Multiblock [-A-B-]_n copolymers of bisphenol-A polycarbonate (I) and several poly(arylether sulfones) (II) have been investigated. The copolymers [see document for a diagram of copolymers (I) and (II)] were prepared from hydroxyl terminated oligomers (4,000 < M̅_n < 30,000) by an interfacial technique which utilized phosgene as the coupling agent. Characterization of the oligomers and copolymers included end group analysis, membrane osmometry, and gel permeation chromatography. One of the most interesting aspects of block copolymers is their ability to undergo microphase separation above a critical block length. Either one or two phase block copolymers can be prepared by controlling the molecular weights of the parent oligomers. In the bisphenol-A polycarbonate/bisphenol-A polysulfone system, for example, strictly one phase materials, with only one intermediate glass transition temperature, were obtained at block lengths of less than 10,000 g/mole. Two-phase copolymers resulted when blocks exceeding 20,000 g/mole were coupled. Copolymers comprised of intermediately sized blocks (M̅_n ≃16,000) could be obtained as either single or multiphase systems depending upon their previous thermal history. Homogeneous films, with a single intermediate Tg, were obtained via solution casting, whereas compression molding provided films exhibiting two Tg's. Subsequent DSC studies pointed out that microphase separation could be thermally, and irreversibly, induced by annealing above the Tg of the polysulfone blocks (190°C). Since polycarbonate and polysulfone are leading examples of tough, amorphous thermoplastics, the effects of microphase separation on the tensile, impact, and melt flow properties of the copolymers were investigated. A novel falling weight impact tester was designed and constructed to meet the needs of this study. The device was fully instrumented to provide a deceleration-time plot of the impact process by means of an accelerometer mounted in the projectile. Fracture energies for commercial homopolymers and graphite reinforced composites, in addition to polysulfone-polycarbonate block copolymers, were calculated from the impact curves. Both the tensile and impact properties of the copolymers improved with increasing polycarbonate content. Both single and multiphase materials were ductile and transparent as opposed to physical blends of the two. oligomers which were opaque and possessed poor mechanical properties. No differences due to microphase separation were observed in either the tensile or impact studies. The homogeneous copolymers displayed melt viscosities and activation energies nearly equal to those of the homopolymers. Much greater viscosities and activation energies were exhibited by the phase separated materials indicating that the heterogeneity was retained in the melt. / Ph. D.

The effect of particle size matching and mismatching on the processability, and the mechanical and physical properties of particulate reinforced composites is investigated in this study. These composites were made from dry powder-powder blends. Polymer and reinforcement materials were chosen, characterized and molded into composite plaques. For the same particle volume fraction (400/0), stiffness was found to increase, in general, as particle size decreased. The intimacy of mixing, stiffness and strength improvements depended upon the reinforcement type. These results were compared with predictions from simple micromechanics models to gain a better understanding of their physical behavior. / Master of Science

Metal matrix composites have two important interfacial problems between the matrix and the reinforcement which can reduce its desirable mechanical properties. Chemical differences between the matrix and the reinforcement can lead to reactions and deterioration of the reinforcement. Secondly, structural differences between the matrix and the reinforcement lead to bonding conditions which are far from ideal. By using a reinforcement which has a similar chemistry and local atomic structure to that of the matrix, these critical problems can be reduced. A crystalline matrix reinforced with an amorphous form of the matrix is a possible solution to the problem. Composites of amorphous Fe-W alloy particles reinforcing an Fe matrix were produced using mechanical alloying. Bulk samples were produced and their properties were studied. After analyzing the results, the amorphous alloys were determined to be effective strengtheners. However, porosity in the composites led to a reduction of the strengthening imparted by the reinforcement. / Master of Science

Fish scales can be considered as a laminated composite based on collagen fibrils arranged in a cross-plywood structure. This collagen-based composite is often partially mineralized (primarily hydroxyapatite) in the scale exterior in order to resist penetration and hence to enhance protection. Together with the overlapping assembly, the fish scales offer an excellent model system for developing fiber composite materials and flexible armor systems. The primary objective of this thesis is to characterize the distribution of the mineral phase within individual scale and to investigate the corresponding mechanical consequences of the scale as a whole and its different fields through experimental and computational approaches. In this thesis, we chose the scales from the black drum (Pogonias cromis) fish as a model system. First of all, the exterior surface morphology of individual scales was systematically studied, from which several distinct structural regions are identified, including focus field (central), lateral field (dorsal and ventral), rostral field (anterior), and caudal field (posterior). In the focus field, the classic two-layer design, i.e., mineralized exterior layer and collagen-based interior layer, was observed, and nanoindentation results revealed that the high mineral exterior layer results in a much higher hardness (800 vs 450 MPa). Moreover, macroscopic tensile tests indicate that the mechanical removal of mineralized layer did not lead to reduction in strength values, whereas acid-treated demineralized scales showed reduced mechanical properties. Finally, we identified a previously unreported mineral distribution pattern in the rostral field, in which the mineral phase is segregated into long strips along the anterior-posterior direction (width, ~300 μm). In addition, towards the interior of the scale, it appears that the mineral deposition is highly correlated with the collagen orientation, resulting a unique mineralized-unmineralized collagen-based composite structure. We built finite element models to compare this unique structure to two other mineral phases in different fields at the individual scale. This unique structure demonstrates a larger deformation displacement when load was applied, indicating that it provides further flexibility in anterior end of an individual scale. The mineralized phases and structures of various fields within a single scale provide different mechanical characteristics and properties. The structural and mechanical analysis of the various regions of the fish scale can further investigate the flexibility and protective capacity of the individual scale. / Master of Science / There are many protective systems that attracted scientists' attention, and the typical examples include the nacre, crustacean exoskeletons, and teleost fish scales. Fish scales can be considered as the most common flexible bio-inspired armor system, because they consist of mostly collagen fiber and a highly mineralized hydroxyapatite external layer. Due to the need for swimming and effective protection from predators, fish scales need to have excellent flexibility and penetration resistance. In the previous studies on fish scales, researchers usually focused on the entire scale as a multilayered composite, looking at their response against tension and fracture. The primary objective of this thesis is to characterize the distribution of the mineral phase within individual scale and to investigate the corresponding mechanical consequences of the scale as a whole and its different fields through experimental and computational approaches. In this thesis, we chose the scales from the black drum (Pogonias cromis) fish as a model system. First of all, the exterior surface morphology of individual scales was systematically studied, from which several distinct structural regions were identified, including the focus field (central), lateral field (dorsal and ventral), rostral field (anterior), and caudal field (posterior). In the focus field, the classic two-layer design, i.e., mineralized exterior layer and collagen-based interior layer, was observed, and nanoindentation results revealed that the high mineral exterior layer results in a much higher hardness (800 vs 450 MPa). In addition, we identified a previously unreported unique mineralized-unmineralized collagen-based composite structure in the rostral field, in which the mineral phase is segregated into long strips along the anterior-posterior direction (width, ~300 μm). We built finite element models to compare this unique structure to two other mineral phases in different fields at the individual scale. This unique structure demonstrates a larger deformation displacement when load was applied, indicating that it provides further flexibility at the anterior end of an individual scale, implying that the flexibility is more important at the anterior end of scales where the multi-scales overlap and are covered. The structural and mechanical analysis of the various regions of the fish scale can further investigate the flexibility and protective capacity of the individual scale, and provide further design inspiration for flexible armor designs.

With the increasing use of aluminum in naval vessels and the ever-present danger of fires, it is important to have a good understanding of the behavior of aluminum at elevated temperatures. The aluminum samples 5083-H116 and 6061-T651 were examined under a variety of loading conditions and temperatures. Tensile testing was completed on both materials to measure strength properties of elastic modulus, yield strength, and ultimate strength as well as reduction of area from room temperature to 500 deg C taking measurements every 50 deg C. These tests showed how much the material weakened as temperature increases. Low temperatures had a minimal effect on strength while exposure to temperatures between 200 and 300 deg C had the most significant impact. Creep testing was also completed for these materials. These tests were completed at temperatures between 200 and 400 deg C in 50 deg C increments. Stresses for these tests were in the range of 13 to 160MPa for 5083 aluminum and between 13 to 220MPa for 6061 aluminum. These tests showed a significant relationship between stress and temperature and how changes to one can cause a very different resulting behavior. In addition to the creep testing, three creep models were examined as a means of predicting creep behavior. These models included a power law, exponential, and hyperbolic-sine versions and were able to predict creep results with decent accuracy depending on the stress used in the model. / Master of Science

Results of an experimental test program are presented to determine the bursting strength of polyethylene terephthalate film and fabric cylinders containing axial silts of various lengths. The results demonstrate that the fabric material is superior to the film material as regards residual strength in the presence of a slit. It is shown that the strength-weight ratio of the fabric cylinders is approximately twice that of the film cylinders, largely due to the strength advantage of fiber over film. The results are compared with the predicted bursting strength obtained from two different semiempirical analyses, one based on notch strength analysis and the other employing fracture mechanics concepts. The comparison demonstrates that large errors can result from the application of the notch-strength analysis yields a scatter band which is consistent with the data scatter and follows the trend of the data. / Master of Science

At the present work the UO2 fuel production process was extensively studied and analyzed. The objectives of such investigation were to understand and analyze the influence of different additives and the variation of the production process steps on the microstructure and consequently in the mechanical strength of the nuclear fuel pellet. Moreover, an improvement of the qualitative characteristics of the ceramic fuel pellets was also aimed. For this purpose UO2 pellets without additives, the so-called standard pellets, pellets containing as additive for example AZB (Azodicarbonamid), black U3O8 (Oxidized uranium pellet scrap - OS), green U3O8 (Oxidized uranium powder - OP), keratin fibers (a non conventional additive) were produced. The introduction of these additives to the UO2 powder mixture prior or after the granulation production step and in different concentrations produced several microstructure configurations. As it would not be possible to analyze all of them here so during the investigation pre-tests some of them were separated to be studied in more detail. Pellets with AZB added after the granulation presented larger grains and larger pores than those with AZB added before granulation, also porosity free grains and a granulate structure instead of a homogeneous one. Pellets with OS present fine porosity distributed all over the pellet matrix with some porosity clusters whereas pellets containing OP show in its matrix porosity agglomerated in form of hooks. As for the grain size, a more uniform grain size distribution can be observed in pellets OS than in pellets with OP. The variations in the amount of keratin fibers added, sintering dwell time and green density resulted indeed in different microstructures. Nevertheless, some common characteristics among them were observed such as the presence of elongated pores, porosity clusters and larger grains located at the pellets borders while the smaller ones were concentrated more in the central part of the pellet. This distribution of grains was identified as bi-modal structure. The mentioned microstructure aspects certainly influence on the mechanical properties of the fuel pellet. However, the sintering parameters, the green and final pellet density and the pellet dimensions also have an influence on the mechanical characteristics of the pellets. For studying the influence of all these parameters on the pellet mechanical properties four testing procedures were utilized the so-called squirrel-cage where the mechanical resistance of the not sintered pellets against mechanical shocks was tested, the diametrical compression test (Brazilian Test) where the strength of sintered and not sintered pellets was studied, the Vickers indentation technique and the creep test where the pellet plasticity respectively at room and at elevated temperatures was analyzed. The squirrel-cage results showed that the pellets with keratin fibers were much more mechanically resistant than those pellets without it, which means that the keratin fibers acted, prior sintering, as a powder binder increasing the cohesion among the powder granules proportionating the green pellets higher mechanical resistance against impacts. The Brazilian test evaluated the influence of the pellet length to the pellet diameter (L/D ratio), the influence of different additives mixed to the UO2 powder and the different pellet production processes. The L/D influence analysis showed that if one fixes the pellet diameter and increase the pellet length the Weibull modulus (here a measure of the pellet lot reliability) will also increase. By comparing pellets with OS, OP and 0.3% keratin fibers it was observed that pellets with OS presented the highest volume of pores smaller than 10 mm while pellets with OP and keratin presented the highest volume of pores larger than 20 mm. It seems that this relevant characteristic favored to the highest Weibull strength value for pellets with OS. In the indentation test standard pellets, pellets with OS and pellets with keratin fibers were tested. The results showed that the calculated hardness for the standard pellets is slightly lower when compared to the values obtained by the pellets with keratin fibers. Also the pellets containing OS when compared to the keratin fibers pellets have in most of the cases a lower hardness. The calculated fracture toughness and fracture surface energy values show also a better mechanical behavior for the keratin fibre pellets than in the standard pellets. Standard pellets, pellets with 30%OP, which had the smallest grain size, pellets with keratin fibers, having the bi-modal structure and pellets with chromium oxide, which had the largest grain size, were tested in the creep furnace. The results showed that all pellets with additives presented a better creep behavior than the standard pellets. Among the pellets prepared with additives the comparison clearly showed that under lower stresses pellets with smaller grains have a better creep rate. By increasing the applied stresses we observe an improvement of the creep rate of the pellets with chromium oxide and keratin fibre even slightly overcoming the pellets with 30%OP at the highest applied stress. / Sacramento Santana, HH. (2014). Improving mechanical properties and microstructure development of fiber reinforced ceramic nuclear fuel [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/37199

Yes / Complex biological tissues are highly viscoelastic and dynamic. Efforts to repair or replace cartilage, tendon, muscle, and vasculature using materials that facilitate repair and regeneration have been ongoing for decades. However, materials that possess the mechanical, chemical and resorption characteristics necessary to recapitulate these tissues have been difficult to mimic using synthetic resorbable biomaterials. Herein, we report a series of resorbable elastomer-like materials that are compositionally identical and possess varying ratios of cis:trans double bonds in the backbone. These features afford concomitant control over the mechanical and surface eroding degradation properties of these materials. We show the materials can be functionalized post-polymerization with bioactive species and enhance cell adhesion. Furthermore, an in vivo rat model demonstrates that degradation and resorption are dependent on succinate stoichiometry in the elastomers and the results show limited inflammation highlighting their potential for use in soft tissue regeneration and drug delivery.

No / The main aim of this study is to investigate the effects of nano-SiO2 (NS), nano-Al2O3 (NA), nano-TiO2 (NT) and nano-Fe2O3 (NF) particles in single, binary, ternary, and quaternary combinations on compressive, splitting tensile, and flexural strengths of concrete. The residual compressive strength of control and nano-added concretes are also determined at 300, 500, and 800 °C elevated temperatures. Furthermore, X-ray diffraction (XRD) and scanning electron microscope (SEM) analyses have been conducted to examine the chemical composition and microstructure of concrete samples. The main parameters investigated were the amount and various combinations of NS, NA, NT and NF, producing thirty-one concrete batches, one control and thirty NS, NA, NT and NF added concrete mixes. The total nanoparticle amounts in the concrete mixes of 0.5%, 1%, and 1.5% by weight of cement were studied. A total of 558 concrete specimens with nanoparticles were tested at 28 days to determine compressive, splitting tensile, flexural, and residual compressive strength of concretes at ambient and elevated temperatures. It can be clearly concluded that NS and NA particles are more effective than NT and NF particles in improving the mechanical properties of concrete. The largest increase in compressive, splitting tensile, and flexural strength was obtained for 1.5% of NS and NA hybrid combination as 13.95%, 18.55%, and 21.88%, respectively. Furthermore, the residual compressive strength of single and hybrid nano-added concrete specimens significantly reduced, especially at 800 °C. Although the largest decrease in residual compressive strength of 57.65% was recorded for control concrete, the lowest reduction of 41.59% was observed for concrete with 1.5% of NS and NA hybrid combination at 800 °C.

Experimental and analytical investigations have shown that the interphase, with properties different from either the fiber or matrix, has a considerable influence composite material strength. The greatest obstacle, however, to this work lies in identifying the specific properties present in the interphase region of a composite and knowing how specific properties affect the performance of the material given particular service conditions. In this work. the author attempts to identify specific properties of two distinct interphases developed from fiber sizings and study their effect on the static and fatigue compression performance. Two different interphases, as formed by the introduction of contrasting fiber sizings, were studied in this dissertation. The interphase produced from the amorphous thermoplastic polyvinylpyrrolidone (PVP) size showed a graded morphology very different from that formed in the presence of the unreacted epoxy size in a thermoplastic toughened epoxy matrix. However, these morphological differences were not introduced in an untoughened epoxy matrix, although many of the differences in composite performance between the two interphase materials were similar. Model studies of PVP modified epoxy showed that at low weight percent loadings of PVP failure strain and mode I toughness were increased but significantly decreased for loadings approaching 20 w%. The effect of this altered interphase zone on elastic and inelastic properties of uniaxial tests was significant. The PVP interphase increased failure strain and strength for both tension and compression. Only the inelastic properties of the off-axis tests were affected by the contrasting interphases, and were similar for both toughened and untoughened epoxy matrix systems. The PVP interphase material showed significant improvements in low cycle notched cross-ply compressive fatigue (one order of magnitude) and fatigue limit (10% of UCS) as compared to the conventional epoxy interphase. These enhancements were the result of the inherent toughness and damage tolerance of the material as influenced by the improved inelastic properties of the PVP interphase. Thus, it is the inelastic characteristics of the interphase (and not strength alone) which are dominant in the understanding of compression strength, as is made further evident by the initial postbuckling description of the fiber-binder system. Completion of the nonlinear (kinematic and constitutive) buckling problem by asymptotic approximation will lead to a fundamental description of the failure mode and strength as related to local inelastic properties and initial imperfections. / Ph. D.