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The Effect of Lubricating Oil Additives on Valve Recession in Stationary

Gaseous-Fueled Four-Cycle Engines

Conference Paper · October 1993

DOI: 10.4271/932780

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SAE TECHNICAL
PAPER SERIES 932780

The Effect of Lubricating Oil Additives

on Valve Recession in Stationary
Gaseous-Fueled Four-Cycle Engines

Walter R. Pyle and Nancy R. Smrcka

Chevron Chemical Co.

Reprinted from: Tribological Insights and Performance

Characteristics of Modern Engine Lubricants
(SP-996)

r The Engineering Society Fuels and Lubricants

For Advancing Mobility Meeting and Exposition
9
iTT TRTA^HTNTL Philadelphia, Pennsylvania
IJ^_I_^_^J^_^J_IJJJ^^ October 18-21,1993
400 Commonwealth Drive, Warrendale, PA 15096-0001 U.S.A. Tel: (412)776-4841 Fax:(412)776-5760
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The Effect of Lubricating Oil Additives
on Valve Recession in Stationary
Gaseous-Fueled Four-Cycle Engines
ABSTRACT
Cylinder head overhaul intervals, in stationary
four-cycle gaseous-fueled engines, are often determined
by the wear of intake and exhaust valves. To extend valve
and seat life, engine manufacturers select premium mate-
rials and use different design criteria (compared to diesel
or gasoline engines) for the valve-faces, seats, and guides
of gas engines. The most demanding design require-
ments for valves and seats are for lean-burn (air/fuel ratio)
and landfill gas high-speed, four-cycle gas engines.
First, this paper defines the three major types of
valve wear (recession, guttering, and torching), describes
valve wear measuring techniques, and reviews valve
recession variables that are not lubricant related (engine
design, mechanical assembly and maintenance, operat-
ing conditions, and metallurgy).
The second part of this paper includes a study of
the effect of lubricants on valve recession wear. Field test
results and analysis of valve, seat, and combustion cham-
ber deposits are covered. Based on results from field
tests, in several types of gas engines, a new family of gas
engine lubricant additive packages has been developed
which can extend valve life and reduce the frequency of
engine cylinder head overhaul.
INTRODUCTION:
TERMINOLOGY AND BACKGROUND
The valve and valve-seat terminology used
throughout this paper is described in Figure 1.
DEFINITION OF VALVE WEAR - There are three
types of valve and seat wear that occur in internal combus-
tion engines: valve recession, guttering, and torching.
Valve recession is the most common form of valve wear in
gas-fired engines; valve recession occurs gradually over
thousands or tens of thousands of hours. Guttering or
932780
Walter R. Pyle and Nancy R. Smrcka
Chevron Chemical Co.
torching failures are seen occasionally. For reference
purposes we now further define each type of wear.
VALVE RECESSION - Valve recession is caused
by wear of both the valve-face and the valve-seat. The
wear occurs by metal abrasion, high temperature corro-
sion, frictional sliding, and adhesion mechanisms [1-5].
Sometimes the wear will be greater on the valve-seat, and
at other times the wear will be greater on the valve-face;
this depends on materials and other factors, such as
operating conditions, fuel type, and lubricant type. Valve
recession occurs on both intake and exhaust valves, but
often occurs more rapidly on exhaust valves due to the
higher operating temperature.
The wear of the valve-face and valve-seat in gas
engines leads to the valve "sinking" or "receding" into the
cylinder head (when viewed from the side), as shown in
Figure 2.
Valve recession can be monitored by a bridge
gauge (a method for gas engines developed by Giles [6])
which measures the change in valve stem tip height above
the cylinder head. (See Figure 3.) When making bridge
gauge measurements, it is important to take the valve
stem temperature into account, since the head and valve
can shrink or grow due to thermal contraction or expan-
sion. To minimize downtime of the engine, the bridge
gauge measurements are usually taken immediately after
engine shutdown. The stem temperature is measured
with a thermocouple and recorded for future reference.
The greater the valve recession becomes, the higher the
valve stem tip height one will measure with a bridge
gauge. If valve recession becomes too great, the valve
will be pulled into the head by the valve springs. Later the
valve may "drop" (a piece may break off into the cylinder,
due to fatigue cracking, and hit the piston or go through the
turbocharger), with catastrophic results. Valve recession
also results in a loss of lash.
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Valve-Seat
Base Metal

Valve Tip
Valve Spring Retainer
(Keeper) Groove(s)
Valve-Seat Hard-Coating

Valve-Seat Angle

Valve Stem

Valve Face
Hard Coating
Valve-Seat Width

Stem-Blend Fillet Area

i
Margin Head Top Valve Face
Combustion Angle
Face
K X
Head Diameter

Figure 1 - Valve and Seat Terminology

i.
Valve Guide

Measure of Valve
and Seat Recession Cylinder Head
Cooling Water
Passage

Cylinder Head
Casting
Valve and Seat Valve and Seat
Recessed Normal

Figure 2 - Valve and Seat Recession

 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014
Figure 3 - Bridge Gauge for Measuring
Valve Stem-Tip Height Above Cylinder Head
Valve recession rates of 50.8-63.5 jam/1000 hours
(0.002-0.0025 inch/1000 hours) or less are considered to
be achievable and desirable today [7,8]. Typically cylin-
der head life should be 15,000 to 25,000 hours. There
have been reports of cylinder head life reaching 50,000
hours in gas engines before valve overhaul under ideal
conditions [7]. Cylinder head life varies depending on the
application (load), size, design, and manufacturer; it can
be shorter than 1 year (8000 hours) in some instances.
VALVE GUTTERING AND TORCHING - The
other form of valve wear is valve "burning," which can
occur in two distinctly different ways: by long-term "gutter-
ing" and by abrupt "torching."
Guttering Wear of the valve usually occurs only
on exhaust valves and is a high temperature corrosive
process that occurs slowly. Guttering will cause a gas
leakage path to form radially across the sealing area,
between the valve-face and valve-seat [9]. The shape of
a typical valve-face leakage path is shown in Figure 4.
A valve-face to valve-seat guttering leakage path
has a minimum diameter "throat" and a larger upstream
and downstream diameter. It is essentially a convergent-
divergent nozzle running choked or sonic (Mach = 1) at the
throat during portions of the engine cycle, when the
pressure ratio across the valve is greater than the critical
pressure. Downstream of the nozzle throat the flow is
transonic for a short distance. Further downstream a
Shockwave forms and creates a pressure discontinuity
which stimulates erosion of the protective metal oxides
from the surface. Removal of the protective metal oxide
film exposes the valve and seat alloys to fresh attack by
intergranular hot corrosion.
Figure 4 - Exhaust Valve-Face Guttering Radial
Gas Leakage Path, Magnification 22x
(Reference 10)
Under magnification, guttered valve surfaces suf-
fering from intergranular corrosion have a characteristic
cobblestone appearance [10,11]. A guttered valve from a
diesel engine is shown in Figure 5. This type of valve and
seat wear is rarely seen in gas engines, since it rapidly
progresses to a "torching" condition (described in the next
section).
Guttering valve wear eventually causes exces-
sive leakage of cylinder compression, and misfiring re-
sults in loss of power. A cylinder head overhaul will then
be required to restore proper operation of the engine.
Mechanical variables that influence valve guttering are
valve-face to valve-seat misalignment, valve stem stick-
ing, insufficient lash, weak or broken valve springs, and
worn valve guides [12].
A common cause for exhaust valve guttering in
diesel and gas engines is ash deposit flaking [13]. The ash
deposits in gas engines are derived from ash containing
lubricant additive components (and sometimes fuel gas
contaminants) due to the dissociating action of the com-
bustion flame plasmaand high exhaust gas temperatures.
An initiating leakage path is formed across the valve-face/
valve-seat interface where the flake is missing; the path
becomes wider and wider through the guttering mecha-
nism described above.
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Torching can occur in gas engines that operate

with excessively advanced spark plug ignition timing for a
given fuel, which produces abnormal combustion. With
abnormal combustion there is a high pressure rise before
or near piston top-dead-center. The high pressure rise
causes compression heating of the burning gases and a
more rapid heat release rate, raising the valve tempera-
ture. Deformation of the valve head and cylinder head is
increased. The higher heat release rate increases radia-
tion and convection heat transfer to the combustion cham-
ber and valve surfaces, causing a large surface
temperature rise.
Figure 6 shows a torched exhaust valve and seat
from a landfill gas engine running on a 1.0% ash zinc-free
gas engine oil.
Valve Sealing Diagnostics - Valve sealing prob-
lems can be detected most easily without disassembly of
the engine by measuring the amount of air leakage from
the cylinder. While the intake and exhaust valves are

Figure 5 - Cobblestone Appearance of Guttering

Leakage Path Showing Intergranular Corrosion,
Magnification 90x (Reference 10)

Torching of Exhaust Valves has been observed to

occur rapidly in just a few engine cycles. Torching is most
commonly associated with engines experiencing: (1)
preignition or (2) abnormal combustion ("knocking" or
destructive detonation) [9]. These modes are described
below.
Valve torching may happen abruptly when the
temperature of the valve-face or valve-seat surface is
elevated to the melting point by preignition. Conversely,
the hot valve can reach the "glow" temperature and
actually be the cause of engine preignition. Preignition-
related valve failures were first observed when gas en-
gines were operated on high ash "Series 3" lubricants
developed for diesel engines [13], presumably because
the ash particles became incandescent.
In a fumigated (carbureted), turbocharged gas
engine, compressed air-fuel mixture enters the combus-
tion chamber while the intake valve is open during the
induction portion of the cycle. The hot surface of a valve
or deposit particle can act as a "glow plug" and ignite the
fumigated fuel-air mixture during the compression cycle,
earlier than the spark plug. The burning gases are driven
through valve and seat interface leakage passages by the
high differential pressure of abnormal combustion, heat-
ing the surface to the melting point. Like a cutting torch,
the molten metal is carried away from the valve surface
into the exhaust passage by the jet of burning fuel gas and
air. This type of abrupt preignition failure is seldom seen
with direct injection gas or diesel engines because there
Figure 6 - Torched Exhaust Valve and Seat
is no fuel with the air during early compression.
 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014
closed and piston ring belt air leakage is eliminated, air is
let into the cylinder through the spark plug hole with a
compressed air "leak-down" tester [12]. Air leakage may
be eliminated in the piston ring belt by applying engine oil
to the rings with an oil gun (through the spark plug hole in
the cylinder head). The "hissing" sound of gas leakage
heard at the intake or exhaust manifold can be helpful in
identifying which valve(s) are leaking. Air leakage through
the valves can be caused by:
Guttering.
* Deposit buildup that is unevenly distributed on
the valve or seat.
* Localized deposit removal (flaking) on the valve
or seat.
• A deposit particle trapped between the valve and
seat that prevents the valve from closing com-
pletely.
• Bent valve.
Leakage due to trapped deposit particles can
often be stopped when doing leak-down testing by striking
the valve tip several times with a rubber hammer to
dislodge the particle and reseat the valve. (This proce-
dure is also used when making valve recession measure-
ments with a bridge gauge.) Sometimes the only way to
confirm that guttering or ash flaking has occurred is to
borescope the engine with the exhaust valve open or to
dismantle the cylinder head.
VALVE RECESSION FACTORS
There are a number of factors that contribute to
valve recession. Some are related to lubricant perfor-
mance and others are not.
The nonlubricant-related variables that aggra-
vate or affect valve recession are:
1. Fuel gas combustion characteristics (antiknock
rating) or contamination (dirt, e.g., silicon
dioxide).
2. Combustion air contamination (dirt, e.g., silicon
dioxide).
3. Metallurgy of valve-seats and valve-faces
(nonuniform or insufficient hardness). There can
be a fundamental material incompatibility
between the valve facing and seat insert.
4. Engine design (head and valve stiffness, valve
and seat angles, seat and guide cooling, valve
spring tension, and valve rotators).
5. Engine operating conditions (high combustion
chamber temperatures, excessive engine speed,
excessive engine load, excessive engine coolant
temperature, ebullient cooling with two coolant
phases).
The lubricant-related variables that affect valve
and seat recession are:
1. The amount and type of solid film and liquid film
lubricant delivered to intake and exhaust valves.
a. Effect of lubricating oil additive ash-sourced
solid film lubricant.
b. Fuel gas contaminants as exhaust valve and
seat deposit source (can interfere with solid
film lubrication).
c. Wear debris as exhaust valve and seat
deposit source (can interfere with solid film
lubrication).
d. Water treatment chemicals as exhaust valve
and seat deposit source (can interfere with
solid film lubrication).
2. Rate of oil consumption in the:
a. Piston ring belt area.
b. Valve guide and stem area.
3. Lubricating oil ash level and composition.
A REVIEW OF VALVE RECESSION
FACTORS THAT ARE NOT LUBRICANT RELATED
First, we will review those factors that are not
lubricant related, then we will review those factors that are
lubricant related. The lubricant can only extend valve life
when engine mechanical and operational factors are
under control.
FUEL EFFECT ON VALVE RECESSION - Natu-
ral gas engines have traditionally used very hard corro-
sion-resistant valve and seat materials to give extended
cylinder head life since gaseous fuels do not provide a
source of liquid or solid film lubrication. Most of the valve
and seat lubrication is sourced from the lubricating oil in a
gas engine. In fact, some gaseous fuels such as landfill
gas can contain antagonistic contaminants, which are
introduced to the engine and form deposits which ad-
versely affect valve lubrication and recession, as we will
show later.
Some properties of gaseous fuels are listed in
Appendices 1 and 2 [14-17].
For natural gas, autoignition characteristics are
normally defined by the methane number; methane num-
ber is analogous to octane number for spark-ignited liquid
fuels. Octane numbers and methane numbers for various
fuel gas sources are shown in Figure 7. The methane
number is based on a 0 to 100 scale with the primary
reference fuels being methane (100) and hydrogen (0).
 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014
0) Biogas
E *oCO CH
4( Methane
) con compounds (particulate and polysiloxanes). Landfill
3
z gas composition changes with time and well-collection-
KButahe) J b r ^ C 2 H 6 (Ethane)
0)
c * Producer Gas
S
o
-C2H4 (Ethylene)
50 100
Methane Number
Figure 7 - Gaseous Fuel Methane Number and
Octane Number Relationship
Fuel gas with an inadequate octane number or
methane number can cause autoignition "knocking" (high
pressure rise) or detonation that can initiate exhaust valve
torching and other engine damage. Today's gas engines
are often equipped with knock sensors which detect the
condition of high pressure rise and retard the spark timing
to prevent knocking with poor quality fuels.
It is important to use a good quality gas or at least
adjust the engine properly for the gas in use. Compres-
sion ratio, ignition timing, and operating temperatures
may be adjusted to provide better engine life on poor
quality gas. There are limits to how much the spark can
be retarded to compensate for a low octane fuel gas,
however. Some gases may be unsuitable for burning in an
engine, no matter how many adjustments are made. As
shown in Figure 7, the methane and octane numbers vary
widely for different fuel gases [14].
Pipeline gas has been processed and is normally
a good quality gas with low sulfur, having few contami-
nants present. A problem frequently encountered with
pipeline gas in engines is knocking, which may occur
during peak shaving. Peak shaving is practiced during
cold winter months when gas demand is exceptionally
high. Peak shaving involves making up for gas demand
shortages by injecting propane and air, which lowers
octane.
Wellhead gas, on the other hand, comes directly
from the ground and has little or no processing so it varies
widely in quality. Gas analysis is an important prerequisite
to good engine operation on wellhead gas. Many well-
head gas sources are sweet (low H2S) and good quality,
so they can be burned directly in wellhead gathering
compressor engines with minimal pretreatment of the gas.
Other wellhead gases can be extremely sour (high H2S)
or have levels of inerts (nitrogen, carbon dioxide) so high
that they are not suitable for engine operation without
major pretreatment.
Landfill gas is an anaerobic biogas created from
decomposition of garbage in a landfill which frequently
contains numerous contaminants. The most severe are
chlorofluorocarbons, halogenated hydrocarbons, and sili-
manifold vacuum. Usually the vacuum is kept at low levels
(1 -1.5 kPa) in the gas collection manifold to prevent the
drawing of high vapor pressure materials. Landfill gas has
a low heating value (typically half that of pipeline gas) and
frequently contains high levels of CO2, typically 50% or
more. Landfill gas must almost always be pretreated
before use in engines.
Leaded Gasoline Engines and Distillate-Fueled
Diesel Engines - Much can be learned about gas engine
valve recession by studying the work done by fuel and
lubricant researchers, engine designers, and valve de-
signers who have reduced valve recession wear in en-
gines using other fuels (gasoline, diesel, residual).
Leaded gasolines and distillate diesel-fueied en-
gines are less prone to valve recession and have valve
and seat materials made of cast iron alloys, since ad-
equate amounts of liquid and solid film lubricants, derived
from both the fuel and lubricating oil, arrive at the valve-
seat and valve-face. Unleaded gasoline engines are
somewhat more demanding of valve materials than leaded
gasoline engines due to lack of lead salt deposits formed
on the valves.
This was shown by Godfrey and Courtney [18],
who found that engines with leaded fuel had PbO*PbSC>4
(oxysulfates) on the hot valve-face and Pb(Clo.75Bro.25)2
(lead chlorobromide) on the cooler seat. The leaded fuel
gasoline engines gave lower valve recession wear than
the unleaded fuel engines. Lead chlorobromides pro-
tected the soft (Re = 40) cast iron seats, and lead
oxysulfates protected the harder (Re = 43) exhaust valves
from high temperature iron oxidation and prevented adhe-
sion, material transfer, and welding of the seat to the
valve. In unleaded fuel gasoline engines, the cast iron
seats became oxidized and produced flakes during opera-
tion; the hard (Re = 45-55) oxide flakes then transferred to
the exhaust valves. The oxide flakes built up layered
nodules which were pounded by the valve closing action
until they became embedded in the valve. The hard
embedded nodules on the valves then abraded the softer
seats, causing valve recession wear. Others have con-
firmed this mechanism and referred to the oxide nodules
as valve "warts" [6,19]. With unleaded gasoline fuel and
cast iron seats, increasing lubricant ash extended engine
exhaust valve life [19].
In diesel engines the combustion process is
thought to provide a certain amount of free carbon or soot
that helps lubricate the valve-seats even when the ex-
haust gas appears clear [20]. Some lubricity is provided
by the heavier ends of the distillate fuel which are similar
 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014

to the hydrocarbon fractions found in lubricating oil base
stocks. Residual-fueled diesel engines require special
valve and seat materials to combat high levels of fuel
sulfur and metallic impurities like vanadium and sodium.
Engine lubricants also provide valve and seat lubrication
in the diesel engine.
Since leaded gasoline and distillate diesel en-
gines get more valve and seat lubricant from the fuel, and
gaseous fuels do not provide this same level of protection,
gaseous fuel engines employ much harder (and more
costly) valve and seat materials to cope with the increased
severity.
VALVE AND SEAT METALLURGY - It has been
found that when plasma-sprayed hard-coatings are ap-
plied to the valve-face they resist recession better than
cast iron due to their higher hardness and superior corro-
sion resistance [9]. Harder alloys prevent the embedding
of oxide particles into the valve-face or valve-seat where
they can cause abrasion. Valve seat inserts are generally
cast from stellite materials, rather than coated.
In gas engines the intake and exhaust valves
have high levels of cobalt, nickel, iron, chromium, and
other elements to increase hardness. Several of the most
popular high speed four-cycle engine valves and seats
were analyzed for their elemental content and hardness,
as shown in Table I below.
It can be seen that most of the valve and seat
hard-coating materials analyzed were stellite, chosen for
their hardness. A table of stellite, stainless, and tool steel
alloys commonly used for valves and seats in gas engines
is given in Appendix 3. Usually the hard coating is about
1.78 to 2.28 mm thick and is applied to a softer base metal
(such as a tool steel).
In the future, ceramic monolithic cast valve seats
may be used to reduce valve recession rates by 60-80%
compared to the rates obtained with metal seats [21, 22].
DESIGN OF VALVES AND SEATS - There are
many other engine design factors which affect valve and
seat recession. These include valve-face and valve-seat
angle, valve-to-seat contact area, seat and guide cooling
rate, valve spring tension, lubrication of stem and guide,
valve rotators, valve "stiffness," and cylinder head distortion.
Valve and Seat Angles - Inrecentyearsoneofthe
most important design factors affecting valve recession in
gas engines has been the angles chosen for valve-face
and valve-seat. Valve-face and valve-seat angles have
evolved from angles of 30 degrees or more, towards
shallower angles such as 20 degrees to give extended
valve life [7, 8]. Design changes affecting valve and seat
angles came in response to increased valve recession
when traditional stoichiometric engines were operated
under lean-burn conditions to reduce NOx emissions, or
were operated on landfill gas. More deposits are formed
on the seat when the shallower angles are used, aiding in
establishing a solid film lubricant layer on the valve-seat
and valve-face. This is acceptable with low ash lubricants,
however with high ash lubricants (>2% ash) excessive
deposits may be formed, making the valve prone to
deposit flaking, guttering, and torching [9]. Angles less
than 20 degrees did not further reduce valve recession
rates [7]. Reducing valve-face and valve-seat angle to 20
degrees has a design trade-off; flow losses are increased

Table I
Valve and Seat Analysis

Probable SAE Composition, Wt %

Alloy* Fe Cr Co Mo Mn W Ni Hardness, Rc

Exhaust Valves Hard-Facing

Exhaust VF6 Stellite No. 1 8.6 28.1 46 0.23 0.56 11.29 1.96 54.7-57.7
Exhaust VF11 55 24.3 - 5.64 0.39 - 10.72 44.7-46.9
Exhaust Stellite No. 6 10.8 27.2 50.8 0.06 4.2 4.1 2.0 38.7-48.9
Exhaust Nimonic81 - 30 70
Intake Valves Hard-Facing
Intake Stellite No. 6 10.8 27.2 50.8 0.06 4.2 4.1 2.0 38.7-48.9
Intake Stellite No. 6 14.5 27.2 50.0 0.02 1.8 3.71 0.44 46,3
Intake EN 52
Seat Hard-Facing - 21.6 69.5 1.0 5.2 1.3 47
*See SAE revised J775 standard for valve alloys and standard for valve-seat insert.

95
 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014
when the exhaust gases pass through the shallower angle
passage when the valve is open.
Contact Area Between Valve and Seat - The area
of contact between the valve-face and the valve-seat
insert is frequently larger in gas engines than diesel or
gasoline engines to contend with high combustion cham-
ber temperatures. A larger area of contact provides a
larger gas sealing area (to prevent combustion chamber
gas from leaking into the exhaust manifold during the
combustion stroke, before the exhaust valve opens, and
to keep air-fuel mixture from leaking into the intake mani-
fold during the compression stroke). A larger contact area
also promotes heat transfer from the exhaust valve into
the seat area and offsets the reduction in heat transfer due
to the insulating nature of a solid film lubricant.
Heat is transferred into the exhaust valve when
the hot exhaust gases impinge on the valve-face and stem
when the exhaust valve is opened at the end of the power
stroke. Heat is then transferred out of the valve (after it
closes) to the relatively cool valve-seat, which is pressed
into the cylinder head and surrounded by engine coolant.
Heat is also transferred out of the valve into the valve
guide. About 75% of the heat transfer between the valve
and the cylinder head occurs by conduction through the
seat [6]. The remainder occurs primarily through valve-
stem to valve-guide conduction. Heat transfer is also
important in maintaining intake valve-seat hardness and
in reducing the tendency for exhaust valves to oxidize and
de-alloy (promoting wear) at the seat.
The importance of cooling the valve and seat
becomes more apparent when one considers that poor
sealing of the valve and the seat (due to excessive
deposits, inadequate valve spring pressure, etc.) will
allow combustion gases to leak through the seal area of
the valve, heating it and promoting guttering erosion or
torching. The effective area of contact between the valve
and its seat and the conduction heat transfer coefficient
will be reduced by excessive deposits, interfering with
proper conduction cooling of the valve. Loss of seat heat
transfer increases the heat that is transferred through the
guide. Excessive heat transfer from the valve to the guide
increases the guide lubricant temperature and reduces
the oil film thickness between the stem and the guide. In
extreme cases, sticking of the valve stem in the guide can
cause the valve to strike the piston top, or cause seizure
of the valve stem in the valve guide and catastrophic
engine failure [24]. The valve may be bent if the valve
strikes the piston top, causing leakage or burning.
A large valve-face to valve-seat contact area aids
the valve and seat to become more tolerant of hard
particles. Hard particles coming from dislodged combus-
tion chamber deposits and wear debris may get crushed
into the solid film lubricants, rather than the valve or seat
metal, when a valve closes on the hard particle before it
passes into the engine's exhaust system. When the
contact area is wide enough, these "damaged" films will
not open a radial guttering channel between the combus-
tion chamber side of the valve and the manifold side. As
long as a radial channel does not form, the "damaged" film
will "heal" as more ash arrives and fills in the hole in the film
made by the hard particle.
Valve Spring Tension - The natural frequency of
the valve spring and the closing forces should be high
enough to prevent valve bounce. Valve spring tension
should not be excessive or pounding of the seat by impact
loading will occur on valve closure.
Lubrication of Valve Stem and Valve Guide -
Lubrication of the valve stem is accomplished by allowing
a small amount of oil from the rocker cover area to come
down the valve stem. Oil control is usually obtained by
maintaining the clearance between the valve stem and
valve guide to prevent too much oil from entering the valve
stem to valve guide interface. Some engine manufactur-
ers use sintered metal valve guide material which is oil
impregnated initially at the factory. Some manufacturers
use a helical groove in the valve guide bore to distribute
the oil film evenly. Another manufacturer uses valve guide
seals to control oil delivery to the valves. Some valve
stems are chrome plated for landfill gas and sour gas
operation, where corrosive wear is a problem. Improper
stem lubrication leads to valve scuffing which results in
high seating velocities, contributing to seat wear.
Valve Rotators - Valve rotators were shown to be
effective in reducing leaded gasoline engine valve reces-
sion. In gas engines, one manufacturer found that no
attempt to control rotation was better than pinned valves
(that prevented any rotation) and better than positive
rotators [20], Another manufacturer found that "rotocoil"
valve rotators, which rotate the valve while the valve is
lifted up off of the seat, helped reduce recession.
Older valve rotator designs, called "rotocaps,"
used in automotive passenger car engines, were differ-
ent; they rotated while the valve was seated/seating [8].
When passenger car engines having rotocap rotators
were converted from gasoline to natural gas or LPG
service they caused high wear of the soft cast iron valve
and seat parts, just like with unleaded gasoline engines as
we described earlier. This led several engine manufactur-
ers and after-market gas conversion carburetor compa-
nies to recommend against the use of valve rotators [25].
Acceptable gas engine valve recession wear rates
have been obtained by Engine Manufacturer A using
rotocoil rotators, and by Engine Manufacturer B using no
positive rotators. Both manufacturers used premium
valve materials in engines designed specifically for use
with natural gas [7, 26]. Too much rotation gives more
recession with rotocoil rotators. Cylinder to cylinder
variations in rotation were noted. If a rotator failed to
 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014
rotate, valves were guttered. Inconsistent rates of rotation
were found from piece to piece (1 rpm to 4 rpm) [26].
Others have found that positive valve rotators produced
higher rates of recession [27]. Engine Manufacturer D
obtained high valve recession with positive rotators when
a rotation rate of 7 rpm was measured [28].
Valve and Seat Misalignment - Cylinder head
distortion can cause the relative valve-seat and guide
geometry to change. This misalignment can occur when
problems such as coolant passage deposits, and thermal
effects (high pressure rise associated with preignition or
knocking) upset the geometry and cause uneven heat
transfer between one area of the valve and seat and
another. The seating contact pressure varies inversely
with contact area. Improper seating may be due to
thermal effects associated with nonsymmetric cylinder
head deformation as a result of defective cooling system
passages (e.g., a casting defect) in the head near the
valve-seat [5].
Excessive valve-stem-to-guide clearance can also
cause misalignment. The valve-face initially contacts only
a portion of the major diameter of the seat insert, as shown
in Figure 8 below. Initial contact is most severe because
of high valve momentum. Ridges are formed in the valve-
face as the valve bounces to self-center, driven by com-
pression and combustion cycle pressures. Valve rotation
results in different portions of the valve-seat impacting the
insert during each cycle of valve closure. "Single wave"
and "multiple wave" ridges were observed by one inves-
tigator [29]. Guide wear is the most common cause of
excessive clearance.
Misalignment can also cause a "Chorda!" failure
of the valve where fatigue cracks form on the valve head
and propagate until a piece of the valve breaks off. A
chordal valve failure is a serious problem because the
turbocharger blades can be destroyed and the piston can
be damaged by the detached piece of valve material [30].
Figure 8 - Off-Center Seating Due to Valve and Seat
Misalignment
EFFECT OF GAS ENGINE OPERATING
CONDITIONS ON VALVE RECESSION
Engine operating conditions that can adversely
affect valve recession include:
1. Overheating
2. Combustion Air or Fuel Abrasive Content
3. Abnormal Combustion
4. Lean Air-Fuel Ratio
5. Overspeeding/Overloading
6. Improper Lash
OVERHEATING - Combustion gas temperatures
can heat the stem-blend fillet area of the exhaust valve to
649-814°C or higher [4]. The exhaust valve temperature
is frequently 200°C or greater than the exhaust tempera-
ture measured in the exhaust manifold [12]. In ebullient
cooled gas engines, exhaust valve fillet area tempera-
tures reached 816-927°C [31 ]. An ash deposit or lacquer-
type deposit on an exhaust valve-face or valve-seat that
is too thick can cause thermal insulation and interfere with
heat conduction from the valve-face through the valve-
seat insert and into the cylinder head. When internal
temperatures in the valve head become excessive, ther-
mal stress cracks can form around the periphery of an
exhaust valve (which may lead to guttering or torching).
Excessive valve temperature can also cause the valve to
become "dished" or "tulipped" (the metal flows or creeps
under the influence of cylinder pressure). In addition, an
overheated valve may experience stress cracks in the
fillet area [30]. We observed peripheral thermal stress
cracking of the exhaust valve in an overloaded gas engine
as shown in Figure 9 below. Most cracking (other than
Figure 9 - Cracked Exhaust Valve from
Overheating, Magnification 3.5x
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Figure 10 - Exhaust Valve from Biogas Engine
Abrasive Particle Erosion, Magnification 3.5x
chordal) is corrosion assisted and initiated; combustion
face cracks are relatively rare but are propagated due to
thermal hoop stresses.
COMBUSTION AIR OR FUEL GAS ABRASIVE
CONTAMINANTS - Combustion air or fuel contaminants
can cause valve recession via abrasive-particle erosion.
We observed this in a digestor plant engine which used
biogas. The biogas digestor contained garbage intention-
ally spiked with fly ash to reduce foaming. The fly ash,
which contained silica (Si02), contaminated the biogas
and caused abrasive particle erosion of the engine ex-
haust valve, as shown in Figure 10.
Proper combustion air and fuel gas filtration is the
best preventive action for removing abrasive particulate
contaminants. Landfill gas pretreatment plants typically
include a <0.5 \im filtration unit to remove silica particulate
contaminants.
ABNORMAL COMBUSTION, preignition, and
detonation all promote valve recession, guttering, and
torching, as mentioned earlier.
LEAN AIR/FUEL RATIO - In recent years turbo-
charged engines have been designed to operate under
lean-burn conditions to reduce NOx emissions. Some
engine manufacturers use a precombustion chamber with
a rich mixture (X <1.0)* and a main chamber with a lean
mixture (k = 1.5-2.2). The spark plug is positioned in the
precombustion chamber for reliable firing of the rich mixture.
Other manufacturers run with a lean main cham-
ber and use high energy spark ignition systems to obtain
reliable combustion without misfiring on the leaner mix-
tures (X= 1.5-1.7).
Running with a "lean" air/fuel ratio can lead to
higher valve recession in naturally aspirated engines (with
*X = 1.0 is a stoichiometric air/fuel ratio.
V-configurations using dual carburetors) when the carbu-
retors are not balanced or the air cleaners have different
flow restrictions [9].
Some differences between lean-burn and stoi-
chiometric (or rich-burn) engines include:
1. Exhaust valves run cooler in the lean-burn en-
gines than their rich-burn counterparts. The influ-
ence of this change alone would tend to decrease
valve recession wear attributed to hot corrosion.
2. Lean-burn engine gas pressures are greater at
the intake valve, and the combustion chamber's
peak pressures are also higher. The influence of
this change alone would tend to increase exhaust
valve recession due to greater valve distortion
and a greater pressure ratio across the valve.
3. There is more gas turbulence in the lean-burn
engine combustion chamber during combustion.
This may alter the heat transfer to and from the
valve and may influence the deposition of ash
deposits on the valve and seat and in the combus-
tion chamber.
4. There are higher levels of oxygen in the exhaust
gases of lean-burn engines. This increases the
formation of oxides on valves, seats, valve and
seat deposits, and combustion chamber depos-
its. This would tend to increase valve recession
if the oxides have greater hardness than the valve
and seat, and decrease valve recession if the
oxides are soft from, say, calcium-based lubricat-
ing oil ash.
5. Exhaust gases of lean-burn engines contain a
reduced amount of nitrogen oxides.
The overall affect of lean-burn operation has been
to increase the severity of exhaust valve recession.
EXCESSIVE ENGINE SPEED AND LOAD can
adversely affect valve recession. Excessive speed causes
high impact pressures on the valve-face and valve-seat,
i.e., high seating velocities. Overloading causes exces-
sive heating and distortion of engine valve train components.
IMPROPER LASH settings may be avoided by
making proper adjustments at regular intervals, following
the engine manufacturer's recommendations.
EFFECT OF LUBRICANTS ON VALVE RECESSION
Chemical additives are carefully formulated and
balanced to make additive packages. Additive packages
are then combined with base oil to make a finished
lubricant which will preserve and enhance the perfor-
mance of the engine. Some of the additives reduce sludge
and varnish deposit formation. Other additives protect the
engine from corrosive wear and inhibit oxygen attack of
the oil and engine metal parts. The additives help to
counteract the negative effects produced by contami-
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nants entering the lubricant. One important source of Usually the main source of gas engine valve and
contaminants comes from the piston ring blow-by gases seat deposits is the lubricating oil additive package. Only
that escape from the combustion chamber during com- with landfill gas engines does the fuel source of deposits
pression and combustion. Blow-by gases are composed become an important consideration. Elements used in
of unburned and partially burned fuel and oil hydrocar- additive packages for control of wear and deposits in-
bons, free radicals, NOx, CO, CO2, N2, O2, and water clude: calcium, barium, magnesium, phosphorus, nitro-
vapor. Blow-by may contain H2S, SO x , acids [halide (HCI, gen, sulfur, and zinc. In recent years barium has been
HF, HBr), nitric, and sulfuric] from burned fuel contami- phased out of most engine lubricants in the U.S.A. due to
nants and particulates from piston deposits and combus- environmental concerns (about improperly disposed used
tion chamber deposits. oil getting into groundwater). Magnesium additives are
Additive packages can play a key role in control- usually only used at very low levels in gas engine lubri-
ling valve recession in four-cycle gas engines, as we will cants to avoid the creation of magnesium oxide deposits
demonstrate in subsequent sections of this paper. which are very hard and can promote abrasive wear.
MECHANISM OF LUBRICANT-RELATED VALVE Some hardness and decomposition temperature data for
RECESSION - Engine lubricants have been found to lubricating oil-sourced deposits are shown in Table II.
increase or reduce vaive wear depending on the additive Too much solid film lubricant coming from lube oil
composition and amount of oil on the valve-seat and ash can be detrimental to exhaust valves and lead to valve
valve-face. If the amount of oil reaching the valve-face is guttering or torching, due to flaking [26,9]. Too much ash
too low, a lack of liquid and/or solid film lubricant will cause can increase the effective compression ratio (due to
excessive valve recession under most engine operating buildup of deposits on the piston fire face and the combus-
conditions. If the amount of the oil at the valve-face is too tion chamber) and lead to preignition or detonation. Too
high, excessive deposit will build on the exhaust valve and much ash makes a thermally insulating coating which
cause guttering or torching (if temperatures are sufficient reduces conduction heat transfer and raises the valve
to initiate a corrosive attack). The amount of deposits that temperature.
could cause guttering or torching depends on both the ash
level in the oil and the oil consumption. For high ash oils
the amount of oil consumption that can be tolerated is Table II
less, and for low ash oils the amount would be greater. Hardness and Decomposition Temperatrue of Some
LIQUID AND SOLID FILM LUBRICANT - Liquid Lubricating Oil Additive-Sourced Deposit Compounds
film lubrication is most often dominant on intake valve-
Decomposition Temperature, °C
faces and valve-seats in gas engines where temperatures | Compound Melting
Mineral Name Hardness, Moh's Boiling
are not high enough to volatilize all of the lubricant CaCOg Aragonite/Calcite 3.5-4 520 825
hydrocarbons and additives. Exhaust valve-faces and CaO Lime/Calcia 3-3.5 2580/2614 2850
valve-seats are lubricated predominantly by solid film Ca5(P04)3OH Hydroxyl Apatite 5
lubricants due to the higher operating temperatures. The Ca(P0 3 ) 2 Metaphosphate 975
solid film lubricant is supplied by lubricating oil additive Ca 2 P20 7 Pyrophosphate 1230
ash compounds such as alkaline-earth and other metal Ca 3 (P0 4 ) 2 Whitlockite 5 1670
oxides, sulfates, and phosphates (e.g., calcium, barium, CaS Oldhamite 4 -
magnesium, sodium, zinc, and molybdenum). The ben- CaS0 4 Anhydrite 3.5 -
(1193 Inverts to a)
efits of very thin metal oxide solid films in reducing seat 1450

wear were noted in previous studies [20]. We elaborate on 2CaS0 4 H 2 0 Bassanite

the deposit composition in a later part of this paper. CaS0 4 -2H 2 0 Gypsum 2 128 (-1 h^O) 163 (-2
H20)
PROPER AMOUNT OF SOLID FILM LUBRICANT - CaZr^(P0 4 ) 2 Calcium Zinc
A "proper balance" of solid film lubricant is needed for Phosphate
MgO Periclase 5.5 2800 3600
good exhaust valve wear control. A number of different
MgS0 4 1124
compounds can be formed in the solid film deposits on
Kieserite 3.5 (H 2 0 Lost at 350)
exhaust valves and seats, depending on: MgS0 4 H 2 0
Na 2 S0 4 Thenardite 2.5-3 884 -
1. The Additives Present in the Oil ZnO Zincite 4 1670 1975 I
2. The Metallurgy of the Valve and Seats ZnS Sphalerite 3.5-4 1020 1185 I
(Inverts to Wurtzite)
3. Contaminants in the Fuel Gas ZnS Wurtzite 3.5-4

4. The Contribution From Engine Wear Debris Zn 3 (P0 4 ) 2 -4H 2 0 Hopeite 3.253.76 (2H 2 0 Lost at
135/139)
5. Water Treatment Chemicals (Due to Leaks) Parahopeite (4H 2 0 Lost at
233/240)
6. Carbon Residue From Base Oil Stocks
and Additives
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Usually the deposit films on the exhaust valve and

Figure 11A - Landfill Gas Engine - Cylinder 10
Exhaust Valve-Face Deposits
Figure 11B - Landfill Gas Engine - Cylinder 9
Exhaust Valve-Face Deposits
seat are constantly in the process of being created and
destroyed [34]. After some time, an equilibrium is reached
where small localized areas of the film are being "dam-
aged" (by closing on hard particulates or by thermal shock
flaking), creating voids or discontinuities of the film; con-
tinued operation restores the "damaged" film areas by
establishing fresh deposit films which fill in the voids and
discontinuities. Some deposit films with "damaged" areas
on exhaust valves and seats from landfill gas engines are
shown in Figures 11 and 12.
Crushed hard particles from combustion chamber
deposits can be seen on the exhaust valve-face from
Cylinder 9 (Figure 11B) and on the seat of Cylinder 9 at 11
o'clock (Figure 12B).
Effect of Lubricating Oil Ash on Valve and Seat
Deposits - Use of a 1.0% ash calcium plus zinc oil gave
lower valve recession than a low ash zinc only oil in
gasoline engines [27,32,33]. Another study by McGeehan
et al. showed that 1.0% ash lubricant provided lower valve
recession and thinner deposit layers than higher ash oils
with a similar detergent type in diesel engines, as shown
in Figure 13 [10].
The powerful influence of ash level on valve
recession in a diesel engine is clear in this example. A
minimum ash level must be defined for gaseous-fueled,
four-cycle engines as we will show later. Too little solid
film lubricant can increase the exhaust valve and seat
wear rate three to five times [20].
Because the "proper balance" of solid film lubri-
cant must be maintained, most engine manufacturers
specify maximum and minimum lubricating oil ash levels
for any given type of gas service.
Fuel Gas Contaminants as Exhaust Valve and
Seat Deposit Source - Deposits were removed from

Figure 12A - Landfill Gas Engine - Cylinder 10 Figure 12B - Landfill Gas Engine - Cylinder 9
Exhaust Valve-Seat Deposits Exhaust Valve-Seat Deposits

100
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< PROPER AMOUNT OF LIQUID FILM LUBRICANT -
•o
100 200 300 400 500 600 700 800 900 1000 1100
Engine Hours to Failure
Figure 13 - Relationship of Oil Sulfated Ash and
Average Valve-Seat Deposit Thickness to Valve
Failure Engine Hours for a Diesel Engine
(Reference 10)
Table III
Composition of Landfill Gas Engine Exhaust Valve
Deposits (Fuel Gas Sourced, Elemental Wt %)
Fuel Gas Cu* Sn* As* Si*
Landfill Gas A, 2.15 0.546 0.064 13.1
Australia
Landfill Gas B, U.S.A. 0.039 0.164 0.127 5.47
Landfill Gas C, 0.137 0.422 - 4.32
Australia
*Not present at high levels in fresh or used lube oil, therefore, sourced by
fuel gas.
landfill gas engine exhaust valves and analyzed by Induc-
tively Coupled Plasma (ICP) Spectroscopy. The results
are listed in Table III. Note that all of the landfill gas engine
deposits contained high levels of copper, tin, iron, and
especially silicon, even with <0.5 jam fuel gas filtration.
Wear Debris as Exhaust Valve and Seat Deposit
Source - Engine wear debris from pistons, rings, cylinder
lines, bearings, cams, gears, valve tips, and crankshaft
can propagate into the combustion chamber with the
consumed oil and leave a residue. Usually these wear
debris elements can be seen in the used oil analysis. The
iron found in the deposits may be ambiguous; it can be
sourced from the fuel gas as well as from wear debris.
Water Treatment Chemicals as Exhaust Valve
and Seat Deposit Source - Engine coolant usually con-
tains water treatment chemicals to prevent corrosion of
ferrous metals, aluminum, and copper parts. Any coolant
leaks into the combustion chamber (due to turbocharger
aftercooler heat exchanger leaks, cylinder head gasket
leaks, etc.) or into the crankcase oil (cylinder liner O-ring
seal leaks, water pump leaks, gasket leaks, etc.) will leave
traces of the coolant treatment chemicals in the valve and
seat deposits. Sodium or potassium metaborate is a
common coolant treatment which can be detected by
boron, sodium, or potassium elemental analysis of the
deposit.
Too much liquid film lubricant (overlubrication) can cause
heavy carbon-rich deposits to form on the stem-blend fillet
area of intake valves. This condition is promoted by loss
of oil consumption control through wear of the intake valve
guide and seal, as well as by cold operating temperatures
(extensive idling). These carbonaceous deposits on the
valve stem, sometimes called "knots," interfere with com-
bustion air flow into the cylinder when the valve is open
[30]. However, the stem deposits can be reduced by
lubricating oil dispersants, detergents, wear inhibitors, and
antioxidants. Base oils with a lower Conradson Carbon
Residue (ASTM D 189) may also help reduce stem deposit
formation. As a practical matter, intake valve deposits are
seldom a problem in stationary gas engines since they are
operated at high load factors and do not idle extensively.
Too little liquid film lubrication (underlubrication)
will increase intake valve recession. In some gas engines
"oilers" are installed in the inlet air manifold prior to the
inlet valve port to supply lubricant to the intake valve [26].
Fe*
Most engine designs supply lubricant to the valve and seat
0.12 via controlled leakage of oil through the valve-guide-to-
valve-stem clearance annulus. Some lubricant is deliv-
0.065
ered to the valve and seat surfaces by oil consumption
0.443 from the piston, rings, and cylinder wall.
Cylinder-to-cylinder variations in valve guide oil
consumption were observed within the same engine (and
from engine to engine) due to production tolerances.
Rebuilt engines sometimes have more variation in toler-
ances than factory engines, depending on quality control
of the parts and processes used. Two intake valves from
Engine A after 5400 hours of operation on landfill gas are
shown in Figure 14.
It can be seen that there are noticeable variations
in the amount of liquid film lubricant on the valves within
the same engine.
Control of Oil Consumption in the Piston Ring Belt
Area will help prevent excessive valve-face and valve-
seat deposit buildup. Oil consumption in the piston ring
belt area of a properly designed gas engine can be
affected by:
• Corrosive and adhesive wear of the rings and
cylinder liner (must be inhibited by lubricant
design, proper engine operating temperature
selection, and proper fuel pretreatment).
• Bore polishing from piston crownland deposits
(must be minimized by lubricating oil, operating
conditions, and engine design).
• Liner lacquering or coating of the cylinder cross-
hatch surface finish (must be prevented by proper
fuel gas pretreatment, proper choice of engine
operating conditions, and lubricating oil).
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Figure 14A - Landfill Gas Engine - Cyulinder 9 Intake
Valve - Higher Oil Consumption 5400 Hr
Figure 14B - Landfill Gas Engine - Cyulinder 10
Intake Valve - Lower Oil Consumption 5400 Hr
• Abrasive wear from combustion air and fuel
particulates (must be reduced through proper
filtration).
Control of Oil Consumption in the Valve Guide
and Stem Area - Control of oil consumption from the valve
guide was shown to have a major effect on valve reces-
sion in diesel engines; guttering was accelerated due to
excessive deposit buildup when valve guide oil consump-
tion and the associated lube oil ash was excessive [9].
EFFECT OF LUBRICATING OIL
ADDITIVE COMPOSITION ON VALVE RECESSION
Numerous gas engine field tests have been con-
ducted by our technical staff on experimental lubricating
oils containing different additive package components.
As much of our product development work as possible is
conducted in field engines to allow proper observation of
long-term performance effects such as:
1. Valve Recession
2. Combustion Chamber Deposit Buildup
3. Spark Plug Fouling
4. Preignition Tendency
Samples of valve-face deposits from gas engine
field tests were analyzed by ICP (Inductively Coupled
Plasma) spectroscopy, XPS (X-Ray Photoelectron Spec-
troscopy), XRD (X-Ray Diffraction), SEM (Scanning Elec-
tron Microscope), and EDXRF (Energy-Dispersive X-Ray
Fluorescence) to determine their composition. ICP spec-
troscopy was used to analyze each valve deposit sample
for elemental composition. XPS was used to determine
the oxidation states of elements present in the valve
deposit. XRD was used to determine the composition of
the crystalline chemical compounds present in the valve
deposit. SEM, in combination with the EDXRF, was used
to identify the structural features and the elemental com-
position of the deposit coated surfaces of valve-faces.
FIELD TESTING: ENGINE MODEL B STOI-
CHIOMETRIC AIR/FUEL WITH WELLHEAD GAS - The
composition of the oil, which depends on the additive
package, has been found to have a significant effect on
valve wear based on field testing. Three oils with different
compositions were tested in Engine Type B for valve
recession. The engines were all turbocharged, 12-cylin-
der, four-cycle with 115.4 liter displacement. The load on
the engines varied between 80 and 110%. The intake and
exhaust valves were measured for recession using a
bridge gauge that measured the change in height of the
valve tips. The valves were measured at the start of the
test and then about every 2000 hours thereafter.
The composition of the test oils is identified in
Table IV.
Table IV
Elemental Compostion of SAE 40 Test Oils
Viscosity
at 100°C,
cSt Ash, % Ca Zn P
| Ashless Oil H 13.5 0 0 0 0.067
| Low Ash Oil E 13.5 0.45 0.12 0.03 0.03
I Low Ash Oil Z 13.5 0.36 0 0.13 0.11
The oils include Oil H (an ashless oil which does
not contain calcium or zinc), Oil Z (0.36% ash oil with zinc
dithiophosphate), and Oil E (0.45% ash oil with calcium
and zinc). Oil changes were made in accordance with the
engine manufacturer's recommended interval (nominally
1500 hours).
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Face of Valve Face of Valve

Figure 15 - Scanning Electron Microscopy Figure 16 - Scanning Electron Microscopy

Exhaust Valve-Face - Stoichiometric Engine Exhaust Valve-Face - Stoichiometric Engine
Type B - Oil H (Ashless) Type B - Oil Z (Low Ash With Zinc)

In the field test, Oil H (ashless) gave high valve elemental composition. Then the deposits were removed
recession on the exhaust and intake valves, Oil Z gave from the valve and analyzed by XRD. Significant differ-
high exhaust and low intake valve recession, and Oil E ences were found between the valve deposits which could
gave low intake and exhaust valve recession. The aver- account for the valve recession performance differences.
age valve recession results from the field test are found in The exhaust valves run on Oil H (ashless) showed
Table V. no visible deposits on the valve-face. Some phospho-
rous, silicon, cobalt, and chromium were present on the
Table V surface. The phosphorous was from the lubricating oil
Valve Recession Reid Data - Engine B and the other metals were from the valve. The valve-face
surface was very rough and it appeared that high tem-
Engine Average Valve Recession,
Load, Ash, jim/1000 Hours perature corrosion had taken place. See Figure 15.
Oil % Wt% Ash Type Exhaust Intake Limit The exhaust valve run on Oil Z showed no visible
H 90-110 0.0 None 94.0 53.3 50.8
deposits, however, using XRDtwocrystallinecompounds,
E 90-110 0.45 Calcium/Zinc 20.3 25.4 50.8
Zn3(P04)2 and Zn2Co(P04)2, were found. See Figure 16.
Z 80-90 0.36 Zinc 147.3 15.2 50.8
This indicates that without calcium detergent in the oil, the
zinc dithiophosphate may be chemically attacking the
valve surface and forming a compound that can be easily
At the end of the field test, the exhaust valves removed. Again, the valve-face surface was very rough
were removed from the engine and the valve-face depos- and it appeared that high temperature corrosion had taken
its were analyzed. The valves were analyzed by SEM and place.
EDXRF to determine the surface morphology and the

1
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The exhaust valve run on Oil E had a thicker,

visible coating on the surface (not found on the other oil's
valves), which reduced valve recession. SEM/EDXRF
showed high levels of Ca, S, and P. Using XRD the
deposit was identified as Ca5(P04)30H, which is calcium
phosphate hydroxide (hydroxylapatite), a form of enamel
that is difficult to remove. It is possible that this deposit
protects or seals the valve from attack of high temperature
exhaust gases and prevents high temperature corrosion.
See Figure 17. Oil E had most of its ash supplied by
calcium.
Effect of Changing From Ashless Oil to Low-Ash
Oil - Additional valve recession tests were run in the field
with Engine Type B running at 100% load. Using Oil H
(ashless oil) we monitored valve recession for 3800 hours.
The engine had high average exhaust valve recession
wear rates of 76.2 to 114.3 [im/1000 hours. See Figure
18. This was over the manufacturer's recommended rate
of 50.8 jLtm/1000 hours. After the inspection, the engine oil
was changed to Oil E (low ash oil with calcium and zinc)
and no immediate effect of the low ash oil on valve
recession was found. However, after another 2000 hours
the valve recession wear rate dropped significantly below
the manufacturer's limit and stayed at the low rate. We
speculate that it took some time to develop a film or
deposit which then began to protect the valve. When the
ash was predominantly calcium, a reduction in valve
recession rate was observed. This was confirmed in
Face of Valve numerous field test experiments.
FIELD TESTING: ENGINE TYPE B LEAN BURN - As
Figure 17 - Scanning Electron Microscopy described earlier in this paper, lean-burn engines can
Exhaust Valve-Face - Stoichiometric Engine have different valve wear performance than stoichiomet-
Type B - Oil E (Low Ash Ca + Zn) ric engines due to the engine operating conditions. Higher
gas pressures, gas turbulence, and oxygen levels with
lean-burn engines can affect valve recession. To deter-
mine the valve wear performance of lean-burn engines, a
•— Ashless Oil H field test was initiated in a lean-burn version of Engine
• Low Ash Oil E Type B running at 60-90% load on Oil E. The valve
recession performance was monitored for 5899 hours and
^ 125
then an exhaust valve was removed for analysis. The
Oil
Changed average exhaust valve recession rate was acceptable
£ 100
CO (45.7 (im/1000 hours - limit = 50.8 jum/1000 hours; how-
c ever, 6 of the 24 exhaust valves had very high valve
o 75
"(7> recession, over the recommended limit. All the intake
CD
0) Limit valves had low valve recession wear.
o 50
0) Representative low wear and high wear exhaust
DC valves were analyzed. One low wear exhaust valve was
25
covered with a protective deposit, however, there was an
2,000 4,000 6,000 8,000 10,000 indication that at least some high temperature corrosion
o>
CO had occurred. See Figure 19. Analysis of the deposit by
1_
0) Hours XRD showed the deposit to be calcium sulfate (CaS04)
3 and calcium zinc phosphate [CaZn2(P04)2]- Analysis of
the high wear exhaust valve showed no protective deposit
Figure 18 - Engine B. Exhaust Valve Recession on the valve.
 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014
Figure 20 - Low Wear Exhaust Valve-Face 19,082
Hours Engine A Depth Profile by XPS
Figure 19 - Scanning Electron Microscopy
Exhaust Valve-Face - Lean-Burn Engine
Type B - Oil E (Low Ash Ca + Zn)
The valve-face deposit morphology from the stoi-
chiometric and lean-burn engines was different, even
when running on the same oil. This can be seen by
comparing Figures 17 and 19. The same hard-facing was
used on the valves in the stoichiometric and lean-burn
engines; the valves ran against the same seat-insert
materials.
ANALYSIS OF VALVE-FACE DEPOSITS FROM
LOW WEAR FIELD TEST ENGINES- Two gas engine
exhaust valves from field tests, with low valve recession
wear rates, were analyzed by XPS to determine the solid
film lubricant deposit and metal surface elemental compo-
sitions. A depth profile was obtained by repetitively ion-
etching the surface with argon.
Some elements were present at low levels and
some were present at high levels. The elemental depth
profile of an exhaust valve from Engine A, was obtained
after 19,082 hours of engine operation on wellhead gas
and Oil E (oil drains were made at the manufacturer's
recommended interval: 750 hours). See Figure 20.
50 100 150
Depth Etched, in Angstroms
Ca Fe, Cr, Co
150
Depth Etched, in Angstroms
S, Oxidized -+- S - A - CI
Na -O- Zn -^- P
Figure 21 - Low Wear Exhaust Valve-Face
19,082 Hours Engine A Depth Profile by XPS
The depth profile shows that Engine Type A valve
surface has a coating which contains oxygen, calcium,
iron, chromium, cobalt, and nitrogen at relatively high
levels. The metals are from the valve and seat hard-
coatings, the calcium is from the lubricating oil detergent/
base-containing additives, and the nitrogen is from com-
bustion air and/or lubricant dispersant additives. The
probable compounds present are metal oxides, calcium
oxide, and metal nitrides. The data shown in Figure 20
have been corrected to provide an ordinate that is the
atom fraction expressed on a carbon-free basis. This
removes the influence of any remaining oil film (hydrocar-
bon) and carbonaceous residues left on the valve surface.
It is possible that metal carbides are also formed on the
exhaust valve surface.
Lower levels of sulfate, sulfide, chlorine, sodium,
zinc, and phosphorous were detected on the exhaust
valve-face of Engine A. See Figure 21.
The sulfur and oxidized sulfur are associated with
the decomposed by-products of the zinc and calcium
inhibitor and detergent/base-containing additives (e.g.,
 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014
50 100
Depth Etched, in Angstroms
-+- Ca - * - Fe, Cr, Co
Figure 22 - Low Wear Exhaust Valve-Face Engine B
Depth Profile by XPS
50 100
Depth Etched, in Angstroms
S, Oxidized - 4 - S -+- CI
Na -O- Zn -*r- p
Figure 23 - Low Wear Exhaust Valve-Face
Engine B Depth Profile by XPS
calcium sulfate and zinc sulfate). Calcium sulfate was
confirmed by XRD. The zinc, phosphorous, and sulfur are
sourced from the antioxidant/antiwear additive, zinc
dithiophosphate. Calcium-zinc phosphate was found by
XRD. The chlorine probably came from the fuel gas, since
it was not present in the new or used lubricating oil or
combustion air in significant quantities.
Another low-wear exhaust valve from Engine Type
B was analyzed by XPS. The exhaust valve was operated
for 6633 hours on wellhead gas and Oil E. The surface of
the exhaust valve-face from Engine Type B contained
oxygen, calcium, metals, and nitrogen similar to that of
Engine Type A, as shown in Figure 22. The major
difference was that the Engine Type B exhaust valve-face
had more calcium compounds and less metal compounds
at the surface.
Lower levels of sulfur, oxidized sulfur, sodium,
zinc, chlorine, and phosphorous were detected on the
Engine Type Bexhaustvalve (also similarto Engine Type A).
See Figure 23.
The major difference was that there was more
phosphorous in this surface film. XRD analysis showed
that calcium sulfate and calcium-zinc phosphate were
present in the film on the valve-face.
An important finding in our study was that the
deposits, on the valve-faces of the best wellhead and
pipeline gas engines, were very thin but continuous. The
deposit coatings on the valve-face were gray-blue colored
[33]. A gray-blue dull deposit coating has been observed
on low recession valves in the literature and found to be
150 beneficial [14].
NEW FAMILY OF GAS ENGINE LUBRICATING
OIL ADDITIVE PACKAGES - As shown in this paper, the
types of lubricating oil additives chosen for a gas engine
oil package can have a significant effect on valve reces-
sion performance. Additives are used for a number of
reasons besides valve recession performance which include:
1. Deposit Control (Pistons, Crankcase, Top
Deck of Valve Train)
2. Acid Neutralization (Oil)
3. Oxidation and Viscosity Control (Oil)
4. Wear Protection (Piston Rings, Cylinder
Liners, Bearings, Gears, Crankshaft,
Cams, Lifters)
150
A new family of four-cycle gas engine lubricating
oil additive packages, based on the same core technol-
ogy, can provide extended valve life in many kinds of
service. Members of that family are characterized below
in Table VI to guide the reader in selecting the appropriate
additive package for a given type of gas engine service.
All of the additive packages shown in Table VI
contain the same core additive components which are
needed to provide exceptional deposit, wear, oxidation,
and nitration control in four-cycle stationary natural gas
engines. However, differences between packages are
available to meet the needs of specific applications.
For example, a low-ash, moderate TBN, oil is
needed for wellhead sweet gas and pipeline quality gas
containing low levels of sulfur in the fuel (<10 ppm), which
can form low levels of sulfuric acid after combustion.
A medium-ash, higher TBN, oil is needed for
engines running on sour wellhead gas or sewage plant
digestor gas to neutralize higher levels of sulfuric acid
after combustion. Some lean-burn engine manufacturers
specify an intermediate ash oil of this type for low valve
recession.
Landfill gas engines require special additives to
promote the neutralization of halide acids, and they re-
quire surfactants to protect the metal surfaces of engine
components from halide acid corrosion.
In summary, the right gas engine oil additive
package must be applied to each type of gas service to
maximize performance in many areas, including valve
recession.
 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014

Table VI
New Family of Four-Cycle Gas Engine Lubricating Oil Additive Packages

Finished Oil TBN, Lubricating Oil

Finished Oil mg KOH/g Additive
Gas Service Ash, Wt % (ASTM D 2896) Composition Special Formulation Features
Wellhead Sweet Gas 0.45 5.1 Ca, Zn, P, S, N Low Ash
and Pipeline Gas Exhaust Emission Catalyst Compatible
Wellhead Sour Gas and 0.89 8.5 Ca, Zn, P, S, N Higher TBN
Sewage Digestor Gas (Increased Ca) Exhaust Emission Catalyst Compatible
Lean-Burn Engines
Landfill Gas 0.7 5.6 Ca, Zn, P, S, N Low Ash
Neutralization Rate Promoters for Halide Acids
Surfactants for Ferrous Metal Corrosion Protection
Landfill Gas 0.99 8.0 Ca, Zn, P, S, N Higher TBN
(Increased Ca) Neutralization Rate Promoters for Halide Acids
Surfactants for Ferrous Metal Corrosion Protection

CONCLUSIONS

Based on laboratory and field test experience in
four-cycle gas engines, we have reached the following
conclusions regarding valve recession performance:
1. The amount of solid lubricant film formed on the valves
is important -- there can not be too much or too little
lubricant film -- if valve life is to be extended. The
amount of film deposited depends on the ash level of
the lubricating oil and the engine oil consumption.
2. Lube oil ash is needed to develop a protective film on
the exhaust valve and seat surfaces. XPS has shown
that calcium oxide and sulfate films, calcium phos-
phate hydroxide, and calcium-zinc phosphate films
are most effective.
3. The composition of the valve solid film lubricant is
important and directly relates to the engine oil additive
components: calcium and zinc containing oils give
superior valve life, compared to an oil containing zinc
alone or an ashless oil.
Lean-burn gas engines are more severe regarding
exhaust valve recession than stoichiometric engines,
largely due to the oxidizing nature of the exhaust
gases.
Valve and seat angles as well as valve-face and valve-
seat hard facing alloys have a large effect in reducing
valve recession of four-cycle gas engines, especially
in lean-burn (air/fuel ratio) and landfill gas applica-
tions. Valve rotation rate must be adequate but not
excessive (approximately 1 -2 rpm gives good results).
A family of new lubricating oil additive packages based
on the same core technology can provide the appropri-
ate amount of ash, and composition of ash, to extend
valve life in any type of four-cycle stationary gas
engine service.

4. Fuel gas must be properly pretreated and have ad-

equate knock resistance for the engine in use to allow
the lubricant to extend valve life. Landfill gas produces
engine combustion chamber and valve deposits, con-
taining high levels of silica, even when elaborate
pretreatment systems are used.

5. Mechanical assembly and maintenance as well as

engine operating conditions must be under good con-
trol to allow the engine lubricant to extend valve life
and give long cylinder head overhaul intervals.
 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014
ACKNOWLEDGMENTS
The authors would like to thank Chevron Chemical Com-
pany for permission to publish this paper and express their
appreciation to:
1. J. A. Petersen of Waukesha Engine Company for
helpful discussions and review of the manuscript.
2. R. Nevenger, J. Passe, M. Quinn, and D. Brandes
of Caterpillar Inc. for helpful discussions and review
of the manuscript.
3. S. Schaefer of Eaton Corporation for review of the
manuscript.
4. J. T. Gilmore for the microprobe analysis.
5. P. R. Ryason and P. R. Keck for the tribology
analysis, SEM photographs, and EDXRF.
6. Sheila Yeh for the ESCA and XPS analysis.
7. K. K. Ong and R. C. Medrud for the XRD analysis.
8. D. S. Ahlwardt and R. Tanaka for deposit sample
analysis.
9. J. L. Greenhill for a review of the literature on valve
recession (while a summer student in 1991 at
Chevron Research and Technology Company as
part of the Summer Professional Program).
10. T. S. Eitzen, J. A. McGeehan, E. J. Gellner, D. W.
Spooner, K. L. McLeod, F. Fernandez, R. A. Reese,
M. Dearing, and M. R. Logan for helpful discussions
and review of this paper.
11. A. P. Horvath, Z. Bishop, D. S. Ahlwardt, J. G.
Robbers, and M. Hern for field test inspections and
surveillance.
12. L. A. Updike, K. A. DeLong, L. A. Steeley, L. S.
Rush, A. A. Hwang, and I. S. Ransley for prepara-
tion of the manuscript and figures.
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October 1960.
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(1963).
6. W. S. Giles, "Valve Problems With Lead-Free
Gasolines," SAE Paper 710368, presented at SAE
Mid-Year Meeting, Montreal, June 1971.
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8. R. D. Nevinger and J. E. Passe, Caterpillar Inc.,
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February 1993.
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Diesel Engine Valve Guttering," SAE Paper 880669
(1988).
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pp 191-195.
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Their Suitability for Wider Applications," NPRA,
Tech 65-29L, September 1965.
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14. Y. Reyraud and S. Michon, "Moteurs Gaz," B2920- 29. R. van Dissel et al., "Engine Valve-Seat and Insert
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16. American Gas Association (1962).
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(1993).
18. D. Godfrey and R. L. Courtney, "Investigation of the
Mechanism of Exhaust Valve Seat Wear in Engines
Run on Unleaded Gasoline," SAE Paper 710356
(1971).
19. W. L. Kent and F. T. Finnegan, "The Effect of Some
Fuel and Operating Parameters on Exhaust Valve-
Seat Wear," SAE Paper710673 (1971).
31. G. C. Clark, "Sulfidation Corrosion of Nickel-Base
Exhaust Valves," SAE Paper 750044 (1975).
32. D. J. Stevenson, "Availability of Additives to Meet
the Changing Automotive Oil Quality Require-
ments," Paper F&L 70-48, presented at NPRA
National Fuels and Lubricants Meeting, NewYork,
September 1970.
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San Francisco, October 1970.
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Engines," ASTM Paper 63-WA-321 (1963).

20. H. M. Wiles, "Gas Engines Valve and Seat Wear,"
SAE Paper650393(1965).
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With Ceramic and Metal Valves in Firing Engines,"
SAE Paper 890177 (1989).
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Inc., personal correspondence with E. J. Gellner,
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Natural Gas Composition in Select Major Metropoli-
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communication with W. R. Pyle, dated May18,1993.
 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014

APPENDIX

Table A-l
Typical Gas Composition (14,15, 35)

% Higher
Gas %S %Cr^ %CO %CG2 %Ng %o2 %H2 % C2H 4 % CgHe % C^Hg % C4H3 %C4H10 %He % C3H 6 HXCV

Wellhead 0.001-15"! 8-984 10-92 10-85 0.2-4.2 1-5 1-5 0.01-15 1-5

Worldwide 0.001 81-97 0.2-1,8 0.3- 0.01- 3-14.7 0.2-2.9 - 0.1-0.9 0.01- 0.01-0.2
Pipeline 14.0 0.1 0.5

U.S. Avg. <0,001 93.2 1.3 1.4 <1 <0.1 3.6 0.8 0.5 <0.1
Pipeline
U.S. Min. <0.001 55.8 0.2 0.3 <1 <0.1 0.7 0 0 <0.1
Pipeline 2

U.S.Max. <0.001 98.1 1.8 15.1 <1 <0.1 14.7 23.7 2.1 <0.1
Pipeline 2

Landfil|3 0-0.2 25-55 45-75 2-6 <2

Digester 0.01-0.04 35-65 - 30-40 1-2 - - - - 1-2

Commercial - Trace - - 0.5 2 65 2 30

"Propane"

Commercial - - - - - 3.2 6.1 21.8 69 -

"Butane"
Producer Gas - 1-3 12-24 10-18 45-60 - 8-24 - - - - <1

Coker Gas 24-29 8-9 2-3 7-10 50 2-3 0.8-1 <1

Water Gas <0.5 40-42 5 3-4 - 48-52 <0.1

Heavy Oil 31-32 4 8-9 15-16 - 38-39 1.0 0.1

Cracking Gas

1
Wells with natural gas having h^S levels up to 88% have been discovered in Alberta (35). Most engineers only operate on gas with less than 2% h£S.
2
With propane-air, peak-shaving.

^Landfill gas can contain other contaminants such as H 2 0 , particulate silica, polysiloxanes, halogenated hydrocarbons, and chlorofluorocarbons. The particulates are normally
removed by 0.4 u.m filtration and h^O is removed by condensation to 2-3°C dew point prior to use in an engine,

4Engines are seldom operated on wellhead gas with a methane content less than 30-40%

Table A-ll
Characteristics of Combustible Gases (15)

HI
Characteristics Specific Density Theoretical Air-
Mass, Relative to Air Fuel Ratio Number, Methane Octane Autoignition Flammability
kg/m 3 (Air = 1.0) Heating Value, mJ/m 3
(Volume), mS/m 3 mJ/m 3 Number Number Temperature, °C Limits, %

Gas Height Lower Lower Upper

Natural Gas 0.74-0.89 0.57-0.66 35.2- 31.7- 8.4-10.6 44-54.6 67-88 100- =580 4.8-6 13.7- 20-35 I
44.4 40.1 125 15.7

Commercial 1.98 1.53 99 91.4 23.5 80 40 95 480 2.4 9.3 30-40 I

Propane
Commercial 2.6 2.00 128.4 118.7 30.7 90.8 28 88 420 1.8 8.8 -
Butane
Biogas 1-1.1 0.77-0.85 23.3-26 21-23.4 5-6.6 25-29 120 125 - -6 =18 10-20

Coker Gas 0.56 0.44 19.9 17.7 4.3 30 - - - 4.6 32 20-50

Producer Gas 1.1-1.2 0.85-0.93 4.8-6.1 4.6-5.8 0.9-1.2 5-7 - 80 - =20 =73 20-40

CH4 (Methane) 0.176 0.554 39.9 35.87 9.6 53.6 100 130 580 5 15 -
H 2 (Hydrogen) 0.09 0.07 12.77 10.76 2.4 48.27 0 60 570 4 75 260

CO 1.25 0,967 12.64 12.64 2.4 12.85 70 100 610 12.5 75

 Downloaded from SAE International by Chevron Global Library, Monday, December 08, 2014

Table A-lll
Data from Reference 36, Values in Weight Percent

Uses and Manufacturers of Materials and Their Compositions of Some Common Valve and Valve-Seat Materials
Use Manufacturer Ni Co Fe C Cr W Si Mn Cu Other
Eatonite Valve Facings Eaton Corporation 37-41 9-11 0-8 2-2.75 27-31 14 0-1
Inconel Exhaust Valves Inco Alloys 72.5 7 0.05 0.5 0.25 Al, Ti, S,
Alloy 751 Base Metal International Inc. Nb, Ta
Stainless Valve-Seats American Stainless Bal. 0.12 Min. 8-60 0.4
Steel A.S.S. Steel Company
Stellite 1 Valve Hard Deloro Stellite Ltd. Bal. 2.4 33 13
Facings
Stellite 6 Valve Hard Deloro Stellite Ltd. Bal. 1 26 5
Facings
Tool Steel Base Metal Slater Steels Bal. 0.45-0.55 3-3.5 0.2-1 0.2-0.8 Mo, V
Type S-7

111

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