Surface modification of low‐density polyethylene (LDPE) film and improvement of adhesion between evaporated copper metal film and LDPE

To improve the interfacial adhesion between evaporated copper film and low‐density polyethylene (LDPE) film, the surface of LDPE films was modified by treating with chromic acid [K₂Cr₂O₇/H₂O/H₂SO₄ (4.4/7.1/88.5)]/oxygen plasma. Chromic‐acid‐etched LDPE was exposed to oxygen plasma to achieve a higher content of polar groups on the LDPE surface. We investigated the effect of the treatment time of chromic acid in the range of 1–60 min at 70°C and oxygen plasma in the range of 30–90 sec on the extent of polar groups created on the LDPE. We also investigated the surface topography of and water contact angle on the LDPE film surface, mechanical properties of the LDPE film, and adhesion strength of the evaporated copper metal film to the LDPE film surface. IR and electron spectroscopy for chemical analysis revealed the introduction of polar groups on the modified LDPE film surface, which exhibited an improved contact angle and copper/LDPE adhesion. The number of polar groups and the surface roughness increased with increasing treatment time of chromic acid/plasma. Water contact angle significantly decreased with increasing treatment time of chromic acid/plasma. Combination treatment of oxygen plasma with chromic acid drastically decreased the contact angle. When the treatment times of chromic acid and oxygen plasma were greater than 10 min and 30 sec, respectively, the contact angle was below 20°. With an increasing treatment time of chromic acid, the tensile strength of the LDPE film decreased, and the film color changed after about 10 min and then became blackened after 30 min. With the scratch test, the adhesion between copper and LDPE was found to increase with an increasing treatment time of chromic acid/oxygen plasma. From these results, we found that the optimum treatment times with chromic acid and oxygen plasma were near 30 min and 30 sec, respectively. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 1677–1690, 2001     

Pretreatment of polypropylene films for the creation of thin polymer layers,part 1: The use of chemical,electrochemical, and UV methods

The surface of a polypropylene (PP) film was activated with chemical, electrochemical, and physical methods, and the effectiveness of these methods was compared. The effects of PP activation were assessed with attenuated total reflection IR spectroscopy (ATR‐IR), SEM microscopy, and an analysis, based on the liquid contact angle, of the free energy components of the surface. The activation of the PP surface, which was dependent on the oxidizing medium, increased the energy of the PP surface layer and formed new chemical (carbonyl) groups, which were identified by IR (ATR) absorption spectroscopy and confirmed by selective surface dyeing. The treatments were ranked in the following order of increasing effectiveness: UV irradiation < 3M nitric acid < 30% hydrogen peroxide < silver nitrate (electrochemical method) < chromic mixture. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

XPS and UPS in situ study of oxygen thermal desorption from nanocrystalline diamond surface oxidized by different process

The chemistry of oxygen bonding on the diamond surface is a rich area of surface science research. It is well known that different surface terminations lead to strong variation of the material work function. This effect in diamond assumes peculiar consequences. In fact the oxidized diamond surface is hydrophilic, due to the high work function it shows a positive electron affinity and it is non conductive. On the contrary hydrogenation completely changes the orientation of the surface dipoles, the surface becomes hydrophobic, the work function lowers leading to a negative electron affinity. In addition hydrogen induces subsurface carriers which render the diamond surface semiconducting. These distinctive electronic properties make the diamond surface very interesting for the fabrication of surface field effect transistors just playing with the oxygen/hydrogen chemistry. Hydrogenation is generally obtained during the diamond synthesis in plasma reactors. Differently, the diamond surface oxidation may be accomplished with different processes (wet chemistry, plasma, UV irradiation).The realization of electronic devices calls for a complete understanding of the carbon-oxygen interactions, their stability and their influence on the electronic properties of diamond. Aim of this work is to explore the properties of diamond surfaces oxidized with piranha mixture, with O₂ plasma and with UV irradiation in a pure O₂ atmosphere. Each of these oxidized surfaces were annealed in situ at different temperatures and analyzed with photoelectron spectroscopies. Decreases of the oxygen concentration obtained via thermal desorption are then correlated with variations of the electronic properties obtained from UPS analyses.     

Deoxycholate‐chitosan nanospheres fabricated by γ‐irradiation and chemical modification: Nanoscale synthesis and controlled studies

A systematic protocol to fabricate self‐assembly deoxycholate‐chitosan nanospheres (DC‐CsNS) by γ‐ray pre‐irradiation and chemical modification was studied. Hydrophobic deoxycholic acid moieties were chemically conjugated to pre‐irradiated chitosan. The influences of chitosan physical forms (i.e., colloid and flake) during irradiation, radiation doses, and the reaction system (heterogeneous or homogeneous) on the chemical modification and the particle shape and size were investigated. Pre‐irradiation of chitosan in colloidal form produced smaller DC‐CsNS particle size than that of flake form. In the heterogeneous reaction, the pre‐irradiated dose influenced the DC‐CsNS particle size, whereas in the homogeneous reaction all pre‐irradiation doses gave an identical average size range of 30–50 nm. By pre‐irradiation (10 kGy) of chitosan in colloidal form before heterogeneous chemical conjugation, it is possible to obtain DC‐CsNS with an average size of 46 nm. DC‐CsNS of about 50 nm in size could also be synthesized using homogeneous chemical conjugation onto non‐irradiated chitosan with the addition of N‐hydroxysuccinimide (NHS). © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Dry Processes for Surface Modification of a Biopolymer: Chitosan

Standard dry surface modification reactions have been applied to partially deacetylated chitosan without affecting its bulk properties. Chitin, extracted from shells of Penaeus vannamei, yielded chitosan with a degree of acetylation of 70% and molecular weight of 250 000 D. The copolymer consists of (β‐(1‐4)‐2‐2‐acetamido‐D ‐glucose) units linked to (β‐(1‐4)‐2‐amino‐D ‐glucose) units. Since the main interest of this work was to study the surface properties of films on substrates, a method to cast this material onto Al‐coated silicon wafers had to be developed. X ray photoelectron spectroscopy (XPS) has been used to determine the surface composition of the unmodified films and to follow modification changes. The films were treated in either an oxygen plasma environment or under UV/ozone irradiation. Water advancing contact angle measurements and infrared spectroscopy (FTIR) were used to complement XPS measurements. The films appeared to orient on the silicon wafer surface in the type II chitin structure. The rates of oxidation are faster for the plasma process but they result in similar changes to those induced by UV/ozone treatment. Atomic force microscopy (AFM) clearly shows the advantage of the milder modification reaction without much change in surface morphology. The oxidation processes, as detected by XPS, proceed without much alteration of the amine nitrogen atoms but carbonyl containing moieties are formed as a function of treatment time. Specific reactions with a fluorosilane to measure the activity of hydroxyl groups indicate that at short treatment times, these groups are essentially inactive. The resulting surfaces can also serve as a potential way to induce silica‐like domains that can function as diffusion barriers. Irradiation of chitosan solutions shows that UV/ozone induces depolymerization. In both cases, i.e., plasma and UV/ozone reactions, the main active component to surface modification appears to be UV irradiation with a wavelength below 360 nm.

AFM surface profile for oxygen plasma treated film in barrel etcher for 1 min.     

紫外屏蔽剂氧化锌表面改性的实验研究

实验采用硬脂酸对紫外屏蔽剂氧化锌进行湿法表面改性研究,考察了浆量浓度、改性剂用量、改性时间和改性温度对粉体改性效果的影响,通过对改性前后氧化锌粉体亲油化度、沉降速率以及320nm处紫外透光率等性能测试,从而确定最佳改性条件。研究结果表明,最佳的改性工艺条件为：浆量浓度为7％,改性剂用量为4％,改性温度为85℃,改性时间为0．5h。由红外光谱分析可知,硬脂酸与氧化锌之间属于化学吸附。     

Femtosecond‐laser‐assisted wet chemical etching of polymer materials

Polymers are modified by femtosecond‐(fs)‐IR‐laser irradiation under various process parameters. Several sorts of thermoplastic polymer are employed: polymethylmethacrylate (PMMA), fluorinated PMMA, poly‐N‐methyl methacrylimide (PMMI), polystyrol, polycarbonate, polyimide, and polyethylene. After the fs‐laser‐induced modification process, the irradiated area is developed by an aqueous solution of a solvent agent (n‐hexane, benzene, and methylisobutylketone). The surface topography of the fs‐laser‐irradiated area is characterized by stylus‐profilometry before and after the development procedure. Some preliminary explanations are given about the solution mechanism of the fs‐laser‐irradiated polymer region. The experimental results are relevant for the fabrication of three‐dimensional (3D)‐structures in the volume of a transparent polymer material by fs‐laser irradiation. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 1229–1238, 2006     

Vaporized solvent bonding of polymethyl methacrylate

This investigation highlights rationale of vaporized solvent bonding for fabrication of transparent polymers such as polymethyl methacrylate (PMMA) in terms of optical transparency and bond strength. Vaporized solvent bonding is employed to fabricate the polymer, and its bonding characteristics with appropriate solvents are analyzed. It is observed that chloroform exhibits superior bonding characteristics in comparison with other solvents such as acetone, ethanol, and dichloromethane. In order to see the effect of prior surface modification carried out by ultraviolet (UV) irradiation and low-pressure plasma, surface energy of the polymer was estimated. It is observed that due to surface modification of PMMA by UV irradiation and low-pressure plasma, surface energy of the polymer increases considerably. However, due to exposure under UV irradiation and low-pressure plasma, molecular weight of PMMA decreases and atomic force microscopy (AFM) studies reveal that the topography of PMMA changes significantly resulting in deterioration of vaporized solvent bonding strength. Therefore, in the case of vaporized solvent bonding, increase in surface energy of the polymer is not a primary factor rather retention of molecular weight is more necessary.     

Surface modification of ABS by photocatalytic treatment for electroless copper plating

Surface roughness of acrylonitrile–butadiene–styrene (ABS) resin prior to metallization is treated generally with sulphuric/chromic acid system. However, the presence of chrominum (VI) ion imposes serious environmental problems. In this work, TiO₂ photocatalytic treatment was used to enhance the adhesion strength between the ABS surface and the electroless copper film. Effects of the TiO₂ content, irradiation time and UV power upon the surface topography, surface characterization and the adhesion strength were investigated. The results indicated that the surface hydrophilicity of ABS resin and the adhesion strength between the electroless copper film and ABS surface increased with an increase in the UV power and a prolongation in irradiation time, and did not increase linearly with an increase of TiO₂ content. Though the surface topography of ABS changed little, the adhesion strength reached 1.25?kN/m, which was higher than that in the optimal H₂SO₄–MnO₂ colloid. The surface chemistry results indicated that –COOH and –OH groups formed with the photocatalytic treatment and the absorption strengths increased with the UV power. XPS analysis results further demonstrated that the contents of C=O and –COOH reached 6.4 and 4.9% with the photocatalytic treatment, which was much higher than that of the H₂SO₄–MnO₂ colloid (3.9 and 3.1%). The high contents of C=O and –COOH groups enhanced the surface hydrophilicity of the ABS resin and improved the adhesion strength between the electroless copper film and ABS resin. The results indicated that the photocatalytic treatment was an environment-friendly and effective method to replace the commercial wet chemical process for ABS surface modification.     

Surface modification of ultra‐flat polydimethylsiloxane by UV‐grafted poly(acrylic acid) brushes

The graft density and surface topography of ultra‐flat polydimethylsiloxan films grafted with poly(acrylic acid) brushes by UV irradiation are investigated. The graft density keeps increase with the irradiation time and with the monomer concentration to a maximum, after which it remains unchanged in the former case or drops in the latter. Atomic force microscopy results show that a longer irradiation time, a higher monomer concentration and the addition of ethanol in the grafting solution are favorable to obtain the grafted polydimethylsiloxan films with flat surface. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Preparation of monodisperse magnetic polystyrene microspheres and its surface chemical modification

Monodisperse magnetic polystyrene (PS) microspheres were prepared in the presence of PS seed particles and styrene‐based magnetic colloid by the method of magnetic colloid swelling polymerization. The PS seed particles were prepared in advance by soap‐free emulsion polymerization. Styrene‐based magnetic colloid was used for swelling the PS seed particles in the magnetic colloid swelling polymerization process. After polymerization, functional amino groups were introduced onto the surface of the magnetic PS microspheres by surface Friedel‐Crafts acylation reaction. The morphology, size distribution, and magnetic properties of magnetic PS microspheres were characterized with scanning electron microscopy (SEM) and vibrating sample magnetometer (VSM), respectively. SEM showed that the magnetic PS microspheres had an average size of 1078 nm with a narrow size distribution. VSM showed that the magnetic PS microspheres were superparamagnetic, and saturation magnetization was found to be 5.714 emu/g. The concentration of functional amino groups on the surface of magnetic PS microspheres was measured by atomic absorption spectroscopy and UV−Vis spectroscopy, and the concentration of amino groups was found to be 0.168 mmol/g. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

PEEK的表面改性和表征

简要介绍了聚醚醚酮(PEEK)的一些特性及应用。综述了近年来用于PEEK薄膜表面改性的几种方法,包括等离子体处理、紫外辐照及湿化学法等。此外,简要概括了改性PEEK表面的表征方法,如扫描电子显微镜、X射线光电子能谱仪和原子力显微镜等。     

Surface modification of polyethylene by diffuse barrier discharge plasma

Low‐density polyethylene (LDPE) modified by atmospheric dielectric surface barrier discharge plasma in oxygen was investigated to improve surface properties and adhesion of LDPE to more polar polymers. The process of plasma modification was investigated using several methods—surface energy measurements, Fourier Transform Infrared Spectroscopy with Attenuated Total Reflectance (FTIR‐ATR), Scanning Electron Microscopy (SEM), and Atomic Force Microscopy (AFM). The surface energy of LDPE increased significantly after activation by oxygen barrier plasma even at very short time of modification. The FTIR‐ATR spectra manifested the presence of carbonyl functional groups on the surface of polymer pre‐treated by oxygen barrier plasma. It was shown by SEM, and AFM, that the topography of modified LDPE was significantly changed and the surface of modified polymer exhibited higher roughness in comparison with unmodified polymer. The surface energy of treated LDPE diminished in the course of ageing especially during the first 10 days after modification by barrier plasma. Hydrophilicity of the modified LDPE surface was stabilized by photochemical post‐functionalization with 2,2,6,6‐tetramethylpiperidin‐4‐yl‐diazoacetate. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Effect of chemical modification of oil fly ash and compatibilization on the rheological and morphological properties of low‐density polyethylene composites

In this study, the effect of oil fly ash (OFA), a by‐product of oil fuel power plants, on the rheological and morphological behavior of low‐density polyethylene (LDPE) is investigated. As received and acid‐functionalized OFA (COOH‐OFA) are used to examine the effect of surface modification of OFA on polymer–filler composites. LDPE/OFA composites were prepared by melt mixing with filler loading in the range 1–10 wt %. The results are compared with pure LDPE. The effect of polyethylene‐grafted‐maleic anhydride (PE‐g‐MA) as a compatibilizer was also studied. Both viscous and elastic properties of composites increased with OFA loading especially at low frequency. The surface modification of OFA has influenced the properties of OFA. As‐received OFA showed some agglomeration at high loading that resulted in two‐phase system as described by scanning electron microscopy (SEM) and Cole–Cole plot. Field emission‐SEM (FE‐SEM) images showed improvement in the dispersion of COOH‐LDPE/OFA composites. In addition, the surface modification reduced the size of agglomeration. In general, the COOH modification of OFA improved both the dispersion and rheological properties of OFA. With chemical modification, the concentration of the filler can be increased to 10% without compromising the properties of the composites. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Covalent immobilization of an antimicrobial peptide on poly(ethylene) film

An antimicrobial film was produced by covalently attaching synthetic peptide E14LKK to poly(ethylene) film. E14LKK is a 14 residue, magainin‐class peptide with broad‐spectrum antimicrobial activity. The poly(ethylene) surface was first oxidized with chromic/sulphuric acid, then PEGylated by using carbodiimide chemistry to attach ω‐amino‐α‐carboxyl‐poly(ethylene glycol) (PEG). The peptide was covalently coupled to the free terminus of the PEG, again using carbodiimide coupling. Surface contact angles for distilled water decreased from 101° initially to 61° following oxidation and 45° following PEGylation. Film surface chemistry showed the expected changes during the modifications: dye adsorption assays indicated changes in the number of acidic and basic groups and X‐ray photoemission spectroscopy showed increasing oxygen and nitrogen levels. Antimicrobial activity was demonstrated in broth cultures against E.coli: growth was reduced by atleast 3 log cycles compared to controls. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Surface Activation and Adhesion Properties of Wood-Fiber Reinforced Thermoplastic Composites

Four surface activation methods were evaluated on a series of wood-fiber reinforced thermoplastic composites (WPCs) as a means to improve the adhesion of a water-based acrylic coating. Treatments with chromic acid and oxygen plasma performed best, increasing the acrylic coating peel load to WPCs by 170 and 122%, respectively, and yielding adhesion levels equivalent to or higher than those obtained on wood. The benzophenone/ultraviolet and flame treatments also improved the coating adhesion by 100 and 64%, respectively, but did not reach the adhesion levels achieved on wood. For both the chromic acid and oxygen plasma treatments, the WPC formulation impacted the treatment efficacy. Profilometry and scanning electron microscopy (SEM) showed that the chromic acid treatment acted mainly by roughening WPC surfaces. While surface oxidation was not evident from attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), the improved wettability of WPCs with water suggested that the oxygen plasma treatment oxidized WPCs.     

Surface Activation and Adhesion Properties of Wood-Fiber Reinforced Thermoplastic Composites

Four surface activation methods were evaluated on a series of wood-fiber reinforced thermoplastic composites (WPCs) as a means to improve the adhesion of a water-based acrylic coating. Treatments with chromic acid and oxygen plasma performed best, increasing the acrylic coating peel load to WPCs by 170 and 122%, respectively, and yielding adhesion levels equivalent to or higher than those obtained on wood. The benzophenone/ultraviolet and flame treatments also improved the coating adhesion by 100 and 64%, respectively, but did not reach the adhesion levels achieved on wood. For both the chromic acid and oxygen plasma treatments, the WPC formulation impacted the treatment efficacy. Profilometry and scanning electron microscopy (SEM) showed that the chromic acid treatment acted mainly by roughening WPC surfaces. While surface oxidation was not evident from attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR), the improved wettability of WPCs with water suggested that the oxygen plasma treatment oxidized WPCs.     

Surface modification of UHMWPE fibers

Ultrahigh molecular weight polyethylene (UHMWPE) fibers have a high specific strength, high specific modulus, and outstanding toughness, but their poor adhesive properties has limited their use for composite material applications. In this research, the effects of chemical etching on the surface chemistry and topography have been explored using chromic acid, potassium permanganate, and hydrogen peroxide etching. The smooth surface observed on the as-received fiber was rich in ether and/or hydroxyl oxygen. This smooth surface resulted from the presence of an outer layer, a weak boundary layer, that was removed by all the etchants. A fibrillar structural hierarchy was revealed beneath this outer layer and the fiber was relatively unchanged by further etching. Chromic acid, the strongest etchant studied, produced a rough and oxidized UHMWPE surface with both ether and carbonyl oxygen. The combination of outer layer removal, roughness, and changes in oxygen bonding helps explain the improved adhesion on chromic acid etching in spite of the reduction in surface oxygen. Neither hydrogen peroxide nor potassium permanganate etching roughened or oxidized the surface to a great extent and neither yielded improved adhesion. © 1994 John Wiley & Sons, Inc.     

The influence of enzymatic treatment on the surface modification of PET fibers

The paper deals with the assessment of the surface modification of glossy continuous poly(ethylene terephthalate) fibers from the point of view of changes in their surface structure in terms of its micro‐topography and the molecular and supermolecular structure of the filament surface layers. The performed SEM and AFM investigations have shown differences in the fiber surface carving before and after modification (smoothing or increased roughness), depending on the type of applied enzymatic preparation. Measurements with the use of the ATR‐IR method have shown changes in the physicochemical character of the investigated fiber surface. The cleavage of the ester bonds in PET macromolecular chains, resulting from the modifications used, leads to the formation of reactive ? OH and ? COOH groups. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface modification of nylon 6 films treated with an He/O2 atmospheric pressure plasma jet

To investigate the effect of the gas composition of the plasma treatment on the surface modification of an atmospheric pressure plasma jet (APPJ), nylon 6 films were treated with APPJ with pure helium (He), He + 1% oxygen (O₂), and He + 2% O₂, respectively. Atomic force microscopy showed increased surface roughness, whereas X‐ray photoelectron spectroscopy revealed increased oxygen contents after the plasma treatments. The plasma‐treated samples had lower water contact angles and higher T‐peel strengths than the control. The addition of a small amount of O₂ to the He plasma increased the effectiveness of the plasma treatment in the polymer surface modification in terms of surface roughness, surface oxygen content, etching rate, water contact angle, and bonding strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011