27 research outputs found

    Layered Al2O3-SiO2 and Al2O3-Ta2O5 thin-film composites for high dielectric strength, deposited by pulsed direct current and radio frequency magnetron sputtering

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    Multilayer thin films have the potential to act as high dielectric strength insulation for wire and microelectronics. In this study, films consisting of 2, 4 or 8 layers, composed of Al2O3 with SiO2 or Ta2O5, were prepared via pulsed direct current and radio frequency magnetron sputtering to a thickness of between 152 and 236ā€Ænm. The dielectric strengths of all films exceeded the 310 VĪ¼māˆ’1 achieved for PDC Al2O3. Maximum dielectric strengths were obtained for four layer composites; Al2O3-SiO2-Al2O3-SiO2 (466 VĪ¼māˆ’1) and Al2O3-Ta2O5-Al2O3-Ta2O5 (513 VĪ¼māˆ’1), each containing two PDC-Al2O3 and two RF-SiO2/Ta2O5 layers. Whilst the average dielectric strength was higher in the Ta2O5 composites, they suffered from higher leakage prior to breakdown with ca. 6.5ā€ÆnA compared to ca. 0.1ā€ÆnA for SiO2 composites. The mechanical properties of the composites were poorer due to increased intrinsic coating stress. Samples exhibited complete interfacial delamination with maximum coating adhesion strengths of 22 and 25ā€ÆMPa. The variance resulted from larger coefficient of thermal expansion for Ta2O5 compared to SiO2. Sputtered composites of Al2O3 and either SiO2 or Ta2O5 had high breakdown strength with reasonable adhesion and could be suitable for insulating copper conductors in the aerospace and automotive industries

    In vitro degradation and mechanical properties of PLA-PCL copolymer unit cell scaffolds generated by two-photon polymerization

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    The manufacture of 3D scaffolds with specific controlled porous architecture, defined microstructure and an adjustable degradation profile was achieved using two-photon polymerization (TPP) with a size of 2 Ɨ 4 Ɨ 2 mm3. Scaffolds made from poly(D,L-lactide-co-Īµ-caprolactone) copolymer with varying lactic acid (LA) and Īµ -caprolactone (CL) ratios (LC16:4, 18:2 and 9:1) were generated via ring-opening-polymerization and photoactivation. The reactivity was quantified using photo-DSC, yielding a double bond conversion ranging from 70% to 90%. The pore sizes for all LC scaffolds were see 300 Ī¼m and throat sizes varied from 152 to 177 Ī¼m. In vitro degradation was conducted at different temperatures; 37, 50 and 65Ā°C. Change in compressive properties immersed at 37Ā°C over time was also measured. Variations in thermal, degradation and mechanical properties of the LC scaffolds were related to the LA/CL ratio. Scaffold LC16:4 showed significantly lower glass transition temperature (T g) (4.8Ā°C) in comparison with the LC 18:2 and 9:1 (see 32Ā°C). Rates of mass loss for the LC16:4 scaffolds at all temperatures were significantly lower than that for LC18:2 and 9:1. The degradation activation energies for scaffold materials ranged from 82.7 to 94.9 kJ mol-1. A prediction for degradation time was applied through a correlation between long-term degradation studies at 37Ā°C and short-term studies at elevated temperatures (50 and 65Ā°C) using the half-life of mass loss (Time (M1/2)) parameter. However, the initial compressive moduli for LC18:2 and 9:1 scaffolds were 7 to 14 times higher than LC16:4 (see 0.27) which was suggested to be due to its higher CL content (20%). All scaffolds showed a gradual loss in their compressive strength and modulus over time as a result of progressive mass loss over time. The manufacturing process utilized and the scaffolds produced have potential for use in tissue engineering and regenerative medicine applications

    Degradation and characterization of resorbable phosphate-based glass thin-film coatings applied by radio-frequency magnetron sputtering

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    Quinternary phosphate-based glasses of up to 2.67 Ī¼m, deposited by radio-frequency magnetron sputtering, were degraded in distilled water and phosphate-buffered saline (PBS) to investigate their degradation characteristics. Magnetron- sputtered coatings have been structurally compared to their compositionally equivalent melt-quenched bulk glass counterparts. The coatings were found to have structurally variable surfaces to melt-quenched glass such that the respective bridging oxygen to nonbridging oxygen bonds were 34.2% to 65.8% versus 20.5% to 79.5%, forming metaphosphate (PO3)āˆ’(Q2) versus less soluble (P2O7)4āˆ’ (Q1) and (PO4)3āˆ’ (Q0), respectively. This factor led to highly soluble coatings, exhibiting a t1/2 degradation dependence in the first 2 h in distilled water, followed by a more characteristic linear profile because the subsequent layers were less soluble. Degradation was observed to preferentially occur, forming voids characteristic of pitting corrosion, which was confirmed by the use of a focused ion beam. Coating degradation in PBS precipitated a (PO3)āˆ’metaphosphate, an X-ray amorphous layer, which remained adherent to the substrate and seemingly formed a protective diffusion barrier, which inhibited further coating degradation. The implications are that while compositionally similar, sputter-deposited coatings and melt-quenched glasses are structurally dissimilar, most notably, with regard to the surface layer. This factor has been attributed to surface etching of the as-deposited coating layer during deposition and variation in the thermal history between the processes of magnetron sputtering and melt quenching

    In vitro degradation and mechanical properties of PLA-PCL copolymer unit cell scaffolds generated by two-photon polymerization

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    The manufacture of 3D scaffolds with specific controlled porous architecture, defined microstructure and an adjustable degradation profile was achieved using two-photon polymerization (TPP) with a size of 2ā€‰ā€‰Ć—ā€‰ā€‰4ā€‰ā€‰Ć—ā€‰ā€‰2ā€‰mm3. Scaffolds made from poly(D,L-lactide-co-ɛ-caprolactone) copolymer with varying lactic acid (LA) and ɛ -caprolactone (CL) ratios (LC16:4, 18:2 and 9:1) were generated via ring-opening-polymerization and photoactivation. The reactivity was quantified using photo-DSC, yielding a double bond conversion ranging from 70% to 90%. The pore sizes for all LC scaffolds were see 300 Ī¼m and throat sizes varied from 152 to 177 Ī¼m. In vitro degradation was conducted at different temperatures; 37, 50 and 65 Ā°C. Change in compressive properties immersed at 37 Ā°C over time was also measured. Variations in thermal, degradation and mechanical properties of the LC scaffolds were related to the LA/CL ratio. Scaffold LC16:4 showed significantly lower glass transition temperature (T g) (4.8 Ā°C) in comparison with the LC 18:2 and 9:1 (see 32 Ā°C). Rates of mass loss for the LC16:4 scaffolds at all temperatures were significantly lower than that for LC18:2 and 9:1. The degradation activation energies for scaffold materials ranged from 82.7 to 94.9 kJ molāˆ’1. A prediction for degradation time was applied through a correlation between long-term degradation studies at 37 Ā°C and short-term studies at elevated temperatures (50 and 65 Ā°C) using the half-life of mass loss (Time (M1/2)) parameter. However, the initial compressive moduli for LC18:2 and 9:1 scaffolds were 7 to 14 times higher than LC16:4 (see 0.27) which was suggested to be due to its higher CL content (20%). All scaffolds showed a gradual loss in their compressive strength and modulus over time as a result of progressive mass loss over time. The manufacturing process utilized and the scaffolds produced have potential for use in tissue engineering and regenerative medicine applications

    Assessing the life cycle environmental impacts of titania nanoparticle production by continuous flow solvo/hydrothermal synthesis

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    Continuous-flow hydrothermal and solvothermal syntheses offer substantial advantages over conventional processes, producing high quality materials from a wide range of precursors. In this study, we evaluate the ā€œcradle-to-gateā€ life cycle environmental impacts of alternative titanium dioxide (TiOā‚‚) nanoparticle production parameters, considering a range of operational conditions, precursors, material properties and production capacities. A detailed characterisation of the nano-TiOā‚‚ products allows us, for the first time, to link key nanoparticle characteristics to production parameters and environmental impacts, providing a useful foundation for future studies evaluating nano-TiOā‚‚ applications. Five different titanium precursors are considered, ranging from simple inorganic precursors, like titanium oxysulphate (TiOS), to complex organic precursors such as titanium bis(ammonium-lactato)dihydroxide (TiBALD). Synthesis at the laboratory scale is used to determine the yield, size distribution, crystallinity and phase of the nanoparticles. The specifications and operating experience of a full scale plant (>1000 t per year) are used to estimate the mass and energy inputs of industrial scale production for the life cycle assessment. Overall, higher process temperatures are linked to larger, more crystalline nanoparticles and higher conversion rates. Precursor selection also influences nano-TiOā‚‚ properties: production from TiOS results in the largest particle sizes, while TiBALD achieves the smallest particles and narrowest size distribution. Precursor selection is the main factor in determining cradle-to-gate environmental impacts (>80% in some cases), due to the production impact of complex organic precursors. Nano-TiO2 production from TiOS shows the lowest global warming potential (GWP) (<12 kg COā‚‚-eq. per kg TiOā‚‚) and cumulative energy demand (CED) (<149 MJ kgĀÆĀ¹ TiOā‚‚) due to the low environmental impact of the precursor, the use of water as a solvent and its high yield even at lower temperatures. Conversely, the TiBALD precursor shows the highest impact (86 kg COā‚‚-eq. per kg TiOā‚‚ and 1952 MJ kgĀÆĀ¹ TiOā‚‚) due to the need for additional post-synthesis steps and complexity of precursor manufacturing. The main purpose of this study is not a direct comparison of the environmental impacts of TiOā‚‚ nanoparticles manufactured utilizing various precursors under different conditions, but to provide an essential foundation for future work evaluating potential applications of nano-TiOā‚‚ and their life cycle environmental impacts

    Continuous synthesis of dispersant-coated hydroxyapatite plates

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    A continuous flow hydrothermal synthetic route which allows the direct ā€œin situā€ capping/coating of hydroxyapatite nanoplates with functional dispersants in a single stage is reported. The methodology induced crystallisation by rapid mixing of streams of preheated water and solutions of reagents in water, whilst the hydrophobic surface modification of the HA platelets was achieved without morphological disruption. The effect of adding the hydrocarbon either before or after the HA platelet formation point has also been assessed, proving that the presence of surfactant at the reaction site does not interfere with the formation of HA and allows for a more efficient binding and extraction of the inorganic materials. The coupling mechanisms between the surfactant and the HA surface have been proposed to be a mixture of covalent and electrostatic interactions (i.e. all forms of chemisorption). This synthesis route is fully scalable to pilot (10 tons per year) and industrial (1000 tons per year) scales

    Dielectric breakdown of alumina thin films produced by pulsed direct current magnetron sputtering

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    Alumina films (~2ā€ÆĪ¼m thick) were deposited with a mixed Cu/Al interlayer onto copper. Direct current (DC)/Pulsed DC (PDC) magnetron sputtering techniques were independently compared for reactive alumina sputtering. In DC sputtered films, elemental aluminium of 9.2 at.% and nano-crystallites were present within the x-ray amorphous matrix, resulting from target arcing. Defects lead to premature dielectric breakdown/increased current leakage. PDC sputtering improved film quality by removing crystallites, metallic clusters and through thickness cracking. Time dependent dielectric breakdown (TDDB) measurements were carried out using conductive atomic force microscopy identified an improvement in dielectric strength (166 to 310ā€ÆVā€ÆĪ¼māˆ’1) when switching from DC to PDC deposition power. TDDB suggested that at high applied field the dominant pre-breakdown conduction mechanism was Fowler-Nordheim tunnelling in DC films. Tensile pull-off adhesion ranged from 56 to 72ā€ÆMPa and was highest following incorporation of an Cu/Al blended interfacial layer. Scratch testing indicated various cracking/buckling failures

    Melt-processed PLA/HA platelet nanoparticle composites produced using tailored dispersants

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    Hydroxyapatite (HA) nanoparticles, similar to those seen in the structure of human bone, have been produced via hydrothermal synthesisand used to produce nanocomposite materials via melt blending with poly(lactic acid)(PLA). Both of these processes are scalable and commercially relevant. Tailored dispersants were developed and used to improve the dispersion of the HA. Modest improvements in flexural properties were observed (max increases 30% of dry modulus, 13% of wet strength). Rheometry is not suggestive of achieving percolation,so there is potential to improve mechanical properties further. It was established that very dry processing conditions are essential to maintaining the molecular weight of the PLA during processing and that the use of the tailored dispersants can also help to mitigateprocess-induced degradation.MicroCT has proved to be a useful quality control tool to support TEM analysis

    Mechanical, structural and dissolution properties of heat treated thin-film phosphate based glasses

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    Here we show the deposition of 2.7 Ī¼m thick phosphate based glass films produced by magnetron sputtering, followed by post heat treatments at 500 Ā°C. Variations in degradation properties pre and post heat treatment were attributed to the formation of Hematite crystals within a glass matrix, iron oxidation and the depletion of hydrophilic P-O-P bonds within the surface layer. As deposited and heat treated coatings showed interfacial tensile adhesion in excess of 73.6 MPa; which surpassed ISO and FDA requirements for HA coatings. Scratch testing of coatings on polished substrates revealed brittle failure mechanisms, amplified due to heat treatment and interfacial failure occurring from 2.3 to 5.0 N. Coatings that were deposited onto sandblasted substrates to mimic commercial implant surfaces, did not suffer from tensile cracking or trackside delamination showing substantial interfacial improvements to between 8.6 and 11.3 N. An exponential dissolution rate was observed from 0 to 2 h for as deposited coatings, which was eliminated via heat treatment. From 2 to 24 h ion release rates ordered P > Na > Mg > Ca > Fe whilst all coatings exhibited linear degradation rates, which reduced by factors of 2.4ā€“3.0 following heat treatments
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