A New Generation Mud-Hammer Drilling Tool Annual Report
A New Generation Mud-Hammer Drilling Tool Annual Report
A New Generation Mud-Hammer Drilling Tool Annual Report
Annual Report
D. Pixton (dpixton@novatekonline.com; (801)374-2755)
Hall (dhall@novatekonline.com; (801)374-6222)
Novatek, Inc.
2185 South Larsen Parkway
Provo, UT 84606
Abstract
The economic and strategic significance of drilling technology has prompted the oil
& gas industry to seek for new drilling tools and systems that increase both the rate and
efficiency of drilling wells. Interest is focused on short-term improvements to drilling rate,
particularly in hard rock formations, as well as on the longer-term development of and
integrated “smart” drilling system. Over the past several years, a novel tool that addresses
both of these issues has been developed. This tool, a mud actuated down-hole hammer
drill, is designed to provide increased rate of penetration. In addition, this tool may be
used as the central engine of an integrated drilling system, providing for electricity, data
transmission, high-pressure mud jets, self-powered rotation, geophysical sensing, and
steering.
At the commencement of the present contract, previous research had verified that
the hammer tool could operate in deep, inclined gas wells, using a weighted drilling mud.
However, improvements were shown to be needed in the life of the tool, the level of
impact energy generated, and the effectiveness of transmitting this energy to the rock
formation. Hence, the present investigation focuses on two primary objectives:
• Determining design and operating parameters of the hammer which will result in
the greatest improvements in drilling rate, and
• Determining appropriate materials and design features which will optimize the
operational life of the hammer.
To date, laboratory testing of a higher energy prototype hammer has shown that an
increase in penetration rate can be obtained, even when using a standard roller-cone bit.
However, the level of increase is dependent on drilling conditions, particularly, weight-on-
bit and the depth of the borehole. The current prototype has produced rate of penetration
increases in Carthage limestone of up to 75% in simulated shallow wells (600 ft), and 10%
in deeper wells (6000 ft). Where weight on bit is constrained to under 10,000 lbf (for
example, in extreme crooked hole territory), penetration rate increases over conventional
drilling of 300% have been observed.
1
Further improvements in hammer effectiveness are currently being pursued in the
following areas:
The ultimate goal of the mud driven hammer developments is to provide a down-
hole power source for future “smart” drilling systems.
2
Introduction
The economic and strategic significance of drilling technology has prompted the oil
and gas industry to seek for new drilling tools and systems that increase both the rate and
efficiency of drilling wells. Interest is focused on short-term improvements to drilling rate,
particularly in hard rock formations, as well as on the longer-term development of and
integrated “smart” drilling system.1 One advanced down-hole drilling system with the
potential of addressing each of these areas is a down-hole hammer. This tool converts a
portion of the power resident in the drilling fluid into mechanical impacts directly upon the
drill bit, thus driving the drill bit into the formation. This percussive action has the effect
of increasing the instantaneous weight on bit (WOB), even though the mean WOB may be
kept at typical or below than typical levels for drilling. The end results of this action are
that the penetration rate of the drill bit may be increased, drill bit life may be increased,
and unplanned borehole deviation may be decreased. Each of these results offer economic
benefits in terms of reducing drilling time by improving productivity during drilling and
reducing costly down-time.
Several down-hole hammer tools are commercially available for boreholes where it is
possible to use air as the drilling fluid. Such hammers have been able to improve upon
drilling rate by a factor of two or three in certain rock formations. Over the past twenty
years, several hammer drills have also been developed which utilize water or water and oil
as the working fluid. Such hammers are typically used in mining applications, where use
of clean water is acceptable. However, in wells where mud is the drilling fluid of choice,
no economically viable down-hole hammer exists.
Mud actuated hammer developments. The large potential commercial benefit of a
down-hole mud actuated hammer has motivated several development efforts over the last
fifty years. Two basic design approaches have been taken: the design of a “native” mud
system, and the conversion of a water-actuated system to mud. The former of these
approaches begins the design process with a consideration of the peculiarities of drilling
mud, while the latter attempts to build upon existing technologies in use in other
applications. While the key in both of these approaches is to successfully utilize a non-
ideal drilling fluid (one which is highly abrasive, contains particulates, and is designed to
clog small fluid passages), the former allows such issues to be addressed from a very
fundamental level – from the basic design of the cycle and valving scheme used by the
tool.
An appreciation of the non-ideal nature of mud as an operating fluid has be gained
over the past four decades of development efforts. Though previous efforts tallied
substantial gains in drilling effectiveness, these efforts failed because of clogging of
________________________
Research sponsored by the U.S. Department of Energy’s Federal Energy Technology Center, under
contract DE-FG03-95ER82042 with Novatek, 2185 South Larsen Parkway, Provo, UT 84606; telefax:
(801) 374-6009.
3
reciprocating members, valve and valve seat wear, deleterious effects of “water hammer”%
on borehole stability and mechanical parts, and premature failure of dynamic mechanical
elements such as springs and seals. 2 ,3,4,5 Current international efforts to convert water-
driven mining tools to the mud environment are likewise being hampered by high erosion
of critical surfaces and clogging of the hammer mechanism.
To minimize these problems, a “native” mud-actuated hammer system has been
designed and built. 6 ,7 Figure 1 shows schematically this tool and its mode of operation.
Basic operation of the tool begins with the tool positioned as shown in Figure 1a. In this
condition, pressurized mud is allowed to flow along the outer path into the upper and
lower chambers as shown. Mud pushing against the large surface in the lower chamber
moves the hammer upward, overcoming the force of the mud pushing against the smaller
surface in the upper chamber. Upward movement of the hammer causes the valve to
move upward until it shuts off flow to the lower chamber as shown in Figure 1b. Mud is
next allowed to exhaust from the lower chamber, causing a net force imbalance
downward. This force acts to slow the upward movement of the hammer and return it
towards its beginning point as shown in Figure 1c. Figure 1d shows the hammer at its
impact point, where the momentum of the valve resets it to its beginning point.
The tool just described is fitted with a hydraulically assisted mechanical shuttle valve.
As mentioned above, this valve is mechanically constrained to move in concert with the
primary motion of the hammer. Therefore, the large forces that move the hammer also
move the valve, thereby reducing the risk of fouling. In addition, the valve is also livened
by hydraulic forces, which tend to prevent dwelling of the valve, even in a particulate
environment. These features, along with the sliding/shearing motion of the valve shown in
Figure 1, minimize the tendency of the valve to become fouled by the drilling mud.
Other design features of this tool have focused on other design weaknesses of
previous attempts. In particular, the tool employs no dynamic springs or seals. Also, to
minimize deleterious “water hammer” effects, the tool utilizes only a portion of the total
flushing flow of mud to effect percussion. The remainder of the flow is allowed to pass
directly to the drill bit, without dropping pressure across the tool, for bottom-hole
cleaning. This is known as “in-parallel” hammer operation.
Objectives
At the commencement of the present work, previous research had verified that the
new generation hammer tool mentioned above could operate in deep (>4000 m, >13,100
ft), inclined gas wells, using a weighted (1.7 kg/L, 14 lbm/gal) drilling mud. The
robustness of the above mentioned cycle has also been shown in preliminary testing: the
hammer was faithful in above-ground operation over a period of at least fifty hours in a
weighted drilling mud with solids. However, this initial testing determined that
improvements were necessary in the life of the tool, resetting the tool after stopping flow,
%
“Water hammer” is a sudden increase in fluid pressure that results most typically from suddenly stopping the
movement of a quantity of incompressible fluid. Such is typical with a liquid driven hammer, wherein the
liquid driving the hammer undergoes sudden changes in direction as the hammer reciprocates.
4
the level of impact energy generated, and the effectiveness of transmitting this energy to
the rock formation. 8 Hence, the present investigation focuses on two primary objectives:
• Determining design and operating parameters of the hammer which will result in
the greatest improvements in drilling rate, and
• Determining appropriate materials and design features that will optimize the
operational life of the hammer.
The goal of these two objectives is to improve the benefit/cost ratio of the tool so
as to provide economic viability.
Approach
To accomplish these overall goals, a systematic study has begun with primary
focus on characterizing and improving the effectiveness and life of the current mud-
actuated hammer design. Three basic areas related to hammer effectiveness and life are
being addressed in this study: system design, wear materials, and bit design.
System design. Hammer output parameters such as the energy, frequency, and
peak force or velocity of hammer blows, as related to the characteristics of the rock
formation being drilled are of particular interest in optimizing the effectiveness of the tool.
Both physical and operational parameters combine to produce the output parameters
above. The pressure of the working fluid and the access of flow to the workings of the
tool are key operational parameters which may be altered during drilling to change energy
and frequency of hammer blows. Physical parameters, such as the geometry and mass of
the hammer, the geometry, stiffness and mass of the drill bit used, and the stroke of the
hammer may likewise be optimized, although not real-time while drilling.
Of a necessity, the consideration of system design implies an ever-improving model
of the hammer. This model includes fundamental mathematical models, as well as a
database of experience with the tool. Of particular interest is the cataloging of drilling
parameters vs. effectiveness in various formations.
Wear materials. As already described a key life and performance-limiting factor
for a down-hole mud-actuated hammer is the effect of the abrasive mud on critical valve
surfaces. Focus in this area is primarily upon hard-facing materials, which enhance the
wear resistance of these surfaces. Of secondary interest are materials and treatments that
help improve the life of impact surfaces. Since all surfaces of a down-hole hammer are
typically bathed in the working fluid, impact surfaces are particularly susceptible to erosive
damage from fluid quickly voiding across the surface just prior to impact. These areas of
focus are critical to the overall economic success of the hammer design.
Bit design. In past development efforts, high-energy hammer drills have broken
welded tri-cone bits. Even when such bits do not fail during hammer drilling, they do not
transmit impact energy ideally. This fact is due to the complexity and the relatively high
5
compliance of a tri-cone bit.% Historically, to compensate for this problem and provide a
more effective application of the hammer impact to the rock being drilled, fixed-cutter,
flat-faced, button bits were developed. However, this type of bit has the disadvantage that
it cannot be used under heavy weight on bit, nor can it be used to ream a tapered hole.
Under heavy axial load, the button cutters or the bit head on a flat faced bit will typically
fail.
It is the authors’ thesis that hammer drills will offer the best gains, particularly in
deep or horizontal wells, if rotary drilling mechanisms as well as percussive drilling
mechanisms are allowed to be operative. In this case, improved penetration due to
hammer impact is followed directly by a shear removal of damaged rock. Hence, in deep
wells where rock formations typically act more plastic due to a high pressure head, the bit
is not relying solely on axial indentation for penetration. Also, in formations where soft
rock is interbedded with hard, pure percussion drilling is not effective, so a rotary element
is of great benefit. Such drilling is known as “rotary-percussion” drilling, as opposed to
percussion or hammer drilling, wherein cutters are simply indexed between hammer blows,
without providing significant rotary drilling action. The present tool’s in-parallel mode of
operation, in combination with rotary-percussion drilling carries with it an added benefit
that the hammer may be modulated or turned on and off to give a particular drilling
performance, tailored to rock formation. Also, with rotary-percussion drilling and in-
parallel operation, drilling need not stop should the hammer fail to operate – it may
continue using rotary mechanisms until a satisfactory time is reached to trip the drill string.
This overall area of focus is expected to significantly improve the efficiency of
energy transfer between hammer and rock and improve particularly deep well drilling.
Each of the above areas of research is fed by continued desk studies, laboratory
evaluations and field testing.
Project Description
Test bed. To accomplish the above research, a second generation prototype
hammer tool (referred to as “N4”) has been designed and built. This tool embodies two
fundamental improvements over earlier prototypes: a capacity to generate higher impact
energy levels, and a hammer which is more optimally matched in mass to the bit that it is
driving. These features permit a greater range of test parameters, while fundamentally
improving the efficiency of energy transfer to the drill bit.
Optimization of system design. Analysis of the operability and effectiveness of
the prototype tools under different sets of operational and physical parameters is
accomplished primarily through instrumented drilling tests. Initial emphasis of the current
project has been placed on optimizing the new hammer’s drilling effectiveness. The
primary success criterion for this optimization process is a measure of hammer tool drilling
rate as compared to a conventional drilling system operating at the same hydraulic
horsepower. Economic advantage is expected to accrue once the hammer increases
%
In this work, the apparent compliance of an 8½-inch tri-cone rock bit was measured to be approximately 4
times that of the striking hammer.
6
drilling rate by a factor of 1.2 to 1.6, depending on the type of rock and cost of rig.9 This
factor is also sensitive to the usable life of the tool, as will be detailed later.
Of first interest is the effectiveness of the tool in rock formations that are typically
difficult to drill using conventional procedures, but which are likely to be encountered in
drilling for gas. Hence, laboratory tests have focused on rocks such as Carthage Marble,
and Crab Orchard Sandstone.
Figure 2 depicts the equipment and setup used in a typical simulated borehole test
at the Terratek Drilling Research Laboratory in Salt Lake City, Utah. This site has been
used for initial quantification and optimization work because of its convenient location and
its ability to provide identical drilling conditions repetitively. This work has been fed and
supported by instrumented flow tests under atmospheric conditions. Such tests offer a
lower cost means of verifying tool operation and putting operating hours on the tool;
however, more importantly, such tests allow iterations which cannot be done while
drilling. For example, during a recent flow test, a means of quickly modifying the stroke
of the hammer, using servo positioning of the test rig, was employed to investigate the
sensitivity of the hammer to variability in its impact point. Such simplified flow tests have
also permitted the use of specialized position sensors that assist in gaining an
understanding of the operation of the tool. Figure 3 shows the output of such a sensor,
depicting the time record of a non-impacting cycle of the N4 hammer.
Other test objectives. The new N4 tool has been the primary vehicle for learning
to date, and will continue to assist the optimization process during the course of the next
year. However, other hammer prototypes will be built as more intensive field studies are
implemented later in the program. Inasmuch as a primary goal for the remainder of the
program is to obtain field experience and exposure of the new design, further use of
previous prototypes is also expected for suitable less severe applications. Such usage will
assist in gaining experience with the tool and in improving wear materials. Each field or
laboratory test iteration offers an opportunity to improve and evaluate wear resistant
materials. Indeed, one parameter that will be closely monitored in such tests will be wear
or other damage to critical tool regions.
Results
Original prototype. Recent laboratory testing has yielded comparative data that
has quantified the potential drilling benefits of the original prototypes. Figure 4 shows the
rate of penetration of a conventional drilling system and the original new-generation
prototype hammer drilling system as a function of WOB. This data is reported for drilling
in Carthage Marble under shallow hole conditions (a simulated hole depth of 200 m, 600
ft) and at near maximum hammer impact levels. As shown, a nearly linear relationship
exists between WOB and rate of penetration (ROP). Other more thorough studies of
conventional drilling have been able to model this relationship reasonably well with a
single line or a double-sloped line with a breakpoint near 65 kN (15,000 lbf) WOB.10, 11
This linear behavior is to be expected, since applying WOB is the mechanism for applying
drilling energy to the hole bottom. However, when the original prototype hammer is
added into the drilling system, the slope of the ROP vs WOB curve does not fall off as
rapidly as the conventional drilling curve. Hence, Figure 4 shows a cumulative effect of
7
rotary and percussive drilling mechanisms. This supports the authors’ thesis that a rotary
percussion drilling system may have advantages over pure percussion drilling systems. At
even lower WOB than that tested in this study,% it is expected that the slope of the ROP vs
WOB curve will approach the horizontal, as the drilling energy supplied by rotary drilling
mechanisms becomes insignificant and percussion energy dominates the process.
It should be noted that at high WOB, comparable to that most often used in
drilling, the original prototype does not supply enough additional energy to significantly
improve drilling rate. However, at low WOB, the original prototype improves drilling rate
by as much as a factor of three. Physical circumstances which could lead to such WOB
constraints include crooked hole territory, and shallow or horizontal wells. Hence, this
data points out the ineffectiveness of the initial prototypes under common drilling
conditions, but indicates possible application to special drilling applications.
Higher energy prototype. As mentioned, this apparent underpowering of the
original hammer tools has led to the development of the N4 prototype. Successful
operation of this significantly larger tool has been verified in both atmospheric and
simulated borehole conditions (simulated depths of up to 6000 ft). This success has given
a first indication that the current design may be scaled for different drilling applications
(e.g., scaled up further for larger wellbores, scaled down for possible application to
slimhole drilling).
Figure 5 shows the improvement in ROP offered by the N4 design, as compared to
conventional drilling. The data reported is for drilling in Carthage Marble. In this figure,
hammer energy level increases with the pressure drop at the bit (shown on the abscissa).
Three different simulated down-hole conditions are also represented: 2070 kPa (300 psi),
6900 kPa (1000 psi), and 20700 kPa (3000 psi) borehole pressure. These pressures
roughly correspond to 200 m (600 ft), 650 m (2000 ft), and 2000 m (6000 ft) drilling
depths. As shown in this figure, the improvement in ROP offered by the hammer increases
with hammer energy. Increases as high as 75% over conventional drilling can be seen for
low borehole pressures. Though exhaustive data is not available at higher borehole
pressures, there is also a distinct trend towards decreasing hammer effectiveness with
increasing drilling depth. As shown, the hammer at 2000 m (6000 ft) simulated depth
produces only a 12% increase in ROP under the same operating parameters which
produce a 53% increase in ROP at 200 m (600 ft) simulated depth. The hammer does not
appreciably change its operating characteristics at higher borehole pressures. Therefore,
the change in hammer effectiveness may be attributed to effects of the higher borehole
pressure on the rock. Such effects have been documented for conventional roller-cone
drilling.12
One means of improving the above-mentioned performance of the N4 tool is to
improve the efficiency of the tool. Inspection of the hammer’s sliding surfaces after this
testing suggested that the actual hammer stroke was not what was expected. Indications
were present that suggested the hammer was short-cycling, i.e., the hammer was
decelerating just prior to impact, reducing the velocity of impact, and therefore reducing
%
This study was limited by the ability of the drill rig to maintain WOB at levels less than 10,000 lbf with the
hammer operating.
8
the effectiveness of the tool. Further investigation wherein the time history of the hammer
position was measured verified this notion. Referring to Figure 6, it can be noted that the
peak velocity (the steepest slope of the position curve) occurs approximately 4.8 cm (1.9
in) above the normal impact point of the tool. As shown, the slowing of the hammer prior
to impact in this particular case is approximately 55%. This represents a large source of
inefficiency of the present tool.
Work subsequent to the testing just mentioned has focused on means of removing
this inefficiency and thereby obtaining greater hammer performance. This work has
determined that simple modifications to the hammer’s valve may reclaim a significant
portion of the lost energy. Preliminary flow testing has verified the feasibility of this
approach. Quantitative drilling tests will follow.
One other significant observation of the current testing program is that the wear of
the hammer valve must be improved to give economic life of the tool. Figure 7 shows
typical wear of the valve. As can be seen, the areas most affected by the abrasive nature
of the drilling fluid are the edges of the valve. As these areas wear, leakage through the
valve increases which worsens the short-cycling problem mentioned above and leads to
lower hammer effectiveness. Tool life may be extended by increasing the wear resistance
of the valve and by decreasing the operating pressure of the hammer.
Benefits
Comparison of the effectiveness of the N4 prototype with earlier versions of the
same overall design indicates that the impact energy levels and the improved energy
transmission offered by the N4 design have certainly improved the drilling effectiveness of
the tool. More improvement is necessary before the tool produces economic benefits for
deep well drilling (high borehole pressure). Estimates of drilling performance of such a
tool show a 20% to 60% increase in ROP, along with a useful hammer life of 720 hours (6
repair cycles anticipated) is needed for the tool to be cost effective.
While this goal is being pursued, current and previous prototypes have the
potential to provide immediate economic benefits to drilling in special applications, such as
shallow and WOB limited wells (crooked-hole, horizontal wells, etc.). Though these latter
applications are not the ultimate target of the current research, such will undoubtedly
assist the learning process by providing experience operating the tools, and opportunities
to field test new materials, new design features, etc.
Beyond the present focus of improving drilling effectiveness, a hammer operating
down-hole may also be used for a number of other functions, much like an automobile
engine is used to drive auxiliary devices such as an air conditioning unit, a water pump,
and an alternator. For example, one particular application that is being developed using an
air hammer is a steerable drilling device that provides down-hole rotation by the recipro-
cation of the hammer.13 Other possible applications of the reciprocating motion of the
hammer include using impacts as an exciter for sonic look-ahead measurements, down-
hole electricity generation, instantaneous geophysical measurements (using the rebound of
the hammer as a transducer for such), and down-hole high-pressure jet intensification.
Such collateral uses of the hammer further improve the benefit/cost ratio of the hammer.
9
Future Activities
Focus in this research remains on improving hammer effectiveness and life.
Further improvements in hammer effectiveness are currently being pursued in the
following areas:
• Cycle Efficiency. The test results discussed above show that the effectiveness
of the current hammer is limited by inefficiencies in its cycle, which cause
premature slowing of the hammer prior to impact. Further optimization of the
hammer valve has begun to improve hammer efficiency. Efforts continue in the
characterization and optimization of the hammer cycle.
• Efficiency of Energy Transfer. It should be noted that each of the drilling
tests reported above have used a standard roller cone bit. As already described,
such a bit is non-ideal for transferring impact energy to rock, although it
preserves the ability to effectively use rotary drilling mechanisms to enhance
percussion mechanisms. A fixed cutter bit, which allows significant rotary
drilling, is seen as ideal for this application.
A common PDC drag bit may lend itself well to this application, and will be
evaluated for this purpose. However, an off-the-shelf bit may not be robust
enough for percussive drilling. Also, a standard bit would need to be connected
to the hammer tool via a rotary-shouldered connection, which attenuates the
impact signal generated by the hammer. For these reasons, a new, fixed cutter
rotary-percussion bit, using advanced polycrystalline diamond inserts, is
currently being considered. New polycrystalline diamond inserts,14 which give
twice the impact resistance of a common PDC bit insert, have been developed
for this bit. Figure 8 displays the basic design of this new insert.%
Figure 9 is a rendering of a promising new bit design. This bit is currently
being developed in a related research project† for use in a jet-assisted
mechanical drilling application (see below), and lends itself well to the current
effort. Unlike common flat-head button bits used in air hammer drilling, the
goal of this new design is to be able to drill interbedded hard and soft
formations, and will be able to exploit rotational drilling energy as well as
percussive energy. Pending final analysis of the cutter pattern by Sandia
National Laboratories, this new bit will be manufactured and tested in future
hammer studies.
• Integration of Advanced Drilling Mechanisms. In cooperation with other
research efforts, the benefits of integrating high-pressure mud jet technology
with rotary-percussion drilling technology is being investigated. Figure 10
shows the basic components of such a system. As shown, this system exploits a
synergistic action between rotary-percussion drilling and high-pressure jet
scouring of the rock surface. In addition, the life of the diamond cutter is
extended due to enhanced cooling of the cutter. Such a system has been shown
%
Patent pending.
†
DOE Grant DE-FG03-96ER82242
10
in recent research to potentially double the ROP of a non-integrated drilling
system.15 These findings have also shown particular benefit to using jet-assisted
drilling with percussive modes of drilling. Hence, this integration is expected to
have particular benefit in deep drilling applications, where hammer drilling
effectiveness is lessened.
Improvements in hammer life are primarily being sought in the following area:
• Materials Improvements. Currently, the valve is protected by a proprietary
tungsten carbide coating. Advanced coating materials, including other tungsten
carbide based coatings and polycrystalline diamond, are being investigated in
high wear regions of the hammer to give improved service life. Super materials,
such as polycrystalline diamond, are expected to be key to achieving the
longevity required for optimal economic service. Figure 11 conceptually
displays an enhanced hammer valve.
Once the above objectives are met, an effective drilling tool will be available to
industry. On a grander scale, it is likely that the usefulness of the down-hole mud-
actuated hammer will extend much farther than this - this tool may conceivably be used as
the central engine of an integrated “smart” drilling system, providing for down-hole
electricity, data transmission, high-pressure mud jets, self-powered rotation, geophysical
sensing, and steering. The system envisioned is shown in Figure 12.
Acknowledgement
The authors wish to thank Mr. Al Yost of the FETC for his support and
permission to publish this paper.
References
1
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"New 'Hammer' Bit Ups Penetration Rate 5 Times." Offshore (June 5, 1968), p. 23.
3
Finger, J.T. "Investigation of Percussion Drills for Geothermal Applications." Journal
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4
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5
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11
7
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8
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9
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10
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11
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(Dec. 1989).
12
Walker, B.H, A.D. Black, W.P. Klauber, T. Little, and M. Khodaverdian, “Roller-Bit
Penetration Rate Response as a Function of Rock Properties and Well Depth,” in
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Petroleum Engineers, SPE 15620, New Orleans (Oct 5-8, 1986).
13
Bui, H., “Steerable Percussion Air Drilling System,” DOE Contractor Review Meeting,
Baton Rouge (April 4-6, 1995).
14
Hall, H.T. Jr., D.R. Hall, “Carbide/Metal Composite Material and a Process Therefor,”
U.S. Patent 5,304,342 (Apr. 1994).
15
Unpublished work done at the University of Missouri-Rolla, in cooperation with
Novatek under Department of Energy Grant DE-FG03-96ER82242.
12