Degradation Behavior of Biodegradable Man-Made Fibers in Natural Soil and in Compost.

In open environment applications, fibers are increasingly being used that are expected to biodegrade in the soil after their desired service life. Biodegradable polymer fibers are a versatile alternative to natural fibers. In this study, the degradation behavior of fibers made from polylactic acid (PLA) and a polyhydroxy alkanoate (PHA) blend with PLA, as well as a bicomponent fiber (BICO) made from polybutylene succinate (PBS) and PLA, was investigated. The fibers were stored in topsoil at 23 °C for 12 weeks. In addition, fibers were stored in compost at 58 °C for 4 weeks to investigate the degradation behavior in an industrial composting plant. Reference materials were also stored without substrate under the same temperatures and humidity conditions. Samples were taken regularly, and mechanical testing, scanning electron microscopy (SEM), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), and infrared spectroscopy (IR) were used to study the degradation of the fibers. After 12 weeks in soil at ambient temperatures, the PLA and BICO fibers showed no degradation. The PHA fibers showed cracks in SEM, a decrease in molecular weight, and changes in the IR spectrum. No evidence of biological influence (bacteria or fungi) was found. Under industrial composting conditions, all fibers showed a decrease in strength and molecular weight. For the BICO and the PHA fibers, the SEM images show significant changes. Especially in the PHA fibers, fungal mycelia can be seen. The studies provide a better insight into the processes involved in the degradation behavior under different environmental conditions.

Experimental Determination of Molecular Weight-Dependent Miscibility of PBAT/PLA Blends.

Blends of poly(butylene adipate-co-terephthalate) (PBAT) and polylactide (PLA) have attracted the attention of academia and industry as a sustainable material. Unfortunately, this combination results in problems related to poor miscibility on the molecular level. This study mainly aims to determine the influence of molecular weights on the miscibility of PBAT/PLA blends. First, polymers with various molecular weights were obtained by the hydrolysis of PBAT and methanolysis of PLA. Second, the two components were solution-blended with different molecular weights and weight ratios. Third, each blend was heated to the molten state and subsequently stored at room temperature. Finally, the samples were tested using DSC and SEM. The thermal analysis indicated that the difference in glass transition temperature between both components decreased from about 91 °C to 57 °C and 0 °C, as the number-average molecular weights (Mn) decreased from 52/127 to 9.4/9 and 6.3/6.6 kg/mol. Moreover, the morphology changed from phase-separated with dispersed large particles gradually to uniform and homogeneous. This experimental work validated the trends predicted in the previous study, namely that PBAT/PLA blends changed the state from immiscible to partially miscible to fully miscible with decreasing Mn values. Moreover, we discussed the influencing factors such as weight ratio, temperature, and molecular structure on the miscibility. Based on the results, this work contributes to developing partially miscible and compatible blends without additives.

Poly(lactic acid)-Poly(butylene succinate)-Sugar Beet Pulp Composites; Part II: Water Absorption Characteristics with Fine and Coarse Sugar Beet Pulp Particles; A Phenomenological Investigation.

Sugar beet pulp (SBP) is a residue available in large quantities from the sugar industry, and can serve as a cost-effective bio-based and biodegradable filler for fully bio-based compounds containing bio-based polyesters. The composition of SBP is characterized by an unusually high content of pectins, which are known as water-binding substances. Their molecular structure and the poor gelling properties, compared to other pectin sources, do not allow industrial use on a larger scale. However, good water absorption capacity can be advantageous for promoting plastics degradation or disintegration in the environment. In this study, we evaluated the water absorption capacity and processes of SBP-filled composites with bio-based polyesters on a longer time scale. We analyzed water absorption from a phenomenological point of view and tried to derive basic parameters for the general description of the composites behavior. We found that polar polyesters or polyester blends filled with higher amounts of especially coarse SBP suffer disintegration within a few weeks when supplied with sufficient water. On the other hand, less polar polyesters filled with fine SBP rather absorb water but do not show disintegration for several months. On a time scale of a few years, catalytic disintegration of the composites appears to be independent of the addition of SBP.

Poly(Lactic Acid)-Poly(Butylene Succinate)-Sugar Beet Pulp Composites; Part I: Mechanics of Composites with Fine and Coarse Sugar Beet Pulp Particles.

Sugar beet pulp (SBP) is a residue available in large quantities from the sugar industry, and can serve as a cost-effective bio-based and biodegradable filler for fully bio-based compounds based on bio-based polyesters. The heterogeneous cell structure of sugar beet suggests that the processing of SBP can affect the properties of the composite. An "Ultra-Rotor" type air turbulence mill was used to produce SBP particles of different sizes. These particles were processed in a twin-screw extruder with poly(lactic acid) (PLA) and poly(butylene succinate) (PBS) and fillers to granules for possible marketable formulations. Different screw designs, compatibilizers and the use of glycerol as a thermoplasticization agent for SBP were also tested. The spherical, cubic, or ellipsoidal-like shaped particles of SBP are not suitable for usage as a fiber-like reinforcement. In addition, the fineness of ground SBP affects the mechanical properties because (i) a high proportion of polar surfaces leads to poor compatibility, and (ii) due to the inner structure of the particulate matter, the strength of the composite is limited to the cohesive strength of compressed sugar-cell compartments of the SBP. The compatibilization of the polymer-matrix-particle interface can be achieved by using compatibilizers of different types. Scanning electron microscopy (SEM) fracture patterns show that the compatibilization can lead to both well-bonded particles and cohesive fracture patterns in the matrix. Nevertheless, the mechanical properties are limited by the impact and elongation behavior. Therefore, the applications of SBP-based composites must be well considered.

Uncompatibilized PBAT/PLA Blends: Manufacturability, Miscibility and Properties.

Polymer blends of poly(butylene adipate-co-terephthalate) (PBAT) and polylactide (PLA) have been drawn attention due to the application potential as packaging or agricultural films. This study aims to determine the manufacturability, miscibility and mechanical properties of uncompatibilized PBAT/PLA blends prepared using different techniques. First, PBAT and PLA are melt-blended in a wide range of ratios from 90/10 to 10/90. The compounds are then processed into pressed panels, flat films and blown films. Finally, the thermal, morphological, rheological and mechanical properties of these blends are investigated. PBAT/PLA blends have a small difference of solubility parameters, predicting theoretically good miscibility. However, they show two almost unchanged glass transition temperatures in the DSC, phase separation in SEM and two relaxation mechanisms in the Cole-Cole plot. The phase morphology varies depending on both the blend ratios and the preparation techniques. Tensile tests indicate that with increasing PLA content the elongation at break decreases. A good correlation between the elongation at break and the tear propagation resistance is found. Furthermore, the trouser tear method is proven to be more applicable to differentiate highly extensible blown films compared with the Elmendorf tear method.

Thermal and Morphological Properties of Poly(L-Lactic Acid)/Poly(D-Lactic Acid)-B-Polycaprolactone Diblock Copolymer Blends.

Due to the brittle nature of poly(lactic acid) many attempts have been made to flexibilize this polyester for applications such as thin films and foils. However, due to complex phase behavior, many drawbacks for plasticizer and blend components are described. To overcome miscibility, post crystallization and migration issues a principle of click-chemistry was employed to change the molecular characteristics from external to internal plasticization by fixation of a plastisizing unit with help of a stereocomplex crystallization. Hydroxyl terminated polycaprolactone oligomers were used as a macroinitiator for the ring opening polymerization of d-lactide, resulting in blockcopolymers with plasticizing unit polycaprolactone and compatibilizing poly(d-lactic acid)-blocks. The generated block copolymers were blended with a poly(l-lactic acid)-matrix and formed so called stereocomplex crystals. In comparison to unbound polycaprolactone the polycaprolactone blocks show a lower migration tendency regarding a solution test in toluene. Besides that, trapping the plasticizing units via stereocomplex also improves the efficiency of the plasticizer. In comparison to polymer blends with the same amount of non-bonded polycaprolactone oligomers of the same molecular weight, block copolymers with poly(d-lactic acid) and polycaprolactone can shift the glass transition temperature to lower values. This effect can be explained by the modulated crystallization of the polycaprolactone-blocks trapped into the matrix, so that a higher effective amount can interact with the poly(l-lactic acid)-matrix.

Compatibility of Chitosan in Polymer Blends by Chemical Modification of Bio-based Polyesters.

For some applications of bioplastics like food packaging or medical devices, applying additives can be necessary to avoid microbial activity and hinder biofilm or fouling formation. A currently promising additive is chitosan (CS), the deacetylated form of the biogenic scaffolding material chitin. Due to its hydrophilicity, chitosan is not compatible with most of the thermoplastic bio-based polymers like poly(lactic acid) (PLA) or polyhydroxyalkanoates (PHA). In this work, compatibilization between chitosan and two selected bio-based polyesters, PLA and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV), was enhanced by grafting maleic anhydride (MAH) and glycidyl methacrylate (GMA), respectively, onto polymer chains using peroxide. The success of grafting was confirmed via titration methods. The effects of grafting agent and peroxide concentrations on grafting reaction and the physical and thermal properties of the functionalized polyesters were investigated. Compounding of the functionalized polyesters with different weight portions of chitosan was accomplished in a discontinuous internal mixer by in-situ functionalization, followed by blending with chitosan. The titration method, scanning electron microscopy, DSC, FTIR and mechanical characterization of the composites showed good interfacial adhesion and suggest the formation of covalent bonds between functional groups of the polyesters and chitosan, especially for the samples functionalized with GMA. The molecular weights (Mw) of the samples showed a change in the molecular weight related to the thermal degradation of the sample. The Mw of the samples grafted with MAH are lower than those functionalized with GMA. Furthermore, integration of chitosan into non-functionalized PLA polymer matrix showed a nucleating effect, while for PHBV, the increase of crystallinity with the content of chitosan was only observed for grafted PHBV.

Polylactide (PLA) and Its Blends with Poly(butylene succinate) (PBS): A Brief Review.

Polylactide (PLA), poly(butylene succinate) (PBS) and blends thereof have been researched in the last two decades due to their commercial availability and the upcoming requirements for using bio-based chemical building blocks. Blends consisting of PLA and PBS offer specific material properties. However, their thermodynamically favored biphasic composition often restricts their applications. Many approaches have been taken to achieve better compatibility for tailored and improved material properties. This review focuses on the modification of PLA/PBS blends in the timeframe from 2007 to early 2019. Firstly, neat polymers of PLA and PBS are introduced in respect of their origin, their chemical structure, thermal and mechanical properties. Secondly, recent studies for improving blend properties are reviewed mainly under the focus of the toughness modification using methods including simple blending, plasticization, reactive compatibilization, and copolymerization. Thirdly, we follow up by reviewing the effect of PBS addition, stereocomplexation, nucleation, and processing parameters on the crystallization of PLA. Next, the biodegradation and disintegration of PLA/PBS blends are summarized regarding the European and International Standards, influencing factors, and degradation mechanisms. Furthermore, the recycling and application potential of the blends are outlined.

Chlorine oxide radicals ClOx (x = 1-4) studied by matrix isolation spectroscopy.

Low pressure flash thermolysis of different precursor molecules containing-ClO, -ClO3 or -OClO3 yield, when highly diluted in Ne or O2 and subsequent quenching of the products in a matrix at 5 or 15 K, ClOx (x = 1, 3, 4) radicals, respectively. If Ne or O2 gas is directed over solid ClO2 at -120 degrees C and the resulting gas mixtures are immediately deposited as a matrix, a high fraction of (OClO)2 is trapped. This enables recording of IR and UV spectra of weakly bonded (OClO)2 dimers and detailed studying of their photochemistry. For Ne or O2 matrix isolated ClO radicals the vibrational wavenumbers and electronic transitions are only slightly affected compared with the gas phase. In this study strong evidence is found for long lived ClO in the electronically excited 2 [symbol: see text] 1/2 state. A comprehensive IR study of Ne matrix isolated ClO3 (fundamentals at 1081, 905, 567, 476 cm-1) yield i) a reliable force field; ii) a OClO bond angle of alpha e = 113.8 +/- 1 degrees and iii) a ClO bond length of 148.5 +/- 2 pm in agreement with predicted data from quantum chemical calculations. The UV/Vis spectrum of ClO3 isolated in a Ne matrix (lambda max at 32,100 and 23,150 cm-1) agrees well with the photoelectron spectrum of ClO3- and theoretical predictions. The origin of the structured high energy absorption is at 22,696 cm-1 and three fundamentals (794, 498, 280 cm-1) are detected in the C2E state. By photolysis of ClO3 with visible light the complex ClO.O2 with ClO in the 2 [symbol: see text] 1/2 state is formed. In an extended spectroscopic study of the elusive ClO4 radical, isolated in a Ne or O2 matrix, three additional IR bands, a complete UV spectrum and a strong interaction with O2 are found. This leads to the conclusion that ClO4 exhibits C2v or Cs symmetry with a shallow potential minimum and forms with O2 the previously unknown peroxy radical O3ClO-O2. All these results are discussed in the context of recent developments in the chemistry and spectroscopy of the important and interesting ClOx (x = 1-4) family of radicals.

Properties of Trifluoroacetyl Peroxynitrate, CF(3)C(O)OONO(2).

The synthesis of CF(3)C(O)OONO(2) is accomplished by the reaction of (CF(3)C(O))(2)O with H(2)O(2) and subsequent nitration of the resulting peracetic acid. The pure product is isolated by trap to trap condensation and removal of the byproducts by treatment with NaHCO(3). At room temperature CF(3)C(O)OONO(2) is stable for days in the gaseous or liquid state. The melting point is -92 degrees C and the boiling point is extrapolated to 42.5 degrees C from the expression ln p = -4045/T + 19.77 (p in mbar, T in K). The compound is characterized further by mass spectrometry and vibrational, NMR, and UV spectroscopy. According to the NMR spectra of CF(3)C(O)OONO(2) as well as CH(3)C(O)OONO(2), both molecules exist in one single conformeric form at room temperature.