1、Designation: E1552 08E1552 15Standard Test Method forDetermining Hafnium in Zirconium and Zirconium Alloys ByDirect Current PlasmaAtomic Emission Spectrometry1This standard is issued under the fixed designation E1552; the number immediately following the designation indicates the year oforiginal ado
2、ption or, in the case of revision, the year of last revision. A number in parentheses indicates the year of last reapproval. Asuperscript epsilon () indicates an editorial change since the last revision or reapproval.1. Scope1.1 This test method covers the determination of hafnium in zirconium and z
3、irconium alloys in concentrationswith compositiongreater than 0.003 %.0.003 % (30 mg/kg).1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.1.3 This standard does not purport to address all of the safety problems, if any, ass
4、ociated with its use. It is the responsibilityof the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatorylimitations prior to use. Specific precautionary statements are given in Section 8.2. Referenced Documents2.1 ASTM Standards:2B
5、349/B349M Specification for Zirconium Sponge and Other Forms of Virgin Metal for Nuclear ApplicationB350/B350M Specification for Zirconium and Zirconium Alloy Ingots for Nuclear ApplicationB351/B351M Specification for Hot-Rolled and Cold-Finished Zirconium and ZirconiumAlloy Bars, Rod, and Wire for
6、NuclearApplicationB352/B352M Specification for Zirconium and Zirconium Alloy Sheet, Strip, and Plate for Nuclear ApplicationB353 Specification for Wrought Zirconium and Zirconium Alloy Seamless and Welded Tubes for Nuclear Service (ExceptNuclear Fuel Cladding)B493 Specification for Zirconium and Zir
7、conium Alloy ForgingsB494/B494M Specification for Primary ZirconiumB495 Specification for Zirconium and Zirconium Alloy IngotsB523/B523M Specification for Seamless and Welded Zirconium and Zirconium Alloy TubesB550/B550M Specification for Zirconium and Zirconium Alloy Bar and WireB551/B551M Specific
8、ation for Zirconium and Zirconium Alloy Strip, Sheet, and PlateB614 Practice for Descaling and Cleaning Zirconium and Zirconium Alloy SurfacesB653/B653M Specification for Seamless and Welded Zirconium and Zirconium Alloy Welding FittingsB658/B658M Specification for Seamless and Welded Zirconium and
9、Zirconium Alloy PipeB752 Specification for Castings, Zirconium-Base, Corrosion Resistant, for General ApplicationB811 Specification for Wrought Zirconium Alloy Seamless Tubes for Nuclear Reactor Fuel CladdingE50 Practices forApparatus, Reagents, and Safety Considerations for ChemicalAnalysis of Meta
10、ls, Ores, and Related MaterialsE135 Terminology Relating to Analytical Chemistry for Metals, Ores, and Related MaterialsE1097 Guide for Determination of Various Elements by Direct Current Plasma Atomic Emission Spectrometry3. Terminology3.1 For definitions of terms used in this test method, refer to
11、 Terminology E135.1 This test method is under the jurisdiction of ASTM Committee E01 on Analytical Chemistry for Metals, Ores, and Related Materials and is the direct responsibility ofSubcommittee E01.06 on Ti, Zr, W, Mo, Ta, Nb, Hf, Re.Current edition approved July 15, 2008May 15, 2015. Published A
12、ugust 2008June 2015. Originally approved in 1993. Last previous edition approved in 20022008 asE1552 93 (2002).E1552 08. DOI: 10.1520/E1552-08.10.1520/E1552-15.2 For referencedASTM standards, visit theASTM website, www.astm.org, or contactASTM Customer Service at serviceastm.org. For Annual Book of
13、ASTM Standardsvolume information, refer to the standards Document Summary page on the ASTM website.This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Becauseit may not be technically
14、 possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current versionof the standard as published by ASTM is to be considered the official document.Copyright ASTM International, 100 Barr Harbor Drive, PO Box C70
15、0, West Conshohocken, PA 19428-2959. United States14. Summary of Test Method4.1 The sample, in the form of drillings, chips, milling, turnings, or powder, is dissolved in dilute hydrofluoric acid (HF). Thehafnium content is measured using a direct current plasma (DCP) spectrometer, which is calibrat
16、ed with reference solutions ofhafnium in the presence of zirconium. The microprocessor is programmed to display the results in micrograms per millilitre(g/mL).5. Significance and Use5.1 When zirconium materials are used in nuclear applications, it is necessary that hafnium, a neutron absorber, be pr
17、esent onlyat very low concentrations.5.2 This test method is useful in testing materials for compliance with the compositional requirements as given in SpecificationsB349/B349M, B350/B350M, B351/B351M, B352/B352M, B353, B493, B494/B494M, B495, B523/B523M, B550/B550M,B551/B551M, B653/B653M, B658/B658
18、M, B752, and B811.6. Apparatus6.1 Plastic Labware:6.1.1 Beakers, 100-mL, 100 mL, disposable, polypropylene, or 125-mL125 mLpolytetrafluoroethylene (PTFE) are satisfactory.6.1.2 Volumetric FlasksLinear polyethylene (LPE) or polymethylpentene (PMP) are satisfactory.NOTE 1Plastic volumetric flasks chan
19、ge dimension as they age and therefore must be recalibrated periodically.6.2 Spectrometer Modified Czerny-Turner, using an Echelle grating with 30 prism for order separation providing a reciprocallinear dispersion of about 0.1 nm/mm in the 80 to 85th order. The instrument is operated in the sequenti
20、al mode.6.3 Excitation Source:36.3.1 D-C Plasma, formed by a tungsten cathode and two carbon anodes in an inverted “Y” configuration, having a currentoutput of 7 A at 40 V.6.3.2 Glass spray tube shall be replaced with one made from PTFE or pyrolytic graphite to prevent hydrofluoric acid attack onthe
21、 glass.6.4 ArgonCommercially available as prepurified gas or liquid is satisfactory.7. Reagents and Materials7.1 Purity and Concentration of ReagentsThe purity and concentration of chemical reagents shall conform to therequirements prescribed in Practices E50.7.2 Pure Metals:7.2.1 Hafnium Metal or H
22、afnium Dioxide, of highest purity available and having a known impurity content.NOTE 2Many hafnium materials contain residual zirconium in quantity sufficient to affect the hafnium value.7.2.2 Zirconium Metal, of the highest purity available and having a known hafnium content.7.3 Reference Materials
23、:7.3.1 Standard Reference Materials (SRM):4One Zircaloy-4, SRM 360b, containing 80 ppm78.5 mg/kg hafnium, is available.7.3.2 Other reference solutions can be prepared by dissolving zirconium metal in HF. A solution of hafnium metal dissolved inHF is added to the zirconium solution to produce the req
24、uired concentrations.8. Hazards8.1 This method involves the use of concentrated hydrofluoric acid. Read and follow label precautions carefully before using.8.2 Refer to Practices E50, 7.4.11,7.5.11, for more information.9. Preparation of Apparatus9.1 Conduct start-up and wavelength adjustment in acc
25、ordance with the manufacturers instructions.9.1.1 Optimize the hafnium wavelength at 264.14 nm or 282.02 nm while introducing the 1-mg/mL 1 mg/mL solution preparedin 10.2.9.1.2 Enter the appropriate concentration values (microgram per millilitre) for the high and low reference materials into themicr
26、oprocessor.3 The sole source of supply of the apparatus known to the committee at this time is Applied Research Laboratories, Inc., 5371 NW 161 St., Miami, FL 33014,http:/www.arl-. This instrument is no longer manufactured; however there are many instruments of this type which are still in current u
27、se. If you are aware ofalternative suppliers, please provide this information to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of the responsibletechnical committee,1 which you may attend.4 Available from National Institute of Standards and Technology
28、 (NIST), 100 Bureau Dr., Stop 1070, Gaithersburg, MD 20899-1070, http:/www.nist.gov.E1552 1529.2 Replication:9.2.1 Set the microprocessor to average three integrations at 10 s each.9.3 Direct Current PlasmaInstrument Parameters:Current, A 7Voltage, V 40Gas Argon, 99.9 % minFlow rate, L/min 8Entrance
29、 slits, m 50 wide by 300 highExit slits, m 25 wide by 300 high10. Preparation of Calibration Solutions and Specimens10.1 Preparation of Calibration Solutions:10.1.1 Weigh 1.0 g SRM to the nearest 1 mg into a plastic beaker. Add 20 mL water and, in small increments, add 10 mL HF(48 %) and cover with
30、a plastic cover. When the reaction subsides, add 2 mL nitric acid (HNO3) and place the beaker on a steambath for 10 min to assure complete dissolution of the specimen.10.1.2 Cool the solution, transfer to a 100-mL 100 mL plastic volumetric flask, dilute to volume and mix.10.2 Preparation of Hafnium
31、Solution (1 mg/mL):10.2.1 Hafnium MetalWeigh 0.1 g of the pure hafnium to the nearest 0.1 mg, into a plastic beaker. Add 20 mL water and, insmall increments, add 10 mL HF. Cover with a plastic cover and place beaker on a steam bath until dissolution is complete. Coolthe beaker, transfer to a 100-mL
32、100 mL plastic volumetric flask, dilute to volume, and mix.10.2.2 Hafnium DioxideWeigh 0.1179 g of the pure HfO2 to the nearest 1 mg into a plastic beaker.Add 30 mLHF, cover witha plastic cover and place the beaker on a steam bath until dissolution is complete. Cool the beaker, transfer to a 100-mL
33、100 mLplastic volumetric flask, dilute to volume, and mix.NOTE 3Hafnium metal and HfO2 weights must be correspondingly increased as total hafnium content decreases because of impurity content.10.3 Preparation of Hafnium Spiking Solutions:10.3.1 Solution (100 g/mL)Transfer 10.0 mL of the 1-mg/mL 1 mg
34、/mL solution, prepared in accordance with 10.2, into a100-mL 100 mL plastic volumetric flask, dilute to volume, and mix.10.3.2 Solution (10 g/mL)Transfer 10.0 mL of the 100-g/mL 100 g/mL solution, prepared in accordance with 10.3.1, intoa 100-mL 100 mL plastic volumetric flask, dilute to volume and
35、mix.10.4 Preparation of Synthetic Reference Materials:10.4.1 For each calibration point required, weigh 0.5 g of the pure zirconium metal to the nearest 1 mg into a plastic beaker.Add 10 mL water and, in small increments, add 5 mL HF (48 %) and cover with a plastic cover. Continue as described in 10
36、.1.1.10.4.2 Cool the solution and transfer to a 50-mL 50 mL plastic volumetric flask. Reserve sufficient volume for the hafniumspike.10.4.3 Transfer known quantities of the appropriate hafnium spiking solution prepared in 10.3 to each flask as given in Table2.10.5 Preparation of Specimens:10.5.1 Sam
37、ples shall be clean and oil free. Refer to Practice B614 for cleaning procedures.10.5.2 Weigh duplicate 1.0-g 1.0 g portions, to the nearest 1 mg, into a plastic beaker. Dissolve the samples as described in10.1.1 and 10.1.2.11. Calibration and Standardization11.1 CalibrationThe system sets a two-poi
38、nt calibration curve in the microprocessor.11.1.1 “Auto/Range” will set the intensity of the high reference material into memory while being introduced into the plasma.11.1.2 “Low Standard” will set the intensity of the low reference material into memory while being introduced into the plasma.11.2 S
39、tandardizationThe frequency of standardization will depend upon the long term stability of the instrument.11.2.1 To ensure that the instrument is in calibration, introduce the high, low, or an intermediate reference material as a testsolution. If the reading deviates by more than 5 % from the establ
40、ished value, recalibrate as described in 11.1.TABLE 1 Statistical InformationTest Sample Certified ppmmg/kg Hf Assigned Value Amount Found Repeatability (R1 E173) Reproducibility (R2 E173)NIST SRM 1234 46 . 46.1 6.4 9.3NIST SRM 1235 95 . 91.7 7.7 15.5NIST SRM 1236 198 . 195.3 14.3 32.1Production Spe
41、cimen . 614 612.3 41.0 87.8E1552 15312. Procedure12.1 Introduce up to four test solutions in a series into the plasma with the instrument set to average three readings for 10 s each.12.2 Check the calibration after every four test solutions by measuring a reference material as a test solution. If th
42、e readingdeviates by less than 5 % from the established value, continue with the next series of tests. If the standard deviates by more than5 %, recalibrate as described in 11.1 and remeasure the test solutions.12.3 Procedures for “drift correction” are described in Guide E1097.13. Calculation13.1 C
43、alculate the average of the three readings (microgram per millilitre) as follows:Hafnium,ppm5A 3B/C (1)Hafnium,mg/kg ppm!5A 3B/C (1)where:A = concentration of hafnium in test solution, g/mL,B = volume of final test solution, mL, andC = weight of sample, g.14. Precision and Bias14.1 PrecisionFive lab
44、oratories cooperated in testing four specimens. Precision data are given in Table 1.14.2 BiasNo bias was detected in the interlaboratory test results of the NIST SRMs that were included, nor in the higherconcentration production sample that had been assigned a concentrationcomposition value for hafn
45、ium.15. Keywords15.1 d-c plasma; hafnium; zirconiumASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentionedin this standard. Users of this standard are expressly advised that determination of the validity of any such patent righ
46、ts, and the riskof infringement of such rights, are entirely their own responsibility.This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years andif not revised, either reapproved or withdrawn.Your comments are invited either for r
47、evision of this standard or for additional standardsand should be addressed to ASTM International Headquarters. Your comments will receive careful consideration at a meeting of theresponsible technical committee, which you may attend. If you feel that your comments have not received a fair hearing y
48、ou shouldmake your views known to the ASTM Committee on Standards, at the address shown below.This standard is copyrighted by ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959,United States. Individual reprints (single or multiple copies) of this standard may b
49、e obtained by contacting ASTM at the aboveaddress or at 610-832-9585 (phone), 610-832-9555 (fax), or serviceastm.org (e-mail); or through the ASTM website(www.astm.org). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center, 222Rosewood Drive, Danvers, MA 01923, Tel: (978) 646-2600; http:/ 2 Preparation of Synthetic Reference SolutionsConcentrationA Concentration ofSpiking Solution,g/mLVolume of SpikingSolution, mLppmmg/kg(ppm) g/mL30 + bB 0.3 10 1.550 + b 0.5 10 2.51
