Adhesion and friction properties of fluoropolymer brushes: On the tribological inertness of fluorine

The effects of fluorination on the adhesion and friction properties of covalently bound poly(fluoroalkyl methacrylate) polymer brushes (thickness ~80 nm) were systematically investigated. Si(111) surfaces were functionalized with a covalently bound initiator via a thiol–yne click reaction to have a high surface coverage for initiator immobilization. Surface-initiated atom-transfer radical polymerization (SI-ATRP) was employed for the synthesis of four different fluoropolymer brushes (SPFx, where x = 0, 3, 7, or 17 F atoms per monomer), based on fluoroalkyl methacrylates. All polymer brushes were characterized with static contact angle measurements, X-ray photoelectron spectroscopy (XPS), and infrared absorption reflection spectroscopy (IRRAS). The polymer brushes exhibited an excellent hydrophobicity, with static water contact angles of up to 121° depending on the number of fluorine atoms per side chain in fluoroalkyl methacrylate. The degree of swelling was precisely studied by using ellipsometry in different solvents such as acetone, hexadecane, hexafluoroisopropanol, nonafluorobutyl methyl ether, and Fluorinert FC-40. The polymer brushes have shown nanoscale swelling behavior in all solvents except hexadecane. The grafting density decreased upon increasing fluorine content in polymer brushes from 0.65 chains/nm2 (SPF0) to 0.10 chains/nm2 (SPF17) as observed in Fluorinert FC-40 as a good solvent. Adhesion and friction force measurements were conducted with silica colloidal probe atomic force microscopy (CP-AFM) under ambient, dry (argon), and lubricating fluid conditions. SPF17 showed the lowest coefficient of friction 0.005 under ambient condition (RH = 44 ± 2%) and a further decrease with 50% under fluidic conditions. These polymer brushes also showed adhesion forces as low as 6.9 nN under ambient conditions, which further went down to 0.003 nN under fluidic conditions (Fluorinert FC-40 and hexadecane) at 10 nN force

Adhesion and friction properties of fluoropolymer brushes: On the tribological inertness of fluorine

The effects of fluorination on the adhesion and friction properties of covalently bound poly(fluoroalkyl methacrylate) polymer brushes (thickness ~80 nm) were systematically investigated. Si(111) surfaces were functionalized with a covalently bound initiator via a thiol–yne click reaction to have a high surface coverage for initiator immobilization. Surface-initiated atom-transfer radical polymerization (SI-ATRP) was employed for the synthesis of four different fluoropolymer brushes (SPFx, where x = 0, 3, 7, or 17 F atoms per monomer), based on fluoroalkyl methacrylates. All polymer brushes were characterized with static contact angle measurements, X-ray photoelectron spectroscopy (XPS), and infrared absorption reflection spectroscopy (IRRAS). The polymer brushes exhibited an excellent hydrophobicity, with static water contact angles of up to 121° depending on the number of fluorine atoms per side chain in fluoroalkyl methacrylate. The degree of swelling was precisely studied by using ellipsometry in different solvents such as acetone, hexadecane, hexafluoroisopropanol, nonafluorobutyl methyl ether, and Fluorinert FC-40. The polymer brushes have shown nanoscale swelling behavior in all solvents except hexadecane. The grafting density decreased upon increasing fluorine content in polymer brushes from 0.65 chains/nm2 (SPF0) to 0.10 chains/nm2 (SPF17) as observed in Fluorinert FC-40 as a good solvent. Adhesion and friction force measurements were conducted with silica colloidal probe atomic force microscopy (CP-AFM) under ambient, dry (argon), and lubricating fluid conditions. SPF17 showed the lowest coefficient of friction 0.005 under ambient condition (RH = 44 ± 2%) and a further decrease with 50% under fluidic conditions. These polymer brushes also showed adhesion forces as low as 6.9 nN under ambient conditions, which further went down to 0.003 nN under fluidic conditions (Fluorinert FC-40 and hexadecane) at 10 nN force

Adhesion and friction properties of polymer brushes: Fluoro versus nonfluoro polymer brushes at varying thickness

A series of different thicknesses of fluoro poly(2,2,2-trifluoroethyl methacrylate) and its analogous nonfluoro poly(ethyl methacrylate) polymer brushes were prepared via surface-initiated ATRP (SI-ATRP) on Si(111) surfaces. The thiol-yne click reaction was used to immobilize the SI-ATRP initiator with a high surface coverage, in order to achieve denser polymer brushes (grafting density from ~0.1 to 0.8 chains/nm2). All polymer brushes were characterized by static water contact angle measurements, infrared absorption reflection spectroscopy, and X-ray photoelectron spectroscopy. Adhesion and friction force measurements were conducted with silica colloidal probe atomic force microscopy (CP-AFM) under ambient and dry (argon) conditions. The fluoro poly(2,2,2-trifluoroethyl methacrylate) polymer showed a decrease in adhesion and friction with increasing thickness. The analogous nonfluoro poly(ethyl methacrylate) polymer brushes showed high adhesion and friction under ambient conditions. Friction coefficients down to 0.0057 (ambient conditions) and 0.0031 (dry argon) were obtained for poly(2,2,2-trifluoroethyl methacrylate) polymer brushes with 140 nm thickness, which are the lowest among these types of polymer brushes

Adhesion and friction properties of polymer brushes: Fluoro versus nonfluoro polymer brushes at varying thickness

A series of different thicknesses of fluoro poly(2,2,2-trifluoroethyl methacrylate) and its analogous nonfluoro poly(ethyl methacrylate) polymer brushes were prepared via surface-initiated ATRP (SI-ATRP) on Si(111) surfaces. The thiol-yne click reaction was used to immobilize the SI-ATRP initiator with a high surface coverage, in order to achieve denser polymer brushes (grafting density from ~0.1 to 0.8 chains/nm2). All polymer brushes were characterized by static water contact angle measurements, infrared absorption reflection spectroscopy, and X-ray photoelectron spectroscopy. Adhesion and friction force measurements were conducted with silica colloidal probe atomic force microscopy (CP-AFM) under ambient and dry (argon) conditions. The fluoro poly(2,2,2-trifluoroethyl methacrylate) polymer showed a decrease in adhesion and friction with increasing thickness. The analogous nonfluoro poly(ethyl methacrylate) polymer brushes showed high adhesion and friction under ambient conditions. Friction coefficients down to 0.0057 (ambient conditions) and 0.0031 (dry argon) were obtained for poly(2,2,2-trifluoroethyl methacrylate) polymer brushes with 140 nm thickness, which are the lowest among these types of polymer brushes

Spinning wave motion in frontal polymerization

Chemical Engineering Science6251448-1455CESC

Hydrolytic and Thermal Stability of Organic Monolayers on Various Inorganic Substrates

A comparative study is presented of the hydrolytic and thermal stability of 24 different kinds of monolayers on Si(111), Si(100), SiC, SiN, SiO2, CrN, ITO, PAO, Au, and stainless steel surfaces. These surfaces were modified utilizing appropriate organic compounds having a constant alkyl chain length (C18), but with different surface-reactive groups, such as 1-octadecene, 1-octadecyne, 1-octadecyltrichlorosilane, 1-octadecanethiol, 1-octadecylamine and 1-octadecylphosphonic acid. The hydrolytic stability of obtained monolayers was systematically investigated in triplicate in constantly flowing aqueous media at room temperature in acidic (pH 3), basic (pH 11), phosphate buffer saline (PBS) and deionized water (neutral conditions), for a period of 1 day, 7 days, and 30 days, yielding 1152 data points for the hydrolytic stability. The hydrolytic stability was monitored by static contact angle measurements and X-ray photoelectron spectroscopy (XPS). The covalently bound alkyne monolayers on Si(111), Si(100), and SiC were shown to be among the most stable monolayers under acidic and neutral conditions. Additionally, the thermal stability of 14 different monolayers was studied in vacuum using XPS at elevated temperatures (25–600 °C). Similar to the hydrolytic stability, the covalently bound both alkyne and alkene monolayers on Si(111), Si(100) and SiC started to degrade from temperatures above 260 °C, whereas on oxide surfaces (e.g., PAO) phosphonate monolayers even displayed thermal stability up to ~500 °C

Elevated CD8 T-cell counts and virological failure in HIV-infected patients after combination antiretroviral therapy

10.1097/MD.0000000000004570Medicine (United States)9532e457