High Glass Transition Temperature Fluorinated Polymers Based on Transfer Learning with Small Experimental Data.

Machine learning can be used to predict the properties of polymers and explore vast chemical spaces. However, the limited number of available experimental datasets hinders the enhancement of the predictive performance of a model. This study proposes a machine learning approach that leverages transfer learning and ensemble modeling to efficiently predict the glass transition temperature (Tg) of fluorinated polymers and guide the design of high Tg copolymers. Initially, the quantum machine 9 (QM9) dataset is employed for model pretraining, thus providing robust molecular representations for the subsequent fine-tuning of a specialized copolymer dataset. Ensemble modeling is used to further enhance prediction robustness and reliability, effectively addressing the problems owing to the limited and unevenly distributed nature of the copolymer dataset. Finally, a fine-tuned ensemble model is used to navigate a vast chemical space comprising 61 monomers and identify promising candidates for high Tg fluorinated polymers. The model predicts 247 entries capable of achieving a Tg over 390 K, of which 14 are experimentally validated. This study demonstrates the potential of machine learning in material design and discovery, highlighting the effectiveness of transfer learning and ensemble modeling strategies for overcoming the challenges posed by small datasets in complex copolymer systems.

Fluorinated Titania Nanoparticle-Induced Piezoelectric Phase Transition of Poly(vinylidene fluoride).

We prepared F-coated rutile titanium dioxide nanoparticles (r-TiO2 NPs) via simple thermal annealing of titania NPs in poly(vinylidene fluoride) (PVDF) and demonstrated that the F-coated r-TiO2 NP-doped composite film could efficiently induce piezoelectric phase transition of non-electroactive PVDF due to highly electronegative F bonds on the surface of these NPs. In the case of a 2.0 wt % composite film, 99.20% of the non-electroactive PVDF was transformed into the electroactive phase. Additionally, utilizing the F-coated r-TiO2 NPs for a piezoelectric device led to an enhancement of the piezoelectric performance. With the 5.0 wt % composite film, the resulting piezoelectric device exhibited voltage generation of 355 mV, whereas a device with the innate r-TiO2 NPs exhibited voltage generation of only 137 mV. Furthermore, because of optical inactivity of F-coated r-TiO2 NPs, the piezoelectric films exhibited high stability under 64 h of photoirradiation at an intensity of 0.1 W/cm2. These results indicate that the F-coated r-TiO2 NP-doped composite films could be useful for various applications, including outdoor energy-harvesting, self-powered wearable devices, and portable sensors.

Controllable Surface and Optical Properties of Methacrylic Copolymer Films Using Various Monomer Combinations.

Various fluorinated methacrylic copolymers (PFPMA- X) were prepared from 2,2,3,3,3-pentafluoropropyl methacrylate (PFPMA), methyl methacrylate (MMA), and three other nonfluorinated monomers. The surface and the optical properties of these copolymers were controlled by changing the ratio of PFPMA to MMA while keeping the sum of the concentration of the two monomers fixed at 60 wt %. The parameter X represents the nominal concentration of PFPMA in various feed ratios of all five monomers. Depending on the increase in PFPMA content in PFPMA- X, the surface energy varied proportionately between 26.7 (PFPMA content: 20 wt %) and 17.4 mN/m (PFPMA content: 60 wt %), which is well-correlated with the fluorine content on the surface. Interestingly, we found that all PFPMA- X-coated glasses showed different transmittance curves in the wavelength range of 300-700 nm, and the wavelength at which maximum transmittance was recorded shifted as a function of the copolymer composition. In addition, the surface coatings of PFPMA- X with higher fluorine contents increased the transmittance of bare glass by approximately 1-2%. Quite lower and tunable refractive indices were obtained depending on the fluorine content, and all PFPMA- X showed extremely lower birefringences. Freestanding films of PFPMA- X were also well-formed, indicating that they can be used in a wide range of applications.

Tuning Surface Properties of Poly(methyl methacrylate) Film Using Poly(perfluoromethyl methacrylate)s with Short Perfluorinated Side Chains.

To control the surface properties of a commonly used polymer, poly(methyl methacrylate) (PMMA), poly(perfluoromethyl methacrylate)s (PFMMAs) with short perfluorinated side groups (i.e., -CF3, -CF2CF3, -(CF3)2, -CF2CF2CF3) were used as blend components because of their good solubility in organic solvents, low surface energies, and high optical transmittance. The surface energies of the blend films of PFMMA with the -CF3 group and PMMA increased continuously with increasing PMMA contents from 17.6 to 26.0 mN/m, whereas those of the other polymer blend films remained at very low levels (10.2-12.6 mN/m), similar to those of pure PFMMAs, even when the blends contained 90 wt %PMMA. Surface morphology and composition measurements revealed that this result originated from the different blend structures, such as lateral and vertical phase separations. We expect that these PFMMAs will be useful in widening the applicable window of PMMA.

Collapse of homeotropic liquid-crystal alignment by increased molecular packing on comb-like polymer surfaces.

We report an unusual alignment behavior of liquid crystals (LCs) on well-ordered comb-like poly(oxyethylene) surfaces. The homeotropic LC alignments that are observed on as-coated surfaces of the polymers are transformed to the random planar type after annealing treatment, even though the molecular structure of the polymer surface becomes more ordered and the surface energy decreases. Studies of the surface properties, such as molecular structure, morphology, and wettability, reveal that such an unexpected alteration of the LC alignment originates from the density of the alkyl side chains being enhanced by localized packing.

Flexible, Elastic, and Superhydrophobic/Superoleophilic Adhesive for Reusable and Durable Water/Oil Separation Coating.

This study investigates a highly flexible/stretchable and mechanically durable superhydrophobic/superoleophilic coating for efficient oil/water separation and oil absorption. The coating is applied via a simple immersion process using a mixed solution of a biocompatible adhesive (ethyl cyanoacrylate, ECA), a highly stretchable polymer (polycaprolactone, PCL), and superhydrophobic/superoleophilic nanoparticles (fluorine-coated silica nanoparticles, F-SiO2 NPs) in a solvent, followed by solvent evaporation and ECA polymerization. Polymerized ECA (poly-ECA) in the coating material strongly adheres the F-SiO2 NPs to the substrate surface, while PCL bestows the rigid poly-ECA with high flexibility. A coated polyurethane sponge exhibits superhydrophobicity (water contact angle of >150°), while retaining robust mechanical stability and flexibility/elasticity. This provides an efficient means of cleaning oil spills with high selectivity, even after mechanical abrasion (>99% separation efficiency is retained after 120 tape test cycles and 50 rubbing test cycles), with excellent reusability.

Effect of n-alkyl and sulfonyl groups on the wetting properties of comblike poly(oxyethylene)s and stick-slip behavior.

The influence of side chain length and sulfonyl moiety on the molecular structures and wettability behavior of poly(oxyethylene)s with alkyl sulfonyl side chains (CH(3)-nSE, n = 1, 2, 3, 4, 5, 6, 8, 10), where n is the number of the carbon atom in the n-alkyl side group, was investigated. CH(3)-nSEs having shorter side chains (n < 5) do not have ordered structures, and their surfaces were found to be more polar than those of CH(3)-nSEs having longer side chains (n ≥ 5). The CH(3)-nSEs having longer side chains show double-layered lamellar structures (n ≥ 5) with well-aligned side chains and low surface energies in the range 21.2-25.8 mN/m. Interestingly, stick-slip behavior was observed only on the surfaces of CH(3)-3SE and CH(3)-4SE when water was used as the test liquid. The surface deformation at the three-phase line was generated from interactions between water and sulfonyl groups, and the optimum side chain lengths were believed to cause the stick-slip behavior.

A strategy for preparing controllable, superhydrophobic, strongly sticky surfaces using SiO2@PVDF raspberry core-shell particles.

In nature, wetting by water droplets on superhydrophobic materials is governed by the Cassie-Baxter or Wenzel models. Moreover, sticky properties, derived from these types of wettings, are required for a wide range of applications involving superhydrophobic materials. As a facile new strategy, a method employing a gaseous fluorine precursor to fabricate core-shell particles, comprising perfectly shaped fluorine shells with adjustable adhesive strength, is described in this paper. Silica was used as the hydrophilic core, while polyvinylidene fluoride (PVDF) was used for the hydrophobic shell coating, forming a raspberry-like shape. In addition, controlling the amount of PVDF coated on the silica surface enabled the water droplets to come into contact with both the PVDF of the shell and the silica of the core, thereby controlling both the superhydrophobicity and the adhesive strength. Thus, the synthesized particles formed a structured coating with controllable stickiness and contact angles of 131-165°. Furthermore, on surfaces with high adhesivity, the water droplets remained stable at tilt angles of 90° and 180° even under a strong centrifugal force, whereas on surfaces with low adhesivity, the water droplets slid off when the substrate was tilted at 4°.

Perfluoropolyether-benzophenone as a highly durable, broadband anti-reflection, and anti-contamination coating.

Anti-reflection and anti-contamination coatings prepared from fluorinated polymers have widespread and important applications, ranging from protective films for corrosion resistance to high-tech microelectronics and medical devices due to their transparency, low refractive index, stain resistance, and antifouling properties. However, the application of existing coatings is hindered by low surface adhesion to the target substrate and weakness when exposed to mechanical stress or damage, resulting in significant limitations to their practical applications. Herein, we incorporate perfluoropolyether (PFPE) with benzophenone (BP) to develop an efficient coating material (PFPE-BP) possessing broadband anti-reflectivity, anti-contamination properties, excellent abrasion resistance, and stability under elevated temperatures and relative humidity. The presence of BP allows the coating materials to be homogeneously mixed with a commercial hard coating solution to uniformly coat the target substrate. Furthermore, UV light irradiation on the coating surface results in excellent adhesion between BP groups of PFPE-BP and the hard coating matrix.

Preparation and electroactive phase adjustment of Ag-doped poly(vinylidene fluoride) (PVDF) films.

The crystallinities of Ag-doped poly(vinylidene fluoride) (PVDF) films were modified by removing Ag+ using a novel washing process, which allowed control of the ratio of γ- and ß-phases. The polarity of the composite film without Ag+ removal through the washing process reached 98%, and the ß-phase content in the total electroactive phase was increased to 61%, according to Fourier-transform infrared spectroscopy. When Ag+ were removed through a process involving several cycles of washing, filtering, drying, and re-dissolving, the highest ratio of the γ-phase was increased to 67%, 28% higher than that before washing. This showed that Ag+ induced ß-phase formation while Ag nanoparticles induced γ-phase formation, and that the ratio of γ- and ß-phases in PVDF composite films can be controlled to suit specific applications by this washing process.

Ultra-hydrophobic sticky polymer surfaces formed by water-induced surface deformation.

Surface properties of poly(oxyethylene)s with alkyl thioether side chains (CH3-nTE; n=carbon atoms in the side chain) were investigated. CH3-nTEs having shorter side chains (n=6, 8, 10) did not have ordered structures, while those with longer chains (n=12, 14) showed well-ordered, lamellar structures with side chain crystalline domains. Accordingly, CH3-12TE and CH3-14TE film surfaces were much more enriched with hydrophobic alkyl side chains than CH3-8TE and CH3-10TE surfaces. However, CH3-12TE and CH3-14TE films had smaller water contact angles (≈114°) than CH3-8TE and CH3-10TE films (>130°). This unexpected behavior is ascribed to the formation of very rough CH3-8TE and CH3-10TE film surfaces (Rrms>100nm) on contact with water. The CH3-10TE/poly(methyl methacrylate) (PMMA) surfaces also showed high water contact angles (>125°), even with low CH3-10TE content (30wt%), because the CH3-10TE moiety roughened the surfaces. Furthermore, ultra-hydrophobic sticky behavior was observed for CH3-nTEs (n=8, 10) and CH3-10TE/PMMA surfaces.

Improved field-effect transistor performance of a benzotrithiophene polymer through ketal cleavage in the solid state.

A benzotrithiophene polymer with a new thermally cleavable ketal substituent is reported. It is shown how this functional group can be used to facilitate solvent processing and, subsequently, how it can be removed by a thermal annealing process to generate a structurally ordered and crystalline thin film with significantly improved field-effect transistor properties.

Surface characterization and liquid crystal alignment behavior of comb-like poly(oxyethylene)/poly(3-hexylthiophene) blend films.

The blend surfaces of poly[oxy(n-decylsulfonylmethyl)ethylene] (CH(3)-10SE) and poly (3-hexylthiophene) (P3HT) with different weight ratios were prepared by spin coating the polymer solution mixtures. In this study, their surface properties such as surface morphology, chemical composition, molecular structure, and wettability were systematically studied and correlated with liquid crystal (LC) alignment behaviors on the blend films. Therefore, we found that CH(3)-10SE part with a well-ordered side chain structure predominantly affects the both of wettability and LC alignment behavior of the blend films while there was no clear association between the wettability and the LC alignment behavior.

Silver-perfluorodecanethiolate complexes having superhydrophobic, antifouling, antibacterial properties.

Silver-perfluorodecanethiolate complexes having superhydrophobic, antifouling, antibacterial properties were prepared by a reaction of silver nitrate with perfluorodecanethiol. When the silver nitrate to perfluorodecanethiol molar ratio was 1/2, silver-perfluorodecanethiolate complexes having hierarchical micro-/nano-sized wire shapes were obtained, and they showed superhydrophobic and antifouling properties. After UV irradiation, silver nanoparticles were generated on the wires and exhibited antibacterial properties.

Bacterial adhesion-resistant poly(2-hydroxyethyl methacrylate) derivative for mammalian cell cultures.

In an attempting to find new biomaterials for mammalian cell culture, PHEMA derivatives with ester side groups are synthesized by one-step polymer-analogous reaction. These polymers show excellent antifouling properties against S. epidermidis and P. aeruginosa while their cytotoxicity and proliferation activity for HDF cell are on a similar level as commercially available TCPS. The interesting bioadhesion property is systematically correlated with surface properties of the PHEMA derivatives.

Surface properties and liquid crystal alignment behavior of poly(2-hydroxyethyl methacrylate) derivatives with alkyl ester side chains.

Poly(2-hydroxyethyl methacrylate) derivatives with amphiphilic side chains composed of polar ester and non-polar alkyl groups (PHEMA#C, #=9, 11, 13, 15, and 17), where # is the number of carbon atoms in the alkyl side groups, were synthesized. In this paper, the influence of ester and alkyl groups on the molecular structure and wettability of the polymers were studied through varying # in the alkyl side groups. PHEMA#Cs with relatively longer alkyl side groups (#≥15) show bilayer lamellar structures with well aligned side chains giving rise to the very low surface energies, calculated from advancing contact angles, in the range of 22.7-22.8 mN/m. In contrast, PHEMA#Cs with shorter alkyl side groups with #≤13 have disordered structures on the polymer surfaces and stick-slip behavior was observed when water was used as the test liquid for the advancing contact angle measurements. Furthermore, the alignment behavior of nematic liquid crystal, 5CB on the PHEMA#C films could be correlated with the molecular structure and wettability of the polymers.

Wettability of the morphologically and compositionally varied surfaces prepared from blends of well ordered comb-like polymer and polystyrene.

Phase-separated surfaces of blends of polystyrene (PS) and well ordered comb-like polymer, poly[(oxy(decylsulfonylmethyl)ethylene)] (CH(3)-10SE), were prepared by spin casting polymer mixtures. Various surface morphologies, such as holes, islands, connected islands and pillars, were prepared by changing the blend compositions. Due to the influence of the CH(3)-10SE domain with a well ordered molecular conformation, a very low energy surface (≈22mN/m) was created, which is close to the value of the pure polymer (≈20mN/m), even when the blends contained only 20wt.% of the pure polymer. Furthermore, by selective etching the PS domain in the blend surfaces, the advancing contact angles of water and n-hexadecane were highly increased from 113.5° and 43.2° for the pure CH(3)-10SE surface to 133.3° and 67.2° for the CH(3)-10SE structural surfaces with holes prepared using the solvent etching method, respectively. The result of the water advancing contact angles measured on the samples immersed in water over 20days showed that the film stability of CH(3)-10SE could be improved considerably by even adding small amounts of PS.

Comb-like polymer blends of poly(oxyethylene)s with CH3-terminated and CF3-terminated alkylsulfonylmethyl side chains: effect of terminal CF3 moiety on the surface properties of the blends.

The surface properties of comb-like polymer blends of poly(oxyethylene)s having CH(3)-terminated and CF(3)-terminated alkylsulfonylmethyl side chains were studied. These side chains were found to be well oriented on the surface of the blends, while being phase separated, forming various surface morphologies composed of holes, islands, or connected islands, because of their immiscibility resulting from their different polarities. The domain size of each polymer on the blend surface was found to be almost linearly proportional to the bulk compositions of the mixture, and the CF(3)-terminated alkylsulfonylmethyl side chain domains were found to be located in the lower region of the surface. The polar CF(3)-terminal groups in the lower regions were deemed to control the surface properties, because the contact angles and stick-slip behaviors of the blends containing more than 40 mol% of poly(oxyethylene) with CF(3)-terminated side chains were almost identical.

Inhibition of bacterial adhesion on well ordered comb-like polymer surfaces.

The surfaces of comb-like poly(oxyethylene) derivatives with n-alkylsulfonyl side groups were more effective at reducing Pseudomonas aeruginosa adhesion than the surfaces of common materials such as polystyrene, poly(methyl methacrylate), poly(dimethylsiloxane), fluorinated polyacrylate, and glass. When the comb-like poly(oxyethylene) was mixed with polystyrene and poly(methyl methacrylate), the topology and roughness of the surfaces varied according to the mixture compositions. However the surface energies of the mixtures were close to that of the comb-like poly(oxyethylene) in the range of 21-23 mN/m and bacterial adhesion resistances of the mixture surfaces were also comparable to that of the pure comb-like poly(oxyethylene) surface.