zissis samaras laboratory of applied thermodynamics aristotle university thessaloniki

7th International ETH Conference on Combustion

Generated Particles

Zurich 18-08-2003

Zissis Samaras

Laboratory of Applied

Thermodynamics

Aristotle University Thessaloniki

Overview of tOverview of the EU DG he EU DG TRENTREN Particulates Particulates

Project on theProject on the

Characterisation of Characterisation of Exhaust Particulate Exhaust Particulate

Emissions from Road Emissions from Road VehiclesVehicles

7th International ETH Conference on

Combustion Generated Particles

Zurich 18-08-2003

Contents of the presentation

1. Outline of the “PARTICULATES” project

2. Measurement Protocols and Common Formats

3. Some Results

4. Preliminary Conclusions



Zurich 18-08-2003

The “PARTICULATES

”

project team

A 5 FP European research programmesponsored by the Directorate General

on TRansport and ENergy

Partners: Associate partners:Aristotle University (GR) – Coord. Renault (F) Concawe (B) INRETS (F) Volvo (S) Dekati (FIN) Tampere University (FIN) Stockholm Univ. (S) EMPA (CH) Athens Uni. (GR) AEAT (UK) TRL (UK)IFP (F) INERIS (F) AVL (AUT) LWA (UK) AVL- MTC (S) Graz University (AUT)Aachen University (D) ConsultantsJRC Peten (NL) D. KittelsonVTT (FIN) G. ReischlFord Forschungszentrum Aachen (D)



Zurich 18-08-2003

The“PARTICULATES

”

relevant info

Project started April 2000 3,5-year duration (ends October

2003) Total cost: 3,6 M€, EU contribution:

2,5 M€ (70%) http://vergina.eng.auth.gr/mech/

lat/particulates



Zurich 18-08-2003

The “PARTICULATES

”

targets

Definition of the exhaust aerosol properties which will be examined and evaluation of available measurement instruments and techniques

Development and introduction of a harmonised protocol for the definition of exhaust aerosol sampling conditions

Examination of the particulate emissions of current light duty vehicles and heavy duty engines

Investigation of the influence of engine technology, fuel quality and after-treatment on particulate emissions



Zurich 18-08-2003

Status and outlook

A commonly agreed test procedure was developed, addressing sampling and dilution conditions

A test protocol was developed based on the selected instruments

The test conditions were evaluated with a round robin exercise

A car chasing study was conducted to check the relevance of the test protocol

Testing of a large number of vehicles and fuels is completed

Collection of all test results is centrally conducted using common formats and methodologies

Final results are expected October 2003



Zurich 18-08-2003

Main Issues in Particle Analysis

Issue 1: What to measure? … instrument Particle property Size range Resolution (time, size) Applicability / cost

Issue 2: How to measure? … sampling method Dilution factor Residence time Temperature RH

Decisions were taken accounting for: Requirements from health and environment

experts Potential for evaluation of technology

measures



Zurich 18-08-2003

Samplingsystem used

Ageing Chamber

2-stage ejector Dilutor

Dilution Air Line

Sample Line

Silica Gel

CharcoalFilter

EjectorDilutor

Heater Denuder

Mass Flow

Controller

ELPI

SMPS

Diffusion

Charger

Cooling Agent Line

Fdddg kjlk

TEOMPump

Throttle Valve

Grav. Impactor

CPC

CO2 analysisCO2 analysis

RawRaw DilutedDiluted



Zurich 18-08-2003

Measurement Equipment

Primary Dilutor

CO2 Analysers

Mass Flow Controller

CO2 Calibration Gases

Thermodenuder

SMPS andELPI

CPC and ASMO

Mass FlowControllerand DGI

Test set up for LDV - ShellTest set up for LDV - Shell



Zurich 18-08-2003

Test set up for HDV - AVLTest set up for HDV - AVL



Zurich 18-08-2003

Linear behavior Linear behavior of nucleation by of nucleation by

varying varying humidityhumidity

0

2

4

6

8

10

12

14

16

18

0 10 20 30 40 50 60

relative humidity of dilution air [%]

rati

o (

mo

de

<30

nm

)/(m

od

e >

30n

m)

[-]

All other parameters were held constant: dilution All other parameters were held constant: dilution ratio: 16-23, residence time: 3.5-3.6 s and dilution air ratio: 16-23, residence time: 3.5-3.6 s and dilution air

temperature: 40-42 °Ctemperature: 40-42 °C



Zurich 18-08-2003

Typical size distribution of a Euro II car at 50 km/h high load

0.0E+00

2.0E+08

4.0E+08

6.0E+08

8.0E+08

1.0E+09

1.2E+09

1.4E+09

1.6E+09

1.8E+09

1 10 100 1000

electrical mobility particle diameter dp [nm]

dN

/dlo

g d

p [

cm-3

]



Zurich 18-08-2003

Selection of sampling

parameters

Similarity to atmospheric dilution Potential to form nucleation mode Small sensitivity to change of parameters Feasibility to reach at the lab

DR: 12.5:1DT: 32°C



Zurich 18-08-2003

Selection of sampling

parameters

Dilution Parameter: Residence Time

0.0E+00

2.0E+08

4.0E+08

6.0E+08

8.0E+08

1.0E+09

1.2E+09

1.4E+09

1 10 100 1000Mobility Diameter [nm]

Nu

mb

er C

on

cen

trat

ion

dN

/dlo

gD

p [

#/cm

3 ]

DR=21, DT=21, RT=0,7

DR=29, DT=24, RT=2,2

50 km/h, 7,6 kW



Zurich 18-08-2003

Conditions at different

instruments

Example: Diesel engine

emissions

Ageing Chamber

2-stage ejector Dilutor

Dilution Air Line

Sample Line

Silica Gel

CharcoalFilter

EjectorDilutor

Heater Denuder

Mass Flow

Controller

ELPI

SMPS

Diffusion

Charger

Cooling Agent Line

Fdddg kjlk

TEOM

DR 12 : 1DR 12 : 1T 30 - 40°CT 30 - 40°C

RT 1 msRT 1 ms

Pump

Throttle Valve

Grav. Impactor

DR 150 : 1DR 150 : 1T ambT amb

RT 3.0 sRT 3.0 s

DR 1000-15000 : DR 1000-15000 : 11

T ambT ambRT 3.5 sRT 3.5 s

DR 120 : 1DR 120 : 1T 30°CT 30°C

RT 3.5 sRT 3.5 s

CPC



Zurich 18-08-2003

Validation of the Particulates

Dilution Protocol

On-road chasing of

exhaust plume

Conducted by Ford

Test vehicle:1.8 l Dieselspeed, fuel consumption exhaust temperatures

Ford Mobile Lab:SMPS, CPC, NOx, CO, T and RH

Test track:

high speed oval, 4 km/lap



Zurich 18-08-2003

Particle size distributions

during chasing and with

PARTICULATES system

1.0E+12

1.0E+13

1.0E+14

1.0E+15

10 100 1000

Mobility diameter [nm] N

um

be

r e

mis

sio

n r

ate

dN

/dlo

g(D

p)

[km -1

]

Chasing

PART.

1.0E+12

1.0E+13

1.0E+14

1.0E+15

1.0E+16

1.0E+17

10 100 1000

Mobility diameter [nm]

Nu

mb

er

em

iss

ion

ra

te

dN

/dlo

g(D

p)

[km

-1 ]

Chasing PART. DT = 32°C LR PART. DT = 32°C SR PART. DT = 10°C SR

50 km/h50 km/h

120 km/h120 km/h



Zurich 18-08-2003

DR fluctuation when sampling close to engine

outlet (1.5 m from

exhaust manifold)

1000 1200 1400 1600 1800 2000 2200 2400 2600RPM

0

5

10

15

20

25

30

35

40

kW

14.0+13.0 to 14.012.0 to 13.011.0 to 12.010.0 to 11.09.0 to 10.08.0 to 9.07.0 to 8.06.0 to 7.05.0 to 6.0

DR map

Initial settingInitial setting

kW

VW 1.9 TDI engine



Zurich 18-08-2003

DR fluctuation when sampling at the end of a

5 m tailpipe with a ceramic DPF installed instead of the

muffler

1000 1200 1400 1600 1800 2000 2200 2400 2600RPM

0

5

10

15

20

25

30

35

40

kW

14.0+13.0 to 14.012.0 to 13.011.0 to 12.010.0 to 11.09.0 to 10.08.0 to 9.07.0 to 8.06.0 to 7.05.0 to 6.0

DR map (Buffered system)

Setting

VW 1.9 TDI engine

kW



Zurich 18-08-2003

Thermodenuder losses

410

0102030405060708090

100

10 100 1000Mobility diameter (nm)

Pen

etra

tio

n (

%)

Operation ~1h

Operation ~22h

from manufacturer

Operation ~1h

0.00E+00

1.00E+07

2.00E+07

3.00E+07

4.00E+07

5.00E+07

6.00E+07

10 100 1000

Nu

mb

er c

on

cen

trat

ion

[#/

cm3]

Operation ~ 22 h

0.00E+00

1.00E+07

2.00E+07

3.00E+07

4.00E+07

5.00E+07

6.00E+07

10 100 1000

Nu

mb

er c

on

cen

trat

ion

[#/

cm3]



Zurich 18-08-2003

Calculated penetration as a function of

particle size for transfer lines to

different instruments

0%

10%

20%

30%

40%

50%

60%

70%

80%

90%

100%

0.001 0.01 0.1 1 10

Dp [µm]

Pen

etra

tio

nELPIDGIDDCSMPSCPC

The low penetration for the ELPI is due to TD losses



Zurich 18-08-2003

Repeatability

Upper figure: solid

(accumulation mode) particles

Lower figure: nucleation and accumulation

mode

0.00E+00

5.00E+14

1.00E+15

1.50E+15

2.00E+15

2.50E+15

3.00E+15

3.50E+15

4.00E+15

4.50E+15

10 100 1000

Mobility Diameter [nm]

Nu

mb

er e

mis

sio

n r

ate

dN

/dlo

gD

p [

km-1

]

0%

5%

10%

15%

20%

25%

30%

35%

40%

45%

Co

V

0

1E+14

2E+14

3E+14

4E+14

5E+14

6E+14

7E+14

8E+14

9E+14

10 100 1000

Mobility Diameter [nm]

Nu

mb

er

em

iss

ion

ra

te

dN

/dlo

gD

p [

kw

h-1

]

0%

5%

10%

15%

20%

25%

30%

35%

40%

45%

Co

V

4 SMPS scans on two consecutive days at 120 km/h

18 SMPS scans of solid particles

performed over two months on a VW Golf

Euro I



Zurich 18-08-2003

Reproducibility: same or similar

vehicle (VW Golf Euro III) at

3 labs

50 km/h steady state

0.000

0.005

0.010

0.015

0.020

0.025

0.030

0.035

0.040

CO*10 NOx/10 HC*10 CO2/10000 CVS PM DGI PM

Em

issi

on

[g

/km

]

SHELL

FFA

AVL MTC

n/d

0.0E+00

5.0E+13

1.0E+14

1.5E+14

2.0E+14

2.5E+14

DDC*1e9 ELPI CPC

Nu

mb

er c

on

cen

trat

ion

[km

-1]

or

Act

ive

Su

rfac

e*1e

9 [

cm2/

km] SHELL

FFA

AVL MTC



Zurich 18-08-2003

Comparison between CVS

and gravimetric impactor

VW Golf TDI Euro III

0

10

20

30

40

50

60

70

80

90

100

50 90 100 110 120 cold UDC hot UDC

Mas

s C

once

ntra

tion

[mg/

km]

-30%

-25%

-20%

-15%

-10%

-5%

0%

5%

10%

15%

% d

iffer

ence

DG

I-CV

S

DGI

CVS

% diff



Zurich 18-08-2003

Comparability between wet

and dry branch

VW Golf TDI Euro III

0

10

20

30

40

50

60

70

80

90

50 km/h 90 km/h 100 km/h 110 km/h 120 km/h

Mea

n D

iam

eter

[n

m]

ELPI mean aerod

SMPS mean mobility

DDC & CPC mean



Zurich 18-08-2003

Sampling: Cycles

NEDC CADC Steady Speeds

(50, 90, 120 km/h)

LDV

ECE R49 ESC ETC

HDV

Some also conduct: Aftertreatment tests More transient cycles More steady state tests



Zurich 18-08-2003

CONCAWE LD Programme

Daily Test Schedule Cold NEDC (1180 s) Hot NEDC (1180 s) Artemis Urban (993 s) Artemis Road (1082 s) Artemis Motorway 130 km/h (1068 s) 120 km/h Road-Load (600 s) 50 km/h High-Load (600 s) 50 km/h Road-Load (600 s) 50 km/h Road-Load with High Dilution

[W1] (600 s)

Fuel Change Pre-condition

Monday – Data processing and Pre-condition

Tuesday to Friday – Full Test Days



Zurich 18-08-2003

Diesel Fuel Analyses

Fuel Code D-1 to D-4 D-5 D6 D7 Fuel Description Units Sulphur

Matrix Swedish Class 1

EN590: pre-2000

5% RME Blend

Cetane Number 54.0 55.1 54.5

Density kg/m3 845 810 856 846

T50 °C 282 226 279 284

T95 °C 358 282 366 358

FBP °C 368 294 373 367

Flash point °C 68 66 71

CFPP °C -33 -39 - 14 - 33

KV @ 40 C mm2/s 3.04 1.79 3.15 3.08

Poly-aromatics % m/m 4.3 <0.1 7.3 5.0 Mono-aromatics % m/m 14.1 1.7 31.0 12.9

Carbon % m/m 86.8 85.9 87.1 86.3

Hydrogen % m/m 13.2 14.4 12.9 13.1

LHV MJ/kg 42.8 43.9 42.4 42.5

Ash % m/m 0 <0.01 <0.01 <0.01

Water mg/kg 36 35 50 40 Oxidation Stability g/m3 <1 10 0.2 0.3 HFRR µm 375 386 389 237 FAME Nil Nil Nil 5% v/v Sulphur mg/kg 3 307 7 D-1 pre-1996 1550 D-2 2000 280 D-3 50 ppm S 38 D-4 10 ppm S 8



Zurich 18-08-2003

Gasoline Analyses

Fuel Code G-1 G-2 G-3 Fuel Description

Units EN 228: Year 2000

EN 228: 50 ppm S

EN 228: 10 ppm S

RON 96.4 96.8 96.8 MON 85.3 86.0 86.0 Density kg/m3 753 749 748 RVP kPa 58.7 57.7 57.7 E70 % v/v 29.4 32.5 32.5 E100 % v/v 50 51.2 51.2 E150 % v/v 85.5 86.1 86.1 FBP °C 195 193 193 Residue % v/v 1.0 1.1 1.1 Olefins % v/v 8.8 9.9 9.9 Aromatics % v/v 35.4 33.4 33.4 Benzene % v/v 0.8 0.6 0.6 Sulphur mg/kg 143 45 6 Induction time minutes 693 >480 Existent gum mg/100ml <1 <1 Cu Corrosion OK OK Lead mg/l <1 <1 <1 Phosphorus mg/l <1 <1 <1 Carbon % m/m 86.3 86.0 86.0 Hydrogen % m/m 13.0 13.2 13.2 Oxygen % m/m 0.7 0.8 0.8



Zurich 18-08-2003

Properties determinationin a single run

Total “active” surface [RT] Total particle number [RT]

Surface and number give mean size [RT] Size segregated solid particle number [RT] Solids particle mass [RT] Gaseous pollutants [RT] Particle mass (VF/nVF) - CVS [CYCLE] Mass weighted size distribution [CYCLE] Number weighted size distribution[SS]

RT: Real Time CYCLE: Mean value over cycle SS: Steady State



Zurich 18-08-2003

Laboratory Vehicle Engine Principle AfterTreatment Fuel

Test Temperature Vehicle Type Cycle Emission Standard

AVLAMTSHTUVOVTEM

AVL SCANIAAVL PROTOTYPE + CRTAVL PROTOTYPE + SCRLAT RENAULT LAGUNALAT TOYOTA COROLLALAT BMW 318LAT VW GOLFMTC PEUGEOT 607MTC HONDA ACCORDMTC MITSUBISHI CHARISMAMTC PEUGEOT 406MTC VW GOLF TDI

DIESELGASOLINE

NOCRTSCRTWCOXICATCAT DPFDPFNOX STORAGEOXICAT + DPF

D6 (300 PPM S)G3G1ETD5OILD5D6D7G2BIODIESELD1RME30UG (33 PPM S)

ESC MODE 1ESC MODE 2ESC MODE 3ESC MODE 4ESC MODE 5ESC MODE 6ESC MODE 7ESC MODE 8ESC MODE 9ESC MODE 10ESC MODE 11ESC MODE 12ESC MODE 13OVERALL ESCETC URBAN STREETSETC RURAL ROADSETC MOTORWAYSETC OVERALLST1 (R49-2)ST2 (ESC 5)

EURO IIIEURO III+CRTEURO III+SCREURO IEURO III+DPFULEVEURO IIEURO II+CRT

AMBIENT-7 C-15 C-20 C

HDELDVHDV



Zurich 18-08-2003

Regulated PM emissions

(LAT data)

NEDC: PM

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0.08

0.09

D2 Laguna D3 Laguna D4 Laguna D5 Laguna D4 Golf D3 Golf D2 Golf D2 Golf(w/o cat.)

D4 Laguna(w. trap)

D3 Laguna(w. trap)

D4 Laguna(w/o trap)

PM

[g

/km

]

Note: Confidence intervals correspont to max, min of all repetitions

Euro III DieselEuro III Diesel

Euro II DieselEuro II Diesel

Euro I Euro I DieselDiesel

Eu

ro I

II D

iesel +

tra

pEu

ro I

II D

iesel +

tra

p



Zurich 18-08-2003

Active surface area

(LAT data)

Active Surface Area - Cold NEDC

1.0E+00

1.0E+01

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

Lag D2 Lag D3 Lag D4 Lag D5 Cor G3 Cor G1 BMWG1

BMWG3

Golf CatD4

Golf CatD3

Golf CatD2

Golf D2 Lag trp1D4

Lag trp1D3

Lag D4 Lag trp2D4

cm

2 k

m-1

Euro III Euro III GasGas

Euro I Euro I GasGas

Euro III DieselEuro III DieselEuro II DieselEuro II Diesel Euro I Euro I

DieselDiesel

Euro III Diesel + trapEuro III Diesel + trap



Zurich 18-08-2003

Total number of particles (wet

branch)

(LAT data)

CPC Total N - Cold NEDC

1.0E+00

1.0E+01

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

1.0E+07

1.0E+08

1.0E+09

1.0E+10

1.0E+11

1.0E+12

1.0E+13

1.0E+14

1.0E+15


BMWG3

Golf CatD4

Golf CatD3

Golf CatD2

Golf D2 Lag trp1D4

Lag trp1D3

Lag D4 Lag trp2D4

km

-1



Euro III DieselEuro III Diesel Euro II DieselEuro II DieselEuro I Euro I DieselDiesel




Zurich 18-08-2003

Total number of particles (wet

branch)

(LAT data)

SMPS Ntot - 120 km/h

1.0E+00

1.0E+01

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

1.0E+07

1.0E+08

1.0E+09

1.0E+10

1.0E+11

1.0E+12

1.0E+13

1.0E+14

1.0E+15

1.0E+16


BMWG3

Golf CatD4

Golf CatD3

Golf CatD2

Golf D2 Lag trp1D4

Lag trp1D3

Lag D4 Lag trp2D4

km-1



Euro III DieselEuro III DieselEuro II DieselEuro II Diesel

Euro I Euro I

DieseDiesell




Zurich 18-08-2003

Number of solid particles (dry

branch)

(LAT data)

ELPI N Stages 1-7 - Cold NEDC

1.0E+00

1.0E+01

1.0E+02

1.0E+03

1.0E+04

1.0E+05

1.0E+06

1.0E+07

1.0E+08

1.0E+09

1.0E+10

1.0E+11

1.0E+12

1.0E+13

1.0E+14

1.0E+15


BMWG3

Golf CatD4

Golf CatD3

Golf CatD2

Golf D2 Lag trp1D4

Lag trp1D3

Lag D4 Lag trp2D4

km

-1



Euro III DieselEuro III Diesel Euro II DieselEuro II DieselEuro I Euro I DieselDiesel




Zurich 18-08-2003

Cumulative emissions

CADC-20 oC

(EMPA data)

CADC

0.0

10.0

20.0

30.0

40.0

50.0

60.0

70.0

80.0

90.0

100.0

0 500 1000 1500 2000 2500 3000

Time [s]

% o

f int

egra

ted

valu

e

0

20

40

60

80

100

120

140

160

spee

d [k

m/h

]

CPC, 555, wet CPC, 358, dry DC, wet ELPI, dry speed [km/h]

Ford Galaxy, 1.9 TD Diesel



Zurich 18-08-2003

Cumulative emissions

CADC-20 oC

(EMPA data)

CADC

0.0

20.0

40.0

60.0

80.0

100.0

0 500 1000 1500 2000 2500 3000

Time [s]

% o

f int

egra

ted

valu

e

0

20

40

60

80

100

120

140

160

spee

d [k

m/h

]

CPC, 555, wet CPC, 358, dry DC, wet ELPI, dry speed [km/h]

Renault Mégane, 1.6 16V Gasoline



Zurich 18-08-2003

Gasoline / Diesel vehicle

emissions comparison

Mnc: Non-cat moped

Mcat: Cat Motorcycle

D: Diesel Euro IIIG: Gasoline Euro III

1,0E+08

1,0E+09

1,0E+10

1,0E+11

1,0E+12

1,0E+13

1,0E+14

1,0E+15

1,0E+16

dN

/dlo

gD

p (

km-1

)

Mnc

Mcat

D

50 km h-1

G

Ambient Equivalent

1,0E+08

1,0E+09

1,0E+10

1,0E+11

1,0E+12

1,0E+13

1,0E+14

1,0E+15

1,0E+16

1 10 100 1000

Mobility diameter (nm)

dN

/dlo

gD

p (

km-1

)

D

G

120 km h-1

Ambient Equivalent

1,0E+08

1,0E+09

1,0E+10

1,0E+11

1,0E+12

1,0E+13

1,0E+14

1,0E+15

1,0E+16

dN

/dlo

gD

p (

km-1

)

G

Mcat

Mnc

D

50 km h-1

1,0E+08

1,0E+09

1,0E+10

1,0E+11

1,0E+12

1,0E+13

1,0E+14

1,0E+15

1,0E+16

1 10 100 1000 10000Aerodynamic diameter (nm)

dN

/dlo

gD

p (

km-1

)

120 km h-1

D

G



Zurich 18-08-2003

Summary& Conclusions

Sampling parameters are critical if nucleation mode particles are to be taken into account

Soot particles are easier to characterise

Necessity to sample and analyze total aerosol but difficult to regulate in certification tests

Candidate metrics: mass: will remain legislation metric “active” surface : more sensitive than

mass, emphasis to small particles total number concentration : nuclei

particles are in general unstable



Zurich 18-08-2003

Summary& Conclusions

Diesel engines and vehicles equipped with a particulate trap produced extremely low particulate mass, low numbers of carbonaceous particles and low total numbers of particles when operating on low sulphur fuels.

The fuel sulphur effect was greatest under high speed/temperature operation. Under these conditions, higher sulphur fuels resulted in both higher particle mass and number emissions

Direct injection gasoline vehicles produced measurable amounts of particulate mass emissions over the NEDC cycle, far below conventional diesel vehicles, but higher than trap-equipped diesels

zissis samaras laboratory of applied thermodynamics aristotle university thessaloniki

Documents

test results

test conditions

test protocoltesting

agreed test procedure

aristotle university

kittelsonvtt fin

particulate emissionsstatus

exhaust aerosol properties