The dimensional control is a crucial aspect for any manufacturing process. In Powder Metallurgy, and in particular in net shape press and sinter process, dimensional control assumes a particular relevance, since sintering of green parts involves dimensional variations that can be from 0 to 2-3% in volume. The dimensional variation in sintering is either shrinkage or swelling. Both depend on the material and on several process parameters relevant to the compaction and the sintering operations. Experimental evidences proved dimensional variations to be affected by an anisotropic behavior. This important phenomenon affects the effectiveness of the dimensional control if not opportunely taken into consideration in the design process. Professor Ilaria Cristofolini and Professor Alberto Molinari have started a deep investigation on this phenomenon, about five years ago, involving an important experimental campaign. The main idea is to collect a large quantity of data, both on ad-hoc designed samples and on parts produced by qualified PM companies cooperating with the University of Trento. The purpose is to develop a realistic model, able to explain and describe the mechanisms involved in the anisotropy of dimensional changes, and the dependence on the geometry of the parts, building a robust knowledge to improve the design methodologies in the industrial production. The present work investigates the effect of the geometrical characteristics of the part on the dimensional variations in sintering, giving a particular importance on its anisotropic behavior. The influence of geometry has been investigated using rings and disks with varying heights, external diameters and internal diameters. The influence of the sintering temperature has been also evaluated. The dimensional variation has been measured by a tri-dimensional Coordinate Measuring Machine. The anisotropy has been defined through a specifically determined parameter, which has been used to develop a predictive model estimating the anisotropy of the dimensional variations. This model has been then validated on complex parts produced by a Powder Metallurgy company.

This work was carried out in the frame of an industrial research project in cooperation with the Eurocoating SpA and K4Sint Srl, aiming at developing the commercial pure titanium, the Ti-6Al-4V and the Co-28Cr-6Mo alloys by Spark Plasma Sintering (SPS) for biomedical application. The definition of the process parameters for the production of a highly porous (cp-Ti), full density materials (Ti-6Al-4V and Co-28Cr-6Mo), and their combination in a surface functionalized full density substrate was the central focus. The SPS parameters were optimized to obtain the Co-28Cr-6Mo alloy in full density state for matching the international standards. Tensile and fatigue were the main properties under investigation. In the case of Ti-6Al-4V alloy the best SPS parameters was defined in a previous work by means of densification curve and tensile properties. Therefore, the fatigue resistance was the main property under investigation. The optimization of the sintering parameters was evaluated by the interdependence between the density, microstructure and hardness. Co-sintering of the cp-Ti with the Co alloy and the cp-Ti with the Ti alloy was carried in order to obtain a porous coated full density substrate in one single step. The SPS parameters were optimized in order to achieve a coating like structure containing macropores with specific range of size and highly interconnected. To that, the space holder technique was chosen since it allows a very good control of the pores characteristics. The interactions at the interfaces were characterized and the best SPS strategy was defined. Subsequently, fatigue tests were carried out in order to assess the influence of the porous coating on the fatigue resistance of the full density substrates. As a general conclusion it may be assessed that the process parameters for the production of the investigated biomaterials have been defined and the microstructural characteristics, as well as mechanical, corrosion properties and wear resistance satisfy the requirements on the international standards. These results have been used to produce implants which are under test.

Metallic biomaterials have an essential portion of uses in biomedical applications. Their properties can be tuned by many factors resulting in their process tuneability. Among metallic biomaterials for biomedical and specifically orthopedic applications, titanium and its alloys exhibit the most suitable characteristics as compared to stainless steels and Co-Cr alloys because of their high biocompatibility, specific strength (strength to density ratio), and corrosion resistance. According to their phase constitution, Ti-alloys are classified into three main groups, namely alpha, beta, and alpha+beta alloys. Depending on the degree of alloying and thermomechanical processing path, it is possible to tune the balance of α and β phases, which permits to tailor properties like strength, toughness, and fatigue resistance. (alpha+beta) Ti alloys, especially Ti-6Al-4V, are widely used alloys in biomedical applications; however, they have some drawbacks like the presence of toxic elements i.e., V and relatively high elastic modulus to that of bones. In view of the lower elastic modulus of body center cubic beta phase (50GPa<100GPa) compared to the alpha+beta, as well as due to their good mechanical properties, excellent corrosion resistance, and biocompatibility, beta-Ti alloys have been recently proposed as a valid alternative to alpha+beta ones. The growing interest in additive manufacturing (AM) techniques opens new and very interesting perspectives to the production of biomedical prosthetic implants. AM will prospectively allow implant customization to the patient and produce it on demand, with large savings on times and costs. Moreover, AM is gaining increasing interest due to the possibility of producing orthopedic implants with functionally graded open-cell porous metals. The main advantages of porous materials are the reduction of the elastic modulus mismatch between bone and implant alloy reducing the stress shielding effect and improving implant morphology providing biological anchorage for tissue in-growth. In this scenario, the first goal of the present PhD thesis work was to identify a high-performance β-Ti alloy formulation suitable to Laser-Powder Bed Fusion (L-PBF) additive manufacturing. In particular, it explores the potential use of a β-metastable Ti alloy, namely Ti-15Mo-2.7Nb-3Al-0.2Si (Beta Ti21S, 21 wt.% of alloying additions, including Silicon) for biomedical applications. Through microstructural, mechanical, and cytotoxicity analyses, it could be shown that this alloy grade exhibits i) an unprecedented ultra-low elastic modulus, ii) improved cytocompatibility due to the lack of Vanadium, and iii) no martensitic transformation responsible for hard and brittle solidification structures. A second goal was to assess the manufacturability of metamaterials made of β-Ti21S via L-PBF. For this purpose, cubic cellular lattice structures of different unit cell sizes (and therefore different strut thickness) have been fabricated and characterized through microstructural analysis using different techniques, and computed tomography combined with linear elastic finite element simulations to identify the minimum cell size that can be printed with adequate dimensional and geometrical accuracy. Samples of the selected unit cell size were also tested to determine their static and fatigue properties. The main results show that i) the suitable manufacturing quality is obtained for strut thickness above 0.5 mm, ii) the mechanical tests place the present cellular structures among the best stretching dominated cellular lattice materials investigated to date in the literature, and iii) the fatigue tests showed a normalized fatigue strength at 107 cycles of close to 0.8, similar to cubic lattices made of Ti-6Al-4V, and higher than most cellular structures in the literature. In the last part of the thesis, a more complex octet truss structure was fabricated in the manufacturable cell size, and its mechanical properties were investigated. The octet truss topology can be beneficial both in terms of mechanical properties and biocompatibility by providing the different types of porosity suitable for bone in-growth.

Brake materials represent an important source of air pollution, especially in urban areas, where they can contribute to approx. 21 % of the traffic-related particulate matter emission. For this reason, the design of new brake materials with low emissions is a topical issue. In addition to low emissions, the design of new friction materials has to ensure excellent performance with stable coefficients of friction and low wear rate. Due to the several requirements that these materials need to fulfill, their development and testing are complex and intercorrelated. Good performance and low emission strongly depend on the mechanisms acting at the disc-pad interfaces. In this thesis, a brake dynamometer testing protocol is developed to better understand the relationships of the braking parameters with the brake performance and emission behavior, correlating them with the surface characteristics. The surface characteristics were investigated with a-posteriori analysis, in terms of extension of the contact area, degree of compaction of the wear particles and relevant composition. The work is focused on the bedding process and the influence of the braking parameters on the frictional, wear and emission behaviors. Regarding the bedding process, run-in, transition stage and steady states were identified as concerns the frictional, wear and emission behaviors. The frictional behavior gets stabilized by the extension of the secondary plateaus, whereas the wear and emission behaviors are stabilized as their degree of compaction increases. The influence of pressure and velocity under mild sliding conditions were studied for a low-met and NAO material, the two most common types of friction materials. The low-met material featured a more stable and higher friction coefficient and lower wear and emissions than the NAO material. The wear behavior is strongly affected by pressure for the NAO material, and for the low-met material, velocity is very influential. Emissions follow a cube relationship with velocity for both materials. The significant differences in the observed behaviors are explained in terms of the different features of the surfaces. The NAO material featured a smooth and uniform surface, with higher coverage than the low-met material, on which steel fibers play important adhesive and abrasive actions. From tests under mild sliding conditions of several friction materials sliding against cast-iron discs, a linear relationship is found between the specific wear rate and the emission factor. This relationship identifies a wear rate below 2.5 10-14 m2/N complying with the Euro 7 limitation of 3 mg/km/vehicle after 2034. Among the friction materials sliding against cast iron discs, the NAO material and only one friction material displayed an emission factor below the limit of 3 mg/km/vehicle. In addition, the emission factor of low-met material sliding against a cermet-coated disc was lower than this limit. These observations confirm that the NAO materials and coated discs are effective systems to mitigate emissions, whereas further efforts are required to improve the emission behavior of low-met materials. Interestingly, the low-met materials with a reduced presence of secondary plateaus featured higher wear and emissions. Regarding the brake performance, under severe sliding conditions, the NAO material displayed worse frictional and wear behaviors than the reference low-met material. For high-pressure ranges, the effect of pressure is to cause a monotonic decrease in the friction coefficient. The effect of temperature on the friction coefficient causes an increase in the friction coefficient when the tribo-oxidative processes are contained up to 300 °C. For combinations of high velocity and temperature, the tribo-oxidative processes are high enough to form a thick glaze layer on the surfaces. The glaze layers were correlated to a lubricating effect, or fade effect, at disc temperatures above 400 °C, especially when their extension covered the steel fibers. The cermet-coated disc displayed the same fade behavior at high velocity-temperature values, although at low velocities and high temperatures, friction instability was observed and related to larger but fewer patches originating to a significant extent from material transfer from the disc. The friction instability in the coated disc was ascribed to the different tribo-oxidative behavior in the formation of ‘glazes’ due to the low source of iron in the disc material.

A metal injected component was produced by overmolding technique. To reach a good result differebnt powder matching were studied. The final mechanical properties and corrosion resistance of the interface microstructure were investigated.

Binderless tungsten carbide (BTC) ceramics are inherently difficult to process and very brittle. Most consolidation techniques for processing pure WC powder require long sintering times and intense energy consumption. High-T pressureless and pressure-assisted sintering processes often lead to low-quality and coarsened microstructures, thus limiting the use of WC ceramics to few niche applications. Field-assisted sintering techniques (FAST), like spark plasma sintering (SPS), significantly improve the densification of fine and ultrafine WC powders. However, SPS requires high current outputs and expensive apparatus. SPS ceramics still lack adequate toughness to extend the use of BTC components in heavy-duty applications requiring reliable load-bearing capability and/or resistance against rapid and unexpected impacts or temperature drops. This research work explored a new consolidation route capable of boosting the mass transport phenomena (accelerated sintering) and, simultaneously, introducing new microstructural features. The process called flash sintering (FS) offers great potential in accelerating diffusion phenomena and altering the crystallographic and/or the defect chemistry of the sintered ceramics. Many scientific studies reported structural alterations, enhanced plastic flow and material softening by introducing “out-of-equilibrium” characteristics. Currently, FS technology requires, for its activation, a negative dependence of the electrical resistivity with temperature (NTC) of the material to be sintered. This is a universal requirement for the flash event to occur thus theoretically inhibiting the flash sintering of conductive materials with a positive temperature coefficient for resistivity (PTC), like metals or WC. In the present work, we reported how during electrical resistance sintering (ERS) experiments conducted on pure WC nanopowders, a flash event was triggered during the first seconds of the process. This was demonstrated to occur thanks to the different evolution of the electrical properties of a granular compact with temperature. WC powders possess an initial NTC behaviour which can activate a transitory thermal runaway phenomenon which makes the activation of a flash event in these materials possible, intense enough to allow ultrafast densification in less than 10 s. This breakthrough allows to verify whether and how the flash event modifies the final sintered material. FS and SPS sintered ceramics were compared in their microstructural, physical and mechanical properties, thus pointing out how some peculiar modifications are exclusively present in the flash-sintered material. FS can stabilize the WC1-x metastable phase after cooling to room temperature, and this was demonstrated to alter the high-temperature deformation of WC micropillars during compression. In addition, FS BTC are inherently softer with respect to SPS ones, resulting in higher fracture toughness and slightly lower hardness. Even if not final, the results indicate how the flash sintering of WC can be explored further to process engineered BTC ceramics with an optimized hardness/toughness ratio and an enhanced deformability.

Peak profiles in X-ray Diffraction (XRD) patterns from nanocrystalline materials are affected by static and dynamic disorder which is specific of the size and shape of the nanocrystalline domains. Owing to their intrinsic differences, the two types of disorder can be separated, providing independent information from the modelling of the XRD patterns. In the present thesis a model for the static strain created by the nanoparticle surface is proposed. The model is built within the frame of the Whole Powder Pattern Modelling (WPPM) approach for XRD line profile analysis, developed at the University of Trento in the past 20 years. The WPPM approach is decribed in details. Based on a complex Fourier Transform of the diffraction profiles, the model leads to general equations to be used with the WPPM approach to represent the distorted atomic configuration with respect to the reference bulk one. The model was also implemented in TOPAS, a commercial and very popular software, developing a specific macro allowing a larger community of users to benefit of this new opportunity of studying nanocrystalline materials. The thesis work also extended to a more traditional and general description of strain broadening of XRD peak profiles, involving invariant forms under the Laue group symmetry operations of the material under study. As for the dynamic strain, the fundamentals of the Thermal Diffuse Scattering (TDS) contribution to the peak profiles are reviewed. Starting from the original work of B.E. Warren, the theory is generalized to account for surface effects, leading to a particular model developed recently at the University of Trento. This model was thoroughly reviewed and corrected. To test the model a parallel computer code in C was written, exploiting Molecular Dynamics simulations for obtaining reliable and independent estimates of static and dynamic disorder in nanocrystals.