Effects of plasma treatments of polypropylene adhesive joints used in the automotive industry

Plasma treatment has been used in recent years to activate the surfaces of adhesive substrates and thus as an adhesion promoter between adhesive and substrates. The use of plasma treatments is widely adopted in the automotive industries especially for polymers that present low surface energy, such as polypropylene. In this work, polypropylene substrates used in the automotive industries have been treated with two different techniques: vacuum and atmospheric plasma. Then, polyurethane and methacrylate adhesives have been used to bond single lap joints (SLJs). Typically, these two adhesives cannot bond polypropylene substrates without surface treatments. An experimental plan has been designed to investigate the process parameters that can increase the functional polar groups (FPGs) maximizing the adhesion strength. Besides the types of plasma, two different gas carriers (air and nitrogen) and different treatment times have been investigated. The substrates, treated and not treated, have been assessed through scanning electron microscopy, energy-dispersive X-ray analysis, and Fourier-transform infrared spectroscopy to quantitatively assess the increment of FPGs after the different treatments. The experimental plan shows that the atmospheric plasma can improve the surface of the substrates by using a smaller time. Mechanical tests on SLJs show that methacrylate and polyurethane cannot bond polypropylene substrates without the plasma treatment. On the other hand, the treated substrates can form a strong bonding with the adhesive since all SLJs exhibit a substrate failure. Mechanical tests have been also carried out after three different aging cycles showing that the adopted plasma treatment is not affected by the aging cycles.

Effectiveness of the iDOP-PH adhesion promoter in relation to adhesion of the pavement bitumen

Asphalt pavement is permanently influenced by various environmental conditions and traffic load. Because of this after a certain period numerous defects may appear on the surface of the road pavement. These defects include peeling, chipping, pots, cracks etc. The low water proof resistance of the asphalt concrete (conditioned by low adhesion of the bitumen to aggregate surface) is considered to be one of the reasons for appearance of these defects. Adhesion promoters’ use is the most common method to increase adhesion activity of pavement bitumen. Goal. The objective of the current research work is the evaluation of influence of the domestic adhesion promoter iDOP on the conventional and adhesion properties of bitumen. Methodology. To achieve this goal, the following was done: the effect of the adhesive promoter iDOP on the standard quality indicators of bitumen was determined according the requirements of the current standards DSTY 4044 and SOU 45.2-00018112-067; the effect of the adhesive promoter on the adhesion of bitumen to the glass surface (according to the DSTU B.V.2.7-81 method) and to the surface of aggregates with different mineralogy was evaluated by the rotating bottle method according to DSTU EN 12697-11; the thermal stability of the iDOP-PH promoter was tested by simulating the technological ageing of bitumen according to the method given in GOST 18180 and the RTFOT method. Results. Grounding on the experimental data obtained, it was found that the adhesive promoter iDOP-PH does not affect the standard indicators of the quality of bitumen (penetration, softening and breaking point temperatures, ductility). During hardening with the RTFOT method, a slight inhibitory effect of the promoter is observed, which appears as an increase in the values of residual penetration and ductility compared to bitumen without promoter. The iDOP-PH promoter increases the adhesive capacity of bitumen, which is confirmed by the adhesion data determined by the improved method given in GOST B.V.2.7-81 and the rolling bottle method. Originality. It is shown that the iDOP-PH promoter has a relevantly low thermal stability. With this the main factor affecting the decrease in thermal stability is the long time exposing of the binder at high temperature by GOST B.V.2.7-81 method. Practical value. It is shown that the promoter concentrations recommended by the supplier are insufficient, and to ensure the required values of the adhesion (standardized in СОУ 45.2-00018112-067) it is advisable to increase the concentration of the iDOP-PH promoter in bitumen to 0.3 - 0.6%.

Evaluation of thermal and physical properties of PMMA/PMVEMA-ES blends as organic coating

Purpose In this work, the blends of poly(methyl methacrylate), PMMA and poly(methyl vinyl ether-alt-maleic acid monoethyl ester), PMVEMA-ES are studied as organic coatings to evaluate the impact of intermolecular hydrogen bonding on the physical and thermal characteristics of the prepared coatings. Design/methodology/approach PMMA (Mw = 120,000 g mol-1) was chosen as our binder material. Due to the low adhesion property of PMMA on polar substrates, it was blended with PMVEMA-ES, which contains polar –COOH groups, to improve the adhesion and thermal properties of the coatings by forming intermolecular hydrogen bonds. A cross-hatch adhesion test was carried out to evaluate the adhesion strength of different ratios of PMMA/PMVEMA-ES blends as coatings. In addition, changes in the glass-transition temperature, Tg as the composition varies were studied using Differential Scanning Calorimetry, DSC. Then, glossiness and hiding power tests were also conducted to evaluate the physical properties of the prepared coatings. Findings Upon a closer look at the DSC results, it was found that blends consisting of 12.5, 25.0 and 87.5 wt. % PMMA were completely compatible due to the presence of only a single Tg in their thermograms. Other blend compositions showed two distinct Tgs, indicating partial compatibility. Furthermore, the addition of PMVEMA-ES caused the Tg of PMMA to shift to lower temperatures, a strong indication of intermolecular hydrogen bonding interactions between the two components. From the cross-hatch adhesion results, the addition of PMVEMA-ES improved the adhesion properties of PMMA coating, except for blends consisting of 62.5 and 75.0 wt. % PMMA possibly due to the partial incompatibility between the two components. These findings were further corroborated with the results of glossiness and hiding power measurements. The superior result was seen for the blend consisting of 12.5 wt. % PMMA with strong adhesion property, high glossiness, compatibility and high translucency. Practical implications PMVEMA-ES can potentially be used as an adhesion promoter in PMMA-based coating formulations. Originality/value This is the first report on the properties of PMMA/PMVEMA-ES blends as coatings.

Delamination-Free In-Air and Underwater Oil-Repellent Filters for Oil-Water Separation: Gravity-Driven and Cross-Flow Operations

Separating oil-water mixtures is critical in a variety of practical applications, including the treatment of industrial wastewater, oil spill cleanups, as well as the purification of petroleum products. Among various methodologies that have been utilized, membranes are the most attractive technology for separating oil-water emulsions. In recent years, selective wettability membranes have attracted particular attention for oil-water separations. The membrane surfaces with hydrophilic and in-air oleophobic wettability have demonstrated enhanced effectiveness for oil-water separations in comparison with underwater oleophobic membranes. However, developing a hydrophilic and in-air oleophobic surface for a membrane is not a trivial task. The coating delamination process is a critical challenge when applying these membranes for separations. Inspired by the above, in this study we utilize poly(ethylene glycol)diacrylate (PEGDA) and 1H,1H,2H,2H-heptadecafluorodecyl acrylate (F-acrylate) to fabricate a hydrophilic and in-air oleophobic coating on a filter. We utilize methacryloxypropyl trimethoxysilane (MEMO) as an adhesion promoter to enhance the adhesion of the coating to the filter. The filter demonstrates robust oil repellency preventing oil adhesion and oil fouling. Utilizing the filter, gravity-driven and continuous separations of surfactant-stabilized oil-water emulsions are demonstrated. Finally, we demonstrate that the filter can be reused multiple times upon rinsing for further oil-water separations.

The Influence of the Affinity between Aggregate and Bitumen on the Mechanical Performance Properties of Asphalt Mixtures

Two of the main problems encountered in flexible pavements are the stripping of coarse aggregates and the formation of rut depth due to increases in the volume of road traffic and heavy vehicle loads, especially in areas where speeds are low. The existence of rut depth also affects the comfort and safety of road users due to the water accumulation on the pavement surface and reducing tire/pavement friction, which can lead to hydroplaning phenomena. In this research, it was proven that the use of fillers of different origins influences the affinity between aggregates and the binder. The effect of an adhesion promoter in the mix design (such as the amine included in cellulosic fiber pellets) was also studied. Several tests were carried out to determine the binder/aggregate adhesiveness, water sensitivity and resistance to permanent deformation, to evaluate the performance of different blends. It was found that the addition of this additive increased 10% of the aggregate surfaces covered with bitumen when compared with the aggregates without this addition. As expected, the water sensitivity tests showed that the mixture with granitic filler had the lowest indirect tensile strength ratio (ITSR) value (70%), while the mixtures with limestone filler led to the highest percentages (ranging from 83 to 93%). As for the results of the wheel tracking tests (WTT), it was confirmed that the use of limestone filler translates into an improvement in the performance against the permanent deformation of the asphalt mixtures. The mixture with higher bitumen content and adhesion promoter revealed the best average results.

Enhancement of Flame Retardancy and Mechanical Properties of Polylactic Acid with a Biodegradable Fire-Retardant Filler System Based on Bamboo Charcoal

A cooperative flame-retardant system based on natural intumescent-grafted bamboo charcoal (BC) and chitosan (CS) was developed for polylactic acid (PLA) with improved flame retardancy and minimal decline in strength properties. Chitosan (CS) as an adhesion promoter improved the interfacial compatibility between graft-modified bamboo charcoal (BC-m) and PLA leading to enhanced tensile properties by 11.11% and 8.42%, respectively for tensile strength and modulus. At 3 wt.% CS and 30 wt.% BC-m, the crystallinity of the composite increased to 38.92%, or 43 times that of pure PLA (0.9%). CS promotes the reorganization of the internal crystal structure. Thermogravimetric analysis showed significantly improved material retention of PLA composites in nitrogen and air atmosphere. Residue rate for 5 wt.% CS and 30 wt.% BC-m was 29.42% which is 55.1% higher than the theoretical value of 18.97%. Flammability tests (limiting oxygen index-LOI and UL-94) indicated significantly improved flame retardancy and evidence of cooperation between CS and BC-m, with calculated cooperative effectiveness index(Ce) >1. From CONE tests, the peak heat release rate (pHRR) and total heat release (THR) were reduced by 26.9% and 30.5%, respectively, for 3% CS + 20% BC-m in PLA compared with adding 20% BC-m alone. Analysis of carbon residue morphology, chemical elements and structure suggest CS and BC-m form a more stable char containing pyrophosphate. This char provides heat insulation to inhibit complete polymer pyrolysis, resulting in improved flame retardancy of PLA composites. Optimal mix may be recommended at 20% BC-m + 3% CS to balance compatibility, composite strength properties and flame retardance.