Standard Practice for Liquid Penetrant Testing for General lndustry

Standard Practice for Liquid Penetrant Testi ng for General lndustry 1 Тhis s1andard is issued under the fixed designation Et 65/El65M: the numЬer immediately fo1tov.ing the designation indicates the year о!" origiш1.J adoptюn or. iл thc casc of re, isi011, thc ycar о!" last rcvision. А пumЬer i11 pare111heses iпdicotes thc ycar of last rcapproval. Л :шpcrscript cpsilon (е) indict11cs un cditor:ial chungc siot·c thc lust rc,,jsion or rcupprovul. 1. Scope* 1 . 1 This practice 2 covers procedures for penen·ant exam iпa­ tion of materials. Penetrant testing is а nondest,·uctive testing method for detecting discontinuities that are open to the surface sucl1 as cracks, seams, laps, cold shuts, shrinkage, lamiпations, through leaks. 01· lack of fusion and is appl icaЫe to in-p,·ocess, fi пal, and mainte,iance exami 11ations. lt can Ье effectively used iл the examination of nonporous. metallic mшerial s. ferrous and пont"errous metals, and of nonmeta l l i c mate1·ials sL1ch as nonporous glazed or fully densi fied cera111ics, as well as certaiп nonporous pl asrics, and glass. 1 .2 Th is practice aJ so provides а refere 11ce: 1 .2. 1 Ву wh ich а liquid peneu·ant exan1i nation process recoпнпended or required Ьу i11di vidual organizations сап Ье revie,ved to ascertai11 i ts applicab l l ity апd co111plete11ess. 1 .2.2 For use in the preparation of process specifications and ргосеdшеs deal i 11g wi tl1 1l1e liquid pe11e1rant 1esting of раг1s and 111aterials. Agrce111ent Ьу tl1e custo111er rcq t1esti ng pe11eu·ai1t testing is strongly recom111cnded. All areas of this practicc may Ье орел to agreement Ьetv.1een the cognizant eпgineering organization and the supplier, or specific clirection from the cognizant engineering organization . 1 .2.3 For L1se in the organi zation of facil ities and personпel concerned ,vi th l iquid penetraill testi11g. 1 .3 Tl1is practice docs not indicate or suggest criterin for evaluation of tl1e i ndicatio11s obtained Ьу perJetrant testing. lt shoL1ld Ье pointed out, however, that after i ndications l1ave been found, tl1ey 111t1st Ье i 1Jterpreted or classified and then evaluated. For this purpose tl1ere must Ье а separate code. standard. or а specific agreement to define the type. si ze. location, and direction of indications considered ассерtаЫе, and tlюse considered llnacceptaЫe. 1 .4 U11its-The va lнes stated i n either SI ttnits ог i nch­ po,rnd units аге to Ье regш-ded separatel y as stш1dard. Тhе values stated in each system 111ау not Ье exact equivalents; 1 111i1) prш.::tict: i� u111Jer 111е juri-.iJii;,1 ior1 of ASThl Coщmittce Е07 uп Nu111.k­ !-Н11c1ive Tes1i11g ancl i� 1he direct re-;pon-.it-iili1y of SL1tx:ommiнee ЕО7.03 nn Liq11id Penetrimt �nd Magnetic Particle Methods. Currcnl cdi1ion .ipprovcd Nov. 15, 20 1 8. PuЫishcd JonLt.try 20 19. Origina11y uppп:ivcd iп 1 960. l...asl prcviou� cditiun uppruvcd iп 20 1 2 щ1 Е 1 65/Е 1 65М - 1 2. DOI: 1 0. 1 520/ЕО 1 65_Е0I 65М- 1 8. 1 For ASME Boilcr tшd Prcssure Vcsscl Codc t1pplicotioвs scc rcla1cd Rccoш­ шendcd Test Method SE- 1 65 in tl1e СООе. therefore, each system shall Ье t1sed iпdependently of the other. Combining values from the two systeшs шау resll lt in non­ cont'ormance with the standard. f 1 . 5 ТЫ., standar,/ doe.s 1101 purport ro addres.s all o rl,e safery concems. if ш,у, шsociated wi1/1. its r,se. lt is rl,e responsibility of 1/1е 11se1· of rl,is srшulard to e,·taЫis/1 appro­ pгiate Jaj'ety. l1ea/t/1, tmd envi,·onmental practit:es and deter� mine t/1e applicaЬility of ,-eg11/a101y limita1io11s р,-iог to use. 1 . 6 Т/1is imernatio,шl sranllaгd 1vas lfeveloped i11 accor• tlance 1-11irh i111emario11ally recogni:e,I pгinciples 011 stall(fanl­ ization establis/1ecl iп 1l1e Decision 011 Pгinciple!J for 1l1e Developmel1/ of lutenюtional Staнdards, Gt.tides and Recom­ meп.dations issued Ьу the Woгld Тгаdе Oгgaпization Teclmical Boгriers to Тгаdе (ТВТ) Committee. 2. Referenced Docuшents 2. 1 ASTM Sttmtlards: 3 D 129 Test Met1юd for SL11fu r in Реtюlеш11 ProdL1cts (General H igh Pressure Decomposition Device Method) D329 Specification for Acetone D770 Speci fication for fsopropy l Alcohol D808 Test Method for Chloгine in New and Used Petroleшп Products (High Pressure Decomposition Device Method) D 1 1 93 Speci fication for Reagent Water D 1552 Test Method for Sulfur in PetroleLin1 Products Ьу High Temperature Combustion and lnf'rared (IR) Detec­ tion or Thermal Conducti vity Detection (TCD) D4327 Test Method For A n ions in \Vater Ьу Suppressed Ion Chro111aюgrapl1y Е43З Refe1·e11ce Pl10tograpl1s for Liquid Penetra11t lnspec­ tion 65 1 6 Practice for Testing Theпnal Conductivity De1ec1ors Used in Gas Chronia1ogгapl1y 6543 Specificalion for Agencies Performi ng Nondestruc1i ve Testi ng Е 1 208 Practice t·or Fluorescent Liquid Penetrant Testing Using tl1e Lipoph i l ic Post-Emulsification Process Е 1 209 Practice for Fluorescent Liquid Penetrant Testing Using the Water-WashaЫe Process 1 Fuг п:rcrcпccd ASTM �tцнdцrЩ,, vi::;it 1l1c ASTM wcb:'litc, "''ww,u..-.i111.u1·.g, ur contac1 АSТМ Custo111er Service at service@3s1ш.org, For Атнт/ Book of ASTM Sraшfшtls volumc infornкнion, rcfer to 1hc stondaгd·s Docu,ncnt Suinrnary p3gc ов tl1e АSТМ website. •л S11ш1ш1rу uГ Cl1ung1..-s se1.:tlun upptшt'S ut tlн.: ешl uГ this stшкlurd etrant out of the disconlin uity and stзi n the developer. The test sшface is then exarru ned to deter111ine the presence or absence of indicatioпs . Е 1 2 1 О Practice for Fluorescent Liquid Penetraпt Testing Usiлg the Hydropl1il.ic Post- Emulsification Process Е 1 2 1 9 Practice for Fluorescent Liquid Penetraпt Testiпg Using the Sol veпt-RenюvaЫe Process Е 1 220 Practice for VisiЫe Penetщnt Testing U sing Solvent­ ReшovaЫe Process Е I З 1 6 Terminology for Nondesrructi ve Exami nations Е 1 4 1 8 Practice for VisiЫe Penetrant Testing U sing the \Vater-WashaЫe Process Е2297 Gu ide for Use of UV-A and YisiЫe Liglн Sources and Meters used in the Liqu id Репеtпшt апd Magпet ic Paпicle Methods Е3022 Practicc for MeasL1rcrncnt of EnU ssion Characteri s­ tics and Require111ents for LED UV-A La111ps U sed i n Fl uorescen t Penetraпt a n d Magnetic Particle Testing 2.2 ASNТ Stш1clanls:4 SNТ-TC- I A Reco111111ended Practice for Nondestructive Testi ng Personпel Qualificalion and Cenification ANS IIASNT СР- 1 89 Standard for Qualification and Ceпifi­ cation of Nondestructi ve Testing Personnel 2.3 /SO Sta11darcl,r: 5 ISO 97 1 2 Noпdestructive Testing - Qualification and Certification of N DT Personnel. General Pri nci ples 2.4 АРНА Sш11dard: 6 429 Method for the Exa111ination of Water and Waste,vater 2.5 А /А S1ш1&11·tl: 7 NAS-4 1 0 Ce11ification зnd Qual ification of Nondestrнctive Test Personnel 2.6 SA E S1a11dm-ds: 8 дМS 2644 lnspection Material . Peпetrant QPL-AMS-2644 Qualified Products or lnspection Matcrials, Penetrant Nore 2-Thc dcvclupcr may Ьс omittcd Ьу agrccmeпt Ьсt\vсеп thc contracting parties. Noru 3-Fluorcscent pencIraI11 ex3mi nation shall 1101 follow а visiЫe penetrant examiшнion unless the pюcedure has Ьес11 quali fied in nccor­ d:.шct: witl1 I 0.2, Ьeclluse Vi:!>iЬle dye:!I inay Ctlш;e dete1·ioп1.1 io11 ш qtienchi ng of f1t1orescen1 dyes. 4.2 Proccssing paramctcrs, such as surface prcclcaning, peпetrant dwell ti rne, and excess penetrant reino,,al rnethods1 are depe11dent оп the specific materials used. t.he 11ature of the рагt under exam ination (that is, size, shape, surface condition, al loy), an(I type of d i scontinн ities expecled . 5. Significance and Use 5. 1 Liquid penetranl testing methods indicate the preseпce. location and, ю а limited extenl, the 1tatt1re and 111agnitt1de of the detected discontinui ties. Each of the various penetraпt 111ethods has Ьееп designed for specific uses such as critical service items, voluшe of pal"ts. portability, or localized areas of exa111i11ation. The method selected will depend accordingly on the desigп апd service reqtiirements of the parts or mзteriaJs being tested. 6. Classifical.ion of Pcnc!rant Matcrials and Mcthods б. 1 Liquid peпetrant 1esti ng methods and 111aterials are class ified in accordance with AMS 2644 as listed in ТаЫе 1 . 6.2 Fl11orescelll Репеrгат Testing ( Туре /)-Fluoresceпt penelrant testing uti l i 1.es penetraпts that fl uoresce bri l l i antly when exci ted Ьу U VA-radiation . The sensitivity of ft uoresceпt penetrants depends on their aЬil ity to Ье retained i n the various size discontinuities during processing, мd then ю Ыееd out intu Lhe dcveloper tOLl.ting '1Ш1 produce iпdkat.iuns Lhat ,vill fluoresce. Fluoгescent inclications ше шану tiшes b1·ighteг than their surroundings whcп vicwcd undcr appropriatc UV-A illumination. 3. Terminology 3. 1 The defi n itions relating to liquid penetrant testi11g, whi cl1 appea.r in Term inology Е 1 3 1 6, shall appl y to the tеппs used in tl1 is practice. б.З Visible Pe11etm11t Testing (Туре //)-VisiЫe penetrant resting uses а penerranr rhat сап Ье seen in visiЫe ligl1t. The penetrant is usually red, so tliat resultant in<.Jications produce а defi nite contrast witl1 the wblte backg,·otшd of tl1e develope1·. YisiЫc pcnctrant indications must Ьс vicwcd undcr adcquatc visiЬ\e li Б ht. 0-11: l �ThroughNII Lhis practice. 1he term Ьlllckligllt has Ьеео changed to UV-A 10 co11for1n \\'ith tl1e latest ter111inology i n Ter111i nology Е 1 3 1 6. Bfacklig/11 сап 111еал а broad range of ulLraviolet radiation fttюrescent pe11etrant testing нses only UV-A light. 4. Summary of Practice 4. 1 Liq uid peпetraп t 111uy co11sist of visiЫe 01· Пuo1·esce11t 111ateri ul. Thc l i quid pcпctraпt is appl icd cveпl y ovcr thc surface being exnmined and allo\ved to enter open discontinuj­ ties. After а suitaЫe dwel l ti 111e, the excess surface penetrant is removed. А deve l oper i s appl ied to dга"' tl1e entrapped реп- 7. MateriaJs 7 . 1 Liquid Penetrant Testing Mate,·ials consist of Auores­ ceпt or visiЫe penetraпts, eшulsifiers (oil-base and water­ base), re111overs (•Ae/opш-s ( Forms D a11d E:J-After the excess penctrant has been renюved алd the surface has been driecl , apply I10naqL1eo11s wet developer Ьу spraying in Sllch а 111anner as to ensure co111pl e1e pan coverage with а thin, even filrn of developer. The developer shall Ье applied i n а nianneг appropriate to the type of peпetrant Ьeing нsed. Рог visiЫe dye, the de,,eloper шust Ье appl ied tl1ickly e110ugh to pmvide а contrasti ng background. Fог fl ,юrescent dye, the developer nшst Ье app J ied th inly to prodL1ce а transl uceпt covering. Dipping or flooding parts ,vith noпaqtIeous develop­ ers is prol1 i blted, because the solvent action 01· these types of developers can llush ог dissolve the penetrant fr'om within the discontinuities. 8. 7 D,}'ing-Regardless of the type and method of penetranl ,ised, dr·ying the surface of the part(s) is necessory prior to applying dry ог nonaq ueous developers ог foll owing the appl ication of the aqueous devel oper. Dryiпg tinie 1vill vary with the type ot· drying used and 1l1e size. nature. geometry. and nu mЬer of parts Ьeing processed. 8.7. 1 Dryi11g Pшшneters-Coniponents shal l Ье air dried at rooni tempe,·aшre or in а drying oven. Room Ie111perature drying сап Ье aided Ьу the tIse of fans. Oven 1e111peraшres shall nol exceed 1 60 °F [7 1 °С] . Dry ing time shall only Ье that necessary to adequately dry the part. Corпponents shal l Ье removed frorп the oven after dryi ng. Compone11ts should not Ье placed i n the oven witl1 pooled water or pooled aqueous soltttions/suspcnsioш;. NоТЕ J З-Tl1e vapors t·гoin the volatile solvent carrier in the developer тау Ье haz,udous. Proper ve111ilation should Ье provided at all ti111es, but especially when the developer is applied i nside а closed area. 8 . 8 .4 Liquitl Film Developиs-Apply Ьу spгaying as rec­ omniended Ьу the 111anu facturel'. Spray parts i,1 such а шanner as to ensure coniplete part coverage of the area Ьeing examined with а thi n, even film of developer. 8 . 8 . 5 De1,elopi11g Тtте-Тhе lengtl1 of 1i111e the developer is to reшain оп the pan prio1· to exarп ination shall Ье not less than 1 О niin. Developing ti111e Ьegins i,шпediately after the appl i­ cation or dry powder developer or as soon as the wet (aqueoL1s ш· пoпaqueous) developer сшнiпg is d1·y (tliat is, tl1e water ш· 8.8 Developeг Application-There are various 111odes of effective application of the vario11s types of developers such as dusting, inimersi 11g, flooding, or spraying. The developer forni, the part size, co11figllration, and surface rot1ghness will inftu­ eпce the c lюice of developer appl i catio11. 8.8. 1 Dry Po,vdef' Develope1· ( Fогт A)-Dry powder· devel­ opers shaJI Ье applied aJtcr tl1e рагt is dгу iп sucl1 а пш11nег as 6 8.9.3 Housekeeping-Keep the exaшination area free of iлterfering debris. including fluorescent residues and objects. 8 .9.4 /11dicatio11 Veгification-For Туре l exшninations only, it is соттоn pract·i ce to verify indications Ьу wiping the indication with а solveпt-dampened swab, brush, or lint-free clot. h allowing the area to dry, and redevelopiпg the area. Redevelopment time shall Ье а шinimum of I О шin, except nonaqueous redevelop111ent time sbould Ье а 111i11i11111111 of 3 01i 11. lf tl1e indication does 1101 rеарреаг, the origi11al indica­ tion 111ау Ье considered false. This procedure may Ье реr­ Гоппеd up 10 1wo liшes Гог апу gi ven original i 11dica1io11. Unless pюh iЫted Ьу tl1e Purclшser, S pecificatio11 D770 isopro­ pyl alcohol a11d Spccification D329 acetonc are comnюnly acccptcd solvents. 8.9.5 E11aluation-AI I indications found during exa111in:э.tion shal l Ье evaluated i11 accordaпce with ассерtапсе criteria as specified. Reference Photograpl1s of indi caIio11s а,·е noted i n Е433). 8. 10 Post Cleaniug-Post clcani.ng is 11cccssary whcп rc­ sidual рс11сtпюt ог dcvclopcr could intcrferc with subscqucпt processing or \vith service гequire111ents. It is particularly impo1·tant where residual peneti·ant testing 1nate1·ials mi g lit coni Ьine with other factors iп service to prodL1ce corro.sioп a11d prior to vарог degreasing ог heat treating the pan as these pюcesses сап bake the develope,· onto the part. А suitaЫe 1echnique, such as а simple 1vater rinse, water spray, machine wash, solvent soak, or ul1rasonic cleaning may Ье employed (see Annex А I for further i11t·ormation оп post cleaning). !t is reco111111ended that if developer removal is necessary, it shot1ld Ье carried out as promptly as possiЫe after exatnination so lhat the developer does not adhere to the pan. solvent carrier lшs evaporated to dгyness). The 111ахi111ш11 per111itted developing ti111es sball Ье 4 h for dгу powde1· developer (Fопп А), 2 h for aqнeous developer (For111s В апd С), and 1 11 for nonaqueous developer (For111s D and Е). &.9 E.xami11atim1-Af1er the applicaЫe development 1ime, perfon11 examination of tl1e parLs under visiЫe l i ght or UV-A radiation as appropriate. lt may Ье helpful to observe the Ыееd ош during the development ri111e as an aid in interpreting iлdications. LED UV-A s01Irces shall 111ее1 the requirements of Practice ЕЗО22. 8.9. 1 UV-A Lig/11 Exa111i11ation-Examine pans tested with Туре I e uorescent penetrant unde1· UV-A light in а darkened агеа. A111Ьient visiЫe light shaH □ot exceed 2 fc [2 1 .5 lx]. The a111Ьient light measurement sl1all Ье made witb а suitaЫe visiЫe light sensor at the exa111i11ation surface, 1vith visiЫe l ight sources off. ОТЕ 1 4---Because thc Пuorescent cons1i1ue111s in the pe11etrant wil1 e\'enшally fade \vith direct exposure to UV-A lighL�. direct expшure of tl1e pan under test to UV-A шdiation should Ье шinin:llzed when пш removing cxccss penctrant or evзluating i 11dicatio11s. 8.9. 1 . 1 UV-A Lig/11 Le,,el Cu11t1vl-UV-A ligl11s shall pro­ vidc а minimt1m light in1cnsi1y of 1 000 µW/cm2 , at а dis1ance of 15 in. [38 . 1 cm]. The intensity shalJ Ье checked daily 10 ensure tJ1e requi.red outplll (see Gtlide Е2297 for rnore iпfor­ mation). ReAectors a11d filters shall aJso Ье cl1ecked daily for cleш1li ness a11d i11tegrity. Cracked ог broken ultra,,iolet filte,·s shall Ье replaced i m111ediately. Si11ce а drop in line voltage can cause decreased lJV-A l i ght outpt1t w ith coпseqL1ent incoпsis­ tent perfoппance, а consta,11-voltage transfoпner should Ье ttsed when there is evidence of voltage ftuctLtation. LED UVA-sources used to examinc pans shall Ье checked daily (or beforc llSe i f not used daily) to ensure that all elements are operational . Lf any diode element is not opera1ional the condition shall Ье corrected or the unit replaced. The opera­ tional check slюuld Ье perfon11ed Ьу placing а white sheel of paper over the la111p and then viewing lhe transn1 i ттed light ft"Om each diode. LED UV-A sot1rces are at Гull in1e11si1y at power-on, a11d tl1e iпtensity п1ау dccrease as the lашр staЬi­ l izcs. 9. Special Requirements 9. 1 lmpul"ities: 9. 1 . 1 When using peпetrant 111aterials 011 aнstenitic stain less steels, titanium, nickel-base, or other high-ten1peratttre alloys, the need to restrict cerшi,1 impurities such as sulfur, halogens, at1d alkaJi metals must Ье considered. These impurities may caL1se embrittlement or corrosion, panicularly at elevated temperatures. Any such evaluatio11 sha\l also include consider­ utior1 of the Соп11 in wblch tl1e impurities ai-e pI·ese11t. Sоше pe11etra11t 111ate1·ials contain sig лificaпt a1110u11ts of these i111pu­ rities i11 the forin of ,,o) atiJc organic solvcnts tLшt norrna.ll y evapor:.He quickl y and usual ly do not cause proЫems. Other rnaterials may contain i 111pL1rities, which аге not volatile апd may react ,vith the pa,·t, part icularly iп the presence ofmoistL1re or elcvated 1emperaшres. 9. 1 .2 Because volatile solvents leave the surface quickly without гeaction under non11al examination procedures, pen­ etrant 111aterials are nonnally subjected to an evaporation procedщ-e to remove the solvents Ьefore the шaterials are analyzed for impurities. The residue fro111 this procedш-e is then analyzed in accordaпce wi tl1 Tes1 Method D 1 552 or Test Method D I 29 decomposition fol lowed Ьу Test Me1hod Е5 I 6, Method В (Turbldi111etric Method) fo1· sulfur. The residue may also Ье analyzed Ьу Test Method D808 ог Annex А2 оп Methods for Measuring TotaJ Chlorine Content in CoшbustiЬ\e Liquid Penetгaпt Mate,·ials (Гоr lшJogeпs ol11er 1lш11 Пuoгine) ОТЕ 1 5--Certaiп higl1-intcnsity UV-A lights niay eшit unacceptaЫe �Lniounts of visiЫe light. which сал cause fluorescent indications ю disappcм. C..'"tre should Ьс tnkcn to only L1se bulbs suitaЫc for t\uorcscenl penetra,н exan1i11ation purposes. &.9. 1 .2 UV-A Ligl,t Waгm- Up-Unless otherwise specified Ьу the manufacшrer. al\ow the UV-A ligllt ю warm ,,р for а minimum of 1 0 mi11 prior to нsе or meшшrernent of its intensi ty. LED U V-A sources do 1101 require war111ttp. 8.9. 1 .3 Visual A eliшiпatcs the iпtcrference and doe!. поt alter the Qllality of lhe titr;::ition. А2. 8 . 3 . 1 Gelшin S0l11rio11-A 1ypi cal preparation i s: Add approxi n,ately I L of hot dist i l led or dei oni zed water to the 6.2 g of dry gelatin mi xшre contained in опе v ial suppl ied Ьу the equipшent man ufacturer. Gently heat with continuous mixi11g until the gelatin is completely dissolved. А2.8.3.2 Divide i nto al iquots each sufficienl for one day's aiialyses. (Th i rty 111 i l l ilit. res is eпough for approxi111ately eleveп titrations.) Кеер t\1e 1·e111ainder in а refrigeraюr, but do not freeze. The sol ution will keep for about six 111on ths i n the refrigerator. W heп ready ю use, i 111л1erse the day's ali quot in hot water to liquefy the gelatin. А2.8.3.3 Glacial Acetic Acid- Nitl'ic Acid Solшion-A typi­ cal rslio is 1 2.5 ю 1 ( 1 2.5 p� rts СН 3СООН to I pan НNO3 ). А2.8. 3 .4 Mix e110L1gl1 gelati11 solution and of acetic acid­ n it:r i c ac id mixturc for 011с titration . (А typical mixture is 2.5 niL of gclatin solutioп and 5 .4 mL of ncctic-n i tric acid mixtt1re.) (А2. 1 ) wl1e1·e: NдgNOЗ N№Cl Vл noппa l i ty or i.he AgN03 sol ution, normality of t\1c NaC\ solution, millil itres of AgNO3 solt1tion used for the titra­ tion including 11,е NaCI solution, and milli l itres of AgNO3 solшion usecl for the t i tra­ tion of the reagents only. А2.7.7 Calcu/шion-Calculate tl1e c\1lorine coпtent оГ the sшпрlе as fo l l ows: Chlorine, weight % = ( Vs - v,) Х N Х З.545 W mi l lilitres of AgNO3 solution used Ьу the Ыank, = norma l i ty of the AgNO3 solt1tion , and = gra111s of sa111ple used. (А2.2) whe1·e: Vs 111 il\ilitres o f AgNO 3 so\utioп used Ь у the sa111ple. н'J l\l�y Ье purchased froш lhe eQ ui pmenl su pp lier. А 1ypicaJ 111i:ent Cleaners: АЗ.4.2.1 Takc t.l1c tare wcight of an alununшn dish. АЗ.4.2.2 Weigl1 100 g of tl1e сlеапег iпto tl1e alш11i11u111 dish. 13 Society. where such specifications are availaЫe. 9 Other grades may Ье used. pгovided it is first ascertaiпed that tlte reageпt is of sufficientJy high purity to per111i t its use w itlюut lesse11i11g the accuracy of the determ inatioп. АЗ.4.2.3 Place the alшninum dish оп а hot plate in а fшne hood. АЗ.4.2.4 Let the material evaporate until the di sl1 is nearly dгу. АЗ.4.2.5 Place the dish into а preheated oven from 1 94 ° F [ 9 0 °CJ t o 2 1 2 °F [ 1 00 °С] for 1 0 mjn, АЗ.4.2.6 Take the djsh out of the oven and allow ю cool. АЗ.4.2 .7 Reweigh the dish and record weight. ОТЕ A3. I -For Cleaners-lf the residue is less Lhan 50 ррп1, rcpon IJ1e re�idue weigl1t. lf tl1e weigl1t i� greater tlшл 50 рр111, рп:х:ееd witl1 Ll1e ЬоmЬ procedttre. А3.6.2 Pш·ity oj Wara,·- Unless otherwise indicated, all references to ,vater shall Ье understood to mea11 Туре l I·eagent water co11t·oгm i ng to Specificatio11 D I 1 93 . А З .6.3 Fluorirle Solшion. Srock (2000 ppm)-Dissolve 4.4200 :!: 0.0005 g оГ predried (at 1 30 ю 1 50 •с Гог I h, tl1en cooled iп а desiccator) sodiL1111 fluo1·ide i11 distilled wateI· апd dilutc to I L. АЗ.5 Apparatus АЗ.6.4 Oxyge11, free оГ combustiЫe material and halogen co111po11nds, availaЫe at а pressure of 40 atm [4.05 МРа]. АЗ.5 . I ВотЬ. having а capacity of 110! less than 300 rnL, so constructed that it will not leak dt1ring the test, and that quantitative recovery of the liquids from the bon1b may Ье readily achieved. Tl1e i n ner surface of tl1e bomb may Ье made of stain less steel 01· any other material that will not Ье affecled Ьу tl1e co111b11stion process ог products . M ateri als used in the bom b assen1 Ыy, sucl1 as tl1e head gasket апd lead,vire instrlation, shall Ье resistant ю heat and chemical action, and shall 1101 undergo апу reaction that will affect the fluorine co11tent of tJ1e liquid iп tl1c bomb. АЗ.6.5 Sndi"m Citrare Solшioп-Dissolve 27 g of sodiu rn citrate dil1ydrate in water and dilute to I L. АЗ.6.6 Sodiшn liycll'Oxide Solшion (5 N)-Dissolve 200 g of sodium hydroxidc (NaOH) pel lets in wutcr ш,d dil ute lo I L; storc in а pol ycthy lcnc contai ncr. АЗ.6.7 \Vash. Solшio11 (Modijie,l ТISА В, Toral lo11ic Strengt/1 Adjustmem Bujj'a)-To 300 mL ot· distil led 1vater, add 32 rnL of glacial acetic acid, 6.6 g of sodi 11n1 citrate dihydrate, апd 32. 1 5 g of sodiнm chloride. Srir to dissolve апd 1l1e11 adj ust the рН to 5.3 usi 11g 5 N NaOH ,ol utio11 . Cool апd dil ute to I L. АЗ.5.2 Sample Сир, nickel, 20 mm in outside diarneter at the bottom, 28 111m i n outside diameter at the top, and 16 11ш1 in height; or plati пurn, 24 n1m iп outside diarneter at the bottom. 27 n1m in outside diarпeter at the юр, 1 2 mm in height, and \\'eighing I О to 1 1 g. АЗ.6.8 \Vhite Oil, ,·efined. АЗ.7 Decoшpositio11 P,·ocedure АЗ.5.3 Fiгing Wil'e, plati num, approxi111ately No. 26 В & S gauge. АЗ.7 . I Ргершаtiоп of ВотЬ ш1d Samp/e-C11t а piece of firing wire approx imately 1 00 Iшn in length . Coi l tl1e middle section (about 20 шm) and attacl1 the free ends to tl1e terminals. Arrange the coi l so tl1at it wi l l Ье above and to опе side of the sample cup. Place I О mL of sod.ium citrate solution in the bomb, place the co,•er оп tl1e bomb, and v i gorously shake for 1 5 s 1О distribute tl1e solt11io11 oveI· tlte iпside of Ll1e Ьо111Ь. Open the l.ю111Ь 1 place the sa111ple-fШed sa111ple cup iп t.l1e terr11 i11al holder, and i nsert а short lcngth of thread betwccn t.h e firi11g wire and tl1e sample. The s.:imple ,vei g ht used slюuld not exceed I g. 1f the sample is а sol id, add а few drops of white oil at this time 1·0 ensLire igni 1-ioп of the saшple. АЗ.5.4 lg11ilion Circuir. сараЫе of supp lying s11fficient cнr­ rent to ignite the nylon thread or cotton wicking without meltiпg the wire . (Warning-The switcl1 in the ignition circuit shot1ld Ье of а rype that remains open, except when held in cl osed position Ьу t. he operator.) АЗ.5.5 Nylm1 Se11•i11g Tlrreatl, or Co1ton \Vicki11g, white. А3.5.6 Funnel, polypropylcne (Notc А3.2). АЗ.5 .7 Vo/umetгic P/ask, polypropy lene, I 00-111L (Note АЗ .2 ). АЗ.5.8 Beaker, pol ypropyleпe, 1 50-mL (Note АЗ .2). NотЕ AЗ.3-Use of sample ,veights containing over 20 mg of chlorine rпау C"d use: соп·о:$iо11 of U1e: ЬотЬ. То avoid tl1is it is reco111111e11ded Llщt for s:101ple..� co11ta.ining over 2 % cl1lorine, the s:1n1ple ,veight Ье ba..�ed on LJ1e fo1lo\\·i11g tаЫе: White Oil Ch1orine Sample Content, о/о weight, g weight, g АЗ.5.9 Pipet. I 00-µ L, Eppendorf-type (Nnte AJ.2). АЗ.5 . 1 0 Magnetic Sti, e,· a11d TFE-coared 1-нagвetic sti1тing bar. т АЗ.5 . I I Fluoгicle Specijic ence electrode. 1011 Electrode апd suitaЫe refer­ 0.4 0.4 2 to 5 >5 10 10 0.2 О.б 0.7 >10 10 20 0. 1 0.7 >20 to 50 0.05 Do по[ use rnorc than g total of sample. and white oil or other fl uorine-f1·ce combustiЫe marerial. АЗ.5 . 1 2 Millivolt Meter сараЫе of measш·ing to 0. 1 mV. om AЗ.2-Glasi.wnrc should ncvcr Ьс uscd to l1andlc з fluoridc solution as it will renюve fluoride ions fron1 solution or оп sнbsequeпt use са.ту Пuoride ion froш а concentr:1.ted solution to опе more dilute. АЗ.6 Reagents АЗ.7.2 Addirion of O.xyge11-Place the sa111ple cup in posi­ tion and arrar1ge the nylon thread, or wisp of cotton so that the e11d dips into the sample. Asse111Ыe the bomb and tighten the cover securcly. Ad mit oxygcn (see the Warning bclow ) slo1vly (10 avoid Ыо"'•iпg Ll1e sa111ple fгoni the cup) uпtil а pressure is АЗ.6. I Ригitу of Reagents-Reagent grade cheшicals shal l Ье нsed in all 1es1s. Unless otherwise indicated, it is intended that aJI reagents shaJI conroпn ю the specifications of the Сошшiнее оп A1шlytical ReL1.geпts оГ tl1e Ашеriси.п Cl1e111ical 14 reacl1ed as indicated in ТаЫе АЗ.1. (Warning-lt is recom­ mended to поt add oxyge11 01· ignite the sample if the Ьо111Ь has Ьееп jarred, dropped, or tilted.) АЗ.7 .3 Combustion-Immerse the bomb in а cold-water bath. Connect the terrninзls to the ореп electricзl circL1it. Close the circuit 10 ignite the sample. Remove tl1e Ьо111Ь from the bath after i11ш1ersio11 fo1· at least I О 111in. Release the pressш·e at а slow. uniforш rare such that the operation requi1·es поt less than 1 111in. Ореп the Ьо111Ь and exa111ine the contents. If traces of unburned oil ог sooty deposits are found, discard the deterшination, and thoroughJy сlеап the bomb before again putting it in use. АЗ. 7.4 Collecrion of F/11ori11e Solmio11-Re111ove the sample cup with clean forceps and rinse ,vith wash solution into а 100-mL volumetric flask. Rinse the walls of the Ьо111Ь shell with а fiпe streaш of wash soltrtion l'rom а 1vash bottle, and add the washings to the flask. Next, rinse the bomb cover and terminals into the volumetric ftask. Finally, add wash solution to bring the contents ot· the ftask ю the line. АЗ.8.3 !mmerse the ftuoride апd reference electrodes in solutions and obtain the equilibrium reading to 0.1 юУ. (The coпditioп of the electrode deter111ines tl1e leпgth of time necessary to reacl1 eq11ilibriuni. This шау Ье as little as 5 1ni11 ог as much as 20 111in.) АЗ.8.4 Add 100 µL of stock fttю1ide soltrtion and obtain the reading after tl1e sa1ne length of tiюe necessary for АЗ.8.3. А3.9 Calculation АЗ.9.1 Calcttlate the nuori11e content of the sample as follows: 2 х 10-, 2 х ю-• [ tOЛE,IS - t tOЛE, IS - t ] х IO' Fliюriпe, ppin = \V (АЗ. t) \Vhcre: .d Е, .d Е, АЗ.8 Proceduгe s w АЗ.8.I Ascertain the slope (111Шivol1s per ten-fold change in conceпtгdtiur1) of t.he electгode а� de�cгibed Ьу Ll1e mшшfac­ turer. АЗ.8.2 Obtain а Ыапk solutio11 Ьу performing the procedure without а sample. А3. 1 О Precisio11 ш1d Вias АЗ.10.1 Repearability-Т11е results ot· t1vo deteпninations Ьу the same analyst shot1ld not Ье considered suspect unless t.hey di1't'er Ьу more tl1an 1.1 ppm (0.00011 %) or В.О% of tl1e TABLE АЗ.1 Gauge Pressures minA ЭОО 1о 350 >350to 400 38 >400 to 450 >450 to 500 aшount detected, wЫchever is greater. АЗ.10.2 Reproclucibllity-The 1·esults of t1vo detem1ina1ions Gauge Pressure atm [�Ра] Сарае� о1 Bomb, mL 35 30 27 n1illivolt cl,ange in sa111ple solutioп оп addition of 100 µL of stock Atюridc solution, millivolt change in Ыank solution оп addition of LOO µL of the stock fluoride solution, slope of fluoride eleшode as determiпed in АЗ.8.1. and granis of san1ple. mак Ьу different laboraюries should not Ье considered suspect unless they differ Ьу 6.7 pp1n or 129.0 % of the amotrnt detected, whichever is greater. АЗ.10.3 Bias-The average recovery of the niethod is 62 to 64 о/о of the amount actually preseпt althougl1 83 to 85 о/о reco1•eries can Ье expected with proper technique. 40 37 32 29 А Тhв minimum pressures are specified to provide sufficient oxygen for complete combustion and the maximum pressures present а sarety requirement. А4. DETERМINATION OF ANIONS ВУ ION CHROMATOGRAPHY \VITII CONDUCTIVJTY МEASUREМENT preseпt iп the bomb at tl1e time ot· ignition. This solution is washed l'rom the bomb, filtered, and diluted to а known volшne. А4.2.1.1 А filtered aliquot of sample is injcctcd into а stream of carbonate-bicarbo11ate elua11t апd passed tlirough а series of ion exchangers. The anions of interest are separated оп the basis or thei,• relative affinities Гоr а low capacity, strongly basic апiоп exchanger (guard and separator colшnn). The separated апiопs are directed опю а stro11gly acidic cation excl1a11ger (suppressor соluпш) wl1e1·e they ше co11ve11ed to their t,i g l,l y co11ductive '1Cid rorm апd tl1e cai·boпate­ Ьicarbonatc cluant is coпvertcd to ,vcakJy coпducti vc carbonic acid. The separaIed anioпs in their acid forn1 are measнrcd Ьу А4.1 Scope and Application А4.1.I This 111etl10d is condensed from ASTM procedures and АРНА Method 429 and optimized for the analysis of detrimental substances in organic based materials. lt provi(les а siпgle instrumental 1echniqt1e for rapid, sequential rneasure111ent of соmлюn апiопs such as bromide, cl1Joride, fluoride, nitrate, nitrite, phosplшte, and sulfate. А4.2 Sumnшry оГ Method А4.2.1 Тhе material nшst Ье put in the forn1 of ап aqueous solutioп ЬеГоге aпalysis сш1 Ье attempted. Tl1e sa111ple is oxidized Ьу co111bustion i11 а Ьо111Ь containing oxygcn under prcssurc. The products liberatcd аге absorbcd in thc clшnt 15 conductivity. They are identified on the basis of retention titne as compared to standards. Quantitation is Ьу 111easure111ent of peak агеа or peak l1eight. Blanks are prepared and anaJyzed i n а simi lar fashioп. А4.2.2 lпteiferences-Any substance that has а retentioп ti111e coincidiпg with that of any aпion to Ье determined will i nterГcre. For exarnple, relatively high conccntrations of low­ molecular-weight organic acids i ntcrfere with the detem1ina­ tion of chloride and fluoride. А high concentration ot· any one ion also interferes with the resolution of others. Sample dilution overcomes тапу interferences. То resolve uncertain­ ties ot· identification ог guaпtitation use the method of kno,vn additioпs. Spurious peaks 111ау resu lt fro111 contaminants in reagent ,vater, glassware, ог sample processiпg appш·arus. Because s111al l sample volu111es are used, scrupulously avoid coпtaп1i11ation. А4.2.3 Minimшn Dе1ес1аЬ/е Co11ce111ratim1-The 111ini111um detectaЫe coпceniтation of an anion is а Function of sa111ple size and conductiviry scale used. Geпerally, 111iniпшm detect­ aЫe co11ceшra1ions are in the range of 0.05 111g/L Гог F" ш,d 0. 1 111g/L fог В,·-, СГ, NO 3-, NO2-, РO43-, a11d SO/- \Yitl1 а 1 00-µL saшple loop and а 1 0-µ111ho full-scalc sctting on thc conductivity detector. Similur vulues may Ье acl1ieved Ьу using а hi g her scale setti ng :.шd ап electronic integrator. te111perature-co111pensated snшll-volшne conductivity cel l (6 µL or less). and а strip chart recorde1· сараЫе of full-scale response of 2 s ог less. An electronic peak integrar.or is oprioпal. Тhе iоп cl1ro111atograplJ sball Ье сараЫе of deliveriпg 2 to 5 111L eluant/111in at а pressure of 1 400 to 6900 kPa. А4.З.7 A n ion Sepcuato,· Со/,.тт, with s1yrene diviny!Ьenzene-based low-capacity pellicular anion-exchange resin сараЫе ot· resolving вr-. СГ. t. NO 3-. NO 2-. Ро,З-. and so,2-; 4 х 250 lllПl, А4.3.8 Guard Column, identical to separпtor column except 4 х 50 mm, to protect separa!or columп from fouling Ьу partict1lates or organics. А4.З.9 Suppressoг Соlитп, l1igh-capacity catioп-excl1a11ge resin сс:1.раЫе of coпve1·ti11g elua11t and sepaл:1ted un ioпs to thei 1· acid forms. А4.3 . I О Syringe, 111ini 1nu111 capacity ot· 2 111L and eguipped with а 111ale pressure fitting. А4.4 Reagents А4.4. I Puriry of Reage,us-Reagent grade cl1e111 ical s shalJ Ье щеd i п al l teыs. U п less otl1erwise i пdicated, i1 is i111e11ded that all reage11ts shall conform to the specifications of the CoinП1ittcc on Analytical Rcagcnts of Lhc Amcrican Chc111ical Society, where such specifications are availaЫe. 9 Other grades may Ье used pro,•ided it is first ascertained that Lhe reagent has sufficiently high pшity to perшit its use without lessening the accuracy of the deter111inarion . А4.З Apparatus А4.3. I ВотЬ. havi ng а capacity of поt less than 300 111.L. so constructed that it will not leak duri пg the test, and that quantitative recovery of the liquids fro111 the bomb 111ау Ье readily achieved. The inner surface of tl1e Ьо111Ь may Ье made of staiпless steel or апу othe,· material tliat wi ll поt Ье affected Ьу the co111bustion process or products. Materials used iп the Ьо111Ь asse111Ыy, sucl1 as the head gasket апd leadwire i nsulatioп, sliall Ье resistant to heat and chemicaJ action, and shaJI not undergo any reaction rhar will alfecr the chlorine content or the liquid in tl1e bomb. А4.3.2 Sample Сир, plati1н1111, 24 111m in outside dia111ete1· at the botto111, 27 111111 in otttside dia111eter at the юр, 1 2 111111 i 11 heigl1t outside, and ,veighing 1 0 to 1 1 g; opaque fused silica, wide-fom1 w ith ап ourside diameter of 29 т111 ar the top, а l1eigl1t of 1 9 111111, апd а 5-шL capacity (Notc А4. I ), or nickel (Кawin capsule fопп), юр d ia111eteг of 28 111ш, 15 111ш in heigl11, апd 5-шL capacity. ОТЕ A4. 1 -fused silica cruciЬlc.s are rnuch more ecoпomical ,шd longc1· las1i11g tl1.:u1 plati11l1 1п. Aftcт cacl1 usc, tl1cy :-.lюuld Ьс sc11.1bhed OLIL wi1h fine, wet emery cloth, hea1ed 10 dнll red l1ea1 over а Ьt1rne.r, soaked in hot waicr for 1 11 tl1en dried and stored in а desiccator Ьeforc reuse. А4.3.3 Firi11g Wire, plati1ш111, approx i inately No. 26 В and S gauge. д4.3.4 lg11ilio11 Ci1·c11i1 (Note А4.2), сараЫе of supplying sufficieвt сштеnt to i g пite the пу lоп threзd oJ· cotton wicking witl1out n,elting the wire. cr11:. А4.2-Т1· 1е �,vitcl1 iп tl1e ignitio11 circuit �liould tX:: or а type (11.11 renшiпs ореп. except ,vhen held in closed po!.ition Ьу the operator. Л4.З.5 Ny/011 Seн iпg Тlrreatl, or Соиоп \Vicking, whjte. А4.З.6 /011 C/1ro11101og1·ap/1, including а,1 i пjectioп valve, а sшпрlе loop, guard, separato1·, ai1d suppгessoг colu111ns, а А4.4.2 Deianiг,ed ог DisJilled Иlcaer, free Гroin i11terfere11ce� at the mi11iml1Пl dctcction limit of each constituent and filtcrcd through а 0.2-µni membranc filter ю avoid plugging columns. А4.4.3 Eluant Solш ion, sodi u tn Ьicarbo11 ate-sod iu111 carbonate, О.ООЗ М NaHCO3_ О.0024М Na2CO3 : dissolve 1 .008 g NaHC03 ш1d 1 .0 1 76 g N32CO3 in ,vater and dilute 1 О 4 L. А4.4.4 Rege11erant Solutio11 1, H2 SO" 1 N, use tl1is regen­ erant wheп suppressor is not а continuously regenerated опе. А4.4.5 Rege11era11I Solшion 2. H 2 SO4. 0.025 N. dilute 2.8 шL conc H 2 S04 to 4 L ог 1 00 111L ,·egeneranl solution 1 to 4 L. Use this гegenerant with continuous regeneration fiЬer suppressoг system. А4.4.6 Standш-d Anion So/11tio11s, 1 ООО mgA.., pI·epare а series of standard anion solutioпs Ьу weighing the i пdicated a111ount of sal t. dried to а coпstan ! weight at 1 05 'С. to 1 ООО mL. Store in plastic bottles iп а refrigerator; tl1ese solutions are staЫe for at least one 111onth. Anion Sall Amount. g/L NaCI NaF NaBr NaNOэ NaNO2 кн�Ро. K2S04 1 1 .6485 2.2 1 00 1 . 2876 1 . 3707 1 . 4998 1 .4330 1 .8 1 4 1 А4.4.7 Comblned Wo rking StaпcfaГ(f SoluIio11, Hig/1 Rш1gе-Со111Ыпе 10 шL of tl1e СГ, F", NO3 -, NO2-, апd 16 Ро,.3- standard anion solutions. 1 111L ot· Ihe вr-. and 1 00 mL of the So,2- standard solutions. di J ute 10 1 000 mL. and slOre in а plast·ic boltle protected from light; contains I О mg/L each of СГ , F", NO3-, NO,-, and РО/-, 1 mg вr- /L, and 1 00 mg SO/-/L. Prepare fresh daily. Chlorinв % weight, g 2 to 5 0.4 content. >10 to 20 0.2 0.1 >20 to 50 0.05 >5 to 10 А4 .4.8 ComЬined Working Srtmdard Solurio11. Lo,v Range­ Dil t1te НЮ tnL comЬined work.ing standзrd solution 1 high гange. to I ООО mL and store in а plastic Ьotlle protected from l igh1 ; contains 1 .0 mgЛ_ each СГ, F", No,-, NO2-, ancl Ро/-, 0. 1 mg ВПL. a11d 10 mg so/-/L . Prepare fresh daily. Samplв Whitв Oil weighl, g 0.4 0.6 0.7 0.7 Waгning-Do not use 111ore than 1 g total ot· sa111ple and white oi l ог other nuorine-free combustible 111arerial. А4.6.2 A,ldirion of Oxygen-P\ace tl1e sa111ple cup i11 posi­ tion and arrange lhe 11ylo11 thread, or wisp of cotton so that the e11d dips into tl1e sa111ple . AssemЫe the bomb апd tighte,1 the cover securely. Admil oxygen (see No!e А4.5 ) slowly (10 avoid Ыowing thc sшnple frum !he cup) until и pre,sure is reached as indica!ed i11 ТаЫе А4. 1 . А4.4.9 A/1emari11e Comblne,t Wo,·king Smnclaгcl So/U1io11s­ P1·epare app,·opriate coinbl11ations ticcordiпg ю нnio11 co11ce11tration to Ьс dcteпnined . 1f N02- ш1d РО/- ai·c 110t i11cludcd, tl1c comЬincd working standard is staЫe Гог ш1с montJ1. Norn A4.5---lt is reco1шnended 1О поt add oxygen ог igлire 1he sainple if the ЬоmЬ has Ьссn jarred. dropped, ог tilted. А4.б.3 Combustio11-lm111erse the Ьо111Ь iп а cold-water bath. Connect 1he 1erminaJs to tl1e ореI1 electricaJ ci,·c11it. Close the circuit to igni te thc sample . Remove the bomb from the bath after immersion for а1 JeasI 1 О min. Release 1he pressure а1 а slow, uni fon11 rate such tha! 1l1e opera1ion requires not less tl1ш1 1 111 j 11. Ореп tl1e bomb and �xam iлe tl1e co11te111s. lf traces of unbu1·ncd oil ог sooty dcJX>sjts arc found, discard thc dcterrnjпation 1 and thoroughl y сlсал tl1c bomb bcforc again putting it in use. А4.5 Sample Preparation А4.5 . 1 Penetгants, Develapeгs, E11шlsifie1·s, 1Wagnetic Oils: А4.5 . I . I Weigh 50 g of test 111a1erial iпю а 1 50-111111 petri dish. А4.5 . I .2 Place the l 50-111m pctri dish into а 1 94 °F (90 °C l to 2 1 2 °F [ 1 00 °С] oven Гоr 60 min. А4.5 . I .З A l low the 1est mateгial to cool to гооп1 lemperature. А4.5.2 So/,,enr С/еапегs: А4.5.2 . I T"ke the tаге weight of an a l шninшn dish. А4 .5.2.2 Weigh 1 00 g of the cleane,· i 11to the alu111 i 1шm dish. А4.5 . 2 . З Placc thc aluminum dish оп а hot platc i n а fllmc hood. А4.5 .2.4 Let tl1e 111ate1·ial evapoшte u11til the di sl1 is 11early dгу. А4.5 .2.5 Place the dish iпю а p1·eJ1eated оvеп rron1 1 94 °F [ 90 °CJ 10 2 1 2 °F [ 1 00 °С] Го1· 10 min. А4.5 .2.б Take the dish ощ о!' tl1e oven апd al low to cool . А4.5 .2.7 Reweigh the disl1 and recoгd weight. ОТЕ A4.3-For Cleaneгs-l f thc residue is lcss than 50 рр111, reIюn. the residuc wcight. If thc wcight is greatcr tl1c1n 50 ppm. procecd with tl1c ЬоюЬ proccdurc. А4.б.4 Collec1io11 of So/111io11-Remove !he sample cup wiU1 clean fшceps and riпse ,vitb deioпjzed water алd fi l Ler l11e washings into а 1 00-111L volumetric Aask . Ri nse the ,val ls of thc ЬошЬ shcll with а finc strcam of dcioпizcd watcr from а wash bottle, ;.шd ndd the washi ngs through the filter р:.1рег to the Пask. Next, rinse tl1e bomb соvег апd terminal s and add the washings thгough the fil ter into the vol umetric flask. Finally, add cleionized water to bring the conlents of Ihe flask to the line. Use aliq uots of this sol 11tion for the ion chro111atograpl1y ( !С) aпa]ysis. А4-7 Procedure А4. 7 . I Sys1e111 E{fиilibrшio11-Turn on i on chromatograph and adjust eluant flo,v rate 10 approxi 111ate the separation acl1ieved in Fig. А4. I (2 to З mL/min). Adjust deiector to desi red selting (usual ly 1О µmho) and lel syste111 come to equilibrium ( 1 5 to 20 ,ni n). А staЫe base l ine indicates equilibrium conditions. Adjt1st de1ector olfset to zero-out eluan! conductivity ; wilh lhe fibcr suppressor adjust the regen­ e,.tion flow ,·ate ю mai,нai п staЬility, ustrally 2 .5 to З 111L/111 in. A4. 7 . l . l Sc! up the ion chromatograph in accordance with thc maпufocturcr' s iпstructions. А4.6 Decomposition Procedure А4.6. I Prepaп11io11 �f ВотЬ a11d Samp/e-Cut а piece of firing wire approx.i matel y 1 00 111m in length. Coil the m i ddle section (aЬout 20 mm) апd attach tl1e free ends to tl1e ter111i 11als. Alтange the coi l so tha! it will Ье above and !О опе side of 1he sample cup. Place 5 111L of Na2COзfNaHCO3 solt1tion in the bonib, place !he cover оп 1he Ьо111Ь, and vigorously sl1ake fo1· 1 5 s to distri bute the sol utioп over the inside of the Ьоn1Ь. Open the bomb, place the san1ple- filled sample cup in !he 1erminal holder, and i nsert а hort length of thread between the firing wire and the sample. The sшnple "'e i ght used should not exceed I g. Tf the sample is а sol id, add а few drops of ,vhite oil at this ti111e to ensure ignition of the sample. TABLE А4.1 Gauge Pressures Capacity of Bomb. mL 300 lo 350 >350 to 400 ;;,400 10 450 Gauge Pressures, atm mmA max 38 35 30 27 40 37 32 29 ::,450 10 500 А The minmum pressures аге specified to provide sufficient oxyoen fог compJete combustion and the maximum pressures present а safety requirement. N0'1'E A4.4--U!\e of" �зn1ple weighв: co111aining over 20 ing of chlorine 111ау cause corrosion of the ЬоmЬ. То avoid this it is recomme11ded that for sumples containi 11g оvег 2 % chlorine, 111е sample weigh1 Ье bascd 011 the following: 17 г Nот·Е A4.6-\Vi.1ter dip occurs Ьecause ,vater conductivity iл s.imple is less 1l1ш1 eluant co11ductivity (elшint is dilutcd Ьу v.•ater). so•>­ ст 10 15 20 Mlnutes AG. А4.1 Typical Anion Prolile А4.7.2 Ca/ibra1io11-lnject standards containing а single anio11 or а 111ixture and determine approximate retention tiines. Observed ti111es vary with conditioпs but if standard eluant and anio11 separator colu11111 are used, rete11tion always is in the order F, □-, N02-, РО4 3-, вг-, NO,-, and S04 2-. Inject at least three ditrerent concentrations Гог еас\1 anion ю Ье 111eusuгed and coпstruct а calibratioп curve Ьу ploнing ренk hcigl1t 01· arca against conccnt.ratio11 оп linear graph papcr. Rccalibrntc whencvcr thc dctcctor sctting is changcd. With а systein requi.ring suppressor regeneration, N02- interaction with the suppressor тау Iead to erroneous N02- results; inake this deter111ination onl y when the st1ppressor is at the sшne stage of exhau�tioп as during standardization ог recalibrate frequently. ln this type of syste111 tl1e water dip (see Note А4.6) шау shift slightly dшing suppressor exhaustion and with а fast ГLIП colunш t\1is тау lead to slight interference Гоr F ог СГ То eliininate this interference, analyze standards that bracket the expected result or eli111inate the water dip Ьу di\uting the sample with eluant or Ьу adding concentrated elllant to the saiпple to give the same нсо3 -1со/- coпceпtration as in the eluant. lf sa111ple adjustшeлts are made, adjust staпdards апd Ыa11ks ideшically. Both caJibra1io11 and calcularion of resulrs may Ье регГопnеd either ma11uully 01· via use or а co111puter a11d uppгopriate soft \va.re. А4.7.2.1 lf linearity is estaЫished fo1· а given detector setting, it is ассерtаЫе to caJibrate wit.h а single standard. Record tl1e peak height or area and reteпtio11 tiшe ю pem1it calculation of the calib1·ation factor, F. А4.7.3 Samp/e Analysis-Remove sa111ple particulates. if necessary, Ьу filtering tlirough а prewashed O.2-µm-pore-diam шешЬrаnе filter. Using а prewashed syringe of I to \О inL capacity equipped with а шаlе lue1· fitting i11ject sa111ple or standai·d. lnject enough saшple to flush sample loop several times: for 0.1 tnL sample loop inject at least 1 111L. Switc\1 ion cliromatograph frolll load to inject 111ode and record peak heights and rete11tioп ti шеs оп strip chart recorder. Af1er tl1e last peak cso;-) has appeared and the conductivity signal has reшrned to base line, another sainple can Ье injected. А4.7.4 Rege11emtio11-Fo1· systeins ,vithout fiber suppressor regenerate with I N H 2S04 in accordance with the шanufac­ turer's instructions when the conductivity base line exceeds 300 µ111ho when the suppressor colu11111 is 011 li11e. А4.8 Calculation А4.8.I Calшlate concentration or each anion, i11 inglL, Ьу referri11g 1О the approp1·iate calibration сшvе. Alteпшtively, whcn thc rcsponsc is slюwn to Ьс Lincar, use thc following cquation: (А4.1) where: С шg anion/L. peak height or агеа, Н F response factor - conceпtration of standard/height (or агеа) of standard, and D d.ilution factor for those san1ples requiring dilution. А4.9 Precision and Bias А4.9.I Sainples of reagent water to \\'hich were added the соI11тоI1 uпioпs wеге шшlyt.ed iн 15 laboп1.ю1·ies with tl1e results showп iп ТаЫе А4.2. TABLE А4.2 Precision and Accuracy Observed for Anions at Various Concentration Levels in Reagent Water Anion FFCI с1- CI N02 NO, вr в Ро"зРО◄ЗNQ3NQ3- so.i2so/- Amount дdded, mg/L 0.48 4.84 0.76 17 455 Amount Fot.nd, mg/L 21.8 0.25 0.49 4.64 0.86 17.2 471 0.09 19.4 0.25 13.7 0.18 12.9 0.10 0.49 0.50 0.34 0.45 15.1 0.51 43.7 Overall Precision, mg/L о.зз 0.05 0.52 0.38 0.82 46 0.09 1.9 0.04 1.0 0.06 0.15 0.16 0.52 43.5 0.07 2.5 14.8 1.15 SingleOperator Precision, mg/L 0.03 0.46 0.11 0.43 13 0-04 1.3 0.02 О.Б 0.03 0.17 0.03 0.9 0.03 2.2 Significant Bias 95 %, Level No No No No No Yes, пеg Yes. neg No No Yes, neg Yes, neg No No No No