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Doctoral Thesis
DOI
https://doi.org/10.11606/T.75.2011.tde-06072011-163715
Document
Author
Full name
Fabiana Diuk de Andrade
E-mail
Institute/School/College
Knowledge Area
Date of Defense
Published
São Carlos, 2011
Supervisor
Committee
Colnago, Luiz Alberto (President)
Tormena, Cláudio Francisco
Villar, Jose Daniel Figueroa
Azevêdo, Eduardo Ribeiro de
Imasato, Hidetake
Title in Portuguese
Desenvolvimento de sequências de pulso de eco de spin de baixa potência para RMN on-line
Keywords in Portuguese
Baixa potência
Eco de spin
RMN on-line
Abstract in Portuguese
A Ressonância Magnética Nuclear em baixa resolução (RMN-BR) vem sendo aplicada no controle e certificação de qualidade na indústria. Para acelerar e automatizar as análises tem sido proposto o uso de RMN online, com carreamento de amostras por uma esteira. Apesar do grande potencial, as metodologias utilizadas podem provocar o aquecimento da amostra, causando erros nas medidas, além de reduzir a vida útil do equipamento. Assim, nesse trabalho de doutorado foram desenvolvidas sequências de eco de spin para medidas de RMN-BR online utilizando baixa potência de RF (radiofrequência), baseadas nas técnicas CP, Carr-Purcell, e CPMG, Carr-Purcell-Meiboom-Gill, utilizando baixos ângulos de refocalização, LRFA (Low Refocusing Flip Angle). Observou-se que LRFA de 45° (CPMG45) pode fornecer valores de tempo de relaxação transversal (T2) com erros inferiores a 5% em campos magnéticos (B0) com homogeneidade equivalente a largura de linha de Δν ≤ 15 Hz. Em B0 menos homogêneos (Δν ≥ 100 Hz), a escolha dos LRFA deve considerar a redução do sinal e o aumento de T2, que se torna dependente do tempo de relaxação longitudinal (T1). CP90 produz ecos entre os pulsos de refocalização que decaem para valores mínimos dependente de T2* (constante de tempo do Decaimento Livre da Indução). O sinal obtido por CP90 aumenta de valores mínimos para o regime de estado estacionário (EE) com constante de tempo T* = 2T1T2/(T1+T2) e amplitude MCP90 = M0T2/(T1+T2), a mesma constante e a mesma amplitude observada para o sinal de Precessão Livre em Onda Contínua (CWFP - Continuous Wave Free Precession), por isso foi denominada CP-CWFP. A principal vantagem de CP-CWFP ocorre para amostras com T1 ~ T2. CP-CWFP apresenta um decaimento abrupto da amplitude do sinal antes de aumentar e alcançar o EE. Essa diferença na amplitude torna o ajuste de T* menos dependente da razão sinal/ruído, sendo mais eficiente que CWFP para medidas de T1 e T2 em B0 baixos, onde T1 e T2 tendem a ter valores similares. No método de alternância de fase (AF) em CPMG90AF (y'/-y') e CP90AF (x'-x') os sinais entraram num EE, nesse caso CPMG90AF e CP90AF tiveram comportamentos similares ao CP-CWFP, sendo mais uma alternativa para obtenção de T1 e T2. Para CPMG, a redução do ângulo de refocalização para 90° equivale a uma redução de 75% da potência incidida na amostra. CP-CWFP pode ser uma técnica mais robusta para análises em espectrômetros de RMN de bancada em controle de qualidade industrial, com B0 < 0,5 T (20 MHz) e em ferramentas de RMN utilizadas em poços de petróleo com B0 ~ 0,05 T (2 MHz). As análises por métodos estatísticos demonstraram que CPMG e CPMG90, CWFP e CP-CWFP apresentam alta correlação entre si, demonstrando que uma técnica pode substituir a outra nas análises online de sementes oleaginosas.
Title in English
Low-power Spin echo pulse sequences to NMR online
Keywords in English
Low-power
NMR online
Spin echo
Abstract in English
Low Resolution Nuclear Magnetic Resonance (LR-NMR) has been applied in quality control and certification in industry. To speed up the analysis the online NMR has been proposed. Despite LR-NMR online potential, some problems related to equipment overload occurs. It is due to methodologies used that can cause an increase in sample temperature and consequently errors in measurements as well reduction on equipment durability. Thus, Carr-Purcell, CP and Meiboom-Gill, CPMG using low refocusing flip angles (LRFA) were developed. It was observed that LRFA as low as 45° (CPMG45) can provide transverse relaxation time values (T2) with errors below 5% for homogeneous field (Δν ≤ 15Hz). For a less homogeneous magnetic field (Δν ≥ 100 Hz) the choice of the LRFA has to take into account the reduction in the intensity of the CPMG signal and the increase in the time constant of the CPMG decay that also becomes dependent on longitudinal relaxation time (T1). The Carr-Purcell (CP) pulse sequence, with LRFA, produces echoes midway between refocusing pulses that decay to a minimum value dependent on T2* (Free Induction Decay time constant - FID). When τ > T2*, the signal increased to reach a Steady-State Free Precession regime (SSFP) after the minimum value and was composed of FID signal after each pulse and an echo, before the next pulse. CP90 signal increased from the minimum value to the steady-state regime with a time constant (T*) = 2T1T2/(T1+T2), identical to the time constant observed Continuous Wave Free Precession (CWFP). The Steady-State amplitude obtained with CP90 (MCP90) = M0T2/(T1+T2) was identical to CWFP. Therefore, this sequence was named CP-CWFP because it is a CP sequence that produces results similar to the CWFP. However, CP-CWFP is a better sequence than CWFP for measuring the longitudinal and transverse relaxation times in single scan, when the sample exhibits T1 ~ T2. When phase alternation is applied in CPMG90AF (y'/-y') e CP90AF (x'-x') the signal reaches a Steady-State. CPMG90AF and CP90AF showed similar behavior to CP-CWFP, so one more alternative method to measure T1 and T2. Therefore, the T2 measurements can be performed with 90° refocusing pulses (CPMG90), which use only 25% of the RF power used in conventional CPMG. This reduces the heating problem in the probe and reduces the power deposition in the samples. The CP-CWFP sequence can be a useful method in low-resolution NMR and can be widely used in the agriculture, food and petrochemical industries because those samples tend to have similar relaxation times in low magnetic fields.
 
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Publishing Date
2011-09-26
 
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