3 cement chemistry cl 26 jun 00 a
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CEMENT
MANUFACTURING
AND
CEMENT CHEMISTRY
Module CMT xxx
26 Jun 2000
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Cement Material & Manufacture of
Cement
Raw Materials
Clinker
Gypsum
Portland Cement
C2S + C3S + C3A + C4AF + CaSO4. 2H2O + CaO + MgO
(depending on the cement)
CALCAREOUS2 pa!t"
# Lime"tone (CaCO3)# Cement !oc$"# Cha%$# Ma!%# Ma!ine "he%%" and co!a%# A%$a%i &a"te
AR'LLACEOUS pa!t# C%a*"# Sha%e"# S%ate and Md"tone"# ,%a"t -!nace "%ag# A"he" (-%* a"h)# Cement !oc$
CEME/ CL0ER
# C3S 1 /!ica%cim Si%icate# C2S 1 ica%cim Si%icate# C3A 1 /!ica%cim A%minate# C4AF 1 /et!aca%cim A%mino-e!!ite# Ca + Mg Oide" Ca (OH)2 CaCO3 a2SO4 etc
A 3 56 '*p"m (Ca.SO4. 2H2O) o! ,%end o- '*p"m + 7%a"te!
7OR/LA CEME/
+ (a2SO4+ a0SO4+ Ca02(SO4)2 o! 02SO4
'!ind + Heat /!eat in 0i%n /empe!at!e + 588oC
Cont!o%%ed Coo%ing /o "econd g!inding mi%%
7%9e!i"e mit!e And ,%end
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ources of Cement !aria"ility
M#$#%G %' PR(P(RT#(%#%G R)MT*R#+
,#+%#%G -./R%#%G
C((+#%G
GR#%'#%G %' ''#T#(% (1 GP/M
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lternati3e .lendin4 of Materials
Schematic -%o& diag!am o- the d!* p!oce"" nepen"i9e incon"i"tent
Schematic -%o& diag!am o- the &et p!oce"" Epen"i9e Con"i"tent
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5eat treatment 4rindin4 and
stora4e
Schematic flow diagram of the burning process
Schematic flow diagram of the grinding and storage
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.urnin4 and Coolin4 (perations
Reaction zones ina rotary cement kiln
Up to 288oC :ate! E9apo!ation
288;88oC + 7!eheating !e%ea"e o- C%a*
&ate!
;88 88oC i""ociation o- Ca!
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Cement Compounds
TR#C+C#/M #+#CT* (CaO)3SiO
2 ,C
3S or Alite
Major Como!e!t "#$
'#C+C#/M #+#CT* (CaO)2SiO2, C2S or %elite Me&i'm Como!e!t 2"$
Eit i! i!ert a!& rea*ti+e orm
TR#C+C#/M +/M#%T* (CaO)3Al2O3 , C3A orAl'm!ateMi!or Como!e!t 3$U!&eira-le
C+C#/M +/M#%( 1*RR#T* (CaO).Al2O3Fe2O3, C.AF orFerrite
Mi!or Como!e!t /2$Slo0 rea*ti!1 a!& re1'late le+el o C3A
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Cement Clinker Grain tructure
C3A1 /!ica%cim A%minate
3CaO. A%2O3
C4AF1 /et!aca%cim A%mino-e!!ite
4CaO. A%2O3.Fe2O3
C3S1 /!ica%cim Si%icate
3CaO. SiO2
C2S1 ica%cim Si%icate
2CaO. SiO2
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*7ects of Ma8or Clinker Components C3S, Tri*al*i'm ili*ate
9 Ma8or component in cement -formed from Ca( and i(29 5ydrates more rapidly t:an C
2 ; Controls settin4 time
9 Contri"utes to all sta4es of stren4t: de3elopment -esp< early
C2S, Di*al*i'm Sili*ate9 1ormed from Ca( and i(29 5ydrates 3ery slowly wit: lowest :eat of :ydration9 7ects lon4;term stren4t:
C3A, Tri*al*i'm Al'mi!ate9 1ormed from Ca( and l2(=9 5ydrates rapidly and produces
:i4:est :eat of :ydration9 Plays important role in>
*arly stren4t: de3elopment R:eolo4y "e:a3iour of slurry
Controllin4 settin4 and t:ickenin4 times9 5ydrated C= is readily attacked "y sulp:ate water9 Concentration controlled in MR & 5R cements
C.AF, Tetra*al*i'm al'mi!oerrite? 1ormed from Ca( l2(=and 1e2(=? Gi3es colour to cement? +ittle e7ect on set cement properti? Produces low :eats of :ydration
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Ee*t o Cooli!1 Rate o! Ceme!t
roertie 4 5ae
4 5 C>min 588oCto 288oC ; 28 C>min to Am
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C:an4es in Gypsum Content
'@7SUM AE /O 7RE=E/ FLASH SE/
F%a"h Set i" the Uncont!o%%ed Reaction o- C3A '*p"m
Rende!" C3A ne!t in Ea!%* Stage" o- H*d!ation C3A
'@7SUM CA EH@RA/E /O FORM 7LAS/ER (o! Anh*d!ite)
CaSO4.2H2O CaSO4.8.5H2O + .5H2O
S
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Ee*t o Ma!'a*t'ri!1 ro*e Ste o! Ceme!t
roertie
Mate!ia%CaOSiO2A%2O3
Fe2O3MgO
# A%%o&" c%in$e! c!*"ta%%i"ation # '%a"" -o!mation
# En"!e"
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P# Cement Classi@cation C6ASS A> #ntended for use from surface to a dept: of 6000 ft -AB=0 m w:en special
properties are not reuired< imilar to TM Type # cement#ntended for use from surface to a dept: of 6000 ft -AB=0 m< Moderate to:i4: sulp:ate resistance< imilar to TM Type ## and :as a lower C= content t:an Class
< C6ASS C > #ntended for use from surface to a dept: of 6000 ft -AB=0 m w:en
conditions reuire early stren4t:< 3aila"le in all t:ree de4rees of sulp:ate resistanceand is rou4:ly eui3alent to TM Type ###< To ac:ie3e :i4: early stren4t: t:e C=content and t:e surface area are relati3ely :i4: #ntended for use from 6000 ft -AB=0 m to A0000 ft -=0D0 m underconditions of moderately :i4: temperatures and pressures< #t is a3aila"le in MR and5R types #ntended for use from A0000 ft -=0D0 m to AE000 ft -E2F0 m underconditions of :i4: temperatures and pressures< #t is a3aila"le in MR and 5R types< C6ASS F > #ntended for use from A0000 ft -=0D0 m to A6000 ft -EBB0 mdept:
under conditions of extremely :i4: temperatures and pressures< #t is a3aila"le in MRand 5R types#ntended for use as a "asic well cement from surface to B000ft -2EE0 m as manufactured or can "e used wit: accelerators and retarders to co3er awide ran4e of well dept:s and temperatures< %o additions ot:er t:an calcium sulp:ate or
water or "ot: s:all "e inter4round or "lended wit: t:e clinker durin4 manufacture ofClass G and 5 well cements< T:ey are a3aila"le in "ot: MR and 5R types 1+5 *T)it: Gypsum>
9 C= = C52 265 ;;HC= < =C< =25
9 C= Gypsum water ;;H*TTR#%G#T*
9 *TTR#%G#T* Produces a protecti3e layer tostop :ydration of C= and pre3ent as: set
ll 4ypsum @nis:ed>
9 C=< =C< =25 2C= E5 ;;H =C=
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5ydration of Cement
. 7RE UC/O 7ERO
. UC/O 7ERO
. ACCELERA/O 7ERO
=. ECELERA/O 7ERO
=. FFUSO 7ERO
O/E1
() Fo! C3S pha"e h*d!ation
(2) Con"tant tempe!at!e
I II III I/ /
min )r days
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TG* A and 2> Pre #nduction and #nductionPeriods
SO4
CaA% OH Ca Si
E//R'/E
C S H 'e%
7RO/EC/=E LA@ERS S/O7S REAC/OS GGGG 7UM7' /ME
Second"
Ho!"
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TG* =
E//R'/E
C S H 'e%
AS 7AR/CLES COEC/ RHEOLO'@ CREASES
ndction 7e!iod A%mo"t nacti9e Ca nc!ea"e" in So%tion
End o- ndction 7e!iod ndicated
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TG* E and D
E//R'/E
C S H 'e%
/HE 7ERO OF ACCELERA/E REAC/O /O '=E A FULL SE/
(HOURS A@S)
SLURR@ E=ELO7S COM7RESS=E S/RE'/H S/A'E 4
REAC/O SLO:S O: S/A'E 5 UE /O FFUSO LM/A/O
Ca(OH)2
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+a"oratory Performance !aria"ility
!aria"ility #n T:ickenin4 Times and Gelation
To Control T:ickenin4 Times or Gelation MeansModifyin4 Retarder or 'ispersants
,c
/ime > ho!"
88 ,c
a4nes um an u p a e
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a4nes um an u p a eResistance
M4 %a ulp:ates in formation uids react wit: Ca-(52crystals in t:e cement to form>
9 Ca-(52 M4(E 252( ;;;H Ca(E < 252( M4-(529 Ca-(52 %a2(E 252( ;;;H Ca(E < 252( %a(5
? Crystals of M4 -(52 weaken cement? solution of %a(5 #ncreases Permea"ility "ecause %a(5 is
olu"le
? #f ource of M4 is t:e Cement t:e lurry R:eolo4y #ncreases'urin4 *arly 5ydration (5 M4 ;;;H M4-(52
1ormation of *ttrin4ite after cement :as set expansion and crackin4 of cement
swellin4 due to t:e replacement of t:e Ca-(52"y
M4-(529 ulp:ate reacts )it: /nreacted C= to form more *ttrin4ite
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olutions Mi!imie C3A i! Ceme!t
9 Hi15 S'l5ate Reita!t (HSR) Ceme!t Ha 6eT5a! 3$
9 Me&i'm S'l5ate Reita!t Ceme!t 3$ to 8$
9 Co!tr'*tio! Ceme!t 8$ 7
Mi!imie Ma1!ei'm Co!te!t o Ceme!t
9 Re1'lar Cla G HSR re9'ire& to 5a+e : ;$
9 T>ola!i* Material U!&er Re+ie0
9 Ca(OH)27 SiO2 ???= Cal*i'm Mo!oili*ate
(D'ra-le, Reit Ea!io!)
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tren4t: Retro4ression at *le3ated
TemperaturesTemperatures a"o3e AA0oC
9 Geot:ermal team )ells
9 'eep (il and Gas
9 )ells /sin4 team #n8ection
Reuire T:ermal Cement ystem
9 +oss of Compressi3e tren4t: Caused "y MineralTransformation "o3e AA0oC< 5i4: Temperature P:ases areweaker T:an +ow Temperature P:asesS and 7!e9ent" Ret!og!e""ion
0
10
!0
$0
0
"0
0 " 10 1" !0 !"
C!ing /ime > Month"
Comp!e""
i9eSt!ength
>p"i
iO !$" 2 B3O-
4eat -ement
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Permea"ility Reduction at 2=0oC L
ADpp4
7e!mea
iO!$"2 B3O-
4eat -ement
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Cement 'ura"ility
Cement " St!ong n Comp!e""ion ,t :ea$ n /en"ion
/he!ma% and 7!e""!e
Change" Ca"e St!e""e"
At nte!-ace"
/en"i%e St!e""e" Lead toCement Sheath Fai%!e
Radia% C!ac$ing
Fo!mation Cement Sheath
Ca"ing
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Cement 'ura"ility )it: '600
Late 7a!tic%e" 7!o9ide /en"i%e St!ength E%a"ticit*
o D88 2 ga%>"$ D88
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AI Se*i@*atio! o Cla G Ceme!t
'alit< Co!trolB Comoitio! a!& erorma!*eSe*i@*atio!
9 AI S*5e&'le " T5i*e!i!1 Time ("2oC)# ? /2# mi!9 Co!ite!*< ater /" mi! Stirri!1 Ma 3# %*9 8 5o'r CS at /##FMi! 3## i9 8 5o'r CS at /.#FMi! /"## i9 Free 0ater Ma 3" ml
9 M1O Ma ;$
9 SO3 Ma 3$
9 6OI Ma 3$9 I!ol'-le Rei&'e Ma #$
9 C3S .8$ to ;"$
9 C3A Ma 3$
9 C.AF 7 2 C3AMa 2.$
9 Total Alali Ma #"