Physical-morphological and chemical changes leading to an increase in adhesion between plasma treated polyester fibres and a rubber matrix

The effects of plasma treatment, used to increase adhesion strength between poly(ethylene terephtalate) (PET) fibres and a rubber matrix, were investigated and compared. Morphological changes as a result of atmospheric plasma treatment were observed using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Wettability analysis using a surface energy evaluation system (SEE system) suggested that the plasma treated fibre was more wetting towards a polar liquid. When treated, these fibres showed a new lamellar crystallization, as shown by a new melting peak using differential scanning calorimetry (DSC). X-ray photoelectron spectroscopy (XPS) has been used to study the chemical effect of inert (argon), active and reactive (nitrogen and oxygen) microwave-plasma treatments of a PET surface. Reactive oxygen plasma treatment by a de-convolution method shows new chemical species that drastically alter the chemical reactivity of the PET surface. These studies have also shown that the surface population of chemical species formed after microwave-plasma treatment is dependent on the plasma gas. All these changes cause better adhesion strength of the PET fibres to the rubber matrix.     

Carbon nanotubes as reinforcement of styrene-butadiene rubber

This study reports an easy technique to produce cured styrene-butadiene rubber (SBR)/multi-walled carbon nanotubes (MWCNT) composites with a sulphur/accelerator system at 150 °C. Significant improvement in Young's modulus and tensile strength were achieved by incorporating 0.66 wt% of filler without sacrificing SBR elastomer high elongation at break. A comparison with carbon black filled SBR was also made. Field emission scanning electron microscopy was used to investigate dispersion and fracture surfaces. Results indicated that the homogeneous dispersion of MWCNT throughout SBR matrix and strong interfacial adhesion between oxidized MWCNT and the matrix are responsible for the considerable enhancement of mechanical properties of the composite.     

Interface effect in the silicone rubber/mineral powder composites

Silicone rubber/mineral powder composites have been prepared by surface modification and ultrafinecrashing of mineral powder, mixing and vulcanizing with silicone rubber resin. The surface and interface energy for mineral filler and silicone rubber matrix were investigated. It was found that there is a correlation between W _a/σ_SL (interfacial adhesive work/interfacial tension) and the tensile strength of the corresponding composite, especially for unmodified ultrafine mineral filler. On the other hand, the chemical modification of the surface changes the surface group on the mineral filler and results in improvement of the interfacial interaction between silicone rubber matrix and mineral filler, consequently, altering the reinforcing effect of the mineral filler.     

Dielectric properties of short sisal/coir hybrid fibre reinforced natural rubber composites

The dielectric properties, such as dielectric constant, volume resistivity and dielectric loss factor, of sisal/coir hybrid fibre reinforced natural rubber composites have been studied as a function of fibre loading, fibre ratio, frequency, chemical modification of fibres and the presence of a bonding agent. The dielectric constant values have been found to be higher for fibre filled systems than pure natural rubber. This has been attributed to the polarization exerted by the incorporation of fibres into the matrix. Dielectric constant values were observed to be decreased with increase in frequency due to the decreased interfacial and orientation polarization at higher frequencies. Whereas dielectric constant increases with fibre loading because of the increment in number of polar groups after the addition of hydrophilic lignocellulosic fibres. The volume resistivity of the composites was found to be decreased with fibre loading and a percolation threshold has been obtained at 15.6% volume of fibres. Fibre treatment, such as alkali, acetylation, benzoylation, peroxide and permanganate, were carried out to improve the adhesion between fibres and matrix. The dielectric constant values were lower for systems consisting of fibres subjected to chemical treatments due to the increased hydrophobicity of fibres. The addition of a two-component dry bonding agent consisting of hexamethylene tetramine and resorcinol, used for the improvement of interfacial adhesion between the matrix and fibres, reduced the dielectric constant of the composites. When the weight percentage of sisal fibre was increased in the total fibre content of the hybrid composites, the dielectric constant was found to increase. The added fibres and different chemical treatments for them increased the dielectric dissipation factor. A dielectric relaxation has been observed at a frequency of 5 MHz.     

Styrene butadiene rubber-clay nanocomposites using a latex method: morphology and mechanical properties

In this study, octadecylamine modified MMT (C18-MMT) filled SBR nanocomposites were manufactured using a latex method and a compounding method. Cure characteristics and mechanical properties of SBR compounds filled with C18-MMT, Cloisite 15A, carbon black and Na-MMT were also evaluated. By using the latex method, the number of layers of the silicates in the SBR matrix reduced from the original 14–15 layers to 1–4 layers. This was due to the presence of octadecyl ammonium ions which reduced the number of layers of the re-aggregated silicates during the process of co-coagulation. The SBR/C18-MMT nanocomposites using the latex method showed the highest oscillating disc rheometer (ODR) torques, tensile strength, modulus and tear energy. These increased mechanical properties can be attributed to the excellent reinforcing effect of the silicates well dispersed in the rubber matrix rather than the effect of the increase in the degree of crosslinking. Without alkyl ammonium ions in the latex method, the level of dispersion of silicates in the SBR matrix was very poor. The SBR/C18-MMT nanocomposites using the compounding method were found to have a lower degree of modulus, tensile strength and tear energy due to the low level of the dispersion of silicates than the SBR/C18-MMT nanocomposites using the latex method.     

Effect of air-jet texturing on adhesion behaviour of polyester yarns to rubber

Air-jet texturing of conventional poly(ethylene terephthalate) (PET) yarns, having the same chemical structure with high modulus and tenacity PET yarns, are studied in order to improve their adhesion to rubber. Air-jet texturing of these yarns is performed without any visible loop formation in order to minimize the mechanical loss, and an improvement in the adhesion to rubber of conventional PET yarns is achieved. This improvement is investigated by means of surface changes of single filaments and yarn geometry changes due to air-jet texturing. Changes of the cross-sectional structure of the yarns after air-jet texturing and therefore a higher surface area is found to be the main reason for this improvement.     

Surface modification of argon/oxygen plasma treated vulcanized ethylene propylene diene polymethylene surfaces for improved adhesion with natural rubber

Vulcanized ethylene propylene diene polymethylene (EPDM) rubber surface was treated in a radio frequency capacitatively coupled low pressure argon/oxygen plasma to improve adhesion with compounded natural rubber (NR) during co-vulcanization. The plasma modified surfaces were analyzed by means of contact angle measurement, surface energy, attenuated total reflection-infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, energy dispersive X-ray sulfur mapping and atomic force microscopy. Several experimental variables such as plasma power, length of exposure time and composition of the argon-oxygen gas mixture were considered. It was delineated that plasma treatment changed both surface composition and roughness, and consequently increased peel strength. The change in surface composition was mainly ascribed to the formation of C-O and -CO functional groups on the vulcanized surfaces. A maximum of 98% improvement in peel strength was observed after plasma treatment.     

Carbon Black–Filled Styrene Butadiene Rubber Masterbatch Based on Simple Mixing of Latex and Carbon Black Suspension: Preparation and Mechanical Properties

An improved process was developed for the production of carbon black (CB)–filled styrene butadiene rubber masterbatch (SBR-CB-MB) using a simple latex/CB mixing technology; the improvement comprised processing the CB as an emulsifier-free aqueous suspension by high-rate shearing. Tensile and tear strength, dynamic compression behaviors, the Payne effect, equilibrium swelling and bound rubber of the SBR-CB-MB and dry mixing CB filled SBR (SBR-CB-DM), covering a wide range of CB loading (45–70 phr), were investigated and compared. It was found that the tensile and tear strength, heat buildup and compression set, abrasion volume loss, and the Payne effect of the SBR-CB-MB were lower than those of the SBR-CB-DM, while the bound rubber content were higher, indicating good CB/rubber interaction in the SBR-CB-MB. SEM analysis showed that no free CB could be found on the surface or inside of the granular SBR-CB-MB particles, indicating good CB dispersion in the rubber matrix.     

Interactions Between an Ionic Liquid and Silica,Silica and Silica,and Rubber and Silica and Their Effects on the Properties of Styrene-Butadiene Rubber Composites

An investigation of the effect of an ionic liquid, 1-butyl-3-methylimidazolium tetrafluoroborate (BMI), on the properties of silica reinforced styrene-butadiene rubber (SBR), aimed to correlate the interactions between the ionic liquid and silica, silica and silica, and silica and rubber with the macro-properties and microstructure of SBR and SBR/silica vulcanizates is described. The interaction between the ionic liquid and silica was characterized by differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR), the interaction between silica and silica was characterized by a rubber processing analyzer (RPA), and the interaction between rubber and silica was characterized by the bound rubber content. The FTIR analysis revealed that BMI can react with the hydroxyl groups on the surface of silica, improving the compatibility between the rubber and silica. The RPA and bound rubber testing indicated that the interactions between silica and silica particles were weakened and the interaction between silica and rubber increased with the incorporation of BMI into the SBR rubber. The bound rubber content showed a maximum with a BMI content of 3 phr. At the same time, the dispersion of silica in SBR was improved with the incorporation of BMI. With the increase of BMI content, the curing rate was greatly improved and the crosslink density increased. BMI also increased the tensile strength and abrasion resistance of the SBR vulcanizates. Most important, the BMI significantly improved the dynamic properties of the rubber composites, especially the wet-skid resistance and rolling resistance. However, excessive BMI (beyond 3 phr) acted as a plasticizer and was detrimental to the mechanical properties, resulting in a decrease of tensile strength and abrasion resistance.     

Atomic force microscopy characterization of the surface wettability of natural fibres

Natural fibres represent a readily available source of ecologically friendly and inexpensive reinforcement in composites with degradable thermoplastics, however chemical treatments of fibres are required to prepare feasible composites. It is desirable to characterize the surface wettability of fibres after chemical treatment as the polarity of cellulose-based fibres influences compatibility with a polymer matrix. Assessment of the surface wettability of natural fibres using conventional methods presents a challenge as the surfaces are morphologically and chemically heterogeneous, rough, and can be strongly wicking. In this work it is shown that under atmospheric conditions the adhesion force between an atomic force microscopy (AFM) tip and the fibre surface can estimate the water contact angle and surface wettability of the fibre. AFM adhesion force measurements are suitable for the more difficult surfaces of natural fibres and in addition allow for correlations between microstructural features and surface wettability characteristics.     

Improved Dispersion of Carbon Nanoparticles Modified by Poly(Sodium 4-Styrenesulfonate) and Its Influence on the Properties of Natural Rubber Latex

A novel strategy of radical polymerization of sodium 4-styrenesulfonate on the surface of carbon black (CB) in the solid state was developed to prepare hydrophilic carbon nanoparticles (PNASS-CB). A high performance natural rubber latex (NRL)/PNASS-CB composite was produced by the latex compounding technique. Scanning electron microscope shows considerable improvement in the dispersion of PNASS-CB in rubber matrix. The lower degree of filler–filler networks and the stronger filler–rubber interaction of PNASS-CB in rubber matrix were confirmed by dynamic mechanical thermal analysis. Rheometric properties of NRL/PNASS-CB, like scorch time and optimum cure time, decreased. Tensile strength, tear strength, and elongation at break increased due to stronger interaction between the PNASS-CB and rubber matrix. Dynamic mechanical properties of the modified carbon nanoparticles further corroborated a significant contribution from the better dispersion and efficient load transfer of PNASS-CB on the static and dynamic mechanical properties of composites.     

Formation of a high hydrophilic/hydrophobic contrast surface on PET substrates by ECR generated sulfur hexafluoride plasma

High hydrophilic/hydrophobic contrast surfaces on polyethylene terephthalate (PET) substrates were formed by shadow mask technique in electron cyclotron resonance generated sulfur hexafluoride plasma atmosphere. The X-ray photoelectron spectroscopy (XPS) analyses indicate that the unmasked PET surfaces contained a high proportion of the CF₂-CF₂ groups, and therefore were hydrophobic with large water contact angle. However, the surface wettability was found to increase drastically on the masked PET surfaces. This could be resulted from a mass of COF (acid fluoride) compounds observed by XPS on the masked film surfaces. The COF compounds could react with atmospheric moisture to form -COOH groups, which in turn increased the surface wettability. In addition, the surface wetting property of the masked areas was found to change significantly with the plasma treatment time, the mask-to-substrate distance and the storage time after the treatment. The best contract in water contact angle obtained from the treated PET samples was larger than 100° after 168 h of storage.     

Insights into the Reinforcement of Butyl Rubber by Carbon Black and Silica with the Aid of Their Dynamic Properties

Carbon black (N234) and silica (Vulksail N) with a silane coupling agent Si-69 were chosen as reinforcing fillers in butyl rubber (IIR). The rheological behavior of the IIR compounds and the dynamic mechanical properties of IIR vulcanizates were investigated with a rubber processing analyzer and dynamic mechanical analysis (DMA) to examine the filler dispersion in the rubber matrix and the interaction between filler and matrix. The data indicated that the N234 filled IIR compounds had more filler networks than those filled with silica. Filler networks first appeared at 30 phr N234 and 45 phr silica with silane coupling agent Si-69. The interaction between N234 and IIR was far stronger than that between silica and IIR. However, the silica Vulksail N filled IIR had better wet-grip and lower rolling resistance compared to the carbon black-filled IIR should IIR be chosen as a substitute of styrene-butadiene rubber (SBR) in tire tread. The reinforcing factor, R, R (related to the difference in tan d peak height at T_g for the filled and nonfilled rubbers), also demonstrated that the N234-IIR interaction was stronger than for the silica. IIR with 30 phr N234 exhibited the largest tensile strength, 20.1 MPa, for those vulcanizates examined. The tensile and tear strengths of N234 filled IIR were higher than those of IIR with similar amounts of silica. Thus, it was concluded that N234 is a more active reinforcing filler in IIR than silica (Vulksail N) even with a silane coupling agent (Si-69).     

The surface modification of cellulose fibres for use as reinforcing elements in composite materials

The interest in using cellulose fibres as reinforcing elements in composite materials based on polymeric matrices is constantly growing, mainly because of the many advantages associated with this renewable material. However, the preparation of cellulose-based composites is perturbed by the highly hydrophilic character of the fibres, which is associated with a low interfacial compatibility with hydrophobic polymeric matrices, as well as with a loss of mechanical properties after moisture uptake. In order to reduce the hydrophilic character of cellulose fibres and to improve the strength of their adhesion to the matrix, it is necessary to undertake a structural modification of their surface. Several approaches have been studied, namely (i) physical treatments such as corona, plasma, laser, vacuum ultraviolet and γ-radiation treatments; (ii) chemical grafting by direct condensation, including surface compatibilisation with hydrophobic moieties and co-polymerisation with the matrix. The copolymerisation approach called upon different strategies: (i) The use of bi-functional molecules capable of reacting with the OH groups of the cellulose surface and leaving the second functions available for further exploitation; (ii) The direct activation of the surface and the subsequent graftingfrom polymerisation; and (iii) The condensation of organometallic compounds, followed by their coupling with suitable reactive molecules or macromolecules. The characterisation of the modified surfaces involved a variety of techniques, including elemental analysis, contact angle measurements, inverse gas chromatography, X-ray photoelectron and FTIR spectroscopy, water uptake, etc. The present survey reviews the different approaches proposed in the literature and critically assesses their respective merits and drawbacks.     

Uniformity analysis of dielectric barrier discharge (DBD) processed polyethylene terephthalate (PET) surface

A dielectric barrier discharge (DBD) plasma, operating in air at atmospheric pressure, has been used to induce changes in the surface properties of polyethylene terephthalate (PET) films. The effects that the key DBD operating parameters: discharge power, processing speed, processing duration, and electrode configurations, have on producing wettability changes in the PET surface region have been investigated. The approach taken involves the application of an Taguchi experimental design and robust analysis methodology. The various data sets obtained from these analyses have been used to studies the effect of the operating parameters on the surface uniformity and efficiency of the said treatment.In general, the results obtained indicate that DBD plasma processing is an effective method for the controlled surface modification of PET. Relatively short exposures to the atmospheric pressure discharge produces significant wettability changes at the polymer film surface, as indicted by pronounced reductions in the water contact angle measured. It was observed that the wettability of the resultant surface shows no significant differences in respect to orientation parallel (L-direction) or perpendicular (T-direction) to the electrode long axis. However, there was significant differences between the data obtained from these two orientations. Analysis of the role of each of the operating parameters concerned shows that they have a selective effectiveness with respect to resultant surface modification in terms of uniformity of modification and wettability. The number of treatment cycles and the electrode configuration used were found to have the most significant effects on the homogeneity of the resultant PET surface changes in L- and T-orientation, respectively. On the other hand, the applied power showed no significant role in this regard. The number of treatment cycles was found to be the dominant factor (at significance level of 0.05) in respect of water contact angle changes at the processed PET surface in both orientations. The driven metal electrodes (stainless steel or aluminium) were apparently superior to the driven dielectric electrode (ceramic or quartz) configurations. The grounded electrode in each case was a silicon rubber-covered aluminium plate (see later). The nature and scale of the surface changes that originate from the various processing conditions employed have been considered so as to determine the optimum treatment conditions in respect of processing outcomes, properties and any orientation dependence. Thus, it was revealed that higher processing speeds and longer processing durations are key for uniformity along the electrode axial orientation, while lower processing speeds and short exposure durations are key considerations, in the corresponding perpendicular orientation. In general, longer processing durations (low processing speeds and a high number of treatment cycles) and higher plasma powers induced greater changes in the surface wettability of the PET, as demonstrated by the observed water contact angles. This behaviour is taken to indicate that different combinations of DBD operating parameters and electrodes produce discharge conditions that can result in different plasma chemical processes in respect of uniformity, treatment efficiency and orientation dependence.     

Functionalization of PET and PA6.6 woven fabrics

In the present work as received woven fabrics of polyethylene terephthalate (PET) and polyamide 6.6 (PA6.6) were exposed to a continuous dielectric barrier discharge (DBD), in air at atmospheric pressure, at selected discharge power values and conveyor speeds. The chemical modification of the fabric surface was studied by contact angle analysis, attenuated total reflection (ATR)-FTIR spectroscopy and X-ray photoelectron spectroscopy (XPS). The results confirmed that the treatment changed the fabric surface chemistry, increasing its wettability by polar liquids and its oxygen content. Contact angle results showed different behaviour of the two polymer fabrics toward ageing effects; while PET showed a contact angle increase along the subsequent days of treatment, the PA6.6 fabric maintained its hydrophilicity even 15 days after treatment. The surface morphology analysed by scanning electron microscopy (SEM), did not show any significant difference before and after treatment.     

Improvement of interfacial adhesion in vertical GaN-based LEDs by introducing O2 plasma cleaning and intermediate layers

Interfacial adhesion between an indium tin oxide (ITO)/Ni/Ag/Ni/Au p-electrode, and Au and Ni/Au seeds in vertical GaN-based light emitting diodes (LEDs) was enhanced by O₂ plasma cleaning treatment of the Au surface in the p-electrode. However, AES and REELS analyses of the Au surface in the p-electrode detected surface damage to the p-electrode and photoresist (PR) passivation structure from O₂ plasma cleaning. W/Ni and Al/Ni adhesion layers were introduced in the Au seed to increase interfacial adhesion between Au seed and untreated PR passivation. Forward leakage current as low as 0.91 nA at 2 V was observed for the vertical LED with the Al/Ni/Au seed, for which adhesion strength to O₂ plasma-cleaned Au and untreated PR was 141.2 MPa and 62.8 MPa, respectively.     

Nanocellulose enhanced interfaces in truly green unidirectional fibre reinforced composites

One of the main problems in fabricating natural fibre reinforced polymers is the poor adhesion between intrinsically polar plant fibres and non-polar polymer matrices. We have developed a truly green technique of modifying natural fibre (hemp and sisal) surfaces to improve the interaction between the fibres and polymers by attaching nano-scale bacterial cellulose to the fibre surfaces. These modified natural fibres were then incorporated into the renewable polymers cellulose acetate butyrate (CAB) and poly-L-lactic acid (PLLA). Unidirectional natural fibre reinforced composites were manufactured to investigate the impact of the surface modification on the fibre and interface dominated composite properties. Both the tensile strength parallel as well as perpendicular to the fibres of the composites reinforced by bacterial cellulose modified natural fibres were found to increase significantly, especially in the case of a PLLA matrix. In case of modified sisal reinforced PLLA the parallel strength increases by 44% and the off-axis composite strength by 68%. Scanning electron microscopy observations of the composite fracture surfaces confirm the improved interaction between the fibre and the polymer matrix.     

Plasma surface treatment of textile fibres for improvement of car tires

A new low-temperature plasma surface modification of advanced polyester tire cord at atmospheric pressure was tested. Plasma surface treatment was performed in the barrier discharge plasmas (BDPs, atmospheric pressure glow discharge (APG) and plasma of gliding are (Glid Arc). The surface properties were characterized by the electron spin resonance spectroscopy (ESR), measurements of the contact angle of various polar and non-polar liquids with polyester cords, H-test, peel test and partially by zeta potential measurements. Further tests have been performed at an industrial testingimpregnation line where the common technology was applied on both plasma treated and untreated fibres. The standard H-test and peel-tests were used to characterize the adhesion of the fibre to usual testingrubbers.     

Fabrication and characterization of jute fabrics reinforced polypropylene-based composites: effects of ionizing radiation and disaccharide (sucrose)

Composites were prepared successfully by compression molding technique using jute fabrics (reinforcing agent) and polypropylene (matrix). Jute fabrics were treated with disaccharide (sucrose) solution and composites were fabricated with the treated fabric and polypropylene. The fiber content of the prepared composites was 40% by weight. It was found that the sucrose (2% solution) decreased the tensile strength (TS) and elongation at break about 6% and 37%, respectively, but tensile modulus and impact strength improved about 27% and 32%, respectively. When gamma radiation was applied through the untreated and treated composites the mechanical properties were improved much higher in non-treated Jute/PP-based composites than that of sucrose treated composites. For 5.0?kGy gamma dose the highest mechanical properties were observed for non-treated composites. At 5.0?kGy gamma dose the improvement of TS was 14% and 2% for non-treated and sucrose treated composites, respectively. The water uptake property of the sucrose treated composites was performed up to 10 days and composites absorbed 18% water. The functional groups of the both composites were analyzed by Fourier transform infrared spectroscopy machine. The scanning electron microscopic images of the both composites were taken for the surface and fiber adhesion analysis.