Carboxylated Polyurethanes Containing Hyperbranched Polyester Soft Segments

hyperbranched polyester soft segments (HB PU) with functional carboxylic groups in order to enable the preparation of stable HB PU dispersions. Carboxylated hyperbranched polyurethanes were synthesized using a hyperbranched polyester based on 2,2-bis(methylol)propionic acid of the fourth pseudo-generation (Boltorn H40) and hexamethylene (HDI) or isophorone diisocyanate (IPDI). The reactivity of hyperbranched polyester with HDI was lower than expected, possibly due to the presence of less reactive hydroxyl groups in the linear repeat units. A gel was formed at mole ratios r_NCO/OH = 1:2 or 1:4. The synthesis of HB PU was performed with partly esterified hyperbranched polyester with lowered hydroxyl functionality. The carboxyl groups were incorporated in the HB PU backbone by reaction of residual hydroxyl groups with cis-1,2-cyclohexanedicarboxylic anhydride. HB PU aqueous dispersions were stable at least for two months, although their films were brittle. The tensile strength and Young's modulus of blends of linear and HB PU decreased with increasing content of HB PU whereas elongation at break remained nearly constant, which was explained in terms of looser chain packing due to more open tree-like hyperbranched structures

Evidence for Archaean lamprophyre from the Kaapvaal Craton, South Africa

A suite of mafic dykes occurs as a late component in a wellcharacterized trondhjemite–tonalite–diorite–granodiorite assemblage in the Johannesburg Dome of the central Kaapvaal Craton, southern Africa. The dykes have been subdivided into two sets, based on their orientation, and major and trace element geochemistry. Set 1 dykes are characterized by elevated SiO2, Al2O3 and TiO2, and particularly by enriched LILE and HSFE (e.g. Zr > 200 ppm, Nb > 20 ppm, Ba > 300 ppm), higher than in any of the accompanying felsic rocks. REE and trace element values for Set 1 dykes are similar to those for calc-alkaline lamprophyres. The Set 2 dykes have similar trace element distributions, but are significantly less enriched in general, and are broadly tholeiitic in composition, with enriched MgO (>11 wt. percentage) indicative of an olivine–phyric tholeiitic basaltic protolith. Field relationships and available U–Pb zircon geochronology indicate that the dykes are contemporaneous with components of the trondhjemitic host rocks, and with late granodiorites. The geochemical, geochronological and field petrological setting indicates partial melting of basaltic and eclogitic lithosphere at c. 3120 Myr ago in the basal Kaapvaal Craton, and subsequent emplacement into pre-existing c. 3430 Myr tonalitic to dioritic crust

The Uitkomst intrusion and Nkomati Ni-Cu-Cr-PGE deposit, South Africa: trace element geochemistry, Nd isotopes and high-precision geochronology

The Uitkomst intrusion is a tubular mafic-ultramafic layered body that hosts one of South Africa’s largest Ni-Cu-Cr-PGE deposits, Nkomati. The sulphide ore occurs in the form of massive lenses in the immediate quartzitic footwall and as disseminations within peridotite. The chromite ore forms an up to ∼10-m-thick layer in the lower portion of the intrusion. Uitkomst has generally been interpreted as a magma conduit, possibly related to the Bushveld event. Here, we present a new high-precision U-Pb zircon date of 2057.64 ± 0.69 Ma that overlaps with the age of the Merensky Reef of the Bushveld Complex and thus demonstrates a coeval relationship between the intrusions. Based on incompatible trace elements as well as O- and Nd isotope data (εNd −4.5 to −6.2), we show that the Uitkomst parent magmas were contaminated with up to 20% Archean upper crust prior to emplacement, and with up to 15% dolomitic country rock during emplacement. Ore formation at Nkomati was critically aided by substantial devolatisation and removal of dolomitic floor rocks leading to hydrodynamic concentration of sulphide and chromite during slumping of crystal mushes into the trough-like centre of the subsiding intrusion and its footwall

Igneous Rock Associations 23. The Bushveld Complex, South Africa: New Insights and Paradigms

SUMMARYThe Bushveld Complex has continued to serve as the basis for study into the fundamental nature of petrological processes for layered intrusion formation and for oxide and sulphide hosted Platinum Group Element (PGE)–Cu–Ni ore deposits. These studies have included discoveries in terms of the physical extent of Bushveld magmatism, both laterally and internally. Lateral variations in the mafic to ultramafic Rustenburg Layered Suite of the Northern Lobe of the complex have also revealed petrologically distinctive Upper Critical Zone equivalent rocks (the so-called Flatreef) with enhanced contamination and mineralization traits that reflect a transition between Eastern and Western Lobe equivalent stratigraphy and Platreef-style complexity. Traditional magma mixing models have been re-examined in light of radiogenic isotopic evidence for crustal involvement early in the chromite precipitation or formation process, combined with evidence for associated heterogeneous fluid contents, cryptic layering profiles, and textural evidence. A wide variety of alternative ore-genesis models have been proposed as a consequence. The fundamental mechanics of magma chamber processes and the existence of the magma chamber as an entity have been called into question through various lines of evidence which have promoted the concept of progressive emplacement of the complex as a stack of not-necessarily-quite-sequentially intruded sills (with or without significant quantities of transported phenocrysts), emplaced into variably crystallized and compacted crystal-liquid mush mixtures, modified by compaction-driven late magmatic fluid (silicate and aqueous) activity. Alternatively, petrological and geochemical observations have been used to discount these interpretations in favour of more conventional cooling and gravity-driven accumulation of silicate and ore minerals in a large, liquid-dominated system.RÉSUMÉLe complexe de Bushveld a demeuré à la base d’études sur la nature fondamentale des processus pétrologiques de formation d’intrusions litées et des gîtes des éléments du groupe platine (ÉGP)-Cu-Ni hébergés dans les oxydes et les sulfures. Ces études ont comporté des découvertes sur l’étendue physique, à la fois latérale et interne, du magmatisme de Bushveld. Les variations latérales de la suite stratifiée et mafique à ultramafique Rustenburg du lobe nord du complexe ont également révélé des roches équivalentes pétrologiquement distinctes de la zone critique supérieure (le communément désigné Flatreef) avec des traits de contamination et de minéralisation accrus qui reflètent une transition entre la stratigraphie équivalente des lobes est et ouest et la complexité de type Platreef. Les modèles traditionnels de mélanges magmatiques ont été réexaminés à la lumière de preuves isotopiques radiogéniques indiquant une implication de la croûte au début du processus de précipitation ou de formation de la chromite, combinées à des preuves de contenu fluide hétérogène associé, de profils de litage cryptique et de preuves texturales. Ainsi, une grande variété de modèles alternatifs de genèse de minerai a été proposée. La mécanique fondamentale des processus de la chambre magmatique et l'existence de la chambre magmatique en tant qu'entité ont été remises en question au moyen de divers éléments de preuve qui ont mis en avant le concept de mise en place progressive du complexe sous forme d'un empilement non-nécessairement séquentiel de sills injectés (avec ou sans quantités significatives de phénocristaux transportés) mis en place dans des mélanges de bouillie cristaux/liquide à cristallisation et compaction variable, modifiés par une activité tardive de fluide magmatique (silicaté et aqueux) induite par la compaction. Alternativement, des observations pétrologiques et géochimiques ont été utilisées pour écarter ces interprétations en faveur d'un processus plus conventionnel de refroidissement et d’accumulation de minérais silicatés et minéralisés induite par la gravité dans un vaste système à dominance liquide

Igneous Rock Associations 23. The Bushveld Complex, South Africa: New Insights and Paradigms

SUMMARYThe Bushveld Complex has continued to serve as the basis for study into the fundamental nature of petrological processes for layered intrusion formation and for oxide and sulphide hosted Platinum Group Element (PGE)–Cu–Ni ore deposits. These studies have included discoveries in terms of the physical extent of Bushveld magmatism, both laterally and internally. Lateral variations in the mafic to ultramafic Rustenburg Layered Suite of the Northern Lobe of the complex have also revealed petrologically distinctive Upper Critical Zone equivalent rocks (the so-called Flatreef) with enhanced contamination and mineralization traits that reflect a transition between Eastern and Western Lobe equivalent stratigraphy and Platreef-style complexity. Traditional magma mixing models have been re-examined in light of radiogenic isotopic evidence for crustal involvement early in the chromite precipitation or formation process, combined with evidence for associated heterogeneous fluid contents, cryptic layering profiles, and textural evidence. A wide variety of alternative ore-genesis models have been proposed as a consequence. The fundamental mechanics of magma chamber processes and the existence of the magma chamber as an entity have been called into question through various lines of evidence which have promoted the concept of progressive emplacement of the complex as a stack of not-necessarily-quite-sequentially intruded sills (with or without significant quantities of transported phenocrysts), emplaced into variably crystallized and compacted crystal-liquid mush mixtures, modified by compaction-driven late magmatic fluid (silicate and aqueous) activity. Alternatively, petrological and geochemical observations have been used to discount these interpretations in favour of more conventional cooling and gravity-driven accumulation of silicate and ore minerals in a large, liquid-dominated system.RÉSUMÉLe complexe de Bushveld a demeuré à la base d’études sur la nature fondamentale des processus pétrologiques de formation d’intrusions litées et des gîtes des éléments du groupe platine (ÉGP)-Cu-Ni hébergés dans les oxydes et les sulfures. Ces études ont comporté des découvertes sur l’étendue physique, à la fois latérale et interne, du magmatisme de Bushveld. Les variations latérales de la suite stratifiée et mafique à ultramafique Rustenburg du lobe nord du complexe ont également révélé des roches équivalentes pétrologiquement distinctes de la zone critique supérieure (le communément désigné Flatreef) avec des traits de contamination et de minéralisation accrus qui reflètent une transition entre la stratigraphie équivalente des lobes est et ouest et la complexité de type Platreef. Les modèles traditionnels de mélanges magmatiques ont été réexaminés à la lumière de preuves isotopiques radiogéniques indiquant une implication de la croûte au début du processus de précipitation ou de formation de la chromite, combinées à des preuves de contenu fluide hétérogène associé, de profils de litage cryptique et de preuves texturales. Ainsi, une grande variété de modèles alternatifs de genèse de minerai a été proposée. La mécanique fondamentale des processus de la chambre magmatique et l'existence de la chambre magmatique en tant qu'entité ont été remises en question au moyen de divers éléments de preuve qui ont mis en avant le concept de mise en place progressive du complexe sous forme d'un empilement non-nécessairement séquentiel de sills injectés (avec ou sans quantités significatives de phénocristaux transportés) mis en place dans des mélanges de bouillie cristaux/liquide à cristallisation et compaction variable, modifiés par une activité tardive de fluide magmatique (silicaté et aqueux) induite par la compaction. Alternativement, des observations pétrologiques et géochimiques ont été utilisées pour écarter ces interprétations en faveur d'un processus plus conventionnel de refroidissement et d’accumulation de minérais silicatés et minéralisés induite par la gravité dans un vaste système à dominance liquide

Petrology, geochemistry, and geochronology of some Precambrian rocks of the north-western Melville Peninsula, Northwest Territories

The northwestern Melville Peninsula in the area of 69°34'N/84°50'W consists of Precambrian Shield rocks that have suffered multiple metamorphic events, including a high grade metamorphic event in the late Archean, ranging from upper amphibolite to granulite grade locally. The oldest unit present is a tonalite-granodiorite-granite suite showing both foliation and lineation and a somewhat migmatic texture. This biotite-hornblende orthogneiss has produced a Rb-Sr whole rock age date of 2.55 +/- 0.2 Ga. Field relationships indicate that this is a metamorphically induced age rather than an emplacement age. A coarse grained granitic pegmatite associated with the orthogneiss has produced a Rb-Sr isochron indicating an age of 1.83 +/- 0.06 Ga. Petrographic and field evidence indicate that this represents the emplacement age of the pegmatite. ThesisBachelor of Science (BSc

Petrology, Geochronology and Geochemistry of the White Bear Arm Complex and Associated Units, Grenville Province, Eastern Labrador

The Hawke River Terrane of the Grenville Province in eastern Labrador is dominated by a coronitic gabbronorite to anorthosite body plus associated amphibolitic to granodioritic bodies known as the White Bear Arm Complex (WBAC). Petrographic and geochemical evidence supports a constant volume sub-solidus diffusion origin for double coronas of orthopyroxene and amphibole around olivine. Geochemical evidence suggests that corona formation was not completely isochemical, requiring an influx of potassium, iron and magnesium, but on a whole-rock scale was probably closed to the latter two elements. Nd and Sr isotopic evidence indicates that the coronas did not form as a response to a much later (eg. Grenville aged) metamorphic event, and probably. developed during post-crystallisational cooling or during a metamorphism shortly thereafter. The WBAC is cut by a monzonitic to granodioritic body mineralogically and chemically similar to the WBAC 'monzonite', known as the Paradise Arm Pluton (PAP). Petrographic, geochemical, and field relationship evidence indicates an igneous origin for the PAP and the WBAC monzonite. Both of these units have been subjected to low grade (greenschist facies) metamorphism. The WBAC and the PAP are hosted by the Paradise Metasedimentary Gneiss Belt, an aluminous paragneiss which has been raised to middle to upper amphibolite grade metamorphism, except immediately adjacent to the contact with the WBAC, where granulite grade has been obtained, forming high-temperature aluminosilicates such as osumilite and sapphirine. The contact zone has also been contaminated by fluids from the gabbronorites, reflected by petrography, elemental and isotopic geochemistry. Field relationships and geochemistry are ambiguous regarding whether the monzonitic units were derived by fractional crystallisation of the gabbronorite or partial melting of the paragneisses, but trace element variation favours the latter model. The PAP is a product of physical, geochemical and Sr isotopic mixing between a granodioritic end-member and a paragneissic one. Sm-Nd isotope systematics on whole-rocks do not provide a precise emplacement age for the WBAC gabbronorite, but indicate a Labradorian age (ca. 1.65 Ga old). Rb-Sr wholerock systematics show a Labradorian-aged trend and a steeply sloping trend interpreted as a mixing line with an unspecified crustal component, possibly corresponding to the potassium metasomatism indicated earlier. Rb-Sr on minerals from two rocks produces a precise age of 1675 ± 15 Ma and a similar, imprecise age. The WBAC monzonite and the Paradise Arm Pluton give Rb-Sr ages of 1621 ± 11 Ma CMSWD=24) and 1573 % 18 Ma (MSWD=9) respectively, with low initial 87Sr/ 86Sr ratios around 0.7040. These are interpreted as a minimum emplacement age and a mixing line, respectively. The PMGB paragneisses give a Rb-Sr age of 1630 ± 16 Ma CMSWD=35), with an initial 87Sr/ 86Sr composition around 0.704. All ages are equal within expanded 2σ error of each other (ie. MSWD=1), and give Labradorian ages. There is no evidence of Grenville-aged (ca. 1.0 Ga old) metamorphism. Rb-Sr isotopic and E Nd -E Br variations suggest crustal contamination of the gabbronorites, although the contaminant cannot be identified. Two separate mechanisms are required to generate the observed trends: a fluid metasomatism and a bulk-rock crustal contamination, or else contamination by currently unidentified low Sr crustal material. The WBAC gabbronorites provide evidence for 'extra'-LREE-depleted mantle beneath eastern Labrador at 1.65 Ga, with E Nd of at least +7.6. ThesisMaster of Science (MSc

Karboksilirani poliuretani s visoko razgranatim poliesterskim mekanim segmentima

hyperbranched polyester soft segments (HB PU) with functional carboxylic groups in order to enable the preparation of stable HB PU dispersions. Carboxylated hyperbranched polyurethanes were synthesized using a hyperbranched polyester based on 2,2-bis(methylol)propionic acid of the fourth pseudo-generation (BoltornŽ H40) and hexamethylene (HDI) or isophorone diisocyanate (IPDI). The reactivity of hyperbranched polyester with HDI was lower than expected, possibly due to the presence of less reactive hydroxyl groups in the linear repeat units. A gel was formed at mole ratios rNCO/OH = 1:2 or 1:4. The synthesis of HB PU was performed with partly esterified hyperbranched polyester with lowered hydroxyl functionality. The carboxyl groups were incorporated in the HB PU backbone by reaction of residual hydroxyl groups with cis-1,2-cyclohexanedicarboxylic anhydride. HB PU aqueous dispersions were stable at least for two months, although their films were brittle. The tensile strength and Young\u27s modulus of blends of linear and HB PU decreased with increasing content of HB PU whereas elongation at break remained nearly constant, which was explained in terms of looser chain packing due to more open tree-like hyperbranched structures.Rad prikazuje sintezu i karakterizaciju poliuretana s mekanim segmentima od visoko razgranatoga poliestera (HB PU) s funkcionalnim karboksilnim skupinama s namjenom pripreme stabilnih disperzija HB PU. Za sintezu karboksiliranih HB PU upotrijebili smo visoko razgranati poliester na osnovi 2,2-bis(metilol)propionske kiseline četvrte pseudo-generacije (Boltorn H40) i heksametilen-diizocijanat (HDI) ili izoforon-diizocijanat (IPDI). Reaktivnost visoko razgranatog poliestra s HDI-om bila je niža od očekivane, vjerojatno zbog postojećih manje reaktivnih hidroksilnih skupina u linearnim jedinicama. Reakcijske smjese gelirale su kod množinskog omjera rNCO/OH = 1:2 i 1:4. HB PU sintetizirali smo iz djelimično preostaloga visoko razgranatoga poliestera s nižom -OH funkcionalnosti. Karboksilne skupine smo u lanac HB PU uveli s esterifikacijom neizreagiranih hidroksilnih skupina s anhidridom cis-1,2-cikloheksandikarboksilne kiseline. Vodene disperzije HB PU bile su stabilne najmanje dva mjeseca, filmovi su bili krhki. Ispitivanja na vučnu čvrstoću i na Youngov modul elastičnosti su pokazali da su se iznosi kod smjesa linearnoga i HB PU s povećavajućim udjelom HB PU se smanjivali, dok je naprezanje na rastezanje do loma ostalo nepromijenjeno, što smo objasnili s manje gustim slaganjem lanaca zbog više otvorenih drvenastih visoko razgranatih struktura

Evidence for Archaean lamprophyre from the Kaapvaal Craton, South Africa

A suite of mafic dykes occurs as a late component in a wellcharacterized trondhjemite–tonalite–diorite–granodiorite assemblage in the Johannesburg Dome of the central Kaapvaal Craton, southern Africa. The dykes have been subdivided into two sets, based on their orientation, and major and trace element geochemistry. Set 1 dykes are characterized by elevated SiO2, Al2O3 and TiO2, and particularly by enriched LILE and HSFE (e.g. Zr > 200 ppm, Nb > 20 ppm, Ba > 300 ppm), higher than in any of the accompanying felsic rocks. REE and trace element values for Set 1 dykes are similar to those for calc-alkaline lamprophyres. The Set 2 dykes have similar trace element distributions, but are significantly less enriched in general, and are broadly tholeiitic in composition, with enriched MgO (>11 wt. percentage) indicative of an olivine–phyric tholeiitic basaltic protolith. Field relationships and available U–Pb zircon geochronology indicate that the dykes are contemporaneous with components of the trondhjemitic host rocks, and with late granodiorites. The geochemical, geochronological and field petrological setting indicates partial melting of basaltic and eclogitic lithosphere at c. 3120 Myr ago in the basal Kaapvaal Craton, and subsequent emplacement into pre-existing c. 3430 Myr tonalitic to dioritic crust