.

We report for the first time the combination of WO3 sensing elements with a non-noble metal-carbon composite, namely a nickel metal nanoparticle-carbon composite (Ni@rGO). Previous work with WO3 had used either NiO (as part of the WO3 lattice), solely carbon, Pd-surface decorated WO3 (Pd@WO3), or Pd or Pt@carbon@WO3. We demonstrate the gas response for pure WO3, rGO/WO3 and Ni@rGO/WO3 sensing elements towards NO2 and acetone in air as well as towards CO in N2. The addition of 0.35 wt % Ni@rGO composite to WO3 enables the increase of the sensory response by more than 1.6 times for NO2 vapors. The gas response towards acetone using 0.35 wt % Ni@rGO/WO3 composite was 1.5 times greater for 3500 ppm than for 35,000 ppm acetone. For 0.35 wt % Ni@rGO/WO3 composite and CO gas, a response time (T res) of 7 min and a recovery time (T rec) of 2 min was determined.

Pandemic-Driven Development of a Medical-Grade, Economic and Decentralized Applicable Polyolefin Filament for Additive Fused Filament Fabrication.

A polyolefin with certified biocompatibility according to USP class VI was used by our group as feedstock for filament-based 3D printing to meet the highest medical standards in order to print personal protective equipment for our university hospital during the ongoing pandemic. Besides the chemical resistance and durability, as well as the ability to withstand steam sterilization, this polypropylene (PP) copolymer is characterized by its high purity, as achieved by highly efficient and selective catalytic polymerization. As the PP copolymer is suited to be printed with all common printers in fused filament fabrication (FFF), it offers an eco-friendly cost-benefit ratio, even for large-scale production. In addition, a digital workflow was established focusing on common desktop FFF printers in the medical sector. It comprises the simulation-based optimization of personalized print objects, considering the inherent material properties such as warping tendency, through to validation of the process chain by 3D scanning, sterilization, and biocompatibility analysis of the printed part. This combination of digital data processing and 3D printing with a sustainable and medically certified material showed great promise in establishing decentralized additive manufacturing in everyday hospital life to meet peaks in demand, supply bottlenecks, and enhanced personalized patient treatment.

Synthesis of Tosyl- and Nosyl-Ended Polyisobutylenes with High Extent of Functionalities: The Effect of Reaction Conditions.

Endfunctional polymers possess significant industrial and scientific importance. Sulfonyl endgroups, such as tosyl and nosyl endfunctionalities, due their ease of substitution are highly desired for a variety of polymer structures. The sulfonylation of hydroxyl-terminated polyisobutylene (PIB-OH), a chemically and thermally stable, biocompatible, fully saturated polymer, with tosyl chloride (TsCl) and nosyl chloride (NsCl) is presented in this study. PIB-OHs derived from commercial exo-olefin-ended PIB (PIBexo-OH) and allyl-terminated polymer made via quasiliving carbocationic polymerization of isobutylene (PIBall-OH) were tosylated and nosylated in the presence of 4-dimethylaminopyridine (DMAP), pyridine and 1-methylimidazole (1-MI) catalysts and triethylamine (TEA). Our systematic investigations revealed that the end product distribution strongly depends on the relative amount of the components, especially that of TEA. While PIBexo-OTs with quantitative endfunctionality is readily formed from PIBexo-OH, its nosylation is not as straightforward. During sulfonylation of PIBall-OH, the formed tosyl and nosyl endgroups are easily substituted with chloride ions, formed in the first step of sulfonylation, leading to chloride termini. We found that decreased amounts of TEA afford the synthesis of PIBall-OTs and PIBall-ONs with higher than 90% endfunctionalities. These sulfonyl-ended PIBs open new ways for utilizing PIB in various fields and in the synthesis of novel PIB-containing macromolecular architectures.

Nanoconfined Crosslinked Poly(ionic liquid)s with Unprecedented Selective Swelling Properties Obtained by Alkylation in Nanophase-Separated Poly(1-vinylimidazole)-l-poly(tetrahydrofuran) Conetworks.

Despite the great interest in nanoconfined materials nowadays, nanocompartmentalized poly(ionic liquid)s (PILs) have been rarely investigated so far. Herein, we report on the successful alkylation of poly(1-vinylimidazole) with methyl iodide in bicontinuous nanophasic poly(1-vinylimidazole)-l-poly(tetrahydrofuran) (PVIm-l-PTHF) amphiphilic conetworks (APCNs) to obtain nanoconfined methylated PVImMe-l-PTHF poly(ionic liquid) conetworks (PIL-CNs). A high extent of alkylation (~95%) was achieved via a simple alkylation process with MeI at room temperature. This does not destroy the bicontinuous nanophasic morphology as proved by SAXS and AFM, and PIL-CNs with 15-20 nm d-spacing and poly(3-methyl-1-vinylimidazolium iodide) PIL nanophases with average domain sizes of 8.2-8.4 nm are formed. Unexpectedly, while the swelling capacity of the PIL-CN dramatically increases in aprotic polar solvents, such as DMF, NMP, and DMSO, reaching higher than 1000% superabsorbent swelling degrees, the equilibrium swelling degrees decrease in even highly polar protic (hydrophilic) solvents, like water and methanol. An unprecedented Gaussian-type relationship was found between the ratios of the swelling degrees versus the polarity index, indicating increased swelling for the nanoconfined PVImMe-l-PTHF PIL-CNs in solvents with a polarity index between ~6 and 9.5. In addition to the nanoconfined structural features, the unique selective superabsorbent swelling behavior of the PIL-CNs can also be utilized in various application fields.

Tailoring Hexagonal Gibbsite Single Crystal Nanoplatelets for Ethylene Polymerization and Nanocomposite Formation on MAO-Free Heterogeneous Bis(imino)pyridine Iron(II) Catalyst.

Ultrathin single crystal γ-Al(OH)3 (Gibbsite) nanoplatelets with average thickness <20 nm and length <800 nm, pretreated with trimethylaluminum (TMA), represent highly efficient activators and supports bis(imino)pyridine iron (II) (FeBIP) complex to produce high density polyethylene (HDPE) as well as gibbsite/HDPE nanocomposites in exceptionally high yields. Opposite to both methylaluminoxane (MAO)-activated homogeneous FeBIP catalyst and heterogenous silica-supported single site catalysts, no addition of MAO is required. At low TMA/Fe = 50 molar ratio, the superior catalyst activity (up to 6500 kg mol-1 h-1 bar-1 ) of FeBIP@TMA@Gibbsite is paralleled by controlled polyethylene particle growth without encountering reactor-fouling problems typical for homogeneous catalysts. TMA@Gibbsite is compared with other AlR3 @Gibbsite activators. The Al/Fe molar ratio governs catalyst activity as well as molar mass, molar mass distribution, and thermal properties of polyethylene. Moreover, hexagonal gibbsite nanoplatelets are uniformly dispersed in polyethylene to yield agglomerate-free polyethylene/gibbsite nanocomposites.

Tailoring Hydrocarbon Polymers and All-Hydrocarbon Composites for Circular Economy.

The world population will rapidly grow from 7 to 9 billion by 2050 and this will parallel a surging annual plastics consumption from today's 350 million tons to well beyond 1 billion tons. The switch from a linear economy with its throwaway culture to a circular economy with efficient reuse of waste plastics is therefore mandatory. Hydrocarbon polymers, accounting for more than half the world's plastics production, enable closed-loop recycling and effective product-stewardship systems. High-molar-mass hydrocarbons serve as highly versatile, cost-, resource-, eco- and energy-efficient, durable lightweight materials produced by solvent-free, environmentally benign catalytic olefin polymerization. Nanophase separation and alignment of unentangled hydrocarbon polymers afford 100% recyclable self-reinforcing all-hydrocarbon composites without requiring the addition of either alien fibers or hazardous nanoparticles. Recycling of durable hydrocarbons is far superior to biodegradation. The facile thermal degradation enables liquefaction and quantitative recovery of low molar mass hydrocarbon oil and gas. Teamed up with biomass-to-liquid and carbon dioxide-to-fuel conversions, powered by renewable energy, waste hydrocarbons serve as renewable hydrocarbon feedstocks for the synthesis of high molar mass hydrocarbon materials. Herein, an overview is given on how innovations in catalyst and process technology enable tailoring of advanced recyclable hydrocarbon materials meeting the needs of sustainable development and a circular economy.

Mechanochemically Carboxylated Multilayer Graphene for Carbon/ABS Composites with Improved Thermal Conductivity.

Dry ball milling of graphite under carbon dioxide pressure affords multilayer-functionalized graphene (MFG) with carboxylic groups as nanofiller for composites of carbon and acrylonitrile⁻butadiene⁻styrene copolymers (ABSs). Produced in a single-step process without requiring purification, MFG nanoplatelets are uniformly dispersed in ABS even in the absence of compatibilizers. As compared to few-layer graphene oxide, much larger amounts of MFG are tolerated in ABS melt processing. Unparalleled by other carbon nanofillers and non-functionalized micronized graphite, the addition of 15 wt % MFG simultaneously results in a Young's modulus of 2550 MPa (+68%), a thermal conductivity of 0.321 W∙m-1∙K-1 (+200%), and a heat distortion temperature of 99 °C (+9%) with respect to neat ABS, without encountering massive embrittlement and melt-viscosity build-up typical of few-layer graphene oxide. With carbon filler at 5 wt %, the Young's modulus increases with increasing aspect ratio of the carbon filler and is superior to spherical hydroxyl-functionalized MFG, which forms large agglomerates. Both MFG and micronized graphite hold promise for designing carbon/ABS compounds with improved thermal management in lightweight engineering applications.

Synthesis of metal-fluoride nanoparticles supported on thermally reduced graphite oxide.

Metal-fluoride nanoparticles, (MF x -NPs) with M = Fe, Co, Pr, Eu, supported on different types of thermally reduced graphite oxide (TRGO) were obtained by microwave-assisted thermal decomposition of transition-metal amidinates, (M{MeC[N(iPr)]2} n ) or [M(AMD) n ] with M = Fe(II), Co(II), Pr(III), and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)europium, Eu(dpm)3, in the presence of TRGO in the ionic liquid (IL) 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIm][BF4]). The crystalline phases of the metal fluorides synthesized in [BMIm][BF4] were identified by powder X-ray diffraction (PXRD) to be MF2 for M = Fe, Co and MF3 for M = Eu, Pr. The diameters and size distributions of MF x @TRGO were from (6 ± 2) to (102 ± 41) nm. Energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) were used for further characterization of the MF x -NPs. Electrochemical investigations of the FeF2-NPs@TRGO as cathode material for lithium-ion batteries were evaluated by galvanostatic charge/discharge profiles. The results indicate that the FeF2-NPs@TRGO as cathode material can present a specific capacity of 500 mAh/g at a current density of 50 mA/g, including a significant interfacial charge storage contribution. The obtained nanomaterials show a good rate capacity as well (220 mAh/g and 130 mAh/g) at a current density of 200 and 500 mA/g, respectively.

Polymers for 3D Printing and Customized Additive Manufacturing.

Additive manufacturing (AM) alias 3D printing translates computer-aided design (CAD) virtual 3D models into physical objects. By digital slicing of CAD, 3D scan, or tomography data, AM builds objects layer by layer without the need for molds or machining. AM enables decentralized fabrication of customized objects on demand by exploiting digital information storage and retrieval via the Internet. The ongoing transition from rapid prototyping to rapid manufacturing prompts new challenges for mechanical engineers and materials scientists alike. Because polymers are by far the most utilized class of materials for AM, this Review focuses on polymer processing and the development of polymers and advanced polymer systems specifically for AM. AM techniques covered include vat photopolymerization (stereolithography), powder bed fusion (SLS), material and binder jetting (inkjet and aerosol 3D printing), sheet lamination (LOM), extrusion (FDM, 3D dispensing, 3D fiber deposition, and 3D plotting), and 3D bioprinting. The range of polymers used in AM encompasses thermoplastics, thermosets, elastomers, hydrogels, functional polymers, polymer blends, composites, and biological systems. Aspects of polymer design, additives, and processing parameters as they relate to enhancing build speed and improving accuracy, functionality, surface finish, stability, mechanical properties, and porosity are addressed. Selected applications demonstrate how polymer-based AM is being exploited in lightweight engineering, architecture, food processing, optics, energy technology, dentistry, drug delivery, and personalized medicine. Unparalleled by metals and ceramics, polymer-based AM plays a key role in the emerging AM of advanced multifunctional and multimaterial systems including living biological systems as well as life-like synthetic systems.

Highly Efficient Multivalent 2D Nanosystems for Inhibition of Orthopoxvirus Particles.

Efficient inhibition of cell-pathogen interaction to prevent subsequent infection is an urgent but yet unsolved problem. In this study, the synthesis and functionalization of novel multivalent 2D carbon nanosystems as well as their antiviral efficacy in vitro are shown. For this reason, a new multivalent 2D flexible carbon architecture is developed in this study, functionalized with sulfated dendritic polyglycerol, to enable virus interaction. A simple "graft from" approach enhances the solubility of thermally reduced graphene oxide and provides a suitable 2D surface for multivalent ligand presentation. Polysulfation is used to mimic the heparan sulfate-containing surface of cells and to compete with this natural binding site of viruses. In correlation with the degree of sulfation and the grafted polymer density, the interaction efficiency of these systems can be varied. In here, orthopoxvirus strains are used as model viruses as they use heparan sulfate for cell entry as other viruses, e.g., herpes simplex virus, dengue virus, or cytomegalovirus. The characterization results of the newly designed graphene derivatives demonstrate excellent binding as well as efficient inhibition of orthopoxvirus infection. Overall, these new multivalent 2D polymer nanosystems are promising candidates to develop potent inhibitors for viruses, which possess a heparan sulfate-dependent cell entry mechanism.

Multivalency at Interfaces: Supramolecular Carbohydrate-Functionalized Graphene Derivatives for Bacterial Capture, Release, and Disinfection.

A supramolecular carbohydrate-functionalized two-dimensional (2D) surface was designed and synthesized by decorating thermally reduced graphene sheets with multivalent sugar ligands. The formation of host-guest inclusions on the carbon surface provides a versatile strategy, not only to increase the intrinsic water solubility of graphene-based materials, but more importantly to let the desired biofunctional binding groups bind to the surface. Combining the vital recognition role of carbohydrates and the unique 2D large flexible surface area of the graphene sheets, the addition of multivalent sugar ligands makes the resulting carbon material an excellent platform for selectively wrapping and agglutinating Escherichia coli (E. coli). By taking advantage of the responsive property of supramolecular interactions, the captured bacteria can then be partially released by adding a competitive guest. Compared to previously reported scaffolds, the unique thermal IR-absorption properties of graphene derivatives provide a facile method to kill the captured bacteria by IR-laser irradiation of the captured graphene-sugar-E. coli complex.

Molecular-weight-dependent changes in morphology of solution-grown polyethylene single crystals.

Polymer single crystals consisting of folded chains are always in a nonequilibrium state, even if they are faceted with a well-defined envelope reflecting the parameters of the crystal unit cell. Heterogeneities like small variations in the degree of chain folding within such crystals are responsible for a rather broad range in melting temperature. Consequently, upon annealing at a given temperature, some parts may be above and some below their respective melting temperatures, inducing a lamellar thickening process, which may vary locally. To emphasize such variations, controlled annealing experiments are performed at comparatively low temperatures and for long times. For single crystals of low-molecular-weight polyethylene, the formation of the well-known "Swiss-cheese"-like morphology with randomly distributed holes of varying sizes within the annealed single crystal is observed. However, for high-molecular-weight polyethylene, a regular pattern appeared upon annealing, characterized by branches of equal width that are oriented perpendicular to the crystal edge. All branches end at the nucleation site. Interestingly, the resulting pattern depends sensitively on both crystallization and annealing conditions. These thermally induced regular patterns within a single crystal are attributed to a stable crystalline framework formed within polyethylene single crystals in the course of growth.

Isocyanate- and phosgene-free routes to polyfunctional cyclic carbonates and green polyurethanes by fixation of carbon dioxide.

The catalytic chemical fixation of carbon dioxide by carbonation of oxiranes, oxetanes, and polyols represents a very versatile green chemistry route to environmentally benign di- and polyfunctional cyclic carbonates as intermediates for the formation of non-isocyanate poly-urethane (NIPU). Two synthetic pathways lead to NIPU thermoplastics and thermosets: i) polycondensation of diacarbamates or acyclic dicarbonates with diols or diamines, respectively, and ii) polyaddition by ring-opening polymerization of di- and polyfunctional cyclic carbonates with di- and polyamines. The absence of hazardous and highly moisture-sensitive isocyanates as intermediates eliminates the need for special safety precautions, drying and handling procedures. Incorporated into polymer backbones and side chains, carbonate groups enable facile tailoring of a great variety of urethane-functional polymers. As compared with conventional polyurethanes, ring-opening polymerization of polyfunctional cyclic carbonates affords polyhydroxyurethanes with unconventional architectures including NIPUs containing carbohydrate segments. NIPU/epoxy hybrid coatings can be applied on wet surfaces and exhibit improved adhesion, thermal stability and wear resistance. Combining chemical with biological carbon dioxide fixation affords 100% bio-based NIPUs derived from plant oils, terpenes, carbohydrates, and bio polyols. Biocompatible and biodegradable NIPU as well as NIPU biocomposites hold great promise for biomedical applications.