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PORTLAND CEMENT
Definition:
A heteregeneous mixture of calcareous and
arcillaceous or other silica, alumina and iron
bearing materials, burning them a clinkering
temperature (1500^C) and grinding the resulting
clinker.
Portland Cement is a hydraulic cement. Such
cements set and develop compressive strength as
a result of a hydration process
2 Cement Chemistry
Cement Materials & Processing of
RAW MATERIALS
Cement :
CEMENT CLINKER
I Up to 200 Evaporation
II 200 to 800 Preheating
III 800 to 1100 Dehydroxylation
IV 1100 to 1300 Exothermic Reactions
V 1300 to 1500 Sintering
VI 1500 to 1250 Cooling
6 Cement Chemistry
Cooling Process
7 Cement Chemistry
Cooling Process
Cooling Rate: Fast (18-20oC/min)
C3A and C4AF remains in glassy phase
C3S and C2S remain highly ordered
Free magnesia remain in glassy phase
Result: More hydraulically active with relatively small
particle size
Less required energy during grinding stage
Lower early strength development (3-7 days)
Higher long term strength (28 days)
More sulphates resistance. Free MgO is less active
8 Cement Chemistry
UNSOUNDNESS IS LESS LIKELY
Cooling Effects
Cooling Rates and Effects
The quality of the clinker and finished cement
depends on rate of cooling
9 Cement Chemistry
Cement Clinker Grain Structure
C4AF: Tetracalcium
C3A: Tricalcium Aluminoferrite
Aluminate 3CaO.Al2O3 4CaO. .Al2O3 .Fe2O3
C3S: Major Component
C2S: Second most
abundant, but very slow
reaction
C3A: Lowest
concentration, hydrates
rapidly C S: Tricalcium Silicate
3 C2S: Dicalcium Silicate
3CaO.SiO2 2CaO.SiO2
C4AF: Interstitial phase,
highly reactive
10 Cement Chemistry
Grinding & Storage Operations
a. Flow diagram of the grinding and storage process:
11 Cement Chemistry
EQUIVALENT SPHERICAL DIAMETER, mm
Effects Manufacturing Process
Steps on Cement Properties
PROPORTIONING OF RAW MATERIALS
12 Cement Chemistry
Effects Manufacturing Process
Steps on Cement Properties
COOLING PROCESS
13 Cement Chemistry
Effects Manufacturing Process
Steps on Cement Properties
GRINDING PROCESS AND GYPSUM ADDITION
14 Cement Chemistry
Effects of Major Clinker
Components
SILICATE PHASE:
C3S, TRICALCIUM SILICATE
Major component in cement (formed from CaO and SiO2)
Hydrates more rapidly than C2S (control setting time)
Contributes to all stages of strength development (esp. early)
C2S, DICALCIUM SILICATE
Formed from CaO and SiO2
Hydrates very slowly with lowest heat of hydration
Affects long term compressive strength
15 Cement Chemistry
Effects of Major Clinker
Components
ALUMINATE PHASE:
C3A, TRICALCIUM ALUMINATE
Formed from CaO and Al2O3
Hydrates rapidly and produces highest heat of hydration
Plays an important role in:
Early strength development
Rehological behavior of slurry
Controlling setting and thickening time
Hydrated C3A is readily attached by sulphate
C4AF, TETRACALCIUM ALUMINOFERRITE
Formed from CaO, Al2O3, and Fe2O3
Gives color to cement
Little effect on set properties
Produces low heat of hydration
16 Cement Chemistry
Hydration of Portland Cement
I II III IV V
60
M.T.
Rate of Hydration
50
40
T.T.
30
20
10
Hydration
Stages
20 Cement Chemistry
C3A AND C4AF Hydration
EFFECT OF GYPSUM ADDITION ON HYDRATION RATE:
WITHOUT GYPSUM
2C3A + 27H C2AH8 + C4AH19
C2AH8 + C4AH19 2C3AH6 + 15H FLASH SET
WITH GYPSUM
2C3A + 3CSH2 + 26H C3A + 3CS + 32H
C3A + Gypsum + Water Ettringite
21 Cement Chemistry
Hydration of Portland Cement
PRE-INDUCTION PERIOD
Pre-induction period lasts 30 sec - 4 mins (just after cement mixing)
Highly exothermic reaction
Initial C-S-H gel layer is formed over the C3S surfaces
Ettringite is formed and precipitates onto the C3A surfaces
Hydration reactions reduced because:
- C3A inhibited by ettringite formation
- C3S inhibited by C-S-H gel layer
- C2S and C4AF naturally slow reactions
Ca(OH)2 concentration starts increasing
22 Cement Chemistry
Hydration of Portland Cement
INDUCTION PERIOD
Hydration activity low and heat liberation falls
Ca2+ and OH- ion concentration increasing to saturation
with respect to Ca(OH)2
Ca2+ and OH- ion critical supersaturation level reached,
Ca(OH)2 starts to precipitate
Period ends with increase in hydration activity and heat
generation
Change C-S-H gel layer allows hydration of C3S to
continue
Gypsum used up so C3A hydration resumes quickly
Only small percentage of C3S hydrated during this period
23 Cement Chemistry
Hydration of Portland Cement
ACCELERATION PERIOD
Most rapid hydration occurs (Still most C3S available
for reaction)
Solid Ca(OH)2 crystallizes from solution
Hydrates interlink and grow, decreasing porosity
Cohesive network is formed, strength developed
DECELERATION PERIOD
System porosity decreases as more hydrates formed
Diffusion of water through hydrate layers is reduced
Transport of ionic species is hindered
Hydration rate decelerates
24 Cement Chemistry
Hydration of Portland Cement
DIFFUSION PERIOD
Hydration continues very slowly
Reducing rate of heat evolution
Thickening of hydration products around cement
phases = Porosity Reduction
No major structural changes occur
Total hydration is never attained under ambient
conditions
25 Cement Chemistry
Hydration of Portland Cement
THE MULTICOMPONENT SYSTEM
12
10 Dissolution: Ettringite
and C-S-H gel formation
Formation of
Formation of Monosulfate
Rate of Evolution
8 C-S-H & CH
6 Diffusion
Controlled
Reaction
Increase Ca++ Final Set
4 and OH- concent.
2 Initial Set
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
min. days
hours
Time of Hydration
26 Cement Chemistry
Temperature Effects
250
Higher temperature,
200
higher hydration rate.
Add retarders to extend
150
induction period.
Heat flow (mW)
25
45
65
100
85 Add accelerators to
reduce induction period.
50
Above 230F, C-S-H gel
not stable and unstable
0
0 5 10
Hydration tim e (hr)
15 20
crystalline products
formed.
27 Cement Chemistry
Cement Volume Changes
PERCENT ABSOLUTE VOLUME REDUCTION
30 Cement Chemistry
Sulphate Resistance
1. Mg + Na SULPHATES IN FORMATION FLUIDS REACT WITH
Ca(OH)2 CRYSTALS IN THE CEMENT TO FORM:
Crystals of Mg(OH)2
Ca(OH)2 + MgSO4 + 2H2O ------> CaSO4.2H2O + Mg(OH)2
A solution of NaOH
Ca(OH)2 + Na2SO4 + 2H2O ------> CaSO4.2H2O + NaOH
2. CHLORIDE ACTION:
32 Cement Chemistry
Strength Retrogression
A DECRESASE IN STRENGTH AT HIGH TEMPERATURES
AMORPHOUS CRYSTALLINE
STABLE Expansion PERMEABLE
C/S RATIO = 1.5 LOW COMPRESSIVE STRENGTH
(C6S3H2) (>300F)
33 Cement Chemistry
Strength Retrogression
1. CS and K - neat cement @ 230oC (450oF)
2. CS and K -
16.0 lb/gal Class G
+ 35% silica
1 D30 @230oC(450oF)
2 D66 @230oC(450oF)
3 D66 @320oC(610oF)
Strength Retrogression
API Cement Classification
CLASS A : Intended for use from surface to a depth of 6,000 ft (1,83
m), when special properties are not required. Similar to ASTM Type I
cement.
39 Cement Chemistry
Why Cement Characterization?
CEMENT IS NOT HOMOGENEOUS
Different raw materials and sources.
Different manufacturing techniques.
COMPOSITION NOT REPRODUCIBLE
Differs from batch to batch.
Cement not homogeneous.
Different classes manufactured.
Large scale manufacturing process.
COMPOSITION CONTROLLED BY MANUFACTURES
Dowell not involved in Q/C of cements.
API specification cover wide range of properties, etc.
DIFFERENT RESPONSE TO CEMENT ADDITIVES
Heterogeneous nature and varying composition.
Inconsistent physical properties (eg., fineness)
Aging phenomenon.
42 Cement Chemistry
Cement Characterization - Phase
Composition
MAJOR PHASES: (Typical concentration, %)
43 Cement Chemistry
Cement Characterization - Physical
Properties
TYPICAL PHYSICAL PROPERTIES OF WELL
CEMENTS
Cement Median % Fines BET Area Blaine Area Silicate Aluminate
Type Dia (mm) (<1 mm) (m2/g) (cm2/g) (%) (%)
1(A ) 20.3 4.7 1.0 3400 54 46
2(G) 24.6 4.6 0.7 2900 43 57
3(H) 25.4 4.0 0.6 3000 53 47
4(H) 24.1 4.0 0.7 3040 82 18
44 Cement Chemistry
Cement Lab Introduction
Laboratory Functions
Performance Evaluation
Slurry Design Stage
Measurement of specific slurry properties under downhole
conditions.
Execution Stage
Monitor preparation of blended material
Chemical Characterization
Quantitative or qualitative analysis of the slurry components
prior to mixing.
Cement
Additives
46
Mix Fluid
Intro to Cement Lab
Performance Evaluation- Slurries
Governed by the API committee on
Standardization of Oilwell Cements (Com. 10)
Publication consists of;
Specification tests for neat cement slurries
Operational testing procedures for all slurries
Procedures designed to simulate downhole
conditions
Pressure
Temperature
47 Intro to Cement Lab
Performance Evaluation-
Spacers/Washes
Evaluation of the cleaning effect
Compatibility with Cement
Thickening Time
Fluid Loss
Compressive Strength
Rheology
Effects on mud
Rheology etc.
Volumen Absoluto de los Materiales Insolubles: Cada material insoluble, incluyendo el cemento,
cuando se mezcla en una lechada, aumentar en volumen por una cantidad especfica por libra de
material. Este volumen es conocido como el volumen absoluto y se expresa en gal/saco o gal/lb. El
volumen absoluto para la mayora de materiales insolubles puede calcularse si se conoce sus gravedades
1
Va =
(S G)x8.33
especficas, de esta manera:
Las gravedades especficas para el cemento y la barita son 3.14 y 4.25 respectivamente.
56
Clculos de Cemento
Cmo calcular la densidad y el rendimiento de la lechada
Se puede calcular la densidad de la lechada mediante la suma del
peso de cada componente de la lechada en lb/saco y dividiendo por el
volumen absoluto total (volumen de la lechada) en gal/saco. Configure
una tabla as:
Material Peso (lbm/sk) Volumen Absoluto (gal/sk)
Cemento 94 {1.0/(3.14 x 8.33)} x 94 = 3.60
Agua 8.33 x Vw Vw
Aditiv.(si hay alguno)lbm/sk gal. (Va x lbm)
Peso Total lbm/sk Volumen Total gal/sk
Densidad de la lechada= Peso Total (lbm/sk)/Volumen Total (gal/sk)=
lbm/gal.
Rendimiento de la lechada = Volumen Total (gal/sk)/7.48 gal/pie3 =
pie3/sk
Vw = Requerimiento de agua (gal/sk)
57
Clculos de Cemento
Ejemplo de Clculo de la Densidad y Rendimiento de la
Lechada
Pregunta: Determine la densidad y el rendimiento de la lechada de
cemento API Clase "G". Requerimiento de agua para mezcla es 5.0
gal/sk. Datos: 1 sk de Clase "G" = 94 lb y su gravedad especfica =
3.14
Solucin: Va = 1.0/(3.14 x 8.33) gal/lbm = 0.03823 gal/lbm
Volumen absoluto/sk = 0.03823 gal/lbm x 94 lbm/sk = 3.60 gal/sk
Material Peso (lbm/sk) Volumen Absoluto (gal/sk)
Cemento 94 {1.0/(3.14 x 8.33)} x 94 = 3.60
Agua 5 x 8.33 = 41.65 5.0
Aditivos 0.0 0.0
Peso Total = 135.65 lbm/sk Volumen Total = 8.60
gal/sk
Densidad de la Lechada = 135.65 lbm/sk/ 8.60 gal/sk = 15.8 lb/gal.
Rendimiento de la Lechada = 8.60 gal/sk)/7.48 gal/pie3 = 1.15 pie3/sk
58
Clculos de Cemento
Ejemplo de Clculo de la Densidad y Rendimiento de la Lechada
Pregunta: Determine la densidad y rendimiento de la lechada de cemento Pozmix
(50:50). Requerimiento de agua de mezcla es 7.0 gal/sk. Nota: Pozmix (50:50)
significa 50% Pozmix y 50% de cemento Clase "G" de tipo Portland. 1 sk Pozmix =
74 lb y gravedad especfica = 2.46; 1 sk de Clase "G" = 94 lb y su gravedad
especfica = 3.14.
Solucin: Va-Pozmix = 1.0/(2.46 x 8.33) gal/lbm = 0.0488 gal/lbm
Volumen absoluto/sk = 0.0488 gal/lbm x 37 lbm/0.5 sk = 1.81 gal/0.5 sk
Va-Clase G" = 1.0/(3.14 x 8.33) gal/lbm = 0.03823 gal/lbm
Vol. Absoluto/sk = 0.03823 gal/lbm x 47 lbm/0.5 sk = 1.80 gal/0.5 sk
Material Peso (lb/sk) Volume absoluto (gal/sk)
Cemento Pozmix 37 {1.0/(2.46 x 8.33)} x 37 = 1.81
Clase "G" 47 {1.0/(3.14 x 8.33)} x 47 = 1.80
Agua 7 x 8.33 = 58.31 7.0
Aditivos (si hay alguno) 0.0 0.0
Peso Total = 142.31 lb/sk Volumen Total =10.61 gal/sk
Densidad de la Lechada = 142.31 lb/sk/ 10.61 gal/sk = 13.4
lb/gal.
Rendimiento de la Lechada= 10.61 gal/sk)/7.48 gal/pie3 = 1.42
pie3/sk
59
Testing Process
LAB ANALYSIS
REQUEST
SLURRY DENSITY
RHEOLOGY
THICKENING TIME
TEST
LABORATORY REPORT
65
Reporting
Intro to Cement Lab
Filtrate Loss
For slurries that dehydrate in less than 30
minutes, Fluid Loss value is obtained by
either:
F 30 = Ft 5.477
t
F30 = Filtrate at 30 minu
tes
Ft = Filtrate at Time
t = Time in minutes
Relationship
Simple calculation = F30 = (F7 x 2)
66 Intro to Cement Lab
Slurry Tests - cont.
Rheology
Calculated by correlation of shrear stress against
shear rate
Tested with Rotational Viscometer (FANN 53)
Rotational speed (Shear rate)
300 RPM
200 RPM
100 RPM
60 RPM
30 RPM
600 RPM not used.
67 Intro to Cement Lab
Rheology
6 RPM and 3 RPM readings omitted.
3 RPM reading is used to determine the
fluid gel strength at;
10 seconds & 10 minutes BOB (Stationary)
Rotational Sleeve
Slurry Cup
70
60
50
40
30
20
10
0 50 100
Bc
Reproducido con el permiso de API RP 10B Prctica Recomendad para las Pruebas de los Cementos y
Aditivos de Cementos de los Pozos Petroleros. Los lmites de profundidad se basan en condiciones
impuestas por las pruebas a revestimientos de estimulacin de pozos y se considerarn como valores
aproximados.
75
Esquema del Tapn Compensado de Cemento
Solucin
1. Punto de igualacin H
= volumen de cemento/((cap. anular entre 7 y 2-7/8) + cap.de tubera 2-7/8.))
= 110 pies cbicos /(0.1697 pies cbicos /pie+ 0.0325 pies cbicos /pie) = 544 pies.
2. La altura del agua por delante = volumen de agua por delante /(capacidad anular entre 7 y 2-7/8)
= 10 bbl x 5.615 pies cbicos/bbl)/(0.1697 pies cbicos/pie) = 331 pies.
3. Volumen de agua por detrs
= Altura de agua por delante x cap. de tubera de 2-7/8 = 331 pies x 0.0325 pies cbicos/pie
= 10.76 pies cbicos = 10.76 pies cbicos /(5.615 pies cbicos /barril) = 1.92 bbls
4. Desplazamiento
= [8000 -(544 + 331)]pies x 0.0325 pies cbicos /ft = 7125 x 0.0325 pies cbicos /pie = 231.56 pies
cbicos = 41.24 bbls.
77