EURAMET 1027) Th E C O Unt Mean Is Defined As the Arithmetic Mean of the Particle Diameter in the System
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EURAMET Project 1027 Comparison of nanoparticle number concentration and size distribution report of results, V2.0 Jürg Schlatter Federal Office of Metrology METAS, Lindenweg 50, CH-3084 Wabern, Switzerland 22 September 2009 Report_EURAMET1027_V2.0.docx/2009-09-22 1/29 Table of contents Table of contents 2 Description and goal 3 Participants 4 Measurement procedure 5 Data analysis and reporting 8 Results for particle number concentration 12 Particle size distribution measurement 16 Results from the raw size data (method 1) 19 Results for particle size parameters using methods 2 and 3 22 Particle shape and size with an atomic force microscope 22 Geometric Standard Deviation 23 Further work 25 Annex A: Table of Instrumentation 26 Annex B: Protocol for number concentration measurements 27 Annex C: Protocol for size distribution measurements 28 Report_EURAMET1027_V2.0.docx/2009-09-22 2/29 Description and goal The experimental work for EURAMET Project 1027 "Comparison of nanoparticle number concentration and size distribution" was hosted on 27 and 28 November 2008 at the Federal Office of Metrology METAS, Switzerland. The particle number concentration and size distribution in a neutral combustion aerosol were measured with two types of instruments. First, the number concentration was measured with particle counters that do not evaluate the particle size (e.g. CPC = condensation particle counter). Second, the particle size distribution was measured through the combination of a particle size classifier and a particle counter (e.g. SMPS = scanning mobility particle sizer, ELPI = electrical low pressure impactor). Particle size distributions can be characterized by the (total) particle number concentration and the geometric mean size. However, this analysis depends on instrumental parameters as well as on algorithms incorporated in the manufacturer’s software. Thus, the separate comparison of simple number concentration allows the participants a direct comparison of their particle counters. The comparison used continuously generated combustion aerosol in the size range 50 to 170 nanometres (nm), with number concentrations in the range 1 000 to 1 000 000 particles per millilitre of air (cm-3). A typical measurement with constant aerosol generation lasted 30 minutes. The reported measurements of the comparison were: Average particle number concentrations at several points between 103 and 106 cm-3. The results are referred to actual ambient conditions (22 °C and 950 hPa). Average particle size at several points between 50 nm and 170 nm. The size is defined separately as the geometric mean or mode of the size distribution, and corresponds to the diameter of a sphere having the equivalent electrical mobility diameter. Degrees of equivalence (DoE) were calculated for these quantities. Report_EURAMET1027_V2.0.docx/2009-09-22 3/29 Participants Participation in this comparison was open to metrology institutes and designated institutes in this field (according to CIPM MRA – Appendix A). There were three categories of instruments involved in the comparison: those measuring particle size distributions (particle sizers); those measuring particle number concentration without any size information (particle counters); and imaging instruments providing supplementary size information. Table 1 Participating institutes and instrumentation grouped in following categories: particle sizers (first group), particle counters (second group), and imaging instruments (third group) Institute Person during Instrument Measurand experiment FORCE Technology, Karsten Fuglsang ELPI aerodynamic diameter DK distribution METAS, Jürg Schlatter SMPS electrical mobility CH diameter distribution NPL, Jordan Tompkins, SMPS electrical mobility UK Richard Gilham diameter distribution UBA, Klaus Wirtz SMPS electrical mobility DE diameter distribution AIST, Hiromu Sakurai CPC number concentration JP METAS, Jürg Schlatter Diluter and CPC number concentration CH METAS, Jürg Schlatter CPC number concentration CH NPL, Jordan Tompkins, CPC number concentration UK Richard Gilham UBA, Klaus Wirtz CPC number concentration DE DFM, (Kai Dirscherl) Atomic Force geometric size DK Microscope SMPS: Scanning mobility particle sizer CPC: Condensation particle counter (as independent instrument or an element of SMPS) ELPI: Electrical low pressure impactor Report_EURAMET1027_V2.0.docx/2009-09-22 4/29 Measurement procedure Schedule Setup with testing: Wednesday 26 November 2008 The instruments were installed and tested. A test combustion aerosol was provided by METAS. The necessary calibrations and adjustments of the components were executed. Comparison Measurements: Thursday and Friday 27 and 28 November 2008 The measurements consisted of a series of 14 measuring points with a “natural” particle size distribution (σ g ≈ 1.6) and a series of 6 measuring points with a “monodisperse” particle size distribution (σ g ≈ 1.1). The aerosol was prepared and fed to the instruments for 30 minutes for each size/concentration combination. All the relevant concentrations at a specific particle size distribution were supplied before changing the size distribution. The general schedule is shown in Figure 1, with the full schedule shown in Table 2. Dismantling: Friday 28 November 2008 The Instruments were dismantled at the second day just after the final measurements. new particle size First concentration: Size fresh new Second concentration: fresh new Third concentration: Size fresh stabilization distribution measurement air conc Size distribution air conc distribution measurement air 15 minutes 30 minutes 5 min 5 min measurement 5 min 5 min 30 minutes 5 min 0 min 30 min 60 min 90 min 120 min Figure 1 Measurement schedule for one particle size with three number concentrations. Table 2 Full measurement schedule. Time frame for Time frame for Time frame for Time frame for the measuring the measuring the measuring the measuring Date σ g Run [nm] [nm] point with point with point with point with [hPa] g 3 -3 4 -3 5 -3 6 -3 d 10 cm 10 cm 10 cm 10 cm Ambient pressure Nominal geo. Mean 27.11.2008 A 100 1.6 959 9:00 to 9:30 9:40 to 10:10 10:20 to 10:50 11:00 to 11:30 27.11.2008 B 140 1.6 957 13:00 to 13:30 13:41 to 14:11 14:20 to 14:50 - 27.11.2008 C 170 1.6 955 15:37 to 16:08 16:49 to 17:20 17:30 to 18:00 - 28.11.2008 D 70 1.6 943 8:15 to 8:45 8:55 to 9:25 9:35 to 10:05 10:15 to 10:45 28.11.2008 E 70 1.1 940 11:40 to 12:10 12:15 to 12:45 - - 28.11.2008 F 50 1.1 937 13:45 to 14:16 14:20 to 14:50 - - 28.11.2008 G 180 1.1 936 15:15 to 15:45 15:50 to 16:20 - - Report_EURAMET1027_V2.0.docx/2009-09-22 5/29 Technica l infrast ruct ure For the generation of “natural” and “monodisperse” particle distributions two types of setup were necessary (Figure 2). The "monodisperse" particle size distribution is not actually monodisperse, it contains also larger particles. When particles of a certain electrical mobility are selected by a DMA, the selection also contains double charged particles with larger diameter (Figure 3). CAST 4-way Aerosol source valve with 2.0 L/min Diluter- neutralizer 20 L/min Air 241 Am source Aerosol manifold with dumping Diluter volume DDS 560 a 20 :1 Tubes (1.5 m to 3.5 m) 2.0 L/min to instruments DMA TSI 3071 Diluter-neutralizer CAST 20 L/min Air Qsh = 241 Aerosol source 20 L/min Am source Aerosol manifold with 2.0 L/min with dumping Qae = 2.0 L/min volume U = variable b Tubes (1.5 m to 3.5 m) to instruments Figure 2 a: Setup for the combustion aerosol with a "natural" size distribution ( ≈ 1.6). b: Setup for the combustion aerosol with a “monodisperse” size distribution ( ≈ 1.1) DMA – differential mobility analyser. Example 70 nm, natural: σg = 1.6 Example 70 nm, "monodisperse", σg ≈ 1.1 tion tion Size distribu 10 100 1000 Electrical mobility diameter (nm) Figure 3 Examples of “natural” and the “mon odisperse” size distributions. Report_EURAMET1027_V2.0.docx/2009-09-22 6/29 The distance between the generator and the measuring instruments was minimized (Figure 4). Nevertheless, connection with long tubes was necessary. Diffusion losses mean that tube lengths were adapted to the flow rate as shown in Annex A. NPL SMPS: 0.3 L/min UBA SMPS: 1.0 L/min NPL CPC 0.3 L/min UBA CPC: 1.0 L/min Cupboard 3 Cupboard 2 AIST CPC 1.0 L/min FORCE: ELPI 10 L/min DFM AFM 0.5 L/min n n n 1 ST ST CA tubing: Tygon R-3603 diameter: 4.8 x 8.0 mm VKL-CPC: 0.3 L/mi VKL-CPC: Cupboard METAS SMPS 0.3 L/min + 0.3 SMPS METAS Grimm CPC+C 0.3 L/min + 1.7 L/mi CPC+C Grimm Figure 4 Arrangement of the measuring instruments. Report_EURAMET1027_V2.0.docx/2009-09-22 7/29 Data analysis and reporting Particle Size Distribution Parameter The size distribution from the instruments’ software consists of a table of values. Particle measurements are normally given with logarithmic spaced size bins d1, d2, d3 … dn normally with constant di+1 / di. For the particle number concentration for each bin i, two measures are used: the first is the average differential number concentration density ci (also indicated as or or and second is the number concentration C in log log ln i the size bin (also indicated as dW). Differential number concentration density is log ln . log ln Here the base chosen for the logarithm affects the result, but the concentration density can log ln be transformed as ln 10 log ln The bin particle number concentration is log ln . As the bin particle number concentration depends on the size bins, the number of bins per size range is important for any comparison (e.g.