A New Concept for Adhesion Promotion in Metal–Polymer Systems by Introduction of Covalently Bonded Spacers at the Interface

A new concept for molecular interface design in metal–polymer systems is presented. The main features of this concept are the replacement of weak physical interactions by strong covalent bonds, the flexibilization of the interface for compensating different thermal expansions of materials by using long-chain flexible and covalently bonded spacers between the metal and the polymer as well as its design as a moisture-repellent structure for hindering diffusion of water molecules into the interface and hydrolysis of chemical bonds. For this purpose, the main task was to develop plasmachemical and chemical techniques for equipping polymer surfaces with monotype functional groups of adjustable concentration. The establishing of monotype functional groups allows grafting the functional groups by spacer molecules by applying usual wet-chemical reactions. Four processes were favoured for production of monotype functional groups by highly selective reactions: the plasma bromination, the plasma deposition of plasma polymers, the post-plasma chemical reduction of O-functionalities to OH-groups, and the chemical replacement of bromine groups by NH₂-groups. The grafting of flexible organic molecules as spacers between the metal layer and polymer improved the peel strength of the metal. To obtain maximal peel strength of aluminium coatings to polypropylene films and occurrence of cohesive failure in the polypropylene substrate, about 27 OH groups per 100 C-atoms or 6 COOH groups per 100 C-atoms were needed. Introducing C_6–11-aliphatic spacers 1 OH or COOH group per 100 C-atoms contributed about 60% of the maximal peel strength of the Al–PP system, i.e. 2 or 3 spacer molecules per 100 C-atoms were sufficient for maximal peel strength.     

Characterization of plasma-polymerized allyl alcohol polymers and copolymers with styrene

Pulsed plasma was used to initiate chemical copolymerization of allyl alcohol and styrene. In this way the concentration of OH groups at the surface of the copolymer layer could be adjusted from 0 (styrene homopolymerization) to 31 OH groups/100 C atoms (allyl alcohol homopolymerization). The copolymerization kinetics correspond to those of a pure chemical (radical) copolymerization. Thus, the variation of OH group density is only possible in a small range of comonomers ratio, otherwise styrene homopolymerization dominates.     

聚烯烃接枝的研究进展

介绍了以过氧化物为中间产物的聚烯烃本体接枝、链转移反应、多单体熔融接枝的进展情况,重点阐述了表面接枝中的化学方法、利用辐照和光照技术对聚烯烃的表面改性、等离子体工艺及相关的聚丙烯表面改性剂。聚烯烃接枝是制备功能性聚烯烃的主要方法,也是高分子与工程材料领域最活跃的研究热点之一。     

Quantum study of hydrogen–oxygen–graphite interactions

Density functional calculations are used to study the reactions of hydrogen and oxygen atoms on the basal plane of graphite. Oxygen atoms can strongly bond to the graphite surface forming an epoxide-like structure. Hydrogen atoms can react with the adsorbed oxygen and form hydroxyl (OH) radicals. The low-energy OH radicals can be retained on the graphite surface and then they can undergo recombination with hydrogen to form water molecules which leave the surface. Both the formation of hydroxyl radicals and water molecules can occur through Eley–Rideal or Langmuir–Hinshelwood mechanisms. The Eley–Rideal mechanism is kinetically favored. The study on formation of OH radicals was completed with quantum molecular dynamics calculations (Verlet algorithm).     

2，4-二氯苯氧乙酸臭氧化过程中过氧化氢的生成

引言2,4-二氯苯氧乙酸(2,4-D,又名2,4-滴)是一种广泛使用的除草剂[1],应用历史较长,是我国主要的除草剂品种之一,用量也比较大。2,4-D属于苯氧羧酸类除草剂的一种,可有效去除阔叶杂草,目前仍广泛用于农作物除草和草坪养护[2]。2,4-D的水溶性较高,挥发性较低,在自然界中难以生物     

Modification of polyolefin surfaces by plasma-induced grafting

Polar monomers have been grafted onto polyolefin surfaces with the aid of inert gas plasma. In the first stage, an inert gas plasma (argon plasma) was used to generate free radicals on the polyolefin surface. In the second stage, the plasma generator was turned off and a vinyl monomer introduced as a vapor. Monomer was surface grafted by free radical polymerization. After cleaning and drying, the samples were analyzed by XPS, IR, and contact angle. LD–PE was successfully grafted with acrylic acid, glycidyl methacrylate, methyl acrylate, and 2-hydroxy ethylacrylate. The grafting of acrylic acid was studied in more detail, and the rate of grafting was observed to increase with increasing monomer pressure and to decrease with time. The increasing of grafting temperature was found to reduce the degree of grafting. This last factor can be explained by the reduced concentration of monomer at the polymer surface or by a deactivation of surface radicals. © 1996 John Wiley & Sons, Inc.     

聚烯烃热塑性弹性体POE官能化及其应用

聚烯烃热塑性弹性体（POE）的非极性限制了它的进一步应用,为了扩大其使用领域,对POE官能化引起关注。将POE作为接枝机体树脂,利用其支化度比较高、容易形成接枝点来获得较高的接枝率;由于其侧链相对较大,有可能降低大分子自由基之间碰撞的几率,从而减轻凝胶化程度,得到具有良好流动性的接枝树脂。本文综述了聚烯烃热塑性弹性体POE官能化几种方法,包括在有机过氧化物引发剂存在下的熔融接枝法、裂解引发接枝、机械力引发接枝、复合引发接枝等等,并对其产物的应用进行概括。     

Adhesion promotion of thick polyphosphate-poly(allylamine) films onto polyolefin substrates by plasma polymers

The adhesion of thick poly(allylamine)-polyphosphate layers (1 μm) deposited by the wet-chemical layer-by-layer (LbL) technique onto polyethylene or polystyrene (each 100 μm) was very low. To promote the adhesion of these LbL deposited layers, the polyolefin substrates were oxidized at the surface by short exposure to the oxygen plasma (2 or 5 s) and subsequently coated with an interlayer of plasma-deposited poly(allylamine) or poly(allyl alcohol) (100 nm). The plasma polymer interlayers have improved strongly the adhesion between polyolefin substrates and polyphosphate coatings. Such phosphate coatings are interesting for life sciences (nucleotide formation) but also for fire retardancy in combination with N-rich compounds such as melamine. The intention was to prefer chemical hydrogen bonds for adhesion promoting because of their high binding energy. Therefore the introduced oxygen-containing groups at the polyolefin surface could interact with the OH or NH₂ groups of the adhesion-promoting plasma polymer interlayer. These groups were also able to interact strongly with the poly(allylamine)-polyphosphate topcoating. The coated polyolefins were investigated using Fourier transform infrared spectroscopy in attenuated total reflectance mode (FTIR-ATR), X-ray photoelectron spectroscopy, thermogravimetric analyses and atomic force spectroscopy, and 90° peel test.     

Nitroxyls for scorch suppression,cure control,and functionalization in free-radical crosslinking of polyethylene

This paper describes the use of 2,2,6,6-tetramethylpiperidinyl-oxy (TEMPO) derivatives for scorch suppression, cure control, and functionalization in peroxide crosslinking of polyethylene. When 4-hydroxy 2,2,6,6-tetramethylpiperidin-1-oxyl was used for scorch suppression, there was often a loss in ultimate degree of crosslinking. In contrast, with bis(1-oxyl-2,2,6,6-tetramethylpiperidine-4-yl)sebacate, both scorch suppression and ultimate degree of crosslinking were enhanced. A model study in hexadecane showed that TEMPO radicals terminate with carbon-centered radicals formed as a consequence of peroxide homolysis and propagation steps. This termination occurs preferentially over peroxide-initiated crosslinking and results in TEMPO-grafted polymer. In addition to polymer radical formation, several additional reaction pathways are available following thermal homolysis of the peroxide, including unimolecular disassociation of the peroxy radical to yield a methyl radical and a ketone, and proton extraction from one of several substrates by the peroxy radical to yield an alkyl radical and an alcohol. This study reveals that the reaction rate is limited by the rate of peroxide homolysis, and proceeds to statistical products with little or no preference for any specific species. The implication is that choice of peroxide is a dominant controlling factor over whether the TEMPO derivatives are ultimately grafted to the polymer or are bound to small alkyl radicals. POLYM. ENG. SCI., 47:50–61, 2007. © 2006 Society of Plastics Engineers     

Contribution of Dissolved Oxygen to Methyl Orange Decomposition by Liquid Phase Plasma Processes System

Degradation of methyl orange (MO) in liquid phase plasma (LPP) was investigated. A bipolar pulsed power supply was used to generate discharges in the aqueous solution. Properties of generated plasma were investigated by electrical and optical emission spectroscopy methods. The MO decomposition rate increased with increasing levels of applied voltage, pulse width and frequency. The concentrations of activated species, including OH? radicals, were increased by the supply of DO. The concentration of OH? increased with increasing DO concentration up to 50 ppm. Further increase in the DO concentration, however, reduced the OH? concentration because of recombination of OH? radicals. The trend of MO decomposition rate with varying DO concentration was the same as that observed for the OH? concentration, suggesting that OH? radicals play a critical role in the decomposition of MO. Therefore, the LPP process for MO decomposition should be operated with an optimum DO concentration where the OH? radical concentration becomes highest.     

Effects of Stabilized Criegee Intermediate and OH Radical Scavengers on Aerosol Formation from Reactions of β-Pinene with O 3

The formation of secondary organic aerosol (SOA) from reactions of O 3 with g -pinene, an exocyclic monoterpene prominent in the ambient atmosphere, was studied in an environmental chamber using a thermal desorption particle beam mass spectrometer for chemical analysis and a scanning mobility particle sizer for aerosol yield measurements. Potential reaction pathways for SOA formation were investigated in a series of experiments conducted using various scavengers for stabilized Criegee intermediates (SCI) and OH radicals, both of which are formed in the reaction. The major particulate products were compounds less volatile than pinic acid, a low-volatility dicarboxylic acid that was identified but was a minor component of the aerosol. The aerosol mass spectrum and yield were relatively insensitive to the identity of the SCI scavenger, indicating that association reactions of scavengers with SCI were not important in SOA formation. The mass spectrum of the aerosol also did not depend on the identity of the OH radical scavenger. SOA yields, on the other hand, were significantly larger when cyclohexane was used as an OH radical scavenger, compared to those measured for reactions conducted using alcohols or aldehydes. This dependence indicates that radical pathways play a major role in SOA formation in this reaction. Furthermore, the results show that reaction of OH radicals with scavengers used in laboratory studies can perturb the radical chemistry in such a way as to significantly impact SOA yields. We propose that this effect is due to increases in the ratio [hydroperoxy radicals]/[organic peroxy radicals] when alcohols or aldehydes are used as OH radical scavengers. This apparently enhances the rate of reaction of hydroperoxy radicals with key radical intermediates in SOA formation, effectively short-circuiting the reaction system into pathways leading to more volatile products.     

Free Radical and Direct Ozone Reaction Competition to Remove Priority and Pharmaceutical Water Contaminants with Single and Hydrogen Peroxide Ozonation Systems

From the application of concepts derived from the gas-liquid absorption film model, the competition between ozone reactions with 72 water emerging or priority contaminants (pharmaceuticals, pesticides, polynuclear aromatic hydrocarbons, etc.) and the initiation steps of the hydroxyl radical decomposition of ozone in ozone alone and combined with hydrogen peroxide oxidation systems has been studied. With this information, the ozone preferential reaction, that is, the ozone direct reaction or the formation of free radicals and the kinetic absorption regime are known. In a second step, the ratio of removal rates of the contaminants studied by reacting with hydroxyl radical and ozone has also been estimated. With this, the way contaminants are preferentially removed (from their reaction with ozone or from the reaction with free radicals) can also be known and, hence, whether or not an ozone advanced oxidation system is convenient to be applied. For instance, most of the contaminants studied in this work at concentrations lower than 50 μgL^?1 and hydrogen peroxide at concentrations lower than 50 mgL^?1 react with ozone under chemical control regime so that both direct and free radical reactions theoretically compete. However, under chemical control, typical concentration of scavengers present in wastewater or surface water would inhibit the free radical reactions and, at least theoretically, for many contaminants studied here, the direct ozone reaction is the principal removal way. When mass transfer controls the process rate only contaminants with a hydroxyl and ozone rate constant ratio ≥ 1.6x10⁶ M^-1s^-1 would be preferentially removed through free radical way.     

Flame surface modification of polypropylene film

Contact-angle measurements, the ASTM standard wetting test for polyolefin films, and X-ray photoelectron spectroscopy (XPS or ESCA) were used to characterize flame-treated polypropylene (PP) films. Two combustion models, STANJAN and PREMIX, were then used to determine the chemical and physical properties of the flames used to treat the PP films. Both the flame equivalence ratio and the position of the PP film in the flame are important variables in determining the extent of oxidation and improvement in wettability obtained by flame treating. The optimal equivalence ratio for the flame treatment of PP is 0.93, while the optimal luminous flame-to-film distance is 0-2 mm. Modeling of the combustion processes occurring in the flame provides evidence that the extent of treatment correlates closely with the concentrations of H, O, and OH radicals present in the flame. The extent of surface modification of the flame-treated PP does not appear to correlate with either the flame temperature or the concentraion of oxygen molecules. The mechanism of surface oxidation by flame treatment probably involves polymer-radical formation by O and OH, followed by rapid reaction of the polymer radicals with O, OH, and O₂.     

Effect of Br gassing after Ar plasma treatment of polyolefins

For simulation and acceleration of artificial polymer ageing, polyolefin foils were exposed to low-pressure Ar plasma. Plasma particle bombardment and irradiation induce C–C and C–H bond scissions by σ?→?σ ^? excitations on the surface and in near-surface layers. Consequently, radicals are generated. They react by recombination, cross-linking, metastable trapping of the radical site or formation of olefinic double bonds. The long-living and metastable trapped C-radicals as well as double bonds in polyolefins were immediately exposed to bromine vapour without breaking the vacuum after switching-off the plasma. These reactive sites rapidly react with the molecular bromine under formation of C–Br bonds. For 5?min of argon plasma exposure, the elemental concentration of bromine was 13% for polyethylene and 22% Br/C for polypropylene as analysed by X-ray photoelectron spectroscopy. Nevertheless, not all C radical sites have reacted with bromine. Later on, when the polyolefins brought in contact with ambient air, an additional post-plasma reaction of the remaining trapped radicals with oxygen was observed. The oxygen concentrations were lower after bromine gassing, thus repressing partially the post-plasma oxidation in the analysed layer (ca. 6?nm) by radical quenching. Such bromination took place either at the surface or in near-surface layers because the Attenuated Total Reflectance (ATR)-FTIR spectra (sampling depth ca. 2500?nm) did not show significant changes for argon plasma-treated PE foils with and without bromine vapour exposure. Further addition of bromine may also occur on C=C double bonds.     

Melt functionalization of EVA copolymers with maleic anhydride

Ethylene vinyl acetate (EVA) copolymers with different amounts of vinyl acetate were melt‐functionalized with maleic anhydride. The effect of benzoyl peroxide, t‐butyl perbenzoate, and dicumyl peroxide (DCP) as free‐radical initiators on the functionalization performance was studied. The crosslinking reactions occur to a larger extent than in polyethylene, indicating that the vinyl acetate groups favor the formation of free radicals. From all the experiments performed in this study, the recommended initiation system to achieve the best values of the functionalization degree and the lower gel content involves the use of DCP in a concentration of about 0.3 wt % and a maleic anhydride concentration around 5.0 wt %. From FTIR and TGA analyses, it is suggested that the hydrogen abstraction in the EVA copolymers occurs both in the methyl group of the acetate moiety and in the tertiary C—H. The free radicals generated in the tertiary C—H react with maleic anhydride in a higher proportion. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1799–1806, 1999     

Characterization of Natural Water for Potential to Oxidize Organic Pollutants with Ozone

A laboratory study has been designed to investigate the decomposition of ozone in natural water and to determine its potential to produce hydroxyl free radicals for the oxidation of micropollutants during the ozonation process of drinking water. This report describes the first data obtained using a continuous flow reactor capable of observing reactions with relatively short time scales (Q = 34 mL/min; 1.4 < t_c < 27 sec). Rates of ozone decay were studied in fulvic acid solution in the presence, or in the absence of radical scavenger (tert-butyl alcohol) or of promoter of ozone decomposition (formic acid), and a micropollutant of interest (tetrachloroethylene). Also, three natural waters were studied, illustrating that OH radical formation depends on chemical composition of the waters.     

Effect of the OH Radical Scavenger Hydrogen Peroxide on Secondary Organic Aerosol Formation from α-Pinene Ozonolysis

Hydrogen peroxide (HOOH) is a potentially valuable hydroxyl radical (OH) scavenger in secondary organic aerosol experiments focused on ozonolysis yields. Here, we present results for α-pinene ozonolysis. The OH scavenging produces solely HO₂ radicals and the resulting high [HO₂]/[RO₂] ratio causes an increase in aerosol formation from α-pinene ozonolysis, compared to experiments performed with butanol OH scavengers. The majority of the increase comes in the 100 μg m^?3 volatility range, suggesting that instead of more volatile products formed under higher RO₂ conditions, less volatile, multifunctional hydroperoxides form under the high-HO₂ conditions here. This dependence on the [HO₂]/[RO₂] ratio can be parameterized in a similar fashion to the way high- and low-NO _x yields are currently treated in models.     

Antioxidants and stabilizers, 117. Contribution to the transformation mechanism of 2,6-di-tert-butyl-4-methylphenol,a processing stabilizer for polyolefins

2,6-Di-tert-butyl-4-methylphenol (1) , a polyolefin processing stabilizer, is transformed during the stabilization process primarily into 2,6-di-tert-butyl-4-methyl-phenoxyl (2) . The important consecutive transformation pathway of 2 involves irreversible C? C coupling giving 4,4′-ethylenebis(2,6-di-tert-butylphenol) (8) and reversible C? C coupling accounting for formation of 2,6-di-tert-butyl-4-methyl-4-(3,5-di-tert-butyl-4-hydroxybenzyl)-2,5-cyclohexadiene-1-one (9) . The stepwise transformation of 9 into the parent phenol 1 , the stable dimer 8 and a variety of other products was found in EPR and chromatographic studies of free radical and molecular products generated from 9 in oxidative environment. It follows that compounds 1, 8 and 9 are stepwise transformed into coloured quinoide and quinonemethinoide compounds in the ultimate phase, and the antioxidant chain-breaking character of 1 is thus lost. It is considered that most of the free radical species formed transiently during transformation of 1 and/or of derived phenolic coupling products disappear from the system via disproportionation and alkylperoxy radicals (RO₂) or oxygen trapping. Labile, cross-conjugated, peroxidic species generated by the latter process contribute to the fragmentation of coupling products.     

Decomposition of hydrogen peroxide in the presence of activated carbons with different characteristics

BACKGROUND: Catalytic ozonation promoted by activated carbon is a promising advanced oxidation process used in water treatment. Hydrogen peroxide generated as a by‐product from the reaction of ozone with some surface groups on the activated carbon or from the oxidation of some organic compounds present in the water being treated seems to play a key role in the catalytic ozonation process. Hydrogen peroxide decomposition promoted by two granular activated carbons (GAC) of different characteristics (Hydraffin P110 and Chemviron SSP‐4) has been studied in a batch reactor. The operating variables investigated were the stirring speed, temperature, pH and particle size. Also, the influence of metals on the GAC surface, that can catalyze hydrogen peroxide decomposition, was observed. RESULTS: Chemviron SSP‐4 showed a higher activity to decompose hydrogen peroxide than HydraffinP110 (70 and 50% of hydrogen peroxide removed after 2 h process, respectively). Regardless of the activated carbon used, hydrogen peroxide decomposition was clearly controlled by the mass transfer, although temperature and pH conditions exerted a remarkable influence on the process. Catalytic ozonation in the presence of activated carbon and hydrogen peroxide greatly improved the mineralization of oxalic acid (a very recalcitrant target compound). About 70% TOC (total organic carbon) depletion was observed after 1 h reaction in this combined system, much higher than the mineralization achieved by the single processes used. CONCLUSIONS: Of the two activated carbons studied, Chemviron SSP‐4 with an acidic nature presented a higher activity to decompose hydrogen peroxide. However the influence of the operating variables was quite similar in both cases. Experiments carried out in the presence of tert‐butanol confirmed the appearance of radical species. A kinetic study indicated that the process was controlled by the internal mass transfer and the chemical reaction on the surface of the activated carbon. The catalytic activity of hydrogen peroxide in oxalic acid ozonation promoted by activated carbon (O₃/AC/H₂O₂) was also studied. The results revealed the synergetic activity of the system O₃/AC/H₂O₂ to remove oxalic acid. Copyright © 2010 Society of Chemical Industry     

Atmospheric-Pressure Plasma Amination of Polymer Surfaces

Using dielectric barrier discharges (DBDs) in suitable gas atmospheres, appreciable densities of amino groups can be generated on polymer surfaces. After the introduction and a few remarks on analytical methods for the determination of functional groups densities, this paper presents a short summary of recent studies on the mechanism of the polymer surface amination from nitrogen and nitrogen/hydrogen mixtures, and possible relevant precursor species. Combination of chemical derivatization with quantitative FT-IR spectroscopy was employed for the determination of primary amino groups densities introduced on polyolefin surfaces in DBD afterglows in N₂ and N₂ + H₂ mixtures. Owing to the possibility to generate atmospheric-pressure plasmas in sub-mm³ volumes, DBD plasmas can be used to modify polymer surfaces area selectively: a new process termed 'plasma printing' can be applied for the achievement of micropatterned surface modifications, such as hydrophilization/hydrophobization or chemical functionalization. Direct-patterning polymer surface modification processes are of interest for biochemical/biomedical applications as well as for polymer electronics. Two examples are presented in more detail: ? the area-selective plasma amination of carbon-filled polypropylene minidiscs to manufacture microarrays with peptide libraries utilizing parallel combinatorial chemical synthesis, and ?the continuous treatment of polymer foils by means of reel-to-reel patterned plasma amination for the subsequent electroless copper metallization, leading to a fast and highly efficient process for the manufacture of structured metallizations for flexible printed circuits or RFID antennas.