REFERENCES

[1] Ali Allahverdi (2001). Nitric acid attack on hardened paste of geo-polymeric

cement. Department of Glass and Ceramics, Institute of Chemical Technology, Czech

Republic. CEZ: MSM 22310002.

[2] ACI Committee 201 (1977). Guide to durable concrete. ACI journal.Vol.74: 574-

606.

[3] Dr. B. K. Sharma (1985) Industrial Chemistry (Including Chemical Engineering).

Meerut: Goal publishing house.

[4] Kolapo O. Olusola and Opeyemi Joshua (2012). Effects of Nitric acid

concentration on the compressive strength of Laterized concrete. ISSN 2222-1719,

Volume 2, No.10.

[5] M.S.J Gan (1997). Cement and Concrete. ISBN-10:0412790505.

[6] Ruth D. Terzaghi (1950). Leaching of lime from concrete. ACI journal, Vol.25:

475-477.

[7] Shintaro Miyamoto, Hiroshi Minagawa, Makoto Hishada, Tohoko (2007).A Study

on the Reaction Mechanism of Hardened Cement Chemically Damaged By Mixed Acid;

University, Department Of Civil Engineering, Sendai, Japan.

[8] Temper, B, (1931), The effect of acidic water on concrete. ACI journal. Vol.

28:1-32.

46
 AN EXPERIMENTAL STUDY ON THE STRENGTH
BEHAVIOR OF CEMENT MORTAR IN NITRIC ACID
SOLUTION

The thesis paper is submitted to the department of Civil Engineering, Chittagong

University of Engineering & Technology, Chittagong in partial fulfillment of the
requirement for the degree of Bachelor of Science (B.Sc.) in Civil Engineering.

January, 2017

SUBMITTED BY

MIJBAH UDDIN AHMED MUHAMMAD SOHEL

ROLL NO: 1101006 ROLL NO: 1101029

SUPERVISED BY
DR. MD. SAIFUL ISLAM
PROFESSOR
DEPARTMENT OF CIVIL ENGINEERING
CHITTAGONG UNIVERSITY OF ENGINEERING & TECHNOLOGY
CHITTAGONG, BANGLADESH
 ACKNOWLEDGEMENT

The authors gratefully acknowledge the support given for successful completion of the

project work in the form of laboratory facilities and materials by Chittagong University

of Engineering and Technology, Bangladesh.

The authors would like to express their appreciation intense gratitude to the supervisor

Prof. Dr. Md. Saiful Islam, Department of Civil Engineering, CUET, for his constant

supervision, continuous guidance, helpful criticisms and encouragement throughout the

Project work.

The authors also express their gratefulness and deep sense to Prof. Dr. Md. Abdur

Rahman Bhuiyan, Head of Department of Civil Engineering for providing all kinds of

possible facilities of the Department.

Special thanks to Lecturer Mr. Opu Debnath and other teachers of the department of

Civil Engineering for their kind co-operation.

Warm appreciation is expressed to all the members of the staff of the laboratory of Civil

Engineering Department of Chittagong University of Engineering and Technology,

CUET, Bangladesh.

January, 2017 Authors

CUET

i
 ABSTRACT

A major consequence of environmental degradation is the adverse effect of pollution on

building materials. With the growing contamination of water by industrial and domestic

waste, building materials, especially concrete and mortar are becoming increasingly

prone to aggressive chemical attack. Concrete is susceptible to acid attack as acid can

attack and leach away the calcium compounds of cement paste formed in concrete

through the hydration process as well as the leaching of calcium in calcareous aggregate.

Though Nitric acid is not as strong as Sulfuric acid, its effect on concrete and cement

mortar at brief exposure is more destructive since it transforms Calcium Hydrates into

highly soluble calcium nitrate salt and low soluble Calcium nitro-aluminate Hydrate.

In the present investigation, a comparative study was carried out on behavior of mortar

cubes exposed to contaminated acidic water with different pH. The mortar cubes of size

2 inch were cast and placed in three types of acid environment which were nitric acid of

pH value of 1,2,3 and pure tap water of pH value 7. The parameters studied include

compressive strength test and weight loss measurements. The Test were carried out at

the different curing age viz. 7, 30, 60, 120 days. The results of the test specimen under

the above stated exposures were compared to those of specimens placed in tap water.

The test results indicate that, the compressive strength of mortar specimens gradually

decreases about 10 to 42 % for ratio 1:3, 20 to 49% for ratio 1:4, 27 to 46% for ratio 1:5,

and the change in weight of the mortar specimens are observed to vary within the range

of 0.46 to 2.13% for pH 1, 16 to 1.36% for pH 2, 0.04 to 1.32% for pH 3 of Nitric acid

solution.

ii
 CONTENTS

Page No.

ACKNOWLEDGEMENT i

ABSTRACT ii

LIST OF TABLES vi

LIST OF FIGURES vii

CHAPTER 01: INTRODUCTION

1.1 General 1

1.2 Statement of the problem 3

1.3 Objectives 3

1.4 Scope 3

CHAPTER 02: LITERATURE REVIEW

2.1 Introduction 5

2.2 Present state of knowledge

2.2.1 Portland Cement 5

2.2.2 Hydration of Portland cement 6

2.2.3 Slag used in cement 9

2.3 Factors affecting waste water analysis

2.3.1 Scope 14

2.3.2 Analytical test 14

iii
 2.4 Acid attack on cement mortar & concrete

2.4.1 General 15

2.4.2 What is acid attack 16

2.4.3 Acid corrosion 17

2.4.4 Chemistry of acid attack 18

2.5.5 Factors affecting acid corrosion 19

2.4.6 Sources of acid attack on concrete 21

2.4.7 Effect of acid attack 22

2.4.8 Corrosion due to various acids 23

2.4.9 Prevention of acid attack on concrete 25

CHAPTER 03: EXPERIMENTAL INVESTIGATION

3.1 Introduction 26

3.2 Material

3.2.1 Sand 26

3.2.2 Cement 27

3.2.3 Acid 27

3.3 Casting

3.3.1 Mix proportion 27

3.3.2 Casting 27

3.3.3 Preparation of acid solution 28

3.4 Experimental program

3.4.1 Casting of specimens 28

iv
 3.4.2 Physical test for Cement

3.4.2.1 Normal consistency 29

3.4.2.2 Initial setting time 29

3.4.2.3 Final setting time 29

3.4.3 Different tests for mortar specimens

3.4.3.1 Compressive strength 30

3.4.3.2 Weight loss 34

CHAPTER 04: RESULTS AND DISCUSSION

4.1 General 35

4.2 Test result for concrete specimens

4.2.1 Compressive strength 35

4.2.2 Weight loss 35

4.3 Discussion on test result 42

CHAPTER 05: CONCLUSION

5.1 General 43

5.2 Conclusion 43

5.3 Suggestion for future work 44

REFERENCES 46

v
 LIST OF TABLES

Table No. Title Page No.

1 Compressive strength (MPa) of mortar specimens in 36

different Nitric acid solution (Mix 1:3)
2 Compressive strength (MPa) of mortar specimens in 37
different Nitric acid solution (M 1:4)
3 Compressive strength (MPa) of mortar specimens in 38
different Nitric acid solution (Mix 1:5)
4 Weight loss (Mortar 1:3) 39

5 Weight loss (Mortar 1:4) 40

6 Weight loss (Mortar 1:5) 41

vi
 LIST OF FIGURES

Figure No. Description Page No.

1 Vicat Apparatus 30

2 Compressive strength Testing Apparatus 32

3 Mortar Specimens 33

4 Mortar Specimens 34

5 Compressive Strength (MPa) of mortar specimens in 36

Different Nitric acid solution (Mix 1:3)
6 Compressive Strength (MPa) of mortar specimens in 37
Different Nitric acid solution (Mix 1:4)
7 Compressive Strength (MPa) of mortar specimens in 38
Different Nitric acid solution (Mix 1:5)
8 Weight Loss of mortar specimens in different Nitric acid 39
solution (Mix 1:3)
9 Weight Loss of mortar specimens in different Nitric acid 40
solution (Mix 1:4)
10 Weight Loss of mortar specimens in different Nitric acid 41
solution (Mix 1:5)

vii
 CHAPTER 1
INTRODUCTION

1.1 General:

Concrete is the most widely used construction material for civil engineering

construction including industrial outlets and sewer structures. These structures are

supposed to carry acidic water as industrial effluent. These acid causes serious damages

to structural concrete (Kejin et al.; 2006). Acidic environment caused by industrial

wastes or chemical residues in the ground could influence the durability of the Portland

cement concrete. When the cement binder in the concrete is exposed to an acid, the

corrosion process is started. During the acid attack the elements leached from the

cement paste has not been quantified. Several researches were carried out to overcome

this deterioration .fiber glass reinforced lining, high performance coating, special

mortars and high proportions of polymer modified binder can be more acid resistant but

they are costly for most practical application.

Concrete can be subjected to attack by various minerals acids which include nitric acid,

sulfuric acid, hydrochloric acid and phosphoric acid. Deterioration of concrete by nitric

acid is found mainly in nitric acid producing plants, fertilizer plants where nitric acid is

used as raw material. When concrete is in contact with this acid, the nitric acid react

with concrete to form highly soluble nitrate salt. The other element in the cement

remains in the form of hydroxides. This coating provides a certain protection against

continued destruction, since the aggressive acid must first diffuse through the hydroxide

layer, before it can reach the attack, the undamaged mortar/concrete. In other word the

layer slows down the attack but does not prevent it.

The loss of strength of mortar/concrete is a function of the total quality of lime leached

either from crystalline Ca(OH)2 or from the gel phase, regardless of whether it is

1
removed from the concrete of re-deposited. This quantity is equal to the sum of lime

lost by leaching from mortar/concrete Plus the quantity of lime precipitated in the form

of Ca(CO)3. Loss of strength becomes complete when concrete has lost about one half

of its original line content. None of the hydrated cement compounds completely

resistance to solutions with a pH value 10-11. All of the constituents in this range have

a tendency to loss Ca to the solution. This does not become noticeable until the pH

drops below an approximate value of 6.5 (unless the water is soft). The risk of rapid

acid attack is higher when the pH value falls below 3.5 Besides loss of strength, acid

attack also affects other important properties such as porosity, water absorption etc. this

is turn further reduces their durability.

The growing threat to concrete structures by acidic attack is a worrying topic of

increasing significance in all over the world. Therefore, information and data on the

principle, rate factors and protection measures against acidic attack of cement based

materials are useful. The aggressive effects of inorganic and organic acids, and acidic

air pollutants, like carbon, nitrogen and sulfur oxides, are reported. Acids can come

from sources external to concrete such as the earth surrounding a concrete structure,

groundwater, rainwater, pollutants in the air. Certain aggregates, including siliceous

(silica-containing), will not be attacked by acid, but calcareous (calcium containing)

aggregates readily react with acids. In this way, calcareous aggregates actually protect

the concrete. Acids attack the paste and aggregate equally spreading and lessening the

damages to the paste. It is shown that the possibility of the acidic attack is conditioned

by the universal alkalinity of cement based materials, making them a willing partner in

the reaction with acidic species.

In the present work the effect of synthetic effluents, having different acid contents, on

the strength, weight loss of the mortar specimens will be studied at different ages.

2
1.2 Statement of the Problem:

Concrete is often exposed to water which may contain domestic and industrial effluents.

With the growing contamination of water by industrial are domestic waste, building

material, especially concrete and mortar are becoming increasingly prone to aggressive

chemical attack, So a comparative study was carried out on behavior of mortar cubes

exposed to acidic water environment.

1.3 Objectives:

The objective of this project are specified below-

To investigate the deteriorative behavior of cement mortar in acidic

environment.

To study the behavior of cement of different mix exposed to acidic as well as

normal water.

To study the parameters related to durability of different mortar mix in acidic

environment.

To compare the test results of specimens test under acidic water and normal

water.

1.4 Scope:

The experimental project has been divided into some tasks to achieve the above

objectives-

Making the acidic solution according to pH of the industrial effluents.

Casting of the mortar cubes of size 2 inch and placing them in normal and three

types of acidic solution.

Testing of the specimens for the physical properties such as compressive

strength, leaching (weight loss).

3
 Carrying out of the test at different ages such as 7 days, 30 days, 60 days and

120 days.

Comparing the result of the test conducted on specimens under acidic solutions
with those of specimens placed in normal water.

4
 CHAPTER 2
LITERATURE REVIEW

2.1 Introduction:

In this chapter, a detailed literature on the behavior of concrete and mortar in acidic

environment will be reviewed. Cement mortar and concrete are susceptible to acid

attack because of their alkaline nature. The components of the cement paste break down

during contact with acids. The decomposition of concrete depends on porosity of

cement paste, concentration of the acid, solubility of acidic calcium salts (CaX2), and

fluid transport through the concrete. Acids such as Nitric acid, Hydrochloric acid and

Acetic acid are very aggressive as their low solubility calcium salts inhibit the attack

by blocking the pathway within the concrete, Sulfuric acid is very damaging to concrete

as it combines an acid and sulfate attack. Absence of calcium hydroxide in the cement

paste and surface dissolution of cement paste exposing aggregates are both signs of acid

attack.

2.2 Present State of Knowledge:

2.2.1 Portland cement:

The term cement paste refers to paste made from Portland cement. Cement paste is

much weaker than aggregate and consequent is responsible for most of the physical and

mechanical properties of the mix. Since the cement paste is more important phase in

Portland cement concrete (PCC), it is essential to understand its structures and its

chemical composition as well as their relation with properties of PCC.

Portland cement is manufactured out of lime, silica, alumina and oxide. These raw

materials when interact in the kiln form several complex chemical compounds, which

are then underground and approximately 5% gypsum. The four main compounds are

5
Tri calcium silicate C3S (55% of weight), Di calcium silicate C2A (20% of weight), Tri

calcium aluminates C3A (10% of weight) Tetra Calcium alumino-ferrite C4AF (8% of

weight). C3S and C3A are responsible for the strength of the paste. Alumina and iron,

which produces C3A and C4AF, are used to reduce the required temperature for

producing C3S. In addition, several minor compounds, such as magnesium oxide,

titanium oxide, manganese oxide, sodium oxide and potassium oxide are present in

smaller percentages of weight. Two of these minor compounds, however, play an

important role in PCC disintegration when they interact chemically with aggregate such

as sodium oxide (Na2O) and potassium oxide (K2O), creating a reaction called alkalis

silica reaction (ASR) at the presence of water under suitable temperature.

2.2.2 Hydration of Portland cement:

Hydration products Calcium silicates (both tri and di), react with water forming calcium

silicate hydrate (C-S-H) and calcium hydroxide (C-H). When hydrated completely,

Cement paste results from the hydration process, is a complex chemical reaction

between Portland cement and water. The main compounds listed above react with water

concurrently and produce calcium silicate produces a higher percentage of C-S-H and

lower percentage of C-H then what tri calcium silicate does. The C-S-H is the strength

producing hydration product of cement paste and the C-H is susceptible of acidic water

and sulfate attack. Therefore, increasing the content of the calcium silicate relative to

the amount of tri calcium silicate will change the ultimate strength of PCC and improve

its durability too. Tri calcium aluminates compound reacts with water in the presence

of gypsum of produce extradite.

Without gypsum, the tri calcium aluminates would react with water vigorously and

produce in a short time a large amount of hydration products, which can cause PCC to

6
set within a few minutes, flash setting, Gypsum is used of prevent flash setting from

occurring in the cement paste because it slows down the hydration process of the

silicate. The presence of gypsum is also beneficial in that it may causes sulfate ions in

the solution to accelerate the hydration process of tri calcium silicate to produce the

calcium silicate hydrate (C-S-H) that contributes to the final set time and early strength

gain of cement paste. As the gypsum is consumed in the hydration process, the extradite

reacts further with the tri calcium aluminates and water to produce

monosulfoaluminate. Tetra calcium alumino-ferrite (C4AF) would react with the water

and ferric-aluminum hydroxide. The reactions of the hydration process can see by the

following equations:

2C3S + 7H C3S2H8 + 3CH

2C3S + 5H C3S2H8 + CH

C3A + 3CSH2 + 26H C6AS3H32

C6AS3H32 + 2C3A + 4H 3C4ASH12

C4AF + 14H +2CH C4(A,F) + (A,F)H3

The aforementioned chemical reactions occur at different rates and strength generated

by the hydration products is different. The strength of cement paste is mostly due to the

hydration product of the calcium silicates. Although the solid phase, which the

aforementioned chemical reactions have produced, significantly affects the properties

of the cement paste, voids have important influences on the cement paste too. Three

types of voids can be identified in the cement paste. Interlayer voids, which consist of

28 percent of the porosity in the solid C-S-H, are too small to have a negative effect on

the strength and the permeability of hydrated cement paste. However, hydrogen

bonding can hold water in these voids and its removal from these voids may leads to

drying shrinkage and creep. Capillary voids represent the space not filled by the solid

7
components of the hydrated cement paste and their shapes are characterized by

irregularities. Porosity is the volume of the capillary voids. Macrospores (>50 nm) are

assumed to be detrimental to strength and impermeability, whereas Microspores (<50

nm) are more important to drying shrinkage and creep. Air voids, which are much larger

in size that capillary voids and spherical in shapes. Adversely PCC strength and

permeability. The existence of water in cement paste also affect the paste significantly.

Its presence there has been grouped into four categories. One, the interlayer water, is

located with C-S-H structured shrinks considerably when the interlayer water is lost,

but this loss occurs only in strong drying, as when the humidity (R H) is 11 percent.

Another category, capillary water is the water that is free from the attractive forces of

the solid surfaces. It is divided into two sub-categories: larger than 50 nm that is held

by capillary tension, and whose removal may cause shrinkage of the system. The third

category, absorbed water is close to solid surfaces where water molecules are physically

absorbed by the surfaces of the solids the hydrated cement paste to 30 percent relative

humidity (RH) will lead to a loss of a major portion of the absorbed water. The

chemically combined water is an integral part of structure of various cement-hydrated

products and it is not lost in drying.

Portland cement concrete properties consisting of strength, dimensional stability and

durability are influenced by proportion and the properties of the hydrated cement paste,

which in turn depends on the microstructure features of the hydrated cement paste; the

types and amount to the hydrated cement paste and the distribution of solids and voids.

Strength results from the existence of the van der Waals forces of attraction. These are

physical forces that exist between two solid adhesive surfaces. Saturated hydrated

cement paste is not dimensionally stable. When the relative humidity starts to drop to

less than 10%, shrinkage will start to occur due to the removal of water. Water removal

8
can also be due to external sustained loads, a phenomenon called creep. Durability

relates to the material service like under given environmental loads. Since the hydrated

cement paste is alkaline, acidic water is detrimental of the material. Consequently,

impermeability, also called water tightness, is a primary factor in determining durability

of the material of hydrated cement paste. Permeability is the ease with which a fluid

can flow through a solid. The size and the continuity of the pores into the structure of

the solid determine its permeability. An increasing degree of hydration greatly reduces

permeability.

2.2.2 Slag used in Cement:

Slag is the by-product of smelting ore to purify metals. They can be considered to be a

mixture of metal oxides; however, they can contain metal sulfides and metal atoms in

the elemental form. While slag are generally used as waste removal mechanism in metal

smelting, they can also serve other purposes, such as assisting in smelt temperature

control minimizing re-oxidation of the final liquid metal product before casting.

In nature, the ores of metals such as iron, copper, lead, aluminum, and other metals are

found impure states, often oxidized and mixed in with silicates of other metals. During

smelting, when the ores is exposed to high temperatures, these impurities are separated

from the molten metal and can be removed. The collection of compounds that is

removed is the slag. However, in many smelting processes, oxides are introduced in

order to control the slag chemistry, assisting in the removal of impurities and protecting

the furnace refractory lining from excessive wear.

Ferrous and non-ferrous smelting process produce different slag. The smelting of

copper and lead is non-ferrous smelting, for instance, is designed to remove the iron

and silica that often with those ores and separates it as an iron silicate based slag. Slag

9
from steel mills in ferrous smelting, on the other hand, is designed to minimize iron

loss and so mainly contains oxides of calcium, magnesium, and aluminum.

Slag has many commercial uses, and is rarely thrown away. It is often reprocessed to

separate any other metals that it may contain. The remnants of this recovery can be used

in railroad track ballast, and as fertilizer. It has been used as a road base material and

as cheap and durable means of roughening sloping faces of seawalls in order to

progressively arrest the movement of waves.

Ground granulated slag is often used in concrete in combination with Portland cement

as a part of blended cement. Ground granulated slag reacts with water to produce

cementitious properties. Concrete containing ground granulated slag develops strength

over a longer period, leading to reduce permeability and better durability properties.

Since the unit volume of Portland cement will also be reduce, concrete is less vulnerable

to alkali-silica and sulfate attack.

As cement mortar is often subjected to acidic environment and their durability and

strength property is affected so use of slag in the cement may reduce the bad effect on

acid on cement mortar. Some of the commonly used slag are:

Ground granulated blast furnace slag

Fly ash

Pozzolan etc.

Pozzolan: A Pozzolan is a material which, when combined with calcium hydroxide,

exhibits cementitious properties. Pozzolans are commonly used as an addition (the

technical term is admixture) to Portland cement concrete mixtures to increase the

long-term strength and other material properties of Portland cement concrete.

Pozzolans are primarily vitreous siliceous materials which reacts with calcium

10
hydroxide to form calcium silicates; other cementitious materials may also be formed

depending on the constituents of the Pozzolan.

The Pozzolanic reaction may be slower than the rest of the reactions that occur during

cement hydration, and thus the short-term strength of concrete made with pozzzolans

may not be as high as concrete made with purely cementitious materials. On the other

hand, highly reactive pozzzolans, such as silica fumes and high reactivity metakaolin

can produce high early strength concrete that increases the rate at which concrete

gains strength. The first known pozzolan was pozzolana, a volcanic ash, for which the

category of materials was named. The most commonly used pozzolan today is fly ash,

though silica fume, high reactivity metakaolin, ground granulated blast furnace slag,

and other materials are also used as pozzolans.

A pozzolan is a siliceous or alumino siliceous material, which is highly vitreous. This

material independently has few/fewer cementitious properties, but in the presence of

lime-rich medium like calcium hydroxide, shows better cementitious properties

towards the later day strength (>28 days). The mechanism for this display of strength

is the reaction of silicates with lime to form secondary cementitious phases (calcium

silicate hydrates with a lower C/S ratio) which display gradual strengthening properties

usually after 7 days.

The extent of the strength development depends upon the chemical composition of the

pozzolan: the greater the composition of alumina and silica along with the vitreous

phase in the material, the better the Pozzolanic reaction and strength display.

Fly ash: Fly ash is one of the residues generated in the combustion of coal. Fly ash is

generally captured from the chimneys of power generation facilities, whereas bottom

ash is, as the same suggests, removed from the bottom of furnace. In the past, fly ash

11
was generally released into the atmosphere via the smoke stack, but pollution control

equipment mandated in recent decades now require that it be captured prior to release.

It is generally stored on site at most US electric power generation facilities. Depending

upon the source and makeup of the coal being burned, the components of the fly ash

produced very considerably, but all fly ash includes substantial amounts of silica

(silicon di oxide SiO2) and lime (calcium oxide CaO). Fly ash is commonly used to

supplement Portland cement in concrete production, where it can bring both

technological economic benefits, and is increasingly finding use in synthesis of

geopolymers and zeolites.

Chemical composition and classification:

Components Bituminous Subbituminous Lignite

SiO2 20-60 40-60 15-45

Al2O3 5-35 20-30 20-25

Fe2O3 10-40 4-10 4-15

CaO 1-12 5-30 14-40

LOI* 0-15 0-3 0-5

*Loss of Ignition

Fly ash material solidifies while suspended in the exhaust gases and is collected by

electrostatic precipitators or filter bags. Since the particles solidify while suspended in

the exhaust gases, fly ash particles are generally spherical in shape and range in size

from 0.5m to 100 m. They consist mostly silicon di oxide, which is present in two

forms amorphous, aluminum oxide and Iron oxide. Fly ash are generally highly

heterogeneous, consisting of a mixture of glassy particles with various identifiable

crystalline phases such as quartz, mullite and various Iron oxide.

12
Two classes of fly ash are defined by ASTM C618: Class F fly ash and Class C fly ash.

The chief difference between these classes is the amount of calcium, silica, alumina,

and iron content in the ash. The chemical property of the fly ash are largely influenced

by the chemical content of the coal burnt.

Class F fly ash:

The burning of harder, older anthracite and bituminous coal typically produces class F

fly ash. This fly ash is pozzolanic in nature, and contains less than 10% of lime.

Processing pozzolanic properties the glassy silica and alumina of class F fly ash requires

a cementing agent, such as Portland cement, quick lime or hydrated lime with the

presence of water in order to react and produce cementitious compounds.

Class C fly ash:

Fly ash produced from the burning of younger lignite or sub bituminous coal, in

addition to having pozzolanic properties, also has some self-cementing properties. In

the presence of water, class C fly ash will harden and gain strength over time. Class C

fly ash generally contains over more than 20% lime. Unlike Class F self-cementing

Class C fly ash does not require an activator.

Fly ash reuse:

The reuse of fly ash as an engineering material primarily stems from its pozzolanic

nature, spherical shape, and relative uniformity. Fly ash recycling, in descending

frequency, includes uses in

Portland cement and grout;

Embankments and structural fills;

13
 Waste stabilization and solidification;

Raw feed for cement clinker;

Road sub base;

Stabilization of soft soil;

Aggregate;

Flow able fill.

2.3 Factors Affecting for Waste Water Analysis:

2.3.1 Scope:

To test the quality of water as the component of cement stabilized base course (CSBS)

mixtures. Water used for CSBS mixtures, should contain no substance which can have

an appreciable harmful effect upon strength.

Water that is appreciable for drinking purposes is satisfactory for use as mixing water.

Water from supply not approved by public health authorities for domestic consumption

should be examined for the nature and extent of contamination.

Substances which present in sufficient amounts in mixing water may have a detrimental

effect on cement mixtures are silt, oil, acid, alkalies, and salt of alkalies, organic matter

and sewage. No general limit of tolerance for degree of contamination has been

developed. The information contained in this procedure is perspective and not as

general substitute for direct testing.

2.3.2 Analytical test:

It is the quantity and nature of the impurities of the dissolved minerals which may have

detrimental effect upon strength

The unusual dissolved solids may be considered to be those not composed of the ions

usually present in natural water namely: Calcium, Magnesium, Sodium, Potassium,

14
Sulphate, Nitrate, and Carbonate. A rapid way of evaluating the quantity of water is to

provide a comparative analysis with local drinking water standards. The method used

by Alberta Transportation is the Hach direct reading engineers laboratory, model DR

EL2.

The Hach Direct Reading Engineers laboratory provides results for the following tests.

pH

Alkalinity

Hardness

Iron

Sulfate

Chloride

Total dissolved Solids

2.4 Acid Attack on Cement Mortar:

2.4.1 General:

Durability is an important engineering property of concrete, which determines the

service life of concrete structures significantly. Due to interactions of concrete with

external influences, the mechanical and physical properties of concrete may be

threatened and lost. Among the threatening factors like freezing and thawing, abrasion,

corrosion of steel, chemical attack may also deteriorate concrete within time.

ACI committee Report 201 (2001) has classified chemical attacks into several types

that include ; acidic attack, alkali attack, carbonation, chloride attack, carbonate attack,

leaching and sulfate attack. It can be accepted as a general rule that acids are detrimental

to concrete. The spectrum of aggressive acidic media is wide.

15
2.4.2 What is Acid Attack? :

Concrete is subjected to acid attack because of its alkaline nature. The components of

the cement paste break down during contact with acids.

Most pronounced is the dissolution of the calcium hydroxide which occurs according

to the following reaction:

2HX + Ca(OH)2 CaX2 +2H2O where X= Negative ions of the acid.

The decomposition of the concrete depend on the porosity of the cement paste, on the

concentration of the acid, the solubility of the acid calcium salts (CaX2) and on the fluid

transport through the concrete. Insoluble calcium salt may precipitate in the voids and

can slow down the attack. Acid such as nitric acid, hydrochloric acid and acetic acid

are very aggressive as their calcium salts are very rapidly soluble and remove from the

attack front. Other acid such as phosphoric acid and humic acid are less harmful as their

calcium salt, due to their low solubility, inhibits the attack by blocking the pathways

within the concrete such as interconnected cracks, voids and porosity. Sulfuric acid is

very damaging to concrete as it combines an acid attack and sulfate attack.

An acid attack is diagnosed primarily by two main features:

Absence of calcium hydroxide in the cement paste

Surface dissolution of cement paste exposing aggregates.

Acid attack increases with

Increase in acid concentration

Higher temperature

Higher pressure

16
 Constant and fast renewal of acidic solution at the concrete/liquid

interface.

2.4.3 Acid corrosion:

Cement mortar and concrete are mechanically very strong but because of the presence

of some free lime (CaO), it becomes highly susceptible to chemical attack, especially

in acidic water (pH>7). In acidic water, the lime present in the mortar and concrete

dissolves and makes the concrete weak in strength. Moreover, lime is more soluble in

soft water than hard water. Consequently concrete undergoes decay or deterioration in

soft water than hard water. Consequently concrete undergoes decay or deterioration in

contact with acidic water and soft water. Hence decay is quicker as the pH decreases

and softness of the water increases from hard to soft.

Acidic corrosion is provoked by any acid. The possible destruction of concrete in an

aqueous medium is determined by the magnitude of the pH value. The final decay

products of the constituents of mortar and concrete are silicic acid gel, calcium and

aluminum salts of the acid attacking the cement stone or when a weak acid is involved

the gel of aluminum hydroxide.

Formation of silicic acid gel :

mCaO.SiO2.aqueous + nH2O SiO2.aqueous + Ca(OH)2

Formation of Aluminum hydroxide gel :

qCaO.Al2O3.aqueous + pH2O 2Al(OH)3 + qCa(OH)2

17
2.4.4 Chemistry of Acidic Attack:

The deterioration of cementations materials, and therefore concrete, by acids is mainly

due to the reaction between acids and calcium hydroxide found in the formation of

water soluble calcium products that are then leached out. Due to this process, the pH

value of pore solution in mortar/concrete decreases, contributing to the instability of the

hydration products in the cement matrix. The quality of the matrix structure is

deteriorated and the results are loss of mass, strength and rigidity (softness).

In the case of the presence of sulfate ions, addition deterioration occurs because of

decalcification of C-S-H, or even unhydrated C3S and C2S, in the presence of sulfate

ions. This supplies Ca2+ to promote the formation of either ettringite or gypsum. It has

been noted that C-S-H around massive gypsum formation has very low calcium to

silicon ration. That type of attack (gypsum formation and decalcification of C-S-H) will

lead to expansion, elastic properties and strength loss due reduction in binding capacity.

Natural soft water containing aggressive CO2 may be very aggressive to the

cementations materials. The majority of natural waters contain certain qualities of

dissolved CO2 in equilibrium with calcium carbonate and bicarbonate. The content of

CO2 becomes significant at pH values less than 8.5. In normal pressure conditions and

temperature 20-15 C, the solution can have a pH value of about 5.6. Depending on

species in equilibrium ( presence of calcium carbonate, bicarbonate and other salts such

as calcium sulfate and sodium chloride), the pH of solution can vary from 8.5 to 5.5 (or

lower, about pH 4, if the higher partial pressure and level of concentration of other

species, such as nitrates, organic matters, sulfate, sulphide. The aggressiveness of this

water, even if they only contain CO2, cannot be judged only by pH values, because pH

values are dependent on the degree of acid dissociation. At equilibrium, CO2, calcium

18
bicarbonate are a stable system; aggressive CO2 is the amount of free carbon dioxide

present in water that is in excess of the quantity required for this equilibrium.

Aggressive CO2 reacts with calcium hydroxide in the cement matrix, from highly

soluble calcium bicarbonate, which is gradually leached out. This process leads to the

gradual decomposition of hydration products. There is no real understanding as to the

limiting values of aggressive CO2 that will lead to a significant rate of attack. It has

been concluded in some studies, that water containing more than 20 ppm of aggressive

CO2 can result in rapid decomposition and in the case of freely moving waters, the limit

could be 10 ppm. Generally, cement and cementitious materials cannot withstand

lengthy exposure to acids. Portland cement concrete is not resistant to pH values below

6 and it is considered that concrete made with any type of cement where the pH values

are less than 3 are at a high risk of damage.

2.4.5 Factor affecting acid corrosion:

Chemical characters of anions present: The degree of aggressivity of an acid is

dependent on the chemical character of anion present. The strength of acid its

dissociation degree in solution and mainly the solubility of the calcium salts formed are

dependent on the chemical character of anion.

Leaching of the constituents of cement matrix: The acidic attack is affected by the

process of decomposition and leaching of the constituents of cement matrix.

pH and acid concentration: An acidic media may achieve pH values under 7,

predominantly 6 and lower. However, pH values give no correct information about th

real quantity of the acid in the solution, because the pH value is dependent on the

dissociation degree of acid. Besides, for the aggressivity of acidic solutions, the real

concentration of acid is more significant than pH value.

19
Type of aggregate: Type also affects the performance of mortar against acid attack.

Limestone aggregate is more vulnerable to acid attacks. However, aggregate like river

gravel and similar silicious materials are more resistant.

Type of cement: The type of cement is another factor affecting the performance of

concrete in an aggressive environment. It is known that acids are always hazardous on

any type of cement. The integrity of hardened Portland cement binders is highly

dependent on maintaining the high levels of alkalinity which normally stabilize the gel

compound responsible for cementitious properties. Acid reacts with alkaline

components of the binders (Calcium hydroxide, Calcium Silicate hydrates and

aluminates hydrates) lowering the degree of alkalinity. In extreme cases acids may

completely neutralize the alkalinity. This chemical changes are disastrous and

disintegration of the matrix is the inevitable result. Portland cements are the most

vulnerable type to acidic attack, since they contains a high proportion of calcium

hydroxide released during hydration of the calcium silicates. According to Zivica and

Bajza (2002) blended Portland cements with pozzolans and slag are considered to be

more resistant to the acidic attack than Portland cements. It should also be considered

that, the efficiency of blending for acid resistance may be affected by other factors e.g

The type of cement used for blending

The amount of fineness of pozzlan used

Especially curing conditions

Nevertheless, the blended Portland cement with pozzlans, such as blast furnace slag,

fly ashes and others, have slow strength gain and hence slow reduction in permeability

properties at early ages. Additionally, these cements are more curing sensitive than

Portland cement. While the cement types differ in their degree of resistance to acid,

20
These differences are small and none of the concretes made with such materials is truly

and continuously resistant to inorganic acids. Currently emphasize is towards

producing dense and compact high performance concrete to achieve durability and

better performance of concrete in aggressive environment.

Other factors: There exist a number of factors that control hardened cement paste

deterioration in acid solution. These include the type, the concentration and pH of the

acid solution, the mobility of the solution and the W/C ratio, the type of cement and

minerals admixtures.

2.4.6 Sources Of Acid Attack on Concrete:

Industrial process: Petroleum refineries and other oil related industries and their

effluent. Various assets such as sulfuric acid, Nitric acid, Phosphoric acid plant are the

source of acid attack on concrete.

Natural sources: Natural exposure condition may cause acid attacks. Free acids in

natural waters are rare. Exceptions are carbonic waters and sulfurous and sulfuric acid

in peat water. Soils may contain huminous acid. Oxidation of sulfide minerals in clay

adjacent to the concrete can produce sulfuric acid which reacts with acids. Several

organic and inorganic acids may occur in shallow regions of sea waters as a

consequences of bacteriological activity. Significant quantities of free acids in plants

and factories may be found.

Unsafe disposal of waste: Landfills or remain the major method used for the disposal

of hazardous industrial waste. Despite continuing efforts to promote waste reduction,

recycling, reuse and clean manufacturing technologies, some waste will require safe

disposal to landfill.

21
Acid rain : The combustion of any sulfur containing materials produces SO2 and SO3.

With the present of sufficient water vapor, SO3 and water combine to form droplets of

H2SO4, which may found in the atmosphere. Similarly NO2 react with HC in the

atmosphere to form HNO3. These acids are washed out of the atmosphere as acid rain.

Other sources : Dairying, Fruit processing, Certain vegetables processing wine

manufacturing, Fish and meat processing, wool scouring and other industries all

produce various form of acids in solution which will attack concrete.

2.4.7 Effect of acid attack :

Loss of alkalinity

Loss of mass

Loss of strength and rigidity

Volume expansion

Loss of bond between the cement paste and aggregate

Alternation of paste composition with mono nitric phase converting to ettrigite

and in later stages, gypsum formation

Major cracking: Calcium hydroxide reacts with the acid and form gypsum and

ettrigite. This causes the concrete to expand. When tensile stress caused by

concrete expansion exceeds the failure tensile strength of the coating, cracking

occurs.

Spalling : When a coating cannot resist nitric acid attack itself or nitric can

easily penetrate through the coating and affect the concrete at multiple

locations, spalling occurs.

22
 Blistering: This type of failure occurs on coating with good ductility. When

concrete expand, coating deform without cracking. In some cases, blisters also

occurs under the coating film.

Eroding: In some coatings, the nitric acid directly attacks the coating film.

So mainly the durability property of the concrete is reduced, which is very important

for any type of structures.

2.4.8 Corrosion due to various acids:

A comparative loss due to solidified waste, which normally contain Pb(OH)2 and

Pb(OH)2 are specified below:

Corrosion due to acetic acids:

Weight change data of cementbased solidified wastes exposed to 0.5 N acetic acid is

a function of time. The percentage weight loss from the samples gradually increased

with increasing exposure duration, but at decreasing rate. A cement based solidified

waste consists of the hydration products of various constituents, mainly CSH gel and

calcium hydroxide , waste components, unreacted cement clinker phases and the

residue of the water- filled pores. These pores in the solidified waste formed the

capillary porosity. The ingression of an aggressive acetic acid leachant into the pore

water disturbs the chemical equilibrium formed with the surrounding solids and this

may result in solubilization of insoluble components Ca(OH)2 is the most readily

available alkali material in solidified waste and is solubilized when the pH drops below

12. The dissolution of Ca(OH)2 result in an increased degree of capillary pore

connectivity and leads to further ingression of the acid leachant. As a result, an

extensive dissolution of Ca(OH)2 and decalcification of CSH gels occurred. This led to

the formation of micro pores and macro cracking in the corroded layer. It was observed

23
that weight loss from the solidified waste increased with rising concentration of

Pb(OH)2 and Cr(OH)3 in the mixes.

Corrosion due to nitric acid:

Similar effects on all cement-based solidified waste after exposure to 0.5H nitric acid

was observed, but at a greater rate of weight loss then acetic acid, nitric acid is a strong

mineral acid, which dissociates completely, and form highly soluble calcium nitrate.

According- to the higher solubility of calcium nitrate (266.0g/100g water at 0oC )

compared to the calcium acetate (43.6g/100g water at 0 oC), calcium nitrate was likely

to precipitate in the porous corroded layer of solidified waste less then calcium acetate.

This resultant in lower diffusion resistance of the corroded layer and a greater rate of

corrosion cost by nitric acid was observed.

Corrosion due to sulfuric acid:

Weight change data of cement-based solidified waste at different exposure durations in

0.5N sulfuric acid. A gain in weight of cement-based solidified wastes after exposure

to sulfuric acid was observed. Similar observation was reported by several researchers

that the weight gain was caused by the deposition of gypsum on the surface and in the

porous corroded layer of the solidified wastes

Ca(OH)2 + H2SO4 = CaSO4 + 2H2O

Gypsum, which is formed by the reaction between sulfate ion and calcium hydroxide,

has very low solubility (0.22 g/100 g water, at 0oC). Formation of this insoluble gypsum

layer can prevent the solidified waste matrices from further deterioration upon contact

with sulfuric acid. However, this gypsum layer was loosely connected with the

24
solidified waste and fell of spontaneously. This implies that the solidified waste was

substantially deteriorated, although at a much slower rate compared to acetic and nitric

acid.

Corrosion due to hydrochloric acid: The action of HCI on cement hydration products,

in particular Ca(OH)2 and the resulting products are presented in the following chemical

equations :

From equation It can be seen that, consumption of Ca(OH)2 results with formation of

salts of CaCl2. By the help of water, these soluble salts may easily be transported to the

outer parts of mortars. In this situation, continuous reactions increase the porosity of

cement paste and increased pore volume speed up the rate of reaction.

2.4.9 Prevention of acid attack on concrete:

Portland cement usually does not have good resistance to acids. Some weak acid

however can be tolerated, particularly if the exposure is occasional. There are essential

three ways to improves concrete resistance to acids:

Choosing the right concrete composition to make it as impermeable as possible.

Isolating it from the environment by using a suitable coating.

Modifying the environment to make it less aggressive to the concrete.

25
 CHAPTER 3
EXPERIMENTAL INVESTIGATION

3.1 Introduction:

The experimental investigation was carried out on 144 members of cement mortar cube

of size 2 inch. Among 144 samples 36 were placed in normal water, among 36 samples

9 were kept under water for 7 days, 9 were under one month another 9 were under 2

months and rest are for 4 months. 3 types of acidic sample were used. They were HNO3

of pH 1, 2, 3. There were 3 variables in cement sand ratio they are 1:3, 1:4, 1:5. Each

acidic sample contains 36 samples in 3 groups with respect to cement sand ratio.

Compressive strength test was induced in this project with these cement mortar

samples. For compressive strength test average of 3 samples are taken as the result for

a particular combination.

3.2 Materials:

3.2.1 Sand

Mainly local sand was used in this experiment. 4 types of sieves were used for casting

of mortar samples. Sieve were No. 16, no. 30, no. 50 and no. 100. The ratios among 16

passing - 30 retained, 30 passing 50 retained and 50 passing 100 retained were 1:2:1.

As 16 passing 30 retained was not available in amount from local sand, so a small

amount of Sylhet sand was used in the sand sample. At a glance

FM =2.5

Absorption Capacity = 1.5%

Moisture Content = 0.35%

26
3.2.2 Cement

Portland Composite Cement was used in the experiment. The used brand was Royal

cement.

3.2.3 Acid

HNO3 acid was used in the experiment. Three pH of acid was made to form the acid

solution which create the similar environment of synthetic acid effluent. These are of

pH 1, 2 & 3.

Cement mortar cubes are placed in this solutions to examine the deterioration due to

acid attack.

3.3 Casting and Re-Molding

3.3.1 Mixed proportion:

To make the mortar cubes three types of cement sand ratios were used to determine the

effect on mortar due to variable ratios. These ratios are 1:3, 1:4, 1:5.

The used water cement ratio was 0.45

3.3.2 Casting:

The following procedures was followed for casting, remolding and curing:

The molds were cleaned and lubricated by grease

Cement and sand were mixed thoroughly with respect to the desire c/s ratio and

then water was added with the following w/c ratio. After adding water the

mixture were mixed properly.

Now 1/3 of the mold were filled with mortar and given 36 blows.

The mold was filled in 3 layers and each layer was subjected to 36 blows.

27
 After 24 hours of casting, cubes were taken out from the mold and then placed

outside for air curing to dry.

Then immersed in water for curing 7 days to gain strength.

The samples are then placed into different exposure for different time period.

At the end of the period they are taken out from the solution for different testing.

3.3.3 Preparation of acid solution:

Acid solution were made similar to the actual environment at which any concrete

structure subjected to. To create this solution trial and error procedure was followed.

The HNO3 which was used to make the solution has the following property:

For 65% HNO3, Molarity = 10.32 M

pH 1 Solution = 8 mg/l

pH 2 Solution = 0.8 mg/l

pH 3 Solution = 0.08 mg/l

3.4 Experimental Program:

3.4.1 Casting of Specimen:

At the time of experiment the test were carried out in different environment for different

curing periods which are shown in the table 3.4.1.

Size of the specimen = 50mm x 50mm x 50mm

Cube specimens 36 nos. for control, 36 nos. for acidic solution of pH 1, 36 nos. for

acidic solution of pH 2, 36 nos. for acidic solution of pH 3,

Total mortar cubes=144 nos.

Exposure period 7 days, 28 days, 60 days, 120 days.

28
3.4.2 Physical Test for Cement:

3.4.2.1 Normal Consistency:

The consistency is measured by the vicat apparatus using a 10 mm diameter plunger

fitted into the needle holder. A trial paste of cement and water is mixed in a prescribed

manner and placed in the cylindrical mold of the vicat apparatus. The plunger is then

brought into contact with the top surface of the paste and releases. Under the action of

its weight the plunger will penetrate the paste. The depth of penetration of plunger into

the paste is observed on the vertical scale. This is considered to be the standard when

the plunger penetrates the paste to a point 10 mm from the top of the mold within 30

seconds. The water cement of the standard paste is expressed as a percentage of the

weight of cement, the cement paste which allows the above penetration of the plunger

is termed as standard cement paste of normal consistency.

3.4.2.2 Initial setting time:

The initial setting time of standard cement paste are determined by vicat apparatus. For

the determination of the initial setting time a round or square needle, with a cross

sectional area of 1 sq. mm is used. The needle, acting under a prescribed weight is used

to penetrate a paste of standard consistency placed in the vicat mold. When the paste

stiffens sufficiently for the needle to penetrate only to a point about 25 mm from the

top initial setting is said to have taken place. Initial setting is expressed as the time

elapsed since the mixing water added to the cement.

3.4.2.3 Final setting time:

Final setting is determined by 1 sq. mm needle fitted with a metal attachment hollowed

out so as to leave a circular cutting edge 5 mm in diameter and set 0.5 mm behind the

29
tip of the needle. The final setting is said to have taken place when the needle, gently

lowered to the surface of the paste, makes an impression on it but the circular cutting

edge fills to do so. The final setting time is reckoned from the moment when mixing

water was added to the cement.

Figure-1: Vicat Apparatus

30
3.4.3 Different test for mortar specimens:

3.4.3.1 Compressive strength:

The mechanical strength of hardened cement is the property of the material that is

perhaps most obviously required for structural uses. It is not surprising, therefore, that

strength tests are prescribed by all specifications for cement.

The strength of mortar or concrete depends on the cohesion of the cement paste, on its

adhesion to the aggregate particles and to a certain extent on the strength of the

aggregate itself. The last factors is not considered at this stages, and eliminated in test

on the quality of cement by the use of standard aggregates. Cement sand mortar of

prescribed proportion and made with specified materials under strictly controlled

conditions are used for the purposes of determining strength of cement.

Compressive strength of the sample was taken the mean of strength of three specimens.

31
Figure-2: Compressive strength testing apparatus

32
Figure-3: Mortar specimens

33
3.4.3.2 Weight loss:

Generally, percentage mass loss after a period of immersion increases with acid

concentration and immersion period for each mix and at each laterite content

investigated. For mix 1:3 and between 0% and 25%, the mass loss increases as laterite

content increases. However, beyond 25% laterite content, the mass loss decreases. This

was clearly observed from Table 3 at 5% and 10% acid concentrations. Similarly, this

second pattern was also exhibited by the lesser rich mix 1:3. Again, the influence of

incorporating concrete on the acid resistance of the resulting concrete is evident. Table

3 shows that more than 10% loss in mass due to immersion in all the nitric acid solutions

was recorded after 28days immersion period for the three mixes tested.

Figure-4: Mortar specimens

34
 CHAPTER 4
RESULT & DISCUSSION

4.1 General:

The test were done in different environment for different curing period. As the end of

7 days 36 samples from different environment were taken out. Among those 36 samples

9 were taken from normal water, 9 from HNO3 of pH 1, 9 from HNO3 pH 2, 9 from

HNO3 of pH 3.Each of 9 samples set contain three different cement ratio, 1:3, 1:4,

1:5.Each ratio contains 3 samples .Then the test are done. After 1 month, 2 months, 3

months, 4 months same procedure were followed.

4.2 Test Results for Concrete Specimens:

4.2.1 Compressive strength:

The compressive strength test results of mortar have been presented in tables 1, 2, and

3. From the observation tables, it is found that the strength of mortar specimens under

normal water is progressively increasing with time. The increase in the strength of

mortar under normal water is obvious because specimens were under continuous

curing. The specimens exposed to acidic solutions are showing in a decreasing trend in

accordance with acid intensity. This is an agreement with fact that the acid attack is

severe with time with the increasing of time.

35
4.2.2 Weight loss:

The weight loss results of mortar have been presented in tables 4, 5, 6. From the

observation of tables, it is found that the weight of mortar specimens under is

progressively decreasing with time. The decrease in the weight mortar specimens under

acidic water is obvious because specimens were under continuous immersed in acidic

water. The percentage of weight loss increasing with the increasing of time and acid

intensity.

Table 1: Compressive strength (MPa) of mortar specimens in different Nitric acid

solution (Mix 1:3)

Curing Period Control HNO3 soln. HNO3 soln. HNO3 soln.

(Days) specimens (pH-1) (pH-2) (pH-3)
(Plain Water)
7 12.4 10.4 10.9 11.2
28 13.6 10.1 10.5 10.8
60 14.4 9.2 9.9 10.5
120 15.6 9.0 9.5 10.0
Compressive strength(MPa)

18
16
14
12
10
8
6
4
2
0
7 days 28 days 60 days 120

Normal water Nitric acid pH 1

Nitric acid pH 2 Nitric acid pH 3

Figure 5: Compressive Strength (MPa) of mortar specimens in Different

Nitric acid solution (Mix 1:3)

36
 Table 2: Compressive strength (MPa) of mortar specimens in different
Nitric acid solution (Mix 1:4)

Curing Period Control HNO3 soln. HNO3 soln. HNO3 soln.

(Days) specimens (pH-1) (pH-2) (pH-3)
(Plain Water)
7 11.0 8.9 9.3 10.0
28 12.5 8.5 8.9 9.8
60 13.6 7.9 8.7 9.1
120 14.2 7.2 7.8 8.9
Compressive strength(Mpa)

16
14
12
10
8
6
4
2
0
7 days 28 days 60 days 120

Normal water Nitric acid pH 1

Nitric acid pH 2 Nitric acid pH 3

Figure 6: Compressive Strength (MPa) of mortar specimens in different

Nitric acid solution (Mix 1:4)

37
 Table 3: Compressive strength (MPa) of mortar specimens in different
Nitric acid solution (Mix 1:5)

Curing Period Control HNO3 soln. HNO3 soln. HNO3 soln.

(Days) specimens (pH-1) (pH-2) (pH-3)
(Plain Water)
7 6.3 4.6 5.4 5.9
28 6.6 5.3 5.4 5.8
60 6.7 5.7 5.4 5.6
120 7.6 4.1 5.1 5.2
Compressive strength(Mpa)

9
8
7
6
5
4
3
2
1
0
7 days 28 days 60 days 120 days

Normal water Nitric acid pH 1

Nitric acid pH 2 Nitric acid pH 3

Figure 7: Compressive Strength (MPa) of mortar specimens in different

Nitric acid solution (Mix 1:5)

38
 Table 4: Weight loss (Mix 1:3)
Period(days) pH Initial weight (gm) Final weight (gm) Weight loss (%)
1 270.3 269.1 0.47
7 2 277.5 277.0 0.16
3 278.6 278.5 0.04
1 279.7 276.6 1.11
28 2 270.3 268.6 0.6
3 277.2 276.8 0.12
1 277.7 273.7 1.44
60 2 274.6 272.0 0.94
3 280.8 279.5 0.45
1 282.4 276.4 2.12
120 2 287.1 283.2 1.36
3 272.0 270.0 0.76

2.5

Nitric acid
2 Soln.(pH 1)
weight loss (%)

Nitric acid
1.5
Soln.(pH 2)

1 Nitric acid
Soln.(pH 3)

0.5

0
0 20 40 60 80 100 120 140
Curing Age (days)

Figure 8: Weight Loss of mortar specimens in different Nitric acid solution

(Mix 1:3)

39
 Table 5: Weight loss (Mortar 1:4)
Period(days) pH Initial weight (gm) Final weight (gm) Weight loss (%)
1 265.6 264.2 0.51
7 2 257.9 256.6 0.5
3 271.4 270.6 0.27
1 261.5 259.3 0.84
28 2 261.6 259.8 0.69
3 268.8 267.3 0.57
1 265.7 262.5 1.20
60 2 266.0 263.9 0.79
3 261.3 259.5 0.69
1 263.1 258.1 1.89
120 2 261.9 259.0 1.13
3 264.8 262.3 0.96

1.8 Nitric acid

Soln. (pH 1)
1.6

1.4
Weight Loss (%)

Nitric acid
1.2 Soln. (pH 2)
1
Nitric acid
0.8 Soln. (pH 3)
0.6

0.4

0.2

0
0 20 40 60 80 100 120 140

Curing Age (days)

Figure 9: Weight Loss of mortar specimens in different Nitric acid solution

(Mix 1:4)

40
 Table 6: Weight loss (Mortar 1:5)
Period(days) pH Initial weight (gm) Final weight (gm) Weight loss (%)
1 262.8 258.9 1.49
7 2 263.5 262.8 0.25
3 262.9 260.2 0.99
1 264.5 259.6 1.84
28 2 263.8 262.9 0.33
3 261.4 258.7 1.02
1 261.3 256.2 1.93
60 2 267.3 265.7 0.61
3 268.3 265.1 1.21
1 258.2 252.7 2.13
120 2 265.5 262.6 1.10
3 266.1 262.6 1.32

2.5
Nitric acid
2
Soln.(pH 1)
weight loss(%)

Nitric acid
1.5 Soln. (pH 2)

Nitric acid
1
pH 3

0.5

0
0 20 40 60 80 100 120 140
Curing Ages (days)

Figure 10: Weight Loss of mortar specimens in different Nitric acid solution
(Mix 1:5)

41
4.3 Discussion on the Results:

1. The cement used to make the cement mortar was sound, fine and of good chemical

composition.

2. In normal water, compressive strength increases with days and in acidic water

compressive strength decreases gradually.

3. In highly intensity of acidic solution, the compressive strength of mortar is reduced

more rapidly than lower intensity acidic solution.

4. In acidic water, the weight of mortar specimens decreases with time.

Thus, it can be noted that if any acid present in water at its higher concentration, mortar

should be of higher strength to offer higher resistance.

42
 CHAPTER 5
CONCLUSION

5.1 General:

Concrete is often exposed to water which may contain domestic and industrial

effluents. In sewers the crowns are severe attacked by the Nitric acid formed in the

present of Nitrogen-di-oxide. Organic acid formed in various industries such as

breweries, dairies, canneries. Nitric acid usually occurs in chemical plants producing

explosives, artificial manure and similar products cause damages to mortar and

concrete surfaces.

5.2 Conclusion:

Adverse effects of the aggressiveness of the acidic sewage on the cement mortar and

concrete is continuous process. Since the project have been carried out over a short

duration the actual behavior of mortar under acidic solution could not be fully observed.

However, based on limited number of test and observation, the following conclusions

can be drawn.

1. The compressive strength of mortar gradually decreases with the increase acid

intensity. The decreases of strength values are observed to be lies between 10 to

42% for ratio 1:3, 20 to 49% for ratio 1:4,27 to 46% for ratio 1:5, compared to the

plane water.

2. Cement mortar of mix 1:3 gives better results than those of mix 1:4, 1:5.

3. The weight of mortar cubes decreases with the increase in intensity of pH values

in acidic solution for any exposure period.

43
 4. The changes in weight of mortar specimens are observed to very within the range

of 0.46 to 2.13% for pH 1, 0.16 to 1.36% for pH 2, 0.04 to 1.32% for pH 3 of Nitric

acid solution.

5.3 Suggestion for Future Work:

The test have been done for three different curing period 7 days, 1 month, 2 month, 4

month which are actually too short to study the behavior of mortar in acidic condition.

However as a result of this study from several aspects, some important points as regards

to the behavior of mortar under aggressive acidic environment have come into view.

So an effort should be taken to the study the behavior of mortar in details. A few of

these efforts have been furnished below as a scope of future work under this context.

Future investigations may be carried out by curing the specimens in the sewage

water directly and also in the acidic solution sample made by those acids which

are present in the waste water.

Since the strength of mortar depend on the cement-sand ratio and w/c ratio,

different mix ratios may be used to determine which one gives better result in

acidic waste water.

As curing period affects the durability of mortar, the same investigation may be

done for several months more to examine the deterioration conditions of mortar

under acidic environment.

Similar study may be carried out for concrete specimens with different mix ratios

and different types of cement by controlling the curing temperature and the quality

of the mortar mix that means good compaction.

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 Change in other properties such as elastic/plastic properties, cracking, water

absorption, and change in volume for the gradual determination of strength.

Acetic and Phosphoric acid solution can be used to place the concrete specimens

because those are also too much responsible for deterioration of concrete.

Wide range of pH such as 3, 4, and 5 may be used.

Correlation among permeability, porosity, and ultrasonic pulse velocity may be

determined.

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