PP PH Tia X PDF

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.
C s ca phng php ph Rnghen
2.
3.
Phng trnh nhiu x Bragg-Vulf.

ng dng ph Rnghen phn tch thnh phn pha ca tinh th
4.
5.
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
http://www.ebook.edu.vn
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
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
a=b=c
= = 90o
a=b c
= = 90o, = 120o
a b c
=
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
Hu ht cc kim loi (khong90%)
kt
tinh
90o trn s ha rn thnh ba cu
trc tinh th xp cht l:
-
Lp phng tm khi (LPTK)

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
(3.1)
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
(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)
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
LPTK
LPTM
Kim loi
Hng s mng
a (nm)
Bn knh nguyn
t R (nm)
Crom (Cr)
0,289
0,125
St (Fe)
Molipden (Mo)
0,287
0,315
0,124
0,136
Kali (K)
0,533
0,231
Natri (Na)
Tantal (Ta)
Vonfram (W)
0,429
0,330
0,186
0,143
0,316
0,137
Vanadi (V)
0,304
0,132
Nhm (Al)
0,405
0,361
0,143
0,128
0,408
0,495
0,144
0,175
0,352
0,125
0,393
0,409
0,139
0,144
ng (Cu)
Vng (Au)
Ch (Pb)
Niken (Ni)
Platin (Pt)
Bc (Ag)
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.
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
Hng s mng
Bn knh
nguyn t
R (nm)
T s
c/a
% lch
khi gi tr
Cadimi (Cd)
0,2973
0,5618
0,149
1,890
+15,7
Km (Zn)
Magie (Mg)
Coban (Co)
Ziriconi (Zr)
Titan (Ti)
Benili
0,2665
0,4947
0,133
1,856
+13,6
0,3209
0,2507
0,3231
0,5204
0,4069
0,5148
0,160
0,125
0,160
1,623
1,623
1,593
-0,61
-0,61
-2,45
0,2950
0,2286
0,4683
0,3584
0,147
0,113
1,587
1,568
-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 (, , )
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.
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 ]
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
1/3
3
2/3
3/2
1
1
Trit tiu phn s
Tiu ch
Ta im ct
Ly nghch o
Trit tiu phn s
1
1
0
0
0
0
Ch s Miller s l (6 3 2)
Tnh ton
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)
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
-a1
+a3
-a2
+a2
o
120 C
+a1
-c
-a3
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 }
10
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
11
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
tinh th LPTM; st delta
t 1394oC
tn ti t
t 912oC
1394oC c cu trc
1539oC cu trc LPTK nhng c hng
s mng ln hn st .
Bng 3.5. Dng tinh th th hnh ca mt s kim lo1.
Kim loi
Cu trc tinh th
o
T phng
To khc
Ca
Co
LPTM
SPXC
LPTK (> 447O C)

LPTM (> 427OC) LPTM
Fe
LPTK
(912oC
Li
Na
Ti
LPTK
LPTK
SPXC
SPXC
Zr
SPXC
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
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
m) c gi l ht c cng cu trc mng nhng vi nh
hng
khc nhau mang tnh ngu nhin v lin kt vi nhau bng bin gii ht.
Hnh 3.11: M hnh n tinh th v a tinh th

13
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.
14
Cp ht
S ht trong
in2, x 100
S ht trong
1 mm 2 x 1
Din tch tht

ca 1 ht (mm2)
1,0
15,5
0,0645
2
3
4
2,0
4,0
8,0
31,0
62,0
124,0
0,0323
0,0161
0,00807
5
6
7
16,0
32,0
64,0
248
496
992
0,00403
0,00202
0,001008
8
9
128
256
1980
3970
0,000504
0,000252
10
512
7940
0,000126
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 f ca n:
E = h.f
lamda
Mt khc tn s f lin quan ti bc sng

hc
lamda=
E
(3.7)
theo cng thc sau:

(3.8)
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
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 <
15
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.
16
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.
alpha
beta
Cc vch Kbeta
c nng lng ln hn so vi L v khng b hp th
alpha
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).
17
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,
=Z .
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
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)
Phng trnh ny biu th mi quan h gia gc cc tia nhiu x
bc sng tia ti, khong cch gia cc mt phng nguyn t. Nu nh lut

Bragg khng c tha mn th s khng xy ra hin tng giao thoa.
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.
19
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
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
2
I
I
o 2 2 4 sin 2
r m ec
(3.14)
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
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
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.
2
sin cos
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.
23
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
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).
25
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
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
27
nhn dng phn tch nh lng.
28
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 w . Detector quay quanh vi vn tc 2 teta
.
Cng tia nhiu x 2tetac 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
Trong :
P
i
i m
i
(3.18)
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.
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
(3.19)
( / )s
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
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
( / )
( / )s
o
( hkl )
(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:
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 )
Trong :
pha
X
X
(3.23)
- l pha cn xc nh.
- l pha chun.
k - h s hiu chnh xc nh t th I ( hkl ) / I ( hkl )
X /X .
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
X (
I ( hkl )
I ( hkl )
s thu c mt ng thng vi h s gc l K
) theo X
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
I ( hkl )
RIR
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
(3.25)
phakhac
( hk l )
j 1
I ( hkl ) j / RIR
rel
( hkl )s
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
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
Cnc
(3.26)
Cch
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
h2
k2
a2
l2
(3.27)
Kt hp phng trnh Bragg vi phng trnh trn ta c:

h2
1
d2
T ta c: sin 2 Q
34
k2
a2
l2
k2
l2
4 si n 2 Q
2
(3.28)
4a 2
(3.29)
Tha s
K l mt hng s cho bt k nh nhiu x no.
4a 2
tng, mt phng vi ch s Miller ln hn s tham gia nhiu x
Khi gc
c th vit theo phng trnh sau:

sin 2 Q1
sin 2 Q2
h12
h2 2
k12 l12
k2 2 l2 2
(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
-
(110) cho lp phng tm khi

(111) cho lp phng tm mt
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
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
l2
hkl
100
110
111
200
210
211
220
300, 221
310
311
222
320
321
400
410, 322
411, 330
331
420
421
332
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
LPG
LPG, LPTK, LPTM
422
5.2. Nhn bit mng Bravais

Theo qui tc chn la gi tr h 2
l 2 cho mng lp phng tun theo
qui lut sau.

n gin: 1, 2, 3, 4, 5, 6, 8, 9,
Tm khi: 2, 4, 6, 8,10, 12,
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
l 2 trong nh nhiu x.
Bng 3.8: Qui tc chn la cho phn x.

Mng Bravais
C phn x
n gin
Tt c cc mt
Tm khi
Tm mt
Khng c phn x
Khng
l - chn
2
l 2 - l
h, k, l hn hp
h, k, l cng chn hoc cng

l
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
l2
2 sin
V d: tnh ton thng s mng ca nguyn t Al
Hnh 3.27.Ph nhiu x ca Al
36
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
38,52
44,76
0,1088
0,1450
65,14
4
5
Sin 2
Sin 2
x3
Sin 2 min
h2+k2+l2
hkl
a (nm)
1,000
1,333
3,000
3,999
3
4
111
200
0,4044
0,4045
0,2898
2,664
7,992
220
0,4047
78,26
82,47
0,3983
0,4345
3,661
3,994
10,983
11,982
11
12
311
222
0,4048
0,4048
6
7
99,11
112,03
0,5792
0,6876
5,324
6,320
15,912
18,960
16
19
400
331
0,4049
0,4049
116,60
0,7238
6,653
19,958
20
420
0,4049
137,47
0,8684
7,982
23,945
24
422
0,4049
Sin2
Sin 2
min
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
Trong :
K
D cos
(3.31)
- chiu rng na pc
K - h s hnh th (thng khong 0,9)

- bc sng pht x
37
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
38
Hnh 3.27: Ph XRD ca vt liu khong cao lanh t nhin, ngun pht CuK
39
Hnh 3.28: Ph XRD ca vt liu canxit, ngun pht CuK
Hnh 3.29: Ph XRD ca vt liu khong Ilit
40
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
41
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
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
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
43
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
44
c= 20.178 Ao
Hnh 3.37: Ph XRD ca vt liu MON

Cng thc ho hc: [ Na
0.1K4.3 (H2O)5[Si11Al4.7O32]
Thng s mng c s:
a = 7.41 Ao
b= 7.41 Ao
c= 17.307Ao
6.3. Nhm vt liu kim loi v oxit kim loi.
Hnh 3.38: Ph XRD ca kim loi Zn vi bc x CuK
45
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
-
46
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
60 (hoc hn tu theo mc ch).

Chp ph XRD ca cc mu chun theo trnh t trn trong cng
t 0
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
47
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
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.
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
4.
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
7.
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.
48
S pic
36.31
2
3
38.98
43.21
54.32
5
6
7
70.08
70.64
77.04
8
9
82.09
83.72
Sin
Sin 2
Sin 2 m in
Sin 2
x3
Sin 2 m in
h2+k2+l2
hkl
a (nm)
49
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
= hc/
= (6,63.10-34x3,0.1010) /5.109 = 4.10-15 Jun
Cu 5.2
Cu 5.3
Cu 5.4
Cu 5.5
Cu 5.6
Cu 5.7
50
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=
= 12,30 thch hp khi phn gii ph vng t
32,50 thch hp khi phn gii ph vng kh kin.
Vic s dng cch t kp

va
va nng cao hiu nng phn gii ph
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
d(nm)
24,3
0,4115
1,87
23,4
21,0
17,5
0,3971
0,3583
0,3007
1,94
2,15
2,56
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
51
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
12400
x
min 103
12400
3,064
4046, 99V
4,04699KV
12400
9, 370
1323 , 4 V
12400
0, 592
20945 , 9 V 20 , 9459 KV
12400
0, 496
25000 V
12400
0, 7
17714 , 3 V 17, 7143 KV
12400
0, 7
17714 , 3 V 17, 7143 KV
25KV
Cu 6
52
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
h, k, l
Gc
Cng
:
:
Hng s Plank
H s hp ph
Khong cch
Khi lng
Mt
Mt phng mng
:
:
h, k, l
Nhit
Nguyn t s
Nng nguyn t
:
:
Z
Xi
c bn
S Avogadro
:
:
a, b, c
NA
Tn s
Th
Tha s cu trc
Vch c trng
Vn tc
Vn tc nh sng
:
:
:
K, L, M
v
C
Cng dng in
A
53
Nng lng
Jun
Lc
in p
:
:
N (Niuton)
V (vn)
Cng in trng :
V/m
in tr
cm ng t
T (tesla).
Nng lng bc x
E (eV)
Mt quang
H s hp th
54
TI LIU THAM KHO

1.
Nguyn nh Triu, Nguyn nh Thnh - Cc phng php phn tch

Vt l v Ho l, NXB KHKT, H ni 2001
2.
3.
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.
4.
Analytical Method for Atomic absorption spectroscopy, The perkin Elmer

Coproration, 1996.
5.
6.
B.C .Smith - Fundamental of Fourier Transform IR Spectroscopy CRC press. FL., 1996
G. Socrates - Infared Characteristic Group frequences Tables and Charts
7.
- Wiley Chichester, 1994

Janusz Ryczkowski - IR spectroscopy in Catalysis - Catal. Today, 68,
263-381, 2001
8.
Roeges - A guide to the Complete interpretation

strucrure - Wiley Chichester, 1994.
9.
http://Zeolites.ethz.ch.
of IR of Organic
10. James R. Connolly - Introduction to X-ray Powder diffraction - EPS 400 002 , 2005
55

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BI 3.

PH NHIU X TIA X (XRD)

M t c s ca phng php ph Rnghen, my o ph

nh tnh v nh lng thnh phn pha ca zeolit

C s ca phng php ph Rnghen

Phng trnh nhiu x Bragg-Vulf.

nh lng thnh phn pha.

6. Mt s ph Rnghen ca vt liu cht rn.

1.1.Mt s khi nim v vt liu rn v cu trc tinh th hc

Cc nh tinh th hc a ra by kiu n v xy dng cc mng

Hnh 3.1: Mng khng gian ca tinh th rn l tng, n v v hng s

Kiu mng Bravais

Lp phng tm khi (LPTK)

Su phng xp cht (SPXC)

Hnh 3.2: Cu trc tinh th ca vt liu rn

i vi cu trc lp phng tm mt, quan h gia chiu di cnh (a) v

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

Trong : V1: s nguyn t trong n v x th tch nguyn t.

Cu trc su phng xp cht (SPXC): trong cu trc ny tng s

Hnh 3.3: V tr cc nguyn t trong mng c s:

1.2.4. Cch k hiu v tr nguyn t trong c bn lp phng

Hnh 3.4: Cc mt phng ca tinh th lp phng n gin

Hnh 3.5: Trc ta vung gc xyz

Chn mt mt phng khng qua gc ta .

Xc nh cc ta giao im ca mt phng vi cc trc x, y, z

Trit tiu cc phn s v xc nh tp s nguyn nh nht, cc s

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.

Trit tiu phn s

Ch s Miller ca mt phng s l (1 0 0).

Trong : a l hng s mng.

Hnh 3.8: Bn trc ta ca tinh th SPXC.

Hnh 3.9: Ch s Miller- Bravais ca mt tinh th SPXC

Nhiu nguyn t c th tn ti cc dng tinh th khc nhau ph thuc

912oC c cu trc tinh th LPTK; st

tinh th LPTM; st delta

1539oC cu trc LPTK nhng c hng

LPTK (> 447O C)

LPTK (> 1394oC)

1.2.10. Sai lch mng tinh th

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

AA - M hnh n tinh th; b - a tinh th, c - Vi hp kim a tinh th

Din tch tht

2. Nhiu x tia X, phng trnh Vulf Bragg

Mt khc tn s f lin quan ti bc sng

theo cng thc sau:

Tn x (Scattering): l qu trnh hp thu v ti bc x th cp theo cc

to thnh sng tng hp.

1% c chuyn thnh tia 10. Do vy cn phi lm ngui ng pht Rnghen

Hnh 3.12: S nguyn tc ng pht tia Rnghen.

Hnh 3.13: M hnh nguyn t v s to thnh tia X c trng. K K , L

Kh nng xuyn thu: tia Rnghen c kh nng xuyn qua mt s

Gy s ion ha ca cht kh.

Hin tng nhiu x

Hnh 3.14: Nhiu x tia X bi cc mt phng ca nguyn t (A-A - B-B ).

Qung ng 1-P-1 v 2-Q-2 bng s nguyn ln bc sng.

Phng trnh ny biu th mi quan h gia gc cc tia nhiu x

bc sng tia ti, khong cch gia cc mt phng nguyn t. Nu nh lut

Thng s d/n l khong cch gia cc mt phng hkl v nh, nk, nl l cc

Hnh 3.14: Nhiu x tia X t cc mt ca mng tinh th.

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

Nhiu x tia X bi in t t do.