cng mn CNSXCM V c

Phn 1: i cng v mu sc v cht mu Chng I: m u Chng 2: i cng v l thuyt mu sc Chng 3: cc h thng so snh mu sc Phn 2: sn xut pigment v c Chng 4:cc phng php sn xut pigment v c Chng 5: k thut sn xut TiO2 t ilmenit Chng 6: k thut sn xut Cr2O3 t qung cromit Chng 7:k thut sn xut mt s pigment v c

Ti liu tham kho

1/Gio trnh CNSXCMVC trng HBKtpHCM 2/Gunter buxbaum Industrial inorganide pigments Federal republic of germany 1998 3/American society for testing and material Paints pigment,resins and polymers 4/M.E O Texoo coe 5/Gio trnh l thuyt mu sc trng HBK H ni 6/G.N phadeev Ha hc v mu sc NXB khoa hc k thut 1985 7/Nguyn nh Soa: Ha v c trng HBKtpHCM

Phn 1: i cng v mu sc v cht mu chng 1: M u I.1-Hin tng mu v i tng ca KHMS Chng ta nhn bit c vt cht l do: + vt cht pht ra ngun bc x + vt cht phn x nh sng chiu vo Hai thuc tnh c bn ca vt cht m mt ta c th nhn bit: + hnh dng ca vt cht: o ,thy c +Mu sc ca vt cht: ch cm nhn

1-Hin tng mu
Gm 3 qu trnh chnh: +Vt l: bc x v phn x nng lng +Sinh l: tc ng ca nng lng vo mt +Tm l: mt th cm mu 1.1-qu trnh vt l: nghin cu v nng lng bc x gm : + s pht v truyn nng lng + s phn b nng lng theo xc nh bi phng php khch quan v biu th bi cc n v o vt l

1.2-qu trnh sinh l +Nghin cu s tc ng ca cc ngun bc x ti c quan th gic +Mi quan h gia cu to ca c quan th gic vi cc mu tng ng 1.3 qu trnh tm l: nghin cu qu trnh th cm mu ca h thn kinh thi gic v cc iu kin th cm mu sc ca con ngi nh :tr nh , kinh nghim,thi quen , i tng ca mn tm l mu phc tp

I.2/s lc lch s pht trin khoa hc mu sc

Gn 4000 nm trc ngi Ai cp s dng cht mu, nhng h cho rng mu l s kt hp sng-ti Th k XV-XVI mt s nh bc hc nh Decac,Huck v Kiple mi nu cc gi thuyt gn lin mu sc vi nh sng nhng cha cp ti vai tr ca c quan th gic Th k XVII ,Newton nghin cu v nh sng v phn tch ph ca n , cho rng mu sc ca vt c to bi qu trnh vt l (khch quan) v phn cm nhn (ch quan) Th k XIX, Thomas young gii thch c s th cm mu ca c quan th gic. Mu sc m ta cm nhn l kt qu ca s kt hp cc kch thch R-G-B c quan ny .S khc bit v cht v lng ca cc kch thch trn to khc bit v mu sc ca th gii vt cht Th k XX ,CIE cng nhn cc nghin cu ca V.Vrai v J>Ghin v mu sc ca th gii vt cht,

I.3.nh ngha-tiu chun nh gi cht mu I.3.1.nh ngha

Cht mu (pigment) c gc t ting latin pigmentum c ngha nguyn thy l mu sc trong Cui i Trung i t pigment ch tt c cc tinh cht chit ra t cc loi cy dng nhum mu Sau ny pigment l tn gi tt c nhng cht dng ht nh khng tan trong dung mi v c kh nng to mu, bo v hay c t tnh C piment v thuc nhum ( dyer) tuy u thuc nhm cht to mu nhng do khc bit v kh nng tan trong dung mi nn pigment thng dng cho cc cht c ngun gc v c

I.3.2 tiu chun

nh gi cht lng pigment thng da vo cc tiu ch: +Thnh phn ha hc +Cc tnh cht quang hc +Kh nng phn tn +Kh nng che ph, bo v +Cc c tnh v mu sc ( tng mu, cng mu,) +Cc c tnh l ha nh t trng ,kch thc ht, thc t trong cht mu ngoi cht chnh l pigment cn c mt cc cht khc gi chung l ph gia (extender) hay cht n. chng c mu trng hay mu rt nht, dng bt, khng tan

I.4.lch s pht trin ngnh sn xut cht mu

T thi tin s con ngi bit dng cht mu c sn trong t nhin Khong 4000 nm trc con ngi bit khai thc, x l , phi trn cc cht mu c sn trong t nhin , tinh lc khong cht v chit t trong cy, c Th k XVIII ra i v pht trin ngnh sn xut pig qui m cng nghip vi cc sn phm nh xanh berlin, crom vng , Hin nay ngnh cng nghip sn xut pig pht trin rt mnh c chiu rng v chiu su ( a dng , sn lng , qui m sn xut ,)

I.5.khi qut v la chn v phn loi pigment I.5.1 la chn pigment

Vic la chn pigment phi cn c vo cc c tnh mu nh tng mu , cng mu , ph, kh nng tn x, phn x , ngoi ra cn phi cn c vo: +Cc tnh cht l ha c bn: thnh phn ha, %m, +Cc c tnh c hc: bn (tnh c bn nh sng,thi tit,), cng , +Kh nng lin kt ,phn tn trong mi trng, +Lnh vc ng dng : Sn , cht do ,vt liu,

I.5.2 phn loi pigment ( pig)

Thut ng Pig trng Pig mu Pig en Pig hiu ng kl Pig mu x c Pig giao thoa Pig pht quang Pig hunh quang Pig ln quang nh ngha Do tn x as khng chn lc Do hp th v tn x as c chn lc Do hp th as khng chn lc Do phn x as u hay giao thoa as Do phn x u trn cc lp ht pig Do giao thoa as Do e* pht x, as pht ra c di, t ngn Do e* pht x, as pht ra c di Do e* pht x, as pht ra c di, t di

I.6 nhng tnh cht ha l ca pigment v c

I.6.1. Thnh phn ca pigment v c 1/ pigment mt thnh phn : thng cha mt cht duy nht nn c s ng nht v tnh cht kh n nh . 2/ pigment hn hp: thc t pigment thng c nhiu thnh phn nhm ci thin tnh cht,gim gi thnh v tng hiu qu s dng . Ty vai tr ca cc thnh phn c trong pigment c th phn thnh pigment hn hp(c hai cht v thng ng nht v d), pigment nn(hay li ) c mt pigment (hay extender) lm nn v c ph cc pigment khc ln trn b mt nn ( loi ny thng khng cng d v khng ng nht gia nn v cht ph )

I.6.2 phn tch cc tnh cht ca pigment 1/tinh th hc v quang ph

a)H lp phng:gm 2 dng lng tr v lng thp,cu trc mng dng spinel(Fe3O4 ,CoAl2O4,...)cc thng s mng a =b=c , ab c b)H t phng(t gic)c 2 dng lng tr, lng thp, mng rutile ( TiO2 ,SnO2 ,), a=bc , abc c)H t phng (thoi): c 2 dng lng tr,lng thp, mng goethete ( FeOOH ) ,abc , abc d)H lc phng ( lc gic) c 2 dng lng tr,lng thp ( Fe2O3 ,Cr2O3) , a=b=c , d (a,b,c) e)H n t:mng monazite (PbCrO4),abc , a(b,c)

f)H tam t : abc , gc

2/bng 1.3 nh ngha v cc loi ht

Thut ng Ht Ht c bn nh ngha n v c bn ca pigment,c th c bt k hnh dng hay cu trc no

L ht c th xc nh bi cc phng php vt l ph hp,v d soi knh hin vi aggregate Gm cc ht c bn nm gn nhau thng hng, S mt phng tng cng < S ca cc ht agglomerate Gm cc ht c bn lin kt dng gc, cnh v c dng aggregate. S mt phng S cc ht flocculate L cc agglomerate tn ti th huyn ph

3/bng 1.4:khi nim v kch thc ht- s phn b kch thc ht

Thut ng nh ngha Kch thc ht d gi tr hnh hc m t trng thi khng gian D hiu dng Deff D ca ht cu hay d c trng mt loi ht D tng ng ng knh ht qui ra dng cu

S b mt sT
Th tch ht VT s phn b d

Gm S b mt trong v S b mt ngoi
Gm V thc (khng tnh l) v V kh kin Biu thng k % cc kch thc ht

I.6.3 cc phng php xc nh tnh cht

1/ cch ly mu: a/iu kin kh hu chun:t0 =230 , m tng i 50% b/ cch ly mu: mu ly phn tch phi i din cho ton b sn phm ( xem cch trn v ly mu trong ha phn tch ) c/ lng v s lng mu em phn tch phi nhiu gim sai s tng i v mang tnh i din cao

2/ xc nh mt s tnh cht l hc
a-% cht d bay hi: em mu c khi lng m0 (g) sy kh ti khi lng khng i m1 (g) t0 = 1050 2 . Thng thng y l gi tr m w = ( m0 m1).100 / m0 ; % b-%Mt khi nung: i lng ny ty thuc t0 nung v xc nh bng cch o bin thin khi lng nh phn a trn c-%cht tan trong dung mi: em mu c khi lng m0 ha tan(chit) trong dung mi thch hp nhit t , lc ra cn , sy kh , ngui cn khi lng m1 % cht tan = ( m0 m1 ).100 / m0 d- axit hay ba z : cn 100g mu em ha tan trong 1lt nc lc ly dung dch em trung ha bi axit hay ba z e- Xc nh gc sulfat, clorua , dng php phn tch ph hp f Xc nh khi lng ring: Ty theo mc ch ,lnh vc ng dng,cn da trn cc tiu chun cht lng c th xc nh , v d TCVN, tiu chun izo ,tiu chun ngnh,

3/ xc nh kch thc v phn b kch thc ht

C nhiu phng php nh: + m ht bng knh hin vi in t + phn tch cc cht lng + sng kh hay sng t, ty theo mc ch c th la chn phng php thch hp.vi mi phng php s c chnh xc ty theo tnh cht ca pigment ,trng thi , dng c s dng ,

Kch thc ht.

a)m ht bng knh hin vi: phn tn u ht( c th dng dung mi tr) trn tm knh v dng knh hin vi m ht ( 2500-10000 ht). Cch ny c th xc nh hnh dng ,phn bit ht c bn hay ht kt t b)Phn tch cht lng: o tc di chuyn ca ht trong mi trng thch hp ( nh lc ly tm hay trng lc). C 2 cch: +cho cc ht phn b u (th huyn ph) + huyn ph pha trn lp dung mi tr da vo tc di chuyn (lng) ca ht tnh d khng o chnh xc d nu h gm nhiu loi ht c d nn ch thch hp khi xc nh s phn b ht

Kch thc ht
c) phn tch bng sng : ( sng kh hay sng t ) Phng php ny nhanh,n gin nhng khng o c kch thc ht m ch xc nh % phn b ht (khi s dng b sng nhiu kch c l ) v tnh ng knh trung bnh d)Ngoi ra c th dng nhiu phng php khc nh phng php quang ,phng php o cc i lng vt l nh dn din ,.

4/ xc nh din tch b mt
din tch b mt ring l din tch ca mt n v khi lng cht rn. l i lng quan trng v n nh gi kh nng tng tc-hp ph ca pigment +phng php hp ph kh brunauer emmett teller (BET): dng cho ht khng tng tc ha hc vi kh s dng v cc ht nonmicroporous (khng c vi mao qun) +phng php hp th kh carman: cho kh hay lng chy qua lp vt liu xp ( iu kin P cao hay chn khng) v o gim p hay vn tc chy

5/ xc nh ph, phn tn,

ph (g/m2 hay m2/g) nh gi kh nng che ph ca pigment ph cng ln cht lng pigment cng cao. Xc nh bng cch tnh lng pigment cn dng che ph hon mt n v din tch b mt phn tn (trong nc, du,) Ngoi cc i lng k trn, ty thuc lnh vc s dng v tiu chun cht lng qui nh cn xc nh thm cc tnh cht khc nh cng , bn nhit,

6/ xc nh tnh cht mu ca pigment

Da trn cc h thng so mu hay o mu xc nh cc tnh cht mu ca pigment nh xc nh tng mu , sng , trng , chnh mu , ( s trnh by phn sau ) Ty theo h o mu c th biu th tnh cht mu ca pigment bi cc n v o khc nhau v d: H RGB biu th mu ca vt di dng h s mu r ; g ; b . Cc h s ny lin h vi nhau bi phng trnh mu M = r R + g G + b B

Chng II.i cng v l thuyt mu sc

II.1/nh sng v mu sc : nh sng l ngun gc ca mu sc khng c nh sng s khng c mu sc II.1.1/Bn cht ca nh sng: nh sng l bc x in t ,c trng bi hai i lng : + di sng (nm) + tn s ( s-1; Hz ) Mi lin h : = c / ; vi c= 3.108 m/s nh sng c c tnh cht sng v tnh cht ht Hai hin tng c trng : nhiu x v giao thoa

Bn cht ca nh sng
a/L thuyt sng: as l s truyn nhng dao ng n hi trong khng gian mt cch tun hon Tng t sng c,sng as tun th hai ng /l: a.1-Nguyn l chng cht: +ti im gp dao ng sng bng tng cc dao ng +Khng gy nhiu lon gia chng a.2-Nguyn l hughens: bt c im no nh sng truyn ti u tr thnh ngun th cp

Bn cht ca nh sng
b/ l thuyt ht:nm 1900 Max. Planck ra thuyt lng t nng lng v nm 1908 Anhxtanh ra thuyt photon coi nh sng cu thnh t cc ht ging nhau gi l lng t nh sng hay photon Vi bc x in t n sc c bc sng ,tn s s c nng lng xc nh = h . = h.c / vi h l hng s planck Trong mi mi trng , photon truyn i vi vn tc bng 3.108 m/s v cng ca chm bc x t l vi s photon pht ra trong mt n v thi gian

II.1.2/ cc i lng o bc x 1/ i vi ngun im: a/ thng lng bc x: o kh nng bc x ca ngun thng lng bc x ton phn l ton b nng lng ca ngun pht ra theo mi phng trong mt n v thi gian W=A/t , j/s , erg/s , w +A l nng lng bc x : j ; erg , (1j=107 erg) +t l thi gian , s Nu tnh trn din tch ds ta c thng lng bc x gi ti b mt ds l : dw = dA / t

Cc i lng o bc x
b/ cng bc x:( Ie ) Gc khi : d , steradian (sr) d = ds.cos /r2 , sr o

ds0

n ds

Ie c trng cho kh nng pht x ca ngun theo tng phng. Ie c tr s bng thng lng bc x ca ngun gi i trong mt d Ie = dw / d , J/s.sr hay w/ sr

Cc i lng o bc x 2/ i vi ngun khi bc x : a/ trng bc x: Re ( w/m2 , J / s.m2 ) Re l kh nng bc x ca mt n v din tch xc nh trn b mt ngun pht ra Re=dw / d + d l phn din tch b mt ngun , m2 + dw l thng lng bc x pht ra t d

Cc i lng o bc x b/ chi bc x: Be ( w/ sr .m2 ) +a0-a0 ngun khi +N-M phng pht x a n d +d phn din tch trn a0-a0 N d +dIe cng bc x ca d a +da hnh chiu ca d trn phng N-M da = d .cos Be = dIe / da = dIe / d.cos
0 a 0

Cc i lng o bc x c/ ri nng lng : Ee ( w/m2 ) Ee l i lng vt l c tr s bng thng lng bc x dw gi ti din tch ca mt ds Ee = dw / ds

II.1.3 -qui lut tng tc gia nh sng-vt cht 1/ hin tng phn x-tn x-khc x: xy ra khi chiu cc tia bc x vo vt cht c c tnh : B mt phng ,nhn : phn x (ng hng) B mt li lm,hn hp nhiu cht : tn x, hay thc t l phn x a hng . Qua hai mi trng khc nhau v n : khc x

Tn x Phn x v khc x

Hin tng phn x-tn x

Khi mt vt c kh nng pht,tn x ngun th cp ( ng l huyghens ) = dw, / dw + ri ca mt : Ee = dw / ds + trng pht sng ca vt: Re, = dw, / ds = Re, / Ee hay Re, = .Ee +Khi 1 : phn x ton b vt mu trng + Khi << 1: hp th hon ton vt mu en +khi 1 > > 0 : hp th chn lc vt c mu

II.1.4 quang ph-phn loi-mu sc

+ bc x gm mt hay nhiu bc x n sc. Kt qu ca qu trnh phn tch bc x t nhin ra cc bc x n sc l quang ph.cc phn b theo chiu di ca ph dng x=f () i vi thit b cch t: quan h trn tuyn tn i vi lng knh : ngn phn tn nhiu hn +a s bc x ph phc tp,mu= f (thnhphn) +ph vng kh kin ca nh sng Mu : ..cam..vnglc ..lamtm. ,nm:700 614 597 582 514 476 400

Ngun bc x
Cc ngun sng s c ph v khi chng tc ng vo cng mt vt c th cho mu sc nh gi thnh phn ph ca ngun c th da vo khi nim nhit mu T0m ( 0K ) lg a(T,) = 6245 ( 1/T0 1/ T0m ) / + C T0m ca ngun l t0 ca vt en tuyt i c mu trng vi mu ca ngun Khi T0m ph c ngn

II.2. S th cm mu
II.2.1 mt b phn th cm mu a/ cu to ca mt : gm 7 b phn chnh 1/gic mc 5/ vng mc 2/ mng mt v ng t 6/h trung tm(im vng) 3/ thy tinh th( nhn mt) 7/ thn kinh th gic 4/ thy tinh dch ( 99% H2O + anbumin ) Ti vng mc c cc t bo th cm dng que (1,2.108 t bo) v dng n hay dng nn ( 7.106 t bo )

b/ s iu tit ca mt Nhng lng t nh sng c s b hp th vi cc mc .Trong t bo que c nhy ph nh nhau nn khng phn bit mu m ch phn bit mc chiu sng
S hp th
S hp th

blue

green

red

Ph hp th t bo que

,nm

Ph hp th t bo n

,nm

II.2.2-cc i lng trc quang

Cc i lng o bc x : c trng cho ngun i lng trc quang :lin quan ngi quan st Thc t ch 60% thng lng bc x (w) gy cm gic sng cho mt ( ring mu lc 100%) a ra cc i lng trc quang da trn cc i lng o bc x

1/ quang thng ( lumen lm)

L i lng vt l c trng cho phn nng lng gy ra cm gic sng a/ quang thng ton phn (): ca ngun l phn nng lng gy ra cm gic sng pht ra theo mi phng trong mt n v thi gian + V l nhy ca mt = V .w.k +k l hng s ty thuc n v o + w l thng lng bc x Quang thng gi ti : d = V .dw.k

2/ Cng sng I (candela-Cd )

I ca ngun pht ra theo mt phng l i lng vt l c tr s bng gi trong mt d I = d / d , (Cd ) Cd l cng sng o theo phng vung gc ca vt bc x c din tch bng 6.10-5 m2 vi bc x nh mt vt bc x ton phn t0 ng c ca Platin di p sut 101325 N/m2 . Nu I ng hng : I = d / d d=I.d khi ly cu v n gin ta c = 4..I Vy 1 lumen = 1 candela . 1 steradian lumen l ca ngun im,ng hng c cng 1 Cd gi i trong 1 steradian

3/ trng R ( lm / m2 )
R l i lng c trng cho kh nng pht sng ca ngun khi - n l quang thng ton phn do phn din tch d ca ngun pht ra R = d / d , lm / m2

4/ chi B , nit ( nt )
B c trng cho s pht sng theo tng phng ca ngun khi . Vy B thay i theo phng chiu (gc ). Nu B khng ph thuc phng chiu ngun c gi l ngun lambe . B = dI / d.cos = dI / da ; (1 nt = 1Cd /1m2 ) nit l chi ca mt mt pht sng c din tch 1m2 pht ra cng sng 1 Cd theo phng vung gc vi n

5/ ri E , lux (lx)
E l i lng vt l c tr s bng quang thng gi ti mt din tch ds E = d / ds ; lm/m2 hay lux (lx) Do d = I . d v d = ds.cos / r2 E = d / ds = I . Cos / r2 lux l ri ca mt mt c din tch 1 m2 nhn c quang thng 1 lumen gi ti

6/ chi ca b mt c chiu ;
Ty thuc : + cng ngun chiu I + tnh cht ca b mt c chiu H s chi lun < chi ca ngun B = B / Blt +B : chi b mt c chiu theo hng gc +Blt : chi ca b mt tn x l tng. Thc t khng c Blt . C th coi b mt ca MgCO3 ( c = 0,96-0,99) hay MgSO4 ( 0,95-0,97) l Blt Do Blt = E / B = . E / i vi nh sng n sc : ,i = B,i / Blt

II.3.tm sinh l hc nim mu sc

II.3.1 phn loi mu sc 1/mu quang ph (mu n sc): thu c khi phn tch bc x theo .Cc bc x vng kh kin gm cc bc x n sc 400 700nm 2/mu v sc: c trng bng I nh nhau ca cc nn khng c tri. V d mu en ,trng, 3/mu hu sc: c trng bi cc c I . Mu ty thuc i c t l max . Mu hu sc bao gm mu n sc v mu a sc

II.3.2. cc i lng c trng ca mu

*Khi cn c vo 3 thng s vt l quan trng ca nh sng : cng , di sng v phn b nng lng ph c th coi mu hu sc c 3 cp thnh phn c trng .chng gn cht vi nhau v h tr nhau biu thi cho s a dng v mu sc ca vt cht + tng mu( khch quan) sc mu (ch quan) + thun sc( khch ) bo ha ( ch ) + chi ( khch ) sng ( ch ) *cc c trng ch quan gn cht vi tm sinh l ngi

1/ tng mu v sc mu Tng mu ca mt cht l mu ca n da trn ca bc x n sc tri,cn sc mu biu th phn bc x cn li V d: hn hp R-G vi R tri c tng mu l R v sc mu G ( nu R=G tng mu Y cn sc ch sng ti: vng sm,vng sng) nh ngha: tng mu ca mt cht ch s khc bit v cm gic mu ca mu hu sc vi mu ghi (v sc) c cng sng

2/ chi sng chi ca mu cng chnh l chi ca cc tia bc x hay cc tia phn x ( chi ca b mt c chiu) v c th xc nh khch quan sng l thc o s th cm mu (sng-ti) ca c quan th gic nn ch cm nhn m kh c th xc nh c

3/ thun sc bo ha thun sc xc nh mc sc thi ca mu (hay t l ca mu tri so vi cc mu cn li ) Mu quang ph c thun sc 100% . +ngun bc x: t s d tia tri : di + vt cht : t s B tia tri : Bi bo ha : l cm gic v s khc bit vi mu trng v mu sc .cc mu quang ph c bo ha tng dn t mu vng ti mu tm Vng - vng lc - lc cam lam - -chm -tm

II.3.3 mt s khi nim v mu

1/ su cao mu :Khi cc i hp th di chuyn v pha : + di hn : Mu tr nn su (sm) hn + ngn hn: Mu tr nn cao hn Cc mu quang ph ( vng kh kin ) c th t tng gim su v cao mu: su mu: Trng- vng chanh- vng- - cnh sen- tm- xanh tm- lc cao mu:

2/ cng mu Ch s m nht ca mu . N ph thuc thnh phn , hm lng cht mu Khi chi cao mu c cng mnh (mu nng ) v ngc li ( mu lnh ) Lu : cng mu khc cao v su mu . Khi chuyn dch su mu cha chc tng cng mu . Khi chuyn dch cao mu cha chc gim cng mu .

II.4. b mt mu mu vt cht
II.4.1 mu vt cht-cc yu t nh hng 1/ mu vt cht: mu sc l mt trong hai thuc tnh cn bn ca vt cht. Mt nhn bit c mu l do t hp ca 3 qu trnh: + c ngun bc x chiu vo vt + vt hp th chn lc cc sng bc x +s th cm mu mt Qu trnh th hai to ra s khc bit v mu sc gia cc vt, khi chiu cc bc x c ngoi vng kh kin vo vt c th pht quang ( hunh ,ln quang)

Bng 2.1: E v mu ca vt
b hp Nng th . lng . nm kj/mol 400-435 299-274 435-480 274-249 480-490 249-244 490-500 244-238 500-560 238-214 560-595 214-200 595-605 200-198 605-750 198-149 Mu ca as b hp th tm Xanh-tm lam Xanh l Lc vng cam Mu ca vt cht Lc-vng vng cam Cnh sen Xanh-tm lam Xanh da tri

2/ cc yu t nh hng ti kh nng hp th as
a/tnh cht lp b mt c chiu

Vt khng ng nht v mt quang

Vt c lp phn x

nh sng tn x

Phn x c hng

b/ chiu dy lp hp th H s hp th : H = ( I I0 ) / I Theo lamber-beer: s hp th tng khi c v x dI = - c.I.dx dI/I = - c dx x Ly xc nh t I0I v t 0 x dI dx Ln I/I0 = - c . X I I Khi xs hp th thun Sc m mu Lu nh lut lamber-beer ch ng c nh
0

c/ kch thc ht Theo l thuyt Mie: da trn phng trnh ca Maxwell tao m hnh gm mt phng sng giao vi vt hnh cu ng hng v phng din quang ,c chit sut n v ch s hp th k . Khi ly phng trnh sng s thu tit din hp th QA v tit din tn x QS . Cc gi tr v hng trn cho bit mi quan h gia kh nng hp th,tn x vi kch thc ht hay gia mu sc vi kch thc ht .

d/ cu trc tinh th S khc bit v cu trc ( v kch thc ht ) s dn ti khc bit v kh nng hp th hay phn x cc bc x chiu vo vt khc bit v mu sc . V d : cacbon dng kim cng , grafit hay than . Trong thc t do pigment thng c dng lm lp ph trang tr hay bo v trn b mt vt nn mu sc ty thuc ch yu vo tnh cht b mt ca vt

II.4.2. bn cht ha hc ca cht mu 1/ electron c s gii thch mu vt cht Trang thi e , linh ng v s chuyn mc nng lng ca e khi b kch thch to ra mu
s2
s1 *

T1*

T0*
s0

Electron. Nng lng chuyn e ca vt t qu o n nh s0 sang qu o kch thch si* nhn c t ngun bc x chiu vo n = Esi Eso = hi . = h.c / i Gi s lp s0 c 2e vi tng spin =0( trng thi singlet ).Khi b kch thch c 1e nhy ln mc s1* nhng spin khng i (trng thi singlet s* ). Nu spin thay i (tng 0) n s mc T0* c nng lng ET* < Es1* v bn hn ( trng thi triplet T0* )

Electron
+ Do e trng thi kch thch khng bn nn sau khong thi gian ngn (10-8 10-9 s ) n tr li qu o s0 km gii phng E dng bc x vi i xc nh. Nu i trong vng kh kin ta s thy mu ca vt cn i ngoi ta thy hin tng hunh quang pht quang hay ln quang

2/ cc cht mu v c
a/ c im chung:mu l do chuyn e (nht l e ho tr) cht v c c mu thng l +Cc cht c mc nng lng gia cc orbitan cha e , orbitan cha e v trng gn nhau, lp v e cha y +Cc cht c nhiu e v c orbitan ha tr cn trng V d : +Ca : 3p6 4s2 : khng mu +Br : 4s2 4p5 : c mu vng cam cht v c khng mu hay mu trng thng l : +cc nguyn t s v p lp y e , cc hp cht kim loi kim, kim th vi phi kim 3 chu k u. V d : NaCl , NaF , CaF2 ,

Cc cht mu v c +Cc cht, hp cht c s khc bit v nng lng gia lp cha e v lp trng qu ln +Cc cht ,hp cht khng cn orbitan (nht l cc orbitan ha tr) trng +Cc hp cht ( ch yu l oxit) ca cc cht nm gia kim loi v phi kim

b/ cc yu t nh hng ti mu cc cht v c b.1/trng thi tn ti:nh hng s chuyn e do + khong cch ion-ion + khong cch nguyn t - nguyn t + khong cch ht nhn electron V d: PbI2 dng dung dch : khng c mu PbI2 dng rn : mu vng Do ion bin dng gim phn cc khong cch cation-anion gimchnh E gimmu

b.2/ s phn cc phn t S phn cc thay i mc nng lng ca e d b kch thch c mu V d : AgCl : mu trng AgI : mu vng AgBr : mu cam

b.3/ trng thi oxy ha Mc oxy ha cng caotc dng phn cc cng ln e d b kch thchc mu v d 1 : + MnO2 : mu xm en + K2MnO4 : mu xanh + KMnO4 : mu tm v d 2 : + V+ : mu xm + V5+ : mu vng cam

c/ kt lun Mu ca cc cht v c b chi phi bi : Trong phn t cc mc nng lng gia cc orbitan ha tr cha e v trng phi gn nhau hay phn t c nhiu e v c orbitan trng Trong phn t c s phn cc mnh hay cation v anion c kh nng phn cc ln

Chng III.cc h thng so snh mu sc III.1. cc nguyn l tng hp mu III.1.1. mu c bn nh ngha : l nhng mu m t chng c th to ra v s v y cc mu khc iu kin : khi phi hp hai mu c bn khng to ra mu c bn th ba V d: (red) lc (green) xanh tm (blue) Mu to t hai mu c bn ( mu hai) nh mu vng t + lc , t ba mu c bn ( mu ba) nh mu en t + lc + xanh tm .

III.1.2 cc phng php tng hp mu

1/phng php cng mu(dnh cho bc x) khi chiu ng thi 3 mu c bn R-G-B thu c + mu hai : mu trung gian + mu ba : mu trng yellow c im:khi thay i green red white lng bc x c bn theo cc t l s thu cyan magenta mu c sng nhng blue lun sng hn mu c bn

2/Phng php tr mu ( mu vt cht) Khi trn cc mu c bn (mc mu, mu v, sn, in chng mu,) s thu: + mu hai : mu trung gian green black yellow + mu ba : mu en cyan c im:khi thay i cht mu theo cc t l s lun blue red thu mu trung gian ti hn mu c bn magenta

III.1.3 Mu i nhau
Mu i nhau l mu khi hn hp s thu c mu quang ph yellow Quang ph : green + cng mu : mu trng red + tr mu : mu en Quang ph Cc mu i nhau nm cyan magenta i din nhau trn vng mu sc .Mu bt k u c tng hp blue t hai mu bn cnh theo cc phng php cng hay tr

III.2. Nhng nguyn l ca php so mu

III2.1 h thng ha v th hin mu v s lng 1/ phng php chun mu:da trn 3 c trng ch quan ca mu: sc - sng - bo ha thit lp h thng b mu ( atlat ) : + dng bng mu + dng thang mu Vi qui lut thay i theo cc tiu ch nh , tng mu , sng , phng php ny c u im l n gin ,d s dng v khng cn thit b hay tnh ton .Nhc im l phu thuc ch quan, khng chnh xc (khi phc ch mu) v kh xc nh mu bc x hay b mt cht khng phng ,

2/ phng php so mu Th hin mu v s lng v gn vi 3 c trng khch quan ca mu C s ca phng php so mu: l c ch 3 thnh phn: mi mu l tng hp ca 3 mu c bn th hin qua 3 s o ( ta mu- TM) Cc c trng ca mu lin h vi nhau qua ta mu u im: chnh xc,th hin mu bt k Nhc :cn thit b ,tru tng v khng cho cm gic mu

III.2.2 Nhng nguyn l ca php so mu 1/ mu n v

3 mu c bn: (red) lc (green)- xanh (blue) V cht(xc nh sc mu): c r = 700 nm , lc c g=546,1 nm , xanh c b = 435,8 nm v lng mun xc nh phi da vo chi R : Br= 683 nt -ng chi pht x Be=243,9w/sr m2 G: Bg =3135nt- ng chi pht x Beg =4,66w/sr.m2 B: Bb=41nt ng chi pht x Beb = 3,37 w/sr.m2 cc bc x trn l mu n v.V d mu G c B=313,5 nt tc c lng 0,1 n v mu lc . Mu M gm hai thnh phn R&G vi Bi=300 nt s c 0,439 v mu (300 :683=0,439) v 0,096 v mu lc (300:3135) . M khng phi mu vng Mu trng gm 0,333R ,0,333G v 0,333B ( lng nh nhau) Mu M c Br=Bg=Bb =300nt khng phi mu trng m l xanh

2/ ta mu-TM
TM l s lng 3 mu c bn sau khi trn s phc ch c mu cn xem xt trong h thng mu nht nh nh r, , g, , b, hay x, ,y, , z, xc nh TM c hai cch: + o trc tip mu bng my o mu + tnh ton theo thnh phn ph bc x,phn x ta ring: l ta bc x n sc vi chi pht x n v. N ch r cn trn cc mu c bn vi lng ra sao thu mu bc x n sc vi chi pht x n v .Gi tr TR o bng thc nghim v ch o 1 ln. = V. / L tnh TM ta nhn TR vi chi pht x:v d r = .Ber vi bc x c ph phc tp, TM ca n l tng ta n sc tng ng c trong ph . V d r = r

3/ phng trnh mu L kt qu o mu M th hin qua TM di dng phng trnh: mM = rR + gG + bB vi m = r + g + b ; ( m l h s chi ) a/ Xt v cht(sc thi mu):cn bit t l 3 mu c bn ca M l cc ta ca sc (hay ta tng i ) r,g,b ; x,y,z , r = r / m ; g = g / m; b = b / m r + g + b=1 * Nh vy bit sc ca mu ch cn bit 2 trong 3 h s mu r , g , b . M = r .R + g . G + b . B

b/ xt v lng Ta tnh B theo : BM = r .683 + g. 3135 + b .41 n gin ta chn chi ca R lm n v v chuyn chi n v v chi n v tng i, tc br=1 ;bg=4,59 ;bb=0,06 BM = 683 .( r. 1 + g.4,59 + b.0,06 ) Hay : BM = 683. m (r.br + g.bg + b.bb ) t FM = r.br + g.bg + b.bb BM = 683.m.FM Vi FM l chi tng i

BI TP
BI 1: cho mu M c phng trnh : 2M = - 2,35R + 2,80G + 1,55B Xc nh ta sc r , g , b v chi

BI 2: So snh hai mu M1 v M2 c phng trnh 2,8M1 = 1,4 R + 1,05G + 0,35B v 1,6M2 = 0,8R + 0,6G + 0,2B
BI 3 : cho hai mu M1 v M2 c phng trnh M1 = 0,40R + 0,50G + 0,1B v M2 = 0,33R + 0,33G + 0,33B 1/ Xc nh mu hn hp M khi trn M1 v M2 vi lng nh nhau 2/ So snh hai mu M v M1

4/ tnh ta mu Bi ton: tnh ta mu ca bc x pht ra t n hi thy ngn .bc x c dng ph vch gm 4 bc x n sc c , cng sut v TR
, nm Cng sut, w Ta ring 0,2937 0,0001

404,7
435,8 546,1

5,2
9,1 10,5

0,0005
0,0002

-0,0002 0,0192
0,2142

-0,0001 0,0001

578

10,2

0,2300

0,1434

-0,0011

III.2.3 th mu 1/ th mu khng gian

M t cc i lng mu bi cc vecto .mi s hng trong phng trnh mu l mt vecto Vic tng hp mu tun theo qui tc cng vecto v tng ca 2 vecto s khc phng nn mu tng hp t 2 mu c bn s c tng mu khc , di ca vecto biu th chi nn nu hai vecto tng c di nh nhau s c chi nh nhau Do m t mu bng vecto l gi nh nn hnh dng khi mu khng gian l ty

 th mu khng gian Trc black-white l trc v sc ( mu xm)

B blue 0,0,1

cyan white

magenta
black

0,1,0
G

red R 1,0,0

green yellow

2/ Tam gic mu M t mu di dng im trong mu. Vic tng hp mu theo qui tc cng
G ( 0,1,0)

B (0,0,1)

R (1,0,0)

III.3 Cc h thng so mu III.3.1 H thng so mu RGB

Mu T :r = -1,1685 ;Fr = -1,1685nt

g= 1,3905 ;Fg = 6,3824 nt

b = 0,7780 ; Fb= 0,0467 nt

T =435,8-700 nm c chia lm 41 bc x n sc ; =10nm

G546,1
Mu T:
r=0 g = 0,567 b = 1-0,567=0,433

500
T E yellow

435,8

B magenta

700 R

H RGB
Xt mu T nm ti giao im E-T vi GB Ptr mu: T = 0,567 G + 0,433 B (1 ) T thu c khi trn: +cch 1: mu E v mu T +cch 2 : mu B v mu G Gi s to mu T theo cch 1: Theo qui tc ng lin hp ( hay qui tc n by ): Lng mu E trong T Lng mu T trong T T T E-T
;

0,778 0,222

Suy ra:

T = 0,778 E + 0,222T

(2)
;

T (1) v ( 2) : 0,567 G + 0,433 B = 0,778 E + 0,222 T

(3)

nh vy khi thm E vo T s lm gim thun sc v lm nht mu T khi thay E = 0,333R + 0,333G + 0,333B vo (3) v rt gn ta thu ptr mu ca T

Nhn xt
Tam gic mu RGB l h thng tiu chun do CIE a ra nm 1931 (da trn kt qu N/C ca WrightGuid) c hai nhc im ln: +lun c ta m vi bc x n sc (thm ch c 2 ta m vi bc x a sc) +la chn thnh phn mu c bn cn ch quan Kt qu t tnh ton trn chng t khng c mu ph T thun khit ( do cm nhn mu ca mt )

III.3.2 H thng so mu XYZ c xy dng da trn cc quan im sau:

+tam gic xyz c 3 nh ng vi 3 thnh phn c bn,trong x,z phi c Fx = Fz = 0 ,tc l x,z phi nm trn ng thng tha mn phng trnh sau: r br + g.bg + b. bb = 0 Hay : 0,9399 R + 4,5306 G + 0,0601 B = 0 Do Fx =Fz = 0 nn x.bx = z.bz bx = bz = 0 chi ca mu tng hp ng bng chi Y v by=1 + cnh xy v yz tip tuyn ng cong mu ph nhm gi n trong xyz trnh cac mu khng thc + im mu trng E nm ti tm ca xyz

H xyz -tnh ton ngha

Cch tnh, ngha cc i lng TM,TS nh h RGB ch thay r,g,b =x,y,z v r,g,b = x,y,z Mi lin h: X = 1,2744R 0,2774G + 0,003B Y = -1,7363R + 2,7692G -0,033B Z = -0,7411R + 0,1429G + 1,5982B V: x = 2,4689 r + 1,7517 g + 1,1302 b y = 1,000 r + 4,5907 g + 0,0601 b z = 0,0565 g + 5,5943 b Ta R,G,B trong xyz: R(700nm): x=0,73467 ; y=0,26533 G(546,1nm) : x=0,27376 ; y=0,71741 B(435,8nm) : x=0,16658 ; y= 0,00886

H xyz-tnh ton Tng mu: biu th bi cc h s mu x,y,z chi :xc nh bi y (y h s phn x ) B = 683. y ; nt thun khit ( Pc): chi bc x tri y P = = Nh RGB nu c im muchi tng c mu M(x,y)s tm y M(x,y) trn ng ph cng tng, c Pc cao hn Gi thit bc x n sc c P,c=100% .vyPc ca M
c

Pc

y y

y ( y y0 ) y ( y y0 )

y ( x x0 ) y ( x x0 )

H thng so mu XYZ (CIE)

1,0

y
500 0,5

520

600

680

700

380

0,5

- x

1,0

III.3.3 H thng UVW- th mu ng tng phn

Trong h RGB v XYZ c nhc im: + TM ( r,g,b x,y,z) nh nhau : mu ging nhau + TM nhng h s mu (r,g,b-xyz) nh nhau: tng mu ging nhau ch khc chi + Khong cch hai mu cng xa cng khc nhau nhng kh xc nh trn th + Trong mu s khc bit v mu th hin qua h s mu bng khong cch gia chng V d: mu F1(x1,y1) v F2(x2,y2) c khong cch l
l = (x2 x1)2 + ( y2 y1)2 Theo tng trn xy dng th mu UVW m trn nu cc im mu cch nhau mt khong cch l nh nhau s c s th cm nh nhau:

H so mu ng tng phn UVW th uvw nhn c khi chiu h xyz ln mt uv hp thnh mt gc nghing khng gian nht nh vi mt xy mi qui tc cng mu,tng hp mu t cc bc x n sc trong xyz u c bo tn trong h uvw mi lin h gia uvw - xyz v TM, h s mu u = 2x/ 3 ; v = y ; w = 1,5y 0,5x + 0,5 z
-4x
U =

x + 15y +3z

V v =

6y
x + 15y + 3z

Ngi ta thng ghi gi tr x , y ln ngay th uv (song lu khong cch cc im mu vi ta x,y trn uv khc vi trn xy)

III.3.4 chnh mu- h thng Munsell

xc nh chnh mu cn thit lp khng gian mu tuyt i da trn mu, sng v bo ha. Cc mu c biu th trn khng gian 3 chiu vi khong cch gia 2 mu ng vi s khc nhau v mu-h thng so mu ph bin nht theo cch trn l h thng Munsell xc nh gi tr tuyt i ca s chnh mu cn chuyn i cc gi tr o c bng h CIE sang h AN(Adams-Nickerson)m sau gi l h CIELAB 3 trc c k hiu: a*(-xanh dng) ; b*(vng-xanh) v L* ( sng)

H thng CIELAB
Vi Xn , Yn , Zn l cc gi tr trn h CIE ca 3 kch thch c bn . S chuyn i X,Y,Z thnh X*,Y*,Z*
X* = 3 X / Xn ; Y* = 3 Y / Yn ; Z* = 3 Z / Zn

Khi gi tr trong cn < 0,008856 cc biu thc trn tr thnh X* = 7,787.X / Xn + 0,138 ; Y* = 7,787 .Y / Yn + 0,138
Z* = 7,787 . Z / Zn + 0,138 a* = 500 ( X* - Y* ) ; b* = 200( Y* - Z*) ; L* = 116 Y* - 16 chnh mu vi mu chun : Eab* = a*2 + b*2 + L*2 Trong : a* = a*T - a*R ; b* = b*T - b*R v L* = L*T - L*R

H CIELAB H CIELAB c u im l c th chia chnh mu thnh 3 thnh phn : + chnh v sng: L* = LT* - LR*

+ chnh v mu sc :

Hab* =

Eab*2-L*2-Cab*2

+ chnh v bo ha: Cab*= aT*2+bT*2 - aR*2- bR*2

Chng IV cc phng php sn xut pigmen IV. M u

+Thc t pigment v c tn ti nhiu dng nh dng oxit, mui, phc ,hay hn hp,nn cc phng php sn xut chng cng c th + v th vic phn loi cc phng php sn xut pigment v c rt kh khn v do c nhiu tiu ch nh gi nn c nhiu cch phn loi +chng ti phn chia da trn qu trnh iu ch chng t dung dch (phng php t) hay qu trnh nung cht rn t0 cao ( phng php kh ).tuy nhin vic phn chia ny cng cha cht ch v hp l lm v c nhiu loi phi kt hp c hai cch trn

IV.2 cc phng php sn xut 1/ phng php t

Do nhiu loi pigment v c ch iu ch c t dung dch hay mt s loi(k c mt s oxit kim loi) thng thay i tnh cht hay b phn hy t0 cao nn phi iu ch t0 thp v thch hp nht l iu ch chng t dung dch V d1:pigmentZn vng: Zn2+ + CrO42- =ZnCrO4 V d 2: pigment Fe2O3 c th iu ch khi nung mui st hay hydroxyt st t0cao, nhng do n d chuyn dng t0 cao lm mu thiu n nh nn c khi phi iu ch t dung dch

2/ phng php kh
Tt c cc loi pigment v c khng th iu ch t dung dch hay iu ch t dung dch lm gim cht lng,tng gi thnh, u phi qua con ng nung , nghin trn kh, +V d1: pigment ultramarine c iu ch khi nung hn hp st,soda,than, t0 cao +V d 2: iu ch pigment oxit crom K2Cr2O7 + S = K2SO4 + Cr2O3

Chng V/K thut sn xut TiO2

Ni dung bao gm: Nguyn liu, ng dng Cht lng, tnh cht ca Pigment TiO2 C s k thut ca phng php sunfat C s k thut ca phng php Clo Vn mi trng

Nguyn liu - ng dng

I. 1. 2. 3. 4. Nguyn liu Qung Rutile Qung Anatase Qung Ilmenit v Leucoxene Qung Rutie tng hp, x titan, Trong ph bin nht v tr lng ln nht l dng Anatase nhng phn ln TiO2 c sn xut ( 95%) t Rutile v Ilmenit

Sn lng khai thc khong cha TiO2 ( 1994 )

Ilmenit : 7,12 . 106 tn (ch yu c, Canada, Nam Phi) Rutile : 5,5 . 105 tn (ch yu c, Xiera Leon ) Rutile tng hp : 6,25 . 105 tn (ch yu c, M ) X titan 1,7 .106 tn (ch yu Canada, Nam Phi, Nauy ) Ngoi ra cn mt lng nh hn c khai thc t cc dng khong cha titan khc nh leucoxene , anatat,

Cc khong ch yu cha Titan

Dng khong Rutile Anatase Brookite Ilmenit Leucoxene Perovskite Sphene(Titanit) Titanomagnetit Cng thc TiO2 TiO2 TiO2 (FeO. TiO2) Fe2O3. TiO2 CaO. TiO2 Cao. TiO2. SiO2 Fe(Ti)Fe2O4 Hm lng TiO2 (%) 92 98 90 95 90 100 35 60 60 90 40 60 30 42 2 20

Thnh phn khong Ilmenit ( ct en)

Thnh phn chnh FeO.TiO2 : 35 60 % TiO2 Khong tp : Zirconi, silicat, hematite, magnetit, Leucoxene : Fe2O3.TiO2 (qu trnh xi mn, phong ha Ilmenit ) Do hm lng Fe cao nn khng th s dng trc tip m phi x l trc loi st ( tuyn trng lc, tuyn t, )

a) b) c) d) e) f) g) h) i) j) k) l)

Dredger : my no vt Sieve : sng Bunker : bunke Reichert cones : Xyclon hnh chp nn Spirals : trc vt Magnetic separator : my tch t tnh Dryer : my sy Electrostatic separator: my tch tnh in Shaking table : bn rung lc Dry magnetic separator : My tch t tnh kh Vertical belt conveyer : gu nng Electrostatic separator : my tch tnh in

II. ng dng
+ 3 dng th hnh ca TiO2 : Rutile, Anatase, Brooktile Trong Rutile v Anatase c sn xut lng ln v s dng lm Pigment, sn xut gm s v vt liu in t + TiO2 c tnh tn x tt hn cc loi pigment trng khc v c bn ha hc cao, t c tnh l pigment v c c sn xut lng ln + Mt s lnh vc ng dng pigment TiO2: sn, cht ph, mc in, nha, giy, si tng hp,

Cht lng, tnh cht TiO2 I. Cht lng: Ty thuc:

Phng php iu ch Hm lng TiO2, dng th hnh ca TiO2 Kch thc, s phn b kch thc ht Qu trnh x l sn phm TiO2

II. Tnh cht:

Cc tnh cht quan trng ca pigment TiO2 sng ph mu Kh nng phn tn bn sng, thi tit, Cc tnh cht trn ty thuc vo phng php iu ch, tinh khit, bn mng cu trc, kch thc ht, s phn b ht, dung mi

II.1 . Kh nng khuych tn:

Chit sut ca Rutile v anatase cao : 2,70 v 2,55 Cc cht kt dnh, mi trng phn tn thp : nc (1,33) polieste (1,73) Kh nng khuch tn nh sng ca TiO2 ty thuc:
- Kch thc ht : Khi d = 0,2 m (Mie) t cc i - Bc sng ca ngun bc x: ngn : mu xanh nht

di : mu hi vng
- Phn b kch thc ht

II.2 . mu ( trng )
Ty thuc ch yu: - Phng php sn xut - Cu trc mang tinh th - tinh khit (tp l oxyt kim loi chuyn tip lm gim trng ) - Kch thc ht v s phn b ht - Bc sng ca ngun bc x, V d: - Dng Anatase hp th max = 385 nm, Rutile l 415 nm - chnh nng lng dy ha tr v dy dn in : Anatase ( 3,29 ev) Rutile ( 3,05 ev) Khi chiu bc x vng t ngoi Rutile vng hn Anatase

II.3 . phn tn:

phn tn ty thuc:
Kch thc ht, s phn b ht Mi trng phn tn

phn tn nh hng ti ph, bng

tng phn tn cn nghin nh pigment hay x l b mt ht

II.4 . bn sng, bn thi tit

Sn, cht ph c TiO2 chu tc ng mnh ca thi tit (nht l Anatase) Nu c m,khng c khng kh (hay cht kt dnh thm thu oxy yu) : xm mu ( grayinh ) Ngc li nu c m v oxy khng kh : ng cc ( lightfastness )

Nguyn nhn do chu trnh sau:

1) 2) Nc bm vo b mt TiO2 to nhm OH- trn b mt v H+ Khi hp th bc x c ngn (A 385 nm ; R 415 nm) s to e t do v cc l khuyt e trn mng tinh th, chng di chuyn ln b mt OH- b l oxy ha thnh OH. v n b phn hy trong mi trng cht kt dnh. E t do kh Ti4+ thnh Ti3+ Oxy oxyha Ti3+ to ra Ti4+ v O2-. N tc dng vi H+ thnh HO2. Nc hp th vo b mt tc dng vi HO2. OH-

3) 4) 5)

Kt lun
Qu trnh vn cc v xm ha ( chalkinh) l do nc ,bc x c ngn v TiO2 lm xc tc .H ca qu trnh 312 Kj /mol ly t bc x c 385 nm c O2 hin tng vn cc(lightfastness) khng c O2 xm mu (grayinh) ng nhin c hai u c mt H2O

Cc bin php x l b mt pigment

tng bn sng, bn thi tit, kh nng phn tn cn kt ta cc cht v c khng mu ln b mt ht Hiu qu ty thuc
Cht che ph, thnh phn cht che ph Phng php tin hnh kt ta

Cht ph c th lm gim phn tn, phn x,

Cc phng php x l b mt TiO2

1. Thng hoa hay bc hi cc cht d bay hi (mui clorua hay c kim). C th s dng hi nc lm tc nhn kch thch. Cc cht ny s ngng t ln b mt 2. Nghin hn hp cc cht ph (oxyt, hydroxyt) vi pigment 3. Kt ta cc cht t dung dch, hay dng th huyn ph cho bm ln b nt pigment qua mt hay nhiu giai on (lin tc hay gin on)

Phn chia pigment da trn bn sng v bn thi tit:

Pigment c lp ph dy (dng cho sn, nha,) c thnh phn sau: a. Kt ta SiO2 (t, pH thch hp):t l TiO2 khong 88% b. Sau x l 2 ln, nung 500-800C :t l TiO2 l 95% c. X l tip bi cc hp cht Zn, Ti, Al, Si, vi ha 500800C. t l ca TiO2 l 95% 2) Lp ph xp dng trong sn th nh tng: Thm hp cht Si, Al, Ti vi t l TiO2 80-85%, Silica 10% 3) Pigment bn sng, lp ph dy dng trong ngnh giy : lp ph l mui Silicat hay Photphat ca Ti, Zn, Al vi TiO2 90% Khi thm cc cation nh Sb, Cs bn sng tng 1)

X l pigment sau khi ph

Lc ra pigment loi mui d, trn lc p hay chn khng. Sy kh bng thi kh hay my sy tng si Trc khi sy kh hay nghin ( thi kh, hi nc ) c th thm cht ph hu c ty theo mc dch (silicon, photphat hu c,k nc hay cn, ete, este,a nc hay c hai loi trn).

3 Cc phng php x l qung Ilmenit

Phng php axit + Ha tan TiO2 bi axit m dc t cao + Kt ta mui st v lc ly dung dch mui titan + Thy phn mui titan + Lc kt ta TiO2.H2O, sy, nghin, x l 2. Phng php clo ha: + Clo ha qung Titan t cao. Thu mui TiCl4 dng hi + Thy phn mui titan bng hi nc hay t chy mui titan (trc tip dng hi hay ngng tu TiCl4) + X l TiO2 1.

4 C s k thut ca phng php axit

I. S cng ngh:

II. Phn ng ha hc:

2FeO.TiO2 + 5H2SO4 = Ti(SO4)2 + Fe(SO4)3 +5H2O FeO.TiO2 + HCl = TiCl4 + FeCl2 + H2O FeTiO3 + HNO3 = Ti(NO3)4 + Fe(NO3)3 +NO +H2O c im: phn ng xy ra T0 cao , HCl v HNO3 d bay hi , phn hy. Mui clorua v nitrat Fe b thy phn, mui sulfat st (III) d b thy phn nhng c th chuyn v mui st (II) kh b thy phn chn H2SO4 lm tc nhn phng php sulfat

C s k thut ca PP sulfat
Phn ng phn hy FeTiO3+H2SO4 =FeSO4+Ti(SO4)2 +H2O FeTiO3+H2SO4 = FeSO4 +TiOSO4 +H2O Ti(SO4)2 + H2O = TiOSO4 + H2SO4 FeSO4 + H2SO4 + O2 = Fe2(SO4)3 Cc tp ( Zr ,Fe ,) to mui sulfat

Cc iu kin k thut
Nng axit : 92-94 % (oleum 20%SO3) T0 p.ng : 125-1350c (sau tng do Hp) T l H2SO4 / TiO2 : 1,8-2,2 C ht Ilmenit : 40 m Thi gian phn ng : 1-12 gi Khuy trn v sc kh Dung dch sau khi lc b cn khng tan cha mui sulfat Ti,Fe3+,Fe2+,

Tch Fe khi dd trch ly

Phn ng :Fe + Fe2(SO4)3 = FeSO4 Dng khi c mu tm ca phc Ti3+ TiOSO4 + Fe = Ti2(SO4)3 +FeSO4 +H2O (do Fe3+ c tnh oxyha v Ti3+ c tnh kh mnh nn phn ng trn ch xy ra khi ht Fe3+ Ti3+ + Fe3+ = Ti4+ + Fe2+ )

 tan ca mui Fe (g /100g H2O)

TC FeSO4.7H2O Fe2(SO4)3.9H2O 10 20.5 20 26.5 440 30 32.9 40 40.2 50 48.6

tan ca Fe2+ < Fe3+ tan ca Fe2+ t thay i theo t Fe2+ kh b thuy phn hn Fe3+ (pH = 5,5 v pH = 2,0

Thy phn mui Ti4+

Cc mui Ti b thy phn pH 1,8 2,2 Phn ng thy phn: Ti(SO4)2 + H2O H2TiO3 + H2SO4 TiOSO4 + H2O H2TiO3 + H2SO4 Phng php thy phn , thnh phn dung dch nh hng ti cht lng ca TiO2 V d: TiO2 : 180 200 g/e : Ht mn TiO2 : 120 150 g/e : Ht th ln Qu trnh xy ra chm l do xy ra phn ng Ti(SO4)2 + H2O = TiO.SO4 + H2SO4

Hai phng php thy phn mui Ti4+ Pha long dung dch Ti4+ Cho mm nhn to Hai phng php to mm nhn to: 1. Ly mt phn dung dch Ti4+ cho tc dng vi NaOH (100g/lt) ti pH = 3. cho hn hp vo dung dch Ti4+cn li (t l 1% TiO2) 2. Cho mt phn TiO2 vo dung dch Ti4+ Nu thy phn t cao (94 110 %) trong 2 4 gi km khuy trn t = 95 96 %

Nhit phn kt ta TiO2.H2O

Do H2TiO3 c ln gc sunfat nn phi nung sn phm thy phn 200- 300C : H2TiO3 = TiO2 + H2O 500- 950C : Ti(SO4)2 = TiO2 + SO3 300C : H2SO4 = H2O + SO3 Dng th hnh ca TiO2 thy thuc t > 950C : Dng R < 950C : Dng A Do kh l c SO3 v H2O nn phi duy tr kh ra 300C v hp th bi dung dch H2SO4 Sn phm TiO2 c x l thu pigment

X l cht thi ca qu trnh sunfat

Cht thi lng:dng 2,4-3,5t H2SO4 /1,0 t TiO2 Ngoi sulfat cn dng lng (H2SO4 20-24%) Cc PP x l: c c thu H2SO4 hay kt ta dng gips ( c th nhit phn sx axit sulfuric) Cht thi kh: ch yu l SO2 hay SO3 c hp th bi dd baz (thu mui) hay nc thu axit

Phng php clo ha

Phn ng ha hc : TiO2 +Cl2 + C = TiCl4 + CO2 (CO) C ch qu trnh phc tp : TiO2 b kh thnh Ti; Ti tc dng vi clo thnh mui TiCl4 Tp cht cng b clo ha : v d V2O5 + Cl2 + C = VCl4 + VOCl3 + CO2 Duy tr nhit bng phn ng C + O2 = CO(CO2) + Cl (C CO2 : 96KCal; C CO : 56.6 KCal; CO CO2 135,4 KCal) Lng cacbon ly theo ngun Cl2 (tinh khit 250- 350 kg; tp: 350 450 kg) v tnh trn 1 tn TiO2 1.

2. L t : C th dng nhiu kiu l : l quay, l tng si, nhng vt liu ch to phi chu c s n mn v kh Nguyn liu vo kh trnh to HCl v H2O trong pha kh Tp (Mg, Ca)Cl2, ZnSiO3 kh bay hi v clo ha s tch t trong l t Khng ngng l t ngt trnh hin tng thiu kt Kh ra khi l (TiCl4, VOCl3,) c lm ngui v tinh ch

Tinh ch TiCl4
+ Lc b mui clorua tp khng tan ,loi b mui tp tan khi chng ct cc t khc nhau (xem bng 5.7 tr 83 CNSXCMVC) + Ngng t kh l theo tng cp h nhit V d : 319C : FeCl3 ngng t 136C : TiCl4 ngng t + B xung cht to kt ta tp (v d thm H2S kt ta Vanadisulfua )

t chy TiCl4
Phn ng: TiCl4 + O2 = TiO2 + Cl2 Lng O2 dng 110-115 % so l thuyt TiCl4 c ha hi v gia nhit 500-10000 B xung 5% AlCl3 to TiO2 dng R ,d nh Nu c SiCl4 hay PCl3 to dng A C th thy phn dd TiCl4 thu TiO2.H2O

Bng 5.7 Nhit si ca mt s mui clorua

Hp cht TiCl4 VOCl3 SiCl4 VCl4 FeCl3 Al2Cl6 SnCl4 CrO2Cl2 TaCl5 Nhit si ; 0C 136 127 58 164 319 180 116 116,7 239

Chng VI / Sn xut oxitcrom

1- Nguyn liu Khong cha crom dng mui kh tan ca ax HCrO2. Nu Cr2O3 35%: khong ngho V d: cromitst FeO.Cr2O3 , khong dng (Fe,Mg)O(Cr,Al,Fe)2 l dd rn ca cc mui (Fe,Mg)(CrO2)2 Cc khong tp nh serpentin, hot thch,.. Khong c lm giu theo phng php tuyn trng lc,tuyn t, ( xem cc bng trang 96 v 97 GTCNSXCMVC)

Cc phng php x l cromit

Nung kh sn xut ferrocrom:(sx thp khng r ,) Phn ng: FeO.Cr2O3 +C = Fe.Cr + CO2 Tp Cr4C ; Cr7C3 ; Cr3C2 , Sx vt liu chu la : Nung cromit vi CaO ,MgO ,Al2O3 t0 cao Nguyn liu cha 20%FeO ,7%SiO2 Cr lm tng t0 chu la :CaO.Al2O3 (t0nc1600) CaO.Cr2O3 (2090 ) Nung oxyha sx mui crom FeO.Cr2O3 + O2 +Na2CO3 = Na2CrO4 +Fe2O3 +CO2

Tnh cht ca Cr v hp cht

+ Crom(24) : thuc nhm IVB, CK 4 : 3d54s1 Bn trong KK v lp oxit ,th ng trong ax C tnh oxyha HNO3 ,dd cng thy ,tan km trong axit khac ngay c khi t nng + Hp cht: ph bin v bn dng Cr6+ ,Cr3+ Dng oxit Cr2O3 khng tan trong axit v kim , c t tnh, t0nc =2435 0c Dng mui sulfua d b thy phn

III. Sn xut Cr2O3 t qung cromit

III.1 Qu trnh ha hc: xy ra rt phc tp Cr2O3 + O2 = CrO3 FeO + O2 = Fe2O3 CrO3 c tnh axit : CrO3 +Na2O =Na2CrO4 Fe2O3 cng to (t) Na3FeO3 v Na4FeO4 Tp Al2O3 ,MgO , SiO2 ,CaO ,Na2O tc dng vi oxitcrom,oxit st hay vi nhau to cc mui aluminat ,cromat,silicat,ferat

Qu trnh ha hc
Lc u p xy ra trong h R K Khi t0 t0 im tecti: h R-L;R-K;R-L;L-L Ty phthc nung,t0,thnh phn phi liu,trong sn phm nung c nhiu cht Phn ng tng: Fe(CrO2)2+Na2CO3+k =Fe2O3+Na2CrO4+CO Mg(CrO2)2+Na2CO3+k=MgO+Na2CrO4+CO2

S tng tc soda-cromit-CaO
Khi t01100 to cromatto otecti vi soda (6550 ,62,5%Na2CO3 )pha lng t0 1000: vp to cromat>vp gia soda vi cc oxit Al,Si,Mg[soda] trong pha L (A) Do [cromat] nn h di chuyn v im cromat

Gin h Na2CO3 Na2CrO4

H tng tc CaCrO4+Na2CO3

Nhn xt
D CaCrO4 tan tt trong pha lng ( 80% 10000) nhng [Ca2+] dng lng khng ln v n to pha rn (silicat,aluminat,ferat,..,) Khi t0 thp (CaCO3 cha b phn hy) h gm 3 cu t: + Pha lng: CaCrO4 ,Na2CrO4 ,Na2CO3 + Pha rn:CaCO3 ,CaCrO4 ,Na2Ca(CO3)2 + Dd rn:mNa2CO3nNa2CO3 ;pNa2CrO4qCaCrO4 Pha lng xut hin ngay 6450 .

Nhn xt
Khi t0 thnh phn pha lng s thay i theo ng lin kt cc im tecti Pha lng xut hin ngay t0 <7000 Cc h bc hai (trn cnh gin )cng to dd rn v im tecti Tp silicat cng to hp cht tecti vi mui cromat ( 7700 ,10% silicat )nhng do hm lng thp nn c t trong pha lng Cc tp khc t nh hng ti mc oxiha

Cht n ( cht lm y HAOHTE )

Khi t0 pha lng nhiu: + Ngn cn pha kh khuych tn ti pha R + Thm thu pha lng vo bn trong pha R (khi t l pha L:R 0,15-0,35g :1,0g ) gy kt khi lm d S tip xc Khc phc:b xung cht n rn kh nng chy lm gim t l L:R gim b dy mng L cn ~ 1m to cho phi liu ti xp d di chuyn trong l t Nh vy: + khi t0 :- lng lng S hiu sut - Tc phn ng - % Cr2O3 thch hp + Khi t0 : lng lng d S Cht n:oxitcanxi,magie,silic. Mui cacbonat canxi,magie.khong canxit,

Hnh 6.3 hiu sut ha tan cromat khi c CaO

100

a
50

Na2CO3

50

b N CaO

Hnh 6.4 s ph thuc mc oxy ha thi gian nung

A,%
100

11600 10500 9300 8300

50

t ,min

Thnh phn khong thiu kt

Ty thuc : Hm lng cc cht trong phi liu T0 ,t nung ,kiu l, Do h khng t cn bng nn kh xc nh chnh xc Thng thng gm:~ 40% cromat Ca,Na trong 80%Na2CrO4 . Khong aluminat silicat,ferat.MgO (~10%MgO to khong)

Tnh ton phi liu

Tnh trn cn bn 100 vkl cromit (C) Tnh lng soda:[Na2CO3] =1,395k[Cr2O3] Trong : +[Na2CO3] l lng soda; kg + [Cr2O3] l hm lng oxitcrom trong (C),% + K l mc oxiha oxitcrom,phn n v + 1,395 t l soda/oxitcrom l thuyt

Tnh lng oxitcanxi

Lng CaO ty thuc vo: + Loi qung cromit + Hm lng cc cht lin kt cvi CaO + Dng khong cha CaO c to thnh Khi t l Al2O3:Fe2O3 0,64 :
[CaO]=1,87[SiO2]+0,91[Al2O3]+0,82[Fe2O3]+0,26[Cr2 O3] Khi t l [Al2O3]:[Fe2O3] 0,64 : [CaO]=1,87[SiO2]+1,1[Al2O3]+0,7[Fe2O3]+0,26[Cr2O3]

Tnh cc thng s k thut

Mc oxiha( % Cr2O3 b oxiha thnh Cr6+ ) khi tc cp liu C 11,5.103 kg/g : A =130,4 -1,125.102 .C Hiu sut l (kg Cr2O3*/g): P= A.B.C.10-4 B l %Cr2O3 trong phi liu i vo l Cng sut l(kg Na2Cr2O7 .2H2O /g) Q = 3,5(100-A)0,45.D1,5.L D l ng knh trong ca l ;m L l chiu di l ;m

BI TP
Phi liu a vo l t kiu thng quay sn xut Natricromat (vi tc cp liu C l 5,0 tn / gi ) gm cc nguyn liu sau: + Qung cromit : 50%Cr2O3 ; 10%Fe2O3 ; 5% Al2O3 ; 2%SiO2 + Soda : 98% Na2CO3 ; 2% m + Oxitcanxi : 95% CaO 1/ Tnh % nguyn liu c trong phi liu trn 2/ Tnh hiu sut l P BI GII 1/ Tnh % nguyn liu: Ly c s tnh ton i vi m0= 100 kg qung cromit a) Tnh mc oxihoa Cr2O3 ( A % ): A = 130,4 0,01125 C = 130,4 0,01125 . 5000 = 74,15 % b) Tnh lng soda ( m1): k = 0,7415 m1 = 1,395. k. [ Cr2O3] . 100/ 98 = 1,395 . 0,7415 . 50 .100/98 = 52,78kg

BI TP
c) Tnh CaO (m2) : t l Al2O3 : Fe2O3 = 5 : 10 = 0,5 0,64 m2 = [1,87SiO2 + 1,1 Al2O3 + 0,7 Fe2O3 + 0,26 Cr2O3 ].100/95 = [ 1,87x 2 + 1,1 x 5 + 0,7x10 + 0,26 x 50 ]x100/95 = 30,78 kg d) Tnh % : Tng nhp liu : m = m0 + m1 + m2 = 100 + 52,78 + 30,78 =183,56kg + % qung cromit : (100 . 100) / 183,56 = 54,48 % + % qung sota : (52,78 . 100) / 183,56 = 28,75 % + % CaO : ( 30,78 . 100) / 183,56 = 16,77 % 2/ Tnh P : + Tnh % Cr2O3 trong phi liu : B = 50 . 100 / 183,56 = 27,24 + Hiu sut l P: P = A . B . C . 10-4 = 74,15 . 27,24 . 5000 . 10-4 = 1009,92 kgCr2O3 / gi

Ha tch cromat t sp thiu kt

Thnh phn khong trong sp thiu kt + Dd rn Na2CrO4.CaCrO4 + Khong silicat 2CaO.SiO2 + Khong aluminat 12CaO.7Al2O3 + Khong Ferat 2CaO.Fe2O3 + Dd rn 4CaO.Al2O3.Fe2O3 + MgO(90%MgO;4CaO.2MgO.Al2O3.Fe2O3) + Na2CO3 ; mui Cr ha tr thp ( < 6)

Nhn xt
Nu dng nc ha tch: + Mui cromat;aluminat;soda b ha tan + Khong silicat;ferat;alumin-ferat chuyn dng + Oxit magie v hp cht ca n khng tan V d: CaO.SiO2+H2O=Ca(OH)2 +H2SiO3 tng hiu qu c th axit ha dd bng axit yu (CO2) kt ta CaCO3 trit khi dd v trnh mt cromat dng kh tan 3CaO.Al2O3.CaCrO4.12H2O

X l dd cromat
Dd cromat thu c sau khi lc b cn + C c kt tinh mui natricromat + Chuyn ha thnh mui natridicromat + Trao i ion thu mui dicromat khc Do nhu cu v gi tr mui dicromat cao; tan ca n km nn hai phng php sau thng c s dng

Cc phng php chuyn ha

Axit ha dung dch cromat +CrO42- + H+ Cr2O72- + H2O Clo ha dung dch cromat +CrO42- + Cl2 = Cr2O72- + Cl- + ClO3 in phn hn hp cromat clorua Thc cht cc pp trn u c th coi l pp axit ha

C s l ha qu trnh axit ha
P tng: 2CrO42- +2H+2HCrO4- Cr2O72-+H2O;(1) HA H+ + A- ; K1 =[H+].[A-] / [HA] ; (2) HCrO4-H++CrO42-; K2=[H+][CrO42-]/[HCrO4-] Cr2O72- +H2O2HCrO4;K3=[HCrO4]/[Cr2O7] Gi: a l nng mol HA ban u C l nng mol cromat ban u

C s l ha qu trnh axit ha
1/ Khi cc mui khng in ly v tan tt 2k12(1-x)2(a-cx)2+k1k2k3.x(1-x)(acx)=k22k3cx3,(8 Khi dng pp th hay xp x gii pt trn s tnh c x Khi k3 ln ta coi lng ion Cr2O72- nh v thu phng trnh tnh x n gin hn (k1-k2)cx2-(a+c)k1x +k1a =0 Gii phng trnh trn tnh c x

C s l ha
Khi a=c t pt trn ta c X=1/1+ k2/k1 ; (10) Trn th vi tung x ,honh -lgk1 ,khi c dnh k2 v tnh s thay i x=f (-lgk1) ta c : +ng s 1 (khi k2 = 10-7 ) +ng s 2 ( khi k2 = 8.10-7 ) Nhn xt : +Khi k1 ln ( axit mnh) x +Khi t0 k2 x

 th x = f (-lgk1) khi k2 = const

x ng 1: k2 = 10-7 ng 2: k2 = 8.10-7

ng 3: k2 = 10-7 b1 = 0,05 c v a = c

- Lg k1

2/ Khi HA tan tt-MA t tan (c MA rn )

K2x = k1(1-x)(a-cx) / (b1-b2x) ; (14) Vi b l tan MA trong dd dicromat , b1 l tan ca MA trong dd cromat , b2 = b - b1 ; Nu tan ca MA =const ta c b2=0 ,khi a=c Gii phng trnh trn tnh x (b nghim x>1), khi biu din x theo lgk1 (vi b1=0,05.c , a=c v k2 = 10-7) ta c ng s 3 trn th Nhn xt: + khi k1 x + khi k1=const ,ta c x ln hn trc

3/ Khi dng HA tan km (v d H2CO3)

Lc ny [HA] const , b2 0 . K2 = k1[HA].(1-x) / b1.x x = k1.[HA] / ( k1.[HA] + k2.b1 ) ; (16) Khi dd cha bo ha MA : [A-] + [HCrO4-] = c.x K2 = k1.[HA].(1-x) / c.x2 Gii phng trnh trn tnh c x ( ly gi tr ca x trong khong 0 x 1 )

4/ Nu HA dng kh (v d CO2 hay H2CO3 )

Lc u c cn bng [HA]k[HA]dd v x=f(p) Gi s h tun theo l Henry :[HA] = k.p vi p l p sut ca HA (hay anhydric ca HA ) trong pha kh 4.1 - Nu c mt MA rn : T (16) x= k1.k.p / (k1.k.p + k2b1) ; (18) Hay : x = 1 / 1 + ( k2b1 / k1.k.p ) ; (20) 4.2 - Nu khng c MA rn : T (17) phng trnh (19) tnh x Nhn xt : khi p x

5/ Kt lun
a/ t0 ch yu nh hng ti tan ca HA v MA cn t s k2 / k1 f ( t0). Khi t0 tan ca kh gim v ca mui thng tng.T (20) thy khi t0 s x ( do b1 v p ) b/ Khi tt c u tan tt x f (nng ) v b1 khi tng nng ( b1 = S / 2c ) .theo (18) x ch tng ng k khi nng v c MA pha rn ( gn ging khi HA tan km ). Cn theo (19) tng nng s x ( khng c MA pha rn ) c/ k1 ( axit cng mnh ) x v ngc li .

Chuyn ha natri bicromat thnh kali bicromat

+ Mui kali bicromat thng c s dng rng ri v c gi tr cao hn mui natri bicromat + tan ca mui kali km mui natri KCl + Na2Cr2O7 = K2Cr2O7 + NaCl + Da trn gin h bc bn tng tc trn thy rng t0 thp ( 250) vng kt tinh K2Cr2O7 rt ln cn t0 cao (1000) l NaCl c th tch mui t hn hp cc t0

Gin h KCl + Na2Cr2O7

Qui trnh sn xut bicromat natri

cromit Soda tinh 1 4 2 CaO 13 Soda hi lu

CaCO3

5
6 9 H2O

38%CO2

10
CO2 thi 11 11

7
bicromat

Cn 90%CO2 50% CO2 Kt tinh Soda hi lu 12 8 L nung

bicacbonat

Ch thch
1/ my nghin qung 2/ my trn phi liu 3/ l nung vi 4/ l nung phi liu 5/ thng cha 6/ my nghin bt t 7/ my lc 8/ thit b ra 9/ thit b bay hi 3 cp 10/ thit b bay hi 2 cp 11/ ni hp ( octocla) 12/ my nn kh 13/ my nghin vi

III.5-qu trnh kh cromat thnh oxit crom

1/ Cc phng php sn xut Cr2O3 a/ Kh cromat nhit cao: Khi kh bicromat (hay cromat) t0 cao bi cht kh mnh (nh C,S,) s thu c oxit crom V d: + K2Cr2O7 + C = Cr2O3 +K2CO3+CO +K2Cr2O7 + S = K2SO4 + Cr2O3 Mc kh ty thuc cc iu kin nh t0 , t , t l cht ,mc trn ln ,sn phm nung c ha tch bng nc nng (50-600)

Kh cromat .
Nung hn hp K2Cr2O7 +C+S t l 15:3:2 thu sn phm 82%Cr2O3 . loi b C d c th nung sn phm vi NH4NO3 + NH4NO3 + C = N2 + CO2 + H2O + NH4NO3 +K2CO3 =NH3+ CO2 +KNO3+H2O 3500 khi t l nitrat : oxit = 1 : 10 sau 1 gi hiu sut kh C t 85-90% .Lu nu nung t0 cao xy ra phn ng lm gim hiu sut KNO3 + Cr2O3 = K2CrO4 + N2O3 + NO2

b/ Nhit phn mui cromat amoni

Khi nung mui amon cromat (bicromat) : (NH4)2Cr2O7 = Cr2O3 + N2 +H2O + 123 kcal C tc gi xut dng NH3 hay mui SA kh ( thc cht cng gn ging phn ng trn) K2Cr2O7+(NH4)2SO4 = Cr2O3 +K2SO4+N2+H2O K2Cr2O7 + NH3 = K2O.Cr2O3 +N2 + H2O Hn hp c tch bng nc (hay axit long)

c/ Kt ta bng dd ba z
Phn ng : Cr3+ + OH- = Cr(OH)3 Khi phn ng xy ra t0 cao Cr(OH)3 = Cr2O3.xH2O + H2O Sn phm thu c sau khi lc ra em nung loi ht nc . Lu : do crom hydroxit lng tnh nn khng dng ba z qu d

Nung CrO3 nhit cao

Phng php ny t c s dng v phn ng xy ra phc tp ,trong sn phm c ln nhiu oxit crom ha tr khc 850-9000 : CrO3 Cr2O3 + O2 450-4900 : CrO3 CrO1,56 + O2 ,

Chng VII : K thut sn xut mt s pigment

.1 Cadimi pigment : 1/ i cng v cadimi pigment Pigment cd c mu hay vng rt p v c bn cao Hu nh tt c pigment Cd u da trn c s CdS. Cu trc tinh th lc din vi Cd chim cc im gia hnh t din v khi thay th mt phn cc ion bi cc cu t khc s lm thay i mu v tnh cht

i cng v Cd pigment
V d : Khi thay mt phn Zn s lm gim cc thng s mng v pigment c mu vng xanh Khi thay bi Hg v Se ty theo hm lng s lm tng kch thc mng v mu chuyn dn sang cam hay Cc mu pigment Cd p do ph phn x tng

Quan h gia h s phn x - di sng

2/ Tnh cht ca Cd & hp cht

Cd thuc nhm IIB chu k 5 : 4s10 5s2 CdS tn ti dng khong greenockite + Dng CdS :lc lng 6 cnh vi mng li c 4 nhm CdS ( a=4,124 v b=6,274 ) mu + Dng CdS: lp phng ( a=b=5,82 ) mu son CdS t tan trong nc(T= 0,4 -1,14.10-28 250) tan trong axit ( nhng kh tan trong axit long, NH4+, H2SO4 ), bn ha, bn sng v bn nhit t0 13500 .khi c mt khng kh : CdS + O2 = CdSO4 ( 300-5000 ) CdS + O2 = CdO + SO2 ( 600-7000 ) CdS b kh thnh Cd trong kh quyn H2 v t0 ,d mt mu khi nghin nh CdS c cng mu (tinting strength) loi trung bnh,

3/ ng dng
Cht mu trong sn ,cao su lu ha ,cht do, Mc mu ,nhum,in la ,x phng , Cht mu trong gm ,s, thy tinh, Khi phi trn vi pigment xanh to mu lc Do hp th v phn x nh sng tt nn dng sn xut pin mt tri: cho CdS thng hoa v ngng t trn mt thy tinh ,sau ngm trong dd CuCl to lp Cu2S (pin ny c =16% ) Do c tnh CdS b han ch ng dng

4/ Vn kinh t , mi trng
CdS v cc hp cht t tan nhng khi vo c th chng tch t (nn khng gy c tc thi) v gy tc hi ( ngng cht LD50 ca chut l 10 g / kg ). Pigment Cd hin gi ch yu dng trong cc lnh vc t gy hai trc tip cho con ngi ( s, gm,hi ha ,)

5/ K thut sn xut pigment CdS

5.1/ Pigment vng CdS ( Cd yellow) Cd2+ + S2- CdS C th thay S2- bng kh H2S . Lc u kt ta CdS dng .Khi t nng n chuyn qua dng mu vng c tnh quang dn . ci thin tnh cht mu v gim gi thnh c th thay th 1/3 Cd bng Zn . Pigment ny c d=4,5-4,8 g/cm3 v n =2,4-2,5

Quy trnh sn xut CdS

5.2/ pigment Cd (Cd.sulfoselenua red )

CdSe mu nu en, c cu trc dimorphous (lng hnh) dng khi hay lc gic v khng c cc tnh cht ca pigment. thay th mt phn S bi Se mu ca n t vng cam (ty mc thay th ).sn phm cui c d=4,6-5,6g/cm2 v n=2,5-2,8 cu trc dng khi hay lc din vi kch thc ht trung bnh 0,3-0,4 m

Qui trnh sx pigment hn hp

5.3/ pigment (Cd,Hg)S

Thay th mt phn Cd bi Hg s thu c sn phm c mu m dn t vngcam (ty mc thay th)gi l cadmicinnabar(thn sa) Pigment cadmi-cinnabar c cc tnh cht mu tng t pigment trn Do Hg rt c v gy nhim mi trng nn hin nay t c sn xut v s dng

.2- sn xut Pigment st-blue

Pigment st-blue l tn gi chung cho nhiu sn phm: berlin.blue ,paris.blue, russian blue ,milori.blue ,v c Diesbach iu ch vo nm 1704 . 2.1/ thnh phn v cu trc: theo Ph X-ray v infra-red : MIFeIIIFeII(CN)6.H2O +M l K+,Na+,NH4+,trong ph bin nht l K+ v cho mu p nht +Cu trc nhm FeIIIFeII(CN)6 cho thy c s xen k cc nt mng FeII v FeIII ,cn CN- nm cnh hnh lp phng .kiu lin kt - FeII C N FeIII - . +M+ v H2O nm pha trong hnh (H2O gip n nh )

2.2/ sn xut pigment st-blue

Gm cc bc: a/ Cho phc Fe(CN)64- tc dng vi FeII thu ta trng M2IFeIIFeII(CN)6 hay MIIFeIIFeII(CN)6 . (Dng mui K , K v Na , K v NH4+ ) b/ Nung ta ( t0, t , [M],..quyt nh hnh dng v kch thc ht ca pigment ) c/ Oxy ha ta (bi H2O2 ,clorat hay cromat kim) d/ Lc ra k loi mui v axit e/ X l b mt pigment

S cng ngh sx pigment st-blue

.
330H2SO4 1095FeSO4 H O 2 p 1732Na4Fe(CN)6 Hi nc Sy Nghn,ry

127NaCl

Lc ra X l

300.SA

1000 st-blue Cn:507CaSO4 Fe4[Fe(CN)6]3 276Ca(OH)2 190Fe2O3 dd 32Fe(OH)2 70NaCl+300SA+1016Na2SO4

2.3 tnh cht &ng dng ca pigment st-blue

Cc tnh cht quan trng: +Bn nhit( 1800 )nhng 1400chy trong kk +Bn nh sng&thi tit( mt khi trn vi mu trng ) +Bn trong axit yu ,khng bn trong ba z ,axit nng ,m c , ng dng : +Lm mc in ,cht mu trong thuc dit nm, phi trn vi cht mu khc n nh mu +Sn xut giy mu xanh +Trong y t dng cha nhim x 137Cs

2.4 sn xut pigment oxit st-red

Phng php kh : cc mui st II( sulfat , clorua,nitrat,oxalat,)c em nung t0 V d: FeSO4 Fe2O3 + SO2 Phng php t: mui st tc dng vi ba z thu kt ta hydroxit , nung hydroxit thu oxit st V d:FeSO4 +NaOH +O2=Fe(OH)3+Na2SO4 Fe(OH)3 = Fe2O3 + H2O

.3-sn xut pigment km-trng &km-vng

3.1/Tnh cht l ha
Tnh cht H s chit xut , n T trng , g/cm3 cng , Mohs tan trong nc (180),% Tc dng ca axit-ba z Tc dng ca dm hu c Tan trong H+ Khng tan khng khng ZnS 2,37 4,08 3,0 BaSO4 1,64 4,48 3,5

3.2/tnh cht mu
ZnS hp th nh sng max 700 nm nn c mu trng xanh Do n ca ZnS (2,37) >> n ca nha v cht kt dnh (1,5-1,6) nn c tnh khuych tn as tt. kh nng khuych tn tt nht l ht hnh cu (D=294 nm).BaSO4 c n nh (1,64) nn n ch l extender.Lithopone dng lm cht ph ZnS v lithopone chu mi mn , ch s hp ph du thp, cng mohs thp

3.3 sn xut
Sn xut lithopone: ZnSO4 + BaS = BaSO4 + ZnS ( 29,4%ZnS) Hm lng ZnS c th thay i khi thay i pp iu ch : v d iu ch lithopone 62,5%ZnS ZnSO4+ BaS + ZnCl2 = ZnS + BaSO4 + BaCl2 Sn xut pigment km-vng : Zn2+ + CrO42- = ZnCrO4 Cht thi c x l thu hi Zn v CrO42-

.4 / pigment ultramarine 4.1 Lch s

+Xanh ultramarine (xanh bin) c ngi trung c ly t lapis laruli Afganistan v rt ph bin vo nhng nm 600-1500 AD nhng dn khan him +Nm 1828 T.B Gumet(Php) v C.Gmelin(c) tm ra phng php tng hp mu ultra t cc nguyn liu ph bin v r tin +Ultra hin c 3 mu : xanh- ,tm v hng vi s khc bit v cu trc v trng thi oxy ha ca lu hunh .Thnh phn ca ultra tng hp c th thay i

4.2 Cu trc ha hc
L dng khong Aluminosilicat 3 chiu vi cc ion Na+ v S-n nm cc nt mng .Cu trc mng dng Sodalite vi cc khi lp phng kch thc 0,9 nm Thnh phn alumosilicat : Na6Al6Si6O24 khi c S trong mng : Na7Al6Si6O24S3 Mu ca ultra do bn cht ca 2 nhm S to ra +Nhm S3- c di S-S l 0,2nm ,gc 1030 n hp th trung bnh 600nm ( green orange) +Nhm S2- hp th 380nm ( violet-ultra violet) Cu trc bn nht ca ultra khi tng in tch bng o

Cu trc ha hc ca ultra
tng phm cht mu ca ultra cn tng [S] gim [Al] v [Na] . Sn phm ultra c trng c cng thc Na6,9Al5,6Si6,4O24S4,2 c mu xanh m nh . Mng tinh th ca ultra tm v hng hi khc ultra xanh ch chuyn dng mt phn cc nhm S-2 , S-3 thnh S3Cl- v S4 S phn b Si4+ v Al3+ trong mng ultra tng hp v trt t cn ultra t nhin ngc li

4.3 -Tnh cht ca ultra

Ultra c mu xanh nh vi sc mu thay i ty theo thnh phn ha hc Kch thc ht trung bnh 0,7-5,0 m. ht cng nh sc xanh nhiu v nht . Khi trn pigment trng s tng sng, bo ha v m c Ultra bn nhit ( 200-4000) ty theo dng . t0 cao ,chiu sng hay trong axit n b mt mu . S thot H2S trong axit dng nhn bit.n bn trong ba z yu ultra khng mi v khng chy . Ultra kh tan trong nc v dung mi hu c nhng n c th hp ph hi nc , n=1,5 ( sn ,cht do)

Tnh cht ca ultra

Tiu chun : ph : 2 % [ S] : 0,05 % Cht tan trong nc : 1,0 % Kch thc ht > 45 nm : 0,1 % m : + loi th : 1,0 % +Loi mn : 2,0 % Kim loi nng : vt

4.4 iu ch ultra thnh phn phi liu (%)

Gam mu lc Gam mu

t st nung
Felspar soda Na2CO3 Lu hunh S Cht kh ,C

32,0
7,0 29,0 34,5 4,5

30,0
.. 27,0 33,0 3,0

iu ch ultra ultra th
Trn v nghin hn hp ti d 15m ,sau nung trong mi trng kh theo tng cp 3000 : Na2CO3 + S + C = Na2Sx + CO2 7000 mng ca st lc u chuyn sang dng 3 chiu v khi c s xm nhp ca Na2Sx n sang dng sodalite Oxy ha bi khng kh < 5000 loi S d to SO2 . Kh SO2 oxy ha cc ion di-triatomic polysulfua thnh S3- , S2- ,S v natri sulfoxit. Ultra th cha 75% ultra xanh, 23% natrisulfoxit , 2%S v mt t S2-

iu ch ultra lm sch v tinh luyn

Mc ch: loi b tp cht dng tan nh cc mui natri sulfoxit , sulfua ,v nghin mn Tc nhn lm sch l nc cc t0 khc nhau

S sn xut ultramarine .
457caolin
940Na2CO3+Na2SO4

1-10 than
1-10 nha

Phn ng

(200SO2+115CO2 + H2O) Lm lnh

Nghin

H2O Lc ra Dd thi

320 thch anh 334 S

1000 st-blue

nung

33 S