1

Introduction of Gas metrology at NMIJ

8th GAS CRM Workshopat NMIJ, Tsukuba, Japan 2010

June 9th -11th 2010

K. Kato

NMIJ, Japan

NMIJ

2

Contents of the presentation

• Introduction of NMIJ/AIST• Gas Lab in NMIJ• Metrology system in Japan• Gas Metrology in Japan• Future plan in NMIJ

3Josephson voltage standard

Optical frequency comb Cesium atomic beam frequency standardLight detector at ultra low temp.

Water triple point cellKilogram prototypeReference materials

Introduction of NMIJ/AIST

Quantum hall resister

m cdS

KkgAmol

4

I. Organization of AIST (1)

AIST Tsukuba Central

5

I. Organization of AIST (2)

$ 1044M

$ 518M

$ 1045M

6

I. Organization of AIST (3)

Metrology Planning Office

Metrology Quality Office

Reference Material Office

International Metrology Office

Metrology Training Center

7

6/10/2010

NMIJ (300, 200)

I. Organization of NMIJ/AIST (June 1st 2010)

Metrology Planning Office, Metrology Quality Office, Reference Material Office, International Metrology Office, Metrology Training Center

Time & Frequency, Length & Dimension, Mechanical, Acoustic & Vibration, Temperature & Humidity, Fluid Flow,

Material Properties & Metrological Statistics, Electricity & Magnetism, Photometry & Radiometry, Quantum radiation

Inorganic analytical chemistry division

Organic analytical chemistry division

Materials characterization division

Inorganic Standards Section (8+7)Environmental Standards Section (5+2)

Organic standard section 1 (6+3)Organic standard section 2 (5+8)Bio-medical standard section (9+3)

Surface and Thin Film section (10+4)Nanopore Standard Section (7+2)Polymer film and Semiconductor Section (6+8)

MIJ (260, 160)

Legal Metrology, Dissemination Technology

Measurement Standards System division (9+7) Total:69+45

8

標準ガス調製用高精度天秤(developed by NMIJ)

Gas Lab in NMIJDr. Kenji Kato Section Leader

Dr. Takuya Shimosaka Oxygen, Zero gases, water, FTIR,

GCs, Laser spectroscopy, .

Dr. Takuro Watanabe VOC, Methane, Propane, etc., GCs

Dr. Nobuhiro Matsumoto CO, CO2, NO, SO2, GCs, balance

Dr. Yuko Kitamaki Sulfur in fuels, LC, GC/MS

Dr. Nobuyuki Aoiki Green House gases, Formaldehyde,

Dynamic generation, GC/MS.

Chisato Nakata Technical staff

Kaoru Kato Technical staff

Yoko Mizuno Technical staff

9

Metrology system in Japan• JCSS : Japan Calibration Service System

Based on the Japan Metrology Law.CERI is a designated calibration bodyHigh purity materials from NMIJSupplied by commercial companies Quality system comply with ISO/IEC 17025 and ISO Guide 34

• NMIJ CRMNMIJ was established in 2001 and Gas Lab arose.Produced and certified by NMIJSI traceability by primary methodsQuality system based on ISO Guide-34 and ISO/IEC 17025Peer review by NMI experts, accredited by AS-NITEParticipation in CIPM international comparison

10

End users （Inspection lab, calibration lab）

SI

NMIJ CRMs

High purity, solution, gases, environmental materiasl, industrial materiasl （soil, water, food, metals, ceramic, oils, environmental, materials, pesticides）

JCSS NMIJ CRMNMIJ

Metrology System of Reference Materials in Japan

外部機関標準物質公表制度（SIトレサ）

臨床関連（１４種）

「標準物質開発・供給システム」の研究

農薬（ポジティブリスト）等、多種類

標準物質、試薬メーカ－等の標準物質

Primary mixturesJCSS specified standards

CIPMKey comparisons

Primary high purity materials

(Gas and reagents makers)Secondary specified standards

[Accredited Calibration Bodies]

CIPMKey comparisons

[Designated Calibration Laboratory](CERI)

11

SI

Calibration & Evaluation : Environment, Soil, Water, Air, Indoor, Emission, etc.

High Purity Organic Chemicals (Solid/Liquid) High Purity Gas

Pure Materials as Traceability Sources

Standard Solution

Matrix Standard

Standard

Gases

Purity Analysis Technique and Gravimetric PreparationFreezing Point Depression

Method (Primary Method)

Calibration Standards

Accurate Balance developed by NMIJ

Adiabatic Calorimeter

developed by NMIJ or DSC

CRMs

JCSS Standards

CERI CRMs

Traceability Sources of JCSS from NMIJ

12

一部のJCSS基準物質含む

National Standard System in Japan

Total Number of JCSS standards and NMIJ CRMs

2nd 5 year term

1st 4 year term

2001 2002 2003 2004 2005 2006 2007 2008 2009

13

Traceability in JCSS

NMIJ

[Registered Calibration Bodies]

・Sumitomo Seika Chemicals Co., Ltd.

・ Japan fine products Inc.

・ Takachihho Chemical Industrial Co., Ltd.

・ Kawasaki Sogo gas center

Calibration

Calibration

Inspection[Registered Calibration Bodies]

・ Kanto Chemical Co., Inc.

・ Wako Pure Chemical Industry Ltd.

・ Nakarai Tesque Inc. (pH)

・ Kishida Chemicals Co., Ltd. (pH)

・ Katayama Chemical Inc. (pH)

[Designated Calibration Laboratory]

Chemical Evaluation and Research Institute (CERI)

SI

Primary Mixtures

Secondary Mixtures

Working Standards

High purity materials

Technical transfer

14

JCSS Inorganic solutions (metals, anions, pH）

Oxalate pH solution, pH 1.68Phthalate pH solution, pH 4.01

Natural phosphate pH solution, pH 6.86Phosphate pH solution, pH 7.41

Borate pH solution, pH 9.18Carbonate pH solution pH 10.01 JCSS 42 CRMs

15

JCSS Organic Solutions (1)

JCSS　Solutions Concentration Development FY JCSS　Solutions Concentration Development FY

Dichloromethane 100～1000 mg/L ＜2001 1,1-Dichloroethylene 100～1000 mg/L ＜2001

Benzene 100～1000 mg/L ＜2001 c-1,2-Dichloroethylene 100～1000 mg/L ＜2001

Toluene 100～1000 mg/L ＜2001 1,1,2-Trichloroethane 100～1000 mg/L ＜2001

1,2-Dichloroethane 100～1000 mg/L ＜2001 t-1,3-Dichloropropene 100～1000 mg/L ＜2001

Tetrachlorocarbon 100～1000 mg/L ＜2001 c-1,3-Dichloropropene 100～1000 mg/L ＜2001

Chroloform 100～1000 mg/L ＜2001 Tribromomethane 100～1000 mg/L 2001

Tetrachloroethylene 100～1000 mg/L ＜2001 Bromo-dichloromethane 100～1000 mg/L 2001

Trichloroethylene 100～1000 mg/L ＜2001 Dibromeo-chloromethane 100～1000 mg/L 2001

1,1,1-Trichlororoethane 100～1000 mg/L ＜2001 t-1,2-Dichloroethylene 100～1000 mg/L 2001

o-Xylene 100～1000 mg/L ＜2001 1,2-Dichloropropane 100～1000 mg/L 2001

m-Xylene 100～1000 mg/L ＜2001 1,4-Dichlorobenzene 100～1000 mg/L 2001

p-Xylene 100～1000 mg/L ＜2001 VOC 23 Mix 100～1000 mg/L 2004

16

JCSS Organic Solutions (2)

JCSS solutions Concentration Development FY JCSS solutions Concentration Development FY

Di-2-ethylehexyl-phthalate 1000 mg/L <2001 Bisphenol-A 1000 mg/L <2001

Di-n-bthyl-phthalate 1000 mg/L <2001 4-n-Nonyl phenol 1000 mg/L <2001

Diethyl-phthalate 1000 mg/L <2001 4-t-Octylphenol 1000 mg/L <2001

Butyle-benzyl-phthalate 1000 mg/L <2001 4-t-Buthylephenol 1000 mg/L <2001

Dipropyl-phthalate 1000 mg/L 2003 4-n-Heptylphenol 1000 mg/L <2001

Dipentyl-phthalate 1000 mg/L 2003 2,4-Dichlorophenol 1000 mg/L <2001

Dihexyl-phthalate 1000 mg/L 2003 Alkylphenol 6 Mix 1000 mg/L 2003

Dicyclehexyl-phthalate 1000 mg/L 2003

Phthalate 8 Mix 1000 mg/L 2003

JCSS solutions Concentration

U (k=2) /%

Formaldehyde 0.1 % 3.2

17

JCSS gasesGases Concentration range U (k=2) /%

CH4/Air 1 - 50 μmol/mol 1

C3H8/Air 3.5 - 500 μmol/mol 1

C3H8/N2 150 μmol/mol - 1.5% 1

CO/N2 3 μmol/mol - 15% 1.5 - 1

CO2/N2 3 μmol/mol - 16% 1

SO2/N2 0.1 μmol/mol - 1% 9 - 1

NO/N2 0.1 μmol/mol - 5% 4.5 - 1

NO2/N2 5 - 50 μmol/mol 5

O2/N2 0.9 – 25 %, 100 % 1

NH3/N2 20 - 100 μmol/mol 6

Gases Concentration range

U (k=2) /%

Chloroform 0.05- 100 μmol/mol

in N2

0.9 - 0.6

Dichloromethane 1.3 – 0.9

Tetrachloroethylene 1.0 – 1.5

Trichloroethylene 0.9 – 0.9

Benzene 1.8 – 0.5

1,2-dichloroethane 1.1 – 0.8

Vinyl Chloride 0.8 – 0.8

1,3-Butadiene 2.6 – 2.6

Acrylonitrile 2.4 – 2.4

BTXE/N2 (MIX) 0.002- 100 μmol/mol

in N2

1.7 – 0.8

Ethanol/N2 100 – 500 μmol/mol

0.9 – 0.6

Ethanol/Air 1.1 – 0.7

Gases Concentration range U (k=2) /%

OC 12MIX 1 μmol/mol Soil gases 1.0 – 2.2

VOC 7MIX 1 μmol/mol Sick house gases 1.0 – 1.8

Acetaldehyde 1 μmol/mol 4

Stylene 1 μmol/mol 1.8

18

National Standard System in Japan

JCSS 校正証明書発行件数の推移 (濃度)（NITE Web Site）

260,000

320,000

300,000

280,000

340,000

200,000

220,000

240,000

180,0002004 2005 200720032000 2001 2002 2006 2008

19

Number of NMIJ CRMs in July 2009 (131 CRMs).

CRM from NMIJ (NMIJ CRM)

Surface analysis by EPMP 18Industrial materials (metal, thin film,

polymer, ceramic) 19High purity inorganic materials 4High purity organic materials 17Organic solutions 12In vitro diagnostic 5

Polymers (molecular weight) 8Environmental materials 12Foods 6Chemical speciation 3Polymers (RoHS) 15Gases 12

Total 131

20

ome comments for consideration when composing the list of exceptions as referred to in the document on "Traceability in the CIPM MRA" (CIPM 2009-24)

by Robert Kaals, 23 March 2010• The CIPM document CIPM 2009-24 clarifies acceptable traceability routes for NMIs[1] wishing to publish CMCs in the KCDB. For an NMI traceability to the SI

has to be realized and delivered by the NMI itself or through the published CMCs of another NMI, or through the calibration and measurement services offered by the BIPM. An NMI cannot have it’s CMCs published if the metrological traceability of these claims is achieved via a non-NMI.

• In the scope of the CIPM MRA, being the top of the metrological pyramid, traceability obtained from a non-NMI, accredited or not, is not acceptable as the CIPM wishes to have the whole system under the full expert control of the participating NMIs and RMOs and the CIPM.

• Whenever possible the traceability should be to the SI, but where this is not yet feasible traceability to other internationally agreed references can be accepted, provided they have been proposed by the CC concerned, approved by the CIPM and published by the BIPM.

• On the highest top of the metrological pyramid primary realizations or representations of the measurement unit(s) concerned establish traceability to the SI. Potentially primary methods can only be considered as primary methods when the whole measurement procedure is fully understood and carefully and competently carried out.

• Certified reference materials for pure substances are used for calibration and to disseminate traceability for chemical analyses. The values assigned to the mass fraction content of pure substance reference materials are based on measurement capabilities for purity analysis.

• Consequently, for chemical analyses a crucial NMI activity is purity analysis of its pure material calibrators. This is most commonly done through a mass balance approach requiring the quantification of impurities in the material.

• In cases as described in point 6. the NMI has to declare itself as the source of traceability to the SI• .• If the NMI uses CRMs for establishing traceability obtained from another recognized NMI, having CMCs published in the KCDB that cover the value assignment

of this CRM, then the source of traceability is the other NMI.• Several NMIs published CMCs for purity analysis and can thus make reference to these CMCs. However, in a number of cases NMIs do not offer their purity

analysis capabilities as a service to external customers. So, these capabilities are not published as calibration and measurement capabilities in the KCDB. Therefore, when an NMI uses internal/in-house purity analysis capabilities it has to demonstrate its purity analysis competence, notably by: fully describing its measurement procedures within its quality documentation; achieving successful on-site peer review of these capabilities; and participating in relevant key comparisons for purity analysis if available.

• In the case of enriched isotopes or isotopic abundance standards delivered by an NMI not having published CMCs, traceability can be declared to this NMI under the condition that the NMI's competence in performing the measurement procedures which are the basis of the values of the standards has been demonstrated, notably by: fully describing its measurement procedures within its quality documentation; achieving successful on-site peer review of these capabilities; and participating in relevant key comparisons if available..

• In exceptional cases where there is no NMI that delivers these isotope CRMs and these isotope CRMs are available only from non-NMIs, the NMI using these isotopes has to demonstrate that the laboratory delivering the isotope CRMs is competent and complies with quality assurance criteria as formulated in ISO/IEC 17025 under the chapter of "sub-contracting". See also the CIPM document on "Subcontracting of measurements under the CIPM MRA", CIPM 2005/09. This means that the subcontracting NMI has to have its sub-contracting process fully described in its quality manual in conformity with ISO/IEC 17025 and ISO Guide 34, while the sub-contractor needs to have a quality system in place in compliance with ISO/IEC 17025 and ISO Guide 34.

• For some type of analysis one likes to apply NAA or NMR methods. As these capabilities require costly facilities and many NMIs do not possess these capabilities, it is permitted to sub-contract these measurements to another competent institute. Like in point 11. the sub-contracting NMI has to ensure that the sub-contractor is competent and has a quality system in place in compliance with ISO/IEC 17025/ISOGuide 34.Results of measurements obtained by sub-contractors should have added-value and be in addition to own in-house measurement competence and capabilities in the field concerned. The NMI cannot claim CMCs based on the capabilities of sub-contractors.

• Traceability is not established through the results of a Key or Supplementary Comparison nor by the results obtained in a PT scheme.•

[1] NMI refers to both National Metrology Institutes and Designated Institutes

21

ome comments for consideration when composing the list of exceptions as referred to in the document on "Traceability in the CIPM MRA" (CIPM 2009-24)

by Robert Kaals, 23 March 2010

• The CIPM document CIPM 2009-24 clarifies acceptable traceability routes for NMIs[1] wishing to publish CMCs in the KCDB. For an NMI traceability to the SI has to be realized and delivered by the NMI itself or through the published CMCs of another NMI, or through the calibration and measurement services offered by the BIPM. An NMI cannot have it’s CMCs published if the metrological traceability of these claims is achieved via a non-NMI.

• In the scope of the CIPM MRA, being the top of the metrological pyramid, traceability obtained from a non-NMI, accredited or not, is not acceptable as the CIPM wishes to have the whole system under the full expert control of the participating NMIs and RMOs and the CIPM.

22

Achievements in the Recent 5 Years • Development of high purity gases for JCSS

Quality system for productionAnalytical methods of purity (GC, FTIR, ..)

• Improvements in precision of gravimetric preparationOptimization of weighingKnowledge of surface and adsorption

• Analytical technique for water measurementDew point meter and CRDS

• Participation in CIPM comparisons

23

High purity gas CRMsStandard gas name Components Purity, U(k=2) Year (FY)NMIJ CRM 3401 Nitrogen monoxide,

NO99.95±0.05% 2002

NMIJ CRM 3402 Sulfur dioxide, SO2 >99.998% 2003, 2009

NMIJ CRM 4051 Methane, CH4 99.9999±0.0001% 2005, 2009

NMIJ CRM 4052 Propane, C3H8 99.99±0.01% 2005NMIJ CRM 4041 Vinyl chloride, 100.0±0.1% 2005NMIJ CRM 3407 Carbon dioxide, CO2 99.99951±0.00036% 2006

NMIJ CRM 3404 Oxygen, O2 99.99993±0.00009% 2006, 2008

NMIJ CRM 4042 1,3-butadiene 99.7±0.6% 2006High purity Carbon monoxide, CO 99.9965±0.0004% 2008High purity Ammonia, NH3 (2012-)Zero gases N2 , Air (2010-13)

CRMs developed in 2006 - 2009

24

NMIJ CRMs （Gas Mixtures）

Standard gas name Components Year (FY)NMIJ CRM 4401 p-Xylene, cis-1,2-Dichloroethylene, 1,1,1-

Trichloroethane / N2, 1 umol/mol2003

NMIJ CRM 4402 cis-1,2-Dichloroethylene, 1,1,1-Trichloroethane / N2, 100 nmol/mol

2003

NMIJ CRM 4403 SF6 ,CF4 / N2, 100 umol/mol 2004NMIJ CRM 4404 SF6 ,CF4 / N2, 5000 umol/mol 2007NMIJ CRM 4405 C2F6 ,CF4 / N2, 5000 umol/mol 2007NMIJ CRM 440X SF6 , C2F6 ,CF4 / N2, 5000 umol/mol 2009NMIJ CRM 440X NF3, C2F6 ,CF4 / N2, 5000 umol/mol 2010-NMIJ CRM 3403 N2O / N2, 200 - 300 umol/mol 2004

Sulfur / N2 H2S, DMS, DES / N2 , 300 nmol/mol PlanningOxygen O2 / N2 Low concentration Planning

Green house gases N2O/N2, CO2/N2, CH4 / N2 PlanningHydrocarbons, Natural gases C2 - C6 / N2 , CH4, C3H8, CO2, N2 etc. Planning

Sick house gases Formaldehyde Planning

25

Methane (6N) 4 impurities

( at 1 - 5 μmol/mol) in 47L AL cylinder12.3 MPa (6000 L)

ParticipantsKRISS, NIM, NMIA, NMISA, NMIJ, BAM, NIST, NPL, VSL, VNIIM

Impurity analysis

Scheme of international comparison CCQM-K66Purity analysis of high purity methane

Homogeneity Test

Pilot lab

Purity analysis

Subsection

Up to ten 3L AL cylinders

>5 MPa (150 L)

Sample Task

Cylinder delivery

Cylinder return

Draft-A

Reporting

2nd Instability test

1st Instability test

Aug. 9 2008

Mar. 31 2008

Mar. 31 2008

2008 Nov. – 2009 Apr.

(one to two months)

(End of June 2009)

(two months)

(one month)

(Dec. 2009)

26

-1.5

-1.0

-0.5

0.0

0.5

1.0

1.5

345 350 355 360 365 370 375 380 385

Gravimetric values reported by the participants / (μmol/mol)Res

idue

of X

-axi

s/

(μm

ol/m

ol)

Optimization of Gravimetric Method(In the Case of CCQM-P41 Sample)

0.4 μmol/molOur resultsfor CCQM-P41

Revised value

Results of NMIJ for CCQM-P41 deviated about 0.4 mmol/mol from KCRV.After optimization our sample was reanalyzed by NMIJ and the deviation

evaluated became smaller than the uncertainty of calibration gas.

CCQM and APMP Comparisons before 2006

27

GAS Key nnumber Year Status Pilot Lab Participant

CO in N2 CCQM-K01a 98 finished NMi CERI

CO2 in N2 CCQM-K01b 98 finished NMi CERI

NO in N2 CCQM-K01c 98 finished NMi CERI

SO2 in N2 CCQM-K01d 98 finished NMi CERI

Natural gas I CCQM-K01e 98 finished NMi CERI

Natural gas II CCQM-K01f 98 finished NMi CERI

Natural gas III CCQM-K01g 98 finished NMi CERI

Automotive emission: CO, CO2 and C3H8/N2 CCQM-K03 98 finished ＮＭｉ-VSL CERI

Ethanol in air CCQM-K04 99-00 finished NPL CERI

Ethanol in air APMP.QM-K04 00-01 finished NMIJ CERI

Automotive emission: CO, CO2 and C3H8/N2 APMP.QM-K03 00-01 finished KRISS CERI

Gravimetric blending, CO/N2 CCQM-P23 00-01 finished NMi CERI

BTX/N2 CCQM-K07 99-00 finished NIST NMIJ

Benzene, Toluene, and Xylene in Air CCQM-K10 01 finished NIST NMIJ

Natural gas type V CCQM-K16,b, CCQM-P49 01 finished BAM,NMi NMIJ

CO2 + CH4/Air CCQM-P41 02 finished NMi-VSL NMIJ

SF6 and CFCs in Nitrogen CCQM-K15, CCQM-P51 02 finished KRISS NMIJ

VOCs CCQM-K22, CCQM-P71 02-03 finished NMIJ CERI

Natural gasⅡ CCQM-K23b 04-05 finished NMi-VSL NMIJ

NO at ambient level CCQM-K26a 04 finished NPL CERI

SO2 at ambient level CCQM-K26b 04-05 finished NPL CERI

CCQM and APMP Comparisons before 2006

28

GAS Key nnumber Year Status Pilot Lab Participant

Gravimetric blending, n-C6H14/CH4 CCQM-K54 05-06 finished NMi-VSL NMIJ

Gravimetric blending, NO/N2 CCQM-P73 06-07 finished NMi CERI

Gravimetric blending, N2/He APMP.QM-S1 05-06 finished KRISS NMIJ

ammonia in N2 CCQM-K46 06-07 draft-B NMi CERI

CO in N2 CCQM-K51 07-08 finished NMISA CERI, NMIJ

CO2 in N2 CCQM-K52 07 finished NMi-VSL, NMISA NMIJ

O2 in N2 CCQM-K53 06-07 finished KRISS NMIJ

Ethanol in air APMP.QM-K4.1 05-07 finished CERI CERI

Ambient ozone CCQM-P28 05 finished BIPM NIES

SO2 in N2 APMP.QM-K1ｄ 05-07 finished CERI CERI

Purity analysis （Methane) CCQM-K66 08-09 running NMIJ NMIJ

N2O ambient Level CCQM-K68 08-09 draft-A KRISS NMIJ

Synthetic natural gas CCQM-P87 07-07 finished NPL NMIJ

O2 ambient Level APMP.QM-S2 08-09 draft-A NMIJ NMIJ

NO2 in nitrogen CCQM-K74/P110 09-10 running BIPM NMIJ

SO2/N2, 100 μmol/mol CCQM-Kxx 09-10 running NIST CERI

Dynamic standards in ppb range CCQM-Pxx 10-11 planning METAS NMIJ

O2/N2 at 5 μmol/mol CCQM-Kxx 10-11 planning NIM NMIJ

29

Future Plan in NMIJ• High purity gases

Traceability source for JCSSZero gases

• Green house gasesCFCs, NF3, CO2, N2O, CH4

• Dynamic generationFormaldehyde

• Analytical methodsSpectroscopic methods (FT-IR, Laser)

• Clean energySulfur, DMS,…

30

NMIJ CRM 3403-a and NMIJ CRM 4403-a

• SI traceability by primary methods• Quality system ISO Guide-34

Participation to International Comparisons

CCQM-K15(SF6, CF4), emission level 2003-2004

CCQM-P41(CO2,CH4), ambient level 2002-2003

NMIJ CRM 3403-a : N2O/N2 (280ppm +/- 1.9ppm)

NMIJ CRM 4403-a : SF6 ＋ CF4/N2 (100ppm +/- 0.5ppm)

NMIJ CRM 4404-a : SF6 ＋ CF4/N2 (～5000ppm)

NMIJ CRM 4405-a : CF4＋C2F6/N2 (～5000ppm)

NMIJ CRM 4406-a : CF4＋C2F6＋SF6 /N2 (～5000ppm)

NMIJ CRM 440x-a : NF3/N2 (～5000ppm)Compounds GWPCO2 1CH4 23N2O 296CFCs 4000-10000Halon1301 5,600HCFCs 100-10000CF4 6,300C2F6 12,500CCl4 1,400SF6 22,200

Dynamic Generation of Formaldehyde Primary Reference

• Traceable to SI• Concentration range 10 ppb - ppm• Uncertainty < 2 – 3 %

Technical issues• Permeation device and balance• Analysis of formaldehyde at ppb level• Impurities in reference gases• Handling of formaldehyde gas

Target

Balance

• Real time monitoring of permeation rate• Isolation between balance and gas flow • Zero adjustment during measurement

BalanceBalance Magnetic

suspension balance（Rubotherm）

Resolution 10 μgCapacity 30 gTemp. range -40℃～50℃Temp. precision ±0.1℃

Dilution gas

Water in

Dilution gas

Permeation device

Gas output

33

Sulfur standards in Liquid Fuels and Liquefied Gases

• NMIJ CRM 4215-a

Sulfur in toluene 0.98+/-0.02 mg/kg

• NMIJ RM ４２１６-a （New)

Sulfur in toluene (Blank) 19+/-5 ug/kg

• NMIJ CRM ４２１X 50 ug/kg (planned)

Slulfur in toluene (low concentration)

• .

34

Thank you for your attention!

35

CRM No. Certified Value(Purity)in%

1 Ethanol NIMC CRM 4001-a 99.895±0.0502 Benzene NMIJ CRM 4002-a 99.992 ±0.003 *3 Toluene NIMC CRM 4003-a 99.984±0.013 *4 1,2-Dichlorethane NIMC CRM 4004-a 99.97 ±0.025 Dichloromethane 99.95 ±0.056 Carbon tetrachloride 99.99 ±0.017 Chloroform 99.91 ±0.098 Tetrachloroethylene 99.95 ±0.059 Trichloroethylene 99.87 ±0.13

10 1,1,1-trichioroethane 99.98 ±0.0211 o-xylene NMIJ CRM 4011-a 99.933 ±0.002 *12 m-xylene NMIJ CRM 4012-a 99.84 ±0.1613 p-xylene 99.82 ±0.1814 1,1-dichloroethylene 99.92 ±0.0815 cis-1,2-dichoroethylene 99.39 ±0.5816 1,1,2-trichoroethane 99.94 ±0.0617 trans-1,3-dichloropropane 98.44 ±1.4918 cis-1,3-dichloropropane 99.59 ±0.4019 Ethyl Benzene NMIJ CRM 4021-a 99.88 ±0.0320 1,3-butadiene 99.50 ±0.29 GC21 Acrylonitrile NMIJ CRM 4040-a 99.97 ± 0.0122 Vinylchloride 99.99 ±0.06 GC

Reference Material

List of High Purity VOCs