Surface modification of HDPE, PP, and PET films with KMnO4/HCl solutions

Surface modification of high-density-polyethylene (HDPE), polypropylene (PP), and poly(ethylene terephthalate) (PET) films was promoted by potassium permanganate solutions in HCl acidic medium using eight conditions by varying time, temperature, and oxidative solution concentration. This oxidation system introduced different amounts of carbonyl-carboxyl and hydroxyl groups onto the polymer surfaces. Drop water contact angle, FTIR, TGA, and SEM were used to assess oxidation efficiency and the surface changes suffered by the polymer film. The hydrophilicity of films obtained by contact angle was analyzed using a 2³ factorial design in Design-Expert^® program to obtain the main effects, the variance, and the interaction between the effects in action in the oxidation process.     

Surface modification of superfine tourmaline powder with titanate coupling agent

The effects of surface modification of the superfine tourmaline powder with a titanate coupling agent were discussed by investigating its hydrophobicity and distribution in poly (ethylene terephthalate) (PET). The modified tourmaline powder became hydrophobic, which resulted in better distribution in the PET matrix. The mechanism of the surface modification was analyzed.     

Surface characterizations of poly(ethylene terephthalate) film modified by a carbohydrate-bearing photoreactive azide group

Grafting of a carbohydrate UV-reactive molecule, the β-d-galactopyranosyl-(1-4)-1-N-[2-(4-azidophenyl amino)-ethylamino]-1-deoxy-d-glucitol (AzPhLac), has been achieved on poly(ethylene terephthalate) film. The dependence of surface density and yield of grafted AzPhLac have been studied versus the number of moles of UV-treated AzPhLac via the deposit of a drop of solution with a known volume and concentration. A nearly complete grafting of initial AzPhLac molecules was reached for the lowest concentration and lowest volume of solution deposit conditions. Grafting density values in the range of 29-181 nmol/cm² confirm the polymeric nature of the grafted layer. FTIR-ATR demonstrated the heterogeneity in thickness of the grafted surface due to the drop-deposit method and solvent evaporation process. AFM (imaging) allowed us to find a correlation between grafting density and rms roughness. Water-contact angle and AFM (contact mode) gave further evidence of the hydrophilic nature of the extreme surface.     

Optimisation of mould surface temperature and bottle residence time in mould for the carbonated soft drink PET containers

Polyethylene terephthalate (PET) bottles, which are usually produced by injection stretch blow moulding (ISBM) are widely used for carbonated soft drinks (CSD) storage and transportation. Stretch rod movement, blow pressure, preform temperature profile, mould surface temperature and material properties are among the most important factors affecting the final product's quality in terms of the thickness distribution, burst pressure and top-load resistance of the bottles. However, the residence time of the blown bottle inside the mould is also an important factor affecting its final properties. Especially in PET bottle production for hot fillings, the residence time is a very important factor because the longer the residence time the better the crystalline structure of the PET. In this production, the lid section is desired to have a fully crystalline form so that it can withstand hot fluids. In this study, the aim was to optimise the mould surface temperature and the blown bottle's residence time inside the mould for 1 L soft drink PET bottle production based on the final properties using the ECHIP 7 design of experiment (DOE) program. The method employed through this program was a quadratic one. Optimum process parameters were determined by the response surface method (RSM) and the process settings ensuring maximum top-load, burst pressure, Tg and degree of crystallinity were regarded to be optimum. It was found that the optimum mould surface temperature and blown bottle residence time inside the mould were 10 °C and 20 s, respectively.     

用X-射线衍射法测定聚对苯二甲酸乙二醇酯/聚对苯二甲酸丁二醇酯共混体系的结晶度

结晶度是表征聚合物性质的重要参数,它对聚合物的物理和机械性能有很大影响,在测定聚合物的结晶度的各种方法中,X-射线衍射法的意义明确且应用最为广泛。然而,用X-射线衍射法测定聚合物结晶度绝大部分只限于单组份体系,用于共混体系的报道尚不     

PET/PEN/DBS共混体系结构与形貌的研究

共混是改善聚合物性能的一种简单而又行之有效的方法,PET和PEN均为结晶性聚酯,由于PEN合成原料的影响,致使PEN的价格较高,但性能比PET优良,通过二者的共混,既可以提高PET的性能,又可以降低PEN成本,有关PET／PEN共混体系的研究已引起人们的关注,而对于共混体系结晶形态和结晶条件的研究较少,由于成核剂能够提高结晶速率,减小球晶尺寸,因此本文对PET／PEN／DBS共混体系中,组分组成的影响及不同结晶条件下共混物的结晶形貌进行研究。     

Permeability of anti-fouling PEGylated surfaces probed by fluorescence correlation spectroscopy

The present work reports on in situ observations of the interaction of organic dye probe molecules and dye-labeled protein with different poly(ethylene glycol) (PEG) architectures (linear, dendron, and bottle brush). Fluorescence correlation spectroscopy (FCS) and single molecule event analysis were used to examine the nature and extent of probe-PEG interactions. The data support a sieve-like model in which size-exclusion principles determine the extent of probe-PEG interactions. Small probes are trapped by more dense PEG architectures and large probes interact more with less dense PEG surfaces. These results, and the tunable pore structure of the PEG dendrons employed in this work, suggest the viability of electrochemically-active materials for tunable surfaces.     

Inhibited transesterification of PET/PBT blends filled with silica nanoparticles during melt processing

The blends of poly(ethylene terephthalate) (PET) and poly(butylene terephthalate) (PBT) undergo transesterification reactions between PET and PBT during melt processing. In this research, PET/PBT transesterification has been investigated in the presence of nano-fillers, including pure SiO₂ and silane-coupling-agent-modified SiO₂. The results show that the incorporation of SiO₂ nanoparticles inhibits PET/PBT transesterification, and the influence of pure SiO₂ is higher than modified SiO₂. The inhibition of SiO₂ on transesterification is explained by the fact that the hydroxyl end groups of PET and PBT react with the surface hydroxyl groups of SiO₂ before transesterification due to the high activity of surface hydroxyl groups of SiO₂, and the reduction of hydroxyl end groups of PET and PBT leads to the inhibition of transesterification between PET and PBT. This has been demonstrated by the experimental data of TGA, FTIR, and XPS. And the reactivity of hydroxyl end groups of PBT is higher than that of PET.     

Enzymatic and chemical hydrolysis of poly(ethylene terephthalate) fabrics

Alkaline and enzymatic hydrolyzes of poly(ethylene terephthalate) fabrics (PET) were mechanistically compared based on released degradation products (HPLC‐UV‐RI) and changes in surface properties [hydrophilicity, cationic dyeing, X‐ray photoelectron spectroscopy (XPS)]. Enzymatic hydrolysis led to an increase in the amount of hydroxyl and carboxyl groups on the surface resulting in an enhanced water absorption and dyeability. Enzymes partially adsorbed to PET fabrics during hydrolysis were completely removed by subsequent extraction according to XPS analysis. In contrast to the enzyme treatment, alkaline hydrolysis did not lead to an increase of hydroxyl and acid groups according to XPS while both treatments caused a substantial increase in hydrophilicity and were more effective on amorphous fibers. Alkaline hydrolysis led to a greater increase in the K/S value after cationic dyeing due to enlarged surface area. Consequently, ESEM‐images demonstrated that alkaline treatment drastically affected the surface morphology of the polymer resulting in crater‐like structures of the fibers, whereas after enzymatic treatment the morphology of the fibers remained unchanged. To reach similar benefits in hydrophilicity, drastically higher amounts of degradation products were released during alkaline hydrolysis as also indicated by >6% weight loss compared to <1% after enzyme treatment. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6435–6443, 2008     

Hydrolytic degradation of carbohydrate-based aromatic homo- and co-polyesters analogous to PET and PEI

The hydrolytic degradation of a series of homo- and co-polyesters analogous to poly(ethylene terephthalate) (PET) and poly(ethylene isophthalate) (PEI), prepared from carbohydrate-based monomers, was studied. The degradation process was carried out at temperatures of approximately 10 °C above the T_g of the polymers. All the studied polyesters were found to degrade at significant rates, and degradability showed a clear dependence on the configuration of the sugar units present in the polymer chain. No weight loss was detected upon degradation, apparently due to the non-solubility of the degraded products in the aqueous incubation medium. Hydrolysis of co-polyesters took place preferentially by cleavage of the ester groups of the sugar units.     

Discrimination of Thermoplastic Polyesters by MALDI-TOF MS and Py-GC/MS

The aim of this work is to discriminate thermoplastic polyester-polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polytrimethylene terephthalate (PTT), which cannot be easily identified by many methods. Both matrix-assisted laser desorption/ionization-time of flight mass spectrometry (MALDI-TOF MS) and pyrolysis gas chromatography/mass spectrometry (Py-GC/MS) were applied to identify these polyesters owing to their analytical ability to determining polymers' chemical structure. The three thermoplastic polyesters can be easily distinguished by MALDI-TOF MS according to their different repeated units. Py-GC/MS was used to analyze their specific pyrolyzates. The three polyesters can be identified through their characteristic pyrolysis products as well.     

Poly(ethylene terephthalate) modified with aromatic bisester diamides: Thermal and oxygen barrier properties

The synthesis and properties of poly(ethylene terephthalate) (PET) copolymers containing four bisester diamide structural units are reported. Two of the bisester diamides consist of three para‐substituted aromatic rings, and the other two consist of three meta‐substituted aromatic rings. The copolymers have been characterized by nuclear magnetic resonance, differential scanning calorimetry, and dilute solution viscometry. Three of the copolymers can be compression‐molded into amorphous films for oxygen barrier testing, and one of these three films can be oriented for additional barrier testing. The three amorphous films all have lower permeabilities than unoriented PET. However, this difference diminishes upon the orientation of the polymer films. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1668–1681, 2004     

Influence of plasma treatment on the molar mass of poly(ethylene terephthalate) investigated by different chromatographic and spectroscopic methods

The influence of different types of low and atmospheric pressure plasma on poly(ethylene terephthalate) (PET) has been studied in terms of changes in molar mass and molar mass distribution. Apart from a variation of plasma gases (oxygen, helium) different types of plasma (microwave, radio frequency, corona discharge) were used for the plasma surface modification. The changes in molar mass and types of functional end groups of lower molar mass products were investigated by means of matrix-assisted laser desorption/ionization time of flight mass spectrometry (MALDI-TOFMS), whereas the high-molar mass fraction was analyzed by means of size-exclusion chromatography (SEC). The formation of crosslinked products during exposure to a helium plasma, which emits preponderately energy-rich and intense ultraviolet radiation, was proved by means of thermal field-flow fractionation (ThFFF). This method combined with a multiangle laser light scattering (MALLS) detector allows detection of weakly crosslinked polymers and microgels. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1639–1648, 1998     

Some Comments on a Recent Article Dealing with Three Aliphatic-Aromatic Polyesters and Their Spectral Identification

This work discusses the results appearing in Wu et al.’s (2014) article dealing with three aliphatic-aromatic polyesters based on terephthalic acid and their spectral identification. Using an instrument equipped with a switch that allows ions with masses below 5 kDa to be discarded (ion deflector), the authors report the MALDI spectrum of a commercial poly(ethylene terephthalate) with signals up to 80 kDa. I plot the spectral intensities and fit them with a Gaussian curve. The result is carefully examined. Thereafter, attention is moved to the MALDI spectra obtained when the ion deflector is turned off. A computation that gives the number-average and the weight-average molar mass (Mn and Mw) was performed, but the result was Mn = 1362 g/mol and Mw = 1416 g/mol. These values are much too low and they cannot be used. In order to explain this failure, I modified a model developed for poly(pentylene adipate). This hypothesis is discarded and the correct explanation is found. I also discuss other types of instrumentation, for instance, Py-GC/MS combined with library-search and also NMR spectroscopy, with specific reference to the chemical shifts of the -CH2- protons in aliphatic-aromatic polyesters.     

Hydrolysis of post-consume poly(ethylene terephthalate) with sulfuric acid and product characterization by WAXD, C NMR and DSC

Post-consume PET was hydrolysed with commercial sulfuric acid (96%) with varying reaction times (5-120 min). The structure of the material obtained was analysed by ¹³C NMR, DSC, and WAXD and the results were correlated with reaction time. ¹³C NMR shows a decrease in chain size with reaction time and an increase in the number of carboxyl groups at the end of the chains. The correlation of DSC and WAXD data indicates the presence of structures of different sizes and an increase in crystallinity with reaction time. The structure of the samples hydrolysed for 5-60 min is less ordered than those of the samples hydrolysed for 60-120 min because the amorphous phase is predominantly quickly dissolved. Dissolution of the crystalline phase is favoured by the increase in reaction time. In this process, the crystalline memory retained in the dissolution of the crystalline phase behaves as nucleation sites which form smaller and more ordered structures compared to those obtained with shorter reaction times.     

The role of crystalline, mobile amorphous and rigid amorphous fractions in the performance of recycled poly (ethylene terephthalate) (PET)

The action of thermo-mechanical degradation induced by mechanical recycling of poly(ethylene terephthalate) was simulated by successive injection moulding cycles. Degradation reactions provoked chain scissions and a reduction in molar mass mainly driven by the reduction of diethyleneglycol to ethylene glycol units in the flexible domain of the PET backbone, and the formation of -OH terminated species with shorter chain length. The consequent microstructural changes were quantified taking into account a three-fraction model involving crystalline, mobile amorphous (MAF) and rigid amorphous fractions (RAF). A remarkable increase of RAF, to a detriment of MAF was observed, while the percentage of crystalline fraction remained nearly constant. A deeper analysis of the melting behaviour, the segmental dynamics around the glass-rubber relaxation, and the macroscopic mechanical performance, showed the role of each fraction leading to a loss of thermal, viscoelastic and mechanical features, particularly remarkable after the first processing cycle.     

Isothermal crystallization kinetics and melting behaviour of PET/ATO nanocomposites prepared by in situ polymerization

Neat poly(ethylene terephthalate) (PET) and PET/antimony doped tin oxide (ATO) nanocomposites were prepared by in situ polymerization. The study of the isothermal crystallization behaviors of neat PET and PET/ATO nanocomposites was carried out using differential scanning calorimetry (DSC). The crystallization kinetics under isothermal conditions could be described by the Avrami equation. For neat PET and PET/ATO nanocomposites, the Avrami exponent n both decreased with increasing crystallization temperature. In addition, for the same crystallization temperature, the value of n increased with increasing ATO content. These suggested that the crystallization types related to the values of n in the Avrami theory could not be suitable for the crystallization of PET and its nanocomposites. The change of the n values indicated that the addition of ATO resulted in the increase of the crystallizing growth points. That is a heterogeneous nucleating effect of ATO on crystallization of PET. In the DSC scan after isothermal crystallization process, multiple melting behavior was found. And the multiple endotherms could be attributed to melting of the recrystallized materials or the secondary lamellae produced during different crystallization processes. The equilibrium melting temperature of PET in the nanocomposites increased with increasing the ATO content. Surface free energy of PET chain folding for crystallization of PET/ATO nanocomposites was lower than that of neat PET, confirming the heterogeneous nucleation effect of ATO.     

Hydrophilic PET surfaces by aminolysis and glycopolymer brushes chemistry

Poly(ethylene terephthalate) (PET) is a semiaromatic thermoplastic polyester used in many fields. For specific applications, controlled of the surface wettability (hydrophily/hydrophoby) could be a great challenge. Aminolysis of PET surfaces with branched polyethylenimine gives amino functional groups on the surface with high grafting density. Then, in a second step, atom transfer radical polymerization (ATRP) initiator was grafted by reaction with 2‐bromoisobutyryl bromide. Surface initiated ATRP of 2‐lactobionamidoethyl methacrylate (LAMA) was performed in solution in the presence of a sacrificial initiator or an appropriate amount of Cu(II) species that act as deactivator. The efficiency of all reactions was confirmed by X‐ray photoelectron spectroscopy. Wetting properties and surface energy were found to vary systematically depending to the type of functionalization and grafting. The quantity of grafted carbohydrate was determined by phenol/sulfuric acid colorimetric titration. The sugar graft density was observed to vary according to the ratio (monomer)/(free initiator). High graft density could be obtained yielding to superhydrophilic polymer brushes. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 2689–2697     

PC/PET/EPDM共混体系的结晶与熔融行为

本文用解偏振光法与DSC法分别测定并研究了PC/PET/EPDM共混体系的结晶速度、结晶度、Avrami指数(n)和熔融温度及其影响因素,共混物中PET的结晶速度、结晶度均随PC含量增加而下降;EPDM用量不超过10%时,可提高PET的结晶速度,但不影响结晶度和成核与增长方式,n值不变。当EPDM为5%时,结晶速度呈现极大值。经退火处理的共混物呈现熔融双峰,PC量增加,高温熔融峰略移向高温方向;热处理温度升高或时间延长,则低温熔融峰移向高温方向。