The uncertainty in standardised sound power measurements: complying with ISO 17025

In the context of “testing laboratory” one of the most important aspect to deal with is the measurement result. Whenever decisions are based on measurement results, it is important to have some indication of the quality of the results. In every area concerning with noise measurement many standards are available but without an expression of uncertainty, it is impossible to judge whether two results are in compliance or not. ISO/IEC 17025 is an international standard related with the competence of calibration and testing laboratories. It contains the requirements that testing and calibration laboratories have to meet if they wish to demonstrate that they operate to a quality system, are technically competent and are able to generate technically valid results. ISO/IEC 17025 deals specifically with the requirements for the competence of laboratories performing testing and calibration and for the reporting of the results, which may or may not contain opinions and interpretations of the results. The standard requires appropriate methods of analysis to be used for estimating uncertainty of measurement. In this point of view, for a testing laboratory performing sound power measurement according to specific ISO standards and European Directives, the measurement of uncertainties is the most important factor to deal with. Sound power level measurement, according to ISO 3744:1994 , performed with a limited number of microphones distributed over a surface enveloping a source is affected by a certain systematic error and a related standard deviation. Making a comparison of measurement carried out with different microphone arrays is difficult because results are affected by systematic errors and standard deviation that are peculiarities of the number of microphones disposed on the surface, their spatial position and the complexity of the sound field. A statistical approach could give an overview of the difference between sound power level evaluated with different microphone arrays and an evaluation of errors that afflict this kind of measurement. Despite the classical approach that tend to follow the ISO GUM this thesis present a different point of view of the problem related to the comparison of result obtained from different microphone arrays.

New materials for electrochemiluminescence

The study of electrochemiluminescence (ECL) involves photophysical and electrochemical aspects. Excited states are populated by an electrical stimulus. The most important applications are in the diagnostic field where a number of different biologically-relevant molecules (e.g. proteins and nucleic acids) can be recognized and quantified with a sensitivity and specificity previously not reachable. As a matter of fact the electrochemistry, differently to the classic techniques as fluorescence and chemiluminescence, allows to control the excited state generation spatially and temporally. The two research visits into A. J. Bard electrochemistry laboratories were priceless. Dr. Bard has been one of ECL pioneers, the first to introduce the technique and the one who discovered in 1972 the surprising emission of Ru(bpy)3 2+. I consider necessary to thank by now my supervisors Massimo and Francesco for their help and for giving me the great opportunity to know this unique science man that made me feel enthusiastic. I will never be grateful enough… Considering that the experimental techniques of ECL did not changed significantly in these last years the most convenient research direction has been the developing of materials with new or improved properties. In Chapter I the basics concepts and mechanisms of ECL are introduced so that the successive experiments can be easily understood. In the final paragraph the scopes of the thesis are briefly described. In Chapter II by starting from ECL experimental apparatus of Dr. Bard’s laboratories the design, assembly and preliminary tests of the new Bologna instrument are carefully described. The instrument assembly required to work hard but resulted in the introduction of the new technique in our labs by allowing the continuation of the ECL studies began in Texas. In Chapter III are described the results of electrochemical and ECL studies performed on new synthesized Ru(II) complexes containing tetrazolate based ligands. ECL emission has been investigated in solution and in solid thin films. The effect of the chemical protonation of the tetrazolate ring on ECL emission has been also investigated evidencing the possibility of a catalytic effect (generation of molecular hydrogen) of one of the complexes in organic media. Finally, after a series of preliminary studies on ECL emission in acqueous buffers, the direct interaction with calf thymus DNA of some complexes has been tested by ECL and photoluminescence (PL) titration. In Chapter IV different Ir(III) complexes have been characterized electrochemically and photophysically (ECL and PL). Some complexes were already well-known in literature for their high quantum efficiency whereas the remaining were new synthesized compounds containing tetrazolate based ligands analogous to those investigated in Chapt. III. During the tests on a halogenated complex was unexpectedly evidenced the possibility to follow the kinetics of an electro-induced chemical reaction by using ECL signal. In the last chapter (V) the possibility to use mono-use silicon chips electrodes as ECL analitycal devices is under investigation. The chapter begins by describing the chip structure and materials then a signal reproducibility study and geometry optimization is carried on by using two different complexes. In the following paragraphs is reported in detail the synthesis of an ECL label based on Ru(bpy)3 2+ and the chip functionalization by using a lipoic acid SAM and the same label. After some preliminary characterizations (mass spectroscopy TOF) has been demonstrated that by mean of a simple and fast ECL measurement it’s possible to confirm the presence of the coupling product SAM-label into the chip with a very high sensitivity. No signal was detected from the same system by using photoluminescence.

Physical and mineralogical changes of Hungarian monumental stones exposed to different conditions: stone-testing in-situ and under laboratory conditions

The Székesfehérvár Ruin Garden is a unique assemblage of monuments belonging to the cultural heritage of Hungary due to its important role in the Middle Ages as the coronation and burial church of the Kings of the Hungarian Christian Kingdom. It has been nominated for “National Monument” and as a consequence, its protection in the present and future is required. Moreover, it was reconstructed and expanded several times throughout Hungarian history. By a quick overview of the current state of the monument, the presence of several lithotypes can be found among the remained building and decorative stones. Therefore, the research related to the materials is crucial not only for the conservation of that specific monument but also for other historic structures in Central Europe. The current research is divided in three main parts: i) description of lithologies and their provenance, ii) physical properties testing of historic material and iii) durability tests of analogous stones obtained from active quarries. The survey of the National Monument of Székesfehérvár, focuses on the historical importance and the architecture of the monument, the different construction periods, the identification of the different building stones and their distribution in the remaining parts of the monument and it also included provenance analyses. The second one was the in situ and laboratory testing of physical properties of historic material. As a final phase samples were taken from local quarries with similar physical and mineralogical characteristics to the ones used in the monument. The three studied lithologies are: fine oolitic limestone, a coarse oolitic limestone and a red compact limestone. These stones were used for rock mechanical and durability tests under laboratory conditions. The following techniques were used: a) in-situ: Schmidt Hammer Values, moisture content measurements, DRMS, mapping (construction ages, lithotypes, weathering forms) b) laboratory: petrographic analysis, XRD, determination of real density by means of helium pycnometer and bulk density by means of mercury pycnometer, pore size distribution by mercury intrusion porosimetry and by nitrogen adsorption, water absorption, determination of open porosity, DRMS, frost resistance, ultrasonic pulse velocity test, uniaxial compressive strength test and dynamic modulus of elasticity. The results show that initial uniaxial compressive strength is not necessarily a clear indicator of the stone durability. Bedding and other lithological heterogeneities can influence the strength and durability of individual specimens. In addition, long-term behaviour is influenced by exposure conditions, fabric and, especially, the pore size distribution of each sample. Therefore, a statistic evaluation of the results is highly recommended and they should be evaluated in combination with other investigations on internal structure and micro-scale heterogeneities of the material, such as petrographic observation, ultrasound pulse velocity and porosimetry. Laboratory tests used to estimate the durability of natural stone may give a good guidance to its short-term performance but they should not be taken as an ultimate indication of the long-term behaviour of the stone. The interdisciplinary study of the results confirms that stones in the monument show deterioration in terms of mineralogy, fabric and physical properties in comparison with quarried stones. Moreover stone-testing proves compatibility between quarried and historical stones. Good correlation is observed between the non-destructive-techniques and laboratory tests results which allow us to minimize sampling and assessing the condition of the materials. Concluding, this research can contribute to the diagnostic knowledge for further studies that are needed in order to evaluate the effect of recent and future protective measures.

Trasmission and Reflection (ATR)Far-Infrared Spectroscopy Applied in the Analysis of Cultural Heritage Materials

FIR spectroscopy is an alternative way of collecting spectra of many inorganic pigments and corrosion products found on art objects, which is not normally observed in the MIR region. Most FIR spectra are traditionally collected in transmission mode but as a real novelty it is now also possible to record FIR spectra in ATR (Attenuated Total Reflectance) mode. In FIR transmission we employ polyethylene (PE) for preparation of pellets by embedding the sample in PE. Unfortunately, the preparation requires heating of the PE in order to produces at transparent pellet. This will affect compounds with low melting points, especially those with structurally incorporated water. Another option in FIR transmission is the use of thin films. We test the use of polyethylene thin film (PETF), both commercial and laboratory-made PETF. ATR collection of samples is possible in both the MIR and FIR region on solid, powdery or liquid samples. Changing from the MIR to the FIR region is easy as it simply requires the change of detector and beamsplitter (which can be performed within a few minutes). No preparation of the sample is necessary, which is a huge advantage over the PE transmission method. The most obvious difference, when comparing transmission with ATR, is the distortion of band shape (which appears asymmetrical in the lower wavenumber region) and intensity differences. However, the biggest difference can be the shift of strong absorbing bands moving to lower wavenumbers in ATR mode. The sometimes huge band shift necessitates the collection of standard library spectra in both FIR transmission and ATR modes, provided these two methods of collecting are to be employed for analyses of unknown samples. Standard samples of 150 pigment and corrosion compounds are thus collected in both FIR transmission and ATR mode in order to build up a digital library of spectra for comparison with unknown samples. XRD, XRF and Raman spectroscopy assists us in confirming the purity or impurity of our standard samples. 24 didactic test tables, with known pigment and binder painted on the surface of a limestone tablet, are used for testing the established library and different ways of collecting in ATR and transmission mode. In ATR, micro samples are scratched from the surface and examined in both the MIR and FIR region. Additionally, direct surface contact of the didactic tablets with the ATR crystal are tested together with water enhanced surface contact. In FIR transmission we compare the powder from our test tablet on the laboratory PETF and embedded in PE. We also compare the PE pellets collected using a 4x beam condenser, focusing the IR beam area from 8 mm to 2 mm. A few samples collected from a mural painting in a Nepalese temple, corrosion products collected from archaeological Chinese bronze objects and samples from a mural paintings in an Italian abbey, are examined by ATR or transmission spectroscopy.

Shape memory and elastoplastic materials: from constitutive and numerical to fatigue modeling

Shape memory materials (SMMs) represent an important class of smart materials that have the ability to return from a deformed state to their original shape. Thanks to such a property, SMMs are utilized in a wide range of innovative applications. The increasing number of applications and the consequent involvement of industrial players in the field have motivated researchers to formulate constitutive models able to catch the complex behavior of these materials and to develop robust computational tools for design purposes. Such a research field is still under progress, especially in the prediction of shape memory polymer (SMP) behavior and of important effects characterizing shape memory alloy (SMA) applications. Moreover, the frequent use of shape memory and metallic materials in biomedical devices, particularly in cardiovascular stents, implanted in the human body and experiencing millions of in-vivo cycles by the blood pressure, clearly indicates the need for a deeper understanding of fatigue/fracture failure in microsize components. The development of reliable stent designs against fatigue is still an open subject in scientific literature. Motivated by the described framework, the thesis focuses on several research issues involving the advanced constitutive, numerical and fatigue modeling of elastoplastic and shape memory materials. Starting from the constitutive modeling, the thesis proposes to develop refined phenomenological models for reliable SMA and SMP behavior descriptions. Then, concerning the numerical modeling, the thesis proposes to implement the models into numerical software by developing implicit/explicit time-integration algorithms, to guarantee robust computational tools for practical purposes. The described modeling activities are completed by experimental investigations on SMA actuator springs and polyethylene polymers. Finally, regarding the fatigue modeling, the thesis proposes the introduction of a general computational approach for the fatigue-life assessment of a classical stent design, in order to exploit computer-based simulations to prevent failures and modify design, without testing numerous devices.

Advanced polymeric materials for applications in technical equipment for snow sports

The thesis is divided in three chapters, each one covering one topic. Initially, the thermo-mechanical and impact properties of materials used for back protectors have been analysed. Dynamical mechanical analysis (DMTA) has shown that materials used for soft-shell protectors present frequency-sensitive properties. Furthermore, through impact tests, the shock absorbing characteristics of the materials have been investigated proving the differences between soft and hard-shell protectors; moreover it has been demonstrated that the materials used for soft-shell protectors maintain their protective properties after multi-impacts. The second chapter covers the effect of the visco-elastic properties of the thermoplastic polymers on the flexural and rebound behaviours of ski boots. DMTA analysis on the materials and flexural and rebound testing on the boots have been performed. A comparison of the results highlighted a correlation between the visco-elastic properties and the flexural and rebound behaviour of ski boots. The same experimental methods have been used to investigate the influence of the design on the flexural and rebound behaviours. Finally in the third chapter the thermoplastic materials employed for the construction of ski boots soles have been characterized in terms of chemical composition, hardness, crystallinity, surface roughness and coefficient of friction (COF). The results showed a relation between material hardness and grip, in particular softer materials provide more grip with respect to harder materials. On the contrary, the surface roughness has a negative effect on friction because of the decrease in contact area. The measure of grip on inclined wet surfaces showed again a relation between hardness and grip. The performance ranking of the different materials has been the same for the COF and for the slip angle tests, indicating that COF can be used as a parameter for the choice of the optimal material to be used for the soles of ski boots.