An Undergraduate Technical Research Submitted to the

College of Engineering, Architecture and technology

Palawan State University
Puerto Princesa City

As Partial Fulfillment of the Requirements

For Degree of
Bachelor of Science in Petroleum Engineering

September 2018

THE POTENTIAL OF LEAUCAENA LEUCOCEPHALA

(IPIL-IPIL SEED EXTRAC/I2SE) AS A RETARDING
ADDITIVE TO PORTLAND
CEMENT CLASS A

by

JEROME N. ADRALES
DANDY V. APGAO
CEDRIC S. BARBA
CRISTOPHER JOSEPH E. MAGDULA

College of Engineering, Architecture and Technology

Palawan State University
Puerto Princesa City
 APPROVAL

This is to certify that we have supervised the preparation of and read the research paper prepared
by Jerome N. Adrales, Dandy V. Apgao, Cedric S. Barba, Cristopher Joseph E. Magdula
entitled The Potential of Leaucaena Leucocephala (Ipil-Ipil Seed Extract/I2SE) as a
Retarding Additive to Portland Cement Class A and that the said paper has been submitted for
final examination by the Oral Examination Committee.

Engr. Dexter B. Tanabe

Adviser

As members of the Oral Examination Committee, we certify that we have examined this paper and hereby
recommend that it be accepted as partial fulfillment of the undergraduate requirement for the Degree
Bachelor of Science in Petroleum Engineering.

Engr. Kristoffer C. Aguirre Engr. Rose Angelie Joy D. Narra Engr. Darwin E. Malazarte
Panel Member 1 Panel Member 2 Panel Member 3

This research paper is hereby approved and accepted by the College of Engineering, Architecture &
Technology as partial fulfillment of the undergraduate requirement for the Degree Bachelor of Science in
Petroleum Engineering.

Elucila M. Sespeñe, PhD

Dean, College of Engineering, Architecture & Technology
 `ACKNOWLEDGEMENT

The researchers would like to express their sincere appreciation and endless recognition to the
individuals who rendered the efforts in this successful research study.
First and foremost, to our Dear Almighty God by giving knowledge and wisdom to continue the
study.
To Adrales, Apgao, Barba and Magdula family who financially and morally supports the needs of
the researchers.
To our good adviser, Engr. Dexter B. Tanabe who offered his brilliant mind to supervise the entire
duration of paper.
To Engr. Rose Angelie Joy D. Narra, Engr. Ryan Kristoffer C. Aguirre and Engr. Darwin E.
Malazarte for guiding the proponents.
 TABLE OF CONTENTS

TITLE PAGE …………………………………………………………………………………...i

APPROVAL PAGE……………………………………………………………………………..ii

ACKNOWLEDGEMENT………………………………………………………………………iii

TABLE OF CONTENTS………………………………………………………………………. iv

LIST OF TABLES………………………………………………………………………………v

LIST OF FIGURES……………………………………………………………………………..vi

ABSTRACT…………………………………………………………………………………….vii

Chapter 1: INTRODUCTION……………………………………………………….1

Chapter 2: REVIEW OF RELATED LITERATURE……………………………….8

2.1 Well Cementing……………………………………………………………….8

2.2 Additives……………………………………………………………………...15

2.3 Leaucaena Leococephala or Ipil-Ipil plant ………………………………….19

2.4 Other Related Studies………………………………………………………...22

Chapter 3: CONCEPTUAL FRAMEWORK………………………………………26

Chapter 4: MATERIALS AND METHODS……………………………………….32

Chapter 5: RESULTS AND FINDINGS…………………………………………...36

Chapter 6: CONCLUSION AND RECOMMENDATIONS……………………….48

GLOSSARY OF TECHNICAL TERMS……………………………………………….50

BIBLIOGRAPHY………………………………………………………………………52

APPENDICES…………………………………………………………………………..55
 LIST OF TABLES

Table 2.1: Chemical compounds present in the Ipil-ipil seeds

Table 2.2: Thickening time values for different C. Fistula

additive concentrations in the cement

Table 4.1 Weight percentage of additive added to the cement

Table 5.2.1 Summary of data gathered from different parameter test

Table 5.2.2 Weight of different concentration of additive relative to moisture loss

Table 5.2.3 Average Weight Loss of the Samples based on Hardening Time

Table 5.2.4 Compressive Strength and Maximum Load on 7 Days

Hardening Time at 25C

 LIST OF FIGURES

Figure 2.1 A photograph of Leaucaena Leococephala (Ipil-ipil) Tree

Figure 3.1 Experimental Set-Up

Figure 5.1.1 Cube Test Specimen with different concentration of I2SE

Figure 5.1.2 Cement Slurry without I2SE additive

Figure 5.1.3 Cement slurry with 0.4g of I2SE additive

Figure 5.1.4 Cement slurry with 0.8g of I2SE additive

Figure 5.1.5 Cement slurry with 1.2g of I2SE additive

Figure 5.1.6 Cement slurry with 2.4g of I2SE additive

Figure 5.1.7 Cement slurry with 3.2 of I2SE additive

Figure 5.1.8 Cement slurry with 4g of I2SE additive

Figure 5.1.4 Cement specimen during Compressive Strength Test

Figure 5.1.5 Final appearance of cement specimen after compressive

strength test

Figure 5.2.1 Percent Weight Loss of Different I2SE Concentration vs.

Untreated Cement

Figure 5.2.2 Daily Moisture Loss Trend from Initial to Final Hardening Time

Figure 5.2.3 Daily Average Moisture Loss

Figure 5.2.4 Compressive Strength (psi) in 48hrs Hardening Time at 25C

Figure 5.2.5 Compressive Strengths of Retarder 0.4g I2SE vs. Average

Untreated Cement
 ABSTRACT

This study aimed to determine the retarding capability of Leaucaena Leucocephala Ipil-
Ipil seed extract (I2SE) to Class A Portland cement. To prove the hypothesis, a laboratory
experiment has been conducted to determine the weight of moisture loss of different concentration
such as 0.05%, 0.1%, 0.15%, 0.3%, 0.4% and 0.5% by weight percentage as well as to determine
the best concentration that shows good compressive strength. The preparation of additive
comprises of gathering seeds, grinding, oil extracting and drying method. Meanwhile, in
preparation of slurries, Portland cement is weighed 800 grams and mixed with I2SE additive by
weight percentage then the water measures 296 ml. They were mixed manually until became
homogenous. The prepared slurries were subjected to 2-inch cubic molders and let the cement
dried within 24 hours. The data for curing time is observed within 7 days, 6 different additive
concentrations were compared to untreated cement. To test its compressive strength, samples were
subjected to the strength testing unit. Then the data were recorded accordingly. Based on
quantitative analysis, results showed that at 0.05% bwoc with 0.4 grams of additive had the positive
result. At the same time, the said concentration also showed the best compressive strength.
 Chapter 1

INTRODUCTION

1.1 Background of the study

Wellbore cementing is an inseparable and a necessary part of the well construction. Cement

has a key role in the life and preserving the long term productivity, longevity and the overall

efficiency of the well. To enhance the characteristics of the cement in the well, various and

numerous additives have been introduced to be used in the cement composition. Generally, there

are 8 categories of additives available: Accelerators for reducing cement setting time and

increasing the rate of compressive strength build up; Retarders for extending the setting time;

Extenders for lowering the density; Weighting agents for increasing the density; Dispersants for

reducing viscosity, Fluid loss controllers for reducing/ceasing cement system water loss, Loss

circulation control agents and special type agents. Some additives however, act as multifunctional

agents affecting several cement properties. Cement settling times can be adjusted with retarders.

Cement retarders control the time when the slurry applied will set hard, keeping the slurry viscous

and pumpable in expected wellbore temperature and for the amount of time required to place the

slurry. Retarders decrease the rate of cement hydration, acting in a manner opposite to that of the

accelerators.

Some types of retarders are lignosulfonates, hydro carboxylic acid, cellulose derivatives,

saccharide compounds, and organophosphonates. Saccharide compounds (also called

carbohydrates) are molecular compounds made from just three elements: carbon, hydrogen and

oxygen. Monosaccharides (e.g. sucrose) are relatively small molecules.

 They are often called sugars. Other carbohydrates molecules are very large

(polysaccharides such as starch and cellulose). Due to the increasing demand in these specific

admixtures, these retarders are industrially available and are bought and sold commercially to

various engineering firms from across the globe. These admixtures however, come at high cost

and so, the research team has tried to come up of organic and cheap alternatives for such

admixtures, without sacrificing effectiveness and availability. To the research team, it would seem

that the locally growing Ipil-Ipil plant would be an interesting bet.

The Leaucaena Leucocephala, which is locally known as the Ipil-Ipil plant, is a small, fast

growing mimosoid tree that evolved in the Guatemalan center of genetic diversity, as a probable

tetraploid hybrid of diploid species in that region. There are two major forms found such as those

growing evidently indigenous to the Yucatan Peninsula that is bushy with heights reaching up to

8 meters as well as the arboreal “Salvador” type which grows up to 16 meters, mostly originating

in the regions of El Salvador, Guatemala and Honduras. These types of Ipil-Ipil were widely

distributed throughout Mexico and Central America to northern South America in the early 1500

AD. A single variety, Salvador forms was probably brought by Spanish galleons to the Philippines

in the early 1600s, from where it was distributed in the 19 th Century. Nowadays, it has adapted to

the Philippines very well and can be found easily and every region has their local names entitled

for this specie.

Ipil-ipil is spike less long-standing plant or tree which may grow to heights 7-20 meters.

The leaves are bipinnate with 6-8 pairs of pinnate bearing 11-23 pairs of leaflets 8-16 mm long.

The inflorescence is a cream colored circular shape which produces a cluster of flat brown pods

13-18 mm long containing 15-20 seeds.

 Three morphological types are noted by a small bushy type less than 5 meters; a giant type

with a trunk and great size to 20 meters. The most common form is the shrubby free-seeding one

which tends to be weedy and low yielding. The flowers are abundant, axillaries on long stalks,

white, and in dense global heads 1-2 cm across. The fruit shells have raised borders and it is flat

and thin. It becomes dark brown and hard, 10-15 cm long, and 1.6-2.5 cm wide. Seeds are

copiously produced, 15-30 per pod, oval, flattish, and shining brown [7].

Based on previous studies, Leaucaena Leucocephala seeds are rich in lipids, crude protein

and carbohydrates. The seeds contain tannin and oxalic acid, while the kernel contains oil content

of about 17 -20 %, crude protein (8.4 %), carbohydrates (45 %), and fatty acids (15 %). The high

amount of saccharide compound contained within the seeds makes the L. Leucocephala a potential

retarding agent for cement. The proponent has then come up with the idea of conducting a study

on determining the retarding effect of the extracted saccharides in the L. Leucocephala. Aside from

saccharides, the seeds also contain generous amounts of fatty acid and crude protein which can

also reinforce the retarding process when added in the cement slurry at specified amount of

pressure and temperature.

1.2 Statement of the problem

Cement jobs determined the whole operation in drilling and production. Associated

problems with cementing involves the early settling of cement before its projected displacement,

some were due to high pressure and temperature and some were migration of water from slurry

due to osmotic reaction between the slurry and formation fluid. To compensate this, retarder is

being pooled in the mixture of cement to enhance the early settling.

Specifically, this study seeks to answer the following questions:

1.) What are the effects of Ipil-ipil Seed Extract (I2SE) in the following properties of

cement slurry?

a. Weight of Moisture loss to curing time

b. Compressive Strength

2.) What are the effects of Ipil-ipil Seed Extract (I2SE) to the rate of hydration of the

cement slurry?

3.) What is the rate of efficiency in retardation of treated with I2SE compared to untreated

cement?

4.) At what concentration by mass of I2SE retarder additive is the best for the compressive

strength of the cement?

1.3 General and specific objectives of the study

The main objectives of this study is to determine the physical properties in the L.

Leucocephala seeds that may help increase the hardening time and performs good compressive

strength.

Specifically:

1. To determine the relationship of Ipil-Ipil seed extract hardening time from a neat cement.

2. To determine the relationship of I2SE compressive strength compared to a 0% additive

cement.

3. To determine which concentration by weight of cement performs longer hardening time.

4. To determine which concentration by mass basis of I2SE retarder additive is

the best for the compressive strength of the cement.

1.4 Significance of the Study

Generally, the result of this study can be any of the following:

Academically, this study shall serve as a future reference material for engineering and

industrial courses. We hope to enlighten our general audience for the potential of organic material

such as the Ipil-Ipil seed and to produce any viable additives for the industry.

For future researchers, this study can be served as a source of knowledge or idea in

determining the capacity of an organic material like Ipil-ipil seeds as an alternative concrete

cement retarder.
 Also, the petroleum industry spends a lot of money on buying expensive commercialized

additives and admixtures as a cement retarder. In our study, we find a way to make an alternative

cement retarder that can help not only the industry but also the local farmer to continually enrich

this specie for a healthy environment.

1.5 Scope and Delimitation of the Study

The focus of this study is to determine the retarding effect of I2SE in a Class A Portland

cement. The adverse chemical effects into cement composition will not be tackled and the

economic value of the experiment and the resulting material will not be considered.

For the materials, we will be using Leaucaena Leucocephala seeds harvested in Tiniguiban

Heights, Puerto Princesa City, Palawan, which will be pulverized using an available grinder that

can be found at New Market, San Jose. Distilled water and ordinary Portland cement class A will

be used. The drying of pulverized Leaucaena Leucocephala seed is to be conducted using a solar

drying method and will be observed as it is left to dry.

The proponent will be conducting three experimental trials. For each trial, 0.0%, 0.05%,

0.10%, 0.15%, 0.3%, 0.4% and 0.5% bwoc concentration will be used.

The curing time test is observed at atmospheric pressure within 7 days wherein the different

samples are weighed using electronic weighing scale and observe every 24 hours.

For compressive strength test, a 2 cubic inches’ molder is fabricated resourcefully as

suggested by the testing center.

The thickening and settling time test are not included in the study due to equipment and

financial constraint.
1.6 Assumptions of the Study

The proponents have assumed that the Ipil-Ipil seed extract admixture would yield

generally the same results as the commercial cement admixture. Also, the Ipil Ipil seed variety

have all the same chemical composition all throughout the countries. Then, the effect of solar

drying can dry enough the additive to remove bacterial growth. That, the Portland Cement Class

A is nearly enough to simulate the cement slurry introduced on oil wells. Measuring the mass

during curing time is done to simulate the moisture loss content.

 Chapter 2
REVIEW OF RELATED LITERATURE

2.1 Well Cementing

It has been said that there are two basic kinds of cementing operation, namely, primary and

secondary cementing. (J. Fink, 2015). Primary cementing is the process of placing cement in the

annulus between the casing and the formations exposed to the wellbore. Its major objective is to

provide zonal isolation in the wellbore of oil, gas and water wells. To accomplish a primary

cementing job, it uses the two-plug method for pumping and displacement. This method was first

used in 1910 in shallow wells in California (Smith, 1984; Smith, 1987). In order to achieve this

objective, a hydraulic seal must be obtained between the casing and the cement, and between the

cement and the formation. (Nelson, 1990). Cementing also protects useable water, provide

structural support for casing, protect casing from corrosion and isolate casing for subsequent

drilling (Tipton, 2013). Meanwhile, another type of cementing, generally referred to as secondary

cementing, refers to cementing operations that are intended to use cement in maintaining or

improving operation of the well (J. Fink, 2015).

2.1.1. Cementing Technology

Well cementing technology is the application of many scientific and engineering

disciplines (Tipton, 2013). It has been stated that the proper set cement is determined by

considering the density and viscosity of the material before actually pumping into the hole.
 Special mixers, including hydraulic jet mixers or batch mixers, are used to create wet

cement, also known as cement slurry. The cement used in the well cementing process is Portland

cement, and it is calibrated with additives to form one of eight different API classes of cement

(Rigzone, n.d.).

2.1.1.1. Portland Cement

Portland cement is a common component consisting of a sealing material for wellbores for

geological carbon storage to prevent vertical fluid migration and provide mechanical support (Lee

et al, 2015). Cement is manufactured through a closely controlled chemical combination of

calcium, silicon, aluminum, iron and other ingredients. Common materials used to manufacture

cement includes limestone, shells, and chalk or marl combined with shale, clay, slate, blast furnace

slag, silica sand and iron ore.

2.1.1.1.1. Classes of Cement

API has defined standard classes for cement, classified as Class A to Class H, as well as

standard types of cement used within oil and gas wells. The standard classes are defined as:

1. Class A: Intended depth range for usage: from surface to 6,000 ft., when special properties

are not required, available in ordinary type only; with temperature ranging between 80 °F -170

°F;
2. Class B: Intended depth range for usage: from surface to 6,000 ft., when conditions require

moderate to high sulfate-resistance, available as moderate and high sulfate-resistance types;

with temperature ranging between 80 °F -170 °F;

3. Class C: Intended depth range for usage: from surface to 6,000 ft., when condition require

high early strength, available in ordinary. Moderate and high sulfate-resistance types; with

temperature ranging between 80 °F -170 °F;

4. Class D: Intended depth range for usage around 6,000 to 10,000 ft., at moderately high

temperature between 170 °F -290 °F and pressure conditions, available in moderate and high

sulfate-resistance types.

5. Class E: Intended depth range for usage around 10,000 to 14,000 ft., at high temperature

between 170 °F -290 °F and pressure conditions, available in moderate and high sulfate-

resistance types.

6. Class F: Intended depth range for usage around 10,000 to 16,000 ft., at extremely high

temperature between 230 °F -320 °F and pressure conditions, available in moderate and high

sulfate-resistance type.

7. Class G: Intended as basic cement in the depth range surface to 8,000 ft., when used with

accelerators and retarders covers wide range of temperatures and pressures, no other additions

than calcium sulfate, water or both are to be blended with the clinker, available in moderate

sulfate-resistance types.
 8. Class H: Intended as basic cement in the depth range surface to 8,000 ft., when used with

accelerators and retarders covers wide range of temperatures and pressures, no other additions

than calcium sulfate, water or both are to be blended with the clinker, available in moderate

sulfate-resistance type only (Hamouda, n.d.).

The above mentioned classes of cement show each type’s respective parameters and

conditions at which they are to be applied. However, the study focuses mainly on Class G cement

due to the reliability and effectiveness its characteristics possess for basic casings.

In accordance with standard 10A API (American Petroleum Institute), the class G cement

is used mostly in offshore platforms. It is an oil well cement with special chemical composition

which become ideal solution for the construction of oil and gas wells, pipe lines and water wells.

Class G cement is characterized by the constancy of important requirements such as predictable

thickening time, high sulphate resistance, high durability, fluid loss control, low viscosity, the

tendency not to segregate and mechanical strength.

2.1.2 Cement Slurry Properties

For better management of cement, the following properties should be taken care of to

maintain well security and integrity such as; slurry density, thickening time, rheology, fluid loss

control, free water content, compressive strength and strength retrogression (Nitharwal).

According to J. Fink, the thickening time is proportional to the setting time, i.e., the longer the

thickening time, the longer the setting time will be.

2.1.2.1 Curing Time

Author stated that curing is the maintaining of an adequate moisture content and

temperature in concrete at early ages so that it can develop properties the mixture was designed to

achieved. Curing begins immediately after placement and finishing so that the concrete may

develop the desired strength and durability. Drying may remove the water needed for this chemical

reaction called hydration and the concrete will not achieve its potential properties. To achieve 50%

of strength, minimum curing period of Type I Cement at temperature - 50°F (10°C) is at least 6

days while at temperature- 70 °F (21°C) (1982).

2.1.2.2 Settling Time of Cement

The settling time of cement is considered as the period wherein the cement loses its

plasticity and has already transitioned into its solid state. The process initially occurs when cement

is mixed with water which hydrates and makes cement paste. For ordinary Portland cement, the

initial setting time is 30 minutes and the final setting is 600 minutes or 10 hours. Some factors that

affect the initial and final setting time of cement are; the fineness of cement, the presence of salt

in sand, as well as atmospheric condition. For instance, cement requires a temperature of 27°C to

complete hydration thus low temperature stops the hydration and takes a longer time to set harden.

2.1.2.3 Thickening Time

As defined by Schlumberger, the thickening time is the duration at which a cement slurry

remains in its fluid state and is capable of being pumped. Thickening time is assessed under

downhole conditions using a pressurized consistometer that plots the viscosity of a slurry over

time under the anticipated temperature and pressure conditions.

 Drilling oil and geothermal wells requires the use of drilling muds and well cements. These

materials are especially designed for their properties at elevated temperatures and pressures. For

development and testing of drilling muds and well cements, pressure vessels are required to

simulate the downhole conditions. Pressurized consistometers for measuring thickening times and

other properties already exist. With them, samples are tested in a rotating slurry cup with a

stationary internal paddle. The consistency of the sample is measured as a function of the time

under carefully controlled conditions of increasing temperature and pressure (Ruyak, et al, 1984).

2.1.2.4 Compressive Strength

It has been stated that compressive strength is the capacity of a material or structure to withstand

loads tending to reduce its size or the maximum compressive stress that under gradually applied

load a given solid material will sustain without fracture (Mishra,2016). Compressive strength of a

cement concrete depends on the type of raw materials including additives used, mixture

proportions, concrete structure, method and time of curing, and exposure conditions (Herianto and

Fathaddin, 2005). Cement with good compressive strength should be able to withstand hard and

corrosive formations, lost circulation zone, carbon (IV) oxide and other toxic gas intrusion, and

extremely high temperatures (Benjamin et al. 2010). To test compressibility, the sample is tested

by applying force to more than one axis of the specimen at elevated and lowered temperatures. It

is measured based on IS: 516-1959. Likewise, the cement slurry is prepared based on ASTM C109,

the standard test method for compressive strength of hydraulic cement mortars using 2-in cube

specimen.
2.1.2.5 Hydration of Cement

It has been stated that hydration is the series of chemical reaction of cement with water to

form the binding material. In other words, in the presence of water, the silicates (C 3S) and

aluminates (C3A and C4AF) form products of hydration which in time produce a firm and hard

mass (Dawood, n.d.).

2.1.2.5.1 Water supply

Fresh water is suitable for cement, provided that is found sufficient quantities. Some water

contains humic acid that acts as a retarder to hardening. Some rig water is found to contain

phosphates (thinners used for mud), and those chemicals can seriously retard the setting of cement.

The usual water cement ratio is 45% (5.2 gal/sack of dry cement; 500 gals per cementing

unit should be provided for priming, testing and cleaning up. An additional 5130 gals should be

provided as a minimum safety margin. Rate of water supply should be based on the rate of mixing

cement: usually this is about 5-6 bbl. /min. for each pumping unit on the job. Hot mixing water

may result in shorter allowable pumping time while cold water may provide viscous slurry during

mixing.
2.2 Additives

Cement additives have played an important role in the advancement of cementing

technology. To properly use the available cements, additives were developed to control the major

cement properties, i.e., thickening time, consistency, fluid-loss rate, free water, setting time, etc.

Consequently, a wide variety of cement additives is now available to alter cement properties to

meet most well conditions. Additives are chemicals and materials combined into base cement

slurries to change the performance of the cement. Due to inherent nature of base cements and

because of the demands placed on the cement sheath throughout the life of the well, the

performance properties of the cementing slurry are modified to address the specific and unique

conditions of well. Many of the additives currently used are organic, polymeric materials which

have been specifically formulated for use in well cementing operations (E. B. Nelson, 2006).

Author cited some important cement additives and its functions; Accelerators are added to shorten

the time for cement to properly set and it will reduce rig time while waiting on the cement (WOC).

Accelerators are crucial in shallow depths where bottom temperature is low. In the deeper section,

it may not require an accelerator, because the well temperature is hot enough and the thickening

time will be normal.

The WOC time is generally based on the time required to obtain 500 psi compressive

strength of the cement. Chemical used as accelerators are as follows; Calcium chloride 1.5-2.0 %,

Sodium chloride 2.0-2.5 % and sea water. If the percentage of these additives is high, they will act

as retarders instead of accelerators.

2.2.1 Retarders

Retarders are chemical additives used to decrease the speed of cement hydration. The

cements commonly used in well applications do not have a sufficient long fluid life (thickening

time) for use at Bottom Hole Circulating Temperatures (BHCTs) above 100 °F (38°C). For

extending the thickening time, additives known as retarders are required. Retarders inhibit

hydration and delay setting, allowing sufficient time for slurry placement in deep and hot well

(Satiyawira et al., 2010)

The whole point is it increases the thickening times for pumping the cement into place. The

retardation process is not completely understood but it is known that retarders bind to calcium ions

and are able to inhibit the growth of ettringite crystals (Magarini et al., 2009). Besides extending

the pumping time of cements, most retarders affect the viscosity to some degree. Retarders do not

decrease the ultimate compressive strength of cement but do slow the rate of strength development.

Retarding effects of a retarder depends upon a number of factors including dosage of the additives,

curing conditions among others. Therefore, Bottom Hole Circulation Temperature (BHCT) should

be carefully predicted so that the correct retarder concentration is used to avoid flash setting or

very long setting up time due to over-retarded cement slurry (H. F. Taylor, 1997).

Retarders are used at higher temperatures to allow time for mixing and placement of the

cement slurry and also when accelerating effect of another additive might dangerously reduce the

time available for pumping the cement (J. P. Nguyen, 1996). The most common retarders are

natural lignosulfonates, cellulose and sugars derivatives. The chemical nature of the retarder to be

used is dependent on the cement phase. Lignosulfonates and hydroxycarboxylic acids are retarders

that are believed to perform well for oil well cements with low C₃A contents. Some admixtures act

as retarders when used in small amounts but behave as accelerators when used in large amounts.
The newest retarders are made from various synthetic compounds. The addition of carbohydrates

such as sucrose can significantly extend thickening time or even prevent setting completely (Bentz

et al., 1994). However, they are not commonly used in oil and gas well cementing because of the

sensitivity of the degree of retardation to small variations in concentration.

Retarders have the opposite function as accelerators because they are used to prolong

thickening time of cement in order to prevent premature setting of cement. Retarders are used in

the deeper hole section where bottom hole pressure is high. Chemical used are as follows; Calcium

lignosulphonate and saturated salt solution. The chemical compounds identified as retarders to

decrease the speed of cement hydration, calcium lignosulfonates are the most widely used. Its

effectiveness is limited in temperatures above 200 °F. Concentrations of 0.1% bwoc - 1.0% bwoc

are used in most slurry applications to give both predictable thickening times and compressive

strengths. However, concentrations range of 0.1% - 0.5% is also used (E. Broni-Bediako, 2016).

2.2.1.1 Hydroxycarboxylic Acids

Hydroxycarboxylic acids are well known for their antioxidant and sequestering properties

that benefit cement-slurry performance. The antioxidant property improves the temperature

stability of soluble compounds such as fluid-loss additives. Commonly used hydroxycarboxylic

acids and their derivatives are Citric acid, Tartaric acid, Gluconic acid, Glucoheptonate and

Glucono-delta-lactone (Anonymous, 2015). The commonly used hydroxycarboxylic acids are

generally derived from naturally occurring sugars. It has been found that sugar acts as a retarder

of cement slurries when added in small concentrations and as an accelerator when added in high

concentration of 0.2% to 1% by the weight of cement. Hydroxycarboxylic acids are efficient to a

temperature of 302 °F (150 °C). However, below 200 °F (93 °C) they can cause over retardation.

One acid used is citric acid with an effective concentration of 0.1% - 0.3% bwoc (Anonymous,

2016).

Fatty acids are carboxylic acids with a long aliphatic tail. Fatty acids are divided into

saturated and unsaturated acid, depending on the presence of unsaturated double bond in the fatty

acid chain (J. H. de Geus et al., 2001). It has been stated that among the fatty acid commonly found

in nuts and seeds, 70-80% are essential fatty acids which are the components of the plasma

membrane and contain a lipoprotein found in brain cells known as lecithin (Chung, et al, 2013).

An example of commercial retarder available in the market costs ₱165/kilo based on

Alibaba.com.

2.2.1.1.1 Oil Extraction

Ethanol is a worthy candidate as an alternative solvent because it is cheap and it can be

produced by fermentation from a large variety of biological materials using simple technology,

and is therefore labeled as “natural” or “bio renewable”.

In addition, although flammable, this alcohol is recognized as non-toxic and has less

handling risks than hexane (Rittner, 1992). The use of ethanol as an extraction solvent also avoids

eventual toxicity problems of meals for animal feedstuff (Ferreira-Dias et al., 2003), but it has

been reported that the solubility of lipids in ethanol is drastically affected by the moisture content

of the solvent and the extraction temperature (Rao and Arnold, 1956, 1957). Due to the lower

selectivity of ethanol towards triglycerides, during the extraction process other compounds such

as phosphatides, polyphenols, pigments and soluble sugars are extracted jointly (Hron et al., 1982;
Hron et al., 1994; Sineiro et al., 1996). After the ethanol extraction, and when the miscella cools

down, it can be expected that part of the extracted material becomes insoluble (in ethanol) and

separates as an emulsion.

Some method in extraction of oils procedure like the plant samples of watermelon

(Citrullus Lanatus), muskmelon (Cucumis Melo) used were ground in grinder in the presence of

anhydrous sodium sulphate and accurately weighed. The ground plant materials (approximately

10g for each macerated with 300 ml 0f n-hexane at temperature for 2 days, the macerates were

shaken occasionally. Following filtration of the organic phases, the n-hexane phases of each

sample was concentrated in vacuum at 40 °C to obtain the oily residue. The chemical analysis of

watermelon and muskmelon revealed that they are similar in saturated fatty acids but differ

unsaturated fatty acids which may be a criterion of differentiation between the two plants.

(Rodrigues, et al, 2008).

The most popular extraction of lipids is that Folch procedure (Folch et al., 1957). It has

been determined that the Folch method is most effective for the extraction of a broad range of lipid

classes in human lipoproteins (Reis A, et al, 1824).

2.3 Leaucaena Leococephala or Ipil-Ipil plant

2.3.1 Availability

The Leaucaena Leococephala, locally known as Ipil-Ipil evolved in the Guatemalan center

of genetic diversity, as a probable tetraploid hybrid of diploid species in that region. There are two

major forms found such as those growing evidently indigenous to the Yucatan Peninsula that is

bushy with heights reaching up to 8 meters; and the other one, called the arboreal “Salvador” type

which grows up to 16 meters, mostly originated in the regions of El Salvador, Guatemala and
Honduras. These types of Ipil-Ipil were widely distributed throughout Mexico and Central

America to northern South America earlier 1500 AD. A single variety, Salvador forms was

probably brought by Spanish galleons to the Philippines in the early 1600s, from where it was

distributed in the 19th Century. Nowadays, it has adapted to the Philippines very well and can be

found easily and every region have their local names entitled for this specie.

Figure 2.1 A photograph of Leaucaena Leococephala (Ipil-ipil) Tree

2.3.2 Morphology

Ipil-ipil is spike less long-standing plant or tree which may grow to heights 7-20 meters.

The leaves are bi-pinnate with 6-8 pairs of pinnate bearing 11-23 pairs of leaflets 8-16 mm long.

The inflorescence is a cream colored circular shape which produces a cluster of flat brown pods

13-18 mm long containing 15-20 seeds. Three morphological types are noted by a small bushy

type less than 5 meters; a giant type with a trunk and great size to 20 meters.
 The most common form is the shrubby free-seeding one which tends to be weedy and low

yielding. The flowers are abundant, axillaries on long stalks, white, and in dense global heads 1-2

cm across. The fruit shells have raised borders and it is flat and thin. It becomes dark brown and

hard, 10-15 cm long, and 1.6-2.5 cm wide. Seeds are copiously produced, 15-30 per pod, oval,

flattish, and shining brown.

2.3.3 Ipil-ipil Seed Composition

Studies were carried out to characterize the oil and seed meal of ipil-ipil (Leaucaena

Leococephala) seed. The seed contains 6.7% oil and 31.6% protein on a dry weight basis. Physical

and chemical characteristics of crude oil were studied and the results indicated that the oil can be

used for edible purposes after refining. The GLC analysis revealed that the oil is composed of

palmitic acid (15.7%), palmitoleic acid (0.2%), stearic acid (3.6%), oleic acid (15.5%), linoleic

acid (63.2%) linolenic acid (0.4%), arachidonic acid (0.5%), and lignoceric acid (0.9%) (Hossain,

M. A. et al., n.d.). It has been stated that the crude protein percentage is about 46 %, carbohydrates

is 45 % (RJPBCS).

Chemical Compound Formula Percent Composition

Palmitic Acid C16H32O2 15.7

Palmitoleic Acid C16H30O2 0.2

Stearic Acid CH3(CH2)16COOH 3.6

Oleic Acid C18H34O2 15.5

Linoleic Acid C18H32O2 63.2

 Linolenic Acid C18H30O2 0.4

Arachidonic Acid C20H32O2 0.5

Lignoceric Acid C24H48O2 0.9

Table 2.1 Table representing the chemical compounds present in the Leaucaena
Leococephala seeds and their corresponding percent compositions.

2.3.4 Ipil-Ipil Uses

It has different importance to people such as a hedge, bush, tree or coppice. It can also be

used to feed grazing or herding animals. Its leaves can also be dried for use in concentrate feeds.

Some people use it in decorated bags.

2.4 Other Related Studies

2.4.1 Cassia Fistula

The Cassia fistula is a semi wild Indian laburnum also known as golden shower, a member

of the Leguminosae family and widely used for its medicinal properties that is recognized by the

British Pharmacopeia (Bahorun et al., 2005; Barthakur et al., 1995).

Based on the previous studies on this substance, C. fistula seeds are rich in glycerides with

linoleic, oleic, stearic and politics acids as major fatty acids. Wild seeds are also a source of crude

proteins comprising mainly globulin and albumin. It has also revealed that C. fistula seeds are rich

sources of cephalin and lecithin phospholipids and contain 11.8% carbohydrates. (Bahorun et al.,

2005; Barthakur et al.,1995).

 The effect of Cassia fistula dry extract additive on the wellbore cement was investigated

and they found out that this agent had no control over the filtration and reduced the free water

content of the 115 pcf slurry from 30 ml to 5 ml in an additive concentration of 0.2% bwoc. The

extract was found to be easy to mix with the cement system and had no adverse effect on the

cement system compressive strength. The optimum range of application for use in the cement was

determined as 0.05%-0.155 bwoc according to rheology test results.

The additive has a strong retardation capability and increased the thickening time of the

cement by 269 mins in low concentration of 0.15%. The author also conclude that this agent is

more effective in temperatures below 93°C. (Velayati, et. al, 2016).

The retardation mechanism of the retarder is an issue of controversy. However, the

probable mechanism of the retardation for C. fistula is investigated in this study. Generally, four

theories describe the possible mechanisms of the cement retardation, including: adsorption,

precipitation, nucleation and complexation theories. Retardation could be caused by a single

mechanism or a combination of the mentioned theories (Nelson, 2006). C. fistula is a source of

phenolic compounds and also amino acids. Phenolics are a class of chemical compounds consisting

of a hydroxyl (-OH) group bonded directly to an aromatic hydrocarbon group. Amino acids are

organic compounds containing amine and carboxylic (-COOH) acid functional groups along with

a side chain specific to each amino acid.

Hydroxycarboxylic acids have a powerful retardation action in medium temperatures. The

retarding action of hydroxycarboxylic acids is generally attributed to the presence of alpha or

betahydroxycarboxylic groups which are capable of strongly chelating a metal cation, such as
calcium. Highly stable 5 or 6 membered rings are formed, which partially adsorb onto the hydrated

cement surface, and poison nucleation sites of hydration products. Therefore, the probable

mechanisms of retardation are adsorption and nucleation.

0 100 200 300 400 500

Thickening Time (in mins.)

Table 2.2 Thickening time values for different C. Fistula additive concentrations in the cement.
2.4.2 The Potential of Ananas Comosus Leaf Fiber as a Retarding Additive to Well Cement

Another alternative to Leaucaena Leucocephala seeds is found to have cement retarding

properties as well. The potential of the pineapple leaf fibers as effective additive to well cements

have also been recorded and studied, with accounts from another study.

The authors from said study prepared slurries with 0.0%, 0.02%, 0.05% and 0.10% by

percent volume of cement and additive and tested them with three trials each in a high pressure-

high temperature (HPHT) consistometer. They used One-way and Two-way analysis of Variance

and Tukey post-hoc test. They found out that there is no statistically significant effect of PALF

content in the thickening time of cement (Arana, et. al, 2016)

 CHAPTER 3

CONCEPTUAL / THEORETICAL FRAMEWORK

3.1 Concept

The proponents intend to investigate the effect of dried Ipil-Ipil seed extract in the increase

of the curing time of cement and compressive strength as the concentration varies. It has been

found that this material has crude properties that may have retarding effects when applied unto

cement slurry. In order to accomplish this objective, an experimental method will be used wherein

the cement slurry will be mixed with the organic material with different concentration by weight

of cement.

The experimentation method starts with gathering raw material (Ipil-Ipil seeds) from our

local area. Then, these seeds will be dried with the appropriate temperature preferably under the

sun so that some water content within the seeds evaporates and to prevent microbial growth.

Afterwards, it will be grinded to maximize the surface area and turn the seeds into coarse powder.

Through filtration, it is easier to acquire the solid material or residue and this will be dried further

to eliminate bacteria. Afterwards, the resulting material will be mixed with the cement slurry. To

make the sample, specifically, the concentration by weight percentage will be observed strictly at

0.05%, 0.1%, 0.15%, 0.3%, 0.4% and 0.5% consecutively. These amounts are used due to retardant

limitations. If the weight composition exceeds these amounts, it will create an accelerating effect

to the hardening of cement, thus deviating the retarding purpose of our additives. The preparation

of additive is based on ASTM C109 which in 800 grams of cement is added with respective amount

of additive. To prepare further the cement slurry, 296 ml of water is added in every prepared

cement-additive mixture according to ASTM C109.

 In a separate set-up, neat cement will also be prepared according to API standards in order

to have data that can be used in comparison to the cement with the seed extract. To have positive

control, another sample of cement concentration shall also be prepared, but will be mixed with

commercial additives instead, and will also be subjected to the same temperatures and will have

the same weight composition. It will be repeated thrice to have better comparison in each

concentration and observe marginal error. Data will be gathered and recorded accordingly.

Figure 3.1 Experimental Set-Up

MOISTURE LOSS IN
CURING TIME

Untreated Cement WITH I2SE (3 samples each)

(3 samples)
0%
0.05% 0.1% 0.15% 0.3% 0.4% 0.5%
%

Compressive Strength Test

0% 0.05% 0.1% 0.15% 0.3% 0.4% 0.5%

Research Paradigm

INPUT OUTPUT
Cementing process is a very
This study will investigate the
critical concern that involves
determining the curing time of effect of the Ipil-Ipil as
cement at a certain depth. cement retarder.

The use of retarder is essential

to prolong the curing time and The sample will be examined
have good compressive by measuring its moisture loss
strength. at different concentrations and
testing the compressive
In response to the demand, strength of each specimen.
this study will focus in the
solid material extracted in
Ipil-Ipil seeds as a potential
retarder. The data will be recorded and
analyzed that could lead to the
conclusion of the study.

Definition of Terms:

API- stands for the American Petroleum Institute, an organization that defines the specifications

of material standards to be used in petroleum industry.

Additive(s) - a substance added to cement to change its characteristics to satisfy specific

conditions in the well.

Filtration- the process of filtering a fluid

Retarder- a substance added to cement to prolong the setting time so that the cement can be

pumped into the proper place.

Thickening time- the amount of time required for cement to reach an API-established degree of

consistency, or thickness. It begins when the slurry is mixed.

Settling time- It is the period wherein the cement loses its plasticity and has hardened to its solid

state.

Neat cement- a cement mixture with no additives other than water.

Nucleation- the initial process that occurs in the formation of a crystal from a solution, liquid or

vapor in which a small number of ions, atoms, or molecules become arranged in a pattern with the

characteristics of a crystalline solid.

Phenolic compounds- a class of chemical compounds in organic chemistry which consist of a

hydroxyl group (-OH) directly bonded to an aromatic hydrocarbon group.

Carbohydrate(s) - any of a large group of organic compounds occurring in foods and living

tissues and including sugars, starch, and cellulose.

Carboxylic acid- is a homologous series in which the compounds contain a functional group

called the carboxyl group (-COOH).

Lignoceric acid- is a normal carboxylic acid, a very long chain fatty acid.

Palmitic acid- is a common saturated fatty acid found in fats and waxes.

Palmitoleic acid- commonly known as omega-7, a rare monounsaturated fatty acid.

Amino acids – are substances containing nitrogen and hydrogen and which are found in proteins.

Linoleic acid- also known as an omega-6 fatty acids and a polyunsaturated essentilal fatty acid.
3.4 Research Hypothesis

Null Hypothesis: Ipil-ipil seed extract cannot delay the moisture content loss of the cement

slurry.

Alternative Hypothesis: Ipil-ipil seed extract can delay the moisture content loss of the cement

slurry.

3.4.1 Variables of the Study

INDEPENDENT DEPENDENT INTERVENING

VARIABLE VARIABLE VARIABLE

Concentration of additives Weight of moisture loss and Water amount per trial
on each trial compressive strength amount of cement
3.5 Research Process Flowchart

3.5.1 Cement Slurry with I2SE additive

Preparation of I2SE
additive and cement

Recording of curing
time of every
specimen every 24
hours
Testing the specimen
for compressive
strength

Recording and
analyzation of gathered
data

3.5.2 I2SE Preparation

Seed preparation

Drying process

Grinding

Extraction with ethanol

Separation of extract from liquid mixture through filtration

Drying the extract (solar drying method)

 CHAPTER 4

METHODS AND MATERIALS

4.1 Research Design and Methods

To make this study be possible, the research design and methods used was derived nearly

to the related studies and adjusted to the level of the researcher’s capabilities, understanding and

accessibility of apparatus and means. This will be done experimentally in order to simulate certain

condition and practical situation. The Ipil-Ipil seeds will be gathered from the vicinity of

Tiniguiban Heights, Puerto Princesa City, Palawan, which are readily available and then will be

dried under the sun to achieve complete drying. It will be grinded, until purely powdered or

pulverized. Then, these are treated in ethanol until seed oil reacts with the alcohol within 2 days.

To obtain the dried extract, the residue from filtered extract will be dried in an oven. It will be

done with permission in the Petroleum Engineering laboratory. Meanwhile to prepare cement

slurry at ASTM C109, some alternatives will be chosen due to unavailability of class G cement in

the local hardware therefore Ordinary Portland cement class A was used. The concentration of the

additive was prepared by mass basis at 0.05%, 0.1%, 0.15%, 0.3%, 0.4% and 0.5% bwoc while

the cement is weighed in 800 grams and the water measures 296 ml. In mixing the cement with

the additive, constant manual mixing will be used until it become homogenous in appearance.

Consequently, curing time will be observed until 7 days and be subjected for compressive strength

test procedure and data will be interpreted and set to conclusions.

4.1.1 Additive Preparation

4.1.1.1 Preparation of the Ipil-Ipil dried seed extract (I2SE)

1. The seed will be collected and dried. The selection of seeds is based on its maturity.

2. The dried seed will be grinded.

3. To achieve its dried extract, the grinded seeds will be treated in ethanol.

4. After 2 days, it will be filtered to remove excess oil and alcohol as well.

5. The solid extract or residue will be dried again.

4.1.2. Cement Slurry Preparation

1. The I2SE powder, Class A Portland cement and distilled water will be weighed using the

electronic balance, respectively.

2. The weighed I2SE and class A Portland cement will be mixed manually until they are

completely homogenous.

3. When I2SE and Class A Portland cement were completely dry mixed, appropriate amount of

purified water will be poured to have a saturated cement slurry and wait for 24 hours to observe

curing time. This is done separately based on respective concentration of additive.

 % Vol of Cement and Amount of retarder Portland Cement Purified Water (mL)
Additive (grams)
0 0 800 296
0.05 0.4 800 296
0.1 0.8 800 296
0.15 1.2 800 296
0.3 2.4 800 296
0.4 3.2 800 296
0.5 4.0 800 296
Table 4.1The table shows the weight percentage of additive added to the cement to meet the
specification of the cement slurry based on ASTM

4.1.3 Moisture Loss Content Procedure

1. The cement slurry being molded in 2 cubic inch molder is removed after 24 hours. Every trial

is measured and set as initial weight.

2. Next weighing method is observed every 24 hours until 7 days to set as final weight.

3 The recorded data in terms of grams will be interpreted if there is moisture loss.

4.1.4 Compressive Strength Test Procedure

1. Cement specimens are subjected to compressor to determine the strength of every trial.

2. Data is analyzed.
4.2 Materials and Instruments

 Pulverized Ipil-Ipil seeds

 Funnel

 Series of 2 cubic-inch cement molder

 Portland Cement

 An electronic balance

 Compressive strength tester or Strength Testing Unit

 Purified water
 Chapter 5

RESULTS, ANALYSIS AND FINDINGS

The collected data gained from series of test concludes that I2SE additives had better

results when introduced to cement slurry. The data indicates that the concentration of additive has

restrictions to accumulate a retarding effect on the samples whereas in higher concentrations the

effects altered into reverse action. Findings and analysis were presented by both qualitative and

quantitative analysis.

5.1 Qualitative Analysis

The figure shows that using the I2SE additive made the cement sample resistant from easily

drying. It has been observed that the moisture content of neat cement has difference compared

from with I2SE additive based on weight basis. Moisture content during hardening time signifies

the retarding or accelerating effect of the cement. All the samples exhibited moisture loss upon

hardening but the least percent I2SE content shows retarding effect.

Figure 5.1.1 Cube Test Specimen with different concentration of I2SE by weight of cement basis
 Figure 5.1.2 Cement Slurry without I2SE additive

Figure 5.1.3 Cement slurry with 0.4g of I2SE additive

Figure 5.1.4 Cement slurry with 0.8g of I2SE additive

Figure 5.1.5 Cement slurry with 1.2g of I2SE additive

Figure 5.1.6 Cement slurry with 2.4g of I2SE additive

Figure 5.1.7 Cement slurry with 3.2 of I2SE additive

 Figure 5.1.8 Cement slurry with 4g of I2SE additive

Figure 5.1.9 Cement specimen during Compressive Strength Test

Figure 5.1. 10 Final appearance of cement specimen after compressive strength test
 5.2 Quantitative Analysis

The data gathered from the test performed indicates a better result of adding I2SE amount
into the cement slurry.

Ave. moisture
Sample Ave. weight loss Ave. max load
loss
1 1.2 0.19 50
2 0.5 0.38 43
3 1.54 0.46 32
4 2.44 0.45 39
5 3.58 0.72 40
6 2.98 0.68 30
7 5.11 1.05 31
Table 5.2.1 Summary of data gathered from different parameter test

T Average weight of cement sample per day in grams

R
I by Amount
A weight of I2SE
L of (grams)
S cement 1 2 3 4 5 6 7
(%)

1 0 0 268.3333 267 266.3333 266.3333 266.3333 265.6667 265

2 0.05 0.4 265.6667 265.3333 264 264.6667 263.3333 265 264.3333
3 0.10 0.8 282 279.6667 278.6667 278.6667 277.6667 279.3333 277.6667
4 0.15 1.2 286.6667 282 281 281 281 281.3333 279.6667
5 0.30 2.4 279.6667 273.3333 270.3333 270.6667 270 270.6667 269.6667
6 0.40 3.2 257 251.6667 250 249.3333 249 250.3333 249.3333
7 0.50 4 248 238.6667 239.3333 237 236 236.6667 235.3333

Table 5.2.2 shows the weight of different concentration of additive relative to moisture loss of the
cement. As the curing time passes by, some of the samples lost its weight differentially relative to
the concentration of the I2SE per sample. It is also being observed that as the concentration of the
I2SE increases the initial weight at day 1 decreases with an increment higher than that of the
untreated cement resulting to acceleration effect.
Table 5.2.3 Average Weight Loss of the Samples based on Hardening Time

SAMPLE By weight of Amount of I2SE (grams) Average Percent Weight

cement (%) Loss %
1 0 0 1.2
2 0.05 0.4 0.5
3 0.10 0.8 1.54
4 0.15 1.2 2.44
5 0.30 2.4 3.58
6 0.40 3.2 2.98
7 0.50 4 5.11

Table 5.2.3 shows the average percent weight loss conducted on the cement from the initial to final

curing time. As the cement hardening time progresses, the weight loss increases accordingly to the

amount of the I2SE added to the slurry whereas percent bwoc also increases similarly.

Nevertheless, not all samples adhere to weight loss. Sample 2 garnered the lowest possible value

compared to the untreated cement, which clearly indicates the retarding effect of the I2SE.

Figure 5.2.1 Percent Weight Loss of Different I2SE Concentration vs. Untreated Cement

Percent Weight Loss

6

0
Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7

Sample 1 Sample 2 Sample 3 Sample 4 Sample 5 Sample 6 Sample 7

Figure 5.2.1 presents the graphical interpretation of the average weight loss of the different

concentrations in comparison to untreated cement at sample 1. . The graph presented shows that

value above the untreated cement automatically considered as accelerator. It was noticeable that

sample 2 at 0.4 concentration yield to minimal weight loss. This was one of the basis of considering

0.4 g I2SE of sample 2 to be tested further to validate the retarding effect of the cement.

Figure 5.2.2 Daily Moisture Loss Trend from Initial to Final Hardening Time

MOISTURE LOSS
4
3.75
3.5
3.25
3
2.75
2.5
2.25
2
1.75
1.5
1.25
1
0.75
0.5
0.25
0
M1 M2 M3 M4 M5 M6

Sample 1 Sample 2 Sample 3 Sample 4

Sample 5 Sample 6 Sample 7

Figure 5.2.2 shows the trend of daily moisture loss of different concentration. It shows the

relative water loss prior to the day which was the moisture content was measured. The data

presented how the moisture loss varied from one point to another, how close the losses were

from each other. Therefore, result of the trend were not the basis to determine the possible

retarder amongst the concentrations experimented.

Figure 5.2.3 Daily Average Moisture Loss

Daily Average Moisture Loss

1.2

0.8

0.6

0.4

0.2

0
1 2 3 4 5 6 7
Samples

Table 5.2.3 Compressive Strength Test Result of Day 2 Curing Time at 25C

I2SE concentration
Sample Trial Mix with
No. Bwoc I2SE (g) Max load (kN) Strength (psi)
1 0% 0 50 2905
2 0.05% 0.4 43 2397
3 0.10% 0.8 32 1751
4 0.15% 1.2 39 2052
5 0.30% 2.4 40 1849
6 0.40% 3.2 30 1640
7 0.50% 4 31 1541

Table 5.2.3 shows the compressive strength of cement on 48 hours hardening time. At 25C,

the compressive strength yielded to 1541-2905 psi overcoming the required WOC strength of 500

psi. The data shows that as the concentration of I2SE in cement sample increases the compressive

strength gradually decreases; and that the relationship of the strength is directly proportional to the

maximum load it can withstand and inversely proportional to the concentration of I2SE.
Figure 5.2.4 Compressive Strength (psi) in 48hrs Hardening Time at 25 °C

Compressive Strength
4000

3000

2000

1000

0
0g 0.4g 0.8g 1.2g 2.4g 3.2g 4g.

0g 0.4g 0.8g 1.2g 2.4g 3.2g 4g.

Table 5.2.4 Compressive Strength and Maximum Load on 7 Days Hardening Time at 25C

Sample 2
0.4g I2SE
0.05 bwoc
Max load (kN) Strength (psi)
TRIALS
1 53.8 2663.3
2 62.5 3109
3 55 2894
Average 57.1 2888.7
Figure 5.2.5 Compressive Strengths of Retarder 0.4g I2SE vs. Average Untreated Cement

Compressive Strength psi

3500

2500

1500

500

Trial 1 Trial 2 Trial 3 Average I2SE Average Untreated

-500

Trial 1 Trial 2 Trial 3 Average I2SE Average Untreated

Table 5.2.4 and Figure 5.2.5 shows the compressive strength of sample 2 that has 0.4 g of I2SE

additive as a retarder to cement slurry. The compressive strength of the three (3) trials of the

given sample produced a relatively close strength that ranges from 2600-3000 psi or about 181

atm- 204 atm. The result clearly shows that the average compressive strength of the 0.4g I2SE is

closely comparable to the untreated cement that indicates that the given concentration can extend

the cement from hardening before it reaches its displacement area.

 Chapter 6

SUMMARY, CONCLUSION AND RECOMMENDATIONS

The main focus of this study is to find an alternative and reduced cost cement retarder to be used

in cementing operation on oil and gas wells. Hypothesis was made throughout the chemical composition of

Ipil-Ipil seed extract as an organic material with higher amount of fatty acids that is enough to slow down

the hardening of the cement.

There were 18 cement specimen for with I2SE additive while 3 samples for neat cement. Some

physical tests were conducted to accumulate data and to support the reliability of the study, where the total

21 cement specimens are measured through determining moisture content loss from initial day of cement

slurry preparation to final day of curing.

Each sample were weighed from its slurry state on daily basis until as its hardened that leads to

determine the moisture content. Graphically, at 0.05% bwoc cement sample has the least amount of

moisture loss compared to neat cement. As the I2SE additive concentration increases, the greater amount

of moisture losses.

After curing time test is conducted, those samples are subjected to compressive strength test which

the data revealed that at 0.05% bwoc cement sample exerted good compressive strength when compared to

neat cement. In concrete cement standard, this concentration complies the desired amount of 2500 psi

compressive strength.
6.1 Conclusion

The following conclusions were made according to the results of the study:

1. The high moisture content in the cement makes a retarding effect at low concentration of the

additive. It is observed that when I2SE is added in high amount it accelerates the rate of

dehydration.

2. The researchers found out that the optimum concentration of the additive that can be added to

retard the hardening rate is 0.05% bwoc.

6.3 Recommendations

The proponents highly recommend the following in order to achieve a more reliable data such as:

1. Conduct other parameter test such as thickening time and settling time test by following

laboratory standards.

2. Add cement-additive concentration that is more closely related to the neat cement properties

aside from what had been tested in the study.

3. In preparation of additive, methanol is more economical to use for oil extraction due to its

minimal cost.

4. . The use of class G cement can be more appropriate to use as the material being blended with

the additive.
 GLOSSARY

Wellbore - A hole that is drilled to aid in the exploration and recovery of natural resources
including oil, gas, and water.

Accelerators - Admixtures that accelerate the hardening of cement slurries.

Retarders - Admixtures that slows down the hardening of cement slurries.

Extenders - Lightweight additives used to reduce the weight of the slurry

Dispersants - Are additives used extensively in cement slurries to improve the rheological
properties that relate to the flow behavior of the slurry.

Viscosity - The state of being thick, sticky, and semifluid in consistency, due to internal friction.

Additives/ Admixtures - Chemicals used to modify the properties of cement slurries for use in
oilfield well-cementing applications

Compressive Strength - The resistance of a material to breaking under compression.

Saccharide - Any of a series of sweet-tasting, crystalline carbohydrates, especially a simple sugar

(a monosaccharide) or a chain of two or more simple sugars (a disaccharide, oligosaccharide, or
polysaccharide).

Weighting Agents - Additives used to increase slurry density for control of highly pressured
wells.

Settling/Setting time - The time taken for a measuring or control instrument to get within a
certain distance of a new equilibrium value without subsequently deviating from it by that
amount.

Slurry - A semiliquid mixture of fine particles of cement suspended in water.

Lignosulfates - Water-soluble anionic polyelectrolyte polymers: they are byproducts from the
production of wood pulp using sulfite pulping.

Hydrocarboxylic acids - A class of chemical compounds that consist of a

carboxylic acid substituted with a hydroxyl group on the adjacent carbon.
Curing/Hardening Time - The time at which a cement slurry loses its plasticity

Neat Cement - Pure cement and water only mix

Primary Cementing - Cementing operations that provide zonal isolation in wellbores.

Secondary Cementing - Cementing operations performed to repair primary cementing problems

Two-plug Method - A technique that involves the drill pipe or tubing to be placed at the
planned plug base depth. Subsequently the cement slurry is placed on top of a mechanical device
(such as a bridge plug) or viscous fluid or mud serving as the plug base.

Density - The mass per unit volume of a substance

API - Abbreviation for American Petroleum Institute

ASTM - Abbreviation for American Society for Testing and Materials; is an international
standards organization that develops and publishes voluntary consensus technical standards for a
wide range of materials, products, systems, and services.
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 APPENDICES
Appendix A: Ethyl Alcohol (Ethanol) Material Safety Data Sheet
Figure A.1 MSDS- Ethyl Alcohol (www.science lab.com/msds/ethylalcohol)
Section 11: Toxicological Information
Appendix B. Materials and Equipment

Photograph of dried Ipil-Ipil seeds using solar method

Pulverized Ipil-Ipil Seed Extract

 Funnel

Series of 2 cubic-inch cement molder

 Portland Cement

An electronic balance
Compressive strength tester or Strength Testing Unit

Purified water
 Ethanol

Empty Bottles