SOCIETYOF PETROLEUMENGINEERSOF AIM3

6200 North CentralExpressway %i%RSPE 4220

Dallas,Texas 7Y_?06

THIS IS A PREPR”~T--- SUBJECTTO CORRECTION

A Review of Corrosion Monitoring Techniques

By

D. R. Fincherand A. C. Nestle,MembersAIME, FincherEngineeringCo.

@ Copyright 1972
American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc.

This paper was preparedfor the Symposiumm the Handlingo.C OilfieldWaters of the Societyof
?etroleuwEngineersof AIME, to be held in Los Angeles,Calif.,Dec. 4-5, 1972. Permissionto &PY
is restrictedto an abstractof not more than 300 words. Illustratiofismay not be capied. The
abstractshouldcontainconspicuousacknowledgmentof where and by Iihomthe paper is presented.
publicationelsewhereafter publicationin the JOURN./ILOF PETROLEUMTECHNOLOGYor the SOCIETYOF
PETROLEUI.1
ENGINEERSJOURNALis usuallygrated upon requestto the Editorof the appropriate
jcurnalprovidedogreementto give proper credit is made.

~isc~ssionof this paper is invited. Three copiesof any discussionshouldbe sent to the
Societyof Petroleuml?mgineers office. Such discussionmay be presentedat the above meetingand,
.,.;ith
the paper,
. . ,Paybe consideredfor publicationin one of the two SPE m~Eazines.

ABSTRACT Perhaps the most desirable monitoring

techniques are those that are used more
Operators of metallic systems have or less continually to determine the
been aware of the damage that is, or can rate of corrosion attack. These methods
be, caused by corrosion processes for also are suitable to assess the success
many years. The search continues for or failure of the corrosion mitigation
new and better tools to monitor, measure, measures used. Such devices include
or detect changes both in the metal coupons, linear polarization type
structure itself and in the rate of instruments, electrical resistance type
attack that the structure is experienc- instruments, galvanic probes and hydro-
ing. To prevent corrosion damage, it is gen probes. Also, a new corrosion
necessary to know when, where, and why mo,litor-controller is described.
the attack is occurring. Otherwise,
damage can occur before the owr.er has Each of the methods has certain
knowledge of the attack. advantages and disadvantages, and this
paper reviews the practical application
Corrosion can be monitored or of all of these different techniques.
detected using “after-the-fact” type
tools for detection. Perhaps the oldest INTRODUCTION
detection technique is simply a visual
inspection coupled with measurement of The field of corrosion detection
pit depths and/or w-all thickness. and control monitoring can be categor-
Ultrasonic and X-ray equipmsnt also can ized conveniently in four parts. These
be used to determine the extent of are: (1) “After-the-fact” methods
damage. Downhole tubing and casing including Equipment Service Records,
calipers, possibly in conjunction with direct and indirect physical examina-
wall thickness measureri.ents,can be tion, “inspection” of the equipment;
used periodically to assess the extent (2) Non-destructive testing methods
of corrosion damage. usable without shut down, i.e., not
necessary to open-up the equipment; (3)
“Probing” methods, using devices to
References and illustrations at end of probe the system, a pilot small scale
paper. system, an alternate (by-pass) system,
 ONITORING TECHNIQUES sP13 422

m laboratory testing, checking with more expense, even capital investment

~oupons or pro,bes, and (4) Corrodants too, besides what the patching or re-
and corrosion products, their sampling,, placement entails. Also, if breaks,
handling analyses and interpretation of leaks and other failures trigger the
the data. need for corrosion control, there will
be a lot more of the same unless every
The choice of categories is based piece of equipment is replaced, as there
on the philosophy that producing opera- may be and probably is much more of the
tions, 1972, require corrosion detection equipment nearly corroded through. Even
to be done with skill and experience if corrosion control on the remaining
with minimum interference to production equipment is started and is close to
and at low cost. The first category, 100% effective, in time the slight cor-
“after-the-fact” is all to often synon- rosion, or some undue severe shock may
ymous with “too-little-too-lake” unless result in leaks, breaks or failures of
the corrosion engineer(s) involved have some of those near-through areas.
had skill, experience, and have a chance Unless and until our technology can re-
to use them, plus, usually some good place lost metal and restore original
fortune. All of this, hopefully, can be strength and thickness as well as fill
done to avoid repetition of the early all pits, etc., we will have the un-
fifties, when some spectacular failures happy and unsafe possibility of trouble
of oil field equipment, often catastro- on corroded equipment which was “dis-
phic, caused loss of property and focus- covered” by leaks and breaks occurring.
ed attention on the need for effective There may be exceptions to this general-
corrosion detection, monitoring, and ity, such as the occurrence of leaks or
control. History should not repeat, now breaks by more severe and abrupt types
we have governmental regulations involv- of corrosion like stress-corrosion-
ed and ecology protection is emphasized. cracking, hydrogen embrittlement, etc.
These are the most dangerous and it is
The last three categories, actually even more important and vital that
the first in importance, can be done corrosion detection and monitoring be
without shut-down, provided some advance implemented which will forewarn of
planning has been utilized effectively impending disaster, catastrophic fail-
to equip the wells with the necessary ures, blowouts, etc. in time to avoid
taps and access fittings, etc. If them.
producing operations had scheduled shut-
downs (“Turnarounds”) like chemical Much can be learned from careful
plants and refineries, it might be inspection by all available means of
simpler. Since it is usually ran.3om any corroded equipment which is or can
opportunity to install the necessary be opened without undue expense or loss
fittings, one must PLAN AHEAD, see that of production or operations shutdowns.
new wells or systems will be completely While it may be after the fact and too
equipped, and be ready to work fast late to remedy some of it, drastic
should wells be shut-in. measures may be necessary and the infor-
mation obtained from the inspection can
The first category deals with be vital in assuring that it will not
direct examination of corroded equip- re-occur.
ment, i.e., “after-the-fact’’--all too
often due to too little corrosion con- AFTER-THE-FACT INSPECTION
trol, too late. It is most unfortunate
to have the need for corrosion control Equipment Service Records
and the price for its lack brought
forcibly to mind by leaks and equipment A great deal can be learned about
breakdown. It is more than unfortunate corrosion and corrosion control by dil-
if this results in loss of property, igent study of equipment service
damage to the environment or casualties. reaordsl if the records aye based on
Not only may that bring the censure of valid and careful inspection of the
civic bodies but it may also cause much equipment. Quoting from Junkin’s2
 29
~E 4220 D. R. FINCHER an A. C. NESTLE

>aper: “without queskion, the system- reconstruct what has been taking place
atic reporting of equipment failures and should be obtained and correlated with
:he electronic processing of data tO other information as to treatments, and
place this information in a useful form ! all secondary type data to improve the
are a good investment of the small value of the monitoring overall, past,
~mount of time and money required. Pos- present and future.
itive management support gave the neces-
sary initial momentum to this program. Emphasis on the necessity of care-
Since then the program has been largely ful and thorough “detective” work is
self sustaining as field personnel have well stated in Byars 3 “Equipment Records
become aware of its usefulness in solv- and Histories” section of his paper,
ing current problems and +n reducing the “Corrosion Detection and Control
probability of future problems. Monitoring” . Excerpts from the Intro-
duction and Summary of Byars’ paper
“Engineering and management have follow: “The prime objective of cor-
used Equipment Failure Summaries to (1) rosion detection is to establish the
quickly detect problem wells and highly severity of corrosion before damage
localized problems on which there is a occurs-- monitoring is required to estab-
quick return for corrosion control ex- lish that conditions have not changed
penditures, (2) tre,in personnel to and/or that control efforts are satis-
better understand occurrences and causes factory. A failure is often the first
of equipment failures, (3) evaluate warning of a corrosion problem. The
routine corrosion control measures, and push is to get back on production.
(4) make annual or other scheduled Since it is impossi’~le to determine the
reviews of the overall corrosion control most economical approach on short
proqram to determine where and how this notice, the control is often selected
program can be made more effective. based on ‘Justification by Panic’. Btit
it does not have to be this way because
“Obviously the emphasis has been detection and monitoring programs can
placed on the useful application of help avoid such predicaments. In
electronically processed data, not on Smnmary: (1) Corrosion detection and
the mechanics of data processing. This monitoring are extremely important parts
is where the emphasis belongs. It is, of corrosion control.. (2) No single
in fact, the responsibility of the detection and monitoring technique can
corrosion engineer to properly use this be used to tell the full story. (3)
technological tool to improve profits Many approaches to detectioil and moni-
through more effective corrosion toring are available, including:
control.” Records and histories, corroding speci-
mens, chemical analysis, electrical
Direct Inspection measurements and inspection. (4) Field
conditions are continually changing and
Inspection to implement the care- you must follow your corrosion control
ful examination of all available equip- programs for maximum effectiveness. (5)
ment at every opportunity enables the Corrosion control is an important part
corrosion engineer to obtain valuable of achieving maximum profit Srom your
direct evider?ce concerning the corrosion company’s operations.”
and its control. Here is where team
work of all availabie experts in met- Direct examination. inspection, of
allurgical corrosion and chemical fields all.equipment after periods of service
should be concentrated to obtain the can provide useful information, and the
maximum amount of information any and need for corrosion control, e~pecially
every time any piece of oil field equip- if the inspection can be done on any
ment is opened up and becomes available. regular scheduled basis and is not
The appearance of the metal, scales, necessitated due to breakdown. The
corrosion products, scoured, eroded Or equipment can be examined carefully
abraded surfaces and their location, visually, measured with micrometers for
every bit of evidence that may help ko wall thickness and pit depth and any
 )NITORING TECHNIQUES _ SPE 422{
—

:elltale corrosion patterns noted. There film, receivers or sources (for radio-
lay be some pieces of the equipment whick graphic) to the external surface of the
:annot be excmined minutely without de- ?ortion of the equipment to be measured.
stroying their usefulness. Sometimes ?lammang4 describes the devices and
:he information that might be gained their operation as follows:
:rom “destructive” testing may be worth
;he expense. Ultrasonic

Indirect Inspection
—. Ultrasonic transmitters for non-
destructive testing consist of flat
Some non-destructive testing can quartz crystals which vibrate mechani-
]e done by instrument “logging” devices cally when a compatible high frequency
:hat will not harm the equipment. Their voltage is applied to them. The sound
lse necessitates opening up equipment to wave generated passes from the transmit-
jain access in at least one end, e.g., ter through the liquid “couplanc” to the
LO inspect downhole casing or tubing, specimen. The ultrasonic waves will
:he logging devices must be inserted at travel through the specimen until they
>ne end. This requires equipment to be encounter an interface or discontinuity,
:emoved from operations for the time usually the opposite surface of the
:equired to make the examination, log specimen. The reflected sound wave is
the pipe, etc. Often this type of infor- received and transformed into an elec-
mation, which should be done on a regu- trical impulse by a piezoelectric
larly scheduled basis is most helpful in element. The impulse is reproduced on
the overall economical picture. Runs of a cathode ray tube screen as a vertical
this type should be made early in the displacement from the zero line on the
life of any equipment to serve as a graticule (Graticule: a scale on trans-
~ase-line and to provide the necessary parent material in the focal plane of an
~ackground for comparing later runs and optical instrument for the location and
assessing corrosion damage or the succ- measurement of objects) . The time be-
ess of corrosion control. Some of tween the initial pulse and the first
these runs and the use of optical bore- reflection is relative to the distance
scopes, etc. can be run on pipe on racks traveled by the sound wave.
before installing, or if removed for
any purpose before being re-used. Often This distance traveled would be
the examination is for the purpose of equal to twice the thickness of the
checking reuseability of the equipment. specimen or twice the distance to the
Downhole inspection with television or discontinuity. The sound velocity is
cameras is a possibility that should constant and therefore it is relative to
not be overlooked in the overall picture the thickness. The reflected sound
where the sizes permit use of this type waves are transformed into electric
of inspection device. Of course, pre- impulses showing up on a cathode ray
ferred examinations would be made in tube screen and forming sequential
equipment while in service and would not “pips”. The distance between
require opening up, shutdown, or lost reflections can be calibrated on the
production. graticule by using a stair-step block
of machined thickness and the thickness
NON-DESTRUCTIVE TESTS measured by referring to the graticule
and its known calibrations. Once the
Non-destructive methods available known thickness is measured and adjus-
for the examination of producing equip- ted on the screen, the operator can then
ment without interfering with operations start his measurements on the specimen,
include ultrasonic and radiation devices reading the thickness direckly from the
These devices car;be used wherever graticule.
access to the outside of the equipment
is convenient, or if buried, can be One unit is a battery operated,
unearthed sufficiently to apply the fully transistorized pulse echo device
transducers (for ultrasonics) or the which weighs less than 12 pounds. Its
r ~. . . ------ ---- . . . - ..---— —

small dimensions and independence of types of radiography are generally used,

electric mains make it suitable for circumferential (or panoramic) and pro-
field use. Testing on site, in Plants, jection radiography. Circumferential
m wells or other locations which are radiography is used for weld quality
difficult to reach is independent of the “=sting and is usually limited to
positions of the apparatus. A large piping. It is used to determine the
fluorescent screen picture is obtained quali~y of a weld as described by depth
by means of a built-in plastic lens with of penetration of the bead, porosity,
two-fold magnification. There are three inclusions, cracks, lack of fusion and
operating controls which are situated so forth. The usual test procedure is
on the front alongside the screen. The to encircle the weld area with three or
“time base” can be adjusted so that the more exposures. The film is taped
graticule represents a convenient dis- against the weld, and the radiation
tance in the specimen. The “zero con- source is positioned on the opposite
trol” moves the trace laterally, while side of the pipe for each expos,:=e.
the “gain control”, which incorporates Large pipe diameters may permit the
the on-off switch varies the echo radiation source to be positioned in-
height. ternall}, in which case only one expo-
sure to a film strip girdling the weld
The maximum thickness testable by is required. With laboratory controlled
the method is governed by the texture processing, the X-ray film may be
of the material tested. A coarse struc- studied by means of a densitometer to
ture is less satisfactory than a fine determine wall thickness.
one because the high frequency sound
waves are scattered by a grainy mater- The profile radiograph is made by
ial. The maximum thickness can vary p%~cing a film holder in a flat plane
from 8 to 25 feet. The minimum value behind the object to be radiographed.
of the measurable flaw or defect posi- The radioactive source is positioned
tion can be closer than 0.25 ins. at a mathematically determined distance
from the object, on the side opposite
Measurements should be made on new to the film. Outlines of the subject
equipment as it is installed and the are discernible, and the practiced in-
record filed for reference during the terpreter can determine most of the de-
life of a piece of equipment. Readings fects needed for weld quality testing.
made later should be made at exactly Additional information may be obtained
the same locations as were used to ob- by means of direct measurement of pro-
tain the original background readings. files of body walls, corrected for ex-
Comparison of the readings yields a posure enlargement by suitable means.
measure of the degree of progress of
corrosion. Limitations: (1) Surfaces Radiography can be used to expand
must be free of scale or other foreign the scope of non-destructive testing,
substances such as liquids so that the particularly in conjunction with ultra-
transducer can be tight against the sonic inspection. Areas of particular
surface. (2) Exact orientation of the suspert from the ultrasonic inspection
detector probe is required in order to may be studied in detail by radiography,
obtain reproducibility. (3) Interpre- This method is particularly applicable
tation of the results requires a traine d where the shape of an object, such as a
operator. choke body, changes rapidly and wall
thickness can only be correlated to a
Radiation previous reading at a marked spot.
Corrosion, erosion, and corrosion-
A non-destructive test procedure erosion may be more easily determlnea
utilizing electron radiation sources, if there is doubt as to the mechanism
either X-rays or gamma rays, has an of wall thickness reduction. Radiation
important place in the technology of sources may be either electronic
detecting and monitoring corrosion. Two devices, such as X-ray machines, or
 . . ------ ----- -------- ---------- ----. .--—--— .--— — -—

radioactive isotopes, such as Cesiurn- rods, even wires on altered ~park plugs
137, Iridium-192, and Cobalt-60. The can be used. These must be inserted
limitations to the use of radiography and usually require insulation from the
are the metal thickness (about 9 inches equipment metal and each other where
with Cobalt-60) and diameter-to-wall multiple coupons are used in a holder,
thickness relationships. A small bore, fitting, etc.
thick walled body does not produce a
distinct image. There is simply not Also included, and more properly
enough difference in metal thickness to termed “probes”, are those pieces of
provide contrast in the picture. The metal, insulated from each other and
use of any radioactive source requires the equipment, and electrically connec-
that a licensed operator be present. table to the appropriate instrumenta-
Unlicensed personnel must remain clear tion, control apparatus, etc. used for
of a prescribed area during the time resistance measurement, polarization,
that an isotope is out of the protective galvanic couple, and film zesistivity
case or an X-ray machine is energized. techniques.
(Shielding with various materials like
lead reduces the critical area) The Before describing some of thejr
object and the surroundings do not uses and characteristics, an excellent
retain any radioactivity upon comple- presentation of the overall problem5is
tion of exposure. If prescribed safety quoted from Chittum and Englander ’s
procedures are followed, the technique paper: “Frequently it is the practice
is harmless to plant and animal iife, to take for granted that.general cor-
and it serves as a valuable method of rosion rates for steel can be measured
non-destructive testing. accurately and unequivocally by using
any type of coupon or probe placed
PROBES OR CORRODING SPECIMENS wherever an attack occurs in a system.
HDwever, experience raises considerable
The term “probes” can be used to doubt as to the reliability of many
designate any device, piece of metal, such measurements, and suggests that
equipment part, made of the equipment many coupons and probes influence the
metals or equivalents, inserted into attack on themselves by changing both
a system under study. Another term for general rate and uniformity of the
“probes”, used by Byars3, is “corroding corrosion. A desired measurement is
specimens” . The system may be the the rate of uniform metal loss from the
equipment or an alternate of substitute, wall of the system suffering corrosion.
simulating the system as perfectly as The actual results obtained by conven-
possible. Standby equipment could be tional means for measuring corrosion
used, or a side-stream or by-pass~ are frequently different from what is
equivalent or identical to the main desired. This paper reports the
parts. Pilot systems could be used if results from a laboratory investigation
and where valid. Laboratory equipment to evaluate several of the common
has been used and can be with reason- methods used for corrosion rate
able care to simulate the equipment measurement. ..“
both as to metal and environment plus
the necessary range of operating para- They conclude: “1. Wall type
meters. weight loss coupons are able to measure
general rates for either oxygen or acid
Included under the category of corrosion with adequate accuracy and
probes are hydrogen probes, coupons, with satisfactory reproducibility. Wa 1
electrodes, and a great many others type split-sleeve coupons make possible
partially listed below: separate and accurate measurements for
the top and bottom of a pipe. 2. Rec-
Coupons, Spools, Nipp lest and tangular plate weight loss coupons,
Other Fittings centrally located in a flowing brine,
are able to measure oxygen corrosion
Pieces of metal such as plates, rates with accuracy that tends to be
YE 4720 D. R. F~

erratic but may be useful for qualita- tance ratio of the probe varies, but
tive work. 3. Rectangular plate weight not linearly with the loss of metal.”
loss coupons, centrally located in a
flowing brine, give high corrosion rates Polarization Resistance Method
for acid attack, but may provide rela-
tive results that are interpretable for The polarization resistance method
experience. 4. Rod type weight loss of corrosion detection is a technique
coupons give corrosion rates for acid for measuring corrosion rates directly
attack that are still higher than the without the necessity of exposing a
rectangular plates and demand more specimen for a time period between
experience for interpretation. 5. Re- readings. The method is based on small
sistance type probes tend to display all current and potential measurements on
possible problems for such corrosion small electrodes. Because of the fact
rate measuring units. The center-strearr that an electrical current flows betweer
specimens give high erratic results for the electrodes, it is necessary that th(
both oxygen and acid corrosion rates. electrolyte in which the tests are
The wall type probes are able to measure performed be a conductive one. ..
oxygen corrosion rates accurate-. , but
must be attached more carefully than The one principal advantage of
those used in the tests to avoid giving the polarization resistance method is
high results for acid corrosion. 6. the determination of instantaneous
Polarization probes tend to display all corrosion rates as compared to other
possible problems for such corrosion methods in which metal loss is measured
specimens. Meaningful rates require over a finite period of time. The term
considerable experience with the design “instantaneous” should be clarified:
and use in the system.” instantaneous means that each reading
on the instr~~ment can be translated
A rt..centNACE Standard6 discusses directly into corrosion rate. However,
the electrical methods as follows: the electrodes must be acclimatized to
“Several relatively new techniques for the environment before meaningful rates
measuring the corrosion rate of metals can be obtained.
are currently finding wide usage in
industry. These techniques are (1) the The instantaneous rate measured by
electrical resistance method, (2) ‘pol- the polarization resistance method is
arization resistance method, and (3) th< an average rate of penetration and does
galvanic method. not measure the pitting rate. However,
since pitting conditions result from
Electrical Resistance Technique nonuniform conditions on the surface of
metals, an indication of these corldi-
The measurement of corrosion by tions can be obtained with the dual
electrical resistance is based on the electrode system and both of the three
change of resistance of a metallic electrode methods of measurement. Sine,
specimen as its cross-section decreases all methods provide a measurement of
from a loss of metal.. . pitting tendency, the advantages of one
over the other will depend mainly on thl
In using the method, the corrosion read-out characteristics of the instru-
probe is exposed to the environment and ment. The read-out should make little
readings are taken on the instrument difference in the manual, portable type
at various intervals of time depending instrument but could make recordings
on the sensitivity of the probe. To either difficult to obtain or interpret
determine the rate of corrosion, the
loss of metal occurring between any A disadvantage in the polarization
two readings is divided by the time resistance method for rate measurement
interval to give a rate of penetration is that the electrodes must be in,a
per unit time... conductive solution. Thus, the tech-
nique cannot be used in gaseous environ.
As corrosion proceeds, the resis- ments or nonconducting liquids such as
 S SPE 42U

hydrocarbons. The upper limit of re- zation effects. Alternating current at

sistivity depends on the method used; 60 Hz can be used to give excellent
the three electrode system can be used reproducibility, with selected operating
in solutions having a resistivity as voltages. The frequency of the alter-
high as 106 ohm-cm since its current nating current is relati-~ely unimportant
and potential circuits are independent to these measurements, provided it does
of each other. The dual electrode sys- not vary much during any series of
tem, according to one instrument manu- measurements.
facturer, is limited to a maximum re-
sistivity of 105 ohm-cm. The dual Resistivity measuring techniques
electrode system also requires a corre- have and can be used to monitor and
lation relating the effects of resisti- control corrosion. Relative values
vity on the relationship between current and changes caused by simulated or
and corrosion rate. I-Zowever,for a actual conditions are noted and com-
given system, the resistivity will pared with reference values, calibra-
remain constant and the corrosion rate tions or known resistances. Determina-
will still be proportional to measured tion of the resistivity changes of a
currents; measured changes will reflect system, by checking sampled fluids can
changes in operation or treatment provide information like that obtain-
regardless of absolute rates. able from resistivity probes in a
system.
Galvanic Method
Resistivity measuring devices can
Measurement of galvanic current car be used in some situations to automate
be used to give a qualitative measure oi inhibitor injection. When resistivity
corr?sion rate. In some respects, the decreases below a level established by
metho~l is similar to the polarization experience ~r pilot experiments, a de-
resistance method in that it can be vice can be actuated to inject inhibi-
used on14r in conductive solutions. tor. Time delays may be required unles:
Instead o: an impressed current as the probes are immediately downstream
used in polarization resistance methods, of the inhibitor treatment injection
the galvanic method uses the driving point. Table I shows typical data.
force supplied by galvanic differences
in two metals. If non-conductive fluids pass the
probes circuit path the equivalent re-
One mus~ consider whether the sistance may be as high as treated
electrodes r,aybe fouled by the environ- (filmed) probes and/or equipment, but
ment.” not long-lasting like a good inhibitor
film.
AC Resistivity Technique
Hydrogen Probes
This technique can be used to
estimate corrosivity and to detect Atomic or nascent hydrogen (H+) is
presence or absence of coated-in-place formed in the corrosion reaction of
inhibitor films. steel in an elec$.rolyte containing
many corrodents. The atomic hydrogen
The resistivity between insulated will penetrate steel, probably along
probes or between a probe (insulated grain boundaries. Inside the steel,
from the equipment) and the equipment the atomic hydrogen can react to form
itself may be determined by a resistant molecular hydrogen (H2). When molecu-
meter. An electrolyte must be present lar hydrogen is formed, a large
between them and the measuring poten- increase in volume occurs, and if the
tial must be sufficient to overcome corrosion reaction is allowed to con-
any surface-effect potentials. Relia- tinue, hydrogen pressure will build up
ble and reproducible resistivity to an intolerable point. The pressure
measurements are difficult to obtain will cause soft steels to blister and
using direct current because of polari- rupture and hard steels to shatter.
r ~, &~~ n. L. ~lt..

Hydrogen probes have been devised CORRODANTS AND CORROSION PRODUCTS

to detect the presence of atomic hydro-
gen and forewarn the operator of pos- Monitorin< information can be
sible catastrophic harm which might obtained from any system by sampling
follow any build-up of atomic hydroger the environment, its fluids, and solids
in his equipment. One model hydrogen The value of this information in detec-
probe is a thick mild steel tube with ting and evaluating corrosion will de-
a very small cavity which is connected penal on the sampling, sample handling
to a pressure gauge and bleeder valve. between sampling and analysis, the
The probe element is constructed of a analytical techniques used, the skill
single piece of steel to prevent hydro- of analysts and the interpretation of
gen leakage. the data. The sampling step alone is
of such importance that kooks8have been
The probe is inserted in a system written on the subject alone.
and any corrosion which occurs is indi-
cated by a build-up of hydrogen pressure Obtaining samples accurately
in the drilled cavity. The rate of representative of the environment dur-
pressure increase is indicative of the ing the sampling becomes more compli-
corrosion that is occurring. Hydrogen cated with non-uniform environments or
pressure increase is slowed, reduced those subject to cyclic or uneven flow
and stopped if the system is well inhi- conditions. After the problem of ob-
bited. The hydrogen probe therefore taining samples representative of the
can be uf:ed tG evaluate the performance environment has been solved in any
of inhibitors in the field or the specific case, information on the
laboratory. placed in “sweet” gas corrosiveness of the environment may be
condensate wells corrosion has been obtained by a well-planned carefully-
monitored without interruption of executed sampling and testing program.
operations. Inhibitor effectiveness Any or all of the following constitu-
and application technique can be ents of the fluids; gas, liquid or
checked by pumping the inhibitor treat- solids, may be of interest and relevant
ment mixture past the probe. Table to the corrosion monitoring: 1. gases
II shows typical data. To test the relating to probability of corrosive-
film life of’ an inhibitor, the probe ness or changes in corrosion, hydrogen,
body can be coated with the inhibitor oxygen, carbon dioxide and hydrogen
prior to placing the probe in service. sulfide: 2. liquids, their pH, total
acidity or alkalinity, salinity,
Among the advantages of a hydro- dissolved corrosion products or salts
gen probe are their usefulness to oper- such as iron compounds, other salts,
sting personnel to determine if correc- buffering capacity, conductivity; 3.
tive measures are necessary before ex- solids, the corrosion products them-
tensive corrosion damage occurs in a selves, scales, waxes, gunks, emul-
system. Once corrective measures have sions, etc. i,lrelation to both
been initiated, the probe is left in corrosion and scaling, and treating;
place to warn operators when and if 4. presence of treating chemicals.
corrosion reoccurs.
Hydrogen
So-called “erosion”, which is
really corrosion caused by high flow Other corrosion products besides
rates and turbulence (cavitation in dissolved iron have been used for
some places, and/or “micro-tornadoes”), monitoring. In most systems hydrogen
can be detected using the hydrogen probe gas is not present except as a product
as a monitor and controlled with inhibi- of corrosion whereas dissolved iron may
tors . The probe is permanent as long be either naturally occurring or a
as corrosion is controlled. Probes can corrosion product. Probably no other
reflect damage by well stimulation material is less likely to be found in
treatments such as acid jobs. producing systems except as a corrosion
 10NITORING TECHNIQUES SPE 4220

prodl~ct than hydrogen. Its use for tion and/or device that will pilot
monitoring should be more extensive accurately enough whether oxygen is
than it is and has been. Only one present or might be suspected of being
reference was found. present may save time and money. AS
long as the simpler device shows no
A method of inhibitor evaluation probability of the harmful effects of
based on measurement of hydrogen trace oxygen presents, it may not be
evolved during corrosion? apparatus necessary to test with sufficiently
used, evaluation procedure and typical sensitive instrumentation as frequently
test results are given. The method or diligently to verify oxygen presence
was developed to simulate oil well or absence as would otherwise be desir-
corrosion as closely as possible and able.
still give rapid evaluation results.
Hot brine is passed continuously by an Carbon Dioxide
iron coupon and subsequently discharged
from the system so prevent build-up of Carbon dioxide10 also plays an
corrosion products. Simulation of important role as discussed below:
fluid flow is accomplished by rotating “Because carbon dioxide plays such a
the sample and provision is made for prominent role in sweet corrosion, some
introduction of a gas in the brine. Thf of the factors governing its behavior
gas and liquid leaving the iron coupon should be considered. The impartant
are separated and the amount of hydro- factors governing the volubility clf
gen in the gas stream determined. This carbon dioxide are pressure, tempera-
provides a means ~f continuously measur. ture, and composition of the wate~.
ing the rate of hydrogen evolution and Pressure increases the volubility (Fig-
consequently of the corrosion rate. ure 5)Y temperature decreases the
Effect of a chemical on this rate is volubility (Figure 6)? and many dis-
determined by injecting it into the solved minerals may buffer the water
flow stream in front of the sample and (prevent PH reduction). In a gas-
recording the change in rate of hydro- condensate well, with almost no dis-
gen evolution. Oil is not used in the solved minerals and at relatively
liquid stream because oil well cor- high temperatures, pressure is the
rosion is an ionic process and occurs controlling factor influencing carbon
only when metal is in contact with dioxide volubility. In fact, the
water. partial pressure of carbon dioxide can
be used as a yardstick to predict
-en Gas corrosiveness of gas-condensate wells.

Numbers quantifying any desired “The partial pressure of carbon

criteria are always needed, and some- dioxide can be determined by the for-
times are indispensable. Often ob- mula: Partial pressure = total
taing them is difficult and expensive. pressure x percent carbon dioxide.
Hence any simpler and cheaper device For example, in a well with a bottom-
or technique which will help deter- hole pressure of 3,500 psi and a gas
mine the need for vital numbers may containing 2 percent C02: Partial
save time and money if there is no pressure = 3,500 x 0,02 = 70 psi at
need for them and until there is. the bottom of the well. Using the
partial pressure of carbon dioxide as
A case in point could be the a yardskick to predict corrosion, the
numbers necessary to critically de- following relationship has been found:
lineate the dissolved oxygen content 1. A partial pressure above 30 psi
of corrosive flaids. Trace amounts of usually indicates corrosion. 2. A
oxygen are often critical. Convention- partial pressure between 7 and 30 psi
al tests are not sensitive enough to may indicate corrosion. 3. A partial
determine these low levels. Any rela- pressure below 7 psi is considered
tively easier-to-operate, less expen- non-corrosive.
sive and less complicated instrumenta- *see Reference 10,
* .

J1
?E_4z2~JuwmRax ~.

The salt water usually produced dictive device. P~oduced fluid samples
by a sweet oil well contains Jissolved can be obtained, possibly from a well
minerals and the foregoing relationship with no previous corrosion problems.
does not always apply. However, corro- TO find if the well might procluce
sion is mcst often encountered where th~ corrosive fluids if the water to oil
carbon dioxide content is high. As a ratio increased (“cut” increased) a
first approximation, the partial pres- number of corrosivity tests c=.nbe made
sure of carbon dioxide is useful in Besides tests at the “as-produced”
predicting corrosivity of sweel oil water-to-oil ratios, both higher and
wells. In Figure 7, the volubility of lower cuts than the as-produced are run
C02 in a typical sweet well has been A “Corrogram” can be made from the
calculated. “ data, in which the corrosivities found
are plotted against the cut. Operators
J&l@12 can be forewarned oi potential corrosio
problems if higher corrosivities are
Liquids obtairted from systems found at higher cuts.
may have dissolved materials or uni-
formly dispersed particles. If Solids
representative sampling can be made
and the materials are obtained on a Results of examination and analy-
reproducible basis related to their sis of any solid materials which can
sources, results of analyses may be be obtained from a system may provide
helpful in corrosim monitoring. additional helpful information. This
type of “detective” work ctirrelated
Dissolved ircn content 11 can be with others may be and aid in obtain-
a valuable detection tool: “Orleof ing a better idea of what is occurring
the first methods of monitoriilg corro- in the system. Is the solid material
sion in oil (and gas) fields utilized scale, wax, corrosion products, gunk,
dissolved iron content data. The crud, stiff emulsion, mill scale or
~method was used extensively in the bits of metal? Is it represerltative
development of systems for controlling of conditions or a random occurrence?
oil (and gas) field equipment corrosion
Procedures, applications and case CONCLUSIONS
histories have been cited in the
literature12. Visual and photoelectric The ideal corrosion monitoring
comparators were used as portable system would not necessarily use a!.1
calorimeters for measuring the available techniques, even if ample
dissolved iron content of produced money and shut down time to implement
water. Titration procedures also all of them were available, or if new
were used in the field and laboratory. installations, wells, plants, etc.
could be planned, designed and built
loof
In 1958, a joint publication using all of them. The wise corrosion
the American Petroleum Institute and engineer might plan his monitoring
the NACE described the methods then with several priorities or levels of
in use. Utilization of dissolved iron necessity and urgency in mind.
content tests may be found in the
minutes of various NACE Technical Unit The foremost criteria would be
Committees, with the currently respon- safety - ecology protection, minimized
sible unit being T-lC on Detection of interference to operations and economy,
Corrosion in Oil Field Equipment. even if the corrosion efigineer were a
Analytical procedures for determining super salesman who could sell the best
iron8are described in an API publica- and/or most expensive to his management
tion . Systems conditions would govern the
monitoring techniques desired. Those
Corroqrams best suited to match specific needs
in plant~ well, well equipment should
Corrograms can be used as a pre- be used, considering the operating
 .
<{J,
—
. . ..-. --------- .------------------ --, -- -- .+.- --u
—J.+. ----

conditions involved. (1964) November.

2. Junkin, E. D. Jr. , “ELECTRONIC
Alterations could be made to DATA PROCESSING OF EQUIPMENT
follow condition changes if access FAILURES - The First Decade”,
fittings were installed in plentiful Materials Protection, 8_, #7, pages
number and were strategically located 31 to 35 (1969) JUly.
for maximum corrosion monitoring inCor- 3. Byars, H, G. “CORROSION DETECTION
T.ation. AND CONTROL MONITORING”, A Digest
of the Proceedings of the Univer-
The highest priority in any instal- sity of Oklahoma CORROSION CONTROL
lation should be for devices which give COURSE , sponsored by The College
warning of impending disaster such as of Engineering and The Extension
catastrophic failure in ample time to Division, presented in cooperation
prevent any occurrences of equipment with National Association cf
breakdown causing serious loss of Corrosion Engineers’ North Texas,
property, damage to the environment, West Kansas, Tulsa, Central Okla-
or casualties. homa and North Central Oklahoma
Sections, Septeniber 11-13, 1972.
Hydrogen probes fit thjs category pages 17/1 to 17/7.
and might be called “be safe” or “stay 4. Elammang, R. F. Chapter on
safe” and be early warning types. They Monitoring, NRCE-API “Primer”
shofild be used in wells or equipment revision.
even where the pressures are low, the ‘). Chittum, J. F. and Englander, H. E.
wells shallow, the fluids rot consider- ‘(EVALUATION OF MEASURING METHCDS
ed severely corrosive and even if they FOR RATES OF GENERAL CORROSION OF
do not have high-strength brittle STEEL”, Rep:ints from “THIRD
alloys susceptible to stress corrosion BZENNIAL SYMPOSIUM ON MICROBIOLOGY,
cracking. They should be usec? in sweet API Pacific Coast District Study
systems, particularly in surface Committee”, pp. 127-145, Disneyland
systems even if not considered sour Hotel, Anaheim, California, Novem-
as they often “sour” unaccountably. ber 29-30, 1966.
6. NACE Publication 3D170 “MODERN
REFERENCES ELECTRICAL METHODS FOR DETERMIN-
ING CORROSION RATES” Issued by
1. Fincher, D. R. and Nunn, G. L., NACE Technical Unit Committee T-3D
“WHERE IS EQTJIPMENT-FAILURE on Instruments for Measuring
EXPENSE MONE”i SPENT?”, API (926- Corrosion. Prepared by NACE Task
9-B) ~stractt p90 237, D&P 1964: Group T-3D-l on Instruments fOr
“A unique system fOr reporting Corrosion Rate Measurement. Ed-
equipment failures dired from field ward Schaschl, Union Oil Company of
to machine processing has been in California, Chairman. Nation21
operation for 3 years. Information Association of Corrosion Engineers
on “how, when, where, and what cost 2400 West Loop South, Houston,
cost” of equipment failure is now Texas 77027. 11 pages and 5
readily available. Data collected pages bibliography.
over a 33-month period indicates
that punping wells are the cause 7. Auer, Leland and F. W. Hewes,
of the greatest portion of failure “Hydrogen Probes, Effective Tools
expense. Down-hole pumps are the for Detection of Hydrogen Forma-
rnost expensive items of failing tion and Maintaining Control Pro-
equipment in the oil field” Titles grams”, Materials Protection, ~
“How to Keep Tabs on Equipment- 4+8, pp. 10-14, (1964) August.
Failure Expense” Oil & Gas G., 62 (has excellent references)
#17, P. 151, (1964) April 27, an= 8. API RP 45 “Recommended Practice
“How to Flag Tool Failures”, —Pe- for Analysis of Oil Field Waters
troleum Management, Z, ++12, p. 177 , (Tentative) First Edition,
,.,
2$,
— —-..--—- . . - . ..-.
”-----
-,

PF 4220 D. R. FINCU 5na A. u.

November, 1965, Division of INSTITUTE, 300 Corrigan Tower
Production, American Petroleum Building, Dallas, Texas 75201, 87
Institute. pgs.
9. Scott, Willard R. and Rohrback, 11. Nestle, A. C., “CORROSION MONITCR-
Gilson H., “A HYDROGEN EVOLUTION ING METHOD REDUCES EFFECT OF
METHOD FOR EVALUATION OF CORROSION VARIABLES IN ANALYZING OIL FIELD
INHIBITORS FOR OIL WELLS” CORRO- WATERS” Materials Protection, 8_,
SION, ~, #7, pp. 234-240 1952 #5, pages 49 to 52, (1969) June.
(July) . 12. “CONDENSATE WELL CORROSION”
10, “CORROSION OF OIL- AND GAS-WELL Condensate Well Corrosion Committee,
EQUIPMENT” page 8, NACE & API, Natural Gas Processors Association@
1958, Published by Division of 1953.
Production, AMERICAN PETROLEUM

TABLE 1 - TYPICALFILM RESITIVITYMEASUREMENTS

PROBE APPARENT
CONDITION RESISTIVITY, OHMS

Uninhibited 2 to 10

Fairly Well Filmed 100

Good Film 1000

Excellent Film over 3000

Excellent Film 1000

With Intermittent
Treatment
 LADU!J d - .LVALUA’I.LUN Ur” Vfwluus LVmublulv UvHLkU”l’uKb,
HIGH PRESSUREGAS CONDENSATEWELL

Pressure Gage Pressure Treating

Date Inhibitor Readinq, psi Increase, psi gate

5/20/7 2 A 10 0 5 qts twice/day

5/21/72 A 23 13 5 qts twice/day
5/22/72 A 29 6 5 qts twice/tlay
5/23/72 A 36 7 3 qts twice/day

5/23/72 B 9 0 4 qts twice/day

5/24/7 2 B 18 9 4 qts twice/day
5/25/72 B 29 11 4 qts twice/day
5/26/7 2 B 52 23 4 qts twice/day

* Well shut down approximately 5 hours

6/5/7 2 c .- 12 3 qts twice/day

6/6/7 2 c -- 10 3 qts twice/day
6/7/72 c .- 22 3 qts twice/day
6/8/7 2 c -- 30 3 qts twice/day
6/9/7 2 c .- 31 3 qts twice/day
6/10/72 c -- 10 3 qts twice/day

6/11/72 D 42 0 3 qts twice/day

6/12/72 D 44 2 3 qts twice/day
6/13/72 D 48 4 3 qts twice/day
6/14/7 2 D 52 3 3 qts twice/day
6/15/72 D 55 3 4 qts twice/day
6/16/72 D 56 1 4 qts twice/day
6/17/72 D 57 1 4 qts twice/day
6/18/72 D 59 2 4 qts twice/day
6/19/72 D 62 3 4 qts twice/day

6/21/72 E 66 2 4 qts twice/day

6/22/72 E 70 4 4 qts twice/day
6/2 3/72 E 77 7 4 qts twice/day

6/24/72 F 10 0 4 qts twice/day

6/25/72 F 24 14 4 qts twice/day