Standardization and certification in the area of environmentally degradable plastics

Environmentally degradable polymers and plastics (EDPs) are a group of polymeric materials experiencing a rapid growth in number as well as in their applications and quantities used. The assessment of their key characteristic - degradability, including eventually biodegradability as the ultimate stage, is scientifically and technically a challenging issue and has led to differing interpretations in the past. In order to standardize techniques and criteria a number of standards were established by different standardization bodies which are also used as a basis for certification schemes. An up-to-date inventory of the rapidly growing standardization body is presented with basic interpretation to help guide the non-expert. A basic introduction to EDPs and polymer degradation is added for clarity.     

Implicitly representing arrangements of lines or segments

Anarrangement ofn lines (or line segments) in the plane is the partition of the plane defined by these objects. Such an arrangement consists ofO(n ²) regions, calledfaces. In this paper we study the problem of calculating and storing arrangementsimplicitly, using subquadratic space and preprocessing, so that, given any query pointp, we can calculate efficiently the face containingp. First, we consider the case of lines and show that with (n) space¹ and (n ^3/2) preprocessing time, we can answer face queries in (n)+O(K) time, whereK is the output size. (The query time is achieved with high probability.) In the process, we solve three interesting subproblems: (1) given a set ofn points, find a straight-edge spanning tree of these points such that any line intersects only a few edges of the tree, (2) given a simple polygonal path , form a data structure from which we can find the convex hull of any subpath of quickly, and (3) given a set of points, organize them so that the convex hull of their subset lying above a query line can be found quickly. Second, using random sampling, we give a tradeoff between increasing space and decreasing query time. Third, we extend our structure to report faces in an arrangement of line segments in (n ^1/3)+O(K) time, given(n ^4/3) space and (n ^5/3) preprocessing time. Lastly, we note that our techniques allow us to computem faces in an arrangement ofn lines in time (m ^2/3 n ^2/3+n), which is nearly optimal.The first author is pleased to acknowledge the support of Amoco Fnd. Fac. Dev. Comput. Sci. 1-6-44862 and National Science Foundation Grant CCR-8714565. Work on this paper by the fifth author has been supported by Office of Naval Research Grant N00014-87-K-0129, by National Science Foundation Grant NSF-DCR-83-20085, by grants from the Digital Equipment Corporation, and the IBM Corporation, and by a research grant from the NCRD—the Israeli National Council for Research and Development. The sixth author was supported in part by a National Science Foundation Graduate Fellowship. This work was begun while the non-DEC authors were visiting at the DEC Systems Research Center.     

Model reactions for stereochemistry of Ziegler-Natta polymerization: Asymmetric hydroisomerization of α-olefins by chiral titanium tetra-alkoxides/tri-isobutyl aluminum catalytic systems

Homogeneous catalytic systems based on optically active low-molecular-weight and macromolecular titanium alcoholates and tri-isobutyl aluminum were used in the isomerization and hydrogenation of chiral and prochiral olefins. The reactions performed in a nitrogen and hydrogen atmosphere show a different behavior in regard to reaction rate, composition of reaction mixture, and stereochemical control. The catalyst based on macromolecular titanium alcoholate displays lower activity and a varying influence on the stereochemical pathway with respect to the catalysts based on low- molecular-weight alcoholates. The data obtained in both cases strongly support the absence of a stereocontrol by the growing chain in the stereoelective polymerization of racemic α-olefins by Ziegler-Natta catalysts based on optically active precursors. Finally evidence is provided in favor of the intermediate step responsible for asymmetric isomerization which does not occur via η-allyl complex.     

Thermal decomposition mechanisms of sequential bipolyesters based on propeneglycol and hydroxybenzoic/phthalic diacid derivatives

Some bipolyesters consisting of 1,2-propene glycol residue (P) and symmetric aromatic diacid residue constituted by two p-oxybenzoyl groups coupled by a terephthaloyl (HTH), phthaloyl (HOH) and isophthaloyl (HIH) group, and a nonsymmetric diacid residue constituted by a p-oxybenzoyl and a terephthaloyl group (HT), have been investigated by direct pyrolysis–mass spectrometry. The results show that intramolecular exchange reactions occurring at the pyrolysis stage cause a reorganization of the copolymer sequences. Sequential bipolyesters I–IV are ideal materials for the investigation of the extent of thermal reorganization induced in the bipolymer sequences by the pyrolytic process.     

Improved bounds on weak ε-nets for convex sets

LetS be a set ofn points in ℝ ^d . A setW is aweak ε-net for (convex ranges of)S if, for anyT⊆S containing εn points, the convex hull ofT intersectsW. We show the existence of weak ε-nets of size , whereβ ₂=0,β ₃=1, andβ _d ≈0.149·2 ^d-1(d-1)!, improving a previous bound of Alonet al. Such a net can be computed effectively. We also consider two special cases: whenS is a planar point set in convex position, we prove the existence of a net of sizeO((1/ε) log^1.6(1/ε)). In the case whereS consists of the vertices of a regular polygon, we use an argument from hyperbolic geometry to exhibit an optimal net of sizeO(1/ε), which improves a previous bound of Capoyleas. Work by Bernard Chazelle has been supported by NSF Grant CCR-90-02352 and the Geometry Center. Work by Herbert Edelsbrunner has been supported by NSF Grant CCR-89-21421. Work by Michelangelo Grigni has been supported by NSERC Operating Grants and NSF Grant DMS-9206251. Work by Leonidas Guibas and Micha Sharir has been supported by a grant from the U.S.-Israeli Binational Science Foundation. Work by Emo Welzl and Micha Sharir has been supported by a grant from the G.I.F., the German-Israeli Foundation for Scientific Research and Development. Work by Micha Sharir has also been supported by NSF Grant CCR-91-22103, and by a grant from the Fund for Basic Research administered by the Israeli Academy of Sciences.     

Environmentally degradable bio-based polymeric blends and composites

Blends and composites based on environmentally degradable-ecocompatible synthetic and natural polymeric materials and fillers of natural origin have been prepared and processed under different conditions. Poly(vinyl alcohol) (PVA) was used as the synthetic polymer of choice by virtue of its capability to be processed from water solution or suspension as well as from the melt by blow extrusion and injection molding. Starch and gelatin were taken as the polymeric materials from renewable resources. The fillers were all of natural origin, as waste from food and agro-industry consisted of sugar cane bagasse (SCB), wheat flour (WF), orange peels (OR), apple peels (AP), corn fibres (CF), saw dust (SD) and wheat straw (WS). All the natural or hybrid formulations were intended to be utilized for the production of: a) Environmentally degradable mulching films (hydro-biomulching) displaying, in some cases, self-fertilizing characteristics by in situ spraying of water solutions or suspensions; b) Laminates and containers to be used in agriculture and food packaging by compression and injection molding followed by baking. Some typical prototype items have been prepared and characterized in relation to their morphological and mechanical properties and tested with different methodology for their propensity to environmental degradation and biodegradation as ultimate stage of their service life. A relationship between chemical composition and mechanical properties and propensity to biodegradation has been discussed in a few representative cases.     

X-ray diffraction study of the smectic mesophase of some azobenzene-containing polyacrylates

Abstract

An X-ray study is performed on powder specimens and on stretched oriented fibres of two liquid crystalline polyacrylates containing the azobenzene mesogenic unit with either a 4′-n-pentyloxy (sample 1–4) or 4′-n-hexyloxy (sample 1–5) substituent. The X-ray diffraction patterns of both samples showed the presence of a bilayer smectic C mesophase with the mesogneic groups tilted by an angle β ～ 45° (1–4) or β ～ 38° (1–5) with respect to the layer normal. The electron density profile p(z) along the direction normal to the smectic layers was calculated by Fourier inversion and possible structural models of the smectic mesophase are discussed. A partial interdigitation of the terminal alkyloxy substituents appears to occur.     

Electroclinic properties of chiral smectic a liquid crystalline polymers and block copolymers

The scope for the synthesis and investigation of chiral smectic A liquid crystalline (LC) polymers and block copolymers is discussed. LC block copolymers can combine the molecular order of liquid crystals and the supramolecular order typical of block copolymers, thus allowing to attain information on mesomorphic responses in restricted geometries. We present a general overview on several aspects of the syntheses and properties of LC block copolymers, specifically those obtained by starting from azomacroinitiators. These materials can exhibit an electroclinic effect, that is an electrically induced molecular tilt, which is characterized by a linear dependence on the applied field and a very fast response time in the paraelectric smectic A phase. The current progress in their potential application in electrooptics is outlined.     

Optically active alternating copolymers of maleic anhydride and alkylvinylethers

Maleic anhydride (MAn) was copolymerized in benzene solution at 60° using AIBN with some optically active alkylvinylethers (RVE) having an asymmetric carbon atom at the α, β, γ or δ position with respect to the oxygen atom [R = (S)-1-methylpropyl, (R)-1-methylbutyl, (S)-2-methylbutyl, (S)-3-methylpentyl, (S)-4-methylhexyl, (S)-1-methylheptyl and (S)-3,7-dimethyloctyl]. Chemical compositions and solubilities of the polymeric products as well as optical rotation properties and spectroscopic measurements (i.r. and NMR) confirmed the formation of copolymers with a predominantly alternating structure. Two Cotton effects of low but definite intensity attributable to $\text{n → π}{}^1$ electronic transitions of carbonyl groups of anhydride moieties were observed between 200 and 250 nm. Failure to achieve complete cleavage of chiral side chains does not enable us to attribute the induced optical activity of anhydride moieties either to the asymmetric carbon atom present in the side chain or to the tertiary chiral centres present in the main chain or both.