CHAPTER ONE

INTRODUCTION AND LITERATURE REVIEW

1.1 Introduction

Every year, a huge amount of cement product is produced and used for the construction

of buildings and roads.In Nigeria, use of poor quality cement In structural and

constructional works has caused loss of lives and properties. So quallty assurance of

cement has become an important and critical factor. The cement to be used in

construction must have certain qualities in order to play its roles effectively in structure.

A number of physical and chemical tests are performed in the laboratories of cement

industries and constructional companies to ensure that the cement is of the desired

quality and it conforms to the requirement of relevant standards as outlined by the

Standard Organization of Nigeria (SON) and American Society for Testing and Materials

(ASTM). There are several brands of OPC (Ordinary Portland Cement) available in the

market but their chemical compositions are the same but often vary in physical

properties due to the variation in the amount of chemical constituents. The study was

aimed to conduct comparative chemical analysis of some cements products by

assessing the chemical constituents that include SiO 2, Al2O3, Fe2O3, lime content,

magnesium oxide, SO3, insolubIe residue (IR) and loss on ignition (LOI). Three brands

of cement that include Sokoto Cement Dangote and BUA Cements were chosen for the

comparative analysis.

Definition of cement

Cements in general are adhesive substances of all kinds but, in a narrow sense they

are binding materials used in building and civil engineering constructions. Cement of

1
this kind are finely ground powder that when mixed with water, set to a hard mass.

Setting and hardening result from hydration, which is a chemical combination of the

cement compounds with water that yields sub microscopic crystals or a gel-like material

with a high surface area. Constructional cements, which will even set and harden under

water are often called hydraulic cements. The most important of these is portland

cement (Encyclopaedia Britannica, 2008).

1 .2 Portland cement
Ordinary Portland cement (OPC) is the most common type of cement in general use

around the world because it is a basic ingredient of concrete. Mortar stucco and most

non specially grout. It is a fine powder produced by grinding Portland cement clinker.

Portland cement clinker is a hydraulic material which shall consist of at least two-third

by mass Of calcium silicates (3CaO.SiO 2 and 2CaO.Si02). The remainder consisting of

aluminium and iron containing clinker phases and other compounds (Aldieb& Ibrahim.

2010).

There are three fundamental stages in the production of Portland cement (Aldieb and

Ibrahim. 2010):

1. Preparation of the raw mixture.

2. Production of the clinker.

3. Preparation of the cement. (Aldieb and lbrah'un. 2010).

The raw materials for Portland cement production are the mixture (as fine powder in the

'dry process') of minerals containing calcium oxide, Silicon oxide, aluminum oxide, ferric

oxide and magnesium oxide. The raw materials are usually quarried from local rocks,

2
which in some places are already practically in the desired composition (homogenous

type) and in other places it requires addition of clay and limestone, as well as iron ore,

bauxite or recycled materials. The homogeneity of feed chemical composition has an

important relationship to fuel consumption, kiln operation, clinker formation and cement

performance.

Cement quality is typically assessed by its compressive strength development in mortar

and concrete. The basis for this property is well burned clinker with consistent chemical

composition and free lime. There are only two reasons for the clinker free lime to

change in a situation with stable kiln operation: Variation in the chemical composition of

the kiln feed or variations in its fineness. Variations in fineness depend on possible

changes in raw materials or in operation of the raw mill. Variation in chemical

composition is related to raw mix control and the homogenization process. To ensure a

constant quality of the product and maintain stable and continuous operation of the kiln,

attention must be paid to storage and homogenization of raw materials and kiln feed

(Aldieb and Ibrahim, 2010).

Cement making is essentially a chemical process industry and has much in common

with the manufacture of so called heavy chemicals such as sodium hydroxide and

calcium chloride. Close control of the chemistry of the product is essential if cement with

consistent properties is to be produced. This control applies not only to the principal

oxides which are present but also to impurities, which can have a marked influence on

both the manufacturing process and cement properties. The major constituents of

cements are presented in Table 1 (Moir, 2010).

3
Table 1.1: Major constituents of cement
Main constituents Cement chemist shorthand %

SiO2 S 21.1

Al2O3 A 5.6
Fe2O3
F 3.0
CaO
C 65.5

Total
95.2

About 1.0-5.0% of the remaining compositions are calcium sulphate, alkali sulphates,

unreacted calcium oxide (free lime), magnesium oxide and other minor constituents

including impurities left over during the clinkering and grinding steps (Taylor, 1997).

Minor constituents are illustrated in Table 2 (Moir, 2010)

Table 1.2: Minor constituents of cement

Minor constituents %
Mn2O3 0.05
P2O5 0.15
TiO2 0.30
MgO 1.50
SO3 1.2
Loss on ignition 0.50
K2O 0.72
Na2O 0.18
Flourine 0.04
Chloride 0.02
Trace metals 0.014

Total 4.674

A chemical analysis of Portland cement clinker shows it to consist mainly four oxides:

CaO (lime), SiO2(silica), Al2O3 (alumina) and Fe2O3 (iron oxide).

4
In Order to simplify the description of chemical composition, a form of shorthand is used

by cement chemists In which the four oxides are referred to respectively C, S, A and F.

By expressing the chemical constituents in the form of oxides rather than the individual

elements of silicon (Si), calcium (Ca), Aluminium (Al) Iron (Fe), has the advantage that

the analysis total should come close to 100 %, and this provides a useful check for

errors. Oxidizing conditions are maintained during the burning process and this ensures

that the metallic elements present are effectively present as oxides although combined

In the clinker as minerals. The source of lime for cement making is usually limestone or

chalk.

Typically. 80% of the raw mix consists of limestone. it is referred to as the primary raw

material. The secondary raw material, which provides the necessary silica, alumina and

iron oxide, is normally shale or clay. Small Quantities of sand or iron oxide may be

added to adjust the levels of silica and Iron oxide in the mix. When proportioning the raw

materials an allowance must be made for ash incorporated into the clinker from the fuel

that fires the kiln. Most cement plants worldwide use finely ground (pulverized) coal as

the primary fuel. By-product fuels such as the residue from oil refining (petroleum coke)

and vehicle tyres are increasingly being used to partially replace some of the coal. The

ratio of CaO to the other oxides is lower in the clinker than in the raw mix as a result of

the incorporation of shale from the coal ash. The levels of the oxides are also increased

as a result of decarbonation (removal of CO2), (Mair. 2010).

The Process of clinker formation is described in Figure 1.

5
Fig 1. A schematic View of the clinker formation reactions

The clinker reactions are summarized below

CaCO3 CaO+CO2................. (1)

Cao+2SiO2 C2S.................. (2)

CaO+C2S C3S..................... (3)

3CaO+Al2O3 C3A................. (4)

4CaO+Al2O3+Fe2O3 C4AF... (5)

About 90-95% of Portland cement is composed of the four main cement tricalcium

minerals, tricalcium silicate (C3S), dicalcium silicate (C2S), tricalcium aluminate (C3A)

and tetracaIcium aluminoferrite (C4AF) with each of them playing different roles in the

hydration process that converts the dry cement into hardened cement paste (Tennis

and Bhatty. 2006).

1.2.1. Functions of clinker minerals

The functions of the clinker minerals are discussed below;

1. Alite (C3S): produce most of the cement strength up to and including 28 days with

the release of moderate quantities of heat. Each 10% increase in the C 3S content

increases the 28 day EN 196 mortar strength by about 5Mpa.

2. Belite (C2S) reacts slowly with low heat evolution to influence mainly later strength

(> 28 days).

3. Aluminate (C3A): reacts rapidly with H 20 releasing large quantity of heat. Higher

aluminate levels usually increase the higher water demands and very early strength

6
 development and shortening setting time. It also enhance hydration of alite (C 3S)

and belite (C2s) but it’s also the most susceptible to sulphate attack.

4. Ferrite (C4AF): reacts rapidly with H20 to give off moderate amount of heat. Ferrite

makes a small contribution to the strength but the Iron fraction is mainly responsible

for the dark coloring of cement (Taylor, 2009).

1.2.2 Cement modulus/ratio

For a long time cement was manufactured on the basis of practical experience collected

from the process of production. When comparing chemical analyses at Portand cement

(Feed raw materials and/or clinker) (Aldaeb and Ibrahim. 2010).

The cement modulus or ratios are:

1.2.3 Silica ratio (SR)

It I the production of SiO2 to the total of Al2O3 and Fe2O3, given as following:

SR= SiO2/Al2O3+Fe2O3

Increase in silica ratio impairs the burnability of the clinker, by reducing liquid phase

content and tendency toward formation of coating in the kiln. Moreover, increase in

silica ratio also causes a slow setting and hardening of the cement. When silica ratio is

decreased, the content of liquid phase increase, this improves the burnability of the

clinker and the formation of coating in the kiln. Generally the silica ratio runs between

(1.9-3.2), low values for silica ratios can be accepted as low down to 1.5.

1.2.4 Alumina ratio (AR)

The cement is characterised by the proportion of alumina to Iron oxide given as follows:

7
AR=Al2O3/Fe2O3

Values of alumina ratio are in the range from 1.5 to 2.5. The alumina ratio (AR)

determines the composition of liquid phase in the clinker, when it is lower than 1.5 both

oxides are present in their molecular ratios and therefore only tetracalcium-alumino

ferrite can be formed in the clinker; therefore, the clinker cannot contain tricalcium

aluminate. This is the case called Ferraricement which is characterized by low heat of

hydration, slow setting and low shrinking. A high alumina ratio together with a low silica

ratio results among other things, in a fast setting of the cement: this requires the

addition of a hiqher gypsum rate to control the setting time.

1.2.5 Lime saturation factor (LSF)

To attain complete lime saturation in the clinker the total silica must be combined as

C3S, all iron oxide must combine with the equivalent amount of alumina to C 4AF, and

the remaining alumina must combine to C 3A. This formula expressed as following for

MgO lower than 2%.

LSF= 100(CaO+ 0.75MgO)/2.85Si02+1.18AI2O3+0.65Fe2O3

For technical purposes good values of LSF ranged between (80-95) (Aldieb and

Ibrahim, 2010).

1.2.6 Chemical analysis of cement

The testing procedures based on American Standards (ASTM, 1986) have been

followed for chemical analysis of Portland cement. Amount of total SiO 2, Al2O3,

Fe2O3,lime content. MgO, SO3, IR, free lime and LOI were determined.

8
1.2.7 Aim

The aim of this work is to determine the chemical properties of three types of cements,

namely: BUA, Dangote and Sokoto Cements.

1.2.8 Objectives

The objectives are as follows:

1. To determine the chemical properties of the three brands of cement (Sokoto,

Dangote and BUA Cements) such as Insoluble residue (IR), free lime, Loss on

ignition(LOI),SiO2, SO3,CaO, Fe2O3, and Al2O3 analysis.

2. Compare the composition of the three bands with the standard established by SON

and ASTM

9
 CHAPTER TWO
MATERIALS AND METHOD
2.1Materials

The samples used for the research are BUA, DANGOTE and SOKOTO Cements,
they were coded with codes known to the researcher.
The materials / equipments used in the analysis are listed in Table 3;
Table 2.1: Materials/ equipments used
MATERIAL Model MANUFACTURER
Claisse M4 fluxer M4-10 Corporation

ScientifiqueClaisse,Canada

Mettler-Toledo MS204TS100 Mettler -Toledo

Weighing Balance GmbH.Switzenand

Thermo Scientific ARL OPTIMX Thermo scientific,USA

XRAY Analyzer

Platinum crucibles .................. Canada

Beakers, conical flasks pyrex

England

Filter paper .................. Whatman GmbH,

Germany

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Table 2.2: Reagents used for the research
REAGENT TYPE PERCENTAGE PURITY

Ammonium chloride AR 99%

Bromophonol BDH -

Ethanol AR 95.6%

Ethylene glycol AR 99%

Methanol AR 99.5%

Methyl red indicator BDH -

Hydrochloric acid AR 36.5-38%

Lithium tetraborate AR 90%

Sodium hydroxide AR 98.9%

2.2 Methods and Procedures

The procedures used during the research are discussed below.

2.2.1 Determination of free lime

The sample (1.0000g + 0.0005g) was weighed into a flask (500mL) and dry sand (2g)

was added. the content was mixed thoroughly and glycol solution (40mL) was added to

it, it was covered with a stopper, the flask was shaked vigorously before it was placed in

the oven at 65-70°C for 30 minutes, the solution was shaken manually after each 5

mins, the mixture was filtered under suction through a dry filter and was washed three

11
times with methanol by carefully rinsing the flask, three drops of bromophenol blue were

added and was titrated with HCI (0.1M) until the color changed (ASTM, 1986).

Calculations

%free lime= factor X Volume (ml) HCl

A sample calculation is presented in Appendix A

2.2 Deteminatlon of Insoluble residue

The sample (1.0000 + 0.0001g) was weighed into a beaker (250mL), the sample was

dissolved in warm distilled water, concentrated HCI (5mL) was added and was diluted

using warm distilled water (100mL), It was stirred well with glass rod (3 times), the

solution was heated to boiling point on a hot plate, It was filtered using whattman filter

paper, the beaker was washed with hot distilled water (4 times), the filter paper with the

residue were transferred into a beaker(250mL), NaOH (100ml, 0.1N), solution was

added into the beaker. The grading of the beaker was used, 3 drops of methyl red

indicator were added, the mixture was boiled on the hot plate, the heat was put off and

4 drops of concentrated HCI were added until the colour changed to pink, the solution

was filtered again using whatman filter paper and the filter paper was washed 4 times

using NH4CI solution (0.2N), a rubber scraper was used to remove all precipitate that

adhered during washing. An empty crucible was ignited for 5 minutes in the furnace

(950°C) and was allowed to cool in a dessicator to ambient room temperature, the

empty crucible was weighed as W1 the filter paper together With the residue were put

into the crucible, the sample was ignited in the furnace at a temperature of 950°C for 30

12
minutes, it was allowed to cool to ambient temperature In a dessicator, it was weighed

again as W2 (ASTM, 1986).

CALCULATION

%IR = final weight (W2) – Initial weight (W1)

A sample calculation is presented in Appendix B

2.2.3 Determination of Loss On ignition

An empty platinum crucible was weighed and recorded as W 1 and The empty crucible

with the sample (4.0000-4.5000g) was weighed as W 2 , The sample was ignited in the

furnace (950°C) for 30 minutes and allowed to cool to ambient temperature and

weighed again after heating and recorded as W 4 and W3 is (W1+W2).

Calculation

%LOI = (W3 – W4/ W2) x 100 (Shinkafi and Vikingson 2003).

A sample calculation is presented in Appendix C

13
 CHAPTER 3

RESULTS AND DISCUSSION

3.1 Results

Results of the clinker minerals in the three brands of cement are given in the table 5:

Table 3.1: percentage composition of clinker minerals.

SAMPLE C3S(%) C2S(%) C3A(%) C4AF(%) TOTAL

SC1 66.12 5.69 9.99 10.41 92.21

DC2
90.76 0.00 7.72 9.80 108.74

BC3
56.58 15.96 6.61 13.17 92.32

3.2 Discussion

SC1 and BC3 cements have their C3S value within the range specified by ASTM which is

45.0-65.0%, however,DC2 cement has its C3S value above that specified by ASTM.

The C2S is responsible for the later strength of cements (taylor, 2009),absence of C2S

in DC2 cement has negatively affected it’s later strength.

14
The C3A is responsible for the early strength (that is 1 day, 2 days, 3 days, and 7 days)

of cement (taylor, 2009), from table 5, all the three brands of cement have their C3A

within the range specified by ASTM which is 10-15%.

The C4AF is responsible for the coloration of cement, because of the higher value C 4AF

in BC3 cement (i.e 13.17 from the table), this make it to be darker than SC 1 and DC2

cements which is 10.41 and 9.80%.

Table 3.2: percentage composition of the major chemical constituents for the three

brands of cement.

SAMPLE CaO% SiO2% Al2O3% Fe2O3%

SC1 65.88 19.91 5.73 3.30

DC2 67.54 17.48 4.52 2.93

BC3 65.67 20.97 5.05 4.16

According to ASTM c150-07 the ranges for percentage CaO, SiO, AL 2O3, Fe2O3 are 61-

67, 19-23, 2.5-6.0 and 0-6.0 (omoniyi and okunola, 2015).

The percentage CaO all the three brands (SC 1, DC2, BC3 cements) is within the

specified range of ASTM.

The three of brands cements have the normal percentage of SiO 2, AL2O3, Fe2O3 within

the ASTM specification as shown in table 6.

15
Table 3.3: loss on ignition and some minor constituents in the three brands of cements

SAMPLE LOI FreeCaO SO3 MgO IR

(%) (%) (%) (%) (%)

SC1 3.72 0.87 1.15 0.00 2.20

DC2 9.12 0.50 2.25 0.00 1.10

BC3 3.90 0.84 2.32 0.00 2.54

According to the ASTM C150 specification, the percentage composition for LOI, free

lime, SO3, MgO and insoluble residue (IR) are 3.0-4.0, 1.00, 2.90, 6.00 and 0.75

(ASTM, 1986).

The percentage LOI of SC1 and BC3 cements are within the specified range of ASTM,

however %LOI in DC2 cement is above the ASTM specification as shown in table 7, this

indicate that the product are poor in mineral content and high in combustible material

(AOAC, 1990).

Furthermore, the percentage free lime content in the three brands of cements are within

the specification of ASTM, but the percentage of insoluble residue in the three brands of

cements is above the specified range of ASTM, with SC 1 and BC3 having the highest

percentage, this can lead to cracking.

16
Table 3.4: LSF (lime saturation factor), AM (alumina modulus) and SM (silica modulus)

SAMPLE LSF AM SM

(%) (%) (%)

SC1 96.33 1.74 2.21

DC2 106.28 1.54 2.35

BC3 91.11 1.21 2.28

According to the ASTM C150 specification, the percentage composition of LSF, AM and

SM are 95-97, 1.5-1.8, 2.4-2.6 (Moir, 2003).

It can be seen in the table 3.4, all the three brands of cements have their AM and SM

value within the specified range, these improve the burn ability of the clinker and

formation of liquid phase in the clinker (Aldieb and Ibrahim, 2010), SC 1 and DC2

cements recorded high LSF value, BC3 has an LSF value that is within the rang

17
 CHAPTER FOUR

CONCLUSION AND RECOMMENDATION

4.1 Conclusion

Based on the research carried out, the three brands of cement have shown conformity
with the specifications of American Society for Testing and Material (ASTM) and
Standard Organization of Nigeria (SON) in their free lime content, SC 1 and BC3 and DC2,
BC3 and SC1 has slight deviation in their free lime content (0.84% and 0.87%
respectively) while DC2 have free lime content far lower than aforementioned brands
(0.49%). SC1 and BC3 have LOI within the standard range and slight deviation in their
LOI value (3.72% and 3.90% respectively) while the LOI value in DC 2 is above the
standard LOI value (9.12%). IR analysis carried out shows that all the cement samples
used for analysis are above the ASTM specification, DC 2 has the lowest IR value among
the three brands of cement (1.05%) while SC 1 and BC3 have higher IR content than DC2
but have slight deviation in their IR Content (2.19% and 2.54% respectively).

4.2 Recommendation

i. there should be proper awareness for construction industries and brick manufacturers

on the quality of cement to be used for various constructional activities to reduce the

case of building collapse which has become a threat to the society.

ii. There should be continous quality development of the three brands of cements and

other brands to meet up with all the requirements of national and international standard.

iii. Further research should also be carried out on the brands of cements

18
References

Aldieb A.M., Ibrahim G.H, (2010), Variation of feeds chemical compositions and its

effects on clinker formationsimulation-Process; Proceedings of World Congress

on Engineering and computer Science (WCECS). V:2 San Francisco, USA

Association of Official Analytical Chemists (1990), Official Methods of Analysis, 15 th

edition (AOAC), Washington DC. P56

ASTM(1986), annual book of ASTM. Cement, lime American society for testing and

materials, PA, USA.

Moir G.(2003), advanced concrete technology constituent materials. Repika Press,

PVT limited, India Pp 4-12

Omoniyi I., Okunola O.J (2015), Comparative Studies of chemical Properties of Some

Selected cements in Nigeria. Nigerian Journal of Technological Developments

2:2: Pp57

Shinkafi H., Vikingson J. (2003). Cement Company of Northern Nigeria Laboratory

Manual. Pp 1-12

Taylor H. F W. (1997). Cement Chemistry, Thomas Telford Publishing, London. Pp 276-

284

Taylor I. (2009), Cement Operation Course. Intake Service Pty Ltd. London Pp 17-23

19
Tennis, P. D., Bhatty J.I (2005), Portland Cement Characteristics. Concrete Technology

Today. USA. (26)3.

APPENDICES

Appendix A: Determination Of Free lime

BUA Cement Sample

%Free lime = Volume of HCl × Factor

= 2.20 × 0.38

=0.84%

Dangote Sample

%Free lime = Volume of HCl × Factor

= 1.3 × 0.38

= 0.494%

Sokoto Cement Sample

%Free lime = Volume of HCl × Factor

= 2.3 × 0.38

=0.874%

Appendix B: Determination of IR

Bua Cement Sample

20
%IR = W2 – W1 × 100

W1= 25.5076%

W2= 25.53306%

%IR = 25.53306 - 25.5076 × 100

=2.54%

Dangote Cement Sample

W1 = 25.5189%

W2 = 25.5408%

%IR = W2 – W1 × 100

= 25.5408 - 25.5189 × 100

= 1.05%

Sokoto Cement Sample

W1 = = 25.5189%

W2 = 25.5408%

%IR = W2 – W1 × 100

= 25.5408 - 25.5189 × 100

= 2.19%

APPENDIX C: Determinationn of LOI

21
%LOI = W3 – W4 /W2 × 100

BUA SAMPLE

W1 = 25.5142g

W2 = 4.4528g

W3 =25.5142 + 4.4528 = 29.9670g

W4 = 29.7932g

%LOI = 29.9670 - 29.7932 / 4.4528 × 100

= 3.90%

DANGOTE SAMPLE

W1 = 17.5721g

W2 = 4.5262g

W3 = 17.5721 + 4.5262 = 22.0983g

W4 = 21.6857g

%LOI = 22.0983 - 21.6857 / 4.5262 × 100

= 9.12%

SOKOTO CEMENT SAMPLE

W1 = 18.8404g

22
W2 = 4.1732g

W3 =18.8404 + 4.1732 = 23.0136g

W4 = 22.8384g

%LOI = = 23.0136 - 22.8384 / 4.1732 × 100

= 3.7189%

23