Organic monolayers and fluoropolymer brushes : functionalization, stability and tribology

This thesis deals with the adhesion and friction properties of densely grafted and covalently bound fluoropolymer brushes on silicon surfaces with varying thickness and fluorine content. A novel surface-functionalizing method is described using the thiol-yne click (TYC) reaction. The TYC reaction is highly useful for the attachment of functional (bio-)molecules and immobilization of radical initiators onto a surface with high density. Next, the hydrolytic and thermal stability of 24 different types of monolayers on Si(111), Si(100), SiC, SiN, SiO2, CrN, ITO, PAO, Au and stainless steel surfaces was evaluated. Subsequently, based on this outcome, highly stable fluorinated polymers are described as obtained using surface-initiated atom transfer radical polymerization (SI-ATRP) reactions. The effects of thickness and fluorine content on tribological properties of these layers were studied. The adhesion and friction properties were investigated using colloidal probe atomic force microscopy under dry and ambient conditions. The solvent-free lubricating properties of obtained fluoropolymer brushes have been characterized in detail, and demonstrate their potential for e.g., MEMS/NEMS devices.</p

Approach Matters: The Kinetics of Interfacial Inverse‐Electron Demand Diels-Alder Reactions

Rapid and quantitative click functionalization of surfaces remains an interesting challenge in surface chemistry. In this regard, inverse electron demand Diels-Alder (IEDDA) reactions represent a promising metal‐free candidate. Herein, we reveal quantitative surface functionalization within 15 min. Furthermore, we report the comprehensive effects of substrate stereochemistry, surrounding microenvironment and substrate order on the reaction kinetics as obtained by surface‐bound mass spectrometry (DART‐HRMS)

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

Efficient Functionalization of Oxide-Free Silicon(111) Surfaces: Thiol-yne versus Thiol-ene Click Chemistry

Thiol-yne click (TYC) chemistry was utilized as a copper-free click reaction for the modification of alkyne-terminated monolayers on oxide-free Si(111) surfaces, and the results were compared with the analogous thiol–ene click (TEC) chemistry. A wide range of thiols such as 9-fluorenylmethoxy-carbonyl cysteine, thio-ß-d-glucose tetraacetate, thioacetic acid, thioglycerol, thioglycolic acid, and 1H,1H,2H,2H-perfluorodecanethiol was immobilized using TYC under photochemical conditions, and all modified surfaces were characterized by static water contact angle measurements, X-ray photoelectron spectroscopy (including a simulation thereof by density functional calculations), and infrared absorption reflection spectroscopy. Surface-bound TYC proceeds with an efficiency of up to 1.5 thiols per alkyne group. This high surface coverage proceeds without oxidizing the Si surface. TYC yielded consistently higher surface coverages than TEC, due to double addition of thiols to alkyne-terminated monolayers. This also allows for the sequential and highly efficient attachment of two different thiols onto an alkyne-terminated monolayer

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 (SPF<i>x</i>, where <i>x</i> = 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

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