Suggested Procedure for Use of the Hanawalt Search Manual “The search manual is organized into “groups” and “sub-groups”. Two lines from the table of “d” values and intensities of the diffraction pattern serve to locate the “entry” of the pattern in the manual. The d value of the strongest line of the pattern determines the group into which the entry falls, the d value of the second strongest line de- termines the sub-group, that is, the location within the group. The entry also includes the next six strongest lines of the pattern in order of de- creasing intensities, ‘Thus, to identify an unknown, we choose the first and second strongest lines of its diffraction pattern as the line-pair with which to look for a ‘matching entry in the search manual. Ifthe other six lines of such a qualifying entry also match lines in the unknown pattern, the identification is prob- ably correct. The final step in the procedure is to confirm the identification by going to the Powder Diffraction File to check the complete pattern. Example I Example I (see Figure 1) tabulates the d values and intensities of the diffraction pattern of an un- known material. We choose the strongest line 3.34 and the second strongest line 4.25 as the line-pair with which to enter the search manual. The line 3.34 (01 since it is necessary to allow for ex- perimental error) lies in group 3.39-3.32. The second strongest line, 4.25 + .02, determines the sub-group, i.e., where we look within the main group. We'see in Figure 2 (portions of pages 393 and 394 in the search manual) BH eatis)vhich satisfy our ine-pair 3.34 = = 02. On examining each of these cight entries, we find only one, SiO,, PDF No. 33-1161, for which the re- maining six lines are in good agreement with lines in our unknown pattern, We therefore refer to the complete pattern of PDF No. 33-1161 and find that the pattern accounts forall ofthe lines of our unknown (see Figure 3). We can conclude that our unknown is composed of a single phase, SiO, (quartz). If any diffraction lines were present in the unknown which were not accounted for by the standard pattern of SiO2, it would mean that an- other phase (or phases) was also present. Figure 1 Example 1 Diffraction data of unknownFigure 2 Example | se ame 3m. esas Ge) eal Ee See it Be 2 a aes ser ae ome ns ERI no, momen m3 aa Sead, ¢ Se ecceen es eee 2 KANO a eee ; Sooo meanest i See hee Eg 5 SEEK no 3.39 - 3.32 (+.02) Me Wik kk Beh. ie St Gard, a 2 Bitow ik ik Bee ie iS ee Bedperee a ae i we ee ie us, oie uh He Py 3 am Bose. ite ER SERS sous 3a $e, Belo ie a teste 1S ue Uk are ie i ie BS = er 17 May 20h” Bue on Me ue ie Reh, cae ate ie im ig SMa, vs i i Ei He is ia Ree 2 PE TR Reosiba tan 355 SR) a maior tanh thy ue a ert ie Te i Se ee 2 3m 30h Ua, ad He ih TR ton, ee uh i ae oy 1 8h HE US FR Beto, ee neFigure 3 Example 1 33-1161 Fe G i 288 568 | ev i 8 0, 7 a 2 i 2 Bean cont ct gi HEE BBS ; E ) ) , J > : p b > ; o o $ 3 2 ° : - . 2 a apa He ies Bay PE om 23) a lie = sors ngs || |B) 2Example I ‘The solution of Example I was simple because it was a single phase. In the more general case in which the pattern is that of a mixture of two or more phases, the manual solution can be tedious, and unless carried out systematically, individual mistakes are likely. It will be found helpful to use a “form” on which a record can be kept of the sequence of steps taken in the process of the solu- tion, thereby avoiding both omissions and repeti- tions. Use of such a “form” is illustrated in the solution of Example II. Fhis form was designed by Dr. Hanawalt, and is referred to as the ‘Hanawait Work Form’ The tabulation of d and I values of the “unknown” pattern is given in Figure 4. We begin by listing the d and I data on the Hanawalt Work Form as shown in Figure 5. For high quali data an allowance for errors of = .O1 is sufficient ‘over most of the range of d values encountered in this particular problem, though in the region of $ A, it is more conservative to allow + .02, ‘We choose from the table of diffraction data pairs of lines with which to enter the search ran ual. We then examine the remainder of the eight lines of any qualifying entry to check whether these lines also match lines of the unknown, We begin with the strongest line available end enter the search manual with line-pairs chosen in order of decreasing intensity until 2 qualifying entry is found. The first step for Example II is to enter the search manual with the line-pair 3.41 + .01 ~ 5.00 .02. We find in group 3.49 ~ 3.40 and subgroup 5.00 .02, four qualifying entries! On examination of these four entries, all the lines of entry K,PtF,, File No. 7-236 are found to check with reasonable exactness lines contained in the 4, List of unknown Example II: When we check the complete pattern of PDF No. 7-236, we find eleven lines of the unknown are accounted for and we can conclude that the phase K3PtF is present. A record of this search is shown in Figure 5, which tabulates the work we did to identify the valid en- try. It requires work each time we enter the man- ual with a line-pair to locate qualifying entries. It requires further work to check all of the lines of each entry against lines of the unknown. The Fie 4 Example I 1 a Ss] n 5.00 % 490 u aol n 401 2 378 0 309 20 3208, 2 so 5 Boll % 007 0 2501 2 2.899 5 2839 13 2787 " a0 ® 26s 2B 2361 | rn 2sit a 2439 | 7 235 i 5 2.06 9 2384 7 ae . 6 236 “ 2a. + 2 2186 é 2130 24 2036 7 2030 8 1997 7 1960 24 1936 i ae? 6 rete a re is 1809 2 1787 6 64 6 1359 2B 146search work is measured by the number of line- pairs used plus the number of entries examined. ‘The next step is to compare the intensities of K,PtF, with those of the unknown pattern and check off those in the unknown which are ade- quately accounted for, remembering that sities are not nearly so exactly measured as are d values. This step is shown in Figure 6 and we can see that the strong line at 2.449 is only about half accounted for by the 2.459 line of K,PtF, This is noted by showing a remainder of 33 for line 2.449. Continuing the solution of the unknown pat- tern, we begin with the strongest of the unac- counted-for lines (see in Figure 6). This would be line-pair 3.04 .01—5.12 = .02. Turing to group 3.04 — 3.00 and sub-group 5.12 = .02, we find two entries only one of which qualifies (COHCI, PDE No. 18-259). On examining the remaining, lines of this entry, we find satisfactory agreement with lines of the unknown. Checking further with the complete pattern of PDF No. 18-259 con- vinees us that C4OHCI is another component of unknown Example II. In Figure 7, the T and d columns show the lines accounted for by the first two components wh have been identified. ‘The strongest of the unac- counted for lines remaining is 2.673. Using line- pair 2.67 + .01—4.90 * .02 to enter the search manual, we find in group 2.69 ~ 2.65 eight qualifying entries. Examination of the other six lines of each of these eight entries quickly elimi- nates four of them. ‘The other four are so similar that its necessary to check the complete File pat- terns in order to make the choice of Caj»Al,,Oss, PDF No. 9-413. When the complete pattern of PDE No. 9-413 is listed in Figure 8, we see twelve more lines of the unknown are accounted for. (Note that line 2.449 of the unknown was not completely accounted for by line 2.45 of PDF No. 7-236 and that line 2.561 was not completely ac- counted for by line 2.56 of PDF No. 18-259.) Figure 8 shows in the I and d columns the re- ‘maining lines we have to work with to continue the search. The strongest of these lines is 2.839. ‘We use the line-pair 2.84 + .01 - 4.01 02and ook in group 2.84 — 2.80 and sub-group 4.01 = 02. We find twenty qualifying entries but only ‘one with other lines which are matches with our unknown, When we list the lines of the complete pattern of NaMnF,, PDF No. 18-1224, we see that all of the lines of unknown Example Il are now satisfactorily matched, We can conclude that the material represented by the diffraction data of Figure 4 is a mixture of the four phases, K,PtF,, CAOHCI, Ca,,Al, Oxy and NaMnF. In Figure 8, is seen that the total work of this manual search is measured by 4 line-pairs plus 34 examinations. I the pattern of the unknown were of lower qual- ity, the + error allowance would have to be larger, and the “L-P” plus “e” total would be cor- respondingly greater (see “Quality of Standard Patterns” for data on + Ad). The above search procedure made use of powder diffraction data only, but if other informa- tion about the unknown sample is available, use should be made of it. Such information might in- clude chemical analysis from X-ray fluorescence, ‘or preconceived possible solutions based on the known history of the sample. If the analyst can make an “educated guess” about the unknown, he should go to the Alphabetical Index and check di- rectly with the three strongest lines given there. Even if the analyst has only partial information about the unknown, for example, what elements are present or not present, this can be very helpful in using the search manual since it is much easier for most people to check a name than a series of numbers. One uses the strong lines of the pattern to locate the correct region in the search manual and then checks entries on the basis of this chem- ical information.aa Arr we. Figure 5 Example I Le ve. 5.00 4.62 3.40 0 2.894 2501, 2459 2.20, 2.10, 1,890, 1.807, T3 Ne line pais (CP) No. of entries (e)Figure 6 Example I 2am wae 14 ee eR ou clone Lr es we immer T]2 [5a ST 5.00 J 1] 4 | 5.01.6 76 4.90 wo 461 4.62 T1401 Ta SarTE 3053400 | | |3.405 , 0 3.208 173180 3.18, as 3.041 v | |3.03%06 36 —~3.007 aT 2501 2.89% 22 (2.889 752839 152.787 172710 270s, = 802673 232361 256, Mg 2511 2.501, wou 249 2.456 T2435 152.406 9 2384 7 2348 | 2326 2.39 4 2a7 22,q 322.186 6 2.50 Be 2.056 2.10 | 72.080 | 1997 7 11990 1.99% 2411936 Br 1887 1.890,; 61846 Zea Ty 3510 1.809 1.807, 2 1787 6 176 61759 Bis T730, - _ No-one pais LP) 1 r No.of entes (@) 4 zFigure 7 Example I rae mas oa Lee Rr Lee CHONG LP € CaaluOy LP ue Slice 1 | 4 |5.01 1] 8 [4.8900 4.62q I S988885 J] |3-4000 | 3.208 3.20445 3.180 3.18.9 3.041 J.) N38 3.007 3.000,5 2901 2.89 2.889 2839 2.787 2710 27:5 2.673 J | | 2.68000 2.561 2.56 ,9 21556, 2511 2501, 2.449 245, 2.45055 2.435 2.406 2.384 2348 2326 2.30 2.207 2.20, 2186 2.190 2.150 2.096 2.105 2.050 2.08445 1997 1.990 1.992 ekkes|aanks)kseks|=kesk) _ 1,940, 1.890, £38 1,850, : 1.830, 1.807, ae eae8 Waadkklok2Wa] Wowk Roe 3 1.75055 No, ofline pais (UP) | T z I Nov of entries () 4 z 3 siiSCPFSESCSCSSseeeseseseeeevseeseseeee ee NNN ee Figure 8 Example Il sa 29 oan wim 4 tre RR LP © CHONG) LP e ConlliOy LP e Masta, 5.12 1]? [Ste 5.00 | 1) 4 |5.01, 4.90 1] 8 |4.8%69 4.61 4.62 401 1 | 20}4.00;00 378 RI, 3.208, 3.180 318.9 3.03500 3.007 3.00055 2.901 2.8949 2.889 2.88, 2.839 vio [tastes 2.787 Bi 270 20, 2613 J) | 2.680, 2.561 2.56, 2.556, 2.501, 2.449 2.4556 2.45059 Rok of RRA BABAR RLRES 2 RREE! z 235 Tay 20s, 2.384 2386 2348 23509 23326 2.359 5 2207 iy 2.186 2.190 2.150 2.182, 2.096 2.1039 2.050 2.05459 1997 2.0005 1,992 1.936 1.94055 1.887 1,890, 1.846 1.8505 1829 T8305 10 1.809 1.807, Yoobk&MSRAS)ARARH RNS 2 1746 T7505 Nordine pas CP) 1 i T i No, of entries (@) a z 3 20]