A polymerizable ionic liquid, N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide (DEMM-TFSI), was polymerized via copper-mediated atom transfer radical polymerization (ATRP). The polymerization proceeded in a living manner producing well-defined poly(DEMM-TFSI) of target molecular weight up to about 400 K (including a polycation and an counter anion). The accurate molecular weight as determined by a GPC analysis combined with a light scattering measurement, and the molecular weight values obtained exhibited good agreement with the theoretical values calculated from the initial molar ratio of DEMM-TFSI and the monomer conversion. Surface-initiated ATRP on the surface of monodisperse silica particles (SiPs) with various diameters was successfully performed, producing SiPs grafted with well-defined poly(DEMM-TFSI) with a graft density as high as 0.15 chains/nm². Since the composite film made from the silica-particle-decorated polymer brush and ionic liquid shows a relatively high ionic conductivity, we have evaluated the relationship between the grafted brush chain length and the ionic conductivity.

Among the possible solutions for achieving low friction, polymer brushes that are grafted onto surfaces are good candidates. The tribological characterization of such layers becomes more difficult when the friction is lower: the signal-to-noise ratio of the friction force that is measured with conventional tribometers impedes the precise quantification. Therefore, we have applied a new technique that has been developed at the Laboratory of Tribology and System Dynamics (LTDS), called the ‘oscillating relaxation tribometer’. The advantage of this original technique is that it characterizes low friction with unequalled sensitivity. The lower the friction, the better the precision, and it permits obtaining the ‘friction law’ directly from robust and rapid experimental tests. In this study, the samples that have been used are the ionic liquid-type polymer brushes (ILPBs) with different thicknesses, which have been grafted onto silicon wafers and steel coupons. The counter-face is a mirror-polished steel ball. We show that (i) a thick ILPB layer on silicon is very resistant to high contact pressure, up to 555 MPa; (ii) the friction behavior that is obtained is close to that of a Newtonian viscous one, even under maximum normal loads; (iii) poorer results are obtained for the thinner sample; and (iv) the repetition, up to 5000 oscillations on the same surface, does not affect the friction damping of the contact, which demonstrates that this film provides a favorable resistance to friction under severe contact conditions. In addition, the feasibility of grafting onto steel surfaces is demonstrated. The results are then discussed, with respect to friction and dissipation.

Researchers around the world are developing technologies to minimize carbon dioxide emissions or carbon neutrality in various fields. In this study, the dry spinning of regenerated silk fibroin (RSF) was achieved as a proof of concept for a process using ionic liquids as dissolution aids and plasticizers in developing natural polymeric materials. A dry spinning equipment system combining a stainless-steel syringe and a brushless motor was built to generate fiber compacts from a dope of silk fibroin obtained by degumming silkworm silk cocoons and ionic liquid 1-hexyl-3-methyl-imidazolium chloride ([HMIM][Cl]) according to a general method. The maximum stress and maximum elongation of the RSF fibers were 159.9 MPa and 31.5%, respectively. RSF fibers containing ionic liquids have a homogeneous internal structure according to morphological investigations. Elemental analysis of fiber cross sections revealed the homogeneous distribution of nonvolatile ionic liquid [HMIM][Cl] in RSF fibers. Furthermore, the removal of ionic liquids from RSF fibers through impregnation washing with organic solvents was verified to enhance industrial applications. Tensile testing showed that the fiber strength could be maintained even after removing the ionic liquid. Thermogravimetric analysis results show that the organic solvent 1,1,1,3,3,3-hexafluoro-2-propanol is chemically coordinated to silk fibroin and, as a natural polymer, can withstand heat up to 250 °C.

Since human body joints have a gel-like structure with low friction that persists for several decades, hydrogels have attracted much interest for developing low-friction materials. However, such advantages can hardly be realized in industrial usage because water in the gel evaporates easily and the gel deswells. The substitution of water with an ionic liquid (IL) is one of the effective ways to overcome this problem. In this study, we substituted water in a double network (DN) hydrogel with 3-ethyl-1-methyl-imidazolium ethylsulfate (EMI-EtSulf), a hydrophilic IL, via a simple solvent exchange method to obtain a DN ion gel. A compressive test and thermogravimetric analysis showed that the DN ion gel has a high compression fracture stress and improved thermal properties, with the difference in 10% loss of temperature being ΔT₁₀ = 234 °C. A friction test conducted using a reciprocating tribometer showed that the friction of a glass ball/DN ion gel was relatively higher than that of a glass ball/DN hydrogel. Because the minimum coefficient of friction (COF) value increased after substitution, the increase in polymer adhesion caused by the electrostatic shielding of the surface moieties of glass and poly 2-acrylamidomethylpropanesulfonic acid (PAMPS) was considered the main contributor to the high friction. As the COF value decreased with increasing temperature, the DN ion gel can achieve low friction via the restriction of polymer adhesion at high temperatures, which is difficult in the DN hydrogel owing to drying.

In this paper, in situ surface-initiated atom-transfer radical polymerization (SI-ATRP) based on both an open and a coated system, without using volatile reagents, was developed to overcome the limited usage of ATRP due to the necessity of sealing. Nonvolatile ionic liquid (IL)-type components were used, specifically N,N-diethyl-N-(2-methacryloylethyl)-N-methylammonium bis(trifluoromethylsulfonyl)imide as the polymerizable monomer and N,N-diethylmethyl(2-methoxyethyl)ammonium bis(trifluoromethylsulfonyl)imide as the polymerization solvent. In the experiment, the reversible-deactivation radical polymerization characteristics are properly ensured in nonvolatile ATRP solution coated on silicon wafer as thin liquid film, to form concentrated polymer brushes (CPBs). The average molecular weight and molecular-weight distribution of the polymer produced in the liquid film and formed on silicon wafer were measured by gel permeation chromatography, which confirms that the polymerization reaction occurred as designed. Furthermore, it is clarified that the surface of the polymer brush synthesized in situ swollen by IL also exhibited low friction characteristics, comparable to that synthesized in a typical immersion process. This paper is the first to establish the effectiveness of in situ preparation for CPBs by using the coating technique.