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NIST SPECIAL PUBLICATION 260-122

U.S. DEPARTMENT OF COMMERCE/Technology Administration

National Institute of Standards and Technology

Standard Reference Materials:

Polystyrene Films for Calibrating the

Wavelength Scale of Infrared

Spectrophotometers — SRM 1921

QC

100

.U57

NO. 260-1 22 Devinder Gupta, Lan Wang, Leonard M. Hanssen,

1995 Jack J. Hsia, and Raju U. Datla
Jhe National Institute of Standards and Technology was established in 1988 by Congress to "assist industry

in the development of technology . . . needed to improve product quality, to modernize manufacturing processes,

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'At Boulder, CO 80303. ^Some elements at Boulder, CO 80303.
NIST Special Publication 260-122

Standard Reference Materials:

Polystyrene Films for Calibrating the

Wavelength Scale of Infrared

Spectrophotometers — SRM 1921

Devinder Gupta, Lang Wang,

Leonard M. Hanssen, Jack J. Hsia, and Raju U. Datla

Radiometric Physics Division

Physics Laboratory

National Institute of Standards and Technology

Gaithersburg, MD 20899-0001

U.S. DEPARTMENT OF COMMERCE, Ronald H. Brown, Secretary

TECHNOLOGY ADMINISTRATION, Mary L. Good, Under Secretary for Technology

NATIONAL INSTITUTE OF STANDARDS AND TECHNOLOGY, Arati Prabhakar, Director

Issued April 1995
National Institute of Standards and Technology Special Publication 260-122

Natl. Inst. Stand. Technol. Spec. Publ. 260-122, 45 pages (April 1995)

CODEN: NSPUE2

U.S. GOVERNMENT PRINTING OFFICE

WASHINGTON: 1995

For sale by the Superintendent of Documents, U.S. Government Printing Office, Washington, DC 20402-9325
Preface

Standard Reference Materials" (SRMs) as defined by the National Institute of Standards and

Technology (NIST) are well-characterized materials, produced in quantity and certified for one

or more physical or chemical properties. They are used to assure the accuracy and

compatibility of measurements throughout the Nation. SRMs are widely used as primary

standards in many diverse fields in science, industry, and technology, both within the United

States and throughout the world. They are also used extensively in the fields of environmental

and clinical analysis. In many applications, traceability of quality control and measurement

processes to the national measurement system is carried out through the mechanism and use of

SRMs. For many of the Nation's scientists and technologists, it is therefore of more than

passing interest to know the details of the measurements made at NIST in arriving at the

certified values of the SRMs produced. The NIST Special Publication 260 Series is a series of

papers reserved for this purpose.

The 260 Series is dedicated to the dissemination of information on different phases of the

preparation, measurement, certification, and use of NIST SRMs. In general, much more detail

will be found in these papers than is generally allowed, or desirable, in scientific journal

articles. This enables the user to assess the validity and accuracy of the measurement

processes employed, to judge the statistical analysis, and to learn details of techniques and

methods utilized for work entailing greatest care and accuracy. These papers also should

provide sufficient additional information so SRMs can be utilized in new applications in

diverse fields not foreseen at the time the SRM was originally issued.

Inquiries concerning the technical content of this paper should be directed to the author(s).

Other questions concerned with the availability, delivery, price, and so forth, will receive

prompt attention from:

Standard Reference Materials Program

Bldg. 202, Rm. 204

National Institute of Standards and Technology

Gaithersburg, MD 20899

Telephone: (301) 975-6776

FAX: (301) 948-3730

Thomas E. Gills, Chief

Standard Reference Materials Program

iii
Foreword

Since its inauguration in 1901, the National Institute of Standards and Technology (NIST),

formerly the National Bureau of Standards (NBS), has issued nearly 2000 different Standard

Samples or Standard Reference Materials* (SRMs). Many of these have been renewed several

times; others have been replaced or discontinued as technology changed. Today, over 1000 SRMs

are available, together with a large number of scientific publications related to the ftindamental

and applied characteristics of these materials. Each material is certified for chemical composition,

chemical properties, or its physical or mechanical characteristics. Each SRM is provided with a

Certificate or a Certificate of Analysis that contains the essential data concerning its properties or

characteristics. The SRMs currently available cover a wide range of chemical, physical, and

mechanical properties, and a corresponding wide range of measurement interests in practically all aspects of fundamental and applied science. These SRMs constitute a unique and invaluable

means of transferring to the user accurate data obtained at NIST, and provide essential tools that can be used to improve accuracy in practically all areas where measurements are performed.

In addition to SRMs, the National Institute of Standards and Technology issues a variety

of Reference Materials (RMs) which are sold, but not certified by NIST. They meet the ISO

Guide 30-1981 (E) definition for RMs, and many meet the definition for CRMs. The

documentation issued with these materials is either a: (1) "Report of Investigation," the sole

authority being the author of the report. RMs are intended to further scientific or technical

research on particular materials. The principal consideration in issuing RMs is to provide a homogeneous material so that investigators in different laboratories are assured that they are investigating the same material. (2) "Certificate," issued by the certifying agency (other than

NIST), e.g., other national laboratories, other government agencies, other standardizing bodies, or other non-profit organizations. When deemed to be in the public interest and when alternate

means of national distribution do not exist, NIST acts as the distributor for such materials.

Further information on the reference materials available from NIST may be obtained from

the Standard Reference Materials Program, National Institute of Standards and Technology.

Information on other NIST services may be obtained from Technology Services, National Institute

of Standards and Technology, Gaithersburg, MD 20899.

In addition to these types of materials, NIST provides a number of additional services.

They include: Calibration and Related Measurement Services, National Standard Reference Data

system. Accreditation of Testing Laboratories, National Center for Standards and Certification

Information, Weights and Measures Program and Proficiency Sample Programs.

iv
OTHER NIST PUBLICATIONS IN TfflS SERIES

Trahey, N.M., ed., NIST Standard Reference

Materials Catalog 1992-93, NIST Spec. Publ. 260

(February 1992). SN003-003-03 146-1*

Michaelis, R.E., and Wyman, L.L., Standard

Reference Materials: Preparation of White Cast

Iron Spectro-chemical Standards, NBS Misc.

Publ. 260-1 (June 1964). COM74-11061**

Michaelis, R.E., Wyman, L.L., and Flitsch, R.,

Standard Reference Materials: Preparation of

NBS Copper-Base Spectrochemical Standards,

NBS Misc. Publ. 260-2 (October 1964).

COM74-11063**

Michaelis, R.E., Yakowitz, H., and Moore, G.A.,

Standard Reference Materials: Metallographic

Char-acterization of an NBS Spectrometric

Low-Alloy Steel Standard, NBS Misc. Publ.

260-3 (October 1964). COM74-11060**

Hague, J.L., Mears, T.W., and Michaelis, R.E.,

Standard Reference Materials: Sources of

Information, Publ. 260-4 (February 1965).

COM74-11059**

Alvarez, R., and Flitsch, R., Standard Reference

Materials: Accuracy of Solution X-Ray

Spectrometric Analysis of Copper-Base Alloys,

NBS Misc. Publ. 260-5 (February 1965).

PB 168068**

Shultz, J.I., Standard Reference Materials: Methods

for the Chemical Analysis of White Cast Iron

Standards, NBS Misc. Publ. 260-6 (July 1965).

COM74-11068**

Bell, R.K., Standard Reference Materials: Methods

for the Chemical Analysis of NBS Copper-Base

Spectro-chemical Standards, NBS Misc. Publ.

260-7 (October 1965). COM74-11067**

Richmond, M.S., Standard Reference Materials:

Analysis of Uranium Concentrates at the National

Bureau of Standards, NBS Misc. Publ. 260-8

(December 1965). COM74-11066**

Anspach, S.C., Cavallo, L.M., Garfinkel, S.B., et

al., Standard Reference Materials: Half Lives of

Mate-rials Used in the Preparation of Standard

Reference Materials of Nineteen Radioactive

Nuclides Issued by the National Bureau of

Standards, NBS Misc. Publ. 260-9 (November

1965) . COM74-11065**

Yakowitz, H., Vieth, D.L., Heinrich, K.F.J. , et al.. Standard Reference Materials: Homogeneity

Charac-terization of NBS Spectrometric Standards

II: Cartridge Brass and Low-Alloy Steel, NBS

Misc. Publ. 260-10 (December 1965).

COM74-11064**

Napolitano, A., and Hawkins, E.G., Standard

Reference Materials: Viscosity of Standard

Lead-Silica Glass, NBS Misc. Publ. 260-11**

(November 1966).

Yakowitz, H., Vieth, D.L., and Michaelis, R.E.,

Standard Reference Materials: Homogeneity

Charac-terization of NBS Spectrometric Standards

III: White Cast Iron and Stainless Steel Powder

Compact, NBS Misc. Publ. 260-12 (September

1966) . Spijkerman, J.J., Snediker, D.K., Ruegg, F.C., et

al.. Standard Reference Materials: Mossbauer

Spectroscopy Standard for the Chemical Shift of

Iron Compounds, NBS Misc. Publ. 260-13**

(July 1967).

Menis, O., and Sterling, J.T., Standard Reference

Materials: Determination of Oxygen in Ferrous

Mate-rials (SRMs 1090, 1091, 1092), NBS Misc.

Publ. 260-14** (September 1966).

Passaglia, E. and Shouse, P.J., Standard Reference

Materials: Recommended Method of Use of

Standard Ligh-Sensitive Paper for Calibrating

Carbon Arcs Used in Testing Testiles for

Colorfastness to Light, NBS Spec. Publ. 260-li5

(July 1967). Superseded by SP 260-41.

V
Yakowitz, H., Michaelis, R.E., and Vieth, D.L.,

Standard Reference Materials: Homogeneity

Charac-terization of NBS Spectrometric Standards

rV: Pre-paration and Microprobe Characterization

of W-20% Mo Alloy Fabricated by Powder

Metallurgical Methods, NBS Spec. Publ. 260-16

(January 1969). COM74-11062**

Catanzaro, E.J., Champion, C.E., Garner, E.L., et

al.. Standard Reference Materials: Boric Acid;

Isotopic, and Assay Standard Reference

Materials, NBS Spec. Publ. 260-17 (February

1970). PB189457**

Geller, S.B., Mantek, P. A., and Cleveland, N.G.,

Calibration of NBS Secondary Standards

Magnetic Tape Computer Amplitude Reference

Amplitude Measurement "Process A", NBS Spec.

Publ. 260-18 (November 1969). Superseded by

SP 260-29.

Paule, R.C., and Mandel, J., Standard Reference

Materials: Analysis of Interlaboratory

Measurements on the Vapor Pressure of Gold

(Certification of SRM 745). NBS Spec. Publ.

260-19 (January 1970). PB 190071**

260-20: Unassigned

Paule, R.C., and Mandel, J., Standard Reference

Materials: Analysis of Interlaboratory

Measurements on the Vapor Pressures of

Cadmium and Silver, NBS Spec. Publ. 260-21

(January 1971). COM74-11359**

Yakowitz, H., Fiori, C.E., and Michaelis, R.E.,

Standard Reference Materials: Homogeneity

Charac-terization of Fe-3 Si Alloy, NBS Spec.

Publ. 260-22 (February 1971). COM74-11357**

Napolitano, A., and Hawkins, E.G., Standard

Reference Materials: Viscosity of a Standard

Borosilicate Glass, NBS Spec. Publ. 260-23

(December 1970). COM71-00157**

Sappenfield, K.M., Marinenko, G., and Hague,

J.L., Standard Reference Materials: Comparison

of Redox Standards, NBS Spec. Publ. 260-24

(January 1972). COM72-50058**

Hicho, G.E., Yakowitz, H., Rasberry, S.D., et al.,

Standard Reference Materials: A Standard

Reference Material Containing Nominally Four

Percent Austenite, NBS Spec. Publ. 260-25

(February 1971). COM74-11356**

Martin, J.F., Standard Reference Materials:

NBS-U.S. Steel Corp. Joint Program for

Determining Oxygen and Nitrogen in Steel, NBS

Spec. Publ. 260-26 (February 1971). PB

81176620**

Garner, E.L., Machlan, L.A., and Shields, W.R.,

Standard Reference Materials: Uranium Isotopic

Standard Reference Materials, NBS Spec. Publ.

260-27 (April 1971). COM74-11358**

Heinrich, K.F.J. , Myklebust, R.L., Rasberry, S.D.,

et al.. Standard Reference Materials: Preparation

and Evaluation of SRMs 481 and 482 Gold-Silver

and Gold-Copper Alloys for Microanalysis, NBS

Spec. Publ. 260-28 (August 1971).

COM71-50365**

Geller, S.B., Standard Reference Materials:

Calibration of NBS Secondary Standard Magnetic

Tape (Computer Amplitude Reference) Using the

Reference Tape Amplitude Measurement "Process

A-Model 2," NBS Spec. Publ. 260-29 (June

1971). COM71-50282** Supersedes

Measurement System in SP 260-18.

Gorozhanina, R.S., Freedman, A.Y., and

Shaievitch, A.B., (translated by M.C. Selby),

Standard Reference Materials: Standard Samples

Issued in the USSR (A Translation from the

Russian), NBS Spec. Publ. 260-30 (June 1971).

COM71-50283**

Hust, J.G., and Sparks, L.L., Standard Reference

Materials: Thermal Conductivity of Electrolytic

Iron SRM 734 from 4 to 300 K, NBS Spec. Publ.

260-31 (November 1971). COM71-50563**

Mavrodineanu, R., and Lazar, J.W., Standard

Reference Materials: Standard Quartz Cuvettes

for High Accu-racy Spectrophotometry, NBS

Spec. Publ. 260-32 (December 1973).

COM74-50018**

vi
Wagner, H.L., Standard Reference Materials:

Compar-ison of Original and Supplemental SRM

705, Narrow Molecular Weight Distribution

Polystyrene, NBS Spec. Publ. 260-33 (May

1972). COM72-50526**

Sparks, L.L., and Hust, J.G., Standard Reference

Material: Thermoelectric Voltage of Silver-28

Atomic Percent Gold Thermocouple Wire, SRM

733, Verses Common Thermocouple Materials

(Between Liquid Helium and Ice Fixed Points),

NBS Spec. Publ. 260-34 (April 1972). COM72-

50371**

Sparks, L.L., and Hust, J.G., Standard Reference

Materials: Thermal Conductivity of Austenitic

Stainless Steel, SRM 735 from 5 to 280 K, NBS

Spec. Publ. 260-35 (April 1972).

COM72-50368**

Call, J. P., Mandel, J., Moore, L.J., et al.. Standard

Reference Materials: A Reference Method for the

Determination of Calcium in Serum NBS SRM

915, NBS Spec. Publ. 260-36 (May 1972).

COM72-50527**

Shultz, J.I., Bell, R.K., Rains, T.C., et al.. Standard

Reference Materials: Methods of Analysis of

NBS Clay Standards, NBS Spec. Publ. 260-37

(June 1972). COM72-50692**

Richard, J.C., and Hsia, J.J., Standard Reference

Materials: Preparation and Calibration of

Standards of Spectral Specular Reflectance, NBS

Spec. Publ. 260-38 (May 1972). COM72-

50528**

Clark, A.F., Denson, V.A., Hust, J.G., et al.,

Standard Reference Materials: The Eddy Current

Decay Method for Resistivity Characterization of

High-Purity Metals, NBS Spec. Publ. 260-39

(May 1972). COM72-50529**

McAdie, H.G., Garn, P.D., and Menis, O.,

Standard Reference Materials: Selection of

Differential Thermal Analysis Temperature

Standards Through a Cooperative Study (SRMs

758, 759, 760), NBS Spec. Publ. 260-40 (August

1972) COM72-50776**

Wood. L.A., and Shouse, P.J., Standard Reference

Materials: Use of Standard Light-Sensitive Paper

for Calibrating Carbon Arcs Used in Testing

Textiles for Colorfastness to Light, NBS Spec.

Publ. 260-41 (August 1972). COM72-50775**

Wagner, H.L., and Verdier, P.H., eds.. Standard

Reference Materials: The Characterization of

Linear Polyethylene, SRM 1475, NBS Spec.

Publ. 260-42 (September 1972).

COM72-50944**

Yakowitz, H., Ruff, A.W., and Michaelis, R.E.,

Standard Reference Materials: Preparation and

Homogeneity Characterization of an Austenitic

Iron-Chromium-Nickel Alloy, NBS Spec. Publ.

260-43 (November 1972). COM73-50760**

Schooley, J. P., Soulen, R.J., Jr., and Evans, G.A.,

Jr., Standard Reference Materials: Preparation

and Use of Superconductive Fixed Point Devices,

SRM 767, NBS Spec. Publ. 260-44 (December

1972). COM73-50037**

Greifer, B., Maienthal, E.J., Rains, T.C., et al.. Standard Reference Materials: Development of

NBS SRM 1579 Powdered Lead-Based Paint,

NBS Spec. Publ. 260-45 (March 1973).

COM73-50226**

Hust, J.G., and Giarratano, P.J., Standard Reference

Materials: Thermal Conductivity and Electrical

Resistivity Standard Reference Materials:

Austenitic Stainless Steel, SRMs 735 and 798,

from 4 to 1200 K, NBS Spec. Publ. 260-46

(March 1975). COM75-10339**

Hust, J.G., Standard Reference Materials: Electrical

Resistivity of Electrolytic Iron, SRM 797, and

Austenitic Stainless Steel, SRM 798, from 5 to 280 K, NBS Spec. Publ. 260-47 (February 1974).

COM74-50176**

Mangum, B.W., and Wise, J. A., Standard Reference

Materials: Description and Use of Precision

Thermo-meters for the Clinical Laboratory, SRM

933 and SRM 934, NBS Spec. Publ. 260-48

(May 1974). Superseded by NIST Spec. Publ.

260-113. COM74-50533**

vii
Carpenter, B.S., and Reimer, G.M., Standard

Reference Materials: Calibrated Glass Standards

for Fission Track Use, NBS Spec. Publ. 260-49

(November 1974). COM74-51185**

Hust, J.G., and Giarratano, P.J., Standard Reference

Materials: Thermal Conductivity and Electrical

Resistivity Standard Reference Materials: Electrolytic Iron, SRMs 734 and 797 from 4 to 1000 K,

NBS Spec. Publ. 260-50 (June 1975).

COM75-10698**

Mavrodineanu, R., and Baldwin, J.R., Standard

Reference Materials: Glass Filters As a SRM for

Spectrophotometry-Selection, Preparation,

Certification, and Use-SRM 930 NBS Spec. Publ.

260-51 (November 1975). COM75-10339**

Hust, J.G., and Giarratano, P.J., Standard Reference

Materials: Thermal Conductivity and Electrical

Resistivity SRMs 730 and 799, from 4 to 3000 K,

NBS Spec. Publ. 260-52 (September 1975).

COM75-11193**

Durst, R.A., Standard Reference Materials:

Standard-ization of pH Measurements, NBS Spec.

Publ. 260-53 (December 1978). Superseded by

SP 260-53 Rev. 1988 Edition. PB88217427**

Burke, R.W., and Mavrodineanu, R., Standard

Reference Materials: Certification and Use of

Acidic Potassium Dichromate Solutions as an

Ultraviolet Absorbance Standard, NBS Spec.

Publ. 260-54 (August 1977). PB272168**

Ditmars, D.A., Cezairliyan, A., Ishihara, S., et al.. Standard Reference Materials: Enthalpy and Heat

Capacity; Molybdenum SRM 781, from 273 to 2800 K, NBS Spec. Publ. 260-55 (September

1977) . PB272127**

Powell, R.L., Sparks, L.L., and Hust, J.G.,

Standard Reference Materials: Standard

Thermocouple Material, Pt-67: SRM 1967, NBS

Spec. Publ. 260-56 (February 1978).

PB277172**

Call, J. P., and Plebanski, T., Standard Reference

Materials: Guide to United States Reference

Materials, NBS Spec. Publ. 260-57 (February

1978) . PB277173**

Barnes, J.D., and Martin, G.M., Standard Reference

Materials: Polyester Film for Oxygen Gas Transmission Measurements SRM 1470, NBS Spec.

Publ. 260-58 (June 1979). PB297098**

Chang, T., and Kahn, A.H., Standard Reference

Materials: Electron Paramagnetic Resonance

Intensity Standard: SRM 2601; Description and

Use, NBS Spec. Publ. 260-59 (August 1978).

PB292097**

Velapoldi, R.A., Paule, R.C., Schaffer, R., et al.. Standard Reference Materials: A Reference

Method for the Determination of Sodium in

Serum, NBS Spec. Publ. 260-60 (August 1978).

PB286944**

Verdier, P.H., and Wagner, H.L., Standard

Reference Materials: The Characterization of

Linear Poly-ethylene (SRMs 1482, 1483, 1484),

NBS Spec. Publ. 260-61 (December 1978).

PB289899**

Soulen, R.J., and Dove, R.B., Standard Reference

Materials: Temperature Reference Standard for

Use Below 0.5 K (SRM 768), NBS Spec. Publ.

260-62 (April 1979). PB294245**

Velapoldi, R.A., Paule, R.C., Schaffer, R., et al.,

Standard Reference Materials: A Reference

Method for the Determination of Potassium in

Serum, NBS Spec. Publ. 260-63 (May 1979).

PB297207**

Velapoldi, R.A., and Mielenz, K.D., Standard

Reference Materials: A Fluorescence SRM

Quinine Sulfate Dihydrate (SRM 936), NBS

Spec. Publ. 260-64 (January 1980).

PB80132046**

Marinenko, R.B., Heinrich, K.F.J. , and Ruegg,

F.C., Standard Reference Materials:

Micro-Homogeneity Studies of NBS SRM, NBS

Research Materials, and Other Related Samples,

NBS Spec. Publ. 260-65 (September 1979).

PB300461**

viii
Venable, W.H., Jr., and Eckerle, K.L., Standard

Reference Materials: Didymium Glass Filters for

Calibrating the Wavelength Scale of Spectrophotometers (SRMs 2009, 2010, 2013, 2014).

NBS Spec. Publ. 260-66 (October 1979).

PB80104961**

Velapoldi, R.A., Paule, R.C., Schaffer, R., et al.. Standard Reference Materials: A Reference

Method for the Determination of Chloride in

Serum, NBS Spec. Publ. 260-67 (November

1979). PB80110117**

Mavrodineanu, R., and Baldwin, J.R., Standard

Reference Materials: Metal-On-Quartz Filters as a SRM for Spectrophotometry SRM 2031, NBS

Spec. Publ. 260-68 (April 1980). PB80197486**

Velapoldi, R.A., Paule, R.C., Schaffer, R., et al.,

Standard Reference Materials: A Reference

Method for the Determination of Lithium in

Serum, NBS Spec. Publ. 260-69 (July 1980).

PB80209117**

Marinenko, R.B., Biancaniello, F., Boyer, P. A., et

al., Standard Reference Materials: Preparation

and Char-acterization of an

Iron-Chromium-Nickel Alloy for Microanalysis:

SRM 479a, NBS Spec. Publ. 260-70 (May 1981).

SN003-003-02328-1*

Seward, R.W., and Mavrodineanu, R., Standard

Reference Materials: Summary of the Clinical

Laboratory Standards Issued by the National

Bureau of Standards, NBS Spec. Publ. 260-71

(November 1981). PB82135161**

Reeder, D.J., Coxon, B., Enagonio, D., et al.. Standard Reference Materials: SRM 900, Antiepilepsy Drug Level Assay Standard, NBS Spec.

Publ. 260-72 (June 1981). PB81220758

Interrante, C.G., and Hicho, G.E., Standard

Reference Materials: A Standard Reference

Material Containing Nominally Fifteen Percent

Austenite (SRM 486), NBS Spec. Publ. 260-73

(January 1982). PB82215559**

Marinenko, R.B., Standard Reference Materials:

Pre-paration and Characterization of K-411 and

K-412 Mineral Glasses for Microanalysis: SRM

470, NBS Spec. Publ. 260-74 (April 1982).

PB82221300**

Weidner, V.R., and Hsia, J.J., Standard Reference

Materials: Preparation and Calibration of First

Surface Aluminum Mirror Specular Reflectance

Standards (SRM 2003a), NBS Spec. Publ. 260-75

(May 1982). PB82221367**

Hicho, G.E., and Eaton, E.E., Standard Reference

Materials: A Standard Reference Material

Containing Nominally Five Percent Austenite

(SRM 485a), NBS Spec. Publ. 260-76 (August

1982). PB83115568**

Furukawa, G.T., Riddle, J.L., Bigge, W.G., et al.,

Standard Reference Materials: Application of

Some Metal SRMs as Thermometric Fixed

Points, NBS Spec. Publ. 260-77 (August 1982).

PB831 17325**

Hicho, G.E., and Eaton, E.E., Standard Reference

Materials: Standard Reference Material

Containing Nominally Thirty Percent Austenite

(SRM 487), NBS Spec. Publ. 260-78 (September

1982). PB831 15576**

Richmond, J.C., Hsia, J.J., Weidner, V.R., et al.. Standard Reference Materials: Second Surface

Mirror Standards of Specular Spectral Reflectance

(SRMs 2023, 2024, 2025), NBS Spec. Publ.

260-79 (October 1982). PB84203447**

Schaffer, R., Mandel, J., Sun, T., et al.. Standard

Reference Materials: Evaluation by an ID/MS

Method of the AACC Reference Method for

Serum Glucose, NBS Spec. Publ. 260-80

(October 1982). PB84216894**

Burke, R.W., and Mavrodineanu, R., Standard

Reference Materials: Accuracy in Analytical

Spectrophoto-metry, NBS Spec. Publ. 260-81

(April 1983). PB83214536**

Weidner, V.R., Standard Reference Materials: White

Opal Glass Diffuse Spectral Reflectance

Standards for the Visible Spectrum (SRMs 2015

and 2016), NBS Spec. Publ. 260-82 (April 1983).

PB83220723**

ix
Bowers, G.N., Jr., Alvarez, R., Cali, J. P., et al.,

Standard Reference Materials: The Measurement

of the Catalytic (Activity) Concentration of Seven

Enzymes in NBS Human Serum (SRM 909), NBS

Spec. Publ. 260-83 (June 1983). PB83239509**

Gills, T.E., Seward, R.W., Collins, R.J., et al.. Standard Reference Materials: Sampling,

Materials Handling, Processing, and Packaging of

NBS Sulfur in Coal SRMs 2682, 2683, 2684, and

2685, NBS Spec. Publ. 260-84 (August 1983).

PB84109552**

Swyt, D.A., Standard Reference Materials: A Look

at Techniques for the Dimensional Calibration of

Standard Microscopic Particles, NBS Spec. Publ.

260-85 (September 1983). PB841 12648**

Hicho, G.E., and Eaton, E.E., Standard Reference

Materials: A SRM Containing Two and One-Half

Percent Austenite, SRM 488, NBS Spec. Publ.

260-86 (December 1983). PB84143296**

Mangum, B.W., Standard Reference Materials: SRM

1969: Rubidium Triple-Point - A Temperature

Reference Standard Near 39.30° C, NBS Spec.

Publ. 260-87 (December 1983). PB84149996**

Gladney, E.S., Burns, C.E., Perrin, D.R., et al.. Standard Reference Materials: 1982 Compilation

of Elemental Concentration Data for NBS

Biological, Geological, and Environmental

Standard Reference Materials, NBS Spec. Publ.

260-88 (March 1984). PB84218338**

Hust, J.G., Standard Reference Materials: A FineGrained, Isotropic Graphite for Use as NBS

Thermophysical Property RMs from 5 to 2500 K,

NBS Spec. Publ. 260-89 (September 1984).

PB85 112886**

Hust, J.G., and Lankford, A.B., Standard Reference

Materials: Update of Thermal Conductivity and

Electrical Resistivity of Electrolytic Iron,

Tungsten, and Stainless Steel, NBS Spec. Publ.

260-90 (September 1984). PB85 115814**

Goodrich, L.F., Vecchia, D.F., Pittman, E.S., et

al.. Standard Reference Materials: Critical

Current Measurements on an NbTi

Superconducting Wire SRM, NBS Spec. Publ.

260-91 (September 1984). PB85118594**

Carpenter, B.S., Standard Reference Materials:

Calibrated Glass Standards for Fission Track Use

(Supplement to NBS Spec. Publ. 260-49), NBS

Spec. Publ. 260-92 (September 1984).

PB851 13025**

Ehrstein, J.R., Standard Reference Materials:

Preparation and Certification of SRM for

Calibration of Spreading Resistance Probes, NBS

Spec. Publ. 260-93 (January 1985).

PB85177921**

Gills, T.E., Koch, W.F., Stolz, J.W., et al.. Standard Reference Materials: Methods and

Procedures Used at the National Bureau of

Standards to Certify Sulfur in Coal SRMs for

Sulfur Content, Calorific Value, Ash Content,

NBS Spec. Publ. 260-94 (December 1984).

PB85 165900**

Mulholland, G.W., Hartman, A.W., Hembree,

G.G., et al., Standard Reference Materials:

Development of a 1mm Diameter Particle Size

Standard, SRM 1690, NBS Spec. Publ. 260-95

(May 1985). PB861 13693**

Carpenter, B.S., Gramlich, J.W., Greenberg, R.R.,

et al.. Standard Reference Materials: Uranium235 Isotopic Abundance Standard Reference

Materials for Gamma Spectrometry

Measurements, NBS Spec. Publ. 260-96

(September 1986). PB87108544**

Mavrodineanu, R., and Gills, T.E., Standard

Reference Materials: Summary of the Coal, Ore,

Mineral, Rock, and Refactory Standards Issued

by the National Bureau of Standards, NBS Spec.

Publ. 260-97 (September 1985). PB861 10830**

Hust, J.G., Standard Reference Materials: Glass

Fiberboard SRM for Thermal Resistance, NBS

Spec. Publ. 260-98 (August 1985).

SN003-003-02674-3*

Callanan, J.E., Sullivan, S.A., and Vecchia, D.F.,

Standard Reference Materials: Feasibility Study

for the Development of Standards Using

Differential Scanning Calorimetry, NBS Spec.

Publ. 260-99 (August 1985). PB86106747**

X
Taylor, J.K., Trahey, N.M., ed., Standard

Reference Materials: Handbook for SRM Users,

NBS Spec. Publ. 260-100 (February 1993).

PB93 183796**

Mangum, B.W., Standard Reference Materials: SRM

1970, Succinonitrile Triple-Point Standard: A

Temperature Reference Standard Near 58.08° C,

NBS Spec. Publ. 260-101 (March 1986).

PB86197100**

Weidner, V.R., Mavrodineanu, R., Mielenz, K.D.,

et al.. Standard Reference Materials: Holmium

Oxide Solution Wavelength Standard from 240 to 640 nm - SRM 2034, NBS Spec. Publ. 260-102

(July 1986). PB86245727**

Hust, J.G., Standard Reference Materials: Glass

Fiberblanket SRM for Thermal Resistance, NBS

Spec. Publ. 260-103 (September 1985).

PB86109949**

Mavrodineanu, R., and Alvarez, R., Standard

Reference Materials: Summary of the Biological

and Botanical Standards Issued by the National

Bureau of Standards, NBS Spec. Publ. 260-104

(November 1985). PB86155561**

Mavrodineanu, R., and Rasberry, S.D., Standard

Reference Materials: Summary of the

Environmental Research, Analysis, and Control

Standards Issued by the National Bureau of

Standards, NBS Spec. Publ. 260-105 (March

1986). PB86204005**

Koch, W.F., ed.. Standard Reference Materials:

Methods and Procedures Used at the National

Bureau of Standards to Prepare, Analyze, and

Certify SRM 2694, Simulated Rainwater, and

Reconmiendations for Use, NBS Spec. Publ.

260-106 (July 1986). PB86247483**

Hartman, A.W., and McKenzie, R.L., Standard

Reference Materials: SRM 1965, Microsphere

Slide (10 /xm Polystyrene Spheres), NBS Spec.

Publ. 260-107 (November 1988). PB89153704**

Mavrodineanu, R., and Gills, T.E., Standard

Reference Materials: Summary of Gas Cylinder

and Permeation Tube Standard Reference

Materials Issued by the National Bureau of

Standards, NBS Spec. Publ. 260-108 (May 1987).

PB87209953**

Candela, G.A., Chandler-Horowitz, D., Novotny,

D.B., et al., Standard Reference Materials:

Preparation and Certification of an

Ellipsometrically Derived Thickness and

Refractive Index Standard of a Silicon Dioxide

Film (SRM 2530), NIST Spec. Publ. 260-109

(October 1988). PB89133573**

Kirby, R.K., and Kanare, H.M., Standard Reference

Materials: Portland Cement Chemical

Composition Standards (Blending, Packaging, and

Testing), NBS Spec. Publ. 260-110 (February

1988). PB88193347**

Gladney, E.S., O'Malley, B.T., Roelandts, I., et al.,

Standard Reference Materials: Compilation of

Elemental Concentration Data for NBS Clinical,

Biological, Geological, and Environmental

Standard Reference Materials, NBS Spec. Publ.

260-111 (November 1987). PB88156708**

Marinenko, R.B., Blackburn, D.H., and Bodkin,

J.B., Standard Reference Materials: Glasses for

Micro-analysis: SRMs 1871-1875, NIST Spec.

Publ. 260-112 (February 1990). PB90215807**

Mangum, B.W., and Wise, J. A., Standard Reference

Materials: Description and Use of a Precision

Thermometer for the Clinical Laboratory, SRM

934, NIST Spec. Publ. 260-113 (June 1990).

PB90257643**

Vezzetti, C.F., Vamer, R.N., and Potzick, J.E.,

Standard Reference Materials: Bright-Chromium

Linewidth Standard, SRM 476, for Calibration of

Optical Microscope Linewidth Measuring

Systems, NIST Spec. Publ. 260-114 (January

1991). PB91 167163**

Williamson, M.P., Willman, N.E., and Grubb,

D.S., Standard Reference Materials: Calibration

of NIST SRM 3201 for 0.5 in. (12.65 mm) Serial

Serpentine Magnetic Tape Cartridge, NIST Spec.

Publ. 260-115 (February 1991). PB91187542**

Mavrodineanu, R., Burke, R.W., Baldwin, J.R., et

al.. Standard Reference Materials: Glass Filters as a Standard Reference Material for

Spectrophotometry -Selection, Preparation,

Certification and Use of SRM 930 and SRM

1930, NIST Spec. Publ. 260-116 (March 1994).

PB94-188844/AS**

xi
Vezzetti, C.F., Vamer, R.N., and Potzick, J.E.,

Standard Reference Materials: Antireflecting-Chromium Linewidth Standard, SRM

475, for Calibration of Optical Microscope

Linewidth Measuring Systems, NIST Spec. Publ.

260-117 (January 1992). PB92-149798**

Williamson, M.P., Standard Reference Materials:

Calibration of NIST Standard Reference Material

3202 for 18-Track, Parallel, and 36-Track,

Parallel Serpentine, 12.65 mm (0.5 in), 1491

cpmm (37871 cpi). Magnetic Tape Cartridge,

NIST Spec. Publ. 260-118 (July 1992). PB92-

226281**

Vezzetti, C.F., Varner, R.N., and Potzick, Standard

Reference Materials: Antireflecting-Chromium

Linewidth Standard, SRM 473, for Calibration of

Optical Microscope Linewidth Measuring

System, NIST Spec. Publ. 260-119 (September

1992).

Caskey, G.W., Philips, S.D., Borchardt., et al.. Standard Reference Materials: A Users' Guide to NIST SRM 2084: CMM Probe Performance

Standard, NIST Spec. Publ. 260-120 (1994).

Rennex, B.C., Standard Reference Materials:

Certification of a Standard Reference Material for

the Determination of Interstitial Oxygen

Concentration in Semiconductor Silicon by

Infrared Spectrophotometry, NIST Spec. Publ.

260-121 (1994) PB95-125076/AS.

*Send order with remittance to: Superintendent of

Documents, U.S. Government Printing Office,

Washington, DC 20102. Remittance from foreign

countries should include an additional one fourth

of the purchase price for postage.

**May be ordered from: National Technical

Information Services (NTIS), Springfield, VA

22161.

For information phone (703-487-4650)

To Place an Order with PB# phone (800-553-

6847)

xii
TABLE OF CONTENTS

Page

Abstract 1

1. Introduction 2

2. Description of the FT-IR spectrophotometer 3

3. FT-IR spectrometer calibrations 3

3.1 Measurement of water vapor and carbon dioxide absorption bands 3

3.2 Effect of instrument resolution 4

4. Description of the material/polystyrene film 5

5. Measurement procedure for polystyrene film characterization 5

6. Calibration of the polystyrene films 5

6. 1 Selection between vacuum and purge 5

6.2 Selection of the peak wavenumber value determination method 6

6.3 Selection of the reference peaks 6

6.4 Calibration of the polystyrene films 7

7. Uncertainty determination 7

7.1 Instrument uncertainty 7

7.2 Sample, run, and measurement uncertainties 7

7.3 Detector uncertainty 8

7.4 Total uncertainty 8

8. SRM 1921 certification 8

9. Summary 9

10. Acknowledgment 9

11. References 9

Tables and Figures 1 1-24

Appendix A. Effects of several parameters 25

A.1 Effect of intensity variation 25

A.2 Effect of beam geometry 25

A.3 Effect of peak-determination method 25

Appendix B. SRM 1921 certificate 25
LIST OF TABLES page

1. Observed and Standard Peak Wavenumbers of 25 Water Vapor Bands 11

2. Observed and Standard Peak Wavenumbers of 22 CO2 Bands 12

3. Peak Wavenumber of Water Vapor Bands and the Effect of Resolution 13

(0.5 cm -1)

4. Peak Wavenumber of Water Vapor Bands and the Effect of Resolution 14

(l.Ocm-1)

5. Peak Wavenumber of Twenty-eight Measured Absorption Bands of

Polystyrene Films (12 films with 6 Measurements on each film) 15

6. Thirteen Certified Peak Wavenumber and Wavelength Values (in vacuum) 16

7. Detector, Sample, Run, and Measurement Uncertainties 17

8. Effect of Intensity Variation on the Peak Wavenumber of the

Absorption Bands of a Polystyrene Film (Ten measurements for each band) 18

9. Effect of Beam Geometry on the Peak Wavenumber of the

Absorption Bands of a Polystyrene Film (Ten measurements for each band) 19

LIST OF FIGURES

1. Spectrum of Polystyrene Film showing Locations of Certified Absorption

Peaks 20

2. Comparison of Peak Positions for Polystyrene Absorption Bands, made under

Vacuum and Purge Conditions:

(a) two standard deviation values 21

(b) Peak position differences 22

3. Comparison of Peak Positions for Polystyrene Absorption Bands, as Determined

by Center-of-Gravity and Minimum-Find Techniques:

(a) two standard deviation values 23

(b) Peak position differences 24

xiv
NIST SPECIAL PUBLICATION 260-122

Standard Reference Materials:

Polystyrene Films for Calibrating the Wavelength Scale of Infrared Spectrophotometers - SRM 1921

Devinder Gupta*, Lan Wang#, Leonard M. Hanssen,

Jack J. Hsia, and Raju U. Datia

Radiometric Physics Division

Physics Laboratory

National Institute of Standards and Technology

Gaithersburg, MD 20899

ABSTRACT

Standard Reference Material (SRM) 1921 is a matte finish polystyrene film and is intended for use in calibrating the wavelength scale of spectrophotometers in the infrared (IR)

spectral region from 545.48 cm-l to 3082.19 cm-i (18.3325 [im to 3.2445 jim). Thirteen

absorption peak positions are certified using a center-of-gravity technique. The expanded

uncertainty values associated with these peak values are between 0.06 cm-^ and 0.66 cm-',

except for 1.84 cm-i at 2850.13 cm-' and 12.29 cm-' at 545.48 cm-'. This publication

describes the IR spectrophotometer, instrument calibration, SRM material, measurement

procedure, calibration of polystyrene films, and uncertainty determination.

Keywords; Fourier transform infrared spectrophotometer; infrared wavelength standard;

polystyrene film; standard reference material; wavelength scale; wavelength standard.

* National Physical Laboratory, New Delhi, India

# University of Hawaii, Honolulu, Hawaii

1
1. Introduction

Fourier transform infrared (FT-IR) spectrophotometers are extensively used for

chemical, optical and astronomical studies and have gained popularity over dispersive

instruments because of high resolution and speed. Although the Michelson interferometer was

invented in the nineteenth century, it only became commercially available much later as a Fourier transform spectrometer with the advent of lasers and high speed computers [1].

The ubiquitous use of FT-ER instruments has led to the need to establish a wavelength

scale compatible with its high resolution. From the beginning of infrared spectroscopy, it was

realized that a stable material for the calibration of spectrometers was required. A number of

materials were suggested including polystyrene, 1,2,4-chlorobenzene, toluene, and other

compounds. Among these materials polystyrene proved the most useful and is often used for

the calibration of infrared spectrometers. Plyler and coworkers [2] at the National Bureau of

Standards (now, the National Institute of Standards and Technology {NIST}) made a careful

evaluation of the wavelengths of the absorption bands in polystyrene. It was noted that a number of absorption bands which were not resolved with a sodium chloride prism, were

resolved with a lithium fluoride prism, thereby indicating that the wavelength designation for

some of the absorption bands would depend upon the resolution of the spectrometer. The

reference wavelengths provided by them are often employed for the calibration of prism and

grating instruments. Hannah and Farnum [3] have investigated the effects of interference and

resolution on the absorption bands of polystyrene using a dispersive infrared spectrometer.

The standard practice for measuring the performance of dispersive infrared spectrometers is described in the American Society for Testing and Materials (ASTM) standard E932-89 [4]. A

similar standard has also been prepared for FT-IR instruments by ASTM : Standard E1421-91

[5].

The present work has been undertaken with the objective of developing polystyrene

film as a Standard Reference Material (SRM) which would provide reference wavenumber and

wavelength values for the calibration of wavenumber and wavelength scales of infrared (IR)

spectrophotometers. This is accomplished by first calibrating a NIST FT-IR spectrometer

using water vapor and carbon dioxide absorption lines. Even in well purged or evacuated FTIR instruments, water vapor and carbon dioxide remain in the residual air in the sample

compartment of the instrument and provide absorption lines with adequate intensities. The

performance of the instrument is evaluated by comparing the measured absorption bands to the

standard bands available in the literature [6]. After the instrument was calibrated,

measurements were performed on a large number of polystyrene films. This has led to the

development of a polystyrene film SRM 1921. For IR spectrophotometers with relatively low

resolution and with less well purged sample compartments having high partial pressure, the

polystyrene film is more useful for wavelength calibration, since water vapor and carbon

dioxide absorption bands cannot be used in this situation.

2
2. Description of the FT-IR spectrophotometer

The instrument employed is a Bomem DA-3.02 [7], which is a FT-IR

spectrophotometer having a maximum optical retardation of 50 cm corresponding to a maximum resolution of 0.02 cm"l . A water cooled SiC source is used for the mid-IR region.

The aperture size can be varied from 10 mm to 0.5 mm in diameter. The system employs a HeNe laser for position measurement and mirror dynamic alignment. The detectors employed

for the mid-IR region are a photoconductive mercury cadmium telluride (MCT) type and a

pyroelectric type, but the more sensitive liquid-nitrogen-cooled MCT detector is generally

preferred. A coated KBr beam splitter has been used for the present experiment whose spectral

range is 500 cm"^ to 5000 cm^'. The throughput of the system is matched from the source to the detector for efficient operation of the instrument at various wavelengths and resolutions.

The instrument can be operated in either a purge or vacuum mode . The interferometer,

the sample compartment, and the detector housing can be evacuated without disturbing the

alignment. The pressure in the sample compartment has been maintained at less than one torr to avoid possible pressure-shift effects on the absorption lines of water vapor and carbon

dioxide [8,9]. The instrument room temperature was maintained near 22 °C and the humidity

ranged from 30 % to 50 % during the measurements.

3. FT-IR spectrometer calibrations

3.1 Measurement of water vapor and carbon dioxide absorption bands

High resolution spectra of water vapor and carbon dioxide have been obtained by

operating the instrument in vacuum mode. The pressure inside the sample compartment was

maintained at 50 Pa (0.4 torr). The measurements were performed in the spectral region of 500

on-i to 2500 cm'^ using apodized resolutions of 0.074 cm-^ and 0.020 cm'^. Sufficiently

strong absorption lines for water vapor have appeared in the spectral region from 1400 cm-' to 2000 cm-', whereas the spectrum has shown carbon dioxide with absorption bands in the

region from 2300 cm-' to 2400 cm-'. The strengths of the various bands depend upon the

partial pressure and temperature of these gases in the instrument.

The water molecule has an intense V2 band covering a broad spectral region centered at 1596 cm-'. A knowledge of this band and the surrounding ones is of interest for various

purposes, particularly for the accurate calibration of the spectral scale. Guelachvili [8] has

provided a high resolution spectrum of the ^2 t>and and reported two thousands absorption

bands from 1066 cm*' to 2296 cm-'. We observed a large number of water vapor bands in the

spectral region from 1350 cm-' to 2100 cm-' and a smaller number in the spectral region from

1100 cm-' to 1350 cm-' [9]. Since it is not possible to tabulate all the bands in the present

work, we have chosen a representative group of 25 bands between 1416 cm-' and 2041 cm-'-

A comparison is provided between the observed absorption bands and the standard bands in

Table 1. Two sets of measurements made within the span of three years are presented. These were taken with an aperture diameter of 1.5 mm. Another set of measurements was also made

3
with an aperture diameter of 1 mm but the results did not vary significantly with the change in

aperture size. In Table 1 the maximum difference between the observed and standard

absorption bands is 0.015 cm"^

Carbon dioxide, being a simple and common molecule, has been the subject of many

spectroscopic investigations [9,10,11]. Guelachvili [12] has reported low pressure Doppler

limited absorption spectra around 2300 cm-' and observed about seven hundred bands. We

have also observed a large number of absorption bands. A representative group of 22 bands

has been selected and compared with the standard values in Table 2. The results of the

measurements of carbon dioxide bands are similar to those obtained for water vapor bands.

Carbon dioxide bands are also not affected by a change of aperture size from 1.5 mm to 1 mm.

Two sets of measurements taken of carbon dioxide bands within a span of about 3 years have

maximum difference of 0.015 cm"' when compared to the standard values.

A linear least squares fit of the difference values observed for the standard absorption

bands of water vapor and carbon dioxide was performed and used to correct the wavelength

scale of the FT-IR instrument. This resulted in a correction of 0.01 cm-' to the certified peak

wavenumber values of the ten largest wavenumber peaks.

3.2 Effect of instrument resolution

Interferograms of water vapor bands in the range from 1850 cm*' to 1950 cm-* were

measured with a resolution of 0.074 cm-V These interferograms were used to compute spectra

with low resolution. The results were compared with water vapor spectra which were measured

with the same low resolution.

A comparison of the computed and measured peak positions of water bands is shown in

Tables 3 and 4. A spectrum with a resolution of 0.5 cm-' and a two-sigma standard deviation

of 0.020 cm-' was computed from a measured interferogram with a resolution of 0.074 cm-'.

Another spectrum with a resolution of 0.5 cm"' was measured directly with a two-sigma

standard deviation of 0.024 cm-'. Table 3 shows that the maximum difference between the two

sets of data is 0.003 cm-'.

A spectrum with a resolution of 1.0 cm*' and a two-sigma standard deviation of 0.042

cm-' was computed from a measured interferogram with a resolution of 0.074 cm-'. Another

spectrum with a resolution of 1.0 cm-' was measured directly with a two-sigma standard

deviation of 0.040 cm-'. Table 4 shows that the maximum difference between the two sets of

data is 0.079 cm-'.

A comparison of spectra with resolutions of 0.074 cm*', 0.5 cm-', and 1.0 cm"'

indicates that the differences are smaller than the combined standard deviation. These data

indicate that it is possible to use the highest possible resolution to calibrate the wavelength

scale and to use a suitable low resolution to measure different samples.

4
4. Description of the material/polystyrene film

A single roll of matte-finish polystyrene film, having the trade name of Trycite

#DWF-6001 manufactured by the Dow Chemical Company [7], was donated by the Coblentz

Society, an affiliation of the Society for Applied Spectroscopy. Two thousand five hundred

samples were cut from different sections of the roll. Each sample was assigned a number

representing the position of the sample on the roll. The thickness of the film is approximately

38 \im and is nearly uniform throughout the entire roll. SRM 1921 has a 25 mm diameter

exposed area, centered 38 mm from the bottom of a cardboard holder which is 5 cm (w) x 1

1

cm (h) X 2 mm (t) in dimension.

5. Measurement procedure for polystyrene film characterization

The polystyrene film transmittance measurements are performed over the spectral range

from 500 cm'^ to 3500 cm'^ with an unapodized resolution of 0.5 cm^^ The Hamming (also

known as Happ-Genzel function) [13] apodization function is used. The source aperture

diameter sizes are 1 mm for the MCT measurements and 10 mm for the DTGS measurements.

The measurements are made in vacuum mode, with a pressure of less than 50 Pa (0.4 Torr).

After a suitable time for the instrument to equilibrate, measurements are begun.

First, a reference spectrum is obtained. It is a Fourier transformed single beam

spectrum of the empty sample holder. Subsequently, a spectrum of the sample at normal

incidence is obtained, which is normalized by the reference spectrum to provide its transmittance spectrum. In each run, twelve samples of polystyrene film have been measured

in groups of four after a single reference measurement. This process is repeated six times for

each group of twelve polystyrene samples. These measurements are made with a remotely

controlled sixteen-position sample changer.

6. Calibration of polystyrene films

6.1 Selection between vacuum and purge

The infrared transmittance spectrum of a polystyrene film obtained in the spectral

region from 500 cm'^ to 3500 cm^' is shown in Fig. 1. Twenty-eight absorption lines were

selected for investigation. Their nominal wavenumbers are similar to the ones in Table 5 with an additional band at 1492 cm-i. Transmittance measurements of polystyrene film samples

were made both in purge and in vacuum modes. Positions of the transmittance minima

("peaks") were obtained by using a center-of-gravity (CO) technique which is described in

detail in Appendix B. Plotted in Fig. 2(a) are the two sigma standard deviation values as a function of wavenumber for the absorption bands, for measurements taken in vacuum mode

(Vacuum, CO) and those taken in purge mode (Purge, CO). The absolute difference of

measurements in these two modes (indicated by the symbol for |Vac Peak- Purge Peak|) is shown in Fig. 2(b). Even though these peak differences are less than the two sigma standard

deviations, it is evident from Fig. 2(a) that the two sigma standard deviation values for vacuum

5
mode are slightly less than those for purge mode. All further measurements were performed

in vacuum.

6.2 Selection of the peak wavenumber value determination method

After a transmittance spectrum has been obtained, the peak positions (in v^^avenumbers)

of the absorption bands have to be determined. The positions of the peaks can be determined

generally by using either a minimum-find technique or a center-of-gravity technique [14]. In the minimum-find technique the derivative of the spectrum is obtained and a threshold limit is set up. The differentiated values are searched to determine the peaks that have excursions both

above and below the threshold level. In the case of the center-of-gravity technique, an initial selection of peaks is made based on a threshold limit and then the peak position is determined

as described in detail in Appendix B. If the peak is symmetric, the peak position at the

minimum (transmittance) is determined. For an asymmetric peak, the results will deviate from

this value dependent on the degree of asymmetry and the number of points around the center

used in the determination of the peak. In Fig. 3(a), as a function of wavenumber values, the

two sigma standard deviations for the peak positions determined by this center-of-gravity

technique (CG, Vacuum) are, in general, one order less than those determined by the

minimum-find technique (Min Find, Vacuum). For the center-of-gravity technique 29

wavenumber values (28 bands as shown in Table 5 plus 1492 cm-') are used. And for the

minimum-find technique 21 wavenumber values (20 bands as shown in Table 5 plus 1492 cm*'

) are used. The absolute difference (indicated by the symbol for |CG Peak - Min Peak|)

between the peak positions determined by the center-of-gravity and the minimum-find

techniques shown in Fig. 3(b), are larger than their two sigma standard deviations. The

number of wavenumber values are the same as that in Fig. 3(a). Therefore, this particular

center-of-gravity method was chosen for all further investigations to determine the peak

positions.

6.3 Selection of the reference peaks

Out of those absorption peaks observed in the spectrum of a polystyrene film (Fig. 1), thirteen peaks have been chosen for further calibration. The criterion for the selection of these

peaks are based on the associated uncertainty and the intensity of the peak. For a selected

peak, the value of the uncertainty associated must be small. Furthermore, the peak should

neither be so strong that its minimum approaches the zero percent transmittance nor should it be so shallow that it is subjected to interference effects.

For the selection of these peaks, 12 polystyrene film samples were measured six times

each. Twenty-eight average peak positions are presented in Table 5. The peaks at approximate

positions of 624 cm-', 1 183 cm"', 1325 cm-', 1368 cm"', 1542 cm-', 1667 cm-', 1746 cm-'. 1873

an-', and 2343 cm-' have large two-standard deviations [15,16]. Their values range from 0.544

cm-' to 4.3 cm-'. Whereas the peaks near 699 cm-', 757 cm-', 1450 cm-', 1492 cm-', 2921 cm*'

and 3026 cm~l are the strongest ones and are likely to approach the zero percent transmittance,

the peaks having approximate positions of 965 cm-', 1003 cm-', 1804 cm-', and 1945 cm-' are generally weak and likely be affected by the interference. Thus, 13 peak positions were selected

for further calibration.

6
6.4 Calibration of the polystyrene films

The certified wavenumbers and wavelengths values of these thirteen peaks are obtained

from the data on 60 representative polystyrene films. In Table 6, four wavenumbers are starred to indicate that for those wavenumbers the difference between the peak values using a centerof-gravity technique and a minimum-find technique is less than 0.1 cm"^ (Refer to Fig. 3b).

Details of sample selection and grand mean peak value calculation are presented in Section 7.2. The peak near 545 cm*' is included in the reference wavenumbers to cover a larger range from

500 cm-^ to 3500 cm'^ although it has a large uncertainty of 12.29 cm'^ Furthermore, the

peak at 3026 cm-^ is also included even though it is highly intense.

The calibration measurements were made with a resolution of 0.5 cm^^ The ambient

temperature of the instrument was maintained near 22 °C and the range of the humidity was

from 30 % to 50 % during the measurements. The calibration measurements were made under

vacuum at pressures of 50 Pa (0.4 Torr). The incident beam was normal to and focused onto

the sample with an f-number of 4. A center-of-gravity method was used to find the peak

wavenumber values from a spctrum of transmittance vs wavenumbers.

The wavelength values in Table 6 are vacuum values (where n=l, the index of

refraction). For measurements of these polystyrene films made under nitrogen gas or dry air

purge, the wavenumber and wavelength values need to be adjusted due to the index of

refraction of air or purge gas (n=l. 00026 for dry nitrogen gas at atmospheric pressure and

T=298 K) [17,18]. The measured wavenumber values should be divided by 1.00026 and the

wavelength values should be multiplied by 1.00026 to compare to the standard vacuum values

[18]. However, for instruments which give vacuum wavenumber and wavelength values, no

adjustment for the index of refraction of air or purge gas should be performed.

7. Uncertainty determination

7.1 Instrument uncertainties

The correction to the wavelength scale of the FT-IR from the instrument calibrations

using water vapor and carbon dioxide absorption bands with standard values resulted in

corrections of 0.01 cm"^ and 0.00 cm-^ with an uncertainty of 0.005 cm-^

7.2 Sample, run, and measurement uncertainties

After the selection of the 13 peak bands, additional measurements were conducted on

polystyrene film samples to determine the representative wavenumber values as well as the

sample-to-sample, run-to-run, and measurement-to-measurement variations. A total of 60

samples were measured in six different runs. The procedure adopted was random sample

selection for a multivariate analysis. In the first four runs, 48 samples roughly evenly

distributed between sample numbers 9 and 315 were selected and measured. Each run had 12

samples. The samples were placed in a carousel, and the carousel was cycled through the

7
measurement process six times. Run 5 was measured in the same manner as the first four,

except that the 12 samples were selected between sample numbers 9 and 2500, i.e., out of the

entire batch of samples. In run 6 the same samples as in run 5 were measured, but with a

different detector. In order to provide each detector the same weight when computing the

grand mean for each peak, the mean for run 6 and the mean from the first five runs were

averaged.

A multivariate analysis of variance on data from these runs was also undertaken and the

results are presented in Table 7 together with the mean wavenumber values. These results

indicate that the sample, run, and measurement uncertainties are statistically significant. A

considerable variability from sample to sample indicates that the material is not homogenous

throughout the entire roll. Furthermore, a significant difference has been observed from run to run and the variability between them may be related to the repeatability of the instrument since

the runs have been measured at different periods of time. The measurement uncertainty is reasonably small, thereby indicating that the measurement procedure adopted is quite reliable.

7.3 Detector uncertainty

In run 6 the samples were measured with a DTGS detector while in runs 1 to 5 all samples were measured with a MCT detector. Table 7 shows the uncertainties of the

absorption peaks due to different detectors. The variability may be due to the following

factors. The DTGS detector requires higher intensity source corresponding to the large source

aperture; hence the sample may be at a higher temperature; the MCT detector has a greater

non-linearity; the large source aperture image on the sample may result in less interference. On

the other hand, water vapor and CO 2 bands are very sharp and were not influenced by

measurements using different detectors.

7.4 Total uncertainty

In Table 7, the combined standard uncertainty, Uc, is the root sum square of the

standard uncertainties from detector, sample, run, and measurement. The combined standard

uncertainty has an estimate of degree of freedom and this was used to determine the coverage

factor, k [15,16 ]. The expanded uncertainty [15,16], U, is the product of the combined

standard uncertainty and the coverage factor which was obtained at a 95% level of confidence.

The effects of intensity variation, beam geometry, and peak-determination method on the peak

wavenumber values are briefly discussed in Appendix A.

8. SRM 1921 certificate

The certificate for SRM 1921 is presented in Appendix B. The following items are included: certified wavenumber and wavelength values with associated uncertainties;

description of the measurement conditions; instructions for storage, handling, and use of SRM

1921.

8
9. Summary

A Fourier transform infrared spectrophotometer has been calibrated using the

absorption bands of water vapor and carbon dioxide. The spectral transmittance of a representative group of polystyrene film samples has been measured in vacuum. The positions

of absorption peaks in the region of 545.48 cm*' to 3082.19 cm*' (18.3325 jim to 3.2445 ^m)

were obtained using a center-of-gravity method. Thirteen wavelength values were selected and

certified along with their associated uncertainties. The measurement uncertainties caused by

detector, sample, and run to run statistical variation are included. Different peak-determination

methods are compared.

10. Acknowledgment

The authors gratefully acknowledge the contributions of Susannah B. Schiller, NIST

Statistical Engineering Division, for performing statistical analyses; Jennifer C. Colbert, NIST

Standard Reference Material Program, for coordinating the certification and issuance of SRM

1921; and the Coblentz Society for donating the roll of polystyrene film.

11. References

[1] R.J. Bell, Introductory Fourier transform spectroscopy, Ch. 18 and Ch. 19, p. 269,

Academic Press, New York (1972).

[2] E. K. Plyler, L. R. Blaine, and M. Nowak, J. Res. NBS 58 195-200 (1957).

[3] R. W. Hannah and R. J. Famum, PEP 573 10, Perkin-Elmer Ltd. (May 1973).

[4] ASTM E 932-89 "Standard practice for describing and measuring performance

of dispersive infrared spectrometers," Annual Book of ASTM Standards, 14.01 (1993).

[5] ASTM E 1421-91 "Standard practice for describing and measuring performance of

Fourier Transform Infrared (FT-IR) Spectrometers: Level zero and Level one tests,"

Annual Book of ASTM Standards, 14.01 (1993).

[6] G. Guelachvili, and K. Narahari Rao, "Handbook of infrared standards,"

Academic Press (1986).

[7] The use of a trade mark in this publication is for identification only and does not imply

endorsement of the product by the National Institute of Standards and Technology.

[8] G. Guelachvili, J. Opt. Soc. Am. 73 137 (1983).

[9] G. Guelachvili, J. Mol. Spectrosc. 75 251 (1979).

9
R. Paso, J. Kauppine, and R. Anttila, J. Mol. Spectrosc. 79 236 (1980).

G. Guelachvili, J. Mol. Spectrosc. 79 72 (1980).

G. Guelachvili, Appl. Opt. 17 1322 (1978).

P.R. Griffiths and J. A. deHaseth, Fourier Transform Infrared Spectrometry, Ch. 1, p. 20

and p.34, John Wiley & Sons, New York (1986).

D. G. Cameron, J. K. Kauppienen, D. J. Moffatt, and H. H. Mantsch, Appl.

Spectrosc. 36 245 (1982).

"Guide to the Expression of Uncertainty in Measurement," ISBN 92-67-10188-9, 1st

Ed., ISO, Geneva, Switzerland (1993)

B. N. Taylor and C. E. Kuyatt, "Guidelines for Evaluating and expressing the

Uncertainty of NIST Measurement Results," NIST Tech. Note 1297 (Jan. 1993).

B. Edlen, "The Refractive Index of Air, " Metrologia 2 12 (1966).

F. G. Smith, ed., "Atmosphere Propagation of Radiation," Ch. 1, p. 88, SPIE Optical

Engineering Press, Bellingham, Washington (1966).

M. Bom and E. Wolf, Principles of Optics, 6th Ed., p. 16, Pergamon Press, New York

(1980).

10
Table 1 Observed and Standard Peak Wavenumbers of 25 Water Vapor Bands

(1) (2) (3) (1)-(3) (2)-(3)

standard

value [6]

(cm-i) (cm-1) (cm-i) (cm-i) (cm-'')

1416.080 1416.08664 -0.007

1417.247 1417.25367 -0.007

1417.492 1417.49879 -0.007

1418.926 1418.93334 -0.007

1419.311 1419.31757 -0.007

1419.502 1419.50841 -0.006

1423.697 1423.70452 -0.008

1424.123 1424.13032 -0.007

1505.599 1505.60461 -0.006

1601.201 1601.20825 -0.007

1602.877 1602.88452 -0.008

1603.313 1603.32020 -0.007

1792.651 1792.652 1792.65937 -0.008 -0.007

1795.793 1795.80232 -0.008

1796.144 1796.13289 -0.008

1799.608 1799.61605 -0.008

1802.472 1802.473 1802.48013 -0.008 -0.007

1807.696 1807.70376 -0.008

1810.621 1810.623 1810.62861 -0.008 -0.006

1942.508 1942.509 1942.51651 -0.009 -0.008

1942.757 1942.76573 -0.009

1945.332 1945.34064 -0.009

1946.357 1946.36477 -0.008

2018.323 2018.33791 -0.015

2041.279 2041.28876 -0.010

(1) 0.074 cm-^ resolution;

(2) 0.02 cm-l resolution measured three years later than (1)

11
Table 2

Observed and Standard Peak Wavenumbers of 22 CO2 Bands

(1) (2) (3) (1)-(3) (2)-(3)

standard

value [6]

2330 .548 2330.550 2330.55754 -0.010 -0.008

2332 .359 2332.360 2332.36934 -0.010 -0.009

2334 .146 2334.146 2334.15678 -0.011 -0.010

2335 .910 2335.909 2335.91984 -0.010 -0.011

2337 648 2337 LkWW / •www 650 2337 65849 -0V/ a 010 W 1 W -0 008

2339..362 2339.364 2339.37269 -0.011 -0.007

2341,.053 2341 .053 2341 .06244 -0.009 -0.005

2342,.738 2342.717 2342.72769 -0.010 -0.011

2344..358 2344.359 2344.36842 -0.010 -0.009

2346 . 000 \J WW 2345FW»W976' W 2345 98461 -0w 015 w 1 w -0w • 009 w w w

2351..437 2351 .437 2351 .44763 -0.010 -0.011

2354,.423 2354.423 2354.43380 -0.011 -0.011

2355.,880 2355.883 2355.88983 -0.010 -0.007

2357..311 2357.311 2357.32133 -0.010 -0.010

2358 ,721 2358 721 2358 73605 -0W 015 W 1 w -0W 015 w 1 w

2361.,457 2361 .459 2361 .46638 -0.009 -0.007

2362..789 2362.790 2362.79850 -0.010 -0.009

2364..095 2364.096 2364.10576 -0.011 -0.010

2365..377 2365.380 2365.37958 -0.003 -0.000

2366..636 2366.637 2366.64560 -0.010 -0.009

2367..870 2367.869 2367.87815 -0.008 -0.009

2369..076 2369.075 2369.08574 -0.010 -0.01

1

(1) 0.074 cm-i resolution;

(2) 0.02 cm"i resolution measured 3 years later than (1)

12
Table 3

Peak Wavenumber of Water Vapor Bands

and the effect of resolution (0.5 cm-*)

(1)

(cm-i) 2(7

(2)

(cm-1) 2a

(1)-(2)

1866.373 0.018 1866.370 0.042 0.003

1869.332 0.012 1869.335 0.012 -0.003

1889.560 0.016 1889.561 0.014 -0.001

1895.187 0.020 1895.190 0.030 -0.003

1907.940 0.042 1907.937 0.028 0.003

1909.951 0.032 1909.948 0.034 0.003

1918.014 0.008 1918.014 0.006 0.000

1923.149 0.018 1923.152 0.018 0.003

(1) Computed for 0.5 cm^^ resolution

(2) Measured at 0.5 cm-^ resolution

13
Table 4

Peak Wavenumber of Water Vapor Bands

and the effect of resolution (1 cni'^)

(1) (2) (1)-(2)

cm-^ 2a cm-'' 2a

1866.389 0.030 1866.363 0.024 0.026

1869.354 0.050 1869.380 0.016 -0.026

1889.558 0.038 1889.550 0.086 -0.008

1895.183 0.044 1895.177 0.018 0.006

1908.007 0.064 1907.928 0.072 0.079

1910.016 0.064 1909.939 0.062 0.077

1918.032 0.018 1917.987 0.012 0.045

1923.144 0.026 1923.140 0.034 0.004

(1) Computed for 1.0 cm*' resolution

(2) Measured at 1.0 cm-^ resolution

14
Table 5

Peak Wavenumber of Twenty-Eight Measured

Absorption Bands of Polystyrene Films

(12 films with 6 measurements on each film)

peak peak

(cm-1) 2a (cm-1) 2a

546.940* 0.240 1542.162* 0.644

623.799* 0.800 1583.147 0.010

699.448 0.034 1601.366 0.016

756.580 0.022 1745.598* 0.896

841 .989 0.154 1803.825 0.516

906.785 0.004 1872.821* 0.602

965.714 0.322 1945.241 0.514

1028.318 0.078 2343.085* 4.300

1069.097 0.120 2849.994 0.012

1154.613 0.004 2920.935 0.042

1183.007 1.056 3001 .424 0.014

1325.065* 2.560 3026.375 0.016

1368.527* 0.544 3060.020 0.012

1449.675 0.038 3082.226 0.008

* These bands are not included for Min. Find, Vacuum in Fig. 3a and

are not included for peak difference in Fig. 3b.

15
Table 6

Thirteen Certified Peak Wavenumber and Wavelength Values

(in vacuum)

peak Wavenumber expanded peak wavelength expanded

(cm-1) uncertainty (^lm) uncertainty

545.48 12.29 18.3325 0.4129

842.08 0.49 1 1 .8754 0.0070

906.82 0.66 1 1 .0275 0.0080

1028.35 0.27 9.7243 0.0026

1069.20 0.46 9.3528 0.0040

1154.64* 0.54 8.6607* 0.0041

1583.13* 0.06 6.3166* 0.0002

1601.35* 0.07 6.2447* 0.0003

2850.13 1.84 3.5086 0.0023

3001 .40 0.12 3.3318 0.0001

3026.42 0.61 3.3042 0.0007

3060.03* 0.14 3.2680* 0.0002

3082.19 0.12 3.2445 0.0001

Peak values less sensitive to peak determination method.

16
Table 7

Detector, Sample, Run, and Measurement Uncertainties

expanded

1 IV. < uncertainties (a)(cm"'')— > UUli i- 1 1 AT- UUvcl

(cm ') detector sample run measure- Dined talnty facto

ment uc U=K Uc k

1 545.48 1.345 0.414 0.049 0.027 1.409 12.287 8.72

2 842.08 0.112 0.199 0.000 0.018 0.228 0.494 2.17

3 906.82 0.053 0.006 0.013 0.002 0.055 0.662 12.05

4 1028.35 0.066 0.080 0.017 0.008 0.106 0.271 2.57

5 1069.20 0.104 0.185 0.000 0.012 0.212 0.456 2.15

6 1154.64 0.038 0.000 0.018 0.001 0.042 0.540 12.83

7 1583.13 0.000 0.012 0.023 0.001 0.025 0.059 2.32

8 1601.35 0.000 0.018 0.024 0.002 0.030 0.066 2.21

9 2850.13 0.134 0.000 0.046 0.004 0.142 1.843 13.01

10 3001.40 0.000 0.012 0.047 0.000 0.048 0.121 2.49

11 3026.42 0.034 0.014 0.049 0.002 0.061 0.609 9.93

12 3060.03 0.000 0.009 0.053 0.002 0.054 0.136 2.53

13 3082.19 0.000 0.011 0.047 0.000 0.048 0.121 2.49

17
Table 8

Effect of Intensity Variation on the Peak Wavenumber of the

Absorption Bands of a Polystyrene Film

(Ten measurements for each band)

(1) (2a) (2) (2a)

(cm -1) (cm -^) (cm -') (cm -')

1 544.824 0.024 545.345 0.036

2 842.328 0.006 842.341 0.008

3 906.800 0.004 906.874 0.006

4 1028.282 0.004 1028.352 0.004

5 1068.976 0.006 1069.006 0.006

6 1154.597 0.004 1154.645 0.002

7 1583.074 0.006 1583.137 0.003

8 1601.279 0.007 1601.351 0.004

9 2849.923 0.020 2849.908 0.020

10 3001.334 0.010 3001.327 0.010

11 3026.266 0.014 3026.301 0.016

12 3059.889 0.012 3059.870 0.008

13 3082.068 0.012 3082.105 0.003

(1) With screen

(2) Without screen

18
Table 9

Effect of Beam Geometry on the Peak Wavenumber

of the Absorption Bands of a Polystyrene Film

(Ten measurements for each band)

(1) (2a) (2) (2a)

1 546.047 0.042 544.824 0.025

2 841.483 0.006 842.328 0.008

3 906.908 0.004 906.800 0.004

4 1028.365 0.039 1028.282 0.004

5 1069.203 0.006 1068.976 0.006

6 1154.676 0.004 1154.597 0.004

7 1583.152 0.003 1583.074 0.006

8 1601.359 0.008 1601.279 0.007

9 2849.920 0.018 2849.923 0.020

10 3001.304 0.008 3001.334 0.010

11 3026.325 0.018 3026.266 0.014

12 3059.869 0.016 3059.899 0.012

13 3082.080 0.010 3082.068 0.012

(1) 45° tilt (2) No tilt

19
500 1000 1500 2000 2500 3000 3500

Wavenumber (cm"^)

Figure 1. Spectrum of polystyrene film showing locations of certified absorption peaks.

20
1

E

o

0)

c

o

CO

>

o

o

(0

c

CO

o

0.1

0.01

o Vacuum, CG

A Purge, CG

O I A

OAI

A o Pa

oo

oi

Al

O

1 A

Ai

A

O

Ol A

U o

O 0 ^

^

..[.A. b

|6>

oo

500 1000 1500 2000 2500 3000 3500

Peak Wavenumber (cm"^)

Figure 2a. Comparison of peak positions for polystyrene absorption bands, made under

vacuum and purge conditions: two standard deviation values.

21
1

.o.. S 0.1

o

o

c

a>

i

•D- •O

(0

o

Q.

!

0.01

-°

Q.

-Q.

Qj.

.Q.4.

|Vac Peak - Purge Peak|

0.001

500 1000 1500 2000 2500 3000

Peak Wavenumber (cm"^)

3500

Figure 2b. Comparison of peak positions for polystyrene absorption bands, made under

vacuum and purge conditions: peak position differences.

22
E

o

(0

c

o

(0

>

o

CO

"D

C

CO

0)

o

10

0.1

0.01

o CG, Vacuum

A Min. Find, Vacuum

A

Ai

I

,Al

^ A

o

-o

o io

^of

o :0

Ob?,

lata

6

A.

...[A... Aa

1^

500 1000 1500 2000 2500 3000

Peak Wavenumber (cm"^)

3500

Figure 3a. Comparison of peak positions for polystyrene absorption bands, as determined

by center-of-gravity and minimum-find techniques: two standard deviation values.

23
10

E

S 1

o

o

c

o

o»*-

»*-

mmm a

CO

0)

0.

0.1

0.01

iak\ •: 1 |CG Peak - Min Pc

HJ

i i D-i -

1 °i

D 4 i \

\ - D : I p

!fh 1 1 i °

[ U i

i

[ !"n

1

[o -

500 1000 1500 2000 2500 3000 3500

-1

Peak Wavenumber (cm )

Figure 3b. Comparison of peak positions for polystyrene absorption bands, as determined

by center-of-gravity and minimum-find techniques: peak position differences.

24
Appendix A. Effects of several parameters

A. 1 effect of intensity variation

The absorption peaks of a polystyrene film were obtained with and without using a screen in the spectrometer. Table 8 indicates that there are statistically significant differences.

The screen was used to reduce the intensity on the detector in a neutral fashion to test for peak

value dependence on source intensity. The variation may be related to the MCT detector

nonlinearity.

A.2 Effect of beam geometry

A polystyrene film has been measured with normal incidence and with 45° incidence.

This was done to reveal any dependence on beam geometry and/or path length in the

polystyrene film. Even with this large incident angle, the absorption-peak difference between

measurements with 45° and with normal angle exceeds the expanded uncertainty at only three

peaks as shown in Table 9.

A.3 Effect of peak-determination method

The exact peak positions of a polystyrene film may be different when using different

peak wavenumber determination methods to obtain the peak wavenumbers. Fig. 3(b) shows

the peak difference obtained by a center-of-gravity (CG) technique and by a minimum-find

(Min Find) technique in vacuum (indicated by the symbol for {CG Peak - Min Peak}). Most

of the differences are larger than the two standard deviations of both techniques shown in Fig.

3(a).

Appendix B. SRM 1921 certificate

(see next six pages)

25

(Etxiiiitnit

Standard Reference Material 1921

Infrared Transmission Wavelength Standard

This Standard Reference Material (SRM) is intended for use in calibrating the wavelength scale of spectrophotometers

in the infrared (IR) spectral region from 3.2 fim to 18 ^m (555 cm ' to 3125 cm '). SRM 1921 is a matte finish polystyrene film approximately 38 jum thick with a 25 mm diameter exposed area, centered 38 mm from the bottom of

a cardboard holder which is 5 cm (w) x 1 1 cm (h) x 2 mm (t) in size. A unit of SRM 1921 consists of five (5) polystyrene

cards.

Certified Wavelength Values: The spectral transmittance of a representative group of samples of polystyrene film was

measured in vacuum. The positions of absorption peaks in the range of 3.2 fim to 18 iim were obtained using a center of gravity method. Thirteen of these peak positions were selected for certification based on experimental and statistical analysis results. The wavelength values of these peaks are certified and are shown in Table 1 along with their associated

uncertainties. The corresponding peak wavenumber values are listed in Table 2. See the section "Peak Wavenumber

and Wavelength Determination" for details. To aid the user in distinguishing among the peaks during measurement, a spectrum is shown in Figure 1, with arrows identifying the certified peaks. For peak wavelength and wavenumber values measured in air or under purge conditions see the section "Correction for Air/Nitrogen Purge".

Measurement Conditions: The calibration measurements were made using a Bomem DA-3.02 Fourier transform

spectrophotometer. The instrument room temperature was maintained near 22 °C and the humidity ranged from 30%

to 50% during the measurements. Calibration measurements were made under vacuum level pressures of 50 Pa (0.4

Torr). Details of the measurements and data analysis can be fotmd in Reference [IJ.

Storage and Handling: When not in use, SRM 1921 should always be kept in its accompanying protective cover. For

storage, it is advisable to keep the SRM in a desiccator cabinet when available. The SRM should always be handled with

care; the exposed film surface should never be touched by fingers or any other objects. Dust may be removed by blowing

with clean, dry air.

Expiration of Certification: The polystyrene films have been measured over a period of approximately one year, without

significant change of any wavelength positions. The measured samples will be monitored over time, and in the event that the certification becomes invalid, users will be notified by NIST. Because of the finite measurement period, this certificate is valid for 3 years from the date of shipment from NIST.

The technical measurements leading to certification were performed by D. Gupta, L.M. Hanssen, and L. Wang of the NIST Radiometric Physics Division. The overall direction and coordination of the technical measurements leading to certification were performed under the supervision of J.J. Hsia, R. Datla, and L.M. Hanssen of the NIST Radiometric

Physics Division.

Statistical consultation was provided by S.B. Schiller of the NIST Statistical Engineering Division.

The technical and support aspects involved in the revision of this certificate were coordinated through the Standard

Reference Materials Program by J.C. Colbert.

Gaithersburg, MD 20899 Thomas E. Gills, Chief

April 7, 1995 Standard Reference Materials Program

(Revision of certificate dated 5-19-94)

Page 1 of 6
Source of Material: The polystyrene film used in SRM 1921 has been taken from a single roll and was manufactured

by the Dow Chemical Company under the trade name Trycite', #DWF-6(X)1. The polystyrene film was donated by the Coblentz Society.

INSTRUCTIONS FOR USE

Calibration Measurements: Prior to calibration with SRM 1921, the spectrophotometer should be set up under the following conditions: 1) the instrumental resolution should be set at 0.5 cm ' (if this is not achievable, the resolution should be set at the highest, (i.e. smallest value in cm ') achievable by the instrument); 2) the spot size on the sample

should be set to the maximum possible, yet not greater than that required to maintain measurement resolution and not greater than that at which the wavenumber shift error becomes significant [2] and not greater than that at which the detector becomes significantly non-linear [3,4]; 3) the sample chamber should be closed and purged or evacuated for a

suitable time, for the instrument to reach pressure and temperature equilibrium; 4) the calibration procedure should begin

with a "reference" measurement with no sample in the sample chamber; 5) SRM 1921 should be placed in the standard sample position, and a "sample" measurement should be made. The ratio of "sample" to "reference" spectra is the transmittance. This process (steps 3 to 5) should be repeated in sequence at least six (6) times. The resulting

transmittance spectra should be analyzed for peak position as described below.

Peak Wavenumber and Wavelength Determination: The method used to determine the peak wavenumber (v) and

wavelength (A.) values of SRM 1921 is the center of gravity technique [5]. This procedure is performed on the

transmittance spectra using wavenumber values only. The wavenumber value is defined as the number of waves per unit length (cm). Refer to Figure 2 for the following peak determination procedure. First, the bounds of an initial wavenimiber range (v^j^ to v^^) enclosing the peak are determined; they are the wavenumber values at which

transmittance relative maxima occur on either side of the peak. Next, the differences between the transmittance values

at each bound and the transmittance at the absorption peak

^T(v^) = [T(v^J-T(Vp^)] and AT(v^i„) = [T(v^i„)-T(vp^)]

are determined. Then half the value of the smaller of AT(v^ and AT(v^jJ, ATy2 is determined. The final wavenumber

range (v, to v 3) to be used in the center of gravity calculation is that between the wavenumber values where the transmittance values on either side of the peak equal the minimum transmittance value plus ATy2.

v..2(T=T(Vp^) + ATy2)

A center of gravity calculation [6] on this region should be performed to obtain the peak wavenumber values to compare

to the certified values. If another peak wavenumber determination method is used, a comparison with the certified values may not be valid. Four peak wavenumber values, noted in Tables 1 and 2, were found to be less sensitive to the technique

used to derive them (see Reference 1). Peak values determined by other techniques may become available in the ftiture. Wavelength values can be obtained from the wavenumber values through the relationship A.v = l, where k is the wavelength in cm.

Correction for Air/Nitrogen Purge: The calibration measurements were performed in vacuum. Hence the wavelength

values in Table 1 are vacuimi values (where n= 1 , the index of refraction). For measurements of SRM 1921 made under

nitrogen gas or air purge, the wavenumber and wavelength values need to be adjusted^ due to the index of refraction of

the air or purge gas (n= 1.00026 for dry nitrogen gas at atmospheric pressure and (T=298 K)) [7,8]. The measured

wavenumber values should be divided by 1.00026 and the wavelength values should be multiplied by 1.00026 to compare

to the standard values.

\

The use ofa trade name on this certificate is for identification only and does not imply endorsement of the product

by the National Institute of Standards and Technology.

^or instruments which give vacuum wavenumber and wavelength values, no adjustment for the index of refi-action of air or purge gas should be performed.

Page 2 of 6
Corrections to Instrument Wavenumber Scale: The resulting N (N >. 6) values for each peak at wavenumber, v

,

should be averaged to obtain a single "peak wavenumber value" (laboratory mean, yj, and the standard deviation of the

values, s„ should be calculated. In order to determine whether the laboratory measurements are biased relative to SRM

1921, calculate the absolute difference, A,, between the laboratory mean, y, and the certified value, C,: A = V I y' V

- C V I The uncertainty associated with this difference is:

A^ = (t^,0.95) s/v^ * U, [9]

where tN.,0.95 is the critical value from the student's distribution with N-1 degrees of freedom for a two-sided 95%

confidence interval and U [10,11] is the uncertainty from the certificate. For example, if N=6, t, 0.95 = 2.571. If A, > A^., then the difference is greater than can be explained by chance, and the wavenumber scale of the instrument

should be corrected to the SRM. If this is the case, generally a linear least squares fit of A, to v for the thirteen peaks

should provide a sufficient correction to the spectrophotometer scale. However, if A, ^ A^, the wavenimiber scale of

the spectrophotometer is accurate and correction is not advised.

REFERENCES

[I] Gupta, D., Wang, L., Hanssen, L.M., Hsia, J.J., and Datla, R.V., Standard Reference Materials: Polystyrene

Films for Calibrating the Wavelength Scale of Infi:ared Spectrophotometers - SRM 1921, NIST Special Publication

260-122.

[2] Griffiths, P.R., and DeHaseth, J. A., Fourier Transform Infrared Spectrometry. Chapter 1, p. 34, John Wiley &

Sons, New York, (1986).

[3] ASTM E 1421-91 "Standard Practice for Describing and Measuring Performance of Fourier Transform Infrared FT-IR Spectrometers: Level Zero and Level One Tests", in Annual Book of ASTM Standards, 14.01, (1991).

[4] Hirschfeld, T., Fourier Transform Infrared Spectroscopv . Chapter 6, Ferraro, J.R. and Basile, L.J. eds.. Applications to Chemical Systems, 2, Academic Press, New York, (1979).

[5] Cameron, D. G., Kauppienen, J.K., Moffatt, D.J., and Mantsch, H.H., Appl. Spectrosc, 36, 245, (1982).

[6] Griffiths, P.R., and Dettaseth, J. A., Fourier Tranform Infrared Spectrometry. Chapter 6, p. 235, John Wiley &

Sons, New York, (1986).

[7] Edlen, B.,"The Refractive Index of Air," Metrologia, 2, 12, (1966).

[8] Smith, F.G., ed.. Atmospheric Propagation of Radiation. Chapter 1, p. 88, SPIE Optical Engineering Press, Bellingham, Washington, (1966).

[9] Becker, D. et.al., "Use of NIST Standard Reference Materials for Decisions of Performance of Analytical

Chemical Methods and Laboratories," NIST Special Publication 829, (1992).

[10] "Guide to the Expression of Uncertainty in Measurement" ISBN 92-67-10188-9, 1st Ed., ISO, Geneva,

Switzerland, (1993).

[I I] Taylor, B.N., and Kuyatt, C.E., "Guidelines for Evaluating and Expressing the Uncertainty of NIST Measurement

Results," NIST Tech. Note 1297, (1994).

Page 3 of 6
Table. 1 Certified Peak Wavelength Values (in vacuum)

Peak Wavelength (/xm) Expanded Uncertainty, U*

1 8 no^ n A 1 TO

1 1 oncA ll.O/JH U.UU/U

1 1 .0275 0.0080

9.7243 0.0026

9.3528 0.0040

8.6607* 0.0041

6.3166* 0.0002

6.2447* 0.0003

3.5086 0.0023

3.3318 0.0001

3.3042 0.0007

3.2680* 0.0002

3.2445 0.0001

Table. 2 Certified Peak Wavenumber Values (in vacuum)

Peak Wavenumber (cm"') Expanded Uncertainty, U*

545.48 12.29 842.08 0.49

906.82 0.66

1028.35 0.27

1069.20 0.46

1154.64* 0.54

1583.13* 0.06

1601.35* 0.07

2850.13 1.84 3001.40 0.12

3026.42 0.61 3060.03* 0.14

3082.19 0.12

The expanded uncertainty, a NIST associated uncertainty of the certified peak value, was calculated according to "The

Guide to Expression of Uncertainty in Measurement" [10, 11]. It is the product of a coverage factor, at the 95% level of confidence, and the combined standard uncertainty. The combined standard uncertainty is the root sum of squares of

components of uncertainty due to detector, sample, run, and measurement.

*Peak values less sensitive to peak determination method [1].

Page 4 of 6
Figure 1. Spectrum of polystyrene film showing locations of certified peaks.

Page 5 of 6
Wavenumber (crrr^

)

Figure 2. Diagram indicating parameters used in the peak wavenimaber

determination method (see text for details).

Page 6 of 6


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