SoobtYd -- Endfmefs

SPE 28773

New Cement Additive Improves Slurry Properties and Saves Cost

Robert Pollard, Total Indonesie, and Jeff Hibbeler,’ Gino DiLullo,* E.A. Shotton,*
SJ Services Co. (S) Pte. Ltd.
“SPE Members

C@wbht 1S94,SadatYot Patrobum EIWIlneam, inc.

This -r was praparad for pr~ntatirm at ttw SPE Ada Pmlfic Oil & San QWarewe bald in Malbwrma, Australia, 7-10 Novambaf 19S4.

Thin papar was sabctad for praaantatbn by an SPE Program (bmmittaa foibwir!g raviaw ot inbmaticm mntainad in an abatmct UIbmiltad by tha author(s). Cmtanta oi tha papar,
aaprasanted, havanotbaan rawawad by tha Smbty o! Patmkum Englnaam and ●m aut+act to mfr.ctbm by tha UdhW(a). TIM mtitil, an PMMnkd. dma ~ Mmaaaliiy raflaa
my ~~ ~ tti SOCW ~ petti~m EWiIWWS, ~ m. w moM~. - PMMm.d Ms= ~ne$ uo au~ @ M-n * by Ed-l xmm ~ t~ H
ti~m~m. tibbnmqk~tom ~dwmti~—.l~ mayrmtbampiad.llw abatmctahould mntalnmwkufwa~
d vAIara and by whom the papar is praaamad. Writs UbMam SPE, P.O. Sox SSSSS9, Rkhardaon. ~ 7EOW49390 U.S.A. Tebx 1S3S45 SPEUT.

STRAC T INTRODUCTION
A new cememt additive has been developed which Prior totkhtmducO “onof CMAS, lead slurries wem
impnms slurry perfommce and leduces cost. ‘me tightened using either Iiquid micm-aika sodium
additive is a vitrified aggregateof calcium-magmsium silicate, bentonite or various combinations. Slumies
alUminosilkam with potential CementitiousIeaclMty, with liquid micxu silica have high compnxsive
heresfter abbreviated W. CMAS has been used Srength but SISOxeladvely high cch% meanwhile
succesfuUy on oil snd gas wells throughout slurries using bentonite am economicalbut have low
Indonesia compressiveatnmgth Slunies extendedwith sodium
silicate are somewhatrestricted by temperature, thus
Thepurpose ofthispaper istoiUustrate tbetedmical
mbancementa and cost effectivemss of slurries - Ck+3ign
cumbersome. Combinations of these
additiveshave not producedsny synergism.
incorporatingCMAs. Laborstory data is pmsenkd
and woddng meckdams aredefined to bighligllt
Wltb tkse technical and economic issues in minda
CMAS’s positive effect q cmnfnessive stxmgtb
fluid loss control, fme water COIIIOLgas migration compmknsive study was initiated with the goal of
cnntml, nAstance to stnmgth n%qpsion and fhdingaw additive thatcouklexten dslurrksand
aggremive fluids. Ftiy, augmentperformance. Gut of the group of materiais
case studies aud an
economic analysis are psented to Showtkcost teste&CMAS~dtiMoveMSurrY and
savings for actualwell applications. cenmt strength pmperries. ‘he most impmtant test
consickralions wenx compatibility with existing
cement and addithm woddng tempemture range,
rheologyand compressivestnmgthdevelopment.

W, beii a powder, is dry Mendedwith cement

at cmcenWions of10%to200%bywei@t of
cement (bwoc) depemhg on the application. For
densides fxom 1.40 to 1.55 specific gravity (S.G.),
60%tollo% c!MAs is ideaL CMAscanilkbe
used onmator densifiedslurries to impmve stabiity,
fluid loss, free water, and compnxisiveWren@h.

Refenmceaand illustrationsat ed of paper.

319
2 NEW CEMENT ADDITIVEIMPROVESSLURRY PROPERTIES AND SAVES COST SPE 28773

ION tiwrawmaterial isde-watenxl andgmundtoa Bk

Fimmxs of 4,000 -4,500 square centimeter per
TIMinitial hydrationof cementis yet to be completely gram. Ourlaboratoly mtinghasshowntha tfinen=
UndmtmL however iteanbe simply qmsentdby oftigrind hasasignificant infknce onalurry
tk Mlowiq$ dMO@Y,* W- contm~ fluid loss control and
other alumyproperties.
CaS04 + A + CS + H+ C-S-H+C-SA-H+(CaOH)2

(Gypsum + Alumina@ + calcium silicates + water ON

+CalchunS ilicateHydrate+Cakium moIMSuMo
AluminateHydrate+ CalciumHydfoxkk) CMAS hydration takes place immediately after
mixing with water. A semi-pemmable wating is
Tk hydration reaction nxadts in a crystal formed on particle surfaces, inhibiting water
&Vd~(Xlt -S whexeby C-S-Hfibrih ~W ~ penetmdon and fiuther dissolution Calcium
bran&s out of b cement@ioks whik kXag03@ hydroxide, a by product of hydmdng ccm~
plates of calcium hydroxide(Ponlamiite) and medles accelemtes tk dissolution of Si and Al ions by
of Ettringite are _ltated a3UO~ tk cem- breaking tbe Si-Oand Al-O bonds in the-
particles. In the eady stages of hydratkah gypsum surface atructm. When * solution becomes over
reacts with C3Atotbrm acoatingof Mringite which ~ @pitation of low volubility calaum
temporarily inhibits the hydration of fast matting silicate hydrate (hmafter abbreviated C-S-H*) and
CY% meanwhilea semi-permeablecoating of C-S-H ~ hydrates occurs. ‘Ibis complex pmceas
geL -g like a check valve, temporally inhibits in altemadng stages thmuglmut lhe
hydrationof the two main soumes of eernentstrcn@L hydration process. Below is a simplifiedsummary of
MM W*) and C3S (Al@. After a cbm3ant the two step Nncdon.
period hydration will proceed to completkm
PI@ucing C-S-H (CS 3’atiO, 3:2), C-SA-H, CS+H+ C-S-H+(CaOH)2
Portlandite and small amounts of Unhydratedcement.
Aslongas themiswater available, tk cement (CaOH)2+
CMAS~ C-S-H2
+ Otherhydrates
particles and their byproducts will mntinue reset to
fonnasolidmass. Thestreqth snddurabiUtyofl& C-S-H2diffem in many ways fmm C-S-H produced
Cementpasteandmdtings etproductdependal argely bypmtlandc ementasi thasahigkalkall content
on the fonowingIelatedpropatk and mom impo~ a lower CS ratio (0.7:1). Mao,
themorphologyof hydmtingwis anincqn=
1. Waterto cementratio. maas&velopmalt asopposed to fibrilim&@ing.
rn terms of physical prqxxties, C-S-H* has higher
2. Porosity of hard set cement. _ d is mom - tM C-S-H gek l&@
bypmtblndcement ‘n3isiadueto:
3. Howthepoms are Memme@W ie. to what
degreeis penneabiity developed. 1. C-S-H*, having more Si- than C-S-H, has a
different atomic bonding which is stronger.
Becauae fluids andgascau flowtbmugh the pore This resultsm higher conqxessive atren@.
channeklhepcmneability oftkmatrix is* decisive
factor influeming the durabilityof the set cement. 2. ~ 3USSSdevdq!mmt of C-S-H*
nxuhsinl essvoids pacethanthellbril
~ IPowthof C-S-H.
. Other major MYemnmsbetweencMAsand Portland
mm&hmng ofcMAsisahnihwto thatof
Mtlandcement ‘lhatis, acombiinofeathen cemcnthydration aretiming andkinetics. Compared
materials are melted together at extremely high to Po-cernen4 cMAs is latently hydmulic,
tempemtums (>2m “F) and cooled rapidly, ibfmirlg _ mo~ active with ~ by temperature
a new multkmide vitreous material. After cooling, mixwateralkaUni~ andadfateconte@and

320
SPE28773 R. Pollard, J. Hibbeler, G. DiLullo, B. Shotton
decmaes in surface tension. Also, CMAS hydration
Pmducea onlyone fbuthof thekatgenemted by
Portland cement hydration. This miuces thermal
atlesaon theaunuhlsdllringt heaettingperiod! thus
nxiucingthe risk of creadng a micm-armulus.
~~S 1 through 6 are S.E.M. photographs showing
tk various stages of CMAS hydration. Note the
.
ddkmces in hydrationbetweenPonlarKIcementand
CMAS. lheaediffexences arepdmarilydue toa
differencein mineralogy.A comparisonof minemlogy
shows that CMAS has a lower C:S ratio (1.1 versus
3.0). This provides a second means of reducing
cakium hydroxideby simply reducingthe amount of
CaO availableto cause its pmipitation. See Table 1.
U&4mhwm
A special accelerator was &veloped in conjunction
with CMAS to provide nxwmnablethickening times
and eady compmsive strength. lhe material is a
liquid blend of alkalinesalts and surf- Imeafter
abtxeviated BASS. BASS speeds tk hydration
pmcesa of CMAS through a combinationof chemical
snd physical interactions. ‘llE most rmtable are the
formation of meta-stable stable Calaum-Aluminum
gel which favom the precipitation of Ethingite at an
.-2.. A.... -Cl... —G—.-A A. Ediictim of I@ri?zkm
WlrlyWlgc LxllydLcllluuUUuLUG
enelgy requhed to activateOxkks and silicates.
Upon wetdng, cement and CMAS particles become
covered by a gelatinous layer. These layers a
L—..1.-.L-
ulUILGLl~LCI~. “l..& -.A...I U1UllW
~1 L~llUU .s &.... k.. E& &k 4A” “
UYlW@jlLG llu+
that gmw rapidly, intemnnedng the hydration
crystals. (see Flglue 3). m gelatinous matedal
created by BASSalso extenda slurries andklps
control iiee water.
While theslurryisaliquid CMAsparticles intemlix
with cement particles producing a lubdcating action
that combined with a POE volume mductiom
impmvcs Siurry dispersion and tmhanws fl-uidioss
contmL Also, most polymer fluid loss addidves am
negatively afkcted by free Ca+ cations. Aa CMAS
consumesCa+cations during its hydration it helps to
stabik tk polymer’sviscosity.(SeeFigure 7).
321
3
MdQgY
CMAS slurries exhibit better dxology (ie. lower
plasticviscosityand yield point) than those previously
used, whichmaks them suitable for long casing jobs
Wheledynamicdownholepessums arecliticaltothe
Successfdplacementof cement.
CMAS is a natural retarder since its hydmtion
process isslowerthan thatofportland cement. TlliS
combined with tbe positive strength Progression
effect makes CMAS slurdes ideal for high
temperaturejobs.
Free Water Como(
CMAS absorbs mont water than Portiand cement
dudng its wetting and hydration stages. By doing so
it helps to “tie up” fm water that may be available
within a slurry. Mso, because cMAscIeatesan
additionalbmnchingand interlockinggel lattice (c-s-
H2)within the slurry POE structure segregationand
fluidmovementwithin@?cementmti am reduced
msive StrtZ@I
Approximately h pounds of PortlaIKliteis produced
during the hydration of one cubic foot of cement.
-*Iow$-
AUlualuw k un mnk
lo “— anlmhlt= material th~ ~S
w....” . . . .. . not
contribute to cement Coxnpmsiveahength and can be
leacki out by downhole fluids. The compressive
atren@hofcement cOntah@ CMAS-is better than
conventionalPortlandcementbecauseOfi
1. The nxhwdon of calcium hydroxide and a
propollional imxease of the insoluble C-S-H
m.
2. FW particles of CMAS produce tighter
z~~~= . tk iIltelWCeSof the larger
‘Ikse two medmiams induce the finalgmwth
plUdUCt to intedock fidy thereby incmsing
compmsive atmgth. ’fhiseffec tcanbeseen when
comparingaCMASalurry to aslurry extmled with
bentonite. At 136 T, a 1.55 S.G. slurry with 65%
CM* h- a stren@ of 1,000 psi &—.p&ti ‘A400
psi foraslurry extmded with bentonite. Also note
that compmsive atnmgthinmaaesas the
comntmdon of CMAS immmses.(See Figwes 8 and
9).
4 NEW mMENT ADDITIVEIMPROVES SLURRY PROPERTIES AND SAVES COST
. .. . _
(h-on control
Slurries ‘mntdning mom than 50% CMAS, and a
viscoelastic, fi forming additive (eg. PVAP, PM)
produce gas tight slurries and cements. CMAs
reduces porosity, providing ad&d structural support
for the film forming additive, thus reducing
deformationand breaking under differentialpmssme.
Redumdpomsity alsodecmses the size oftk
natural matrix capillaries in the set ceme@ thtmby
incmsing the pressme losses applied to a potentially
mobiie gas. Ftiy, by nducing pemwability,
CMAS creates a cementmWix whichresists gas flow
by maldngthe path of movementmom disjointed.
Retr-,on Control
Above 230 “P the calcium rich C-S-H gel partially
transforms to tdph dkxdciumsilicate hydrate (@~)
which hasaweak pomusstrucme. l%is
transformation, commonly known as strength
IIXmglessim increases cement matrix porosity and
permeabilitytheseby redwing shength. An increase
in permeabilitym~ zonalisolation.
Unlikethe C-S-H Ibxmedby Portlami ceme@ C-S-H2
-. . . .
ibnneti fmm uwm nydradon has a high Si content
which makes it less soluble aud mctive. Long term
compressivestmgth testing indicatesthat silica flour
isnotnecesssly attemperatures upto 260 Twkn
using 65% CMAS or mom.
. . .
e to Corroswe a~ve FIM&
Downhole waters retaining sulfate, particularly
sodium sulfate, Sre very &trimezltal to set cement.
Sulfate IWCWwith calcium hydroxide and CA to
form volumetrically larger crystals of calcium
aulfoaluminate. These crystals IW@IEmm pm
space than the set cement can provide, m cracking
and deterioration occurs. Sulfate attack is most
pronouncedat temperanues iiorn 80 to 120“P.
CMAs PaItislly replaces CA and Ieacts with Calcium
hydroxide befo~ sulfate water can contact tk set
cemenGthmby reducing th mactams _ fir
calcium sulfoaluminate fonnadon. Also, CMAs
cement physically Ilx&ts ti encroachment of
aggressivefluids by imparting very low peIIu@ility
on the final set material (< 0.001 red.). See Tables 3
and4forasummary ofacidaml suUhtetesting.
SPE 28773
n A “m .- mm”
‘nmsfar, cMAshas beenusedin the’Itlmlgaa field
offshoreof East Kalimantan and the Ogan Komering
Block in South Sumatra. ‘fbnu is a large, shallow-
water field that stmtcks across the Mahakam river
delta mme 60 kilometem. zones of interest ale
sandstones at depths of 2,800 to 4,200 meters. TIE
Ogan KomeringBlock is a developmentoil field that
producesfrom intends of 1,500to 1,800meters.
. .
Convea&uuzlSlumes - Tunu
Lead slurks in the llmu field have been tailonxl for
specificneeds. A low bottom hole pressure tolerance
- . -::
in the i7-lfz and i2-ii40pen tile secdons requires
a 1.40 S.G. and 1.55 S.G. slurry mspecdvely.
Slurries across these sections must have good fluid
loss control because several permeable zones are
emounted. Intkpas%losses haveoccmmddwing
these ceuleutationsduetothe highviscosity andgel
strength of pvious slurries. Slunk with CMAS
have relatively low gel stmgths, thus are peferred
for &se cementations. Severaljobs have been &m
using ihe slurries in Table 2 without any losses. TsiI
.*.-J _. .--:__
slurrles mlllg CM’L%Siwe - proved ● @ be
economical snd teclmically superior to previous
Shlrries.
For these wells all cementationswen perfmmedusing
allO%CMAS and Pwtlamicemen tblend, Casings
fix the typical well arq 13-3/8”casing at 150 metem,
9-5/8” csaing at 1,000meters, and7° casing at 1,800
meters. Temperaturesrauge from 120 to 220 T. See
Table 2fbrtkslurry dekgnusedontk7° casing.
lbisslurry qlaceda more expensive design using
LMS for compressive strength and borx?ing
enkwerntxlt.
ECONO~C ANALYSU
‘W averagecost savings using the Tunu CMAS lead
slurries has beeIL$US 3.95 snd $US 1.40 per cubic
foot of slurry for tiw 13-3/8”and 9-5/8” mpectively.
See F@melOfO racostco mparisonoftk old and
H slurries. FIguma 11 and 12 show the mklitive
cost breakdown of tk old and new 13-3/8” lead
slurIies.
SPE 28773 R. Pollad, J. Hibbeler, G. DiLullo, B. Shotton 5

The average cost savings in the Ogsn Komeringfield

has been $US 5,700 per welLas cementconsumption
has been reduced by51%and LMS has been 1. Sabines, J.M. Tinsley and D.L. Sutton :
“Transition time of Cement Shmies Betweenthe
Fklhi state
e- am aP*
SF-I $x% cmdG
Q- 09Q<
. UIu >AU.J,
10CMl
./.”.
,

C!z N 2 G. DiLuUoand J. Tan : “An Evaluation of Gas

Control Additives”, OSEA 92167, pmented at
CMAS provides a simple cost effemive means to GilhhomSouthEast Asia Conference,1992.
extend siurrks.Cemeniing
costs have bem reduced
by as much as $US 13,500 per well, Case studies 3. J.C. Hibbeler, G. DiLullo and M. Thay : “Cost-
!-me proven *. c@ eff@km?as and technical Effective Gas Control: A Case Study of
enhancementsof CMAS sluny designs. Surfactsnt Cement”, SPE 25323, presented at
SPE Asia PacMc Oil W Gas Conference,1993.
CMAS and Po- cemem have a synmgkdc
&tiOI@lip. CMAS hydrates by matting with the 4. J.J. Fery and J. Romieu : “Impmved Gas
undeakd byproduct of -eat - calcium hydroxide, Migradon Control in a New Oil Well Cement”,
thus improving a varietyof slurry properties. SPE 17926,1988.

Fluid loss, fke water, compressiveatreng@ atnmgth 5. ASTM Stan@@ Designation C 989-82,
mtmgression and gas migmtion control properties of February 1983.
slurries comining CMASare allimpmved by the
chemical and physical Ieactions between CMAs and 6. F.D. Patchen : ‘‘Reactions and Properties of
Portlandcement Silica-Pcnthnd Cement Mixhues Cured at
Elevated Temperatures”, Trans., AIME (1960),
A new accelerator has been developedwhich speeds 281-87.
up tk hydradon of CMAS at low temperatuma. ‘IIM
workingrauge of the system is 70 to 350+”F. 7. D.D. Double and A. Hellawell : “The
Solidification of Cement”, scientific American
(Jtiy 1977)237, No. 1,82-90.

C3A = ‘hi Calcium Aluminate

C@ = Di Calciumsilicate
C& = Tri calcium silicate
CMAs= Calcium- MagnesiumAluminosilicate
BASS = Blend of AlkWne Salts and Surfactant
PVAP = Copolymerof Poly Viii Alcohol
LMS = Liquid Micro Sica
W= Gallonsper sack of cement
bwow = By weightof mix water
bwoc= By weight of cement(sUCMAS
concentrationsam bwoc)

The authors would like tothank b managementof

Total hxlonesie and BJ Services for permission to
publish this jqwr.

323
6 NEW CEMENT ADDITIVEIMPROVESSLURRY PROPERTIES AND SAVES COST SPE 28773

Fig. 1. Notethe diffenmcein hydrstion moqhology Fig. 4. ‘l%ephoto above was taken 105 minutes
snd timing. The cementhydrates fsster and in fibxiis into hydration. Note the advanced stages of C-S-H
whilethe CMAS grows slowly by mass development. gel fibrils snd plSStiCjymvth of C-S-H2,which ~
(Time-15min., 2,400X) the voids behveencementgrains.(2,400M

. .
I

Fig. 5. After 200 minutes of hydration, CMAS

growrh hss spti tidging pom threats and
intemmmecbg cementparticles.(2,400X)

fig. 3. Note the “web-like” reaction products of Fig. 6. h @iJN into hydratim the System k
BASS; at bottom and left-hand side of photo. (’llme extremelylow porosity.(7,000X)
15min., 5,0(M)X)

324
SPE 28773 R. Pollard, J. Hibbeler,G. DiLullo, B. Shotton 7

Table 4. A comparison of 48 hour compressive

stnm@hshowstim cOmdning CMAS hasa
higher Xeskan@ to sulfatewater. ~difkmnm”
stmngthbetwmtimmmh~ :
expostue time imeaaes. (Temp. lM ~$ dq
density 1.90 S.G, cuting time 24 ho-m, sidffa
exposuretime 24 bus).
Table 1. A comparisonof oxide mineral composition
shows that tk C.s ratio of CMAs approaches 1:1,
Efhctof CMAS%a’IFiIML-
Which tends tostabilize thesltlrryat high
temperaturesby making it less xeactive.

%clMs@mO)
LAN (%bwoc) o 0 0
.
DWersant(m) o 0.05 0.12
Gel(%bwoc) 4 Fig. 7. Fmm the graph, We that as CMAS
BASS(gps) 0.50 0 0 wncemadon inmases, fluid 10SS~S. Data
CaCIZ(%bwoc) 0.5 0 0 was taken at 150 “F with a 1.90 S.G. slurry
.
Demsity(SG) 1.40 1.55 1.90
contain@ 3% bwow PVAP + Dispemant.
BHST~ 136 200 220
BHCI’~ 103 150 160
Fluidhas 186 190 94 MBotof cMAs%alcmlp.stlul@l
(cc /30 Inin)
Freewater (%)
Comp.strength
0.50
w
TrWe
120
T=
3,350
I
I
Pv-Yp 14-9 9-6 89-14
. [ ~
Cp- iiilw)

Table 2. A summary of CMAS properties for case

study slurries shows high compmsive mengths, low
yieldpoints andgoodfiuidloss contmL
Fig. 8. Incn?asing the concdmdon of ( VfAs.
imeases compmsske stmrtgth. From 50 to 100%&
slopeishigh(l:l), whilealwve 100%the slope of the
15% HCL M% 16%
line decnmes. Critical conwntmtion for maximum
I I
28% HCL 35% 26%
@lengthbenefit varies, depding mairdy on slurry
density. (TemP.200 “F,Slurry Density 1.55 S.G.)
Table 3. Solubiity tests on co= show that cement
~ CMAShave higher acid resistance.

325
8 NEW CEMENT ADDITIVEIMPROVES SLURRY PROPERTIES AND SAVES COST SPE 28773

Whctofnllloon ~stm

0.S124 102030
lhw(~

Fig. 9. Astimekreases compressive ahength Rg. 12. A cost breakdownof the CMAS 13-3/8”
incnmses, with most of the strength generatedin the lead sluny showsa lower total coat and more even
fimt 4 days. The solid line is a 65% CMAS slurry, distributionof additivecost
the dotted k is a 2.5% bentonite slurry, both 1.55
S.G. (Temp. 200 “F)

Fig. 13. ‘l’he map above shows IWman@n and

Fig. 10. A cost comparisonof CMAS slurriesvemus Sum- tk locations whm case study field wmk
previouslead slurriesshows a significantsavings with has beenperformed.
the new system.

old Systun
(cast
.---- —- ——.—- ---- . Slnluclm.1
Blmlkdawn - . -. .---...,

\-l lW4cc2kakx

Fig. 11. A cost bmkdown of tk old 13-3/8” lead

tiller slurry nmals that 70% of the cost of the slurry
is fhm LMS.

326