This thesis aims to evaluate the compositional changes that occur when raw clays are transformed into finished vessels, and how these compositional changes impact provenance research. Petrographic and chemical techniques are used to analyse clays at each stage in the production sequence used by Zulu potters in KwaZulu-Natal, South Africa. The results of this research demonstrate that tempering behaviour, particularly the mixing of clays, can significantly alter the composition of ceramic vessels, depending on the ratio of clay types. The provenance of mixed clays and vessels can be determined when the range of variation between clay sources is known. Different ratios of constituent clays significantly affect the composition of finished vessels.

This thesis aims to evaluate the compositional changes that occur when raw clays are transformed into finished vessels, and how these compositional changes impact provenance research. Petrographic and chemical techniques are used to analyse clays at each stage in the production sequence used by Zulu potters in KwaZulu-Natal, South Africa. The results of this research demonstrate that tempering behaviour, particularly the mixing of clays, can significantly alter the composition of ceramic vessels, depending on the ratio of clay types. The provenance of mixed clays and vessels can be determined when the range of variation between clay sources is known. Different ratios of constituent clays significantly affect the composition of finished vessels.

This study considers how significant multi-regional processes, such as Spanish colonization of the U.S. Southwest and the later Puebloan diaspora, affected the lives of Native peoples living on the Central Great Plains. Social and economic connections existed between Puebloan people and several Great Plains groups, including those known to archaeologists as the Dismal River Aspect (AD 1600-1750). One significant Dismal River site in western Kansas, the Scott County Pueblo (14SC1), includes the remains of a Dismal River occupation, a seven-room masonry pueblo, and Puebloan material culture. Previous researchers interested in 14SC1 have used Spanish historical documents and archaeological evidence to focus on who built the structure and why. To date, very few attempts have been made to move beyond this pueblo to consider how Puebloan migrants who moved to the Central High Plains were influencing Dismal River communities. The primary goal of this research was to determine the nature and extent to which Puebloan migrants impacted the lives of Dismal River groups, and how far these influences may have spread to Dismal River people living outside of western Kansas. This research employed reviews of available ethnographic and Spanish historic documents, the analysis of Dismal River ceramic assemblages, and the mineral and chemical characterization of raw material sources and ceramic samples. Ethnographic accounts provided evidence for variation found in foodways practices and ceramic vessel use between Great Plains and Puebloan groups, providing a baseline for Plains technological styles versus those commonly found in northern New Mexico. A careful analysis of how ceramic vessels were manufactured and used can provide insights into the practices and identity of the people who made them, and whether Puebloan practices were shared with Dismal River groups. The analysis of archaeological specimens, using both whole vessels and sherds, showed that Dismal River people living at and near the Scott County Pueblo in western Kansas were influenced by their interactions with Puebloan migrants. However, there was no ceramic evidence indicating that Puebloan migrants or their practices were present at Dismal River sites outside of Kansas. Evidence of Puebloan manufacturing practices, vessel forms, and foodways are present at three sites in western Kansas. Compositional analyses confirmed that while Dismal River Gray Ware ceramics were locally made, possible examples of Tewa Red Ware and Kapo Black recovered from Scott County sites were also locally made. These data indicate that adult Puebloan women were living in western Kansas, making pottery in culturally significant styles that they learned in their natal communities. These Puebloan women, while preserving their cultural heritage, were also influencing the Dismal River community they joined and likely passed their cultural practices on to their children. The characterization of micaceous ceramics recovered from many Dismal River sites indicates that they may have origins in both New Mexico and the Front Range and Laramie Mountains of Colorado and Wyoming. Dismal River people living across the Central High Plains were tied into larger inter- and intra- regional exchange networks and much of their observed cultural variation likely stems from their interaction with different neighboring groups. Additional research is needed to identify the possible sources of these micaceous ceramics and to better understand how Native American-Native American interactions were impacting the identity, practice, and technology of groups living on the Plains during the Protohistoric period.

O presente estudo aborda a fronteira da manufatura de ultraprecisão (UP) da zircônia tetragonal policristalina estabilizada com 3 mol% de ítria (3Y-TZP), realizado por meio da lapidorretificação Ud. A crescente demanda por produtos de cerâmicas avançadas com: elevado acabamento e integridade superficial; alta exatidão de forma; e menor custo de fabricação, tem fomentado pesquisas em diversas áreas da nanociência e nanotecnologia (N&N), visando sobrepujar as limitações ou agregando as principais vantagens dos tradicionais processos de retificação, lapidação e polimento. Em decorrência das excepcionais propriedades mecânicas, a cerâmica 3Y-TZP tem sido extensivamente aplicada na indústria. A 3Y-TZP, entretanto, pode apresentar a desestabilização da sua fase tetragonal em diferentes situações e condições, por exemplo, tendo início na própria manufatura, durante sua usinagem, podendo comprometer seu desempenho. Dessa forma, a 3Y-TZP pode ser considerada um material chave para avaliar e qualificar os processos abrasivos que visam padrão ouro de qualidade que, portanto, não devem suscitar a transformação martensítica. Em meio à pluralidade de processos, destaca-se a lapidorretificação Ud. A presente pesquisa estudou a manufatura UP de superfícies planas de zircônia TZ-3Y-E lapidorretificadas com rebolos de SiC de liga epóxi, almejando rugosidade nanométrica e integridade superficial sem danos microestruturais. Discos de TZ-3Y-E foram prensados isostaticamente a 200 MPa e sinterizados a 1400°C por 2 horas. Os discos foram caracterizados por meio de ensaios de: microdureza; perfilometria de contato e óptica; MEV-FEG; espectroscopia Raman; DRX; e microscopia confocal de epi-fluorescência. Os projetos mecânico e eletroeletrônico da Lapidorretificadora Fiocchi foram evoluídos na direção da retificação cerâmica UP. Os resultados demostraram que o projeto evolutivo da lapidorretificadora Fiocchi foi bem sucedido. A execução e controle das etapas de processamento cerâmico foram fundamentais para obter corpos cerâmicos densos e homogêneos, compatíveis com o acabamento aspirado. Os parâmetros de usinagem que se destacaram foram: profundidade de dressagem de 0,1 mm; pressão de lapidorretificação de 100 kPa; 100 rpm do rebolo e porta-peça; e emulsão (1:40) aplicada por MQF. A aspiração dos resíduos sobre o rebolo melhorou em 21,6% o acabamento, todavia a associação de abrasão dois (rebolo) e três corpos (abrasivos soltos) reduziu em 57,15% a rugosidade. O macroefeito foi visível nos rebolos de #800, #600 e #300 dressados com Ud = 1. A menor rugosidade, Ra = 60,63 nm, proveio do rebolo #300 dressado com Ud=5. O menor desvio de planeza, 0,308 μm, foi obtido com o rebolo de #800 e Ud = 3. O processo alcançou condições de plasticidade da zircônia que apontam para o predomínio dos mecanismos de remoção de microcorte e pulverização de material, sem ocorrência de microtrinca. Segundo ensaios de DRX e Espectroscopia Raman, a lapidorretificação Ud não provocou transformação martensítica. Todavia, o rebolo de #300 gerou alargamento assimétrico dos picos tetragonais nas proximidades de 2θ = 35° e 39° e a reversão das intensidades dos picos tetragonais a 40° e 41°. A reversão foi atribuída a mudança do domínio ferroelástico e a reorientação de planos cristalográficos em nível de cristalito. Os estudos sugerem que a usinagem introduziu tensão residual de compressão que pode ter estabilizado a fase romboédrica. Não há relato de processo capaz de alcançar acabamento nanométrico similar com mesmo tamanho e tipo de abrasivo. A lapidorretificação Ud pode substituir o engajamento da retificação, lapidação e polimento de cerâmica avançada. / The present study focuses on the border of ultra-precision (UP) manufacturing of 3 mol% yttria tetragonal zirconia polycrystal (3Y-TZP), carried out by Ud-lap grinding. The increasing demand for advanced ceramic products with: high surface finish and integrity; high form accuracy; and lower manufacturing cost, has encourage research in several areas of nanoscience and nanotechnology (N&N), to overcome the limitations or adding the main advantages of traditional grinding, lapping, and polishing processes. 3Y-TZP ceramics has been extensively applied by industry due to its exceptional mechanical properties. The 3Y-TZP, however, can present destabilization of its tetragonal phase in different situations and conditions. In the beginning of its manufacture, during its machining for instance, which may compromise its performance. Thus, the 3Y-TZP can be considered a key material to evaluate and qualify abrasive processes aiming gold standard quality that, therefore, should not raise the martensitic transformation. In the midst of plurality of processes, it is noteworthy the Ud-lap grinding. This research studied the UP manufacture of flat TZ-3Y-E zirconia surfaces lap ground with epoxy binder SiC grinding wheels, aiming to nanometer roughness and microstructural integrity without damage. Discs of TZ-3Y-E were isostatically pressed at 200 MPa and sintered at 1400 °C for 2 hours. The discs were characterized by tests of: microhardness; contact and optical profilometry; FEG-SEM; Raman spectroscopy; XRD; and confocal epi-fluorescence. Mechanical and electric-electronic designs of Fiocchi lap grinder were developed toward the UP ceramic grinding. Results showed that the developmental design of Fiocchi lap grinder was successful. The accomplishment and control of ceramic processing stages were essential for dense and homogenous ceramic bodies, compatible with the finish aspired. The machining parameters that stood out were: 0.1 mm depth of dressing; 100 kPa lap grinding pressure; 100 rpm grinding wheel and workpiece-holder; and emulsion applied by MQF. Suction of debris on the grinding wheel has improved finishing in 21.6%, however the combination of two-body abrasion (grinding wheel) and three-body abrasion (loose abrasives) decreased roughness in 57.15%. The macroeffect was visible on #800, #600, and #300 dressed with Ud = 1. The best finishing, Ra = 60.63 nm, came from #300 grinding wheel dressed with Ud = 5. The smallest flatness deviation, 0.308 μm, was obtained with the #800 grinding wheel and Ud = 3. The process has achieved zirconia plasticity conditions pointing towards predominance of microcutting and pulverization material removal mechanism without causing microcrack. According to XRD and Raman spectroscopy, the Ud-lap grinding caused no martensitic transformation. However, #300 grinding wheel has generated asymmetric broadening of the tetragonal peaks close to 2θ = 35° e 39° and reversal of the intensities of 40° and 41° tetragonal peaks. The reversal was attributed to ferroelastic switching and reorientation of crystallographic planes into crystallite level. Studies suggest that the machining has introduced compressive residual stress that may have stabilized rhombohedral phase. There is no report of an abrasive process capable of achieving similar nanometric finish with same grit size and type of abrasive. The Ud-lap grinding can replace the engagement of grinding, lapping, and polishing of advanced ceramics.

O presente estudo aborda a fronteira da manufatura de ultraprecisão (UP) da zircônia tetragonal policristalina estabilizada com 3 mol% de ítria (3Y-TZP), realizado por meio da lapidorretificação Ud. A crescente demanda por produtos de cerâmicas avançadas com: elevado acabamento e integridade superficial; alta exatidão de forma; e menor custo de fabricação, tem fomentado pesquisas em diversas áreas da nanociência e nanotecnologia (N&N), visando sobrepujar as limitações ou agregando as principais vantagens dos tradicionais processos de retificação, lapidação e polimento. Em decorrência das excepcionais propriedades mecânicas, a cerâmica 3Y-TZP tem sido extensivamente aplicada na indústria. A 3Y-TZP, entretanto, pode apresentar a desestabilização da sua fase tetragonal em diferentes situações e condições, por exemplo, tendo início na própria manufatura, durante sua usinagem, podendo comprometer seu desempenho. Dessa forma, a 3Y-TZP pode ser considerada um material chave para avaliar e qualificar os processos abrasivos que visam padrão ouro de qualidade que, portanto, não devem suscitar a transformação martensítica. Em meio à pluralidade de processos, destaca-se a lapidorretificação Ud. A presente pesquisa estudou a manufatura UP de superfícies planas de zircônia TZ-3Y-E lapidorretificadas com rebolos de SiC de liga epóxi, almejando rugosidade nanométrica e integridade superficial sem danos microestruturais. Discos de TZ-3Y-E foram prensados isostaticamente a 200 MPa e sinterizados a 1400°C por 2 horas. Os discos foram caracterizados por meio de ensaios de: microdureza; perfilometria de contato e óptica; MEV-FEG; espectroscopia Raman; DRX; e microscopia confocal de epi-fluorescência. Os projetos mecânico e eletroeletrônico da Lapidorretificadora Fiocchi foram evoluídos na direção da retificação cerâmica UP. Os resultados demostraram que o projeto evolutivo da lapidorretificadora Fiocchi foi bem sucedido. A execução e controle das etapas de processamento cerâmico foram fundamentais para obter corpos cerâmicos densos e homogêneos, compatíveis com o acabamento aspirado. Os parâmetros de usinagem que se destacaram foram: profundidade de dressagem de 0,1 mm; pressão de lapidorretificação de 100 kPa; 100 rpm do rebolo e porta-peça; e emulsão (1:40) aplicada por MQF. A aspiração dos resíduos sobre o rebolo melhorou em 21,6% o acabamento, todavia a associação de abrasão dois (rebolo) e três corpos (abrasivos soltos) reduziu em 57,15% a rugosidade. O macroefeito foi visível nos rebolos de #800, #600 e #300 dressados com Ud = 1. A menor rugosidade, Ra = 60,63 nm, proveio do rebolo #300 dressado com Ud=5. O menor desvio de planeza, 0,308 μm, foi obtido com o rebolo de #800 e Ud = 3. O processo alcançou condições de plasticidade da zircônia que apontam para o predomínio dos mecanismos de remoção de microcorte e pulverização de material, sem ocorrência de microtrinca. Segundo ensaios de DRX e Espectroscopia Raman, a lapidorretificação Ud não provocou transformação martensítica. Todavia, o rebolo de #300 gerou alargamento assimétrico dos picos tetragonais nas proximidades de 2θ = 35° e 39° e a reversão das intensidades dos picos tetragonais a 40° e 41°. A reversão foi atribuída a mudança do domínio ferroelástico e a reorientação de planos cristalográficos em nível de cristalito. Os estudos sugerem que a usinagem introduziu tensão residual de compressão que pode ter estabilizado a fase romboédrica. Não há relato de processo capaz de alcançar acabamento nanométrico similar com mesmo tamanho e tipo de abrasivo. A lapidorretificação Ud pode substituir o engajamento da retificação, lapidação e polimento de cerâmica avançada. / The present study focuses on the border of ultra-precision (UP) manufacturing of 3 mol% yttria tetragonal zirconia polycrystal (3Y-TZP), carried out by Ud-lap grinding. The increasing demand for advanced ceramic products with: high surface finish and integrity; high form accuracy; and lower manufacturing cost, has encourage research in several areas of nanoscience and nanotechnology (N&N), to overcome the limitations or adding the main advantages of traditional grinding, lapping, and polishing processes. 3Y-TZP ceramics has been extensively applied by industry due to its exceptional mechanical properties. The 3Y-TZP, however, can present destabilization of its tetragonal phase in different situations and conditions. In the beginning of its manufacture, during its machining for instance, which may compromise its performance. Thus, the 3Y-TZP can be considered a key material to evaluate and qualify abrasive processes aiming gold standard quality that, therefore, should not raise the martensitic transformation. In the midst of plurality of processes, it is noteworthy the Ud-lap grinding. This research studied the UP manufacture of flat TZ-3Y-E zirconia surfaces lap ground with epoxy binder SiC grinding wheels, aiming to nanometer roughness and microstructural integrity without damage. Discs of TZ-3Y-E were isostatically pressed at 200 MPa and sintered at 1400 °C for 2 hours. The discs were characterized by tests of: microhardness; contact and optical profilometry; FEG-SEM; Raman spectroscopy; XRD; and confocal epi-fluorescence. Mechanical and electric-electronic designs of Fiocchi lap grinder were developed toward the UP ceramic grinding. Results showed that the developmental design of Fiocchi lap grinder was successful. The accomplishment and control of ceramic processing stages were essential for dense and homogenous ceramic bodies, compatible with the finish aspired. The machining parameters that stood out were: 0.1 mm depth of dressing; 100 kPa lap grinding pressure; 100 rpm grinding wheel and workpiece-holder; and emulsion applied by MQF. Suction of debris on the grinding wheel has improved finishing in 21.6%, however the combination of two-body abrasion (grinding wheel) and three-body abrasion (loose abrasives) decreased roughness in 57.15%. The macroeffect was visible on #800, #600, and #300 dressed with Ud = 1. The best finishing, Ra = 60.63 nm, came from #300 grinding wheel dressed with Ud = 5. The smallest flatness deviation, 0.308 μm, was obtained with the #800 grinding wheel and Ud = 3. The process has achieved zirconia plasticity conditions pointing towards predominance of microcutting and pulverization material removal mechanism without causing microcrack. According to XRD and Raman spectroscopy, the Ud-lap grinding caused no martensitic transformation. However, #300 grinding wheel has generated asymmetric broadening of the tetragonal peaks close to 2θ = 35° e 39° and reversal of the intensities of 40° and 41° tetragonal peaks. The reversal was attributed to ferroelastic switching and reorientation of crystallographic planes into crystallite level. Studies suggest that the machining has introduced compressive residual stress that may have stabilized rhombohedral phase. There is no report of an abrasive process capable of achieving similar nanometric finish with same grit size and type of abrasive. The Ud-lap grinding can replace the engagement of grinding, lapping, and polishing of advanced ceramics.