Functionalization of HDPE powder by CF4 plasma surface treatment in a fluidized bed reactor

The surface of HDPE polymer powder was fluorinated by CF₄ plasma in a fluidized bed reactor. Plasma is generated by an inductively coupled electrode at 13.56 MHz (rf) frequency, connected to an auto matching network and an rf power generator. In plasma surface fluorination, the CF₄ gas is diluted with He gas. The experimental variables are treatment time and rf power. The chemical property of the modified powder has been determined by using ESCA and FTIR. Plasma surface fluorination with the powder in a fluidized bed reactor results from the formation of CHF-CF₂, CHF-CHF and CF₂ groups. These fluorine functionalities and the fluorine atomic ratio on the surface increase with the treatment time and rf power. It has been found that the composite parameter is a good measure for determining the effect of total energy input on the plasma surface treatment of polymer powder in a fluidized bed reactor.     

Experimental investigation into the effect of DC glow discharge pretreatment of HDPE on tensile lap shear strength

The present investigation aims to optimise the process parameters of DC glow discharge treatment through air in terms of discharge power and time of exposure for attaining best adhesive joint of high-density polyethylene (HDPE) to mild steel. The as- received and DC glow discharge exposed HDPE surfaces have been characterised by energy dispersive spectra (EDS). It is observed that with increasing power level up to 13 W, tensile lap shear strength of adhesive (Araldite AY 105) joint of HDPE to mild steel increases and then decreases. At 13 W power level, joint strength increases up to 120 s of exposure and then decreases. At the optimised condition for the surface modification, the effect of two different adhesives Araldite AY 105 and Araldite 2011 on the strength of polymer to mild steel, polymer to polymer and mild steel to mild steel joints have been examined. It is observed that tensile lap shear strength of HDPE–HDPE joint and HDPE–mild steel joint does not change with the change of adhesive and this could be possible as initiation of fracture takes place from subsurface layer of the polymer. This is confirmed by studies under optical microscopy and EDS, which shows when the polymer has been modified by exposure under glow discharge the failure is observed to initiate from subsurface layer of the HDPE, then within the adhesive cohesively and thereafter in the mild steel to adhesive interface.     

Surface modification of HDPE and PP by mechanical polishing and DC glow discharge and their adhesive joining to steel

To improve the strengths of the adhesive joints of high density polyethylene (HDPE) and polypropylene (PP) to steel, the surfaces of HDPE and PP sheets have been treated by DC glow discharge to increase the polar component of surface energy significantly. Present study investigates the effect of mechanical polishing prior to surface modification of substrates of HDPE and PP sheets by exposure to DC glow discharge, on the surface energy and their adhesive joint strength to steel. The mechanical polishing has been carried out by abrading with 120, 220, 400, 600, 800, and 1000 grade emery paper of grit sizes 8.33, 4.54, 2.5, 1.67, 1.2, and 1 micron, respectively. The surface energy of a given surface has been evaluated by measuring contact angles of sessile drops of two test liquids of known surface tension components, such as deionized water and formamide. It is observed that 800‐grade emery paper of grit size 1.2 micron has been found most effective in terms of their reduction in contact angles and enhancement of their surface energies. The change in surface energy due to surface modification has also been evaluated by measuring the surface energies of unpolished sheets exposed to DC glow discharge. The surface modification of the polymers by glow discharge for 120 s at a power level of 13 W decreases the contact angle more on mechanically polished specimens than that observed on unpolished sheets. Due to glow discharge treatment, the polar component of surface energy increases significantly in HDPE and PP, especially when they are mechanically polished (800 grade) prior to glow discharge. However, in case of the HDPE sheets, the effect of glow discharge on the polar component of surface energy is significantly higher compared to that for dispersion component of surface energy, whereas the polar component of surface energy of the PP sheet is lower than the dispersion component of surface energy. But in both the cases, mechanical polishing prior to glow discharge appears to affect the polar component of surface energy. Mechanical polishing of the HDPE and PP sheets by abrading with 800‐grade emery paper prior to glow discharge treatment, increases the adhesive joint strengths over those observed in case of unpolished polymers exposed to glow discharge. However, the use of prior mechanical polishing increases the joint strength only by a little more than 10% compared to a five to seven times increase in strength observed as a consequence of exposure to glow discharge of as received samples. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1140–1149, 2001     

用接触角法测量聚合物共混体系的表面性能

利用接触角的方法研究了聚合物HDPF、PET及其共混物HDPE／PET的表面自由能、极化度以及与不同液体一水和甘油间界面张力的大小。     

Adhesion modification of polyolefin surfaces with sodium hypochlorite in acidic media

Increased surface adhesiveness of HDPE is achieved by immersing it in an aqueous solution of sodium hypochlorite (bleach) mixed with an acid. This process results in the addition of functionality to the polymer surface vastly altering its adhesive, polarity and surface reactivity. Analysis of the modified polymer surfaces by ESCA has shown that chlorine atoms have been added to the surface. Studies regarding the chlorination of small molecules have also shown that the chlorination process is amenable to a variety of chlorination objectives and offers a route toward the functionalization of a variety of polymeric and non-polymeric substrates. In particular, this treatment renders unpaintable substrates such as HDPE more receptive to application of paints and adhesives. In this paper, we report the results of paint adhesion studies on treated polymer surfaces.     

Structural studies of electrochemically activated glassy carbon electrode: Effects of chloride anion on the redox responses of copper deposition

The redox behaviors of copper species at electrochemically activated glassy carbon electrodes have been investigated in aqueous solutions containing chloride anions. Experimental results showed that the voltammetric responses of copper species were influenced by the electrochemical activation means employed. Abnormal copper stripping was observed at electrodes obtained by cyclic polarization. Cyclic polarization would cause changes in the interwoven graphitic crystalline surface of glassy carbon, producing electrode interface with low distribution density of electron transfer sites for the early nucleation of metallic copper in the presence of chloride anion. Potentiostatic activation would generate oxygen-containing functionalities and maintain the basic surface structure of graphitic crystalline with high distribution density of electron transfer sites.     

Experimental investigation into the effect of adhesion properties of PEEK modified by atmospheric pressure plasma and low pressure plasma

High performance polymer, Polyether Ether Ketone (PEEK) (service temperature ?250°C to +300°C, tensile strength: 120 MPa) is gaining significant interest in aerospace and automotive industries. In this investigation, attention is given to understand adhesion properties of PEEK, when surface of the PEEK is modified by two different plasma processes (i) atmospheric pressure plasma and (ii) low pressure plasma under DC Glow Discharge. The PEEK sheets are fabricated by ultra high temperature resistant epoxy adhesive (DURALCO 4703, service temperature ?260°C to +350°C). The surface of the PEEK is modified through atmospheric pressure plasma with 30 and 60 s of exposure and low pressure plasma with 30, 60, 120, 240, and 480 s of exposure. It is observed that polar component of surface energy leading to total surface energy of the polymer increases significantly when exposed to atmospheric pressure plasma. In the case of low pressure plasma, polar component of surface energy leading to total surface energy of the polymer increases with time of exposure up to 120 s and thereafter, it deteriorates with increasing time of exposure. The fractured surface of the adhesively bonded PEEK is examined under SEM. It is observed that unmodified PEEK fails essentially from the adhesive to PEEK interface resulting in low adhesive bond strength. In the case of surface modified PEEK under atmospheric pressure plasma, the failure is entirely from the PEEK and essentially tensile failure at the end of the overlap resulting in significant increase in adhesive bond strength. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

不同基底材料复合电极对热再生氨电池产电性能的影响

针对热再生氨电池（thermally regenerative ammonia-based battery,TRAB）铜电极局部结构易被腐蚀断裂这一问题,构建了骨架结构相对较稳定的复合电极并应用于TRAB,研究了不同基底材料复合电极的电镀特性及其对TRAB产电特性和最大功率输出的影响。研究结果表明,与其他基底材料复合电极的电池相比,采用泡沫镍基底材料复合电极的TRAB虽电极表面积和镀铜量相对较小,但是具有较低的物质传输阻力和最小的欧姆内阻,从而获得最大的电压输出、最大的产电量和能量密度、最高的库仑效率和最高的功率输出（11.5 mW）。可见,泡沫镍作为TRAB复合电极的基底材料是一个相对较好的选择,同时需针对复合电极孔隙大小的影响规律开展后续研究。     

A Study of Ozone Formation on the Surfaces of Electrodes

It had been previously thought that ozone production occurred in gaseous space, especially the space between electrodes. However, based on our research, we believe that may only be one of the ozone-producing processes. In this study, we aimed to confirm that a third body, which is present at the interface between oxygen gas and a metal electrode, works to compose ozone. Ozone was not observed in pure oxygen (400x10^?6 Nm³/min flow rate) when electrical discharge was supplied after approximately 6 months. The concentration of ozone increased (approximately 0.07 ppm) when nitrogen (approximately 20x10^?6 Nm³/min flow rate) was added to a gas-mixing chamber. A third body was required to produce ozone when an oxygen molecule and an oxygen atom collided. The same phenomenon was observed on the surface of a copper anode. A simulation confirmed this. Using an industrial ozone generator which utilized ceramic dielectrics and expanded metal electrodes, an increase in the temperature of the cooling water led to a proportional decrease in ozone concentration. After changing from the titanium electrode to a nickel electrode and an antimony electrode, we observed the difference in the enthalpy changes which were calculated using van't Hoff's formula. The antimony electrode increases the efficiency of the ozone generator to produce ozone. We have come to believe that ozone can be composed on the surface of a metal electrode.     

Ethylene/ ammonia plasma polymer deposition for controlled adhesion of graphite fibers to PEEK

Plasma polymerization of ethylene and ammonia gas mixtures is used to obtain uniform polymer coatings on the surface of AS4 graphite fibers. The polymer deposition rates were determined for processing parameters such as composition of the monomer mix, monomer flow rate, chamber pressure, and power input of the radio frequency field. Plasma formed polymers were characterized using Fourier Transform Infrared (FTIR) and X-ray Photoelectron Spectroscopy (XPS). XPS spectra were collected at 75° and 30° takeoff angles to obtain elemental composition and functional group populations at different sampling depths. Plasma deposition rate was the smallest for 100% ethylene and increased by three to four fold when ammonia was added to the monomer mixture. The polymer coatings were of uniform thickness and exhibited a complex crosslinked structure. The 100% ethylene plasma polymer was strongly hydrocarbon in nature but had some oxygen and nitrogen containing groups. Plasma polymers from ethylene/ammonia mixture were much more polar and contained reactive and polar group constituents, including carbonyl, ether, primary and secondary amines, and hydroxyl groups. The presence of oxygen and nitrogen functionalities is presumed to arise primarily from the reaction of trapped radicals with oxygen and nitrogen when exposed to air. Small amounts of silicon were also detected in the plasma formed films.     

Evaluation of carbon electrodes and electrosynthesis of coumestan and catecholamine derivatives in the FM01-LC electrolyser

This work extends the range of electrodes and conditions under which the FM01-LC reactor has been used in a laboratory environment and evaluates the performance of carbon electrodes. Reticulated vitreous carbon (RVC) has been used to provide a stable, inert, three-dimensional electrode surface for organic electrosynthesis; its performance is compared to that of nickel mesh for the oxidation of catechol to o-quinone. This product was then reacted in situ with (i) 4-hydroxycoumarin and (ii) 1,3-dimethylbarbituric acid to produce, respectively, coumestan and catecholamine, products of synthetic interest. In mass transport experiments using hydroquinone oxidation as a model reaction, performance was similar to nickel electrodes, but Sherwood numbers were reduced by about 5–10% when carbon electrodes were used. The best-performing RVC electrode, however, showed poorer behaviour than its nickel counterpart. Yields for the production of coumestan and catecholamine were approximately 45% and 25%, respectively, although this was mostly due to extraction problems, since current efficiencies were both in the region of 65–70%. The electrode material, rather than the fluid flow behaviour, leads to a reduction in overall cell efficiency; this is confirmed by studies which show a film forming on the surface of the electrode.     

New Pathways for Modifying the Surface of High Density Polyethylene: Chemically Benign Adhesion Promotion and Subsequent Reactivity

Summary The surface of high density polyethylene (HDPE) was modified using a two-step chemical process. HDPE panels were initially immersed in a heated, aqueous hypochlorite solution containing a carboxylic acid promoter and quenched with deionized water at room temperature following a heterogeneous chemical reaction process patented by Beholz (U.S. Patents 6,077,913 and 6,100,343). 1-5 mole percent chlorine heteroatoms were identified on the resulting HDPE surface using ESCA techniques. The surface chlorine concentration was optimized as a function of reaction time, reaction stoichiometry and number of repeated chemical treatments. The chlorinated HDPE surface was subsequently exposed to ultra-violet (UV) light and surface alkene moieties were noted using ATR FT-IR methods along with a concomitant reduction in surface chlorine from ESCA measurements. The photochemically induced free radical surface dehydrochlorination mechanism was observed to follow first-order kinetics and potentially produce a focussed pattern for information storage. Facile subsequent reactivity of the isolated surface alkene groups was demonstrated using electrophilic addition of Br₂. Furthermore, poly(4-hydroxy styrene) architectures were covalently tethered to either the chlorinated or unsaturated HDPE surface in an effort to ultimately tailor surface polarity and adhesiveness as well as create laminate poly(-olefin) containing structures. This economical and benign surface chlorination/photochemical two-step treatment process produced relatively small disposal risks as well as no apparent polymer degradation.     

Electrochemical and XPS studies of the surface oxidation of synthetic heazlewoodite (Ni3S2)

X-ray photoelectron spectroscopic (XPS) and electrochemical techniques have been applied to the investigation of the surface oxidation of synthetic heazlewoodite (Ni₃S₂). The XPS data showed that exposure of the sulphide to air resulted in nickel atoms migrating to the surface to form an overlayer of a hydrated nickel oxide and leave a sulphur-rich heazlewoodite. A hydrated nickel oxide was also produced on immersion of heazlewoodite in acetic acid solution in equilibrium with air, despite nickel being soluble under these conditions. After the acetic acid treatment, the S(2p) spectrum had a component at the binding energy of NiS and a small contribution due to sulphur-oxygen species. Voltammetry with bulk heazlewoodite electrodes, and the ground sulphide in a carbon paste electrode, indicated that, at pH 4.6, the initial anodic product was a sulphur-rich heazlewoodite and that oxidation was inhibited when NiS was formed on the surface. Further oxidation to higher nickel sulphides and elemental sulphur occurred at high potentials. In basic solutions, oxidation was restricted due to the formation of nickel oxide.     

Functionalization of Polymer Surfaces Using Excimer VUV Systems and Silent Discharges. Application to Electroless Metallization

New approaches for electroless plating of nonconductive polymers or polymer-based materials are described. In this work, polyimide substrates were surface-functionalized (i) in nitrogenated (ammonia at reduced pressure) and oxygenated (air at atmospheric pressure) atmospheres under assistance of vacuum-ultraviolet (VUV) irradiation (use of a xenon silent discharge excimer source) or (ii) directly in air at atmospheric pressure using a dielectric-barrier discharge (DBD) device. After functionalization, the substrates were “activated” by dipping in a dilute acidic PdCl₂ solution or by spin-coating of a thin metal-organic film (from a solution of palladium acetate (PdAc) in chloroform). The catalytic activity of the so-deposited palladium species toward the electroless deposition of nickel was studied before and after a VUV post-irradiation (in air at atmospheric or reduced pressure) with a view to understanding better the role of the reducer (sodium hypophosphite) within the electroless bath.

This work confirms the specific interest of grafting nitrogenated functionalities onto polymer surfaces for attaching covalently the palladium-based catalyst (in particular in the case of the PdCl₂ route), forming thus strong Pd - N - C bonds at the metal/polymer interface. This results from the strong chemical affinity of palladium toward nitrogen. On the other hand, when oxygenated functionalities are surface-grafted, the conventional two-step procedure using SnCl₂ and PdCl₂ solutions can be proposed due to the strong chemical affinity of tin toward oxygen. The Ni deposits obtained under these different conditions pass the standard Scotch^®-tape test and, therefore, exhibit a good practical adhesion. For this same purpose, it is interesting to note that the DBD treatment operating in air at atmospheric pressure causes an increase of the surface roughness and, therefore, an improvement in adhesion of metallic films when their initiation is catalyzed through the PdAc route. In addition, this work demonstrates that extensive research still has to be performed to understand and improve the Ni/polymer adhesion when the PdAc route associated with a VUV irradiation is considered.     

An XPS study of argon ion beam and oxygen RIE modified BPDA-PDA polyimide as related to adhesion

Modification of polymer surfaces by changing the chemical structure, surface energy, and bonding characteristics has considerable technological importance in the area of adhesion. Reactive ion etching (RIE) and ion beam (IB) bombardment were employed to modify the surfaces of fully imidized 3,3',4,4'-biphenyl tetracarboxylic acid dianhydride-p-diaminophenyl (BPDA-PDA)-based polyimide (PI) films. These modification techniques affect only a shallow surface region, approximately 10-20 nm, and the bulk properties of the polymer are unaffected. The angle-resolved X-ray photoelectron spectroscopy (XPS) technique was used to characterize the PI surfaces modified by argon IB bombardment or oxygen RIE treatment. On the argon ion-bombarded surfaces, the XPS spectra indicate that the carbonyl and imide groups are decreased. Oxygen RIE treatment resulted in an increase in the atomic concentration of oxygen. To understand the surface aging effect, the freshly modified PI surfaces were exposed to laboratory air for 1 and 2 days. The changes in composition as a function of the depth of the modified surface region right after treatment and after aging were determined by the angle-resolved XPS technique (ARXPS). Contact angle measurements were used to determine the polar and dispersion components, the sum of which is the surface free energy. The polar component of the surface free energy shows the greatest change, with an increase of 8.0-9.4 times for both the oxygen RIE and ion beam treatments as compared with the as-cured PI surface. Aging of these modified surfaces resulted in a decrease of surface free energy as compared with the just-modified surfaces. In the case of oxygen RIE treatment, the dispersion component of the surface free energy showed little or no change from the as-cured sample. Adhesion of chromium/copper/chromium (Cr/Cu/Cr) films on PI was determined by peel strength measurements. Significant increases in peel strength, by a factor of 10-80, were shown for the modified surfaces. A good correlation between the peel strength and the experimentally determined polar component of surface energy was shown.     

Effects of moisture on interface modified graphite epoxy composites

Graphite epoxy composites which are exposed to high humidity environments suffer a loss in their shear and transverse properties. In addition to the effect of moisture on the matrix, thermodynamic theories suggest that the interface may suffer irreversible damage. In this study, we investigated if fiber surface treatments could improve fiber matrix adhesion as well as the wet composite properties. Plasma polymerization was used to generate very thin coatings with the polar component of the surface energy varying from 1.8 to 5.3 (dyne/cm)^1/2. These coatings were characterized by ESCA and SEM, and a micro-Wilhelmy technique was used to determine the dispersive and polar components of the surface energy. The uniaxial composites made with the treated fibers were tested wet and dry in short beam shear. It was found, as is well known, that the dry shear properties could be improved by up to 40 percent. Two effective treatments were oxygen etching and polymerization with methylmethacrylate monomer. However, all the wet samples failed at the same stress regardless of the surface treatment used. These results strongly suggest that the shear and transverse properties of the wet composites are dominated by the epoxy and cannot be improved by interface treatments.     

The role of iron in the prevention of nickel electrode deactivation in alkaline electrolysis

There is some uncertainty concerning the role of iron deposits on the surface of nickel electrodes with respect to electrode activity during alkaline water electrolysis. Iron deposits variously have been reported to enhance nickel electrode activity by providing additional surface area from electrolytic deposition of solution phase iron species or to depassivate nickel electrodes via a surface interaction effect. In this study, nickel electrodes were sputtered with a smooth iron layer to determine the effect of metallic iron on the electrode surface without significantly changing the electrode surface area. A permeation cell with 8 mol/L KOH at 70 °C was used to follow nickel electrode potentials during hydrogen evolution while the permeation current was used to detect changes in the electrode structure.Short term measurements reveal no difference in behavior of coated and non-coated electrodes. Longer term results showed that a metallic iron coating on nickel electrodes prevented deactivation of the electrodes. The deactivation effect was associated with an increased hydrogen flux through the electrodes indicative of an elevated hydrogen concentration at the electrode surface. This high surface concentration is concluded to be the result of nickel hydride phase formation at the surface of the nickel electrodes. The iron coating prevents this surface phase from forming and hence prevents deactivation of the electrode.     

Complex-induced coupling effect: adhesion of some polymers to copper metal promoted by benzimidazole

Improved adhesion of a polymer with polar functional groups to copper has been achieved by pretreating the copper surface with benzimidazole solution. The adhesion strength was found to increase by two to three times. The coupling mechanism and interfacial structure of the copper-polymer composite have been investigated by X-ray photoelectron and Fourier transform infrared relection-absorption spectroscopies. We found that benzimidazole reacted with copper metal in the presence of oxygen to form benzimidazolato copper(+1), which covered the surface in the form of a thin polymeric layer. As the surface was exposed to air, some of the cuprous cations were oxidized to cupric ions. When poly(vinylpyridine) was coated onto the pretreated surface, the nitrogen atoms of the side groups of the polymer chains co-ordinated to the cupric cation to form interfacial bonding connecting the polymer to the copper metal.     

A novel plasma-enhanced way for surface-functionalization of polymeric substrates

Summary In this contribution a novel, low-pressure RF-plasma-enhanced approach is suggested for the surface functionalization of polymeric substrates. The method takes advantage of the high reactivity Ar-plasma generated free radical sites located on PE substrate surfaces, which can promote under in situ conditions, heterogeneous chemical reactions with stable gas-phase molecules, such as 1,3 diamino propane, in the absence of plasma. The presence of covalently attached primary amine functionalities was demonstrated by fluorescamine-labeling technique, further oxallyl chloride-based derivatization, and immobilization of horseradish peroxidase. The existence of specific functionalities on modified PE surfaces at different derivatization stages, was evidenced by ESCA, ATR-FTIR, and enzyme assay tests. Received: 16 May 2001/Revised version: 17 July 2001/Accepted: 19 September 2001