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University of Cape Town THE COMPRESSIVE STRENGTH OF FLY ASH CONCRETE AND ITS MINERALOGY by . Volker R. Gogol A thesis submitted for the degree of Master of Science in Applied Science to the Faculty of Engineering at the University of Cape Town. Department of Civil Engineering University of Cape Town February 1994 .: .. ... ....... ......... , ..... · : . t Tlie .. > ( , , , .... _.,1 (:q3 0 ,vcn ·"" 1 the ri:;;:1c l<• , .. ,,,,,,: .. ;•y, _ in ._;;ho!G or In p;;rt. i:: i;E:i..; by 1.:10 author. f; ·u,•·· ·.-;.-·:., ..

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Page 1: Town Cape of University

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THE COMPRESSIVE STRENGTH OF FLY ASH

CONCRETE AND ITS MINERALOGY

by .

Volker R. Gogol

A thesis submitted for the degree of Master of Science in Applied Science to

the Faculty of Engineering at the University of Cape Town.

Department of Civil Engineering

University of Cape Town

February 1994

[~·--.,~~.~-'··;.~. -~·~ .: .. ~:., ... '· ....... _·.,~ ......... , ..... · : . ·.~·.··~:.'..·,·.~7?';_-i t Tlie l..n1v~1,~i .. > ( , ~.·r:~·, , , .... _.,1 (:q3 ~.\::Gt"? 0,vcn ·"" 1 the ri:;;:1c l<• , .. ,,,,,,: .. ;•y, _ ,:.=~.: ~L.:::':; in ._;;ho!G ~ ~ or In p;;rt. C:·J:'y;·i~J!~: i:: i;E:i..; by 1.:10 author. f; ~!:;~---~l',7"_~'1""~'.• •.,.-·..1:~·1 ·~ ·u,•·· ·.-;.-·:., ~:-w-:_'::"7.--~:' :-:''~"'-~; ·~ .. ·.•;>!"'<-lQ»~

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The copyright of this thesis vests in the author. No quotation from it or information derived from it is to be published without full acknowledgement of the source. The thesis is to be used for private study or non-commercial research purposes only.

Published by the University of Cape Town (UCT) in terms of the non-exclusive license granted to UCT by the author.

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THE COMPRESSIVE STRENGTH OF FLY ASH

CONCRETE AND ITS MINERALOGY

by Volker R.Gogol

The use of fly ash as a cement extender in portland cement concrete is well

established. Strict requirements are set for the fly ash on its physical properties

and chemical composition to ensme its successful application as a partial

replacement material for cement.

An investigation was undertaken into the effectiveness and properties of a high

carbon clinker ash when used as a cement extender at a 30% direct mass to mass

substitution for portland cement. The clinker ash came from the Van Eck power

station in Windhoek, Namibia and was milled to pass a 63micron sieve. For

comparison fly ashes from the Escom power stations of Lethabo, Duvha and Matla

were used. Both concrete and pure paste specimens were prepared for. the

evaluations.

The compressive strengths of the con,cretes were tested at different time intervals

on cubes cured for up to 28 days. Samples from the paste cubes were prepared by

crushing and freeze-drying, to be used in differential thennal analysis (DTA) and

the1mogravimetric analysis (TGA), which gave infonnation on the mineralogy and·

hydration progress respectively. Ultimately, the results from the paste analyses

were related to the strength development of the concretes. A good correlation was

found between the total amount of bound water in the pa5tes and the compressive

strength of the concretes.

The study showed that, even with the milled clinker ash containing >30% carbon,

it could successfully be used as a cement extender in concrete. In addition to

pozzolanic reactivity of the ash, it also had some inherent cementicious character.

The long-term effects, that is to say at times after 28 days o~ curing, have still to be

investigated to determine the effect, if any, on the durability ?f concrete containing

the high carbon milled clinker ash. \

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INDEX

Page

1. Introduction 1

2. Literature Survey 3

2.1 Fly Ash - The Material 3

2.2 Fly Ash in Concrete 7

2.2.1 Fly Ash and Portland Cement 7

2.2.2 Fly Ash and the Hydration of C3S 13

2.2.3 Fly Ash and the Hydration of C3A 16

2.2.4 Fly Ash and the Hydration of Portland Cement 18

2.3 The Performance of Fly Ash Concrete 20

2.3.1 Workability of Fly Ash Concrete 20

2.3.2 Strength Development of Fly Ash Concrete 26

2.3.3 Durability of and Properties of Fly Ash Concrete 33

2.4 Summary 40

3. Experimental Approach 41

3.1 Materials 41

3.1.1 Cement 41

3.1.2 Cement Extenders 41

3.1.3 Aggregates 46

3.1.4 Mixing Water 46

3.2 Mix Design and Sample Preparation 48

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4.

4.1

4.2

5.

5.1

5.2

5.2.1

6.

7.

Results and Discussion - Concrete

The Fresh State

The Hardened State

Results and Discussion - Pastes

Identification of Peaks

Thermogravimetric Analysis

Quantitative Analysis - the Amount of Bound Water

Summary and Discussion

References

Appendices

Appendix A - Materials

Appendix B - Concrete Results

Appendix C - DT A , TGA and DTG Results

Appendix D - Fly Ash Concrete Mix Design

51

51

53

59

62

67

68

74

79

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1. INTRODUCTION

The use of Fly Ash as a mineral additive to Portland Cement Concrete has been

known since early this century, however extensive research during the past two to

three decades is responsible for the present knowledge about the topic. Being a

waste product of thermal power stations and available in huge quantities, fly ash as

a cement extender presents itself as a very attractive application in terms of

economic considerations. In addition to the benefits gained by lowering of

building costs (due to a reduction in cement consumption), the incorporation of fly

ash into concrete yields many more desirable benefits in the field of general

concrete properties in the fresh as well as hardened state. Further aspects like

improved durability and increased resistance to degradation (chemical and

physical) enhance -the offset against the disadvantages involved with the blending

of cement with fly ash.

The main drawback arising from fly ash being added to or partially substituted for

the cementitious content of a concrete mix, is the retarded strength development

during early age relative to the mix with only cement as binder material. This

drawback can be bypassed with appropriate adjustment of the particular mix

design by increasing the cement/water ratio, thus increasing the cement content.

In other words a higher target strength may be aimed for in the design of the

concrete mix to ensure comparative strength values. However this would

adversely affect the improved cost factor and hence point back to using a straight

cement component in the mix design on the basis of economic considerations.

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The use of fly ash as a cement extender is not a trivial ·matter and requires careful

consideration and planning, taking into account all the participating factors in

preparing the mix design.

In the presented work, an investigation was undertaken into the relationships

between the properties of fly ash (chemical, mineralogical and physical) and

strength development of the fly ash concrete up to 28 days of age. Compressive

strength was chosen as the comparative parameter, as this is generally still the

concrete property on which the largest emphasis is placed in determining quality

of the material.

The following four coal ashes were compared in their performance as cement

extenders in concrete:

• fly ash from the Lethabo power station,

• fly ash from the Duvha power station,

• fly ash from the Mada power station and

• a milled clinker ash from the Van Eck power station m Windhoek,

Namibia.

Samples of the ashes and the cement used were characterized according to their

chemical composition, mineralogy and fineness. For each type of ash, a concrete

mix was prepared and the compressive strength of cubes tested at the time

intervals of 3, 7, 14, 21 and 28 days after casting. In parallel, pastes were made up

with the same ratio of cement to ash. The paste cubes were cured under the same

conditions as the concrete cubes. At the particular time intervals, these were used

to carry out differential thermal analyses as well as thermogravimetric analyses.

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2. LITERATURE SURVEY

2.1 FLY ASH - THE MATERIAL

The residue of the coal burning process in modem thermal power stations is

referred to as pulverized fuel ash (pfa) of which fly ash is the portion of fine

material. Fly ash is classified as a pozzolanic material. Pozzolans are defined

as "siliceous or siliceous and aluminous materials which in themselves possess

little or no cementitious value but will, in finely divided from and in the

presence of moisture, chemically react with calcium hydroxide at ordinary

temperatures to form compounds possessing cementitious properties" (ASTM-

618-89, 1988).

Generally one can differentiate between two classes of fly ash: either 'low-lime

fly ash' with truly pozzolanic characteristics or 'high-lime fly ash' showing

some cementitious properties in addition to the pozzolanic reactivity. This

classification is mainly determined by the type of coal that is burnt to produce

the ash. The low-lime fly ash (CaO < 10%) results from the burning of

anthracite and bituminous coals, whereas the high-lime fly ash (CaO > 10%) is

produced from sub-bituminous and lignite coals. Under the additional

condition that the sum of the oxides (Si02 + Al20 3 + Fe20 3) has a minimum of

70%, the low-lime fly ash corresponds to the ASTM-618 specification for type

F-fly ash, whereas in the case that the sum of the three oxides has a minimum

of 50%, the high-lime fly ash complies with the ASTM-618 type C-fly ash.

Truly pozzolanic ashes are referred to as type-F (ASTM), whereas ashes

displaying some hydraulic properties are classified as type-C (ASTM).

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The situation with South African fly ashes is clear-cut in terms of the above

definitions and terminology: All the ashes comply with the definition of type-F

fly ash. The composition of different fly ashes is given in Table 2.1.

Fly ash is a product of the combustion process of finely ground coal at thermal

power stations. In the furnace, which operates at a temperature of about

1500°C, the carbonaceous content of the coal is burnt very rapidly. The

remaining material, consisting of mainly silica, alumina and iron oxide, melts

while still being suspended in the injection gas stream. The very rapid cooling

of the flue gases results in the solidification of the melt droplets into fine

spherical hollow particles of fly ash. Such rapid cooling yields incomplete

crystallization and hence a partly amorphous material is formed. It is this

glassy phase which is responsible for the pozzolanic activity of the fly ash.

The glassy phase is a typical silica-alumina glass, whereas mullite (3Al20 3·

2Si02) is the main constituent of the crystalline phase. In addition, the

crystalline iron oxides of haematite (Fe20 3) and magnetite (Fe30 4) are found as

separate paiticles, as is quaitz. Types of fly ash with high alkaline earth

contents often contain spinel (MgO·Al20 3) and wollastonite (CaO·Si02). Any

carbon that may still be present, is in the form of char particles.

Initial mechanical means, followed by electrostatic precipitators, collect the ash

according to particle size, the largest ash particles being collected first. The

coal characteristics, the burning profile at the power station and the collection

setup are all important variables influencing the properties and consistency of

the fly ash. The issue of characterizing the fly ash is not a simple task, as a

wide range of properties needs to be taken into consideration.

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The pozzolanic activity of fly ash in concrete is largely dependent on the

fineness (particle size and particle size distribution) of the ash. The smaller the

ash particles, the bigger is the surface area for a given mass of material and

hence more reaction sites are present for the hydration process to initiate.

However, a lower limit to particle size also exists from a practical point of

view, for example, the finer the ash, the more difficult its the handling and

storing becomes.

The compatibility of portland cement and fly ash arises from the mineralogical

and chemical composition of the two materials. To produce portland cement a

finely ground mixture of calcareous materials (commonly limestone or chalk)

and argillaceous materials (commonly clay or shales) and/or other silica,

alumina or iron oxide bearing materials is burned at a temperature of above

1400°C to produce clinker. The clinker is then cooled, ground and intermixed

with a small proportion of gypsum (to delay setting time) and possibly some

other inorganic additives for specialized applications (Mantel, 1992).

As is shown in Table 2.1 below, both portland cement and fly ash consist

essentially of silica, alumina, calcium and iron (all in oxide form), but in

varying proportions. The exact chemical composition, as well as physical

properties, differentiate cement and fly ash into the groups of a hydraulic

binder and pozzolan respectively. Portland cement (ordinary and rapid­

hardening) are covered by the specification SABS 471, whereas fly ash to be

used as cement extender has to comply with the specification SABS 1491-2.

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Table 2.1 : Chemical Analysis of Portland Cement and Fly Ash.

a after Mantel, 1992

Oxide

Si07

Ah01

Fe20.~

Cao

MgO

S01

Na20

K70

b Lethabo fly ash (Grieve, 1991)

c CANMET data for ASTM class F fly ash (Malhotra and

Painter, 1988)

d AST:\1 class F fly ash (Galeota et al., 1992)

Portland

Cementa Fly Ash

South Africab Canadac Ital yd

22.9o/o 52.55% 47.1% 45.8%

4.2 29.75 23.0 31.2

3.8 3.95 20.4 3.96

65.0 5.45 1.21 6.90

3.3 1.35 1.17 1.79

0.2 2.10 0.67 1.00

0.1 0.20 0.54 0.24

0.6 0.50 3.16 0.84

6

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2.2 FLY ASH IN CONCRETE

The use of fly ash as a cement extender in concrete affects both the fresh and

hardened properties ,of the material. In general, the early-age strength

development of fly ash concrete is retarded in relation to a mix without any fly

ash added, even though its long-term strength may be comparable. Much too

often however, the early-age compressive strength of concrete is considered the

sole and absolute indicator of quality, and this aspect is the reason for much

criticism of fly ash concrete. Another aspect is that the benefits gained from

correct curing are often not recognized and instead higher costs are incurred by

increasing the cement content of a mix in order to meet specifications. If the

above attitude about concrete strength can be changed, much can be achieved

in the fields of economics and concrete quality by only changing the

methodology and practice of concreting.

2.2.1 FLY ASHMTIPORTLANDCEMENT

There are two basic methods of fly ash inclusion in concrete: (1) to use a

composite cement containing fly ash produced either by blending or

intergrinding, and ( 2) to introduce the fly ash as a direct admixture during

mixing. The main benefit of the second method is that the mix design may be

proportioned to meet the exact requirements of the specific application, without

being limited by the fixed cement-to-fly ash ratios set by the supplier of

blended cement. There are two approaches. Using the 'replacement method',

the cement is simply replaced on a mass-to-mass basis, which results in an

increase in the binder volume due to the lower density of fly ash in relation to

cement. Hence an adjustment in the aggregate content is required to

incorporate this volume change. The second approach, referred to as the

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'design method', is based on the underlying principle that there exists an

optimum amount of fly ash for a specific concrete mix, which is a function of

its water-portland cement ratio (Dhir, 1986). Swamy (1990) presents some

guidelines on fly ash concrete mix proportioning and concludes that, for given

conditions of curing and age of testing, the properties developed by the material

are greatly influenced by the particular method used to determine the mix

design. In Appendix D different methods of mix design incorporating fly ash

into concrete are presented.

In the following text where the chemistry of cement hydration and cement-fly

ash hydration is discussed, the practice of using cement chemistry notation is

followd. The accepted abbreviations used are as follows.

Table 2.2 : Cement chemistry notation as in Fulton (Addis, 1986).

Oxide Abbreviation

Cao c AhO~ A

SiO? s

Fe.,o~ F

MgO M

Na.,O N

K?O K

H?O H

so~ S"

The detailed interaction of fly ash and portland cement during the hydration

and hardening process is not yet fully understood. It has been established

however that the pozzolanic reaction of fly ash may be summarized as the

reaction of the free lime or portlandite (Ca(OH)i), produced in the cement

hydration, with the glassy phase of the fly ash to produce calcium silicate- and

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aluminate hydrates. However, the cement hydration and the pozzolanic

reaction of the fly ash do not proceed independently and hence mutually

influence one another. Reaction profiles (rates, surface reactions, nucleation

and crystallization) and reaction products formed cannot be considered

individually as they are interdependent, adding to the complexity of the system.

Research by Bijen ( 1992) on the pozzolanic reaction of fly ash in concrete has

been reported by the Dutch Concrete Society. Under ambient conditions, the

reaction of fly ash with portland cement does not start immediately when the

mixing water is added. During this period of passivity, the fly ash acts mainly

as precipitation sites for lime and calcium-silicate-hydrate-gel (CSH) resulting

from the cement hydration. After this dormant period, the pozzolanic activity

starts, which is a slow process in terms of reaction rate. This delayed fly ash

reaction is the basis for the different behavior in the fresh state of concrete

which incorporates fly ash. As the fly ash initially behaves more or less as

ine11 material, it essentially produces a higher water-to-cement ratio (W/C).

Hence the concrete will initially be less strong and have a higher permeability.

Figure 2.1 : Illustration of the effectively higher W/C ratio due to the presence

of 'inert' fly ash during the dormant period (Bijen, 1992).

Once the pozzolanic reaction is initiated, the negative effects due to the higher

W IC ratio are reduced in the sense that the fly ash contributes to the

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development of strength. The extent of reaction is a function of the

composition and physical properties of the ash, with fineness and smface area

being of particular importance. The start of the pozzolanic reaction is

associated with the decomposition of the glass phase of the ash. Because the

glassy phase is the active component in the material, the ratio of glass to

crystalline phases is of prime importance. The pozzolanic activity of fly ash in

concrete is greatly determined by the alkalinity of the pore water. Generally

speaking, a pH of greater than 13 has to be attained before effective dissolution

of the glassy phase takes place. The hydration reaction of the cement increases

the pH by releasing Ca(OH)2 into the pore water, hence the rate of the cement

hydration reaction plays an important part in determining the length of the

dormant period of the fly ash.

The following factors influence the development of alkalinity and thus

ultimately the pozzolanic activity (Bijen, 1992):

• The type of fly ash and type of cement used will have a particular alkaline

content in terms of their chemical composition.

• The fineness of cement used. The finer the cement, the higher the rate of

hydration, thus the faster the increase of the pH of the pore water.

• For a higher W/C ratio, the alkalinity of the pore water will be lower and

hence the pozzolanic reaction retarded.

• A higher temperature will result in an increased rate of development of

alkalinity and hence faster reaction of the glassy phase of the fly ash.

• The effect of curing, especially during the dormant period, is very

pronounced for fly ash concrete in the sense that a deficiency in water will

te1minate any pozzolanic reaction.

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The dissolution of the fly ash in the pore water results in the reduction of the

free lime concentration of the water. The effect of reducing the free lime

content and actually transforming it into a cementitious binder material and

thus aiding in the strength development of the concrete, is one of the most

beneficial consequences derived from using fly ash. The pozzolanic reaction

would be terminated, if the free lime content were to be exhausted. However in

practice such a situation will not be reached with portland cements as the latter

will, in the presence of moisture, continue to hydrate for many years. As long

as lime is made available from the cement hydration, the fly ash-lime reaction

will result in a gain in strength. Nevertheless the hydration of the cement and

as a consequence the pozzolanic reaction, will slow down with time. The

decrease in permeability, which may be visualized as less space being available

for the pozzolanic reaction products to form, as well as a reduction in the

alkalinity with time, are two factors which limit the pozzolanic reaction in

concrete with progressing time.

The calcium silicate hydrate gel formed in the pozzolanic reaction is not of

uniform compositio~ nor does it show consistency in its degree of crystallinity.

Two types of CSH are distinguished: 'Type One', being poorly crystalline with

· a molar ratio CaO to Si02 between 0.8 and 1.5, whereas type 'Type Two' shows I

a higher degree of crystallinity with ratios between 1.5 and 2.0.

The hydration of portland cement is a complex process where numerous

chemical reactions take place, which form a variety of products (Mantel, 1992,

Heckroodt, 1990 and Bye, 1983). On the addition of water, the first compound

to react is tri-calcium aluminate (C3A). The reaction would proceed virtually

instantaneously in the absence of gypsum (CaS04·2H20), leading to the

phenomenon of 'flash-set' where the concrete sets in seconds. The gypsum,

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which is introduced during the clinker milling stage of cement production,

dissolves in the water and reacts with the reaction products of C3A to form

ettringite (C3A·3CS"·H32), which is an insoluble calcium sulphoaluminate

hydrate. The ettringite forms a framework for subsequent hydration reactions.

The next compound to react with water and calcium hydr.oxide is tetra-calciwn

alumino ferrite (C4AF) to produce mainly hydrogarnet (C6AFH 12).

Subsequently tri-calcium silicate (C3S) and then di-calcium silicate (C2S)

undergo hydration to fmm C3S2H3 (and Ca(OH)i), with the calcium- silicate

hydrate further strengthening the framework of hydration products. The

structure of the hydrated cement paste is made up of precipitated solid material,

which consists mainly of porous calcium silicate hydrate gel (tobennorite gel),

well-crystallized calciwn hydroxide and ettringite .

.c.

"' c .. "' .. . ::: "' "' .. c. E 0 u

0 28 90 180

Age (days)

Figure 2.2: Relative rates of strength development for the clinker compounds

of portland cement (Addis, 1986).

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The contributions which the above clinker compounds offer to the actual

strength development of portland cement show markedly different trends. C3S

and C3S are responsible for the development of strength with C3A and C4AF

playing a rather insignificant role. These trends are depicted graphically in

Figure 2.2.

Helmuth (1987), Jawed et al.(1991) and Kriiger (1990) have reported on the

effect of fly ash on the process of hydration of portland cement, specifically on

the hydration of C3S and C3A.

2.2.2 FLY ASH Al\D THE HYDRATION OF C3S

The hydration of tri-calcium silicate (C3S) in the presence of fly ash is initially

retarded, then after this induction period of about 24 hours, the rate accelerates.

The retardation is illustrated in Figure 2.3 which shows that the main heat

evolution peak due to the hydration of C3S is delayed to a later time. The

reasoning for this behaviour is as follows. The process of chemisorption of

Ca2+ -ions onto the surface of fly ash particles results in a decrease in the

calcium ion concentration in the pore water. As a result, the homogeneous

nucleation of Ca(OH)2 (formed as hydration by-product) is retarded. However,

if the reaction mechanism proceeds via heterogeneous nucleation, the

chemisorption would accelerate the nucleation of the calcium hydroxide.

Furthermore, the 'poisoning effect' of soluble silicate, aluminate and especially

organic species which oppose the nucleation and growth mechanisms of

calcium hydroxide and calcium silicate hydrates, retard the reaction of C3S.

In addition to the chemical effects, there is the physical effect of fine fly ash

particles adhering to the surface of cement grains, thereby hindering the

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interaction of the cement with water. The fly ash particles thus effectively

create space between individual cement paiticles thereby providing additional

volume for the deposition of hydrates formed by the cement particles. This

deflocculation process is another example in which the fineness of the fly ash

used is the determining factor for efficiency.

A further consequence of the availability of space is the fact that, once a

hydrate structure is formed, the presence of the fly ash enhances the continued

growth of the hydration products as it provides the space needed for further

hydrates to form.

-0

l

0 5

--

10 15

Hydrotion time, t101,1ri

Control Fly o $1'

Fly 0$1'

20

Figure 2.3 : Heat evolution profiles for C3S systems hydrated m water

(Helmuth 1987).

The following schematic diagram (Figure 2.4) depicts the hydration mechanism

for the C3S-fly ash system. The pozzolanic reaction is simplified, but it shows

the following important steps.

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Pozzolan 1 gra n

® .... ..

K+ OH-

~ Na•~30• Y@/ Amorphous film + + (Si, Al-rich)

Ca 2•

Ca~• Ca2• Na• (Ca21

H20 Ca 2• K·~1 •• Al.-r!ch solut~on

Si-rich solution H o Na, K -rich solution • Q4- 2 ....

4.... 4- ~ ·~104 4-~ ... ca2• SIO .; ,

- 4 :. ca-si-AI Ca(OH Type I AI02 ·. . . . a~orphous

2 • c-s·H • f 11m

ca2• AI02~~ca2; ca2• Inner ~ti...__:.-~c .. ··.· C-S-H product ... ~ Ca 2• Co2~''. §® · · Co -Al

~ .. Type I C-S-H . . hydrate

ype Ill c-s·H CoCOH)~ ... ... \ ~ -tro·., o~~ ~

. $@~ ' dO, I

D8~se •'PorO"J 1(1"

15

Figure 2.4 : Schematic representation of the hydration mechanism for the C3S­

fly ash system (Helmuth 1987).

The C3S surfaces release calcium ions into the liquid phase thereby saturating

it. A proportion of these ions is adsorbed onto the pozzolan particle (fly ash)

surface. The surfaces of the C3S particles, in contact with water, are hydrated

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to form calcium silicate hydrate. Surface reactions on the fly ash particles

result in the precipitation of porous hydrate structures with low Ca-to-Si ratio

on these surfaces. Sodium and potassium ions are removed from the pozzolan

surface by the action of the surrounding water, leaving behind a Si-rich and Al­

rich amorphous surface layer. The dissolving Na+ and K+ ions increase the

hydroxyl concentration in the liquid phase and thereby enhance the dissolution

of (Si04)4- and (AI02)-, which readily combine with Ca2+ from the liquid phase

to build up the hydrate layer on the fly ash particle

The action of osmotic pressure brings about a swelling of the hydrate layer and

a void is formed between the layer and the pozzolan particle. If the pressure in

the void fmther increases, the film of the void ruptures and (Si04)4-, (Al02)-,

Na+ and K+ ions are released into the solution (which is still at a high calcium

ion concentration). Combination of (Si04)4- and (Al02)- with Ca2+ results in

more calcium silicate and aluminate hydrates being fo1med. The presence of

alkalis opposes the precipitation of hydrates. The glassy phase of fly ash tends

to have a high sulphur and alkali content concentrated in the surface of the

particle, which often leads to void space in the form of a complete shell around

individual particles where very little activity occurs.

2.2.3 FLY ASH AND THE HYDRATION OF C3A

Helmuth (1987) reports that the pozzolanic action of the fly ash again results in

a retardation of the hydration dm·ing the very early stages which changes to an

acceleration with time.

In the schematic diagram (Figure 2.5), the mechanism for the hydration of the

pozzolan-C3A system in the presence of calcium hydroxide as well as ettringite

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is presented. The mechanism depicted explains the accelerating action of the

fly ash on the C3A hydration. The pozzolan adsorbs calcium ions from the

liquid phase and provides precipitation sites for ettringite and other hydrates.

In this way the fly ash promotes the formation of ettringite as well as the

. consequent transformation of the latter to mono-sulphoaluminate hydrate. The

pozzolanic reaction follows a similar reaction profile as in the hydration of C3S

described above. In addition to ettringite and mono-sulphoaluminate, calcium

aluminate hydrate and calcium silicate hydrate precipitate on the surface film

outside the pozzolan particles and on the hydrate layer of the C3A particles,

depending on the concentration of the calcium- and sulphate ions in solution.

The sulphate concentration is thus very important in so far as influencing the

precipitation site: Calcium aluminate hydrate is found preferentially at a

surface of low sulphate concentration.

It becomes evident how imp01tant the knowledge of the particular fly ash

composition is if a homogeneous microstructure in the final concrete is aimed

for. For example a high sulphate concentration of the fly ash, which will be

concentrated in the surface of individual particles, will determine the hydrate

structure forming around it.

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C3A Qroln

~ ... ~

Pozzolon Qr a In

• Al-rich No• • AI02 .amorphous K~(Co~ film ....._ rich 2• SI, Al-rich solvtion ca2,·s~· Co ' sol~tio.n

crJ• rich solution H 0 No. K ·rich • H20 2 • solution

Ca2-i6AIO. AI02~ ,sd4 ~ 2

s104• ~Co·Si·AI

4 ~ amorphous film

~ • ca 2• aS04 •H20 /

~~.,"VJ(£. ~ ~~·~ 0JJ,.,~ ®.. C·S·H -....:~f~~~)E11rln9lte ~ ~So.;ooP.t"<-"llllt~·~lf"' .... Monosulfote hydrate (Monos ulfo1e hydrate end

... ~Co·Alhydrotelu 1.{'ef~..eyj~ f-'J·S·H

$._,. -~- ..,·-~ "":O·'g-~'- ·~~S\>J,...~ ~~M~~ Co-Al hydrate

C·A·H - Monosulfote hydrate Ettringite lor9e crystal

cord house structure

18

Figure 2.5: Schematic representation of the hydration mechanism for the C3A­

fly ash system (Helmuth 1987).

2.2.4 FLY ASH AND THE HYDRATION OF PORTLAND CEMENT

The overall hydration of portland cement under the influence of fly ash, is

expected to follow similar reaction paths and mechanisms as described for the

individual clinker minerals. However, the fact that the reactions take place

simultaneously and consecutively, will certainly influence the kinetics and

characteristics of individual reactions. The role which water-soluble

components of the ash play, is extremely complex and cannot be generalized,

as it depends on the particular fly ash used. It can be concluded though, that

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the pozzolanic reaction decreases the free lime content and is responsible for

the lowering of the Ca-to-Si ratio of the calcium silicate hydrate in the

cement/fly ash concrete mix.

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2.3 THE PERFORMANCE OF FLY ASH CONCRETE

The aim of a great deal of research on fly ash concrete is to attain the ability to .

accurately predict the early-age as well as long-term characteristics of the

concrete from the measurable properties of the fly ash to be used. However, as

pointed out in previous discussions, the complexity of the component

interactions in the mix is the biggest stumbling block in achieving this aim. If

the processes of the chemical and physical interactions of the systems on the

addition of water could be fully understood, the variability in properties of a

particular fly ash could be incorporated in the mix design. Until such time as

our understanding grows considerably, each fly ash-concrete system has to be

treated as a separate entity, allowing for unforeseen effects which will

hopefully show up during the preparation and evaluation of trial mixes for the

particular mix design. The status of fly ash is lifted more and more from the

misconception of a useless waste material to a beneficial cementitious binder

material. This change in attitude will certainly continue, even if the material is

only judged by the most conservative critics in terms of the economic savings

achieved.

2.3.1 WORKABILITY OF FLY ASH CONCRETE

The workability of a concrete mix is a broad term covering numerous aspects of

the performance of the material in the fresh state. Terminology like 'plasticity',

'mobility' and 'consistency' is often used synonymously for the concept of

workability. Such loose definitions lead to confusion. In Fulton (Addis, 1986)

workability is related to the ease of transporting, placing and compacting

concrete in such a way as to minimize segregation or separation of individual

constituents. According to this view, workability is merely a characteristic of

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the particular mix which gives an indication of the flow properties. It is not at

all an absolute figure that allows comparisons of concretes containing different

materials or produced under different conditions. A suitably workable mix for

mass concreting of a dam wall will certainly be unsuitable to be placed and

compacted in a heavily reinforced structure.

Further difficulties anse from the methods of assessmg the workability.

Different tests have been formulated, for example, flow test, ball penetration

test, compacting factor test, K-slump test, slump test and the Vebe

consistometer. Results cannot be interpreted interchangeably between different

test methods, nor will the results of tests carried out by different operators

necessarily be consistent. For example, it may well be that two mixes give a

zero slump value but at the same time may be differentiated very clearly on

grounds of their Vebe time values. It is not surprising that in practice

workability judgment based on experience is often considered of more value

than, for example, a figure obtained from the slump test.

Factors influencing the workability of concrete include particle interference

(interlock) and specific surface area, in so far as any increase in either of these

will reduce the workability (Addis, 1986). The concrete mix design, the texture

and shape of the coarse aggregate, the fmeness of the fme aggregate as well as

the interaction of individual concrete components all influence its workability

and are all aspects contributing to the behaviour of the concrete in the fresh

state.

The introduction of fly ash as a cement replacement will further govern the

flow characteristics of the paste. It is generally accepted that fly ash improves

the workability of concrete (Krtiger and Van Dijk, 1985). For example, an

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under-sanded mix will benefit from fly ash replacement for part of the portland

cement on a mass-to-mass basis. This is due to the lower density fly ash which

results in an increase in the volume of the paste, as well as the so called

lubricating effect of the fine ash.

Dartsch and Herten ( 1992), in their study of using fly ash in concrete and

precast concrete applications, contrasted the 'filler effect' against the

'lubrication effect' of fly ash in concrete. Figure 2.6 gives a schematic

representation of the two concepts. It must be noted however that this

approach is a very simplistic one based on numerous assumptions and is merely

used to illustrate the concepts graphically.

Figure 2.6 : Filler effect in relation to lubrication effect (Dartsch and Herten 1992).

The first illustration shows the filler effect for spheres of diameter d and di 10

packing in such a way as to give the densest filling, where the di l 0 spheres

resemble the fine fly ash. In the second diagram, the lubrication effect of fly

ash is visualized. The spheres are arranged according to the 'planetary system'

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with the larger spheres being encircled by a large n1imber of spheres of the

smaller size. In this case the relationship between individual sizes is more

important than the absolute size of the particle. The second diagram is

applicable to the improved workability accounted to the 'ball-bearing effect',

recognizing the fact that actual fly ash particles are spherical in shape.

Both the filler and lubrication effects are present wheri fly ash is added to

concrete and both of these effects contribute to the reduced water requirement

of the concrete. The filler effect improves the particle packing by filling

interstices and contributes to a more compact final material. Another important

consequence of the filler effect is the reduction of air entrapment and hence a

decrease in total porosity. The compacting and homogenizing action of the fine

fly ash particles is very beneficial in decreasing permeability, but it is even

more advantageous in the interfacial zone between the aggregate and matrix.

Filling this space solves many problems of non-uniformity on a microscale.

The generally improved particle packing reduces the amount of non-surface

adsorbed water in the concrete, hence the observation that fly ash addition to

concrete reduces the amount of bleeding. It must be remembered that the

above diagrammatic representation deals merely with the physical size

relationships, ignoring any adhesive, cohesive or chemical interactions.

Hansen and Hedegaard (1992) investigated the effect of the amount of fly ash

in a concrete mix with special reference to the plasticizing ability of such an

addition. Their work showed that Lyse's Rule (which states that 'for given

materials, the consistency of fresh portland cement concrete is determined

exclusively by the free water content of the concrete mix'), also applies to fly

ash concretes, although in a slightly modified form. The enhanced

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w ----,---c- = a c+F(dc/ ) /df

25

where a is a constant and is equal to the minimum modified water-to-( cement

plus fly ash) ratio (by equivalent volumes) at which it is possible to mix, cast

and compact fresh concrete to maximum density by traditional means. The

value of a ranges between 0.35 and 0.38 when no superplasticizers are used

and will be lower if the latter are correctly employed in the mix design. The

other symbols used in the equation above are :

W = free water content (kg per m3)

c = portland cement content (kg per m3)

F =fly ash content (kg per m3)

de and df represent the particle density of the cement and fly ash respectively

(kg per m3).

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2.3.2 STRENGTH DEVELOPMENT OF FLY ASH CONCRETE

The following discussion concentrates on the development of compressive

strength of fly ash concrete. The compressive strength is indeed a very

important parameter of the material which is reflected in the habit of concrete

users to rationalize general quality of the concrete by the universal indicator of

compressive strength.

The intricate details of the interactions between cement, mineral admixture (fly

ash), aggregate and water have not yet been resolved. However the progress

made in research on this topic reveals more and more information which leads

to a better understanding of the general topic of concrete technology.

Figure 2.7 below is taken from work published by Dhir (1986). This graphical

representation of strength development patterns serves as a good starting point

to compare the strengths of OPC and fly ash concretes. Both concretes have

been designed for the same workability and 28-day wet-cured characteristic

compressive strength. The philosophy of mix design is the first factor

influencing early-age and long-term strength. Design criteria according to

specifications have to be aimed for in a very specific way. The two basic

principles governing the achievement of set requirements are the quantity of

cement ( cementitious material) to be used and the water to total cementitious

material ratio.

For the two concretes designed to the same 28 day specifications, no significant

difference in the strength development before the age of 28 days is observed.

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80

70

80

;; 50 e ~ .:. <10 0 . c ~ • 30

20

10

0 3 7

.. · .. / .• ...... ..

pfa concrete 11< / .. /

... ...

... ... /

·"" ..

28 90 180 385 •a• (dayl)

Figure 2.7: Strength development as a function of time for concretes cured at 20°c (Dhir, 1986).

27

However, after 28 days the fly ash concrete shows a gradual increase in

strength over the OPC mix and it is this effect of fly ash which makes it a

beneficial concrete ingredient in situations where high ultimate strengths are to

be achieved. The strength-age factor (the ratio of compressive strength at any

age to the strength value at 28 days) which relates the gain in strength to the

28-day strength, shows the same trend for OPC as well as fly ash mixes: With

increasing design strength, the strength-age factor decreases. This factor is

specific to the materials used for a particular mix.

Berry and Malhotra ( 1987), in addition to the selection of mix proportions,

listed the following variables influencing the strength development of fly ash

concretes:

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• the properties of the fly ash

• chemical composition

• particle size

• reactivity

• temperature and other curing conditions.

Dhir ( 1986) referred to the availability of moisture and the prevailing

temperature as being two factors of utmost importance to the development of

strength.

The particle size iniluence is twofold. Firstly, the fineness of the fly ash

particles determines its efficiency in dispersing the cement clusters, which

improves the hydration process and hence enhances strength development.

Secondly, the finer the ash, the more surface area is available. Generally,

cementing activity takes place on the surface of the solid phases, through

various heterogeneous processes of diffusion, dissolution and precipitation of

reaction products. Thus surface area plays an important role in determining the

kinetics of such processes in that a fine ash renders a large number of

precipitation sites during the hydration of the cement. Feldman ( 1989) pointed

to the controlling factors for cement hydration as being the availability of water

and the availability of space for the hydration products to form. The author

characterized the fly ash in the early periods of hydration as inert material

hence the high effective water to cement ratio will allow a greater degree of

hydration of the cement. The author concluded from his work that blending of

cement pastes with fly ash resulted in a homogeneous hydrate product with a

low C/S ratio CSH gel which gave a stronger body.

Fly ash reactivity refers to the pozzolanic activity of the material. The rate of

this process, as described earlier, is slow to start with, but increases with time

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and eventually, after 28 days, the steady increase in strength can be ascribed to

the contribution of the pozzolanic reaction. This strength contribution is a

function of the availability of moisture, the absence of which will limit the

continued long-tenn strengthening of the concrete (hence the influence of

curing). In fact, fly ash incorporation as a mineral admixture makes the

concrete more sensitive to proper curing than an equivalent OPC mix. This is

due to the fact that as far as the strength development is conceme~ the

pozzolanic contribution is relied upon to make up for the reduced portland

cement content.

The effect of temperarure on the strength development clearly distinguishes the

fly ash concrete from a OPC mix. On heating, fly ash concretes exhibit a gain

in strength as is depicted in Figure 2.8 below.

1.2-------------,

""' 1.1 0 .. CJ IV '"i 1.0 .c .. Cl

~ 0.9 .. G'l

> ~ o.a Q co N 0.7

0.6

-----------

0·5o 10 20 30 40 50 60

Temperature rlse,°C

Figure 2.8: Effect of temperature rise during curing on the development of compressive strength (Beny and Malhotra, 1987).

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The explanation given for strength gain of fly ash concretes on heating is that

the heat initiates the pozzolanic reaction The pozzolanic strengthening

continues even if the initiating external heating is discontinued. On the other

hand, Alis et al. (1992) showed that low temperature curing (10°C) severely

retards the development of compressive strength of fly ash concrete at early

ages and at least up to 90 days (as measured in his work).

Hedegaard and Hansen (1992) attempted to explain the mechanism behind the

compressive strength development of fly ash concretes. Their work was based

on the principle that the portland cement and the fly ash may be considered as

contributing independently to the development of concrete strength. This

principle was also used by Popovics ( 1991 ), in proposing a model based on the

'Breakdown Method' to mathematically identify the fly ash contribution to

measured strength. The former authors visualized a superposition of two

independent mechanical pore-filling mechanisms being active in the cement-fly

ash paste: the one mechanism due to pore-filling stemming from the cement

hydration and the other derived from the reaction of the fly ash. Reasoning for

such a proposal is giYen by the fact that the CSH gel formed during the cement

hydration is similar in structure and properties to the gel formed by the

(pozzolanic) reaction of fly ash combining with Ca(OH)z. Hence the hydration

reaction of the portland cement as well as the pozzolanic reaction of the fly ash

lead to very much the same reaction product.

If the assumption holds, that the fly ash concrete strength development may be

described in these simple terms, then it should be possible to express the

process in terms of a modified Bolomey equation. The original Bolomey

equation is given by Hedegaard and Hansen (1992) as S = A(C/W) + E where

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S = strength of concrete (MPa), C = cement content (kgm-3), W = free water

content (kgm-3), and A and E = constants for given materials, age and curing

conditions of the concrete. The equation was suggested by Bolomey in 1927

on a purely empirical basis.

The modified equation as proposed by the authors is as follows:

St= A(~)+B(:)~E where Sr= strength of fly ash concrete (MPa)

C = cement content (kg per m3)

F = Fly ash content (kg per m3)

W = Water content (kg per m3)

A, B, E, = constants for given materials, age and curing conditions of the

concrete

The above equation may be rewritten in the following way:

S,-A( C+~,)F}-E where ks = cementing efficiency index of the fly ash

=(BIA)

ks relates the reactivity of fly ash in relation to the reactivity of cement on the

basis of strength. (For example if ks = 0.2, for a specific amount of cement to

be replaced by fly ash while maintaining the strength of the concrete, it would

take five times by mass the amount of fly ash.) The value of ks is specific to a

concrete in terms of materials, age and curing regime and has to be determined.

A value for ks = 0.20 is generally taken as a first estimate.

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Hedegaard and Hansen (1992) further postulated that the traditional

water/cement ratio for normal portland cement concretes also applies in a

modified form to the fly ash concrete situation:

"For given materials, age and curing conditions, the strength of hardened

concrete is determined exclusively by the ratio between the content of

free water and portland cement in the concrete, jointly with the ratio

between the content of free water and fly ash. Thus, the strength of fly

ash concrete is independent of the absolute content of free water, portland

cement and fly ash in the concrete."

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2.3.3 DURABILITY AND PROPERTIES OF FLY ASH CONCRETE

In Fulton (Addis, 1986) the concept of durability of concrete is defined as "the

ability of concrete to retain its strength, impermeability, dimensional stability

and appearance over a prolonged period of service under the conditions for

which it was designed".

The durability of concrete depends to a very large extent on its permeability.

Ballim (1993) defines permeability as a transport concept which relates to the

ease of fluid (gases and liquids) passage through the material. Permeability

indicates the degree of interconnection of the pore structure of the concrete.

This terminology contrasts the definition of porosity which is a bulk concept,

referring to the non-solid component of the material. It is important to

differentiate between these two concepts for the sake of investigating durability

aspects of concrete. There is no doubt that with advance in adequate and

reliable test procedures for permeability, this property of concrete will gain

more and more importance and validity as a measure of short-term and long­

term performance of the material.

The permeability of the concrete determines to a large extent its durability in

that it controls the ingress and permeation of (aggressive) agents. Chemical

deterioration processes are a function of the availability of the reacting species,

which is governed by permeability, as well as the reaction conditions prevailing

in the concrete environment, which is the pore structure in this case. For

example, the particular mechanism of fluid transfer is a function of the relative

humidity in the pore structure. The actual movement of molecules is either by:

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• Adsorption, with bonding either van der W aal type or of chemical nature.

• Diffusion, driven by a concentration gradient.

• Mass flow under the influence of a pressure gradient.

The change of movement of water from adsorption to diffusion to mass flow is

a function of the increase in the relative humidity in the pore structure.

Many destructive forces act on concrete in service which set up internal and

external stresses. These forces, which are either material-related or

environmental, may lead to premature deterioration of the concrete and result

in a reduction in sen ice life or unexpected failure of the structural member.

Mechanisms of deterioration caused be chemical reactions (Ballim, 1993)

include:

• Dissolution of products of cement hydration.

• Exchange reactions between acids and the alkaline components of the

hardened cement paste.

• Conversion of the products of hydration by external agents, with

associated expansive forces causing deterioration.

• Internal processes of deterioration, which are due to incompatibilities

between individual concrete constituents and can lead to alkali-silica

reaction or delayed ettringite formation for example.

• Steel corrosion in reinforced concrete caused by de-passivation 9f the

steel.

In the context of the presented topic, the effect of fly ash addition on the

durability of concrete is to be emphasized. Ellis ( 1992) pointed out that for

durable concrete, fly ash does not replace portland cement in the true meaning

of the word, but due to its presence and influence rather contributes as an

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additional factor to improve durability. The author lists five ways by which fly

ash in concrete improves the durability of the material:

• Reduction in permeability.

• Improving the sulphate resistance.

• Lowering the potential of alkali-silica reaction.

• Increasing the resistance to freezing and thawing.

• Enhancing the resistance to corrosion in aggressive environments like

marine conditions.

A high degree of impermeability is an important prerequisite for achieving

durable concrete. Fly ash densifies the microstructure of concrete in two ways.

The presence of the ash as a fine powder improves the physical particle packing

by filling voids and interstices. However, a different mechanism of

densification is even more important, namely the pozzolanic reaction of the fly

ash which provides additional calcium silicate gel which further fills the

available pore space. The deposition of the extra hydration products creates a

more discontinuous pore structure and clogs pore channels. The result is that

fluid transport is slowed down dramatically and hence the ingress of aggressive

chemicals is limited (see Figure 2.9 below).

If sulphates enter the pore structure of set concrete, they chemically react with

calcium hydroxide to form gypsum compounds and with hydrated calcium

aluminate to form ettringite. The formation of both of these reaction products

results in an increase in the solid volume of the cement matrix and the resultant

expansive forces could lead to disruption. Fly ash enhances the resistance to

sulfate attack by a threefold mechanism:

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• The pozzolanic reaction of fly ash reduces the amount of Ca(OH)2 present

by consuming it.

• Fly ash as a cement replacement reduces the amount of portland cement,

which lowers the absolute calcium aluminate content and then decreases

ettringite formation.

• By reducing the permeability, the fly ash limits the penetration of sulphates

into the material.

9,0

- 8.0 ..: >-I

('I 7.0 E

-~ ...... -.... ....

I'-- ........ ---........ ~~ / -

100 '/, 0. pc. --"' 6,0 E

~ 5,0 -0 ... >- 4,0 -

..0 3,0 0 ~

E 2,0 ...

!>I a..

1,0

70'/, 0. P. C.-dO '/,Fly ash -- \ --...... ... - ... • ------ ------ P-c - ----

120 150 1ao 210 240

c~menting materials in concrete ( kg/m?>)

Figure 2.9: Permeability of fly ash concrete (Elfert, 1987).

Another deterioration process which limits the durability of concrete in service,

is that of alkali-aggregate reactions (AAR). Under certain conditions, the

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aggregates are not chemically inert and widergo reaction with alkalies present

in the concrete to form expansive reaction products. It is a slow process, often

taking years, but can lead to the disruptive expansion and failure of the

concrete. Three conditions have to be met for AAR to take place (Davies and

Coull, 1991):

• The aggregate must contain reactive constituents.

• The alkali content of the concrete itself must be sufficiently high to initiate

and feed the reaction.

• A favorable environment of temperature and moisture must exist.

If the addition of fly ash to concrete restricts any of these necessary conditions,

it will effectively oppose alkali-aggregate deterioration.

Three types of alkali-aggregate reaction are can occur (Ballim, 1993):

• Alkali-silicate reaction, where alkalies present in the pore water of the

concrete react with silicates in the aggregate.

• Alkali-silica reaction, where the reaction is between alkalies in the pore

water and amorphous or crypto-crystalline silica in the aggregate.

• Alkali-carbonite reaction which is found in concretes containing carbonate

rock aggregates.

Fly ash is particularly effective in limiting AAR in the case of the alkali-silica

reaction. In generaL the contribution of fly ash to the total alkalinity is not

significant, compared to portland cement. The total alkali content of the

concrete is a function of the cement content (which is the largest source of

soluble alkalis), the quantity of Ca(OH)z produced during hydration, as well as

the amount of sodium and potassium hydroxide formed as by-products during

the cement hydration. The mere presence of fly ash thus lowers, the alkali

concentration in the gel/pore structure of the concrete, because of the lower

cement content. Furthermore, during the pozzolanic reaction of fly ash,

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Ca(OHh is consumed and alkali metals are combined into the calcium silicate

matrix (Ellis, 1992). The second condition for AAR described above is

counter-acted by the fly ash, in that it lowers the alkalis present, which would

be necessary to support the alkali-silica reaction.

The resistance of fly ash concrete to cycles of freezing and thawing is another

bonus. derived from the improved impermeability of the material. Saturation is

a prerequisite for damage by freezing and thawing, and hence the mechanism of

enhancing the resistance is by limiting the ingress of water into the structure.

Fulton (Addis, 1986) referred to the action of fly ash as enhancing the

"watertightness" of the concrete. Nasser and Lai (1992) found that the

resistance of fly ash concretes to freeze-thaw damage could weaken on

continued cycling and proposed that it was due to a mechanism of slow

displacement of microcrystalline Ca(OHh and fibrous ettringite hydrates from

the dense CSH zones to air voids in the structure.

The corrosion of reinforced steel in concrete is a major source of deterioration

of structural members, especially in aggressive environments like marine

conditions. The densification of the microstructure due to fly ash in the

concrete is again the important parameter, this time limiting the chloride

diffusion and preventing oxygen from entering the concrete. As the pH

decreases due to the ingress of chlorides, a point is reached where the

passivation layer of the steel is destroyed and corrosion is initiated. To achieve

improved corrosion resistance of the reinforcing steel, the use of fly ash is more

and more frequently exploited. The research of Ellis (1992) has shown that

this philosophy is indeed a valid one. The corrosion resistance of the steel

improved as the fly ash content increased as a fraction of the total cementitious

material, even though the 28-day strength decreased as the cement was

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replaced. Maslehuddin et al. ( 1989) investigated the steel corrosion

characteristics of fly ash concretes and concluded that the steel corrosion

resistance was even better when, at a constant cement level, the sand content of

the mix was adjusted on a mass-to-mass replacement basis with fly ash.

The above characteristics of fly ash concrete proving it to be a high quality,

durable material, have been found to apply in various investigations of high­

volume fly ash concretes (substitution up to > 50% used) carried out by

Malhotra (1989 and 1992) and Sivasundaram (1989). Because fly ash

concretes show a lower temperature rise during initial hydration, a very useful

structural application is that of mass concreting, for example in mat

foundations, large retaining walls and dams. Botha (1990) investigated the heat

development of fly ash concrete during building of two dams in Venda and

Botswana. It was concluded that the concrete performed well in terms of

keeping the heat of hydration low while maintaining good strength

development which made shutter stripping possible after 48 hours.

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2.4 CONCLUSION

There is no doubt that the correct use of fly ash as a mineral admixture in

concrete offers many advantages. The benefits range from cost savings to

enhanced material quality of the concrete. With special emphasis on the long­

term durability aspects of fly ash concrete, the possibility of incorporating fly

ash points in new directions that can be followed in mix design philosophy. A

challenge certainly lies in optimizing the amount of fly ash used in concrete for

a particular application as this will greatly influence the effectiveness of the

material.

With continued research finding new and enhanced applications, the topic of

fly ash concrete will continue to gain importance and acceptance. The correct

utilization of fly ash in concrete ensures a prolonged densification of the

microstmcture due to the pozzolanic reaction. The improved impermeability

achieved in this way may well become a significant factor in guarding concrete

stmctures in urban environments against the aggressive chemicals of pollution.

The importance of curing of fly ash concrete must be stressed. Without

effective curing of the concrete, the presence of the fly ash as a replacement for

portlartd cement may possibly cause adverse effects leading to a less stable

microstmcture with subsequent accelerated deterioration.

Whichever criticism is raised against fly ash as a cement extender, the fact

remains that, using a waste material available in large amounts to achieve

improved quality concrete is a very attractive venture.

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3. EXPERIMENTAL APPROACH

3.1 MATERIALS

3.1.1 CEMENT

The cement used in all the concretes and pastes was the ordinary portland cement

(OPC) from the Uko factory of Anglo Alpha.

The compositional analysis of the cement, carried out by the Blue Circle Cement

(Pty) Ltd Laboratories, is given in Table 3.1. The fineness measurements, as

determined on a l'vlalvern 2600 HSD laser diffraction spectrometer in the Physics

Department of the University of Cape Town, are tabulated in Table 3.2 (with

complete data of the fineness measurements provided in Appendix A). The

Malvern spectrometer was supported by the Malvern version B software package.

Two sets of data were collected, one using a 300mm focal lens and the other a

63mm focal lens.

3 .1.2 CEMENT EXTENDERS

The cement extenders introduced into the concretes and pastes as partial

substitution for the cement were fly ash from the Lethabo, Duvha and Matla power

stations as well as a milled clinker ash from the Van Eck power station in

Windhoek, Namibia. The Van Eck ash has been classified as a clinker ash

according to the definitions given by Kruger (1990). At the Van Eck power

station, the coal is introduced in pellet form of size about 2cm to 4cm and the

produced ash is a combination of the coarser bottom ash and fine fly ash.

All the coal ashes were analyzed for their chemical composition by the Blue Circle

Cement (Pty) Ltd Laboratories (Table 3.1). The fineness was determined with the

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Malvern laser diffraction spectrometer (Physics Department of the University of

Cape Town). Some important results from the fineness measurements are listed in

Table 3.2, with complete data sheets attached in Appendix A. Figure 3.1 and 3.2

show the histograms of frequencies of particle size distributions obtained from the

laser diffraction experiments (300mm lens) on the Van Eck material as collected

and the commercially available Lethabo fly ash. It is clear how coarse the clinker

ash is in comparison to the fly ash.

Interval percentage ----------------·--------·-·-----

.1 I. 5)

10 Particle size (µ~).

Figure 3.1: Particle size distribution for the collected Van Eck clinker ash.

Interval percentage r----- -----···- ······-·--·--·-·-·

10 100 1000 Particle size (~u11).

Figure 3.2: Particle size distribution for commercially available Lethabo fly ash.

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The American standard, ASTM C618-89 differentiates fly ashes on the basis of the

sum of the percentages of Si02, AI20 3 and Fe20 3 into Type F or Type C. The fly

ashes of Lethabo, Duvha and Mada all comply with the Type F specification, with

the sum being greater than or equal to 70%. For the clinker ash from the Van Eck

power station the quantities of the three compounds add up to 59.55% and under

the above classification the ash would fall under the category of Type C.

However, because the Van Eck material is not a true fly ash and contains carbon in

excess of 30o/o by mass, it is suggested that the above classification should not be

accepted as absolute. This proposition is further emphasized when looking at the

calculated chemical composition of the Van Eck material based on 0% carbon

(also given in Table 3.1). If thus only the non-volatile constituents are considered,

the chemical composition of the Van Eck clinker ash is remarkably similar to that

of the fly ashes and the sum of the oxides, Si02, AI20 3 and Fe20 3, is greater than

70%. The only noticeable difference is that the lime content of the Mada fly ash is

about double that of the other ashes. However, the carbon content, as determined

by loss on ignition at 950°C, is 35.38% for the Van Eck material which, according

to the ASTM C618-89 standard (which allows a maximum carbon content of 12%

for Type F and 6~fo for Type C), renders it totally unsuitable for use as a cement

extender in concrete.

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Table 3.1: Chemical composition of the cementicious materials used.

Ulco Lethabo Duvha Van Eck Van Eck Matta OPC Fly Ash Fly Ash Clinker Clinker Fly Ash

Ash Ash* --

Cao (%) 65.61 4.69 4.47 2.76 4.27 9.30

Si02 (%) 21.51 54.07 53.11 35.89 tiS.54 47.84

Fe20 3 (%) 2.68 3.30 ~ 5.71 3.78 5.85 3.78

Al 20 3 (%) 4.50 32.85 30.76 19.88 30.76 30.18

MgO (%) 2.28 1.27 0.97 0.64 2.46

Ti02 (%) 0.28 1.66 1.64 0.97 1.58

Mn20 3 (%) 1.06 0.04 0.06 0.03 0.06

K20 (%) 0.57 0.55 0.63 0.34 0.72

Na20 (%) n.a. 0.55 n.a. 0.16 0.55

503 (%) n.a. 0.35 n.a. 0.01 0.36

LOI, 950°C (%) n.a. 0.50 n.a. 35.38 3.00

Van Eck Clinker Ash* = Calculated composition of Van Eck ash based on 0.0 LOI n.a. = not analysed for.

To standardize the influence of particle size on the concrete properties and the

reactivity, the ashes were passed through a 63 µm sieve and only the fraction

passing was used in the concretes and pastes. In Table 3.2, the designation

Lethabo(-63) thus refers to fly ash from the Lethabo power station which has been

passed through a 63µm sieve. For the Van Eck ash, the sample designated as

'collected' represents the form of the material as being collected at the power

station prior to milling. The milling of the ash was carried out by Scientific

Services Namibia f Pty) Ltd Laboratory in Windhoek.

Samples of the four ashes, before sieving, were sent to the Division of Building

Technology, CSIR, Pretoria. The samples were analyzed by X-ray diffraction to

obtain a comparative estimate of the amount of glassy phase present. The four

diffractogrammes are provided in Appendix A. A visual inspection of these

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diagrams gave the following ranking of the ashes as a function of decreasing glass

content:

Van Eck> Lethabo > Matla > Duvha.

The above sequence was supported by Kruger (1993). It must, however, be

mentioned that, on visual inspection, the diagrams of Lethabo and Mada are very

similar. Bosch and Willis (1990) found the ranking of the glass content for fly

ashes collected during 1987 and 1988 to be as follows:

Matla > Lethabo > Duvha.

The important conclusion that may be drawn from both sequences is that Duvha

fly ash has the least amount of glass, Lethabo and Mada have similar amounts and

Van Eck contains the highest percentage of glassy phase.

To be able to comment on the repeatability of the fineness results, three

determinations for the Van Eck(-63) material were carried out using the 63mm

focal lens. The three results for the specific surface area in m2/cc were 1.0206,

1.1117 and 1.0901. Based on these values, the 95% confidence interval was

calculated to be 1.0741 ± 0.118 m2/cc. by the statistical equation (Skoog et al.,

1988):

Confidence limits forµ = x +

where µ = population mean

X = sample mean

t = statistical parameter

s = standard deviation

N = number of replicate measurements

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The three values for specific surface area used in the calculation do fall into the

calculated interval and thus, assuming the sample is representative, it may be

concluded that the results tabulated comply with a 95% confidence level.

Table 3.2: Results from the fineness measurements carried out on the Malvern laser diffraction spectrometer.

Span* Specific Surface Area, m2/cc** Focal Length 63mm 300mm 63mm 300mm Ulco OPC 2.21 2.14 0.5819 0.6128 Lethabo 2.60 3.09 0.7712 0.7472 Lethabo(-63) 2.35 2.37 0.7722 0.9393 Duvha 2.82 2.19 0.6393 0.7529 Duvha(-63) 2.20 2.33 0.6607 '0.7201, Van Eck, collected 2.29 4.08 0.2838 0.1627 Van Eck, milled (not sieved) 1.83 2.26 1.2492 1.1354 Van Eck( -63) 2.12 1.99 1.1117 1.1510 Mada 2.56 2.17 0.7626 0.7694 Matla(-63) 2.15 1.98 0.8388 0.7732

Span*= measure of the range of particle sizes Specific Surface Area**= calculated value based on the laser diffraction pattern

3.1.3 AGGREGATES

The 19mm Malmes bury Greywacke stone served as coarse aggregate whereas the

Klipheuwel pit sand (FM = 1.83) made up the fine aggregate in the concrete

mixes.

3.1.4 MIXING WATER

The mixing water used for the concrete mixes and pastes was Cape Town tap

water as supplied to the Civil Engineering Concrete Laboratory. A sample of the

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water was analyzed by J.Muller Laboratories in Cape Town. The results reported

for the parameters of significance to concrete are tabulated in Table 3.3.

Table 3.3: Important parameters of the chemical composition of concrete and paste mixing water.

H 8.47 Total Dissolved Solids 180°C Cale Chloride Total Alkalini

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3.2 MIX DESIGN AND SAMPLE PREPARATION

The calculations of mix proportions for the concretes were based on the mix

design method as suggested in Fulton (Addis, 1986). The mixes were designed

with a W/(C+FA) ratio (water-to-cement-plus-fly-ash-ratio) of 0.56. The same

ratio was used for the clinker ash. Table 3.4 summarizes the mix proportions of

the concrete mixes.

Table 3.4: Concrete Mix Proportions.

Material Mass perm3 Cement 227 Fly Ash 97 Water 180 Stone 1150 Sand 770

A constant water to total cementitious material ratio of 0.56 as design criterion

means constant mix proportions for all the concretes prepared. The fly ashes and

clinker ash were introduced at a 30% straight mass to mass substitution for

portland cement. Thus the type of cement extender is the only entity changing

between different concretes (and pastes) - no adjustments in water or aggregate

content were made to incorporate differences in the characteristics of the ashes.

The control mix was designed for a workability of between 60mm and 70mm

slump. The slump measurements obtained for the fly ash concretes and clinker ash

concrete would be a reflection of the influence of the particular cement extender

on the water requirement of the mix as well as its plasticizing abilities.

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Six concrete mixes were prepared, which are designated as follows:

Designation

Ml

M2

M3

M4

M5

M6

Description

Control mix, no fly ash added

Extender: Lethabo (-63 µm) fly ash

Extender:

Extender:

Extender:

Extender:

Commercially available Lethabo fly ash

Duvha (-63 µm) fly ash

Van Eck (-63 µm) milled clinker ash .

Mada (-63µm) fly ash

49

The concrete designated M3 in comparison to M2 would show any effect which

the sieving procedure had on the concrete properties. For every mix, 20 concrete

cubes of size lOOmm were cast and compacted for 30 seconds on a vibrating table.

After 24 hours in the humid room the cubes were demoulded and standard cured in

water (22-25°C). At time intervals of 3, 7, 14, 21 and 28 days respectively, the

density of four cubes was calculated (from the saturated mass and saturated

volume) and the compressive strength determined with an Amstler compression

tester (loading rate= about 15MPa/min).

In parallel, pastes were prepared from cement plus extender (at a W/(C+FA) ratio

of about 0.4), without any aggregate additions. Because no microstructural

investigation was going to be carried out on the paste samples, the exact amount of

mixing water added was not a significant factor. Five cubes of size 70mm were

cast for each blend, compacted for a few seconds on a vibrating table, stored in the

humid room for a day, demoulded and then wet cured with the concrete cubes. At

each particular time interval (as above) of the sample, a cube was crushed,

material removed from the center of the cube (to minimize the effect of

carbonation) and milled by mortar and pestle to pass a 106µm sieve. This paste

sample was then immediately frozen at -7 4 °C to te1minate the hydration reaction

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and the ice removed by sublimation under vacuum overnight. (The freeze-drying

facility of the Department of Biochemistry at the University of Cape Town was

used.) The dried sample was milled again by motar and pestle to pass a 63 µm

sieve. In this form, the samples were studied by differential thermal analysis

(DTA) and thermogravimetric analysis (TGA) techniques.

The thermal properties of the samples prepared from the pastes were studied with

a TGDTA Stanton Redcroft 780 Thermal Analyzer at the Chemical Engineering

Department of the University of Cape Town. The apparatus records

simultaneously the differential thermal changes as well as the change in mass for a

sample. Alumina ( 25mg) served as reference material. A constant heating rate of

10°C/min from ambient temperature to 600°C under controlled atmospheres was

set. All the samples were analyzed in dry nitrogen, introduced at a flow rate of

30ml/min. Material from the pastes containing the Van Eck ash were also

analyzed in normal air atmosphere (also at a flow rate of 30ml/min). From the

thermogravimetric traces, the derivative thermogravimetric plots were generated

by manipulating the data with the aid of computer spreadsheet functions.

The DTA, TGA and DIG (derivative of TGA) plots for the different pastes are

given in Appendix C.

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4. RESULTS AND DISCUSSION - CONCRETE PROPERTIES

4.1 THE FRESH STATE

To quantify the workability of the fresh concretes, the standard slump test was

carried out. The results are quoted in Table 4 .1.

Table 4.1: Workability of concretes.

Concrete Mix Extender Slump (mm) :\11 None 65 :\12 Lethabo(-63) 170 :\13 Lethabo 160 :\14 Duvha(-63) 80 :\15 Van Eck(-63) 70 :\16 Matla(-63) 125

The workability of a concrete is directly related to the water requirement of the

mix, that is, the more water added to the mix, the greater the slump. The partial

substitution of fly ash for cement increases the fraction of fines, thus increasing

the total surface area. The larger surface area requires more water to wet all the

surfaces during the mixing process and there should thus be an inverse correlation

between the slump and the surface area of the mix components if the water content

is kept constant. Plotting the values from Table 4.1 against the specific surface

areas given in Table 3.2, yields the graphical representation given in Figure 4.1.

As far as the fly ash concretes are concerned, it appears that, for constant water

content of the concrete, the increase in surface area due to the fly ash addition

actually increases the slump. This finding contradicts the expected trend. The

reason is that the increase in workability (which is due to the larger plasticizing

effect of the finer ash and which results in a larger slump), overrides the increase

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in water requirement (which is due to the larger surface area to be wetted and

which results in a smaller slump).

1.2

1.1

~Different Behaviour due to 1111 ~ Carbon Content

ns e 1 ~ • CD u 0.9 ~ ::I

0.8 Cl)

u CD 0.7 Q. Cl)

0.6

• 1111 8 • 1111

• 1111300mm lensl I •63mmlens

0.5

50 70 90 110 130 150 170

Slump (mm)

Figure 4.1: Relationship between the specific surface area of the ash and the

workability of the test mix.

The Van Eck material does not follow this trend, probably because the

exceptionally 'high carbon content of the ash dominates its behaviour. Although

the ash has the highest surface area, it is thought that the porous carbon absorbs a

large amount of water, with the result that the slump is decreased.

Comparing the slump values for mixes Ml and M2, it can be concluded that the

absence of ash particles greater than 63 µm did not influence the workability of the

two concretes significantly. The difference of lOmm recorded by the slump test

does not differentiate the two concrete mixes meaningfully.

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4.2 THE HARDENED STATE

For each concrete cube the saturated mass and saturated volume was determined

prior to compression testing, in order to calculate the density. The complete set of

data, including the saturated volume, saturated mass and density together with

standard deviations is given in Appendix B.

2.45 I •M2 lllM5 AM4 XM6 )KM31

2.445 x x x x 2.44 x •

;:; 2.435 • x • t x < .e

2.43 • x Cl ~ x > 2.425 ;t:: • en c 2.42 Ill GI c 1111 2.415 • 1111

2.41 • 1111

2.405

0 5 10 15 20 25 30

Age of Concrete (Days)

Figure 4.2: Graphical representation of the concrete densities.

As can be seen from Figure 4.2, the densities of the various concretes fall within a

narrow range and remain relatively constant over the curing period. The concrete

containing the Van Eck material, though tending towards the lower range of

calculated densities, is not significantly different from the other concretes. Thus

the influence of the high carbon content on the density of the concrete is minimal.

The compressive strength of the concretes was tested at the different time

intervals after casting. Table 4.2 lists the average results for the six concrete mixes

together with the calculated strength of a control mix with only 70% of the cement

content used in the present mix design. If the 70% strength value of the -~ontrol

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mix is used for comparison, any inherently cementicious character of the ashes

should be easier to detect.

Table 4.2: Compressive strength of concretes.

Average Compressive Strength of Concrete Cubes (MPa)

Mix Ex-render 3 Days 7 Days 14 Days 21 Days 28 Days Ml None 17.8 26.1 33.2 36.8 39.0

70% Ml None 12.5 18.3 23.2 25.8 27.3 M2 Lethabo( -63) 11.3 17.9 21.8 26.3 28.3 M3 Lethabo 10.0 15.8 21.0 25.1 26.8 M4 DuYha(-63) 11.0 16.7 22.1 25.7 28.4 M5 Van Eck(-63) 12.8 20.1 25.0 28.3 30.7 M6 Matla(-63) 10.7 18.0 22.6 25.5 28.1

Compared to the fly ash concretes, the Van Eck concrete recorded higher values of

compressive strength at all test dates, particularly after three and seven days of

curing, when the differences in strengths were most noticeable.

35

30

25

20 MP a

15

10

5

0 70% M1 M2 M3 M4 M5 M6

Figure 4.3: Compressive strengths of concretes.

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If a fly ash is a truly pozzolanic material, it will initially merely resemble a filler

material which aids the dispersion of cement particles and renders additional sites

for hydration products to form. In other words, until the pozzolanic reaction starts,

the strength of the concrete containing the fly ash should be about 30% less than

that of the control mix. However? this is a very simplistic approach which does

not take into account possible enhancing effects, such as improved packing, or

more important, the influence of the resulting change of actual (W/C) ratio.

In Table 4.3 the compressive strengths of the different concretes are compared

with the calculated 70% strength of the control mix. A plus and minus sign show

higher or lower values respectively. In Figure 4.4, the data is presented in

graphical format with the zero line indicating the position of the 70% control

reference strength.

Table 4.3: Comparison between strengths of test concretes and the calculated

70% strength of the control mix.

3 Days 7Days 14 Days 21 Days 28 Days M2 - Lethabo(-63) - - - + +

M3 - Lethabo - - - - -M4 - Duvha( -63) - - - - +

M5 - Van Eck(-63) + + + + + M6 - Matla(-63) - - - - +

The concrete with the milled (and sieved) Van Eck clinker ash distinguishes itself

clearly from the concretes containing the fly ashes. Right from the start the Van

Eck mix developed a higher compressive strength than the calculated 70% strength

value of the of the control mix cured for the same period. The milled clinker ash

thus contributed significantly to the strength development of the concrete over the

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time span tested, particularly during the first seven days of curing. The fly ash

concrete, on the other hand, had initially lower strengths than that expected from

the simple dilution model, but after about seven days of c~ng, their strengths

increased at a faster rate than that of the control mix, eventually exceeding the

calculated 70% strength values after about 21 days of curing.

Taking into account the degree of reproducibility of strength determinations, the

results indicate that the four fly ashes seem not to possess any significant

cementicious character of their own. The reason for the relatively low initial

strengths of the fly ash concretes are not clear, but it is probably the combined

result of changes in specific surface areas, packing efficiencies and actual (W /C)

ratios. The pozzolanic activity of the fly ashes becomes noticeable after about

seven days of curing.

<a a.

6

1-- M2 + M3 * M4 ----~5 * ~.'f I

~ 4 ·--

_4L_~~l--~~.J........~~...L-~~-'--~~-'-~~~

0 5 10 15 20 25 '1')

Age of curing (Days)

Figure 4.4: Strength differentials between test mixes and calculated 70% strength

of the control mix.

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In contrast, the milled clinker ash appears to have a definite cementicious character

of its own, which is mainly active during the first seven days of curing, with the

result that the compressive strength of its mix is consistently higher than that of the

fly ash mixes. The reasons why this material shows cementicious behaviour do

not lie in its chemistry (it has practically the same chemical composition as the fly

ashes), but it could be the result of its higher glassy phase content and the higher

specific surface area, compared to the fly ashes. On the other hand, the pozzolanic

reactivity of the milled clinker ash is very similar to that of the fly ashes, as shown

by the similarity of the slopes of the curves after 14 days of curing.

To use fly ash effectively as a cement extender in concrete, it is important to

understand the pozzolanicity of the material. In order to quantify this aspect,

various test methods have been developed (Wesche, 1991). One of these is to

calculate the pozzolanic activity index (PAI) relative to portland cement which is

given by PAI = NB · 100 where A is the average compressive strength of test mix

cubes and B is the average compressive strength of control mix cubes. The

pozzolanic activity index is generally quoted at 28 days, although calculated at any

time interval (Table .+.4).

Table 4.4: Pozzolanic activity indices.

Days M2 M3 M4 MS M6 3 63.5 56.2 61.8 71.9 60.1 7 68.6 60.5 64.0 77.0 69.0 14 65.7 63.3 66.6 75.3 68.1 21 71.5 68.2 69.8 76.9 69.3 28 72.6 68.7 72.8 78.7 72.1

Average 68.4 63.4 67.0 76.0 67.7

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The PAI values are the highest for the Van Eck concrete. It must however be

remembered that the higher strength for the Van Eck mix does not result only from

pozzolanic strengthening, but is aided by the additional binding capacity of the

material. According to Wesche (1991), pozzolanic activity of fly ash commences

after 14 days and thus calculated PAI values for three and seven days resemble

more a strength index than a measure of pozzolanicity.

The presence of the high percentage of carbon in the Van Eck material dominates

the colour of the concrete prepared with the ash. On the photograph (Figure 4.5)

the colour difference between a lOOmm cube of concrete containing the black Van

Eck(-63) material and Lethabo(-63) fly ash is shown.

Figure 4.5 : Photograph showing a cube of concrete with Van Eck(-63) milled

clinker ash (left) and one with Lethabo(-63) fly ash (right), both at a 30% direct

substitution level of the cement extender.

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5. RESULTS AND DISCUSSION - PASTES

The study of the thermal decomposition behaviour of cements and cement blends

is of a complex nature. Differential thermal analysis (DTA) and

thermogravimetric analysis (TGA) are two dynamic thermal methods

complementing each other and if used together can lead to successful

interpretations and findings which would be difficult to achieve with other

experimental tools. Both methods however are very sensitive to procedure details

and instrumental factors like heating rate and furnace atmosphere, as well as

sample details such as particle size and packing density.

Soomro (1988) summarizes the method of differential thermal analysis as follows.

It involves measuring the heat changes associated with chemical and physical

transformations taking place on gradual heating of a test sample. Transformations

such as dehydration, crystalline transition, lattice destruction, oxidation and

decomposition are generally accompanied by thermal changes which can be

detected by DT A . In order to relate a peak in a DTA plot to a specific phase or

phase change in the material, its temperature, endothermal or exothermal

character, intensity and other general characteristics (like peak shape) need to be

determined. The application of DT A as an experimental tool shows limitations in

cases where overlap of thermal reactions occurs, as this leads to difficulties in

resolution of the peaks. Other important factors influencing the success of DTA as

an analysis tool, include equipment parameters like heating rate, sample

characteristics such as size and packing as well as the stoichiometry and

crystallography of the phase or compound.

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A comprehensive guide to differential thermal analysis is given by MacKenzie

( 1957). With the use of figure 5.1, which shows an idealized peak, the

significance of the peak characteristics may be explained as follows. Along the

line AB, no reaction is taking place, as the temperature difference remains zero.

At B an endothermic reaction starts giving rise to the peak BCD. At C, the

minimum of the peak, the rate of heat absorption by the reaction, equals the

difference between the rate of heat supply to the test sample and to the reference

material. It is important to note that point C does not correspond to the

temperature where the reaction rate is at maximum or the temperature where the

reaction is completed. The temperature of the reaction rate maximum is given by

the inflection point of the curve between points B and C, while the reaction is

terminated at the.inflection point between C and D.

-· (.... '

<l - 0 .• A...__ ___ ~

8 Cl ~­... ~ :.a e = l e ~

Temperature (T)

c

Figure 5.1: Idealized endothermic peak on a differential thermal curve (MacKenzie, 1957).

,.•

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From point D onwards the temperature difference between the sample and the

reference material is zero again until another transformation occurs. The

temperature at point C is referred to as the peak temperature and is taken by

convention as a characteristic of the phase or compound present. The peak area

(area BCD) is proportional to the amount of reactant. BD is termed the peak width

whereas the distance EC is known as the peak height.

The qualitative aspect of differential thermal analysis involves the identification of

peaks obtained. From literature it is evident that no characteristic values for peak

temperatures apply for the same minerals. For example, Marchese and Sersale

(1986) quote the peak temperature for ettringite (calcium aluminate trisulphate

hydrate) as 150°C , Bye (1983) quotes 132°C , whereas Soomro (1988) notes a

temperature of 130°C. In the temperature range of 225°C to 400°C, the first peak

for hydrogamet (tricalcium aluminate hexahydrate) was reported by Marchese and

Sersale (1986) as well as Taylor (1964). The latter lists 120°C as the DTA

temperature characteristic for tobermorite gel. An endothermic peak at 200°C is

evidence of either low-sulphate calcium sulpho-aluminate hydrate or of a solid

solution of this compound with tetra-calcium aluminate hydrate (Soomro, 1988).

Between 400°C and 600°C the thermal effect of portlandite in the form of a well

defined endothermic peak has been reported by all the above authors.

Generally, the degree of overlap between the endotherms of ettringite and calcium

silicate hydrate gel is extensive so that resolution of these is difficult, if not

impossible. It is for this reason that Soomro (1988) summarizes the peaks on a

DT A thermogram into three temperature regions showing the major decomposition

reactions:

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• The endotherms occurring between 105° and 440°C are related to the

dehydration or water loss by calcium silicate hydrate. (The hydrogarnets and

ettringite also fall in this temperature range.)

• The temperature range between 440° and 580°C holds the peak due to the

dehydroxylation of calcium hydroxide, which was formed by the hydrolysis of

the calcium silicates during the hydration reaction;

• Between 580° and 1000°C decarbonation of calcium carbonate formed

during exposure to air occurs.

5.1.1 IDENTIFICATION OF PEAKS

With reference to Figure 5.2 and Figure 5.3 (as well as the thermograms attached

in Appendix C), the following minerals are identified according to their

characteristic peak temperatures.

a.) Evaporation: None

b.) Dehydration reactions:

• The ettringite (C3A·3~S"·31-32H) and tobermorite (C-S-H) gel

(3Ca0·2Si02·3H20) endotherms occur between 105°C and 150°C. The

ettringite thermal effect overlaps the tobermorite peak. It should be noted

that, per molecule, ettringite contains 31 to 32 water molecules in contrast

to the 3 water molecules of the gel. The combined peak of ettringite and

tobermorite broadens towards higher temperatures as the hydration reaction

proceeds with time (comparing the DT A thermo gram after 3 days of curing,

Figure 5.2, with that given in Figure 5.3 after 28 days of curing).

• The endotherm at 190°C is ascribed to low-sulphate calcium sulpho­

aluminate hydrate (3CaO·A120 3·CaS04 · 12H20), possibly in solid solution

with tetra-calcium aluminate hydrate (4CaO·Al20 3·12H20). This peak

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Figure 5.2: OTA and TGA plots (dry nitrogen atmosphere) for the pastes

containing the Van Eck(-63) and Lethabo(-63) ashes after 3 days of curing

7 2

6 .......................... :::·:· .. ···! Letiiabo TGA 1 .................... 1 Lethabo DTA 1.... ................... ...................... 0

~ 5 ·················~········ ..... ::: .. ,, ........ .; .................................................................. , ............................................................................... . c: '·,·~ .. , _,_ ...... _ .. ~ ~ 4 ············································· \.,-::··········································;-;~: ...................... -::::::.:::::::: ;\···· ........ ·············································· -2 ~ '\·\ _,/' \ : '··, 0 3 .................................................. -..... :.-..:; ................. ;/................................. .. ......................... \.... .. .. ; ...... ::::'-.,;;~-....................... . Q) \.. ... ' i '- -4 .._ \.~ ,/ \ ? ~\~ .• ~ 2 ,. . .

i : -1~::,:c:~~:-J1 =::·~~,~~;\-}:-.-=-:::::~---.----.-.- : g -1 ........................... ~\,.,::;,-:::::: .. - ..................... ,..................................................... ...'\.;:~ ................................................... ..

-2 ................................ ............... · .............................. 1 Van Eck DT A ! ................ '::::::... ·-.::::::~:::.::::...... -1 O

-3 -12 0 100 200 300 400 500 600

Temperature (Degrees Celsius)

Figure 5.3: OTA and TGA plots (dry nitrogen atmosphere) for the pastes

containing the Van Eck(-63) and Lethabo (-63) ashes after 28 days of curing

63

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appears to be more pronowiced for the pastes containing fly ash or the

clinker ash than for the control mix (see Figure 5.4). The chemical

compositions given in Table 3.1 show markedly higher values for alumina

in the ashes than in the OPC, which could be the reason for the formation

of larger amounts of the above-mentioned hydrates in the pastes containing

the ashes.

• Hydrogamet (3CaO·Al20 3·6H20) appears as a small endothermic peak at

about 3 70°C.

1.5 .......................................... - ...................................................................................................................................................... ..

1 ~-8 /,

/',,. ,

c: ,•

~ 0 5 ............................................................................................................................................................ /.< ............................. .. :t: . / 0 i f 0 .................... -................... - ....................................................................................... c .......... /~ ................................................ . 2 / ~ .i ~ I ~ -0 .5 ......................................... _ ................................ ';:' .. '""'" ___ -. ........................ /" .......................................................... .

; E .i ID ' I- ................................................................................... ~ ................................................................... . ,.··--·-..111 I ,,, .,_ ,. ,- ........ ,

······-····-··-·-·-· ',, I -1 .5 ........................................... _ .............................................................. , ........... / .......................................................................... . ···-"

-2+-~-.-~~~~-.--~---.-~~...--~~~~~~~~-l

140 150 160 170 180 190 200 210 220 230 Temperature {Degrees Celsius)

Control

Matla(-63)

Figure 5.4: DTA thermogram showing the endothermic peak for low-sulphate

calcium sulpho-aluminate hydrate for the OPC and Matla(-63) pastes (dry nitrogen

atmospheres) after 28 days of curing

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b.) Dehydroxylation reactions:

• The portlandite (Ca(OH)i) endotherm is identified at 450°C. The

portlandite peaks for all the pastes are very similar in shape. The peaks are

strong and sharp with the maxima very close at 450°C. This peak shape does

not change over the curing period. For the pastes containing the Van Eck(-63)

material, the portlandite peak is displaced upward as well as to a slightly higher

temperature. This shift is due to the superposition effect of a large exothermic

effect following immediately on the dehydroxylation reaction.

In the temperature range between 350°C and 580°C the paste samples containing

the Van Eck ash show a different thermal behaviour to the other materials. To

explain this behaviour, reference is made to Figure 5.5 and Figure 5.6. The DTA

thermograms show the Control, Lethabo(-63), Lethabo, Duvha(-63) and Matla(-

63) paste samples heated in a dry nitrogen atmosphere and the Van Eck(-63) paste

sample in air, all after 28 days of curing. The oxygen present in the air

atmosphere allowed oxidation reactions to take place and hence differentiated the

Van Eck material even more clearly from the other pastes.

The letter A (Figure 5.5) denotes the portlandite peak at 450°C for the fly ash

pastes. For the Van Eck paste, three peaks are superimposed in this temperature

reg10n. Peak C is identified as the endothermic portlandite peak whereas it is

suggested that B points to a exothermic peak resulting from the oxidation reaction

of mainly maghernite, Fe20 3 (MacKenzie, 1957) as well as magnetite, Fe30 4.

Overlapping these two peaks, a third peak D starts at about 3 70°C, and extends to

temperatures beyond 580°C. This exothermic peak is ascribed to carbon burning

off.

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The above explanation is substantiated by the thennogravimetric data presented in

Figure 5.6. After about 450°C the TGA curve for the Lethabo(-63) paste

decreases, which indicates a mass loss.

Control

Lethabo(-63)

Lethabo

Duvha(-63)

Van Eck(-63)

Matla{-63)

-54---~--~-~~--~-~~-~~ 300 350 400 450 500 550 600

Temperature (Degrees Celsius)

Figure 5.5: DTA Thennogram after 28 days of curing for the Van Eck (-63) paste

in an air atmosphere and the other samples heated in a dry nitrogen atmosphere.

............................................................................................................................. Van Eck(-63) in Air

-8 ...... ~ .............. . ... ,, ... ~.,,, ............................ . ~ '··.

~ -9 .......... :. .. -~'.~~ ·:·\··············· ·········································· ............. .

j ::~ =::_-=:==~:;~~:::::: Lethabo(-63)

Van Eck(-63)

* -12 ................................ --...................................................... - ..................................... ··································

-13 ································--··········································································································

-14 ................................ _ ............................ ·-·················································································\·········

-15+----.,.----,---...,.-----.---,.--~ 300 350 400 450 500 550 600

Temperature (Degrees Celsius)

Figure 5.6: TGA plots for the Van Eck(-63) pastes in dry nitrogen and air as well

as the plot for the Lethabo(-63) paste heated in dry nitrogen after 28 days of cunng.

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The Van Eck(-63) pastes however, show an initial mass gain after 450°C followed

by a mass loss. This effect is more pronounced when the sample was heated in an

air atmosphere where oxidation reactions took place. In relation to the fly ashes,

the Van Eck material is in a much more reduced form because of the lower

burning temperatures of the coal in the power station. Hence a large amount of

volatile matter is still present in the clinker ash which starts to burn off beyond

400°C (Figure 5.5, curve D).

c.) Decarbonation reactions: These are not observed. Samples of the pastes were

taken from the center of the cubes and exposure to air was very limited which

practically excluded any carbonation from taking place.

5.2 THERMOGRAVIMETRIC ANALYSIS

Whereas differential thermal analysis (DTA) is based on energy changes,

thermogravimetry (TGA) is based on mass changes. The decomposition reactions

like dehydration or dehydroxylation are associated with a loss in mass (water in

these cases). The mass change is measured against the inert reference material and

expressed as a percentage of the test sample mass. All the TGA plots of

percentage mass loss against temperature for the different ashes and the control

paste are given in Appendix C.

In addition to the thermogravimetric plots, the data was further manipulated and

the derivative of the thermogravimetric plots calculated, which gives the rate of

mass change and can be plotted either against temperature or time. Such

derivative thermogravimetric analysis (DIGA) curves are provided in Appendix C.

The advantage of DTGA plots is that they help to establish temperatures where

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thennal reactions start and end. Another advantage of DTGA is that reactions with

overlapping peaks in DT A and TGA curves are often successfully separated.

DTGA plots for the different ashes and the control mix are attached in Appendix

c.

5.2.1 QUANTITATIVE ANALYSIS -THE AMOUNT OF BOUND WATER

The total amount of bound water present in the hydrated phases of the pastes was

estimated as follows. The limiting temperatures of the thennal decomposition

reactions were established from the DTGA curves in that maxima (turning points)

on these traces corresponded to maximum rates of mass change. The vertical lines

marked x and y (see Figure 5. 7) depict how the limiting temperatures were

obtained.

Dry Nitrogen Atmosphere

0.04 ···-----··· -··· ·-· --·

o.oe...------------------------,I y 3 Daya

0.02 . 7 Oay1 Q)

g> 0

6 1'4 Oay1

·0.02

~ """" ·0.04 ·-·-· '5 ~ ~

·0.12+---T----....---,....----,....---------1

·-I 21 Oay1

28 Oay1

0 100 200 300 400 500 600 Temperature (Degrees Celsius)

Figure 5.7: DTGA plot for the Van Eck(-63) paste samples over the total curing period.

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The thermal decomposition reactions between 100°C and 600°C resulting in water

loss were divided into two groups. The first group included the temperature range

of 100°C to 400°C over which the mass loss due to dehydration (DH) was

obtained, whereas the second group ranged from 400°C to 4 70°C to account for

the mass loss as a result of the process of dehydroxylation (DX) of portlandite

formed by the hydrolysis of calcium silicates. Figure 5.7 was used as the basis to

choose the maximum temperature of the dehydroxylation reaction. The choice of

4 70°C was made in order to exclude the effects due to mass gain for the Van Eck

(-63) material at temperatures higher than 470°C.

As shown in Figure 5.8, the amount of water and hydroxyl lost was estimated by

reading off the corresponding mass changes as percentages between the specified

temperatures and calculating the absolute value of the incremental weight change.

1

0 ..... ...... Control

-1 Lethabo(-63}

-2 Q)

Ol -3 c: Van Eck(-63)

<'Cl .r:: -4 (.) (/)

-5 (/)

<'Cl :?

-6 '#. -7

-8

-9

-10 0 100 200 300 400 500 600

Temperature (Degrees Celsius)

Figure 5.8: Determination of mass loss.

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The percentage mass losses due to dehydration and dehydroxylation for the

different pastes at the various curing times are tabulated in Table 5.1.

Table 5.1: Percentage mass loss due to dehydration and dehydroxylation, as well

as total amount of bound water. Curing Time (Days)

..... 7 I4 2I 28 .)

. Control %DH 5.9 6.7 8.0 8.I 8.2 %DX 2.2 2.5 2.6 2.7 3.3

DH+DX 8.1 9.2 I0.6 10.8 I 1.5

Lethabo(-63' %DH 4.3 5.8 6.6 7.5 7.7 o/oDX 1.7 2.3 2.3 2.4 2.5

DH+DX 6.0 8.1 8.9 9.9 I0.2

Letha ho %DH 4.3 6.2 6.7 7.5 7.6 %DX 1.8 2.4 2.3 2.4 2.4

DH+DX 6.1 8.6 9.0 9.9 10.0

Duvha(-63) %DH 4.3 6.2 6.6 7.5 8.I %DX 2.0 2.3 2.8 2.6 2.3

DH+DX 6.3 8.5 9.4 10. l I0.4

Van Eck(-63 , %DH 4.8 6.7 8.I 8.4 ' 8.6 %DX 1.3 1.8 1.6 1.7 1.8

DH+DX 6.1 8.5 9.7 IO.I I0.4

Matla(-63) %DH 4.5 5.6 6.6 7.5 7.8 %DX 1.7 2.1 2.2 2.6 2.7

DH+DX 6.2 7.7 8.8 10.I I0.5

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In Figure 5.9, the compressive strength of the concrete mixes is plotted as a

function of the total amount of bound water detennined in the corresponding

pastes. A good correlation is found. As the· amount of bound water in the paste

increases, so does the compressive strength of the concrete. The total amount of

bound water as determined from the TGA plots relates to the amount of hydrates

formed during the hydration and can be used as an indication of the strength

development. Assuming that the extrapolated curve starts ·at the point (0,0), it can

be concluded that the rate of hydration increases (the slope increases). This

conclusion is valid only up to 28 days after casting as this is the curing period over

which the samples were tested.

40 • • l 35

!. • i 30 u c 8 25 'O & 20 .. ~ 0 • c ~ (I') 15

6 c ., •

.~ • "' ei 10

019 Q.

8 5 u

0

0 2 4 • I 10 12

Total Amount of Bound Water (04 by Ma11)

Figure 5.9: Compressive strength of concrete as a function of the total amount of

bound water in the corresponding pastes.

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Figure 5.10 gives the compressive strength of the concretes as a function of the

amount of water lost due to dehydration reactions in the pastes, whereas Figure

5.11 relates the compressive strength of the concretes to the amount of water lost

40

l 35

!. i 30 u c:

c'3 26 'O i 20 c: ! II) 15

.~ ,,, e 10 Q,

3 5

2

• €!. •

,, •

3 4 5 6 1 Amount of Water lost by Dehydration (% by Ma11)

• • •

9 10

Figure 5.1 O: Compressive strength of concrete as a function of the amount of water lost due to dehydration reactions in the corresponding pastes.

40

f 31 !. i 30 u c:

c'3 25 'g

i 20 c: !! ~ 15 . ! ,,, ! 10 Q,

3 5

0

0 0.5

• •

• •

• 9. 0

2

• •

0 0 6

~o 6 • 0 0

6. 0 0 •

3 A.mount of Water lost by Dehydroxylatlon (%byM111)

4

Figure 5.11: Compressive strength of concrete as a function of the amount of

water lost due to dehydroxylation reactions in the corresponding pastes.

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by dehydroxylation reactions m the pastes. The degree of scatter for the

dehydroxylation plot is much greater than that of the dehydration plot. This is to

be expected from the fact that the amount of portlandite (which is given by the

percentage water lost by dehydroxylation), makes no direct contribution to the

strength development of the paste (and hence the concrete). Nevertheless the trend

of increasing concrete strength for increasing amount of water lost is still

observed.

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6. SUMMARY AND DISCUSSION

The effectiveness and properties of a clinker ash from the Van Eck power station

in Windhoek (Namibia) if used as cement extender in concrete were investigated.

The milled clinker ash was compared to three fly ashes (Lethabo, Duvha and

Mada) on the basis of the effect on strength development of concrete prepared

with the ashes introduced as a 30o/o direct mass to mass substitution for cement.

The concrete with the Van Eck milled clinker ash unexpectedly yielded the highest

values of compressive strength over the cwing period tested.

The approach used for the investigation into the effect of the different ashes on

compressive strength was to keep all the parameters in the concrete mix design

constant and only change the type of ash to be used as cement extender. By only

substituting the type of extender, the effect that the ashes have on the mixing water

requirement was not adjusted for. In other words, by using constant proportions of

water, cement and aggregates, the consistency or workability of the mixes was not

kept constant.

The effect which the different ashes had on the workabilities of the concretes were

quite different and the slump values show a large variation. The Van Eck mix,

with a slump of 70mm, was very similar to the control mix (containing only OPC

and no extender) in the fresh state, whereas the Lethabo(-63) mix, with a slump of

170mm, showed very different flow characteristics. Because of the fact that

virtually no change ( 5mm difference in slump) in the flow properties occurred

when partially substituting milled Van Eck ash for the cement, it must be

concluded that the clinker ash has no influence on the water requirement of the

concrete mix. Although the milled clinker ash had the largest surface area, as

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determined by laser diffraction spectrometry, the water requirement of the

concrete was not reduced. It is thus concluded that the presence of >30% carbon

in the Van Eck material is responsible for the fact that no water reduction has been

achieved. In Fulton (Addis, 1986), the porosity of carbon, leading to additional

water absorption, is mentioned as being the factor responsible for the adverse

effect of the material on the workability of a concrete. However, keeping in mind

that a maximum of 12% carbon in fly ash is specified in ASTM 618-89 (1988), the

Van Eck ash performed well.

Due to the water reducing capabilities of the Lethabo fly ash, less mixing water

would have been needed in the concrete to obtain a specific slump value if

compared to the Van Eck ash. The Lethabo mix, in contrast to the Van Eck mix,

is thus essentially at a higher water to cementitious material ratio if the mix design

of constant mix proportions is followed. Because the W/C ratio of concrete is

inversely proportional to the compressive strength of a concrete, the lower

strengths tested for the fly ash concretes in relation to the clinker ash concrete

must be interpreted in the context explained above. It should thus not be

concluded, by judging on the criterion of compressive strength up to 28 days, that

the Van Eck ash necessarily outperforms, for example, the high quality fly ash

from the Lethabo power station. The performance of a concrete with or without an

extender is primarily influenced by the mix design. An aspect that is still to be

investigated is thus the strength development of concretes containing the ashes

used in this study, but with the concretes designed to yield a constant slump.

The pozzolanic reactivity of the Van Eck material is very similar to that of the fly

ashes. This important parameter (obtained from comparing the slopes on the plot

of strength differentials versus curing period in Figure 4.4 as well as calculating

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the pozzolanic activity indices in Table 4.4) seems to be unaffected by the carbon

present in the clinker ash. In addition to a similar pozzolanic reactivity as the fly

ashes, the milled clinker ash possesses some inherent cementicious character

which is clearly noticeable in the time period before the pozzolanic reaction starts.

This behaviour is normally found only with Type C fly ashes. But the fact that, on

correcting the chemical composition for the carbon, the criterion set in the ASTM

Standard 618-89 (1988) for the sum of the oxides of Si02, Al20 3 and Fe20 3

having a minimum of 50% is not met any longer, the classification of the ash as

being similar to a Type C fly ash is not correct. It is suggested that the milled Van

Eck material be classified as a clinker ash resembling a Type F fly ash (based on

the corrected chemical composition) which possesses some cementicious character

in addition to the pozzolanic reactivity.

The densities of the concretes with cement extenders compare well. Again, the

effect of a large amount of porous carbon present in the Van Eck mix is

insignificant in changing the density of the concrete.

In conclusion, the exceptionally high carbon content of the Van Eck material

(35.38%) showed a surprisingly small influence on the properties of the concrete

containing the ash. Contrary to general belief, the research proved that, up to 28

days after casting the concrete, the high carbon clinker ash is a very effective

cement extender. However, the fact that concrete prepared with the Van Eck

material as cement extender is dark gray or black, as depicted on the

photomicrograph in Chapter Four, must be taken into consideration in those

applications of the material where the aesthetics are of importance.

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Differential thermal analysis as a qualitative method could successfully be used to

identify various phases at different stages in the hydration reactions of the pastes.

Pastes of OPC plus 30% of fly ashes of Lethabo(-63), Lethabo, Duvha(-63) and

Matla(-63) show a very similar thermal behaviour up 600°C. On the other hand,

for the Van Eck(-63) material on the other hand additional peaks as well as

different peak characteristics are observed. Peaks for ettringite, tobermorite, low­

sulphate calcium sulpho-aluminate hydrate and tetra-calcium aluminate hydrate,

hydrogamet and portlandite are identified for all the pastes. The analysis of the

paste containing the Van Eck material, shows additional peaks for the iron oxides

of maghemite and magnetite as well as for the carbon burning off.

Thermogravimetric analysis of the paste samples clearly distinguishes between the

fly ash pastes from the clinker ash paste at temperatures higher than 470°C. For

the Van Eck paste, an initial mass gain is observed after 4 70°C which is

accentuated when the samples were heated in air rather than a city nitrogen

atmosphere. The oxidation of maghemite and magnetite which shows as a

exothermal peak results in this mass gain.

The quantitative analysis of the amount of water lost by dehydration and

dehydroxylation could successfully be determined from the TGA plots. The

important result however, is that these figures, obtained from the paste samples,

could be related to the strength development of the respective concrete. The

correlation between the compressive strength of concrete and the amount of water

lost by dehydration was better than that between the compressive strength of the

concrete and the dehydroxylation losses. This finding is consistent with the fact

that it is mainly the hydrates dehydrating in the temperature range between 100°

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and 4 70°C that contribute significantly to strength development, whereas the

portlandite is ineffective in this respect.

More work needs to be done to fully evaluate the effectiveness of the Van Eck

material, for example a comparison of concretes containing the ashes which are

designed to constant slump, as well as a study on the durability of Van Eck

concrete. However, the fact that a milled clinker ash containing over 30% carbon

has successfully been used as a cement extender may be of benefit to some of the

older type power stations still in use today. In most of these power stations, the

ash is collected as clinker ash which includes coarse bottom ash and the fly ash. It

is indeed a positive prospect that these ashes, which generally have high carbon

contents, can nevertheless be used as portland cement extenders in concrete.

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7. REFERENCES

Addis, B.J. (Editor) (1986) Fulton's Concrete Technology, Sixth Revised

Edition, Portland Cement Institute, Midrand, South Africa.

79

Alis, J.C. et al. (1992) Mechanical Properties of Fly Ash Concrete Cured under

different Temperatures and Humidity Conditions, Fly Ash, Silica Fume,

Slag and Natural Pozzo/ans in Concrete, Proceedings Fourth International

CANMET /ACI Conference, Instanbul, Turkey, Supplementary Papers,

pp.1023-40.

American Society for Testing and Materials, ASTM (C618-89) (1988) Standard

Specification for Fly Ash and Raw or Calcined Natural Pozzolan for Use as

a Mineral Admixture in Portland Cement Concrete, Philadelphia.

Ballim, Y. Chemical deterioration processes, Personal Notes, presented at the

University of Cape Town, February 1993.

Ballim. Y. Permeability of Concrete, Personal Notes, presented at the University

of Cape Town, February 1993.

Berry, E.E. and Malhotra, V.M. (1987) Fly Ash in Concrete, Supplementary

Cementing }vfaterials for Concrete, edited by Malhotra, V.M., Energy,

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CANMET.

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Bijen, J.M.J.M.et al. (1992) Fly Ash as Addition to Concrete, A.A.Balkema

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Bosch, G.L and Willis, J.P. (1990) The Chemical and Mineralogical

Compostions, and Particle Size Distribution, of Fly Ash form three South

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80

Botha, J. and Amtsbiichler, R. (1990) Heat Development in FA Concrete, First

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Bye, G.C. (1983) Portland Cement: Composition, Production and Properties,

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Dartsch, B. and Herten, D.L. (1992) Einsatz von Steinkohlenflugasche im Beton­

und Fertigteilwerk, Concrete ?recasting Plant and Technology, 1.

Davis, D.E. and Coull, W.A. (1991) Alkali-Aggregate Reaction, Choosing the

right Aggregate and Cement for Concrete, A Hippo Quarries Technical

Publication, Second Edition.

Dhir, R.K. (1986) Pulverized Fuel Ash: Concrete Technology and Design,

Cement Replacement Materials, Volume 3, edited by Swamy, R.N.,

pp.197-255, Blackie & Son Ltd.

Elfert, R.J. (March 1987) Bureau of Reclamation Experiences with Fly ash and

other pozzolans in Concrete, Proceedings Third International Ash

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Utilization Symposium, Pittsburgh, Pa, US Bureau of Mines Information

Circular IC 8640, pp.80-93.

Ellis, W.E. (1992) For Durable Concrete, Fly ash does not "replace" Cement,

Concrete International, July, pp.47-51.

Feldman, R.N. (1989) Studies on Mechanism of Development of Physical and

Mechanical Properties of High Volume Fly Ash-Cement Pastes, Third

CANMET/ACI International Conference on Fly Ash, Silica Fume, Slag

and Natural Pozzo/ans in Concrete, Supplementary Papers, Trondheim,

Norway.

Galeota, D. et al. (May 1992) Mechanical Properties of Concretes containing Fly

Ash, Fly Ash, Silica Fume, Slag and Natural Pozzo/ans in Concrete,

Proceedings Fourth International CANMET I ACI Conference, Instanbul,

Turkey, Supplementary Papers.

Grieve, G.R.H. (1991) The Influence of two South African Fly Ashes on the

Engineering Properties of Concrete, Ph.D. Thesis, University of the

Witwatersrand, Johannesburg.

Hansen, T.C. and Hedegaard, S.E. (1992) Modified Rule of Constant Water

Content for Constant Consistency of fresh Fly Ash Concrete Mixes,

Materials and Structures, 25, pp.347-354.

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82

Hansen, S.E. and Hedegaard, T.C. (1992) Modified Water/Cement Ratio Law for

Compressive Strength of Fly Ash Concretes, Materials and Structures, 25,

pp.273-283.

Helmuth, R. (1987) Fly Ash in Cement and Concrete, Portland Cement

association, Illinois, U.S.A ..

Heckroodt, R. (1990) The Hydration of Portland Cement, Personal Notes.

Jawed, I. et al. (1991) Hardened Mortar and Concrete with Fly ash, RILEM

Report 7: Fly Ash in Concrete - Properties and Performance, edited by

Wesche, K., Chapman & Hall.

Kriiger, J.E. and Van Djik, J. (1985) Fly Ash Concrete, Personal Notes,

Inorganic 11aterials Division, National Building Research Institute, CSIR.

Kruger, R.A. ( 1990) The Chemistry of Fly Ash and the Pozzolanic Reaction,

ChemSA, November 1990, pp.301.

Kruger, R.A. (1990) Ten Years of Research into Ash Utilisation, First National

Symposium, CSIR Conference Centre, Pretoria.

·Kruger, R.A. (1993) Personal Communication.

MacKenzie, R.C. (Editor) (1957) The Differential Thermal Investigation of Clays,

The Central Press, Aberdeen.

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83

Malhotra, V.M. and Painter, K.E. (1988) Early-age Strength Properties and

Freezing and Thawing Resistance of Concrete incorporating High Volumes

of ASTM class F Fly Ash, Int. J. Cement Composites and Lightweight

Concrete, 11, no.1, pp.37-46.

Mantel, D.G. (1992) The Manufacture, Properties and Applications of Portland

Cements, Cement Additives and Blended Cements, Pretoria Portland

Cement 64pp.

Malhotra, V.M. (June 1989) Durability of Concrete incorporating high-volume of

low-calcium (ASTM F) Fly Ash, Durability of Concrete, Aspects of

Admixtures and Industrial By-Products, Second International, pp.93-104.

Malhotra. V.M. (~ay 1992) CANMET Investigation dealing with high-volume

Fly ash Concrete, Advances in Concrete Technology, Proceedings of

International Conference, Athens, Greece, pp.433.470.

Marchese, B. and Sersale, R. (1968) Stability ofHydrogamet Series Terms to

Sulphate Attack, Supplementary Paper 2-6, Proceedings of the Fifth

International Symposium on the Chemistry of Cement, Tokyo, pp.133-

137.

Maslehuddin, M. et al. (1987) Effect of Fly ash addition on the Corrosion

Resisting Characteristics of Concrete, AC! Materials Journal, Jan-Feb,

pp.42-50.

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Nasser, K.W. and Lai, P.S.H. (1992) Resistance of Fly Ash Concrete to freezing

and thawing, Fly ash, Silica Fume, Slag and Natural Pozzo/ans in

Concrete, Proceedings Fourth International CANMET/ACI Conference,

Instanbul, Turkey, 1, pp.205-26.

National Building Research Institute (1985) Final Report on the Development of

a Mix Design Method for FA Concrete, Pretoria, R.S.A ..

Popovics, S. (1991) A Model for Estimation of the Contribution of Fly Ash to

Concrete Strength, Blended Cements in Construction, Papers presented at

the International Conference on Blended Cements in Construction,

University of Sheffield.

Sivasundaram, V. (June 1989) Long-term Strength Development of high-volume

Fly Ash Concrete, Third International Conference on the Use of Fly ash,

Silica Fume, Slag and Natural Pozzo/ans, Trondheim, Norway.

Skoog, D.A. et al. (1988) Fundamentals of Analytical Chemsitry 5th Edition,

Saunders College Publishing, U.S.A., 894pp.

Soomro, M.A. ( 1980) Thermal Analysis and its Applications in the Study of

Cement, Mehran University Research Journal of engineering and

Technology, 7, no. 4, October 1988, pp. 17-22.

South African Bureau of Standards, The Structural Use of Concrete, Part 2:

Materials and Execution of Work, SABS 0100-2:1992.

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Swamy, R.N. (1990) The Role of Mineral Admixtures on enhancing the Quality

of Concrete, Properties of Fresh Concrete, Proceedings of the RILEM

Colloquium, Hanover, pp.125-133.

Swamy, R.N. (1990) Fly ash Concrete - Potential without Misuse, Materials and

Structures, 23, pp.397-411.

Wesche, K. (Editor) (1991) Fly Ash in Concrete Properties and Performance,

Rilem Report 7, E & FN Spon (Chapman & Hall), London.

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APPENDIX A

Page • Particle size distributions determined with a 63mm lens for:

OPC from Ulco, Anglo Alhpa Al

Lethabo fly ash as supplied A2

Lethabo( -63) fly ash A3

Duvha fly ash as supplied A4

Duvha(-63) fly ash A5

Van Eck clinker ash as collected A6

Van Eck milled clinker ash A7

Van Eck(-63) milled clinker ash A8

Van Eck(-63) milled clinker ash (repeat) A9

Van Eck(-63) milled clinker ash (repeat) AlO

Matla fly ash as supplied· All

Matla(-63) fly ash A12

• Particle size distributions determined with a 300mm lens for:

OPC from Ulco, Anglo Alhpa A13

· Lethabo fly ash as supplied A14

Lethabo(-63) fly ash A15

Duvha fly ash as supplied A16

Duvha(-63) fly ash A17

Van Eck clinker ash as collected A18

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Sample: Ordinary portland cement from Ulco factory, Anglo Alpha.

Focal Length: 63mm

Interval percentage

10t

I. :i1 \

! ~i:~ 1n 1-:oh fi Sde ·, 1 :ize L

.: I , ~ t • • I .'

0.:!:~.4 0 .. ?. ! : : . 0 !:j.: ! : ~-. 8 1'; ~ ! - '"'.' 7 "I 'f' - • I I

t: ".'I - :: 0 './•: ' - ... u

1 10 Particle size (um).

l. 3124. i) 2.l f 22.3 : . 2120. 7 . : .. :119.:. 3.5.~:7.9 .., L I ! t. ~ •'I \.ii • ..,; I I

3.6t::,.:, 3.5)14.4 3 .. 3 13.4 ., ""!I '.., c ¥·f 1ff·~ •JI • I .i. .l I,_.

I

In 'l.

In IHiah % ! Siie

I l.4'2.:5 ' •I 1 A" L' .,.\ j.;.' •~.; 1.2 1.98 1.1': ~c. : I ~ t l I 0 ~ • '' I ~ C I

1:011:41 0.9 11.31

t~il.: 2

f),3 0.2 0 ' .. (; t

I \ ...... j

l I

1 t

j

100

M Df·i,G,9Jn !~· '"1J"··

... I • "'"'I

.. ' ' 'i ··~ 4:38-~i~~

UCT DE!' pea...- tme=-n t

Al

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Sample: Lethabo fly ash as supplied.

Focal Length: 63mm

rn i I

i I I I

t I I ~ I ' I t \ I

% c. l J,,

I I

t I I

t ' I

Interval percentage

.1

~ 11'2 ~ f.; g !i 9 :,: : I 8S.6 ~ e:.4 I 76.6 Q 71. 2 h 66.2 ~ 61. 6 ff c:~ ., M ~I'~

u :· .-·.·,. - -;; ... ·-JW· '.C' ff :" ~Foc;l ~e~·::· ~. c·,;·;2r: ta ti~n

UCT

1 Particle size (u~).

p hy "S .i. C:S>

10

I

t I I • I i l i

1 ~

i

i ~

A2

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Sample: Lethabo(-63) fly ash.

Focal Length: 63mm

/. 5

Interval percentage

I

t !

.1 1 10 Particle size (uM).

In 1 -iioh Jn 7. I: i ie 'f.

Hiqh Siie

In jHiah Jn 11 ~;gh X .Siie X ~1ze Jn , Higi"1 Irr

i. I ~i ze i.

100

I t {

1

I t I 1 I

! !

o. ;:3.3 0.2\24.0 2.7 , .... ·" 3.3!4.84 2.212.1a 0. nr4 11

o, ~t;.s o.s 22.3 2.7 !'I~~~ 3.2\4.50 2.1 2.03 o. ~ "t:'.~Surn 0. 1!6,1 0.8120.7 2.8 9 . .,,. 3.014.19 1.911.88 6. M I

~ I!~ 8 1.0\19.3 i O ,8,66 3,0,3,89 1.8,1,75 ), ~ :~3,2} ! ~: i:ij:s l.3117.9 ~:~ 8.05 3.0 3.62 l.7 1.63 n ~ 7.77ur~ 0. 1:7.0 1.6,16.7 3.0 !7.49 2.9,3.37 :.=· 1.51 o: ~ '· C 1-, 4 1 n7 !C c ~ 1 le' ,Q,•,, ?,Q, ,1,1~ 1,A l,11 ~ "r,, 0 91•

' 1 ·'" ~ • .'-,·1•-"J "'" - ··- .'T' .,, 1•"'~ .. :_·,~.~·.·,J,U 0, ,-, 0 k•k114.4 3.3 6.48 2.812.91 1.3 1.31 0. , ... ~~.rn" o. i:?:e 2.4!13.4 3.4 16.02 2.712.71 1.1r1.22 o. 0

0. !:7.7 2.5112.5 3.~! ,5.60 2.6!2.52 ':;.3~ D[v,0.1}~ O. 1 ::.2 2.t11:.6 3.4 1:,.21 2.4!2.34 O.t! 3.bbuml

S::,;rce : . . • • . I ~ ' . . I •• . < ~

A3

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Sample: Duvha fly ash as supplied:

Focal Length: 63mm

' • I t I

I t I

'J c ' ,, ...J•

} I I I

f i

t I I I •

Interval percentage

UCT

1 10 Particle size (un).

In !Hioh ~.: ! s i z ::·

'l c ... .; 2.9 ~ ·~ .;; . .:: ~ ~

3.3 4.84 3.4 4.50 3. 4 4, 1,' 3.S\3.SS ·-·. 413. 62 3.3!3.37 3 Ir;, 3 1 l: '") '=I~ r. ! .;_I.) j .,_I 7 .i. -~, ~ I "'.· "'r 1

l:S!.:<~.2 1.6 2.34

ln IH1gh In Z !Size

i:Fs:t3 1 :~ I 1 OC· •• .,. l • ·~,.,,

1.411.75 1.411.63 t ~I . c.1 J. I ·.I I .. I ·-· 4

: "'.t I 1 .~ ~ 0, I ,0. . .i, I 'T. l.lli 31 0.911.22 0.5' 0.2!

100

t l

1 I f I i

i t

I t I

l !

I

- . :Sample !Beam lenq~h = 2 0 mm~~cdel indp 3 ~~v,o.~:e ' Loq. Dif!, = .30?1 Pr 12.42Ui!~

= 63 mmfOtscutatior = C.! :~ !V~~~~e Cone. 0.033~Z~ ' = 011 JVolume distri~~t on !5~.S.A 0.6393 m?/:~.t~·~:; :=F~

phys;. i C::=>

A4

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Sample: Duvha(-63) fly ash.

Focal Length: 63mm

Interval percentage 10

:1. Si l r I

t '·

01 .1 1 10

Particle size (ur.d.

,, :iQh In 1-iah ln HiQh In .~1ze 'I. : :~ie X SiZe %

Fc~:·ce =

n~g,,l~~16; u

I), 3124. () 0.6122.3 I), 9120. 7 1. 2119 .3 I 'It" ,-, i. I.JI. i • 7

1.8\16.7 ·! 1 I ~ c C, 4 t .I. i J. .J l\I ') '11 .• 4 ". ~ . ~. 2.6 13.4 2. 7112. 5 2.7f 11.6

2.6 2.6 2.6 2.2 3. (j ~ ~ ·-' f ·./

3.6 3.8 4.0 4.1 4 ,\)

High In Hiah ·Size % S1ie

11(). 8 110.0 ,9.31 \8,66 t ~~. C' :1 !7.49 16. S7

16.48 6.02

! .:'. 60 I~. , ~ , .... , ....

1.8 2.18 1.512JJ3 1.3! 1.SE •. 'i I ~ 1 c.

i:rl·i:63 1.1 1.51 1.1 1.41 1.111 .. 31 (' -1 · -. •, ) I~ ,l_ I.:" o.~I 0 • ..;

100

A5

1 J I I I

~ I I i

l l I I I

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Sample: Van Eck clinker ash as collected.

Focal Length: 63mm

Interval percentage 10'i ---..-----r---M""'--~--~-r~-H....,.....-----...-~ ............... ---.

I

t l

;I, 5, ~ I I

t

High " Size

1 Particle

In -iah In High % :iie :~ fSize

" .::. ') ~.

" i.1

" .:: . " .::. 2, 2. 2. .. .;, 1 ~· .;;.

: ~ ~ • •'I ·J

~ ~. 5 • t • ; ' L !2,8 :1.8 :7.0 ~~.4 . .::.0 :~.8 - "'1 ! - ' , .. = {"\ - •'I 0

I

.3 •. 3!'24.0 1 i: I"),_, 1 ······'!._ .. , ... ; "'.I")!\ 1 .•••. .,.!.:,,,,, 3 •. 311c.3 3.2117.9 3.l\16.7 ,. i' I I c c JI I J..J t .J

2.9 14.4 "• "'117 4 .:: . 01 ·,). ,.., ,., t .... c ~' 0 L::. I,; 2.7,11.6

10 (u/ll) .

\ H lQI: !Siie

1. 414. 84 •. 2\4.% 1.'.J!4.19 0.913.89 0.813.62 0.7!3.37 (). 7f3.13 0.6\2.91 1), c I 2. 71 :) t .: '~I 5 2 0 .. 512.34

UCT Phys..i cs.

Ir. IHia~1 In 7. ISiZe X

0 1 :; ! : . : ·,3 ;J.4!:.o~. 0.4\1.88 • .,, 1 c (J,.;.,]; '· '71• ,., 11 •• :,, IL I c.:,, 0.3t 11 :.1 i) I 211. 4 i 0. 211 .. 31 ,., · 1 · "" v, ! L, ..::..;;.

0.0 (\ ;"·, '.i I ·~· 1

;,,:,: ... i) I'.) (1 (\ './1'/

•" '.),ii

o.c i} t ~:~ .., ,., v.1.: 1),1) o.o

Spn '1 ..,,,.. - I .. 7

I

t

I

1 l I !

A6

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Sample: Van Eck milled clinker ash.

Focal Length: 63mm

Interval percentage

r !

i I i

;t, 5 t

l I i l j I t I

I r i

1 10 100 Particle size (~~).

i Mi·~ In. !~igh In IHioh In \Hioh In !H~a~ In !Hiah ln ~ S~~n i t 31~~ ;, 1 J!Z2 'I. \S!Z!? 7. \Siie Z \:i~e '· !Size Z ~ · l.33 ~

II '!9 i),0153.3 (),i)l24,(• (i,4 /1(',2 3,8f4.84 .3.412.18 1. ~ ~'~4,3l W

M iio o.~· 1 ~9.5 0.01122.3 1.~ 11c.o 3.:.t4.:.o 3.312.03 t ~ 7.~.c~irft

~ 102 o.0'46.: o.o 20.1 1.s 19.31 3.011

4.19 3.111.22 a: ~ ,

r. 95.2 0.0142.8 0.0,19.3 1.5 18.66 3.! 3.89 3.0 1.75 0 ft D[3,2; ft ! 38.6 0.0 139.8 0.0

111.9 1.4 ls.cs 3.4,3.62 2.9 l.b3 o: ~ 4;auµml

ft 82,4 0.0~37,0 0.0116,7 l,4 7,49 3,6113,37 2.9 1.51 0, 1

! ~6 6 0.0 134.4 A n 15 ~ , o !6 °1 l , 7 '

7 , 9 1 41 o ~ ~:v,o.9· .. , ..

ft ~.·~ n (ll~.! 0 c,:!)114',4 2:8 i6:4a ·1·1·1·~.'~.1 ... ,, o: ~ ,,,_ t"'.!··:~• 'tt u.:2 6:6i29:e i) ···11"' 4 7 8 !6 01 -;•4 ~·Z~ ~·%,~·~~ O. u .~ .• ,~. i

. I I l': :·· ! - . ., i /1 I x I ' -~ . c ~ I ... c I l. fr\ -~ ' ~ ~ ' ~ :. ; ' ~ ~ l • .;. ' II .. ,. ,., t ·, I v •• c, ··'•'.i .... ,, :_;.•) !.::.,.; 't,'t ... :,J\.. .J.v '-•·-·~ .;.,.,;j iJL·,;,•J••jll I c., ., ,-, .-, I -, C. 0 i"\ ti f 11 I. 4 ~ I r:: ·1 ~ ".! c I "! ~ .~ ~ ri I .. r:: c I ~ ..; ,. , .j ._, •• , .. .1, u "', ...

1 ... w , ·.J i.;. .... ·.1 • • .i, .. , . .;.. i,' I ~, .. .;.;Ulna

!Source =. :Samole !Beam lengtn = : 0 mmlModel indc ~ D:r·~:~!i n ~~q. v~ tt. = • 982J o w •.•• J.~P.111 UF~:al l~n~t~ = 63 mm,Obscufat1or = 0.1 14 ,Volume Cone. = 0.0170%~ ~ nPresentation = pil Volume distr1but on !Sp.S.A 1.2•S2 ~!/cc. Shape OFFI

A7

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Sample: Van Eck(-63) milled clinker ash.

Focal Length: 63mm

Interval percentage 101,

i l ! I I I I • I I t I ' I r j

5 '. I I. 1

' i

t I I

t l ~ I

i I

t f ' ' I I ' i 01 .1 1 10 180

Particle size (1,1r.d.

ff ~ioh Sl~e

L3 ; .... .L~ ; .. '

In 'Hiah In Hiah r. iSiie ~~ 1SiZe

!). I 53 • 3 iJ, I 4't • 5 C It:, 1 ) , I 42. 2 o. ! 39. 8 0. 137.0 '.', I :,4, 4 :) • ! ~,, 0 o. i29:s (\ 1..,, 1 'I• ~( 1 I

'.°)I ! 25 I 8

0.0!24.0 0t!)122 I 3 (l, I) t 20. 7 ').0119.3 0.011'.9 !) I 0116 I 7 (\ . ., I · c .:; .; • :; i .J • . J

0.1~14.4 0.3113 4 ;''\ : I 1"' c. ,,,, 1 J..:.1,,; ~ '1 t ! 1 L ••.:.I•"-' v

UCT p hy 'Si .i c:s:.

" . ' '-l I "1 I µ1· ·'h ., :: .;. . " .. ,1.e

De:o pea. r tme:on t

A8

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Sample: Van Eck(-63) milled clinker ash (repeat).

Focal Length: 63mm

[ ! .,

Interval percentage

! l

I T

/. Ci . "' ·r

t t I I • i

1

i ~ I

a~: ~~;--....-...........,,_,_+-+++= ....... ..i.µ>.J..l..llU ......... ~~llL+-l.l..u..:...l..w..+~ .......... ._..... .......... ~~~' .1 1 10 100

Particle size (u~).

ft Hiah ~ Siie

In 1 ~i~h % 1 ~l2E

?n 11H1ah

I. , Siie In 'Hia~ In 'High

X .Si~e % Size

pou~ce =

2. :,! 2' l8 "I 4 I? 07 i.. .. • .J

2.311.88 "'.· ~I ~ 7C . ... I J i ~ t ' "•'

•.•~·It 1 o: ~ , 1 • ~, ... I~ • t V 4

2.4 1.41 "'.• .. 11 1• .;.,'ti.&.1·,J.L ; "'.·It ~"'. .:.1.;.; • ..:..;.

~ ~· I .;. '"". 1. 4 I

:Sa1ple !Beam !en~th = 2.0 mm/Medel indp ~ s:~.o.SJW Leo. viff. = 2.363, ft ,,:-~~ir~

63 mmJObscufation = 0.2012 fVolJm; c~~:. = ).~220%~ ' :i! fVolu~e distrib~t1on !Sc.S.~ ~.0:06 mt/c~.!Shape Q~F~

I I

A9

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Sample: Van Eck(-63) milled clinker ash (repeat).

Focal Length: 63mm

1B ; ·r

i

t I I

~~ s I r '

0i

Interval percentage

.1

n!11~ I \ II I 1 q I I [\

rfirnii 1·1, ililil1 l11h "1!1l 1!1i!il·i 1!jll!l 1l 111: J11

1111li1J'iJI' II 1111111'11~ 111111 'II I 1· I 11\ 11:q1 di Ill 'ii I I ii I I I 1111 I ili;I I )! .. J . ! ! ! I I I l ! i 1 \I! ! '. ! j lj i \11;111 111111 11 I 11: i

rf'll''"'''l''111°!1 1.l11J!11 !Ill~ II 11 ltl L I l i; 1:( 1 Iii Ii Ii ff 1:•• I!'

1 10 mo Particle size (vm).

Hioh Jn 1 ~ioh In Hioh In !Hior. In !Hioh In Hioh I~,, ~ 3;;r, Siie i. 15iie % isiie ;: tSiie i. fSi~e 'I. !Siie ~ 2.13

0. I :.3 .. 3 0, 1 L9, 5 o. ! ~6. 1 (), I !2, 8 0. ':9. 8 0. \ ;,7. () (I, I;!, 4 ,·, I - .., !°: '..,; t • • ~I 'I

I), : 29 I 8 I) I ! :7 I 7 0 I ! : ~ 18

0.0!24.0 0.0!22.3 0.0120.7 ··; ()I '" ., 'I J.71.J

0. (}' 17. 9 0.0116.7 (l,0!15.5 :),:)\1~.4 !) .111.3. 4 11 "i i '"') ::. '/ 1 \,,,; j • - I •'

1 .. 3f11. 6

2.1 10.8 2 I 7 110 I:) 3. l 1 ·:i ~.

3.2 ,. :3'.66 3.1 8.05 2 t 9 17 I 4q 2 I 9 j 6 1 97 ~·V ;~·~? .,;.: I c. '>'~ "I: ~ l '· ~ (•

' , .j, . .;

j ·J. '...!',' ,5.2: pc~rce = ~Fc::Ql lerigt~ ~Pre·;er1tat1c:

:Sample !Bea~ l;ngt I LOG, ~i

= 63 mm Qbscutatio = oil Volume di

AlO

I . ' ~ I

i ~

l I I I t

l I

t 1 ! . i I ! \

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Sample: Matla fly ash as supplied.

Focal Length: 63mm

Interval percentage 10 1r-~-t-~"'!'-~~T-t-,...,_.~--t~"'1'---1-t--f-T~~~--...,......,......,.....,...,....,~~--,i

I I

f t l ~ I I

~ ~ I i I I

t 1 Y. s f ~

I I f ! i

t • I I

0r~~__,_~~~;......;....-1-1-;...;....::lll..l.J...U..f..U..U4WLJ!..W41-4-4J.i.Ji:.+J...U.U~~..l.\-U..i.,..:.;~-1-t...;..;..~--J

.1

ii ~:er: In 1. 5iie .,

" P, :12 o. j : 1 (i 0.

!02 0. r. 95,2 (j ' . ! 88.6 o. ft 82.4 ,,

IJ'

n 76.6 0.

' 7 ~ .. ...

.;.,..:, v •

i ti:..: ,.~

'/. 61. b o. " < ,"\

;, .. ·! ···' 'J.

'1 -:oh I :1:2 I

I .: ~ < ··.I' ·J

~ ~ 9. 5 1!6.1 I '~ 0

i -~.w I :9.8 !:7.0 1- I A l ... •t. If ! :2.0 i - ... ti ..... . c i -~ ~

:i.' i !

,, _ :.. c I

1 Particle size(~~).

10

\Hioh f Siie

ln lHioh I: SiiE

100

'n i ~p·" j I ~ ·..; ~,I

7. n ~.56

0.9124.0 2.8 110.e 2.9!4.84 1.7 2.18 O. A ~r4 <1 1 ~I~, 1 ~ ~ t•A ~ ~~IA en ~ LI~ A~ ~ ~ '~~~~ • 2:r1~5:1 i:r 1$~±r ~:~ i:t~ t:~.t:~~ 6: ~ ···=·j·~ 2.4119.3 3.1 !8.66 2.6,3.89 1.4!1.7~· 0. ft D[.3,2' ft 2.6117.9 3.0 18.05 2.5 3.62 1.311.&3 o. n 1;a1umn 2.6!16.7 3.0 17.~9 2.4,3.37 1.211.51 o. ~ ' 2.~t15.5 3.0 !6.97 2.313.13 1.111.41 o. ~ D[v,0,9Je 2.4i14.4 3.1 16.43 2.2t2.91 1.0f!.31 0. ~ 36.22~mft 2.3113.4 3.1 !6,02 2.1f2,71 A Oti ~~ 0, ~ . ~ 2.Jl:.·2.5 3.1

115.60 1.9!2.52 ~:a!•·•• ! D[~ ... ·10.!,l.ll 'i ,~ ~ 3.1 .5.21 1.812.34 0.71 ft ~·6~u.· ~ft •'"1··.. ~

~Sourc~: :Sam~:e :eeam lenath = :.o mm!Mocel ind~ ~ 8'.v,:.~: , I Loa .• 1ff. : 3.450! ~ 12.97u~! K~oci: ;enct~ = 63 mmlCtscu~iti0~ = ~.!921

1.vo:ume Con~. = 0.0290%; 1

~Presentatiofi = pi! jVolume distribut1:n ,Sp.S.A 0.7626 m2/cc.~Shape OFF

All

Page 102: Town Cape of University

Univers

ity of

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e Tow

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Sample: Matla(-63) fly ash.

Focal Length: 63mm

Interval percentage

4 ,J.

UCT

1 Particle size (l1r:i).

p hy Si .i C::Si

Al2

10 100

De-pa.rtme-nt

Page 103: Town Cape of University

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e Tow

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Sample: Ordinary portland cement from Ulco factory, Anglo Alpha

Focal Length: 300mm

Interval percentage

I. 5

1 I t

I l 1 I

0:~~--1---1-~-1-~---~........,...._ ........ ""l'-"" ......... _..-4-l-+'lo~---4---+-..;--.__-+-+_.,.~___.1 1

i Hiah In ~iah Siie i :·iie

o. ~s~ o. :36 0 I :'l 9 (i. ..·;:4

6: :~~ o. :64 o. : 53 o. :42 o. :.32 ()I ~23

10 100 Particle size (u~).

In \Hiah In \~igh i. !Siie i. 1 :;1ze

0.0! 114 0.)1106 !),I) 198 .6 0.0~?1.7 0.0185.3 o.:)t 79 .:, 0.0!73.8 (l,(1 63.6 o.o 63.8 0.0 5i:;,3 0.f) :,~. 2

i),0 151.3 0.0 14i.7 0.0 144.4 o.o 141.2 0 I 0 l.32 I 4 ;) . () \ :.:1, 7 0 I 0 / ,3.3 I 2 o.o !30.3 o.o 122.7 o·J; 26 I 7 c).~ !2~.s

In .,HiQh 7. Siie

2,:;f 23.1 3,1'!21.4 4.4119. 9 4.1~18.5 .3, 5' 17 I 2 ~ ' I t L '' ... i I 4 \ .I. U t !}

2.9114.9 ., ,., 11"' 9 .JI \I •)I

3.·2 12.9 .., ., t "') ,,

.J,.J .!,.;. • v -, -.: I , ~ "':-·.JI·.,'! • ,i. I.;.

1000

Al3

Page 104: Town Cape of University

Univers

ity of

Cap

e Tow

n

Sample: Lethabo fly ash as supplied.

Focal Length: 300mm

i I

t i

r - i I. ~ .

Interval percentage

I ~ I i t I

1 t i I

i I

t l I

I I

1

0i..._~~~-+----t-+--t'"'"i'"""1"'~ ....... -+ .......... "'+-""""'l'-~-'-'+'"l""-"'--~-+-~+-+-~.........,--~--

1 10 100 Particle size (u~).

, Hiah In ~~igh In Hioh In Hian ~ Siie 'I. ! '5ize 'I. Siz~ :( ISiZe

0.0::54 0.0 1 :36 0. r; ! :19 I\, ............. ., v • v ... v~ 0.0~:90 l),(1!:76 o.:;1::4 G.C~.53 o n · 4~· 0. f· 1: ... ~ I)' • ·.J~

0.0':23

no 11 4 o: i) ! 106 0I()198.t, ,, r"• I-~~ , ~·;:: 1 1 ~.4 •.I. •J. 8..;. ~· 0 rd 7n <

• ,, 1. , •. .,

0.0 73.9 :) . :) 168. 6 OJl6.3.S 0.0159.:i (J,0155.2

T •· j H: • ;.1· r~ ~g Ii I. .~1:e

l. 7 .. !':". l ,..,, 1 IJ ...... • '"' :,. .....

1 .S! 19. ·~ • < ; I '·~ ~. . . ' I • .J • ..J , ; ! < , " .i.1/ Li,.:

1. 7' j J ,., ! Ci.!)

1. 9 I 14.~ 2. l ! 13.9 ~· " i l:.9 2'. 5 \ l"'; ;", i.:. l •i

2.6! '< " .! .i.. ~

In I.

.;,;,

" ,;. . ~ ~I

" '"' , ... ~I

-~' ; ... ., ~· ~ .

Hi ah ln So an SiZi ., . ., ,,,, ,, .; . v' .

I ; ·:. ~ .-, ~ D~~·l~ ~~ ; ~· I

0 '' ~ :o .. •1;.••; I , ... ~ ~I -. ,, " i o. )/ •• lo ~· " ' ~='~ 11 ; u ,.j<lf :,..

~ ~ e: t~ U! I . 1.n ~ i ·~ . i ~ ~ ~ i

; f • .:. • ·~I

~ I I) I~· j ff I r , 1 , :t i6'~4 ~·

. ! " lL.t11ft I '• 'i' ~ .. '

Jc: or' .JI I ., ,J,1,,11)

~ -I ,, , . I - \.:,L.', • J ~ I n ! .. : :.~ ;T, ~

! ~

Al4

Page 105: Town Cape of University

Univers

ity of

Cap

e Tow

n

Sample: Lethabo(-63) fly ash.

Focal Length: 300mm

:t. 5 t I I

~

Interval percentage

t I

i

1 t

I 1

01~~~~-+---+--+-'i'-'i'-"l'+'T' .................. '-!-'..l.~~ ..... -H-+++-~--~+---+-+-H-+-~---

1

9 Hiqtj ft Siie

Jn ;~f~; •;

'· ' !), I ?54 0. ~ :36 I). ! ?\ 9 0 I 1204 (l. l 190 o. l 176 0. ! 164 i)' ~ 1 :,3 0' I ·. ~ ~· r, '1: ~~ \i. i; ~~ i). - ~··

In

·10 100 1000 Particle size (u~).

I Hior1 ., 1Siie ;, Jn !Hioh In !Hiqh ~ ,.. l~iah In ft Soar: '" I. !Sit; .,

lSiZe '!. !Siie 'I I ~ ,.,

/, ,, .;. .. ; (

I

o.o 1s1.3 o. 1~·~ ~ :, :io.4 .J, r::!,:~ fl o,o \47.7 o. \~l:a 2. \9.64 ~ ~ :~.0s~mft o_,1 .11~. !4_.1,·~.- o. 119.9 ~. J1 C·o=···.~._: .. ;.:_ 2. ~ ~ '····· .- .... 0. l:S.5 2. 2. ft D{3,2 1 ft o.o 1:e.' 1. 117.' 2. 17.76 1. ~ 6.34u~ft 0.0 l.3:;,7 l.· 116.3 3. 17.21 1. ~ '1 0.0 133.2 A· !:~.9 ~· 16.71 £· a D~).~.?'~ o.o 1

130.s ~. 11.:.? .2• ~~·,;_·: .. ~ ), ~ ~··: =·:;!r'

0 , G 2 8 , 7 : , ~ ":• '= .= • I ... · • l,,i v ~ , P1.~···· ".·. ~-.. :.(· ·: c·.··.·.,· .. -;:. ·•••• •• ·ir,···, ~,',, ;),G 1:.:.7 i. \i~:b I ~ n (;.c ~:4.b ... !!i.2 3. I

I I I i

A15

Page 106: Town Cape of University

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e Tow

n

A16 Sample: Duvha fly ash as supplied.

Focal Length: 300mm

Interval percentage 10.

/. r .J·

I I

I ' I ! I t I I I t

I I

0; I. i:

1 10 100 1000 Particle size (ttr.i).

I I I I

~iah In : j ~ g ~f In !YiQh ln !Hiah In I Hia h In I Hio r1 In Spin Size " ., 'S1Ze

., !Siie I. !Size ., ISiie ., ":I ~ c

/, :il ze lo '· /, i, "°'"''

~ :.c,4 r•. '254 0.01114 0.0 151.3 0.0123.l 2.4f10.4 1 I D~4,3; ft ..... ., . 524 0. ; 236 O.Ot106 o.o ... 0.1121.4 2.2f'1,b4

., "• 1 . ;;;,,: ·). 4.~.µ.n, ft ~88 o. ~ '"H n 0.0198.6 o. o ! 44. 4 ;).4!19.1 2.418.97 1 ~ . .. ,.., ~ ~u "' ! 4 :.4 I). · :o4 c~.091.7 o. f) 141. 2 i.:11e.s i.7,~.34

. • q.:i,.q ~ .,. ,,

" ,.,., 0. ; 190 0. I) 1e:\I3 0 I\ !38.4 l.81i7.2 ~

' "· '.v .;.,()I., 76 •.it 7; 1' UK:~ ~ :.~·? 0. ; . 1 L tJ.0~79.3 o. () f 35. 7 2.4116.0 .3, .3 ! 7 I 21 ., i ' ... :v ,J,

! n .:65 ... ... '.)I 0' 73. 8 (j, c l'P "! 2,'1! 14. 9 3.~!6.71 ' D~v,f.\.9}ft ij

1;. -~"' ' .. .; ... 1, -" ('t I ' ~ ; ~ ;) I(;\ 68 I 6 o.o 1-3~) I 8 ~ "'!I 4 ~ ..., 3.616.24 1 i .. 9.89um J•) i ... J ... • .• , ... , ........ 7 ., .

~ •• t ,., '142 /', r1IL1 •: ... ,, I ""tO -, 1' i I!":' n " 61 • "O < 8

ft ,.J .,, '"•"\'.J· .. '1•.J Y: ~< 'i.u.,. ·;I .. It~. I~. •)I \ ,j I 0 . :13 ,. '~~1 0 I!) :j9 I 3 \26. 7 ' c ~ :! [ .._, ' ::~ ' 1 : ij t ... : .; v. 1.: .j I 0 \ .i41 iJ .j. ··'

I 17'! c. I ~ ..,.1 0.(1155.2 0.0 124.8 2.7 11.2 3.4f ~ ! . ·i'2Ulf;~ ,. .. I ·J ...... ..;

;source = ii:--·1 1 ·-,j· ..,:;_a er1c I.

,~·resentatic~

"

:SamDIE 1sea~ len~:h = 2.0 mm!Model indp I o;~.g~~:~ I Loo. Jiff. : ~.~.271 , ....... ~rr,,.

= 300 mm,Obscufation = 0.1934 !Volume Cone. = O.C286Zr ' = pil !Voluffie distribution ~Sc.S.A 0.7529 m~!c~.,Sha=e OF~~ . I .

Page 107: Town Cape of University

Univers

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Cap

e Tow

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Sample: Duvha(-63) fly ash.

Focal Length: 300mm

Interval percentage

I

t I

l

t I r i I

t i

:I. 5 t ~ !

1

• ~iqh Size

In \ \.1iah ~ !3iie

(', ! -.c,4 (I I-::;.~'-"' ~,.;~ 0. ~ 219 0, I :of 0. I: 90 0. i: 76 f i. ' .. ) ' i ~~~ i)' l • .J.J

0. ! ; ~~ 0. '. ,, .. o. : :23

In Hiqh ;: Size

\),!) 1114 :) I 0 \ 1 !),~ :: .• f;f 98 .. ~ o. 0191. 7 O.Of85.3 0.0!79.3 0.011:.s 0.0168.b O.Cf6.3.8 0.1), 59. 3 f.. !·. cc "i iJ',\..', )..,i,4

In IHiah 7. I Size

0.0 !~;1,3 (;': ! 47. 7 ()' 1 ! 44' 4 0.1 \41.2 0.1 f 38.4 ()' 1 135. 7 0. i '3.3. 2 0. l ) 30 I B 0. ~ l 28. ; 0 •. 3 126. 7 (i,6 24.8

I

l « I niah I. ISiZe

I).·;: !23. l 1 .-,l"H '1 .. I.:,.' ... I~

1.~1119.9 1. 7118 '5 1.8117.2 2.011.~.o 2.2!14.9 ~ , I l' C· -.. ; I .; .. , ·! c 1 ·"':· 9

r~1H:~

In l~igh In 7. I 01 :e 7.

:. 9.! 10. 4 3.019.64 3.0!8.97 3. 1!9 .34 3.1!7.76 ~ "'I 1 "') t

3:41,;:7: 3.5!6.24 3.5!5.80 ~·11 ... ~ !

1000

~s~~~c~ = :S~mpl& !Bea~ lensth = 2 O mrn!Moc~l indo ' :~v~O.S)~ ' I Lo:J, ~:iff, = .9101 ~ 1~.601.rn:ft ~Focal len:t~ = 300 rnm!Obscufation = 0.1 69 !Volume Ccnc. = 0.0305%• ~ !Pr~;entatlon = pil 1Volume distribut on Sp.S.A 0.7:01 m?/::.,Sn~:e OFF'

A17

Page 108: Town Cape of University

Univers

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e Tow

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Sample: Van Eck clinker ash as collected.

Focal Length: 300mm

Interval percentage i0 ,.--.--~.-------......... --.......... ,......,......--._.__.._..-t--1 __ .,......,...... __ ~--...-~__,. ....... ~---,

t i I • i I i t I i t I i

'.I. s. t I I !

r !

~ t I ~ I l

Hi ah In '1ioh ft SiZe ~ lSiZe

c ! •

"

~o~ c ~ . .II . .-.: ..

! 482 R 454 ! 4"' ft :92 I °' !. c.

~ ~339 ~

~ ! c ·J .. .,; ,..,..._~

i! ... : j

ft 273

3 I ~ 254 3. '"'6 3, I 219 2. ! 204 2. j 190 2. ~ 176

~: : i~f~ ., ... ,, ~· ~~~ .: I i 132 ,, '';~ i. I • .:.·.•

10 100 Particle size (u!ll).

ln !Hioh In 'l. ! Si ie 7.

'

Hioh In Si ie 7,

Hi ah Siie

l.6 151..3 1.5 147.7 t c I.,,• " ~·i· I~~·~ 4.1...J ,Jot .... 1.5 138.4 !.5 .3~1.7 1.6 133.2 1. 7 t .3() I 8 1.7 128.7 i .., i "6 1 .i. t cj 0:. I I

1.3 !24.8

1.8 23.1 1.7\21.4 1.7119.9 1.6118.~1 • 'lt'7"" ! • b I J.1 I' 1.6\H.O 1 c 1" ..,

1 '•I 1J.'+1' 1.S 13.9 ! c. I ~ ~ ,., • ' J \ • .:.. 7 l.~;i12.0 l.4!11.2

In Hiah In 7. Siie 7.

l.4110.4 ;), 1.3~9 .64 o. l.2!8.97 I). l.118.34 o. 1.17.76 0 . 1.0 7.21 9.· 0.9!6.71 1;, 0.8t6.24 (), o.s1s.ao o . 0.7 . i), 71

1000

Span ~.~a

~Source= :Sample !Bea~ length = 2 0 mm!Model ind: ft D(v,0.5]~ ~ 1 Loe. ~1rf. = .:1421 ~ lii4.70uml ftFocal lenct· = 300 mm10bscufat1on = C1.2 ?t:1 !Volume Cone. = 0.152:,1.t . ' jPresentat:c~ = pil

1Volume distr1but en

1Sp.S.A 0.1627 ,,: /cc.ph;;;e DFFij

Al8

Page 109: Town Cape of University

Univers

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e Tow

n

Sample: Van Eck milled clinker ash.

Focal Length: 300mm

Interval percentage

10 100 Particle size (u~).

I HiQ~r Siie

564 I s24 I 48a " 454

"i· ~~~ 365 ' 339 n 31s ft 293

...,,~

~I ·J

In 1Hioh 'I !Siie ~

i

O.C!254 0.0,236 l),i) 219 O.C\204 0. (; l 190 0. 0l176 o.'~116; o.c 15.; 0.::1142 O.Cl132 0.Cf 123

In High z Size

0.0 114 I) ~,. ''6 11..• l 11

0.0 98.6 O.Oj91. 7 0.0 85.3 ,., ''11"' 1 >J 1 I_. I 7 I •J

0.0 73.8 0.0,68.6 0.0163.8 O.Oj59.3 I (\ c.c ') C, ; v·J, o.

In ! HiQh % Siie

o.o I c ! ~ i"''i.1·.'

O.G 47.7 0.0 44.4 o.o 41.2 0.0 38.4 0.0 13~1, 7 0.0 133.2 o.o 30.2 0. 0 128. 7 0.0 126.7 0.1) f 24.8

In IHiQh Z ;Siie

(1 f'! I'°'.'~ • ·JI 1.J IL·~ • .L r, r·, 1 "°'.'1. 4 .) I',/, ... J. I 0.0 19.9 0.0118.5 0.1 17.2 0.3116.0 . 0. 6' 14. 9 0.9113.9 1.2112.9 t·4112·Q •• 6: 11 ...

In I HiQ r1 ., Si ie '· i

1.6 l 0. 4 1.819.64 2.0 8.97 i.318 .. 34 2.6~7.76 ,, t"".I"' ..... 'IC j I"' .L 3.0 6.71 3.116.24 3.215.80 ., ,.. ~·41 .j • . ; j

1000

In ! Spa:--i 'I 2.26 '•

3.4 ! 0(4,3

.,.. s I B l t• • . 111 d . . d • - ' . • " pource = : amp1e eam eng r; = .::.o ;U;,,,o El in p ~ . .'.\,i).:Jr. r. Loa. Diff. = 4.4161 ' 7.~3~;;~ ;Ecc;l len;~h = 300 mm!Obscutation =.0.1986 !Vclu~,e CuC;:. = e.01·;:,f.l_ ~ .. fre;?ntat1:~ = 011 1Volume a1str1but1on ~Sp.S.A !.!354 m2/cc. 1 ~hape OFF

Al9

Page 110: Town Cape of University

Univers

ity of

Cap

e Tow

n

Sample: Van Eck(-63) milled clinker ash.

Focal Length: 300mm

Interval percentage 10 r----"1""-1--.~'"i"""t"~--...,.._---.-__......,..,..~--....--,_...-i-...,.-----.1 '·-

% 5

!

j I I I

t

l t

1 ~ i

1ff11!11111n1~ t 1

1W111lli11

111111, h~ 1

ii lii1! 1'1'111 ~ I 1·11 ;il1i !11' I 11:1111 1!1

liil\il!i111'1i 1 I · 4 l 11 , ·I'' I' i • ! 11 '11· ,!"i '· 11 1 I "I 1 I 1 'It;

l ii l 1'11 11111111'1 !liii., l 0·~~~-+--+~--+1~11~11 1~111~1~1 1•1 '~1!~·~1 ~q~·1 ~·~...,_~l-+l~l~l~l~l+l~~...;......--;-~l-+l~i~i~l---i~--'I

1 10 100 1000 Particle size (uM),

A20

Page 111: Town Cape of University

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e Tow

n

A21 Sample: Mada fly ash as supplied.

Focal Length: 300mm

Interval percentage 10 i,--~-----~..--~..--~-----.------i~~~--~----.--.-........... ~-,

I

t i i I

i t l + I I I I

x 5 I l I I

t 1!

I I

t i • I t 1

\ i t 1' !

0~i~~----1~--+-'ll-'.jUjj.11-11'-1-~""'"'"4"""'-""""""''"'ll---+-l~H-+-~~------1-+.-+-'4-I..+-~-''' 1 10 100 1800

Particle size (um).

Page 112: Town Cape of University

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e Tow

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A22 Sample: Matla(-63) fly ash.

Focal Length: 300mm

.. Interval percentage 10'i~ ~~---.--.-.......... ._..,H'"t"~~~---.-.,.........._.~~--.~----,....,....,....,..'1"1-~--.

~ i i I

f 1 t ~ i i ~ I ~

~ 5 i n~ J~ll

, ~ 11, n 11,

t I I 11111

1

1

I t I I I 1 '111I1 I l I I \ 1 I 1111' II I 111 I 1· 11 I l I i lildiili II I lill 1 I ii!: I 111 '1 I I II I I' l 1111\ i \ 11• i lli!l!d ''"' i iii !lf'il 0~' ~~-----~--! +:l1~q1~111~:11-'l~!!~l!~l1~q~11~11~·,1~·h~1-;-1~1~1~1+1~1~~;-.-1--1i--+-1-1~. ~· ·~, .~i~--''

1 10 100 1000 Particle size (u~).

:,1oh In :-:oh In HiQh In High !:-1 I Hi oh In H~gh l" Sp.sri P.

.. I

; ~ Ze 7. I: lie ,,

lsii.e ~ .Size ., Siie z ,Size " t.98 '· ,, ;, ;,

~ :.:4 o. ! : 54 0I01114 0.0 51.3 o.o "'' . ' 61 ',.. 4 • ;, ' ~ : , . ft

i.·J' L .J. J..;,

ft "\;. c ~··~ft : ,.., ~ (\ I.-: I. 0. 0!1Ci6 ;\I\ l47,7 ()I 0, 21. 4 2.7,9.64 ~ ,,,;,; , '. : -··'-' v. !) .,, J.·J t .,1.;.1.';11 I

"

488 o. I:: 9 0.(;198.6 iJ.O 144.4 O.Of 19.9 2.318.97 ..

~ ~ .j.

454 "· ! : )4 l) I 0' 91. 7 0 ,, 141.1 o ,. ! ·a • ,., ., .,. ' ' ~ ~ ~ . ., ' ft IJ' ,\; .• ,, 1 ',J ,, .• i 8 ... i't .J.

I ".,., 0. •:=o ,. ') r~ . 0.0 l"'r. 4 o.o 17.2 2.4 7.70 ..

ft ··7:16u~;J ... ,..::. 1).. Q .•. ! • .:;; .,j·j I ., . 392 0. 1. ~ .. !), c; i9 I 3 0.0 , •. 7 0.5116.C . , '7 I -r '".= ~ 4 • ~ I • " . ,;.;,, ... I' I,·.--·

~ .,. ~ c. " I • - 4 0. 1)

173.8 0.0 1~1 "I 2.2114.9 3.:)16.71 4' ~ ~v.o.911 '•'""'" ., , \·.•·.JI~ '1"'.'r"\ !l t I ~.3 (; ,, ] •·:J i (I. i) l"U\ O ",., . .,. ,., 3.3 6.24 . .;;,,:.7 .,, 'I 1 ·~ 1.., 1~ 1 Q j ·J~' I'-/ • • i ;.; • 'i

~· •6~91um

~ ., ( c 0. I' { -. (• ,., L • •· (• (• 128.7 ~i,112.9 "1 I C l"\1"\ ~ ! . .;; • J -"':' i I (.,I' l..·.'t C ,,v .J. 4 .J. Q!,1 ,, -.r-.~ '" ~ -':'.· o. !) 5'?' 3 o.o , .... , i c 6 j t"' . 3.4, I :·: l; ~:~J.; .;, '..; •1, i ~ :~ I .:,.•j I ( .J • '~ • IJ

' ft ,..,.,,,,

0. 0.01 ~15,2 o.o 124.8 4.6, 11.2 3.3! .:.. : .j I•_..,.

1 ·=c"'"e - .C,mple 1Be'm 1 ""·nt"i.. - '\ ,., •·•· 1Mc"e·l 1"•dp I ~[v L'l c,, (l..,.,_.11. - • ..,g t I "" ~t:•I'~·:· - ._,.,1 •11'1!1 IJ II fl i.J{.,, '""J ~ I Log. uiff. = 4.8581 · W .1.1:urn Fc:al le~at~; = 300 udOb;:uration = 0.1962 1vcluJ1e Cone. = 0.0283::tl:;==::::;:;;:;;:::i ~Pres~ntaticn =pi! Volume distribution So.S.A 0.7732 ml/cc .. SM~pe OFF

Page 113: Town Cape of University

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e Tow

n

tn - 0 C\J U) 0 N

""" Q'l ..... c:

~ 0 (J .....

X-ray diffractogram for the Lethabo fly ash

1-- I T IJ') 0 IJ') 0 C\I c (\J 0 UJ ~ (\J ....

It) N

A23

• ....

--~O

0

0

Page 114: Town Cape of University

Univers

ity of

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e Tow

n

tn - 0 C\J en 0 (\I +J O"l ..... c:

~ c f.J -

X-ray diffractogram for the Duvha fly ash

T •• r 1-·1 LO 0 In c C\I 0 (\I c ~ oq' (\J .....

A24

-.-\{')

C\J

• -..

0 •

Q

Page 115: Town Cape of University

Univers

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e Tow

n

X-ray diffractogram for the Van Eck clinker ash A25

.... co

-------·--------------------------~------_.. __ , __ .,._ __ , __________ _.,{\I

F I in ~ c in (\J en 0 (\J (\J ..., Q'I ID ..... c::

~ Q CJ

'-"'

I 0 Ln c 0 C\J 0 ~ C\J ~

• -

---=~====~

0

--~~--~-----~ 0

Ln Q

N 0

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A26.

X-ray diffractogram for the Matla fly ash

-en

0

-----------

0

0

I -, t t= \Cl ,..., c In 0 in 0 \l) 0 C\1 en 0 (\J 0 C\J 0 C\I I

C\J ~ O'l tO 'oe:f C\J """ Q ... c: :;, c tJ ~

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APPENDIXB

• Concrete cube results for Ml, the control mix

• Concrete cube results for M2, the Lethabo(-63) mix

• Concrete cube results for M3, the Lethabo mix

• Concrete cube results for M4, the Duvha(-63) mix

• Concrete cube results for M5, the Van Eck(-63) mix

• Concrete cube results for M6, the Matla(-63) mix

• Concrete cube results after 3 days of curing

• Concrete cube results after 7 days of curing

• Concrete cube results after 14 days of curing

• Concrete cube results after 21 days of curing

• Concrete cube results after 28 days of curing

Page

Bl

B2

B3

B4

B5

B6

B7

B8

B9

BIO

Bll

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Concrete Cube Results for Control Mix Bl

Cube Sat. Vol. •Sat. Mass: Density • Compr.Str • (ml) (g) ((kg/mA3) • (MPa)

3 Days : 17109/1993 A 1016.8 2473.7 2.433 18.3 B 1012.3 2462.8 2.433 16.4 r---·-----.. -·--·· .. -·-·---7-·-·--·-------·-----------~---· c . 1020.1 . 2484.3 2.435 . 18. 1 D 1004.3 2444.4 2.434 18.3

Average • 1013.4 2466.3 ' 2.434 -,-~ Std. Dev. • 5.926 14.753 0.001 0.798

7 Davs : 21/09/1993 A 1014.9 2466.5 2.430 24.5 B 1016.1

• 2494.3 2.455 27.6

c 1005.2 2459.9 2.447 • 26.1 D 1016.3 2470.9 2.431 • 26.1 . ........ ... -

Average • 1013.1 2472.9 2.441 26.1 Ste. Dev.• 4.607 12.961 0.010 1.096

14 Days : 28/09/1993 A 1019.6 2488.2 2.440 32.4 B 1020.3 2490.1 2.441 33.4 ·--'--------'-----I c 1014.0 2476.8 2.443 32.4 D 1012.9 2469.1 2.438 34.5

Average-101-6-.7·--+-24_8_1-.1__,._2_.4 __ 4_0 __ 3_3_.2---1

Ste. Dev. • 3.283 8.572 0.002 0.867

21 Davs : 05/10/1993 A 1017.6 2491.2 2.448 36.6 B 1020.7 2491.3 2.441 36.1

~--~-~--~------4 c • 1013.0 2475.5 2.444 37., D • 1012.0 2464.7 2.435 37.4

Average--·-1-0-1-5.-8--2-4-80-.-7--'--2-.-44--2--36.8

Std. Dev. • 3.519 11 .243 0.005 0.495

28 Days : 12/1 0/1993 A 1019.6 2483.8 2.436 38.4 8 1005.2 2448.2 2.436 39.8

>--.. ····--·-------·--·-·····--............ --· ----·---·-· .... -_ ......... __.__ c 1008.3 . 2460.8 2.441 38.7 D 1001.3 2438.4 2.435 39.1

-- .. ···-·· --·····--··--- ····-······-·-··· --·· ···--··-·· .. ---··-... .

Average . 1008.6 2457.8 2.437 39.0 Ste Dev. • 6.818 16.982 0.002 • 0.524

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Concrete Cube Results for Lethabo (-63) Mix B2

Cube Sat. Vol. ·Sat. Mass Density •eompr.Str (ml) (g) ((kq/mA3) (MPa)

3 Days : 17 /09/1993

A 1018.1 2491.8 2.448 12.5 B 1007.8 2455.3 2.436 11 .4

. -····-.. -··-···---······--·-·····--·· -····· -... ·-·····- --·· ----·-·--·--·-----· ·- ·-·----·· c 1009.0 2453.6 2.432 10.5 D 1019.0 . 2478.6 2.432 10.8

Average • 1013~2469.8 -·

2.437 11 .3 Std. Dev.• 5.103 16.079 0.006 0.765

7 Days : 21/09/1993

A 1013.6 2461.0 2.428 16.9 B 1017.5 2477.8 . 2.435 18.8

~434 -·---c 1015.5 2471.9 19.0

D 1000.3 2427.0 2.426 16.9 -------•••--:-"'"""•"--•-''"" __ , ___ ,,, ___ ,,,,._, ___ ,.,., ... ,, . ., .. ""'-"'"' •••"'"''"'' ' ''-'""--. ----"'"'"·--• Average · 1011.7 2459.4 2.431 17.9 Std. Dev.• 6.739 19.667 0.004 1 .002

1 4 Days : 28/09/1993 A 1007.2 2454.8 2.437 22.2 B • 1009.6 2447.6 2.424 . 21.6 c .

013.7 2473.2 2.440 22.4 D 1015.7 2475.9 2.438 20.9

Average . 1011.6 2462.9 2.435 21.8 Std. Dev. 3.338 11 .987 0.006 0.585

21 Days : 05/10/1993

A 1014. 1 • 2469.8 2.435 26.6 B . 1007.3 • 2457.6 . 2.440 26.0 ,....

• 013.6 .

2472.9 .

2.440 26.3 '-'

D 1009.3 •

2458.5 2.436 26.4 .... _ -· Ave~age 1011 2464.7 2.438 26.3 Std. Dev. • 2.869 6.747 0.002 0.217

28 Days : 1 211 0/1 993 A 1020.1 2489.2 2.440 28.5 3 1017.8 2496.5 2.453

• 27.5

,.... 1008.3 2460.8 2.441 28.4 '-'

'.:) 1001.3 2438.4 2.435 •

28.6 ·-···· -·····--""' ···-··-··········-··· ... ~·-····-···· ···-···-·-.. ······· Ave~age . 1011 .9 2471.2 2.442 28.3 Std. Dev.· 7.539 23.174 0.006 0.439

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Concrete Cube Results for Lethabo Mix B3

Cube Sat. Vol. . Sat. Mass· Density · Compr.Str (ml) (q) • ((kg/mA3) . (MPal

3 Days : 1 8/09/1 993 A 1012.5 2445.7 2.416 10.3 B 1004.9 2446.7 2.435 10.4

··----~-·- -···--c 1005.9 2446.7 2.432 10.0 D 1011.2 2451.8 2.425 9.4

-· Average 1008.6 2447.7 2.427 10.0 Std. Dev. 3.277 2.388 0.008 0.390

7 Davs : 22/09/1993 A 1000.9 2431 .6 2.429 15.5 B 1005.8 2449. 7 • 2.436 16.1 -----·--· c 1007.0 2460.2 . 2.443 15.3

.... _ ... _c:> ·" _ _J_qQ_?_:~--?~~~-2---• _?:~_??_ -i------I~-"-~---·· Average 1004.1 2445. 1 2.435 15.8 Std. Dev. • 2.454 10.824 0.005 0.444

14 Days : 29/09/1993 A 1013.7 2466.6 2.433 21.9 B 1005.3 2437.4 2.425 20.4

1----------~-----~---··-··-·------·-c 1007.1 2457.2 2.440 . 21 .4 ,____D _____ ~J.!~§ ____ 2454.9 __ ___?_:_~~? 20.1

Average . 1009.4 · 2454.0 2.431 21 .0 Std. Dev. • 3.370 10.552 0.006 0.730

21 Days : 06/10/1993 A 999.3 2424.3 2.426 25.5 B 1013.3 2467.3 2.435 25.0

------c------·;o-;4~-24:;:;-:22.441 __ ._ -24.9-D 1008.0 2459.9 . 2.440 . 25.1

-Ave~a.90~08-:9-r-2457.2-· -2.43-S-_2_5_. 1-1

Std. Dev. • 6.065 19.948 0.006 0.228

28 Days : 13/1 0/1 993 A 1010.4 2461.5 2.436 27.3 a 1006.4 2450.4 2.435 21.2 c 1-01ia··-·--24sa:o--+--2-:-434--·-2-s:2-o 1008.8 2459.5 • 2.438 27.5

-·-· - ··---·-··-······ ........ - ·-···· Average 1009.9 2459.9 2.436 26.8 Std. Dev. 2.688 6.296 0.001 0.930

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Concrete Cube Results for Duvha (-63) Mix

Cube Sat. Vol. Sat. Mass Density • Compr.Str (ml) (q) • ((kg/m~3l · (MPa)

3 Days : 18/09/1993 A 1003.1 2412.6 2.405 9.9 B 101 1. 1 2444.0 2.417 12.5

·--··"·----·------·-· ··-·-·-c 1011 .6 2428.0 . 2.400 10.5

D 1011.0 2443.0 2.416 . 10.9 Average 1009.2 2431.9 2.410

. 11.0

Std. Dev.• 3.529 12.819 0.007 0.963

7 Days : 22109/1993 A 1010.2 2436.4 2.412 16.2 B 1002.5 2419.1 . 2.413 . 16.9 ---~- _____ ... ___ . ______ _.:_ ________ , __ _ c 1007.3 2434.8 2.417 16.7 D 1020.8 2462.8 2.413 16.9

--A.~e~a9e-'--1-ofa.·2·--~--243a·:3-~- -2:414---~. -16:1--· Std. Dev. •. 6.709 15.690 0.002 0.286

14 Days : 29/09/1993 A 1012.9 2446.1 2.415 22.0

1 __ B ___ 1_01 __ 7.1 2455:_~---~--.?..:~]~ 22.4

c 1019.3 2464.9 2.418 22.4

~ __ p ___ 10 __ 1_4_.2 _._~~~o.'!__~26_~• -~~-:~-----Average · 1015.9 2456.7 2.418 22.1 Std. Dev. • 2.494 6.987 0.005 0.295

21 Days : 06/10/1993 A 1026.1 2498.7 2.435 27.7 B 1008.0 2441.1 2.422 26.7 -e:· _ _,__1_0_22."7-• -2474~2---2.4;9--• -2-3".4-D 1008.8 . 2444.4 . 2.423 • 25.0

·-Av-e-ra_g_e--1-o·-1-6.4-. ·2464~6··-··2:425---~-25.·7"--

Stt. Dev. • 8.095 23.533 0.006 1 .642

28 Days : 13/1 0/1993 A 1014.8 2459.9 2.424 29.7 B 1022.4 2470.9 2.417 27.2 ,___c ____ 1_0_22~2478T.-;-.-2.:·424---• -27~2----D 1000.8

-·--··· ····-·······--··

Average . 1015.1 Stt. Dev. 8.779

2428.7 2459.5 18.922

2.427 . 29.3 - 2.423 --~-----28.4 ---

0.004 1.159

B4

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Concrete Cube Results for Van Eck (-63) Mix

Cube Sat. Vol. •Sat. Mass• Density \ Comor.Str (ml) (q) ((kq/mA3). (MPa) .

3 Davs : 1.9/09/1993 A 1022.0 2473.6 2.420 12.5 B 1004.5 2423.7 2.413 ; 12.4 c : 1012.1 2446.4

i 2.417 12.8

D 1020.1 : 2466.3 2.418 13.5 Average 1014.7 2452.5 2.417 12.8 Std. Dev.• 6.951 19.380 0.003 0.430

7 Days : 23/09/1993 A 1013.0 2446. 1 2.415 19.2 B 1022.9 2467.9 2.413 20.8 c 1004.5 2414.7 2.404 19.9 .

--··-··Q-··-----: 1-9?§_'.~--·i--·?.~?~:.~ ... ;--~:~~--~g.:~---Average 1016.8 2450.3 2.410 20.1 Std. Dev. · 8.645 22.821 0.004 0.612

14 Davs : 30/09/1993 A 1011.8 2446.3 2.418 23.7 B 1013.6 2451.6 2.419 24.7

f~-----~·~·-'--·-c 1013.6 2449.0 2.416 25.6 D 999.5 2424.1 2.425 26.0

,_A_v_e-rage_: _1 a°0-9-.6---+--2-4_4_2-.8--'--2-.4-19 _ _.___2_5-.0--i

Std. Dev. 5.892 10.929 0.003 0.886

21 Davs: 07/10/1993 A 1009.6 2433.2 2.410 B 1014.6 2447.3 2.412

1----~--~~-c , 012.3 2439.0 2.409 __ D __ ._J _ _g~_Q_:.4. __ 2413.9 2.389

Average 1011.7 2433.4 2.405 Std. Dev.• 1.928 12.297 0.009

28 Davs : 14/10/1993

29.3 25.9 30.3 27.8 28.3 1.659

A 1014.6 2461.1 2.426 30.7 B 1020.3 2453.0 2.404 31 .1

-c-·----~-,-014·:a·--'- 2439-.-9 2.406--30:1 __ _ _ . ___ D. .. 1024.0 2484.5 2.426 ----•------~g.9 ___ _

Average 1018.f'- 245ifEf ___ 2:415 · 30.7 Ste. Dev.: 4.068 16.232 0.011 0.374

BS

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Concrete Cube Results for Matla (-63) Mix B6

Cube Sat. Vol. ·Sat. Mass. Density Compr.Str (ml) (q) ((kg/m~3) (MPa)

3 Days : 19/09/1993 A 1003.9 2459.3 2.450 11.0 B 1007.0 2458.3 2.441 10.0

..... ---·-·--·--·····-·-······-·-·-·-c 1005.2 2457.6 2.445 10.4 D 999.4

2450.7 : 2.452 . 11 .2 Average 1003.9 2456.5 2.447 0.7 S:d. Dev.· 2.808 3.388 0.004 . 0.477

7 Days : 23/09/1993 A 1007.7 2461.1 2.442 18.6 B 996.4 2424.2 2.433 16.4 ----c---· 1002.s-· ·245s.,----2:441-· ---:;-g~1 D : 1003.6 2450.9 2.442 17.7

Average · 1002.5 2447.3 • 2.441··--·-1a.o ---

S:d. Dev. 4.047 13.880 0.005 1.026

1 4 Davs : 30/09/1993 A . 1006.3 2463.4 2.448 23.7 B 1004.2 2456.7 2.446 22.2 -----····---.-;--------·--------··-.. --··-·-··-···-· --····---c 998.2 . 2438.4 2.443 22.3 D 1010.0 2469.0 2.445 22.0

Average·-'---1-oo~f1-· ··2455~9··--;.-2:445--~-- ·22~·--··

S:.:::L Dev. • 4.276 11 .521 0.002 0.673

21 Davs : 07 /10/1 993 A 1004.0 2457.1 2.447 . 26.3 B . 1013.8 2475.8 2.442 : 25.7 c .

1005.3 2457.3 . 2.444 24.4 D 1002.9 2453.4 2.446 25.7

Average 1006.5 . 2460.9 2.445 . 25.5 S:d. Dev.• 4.299 . 8.742 0.002 . 0.694

28 Days : 1 4/1 0/1993 A 1003.3 2461.7 2.454 29.2 B 1009.2 2465.8 2.443 26.4

-······-- ······--~· .. ·--·······-·--· .. ·---·-··-· -·······--·---·-·---····--;o---·-.. -·····"'""·-·-·····-··..:... ...... --·-········ ········---·-'" c 1008.5 2465.7 2.445 27.4 D 1002.1 2449.5 2.444 . 29.2 ......... -......... _____ ,, .... --······-·-·-····-

Average 1005.8 2460.7 2.447 . 28.1 S~.::::l. Dev. 3.114 6.660 0.004

1.203

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Concrete Cube Results at 3 Days B7

Sat. Vol. Sat. Mass Density Compr.Str Sat. Vol. Sat. Mass Density Compr.Str (ml) (q) ((kg/mA3) · MPa) ml) (g) ((kg/mA3) (MPa)

Date of Testing: 17 /09/1993 Date of Testing: 18/09/1993 M1A 1016.8 2473.7 2.433 18.3 M4A 1003.1. 2412.6 2.405 9.9 M1B 1012.3 2462.8 2.433 16.4 M48 1011.1 2444.0 2.4!? _____ ~~§ --·········---··----···---·-···--···-···-----····-- ·····-· ···-------····---···-··---········-·--·---·-----•·------·---'-------~-----------------···-···-

M 1 C 1020.1 2484.3 2.435 18.1 M4C 1011.6' 2428.0 2.400. 10.5 }v11 D 1004.3 2444.4 2.434· _J_~:? ~~g ____ _J_g~_! .0 2443.0 2.416 10.9 Average 1013.4 2466.3 2.434 17 .8 Average 1009.2: 2431.9 2.410 11 .0 Std. Dev. 5.926 14.753 0.001 0.798 Std. Dev. 3.529 12.819 0.007 0.963

Date of Testing: 17/09/1993 Date of Testing: 19/09/1993 M2A 1018.1 2491.8 2.448 12.5 M5A 1022.0. 2473.6 • 2.420 • 12.5 M2B 1007.8 2455.3 2.436 11.4 M58 1004.5 2423.7 _ 2.413. 12.4 M2c____ - --- --·1oc59~o-·----24s3~s---2~4·32··-------,0~5 Msc 1012.1 • 2446.4. 2.411 • 12.8

M2D 1019.0 ____ ?.~.?.~.§ ____ ?:~_??___ 10.8 M5D 1020.1 • 2466.3 2.418 13.5 Average + ··-1013.5 2469.8 2.437• ----,-f3 Average---;-1014~7·-2452_-5-- ----2_417·--·12.8

Std. Dev. 5.103 16.079 0.006 0.765 Std. Dev. 6.951 • 19.380 0.003 0.430

Date of Testing: 18/09/1993 Date of Testing: 19/09/1993 M3A 1012.5 2445.7 2.416 10.3 M6A 1003.9 2459.3 2.450 11.0 M38 1004.9 2446.7 2.435 10.4 M68 1007.0 2458.3 2.441 • 10.0 M·3c .. ··---"-·····- ·-··· ·-·· ,·oos~-·24-45~··--·----·2·~43·2-~-·--·, a·~o· ·t~;fs·c--·--.. ---·--1oos.~2457~·s·--··--·-2~·445~--,.-0~4-M3D 1011.2 2451.8 2.425 9.4 M6D 999.4 2450. 7 2.452 11.2 A~erage _____ foo8.6--2447~--2~427 1 o.O Average 1003-:-9~--2456~5------2~447·-----;·o.-7

Std. Dev. 3.277 2.388 0.008 0.390 Std. Dev. 2.808 3.388 0.004' 0.477

--·---·-.. --Mix Compr.Str

(MPa) M1 17.8 M2 11.3 r------·--------'---------+-------------------+-------_,.:_--------1 M3 10.0 M4 11.0

1---------·---~--------+-----'------11------'-------+-----'-------t

MS 12.8 MS 10.7

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Concrete Cube Results at 7 Days B8

Sat. Vol. Sat. Mass Density Compr.Str Sat. Vol. Sat. Mass Density Compr.Str (ml) (g) ((kg/mA3) (MPa) · ml) (g) · ((kg/mA3) · (MPa)

Date of Testing: 21 /09/1993 Date of Testing: 22109/1993 M1A 1014.9 2466.5 2.430" 24.5 M4A 1010.2 2436.4• 2.412 16.2 M1B 1016.1 . 2494.3 2.455 27.6 M4B 1002.5. 2419.1 2.413 16.9 • • •-•-nn·-•---•·•--·-·-••••••-- ....... ,_, __ , ...... , ___ ,,,,, ___ , _ __,___, ______ , ___ ...... - ....... _,_,,, _________________ , M1C 1005.2 2459.9 2.447· 26.1 M4C 1007.3 2434.8 2.417 16.7 M1D 1016.3 2470.9 2.431. 26.1 M4D • 1020.8 2462.8• 2.413 16.9 ··-··-···---.. ···----·· .. ··--_,,. __ ,,,, ----······· ·-·-

2.441 . Average 1013.1 2472.9 26.1 Average 1010.2 2438.3• 2.414 16.7 Std. Dev. 4.607. 12.961 0.010 1.096 Std. Dev. 6.709 15.690• 0.002 0.286 .

Date of Testincr 21109/1993 Date of Testing: 23/09/1993 M2A 1013.6 2461.0 2.428 16.9 MSA 1013.0 2446.1 • 2.415 19.2 M2B 1017.5 2477.8 2.435 18.8 M5B 1022.9 2467.9 2.413 20.8 M2c-----~-,-01s~s--2471.s---2~434'--19.o Msc-----10-04:s---·2414·.-r·--·-2:4-04:--;-9.s M2D 1000.3 __ 24?_?.0 _ _____ ?:_~2~_ 16.9 M5D 1026.6 24?2.4 2.4Q~,·-···-· _?0.5 Average 1011.7 2459.4 2.431 • 17.9 Average 1016.8 2450.3 2.410. 20.1 Std. Dev. 6.739 19.667 0.004 1.002 Std. Dev. 8.645 22.821 0.004 0.612

Date of Testing: 22109/1993 Date of Testing: 23/09/1993 M3A 1000.9 2431.6 2.429· 15.5 M6A 1007.7: 2461 .1 2.442. 18.6 M3B 1005.8 2449.7 2.436• 16.1 M6B . 996.4. 2424.2· 2.433 16.4 __ ., ..

M3C 1007.0 2460.2 2.443 15.3 M6C • 1002.3 2453.1. 2.447 19.1 M3D 1002.5 2439.0 2.433 16.4 M6D 1003.6 2450.9 2.442 17.7

··-·-···""" .. -······ - ... .. -- ... ,. .. ---··· ·-· ---··--- -·-·--··-···-·-···· ··-· .. ·---·····---·---·-"""" -- .... __ ,. ____

········- . ·--·······-··-· ...... _ ............ _ ... ·····-··-·-··--- .... _, ........... -···· ···---· .. - ............. - --···-·---···· ·-- ... "·-· . Average 1004.1 2445.1 2.435 15.8 Average 1002.5 2447.3 2.441 18.0 Std. Dev. 2.454 10.82d 0.005. 0.444 Std. Dev. 4.047 13.880 0.005 1.026

-··---··-----'--··------~------··-----------;----·--'-------~---·-···-·~----t

Mix Compr.Str (MPa)

·--······-----;-------------+-----:__. _ _,__-+-···--···--;-----..;__----'-----l M1 M2

26.1 17.9 15.8

M4 16.7 ·····-···---------.--··-·-----------+-----·····-······----··---······--···1-----------··· .. ·"-·---·-----'-----l

MS 20.1 M6 18.0

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Concrete Cube Results at 14 Days B9

Sat. Val. Sat. Mass Density Compr.Str Sat. Val. Sat. Mass Densitv Compr.Str (ml) (g) ((kg/mA3) (MPa) ml) (g) ((kg/mA3) (MPa)

Date of Testing: 28/09/1993 Date of Testinq: 29/09/1993 MlA 1019.6 2488.2 2.440. 32.4 M4A 1012.9 2446.1 · 2.41S 22.0 MlB 1020.3 2490.1 2.441: 33.4 M._4_8 ____ 10_1_7._1~• _2._~SS.3• 2.414• 22.4 MlC 32.4 M4C 1019.3 2464.9: 2.418 22.4

~-!-~----~-----·--------- 34.S M4D 1014.2: 2460.4 _?.426 21.7 Average 33.2 Average 101S.9 24S6.7 2.418 22.1 Std. Dev. 0.867 Std. Dev. 2.494 6.987 · O.OOS. 0.29S

Date of Testing: 28/09/1993 Date of Testing: 30/09/1993 M2A 1007.2 24S4.8 2.437 22.2 MSA • 1011.8 2446.3 2.418 23.7 -~-?~_, _____ . __ i_q99.~. 2447.6 2:~?4 ___ __1_!:§ ~-~~--~-_J013.6___1_4S~ 2.419 24.7 M2C 1013.7 2473.2 2.440 22.4 MSC 1013.6 2449.0 2.416 2S.6 M2D 101S.7 247S.9 2.438 20.9 MSD 999.5 2424.1 2.42S 26.0

. "*-· --- • --· ,,_ - • • - - - - -- .•.. ··--- •.• ···-- • ·- -- -- •. - • • •• • ·-·-·-·-.. -----· ·- ·--- •.

Average 1011.6 2462.9 2.43S 21.8 Average 1009.6 2442.8 2.419 2S.O Std. Dev. 3.338 11.987 0.006 O.S8S Std. Dev. S.892 10.929 0.003 0.886

Date of Testing: 29/09/1993 Date of Testing: 30/09/1993 M3A 1013.7 2466.6 2.433 21.9 M6A 1006.3 2463.4 2.448 23.7 M38 100S.3 2437.4 2.42S 20.4 M68 1004.2 24S6.7 2.446 22.2 - -·· .. ·"···-·······---- ...... --.. ······-- ...... .. ·"'--·--··----·------·-·---·-·-·~--·---.. ·-·· -·-····--··-·----·-·---·---· M3C 1007.1 24S7.2 2.440 21.4 MSC 998.2 2438.4 2.443 22.3 M3D 1011.6 24S4.9 2.427 20.1 M6D 1010.0. 2469.0 · 2.44S 22.0 Average -- ·---·· , oos.4·-----2454~0- -------2:.431----21--.0- Average-: -foo4.f24ss:s·----2:445-----22:s

Std. Dev. . 3.370 1 O.SS2 0.006 · 0.730 Std. Dev. 4.276 11 .521 • 0.002 0.673 .

----------+---~-------...-------..... _______ _.___, __ _,__ ___ 1

Mix Compr.Str (MPa) ............. , ______ ,, ___ .. _____ ,, ___ .. ·-----··-··---···---···--.. r-----------"---'f-----·-·--------.,------i

M1 33.2 M2 21.8 ,,_,, __ _._, _____ ~----------------·t--------.. --~·----1----~---M3 21.0 M4 • 22.1 ---··-··--··--· ... - ... ·---·-·---·-·---··---·------·-· -·····-~- ............ ___ .. -~ .... , ... _ .......... _.,, ___ ... _____ ~------<----'----t MS 2S.O M6 22.6

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M1A M18 MlC M1D Average Std. Dev.

Concrete Cube Results at 21 Days BiO

Sat. Vol. . Sat. Mass Density Compr.Str Sat. Vol. Sat. Mass · Density Compr.Str (ml) (g) ((kg/mA3) (MPa) ml) (g) ((kg/mA3) (MPa)

Date ofTestinq: OS/10/1993 Date of Testing: 06/10/1993 1017.6 2491.2 2.448 36.6 M4A 1026.1. 2498.7~ 2.435 27.7 1020.7 2491.3 2.441. 36.1 M48 1008.0 2441.1• 2.422 26.7 1013.0 247S.5 2.444 37.1 M4C 1022.7 2474.2 2.419. 23.4

i 01.?:q _____ .1~~~: I_. ___ ?_:4_~§~ ______ ?_?_~~ -~~!?__________ J99-~:-~-~_24_44.~---------?~?~ ____ 1?.:9-1015.8 2480.7 2.442 36.8 Average 1016.4 2464.6· 2.425 2S.7

3.S19 11 .243 · O.OOS • 0.49S Std. Dev. 8.095 · 23.S33. 0.006 · 1 .642

Date of Testing: OS/10/1993 Date of Testing: 07/10/1993 M2A 1014.1 • 2469.8 2.435 26.6 M5A 1009.6 2433.2 2.410 29.3 M28 1007.3 24S7.6 2.440 26.0 MSB 1014.6 2447.3 2.412 2S.9 -·-"''"--·-·-·--··-·-···-·"···---.. --··•"""-··-······--····-~·--·----·-------·-····· ......... -··---·-·-·" ..... -----~-·-·--····--··---·····--;., __ .. _____ ,_, ____ ,...:...._, ... ____________ , __ . ------<

M2C 1013.6 2472.9 2.440 26.3 MSC 1012.3 2439.0 2.409 30.3 M2D , ___ 1_Q_09:3• __ 2_~5~:_S _____ ?:.~?-~ 26.4 MSD . 1010.4 2413.9 2.389 27.8 Average 1011.1 • 2464. 7 2.438 26.3 Average 1011. 7 2433.4 2.40S 28.3 Std. Dev. 2.869 6.747. 0.002 0.217 Std. Dev. 1 .928 12.297 0.009 1 .6S9

Date of Testing: 06/10/1993 Date of Testing: 07/10/1993 M3A 999.3 2424.3 2.426 2S.5 M6A 1004.0 2457.1 2.447 26.3 M38 1013.3 2467.3 2.435 2S.O M68 1013.8. 247S.8 · 2.442 · 2S.7 -··--· ·----.... ____ ... --- '"""·-·-····--· .. ·····-··--"·-·"··--·------ -----···---"""'""'"""''_...._ ____ ...... ............. "'"""·-·-······-...... , ___ , .................. ____ ... -··--· .. ·· .... -... ......:_ ____ , .. _ .................... .:--....... - ........ -........... ____ .... ---·--- ·-·· ..

M3C 1014.8 2477.2 2.441 24.9 MSC 1005.3 2457 .3 2.444 24.4 M31:) __ .. _ __ 1008.0 ____ ~-~?~9 ____ ?_:~-~g ___ _?_?_:J ~~_f?_ ------~_QQ?_.9. _____ 2~53-:~ · .. _____ 2_.~~§~ ______ .2S.7 Average 1008.9 2457.2 2.436 25.1 Average · 1006.5 2460.9 2.445 25.S Std. Dev. 6.065 19.948 0.006 0.228 Std. Dev. 4.299 8.742 0.002 0.694

.................... --·-··---·-.. ·-·----····-·-.. - ·-·-.. ·-·--·--·- · ·--·----·-···-·······--r--------.----·····-·-.. ····"'"'""--"·---···--·-i·-·--··--"--"-------1

Mix Compr.Str (MPa) •

···-·····--·---··-------'----+-----;.---------+-·------'-----------····-·····"·"----~----; Ml ~B .

M2 • 26.3 . r------___.__. ___ _..._ ________ M3----~---·2-5:;--- --------------------. _________ _,

M4 • 2S.7 --·--~----- --+--.. ··--· .. --------.. -----·"--... -------··--··· .. ···-----.. ··----------'-------1

MS • 28.3 M6 25.S

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Concrete Cube Results at 28 Days Bll

Sat. Vol. Sat. Mass Density Compr.Str Sat. Vol. Sat. Mass Density Compr.Str {ml) {g) {{kg/m-3) MPa) · ml) {q) {(kq/m-3) {MPa)

Date of Testing: 12110/1993 Date of Testing: 13/10/1993 M1A 1019.6 2483.8 2.436 38.4 M4A 1014.8 2459.9 2.424 29.7 M18 1005.2 2448 .. 2 2.436 39.8 t:-1~~--------1_9~?.:~_1.._~_?_Q.9. 2.417. 27.2 M1C·-----..,-----1o68~3-246-0.8 ___ 2)i41_. ____ 3~i-7 M4C 1022.2: 2478.3. 2.424. 27.2

.~ .. !!?_ .. ___ ~ ____ 1_99 .. !:~~?8·~----~:_~~-?.~ __ 39:! -~41? !29..9J! __ • _?_'!..?. .. ~_I..:__ ___ ?....:~?.?~---~9~~-Average 1008.6 2457.8 2.437 39.0 Average 1015.1 • 2459.5 2.423 28.4 Std.Dev. 6.818 16.982 0.002 0.524 Std.Dev. 8.779 18.922 0.004 1.159

Date of Testing: 12/10/1993 M2A 1020.1 2489.2 2.440 28.5 M5A M2B . 1017.8 2496.5 2.453 27.5 M5B M2-c-------c--·--;oo-s~3 2460.8 2.44f' ______ 2a:4 Msc M2D 1001.3 2438.4 2.435 28.6 M5D

Date of Testinci: 14/10/1993 1014.6 2461.1 • 2.426 30. 7 1020.3 1014.3

• 1024.0

2453.0. 2.404. 31.1 2439.9 2.406 30.1 2484.5. 2.426 30.9

·-···· ...... ·-···-- ............................. .... _..., .................. _ 2459.6·:-........ _, ....... 2 ....... 415 ~-·------36) Average 1011.9 2471.2 2.442 Std. Dev. 7.539 23.174 0.005•

28.3 Average 0.439 Std. Dev.

1018.3 4.068 16.232 0.011 : 0.37 4

Date ofTesti:tg: 13/10/1993 Date ofTestinci: 14/10/1993 M3A 1010.4 2461.5 2.436 27.3 M6A 1003.3 2461.7 2.454 29.2

~-~§_ _________ 1__QQ~.4. 24_50.~----~'.~~5. 27.2 M6B 1 OQ.~_:_s__~~-~§:_~~----2....:~~~---__?.·~~ M3C 1013.8 2468.0 2.434 25.2 M6C 1008.5 2465.7 2.445. 27.4 M3D 1008.8 2459.5 2.438: 27.5 M6D 1002.1 • 2449.5. 2.444 · 29.2

•••••--•••""·-•-•"---••••·-"---··-•••n"'""'"------·-- ·------··-·-----•••••"':._,_, ___ '"'''""''''" ''-'""'-"''''''"'""'"''""-"""""'•--·•·•-·••••••·-•- •••·-•--••--··•••••""" """" .. "'""" •••••-""""'"~-- •

Average 1009.9 2459.9 2.436 26.8 Average 1005.8 2460.7 2.447 28.1 Std. Dev. 2.688 6.296 0.001 · 0.930 Std. Dev. 3.114 • 6.660 0.004 • 1.203

__ ,, ___ ,, __ .. ~---·--.. --·-------;--------;---~"-----;-

----:------------------------'-........ -+-------'----~---'----!

-·--.... --~--... - ..... --.. -·--------··r---Ma-~-2--6-.8--.--·---------- ..

M4 28.4 ---•••-··-n-••·-"-•••·-•--••••· .. --•··-·-·-•••••--··-----·-------•••••--•.,---·-"'" _____ ,.,,,_,.,,

MS • 30.7 ·-·-----·-·---·--·-----·-----'------l

M6 28.1

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APPENDIX C

• DT A thermograms for the respective test intervals, all

samples analyzed in a dry nitrogen atmosphere.

• DTA the1mograms for the respective test intervals,

samples analyzed in a dry nitrogen atmosphere only the

Van Eck(-63) paste analyzed in a normal air atmosphere.

• DT A thermograms for the different pastes over the

complete curing period, all analyzed in a dry nitrogen

atmosphere.

• DTA thermograms for the Van Eck(-63) paste over the

complete curing period, analyzed in a normal air

atmosphere.

• TGA plots for the respective test intervals, all

samples analyzed in a dry nitrogen atmosphere.

• TGA plots for the respective test intervals, samples

analyzed in a ch:· nitrogen atmosphere only the

Van Eck(-63) paste analyzed in a normal air atmosphere.

• TGA p~ots for the different pastes over the complete

curing period, all analyzed in a dry nitrogen

atmosphere.

• TGA plots for the Van Eck(-63) paste over the

complete curing period, analyzed in a normal air

atmosphere.

• DTG plots for the different pastes over the complete

curing period.

Page

Cl to C5

C6 to ClO

Cll to C16

C17

CI8 to C22

C23 to C27

C28 to C33

C34

C35 to C40

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• DTG plots for the Van Eck(-63) paste over the

complete curing period, analyzed in a normal air

atmosphere. C41

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0 c Q) '-Q)

~

0 Q) '-::J _. cu '-Q) Q. E Q)

I-

OTA Thermogram after 3 Days Dry Nitrogen Atmosphere

6~~~~~--~~~~~--~~~·~~~~--~~~~~

5

4-·

3- .. ························ ..

2- ···································

1

01···~

-1-·····

..... ~'"\ ----............" \

......................................... 'I\'

-2---~~~~~~~~~~- ·~~~~---r--~~~-.-~~~~

0 100 200 300 400 500 600 Temperature (Degrees Celsius)

- Control ·-·····-···-·-···· Lethabo(-63) --------- Lethabo

- Duvha(-63) .................. Van Eck(-63) -·-·-·-·- Matla(-63)

I

0 .......

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n Q) (.) c Q) i.. Q)

::t:: 0 Q) i..

:::J ........ cu i.. Q) Q.

E

DTA Thermogram after 7 Days Dry Nitrogen Atmosphere

5.-~~-~~~~~~~~--~~--~-~~~~~~~~~

5-1 .............. . ·········-············ ........... . ·-- ... -.... . . I<~:···~-·~~:=·~_·, ... ,·~~-··,

4 ..................

3-----·---·-·-----·---···---------

2--------··--·-----·-- ..................................... ·········-·

~·················· - -1L.................................................................................. \ ···-- -----·-----1

1 ------·· ................ ····················-·

o---

~ -1

-2-l·····································----·-·---·-·--'~:'Y· ·--·-------------·-···-·--··-··-···················-······-·--·-·---------·····-·························-················································

-3--+-~~~~~~~~~~~~~~~~~~~~~~~

0 100 200 300 400 500 600 Temperature (Degrees Celsfus)

-- Control ------·-···· Lethabo(-63) --------- Lethabo

- Duvha(-63) .................. Van Eck(-63) --------- Matla(-63) Q

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OTA Themogram after 14 Days Dry Nitrogen Atmosphere

5-.---~~~~~-~~~~~~~~~

s-··········· ···································································································································································································· ............ .

4·+ ...........

.......... ;~;·/_·· ... \ 3-+ ························ ······················

0 2-+········· ...... . -.·~

Q) s... :::J +-'

'° s... Q) 0. E

,,, .. ~

11 ............ . .. . ................... . ....... ················· lj;I:~-- . ............... . ......... . ,_.

01····-~-·-·······························-~---JH·······························································································

~ -1

-2-··················· ' v --····-·················-········-·-··-·-·····················-··-····- ·······················-······--·-··--·-······-························-.····

_3-4-~~~~~~~~~~~~~~-,.-~~~----.-~~~-J

0 100 200 300 400 500 600 Temperature (Degrees Celsius)

-- Control ·················· Lethabo(-63) --------- Lethabo

- Duvha(-63) .................. Van Eck(-63) -·-·---·- Matla(-63) () v)

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n a> (.) c <D s.... <D ~

0 <D s.... :l ...... lU s.... <D Q.

E <D I-

DTA Thermogram after 21 Days Dry Nitrogen Atmosphere

10.-~~~~~~~~~~~~~~~~~~~~~~----.,

a~·-·················

6~·································-·--···--·--·····-····-······-···-···--·--·······-·······-········-····························--·-·············-··-·· .................. "'\

.,.,,.,,,.,. ..

4+mm mm mm m m mmmmm~:.~----~~ _,,,__

01----------bi~i;:::~:-.~~---------------·--·-----·--·-----·---------·::.:.:.:.:········r·"--·----··----···------------------·-------·------------------------------------------··---··--···--····--~

-2

_4-1-~~~~~~~..--~~---,~~~------,-~~~~~~~~

0 100 200 300 400 500 600 Temperature (Degrees Celsius)

-- Control ··············-··· Lethabo(-63) --------- Lethabo

- Duvha(-63) .................. Van Eck(-63) ··-·····- Matla(-63) (") +>-

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OTA Thermogram after 28 Days Dry Nitrogen Atmosphere

a-.--~~~~~~~~~~~~~~~~~~~~~~---,

., .. -..... ,, .I' ••

.;'° "

O> 0 c

;I" '

6-i······· .. ·· .. ···· .. ········································ .. ···························································· ································································-························ ................................... /. ............................... ~'::::::-:::::~ ............... . I ..... .

O> L. Q) ~

0

.,..,., i ,... : !

~ : 1:~- -~~~~ ~~-~ ~ ~~ :~~~-~ ~~::~~~~:-:~.~ -~~~~~:~;~~:~-~~-~::~-~,-t~-----::J I / \ +-' .. , \ n::s f I :;' ,,

[ 0 ........... / /;..<~ ........................................................................................................... \' ..... .f1.

E u d 1:

Q) • ~ 1 r- ' . .--' ' ; -2 ···················································-~.:~··············~·;.· . .-!:'. ................. ~,,./-·········· -··············-····················································-·················--···········-·····- ----------·-·\I···-···········-·····························································-~ ''-............ ,.

-4-+-~~~-.--~~~-.--~~~.--~~~-,--~~~.--~~---;

0 100 200 300 400 500 600 Temperature (Degrees Celsius)

-- Control ·················· Lethabo(-63) -------·- Lethabo

- Duvha(-63) ----------- Van Eck(-63) -·-·····- Matla(-63) 0 v..

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DTA 'Thermogram after 3 Days Van Eck(--63) \Paste in Normal Air

20~-------------------------------------------------------------------------------------------

/ ......... , ..... , .. f'/ · .. ..,.

{\ ...... \\ l \ / \

j \",J,/ \ ~ 15-• c (J) L. Q)

::i:: 0 (J) L.

::J ·+-' ro L. (J)

0. E Q)

I-

I ,., ..... j·· -------------- ----·-----·-----------------,,

1 o-···---·----··----···--·----------·---····----·- ·------------------------------------------·--·- -····----------·--·----------------··-·-----------···-·· -------···--·----··--··

,.·"' ,, ,.

/ s-+- ----------------- ----- ----------------------------------- --------------- ---------- ------ ~:.::~·<--~;;------------- --------------------- ------------------------·-----------

01--------~~

-5-1-----r·------r ----- r· r---------,-------

0 100 200 3001 400 500 1600 Ten1perature (Degrees Cel.sius)

--------------------- - - --] -- Control ----·---·-----·- Lethabo,(-63) --------- Lethabo

-- Duvha(-63) .................. Van Eck(-.63) -·-·-·-·· Matla(-6·3) -----------------------------------------------------------------------------------

0 o.

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20·

~ 15--· . c Q) L... Q)

~

0 (]) .!.....

:J

1 o-

+-' h-···· co ,) .L. Q)

0.. E (]) o-, . ~-

OTA 'Thermogram after 7 Days Van Eck(--63) 1Paste in f\Jormal Air

.. .1·····-·········,\,\,

'\\ ·, '\

~~;;;:~ ¥::~~

-5--1---------------r------------------r------------------T-------------------T-----------------,------~---

O 100 200 300 400 500 600 TerTiperature (Degrees Celsius)

r-----------------------------------------------------------------------~

------ Control ··········· ·- Lethaboi(-63) --------- Letha.Ibo

- Duvha(-63) .................. Van Eck(-.63) -·······- Matla(-63) ---------------·---·--------·------·----·-----·--------------·--·----··---------·------··----·-------------------

0 --.:1

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OTA Ther:mogram after 14· 1Days Van Eck(-63) 1Paste in Norimal Air

20-·---------------------------------------------------------------------------------------------

15. ' ,~

:'i I\ ___ ./ ... -···,.,,.\ : '\

~ 10 0

-·----·--· -·· - --·······-------···--·--·--···-·-- ···- ---· -· -----· ·---·-······· ............ ...1 ....................... ······ ....... >. ..... .

/J (]) ,_ :J 1ti ,_ Q)

0. E (]) I-

_,..J ... ,.

5-+·· ············-···················· ····························································--····-······· ·---···---·-········---········;:.,.1<'.: ........ ······-··--·-··················-·······-··-······-·-··--····-····-·······--··-··· ~··' ...

__ ,.,?.!!!!~--------~-~

---~~

01--- .......... ·~~::~~

-5-+---· 1· T -i--------r i-----

0 100 200 30Qi 400 500 1600 Temperature (Degrees Celsius)

~--- ----------------------]

-- Contro1I ·------···-· Lethabo:(-63) --------- Lethabo

- Duvha(-63) .................. Van Eck(-.63) ········· Matla(-63} -----------------------------------------------------------

0 00

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D'TA Thermogram a~fter 21 10 1ays Van Eck(--63) Paste in 1Norimal )\iir

20-,-----------------------------------------------------------------------------------------------------------,

15.

! ..

j \._ f. \ ,, .. .,.., .... I \ ____ ,.-"" -..... \

!:t: 10 0

.... ... .. ... . . .. . J \ ....... : '

...................... ············ :.~. l·························· .......... '> Ql ,_ :J +-' ro ,_ (]) Q.. E Ql ~-

•. _ .. ,.,.1" ... ~

•·•· ... _;;;,;:;;,C'"''"_,,,~,.·-~ ··•• m • ••·••·•·••• ••• m ••··• m ......... , ......... .

o+- -----..... ------- - ~·~~~~~~::::~~~-:=";;:::;~,~ ~!~~==c.i:::ioo:.., ~ :::=dJZ '\ /(~£c=c~ "'~~~ ' ················································································ 'v,7···················· ~=:~ '\'.!

-5-1----------·--r-·-·-·--·--·-·-r--·---------1·--------------T·----·--·--·---·r------------

0 100 200 300 400 500 600 TerTiperature (Degrees Celsius)

[-·------------------------------------------------------------------------1 ------ Control ······-··········· Lethabo(-·63) -------- Lethabo

--- Duvha(-63) .................. Van Edk(-630 -·-·····- Matla(-63) ---------------------------~-------------------------------------------------·--------------------·-

0 '-0

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OTA Ther:mogram after 28 !Days Van Eck(-63) :Paste in .Normal Air

20-,------------------------------------------------------------------------------------------------

~':.

~ 15-· -·· .. c Q) ll-Q)

::i:: i:5 Q) ll-

:J +-' ro ll-Q) Q.

E ~

_-=:_.~- : :•••:,:;L;o·<C~~~~~ ................................. _ ..... . ........... 5-+-··-···

~

O-r---···-· . ~

-5-i-------r I r~---- ~-------

0 100 200 300 400 500 600 Temperature (Degrees Celsius)

l---------- - ---------] -- Contro'I ·-----··-··- Letrnabo:(-63) --------- Lethabo

- Duvha(-·63) .................. Van Eck(-.63) ········· Matla(-6:3)· -----------------------------------------------------------

() -0

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0 c Q) s... (])

::i:: 0 (]) L. :J ........ co s... Q)

0.. E Q) ~-

5~

4

3

2

1

0

-1

-2

DTA Thermogram for the Contra/I Paste Dry Nitrogen Atmosphe~e

Jr ,.. ;;;·~~r...,.~·'··~.~~.1;;;-;:;~:;~';;)."~

/~":-~\, :~······················ '/- '.;., ,./~ .,,,,,.. '' ;/ .~ .,._

,,,.,, ..•.............. ,,,.,,,,,,., //) '.,,,,,,,,,,,,,, :~ ][ ~ /

_,,..,, ,'i / : l '{ / ' ' ' ~' //jd/ .... ,,.,,,,,,,, .,, ..... ,,,,,,,,,,,,,.,,,,. - -·- ........... ,,,.,, , ..... , .. ,,.,,

,~. / _,,,,_...r r 1 ~ / ,,.r· I

\ . J.r""')/:-~1' / , ' ;;,.•· F . . ,./'......,

\ \ --.....___.. .· ,,/~/ ·\ ,/ ,..

I ' / ---·-···-·· ....................... -- "\"\· .. ::;./~~? .... ... - .......... ...... ................ .. . ..... ._ . .,..... . . ............................................ ..

\_,.r . 'I ·'·)

-31-----------T--------·----i-----------r-------------T--------------,---------------Q 100 200 300 400 500 600

Temperature (Degrees Celsius)

- --------] ------ 3 Days ·· --- ··· 7 Days --------- 14 Days

--------- 21 Days ,, ... ., .......... 28 Days ---------~------~---~-

(") ,_. -

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5

4

3

2

1

0

-1

-2

-3 0

OTA Thermogram - Lethabo(-,63) Paste Dry Nitrogen Atmosphe~e

-----, .. ;.-r:~:··-····'''·_-··:·,, ... ,,~ ......... ···-"~·:'.~>\- -------- --- ---------,. .

/;;~ ,.' c::=~~==-~I \ ···· I;;:~---~. ············ / / _/ _ .. -- ·---- - -- -- ·-- - '· ~- -----~ .. j/ ,., - . ~------------ '• :;, / .. - , : r -~--.,:,..,~· ..... ,

; / ,,---/ __ -- ._ i r------~'"""':::~-:----.. ·-.,.._

.................. .....•............ • ••••••••.•........• ;1~2r_·········································· •••............... \~\---······'if••-·········''·:~·-······ !! / :•

/ ii I l ;• / ii ) It d

/ ..... ~\ f ... / ·~~~ .:1 ---t~::~-~~=< ______ >~::>:~;::"'/~'1/r- - -- - ---- - --- -- -- ----- --- -'.:r1 .n- -- ---- ---------------- --- ------------------

~~ ( -'/-- i : -_q; .-.-

• >tt~=, v:·t ---~---------T- ,--- -----r -r---------

10Q 200 300 400 500 600 ·temperature (Degrees Celsius}

l------------- ----1 ----- 3 Days ----------- 7 Days ---------- 14 !Days

--------- 21 Days .................. 28 Days ---------------~------------------------·------------·-----

() ,__. N

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OTA Thermogiram - :Let;habo Paste Dry Nitrogen Atmosphe~e

5-.-----------------------------·-------------------------------·------------------------------------------------------·-----------,

4-•'/ I

g 3 7~::~:;s;:::::::::::::·~, ;\ iz::~'"'''·~ Cl!) / / _.- ,.,. ,_,.,,_,,,. ,._ : •:1• '---- "·.---

~ 2···· ······································································· /t;f'< \i·······ff···········~~'.~········· 0 I f'~:f .; •;

C1l 1 - ---- ----- - - -7/ -II - - --- --- --- --- ~~i;- --iU - --lo.. / .'i J ,.: ~i -. .- i! I •, ~ :1 -' / ,.,, t:; .,t

~ Q· ·~=<··················;?/··························· ······· ····l~t············ ............... . o.. ".. . ..... -, ,: :tVi: E -1 - --- ------ ---------~\\--- ,,;7'/~~.l>~.,,r --- - - - ---- -- -- --- -- -\W--- ---- -------(]) ;__\ /-- ,,/ \J I- \'--,/ ,.., '1/

-2 . --- ------ ---- __ \,.,";;;;r"/;(_.', ___ . '

-3--t· r·--------------T---------~------------T

0 100 200 300 400 Temperature (Degrees Celsius)

-=-- 3oays -- - 7 Days ~-----:~14 !Day~-]' I

.................. 21 Day.s -·-·····- 28 Days I -------------------·---·-----------------------------------------------

-----i--------------------

500 600

0 ,__ w

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Cl)) 0 c.: <ll.l s... Cl))

::t:: i:5

Cl)) s... :J ....... ro s... Cl)) 0.. E Cl)) I-

5

4--

3

2

1

0

·1

·2

OTA Therm:ogram .- Duvha(-163) Paste Dry Nitrogen Atimosphe~e

------------------------------------------------------------------------------

r r~,

/ /' .,.,., ..... '' ,, '·

.3----·--------,~·-~---.---------r--------,.----,------,--------------1

0 100' 200' 300 400 500 600 temperatwre (:Deg1rees Celsius):

~~-- 3 :DAYS. m 7 DAYS ummm 14 DAYS l .......... 21 DAYS ···-·····- 2·8 DAYS ·

------------------------------,-.---~-----

0 ,_. J4

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(() 0 c (ill s... (ii) 4: ·-0

C!1) s... :J

·+' ro ,_ (I) Q. E (J) I-

DTAThermogram - Van Eck.(-63) /Paste Dry Nitrogen Atmosphe~e

10-1-------------------------------------------·---------------------------------------------------

8-

:6

4

2

O-·

-2

--···------

······ ...... ··········· . ······ .. . ................. ······ ............ .... ..---------~~-·--~~----==-\· ~ .... . ~,, ~y~;?~\~J.r:-~

"'0 - -··· ,.,. ·~ J . . .. ,,,~~s~?l ·········· ·········· ··········· ············ ........................ ~, ················ ... .

-4 -r----------------r-----------------·---r-··--------------T-----------------T-------------,-----------

0 100 :200 300 400 500 r600 Temperature (Degrees Ce:lsius)

[--------------------------------------------------------] 1

----.-------- :3 Days ········· ····· .7 Days ---------- 14 Days

................... 21 Days ·········· 28 Days ___________ ,.__ ____________________________________________ _ Q

Vt

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DTA Thermogra:m - Matla(-63) Paste Dry Nitrogen At:mosphe~e

4 ---,----------·--·---------------------------------------------------·---------------------------------- ------------------------------ ---· --------------------------------------·-------------,

3 0 ,,,, ... ·/ ,'• ,.:,: "~·~···ll;~·~ ......

'!1~,~-···-

'~ .. --.. ~-~- ··-···· f .. .. I(. .. .. ··-- 'l

GD ff' •'I" C ~. ~ I ,,

/ ,., ... ~ 2 .................................................................................... l!:l ············ :'' Ii ....... ·--·--·--- ........... -·-·- ..... .

' ....... ..... ...... ... -···--1.

.... I / /J'~ ~ 1 ··························· ................ ········· ········· ··········:;tt········· ······ ........................................... . CO

/ ":• ' .. c:, ®o.. o- .. "t·:.::~~~\-- ....... ~~>~"'"If"'"

~~~' ,~~----"·,\J ~ E \ '--v_~/ ./ . ·· .... / ff: /"'?'--....,__, ., Q) ~, i ····~-.............. ~· .... .__ h ... .. .................... , ............................... , ...... . I- 1 . . .. - . .. .... ... . "''<' .;/ r\.·\ " .. ·~-- ·\·:' .,\··!

' \/

.. 2--r--~__.__,._-. l

0 100· 200· 300 400 ·temperatwre (1Degrees Celsiu:S):

' JI

"I

-- :3 Days --·--·-··· 7 Days ---------- 14 Days

~. -

.. .-......... :21 Days ····-····· ,28 Days -----------------------------------------------------

500 600

0 ...... 0\

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··--------· OTA Thermogram - Van Eck(-63) !Paste

Normal Air Atmosphere 20 ~---------------------------------------------------------------

--""" R\. // "

/ --::::~. \\ Q) ·1 5 't '·\ / ,:::·-- .. ·-.'· .. , ' 0

'

t \· / ., ' \ ;I \l _/ -:. c ;: ,_.. \,~ \

Q) 1 >\'~ \

~ 10···· ················································································································ ...... ····~······················~······· 0 ff,Jf Q) ~----N.1 ~ /•

:J h'' ~ ~ i 5················· ..................................................... ;,;~~·····················································

E ,//:/--·" :.--------,.,-,(, .... ~p--

1-1(]) 0 _ ..... --~~~:=~=>-=-=::.:::>~~?/,./~,/_.J-e _ _ _____ .. . _________ . __ ..... _____ ........... __ . . ___ .................. ____________ ........ _ ....... ________ _

~~ .-- --~,~-· --"'-':/ J ~u~-

.5-1-___ .:_:..____ __ ,---------,-----------~-------------,----------0 100 200 300 400 500 :600

Temperature (Degrees Celsius)

11·-=:=-- :3 oay;-~:=-=-=-7-oay;------------------ll ---- ------ 21 Days -·-···-··· 28 Days I---------------------------·----------------------------------------,

14 Days 0 ,_. -.)

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(])

rn c m ..c 0 en en m ~ ~ ~·

TGA Plot after 3 Days Dry Nitrogen Atmosphere

1 ·-----------------------------------------------------------------

o-~·····

..... '~·· ····································· ·········· ·················· .............................................. . -1 + ....... · •. :::<:~············ .... .

g _J········-- ................................................ .. - I

-10· 0

------y--- --i-----------r-- ~

100 200 300 400 500 600 Temperature (Degrees Celsius)

[---------- - - - l --- Contro1I ............... Lethaboi(-63) --------- Lethabo

- Duvha(-63) ., ................ Van Eck(-63) -·-··-~-- Matla(-63) ------------~------------------------------:-----------------------

0 ..... 00

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(J) Ol c

TGA Plot after 7 'Days Dry Nitrogen Atmosphere

2-~--------------------------------------------------------------------------

(ti 6 _4 .................................... .

(/J en (\j

~ ~ 0·

_5 ................................................ ..

-8·-<-------------------------------------------------

-10·-<· ...... .

-121---------,----------1------------,----------,--------------.------------0 1 00 200 300 400 500 600

Temperature (Degrees Celsius)

[----------------- ---------------] --- Control ............... Lethabo(-63) --------- Letha.be

- Duvha(-63) .......... , ....... Van Eck(-.63) ········· Matla(-63) ·-------------·-----------------------------·---------------·---------

(J ..... '-0

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Q)

Ol c ro

,.C

0 en en ro ~ .-,0 ,o""-

TGA Plot after 14 Days Dry Nitrogen Atmosphere

2~---------------------------------------------------------

~:,:······· o+···· ~ .................. . . \. '

.\,,, -2-; .......................................... ..

-· 4 __. ............................................... ..

-6·-..._ ........................................................................... ..

-12-r-·--· 0

-1

100 ,-----

200 r r-

300 400 Temperature (Degrees Celsius)

-, :500

~- Control ............... Letrnaboi(-63) --------- Lethabo J

- Duvha(-63) .................. VanEck(-63) -···~·-·- Matla(-63) --------------------------------------------------

600

(') t-.,;i 0

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Q) 0) c co ..c 0 en en ('CS

~ -,0 o"-

TGA Plot after 21 Da.ys Dry Nitrogen Atmosphere

2T-----------------------------------------------------------------

Q-I-----~-----

-2--· ------

-4 _ _, ______________________ ................. ----·····----

-6---·- ·······--········ ............ ··········

-8----<···-------·-···- ---·------·---·------------·----------···

......... ._ .. _ ... -1 o-~------------·

-12-+-- --·-·-··-··--·-------

-14-r---------r--------------·-r-·-----'-----,-------------i--------------i------------0 100 200 300 400 500 600

Temperature (De.grees Celsius)

[------------------------------------------------------] ----- Contro:I ·· ------ Lethabo(-63) --------- Lethabo

- Duvha(-63) .................. Van Eck(-:63) -·-·-·-·- Matla(-63) --------------~-------~-----------------·----------------------------------

G -

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Q) CJ) c (U

.I: 0 en en (U

~

TGA Plot after 28 Days Dry Nitro,gen Atmosphere

2~-------------------------------·------------------------------------------

~ ............. .

o+·· -~~ '• .,

.... ·.\~~~~ _;~. . ......... .

-12·-+···················································

·········--·················· ............................. ····························

-14 r-------y--------1 I ~

0 100 200 300 400 Temperature (Degrees Celsius)

I

:500

~ ---- ---------- J

----- Contro,I ·· ·· · · · Lethabo.(-63) -·------- Lethabo

- Duvha(-63) ., ........... , .... Van Eck(-63) -·-···-·· Matla(-63) _____________________________ ........_ _______________________ .,

600

() tv tv

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TGA Plot after 3 Days Van Eck(-63) :Paste in Normal Air

2~-------------------------------------·----------------------------

~ -2·-4 ·····--·-··- - ----······-·. c eel

..c: -4 u en en eel ~ ,,o o"-

-6

-,s·_. __ .. ______ __ _________ .. _ --------------------------- --------- . ----------

-1 o~---

-12-1-------------,--------------r----------------,-------------1-·--------------i-----·----------O 1 00 200 300 400 :500 600

Temperature (Deg:rees Celsius)

r

---------------------------------------------i ---- Control .. - _____ .. Lethabo(-63) --------- Lethabo

-- Duvha(~63) .................. Van Eck(-,63) -·-···-·- Matla(-63) ----·--·----·------~----·--·----·-------------------------------------------

\:) N w

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~ ~ ~

TGA Plot after 7 iDays Van Eck(.:63)Paste in JNorimal Air

2 ~------------------------------------·-------------------------

-4·

-fr

............... ........ --10+--···········--········ ·················

-12·-t-·----~--------r-------,-· ---y-- I

0 100 200 300 400 :500 600 Temperature (Degrrees Celsius)

~~---- ~l - Contro'I ·················· Lethabo;(-63) --------.- Lethabo

- Duvha(~63) .................. Van Eck(-.63) ··-·····- Matla(-63) -------------------------------------------...---------

0 N -"'-

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.i::. 0 en en ro ~ .... o .o""-

TGA Plot after 14 Days Van Eck(-63) iPaste in Nonmal Air

2~------------------------------------------------------------------------·

0

-2· ···-············· ........................... .

-4·-I··········· ............... . ................

-8·

-1 o-~···· --·-··············

"""--....---..._ ......... ...._....___ ... ___ _ -12 ·1-----------·1-··-------·-i-------------,-------------~1·--------------,-------------

0 100 200 300 400 500 600 Temperature (Degrees Celsius)

----------------------------------------------------------J ----- Contro 11 ······ ··· · Lethabo:(-63) -·--·---- Lethabo

- Duvha(-63) ............. , .... Van Eck(-63) -·-···-·- Matla(-63) --------------------------------------------------------------------

n N Vi

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(]) rn c (U

..c: 0 en en ro

:?-

TGA. Plot after 21 Days Van Eck(-63) 1Paste in Norimal Air

2-------·-·------·-·--·-·-·-·---------·--·-·-·--·-·-·---·---·--·--·-

..... ······················ ··········· ·····-· ········ ........ ............. --····· .... . ....... ···········-·-·······

................... ''~~~~:·······~··~························· ·····••••••·

"~,~~--······.~ .....

-2-~··

-4

-6--'·· ··········· , .......... , ... .

-8·-+······················--····-- ........... , .. ---············· ....

m m m m m . •'..mm -~;:~~ •• ,~,\'~E~;;:~mm . . . . . .. ....... \""' --, ...... . ..... ~~

· ~ -1 o~ ······· ···· ········· ········· ······· ...••••... .•.•••.. .•••••.•••••.•.••••••..... .... ···· ······ ···· ···· ······ ··········· ······· ····· ···· ····· ........ ······ .... ..... .... ........ .... ........... "",, -12+································--··················

-140-·-100 200 -------1 1 r I

300 400 :500 600 Temper.a:ture (Deg:rees Celsius)

~ --------·] Contro,I ·· ···· ··· Lethabo:(-63) ---·-·-·- Lethabo

Duvha(-63) .................. Van Eck(-,63) -···-·-·· Matla(-6'3) -- --- _____________ .._ ____ ----------·~------·------------------

0 I'-) 0\

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Q)

Ol c ('Cl

...c 0

CJ) CJ)

TG.A Pl·ot after 28 Days Van Eck(-63) Paste in 1No11mal Air

2·~-------------------------------------------------------------------

=,,~~-... ..... ·············· 0 ,. ... - ~""" ········

• "i"l.,, ••··• m ••••••••••• ••••••• •••••••••••• •••••• •••••••••••••••••••• \Q~'~ ........... .

-2

•4+ m ~~§~~-~~· ~. ····•• 6+·· ..... ~~······

• ('Cl ... . .... . .......... . :2 -10-' ....... . :a+ ••·•··. mrnm m •• • • >Z~:~~. "~ 0

-12·~······

-14~······ ........... ············ ·········-·--·-···· ·······--···· ··································----··············--

-16 .. 1-----------1------------1----------,---------T·-------1---------

Q 100 200 300 400 500 600 Temperature (De9rees Celsius)

r

----------------- -------] ---·- Control ············· Lethabo(-63) --------- Lethabo

- Duvha(~63) .................. Van Eck(-.63) -·-·-·-·- Matla{-63) --------------~---------------------------------------·---------

n IV --Cl

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O> c ro

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CJ) CJ)

ro ~ (fl.

2] Q·········~.··

-2

TGA Plot for the Control Paste Dry Nitrogen Atmosphere

-4-l······· ............................................... .

-6 .. , .......

-8-'···············································

-10+········ ·························

-12

-·--··- ........... _

-14-+--~~~,--~~--.,.~~~-,-~~~-.-~~~-,-~~_____,

0 100 200 300 400 Temperature (Degrees Celsius)

~- 3 Days ··· · ········· 7 Days --------- 14 Days

--------- 21 Days - 28 Days

500 600

0 N 00

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2

o~······

(]) -2 O> c ccs

-4 ...c 0 en en -6 ccs

:.?! cf!. -8

-10

-12 0

TGA Plot for the Lethabo(-63) Paste Dry Nitrogen Atmosphere

....... ~-:::::.:·;:::~~~······-··-' ····-.... \

..... ·················· ... :\~······ 100 200 300 400

Temperature (Degrees Celsius)

-- 3 Days ·················· 7 Days --------- 14 Days

--------- 21 Days - 28 Days

500 600

() I'-..> 'D

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2

o~---

(]) -2 O> c res

-4 ..c 0

CJ) CJ) -6 res ~

*- -8

-10

-12 0

TGA Plot for the Lethabo Paste Dry Nitrogen Atmosphere

100 200 300 400 Temperature (Degrees Celsius)

-- 3 Days --···········- 7 Days --------- 14 Days

--------- 21 Days - 28 Days

500 600

() w 0

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2-·

o-·········

Q) -2 en c co

-4 ..c 0 en en -6 co ~

~ -8

-10

-12 0

TGA Plot for the Duvha(-63) Paste Dry Nitrogen Atmosphere

······· ································ ................ ·····~~······· >::::: .. ,, .. .,,.~ .. "'.::::~·-·.:::::·.~:···· .............. ··········

·"-···~ .. "-1.

································~~··\············································································· ..

'~ \-----·----~·---···--······-·-··-·····--~. ···-...•.....

\~~························ ~

100 200 300 400 500 600 Temperature (Degrees Celsius)

--· 3 Days ·················· 7 Days --------- 14 Days

--------- 21 Days - 28 Days () \.>.) ......

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Q) O> c n1

..c 0 en en n1 ~ (fa

TGA Plot for the Van Eck(-63)Paste Dry Nitrogen Atmosphere

2-,---~~~~~~~~~~~~~~~~~~~~~~

o~·····

-2~········································

-4-+ ...... . ...... .

-6-+ ........ . ...... ········· .......................... . "-···································~················

-a~················ ········ -···.,\ .. ······· :~::::.:: :::·~7· ___ , .. '..~.~:... .: ~.::.: ::· ..... .

-1 o-

-12--+-~~~~-~~~~~~~~~-~~~~~~~~----i

0 1 00 200 300 400 500 600 Temperature (Degrees Celsius)

-- 3 Days ··· ······· · 7 Days -·-·----- 14 Days

--------- 21 Days - 28 Days (") VJ N

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O> c (\1

..c 0 en en (\1

~ <fl.

TGA Plot for the Matla(-63)Paste Dry Nitrogen Atmosphere

2~~~~~~~~~~~~--~~~~~~~~~~~

o--

-2-+·······'-········ ·················

-4 .... ~-- ...... -----..

-6 ·······.:.~:::::::~:·.>::·.-.-.~.·c~::; ···· ········ ·'\···· ·········· ·········· ········· ············································! ....... \,

-a-+···················--·················-'························································-·········---·······------····-----·····---·····-------·~

\\

-···--·---... -- ..... -........ .._ _______ ...

-10+-·········································· ·························································································································································~ ~

-12-+-~~--,-~~~-,-~~~T~~~~~~~--r-~~__,

0 100 200 300 400 500 600 Temperature (Degrees Celsius)

-- 3 Days ············· 7 Days --------- 14 Days

--------- 21 Days - 28 Days Cl VJ VJ

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Q) O> c: cu

..c 0

TGA Plot for the Van Eck(-63)Paste Normal Air Atmosphere

~[~ -2

-4~- ························ .

-6 -·- _, ___ _

.......... --.,, __ -.. <·::~-~-----~~-~-:~----~=~- .. ······· .. ················-- .....

·-····-· ......... ·······--····· cn a~-- ····················· ····· .... ······-····-·--·····----········ CJ) -cu

........ __

~ 10~---···· ······· -cf..

-12~·-······ ······························· ..... ... . ...... ··········· .................. . ..................... .

. -14~---- ........................................................................ ··········································

-16 -4

0 100 200 300 400 500 600 Temperature (Degrees Celsius)

-- 3 Days ··············· 7 Days --------- 14 Days

--------- 21 Days - 28 Days () (.;..) .p.

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0.02-

o-···

~) ·0.02 c ~ ·0.04 0

;,

en ·O. 06 -J. ····················· ···-·····~ en ro

-== .a oa-·····························-······· ..:::: . ~0.1-

0 ® 15 a: ·0.12-

DT,G Pilot for the Control Paste Dry Nitrogen Atmosphere

~----. -~-----r- r

100 200 300 400 'Temperature (Degrees Celsius)

l- 3 Day~. ·················· 7 Days ----- 14 OaysJ - 21 Day.s .................. 28 Days ------------------------------------

·--r-~--~

500 1600

0 w Vt

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..c 0 en en co ~ ,,._ 0 (I) ....... co a:

0.04-

0.02-··

0

-0.02-

-0.04-

-0.06-

-0.08-·

-0.1-·· .

DTG Plot for the Lethabo(-'63) Paste Dry Nitrogen Atmospher,e

-0. U 2-1-----------1·------------T----------·-1·---------T·-------·-·1·-----------

Q 100 200 300 400 500 1600 Temperature (Degrees Celsius)

l-----------------------------J -------- 3 Days ··· ······ · · 7 Days ··--·----- 14 !Days

- 21 Days .................. 28 Days -------------------------------------------

0 w o,

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0.04

0.02-(J)

Ol o-··· c '° ..c ·0.02-············ 0 en en ·0.04-'° ~ 0 ·0.06 Q) .......

'° ·0.08-a:

·0.1·

·O: ttr2 0

DiG Plot for the Lethabo Paste Dry Nitrogen At!mosphe~e

- ~ --~ --r--.--, 100 200 .300 400 500

"Temperature (Degtees Celsius)

l-- 3 Days . ················ 7 D'ay.s --------- 14 !Days

- 21 Day:s .................. 28 Days ------------~-----------------

1600

0 w -.:i

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DTG Plot for the Duvha(-63) Paste Dry Nitrogen Atmospher.e

0. 04-·-------------------------------------------------------

Cll> Ol c ra

..c. 0

CJ) C1l ra

0. 02-1 · t··········. . .

0

~ -0.06-···· 0 G.l -0.08-

....... ra a: .. 0.1

-0.12-

···#rV\~...A":)Af\:;~.._j\_r:+_M / .. ·::,::.~;:.r~.,,2."'~~-:::Jfrll.,,

-0. 14-1----------r-------------r----------1---------T--------i--------Q 1 00 200 300 400 500 1600

Temperature (Degrees Celsius)

~=-= 3 D~ys --=: ....... 7 Days -·----·--- 14 IDayjs

- 21 Days .................. 28 Days --------------------------------------------

~

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0.06-

0.04

Q) 0.02 Ol c '° ...c 0 en -0.02 en '° :2 -0.04 -0 -0.06 Q) ..... '° -0.08 a:

-0.1

-o. n2 0'

DTG Plot for the Van Eck(-:63) Paste Dry Nitrogen Atmosphere

.........................................................

100 200 300 400 500 Temperature {Degrees Celsius)

-- 3 Days · ·-···-····-· 7 Days --------- 14 Days

- 21 Day.s ................ 28 Days

1600

(') w 'O

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..

0.02

DTG Plot for the 1

Matla(·63) Paste Dry Nitrogen At1mosphe~·e

iQ--1·····-··-1i'\fC- -· . . - - . . ..... (l~~~~\I

(!))

Ol c ru ..c

\~.;

·0.02+ ~;\ .................. .

u .0.04--cn 00 ru ~ ·0.06-~--------· '+-0

-~ ·0.08+·-·- ·-····· ··­ru a: ·0.1-

·O. ~ 2 -1-----------i r----~---- -----,--0 100 200 .300 400 500 1600

Temperature (Degrees .Ce·lsius)

l --- J ----- 3 Days ------------ 7 Days --------- 14 Days

- 21 Days .................. 28 Days ------~---------·------------------·-----·-------~-------------

0 i§>

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n (!J) Ol c co ..c

0 CIJ' CIJ' co ~ "t-o Cil)'

o·.04

Cl.02-

o-· ..

·+-'

~ ·0~08

-:0.11

DTG Plot for the Van IEck(-163) Paste Normal Air Atmosphere

....................... u ...... ,

·O: 112 L----..~~~___,._._----~~--~-'-1~---~~~~~------:; 0 100 300 1600 400 500 200

·verrnperature (Degrees Celsius)

- 3 Days ................. 7 Days -------·- 14 ID.ays:

- 21 Days .................. 2.8 Days ~ -

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APPENDIX D

• Concrete mix design incorporating fly ash.

• Portland Cement Institute method of concrete mix design

incorporating fly ash.

• Modified PCI method for fly ash concrete mix design

• Conclusions

Page

Dl

D6

D12

Dl6

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APPENDIXD

METHOD 1: CONCRETE MIX DESIGN INCORPORATING FLY ASH

Dhir ( 1986) gives the main steps to mix design of fly ash concrete as follows :

I. Determination of.free water/port/and cement ratio {WIC)

For a given target strength (28 days), Figure D. l is used to find the relevant (W/C)

ratio.

.. " ::' 80 g, . QI

• ~ 70

" g, I

... 60 N

E E

! 50 &.

c. c ~ 40 ;; c • .. E 3 .. QI

~

.. 2

" .,, I Ill N

0

0

0

\ I \

' \. ' ----- 'rhpc/pla \

i\ I I I I I \ I \ -opc:/pla

' ' I :\.

\!. ', !\ \

\

~ \ ! ' ' '

r\. ' ', I I i

'!\.... ', I ... I

'f'.... ... ,1 ... ['._ ' ... ...

....... ... ......... ... ...

'-. i-....

...... I'.

0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

free warer/portland cemenl 111io

7

.. :; QI .. r. QI

" ~ u 0

0 ; .. &. .. "

60 u I

N E

50 E ! &.

0 40 ~

;; c

30 : E

.. QI

20 ~ .. " .,, I

CD 10 N

Figure D.1 : Relationship between 28-day strength and free water to portland cement ratio.

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2. Determination of.fly ash/composite cement ratio (FIF+C)

Figure D.2 is used to obtain the value for (F/F+C) in relation to the free

water/portland cement ratio. The value from the graph is a first approximation and

might be changed due to additional design requirements.

1.2

0

~ c 1.0 .. E

" u

" c .. :;: o.e 0 Q ... 0

i 0.6

0.4 /,:'. b% :/' 10

J I I

I I I I V / J J

I/ j /

J I v / v / pla grade ---..,l1 .,_ p

/ / v /

/ / v / v '/

~/ ~ v 'l,r

20 30 40 50

optimum F/(F+Cl ratio 'II.

Figure D.2 : Relationship between free water/portland cement ratio and fly ash/total composite cement content.

3. Determination of.free water content (W)

The free water content is chosen in terms of the coarse aggregate used and the

required workability (measured as the slump). Table D.1 lists values for the water

content for concrete containing 30°/o fly ash. For different percentages of fly ash,

adjust as follows :

For fly ash >30%, subtract 1 litre/m3 per 2% deviation.

For fly ash <30%, add llitre/m3 per 2% deviation.

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Free waler content, l/m> Maximum aggregate Aggregale Grade• or Slump (mm) size (mm) &ype pfa 10-30 30-60 60-120

JO Gravel Premium 160 i75 190 I 170 18S 200 2 180 195 210

Crushed Premium 180 195 210 I 190 205 220 2 200 215 230

20 Gravel Premium 140 155 170 I 150 165 180 2 160 175 190

Crushed Premium 160 175 190 I 170 185 200 2 180 195 210

Table D.1 : Approximate values for the free water content for fly ash concretes

containing 30% fly ash.

4. Determination o(portland cement (C) and fly ash (F) contents

The following equations are used with X = 100( F ) . F+C

C=( %) and F = ( c( Yi oo) ) 1-( Yioo)

5. Determination of the total aggregate content (A)

D3'

The first step is to estimate the plastic density of the concrete, a, from Figure D.3.

-... ! aoo .. ~

• i~OO ~ .. c 0

" .. ;; "2>00 c . .. ; 2200 •

2.9

2.e

2. 7

2.9

2.$

2.• 100 120 ·UO 1eo 110 200 no

lrte w•ttr contenl Ck91m3 )

Figure D.3 : Relationship between the plastic density and free water content of

compacted fly ash concrete.

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The second step involves the calculation of the total aggregate content, A from the

formula given by :A= a-(C+F +W)

From the value obtained for the total aggregate, find the fine aggregate content,

Af, using figure D.4 or D.5.

slump 10-30mm 30-60mm 60-120mm

~ I "

-- 70 -- - ! "·· -~-·-- ,___ - ·-·- - ~ .. ---+----i-t ! ······.... ······· ... ~ 6 0 ,.:::-. .. • .. .... c ! 50 ........... ~..... • ......... . .... ···~ ..... ~~::·::·~.:\~ .!: •• ... M ....... ......... ·... ..... 1 •• .. !-4r - ...... ..... .......... "·!:! ...... _ .... _ ......... l '\.· 0 ,0 •. ! ••••• ••• -~ l'•~ g ........ ··f...... ""··· F ""·..... ·····.,f ..

········· ······ -~ 30 t----t·---+_,_-.,,-<-- , ___ , _ ___:::_. --t--'1----i·-- -

g ········· ···· ... 0 Q20...__... _ _...__......__~ _ _.__...__._____. _ _... _ _.__~

200 300 400 500 200 300 400 500 200 300 400 500

total composite cement content (~gtm 3 )

Figure D.4: Determination of Affor IOmm maximum aggregate size.

1lu"'1> 10-30mm 30-60mm 60· 120mm

! 601----+---+--+---f-- >----- --- ·----.. -·~: ___ , _____ _

; 50 ...... ·~~ .. -- ·--.. ~

r :: ::~:::: :::.;··· ········1· .__ :~s ~~~~>. ~~= ·:~:~ ~:;~\·:~~: g .... "··~ ... ··.......... ..... ·· .. , ..... ~... .......... . ............ . -~ 20 "·:.:_,r:"" ... · ·-____ :_: :"-.;·· . -~ 0 ••• • •• g ...... I Q 10....._ ....... _ _.._ _ _._ _ _.__....___...___._____..___._ _ _._ _ _._--..,...;

200 300 400 500 200 300 400 500 200 300 400 500 600

total composite cement contenl (kgtm3 )

Figure D.5 : Determination of Af for 20mm maximum aggregate size.

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6. Conduct a trial mix

From the mix proportions detennined so far, a trial mix is prepared and then

characterized in terms of properties. If the workability (from slump test) differs

from the design value, W, the free water content, has to be adjusted. If the

strength (e.g. compressive cube strength) does not meet the set requirement, (W/C)

has to be modified.

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METHOD 2 : PCI METHOD OF CONCRETE MIX DESIGN

INCORPORATING FLY ASH

D6

A widely accepted method of concrete mix design has been developed by the

Portland Cement Institute of South Africa. In the context of the presented topic of

fly ash addition to concrete, the following report summarizes the important steps

of the PCI method as given in Fulton's Concrete Technology (Addis, 1986).

1. Selection ofthe fly ash content

The nonnal practice is to use between 15% and 30% of fly ash by mass of total

cementitious material. However mixes with up to 50% fly ash _have proved

successful in special applications. If the fineness of the ash is known, Figure D.6

gives information about fly ash content as a function of free water content.

220-----.,...------.----..----...----.-----,

Fly ash ;; 200 in cement ----+--=r"c:....+--_,,,1-~~~---f ~ ~o.ot.r2l __ _ 0:_1. ____ __ _ .. ~ 190~~-~l-~~~--,,.,,....q.--::.,,,,C-'7""f-~c;..._-+----!

ISO'--'---~~---'----"--_.... __ __.._ __ __. IS 2S 3S 4S SS s

Fly ash sieve residue at 4S }'m ('kl

Figure D.6 : Relationship between fly ash fineness and free water content of

concrete with 50-75mm slump as a function of different fly ash percentages;

nominal cement content 300kglm3.

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2. Determination o((CTIW) ratio for a given target strength where CT represents

the total cementitious material content and W refers to the quantity o((ree water

Figure D. 7 gives some combinations of fly ash and concrete. In the case where

different ratios are to be used, the presented curves may be extrapolated to find the

value for (CT/W).

Average 28-day st rcng th

50 i----+---r-

-l. 40 1----------¥----:l-~-+---+---+--:I 2:

! j5 i----i.------+.1''--'"~_..,,_---_..~ • .. u c 0

~ 30 ----t-il" ~~~--+-0

.&. -~251----+--1-~~.__---+------_..--+----+--f • .. -;; w .~ 20 t---.."t-f-~--t Ill Ill Ill

ii. & 15 ......_ __ ·.II---- -----t---t--t---+---i

u These curve:; aroi based on Transvaal

10

5

0

OPC & Malla FA and arc the result of a largq number of 100-mm concrete cube tests by D&H Ash Resources and the Portland

Cement Institute

1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2.6 Cement water ratio by mass

(Ratio of total ccmenlitious material to water l

Figure D. 7 : Relationship between the 28-day target strength and total

cementitious material to water ratio for different proportions of fly ash additions.

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Figure D.7 may also be used as starting point in the design of the mix. Then, ifthe

target strength is known as well as the ratio of (CT/W), the relevant proportion of

fly ash is chosen from the graph.

3. Determination ofthe water content

Fulton (Addis, l 986)indicates the approximate water contents for concrete with

optimum 19mm stone quantity and slump of75mm to be as given in Table D.2.

Table D.2: Water content as a function of sand quality.

Sand Quality Water Content (IJm3)

Natural Sand Crusher Sand

Very Poor 240 235

Poor 225 225

Average 210 215

Good 195 205

Excellent 180 195

An important step at this stage is to incorporate the reduced water requirement of a

fly ash mix. A l 0~'0 reduction in water content relative to the straight cement mix

is a commonly used figure.

Figure D.8 below relates the change in slump to a change in the water content.

This presentation often becomes very useful once the first trial mix has }?een

prepared.

'Now that the figures for cement -, fly ash - and water content are known, the

proportions of coarse and fine aggregate to be used are calculated.

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0 12511--+4~-++-~"ll"t-~~~ttb'--t~-1 a. E ~

~ 100~--l~--l.l~~~-+7":....-+--~'--t 0

t!l

2 5 so 75 100 125 150 175 200 mm

To change slwmp from

Figure D.8 : Change in water content required to bring about the desired change in slump.

4. Determination ofstone content

The stone content is given by the fonnula:

S = CBD(K-0.IFM)

where CBD = dry compacted bulk density of the stone

K = a factor which depends on the maximum stone size as well as

the workability of the concrete

Fulton (Addis, 1986) lists the following values for the factor K as in Table D.3.

Table D.3 : Values for the factor K.

Slump range Placing Method K-Values (mm) Maximum Stone Size (mm)

9.5 13.2 19.0 26.5

75-150 Hand Compaction 0.75 0.84 0.94 0.99

25-100 Moderate Vibration 0.80 0.90 1.00 1.02

37.5

I.OS

1.10

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If the compacted bulk density of the stone equals the value of l 529kg!m3, then the

above table expressed graphically is presented in Figure D.9.

In the case where the CBD value of the stone to be used differs from l 520kglm3,

Figure D.9 may still be used; the only alteration being that the value obtained from

the graph for the stone content is to be multiplied by a factor of (actual CBD/1520)

to compensate for the difference.

112 19 37,5 Maximum size of stone (mml

3,0 ~ c c .. 0 .. ~ 7,5 :> r .. c c • 7,0 c ii:

1,6 ~-----__. __ ...___.._._ ......... __. ____ ....___ ......... __ .......,._ _ _,

600 70:l 800 900 1000 1100 1200 1300 1400 1500

Mass of st one ( kg /m~ )

Figure D.9 : Stone content as a function of the fineness modulus of the sand as

well as the method of placing.

The stone content calculated has to be adjusted to account for the increase in the

volume of fines due to the fly ash addition. Use is made of Figure D .10 to find the

percentage adjustment.

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8

7

6

! 5 0

iii

g 4 .2 -~ "8 3 g, ~ 2 ~ "' CL. 1

0

/ ~

_,,. v ~v

,,

,/ v

15 20 30 40 Fly ash content as a percentage

of total cementltious material

Figure D.10: Chart for increasing the stone content.

5. Calculation ofthe sand content

The following fonnula applies in this case :

Dll

50

Sand= RDsand• 1 ooo[i -( Cement )-( Stone )-( FlyAsh )-( Water )]w RD•IOOO RD•IOOO RD•IOOO RD•IOOO

here RD refers to the relative density of the material.

(If not specified, use RD=2.30 for fly ash.)

6. Conduction ofa trial mix

A trial mix is prepared and its properties examined, leaving room for possible

adjustment of the parameters used in the design.

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METHOD 3 : MODIFIED PCI METHOD FOR FLY ASH CONCRETE

MIX DESIGN (National Building Research Institute, 1985)

The method which was developed by the National Building Research Institute and

is based on the PCI method of concrete mix design for ordinary OPC mixes not

containing mineral admixtures. The principle is to design a concrete which will

have the same workability and 28-day compressive strength as the corresponding

OPC concrete.

1. Given the specified 28-day cube compressive strength. the target strength is

chosen. \,

According to SABS 0100-2(1992), the characteristic strength is the value of the

compressive strength of the concrete, below which not more than 5% of the valid

test results obtained from cubes of concrete of the same grade fall. The target

strength is an average value of concrete strength which is higher that the specified

strength, and that is aimed for to ensure that the characteristic strength is attained.

Based on statistical analyses, a formula was derived to calculate the target

strength:

fi = fc + (I. 7• 8)

where ft = target strength in MPa

fc = characteristic strength in MPa

o = standard deviation in MPa

The standard deviation is a characteristic of the materials, the mix proportioning,

mixing methodology employed, as well as the curing conditions prevailing.

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2. Choice of water/cement ratio to give required target strength.

The (W/C) ratio is obtained from Figure 0:11 which is based on ordinary Portland

cement concrete mixes.

Use a.= 1.0 for average 28-day strength

Use a.= 1.85 for minimum 28-day strength for ordinary portland cement.

Nonoal Portland ct~tftt and P.l.F.C.

~~'t-+.--f-+--+--+--t-t-"t(4pproaiir.ue)

O,l 0,4 0,)

VATEl:C~T llAT10 IY KASS

Figure D.11 : Relationship between the compressive strength and water to cement ratio.

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D14

3. Determination of the water content.

The water content is greatly influenced by the (fine) aggregate used. Table D.2

presented earlier, gives guidelines in choosing the water content as a function of

the quality of the sand used. The water content for fly ash concretes is about 10%

less than that of portland cement concretes (for the same workability and 28-day

strength). This 10% deduction has to be incorporated for.

4. Calculation of the cement content.

Based on a cementing efficiency equal to 0.4, the following formula has been

derived:

C=( ;c}L~~=~] where C = portland cement content in kg per m3

W = water content in liters per m3

P = fly ash fraction of total cementitious binder content.

5. Determination of the fly ash content

The following formula is used:

F= P*C 1-P

where F = fly ash content in kg per m3

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6. Determination of the stone content

Figure D.9 given previously is used to obtain the stone content. This figure is

based on a consolidated bulk density for the stone of 1520kglm3 and the stone

content has to be adjusted if the CBD value differs.

Adjusted SC =.SC* (Bulk Density) 1520

where SC = stone content in kg per m3

The fineness of the fly ash, the reduced portland cement content as well as the

reduced water content all influence the quantity of aggregate. This is why a

further modification to the stone content is prescribed:

SC1 =SC +(F(~)) where SCf = final stone content for the particular mix

7. Calculation o(the sand content.

The following formula applies:

Sand= [1000-(~ )-(i~ )-(~ )-w }RD-where Sand = sand content in kg per m3

RD = respective relative densities

8. Trial mix

When the quantities for all the concrete components have been calculated, a trial

mix is made. If the required slump has not been achieved, Figure D.8 given earlier

is used to find the relevant adjustment.

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D16 CONCLUSIONS

Three methods of fly ash concrete mix design have been presented. The common

aim is to calculate the quantities of concrete constituents on the basis of certain

criteria. Each method approaches the topic from a different angle which is

determined by the knowledge of material properties and relative material

interactions. Apart from these more theoretical considerations, the practical

· expenence of concreting has greatly aided the development of such design

methods.

The first method approaches the free water to cementitious material ratio in two

steps. Firstly, for a specified target strength (28-day compressive), a free water to

portland cement ratio is chosen. Secondly, an optimum ratio of fly ash to fly ash

plus portland cement is determined which is a function of the grade of fly ash

used. The different grades are summarized in Table D.4.

Table D.4 : Classification of fly ash for the use in concrete (Dhir, 1986).

Grade of Fly Ash % Fineness* Characteristic

Premium <5 Excellent Properties

1 5-20 / Good Properties

2 20-35 Good to Adequate Properties

3 >35 Doubtful economic

viability

* Percentage fly ash sieve residue at 45 µm

The second method, developed by the Portland Cement Institute of South Africa,

requires the prior knowledge of the percentage fly ash to be used. With this in

mind, the ratio of total cementitious material to water is chosen as a function of the

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017

28-day target strength. The free water content is related to the quality of the fine

aggregate to be used. (In the case where a detailed sieve analysis of the ash is

available, the percentage ash retained on the 45µm sieve may be used as a further

guideline to determine the water content of the mix.)

The third method relies on the principle that the fly ash concrete designed

according to it, will have the same 28-day wet-cured compressive strength and

workability as a comparable OPC mix designed according to the PCI method for

OPC mixes .. The selection of water to cement ratio is based on a straight OPC mix

and is influenced by alpha, a factor indicating the cementing efficiency. The water

content is determined in relation to the quality of the (fine) aggregate.

The· relevance ~f a particular method can not be predicted with absolute

confidence and the concrete technologist has thus to rely on trial mixes to show

whether the required specifications have indeed been met. The adjustment of a

concrete mix after unsatisfactory performance of the trial mix is often influenced

by experience more. than by finite numbers.

In general, the availability of a wide range of admixtures for concrete, opens up

the overall scope of mix design. However the application of admixtures should

always be given careful consideration in terms of type and quantity, as the

effect(s) derived from using these might have unforeseen consequences. These

might be short-term, for example the incompatibility with other concrete

constituents, or long-term, for example reduced durability performance.