Phase Behavior of Aqueous Biphasic Systems with Choline Alkanoate Ionic Liquids and Phosphate Solutions: The Influence of pH

Aqueous biphasic systems (ABS) composed of the choline alkanoate ionic liquids (ILs) choline acetate [Cho][OAc], choline propanoate [Cho][Pro], choline butyrate [Cho][But], and choline hexanoate [Cho][Hex], mixed with K₃PO₄ solutions at pH 7.2 and 14.5, were prepared and their phase diagrams were compared. The ability to form ABS with alkaline K₃PO₄ solutions decreased in the order [Cho][OAc] ≈ [Cho][Pro] > [Cho][But] > [Cho][Hex], while with neutral K₃PO₄ solutions, [Cho][OAc] could not form an ABS, and the other three ILs performed similarly. All of the biphasic regions of the ABS decreased with the increase in pH. ¹H-NMR data indicated anion exchange between phases in ABS at neutral pH. The ABS at neutral pH were evaluated to extract the triazine herbicides simazine, cyanazine, and atrazine, and the ABS formed by [Cho][Pro] and the pH 7.2 K₃PO₄ solution has shown extraction recoveries higher than 90%.     

Preferential melt intercalation of clay in ABS/brominated epoxy resin-antimony oxide (BER-AO) nanocomposites and its synergistic effect on thermal degradation and combustion behavior

ABS/organo montmorillonite (OMT) nanocomposites and ABS/brominated epoxy resin-antimony oxide (BER-AO)/OMT nanocomposites were prepared via melt compounding. The dispersion of OMT in nanocomposites was investigated by wide-angle X-ray diffraction and transmission electron microscopy. The results revealed an intercalated structure in ABS/OMT nanocomposites and the OMT layers mainly distribute in SAN phase. However, a completely exfoliated structure was found in ABS/BER-AO/OMT nanocomposites and OMT layers preferentially located in the BER phase which indicated that the OMT platelets had a much higher affinity with brominated epoxy resin than ABS resin. Based on the above morphological results, a schematic diagram of the ABS/OMT, ABS/BER-AO/OMT nanocomposites was established. The thermal degradation behavior was characterized by thermogravimetry. The results showed that the exfoliation of OMT can enhance the thermal stability of pure ABS resin and ABS/BER blends. An increase in the limited oxygen index (LOI) value was observed with the addition of OMT and it was found that such an enhancement is closely related to the morphologies of the chars formed after combustion. A synergistic effect between OMT and BER-AO during the combustion of the nanocomposites was found and a schematic mechanism was presented.     

THERMAL DECOMPOSITION AND FLAMMABILITY OF ACRYLONITRILE-BUTADIENE-STYRENE/MULTI-WALLED CARBON NANOTUBES COMPOSITES

Thermal and flammability properties of acrylonitrile-butadiene-styrene copolymer (ABS) with the addition of multi-walled carbon nanotubes (MWNTs) were studied.ABS/MWNTs composites were prepared via melt blending with the MWNTs content varied from 0.2% to 4.0% by mass.Thermogravimetry results showed that the addition of MWNTs accelerated the degradation of ABS during the whole process under air atmosphere,and both onset and maximum degradation temperature were lower than those of pure ABS.The destabilizat...     

Aspects of degradation and stability of ABS copolymers. I. Effect of β-carotene as antioxidant

The oxidative degradation of polybutadiene–styrene–acrylonitrile (ABS) copolymer was extensively investigated. Three factors were studied: the influence of ageing temperature on the rate of the oxidation of the copolymer; the efficiency of β-carotene as chain breaking antioxidant; and the effect of butadiene content on the rate of the oxidative degradation of the ABS copolymer.     

Effect of selected scavengers on radiolytic degradation of 2,4-dichlorophenol for environmental purposes

The effect of pH of irradiated aerated solutions and the presence of various concentrations of bicarbonate and nitrate on radiolytic degradation of 2,4-dichlorophenol in aqueous solutions with γ-irradiation was examined using reversed phase HPLC and ion chromatography. The obtaining complete decomposition and dehalogenation of 2,4-dichlorophenol in the presence of naturally occurring inorganic scavengers may require to increase the irradiation dose in batch conditions up to 10 kGy. The presence of scavengers at different doses affects both efficiency of radiolytic degradation and its mechanism.     

Recycling of ABS and PC from electrical and electronic waste. Effect of miscibility and previous degradation on final performance of industrial blends

The aim of this work, within the framework of polymer recycling, is to upgrade waste from electrical and electronic equipment. Blends of the two major residues were prepared via a melt blending process. These are ABS consisting of a SAN thermoplastic matrix with a dispersed elastomeric (polybutadiene rubber) component and polycarbonate (PC). The effect of partial miscibility and previous degradation levels was investigated. Mechanical characterization of ABS/PC systems was carried out to determine the optimum composition range. Previous degradation levels of the two wastes were investigated by FTIR and little degradation was found on ABS due to the presence of a polybutadiene rubber which is more sensitive to thermo-oxidative processes but no significant degradation was found on PC. Differential scanning calorimetry (DSC) tests demonstrated certain miscibility between the two components by identifying two glass transition temperatures. This partial miscibility, together with the small degradation of the elastomeric component, contributes to a low interaction promoting a decrease on mechanical performance. Scanning electron micrographs (SEM) showed the system morphology and certain lack of adherence along SAN/polybutadiene interface related to degradation of polybutadiene spheres which act as stress concentrators. The use of the equivalent box model (EBM) allowed to quantify the interaction level by determining an interaction/adherence parameter “A”, which turned to be lower than 1 and corroborated the lack of interaction.     

Kinetics study of thermal oxidative degradation of ABS containing flame retardant components

The thermal oxidative degradation kinetics of pure acrylonitrile–butadiene–styrene (ABS) and the flame-retarded ABS materials with intumescent flame retardant (IFR) were investigated using Kissinger, Flynn–Wall–Ozawa, and Horowitz–Metzger methods. The results showed that the degradation of all samples included two stages, the activation energy at the first stage decreased by the incorporation of these flame retardant components, while increased at the second stage. The activation energy order of the flame-retarded ABS samples at stage 2 illustrates the relationship between the composition of IFRs and their flame retardancy, FR materials with appropriate acid agent/char former ratio has higher activation energy and better flame retardancy.     

Degradation behavior and kinetic study of ABS polymer

The degradation kinetics of the ABS terpolymer (acrylonitrile-butadiene-styrene) was investigated by means of thermogravimetric analysis. The samples were heated from 30 to 900°C in nitrogen atmosphere applying three different heating rates: 5, 10 and 20°C min⁻¹. The Vyazovkin model-free kinetic method was used to calculate the activation energy (E) of the degradation process as a function of conversion and temperature. Between 20 and 80% of conversion, E was calculated and the figures were: for ABS GP, E is 204.5±11.5 kJ mol⁻¹ (medium value); for ABS HI, E is 239.0±9.8 kJ mol⁻¹; for ABS HH, E is 242.4±5.4 kJ mol⁻¹.     

Thermal behaviour of binary and ternary copolymers containing acrylonitrile

Three types of acrylonitrile copolymers (acrylonitrile-styrene-butadiene copolymer (ABS¹), acrylonitrile-styrene random copolymer (SAN²) and acrylonitrile-butadiene random copolymer (BAN³) were studied by thermogravimetry (TG/DTG⁴) and by pyrolysis in a semi-batch process at 450 °C in order to find structure–thermal behaviour relationships. The overlapped thermo-oxidative degradation processes were separated and the corresponding kinetic parameters were calculated. The TG/DTG studies have evidenced that the styrene-acrylonitrile interactions stabilize the nitrile groups reacting by chain scission rather than cyclization and destabilize the styrene units. Also, the cyclization of the acrylonitrile units in ABS is favoured by interactions with the styrene and butadiene units. The pyrolysis behaviour evidenced that the styrene-acrylonitrile interactions in SAN and ABS lead to the formation of 4-phenylbutyronitrile as the most important decomposition compound. ABS shows similar composition of the degradation oil with SAN copolymer therefore in the ABS the styrene-butadiene interactions are less important than those between styrene and acrylonitrile units.     

Fuel oil from ABS using a tandem PEG-enhanced denitrogenation-pyrolysis method: Thermal degradation of denitrogenated ABS

Thermal degradation of ABS and denitrogenated ABS samples (DABS), prepared by sequential hydrolysis of ABS using PEG/NaOH, has been investigated under inert gas and at atmospheric pressure in a temperature range between 40 and 700 °C, by means of TGA, TGA-IR, and TGA-MS, to study the link between original structure of DABS and eventual pyrolysis. For DABS, thermal decomposition begins at the side groups of -CONH₂ and/or -COOH, resulting in a lower initial degradation temperature of DABS (around 330 °C) relative to ABS (372.5 °C). Moreover, less HCN and acrylonitrile evolve from the DABS samples, while the evolution of CO₂ starts earlier and becomes more important, in line with the decreased number of -CN groups and the increased number of -COOH functional groups due to hydrolysis. The results from thermo-analytical experiments were confirmed by batch pyrolysis tests: the nitrogen content of oil produced from DABS pyrolysis is much lower, compared with that from ABS, proving that effective denitrogenation of ABS prior to pyrolysis is beneficial to the quality of pyrolysis oil.     

The application of transition metal molybdates (AMoO4, A = Co,Ni, Cu) as additives in acrylonitrile‐butadiene‐styrene with improved flame retardant and smoke suppression properties

In this paper, three different kinds of typical transition metal molybdates (AMoO₄, A = Co, Ni, Cu) were synthesized via a hydrothermal method. X‐ray diffraction and scanning electron microscopy (SEM) were used to characterize their structures. Then, the synthesized molybdates were incorporated into acrylonitrile‐butadiene‐styrene (ABS) matrix via a masterbatch‐based melt blending method. SEM images showed that transition metal molybdates (AMoO₄, A = Co, Ni, Cu) are homogeneously dispersed in the ABS matrix. Thermogravimetric analysis (TGA) results indicated that the introduction of these transition metal molybdates (AMoO₄, A = Co, Ni, Cu) could accelerate the degradation of ABS, especially for the CuMoO₄. The initial thermal degradation temperatures are decreased by 9–12°C for ABS/CoMoO₄ and ABS/NiMoO₄ composites. But for the ABS/CuMoO₄ composite, it is decreased by 45°C. Meanwhile, the peak of heat release rate is decreased by 10%–13% for ABS/CoMoO₄ and ABS/NiMoO₄ composites, and it is decreased by 26% for ABS/CuMoO₄ composite. Moreover, TGA/infrared spectrometry was used to investigate the smoke suppression effect of CuMoO₄ in ABS indirectly; it showed that the addition of CuMoO₄ inhibits the release of hydrocarbons, aromatic compounds, and CO and promotes the generation of CO₂. Copyright © 2014 John Wiley & Sons, Ltd.     

Radiolysis of NTA complexes with U(VI), Fe(III) and Ni(II)

The radiolysis of NTA complexes with U(VI), Fe(III) and Ni(II) has been studied spectrophotometrically at different pH values, at different doses of⁶⁰Co gamma-radiation. The absorbed doses were measured using the Fricke dosimeter. A clear relation between the radiolytic degradation of the complexes and the ligand concentration was observed. The G values were computed and compared with that of G(OH).     

Thermal and structural analysis of ultrasonic-welded PC/ABS blend for automobile applications

PC/ABS thermoplastic blends are widely employed in manufacturing sectors, as it yields good mechanical behavior when subjected to dynamic loading conditions. While investigating the fundamental nature of PC/ABS blends, ultrasonic welding process appears to suit their joining as compared to other conventional techniques. This paper focuses on PC/ABS welding using ultrasonic and the subsequent investigation from the insight of thermal science. It is imperative for the materials to retain key properties after subjecting it to welding. Examinations to evaluate these properties through DSC reveal a lower onset temperature change and a small variation of glass transition temperature, respectively, for parts which indicate minimal changes in thermal properties in welded and non-welded specimens. Apparent activation energies determined from TG data are practically independent of heating rates, which suggests that the most important process in the degradation of these materials corresponds to ABS. Those mixtures with high PC content show a clear increase in apparent activation energies with heating rate, suggesting that the thermal degradation mechanism of these samples is composed of several complex processes, each predominant during different stages of the overall process. SEM is used to investigate the structural morphology of the welded parts.     

Improved cell morphology and reduced shrinkage ratio of ETPU beads by reactive blending

Thermoplastic polyurethane foam beads (ETPU) have attracted attention of researchers in recent years due to their wide use in industrial applications. In this study, a small amount of acrylonitrile-butadiene-styrene copolymer (ABS) was blended with TPU under the assistance of dicumyl peroxide (DCP) and maleic anhydride (MAH) to improve the cell morphology and reduce shrinkage ratio of the resulting blends. These blends were then foamed to prepare TPU/ABS blends foam beads in an autoclave using supercritical CO₂ as the blowing agent at different temperatures and FTIR spectra, and rheological and foaming properties of the samples were evaluated. The melt viscosity, melt strength and elasticity of TPU/ABS were improved with the increase of the ABS content. These results were attributed to the grafting and heterogeneous nucleation points provided by the ABS. These enhanced properties were used to produce foams with better cell morphology and increased expansion ratio. Furthermore, the TPU/ABS blends foam beads showed lower shrinkage ratios with increasing ABS content. Thus, the addition of ABS is a facile method for improving the cell morphology and anti-shrinkage properties of ETPU.     

The investigation of intumescent flame-retarded ABS using zinc borate as synergist

The influence of zinc borate (ZB) on the flammability and thermal properties of acrylonitrile–butadiene–styrene copolymer (ABS)/ammonium polyphosphate (APP)/poly(p-ethylene terephthalamide) (PETA) system was investigated. When the loadings of ABS, APP, PETA, and ZB were 70, 20.8, 6.9, and 2.3 %, respectively, the LOI value reached 36 and UL-94 vertical burning test was V-0. Even when 1.5 % ZB was added into ABS/APP/PETA (80/13.9/4.6) system, the LOI value was also 27. The thermal degradation of the composites was investigated by means of thermogravimetric analysis (TG) and Fourier transform infrared spectroscopy (FTIR). The TG indicated that the addition of ZB improved the thermal stability and the char residue of the ABS/APP/PETA system. What’s more, the mechanism was investigated by FTIR. The spectrum of flame retardant residue suggested that ZB reacted with APP/PETA physically. Additionally, scanning electron microscopy showed that the surface of intumescent charred layer obtained after combustion of ABS/APP/PETA/ZB (70/20.8/6.9/2.3) was compact and thick.     

Synchrotron-based FTIR microspectroscopy for the mapping of photo-oxidation and additives in acrylonitrile–butadiene–styrene model samples and historical objects

Synchrotron-based Fourier transform infrared micro-spectroscopy (SR-μFTIR) was used to map photo-oxidative degradation of acrylonitrile–butadiene–styrene (ABS) and to investigate the presence and the migration of additives in historical samples from important Italian design objects. High resolution (3 × 3 μm²) molecular maps were obtained by FTIR microspectroscopy in transmission mode, using a new method for the preparation of polymer thin sections. The depth of photo-oxidation in samples was evaluated and accompanied by the formation of ketones, aldehydes, esters, and unsaturated carbonyl compounds. This study demonstrates selective surface oxidation and a probable passivation of material against further degradation. In polymer fragments from design objects made of ABS from the 1960s, UV-stabilizers were detected and mapped, and microscopic inclusions of proteinaceous material were identified and mapped for the first time.     

Evaluation of the thermal degradation of PC/ABS/montmorillonite nanocomposites

Polycarbonate (PC)/acrylonitrile‐butadiene‐styrene (ABS) polymer alloy/montmorillonite (MMT) nanocomposites were prepared using a direct melt intercalation technique. The pyrolytic degradation and the thermo‐oxidative degradation of the polymer alloy and the nanocomposites were studied by thermogravimetric analysis (TGA). The kinetic evaluations were performed by the model‐free kinetic analysis and the multivariate non‐linear regression. Apparent kinetic parameters for the overall degradation were calculated. The results show that PC/ABS/MMT nanocomposites have high thermal stability and low flammability. Their pyrolytic degradation and the thermo‐oxidative degradation model are different. The pyrolytic degradation reaction of the polymer is a two‐step parallel reaction model: nth‐order reaction model, and ath‐degree autocatalytic reaction with an nth‐order reaction autocatalytic reaction, whereas the thermal oxidative degradation reaction of the polymer is a two‐step following reaction model: A → B → C of nth‐order reaction model, and autocatalytic reaction model. Copyright © 2005 John Wiley & Sons, Ltd.     

Thermal and photo-degradation of unstabilized ABS

Thermal- and photo-stabilities of unstabilized acrylonitrile-butadiene-styrene terpolymer, ABS, have been investigated by i.r. spectroscopy. Degradation of ABS samples is initiated by attack on the polybutadiene (PB) component; oxidation products containing hydroxyl and carbonyl groups are produced. The effect of prior thermal processing is to introduce into the polymer hydroperoxides arising from oxidative destruction of PB-unsaturation; these hydroperoxides act as catalysts during subsequent u.v. irradiation. The insolubility of degraded samples of ABS is associated with the formation of cross-linked structures and occurs mainly in the PB segment. It is concluded that the degradation characteristics of ABS are essentially those of the polybutadiene component.     

Kinetics of isothermal thermogravimetrical degradation of PVC/ABS blends

The PVC/ABS blends were degradated by means of isothermal thermogravimetry at temperatures at 210...240°C in nitrogen. Applying the stationary point method to the data obtained from thermogravimetric curves, apparent activation energy, preexponential factor and compensation parameter for each blend were calculated. The constancy of compensation parameters points to an unchanged mechanism of poly (vinyl-chloride) (PVC) thermal degradation in the presence of acrylonitrile butadiene-styrene (ABS). Upon increasing the fraction of ABS in the blend up to 50% only the kinetics of the process is changed.     

磷酸酯阻燃剂HDP的合成工艺及其在ABS中的阻燃作用

采用新工艺路线合成高熔点磷酸酯阻燃剂———对苯二酚双(二苯基磷酸酯)(HDP).首先采用对苯二酚和三氯氧磷合成中间产物,再将中间产物与苯酚反应,经分离纯化得到产品HDP,收率达到90%以上,常温下为白色固体.采用傅里叶红外光谱、氢谱、磷谱和质谱测试确定了其结构.同时,研究了HDP的阻燃性,并与间苯二酚双(二苯基磷酸酯)(RDP)进行了比较,研究发现当HDP和RDP分别与成炭剂酚醛树脂(NP)按20/10比例添加到丙烯腈-丁二烯-苯乙烯(ABS)树脂中,增强了复合材料凝聚相阻燃作用,极限氧指数(LOI)有所提高.通过热重及锥形量热分析两种复合材料以及各种组分的热降解过程,阻燃剂的添加对ABS树脂的热稳定性和残炭量明显提高,而且ABS/HDP/NP复合材料的抑烟性更好;同时采用扫描电镜(SEM)和X射线能量色散谱(EDS),发现ABS/HDP/NP复合材料燃烧后成炭空隙均匀,其残炭中磷分布比ABS/RDP/NP复合材料残炭中的磷分布更加均匀.研究表明,HDP与NP互配添加到ABS中,在凝聚相阻燃作用优于RDP.