The synthesis, characterization and reactivity of linear and network macromolecules by chemical modification of amorphous poly(arylene ethers) with pendant amines were investigated. A new monomer, 3-aminophenyl-bis(4-fluoro phenyl)phosphine oxide was prepared by nitration and reduction of bis(4-fluoro phenyl)phenylphosphine oxide. Statistical incorporation of pendant aryl amines into linear polymers was achieved by copolymerization of the 3-aminophenyl-bis(4-fluorophenyl)phosphine oxide with another activated dihalide monomer such as 4,4'-dichlorodiphenylsulfone and bisphenol-A. Step polymerizations employing nucleophilic aromatic substitution with a dipolar aprotic solvent, toluene as the azeotroping agent, and a slight excess of potassium carbonate as the weak base was the preferred methodology. The concentration of amines along the polymer backbone was successfully controlled by varying the ratio of 3-aminophenyl-bis(4-fluorophenyl)phosphine oxide monomer relative to the other comonomers. Characterization of the pendant amines by proton NMR and potentiometric titration indicated good agreement between the charged amount and the incorporation of this monomer into the copolymer backbone. The pendant amines could be quantitatively converted to pendant phthalimides by reaction with phthalic anhydride. The pendant amines were also reacted to form crosslinkable groups such as maleimides and phenylethynyl phenyl imides. These were thermally treated to induce crosslinking and formed ductile networks which had improved solvent resistance and higher glass transition temperatures. The poly(arylene ethers) containing pendant amines were also reacted with an epoxy resin and 4,4'-diaminodiphenylsulfone to afford epoxy networks which had significant improvement in fracture toughness at selected compositions. Bis(o-aminophenol) monomers were investigated as precursors to poly(arylene ethers) having pendant amines by copolymerization with 4,4'-dichlorodiphenylsulfone and bisphenol-A. These studies resulted in insoluble gels, which suggested that reaction of both the o-aromatic amine and the phenolate with the activated dinalide was occurring. This was further confirmed by the successful oligomerization of o-aminophenol itself with 4,4'-dichloro diphenylsulfone, which afforded NMP soluble novel poly(sec-amino phenoxy diphenylsulfones) with high glass transition temperatures (Tg~276°C). / Ph. D.

Three block copolymer systems where one block was that of an engineering thermoplastic were examined. The first was that of polysulfone-polyarylester block copolymers where glassy-crystalline block copolymers were synthesized and characterized. The morphology of the block copolymers could be controlled by varying the chemical microstructure of the polyester segment. Solvent resistance was shown to improve as the level of crystallinity was increased. Segmented block copolymers of an amorphous polyarylester and polydimethylsiloxane were also investigated. Both the random-block and perfectly alternating synthetic routes were used and it was found that the perfectly alternating technique produced a more regular morphology; than the random-block technique. A study was also carried out on the incorporation of small amounts of polysulfone-polydimethylsiloxane block copolymers blended into homopolysulfone. Improved fracture toughness was observed without a significant loss of stiffness. The morphology of block copolymer particles dispersed in the polysulfone matrix was directly observed through transmission electron microscopy. / Ph. D.

Yes / Natural rubber (NR) and crosslinked polyethylene (XLPE) waste streams were devulcanized by solid state shear milling (S3M), producing a fine powder that may be more easily reprocessed. Understanding devulcanization and the nature of decrosslinked thermoset materials is of utmost importance for turning these waste steams into functional products. It was found that the devulcanized powders contained significant concentrations of radicals, which may be active in the subsequent revulcanization process. The produced devulcanized powders were converted into recyclable thermoplastic vulcanizates (TPVs) by twin screw extrusion. Reprocessing of these powders into value-added products is an important step in recycling and the use of extrusion allows for high throughput and industrial viability. Herein, we demonstrate that the optimal conditions for reprocessing are dependent upon the particle size of the devulcanized powder. Furthermore, dynamic vulcanization is affected by the nature of these recyclate powders. The successfully prepared TPVs showed similar properties to virgin materials, with a high elongation to failure. Therefore, the conversion of waste rubber into the rubber phase of a TPV shows significant promise in moving towards sustainable products, providing the revulcanization step can be well controlled. / EPSRC and NSFC for their funding of this work through the Joint UK-China Low Carbon Manufacturing Grant, Grant number EP/S018573/1.

Thesis (MScEng)--Stellenbosch University, 2013. / AFRIKAANSE OPSOMMING: Saamgestelde materiale het baie gewilde materiale in die lugvaart- en motor industrië geword as gevolg van die gewigsbesparende voordele wat dit inhou. Kostes en ander verwerkingsprobleme het tradisioneel die wydverspreide gebruik van spesifiek termoplasties-versterkte vesels in hierdie areas verhinder. Baie van die vervaardigingsprobleme (spesifiek lang siklusse) is aangespreek met die aanvang van termoplastiese matriks materiaal soos Polyphenolien Sulfied (PPS). Hierdie materiaal voldoen ook aan die lugvaart-industrie se brand-, rook- en giftigheidstandaarde. Termoplastiese saamgestelde materiale kan byvoorbeeld gevind word op komponente in vliegtuie se binneruimtes en ook die voorste rand van die vlerke. Hierdie komponente is hoogs vatbaar vir impakskade. Die hoë sterkte en styfheid tot gewig verhoudings van saamgestelde materiale laat toe vir dun materiaal dwarssnitte. Komponente is dus kwesbaar vir uit-vlakkige impak beladings. Saamgestelde materiale kan ook intern deur hierdie beladings beskadig word en kan nie met die blote oog waargeneem kan word nie. Dit is dus nodig om die skade weens hierdie beladings tydens normale gebruik akkuraat te voorspel. Verder sal dit nuttig wees om die struktuur se gedrag te bepaal in toepassings waar byvoorbeeld passasier veiligheid krities is, soos op vliegtuig ruglenings tydens noodlandings. In hierdie studie is die potensiële vervaardigingsvoordele van termoplastiese saamgestelde materiale gedemonstreer. Daarbenewens is 'n uit-vlakkige impak deur 'n sagte liggaam herbou in 'n laboratorium omgewing. Die primêre doelwit van hierdie studie was om die impak numeries te modelleer. Vervaardigingsvoordele van `n vesel versterkte termoplastiese laminaat is gedemonstreer deur die vervaardiging van 'n konkawe, agt laag laminaat uit 'n vooraf gekonsolideerde geweefde doek. Die totale verwerkingstyd van die plat laminaat na 'n konkawe laminaat was minder as vyf minute. 'n Eenvoudige plat laminaat en 'n konkawe laminaat is onderwerp aan 'n lae snelheid impak deur 'n sagte projektiel. Die impak is gemodelleer deur die evaluering van drie modelleringsmetodes vir die saamgestelde paneel. Die evalueringskriteria het o.a. ingesluit of laminaat se volle gedrag suksesvol gemodelleer kon word met behulp van slegs 2D dop elemente. Die reaksie van die saamgestelde paneel en gepaardgaande faling is met wisselende vlakke van sukses deur die drie geëvalueerde modelle voorspel. Die faling van tussen-laminêre bindings (verwys na as delaminasie) kon nie deur enige van die modelle voorspel word nie. Twee van die modelle het egter in-vlak faling met redelike akkuraatheid voorspel. / ENGLISH ABSTRACT: Due to weight saving advantages composite materials have become a highly popular material in the aerospace and automotive industries. Traditionally processing difficulties and costs have been a barrier to widespread composite material use in these industries. With the advent of thermoplastic matrix materials such as Polyphenoline Sulphide (PPS) the processing difficulties (especially long cycle times) experienced with traditional thermosetting resins can be addressed while maintaining aerospace Fire-Smoke and Toxicity (FST) approval. Thermoplastic composites can for example be found on aircraft interior components and leading edges of the wings. These areas are highly susceptible to impact damage. The high strength- and stiffness to weight ratios of composites allows for thin material cross sections. This leaves the components vulnerable to out-of-plane impact loads. Composite materials may also be damaged internally by these loads, leaving the damage undetectable through visual inspections. It may therefore be necessary to predict the amount of damage a component would sustain during normal operation. Additionally, it would be useful to predict structural response of these materials in applications where passenger safety is crucial, such as aircraft seat backrests during emergency landings. In this study the potential processing benefits of thermoplastic composite materials were demonstrated. Additionally an out-of-plane impact from a soft bodied projectile was reconstructed in a laboratory environment. The primary objective was to numerically model the impact event. Processing benefits of thermoplastics were demonstrated by producing a single curvature eight layered laminate from a pre-consolidated woven sheet. The total processing time from flat panel to a single curvature panel was below five minutes. A simple flat laminate and a single curvature laminate were subjected to a low velocity drop weight impact load from a soft bodied projectile. These impact events were modelled by evaluating three modelling methods for the composite panel structural response and damage evolution. Part of the evaluation criteria included whether laminate failure could be modelled successfully using only 2D shell elements. The response of the composite panel and accompanying failure were predicted with varying levels of success by the three evaluated models. The failure of interlaminar bonds (referred to as delamination) could not be predicted by either model. However two of the models predicted in-plane failure with reasonable accuracy.

Materialdaten sind die Grundlage für belastbare und zuverlässige Simulationsvorhersagen nicht nur Formfüllanalysen sondern auch für Verzugsvorhersagen. SIGMASOFT® Virtual Thermoplastics ist eine zuverlässige Methode, um prozessabhängige Materialdaten für die Spritzgusssimulation verfügbar zu machen. / Material data is the basis for robust and reliable simulation predictions not only for mould filling analyses but also for warpage predictions. SIGMASOFT® Virtual Thermoplastics is a reliable method to make process-dependent material data available for injection moulding simulation.

Thesis (M.Tech.: Mechanical Engineering)-Dept. of Mechanical Engineering, Durban University of Technology, 2007 xiii, 101 leaves / Polymer nanocomposites may be defined as structures that are formed by infusing layered-silicate clay into a thermosetting orthermoplastic polymer matrix. The nanocomposites are normally particle-filled polymers for which at least one dimension of the dispersed particles is in nanoscale. These clay-polymer nanocomposites have thus attracted great interest in industry and academia due to their exhibition of remarkable enhancements in material properties when compared to the virgin polymer or conventional micro and macro-composites. The present work describes the synthesis, mechanical properties and morphology of nano-phased polypropylene structures. The structures were manufactured by melt- blending low weight percentages of montmorillonite (MMT) nanoclays (0.5, 1, 2, 3, 5 wt. %) and polypropylene (PP) thermoplastic. Both virgin and infused polypropylene structures were then subjected to quasi-static tensile tests, flexural tests, micro-hardness tests, impact testing, compression testing, fracture toughness analysis, dynamic mechanical analysis, tribological testing. Scanning electron microscopy studies were then conducted to analyse the fracture surfaces of pristine PP and PP nanocomposite. X-ray diffraction studies were performed on closite 15A clay and polypropylene composites containing 0.5, 1, 2, 3 and 5 wt. % closite 15A nanoclay to confirm the formation of nanocomposites on the addition of organo clays. Transmission electron miscopy studies were then performed on the PP nanocomposites to determine the formation of intercalated, exfoliated or agglomerated nanoclay structures. Analysis of test data show that the mechanical properties increase with an increase in nanoclay loading up to a threshold of 2 wt. %, thereafter the material properties degrade. At low weight nanoclay loadings the enhancement of properties is attributed to the lower percolation points created by the high aspect ratio nanoclays. The increase in properties may also be attributed to the formation of intercalated and exfoliated nanocomposite structures formed at these loadings of clay. At higher weight loading, degradation in mechanical properties may be attributed to the formation of agglomerated clay tactoids. Results of XRD, transmission electron microscopy studies and scanning electron microscopy studies of the fractured surface of tensile specimens verify these hypotheses.

Thesis (PhD (Process Engineering))--University of Stellenbosch, 2006. / Existing thermoplastic polyurethanes (TPUs), used in the manufacturing of cardiovascular devices, still have unproven long-term biostability and may be prone to excessive plastic deformation when subjected to cyclic loading. These negative aspects can be attributed to, among other factors, the weak nature of virtual crosslinking through microphase separation. The modification and covalent crosslinking of existing medical grade polyurethanes with unsaturated acyl chlorides are thus proposed to improve these properties. A model compound study was used to find a suitable acyl chloride (4-pentenoyl chloride), confirm the intended carbamate nitrogen as successful reaction site and to optimize the chemistry of the reaction. Two medical grade polyurethanes, Pellethane® 2363- 80AE (Pellethane) and PurSil 35-80A (PurSil), were subsequently successfully modified with 4-pentenoyl chloride. The degree of modification could be accurately controlled (R2 = 0.99) to between 4.5% to 20.0% and between 11.5% to 18.5% for the respective polyurethanes. The degree of modification and method of crosslinking were then optimized to obtain the required mechanical properties (i.e. minimum hysteresis). The hysteresis and creep of the modified and crosslinked Pellethane were reduced by 42.5% and 44.0%, respectively, while the hysteresis of the modified and crosslinked PurSil was reduced by 12.9%. The chemical stability of Pellethane (control) modified Pellethane (15% modification) and crosslinked Pellethane (Pell15.0) was evaluated in an in vitro degradation study. The hysteresis of the crosslinked polymer was at least 27.5% better when compared to Pellethane, and showed a significant resistance to surface degradation (as studied with scanning electron microscopy). Although the soft phases in both polyurethanes are vulnerable toward degradation, it was not as pronounced in Pell15.0, mainly due to the restriction of chain movement resulting from the crosslinking. Small-diameter tubular constructs, with similar fiber and wall thicknesses, were electrospun from Pellethane and the 15% modified Pellethane. A standard electrospinning technique was used in the case of the former while in the case of the latter a novel “reactive” electrospinning technique was used for the in situ crosslinking of the novel material, while simultaneously forming the tubular constructs. It is suggested that the manufacturing of Pell15.0 be scaled up to produce adequate amounts of material to enable the extrusion and in vivo evaluation of e.g. pacemaker leads. A circulatory animal model, e.g. a senescent baboon model, could be used to evaluate and further optimize the electrospun tubular constructs.

Die vorliegende Arbeit wurde im Rahmen des DFG Graduiertenkollegs 1703 „Ressourceneffizienz in Unternehmensnetzwerken – Methoden zur betrieblichen und überbetrieblichen Planung für die Nutzung erneuerbarer Rohstoffe“ durchgeführt. Es wurde der Einfluss verschiedener Prozessparameter auf die Morphologie der Holzkomponente von Holz-Kunststoff-Kompositen (Wood Plastic Composites – WPC) untersucht. Die Ergebnisse wurden bereits anderswo publiziert bzw. zur Publikation eingereicht (insgesamt vier Publikationen) und werden innerhalb individueller Kapitel der vorliegenden Arbeit wiedergegeben. WPC vereinen die Eigenschaften von Holz als Füllstoff mit den Eigenschaften von Polymeren als Matrixmaterial. Aktuelle Literatur und Forschungsarbeiten wurden gesichtet, um Möglichkeiten zu identifizieren, wie WPC zu einer effizienten Ressourcennutzung beitragen kann. Die Ergebnisse zeigen, dass eine Vielzahl von Abfall- und Nebenprodukten aus Holz- und Agrarwirtschaft zur Herstellung von WPC verwendet werden kann, z.B. Sägespäne, Reststoffe aus der Plattenproduktion und Schlämme aus der Faserstoffproduktion. Darüber hinaus können auch Kunststoff-Rezyklate und Biokunststoffe als Rohstoff dienen. Für die Eigenschaften von WPC spielt die Morphologie der Holzkomponente – Fasern oder Partikel – eine entscheidende Rolle. Während der Verarbeitung von WPC treten hohe Temperaturen und Scherkräfte auf, welche zur Zerkleinerung der Holzkomponente führen. Um die Zerkleinerung während der Verarbeitung analysieren zu können, wurde die Eignung der Partikel¬charakterisierung mittels dynamischer Bildanalyse zur Größenbestimmung von WPC-Füllstoffen geprüft. Dafür wurden Holzpartikel aus der Polymermatrix gelöst und ihre Morphologie vor und nach der Verarbeitung verglichen. Es zeigte sich, dass eine Auswertung bezüglich der längenbasierten Größenverteilung am besten geeignet ist, um Prozess-Effekte zu analysieren, da Partikel an beiden Enden der Größenverteilung gut abgebildet werden. Die Effekte von Prozessparametern wie Holzanteil, Beschickungsmethode, Vorwärmen des Holzes, Polymerviskosität, Rotor-/Schneckendrehzahl, Förderrate und Schneckenkonfiguration auf die Holzzerkleinerung wurden untersucht. Dazu wurden Fichtenholz-Partikel (Picea abies) entweder unter Verwendung eines Innenmischers oder eines Doppelschnecken-Extruders mit Polypropylen (PP) compoundiert. Zur Bestimmung des Einflusses der Polymerviskosität wurden verschiedene Sorten PP und schwachverzweigtes Polyethylen (HDPE) verwendet, welche sich in ihrem Schmelzflussindex (melt flow rate – MFR) unterscheiden. Nach dem Compoundieren betrug die Partikelgröße nur noch < 3 % der ursprünglichen Größe. Bei den PP-Kompositen nahm die Partikelzerkleinerung sowohl im Innenmischer als auch im Extruder mit zunehmendem Holzanteil zu. Auch eine zunehmende Anzahl an Knetelementen im Schneckenprofil führte zu einer stärkeren Partikelzerstörung. Bei den HDPE-Kompositen war der Einfluss des Holzanteils nur gering. Wurden die Holzpartikel und das Polymer dem Prozess gleichzeitig zugeführt, war die Partikelzerstörung intensiver als wenn die Partikel dem bereits geschmolzenen Polymer zugegeben wurden. Auch ein Vorwärmen der Partikel führte zu einer stärkeren Zerkleinerung. Die Zerkleinerung konnte unter Verwendung eines Matrixpolymers mit hohem MFR reduziert werden. Zum einen variierte der Einfluss der Förderrate mit der Schneckendrehzahl, zum anderen variierte der Einfluss von Förderrate und Schneckendrehzahl auch mit dem Holzanteil. Da die Bedingungen des Compoundierprozesses im Labormaßstab üblicherweise nicht mit Bedingungen im Industriemaßstab vergleichbar sind, wurden die Prozessparameter an einem Labor-Extruder so gewählt, dass sie industrielle Bedingungen imitieren. Die Einkürzung von Kiefernholzfasern (Pinus radiata) wurde mit der Einkürzung von Glasfasern verglichen, da diese ein Standardmaterial in der industriellen Kompositfertigung darstellen. Mittels sogenannter „Dead-stop“-Versuche und Probennahme entlang der Extruderschnecken wurde der Einfluss von Schneckenkonfiguration, Schneckendrehzahl und Förderrate analysiert. Prozesseinstellungen, die einen geringeren Anteil an spezifischer mechanischer Energie ins Material eintrugen, sowie eine schonende Schneckenkonfiguration verzögerten die Fasereinkürzung entlang der Extruderschnecken. Für eingangs längere Glasfasern war dieser Effekt ausgeprägter als für eingangs kürzere Holzfasern. Die Faserlänge im Endprodukt zeigte jedoch keine Unterschiede bezüglich der Prozesseinstellungen. Glasfasern zeigten deutlichere Unterschiede in der Faserlänge aufgrund der Schneckenkonfiguration als Holzfasern. Diese spiegelten sich auch in den mechanischen Eigenschaften wieder: ein aggressiveres Schneckenprofil resultierte in geringeren Festigkeiten bei den Glasfaser-Kompositen, jedoch nicht bei den Holzfaser-Kompositen.

Bio-basedcomposites are being increasingly used in applications where weight saving,and environmental friendliness is as important as structural performance. Obviously, bio-based materials have their limitations regarding durability and stability of the properties,but their potential in use for advanced applications can be expanded if they were functionalized and considered beyond their structural performance. Multifunctionalityincomposites can be achieved by modifyingeither of the composite constituents at different levelsso that they can perform energy-associated roles besides their structural reinforcement in the system. For the fibers, this can be done at the microscale by altering theirmicrostructure during spinning process or by applying functional coatings. As for the matrix, it is usually done by incorporating additives that can impart the required characteristics to the matrix. The nano-sized additives that mightbe considered for this objective are graphene and carbon nano-tubes. A big challenge with such materials is the difficulty to reachthe dispersionstate necessary for formation ofstable network to overcome the percolation threshold for conductivity. However, once the network is formed, the composite can have improved mechanical performance together with one or more of the added functionalities such as barrier capabilities,thermal and/or electrical conductivities or electromagnetic interference ability. Enormous work has been done to achieve the functionality incomposites produced with special care in laboratories. However, when it comes to mass production, it is both cost and energy inefficient to use tedious,complex methods for the manufacturing. Hence there is a need to investigate the potential of using scalable and industrial-relevant techniques and materials with acceptable compromise between cost and properties. The work presented in this thesis is performedwithin two projects aiming to achieve functional composites based on natural and man-made cellulosic fibers suitable for industrial upscaling. Conductive Regenerated Cellulose Fibers (RCFs) were produced by coating them with copper by electroless coating process using commercial materials. On the other hand, commercial masterbatches based on Graphene Nano-Platelets (GNPs) were used to produce wood polymer composites (WPC) with added multifunctionality by melt extrusion process. The process is one of the conventional methods used inpolymerproductionand needsno modifications for processingfunctional composites. Both materials together can be used to produce hybrid functional composites. The incorporation of the GNP into HDPE has resulted in improvement in the mechanical propertiesof polymer as well as composite reinforced with wood fibers. Stiffness has increased to a large extent while effect on the strength was less pronounced(&gt;100% and 18% for stiffness and strength at 15%GNP loading). The enhancement of thermal conductivityat higher graphene loadingswas also observed. Moreover, time-dependent response of the polymer has also been affected and the addition of GNP has resulted in reduced viscoplastic strains and improved creep behavior. The copper-coated cellulose fibers showed a significant increasein electrical conductivity(&lt;1Ω/50mm of coated samples) and a potential in use as sensor materials. However, these results come with the cost of reduction in mechanical properties of fibers (10% and 70% for tensile stiffness and strength, respectively) due to theeffect ofchemicals involved in the process.

Esta tese apresenta, primeiramente, revisões sobre polímeros, métodos para obtenção das propriedades mecânica de um material em uma ampla faixa de taxas de deformação além de uma revisão da mecânica do contínuo não linear, estruturas cinemáticas com divisão multiplicativa do gradiente de deformação e modelos de material para polímeros termoplásticos. Posteriormente são apresentados ensaios experimentais de relaxação, quase-estáticos e dinâmicos de tração e compressão em PEAD e PVC, seguidos por impactos em placas dos mesmos materiais. A grande quantidade de ensaios quase-estáticos objetivaram a análise da sensibilidade à taxa de deformação e ao tipo de carregamento, além do grau de anisotropia. Nestes e nos de relaxação, foi utilizada uma técnica de correlação de imagens digitais, DIC, mensurando as deformações longitudinais e transversais no plano, permitindo a obtenção de curvas tensão real deformação verdadeira em diversas secções transversais de um mesmo corpo de prova. Uma nova metodologia proposta para a obtenção de mapa de correções na análise da dispersão e atenuação na propagação de ondas em barras cilíndricas de materiais viscoelásticos permitiu uma maior confiabilidade e acurácia do comportamento viscoplástico obtido na Barra de Hopkinson dividida de pressão. Por fim, um modelo de material é proposto e tem seus parâmetros calibrados utilizando-se os ensaios de relaxação, quase-estáticos e de propagação de ondas em sua parte viscoelástica e a parte plástica dos ensaios quase-estáticos juntamente com os dados obtidos na Barra de Hopkinson em sua parte viscoplástica, na intenção de verificar seu funcionamento, simulando o impacto nas placas. / This thesis first presents a review on polymers, methods for measuring the material mechanical properties of in a wide range of strain rates and a review of nonlinear continuum mechanics, kinematic frameworks with multiplicative split of the deformation gradient altogether with models material for thermoplastic polymers. Later, This thesis presents results of relaxation, quasi-static and dynamic tests under tensile and compressive loads for HDPE and PVC, and subsequently impacts on plates of the same materials. The large number of quasi-static tests aimed to analyze the sensitivity to strain rate and to the type of loading, and also the degree of anisotropy. During these later tests and the relaxation ones, it was used a technique called digital image correlation, DIC, measuring the longitudinal and transverse strains in a plane and allowing the attainment of true stress true strain curves in various cross sections of the same specimen. A proposed new methodology for obtaining corrections map for the analysis of the dispersion and attenuation in wave propagation on cylindrical bars made of viscoelastic materials allowed greater reliability and accuracy of the viscoplastic behavior obtained in split Hopkinson bar pressure. Finally, a model material is proposed and has its parameters calibrated using relaxation, quasi-static and wave propagation tests in its viscoelastic part and plastic part of the quasi-static tests with the data obtained in bar Hopkinson in its viscoplastic part, in order to verify its behavior while simulating the plate impact tests.