This research project investigates a new technique to efficiently mix crystalline solid additives with polymers by gentle ball milling with steel balls in the presence of carbon dioxide (C02) at 17 to 30°C and 1300 to 2500 psig. As the ball milling system is agitated, the steel balls transfer mechanical energy to the fluoropolymer and additive thereby converting them to powders. C02 is added into the chamber to expand the polymer and make it amenable to impregnation by the additive. At the end of the mixing process, a free flowing powder is produced consisting of the additive coated with fluoropolymer. The additives were extracted from the powders and intrinsic viscosity measurements were done on the remnant fluoropolymer. Viscosity studies showed that the virgin and post-ball milled fluoropolymers had similar intrinsic viscosities, hence similar molecular weights within experimental error limits. This implies that most of the polymer chains were simply disentangled during the mixing process and not broken. Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analysis (TGA) were done on the virgin polymer, the additives and the fabricated powders to determine the loading levels and to ascertain if there were any changes to the physical properties of the polymer. Scanning electron micrographs showed that some of the powder particles had additive particles stuck on the surface, but when these additives were washed off the surface of the powders with a suitable solvent that did not dissolve the polymer, DSC analysis showed the presence of additive incorporated into the polymer matrix.

Orientador: Célia Maria Landi Franco / Banca: Thais de Souza Rocha / Banca: Ana Carolina Conti e Silva / Resumo: Amidos modificados são utilizados pela indústria de alimentos por apresentarem melhor comportamento que amidos nativos. Modificações visando a redução do diâmetro granular para a obtenção de grânulos de tamanho similar aos da molécula de gordura tem sido de grande interesse, pois este amido modificado pode ser usado como substituto de gordura em diversas formulações. Para isso, o pré-tratamento enzimático pode ser usado para fragilizar a estrutura granular do amido e facilitar um posterior tratamento físico como a moagem, obtendo grânulos com menor diâmetro. O objetivo deste trabalho foi investigar o efeito da hidrólise enzimática seguida de moagem em moinho de bolas sobre as características estruturais e físico-químicas do amido de mandioquinha-salsa (Arracacia xanthorrhiza). Amido isolado de raízes de mandioquinha-salsa foi hidrolisado com α-amilase bacteriana e/ou amiloglucosidase fúngica, a 37 o C, em três diferentes condições: A: 40 SKB/g de α-amilase e 10 U/g amiloglucosidase por 36 h; B: 20 SKB/g de α-amilase e 5 U/g amiloglucosidase por 12 h; C: 5 U/g amiloglucosidase por 12 h. Após hidrólise os mesmos foram moídos por 1 e 2 h. Os amidos nativos e modificados foram analisados quanto à distribuição de tamanho de grânulos. Houve redução do diâmetro dos grânulos para todos os amidos tratados, mas a condição de hidrólise B foi a escolhida para a continuidade dos experimentos, por ter apresentado uma distribuição de tamanho de grânulos após moagem mais homogênea. Os amidos nativos e hidrolisados com 20 SKB/g de α-amilase e 5 U/g amiloglucosidase por 12 h foram analisados quanto a forma dos grânulos, distribuição do comprimento das cadeias laterais da amilopectina, distribuição do tamanho molecular dos componentes do amido, teor de amilose, difração de raios-X... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Modified starches are used by food industry because they have better performance than native starches. Modifications in order to reduce granular diameter to obtain granules of similar size to those of fat molecules has been of great interest, for this modified starch can be used as a fat substitute in various formulations. For this purpose, a enzymatic pretreatment can be used to weaken the granular structure of starch and facilitate a subsequent physical treatment such as grinding. The objective of this study was to investigate the effect of enzymatic hydrolysis followed by milling in a ball mill on the structural and physicochemical characteristics of Peruvian carrot (Arracacia xanthorrhiza) starch. Starch isolated from roots of Peruvian Carrot was hydrolyzed with bacterial α-amylase and fungal amyloglucosidase at 37 °C in three different conditions: A: 40 SKB/g of α-amylase and 10 U/g amyloglucosidase for 36 h; B: 20 SKB/g of α-amylase and 5 U/g amyloglucosidase for 12 h; C: 5 U/g amyloglucosidase for 12 h. After hydrolysis, the starches were ball milled for 1 and 2 h. The native and modified starches were analyzed for granular size distribution. There was reduction of the granular diameter for all modified starches, but the B condition of hydrolysis was choosen to continue the experiments because the starches modified in this condition displayed a more homogeneous granular size distribution after milling. The native and hydrolyzed with 20 SKB / g of α-amylase and 5 U / g amyloglucosidase for 12 h starches were analyzed for granule shape, distribution of branch chain length of amylopectin, molecular size distribution of the starch components, apparent amylose content, X-ray diffraction, thermal and pasting properties, swelling power and solubility. The native starch granules, analyzed in optical microscope... (Complete abstract click electronic access below) / Mestre

Made available in DSpace on 2014-06-11T19:23:26Z (GMT). No. of bitstreams: 0 Previous issue date: 2012-08-02Bitstream added on 2014-06-13T19:50:08Z : No. of bitstreams: 1 conceicao_fs_me_sjrp.pdf: 781570 bytes, checksum: 15b43ff1876929d7de91439fa3fa6f0b (MD5) / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / Amidos modificados são utilizados pela indústria de alimentos por apresentarem melhor comportamento que amidos nativos. Modificações visando a redução do diâmetro granular para a obtenção de grânulos de tamanho similar aos da molécula de gordura tem sido de grande interesse, pois este amido modificado pode ser usado como substituto de gordura em diversas formulações. Para isso, o pré-tratamento enzimático pode ser usado para fragilizar a estrutura granular do amido e facilitar um posterior tratamento físico como a moagem, obtendo grânulos com menor diâmetro. O objetivo deste trabalho foi investigar o efeito da hidrólise enzimática seguida de moagem em moinho de bolas sobre as características estruturais e físico-químicas do amido de mandioquinha-salsa (Arracacia xanthorrhiza). Amido isolado de raízes de mandioquinha-salsa foi hidrolisado com α-amilase bacteriana e/ou amiloglucosidase fúngica, a 37 o C, em três diferentes condições: A: 40 SKB/g de α-amilase e 10 U/g amiloglucosidase por 36 h; B: 20 SKB/g de α-amilase e 5 U/g amiloglucosidase por 12 h; C: 5 U/g amiloglucosidase por 12 h. Após hidrólise os mesmos foram moídos por 1 e 2 h. Os amidos nativos e modificados foram analisados quanto à distribuição de tamanho de grânulos. Houve redução do diâmetro dos grânulos para todos os amidos tratados, mas a condição de hidrólise B foi a escolhida para a continuidade dos experimentos, por ter apresentado uma distribuição de tamanho de grânulos após moagem mais homogênea. Os amidos nativos e hidrolisados com 20 SKB/g de α-amilase e 5 U/g amiloglucosidase por 12 h foram analisados quanto a forma dos grânulos, distribuição do comprimento das cadeias laterais da amilopectina, distribuição do tamanho molecular dos componentes do amido, teor de amilose, difração de raios-X... / Modified starches are used by food industry because they have better performance than native starches. Modifications in order to reduce granular diameter to obtain granules of similar size to those of fat molecules has been of great interest, for this modified starch can be used as a fat substitute in various formulations. For this purpose, a enzymatic pretreatment can be used to weaken the granular structure of starch and facilitate a subsequent physical treatment such as grinding. The objective of this study was to investigate the effect of enzymatic hydrolysis followed by milling in a ball mill on the structural and physicochemical characteristics of Peruvian carrot (Arracacia xanthorrhiza) starch. Starch isolated from roots of Peruvian Carrot was hydrolyzed with bacterial α-amylase and fungal amyloglucosidase at 37 °C in three different conditions: A: 40 SKB/g of α-amylase and 10 U/g amyloglucosidase for 36 h; B: 20 SKB/g of α-amylase and 5 U/g amyloglucosidase for 12 h; C: 5 U/g amyloglucosidase for 12 h. After hydrolysis, the starches were ball milled for 1 and 2 h. The native and modified starches were analyzed for granular size distribution. There was reduction of the granular diameter for all modified starches, but the B condition of hydrolysis was choosen to continue the experiments because the starches modified in this condition displayed a more homogeneous granular size distribution after milling. The native and hydrolyzed with 20 SKB / g of α-amylase and 5 U / g amyloglucosidase for 12 h starches were analyzed for granule shape, distribution of branch chain length of amylopectin, molecular size distribution of the starch components, apparent amylose content, X-ray diffraction, thermal and pasting properties, swelling power and solubility. The native starch granules, analyzed in optical microscope... (Complete abstract click electronic access below)

No / Mechanochemistry enabled the selective synthesis of the recherche´ orange polymorph of Wilkinson’s catalyst [RhCl(PPh3)3]. The mechanochemically prepared Rh-complex catalysed the solvent-free dehydrogenation of Me2NHBH3 in a ball mill. The in situ-generated hydrogen (H2) could be utilised for Rh-catalysed hydrogenation reactions by ball milling. / We thank the RWTH Aachen University for support from the Distinguished Professorship Program funded by the Excellence Initiative of the German federal and state governments, and the EPSRC for funding (EP/L019655/1).

Philosophiae Doctor - PhD / Magnesium hydride has long been regarded as a promising candidate for lightweight hydrogen storage applications, owing to reasonably high theoretical capacity (7.6 wt. %). It is burdened by slow absorption/desorption kinetics which has been the target for improvement of many research groups over the years. Nanostructured MgH2 prepared by high energy reactive ball milling (HRBM) of Mg under hydrogen atmosphere with the addition of V or Ti results in modified MgH2 that demonstrates superior hydrogenation/dehydrogenation kinetics without a crippling compromise in storage capacity. Mg – FeV nanocomposites prepared via ball milling of Mg and FeV raw materials demonstrated up to 96.4% of the theoretical storage capacity and comparable kinetics to Mg - V prepared via the same method using pure refined V (which is far costlier than FeV). In both cases, the hydrogenation/dehydrogenation kinetics was much improved than pure Mg alone, as evidenced by faster hydrogenation times. In terms of cyclic stability, Mg – 10FeV demonstrated improvement over pure Mg with final absorption and desorption capacities of 4.93 ± 0.02 wt. % and 4.82 ± 0.02 wt. % respectively over 30 cycles. When compared against Mg – V, Mg – FeV showed slightly inferior improvements, attributed to incomplete hydrogenation of V in the presence of Fe. However, they share similar crystalline BCC, BCT – V2H and FCC - VH phases with the size of less than 10 nm and demonstrated the same behaviour at high temperatures; at temperatures approaching 400 °C, particle sintering became an issue for both nanocomposites resulting in a drop in absorption capacity even in the first cycle. The further inclusion of carbonaceous species showed several effects, one of which was an improvement in hydrogen uptake speed as well as kinetics for the addition of 5 wt. % activated carbon. For the sample with 5 wt. % graphite, the appearance of an initial incubation period of up to 60 minutes was noted, presumably corresponding to the duration of time when the carbon was sheared and crushed before hydrogenation commences.

The transformations occurring in the sub-stoichiometric Ti(C,N) – W - Al system processed by high energy ball mill were investigated. The milling parameters included the milling time and the temperature comprising milling at subzero temperature and above 25°C. Two sub-stoichiometric Ti(C,N) stocks were selected, the Ti(C0.5N0.05) containing more interstitial elements than the Ti(C0.5N0.5)0.6.The transformation stages and mechanisms of alloying are discussed with respect to the changes in crystal structures of the powder constituents. The milling atmosphere had an effect on the lattice strain of milled products, and hence on the kinetics of solid state dissolution between the powder constituents, but it did not affect the fracturing process. The release of the stored crystallite lattice strain energy was the major determinant in mechanical alloying, with particle size reduction playing a necessary, but less significant role. The strain energy and the fine particle size contributed to the increased chemical reactivity with oxygen of the powders milled for shorter times. The affinity of the powders with oxygen decreased after W dissolution in Ti(C,N), and the subsequent decrease in lattice strains. The annealing behaviour of Ti(C0.5N0.05) - 40wt% W and Ti(C0.5N0.5)0.6 - 40wt% W mechanically alloyed powders were investigated using XRD, TEM, SEM and DTA techniques. It was observed that the reaction start and finish temperatures between constituents were lower in the system that had higher residual lattice strains after milling. The compositions of the intermetallic compounds and the solid solutions formed were dependent on the milling conditions and the annealing temperature. Thermal alloying was observed during annealing of Ti(C0.5N0.05) - 40wt% W mechanically alloyed products, whereas de-mixing of W-rich phases from the metastable solid solution occurred during annealing of the Ti(C0.5N0.5)0.6 - 40wt% W milled powders. The effects of Al addition and milling at subzero temperatures on the transformation of Ti(C0.5N0.05)-W powder mixtures were investigated. Addition of Al powder improved the kinetics of solid solution between powder constituents. The effect of Al was ascribed to the increase of lattice strain during short milling time followed of relaxation at longer time, and to the fast diffusion of atoms. Also, it was noticed that the high viscosity of the process control agent could inhibit the alloying process. Multiple three-component compounds could be formed. Aluminium preferably reacted with tungsten. The W(Al,C) and W(Al,Ti) formed were stable, thus solubility of W in Ti(C0.5N0.05) in the presence of Al was limited. The evolution of the morphologies of Ti(C,N)-W mixtures show that fracturing of hard particles dominated in the early stage of milling in the absence of Al, whereas with Al, plastic deformation of particles and cold welding of Ti(C,N) and W particles by the softer Al prevailed at the same time. Longer milling time improved the homogeneity and the formation of nanostructured binder pools in the sintered products. Lower oxygen contents in sintered PcBN were achieved by mechanically alloying Ti(C,N), W and Al in the high energy ball milling stage. Low level of Co in the infiltration layer was also achieved when sintering PcBN with this type of binder. A link was established between the addition of Al at the attrition milling stage and high oxygen content in the sintered PcBN, thus should be avoided. The pressure and temperature applied during sintering or annealing had a strong effect on the compositions and the crystal structures of the phases formed in the mechanically alloyed binder. The lattice strains of the binder and the PcBN were higher in the sintered materials prepared with the Ti(C0.5N0.5)0.6-W binder than in those made using the Ti(C0.5N0.05)-W alloys.

Thesis advisor: Zhifeng Ren / Thermoelectric (TE) technology is an environment-friendly one due to reduction of carbon emission, which can be widely used either for power generation or for refrigeration. Basically applications of TEs are based on TE effects, which involve the transition between heat and electricity. Despite the superior advantages of being solid state and providing a clean form of energy, TE technology so far only finds its niche area of application due to the relatively less efficiency compared to traditional methods. The efficiency of a thermoelectric device is solely determined by the dimensionless figure-of-merit (ZT) of thermoelectric materials. According to the definition, ZT is equal to square of Seebeck coefficient times electrical conductivity times absolute temperature divided by thermal conductivity. Therefore, a good thermoelectric material should possess high Seebeck coefficient and electrical conductivity while low thermal conductivity, so called phonon glass electron crystal (PGEC). In bulk materials, it is challenging to further improve ZT or independently vary individual parameters without affecting others, mainly due to the interrelated relationships among these three parameters. Fortunately, nano approach gives us some independent control in parameters adjustment. One important aspect of nano idea lies in the fact that enhanced boundary scattering due to the increased intensities of interfaces arising from nano-sized grains could reduce the thermal conductivity more than the electrical conductivity, which is practically realized in our material system. Since the introduction of nano idea, large ZT as high as above two has been achieved in the superlattice system. Due to the high fabrication cost of superlattices, they are not scalable for mass production. Theoretical calculations indicate that thermal boundary resistance is the main mechanism for the low thermal conductivity in superlattices, rather than the periodicity. Basically, we hope to achieve the supplattice-like ZT in the less costly bulk nanograined materials, based on the idea that reduction of thermal conductivity which is responsible for ZT enhancement in superlattices can be realized in bulk materials with embedded nanostructures as well. Inspired by the nanocomposite idea, in my thesis work I applied the technique of ball milling and then hot press to various thermoelectric materials, from low temperature to high temperature, demonstrating the feasibility of the approach. By ball milling alloyed ingot into nanopowders and DC hot pressing them, we have achieved a 62-89% ZT improvement for p-type half-Heusler samples, mainly due to the significantly enhanced Seebeck coefficient and partially due to the moderately reduced thermal conductivity. Microstructure studies indicated that increased boundaries due to smaller nano-sized grains is the cause for change of parameters. For our ball milled samples, the trend of decreasing thermal conductivities with increasing ball milling time is observed, further substantiating our nano-approach idea because longer ball milling time gives rise to smaller grain sizes and thus stronger boundary scattering. By applying the same technique to n-type half-Heuslers, we also successfully obtained pronounced enhancement in ZT especially at medium and low temperature ranges, which might be useful in medium temperature power generation. By ball milling a mixture of individual constituent elements into alloyed nanopowders and then DC hot pressing them, we did not gain improvement in ZT initially for n-type BiTeSe system mainly due to the simultaneous reduced power factor with the thermal conductivity. Considering anisotropic properties of the n-type BiTeSe single crystal and randomization effect of ball milling process, we repressed the as-pressed bulk samples in a bigger diameter die, during which lateral flow took place, resulting in preferred grain orientation. As a result, a 22% improvement in the peak ZT from 0.85 to 1.04 at 125 oC in n-type Bi₂Te_2.7Se_0.3 has been successfully achieved, arising from the more enhanced power factor than the thermal conductivity. Compared with single crystal, we benefit from the small nano-sized grains in bulk materials. Taking into account the in-plane power factor of single crystal, we still have much room for further ZT improvement if more ab orientation is promoted into the disk plane and/or the crystal plate size and thickness are reduced. By applying our technique of ball milling and then hot press to p-type skutterudites system, we have achieved a peak ZT of 0.95 at 450 <super>o</super>C in NdFe_3.5Co_0.5Sb₁₂, which is comparable to that of the state-of-the-art ingot. Our approach has the advantage of being less costly and more time-efficient compared to traditional fabrication methods. Besides, even lower thermal conductivity and hence higher ZT can be expected, provided that the nanosize of the precursor powder is preserved during hot press. The nanocomposite idea has been substantiated and the feasibility and generality of our ball milling and then hot press approach has been demonstrated, based on the thermoelectric properties data we obtained and the microstructure studies we carried out from various thermoelectric material systems, from low temperature to high temperature. We believe that continued effort in the area of thermoelectrics by our approach should be paid with superlattice-like ZT if ingenious methods are devised to control the grain growth during consolidation. / Thesis (PhD) — Boston College, 2010. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Physics.

The environmentally friendly n-type Mg2(Si, Sn) thermoelectric solid solutions have a strong potential of commercial utilization in thermoelectric (TE) energy conversion due to their availability, low density (~3.02 g/cm3), and high stability at middle temperature range (400-600 ▫C) that are typically observed from waste heat dissipating systems. The bulk materials were prepared from element powders via slow cooking under vacuum condition and current-assisted hot-press sintering. Temperature vs time curves have been researched in this thesis for fully reacted magnesium-silicide & magnesium-stannide green ingots with doping materials i.e. antimony, bismuth by different doping ratios. These ingots were ground by a high energy ball miller, uniaxial cold pressed into half inch pallets and then sintered by Direct Current-assisted hot pressing. Different synthesis conditions such as ball milling, sintering time, pressure, have been compared by SEM images and XRD tests analysis to figure out optimized process parameters. Several samples’ thermal conductivities (κ) were plotted as a function of temperature to study different synthesis strategies and doping materials’ effects on phonon scattering inside bulk thermoelectric materials.

Mechanical Alloying is a manufacturing process that produces alloys by cold welding of powders. Usually, a vial containing both the powder and steel balls is agitated. Due to impact between the balls and balls and the vial, the powder is mechanically deformed, crushed, and mixed at nano-scales. In this thesis, a numerical model is developed to simulate the dynamics of the vial and the grinding balls of the SPEX 8000 ball milling device, a standardized equipment in both industrial and academic investigations of ball milling. The numerical model is based on the Event Driven Method, typically used to model granular flows. The method implemented is more efficient than the discrete element method used previously to study ball milling dynamics. The numerical tool obtained is useful for scale-up and optimization of mechanical alloying of various materials. An optimization study is presented for the SPEX 8000.

Mechanical Alloying is a manufacturing process that produces alloys by cold welding of powders. Usually, a vial containing both the powder and steel balls is agitated. Due to impact between the balls and balls and the vial, the powder is mechanically deformed, crushed, and mixed at nano-scales. In this thesis, a numerical model is developed to simulate the dynamics of the vial and the grinding balls of the SPEX 8000 ball milling device, a standardized equipment in both industrial and academic investigations of ball milling. The numerical model is based on the Event Driven Method, typically used to model granular flows. The method implemented is more efficient than the discrete element method used previously to study ball milling dynamics. The numerical tool obtained is useful for scale-up and optimization of mechanical alloying of various materials. An optimization study is presented for the SPEX 8000.