Submitted to:

Sir Hassan Jahanzeb

Submitted by:
Ameer Hamza
2015-PET-14

ABSTRACT
This assignment is about to give the basic principle,
applications and outputs of the nuclear magnetic
resonance (NMR) tools.

“NUCLEAR
MAGNETIC
RESONANCE”
Subject: Well logging
 “Nuclear Magnetic Resonance”
Historical development
Within a few years after the first successful observations of NMR in 1946, and the
demonstration of free-precession NMR in the earth’s magnetic field in 1948, the petroleum
industry recognized the potential of NMR measurements for evaluating:

 Reservoir rocks
 Pore fluids
 Fluid displacement (flow)

In the early 1950s, several companies, particularly California Research (Chevron), Magnolia
(Mobil), Texaco, Schlumberger, and Shell, began extensive investigations to understand the
NMR properties of fluids in porous media. Limited commercial service of some devices was
introduced in 1962 by Atlas, using the Chevron centralized design, and followed in 1965 by
Schlumberger, using a pad-type tool of its own design. An improved version of the
Schlumberger tool was introduced in 1978. Tool reliability and operational limitations proved to
be major obstacles:

 The tool was not combinable, it required high (surface) power

 The signal level varied geographically and was generally very low as a result of the low-
operational frequency (2 kHz)
 The borehole had to be doped with powdered magnetite to suppress the proton signal
from the mud.

The final version of the Schlumberger NML tool—a centralized tool introduced in 1984—proved
reliable and commercially successful.

In 1978, the Los Alamos Natl. Laboratory developed a logging tool that employed permanent
magnets and used a pulsed radio frequency (RF) (pulse-echo) NMR method. Ultimately, two
wireline tools using different magnet and coil configurations emerged from these efforts:

 Numar’s mandrel device (MRIL)

 Schlumberger’s skid (sometimes called "pad") design [combinable magnetic resonance
(CMR) tool]

Commercial logging began with these tools in 1991 and 1995, respectively. These wireline-tool
designs continue to evolve. Recent improvements allow simultaneous acquisition of more
measurements, operation in a wider range of borehole conditions, and faster logging speeds. In
addition to improvements in wireline tools, new acquisition schemes and processing methods
have improved the resolution, quality, and utility of the acquired data and enabled enhanced
interpretation methods and data analysis.
PRINCIPLE & PHYSICS OF NMR:
The nuclei of all elements carry a charge. When the spins of the protons and neutrons
comprising these nuclei are not paired, the overall spin of the charged nucleus generates a
magnetic dipole along the spin axis, and the intrinsic magnitude of this dipole is a fundamental
nuclear property called the nuclear magnetic moment, µ. The symmetry of the charge
distribution in the nucleus is a function of its internal structure and if this is spherical (ie
analogous to the symmetry of a 1s hydrogen orbital), it is said to have a corresponding spin
angular momentum number of I=1/2, of which examples are 1H, 13C, 15N, 19F, 31P etc. Nuclei
which have a non-spherical charge distribution (analogous to e.g. a hydrogen 3d orbital) have
higher spin numbers (eg 10B, 14N etc) outside the scope of this particular lecture course.

In quantum mechanical terms, the nuclear magnetic moment of a nucleus can align with an
externally applied magnetic field of strength Bo in only 2I+1 ways, either re-inforcing or
opposing Bo. The energetically preferred orientation has the magnetic moment aligned parallel
with the applied field (spin +1/2) and is often given the notation a, whereas the higher energy
anti-parallel orientation (spin -1/2) is referred to as b. The rotational axis of the spinning
nucleus cannot be orientated exactly parallel (or anti-parallel) with the direction of the applied
field Bo (defined in our coordinate system as about the z axis) but must precess about this field
at an angle (for protons about 54) with an angular velocity given by the expression;

wo = gBo ...(1) (the Larmor frequency, in Hz)

g = magnetogyric ratio & relates magnetic moment (m) and spin number (I)) for any nucleus.

g = 2pm/hI ...(2) (h is Planck's constant)

(Pictorial representation of atomic spin)

For a single nucleus with I=1/2 and positive g, only one transition is possible (D I=1, a single
quantum transition)
between the two energy
levels;

NMR is all about how to interpret such transitions in terms of chemical structure. We will first
consider the energy of a typical NMR transition. If angular velocity is related to frequency
by wo = 2¼n, then

n = gBo/2¼ ...(3)

It follows that proton NMR transitions (DI=1) have the following energy;

hn = DE = hgBo./2p ...(4)

For a proton g = 26.75 x 107 rad T-1 s-1 and Bo ~ 2T, DE = 6 x 10-26 J. The relative populations of
the higher (n2) and lower (n1) energy levels at room temperature are given by the Boltzmann
law;

n2/n1 = e-DE/kT ~ 0.99999. ...(5)

For NMR, this means that the probability of observing a transition from n 1 to n2 is only slightly
greater than that for a downward transition, ie the overall probability of observing absorption
of energy is quite small. This relationship also explains why a larger Bo favours sensitivity in
NMR measurements, increasing as it does the difference between the two Boltzmann levels,
and why NMR becomes more sensitive at lower temperatures.

(1) Relaxation Process:

Relaxation processes are defined as different types of radiation-less transitions by which a

nucleus in an upper spin slate returns to a lower spin state. Generally, there are two types of
relaxation processes:

(a) Spin-spin Relaxation:

It is affected by mutual exchange of spins by two processing nuclei in close proximity to each
other.

(b) Spin Lattice Relaxation (lattice term refers to frame work of molecules containing the
processing nuclei):

This process maintains an excess of nuclei in a lower state, which is the essential basic condition
for the observation of nuclear resonance phenomenon.

In a NMR spectroscopy the sharp resonance lines are observed for stales of extended
excitation, and broad lines are observed for short-lived excited stales. Both the processes, spin-
spin relaxation and spin lattice relaxation contribute to the width of a spectral line.

(2) Condition of Resonance Signals:

The atoms like O16 and C12 which have even number of protons and neutrons have no magnetic
moment and hence refuse to give resonance signals. While atoms such as P21, F19, which have
odd number of protons and even numbers of neutrons, if any, generate nuclear magnetic
moments and “hence give resonance signals.

(3) Units of NMR:

The nuclear magnetic resonance values are expressed in any of three ways:

(a) δ-the reference compound be quoted (δ denotes that chemical shift is independent of
oscillator frequency).
(b) Cps — the reference compound must be quoted and the oscillator frequency given.

(c) τ-TMS (tetra methylsilane) or DSS (2, 2 dimethyl-2 silapentane-5 sulphonate) is assumed
independent of both oscillator frequency and reference compound.

Outputs of NMR tools:

Some important outputs of NMR tools are given below:

 Porosity
 Lithology identification
 Gas indication
 Permeability
 Clay content
 Correlation (especially in cased holes)
 Pore space distribution
 Reservoir quality
 Hydrocarbon quality
 Producible fluid and some others
Advantages of NMR

 Only fluids are visible to NMR technology so porosity measurement independent of

lithology.
 Producible zones with high percentage of clay bound-water can identified.
 A better measurement of permeability s possible than traditional plots.
 In-situ measurement of oil viscosity.
 Differentiation of oil/gas zones.
Disadvantages of NMR:

 Any diamagnetic or paramagnetic ions present in the formation can affect the tool
response
 A limitation in using NMR for food authentication (and the most prohibitive one) is the
cost of the equipment. A new 500 MHz NMR spectrometer might cost 7-8 times as much
as a new HPLC/UV-DAD system.
  Another limiting reason is the relatively low sensitivity of NMR compared to other
techniques such as HPLC or GC.
 Slower logging speeds
 Slim-hole tools re not available
 Shallow depth of penetration
 Permeability measurement is actually an empirical measurement and should only be
used to compare to permeabilities.
 NMR is a less sensitive technique compared to MS and hence requires much larger samples for
analysis. MS analysis is routinely carried out in the picogram range.

(Schematic setup for the LC–MS–NMR system)

APPLICATIONS:
Data acquisition in the petroleum industry
One of the important use for nuclear magnetic resonance is data acquisition in the petroleum
industry for petroleum and natural gas exploration and recovery. Initial research in this domain
began in the 1950s, however, the first commercial instruments were not released until the
early 1990s. A borehole is drilled into rock and sedimentary strata into which nuclear magnetic
resonance logging equipment is lowered. Nuclear magnetic resonance analysis of these
boreholes is used to measure rock porosity, estimate permeability from pore size distribution
and identify pore fluids (water, oil and gas). These instruments are typically low field
NMR spectrometers.
NMR logging, a subcategory of electromagnetic logging, measures the induced magnet moment
of hydrogen nuclei (protons) contained within the fluid-filled pore space of porous media
(reservoir rocks). Unlike conventional logging measurements (e.g., acoustic, density, neutron,
and resistivity), which respond to both the rock matrix and fluid properties and are strongly
dependent on mineralogy, NMR-logging measurements respond to the presence of hydrogen
protons. Because these protons primarily occur in pore fluids, NMR effectively responds to the
volume, composition, viscosity, and distribution of these fluids, for example oil, gas or water.
NMR logs provide information about the quantities of fluids present, the properties of these
fluids, and the sizes of the pores containing these fluids. From this information, it is possible to
infer or estimate:

 The volume (porosity) and distribution (permeability) of the rock pore space
 Rock composition
 Type and quantity of fluid hydrocarbons
 Hydrocarbon producibility

The basic core and log measurement is the T2 decay, presented as a distribution
of T2 amplitudes versus time at each sample depth, typically from 0.3 ms to 3 s. The T2 decay is
further processed to give the total pore volume (the total porosity) and pore volumes within
different ranges of T2. The most common volumes are the bound fluid and free fluid. A
permeability estimate is made using a transform such as the Timur-Coates or SDR permeability
transforms. By running the log with different acquisition parameters, direct hydrocarbon typing
and enhanced diffusion are possible.

Medicine:
The application of nuclear magnetic resonance best known to the general public is magnetic
resonance imaging for medical diagnosis and magnetic resonance microscopy in research
settings, however, it is also widely used in chemical studies, notably in NMR spectroscopy such
as proton NMR, carbon-13 NMR, deuterium NMR and phosphorus-31 NMR. Biochemical
information can also be obtained from living tissue (e.g. human brain tumors) with the
technique known as in vivo magnetic resonance spectroscopy or chemical shift NMR
Microscopy.
As one of the two major spectroscopic techniques used in metabolomics, NMR is used to
generate metabolic fingerprints from biological fluids to obtain information about disease
states or toxic insults.
Chemistry
By studying the peaks of nuclear magnetic resonance spectra, chemists can determine the
structure of many compounds. It can be a very selective technique, distinguishing among many
atoms within a molecule or collection of molecules of the same type but which differ only in
terms of their local chemical environment. NMR spectroscopy is used to unambiguously identify
known and novel compounds, and as such, is usually required by scientific journals for identity
confirmation of synthesized new compounds. See the articles on carbon-13 NMR and proton
NMR for detailed discussions.
An example of nuclear magnetic resonance being used in the determination of a structure is
that of buckminsterfullerene (often called "buckyballs", composition C60). This now famous
form of carbon has 60 carbon atoms forming a sphere. The carbon atoms are all in identical
environments and so should see the same internal H field.

Non-destructive testing
Nuclear magnetic resonance is extremely useful for analyzing samples non-destructively. Radio
waves and static magnetic fields easily penetrate many types of matter and anything that is not
inherently ferromagnetic. For example, various expensive biological samples, such as nucleic
acids, including RNA and DNA, or proteins, can be studied using nuclear magnetic resonance for
weeks or months before using destructive biochemical experiments. This also makes nuclear
magnetic resonance a good choice for analyzing dangerous samples.
Acquisition of dynamic information
In addition to providing static information on molecules by determining their 3D structures in
solution, one of the remarkable advantages of NMR over X-ray crystallography is that it can be
used to obtain important dynamic information.
Process control:
NMR has now entered the arena of real-time process control and process optimization in oil
refineries and petrochemical plants. Two different types of NMR analysis are utilized to provide
real time analysis of feeds and products in order to control and optimize unit operations. Time-
domain NMR (TD-NMR) spectrometers operating at low field yield free induction decay data
that can be used to determine absolute hydrogen content values, rheological information, and
component composition. These spectrometers are used
in mining, polymer production, cosmetics and food manufacturing as well as coal analysis. The
variation observed in these spectra with changing physical and chemical properties is modeled
using chemometrics to yield predictions on unknown samples. The prediction results are
provided to control systems via analogue or digital outputs from the spectrometer.
Earth's field NMR
In the Earth's magnetic field, NMR frequencies are in the audio frequency range, or the very low
frequency and ultra low frequency bands of the radio frequency spectrum. Earth's field NMR
(EFNMR) is typically stimulated by applying a relatively strong dc magnetic field pulse to the
sample and, after the end of the pulse, analyzing the resulting low frequency alternating
magnetic field that occurs in the Earth's magnetic field due to free induction decay (FID). These
effects are exploited in some types of magnetometers, EFNMR spectrometers, and MRI
imagers. Their inexpensive portable nature makes these instruments valuable for field use and
for teaching the principles of NMR and MRI.
An important feature of EFNMR spectrometry compared with high-field NMR is that some
aspects of molecular structure can be observed more clearly at low fields and low frequencies,
whereas other aspects observable at high fields are not observable at low fields. This is
because:

 Electron-mediated heteronuclear J-couplings (spin-spin couplings) are field

independent, producing clusters of two or more frequencies separated by several Hz,
which are more easily observed in a fundamental resonance of about 2 kHz."Indeed it
appears that enhanced resolution is possible due to the long spin relaxation times and
high field homogeneity which prevail in EFNMR.
 Chemical shifts of several ppm are clearly separated in high field NMR spectra, but have
separations of only a few millihertz at proton EFNMR frequencies, so are usually lost in
noise etc.
Zero field NMR
In zero field NMR all magnetic fields are shielded such that magnetic fields below 1 nT
(nanotesla) are achieved and the nuclear precession frequencies of all nuclei are close to zero
and indistinguishable. Under those circumstances the observed spectra are no-longer dictated
by chemical shifts but primarily by J-coupling interactions which are independent of the
external magnetic field. Since inductive detection schemes are not sensitive at very low
frequencies, on the order of the J-couplings (typically between 0 and 1000 Hz), alternative
detection schemes are used. Specifically, sensitive magnetometers turn out to be good
detectors for zero field NMR. A zero magnetic field environment does not provide any
polarization hence it is the combination of zero field NMR with hyperpolarization schemes that
makes zero field NMR attractive.