Binary Additive Systems Research Articles

Enhancing efficiency and stability of non-fullerene organic solar cells via volatilizable solid-liquid-mixed additive system

While traditional high-boiling-point liquid additives like 1,8-diiodooctane (DIO) and 1-chloronaphthalene (CN) et al. are commonly used, here we explore the potential of solid additives to optimize organic solar cells (OSCs) performance. Thieno[3,2-b]thiophene (TT), a volatilizable solid additive (VSA), is introduced into the PM6:Y6 OSCs system. TT's similarity to the Y6 backbone allows it high miscibility with Y6 molecules. In light of the fully volatile property, TT induces more uniform and condensed intermolecular packing of the active layer. This refinement increases the power conversion efficiency (PCE) from 14.45% to 15.31%. To further optimize morphology, TT is combined with the liquid additive CN, creating a binary liquid-solid additive system. This combination promotes favorable nanoscale phase separation within the PM6:Y6 active layer. Overall, the OSCs processed with TT+CN achieve an impressive efficiency of 16.43%, attributed to improved charge transport and reduced exciton recombination losses from the dual additives' synergistic effects. Importantly, the OSCs processed with TT demonstrate enhanced long-term stability, retaining 89.5% of their initial performance after 30 days, outperforming devices without additives (87.3%) and those processed with CN alone (80.5%). In summary, this research introduces TT as a promising volatilizable solid additive and a rational additive strategy to manipulate active layer film morphology. These advances hold significant potential for developing high-efficiency and stable OSCs, contributing to sustainable energy solutions.

Atomic-Scale Insights Into Graphene/Fullerene Tribological Mechanisms and Machine Learning Prediction of Properties

Abstract Graphene/fullerene carbon–based nanoparticles exhibit excellent tribological properties in solid–liquid two-phase lubrication systems. However, the tribological mechanism still lacks profound insights into dynamic friction processes at the atomic scale. In this paper, the friction reduction and anti-wear mechanism of graphene/fullerene nanoparticles and the synergistic lubrication effect of the binary additive system were investigated by molecular dynamics simulations and tribological experiments. The friction performance was predicted based on six machine learning algorithms. The results indicated that in fluid lubrication, graphene promoted “liquid–liquid” interlayer sliding, whereas fullerene facilitated “solid–liquid” interface sliding, resulting in a decrease or increase in friction force. Under boundary lubrication, graphene/fullerene nanoparticles were adsorbed and anchored at the metal interface to form a physical protective film, which improved the bearing capacity of the lubricating oil film, transformed the direct contact between asperities into interlayer sliding of graphene and roll–slide polishing, filling, and repairing of fullerene, thus improving the frictional wear of the lubrication system as well as the friction temperature rise and stress concentration of the asperities. Furthermore, six machine learning algorithms showed low error and high precision, and the coefficient of determination was greater than 0.9, indicating that all models had good prediction and generalization capabilities, fully demonstrating the feasibility of combining molecular simulation and machine learning applications in the field of tribology.

Synergistic effects of microencapsulated bacterial spores and superabsorbent polymer on self-healing performance in mortar

This study explores the feasibility of utilizing a superabsorbent polymer (SAP) to improve the self-healing performance of microbial-induced calcium carbonate precipitation (MICP) in cement-based materials. The amount of microencapsulated bacterial spores was varied from 0.25–1 % by cement weight. The SAP content was set to either 0 or 4 % by cement weight. As additives, the impact of SAP and MICP bacteria on mortar properties, including flowability and compressive strength, was assessed. The self-healing performance was evaluated based on crack-healing percentage and water permeability recovery. Microstructural analyses, including thermogravimetry/differential thermal analysis (TG/DTA), X-ray diffraction (XRD), and scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM-EDS), were performed to investigate the microstructural and chemical changes during the healing process. The findings revealed that specimens exclusively mixed with 4 % SAP exhibited a slightly lower crack-closure efficiency compared to those mixed exclusively with 1 % MICP bacteria. However, the SAP-containing specimens exhibited a higher degree of permeability recovery. Meanwhile, in the binary additive system with 0.5 % MICP bacteria and 4 % SAP, the specimens exhibited the highest crack-closure percentage of 91 % and a final water discharge rate of 15 mL/min after 45 days of healing. In contrast, specimens mixed exclusively with 1 % MICP bacteria showed a crack-closure percentage of 76 % and a final water discharge rate of 59 mL/min. These results suggest that incorporating SAP into the MICP system enables a reduction in MICP bacterial content without compromising self-healing performance.

Highly Efficient Hole Transport Layer‐Free Low Bandgap Mixed Pb–Sn Perovskite Solar Cells Enabled by a Binary Additive System

AbstractThe development of high‐performance hole transport layer (HTL)‐free perovskite solar cells (PSCs) with a simplified device structure has been a major goal in the commercialization of PSCs due to the economic advantage of low manufacturing cost. Unfortunately, low bandgap (Eg) mixed Pb–Sn perovskites, which have promising utility for constructing efficient all‐perovskite tandem solar cells, have rarely been explored in simplified HTL‐free device configurations. In this study, efficient band bending and defect engineering at the interface between perovskite and indium tin oxide (ITO) are realized via a binary additive system using copper thiocyanate (CuSCN) and glycine hydrochloride (GlyHCl). Using mixed Pb–Sn perovskites decorated with crystalline p‐type CuSCN, the energy level alignment at the hole extractive interface is modulated in favor of hole extraction, simultaneously increasing hole mobility. Suppressed nonradiative carrier recombination in the perovskite bulk, or across the charge extractive interface, is further achieved by GlyHCl without disturbing the efficient hole transfer characteristics. Notably, a more optimized band alignment is achieved at the hole extractive interface with the addition of GlyHCl. The HTL‐free mixed Pb–Sn PSC shows an efficiency up to 20.1% under forward bias with negligible hysteresis, comparable to state‐of‐the‐art high‐performance full‐structured mixed Pb–Sn PSCs.

Mechanistic insights into the effect of structural factors on film formation and tribological performance of organic friction modifiers

The influence of molecular structure of organic friction modifiers (OFMs) on their adsorption behaviour on iron oxide surface immersed in PAO oil was investigated using neutron reflectometry (NR). The effects of carbon chain length and levels of unsaturation on film formation was studied using a series of fatty acids with 18–20 carbon atoms in the temperature range between 25 and 100 °C. The results revealed that saturated OFM molecules generate thicker films compared to its unsaturated counterparts. Further, a decrease in film thickness was observed with the degree of unsaturation with the exception of linolenic acid. The film thickness and grafting density of the OFM increased with temperature. A decreased film thickness for the binary additive system comprising GMO and saturated molecules suggested that the adsorption of OFMs on the surface is hindered in the presence of glycerol mono oleate (GMO). A lower boundary friction coefficient and wear exhibited by OFMs with longer chain and linear structure suggest that their tribofilms are more effective in withstanding shear. The tribofilm thickness measured using optical interferometry showed no correlation with the adsorbed layer thickness determined from NR data; this lack of correspondence is attributed to the load and shearing forces experienced by the OFM molecules at the contact surfaces during friction measurements.

Behavior and interaction of boundary lubricating additives on steel and DLC-coated steel surfaces

Tribofilm formation and frictional performance of lubricant additives — oleamide, ZDDP and their mixture formulated in PAO — on steel and diamond-like carbon (DLC)-coated steel surfaces was studied under severe boundary lubrication conditions. The binary additive system reduced friction to a greater extent compared to the individual additives for all the surfaces. Chemical composition analysis of the tribofilms using surface spectroscopic techniques (ToF-SIMS and EDX) revealed that the formation of tribo-reactive ZDDP film on steel surface is suppressed in the presence of oleamide. In turn, this results in lower friction. Frictional performance of the additives on diamond DLC and graphite DLC-coated steel surfaces was evaluated and correlated with their wear performance. Analysis of tribofilm thickness and chemical composition revealed that the additives did not form a cohesive film on diamond DLC surface. On the contrary, graphite DLC coating completely worn out from the substrate when additives were present singly in the formulation. However, the additives in combination prevented delamination of graphite DLC coating.

Influence of Base oil Polarity on the Tribological Performance of Surface-Active Engine Oil Additives

Friction, wear and tribofilm growth of organic friction modifiers (glycerol monooleate and oleamide), anti-wear additive (ZDDP) and binary additive system comprising the organic friction modifiers and ZDDP were studied in polyalphaolefin (PAO) and ester oil. The mechanisms underlying base oil polarity-dependent frictional performance of the OFM and AW additives at high temperature (140 ℃), either singly or in combination, were investigated in the light of chemical composition analysis of the tribofilms post friction measurements using energy dispersive X-ray spectroscopy (EDX), static and dynamic time-of-flight secondary ion mass spectrometry (ToF–SIMS). Depending on the rubbing conditions, the boundary friction coefficient of the binary additive systems was found to be either lower than that of individual additives or to lay between the values for the individual additives. Chemical composition analysis of the tribofilms indicated that the nature of base oil controlled interactions between ZDDP and OFM and consequently adsorption and reactive tribofilm formation in the boundary lubrication layer. Surface roughness and wear scar width measured post tribological tests using 3D surface profiler showed improved wear performance in both PAO and ester-based additive formulations.

XANES Study of Tribofilm Formation With Low Phosphorus Additive Mixtures of Phosphonium Ionic Liquid and Borate Ester

The development of low phosphorus engine oils is important to minimize phosphorus-induced exhaust catalyst poisoning and resulting in harmful emissions. In this study, low phosphorus oil formulations were prepared by using an ashless additive mixture of borate ester (SB) with ionic liquid composed of a phosphonium cation and phosphate anion (P_DEHP) at 350 and 700 ppm phosphorus. Tribological properties of this binary additive system were evaluated using a reciprocating cylinder on a flat test configuration. Favorable interaction between P_DEHP and SB resulted in a significant reduction in friction coefficient and wear volume, in particular for P_DEHP(700P) + SB oil blend. Time-scale analysis of tribofilm formation was determined by running the tribological experiments for 5, 15, and 60 min duration. Electrical contact resistance (ECR) results revealed that the addition of P_DEHP at 350 ppm of phosphorus to SB at 500 ppm of boron can reduce the incubation time from 300 to 100 s for stable tribofilm formation. X-ray absorption near-edge spectroscopy (XANES) analysis of tribofilms indicates that the tribofilm mechanism for additive mixtures of P_DEHP and SB initially involves the formation of boron oxide-based films, which later interact with phosphorus to form boron phosphates in addition to iron phosphates. Incorporation of the high amount of boron phosphates in addition to boron oxide/acid and iron phosphates in the tribofilms contributed to the improved tribological performance of P_DEHP(700P) + SB oil. XANES results reveal that tribofilms formed due to the interaction of SB and P_DEHP evolve to a cross-linked structure, wherein the chain length of polyphosphates is increased with the increase in rubbing time.

Effect of temperature on tribological performance of organic friction modifier and anti-wear additive: Insights from friction, surface (ToF-SIMS and EDX) and wear analysis

Tribological performance of an organic friction modifier (glycerol monooleate – GMO), an anti-wear additive (zinc dialkyldithiophosphate – ZDDP) and its combination was studied using a ball-on-disc tribometer equipped with optical interferometry at 90 °C and 140 °C. Higher temperatures were needed for the formation of additive layers and chemically reactive anti-wear protective layers. Comparison of Stribeck curves obtained after different rubbing durations showed that GMO reduced friction at low speed sliding-rolling contact. Despite notable decrease in the base oil viscosity with increase in temperature — in turn, increasing the severity of asperity contact — GMO exhibited enhanced frictional performance. The presence of ZDDP alone in the formulation led to significant increase in friction at both low and high temperatures, with the thickness of tribofilm unaffected after prolonged rubbing. The addition of friction modifier to ZDDP-based formulation reduced the friction in the boundary lubrication regime where longer rubbing aided in effective friction reduction at higher temperature. For the binary additive system, the friction coefficient was found to lie between the values corresponding to the single additives. The observed tribological response is attributed to preferential adsorption of the friction modifier over ZDDP and/or ZDDP decomposition products. This notion was corroborated by the results obtained from static and dynamic time-of-flight secondary ion mass spectrometry (ToF-SIMS) and energy-dispersive X-ray spectroscopy (EDX) analysis of the disc surface post tribological measurement. The concentration gradient of different chemical species detected in the tribofilm correlated with the frictional performance of the additives. Analysis of surface roughness and wear scar width showed an improvement in wear performance at higher temperature suggesting the friction modifier and anti-wear additive adsorbed on the surface providing a mechanical barrier. A synergistic effect on the wear performance was observed for GMO + ZDDP-based formulations, which resulted in a smaller wear scar compared to the individual additives.

Improving sizing performance of middle layer of liquid packaging board containing high-yield pulp

As the important part of liquid packaging board, the middle layer is generally produced from a mixed pulp furnish by unbleached softwood kraft pulp and high-yield pulp (HYP). However, the addition of HYP would bring unsatisfactory properties (e.g. hydrophilicity) to liquid packaging board. Herein, in this study, the sizing performance of middle layer of liquid packaging board was evaluated by varying the kraft pulp to HYP ratios of middle layer, the dosage of sizing agent and cationic additives etc. It showed that the edge penetration value and Cobb value of middle layer illustrated a better liquid repellence with the addition of sizing agent. The improved sizing performance of the middle layer of liquid packaging board can be ascribed to the excellent performance of the added cationic additive (polyethyleneimine (PEI), alums) for trapping anionic trash via neutralization/flocculation effects. In addition, a binary cationic additive system (Al2(SO4)3-PEI) was proposed to study the improvement on the sizing performance. It was found that a desirable liquid repellence ability can be successfully achieved at a binary additive system containing 1.5% of Al2(SO4)3 and 0.2% of PEI, even when dosage of rosin sizing agent was reduced to 0.5%. The study put forwards a practical approach to improve the sizing performance, especially the liquid repellence ability of liquid packaging board when containing HYP.

Tribological Properties of Novel Multi-Walled Carbon Nanotubes and Phosphorus Containing Ionic Liquid Hybrids in Grease

A continuing quest exists to develop high-performance grease capable of meeting extreme demands of high energy efficiency and durability of modern mechanical systems. In this study, multi-walled carbon nanotubes (MWCNT) and ionic liquids (IL) either singly or as a binary additive system were prepared to study the tribological performance of lithium greases under boundary lubrication condition. The combination of MWCNT and IL can benefit from their respective lubricating mechanism to minimize friction and wear. To test this hypothesis, MWCNT and IL are tested individually and compared with combined MWCNT-IL additive mixture within lithium-based greases. MWCNT-IL gelatinous hybrids were prepared by inducing physical non-covalent interactions between MWCNTs and phosphorous based ILs through ultrasonication and magnetic stirring. Four different phosphorous based ILs, Choline bis(2-ethylhexyl)-phosphate, Choline dibutyl-dithiophosphate, Methyl-tributyl-phosphonium dimethyl-phosphate, Tetra-n-butyl-phosphonium O,O-diethyl-dithiophosphate were used. Four ball tribological test configuration was used to assess wear and friction properties of fabricated greases. The lubrication mechanism of these additives was elucidated through analysis of worn surfaces using surface characterization techniques like SEM, EDS, and stereo optical microscopy. All greases that contain ionic liquid exhibited better tribological performance compared to grease with ZDDP. The maximum reduction of the coefficient of friction (COF) of 60% and wear scar diameter (WSD) reduction of 25% was observed for greases containing MWCNTs and phosphonium cation based ILs hybrids as an additive. Results indicated either worse or comparable anti-wear behavior in greases with MWCNT-IL hybrids as compared to greases that only contained IL or MWCNT. The antagonistic interaction between MWCNT and IL has been postulated to occur when MWCNT adversely interacts with IL formed tribofilms, negating the benefit from IL resulting in increased wear in greases with binary mixtures of MWCNT-IL.

One-Step Printable Perovskite Films Fabricated under Ambient Conditions for Efficient and Reproducible Solar Cells.

Despite the potential of roll-to-roll processing for the fabrication of perovskite films, the realization of highly efficient and reproducible perovskite solar cells (PeSCs) through continuous coating techniques and low-temperature processing is still challenging. Here, we demonstrate that efficient and reliable CH3NH3PbI3 (MAPbI3) films fabricated by a printing process can be achieved through synergetic effects of binary processing additives, N-cyclohexyl-2-pyrrolidone (CHP) and dimethyl sulfoxide (DMSO). Notably, these perovskite films are deposited from premixed perovskite solutions for facile one-step processing under a room-temperature and ambient atmosphere. The CHP molecules result in the uniform and homogeneous perovskite films even in the one-step slot-die system, which originate from the high boiling point and low vapor pressure of CHP. Meanwhile, the DMSO molecules facilitate the growth of perovskite grains by forming intermediate states with the perovskite precursor molecules. Consequently, fully printed PeSC based on the binary additive system exhibits a high PCE of 12.56% with a high reproducibility.

Stabilization of \u03b3-sterilized low-density polyethylene by synergistic mixtures of food-contact approval stabilizers

In our previous studies, we have found the synergistic combinations of stabilizers which follow different mechanisms of stabilization and are approved for food contact applications. The present attempt is to test the potentials of those systems in stabilizing γ-sterilized low-density polyethylene (LDPE). The results were discussed by comparing the stabilizing efficiency of mixtures with and without phenol systems as well as with their counterparts of isotactic polypropylene (iPP) and ethylene-propylene copolymers (EP) matrices. LDPE has been melt-mixed with tertiary hindered amine stabilizer (tert-HAS), oligomeric HAS stabilizer, phenolic and organo-phosphite antioxidants and subjected to γ-sterilization. Stabilization in terms of changes in oxidation products, tensile properties, yellowing and surface morphology was evaluated by FT-IR spectroscopy, Instron, colorimetry, and scanning electron microscopy (SEM), respectively. The results of the present study confirm the validity of those systems for protecting various polyolefins against γ-sterilization. The results showed that the synergism, antagonism and the trend in stabilization efficiency of the binary, ternary and quaternary stabilizer systems were almost similar in LDPE, iPP and EP matrices. The binary system of oligomeric HAS and tert-HAS has shown the antagonistic effect of stabilization, whereas their combination with organo-phosphite has exhibited synergistic effect even at higher doses of γ-sterilization. The combination of oligomeric HAS, tert-HAS, organo-phosphite and hindered phenol exhibited improved stabilization efficiency than single or binary additive systems. The phenol systems have shown long term of stability than that of phenol-free systems. It was found that the consumption of oligomeric stabilizer significantly depends on the components of stabilization mixture. It was concluded that the stability of polyolefins (LDPE, iPP and EP) against γ-sterilization can be achieved by blends of different stabilizers which are approved for food contact applications.

A Mechanistic Understanding of a Binary Additive System to Synergistically Boost Efficiency in All-Polymer Solar Cells.

All-polymer solar cells are herein presented utilizing the PBDTTT-CT donor and the P(NDI2OD-T2) acceptor with 1,8-diiodooctane (DIO) and 1-chloronaphthalene (CN) binary solvent additives. A systematic study of the polymer/polymer bulk heterojunction photovoltaic cells processed from the binary additives revealed that the microstructures and photophysics were quite different from those of a pristine system. The combination of DIO and CN with a DIO/CN ratio of 3:1 (3 vol% DIO, 1 vol% CN and 96 vol% o-DCB) led to suitable penetrating polymer networks, efficient charge generation and balanced charge transport, which were all beneficial to improving the efficiency. This improvement is attributed to increase in power conversion efficiency from 2.81% for a device without additives to 4.39% for a device with the binary processing additives. A detailed investigation indicates that the changes in the polymer:polymer interactions resulted in the formation of a percolating nasnoscale morphology upon processing with the binary additives. Depth profile measurements with a two-dimensional grazing incidence wide-angle X-ray scattering confirm this optimum phase feature. Furthermore impedance spectroscopy also finds evidence for synergistically boosting the device performance.

Binary-additives Toughened Biopolymer for Packaging Application

The toughening of poly(lactic acid) or PLA with Monmorillonite clay (MMT), polyamide-block-ether (PEBAX) and hyperbranched polymer (Boltorn®) was investigated. PLA was first blended with 1, 2, 2.5, 3 and 4%wt of MMT, 5-20%wt of PEBAX and Boltorn® for a single additive system. For the binary additive system, PEBAX and Boltorn® 5-20%wt were pre-mixed with 2.5%wt of MMT, and then they were added to PLA. PLA blendes were prepared by an internal mixer. Tensile properties, impact properties and morphology of PLA blends were investigated. For single additive with PLA, adding MMT showed the increasing of toughness of PLA. PLA/PEBAX blends were shown the increasing of elongation and impact strength with containing PEBAX content, but modulus and tensile strength decreased. The results of PLA/Boltorn® blends were similar with PLA/PEBAX blends. Furthermore, elongation and impact strength of PLA blends can be improved by adding PEBAX binary additive, modulus and tensile strength decreased but not as severe as single additive. Adding Boltorn® as in a binary additive led to the brittleness and less elongation of blends when compared to adding a single additive and neat PLA.

Modification of the molar anionic charge density of acetone–formaldehyde–sulfite dispersant to improve adsorption behavior and effectiveness in the presence of CaAMPS®‐co‐NNDMA cement fluid loss polymer

AbstractSulfonated aldol polycondensates were synthesized from acetone, formaldehyde, and different amounts of sodium sulfite, resulting in polymers with varying degrees of sulfonation (DS). The anionic charge amount of these macromolecules measured by polyelectrolyte titration decreased with lower DS. The effectiveness of the acetone–formaldehyde–sulfite (AFS) polycondensates as cement dispersant was found to depend on the amount of polymer adsorbed on cement. AFS adsorption decreases with lower DS. Interaction and compatibility between AFS and CaAMPS®‐co‐NNDMA fluid loss additive was studied by formulating binary additive systems composed of one of the modified AFS polymers and CaAMPS‐co‐NNDMA. At high DS, AFS adsorbs strongly and prevents CaAMPS‐co‐NNDMA from adsorbing in sufficient amounts on the cement surface. The result is poor fluid loss control of the cement slurry. AFS polymers with lower DS, however, allow simultaneous adsorption of both polymers in sufficient quantities to provide good fluid loss control and low rheology at the same time. Thus, effectiveness of both additives was retained. Obviously, effectiveness of such multi‐admixture systems depends on the adjustment of the adsorption behavior of the individual components relative to each other. Molar anionic charge density of the polymers was found to be a major parameter influencing their relative adsorption behavior. The AFS polymer with DS = 0.2 possesses a molar anionic charge density comparable to CaAMPS‐co‐NNDMA. Thus, when admixtures with similar molar anionic charge densities are used, the performance of one component is not negatively influenced by the other. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009

Stabilization of γ-sterilized biomedical polyolefins by synergistic mixtures of oligomeric stabilizers. Part II. Polypropylene matrix

In our previous study we have found the synergistic combinations of stabilizers which follow different mechanisms of stabilization and are approved for food contact and biomedical applications. The present attempt is to test the potentials of those systems in stabilizing γ-sterilized isotactic polypropylene (i-PP). Isotactic polypropylene was melt-mixed with hindered amine stabilizers (HAS), phenolic antioxidants and organo-phosphites (hydroperoxide decomposer) and sterilized with different doses of γ-radiation. Stabilization was monitored in terms of changes in the functional groups (oxidation products), tensile properties, yellowing and surface morphology by FTIR spectroscopy, Instron, colorimetry (reflectance) and scanning electron microscopy (SEM), respectively. The trend in stabilizing the efficiency of binary (1:1), ternary (1:1:1) and quaternary (1:1:1:1) additive systems was confirmed by comparing the stabilizing efficiency of mixtures with and without phenol system as well as with their counter parts of EP copolymer matrix. The binary system of secondary HAS and tertiary HAS, has shown antagonistic effect of stabilization whereas their combination with organo-phosphite has exhibited synergistic effect even at higher doses of γ-sterilization. Due to the oxidation of hindered phenol, phenol systems have shown discoloration and it was reduced by mixing with secondary HAS, tertiary HAS and organo-phosphite. The response of the stabilizer systems is better to ethylene–propylene (EP) copolymer than to i-PP in terms of stabilization.

Stabilization of γ-sterilized biomedical polyolefins by synergistic mixtures of oligomeric stabilizers

The stabilization of polyolefins against γ-sterilization has been studied with single or binary additive system. The present attempt is to utilize synergistic mixtures of stabilizers which are approved for food contact applications. Ethylene–propylene (EP) copolymer has been melt-mixed with hindered amine stabilizers (HAS), phenolic antioxidants and organo-phosphites (hydroperoxide decomposer). Samples were sterilized with different doses of γ-radiation. Stabilization was characterized in terms of changes in the functional groups (oxidation products), tensile properties, yellowing and surface morphology by FTIR spectroscopy, Instron, colorimetry (reflectance) and scanning electron microscopy (SEM), respectively. Results were discussed by comparing the stabilizing efficiency of mixtures with and without phenol system. Among phenol containing systems, where we mostly observe discoloration due to the oxidation of hindered phenol and the combination of secondary HAS, tertiary HAS, organo-phosphite and hindered phenol exhibited improved stabilization efficiency than single or binary additive systems. The mixture of secondary HAS and tertiary HAS, has shown antagonistic effect of stabilization whereas their combination with organo-phosphite has exhibited synergistic effect of stabilization even at higher doses of γ-sterilization. The effects have been explained through the interaction between the stabilizers.

Additive quantification on polymer thin films by ToF-SIMS: aging sample effects

Thin films (150 nm) of an amorphous polyester (polyethylene(terephthalate–isophthalate)) containing variable concentrations of an antioxidant (Irgafos™ 168) and a UV-stabilizer (Hostavin™ N30) have been prepared by spin-coating. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) results showed, in the case of a single additive system (antioxidant), that the additive intensity increased on the polymer surface during the first five aging days (exudation phenomenon), followed by an intensity decrease, which was related to the adsorption of hydrocarbon contaminations on the sample surface. This kinetic competition was observed whatever the used additive concentration. In the case of the binary additive system (antioxidant and UV-stabilizer), the antioxidant behavior was similar to the single additive system, whereas, the UV-stabilizer evolution corresponded to an additive depletion, followed by an exudation. These results indicate that it is necessary to be very careful when comparing ToF-SIMS data for additive quantification on polymer surfaces. It is strongly recommended to compare samples having the same aging time, because the surface composition was seen to be strongly dependent of the aging time.

Additive quantification on polymer thin films by ToF-SIMS: aging sample effects

Thin films (150 nm) of an amorphous polyester (polyethylene(terephthalate–isophthalate)) containing variable concentrations of an antioxidant (Irgafos™ 168) and a UV-stabilizer (Hostavin™ N30) have been prepared by spin-coating. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) results showed, in the case of a single additive system (antioxidant), that the additive intensity increased on the polymer surface during the first five aging days (exudation phenomenon), followed by an intensity decrease, which was related to the adsorption of hydrocarbon contaminations on the sample surface. This kinetic competition was observed whatever the used additive concentration. In the case of the binary additive system (antioxidant and UV-stabilizer), the antioxidant behavior was similar to the single additive system, whereas, the UV-stabilizer evolution corresponded to an additive depletion, followed by an exudation. These results indicate that it is necessary to be very careful when comparing ToF-SIMS data for additive quantification on polymer surfaces. It is strongly recommended to compare samples having the same aging time, because the surface composition was seen to be strongly dependent of the aging time.