1 s2.0 S0021850214000032 Main PDF
1 s2.0 S0021850214000032 Main PDF
1 s2.0 S0021850214000032 Main PDF
N
i 1
i
2
s
s
2
i
; 4
where
i
are the individual measured values for n
CPC
, n
FCE
and s
i
their standard deviation. All data was collected in parallel
with an analogdigital converter and recorded with a PC.
2.5. Setup for comparison (with Kr-85 charger)
For comparison only, a parallel setup was built up which is equal to the system described above, but it contained a
radioactive bipolar charger (Kr-85, approximately 95 MBq) for charge conditioning instead of the ESP and IPC and used a TSI
long column cylindrical DMA (Model 3071, TSI Incorporated, USA) operating with 20 l/min sheath air and 3 l/min sample air.
With this setup counting efficiencies were measured with a GFG aerosol as well as with a Combustion Aerosol Standard
(CAST) aerosol. The CAST implemented a dilution and an evaporation tube to remove the volatile species (AVL Particle
Generator, AVL LIST GmbH, Austria). For the realized experiments the evaporation tube as well as the first dilution step was
held constant at 314 K. At the inlet of the volatile particle remover the aerosol was diluted with dry particle free air with
Fig. 2. Setup to prove CPC calibration. The reference CPC TSI 3775 and the diffusion battery are optional to validate the CPC calibration system.
B. Grob et al. / Journal of Aerosol Science 70 (2014) 5058 53
a ratio of 1:3 by volume. After passing the evaporation tube a cold dilution (dilution factor: 4:1, ambient temperature
approximately 293 K) took place.
3. Results
The above-described system for measuring the counting efficiency of a UN-ECE Regulation 83 compliant CPC was
evaluated in detail. Three independent series of measurements have been performed, comparing the measured number
concentration of the reference CPC with the FCE, as well as applying a counting efficiency curve and a linearity check for the
regulation compliant CPC. Additionally the results are compared with the conventional method using a radioactive source as
the charge-conditioner. Furthermore we checked the difference between the CAST aerosol and the GFG aerosol as the
calibration material.
3.1. Particle size control
At the beginning of every series of measurements the setup was checked by the diffusion battery in combination with the
reference CPC. As an example Fig. 3 shows for the three series the penetration through the screens versus the number of the
screens for 23-nm particles. By the linearity of the data in the semilogarithmic plot it can be seen that the penetration scales
with the exponential function of the screen number. The high coefficient of determination (R
2
40:999) indicates that the
data fits perfectly to the model and evidences the monodispersity of the aerosol. Moreover the very low standard deviation
between the slopes of 0.13% demonstrates the high repeatability of the system.
3.2. FCE compared to reference CPC
The key point for the usability of the indirect photoelectric charger as an alternative to a radioactive bipolar charger is the
number of multiple charged particles, which influence the charge number concentration directly. The charge number
concentration calculated by Eq. (1) has to be equal to the effective number concentration; otherwise a significant number of
multiple charged particles are present. Figure 4 shows the number concentration measured with the reference CPC versus
the charge number concentration of the FCE for 55-nm particles. The different concentrations were achieved by adjusting
the discharge frequency of the GFG (between 7 Hz and 22 Hz). Again the perfect linearity demonstrates that there are no
unexpected errors or artifacts in the system. The low standard deviation of 0.5% of the mean value of the slopes indicates a
high repeatability of the calibration system. The deviation between the lines through origin and the mean value of the
slopes of the three lines is only 1.1%. Apparently the number of multiple charged particles is so low that there is no
significant effect measurable for this particles size.
3.3. Counting efficiency curve and linearity check of a UN-ECE Regulation 83 compliant CPC
Figure 5 shows the counting efficiency versus the particle size of the regulation compliant CPC for the three
measurements. All three data points for every particle size lie within the single standard deviation of every point. The
error bars significantly increase for particle sizes larger than 30 nm, due to the fact that the particle concentration was
Fig. 3. Particle size control by the diffusion battery for three measurements. The particle size was set to 23 nm at the DMA. The data was fitted for n10
data points for every single measurement (m1). The gray lines indicate the expected lines for 22-nm and 24-nm particles.
B. Grob et al. / Journal of Aerosol Science 70 (2014) 5058 54
getting lower as the median of the size distribution of the spark discharge generator was about 23 nm. From 37 nm the
number concentration was kept over 5000 cm
3
by adapting the discharge frequency of the GFG (about 3.522 Hz).
In Fig. 6 the linear response of the regulation compliant counter is shown for the three measurement series in the
concentration range of 1000 cm
3
up to 10 000 cm
3
. Taking into account the coefficients of determination of about 1, the
regulation compliant CPC shows a perfect linear response. Nevertheless the slope reaches tightly the requirement value of
0.9. The very low variations are comparable to the other results described above.
3.4. New calibration system compared to conventional method
In view of the fact that the common setup for charge conditioning before an electrostatic classification is a bipolar
charger, a comparison was done between the IPC and a Kr-85 bipolar charger. As Fig. 7 demonstrates there is no significant
difference between both methods in the range from 13 nm to 55 nm. All data points are the average of three single
measurement series, whereas the error bars are the single standard deviation in consideration of Gaussian error
propagation. For comparison the cutoff curve measured relative to the reference CPC is also plotted. The three curves
confirm the high repeatability as well as the negligible effect of multiple charged particles for the indirect photoelectric
charger.
Fig. 4. Number concentration of the reference CPC versus the charge number concentration of the FCE for a particle size of 55 nm. The linear fit includes
n6 data points for every single measurement (m1). The error bars show the single standard deviation.
Fig. 5. Counting efficiency measurement of a regulation compliant CPC with a supposed 50%-cut off of 23 nm. The error bars show the single standard
deviation in consideration of Gaussian error propagation.
B. Grob et al. / Journal of Aerosol Science 70 (2014) 5058 55
The average of three measurements of a CAST in combination with the Kr-85 charger is plotted as the fourth dataset in
Fig. 7. The evaporation tube implemented in the device was fixed at a temperature of 314 K. At this low temperature only
highly volatile materials are evaporated from the particles. It can be assumed that there are still hydrocarbons adsorbed on
the surface. Up to 35 nm the counting efficiency of the regulation compliant CPC with CAST soot is almost equal to the GFG
aerosol. For larger particles a difference to the mean values of the GFG is noticeable, whereas they are still within the single
standard deviation range of both methods. It has to be mentioned that in this size range the number concentration of the
CAST aerosol was only about 2000 cm
3
after the VKL, which leads to a considerable error due to an average noise level of
the FCE of 7400 cm
3
. At the relevant points of the regulation (23 nm & 41 nm) the difference between the GFG and the
CAST aerosol is 1% and 8%, respectively.
4. Discussion
The UN-ECE Regulation 83 for light duty vehicles as well as the UN-ECE Regulation 49 for heavy duty engines dictates
counting efficiencies at particle sizes (electrical mobility diameter) of 23 nm (71 nm) and 41 nm (71 nm) of 50% (712 %)
and 490%, respectively. As illustrated in the results previously it is possible with our calibration setup to validate a
regulation compliant counter in the size range from 13 nm up to 60 nm. The excellent agreement between the reference CPC
and the charge number concentration measured with the FCE demonstrates that the indirect photoelectric charger in
Fig. 6. Linearity check of a regulation compliant CPC. The error bars show the single standard deviation.
Fig. 7. Comparison of the counting efficiency measurement between the Faraday cup electrometer and the CPC as reference. The third dataset shows the
mean value of three measurements with a comparable system but a Kr-85 bipolar charger for charge conditioning compared to the fourth where a CAST
aerosol was used. The error bars show the single standard deviation in consideration of Gaussian error propagation.
B. Grob et al. / Journal of Aerosol Science 70 (2014) 5058 56
combination with the ESP leads to a negligible fraction of multiple charged particles. Measurements with the bipolar
charger confirm the result. The high repeatability and the low standard deviation of the three datasets show that the
charging conditioner in combination with the GFG leads to a constant aerosol production with a stable charging process
over time. In fact the lownumber of multiple charged particles is only possible with a lowcharging efficiency of the unipolar
charger (low Nt-product) but the number concentration the system delivers is still high enough for the calibration of a
CPC in the single counting mode up to 10 000 cm
3
. Compared to other setups for calibration described in the literature our
system requires no dilution bridge. The concentration can be modified easily by adjusting the discharge frequency of
the GFG.
As long as there is no calibration material prescribed for calibration in the regulation often emery oil or CAST is used.
It was reported by Wang et al. (2010) and Giechaskiel et al. (2011) that the counting efficiency of emery oil is about 16% for
23 nm and 10% for 41 nm higher than for CAST particles. This strong discrepancy leads to significant differences in the total
number concentration measured for diesel engines (Wang et al., 2010). Therefore an inert material is needed which can be
delivered everywhere and is standardized. The CAST delivers particles generated by a flame soot generator operating with
propane and air. Since the aerosol is generated by combustion it may be close to a real diesel soot. However, it is very
difficult and complex to achieve a high repeatability of the particle composition. To achieve a repeatable particle surface and
the identical surface property, which is necessary for the condensation process in the CPC, volatiles have to be removed and
it has to be guaranteed that the morphology of the particles stays constant. This can only be done by a thermal treatment
and a costly flow control of the fuel, air and the quench gas stream.
The spark discharge generator equipped with carbon electrodes has the advantage that the particles consist of an
analytically pure material (purity 99.9995%, spectrograde quality) and is operated only with the noble gas argon as the
carrier gas. This allows the production of carbon particles with a highly repeatable morphology. The effect of volatiles on the
calibration process can be excluded. As evident from the results the GFG aerosol at least for a particle size of about 23 nm
leads to nearly the same response of the CPC as the CAST aerosol. For 41 nm the difference is still only about 8%. Therefore
for a CPC calibrated with a GFG a similar response to diesel soot can be expected when compared to a CPC calibrated with
a CAST.
The GFG 1000, operated with argon, yields much higher particle numbers than operated with nitrogen. This is due to a
much lower breakthrough threshold under sparking.
5. Conclusion
The described CPC calibration system allows the calibration or the periodical check of UN-ECE Regulation 83 compliant
counters. As a test aerosol generator a GFG 1000 was used which showed similar counting efficiencies as a CAST aerosol. For
charge conditioning an indirect photoelectric charger was implemented in combination with an electrostatic precipitator.
This allowed the reproducible production of a monodisperse aerosol by an electrostatic classifier. Through an ejector diluter
the aerosol was sucked through the system and delivered a maximum sample flow of about 7 l/min. The response of the CPC
for calibration was compared with a Faraday cup electrometer.
The results demonstrated that the setup fulfills the required guidelines of the regulation and delivers a highly
reproducible monodisperse aerosol, whereas the concentration can be easily changed by the discharge frequency of the
GFG. Therefore the counting efficiency in a size range from 13 nm to 60 nm with particle concentrations between
1000 cm
3
and 10 000 cm
3
can be determined.
With the indirect photoelectric charger it is possible to replace usually used bipolar chargers containing radioactive
sources. Moreover by monitoring the ion current and the possibility to adapt the light power a stable process can be
achieved.
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