Fuel Blend and Mixture Strength Effects on Autoignition Heat Release Rates and Knock

Intensity in S.I. Engines

Author(s): D. Bradley, G. T. Kalghatgi and M. Golombok
Source: SAE Transactions , 1996, Vol. 105, Section 4: JOURNAL OF FUELS AND
LUBRICANTS (1996), pp. 2224-2237
Published by: SAE International

Stable URL: https://www.jstor.org/stable/44729205

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 962105

Fuel Blend and Mixture Strength Effects

Autoignition Heat Release Rates and
Knock Intensity in S.I. Engines
D. Bradley, G. T. Kalghatgi, and M. Golombok
Shell Research Ltd., Chester UK.

ABSTRACT 1. INTRODUCTION

In general, the rate of heat release during combustion

The in a
purpose of this study is to measure experimentally
spark ignition engine, can have two components:heat one release
due rate due to knock for a variety of fuel mixt
to normal burning in a propagating flame, and anotherand todue
study the influence of this upon the knock inten
to autoignition in the end gas. It has been possible Knock to is the result of a string of processes. Th
ultimately involve autoignition of unburned gas
separate these two components by analysing the pressure
acoustic ringing (1). The connection between explo
trace of a single cylinder engine. From this, the volumetric
autoignition
autoignition heat release rate can be inferred and studied in and the noise is the volumetric heat re
rate
some detail. To approximate this rate in an Arrhenius (2,3). In normal combustion the pressure in
form
combustion
presents difficulties, in so far as it is not possible to chamber is rapidly equalised by acou
measure the temperature at the instant of maximum heat at the speed of sound - typically on a time scal
transfer
release rate, at the onset of knock. However, it was milliseconds.
possible However, with autoignition, it is possible
to measure end gas temperatures by the CARS techniquelarge amounts of chemical energy to be released locally
a time scale of microseconds. This can cause a very h
prior to autoignition and then to estimate the temperature
localised
at the onset of autoignition by extrapolation. Estimation ofoverpressure to be developed, faster than it ca
the temperature at the instant of maximum heat release (4). A strong pressure pulse is created that mo
equalised
rate has enabled kinetic parameters to be assigned in from
away an the autoigniting centre. It is not surprising
Arrhenius expression for this rate over a range of intensity is found to be related to the locali
the knock
heat release
temperatures. These parameters have been measured for rate.
fuels of different octane number, and for an aromatic and
paraffinic fuel blend of identical MON at different Extensive
mixture studies of the end-gas using flame emission
schlieren
strengths. From these parameters and an earlier analysis of photography show autoignition usually to beg
the coupling of pressure waves generated during at localised centres, termed variously autoignition cent
autoignition with chemical reaction, the likelihood of a
exothermic centres, and hot spots, which may then me
(5-10).of
particular fuel blend giving rise to a particular mode Here we shall use 'autoignition centre' in a gen
autoignition can be assessed. The most damaging sense
mode and
is reserve 'hot spot1 to indicate the region
localised
a developing detonation, which occurs at high values of the explosion. At the onset of knock, which
originates
autoignition volumetric heat release rate. Such rates are at a hot spot, the end gas is occupied by
higher for paraffinic than for aromatic fuels under the centres (at least one of which has just become
autoignition
same conditions of temperature and pressure. As a aresult,
hot spot),
a deflagrating kernels originating from such
centres,
developing detonation is more likely for a paraffinic thanand unburned gas. Centres of autoignition can
originate
for an aromatic fuel blend. For the paraffinic blends, the from imperfect mixing of the fuel and air, the
lower are both the octane number and the air/fuel ratio,
mixingthe
of residual hot gas from the previous cycle with the
colder
higher is the volumetric heat release rate, and hence alsofresh charge, heat transfer at the walls, and the
the knock intensity. desorption of reactive species from wall deposits. Initially,
they are approximately equal in size to the integral length
scale of turbulence, which is about 1 mm in a conventional
gasoline engine. To become a locally explosive hot spot
their size must be greater than a critical value that can be

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estimated from thermal explosion theory (1 1), or computed
with a full kinetic model (4)
Autoignition and knock are not identical. A benign
autoignition is possible, in which the acoustic disturbance
is much less than that with knock, a consequence of a
relatively low volumetric heat release rate. Although knock
intensity correlates with the mean temperature of the end-
gas (12), the knock starts as a localised hot spot explosion
In general, the temperatures at hot spots soon become
much higher than the mean temperature of the end gas.
Indeed, these local hot-spot temperatures would appear, at
present, to be experimentally inaccessible, due to the
difficulty of predicting where, and when, autoignition
might occur.
König et al. (6) characterised three different reaction
propagation modes after initial autoignition at a hot spot,
dependent upon the temperature gradient. These are: (i) for
a veiy small temperature gradient: very rapid thermal
explosion; (ii) for an intermediate temperature gradient:
developing detonation in which the reaction is coupled
with the pressure wave; and (iii) for a large temperature
gradient: a deflagration in which the pressure wave
attenuates and outruns the reaction wave. Of greatest
concern is a developing detonation, which gives rise to
severe and damaging knock. The other two modes tend to
be associated with trace and moderate knock, although Pan
and Sheppard (7) have shown the additional influence of
the interactions from multi-centre autoignition. Using the
same mathematical model as in (6), Bradley et al. (13)
have demonstrated that, for a fixed temperature gradient, a
reactive mixture is conducive to the developing detonation
mode, while a less reactive one is conducive to the
deflagration mode.
Much attention has been devoted to the autoignition delay
time (14), which determines whether autoignition will
occur, but it is the volumetric heat release rate at
autoignition that determines the severity of any knock and
is the subject of the present paper. To analyse knock it is
necessary to derive the heat release rate from engine
pressure traces and Refs. (2,3) describe previous work on
this theme at the Shell Research and Technology Centre,
Thornton, using the adapted analyses of Heywood and co-
workers (15,16). This work shows the knock intensity to
increase with the overall maximum heat release rate. It was
extended in (13) to enable the heat release rate due to
autoignition to be separated from that due to flame
propagation. This enabled a closer, albeit very
approximate, analysis to be made of the chemistry of
autoignition. It was shown that when knock occurs, the
localised maximum volumetric heat release rate due to
autoignition was significantly lower for aromatic than for
paraffinic fuels - the quantitative explanation for the
observation that aromatics "knock more quietly."
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In this work, as in (6). an Arrhcnius global expression for
volumetric heat release that is first order in fuel
concentration is assumed for autoignition. If an estimate of
this heat release rale can be made and if an appropriate
mean temperature can be attributed to the autoigniting gas,
then from results over a sufficiently wide range of
temperature, it is possible to derive an Arrhenius 'A ' factor
and activation temperature from Arrhenius plots. Such
values are shown to provide a rough basis for assessing the
propensity of different fuels to damaging knock.
The overall heat release rate during knocking combustion
comes from normal flame progression as well as
autoignition. The paper presents an improved method for
identifying the point of autoignition. The net rate of heat
gain after this point in non-autoigniting combustion is
subtracted from that in autoigniting combustion to give the
heat release rate from autoignition. The peak heat release
rate due to autoignition coincides with the onset of knock.
From the total heat release due to autoignition up to this
point it is possible to estimate an equivalent mass that is
autoigniting , and hence find the autoignition heat release
rate per unit mass. The details are discussed in Section 2.1
below.
Mean temperatures in the unburned gas prior to
autoignition have been measured using the CARS
technique (3,12,17), at different pressures. The
temperature in the unburned end-gas prior to the
maximum heat release rate was estimated from an
extrapolation of these earlier values. As in (13), it is
assumed that the effective temperature in an Arrhenius
expression for the maximum volumetric heat release rate is
elevated by a fixed amount above this estimated mean
temperature of the unburned end-gas. The details are
discussed in section 3.3 below.
Measurements in a Ricardo E6 engine for iso-octane/n-
heptane mixtures and toluene/n-heptane mixtures have
been analysed over a range of normalised air-fuel ratios.
There is some influence of octane number over the range
covered, as well as one of air/fuel ratio. The nature of the
fuel blend is important. The aromatic fuel blend displays
smaller volumetric heat release rates at autoignition, and it
is because of this that it is less prone to severe knock.
2. THEORY
2.1 Heat release analysis
The zonal analysis of Refs. (15) and (16) applies ene
conservation to the charge in the cylinder. A net heat
by the charge, dQ , is comprised of a contribution from
propagating flame, dQj, and sometimes an autoignition hown in Fig 1 are typical profiles of the net rate of heat
gain by the charge, Q , in MW against 0 for both a
contribution, dQa , minus the heat loss, dQ Thus
knocking and a non-knocking cycle. The start of
autoignition is identified by the change in gradient of this
dQ = dQf{+dQa)-dQl (1) curve at point 'A' at a value of 0 equal to 0 A. The
pressure record from which these data were obtained is
The last term becomes much more important after the peak
shown in Fig. 2. Knock, as indicated by the onset of
value of Q has been attained (1,2). The analysis is only
oscillations on the pressure record, was observed to begin
valid when the pressure is uniform and cannot be used
very soon after the maximum value of Q, (Qm), had been
once knock has developed. The variation of Q with crank
angle 0, charge volume V, and pressure p is given attained
by at a value of 0 equal to 0 * (Fig. 1). It was
assumed that during the short interval of time from the
dQ _ 1 dp y dV start of autoignition to the attainment of Qm, the
contribution of flame heat release and heat loss to the wall
d6 y - 1 V d8 y-'pd0 (2)
could be found by extrapolation of the Q profile from the

The onset of knock was associated closely with the prior period in which there was no autoignition.

maximum value of dQ/d0 (2,3). In (15) Chun and

Heywood used a two zone analysis to determine the
appropriate value of y , the ratio of specific heats, for use
in the above one zone expression, to give the chemical heat
release.
The three components of dQ are separately unknown and a
differencing procedure was adopted to evaluate dQa . This
rested upon the identification of the start of the
autoignition heat release.
That this combined contribution was substantially constant
and equal to the value of Q at 'A', namely QA , was
confirmed by examination of Q profiles in non-knocking
cycles. The autoignition heat release rate, Qa , is given by
the difference between the value of Q in an autoigniting
cycle and the extrapolated value at that instant, QA . Below
we shall analyse the maximum value of Qa , denoted by
Qam- ( Qam~ Qm ' Qa )■

Fig. 2. Pressure records for a strongly knocking (full line)

Fig. 1. Variation of net rate of heat gain, Q, for a strongly
knocking (full line) and a non-knocking (broken line)
cycle. The knocking cycle has a high maximum heat
release rate due to autoignition. 'A' marks the start of
autoignition. qa is the heat release rate at 'A', due to flame
propagation minus the heat loss rate. It is assumed to be
constant from 'A' up to the time when Q attains its
maximum value of Qm. 6* is the crank angle at Qm.
and a non-knocking (broken line) cycle. 0O marks the start
of combustion by spark ignition.
2.2 Autoignition model
The chemical kinetics for the autoignition of gasoline fuels
are extremely complex and imperfectly understood. For
present purposes it is sufficient to simplify them by
imposing an Arrhenius global expression that is first order
in fuel concentration. This gives an autoignition
volumetric heat release rate:

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 qa = A p/ j f Al / cxp(- E / Ri) (3) The value of the mass fraction p f in zone 'A', associated
with 7 , decreases as the autoignition reactions proceed.
in which A is an Arrhcnius constant, p is the density of the For a lean mixture, it can be related to a reaction progress

mass of mixture, p j- the mass fraction of the fuel, A// the

variable, c, expressed as the fractional temperature
increase It readily can be shown that
heat of reaction. 7 the temperature, E the activation energy
and R the universal gas constant. The central problem is to
find, for the known value of Qam, the volume and mass Rf ~ Rfu^~ci ~ R fu'S^b ~ 7 ) / '('0) ~ Tu)' (6)
over which this reaction is occurring, and the appropriate
value of T to substitute into Eq. (3) in which p and Tu arc the initial mass fraction and
temperature just prior to autoignition, and 7¿ is the burned
Because of prior autoignition, just before the onset of
gas adiabatic temperature. Because of the impossibility of
knock, originating at a hot spot, the end gas is occupied by
measuring the temperatures within the autoigniting
already autoignited, autoigniting, and unburned gas. A
volume, zone 'A', at the instant of maximum heat release,
three zone model is postulated which lumps all the
the estimation of the temperature, T , appropriate to Eq. (4)
dispersed autoignited and autoigniting gas in one
presents problems. This necessitates further assumptions.
autoignition zone, 'A', as shown in Figure 3b. All the
unburned gas occupies zone 'U', and burned gas is
Let the temperature, T, at which qam is attained be
contained in zone 'B'. Figure 3a shows the prior position of
elevated by an amount AT above the unburned gas
the propagating flame just after the onset of autoignition
temperature prior to autoignition. Hence
and, more realistically than in Fig. 3b. It also illustrates the
way in which the centres of autoignition are dispersed in
the end gas.
T = Tu + AT (7)

The numerical solutions for hot spot pressure generation, which, with Eqs. (4) and (6), gives
based on full chemical kinetics and the momentum
equation, of Lutz et al. (4) show the pressure wave to move I" (Qamha) " ln(l-(A7V(7¿
away from the hot spot as the autoignition heat release rate
attains its maximum value. In the present work, the onset ltĻl/^Atf) - E/R(T
of knock occurs very soon after Qam is attained (2,3). The
associated mean volumetric autoignition heat release rateIn the early stage of autoignition the
rate is low. The present analysis appli
in the autoigniting volume at the instant Qam is attained is
at the initiation of knock, where it is
given by qam = Qamplma » *n which ma is the mass of
temperature is higher. If the tempe
autoigniting gas in zone 'A1, of mean density p . Equation
within the autoigniting volume, the h
(3) then gives
be a maximum with a value of A T
also (4)). However, some of the gas
in (ôamK) = ln^yA//) - E/ET (4) volume will be at a lower temperatur
the effective temperature in the reac
Thus Tu < T< Tu +1,100 K. Some nu
that cannot be precise, suggest that t
The mass, ma , as a fraction of the total charge mass, mtot ,
in temperature, A T, in Eq. (8) might
is given by the ratio of the total heat released by
K. We report below, two sets of result
autoignition up to this instant to the total overall heat
800 K, as well as 700 K.
release. Thus
6*
Values of 7¿,, R ju> and A H we
'QaM
Tu = 1,000 K , with the computer
^
developed by Morley (18) at a fixe
mtot tot °e?
mtot The programme
tot computes
)and Q an a
Oo
at constant pressure, Cp, that allows
value of A H is found from the expres
where 60 and 6encj represent the start and end of burning

and 0* is the crank angle at which Qam is attained.

cp^Tb ~ Tu) - &H

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 (a) (b)
Fig. 3a. Position of the
Fig. 3b shows the flam
The flame has propagat

Values of 7¿, and

Table 1 A H
condition in Table 2.
derived from Engine
CARS Characteristics tem
side of Eq. (8) evaluat
Cylinder bore: 76.2 mm
When this is plotted
Stroke: 111 mm
best fit line yields an a
Connecting rod length : 241.3 mm
Inlet valve diameter: 34.6 mm
Exhaust valve diameter: 30.1 mm
3. EXPERIMENT
Compression ratio: 10.18
Valve timings (ATDC) in C4 deg:
3.1 Test Engine and Fuels
Exhaust valve opens 140, closes 365
Inlet valve opens 360, closes 575
Measurements were made in a single-cylinder Ricardo E6
Oil and coolant temperature : 70° C
research engine, modified for optical experiments as
Engine speed: 1200 rpm
described in Refs. (2,3,17). The compression ratio was
Throttle fully open
10.18 and other engine details are listed in Table 1. The
engine was run on different fuels at full throttle at a
constant speed of 1,200 rpm , with different air/fuel ratios
and ignition timings. The normalised air/fuel ratio, A, was measured by a
Lambdascan analyser. The effects of octane number were
Different, and contrasting, fuel blends were preparedstudied
for by varying the relative iso-octane/n-heptane ratios.
the experiments. There are two major base fuel It was necessary to vary the ignition angle of advance for
components of gasoline, namely catalytic reformate (or the various mixtures to generate the different knock
"platformate") and light alkylate. They have different intensities. The motor and research octane numbers (MON
knocking behaviours as a consequence of their different and RON) for these fuels were measured in a CFR engine
aromatic and paraffinic components (2). Similar according to ASTM procedures (D-2699 and D-2700). The
data for all the fuel blends and the normalised air/fuel
differences in knocking characteristics and autoignition
heat release rates are observed with idealized fuel blends ratios employed are given in Table 2. The paper reports on
consisting of toluene/n-heptane (TOLHEP) and iso- three PRF fuel blends and a simple aromatic fuel blend of
octane/n-heptane mixtures (Primary Reference Fuel, PRF) toluene and n-heptane (TOLHEP), at three different
air/fuel ratios.
at the same motor octane number of 91.7 (2,3). These
blends were employed at different air/fuel ratios in the
present tests.

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 Tahle 2

Fuels and mixture properties used in the tests ( Tu = 1,000 K )

FUEL Fuel blend MON RON X spark m p A// 7^

( %v ) advance ioi (M.J/kg) ^
(CAD <"'*)

PRF91.7 91.7% iso-octane 91.7 91.7 0.88 13 550.5 0.0707 34.27 2767
8.3% n-heptane 1.0 19 545.9 0.0622 37.8 2756
1.1 22,25 542.8 0.0566 40.13 2693

PRF 89 89% iso-oclane 89 89 1.0 7,8 545 0.0623 37.36 2756

1 1% n-heplane

PRF 98 98% iso-octane 98 98 1.0 15,16,17 547 0.0615 37.38 2756

2% n-heptane

TOLHEP 85% toluene 91.7 102 0.88 28 554.8 0.0774 31.5 2818
15% n-heptane 1.0 32 549.6 0.0681 34.93 2796

Thedata
Overall, there are seven different knock intensity,
sets. For KI, is a
thegiven
difference between the
set,
the knocking characteristics canmaximum
be expressed
and minimum ofin the terms of signal. A
filtered pressure
the pressure and temperature of knocking
the cycle
end-gas
is arbitrarily
justdefined
prior
as one in
towhich the
knock, irrespective of how this state
value of has
KI exceeds been
0.2 bar reached
(17,3). In Figs. 1, 2, 4 and 6
(3,17). Other experimental details and
different pressure and the mixture
heat release parameters are shown
properties are shown in Table 2,for
as is the mean total mass
a knocking (full line) and a non-knocking (broken line)
of the mixture in the cycle, mļot cycle,. for a stoichiometric
This last ismixture of PRF 91.7,
required for namely a
PRF fuel of 91.7
the calculation of ma , and is estimated octane number.
from Figure 2 shows a pressure
measurements
trace
of the mean air consumption rate around top centre (TC). This knocking cycle has a
(17).
high knock intensity of 3.2 MP a and a significantly higher
3.2 Pressure data and heat release rates peak pressure than has a corresponding non-knocking
cycle.

Pressure is measured using a Kistler type 6001 fast

response piezoelectric transducer. This is an AC detector, The value of £), is obtained from Eq. (2). Figure 1 shows
and is calibrated against known standardisation pressures. the variation of this net rate of heat gain with crank angle
The base line pressure is assumed equal to the average for both cycles. Shown in Fig. 4 are the two net overall
pressure in the intake manifold; for wide open throttle this heat releases Q, obtained by integrating the Q profiles over
is atmospheric pressure. An optical encoder provides a the two cycles in Fig. 3. The end of combustion is assumed
timing mark on a second channel which allows the data to to occur when Q is a maximum and the crank angle is
be calibrated against the crank angle. Cycles are sampled 6end , as marked on Fig. 4. The fraction of burned mixture
following a trigger that activates a high speed data mass at a given crank angle, 6y is given by the ratio,
acquisition computer. The sampling rate is 500 kHz , which
Q(ö)/Qm> where Qm is the maximum value of Q and also
at the engine speed of 1,200 rpm corresponds to a
is marked on Fig. 4.
resolution of 139 ps. The data were analysed using
FAMOS waveform analysis software (2,17).
3.3 Estimation of the unburned gas temperature, at
The voltage-time trace was converted to one of absolute the point of maximum heat release rate
pressure against crank angle. The knock signature was
obtained by filtering the pressure between 5 and 25 kHz. The temperature of the unburned end-gas prior to
autoignition was measured by Coherent Anti-stokes Raman

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 pressure, p . in bar , by a best-fit cune through all the
^ +1.60
measured data points for fuels that has the form
^ + 1 .40
2" Ö m , Qnd
II +1.20

01 / ^ 7 = 34 0(p) (10)
% +1.00
<
/
/
~7^"
m
ÏÏ
+0.80
/
- / These results are reproduced in Fig.
2 / /
<£ <
+0.60- /
/ / 7
/
+
S
0.40
/
- / •"

+ 0.20 ^ "" '

Filled Symbols, knocking

linn
linn UUU
UUU" "
□ vFuel (PRF 90) I
+ 0.00 -

Fuel (IsoOcune) , . „
innnA~ °Fuel (Tol/Hcp)
Fuel (Buone) T1 It łTlT1 1
It +
O.20 ¿j
A Fuel (Tol/Hcp) 1
innn lwu ~ O Fuel (Propane* . 1 . . j - '
i r «o H

-30.0 -20.0 -10.0 + 0.0 +10.0 + 20.0 + 30.0 + 40.0 + 50.0 + 60.0

CRANK ANGLE DEGREES (CAD) AFTER TOP CENTRE (ATC)

900 - I J Jj
ł
I 800 - » *
Fig. 4. Net overall heat release, Q, from integration of Q
curves in Fig. 1. 6en(j is the crank angle at theii
end700
of " -JL- -
burning. Reduction in Q after dencļ is due to heat Q
losses.
n ■
« r/y.

1-25. T# ■ 340K
Knocking cycle, full line, non-knocking cycle, broken-line.

400 - /
2.0 3.0 4.0 1.0
Spectroscopy (CARS). With this, a frequency doubled
Pressure. MPa
Nd:YAG laser (532 nm) pumps the transitions in the
nitrogen molecule and a YAG pumped Rhodamine 6G dye
laser provides the probe. Laser access to the engine is
Fig. 5. Mean CARS tem
through windows in a slice inserted between the cylinder
vs mean pressure at w
head and the block of the engine. The point of
different fuels. Repro
measurement in the end gas is about 5 mm from the wall in
than propane show sig
the end-gas region. The sampling volume (corresponding
expected from compre
to the depth of focus of the collinear lasers) is about 1
mm* . The laser is triggered to sample at controlled times
during the compression stroke and after ignition. In fact,
CARS measurements are not possible up to the instant of For each knocking cy
flame arrival, because the developing thermal gradients a maximum was foun
around the optical measurement point scatter the laser gave Tu. Shown in
beam and make signal collection impossible. Typically, unburned mixture m
sampling was possible up to 25° after TC. Since the mixtur dmtot), also
pressure data and laser measurements are synchronised, it
against the crank ang
is possible to obtain the pressure in the chamber at the Figs. 1, 2 and 4. The
instant of temperature measurement. This pressure is
terminated at 0* .
required in order to calculate the temperature from the
spectral analysis of the CARS signal.

4. RESULTS AND DISCUSSION

Further details of the technique are given in (17), where it
is shown that it yields reliable mean temperatures in the
unburned end-gas. Measurements were made at different 4.1 Volumetric Heat Release Rates, Knock Intensit
and Arrhenius Constants
crank angles and hence different pressures with different
fuel/air mixtures. It was found that when the mean
temperature in the end-gas is plotted against the meanShown in Fig. 7, for the PRF blends, are Arrhenius plots of
pressure, the results for propane/air mixtures fall on Eq. a (8), with the left side, derived from experiment, plotted
polytropic line and the temperature increases solely due toagainst the reciprocal of temperature T=(tu + A t) , with
compression. However, for other fuels, the measuredAT = 800 K . Plots of the same parameters, but for the
temperatures increase as a result of some heat release fromtoluene/n-heptane blend (TOLHEP) are shown in Fig. 8
which is drawn to the same scale as Fig. 7. For the
pre-flame reactions (17,3). For all the mixtures reported in
the present work it was possible to relate the mean TOLHEP blend there were many cycles which showed
temperature, 7' (°K), in the unburned end-gas to the multiple peaks in the heat release rate curve, indicative of

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 difficulties and the necessary assumptions that have had to
be made, it is not surprising that there is considerable
scatter in the data points. A best-fit straight line can be
fitted to the experimental points for each condition listed in
Table 2 by regression. Cycles which yielded values of less
than 22.5 for the left side of Eq.(8) have been ignored in
the regression. This is because they are considered to be in
the very low knock, low temperature regime (see (13) and
section 4.2 below). The regression parameters, assuming
AT = 800 K, are listed for each condition in Table 3a: for
AT = 700 Ky they are listed in Table 3b. In these tables, R
is the correlation coefficient. The spread of data points is
such that the differences between individual conditions
cannot be established with sufficient confidence, although
some general trends can be discerned and these are
discussed below

Fig 6. Temperature of unburned end-gas, Tu, estimated
from Eq. (10) and the unburned mixture mass fraction for
the two cycles in Figs. 1, 2, and 4. The curves for the
knocking cycle are terminated at 0* . Knocking cycle, full
line: non-knocking, broken line.
multiple, but non-violent, autoignitions. Such cycles have
not been considered. In view of the experimental
The value of AT is, of course, uncertain; and the validity of
the assumption that it is constant unproven. Hence there is
uncertainty as to the absolute values of lhe Arrhenius
parameters listed in Tables 3a and 3b. Nevertheless, this
analysis does allow different fuels to be compared. It also
provides a link between the observed behaviour of knock
intensity and earlier theoretical work on modes of
autoignition, to be discussed in section 4.2.

24 "I PRF 89
pRF91 7 * x
"5 PRF 98 £x

^ ° O Xx
ä 23 " °

□ PRF91.7 (1.0) © ixc^ xxx ^

o PRF91.7(1.1) P0,ntS ab0Ve this line used in regression ļ □ oď X x
S x
22 _ x PRF89 (1 .0) □
o PRF98 (1 .0) 0 °
° D
a PRF91.7 (0.88)

21 -]

0.00052 0.00053 0.00054 0.00055 0.00056 0.00057 0.00058 0.00059 0.0006 0.00061

1/(71, +800), l/K

Fig. 7. The left side of Eq. (8) plotted against 1 IT for the PRF

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 24 1

_ .¿V; «
râ 4^' -■ <• # ♦ . -
S
£ 23 " ■' " ,|ř"ířx1' ■
< " :;" ■ />■ " */'
i "'f " Sv. ■ X
■ ■ «
je
I

gQ
^ 22 -
S
.çg ■ TOLHEP (0.88)
"jg" ♦ TOLHEP (1.0)

21 H

0.00052 0.00053 0.00054 0.00055 0.00056 0.00057 0.00058 0.00059 0.0006 0.00061

1 /(Tu +800), 1/K

Fig. 8. The left side of Eq. (8) plotted against l/T for the toluene/n-heptane blend, (T =

Table 3a
Results of Regression Analysis to Points in Figs. 6 and 7. AT = 800 K

Fuel X Slope of Standard In ( A) Standard Number of

line, "Tact* I error on I A in | error on I | observa
K 1 act* K I sec'1 I In (A ) IR2 I
PRF91.7 LO 27500 2300 24.14 L3 067 74

PRF91.7 1.1 29800 2300 25.46 1.32 0.79 45

PRF91.7 0.88 28400 3700 24.91 2.12 0.76 21

TOLHEP 0*88 30000 2900 24.78 L58 (L43 144

TOLHEP 1.0 21000 4700 20.09 2.56 0.29 52

PRF89 L0 26600 1900 23.77 L19 074 68

PRF98 L0 34400 3300 2T8 L85 062 69

PRF91.7 ALL 27000 1700 23.98 0*95 066 140

ALL PRF ALL 22400 1200 21.27 069 055 277

TOLHEP ALL 26500 2600 22.89 L39 (L35 197

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 *

Fig. 9. Knock intensity plotted against the autoignition volumetric heat release rate, qam , at 6 for the seven cases (see Table 2)
considered.

For PRF 91.7, the influence of mixture strength cannot be
discerned clearly in Fig. 7; this is also true for the
TOLHEP blend in Fig. 8. Earlier work (3) showed that the
inherent susceptibility to knock does not depend strongly
on mixture strength for a given fuel. We therefore combine
the results for different mixture strengths for a given fuel.
In Tables 3 a and 3b the results of regression analysis,
irrespective of mixture strength differences for PRF 91.7
and TOLHEP also are listed. Neglecting, in Fig. 7, the
small differences between the primary reference fuels with
different octane number and mixture strengths, a single
straight line was fitted to all the data points. The
regression parameters of such a fit also are listed in Tables
3a and 3b. The slope of the straight lines yields the
activation temperature, Tact- The overall value using all
the PRF data with AT = 800 K and suitable rounding , is
22,400 ± 1,200 K (mean ± standard error). With
AT = 700 K, this becomes 19,700 ± 1,100 K . The
corresponding temperatures for the TOLHEP blend,
obtained by fitting the data in Fig. 8, are 26,500 ± 2,600 K
and 23,600 ± 2,300 K , respectively. This difference in
Tact between the PRF and TOLHEP data for a given value
of AT is statistically significant at the 95% confidence
limit. Values of the Arrhenius constant, A , for the four
straight lines in these two figures are given in Tables 2.
The best-fit lines for PRF 89, PRF 91.7 (for all mixture
strengths) and PRF 98 in Fig. 7 suggest that as octane
number decreases, the heat release rate increases at a given
temperature. Consideration of all the data for PRF 91.7
suggests that the heat release rate for the richer mixture is
marginally higher than for the leaner mixture. The best-fit
line for all mixture strengths is shown for the TOLHEP
blend in Fig. 8. It can be seen that for this fuel, the
temperature regime in which autoignition occurs is higher
than for the primary reference fuels; the points lie to the
left of the points in Fig. 7. For a given temperature the heat
release rate is smaller for the TOLHEP blend than for the
primary reference fuels. The difference between the two
blends of fuels in Figs 7 and 8 is significantly larger than
are the variations within each blend.
4.2. Modes of Autoignition
Simplified theory (11) suggests that the localised
overpressure generated at a given hot spot is proportional
to the volumetric heat release rate. This suggests a
relationship between the heat release rate and the knock

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 Tahle 3b

Results of Regression Analysis to Points in Figs. 6 and 7. AT = 700 K

Fuel ' Slope of Standard In ( A) Standard Number of

line, -Tacf, error on A in error on observations
K Tact, K see' In (A) R2
PRF 91.7 TÕ : 24200 2000 23.00 ¡L23 067 74

PRF 91.7 1.1 26200 2100 24.22 1.24 0.79 45

PRF 91.7 0.88 27000 3900 24.99 2.35 0.72 21

TOLHEP 088 26800 2600 23.90 FM) 043 144

TOLHEP 1.0 18800 4200 19.42 2.42 0.29 52

PRF 89 To 23400 1700 22.66 L05 074 68

PRF 98 TÕ 30300 2900 26.46 L75 061 69

PRF 91.7 ALL 23900 1500 22.82 065 065 140

ALL PRF ALL 19700 LUX) 20.29 065 055 277

TOLHEP ALL 23600 2300 22.11 L32 035 197

intensity, and this is explored in at

chemical reaction Fig.
a shock 9.
frontThis shows
in the unburned gas. th
This reinforces the
knock intensity (KI) for knocking wave, which
cycles (KItakes>on0.02
the MPa
plotted against the estimated maximum
characteristics volumetric
of a developing hea
detonation. The pressure
wave and chemical reaction are coupled. In the limited
release rate at 8 *, qam = Qari¿>lmai for the seven
space of the cylinder, although it cannot become a fully
combinations of fuel blend and mixture strength. The gas
developed detonation, the overpressures can be sufficient to
density, p at 8* is estimated from
cause the
severe engine ideal
damage gas
(6). There law
is no using
such tendency
at the lower volumetricT.
the known pressure and temperature, heat release rates: here the weaker
pressure wave outruns the reaction wave, it is not
Relationships for PRF 89, PRF
reinforced 98 and
by reaction and itTOLHEP are show
attenuates, in this deflagration
mode. There appears
by the full lines. As previously noted to be no(13),
tendency for
at a detonation
the to highe
octane numbers, two regimes can
begin to develop be
with discerned,
the toluene/n-heptane blend. one fo
reaction at lower temperatures, with small volumetric hea
The detailed study
release rates and knock intensities, the of these
other effects for
involvedreaction
numerical a
higher temperatures withanalysis
larger of the propagation
heat of release
a pressure wave originating
rates and
knock intensities. at a hot spot and its chemical interactions. Details of this
analysis are given in (6,13). An example of the result of
Within both regimes the relationship between knock such an analysis, for a cylindrical geometry (13), is shown
intensity and volumetric heat release rate is close to linear. in Fig. 10. Here computed dimensionless profiles of
However, at the lower octane numbers, demonstrated by pressure and temperature, for two different activation
the curve for PRF 89, this linearity disappears at the higher temperatures, are plotted against radius at three different
heat release rates, a small increase in which can produce a times. Pressures are normalised by the initial pressure, p0 ,
large increase in knock intensity. This can become of 4 MPa, temperatures by the initial temperature, T0, of
sufficiently high to be seriously damaging. The reason for 1 ,000 K at the axis, and radii by the cylinder diameter, D ,
this is discussed in (13) and is summarised below. of 85 mm. The initial temperature gradient away from the
hot spot, or more correctly, hot line, is linear and equal to -
If the localised hot spot overpressure is high enough, when
it propagates as a pressure wave outwards it can induce

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 "[ 15 - I 1 15 ì
15 - 16MS 15 /
24MS

Í '« ^ S°10 " 16,5

32,s A/

5^JL¿ A/
OÍ
r/D rlD
5 i

^ ' 1 1 '
°oo olí 0I2 o!3 o!4 o!s 0.0 0.1 ' u 1 <u 1 0.4 ' as
r/D r/D

(a) W
Fig. 10. Computed radial propaga
is radius normalised by cylinder
mode. See text for other paramet

23.5 KJmm but , when

reaction, but subsequently is attenuated;the tem
an initial coupling
remains constant at this value. The influence of of chemical reaction and shock, later to be uncoupled.
temperature gradients in the unburned gas is discussed in
[6]. The initial value of ppfuAH at the centre is The 32 results of extensive computations over a range of
values of A and Tact are summarised in the plots of
MJ m 3, and the value of A is 3x10^ sec'1. In Fig. 10(a)
ApuPfu&H at the same initial, normalising conditions,
Tact is 20,000 K. The pressure wave is weak and it
against TqcV normalised by the initial temperature at the
attenuates as it moves outwards. The temperature wave
moves outwards with a lower velocity and the two waves hot line, 1,000 K , in Fig. 11. The thick lines delineate the
modes of autoignition. With the volumetric heat release
are uncoupled. These aspects characterise the deflagration
mode [6]. In Fig. 10(b), for the lower activation rate expressed by A pup AH exp( ^ - TactlT) 311(1
temperature of 15,000 K , the pressure pulse is reinforced as
T = 1,000 K, an indication of its range of values is given
it propagates and both waves are strongly coupled
by the two thinner lines on the diagram for 0.01 and 1.0
throughout the propagation in a developing detonation. At
an intermediate activation temperature, Tact, of 17,000 K G W m , at the initial conditions. The bounds for the
the pressure pulse initially is amplified by chemical developing detonation and deflagration modes, as well as
the transition regime between them, are shown by the two
bold straight lines. In the transition regime, initially, the

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pressure pulse is coupled to reaction and is amplified, but schlieren photography. Knock intensity has been shown to
subsequently it becomes uncoupled and decays. For the be related to this volumetric heat release rale
same initial normalising conditions, the present
experimentally measured bounds for the values of 2. The knock phenomenon has been described in terms of
A pufifu AH , that arise from the error bands on A, and
an Arrhenius global kinetic equation that relates the
volumetric heat release rate to the temperature and
Tact are shown by four rectangles. These arc for both the
pressure. However, because temperatures can only be
TOLHEP and PRF blends (ignoring octane number and measured prior to autoignition, and because the
mixture strength effects). The rectangles for A T = 800 K autoigniting volume is not accurately known, it is difficult
have full lines and those for AT = 700 K have broken
to derive the volumetric heat release rate accurately.
lines. The length of the side of each rectangle is two Nevertheless, by making some assumptions, it has been
standard errors of the relevant parameter. Despite the wide estimated and Arrhenius constants and activation
uncertainty bands, it is clear that the PRF blends are closer
temperatures are presented.
to the developing detonation mode than is the toluene/n-
heptane blend .
3. In spite of the many assumptions made, there are clear
differences between the primary reference (paraffinic) fuel
blends and the toluene/n-heptane (predominantly aromatic)
blend. For similar temperatures and pressures, the
ieL ,
maximum autoignition heat release rates for the paraffinic
10 " {Developing
fuel are higher than those for the aromatic fuel.
17 ļ Transi
4. For the same conditions of temperature and pressure,
'g 16ļ / ' TOLHEP AT=800 K fuel blends with a lower octane number give a higher
£ 10 ! ¡/ _Áy ' TOLHEP, AT=700 K
X ' , 7 / S ' PRp. AT=800 K volumetric heat release rate. Though less marked, there is
il <n15U-=,GWto , / // ' '
^ 10; / // PRF ÓT = 700 K a similar trend of a higher heat release rate with a lower
à / yC air/fuel ratio. These differences are not statistically
~ ioļ y ' [ Deflagration ļ significant in the context of the data collected here but the
trends are in line with observations on knock intensity.
IO13" <k=o.oi GW/m3
12l

5. With the lower octane numbers the knock intensity can

10 15 17 19 21 23 25 27 29
increase very rapidly with volumetric heat release rate. It
( w 1000 ), TaCļ in K
would appear that this is associated with transition to the
developing detonation mode.

Fig. 11. Diagram showing modes of autoignition

6. Plots ofin terms
initial heat release rate parameters against
of kinetic parameters. Initial hot spot conditions 4 MPa ,
activation temperature can delineate the modes of
autoignition.
1,000 K and pupfuAH = 32 MJ m~~3 . Thin linesThe present observations with different fuel
show
_3 blends suggest that their knocking behaviour aligns
volumetric heat release rates of 0.01 and 1.0 GW m for
approximately with these regimes.
these conditions. Kinetic parameters listed in Tables 3a
and 3b. Rectangles show error bands. Full line rectangle is
for AT = 800 K , broken line rectangle is for AT = 700 K . ACKNOWLEDGEMENTS

We wish to thank Professor Chris Morley, our colleague a

5. CONCLUSIONS Shell Research and Technology Centre Thornton, for
stimulating discussions and for his computer programme t
1. It has been shown possible to evaluate the maximum calculate combustion parameters. We also thank Messr
autoignition volumetric heat release rate, W. A. Clowes and K. I'anson for their help with the
qam = QamPl ma » ^ judicious estimates of the terms on experiments.
the right of the expression, on the basis of a three zone
model. The crucial step is to relate the experimental
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