title: Dinuclear platinum(II) sulfide–thiolate complexes [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ containing fluorinated substituents and the identification of a SC₆F₅ π interaction in the crystal structure of [Pt₂(μ-S)(μ-SCH₂C₆F₅)(PPh₃)₄]BPh₄•2C₆H₆

authors: Henderson, William

subjects: platinum complexes

abstract: Reactions of the platinum(II) sulfido complex [Pt₂(μ-S)₂(PPh₃)₄] with the alkyl iodides ICH₂CH₂(CF₂)nCF₃ (n = 3, 7) gives good yields of the monoalkylated products [Pt₂(μ-S){μ-SCH₂CH₂(CF₂)nCF₃}(PPh₃)₄]⁺, which were isolated as  PF₆⁺or  BPH₄⁻ salts, and characterised by ESI mass spectrometry, NMR spectroscopy and elemental analysis. The complex [Pt₂(μ-S){μ-SCH₂CH₂(CF₂)nCF₃}(PPh₃)₄]⁺ appears to have normal reactivity for this type of complex, namely reaction with Ph₃PAuCl to give [Pt₂(μ-SAuPPh₃){μ-SCH₂CH₂(CF₂)nCF₃}(PPh₃)₄]₂⁺, and reaction with Me₂SO₄ to give [Pt₂(μ-SMe){μ-SCH₂CH₂(CF₂)nCF₃}(PPh₃)₄]₂⁺. Reaction of [Pt₂(μ-S)₂(PPh₃)₄] with C₆F₅CH₂Br gave [Pt₂(μ-S)(μ-SCH₂C₆F₅)(PPh₃)₄]⁺, isolated as BPh₄⁻ its  salt, and characterised by NMR spectroscopy and a single-crystal X-ray structure determination. The C₆F₅ group lies above the {Pt₂S₂} core of the complex as a result of a SC₆F₅ π interaction, in contrast to the published structure of [Pt₂(μ-S)(μ-SCH₂C₆H₅)(PPh₃)₄]PF₆, where the C₆H₅ group projects away from the {Pt₂S₂} core.

text: Dinuclear platinum(II) sulfide–thiolate complexes [Pt₂(μ-S)(μ-SR)(PPh₃)₄]⁺ containing fluorinated substituents and the identification of a SC₆F₅ π interaction in the crystal structure of [Pt₂(μ-S)(μ-SCH₂C₆F₅)(PPh₃)₄]BPh₄•2C₆H₆ Reactions of the platinum(II) sulfido complex [Pt₂(μ-S)₂(PPh₃)₄] with the alkyl iodides ICH₂CH₂(CF₂)nCF₃ (n = 3, 7) gives good yields of the monoalkylated products [Pt₂(μ-S){μ-SCH₂CH₂(CF₂)nCF₃}(PPh₃)₄]⁺, which were isolated as  PF₆⁺or  BPH₄⁻ salts, and characterised by ESI mass spectrometry, NMR spectroscopy and elemental analysis. The complex [Pt₂(μ-S){μ-SCH₂CH₂(CF₂)nCF₃}(PPh₃)₄]⁺ appears to have normal reactivity for this type of complex, namely reaction with Ph₃PAuCl to give [Pt₂(μ-SAuPPh₃){μ-SCH₂CH₂(CF₂)nCF₃}(PPh₃)₄]₂⁺, and reaction with Me₂SO₄ to give [Pt₂(μ-SMe){μ-SCH₂CH₂(CF₂)nCF₃}(PPh₃)₄]₂⁺. Reaction of [Pt₂(μ-S)₂(PPh₃)₄] with C₆F₅CH₂Br gave [Pt₂(μ-S)(μ-SCH₂C₆F₅)(PPh₃)₄]⁺, isolated as BPh₄⁻ its  salt, and characterised by NMR spectroscopy and a single-crystal X-ray structure determination. The C₆F₅ group lies above the {Pt₂S₂} core of the complex as a result of a SC₆F₅ π interaction, in contrast to the published structure of [Pt₂(μ-S)(μ-SCH₂C₆H₅)(PPh₃)₄]PF₆, where the C₆H₅ group projects away from the {Pt₂S₂} core.

year: 2011

title: Tensile properties and fracture behaviour of an ultrafine grained Ti–47Al–2Cr (at.%) alloy at room and elevated temperatures

authors: Nadakuduru, Vijay Navaratna

subjects: brittle to ductile transition temperature

abstract: An ultrafine grained (UFG) Ti–47Al–2Cr (at.%) alloy has been synthesized using a combination of high energy mechanical milling and hot isostatic pressing (HIP) of a Ti/Al/Cr composite powder compact. The material produced has been tensile tested at room temperature, 700 and 800 °C, respectively, and the microstructure of the as-HIPed material and the microstructure and fracture surfaces of the tensile tested specimens have been examined using X-ray diffractometry, optical microscopy, scanning electron microscopy and transmission electron microscopy. The alloy shows no ductility during tensile testing at room temperature and 700 °C, respectively, but very high ductility (elongation to fracture 70–100%) when tensile tested 800 °C, indicating that its brittle to ductile transition temperature (BDTT) falls within the temperature range of 700–800 °C. The retaining of ultrafine fine equiaxed grain morphology after the large amount of plastic deformation of the specimens tensile tested at 800 °C and the clear morphology of individual grains in the fractured surface indicate that grain boundary sliding is the predominant deformation mechanism of plastic deformation of the UFG TiAl based alloy at 800 °C. Cavitation occurs at locations fairly uniformly distributed throughout the gauge length sections of the specimens tensile tested at 800 °C, again supporting the postulation that grain boundary sliding is the dominant mechanism of the plastic deformation of the UFG TiAl alloys at temperatures above their BDTT. The high ductility of the UFG alloy at 800 °C and its fairly low BDTT indicates that the material a highly favourable precursor for secondary thermomechanical processing.

text: Tensile properties and fracture behaviour of an ultrafine grained Ti–47Al–2Cr (at.%) alloy at room and elevated temperatures An ultrafine grained (UFG) Ti–47Al–2Cr (at.%) alloy has been synthesized using a combination of high energy mechanical milling and hot isostatic pressing (HIP) of a Ti/Al/Cr composite powder compact. The material produced has been tensile tested at room temperature, 700 and 800 °C, respectively, and the microstructure of the as-HIPed material and the microstructure and fracture surfaces of the tensile tested specimens have been examined using X-ray diffractometry, optical microscopy, scanning electron microscopy and transmission electron microscopy. The alloy shows no ductility during tensile testing at room temperature and 700 °C, respectively, but very high ductility (elongation to fracture 70–100%) when tensile tested 800 °C, indicating that its brittle to ductile transition temperature (BDTT) falls within the temperature range of 700–800 °C. The retaining of ultrafine fine equiaxed grain morphology after the large amount of plastic deformation of the specimens tensile tested at 800 °C and the clear morphology of individual grains in the fractured surface indicate that grain boundary sliding is the predominant deformation mechanism of plastic deformation of the UFG TiAl based alloy at 800 °C. Cavitation occurs at locations fairly uniformly distributed throughout the gauge length sections of the specimens tensile tested at 800 °C, again supporting the postulation that grain boundary sliding is the dominant mechanism of the plastic deformation of the UFG TiAl alloys at temperatures above their BDTT. The high ductility of the UFG alloy at 800 °C and its fairly low BDTT indicates that the material a highly favourable precursor for secondary thermomechanical processing.

year: 2012

title: Ngā hau pūkeri e tīhaehae nei i ā tātou tikanga Māori

authors: Nock, Sophie

subjects: Tikanga Māori

abstract: Ko te wherawhera a tēnei tuhinga he titiro ki ngā io mai i ngā tikanga o te ao Māori, ā, ki ngā hau kino e whakataurekareka ana i ā tātou tikanga Māori. Kei roto i ngā iwi katoa o te ao ā rātau tikanga, engari, ko ngā whakamāramatanga o aua tikanga kei te mau ruhiruhi noa i roto i ngā hinengaro o ngā tāngata o tēnā iwi, tēnā iwi, ā, kua ngaro katoa atu rānei. Nā reira, ko tāku he rapu i aua māramatanga kei muri i ngā tikanga Māori, ā, he rapu anō hoki i ngā tāmitanga, i ngā pēhitanga a tauiwi mā, ko te mutunga ka whakapōrearea i ā tātou tikanga Māori.
Ko te aronga rangahau mō tēnei kaupapa he whai i ngā tuhinga me ngā kōrero i ahu mai i te ao Māori me te ao Pākehā. Ko ngā rauemi nei i ahu mai i ngā kohikohinga kōrero tawhito me ngā tuhinga a te hunga o roto i ngā tau kātahi anō ka pahure ake. Ko ngā kōrero tawhito nei hei whakaata ake i te huringa o te ao, ā, ka tīkina atu aua kōrero hei ārahi i te hunga ora kia mau tonu ai ā tātou tikanga Māori.
Ki te whai haere i tēnei momo kaupapa, me mātua whai rawa i ngā kōrero ā-waha hei whakaatu mai, ina kāore hoki i āta tuhia whānuihia ngā kōrero i maringi mai i te hinengaro o te hunga whakautu pātai. Ko ngā kohinga kōrero ā-waha hei tohu i ngā tikanga me ngā whakapono ake i pā mai ki a rātou i te wā e tipu ake ana.
Ko ētahi o ngā kaikōrero i tipu ake i roto i te tūturutanga o te ao Māori, arā, i tipu ake i ngā rekereke o ō rātou kuia, koroua, ā, ko ētahi ahakoa he Māori, i tipu ake anō i roto i te reo me ētahi o ngā tikanga Māori, ko ētahi anō i noho hoki i te tāone.
Ko ngā kaupapa ka whakaarahia ake e tēnei rangahau ko ngā tikanga e hāngai pū ana, e whakamahia ana, e kitea ana, e whakaatu ana anō hoki i ngā whakapono o te Māori. Kāti, ka tirohia ētahi tikanga i waenga i te whānau, ētahi atu tikanga hāngai pū ana ki te manaaki tangata i runga marae me te whakaaro ake ki ngā tohu e tika ana ki te whakanui manuhiri.
He roa te Māori e noho ana i te ao Pākehā, mai i tō rātou taenga mai i te rau tau tekau mā waru. Ko te nuinga o tātau kua roa kē te wehenga mai i te ao tūturu ake o te Māori. Ko ētahi tāngata e pupuri tonu ana i ētahi o ā tātou tikanga, ko ētahi kāhore noa e mōhio ana. Tēnā pea, ko ngā whakatūpato i mau, engari, ko ngā whakamārama kei te ngaro. Kāti, ko te tūmanako mō tēnei tuhingaroa ko te whakahoutia anō o te here ki ā tātou tikanga. Ka āhei hoki te hunga e ngākaunui ana ki te kaupapa nei ki te whai whakaaro, te whai māramatanga.
Ko tēnei tuhinga he tauira hei whakaatu atu he mahi pakeke te hopu, te tiaki, te manaaki me te ako hoki i ngā mātauranga o tuawhakarere. He pēnei anō ēnei tikanga mō nāianei, he toimaha tonu te kawe, te whakaū.
Heoi, ka whakatakia mai ngā kōrero i te orokohanga o te ao hei raranga ake hei whāriki mō te tikanga Māori. Tuatahi, ka tirohia ētahi o ngā whenu o tēnei mahi whata, arā, te ahunga mai o te tikanga Māori me ngā tikanga huhua i whakatauiratia mai e ngā atua Māori. Whai muri atu kei te upoko tuarua, ka whakaraupapahia mai ngā kōrero a te hunga whakautu pātai kia āta kitea ai ō rātou whakaaro mō te tikanga Māori. Ka hāngai pū tonu tēnei titiro ki ngā momo pātai, ā, ka tirohia hoki ngā whakahokinga a taua hunga nā.
Kei te upoko tuatoru ka huri te titiro ki ngā hau pūkeri e tūkino nei i ā tātou tikanga Māori. Tuatahi, ka horahia ngā kōrero, ngā tikanga mō te āhua o te noho a te Māori o mua, kia āta kitea ai i pēhea te āhua o tōna whakahaere i tōna ao o mua. Kātahi, ka āta tirohia ētahi ture Pākehā e tīhaehae nei i ā tātou tikanga, pēnei i te ngaro haere o te reo Māori, te haehae haere o ā tātou tikanga Māori. Ka mutu, ka huri ake ki te whai whakaaro ki ētahi o ngā raru i pā mai ki te tikanga Māori i te neketanga o te Māori ki te tāone noho ai, mahi ai.
Kei te upoko tuawhā ētahi tauira mō ngā tūmomo tikanga e mahia ana e te Māori i waenganui i tōna whānau. Ka tirohia te ringa tapu o te tikanga hei whakaohooho ake i te hinengaro, hei whakatakoto māramatanga mō aua tikanga hoki.
Kei te upoko tuarima te tirohanga ki ngā momo tikanga i runga marae, me ngā momo tohu Māori e whakaatu mai ana i te rangatiratanga o te iwi, pēnei i ngā tohu kino, i ngā tohu ora rānei. Ka tirohia ētahi whakamāramatanga mō te āhua o te noho piri o te Māori ki tōna taiao, he aha ngā kōrero a te taiao ki te Māori, he aha hoki ngā kōrero a ngā kararehe o te taiao.
Hei whakakapi ake i te tuhinga nei ko te whakarāpopototanga. I konei ka titiro whakamuri ki ngā āhuatanga kua ara ake. Ka whakaraupapahia ngā whakakitenga me ngā whakaputanga hei whakaohooho, hei whakaarotanga ake mō te ao kei mua e pā ana ki ā tātou tikanga Māori.

text: Ngā hau pūkeri e tīhaehae nei i ā tātou tikanga Māori Ko te wherawhera a tēnei tuhinga he titiro ki ngā io mai i ngā tikanga o te ao Māori, ā, ki ngā hau kino e whakataurekareka ana i ā tātou tikanga Māori. Kei roto i ngā iwi katoa o te ao ā rātau tikanga, engari, ko ngā whakamāramatanga o aua tikanga kei te mau ruhiruhi noa i roto i ngā hinengaro o ngā tāngata o tēnā iwi, tēnā iwi, ā, kua ngaro katoa atu rānei. Nā reira, ko tāku he rapu i aua māramatanga kei muri i ngā tikanga Māori, ā, he rapu anō hoki i ngā tāmitanga, i ngā pēhitanga a tauiwi mā, ko te mutunga ka whakapōrearea i ā tātou tikanga Māori.
Ko te aronga rangahau mō tēnei kaupapa he whai i ngā tuhinga me ngā kōrero i ahu mai i te ao Māori me te ao Pākehā. Ko ngā rauemi nei i ahu mai i ngā kohikohinga kōrero tawhito me ngā tuhinga a te hunga o roto i ngā tau kātahi anō ka pahure ake. Ko ngā kōrero tawhito nei hei whakaata ake i te huringa o te ao, ā, ka tīkina atu aua kōrero hei ārahi i te hunga ora kia mau tonu ai ā tātou tikanga Māori.
Ki te whai haere i tēnei momo kaupapa, me mātua whai rawa i ngā kōrero ā-waha hei whakaatu mai, ina kāore hoki i āta tuhia whānuihia ngā kōrero i maringi mai i te hinengaro o te hunga whakautu pātai. Ko ngā kohinga kōrero ā-waha hei tohu i ngā tikanga me ngā whakapono ake i pā mai ki a rātou i te wā e tipu ake ana.
Ko ētahi o ngā kaikōrero i tipu ake i roto i te tūturutanga o te ao Māori, arā, i tipu ake i ngā rekereke o ō rātou kuia, koroua, ā, ko ētahi ahakoa he Māori, i tipu ake anō i roto i te reo me ētahi o ngā tikanga Māori, ko ētahi anō i noho hoki i te tāone.
Ko ngā kaupapa ka whakaarahia ake e tēnei rangahau ko ngā tikanga e hāngai pū ana, e whakamahia ana, e kitea ana, e whakaatu ana anō hoki i ngā whakapono o te Māori. Kāti, ka tirohia ētahi tikanga i waenga i te whānau, ētahi atu tikanga hāngai pū ana ki te manaaki tangata i runga marae me te whakaaro ake ki ngā tohu e tika ana ki te whakanui manuhiri.
He roa te Māori e noho ana i te ao Pākehā, mai i tō rātou taenga mai i te rau tau tekau mā waru. Ko te nuinga o tātau kua roa kē te wehenga mai i te ao tūturu ake o te Māori. Ko ētahi tāngata e pupuri tonu ana i ētahi o ā tātou tikanga, ko ētahi kāhore noa e mōhio ana. Tēnā pea, ko ngā whakatūpato i mau, engari, ko ngā whakamārama kei te ngaro. Kāti, ko te tūmanako mō tēnei tuhingaroa ko te whakahoutia anō o te here ki ā tātou tikanga. Ka āhei hoki te hunga e ngākaunui ana ki te kaupapa nei ki te whai whakaaro, te whai māramatanga.
Ko tēnei tuhinga he tauira hei whakaatu atu he mahi pakeke te hopu, te tiaki, te manaaki me te ako hoki i ngā mātauranga o tuawhakarere. He pēnei anō ēnei tikanga mō nāianei, he toimaha tonu te kawe, te whakaū.
Heoi, ka whakatakia mai ngā kōrero i te orokohanga o te ao hei raranga ake hei whāriki mō te tikanga Māori. Tuatahi, ka tirohia ētahi o ngā whenu o tēnei mahi whata, arā, te ahunga mai o te tikanga Māori me ngā tikanga huhua i whakatauiratia mai e ngā atua Māori. Whai muri atu kei te upoko tuarua, ka whakaraupapahia mai ngā kōrero a te hunga whakautu pātai kia āta kitea ai ō rātou whakaaro mō te tikanga Māori. Ka hāngai pū tonu tēnei titiro ki ngā momo pātai, ā, ka tirohia hoki ngā whakahokinga a taua hunga nā.
Kei te upoko tuatoru ka huri te titiro ki ngā hau pūkeri e tūkino nei i ā tātou tikanga Māori. Tuatahi, ka horahia ngā kōrero, ngā tikanga mō te āhua o te noho a te Māori o mua, kia āta kitea ai i pēhea te āhua o tōna whakahaere i tōna ao o mua. Kātahi, ka āta tirohia ētahi ture Pākehā e tīhaehae nei i ā tātou tikanga, pēnei i te ngaro haere o te reo Māori, te haehae haere o ā tātou tikanga Māori. Ka mutu, ka huri ake ki te whai whakaaro ki ētahi o ngā raru i pā mai ki te tikanga Māori i te neketanga o te Māori ki te tāone noho ai, mahi ai.
Kei te upoko tuawhā ētahi tauira mō ngā tūmomo tikanga e mahia ana e te Māori i waenganui i tōna whānau. Ka tirohia te ringa tapu o te tikanga hei whakaohooho ake i te hinengaro, hei whakatakoto māramatanga mō aua tikanga hoki.
Kei te upoko tuarima te tirohanga ki ngā momo tikanga i runga marae, me ngā momo tohu Māori e whakaatu mai ana i te rangatiratanga o te iwi, pēnei i ngā tohu kino, i ngā tohu ora rānei. Ka tirohia ētahi whakamāramatanga mō te āhua o te noho piri o te Māori ki tōna taiao, he aha ngā kōrero a te taiao ki te Māori, he aha hoki ngā kōrero a ngā kararehe o te taiao.
Hei whakakapi ake i te tuhinga nei ko te whakarāpopototanga. I konei ka titiro whakamuri ki ngā āhuatanga kua ara ake. Ka whakaraupapahia ngā whakakitenga me ngā whakaputanga hei whakaohooho, hei whakaarotanga ake mō te ao kei mua e pā ana ki ā tātou tikanga Māori.

year: 2003