BAB IIT 2.1. Pendahuluan Setelah uraian singkat mengenai fisika sinaz x dan geonetri kristal, maka kini ke dua hal tersebut akan di gabung dan akan dibahas mengenai gejala difraksi sina X, yang merupakan antarakei dari dua hal tersebut. telah lama ahlimineralogi dan kristalografi mampu mengidentifikasi kristal lewat sudut antarmuka, anali- sa kimia, dan penentuan sifat fisiknya. Pula ada duga an, bahwa sinar X yang merupakan gelombang elektromak~ retik, akan menunjukkan gejala difraksi bila sinar ter sebut jatuh pada benda yang jarak antar-atomnya kira~ kira sama dengan panjang gelombang sinar tersebut. Pada tahun 1912 Laue melakukan percobaan berdasar- kan hipotesanya sebagai berikut Bila kristal terdir{ dart atom yang berjarak secara teratur, maka atom-atom tersebut dapat berfungsi seba~ gai pusat penghambur untuk sinar x, dan bila sinar x merupakan gelombang elektromaknetik dengan panjang ge- lombang yang kira-kira sama dengan jarak antar-atom dalam Kristal, maka sinar x tersebut dapat didifrakst oleh Kristal. : Dua ahli fisika, yaitu W.l. Bragg dan puteranya W.b. Bragg, Kemudian menganalisa percobaan Laue dan me 2728 hyusun bentuk matemacik untuk menerangkan struktur kris= ear. bila sinar X jatuh pada kisi Kristal, maka sinar akan didifrakst, artinya sinar yany sefasa akan @iper- kuat, yang tidak saling moniadakan (gb. 16). Garis ho- risontal menggambarkan bidang-bidang dalam kristal yang terpisah oleh jarak 4. idang ABC adalah tegaklurus pa~ paralel, dan bidang EMW tegakiurus pada berkas yang @t- pantulkan. Bila sudut macuk ¢ diubah, refieksi hanya a— kan didapat bila ge~ lombang sefasa pada bidang LMN, areinya bila perbedaan dalam Jarak antara bidang ABC dan INN, yang ai ukur sepanjang sinar OP 17 SARSEARANES SIGUE, yang direfiekat dart pA raiadiaiai/e'y, panjang gelombang. Fs-+ sc =k G-1 Karena sin © = Ps/a = c/a, 2a'sin © = na -2) Persamaan ini adalah hukum Bragg yang memberikan hubung— an antara jarak antara Bidang dalam kristal dan sudut yang radiaci refleksinya menunjukkan intensitas maksimimuntuk panjang gelombang tertentu, x ; yaitu semua ai- nar X yang sefasa. Bila i lebih panjang dari 2a, tak ada penyelesaian untuk n dan tak’ada difraket. * Refleksi yang sesuai dengan n = 1 disebut refick- si orde satu,n = 2 adalah refieksi orde 2, dan seterus- nya. Makin meningkat ordenya makin bosar sudutnya. Persancan (3-2) dapat diculis sebagai A= 2a sina asaya o-3) Secara umun, refleksi orde a dari bidang (hkl) dengan jarak a! dapat dianggap sebagai reflekei orde 1 dari Bidang (nh nk nl) dengan jarak d= a'/n. Konvensi ing sesuat dengan definis{ indeks Miller, karena (nh nk nl) adalah indeks Miller dari bidang yang paralel denga: bidang (hkL) tetapi dengan jarak 1/n- 3.3. Spektroskopi sinar x Secara eksperimen, hukum Bragg dapat digunakan me- nurut dua cara. Dengan menggunakan sinar x dari panjang gelombang A dan menentukan 9 , maka dapat ditentukan jarak @ dari berbagai bidang dalam kristal: ini merupa- yan analiea etruktur. cara lain islah menggunakan suatu kristal dengan bidang yang diketahui jarak d nya, ditentukan 6 , dan kemudian Panjang gelombang 4 dari radiasi yang digunakan dapat Acari: ini adalah spekeroskopi sinar x.Sinar X dari tabung T jatuh pada Kristal C yang dapat Ailetakkua pada sudut tertentu terhadap sinar datang. 0 = alat pengu~ kur fntensitas/alat Aiukur dan dinitung 2e- Gb. 18. Spekerometer ele ngan hukum Bragg. Kris- tal harus dipoteng cedemikian rupa sehinggs menghssil- kan bidang refleksi dengan d yang diketehui paralel terhadap permukaan. Penentuan cara ini adalah relacif dan ketelitian ser- gantung pada ketelitian mendapatkan jarak antar-bidang dalam keistal. Untuk Kristal kubus Jarak ini didapat secara ter- eendiri daré repat massa. Untuk setiap keistel + berat atom-atom dalam sel satuan © A (5-4) As jumiah berate atom dari atom-atom dalam sel satuan; 9 rapat masea (g/en9); N = Bilangan Avogadro; v = vo- jum sel satuan. Untuk NaCl, se gatuan mengandung 4 atom Na dan 4 atom C1 per sel satuan, seningga EA = 4 (berat atom Na) + 4(berat atom C1). Bila nilai int @isubstitusikan dalam pers. (2-4), bersa- ma~sama dengan N bilangan Avogadro, dan rapat massa,.ma- ka volum sel satuan V dapat dicari: Karena NaCl berupa kubus, parameter kisi a sama dengan akar V. Dari nilea1 a ini dan dari persamaan (2-3), jarak dari setiap kum- palan bidang dapat dicari. Untuk garam dapur ditemskan 4+ 2,814 8 untuk Bidang (200) atau 2814,00 xu satuan x), yaitu suacu satuan baru yang hampix sama dengan 0,001 8. Selanjutnya Siegbann menganjurkan kalsit se- 5 XU untuk biaang (200). Ke~ baat standar, yatta 3029, mudian didefinisikan satuan KX (kilo x) + Lux = Aszak bidang, Goo) dalam kalsit (3-5) Lx = 1,00202 R21 R Gs) Parameter kisi Kristal untuk selanjutnya dinyatakan aa- aan Ketelitien dalam menyatakan parameter kristal adalah an tara lain dengan momberikan panjang gelombang radiasi yang @igunakan. Dalam hal ini radiasi yang digunakan aaalen garis Khas Acuexe 4) = 2+54052 R. Ke 3.4, Arah pigraksi Yang menentukan arsh difraks{ atau sudut 9 dalam keistal, alah efstem kristal dan parameter kisinya, atau secara singkat, arah difrakei ditentukan oleh ben- oneuk keistal kubus: A = 2a sine aan) 2g 4 22)32 Dengan menggabungkan Kedua persamaan ini, didapat 2 a2. sin? 9 = cn? +e? 427), on Persamaan ind meramalkan untuk panjang gelombang \ ter- tentu dan kristal kubus tertentu dengan ukuran sel sa~ tuan a, semua sudut Bragg yang memungkinkan difraksi berlangsung dari bidang (hkl). Untuk bidang (110) mi- salaya, persamaan (3-7) menjadi seg 7 Se Dengan cara yang sama data untuk Kristal lain dapat ai- hitung. Ada tiga metoda difraksi yang didasarkan atas hu- kum nags, 4 = 24 sine Metoga Laue variabel tertente Metoda krista tertentu vartabel (se- berputse Bagiand Metoda bubuk tertentu variabe Metoda Laue adalah cara difraksi yang pertama. Radiasi kontinu dijatunken pada kristal tunggal. sudut Brags 0 tertentu untuk setiap kumpulan bidang dari kristal. Setiap berkas difraksi mempunyai 1 berbeda-beda. Ada dua variasi dari metoda Lave, yaitu cara transmisi dancara refleksi balik (Cb. 19). Dalam masing-masing me- toda, film adalah datar dan diletakkan tegaklurus ter- Gb. 19. wecoda Laue (a) transmiss dan Vb) weclakes Baaike hadap berkas sinar yang masuk. Dalam meteda tranemiet, ehingga dapat film @iletakkan ai belakang kristal, merekam berkas yang didifrakei dalam arah maju. Dalam netoda refleksi balik film diletakkan antara kristal dan sunber sinar x, berkas einar masuk lewat lubang dalam fitm, dan berkas yang €i aifraksi @irekam dalam arsh balix. batan kedua cara, berkas difrake{ membentuk kumpulan bineik-bintik pada iim. Kumpulan bintik ini disepse pola. Lewat bintik-bintik int dapat digambarkan garis~ garis berbentuk kurva tertentu. Untuk pola transmisi bentuknya elips atau hiperbola, sedangkan untuk cara refleksi balik adalah hiperbola. Cara Laue aipakat un- tuk penentuan orientasi kéistal dan penentuan penyim- Pangan dari keteraturan kristal. Netoda kristal berputar ~ dalam metoda ini krista tunggalnya dipasang eedemikian rupa sehingga salan satu sumbu kristalografinya tagaklurus terhadap borkss34 sinar X. Kristal berputar, film sinar x dipasang sekeli- Ling kristal. Tidak semua nilai dari 6 teramati dan ti- tik-titik yang teramati terletak pada garis-garis hori- zontal. Penggunaan metoda ini adalah untuk penentuan struktur kristal yang tak diketahut. Metoda bubuk - Kristal zat padat dibuat bubuk dan pa~ denya dijatuhi berkas sinar x yang monokhromatik. Seti- ap partikel dari: bubuk terorientasi acak terhadap ber- kas yang masuk. Secara kebetulan, beberapa partikel é: pat terorientasi tepat sehingga bidang (100) misalnya, dapat merefieksi sinar yang masuk. Partikel lain dapat terorientasi tepat untuk refleks{ (110), dan sebagai- nya. Hasilnya ialah bahwa setiap kumpulan bidang kisi dapat direfleksi. Kita tinjau suatu refleksi hkl yang khusus. Bebe rapa partikel Gari bubuk secara kebetulan dapat terori~ fentasi sedemikian sehingga bidang (hkl) dapat menbuat sudut Bragg untuk refleksi. Gb. 20 menunjukkan bidang ini dan terjadinya berkas yang aidifraksi. Bila bi- dang ink dirotasi melalui berkas masuk sebagai sumbu fan dengan menjaga agar @ tetap, maka berkas yang di- refleksi akan menbentuk kerucut seperti yang ditunjuk- kan pada Gb. 20 (b).as ob. 20, Pembentukan kerucut difraksi radiasi dalam metoda bubuk. Gb. 21 menunjukkan empat kerucut dan juga menggambar~ kan terjadinya garis garis pada film bila film dilurus- kan. Metoda ini juga sering disebut metoda Deby Scherrer. Dalam hal ini, spesimen diletakkan di tengah tengah kamera dan filmnya diletakkan di sekelilingnya. Gb, 22 menunjukxan pola bubuk Debye Scherrer untuk struktur berturut-turut (FCC1, (BCC) dan (HCB). Metoda bubuk umumnya digunakan untuk penentuan paraneter kisi, identifikasi fasa (apakah berupa cam= puran, aliasi, polifasa), hasil korosi, bata tahan api dan batuan-batuan.36 Gb. 21. Metoda bubuk Debye Scherrer; (a) hu bungan film terhadap spesinen dan si- nar masuk; (b] kenampakan film bila diletakkan datar, Sebagai kesimpulan, pada difrektoneter digunakan sinar X dengan A tertentu untuk penentuan jarak antar- bidang kisi kristal yang tak diketahui. Di sini selalu digunakan radiasi monokhromatik. Pada spektroneter sinar X digunakan kristal yang dike~ tehui d nya, dan alat tersebut digunakan untuk penentu- an} dari sinar x.37 Gb. 22, Pola bubuk Debye~Scherrer: (a) tembaga (FCC), (b) wolfran (BCC), dan (c) seng (HCP). Radiasi Cu dengan filter, dia- meter kamera = 5,73 cn.49 5.2. Cara Mengindeké Kristal Kubus Untuk sistem kubus berlaku + sin? 6 sino Sara erat d = (3-2) wee ed 2 2 s =n? 4? 41? —. narus selalu bilangan bulat. palam contoh ini digunakan radiasi Cu K, dan ditemukan 8 garis Aifraksi. Nilad sin? terdapat pada kolom 2. Bilangan bulat = dicari sehingga pembagiannya terhadap bilangan é{ kolom 2 menghasilkan bilangan ai kolom 4. Kolom 5 merupakan parameter kisi yang dihitung untuk setiap garis. Kolom 6 merupakan indeks Miller dari se~ tiap garis. Kesimpulan: zat adalah Cu kubus dengan a = 3,62 R. vabel S-1 L 2 4 5 6 z Baris sin’e 5 cen er 4a vt 1 0,180 3 0,0466 3,57 aaa 2 0,185 4 0.0463 3,58 200 3 0,369 8 0.0462 3,59 220 4 0,503 rey 0,0457 3,62 312. 5 0,548 12 0,0456 = 3,61 222 6 0,726 1s 0.0454 = 3,62 400 7 0,862 19 09,0453 3,62 331, e 0,905 20 0.0453 3,62 420so Kisi Bravais dari spesimen dapat pula ditentukan dengan mengamati garis mana yang ada dan yang tak ada. bari kolom 6 tabel $-1 tampak bahwa semua garis yang mempunyai indeks campuran ganjil dan genap, seperti 100, 110, deb. tak ada dalam pola. Untuk ini harus diperhatikan déret nilai s dari kisi kubus yang unum terdapat: Kubus sedechana : 1,2,3A,5;6,8,9,10,11,12,13 14,16, Kubus pusat tubuh + 2,4,6,8,10,12,14,16, . Kubus pusat maka + 3,4,8,12,12,/16, 121074 kubus inten #°3,8,Al 266% 005 Keterangan yang sama ditunjukkan secara grafik pada Gb. 25. Dari keterengan ini tampak bahwa kisi Bravais dari contoh tersebut di atas adalah tembaga FCC (kubus pusat muka). fat dengan pola kubus biasanya mudah dikenal dari yang non kubus, karena yang non kubus mengandung lebih banyak garis. Bila ditinjau kisi Braveis-nya, maka struktur kubus sederhana dan kubus pusat tubuh mudah di- bedakan, karena keteraturan garis-garisnya. Kekhasan dari struktur FCC adalah bahwa ada pasangan garis ai- ikuti oleh garis tunggal, diikuti lagi oleh sepasang garis, garis tunegal lagi, dan seterusnya.SL Pongindeksan pola dari Kristal kubus ies ae ceteris Somunan ae F a Le] | | Jarak pala file atou kortae geafike LTT Gb. 25. Pola aifraksi hitungan untuk ber- bagai kisi.For a primitive cubic class, all integral values of the indices h, k, and / are possible. AkI 100 110 11 200 210 21 220 300, 221 in? (@) = sin’ (@) 7 net ket a a 1 2 3 4 5 6 8 9 (IP + +P) Note that the value 7 is missing in the sequence, since there is no possible integral value that h? + k?+ /?=7 If the intensity of diffraction of the pattern is plotted against sin2(@), one would obtain equally spaced lines with the 7%, 15%, 23", etc. missing. -it is easy to identify a primitive cubic system and (by inspection) assign Indices to each of the reflections. -the cubic unit cell dimension a can be obtained from any of the indexed reflections. -since the experimental error is relatively constant, the reflection with the largest Bragg angle is chosen to minimize error in the lattice parameter calculation (or perform least squares on all reflections).28 =26.52° 37.85° e000 2 61.70° 5 sono z 68.35° = 46.81° 86.94) 54.60° zane 80.88° r r r r r r r Diffractometer equipped with a copper X-ray source. -copper sources emit X-rays with a wavelength, 4 = 1.5406 A.Absences due to lattice centering The pattern of observed lines for the two other cubic crystalline systems, body-centered and face-centered is different from primitive. eThe differences arise because the centering leads to destructive interference for some reflections and the missing reflections are known as systematic absences. 4 The reflection from A a A the 200 plane is | exactly out of phase "le with the 100 Pam) reflection and 200 pl F two f destructive planes of two face centered unit cells interference occurs and no 100 reflection \\_ is observed. -furthermore, in If ais the cell dimension, the order for a reflection planes have a to be observed for spacing a/2. fec, the AkI indices The 100 refleion kom an Feented abe let mst be all odd or all even.A similar analysis of the bec system would find that the sum of the reflections must be even (h+K+/ = 2n) -these absences apply to all crystal systems, not just cubic. Allowed list of h? + k? + /? for cubic crystals Forbiddennumbers Primitive, P 1 2 3 4 10 u 12 3 “4 Face Centered, u 2 Body Certere: T_ Corresponding iki 2 100 110 m 200 210 2 220 300 310 ai 400 If the observed sin?(@) follows in a ratio of 1, 2,3,4,5,6, 8, then the unit cell is likely primitive cubic. -the common factor is 27/4a?Intensity Indexing Example - srTiOz Int, 25000 ® 200004 . = 0004 govt 100005 ‘ 3 8 8 oft 4 1. | i T T T T T T 20 30 40 50 60 70 80 20 (°) Diffractometer equipped with a copper X-ray source. -copper sources emit X-rays with a wavelength, & = 1.5406 A.Look for a common factor, Z, which can be divided into each value to give an integer quotient. Let Z = Using Bragg’s Law, A = 2d,,Sin@ 0.0654 in this example. Pak? | 20) | 00 aa) Pak? | 20@ | e@ [am | awe | auZ H zn | uss | 3910 1 | 27 | m3 | as | ows | 1 2 zeso | 1028 | 2.705 2 [3250 | 1928 | 270s | 01008 | 2 3 zoo | 1995 | 2257 | x90 | 1995 | 2257 | o1m9 | 3 1 wat_| 23m | 195s + [en _[ 2300 | 1985 | ovis | a 5 seat | anaa | _aa9 5 | sea | 200 | ur | ova | 5 § 5 2835 | 1506 6 26 | 159 | osm | 6 7 was | 1382 7 sae | ieee | osm | 8 8 aazs | 130s 8 | reas | 02s | 1am | oso | 9 9 vast | 1236 9 | zor | sast | 12% | ons | 10 10 wav | tars 10 | s160 | som | uo | ono | Note that in this example, we obtain all integers and all the quotients are integers that indicate a primitive unit cell.Assignment of Miller indices Peak # 20(°) 6) a(Ay Wd? bh} kf Lae [us | soo [oom] 1 [a pelo ase [isa | ares [orm [2 [pa fo [ww [ees [oar [ows [spa pe fa + [ea [a [ae [oz | pepe po = pea fan pane [osm [spe [1 fo [Lam [ssa [ase [osm fe pepe pa 7 [ors [ses Dis [osm |» [ele fo 3 | rm | a2 fiom | osor fo fs fee 7 [aa [wa pie [osm | ps pa po | sso [wow [ome pone [om [spe The (300) and (221) peaks fall at the same location, both give h? 2asin(6) +K+P=9, The lattice parameter, a, is 3.91 ASystematic absences Symmetry element ‘Affected reflection Condition for reflection to be present Primitive lattice P kd none Body-centered lattice I ki h+k+/=even Face-centered latice A kd k+/=even B hkd h+ leven c hkl h+k=even Face-centered latice F kd hk Lall odd or even twofold screw, 2, along a hoo h=even fourfold screw, 4, along a hoo h=even sixfold screw, 6, along c oo! Idivisible by 3 threefold screw, 3,, 3, along ¢ oo! Idivisible by 3 sixfold screw, 6,, 6, along 2 hoo h divisible by 4 fourfold screw, 4,4; along a hoo h divisible by 4 sixfold screw, 6;, 65 along ¢ oo! Idivisible by 6 Glide plane perpendicular to b Translation al2 (a glide) hol h=even Translation c/2 (c glide) hol I= even bi2 + cl2 (n glide) hol h+l=even bl4 + cl4 (d glide) hol h + | divisible by 4Systematic absences due to screw axes and glide planes a -Translational symmetry elements lead to a set of systematic absences in the A&/ reflections. -The effect of a glide plane Is to introduce a plane of atoms halfway along the unit cell in the direction of the glide.Pattern Indexing using Computer Software Programs Biriesicaer ‘Sets Help| Datafed chexcraup Dieu Tiear50 alec vane Fou DICVOLO6 casi ent 1T013 CRYSFIRE MeMaille .. and several others. FullProf -Treor-90 Once the pattern is indexed, the lattice parameters can also be determined from a least squares analysis.The volume of the unit cell can be calculated from the lattice parameters. elf the density of the crystals are known, then the mass of the contents of the unit cell can be calculated. *From a knowledge of formula weight, the number of formula units, Z, can be calculated. eThe density can be measured using a mixture of liquids such that the crystals neither float nor sink. The density of the liquid can then be measured using a density bottle or equivalent technique. Crystal system: Unit Cell Volume. Cubic Vea Tetragonal Vea Hexagonal V = atcsin(60") Trigonal V = atcsin(60) Orthothombic V=abe Monoclinic V = abesinip) Triclinic V = abe (1- costa - cos?B - cos?y} + 2(cos(«) cos(B) cos(y))¥2 m Density = — vIdentification of Unknowns and Phase Purity rane) MnO, BiMn,Os NiMn,O, Sample A database from the Joint Committee for Powder Diffraction Standards has ~340,000 data sets in the Powder Diffraction File (PDF-4). A computerized search-match program may be used to compare the d- spacings and intensity of the recorded peaks to the database. -powder diffraction typically has a limit of a few percent for detection of phases.Destructive Interference Intuitively, you might expect a plane of atoms with larger Z will give amore intense reflection, because the heavier an atom is, it is better at scattering X-rays. *However, there are interactions with reflected X-rays from other planes that may produce destructive interference. Nacl KCl The structures may be thought of as two interlocking ccp arrays of Na* and Cr ions. Close packed layers of CI lie parallel to the body diagonal. Halfway between the 111 layers, there are close packed layers of Nat. *A reflection from a Cl’ close packed layer is exactly out of phase with the Na* layer#Since a Cl has 18 electrons it scatters X-rays more that a Na* with 10 electrons, the reflections will partially cancel and the intensity of the 111 reflection will be weak. eThe 222 layers contain the close-packed layers of Na* and Cl, which will be a strong reflection since the X-rays will reinforce each other.In KCl, the reflection from the 111 layers containing K* ions is exactly out of phase with the reflection from the Cl close packed layers. *K* and Cl are isoelectronic and the scattering factors are nearly identical, so the net effect is that the two reflections cancel and the 111 reflection appears to be absent. eThis means the first reflection Is the 200, which Is easy to mistake for the 100 reflection from a primitive cubic cell with a unit cell length half that of the actual fec cell. [220Crystallite Size A decrease In the crystallite size causes an increase in the width of the diffraction. + On either side of the Bragg angle, the diffracted beam will destructively interfere and result in a sharp peak. + The destructive interference is a result of the summation of all the diffracted beams. + Close to the Bragg angle it takes diffraction from a large number of planes to produce complete destructive interference. In very small crystallites, there are not enough planes to produce complete destructive interference, so a broadened peak is observed.Polymers * Polymers come in many forms. They can be crystalline, microcrystalline or amorphous. In a single polymer, you often find all three forms depending on how the polymer was made and processed, frequently, forms are mixed in a single sample. Polymers, like other crystalline solids, can also have polymorphs, polytypes, and all types of solid state molecular arrangements.Polymer States of Matter and the XRD pattern of | Highly known examples Crystalline (very small amorphous) Polyethylene Semi-crystalline (partially crystalline partially amorphous) Microcrystalline AmorphousPolystyrene free radical HH H 4H i ‘nati , h vinyl polymerization Lo es a eG H H styrene polystyrene Monomer Polymer Polymers are created from monomers as shown above for Polystyrene. There are many ways for monomers to link together to form polymers, creating a wide diversity of polymers. The example shown is one mechanism, a free radical polymerization.Once the monomers link together they form long chains sort of like strands of spaghetti. The chains can move and fold ~ chain folding is one means by which crystalline regions can form, hydrogen bonds (and other types of intermolecular forces) often help in linking chains together. Crystalline regionSharp well-defined peaks = tl Peaks are broad due to small cystallites, can be assigned with 2 ental structure From “Selected Papers Of Turner Alfrey”, Marcel Dekker Inc, 1986 Very broad features, not defined bya crystalline model =| Highly crystalline Semi-crystalline (partially crystalline partially emorphous AmorphousHighly A h Semi talli ; morphous emicrystalline Crystalline In many cases, we do not have a crystal structure available, the state of matter can be inferred from the pattern appearance. On the far right, the polymer patterns consist of multiple sharp peaks consistent with “diffraction” from a crystalline lattice. On the far Left, the patterns have very broad features consistent with “incoherent scatter” from an amorphous solid. The patterns in the middle are more complex, exhibiting a mix.Crystalline Polymers nA = 2d sind + nis an integer * Ais the wavelength * dis the interplanar spacing * 6is the diffraction angle inenty If the polymer is crystalline, then the diffraction pattern (middle right) is a result of a crystal structure (top right) as related by Brage’s law (left) and the pattern can be indexed (bottom right) and represented by a stick pattern of positions and intensities.20 100 2 2 & 8 8 Relative Intensity x 8 19 20 21 22 23 24 25 5 8 13 1g cd 7 10 3 pda, NAT 27 11| | 4 9: 14 15 |: 18 T T T — i 7 30 40 50 60 70 80 90 100 30.00 40.00 50.00 60.00 70.00 80.00 90.00 100.00 20 (DEGREES)Intensity — Beers one Mn one Peek harcore ictaiees Pru RUC ene cokes tors and as shown below for polyethylene. CRYSTALLINE POLYETHYLENE Orthorhombic 4. bu Sonik 318 ear oo 3208 zoe io 3500 Ea 18 East ot 23 ber 3540 aise too Sarr iiss a20 Bar dea Gt ean Bose {922 ‘Tumer—Jones ites 41 Polymer Scl, 62 ,S53(1962) tr te ei Hse vee Wolter a Reding 010 Tricine 7 2Reference Data For Polymers In ICDD reference databases (PDF-2, PDF- 4+, POF-4/Organics) we now have over 1200 reference patterns of polymers. Most have been collected from decades of work. In the twentieth century most polymer data were represented by using dl pairs such as the data shown on the bottom, This was good for identification purposes, ‘which searches 4,! pairs, but not for measuring crystallinity, Since 2003, ICDD has been collecting polymer data as full digital patterns. In Release 2011 there are 43 digital polymer patterns (middle). The data collection process is focused on high volume ‘commercial polymers.Polymer patterns are additive. In this example, we see a crystalline polymer (polyethylene) is added to a noncrystalline polymer (polyisobutene) and the resulting pattern (top) shows contributions from both polymers. a INTENSITY This probably indicates that these two materials were not miscible. If the polymers were atomically mixed, then a different pattern would be produced based on the new unit cell or atomic arrangement. XRD is often used to distinguish between block copolymers, alternating or randomly mixed copolymers.Inerety j Patterns are additive: in this example, 2 polymer patterns are added with 2 patterns of inorganic oxides — to identify a corrosion residue collected on a cloth. The cloth is made of two polymers- PET and cotton. Four pattern refined fit 65.502) 34.5(4) 97.8(7)Always search on the polymer subfile in an ICDD database. Polymers are weak scatterers and frequently have only 2 few weak peaks, you need to help the automated search process. The peaks are frequently broad so make sure your automated software is detecting them (you may need to change the program defaults). Crystalline polymers: Crystalline polymers can be readily identified by most search/match software on the market today. The d-spacings can be searched and d,l pairs used in the identification process, If the polymer is present in small concentrations, please keep in mind that many, if not most polymers, have only 1-3 intense peaks usually associated with interplanar spacings between polymer chains. You may need to use trace identification methods since the lack of peaks will often limit automated processes. See the tutorial: “Data ing-Trace Phase Analysis” com/resources/tutorials/ Non-crystalline polymer: Special methods are required that identify non-crystalline materials besed on full patterns and not | listings, Integral indices and cluster anelyses are examples of these methods. Specialized Reftveld and Le8ail refinements can also be used. They are beyond the scope of this tutorial, but examples are given in other tutorials, See the tutorial: “Using Si hitpy ity Indexes — Integral index” id. com/resources/tutorials/ www 19Examples of Analyses — Identification of Polymers Microcrystalline Cellulose Pharmaceutical grade microcrystalline cellulose is used in a wide variaty of tablets as both an excipient filler and an |< + > additive to modify drug time release. The reference pattern of microcrystalline | cellulose is shown at the top. The middle pattern is the diffraction pattern fram a ground Pepcid AC tablet, Pepcid AC The sharp crystalline peaks are due to the Latah active ingredient famotidine and one can Pi ae easily see the microcrystalline cellulose = a = pattern. This identification would be easy é by either automated or manual methods. The bottom pattern is from a ground Benedryl tablet. Tis is far more typical of Boned what ICDD has seen in pharmaceutical eneary! formulations. The microcrystalline cellulose (in bor) is 2 much weaker eek pattern than the crystalline inorganic excipients (brushite reference in blue), ‘The weak pattern and broad peaks meke this a much more difficult identification.The following slide shows a classical method for measuring crystallinity in polypropylene. It is assumed that the polymer has regions of aligned chains in small crystallites that diffract and that the remaining chains have no order and contribute to an incoherent scatter. The scientist trys to measure the area of both components and estimate a crystallinity. This method can be applicable in cases where the amorphous region is well defined within a relatively narrow angular range —as in polyethylene and polypropylene. Absolute standards are not necessary and this method yields a relative crystallinity. Care must be taken that the amorphous area is measured the exact same way in the exact same angular range for each specimen analyzed. With this relative method, all specimens need to be analyzed under identical conditions on the same instrument.Based on the premise that patterns are additive Requires both a 100% crystalline reference and an amorphous reference. The ICDD database can provide many high volume commercial polymers with full digital pattern references. Full digital patterns are used; they need to be treated to remove background and have identical data collection ranges. Because most data scans consist of thousands of data points, it is preferred that this is a computer automated method. Graphical interfaces are advised so that the user can judge the appropriateness of the background removal and other data treatment steps. The references can be used to calculate crystallinity using pattern fitting methods (several software packages are currently available). If an I/Ic value is available, or if an internal standard is used, concentrations can be calculated. This method is preferred in cases, like cellulose, where both the crystalline pattern and amorphous pattern heavily overlap and cover most of the measurement range.Patterns are Additive- Measuring Crystallinity in Cellulose aoa 7 Standards of native om | cellulose, crystalline and ow amorphous. The 10000 S| crystalline form is | beta. _