Sunteți pe pagina 1din 259
R.E. Whan, Materials Characterization Department, Sandia National Laboratories Materials Characterization has been de- veloped with the goal of providing the eng reer or scientist who has litle background in materials analysis with an easily understood reference hook on analytical methods. Al though there is an abundance of excellent ln-depth texts and manuals on specific char acterization methods, they frequently are t00 Aetsiled andor theoretical to serve as useful ides forthe average engincer who is pri- ‘marily concerned with getting his problem solved rather than becoming” an analytical, specialist, This Handbook describes modem analytical methods in simplified terms and emphasizes the most common applications an limitations ofeach method. The intent i to familiarize the reader withthe techniques. that may be applied to his problem, help him identify the most appropriate technique(s), and give him sufficient knowledge to interact, with the appropriate analytical specialists, thereby enabling materials characterization and troubleshooting to be conducted effec tively and efficiently. The intent of this Handbook 3s not to make an engineer a ‘materials characterization specialist. During the planning of this Handbook, it became obvious that the phrase “materials characterization” had to be carefully defined ‘in onder to limit the scape of the book (0 a ‘manageable size. Materials characterization represeats many different disciplines. de pending upon the background of the user. ‘These concepts range from that ofthe scien- fist, who thinks of iin atomic terms, to that ‘ofthe process engineer, who thinks of it in terms of properties. procedures, and quality assurance, to that of the mechanical eng reer, who thinks of it in terms of stress ddisinbutions and heat transfer. The defini tion selected for this book is adopted from at developed by the Committee on Charac terization of Materials, Materials Advisory Board, National Research Council (Ref 1): Characterization describes those features ot ‘componition and structure (including de- fects) of a material that are significant for a particular preparation, study of properties. or tse, and ‘suffice for reproduction of the material,” This definition limits the charac- terization methods included herein to those that provide information about composition, structure, and defects and excludes those ‘methods that yield information primarily re lated to materials properties, such as ther imal, electrical, and mechanical properties ‘Most characterization techniques (as de fined above) that are in general use in well ‘equipped materials analysis laboratories are ‘described in this Handbook. These include ‘methods used to characterize materials such asalloys, glasses, ceramics, organies, gases, inorganics, and so on. Techniques used pri ‘marily for biological or medical analysis are hot included. Some methods that are not ‘widely used bur that give unique or critical information are also described. Techniques that are used primarily for highly specialized fundamental esearch or that yield informa tion not consistent with our definition of materials characterization have been oF ted. Several techniques may be applicable for solving a particular problem, providing the engineer, materials scientist, andlor an lyst with a choice or with the possibilty of using complementary methods. With the ex- ception of gas chromategraphy/mass spec troscopy, tandem methods that combine to for more ‘ochniques are not discussed. and the feader is encouraged 10 refer 10 the sSescriptions of the individual methods ‘The Handbook has heen organized for case of reference by the user. The article “How To Use the Handbook" describes the tables, flow charts, and extensive cross referenced index that can be used to quickly ‘identify techniques applicable 1 a given problem, The article “Sampling” alerts the Feader 0 the importance of sampling. and ‘describes proper methods for obtaining rep- resentative samp “The largest subdivisions of the Handbook have boon designated as Sections, each of which deals with a set of related techniques, for example, "Electron Optical Methods Within each Section are se cles, cach describing a separa al technique, For example, in d fon “Electron Optical Methods” ‘area cles on “Analytical Transmission Electron Microscopy.” "’Seanning Electron Micros: copy,” “"Eleetron Probe X-Ray Microan- alysis,"" and “Low-Energy Electron Diffrac tion.” Each article begins with a boxed summary of general uses, applications, lim- tations, sample requirements, and capabili: ties of related techniques, which is designed to give the reader a quick overview of the technique. and to help him decide whether the technique might be applicable to hi problem. This summary is followed by text that describes in simplified terms how the technique works, how the analyses are pet Formed, what kinds of information can be ‘bained, and what types of materials prob- Jems can be addressed. Included are several brief examples that illustrate how the tech. nique has been used to solve typical prob- Jems, A list of references atthe end of each anicle directs the reader to more detailed information on the technique Following the last Section is a “Glossary (of Terms" and appendices on metric conver- Sion data and abbreviations, acronyms, and Symbols used throughout the Volume. The Handbook concludes with a detailed cross referenced index that classifies the entries by technique names, types of information or analyses desired, and classes of materials, This index, combined with the tables and flow charts in the article “How To Use the Handbook," is designed! o enable the user 10 (quickly determine which techniques are most appropriate for his problem. REFERENCE 1. Characterization of Materials, prepared by The Committee on Characterization of Materials, Materials Advisory Board, MAB-220-M, March 1967 How To Use the Handbook R.E. Whan, K.H. Eckelmeyer, and S.H. Weissman, Sandia National Laboratories Effective Analytical Approach ‘The key tothe successful solution of most, materials problems is close interaction be tween the appropriate engineers, meri scientists, and analytical specialists. Engi neers and other applcations-oriented person nel are often the first w encounter material failures or other problems. When this oc curs, consultation with a materials specialist is an essential first step in the troubleshoot ing process. By vinue of his knowledge of materials, the materials specialist ean help the engineer define the problem, identify possible causes, and determine what type of Information (analytical or otherwise). is needed to verify or refute cach possible fase. Once a decision has been made re ‘garding the information needed, they must ‘determine which analytical techniques. ap ‘pear most applicable 10 the problem. With the large number of techniques avai able, its eften difficult co identity the best method or methods for a given problem. The goal of this Handbook is to belp engineers and. mterials. scientists identify the most applicable analytical methods and interact clfectively with the appropriate analytical specialists, who can help define the analy cal test matrix, determine sampling proce: dues, take the data, and assist in interpreting the data, Together, these workers ean solve problems much more effectively than could bbe done by any one, of even any two, of ther, This collaborative approach to solving & problem has many benefits, When the ana Iystis fully informed about the nature ofthe problem and its possible causes, he is much fore Tikely 10 understand what 10 look for and how best to fook for it. He may be able to suggest complementary or alternative techniques that will yield supplemental andior more useful information, He will also be better equipped to detect features or data trends that are tnexpocted and that can have substantial impact on the problem solution In shon, involving the analyst as a. fully informed member of the team is by far the mont effective approach wo solving problems process, this Handhook contains several ref ference tools that can be used to screen the analytical methods for applicability. The First of these tools isa set of tables of ‘common methods for designated classes of materials. In the next section of this ance, ‘separate table has been developed For each fof several classes of materials: inorganic Solids ¢metals, alloys, and semiconductors, lasses and ceramics: minerals, oes. ete) Inorganic liguids, inorganic gases. organic Solids, organic liquids, and organic ‘The most common methis (1 neces all-inclusive) for analyzing a particular class ‘of materials are listed on the lft. The kinds ‘of information available are listed as column headings. When a particular technique is applicable, an entry appears in the appropri ate column, It should be emphasized that lack of an entry for @ given technique does rot mean that it eannot be adapted to perfor the desired analysis: means Simply that that technique isnot usually used and others are izenerally more suitable. Because there are always situations that require special condi tions, the entries are coded according to the legend above cach table. For example, an "e" indicates thatthe technique is generally usable, whereas an "°N" indicates that the technique is usable only fora limited number ff elements or groups As a simple example of how to use the tables, suppose that an engineer has a bar of ‘material labeled only “18-8 stainless steel.” and he wants to know whether it can be ‘welded, Through consultation with a weld- 12 metallugist he would find that weldable sinless steels contain very small amounts ‘of carboa oF alloying. elements, such as niobium or titanium, that ie up carbon in fonder © avoid formation of chromium ear bides at the grain boundaries during cooling Im addition, stainless steels that contain se- Jenium or sulfur to improve their machin. ability are extremely. dificult to weld ‘Therefore, to determine whether the ste! weldable, quantitative analyses for niobium. titanium,” selenium, sulfur, and earbon should be performed, as well as for chro: ‘mium and nickel to document thatthe mate tial really isan 18-8 type of stainless Referring t the table “Inorganic Solids: Metals, Alloys, and Semiconductors,” then, the engineer can look down the list of ana Iytical methods for one having “e's under the “"Macro/Bulk"” colurma, the "Quant column, and the "°Major” and. “Minor columns. This quickly shows that optical femission spectroscopy, spark source mass spectrometry, and. x-ray spectrometry are potentially useful methods, The engineer ean then refer to the boxed summaries in the individual articles on these methods to check limitations. For instance, he would find that X-ray spectrometry cannot generally analyz for elements with atomic numbers less th 11, so if this method was selected for anal ysis of niobium, titanium, selenium, sullut ‘hromium, and nickel, another technique such as high-temperature combustion, inert fais fusion, or vacuum fusion analysis (all having “G's in the appropriate columns) ‘would have 10 be employed for termination. The boxed summa articles “Optical Emission Spectroscopy” fand “Spark Source Mass. Spectrometry. however, indicate that these: methods can analyze Tor all the clements of interest: therefore, one of these would be a logical choice. ‘Another method for selecting analytical methods is by use of the flow chars shown under the tables. Again, a separate chart for ‘each ofthe different elasses of materials has heen developed, ‘The charts are based on the type of analyses andior the type of information ‘desired. The subdivisions Separate the analyses into several different categories, depending on the class of mate rials. For example, the flow chart for “Inor- ganic Solids: Metals, Alloys, and Semicon: ductors” is divided into bulkelemmental anal ysis, microanalysivstrucure, and surface analysis, Each of these categories is then further subuivided so that the user can follow the flow to exactly the kinds of information ‘or analyses that he needs, Under each cate~ gory only the most commonly used tech rigues ate Tisted, in order wo keep the flow ‘chart readable, Several other methoxls may be adapted for use under special conditions ‘or with special attachments oF modifications as described in the individual articles ‘Taking the stainless sicel example dis: cussed above, the engineer could examine the flow chart for “Inorganie Solids: Metals, Alloys. and. Semiconductors.” follow the Now’ to. “"Bulk/Elemental—Quanttaive.” and look for entries under “ MajotrMinor. * ‘The same techniques identified in the table are cited in the chat, leading the engineer to the appropriate articles in the Handbook Finally, the detailed cross-referenced in- dex at the back of the Handbook can be ‘omsulled under aay or all of the pertinent talegores cited above. In this index. tech- niques ae listed not only by eategories such fs qualitative vs quantitative, macro vs «ero, and major vs minor vs trace, but also by typical ways in which they are applied to the solution of materials problems. For example, under the beading **Twinning,”* the entries listed are metalography, by which winning can be detected; xray diffraction, by which twinning in single crystals can be eharacter- ized; and transmission electron microscopy, by which twinning in polycrystalline sam: piles can be characterized. Similarly. under the heading “Inclusions,” the entses listed ‘are metallogrephy, by whieh inclusion mor- phology can be documented; image analysis, ‘by which inclusion numers, spacings. and morphologies ean be quantified, and sean- hing electron microscopy, transmission clectron microscopy, electron probe x-ray microanalysis, and Auger electron spectros ‘copy. by which inclusion chemistries ean be determined. Again, it should be emphasized that this Handbook. is meant as a tool to familiarize te nonanalytical specialist with modern an- lytical techniques and to help him identify techniques that might be applied to his prab- lems. The Handbook is not meant to be an analytical textbook or to replace indispens: fable consultation with materials and analyt- cal specialists Tables and Flow Charts ‘The tables and flow chars in this seetion hhave been developcd as tools 10 provide information about the most widely used ‘methods of analysis for different classes of materials. These tables and chants are not inended to be alkinclusive but co identity the most commonly used tevhniques for the types of materials to be characterized and the types of information needed. As a result, How To Use the Handbook / 3 many techniques that require special modifi cations ot conditions to perform the desired analysis are omitted. The previous section of, this article describes how to use these tools ‘After examining the tables or charts. the reader is encouraged 1 refer to the appropri- fate articles in the Handbook for adcitional information prior to consultation with an analytical specialist, “Ablaeviations used in the headings of the lables and charts are Ten Benen aa fy sor Ally seats fue ep ae nay ual ‘Galveston of Scigunt Semin analysis nde of ome quate mays precision of Macs ak... Macamaly or bela Mire Méroanbys (210 a Sat Sure anal Mine Minor orpoent (01 10 8) Te “racy compen (1 108 ppm or ‘aot wot) Ura... Uae crmponee 1 ppm ot “=D wh) The acronyms listed below ane used in the tables and chars (Cor addi and abbreviations, see the s ations and Symbols" in ms “None aboion pestoney as dope eaten specs Cone 5 Riahtonpere sombuson ie ‘Bows sal nal EMA... Hn pb yin se Eicton spn rseomee i ser om eed CGOMS Gat eonsogapy ma os, oatnusr geomet i the ana e Ion chewy IeP AES Tndacicly cowed pon ae ise ypc) tok Inet non we Ina pttecgy Isls lve gait esa Ciiss ecoetey arseig ss ols resem ‘ecco Naa Nelo etiam sont nue Neel poet ome oes Cpl rae pocescoy fo pc ater rs und aang . ‘pstmt Sans. Salt angle cay saeing sex ‘caning lesen miconcopy sins Scocmday ion ss peRcOPY sss Sart sce mat poromin Test ‘eameison ern microscopy UVINIS |. Uhavne ae drpon x apples peemncopy xKS Seay sete 4/ How To Use the Handbook INORGANIC SOLIDS: Metals, loys, semiconductors Wet coals chenisry,eacrochenisy, uraoltviible abrrpion speoscopy, ond molclorfunrescence spectroscopy can gneelly be adopted Yo frrform mony af he bulk onses ite fygen soe Boned srmery i rte fr deta S wgeneely wibies Nor | ited mbt of elements or groups; G ~ carbon, nrogen hydrogen. ur, oF ort = under pede condor; D-— ahr Gestion, Zor ** = weiconducor oly sm Semi sce! fe Pane Stae Mem ae tm a! nn at germ atu ero ce Mor Marra =e os >» > > cont r cs oa ‘ ia . . ic DN BN DN bw bx reas » pb » heer Zz 2 Leis o soe oe RBS oe eos . . s ks te 2 a 2 £ ® 2 Sixt wos 28S . s . sins ss 2G . s Tes wos <8 & . : oe ee xs wes 2G o ® XRD. es fos se : oo xn eos oe poof foe al ema cuir Sarai P q q q t 1 f + uae uate Coils) Phe don Elemorat ‘Dees leenal Maula ho 1D Mapes Compan Mae? Tries Mae) Tre 4 4 4 4 K ' Aas ass Ese ais see rik werars Fri ier cOMB test eM Taw ks NAR Ie hacs “EK XRD Sen XRD sivse Om enags Gr FTIR mM xs sous ia NAA 1c xR Naa. OES CARS. ors sss Grr sss Kes ry How To Use the Handbook / 5 INORGANIC SOLID! Wet onaiia chemiany, uravetvsible dbsorption sprcroxcopy, and molclr fherescence specrascopy cen general be adopted 10 perform mony othe bik ona: Ind. generally sable, Nr} ~ limted numberof elements or group S or” — under spel conditions, D = after dschtion lasses, ceramics Spe bw sem Moers Sore ime Sieve pk meat age thm Moe Mm Qual geo! uate ero ce me oT ee we ry > > Fist ra . : re ex ON DN BN DN DIN b.N reoiags nb i > TRePTR w oS os s 8 $8 § sos os ons : sof oes : OM. a toe a sis 10 . s sas i soe : xn a sot tos ah Elemental rane Sorte nays L f + 1 1 t 1 t \ uate cutive Cost ace) Page inhuion! Ekta! Defect metal Molla inet Sasi Compan Moje Tre Ms Trace Mer Ulta Minor ce Fri FTIR AAS. Mas 1 Phin AS SEME ABS rine Wr rnIRIY ran XRD ws EM TM Less Pe chars i on ‘Seu kas as sce aks so TEM sims tke ia Tes xs XPS OES 6/ How To Use the Handbook INORGANIC SOLIDS: Minerals, ores, slags, pigments, composites, catalysts Wet enalial chemistry, eacrchamishy, utraletvsble absorption ypeckonopy, nd moleclar fuorescence ypecroxopy con ganeally be elope Yo perform mony of he bk anlaes ited. © — generally uscble, © ~ carbon, mirage, hyrogen, slr, er oxygen sxe boned uta ‘atic for dea Nort = lined nurbar of elements or groups Sr * = unde spacial conditions, D'~ r daslaon organic compounds, effluents, chomical reagents, tt ae tam ore geet et Mem te roe oe mas rn > B con mG “Ge 6 fo oan sie oe 8 . s . Bx a x oR OS x « ose > pb op . reraks St 5 8B eerie io sb s ) = i a8 ies a ee Gf . Ss = slo slo sto 5 sp 8D an oo . : . 3 Sis na : re xes moe pobof os ss aire seein ‘en i + mr mn) te aan a ies a tie | | How To Use the Handbook / 7 INORGANIC LIQUIDS AND SOLUTIONS: Water, effluents, leachates, acids, bases, chemical reagents ‘Wet onollical chemistry, elecrochmisry, rales absorption spacroscapy, ard molecular orescence spectroscopy ean generally be edoped 12 Jarform the bk analyes ted, Mest ef ecniges Sine For naga sds an be ted he ride ater the soltion is evoporated to dryness ® (every wale, Nor Init number of elemens or groups: S = under special codons; Vor * = vole Ids or components ae Cas ar Sar eae tom “Mim pand Nowe unt “Waste Me tree x N x oOS 8 x s x ie x oo © Nn S x oN Gus yoy vy v y y y ¥ Icha : : : : : : Ise nr : : : : : : sai ‘ 8 yO k 5 x te ‘usitatveravantianne ‘Quatave eave Maj) Trace Mor) Trae Mine Uke Mine Clase ESR ESR GoMstGOMS* censs GeMs rs 1c ic c te Tm chars rer aes Nuk ist Ise " Sue kM 8 / How To Use the Handbook INORGANIC GASES: Air, effluents, process gases ‘Most ofthe ecviqus lite for inorganic solid od inorganic luis con be und if he gos sorb ona sido nt eligi. © ~ generally sable = co to tar Med Pa thm Monn Mw ud ee Gs ad eerie 8 ‘ Bs bee : 4 lence ect nulaiveQuetiative Co Minor i FraR i ‘GMS Ms How To Use the Handbook / 9 ORGANIC SOLIDS: Polymers, plastics, epoxies, long-chain hydrocarbons, esters, foams, detergents, dyes, organic composites, coal and coal derivatives, wood products, chemi organometallics ‘os of totus for inorganic sods and inorganic gids con be wed on ony reside ater oshng. @ — gerraly uable; N or |= lined numberof Cements or groups § oF "= under spec corto, D ~ offer Sioliiowentracion V = voloie solids or corponens (can aso be oncyzed by GCIMS), prrlyed vliee € ~ cystine shes Spee Cm a e se ne Meat im "Hoe pwr Me Ghat ent Gua tery Tce Mor wine trace trea ies * oo - oe oe Ena N s ‘ No oN ow N c D.N Dw Dx DN DN DN DN her X pe De be be bs de De be ps te > DDD is BIN BN BN DN DN DN BN DN ow. se . ks be be De Ss ope De bs se : . tet c : coe xb is c 6i xs moN e ON N uth Maeroanalss ‘Structure Morpholory Surtace amass f + f ¥ ? f + Beneor uklaCorpnnd Catal Pine diuibuon’ Molecular lemectal Mee? Calgatve yinive aaatve uae Mar) Trae! Majo Trae) Maj) Tine) Maori Tce Ming Uhre Mime Utraace —Mioor—Ultarce Mirar—Ulsarace coms! coMB} COMB? COMB) ERG FTIR ERG FREY PMA SR AS FTIRY ee) rSRY Ceres) FTIR ICP FTIR Ich XRD a frie uniss "ies gst Sie) ese eich ich on te SIMS Se meee Ch MSR tce Lt sen nar XPS) SIMS MS) NAAL MES NAAT Mist LC MES Tex Ks XPS! Kast UWIS NAL UVM UVNIs Msi UVvIS SAXS NMR ovis RS tos xs uviis ‘xs! 10/ How To Use the Handbook ORGANIC LIQUIDS AND SOLUTIONS: Hydrocarbons, petroleum and petroleum derivatives, solvents, reagents ‘Most of the teceiges lined for inorganic st ad incrgoic iq con be uted on any residue afer ashing, Mony wet chemical lechriquts con be adopted fo pertoom fe arly sted © gorerall usable; Nor Kad number of elomers or groupe; 5 ~ under special codons Vor * ~ volte huis sat amt thn npn Monat game Quant Hk Maar Mine Trae He oe > _ ee * . . . se BON ON oN 8 * ‘ yoo cons os yoyovoy ¥ y v y y Ms m ON nN a x SN Naa. m ON NON ON ON x SN vais wo” foe ema \ atte Quine | 86 Naat san ree Est (Gait Qeansie Make’ Tate Mn hate BG es frm Prk censy cuMse ose GMS" uc Mts sis US SMa ovis es How To Use the Handbook / 11 ORGANIC GASES: Natural gas, effluents, pyrolysis products, process gas ‘Mos ofthe tecigus lite for organic sl ond orgonic luis can be used he gs is sorbed ono sald or into gud. © Ander specal conden -~ aber sorption ato sod or imo © hid generally ssable: 5 Manse astm pond Mom ge tar Mowe Tet cows ary 7 ea” 2 8 : : . cas me foe ob eS 2 tc te t t c t t r Rs mee os : oe oe : : . Genera sates Frik oe Sampling* John K. Taylor, Center for Analytical Chemistry, National Bureau of Standards Byron Kratochwil, Department of Chemistry, University of Alberta Introduction Sampling isthe selection for testing of a portion of a population. Portions are used for fconomic and technical reasons for. the Chemical and physical measurement of raw materials, plant process streams, and the final products and wastes produced by indus- try. Many industrial decisions relating to ‘quality control of raw materials and end products and to environmental: monitoring fre based on sich measurements “The reliability of any measurement de- pends on sample quality. A poorly devised ampling plan or uncertainties in the sam- pling process, in sample storage, preserva tion, oF pretreatment may obscure results or prevent their interpretation, This article will primarily consider the problem of sampling bulk materials, including minerals, metals, ‘environmentally important substances, and industrial raw materials and waste products “The design of bulk sampling programs involves: + Adentifying the population from which the sample is to be obtained + Selecting and withdrawing. valid. gross samples of this population + Reducing each gross sample to a labora tory sample suitable for the analytical techniques to be used Inherent in the design should be an effort to maintain sampling conditions that yield ac: curate results rapidly and economically ‘Commonly used terminology is defined in the section “Glossary of Terms” in this Volume. Many sources of error, such a contami nated apparatus or reagents, biased methods, aes 1201S fom Sampling Bul Mates foe for operator errors, can be controlled by [proper use of blanks (a measurement involy~ ing addition ofall the reagents, but not the sample), standards, and reference materials However. controls and blanks will not be ‘useful ifthe sample is invalid. Accordingly, sampling uncenainy is often treated sepa: rately from other uncertainties. For random errors, the overall standard deviation, 3. is felated to the standard deviation for the Sampling operations, s, and 10 that for the femaining “analytical operations, 5, by 2 = 2 + sf, Whenever possible, measure: ments should be conducted so that sample ‘variability and measurement variability can be separately evaluated. For a measurement process in statistical control where sis Known, s, can be evaluated from sy, which is ‘etermined by analysis of the samples. AL tematively, an appropriate series of replicate measurements or samples can be devised to evaluate both stindard deviations. Funher reduction in measurement uncer- tainty is unimportant once itis one third or Jess of the sampling uncertainty (Ref 1) ‘Therefore, if the sampling uncertainty is large and’ cannot be reduced. a rapid, sp- proximate analytical method may be suf ent, and further refinements in meusure~ ment” may not significantly improve the ‘overall results, In such cases, a rapid method of low precision that permits more samples to be examined may seduce the uncertainty in the average value Sampling is occu sionally directed at obtaining an extreme value, such as the best or worst case. How: ‘ever, a simple usualy is collected to deter mine the distibution of some characteristic fmnong the population. To obtain the best es- timate ofthis distribution, random sampling ‘may be performed. In random sampling, ev- ‘ery part of the population has an equal chance ‘of being included inthe sample, regardless of the location oF nature of that par. “The distinction between the target popul- tion to which conclusions should apply an the parent population from which these sam- ples ate actually drawn is important practice, these are rarely identical, although the difference may be small. Ths uitference may be minimized by random selection of portions for examination, in which each part fof the population has an equal chance of Selection, Generalizations based on mathe: Inatical probability can be made from such random samples, "A random sample is obtained by basing sample collection on a table of random numbers: it is. not selected haphazardly However, samples selected using a defined protocol tend t reflect biases brought about by decisions of the sampler and the equip- ment used. In addition, individuals who ‘obtain samples must understand that the fpparently unsystematic collection pattern rust be followed closely to be valid Tn random sampling ofan entire lot of butk tral, the material is divided ino-a number fof real or imaginary segments, For example, {bin of raw material can be conceptually Subiivided horizontally and vertically into cells. Each segment is then assigned 8 num ber. Segments from which sample increments will come are selected by starting in an ar bitrary place in a random number table (Ref 2} and choosing numbers according toa pre: Sef pattern, such as adjacent alternate, or th centres, then sampling those segments Tor the ‘determined number of samples. Because of its simplicity, sampling at evenly spaced in- tervals over the bulk is often uscd instead of random sampling, although results must be closely monitored to prevent errors from pe- rhodicity in the material Systematic Samples. Hach sample collected systematically and analyzed to re (Cems Analyse Amat Chem. Vo $3 (No. A), 1, p DAA, wih permison Fig. 1 Sequence for an overall operation to estimate a property of a system i I Some I I a ey flect or test some systematic hypothesis, such as changes in composition with time, tem- perature, or spatial locations, should be con- sidered representative ofa separate, diserete population under the existing conditions However, the results may stil be statistically tested for the significance of any apparent diferences, ‘A carefully designed sampling plan in cludes the possibility of unanticipated events fr phenomens that could prejudice the anal- yses, For example, measurements at timed intervals are sometimes made with random SMart or other superimposed random time clement. The less known about given Process, the more randomness is merited Conversely, the more fully a process is understood, the more efficient is a system: lic approach to data acquisition. Representative sample frequently connotes a single sample of a universe or population expected to exhibit average prop- ‘eres of the population, It isnot possible to select such a sample by a random process, or to verify if it is representative, A wuly representative sample seems valid only i the sample is defined a prior! as representing a specific purpose, such as the Hazardous Waste Management System, which pre- seribes seven protocols for obtaining sam- ples that “will be considered by the agency [Environmental Protection Agency} to be representative of the waste” (Ref 3), 0€ if truly homogeneous materials are sampled ‘Although it may reduce costs, measure iment of samples defined as representative yields information not equaling that from valid random samples of the population, except when the poptlation is homogenized here sampling to produce a number of similar subsamples. A properly designed and ‘executed random sampling plan provides ‘sumple mean and variation between mem= bers, neither of which can be obtained by analysis of one ‘representative sample.”” ‘A composite sample may be consid- ‘ered a special type of representative sample. Many sampling procedures assume that only average composition is desired, such as bulk, time-weighted, or flow-proportional averages, and specify collection or prepara- ion of a suitable composite. Elaborate feushing, grinding, mixing, and blending procedures have been developed and stan- ‘ardied for preparing solid composites (see the anicles “Milling of Britle and Ductile Materials” and “Blending and Premixing of Metal Powders" in Volume 7 of the Sth Editon of Merals Handbook). Sampling ss: tems have been developed to obiain liquid {especially water) composiies (Ref 4, 5). ‘Analysis of individual samples. permits determination of the average (atthe expense ‘of additional analytical effort) of the distr bution of samples within the population (between-sample variability), and of within- sample variability (if replicate analyses are ‘eonducted). Composite samples provide im: ited information, and the consequences should be carefully considered before deci- between this approach and the analysis of individual samples. ‘Subsampling is necessary, because the sample oceived by the analytical laboratory ‘usually larger than that required fora single ‘measurement, Test portions taken for repli cae measurements or for measurement of df= ferent constituents by several techniques must be sufficiently alike so that results are com: patible, The effont necessary to reduce pat- ticle size, mix, or otherwise process the lab- oratory sample before withdrawing portions (subsamples) for analysis depends on the ho. ‘ogencity of the original sample. The Sampling Plan Before sampling begins, a model of the ‘overall operation should be established (Fig 1). The model should define the objectives of the study, although multiple objectives ‘may compete for limited resources. Typical ‘objectives include estimation oF evaluation ofthe average of characteristics in a popula ‘ion and their variability or distribution and determination of whether characteristics of interest in the population meet. specified standards or pre-established erteria (Ref 6) “The model should also define the popula- tion studied, substance(s) to be meusured, extent of speciation and distribution within the population, and precision required as wwell-as identify all assumptions about the population, Once the model is complete, a ‘sampling plan can be established. "The plan should specty the size, number, and location of the sample inerements, the Sampling / 13 extent of compositing. if applicable, and procedures fr reducing the gross sample toa laboratory sample and (0 test portions. Be- fore work begins, this should be written ss a detailed protocol that includes procedures for ‘steps, from sampling 1 sample treatment, ‘measurement, and data evaluation. It should be revised as nocossary for new information, ‘The protocol dictates when, where, and ‘how to take the sample increments and will establish on-site entera for collection of a valid sample, Decisions about whether a ‘component is foreign (not part of the pops: Tation) often must be made at the time of sampling. If possible, criteria for such deci- Togieally and sys- 1 begins, The type of container, cleaning procedure, protection from contamination before and after sam pling, storage conditions and possible ald tion of preservatives should be specified "The analyst should perform or supervise the sampling operation or should provide ‘written protocol to well-trained individuals Aware of the importance of minimizing bias land contamination, Also important are care~ Tul labeling and recording of samples. A hain of custody to ensure the integniy ofthe Samples from source 10 measurement is es- sential. Details such as temperature position ‘of the collecting probe in the sample stream tnd flow velocity of the stream should be recorded when the sample i taken. Omission ‘oF loss of such information may greatly de ferease the value of a sample or render it worthless ‘Sampling Bulk Materials. Once the substances to be determined and the preci sion desired have been specified, a sampling. plan can be designed that considers; + Quantity of samples to be taken + Their sizes + Location inthe bulk material (population) from which they should be taken ‘+ Whether individual samples should be analyzed oF a composite prepared ‘The ‘lative homogeneity of the system fects sample size. Gross samples should be lunbiased with respect to the different sizes tnd types off particles present in the bulk material. The size of the gross sample is often « compromise betwoen the heteropene- ‘of the bulk material andthe cost. ‘When the properties of a material to be sampled are unknown, a. useful approach isto collect a small number of samples, using ex- perience and intuition asa guide to make them ‘as representaive of the population as possi be, then to analyze forthe component of i terest, From these preliminary analyses, the standard deviation 5, of the individual sam ples can be calculated, and confidence limits forthe average compositionestablished using: 4 Sampling (eq) “Vn where jis the true mean value of the population, «isthe average of the analytical measurements, and i obtained from statis tical tables for n measurements (often given sn — 1 degrees of freedom) at the desired level of confidence, usually 95%. Tables of ‘values ate provided in Ref 2 and IL ‘On the bass of this preliminary informa tion, a more refined simpling plan can be evised, After one oF two cycles the pare ‘eles should be known with sufficient confi- dence to estimate the optimum size and humer of the samples with a high level of confidence. Considerable savings in time and cost result from optimizing the sample imum Size of Individual Incre- ments. ‘There are several methods for esti- mating the amount of sample required in 3 given increment so as not to exceed deter: ‘mined sampling uncertainty. One method uses Ingamells’ sampling constant (Ref 7-9) Because the between-sample standard devi- ation, s,, decreases with increasing sample Size, the following relation is often valid: where w isthe weight of a is the relative standard devi of sample composition, and A, is the sam- pling constant, corresponding fo the weight fof single sample required to Timit the sampling uncertainty to 1% with 68% conf ‘dence; K, may be determined by estimating 5, from a series of measurements of samples cof weight w, Once K, is evaluated fora given, ‘ample, the minimum weight we required for ‘predetermined maximum relative standard ‘deviation of R percent ean be readily ealeu- lated. This method applies only to subsam- pling of well-mixed samples and cannot be ‘sed i segregation is present. ‘Minimum Number of Individual In- crements. Unless the population is known to be homogeneous, or unless an analy: sal problem necessitates. a representative ssumple, sufficient replicate samples. (in- temienis) must be analyzed for the compo- rent under study. The minimum number of sample increments necessary to achieve 3 given level of confidence can be estimated from be en B where is the Student's able vale forthe ieel of confidence desired (Re 2,11), 31s tclinsied fom preliminary composite fmeaturements on, or fom previous kno edge of, the bulk materi, and £ is the standard deviation acceptable in the average ly, ¢ can be set at 1.96 for 95% ‘confidence limits, and a preliminary value of in caleulated. The £ value for this r can then ‘be substituted and the system iterated. to constant 1. The expression applies if the soughtfor component is distributed in the population in a postive binomial, oF Gaus sian, distribution, which is characterized by amaverage, larger than the variance of the ‘Values of w, (and s,) may depend greatly ‘on the size of the individual samples. The value of may also depend on concentra tion, If the relative standard deviation is ‘constant with respect to concentration, reli- tive standard deviation and relative’ ertor ‘may be substituted for s, and ‘Sampling a Segregated (Stratified) Material. Special care must be taken when assessing the average amount of a substance distributed nonrandomly throughout a bulk ‘material. Suh segregation may be found, for example, in ore bodies, in different production batches in a plant, or in samples ‘n which settling produces variable compo: tion, To obtain a valid sample of a stat sd material + Divide the material ito eal or imaginary segments (strata) based on the knovin oF Suspected patter of sepregation + Further divide the major strata into real or imaginary subsections and select the re- quired number of samples randomly (preferably with the aid of a table of random numbers) + Take samples proportional in number to the size of each sttatum if the major strata are not equal in size In genera, stratified random sampling is preferred to unrestricted random sampling if {he aumber of strata is kept sufficiently small that several samples can be taken from each, In this way, possible variations within the parent poptlation can be detected and as- essed without increasing the standard devi ation ofthe sampling step. ‘Minimum Number of Individval In- crements in Segregated Material. ‘When a bulk material is highly segregated many samples must be taken from different segments. A useful guide to estimating the number of samples needed is cited in Ret 10. The variance in sample composition depends on the degree of homogeneity ‘within a given sample increment and the degree of segregation between sample inere- ments (Ref 10) g-AaB (Eqs) where 2 isthe variance of the average of ‘amples using a sample increment weight and A and B are constants for a given bulk ‘material; A is homogeneity constant, and B ‘segregation constant Values for A and B can be obtained experimentally for a bulk population in «wo ‘ways, In the first, two sets of inerements are collected, one with w ay small and the ther fas large as feasible. The component of interest s measured and a sampling variance calculated for each set, Values for A und B cean be calculated from A= ww (55 Si my — Weand B= (Any). second upproach, applicable only to maierial for which the reciprocal of the average particle mass m can be estimated. is to collect a series of pais of inerements, cach ‘member of a pair being of weight w and collected from near its partner. ‘The incre- Imenis are then analyzed or tested, and an intraclass correlation coefficient r is calew lated (Ref 11). Values for A and B are then calculated using Eq 4 and the relationship r= BiAm Sampling Materials iscrete Units. If the lot of material under study ‘occurs in discrete units, such as truckloads, drums, botles, or tank cars, the variance of the analytical result is the sum of the variance between units inthe ot, the average variance of sets of samples taken {rom within one unit, and the variance of the analytical operations. The contribution from each depends on the number of units in the lot and the number of samples taken (Ref 6x: 18 at ny where a is variance of the mean, of is variance ofthe units inthe lot, os average variance, of the samples taken from a sez ment, «is vatiance of the analytical opera tions, Nis number of units in the Tot, ny, is ‘umber of randomly selected units sampled, fi. is number of randomly draven samples {fom each unit selected for sampling, and a, is total number of analyses, including repli cates, run on all samples If stratification is known 1 be absent, preparing a composite sample saves mes ‘surement time and effort. Equation 5 also applies to this situation I the units vary Sighificandy in weight or yolume, resulls should be weighted accordingly. For homogeneous materials, including many liquids and gases. eis zero, and the second term on the right side of Ea $ drops ‘ut. If all units are sampled, n= and the first term on the right of Eq also drops ‘Sampling plans must inelude minimizing the cost of determining an estimation of the population mean to within a specified vari nce or minimizing the variance for a given allocation of funds. Fora stratified sampling plan, assuming the strata to be equal in size 8nd in variance within strata, the total cost ¢ ct cyt mc, + mimes + nynanes a) where «is the overhead cost ¢ isthe cost Of selecting each of the my strata, ¢ is the fast per sample of collecting ‘within cach strata, and cy is the cost per analysis form, analyses per sample (Ref 12) For example, if an analysis of variance has frovided estimates of «ro, and for the Selection of strata, the simpling within each strata, and the measurement, each contrib: tutes tothe overall variance by: (a7) ‘The minimum cost ¢ for a fixed value of is obtained (Ret 13): WETE or. = Wire + (Eq 8) (49) fe (Bq 10) Because my and ny are not alfected by the value selected for °, ila” is to be reduced the aumber of strata m, sampled should be reduced while holding ns and. constant. For a fixed total cost ¢, the optimum values of ny nay and my ate ever, 8 eee) ia + Vere (6 12) (Eq 13) For this system, the optimom allocation Deyond the first stage of sampling is the same for fixed total cost as for fixed total Example 1. In sampling a trainload of metal pipe for the percentage of an alloying clement, the standard deviation is 0.25 be- tween cars, 0.15 within a ca, and 0,08 for determination, The relative costs of the op- eration are 54:1, The overall standard devi- ation «yi the result is not to exeeed 0.10, “The Optimum sampling sebeme is: [Svea + VOTH + VOR se _ Vora) or (Woe) OK = 107 (Eq 16) Taking a 02571 + DISA + BORIC) (1) =0.008, andor, = 0.09. The cost = (11 XS)H (4) + tL 1) = 6onthe sel tive seal the costs were fixed at, for example, 40 times that of a single determination on the relative seale, the minimum standard devia tion that could be obtained would be: =4 = 1 VOB a + VOTED + VOOR 1 = 48 am foray = (TBD 96 qi Voasva * 4 tty = fO98DD ~ 1.97 (Bq 19) Vos Taking m, = 5, m= Land ny = Le = x8) + VUKS) + OXDUT) = 50 and of = 0.2595 + O.1S4S(L) + 0.08/5(1) (= 0018, then, = 0.14. Caleulating Statistical Sampling Uncertainties. Sampling is most impor Sampling / 15 tant when significant heterogeneity or segre gation exists. When &, 5, K,. A, and B are Known exactly, itis easy (0 calculate the Statistical sampling uncertainty and to deter ‘mine the number and size of the samples needed for a given precision. If, as is more Usual, these quantiies are knosen only ap. proximately oF not at all, preliminary sam: ples and measurements must be taken, and from these more precise sampling. proce: dures developed Practical Aspects of Samplin, Chemical analysis is typically performed ‘om a material that is a subset of some other ‘material or even of a system of materials of imerest, Although the actual sample ana- lyzed may be so small that its ratio to its parent is almost infinitesimal, for example, & Few milligrams of sample as related to thou- sands of tons of an ore, ik must represent the population of interest. ‘All aspects of the sample must be consid ered in relation tothe model of the analytical problem (Ref 14). It must be taken according tova specific strategy, preserved to minimize deterioration, contained to prevent intrusion ‘of Foreign substances or to minimize escape fof constituents of inlerest, processed 10 Te tain is integrity, and subsampled as neces- sity, while maintaining its correspondence {o ther members of its immediate family Because al these axpeets cannot be guaran teed, it may be necessary to analyze ‘number of subsamples. to perform related measurements to evaluate the magnitude of any atual or potential complication, or bath For example, the appearance of a lump of ‘ore under analysis may’ suggest heterogene- ity and that care should be exercised in sampling it. A sample such as a piece of metal may appear uniform and provide no indication of microheterogeneity. Even ifthe ‘material is uniform in structure, different ‘leed particles of chips obtained by crushing or machining may have significantly difer: cent compositions. 1g Protocol. The model of the ind planning of the measurement Program should specify the location of sam pling sites, the number of samples required, And how the actual samples are to be taken ‘There should be no uncertainty as to what the sample is, which requires that it be taken according to a protocol ideally codeveloped by the problem-area specialist, the analyst and a statistician. Therefore, 2 minimum of ‘these theee disciplines must be represented in planning In many cases, such as failure analysis, field examination of the material or structure being analyzed is required. Such on-site 16/ Sampling ‘examination frequently reveals information ‘essential fo problem solving that may either 0 undetected or be permanently lost if the ‘description ofthe incident and sample-taking fare left to personnel who are not familiar ‘with metallgical, analytical, and statistical principles. ‘Mechanism of Field Sampling. Sampling usually equites equipment. Buck- ets, scoops, of shovels are useful fr fluid or tgranalar materials (Ref 15). Special devices Called thieves are used (0 sample granular ‘materials at various levels within a container for mound (Ref 15). The use of thieves is discussed in the atele "Sampling of Metal Powders” in Volume 7 of the th Edition of Metals Handbook. Dredges. drills, saws, ‘eutting torches, augers, or corers may be needed to obtain samples from massive ms terials. In some cases, the sample may be ‘extracted using fillers, sieves, oF absorption devices. It may be obiained ina form ready for analysis or may require further extraction for processing in the laboratory Samples must be taken ina way that does not infvence the measurements to be made For example, the use of cutting for removing samples from metal structures for: metal~ Jographic examination should be avoided, be: cause the heat generated by cutting can sig nificantly alter the microstructure. If eutting torches mustbe used, large samples shoul! be taken and subsequent metallography per formed at locations where microstructural al~ teration from the euts has not occurred ‘Similarly, gas samples must be taken in uncontaminated containers that can be sub sequently sealed to prevent material leakage into or out of the container before analysis, ‘Many incorrect conclusions have been drawn because samples were altered during. stm- pling. ‘To prevent this, knowledgeable met- fllurgical and analytical personnel must be involved in sampling, "Any device used for sampling. must con- form to the sumpling protocol. Sampling devices may have enitical dimensions or ‘operational parameters, such as those used or sampling respirable matter, or filters used to separate "dissolved" o particulate frac tions, or in isokinetic sampling. Failure to conten critical dimensions or operational parameters can produce crroneous results Sampling equipment such as pumps. and sieves may require calibration to verify thei performance characteristics at the time of tse. Sampling devices idealy should not be made of or contain the analyte of interest “Therefore, plastic scoops are more suitable ‘when taking metal samples, but metal scoops may be more appropriate for sampling or ‘ganic materials Preservation of the sample may be required unless itis measured immediately ‘Changes in sample composition can result from oxidation, radiation, differential evap ‘oration, 1oss of volatile constituents, ther mally induced degradation. und interaction ‘with other constituents of the sample oF the ‘container. Contamination from airborne dust fan be important, and the introduction of foreign substances can occur, Protection from airborne contamination may require hhandting of samples in ultr-clean rooms (Ref 16). Preservation techniques include fadition of preservatives, low-temperature Storage, enclosure im inert atmospheres, het= metic sealing, and the use of nonactini glass ‘or opaque containers. ‘The concept of holding time can be ap- plied to evaluating preservation techniques Samples preserved in a given say can be analyzed periodically to determine the inter ‘val that occurs before a tolerable smount of, deterioration has taken place. If this is con- ‘sidered the first indication of significant deterioration, it is equivalemt to three stan- ‘dard deviations of the measurement tech: nique used to evaluate it (comresponding to a fonfidence level of 954), If unknown. the Standard deviation of measurement may be ‘evaluated concurrently with the holding time ‘evaluation by duplicate measurement of Subsamples. For some samples, dhe bolding time may be so short as to require field analysis or atleast measurement on a rigid time schedule Discrimination. Decisions should be made that define whether certain constituents ‘of a population should be included or re- jected. A particular material may be for~ ign object (rejected) or & constituent (in- cluded). The model should anticipate such situations and provide the basis or decision, depending on the use to be made ofthe data, Thus, sieves may be specified to separate course objects or materials from fines if the former are believed to be foreign ‘Moisture, If the original population contains water, the model should define if the analytical result should be reported on a dy or “as-received” basis. Moisture [oss oF ‘gain from the time of sampling to analysis also can introduce problems. When differ laboratories treat the question of moisture differently {and sometimes in an unspecified ‘manner), disparity in results ean occur. “The moisture content may not be theoret- ically defined, but based on arbitrary cons crations. Arbitrary drying procedures must be described or documented. Above all, the basis for the analytical result, sueh a ""as- received," or dried by a specific procedure, must be stated whenever the moisture con tent ofa sample isa significant consideration (Ref 17) Because of moisture problems, analytical results on solid materials are frequently re ported on a dry-weight basis. The sample ray be dried before analysis, or the wet sample may be analyzed and corrected for its ‘moisture content, which is measured inde- pendently (Ref 17). The nature of the sample Ima dictate the procedure. Whenever signit- ieant volatile components could be fost, the latter approach may be necessary, Homogenization or blending proce- dures may be required in subsampling and field sampling. Because it may sometimes be dificult or impossible to blend in the field, final homogenization is left to laboratory personnel ‘Liquid samples may require only mixing before analysis. However, if immiscible ‘components of differing densities are present, blending may be required continu- ‘ously during subsampling. The shape of the ‘container and type of mixer may be impor tant in ensuring a proper blending of the ‘constituents. ‘When the sample contains liquid und solid constituents, the phases may be separated fd analyzed separately, in which ease the amount and the composition of each phase present may need to be known. Complete Separation ofthe phases could be a problem, and the definition of dissolved and sus- ‘pended matter may be arbitrary, for exam Ple, based on separability by a filter of spetified porosity. Filtered solids may con- {ain absorbed or occluded liquids that may be tificult to remove. The alternative of ana- Iyzing a suspension could cause even greater problems if any difficulties of maintaining suspendibility are expected, Blending of heterogeneous solids is fre ‘quently performed, Such samples are often mused to obtain small particle sizes that pro- tmoxe improved mixing. Crushers ean range from the familiar mortar and pestle 1 spe: cially designed mulls. They must be made of roncontamsinating materials harder than the ‘materials processed to minimize abrasion and should have chemical resistivity to the sam- piles. The fineness of grinding required will ‘depend on the heterogeneity ofthe sample, but fine grinding is ordinarily preferred, Siew ing may be performed at intermediate stages to separate fines. and coarses that are later reground, When the coarses differ in com position from the fines, each may be ground tsing a different process, then combined 0 compose the analytical sample. "The grinding of soft materials, especially those with appreciable water content, may requite special grinders. Special mills have been developed for such materials as food samples and feeds. Cryogenic grinding and blending may also be used (Ref 18). In such cases, prevention of condensation of atmo- spheric moisture may be a problem. Caking and electrostati clinging of material to parts of prinders and blenders ean problems as wel Blending is often necessary after grinding. Blenders include rifles in which the sample emerges from a container in preset actions Cone and V-blenders have been designed for ‘ining materials. Cones ae often double and {ined ar their bases. Rotation produces switl {ing or tumbling. V-blenders achieve the same result by alternately pouring their contents from one arm to the other as the device is rotated, Forbest results, mixers should not be foverloaded and should be operated slowly {enough to produce alternate interchanges of the contents. Holdup due to caking can de- crease ther efficiency. The number of cycles required rust be determined empirically in the simple process of quartering, the saimple is placed on a sheet of suitable material, and altemate edges are pulled 10 gether 10 achieve mixing. Shoveling from the edges of a cone of material tothe top is sometimes effective se mixing Many sampling enrors can be eliminated ‘or ‘minimized by an appropriate quality- assurance program (Ref 19). Quality conirol tay be achieved by following standard ‘operating procedures and recommended laboratory and measurement practices. Pro- tocols should be developed as part of the planning program to define how each aspect ‘of sampling will be executed. They should specify related calibration procedures and Schedules and provide for controls such as field blanks and for the container cleaning process of personnel should provide 1 thorough knowledge of the elementary Saistics of sampling. Specific taining to the operation concerned ie measurement program, including a thorough review of the protocols to be followed. Critical steps should be ‘identified and explained, and any. special documentation reviewed. random or systematic, result from the sample or from the sampling operation. Population-retated variability has been discussed above. How. ever, unless the entire sample is analyzed, 4 subsample may be required that-may hhave some of the problems encountered in the original considerations. ‘Thus, subsam- pling may be considered as sampling the Sample, Unless proven otherwise, subsam pling error should be assumed to be present Ref 20) ‘Sampling can introduce uncertainties su perimposed on that ofthe sample variability Faulty calibration of sampling equipssent, Introduction of contamination, malfunction ‘of equipment, and differences between ‘equipment used can introduce systematic femrs, and variation of these factors can produce random etrors Rigorous cleaning of equipment between samples may be necessary to minimize error from contamination or carryover problems. Evaluating the effectiveness of cleaning mi be difficult. Containment may contribute 10 contamination, especially in trace analysis. Virgin containers usually eequire cleaning. If conlainers are to be reused, cleaning may reed o be monitored, It may be necessary 10 restrict reuse 10 a certain class of samples and even to restricted levels within such ‘lasses if memory or cross contamination isa possibility Rigid calibration programs and checks may’ be necessary to ensure proper function ing of some sampling equipment, If calibra- tion is performed in the laboratory. periodic Field checks may be required to confirm retention of calibration, especially if the usage is severe. Sample Identification. Definite pro- ‘cedures may be requited to ensure the iden- tity of samples that are analyzed. Well designed labels can document the details of ‘sample location and of the sampling opera- tion. Critical aspects of their transport and storage can also be attested. Breakage-proof ‘containers and tamper-proof closures may be required. A sample custodian may be neces- sary in some cases. There should be no reasonable doubt about the iemity and the integrity of any sample analyzed. Sampling Specific Materials. The general principles discussed above apply 0 the major problems of sampling for chemical ‘analysis, Sources of information on proce- ‘dures for sampling specific materials are cited in Ref 15 and 21 10 25, REFERENCES 1 WA. Youden, The Roles of Statistics in Regulatory Work, J. Assoc. Off. Anal. Chem., Vol 50, 1967, p 1007 2. MG, Natrella, Experimental Statistics, [National Bureau of Standards Handbook ‘1, U.S. Government Printing Office, Wishingion, Aug 1963, p 2-13. 3. Hazardous Waste Monitoring. System, General, Fed. Regist., Vol 45 (No. 98), 1980, p 33075-33127 4. Standard Practices for Sampling: Wae ter,” ASTM D 3370, Vol 11.01, An- ‘ual Book of ASTM Standards, ASTM, Philadelphia, 1984, p 85-08 “Standard. Practice for Manual Sam- pling of Petroleum and Petroleum Prod- wets.” ASTM D 4057, Vol 05.03, An 8 Sampling / 17 ‘nual Book of ASTM Standards, ASTM, iladelphia, 1984, p 663-686 ‘Standard Practice for Sampling Indus- trial Chemicals,” ASTM E300, Vol 15.08, Annual’ Boot of ASTM Stan dards, ASTM, Philadelphia, 1984, p 410-433 C.O. Ingamells and P. Switzer, A Pro posed Sampling Constant for Use in Geochemical Analysis, Talanta, Vol 20, 1973, p 547 C0. Ingamells, New Approaches 10 ‘Geochemical Analysis and. Sampling, Talanta, Vol 21, 1974, p 141 CO. Ingamelis, Derivation of the pling Constant Equation, Talanta, Vol 23, 1976, p 263 1, Visman, A General Sampling, The- ony, Mat. Res. Stand., Nov, 1969, p 8 GW. Snedecor and’ W.G. Cochran, Statistical Methods, Th ed. lowa State University Press, 1980, p 243 HLA. Laitinen and W.E. Harris, Chem fcal Analysis, McGraw-Hill, 1975, p. 576 C.A, Bennett and N.L. Franklin, Stats tical Analysis in Chemistry and the Chemical Industry John Wiley & Sons, 1954, p 62, 482 LK. Taylor, Quality Assurance of Chemical Measurements, Anal. Chem.. Vor 83 198tsp 13888-15958 C.A. Bicking, in Treatise on Analytical Chemistry, 2nd ed. Vol 1, LM. Kolt- hoff and PJ. Elving, Ed., John Wiley & Sons, 1979, p 299-359 TER. Moody’, NBS Clean Laboratories for ‘Trace Elemental Analysis, Anu! Chem., Nol 54, 1982, p 1358A-1376A Standard Practice for Preparation of Sediment Sumples for Chemical Analy Sis." D 3976, Annual Book of ASTM Standards, ASTM, Philadelphia, 1984, 1 673:676 R. Zeisler, LK. Langland, and $.H. Harrison, Chemical Homogenization of Biological Tissues, Anal. Chem, Vol 55, 1983, p 2431 LK. Taylor, Principles of Quality As: surance, NBSIR. 85-3105, National Bu: reau of Standards, Gaithersburg, MD. 1985 G.E.F. Lundell and J.1. Hoffman, Out lines of Methods of Chemical Analysis, John Wiley & Sons, 1938 BG. Kratochvil and J.K. Taylor, Survey of the Reveat Literature on Sam- pling for Chemical Analysis," NBS Technical Note 1153, National Bureau of Standards, Gaithersburg, MD, 1982 B.G. Kratochvil, D, Wallace, and J.K Taylor, Sampling for Chemical Analy. sis, Anal. Chem, Rev., Vol 56, 1984, p TR 18 / Sampling “General Rules for Methods of Sam- pling Bulk Materials,” Japanese Indus- teil Standard (JIS) M1800-1973, Japa- nese Standards Association, Tokyo, 23. “Methods for Sampling Chemical 24 Products,” Pars 1, 2, 3, 4, BS 5309, British Standards Institution, London, 1976 1975 (in English) 25. Subject Index: Alphanumeric List, Vol 00.01, Annual Book of ASTM: Stan dards, ASTM, 1984, p 1-726 Optical and X-Ray Spectroscopy Optical Emission Spectroscopy Paul B. Farnsworth, Department of Chemistry, Brigham Young University General Uses + Quantitative determination of major end troce elemental constituents in various sample types + Qualitative elemenial analysis Examples of Applications + Ropid determinotion of concentrations of alloying elements in steels and other alloys + Elemental analysis of geological materials + Determination of trace impurity concentrations in semiconductor materials + Wear metals analysis in oils + Determination of eikali end alkaline earth concentrations in aqueous somples + Determination of calcium in cement Samples + Form: Condveting solids (ares, sparks, glow discharges), powders (arcs), and solutions (flames) + Size: Depends on specific technique; from ‘approximately 10”* g to several grams + Preperation: Machining or grinding (metals), dissolution (for flames), and digestion or ashing {orgonic samples) Limitations + Some elements are dificult or impossible to determine, such as nitrogen, oxygen, hydrogen, halogens, and noble gases + Sample form must be compatible with specific technique + All methods provide mat Estimated Analysis Time + 30 5 to several hours, depending on sample preparation requirements Capabilities of Related Techniques + X-ray fluorescence: Bulk ond minor constituent elemental analysis; requires sophisticated date reduction for quantitative analysis; not useful for light elements (atomic number = 9) + Inductively coupled plasmo emission spectroscopy: Rapid quantitative elemental analysis with ports pet billion detection limits; samples must be in solution; not useful for hydrogen, nitrogen, oxygen, halides, and noble gases + Direct-current plasma emission spectroscopy: Similar in performance 10 inductively coupled plasma emission spectroscopy + Atomic absorption spectroscopy: Favorable sensitivity ond precision for most elements; single- channel technique; inefficient for multielement analysis dependent responses Introduction Optical emission spectroscopic methods originated in experiments performed in the ‘mid-1800, yet they remain some of the most tuseful and exible means of ‘performing elemental analysis. Free atoms, when placed fn an energetic environment, emit light at series of narrow wavelength intervals. These intervals, termed emission lines, form a patter, the emission spectrum, that is, char- acteristic of the atom producing it. The Inonsities of the lines are usually propor. tional to the number of atoms producing them. The presence of an element in a sample is indicated by the presence in light from the excitation source of one or more of its characteristic lines. The concentration of that element ean be determined by measuring Tine intensities, Thus, the characteristic emission spectrum forms the basis for qual itative elemental analysis, and the measure: ‘ment of intensities of the emission lines forms the basis of quantitative elemental analysis, ‘The characteristic spectrum an atom pro- duces reflects the electronic structure ofthe atom. Changes in the energy of the valence for outer shell electrons result in the atomic Fines used in emission spectroscopy. Each atom has a ground state in which all ofits ‘electrons occupy positions of minimum po- tential energy. As an atom absorbs energy, ‘one oF more of the outer electrons may be Promoted to higher energies, producing an ‘excited state. The energy of an atomic state isa function ofthe energies ofthe individual electrons and of energy changes resulting from interactions among the electrons. Each ‘possible combination of electron configurs- tions produces a spectroscopic term. that deserites the state of the atom.