US007540915B2

( 12) United Sta tes Pa tent

L ec o l ier et a ] .
US 7, 540, 915 B2
J u n. 2, 2009
( 10) Pa tent N 0. :
( 45) Da te o f Pa tent:
( 54) OIL -WEL L CEMEN T SL URRY
( 75) Inv ento r s : Er ic L ec o l ier , Ch a v il l e ( F R) ; A l a in
Riv er ea u , Ru eil Ma l m a is o n ( F R) ; A nnie
A u dib er t, Cr o is s y s u r Seine ( F R)
( 73 ) Ins titu t F r a nc a is du Petr o l e, Ru eil
Ma l m a is o n Cedex ( F R)
A s s ig nee:
( * ) N o tic e: Su b j ec t to a ny dis c l a im er , th e ter m o f th is
p a tent is ex tended o r a dj u s ted u nder 3 5
U. S. C. 154( b ) b y 46 8 da y s .
( 21)
( 22)
A p p l . N 0. : 10/ 573 , 596
PCT F il ed: Sep . 17, 2004
( 8 6 ) PCT N 0. :
3 71 ( 0X 1)
( 2) , ( 4) Da te:
PCT/ F R2004/ 0023 6 2
Ma r . 24, 2006
( 8 7) PCTPu b . N o . : WO2005/ 03 1114
PCT Pu b . Da te: A p r . 7, 2005
Pr io r Pu b l ic a tio n Da ta
US 2006 / 028 916 3 A 1 Dec . 28 , 2006
F o r eig n A p p l ic a tio n Pr io r ity Da ta
( F R) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 03 11195
( 6 5)
( 3 0)
Sep . 24, 2003
( 51) Int. Cl .
C04B 7/ 3 2 ( 2006 . 01)
( 52) US. Cl . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106 / 6 92; 16 6 / 28 5
( 58 ) F iel d o f Cl a s s i?c a tio n Sea r c h . . . . . . . . . . . . . . . . . . 106 / 6 92
See a p p l ic a tio n ?l e f o r c o m p l ete s ea r c h h is to r y .
( 56 ) Ref er enc es Cited
U. S. PA TEN T DOCUMEN TS
6 , 06 0, 53 5 A * 5/ 2000 Vil l a r et a 1. . . . . . . . . . . . . . . . . . 16 6 / 293
6 , 3 3 2, 920 B1* 12/ 2001 N o ik et a 1. . . . . . . . . 106 / 6 92
6 , 417, 26 8 B1 * 7/ 2002 Zh a ng et a 1. . . . . . . . . . . . . . . . . 524/ 8 3 3
F OREIGN PA TEN T DOCUMEN TS
DD 152 776
WO 99/ 23 046
DE
WO
12/ 198 1
5/ 1999
* c ited b y ex a m iner
Pr im a r y Ex a m iner il ennif er H Ga y
( 74) A tto r ney , A g ent, o r F ir m iA nto nel l i, Ter r y , Sto u t &
K r a u s , L L P.
( 57) A BSTRA CT
Th e inv entio n r el a tes to a h ig h -p er f o r m a nc e c em ent c o m p r is
ing a n a l u m nic c em ent With a n a l u m iniu m c o ntent o f a t l ea s t
m o r e th a n 3 0%; m ic r o s il ic a With a g r a in s iZe o f 0. 1 - 20 u m
Wh er eb y th e p er c enta g e th er eo f is 3 5 % l es s b y Weig h t in
c o m p a r is o n With th e Weig h t o f th e c em ent; m iner a l p a r tic l es
With a g r a in s iZe o f 0. 5 - 500 u m Wh er eb y th e p er c enta g e
th er eo f is 3 5% l es s b y Weig h t in c o m p a r is o n With th e Weig h t
o f th e c em ent, th e p er c enta g e o f s a id p a r tic l es b eing l es s th a n
th a t o f th e m ic r o s il ic a ; a Wa ter -s o l u b l e p o l y m er ?u idif y ing
a g ent Wh er eb y th e p er c enta g e th er eo f is 0. 2 to 3 . 0% in c o m
p a r is o n With th e Weig h t o f th e c em ent; a r eta r ding a g ent
Wh ic h is u s ed to c o ntr o l th e s etting tim e o f th e s l u r r y ; a n
a m o u nt o f Wa ter th e m a x im u m th er eo f c o r r es p o nding to 40 %
in r el a tio n to th e c em ent.
13 Cl a im s , 2 Dr a wing Sh eets
t( Pa )
149_"'1'?"l ""|' |"'|" T F '
- _ BEL A - Po r tl a nd G
120 : - E-BEL A -Sec a r 51 _
. BEL A -Ter na l
100 : -
E :
i.
I 1
6 0 f _.
40: -
;
20: -
, -. - 144. . |L L . . |. . . r . . L . |. . 14J . . . L L J .
1' ( 8 -1)
>
100 150 200 250 3 00 3 50 400 450
US. Pa tent J u n. 2, 2009 Sh eet 1 o f 2 US 7, 540, 915 B2
u h ) F IGJ
140_- I1' T . m . -- l
- _ BEL A - Po r tl a nd G
120 : - '5- BEL A - Sec a r 51
A BEL A -Ter na l
100
s 0:
6 0:
40_
20:
7( 8 -1)
50 100 150 200 250 3 00 3 50 400 450
I
( 1111)
F IG. 2A
_ T ( S)
I | l I | | | | | | 4l l J _>
U 500 100i] 1500 2000
US. Pa tent J u n. 2, 2009 Sh eet 2 o f 2 US 7, 540, 915 B2
F IG. 3
( m il l )
I I I I I I | l | I I I I I I I l | I l I I I I
250
200
150
100
Ij l 'l l l l l l l l l l l l l l l l l l l
l l l l l l l l l l l l l l l l l l l l l l l IL l l l l
50
%
0 l I | I p
0 0 5 1 1. 5 2 2 5
f ( M Pa ) F IG. 4
- I | I l | | I I l I I | | I | I I | I I | I | I | I I | -
. - ' " 20C , ~_ -
- ------ n ' \ _
I \ -
I ~~ _
. I \s _ _
_ I ~~_ x I _
. I _
I 11111 -\
' I . . . . . . -'
8 0 - 1 _____-
- I ____" -
L I -------- f
---------- h I "nu n".
6 0 m " J - . . . . . . . . . . . . . . . . . . -' _
. __ _ __ z
40 l _
20 ' -_
. , j T ( j )
0 g I I 1 I l 1 1 l I 1 I | l I l l 1 J _[1 l n | | I | | | >
10 20 3 0 40 50 6 0 70
US 7, 540, 915 B2
1
OIL -WEL L CEMEN T SL URRY
Th e inv entio n r el a tes to no v el f o r m u l a tio ns f o r c em enting
s l u r r ies s im u l ta neo u s l y h a v ing g o o d m ec h a nic a l p r o p er ties
a nd v er y g o o d c h em ic a l s ta b il ity r eg a r dl es s o f th e c h em ic a l
env ir o nm ent in Wh ic h th ey a r e em p l o y ed. In p a r tic u l a r , s a id
s l u r r ies m a y b e u s ed f o r c em enting o p er a tio ns in ex p l o r a tio n
Wel l s o r Wel l s f o r ex p l o ita tio n o f s u b ter r a nea n ?el ds s u c h a s
h y dr o c a r b o n r es er v o ir s o r g eo th er m a l r es er v o ir s .
Wel l c em enting o p er a tio ns a r e c o m p l ex a nd h a v e m u l tip l e
a im s : ens u r ing m ec h a nic a l h o l d o f c a s ing s in th e g eo l o g ic a l
f o r m a tio n, is o l a ting a p r o du c tiv e b ed f r o m a dj a c ent b eds ,
p r o tec ting c a s ing s a g a ins t c o r r o s io n du e to ?u ids Wh ic h c o u l d
b e c o nta ined in th e tr a v er s ed b ed. Th u s , c em ent s h ea th s m u s t
h a v e g o o d m ec h a nic a l s tr eng th a nd l o W p er m ea b il ity to ?u ids
a nd g a s es Wh ic h m a y b e c o nta ined in th e f o r m a tio ns .
To g u a r a ntee h y dr o c a r b o n p r o du c tio n th r o u g h o u t th e
ex p l o ita tio n o f a ?el d a nd f o r env ir o nm enta l p r o tec tio n
a s p ec ts , it is v ita l to p r o v ide c em enting m a ter ia l s With a v er y
l o W p er m ea b il ity , ex c el l ent m ec h a nic a l p r o p er ties a nd l o ng
ter m c h em ic a l r es is ta nc e. Cem enting m a ter ia l s h a v ing a l l
th es e q u a l ities s im u l ta neo u s l y Wo u l d g u a r a ntee s a f e c o n?ne
m ent o f ?u ids a nd th u s Wo u l d c o ntr ib u te to env ir o nm enta l
p r o tec tio n.
To s a tis f y du r a b il ity o b j ec tiv es , it a p p ea r s j u dic io u s to u s e
a m a ter ia l h a v ing a v er y l o W p er m ea b il ity . In f a c t, in th is c a s e,
th e l o W p o r o s ity a nd l o W p er m ea b il ity v a l u es Wh ic h r es u l t
th er ef r o m l im it th e p enetr a tio n o f a g g r es s iv e s p ec ies in th e
m a tr ix .
F o r m u l a tio ns f o r c em enting m a ter ia l s a r e kno Wn Wh ic h
r es u l t in th es e v er y g o o d m ec h a nic a l p r o p er ties a nd du r a b il
ity , f o r ex a m p l e a s des c r ib ed in Eu r o p ea n do c u m ent EP-A -0
950 03 4. Ho Wev er , th a t c o nditio n is no t s u f ?c ient to o b ta in a
h ig h du r a b il ity c em enting m a ter ia l in p a r tic u l a r in a g g r es s iv e
env ir o nm ents , a nd in p a r tic u l a r f o r ex ter na l a c idic m edia , f o r
ex a m p l e in r es er v o ir s With a h ig h H2S c o ntent, o r intended f o r
CO2 s eq u es tr a tio n.
Th u s , th e p r es ent inv entio n c o nc er ns a h ig h p er f o r m a nc e
c em ent c o m p r is ing :
a n a l u m ino u s c em ent th e a l u m ina c o ntent o f Wh ic h is a t
l ea s t 3 0%;
a m ic r o s il ic a With a g r a nu l o m etr y in th e r a ng e 0. 1 to 20 p m
th e p er c enta g e o f Wh ic h is l es s th a n 3 5% b y Weig h t With
r es p ec t to th e Weig h t o f c em ent;
m iner a l p a r tic l es With a g r a nu l o m etr y in th e r a ng e 0. 5 to
500 p m th e p er c enta g e o f Wh ic h is l es s th a n 3 5% b y
Weig h t With r es p ec t to th e c em ent, th e p er c enta g e o f s a id
p a r tic l es r em a ining b el o W th e p er c enta g e o f s a id m ic r o
s il ic a ;
a h y dr o s o l u b l e ?u idif y ing a g ent th e p er c enta g e o f Wh ic h is
in th e r a ng e 0. 2% to 3 % With r es p ec t to th e Weig h t o f
c em ent;
a r eta r ding a g ent to c o ntr o l th e s etting tim e o f th e s l u r r y ;
Wa ter in a q u a ntity o f a t m o s t 40% With r es p ec t to th e
c em ent.
Th e h y dr o s o l u b l e p o l y m er m a y b e a p o l y na p h th a l ene s u l
p h o na te a nd/ o r a p o l y x y eth y l ene p o l y c a r b o x y l a te.
Th e Wa ter c o ntent m a y b e l es s th a n 3 0%, in p a r tic u l a r eq u a l
to 27%.
Th e s l u r r y m a y a l s o c o m p r is e a q u a ntity , in a q u eo u s s o l u
tio n, o f a t l ea s t o ne a s s o c ia tiv e p o l y m er c o nta ining h y dr o
p h il ic m o tif s Hy a nd h y dr o p h o b ic m o tif s Hb c o nta ining C1 to
C3 0 a l ky l , a r y l o r a l ky l -a r y l g r o u p s .
Th e a s s o c ia tiv e p o l y m er m a y h a v e a m o l ec u l a r m a s s in th e
r a ng e 104 to 5>< 106 da l to ns a nd a nu m b er o f h y dr o p h o b ic
m o tif s Hb in th e r a ng e 0. 5% to 6 0%.
20
25
3 0
3 5
40
45
50
55
6 0
6 5
2
In a c c o r da nc e With th e inv entio n, th e s l u r r y m a y c o m p r is e
( With r es p ec t to th e Weig h t o f c em ent) :
24% o f m ic r o s il ic a ;
20% o f m iner a l p a r tic l es ;
0. 5% o f ?u idif y ing p o l y m er .
Th e s l u r r y m a y c o m p r is e 0. 5% o f a s s o c ia tiv e p o l y m er .
Th e inv entio n a l s o c o nc er ns a u s e o f th e s l u r r y des c r ib ed
a b o v e, to c em ent a Wel l in a n a c idic env ir o nm ent.
Th e A p p l ic a nt h a s dem o ns tr a ted th a t th e c em ent s l u r r y
m u s t r es u l t f r o m a c o m b ina tio n o f m iner a l c o m p o nents Wh ic h
a r e c h em ic a l l y s ta b l e o nc e p l a c ed in c o nta c t With a g g r es s iv e
ex ter na l m edia .
To th is end, th e inv entio n r ec o m m ends u s ing c a l c iu m a l u
m ina te c em ents Wh ic h h a v e ex c el l ent b eh a v io u r in a g g r es s iv e
m edia ( in p a r tic u l a r a t v er y l o W p H) a s th ey do no t l ib er a te
p o r tl a ndite du r ing h y dr a tio n. F u r th er , th e h y dr a tes f o r m ed,
tr ic a l c iu m a l u m ina te h ex a h y dr a te a nd g ib b s ite, a r e c h em i
c a l l y m o r e r es is ta nt, u nder th e tem p er a tu r e c o nditio ns
o b s er v ed in o il Wel l s , th a n th e h y dr a ted c a l c iu m s il ic a tes
r es u l ting f r o m Po r tl a nd c em ents .
Th e p r o du c ts f r o m h y dr a tio n o f a l u m ino u s c em ents v a r y in
na tu r e dep ending o n th e tem p er a tu r e a t Wh ic h th ey o c c u r .
Henc e, f o r tem p er a tu r es o f l es s th a n 500 C. , m o no c a l c iu m
a l u m ina te h y dr a te ( CA H 1O) , dic a l c iu m a l u m ina te h y dr a te
( CZA HS) a nd g ib b s ite ( A H3 ) a r e th e p r inc ip a l h y dr a ted
p h a s es f o r m ed. Ho Wev er , m o no c a l c iu m a l u m ina te h y dr a te
a nd dic a l c iu m a l u m ina te h y dr a te a r e tWo m eta s ta b l e c o m
p o u nds . Ov er tim e, th es e c h em ic a l c o m p o u nds Wil l b e tr a ns
f o r m ed into tr ic a l c iu m a l u m ina te h ex a h y dr a te ( C3 A H6 ) ,
Wh ic h is th e th er m o dy na m ic a l l y s ta b l e c o m p o u nd in th e
A l 2O3 iCa OiH2O s y s tem . Th is c h em ic a l tr a ns f o r m a tio n is
a c c o m p a nied b y a n inc r ea s e in p o r o s ity a nd th u s a r edu c tio n
in m ec h a nic a l s tr eng th . Th is p h eno m eno n c o ns titu tes o ne o f
th e m a j o r dis a dv a nta g es o f a l u m ino u s c em ents . Ho Wev er , it
h a s b een s h o Wn th a t th is p h a s e tr a ns f o r m a tio n is no t a p r o b
l em Wh en u s ing a l u m ino u s c em ent s l u r r ies in o il Wel l s . In
f a c t, f o r tem p er a tu r es o f o v er 500 C. , Wh ic h a r e r o u tinel y
enc o u nter ed in o il Wel l s , th e h y dr a te f o r m ed is tr ic a l c iu m
a l u m ina te h ex a h y dr a te Wh ic h is th e s ta b l e c o m p o u nd; in th is
c a s e, th er e is no dr o p in m ec h a nic a l s tr eng th .
F u r th er , th e h y dr a tes f o r m ed p r ec ip ita te in th e Wh o l e o f th e
p o r o s ity o f th e m a ter ia l , a nd no t o n th e g r a in s u r f a c e a s is th e
c a s e With Po r tl a nd c em ent. Th u s , th e p o r o s ity o f m a ter ia l s
o b ta ined With c a l c iu m a l u m ina te c em ents a r e r edu c ed, Wh ic h
g o es to Wa r ds im p r o v ing th e m ec h a nic a l s tr eng th a nd th e
du r a b il ity .
Th e inv entio n Wil l b e b etter u nder s to o d a nd its a dv a nta g es
Wil l b ec o m e c l ea r er f r o m th e f o l l o Wing ex a m p l es a nd tes ts
Wh ic h a r e in no Wa y l im iting a nd a r e il l u s tr a ted b y th e a c c o m
p a ny ing dr a Wing s , in Wh ic h :
F IG. 1 s h o Ws th e r h eo l o g ic a l c u r v es f o r th e f o r m u l a tio ns o f
th e ex a m p l es ;
F IGS. 2a a nd 2b s h o W ?l tr a tio n c u r v es a t a m b ient tem p er a
tu r e a nd a t 8 0C. f o r th e BEL A -Tem a l f o r m u l a tio n;
F IG. 3 s h o Ws th e r eta r ding a g ent c o nc entr a tio n a s a f u nc
tio n o f th e s etting tim e o f th e BEL A -Tem a l f o r m u l a tio n;
F IG. 4 s h o Ws th e c h a ng e in c o m p r es s iv e s tr eng th o f a
m a ter ia l s a m p l e a s a f u nc tio n o f tim e.
In th e ex a m p l es o f s l u r r y f o r m u l a tio ns o f th e inv entio n, th e
a l u m ino u s c em ents u s ed in th is inv entio n Wer e a s f o l l o Ws :
Sec a r 51 a nd Ter na l p r o du c ed b y L a f a r g e A l u m ina tes
( F r a nc e) .
Th e o x ide c o m p o s itio ns f o r Ter na l a nd Sec a r 51 a r e s h o Wn
in Ta b l e 1.
US 7, 540, 915 B2
3
TA BL E 1
Ox ide c o m p o s itio ns f o r c a l c iu m a l u m ina te c em ents
Ter na l Sec a r 51
Ox ide c o m p o s itio n A 1203 3 9. 3 52. 0
Ca O 3 5. 4 3 6 . 7
SiO2 4. 0 4. 3
F e2O3 + F eO 14. 6 1. 3
( a s a p er c enta g e with r es p ec t to th e to ta l Weig h t)
Th e m ea n dia m eter s o f th e a l u m ino u s c em ents u s ed wer e
a s f o l l o ws :
Sec a r 51: D50: 19 u m ( Dm ini: 0. 4 u m , Dm a x i: 16 0 u m )
s p ec i?c s u r f a c e a r ea : 23 m Z/ g ;
Ter na l : D50: 21 u m ( Dm ini: 0. 4 u m , Dm a X i: 18 2 u m )
s p ec i?c s u r f a c e a r ea : 23 8 m Z/ g .
Th e v a l u e D50 r ep r es ents th e p a r tic l e s ize b el o w wh ic h
50% o f th e p a r tic l es h a v e a dim ens io n o f l es s th a n th is D50
v a l u e.
Th e c o m p a c tnes s o f th e c em enting m a ter ia l s b a s ed o n a l u
m ino u s c em ents wa s o p tim ized b y c o m b ining th e f o l l o wing
c o m p o nents :
a Tem a l o r Sec a r 51 ty p e a l u m ino u s c em ent th e a l u m ina
c o ntent o f wh ic h is a t l ea s t 3 0%;
a m ic r o s il ic a with a g r a nu l o m etr y in th e r a ng e 0. 1 to 3 0 u m
( BET s p ec i?c s u r f a c e a r ea o f 18 m 2/ g ) wh er ein th e p er
c enta g e in th e c o m p o s itio n o f th e inv entio n is in th e
r a ng e 15% to 3 5% b y weig h t with r es p ec t to th e c em ent;
a n a dditio n o f m iner a l p a r tic l es with a g r a nu l o m etr y in th e
r a ng e 1 to 400 u m ( D50: 42 u m -s p ec i?c s u r f a c e
a r ea : 0. 46 m 2/ g ) th e p er c enta g e o f wh ic h in th e f o r m u
l a tio n is in th e r a ng e 10% to 3 5% b y weig h t with r es p ec t
to th e c em ent, with th e s u p p l em enta l c o nditio n th a t th is
p er c enta g e r em a ins l o wer th a n th e p er c enta g e o f m ic r o
s il ic a , to s a tis f y c o m p a c tio n o p tim iza tio n;
a h y dr o s o l u b l e p o l y m er a g ent to ?u idif y th e s l u r r y . Th e
p er c enta g e o f ?u idif y ing a g ent is in th e r a ng e 0. 2% to
3 . 0% with r es p ec t to th e a l u m ino u s c em ent. Th e h y dr o
s o l u b l e p o l y m er m a y b e eith er a p o l y na p th a l ene s u l p h o
na te o r a p o l y o x y eth y l ene p o l y c a r b o x y l a te;
a r eta r ding a g ent to c o ntr o l s etting f o r tem p er a tu r es o f
m o r e th a n 3 0C. ;
wa ter in a q u a ntity o f a t m o s t 40% with r es p ec t to th e
weig h t o f c em ent, a nd p r ef er a b l y l es s th a n 3 0%, in p a r
tic u l a r eq u a l to 27%.
Th e f o r m u l a tio n m a y a l s o c o nta in a s s o c ia tiv e p o l y m er s to
c o ntr o l a ny p r o b l em s with s ta b il ity o f th e s l u r r y ( i. e. a v o id th e
p h eno m eno n o f s edim enta tio n o f m iner a l p a r tic l es : c em ents ,
s il ic a , etc ) .
Th es e a s s o c ia tiv e p o l y m er s m a y b e a p o l y m er with h y dr o
p h il ic m o tif s ( Hy ) a nd h y dr o p h o b ic m o tif s ( Hb ) in a q u eo u s
s o l u tio n, th e h y dr o p h o b ic m o tif s ( Hb ) c o nta ining C1 to
C3 0a l ky l , a r y l o r a l ky l -a r y l g r o u p s , th e p o l y m er h a v ing th e
f o l l o wing s tr u c tu r e: -( Hb ) -( Hy ) -, in a r a ndo m dis tr ib u tio n, in
wh ic h :
Hy is o f th e f o r m :
R5
CH2C
Z1
in wh ic h R5 is H o r CH3 , a nd Z1 is COOH o r CON H2 o r
CON HR1SO3 o r CON HR"1, wh er e R"1 is CH3 ;
20
25
3 0
3 5
50
55
6 0
6 5
o r o f th e f o r m :
R5 R"5
CH2C CH2C
Z1 Z3
in wh ic h R5 is H o r CH3 , a nd Z1 is CON H2 o r
CON HR"1, R"1 is CH3 a nd in wh ic h R"5 is H o r CH3 ,
a nd Z3 is COOH o r CON HR1SO3 , in wh ic h R1 is
C3 H8 , o r C6 H5;
Hb is o f th e f o r m :
R'5
in wh ic h R'5 is H o r CH3 a nd Z2 is COOR7, COOR'l ,
CON R1R'1 o r CON R1R7, R7 b eing a no n io nic s u r f a c
ta nt c o ns titu ted b y a n a l ky l p o l y o x y eth y l enic c h a in, R1
is H o r a C1-C3 0 a l ky l , a r y l o r a l ky l -a r y l r a dic a l , a nd R'1
is a C1-C3 0 a l ky l , a r y l o r a l ky l -a r y l r a dic a l .
In a v a r ia tio n, th e p o l y m er m a y h a v e a m o l ec u l a r m a s s in
th e r a ng e 104 to 5>< 108 Da l to ns a nd with a h y dr o p h o b ic m o tif
Hb c o ntent in th e r a ng e 0. 5% to 6 0%.
Th e a s s o c ia tiv e p o l y m er m a y b e s el ec ted f r o m th e g r o u p
c o ns titu ted b y :
HMPA Ml : in wh ic h R5 is H a nd Z1 is CON H2, R'5: CH3 ,
Z2 is COOR'l , in wh ic h R'1IC9H19;
HMPA M2: in wh ic h R5 is H a nd Z1 is CON H2, R'SIH, Z2
is CON R'1R'1, in wh ic h R'1IC6 H13 ;
HMPA M3 : in wh ic h R5 is H a nd Z1 is CON H2, R"5: H, Z3
is COOH o r CON HR1SO3 , in wh ic h R1 is C3 H8
( A MPS) , R'SIH, Z2 is CON R'1R'1, in wh ic h
R'1IC6 H13 ;
S1: in wh ic h R5 is H a nd Z1 is CON H2, R'5: H a nd Z2 is
C6 H4SO3 H;
HB1: in wh ic h R5 is H, Z1 is COOH, R'5 is H a nd Z2 is
COOR'l , in wh ic h R'1IC4H9.
In p a r tic u l a r , th e p o l y m er deno ted HMPA Ml o r HMPA M2
o r HMPA M3 m a y h a v e a m o l ec u l a r m a s s in th e r a ng e 5>< 105
to 2>< 106 da l to ns a nd with a h y dr o p h o b e c o ntent ( Hb ) in th e
r a ng e 0. 5% to 3 %.
Th e p o l y m er S1, a c r y l a m ide ( Hy ) / s ty r ene s u l p h o na te ( Hb )
c o p o l y m er , wh ic h m a y o r m a y no t b e b r a nc h ed, a s des c r ib ed
a b o v e m a y h a v e a m o l a r r a tio o f a b o u t 50/ 50 a nd a m o l a r m a s s
in th e r a ng e 5>< 105 to 5>< 106 da l to ns . In th e c a s e in wh ic h it is
b r a nc h ed, it is deno ted S2. Th e b r a nc h ing a g ent u s ed in th is
c a s e m a y b e N , N '-m eth y l ene b is a c r y l a m ide, MBA .
Th e p o l y m er HB1, a c r y l a te ( Hy ) / b u ty l a c r y l a te ( Hb )
c o p o l y m er , in wh ic h R5 is H, Z1 is COOH, R'5 is H a nd Z2 is
COOR'l , in wh ic h R'1 is a C4 m o tif , m a y c o m p r is e a b o u t
8 0% o f a c r y l a te m o tif s , a nd h a v e a m o l ec u l a r m a s s in th e
r a ng e 104 to 5>< 104 da l to ns .
Th e f o l l o wing v a r io u s f o r m u l a tio ns wer e tes ted:
BEL A -Po r tl a nd G:
Po r tl a nd G c em ent: 100;
Sil ic a f u m e: 24;
Gr o u nd s a nd: 20;
F l u idif y ing a g ent: 0. 5 g dr y m a tter ;
BEL A -Sec a r 51:
Sec a r c em ent 51: 100;
Sil ic a f u m e: 24
US 7, 540, 915 B2
5
Gr o u nd s a nd: 20;
F l u idif y ing a g ent: 0. 5 g o f dr y m a tter
A s s o c ia tiv e p o l y m er : 0. 5 g o f dr y m a tter ;
BEL A -Tem a l :
Ter na l c em ent: 100;
Sil ic a f u m e: 24;
Gr o u nd s a nd: 20;
F l u idif y ing a g ent: 0. 5 g dr y m a tter ;
Tes t 1: Dis p er s io n
Dis p er s io n Wa s ev a l u a ted b y m ea s u r ing th e dens ity o f v a r i
o u s s ec tio ns o f a 20 c entim etr e h ig h c y l indr ic a l s a m p l e.
a ) BEL A -Sec a r 51 f o r m u l a tio n With o u t a s s o c ia tiv e p o l y
m er ( in g r a m s ) .
Th e dens ity o f a s ec tio n o f th e s a m p l e ta ken f r o m th e to p o f
th e c y l inder Wa s 2. 0 g / c m 3 , Wh il e a s ec tio n ta ken f r o m
th e b o tto m o f th e s a m p l e h a d a dens ity o f 2. 4 g / c m 3 .
b ) BEL A -Sec a r 51 ( With a s s o c ia tiv e p o l y m er ) .
Th e dens ity o f a s ec tio n o f th e s a m p l e ta ken f r o m th e to p o f
th e c y l inder Wa s 2. 25 g / c m 3 , Wh il e a s ec tio n ta ken f r o m
th e b o tto m o f th e s a m p l e h a d a dens ity o f 2. 23 g / c m 3 .
Th e a s s o c ia tiv e p o l y m er Wa s ef f ec tiv e ev en in s m a l l q u a n
tities , a s r eg a r ds c o ntr o l l ing th e dis p er s io n o f s o l ids in th e
s l u r r y .
Th e c o nc entr a tio n o f a s s o c ia tiv e p o l y m er Wa s a dj u s ted a s a
f u nc tio n o f th e r es p ec tiv e p r o p o r tio ns o f th e v a r io u s m iner a l
c o m p o u nds o f th e f o r m u l a tio n.
Tes t 2: Rh eo l o g ic a l Pr o p er ties
F IG. 1 s h o Ws th e th r ee Th eo l o g ic a l c u r v es f o r th e th r ee
f o r m u l a tio ns in th e ex a m p l es , With th e s h ea r r a te ( in s _l )
a l o ng th e a b s c is s a a nd th e s h ea r s tr es s ( in Pa s c a l s ) u p th e
o r dina te.
Th e m ea s u r em ents Wer e c a r r ied o u t in a Ha a ke ty p e v is c o
s im eter With g r o o v ed c o a x ia l c y l inder s .
Th e r h eo l o g ic a l p a r a m eter s o f h ig h p er f o r m a nc e c em ents
b a s ed o n Po r tl a nd c em ent ( c l a s s G) a nd a l u m ino u s c em ents
( Sec a r 51 a nd Ter na l ) a r e s h o Wn in th e f o l l o Wing ta b l e:
Vis c o s ity ( m Pa - s l ) F l o W th r es h o l d ( Pa )
BEL A -Po r tl a nd Cl a s s G 3 43 3 . 6
BEL A -Sec a r 51 148 0
BEL A -Ter na l 16 8 0
Tes t 3 : F il tr a tio n Pr o p er ties :
F IGS. 2a a nd 2b r es p ec tiv el y s h o W th e ?l tr a te ( in m il l il iter s
u p th e o r dina te) a s a f u nc tio n o f tim e ( in s ec o nds , a l o ng th e
a b s c is s a ) f o r a tem p er a tu r e o f 20C. a nd a tem p er a tu r e o f 8 0
C. in th e c a s e o f a BEL A -Ter na l f o r m u l a tio n th e ?u idif y ing
p o l y m er f o r Wh ic h Wa s p o l y na p h th a l ene s u l p h o na te ( f o r
ex a m p l e f r o m HA N DY Ch em ic a l , Ca na da ) .
Th e m ea s u r em ents Wer e m a de in s ta tic ?l tr a tio n m o de in a
Ba r o id ty p e HP/ HT c el l .
It Wa s s h o Wn th a t th e ?l tr a te a t 3 0 m inu tes f o r a BEL A
Tem a l a t a m b ient tem p er a tu r e Wa s 2. 75 m l , a nd a t 8 0C. , it
Wa s 53 m l .
By c o m p a r is o n, th e 3 0 m inu te ?l tr a te f o r BEL A -Po r tl a nd
G a t a m b ient tem p er a tu r e Wa s 12. 5 m l With th e s a m e ?u idi
f y ing p o l y m er .
Tes t 4: Pu m p a b il ity Tim e
Th e m ea s u r em ents Wer e m a de in a Ch a ndl er ty p e c o ns is
to m eter ( Mo del 8 240) .
20
25
3 0
3 5
40
45
50
55
6 0
6 5
6
Th e p u m p a b il ity tim es f o r th e v a r io u s f o r m u l a tio ns a t
a m b ient tem p er a tu r e a nd p r es s u r e a nd a t 8 0C. a nd 18 0 b a r
a r e g iv en in th e f o l l o Wing ta b l e:
T ( C. ) a nd P ( b a r ) BEL A -c l a s s G BEL A Sec a r 51 BEL A -Ter na l
20 5 25h 26 h 17 12h 3 3
8 0 18 0 1 h 50 49 m in 49 m in
It is p o s s ib l e to r eta r d th e s etting o f a l u m ino u s c em ents , in
p a r tic u l a r Wh en th e tem p er a tu r e is h ig h ( 8 0C. ) . To th is end,
a r eta r ding a dditiv e is u s ed, f o r ex a m p l e th e A L 8 10 r eta r ding
a g ent p r o du c ed b y Ch r y s o SA ( F r a nc e) . By a dj u s ting th e
c o nc entr a tio n o f A L 8 10 in th e c em ent s l u r r y , it is p o s s ib l e to
a dj u s t th e s etting tim e a t 8 0C. to b etWeen 49 m inu tes a nd 4
h 3 0.
F IG. 3 s h o Ws th e c u r v e o f p u m p a b il ity tim e ( u p th e o r di
na te, in m inu tes ) a s a f u nc tio n o f th e c o nc entr a tio n o f r eta r d
ing a g ent ( a s a p er c enta g e With r es p ec t to th e c em ent, a l o ng
th e a b s c is s a ) .
Tes t 5: Mec h a nic a l Pr o p er ties :
Th e tes ts Wer e c a r r ied o u t o n a c o nv entio na l c o m p r es s io n
r ig .
Th e c o m p r es s iv e s tr eng th f o r a BEL A -c l a s s G a t a m b ient
p r es s u r e a nd tem p er a tu r e Wa s in th e r a ng e 90 to 110 Mp a .
Th e c o m p r es s iv e s tr eng th f o r a BEL A -Sec a r 51 a t a m b ient
p r es s u r e a nd tem p er a tu r e Wa s in th e r a ng e 100 to 13 0 MPa
Th e c o m p r es s iv e s tr eng th f o r a BEL A -Tem a l a t a m b ient
p r es s u r e a nd tem p er a tu r e Wa s in th e r a ng e 90 to 110 MPa
It c a n b e s een th a t a l u m ino u s c em ents f o r m ed f r o m th e
f o r m u l a tio ns o f th e inv entio n c o u l d p r o du c e h ig h m ec h a nic a l
s tr eng th m a ter ia l s .
F IG. 4 s h o Ws th e c h a ng e With tim e ( in da y s ) o f th e c o m
p r es s iv e s tr eng th ( in MPa ) o f a BEL A -Tem a l c em ent s a m p l e
a t 20C. ( c u r v e A ) a nd a t 8 0C. ( c u r v e B) .
It c a n b e s een th a t th e BEL A -Ter na l , Wh ic h a g es a t tem
p er a tu r e, do es no t ex h ib it a r edu c tio n in c o m p r es s iv e
s tr eng th .
Tes t 6 : Res is ta nc e to A c idic Media :
Th e BEL A -Tem a l a nd BEL A -Sec a r 51 h a d g o o d du r a b il
ity in c o nta c t With a g g r es s iv e ?u ids . A f ter a g eing f o r 28 da y s
in a n a c idic s o l u tio n a t a p H o f 1, th e c o m p r es s iv e s tr eng th o f
a BEL A -Tem a l s a m p l e Wa s 95 Mp a , Wh il e th e c o m p r es s iv e
s tr eng th o f a BEL A -Tem a l s a m p l e im m er s ed in Wa ter f o r th e
s a m e p er io d Wa s 98 MPa . Th e dr o p in m ec h a nic a l s tr eng th
Wa s th u s o nl y 3 % f o r th is m a ter ia l , Wh en it is a g ed in a n a c idic
?u id.
Th e c o m p r es s iv e s tr eng th o f a c o nv entio na l Ter na l c em ent
a t 28 da y s a g ed in a n a c id s o l u tio n a t a p H o f 1 is 6 7 MPa ,
Wh il e it is 100 MPa f o r th e s a m e c em ent a g ed in Wa ter . Th e
dr o p in m ec h a nic a l s tr eng th f o r th is c em ent in c o nta c t With a n
a g g r es s iv e ?u id is m o r e th a n 3 0%.
Th e el a s tic m o du l u s o f BEL A -Ter na l a g ed f o r 70 da y s in a n
a c idic s o l u tio n a t a p H o f 1 dec r ea s ed b y 15% to 20% With
r es p ec t to th e s a m e m a ter ia l a g ed in a no n a g g r es s iv e m ediu m .
Th e el a s tic m o du l u s o f BEL A -Po r tl a nd a g ed f o r 70 da y s in a n
a c idic s o l u tio n a t a p H o f 1 dec r ea s ed b y 3 0% With r es p ec t to
th e s a m e m a ter ia l a g ed in Wa ter .
Th u s , it is c l ea r th a t f o r m u l a tio ns o f th e inv entio n o f th e
BEL A -Tem a l a nd BEL A -Sec a r 51 ty p e c a n im p r o v e th e
du r a b il ity o f c em enting m a ter ia l s , in p a r tic u l a r in a n a c idic
m ediu m .
F u r th er , o p tim iZa tio n o f c o m p a c tnes s c o m b ined With a
r edu c tio n in p o r o s ity r es u l t in im p r o v ed r es is ta nc e o f th e
US 7, 540, 915 B2
7
du r a b il ity o f th e m a ter ia l b ec a u s e o f th e g o o d r es is ta nc e o f
a l u m ino u s c em ents to a g g r es s iv e a g ents a nd th e l o W p enetr a
tio n o f th es e a g ents du e to l o W p er m ea b il ity .
Th e inv entio n c l a im ed is :
1. A c em enting s l u r r y c o m p r is ing :
a n a l u m ino u s c em ent th e a l u m ina c o ntent o f Wh ic h is a t
l ea s t 3 0%;
a m ic r o s il ic a With a g r a nu l o m etr y in th e r a ng e 0. 1 to 20 p m
th e p er c enta g e o f Wh ic h is l es s th a n 3 5% b y Weig h t With
r es p ec t to th e Weig h t o f c em ent;
m iner a l p a r tic l es With a g r a nu l o m etr y in th e r a ng e 0. 5 to
500 p m th e p er c enta g e o f Wh ic h is l es s th a n 3 5% b y
Weig h t With r es p ec t to th e c em ent, th e p er c enta g e o f s a id
p a r tic l es r em a ining b el o W th e p er c enta g e o f s a id m ic r o
s il ic a ;
a h y dr o s o l u b l e ?u idif y ing a g ent th e p er c enta g e o f Wh ic h is
in th e r a ng e 0. 2% to 3 % With r es p ec t to th e Weig h t o f
c em ent;
a r eta r ding a g ent to c o ntr o l th e s etting tim e o f th e s l u r r y ;
Wa ter in a q u a ntity o f a t m o s t 40% With r es p ec t to th e
c em ent.
2. A s l u r r y a c c o r ding to c l a im 1, in Wh ic h th e h y dr o s o l u b l e
?u idif y ing a g ent is a t l ea s t o ne m em b er s el ec ted f r o m th e
g r o u p c o ns is ting o f a p o l y na p th a l ene s u l p h o na te a nd a
p o l y x y eth y l ene p o l y c a r b o x y l a te.
3 . A s l u r r y a c c o r ding to c l a im 1, in Wh ic h th e Wa ter c o ntent
is b el o W 3 0%.
4. A s l u r r y a c c o r ding to c l a im 1, f u r th er c o m p r is ing a
q u a ntity , in a q u eo u s s o l u tio n, o f a t l ea s t o ne a s s o c ia tiv e p o l y
20
25
3 0
8
m er c o nta ining h y dr o p h il ic m o tif s Hy a nd h y dr o p h o b ic
m o tif s Hb c o nta ining C1 to C3 0 a l ky l , a r y l o r a l ky l -a r y l
g r o u p s .
5. A s l u r r y a c c o r ding to c l a im 4, in Wh ic h s a id p o l y m er h a s
a m o l ec u l a r m a s s in th e r a ng e 104 to 5 >< 106 da l to ns a nd a
nu m b er o f h y dr o p h o b ic m o tif s Hb in th e r a ng e 0. 5% to 6 0%.
6 . A s l u r r y a c c o r ding to c l a im 4, c o m p r is ing 0. 5% o f a s s o
c ia tiv e p o l y m er .
7. A s l u r r y a c c o r ding to c l a im 1, c o m p r is ing ( With r es p ec t
to th e Weig h t o f c em ent) :
24% o f m ic r o s il ic a ;
20% o f m iner a l p a r tic l es ;
0. 5% o f ?u idif y ing p o l y m er .
8 . A m eth o d f o r u s ing a s l u r r y , c o m p r is ing c em enting a
Wel l in a n a c idic env ir o nm ent With th e s l u r r y a c c o r ding to
c l a im 1.
9. Th e m eth o d a c c o r ding to c l a im 8 , Wh er ein th e c em enting
p r o du c es a c em ent With a c o m p r es s iv e s tr eng th o f a t l ea s t 90
MPa .
10. Th e m eth o d a c c o r ding to c l a im 8 , Wh er ein th e c em ent
ing p r o du c es a c em ent With a c o m p r es s iv e s tr eng th o f a t l ea s t
100 MPa .
11. A s l u r r y a c c o r ding to c l a im 1, in Wh ic h th e Wa ter
c o ntent is 27%.
12. A s l u r r y a c c o r ding to c l a im 1, in Wh ic h a c em ent p r o
du c ed f r o m th e s l u r r y h a s a c o m p r es s iv e s tr eng th o f a t l ea s t 90
MPa .
13 . A s l u r r y a c c o r ding to c l a im 1, in Wh ic h a c em ent p r o
du c ed f r o m th e s l u r r y h a s a c o m p r es s iv e s tr eng th o f a t l ea s t
100 MPa .