University of Nigeria

Research Publications

AGBAZUE, Vitus E.
Author

PG/M.Sc./88/6654
Title

Comparative Studies of Quality and Standards of

Cement Manuifactured
Department Faculty

Physical Sciences

Pure and Industrial Chemistry

October, 1990
Date

Digitally signed by Omenuko

Omenuko Sunday Ogbonna
Signature

DN: CN = Omenuko Sunday

Ogbonna, C = NG, O = University
Sunday of Nigeria, OU = Innovation Centre
Reason: I have reviewed this
Ogbonna document
Date: 2008.12.09 23:34:43 -12'00'
 COMPARATIVE S T U D I E S O F QUALITY AND
STANDARDS O F CENENT MANUFACTURED I N N I G E R I A

V I T U S E Z E AGBAZUE
( P G .~c./88/6654)
~

DEPARTMENT O F PURE AND I N D U S T R I A L CHEMISTRY

UNIVERSITY O F N I G E R I A , NSUKKAe

OCTOBER, 1990.
 UNIVERSITY O F N I G E R I A , NSUI(KR
DEPARTIWNT O F PURE AND INDUSTRIAL CHENI STRY

RESEARCH PROJECT
(cHEN. 582)

TITLE: COMPARATIVE S T U D I E S O F QUALITY AND STANDARDS

O F CEMENT MANUFACTURED I N N I G E R I A .

V I T U S E Z E AGBAZUE
(P~D.Sc./88/6654)

A RESEARCH PROJECT SUBMITTED I N PARTIAL FULFILMENT

O F THE REQUtREMENTS FOR THE AWARD O F MASTER O F
SCIENCE DEGREE I N THE DEPARTMENT O F PURE AND
INDUSTRIAL CHHVIISTRY, UNIVERSITY O F N I G E R I A , NSUKKA.

SUPERVISOR: DR. F. I. NWABUE

OCTOBER, 1990-
 CERTIFICATION

VITUS EZE AGBAZUE, a postgraduate student in t h e

Department of Pure and I n d u s t r i a l Chemistry, with
R e g i s t r a t i o n Number PG/iq. Sc. /88/6654 has sa-tisfa c t o r i l y
completed t h e requirements f o r course and r e s e a r c h work
f o r t h e degree of Master of Science (M,SC.) in
I n d u s t r i a l Chemistry.
The work embodied i n t h i s p r o j e c t r e p o r t i s
o r i g i n a l - and has n o t been submitted i n p a r t o r f u l l
f o r any o t h e r diploma o r degree of this or any o t h e r
University.

- - -

Prof. C. 0. Okafor D r . F. I, Nwabue

Head of Department Supervisor
 DEDI CAT I ON

D e d i c ~ t e dt o Benue Cement Company PLC.,

t h e producer of h i g h q u a l i t y Lion Brand
P o r t l a n d Cement - t h e Builders' F i r s t Choice.
 iii

I wish t o express my profound g r a t i t u d e t o my

p r o j e c t s u p e r v i s o r , Dr. Frank Ikenna Nwabue who
formulated t h i s p r o j e c t t o p i c and guided me s o l i d l y
throughout t h e work, even during h i s l e a v e of absence
from t h e LhiverQity. My s p e c i a l t h a n k s a l s o go t o t h e
Dept. of Pure and I n d u s t r i a l Chemistry (UNN) f o r
o f f e r i n g me p a r t - t i m e admission t o pursue p o s t g r a d u a t e
studies. I s a l u t e a l l t h e l e c t u r e r s of t h e Dept, f o r
t h e i r maximum co-operation. In particular I greet
D r . M.J. K e l l e h e r , Dr. V. C. Agwada and Dr. C.A. Nwadinigwe
f o r t h e i r most i n s p i r i n g encouragement,
I w i l l ever c h e r i s h t h e memory of my l a t e mother,
Madam Mgbafor Ejemennu Agbazue, t h e prime mover of my
e d u c a t i o n a l p u r s u i t s , whose sudden d e a t h o c c u r r e d while
t h i s c o u r s e was s t i l l on. My a p p r e c i a t i o n a l s o goes
t o my most s e n i o r b r o t h e r , I c h i e S, A. Agbazue who
sponsored me upto my f i r s t degree l e v e l , 1

T h i s programme would n o t have been p o s s i b l e i f n o t

f o r t h e approval, sponsorship and support it r e c e i v e d
from t h e Management of Benue Cement Company PLC, my
employer, I am t h e r e f o r e h i g h l y i n d e b t e d t o t h e
Managing D i r e c t o r and Chief Executive, Engr, B. A.1, Gemade; I

General Manager ( T e c h n i c a l ) , Engr, C. C, Aningo;

Assistant General Manager ( p r o d u c t i o n ) , Engr. S.I. Nyagba;
T r a i n i n g and Manpower Development Manager,
&gr. Onuonye Eluekezi a s w e l l a s a l l t h e s t a f f of
Q u a l i t y C o n t r o l Department. S p e c i a l t h a n k s a l s o go t o
t h e A s s i s t a n t General Manager (Ehgineering s e r v i c e s ) ,
Ehgr. M. I. Aende who has k i n d l y allowed me "ce use of
h i s cement technology t e x t books.
I cannot f o r g e t t h e courage and understanding of
my wife, Mrs. B. Ngo Eze Agbazue and my c h i l d r e n who
missed me s e v e r a l days and n i g h t s of my absence from home.
I acknowledge t h e i n v a l u a b l e c o n t r i b u t i o n of t h e
following people i n t h e c o u r s e of t h i s r e s e a r c h :
Dr. R.K. Sood of t h e U n i v e r s i t y of Calabar who i s my
former l e c t u r e r and a l l t i m e i n s p i r e r ; Nr. Ude Nba, a
f e l l o w p o s t g r a d u a t e s t u d e n t , being a l s o my one t i m e
s t u d e n t and a t r u s t e d f r i e n d ; M r . John I g o l i , a f e l l o w
p o s t g r a d u a t e s t u d e n t ; Mrs. Uche Igbokwe, a s e n i o r s t a f f
of t h e School of P o s t g r a d u a t e S t u d i e s ; Dr,-Ing. C. George,
a M a t e r i a l s b g i n e e r i n g C o n s u l t a n t whose r e f e r e n c e books
have been of immense help t o me.
F i n a l l y , I am very g r a t e f u l t o M r . R. FI. Gnwuka who
t y p e d this p r o j e c t and a l l t h e o t h e r s n o t mentioned h e r e
whose e f f o r t s have c o n t r i b u t e d t o make this work p o s s i b l e ,

NSUKKA AGBAZUE, V. E.
OCUOBER, 1990.
 A13 STRACT

R e p r e s e n t a t i v e samples of raw m a t e r i a l s and

f i n i s h e d p r o d u c t s from t h r e e N i g e r i a n C e m e n t Companies -
Calabar Cement Company, Calabar, t h e N i g e r i a n Cement
Company, Nkalagu and Benue Cement Company, Gbolto - and
one f o r e i g n made cement, Eagle Cement were t e s t e d
according t o t h e Nigerian I n d u s t r i a l Standards (NIS)
f o r chemical and p h y s i c a l p r o p e r t i e s .
The raw m a t e r i a l s , manufacturing technology and
p r o c e s s c o n d i t i o n s f o r t h e N i g e r i a n Cement Companies
were s t u d i e d t o a p p r a i s e how t h e s e have a f f e c t e d t h e
product q u a l i t y . 'Test r e s u l t s of t h e f i n i s h e d p r o d u c t s
were compared w i t h one a n o t h e r , t o e s t a b l i s h t h e i r e x t e n t
of co~flpliancew i t h t h e c u r r e n t Nigerian S a n d a r d
S p e c i f i c a t i o n on cement.
From t h e t e s t d a t a o b t a i n e d it was found t h a t a l l
t h e cement companies s t u d i e d used s u i t a b l e raw m a t e r i a l s
f o r cement production. Furthermore, f i n i s h e d product
a n a l y s i s showed t h a t t h r e e of t h e f o u r b r a n d s t e s t e d
f u l l y complied w i t h t h e N i g e r i a n S p e c i f i c a t i o n f o r
Ordinary ~ o r t l a n dCement (OPC) . The f o m h brand
d i s p l a y e d unsoundness i n t h e form of expansion phenomenan
a t t r i b u t e d t o unf avourable p r o c e s s / q u a l i t y c o n t r o l
factors.
 TABLE OF CONTmTS
Page
CERTIFICATION .. .. .. .. .. . .. i
.. .. .. .. .. .. ..
o

DEDICATION ii
.. .. .. .. .. .. ..
0.

ACKNOWLEDGEMENT iii
ABSTRACT v
TABLE OF CONTENTS . vi
LIST OF TABLES .. .. .. .. .. .. .. viii
LIST OF FIGURES .. .. .. .. .. .. .. ix
CHAPTER 1
INTRODUCTION
CEG.IENT MANUFACTURING PROCESS
Fundamental S t a g e s of Manufacture .. ..
Wet P r o c e s s .. .. .. .. .. ..
Dry P r o c e s s .. .. .. .. .. ..
Semi-Dry P r o c e s s .. .. .. .. ..
Semi-Wet P r o c e s s .. .. .. .. ..
QUALITY CONTROL 0 0

Raw M a t e r i a l S e l e c t i o n and P r o p o r t i o n i n g
E s s e n t i a l P a r a m e t e r s in Q u a l i t y C o n t r o l ..
P r o p e r t i e s of C l i n k e r P h a s e s .. .. ..
EFFECT OF IMPURITIES
Magnesium Oxide .. .... .. .. ..
Alkalies .. .. .. .. .. .. ..
Sulphur .. .. .. .. .. .. ..
Chlorides .. .. .. .. .. .. ..
Fluorides .. .. .. .. .. .. ..
Phosphates .. .. .. .. .. ..
STA<NDARD SPECIFICATION FOR CENENT . ..
CHAPTER 2
2.0 LITERATURE REVIEW .. .. .. .. .. 34
.
2 1 A I M AND JUSTIFICATION OF RESEARCH .. .. 36
 vii
T ~ L OF
E C O N T ~ T S(CONTD.)
Page
CHAPTER 3
300 EXPERD1ENTAL o a a a a a 39
.. .. ..
a 0 0 0 0

3.1 MATERIALS AND REAGENTS 0. 39

3.2 SAMPLE COLLECTION a a 39
..
0 0 0 .0 0

3.3 SAMPLE PREPARATION 0 0 a a a 0 40

3.4
.. ..RAW.. .. . ..
CHE['/IICAL ANALYSES OF
PRO DUCTS
MATEFEALS &
40
3.4.1 Loss On I g n i t i o n(LOI) .. .. .. .. 40
3.4.2 I n s o l & l e Residue (IR) .. .. .. .. 41
3.403 . .. ..
S i l i c a ( s i 0 2 ) Determination 41
3.4.4 Determination of CaO, MeO, Fe203 & f'a203 41
3.4.5 Determination of Lime ( c ~ O ) .. .. .. 42
3.4.6 .. .
Determination of Magnesia ( M ~ O ) 47
3.4.7 ..
Determination of Iron Oxide (Fe203) 50
3.4.8 .. ..
Determination of Alunina (A1203) 53
3 a4 a9 Determination of o t h e r Chemical Parameters 56
3 a5 PHYSICAL ANALYSES OF PRODUCTS . 57
.. .. .. .. .. .. ..
a .a

3.5 .I Fineness 57
305.2 S e t t i n g Time. .. . .. .. .. 57
305.3 Soundness .. .. .. .. .. .. 58
305.4 Compressive Strength .. .. . * a 58
CHAPTER 4
4 .O RESULTS AND DISCUSSION .. .. . ern 0 59
4.1 SAMPLE COLLECTION 0 0 .a a. a 0 59
4.2 SM'IPLE PREPARATION a a. - 0 a 59
..
0 0

4.3 SUITABILITY OF RAW MATERIALS .a 60

4.4 CHEMICAL AND PHYSICAL PROPERTIES OF
CEMENT SADlPLES 0. e. .0 0 . a. 62
4.5 COMPARISON OF FOUR CEMENT BRANDS a a. 65
CHAPTER 5
5 00 CON CL USION 0 0 a 0 0 0 0 0 e o .0 68
REFERENCES .. 0 a 0 0 .0 .0 0 ..a - 0 0 . 71

APPENDIX I: Overseas Report on T e s t s

Sample of Cement . .. .. .. ..
of
75
 LIST OF TABLES

TABLE
I Limiting Values of Chemical Composition
of Cement Raw M a t e r i a l ( a f t e r i g n i t i o n )
Comparison of B r i t i s h and N i g e r i a n
.. .. .. .. .. .. ..
Standards f o r Ordinary P o r t l a n d Cement
(OPC)

.. .. .. .
The Cement Standards f o r Some C o u n t r i e s
of t h e World 0 .

C e r t i f i c a t e of T e s t s ..
13enue Cement Company Ltd.:
.. ..
a *

Raw Mix P o t e n t i a l Composition: Sample A

Raw Mix P o t e n t i a l Composition: Sample 13
Raw Mix P o t e n t i a l Composition: Sanlple C 84 I

Proximate Analysis of Raw Coal from Enugu 85.

Ultimate Analysis of Coal Ash .. . 85

Chemical and P h y s i c a l P r o p e r t i e s of Two

Cement Samples each from Three N i g e r i a n
Cement Companies Designated A, B & C
and a Foreign Cement Brand Designated D 86
I

Average Chemical and P h y s i c a l P r o p e r t i e s

of Two Cement Samples each from Three
Nigerian Cement Companies Designated ,

Designated D .. .. .. . ..
A , B & C and a Foreign Cement Brand
87
 L I S T OF FIGURES

Fig. 1.
Semi-Dry P r o c e s s e s .. .. .. ..
P r e p a r a t i o n of R a w Meal f o r Urry and

Fig. 2. Compressive S t r e n g t h of C l i n k e r Phases 89-

Fig. 3. I l l u s t r a t i o n of Compressive S t r e n g t h of
Three N i g e r i a n OPC and one Foreign Made
,
OPC T e s t e d According t o N I S. 11/I 974 90

Fig. 4. Comparative R e p r e s e n t a t i o n of t h e
Compressive S t r e n g t h s of Three N i g e r i a n
OPC and one Foreign OPC, T e s t e d
According t o N I L 11/'I974 . .. 9%
 CHAPTER I

1 .O INTRODUCTION

I n i t s b r o a d e s t sense t h e word cement denotes any

kind of adhesive 1 . I n b u i l d i n g and c i v i l engineering,
it denotes a substance which can be used t o b k d
t o g e t her sand and broken s t o n e , o r o t h e r f o m s of
aggregate, i n t o a s o l i d mass. I n t h i s way a r e produced
such m a t e r i a l s a s concrete, mortars and v a r i o u s k i n d s
of a s b e s t o s cement products. A cement may b e a simple
chemical compomd, b u t more o f t e n it i s a mixture.
More important today a r e h y d r a u l i c cements, of
which p o r t l a n d cement i s t h e most f a m i l i a r example.
When made i n t o a p a s t e with water and aggregate, t h e s e
s e t and harden a s a r e s f i t of chemical r e a c t i o n s between
t h e water and t h e compounds ( p r i n c i p a l l y c a l c i u n
s i l i c a t e s ) p r e s e n t i n t h e cement: simply r e p r e s e n t e d
a s follows.

Such r e a c t i o n s occur n o t only i f t h e p a s t e i s l e f t t o

s t a n d i n a i r b u t a l s o if it i s p l a c e d i n water.
I n 1796' James Parker made a hydralilic cement
from t h e c a l c i n e d nodules of a r g i l l a c e o u s l i m e s t o n e
known a s s e p t a r i a . The f i r s t a t t e m p t s t o produce
cement by t h e burning of an a r t i f i c i a l m i x t u r e of
l i m e s t o n e and c l a y were made i n France, e s p e c i a l l y by
V i c a t , i n t h e e a r l y y e a r s of t h e 1 9 t h century. Later
on, Joseph Aspdin, a b r i c k l a y e r of Leeds, B r i t a i n ,
produced an e x c e l l e n t h y d r a u l i c cement, i n 1 8 2 4 , ~by
burning a mixture c o n t a i n i n g c e r t a i n p r o p o r t i o n s of
l i m e s t o n e and c l a y a t a h i g h temperature. T h i s was a
p a t e n t , I t a n improvement i n t h e modes of producing
a r t i f i c i a l stonett. He c a l l e d h i s product ItPortland
Cement1!, a name which has s u r v i v e d as a g e n e r i c
d e s i g n a t i o n and which was o r i g i n a l l y chosen by Aspdin
because t h e a r t i f i c i a l s t o n e made w i t h t h i s cement
(and aggregates) resembled " P o r t l a n d StoneI1, a t y p e of
l i m e s t o n e found i n I s l e of P o r t l a n d in Southern B r i t a i n
4 .
P r o g r e s s i v e l y , two fundamental developments have
improved on t h e e a r l y product: t h e i n t r o d u c t i o n of

gypsum, added when g r i n d i n g t h e c l i n k e r (semi-f i n i s h e d

product o b t a i n e d by burning t o g e t h e r l i m e s t o n e and
\

c l a y ) , t o a c t as a s e t r e t a r d e r and t h e use of h i g h e r
burning t e m p e r a t u r e s t o allow t h e production of h i g h e r
l i m e c o n t e n t s i l i c a t e s which a r e necessary f o r more
r a p i d s t r e n g t h development i n c o n c r e t e 5 . Such improve-
ments were a i d e d by t h e g r a d u a l replacement of v e r t i c a l
s h a f t k i l n w i t h t h e r o t a r y k i l n and t h e i n t r o d u c t i o n
of t h e b a l l m i l l f o r t h e f i n e r grinding of cement.
The most important reaction i n cement manufacture
occurs i n t h e k i l n , being t h e formation of tricalcium
s i l i c a t e , taking place a t t h e temperature of about
1 4 0 0 ~ as
~ , shown in t h e equation below.

The f i r s t cement company i n Nigeria, t h e Nigerian

b
Cement Company Ltd., Nkalagu was established i n 1957 ,
with t h e r a t e d capacity then a t 240,000 t o m e s per
annum, followed by t h e establishment of West African
Portland Cement Company (WAPCO)
Ltd. Ewekoro a t t h e
dawn of Independence i n 1960. Today, t h e r e a r e seven
cement companies i n t h e country, l o c a t e d a s follows:
1. West A f ~ i c a nPortland Cement Company a t
Ewekoro and Shagamu.
2. Benue Cement Company a t Yandev near Gboko.
3. Ashaka Cement Company a t Bauchi.
4. Bendel Cement Company a t Ukpilla.
5. Calabar Cement Company a t Calabar.
6. ~ i ~ e r i aCement
n Company a t Nkalagu.
7. Cement Company of Northern Nigeria a t Sokoto.
Cement q u a l i t y i s of primary importance t o t h e
ultimate consumers of t h e product. I n t h i s work an
a t t e m p t i s made t o a s s e s s t h e q u a l i t y of some made i n
N i g e r i a cement brands; c o n s i d e r i n g t h e i r p r o c e s s e s of
manufacture; comparing t h e i r q u a l i t i e s and w i t h an
imported brand; t h e e x t e n t of t h e i r compliance w i t h
t h e l a i d down s t a n d a r d s p e c i f i c a t i o n s was a l s o
investigated.
The s t u d i e s c e n t r e d on t h r e e N i g e r i a n cement
companies, namely, Benue Cement Company Ltd. Gboko,
t h e N i g e r i a n Cement Company Ltd. Nkalagu, and Calabar
Cement Company Ltd. Calabar, a s well a s an imported
cement brand, Eagle Cement.

.
II CEMEliT MANUFAC'URING PROCESS
The b a s i c cement manufacturing p r o c e s s c o n s i s t s
quarrying c a l c a r e o u s and a r g i l l a c e o u s m a t e r i a l s in
t h e r e q u i r e d p r o p o r t i o n s , reducing t h e s e m a t e r i a l s t o
a f i n e l y d i v i d e d s t a t e , b l e n d i n g them t o a uniform
composition and h e a t i n g them - f i r s t , t o d r i v e off any
water and carbon d i o x i d e , and secondly, t o t h e p o i n t
of i n c i p i e n t f u s i o n when t h e p r i n c i p a l cement compounds
a r e formed. Finally t h e resulting clinker,
termed, i s cooled and ground w i t h about 3 ~ 5 %gypsum t o
a f i n e powder which i s p o r t l a n d cement 7 .
 TWO p r i n c i p a l processes known a s t h e wet and dry
processes according a s t o whether t h e raw m a t e r i a l s
a r e ground and mixed i n a wet o r dry c o n d i t i o n , a r e
used. I n a v a r i a n t of t h e s e p r o c e s s e s , t h e semi-rlry
process, t h e raw m a t e r i a l s a r e ground dry and t h e n
mixed with 10 - 14 percent water and f orrned i n t o
noddes. The wet p r o c e s s was o r i g i n a l l y used f o r
very f r i a b l e m a t e r i a l s such a s chalk and c l a y and
l a t e r extended t o t h e harder l i m e s t o n e s and shales.
For many y e a r s t h e wet p r o c e s s was p r e f e r r e d in many
c o u n t r i e s because of t h e more a c c u r a t e c o n t r o l of t h e
raw mix which was p o s s i b l e w i t h it. With improved
c o n t r o l , t h e r e has been a swing back t o t h e dry
p r o c e s s , f o r l e s s f u e l i s r e q u i r e d f o r burning t h a n
in t h e wet process. Modern developments in t h e dry
mixing of powdered m a t e r i a l s have, moreover, now
removed t h e disadvantage of t h e dry process.
Cement manufacture a s it i s p r a c t i s e d today has
come a long way through v a r i o u s t e c h n i c a l and
t e c h n o l o g i c a l r e s e a r c h e s and changes aimed a t
improving b o t h t h e p r o c e s s and product q u a l i t y . The
i n i t i a l s h a f t k i l n gave way t o t h e modern r o t a r y k i l n s
which a r e more convenient f o r achieving d e s i r e d burning
temperatures.
 The use of cyclone p r e h e a t e r system f o r raw
m a t e r i a l d r y i n g was f i r s t p a t e n t e d i n 1934 by M. Vogel-

Jorgensen, an employee of Fa L. Srnidth company,

Copenhagen
8
.
By t h i s development it became p o s s i b l e
t o u t i l i z e t h e k i l n e x i t g a s e s f o r raw m a t e r i a l d r y i n g ,
t h e r e b y enhancing t h e economy of process. 17 years
l a t e r , in 1951, t h e f i r s t Humboldt cyclone suspension
p r e h e a t e r , modified by Fa Muller, was p u t in o p e r a t i o n .
The Humboldt p r e h e a t e r k i l n d i v i d e s t h e burning p r o c e s s
i n t o two phases: t h e conventional burning c y l i n d e r i s
c o n s i d e r a b l y shortened, and t h e p r e h e a t i n g and p a r t i a l
c a l c i n i n g of t h e raw mix by t h e hot k i l n e x i t g a s e s i s
performed i n t h e cyclone raw mix suspension p r e h e a t e r .
Most r e c e n t i n n o v a t i o n s i n t h e cement i n d u s t r y
include t h e pre-calcination system of k i l n f i r i n g .
T h i s i n v o l v e s i n s t a l l a t i o n of p r e h e a t e r t o g e t h e r w i t h
a secondary b u r n e r j u s t b e f o r e m a t e r i a l i n l e t t o t h e
k i l n , t o increase productivity.
I n t h e comminution ( o r s i z e - r e d u c t i o n ) p r o c e s s
t h e R o l l e r p r e s s technology i n v e n t e d by 1<. 1-1. D. Humboldt
i s t h e l a t e s t i d e a t o make l i f e e a s i e r . The R o l l e r
p r e s s i s normally i n s t a l l e d upstream of Raw M i l l o r
Cement M i l l and can i n c r e a s e o u t p u t of t h e Piills by as
much as 80% of Raw M i l l s and 40% f o r t h e Cement M i l l s .
T h i s i s a s d s t a n t i a l energy saving when we c o n s i d e r
t h a t cement g r i n d i n g a l o n e consumes about 75% of t o t a l
energy requirement of a cement p l a n t .
Generally r e c e n t advancements i n cement
manufacture a r e c h a r a c t e r i z e d by h i g h automation in
p r o c e s s and q u a l i t y c o n t r o l . However, t h e b a s i c cement
chemistry and manufacturing technology remain e s s e n t i a l l y
t h e same.

1 .I.I Fundamental Stages of Manufacture

R e g a r d l e s s of v a r i a t i o n s of d e t a i l , which may b e
c o n s i d e r a b l e , a l l methods of cement manufact w e a r e
aimed a t producing t h e same end product and a l l i n v o l v e
t h e same fundamental s t a g e s .
(i) Raw M a t e r i a l comminution
The raw m a t e r i a l s a r e reduced t o f i n e p a r t i c l e
s i z e s o t h a t t h e y can b e i n t i m a t e l y mixed.
(ii) Blending P r o c e s s
Raw m a t e r i a l s a r e blended and mixed t o produce a
raw f e e d mix of uniform chemical composition c o n t a i n i n g
calcium c a r b o n a t e , s i l i c a , alumina, i r o n o x i d e and
o t h e r compounds i n t h e r e q u i r e d p r o p o r t i o n s .
(iii) Drying
The blended raw mix i s heated t o t h e point where
a l l moisture i s driven off a s steam or water vapour.
(iv) Clinker Burnhg
The following abbreviated notation i s commonly
employed f o r i n d i c a t i n g t h e c l i n k e r c o n s t i t uent s:
C = CaO. F = Fe2O3 N = Na20 P = P205

A = A1203 M = MgO K = K20

S = Slop H = H20 L = Li20 T = Ti02

-
S = SO3
-
C = cop
Chemical formulae in cement chemistry a r e often
expressed a s a sum of oxides; t h u s t r i c a l c i m s i l i c a t e ,
Ca3Si0 can be w r i t t e n a s 3Ca0.Si02. This way of
5'
writing t h e formulae does n o t , of course, imply t h a t
t h e constituent oxides have any separate existence
within t h e s t r u c t u r e of t h e compound. Thus, f o r example:

I n t h e course of t h e burning process t h e formation of

c l i n k e r i s accomplished i n t h e following s t a g e s which
merge i n t o one a n o t h e r :

Ambient temp. t o 2 0 0 ~ ~
200
450

1000

C A,
3

1200
-
- 950'~

4CaO
450'~

650 - 1 0 0 0 ' ~

1 200°c

2Ca0

- 1450'~

+
+ Si02

N203 +
-
-+
C2S, e t c a r e formed:

3Ca0 + N203
9

Drying t h e raw m i x

2Ca0 .Si02
--j

Fe20j )
No s i g n i f i c a n t changes o c c u r
Dehydration of c l a y components

- ,
e x p u l s i o n of C02
Commencement of t h e r e a c t i o n between

CaO and o t h e r c o n s t i t u e n t s

such a s S, A, F and o t h e r s ; i n t h i s r a n g e t h e compounds

3Ca0.A1203

3 C a O .Si02 =
=

C3S
C3A
C2S

S i n t e r i n g ( o r c l i n k e r i n g ) i s accomplished
here; a s a r e s u l t of a t t a i n i n g f u s i o n ,

which i s i m p o r t a n t t o t h e f u r t h e r develop-

ment of t h e m i n e r a l s , t h e p r i n c i p a l c l i n k e r

m i n e r a l C S i s formed by r e a c t i o n of C2S
3
w i t h C, w h i l e C4AF i s a l s o formed:
2CaO. S i 0 2 + CaO
4Ca0 .N2O3.Fe2O3=Ca4AF

The f i n a l s t a g e i s t h e c o o l i n g o f t h e c l i n k e r , i n t h e
c o u r s e o f which t h e t o t a l i t y of t h e minerals s o l i d i f i e s

from a s t a t e of l i q u i d - s o l i d e q u i l i b r i u m .
.
C a l c i n a t i o n of t h e l i m e s t o n e ,

i.e.

The c l i n k e r i s

c o o l e d t o a t e m p e r a t u r e a t which it can c o n v e n i e n t l y b e
handled, 60 - 1 5 0 ~ ~Clinker
. may b e sent d i r e c t l y t o t h e
f i n i s h grinding m i l l s but i s usually stockpiled. All

temperature measurements a r e c a r r i e d o u t w i t h pyrometers

i n s t a l l e d on t h e p r o c e s s l i n e .
(v) C l i n k e r Grinding
C l i n k e r i s ground t o t h e s p e c i f i e d f i n e n e s s , w i t h
t h e a d d i t i o n of a small p r o p o r t i o n ( 3 - 5%) of gypsum t o
c o n t r o l t h e s e t t i n g t i m e of t h e f i n i s h e d cement.

1 .I .2 Wet Process
Although, it can b e used f o r a l l t y p e s of raw
m a t e r i a l t h e wet p r o c e s s i s now more commonly used w i t h
t h e "softu materials - chalk and c l a y - which have a
r e l a t i v e l y h i g h n a t u r a l m o i s t u r e c o n t e n t and can g e n e r a l l y
b e most e a s i l y and economically reduced t o raw f e e d
f i n e n e s s and blended a s s l u r r y .
Because t h e thermal e f f i c i e n c y of t h e wet p r o c e s s
i s much lower t h a n t h a t of o t h e r p r o c e s s e s , t h e wet
p r o c e s s i s almost u n i v e r s a l l y b e i n g r e p l a c e d by t h e d r y
o r semi-dry p r o c e s s f o r hard m a t e r i a l s l i k e l i m e s t o n e
and s h a l e and even f o r ''soft" m a t e r i a l s , as new works
a r e b u i l t o r e x i s t i n g works modernized o r extended.
S o f t m a t e r i a l s a r e converted t o a s l u r r y w i t h water i n
a wash-mill. F i n e m a t e r i a l i n suspension p a s s e s through
a v e r t i c a l screen ( a p e r f o r a t e d p l a t e c o n t a i n i n g 6 mm
holes) a t t h e s i d e s of t h e tank against which it i s
thrown by t h e harrows.
The refined s l u r r y i s monitored by determination
of residues when a sample i s washed through standard
sieves. Acceptable residues depend on t h e chemical
r e a c t i v i t y of t h e coarse material b u t 0,556 g r e a t e r than
300 pn and 12% g r e a t e r than 90 p.n would be t y p i c a l I0 .
Chemical composition i s checked by sampling a t several
stages. The simplest method i s a d i r e c t t i t r a t i o n of
calcium carbonate in t h e composite s l u r r y by standard
d i l u t e hydrochloric acid w i t h which t h e s i l i c e o u s
components do not react. However, t h i s w i l l not d e t e c t
s u b t l e v a r i a t i o n s i n raw material composition and i n
modern p l a n t s an automated X-ray fluorescence spectro-
meter i s used t o determine s i l i c o n , aluminium, iron and
calcium. T h i s takes about 10 minutes and an on-line
instrument would control equipment feeding t h e blending
mill.
A t t h i s stage t h e s l u r r y i s held i n tanks i n which
it i s a g i t a t e d both mechanically and by compressed a i r
t o prevent segregation. After chemical a n a l y s i s small
adjustments may be necessary involving mixing s l u r r y
from two tanks, one high i n calcium carbonate, t h e other
low, i n t o a t h i r d tank.
1.1.3 Dry P r o c e s s
A s t h e name i m p l i e s , raw m a t e r i a l s in t h e dry
p r o c e s s a r e m i l l e d , blended and f e d t o t h e k i l n in a
dry s t a t e , r a t h e r than i n s l u r r y a s i s t h e c a s e w i t h
t h e wet p r o c e s s . For this reason t h e dry p r o c e s s i s
b e s t s u i t e d t o raw m a t e r i a l s having r e l a t i v e l y low
n a t u r a l moist w e c o n t e n t .
T y p i c a l l y , t h e dry p r o c e s s i s used w i t h hard
materials - say l i m e s t o n e and s h a l e - but i n recent
y e a r s it has come t o b e used a l s o f o r c e r t a i n s o f t e r
m a t e r i a l s formerly handled by t h e wet process. With
t h e r i g h t m a t e r i a l s t h e dry p r o c e s s i s much l e s s f u e l -
i n t e n s i v e t h a n t h e wet p r o c e s s and f o r t h a t reason i s
now favoured whenever t h e m a t e r i a l s a r e s u i t a b l e .
The sequences of o p e r a t i o n s used i n p r e p a r i n g t h e
raw meal f o r t h e dry and semi-dry p r o c e s s e s a r e shown
s c h e m a t i c a l l y in Fig. 1.
The raw m a t e r i a l s a r e crushed and p u t i n t o s t o c k
p i l e s u s u a l l y under cover. A c o n s i d e r a b l e degree of
homogenisation i s o b t a i n e d by l a y i n g each of them down
i n s t r i p s o r l a y e r s and t h e n s y s t e m a t i c a l l y r e c l a i m i n g
from t h e s t o c k p i l e s produced. They a r e t h e n p r o p o r t i o n e d
i n t o t h e m i l l i n g / d r y i n g system continuously by weight.
Gases from t h e k i l n o r t h e c o o l e r a r e used f o r drying
although supplementary f i r i n g may b e necessary.
Grinding i s c a r r i e d o u t i n e i t h e r a b a l l m i l l o r a
r o l l e r m i l l ; t h e l a t t e r uses l e s s energy f o r a given
product f i n e n e s s t h a n a b a l l m i l l b u t w i t h very hard
a b r a i s i v e m a t e r i a l s it l o s e s e f f i c i e n c y and p r e s e n t s a
maintenance problem.
S e p a r a t i o n of c o a r s e from f i n e m a t e r i a l l e a v i n g
t h e m i l l may b e a f f e c t e d by e n t r a i n i n g t h e powder in
t h e g a s stream from t h e k i l n followed by s e p a r a t i o n of
c o a r s e m a t e r i a l i n a s e p a r a t o r and/or cyclone system.
A l t e r n a t i v e l y , t h e m i l l product may b e f e d d i r e c t l y t o
t h e s e p a r a t o r using a bucket e l e v a t o r . The s e p a r a t o r
o r c l a s s i f i e r makes use of t h e b a l a n c e between
c e n t r i f u g a l and a i r - d r a g f o r c e s produced by a r o t a t i n g
p l a t e which s t r i k e s t h e p a r t i c l e s and by a f a n . The
separated coarse f r a c t i o n i s returned t o t h e m i l l .
The m i l l e d raw meal i s t h e n t r a n s f e r r e d t o blending
s i l o s which may b e over 30m h i g h followed by f i n a l - s t a g e
s i l o s (called storage s i l o s ) .

1. I . 4 Semi-Dry P r o c e s s
Here t h e raw m a t e r i a l s a r e f i r s t p r o c e s s e d i n t o
raw meal a s f o r t h e dry process. Water i s t h e n added
t o t h e raw meal t o g i v e a m o i s t u r e c o n t e n t of about
2 - I . The water may b e added in a p a d d l e mixer,
from which t h e mix i s f e d t o a r o t a t i n g i n c l i n e d d i s h
n o d u l i z e r , o r t h e meal may b e f e d d i r e c t l y i n t o t h e
n o d u l i z e r and water added by sprays.
A s t h e d i s h n o d u l i z e r r e v o l v e s , t h e moist meal i s
formed i n t o roughly s p h e r i c a l p e l l e t s o r nodules.
Nodule s i z e depends on t h e works: in some i n s t a l l a t i o n s
t h e p r e f e r r s d nodule s i z e i s 10 - 1 6 mm and in o t h e r s
25 - 40 mm, depending on t h e p l a n t s i z e and o t h e r
process characteristics.

I . 1.5 Semi-wet P r o c e s s
The a l t e r n a t i v e , used w i t h s o f t m a t e r i a l s having a
r e l a t i v e l y high n a t u r a l moisture content, i s t o prepare
t h e raw f e e d i n s l u r r y form, a s f o r t h e wet p r o c e s s ,
and t h e n remove enough m o i s t u r e t o enable t h e f e e d t o
b e formed i n t o p i e c e s which can b e handled by a d r y
process k i l n .
To accomplish t h i s t h e s l u r r y i s f e d t o a f i l t e r
press. F i l t e r p r e s s i n g i s a b a t c h o p e r a t i o n , each
p r e s s i n g t a k i n g some 25 - 30 minutes. 13y p r e s s i n g , t h e
raw m a t e r i a l i s reduced t o a ttcakettw i t h a m o i s t u r e
c o n t e n t of around 18 - 20%, which i s t h e n kneaded and
extruded i n t o IffingerI1 about 20 mm in diameter and 80 mm
long.
 The semi wet p r o c e s s i s i n l i m i t e d use. However
w i t h t h e p r e s e n t high c o s t of energy it i s being much
more favourably considered a s a replacement f o r t h e
energy-intensive wet process.

1.2 QUALITY CONTROL

Q u a l i t y c o n t r o l i n cement manufacture i s a
continuous p r o c e s s i n v o l v i n g every s t a g e of production
from t h e quarry f a c e t o t h e f i n i s h e d product, The
e n t i r e manufact w i n g o p e r a t i o n depends on t h e l a b o r a t o r y ,
f o r it i s l a b o r a t o r y a n a l y s i s a t every s t a g e , f e d back
r a p i d l y t o t h o s e c o n t r o l l i n g t h e production p r o c e s s ,
which governs t h e quarrying of raw m a t e r i a l s , t h e i r
b l e n d i n g , t h e f i r i n g i n t h e k i l n , t h e g r i n d i n g of t h e
,
c l i n k e r and, in t h e end, t h e q u a l i t y of t h e cement
produced.
R e p r e s e n t a t i v e samples a r e c o l l e c t e d a t r e g u l a r
i n t e r v a l s from each of t h e manufacturing s t a g e s and
t e s t e d chemically and p h y s i c a l l y i n t h e l a b o r a t o r y .
Today, i n s t a n d a r d l a b o r a t o r i e s , much of t h e r o u t i n e
t e s t i n g i s c a r r i e d out by automatic equipment which
provides a rapid analysis t h a t shortens t h e time l a g
between sampling and any n e c e s s a r y adjustments t o t h e
manufacturing process. X-ray s p e c t r o m e t e r s , f o r example,
a r e e x t e n s i v e l y used t o a n a l y s e t h e chemical c o ~ n p o s i t i o n
of raw m a t e r i a l s , blended f e e d s t o c k , and f i n i s h e d
cement. Other automatic equipment i s used t o determine
t h e s p e c i f i c s u r f a c e o r f i n e n e s s of ground raw m a t e r i a l s
and cement.
I n l a b o r a t o r i e s , where automatic t e s t i n g equipment
a r e employed " c l a s s i c a l t 1 chemical and p h y s i c a l a n a l y s i s
methods a r e s t i l l used t o monitor t h e r e s u l t s and t o
c a l i b r a t e t h e automatic equipment. Automation in
q u a l i t y c o n t r o l i s y e t t o b e well developed in t h e
N i g e r i a n Cement I n d u s t r y .

1.2.1 Raw M a t e r i a l S e l e c t i o n and P r o p o r t i o n i n g

The main chemical components of cement c l i n k e r are
c a l c i u n o x i d e ( c ~ o ,) S i l i c a ( s i o 2 ) , Alumina ( m 2 0 3 ) ,
. i s necessary
I r o n oxide (Fe203) and Magnesia ( ~ ~ 0 ) It
t o p r e p a r e cement raw meal. i n which t h e above mentioned
components a r e w i t h i n t h e p r o p e r range 11 If n o t ,.
c l i n k e r burning w i l l b e d i f f i c u l t o r c l i n k e r quality
w i l l deteriorate.
CaO, Si02, A1203 and Fe 0 form t h e f o u r main
2 3
c l i n k e r m i n e r a l s which a r e a l i t e , C S; b e l i t e , C2S;
3
aluminate, C3A and f e r r i t e , CkM. A p r o p e r q u a n t i t y of
MgO should b e p r e s e n t i n o r d e r t o p r o v i d e cement a good
colour. It i s a l s o s a i d t h a t MgO has f l u x e f f e c t .
A s a r u l e , t h e following main raw m a t e r i a l s
12
p r o v i d e t h e components f o r t h e raw mix.
- calcareous materials:
l i m e s t o n e from a v a r i e t y of g e o l o g i c a l
f o r m a t i o n s , l i m e marl ( n a t u r a l mixture of
l i m e s t o n e w i t h a low p r o p o r t i o n of clayey
substance) .
- argillaceous materials:
marl, c l a y , s h a l e , e t c .
A s r e q u i r e d , t h e following c o r r e c t i n g m a t e r i d s can b e
added t o t h e raw mixes made from t h e above-maitioned
components:
s i l i c e o u s materials:
sand, s i l i c a rock, q u a r t z ;
- m a t e r i a l s c o n t a i n i n g aluminium:
bauxite, kaolin;
- materials containing Iron:
Iron ores, roasted pyrites.
Components c o n t a i n i n g l i m e s t o n e and c l a y fonm t h e
g r e a t e r p a r t of t h e mixture. A f e a t u r e t h a t t h e s e two
raw m a t e r i a l s s h a r e i n common i s t h e i r q u a l i t a t i v e equal
chemical composition, b u t d i f f e r i n g i n t h e q u a n t i t a t i v e
p r o p o r t i o n s of t h e i r main chemical compounds.
T h i s f a c t i s manifested in t h e s u b d i v i s i o n of t h e s e
m a t e r i a l s a c c o r d i n g t o t h e i r CaCO c o n t e n t s .
3
-
- high-grade l i m e s t o n e 9 6 100% CaCO3
- marly l i m e s t o n e 90 - 96ii 11

- l i m e marl 75 - 9056 11

- marl
- c l a y marl
- marly c l a y
- clay
Since t h e C a C Oc o n t e n t of raw mixes i s normally between
3
75 and 78% a l i m e marl having t h i s composition i s a
highly d e s i r a b l e raw m a t e r i a l , b u t i s seldom found in
t h e natural state.
For t h e cement p r o d u c t i o n , it i s n e c e s s a r y t o have
raw m a t e r i a l m i x t u r e s whose chemical composition i s
within c e r t a i n l i m i t s . The continuous p r o d u c t i o n of
h i g h - q u a l i t y cement i s p o s s i b l e only i f t h e raw mix
p o s s e s s e s optimum composition and f u r t h e r m o r e i f
v a r i a t i o n s i n t h i s composition remain with t h e narrowest
p o s s i b l e range. The l i m i t i n g v a l u e s shown i n T a b l e 1
a r e t o b e regarded a s v a l i d f o r t h e manufacture of
cement g e n e r a l l y , i. e m, t h e y r e l a t e t o t h e manner of
cement works. l 3 Within any p a r t i c u l a r works t h e
v a r i a t i o n s have t o b e much s m a l l e r .
1.2.2 E s s e n t i a l Parameters i n Q u a l i t y C o n t r o l
For p r a c t i c a l purposes t h e raw m a t e r i a l composition
(and a l s o t h e composition of t h e cement c l i n k e r ) i s
u s u a l l y c h a r a c t e r i z e d by c e r t a i n r a t i o s , o f t e n c a l l e d
ttmodulilt. For t h e monitoring and c o n t r o l of
p r o d u c t i o n t h e f o l l o w i n g formulae have been found u s e f u l
f o r a d j u s t i n g t h e composition of t h e raw meal on t h e
b a s i s of l a b o r a t o r y a n a l y s i s of t h e components
( p r o p o r t i o n i n g formulae) . Compliance w i t h t h e l i m i t i n g
v a l u e s ( i n b r a c k e t s ) of t h e s e moduli can b e expected t o
r e s u l t i n a good product of t h e burning p r o c e s s , w i t h
minimum o p e r a t i o n a l d i f f i c u l t i e s . 1 4

Lime S a t u r a t i o n F a c t o r (LsF) :
Lime S a t u r a t i o n F a c t o r i s d e f i n e d in B r i t i s h
s t a n d a r d as well as i n N i g e r i a n I n d u s t r i a l Standardq5 as
CaO -
0.7$0,
3
LSF =
2.8Si02 + 1.2A1203 + 0.69 J? (0.92-0.98)
e2°3
Where each of t h e symbols r e f e r s t o t h e p e r c e n t a g e (by
weight of t o t a l sample) of t h e oxide excluding any
c o n t a i n e d in t h e i n s o l u b l e r e s i d u e . When t h e LSF
approaches u n i t y t h i s c l i n k e r i s d i f f i c u l t t o burn and
o f t e n shows e x c e s s i v e f r e e l i m e contents. I 6
Lime Combination Fact o r (LCF)
An improvement on t h e formula f o r LSF was made.
A new formula known as Lime Combination F a c t o r (LCF)
was i n t r o d u c e d i n which f r e e l i m e was sLibstracted from
t o t a l l i m e s i n c e t h i s ( f r e e lime) does n o t a c t u a l l y
c o n t r i b u t e t o t h e q u a l i t y of cement, Thus f o r c l i n k e r
and cement samples

CaO - 0.7SOj -
Free CaO
LCF =
2.8 Si02 + 1.2 A1203 + O,b5 hUe2O3

However, LSF has continued t o b e used t o a s s e s s cement

quality.

S i l i c a Ratio ( s ~ R )

In g e n e r a l , c l i n k e r w i t h a h i g h s i l i c a r a t i o i s more
d i f f i c u l t t o burn and e x h i b i t s poor c o a t i n g c h a r a c t e r -
istics. Low v a l u e of S i R o f t e n l e a d s t o r i n g formations
and low e a r l y s t r e n g t h (1 - 3 days) i n t h e cement,

Alumina R a t i o (LR)
Clinker with high alumina r a t i o produces cement with
high early s t r e n g t h (I - 3 days) but makes t h e reaction
between t h e s i l i c a and calcium oxide i n t h e burning
zone more d i f f i c u l t .

Liquid phase
Beside t h e s e various moduli r e s u l t i n g from t h e
desired adjustment of t h e raw mix composition, t h e
amount of l i q u i d phase formed (due t o fusion) a t t h e
s i n t e r i n g temperature of t h e material a l s o a f f e c t s t h e
course of t h e reaction t h a t develops in t h e burning
process. The content of l i q u i d phase in t h e c l i n k e r
can, according t o Lea, be calculated from t h e following
formula 17. .

(at 1 4 0 0 ~ ~ )
+ MgO (max 2Y6) + Na20

If t h e proportion of l i q u i d i s below 24% t h e raw mix

w i l l in general b e d i f f i c u l t t o burn, i. e. i t s s i n t e r i n g
temperature w i l l be high. Conversely, i f it i s above
28% t h e raw mix w i l l s i n t e r t o o r e a d i l y and d i f f i c u l t i e s
may a r i s e a s a r e s u l t of coating formation i n t h e k i l n .
In both cases it may moreover occur t h a t t h e formation
of t h e c l i n k e r minerals, and t h u s t h e quality of t h e
cement, a r e adversely affected.
Compound Composition of P o r t l a n d Cement
The p o t e n t i a l compound composition of c l i n k e r
could b e determined from simple computational method
given by Bogue. l8 The term p o t e n t i a l i s used because
it i s assumed t h a t t h e s e t of o x i d e s i s brought t o
e q u i l i b r i u m and k e p t i n e q u i l i b r i u m d u r i n g c o o l i n g , a
s i t u a t i o n which i s n o t f u l l y r e a l i z e d i n p r a c t i c e .
I n t h e c a l c u l a t i o n a l l t h e i r o n oxide i s assumed
t o b e p r e s e n t i n an a l u m i n o f e r r i t e s o l i d s o l u t i o n of
composition C4AF and all t h e alumina n o t r e q u i r e d t o
s a t i s f y t h e i r o n i n t h e f e r r i t e i s considered t o b e
p r e s e n t as C A. The l i m e remaining, a f t e r t h a t r e q u i r e d
3
f o r t h e s e compounds i s deducted from t h e combined l i m e ,
i s t h e n p r o p o r t i o n e d between C S and C2S. The combined
3
l i m e i s simply t h e t o t a l found by chemical a n a l y s i s
minus t h e f r e e l i m e which can b e determined by
e x t r a c t i o n w i t h e t h y l e n e g l y c o l . 19
The g e n e r a l s o l u t i o n t o t h e c a l c u l a t i o n i s expressed
i n t h e f o l l o w i n g e q u a t i o n s ( ~ o g u e , 1955) in which t h e
chemical formulae r e p r e s e n t t h e weight p e r c e n t of each
oxide:
 23

T he c a l c u l a t i o n can b e modified f o r c l i n k e r s i n which

t h e composition of t h e f e r r i t e phase d i f f e r s
s i g n i f i c a n t l y from C4hF a s t h e composition can b e
determined by x-ray d i f f r a c t i o n . This i s not usual
f o r o r d i n a r y p o r t l a n d cement c l i n k e r s b u t it i s
e s s e n t i a l w i t h s u l p h a t e r e s i s t i n g p o r t l a n d cement
where t h e s o l i d s o l u t i o n approaches t h e formula C6AF2.

1.2.3 P r o p e r t i e s of c l i n k e r p h a s e s
P o r t l a n d cement c l i n k e r c o n s i s t s of f o u r
c r y s t a l l i n e phases: a l i t e ( C S ) , b e l i t e ( c ~ s ) , c a l c i u n
3
alutninat e ( C A) and c a l c i u n alumino-f e r r i t e (C4AF)
3
c l o s e l y i n t e r l o c k i n g one another.

C S i s t h e most important c o n s t i t u e n t of p o r t l a n d
3
cement c l i n k e r and i s r e s p o n s i b l e f o r t h e e a r l y s t r e n g t h
development due t o i t s c h a r a c t e r i s t i c c r y s t a l
structure. Ordinary p o r t l a n d cement c l i n k e r should have
about 50 - 64% C3Se C l i n k e r w i t h more t h a n 65% C3S i s
d i f f i c u l t ' t o b u r n , has poor c o a t i n g c h a r a c t e r i s t i c s
and u s u a l l y produces unsound cement. I n portland
cement c l i n k e r C S does n o t e x i s t i n p u r e form, It
3
always i n c o r p o r a t e s f o r e i g n o x i d e s l i k e NgO, A1203,
Fe203, Ti02, e t c . The amount of f o r e i g n oxide p r e s e n t

i n it depends on t h e composition of t h e c l i n k e r , t h e
t e m p e r a t u r e a t which it was b u r n t and t h e r a t e of
cooling. These c o n d i t i o n s modify t h e p r o p e r t i e s of
t h e a l i t e ; t h e i n c o r p o r a t i o n of f o r e i g n o x i d e s u s u a l l y
increases t h e strength. Below 1 2 5 0 ~C ~S may decompose
3
i n t o CaO and C2S i f s u b j e c t e d t o very slow cooling.
Fig. 2 shows t h e compressive s t r e n g t h s of t h e
f o u r c l i n k e r phases, i n d i c a t i n g t h a t C S develops h i g h
3
e a r l y s t r e n g t h ; C2S g a t h e r s s t r e n g t h a t l a t e r a g e s
while C A and C4AF have l i t t l e c o n t r i b u t i o n t o s t r e n g t h
3
development.

B e l i t e (c2S)

C2S r e a c h e s about 25% i n o r d i n a r y p o r t l a n d cement

c l i n k e r and i s r e s p o n s i b l e f o r l a t e s t r e n g t h . The
p e r c e n t a g e of C S and C2S i s a f u n c t i o n of t h e raw meal
3
( s l u r r y ) composition and t h e burning temperature.
C S i s formed a t a h i g h e r t e m p e r a t u r e t h a n C2S; f o r
3
t h i s reason a h i g h e r t e m p e r a t u r e i s r e q u i r e d f o r t h e

s i n t e r i n g process. Lower t e m p e r a t u r e r e s u l t s i n a
h i g h e r c o n t e n t of C2S, a lower c o n t e n t of C S and a
3
higher p e r c e n t a g e of f r e e lime. High C S (LOWC2s)
3
l a a d s t o h i g h e a r l y s t r e n g t h and h i g h h e a t g e n e r a t i o n .
CJS and C2S c o n t r o l most of t h e s t r e n g t h developing
c h a r a c t e r i s t i c s of a cement.

Calcium Aluminate (c,A)

C3A i s responsible f o r p l a s t i c i t y (workability)

of t h e c l i n k e r . I n an ordinary p o r t l a n d cement c l i n k e r ,
C A content i s p r e f e r r e d t o b e about 10% a s cement high
3
i n C A i s n o t r e s i s t a n t t o sulphate attack. C3A
3
generates much more heat than does an equal amount of
t h e other components,

Calcium Allminof e r r i t e ( C ~ A F )

C4AF governs t h e colour of t h e cement; t h e higher

t h e C4AF t h e darker t h e cement. Actually, pure C4AF i s
brown but incorporation of MgO makes it dark grey/green
colour. T h i s component r e a c t s very slowly and i s of
l i t t l e importance t o t h e p r o p e r t i e s of cement, except
t h e colour.

1,,3 EFFECT OF IMPURITIES

Beside t h e f i v e main components (cao2, Si02, A1203,
Fe20j & M ~ O ) c l i n k e r contains sulphate, a l k a l i e s
( N ~ ~ K20)
o , and other minor components. These
components, which contaminate c l i n k e r owing t o i m p u r i t i e s
i n t h e raw m a t e r i a l and/or f u e l , a r e generally
undesirable.
The q u a n t i t i e s of such components in cement a r e
l i m i t e d e i t h e r by standard s p e c i f i c a t i o n s or by
manufact w i n g experience
19
.
.
I 3 I Magnesium Oxide
This component i s combined up t o 2%by weight with
t h e main c l i n k e r phases; beyond t h a t amount it appears
i n t h e c l i n k e r a s f r e e MgO ( ~ e r i c l a s e ) . P e r i c l a s e
r e a c t s with water t o f o m ~ g(OH) 2:

MgO + H20 3
- Mg(0~)~.

This reaction proceeds slowly, while t h e other hardening

reactions a r e already concluded. Since t h e Fig (OH)
occupies a l a r g e r volume than t h e MgO and i s l o c a t e d
t h e same spot where t h e p e r i c l a s e p a r t i c l e i s l o c a t e d
it can s p l i t a p a r t t h e binding of t h e hardened cement
p a s t e , r e s u l t i n g i n expansion cracks (magnesia expansion).
MgO appears i n limestone mainly a s dolomite (CaCo3.MgC03)

I . 3.2 Alkalies
K20 and. Na20 o r i g i n a t e from such raw m a t e r i a l s a s

clay and marl, where t h e s e compounds a r e present i n

f i n e l y dispersed f e l d s p a r , mica and i l l i t e p a r t i c l e s
 and t o a s m a l l e x t e n t - when using coal a s f u e l - from
, t h e c o a l ash. During t h e burning process in t h e r o t a r y
k i l n , p a r t s of t h e a l k a l i e s evaporate in t h e burning
zone, causing t h e so-called a l k a l i c i r c u l a t i o n , a
p r o c e s s impediment.
C e r t a i n concrete aggregates, appearing in some
p l a c e s l i k e USA, Denmark and Northern Germany contain
a l k a l i - s e n s i t i v e components e.g. opal (hydrated s i l i c a )
r e a c t i n g with a l k a l i of t h e cement, which under c e r t a i n
unfavourable c o n d i t i o n s can r e s u l t i n an expansion
phenomena ( a l k a l i expansion). A l k a l i expansion can be
prevented by using cement with low a l k a l i content; i n
t h i s case t h e t o t a l a l k a l i , c a l c u l a t e d a s Na20
(96 by weight Na20 + 0.659 K20) should n o t exceed 0.6%
by weight.

1.3.3 Sulphur
Sulphur appears predominantly a s sulphide ( p y r i t e s
and m a r c a s i t e , F e s 2 ) , i n almost all cement raw m a t e r i a l s .
A s a r e s u l t of t h e combustion, t h e sulphur of t h e
raw mix and of t h e f u e l evaporates i n t h e burning zone
t o SO2, which i n t h e Kiln atmosphere combines with a l k a l i
and oxygen, generating vaporized a l k a l i s u l p h a t e , which
condenses on. raw mix p a r t i c l e s i n c o l d e r Kiln zones a s
 as
wellLin t h e preheater. With t h e exception of a small
p a r t which i s c a r r i e d away by t h e Kiln d u s t , t h e a l k a l i
sulphate r e t u r n s with t h e Kiln feed i n t o -the burning
zone and - due t o i t s l o w v o l a t i l i t y - l e a v e s t h e Kiln
w i t h t h e clinker.
I f t h e SO2 content i s i n s u f f i c i e n t t o combine all
t h e a l k a l i e s , t h e c i r c u l a t i o n of t h e medium v o l a t i l e
a l k a l i carbonates or t h e high v o l a t i l e a l k a l i chlorides
begins. So f a r a s t h e a l k a l i carbonates a r e not bound
i n t h e c l i n k e r phases they evaporate again in t h e
burning zone.
I n t h e preheater, an excess of SO2 i s able t o r e a c t
with t h e CaC03, and t o r e t u r n t o t h e Kiln a s CaS04.
Then i n t h e burning zone, it decomposes again and t h u s
increases t h e SO2 - c i r c u l a t i o n of t h e Kiln gas.
However, a c e r t a i n p a r t w i l l appear i n t h e c l i n k e r a s
mdecomposed CaS04.
The presence of a l k a l i e s i n t h e raw mix i n excess
of t h e amomt which i s already combined by t h e sulphur
contained i n t h e raw mix, allows t h e use of high sulphur
f u e l s without emitting noteworthy q u a n t i t i e s of SO2 by
t h e Kiln e x i t gases. The a l k a l i sulphate combined by
t h e c l i n k e r i s of advantage f o r t h e early s t r e n g t h of
t h e cement, but diminishes i t s f i n a l strength. 20
On t h e o t h e r hand, h i g h e r s u l p h u r c o n t e n t s can r e s u l t
i n i n c r e a s e d SO2 einission w i t h t h e e x i t g a s e s , choking
t h e suspension p r e h e a t e r , as well as formation of Kiln
coating rings.
Hence it i s p o s s i b l e , by a d d i t i o n of c e r t a i n
c h l o r i d e s t o t h e Kiln charge, t o i n c r e a s e t h e v o l a t i l i t y
of t h e a l k a l i e s , t o remove by means of a bypass system
t h e a l k a l i c h l o r i d e t h a t i s formed, and in this way t o
lower t h e a l k a l i c o n t e n t of t h e c l i n k e r . The e f f e c t
of adding calcium c h l o r i d e has been r e p o r t e d i n Bohmanl s
paper. 21 I n most c a s e s t h e cheaper magnesium c l i l o r i d e
can s u i t a b l y b e used i n s t e a d of calcium c h l o r i d e . As
only small amounts a r e added (about 0,2% by Wt) , the
MgO c o n t e n t of t h e c l i n k e r i s n o t s i g n i f i c a n t l y i n c r e a s e d .
To c o n t r o l t h e s e t t i n g t i m e cement n e e d s a minimum
amount of calcium s u l p h a t e mostly i n t h e form of gypsum
added t o c l i n k e r . On t h e o t h e r hand, t h e maximum

allowable SO -content i n cement

3
t o prevent -
tlsulphate expansion ( i . e. formation of CaS04. 2 4 ~ ~ 0 ) -
i s e s t a b l i s h e d according t o t h e v a r i o u s cement
s t a n d a r d s , between 2.5 and 4.096 SO3. A t t h e lowest
l i m i t imposed by cement s t a n d a r d s p e c i f i c a t i o n , it
could b e p o s s i b l e t h a t t h e r e i s n o s u f f i c i e n t scope
l e f t f o r an e x t e n s i v e s u l p h a t i z a t i o n of t h e a l k a l i e s .
1.3.4 Chlorides
Since they condense q u a n t i t a t i v e l y in t h e preheater
they c i r c u l a t e between burning zone and preheater, u n t i l
incrqasing coating requires shut down of Kiln operation.
To prevat t h i s phenomenon, p a r t of the Kiln gases
( q t o 10-25%) a r e bypassed and do not e n t e r t h e
preheater. A s i s known from p r a c t i c e , bypassing of Kiln
gases is necessary a t a chloride content of more than
0.015"/0chloride i n t h e raw mix. 22
Previously, calcium chloride was added t o high
early s t r e n g t h cements t o boost t h e i n i t i a l s t r e n g t h
of t h e cement. However, it appears t h a t chloride
promotes corrosion of s t e e l , which had a detrimental
e f f e c t on t h e tension wires i n prestressed concrete.

1.3.5 Fluorides
Since t h e s e do not e a s i l y v o l a t i l i z e t h e f l u o r i d e
content of conventional cement raw m a t e r i a l s f l u c t u a t e s
within t h e l i m i t s of 0.03 and 0.08%.
The former p r a c t i c e of adding up t o approximately
1%of calcium f l u o r i d e t o t h e raw mix t o f a c i l i t a t e

c l i n k e r burning i s now mostly abandoned since t h e binding

of lime can b e achieved by a higher degree of homogenizFng
and f i n e r grinding of t h e raw mix.
1.3.6 Phosphorus
I n c a s e of raw m a t e r i a l ( s a y l i m e s t o n e ) w i t h a
h i g h P205 c o n t e n t , an a d m i s s i b l e l i m i t of about 2.5%
P205 i n t h e c l i n k e r i s advisable. However it should b e
n o t e d t h a t sometimes P205 c o n t e n t s as low as 0.5% can
a l r e a d y cause a c o n s i d e r a b l e d e c r e a s e in s t r e n g t h
e s p e c i a l l y i n t h e e a r l y s t r e n g t h of cement.

1.4 STANDARD SPECIFICATION

The aim of Q u a l i t y Control i s t o e n s u r e t h a t

f i n i s h e d product conforms t o t h e l a i d down s t a n d a r d
specification. These s t a n d a r d s a r e s e t t o g u i d e t h e
manufacturing p r o c e s s t o avoid producing poor q u a l i t y
goods, t h e r e b y p r o t e c t i n g t h e consumer.
According t o Standards Organisation of N i g e r i a
(SON) Amendment Decree 1 8 , 1990 SON has been empowered
t o t a k e any d e a l e r o r manufacturer of sub-standard
p r o d u c t s t o c o u r t i n a d d i t i o n t o s e a l i n g up his shop;
i f found g u i l t y , such e r r i n g d e a l e r would b e r e q u i r e d

t o pay a f i n e of W10,000, while a manufacturer would

pay W50 ,000 o r f i v e y e a r s imprisonment o r both. 23
Cement manufacture a l l over t h e world f o l l o w s some
u n i v e r s a l l y accepted s t a n d a r d s . However every country
u s u a l l y develops a s t a n d a r d s p e c i f i c a t i o n s p e c i a l l y
designed t o meet some l o c a l t e s t s / p e c u l i a r i t i e s .
Sub-standard cement can l e a d t o c o n s t r u c t i o n
d i f f i c u l t i e s and s t r u c t u r a l f a i l u r e s .
A s t a n d a r d s p e c i f i c a t i o n i s a complete d e s c r i p t i o n
of t h e q u a l i t y requirements t h a t must b e met d u r i n g
t h e p r o c e s s of manufacture f o r t h e f i n i s h e d product t o
b e considered good. Cement s p e c i f i c a t i o n s a r e g e n e r a l l y
b r o a d l y d i v i d e d i n t o chemical and p h y s i c a l p r o p e r t i e s .
The chemical p r o p e r t i e s a s e a r l i e r mentioned u s u a l l y
show t h e l i m i t s of parameters l i k e LSF, PIgO, S O 3 ,
I n s o l u b l e Residue (determined a s p e r a s p e c i f i e d
chemical t e s t ) and Loss On I g n i t i o n ( u s u a l l y a t 950 -+ 50°c).
P h y s i c a l p r o p e r t i e s normally s p e c i f i e d i n c l u d e t h e
f o l l o w i n g parameters which w i l l b e b r i e f l y explained
under experimental :
(i) F i n e n e s s which i n c l u d e s s p e c i f i c surf a c e
a r e a ( b l a i n e ) and s i e v i n g r e s i d u e .
( i i ) I n i t i a l and F i n a l S e t t i n g Times.
(iii) Soundness.
(iv) Compressive and/or bending s t r e n g t h .
The N i g e r i a n s t a n d a r d s p e c i f i c a t i o n on cement i s
Nigerian I n d u s t r i a l Standards, 111S . 11'/1974.
I n B r i t a i n t h e c u r r e n t s p e c i f i c a t i o n f o r Ordinary and
Rapid-Hardening P o r t l a n d Cement i s d r i t i s h Lkandard,
8~,12/1978. The AmericarS have t h e American Society f o r
Testing and Dlaterials (ASTM)which provides t h e
s p e c i f i c a t i o n f o r a l l v a r i e t i e s of m a t e r i a l s includbqg
cement. Table 3 shows t h e designations of cement
standards of some countries of t h e world; 24 t h e symbols
used being explained below t h e t a b l e .
It i s common p r a c t i c e i n any cement f a c t o r y t o
i s s u e regular t e s t c e r t i f i c a t e which shows t h e standard
s p e c i f i c a t i o n adopted and t h e t e s t r e s u l t s obtained
from t h e chemical and physical a n a l y s i s of a production
batch. A t y p i c a l c e r t i f i c a t e of t e s t s can be seen on
Table 4.
 CHAPTER 2

LITERATURE REVIEW

I n v e s t i g a t i o n s i n t o v a r i o u s a s p e c t s of cement
manufacture a r e continuously undertaken by s c h o l a r s
s i n c e t h e o r i g i n of cement i n t h e a n c i e n t Roman times.
A s f a r back as 1724 t h e B r i t i s h engineer, Lineaton 25
recognised t h e importance of t h e c l a y component as
e s s e n t i a l t o t h e h y d r a u l i c s e t t i n g and hardening
behaviour. ~ a t e e1s t a~b l~i s h e d t h a t t h e r e i s a d i r e c t
r e l a t i o n s h i p between t h e n a t u r e of raw m a t e r i a l s and
t h e p h a s e s formed i n cement c l i n k e r . Further studies
were a l s o c a r r i e d o h by Reuss and 6abich,28 bordering
on homogenization and o p t i m i z a t i o n of raw m a t e r i a l
mixtures f o r burning c l i n k e r i n dry p r o c e s s k i l n s . The
more homogeneous a raw f e e d i s t h e b e t t e r w i l l b e i t s
performance in t h e k i l n . To demonstrate t h e e f f e c t of
physicochemical p r o p e r t i e s of raw m a t e r i a l s on cement
q u a l i t y ~ u d n i k o v ~produced
' t h e r e s u l t s of Laboratory
experiments w i t h Biff e r e n t raw m a t e r i a l s as well as t h e
r e s u l t s of r o t a r y k i l n performance i n some Soviet cement
plants. D i f f e r e n t works 30-33 by many s c h o l a r s have
confirmed t h a t e x c e s s i v e l e v e l s of a l k a l i e s and sulphur
i n t h e raw m a t e r i a l s a r e very dangerous from b o t h
p r o c e s s and q u a l i t y c o n t r o l p o i n t of view.
Improvements i n t h e manufacturing p r o c e s s have been
sought w i t h emphasis on energy s a v i n g s through economic
f u e l u t i l i z a t i o n 3 ' -36 o r manipulation of p r o c e s s
39
c o n d i t i o n s37938. 1933 saw t h e e s t a b l i s h m e n t by Knehl
of l i m e s t a n d a r d formula which can b e used i n conjunction
w i t h s i l i c a r a t i o and alumina r a t i o t o judge t h e cement
properties. I n 1969 ~ o r n i t a ~showed
' how t h e r a t e of
c o o l i n g c l i n k e r below 1 . 2 0 0 ~t o~ ambient t e m p e r a t u r e
a f f e c t e d t h e q u z l i t y of c l i n k e r produced.
S t u d i e s on cement t e s t i n g and q u a l i t y c o n t r o l have
s p r e a d a c r o s s a l l p o s s i b l e t e s t i n g procedures i n c l u d i n g
g r a v i m e t r y , t i t r i m e t r y , complexometry and i n s t r u m e n t a l
techniques. Wang and chen4' determined alumina i n
cement samples by EDTA complexometric t i t r a t i o n .
S i m i l a r t e s t i n g methods have been a p p l i e d f o r
q ~ ~ a n t i t a t i vees t i m a t i o n of o t h e r elements l i k e Ca, Mg
and Fe.
I n 1970 I3aiL2 a p p l i e d D i f f e r e n t i a l Thermal A n a l y s i s
(DTA) t o s t u d y hydrated h y d r a u l i c lime. L a t e r on, in
1976, P e r i c and ~ r s t u t o vcL3
i c a r r i e d o u t comparative
t e s t i n g of cement raw m a t e r i a l s by thermometric methods.
Four raw m a t e r i a l samples were analysed. The accuracy
of t h e method, a s compared t o c l a s s i c a l chemical a n d l y s i s
was e s t a b l i s h e d by s t a t i s t i c a l v a l u e s . Comparative
examinations w i t h o t h e r methods such a s X-ray f l u o r e s -
cence show t h e i r equivalence and t h e advantages of one
method over t h e o t h e r . I n modern cement t e s t i n g
L a b o r a t o r i e s high degree of instrumentation/a&omation
i s r e q u i r e d , with p a r t i c u l a r emphasis on X-ray
analyzer. 44-46 ~ o m i an ~
his~ work i n 1985 had given
g e n e r a l recommendations f o r a n a l y t i c a l work in carrying
out standard chemical a n a l y t i c a l procedures f o r
hydraulic binders.
From a l l a v a i l a b l e l i t e r a t u r e no published work
has so f a r been done on comparative s t u d i e s of cement
q u a l i t y and s t a n d a r d s of Nigerian cement manuf a c t w e .
The economic n e c e s s i t y f o r a c c e l e r a t e d development of
Nigerian cement i n d u s t r y as e a r l i e r explained, coupled
with t h e p i t i a b l e absence of a cement Research and
Development Centre i n t h e country makes such a r e s e a r c h
of prime importance, It would even b e of b o t h academic
and i n d u s t r i a l i n t e r e s t t h a t such an i n v e s t i g a t i o n i s
undertaken from time t o time.

2.1 A I M AND JUSTIFICATION OF RESEARCH

Cement has become a major b u i l d i n g m a t e r i a l f o r
c i v i l engineering c o n s t r u c t i o n s l i k e skyscrappers, f l y -
overs, roads, houses, c u l v e r t s , b r i d g e s , etc. Inspite
of t h e growing r a t e of i n d u s t r i a l i z a t i o n and u r b a n i z a t i o n
i n N i g e r i a t h e b u i l d e r i s more o r l e s s r e s t r i c t e d t o
use m a d e - i n - ~ i ~ e r icement,
a due t o import r e s t r i c t i o n s
imposed by t h e p r e s e n t economic c l i m a t e of t h e country,
T h i s r e s e a r c h was designed t o i n v e s t i g a t e , i n
s e l e c t e d N i g e r i a n Cement Companies, t h e f o l l o w i n g
manufacturing and q u a l i t y i s s u e s which would b e of
p a r t i c u l a r i n t e r e s t t o t h e consumers of t h e v a r i o u s
cement brands manufactured i n Nigeria:
How i s t h e comparison of q u a l i t y and s t a n d a r d s
of t h e s e cement brands and how do t h e y r e l a t e
t o f o r e i g n made brands?
I n p a r t i c u l a r , what i s t h e degree of
consistency i n t h e q u a l i t y of t h e i r b a t c h
productions?
How f a r does t h e raw m a t e r i a l q u a l i t y i n f l u e n c e
t h e f i n i s h e d product?
What a r e t h e e f f e c t s , i f any, of t h e production
methods (wet o r dry) on t h e product q u a l i t y ?
From a l l i n d i c a t i o n s t h e Nigerian b u i l d i n g
i n d u s t r y w i l l c o n t i n u e t o depend predominantly on t h e
Nigerian made cement a s we c o n t i n u e t o march t o s e l f
r e l i a n t economy, However t h e p r e s e n t t o t a l cement
production of t h e country which s t a n d s a t about 3.5
m i l l i o n tonnes per annum can only s a t i s f y about 40%
of t h e n a t i o n ' s need a t t h e moment. Many of t h e
48
e x i s t i n g cement companies have mapped out optimization
and/or expansion programmes t o boost production, More

S t a t e s l i k e Gongola have planned t o e s t a b l i s h new

cement companies. 49
T h i s work t h e r e f o r e f o c u s e s on t h e comparative
s t u d i e s of q u a l i t y and standards of some Nigerian made
cement brands and a f o r e i g n cement brand, i n l i n e with
t h e above-mentioned i n v e s t i g a t i v e guidelines.
 CHAPTER 3
EXPERIMENTAL

3.1 MATERIALS, REAGESJTS AND EQUIPMENT

A l l t e s t i n g m a t e r i a l s and reagents used were of t h e

standard requirement. Wet chemical a n a l y s i s by Quick

Wet Method (QWM) employed combined complexometry and
gravimetry , using analar grade reagents and weighing
with Mettler AE 163 a n a l y t i c a l balance.
Equipment f o r t e s t i n g include flame photometer f o r
determination of t h e a l k a l i e s , Toni Technik Compressive
s t r e n g t h machine and Electronic A i r Permeability t e s t e r
( ~ o d e l7207) f o r b l a i n e det erminatioii.
A l l m a t e r i a l s , reagents and equipment f o r Laboratory
a n a l y s i s met Nigerian I n d u s t r i a l Standards (NIS) .
3.2 SAMPLE COLLECTION
Samples of cement were c o l l e c t e d from batches
produced within t h e same week i n t h r e e Nigerian Cement
Companies, namely, The Nigerian Cement Company, Nkalagu,
Calabar Cement Company, Calabar, and rjenue Cement
Company, Gboko. Also t h e raw m a t e r i a l s used f o r t h e s e
batch productions were collected. A f o r e i g n Ordinary
Portland Cement brand, Eagle Cement, was a s well
sampled from Kenyatta market, Ehugu within t h e same
sampling period. These samples were t e s t e d p a r t l y
g r a v i m e t r i c a l l y and p a r t l y complexometrically ,
according t o standard methods of analysis. 50 951
After one month i n t e r v a l a second s e t of samples from
t h e same sources mentioned above were again c o l l e c t e d
and t e s t e d .

3.3 SAMPLE PREPARATION

For uniformity of t e s t i n g and t o obtain b e s t
r e s u l t s a l l raw m a t e r i a l or cement samples f o r chemical
and p h y s i c a l a n a l y s i s were reduced t o f i n e powder having
a f i n e n e s s of 0% r e s i d u e on 90 \un sieve. Also t e s t s
were c a r r i e d out with dry samples.

3.4 CHEKCCAL A N A L Y S B OF RAW 1VIATERIALS ,4ND PRGDUCTS

The following p r i n c i p a l parameters were t e s t e d f o r :

3.4.1 Loss On I g n i t i o n (LOI)

This i s c a r r i e d out a s s t i p u l a t e d i n t h e i4igerian
I n d u s t r i a l Standards (NIs. 11 /1974) 52 by i g n i t i n g l g of
sample a t a temperature of 950 -+ 5 0 ' ~ till constant
weight. The percentage l o s s i n weight i s t h e n determined.
I g n i t i o n l o s s f o r cement and i t s raw m a t e r i a l s usually
c o n s i s t s of moisture and/or C02 contents.
3.4.2 I n s o l u b l e Residue (IR)
The t e s t i s designed i n t h e s p e c i f i c a ' t i o n f o r
estimation of t h e q u a n t i t y of cement which i s i n s o l u b l e
in hydrochloric a c i d of s p e c i f i e d m o l a r i t y .
This i n v o l v e s d i s s o l v i n g one gram of sample i n hot
d i l u t e HC1 and f i l t e r i n g with a s p e c i f i e d f i l t e r paper.
The r e s i d u e i s again d i s s o l v e d w i t h 1 M N a 2 C O j s o l u t i o n and
also filtered. The r e s i d u e a t each s t a g e i s washed s e v e r a l
t i m e s , following t h e s t i p u l a t e d standard procedure. The
f i l t e r paper w i t h t h e f i n a l r e s i d u e i s d r i e d , i g n i t e d a t
-
950 + 5 0 ' ~ and weighed a s " i n s o l u b l e residue".

3.4.3 S i l i c a ( s ~ o , ) De-teniination

S i l i c a determination was done g r a v i m e t r i c a l l y by

Quick Wet Method (QWM), p r e c i p i t a t i n g t h e s i l i c a w i t h a c e t i c
anhydride and c a r r y i n g o u t t h e t e s t according t o t h e
standard procedures,53 t o o b t a i n t h e percentage s i l i c a i n
t h e sample. For cement, c l i n k e r o r raw meal l.g of sample
i s used; f o r raw m a t e r i a l s 0.5g of sample i s used.

3.4.4 Determination of CaO, MgO, Fe203 and N 2 0 3

The percentage of t h e s e o x i d e s in cement and raw

m a t e r i a l s were determined by a complexometric t i t r i m e t r y ,
s t i l l under t h e Quick Wet Method. The f i l t r a t e from t h e
 corresponding Si02 determination was used. The

f i l t r a t e c o l l e c t e d in a 250 m l volumetric f l a s k was

allowed t o c o o l t o room temperature. I t was t h e n made
up t o t h e mark using d i s t i l l e d water.
A demonstration of t h e procedure i s shown below
f o r lime ( c ~ o )determination:

3.4.5 -
~ c t e w b f n a Z 1 0 nof' Lime ( c ~ o )
A. Reagents
(i) a h y l e n e g l y c o l - b i s - (2-aminoethyl) t e t r a a c e t i c
a c i d , C14H26N2010 (otherwise denoted a s K ).
5
(ii) T r i e t hanolamine hydrochloride
(iii) Potassium hydroxide
(iv) Murexide

(v) N ap h t hol G r e en-B

(vi) Sodium chloride.

B. Equipment
(i) Pipette
(ii) .Stirring bar
(iii) Watch g l a s s
(iv) Beaker
(v) Magnetic s t i r r e r
(vi) Automatic B u r e t t e s e t
 (vii) Spatular
(viii) pH meter.

C. P r e p a r a t i o n of s o l u t i o n s / r e a g e n t s
The s o l u t i o n s / r e a g e n t s used in l i m e d e t e m i n a t i o n
were p r e p a r e d a s follows:
(i) K, ( 0 . 0 5 ~ ): hxhylene g l y c o l - b i s - (2-aminoethyl)
t e t r a a c e t i c a c i d , 1' 4H26'q20~
0
pour 1.6 l i t r e s of 0.5M KOH i n t o 2 l i t r e beaker.
Add 97g of Kg. Cover t h e b e a k e r and p l a c e it on a hot
p l a t e t o b o i l f o r 3-4 minutes. Cool t o room temperature.
I n t o a 5 l i t r e beaker pour 2 l i t r e s of d i s t i l l e d water.
Add t h e whole of t h e s o l u t i o n p r e p a r e d above, Mix
thoroughly (using a g l a s s r o d o r a magnetic s t i r r e r ) .
By using t h e pH meter a d j u s t t h e pH t o j u s t above 10,
by adding more 0,5M KOH,
T r a n s f e r t h e whole l i q u i d i n t o a 5 l i t r e v o l u m e t r i c
f l a s k and make up t o t h e mark adding more d i s t i l l e d
water. Before t h e s o l u t i o n i s used f o r a n a l y s i s i t s
f a c t o r should f i r s t b e determined.

F a c t o r Determination
Obtain t h e f i l t r a t e from t h e s i l i c a d e t e r m i n a t i o n
of a s t a n d a r d sample ( i . e, a sample whose CaO v a l u e i s
a c c u r a t e l y known). Use t h i s f i l t r a t e t o c a r r y out
t i t r a t i o n f o r CaO i n t h e usual way. Using t h e t i t r e
c a l c u l a t e t h e percentage CaO, assuming a f a c t o r of 1.

3tandard v a l u e
Fact o r =
e m e r i m e n t a l value obtained with t h e
new s o l u t i o n (assuming a f a c t o r of I ) .

However i f t h e L.O.I. of t h e standard sample has changed

from t h e o r i g i n a l v a l u e t h i s must be r e f l e c t e d i n
obtaining t h e experimental v a l u e i n t h e equation above.
For example i f x i s t h e experimental v a l u e obtained by
c a l c u l a t i o n using t h e t i t r e v a l u e , t h e n t h e c o r r e c t
v a l u e of x i s given by
x, 100 - L.O.I. (original)
'I00 - L.O.I. (experimental)

(ii) Potassium Hydroxide (20~6)

I n t o a 600 m l beaker pour 400 m l of d i s t i l l e d
water. Then add 200g KOH and d i s s o l v e it by s t i r r i n g
( e i t h e r with a g l a s s rod or a magnetic s t i r r e r ) .
Transfer t h e l i q u i d i n t o a I l i t r e volwnetric f l a s k ,
washing out t h e beaker with d i s t i l l e d water i n t o t h e
volumetric f l a s k , but making s u r e t h a t t h e I l i t r e mark
i s not exceeded. Make up t o t h e mark and shake t h e
volumetric f l a s k thoroughly. Ifransf e r t h e s o l u t i o n t o
a polyethylene vessel.
(iii) Lime I n d i c a t o r
Weigh t h e following chemicals as given and g r i n d
i n a mortar t o a f i n e powder:
I g murexide (otherwise known a s ammoniun p u r p u r a t e a c i d ) ,

C8H8N606a
2.5g Naphthol Green-B and
100g Sodiwn Chloride.

D. Procedure f o r Lime ( c ~ o )Determination

25 m l of t h e s o l u t i o n prepared with t h e f i l t r a t e
from s i l i c a d e t e r m i n a t i o n , a s e a r l i e r d e s c r i b e d , i s
p i p e t t e d i n t o a 250 m l beaker c o n t a i n i n g a s t i r r i n g b a r
and covered w i t h a watch g l a s s . P l a c e t h e beaker on
t h e magnetic s t i r r e r s o t h a t t h e t o p of an aut;ornatic
b u r e t t e i s poin&ing i n t o t h e beaker.
I n t o t h e b u r e t t e i s poured a s t a n d a r d s o l u t i o n of
ethyleneglycol-bis- (2-aminocthyl) t e t r a a c e t i c a c i d ,
C14H26N2010 ( h e r e a f t e r t o be r e f e r r e d t o a s $ ) . To
t h e beaker add about 0.5g of t r i e t h a n o l a m i n e hydrochloride
(using a s p a t u l a r ) and allow it t o d i s s o l v e by s t i r r i n g .
Then t h e s o l u t i o n i n t h e beaker i s d i l u t e d ( w i t h
d i s t i l l e d water) upto 150 m l mark on t h e beaker wall.
Now t h e pH meter i s g o t ready t o measure t h e pH of t h e
solution. A f t e r s e t t i n g t h e automatic b u r e t t e t o dosage
p o s i t i o n 20% KOH s o l u t i o n i s added dropwise from a
p i p e t t e i n t o t h e beaker u n t i l t h e pH i s 8 (watch t h a t
a t t h i s p o i n t t h e brownish c o l o u r of t h e s o l u t i o n changes
t o near colourless). More 2036 KOH s o l u t i o n i s now added
f a s t till t h e pH of t h e s o l u t i o n i n t h e b e a k e r i s 12.5 -
13.5. About 1 7 m l of 20% KKO s o l u t i o n w i l l b e enough t o
come t o t h i s pH range. The KOH a d d i t i o n i s followed a s
f a s t a s p o s s i b l e by a d d i t i o n from t h e b u r e t t e of about
90% volume of expected K t i t r e ; t h e f o l l o w i n g volumes
5
have been recommended (based on experimental d a t a ) f o r
immediate a d d i t i o n i n t h e corresponding sample a n a l y s i s :
C l i n k e r and cement - 22 m l
Raw meal - 14ml

By e x p e r i e n c e an a n a l y s t w i l l f i n d out f o r himself
what i n i t i a l volume of K i s most a p p r o p r i a t e . Lime
5
i n d i c a t o r i s now added j u s t enough t o make t h e s o l u t i o n
reddish. F i n a l l y t h e t i t r a t i o n i s continued dropwise
till t h e end-point ( b l u i s h c o l o u r ) i s reached. The end-
p o i n t should b e p r e c i s e . We g e t a c l e a r i n d i c a t i o n t h a t
this has b.een reached when an a d d i t i o n a l drop of K
\ 5 into
t h e beaker does n o t g i v e r i s e t o any v i s i b l e c o l o u r
change of t h e l i q u i d i n t h e beaker. Then t h e r e a d i n g of
t h e b u r e t t e j u s t b e f o r e t h e a d d i t i o n of t h a t l a s t drop i s
the titre. To confirm t h a t t h e end-point h a s been reached,
 two more drops a r e added t o g e t h e r from t h e b u r e t t e t o
t h e beaker (and t h e r e should be no v i s i b l e colour change)

-C a l c u l a t i o n
For c l i n k e r , cement and Raw Meal:
t i t r e x 10 x 2.804 x fKg
O/o CaO =
10

where 10 (above) = d i l u t i o n f a c t o r
10 (below) = n m b e r i n d i c a t i n g "per 100"
1000 me: = 10)
(i.e.

Since I g ( o r 1000 mg) of sample was weighed.

2.804 = S p e c i f i c v a l u e f o r C a O

(i.e. 1 m l of 0.05M K5 = 2.804 mg C ~ O )

,
fK5 = c a l c u l a t e d f a c t o r f o r
For raw m a t e r i a l s :
Ks .
% CaO = ( t i t r e x 10 x 2.804 x f ? ) - (CaO equivalent of
CaCO, weighed)
5 J

The c o n s t a n t s a r e a s described above; here we d i v i d e by 5

s i n c e 500 mg ( i n s t e a d of 1000 mg above) i s t h e e f f e c t i v e

weight of sample used. Note t h a t C a O e q u i v a l e a t of

500 mg CaC03 = 280 .I mg.

3.4 .,6 Determination of Magnesia ( ~ ~ 0 )

A. Preparation of s o l u t i o n s / r e a g e n t s

The s o l u t i o n s / r e a g e n t s used in magnesia determination

were prepared a s follows:

 (i) Eriochrome Black T
Weigh 1.0g Eriochrome Black T and 200.0g K C 1 i n t o a

dry mortar. Grind t h e two t o g e t h e r w i t h a p e s t l e , t o

o b t a i n a homogeneous mix.

(i i ) E t h y l e n e glycol-bis-(2-arninoethyl)
t e t r a a c e t i c a c i d , C14H26N2010 ( d e n o t e d a s ~ g )
Prepared a s a l r e a d y d e s c r i b e d e a r l i e r .

(iii) I -2-3( c y c l o h e x e l e n e d i n i t r i l o ) - t e t r a a c e t i c a c i d ,
C1 4H22N 208 .H20 ( denoted a s K ~ )

Pour I .6 l i t r e s of 0.5M KOH i n t o a 2 l i t r e b e a k e r .

Add 92.5g of K4. Cover t h e b e a k e r and p l a c e it on a h o t

p l a t e t o b o i l f o r 3-4 rnins. Cool t o room t e m p e r a t u r e .

I n t o a 5 l i t r e b e a k e r pour 2 l i t r e s o f d i s t i l l e d w a t e r .

Add t h e whole of t h e above-prepared l i q u i d , u s i n g a g l a s s

r o d and d i s t i l l e d w a t e r f o r a thorough t r a n s f e r of t h e

l i q u i d i n t o t h e 5 l i t r e beaker, By u s i n g a pH m e t e r and

adding more of 0,5M KOH ( w h i l e s t i l l s t i r r i n g t h e l i q u i d )

a d j u s t t h e pH t o t h e v a l u e 7.8 - 8.2. Then t r a n s f e r t h e

whole l i q u i d i n t o a 5 l i t r e v o l u m e t r i c f l a s k and make up

t o t h e mark by adding more d i s t i l l e d water. Before t h e

used
-
s o l u t i o n i s / f o r a n a l y s i s i t s f a c t o r s h o d d b e determined

a s e a r l i e r described f o r K
5'

B . Procedure f o r Magnesia (MRO)Determination

25 m l of t h e s o l u t i o n p r e p a r e d w i t h t h e f i l t r a t e from

s i l i c a determination, as e a r l i e r described, i s p i p e t t e d
i n t o a 250 m l b e a k e r c o n t a i n i n g a s t i r r i n g b a r and covered

w i t h a watch g l a s s . To t h i s b e a k e r add about I g of

NH4C1 s o l i d , and p l a c e it on t h e magnetic s t i r r e r .

Add 10 m l t r i e t h a n o l a m i n e ( I : I s o l u t i o n ) , followed by
4 m l of HC1 ( 1 : l s o l u t i o n ) . Then more of t h e HC1 i s
added drop-wise u n t i l t h e s o l u t i o n j u s t t u r n s g r e e n i s h w i t h
o n l y one a d d i t i o n a l drop of HC1.
\
Using a s p a t u l a r add
about 0.5g of hydroxylamine hydrochloride. Cover t h e
b e a k e r and a l l o w t h e s o l i d t o d i s s o l v e f u l l y and b e s t i r r e d
f o r about 2 mins. Using c o n c e n t r a t e d ammonia solu-tion
a d j u s t t h e pH of t h e s o l u t i o n t o 10.1 - 10.2, w i t h t h e
h e l p of t h e pH meter. Then w i t h a s p a t u l a r add about 0.5g
of KCN (care! t h e substance i s v e r y poisonous). Transfer

t h e b e a k e r c o n t a i n i n g t h e s o l u t i o n t o a hot p l a t e and l e t
it b o i l f o r about 30 seconds in t h e fume chamber. Leave
t h e s o l u t i o n h t h e fume chamber t o cool t o room
temperature. PJow p l a c e back t h e b e a k e r on t h e magnetic
s t i r r e r and d i l u t e t h e s o l u t i o n ( u s i n g c o l d d i s t i l l e d
water) t o about 180 m l . Add t o t h e s o l u t i o n ( c ~ Ot i t r e +
1 ml) K5, followed by a pinch (about 0.1 mg) of magnesium
complexonate ( i .e . magnesium EDTA) and about two s p a t u l a r -
f u l l s of Eriochrome Black T i n d i c a t o r . Now t i t r a t e drop-
wise w i t h K4 u n t i l (copper-sulphate b l u e ) end-point i s
reached. Confirmation of end-point i s as d e s c r i b e d i n l i m e
determination. Volume of K4 used i s t h e t i t r e t o b e

a p p l i e d in t h e c a l c u l a t i o n .

-Calculation:
Case I: For c l i n k e r , cement and raw meal samples.

% MgO =
t i t r e x 10 x 2.016 x fKq
10

CaseII: For raw m a t e r i a l s :

% MgO =
t i t r e x 10 x 2.016 x fK4
&
The c o n s t a n t s a r e a s described in t h e procedure f o r l i m e
determination. Here we d i v i d e by 5 s i n c e 500 mg ( i n s t e a d
of 1000 mg above) i s t h e e f f e c t i v e weight of sample used.
2.016 = s p e c i f i c v a l u e f o r MgO.

3.4.. 7 Determination of I r o n Oxide (F~,o,)

A. Preparation of s o l u t f o n s / r e a g e n t s
(i) Ammonium Acetate (50%)
I n t o a 600 m l beaker pour 400 r n l of d i s t i l l e d water.
Then add 500g of ammonium a c e t a t e and s t i r thoroughly
( e i t h e r w i t h a g l a s s rod o r a magnetic s t i r r e r ) ,
T r a n s f e r t h e l i q u i d i n t o a 1 l i t r e volumetric f l a s k ,
washing o u t t h e beaker w i t h d i s t i l l e d water, i n t o t h e
volumetric f l a s k , b u t making s u r e t h a t t h o 1 l i t r e mark i s
n o t exceeded. By adding more d i s t i l l e d water t h e volumetric
f l a s k i s made up t o t h e mark and shaken thorougldy.
 T r a n s f e r t h e s o l u t i o n t o a polyethylene v e s s e l ,
( ~ o t teh a t ammonium a c e t a t e can r e a c t w i t h c o n t a i n e r s
made of s i l i c e o u s m a t e r i a l ) .

(ii) 5-Sulphc?salicylic a c i d (20%),

0 --

I n t o a 100 m l beaker pour 60 m l d i s t i l l e d water. Add

20g of 5 - s u l p h o s a l i c y l i c a c i d. Transfer t h e l i q u i d i n t o a
100 m l v o l u m e t r i c f l a s k and make up t o t h e mark u s i n g
d i s t i l l e d water.

(i i i ) I-2-( cyclohexehenedinitri10)-tetraacetic acid,

C1 4H22N208 .H20 ( denoted as K ~ )

T h i s was prepared a s e a r l i e r described.

B. Procedure f o r I r o n Oxide ( F ~ , o , ) Determination

50 m l of t h e s o l u t i o n prepared w i t h t h e f i l t r a t e from
s i l i c a determination i s p i p e t t e d i n t o a 250 m l b e a k e r
c o n t a i n i n g a s t i r r i n g b a r and covered w i t h a watch g l a s s .
i
Then add 1 m l H202 and 10 m l of water. B o i l i n t h e fume
minute
chamber f o r 10 . . $while s t i l l covered w i t h watch g l a s s )
and cool t o room temperature s t i l l i n t h e f u n e chamber.
P l a c e t h e beaker c o n t a i n i n g t h e s o l u t i o n on t h e magnetic
s t i r r e r (which i s p o s i t i o n e d by t h e s i d e of t h e automatic
, b u r e t t e f o r t h e t i t r a t i o n ) and d i l u t e t h e s o l u t i o n t o 200 m l .
 52

Using t h e pH meter and by adding 50% ammonium a c e t a t e

a d j u s t t h e pH of t h e solution t o 1.4 - 1.5.

Into t h e automatic b u r e t t e pour a standard s o l u t i o n
of K4 and ad j u s t t h e b u r e t t e t o dosage p o s i t i o n . Then
add about 90% volume of t h e expected t i t r e of K4
(recommended volumes t o b e added are: c l i n k e r o r cement -
1.70 m l ; Raw meal - 1 -00 ml) followed by 1 m l 20%
s u l p h o s a l i c y l i c a c i d s o l u t i o n ( c o l o u r changes t o v i o l e t ) .
Mow t r a n s f e r t h e beaker unto a hot plate/magnetic s t i r r e r
(which has been pre-heated); f i x a thermometer and t h e
pH meter e l e c t r o d e in t h e s o l u t i o n . The s o l u t i o n i s l e f t
t o be heated a s well a s s t i r r e d f o r a t l e a s t 5 mins.
Within t h i s i n t e r v a l t h e temperature of l i q u i d in t h e
beaker i s expected t o have r i s e n t o 90 - 95'~. Under t h i s
temperature range t h e t i t r a t i o n i s continued drop-wise
till t h e ( yellow-green) end-point i s reached.
Confirmation of end-point i s a s described in lime
determination.
CALCULATION :
Case I: For c l i n k e r , cement and Raw meal:

where 5 = dilution factor

3.9925 = s p e c i f i c v a l u e f o r Fe 0
2 3

number i n d i c a t i n g "per 100 mg"

 53

100 I), s i n c e 1000 mg of sample was weighed

(1.e. = qJ
fK4 = c a l c u l a t e d f a c t o r f o r K4.

Case 11: For raw m a t e r i a l s :

The c o n s t a n t s a r e a s d e s c r i b e d i n Case I above; here we

d i v i d e by 5 s i n c e 500 mg ( i n s t e a d of 1000 mg above) i s
t h e e f f e c t i v e weight of sample used.

3 -4.8 Determination of Alumina ( ~ 1 9 ~ )

A. P r e p a r a t i o n of s o l u t i o n s / r e a g e n t s
(i) Ammonium Acetate (50%)
This was prepared a s e a r l i e r described in s e c t i o n

(ii) 1-2-( cyclohexelene d i n i t r i l o l - t e t r a a c e t i c a c i d ,

C,4H22N208-H20 (denoted a s K ~ )
- - -- -

Prepared a s e a r l i e r described in s e c t i o n (3.4.7).

(iii) Copper-EDTA (copper complexonate) ( 0 . 0 1 ~ )

I n t o a 100 m l beaker pour 60 m l d i s t i l l e d water.
Add 0.3977g of Copper-EDTA (copper complexonate) and s t i r
t o d i s s o l v e thoroughly. T r a n s f e r t h e l i q u i d i n t o a 100 r n l
w l u m e t r i c f l a s k and make up t o t h e mark. P o w t h e prepared
s o l u t i o n i n t o a dropper b o t t l e .
(iv) PAN I n d i c a t o r (0.2% i n e t h a n o l )

I n t o a 250 m l b e a k e r pour 100 m l of e t h a n o l .

Add O.2g PAN i n d i c a t o r -/i-(2 - p y r i d y l a z o ) - 2 - ~ a ~ h t h 1 _ 7 .
Cover t h e b e a k e r w i t h a watch g l a s s and h e a t t o b o i l i n g

on a h ~ ptl a t e ; till a l l t h e s o l i d h a s gone i n t o s o l u t i o n .

Remove t h e b e a k e r from t h e h o t p l a t e and c o o l t o room

temperature. Pour t h e s o l u t i o n i n t o a 100 m l g l a s s

dropping b o t t l e . ( ~ o t et h a t a l c o h o l e a s i l y r e a c t s w i t h

polyethylene v e s s e l s ) .
B . P r o c e d u r e f o r Alunina (A1203) D e t e r m i n a t i o n
--- - --- - - - - -

To t h e same l i q u i d in t h e b e a k e r u s e d f o r Fe203

d e t e r m i n a t i o n ( a f t e r t h e Fe2O3 end-point h a s b e e n r e a c h e d )

fix t h e pH meter e l e c t r o d e and a d j u s t t h e pH m e t e r f o r

temperature. Now add t o t h e b e a k e r 50% ammonium a c e t a t e

s o l u t i o n ( w h i l e t h e l i q u i d in t h e b e a k e r i s s t i l l b e i n g

h e a t e d and s t i r r e d ) till t h e pH = 3.2 - 3.5. Add more K4

from t h e same b u r e t t e s t i l l having t h e r e a d i n g of t h e

c o r r e s p o n d i n g Fe203 d e t e r m i n a t i o n . Make t h e t o t a l volume

o f K4 added f o r b o t h Fe203 and A1203 = 6.0 m l f o r c l i n k e r

a n d cement, 4.0 m l f o r raw meal and 2.5 m l f o r raw

material. The most a p p r o p r i a t e i n i t i a l volume o f K4 t o b e
added can b e d e t e r m i n e d t h r o u g h working e x p e r i e n c e w i t h a

p a r t i c u l a r sample t y p e . To t h e b e a k e r p u t 3 d r o p s of

copper-EDTA ( o t h e r w i s e known a s C U K ~ and ) m 02 PAN

~ ~ 1
indicator. When t h e t e m p e r a t u r e i s 90 - 95'~titrate drop-

wise w i t h K4 till (brownish-yellow) end-point i s reached.

Here slow t i t r a t i o n i s e s s e n t i a l s i n c e t h e r e a c t i o n r a t e
i s low. Confirmation of t h e end-point i s as d e s c r i b e d
i n 1ime d e t e r m i n a t i o n .

-CALCULATION :
-Case I
96 Al2O3 =
(total t i t r e - Fe2O3 t i t r e ) x 5 x 2.5490 x f K 4
--
10
where,
5 = dilution factor
2.5490 = s p e c i f i c v a l u e f o r A1203
fK4 = c a l c u l a t e d f a c t o r f o r K4
10 = nunber i n d i c a t i n g "per 100 mg" .
Case 11:
For raw n a t e r i a l s :
(total t i t r e - Fe,03 t i t r e ) x 5 x 2.5490 x fKl,

The c o n s t a n t s a r e a s d e s c r i b e d in c a s e I above; here we

d i v i d e by 5. s i n c e 500 mg ( i n s t e a d of 1000 mg above) i s t h e
e f f e c t i v e wel.ght of sample. used
3.4.9 Detemina-tion of o t h e r Chemical Parameters
Other chemical parameters determined i n c l u d e
a l k a l i e s (IIa2O & K20), SO 3 and f r e e ( o r uncombined)
l i m e ( c ~ o )i n t h e cement.
The a l k a l i e s were determined using a flame photo-
m e t e r , Model IL 243. t e s t was g r a v i m e t r i c ; one
%3
gram of c l i n k e r o r cement sample b e i n g d i s s o l v e d i n a
l i t t l e volume of warm HC1 s o l u t i o n and t h e n p r e c i p i t a t i n g
w i t h barium c h l o r i d e s o l u t i o n . The f r e e l i m e was
e x t r a c t e d from g r o ~ m dc l i n k e r o r cement by t r e a t m a i t w i t h
hot ethanediol. The e x t r a c t i o n produces a s o l u t i o n of
calcium g l y c o l l a t e which, a s a s a l t of a v e r y weak a c i d ,
i s t i t r a t e d a f t e r f i l t r a t i o n w i t h a s t a n d a r d s o l u t i o n of
H C 1 using a methyl red-bromocresol green i n d i c a t o r . Any
calcium hydroxide p r e s e q t a s a r e s u l t of c o n t a c t w i t h
a i r i s also extracted. F i n a l l y CaC03 d e t e r m i n a t i o n was
c a r r i e d o u t by simple acid-base t i t r a t i o n using IM HC1 and
0.5M NaOH s o l u t i o n s . It was n o t p o s s i b l e t o t e s t f o r o t h e r
u s u a l l y minor c o n s t i t u e n t s of cement l i k e c h l o r i d e P205,
MnZ03 & Ti02, due t o o p e r a t i o n a l c o n s t r a i n t . However,
t h i s is n o t .expected t o i n v a l i d a t e -the c o n c l u s i o n s arrj-ved
i n t h e work s i n c e i f any of t h e elements were p r e s e n t i n
e x c e s s i v e p r o p o r t i o n it tsoclld have m a n i f e s t e d i n p r o c e s s
o r Qua1i t y Control problems.
3.5 PHYSICAL ANALYSES
Any p h y s i c a l t e s t h g requirements u s u a l l y i n c l u d e
t h e determina-tion of f i n e n e s s , s e t t i n g time, soundness
and s t r e n g t h .

3.5 .I Fineness

Fineness of cement i s based on t h e s i e v i n g r e s i d u e

o b t a i n e d using t h e s t a n d a r d s i e v e s p e c i f i e d and t h e b l a i n e
2
o r s p e c i f i c a r e a i n m /Kg c a l c u l a t e d froin t h e p e r m e a b i l i t y
of a bed of cement, i t s p o r o s i t y , t h e d e n s i t y o f t h e
cement and t h e v i s c o s i t y of a i r . The measure of b l a i n e i s
t h e time it t a k e s a c e r t a i n q u a n t i t y of a i r t o flow
thrtsugh t h e bed under s p e c i f i e d c o n d i t i o n . The equipment
used was E l e c t r o n i c A i r P e r m e a b i l i t y t e s t e r , Model 7207.

3.5 .2 S e t t i n g Time
It i s n e c e s s a r y t h a t cement must n o t s e t t o o quickly,
allow s u f f i c i e n t time f o r t h e mortar o r placing
t h e concrete. T h i s i s taken c a r e of in q u a l i t y c o n t r o l
through monitoring of i n i t i a l and f i n a l s e t t i n g t i m e s
which a r e t e s t e d w i t h Vicat n e e d l e a p p a r a t u s on a cerneqt
p a s t e , according t o Nigerian I n d u s t r i a l Standards.
3.5 .3 Soundness
Soundness means t h e a b i l i t y of t h e cement t o
maintain a c o n s t a n t volume a t a l l times. A cement i s
s a i d t o b e sound i f a f t e r hardening, it i s f r e e from
expansion ( i . e . no c r a c k s ) . Unsoundness i s u s u a l l y
caused by high c o n t e n t of f r e e MgO causing Magnesia
expansion, excess s u l p h a t e causing s u p h a t e expansion
and by s u b s t a n t i a l amomts of f r e e CaO causing l i m e
expansion. Autoclave o r Le C h a t e l i e r l s expansion,
measured in mm, i s u s u a l l y t e s t e d a s s p e c i f i e d i n t h e
standard, and g i v e s a measure of msoundness of cement.
'\

3 -5.4 Compressive S t r e n g t h
The v a l u e of cement when it i s used a s a c o n s t r u c t i o n
m a t e r i a l ;depends p r i m a r i l y on i t s mechanical. s t r e n g t h
under s e t ' and hardened condition. T h i s s t r e n g t h i s due

t o t h e adhesion of t h e p a r t i d e s of cement a s well a s

t h e i r adhesion t o t h e g r a i n s of sand o r o t h e r aggregate
with which t h e y a r e mixed. Ebery s p e c i f i c a t i o n , t h e r e f o r e
r e q u i r e s a m i n i m u m s t r e n g t h t h a t must b e a t t a i n e d under
given conditions. Compressive s t r e n g t h , measured i n
~ / m m2 i s t h e most common measure applied; i n t h i s case t h e
t e s t s were c a r r i e d o u t using Toni Technik Compressive
s t r e n g t h machine.
 CHAPTER 4

4.0 RESULTS AN13 DISCUSSION

4,l SAMPLE COLLECTTION

A l l t h e cement samples i n one s e t were c o l l e c t e d

w i t h i n t h e same week, .41so t h e raw m a t e r i a l s from t h e

Nigerian Cement Companies were obtained from t h e
f a c t o r i e s i n t h e corresponding sampling p e r i o d , A
f o r e i g n cement brand was purchased from Menyatta
market, ESnugu, a t t h e same t i m e of sampling f o r each
set. I t i s t h e r e f o r e s a f e t o conclude tha-t a l l t h e
Nigerian cement brands d i d n o t s u f f e r any d e t e r i o r a t i o n
due t o long s t o r a g e . However, t h i s was an assumption
i n t h e c a s e of f o r e i g n made cement.

4.2 SAMPLE PREPARATION AN0 TESTING

Sample p r e p a r a t i o n and t e s t i n g were uniform f o r
t h e f o u r brand samples. T h i s formed a good b a s i s f o r
t h e comparison of t e s t r e s u l t s .
1 1

I h e d i f f e r e n t methods of raw m a t e r i a l p r e p a r a t i o n
(wet o r dry p r o c e s s ) f o r i n d . u s t r i a 1 p l a n t do n o t a f f e c t
t h e chemical composition of m a t e r i a l s processed; t h e
same s i t u a t i o n a p p l i e s i n p r e p a r a t i o n f o r samples i n t e n d e d
f o r Laboratory a n a l y s i s .
 d e s u l t s of t y p i c a l raw m a t e r i a l t e s t s s h o w on
Tables 5 - 7 were obtained from average of two sample
tests.

4.3 SUITABILITY OF RAW MATERIALS

Tables 5 -7 show t y p i c a l raw m a t e r i a l s used in
t h e t h r e e cement companies s t u d i e d , namely, Benue
Cement Company, Gboko, t h e Nigerian Cement Company,
Nkalagu and Calabar Cement Company, Calabar. Also t h e i r
p o t e n t i a l raw mix compositions were c a l c u l a t e d by
Allegation a l t e r n a t e method i n which t h e r e q u i r e d lime
content of t h e raw mix i s f i x e d a s a s e t p o i n t t o
determine t h e p r o p o r t i o n s of both components t o achieve
desired target. IIere raw mix CaCO- t a r g e t was f i x e d at
3
77.00%. The t h r e e companies mentioned above a r e
designated a s A, B and C , f o r t h e purpose of t h i s
d i s c u s s i o n ( s e e Tables 5 - 7).
For cement p l a n t A , blending of two p r i n c i p a l raw
materials lead t o
SiR = 3.12

While it may b e p o s s i b l e t o use t h e raw mix'cornposi~ion

a s it i s , a l i t t l e i r o n o r e i n t h e form of l a t e r i t e
was employed h e r e t o b r i n g t h e Q u a l i t y C o n t r o l
parameters t o optimal l e v e l s by i n c r e a s i n g t h e f l u x
and reducing t h e SiR.
P o t e n t i a l raw mix c a l c u l a t i o n from B showed
SiR = 4.30
AIR = 3.89
LSF = 84.19%

Both t h e SiR and IUR v a l u e s a r e t o o high and hence LSF

i s on t h e low s i d e . However t h i s Company u s e s c o a l
a s f u e l and c o a l a s h c o n s t i t u t e s about 30~6of c l i n k e r .
T y p i c a l a n a l y s i s of raw c o a l and c o a l a s h (Enugu c o a l )
a r e shown i n T a b l e s 8 and 9.
It can b e seen t h a t i n t r o d u c t i o n of c o a l f o r
c l i n k e r burning c o n t r i b u t e s t o t h e chemical composition
of c l i n k e r and hence of f i n i s h e d product. I n this p l a n t ,
1
t h e r e f o r e c o a l a s h combines w i t h t h e raw m a t e r i a l s t o
produce c l i n k e r . Changes i n c o a l q m l i t y a u t o m a t i c a l l y
l e a d t o changt2s i n c l i n k e d q u a l i t y ; a p p l i c a t i o n of
Q u a l i t y C o n t r o l i s aimed a t achieving t h e d e s i r e d r e s u l t s .
For 'c, blending of t h e two p r i n c i p a l raw m a t e r i a l s ,
l i m e s t o n e and c l a y , y i e l d t h e following parameters:
 Because of h i g h s i l i c a r a t i o , i r o n o r e a s
a d d i t i v e forms p a r t of raw m a t e r i a l p r o c e s s i n g ,

4,4 CHD'IICAL AND PHYSICAL PROPERTIES OF CEbIEiW! SAMPLES

The t e s t r e s u l t s of two cement samples each from
A, B and C companies a r e shown on Table 10 which a l s o

c o n t a i n s a n a l y s i s r e s u l t s of t h e f o r e i g n cement sample
marked D,
,Both chemical and p h y s i c a l p r o p e r t i e s of a l l t h e
samples were t e s t e d by t h e same method a s d e s c r i b e d i n
t h e experimental, An o v e r s e a s v e r i f i c a t i o n t e s t by an
independent Lab o r a t o r y i n t h e United Lingdom was
conducted on one sample from A; t h e r e s u l t s a r e shown
in Appendix I, Close examination of a l l t h e t e s t
r e s u l t s i n d i c a t e t h a t experimental v a l u e s o b t a i n e d i n
t h i s work a g r e e q u i t e well w i t h t h o s e o b t a i n e d i n t h e
U,K. Lab ( s e e t a b u l a t e d r e s u l t s i n Appendix I and
r e s u l t s of A i n Table 10). Also t h e o v e r s e a s
i
c o n s u l t a n t s confirmed t h a t t h e cement sample t h e y t e s t e d
i s i n conformity w i t h c u r r e n t B r i t i s h Standard \

S p e c i f i c a t i o n f o r Ordinary p o r t l a n d cement,
 (i) A Samples
For samples from A t h e low v a l u e s of LO1 and I R
p o i n t t o t h e good p r o c e s s of g r i n d i n g c l i n k e r without
e x t r a a d d i t i v e ( o t h e r t h a n gypsum) as r e q u i r e d by t h e
standard. Low v a l u e s of MgO, K20, Na20 and f r e e l i m e
a r e in conformity w i t h smooth p r o c e s s conditioiis; such
f a c t o r s u s u a l l y e x h i b i t minimal expansion e f f e c t as
shown by t h e samples.
The compound compositions d i s p l a y a good t r e n d
l e a d i n g t o comfortably high c~3~1!psessive
strengths i n

a l l t h e ages of 3, 7 and 28 days. The h i g h f i n e n e s s of

t h e samples a l s o c o n t r i b u t e d t o t h e n i c e s t r e n g t h s
achieved.
The i n i t i a l and f i n a l s e t t i n g t i m e s of A a r e
normal, confirming c o r r e c t gypsum p r o p o r t i o n i n g .

(ii) B Samples

These samples came out w i t h good compound

compositions, a l t h o u g h t h e s i l i c a r a t i o of %he two
samples were v e r y high. T h i s i s t h e p l a n t us.ing c o a l
a s f u e l ; t h e c o a l a s h might have i n t r o d u c e d e x c e s s i v e
Si02 i n t h e c l i n k e r ( s i n c e c o a l a s h i s v e r y r i c h i n s ~ o * ) .
destabilize
Such a s i t u a t i o n can t h e p r o c e s s and may even
l e a d t o reduced s t r e n g t h s depending on t h e extent of k i l n
i n s t a b i l i t y experienced during t h e process rm.
However f o r t h e s e two samples a l l t h e p h y s i c a l parameters
a r e i n conformity with standard.

(iii) 6_, Samples-

For sample C, t h e SIR was 2.80 which i s a b i t on
t h e high side. T h i s might have l e d t o k i l n i n s t a b i l i t y

a s manifested i n high expansion (34 mrn) , rendering the

cement unsound.
However because of t h e good t r e n d of compound
composition combined with high l e v e l of cement f i n e n e s s
t h e compressive s t r e n g t h of t h e end product s t i l l came
out very high.
C2 appears t o have an i n p u t of e x t r a a d d i t i v e which

has made t h e LO1 and I R t o be high (though within t h e

specification). The compound compositions were q u i t e
i n order, except excessive SO content
3
-
signifying
over-proportioning of gypsum. It i s b e l i e v e d t h a t t h i s
excess gypsum l e v e l had an adverse e f f e c t t h a t rendered
t h e cement unsound due t o s u l p h a t e expansion hence

dragging down t h e compressive s t r e n g t h t o sub-standard

level.
(iv) D Samples
The D samples a r e characterized by high LO1 and
I R i n d i c a t i v e of use of e x t r a a d d i t i v e contrary t o t h e

s t i p u l a t i o n of t h e specification. The other chemical

parameters came out f i n e and with high b l a i n e values
t h e compressive s t r e n g t h s appear i n order.
For Dl t h e values of C S and C2S a r e almost even,
3
r e s u l t i n g i n -the r i s e between early s t r e n g t h and l a t e
s t r e n g t h not being a l l t h a t high a s i n Aq & ri2 samples.
The r e l a t i v e l y low L S i n LI1 i s i n t h e same tune with
i t s low CjS. Effect of possible e x t r a a d d i t i v e
combined with low LSF' and C S can be extrapolated t o
3
lower strengths. However t h e compressive s t r e n g t h s did
not f a l l t o o much and a c t u a l l y P) samples very much met
t h e standard s p e c i f i c a t i o n .

4.5. , Comparison of Four Cement Brands

From t h e discussions i n Section 4.4 above, t h e
following conclusions can be reached on t h e comparat i v e
q u a l i t i e s of A, B, C and D samples vis-a-vis t h e i r
extent oP compliance with standards.
'A' samples f u l l y s a t i s f y a l l t h e chemical and
physical requirements f o r Ordinary Portland Cement a s
s t i p u l a t e d i n t h e current Nigerian I n d u s t r i a l Standards
(NIS) a s well a s B r i t i s h Standards (BS). The two
samples from t h i s p l a n t a l s o i n d i c a t e a r e a s o n a b l e
l e v e l of c o n s i s t e n c y i n p r o d u c t i o n , a s t h e r e i s minimal
v a r i a t i o n between t h e two t e s t results.
The two 13 samples gave chemical and p h y s i c a l
parameters s a t i s f y i n g a l l t h e r e l e v a n t standards.
However, t h e l e v e l of c o n s i s t e n c y i n t h e two samples
i s l e s s t h a n t h a t found i n A, p a r t i c u l a r l y when we
c o n s i d e r t h e i r SiK v a l u e s which have d i r e c t impact on
process; it i s noteworthy t h a t t h e s i l i c a r a t i o s of
B samples approach t h e upper extreme l i m i t s .

For C samples t h e f l u c t u a t i n g SOj v a l u e s a r e

i n d i c a t i v e of gypsum p r o p o r t i o n i n g problem. iben t h e
SO c o n t e n t of sample C2 i s o u t s i d e t h e s p e c i f i e d l i m i t
3
and this might have accounted f o r t h e substandard

compressive s t r e n g t h s a s w e l l a s Le C h a t e l i e r t s expansion
l o g i c a l l y a t t r i b u t e d t o s u l p h a t e expansion.
Analysis of D samples a l s o show h i g h q u a l i t y cement
conforming t o b o t h t h e B r i t i s h and N i g e r i a n s t a n d a r d s
f o r Ordinary P o r t l a n d Cement. Although t h e s e two D
samples w i t h h i g h v a l u e s of L O 1 and IH might have
contained e x t r a a d d i t i v e t h e y a r e w i t h i n s p e c i f i c a t i o n .
However, t h e samples show s l i g h t i n c o n s i s t e n c y in t h e

t r e n d of CjS and C2S.

 The p a t t e r n of compound composition, o t h e r w i s e
known a s c l i n k e r phases ( e s p e c i a l l y C3S and C ~ S )i n
each sample, coupled w i t h o t h e r cement p r o p e r t i e s ,
determine t h e l e v e l of s t r e n g t h development - a key
f a c t o r i n cement u t i l i z a t i o n . The average compressive
s t r e n g t h s of t h e f o u r cement b r a n d s can b e seen on
Table 11. These v a l u e s a r e i l l u s t r a t e d i n a p i e graph
on Fig. 3. The comparison of t h e compressive s t r e n g t h s
of t h e f o u r samples a s demonstrated i n Fig. 4 g i v e s t h e
f o l l o w i n g d e c r e a s i n g o r d e r (on t h e average) f o r t h e s e
samples:
 CHAPTER 5

CON CL US1 ON

Analysis of t h e raw m a t e r i a l s used by t h r e e

Nigerian cement brands s t u d i e d showed t h a t t h e raw
m a t e r i a l s were s u i t a b l e f o r cement manufacture,
However, adequate proportioning and processing of t h e s e
raw m a t e r i a l s a r e very v i t a l t o achieve t h e d e s i r e d
end product q u a l i t y , Any problems encountered a t t h e s e
s t a g e s a r e bound t o b e r e f l e c t e d i n t h e p r o c e s s and
u l t i m a t e cement q u a l i t y .
Three made i n Nigeria cement brands designated
A, B & C, along w i t h a f o r e i g n brand denoted by D were
t e s t e d f o r chemical and p h y s i c a l p r o p e r t i e s , i n
accordance w i t h Nigerian s t a n d a r d s p e c i f i c a t i o n ,
I1Al1 shows a high l e v e l of consistency, w i t h a l l t h e
t e s t parameters meeting t h e l a i d down s t a n d a r d s p e c i f i c a -
tion, The S i l i c a Ratio, Alumina Ratio and t h e Lime
S a t u r a t i o n F a c t o r f o r t h i s brand a l l p o i n t t o a smooth
manufacturing process, a f a c t o r which has tremendous
impact on q u a l i t y .
Although Y3I1 samples show high S i l i c a R a t i o which
i s capable of causing k i l n i n s t a b i l i t y a l l -tile t e s t
r e s u l t s were i n conformity with standard, Since t h i s
company u s e s c o a l as f u e l t h e h i g h and f l u c t u a t i n g
S i l i c a R a t i o observed i s b e l i e v e d t o a r i s e from changes
i n c o a l q u a l i t y / p r o p o r t i o n i n g ; c o a l a s h which can c o n t a i n
upto 60% Si02 c o n s t i t u t e s about 30% of cement c l i n k e r .
Q u a l i t y Control i n t h i s f a c t o r y may need t o f o c u s on
t h e impact of c o a l u t i l i z a t i o n .
The two samples from C gave unsound cement
c l e a r l y manifested by one sample t e s t r e s u l t i n g i n
exceeding high f r e e l i m e expansion e f f e c t . Such a
phenomenon normally l e a d s t o s t r u c t u r a l f a i l u r e i n t h e
form of c r a c k s on t h e b u i l d i n g walls. The second C
sample a l s o showed t h e same problem of expansion b u t
to
this t i m e dueLexcess s u l p h a t e c o n t e n t coming from over
p r o p o r t i o n i n g of gypsum.
"D" samples manufactured i n t h e United Iiingdom
were t e s t e d i n t h e same manner w i t h o t h e r t h r e e
Nigerian cement brands. The r e s u l t s o b t a i n e d were in
agreement w i t h b o t h Nigerian and B r i t i s h s t a n d a r d
s p e c i f i c a t i o n f o r Ordinary P o r t l a n d Cement. However,
c l o s e a n a l y s i s of t e s t r e s u l t s t e n d t o show t h a t D
c o n t a i n s some e x t r a a d d i t i v e o t h e r t h a n gypsum, as can
b e deduced from t h e high v a l u e s of Loss On I g n i t i o n and
I n s o l u b l e Residue. Furthermore, t h e two samples of D
t e s t e d d i d n o t d i s p l a y h i g h l e v e l of cortsistency i n
r e s p e c t of some v e r y important i n d i c e s of product q u a l i t y
l i k e CjS and C2S.
The cement samples taken from t h r e e N i g e r i a n cement
companies were r e p r e s e n t a t i v e of t h e i r r e s p e c t i v e b a t c h
productions. One b a t c h of raw m a t e r i a l p r e p a r a t i o n i n a
f a c t o r y can y i e l d up t o 500 - 1000 t o n n e s ( o r 10,000 -
20,000 bags) of cement.
Although t h e c o n c l u s i o n s reached i n this work a r e
t a k e n t o b e v a l i d f o r t h e samples t e s t e d , such may n o t b e
tenable f o r e n t i r e factory operations considering t h e
sample population i n v e s t i g a t e d . However, t h e r e s u l t s
g i v e a f a i r i d e a of comparison of q u a l i t y ar-d s t a n d a r d s
in cement manufacture - p o r t r a y i n g t h e salievlt f a c t o r s
involved, A v i t a l i n f e r e n c e i s t h a t p r o c e s s technology
(wet, dry o r any hybrid of t h e two) does n o t d i r e c t l y
i n f l u e n c e t h e product q u a l i t y , T h i s f o l l o w s from t h e

s t u d i e s of Benue Cement Company and Calabar Cernmt Company

b o t h of which apply d r y p r o c e s s technology, and t h e Nigerian
Cement Company, Nkalagu o p e r a t i n g w i t h t h e wet process.
But a narrow range of good o p e r a t i n g c o n d i t i o n s n e e d s t o b e
maintained f o r a r e a s o n a b l e degree of c o n s i s t e n c y i n product
qua1 i t y w i t h i n t h e s p e c t r m of a p p r o p r i a t e s t a n d a r d
specification
J
Shreve, R. N. and Brink, J. A. Chemical P r o c e s s
I n d u s t r i e s , 4 t h Ed., McGraw-Hill I n t e r n a t i o n a l Book
c o o , Tokyo, I , (1977).

Labahn, O., Kohthaas, B. Cement Ehgineers' Handbook,

4 t h Ed., Bauverlag GmbH, B e r l i n , 105, (1985).

Story of Cement, Onoda Engineering and Consulting

Coo, Tokyo, 1 , (1988).

Bye, G. C. P o r t l a n d Cement: Composition, Production

and P r o p e r t i e s , Pergamon P r e s s , Oxford, 4, (1985).

Story of Cement Onoda Engineering and Consulting

Co., Tokyo, 1 , (1989).

The Punch, Wigercem goes t o t h e s t o c k market f o r a

$?om A~B?Loanl',Vol. 1 4 , No. 16146, J u l y 24, 1990, p . 30

Taylor, H. F. W. The Chemistry of Cements, Vol. I,

Academic P r e s s , London, 28, (1964).

Duda, W. H. Cement Data Book 3 r d Ed.,

B a w e r l a g GmbH, B e r l i n , 445, (1985).

Helming, B. Cement Manufacture I, Krupp P o l y s i u s A.G.,

Ger., I , (1989).

Bye, G. C . P o r t l a n d Cement: Composition, Production

and P r o p e r t i e s , Pergamon P r e s s , Oxford, 3 2 , (1983) .
.
Cement M a r u f a c t u r h g Technology, Vol I, Section V,
Onoda Ehgineering and Consulting Coo, Tokyo, 2 , (1985).

Helming, B. Cement Manufacture I, Krupp P o l y s i u s A.G.,

Ger., 8, (198'/) .
Labahn and Kohlhaas, Cement 1 3 g i n c e r s t Handbook,
4 t h Ed., B a w e r l a g ~ m b H , B e r l i n , 110, (1983).
14. Labahn and Kohlhaas, Cement E h g i n e e r s t Handbook,
4 t h Ed., Bauverlag GmbH, B e r l i n , 111, ( I ~ R F

15. S p e c i f i c a t i o n . f o r Ordinary P o r t l a n d Cement,

N i ~ e r i a nI n d u s t r i a l Standard 11: stan=
~ r i a n i s a t i o nof N i g e r i a , F e d e r a l M i n i s t r y o f
I n d u s t r i e s , Lagos, 1 , ( 1974).

16. Agbazue, V. E., 1 9 t h Annual Conference on M a t e r i a l s

T e s t i n g , C o n t r o l and Research ( P r o c . ) , 219 ,
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17. Helming, B. Cement Manufacture I, Krupp P o l y s i u s A.G.,
Ger., 1 0 , (1987).

18. Rye, G. C. Portland. Cement: Composition, Production

and P r o p e r t i e s , Pergamon P r e s s , Oxford, '1, (1983).

19. Bye, G. C. P o r t l a n d Cement: Composition, P r o d u c t i ~ n

--
and P r o p e r t i . e s , Pergamon P r e s s , Oxford, 31, (1985).

20. Cement Manufacturing Technology, Vol

Onoda h h g b e e r i n ~and C o n s u l t i n g Co.,
. Tokyo,
I, S e c t i o n V,
8, (1985).

21 . VDZ Congress '77, P r o c e s s Technology of Cement

~ 1 9 7 0

22. VDZ Congress 77, P r o c e s s Techol-ogy of Cement

Manufacturing, Bauverlag GmbH, B e r l i n , 640, (1979) .
23. I1SOnT moves t o check i n f l u x of f a k e
.Dail Times,
279559, August 3 , 1990, P. 14.

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Cement and B u i l d i n g M a t e r i a l s , New Delhi,
134, (1.988).

25. Labahn and Kohlhaas, Ceinent E h g i n e e r s l Handbook,

4 t h Ed., Bauverlag GmbR, B e r l i n , 110, (1985).

26. P a t e l , M., Chem. Abstr., -

104, 191853d, (1986).

27. Reuss, A., Chem. Abstr., -

74, 115409k, (1972).
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68, 81116w, (1968).

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Concrete Research, 12, 51, (1982) . Cement and

Johansen, V., Chem. Abstr., 97, 97173x, (1982).

O d l e r and IVsnnemann, R., Cement and Concrete Research,

-
1 3 , 771, (1983).

Strunge, J., Knsef, D. and D r e i z l e n , I.,

-
Chem. Abstr., 105, 138748t, (1986).

Rechrneier, H., 7 t h I n t e r n a t i o n a l Congress on t h e

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97, 41189q, (1952).

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98, 94607b, (1983).

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99, 57911w, (1983).

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74, 452779, ('1971).

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( 1982) ,
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Chem. Abstr,', 97, 132388v,

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73, 58998e, (1970)

P e r r i c , J. and K r s t d o r i c , R., Chem. Abstr., 87

-9
57409r, (1977).

Chang, S I , Chem. Abstr., -

105, 177426f, ( 1 9 8 6 ) ~
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105, 196257t, (1986).

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105, 777426f, (1986).

47. Goma, F., Chem. Abstr., -

104, 173271h, (1986)

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NO. 2618, June 15, 1990, P. 7-

49. National Concord, 11N700m i l l i o n cement firm f o r Yola",

Val. 10, N O . 2'182, May 23, 1989, P o 16.

TO. S p e c i f i c a t i o n f o r Ordinary P o r t l a n d Cement,

N i a e r i a n I n d u s t r i a l Standards 11 : ~ t a n d a r d ' sOrwanisa-
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104, 173271h, (1986).

5 2. Spec.ifi c a t i o n f o r Ordinary P o r t l a n d Cement,

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I n d u s t r i e s , Lagos, 10, (1974).

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104, 173271h, (1986).
/-.-'
APPENDIX I 7.72
OVERSEAS REPORT CIN TESrS OF SWPLE OF CE5Rl'r
. .

,,.,,. , i , , , I , , , , , - I ,,,,,..I
1 .lll,llll 1 111

Your Ref: L e t t e r UIB/5029/90 1 I.,.,. I1.P' ',<I"." 1 5 :

Our Ref:
Date:
202/2805/90/KW/ls
1 6 t h Aueust 1990
1
I,(,,.,
,~ 1 1 1 1
I,,, I ','"I.'
',,
'1
tI.1
i'. .

Sant Engineering Ltd

S a n t llouse
46 Wise Lane
London
NU7 2KE

T e s t No: IX 1203

REPORT ON TESTS OF SAMPLE OF CkXENT

, K e c e i v c d From Yourselves

Cons ty,ned Via DHI.

Marks o n Sample BCC Pnckirlg I ' l a n t CernenL oE 1 2 / 2 / 9 0

Sample H e i g h t , kg, 5.0

A uample o f c e m e n t , a s r e E e r e n c e d a b o v e , was t c s t c d f o r c i ~ n f n r n r~yl w i t l l Ille

r e q u i r e m e n t s o f BS 1 2 : 1 9 7 8 " S p e c i f i c a t i o n f o r O r r l Lnary dnri K , ~ p t d H ~ r d c r n~ ~l ,
P o r t l a n d Cement" as i n s t r u c t e d by y o u r l e t t e r KMI1/5029 /9O d ~ t c dt h e 1 7 ~ 1 1Nay IO'JC).

TEST METllODS

7:rc s a m p l e was t e s t e d by t h e m e t h o d s d e t i c r l h e d i n llS (1550:1')70 " M c t l ~ ~ ~ t oi :f;

T e s t i n g Cement".

The t e s t i n g was c a r r l e d o u t b e t w e e n 1 5 t h J u n e 1 9 9 0 a n d 271-11 J u l y 1990.

?GSULTS OF TESTS

The r e s u l t s a n d t h e B r i t l s h S t a n d a r d s p e c l f Led r c q u i r e ~ n c n L s art: givc>n o n t h r

attached sheet.

The r e u u l t ~o f b o t h Llic phy:;lcol o!ld ' l ~ e n ~ l r a l~cst:!: w(:rc I 11 conl'ol-IIIIl y w l 1.11 111,.
r e q u i r e m e n t s o f BS 1 2 : 1 9 7 0 f o r O r d i n a r y P o r t l a n d Celncnt.
 Our Ref: 202/2805/90/KW/ls Page No: 2
,~ln~rgcr's
2
, ' ,

To: S e n t E n g i n e e r i n g Ltd Dote: l6Ll1 A k r l : w L 19'30

T e s t No: EC 1293

--
C o m p r e e ~ i v eS t r e n g t h N/mmL 1'e r C v II L
Age Days 3 28
S i l i c a , Si02 19.5G
Mortar 29.0 46.0 I n ~ i o l u b l eResidue 0.5G
27.5 46.5 Alum 1 nn, A1203 6.50
31.0 44.5 F e r r i c Oxide, Fe203 3.09
- - Lime, CnO 62.02
29.0 45.5 Magnc.;ia, FlgO 0. 7 2
Sulpllurl c Anl~yrlr i d e , SO3 2.39
Concrete 18.5 35.5 Loss on I ~ n i t l o n 1.70

Ltandard C o n s i ~ t e n c e ,X 25.0 T o t a l Sulpllur e x p r e ~ s c da s SO3 2.39

Sulphur present a s Sulphlde, S !lone
S e t t i n g Time Ilet e c ~ r l l
I n i t 1.2. : 150 m i n u t c s
Flnal: 4 hours 0 m l n u ~ e s --
Soundne:;.a Lime S a t u r n t ton F.ictor
Expansion a s r e c e i v e d , mm 0.5 T r i c a l c i u m A l ~ ~ m i n ; l L cC, 3 A
Proyylcnu G l y c o l Contcnt
Fineness
Spocif i c S u r f a c e , rn2/kg: 293

SPECIFICATION REQUIMENTS - BS 12:1978

mpressive Strength, ~ / m m ~ Fineness

3 d a y s 20 d a y s OPC, not l e s s tl1:111
Mortar KHPC, n o t l e s s Lllan
mtnimum, OPC 23.0 41.0
minimum, RHPC 29.0 46.0 Chemical C h n p o s l t i o n
I n s o l u b l e R e s i d u e , mnx
Concrete t l a g n c s i a , Mg0, nl;lx
minimum, OPC 13.0 29.0 T o t a l S u l p l ~ u r , SO.), tnax
minimum, KliPC 18.0 33.0 Cjh i s 5% o r l c s s
C3A more t l ~ a n5%
S e t t i n g Time 1,oss on Igrll t i o n
I n i t i a l , not l e s s than 45 m l n u t e s tcmpcr;lte climnl:c!r,, m.ix
F i n a l , n o t more t h a n 1 0 hours t r o p l c ; ~ l c l 11!1alr::;, mix
Lime S a t n r n t l o n F a c t o r
Soundness not ' l e ! ; ~ 1.111n
Expnnsion, a s r e c c i v c d mnx l O m m nt,t mor? I11:ln
I I?ropylcne C 1 y<:ol I : I . I I I L ~ IIn:lx
I~,

S t a n g e r C o n s u l t a n t s Ltd
T a b l e 1 : Limiting values of chemical
composition of cement raw material
G f t e r iqnition)

Oxide Limiting value (% b y wt.)

CaO 60 - 69
18-24

443

1-8

-.
C4.0

.L,2.0
<3 . ~
 TABLE 2 : COMPARISON OF BRITISH AND
NIGERIAN STANDARDS FOR ORDINARY
PORTLAND CEMENT (OPC)
CHEMICAL PROPERTIES PHYSICAL PROPERTIES
--
4TION
- -
'ROPERTIES PROPERTIES
NIS. I1

LO I Setting Tirne

IR Initial

Si02 Final

*I203 Fineness

Fe203

Ca 0 Blaine: m2 /Kg

mgO Comp. Strength:

Na2O Mortar cubes

K20 3 days ~ / r n r n ~

9'3 7 days "

SIR 2 0 duys "

A1.R

LSF Concrete cubes

LCF 3 days ll/md

Fr. Lime 7 days "

c3s 20 days "

c2 s Soundness:

C3 A Le chateliers expansion

CLAF
 79
T a b l e 3: T h e c e m e n t s t a n d a r d s of some c o u n t r i c z o f t h e w o r z

Country and/or Type o f cement

--
Issuing Authority
UK
~ritiz
Standards DPC, IIHC
Institution SflC
2 park S t r e e t LIiC
London WlAZBS PDS 1
PUS2
Super Sulphate
Cement
Hiqh Alumina
Cement
M a s o n r y Cement
PP ( 2 c l a s : : ~ ~ )

-
USA
American S o c i e t y f o r T c s t i n '
a n d M a t e r i a l s (ASTM)
1 9 1 6 Race S t r e e t

Philadelphia M a s o n r y cenierit
Pa 19103 Expansive hydra-
ulic (3 classes)
S l a g Lime & A i r
entraining
American Petroleum I n s t i t u t
)roduct i o n Department
!ll N. E r v a y , S u i t e 1 7 0 0
) a l l a s TX 7 5 2 0 1

k r m a n y , Fed. Rep.
) I N Deutsches OPC ( 2 c l a s s e s )
E n s t i t u t e F u r Normunq e.v. HSC ( 2 c l a s s e s )
1-1000, p o s t f a c h 1 1 0 7 RHC, P B S l ( 3
classes
PDS2 ( 3 c l a s s e s :
C P ( 2 classc,:;)
Masonry Cement

Nigeria
Federal Ministry of Indust-
ries, S t a n d a r d s O r g a n i s a t i o
o f N i g e r i a , 11 K o f o
Abayomi S t r e e t V i c t o r i a
I s l a n d , Lagos
Key t o T a b l e 3

OPC O r d i n a r y P o r t l a n d Cement
HSC High S t r % n g t h P e t l m d C e m e n t
RHC Raid-Hardening ( o r High-Early S t r e n g t h o r
High I n i t i a l S t r e n g t h ) P o r t l a n d Cement.

PBS P o r t l a n d B l a s t F'urni~ceS l a y C~nrerit

PP P o r t l a n d P o z z o l a n a Cerncnt
S RC I S u l p h a t e R e s i s t i n g P o r t l a n d Ccrrlent
LHC Low H e a t ( o r S l o w H a r d e n i n g , Low H e a t o f
H y d r a t i o n ) P o r t l a n d Cement.
 BErJUE CEhiENT COMPANY LIMITED
- = ,'-- - -----
c E - - - m . - .,-
? I- => a i-
I
CHEhllCAL AND PHYSICAL PROPERTIES Of LlOK B?Ah!D CEMENT SAMPLED A T THE
dfi X . 3 , i I u G J U L Y 1090 !I
CHEMICAL PROPERTIES
PHYSILAL PROPERTIES Speci Lion Brand
Properties if;c Lion Brand
-- 2s. 12
L.O.1 Sening T m e
1.R Initial
745~1t4: 110 MINS
-2 Final
L lOHRS 4HRS.C2MINS
Finess
AL203
Blaine m2/~g 5 225
~ e p ~

CaO Cornpr. Strength

MgO (hlo-rar Cubes)
Ra20
K20
so3
SIR 3days #/mm 2 z23
AIR
?days "

'I'
LSF
LCF
28 days '1
Z41
Fr.Lirne

C3S
L lorn
C2S

Cj4
C4AF

I eEREBY CERTIFY T H A T LION aRAFjD FULLY COMPL!ES W I T H SPECIF;CATlON OF ES12ji978 At:D .

NIS 11/1974
Table 5 : R a w Mix Potentlal Compostion

Sample A

Properties

ffl
LI X
04
aE

Na20

K2°
Unde terrnined

Total
T , i l ) l c 6 r I t n w Mix P o t ~ n t i a lC o m p o r , i t i o n

Sample D
 T a b l e 7 r Raw Mix P o t e n t i a l C o m p o s t i o n

Sample C

Properties

LO I

IR

S1O2

A1203

Fe203

CaO

w'
Na20

K2°
Undetermined

Total

SIR

A1R

LS F
Table 8: Proximate A n a l y s i s of Raw Coal f r o m Enugu

X
V o l a t i l e matter : 47,OO

Residual Moisture : 6.00

Fixed carbon 40.24

Total moisture 6,56

T a b l e 9: U l t l m a t e A n a l y s l s of coal Ash

CaO 10.69

Undetermined 0.22
Total 100oOO
 T a b l e 10: Chemical and P h y s i c a l p r o p e r t i e s of two
cement samples e a c h from t h r e e Nigerian
cement companies d e s i g n a t e d A, B & C and
a f o r e i g n cement brand d c s i q n a t e d D

Properties ~ ~ I " ~ [ T ~ ~ ~ ] T

Fe203 2.43 -2.18 2.06 229 2.93

2.53
CaO - 26.82 61.99 62.30- 6=622( 62.56
MgO 0.97 0.96 0.85 0,90 7.91 1.00
0.11 0.14 0.15 0.12 11-00 0. 13

K2° 1.28 0,7L -- 0.53

s03 2.52 2.22 '- 4.04
--
Undetermined 3.29 2.79 - --2.30
- Total 100.00 lOO.OC -- 1 00
SIR 3.38 7-20
ALR 2.39 7,40 1.7G
LSF 94.56 92.64
- LCF 92.38 90.83
-. F/Lime 1,38 1.18
c3S > 53-87 04,,09
C?S 16040 21.15
11.24 12.34
C3A --~ - - ---
C AF
4 7.38 7.70 '.tuG
- -.
I n i t i a l S e t t i n q Time ( M i n s ) 105 ---
I??
F i n a l S e t t i n q Time ( H r s . ) 3:7R )2 4 3
LwLl
B l a i n e ( m2/Kq) 3.15 335
-- 303
Compr. S t r e n q t h 3 days(Nirnm 2 ) 30.0 30.0
-- 13.5
I1 I1 7 I' ( "
37.0 . 35.5 !&I-
" 20 " 1
-4
I1 ( I 1
g15.5 x '7.5
--
Le c h a r t e l i e r ' s exopnsion(rntn) l
-
1
--
13
 T a b l e 11: A v e r a g e C h e m i c a l a n d Physical p r o p c . r t i c s
o f two c e m e n t s a m p l e s e a c h f r o m
t h r e e N i g e r i a n c e m e n t C o m p c ~ n i r sd e s i g n a t e d
A , B & C and a f o r e i g n cement brand
designated D

Samples

Properties

LO I
'IR
Si O 2

A1 0
2 3

Fe203
CaO
M9 0
Na20

K2°
S03
Undetermined

Total
SIR
A1R
LSF
LCF
F/Lime

C38
=zs
C3A
C4AF

I n i t i a l S e t t i n g Time ( M i n s )
F i n a l S e t t i n g Time ( H r s . )
2
B l a i n e (rn /Kg)
2
Compr. Strength 3 d a y s (N/mm )
I* Il
7 'I ( " )
\
It II
28 " ( I' )
L e c h a t e l i e r l s e x p a n s i b n (mm)
 3
L
-
0 Uays

>- Hardening Time

fig :,2
Compressive strengths of clinker phases
(Water - Cement ratio = 0.5; 1 = C 3 S; 2 :CZS; 3 q ~ ;
4 = C4AF )
 , ,
x.
llEY
comp strength 3 days ( N / m d )
ccmp,strength 7days(~/mm2) lBl!IN
comp.';strength.,28 days LN lmm2) 0
a ,

..
fig 3.
Illustration of compressive strengths of three Nigerian OPC.
and one foreign made OPC. tested according to NIS.l l / l W + ;
mortar cubes at 270C4
 - .- -..---..-
C B D A C D A B C D B J \

-----+3 Hardening time ( t ) : days.

fig 4 -
Cornpamtive representation of the compressive strengths of three Nigerian OPC.
and one foreign mode .OP C. tested according to N I S . 1 1 / 1974; mortar cubes
cured at 27'C