1 Cement Chemistry

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 :

Calcareous - 2 Parts Argillaceous - 1 Part

Limestone (CaCO3) Clays
Cement rocks Shales
Chalk Slate and Mudstone
Marl Blast furnace slag
Marine shells and coral Ashes (fly ash)
Alkali wastes Cement rock

Grind and heat treating processing a kiln at 1500oC

3 Cement Chemistry
 Cement Materials & Processing of
Cement
CLINKER - Grind and Heat Treat in kiln at 1500o C

CEMENT CLINKER

C3S : Tricalcium Silicate

C2S : Dicalcium Silicate
C3A : Tricalcium Aluminate
C4AF : Tetracalcium Aluminoferrate
Ca + Mg Oxides, Ca(OH)2, CaCO3, Na2NO4.
etc

Controlled cooling to second grinding mill

4 Cement Chemistry
 Cement Materials & Processing of
GYPSUM Cement
Add 3 - 5% GYPSUM (Ca.SO4.2H2O) or Blend Of
Gypsum
+
Calcium Sulphate Hemihydrate (CaSO4.1/2H2O)
or Anhydrate (CaSO4)

Pulverize Mixture and Blend

PORTLAND CEMENT

C3S + C2S + C3A + C4AF + CaSO4.2H2O + CaO + MgO

+ (Na2SO4 + NaKSO4 + CaK2(SO4)2, or K2SO4)
5 Cement Chemistry (depending on the cement)
 Burning Process/Heat Treatment
Reaction zones in a rotary cement kiln.
ZONE TEMPERATURE REACTION
RANGE (oC) PROFILE

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

Cooling Rate: Slow (4-5oC/min)

C3A and C4AF develop a high degree of cristalinity
C3S and C2S crystals become highly ordered
Free Magnesia forms periclase crystals
Result: Less hydraulically active with large particle size
More required energy during grinding stage
Quicker early strength development (3-7 days)
Lower long term strength(28 days)
Lower sulphates resistance
HIGHER DEGREE OF UNSOUNDNESS

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

The best way:

1 ) Cool slowly to +/- 2,282 oF (1,250 oC), (7-9
oF/min)

2 ) Cool fast 32-36 oF/min (18 - 20 oC/min)

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:

b. Particle size distribution: (Typical sending output)

100
80
60
%
40
20
0
100 10 1

11 Cement Chemistry
EQUIVALENT SPHERICAL DIAMETER, mm
 Effects Manufacturing Process
Steps on Cement Properties
PROPORTIONING OF RAW MATERIALS

Material Conc. % Too Low Too

High

CaO 65 Low early Stgn. Cracking, Unsoundnes

SiO2 22 Rapid Setting Slow Setting
Al2O3 5 Increased Kiln Rapid Setting
Temp. req. for burning
Fe2O3 4 Rapid Setting
MgO 1 Unsoundness (>5%)

12 Cement Chemistry
 Effects Manufacturing Process
Steps on Cement Properties
COOLING PROCESS

SLOW COOLING FAST COOLING

Allows clinker crystallization Allows Glass

Formation
Ensures Better Grinding Clinker Difficult to Grind
More C3A + MgO to Crystallize Prevents Beta Form of
C2S
Produces alpha C2S (almost inert) Causes less C3A
+ MgO to form

13 Cement Chemistry
 Effects Manufacturing Process
Steps on Cement Properties
GRINDING PROCESS AND GYPSUM ADDITION

FINER GRIND Increased Proportion of cement

reacts. Rate of Hydration Increased.
Higher Early Strength
Development.

GYPSUM Controlled Addition Difficult.

Calcium Sulphate Hemi-Hydrate
formation leads to shorter Hydration
times.
Too Little gives Gelation Problems.

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

min hrs days

0
0
4
5
8
12
16
20
24
28
32
36
40
44
48
52
56
60
64
68
72
76
80
84
88
92
96
100
104
108
112
116
120
Time of Hydration

I. Preinduction Period IV. Deceleration Period

II. Induction Period V. Diffusion Period
III. Acceleration Period Note: T.T. Thickening time
M.T. Mixing time
17 Cement Chemistry
18 Cement Chemistry
 C3S & C2S Hydration
2C3S + 6H C3S2H3 + 3CH (FAST)
2C2S + 4H C3S2H3 + CH (SLOW)
2C3S + C2S + water C-S-H GEL +
PORTLANDITE (Ca(OH)2)
C3S major constituent (up to 60 - 65 %)
C2S normally less than 20%
C3S hydrates much faster than C2S
C-S-H gel + 70% hydrated cement and is principle binding
material
19 Cement Chemistry
 C3S AND C2S Hydration

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

ALL GYPSUM FINISHED

C3A.3CS.32H + 2C3A + 4H C3A. CS.12H

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

No 1 Day 7 Days 28 Days100 Days

Portland cement 1 2.8 4.8 6 6.9
Portland cement 2 1.7 4.4 6.3
Portland cement 3 2.7 8 8.6 8.7
without gypsum 4 2.6 6.3 7.5 7.6

- Cement chemical concentration

- Bulk or outer schrinkage : +/- 0.1% BV cement
- Inner concentration : 4 - 6% BV cement
- Inner shrinkage creates secondary (or extra porosity) in set
cement matrix
28 Cement Chemistry
 Aging Effects
A Result Of:
Long Storage Periods
High Humidity
Hot Temperatures
Carbonation
Effect Cement By:
Increased Thickening Time
Decreased Compressive Strength
Decreased Heat Of Hydration
Increased Slurry Viscosity
Unpredictable Slurry Viscosity
Bulk Handling More Difficult
29 Cement Chemistry
 Particle Size Distribution (PSD)
SURFACE AREA OF ANHYDROUS CLASS G CEMENTS

SAMPLE SURFACE AREA (m2/g)

Blaine BET
A 0.2 0.8
B 0.3 0.5
C 0.4 1.2

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. SWELLING OCCURS DUE TO REPLACEMENT OF Ca(OH)2 BY

Mg(OH)2

3. GET INCREASE IN CEMENT POROSITY BECAUSE NaOH IS

MUCH MORE SOLUBLE THAN Ca(OH)2

4. FORMATION OF ETTRINGITE ARTER CEMENT HAS SET

-----> EXPANSION AND CRACKING OF CEMENT <-----

C3AH6 + 3CSH2 + 2OH -----> C3A.3CS.32H (2ndry Ettringite)

C3A + 3CSH2 + 26H ------> C3A3CS.32H (Ettringite)

31 Cement Chemistry
 Salt Aggression of Set Cements
1. SULPHATE ACTION:

Ca(OH)2 + MgSO4 -----> Mg(OH)2 + CaSO4

3CaSO4 + C3A + 32H2O ----->C3A.3CaSO4.32H2O

------> SWELLING AND CRACKING <------

2. CHLORIDE ACTION:

Ca(OH)2 + MgCl2 -----> Mg(OH)2 + CaCl2

CaCl2 + C3A + 10H20 ------> C3A.CaCl2.10H2O (Unstable monochloroaluminate)

C3A.CaCl2.10H2O + 3CaSO4 -----> Secondary Ettringite

------> SWELLING AND CRACKING <------

3. ALKALI SALT ACTION:

Ca(OH)2 + Na2SO4 ------> CaSO4 + 2NaOH

---------> EROSION <---------

32 Cement Chemistry
 Strength Retrogression
A DECRESASE IN STRENGTH AT HIGH TEMPERATURES

At 250F (120C) Slow decrease

At 450F (232C) Within a few days
At 600F (315C) Within days

DUE TO STRUCTURAL CHANGE OF THE HYDRATED CEMENT ABOVE 230F (110C)

C-S-H GEL + Ca(OH)2 ------> a - C2SH (>230F)

AMORPHOUS CRYSTALLINE
STABLE Expansion PERMEABLE
C/S RATIO = 1.5 LOW COMPRESSIVE STRENGTH

PREVENT BY REDUCING CEMENT C/S RATIO BY ADDITON OF 35 - 40% BWOC SILICA

C-S-H + SILICA ------> TOBERMORITE (C5S6H5) (>230F)

TOBERMORITE ------> XONOTLITE (C6S6H) + GYROLITE

(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. Class G + 44% water

2. Class G + 38% water
3. Class H + 32% water 1 D30 @230oC(450oF)
4. Extended cement 2 D66 @230oC(450oF)
3 D66 @320oC(610oF)

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.

CLASS B : Intended for use from a depth of 6,000 ft (1,830 m ),

Moderate to high sulphate resistance. Similar to ASTM Type II, and
has a lower C3A content than class A.

CLASS C : Intended for use from surface to a depth of 6,000 ft (1,800

m), when conditions require early strength. Available in all three
degrees of sulphate resistance, and is roughly equivalent to ASTM
Type III. To achieve high early strength. The C3S content and the
surface area are relatively high.
 cont . . . .
CLASS E : Intended from use from 10,000 ft (3,050 m) to
14,000 ft (4,270 m) under conditions of high temperatures
and pressures. It is available in MSR and HSR types.
CLASS D : Intended for use from 6,000 ft (1,830 m) to
10,000 ft (3,050 m) under conditions of moderately high
temperature and pressure. It is available in MSR and
HSR types.
CLASS F : Intended from use from 10,000 ft (3,050 m) to
16,000 ft (4,880 m) depth under conditions of extremely
high temperature and pressure. It is available in MSR and
HSR types.
 cont . . .

CLASS G and H : Intended for use as a basic well

cement from surface to 8,000 ft (2,440 m) as
manufactured, or can be use with accelerators and
retarder to cover a wide range of well depths and
temperatures. No additions other than calcium
sulphate or water, or both , shall be interground or
blended with the clinker during manufacture of class
G and H well cements. They are available in both
MSR and HSR types.
38 Cement Chemistry
 API Cement Typical Phase Compositions
TYPICAL POTENTIAL PHASE COMPOSITION (%)

API ASTM C3S C2S C3A C4AF FINENESS

SPECIAL
CLAS TYPE (cm2/g) APPLICATION

A I 45 27 11 8 1600 Surface Csg.

B II 44 31 5 13 1600 < 6000 ft
C III 53 19 11 9 2200 High strength
D - 28 49 4 12 1500 6 - 10000 ft
E - 38 43 5 9 1500 10 - 14000 ft
G (II) 50 30 5 12 1800 > 8000 w add.
H (II) 50 30 5 12 1600 Same as G

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.

CHARACTERIZE TO BETTER UTILIZE CEMENT AND ADDITIVES FOR

BETTER SERVICE
40 Cement Chemistry
 Methods of Cement
Characterization
CHEMICAL NATURE
Major oxide (CaO. SiO2, Fe2O3, SO3, etc. )
Minor oxide content (ZnO, P2O5, Mn2O3, etc. )
Soluble / Insoluble alkali content
Major phase content ( C3S, C2S, C4AF, C3A )
Minor phase content (Gypsum, Free lime Synergite, Hemihydrate,
Calcite)
PHYSICAL NATURE
Particle size distribution
Specific surface area (Blaine fineness)
RESPONSE TO CEMENT ADDITIVES
Retarders
Dispersants
API PERFORMANCE TESTS
Thickening time
Free Water
Chemistry
41 Cement Compressive strength
 Cement Characterization - Oxide
Contents
MAJOR OXIDES: (Typical concentrations, %)

CaO SiO2 Fe2O3 Al2O3 MgO Na2O K2O SO3 Na2O

64.1 21.2 5.2 3.7 1.5 0.17 0.49 2.19 0.49
Na2O = (0.658 x %K2O) + Na2O
By API: - MgO < 6.0 %
- Na2 equiv. < 0.75 %
- SO3 < 3.0 % (for Class G)
MINOR OXIDES: (Typical concentrations, %)
ZnO P2O5 Mn2O3 Cr2O3 TiO2 SrO
0.03 0.15 0.08 0.01 0.21 0.08
<0.3 - 0.5 <0.3 - 0.5 <0.5 - 1.0 <0.3 - 0.5 <1.5 - 2.0 <0.5 - 1.0

Bottom row is recommended range.

42 Cement Chemistry
 Cement Characterization - Phase
Composition
MAJOR PHASES: (Typical concentration, %)

C3S C2S C4AF C3A (C3S + C2S)

61.3 14.6 15.8 0.9 78.9

1. C 3 S, C 2 S, C 4 AF and C 3 A: From Bogue Method

2. ( C 3 S + C 2 S ): After extraction by maleic acid in methanol

FOR API Requirements:

- HSR Cements: 48% < C 3 S < 65%, and C 3 A < 3%
C 4 AF + ( 2 x C 3 A ) < 24%
- MSR Cements: 48% < C 3 S < 58%, and C 3 A < 8%
MINOR PHASES: (Typical concentration, %)

Gypsum Hemi- Ca(OH)2 Sinergite CaCO3 Loss on Free Insol.

Hydrates Ignition Lime
Residue
1.39 1.22 0.72 0.40 0.72 1.05 0.73 0.53

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

For comparison purposes only

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.

48 Intro to Cement Lab

 Chemical Characterization
Four types of samples are examined;
Cement Powder
C3A, C3S, C2S, C4AF and Gypsum
Dry Blended Cement
Consistency
Set Cement
Mix water

49 Intro to Cement Lab

 Sample Preparation

50 Intro to Cement Lab

 Sample Preparation
Use representative samples.
Sample acquisition
Prior to shipment
No additive should be used that is not from
actual field samples
Sample and handling procedures
SPEC 10 Section 3

51 Intro to Cement Lab

 Slurry Design

52 Intro to Cement Lab

 Slurry Properties
Free Water & Slurry Sedimentation
Water separation from static slurry
Migrates upward, accumulates in pockets or at top
of cement column.
Results in incomplete zonal isolation
Density
Balance sub-surface pressures
Cement final strength

53 Intro to Cement Lab

 Slurry Properties - cont.
Pumpability (Slurry Consistency)
Length of time slurry remains in a pumpable fluid
state (Job Time + 1 Hour)
Fluid Loss
Slurry dehydration during placement phase
Rheology
Slurry flow modeling

54 Intro to Cement Lab

 Set Cement Properties
Bonding
Cement - Casing & Cement - Formation
Sulfate Resistance
Reaction to magnesium and sodium sulfates;
Loss of compressive strength
Stress cracking
Strength Retrogression
Cement Shrinkage occurs at >230o F.
Permeability
Lightweight slurries
55 Intro to Cement Lab
 Principios Bsicos para el clculo de
cemento
Constantes Usadas Generalmente en los Clculos de Cementos
Gravedad especfica del cemento = 3.15
Peso de 1 saco de cemento (1 pie cbico.) = 94 libras
Volumen Absoluto por saco de cemento, Va = 3.60 gal/saco = 0.03823 gal/lbm
Densidad del agua a 80oF = 8.33 lbm/gal = 62.23 lbm/pie3
Galones por Pie Cbico = 7.48

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:

en donde Va = volumen Absoluto gal/lbm y SG.= gravedad especfica del material

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

FREE WATER FLUID LOSS

TEST TEST

RHEOLOGY

CEMENT - SPACER - MUD COMPRESSIVE STRENGTH

COMPATABILITY TEST

THICKENING TIME
TEST

LABORATORY REPORT

60 Intro to Cement Lab

 Laboratory Analysis Request -
(LAR)
Submitted to lab requesting formulation of cement slurry
Designate additives available for slurry
Request specific performance parameters;
Density
Rheology ( Plastic Viscosity & Yield Point)
Fluid Loss
Thickening Time
Free Water
Provide information on well parameters
Job Type, Depth, BHT & mix water type etc.
61 Intro to Cement Lab
 Sample Calculation
Sample volume for slurry testing is 600 ml
Consider the following slurry composed of;
Class G Cement & 44% water

Material Weight
(lbs)
Absolute Volume
(gal)
Volume
(gal)
Weight
(gram)
Volume
(ml)
Class G Cement 94 0.0382 3.59 42637.7 13589.6
Water 44% 41.36 0.1202 4.97 18760.6 18813.5

TOTAL 135.36 8.56 61398.3 32403.1

Calculate for 600 ml

ratio equal to Total Volume / 600 ml
ratio = 54:1
62 Intro to Cement Lab
 Slurry Preparation
Mixed with a high shear mixer (Waring Blender)
Two rotational speeds
4000 RPM
12000 RPM
Water and Liquid Additives mixed first
Add Cement /Solids at 4000 rpm (15 seconds)
12,000 RPM for 35 seconds
Mixing procedure not suitable for;
Microspheres (D124)
Nitrogen (Foam slurries)
63 Intro to Cement Lab
 Slurry Tests
Density Measurement
Measured with an Atmospheric or Pressurized
Balance
units are ppg, Kg/m3, SG
Free Water Test (API spec 10 sect. 6)
Slurry placed in 250ml graduated glass test tube
Free water (ml) measured after 2 hours

64 Intro to Cement Lab

 Slurry Tests - cont.
Fluid Loss Test
Simulates amount of filtrate lost under pressure against a permeable
formation
Two types of filter press available;
Low pressure (100 psi)
HPHT, high pressure, high temperature (1000 psi)
HPHT is used for slurry test (simulates conditions)
Permeable formation simulated by 325 mesh screen
Backed up by a 60 mesh screen
Test Parameters

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

68 Intro to Cement Lab

 Slurry Tests - cont.
Thickening Time
Determine length of time a slurry remains fluid
Pressurized consistometer simulates both;
Temperature
Pressure
Reported in Beardon units of consistency (BC)
Upper fluid limit (API) 100 BC
API spec 10 for schedules (example Fig B-7 in
Well Cementing)
Casing (1g - 11g)
Liners (22 - 32)
69 Intro to Cement Lab

Squeeze cementing (12 - 21)

 API Schedules
Pressure and Temperature changes
Effect on Thickening Time
Realistic Laboratory Evaluation
Computer Simulation (CemCADE)
New Instrumentation

70 Intro to Cement Lab

 Thickening Time Test Curve
Temperature deg.F
0 100 200 300 400 500
140
130
120 Bc
110
100
90
80 Temp.
Time (min)

70
60
50
40
30
20
10
0 50 100
Bc

71 Intro to Cement Lab

 Slurry Tests - cont
Compressive Strength
Set cement strength under downhole conditions
Apparatus;
Curing Bath (ATM pressure & 82oC)
Curing Chamber (3000 psi & 193oC)
Procedure.
Measurement Unit
Other methods

72 Intro to Cement Lab

 Laboratory Analysis Report
At the conclusion of Cement Slurry formulation and
subsequent testing a report is produced outlining the
following;
Part 1
Information requested
Summary of results
Conclusions and recommendations
Part 2
Laboratory Tests and Results
Part 3
73 Intro to Cement Lab
Appendices as necessary
 Summary of Test Procedures
Test Category Equipment Procedure Reference
Sampling Diverted Flow sampler ASTM C702, API SPEC 10 (3)
Slurry Preparation Two speed propellar mixer API SPEC 10 (5)
Thickening Time Atmospheric consistometer API SPEC 10 (8)
pressurized consistometer
Fluid Loss HPHP fluid loss cell API SPEC 10 (app. F)
Compressive Strength Water bath, curing chamber API SPEC 10 (7)
Hydraulic press
Free Water 250 ml graduated cylinder api spec 10 (6) app. M
Permeability Water permeameter API SPEC 10 (app. G)
Rheology Rotational viscometer API SPEC 10 (app. H)
Static gel strength Rotational viscometer API RP 13B (section 2)
Expansion Bar mould, Cylindrical sleeves ASTM C 151
Spacer/Wash/Cement Compatibility Rotational viscometer Fluid loss cell API SPEC 10 (app. P)
consistometer, hydraulic press
Particle Analysis (Portland Cement) Blaine permeameter, ASTM C 204
Chemical Analysis of Dry Blends UV absorbtion spectrophotometry ASTM C 114
Chemical Analysis of Mix Water Wet chemical method API RP 45

74 Intro to Cement Lab

 Clasificacin API para Cementos de Pozos Petroleros o de Gas
Clase A: Se recomienda su uso para los 6000 pies. (1829 m) profundidad** (170oF.) (77oC) cuando no
se requieren propiedades especiales. Similar a ASTM C 150, Cemento de Tipo I.
Clase B: Se recomienda su uso para los 6000 pies. (1829 m) profundidad** (170oF) (77oC) cuando se
requiere resistencia moderada de sulfato. Similar a ASTM C 150, Cemento de Tipo II.
Clase C: Se recomienda su uso para profundidades de 6000 pies (1829 m)**. (170oF) (77oC) cuando
se requiere gran fuerza inicial. Similar a ASTM C 150, Cemento de Tipo III. Est disponible
en tipos normal y de gran resistencia a sulfato.
Clase D: Se recomienda su uso para los 6000 a 10000 pies. (1829 m a 3048 m) de profundidad **
(230oF) (110oC) cuando existan temperaturas relativamente altas y altas. Est disponible en
tipos normal y de gran resistencia a sulfato.
Clase E: Se recomienda su uso para los 6000 a 14000 pies. (1829 m a 4267 m) de profundidad **
(290oF) (143oC) cuando existan temperaturas altas y grandes presiones. Est disponible en
tipos normal y de gran resistencia a sulfato.
Clase F: Se recomienda su uso para los 10000 a 16000 pies. (3048 m a 4877 m) de profundidad **
(320oF) (160oC) cuando existan temperaturas y presiones extremadamente altas. Est
disponible en tipos normal y de gran resistencia a sulfato.
Clase G: Es un cemento bsico y su uso se recomienda para los 8000 pies. (2438 m) profundidad**
(200oF) (93oC) y compatible con aceleradores o retardadores y para usarse en un rango
completo de Clases A a E. Es similar en su composicin qumica a API Clase B.
Clase H: Es un cemento bsico y su uso se recomienda para los 8000 pies. (2438 m) profundidad**
(200oF) (93oC) y compatible con aceleradores o retardadores y para usarse en un rango
completo de Clases A a E. Es similar en su composicin qumica a API Clase B.

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

Durante su vida, cada pozo

requerir de un
taponamiento con tapones
de cemento. Generalmente
se tapona un pozo por los
siguientes motivos:
-Aislamiento de zona
-Prdida de Circulacin
-Perforacin direccional
-Abandono
Los 4 mtodos comunes de
colocar un tapn de
cemento son compensado,
cuchara volcadora, doble
tapn y doble tapn
modificado
76
 Problema de Ejemplo Tapn Compensado de Cemento
Se requiere colocar un tapn de cemento de 110 pies cbicos en el fondo de 8.000 pies de revestimiento
de 7, 26 #/pies,
usando tubera de 2.875, 6.85 #/pie.
El operador desea que la columna de cemento est compensada o equilibrada.
Tambin desea una columna equilibrada de agua
(que la altura de agua en el espacio entre la tubera y revestimiento sea igual a aquella dentro de la
tubera)
Agua por delante = 10 bbl.
Calcule lo siguiente: (a) el punto de equilibrio; (b) la altura de la columna de agua; (c) el volumen de agua
por detrs; y (d) el volumen de desplazamiento del lodo requerido para igualar la columna 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