Facile preparation of bimodal polyethylene with tunable molecular weight distribution from ethylene polymerization catalyzed by binary catalytic system in the presence of diethyl zinc

A series of novel honeycomb films of tri- and octa-arm polystyrene-b-poly(tert-butyl acrylate) star polymers prepared by atom transfer radical polymerization and nitroxide mediated radical polymerization, respectively, have been fabricated. The type of solvents, specifically their miscibility in water is one of essential parameters to construct ordered pore structures. The tri- and octa-arm star polymers yield well-ordered microporous film specifically in 10 to 30 g/L CHCl₃ solution. The contact angle of glass slide substrate (54.57°) is adjusted to 41.06° by plasma treatment and to 12.21° by coating the glass slide with highly hydrophilic hyperbranched polyglycidol. The ordered honeycomb films are created on the hydrophobic substrates, but the ordered films are not formed on the hydrophilic substrates. Microspheres with the diameters ranging from hundreds of nanometers to several micrometers are also obtained by a slight modification of breath figure method.     

Ice adhesion to rubber materials

The aim of this study was to investigate the interfacial shear strength between ice and rubbers. Different rubber materials containing only a polymer and curing agent (peroxide) were tested with regard to surface wettability and interfacial shear strength. The effect of different grades and amounts of carbon black filler was also studied. The wettability was determined from contact angles, using water and diiodomethane as test liquids, measured on carefully cleaned and mirror smooth rubber sheets. The test showed that there is a correlation between ice adhesion and rubber substrate wettability. Below a water contact angle of 90°, the interfacial shear strength of ice decreases linearly with increasing contact angle. For contact angles above 90°, the interfacial shear strength of ice stays practically the same. The presence of high surface energy additives such as reinforcing carbon black (e.g. N220 ISAF) significantly increases the interfacial shear strength. The highly hydrophobic behaviour of different plant surface textures was also investigated regarding ice adhesion strength. The combination of a submicrometer textured surface and a hydrophobic surface characteristic showed an abrupt decrease in the adhesion force of a water droplet at measured macroscopic contact angles above approximately 150°. Despite this water repellency, the ice adhesion strength is not nil. However, it was among the lowest values experienced in the test.     

Properties of composite films comprising surface modified fine collagen particles dispersed in polyurethane matrix

Collagen-rich natural leather powders (PPd) with average particle size of 12 μm were modified and dispersed in a polyurethane (PU) matrix. Three kinds of surface modification techniques were employed; surface polyaddition of PU, copolymerization with acrylamide (AAm), and grinding of the PPd with PU powder in a planetary ball mill. Surface modification was confirmed mainly by FTIR signals from the modifier. The DTA exothermic peak shifted toward a higher temperature by 260 K when copolymerized with AAm. On the copolymerized sample, the IR peak due to C(DOUBLE BOND)O stretching appeared between those of the original AAm and PPd, indicating the mutual chemical interaction. The tensile yield stress and critical strain of the composite films increased by surface modification with PU, while the latter decreased for the film containing the PPd powders copolymerized with AAm. Judging from the micrographs of the expanded films, the increase in the adhesive strength between the powder surface and the matrix after modification by AAm was larger than those by PU. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 63: 1693–1700, 1997     

Design factors for reducing ice adhesion

The purpose of this study was to investigate the relationships between a type of engineering material and the ice adhesion strength while in direct application in icing conditions. Ice adhesion tests were conducted on various materials with different surface conditions. There is an identified need for systematic studies on the effects of varying surface conditions with well-characterized roughness and accurate adhesion measurement. This information is key in understanding the adhering behaviour of ice which is a necessary prerequisite for modelling the behaviour of ice adhesion to other surfaces and for icing prevention. Results show that the type of material will determine, in large, the strength of the ice adhesion between surfaces with similar roughness characteristics and the receding contact angle of water can be used as a predictor of relative ice adhesion. The adhesive strength of ice can be increased or decreased dramatically by means of adjusting the surface roughness with a uniform process. Each material tested exhibits a similar linear relationship. There was a stark contrast in the ice adhesion between the varying materials despite very similar polished surface conditions and static water contact angles. Ice bonded to the glass surface with an adhesion of 1562 ± 113 kPa, and to aluminum at 1039 ± 117 kPa, and stainless steel at 1022 ± 115 kPa, and finally Teflon at only 33 ± 52 kPa and during 80% of trials the ice/substrate interface was broken with no measured adhesion. The information gathered can be used to improve designs for a number of devices needed in cold weather climates.     

Effects of wood-surface roughness,adhesive viscosity and processing pressure on adhesion strength of protein adhesive

The objective of this research was to study the effects of wood-surface roughness, adhesive viscosity and processing pressure on adhesion strength between soybean protein adhesive and wood, and to seek the relative importance of the individual factors in determining adhesion strength. Processing pressure was found to be the most important factor in determining adhesion strength. An optimum pressure, which was about 4.55 MPa in this research, is needed for development of a strong bond. A higher pressure resulted in reduced adhesion strength, possibly due to damage to the wood surface; a lower pressure also resulted in decreased adhesion strength because of the lack of bond formation. Adhesive viscosity had greater effect on adhesion strength than surface roughness. Contact angle, which was found to be mainly determined by adhesive viscosity and surface roughness, was a major factor controlling adhesive penetration. A smaller contact angle, resulting from lower viscosity and rougher surface, produced deeper penetration, while a larger contact angle, resulting from higher viscosity and smoother surface, produced shallower penetration. An optimum penetration is needed to enhance adhesion strength by developing a three-dimensional interactive zone at the interface. Too deep or too much penetration would result in 'dry-out' at the interface; less penetration would limit the formation of the three-dimensional zone at the interface. Both cases resulted in reduced adhesion strength. Contact angles ranging from 35 to 47° provided the optimum penetration needed for good adhesion. The results of this research could be used as reference to determine optimum process parameters in plywood manufacturing when an aqueous based adhesive is used.     

PDA/SiO2改性聚氨酯制备含结构色复合材料

采用改良St?ber法制得187、245、274 nm 3种粒径的SiO2微球，使用聚多巴胺（PDA）对SiO2微球进行包覆，制备了蓝色、绿色、红色3种不同颜色的非晶光子晶体PDA/SiO2（APCs）；将非晶光子晶体PDA/SiO2引入聚氨酯（PU）制得复合材料PDA/SiO2/PU 。利用FT-IR、CA、SEM、TEM、UV-Vis、DLS及万能试验机对PDA/SiO2及复合材料PDA/SiO2/PU的结构与性能进行表征分析。结果表明：APCs的颜色取决于SiO2微球的粒径；通过调节PDA的包覆量可调整APCs的色彩饱和度；APCs引入PU后可得到呈暗红结构色聚氨酯，其最大拉伸强度可达40.28 MPa，水接触角达113°，使得聚氨酯具有结构生色性和优异的机械性能与疏水性。     

Hydrophilic and hydrophobic poly(l‐lactic acid) films by building porous topological surfaces

Surface wettability of thin films is significant for their functional properties. Poly(l ‐lactic acid) (PLLA) is proposed as film matrix for building porous topological surfaces. By controlling the dope composition and ambient conditions, the films with ordered pores at micrometer scale are obtained. The results demonstrate that the hydrophilic or hydrophobic surface can be realized by building the porous topological surfaces. Increasing polymer concentration can lead to decreased pore size. The transition behavior of surface pores from discrete bowl‐like to interconnected honeycomb‐like structure with the increasing humidity is observed. The contact angle of top surface of film is higher than that of bottom surface, which verified the different roughness performance. The morphology and scale of topological structure are markedly related with the template effect of water droplets. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44572.     

Underwater polyurethane adhesive with enhanced cohesion by postcrosslinking of glycerol monomethacrylate

Polyurethane (PU) has been widely used as a glue in various areas. However, adhesion in the presence of water is greatly impeded and results in most synthetic adhesive failure. In this study, we designed and synthesized a novel PU construction; underwater PU adhesives were created by the incorporation of synthetic glycerol monomethacrylate (GMA). Furthermore, the urethane structure helped the adhesive eliminate the interfacial water barrier through interactions that were stronger than hydrogen bonding, and GMA as a crosslinking agent was used to generate post‐covalent‐crosslinking networks through radical polymerization. This enhanced the cohesion so the diffusion of water molecules could be overcome. Fourier transform infrared spectroscopy, thermogravimetric analysis, underwater adhesion measurements, and tensile tests were used to characterize the chemical and mechanical properties of the as‐obtained adhesive. This led to an adhesive with a better mechanical strength and interfacial adhesion in water, and the results show that the mechanical properties (tensile strength, Young's modulus, and tensile elongation) of the GMA–PU adhesive were higher than those of the pure PU. As for the 4% GMA, the tensile strength was enhanced by 24.3% and the elongation was enhanced by 125.23% over those of the pure PU. This confirmed that the incorporation of GMA into the PU matrix indeed induced increasing cohesion, and the sample's adhesive strength was 21.19 ± 3.9 MPa; this indicated a superior adhesive strength over that of the pure PU. In addition, we can foresee that underwater adhesion will play an important role in prospective surgery and engineering areas. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46579.     

Hemocompatibility evaluation of polyurethane film with surface‐grafted poly(ethylene glycol) and carboxymethyl‐chitosan

To improve the hemocompatibility and biocompatibility of polyurethanes (PUs), PU surface was firstly modified by poly(ethylene glycol) PEG through acryloyl chloride and subsequently grafted on carboxymethyl‐chitosan (CMCS). Attenuated total reflection Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy analysis confirmed that carboxyl‐chitosan was grafted onto PUs surface. The surface properties of unmodified and modified PU films were determined and compared by water contact angle assessment. After PEG and CMCS grafting, the surface energy of the PU film was increased. Furthermore, the hemocompatibility of the modified PU films was systematically evaluated by bovine serum albumin (BSA) adsorption, the dynamic blood clotting test, the platelet adhesion test, and the hemolytic test. It appears that BSA adsorption and platelet adhesion were significantly curtailed for the modified PU films. Therefore, the obtained results showed the modified PU film has better hemocompatibility. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Enhancing adhesive joints between commercial rubber (SBS) and polyurethane by low-pressure plasma surface modification

The paper presents research on the two-stage process of low-pressure plasma surface modification of a commercial SBS rubber, improving its adhesion to both the polyurethane adhesive in an organic solvent (PU) and the aqueous polyurethane adhesive dispersion (ADPU). The plasma surface modification process was carried out in a flow reactor with parallel plate electrodes, in which plasma was generated by an RF glow discharge (13.56 MHz). In the first stage of the process, the Ar or O₂ plasma was used, and then, as the second stage of the modification process, the treatment was performed in H₂O plasma. The adhesive properties of the plasma-modified SBS rubber surface were determined using the 180^o-peel strength test (PS). These results were correlated with surface properties investigated using contact angle (CA) measurements, FTIR-ATR spectroscopy, XPS spectroscopy and scanning electron microscopy (SEM). The observed improvement in wettability of the plasma modified surface was attributed to the formation of hydroxyl groups, which was confirmed by spectroscopic methods (FTiR-ATR and XPS). The results of the 180^o-peel strength test showed, in turn, a clear relationship between the capacity of adhesive bonding and the amount of oxygen groups (mainly the hydroxyl groups) as well as the surface roughness, determined by SEM microscopy. It was also found that the effects of the plasma surface modification of the SBS rubber were stable for at least 72 h. The results of this work prove that cleaning and etching of the commercial SBS rubber surface in the first stage of its plasma treatment, followed by chemical modification in the second stage, lead to very strong adhesive joints.     

Adhesive and repulsive properties of water droplet impact on honeycomb surfaces through breath figure method

The honeycomb porous films of tadpole‐shaped polyhedral oligomeric silsesquioxane fluorinated acrylates copolymers were fabricated through breath figure method. The static hydrophobic properties were studied through water contact angles (CAs) and the rim width/pore size (W/D) values. It was found that the low W/D value and high fluorine content generally indicated a high water CA. The properties such as morphology variations, energy conversion, contact diameter, adhesive, and repulsive forces were investigated on the porous and pincushion films. Furthermore, the kinetic energy of the droplet was converted into surface energy and internal energy dissipation after it impacted the surface. The residual energy made the droplet to recoil and influenced the bouncing height. The contact diameter and bouncing height characterized the energy level of the surface, and determined the surface energies of the copolymer/water/air system as well as the wettability. Finally, the adhesion and repulsion of water droplet on different surface at the times of establish contact, maximum contact diameter, and maximum bouncing height were compared. This work was helpful for us to further understand and control the adhesive force and the repulsive force on the porous and pincushion structure films. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45476.     

The influence of temperature and cyclic loading on adhesion in polycarbonate-polyurethane-glass adhesive joint

The paper deals with the influence of temperature and cyclic loading on adhesion and transparency of the adhesive joint consisting of soda-lime-silica glass and polycarbonate (PC) bonded with polyurethane (PU) adhesive film. The tested joint represents critical part of transparent armored glass used in vehicles. Dynamic tension creep tests were performed at temperatures to which armored glass is commonly exposed (25, 50, 60, 70, and 80?°C). Sawtooth loading mode was performed to 650?N and the sine loading in the force range 0–1550?N. The aim of the paper was to discover conditions causing delamination of the adhesive joint and glass milky appearance during the use. Delamination of soda-lime-silica glass/PU adhesive interface occurred at 25?°C after load to 1550?N without the change of transparency. Both dynamic and static tension creep tests performed to 400?N led to plastic deformation of PU adhesive at and above 70?°C, in preference at both ends and circumference edges of adhesive joint, and thus, to loss of transparency, but extent of deformation differed. Milky maps observed after sawtooth load to 650?N at 80?°C reflected delaminated areas of highly deformed PU adhesive. Temperature of 70?°C was found out to be the critical parameter being in synergy effect with different thermal expansion of PC and PU adhesive.     

Development of improved polypropylene adhesive bonding by abrasion and atmospheric plasma surface modifications

The present work deals with the problematic adhesive bonding of substrates with low surface energy. Different approaches have been explored with the aim of creating adequate adhesive joints based on polyolefinic substrate and polyurethane adhesive. The selected material under study was polypropylene (PP) as adherend, and a commercial Sikaflex^®-252 polyurethane one component based structural adhesive (PU) as joint fluid. Among the diverse pre-treatments typically used to prepare surfaces prior to bonding, mechanical abrasion with emery paper of 80 grain size, the use of a chemical primer and atmospheric pressure air plasma torch (APPT) were the selected methods to facilitate the application of the PU by means of surface energy enhancement as well as to create a correct mechanical interlocking of the adherent–adhesive interface. Changes in the wettability of the polymer were evaluated by contact angle measurements following the UNE EN 828:2010. Surface energy was calculated both in terms of Owens approximation and acid–base considerations, leading to the possibility of determining a relationship between changes in surface energy and adhesion. Changes in the chemical composition of the surface were studied by X-ray photoelectron spectroscopy (XPS), electron diffraction X-Ray (EDX) probe and attenuated total multiple reflection mode infrared spectroscopy (ATR-FTIR). Morphological modifications were investigated with scanning electron microscopy (SEM). Variations in the strength of single-lap PP–PP joints with the treatments were evaluated by lap shear tests following the UNE-EN 1465:2008 standard. Experimental evidence supports the superiority of the APPT treatment to increase wettability and adhesion of polyolefinic surfaces, especially when combined with the use of a primer.     

Some Effects of Corona Discharge Treatment of Biaxially-Oriented Polypropylene Film

The effects of the unit corona-treatment energy on the contact angle of various liquids, on the surface free energy, on the extent of oxidation of a surface layer, and on the adhesion of acrylic adhesive were studied using a biaxially-oriented polypropylene (BOPP) film. The surface free energy was determined with the van Oss-Chaudhury-Good (VCG) approach as well as with the wettability method. The extent of oxidation of the surface layer of the corona-treated BOPP film was evaluated with X-ray photoelectron spectroscopy. The adhesion strength of joints between the BOPP film and the acrylic adhesive was measured using the 180°-peel test.

In the range of the unit corona-treatment energy up to 1.2 kJ/m², a rapid increase in the surface free energy with the treatment energy is observed. In the range above that value, the surface free energy rises relatively slowly. The extent of oxidation of the surface layer and the adhesion strength of joints between the BOPP film and the acrylic adhesive are approximately in direct proportion to the unit energy of the corona treatment. A five-fold growth of the adhesion strength of the studied joints within the examined range of the treatment energy was found.     

Study of the correlation between flexible food packaging peeling resistance and surface composition for aluminum-metallized BOPP films aged at 60°C

ABSTRACT

This study investigated the correlation between surface composition and peeling resistance in food packaging films by studying the heat aging of fabricated films over varying periods of time. The films consisted of a layer of aluminum (Al) metallized, biaxially oriented polypropylene (BOPP) bonded with a polyurethane (PU) adhesive onto another polymeric layer of low-density polyethylene (LDPE). The Al metallized films were prepared by physical vapor deposition (PVD) and aged at 60°C for either 5 or 15 days. The resulting aluminum surfaces were analyzed using X-ray photoelectron spectroscopy (XPS) and found to contain aluminum oxide (Al₂O₃) and trihydroxide (Al(OH)₃). The XPS characterization also revealed a 29% increase in the Al(OH)₃ layer thickness of the aged sample relative to a non-aged sample. Atomic force microscopy (AFM) was applied on investigations of possible morphology changes. The aluminum and PU adhesive surface energies were also determined using contact angles measurements and the aluminum surface energy was found to increase by as much as 11.7% compared to the non-aged sample, while the PU adhesive surface energy was at least 65% higher than that of the metallic substrate. The peeling resistance of the laminated aluminum was determined by average peel strength measurements and it was found that the variation in peel strength was related to changes in the Al₂O₃ layer thickness. The delaminated samples were analyzed using scanning electron microscopy/energy dispersive X-ray spectrometry (SEM/EDS) and showed the cohesive failure of the aluminum film.     

Improved adhesion of EVAs with different vinyl acetate contents treated with sulphuric acid

Four ethylene vinyl acetate copolymers (EVAs) containing 9, 12, 18 and 20 wt% vinyl acetate (VA) were treated with concentrated sulphuric acid to improve their adhesion to polychloroprene (PCP) adhesive. The tensile strength and Young's modulus of EVAs decreased as the VA content increased, due to the reduction in crystallinity of the polyethylene blocks in the copolymer. The modifications produced in the EVAs by treatment with sulphuric acid were followed using contact angle measurements (water, 25 °C), ATR-IR spectroscopy and scanning electron microscopy (SEM). Adhesive-bond strength was obtained by T-peel tests on treated EVA/polychloroprene adhesive joints. The vinyl acetate content in the EVA affected the extent, but not the nature, of the surface modification produced by treatment with sulphuric acid. The treatment produced both sulfonation and oxidation on the EVA surfaces. The higher the vinyl acetate content in the EVA, the more significant the modifications produced. Increased T-peel strengths of EVA/polychloroprene adhesive + 5 wt% polyisocyanate joints were obtained and a mixed failure (adhesion failure + cohesive failure in the adhesive) was produced. It was found that, to be effective, the treatment of EVAs must be carried out with 96 wt% sulphuric acid.     

Effect of Temperature on the Joints Strength of an Automotive Polyurethane Adhesive

In this paper, the performance of an automotive polyurethane adhesive was studied through adhesive joints tests. Butt joints and single lap joints were fabricated and tested at seven temperature measuring points (TMPs). It is shown that both the tensile strength and lap shear strength decrease with the increasing of temperature. Quadratic polynomial expression obtained by the least square method can represent the tensile and lap shear strength as a function of temperature very well. ?40°C, 0°C, and 90°C were selected as the most ideal TMPs for this adhesive through the comparison of the residual sums of squares of 35 fitting curves with different combination of TMPs. Scarf joints with adhesive angles of 60° and 30° were fabricated and tested at ?40°C, 0°C, and 90°C. It also showed a decrease in joint strength with the increasing temperature. Joint strength as a function of adhesive angle is presented. It was found to closely follow a linear behaviour. A three-dimensional surface, consisting of temperature, adhesive angle, and joint strength, is presented finally to facilitate the design of automotive bonding structures.     

Fabrication of biomimetic gecko toe pads and their characterization

The mimicking and fabrication of gecko toe pads structures can lead to limitless applications. In this study, polypropylene (PP), polyethylene (PE) and polycaprolactone (PCL) nano‐fibers are fabricated using a porous membrane as template. The surface characteristics and physical properties of the samples yield different geometries, which determine the wetting and adhesive properties of the fabricated samples. Oriented and wave‐like shapes fibers present the Gecko effect, thanks to their ability to comply and hydrophobic asperities that uphold the water droplet when the wetting properties were tested. The samples are also found to be self‐cleaning due to their high contact angles and low contact angle hysteresis. Adhesion tests results prove that the samples are high reversible adhesion with the ability to stick to smooth surface in a dry and underwater environment. The adhesion on the samples can be enhanced with a double fibril layer or buckling property. They adhere better when the surface is not hydrophilic. By behaving in similar way as the real geckos, the results of this study show that the fabricated samples effectively present the Gecko effect. POLYM. ENG. SCI., 57:283–290, 2017. © 2016 Society of Plastics Engineers     

The effect of TiO2 morphology on the surface modification of poly (ethylene terephthalate) for electroless plating

In this study, a surface modification of the poly (ethylene terephthalate) (PET) film using TiO₂ photocatalytic treatment was investigated. In order to enhance the adhesion strength between the PET film and the electroless copper film, the effects of TiO₂ crystal forms, TiO₂ particle sizes, and TiO₂ content, as well as treatment condition, upon the surface contact angle, surface characterization, and adhesion strength were investigated. Anatase TiO₂ with a particle size of 5 nm had a high catalytic activity and dispersibility in aqueous solution. After the optimal photocatalytic treatment, the surface contact angle of the PET film decreased from 84.4° to 19.8°, and the surface roughness of the PET film increased from 36 to 117 nm. The adhesion strength between the PET film and the electroless copper film reached 0.89?KN?m^?1. X-ray photoelectron spectroscopy analyses indicated the carbonyl group was formed on the PET surface after photocatalytic treatment, and the surface hydrophilicity was improved. Consequently, TiO₂ photocatalytic treatment is an environmentally friendly and effective method for the surface modification of the PET film.     

Prevention of Ice Accretion on Aluminum Surfaces by Enhancing Their Hydrophobic Properties

The accretion of ice on the surfaces of power network systems, aircraft, communication networks, etc., is known to cause serious problems that often lead to costly safety issues. An ideal solution would be to prevent ice from accumulating in the first place, rather than waiting for ice to accrete and then to de-ice which is both time-consuming and expensive. This may be accomplished by depositing coating materials that are icephobic. A low dielectric constant surface is expected to reduce the adhesion of ice due to the screening of mirror charges, thereby eliminating one of the strongest interaction forces — the electrostatic force of attraction — at the ice–surface interface. Superhydrophobic surfaces, which demonstrate high water-repellency due to the negligible contact area of water with these surfaces, are also expected to minimize the contact area of ice. In the present research work, both concepts were studied by producing superhydrophobic nanorough low-ε (dielectric) surfaces on aluminum. Superhydrophobic properties were achieved on surfaces of aluminum by creating a certain nanoroughness using a chemical etch followed by 'passivation' of the surface by a low surface energy coating of rf-sputtered Teflon, providing a water contact angle greater than 160°. The same behavior is reported even when the nanorough substrates were coated with dielectric thin films of ZnO (lower ε) or TiO 2 (higher ε) prior to passivation. It is found that the superhydrophobic nanorough low energy surfaces are also icephobic and the presence of a low dielectric constant surface coating of Teflon (ε = 2) allows a considerable reduction of the ice adhesion strength. Ice adhesion strengths were determined using a centrifugal ice adhesion test apparatus.