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BI 3. PH NHIU X TIA X (XRD) M bi.

HD K3
Gii thiu Phng php ph Rnghen l phng php vt l rt hu hiu nghin cu cu trc, thnh phn pha ca cc tinh th cht rn. C s ca phng php da trn hin tng bc x in t t ngun pht cc tia m cc (tia X) c kh nng xuyn qua mt s tm chn thng thng lm en phim, knh nh. Cc ngun pht tia m cc c tnh cht c bit ny gi l nhng ng pht tia X c nh khoa hc Ronghen pht hin v to ra t nhng nm cui ca th k 19 c cu to gm c hai b phn chnh l catt v ant.Chm tia in t pht ra t catt s c gia tc do in p ln ant s bay v ant vi vn tc ln c ng nng ln va p vo ant bin thnh nhit nng v mt phn c pht ra di dng bc x tia 10. Vic ng dng phng php ph Rnghen ngy cng rng ri trong nhiu lnh vc nghin cu khc nhau khng nh v tr quan trng ca phng php trong nghin cu khoa hc cng nh trong phn tch cu trc pha tinh th ca cc vt liu rn, cc hn hp oxit kim loi, cc cht xc tc rn, cc cht khong v c, t ...V vy vic tip thu c c s l thuyt ca phng php v k thut thao tc vn hnh my mc thit b o ph Ronghen l rt quan trng v cn thit. Mc tiu thc hin Hc xong bi ny hc vin s c kh nng M t c s ca phng php ph Rnghen, my o ph Phn tch cu trc tinh th ca Zeolit bng ph XRD

nh tnh v nh lng thnh phn pha ca zeolit Th nghim, thc hnh o trn my trong phng th nghim. Ni dung chnh 1. 2. 3. 4. 5. C s ca phng php ph Rnghen Phng trnh nhiu x Bragg-Vulf. ng dng ph Rnghen phn tch thnh phn pha ca tinh th nh lng thnh phn pha. Phn tch cu trc pha.

6. Mt s ph Rnghen ca vt liu cht rn. 1. C s ca phng php Rnghen


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1.1.Mt s khi nim v vt liu rn v cu trc tinh th hc Cu trc ca vt liu rn ph thuc vo s sp xp cc nguyn t, ion hoc cc phn t v lc lin kt gia chng. Vt liu rn c th c cu trc tinh th khi cc nguyn t hoc ion sp xp mt cch c trn t trong mt mu hnh lp li trong khng gian ba chiu. Vt liu rn c sinh ra trong t nhin hoc c ch to bi con ngi, c cc tnh cht c bit v ha hc v vt l. Vic ch to cc loi vt liu mi ang c pht trin rt nhanh nhm p ng c cho nhu cu ca khoa hc k thut, do vic hiu bit v cu trc v cc tnh cht ca chng l v cng quan trng v cn thit. Trong cc nhm vt liu th vt liu kim loi v vt liu gm l hai i tng nghin cu ch yu ca phng php Rnghen. Vt liu kim loi c cu trc tinh th, trong cc nguyn t c sp xp mt cch trt t. Vt liu gm c th c cu trc tinh th hoc khng tinh th hoc hn hp ca c hai cu trc trn. Vt liu gm l vt liu v c bao gm nguyn t kim loi v phi kim lin kt ha hc vi nhau. 1.2. Cu trc v hng s mng hnh hc tinh th 1.2.1.Mng khng gian v c s Cc nguyn t hoc ion nu c sp xp mt cch trt t lp i lp li trong khng gian ba chiu th chng to thnh vt rn cu trc tinh th v c gi l vt liu tinh th. S sp xp cc nguyn t trong vt rn c th c m t bng mt mng li 3 chiu m nt mng l cc nguyn t (hoc ion), v c gi l ma trn im ba chiu v hn. Trong tinh th l tng tp hp cc nt mng quanh bt k mt nt no cho cng ging nh cc nt mng xung quanh. Nh vy mi mng khng gian c th c m t bi cc v tr nguyn t xc nh trong mt n v ( c bn). Kch thc v hnh dng ca n v c th c biu din bng 3 vect c s a, b, c xut pht t 1 gc ca n v. Chiu di ca ba vect ny v gc gia chng , , 1.2.2. Mng Bravais c gi l hng s mng.

Cc nh tinh th hc a ra by kiu n v xy dng cc mng im ca tinh th. A.J.Bravais a ra 14 kiu mng tinh th ca cht rn v 4 kiu n v: 2
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n gin Tm khi Tm mt Tm y

Hnh 3.1: Mng khng gian ca tinh th rn l tng, n v v hng s mng T cc kiu n v c th phn lp mng khng gian theo h tinh th nh sau: Bng 3.1: Mng khng gian ca h tinh th H tinh th Lp phng (Cubic) Bn phng (Tetragoral) Trc thoi (Orthorombic) Ba phng (orhombohechal) Su phng (hexagoral) Mt nghing (monoclinic) Ba nghing (Triclinic) c trng hnh hc a=b=c = = = 90o a=b c = = = 90o a b c = = = 90o Kiu mng Bravais Lp phng n gin Lp phng tm khi Lp phng tm mt Bn phng n gin Bn phng tm khi Trc thoi n gin Trc thoi tm khi Trc thoi tm mt Trc thoi tm y Ba phng n gin Su phng n gin Mt nghing n gin Mt nghing tm y Ba nghing n gin

a=b=c = = 90o a=b c = = 90o, = 120o a b c =

a b c Hu ht cc kim loi (khong 90%) kt tinh trn s ha rn thnh ba cu 90o trc tinh th xp cht l: Lp phng tm khi (LPTK)
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Lp phng tm mt (LPTM) Su phng xp cht (SPXC)

Hnh 3.2: Cu trc tinh th ca vt liu rn Cc cu trc ny c lin kt nguyn t cht ch hn v c nng lng thp hn. n v c kch thc v cng nh ch c nonamet (nm). V d kim loi Fe c cu trc lp phng tm khi nhit phng l 0,287 nm c th tnh ton c s lng n v trong 1 mm
1nm.10 6 6 1x n m 3.48x10 0.287nm

1.2.3. H s xp v s sp xp i vi kim loi mi nguyn t u c mt s lng nguyn t tip xc hoc cch u gn nht, gi l s sp xp (s phi t). S phi t cng ln mng tinh th cng dy c. Trong cu trc ca tinh th lp phng tm khi mi quan h gia chiu di cnh lp phng (a) v bn knh nguyn t (R) c biu din nh sau:
a 4R 3

(3.1)

i vi cu trc lp phng tm mt, quan h gia chiu di cnh (a) v bn knh nguyn t (R) nh sau:
a 4R 2

(3.2)

H s xp (HSX) l phn th tch chim ch bi cc qu cu nguyn t trong n v:


HSX V1 V

(3.3)

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Trong : V1: s nguyn t trong n v x th tch nguyn t. V: Th tch n v. Cu trc lp phng tm mt c HSX cao nht bng 0,74 v c gi l cu trc xp cht. Cc cu trc lp phng khc l khng xp cht. Bng 3.2. Quan h gia hng s mng v bn knh nguyn t ca kim loi c cu trc tinh th lp phng tm mt v lp phng tm khi. Loi cu trc tinh th Kim loi Crom (Cr) St (Fe) Molipden (Mo) LPTK Kali (K) Natri (Na) Tantal (Ta) Vonfram (W) Vanadi (V) Nhm (Al) ng (Cu) Vng (Au) Ch (Pb) Niken (Ni) Platin (Pt) Bc (Ag) Hng s mng a (nm) 0,289 0,287 0,315 0,533 0,429 0,330 0,316 0,304 0,405 0,361 0,408 0,495 0,352 0,393 0,409 Bn knh nguyn t R (nm) 0,125 0,124 0,136 0,231 0,186 0,143 0,137 0,132 0,143 0,128 0,144 0,175 0,125 0,139 0,144

LPTM

Cu trc su phng xp cht (SPXC): trong cu trc ny tng s nguyn t trong mt n v l 6. T s chiu cao ca lng tr v cnh y c gi l t s c/a. c bn ca SPXC l khi lng tr lc gic gm 6 lng tr tam gic u.

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Hnh 3.3: V tr cc nguyn t trong mng c s: a.- LPTK , b LPTM , c - SPXC Bng 3.3. Hng s mng v bn knh nguyn t ca mt s kim loi c cu trc tinh th SPXC (To = 200C) Kim loi Cadimi (Cd) Km (Zn) Magie (Mg) Coban (Co) Ziriconi (Zr) Titan (Ti) Benili Hng s mng a 0,2973 0,2665 0,3209 0,2507 0,3231 0,2950 0,2286 c 0,5618 0,4947 0,5204 0,4069 0,5148 0,4683 0,3584 Bn knh nguyn t R (nm) 0,149 0,133 0,160 0,125 0,160 0,147 0,113 T s c/a 1,890 1,856 1,623 1,623 1,593 1,587 1,568 % lch khi gi tr +15,7 +13,6 -0,61 -0,61 -2,45 -2,82 -3,98

1.2.4. Cch k hiu v tr nguyn t trong c bn lp phng S dng h ta vung gc x, y, z. V tr nguyn t trong c bn c xc nh bng khong cch n v dc theo trc x, y, z. Th d: ta v tr ca tm nguyn t gc trong c bn lp phng tm khi c th biu din nh hnh sau: nguyn t tm (, , )

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Hnh 3.4: Cc mt phng ca tinh th lp phng n gin 1.2.5. Phng tinh th trong mng lp phng i vi tinh th lp phng ch s phng tinh th l cc thnh phn vect ca phng cn tm dc theo cc trc ta x y z v gim n s nguyn nh nht. K hiu chung cho cc ch s phng l [ u v w ]. Ch s phng m k hiu l mt gch ngang trn ch s, v d [ 1 ]. Mi vect ch phng song song u c ch s phng nh nhau.

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Hnh 3.5: Trc ta vung gc xyz 1.2.6. Ch s Miller xc nh mt phng tinh th trong cu trc lp phng, thng s dng ch s Miller. a. Ch s Miller c nh ngha nh sau Ch s Miller l i lng nghch o giao im phn s ca mt tinh th ct trn trc tinh th x, y, z ca ba cnh khng song song ca c bn lp phng. Cnh lp phng ca c bn l n v o chiu di v v tr ct ca mt tinh th c o theo thnh phn ca chiu di n v ny. b. xc nh ch s Miller cn phi theo trnh t sau: Chn mt mt phng khng qua gc ta . Xc nh cc ta giao im ca mt phng vi cc trc x, y, z (ta c th l phn s). Ly nghch o ca cc ta ny. Trit tiu cc phn s v xc nh tp s nguyn nh nht, cc s ny chnh l ch s Miller ca mt phng tinh th v c k hiu bng cc ch sau h, k, l theo trc x, y, z tng ng. S m c vit bng mt gch ngang trn [ hk l ]

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Hnh 3.6: Ch s Miller ca mt s mt tinh th lp phng quan trng.

Hnh 3.7: Mt tinh th lp phng c cc im ct. V d: Xc nh ch s Miller ca mt s mt tinh th lp phng quan trng sau. Bng 3.4 Tiu ch Ta im ct Ly nghch o Trit tiu phn s Ch s Miller s l (6 3 2) Tnh ton Tiu ch Ta im ct Ly nghch o Trit tiu phn s X 1 1 1 0 0 0 0 y z X 1/3 3 6 y 2/3 3/2 3 z 1 1 2

Ch s Miller ca mt phng s l (1 0 0). Bng cch tng t c th xc nh c ch s Miller ca cc i lng trn. Trong cu trc tinh th lp phng khong cch (d) gia cc mt phng song song gn nhau nht c cng ch s Miller c k hiu l dhkl v c tnh ton theo cng thc sau:
1 d2 h2 k2 a2 l2

(3.4)

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Trong : a l hng s mng. 1.2.7.Ch s mt tinh th trong mng su phng xp cht (SPXC) Ch s ny cn c gi l ch s Miller- Bravais v c k hiu bng 4 ch h, k, i, l, (h k i l) v c thit lp trong h ta 4 trc trong c bn.
+c

+a3

-a1

-a2

+a2 120 C +a1 -c -a3


o

Hnh 3.8: Bn trc ta ca tinh th SPXC. Ba trc c s l a1, a2, a3 hp vi nhau tng i, mt gc 1200, trc th 4 (c) t ti tm ca c bn. Nghch o ca cc giao im ca mt phng tinh th vi trc a1, a2, a3, c s c cc ch s h, k, i, v l. Mt y ca cc c bn ca SPXC c k hiu l (0001). Mt bn hay mt lng knh ty theo v tr ca n m c cc ch s, cc k hiu khc nhau v to thnh h mt { 1010 }

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Hnh 3.9: Ch s Miller- Bravais ca mt tinh th SPXC 1.2.8.L hng trong cu trc mng. L hng l khng gian trng b gii hn bi hnh khi nhiu mt m mi khi l tm nguyn t hoc ion nt mng. Kch thc l hng c nh gi bng bn knh ca qu cu ln nht c th t lt vo khng gian trng . Hnh dng, kch thc l hng ph thuc vo kiu cu trc mng. L hng thng gp c dng khi bn mt hoc tm mt nh m t trong hnh sau:

Hnh 3.10: Cc loi l hng trong mng LPTM (a) v LPTK (b) 1.2.9.Tnh th hnh
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Nhiu nguyn t c th tn ti cc dng tinh th khc nhau ph thuc vo nhit v p sut. V d: St tn ti c hai cu trc tinh th LPTK v LPTM trong sut thang nhit t nhit phng n Tnc = 1539oC. St -273oC 912oC c cu trc tinh th LPTK; st t 1394oC t 912oC tinh th LPTM; st delta s mng ln hn st . Bng 3.5. Dng tinh th th hnh ca mt s kim lo1. Kim loi Ca Co Fe Li Na Ti Y Zr Cu trc tinh th T phng LPTM SPXC LPTK LPTK LPTK SPXC SPXC SPXC
o

tn ti t 1394oC c cu trc

1539oC cu trc LPTK nhng c hng

To khc LPTK (> 447O C) LPTM (> 427OC) LPTM (912oC 1394oC) LPTK (> 1394oC) SPXC (< -193oC) SPXC (< -233oC) LPTK (> 880O C) LPTK (> 1481OC) LPTK (> 872O C)

1.2.10. Sai lch mng tinh th Trong thc t tinh th khng hon chnh m thng cha cc dng khuyt tt khc nhau dn n tnh cht c hc v vt l nh tnh dn in, n mn kim loi.... Sai lch mng tinh th c th tn ti 3 dng chnh sau: Khuyt tt im. Khuyt tt ng lch. Khuyt tt mt. Khuyt tt im n gin nht l v tr khuyt nguyn t to thnh l trng (vacancy) trong qu trnh to tinh th. Nng lng hnh thnh cc khuyt tt cn bng c 1ev v s lng cc khuyt tt cn bng ph thuc vo nhit theo hm m:
Nv N * exp( Q ) RT

(3.5)

Trong : N S nt mng. Q Nng lng to thnh l trng. 12


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k Hng s Boltzmann. T nhit tuyt i (K). Theo phng trnh trn th s lng tng rt nhanh theo nhit . Vacancy trong kim loi cng c th c to thnh khi c s bin dng n hi, ngui nhanh hoc bn ph bng cc ht nng lng cao nh ntron. Vacancy khng cn bng c xu hng to thnh cc m vacancy. i khi nguyn t trong tinh th chim mt v tr ngoi nt gia cc nguyn t xung quanh to ra khuyt tt ngoi nt hay nguyn t xen k. Tronh thc t khng c vt liu hoc kim loi no sch tuyt i 100% m ch t 99,9999%. V vy mt lng rt nh nguyn t pha tp thay th trong silic nguyn cht c th nh hng rt ln n tnh dn in ca silic. Khuyt tt ng lch trong tinh th c to thnh bi bin dng thng xuyn hoc bin dng n hi hoc trong qu trnh ho rn ca tinh th. Khuyt tt mt l s sai lch mt trong vt liu a tinh th gm nhiu ht vi nh hng tinh th khc nhau. 1.2.11. n tinh th n tinh th l vt tinh h c mng ng nht v nh hng khng i trong ton b th tch. Trong t nhin hu nh n tinh th kim loi khng tn ti, phn ln n c to ra bng cng ngh tng hp. Cc loi n tinh th c ng dng nhiu trong cng nghip bn dn v vt liu in t. 1.2.12. a tinh th Trong thc t hu nh ch gp vt liu a tinh th gm rt nhiu tinh th nh (c 1 hng khc nhau mang tnh ngu nhin v lin kt vi nhau bng bin gii ht. m) c gi l ht c cng cu trc mng nhng vi nh

Hnh 3.11: M hnh n tinh th v a tinh th


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AA - M hnh n tinh th; b - a tinh th, c - Vi hp kim a tinh th 1.2.13. Kch thc ht Kch thc ht ca vt liu a tinh th c ngha quan trng v nh hng nhiu n tnh cht ca kim lo1. Mt trong nhng phng php o kch thc ht thng dng theo ASTM trong cp ht n c xc nh theo cng thc sau: N = 2 n-1 (3.6) Trong : N - l s ht trn mt . vung b mt phng i cao. n - l s nguyn c gi l cp ht ASTM. C 16 cp ht khc nhau theo th t ht nh dn. Nh vy mt cp ht tng ng vi s lng ht trn mt n v din tch. Ngi ta thng xc nh cp ht bng cch so snh cng mt phng i (thng l 100) gia vt liu nghin cu vi thang nh cp ht chun ASTM vi kch thc ht khc nhau. Siu ht c cu trc tinh th kh hon chnh v c kch thc rt nh (nm). C cu trc tinh th kh hon chnh nh hng lnh nhau mt gc rt nh (1-2 o0)v ngn cch nhau bng bin gii siu ht.Bin gi7i nu thc cht l nhng lnh bin c chiu dy nh hn so vi bin gi7i ht a tinh th. Trong khi a tinh th c cu trc hng chc m, thm ch hng trm m. Bng 3.6: Cp ht theo ASTM. Cp ht 1 2 3 4 5 6 7 8 9 10 S ht trong in2, x 100 1,0 2,0 4,0 8,0 16,0 32,0 64,0 128 256 512 S ht trong 1 mm 2 x 1 15,5 31,0 62,0 124,0 248 496 992 1980 3970 7940 Din tch tht ca 1 ht (mm2) 0,0645 0,0323 0,0161 0,00807 0,00403 0,00202 0,001008 0,000504 0,000252 0,000126

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2. Nhiu x tia X, phng trnh Vulf Bragg 2.1.Khi nim nhiu x tia X Nhiu x l c tnh chung ca cc sng b thay i khi tng tc vi vt cht v l s giao thoa tng cng ca nhiu hn mt sng tn x. Qu trnh hp th v ti pht bc x in t cn gi l tn x. Mi photon c nng lng E t l vi tn s ca n: E = h. Mt khc tn s lin quan ti bc sng hc E Trong : h - hng s Plank, h = 4,136. 10-15 e5.s hay 6,626.10-34 J.s. c tc nh sng c = 2,998. 10-8 m/s. Theo tnh ton bc sng tia X khong 0,2 nm (2Ao). m t hin tng nhiu x ngi ta a ra ba thut ng sau: Tn x (Scattering): l qu trnh hp thu v ti bc x th cp theo cc hng khc nhau. Giao thoa (Interference): l s chng cht ca hai hoc nhiu sng tn x (3.7) theo cng thc sau: (3.8)

to thnh sng tng hp. Nhiu x (Diffraction): l s giao thoa tng cng ca nhiu sng tn x. 2.2. To ngun tia X Tia X c to ra khi cc in t vi tc ln b km hm bi mt vt chn. Rnghen pht hin ch pht tia X chnh l ch c chm in t p vo, v ng to ra ng pht tia Rnghen. Ngy nay, ng pht tia Rnghen ngy cng c hon thin hn nhng chng u c nhng b phn chnh sau: Hai in cc Catot v Anot t trong ng thy tinh bng thch anh c chn khng cao (10-6 10-7 mmHg). Catot K thng c lm bng dy Vonfram v pht ra chm in t khi c t nng. Anot l mt a cng c lm bng Vonfram hay Platin. Ngi ta t vo anot mt in p rt cao (hng trm kV). Chm tia in t pht ra t catot c gia tc do in p ln Anot s bay v pha anot vi vn tc ln. Khi cc in t c ng nng ln va p vo anot phn ln nng lng s bin thnh nhit nng, ch c mt phn rt nh <

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1% c chuyn thnh tia 10. Do vy cn phi lm ngui ng pht Rnghen bng nc. Tia Rnghen pht ra t cc ng pht thng l cc bc x lin tc gm nhiu bc sng khc nhau do cc in t mt nng lng trong mt lot va chm vi cc nguyn t anot, v mi mt in t mt nng lng theo cch khc nhau cho nn cc bc sng tia x cng khc nhau. Ty theo tng iu kin nht nh (in th anot, cht liu lm anot) c th thu c cc bc x hu nh n sc gi l cc tia Rnghen c trng.

Hnh 3.12: S nguyn tc ng pht tia Rnghen. Cc vch c trng khc nhau s tng ng vi cc dch chuyn in t gia cc mc nng lng v c k kiu l K, L, M theo m hnh cu trc nguyn t ca Bohr.

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Hnh 3.13: M hnh nguyn t v s to thnh tia X c trng. K K , L Mt s kim loi lm vt liu anot s cho cc vch c trng sau: Mg - K = 0,95 Ao. Fe - K = 1,7 Ao. Cu - K = 1,5 Ao. Ag - K = 0,7 Ao. W - K = 0,5 Ao. Trong nghin cu bng nhiu x tia X thng chn tia c trng l K v tia K Cu l bc x thng c s dng rng ri nht. Cc vch K c nng lng ln hn so vi L v khng b hp th mnh bi vt liu nghin cu. 2.3. Mt s tnh cht ca tia Rnghen Tia X c nhng tnh cht c bn sau: Kh nng xuyn thu: tia Rnghen c kh nng xuyn qua mt s tm chn sng thng thng, lm en phim nh. Kh nng gy hin tng pht quang (ph hunh quanh tia X).
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Gy s ion ha ca cht kh.

Hin tng nhiu x Nhiu x l s thay i ca cc tia sng hoc cc sng do s tng tc ca chng vi vt cht. Khi chm tia X chiu vo vt cht s xy ra tng tc vi cc in t trong nguyn t (hoc ht nhn nguyn t nu chm tia X c nng lng ln). Khi tng tc vi vt cht chm tia X c th mt mt phn nng lng do cc hiu ng hiu ng hp th: xy ra khi tia X truyn qua vt liu. Chng s b hp th v cng chm tia s gim. S gim ny tun theo nh lut c bn ca s hp ph sng in t nh sau:
I I o10

(3.9)

Trong : I, Io cng ca tia X ti v tia X truyn qua. - h s hp thu khi, L - dy lp vy cht. Z - th t nguyn t. - bc sng nh sng ti. 2.4. nh lut Vulf-Bragg nh lut Vulf-Bragg c a ra nm 1913 th hin mi quan h gia bc sng tia X v khong cch gia cc mt phng nguyn t. Theo l thuyt v cu to tinh th, nhng nguyn t hay ion phn b mt cch trt t u n trong khng gian theo mt quy lut xc nh. Khong cch gia cc nguyn t (ion) khong vi Ao v gn tng ng vi bc sng tia 10. Khi chm tia X p vo tinh th th xut hin cc tia nhiu x vi cng v cc hng khc nhau. nh lut Bragg gi thit rng mi mt phng nguyn t phn x sng ti c lp nh phn x gng, Gi s c hai mt phng song song AA v BB (hnh 10). C cng ch s Miller h, k, l, v cch nhau bi khong cch gia cc mt phng nguyn t dhkl. Gi thit rng tia ti l tia n sc song song v cng pha vi bc sng chiu vo hai mt phng ny vi mt gc . Hai tia 1 v 2 b tn x bi nguyn t Q v P cho hai tia phn x 1 v 2 cng vi mt gc so vi cc mt phng A, B. 18
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=Z .

Hnh 3.14: Nhiu x tia X bi cc mt phng ca nguyn t (A-A - B-B ). iu kin nhiu x l: n = SQ + QT = 2dhklSin (3.10) Qung ng 1-P-1 v 2-Q-2 bng s nguyn ln bc sng. Trong : n = 1, 2, 3,gi l bc phn x. Phng trnh Bragg c dng sau: n = 2dhklSin

(3.11) v

Phng trnh ny biu th mi quan h gia gc cc tia nhiu x Bragg khng c tha mn th s khng xy ra hin tng giao thoa.

bc sng tia ti, khong cch gia cc mt phng nguyn t. Nu nh lut Khi n > 1 cc phn x c coi l phn x bc cao v phng trnh Bragg c th vit nh sau: = 2(dhkl/n) Sin (3.12) Thng s d/n l khong cch gia cc mt phng hkl v nh, nk, nl l cc ch s Miller c khong cch bng l/n cch khong gia cc mt h, k, l. nh lut Bragg l iu kin cn nhng cha cho nhiu x tia X, v nhiu x ch c th chc chn xy ra vi cc n v c cc nguyn t gc mng. Cn cc nguyn t khng gc mng m trong cc v tr khc, chng hot ng nh cc tm tn x ph lch pha vi cc gc Bragg no , kt qu l mt i mt s tia nhiu x theo phng trnh phi c mt.

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Hnh 3.14: Nhiu x tia X t cc mt ca mng tinh th. 2.5.Mng o Mt phng trong khng gian thc c th biu din bng mt nt mng trong khng gian o. c bn ca mng o c xc nh bi cc vect a*, b*, c* tha mn h thc sau: a*a = b*b = c*c = 1 a*b = b*c = c*a = 0 Trong a, b, c l cc vect n v tinh th. Mng o c nhng tnh cht sau: Mi nt mng o tng ng vi mt mt (hkl) ca tinh th. Vect mng o ghkl = ha* + kb* + lc* vung gc vi mt phng mang (hkl) ca mng tinh th v Ghkl = 1/d hkl ghkl th.
1 d hkl

(3.13)

Trong dhkl l khong cch gia cc mt phng (hkl) trong mng tinh

Mng o xc nh mt khong cch v tr mng c kh nng dn n s nhiu x.

20

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Hnh 3.15: Quan h gia trc mng thun a, b, c v mng o a*, b*, c*. Mi cu trc tinh th c hai mng lin hp vi n, mng tinh th v mng o v nh nhiu x ca tinh th l mt bc tranh mng o ca tinh th. 2.6. Cng nhiu x C th tnh ton c cng nhiu x bng cch cng sng hnh sin vi pha v bin khc nhau. Hng ca tia nhiu x khng b nh hng bi loi nguyn t tng v tr ring bit v hai mng n v c cng kch thc nhng vi s sp xp nguyn t khc nhau s nhiu x tia X trn cng mt hng. Tuy nhin cng ca cc tia nhiu x ny khc nhau. xc nh cng nhiu x thng tin hnh theo 3 bc sau: Nhiu x tia X bi in t t do. Nhiu x tia X bi nguyn t. Nhiu x bi mng c bn. 2.6.1. Cng nhiu x bi in t t do c xc nh theo cng thc sau: e4 Io I sin2 2 2 m2 c 4 r e Trong : Io Cng tia t1. e in tch in t. me Khi lng ca in t. c Tc nh sng. r Khong cch gia tn x in t n u d (detect). Biu thc trn cho thy nng lng tn x t cc in t n l rt nh. 2.6.2. Nhiu x bi mt nguyn t Nguyn t c nhiu m my in t quay xung quanh ht nhn. Tia ti b tn x bi in t v ht nhn. Nhng ht nhn ca nguyn t rt ln cho
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(3.14)

21

nn c th b qua tn x bi ht nhn, do tn x ton phn ch yu bi cc in t ring bit. Cc in t quay quanh ht nhn cc v tr khc nhau s sinh ra sng tn x vi pha khc nhau v s giao thoa vi nhau. i lng tha s tn x nguyn t f m t hiu xut tn x trn mt hng ring bit c xc nh bng t s sau: f = bd1/bd2 f
bd1 bd 2

(3.15)

bd1 Bin sng tn x bi mt nguyn t. bd2 Bin sng tn x bi mt in t.

Hnh 3.16: Tn x tia X bi mt nguyn t gi tr f bng s in t trong 0 hay f = Z (nguyn t s). nguyn t khi 2.6.3. Nhiu x bi mng c bn mng c bn l phn nh nht lp li tun hon to thnh tinh th. Thng trong tinh th c cha cc nguyn t khc nhau sp xp cc v tr khc nhau do cc sng c bin khc nhau s t hp li cho cng tng cng v c biu din nh mt hm m phc nh sau:

Aei
Trong :

fe 2

i ( hu k

l )

(3.16)

- l s chnh lch pha gia sng tn x bi nguyn t B v

sng tn x bi nguyn t A i vi mt phn x hkl. Cng nhiu x c d on bi nh lut Bragg v t l vi bnh phng tha s cu trc F .
2

bn.

Tha s cu trc khng ph thuc vo hnh dng v kch thc c

Tuy vy cng nhiu x khng ch ph thuc vo tha s cu trc m cn vo cc tha s khc. V c th biu din bng biu thc tng qut sau: 22
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1 cos2 2 p sin2 cos

(3.17)

Trong : p L tha s lp. e-2 L tha s nhit. 1+ cos 2 2 Tha s Lorent. 2cos sin 3. ng dng ph nhiu x tia X phn tch thnh phn cu trc tinh th Nhiu x tia X c s dng phn tch cu trc vt liu rn, mc tinh th ha ca vt liu. Vt liu c th c cu trc tinh th, v nh hnh, thy tinh hoc vt liu polymer. Trong mt s polymer, c bit l cc polymer si n, chui c th sp xp thnh cc min c trt t. Cc min trt t ny c gi l cc tinh th nh hay vi tinh th. Zeolit Zeolit t nhin v tng hp l alumosilicat c cu trc tinh th xc nh vi cc l xp c kch thc u n. Cc l ny c ni thng vi nhau bng nhng ng rnh cng c kch thc n nh to thnh mt h thng l v ng rnh pht trin c kh nng hp ph cc phn t c kch thc nh hn. Zeolit cn c gi l "ry phn t". Cng thc thc nhim ca zeolit nh sau: M2/m O.Al2O3.nSiO2.pH2O Trong : M cation kim loi ha tr m. P s phn t H2O kt tinh. to thnh tinh th zeolit cc t din SiO4/2 v AlO4/2 lin kt vi nhau qua nguyn t Oxy. T s gia Si v Al l i lng quan trng. Thng thng t l SiO4/2 v AlO4/2 = n. Trong n s nguyn dng, n = 1, 2, 3... Khi tng n bn ca cu trc zeolit tng. Nhng t din SiO4/2 v AlO4/2 l n v cu trc s cp. Nhng n v ny lin kt vi nhau to thnh n v th cp. Hin nay tng hp v pht hin ra khong 7100 lai zeolit khc nhau nhung trong thc t ch c khong 710 loi c ng dng tch cc, trong cc loi quan trng nht l zeolit Y, X, v ZSM-5. Cc zeolit X, Y c cu trc tng t vi cu trc ca fausasit l mt loi zeolit t nhin. Zeolit X, Y c ng knh hc ln l 13Ao, th tch 811 A03, ng knh ca s thng vi hc ln l 8-9 A0.
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n v cu trc th cp ca zeolit X, Y l nhng sodalit c to thnh t 24 t din SiO2 v Al2O3.

nh 3.17: S cu trc mng tinh th zeolit Y: Zeolit ZSM-5 tng hp khng c trong t nhin. T s SiO2 /Al2O3 rt ln, thng l 90-100. Thnh phn ha hc ca SZM-5 dng Na NanAlnSi96-nO192.16H2O Trong n < 27 (thng khong 3) Hng s mang cc gi tr sau: a = 20.1, b = 19.9, c = 13.4 A0 Mng li khng gian ca ZSM-5 gm nhng h thng ng ct nhau to thnh mng khng gian 3 chiu.

Hnh 3.18: Zeolit ZSM 5 Zeolit ZSM-5 hp ph c cc phn t n-parafin, o,p-xylen, 1,2,3trimetylbenzen, khng hp ph cc phn t ln, cng knh nh penta metyl benzen, 1,2,3- trimetylbenzen. Trong thc t ch c mt s lai zeolit t nhin v tng hp c s dng rng ri trong cng nghip c bit l cng nghip ch bin du m v 24
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ha du nh zeolit X, zeolit Y, zeolit ZSM5,... mt s cc vt liu polymer cng c cu trc rt c bit nh lai polymer tinh th lng. Tn ti mt s loi polymer bao gm cc phn ht vi tinh th phn tn trong nn v nh hnh. V d: Cc chui PE (CH 2 CH2)n hoc poly tetra fluoroetylen (CF2 CF2)n u c phn trm khi lng ln vi tinh th. Kch thc ca cc vi tinh th ny c th xc nh bng s m rng ca pic nhiu x.

Hnh 3.19: Vi tinh th trong polymer Vt liu tinh th cho mt loi pic nt do tia nhiu x pht sinh t cc mt phng mng khc nhau. Vt liu v nh hnh cho pic m rng m v tr nh pic trng vi v tr pic mnh quan st thy trong nh nhiu x ca vt liu tinh th ca cht . V d: nh nhiu x ca SiO2 v nh hnh (thy tinh) v SiO2 tinh th (cristo latite) c a ra trong hnh sau:

Hnh 3.20: Nhiu x tia X ca SiO2 tinh th (a) v SiO2 v nh hnh (b).

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Trong vt liu v nh hnh khng c trt t xa nh trong tinh th. Vt liu v nh hnh ch c trt t gn.

Hnh 3.21: Trt t mng dng tinh th v dng v nh hnh. 4. nh lng thnh phn pha tinh th. 4.1.Cu to my nhiu x: gm 3 b phn chnh Ngun to tia 10. Detect tia 10. B phn mu.

Hnh 3.23: Cc loi gi mu chp ph XRD

26

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Loi ng mao qun Loi truyn qua Loi phn x

Cc b phn ny nm trn chu vi ca vng trn tiu t (hnh 15). Gc gia mt phng mu v gc tia ti l . Gc gia phng chiu tia X v tia nhiu x l 2 . Gin nhiu x theo hnh hc ny thng c gi l gin qut 0- 2 . Trong ngun tia X c gia c nh cn detect chuyn ng sut trong thang o gc. Thang o 2 thng l t 0o 170o. Thng thng ngi ta qut t 0o 140o.

Hnh 3.24: Hnh hc nhiu x k tia 10. chp ph nhiu x tia X, mu thng c ch to dng bt vi mc ch nhiu tinh th c nh hng ngu nhin v chc chn rng mt s ln ht tha mn iu kin nhiu x Bragg n n 2 d sin . 4.2. Phng php Rnghen dng bt phn tch cu trc vt liu Mu vt liu dng rn Mu c nghin nh c 1,0 3,0m v c to di dng lp mng vi miligram trn phng. Kch thc bt c nh hng n sai s ca cng peak. sai s ny nh hn1% i hi phi nghin vt liu n kch thc ht c 0,5 1m. Trong thc t t kch thc ht ny rt kh thc hin, cho nn thng th kch thc ht t khong 1 - 5m l kh thi v sai s trong trng hp ny cho php l khong 5% c th chp http://www.ebook.edu.vn 27

nhn dng phn tch nh lng.

28

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S ng u ca kch thc ht cng c ngha quan trng khi chm tia X chiu vo mt phng cha mu, m bo s sp xp ngu nhin m phn ln cc tinh th tun theo nh lut Bragg. Tia X c chiu ti vi cng tia nhiu x c thu bng detector, b chun trc c t trn ng tia to tia mnh v tch t. B lc n sc thng l tinh th. Mu c quay vi tc . Detector quay quanh vi vn tc 2 . Cng tia nhiu x 2 c ghi t ng trn giy v v tn hiu c x l bng my vi tnh cho ngay kt qu. Hnh hc v kch thc n v c th xc nh t v tr gc ca cc pic nhiu x, cn s sp xp ca cc nguyn t trong n v lin quan n cng tng i ca cc pc. Trong ph nhiu x Rnghen bt c th xc nh thnh phn cc pha ha hc ca mu phn tch v cc dng tn ti ca cng mt hp cht v nh lng cc pha. Mi pha gm mt mng nht nh v cho mt h vch nhiu x tng ng trn gin nhiu x. Nu mu gm nhiu pha th trn gin nhiu x s tn ti ng thi nhiu h vch c lp vi nhau. S c mt ca cc vch nhiu x c trng l c s xc nh nh tnh pha c trong mu. 4.3. Phn tch nh lng bng ph nhiu x tia X Da vo s ph thuc cng nhiu x v nng pha theo biu thc sau: I=K P i i m i (3.18)

Trong :

Ki- hng s (Xc nh bng thc nghim) Pi - t l trng lng pha. i - mt pha
m - h s suy gim khi lng ca hn hp

Cc pha cha bit trong vt liu c th xc nh bng cch so snh s liu nhn c t gin nhiu x thc nghim vi s liu chun trong ti liu tham kho.
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29

Trong gin nhiu x, v tr pc ni ln cu trc v i xng ca pha, cn cng pc phn nh tng ca cc pha nhiu x t mi mt phng trong pha tinh th v ph thuc trc tip vo s phn b ca nguyn t trong cu trc tinh th. Nh vy cng pc khng nhng ch lin quan n thnh phn nh lng pha m cn cu trc ca pha. 4.4. o cng vch ph Vic o c cng vch ph trong phn tch nh lng rt quan trng v ph thuc vo cc yu t sau: nhy cu trc nhy ca thit b nhy ca mu o

nhy ca php o Tt c cc yu t ny phn ln u cha trong tha s Khkl cu trc mng. Cng nhiu x lin quan n thnh phn pha, cu trc tinh th ca pha v c biu din qua biu thc sau:
I Ke K( hkl ) X ( / )s

(3.19)

Trong : Ke - h s ph thuc vo iu kin th nghim.


K ( hkl ) - tha s cu trc cho pha X

- t s gia khi lng v th tch ca phn on. - t trng pha

( / ) s - h s hp ph khi, h s ny l mt hm ca nhiu cc

yu t. C th lit k nhng thng s nh hng nh sau:

30

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4.5. Phng php inh lng da trn t l cng nhiu x Phng php hp th nhiu x Da trn t s cng ca pha trong mu phn tch v trong mu tinh khit chun theo biu thc sau:
I ( hkl ) I
o ( hkl )

( / ) ( / )s

(3.20)

Trong :
I o - cng ca pc trong pha tinh khit. I - cng ca pc trong mu phn tch.
( / ) - h s hp ph khi trong hn hp.

Trong nhiu trng hp h s ny thng kh xc nh nn n gin, h s ny c coi nh trong pha cn xc nh. Khi biu thc trn c th vit n gin nh sau:
X I ( hkl ) I o ( hkl )

(3.21)

Trng hp vi hn hp 2 pha h s hp ph khi (/ ) cho mi pha tinh khit c bit trc, cho php tnh ton hm lng mi pha m khng cn h s (/ )s bi biu thc sau:

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31

(I ( hkl ) / I o ( hkl ) )( / ) ( / ) (I ( hkl ) / I o ( hkl ) ) ( / ) ( / )

(3.22)

Biu thc ny c gi l biu thc Klug. Ni chung phng php ny i hi h s hp ph khi ca mu phi c bit trc. Do vy, nu dng phng php ny nh lng pha s c sai s ng k. Trong ti liu c th tra cu h s ny theo tha s tn x nu ha hc ca mu phn tch c bit r. 4.6. Phng php chun ni Phng php chun ni l phng php ph bin nht nh lng pha trong phn tch bng XRD. Phng php ny s loi tr c vn v h s hp ph khi bng cch chia cng ca mi pha cho nhau ( v )
I ( hkl ) I ( hkl ) k X X

(3.23)

Trong : pha

- l pha cn xc nh.
X /X .

- l pha chun.
k - h s hiu chnh xc nh t th I ( hkl ) / I ( hkl )

Hnh 3.25. th chun ni Phng php ny i hi dng ng chun mt cch cn thn v c th nh lng mt pha no khng ph thuc vo nhng pha khc c trong mu. Cn phi chn cc pic chun r rng, khng b chng ln v kch thc ht ca mu phn tch phi ging nhau i vi mu chun v mu phn tch, thch hp nht l khong 1m. 4.7. Phng php so snh cng nhiu x vi cht chun l Corundum (Al2O3). (Saphia hng ngc) I/Icorundum Phng php ny i hi dng Corundum l pha t l 50/50 so vi mu phn tch v dng th ca biu thc

32

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X (

I ( hkl ) I ( hkl )

) theo X

s thu c mt ng thng vi h s gc l K

Hnh 3.26. th ng chun theo cht chun Corundum Al2O3. Kch thc ca corundum ti u l 1m. Trong thc t c th dng cng thc tng qut xc nh pha trong vt liu so vi pha chun theo cng thc sau
RIR I ( hkl ) I ( hkl ) I rel( hkl ) I
rel ( hkl )

X X

(3.24)

Trong Irel - t l ca pic no s dng trong ph XRD.Nu 100% peak trong ph XRD c s dng th gi tr ca t l ny l 1. i lng RIR c th xc nh bng thc nghim cho bt k pha no khi s dng bt k vt liu no lm cht chun: Al2O3 (corundum), SiO2 (thch anh) thng s dng lm cht chun n1. ZnO l cht chun ph bin vi nhng pc r rng. chun ha phng php RIR, Chung(1974) nhn thy rng nu tt c cc pha trong hn hp c bit v nu RIRs cng c xc nh, c th dng biu thc sau tnh ton khi lng ca pha cn bit
I ( hkl ) RIR I
rel ( hk l ) j 1 phakhac

1 I ( hkl ) j / RIR
rel ( hkl )s

(3.25)

Cng thc ny cho php tnh ton khi lng pha m khng cn c cht chun ni. Tuy vy trong thc t ph XRD ca hn hp cht thng c cc pic l khng c xc nh cho nn nu dng cng thc ny dn n sai s ng k. Phn tch nh lng nguyn t bng ph XRD da vo t l cng ca cc vch c trng trong mu vi nng ca nguyn t nghin cu

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33

trong. Vch so snh cn c th kch thch gn vi vch nghin cu,ngha l chng c di sng bng nhau. T l cng vch nguyn t cn xc nh v vch cht chun theo biu thc sau:
I nc I ch K Cnc Cch

(3.26)

Trong : I nc , I ch - cng vch nghin cu v vch chun.


Cnc , Cch - nng nguyn t nghin cu v nguyn t chun.

Phng php Rnghen c th p dng xc nh cc nguyn t c nng ln (hng chc phn trm > 10%) hoc nng nh (2 10%), sai s trung bnh ca phng php l 2 5%. 5. Phn tch cu trc pha Phng trnh nhiu x tia X c th xc nh c cu trc vt rn tinh th. Vic phn tch cc s liu nhiu x thng rt phc tp v tnh a dng ca vt liu. V vy vic phn tch cu trc ch kho st trong trng hp vt liu tinh th c cu trc n gin da trn tinh th lp phng. S sp xp cc nguyn t hay n v quyt nh cng ca pic, cn kch thc v hnh dng ca n v quyt nh v tr gc ca pic. Vic xc nh cu trc tinh th cha bit gm cc bc sau: Tnh kch thc v hnh dng n v t v tr ca pic nhiu x. Tnh s nguyn t thuc n v v hnh dng ca n v, thnh phn ha hc ca mu v mt o c ca n.

Suy ra cc v tr nguyn t thuc n v t cng ca pic. 5.1. Xc nh ch s Miller Khong cch gia cc mt phng d, khang cch gia cc mt ln cn trong mt phng hkl vi cc thng s mng a ca vt liu c cu trc lp phng c th c xc nh t phng trrnh:
1 d2 1 d2 h2
2

h2

k2 a2 l2

l2

(3.27)

Kt hp phng trnh Bragg vi phng trnh trn ta c:


k2 a2 k2 4 si n 2 Q
2

(3.28) (3.29)

T ta c: sin 2 Q

4a 2

l2

34

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Tha s Khi gc

4a 2

K l mt hng s cho bt k nh nhiu x no.

tng, mt phng vi ch s Miller ln hn s tham gia nhiu x


sin 2 Q1 sin 2 Q2 h12 h2 2 k12 l12 k2 2 l2 2

c th vit theo phng trnh sau: (3.30)

Trong h lp phng i vi mng lp phng, phn x bc nht do phn x t cc mt vi ch s Miller kiu: (100) cho lp phng n gin 2

(110) cho lp phng tm khi (111) cho lp phng tm mt


k
2

Tng ng vi tng h

l 2 = 1, 2, hoc 3.

Bng cch chia cc gi tr sin2

ca cc phn x khc nhau cho sin2

ca cc phn x bc nht v nhn cc t s thu c vi s nguyn thch hp thng l 2 hoc 3 s thu c cc gi tr ca hkl tng ng. Bng 3.7: Dng tng bnh phng ca mt s ch s Miller cho h lp phng.
h
2

l2

1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

hkl 100 110 111 200 210 211 220 300, 221 310 311 222 320 321 400 410, 322 411, 330 331 420 421 332

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Mng LPG LPG, LPTK LPG, LPTM LPG, LPTK, LPTM LPG LPG, LPTK LPG LPG, LPTK, LPTM LPG LPG, LPTK LPG, LPTM LPG, LPTK, LPTM LPG LPG, LPTK LPG LPG, LPTK, LPTM LPG LPG, LPTK LPG, LPTM LPG, LPTK, LPTM LPG LPG, LPTK

35

23 24 5.2. Nhn bit mng Bravais

422

LPG LPG, LPTK, LPTM

Theo qui tc chn la gi tr h 2 qui lut sau. n gin: 1, 2, 3, 4, 5, 6, 8, 9, Tm khi: 2, 4, 6, 8,10, 12,

l 2 cho mng lp phng tun theo

Tm mt: 2, 4, 8, 11, 12, 16, 19, 20, Mng Bravais v cu trc tinh th c th nhn bit c t trnh t cc gi tr h 2
k
2

l 2 trong nh nhiu x.

Bng 3.8: Qui tc chn la cho phn x. Mng Bravais n gin Tm khi Tm mt
h

C phn x Tt c cc mt
2

Khng c phn x Khng


h
2

l - chn
2

l 2 - l

h, k, l cng chn hoc cng l

h, k, l hn hp

nh nhiu x t vt liu c cu trc lp phng c th phn bit c ngay vi nh nhiu x t vt liu khng phi lp phng c tnh i xng thp. Trong cu trc lp phng n gin v LPTK khong cch gia cc pic gn bng nhau. Thng s mng a c th tnh ton theo cng thc sau:
a h2 2 sin k
2

l2

V d: tnh ton thng s mng ca nguyn t Al

Hnh 3.27.Ph nhiu x ca Al

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Ta c th t

4a 2

= A v y l hng s cho bt k nh nhiu x no.

Gi tr A tng ng vi h2 + k2 +l2 = 1 V d: Xc nh ch s nh nhiu x ca vt liu c cu trc lp phng nh sau (nh ghi nhn vi bc x CuK ) thu c 9 pc vi cc gc 2 nh sau: Bng 3.9.Cc thng s mng ca Al-Cu- (K 1) = 0,254056nm S pic 1 2 3 4 5 6 7 8 9 2 38,52 44,76 65,14 78,26 82,47 99,11 112,03 116,60 137,47 Sin2 0,1088 0,1450 0,2898 0,3983 0,4345 0,5792 0,6876 0,7238 0,8684
Sin 2 Sin 2
min

Sin 2 x3 Sin 2 min

h2+k2+l2 3 4 8 11 12 16 19 20 24

hkl 111 200 220 311 222 400 331 420 422

a (nm) 0,4044 0,4045 0,4047 0,4048 0,4048 0,4049 0,4049 0,4049 0,4049

1,000 1,333 2,664 3,661 3,994 5,324 6,320 6,653 7,982

3,000 3,999 7,992 10,983 11,982 15,912 18,960 19,958 23,945

Nh bng trn tnh ton cho thy ch c cc phn x vi cc gi tr hkl chn c hoc l c l hin din. Theo quy tc chn lc c th kt lun rng mng Bravais l LPTM v cu trc tinh th l cu trc LPTM. 5.3. Kch thc tinh th i vi nhng tinh th kch thc ln (khong 1000 n v c s), ph nhiu x th hin bng nhng pc nhiu x v tr gn gc Bragg. Cn nhng pc khc b trit tiu khng th hin trn ph nhiu x. i vi nhng tinh th c kch thc nh (khong 1 m) c th dng cng thc Sherrer tnh ton kch thc tht t ph nhiu x nh sau
D K D cos

(3.31)

Trong :

- chiu rng na pc

K - h s hnh th (thng khong 0,9) - bc sng pht x

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Quan h gia b rng pc nhiu x thu c trn ph v kch thc ht nh sau

Hnh 3.28. th ph thuc dong pc v cng nhiu x 6. c trng ph XRD ca mt s vt liu C th ni khong 90% vt liu rn v c nhn to hoc t nhin c cu trc tinh th.Trong s cc nhm vt liu khong v vt liu xc tc cho ngnh cng nghip du kh v cc ngnh khc thung c s dng l cc nhm sau. Vt liu khong st Vt liu zeolit Vt liu kim loi v oxit kim loi Sau dy l mt s th d v cc ph c trng ca chng. 6.1. Nhm vt liu khong st

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Hnh 3.27: Ph XRD ca vt liu khong cao lanh t nhin, ngun pht CuK

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Hnh 3.28: Ph XRD ca vt liu canxit, ngun pht CuK

Hnh 3.29: Ph XRD ca vt liu khong Ilit

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Hnh 3.30: Ph XRD ca vt liu thch anh

Hnh 3.31: Ph XRD ca vt liu Analcim 6.2. Nhm vt liu zeolit

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Hnh 3.32: Ph XRD ca vt liu zeolit Li-ABW Cng thc ho hc: [Li4(H2O)4][Si4Al4O16] Thng s mng c s: a =10,313 Ao b=8,914 Ao c= 4,993 Ao Gc alpha =90o, beta =90,o gama =90 o

Hnh 3.33:Ph XRD ca vt liu Zeolit AlPO-18 Cng thc ho hc: Al24P24O96 42
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Thng s mng c s: a =13,711Ao b=12,731 Ao c= 18,570 Ao Gc: alpha = 90, beta =90,01, gama =90 o

Hnh 3.34:Ph XRD ca vt liu AFG Cng thc ho hc: [ Na 17K4.7 Ca 10](SO4)6 [Si24Al24O96] Thng s mng c s: a = 12.76 Ao b= 12.76 Ao c= 21.41 Ao Gc alpha =90o, beta =90,o gama =120 o Cng thc ho hc: [C2H8N2)(H2O)16[Al24P24O96] Thng s mng c s: a = 10.321 Ao b= 13.631 Ao c= 17.454 Ao Gc alpha =90o, beta =90,o gama =90 o

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Hnh 3.35:. Ph XRD ca vt liu ALPO-EN3

Hnh 3.36: Ph XRD ca vt liu euo Cng thc ho hc: [H2O]36[Si112O224] Thng s mng c s: a = 13.695 Ao b= 22.326 Ao

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c= 20.178 Ao Gc alpha =90o, beta =90,o gama =90 o

Hnh 3.37: Ph XRD ca vt liu MON Cng thc ho hc: [ Na Thng s mng c s: a = 7.41 Ao b= 7.41 Ao c= 17.307Ao Gc alpha =90o, beta =90,o gama =90 o 6.3. Nhm vt liu kim loi v oxit kim loi.
0.1K4.3 (H2O)5[Si11Al4.7O32]

Hnh 3.38: Ph XRD ca kim loi Zn vi bc x CuK

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Hnh 3.39: Ph XRD ca vt liu TiO2 bc x CuK 7. Thc hnh chp ph XRD ca vt liu xc tc phng php rnghen bt Mc ch: Gip hc vin nm vng cch chun b mu o, cch thao tc vn hnh trn my XRD v gii c cc ph , tnh ton thnh phn pha v xc nh cu trc pha. nh gi kt qu phn tch, vit bo co th nghim. 7.1. Cc cng vic chun b 7.1.1. Thit b o ph vi cc cu hnh gm ng pht tia X, b lc sng. Gi mu, thu tinh mu.

B nhn tn hiu v khuch i tn hiu. B phn x l s liu. 7.1.2. Dng c, ho cht, ti liu tra cu Kh N2, H2. Ci nghin mu (ci m no). Bnh ht m.

Cc mu vt liu chun v cc mu phn tch. B ti liu tra cu thng s (ATLAS XRD ASTM). 7.2. Tin hnh th nghim 7.2.1. Chun b mu bt phn tch Nghin nh mu phn tch sao cho t mn khong 1 - 5 m. Cho mt lp mng mu bt v dn tht u trn mt knh lm gi , sau t vo hp mu phn tch trn my. 7.2.2. Tin hnh chp ph XRD

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Trc tin phi kim tra an ton v tnh trng hot ng ca my, kim tra in v kh. Kim tra ng pht tia X, dng ngun pht t kim loi no bit r bc sng ti ( ). Thng thng dng ngun l CuK vi = 1,54 M my chy vo ch lm vic v ci t cc thng s theo hng dn thao tc vn hnh ca tng loi my (ch c k hng dn trc khi thao tc). my n nh. Tin hnh chp ph XRD ca cc mu phn tch theo gc 2 t 0 60 (hoc hn tu theo mc ch). Chp ph XRD ca cc mu chun theo trnh t trn trong cng iu kin nh nhau.

Kt thc php o v thu nhn cc ph . X l cc ph . 7.2.3. Tnh ton thnh phn pha Thnh phn pha mi vt liu c tnh ton theo cng thc trong ti liu gio trnh Kch thc ht tinh th theo cng thc Sherrer. Xc nh cu trc pha tinh th. Tnh ton thng s mng t cc s liu ca ph theo cng thc nh trnh by trn khi bit v tr ca cc peak (gc 2 ). T tnh c cc thng s mng hkl (ch s Miller) v xc nh cu trc tinh th ca vt liu. Xc nh cng tng i ca cc peak trong ph v nh tnh, nh lng cc pha trong mu. Vit phiu nh gi thc hnh (theo mu). Bng tng kt thc hnh phn tch xc nh cu trc v thnh phn pha Tn mu A (nm) h2 + k2 + l2 hkl

Vit bi thc hnh v cc ch thch trong qu trnh thao tc Nhn xt v quan h gia cng pic v thng s mng Nhn xt v phn gii ca cc pic 8. Cu hi bi tp gii ph nhiu x tia X

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8.1. Cu hi l thuyt Cu 1. Mng khng gian v c bn. M s cu trc tinh th in hnh. Cu 2. Ch s Miller ca mt tinh th v cch xc nh. Cu 3. Bn cht ca phng php nhiu x tia 10. S to thnh tia X v tnh cht ca n. Cu 4. C s ca phng php nh tnh v nh lng thnh phn pha tinh th 8.2. Bi tp 1. Ph XRD ca kim loi Pb chp theo phng php bt vi bc x CuK ( =1.539 Ao). Tnh gi tr ca khong cch mt mng tinh th theo cc ng bc 1 v gc l =67.1 o 2. Ph XRD ca vt liu c cc pc nhiu x tng ng vi gc l 24.3;23.4;21;v 17.5. Dng ng pht tia l Cu c bc sng l ( =1.539 Ao) Hy tnh phong cch mt phng d cc gc nhiu x theo phng trnh Bragg. 3. 4. Tnh chiu di cng tinh th dng LPTK ca Fe bit rng ph XRD vi =2Ao. o khong cch mt cho tinh th (110) c gc =30o Tnh gc 2 ca gic k khi vch K ca cc nguyn t Fe (1.76 A0) Se(0.992 A0) Ag (0.497 A0) vi cc tinh th phn tch l: a. Topaz d= 1.356 b. LiF d=2.014 5. c. NaCl d=2.820 Tnh th vn hnh ti thiuu kch thch cc vch sau y: a. Vch K ca Ca (3.064 A) b. Vch ca L As (9.370 A) c. Vch L ca U (0.592 A) d. Vch K ca Na (0.496 A) 6. Chiu di sng cc tiu khi cc electron lp K ca Zirconi l 0.7 A0. Tnh th cc tiu cn thit kch thch cc electron lp K trong ng pht tia 10. Xc nh thng s mng v ch s Miller ca kim loi Zn c ph XRD nh sau.

7.

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S pic 1 2 3 4 5 6 7 8 9

2 36.31 38.98 43.21 54.32 70.08 70.64 77.04 82.09 83.72

Sin

Sin 2 Sin 2 m in

Sin 2 x3 Sin 2 m in

h2+k2+l2

hkl

a (nm)

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P N CU HI V BI TP
Bi 1: Ph hng ngoi (IR) Cu 1 1 cm vi sng 0,8 m -kh kin 10 m -hng ngoi 100 nm- t ngoi 10nm ta 10. (Rnghen) Cu 2 893 cm -1 hng ngoi 3.104 cm-1 kh kin 5,0 cm -1 vi sng 8,7.10 -4 cm-1 t ngo1. Cu 3 E=h Cu 5.2 = hc/ = (6,63.10-34x3,0.1010) /5.109 = 4.10-15 Jun

Cu 5.3

Cu 5.4

Cu 5.5

Cu 5.6

Cu 5.7 50
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Cu 5.8

Bi 2: Ph hp thu nguyn t (AAS) Cu 6 Phng ca tia = 300 nm (m = 1) ng thi trng chp phng ca tia = 150 nm (m = 2). Vy c tia 300 nm thun khit phi dng thm knh lc thch hp gi li tia 150 nm. Trong my n sc cch t u c thm knh lc gi li cc tia thuc bc nhiu x khc. Cu 7 Nhn xt: Gc nghing ngoi, cn gc nghing
2= 1

= 12,30 thch hp khi phn gii ph vng t va nng cao hiu nng phn gii ph

32,50 thch hp khi phn gii ph vng kh kin.

Vic s dng cch t kp va tn mt cch t na. Cu 8 f= 347 mm Bi 3: Ph nhiu x tia X (XRD) Cu 1 d=0.8109Ao Cu 2
o

sin 0,4115 0,3971 0,3583 0,3007

d(nm) 1,87 1,94 2,15 2,56

24,3 23,4 21,0 17,5 Cu 3


a d 2

2 2

2, 828 A o

Cu 4 a. Tinh th phn tch Topar i vi Se: 2 = 42,90


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b.

i vi Ag: 2 = 21,10 Tnh tng t cho tinh th phn tch l LiF Ta c kt qu sau 2 : Fe = 31,80 Se = 28,50 Ag = 14,20

c.

Tinh th phn tch NaCl 2 Fe = 36,40 Se = 20,30 Ag = 10,10

Cu 5 V
V V V

12400 x min 103


12400 9, 370 12400 0, 592 12400 0, 496 12400 0, 7 12400 0, 7

12400 3,064
1323 , 4 V

4046, 99V

4,04699KV

20945 , 9 V 20 , 9459 KV 25000 V 25KV

Cu 6
V V 17714 , 3 V 17, 7143 KV 17714 , 3 V 17, 7143 KV

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CC THUT NG CHUYN MN V CC CH VIT TT


IR - InfraRed spectroscopy -Quang ph hng ngoi XRD X-ray Diffraction spectroscopy Ph nhiu x tia X. AAS Atomic Absorption Spectroscopy Ph hp thu nguyn t. ASTM - The Americal Society for tesying and materials. HSX h s xp. LPG Lp phng n gin. PLTK - Lp phng tm khi. LPTM Lp phng tm mt SPXC - su phng xp cht. Bn knh : r, R Bc sng in tch in t Ch s Miller Gc Cng Hng s Plank H s hp ph Khong cch Khi lng Mt Mt phng mng Nhit Nguyn t s Nng nguyn t c bn S Avogadro Tn s Th Tha s cu trc Vch c trng Vn tc Vn tc nh sng Cng dng in : : : : : : : : : : : : : : : : : : : : : : : V F K, L, M v C A
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e h, k, l I h d M h, k, l T Z Xi a, b, c NA

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Nng lng Lc in p in tr cm ng t Nng lng bc x Mt quang H s hp th

: : : : : : : :

Jun N (Niuton) V (vn) V/m T (tesla). E (eV) D

Cng in trng :

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TI LIU THAM KHO


1. 2. 3. 4. 5. 6. 7. 8. 9. Nguyn nh Triu, Nguyn nh Thnh - Cc phng php phn tch Vt l v Ho l, NXB KHKT, H ni 2001 T Vn Mc - Phn tch dng c - NXB KH&KT, H ni 1999. Nguyn Hu nh, Trn th - ng dng mt s phng php ph nghin cu cu trc phn t - NXB Gio dc, H ni 1999. Analytical Method for Atomic absorption spectroscopy, The perkin Elmer Coproration, 1996. B.C .Smith - Fundamental of Fourier Transform IR Spectroscopy CRC press. FL., 1996 G. Socrates - Infared Characteristic Group frequences Tables and Charts - Wiley Chichester, 1994 Janusz Ryczkowski - IR spectroscopy in Catalysis - Catal. Today, 68, 263-381, 2001 Roeges - A guide to the Complete interpretation strucrure - Wiley Chichester, 1994. http://Zeolites.ethz.ch. of IR of Organic

10. James R. Connolly - Introduction to X-ray Powder diffraction - EPS 400 002 , 2005

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