Hydrosilane-Modified Poly(2-Hydroxyethyl Methacrylate) Brush as a Nanoadhesive for Efficient Silicone Bonding.

Leaching of chemicals from adhesion promoters is, in particular, problematic for the food, water, pharmaceutical, and MedTech industries where any chemical contamination is unacceptable. A solution to this issue is to employ covalently attached nanoscale polymer brushes as adhesive layers for plastics. One of the industrially most relevant adhesion targets in that respect is poly(dimethylsiloxane) (PDMS), being used for many high-end applications such as catheters and breast implants. In this work, we have synthesized a novel surface-immobilized poly(2-hydroxyethyl methacrylate)-based brush adhesive containing reactive hydrosilane groups that can bond directly to PDMS. Two different medical grades of addition-cured PDMS were molded on top of titanium substrates already coated with the polymer brush. Titanium plates were used for the chemical analysis, and titanium rods were used for adhesion testing. Adhesion testing revealed a high adhesive force, in which cohesive failure was observed in the bulk PDMS. The necessity of the hydrosilane group in the polymer brush adhesive layer was demonstrated in comparative studies using similar brushes lacking this functionality.

Correction to "Hydrosilane Modified Poly(2-Hydroxyethyl Methacrylate) Brush as a Nanoadhesive for Efficient Silicone Bonding".

[This corrects the article DOI: 10.1021/acsomega.9b01282.].

Highly Efficient Rubber-to-Stainless Steel Bonding by Nanometer-Thin Cross-linked Polymer Brushes.

Stainless steel (SS) surfaces were grafted with poly(glycidyl methacrylate) (PGMA) brushes that were post-modified using allylamine, diallylamine, and propylamine as reagents. Likewise, poly[2-(diethylamino)ethyl methacrylate] brushes were synthesized. All samples were compression molded with uncured ethylene-propylene-diene M-class rubber and dicumyl peroxide and vulcanized for 12 min at 170 °C. The efficiency of the novel bonding solution was evaluated through peel experiments. Two parameters, the fracture toughness () and the cohesive-to-adhesive fracture ratio (A r), were calculated to evaluate the strength and the performance of the coupling, respectively. For the nanometer-thin PGMA films modified with allylamine, in particular, full cohesive fracture was obtained. The obtained values of (15.4 ± 1.1 N mm-1) and A r (1.00 ± 0.01) matched those obtained for a micrometer-thick commercial bonding agent. Cross-linking of polymer brushes by intermolecular reactions by the primary amines proved to have a significant impact on the type of fracture (cohesive/adhesive) and the performance of the adhesives.

Patterned Carboxylation of Graphene Using Scanning Electrochemical Microscopy.

A simple, direct, and versatile scanning electrochemical microscopy (SECM) approach for local carboxylation of multilayered graphene on nickel is demonstrated, in which carbon dioxide serves as the carboxylation agent under reductive conditions in N,N-dimethylformamide. The use of SECM gives control over both the spatial dimensions and the degree of carboxylation. While the pattern size, in general, is governed by the dimension of the SECM tip, the degree of modification, expressed as the surface coverage of carboxylate groups introduced at the graphene substrate, is found to be controlled by the electrolysis time. This is supported by electrochemical measurements, two-dimensional X-ray photoelectron spectroscopy, Raman spectroscopy mapping, and He ion microscopy. Surprisingly, intercalation of the supporting electrolyte in the multilayered graphene on nickel occurs to a relatively small extent when compared to corresponding results obtained in previously described carboxylations of this kind of multilayered graphene.

Controlled electrochemical carboxylation of graphene to create a versatile chemical platform for further functionalization.

An electrochemical approach is introduced for the versatile carboxylation of multi-layered graphene in 0.1 M Bu4NBF4/MeCN. First, the graphene substrate (i.e., graphene chemically vapor-deposited on Ni) is negatively charged at -1.9 V versus Ag/AgI in a degassed solution to allow for intercalation of Bu4N(+) and, thereby, separation of the individual graphene sheets. In the next step, the strongly activated and nucleophilic graphene is allowed to react with added carbon dioxide in an addition reaction, introducing carboxylate groups stabilized by Bu4N(+) already present. This procedure may be carried out repetitively to further enhance the carboxylation degree under controlled conditions. Encouragingly, the same degree of control is even attainable, if the intercalation and carboxylation is carried out simultaneously in a one-step procedure, consisting of simply electrolyzing in a CO2-saturated solution at the graphene electrode for a given time. The same functionalization degree is obtained for all multi-layered regions, independent of the number of graphene sheets, which is due to the fact that the entire graphene structure is opened in response to the intercalation of Bu4N(+). Hence, this electrochemical method offers a versatile procedure to make all graphene sheets in a multi-layered but expanded structure accessible for functionalization. On a more general level, this approach will provide a versatile way of forming new hybrid materials based on intimate bond coupling to graphene via carboxylate groups.

High- versus low-quality graphene: a mechanistic investigation of electrografted diazonium-based films for growth of polymer brushes.

Electrografting using aryldiazonium salts provides a fast and efficient technique to functionalize commercially available 3-5 layered graphene (vapour-deposited) on nickel. In this study, Raman spectroscopy is used to quantify the grafting efficiency of cyclic voltammetry which is one of the most versatile, yet simple, electrochemical techniques available. To a large extent the number of defects/substituents introduced to the basal plane of high-quality graphene by this procedure can be controlled through the sweeping conditions employed. After extended electrografting the defect density reaches a saturation level ( ∼ 10(13) cm(-2)) which is independent of the quality of the graphene expressed through its initial content of defects. However, it is reached within fewer voltammetric cycles for low-quality graphene. Based on these results it is suggested that the grafting occurs (a) directly at defect sites for, in particular, low-quality graphene, (b) directly at the basal plane for, in particular, high-quality graphene, and/or (c) at already grafted molecules to give a mushroom-like film growth for all films. Moreover, it is shown that a tertiary alkyl bromide can be introduced at a given surface density to serve as radical initiator for surface-initiated atom transfer radical polymerization (SI-ATRP). Brushes of poly(methyl methacrylate) are grown from these substrates, and the relationship between polymer thickness and sweeping conditions is studied.

Combining aryltriazenes and electrogenerated acids to create well-defined aryl-tethered films and patterns on surfaces.

Immobilization of submonolayers to 4-5 multilayers of organic molecules on carbon surfaces can be performed by in situ generation of aryl radicals from aryltriazenes. The central idea consists of oxidatively forming an electrogenerated acid of N,N'-diphenylhydrazine to convert the aryltriazene to the corresponding diazonium salt in the diffusion layer of the electrode. In a second step, the diazonium salt is reduced at the same electrode to give a surface of covalently attached aryl groups. In this manner, various moieties tethered to the aryl groups can be immobilized on the surface. Here a ferrocenyl group was introduced as redox marker, the electrochemical signal of which is extraordinarily well-defined. This behavior is independent of film thickness, the latter being easily controlled by the number of repetitive cycles performed. It is also demonstrated that the new approach is suitable for patterning of surfaces using scanning electrochemical microscopy.