| NIST Measurement Services: The Calibration of Thermocouples and Thermocouple Materials ee Ci Publication 250-35 G. W. Burns and M. G. Scroger U.S. Department of Commerce National Institute of Standards and TechnologyNIST MEASUREMENT SERVICES: The Calibration of Thermocouples and Thermocouple Materials G. W. Bums and M. G. Scroger April 1989 oor NOTE: As of 23 August 1988, the National Bureau of Xe ‘Standards (NBS) became the Nationa Insttute of Standaras and Tecrnoiogy (NIST) when Fresigene Reagan signed into law the Omnibus Trade and %, BS J Compettiveness Ac. U.S. DEPARTMENT OF COMMERCE, Robert A. Mosbacher, Secretary NATIONAL INSTITUTE OF STANDARDS AND TECHNOLOGY, Raymond G. Kammer, Acting DirectorLibrary of Congress Catalog Card Number: 89-600732 National institute of Standards and Technology Special Publication 250-35 Natl. inst. Stand. Technol. Spec. Publ. 250-35, 201 pages (Apr. 1989) CODEN: NSPUE2 Certain commercial equipment, instruments, of materials are iientiied in this paper in order to adequately specity the experimental procedure. Such identification does not imply recommendation or endorsement by tha National Inatinta of Standage and Tachnalogy, ror does it imply that the materials or equipment ilentified are necessarily the best avaliable for the purpose. U.S. GOVERNMENT PRINTING OFFICE WASHINGTON: 1989 For oale by the Ouperintendent of Documents, U.S. Govemmont Printing Offee, Washington, BC 0102 0226PREFACE Calibrations and related measurement services of the National Institute of Standards and Technology provide the means for makers and users of measuring teole to achieve levels of meacurenent accuracy that are necereary to attain quality, productivity and competitiveness. These requirements include the highest’ levels of accuracy that are possible on the basis of the most modern advances in science and technology as vell as the levels of accuracy that are necessary in the routine production of goods and services. More than 300 different calibrations, measurement assurance services and special tests are available from NIST ‘to support the activities of public and private organizations. These services enable users to link their measurements to the reference standards maintained by NIST and, thereby, to the measurement systens of other countries throughout the world. NIST Special Publication 250, NIGT Calibration Comicce Users Guide, describes che calibrations and related services that are offered, provides essential information for placing orders for these services and identifies expert persons to be contacted for technical assistancé - NIST Special Publication 250 has recently been expanded by the addition of supplementary publications that provide detailed technical descriptions of specific NIST calibration services and, together with the NIST Calibration Services Users Guide, they constitute a topical series. Each technical supplement (NIST SP 250- ) on a particular calibration service includes: © specifications for the service © design philosophy and theory © description of the NIST measurement system © NIST operational procedures © measurement uncertainty assessment error budget systematic errors random errors © NIST internal quality control procedures ‘The new publications will present more technical detail than the information that can be included in NIST Reports of Calibration. In general they will also provide more detail than past publications in the scientific and technical literature; such publications, when they exist, tend to focus upon a particular element’ ot the topic and other elements may have been published in different places at different times. The new series will integrate the description of NIST calibration technologies in a form that is more readily accessible and more useful to the technical user: ‘The present publication, SP 250-35, NIST Measurement Services: The Calibration of Thermocouples and Thermocouple Materials, by G. W. Burns and M. G. Scroger, iiiis one of approximately 20 documents in the new series published or in preparation by the Center for Basic Standards. It describes calibration technology and procedures utilized in connection with NIST Service Identification Numbers from 32010C to 32150S listed in the NIST Calibration Services Users Guide 1989, pages 54 to 55. Inquiries concerning the contents of these documents may be directed to the author(s) or to one of the technical contact persons identified in the Users Guide. Suggestions for improving the effectiveness and usefulness of the new series would be very much appreciated at NIST. Likewise, suggestions concerning the need for new calibration services, special tests, and measurement assurance programs are always welcome. Joe D. Simmons, Acting Chief Office of Physical Measurement Services katherine Gebbie, Acting Director Genter for Basic StandardsCONTENTS Page DESCRIPTION OF SERVICES. ©... - 1. eee eee 1 2. PRINCIPLES OF THERMOELECTRIC THERMOMETRY... ...... aCe) 2.1 Thermoelectric Phenomena... ee 4 2.2 Choice of the Thermocouple Materials». ts 6 2.2.1 ‘Temperatures from 0 K to 450 8 212.2 ‘Temperatures from 450 "¢ to 1100“c. 21)... 10 21213 ‘Temperatures above 1100 °C... . 1.11. ua 2.3 Inhomogeneity. ©. ee ee eee BD 2.4 Galibration. 6 ees 5s 9° Inatallation 45 2.6 Sumary of the Laws of Thermoelectric Circuits |. |.) - 16 Law of Homogeneous Metals... . . ere 16 Law of Intermediate Metals...) 16 Law of Successive or Intermediate Temperatures... 0. ee eee 2.7 References... 22 es 18 3 CALIBRATION METHODS AND PROCEDURES FOR THERMOCOUPLES AND THERMOCOUPLE MATERIALS... 2. eee eee ee 25 31 Galihration by Comparison with a Reference Thermocouple... ee Seon 3.1.1 Type S, Type R, and Type B Thermocouples || | | 25 3.1.1.1 “Preliminary Examination... . 2. 25 34 Electrical Anneal. .. 2.1) 1). 25 3.1.1.3 Mounting for Calibration.) 111.) (26 3.1.1.4 Furnace Anneal..... 0.0. 26 3B\L1,5 Calibration Data, 27 3.1.1.6 Packing and Shipping») 2). 1) 27 3.1.1.7 Calibration Report. 2... 2... 28 3111118 Apparatus Buoodsece 31 3.1.2 Base Metal Thermocouples. 2)... 33 3.13 Thermoelements versus Platinum Thermoelectric Reference Standard, Pt-67.... 35 3.1.4 — Metal-Sheathed Thermocouples... 1... 2. 35 3.2 Calibration by Comparison with a Standard Platinum Resistance Thermometer... ..-. 0... 0 36 $2.4 Galipration satns. lt 38 3.2.1.1 Water and Oil Baths. |) 1.) | : 36 3.2.1.2 TinBath.. 2... 00.00.00. 397 3B Geyooeae 38 3.2.1.4 Liquid Oxygen and Liquid Nitrogen Points... .. 2... - 383. 4.5 46 3 3.2.2 Equipment... . eogoccdn 3.2.2.1 Standard Platinum Resists rie emome cer ec oie 3.2.2.2 AC Bridge. . 3.2.2.3 Potentionete: Calibration Procedur. oo Computation of Bath Temperature... 2... Calibration Report... ... - BuGus05 sry Calibration of Type $ Thermocouples tal Freezing-Point Cells... . Preliminary Examination... 2... 11. Electrical anneal... 2... se Mounting for Calibration) | 2222221! pi yrs pac oGacsdas Preliminary Tests. . : Eu Measuscwents at Fieezing Points. || | | 3.3.6.1 Gold and Silver Freezing Points. | | 3.3.6.2 antimony Freezing Point... . 1... 3.3.6.3 Zinc Freezing Point Packing and Shipping... . Gaob5baq0 Calibration Report. 22... le Electrical Annealing System. |< Welding Station... ... 0... Annealing Furnace... ee Furnace For Preliminary Tests. | | | Freezing-Point Cells... 2... Furnace for Gold and Silver Treesing Toint Gella ss ss se Furnace for Antimony and Zinc’ Freezing-Point Cells... . 3.3.9.8 Ice Baths... .. Boe 3.3.9.9 Measuring Instrument . ube s Peeuvermues Voltage Standards. . . ee ae Voltage Measuring Instruments. 1) 122221111) tt 4.2.1 Potentiometers... 1... ee 4.2.2 Digital Voltmeters. 2... 2... 00. 4.2.3. Thermocouple Measuring Circuitry... . Resistance Measuring Instrument... . . « Temperature Measuring Instruments. 2&1 Working-Standard Raforancn Tharnacauniax 4.4.2 Standard Platinum Resistance Thermometers. . . Platinum Thermoelectric Reference Standard... . a Thermocouple Fixed-Point Check Standards... . vi Page 39 My 40 40 rst 46 46 46 46 47 a7 49 50 50 51 33 53 53 53 53 35. 35 55 56 69Page 4.7 Thermometric Fixed Points... 2.2... ...00. 2B 4.7.1 Metal Freezing-Point Geils...) 1.2.11. 73 4.7.2 Water Triple-Point ells... 1... 1. OB taS7 ton teclibeacina ett rire pobccoD 4.8 References... ... Be era 5 ASSRSEMENT OF TINCERTATNTTRS 103 5.1 Uncertainties in Primary Calibrations of Type S$ Thermocouples... ee 103 5.2 Uncertainties in Comparison Calibrations of ‘Type S Thermocouples... 2... 0. 2 ee eee - 10 5.3 References... 0... ee Be segs einiiy FUTURE DIRECTIONS... 6... 0... See ee 122 7. prpLrocpapiy. a 123 7.1 National Bureau of Standards Publications... ...... 123 7:2 American Society for Testing and Materials Publications. | 123 7:3 Instrument Society of America Publications... .... 212% 7.4 International Electrotechnical Commission Publications . . 124 7.8 Other Publications. ............ pees 18h 8 APPENDICES. ©... 2... eee ce 126 1 Calibration Reports... 2 ee se 126 8.1.1 Type § Thermocouple - Fixed-Point Calibration... 2... . - 126 8.1.1.1 Covering Letter and Bound Calibration Report for Customer. . . . 126 8.1.1.2 Sumary of Calibration Results for NIST Record... 0... .. 136 8.1.2 ‘Type S$ Thermocouple - Comparison Calibration | | 148 1.2.1 Covering Letter and Bound Calibration Report for Customer. . . . 148 8.1.2.2 Summary of Calibration Results for NIST Record -. 157 8.1.3 Type R Thermocouple - Comparison Calibration | | 164 1.3.1 Covering Letter and Bound Calibration Report for Customer. . . . 164 8.1.3.2 Summary of Calibration Results for NIST Record . 173 8.1.4 Type T Thermocouple - Comparison with SPRT | | | 180 8.1.5 Base fatal Thermocouple - Conparison Calibration... 2... ee ee ee 186 vitLIST OF FIGURES Figure Page aie ‘Schematic diagram of thermocouples with a Junction box... 21 2.2. Thermoelectric power of some low-temperature thermocouples... 0.2. eee ey 2d 2.3, Calibration emf’s of three standard thermocoupl at the zine point and at the gold point. Time at Inigh Lomperature Le about 5h for each oot 1. ee 22 2.4. ‘Temperature-enf relationships of some high-tomperature thermanaupla - 2 2.5. Thermoelectric power of some high-temperature thermocouples... . 21... 2.4555 23 2.6. Enf (E) unaffected by third material, C........-.- 23 2.7. Ents are additive for materials... ......- ey ae 2.8. Enfs are additive for temperature intervals... ...... 2% a Schematic of automatic thermocouple calibration system for comparison calibrations ....... . ey 3.2, Chromel tube furnace (50 to 110°C)... ...-....- 58 3.3. Silicon carbide tube furnace (50 to 1600°C)........ 59 3.4, Oi bath eee ee ee OO 3.5. Oil bath and water bath. 2. ee cee OL 3.6. Tin bath. 2... ee eee 3.7. Tin bath 0 eee ee 6B 2.8. cryoetat 2. 64 3.9. Gryostat.. 2... ee ee 3.10, Metal freezing-point cell... 2... ee es 66 3.11, Freezing-point furnace for gold and silver... ...... 67 3.12,‘ Freezing-point furnace for antimony and zinc... ..... 68 4a. calibration history of saturated standard cells, ©... 2. 77 viiiFigure Page 4.2. Calibration corrections for Guildline potentiometer... .. 78 4.3. calibration history of type $ standard thermocouple S8C-68-2 at the gold point (1064.43 °C)... ... Bs) 4h, Calibration history of type $ standard thermocouple SC-68-2 at the silver point (961.93 °C)........... 80 4.5. Calibration history of type $ standard thermocouple $0-68-2 at 630.74 °C... ee eee ee ee BL 4.6. Calibration history of type $ standard thermocouple SC-68-2 at the zinc point (419.58 °C)... . 2... 2... 82 4.7. calibration history of type $ standard thermocouple 8C-68-7 at the gold point (1064.43 °C). ......... - 83 4.8. Calibration Wetury vf Lyye 8 stamlard chermvcouple SC-68-7 at the silver point (961.93 °C)... ... . we 8h 49) calibration history of type § standard thermocouple $0-68-7 at 630.74 °C... 2. ee ee cee BS 4.10. Galthratton history of type §,standard thermocouple: SC-68-7 at the zinc point (419.58 °C)... . . te 86 4.11, Calibration history of type S standard thermocouple SC-71-5 at the gold point (1064.43 °c)... ...... .. 87 4.12, Calibration history of type § standard thermocouple: 06 71 5 at the aflver poine (961.93 °C)... ce 88 4.13. Calibration history of type S standard thermocouple SO-71-5 at 630.74 °C. - 89 4.14. Galtbration history of type $ standard thermocouple SC-71-5 at the zine point (419.58 °C)... . . . ar) 4.15. Calibration history of type S standard thermocouple SC-71-6 at the gold point (1064.43°C)........... 92 4.16. Calibration history of type S standard thermocouple SC-71-6 at the silver point (961.93 °C)... ........ 92 4.17 Galthratton hlacory of type 8 standard thersocouple 80-71-6 at 630.74 °C... 2... ee 2) 4.18 Calibration history of type $ standard thermocouple SC-71-6 at the zine point (419.58 °C)... .. 2... 94, ixFigure 4.19 4.20, 4.21. 4.22. 4.23. 4.2, 4.25, 4.26. set stay 5.3. 5.4. Calibration history of type S standard thermocouple SC-72-1 at the gold point (1064.43 °C)... .. . : Galibration history of type § standard thermocouple SC-72-1 at the silver point (961.93 °C)... ........ Calibration history of type S standard thermocouple Perrot aude sen oe coun eo bec oon Calibration history of type $ standard thermocouple 6¢ 72 1 at the cine point (419.58 °C). ee ee Calibration history of type S standard thermocouple SC-72-2 at the gold point (1064.43 °c)... Calibration history of type S standard thermocouple SC-72-2 at the silver point (961.93 °C)... ........ Galtheation history of type 8 standard thermocouple SC-72-2 at 630.74 °C... 2... PPeesoca- Calibration history of type $ standard thermocouple SC-72-2 at the zinc point (419.58 °C)....... ee Error per unit emf error at the fixed points in thermocouple emfs calculated from the Sh-Ag-Au calibration quadratic Error per unit emf error at the fixed points calculated from the 0 °C-Zn-Sb quadratic used to represent the emf difference between the calibration values and the NBS Monograph 125, reference table values at the fixed-points . . . Emf difference between values of emf determined in a comparison calibration using type $ reference thermocouple 3C-83-7 and emf values obtained in « primary calibration at the fixed points for 23 type § test thermocouples. (Eaf difference ~ primary comparison) Enf difference between values of emf determined in a comparison calibration using type S reference thermocouple SC-83-8 and emf values obtained in a primary calibration at the fixed points for 16 type S$ test thermocouples. (Emf difference = primary - comparison) ........ Page 95 96 97 208 09 101 102 18 119 120 121table al. 2A. 2.2. 4a. 4.2, 5.1. 5.2. 5.3. 5.4. 5.5. 5.6. 5.7. LIST OF TABLES Page NIST thermocouple calibration capability. ......... 3 Compositions, trade names and letter designations for standardized thermocouples... ..-... +--+ a Suggested upper temperature limits for protected thermocouples and various wire sizes... ....-...- 9 Freezing-point differences for gold and silver cells... . 74 Antimony cell freezing points... ...... Gbeaaes Standard deviations associated with fixed-point cell calibrations... .......---+-55 ee 108 Uncertainty in the temperature of the liquidus points. . . . 108 Sunmary of systematic errors in primary calibrations of type S thermocouples at the fixed points... ...... 109 Propagated uncertainties from total uncertainties at the four fixed points... .......---.0- poe tail Means and standard deviations for differences Detween primary and comparison calibrations. ........ 113 Standard deviations for comparison calibrations... .. . . 114 Total uncertainties in comparison calibrations of type § thermocouples... .. 0... see M6 xt1. DESCRIPTION OF SERVICES calibration services for all commonly used types of tharmocouplas and thermocouple materials are provided by NIST from -196 to +2100 °C. The temperature range for a particular calibration depends on the type of wire or thermocouple submitted. The thermocouples are calibrated by one or more of three general methods, depending on the type of thermocouple, the temperature range, and the accuracy required. All three methods provide traceability to the IPTS-68. In the first method, thermocouples are calibrated by comparison with a standard thermocouple maintained at NIST. In the second method, thermocouples are calibrated against a standard platinum resistance thermometer (SPRT). In the third method, thermocouples are calibrated at 630.7% °0 and at tluce defining temperatures vu the Iuteruativial Fuavtival ‘Temperature Scale (IPTS): the freezing points of Zn, Ag, and Au. Single-leg thermoelements are tested against the NIST maintained platinum thermoelectric reference cfandard, Pr-R7, hy the Firet ar cacand mathad Thermocouple and thermoelement calibrations below 0 °C are made in a cryostat; those above 0 °C are made in stirred liquid baths, metal freezing-point cells, or electric tube-type furnaces. Vacuum or inert-gas furnaces are also available if needed. ‘Test data are processed on a laboratory computer and calibration tables giving values of the thermocouple emf at 1 degree intervals are provided for B, S, R, and T types of thermocouples. An automatic data acquisition system is used to record the test data for calibrations performed by the comparison method, ‘The temperature ranges and calibration uncertainties for standard letter- designated thermocouples calibrated by the three methods described ahove are given in table 1.1. While over 90% of the thermocouples calibrated at NIST are letter-designated types, calibration services are also provided to temperatures as high as 2100 °C for non-standard types of thermocouples formed from various W-Re, Ir-Rh, and Pt-Rh alloys. Calibrations for the non-standard types are performed as special tests on an actual cost basis, and the temperature ranges and calibration uncertainties depend on the thermocouple vype. Only bare wires are needed for NIST thermocouple calibrations. We would prefer customers not to send ceramic insulating end piulectluy Lubes since they may get broken during shipment. If the thermocouple is shipped in a mount such as a protection tube assembly, a special dismantling fee may be charged and the parte will he returned unaccombled, Leade and outonsion vires need not be sent to NIST with the thermocouples. All thermocouple calibration data furnished in reports are based on a reference junction temperature of 0 ‘C (32 °F). The customer may request that calibration results be given either in degrees Celsius or Fahrenheit. For base-metal thermocouples (types E, J, K, N, and 7) and thermocouple materials, only those that are unused will be accepted for test. A cali- bration will be undertaken only if the thermocouple is likely to yield the specified accuracy.