Aerosol Science and Technology

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Structural Properties of Diesel Exhaust Particles

Measured by Transmission Electron Microscopy
(TEM): Relationships to Particle Mass and Mobility

Kihong Park, David B. Kittelson & Peter H. McMurry

To cite this article: Kihong Park, David B. Kittelson & Peter H. McMurry (2004) Structural
Properties of Diesel Exhaust Particles Measured by Transmission Electron Microscopy (TEM):
Relationships to Particle Mass and Mobility, Aerosol Science and Technology, 38:9, 881-889,
DOI: 10.1080/027868290505189

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Aerosol Science and Technology, 38:881-889, 2004
Copyright © American Association for Aerosol Research
ISSN: 0278-6826 print I 1521-7388 online
DOl: I 0.1080/027868290505189
Structural Properties of Diesel Exhaust Particles Measured
by Transmission Electron Microscopy (TEM): Relationships
to Particle Mass and Mobility
Kihong Park, David B. Kittelson, and Peter H. McMurry
Department of Mechanical Engineering, University of Minnesota, Minneapolis, Minnesota
Structural properties of diesel particles preclassified by particle
mobility and mass are measured using transmission electron mi-
croscopy (TEM). These measurements enable us to determine the
dynamic shape factor and inherent material density of diesel par-
ticles. We also compare fractal dimensions obtained independently
using two different approaches.
We show that the projected area equivalent diameter of
mobility-classified diesel particles nearly equals the mobility di-
ameter in the size range reported here (50 to 220 nm). Evidence for
doubly charged particles and possible "fragments" are observed
for DMA-classified particles on TEM substrates. The fractal di-
mension was obtained using two independent approaches. Images
obtained by TEM were analyzed to determine the maximum length
and the number of primary particles. The fractal dimension ob-
tained from these measurements, DfL, was 1.75. The fractal dimen-
sion obtained from the mass-mobility relationship, Drn, was 2.35.
We found that these values are in reasonable agreement after ac-
counting for the relationship between the projected area diameter
and maximum length. The size-dependent dynamic shape factor
and inherent material density of diesel particles are obtained from
independent measurements of mobility (DMA), mass (APM), and
volume (TEM). We found that the dynamic shape factor increased
from 1.11 to 2.21, and that the inherent material density increased
from 1.27 to 1.78 g!cm 3 as particle mobility size increased from 50
to 220 nm. The increase in dynamic shape factor with size occurs
because large particles are more irregular than smaller ones. The
increase in density occurs because the ratio of elemental carbon to
condensed organics increases with increasing size.
Received 3 November 2003; accepted 28 June 2004.
Although the research described in this article has been funded
wholly or in part by the United States Environmental Protection Agency
through Grant Number R 826372-01-0 to the Georgia Institute of Tech-
nology and GIT Subcontract Number G-35-W62-GI to the University
of Minnesota, it has not been subjected to the Agency's required peer re-
view and therefore does not necessarily reflect the views of the Agency,
and no official endorsement should be inferred . We also acknowledge
support from NSF Grant Number NSF/ATM-0096555.
Address correspondence to Peter H. McMurry, Department of Me-
chanical Engineering, University of Minnesota, Ill Church Street SE,
Minneapolis, MN 55455, USA. E-mail: mcmurry@me.urnn.edu
][
INTRODUCTION
Diesel particulate emissions are a major source of fine and
ultrafine atmospheric particles. These particles are of current
interest due to their suspected adverse health effects and their
impacts on the earth's radiation balance, visibility impairment,
and atmospheric chemistry. Since diesel particles are geomet-
rically complex and consist of multicomponent mixtures in-
cluding semivolatile compounds (Kittelson 1998; Sakurai et al.
2003b), a comprehensive knowledge of their size, morphology,
and composition is needed to characterize them adequately.
The structure of particles is directly related to their transport
properties and plays an important role in determining their atmo-
spheric residence time and their deposition pattern in the human
respiratory system. Diesel particles in the size range reported
here (50 to ~300 nm) are agglomerates of fine primary par-
ticles coated with condensed organic films. The most common
method to characterize the structure of agglomerates is transmis-
sion electron microscopy (TEM), which provides projected two-
dimensional properties of agglomerates. Thus, the actual struc-
tural properties of agglomerates are inferred from the projected
properties. However, few studies of the structural properties of
agglomerates produced from diesel engines have been reported.
Most measurements have been carried out for flame-generated
agglomerates, for which the relationships between the actual
properties and proj ected properties have been tested (Schaefer
1988; Schmidt-Ott 1988; Megaridis and Dobbins 1990; Koylu
and Faeth 1992; Cai et al. 1995; Sorensen and Feke 1996; Brasil
et al. 1999).
The fractal dimension provides useful insights into the struc-
ture of diesel agglomerates. The number of primary particles in
an agglomerate (N) scales with the radius of gyration (Rg) as
follows (Mandelbrot 1982):
[1]
where kg is the fractal prefactor, dp is the primary particle
diameter, and D 1 is the mass fractal dimension. The fractal
881
882 K. PARK ET AL.
dimension also provides useful insights into the agglomeration
mechanism. Previous work has shown that different agglomer-
ation regimes result in different values of the fractal dimension
(Schaefer 1988).
In this study, the differential mobility analyzer (DMA)-
aerosol particle mass analyzer (APM) technique (McMurry et al.
2002; Park et al. 2003) is combined with TEM to measure struc-
tural properties of diesel exhaust particles that are preclassified
according to particle mobility and mass. The structural prop-
erties of mobility-classified particles are used to determine the
fractal dimension and the dynamic shape factor, while those of
mobility- and mass-classified particles are used to determine the
inherent material density as a function of mobility size. The frac-
tal dimension measured with the TEM is also compared with the
value obtained from the mass-mobility relationship measured
with the DMA- APM technique.
EXPERIMENTAL
Particles were sampled from the exhaust of a John Deere
diesel engine (John Deere 4045, 4 cylinder, 4.5 l, 75 kW). The
variable residence time dilution system (VRTDS; Abdul-Khalek
et al. 1999) was employed to dilute diesel exhaust with clean
cooled air. Kittelson et al. (1998) showed that the particle prop-
erties in the nuclei mode diameter range are extremely sensi-
tive to sampling and dilution conditions. Distributions of larger
accumulation-mode particles, the focus of the current study, are
much less sensitive to sampling conditions. For this study the
VRTDS was operated under conditions that yielded primary di-
lution ratio of ~16:1 and secondary dilution of ~22:1, and a
dilution temperature of ~36° C . The primary stage is designed
to produce high saturation ratios, and thus nucleation, while the
second stage is designed to quickly dilute, to stop nucleation and
Diesel aerosols
Vacuum pump
Figure 1. Schematic of the DMA-APM system.
slow coagulation. Experiments were performed at a constant en-
gine speed of 1400 rpm at an engine load of 50% with EPA fuel
(~ 360 ppm S) and with a commercially available 15W-40 lu-
bricating oil. Note that at the 50% engine load employed in this
study, the larger accumulation-mode particles were dominant
with almost no nucleation mode.
A schematic of the experimental setup is shown in Figure 1.
The diesel exhaust particles are brought to Boltzmann equilib-
rium with a Po-210 neutralizer before they enter the DMA. The
DMA selects particles of a known mobility, and these mobility-
classified particles (50-220 nm) are deposited on TEM grids us-
ing a low pressure impactor (LPI; Hering et al. 1979). A JEOL
1210 TEM (accelerating voltage: 40 to ~ 120 kV, magnifica-
tion: 50 x to ~8 00,000 x) was used to obtain the TEM images.
Copper 200 mesh grids coated with carbon or silicon monoxide
films were used as TEM substrates. The structural properties of
mobility-classified particles are used to determine the fractal di-
mension and the dynamic shape factor. Also, the DMA-selected
particles were classified according to mass with the APM (Ebara
et al. 1996) prior to sampling by the LPI. The structural proper-
ties of those mobility- and mass-classified particles are used to
determine the inherent material density as a function of mobil-
ity size. The APM consists of two cylindrical electrodes rotating
together at the same controlled speed (~ 3000 rpm). A voltage is
applied to the inner electrode with the outer electrode grounded.
Particles are introduced into the small gap between two elec-
trodes and experience centrifugal and electrostatic forces. The
APM transmits particles of a known mass (independent of par-
ticle shape or composition), determined by the balance of the
centrifugal and electrostatic forces. More details on the APM
can be found in Ebara et al. (1996). The relationship between
mass and mobility size can then be used to determine the effec-
tive density as well as fractal dimension of the diesel exhaust
 STRUCTURAL PROPERTIES OF DIESEL PARTICLES
particles. Such measurements are discussed in detail by Park
eta!. (2003). In this article we focus on additional information
that can be obtained when mass- and mobility-classified parti-
cles are analyzed by TEM.
RESULTS AND DISCUSSION
Projected Properties of Diesel Agglomerates
In the measurements reported below, particles are preclassi-
fied by the DMA (mobility) or DMA-APM (mobility + mass)
and then their projected properties are measured. TEM measure-
ments of primary particles include primary particle diameter (dp)
and primary particle projected area (A p) . Measurements of the
agglomerates include projected area (Aa), maximum projected
length (L), and maximum projected width (W) normal to L, as
illustrated in Figure 2. These measurements are done with the
aid of image analysis software (Digital Micrograph 3, Gatan
Inc.).
To measure the primary particle properties, primary parti-
cles clearly distinguishable in agglomerates are selected and
their diameters are measured. Koylu and Faeth (1992) showed
that for flame-generated agglomerates, the primary particle di-
ameter typically follows a normal distribution with a standard
deviation up to 25o/t:. Lee eta!. (2001) measured primary par-
ticle diameters of diesel agglomerates and found that the mean
primary particle diameter ranged from 28.5 to 34.4 nm with a
nearly normal distribution. Figure 3 shows our result for primary
Figure 2. Major parameters measured from projected images:
projected area (Ap) of primary particles, and projected area (A 0 ),
maximum projected length (L) , and maximum projected width
(W) of the agglomerate.
883
70
Points 223
60 Mean
Median
Std Deviation
50
40
c
::l
0
0
30
20
10
0
0 10 20 30 40 50 60
Primary particle diameter (nm)
Figure 3. Primary particle diameter distribution for diesel ag-
glomerates with fitted normal distribution: John Deere engine,
50% load, 1400 rpm, EPA fuel (360 ppm S).
particle size distribution for diesel agglomerates. We observed
that the mean primary particle diameter is 31.9 nm with a stan-
dard deviation of 7.2 nm. This suggests that primary particles
of diesel agglomerates can be reasonably approximated by a
normal distribution.
We measured the projected area of agglomerates by image
analysis, and calculated the projected area equivalent diameter
(Dprojected) from the projected area. Rogak and Flagan (1993)
showed that projected area diameters of Ti0 2 and Si agglom-
erates are nearly equal to mobility diameters for particles with
mobility diameters up to 400 nm. Our results show that this
also applies to diesel agglomerates in the 50-220 nm mobility
diameter range. Figure 4 shows the projected area diameter dis-
tribution for particles with a mobility size of 120 nm. Also shown
in Figure 4 are the expected mobility distributions of singly and
doubly charged particles exiting the DMA. These distributions
are based on the Gaussian expressions for the DMA transfer
function given by Stolzenburg (1988). A constant inlet size dis-
tribution over the DMA mobility window is assumed in obtain-
ing these results. Note that the heights of these distributions were
arbitrarily adjusted to match the frequency observed by TEM at
120 and 182 nm. The maximum count is observed between 120
and 130 nm projected area diameters, suggesting that the pro-
jected area diameter nearly equals the mobility diameter. Since
the loss of semivolatile materials is possible in the TEM, we
indirectly addressed the effect of the semivolatile component on
the projected area diameter by carrying out TDMA measure-
ments (Sakurai et a!. 2003a). When particles of 70 nm mobility
size were heated to 300°C to remove the volatile organic, the
mobility size decreased by ""3 nm. This would give an upper
limit for the difference between the projected area diameter and
884 K. PARK ET AL.

10 7

6
8
5
E' E'
c E'c
c
0l )
~ 6 ~ 4
~ "
~ ~
0
·o
a. f E 0
"[
3
.::;1 4 0 .:;:1
z ~ z
<l z <l
"0 2

0~~~----~L---~~~~--~~--~
0 200 240 280
40 80 120 160
40 80 120 160 200 240 280
Projected area or mobility diameter (nm)
Projected area or mobility diameter (nm)
Figure 5. Projected area diameter distribution for particles
Figure 4. Projected area diameter distribution for particles
with a mobility size of 150 nm for singly charged particles and
with a mobility size of 120 nm for singly charged particles and
~230 nm for doubly charged particles. The solid curve shows
~ 182 nm for doubly charged particles. The solid curve shows
the expected number distribution (dNI dD p) of singly and doubly
the expected number distribution (dNI dDp) of singly and doubly
charged particles downstream of the DMA. The peak heights of
charged particles downstream of the DMA. The peak heights of
the singly and doubly charged particles were arbitrarily scaled
the singly and doubly charged particles were arbitrarily scaled
to match the count frequency at 150 nm and 230 nm observed
to match the count frequency at 120 nm and 182 nm observed
with the TEM. John Deere engine, 50% load, 1400 rpm, EPA
with the TEM. John Deere engine, 50% load, 1400 rpm, EPA
fuel (360 ppm S).
fuel (360 ppm S).

mobility diameter when all condensed materials are assumed to

be lost in the TEM.
The small peak around ~182 nm is probably due to doubly
charged particles. As we discuss below, we hypothesize that the
peaks around 80 and 160 nm are due to fragmentation oflarger
particles during sampling by the LPI. Figure 5 shows the pro-
jected area diameter distribution for particles with a mobility size
of 150 nm for singly charged particles and ~230 nm for doubly
charged particles. The maximum count occurs between 140 and
150 nm. Evidence for doubly charged particles and "fragments"
is again observed. Note that the abundance of "fragments" in-
creases as particle size increases from 120 to 150 nm. This might
occur because the larger particles have a higher probability of
fragmenting upon impact. Evidence for "fragments" is shown
in the TEM image of mobility-classified particles (220 nm) in
Figure 6. Note that since particles are preselected by the DMA, it
is not likely that such small particles are present in the mobility-
classified samples. Also, note that when samples were collected
using an electrostatic sampler, such fragmentation was not ob-
served, suggesting that inertial sampling by the low-pressure im-
pactor caused this artifact. Froeschke et al. (2003) also observed
that Ag, Ni, and Ti0 2 agglomerates experience fragmentation
when collected on TEM grids using a single-stage low-pressure
impactor. Figure 6. TEM image for mobility-classified particles
The maximum length (L) and width (W) of diesel particles (220 nm mobility size) showing "fragments." John Deere engine,
were also measured. When the average values of L and W for 50% load, 1400 rpm, EPA fuel (360 ppm S).
 STRUCTURAL PROPERTIES OF DIESEL PARTICLES 885

Table 1 ameter, the maximum length should also scale to the mobility
Average values and standard deviations of the maximum diameter with the same power (1.26) as shown below:
length (Lavg), width (Wavg), and axial ratio ((L/ W)avg) of
diesel agglomerates as a function of mobility diameter L ~ D!.26 ~ D!.26
projected mobility· [2]
Dmobility Number Dprojected Lavg Wavg
(nm) of particles (nm) (nm) (nm) (L/W)avg This relationship will be utilized in our discussion of fractal
dimensions.
50 157 45 61 ± 15 43 ± 7 1.5 ± 0.4
80 158 85 117 ± 22 61 ± 9 2.0 ± 0.6
100 305 95 155 ± 26 65 ± 10 2.5 ± 0.7 Fractal Dimension of Diesel Agglomerates
120 209 125 194 ± 37 80 ± 12 2.5 ± 0.8
In order to determine the fractal dimension, the number of
150 159 145 238 ± 47 90 ± 15 2.8 ± 1.0
primary particles (N) and the radius of gyration (Rg) need to
220 77 215 387±77 119±20 3.4± 1.2
be determined, as shown in Equation (1). In this study, the ac-
John Deere engine, 50% load, 1400 rpm, EPA fuel (360 ppm S). tual fractal properties of agglomerates are estimated using previ-
ously published approximations relating the projected properties
to three-dimensional values (i.e., N , Rg). Several studies sug-
a given mobility size are evaluated, doubly charged particles
gested the following relationship between the projected area and
and "fragments" for a given mobility are excluded (i.e., only
number of primary particles (Samson et al. 1987; Meakin et al.
singly charged particles are selected). This was done by using
1989; Megaridis and Dobbins 1990; Koylu et al. 1995a; Brasil
the results of projected area diameter, since the projected area
et al. 1999):
diameter nearly equals the mobility diameter (see Figures 4 and
5). The average values of the maximum length (Lavg), width
(Wavg), and axial ratio ((L/ W)avg) with standard deviations de- [3]
termined in this way are shown in Table 1. The projected area
diameter (Dprojected) is evaluated at the center of the bin where
the maximum count occurred (see Figures 4 and 5). where Aa is the projected area of the agglomerate, A P is the
Figure 7 shows the relationship between the maximum pro- mean projected area of primary particles, ka is an empirical
jected length and projected area diameter for mobility classified constant, and a is an empirical projected area exponent. By
diesel particles of all sizes in this study (50, 80, 100, 120, 150, means of numerical simulations, they found that ka and a fall
and 220 nm). Note that the maximum length scales to the pro- in the following ranges: a = 1.08-1.19 and ka = 1.00-1.81.
jected area diameter with a power of 1.26 rather than linearly. Koylu et al. (1995b) suggested a = 1.09 and ka = 1.15 by
Since the projected area diameter nearly equals the mobility di- their extensive analysis of particle morphology. Oh and Sorensen
( 1997) took the overlapping of primary particles into account and
1000 found that a = 1.19 and ka = 1.81 when the overlap parameter,
which is the ratio of the primary particle diameter to the distance
L =0.440 1 26
.
between two touching particles, is 2. They showed that in their
p
simulated agglomerates, accounting for overlap leads to more
R= 0.94, power relationship
primary particles per agglomerate, and therefore to agglomerates
that are more dense and that have a higher fractal dimension
and prefactor (D 1 = 2.01, kg = 3.0) compared to values when
'E
.s 100 overlapping is ignored (D 1 = 1.80, kg = 1.30). In the present
_j
study, the values of a and ka suggested by Koylu et al. (1995b;
a = 1.09, ka = 1.15) and Oh and Sorensen (1997; a = 1.19,
ka = 1.81) are employed when using Equation (3) to determine
the number of primary particles in diesel agglomerates.
The radius of gyration can also be extracted from projected
properties. Several studies (Samson et al. 1987; Koylu et al.
1995a; Brasil et al. 1999) suggested the maximum projected
10 100 1000 length (L) could be used as a substitute of Rg (i.e., L/2Rg =
Projected area diameter (nm) constant). Based on numerical and experimental work, Koylu
et al. (1995a) suggested L/2Rg = 1.49 for N > 100. Using
Figure 7. Relationship between the maximum projected numerical simulations, Oh and Sorensen ( 1997) and Brasil et al.
length and projected area diameter for diesel particles. John (1999) respectively found that L/2R 8 = 1.45 and L/2R8 =
Deere engine, 50% load, 1400 rpm, EPA fuel (360 ppm S). 1.50. With this approximation, the fractal dimension based on
886
maximum length can be determined as follows:
L )DfL
N = kL ( dp ' overlap in the two-dimensional TEM images.
where dp is the primary particle diameter, kL is the prefactor,
and DfL is the fractal dimension when the maximum projected
length (L) is treated as the characteristic size instead of the radius
of gyration.
However, for small agglomerates (N < 100), the ratio
(Lj2Rg) is not constant (Koylu et al. 1995a), and its value is
sensitive to the degree of overlapping (Oh and Sorensen 1997).
Koylu et al. (1995a) suggested that for agglomerates with D f <
2, projected properties found using TEM can be used to de-
termine the fractal dimension with good accuracy. For D f > 2,
however, projected properties fail to predict the actual properties
accurately, probably due to primary particle screening effects.
Note that diesel agglomerates in the mobility size range from
50 to 220 nm are relatively compact compared to the flame-
generated agglomerates and the cluster-cluster simulated ag-
glomerates studied by previous investigators.
Figure 8 shows the fractal dimensions (DnJ of diesel ag-
glomerates calculated with Equation (4). The projected length
(L) is obtained by direct measurement, while N is determined
from Equation (3) by using a = 1.09, ka = 1.15 (Koylu et al.
1995a) and a= 1.19, ka = 1.81 (Oh and Sorensen 1997). As ex-
pected, a higher fractal dimension (1.75 versus 1.61) is obtained
1000 ,----,...----.-,...-~--.--~,...---,...----.-,...-~--r-~
175
N = 1.91(Lidp) , R2=0.93
Oh and Sorensen ( 1997)
100
~- N (with overlapping)
10
- - N (without overlapping)
161
N = 1.21(Lidp) , R2=0.93
Kyolu et al. (1995b)
10
Lldp
Figure 8. The relationship between the number of primary
particles, N, and the maximum projected length, L, normalized
with respect to primary particle diameter, dp, where the power
represents the fractal dimensions (DrrJ. N is determined from
Equation (3) by using a = 1.09, ka = 1.15 (Koylu et al. 1995b)
and a= 1.19, ka = 1.81 (Oh and Sorensen 1997): John Deere
engine, 50% load, 1400 rpm, EPA fuel (360 ppm S).
K. PARK ET AL.
when using the values of a and ka provided by Oh and Sorensen
(1997) than those of Koylu et al. (1995b).This is because Oh
[4]
and Sorensen (1997) account for the effect of primary particle
We also determined the fractal dimension using the rela-
tionship between mobility size and mass measured with the
DMA-APM technique. These measurements were done on gas-
borne particles. Therefore, these observations reflect true three-
dimensional properties of the agglomerates. Schmidt-Ott ( 1988)
showed that the mobility diameter varies linearly with the radius
of gyration (Dmobiliry ~ Rg) in the continuum regime. This rela-
tionship is also linear in the free molecular regime for particles
with D 1 > 2.0. Since the mass of agglomerates (M p) is pro-
portional to N when primary particle mass is constant over the
size range, the fractal dimension based on mobility diameter and
particle mass, Drm, defined by
M =k ( Dmobility ) Drm
m d , [5]
p
where k111 is the prefactor. The relationship between particle mass
and mobility size measured with the DMA-APM technique is
shown in Figure 9 where the power (2.35) represents the fractal
dimension (Dfm) based on mass and mobility size.
As shown in Figures 8 and 9, different approaches lead to
different values of the fractal dimension (DfL, Dfm). The rela-
tionship between the projected area diameter and the maximum
projected length can be used to find the relationship between
DfL and Dfm. In the previous section, we showed that the mo-
bility diameter nearly equals the projected area diameter. Thus,
10·17 , . . . - - - - - - - - - - , - - - - - - - - - - - - ,
0
100 2 35
- - M = 7.35e-24 * D · R= 0 .99
p me
10·20 '-------------L---------1
10 100 1000
Mobility diameter (nm)
Figure 9. The relationship between particle mass and mobility
size for diesel agglomerates where the power represents the frac-
tal dimension (Drm): John Deere engine, 50% load, 1400 rpm,
EPA fuel (360 ppm S).
 STRUCTURAL PROPERTIES OF DIESEL PARTICLES 887

Equation (5) can be rewritten as 30

M ,.,_, DDrm DDrm [6]

P mobility "' projected· 25

Using the relationship between the maximum projected length

and proiected 126 t d)
area diameter shown in Figure 7 (L "' D proJec 20 Points 58.0
J e '
Equation (6) can be rewritten as Mean 64.5
"E Std Deviation 7.8
N ,.,_, M ~ DDrm ~ DDrm ~ L Drm/1.26 _ u
5 15
P mobility projected [7]

It follows from Equation (4) that 10

Drm
1.26 = DfL. [8] 5

This represents the relationship between Drm and DfL for diesel
particles reported here. From Equation (8) by using the measured 0
30 40 50 60 70 80 90 100
value of Drm (= 2.35), one obtains DfL = 1.87, which is close
to values (DfL = 1.75, 1.61) obtained from measurements of Volume equivalent diameter (nm)
projected properties (i.e., the relationship between the N and L
as shown in Figure 8). Figure 10. Distribution of the volume-equivalent diameters
for mass-classified particles (mobility size: 80 nm, mass:
Dynamic Shape Factor and Inherent Material Density 0.225 fg): John Deere engine, 50% load, 1400 rpm, EPA fuel
(360 ppm S).
In this section, structural properties of diesel particles that
are preclassified by particle mobility and mass are used to deter-
mine the dynamic shape factor and inherent material density. If factors determined in this way. We found that as particle mobil-
the volume equivalent diameter (Dvolume) of a particle having a ity size increases from 50 to 220 nm, the dynamic shape factor
known mobility size is known, the dynamic shape factor (x) can increases from 1.11 to 2.21 (i.e., the drag force increases), sug-
be determined by the following equation (Kasper 1982; Kelly gesting that particles become more irregular (i.e., more highly
and McMurry 1992): agglomerated) with size. This result is consistent with the lower
effective density reported previously for larger particles (Park
Dmobility / Cmobility et al. 2003). Rogak and Flagan ( 1993) numerically calculated the
X= [9]
Dvolume/ Cvolume '

where C is the slip correction factor. The mean volume (V) of 3

n agglomerates can be estimated from the number of primary
particles (N) in each agglomerate and the mean primary particle
diameter (dp) as follows:
:8:
...
2.5

v = Lt N,~di, [10]
-§
n ~
Q)
a.
ro
f
f
..c 2
The number of primary particles and the mean primary particle !/)

diameter are determined by the method described in the previ- .E0

ff
ous section. Since we showed that the projected area diameter ro
c
ro
nearly equals the mobility diameter, the results of projected area >-
0 1.5
diameter can be used to exclude doubly charged particles and
"fragments" for a given mobility size (i.e., we can select only f
'
single-charged particles for a given mobility). In this way, we
can estimate the volume-equivalent size of particles having a
certain mobility size. Figure I 0 shows a distribution of volume- 0 50 100 150 200 250
equivalent diameters for particles of 80 nm mobility diameter Mobility diameter (nm)
where the mean volume-equivalent diameter and standard de-
viation are 64.5 nm and 7.8 nm, respectively. Using Equation Figure 11. The dynamic shape factor as a function of mobility
(9), the dynamic shape factor for these particles is found to be diameter. The error bars represent the standard deviations. John
1.53 ± 0.36. Figure 11 shows size-dependent dynamic shape Deere engine, 50% load, 1400 rpm, EPA fuel (360 ppm S).
888 K. PARK ET AL.
dynamic shape factor for agglomerates with fractal dimension
of 1.8 and containing 50-500 primary particles. They found
that the dynamic shape factor ranged from 1.5 to 2.0. Tohno
and Takahashi (1990) measured the dynamic shape factor of
Pb agglomerates using the relationship between the volume-
equivalent diameter and projected area diameter, providing val-
ues of 2 to 3 in the size range reported here.
The inherent material density equals to the ratio of particle
mass to volume. We evaluated the inherent material density
for particles of several mobilities using mobility- and mass-
classified particles. Masses were determined with APM and vol-
umes by TEM, as described above. The results of these measure-
ments are shown in Figure 12. Note that the inherent material
density is less than 2 g/cm 3 in the size range reported here. This
value is consistent with previous results (Sakurai et al. 2003a)
showing that such particles contain a mixture of organic carbon
(OC), consisting primarily oflubricating oil (Poe = 0.8 g/cm3 ),
and amorphous elemental carbon (EC; PEe = 2 g/cm3 ; CRC
2002). Also note that as the mobility size increases, the inher-
ent material density (1.78 g/cm 3 at 220 nm) increases, suggest-
ing that the contribution of condensable OC is much lower for
larger particles. This is consistent with the results of Sakurai
et al. (2003a). In our other paper (Park et al. 2004), we indi-
rectly addressed the effect of the semivolatile component on the
inherent material density, showing that density for diesel soot
particles was 1.77 ± 0.07 g/cm3 , after they were heated to 300°C
to remove the volatile organics.
• deMity Obtained l'rcrn p311itae m:m ~~~VOlume (50% 1~11)
A del'dity C31CtJI3ted U5ln.g Equallon (11) (II)% IO&CI)
0 derrsity caloolated using Equallon (11) (75% load)
2. 5
..e- 2 -
~ •
~
-..;
c I !I
o•
A
•o • A
«> AA
~ Ae
~
~
E
1:
• obtained from these measurements, DfL, was 1.75. The fractal
e«>
~ 0.5
0 I I I
0 50 100 150 XIO 250
Mob.'lty ~ (nm)
Figure 12. The inherent material density obtained from parti-
cle mass and volume and the inherent material density obtained
from the mass fraction of condensed organic carbon as a func-
tion of mobility diameter. John Deere engine, 10, 50, 75% load,
1400 rpm, EPA fuel (360 ppm S).
Also, we have independently obtained the inherent material
density by assuming that particles contain a mixture of amor-
phous EC and lubricating oil. The relative proportions of these
materials were determined by using the TDMA-APM technique
to measure the decrease in mass that occurred when particles
were heated to ~300°C (Sakurai et al. 2003). We assumed that
all of the organics (and none of the EC) evaporates in the heater.
The inherent material density (Pinherent) can be expressed as:
Moe+ MEe Moe+ MEc x+(l-x)
Pinherent = V.
Oe
+ ViEe Moe + MEc -"'-- + 1- x '
Poe PEC Poe PEC
[11]
where Moe is the mass of condensed OC, MEc is the mass ofEC,
Voe is the volume of condensed OC, VEe is the volume of EC,
and x is the mass fraction of condensed OC (x = M OCM~~EC ) ,
which is obtained from the TDMA-APM volatility measure-
ments. Figure 12 also compares the inherent material densities
determined in this way with values obtained directly from inde-
pendent measurements of mass and volume. We found that the
inherent material densities obtained using these independent ap-
proaches are in good agreement. Note that the inherent material
densities tend to be lower for lower engine loads (10% load),
where particles contain more condensed organics. Also, note
that the inherent material densities of particles tend to decrease
with decreasing mobility size, suggesting that the contribution
of condensed organics ( ~0.8 g/cm3 ) increases.
CONCLUSIONS
TEM measurements for mobility-classified particles showed
that the projected area equivalent diameter nearly equals the
mobility diameter in the mobility size range from 50 to 220 nm.
Doubly charged particles and possible "fragments" were ob-
served for the DMA-classified particles. Two approaches were
used to calculate fractal dimensions. TEM images of mobility-
classified agglomerates were analyzed to obtain the maximum
length and number of primary particles. The fractal dimension
dimension determined in this way was found to be in reasonable
agreement with the value (Dtm = 2.35) determined using parti-
cle mass and mobility size after accounting for the relationship
between the projected area diameter and maximum length.
The combination of DMA-APM and TEM measurements
enabled us to determine the dynamic shape factor and inherent
material density as a function of mobility size. The dynamic
shape factor of diesel particles was obtained from the relation-
ship between mobility and volume-equivalent sizes. The mean
dynamic shape factor increased from 1.11 to 2.21 as mobility
size increased from 50 to 220 nm. This suggests that diesel par-
ticles become more irregular (i.e., the drag force increases) with
size. This result is consistent with the decrease of effective den-
sity with size, which has been reported previously. Results show
that as the mobility size decreases, the inherent material density
 STRUCTURAL PROPERTIES OF DIESEL PARTICLES
decreases, suggesting that the contribution of condensed or-
ganics increases with decreasing size. Inherent material den-
sities found using TEM and DMA-APM are in good agree-
ment with values estimated from the TDMA-APM volatility
measurements.
REFERENCES
Abdui-Khalek, 1. , Kittelson, D. B., and Brear, F. (1999). The Influence of
Dilution Conditions on Diesel Exhaust Particle Size Distribution Measure-
ments, SAE 991142:1-9.
Brasil, A.M. , Farias, T. L., and Carvalho, M.G. (1999). A Recipe for Image
Characterization of Fractal-Like Aggregates, J. Aerosol Sci. 30:1379- 1389.
CRC. (2002). CRC Handbook of Chemistry and Physics, CRC Press, Boca
Raton, FL.
Cai, J., Lu, N., and Sorensen, C. M. ( 1995). Analysis of Fractal Cluster Morphol-
ogy Parameters: Structural Coefficient and Density Autocorrelation Function
Cutoff, J. Colloid lnte!face Sci. 171:470-473.
Ehara, K., Hagwood, C., and Coakley, K. J. (1996). Novel Method to Classify
Aerosol Particles According to Their Mass-to-Charge Ratio Aerosol Particle
Mass Analyser, J. Aerosol Sci. 27(2):217- 234.
Froeschke, S., Kohler, S., Weber, A. P. , and Kasper, G. (2003). Impact
of Fragmentation of Nanoparticle Agglomerates, J. Aerosol Sci. 34:275-
287.
Hering, S. V. , Friedlander, S. K. , Collins, J. J., and Richard, L. W. (1979). Design
and Evaluation of a New Low Pressure Impactor. 2, Environ. Sci. Techno!.
13:184- 188.
Kasper, G. (1982). Dynamics and Measurement of Smokes 1: Size Characteri-
zation of Nonspherical Particles, Aerosol Sci. Techno!. I: 187-199.
Kelly, W. P., and McMurry, P. H. ( 1992). Measurement of Particle Density by
Inertial Classification of Differential Mobility Analyzer-Generated Monodis-
perse Aerosols, Aerosol Sci. Tee/mol. 17:199-212.
](jttelson, D. B. (1998). Engines and Nanoparticles: A Review, J. Aerosol Sci.
29:575-588.
Koylu, U. 0., and Faeth, G. M. (1992). Structure of Overfire Soot in Buoyant
Turbulent Diffusion Flames at Long Residence Times, Comb. and Flame
89:140- 156.
Koylu , U. 0., Faeth, G. M. ,Farias, T. L., and Carvalho, M.G. (1995a). Fractal and
Projected Structure Properties of Soot Aggregates, Comb. Flame 100:621-
633.
Koylu, U. 0., Xing, Y., and Rosner, D. E. (1995b). Fractal Morphology Analysis
of Combustion-Generated Aggregates Using Angular Light Scattering and
Electron Microscope Image, Langmuir II :4848-4854.
889
Lee, K. 0., Cole, R., Sekar, R., Choi, M. Y. , Zhu, J., Kang J. , and Bae, C.
(200 I). Detailed Characterization of Morphology and Dimensions of Diesel
Particulates via Thermophoretic Sampling, SAETechnical Paper Series 200 1-
01-3572.
Mandelbrot, B. (1982). The Fractal Geometry of Nature, San Francisco,
Freeman.
McMurry, P. H., Wang, X. , Park, K., and Ehara, K. (2002). The Relationship
between Mass and Mobility for Atmospheric Particles: A New Technique for
Measuring Particle Density, Aerosol Sci. Techno!. 36:227-238.
Meakin, P., Donn, B., and Mulholland, G. W. (1989). Collisions between Point
Masses and Fractal Aggregates , Langmuir 5:510-518.
Megaridis, C. M. , and Dobbins, R. A. (1990) . Morphological Description of
Flame-Generated Materials, Comb. Sci. Techno/. 71 :95-109.
Oh, C., and Sorensen, C. M. ( 1997). The Effect of Overlap between Monomers
on the Determination of Fractal Cluster Morphology, J. Colloid lnteiface Sci.
193:17-25.
Park, K., Feng, C., Kittelson, D. B., and McMurry, P. H. (2003). Relationship
between Particle Mass and Mobility for Diesel Exhaust Particles, Environ.
Sci. Techno/. 37:577-583.
Park, K., Kittelson, D. B., Zachariah, M. R., and McMurry, P. H. (2004).
Measurement of Inherent Material Density of Nanoparticle Agglomerates,
J. Nanoparticle Res. 6:267- 272.
Rogak, S. N., and Flagan, R. C. (1993). The Mobility and Structure of Aerosol
Agglomerates, Aerosol Sci. Techno!. 18:25-47.
Sakurai, H., Park, K., McMurry, P. H., Zarling, D. D., Kittelson, D. B., and
Ziemann, P. J. (2003a). Size-Dependent Mixing Characteristics of Volatile
and Non-Volatile Particles in Diesel Exhaust Aerosols, Environ. Sci. Techno!.
37:5487-5495.
Sakurai, H., Tobias, H. J. , Park, K. , Zarling, D., Docherty, K. S., Kittelson , D. B.,
McMurry, P. H., and Ziemann, P. J. (2003b). On-Line Measurements of Diesel
Nanoparticle Composition and Volatility, Atmos. Environ. 37:1199- 1210.
Samson, R. J. , Mulholland, G. W., and Gentry, J. W. (1987). Structural Analysis
of Soot Agglomerates, Langmuir 3:272- 281.
Schaefer, D. W. (1988). Fractal Models and the Structure of Materials, MRS
BULLETIN 13:22.
Schmidt-Ott, A. (1988). Physical Characterization of Agglomerated Aerosol
Particles Through Size-Invariant Fractal Properties, Physics 309:113-115.
Sorensen, C. M. , and Peke, G. D. (1996). The Morphology of Macroscopic Soot,
Aerosol Sci. Techno/. 25:328- 337.
Stolzenburg, M. R. ( 1988). An Ultrafine Aerosol Size Distribution Mea-
suring System, Mechanical Engineering, Ph.D. Dissertation, University of
Minnesota, Minneapolis, MN.
Tonho, S., and Takahashi, K. (1990). Morphological and Dynamic Character-
ization of Pb Fume Particle Undergoing Brownian Coagulation, J. Aerosol
Sci. 21:719- 732.