Surface Properties Of Polymers Research Articles

Non-Equilibrium Plasma Methods for Tailoring Surface Properties of Polyvinylidene Fluoride: Review and Challenges.

Modification and functionalization of polymer surface properties is desired in numerous applications, and a standard technique is a treatment with non-equilibrium gaseous plasma. Fluorinated polymers exhibit specific properties and are regarded as difficult to functionalize with polar functional groups. Plasma methods for functionalization of polyvinylidene fluoride (PVDF) are reviewed and different mechanisms involved in the surface modification are presented and explained by the interaction of various reactive species and far ultraviolet radiation. Most authors used argon plasma but reported various results. The discrepancy between the reported results is explained by peculiarities of the experimental systems and illustrated by three mechanisms. More versatile reaction mechanisms were reported by authors who used oxygen plasma for surface modification of PVDF, while plasma sustained in other gases was rarely used. The results reported by various authors are analyzed, and correlations are drawn where feasible. The processing parameters reported by different authors were the gas pressure and purity, the discharge configuration and power, while the surface finish was predominantly determined by X-ray photoelectron spectroscopy (XPS) and static water contact angle (WCA). A reasonably good correlation was found between the surface wettability as probed by WCA and the oxygen concentration as probed by XPS, but there is hardly any correlation between the discharge parameters and the wettability.

Experimental and Numerical Study of the Effect of Surface Patterning on the Frictional Properties of Polymer Surfaces

Abstract We describe benchmark experiments to evaluate the frictional properties of laser patterned low-density polyethylene as a function of sliding velocity, normal force, and humidity. The pattern is a square lattice of square cavities with sub-mm spacing. We find that dynamic friction decreases compared to nonpatterned surfaces, since stress concentrations lead to early detachment, and that stick-slip behavior is also affected. Friction increases with humidity, and the onset of stick-slip events occurs in the high humidity regime. Experimental results are compared with numerical simulations of a simplified 2D spring-block model. A good qualitative agreement can be obtained by introducing a deviation from the linear behavior of the Amontons-Coulomb law with the load due to a saturation in the effective contact area with pressure. This also leads to the improvement of the quantitative results of the spring-block model by reducing the discrepancy with the experimental results, indicating the robustness of the adopted simplified approach, which could be adopted to design patterned surfaces with controlled friction properties.

Cytocompatibility of Polymethyl Methacrylate Honeycomb-like Pattern on Perfluorinated Polymer.

In this study, we present a simple approach for developing a biocompatible polymer scaffold with a honeycomb-like micropattern. We aimed to combine a plasma treatment of fluorinated ethylene propylene (FEP) substrate with an improved phase separation technique. The plasma exposure served for modification of the polymer surface properties, such as roughness, surface chemistry, and wettability. The treated FEP substrate was applied for the growth of a honeycomb-like pattern from a solution of polymethyl methacrylate (PMMA). The properties of the pattern were strongly dependent on the conditions of plasma exposure of the FEP substrate. The physico-chemical properties of the prepared pattern, such as changes in wettability, aging, morphology, and surface chemistry, were determined. Further, we have examined the cellular response of human osteoblasts (U-2 OS) on the modified substrates. The micropattern prepared with a selected combination of surface activation and amount of PMMA for honeycomb construction showed a positive effect on U-2 OS cell adhesion and proliferation. Samples with higher PMMA content (3 and 4 g) formed more periodic hexagonal structures on the surface compared to its lower amount (1 and 2 g), which led to a significant increase in the pattern cytocompatibility compared to pristine or plasma-treated FEP.

Effect of Cold Plasma Treatment of Polymer Fibers on the Mechanical Behavior of Fiber-Reinforced Cementitious Composites

Fiber-reinforced cementitious composites (FRCC) are a class of materials made by adding randomly distributed fibers to a cementitious matrix, providing better material toughness through the crack bridging behavior of the fibers. One of the primary concerns with FRCCs is the behavior of the fiber when a crack is formed. The fibers provide a stress-bridging mechanism, which is largely determined by the bond that exists between the concrete and the fiber’s outer surface. While many studies have determined the properties of FRCCs and potential benefits of using specific fiber types, the effects of low temperature or cold plasma treatment of polymer fibers on the mechanical behavior of the composite material are limited. Polymer fibers are notable for their low density, ductility, ease of manufacture, and cost-effectiveness. Despite these advantages, the surface properties of polymers do not enable the bonding potential given by steel or glass fibers when used in untreated FRCC, resulting in pull-out failures before the full displacement capacity of the fiber is utilized. For this reason, modification of the surface characteristics of polymer fibers can aid in higher bonding potential. Plasma treatment is a process wherein surfaces are modified through the kinetics of electrically charged and reactive species in a gaseous discharge environment. This paper is a preliminary study on the use of atmospheric pressure plasma generated at approximately room temperature. This atmospheric, cold plasma treatment is a method for improving the mechanical properties of FRCC using polymeric fibers. In this study, polypropylene and polyvinyl-alcohol fibers were cold plasma treated for 0, 30, 60, and 120 s before being used in cementitious mortar mixtures. Compression and flexure tests were performed using a displacement-based loading protocol to examine the impact of plasma treatment time on the corresponding mechanical performance of the fiber-reinforced cementitious composite. The experimental results obtained from this study indicate that there is a positive correlation between fiber treatment time and post-peak load-carrying capacity, especially for specimens subjected to flexural loading.

Strength and Surface Properties of a 3D-Printed Denture Base Polymer.

This in vitro study evaluated the flexural strength, impact strength, hardness, and surface roughness of 3D-printed denture base resin subjected to thermal cycling treatment. According to ISO 20795-1:2013 standards, 120 acrylic resin specimens (40/flexural strength test, 40/impact strength, and 40/surface roughness and hardness test, n = 10) were fabricated and distributed into two groups: heat-polymerized; (Major.Base.20) as control and 3D-printed (NextDent) as experimental group. Half of the specimens of each group were subjected to 10,000 thermal cycles of 5 to 55°C simulating 1 year of clinical use. Flexural strength (MPa), impact strength (KJ/m2 ), hardness (VHN), and surface roughness (μm) were measured using universal testing machine, Charpy's impact tester, Vickers hardness tester, and profilometer, respectively. Data were analyzed by ANOVA and Tukey honestly significant difference (HSD) test (α = 0.05). The values of flexural strength (MPa) were 86.63 ± 1.0 and 69.15 ± 0.88; impact strength (KJ/m2 )-6.32 ± 0.50 and 2.44 ± 0.31; hardness (VHN)-41.63 ± 2.03 and 34.62 ± 2.1; and surface roughness (μm)-0.18 ± 0.01 and 0.12 ± 0.02 for heat-polymerized and 3D-printed denture base materials, respectively. Significant differences in all tested properties were recorded between heat-polymerized and 3D-printed denture base materials (P < 0.001). Thermal cycling significantly lowered the flexural strength (63.93 ± 1.54 MPa), impact strength (2.40 ± 0.35 KJ/m2 ), and hardness (30.17 ± 1.38 VHN) of 3D-printed resin in comparison to thermal cycled heat-polymerized resin, but surface roughness showed non-significant difference (p = 0.262). 3D-printed resin had inferior flexural strength, impact strength, and hardness values than heat-polymerized resin, but showed superior surface roughness. Temperature changes (thermal cycling) significantly reduced the hardness and flexural strength and increased surface roughness, but did not affect the impact strength.

Biodistribution of 68/67Ga-Radiolabeled Sphingolipid Nanoemulsions by PET and SPECT Imaging.

Background and PurposeNon-invasive imaging methodologies, especially nuclear imaging techniques, have undergone an extraordinary development over the last years. Interest in the development of innovative tracers has prompted the emergence of new nanomaterials with a focus on nuclear imaging and therapeutical applications. Among others, organic nanoparticles are of the highest interest due to their translational potential related to their biocompatibility and biodegradability. Our group has developed a promising new type of biocompatible nanomaterials, sphingomyelin nanoemulsions (SNs). The aim of this study is to explore the potential of SNs for nuclear imaging applications.MethodsReady-to-label SNs were prepared by a one-step method using lipid derivative chelators and characterized in terms of their physicochemical properties. Stability was assessed under storage and after incubation with human serum. Chelator-functionalized SNs were radiolabeled with 67Ga and 68Ga, and the radiochemical yield (RCY), radiochemical purity (RCP) and radiochemical stability (RCS) were determined. Finally, the biodistribution of 67/68Ga-SNs was evaluated in vivo and ex vivo.ResultsHere, we describe a simple and mild one-step method for fast and efficient radiolabeling of SNs with 68Ga and 67Ga radioisotopes. In vivo experiments showed that 67/68Ga-SNs can efficiently and indistinctly be followed up by PET and SPECT. Additionally, we proved that the biodistribution of the 67/68Ga-SNs can be conveniently modulated by modifying the surface properties of different hydrophilic polymers, and therefore the formulation can be further adapted to the specific requirements of different biomedical applications.ConclusionThis work supports 67/68Ga-SNs as a novel probe for nuclear imaging with tunable biodistribution and with great potential for the future development of nanotheranostics.

Effect of molecular weight and architecture on nanoscale viscoelastic heterogeneity at the surface of polymer films

Dissipated energy mapping in amplitude-modulation atomic force microscopy was employed to characterize the nanoscale heterogeneous behavior of the viscoelastic response at the surface of polystyrene (PS) films of different molecular weight and architecture. By using an ultra-sharp probe with tip radius of ~1 nm, we were able to visualize the viscoelastic heterogeneities at the free surface of all PS samples. While the length scale of these heterogeneities at the surface of linear PS films was measured to be ~2.2 nm nearly independent of the molecular weight, it was significantly increased to ~3.1 nm at the surface of four-arm star-shaped PS films. We also demonstrated that similar nanoscale heterogeneous features were not observed when using a common probe with tip radius of ~10 nm, thereby confirming the intrinsic nature of the observed viscoelastic heterogeneities with sizes on the order of a few nanometers at the surface of PS films. This result provides important insights into the fundamental role of the molecular architecture in controlling the heterogeneous dynamics and many associated physical properties of amorphous polymer surfaces.

Utilizing Radio Frequency Plasma Treatment to Modify Polymeric Materials for Biomedical Applications.

Studies that utilize radio frequency plasma modification as a strategy to tune the surface properties of polymeric constructs with the goal of enhancing their use as biomedical devices have grown considerably in number over the past decade. In this Review, we present the importance of plasma surface treatment to biomedical applications, including tissue engineering and wound healing. First, we introduce several key polymeric materials of interest for use as biomaterials, including those that are naturally derived and synthetic. We, then, provide an overview of possible outcomes of plasma modification, such as surface activation, etching, and deposition of a thin film, all of which can be used to alter the surface properties of a given polymer. Following this discussion, we review the methods used to characterize plasma-treated polymer surface properties, as well as the techniques used to evaluate their interactions with biological species of interest such as mammalian cells, bacteria, and blood components. To close, we provide a perspective on future outlooks of this exciting and rapidly evolving field.

Superficial Surface Treatment using Atmospheric Plasma on Recycled Nylon 6,6

Polymers currently represent materials that are cost-effective, while its recycled nature is significant in terms of environmental protection. However, the surface properties of polymers often do not meet the demands of wettability, adhesion, and friction, among others. Atmospheric plasma treatment on the surface of polymers improves its physical-chemistry properties. In this work, a recycled nylon coating was prepared by the spin coating technique and characterized by Fourier transform infrared spectroscopy and X-ray diffraction. This coating was treated by atmospheric plasma, and Raman spectroscopy was performed to analyze the signals related to different functional groups present in the coating surface after plasma treatment. The action of plasma on the surface morphology was observed by scanning electron microscopy. The contact angle results showed an improvement in surface wettability.

Heads or tails: Nanostructure and molecular orientations in organised erucamide surface layers

HypothesisDespite the widespread industrial usage of erucamide as a slip additive to modify polymer surface properties, a controversy appears to have persisted regarding the nanostructure of erucamide surface layers, particularly the molecular orientation at the outermost layer. The erucamide nanostructure and molecular orientation, along with its surface coverage, hydrophobicity, and adhesive response, can be tuned by simply varying the erucamide concentration in the solution from which the spin coated layer is prepared. ExperimentsSynchrotron X-ray reflectivity (XRR) allowed a comprehensive characterisation of the out-of-plane structural parameters (e.g. molecular packing and thickness) of the erucamide layers prepared via spin coating from nonaqueous solution on silica. Complementary Atomic Force Microscopy (AFM) imaging with high lateral resolution revealed localised in-plane structures. Contact angle measurements provided information on the wettability of erucamide-coated surfaces. Peak Force Quantitative Nanomechanical Mapping (QNM) allowed a correlation between the erucamide nanostructure with the surface nanomechanical properties (i.e. adhesive response). FindingsOur results reveal erucamide surface nanostructures on silica as patchy monolayers, isolated circular bilayers/rounded rectangle-like aggregates and overlapping plate-like multilayers as the erucamide concentration in the spin coating solution was varied. In all the cases, XRR and AFM results were consistent with the picture that the erucamide tails were oriented outwards. The QNM adhesion force mapping of all the observed morphologies also supported this molecular orientation at the outermost erucamide monolayer. The wettability study further confirmed this conclusion with the observed increase in the surface hydrophobicity and coverage upon increasing erucamide concentration, with the macroscopic water contact angle θ = 92.9° ± 2.9° at the highest erucamide concentration of 2 wt%.

Surface characterization of plasma-modified low density polyethylene by attenuated total reflectance fourier-transform infrared (ATR-FTIR) spectroscopy combined with chemometrics

Atomic layer deposition (ALD) on polymer substrates often requires a modification of the polymer surface properties. Plasma-enhanced ALD (PE-ALD) process is capable of establishing improved coating/substrate adhesion and layer properties by a plasma pre-treatment prior to the layer deposition. Low density polyethylene (LDPE) films were plasma treated using different gases (N2, O2, and N2+O2 mixture) for various exposure times. A novel method was proposed to reveal the chemical changes in the surface region of LDPE films with attenuated total reflectance Fourier-transform infrared (ATR-FTIR) spectroscopy combined with multivariate analysis. The loading plots of principal component analysis (PCA) revealed the formation of polar functional groups on the surface of LDPE films, as a result of plasma pre-treatment. PCA was also able to explore the differences and similarities in the chemical modifications of LDPE originated from different plasma gas and exposure time.

Surface Modification With Gelatin For Polyurethane Vascular Grafts: A Review

The means for developing synthetic vascular grafts to replace blood vessels is increasing extensively because of the limited supply of autologous vessels. Synthetic polymers as the alternatives still suffer from restenosis and thrombus formation. Natural polymers, on the other hand, are commonly biocompatible and biodegradable, compliment the synthetic ones. Blending, grafting and coating of natural polymers have been proposed to improve surface properties of synthetic polymers. Gelatin is a promising candidate to help improving synthetic vascular grafts surface owing to its ability to promote cell adhesion without promoting platelet aggregation at its surface. In this review, several techniques to incorporate gelatin onto synthetic polymers, mainly polyurethane, for vascular grafts application are summarized, together with the recent updates and potential development in the future.

The Evaluation of the Hemocompatibility of Polymer Membrane Materials for Blood Oxygenation

A comprehensive interdisciplinary study is performed for 12 polymers promising for the fabrication of membranes for extracorporeal membrane oxygenation based on them by methods of gas permeability, wetting, piezoelectric microweighing, and direct biomedical methods for determining hemocompatibility of whole blood from healthy donors. It is found that trimethylsilyl-substituted polytricyclononene, polyhexafluoropropylene, and semicrystalline polyphenylene oxide are the best polymer materials for the diffusion membranes of oxygenators. It is shown that traditional approaches that associate the surface properties of polymers (water wettability, plasma protein adsorption, energy characteristics of surfaces) with their hemocompatibility do not provide precise correlations with the biomedical methods based on the analysis of the changes in the shape of blood cells as a result of adhesion on the surface of the polymer. The complexity of the mechanism of interaction of the surface of polymers with blood also does not allow for clear structure–property correlations traditional for membrane gas separation. The directions of further research in this area are defined.

Influence of synthetic wastewater on entrapped air on the isotactic and atactic polypropylene microplastic surfaces.

The municipal wastewater collection system is recognized as an initial point of interaction between microplastics (MPs) and the urban wastewater matrix. The raw wastewater contains a wide variety of organic and inorganic substances including chemicals and heavy metals. However, the fate of MPs in urban sewer systems is not yet well understood. In this work two types of virgin polypropylene (PP) samples, isotactic (iPP) and atactic (aPP), were exposed to two synthetic wastewater solutions in order to study their effects on the physical properties of the hydrophobic polymer surfaces. Particular attention was paid to the pollution adhesion at the air-liquid-solid interfaces of the surface air pockets entrapped on the polymer surfaces. The first wastewater solution consists of mixed fat, oil and grease (FOG) - surfactant and another which is an exclusively contained wastewater surfactant. The interaction experiment over a period of 10min between the polymer's air pocket and solutions indicated that the size of the bubble in the mixed FOG-surfactant solution increased more pronouncedly for iPP (%152) in contrast to aPP (%31) and was also compared with the greater surface roughness of the polymers. The size variation of the spherical cap on the immersed polymer surfaces were measured between 17µm and 85µm using image processing techniques while the data was analyzed by the Young-Laplace equation. The corresponding technical surface roughness of the polymers, the surface tension of the liquids and their air/water contact angle on the flat polymer surfaces were also measured. The results of this study indicated that surface air pockets influence the adsorption capacity of MPs and thus their buoyancy and contamination potential.

Friction at nanopillared polymer surfaces beyond Amontons’ laws: Stick-slip amplitude coefficient (SSAC) and multiparametric nanotribological properties

Frictional and nanomechanical properties of nanostructured polymer surfaces are important to their technological and biomedical applications. In this work, poly(ethylene terephthalate) (PET) surfaces with a periodic distribution of well-defined nanopillars were fabricated through an anodization/embossing process. The apparent surface energy of the nanopillared surfaces was evaluated using the Fowkes acid-base approach, and the surface morphology was characterized using scanning electron microscope (SEM) and atomic force microscope (AFM). The normal and lateral forces between a silica microparticle and these surfaces were quantified using colloidal probe atomic force microscopy (CP-AFM). The friction-load relationship followed Amonton’s first law, and the friction coefficient appeared to scale linearly with the nanopillar height. Furthermore, all the nanopillared surfaces showed pronounced frictional instabilities compared to the smooth sliding friction loop on the flat control. Performing the stick–slip amplitude coefficient (SSAC) analysis, we found a correlation between the frictional instabilities and the nanopillars density, pull-off force and work of adhesion. We have summarised the dependence of the nanotribological properties on such nanopillared surfaces on five relevant parameters, i.e. pull-off force fp, Amontons’ friction coefficient μ, RMS roughness Rq, stick–slip amplitude friction coefficient SSAC, and work of adhesion between the substrate and water Wadh in a radar chart. Whilst demonstrating the complexity of the frictional behaviour of nanopillared polymer surfaces, our results show that analyses of multiparametric nanotribological properties of nanostructured surfaces should go beyond classic Amontons’ laws, with the SSAC more representative of the frictional properties compared to the friction coefficient.

Argon gas cluster fragmentation and scattering as a probe of the surface physics of thermoset polymers

Surface and thin films are important in modern technologies and there is growing demand for their characterization. Secondary ion mass spectrometry (SIMS) is universally used for extracting information on the chemical composition of surfaces. This study shows that it can provide information about the physical (mechanical) properties of thermoset polymer surfaces. The intensities of backscattered Arn+ clusters were measured upon 10 keV Ar3000+ gas cluster ion bombardment of polymer films. Tyrosol diaminodiphenylmethane based benzoxazine thermosets with different curing cycles were used. The intensity ratios Ar2+/(Ar2++Ar3+) and Ar2+/(Ar2++Ar4+) were highly sensitive to the physical changes of the thermoset coating surfaces as a function of their curing cycle and of temperature. These intensity ratios provide direct access to the surface transition temperature TT (related to the bulk glass transition Tg), and show a dependence on the curing degree below and above TT. Moreover, we discuss the influence of surface contamination and clusters induced roughness on the measured values. Our results suggest that contamination has a dramatic influence on the intensity of backscattered Arn+ clusters, while that of roughness appears to be minor. This study constitutes a step forward towards a quantitative assessment of the mechanical properties of polymer coating surfaces using SIMS.

Migration Effects of Fluorochemical Melt Additives for Alcohol Repellency in Polypropylene Nonwoven Materials.

The use of bulk polymer melt additives provides a facile, industrially relevant approach to tailor properties of polymer surfaces for many different applications. These melt additives, when blended with polymers prior to melt spinning, migrate to the fiber surface and influence surface functionality. While the use of bulk polymer melt additives to impart hydrophilicity or oleophobicity is well studied, the impact of the fiber formation process on additive migration and resultant repellency of nonwoven media products remains largely unexplored. In this study, we produce fluorochemical melt additive containing meltblown nonwovens, and establish methods for characterization of fiber mat surface composition and repellency. Repellency of low surface tension fluids is a significant challenge and is of particular importance in the creation of medical garments such as surgical gowns and masks which must perform as liquid barriers even when exposed to alcohol based solutions. Similarly, melt additives are also used in the production of electret air filtration devices. Electret filters are imbued with charges to enhance particle capture performance, but this charge can be negated through wetting by low surface tension fluids. To address this challenge, the changing composition of fiber surfaces due to the migration of additives is monitored via X-ray Photoelectron Spectroscopy, then related to repellency of alcohol solutions by contact angle analysis. We demonstrate that for the samples tested a fluorine to carbon (F/C) ratio of 0.35 is sufficient to prevent wicking of isopropanol droplets, and higher surface tension fluids could be repelled by fiber mats with lower fluorine content. Through the use of cross-sectional ToF-SIMS analysis, we find that migration of additives is key to the performance of samples with low additive loadings, and that these phenomena are heavily influenced by many nonwoven manufacturing parameters including fiber size, die-to-collector distance, and polymer resin melt flow rates.

Atmospheric-pressure plasma assisted engineering of polymer surfaces: From high hydrophobicity to superhydrophilicity

To engineer polymer surfaces with long-lasting wettability properties and with high coating stability in aqueous media, we investigated the surface wettability of polyethylene terephthalate (PET) films treated by radio frequency (RF) atmospheric-pressure plasma. By combining plasma activation and hexamethyldisiloxane (HMDSO)-based plasma polymerization, stable PET surface properties from highly hydrophobic to superhydrophilic were achieved. The results clearly showed that the wettability of PET surfaces could be tuned from stable high hydrophobicity (>140°) to stable superhydrophilicity (<10°) with a minimized aging effect by using plasma activation of plasma deposited coatings. Surface roughness increase and CH3 groups introduction are primarily responsible for the coating hydrophobization, while the introduction of more oxygen-containing polar functional groups is the main factor leading to superhydrophilization. Importantly, the coatings engineered by this unique combination showed high stability in water over 14 days. Overall, this work contributes to the easy-to-overlook links between plasma activation and plasma polymerization, demonstrates that atmospheric-pressure RF plasma can be a versatile tool to control surface properties of polymers in a wide range from high hydrophobicity to superhydrophilicity with high coating stability in aqueous media and a negligible aging effect, which is promising for emerging biomedical applications.

Effect of plasma treatment on some surface properties of acrylic resin polymer

Background: Polymer surfaces usually present problems in bonding and finishing due to their low hydrophilicity. The aim of this study is to investigate the effect of plasma treatment with the use of two types of gases (oxygen and argon) on surface roughness, and chemical surface properties of acrylic resin denture base polymer material. Materials and Methods: Three heat cured acrylic resin specimens of (2*8*30 mm) dimensions were prepared for each test carried out in this study. Two tests were conducted, surface roughness test and chemical surface analysis test. Results: Application of plasma treatment increased surface roughness for both oxygen and argon plasma treated acrylic resin specimen groups compared with control untreated group, with a highly significant difference (P &lt;0.01) among groups. FTIR chemical analysis for oxygen plasma treated acrylic resin specimen group showed a spectrum with a broad peak, which represents the hydroxyl group (-OH). This was an important chemical change that increased the hydrophilicity as compared with FTIR spectrums of control and argon plasma treated acrylic resin groups which exhibited relatively the same peaks with mild chemical changes. Conclusion: Application of oxygen and argon plasma treatment represents an effective surface treatment method for increasing the surface roughness of acrylic resin denture base polymer material. Oxygen plasma treatment can activate the treated surface towards further chemical reactions, and increase the hydrophilicity of the acrylic resin denture base polymer material. Key words: Acrylic resin polymer, plasma treatment, surface roughness, FTIR analysis.

Early Transition Metal Catalysis for Olefin-Polar Monomer Copolymerization.

Introducing polar functional groups into widely used polyolefins can enhance polymer surface, rheological, mixing, and other properties, potentially upgrading polyolefins for advanced, value-added applications. The metal catalyst-mediated copolymerization of non-polar olefins with polar comonomers represents the seemingly most straightforward, atom- and energy-efficient approach for synthesizing polar functionalized polyolefins. However, electrophilic early transition metal (groups 3 and 4)-catalyzed processes which have achieved remarkable success in conventional olefin polymerizations, encounter severe limitations here, largely associated with the Lewis basicity of the polar co-monomers. In recent years, however, new catalytic systems have been developed and successful strategies have emerged. In this Minireview, we summarize the recent progress in early transition metal polymerization catalyst development, categorized by the catalytic metal complex and polar comonomer identity. Furthermore, we discuss advances in the mechanistic understanding of these polymerizations, focusing on critical challenges and strategies that mitigate them.