Polymer modification pretreatment

To improve collagen s potential as a biomaterial, it has been modified or combined with other resorbable polymers. Modifications like cross-linking, addition of bioactive molecules, and enzymatic pretreatment have resulted in novel coUagen-based materials with improved fimctionality [10, 11]. Moreover, to facilitate the formation of fibers for biomedical textile applications, composite materials combining coUagen with other resorbable polymers like PLA, PLGA, and PCL have been studied extensively [12-15]. 

It was shown (8,9) that the pretreatment of PET yarns with certain strongly interacting solvents can lead not only to swelling but also to irreversible modifications of polymers structure. The basis of structural modification during the DMF treatment of PET is solvent-induced crystallization which occurs while the PET structure is swollen by DMF. At low treatment temperatures (i.e., 50-100°C, Table I), only small crystallites are formed and after removal of the solvent the swollen structure cannot be supported by the small crystallites and consequently collapses. 

The common polymers are composed of a small number of elements whose XP spectra are simple (generally C Is plus one or two peaks from Ols, Nls, FIs and Cl 2s, 2p). Common contaminants contain additional elements such as S, P, Si, A1 and heavy metals, and the presence of these elements, even in low concentrations, can be detected very easily. Polymer surface modification is an area in which XPS has been fruitfully applied, notably in the study of commercial pretreatments aimed at improving wettability and general adhesion characteristics. 

The efficacy of CE separation depends considerably on the type of capillary. Fused-silica capillaries without pretreatment are used most frequently. Its outside is coated with a polymer layer to make it flexible and to lessen the occurrence of breakage. The polymer coating has to be dissolved with acid or burned away at the detection point. Capillaries with an optically transparent outer coating have also found application in CE. The objectives of the development of chemically modified capillary walls were the elimination of electro-osmotic flow and the prevention of adsorption on the inner wall of the capillary. Another method to prevent the adsorption of cationic analyses and proteins is the use of mobile phase additives. The modification of the pH of the buffer, the addition of salts, amines and polymers have all been successfully employed for the improvement of separation. 

In order to metallize a polymer surface, electroless plating can be applied. This process typically consists of a pretreatment process in order to improve the adhesion. In the second step a surface seeding of the electroless catalyst is done. Wet chemical methods of pretreatment are using strong acids such as chromic acid, sulfuric acid and acidified potassium permanganate in order to achieve a surface modification of the polymers (96). 

In contrast to the EPOS system, a modification of the highly sensitive two-step immunohistochemical EnVision system allows the detection of a broad spectrum of antigens in frozen sections in less than 13 min (Kammerer et al., 2001). In this study 38 out of 45 antibodies tested showed specific staining. In fact, the modified EnVision procedure allows the use of any suitable primary antibody, preferably monoclonal antibodies. Like the EPOS system, EnVision employs a dextran polymer coupled to horseradish peroxidase molecules for detection. No attempt was made to block endogenous peroxidase, nor was any antigen retrieval pretreatment used. Because of the very short incubation durations, a humid chamber is not required to avoid evaporation of immunoreagents. 

Chemical modification reactions continue to play a dominant role in improving the overall utilization of lignocellulosic materials [1,2]. The nature of modification may vary from mild pretreatment of wood with alkali or sulfite as used in the production of mechanical pulp fibers [3] to a variety of etherification, esterification, or copolymerization processes applied in the preparation of wood- [4], cellulose- [5] or lignin- [6] based materials. Since the modification of wood polymers is generally conducted in a heterogeneous system, the apparent reactivity would be influenced by both the chemical and the physical nature of the substrate as well as of the reactant molecules involved. 

Postdeposition plasma modifications to the plasma polymer of TMS have been seen to greatly improve bonding to various primers and paints [18-20]. One particular system has been observed to have tremendous adhesion between plasma-coated A1 alloy panels and paint applied to them. This system involves cathodic DC plasma deposition of a roughly 50-nm primary plasma polymer film from TMS onto a properly pretreated alloy substrate, followed by the deposition of an extremely thin fluorocarbon film by DC cathodic deposition of hexafluoroethane (HFE). It was the superadhesion aspect of this particular system that triggered the series of ESR studies [3,21]. 

The previously discussed principles of grafting-to and grafting-from can also be applied for the modification of polymer surfaces with polymer brushes. However, the binding of linkers and polymerization initiators to polymer surfaces is not as straightforward as it is for oxidic inorganic materials. Thus, dedicated pretreatments are usually necessary. These may include rather harsh reaction conditions due to the chemical inertness of many polymers (see Chapter 3). Alternatively, radiation treatment of polymers (to form radicals) followed by exposure to air may be used to form peroxides and hydroperoxides, which can be directly used as initiators for thermally or ultraviolet-induced graft polymerizations [16,17] (see Chapter 2). 

Polyolefins, such as PE and PP, are commonly used in many applications in the biomedical sector. PE and PP can achieve biocompatible and antimicrobial properties using the suitable surface treatment [131, 132]. Many modification methods of the polymer surfaces have been employed, for example, techniques based on the plasma treatment [133]. A deposition of chitosan on the plasma-pretreated PP surface provides antifungal and antibacterial properties because chitosan exhibits an efficient antimicrobial activity [134]. If PE films were modified by a multistep process using plasma discharge, carboxylic groups and antibacterial agent can be developed over the surface. Immersion of these films into the solution of chitosan leads most likely to the adherence of a chitosan monolayer on the treated film. Small concentration of chitosan was enough for the induction of antimicrobial properties to the modified material [135]. 

An overview of the chemical methods employed to pretreat the polyetherimide is outlined in Figure 1. Removal of 0.5 )im of the polymer surface was accomplished via brief, 0.5 minute, contact with concentrated sulfuric acid. The subsequent water rinse resulted in the formation of a white film or residue. This layer could be removed either through solubilization or oxidation. Utilization of a solubilizer for the debris removal step also required a separate adhesion promotion step. The Standard 2312 process described previouslyS. 10,11 js solubilizer-free and depends on oxidation of the white residue to effect its removal. In this case, no separate adhesion promotion step is necessary and chemical modification of the polymer occurs in each of the principal pretreatment steps. ... 

It has been found that the surface energy of iPP pretreated by chromyl chloride versus modification time rapidly increases and assumes a constant value. Equal character was observed for the relationship between free surface energy and carbonyl group concentration of modified polymer. After a certain time interval subsequent to modification the decrease in surface energy of treated iPP is negligible. A maximum of the relationship between PC of the surface energy and modification time was revealed. 

Plasma treatment of microchannels can be useful for improving the functionality of microdevices. For example, previous studies have shown that PDMS microchannels can be made hydrophilic by the addition of silane molecules with polar head groups [6]. In this process (3-mercaptopropyl)trimethoxysilane (3-MPS) was absorbed to PDMS to increase the hydrophilic properties of microchannels. Additionally, plasma polymerization has been used to induce in the long-term hydrophilic surface modification by covalently bonding a polymer layer to the surface. Barbier et al. [7] describe a method based on plasma polymerization modification with acrylic acid coatings. First, argon plasma pretreatment was used to activate trace oxygen molecules in the chamber, which partially oxidize the top layer of the substrate. This step cross-linked the surface to reduce ablation of silicon... 

Fibre surface modification. The surface energy is closely related to the hydrophilicity of the UgnoceUulosic fibres. Use of dispersing agents, such as stearic acid or a mineral oil. The dispersion of lignocellulosic fibres can be improved by pretreatment with lubricants or thermoplastic polymers. An addition of 1-3 per cent stearic acid is sufficient to achieve a maximum reduction in size and number of aggregates in PP and polyethylene [7]. The use of stearic acid in HDPE/wood fibres was reported to improve the fibre dispersion and the wetting between the fibre and the matrix [9]. 

Liu, C.-B., Tang, T., and Huang, B.-T. 2004. Zirconocene catalyst well spaced inside modified montmorillonite for ethylene polymerization Role of pretreatment and modification of mont-morillonite in tailoring polymer properties. Journal of Catalysis 221 162-169. 

There are a number of materials used for the fabrication of pTAS devices. Perhaps the most common is glass due to its low cost, ease of machining, and suitability for electrophoresis and electroosmotic flow (EOF) applications without requiring surface modifications. It is also chemically inert to most reagents (apart from hydrofluoric acid and concentrated alkali). Silicon is also a valuable material that has similar chemical inermess and can easily be machined by chemical etching. While it is more expensive, it can be easily chemically etched to yield far higher aspect ratios than are possible with glass. Silicon is not suitable for electrophoresis or EOF applications without surface pretreatment. Devices fabricated from polymers such as polymethylmethacrylate (PMMA) and polydimethylsiloxane (PDMS) are also frequently used due to the low cost of the material (especially important for disposable devices) and the ease of fabrication. Perhaps one drawback with polymers is their incompatibility with solvents. They are suited to electrophoretic applications but frequently require surface modification to support EOF. Occasionally, metals are used however, these are far more frequently encountered in chemical microreactors. 

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