FAPEMIG - Fundação de Amparo a Pesquisa do Estado de Minas Gerais / A fragilização por hidrogênio tem sido um problema constante em diferentes setores da indústria. Por ser o menor átomo existente, o hidrogênio difunde-se na microestrutura dos materiais metálicos, inserindo tensões mecânicas internas que podem, eventualmente, levar a uma falha catastrófica. Atualmente, os métodos mais comuns existentes para analisar este fenômeno são lentos e caros, configurando-se assim a necessidade de desenvolver um método de ensaio que não possua tais desvantagens. No presente trabalho, apresenta-se o desenvolvimento de um equipamento cuja função é avaliar de forma rápida a susceptibilidade à fragilização por hidrogênio (SFH) dos materiais metálicos através de ensaios de carregamento progressivo em meio assistido (RSL). Este equipamento apresenta uma grande vantagem em relação aos outros métodos avaliação da SFH, que é o menor tempo de ensaio para se ter resultados representativos. Na presente dissertação foram realizadas a concepção, projeto, simulação em elementos finitos, construção e validação do equipamento. Sua validação foi realizada ensaiando-se uma amostra sem entalhe,cuja tensão mecânica medida foi comparada com aquela retornada pelo software do RSL. Além disso, foi calculada a incerteza de medição relacionada ao cálculo da tensão mecânica na amostra. Os ensaios de verificação do desempenho do RSL foram realizados em amostras de aço AISI 4140 beneficiado com dureza de 40HRC, onde foi avaliada a relação entre o nível de potencial catódico aplicado e a SFH do material das amostras. Os resultados obtidos na validação do equipamento mostraram erros inferiores a 1%. Os resultados mostraram um aumento da SFH com o aumento da dureza indicando que há uma elevada sensibilidade da SFH em relação à dureza da amostra. Os ensaios com variação do potencial catódico mostraram uma relação direta entre esse parâmetro e a SFH da amostra, havendo uma saturação na SFH a partir de -1,1 VAg/AgCl. / Hydrogen embrittlement of metallic materials has been a frequent problem in different industry sectors. Because it is the smallest existing atom, hydrogen diffuses into the microstructure of metallic materials, resulting in internal mechanical stresses that may eventually lead to a catastrophic failure. The most common methods available to analyze this phenomenon are time consuming and expensive. For this reason, it is desired to develop a test method that does not have such disadvantages. In this work it is presented the development of an equipment to rapidly evaluate the susceptibility to hydrogen embrittlement (SHE) of the metallic materials using the rising step load (RSL) bend testing in assisted environment. This equipment has a great advantage over the other evaluation methods of SHE, which is the shortest test time to have representative results. The validation of the infrastructure was performed by testing bars without notches to, whose measured mechanical stress was compared with that returned by the RSL software. In addition, the measurement uncertainty related to the calculation of the mechanical stress in the sample was calculated. The tests to verify the performance of the RSL equipment were carried out on samples of steel AISI 4140 heat treated to a hardness of 40HRC. The effect of the cathodic potential applied to notched bars of AISI 4140 on the SHE was evaluated. The results obtained in the validation phase of the equipment showed errors lower than 1%. The results showed also an increase in SHE with increasing material hardness indicating that there is a high sensitivity to the SHE with respect to the hardness of the sample. The tests carried out using cathodic potential variation showed a direct relationship between this parameter and the SHE of the sample, with saturation of the SHE at -1.1 VAg/AgCl. / Dissertação (Mestrado)

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<p>Cilj ove doktorske disertacija&nbsp; bio je razvoj&nbsp; novih, osetljivih, selektivnih i ekonomski<br />isplativih&nbsp; voltametrijskih&nbsp; radnih&nbsp; elektroda&nbsp; za&nbsp; praćenje&nbsp; odabranih&nbsp; analita&nbsp; kako&nbsp; u<br />laboratorijskim tako i pri terenskim uslovima.&nbsp; Ispitivana je&nbsp; mogućnost primene&nbsp; ovih&nbsp; radnih&nbsp; elektroda&nbsp; primenom&nbsp; voltametrijskih&nbsp; metoda&nbsp; kako&nbsp; u&nbsp; model&nbsp; rastvorima&nbsp; tako&nbsp; i&nbsp; u&nbsp; pojedinim realnim sistemima. SW-ASV&nbsp; zasnovana&nbsp; na&nbsp; elektrodama&nbsp; od&nbsp; staklastog&nbsp; ugljenika&nbsp; povr&scaron;inski modifikovanim&nbsp; Bi-MWCNT&nbsp; i&nbsp; BiOCl-MWCNT&nbsp; je&nbsp; primenjena&nbsp; za&nbsp; određivanje&nbsp; jona&nbsp; Pb(II)&nbsp; i Cd(II)&nbsp; pri&nbsp; optimizovanim&nbsp; uslovima&nbsp; merenja.&nbsp; Određivanje&nbsp; ciljnih&nbsp; jona&nbsp; vr&scaron;eno&nbsp; je&nbsp; pri&nbsp; radnom potencijalu&nbsp; od&nbsp; -1,2&nbsp; V&nbsp; (izmeren&nbsp; u&nbsp; odnosu&nbsp; na&nbsp; zasićenu&nbsp; kalomelovu&nbsp; elektrodu)&nbsp; i&nbsp; vremenu<br />elektrodepozicije jona&nbsp; od 120 s. Sva merenja su izvr&scaron;ena u rastvoru acetatnog pufera čija je pH-vrednost iznosila&nbsp; 4,0. Primenjeni koncentracioni opseg ciljnih analita iznosio je&nbsp; od 5 do 50&nbsp; &mu;g&nbsp; dm ^-3 .&nbsp; Primenom&nbsp; ovog&nbsp; tipa&nbsp; elektrode&nbsp; dobijene&nbsp; su&nbsp; vrednosti&nbsp; granice&nbsp; detekcije&nbsp; za&nbsp; jone Pb(II) i Cd(II) 0,57&nbsp; &mu;g dm ^-3i 1,2 &mu;g dm^-3 , redom. Dobijena RSD iznosila je manje od 10% za oba&nbsp; jona.&nbsp; Ova&nbsp; metoda&nbsp; je&nbsp; primenjena&nbsp; i&nbsp; za&nbsp; određivanje&nbsp; ciljnih&nbsp; jona&nbsp; u&nbsp; realnom&nbsp; uzorku&nbsp; porne vode&nbsp; sedimenta&nbsp; a&nbsp; rezultati&nbsp; dobijeni&nbsp; optimizovanom&nbsp; voltametrijskom&nbsp; metodom&nbsp; su&nbsp; u&nbsp; dobroj saglasnosti sa rezultatima koji su dobijeni primenom komparativne GFAAS metode. Bizmut oksihlorid-vi&scaron;ezidne ugljenične nanocevi kompozitni materijal je primenjen za povr&scaron;insko&nbsp; modifikovanje&nbsp; elektrode&nbsp; od&nbsp; staklastog&nbsp; ugljenika&nbsp; za&nbsp; brzo&nbsp; i&nbsp; jednostavno voltametrijsko&nbsp; određivanje&nbsp; tragova&nbsp; Zn(II)-jona&nbsp; primenom&nbsp; SW-ASV&nbsp; metode.&nbsp; BiOClMWCNT/GCE je pokazala linearan analitički odgovor u&nbsp; osegu koncentracija od&nbsp; 2,50 do&nbsp; 80,0 &mu;g&nbsp; dm ^-3sa dobijenom vredno&scaron;ću GD 0,75 &mu;g&nbsp; dm^-3pri akumulacionom vremenu od&nbsp; 120 s&nbsp; i potencijalu&nbsp; elektrodepozicije&nbsp; -1,40&nbsp; V&nbsp; u&nbsp; odnosu&nbsp; na&nbsp; ZKE.&nbsp; Merenja&nbsp; su&nbsp; vr&scaron;ena&nbsp; u&nbsp; acetatnom puferu pH 4,5. Dobijena RSD iznosila je 4,8 %. Upoređene su performanse novodizajnirane BiOCl-MWCNT/GCE elektrode&nbsp; i&nbsp; tradicionalne elektrode na bazi bizmut filma (BiF/GCE), MWCNT/GCE,&nbsp; BiF-MWCNT/GCE&nbsp; i&nbsp; nemodifikovane&nbsp; GC&nbsp; elektrode.&nbsp; Novodizajnirana elektroda je primenjena za&nbsp; detekciju&nbsp; i određivanje&nbsp; Zn(II)-jona&nbsp; u realnim&nbsp; uzorcima kao &scaron;to su<br />dijetetski&nbsp; suplement&nbsp; i&nbsp; pekarski&nbsp; kvasac.&nbsp; Dobijeni&nbsp; rezultati&nbsp; su&nbsp; uporedivi&nbsp; sa&nbsp; deklarisanom vredno&scaron;ću&nbsp; u&nbsp; slučaju&nbsp; dijetetskog&nbsp; suplementa&nbsp; a&nbsp; u&nbsp; slučaju&nbsp; pekarskog&nbsp; kvasca&nbsp; sa&nbsp; rezultatima dobijenih komparativnom FAAS .<br />Elektroda od ugljenične paste je povr&scaron;inski modifikovana pripremljenim kompozitom<br />koji je&nbsp; izgrađen od vi&scaron;ezidnih ugljeničnih nanocevi i čestica&nbsp; Sb₂O_3.&nbsp; Kompozitni&nbsp; materijal&nbsp; je okarakterisan&nbsp; primenom&nbsp; TEM,&nbsp; EDS&nbsp; i&nbsp; XRD&nbsp; mernih&nbsp; tehnika.&nbsp; Sb₂O₃-MWCNT/CPE&nbsp; je okarakterisana primenom ciklične voltametrije a merenja su vr&scaron;ena u rastvoru hlorovodonične kiseline&nbsp; (pH&nbsp; 2,0).&nbsp; Primenom&nbsp; SW-ASV&nbsp; metode&nbsp; ova&nbsp; radna&nbsp; elektroda&nbsp; je&nbsp; upotrebljena&nbsp; za određivanje&nbsp; jona Pb(II) i Cd(II)&nbsp; u&nbsp; koncentracionom opsegu 2,0-40,0&nbsp; &mu;g&nbsp; dm&nbsp; ^-3za&nbsp; Pb(II)-jon&nbsp; i 2,0-40,0&nbsp; &mu;g&nbsp; dm ^-3 za&nbsp; Cd(II)-jon&nbsp; pri&nbsp; čemu&nbsp; su&nbsp; dobijene&nbsp; dobre&nbsp; linearne&nbsp; zavisnosti&nbsp; za&nbsp; oba&nbsp; ciljna jona.&nbsp; Optimalna&nbsp; procedura&nbsp; uključuje&nbsp; primenu&nbsp; Sb2O3-MWCNT/CPE&nbsp; u&nbsp; 0,01&nbsp; mol dm ^-3<br />hlorovodoničnoj kiselini uz vreme elektrodepozicije jona iz rastvora od 120&nbsp; s&nbsp; na&nbsp; potencijaluod&nbsp; -1,2&nbsp; V,&nbsp; pri&nbsp; čemu&nbsp; su&nbsp; dobijene&nbsp; vrednosti&nbsp; za&nbsp; GD&nbsp; 1,1&nbsp; &mu;g&nbsp; dm ^-3 Cd(II)&nbsp; i&nbsp; 1,6&nbsp; &mu;g&nbsp; dm ^-3 Pb(II). Optimizovana&nbsp; metoda&nbsp; zasnovana&nbsp; na&nbsp; ovom&nbsp; tipu&nbsp; voltametrijskog&nbsp; senzora&nbsp; je&nbsp; uspe&scaron;no primenjena&nbsp; za&nbsp; određivanje&nbsp; jona&nbsp; Cd(II)&nbsp; u&nbsp; obogaćenom&nbsp; uzorku&nbsp; česmenske&nbsp; vode,&nbsp; gde&nbsp; su&nbsp; se dobijene vrednosti u&nbsp; saglasnosti sa očekivanom. Elektroda od ugljenične paste povr&scaron;inski je&nbsp; modifikovana primenom&nbsp; Sb₂O₃-MWCNT nanokompozitnog&nbsp; materijala&nbsp; i&nbsp; primenjena&nbsp; za&nbsp; direktno&nbsp; voltametrijsko&nbsp; određivanje imidakloprida&nbsp; u&nbsp; model&nbsp; rastvorima.&nbsp; U&nbsp; cilju&nbsp; postizanja&nbsp; &scaron;to&nbsp; boljih&nbsp; analitičkih&nbsp; performansi optimizovani su eksperimentalni uslovi merenja kao &scaron;to su pH-vrednost rastvora pomoćnog elektrolita&nbsp; i&nbsp; kondicioniranje&nbsp; povr&scaron;ine&nbsp; voltametrijskog&nbsp; senzora.&nbsp; Kao&nbsp; optimalna&nbsp; pH-vrednost pomoćnog elektolita (Britton-Robinsonovog pufera) odabrana je pH 7,0, a ponavljanje ciklusa cikliranja najmanje 4 puta povoljno utiče na stabilnost&nbsp; voltametrijskih signala. Optimizovana metoda primenjena je za SW direktno katodno određivanje imidakloprida u koncentracionom intervalu od 1,41 do 32,77 &mu;g cm ^-3 uz dobijeni korelacioni faktor od 0,9995. Na osnovu dobijenih rezultata može se zaključiti da su razvijene analitičke metode pre svega&nbsp; osetljive,&nbsp; selektivne,&nbsp; reproduktivne&nbsp; i&nbsp;&nbsp; jednostavne&nbsp; &scaron;to&nbsp; omogućava&nbsp; njihovu&nbsp; primenu&nbsp; za veliki broj uzoraka.&nbsp; Merenjima u model i realnim rastvorima dokazana je mogućnost njihove primene&nbsp; u&nbsp;&nbsp; komplikovanim&nbsp; matriksima,&nbsp; pri&nbsp; različitim&nbsp; pH&nbsp; vredostima&nbsp; pri&nbsp; čemu&nbsp; su&nbsp; dobijeni<br />rezultati koji su u saglasnosti sa rezultatima primenjenih komparativnih metoda. Naravno, za dobijanje&nbsp; reprezentativnih&nbsp; rezultata&nbsp; neohodno&nbsp; je&nbsp; izvr&scaron;iti&nbsp; optimizaciju&nbsp; uslova&nbsp; merenja&nbsp; &scaron;to podrazumeva sam odabir supstrat-elektrode, odabir povr&scaron;inskog modifikatora i optimizaciju eksperimentalnih uslova merenja.</p> / <p>The&nbsp; aim of this&nbsp; Ph.D. thesis&nbsp; was the development of new, sensitive, selective and economically&nbsp; viable&nbsp; voltametric&nbsp; working&nbsp; electrode&nbsp; for&nbsp; continuous&nbsp; monitoring&nbsp; of&nbsp; different target&nbsp; analytes.&nbsp; The&nbsp; use&nbsp; of&nbsp; these&nbsp; advantaged&nbsp; working&nbsp; electrodes&nbsp; was&nbsp; investigated&nbsp; using voltametric methods both in model solutions and in certain real systems.SW-ASV&nbsp; based on glassy carbon&nbsp; electrode surface modified with&nbsp; Bi- MWCNT and BiOCl-MWCNT&nbsp; were&nbsp; applied&nbsp; for&nbsp; determination&nbsp; of&nbsp; Pb(II)&nbsp; and&nbsp; Cd(II)&nbsp; ions.&nbsp; Voltametric determination&nbsp; of&nbsp; Pb(II)&nbsp; and&nbsp; Cd(II)&nbsp; ions&nbsp; was&nbsp; performed&nbsp; at&nbsp; working&nbsp; potential&nbsp; of&nbsp; -1.2&nbsp; V (measured against the saturated calomel electrode) and time of electrodeposition of 120 s. All measurements were performed in acetate buffer solution pH 4.0. Concentration range of targetanalites were&nbsp; 5-50 &mu;g&nbsp; dm -3 . Using this type of electrode,&nbsp; obtained&nbsp; detection limits for&nbsp; Pb(II) and Cd(II) ions&nbsp; were&nbsp; 0.57&nbsp; &mu;g&nbsp; dm -3 and 1.2&nbsp; &mu;g&nbsp; dm -3 , respectively, with RSD lower than 10%.This&nbsp; method&nbsp; was&nbsp; applied&nbsp; for&nbsp; target&nbsp; ions&nbsp; determination&nbsp; in&nbsp; sediment&nbsp; pore&nbsp; water&nbsp; sample,&nbsp; and obtained results are comparable with those who are obtained using GFAAS method. Bismuth oxychloride-multiwalled carbon nanotubes composite material was applied for&nbsp; surface&nbsp; modification&nbsp; of&nbsp; the&nbsp; glass-carbon&nbsp; electrode&nbsp; for&nbsp; quick&nbsp; and&nbsp; simple&nbsp; voltametric determination&nbsp; of&nbsp; Zn(II)&nbsp; ions&nbsp; using&nbsp; the&nbsp; SW-ASV&nbsp; method.&nbsp; BiOCl-MWCNT/GCE&nbsp; showed&nbsp; a linear&nbsp; analytical&nbsp; response&nbsp; in&nbsp; a&nbsp;&nbsp; concentration&nbsp; from&nbsp; 2.50&nbsp; to&nbsp; 80.0&nbsp; &mu;g&nbsp; dm -3 with&nbsp; a&nbsp; value&nbsp; of detection limit 0.75 &mu;g dm -3 at a acumulation time of 120 s and an electrodeposition potential of&nbsp; -1.40 V vs. saturated&nbsp; calomel electrode.&nbsp; Measurements were carried out in acetate buffer pH 4.5. The obtained&nbsp; value of the RSD&nbsp; was&nbsp; 4.8%. The performance of the newly designed BiOCl-MWCNT/GCE&nbsp; electrode,&nbsp; traditional&nbsp; bismuth-based&nbsp; electrode&nbsp; (BiF/GCE), MWCNT/GCE,&nbsp; BiF-MWCNT/GCE&nbsp; and&nbsp; unmodified&nbsp; GC&nbsp; electrodes&nbsp; were&nbsp; compared.&nbsp; The applied electrode shows very good electroanalytic properties when determining this target ion. Obtained results are in good agreement with declared value in case of dietetic suplement, and in the brewer&rsquo;s yeast sample results were comparable with FAAS results. Carbon&nbsp; paste&nbsp; electrode&nbsp; surface&nbsp; modified&nbsp; with&nbsp; new&nbsp; composite&nbsp; material&nbsp; based&nbsp; on multiwalled carbon nanotubes and&nbsp; Sb2O3&nbsp; particles. The composite is characterized by TEM, EDS and&nbsp; XRD measurment. Sb2O3- MWCNT/CPE was characterized by cyclic voltammetry and measurements were carried out in a&nbsp; hydrochloric acid&nbsp; solution&nbsp; (pH 2.0). Using the SWASV&nbsp; method,&nbsp; this&nbsp; working&nbsp; electrode&nbsp; was&nbsp; used&nbsp; to&nbsp; determine&nbsp; Pb(II),&nbsp; Cd(II)&nbsp; ions&nbsp; in&nbsp; the concentration range&nbsp; from&nbsp; 2.0&nbsp; to 40.0&nbsp; &mu;g dm -3 for Pb(II) and 2.0-40.0&nbsp; &mu;g dm -3 for Cd(II) ions. Newly&nbsp; designed&nbsp; sensor&nbsp; showed&nbsp; good&nbsp; linear&nbsp; dependences&nbsp; for&nbsp; both&nbsp; target&nbsp; ions.&nbsp; The&nbsp; most optimal&nbsp; procedure&nbsp; involving&nbsp; application&nbsp; of&nbsp; Sb2O3-MWCNT/CPE&nbsp; in&nbsp;&nbsp; .01&nbsp; mol&nbsp; dm -3 hydrochloric&nbsp; acid,&nbsp; with&nbsp; electroposition&nbsp; time&nbsp; of&nbsp; target&nbsp; ions&nbsp; 120&nbsp; s&nbsp; at&nbsp; a&nbsp; electrodeposition potential&nbsp; of&nbsp; -1.2&nbsp; V.&nbsp; Obtained&nbsp;&nbsp; values&nbsp; of&nbsp;&nbsp;&nbsp; LOD&nbsp; 1,1&nbsp; &mu;g&nbsp; dm -3 for&nbsp; Cd(II)&nbsp; and&nbsp; for&nbsp; 1,6&nbsp; &mu;g&nbsp; dm -3 Pb(II)&nbsp; ions.&nbsp; An&nbsp; optimized&nbsp; method&nbsp; based&nbsp; on&nbsp; this&nbsp; type&nbsp; of&nbsp; voltametric&nbsp; sensor&nbsp; has&nbsp; been successfully&nbsp; applied&nbsp; for&nbsp; determination&nbsp; of&nbsp; Cd(II)&nbsp; ion&nbsp; in&nbsp; a&nbsp; spiked&nbsp; tap&nbsp; water&nbsp; sample.&nbsp; Results obtained during this measurment were in tune with expected results. CPE&nbsp; was&nbsp; surface&nbsp; modified&nbsp; using&nbsp; Sb2O3-MWCNT&nbsp; nanocomposite&nbsp; material&nbsp; and tested&nbsp; for&nbsp; direct&nbsp; voltametric&nbsp; determination&nbsp; of&nbsp; imidacloprid&nbsp; in&nbsp; model&nbsp; solutions.&nbsp; In&nbsp; order&nbsp; to achieve the best analytical performance, experimental conditions of measurement such as the pH value of the supporting electrolyte and conditioning of the voltametric sensor surface havebeen&nbsp; optimized.&nbsp; As&nbsp; an&nbsp; optimum&nbsp; pH&nbsp; value&nbsp; of&nbsp; the&nbsp; supporting&nbsp; electrolyte&nbsp; (Britton-Robinson buffer), a pH 7.0 was selected, and the repeating cycles of the cycling process at least 4 times favorably&nbsp; influenced&nbsp; the&nbsp; stability&nbsp; of&nbsp; the&nbsp; voltametric&nbsp; signals.&nbsp; The&nbsp; optimized&nbsp; method&nbsp; was applied for the SW direct cathodic determination&nbsp; of&nbsp; imidacloprid in the concentration range from 1.41 to 32.77 &mu;g cm -3&nbsp; with obtained correlation factor of 0.9995. Based on results it can be concluded that developed analytical methods are sensitive, selective, reproducibile and simple, which can enable their application for various number of samples. Measurements in the model and real solutions have demonstrated the possibility of their&nbsp; application&nbsp; in&nbsp; complicated&nbsp; matrices,&nbsp; at&nbsp; different&nbsp; pH,&nbsp; whereby&nbsp; obtained&nbsp; results&nbsp; are&nbsp; in accordance&nbsp; with&nbsp; the&nbsp; results&nbsp; of&nbsp; the&nbsp; applied&nbsp; comparative&nbsp; methods.&nbsp; For&nbsp; obtainig&nbsp; of representative&nbsp; results&nbsp; it&nbsp; is&nbsp; necessary&nbsp; to&nbsp; optimize&nbsp; conditions&nbsp; of&nbsp; measurment&nbsp; which&nbsp; include: selection of substrat electrode, surface modifier and optimization of experimental condition.</p>