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1 Nuclear Magnetic Resonance Spectrometer Aline Elad, Mengting Nan, Zachary Henderson Abstract— Our senior design project this year is to design and build a nuclear magnetic resonance spectrometer (NMR) that is accessible to high school laboratories so that high school students can gain access to important technology in the field of biology and chemistry. A NMR spectrometer works by manipulating unique spin properties of atomic elements such as hydrogen, carbon and nitrogen. A NMR spectrometer is capable of determining the chemical composition and chemical structure of molecules by measuring the relative intensity of the atomic elements with the substance. The NMR spectrometer outputs a graph of relative intensity against parts per million and this data allows scientists to work out the important details about the substance. Details such as specific element percentage, element isotopes, and types of connecting bonds are all available in the output of an NMR spectrometer. The field of biology and chemistry advances so dramatically and relies so much on the data obtained from a NMR spectrometer that it is critical to introduce it to young, up incoming scientists who wish to advance our scientific knowledge. Currently however students lack access to NMR spectrometers due to the high maintenance and purchase cost, which, as a result allows only research labs, and universities access to these powerful machines. Commercial NMR spectrometers can cost anywhere from $20,000 to beyond $100,000. This cost is unfathomable for almost all high school districts across the United States. Thus, there is an open market for introducing NMR spectrometers to high school and the potential benefits include giving students more experience that they can use for applying to colleges and jobs later on in their life. Our NMR spectrometer will be built with the following goals in mind: a $500 budget, an easy to use and understandble interface, and a reliable results comparable to commercial devices. I. INTRODUCTION O ur objective with this project is to deliver a working Nuclear Magnetic Resonance spectrometer that is capable of being used in high school curriculums. Our spectrometer will follow the standard operation and procedure of current commercial spectrometers. We foresee our spectrometer becoming a useful tool in high school curriculums as it will not only allow students to use an advanced research tool but will allow them to understand the inner workings of it as well. NMR spectroscopy is a powerful research tool used for identifying chemical structures in fields of the physical sciences.[1] NMR spectroscopy exploits fundamental spin characteristics of individual atoms in a chemical compound to determine the composition and structure. [2] Our project is to build a cost effective, easy to use and reliable NMR spectrometer that can easily be used in high school laboratories that are unable to purchase high-end NMR spectrometers. Modern physical sciences are increasingly becoming dependent on the understanding of complex chemical structures that are increasingly being taught in universities and high schools around the country. [1] In order for future students to gain a sense of modern scientific tools and practice it is necessary to introduce and orient them to NMR spectroscopy as early as possible. Currently however commercial NMR spectrometers can cost anywhere between $25,000 and $100,000. [3] An example of a commercial NMR spectrometer can be seen in Figure 1. This NMR spectrometer is different than our spectrometer as it houses the entire machine in one box and the solution is injected via a syringe into a capillary test chamber. [4] Figure 1[5] Our project aims to provide comparable results of higher end NMR spectrometers to these schools and helps introduce this modern scientific tool to an important and expanding market. NMR spectroscopy relies on a being able to exploit the spin properties of certain elements such as hydrogen, carbon 13, nitrogen, fluorine and phosphorous. [2] These unique elements naturally have a quantum spin number of ½ which is crucial to being detected by an NMR spectrometer. [2] The NMR spectrometer exploits this spin ½ because it applies a powerful external magnetic field that forces each of these nuclei into one of two of their spin states, +½ or -½ as seen in Figure 2. [2] Figure 2[2] These spin states can be understood as miniature magnetic moments that are responding to the larger external magnetic field as seen in Figure 3.[2] 2 field and so based on this information the necessary Larmor frequency will be around 14MHz – 20 MHz. When the chemical compound is placed within the magnetic field the atoms either align in the + ½ or – ½ alignment and remain in this equilibrium state until disturbed.[2] The number of atoms in each spin state is determined by Boltzmann statistics where the ratio of lower energy spin states ! ! to upper energy spin states ! ! is given by equation (5): [2] Figure 3[2] !! These + ½ and – ½ spin states exhibit different energy levels and the difference in the energy levels is proportional to the strength of the external magnetic field as seen in Equation (1). [2] ∆! = ! ∗ ! ! (1) where the magnetic moment, ! is dependent on the material being studied. When the nuclei are placed in the magnetic field the nuclei is able to absorb a photon with a specific frequency of ν. The frequency depends on the specific gyromagnetic rotation, γ of the particle and by the external magnetic field Β given by equation (2): [2] ! = ! ∗ ! (2) An example of γ, in MHz/T for the following elements is shown in table 1. [2] Table 1[2] The particles of the element in the magnetic field can transition between the two energy states when the particle in the lower energy state absorbs a photon and transitions to the higher energy state. The energy, ! of the photon has to match the energy difference between the two states and is directly related to the frequency by Planck’s constant, ℎ as seen in Equation 3. [2] ! =ℎ∗! (3) The technical term used in NMR spectroscopy for the specific frequency ! is the Larmor frequency. [2] Since we know that the energy of the photon needed is ! = ℎ ∗ ! and that ! = ! ∗ ! the energy of the photon in terms of the magnetic field is then given in equation (4). [2] ! = ℎ ∗ ! ∗ ! (4) In our NMR experiment our goal is to successfully measure multiple chemical structures within a 0.3 - .5 Tesla magnetic !! !! = ! !∗! (5) Where !, the energy difference between the spin is states, ! is the Boltzmann constant and ! is the temperature in Kelvin. At room temperature of ! = 273 Kelvin typically the number of lower energy spin states outnumber the number of higher energy spin states.[2] Individual spins and their respective magnetic moment that are in close proximity are then summed together to form spin packets with net magnetization vectors; this helps form a macroscopic image overall spin orientation.[2] When in the equilibrium state the net magnetization vector is parallel to the direction of the external magnetic field,!! which in this case is oriented along the z-axis; this orientation is called the equilibrium magnetization, !! .[2] Introducing energy with a frequency equal to the difference in energy states as shown in equation (4) can change the equilibrium magnetization. If enough energy is put into the system it will eventually become saturated and the overall magnetization vector will transition to when !! is 0, also known as !! .[2] The energy source in NMR spectrometers is a probe coil that produces an RF signal to change the equilibrium magnetization of the system. After the energy source is removed, the magnetization vector will return to the equilibrium state and the time constant of this transition is called the spin lattice relaxation time, !! . The transition is governed by time, ! dependent equation shown in (6): [2] !! = !! ∗ (1 − 2 !! !! ) (6) So as a result !! is the time needed to change the magnetization vector by a factor of the natural number e. Sometimes due to the Heisenberg uncertainty principle which correlates the energy level and the lifetime of the spin states the net magnetization vector will be placed not only in the z-direction but it will rotate about the z-axis in the XY plane as shown in Figure 6.[6] This rotation occurs at the Larmor frequency where it is equal to the necessary photon frequency that would cause a transition between energy levels. [2] 3 Figure 3[2] As the sample returns to the equilibrium magnetization vector it will emit an RF signal at the Larmor frequency. This RF signal is called the free induction decay (FID) signal shown in Figure 7 and it contains the specific atomic information about the atom. [3] where σ is a fraction that is specific to each individual atom. The reason σ is specific to each individual atom is that the electron density around each atomic nucleus varies according the local chemical bonds and nuclei properties. Since the electron density varies the effective magnetic field varies as well. The difference in effective magnetic field due to differing electron densities is called the chemical shift phenomenon. [2] Since different NMR’s are capable of producing different field strengths the effective field produced by the individual atoms will vary from NMR to NMR. [2] In order to keep measurements consistent between NMRs the chemical shift and magnetic field strength should be normalized based on the NMR’s specifications and a reference substance’s resonance. The chemical shift is measured in parts per million (ppm) and is referred to as δ, given by equation (8). [2] != !!!!"# !!"#$%&'() (8) where ! is the measured frequency of a substance, !!"# is the standard frequency of a reference substance and !!"#$%&'() is the operational frequency of the NMR spectrometer. The chemical shift is applied to the FID signal after the probe coil receives the signal and it is converted into the frequency domain via a Fourier transform. The frequency domain signal is then displayed on a ppm vs. intensity graph as shown in Figure 9. This is the final output of the NMR spectrometer and will be further discussed in section III. Figure 4[2] The FID signal is then collected and examined by a separate receiving coil. The FID signal is then converted via a Fourier transform into the frequency domain which shows the different frequency components and thus different atomic nuclei of the sample. An important factor however is the chemical shift phenomenon. This occurs because the sample is placed within the magnetic field and the electrons of the sample circulate about the applied magnetic field direction.[2] The circulation of these electrons causes a small magnetic field at the nucleus that opposes the externally applied field as seen in Figure 8. [2] Figure 5[2] The effective field at the nucleus is related to the applied magnetic field by equation (7). [2] ! = !! ∗ (1 − !) (7) Figure 6 [2] There are two types of NMR set-ups, Continuous Wave (CW) NMR and Fourier Transform (FT) NMR. The CW experiment set-up is the simplest NMR experiment because it involves either having a constant RF and a changing magnetic field or a constant magnetic field and a changing RF. Fourier transform NMR techniques are more popular than CW techniques because they are able to scan and identify multiple components at once whereas CW techniques requires a time consuming process that involves testing for each individual components in succession. [2] For our NMR we chose to use a CW NMR system and this will be explained in the overall NMR system in section III. In order to test our design against contemporary machines and to prove it works correctly we are going to run experiments on the NMR spectrometer that are also used in a standard MIT junior physics lab such as the FID and spin echo 4 experiments. [7] The lab involves junior students at MIT to study the physics and properties of a NMR such as measuring the effect of field homogeneity on NMR performance, measuring the chemical composition of water and determining the effect of field strength on NMR performance.[7] The results gathered from our NMR will be tested against these base line experiments to see if it is functioning properly. As you can see the idea of teaching young students NMR spectroscopy is already an established course at MIT and this shows that understanding NMR spectroscopy gives the students a better advantage in the future. It is this advantage that we are going to bring to high school students with our inexpensive and easy to use NMR spectrometer. II. REQUIREMENTS AND SPECIFICATION A. Review Stage The primary and general specifications of our design for the NMR spectrometer are that the spectrometer should be inexpensive, safe, simple and accurate. We are planning on staying within our allotted $500 senior design project budget. This $500 budget has forced us to design the NMR spectrometer around easy to obtain, simple parts. For instance many of the parts for the RF circuitry typically have been samples from Analog Devices or cheaper parts from Digikey. In fact the most expensive part of the NMR spectrometer to date has been purchasing the magnets and machining the magnetic array. Safety is a big concern for this project because the NMR requires a strong magnetic field in order to properly function. The magnetic field effortlessly attracts and accelerates nearby ferrous materials towards it and that can easily cause harm to an individual nearby or the magnet. The reason for the NMR spectrometer to be simple is that it will be hopefully used in a high school laboratory setting and as a result the students should be able to run it easily and quickly. If the machine is difficult to use or requires intensive knowledge on how it works it won’t be suitable for use in a high school setting. To meet the primary specifications of our NMR spectrometer we need to set technical specifications of the system. The technical specifications for the NMR spectrometer are that it should have around a 0.4 Tesla uniform and homogenous magnetic field, produce RF around 14MHz – 20 MHz and display the ppm curve of simple molecules such as water or methanol with results comparable to commercial NMR spectrometers. The 0.4 Tesla magnetic field strength is an important requirement for our NMR to function properly and to meet out general specifications of performance, safety and cost. Our research into NMR spectrometers led us to find that a magnetic field from 0.5 T – 1 T was a good compromise for general purpose NMR imaging. [8] Given the available permanent magnets and our cost restraint, the optimal theoretical magnetic configuration we are able to achieve is 0.49 Tesla. Although this is more than was the minimum described in [8] we have found examples of other research groups working on permanent magnet NMRs that exhibited field strengths between .2 T - .5 T as it is in our case. [9] The field strength must also be uniform in direction as well as in magnitude so that all of the nuclei of the substance are all affected by the same magnetic field, no matter the location within the substance. [10] High field homogeneity results in higher resolution data gained from NMR spectroscopy that reveals detailed information about the chemical structure. [10] The magnet will be designed and tested as such to prove that the field lines are homogeneous and uniform as possible within the sample area itself. The RF generation and receiving is also being designed with correct components to meet the specification of around 14 MHz – 20 MHz. The RF needs to be in this range because of our designed magnetic field strength and the properties of hydrogen as seen in Table 1. The RF generation also needs to be tunable to adjust for the actual measured field strength of the magnet and not the absolute designed value. III. DESIGN A. System Overview Figure 10[2] Our built NMR spectrometer system diagram is displayed in block diagram form in Figure 10 and for our final project accomplishments we have broken it up into five block components. The first component is the magnetic field itself and it is the building block upon which all of the other blocks rely on to function properly. [8] The magnet is essential to the NMR process and it is entirely its own standalone part of the device. The second part of our design is a magnetic field sensor whose role is to measure the homogeneity and field strength of the magnetic design and provide verification of the magnet functioning properly. The field sensor we have designed is inexpensive and is fine tuned toward our magnetic field design. In addition, the field sensor we have designed is considerably less expensive than commercial magnetic sensors while still giving correct information. The addition of a field sensor gives further value of our project to being used in high school laboratories as it allows students to study the effect of field strength and homogeneity on the outcome of NMR spectroscopy. Our magnetic field design also lacks the proper shimming coils necessary to correct any inhomogeneous fields within the magnet and so it is important to measure field homogeneity before performing a NMR spectroscopy. [10] The third part of our design is the RF generation = circuitry which is connected to both the transmission coil. Also the 5 receiving coil and oscilloscope form the fourth component block and the software interface that controls the pulse length and pulse frequency is the fifth block. The design explanation and reasoning of each of the components will now be explained. A homogeneous and uniform magnetic field of 0.4 T is our design specification based on the overall project goals and specifications. After conducting initial research into magnetic field design and weighing it against our project goals it was determined that a Halbach cylindrical magnetic array was the best choice for the permanent magnet. An example of an eight segment Halbach array is shown in Figure 11. [11] magnetic remanence in Tesla (Br), the field orientation of each magnet relative to overall magnetic field Bo, and finally the inner (r1) and outer radius (r2) of the cylinder. The magnetic field, Bo inside the cylindrical array is determined by the equation (9). [12] ! !! = !! ∗ !! ∗ ln ( !) !! The constant Cn is determined by the number of individual magnets and is calculated by equation (10): [12] !! = Figure 11[12] The array works by arranging individual smaller magnets in orientations such that all of the individual magnetic fields add up to form a homogeneous and uniform field within the center of the cylinder and little to no field outside of the cylinder. The uniform field lines are an important and integral part of the NMR spectrometer working properly.[10] A homogeneous field is necessary because it directly affects the alignment of the molecules in the substance. If the field is inhomogeneous molecules of similar elements will experience different relaxation times and thus emit different frequencies when returning to the equilibrium state.[10] These frequency differences can cause the spectral lines shown in Figure 9 to appear wider, lessening the spectral resolution of the spectrometer. [10] A simulation of the homogeneous field lines within an eight-segment Halbach array is shown in Figure 12. [13] (9) !! ) ! !π ! !"# ( (10) Using vector and matrix analysis it is possible to analyze the magnetic contribution of each individual magnet in the Halbach array and derive equations (9) and (10). These equation derivations can be seen in reference [14]. The upcoming analysis concerning the Halbach array layout concerns a densely packed magnetic structure. A densely packed magnetic structure as seen in Figure 13 would be preferable as it increases the overall field homogeneity throughout the inner cylinder but a compromise must have been made with cost and feasibility. It is important to understand however how the ideal Halbach cylinder functions and is formed in order to fabricate as much of an ideal cylinder as possible. The orientation of each magnetic field is important to understand how orientation affects the overall magnetic field. To understand how the orientation affects the Halbach array we first must assign each individual magnet a position on a ZY coordinate axis such that the center of each magnet is a standard distance r from the origin or center of the Halbach cylinder. [15] This coordination of the magnets can be partly seen in Figure 13. Figure 13[15] The coordinates of the magnet center, denoted by vector !!! are then easily represented with a matrix equation (11): [15] Figure 12[13] The important specifications and properties of the Halbach cylindrical array that need to be considered are the number of individual magnet segments (M), the cross sectional dimensions of each square magnet face (a), the individual !! sin ! !!! = ! ! = ! !! !"#$ (11) where B is the angle between the magnet center and the direction of the desired magnetic !! and 6 ! = ! ∗ !, (12) ! = 0, 1, 2, … , ! − 2, ! − 1 Then we consider having M magnets leads to having the following coordinates for each Mth magnet: [15] ! !!! = cos( − 2 ∗ !! ) !!! ! ! = (!!! + ) ∗ (13) ! ! !!! sin( − 2 ∗ !! ) ! The sign of the cos and sin are dependent on where the magnet is ultimately oriented within the coordinate system. It is then possible to solve for a, the cross-sectional dimensions of the individual magnets as seen in equation (14). ! =2∗!∗!∗! Figure 14 (14) ! where ! = − 2 ∗ !! ! From there given the fact that the area, A occupied by the magnets is densely packed then it can found to be as seen in equation 15. ! = ! ∗ ! ! = 4 ∗ ! ∗ ! ! ∗ ! ∗ ! ! (15) and so the inner and outer radius can be found in terms of the magnetic center radius and the orientation angle as seen in equations (16) and (17) for inner and outer radii respectively. !! = ! ∗ (1 − 2 ∗ ! ∗ !) (16) !! = ! ∗ (1 + 2 ∗ ! ∗ !) (17) The orientation of the magnet can be seen as having an effect on both the inner and outer radius as well as the cross sectional dimensions of the individual magnets. This analysis also shows how each parameter is interconnected with each other and that by changing one parameter will affect the other parameters as well. Based on these calculation we were able to purchase the correct magnets and design the array that would give us approximately 0.4 Tesla field strength within the cylinder. The magnets ultimately chosen for the Halbach array were 16 1.27 cm x 1.27cm x 3.81cm neodymium N42 grade (NdFeB) magnets each with an individual remanence of 1.3 Tesla. The layout of the Halbach cylinder was chosen to be as seen in Figure 14. The notches in the cylinder are the places for the magnets to be secured and the magnets individual orientations are shown in the red arrows. Figure 15 The cross sectional view displays eight magnets and the three dimensional view shows how the 16 magnets can be stacked in order to create a longer cylinder. The cylinder length was made to be 7.62 cm as it fits the length of the two bar magnets stacked lengthwise. An aluminum casing for the magnets was designed and machined with the end result shown in Figure 15. Aluminum is a non-ferrous material and does not interact destructively with the intended magnetic field lines as a steel or iron casing would. The aluminum casing was designed with ease of manufacturability in mind and as much reduction in machine costs as possible. The design was a collaborative process with machinists employed in both the Hasbrouck physics machine shop located on campus and the Amherst Machine Company located off campus. We chose to have a cylinder with an inner radius of 3.5 cm and thus the outer diameter is around 5.29 cm because of the diagonal of the magnet extending 1.79 cm from the inner radius. Thus with an inner radius r1 of 3.5 cm, outer radius r2 of 5.29, individual magnetic remanence Br of 1.32 T, and 8 (M) magnet segments it is possible to calculate !! and thus calculate the desired magnetic field !! . Following equation (10) we see that !! is equivalent to 0.9003. Using this value in equation (9) leads us to a desired !! of .49 T. This value is indeed higher than the desired .4 7 Tesla but it is the closest we could get with the available magnetic stock while still remaining in our tight budget. The Halbach cylinder array also has the advantage of producing the field strength required but also gives us the optimal field homogeneity that keeps us within our budget. Typically the magnet systems of NMR spectrometers include shimming coils within the magnet field that help to offset any stray field lines that naturally occur in the magnetic field.[2] The shimming coils are typically electromagnetic coils that produce small magnetic fields in order to direct the magnetic flux in certain areas and create a more homogenous field. [16] In our design however we will not include shimming coils as our sample area space is limited and we foresee that we will not have time to properly complete the shimming coils. The magnetic field sensor will be used to measure the magnitude and homogeneity of the field within the interior of the magnet. The sensor design involved the programming of the hall-effect sensor and the design of a mechanical device used to freely move the device within the magnet as well as determine the strength and homogeneity of the field with the highest possible precision. The accuracy and stability of the MLX90215 hall-effect sensor was improved by programming the chip using the PIC18F4550 microcontroller in MPLAB. The programming was done by setting the 10-bit quiescent voltage (voltage at B=0 Tesla) to half of the total voltage across the sensor in order to maximize the output swing and the linearity. The sensitivity of the sensor was programmed by adjusting its rough gain (with 3-bit) and its fine gain (with 10-bits) to zero. Setting both gains in this manner offered the highest level of sensitivity provided by the chip, 4.1mV/mT, or 0.41V/.1T. At the highest value of the field generated by the magnet (0.49 T) the sensor should output a corresponding voltage of 1.96 V which is largely within the 4.5~5 V specifications. Moreover, we used a 1-bit inverse slope function to program the chip in such a way that an increase or a decrease in the magnitude of the output voltage indicates the presence of a North magnetic pole or a South magnetic pole respectively. The signal input signal of the sensor was set to 1 a pulse greater than 150us and 0 for a pulse less than 150us as seen in Figure 16. The mechanical device used for the motion of the sensor was made out of a non-ferromagnetic material in order to keep it from interfering with the magnetic field. It had to be very stable and balanced in order to hold the chip still during measurement, and it had to be able to freely move the chip in the XYZ directions. We chose aluminum and brass as our nonferromagnetic materials because they were within our budget and we used two materials instead of one in order to avoid connections between the same materials and reduce the quantity of aluminum used given its large weight. Our design is made of a wide square base (7*7 inches) 1.5 inch thick, which gives us the support we need for foundations. We used three ½-20 brass threaded rods, 4 inch tall, on which aluminum knurl knobs are used to move the sensor in all three dimensions and allow us to keep track of the exact position of the sensor (1/20inch travelled per turn). The final product of our design is shown in Figure 17 and temporary measurements of the magnetic array are depicted in Figure 18. Figure 17 Figure 18 Figure 16 The RF signal generator sends pulses to the testing sample via a single probe coil wrapped by thick copper wires since the coil is supposed to place in the center of the magnetic field and copper is not magnetic material. The coil is created from 24 gauge enameled copper wire that is wrapped in a 2 cm diameter cylinder, which allows enough space for the sample to interact with the coil. The coil is also encased within heat shrink so that it will remain rigid and be easier to use. The designed transmission coil is shown in Figure 19 though the receiving coil is created exactly the same. 8 programmable waveform generator PCB implementation is shown in Figure 22. Figure 19 The most significant part of the RF signal generator is a RF switch circuit to provide a 50 microsecond on/off signal (which has a 1 Hz frequency) up sampling with around 14.9 MHz local frequency. The RF switch circuit works by using a square wave gate signal to switch on and off the RF source with a J310 RF MOSFET. The designed circuit diagram is shown in FIGURE 20 with the final design shown in FIGURE 21. Figure 22 B. Design Alternatives IV. FINAL PROTOTYPE IMPLEMENTATION AND RESULTS For our final prototype implementation we have created a two coil system, one receiving coil and one transmission coil that can demonstrate a unique but questionable free induction decay signal for different chemical compounds such as water and ethanol. Although our goal was to have a fully working NMR spectrometer by our final prototype we have encountered a great deal of problems that have prevented us from doing so. The final system set-up is shown in Figure 23. Figure 20 Figure 23 Figure 21 When the square wave gate signal is low, the coil provides external energy to the sample to interrupt the atoms’ equilibrium. While when the square wave gate signal is high, the coil collects the FID voltage generated by the sample.The square wave gate signal is generated from a PIC18F4500 microcontroller. The LO signal is created by a programmable waveform generator, AD 9834 evaluation board from Analog Devices. This chip is able to provide sinusoidal signals up to 37.5 MHz. PCB design is required for this circuit due to the package of the chip is too tiny to apply to breadboard. The The first problem we encountered was involving the AD 9834 frequency synthesizer on the transmitting PCB board. The synthesizer PCB board, shown in Figure 19 was fabricated according to our design but was not producing the required sine wave output or outputting a signal at the desired 14.9 MHz frequency. We have still yet to determine the actual cause of the frequency synthesizer malfunction but we have tried to troubleshoot a few areas in order to make it function properly. We started by double-checking that the chip was successfully soldered onto the PCB and that all the proper signals were being inputted into the pins correctly such as grounding the RESET and SLEEP pins. After that we went through the programming message protocol and determined via an oscilloscope that the correct message was indeed being sent to the frequency synthesizer, shown in Figure 24. 9 However at and even above our intended frequency of 1 Hz for the RF input and 14.9 MHz for the LO signal we have been unable to obtain a satisfactory output signal (yellow) when mixing a 30 MHz LO signal (blue) with a 14.9 MHz RF signal (purple) which can be seen in Figure 26. Figure 24 We obtained the programming message by following the programming equation shown in equation (18) and by following the data sheet application notes for the correct bit assignment. [17] In our case the required frequency, fout is 14.9 MHz and the frequency of the master clock, fMCLK was 50 MHz which we generated with a function generator. Freq Re g = fout * 2 28 f * 2 28 (18) FreqR e g = out fMCLK fMCLK Figure 26 We theorized that this was due to the 1 nF capacitor at the input of the RF signal which was acting which was acting as a low pass filter and filtering out the lower frequencies. In order to prove this idea we performed a frequency sweep on the RF input of the mixer and found its 3dB drop off point. This frequency sweep vs. signal amplitude is shown in Figure 27. The second problem that we encountered was involving the transmitting function of the AD8342 mixer that we originally intended to use instead of the RF switch. We tested the mixer by inputting two sinusoidal waves into the RF and LO inputs of the mixer and it operates properly when the waves are at high enough frequencies as seen in the yellow signal in Figure 25 where the RF frequency was 60 MHz (purple) and the LO frequency (blue) was 80 MHz. RF Input Frequency vs. Mixer 10 Output Amplitude (No Capacitor) Vpp (V) And finally in order to check out programming code we used it to program the AD9834 evaluation board. Our programming message was indeed correct as it was successfully programmed and outputted a sine wave at our defined frequency. In the end we determined that it the soldering of our PCB board that caused our transmission circuitry to fail. 1 13 15 17 19 21 23 25 27 29 31 Frequency (MHz) Figure 27 Figure 25 After that frequency sweep we increased the capacitor’s value by an additional 1 nF and ran another frequency sweep which showed that the 3dB drop off point was indeed changed. The new frequency sweep can be seen in Figure 28. However we were still unable to get a satisfactory result from the mixer at 10 our desired frequency so these results were collected with an LO of 35 MHz in order to show the effect of the input capacitance. The overall amplitude of the addition capacitor was greater over the frequency range but the actual mixing waveforms at lower frequencies ended up looking like Figure 26. 10 Vpp (V) RF Input Frequency vs. Mixer Output Amplitude (With added capacitor) The transmission coil is oriented 90° to the receiving coil so that the mutual inductance between the two coils is reduced as much as possible which was partly obtainable during our CDR presentation. The mutual inductance however is not fully removed in our FPR progress and it introduces some uncertainty into our results. The uncertainty arises from being unable to determine of the receiver coil is primarily driven by mutual inductance or by the free induction decay. Our results suggest that it is a combination of the two and will be discussed later on. The receiving coil contains the sample and due to it’s close proximity it is the strongest coupled to the free induction decay from the sample. The two coil transmit and receive system is visible in Figure 15. In order to tell if we were receiving any sort of response from the sample at any RF pulse frequency we performed a RF frequency sweep from 12 MHz – 18 MHz and plotted the RMS value of the amplitude. The result of the sweep for an ethanol sample, water sample and no sample is shown in Figure 30. 1 13 15 17 19 21 23 25 27 29 31 Frequency (MHz) Figure 28 In order to obtain some kind of free induction decay signal we needed to try a different method other than using the PCB transmitting and receiving boards. In order to replicate the pulsed RF signal we obtained a J310 RF MOSFET switch that is driven by a square wave input. Our 14.9 MHz signal from the function generator and through our transmission coil is connected to the drain of the switch, the source is grounded and the square wave is connected through a voltage divider into the gate as seen in FIGURE 20. The switch acts as a transmission and receive switch and is used to turn the 14.9 MHz signal on and off. The resulting signal across the transmission coil is the signal in Figure 29. Figure 29 Figure 30 An analysis of this data shows that there is a peak in the RMS amplitude around 16.5 MHz for all the different 11 samples. The samples do exhibit some variation in their amplitude peaks as for water and ethanol the curve is slightly shifted to the right with ethanol experiencing more of a shift than just water. A proposed reason for this change in amount of total shift is that the higher percent of hydrogen in ethanol over water. Also ethanol experiences some electron shielding on the hydrogen atom from the carbon and oxygen that the water sample does not experience. The electron shielding should result in a wider range of larmor frequencies.[2] Another important experiment we performed was to see if the RF pulse length had an affect on the RMS value of the post-pulse receiving coil amplitude. The pulse was pulsing at a period of 2.5s and the pulse length was swept from 0 to 1.5 seconds. The RF amplitude did experience an increase in amplitude around .83 seconds as seen in figure 31. V. PROJECT MANAGEMENT A. Team Member Roles An important part of this project was determining and dividing the tasks correctly so that we can quickly and efficiently complete it on time. Our system as has been designed and intended for FPR has been broken into three separate components which are the magnet design, the magnetic field sensor and the RF generation and receiving circuitry. Since we have three team members it was simple to devise the tasks between ourselves. We broke down the roles as follows; Zach will be in charge of the magnetic field design, Aline will be in charge of creating the magnetic field sensor and Mandy will be in charge of the RF generation and receiving circuitry. B. Project Outlook The outlook on the project as of right now is that we would need some more time in order to get a workable NMR spectrometer. We do believe however that we are very close to detecting the different FID signals in a variety of substances such as water and ethanol because we can see a varied response in the amplitude change around 16.5 MHz for the different substances. VI. SUMMARY AND CONCLUSIONS Figure 31 It is necessary to study the pulse length of the RF pulse because many NMR experiments are based around changing the pulse length. The standard NMR experiment involves finding the FID signal but by doubling the FID pulse length it is possible to view the spin echo response. The spin echo occurs when the atoms magnetization is flipped 180 degrees rather than the 90 degrees during a regular FID pulse. This 180 degree flip causes a sample response where after receiving sequence of 90 degree pulse the 180 degree pulse the sample emits a sine wave that exponentially increases and then exponentially decreases. This spin echo response is important as it reveals more information about the molecules full composition. The two different samples we tested water (H20) and ethanol (C2H60) are common samples in NMR spectroscopy. [reference] However due to the inability to totally remove the mutual inductance we are unable to purely isolate the pure FID signal. If the mutual inductance signal were totally removed then the signal should decay and not return until the RF pulses again. This report has summarized, clarified and outlined the purpose of our NMR spectrometer as a senior design project. We have described the necessary background behind the functioning of NMR spectrometers while showing the motivation and reason for it as our SDP project. An NMR spectrometer will be a strong tool for high school students to use in the understanding and comprehension of the fields of biological and chemical sciences. Our progress so far has involved us using techniques we have learned in the field of electrical engineering and learning new techniques in related fields. The NMR spectrometer as designed but not fully implemented will be able to decipher the chemical structure in both water and benzene. Our progress so far up until this final design review has taught us a great deal about designing and implementing complex engineering systems. We have experienced a great amount of setbacks with the machining of the aluminum magnetic array, the magnetic field sensor, the frequency synthesizer and the mixer necessary for the RF circuitry. As a result we had to find another method for obtaining a FID signal in order to give a demonstration of a working NMR response. We do feel however that our progress up to this point has allowed us to understand the workings of an NMR machine VII. REFERENCES [1] B. Esselman and D. E. Mencer, “Inclusion of NMR spectroscopy in high school chemistry: Two approaches,” Modern NMR spectroscopy in education, vol. 969, p. 77, 2007. [2] J. Hornak, The Basics of NMR, online manual of the Magnetic Resonance Laboratory, Rochester Institute of Technology. 2003. 12 [3] M. Edgar, “Physical methods and techniques: NMR spectroscopy,” Annu. Rep. Prog. Chem., Sect. B: Org. Chem., vol. 107, pp. 308–327, Jun. 2011. [4] M. Edgar, “Physical methods and techniques: NMR spectroscopy,” Annu. Rep. Prog. Chem., Sect. B: Org. Chem., vol. 107, pp. 308–327, Jun. 2011. [5] M. Edgar, “Physical methods and techniques: NMR spectroscopy,” Annu. Rep. Prog. Chem., Sect. B: Org. Chem., vol. 107, pp. 308–327, Jun. 2011. [6] F. P. Gasparro and N. H. Kolodny, “NMR determination of the rotational barrier in N, N-dimethylacetamide. A physical chemistry experiment,” Journal of Chemical Education, vol. 54, no. 4, p. 258, 1977. [7] S. D. Sewell, G. W. Clark, U. J. Becker, and J. Kirsch, “8.13/8.14 Experimental Physics I & II‘ Junior Lab’, Fall 2002,” 2002. [8] D. I. Hoult, C. Chen, and V. J. Sank, “The field dependence of NMR imaging. II. Arguments concerning an optimal field strength,” Magnetic Resonance in Medicine, vol. 3, no. 5, pp. 730–746, Oct. 1986. [9] E. Danieli, J. Perlo, B. Blümich, and F. Casanova, “Small Magnets for Portable NMR Spectrometers,” Angewandte Chemie International Edition, vol. 49, no. 24, pp. 4133–4135, Jun. 2010. [10] S. Vathyam, S. Lee, and W. S. Warren, “Homogeneous NMR spectra in inhomogeneous fields,” Science, vol. 272, no. 5258, p. 92, 1996. [11] H. Raich and P. Blümler, “Design and construction of a dipolar Halbach array with a homogeneous field from identical bar magnets: NMR Mandhalas,” Concepts in Magnetic Resonance Part B: Magnetic Resonance Engineering, vol. 23B, no. 1, pp. 16–25, Oct. 2004. [12] B. T. Merritt, R. F. Post, G. R. Dreifuerst, and D. A. Bender, “Halbach array motor/generators-A novel generalized electric machine,” Halbach Festschrift Syposium February, vol. 3, 1995. [13] G. Küstler, “Computation of NdFeB-Halbach Cylinders With Circular and Elliptical Cross Sections in Three Dimensions,” Magnetics, IEEE Transactions on, vol. 46, no. 9, pp. 3601–3607, 2010. [14] K. Halbach, “Design of permanent multipole magnets with oriented rare earth cobalt material,” Nuclear Instruments and Methods, vol. 169, no. 1, pp. 1–10, 1980. [15] N. Doğan, R. Topkaya, H. Subaşi, Y. Yerli, and B. Rameev, “Development of Halbach magnet for portable NMR device,” in Journal of Physics: Conference Series, 2009, vol. 153, p. 012047. [16] P. Konzbul and K. Sveda, “Shim coils for NMR and MRI solenoid magnets,” Measurement Science and Technology, vol. 6, p. 1116, 1995. [17] A. Devices, “AD9834 Specifications,” AD9834 Datasheet, Feb, 2003. [18] J. P. Heremans, “Magnetic field sensors for magnetic position sensing in automotive applications,” in MRS Proceedings, 1997, vol. 475. [19] T. F. Budinger and others, “Nuclear magnetic resonance (NMR) in vivo studies: known thresholds for health effects.,” Journal of computer assisted tomography, vol. 5, no. 6, p. 800, 1981. VIII. APPENDIX A. Application of Mathematics, Science and Engineering Our project involves multiple disciplines from the fields of mathematics, science and engineering such as circuit design and analysis, electromagnetic fields and waves, and computer interfacing. Our course history here at the University of Massachusetts has prepared us well for this project. For instance our use of microcontrollers within the RF circuitry draws heavily from ECE 353, Computer Systems as well as ECE 313, Signals and Systems. The circuit design has been strongly influenced by the design oriented ECE 323 and 324, Electronics I & II respectively. The magnetic field aspect of our project draws heavily from our work in ECE 333, Fields and Waves. A specific example of us applying our coursework in this project can easily be seen in the RF generation and receiving circuitry. This part of our project is heavily influenced ECE 353 because it involves the use of a programmable microcontroller, the PIC18F4500 which provides the IF square wave signal for the mixer. This is reminiscent of last project we worked on in ECE 353 where we had to program a microcontroller to do the same function but in that case the signal was acting as a clock for the rest of the circuit. ECE 323 and 324 were useful when designing both the magnetic sensor circuit and the RF component because it gave us a strong background in understanding how to arrange the circuit together. To be specific our experience in trouble shooting the programming of the magnetic sensor involved measuring the output signal of the microcontroller with an oscilloscope, a common tool used in ECE 323 and 324. Of course our individual academic experiences have shaped how we apply the fields of mathematics, science and engineering. Zach, being in charge of the magnet design process has drawn heavily on his interest in the physics side of electrical engineering while Mengting has used her previous REU experience designing circuits in her RF circuitry design. Aline has also drawn upon her experience as a TA in electronics and her knowledge of MRI technologies as a research intern at Massachusetts General Hospital. B. Design and Performance of Experiments, Data, Analysis, and Interpretation Prior to our midway design review we had performed a very basic experiment that involved measuring the field strength vs. distance of an individual NdFeB bar magnet at pole the north and south poles. This was primarily a test of our working magnetic sensor design as well as to see if the desired magnets behaved as planned. The study involved changing the vertical position of the bar magnet over the sensor in 0.2 cm intervals and recording the change in magnetic field strength until the magnetic field strength reached a value of 0. The data we collected is shown in Figure 32 and it correlates well to other magnetization versus distance curves in similar hall effect sensors. [18] 13 Figure 32 The experiment showed us a few different facts about our sensor and a few parts that need to be adjusted for perfect performance. The experiment showed us that the sensor was being pulled completely up to the supply voltage, Vdd and also down to ground thus causing the inability to measure stronger magnetic fields such as the 1.32 T produced by the individual magnets. This affect however was accounted for in our design because the magnetic field sensor was picked so it could measure the Halbach cylindrical array and it’s 0.4 – 0.5 T field. This field range is easily within the sensitivity of the sensor to measure accurately. This experiment also let us know the effects of having not optimum voltage swing as the quiescent voltage was not at the specified ½ of the 5V supply. This brief collection of data will lead us to further improving our design and will also allow us to practice creating scientifically correct experiments for the final testing of the NMR spectrometer in April. C. Design of System, Components or Process Meet Desired Needs within Realistic Constraints The system requirements of our design are that the NMR spectrometer should easy to use and to understand so that high school students can use it successfully in a laboratory setting. This is so that students can use the device with as little hassle as possible while gaining as much information about their sample. Our NMR spectrometer is designed to be able to give results comparable with similar commercial devices although not necessarily with the precision as higher end devices are capable. The device should also be a reasonable size and be safe to use because it will have be located primarily within a high school laboratory setting. Realistic constraints with our design are based around the safety of the device and the performance of the device to accurately measure chemical properties close to that of commercial devices. Since typical commercial devices use strong superconducting magnetic fields of around 18T we needed to use a lower magnetic field that would be considered safe in a high school setting. We have decided to use field strength of around 0.4 – 0.5 Tesla. This magnetic field strength is more manageable and easier to design in a safe working environment. A magnetic field of this strength can still be dangerous if used improperly however so we have designed the magnetic field array to be safely housed in an aluminum casing that is fastened to a stand so it won’t move in the presence of magnetic materials. Since the aluminum casing is a non-ferromagnetic material it should not destructively interfere with the magnetic field within the cylinder and provide strong enough housing to hold the magnets in place. [11] The rest of the device is relatively safe as it is railed at +/- 9 volts. The accuracy of the device is perhaps the most realistic constraint in our design as we will not be able to directly compete with similar commercial devices for enhanced resolution in identifying chemical compounds. Our design should deliver reasonable results given our $500 budget because we have kept the design specifications within reasonable limits such as the .49 Tesla field that is strong enough to properly align the atoms but low enough so we can generate the proper 15.9 MHz Larmor frequency necessary using conventional circuitry. D. Multi-Disciplinary Team Functions Our team has worked well to split up the necessary tasks for completing this project with satisfactory results. We feel that the work load has been distributed as evenly as possible and that we are all contributing equally to the final design. Aline Elad, an electrical engineering major has been responsible for designing the magnetic field sensor and sensing apparatus. Aline has been performing research into magnetic sensors and has chosen the MLX90215 sensor as it is fits the requirements of the designed magnetic field. Aline has also contributed to part of the comprehensive report on our NMR spectrometer as well as to all of our review presentations. Mengting Nan, also an electrical engineering major has been responsible for designing the RF component of the NMR spectrometer. Mengting has been busy designing the RF component from parts that are available to us and she also has been creating printed circuit board design that can be manufactured in a future date. Mengting has also contributed to the NMR design report as well as created contributions for the PDR and MDR presentations. Zachary Henderson has been responsible for researching, designing and machining the magnetic field array that is crucial to the functioning of the NMR spectrometer. Zachary has found a suitable solution in the Halbach cylindrical array and designed, via AutoCad a drawing that is capable of being machined in aluminum via an automated CNC milling machine. Zachary has also been the primary author of the NMR design report as he has primarily written and proofread the entire report. E. Identification, Formulation and Solution of Engineering Problems An example of an engineering problem that was encountered during this project was in the design of the 14 magnetic array. The problem primarily consisted of the orientation of the magnets in the actual array. Since the magnets we ordered are square faced magnets measuring 1.27 cm x 1.27 cm and the orientation had to be as described in Figure 15 it was necessary to have the face of the square magnets not form 90 degree angles with the tangent of the inner circumference. The machinists preferred this orientation as it allowed them to fabricate the aluminum casing easier. The ease of manufacturing the part in the radial manner is that they could clamp the part in one single vice that is capable of rotating a full 360 degrees and mill out each notch one after another, instead of needing to realign each time. After explaining the situation to the machinists at the machine shop we had to come up with other manufacturing solutions that would allow us to have the orientation necessary for the Halbach cylindrical array. In the end it was decided that the notches in the aluminum casing that would hold the magnets could be fabricated using another technique that was machined in a computer controlled milling machine that was capable of running the entire process unassisted. This technique will be done at the Amherst Machine Company using their CNC milling machine. This problem was efficiently overcome by communicating to the machine shop the necessity of the particular design and by then brainstorming other ideas that could fabricate the part as quickly and successfully. The problem was quickly identified as we communicated with the machine shop and they understood the situation and took more time to brainstorm some more ideas with us. Ultimately it was their expertise in the area of machining metal that helped us find the solution to the issue and it served as a great learning tool for us in dealing with engineering problems. This example serves as a great problem for us to solve as engineers because it involved identifying the problem, communicating together as teammates with outside sources and working with outside sources to solve a problem that we couldn’t solve with our own skill set. F. Understanding of Professional and Ethical Responsibilities An example of an ethical consideration that was inherent in the design and building of our NMR spectrometer was the safety concerns involving the use of a strong magnetic field. Since our project goal was to introduce an NMR spectrometer into a high school student science curriculums it was critical that it’d be as safe as possible for students to operate. In order to deal with the safety issue of the strong magnetic field we had to design the NMR around a lower field strength magnet. The issues and concerns that arose with having a lower field strength magnet were that the field might lose field strength homogeneity over the sample area. Researching different magnetic field solutions that had high field homogeneity at lower magnetic fields as well as being easy and cheap to manufacture dealt with this issue. The chosen magnetic array design of a Halbach array was the best possible solution since it created a much lower magnetic field of approximately .49 T. This lower magnetic field will still attract nearby ferrous materials such as iron or steel so the operators will still need to be careful of what is placed near the magnet. Insuring that any operators receive thorough instructions on the proper handling on the equipment can solve the issue of attracting nearby ferrous materials. G. Team Communication Our team has been constantly communicating through multiple and varied channels. We have been in contact via email and via telephone almost on a daily basis. Our team also meets regularly on a person-to-person basis in team meetings usually in the senior design lab. Our team has valued communication and sees it as a powerful and useful asset in the completion of our senior design project. We find that our communication has helped us to identify and overcome obstacles that we have encountered. H. Understanding of the Impact of Engineering Solutions in a Global, Economic, Environmental and Societal Context Based on our research on the importance of NMR spectrometers in the field of biology and chemistry we saw the positive benefits of introducing this technology to students in their high school curriculum. Our research has revealed that many of the topics taught in high school chemistry such as chemical structure and composition are direct applications of NMR spectroscopy. A societal context of introducing NMR spectrometers to high school students is that we are preparing them for future school and work responsibilities. For students who are interested in the field of biology and chemistry experience in NMR spectroscopy will potentially allow them to attend more competitive colleges and obtain undergraduate research roles. So when it comes to obtaining a job or attending graduate school students with undergraduate research roles will be favored over other students. As a result the overall workforce in biology and chemistry would not only be more proficient in an important area of their field but would also be a more focused and experienced workforce. Having a more focused and experienced workforce could further increase a company’s profitability and allow for economic growth in today’s slow economy. Our NMR design has influenced primarily by the negative societal consequences of how unsafe equipment can be potentially harmful to people. The issue of safety was an important aspect of our NMR design and was dealt with by using a relatively low and safe magnetic field strength. [19] A higher magnetic field strength could cause magnetic materials to accelerate toward the magnet. These materials could hurt an individual or they could break the system in unintended ways. This is why we have tried to create as safe as magnetic field system as possible by using a field strength between 0.4 – 0.5 T which is much less than standard NMR field strengths of 18 T.[19] If our device was unsafe to operate or if it could potentially cause harm to an individual while operating it would be a harmful and negative consequence of our project. I. Application of Material Acquired Outside of Coursework This project involved incorporating a great amount of material and knowledge outside of our typical coursework in the field of electrical engineering. Examples of sources we had to obtain are the local machine shops, the hall-effect sensor manufacturers and sources describing the technical operation of NMR spectrometers. 15 For designing and manufacturing both the magnetic field array and the magnetic field sensor apparatus we had to learn a great deal about different machining strategies and concepts. Our work involved designing two-dimensional and threedimensional models in AutoCad and then bringing them over to the machine shops for consultation. The use of AutoCad was a huge hurdle for us as we had never needed to use an advanced drafting tool in our curriculum as electrical engineers. The best help we acquired for learning AutoCad was online tutorials and instruction for simple tasks such as inserting scale dimensions, combining shapes and extruding two-dimensional objects into three-dimensional shapes. The machinists at the machine shop were especially useful when it came to actually designing the parts, as they would let us know how feasible our entire design actually was. For the fabrication of the magnet array we had discussions with the machinists on aluminum thickness, individual magnet orientation, and individual magnet depth. We also learned a great deal about different machining practices such as milling, boring and finishing that were required to finish the machining but we never would have known about if we hadn’t attempted this project. Initially we needed to understand what type of field effect sensor we needed to have to accurately measure the intended field strength of our magnet. After doing some preliminary research on magnetic sensor chips and systems, we decided on a Hall effect sensor based on its capabilities of measuring magnetic fields down to below .48 T. The problem we needed to clarify is what actual Hall effect sensor we should purchase that would be easy enough to manufacture and use. Therefore, we called a manufacturer, Melexis who makes a great deal of these Hall effect sensors and they recommended a few different ones that they felt could be used in this project. This helped to clarify the data sheets we were finding on sites such as digikey and it ultimately led to our choice of choosing the MLX90215 as its operating parameters such as supply voltage and sensitivity fit well into our designed system. The final piece of outside information that we obtained was the actual functioning of an NMR spectrometer itself. When we first decided to tackle this project barely any of us knew how an actual NMR spectrometer works but through diligent research we discovered the basic fundamentals of NMR spectroscopy. In particular reference [2] was extremely helpful in decoding the inner workings on an NMR spectrometer as it started with explaining the fundamental spin physics and went directly into the basic hardware overview that was necessary to implement the NMR spectrometer. Our background in physics and electromagnetic fields and waves did aid us and allowed us to understand the NMR spectrometer faster but we still had to learn a great deal about the fundamental spin properties. J. Knowledge of Contemporary Issues Our project was directly aimed at helping and aiding students in the field of biology and chemistry. As students ourselves we know of the importance of achieving experience in a field early and often as it grants you more opportunities when it comes to applying to graduate school and for full-time work positions. This and will always be a contemporary issue because the fields of physical sciences will constantly be advancing and it will be necessary for students to understand fundamental tools such as NMR spectrometers which are the building blocks of a number of cutting edge research. Our goal of this project is to make sure that students can find a cost effective and simple way of using an NMR spectrometer so they can increase their tool set, thus potentially advancing the fields of physical sciences even further. K. Use of Modern Engineering Techniques and Tools Our project involves the use of many different modern engineering techniques and tools that are commonly used today. Such techniques include printed circuit board design, two/three dimensional computer aided drafting and knowledge of electronic circuitry and electronic systems. For the printed circuit board design of the RF generation circuitry we used software called PCB artist. For the two/three dimensional computer aided drafting we used AutoCad 2011 Student Edition. The tool set available to us in AutoCad was powerful and allowed us to accurately design both the magnetic circuit array and the magnetic field sensor apparatus. Finally our knowledge of reading datasheets and prototyping circuits on breadboards has been helpful in putting together both the field sensor circuitry and the RF generation and receiving circuitry.