TOME PhD's Thesis

REPUBLIC OF CAMEROON REPUBLIQUE DU CAMEROUN
UNIVERSITY OF DOUALA. UNIVERSITE DE DOUALA.

************* **************
GRADUATE SCHOOL IN ECOLE DOCTORALE DES SCIENCES
FONDAMENTAL FONDAMENTALES ET APPLIQUEES.
AND APPLIED SCIENCES
**************
*************
UNITE DE FORMATION DOCTORALE
GRADUATE TRAINING UNIT IN DE CHIMIE ET BIOCHIMIE.
CHEMISTRY AND BIOCHEMISTRY
CHEMISTRY LABORATORY
LABORATOIRE DE CHIMIE
Synergistic use of municipal solid waste

incinerator fly ash and volcanic ash for
alkaline activated cement synthesis
A thesis submitted in total fulfillment of the requirements for the

degree of Doctor of Philosophy in Chemistry
By
TOME Sylvain (Mat: 09S09088)
M.Sc. in Physical-Chemistry
Under the Supervision of:
Pr Jacques ETAME Pr Marie Annie ETOH Dr Sanjay Kumar

Full Professor Associate Professor Senior Scientist Principal
Faculty of Science Faculty of Science MER Division
University of Douala, Cameroon University of Douala, Cameroon CSIR-National Metallurgical Laboratory, India
Year 2020
i
CERTIFICATION
To certify that this thesis have been completed to our satisfaction and
that in our opinion it is fully adequate, in scope and quality, as a thesis
and for degree of Doctor of Philosophy (PhD) in Materials Chemistry.
ii
iii
LIST OF ADMINISTRATOR STAFF AND TEACHER OF THE
FACULTY OF SCIENCES
REPUBLIC OF CAMEROON UNIVERSITY OF DOUALA

REPUBLIQUE DU CAMEROUN UNIVERSITE DE DOUALA
******* *******
Paix – Travail – Patrie FACULTY OF SCIENCES
Peace – Work – Fatherland FACULTE DES SCIENCES
******* *******
PO BOX : 24157 Douala
Email : fsc-ud@yahoo.fr
*********
Phone/Fax : (+237) 699454411
ACADEMIC YEAR 2019/2020
Updated : 20 June 2020
ADMINISTRATION
DEAN : NIDA Marie Joseph épse NTAMACK (Professor)
VICE DEAN/DPSAA : AZEBAZE Anatole Guy Blaise (Associate Professor)
VICE DEAN/ DSSE : PRISO Richard (Associate Professor)
VICE DEAN/ DRC : NDOM Jean Claude (Associate Professor)
1. DEPARTEMENT OF BIOLOGY AND ANIMAL PHYSIOLOGY (BA) (23)
N° Noms et Prénoms Grade Observations

1 1 MASSOMA LEMBE Dieudonné Associate Professor Head of Departement
2 2 MANDENGUE Samuel Honoré Professor Full Time
3 3 AKONO NTONGA Patrick Associate Professor Full Time

4 4 DONGMO Alain Bertrand Professor Full Time
5 5 KENNE Martin Associate Professor Full Time
6 6 LEHMAN Léopold Associate Professor Full Time
7 7 TINDO Maurice Associate Professor Full Time
8 8 MBIDA MBIDA Jean Arthur Associate Professor Full Time
iv
AYINA AYINA Clarisse Noel
9 9 Senior Lecturer Full Time
épse LISSOCK
10 10 MISSOUP Alain Didier Senior Lecturer Full Time
11 11 ENDOUGOU EFFA Anne Marie Senior Lecturer Full Time
12 12 KOJI Ernest Senior Lecturer Full Time
Senior Lecturer Head of Departement

12 12 NACK Jacques
ISH
14 14 TCHAMADEU Marie Claire Senior Lecturer Full Time
15 15 WANKEU NYA Modeste Senior Lecturer Full Time
16 16 AHMADOU Senior Lecturer Full Time
17 17 KOJI Ernest Senior Lecturer Full Time
18 18 Aïcha De NKAINSA LINDOUX II Assistant Lecturer Full Time

19 19 ATEBA Sylvain Benjamin Assistant Lecturer Full Time
20 20 BIKA LELE Elysée Claude Assistant Lecturer Full Time
21 21 BOGNING Zangue Calvin Assistant Lecturer Full Time
22 22 KAPSO TCHOUANKEP Mireille Assistant Lecturer Full Time
23 23 MEKOULOU NDONGO Jerson Assistant Lecturer Full Time
2. DEPARTEMENT OF BIOLOGY AND PLANT PHYSIOLOGY (BV) (19)
24 1 NGO NKOT Laurette épse EKOUE Associate Professor Head of Departement

25 2 NDONGO DIN Professor Full Time
26 3 TAFFOUO Victor Désiré Professor Full Time
27 4 ASSENG Charles Carnot Associate Professor Full Time
28 5 BETTY Jean Lagarde Associate Professor Full Time
29 6 DIBONG Siegfried Didier Associate Professor Full Time
30 7 FANKEM Henri Associate Professor Full Time
31 8 PRISO Richard Associate Professor Vice Dean
32 9 NDIANG Zenabou Senior Lecturer Full Time
v
33 10 NGOTTA BIYON Jacques Bruno Senior Lecturer Full Time
34 11 SIMO Claude Senior Lecturer Full Time
TCHIAZE OFOUE Alice Virginie

35 12 Senior Lecturer Full Time
épse GOUADO
36 13 Séraphine EBENGNE MOKAkE Assistant Lecturer Full Time
37 14 LADOH YEMEDA Christelle Flora Assistant Lecturer Full Time
38 15 MADOUNTSAP TAGNANG Nadège Assistant Lecturer Full Time
39 16 MBOUSSI Serges Bertrand Assistant Lecturer Full Time
40 17 MFONKA Zakari Assistant Lecturer Full Time
41 18 MVOGO OTTOU Patrice Brice Assistant Lecturer Full Time
42 19 WAMBA FOTSO Oscar Simple Assistant Lecturer Full Time
3. DEPARTEMENT OF BIOCHEMISTRY (BC) (27)
43 1 NGONO NGANE Rosalie Annie Professor Head of Departement

44 2 GOUADO Innocent Professor Full Time
45 3 JAZET DONGMO Pierre Professor Full Time
46 4 KANA MARIE Modestine épse SOP Associate Professor Full Time
KOANGA MOGTOMO Martin Associate Professor

47 5 Full Time
Luther
48 6 SAMEZA Modeste Lambert Associate Professor Full Time
Associate Professor Chief of service of

49 7 TAVEA Fréderic Marie
programming / FMSP
50 8 MINYAKA Emile Associate Professor Chief DFI – IUT
51 9 NDOMOU Mathieu Associate Professor Full Time
Senior Lecturer Chief of service

52 10 KORO KORO Francioli
DAAC
53 11 LENG Marlyse Solange Associate Professor Full Time
54 12 NJINKOUE Jean Michel Senior Lecturer Full Time
55 13 EBELLE ETAME Rebecca Senior Lecturer S.G MINRESI
vi
56 14 ETOUNDI Blanche Cumégonde Senior Lecturer Full Time
57 15 TCHAMENI NGUEMZI Severin Senior Lecturer Full Time
58 16 NOAH MBOENE Alexandre Assistant Lecturer Full Time

59 17 TAMGUE Ousmane Senior Lecturer Full Time
60 18 FOUELIFACK Eric Assistant Lecturer Full Time
61 19 AKAMI Mazarin Assistant Lecturer Full Time
62 20 DEMASSE MAWAMBA Adelaide Assistant Lecturer Full Time
63 21 DONGHO DONGMO Fabrice Fabien Assistant Lecturer Full Time
64 22 FOGANG MBA Aymar Rodrigue Assistant Lecturer Full Time
65 23 FOUELIFACK NZEKO Eric Assistant Lecturer Full Time
66 24 LIENOU LIENOU Landry Assistant Lecturer Full Time
NGUIKWIE KWANGA Sylvie épse
67 25 Assistant Lecturer Full Time
MEKONDANE
68 26 NOLLA Nicolas Policarpe Assistant Lecturer Full Time
69 27 SOH OUMBE Aimé Valère Assistant Lecturer Full Time
4. DEPARTEMENT OF CHEMISTRY (CH) (31)
70 1 ETOH Marie Annie Associate Professor Head of Departement

71 2 WANSI Jean Duplex Professor Full Time
VARDAMIDES Catherine épse
72 3 Professor Full Time
MASSOMA
73 4 MBAZE MEVA’A Luc Leonard Professor DSAAR UY1 FS
74 5 AZEBAZE Anatole Guy Blaise Associate Professor Vice Dean / DPSAA
75 6 NDOM Jean Claude Associate Professor Vice Dean / DRC
76 7 KAMDEM WAFFO Alain Associate Professor Full Time
77 8 NGUEFA HAPPI Emmanuel Associate Professor Full Time
DIKA MANGA Joseph Marchand Associate Professor

78 9 Full Time
Robert
79 10 NASSI Achille Associate Professor Full Time
vii
Associate Professor Chief of service
80 11 TOZE Flavien Aristide Alfred
DAAC
Associate Professor Head of Departement
81 12 NOUGA BISSOUE Achille
GC/ ENSET
82 13 AKONE Hervé Sergi Senior Lecturer Full Time
BASSOMO Monique Yolande épse Senior Lecturer

83 14 Full Time
EWONKEM
84 15 BIKELE MAMA Désiré Associate Professor Full Time
85 16 CONDE Mariam épse ASSENG Senior Lecturer Full Time
86 17 DINA David John Daniel Senior Lecturer Full Time
87 18 KEDE Charles Melea Senior Lecturer Full Time
88 19 KENMOGNE Sidonie épse TAVEA Senior Lecturer Full Time
89 20 LOBE SONGUE Jules Senior Lecturer Full Time
90 21 MAKOTA Suzanne épse NDI Senior Lecturer Full Time
91 22 BANENZOUE Charles Senior Lecturer Full Time
92 23 TCHIETA Pierre Gérard Senior Lecturer Full Time
TCHOUANKWE KAMGA Emile Senior Lecturer

93 24 Full Time
Duclo
94 25 AKONE Hervé Sergi Senior Lecturer Full Time
95 26 NGO HANNA Joelle Assistant Lecturer Full Time

96 27 ATEBA AMANA Baruch Assistant Lecturer Full Time
97 28 AWAZI TENGU épse NYONGHA Assistant Lecturer Full Time
98 29 LONGUE EKON Jean Pierre Assistant Lecturer Full Time
99 30 MABOU LEUNA Jules Blaise Assistant Lecturer Full Time
100 31 MAZA DJONKAM Hermine Laure Assistant Lecturer Full Time
101 32 NGASSA PIEGANG Guy Bertrand Assistant Lecturer Full Time
5. DEPARTEMENT OF MATHEMATICS AND COMPUTER SCIENCE (MI) (18)
viii
102 1 BOWONG TSAKOU Samuel Associate Professor Head of Departement
103 2 FONO Louis Aime Associate Professor Full Time
DONFACK Véronique épse Senior Lecturer
104 3 Full Time
KOMMOGNE
105 4 MBAMA ENGOULOU Bertrand Senior Lecturer Full Time
106 5 NGAkEU Ferdinand Senior Lecturer Full Time
107 6 NOUMSI WOGUIA Vigny Auguste Senior Lecturer Full Time
108 7 TAGNE WAFO Roger Senior Lecturer Full Time
109 8 TEMGOUA KAGOU Anatole Senior Lecturer Full Time
110 9 TSIMI JEAN Armand Senior Lecturer Full Time
DJEUMEN DJATCHA Rodrigue Assistant Lecturer

111 10 Full Time
Aime
112 11 NDJE Yves Jonathan Assistant Lecturer Full Time
113 12 ONANA NDZANA Assistant Lecturer Full Time
114 13 UM Laurence Assistant Lecturer Full Time
115 14 PEMHA Gabriel Cedric Assistant Lecturer Full Time
116 15 FOTSING TETSING Hans Assistant Lecturer Full Time
117 16 MOSKOLAI NGASSAHA Justin Assistant Lecturer Full Time
118 17 KOKOMO AYISSI Eric Brice Assistant Lecturer Full Time
119 18 DJIKEN Guy Lahlou Assistant Lecturer Full Time
6. DEPARTEMENT OF PHYSICS (PH) (26)
120 1 NGUENANG Jean Pierre Associate Professor Head of Departement

121 2 MOUKENGUE IMANO Adolphe Professor Dean -FGI
DAAF University of
122 3 MOTAPON Ousmanou Professor
Maroua
Chief of service
123 4 MONKAM David Professor
CSDPR
ix
Dean of FS University
124 5 MOHAMADOU Alidou Professor
of Maroua
125 6 LENOUO Andre Associate Professor Full Time
126 7 NANA Laurent Associate Professor Full Time
127 8 YAMAPI Rene Associate Professor Full Time
128 9 WEMBE TAFO Evariste Associate Professor Full Time
Associate Professor Chief of Service

129 10 NDONTCHEUNG MOYO Maurice
ANRP
130 11 DAFOUNANSOU Ousmanou Senior Lecturer Full Time
Senior Lecturer Head of Division

131 12 EYIKE Albert
MINRESI
132 13 LISSOUK Daniel Senior Lecturer S.G ENS Kumba
133 15 MBIAKE Robert Senior Lecturer Full Time
134 15 NOUPA Claude Senior Lecturer Full Time
135 16 NGWA EBONGUE Alexandre Senior Lecturer Full Time
136 17 ZANGA AMOUGOU Alain Senior Lecturer Full Time
137 18 EKOE A AkATA Aloys Martial Senior Lecturer Full Time
138 19 EPEE EPEE Michel Douglas Senior Lecturer Full Time
139 20 KENGANG KANA Lucas Zephirin Senior Lecturer Full Time
140 21 ATANGANA NKENE épse NDOP Assistant Lecturer Full Time

141 22 BELL Jean Pierre Assistant Lecturer Full Time
142 23 LEKEUFACK TIOKENG Olivier Assistant Lecturer Full Time
143 24 MENYE Cyrille Assistant Lecturer Full Time
144 25 MEYAP SOH Cladisse Assistant Lecturer Full Time
145 26 ONDOUA Rodrigue Yanick Assistant Lecturer Full Time
7. DEPARTEMENT OF EARTH SCIENCES (ST) (22)
146 1 NIDA Marie Joseph épse Professor Head of Departement
x
NTAMACK
147 2 ETAME Jacques Professor Director IUT Douala
Associate Professor Assistant Director
148 3 NGON NGON Gilbert
EGEM Ngaoundéré
149 4 OWONA Sebastien Associate Professor Full Time
150 5 BASSEKA Charles Antoine Senior Lecturer Full Time
151 6 BAYIGA ELIE Constantin Senior Lecturer Full Time
152 7 Christophe WONKAM Senior Lecturer Full Time
153 8 LISSOM Justin Senior Lecturer Full Time
Senior Lecturer Head of Departement

154 9 MPESSE Jean Engelbert University of
Ngaoundéré/EGEM
155 10 MVONDO OWONO François Senior Lecturer Full Time
156 11 NGO BOUM Suzane épse NKOT Senior Lecturer Full Time
Senior Lecturer Director of Research

157 12 NKOUE NDONDO Gustave Raoul
N01 MINSUP
OUAFO MENDO Marie Roumy épse Senior Lecturer
158 13 Full Time
LEUMBE
159 14 YOUMEN Dieudonné Senior Lecturer Full Time
160 15 EMVOUTOU Huguette Christiane Assistant Lecturer Full Time
161 16 IBOUM KISSAAKA Joseph Bertrand Assistant Lecturer Full Time
162 17 EMVOUTOU Huguette Christiane Assistant Lecturer Full Time
163 18 ITIGA Zenon Assistant Lecturer Full Time
164 19 NJO MBIE WANGSONG Patrick Assistant Lecturer Full Time
165 20 NSANGOU NGAPNA Moussa Assistant Lecturer Full Time
TCHUIMEGNIE NGONGANG Assistant Lecturer

166 21 Full Time
Nicaise Blaise
167 22 TCHEUMEUNACK KOUEMO Jules Assistant Lecturer Full Time
xi
8. CEPAMOQ (10)
168 1 KWATO NJOCK Moise Godfroy Professor Chief of centre

169 2 KENFACK ASSONGO Cyril Associate Professor Full Time
170 3 BOURI Celsus Senior Lecturer Full Time
171 4 DJIEUDEU Nicodème Senior Lecturer Full Time
172 5 MOHAMADOU BALLO Senior Lecturer Full Time
173 6 NKEM Christophe Senior Lecturer Full Time
174 7 SILENOU MENGOUE Marius Senior Lecturer Full Time
TETCHOU NGANSO Hugues Senior Lecturer

175 8 Full Time
Merlain
176 MBOGNING FEUDJO William Senior Lecturer Full Time
177 9 BONGUE Daniel Senior Lecturer Chief of service
Departmental allotment of parmanent Lecturers
Départements Number of Lecturers
xii
Professors Associate Senior Assistant Total
Professors Lecturers Lecturers
BA 2 (0) 7 (0) 8 (3) 6 (2) 23 (5)
BV 3 (0) 5 (1) 5 (2) 6 (2) 19 (5)
BC 3 (1) 8 (2) 5 (2) 9 (2) 25 (7)
CH 3 (1) 10 (1) 11 (4) 7 (3) 31 (9)
MI 1 (0) 1 (0) 7 (1) 9 (1) 18 (2)
PH 4 (0) 5 (0) 10 (0) 6 (2) 25 (2)
ST 1 (0) 4 (1) 9 (2) 6 (2) 20 (5)
CEPAMOQ 1 (0) 1 (0) 7 (0) 1 (0) 10 (0)
Total 18 (2) 41 (5) 62 (14) 50 (14) 171 (35)
Giving a total of : 177

- Professors : 18 (2)
- Associate Professors : 41 (5)
- Senior Lecturers : 62 (14)
- Assistant Lecturers : 56 (6)
- ( ) = Number of women
The Dean of the Faculty of Science
xiii
Dedication
For THE Nana’s family owing to immEasURaBlE

support THROUGHOUT my education.
xiv
Acknowledgments
It is a pleasure for me to express my gratitude to all those who in one way or another
have contributed to the success of this work.
Firstly, I would also like to express my gratitude to Professor Jacques ETAME and
Professor ETOH Marie Annie for supervising this work and for all their dynamism and
scientific skills that have enabled me to carry out this work successfully. That they find here
the assurance of my deep respect and thankfulness.
I would like to express my gratitude to the lecturers of the Faculty of Science in

general and the Department of Chemistry in particular at the University of Douala for their
teachings and knowledge that have enabled me to progress in my studies.
I would like to be thankful to the Third World Academy of Sciences, Italy (TWAS)
and the Council of Science and Industrial Research, India (CSIR) for financial support of this
thesis under 2016 TWAS-CSIR sandwich postgraduate fellowship award FR number:
3240293597.
A special thanks to Dr Sanjay Kumar, for the honour he gave me to be part of this
research. May he receive my full appreciation for helping me in the choice of this research
topic, in the revision of the articles and thesis. I would like to take this opportunity to express
my high esteem, consideration and gratitude to him.
I’m grateful to the Director of CSIR-National Metallurgical Laboratory for having

made available all facilities for carrying out this work through In-House Project Support
Group (IPSG) with project number: OLP-0282.
I would also like to thank the division heads, scientists, technicians and support staff
of the CSIR-National laboratory for their hospitality and love, which enabled me to spend an
unforgettable stay at the said Metallurgical institution.
I’m glad to the MIPROMALO-CAMEROON’s scientists for having made accessible

all facilities during the three months academic internship at 2016, which initiate me on
geopolymer technology.
I express my thankfulness to BOCOM incinerator Cameroon to allow us to collect the

incinerator fly ash in their company.
xv
I would like to thank Dr KAMSEU Elie, Dr DJOBO Jean Noel, Dr SHIKUKUKU
Victor and Dr AKUMBOM Virgity for their scientific contribution and the revision of my
articles and thesis.
I would like to thank Pr Nana Laurent in particular for all the support he gave me over
and over. May he find here the assurance of my gratitude and may the Lord GOD bless him.
I would also like to thank my classmates, TABEKOUENG.G, AKOSUNG.E for the

time we spent together.
I would also like to thank all those I did not mention but who nevertheless answered
my questions, advised me, made themselves available to help me or simply supported me in
this work. May those I have forgotten forgive me.
xvi
Table of Content
List of administrator staff and teacher of the Faculty of Sciences .............................................. i
Dedication ............................................................................................................................... xiv
Acknowledgments.................................................................................................................... xv
Table of Content ....................................................................................................................xvii
List of Figures ......................................................................................................................... xxi
List of abbreviation ................................................................................................................ xxv
Abstract ................................................................................................................................xxvii
Résumé............................................................................................................................... xxviii
Introduction ................................................................................................................................ 1
CHAPTER I: Literature review ................................................................................................. 4
I.1. Volcanic ash ..................................................................................................................... 4

I.1.1. Definition of volcanic ash ......................................................................................... 4
I.1.2. Physical and chemical properties of volcanic ash ..................................................... 4
I.1.3. Pozzolanic activities of volcanic ash ......................................................................... 5
II.1.4. Use of volcanic ash .................................................................................................. 5
I.1.5. Pozzolana in Cameroon ............................................................................................. 6
I.2. Municipal solid waste ashes and municipal solid waste incinerator fly ash (MSWI-FA)
................................................................................................................................................ 7
I.2.1. Definition of municipal solid waste ashes................................................................. 7
I.2.2. Properties of Municipal solid waste fly ashes ........................................................... 8
I.2.3. Uses of Municipal solid waste ashes ......................................................................... 9
I.3. Alkali activated materials science. ................................................................................. 10

I.3.1. Definition of alkali activated material ..................................................................... 10
I.3.2. Alkaline activation reaction and its chemistry ........................................................ 10
I.4. Material used in alkali activation ................................................................................... 12

I.4.1. use of volcanic ash in alkali activation.................................................................... 12
I.4.2. Use of MSWI-FA in alkali activated materials ....................................................... 14
I.4.3. Alkali hydroxide ...................................................................................................... 14
xvii
I.4.4. Alkali silicate........................................................................................................... 15
I.5. Factors influencing geopolymer properties ................................................................... 15

I.5.1. Feedstock material................................................................................................... 15
I.5.2. Nature and concentration of alkaline solutions ....................................................... 16
I.5.3. Solid/Activator ratios .............................................................................................. 16
I.5.4. Curing temperature .................................................................................................. 17
I.6. Characterization methods of alkali-activated cement (AAC) and mortar (AAM). ....... 17
I.6.1. Cement alkalinization .............................................................................................. 17
I.6.2. Mineral phases (XRD and FT-IR) ........................................................................... 18
I.6.3. Microstructure ......................................................................................................... 19
I.6.4. Thermal analysis ..................................................................................................... 20
II.6.5. Compressive strength ............................................................................................. 20
I.6.6. Toxicity test ............................................................................................................. 20
I.6.7. Durability ................................................................................................................ 21
I.7. Application of alkaline activated materials.................................................................... 23
I.8. Summary and motivations of the thesis ......................................................................... 24
Chapter II: Materials and experimental procedures ................................................................. 26
II.1. Materials ....................................................................................................................... 26

II.1.1. Volcanic ash ........................................................................................................... 26
II.1.2. Municipal solid waste incinerator fly ash (MSWI-FA) ......................................... 28
II.1.3. Sand........................................................................................................................ 28
II.1.4. Alkaline solution .................................................................................................... 28
II.2. Workability and Consistency of the Paste .................................................................... 29
II.3. Mix design and experimental procedure ...................................................................... 29

II.3.1. Mix design ............................................................................................................. 29
II.3.1. Experimental procedure ......................................................................................... 30
II.4. Characterization of raw materials and alkaline activated samples ............................... 34

II.4.1. Chemical composition ........................................................................................... 34
II.4.3. Mineralogical composition .................................................................................... 35
II.4.4. Physical properties of raw materials ...................................................................... 36
II.4.5. Microstructure ........................................................................................................ 37
xviii
II.4.6. Compressive strength ............................................................................................. 37
II.4.7. Bulk density, water absorption and apparent porosity ........................................... 37
II.4.8. Thermal analysis (DTG/DTA) ............................................................................... 38
II.4.9. Leaching test characterization................................................................................ 39
II.5. Durability test ............................................................................................................... 39

II.5.1. Artificial sea water resistance ................................................................................ 40
II.5.2. Sulphuric acid resistance........................................................................................ 40
Chapter III: Results and discussion.......................................................................................... 42
III.1. Characterization of raw materials ............................................................................... 42

III.1.1. Physical properties ................................................................................................ 42
III.1.2. Chemical composition .......................................................................................... 43
III.1.3. Mineralogical properties of VA and MSWI-FA................................................... 44
III.1.4. Structural characterization .................................................................................... 45
III.1.5. Microstructure characterization ............................................................................ 48
III.2. Workability and Consistency of the Paste................................................................... 49

III.2.1. Workability and Consistency of the Paste of alkaline activated based MSWI-FA
.......................................................................................................................................... 49
III.2.2. Workability and Consistency of the Paste of alkaline activated based VA.......... 49
III.3. Study of cement alkalinization .................................................................................... 49

III.3.1. Alkaline activated based VA ................................................................................ 50
III.3.2. Alkaline activated based MSWI-FA..................................................................... 52
III.3.2. Conclusion ............................................................................................................ 56
III.4. Characterization of alkaline activated binders ............................................................ 56

III.4.1. Improved reactivity of volcanic ash using municipal solid incinerator fly ash for
alkali-activated cement synthesis ..................................................................................... 56
III.4.1.1. Visual aspect of cement after demoulding ........................................................ 56
III.4.1.3. Phases evolution (FTIR and XRD) .................................................................... 57
III.4.1.4. Compressive strength, water absorption, bulk density and apparent porosity
analyses ............................................................................................................................. 60
III.4.1.5. Microstructure ................................................................................................... 61
III.4.1.6. Thermal analysis of binders ............................................................................... 65
III.3.2.7. Toxicity.............................................................................................................. 67
xix
III.3.2.8. Conclusion ......................................................................................................... 68
III.4.2. Incorporation of VA in binder based MSWI-FA.................................................. 69
III.5. Durability of alkali activated mortars.......................................................................... 81

III.5.1. Visual inspection .................................................................................................. 81
III.5.2. Residual compressive strength and weight loss evolution of alkaline activated
mortar after exposure to aggressive media ....................................................................... 83
III.5.3. Structuring and microstructuring of alkaline activated mortar before and after
exposure to aggressive media ........................................................................................... 87
III.5.4. Conclusion ............................................................................................................ 93
III.6. Development of VA+MSWI-FA matrix based alkaline activated pavement blocks. . 94
General conclusion and perspective......................................................................................... 96
References ................................................................................................................................ 98
Annex ..................................................................................................................................... 111
xx
List of Figures
Figure 1. Regional geological setting of Mount Cameroon and sketch geology of the volcano
.................................................................................................................................................... 7
Figure 2. Schematic Diagram of the MSW incineration process (Reproduced with permission
from [25], published by Environmental Protection Department, the Government of the Hong
Kong Special Administrative Region, 2009). ............................................................................ 8
Figure 3. Schematic outline of the reaction processes involved in alkalinisation .................. 11
Figure 4. Structure of geopolymer proposed by Davidovit .................................................... 12
Figure 5. Different applications of geopolymer materials [85] .............................................. 24
Figure 6. Deposit of Volcanic ash located at Loum (Moungo-Littoral-Cameroon) ................ 27
Figure 7. Location of the sample collection sites.................................................................... 27
Figure 8. Municipal Solid Waste Incinerator Fly Ash ............................................................ 28
Figure 9. Different steps handle to produce and different analyses used to characterize
alkaline activated binder and mortars ...................................................................................... 31
Figure 10. TCPL equipment (a) Millipore Rotary Agitaror (Y132 ORA HW-India), (b)
Millipore filter, (c) Inductively Coupled Plasma – Optical Emission Spectrometer (ICP-OES)
(Made by Varian) ..................................................................................................................... 39
Figure 11. Different steps handle, and analyses used to study the durability of alkaline
activated mortars. ..................................................................................................................... 40
Figure 12. Alkaline activated samples into sulphuric acid and artificial sea water. ............... 41
Figure 13. The density distribution and cumulative distribution of municipal solid waste fly
ash and volcanic ash................................................................................................................. 43
Figure 14. XRD patterns of volcanic ash and municipal solid waste fly ash ......................... 45
Figure 15. FTIR spectra of volcanic ash and municipal solid waste fly ash........................... 46
Figure 16. TG-DTA curves of volcanic ash and municipal solid waste fly ash; (a) MSWI-FA
(b) VA ...................................................................................................................................... 47
Figure 17. FEG-SEM/EDS of raw materials. (a) MSWI-FA; (a) VA and (c) EDS of
crystalline phases. .................................................................................................................... 48
Figure 18. ICC plots of VA and VA-MSWI-FA alkaline activated at different silicate moduli
(Ms=1.0, 1.2 and 1.4) ............................................................................................................... 51
Figure 19. The total heat released at 48h during alkalinisation of alkali activated cements at
different alkali moduli (Ms=1.0, 1.2 and 1.4) .......................................................................... 51
xxi
Figure 20. ICC plots of MSWI-FA and MSWI-FA-VA alkaline activated with different
alkali concentrations at 27 oC (a) 6M, (b) 8M, (c) 10M .......................................................... 54
Figure 21. Cumulated heat plot of GP0 (6), GP30(6), GP50(6), GP50(8) and GP50(10) ...... 55
Figure 22. Visual aspect of alkaline activated samples after demoulding. ............................. 57
Figure 23. FTIR spectra of VA and VA-MSWI-FA based alkali-activated cements obtained
at 27 oC with different values of silica modulus (Ms) ............................................................. 59
Figure 24. XRD diffractogram of VA and VA-MSWI-FA based alkali-activated cements
obtained at 27 oC with different values of silica modulus (Ms) .............................................. 59
Figure 25. Compressive strength of the alkali-activated cements cured at room temperature
during 28 days. ......................................................................................................................... 61
Figure 26. Low magnification microstructures features of VA and VA-MSWI-FA based
alkaline activated at high magnification: (a) GP0(1.2); (b) GP10(1.2); (c) GP20(1.2). .......... 63
Figure 27. High magnification microstructures features of VA and VA-MSWI-FA based
alkaline activated at high magnification: (a) GP0(1.2); (b) GP10(1.2); (c) GP20(1.2) ........... 64
Figure 28. Microstructures features of VA-MSWI-FA based alkaline activated with 10%wt
of MSWI-FA at Ms=1.2 ........................................................................................................... 65
Figure 29. DTG/TG curves of alkaline activated cement cured at room temperature during
28 days. (a) DTG curves and (b) TG curves ............................................................................ 67
Figure 30. X-ray diffractogram of alkali-activated cement without VA and alkali-activated
cement with VA. ...................................................................................................................... 71
Figure 31. FTIR spectra for the alkali-activated cement without volcanic ash and alkali-
activated cement based MSWI-FA +VA system ..................................................................... 72
Figure 32. TGA-DTG curves of cements without VA and alkali-activated cement based
MSWI-FA +VA system. (a) TG curves and (b) DTA curves .................................................. 74
Figure 33. FEG-SEM/EDS analysis of GPX (6) and GPX (10). ............................................ 76
Figure 34. Compressive strength of alkaline activated samples cured at 14 days (a) and 28
days (b)..................................................................................................................................... 78
Figure 35. Water absorption (WA), apparent porosity (AP) and bulk density (BD) of alkaline
activated with and without VA at different concentrations of alkaline solution; (a) Water
absorption; (b) apparent porosity; (c) bulk density .................................................................. 79
Figure 36. Appearance of mortars specimens exposed in 2 and 4% sulphuric acid and sea
water after 56 days ................................................................................................................... 82
Figure 37. Visual aspect of broken alkaline activated mortar immersed in sulphuric acid after
56 days ..................................................................................................................................... 83
xxii
Figure 38. Percentage of weight loss of alkali activated mortars immersed in aggressive
media: (a) GP10 (1.2) mortars; (b) GP50 (6) mortars ............................................................. 84
Figure 39. Compressive strength change of alkali activated mortars immersed in aggressive
media: (a) GP10(1.2) mortars; (b) GP50(6) mortars. ............................................................. 86
Figure 40. Illustration of depolymerisation of geopolymer gel in acid medium .................... 87
Figure 41. FTIR spectra of alkaline activated mortars before and after immersion in
aggressive media for 56 days: (a) GP10 (1.2) mortars; (b) GP50 (6) mortars......................... 88
Figure 42. XRD diffractograms of alkali activated mortars before and after immersion in
aggressive media for 56 days: (a) GP10 (1.2) mortars; (b) GP50 (6) mortars......................... 90
Figure 43. Microstructures features of alkali activated mortars before and after immersion in
aggressive media for 56 days: (a) alkali activated mortar; (b) mortar immersed in sea water;
(c) mortar immersed in acid ..................................................................................................... 92
Figure 44. Microstructure feature presenting the effect of sea water on gel structure ........... 92
Figure 45. Microstructure feature presenting the effect of acid on the structure of alkaline
activated mortars ...................................................................................................................... 93
Figure 46. Paving tiles developed from VA+MSWI-FA matrices (a) 50% MSWI-
FA+10%VA; (b) 90% VA+10% MSWI-FA ........................................................................... 95
xxiii
List of Tables
Table 1. Chemical composition of some volcanic ashes used for alkali-activated synthesis [9]
.................................................................................................................................................. 13
Table 2. Physical properties of municipal solid waste fly ash and volcanic ash..................... 43
Table 3. Chemical composition of volcanic ash and municipal solid waste fly ash. .............. 44
Table 4. Kinetic parameter values of alkali activated cements at different alkali moduli
(Ms=1.0, 1.2 and 1.4) ............................................................................................................... 52
Table 5. Kinetic parameter values of alkali activated cements at different concentration (6, 8
and 10M) .................................................................................................................................. 55
Table 6. Water absorption, apparent porosity and bulk density analyses of the alkali-activated
cements based VA and VA+MSWI-FA cured at room temperature during 28 days .............. 61
Table 7. Mass loss of alkaline activated cement pastes occurring at different temperature
ranges during heating ............................................................................................................... 67
Table 8. Leaching concentration (mg·L-1) of MSWI-FA, MSWI-FA-VA based alkaline
activated and landfill limit of leach metal................................................................................ 68
Table 9. IR Characteristic bands of alkali-activated MSWI-FA and MSWI-FA-VA ............. 72
activated, landfill limit and percentage of leach metal. ........................................................... 80
xxiv
List of abbreviation
AAC: Alkali-activated Cement
AAM: Alkali-activated Material
ANS: American National Standards
ANSI: American National Standards Institute
AP: Apparent Porosity
APC: Air Pollution Control
ASTM: American Society for Testing and Materials
BA: Bottom Ash
BD: Bulk Density
BET: Brunauer-Emmett-Teller
BO: Bridging Oxygen
C3A: Tricalcium Aluminate
C-S-H: Calcium-Silicate-Hydrate
DTA: Differential Thermal Analysis
EDS: Energy Dispersive X-ray Spectrometry
FA: Fly Ash
FEG-SEM: Field Emission Gun Scanning Electron
FTIR: Fourier Transform Infrared Spectrometry
ICC: Isothermal Conduction Calorimetry
ICP-OES: Inductive Coupled Plasma-Optical Emission Spectrometer
ICDD: International Centre for Diffraction Data
JCPDS: Joint Committee on Powder Diffraction Standards
LOI: Loss of Ignition
L/S: Liquid/Solid
MSWI-BA: Municipal Solid Waste Incineration Bottom Ash
MSWI-FA: Municipal Solid Waste Incineration Fly Ash
xxv
N-A-S-H: Sodium-Aluminate-Silicate-Hydrate
NBO: Non-Bridging Oxygen
SEM: Scanning Electron Microscopy
OPC: Ordinary Portland Cement
PCC: Portland Cement Concrete
PSD: Particle Size Distribution
SEM: Scanning Electron Microscopy
S/S: Solidification/Stabilisation
TGA: Thermo-Gravimetric Analysis
TPLC: Toxicity Characteristic Leaching Procedure
USEPA: United State Environmental Protection Agency
VA: Volcanic ash
WA: Water Absorption
XRD: X-Ray Diffraction
XRF: X-ray Fluorescence Spectrometry
xxvi
Abstract
Volcanic ash (VA) and Municipal solid waste incineration fly ash (MSWI-FA)
collected from two localities of the Littoral-Cameroon, i.e Loum (VA) and Douala (MSWI-
FA), were subjected to mineralogical and physico-chemical characterization in order to use
them in the synthesis of alkali activated materials at room temperature. The various cement
matrices were subjected to workability and reactivity tests using induction conduction
calorimetry. The products of different formulations with good workability have been
characterized by X-ray diffraction (XRD), Fourier Transform infrared spectrometry (FTIR),
differential thermal analysis (DTA), thermo-gravimetric analysis (TGA), water absorption,
bulk density, apparent porosity, compressive strength and scanning electron microscopy
(SEM). Toxicity test was carried out on cements following the toxicity characteristic leaching
procedure (TPLC). The durability of alkaline activated mortars obtained in sulphuric acid and
artificial seawater was also studied.
The synthesis of binders consisted to use MSWI-FA as an additive to enhance the
properties of alkali-activated matrices from low reactive VA and VA to supplement the
Alumina and silicon deficiency in MSWI-FA. The results indicated the possibility to use VA
and MSWI-FA to synthesize room temperature alkali-activated matrices applicable in the
manufacture of non-structural materials. MSWI-FA appears to be an energy-efficient and
sustainable solution for the improvement of the volcanic ash based alkaline activated
materials but the percentage of incorporation must not exceed 10% wt and the suitable silicic
modulus of activated solution is 1.2. The use of MSWI-FA as feedstock shows the possibility
of using VA as an adjuvant to MSWI-FA based alkali-activated cement in the same way as
calcined clays, fly ash, slag, red mud etc. Whereas, the better formulation to achieve good
properties is the 50% MSWI-FA-50%VA system mixed with the activating solution at 6 M
and Ms=0.66.
The binders obtained are appropriated to the environment due to the amount of heavy
leach after digestion in acid medium. The results of the durability study of alkaline activated
mortars in aggressive media disclose that both alkali activated materials have the potentiality
to resist in sea water. The formulation with high amount of MSWI-FA (50%MSWI-
FA+50%VA) has less resistant in acid medium.
Keywords: Volcanic ash; Municipal Solid Waste Incineration Fly Ash; Alkaline Activated
Cement; Toxicity; Durability
xxvii
Résumé
Les scories volcaniques (VA) et les cendres volantes d'incinération de déchets solides
municipaux (MSWI-FA) collectées dans deux localités du Littoral-Cameroun i.e Loum (VA)
et Douala (MSWI-FA), ont fait l’objet d’une caractérisation, minéralogique et physico-
chimique afin de les utiliser pour la synthèse à température ambiante du ciment à activation
alcaline. Les différentes matrices de ciment ont été soumises à des essais de maniabilité et de
réactivité via la calorimétrie à conduction inductive. Les produits de différentes formulations
ayant une bonne maniabilité ont été caractérisés par Diffraction des rayons X (DRX),
Spectrométrie Infrarouge à Transformée de Fourier (IRTF), Analyses thermique
Différentielle et gravimétrique (ATD/ATG), absorption d'eau, densité apparente, porosité
apparente, résistance à la compression et microscopie électronique à balayage (MEB/EDX).
Des essais de toxicité ont été effectués sur des ciments selon la Procédure de Lixiviation
Caractéristique de Toxicité (TPLC). La durabilité des mortiers à activation alcaline obtenus
dans l'acide sulfurique et l'eau de mer artificielle a également été étudiée.
La synthèse des liants a consisté à utiliser les MSWI-FA comme additif pour
améliorer les propriétés des matrices cimentières à base des VA et les VA pour compléter la
carence en alumine et en silicium dans les matrices cimentière à base des MSWI-FA. Les
résultats ont indiqué la possibilité d'utiliser les VA et les MSWI-FA pour synthétiser des
xxviii
matrices activées en milieu alcalin à température ambiante applicables dans la fabrication des
matériaux non-structurels. L’utilisation des MSWI-FA apparait comme une solution efficace
et durable pour l'amélioration des matériaux activés en milieu alcalin à base des cendres
volcaniques, mais le pourcentage d'incorporation ne doit pas dépasser 10 % en masse et le
module silicique de la solution activatrice approprié est de 1.2. L'utilisation des MSWI-FA
comme matière première montre la possibilité d'utiliser les VA comme adjuvant au ciment
activé en milieu alcalin à base des MSWI-FA au même titre que les argiles calcinées, les
cendres volantes, les laitiers, la boue rouge, etc. Cependant, la meilleure formulation pour
obtenir des bonnes propriétés est le système 50% MSWI-FA-50%VA activée une solution de
6 M et Ms=0,66.
Les liants obtenus sont appropriés à l'environnement en raison de la quantité des
métaux lourds lixivée après digestion en milieu acide. Les résultats de l'étude de durabilité
des mortiers activés alcalins en milieu agressif révèlent que les deux matériaux activés
alcalins ont la potentialité de résister à l'eau de mer. La formulation avec une quantité élevée
de MSWI-FA (50%MSWI-FA+50%VA) est moins résistante en milieu acide.
Mots clés: Scories volcaniques ; Cendres volantes d'incinération des déchets solides
municipaux ; Ciment activé en milieu alcalin ; Toxicité ; Durabilité
xxix
Introduction
The production of Ordinary Portland Cement (OPC) has grown considerably these
recent years in developing countries. This can be attributed to the rapid progress of
urbanization. In Cameroon, for example, the number of OPC cement plants has risen from
one in 2010 to five in 2016. The Portland cement manufacturing is a resource exhausting,
energy intensive process that releases large amounts of the greenhouse gas CO2 into the
atmosphere. The cement industry is the third largest cause of artificial CO2 emissions in the
world [1,2]. Thus, many research efforts are being made in quest for a more eco-friendly
binder. Alkali-activated cement is one of those binders which has the potential to achieve
properties similar to OPC [3,4]. Alkali-activated Cement (AAC) is a class of inorganic
polymer synthesised by the reaction of amorphous aluminosilicates powder with an alkaline
solution [5]. The final product is also amorphous to semi-crystalline structure with three-
dimensional Si-O-Al polymeric networks [6]. Recently this material has been extensively
studied due to its exceptional mechanical, chemical, and physical properties and potentially
broad practical application in construction of civil infrastructure, waste encapsulation, and
sustainable development [2,5,7,8].
According to the reaction process, two factors have a direct effect on the final
product, namely, the starting raw materials and activator. The parameters such as the curing
temperature and regime, the composition of the alkaline solution and the liquid to solid mass
ratio can also affect the properties of the AAC. The use of several types of aluminosilicate
materials was reported in the literature including metakaolin, volcanic wastes (pozzolana,
volcanic ashes and pumice) and some industrial wastes like fly ash, slag, red mud, rice husk
ash, coal bottom ash and municipal solid ashes etc. It is also notable that there are certain,
usually relatively isolated, geographic regions in which AAC binders derived from local
materials may provide a distinct cost advantage over importation of Portland cement.
Cameroon has many active volcanoes and the recent eruption occurred in 2000 on
Mount Cameroon leaving behind huge quantities of volcanic ash [9]. Recent studies [10–13]
have examined the usability of volcanic ash in AAC. These studies unequivocally reveal that
volcanic ashes have low reactivity. Consequently, various efforts have been made to alter the
reactivity of volcanic ash by hydrothermal, alkaline fusion and mechanical activation
treatments. Though, these treatments give satisfactory results with low energy efficiency.
However, they also increase the energy demand resulting to high cost of the synthesis.
1
Another approach to improve the reactivity of volcanic ash consist of the using of
cementitious materials such as metakaolin, amorphous calcium source, other calcined
pozzolans etc. [13–16]. These results revealed that these materials are the supplementary
cementitious materials for the synthesis of alkali-activated based natural pozzolan. The use of
landfill waste such as Municipal solid waste incinerator fly ash (MSWI-FA) for the same
issue can be an energy-efficient solution and sustainable to produce green building materials.
MSWI-FA is of the ashes produced during the upcoming trends to treat MSW i.e.
incineration [17]. Previous works have demonstrated that the MSWI-FA has good reactivity
in alkaline medium [18–23] and can be used as supplementary material in alkali-activated
manufacturing. The MSWI-FA can also be used as feedstock for AAC synthesis [24,25].
However, the percentage of AA ingredient elements (Aluminium, Silicon) in this hazardous
waste is less to produce binder. Another waste material like volcanic ash is used to
supplement the Alumina and Silicon deficiency in MSWI-FA in order to promote
polycondensation/polymerization and enhance the immobilization of heavy metal content in
MSWI-FA.
This thesis aims to valorise VA and MSWI-FA through alkaline activated technology
for the solidification/stabilisation concern. The specifics objectives consist to assess the
reactivity of VA+MSWA-FA using isothermal (heat conduction) calorimeter, to propose
MSWI-FA as additive to enhance the properties of alkali-activated matrices from low
reactive VA, to use volcanic ash to supplement the Alumina and Silicon deficiency in MSWI-
FA in order to promote geopolymerization and to study the immobilization’s efficiency of
heavy metal content in MSWI-F. It also deals with the resistance study of AAM based VA-
MSWI-FA and MSWI-FA-VA in acid and sea water medium. The thesis is divided into three
chapters:
 The first chapter provides detailed information on volcanic ashes and MSWI-FA, their
uses and properties. It also presents the AAC process, the use of VA and MSWI-FA
on AAM; the techniques used to characterize AAC and the factors affecting the alkali
activation reaction.
 The second chapter reports in details the experimental procedures and describes the
raw materials and analytical techniques used.
 The third chapter presents the results and discussion obtained from the experiments. It
is subdivided into 5 subparts:
2
 The first subpart presents and discusses the results of the kinetic study of the
alkaline activation of VA-MSWI-FA and MSWI-FA-VA cements.
 The second subpart studies the effects of incorporation of 5, 10, 15 and 20% of
MSWI-FA by mass and the silica modulus (SiO2/Na2O molar ratio) 1.0, 1.2 and
1.4 on structure, microstructure and physical properties of final products. It also
reports the leachability analysis of the final product through toxicity characteristic
leaching procedure (TCLP).
 The third subpart deals with the effects of the incorporation of 0%, 10%, 30% and
50% of VA and the alkalinity of activating solution on the structure, microstructure
and physical properties of the final products. It also studies the encapsulation
efficiency of the cements through toxicity characteristic leaching procedure
(TCLP).
 The fourth subpart reports the results of the effect of the aggressive media namely
sea water and sulphuric acid on the physical, structural, mechanical and
microstructural properties of alkali activated mortars will be achieved. It also
points out the difference between acid attack and sea water attack on the
properties.
3
CHAPTER I: LITERATURE REVIEW
The first chapter gives detailed information on volcanic ashes (VA) and Municipal
solid waste incineration fly ash (MSWI-FA), their uses and properties. It also presents the
alkaine activated cement (AAC) synthesis process, the use of VA and MSWI-FA on AAC
technology; the techniques used to characterize AAC and the factors affecting the alkali
activation reaction.
I.1. Volcanic ash
I.1.1. Definition of volcanic ash
In explosive eruptions, magma is fragmented by rapid ex-solution of dissolved

volatile components to produce pyroclastic materials. Fine-grained portions of these materials
are called volcanic ash, and are distributed over a wide area far from the source volcano
according to the dominant wind direction above the volcano [26]. Volcanic ash (VA) is
considered as natural pozzolan as per ASTM C618-93 [27], a standard specification for ‘Fly
Ash and Raw or calcinated Natural Pozzolan for use as a Mineral Admixture in Portland
Cement Concrete’[28]. The pozzolan is defined as a siliceous or siliceous and aluminous
material which in itself possesses little or no cementations value but will, in finely divided
form and in the presence of moisture, chemically reacts with calcium hydroxide at ordinary
temperature to form compounds possessing cementations properties (ASTM C618 (2003).
The volcanic rocks or effusive deposits covers around 5% of the solid surface of the earth
[29].
I.1.2. Physical and chemical properties of volcanic ash
Three main parameters determine the reactivity of materials: their chemical

composition (silica, alumina, and lime), their degree of vitrosity (vitreous elements are
immediately available during solubilisation) and their fineness (improved by grinding).
pozzolanic activity depends in the short term on the specific surface area of the material, and
in the long term it is closely correlated with its silica and alumina "reactive" content i.e., its
vitreous fraction.
The other properties of pozzolan that induce specific applications are as follows:
4
 The density varies according to the grain size (the finest elements are the densest)
and the ambient hygrometry. In their raw state, these materials have a density greater
than 1.
 The porosity, which varies volumetrically from 30 to 60% depending on the
granulometry, is very coarse (vacuoles ˃100µm) and closed;
 The cellular structure of pozzolans and their resulting porosity give these materials a
water absorption capacity (20 to 30% of their dry weight) and thermal and/or acoustic
insulation;
 Regarding their thermal behaviour, pozzolana has an average melting temperature of
1140 oC and poor thermal conductivity.
I.1.3. Pozzolanic activities of volcanic ash
The pozzolanic activity includes two parameters, the maximal amount of lime that
volcanic ash can consume and the rate at which this occurs. These depend on the content of
dissolved (amorphous) SiO2 or AlO3+SiO2. Lime absorption, solubility of a volcanic ash in
saturated Ca(OH)2, alkali, acid, or alkali and then acid solution or electrical conductivity
change of a solution due to the dissolution of a volcanic ash may be used for evaluation of
pozzolanic reactivity of natural pozzolans [30]. The performance of a hardened paste depends
not only on the reaction rate and degree, but also on the nature of reaction products [30].
Ogawa et al [31] (1980) also suggested that the quality of natural or artificial pozzolanic
cement should be evaluated by strength tests. Many standards now use compressive or tensile
strength of mortars to show the quality of pozzolans [30]. The pozzolanic activity of volcanic
ash is affected by many factors. The main factors include [32]:
 Nature and composition of the active phases;

 Specific surface;
 The lime/pozzolana ratio of the mix;
 The water/mix ratio;
 The curing time and temperature.
II.1.4. Use of volcanic ash
The volcanic ash is a part of pozzolana, which has the diameter less than 2 mm and
has approximately the same applications with the pozzolana. The aforementioned properties
of this material give rise to plethora applications.
5
The main uses are as follows [33]:
 Agriculture: drainage, soil improvement and crop substrates;

 Sanitation: drinking water filter systems (double-layer filters), absorbent trays and
bacterial beds in waste water treatment plants, septic tank filters, biological waste
water treatment;
 Sports soils: grassed or stabilized soils (drainage base layer, intermediate layer,
surface layer or screed), filling of drainage slots; tennis, football, golf, athletics, race
tracks and other tracks and other evolution boards.
 Viability: construction of the foundations and structuring of the pavements;
construction of drains and embankments, winter sandblasting of the pavements,
covering of underground cables and pipes; pozzolan limestone gravel; ornamentation
and decoration;
 Building : manufacture of light weight, hollow or solid concretes; light weight blocks
(cinder blocks), rubble, agglomerates, nozzles, pre-fabricated elements, walls and
partitions, floors, roofs and terraces, kerbs and self-locking paving stones; formation
of layers under slabs and tiles, filling of floors and ceilings, pozzolan concretes,
refractory pozzolan-based concretes used to manufacture bushels (pipes) and chimney
drains, additives in mass concretes;
 Precursors and adjuvants for alkali activated materials.
I.1.5. Pozzolana in Cameroon
Figure 1 bellow depicts the pozzolana area in Cameroon. The yellow zone depicts the
regions where the pozzolana is abundant. The red lines symbolise the volcanic line of
Cameroon. The pozzolana is scattering around these lines. In the view of the figure,
Cameroon appears as one of the countries that has huge amount of pozzolana.
6
Figure 1. Regional geological setting of mount Cameroon and sketch geology of the volcano
I.2. Municipal solid waste ashes and municipal solid waste incinerator fly
ash (MSWI-FA)
I.2.1. Definition of municipal solid waste ashes
The municipal solid ashes (Bottom Ash (BA), Fly Ash (FA) and air pollution control
(APC) residue) are the main products of the emerging concern of the management of
municipal solid waste. This process reduces waste to ash by about 75% and generates energy
during the combustion process. MSWI-BA is referred to a grate ash discharged from the
furnace grate and collected in the water-quenching tank. During the process, the BA is
combined with grate shifting (fine particles falling through the furnace) and heat recovery ash
(particulate matter collected from the heat recovery system). MSWI-FA is fine particles
carried over the furnace and separated prior injecting sorbents to treat the gaseous effluent.
Gas condensate and reaction products are produced from APC devices, such as electrostatic
precipitator, scrubber, etc. APC residue is then produced by combining the FA, sorbents, gas
condensates, and reaction products together in APC devices [34]. In the process of
incineration (Figure 2), about 80 to 90% of the MSW by weight are BA and 10 to 20% are
7
FA [2]. The MSWI-FA has the same feature with coal FA which is a by-product of
pulverized coal combustion in electric power plants and widely known as supplementary
cementitious material in concrete manufacture.
Figure 2. Schematic Diagram of the MSW incineration process (Reproduced with permission
from [25], published by Environmental Protection Department, the Government of the Hong
Kong Special Administrative Region, 2009).
I.2.2. Properties of Municipal solid waste fly ashes
In general, MSWI FA is referred to as the entire ash residues from the APC devices.
Hence, properties of FA greatly vary with different APC systems, such as dry/semi-dry or
wet scrubber equipped with electrostatic precipitator or fabric filter [35]. The FA is
characterized with fine particulate matters, dusty appearance with gray to dark gray colour
[36]. The FA mostly contains oxide form of calcium, different metal salts, chloride
compounds, and heavy metals [37]. The major elements found in FA are O, Cl, Ca, Fe, Al,
Na, K, Pb, Zn, and S, whereas trace elements are Hg, Cd, Cr, Ni, As, and Co. CaO is found to
be predominant compound in FA, which constitutes up to 46% [20]. When FA is subjected to
a treatment with lime (CaO) scrubber, Ca(OH)2 is obtained as end product [35,37]. FA is
generally considered more toxic material than BA, because the FA comprises higher
concentration of heavy metals, salts, and organic micro-pollutants due to the volatilization
and condensation of different elements during the incineration [25]. Due to the presence of
highly soluble salts, Cl, and heavy metals, the FA is not considered for direct utilization as
8
transportation materials [38]. Especially, high content of Cl in FA may increase corrosion
probability of reinforced concrete structure when mixed with cement. In addition, when the
FA with lime scrubber treatment is incorporated in construction materials, the workability is
considerably reduced due to the high-water absorption characteristic of hygroscopic CaCl2.
Moreover, similar to the BA, large content of metallic Al in FA makes the utilization of FA
uncertain [39]. The presence of readily soluble salt, such as Cl and Na in FA can significantly
contaminate drinking water system [25]. Although dioxin and furan do not leach easily, high
potential of heavy metals and trace metals is another concern that can pose a threat to human
health [40]. In order to reduce the adverse effect of FA, different treatment techniques are
being practiced. These treatments are (1) extraction and separation using water or acid, (2)
chemical stabilization using carbon dioxide/phosphoric acid (CO2/H3PO4), ferrous sulphate
(FeSO4), sodium sulphide (Na2S), and orthophosphate (PO43-) [25], (3) solidification using
lime, cement, asphalt, and gypsum, (4) thermal treatment, such as vitrification and pyrolysis
[34], and stabilisation/solidification through alkaline activation.
I.2.3. Uses of Municipal solid waste ashes
Despite the fact that MSWI-FA is considered as toxic, some properties and
composition give rise to some utilizations [25,34]:
 The Netherland has implemented the use of FA in asphalt application as a substitute

of natural aggregate;
 One of the possible utilizations of MSWI-FA is soil stabilization as a replacement of
lime or cement due to having pozzolanic reactivity;
 MSWI-FA ashes are desirably applicable as base and filler material due to having
high stability and low density with some consideration of low durability;
 In European countries, several studies used the MSWI-FA as partial replacement of
cement to investigate their effect on the cement paste and PCC;
 The MSWI-FA is used as adjuvant in concrete to reduce the workability due to its
smaller particles;
 A mixed fly ash of MSW and coal is one of the new trends for improving the quality
of the zeolite and the use of MSW ash for zeolite production. However, the properties
of zeolite products mainly depend on NaOH concentration, reaction temperature and
crystallization time [38];
 Precursors and adjuvant of alkali activated materials.
9
I.3. Alkali activated materials science.
I.3.1. Definition of alkali activated material
Alkali activated material (AAM) is the broadest classification, encompassing

essentially any binder system derived by the polymerization/polycondensation of a solid
alumina- silicate (termed the ‘precursor’) under alkaline conditions (induced by the ‘alkali
activator’), to produce a hardened binder [41]. The alkali metal sources commonly used are
sodium or potassium hydroxide, water glass (sodium or potassium silicate solution), and a
mixture of alkali hydroxide and water glass activator liquids in the synthesis of AAM. The
alkaline liquid containing the silicate species, i.e. water glass, increases the rate of the
reaction compared to the alkaline solutions containing sodium or potassium hydroxide only.
Sodium containing solutions are generally the favourite activators in the preparation of AAM
because they promote dissolution of glassy alumina-silicates and also invite low costs and
wide availability than other metal hydroxides [42].
The AAM feedstock materials include high calcium content materials such as class C
fly ash, conventional clinkers, Blast furnace slag, MSWI ashes etc, whereas the feedstock
materials for geo-polymer include only the low calcium content alumina-silicate materials
such as metakaolin, class F fly ash, red mud etc. The difference between AAM and geo-
polymer resides on raw material and the condition to prepare alkaline activator. For the geo-
polymer the mix of alkali hydroxide solution and water glass must be used after 24 h for geo-
polymer synthesis and concerning AAM any condition is herein reported.
I.3.2. Alkaline activation reaction and its chemistry
I.3.2.1. Mechanism of formation of alkali activated material
The formation of AAM has the same mechanism with geo-polymer. It involves the
mixing of solid precursors (alumina-silicates sources) such as metakaolin, Fly ash, volcanic
ash, slag etc. with alkaline activator solution (alkali hydroxide and meta-silicate). After the
mixing, multi steps of reactions occur namely:
(a) Dissolution of glassy alumina-silicates;
(b) Reorganization and diffusion of dissolved ions with formation of small-coagulated

structures;
10
(c) Poly-condensation to form alumina-silicate gel phases; and
(d) Solid state transformation and hardening to form hard solid.
The aforementioned geopolymerization reaction steps are summarized in Figure 3. [43].
Solid alumina-silicates source +Alkali silicate/hydroxide activating solution
Dissolution
Oligomeric
Silicate monomer Aluminate monomer
silicate species
Oligomerisation
Alumina-silicate oligomers
Polymerisation Nucleation
Alumina-silicate polymer Alumina-silicate ‘nuclei’

(amorphous) (quasi-or nanocrystalline)
Gelation Crystallisation
Transformation
Alumina-silicate gel ‘Zeolite’ phase
(amorphous) (nanocrystalline)
Figure 3. Schematic outline of the reaction processes involved in alkalinisation
Due to the high calcium content in some raw materials the C-S-H gel is formed
synergistic with N-A-S-H and C-A-S-H. This coexistence improves the mechanical
properties of AAM compared to systems with only geopolymer gel (N-A-S-H).
11
I.3.2.2. Structure of geopolymer
The structure of geo-polymer materials are similar to zeolites, but the microstructure
of a geopolymeric material is a three dimensional silica-aluminates amorphous or semi-
amorphous structure instead of crystalline [42,44]. The geo-polymer network consists of
SiO4 and AlO4 tetrahedra linked alternately by sharing all the oxygen. Positive ions (Na+, K+,
Li+, Ca2+, Ba2+, NH4+, H3O+) must be present in the framework cavities to balance the
negative charge of Al3+ in IV-fold coordination. The poly-silicate is designation of
geopolymer based on silica-aluminates where silicate is an abbreviation for silicon oxo-
aluminate. The empirical formula of poly(silicates) is Mn{-(SiO2)z-AlO2}n, wH2O where M
is a cation such as potassium, sodium or calcium, and «n» is the degree of polycondensation;
«z» is an integer1, 2, 3 [45]. Geo-polymers comprise the following molecular units: siloxo (-
Si-O-Si-O-), silicate (-Si-O-Al-O-), silicate-siloxo (-Si-O-Al-O-Si-O-), silicate-disiloxo (-Si-
O-Al-O-Si-O-Si-O-), ferro-silicate (-Fe-O-Si-O-Al-O-Si-O-). Figure 4 is a representation of
the structure of geo-polymer as proposed by Davidovict in 1994 [5].
Figure 4. Structure of geopolymer proposed by Davidovit
I.4. Material used in alkali activation
I.4.1. use of volcanic ash in alkali activation
The volcanic ashes are the potential raw materials for alkali activated due to its
SiO2+Al2O3 content (60-78 wt%) and pozzolanic properties. Table 1.1 depicts the chemical
composition of some volcanic ashes used for alkali-activated synthesis. However, the
12
relativities of volcanic ashes depend on the chemical and mineralogical compositions along
with the fineness of its particles. Lemougna et al (2014) [46] observed that the mineralogical
composition is the main factor affecting the heat released during the alkalinisation of four
Cameroonian volcanic ashes. In volcanic ashes, the mineral phases are immerged in glassy
phases, which are characterized by the broad hump in XRD diffract gram located between
27-37o. The prominence of glassy phases also improved the reactivity of volcanic ashes. It
was also reported by Tchakoute et al (2013) [47] that the presence of clay which increase the
LOI of volcanic ash affect its reactivity. Some processes have been proposed in literature to
alter the reactivity of volcanic ashes. They are:
 The thermal treatment by bender et al (2011) [48] it consisted of the calcination of

clay content of volcanic ashes at 700-800oC range.
 The alkali fusion by Tchakoute et al (2015) [14], it consisted of the calcination of
volcanic ashes in the presence of NaOH for 2h.
 The mechanical activation by Djobo et al (2016) [49], through the milling in vibratory
mil at different times up to 120 min.
 The hydrothermal curing at temperatures less than 100oC [12] (40-100oC).
 The addition of supplementary cementations material such as calcinated clay, blast
furnace slag, MSWI-FA etc.
Table 1. Chemical composition of some volcanic ashes used for alkali-activated synthesis [9]
Oxides Concentration (wt %)

Volcanic Scoria Andesite or dacite Volcanic pumice
I II III IV V VI VII VIII IX X XI XII
SiO2 46.28 41.36 47.74 43 40.17 46.48 54.93 59.5 61.57 70.13 64.67 67.08
Al2O3 15.41 15.41 15.41 15 13.86 17.74 16.44 19 18 11.11 11.85 14.06
Fe2O3 13.32 12.88 12.88 12 15.16 12.16 10.89 6.5 4.93 1.27 3.03 1.91
CaO 9.07 7.88 8.25 11 9.7 8.78 8.79 4 6.69 2.52 6.79 0.87
MgO 6.74 6.45 6.45 6.8 9.57 8.73 3.30 4.25 2.63 0.92 1.11 0.25
Na2O 3.88 2.22 3.62 4.6 3.66 3.39 2.84 6 1.65 1.01 2.30 0.11
TiO2 2.84 3.04 2.8 2.9 - 2.31 0.75 - - 0.14 0.54 -
K2O 1.42 0.90 1.11 1.7 1.53 1.27 1.72 - 1.95 2.25 4.26 -
P2O 0.63 0.48 0.48 0.9 - 0.63 - - - - - -
MnO 0.19 0.20 0.17 0.19 - 0.19 0.21 - - - - -
SO3 0.04 - 0.04 - 0.09 - - - 0.10 - - -
LOI -0.4 9.31 0.66 - 4.75 1.32 - - 2.15 10.28 5.15 3.94
LOI: Loss on Ignition; I-IV: Cameroon, V: Jordan, VI: Kingdom of Saudi Arabia, VII: Japan,
VIII: Italy, IX-XI: Iran and XII: Turkey.
13
I.4.2. Use of MSWI-FA in alkali activated materials
The disposal of Municipal solid waste incinerator fly ash (MSWI-FA) causes another
unresolved environmental concern. It is potentially harmful to the environment due to its high
heavy metals content. Owing to its chemistry, fine particle size and pozzolanic behaviour,
MSWI-FA has the potential to be used as a mineral additive in cement. However, its high
chlorine content restricts its application in construction material. Although the cement paste
is not much affected by chloride except for increased solubilisation of cement solids, chlorine
is detrimental to the passivation of embedded steel [50]. To avoid this problem, some pre-
treatment methods such as water washing and thermal treatment have been proposed [51–53].
These pre-treatments certainly eliminate the chlorine and inorganic salts in MSWI-FA but
generate other wastes, increase the quantity of energy required for the synthesis and the total
cost of the product. In addition, MSWI-FA contains considerable amount of metallic Al that
can generate hydrogen gas, resulting in volume expansion, cracks and voids in cement paste
specimens [34]. The efficient way to valorise MSWI-FA in construction is its use in the
process which displays limited signs of heavy metals leaching, volume expansion, crack, and
formation of corrosion product in the presence of chlorine such as alkali activation[54–56].
The main uses of MSWI-FA on alkali activation in literature consist to use synergetic with
some alkali activated precursors (solidification/solidification) in order to produce green
building materials. The precursors used are: metakaolin, coal fly ash, red mud, volcanic ash
[23].
I.4.3. Alkali hydroxide
The alkali hydroxides most commonly used as alkali activators are those of sodium
and/or potassium. Lithium, rubidium and caesium hydroxides are of limited large-scale
application due to their cost and scarcity, as well as the relatively low solubility of LiOH in
water (just under 5.4 mol/kg H2O at 25°C [57]. Sodium, hydroxide appears as the cheapest
alkali hydroxide. In a processing context, aside from their obviously highly corrosive nature,
the most important properties of concentrated hydroxide solutions that must be considered are
viscosity, and the heat released by the dissolution of the solid alkali hydroxide compounds
during preparation of the solutions. The viscosity of even highly concentrated alkali
hydroxide solutions rarely exceeds that of water by more than a factor of 10, and this is a
marked advantage over comparable alkali silicate solutions [58]. Efflorescence (particularly
due to the formation of white carbonate or bicarbonate crystals) is also a known issue in
14
binders activated with too high a concentration of hydroxide solutions, where the excess
alkali reacts with atmospheric CO2. This is unsightly, but not always harmful to the structural
integrity of the material. Efflorescence is generally more marked in the presence of Na than K
in hydroxide-activated binders.
I.4.4. Alkali silicate
Alkali silicates are generally produced from carbonate salts and silica via calcination
then dissolution in water at the desired ratios, which brings associated energy consumption
and CO2 emissions. However, due to the relatively low content (by mass) of activator in most
alkali-activated binders, the CO2 emission process rate induced by the calcination of
carbonates here is much lower per tonne of binder than the CO2 emissions process associated
with Portland cement production [59]. As for the case of hydroxides, the silicates of sodium
and potassium are those with the greatest industrial relevance in alkali activation. The sodium
silicate solution is cheaper than potassium silicate. The alkaline sodium silicate solutions,
also known as water glass, are a combination of sodium oxide (Na2O), silica (SiO2) and water
(H2O). The various grades of sodium silicate are characterized by their SiO2/Na2O weight
ratio which can vary between 2:1 and 3.75:1 [60]. In the view of the composition of water
glass, its use in alkali activation presents two advantages: (i) supplement the oligomer silicate
in the matrix and (b) facilitate the dissolution of gassy alumina-silicate powder through Na2O.
I.5. Factors influencing geopolymer properties

Several factors have been shown to affect the geopolymerization reaction and
consequently the properties of the so-formed geo-polymer. The factors include:
I.5.1. Feedstock material
The precursors play an important role in the formation of geo-polymer. Materials rich
in Si (like fly ash, volcanic ash, and slag and rice husk) and materials rich in Al (clays like
kaolin and alloy site, betonies) are the primary requirements to undergo geopolymerization.
However, some materials have low reactivity in alkaline medium and require pre-treatment
before using at room temperature such as calcination (clay, volcanic ash etc), alkaline fusion
(volcanic ash) and mechanical activation (fly ash, volcanic ash). Sanjay et al (2010) [61] and
Djobo et al (2016) [11] showed that mechanical activation cure, improves the reactivity of
coal fly ash and volcanic ash, respectively through the physicochemical changes of the bulk
and reactive surface. Tchakoute et al (2013) [10] revealed that the alkaline fusion treatment
15
promotes the glassy phases in volcanic ash, thus enhances its reactivity. The addition of
supplementary material is usually used to improve the setting and the Si/Al ratio in some
alumina-silicates materials. Silica fume from smelting operations, metakaolin, rice husk
ashes, waste glass etc. are used to supplement silicon content. Sodium aluminates (Bayer
liquor) (Jamieson et al. 2012), metakaolin, aluminium smelting slag, waste water treatment
sludge (Babatunde and Zhao 2007) etc. are used to adjust the alumina content.
I.5.2. Nature and concentration of alkaline solutions
Sodium or potassium hydroxide, water glass (sodium or potassium silicate solution),

and a mixture of alkali hydroxide and water glass are the commonly used activator liquids in
the synthesis of geo-polymers. The alkaline liquid containing the silicate species, i.e. water
glass, increases the rate of the reaction compared to the alkaline solutions containing sodium
or potassium hydroxide only. Sodium containing solutions are generally the favourite
activators in preparation of geo-polymers because, they promote dissolution of glassy
alumina-silicates and also invite low costs and wide availability than other metal hydroxides
[42]. Besides the identity of the alkali, a rise in alkali concentration increases the dissolution
of glassy phases and accelerates the geopolymerization reaction rate as well. However, excess
OH- specie is detrimental to the geopolymerization. The appropriate alkali concentration and
hydroxide/silicate ratios depend on the composition and the reactivity of the precursors.
Rashidah Mohamed Hamidi et al [62] ; Siti Fatimah Azzahran Abdullah et al [63] studied the
effect of Alkali Concentration (4 to 18 M) on Fly Ash Geo-polymers, based on the results
obtained, the properties (higher strength, water absorption and porosity) of product rise up
to 12 M and decrease from 13 M to 18M. A Nmiri et al [64]investigated the effect of the
concentration of alkaline activator (5 to 18M) on calcined kaolinitic clay at different
temperatures (550 to 1100 oC), the various physical properties reached optimum values were
700 oC and 13 M. These values decreased at higher temperature and concentration. Sylvain
Tome et al studied the effect of the concentration of alkaline solution (6 to 10M) on MSWI-
FA-volcanic ash geo-polymer at room temperature, and the results revealed that the 6 M
concentration promotes the best properties.
I.5.3. Solid/Activator ratios
The fraction of solid to liquid had also been documented to have significant effect on
the formation and properties of geo-polymers. The high Solid/Activator (S/A) ratio had a low
16
viscosity, while geo-polymer paste with a low S/A ratio resulted in high viscosity [65].
Besides that, geo-polymer with a low S/A ratio could accelerate the dissolution rate, but it
was not applicable to the polycondensation process when high concentrations of NaOH were
used [66]. In addition, the low S/A ratio resulted in low strength geo-polymers due to
insufficient formation of binder and increase of water in system[67]. The S/A ratio value vary
from one solid to another and depend on the physical properties of the solid (finesse, specific
surface area, particle shape). The S/A ratio by mass to achieve the optimum setting time and
compressive strength in fly ash geo-polymers is recommended to be maintained in the range
of 0.30 to 0.45 [42,68,69]. Metkaolin (calcite clay) has higher liquid demand than fly ash due
to the difference in particle shape and a lower S/A ratio to provide the near optimum strength
and good workability is 0.80 [70]. The surplus of activator promotes the free alkali ions and
water in the system, which affect the strength and microstructure of the geopolymer.
I.5.4. Curing temperature
Temperature plays a vital role in geopolymer formation. Generally, elevating curing

temperature (27oC˂T<100oC) accelerates the dissolution, polymerization, precipitation
processes of the geopolymerization reaction [71]. However, the hydrothermal synthesis
promotes the coexistence of three-dimensional amorphous alumina-silicates (geo-polymer)
and the nanocrystalline structure such as zeolite. Djobo et al studied the reactivity of volcanic
ash at 27-80oC range. The authors reported that, the degree of crystalline and the extent of
geopolymerization increase with curing temperature [72].A.M. Mustafa Al Bakri et al [73]
reported that the maximum compressive strength (67.04 MPa) achieved at a temperature of
60 °C in fly ash geo-polymer and the strength decreases at temperature more than 60 °C.
I.6. Characterization methods of alkali-activated cement (AAC) and

mortar (AAM).
I.6.1. Cement alkalinization
Isothermal heat conduction calorimetry is a useful method for determining the heat
production rate and the developed heat during cement hydration or alkalinization [74]. It may
be used for several different purposes:
 To determine the total heat of reaction;

 To determine the rate of heat production during reaction and
 As a general tool to investigate the poly-condensation/polymerization process.
17
There are many challenges which make the reaction kinetics study of alkaline activation
reaction complex such as:
 Heterogeneous nature of raw materials,

 Non-uniform reaction of precursors with alkali,
 Presence of significant amounts of impurities in the reaction system, leading to
multiple reaction paths and consequent change in reaction mechanism,
 Low and narrow temperature range of reaction, and
 Difficulties in characterizations of reaction products due to the presence of unreacted
particles in the system [75].
The method comprises the measurement of thermal power (heat production rate) and
specific thermal power (heat production rate per gram cement) of the cement poly-
condensation/polymerization reaction at essentially constant temperature. The primary result
of a measurement with an isothermal heat conduction calorimeter is the thermal power as a
function of time. This result is often rather detailed and one can usually pinpoint the exact
time when the main reaction starts, find multiple peaks etc. Because of this, isothermal
calorimetry can have many different uses, some of which are described above.
I.6.2. Mineral phases (XRD and FT-IR)
 X-ray Diffraction
X-ray diffraction (XRD) is an important tool for identifying, characterizing, and

quantifying minerals. It is widely used for examination of crystalline materials. The
wavelengths of X-rays range from 0.1 to 20 Å, which is in the order of atomic unit cells [51].
When an X-ray interacts with atomic structures of the same magnitude, it is diffracted. The
diffracted X-rays are depicted as peaks, diffuse halos or combination of both for crystalline,
amorphous and semi-crystalline materials respectively. Despite the substantial amorphous
nature of geopolymers, XRD is often used to identify newly formed phases, define the degree
to which starting materials have reacted and assess the degree of crystallinity of the final
products.
The amorphous nature of AAM is characterized by the diffuse halo which is often
observed between 2θ =20º- 40º with a peak at 2θmax =27º - 29º [76,77]. XRD cannot solely
be used to characterize AAM structures due to their inherent amorphous nature; however, it is
18
a useful tool that gives an indication of whether a material may be a geo-polymer warranting
further examination.
 Fourier Transform Infrared Spectroscopy, FTIR
Fourier Transform Infrared Spectroscopy (FTIR) analysis is considered as an

appropriate method to study the structural evolution of amorphous alumina-silicates
exhibiting high heterogeneity [78]. It is a practical technique to characterize the structure of
AAM in conjunction with XRD. During alkali-activation, every bridging oxygen atom (BO)
of the original alumina-silicate replaced by two negatively charged non- bridging oxygen
atoms (NBO), which are charge compensated by the alkalis. Micro-structurally, this is similar
to adding alkalis to synthetic silicate or alumina-silicate glasses, whose alkali and water
contents can be artificially controlled. From the literature, it is mentioned that addition of
alkalis as network modifiers to an alumina-silicate known to generate a greater concentration
of NBOs within the structure. The TO4 (T =Al or Si) units within the silicate network have
become more isolated with increasing alkali inclusion and thus lower the molecular vibration
force constant of the T-O bond. As a result, an infrared (IR) band attributable to the T-O-Si
asymmetric stretching vibration of the TO4 tetrahedra of an alumina-silicate glass has been
found to shift to the lower energy end with increasing alkali content [79]. The extent of the
shift is approximately linear to the alkali content with the view that a greater extent of alkali-
activation of alumina-silicates should give rise to products of greater NBO concentrations.
I.6.3. Microstructure
Scanning Electron Microscopy (SEM) is used to study the morphology of the surface
of samples. It allows observing surfaces up to a nanometre scale. The operation of the
scanning electron microscope is based on the strong interaction between the emitted and
backscattered secondary electrons that allow the image of the object's surface to be
reconstituted in high resolution [80]. To perform this analysis, the sample must be metallised
before being introduced into the analysis chamber to avoid a significant accumulation of
charge on the surface of the material and to reduce the depth of penetration of the beam, thus
improving image quality. The scanning electron microscope is equipped with a complete
microanalysis system (EDS detector) and used for chemical analysis and mapping of certain
samples. The microstructural features of AAM are important for understanding mechanical
properties of AAM. The SEM/EDS reveals the morphology feature and the composition of
gels, crystalline phases and unreacted particle into the AA matrix.
19
I.6.4. Thermal analysis
Thermal analysis allows studying the phase transformations, structural modifications,

decomposition, volume variations, etc. as a function of temperature. Techniques used include
differential thermal analysis (DTA), thermo-gravimetric analysis (TGA), differential
scanning calorimetry and dilatometric analysis [81]. DTA and TGA are the most used for
determining the temperature behavior of concrete after fire exposure. TGA is an analytical
technique that consists in recording mass variations during a thermal cycle, related to
chemical reactions or water departures of volatile constituents adsorbed or combined in a
material. The temperatures at which these mass losses occur are additional information to that
obtained by DTA for the identification of the physical-chemical phenomena (exothermic,
thermic and endothermic) involved. These two types of thermal analyses are often performed
simultaneously in the same apparatus.
II.6.5. Compressive strength
The mechanical properties (strength, flexural strength etc.) of a material describe how
that material behaves when subjected to an applied force. Strength is the design property of
the specimen from cement such as pastes, mortar, concrete etc. Characteristics like,
durability, impermeability, volume stability may be important in some cases of designing
specimen structure, but strength is the most important one. In the construction process, it is
always important to know the specimens (paste, mortar, concrete etc.) compressive strength.
The recommended procedure to ensure the strength depends on the standard carried out. It
can be performed using cubic or cylinder test. The days less than 28 tests are done to assess
the early gain of specimen strength. However, 28- days tests are mandatory as per
design/construction code requirements [82]. 28 days is considerable time to wait for the test
results of specimen strength, while it also represents the quality control process of specimen
mixing, placing, proper curing etc. Specimens mix design is a process done by using code
recommendation and sometimes by experience. The extending of strength gain can be also
done after 28 days of curing. The field of application of cement products depend on the
mechanical achieved and the parameters such as permeability, durability etc.
I.6.6. Toxicity test
One of the applications of AA technology is to reduce the likelihood of release of

hazardous components to the environment via solidification/stabilisation (S/S).S/S is the
20
general terms of the mixing of a waste with a binder to convert it into a monolithic solid. The
mechanisms effective in S/S of contaminants by cements and related binders can include
chemical fixation by interactions between contaminants and binder phases, physical
adsorption of the contaminants onto the surfaces within the pore structure of the solidified
binder, and/or physical encapsulation within a low-permeability phase to reduce accessibility
during exposure to potentially aggressive environments[58]. The leaching test is the common
test used to access the stabilisation or immobilisation efficiency of AAM. The TCLP test has
been widely used, both unmodified and in slightly adapted forms, and the ANSI/ANS 16.1
test is popular in testing of alkali-activated nuclear waste-forms.
I.6.7. Durability
AACs are inherently resistant to chemical attack and thermal loading due to their
reduced porosity and thermal conductivity characteristics. Many of the durability problems
associated with PCC arise from its calcium content in the main phases. The C3A reacts with
sulphate ions in the presence of Ca(OH)2 to form ignite and gypsum, which in turn cause
expansion and degradation of the cement into a non-cohesive granular mass [25]. It is the low
calcium content found within pozzolanic materials that prevents geopolymers from
experiencing such negative effects.
While geo-polymeric materials possess an enhanced level of durability over Portland-

based cements, they are not immune to environmental threats. Immersion in seawater slightly
affects internal porosity because of Na ions being replaced by Mg ions in the gel
microstructure. Highly acidic media cause a de-alumination to occur in alkali-activated
cements, thus resulting in loss of mass and a decline in mechanical strength. It is noted,
however, that the strength loss in comparison to PCC is much less.
Specimen from cement durability is generally defined as ability to resist weathering

action, chemical attack, abrasion, or any process of deterioration. Durability is largely
dependent on transport properties which are highly influenced by the pore system. As such,
the transport resistance evaluation of the concrete cover can be a good index to ensure as to
whether the specimen structure element is durable enough or not.
21
I.6.7.1. Water absorption test
The main reason for specimen degradation is penetration of deleterious substances

through the pore system. As most of these substances are dissolved in water, one of the most
promising evaluation methods regarding specimen durability is water penetration. Specimen
water absorption tests are potentially fast and practical tests in the means of durability
evaluation. Results of these measurements can provide engineers with information to estimate
the pore structure in a specimen. Thus, during the last decades researchers have completed
several investigations regarding Standardizing laboratory test methods. There are a few
Standard methods for water absorption measurement in laboratory conditions. ASTM C1585
and ASTM C642 are the most used Standard approaches for concrete water absorption.
I.6.7.2. Acid resistance test
Although most concrete is not subjected to highly acidic conditions, there are some
applications where this does become an issue, and in these circumstances the lifetime of
concretes can be severely curtailed. Acid rain, acid sulfate soils, animal husbandry and
industrial processes can all produce acids which could potentially degrade concrete [58]. The
most important mode of acid attack on a binder, whether based on OPC or AAM, takes place
via degradation of concrete by ion exchange reactions. This leads to a breakdown of the
matrix nano- and microstructure and weakening of the material. In some cases this can be
extremely rapid and serious, and the acidic conditions may be induced by either industrial or
biogenic processes. The test in the laboratory consists to immerse sample in acid for many
weeks. Different parameters are adjusted in order to mimic the real-life situation as closely as
possible, or to accelerate the degradation and thus obtain results more rapidly. These
parameters include the pH and concentration of the acidic solution, the physical state of the
sample (monolith or powder; paste mortar or concrete), temperature, rate of acid
replenishment, presence or absence of mechanical action/flow, alternate wetting and drying,
alternate heating and cooling, and pressure[58]. The parameters used in degradation
measurements may include change in the dimensions or mass of the specimen, loss of
strength or elastic modulus of monolithic specimens, depth of acid penetration/binder
alteration, pH change of the leaching liquid or of the binder pore solution, the concentrations
of calcium or network-forming elements released into the liquid, and others. These direct
measurements may be supplemented by SEM, XRD or spectroscopic analysis to examine the
microstructure and nanostructure of the altered binder regions.
22
I.6.7.3. Seawater attack
The immersion of alkali-activated binders in artificial seawater has long been known
to give good performance outcomes, with an increase in compressive strength and no
corrosion of embedded steel (with 16 mm cover depth) observed during 12 months of
exposure [58]. Puertas et al. [83] showed that the degree of alteration of the binder pore
structure during seawater immersion was lower for alkali silicate-activated BFS than when a
NaOH activator was used, although all samples proved resistant to degradation during 180
days of exposure. Zhang et al. [84] developed alkali silicate-activated fibre-reinforced
BFS/met kaolin pastes for application as a coating for marine concrete structures, with results
to date showing good resistance and durability under the intermittent exposure conditions
which are well known to be damaging to Portland cement binders (minor surface cracking but
a very strong bond to the underlying concrete).
I.7. Application of alkaline activated materials

AA mortars and concretes possess a high potential for use in commercial applications.
This is due to their enhanced durability, thermal and chemical resistance properties,
mechanical strength, adherence to reinforcements/aggregates and economic benefit as an
industrial by-product material. Compressive strength values over 70 MPa within 24 hours and
high resistance to sulphates and various acids allow AAMs to bear potential for a variety of
commercial applications and industrial use. However, the different applications of AAM
depend of Si/Al ratio. Figure 5 proposed by Davidovits et al (2015) [85] summarizes the
different applications of geo-polymer with respect to Si/Al ratio.
23
Figure 5. Different applications of geopolymer materials [85]
I.8. Summary and motivations of the thesis

One of the particularities of Alkali-Activated Cement is the possibility of using a wide
range of alumina-silicate materials as raw material, thus limiting the depletion of ores. The
synthesis of new generation cement by most countries results from the great use of good
potential materials. Countries near the volcanic line benefit from volcanic ashes as a raw
material for alkali-activated cement development. Despite their high alkalinization ingredient
content (Al+Si65%), literature reveals their low reactivity in alkaline environments. It also
highlights solutions to increase their reactivity, by alkaline, thermal and mechanical
activation. Another method is the addition of supplementary cementituous materials such as
metakaolin, materials rich in active calcium to facilitate the setting of the cement matrix. The
addition of a toxic pozzolanic waste such as MSWI-FA has not yet been studied in this
matrix. However, the use of such waste is an efficient solution for its stabilization and thus
24
increasing the reactivity of volcanic ashes. MSWI-FA can be used as an alkalinization
precursor, where its deficiency in alkalinization ingredient is supplemented by the addition of
materials rich in these elements. Volcanic ashes have not yet been the subject of this study.
There is also limited research in the study of the kinetics of the cement matrix containing
MSWI-FA and its durability.
The broad aim of the thesis is to provide a fundamental understanding of the effect of
addition of MSWI-FA in VA and vice- versa at different alkaline medium in order to try to
clarify and shed light to the underlying focuses below. It will also extend the utilization of
VA and will contribute to the solidification/stabilization concern of MSWI-FA.
25
Chapter II: Materials and experimental procedures
This chapter describes the raw materials, the research methodology and experimental
methods utilised in this thesis. A brief technical background to the fundamental basis for each
of the techniques is provided as well as sampling procedures. Techniques used include:
Isothermal (heat conduction) calorimetry (ICC), X-ray Fluorescence, X-ray Diffraction
(XRD), Particle Size Distribution (PSD), Fourier Transform spectroscopy (FTIR),
Differential Thermogravimetry (DTG), Thermogravimetry (TG), Scanning Electron
Microscopy (SEM) incorporating Energy Dispersive X-ray Spectrometry (EDS), specific
surface area measurement using the Brunauer-Emmett-Teller (BET) method, water
absorption, apparent porosity and bulk density, compressive strength and Toxicity
Characteristic Leaching Procedure (TCLP). The aforementioned experiments were achieved
in synergy between the Laboratory of Bio-organic, Analytical and Structural Chemistry of the
University of Douala-Cameroon and the Geopolymer Laboratory of the CSIR-National
Metallurgical Laboratory, Jamshedpur, India.
II.1. Materials
II.1.1. Volcanic ash
The Volcanic Ash (VA, Figure. 6) used in this study was collected from one of the
Cameroon’s reserve of pozzolana located in Loum-Moungo Division-Littoral Region (Figure
7). Sampling consisted of collecting small particles (4mm). The samples were stored in
different plastic bags and transported in load-resistant waterproof bags.
In order to transform volcanic ash into particles less than 200 µm, the collected sample was
oven dried for 24 h at 105oC and pulverized in a ball mill for 30 minutes.
26
Figure 6. Deposit of Volcanic ash located at Loum (Moungo-Littoral-Cameroon)
Figure 7. Location of the sample collection sites
27
II.1.2. Municipal solid waste incinerator fly ash (MSWI-FA)
The MSWI-FA (Figure. 8) used in this study, was collected in one of the incinerator
plants of the city of Douala-Cameroon. It results from the incineration of main municipal
solid waste (MSW) and incinerated at a temperature range from 500 to700 °C.
Figure 8. Municipal Solid Waste Incinerator Fly Ash
II.1.3. Sand
Locally available sand was collected from Jamshedpur’s river. The sand was washed
with tap water in order to eliminate the impurities, then air dried for a minimum of 7 days. It
was then sieved to obtain the 1 mm size (aggregate) fraction.
II.1.4. Alkaline solution
A combination of sodium silicate solution and sodium hydroxide solution were

chosen as the alkaline liquid [86]. Analytical grade sodium hydroxide in flake form (98%
purity, make: Emplura Chemical, India) was used to prepare alkaline solutions. The sodium
hydroxide was dissolved in distilled water in order to produce the desired concentration (6, 8
and 10M). The sodium hydroxide solutions were stored for a minimum of 24 hours before
use. The NaOH solution was blended with commercial water glass supplied by SDFCL-India
(With 28.7 wt.% SiO2, 8.9 wt.% Na2O and 62.4 wt.% H2O; density 1.37 g/mL) to produce the
28
alkaline activator solution based on the bulk composition. Six SiO2/Na2O molar ratios were
achieved by mixing the appropriate amount of sodium hydroxide and sodium silicate
solutions. The aforementioned solutions were packaged in closed plastic in order to avoid
their contamination by atmospheric carbonation.
II.2. Workability and Consistency of the Paste

Workability is one of the early salient factors which can affect the final properties of
alkaline activator. The workability was manually checked on each batch mixing to limit this
effect. The different batch mixing were chosen in accordance with chemical composition of
the raw material which showed that the MSWI-FA can be used as supplementary
cementitious for VA based alkali activated cement and vis versa. Five ratios of silicate
solution/NaOH solution 1.5, 2.0, 2.5, 3.0, and 3.5; for VA+MSWI-FA matrices and 0.8, 1.0,
1.2, 1.4 and 1.6 for MSWI-FA +VA matrices were chosen. After mixing the powder with
activator liquor the workability was studied manually for 5 mins.
II.3. Mix design and experimental procedure
II.3.1. Mix design
The mixing consisted of incorporating the VA in MSWI-FA and vice versa. The
ranges of silicate modulus for each mixing were chosen after the manual workability test.
Table 2 depicts the different mixing and the respective codes. In this table the subscript
number after GP indicates the percentage of VA or MSWI-FA incorporated depending of
system and X in bracket represents the Ms used.
29
Table 2. Bulk composition and batch mixing of alkaline activated cement
Mix SiO2/Al2O3 CaO/SiO2 NaOH (M) Na2SiO3/NaOH Ms L/S in

designation in weight in weight in volume volume
Incorporation of VA
GP0(X) 2.95 2.48 6, 8, 10 1.0 0.66, 0.56, 0.36 0.75
GP10(X) 3.17 1.71 6, 8, 10 1.0 0.66, 0.56, 0.36 0.70
GP30(X) 3.11 0.95 6, 8, 10 1.0 0.66, 0.56, 0.36 0.60
GP50(X) 3.11 0.59 6, 8, 10 1.0 0.66, 0.56, 0.36 0.50
Incorporation of MSWI-FA
GP0(Y) 3.11 0.17 10 1.5, 2.0, 2.4 1.0, 1.2, 1.4 0.25
GP5(Y) 3.11 0.2 10 1.5, 2.0, 2.4 1.0, 1.2, 1.4 0.30
GP10(Y) 3.11 0.23 10 1.5, 2.0, 2.4 1.0, 1.2, 1.4 0.35
GP15(Y) 3.11 0.26 10 1.5, 2.0, 2.4 1.0, 1.2, 1.4 0.40
GP20(Y) 3.11 0.29 10 1.5, 2.0, 2.4 1.0, 1.2, 1.4 0.45
Y=MS: silicate modulus; L/S: Liquid/Solid; X: Ms used for the considered system
II.3.1. Experimental procedure
The procedure consisted on weighing the respective masses of the ingredients, namely
MSWI-FA and VA for the synthesis of the alkaline activated binder and MSWI-FA, VA and
sand for the alkaline activated mortar, then homogenizing the mixing of the solids and then
mixing the solid with the volume of the appropriate activating solution. The mixing time was
set at 5 minutes. The mixture was poured into cubic steel molds (2.5cm for the cement paste
and 5.0cm for the mortar) and vibrated manually for 3 minutes. The samples are stored in
plastic sealed until they were demoulded (after 24 hours). The samples were stored in the
plastic sealed bags until the time of analysis. Figure 9 depicts the different steps handled to
produce and different analyses used to characterize alkaline activated binder and mortars.
30
Figure 9. Different steps handle to produce and different analyses used to characterize
alkaline activated binder and mortars
 Isothermal conduction calorimetry study
Isothermal (heat conduction) calorimetry was used to study the stages related to the
alkalinisation of cement pastes at 27 oC on the early age (48h). The rate of heat evolution
during the reaction (dq/dt) was evaluated using an eight channel isothermal conduction
calorimeter (TAM AIR, Thermometric AB, Jarafalla, Sweden). The equipment was calibrated
with the standard power of 60 mW using the procedure given in the equipment manual. The
main steps of the sample preparation were:
 Preparation of the alkaline activator solution,

 Mixing of the alkaline activator with the powder sample
 Loading of the mix in calorimeter.
31
5g of powder were used through the study and the ratio of the powder/alkaline activator
solution depended on the mixture. Instead of using 7 g for each channel of calorimeter,
(TAM AIR, Thermometric AB, Jarafalla, Sweden) 5g was used due to the high density of
MSWI-FA, which allows workability inside the bottle compared to 7g.
The time-dependent degree of reaction 𝛼(𝑡) was determined with the calorimetry data
following the Stutter method [16], according to Eq. (2.1) [13].
 t   Qt Q;max (2.1)
Where 𝑄(𝑡) is the cumulative heat, released at time t, and 𝑄𝑚𝑎𝑥 is the total or the
maximum heat released to complete the reaction. 𝑄𝑚𝑎𝑥 can be obtained from experimental
data of ICC [17], or can be predicted through model [75,87]. In order to determine the
kinetic parameters of the MSWI-FA, VA and MSWI-FA-VA alkaline activated reaction the
modified Jander Eq. (2.3) below was used [88].

lnt   N ln 1  1   
1/ 3
 ln K N (2.2)
Where α = degree of reaction; KN = rate constant; t = alkalinisatiion time; values of N

vary according to mechanism of reaction governing the process. N values can be obtained
from the slope of the plot of lnt versus 𝑙𝑛(1 − (1 − 𝛼)1/3 of the graph.
 Preparation of alkaline activated samples
 Alkaline activated pastes
 Incorporation of VA in MSWI-FA
NaOH solutions (6, 8 and 10 M) concentrations were used for the preparation of
samples. The solution was prepared at least 24 h before use. The sodium silicate/sodium
hydroxide volume’s ratio was kept at 1.0. The hot liquid was sealed to avoid carbonation and
left overnight to cool to ambient temperature in order to allow full depolymerisation of
sodium silicate. The specimens for compressive strength test were prepared by mixing
MSWI-FA-VA powder with the alkaline activator solution in the liquid/ MSWI-FA-VA ratio
that varied from 0.45 to 0.75 depending on the mixture. The matrix was mixed for 5 min. The
fresh paste was cast in 25 mm cubic moulds, followed by vibration for 2 min to remove
entrapped air bubbles during pouring. After casting, the samples were cured at room
32
temperature (20 ± 2 oC), then demoulded after 24 h and stored in sealed plastic awaiting
further tests. Table2. 1 presents the details of the bulk composition.
II.3.4.1.1. Incorporation of MSWI-FA in VA
Three SiO2/Na2O molar ratio (Ms=1.0, 1.2 and 1.4) were achieved by mixing the
appropriate amount of sodium hydroxide and sodium silicate solutions. The paste preparation
consisted of 0, 5, 10, 15 and 20% of MSWI-FA in VA. The GPX(Y) code was assigned to
each formulation. X corresponds to the percentage of MSWI-FA and Y the ratio of alkali
activator solution used. The specimens for compressive strength, water absorption, apparent
porosity and bulk density were prepared by mixing powder with the alkaline activator
solution. In order to achieve good workability the liquid/solid ratios used were 0.25, 0.30,
0.35, 0.40 and 0.45 for 0, 5, 10, 15 and 20% of MSWI-FA incorporation, respectively. After
mixing mechanically for 5 min the fresh paste was casted in 25 mm cubic moulds then
vibrated for 2 min to remove the entrapped air bubbles during pouring. The casted samples
were cured at room temperature (27 ± 5oC, relative humidity 60%), then demoulded after 24
h, except the GP0(X) samples, which were demoulded after 7 days and cured in sealed plastic
until the tests were performed.
II.3.4.2. Alkaline activated mortars
The best mixing according to mechanical properties of the aforementioned batch

mixing were selected to make alkaline activated mortars. The alkaline activated mortars were
obtained by first mixing the powder samples with sand for 2 min. The ratio of sand/powder
equal to 2 was used for all the batch compositions. The mixing of powders with sand for 1
min was followed by the addition of the corresponding alkaline solution and mixed for 5 min.
The above-mentioned mixtures were carried out via DIGI MORTAR MIXER (Made by Amil
Ltd, India). The geopolymer mortars obtained were then poured into 5 cm cubic moulds.
After casting specimens were cured at room temperature (27±5 °C and 65% RH), then
demoulded after 24h and kept in closed plastic at room temperature until the mechanical test
performed (28 days).
33
II.3.5. Preparation of aggressive media
II.3.5.1. Preparation of acid
Sulphuric acid (purity 98.08 %) was mixed with tap water to obtain the acid solution.
20 mL and 40 ml of concentrated acid were poured into 1L of tap water very slowly to
achieve 2% and 4% of acid solution, respectively. The solutions were used after minimum
24h.
II.3.5.2. Preparation of sea water
The artificial sea water (pH=7.5±0.5) was prepared following M1942 procedure [89]
by dissolving NaCl (24.600g), KCl (0.67g), CaCl2.2H2O (1.360g), MgCl2.6 H2O (6.290g)
and NaCO3 (0.180g) in tap water (1L). The solutions were used after minimum 24h.
II.4. Characterization of raw materials and alkaline activated samples

Different analyses were carried out in order to have the chemical composition,
mineral phases content, microstructure, physical and mechanical properties of MSWI-FA,
volcanic ash and alkaline activated samples.
II.4.1. Chemical composition
Two chemical analyses were carried out to determine the chemical composition of
raw materials. The Bruker-SRS 3400 x-ray fluorescence spectrometry (XRF) method was
used to check the bulk oxide composition of the both ashes. The principle of X-ray
fluorescence consists in sending X-rays to stimulate an electron in the inner shell. During the
de-excitation process, an electron jumps from a higher energy level to fill the gap thus
formed. The difference in energy between the two layers appears as an X-ray emitted by the
atom. The X-ray spectrum accumulated during this process reveals a number of characteristic
peaks. The elements present in the samples were determined using peak energies (qualitative
analysis), while peak intensities provide the relative or absolute concentration (semi-
quantitative or quantitative analysis) of the elements.
The inductive coupled plasma optical emission spectrometer coupled to ICP (ICP-
OES) (Vista MPX, Varian) method was used to determine the content of heavy metals in ash
after acid digestion. ICP-OES is based on the thermal excitation of ions in plasma and the
analysis of light emitted by these excited ions. Each element emits characteristic
34
wavelengths. The wavelengths were then separated, identified and their intensities measured
by a spectrometer. The elementary concentrations were then determined by comparison with
an external calibration. This spectrometer has advantage to detect trace elements in a range
from ppt (part per trillion) or ppb (part per billion) to mass percentage. The only elements
that cannot be measured by these methods are H, C, O, O, N and halogens.
II.4.3. Mineralogical composition
The recording of powder diffractograms of raw material powders and alkaline

activated samples were done using a Bruker X-ray diffractometer (D8 Discovery, US) using
radiation Cu Kα. Before the samples are analysed, the powders of the raw materials were
sieved to 100 µm in order to standardize the particle size. The pieces of alkaline activated
binder were collected during compressive test at 28 days of curing, then dried, grounded and
sieved at 100µm. Concerning the alkaline activated mortar samples, the pieces were collected
during the compressive strength test of non-immersed and immersed in aggressive medium
for 60 days samples. The mortar pieces after drying were ground and sieved carefully in order
to eliminate sand particles. The passing powder obtain was then ground and sieved at 100µm.
Sample preparation for scanning consists of placing the powder on a sample holder
while ensuring that the surface of the powder that will be subjected to the effect of x-rays is
flat. The rotation speed of 2o /min and the scan angle of 10o to 70o was used. The phases
present were identified by comparing the powder XRD patterns with the standard powder
diffraction database of International Centre for Diffraction Data (ICDD PDF-2 Release
2016).
The different chemical bonds of volcanic ash, MSWI-FA and alkali activated samples
were determined through a Fourier transform infrared spectroscopy (Nicolet 5700 FTIR,
Thermo Electron Corporation) in reflectance mode in the range of 400-4000 cm-1. A small
amount (1mg) of sample prepared for XRD analysis was incorporated into a support that does
not absorb in the medium IR, here KBr (potassium bromide). A homogeneous mixture of
approximately 1% sample powder/KBr powder was prepared and finely ground. It was
placed in a mould and then subjected to very high pressure in a press. The pellet extracted
from the mould was placed on a sample holder and placed in the spectrum measurement
compartment along the path of the incident beam. After folding the crank handle down to
cover the sample, the spectrum recording is directly performed. Once the recording was
completed, a treatment was done to remove the parasitic absorptions by subtracting the
35
background noise spectrum (spectrum of a pure KBr pellet) from the sample spectrum. The
spectra were recorded in transmittance.
II.4.4. Physical properties of raw materials
The laser particle size analyser (Mastersizer 2000, Malvern, UK) was used to measure
the size distribution of particles (volume and number) of MSWI-FA powders and VA.
Around 0.3g of powder sieved to 100 µm is dispersed in distilled water, by means of
ultrasound and without dispersing agent. It consists of sending the laser beam (He-Ne)
through the dispersed material particles. Each particle will diffract the radius at an angle that
depends on its own diameter (particle size). Large particles diffract light at a small angle,
while small particles diffract the beam at a larger angle. The particles scatter the incident
beam and the Fourier lenses allow the detection range of the scattered beam to be focused
towards the same point.
The Brunauer-Emmett-Teller (BET) surface area of each powder was determined by

nitrogen sorption on a Micromeritics (Norcross, GA) ASAP2010 instrument. The specific
surface area is determined by physical adsorption of a gas on the surface of the solid and by
calculating the amount of adsorbate gas corresponding to a mono molecular layer on the
surface. Physical adsorption results from relatively weak forces (van der Waals forces)
between the adsorbate gas molecules and the adsorbent surface area of the test powder. The
determination is carried out at the temperature of liquid nitrogen. The amount of gas adsorbed
can be measured by a volumetric or continuous flow procedure.
The bulk density (BD) was obtained by using the ASTM Standard Testing Procedure
(ASTM D7481-09) [90]. The tapped density is an increased bulk density attained after
mechanically tapping a container containing the powder sample. The tapped density is
obtained by mechanically tapping a graduated measuring cylinder or vessel containing the
powder sample. After observing the initial powder volume or mass, the measuring cylinder is
mechanically tapped, and volume or mass readings are taken until little further volume or
mass change is observed. The tapped bulk density is calculated by dividing the mass of the
sample by the final tapped.
36
II.4.5. Microstructure
The scanning electron microscopy (SEM) allows the surface of a sample to be imaged
on the nanometer scale. The technique relies on surface bombardment with high energy
electrons in an evacuated chamber. The surfaces of the solids being analysed must be
conductive and are thus coated with monolayers of a conductive substance such as carbon,
gold etc. A Nova Nano SEM, FEI 430, Field Emission Gun Scanning Electron (FEG-SEM)
operating at 15 keV was used for SEM imaging. Elemental analysis was conducted randomly
across the area of interest equipped with energy dispersive X-ray analysis (EDX) operating at
15.0 kV for raw materials and MSWI-FA+VA matrices products. HITACHI S-3400N
Scaning Electron Microscope equipped with Energy Dispersive X-ray Spectrometry analysis
(EDS), operating at 15.0 kV was used for VA+MSWI-FA matrices products and alkaline
activated mortars. A DYNAVAC sputter coater was used in coating the fractured specimens
with carbon.
II.4.6. Compressive strength
The compressive strength tests of alkaline activated based MSWI-FA and VA ash
blends and mortars were done on 2.5 x 2.5 x 2.5 cm and 5.0 x 5.0 x 5.0 cm cube specimens,
respectively. Geopolymer blends cubes were cast in steel moulds. Each mould was well
compacted by vibrating for two minutes. After compaction, the top surface was covered with
polythene sheet to prevent evaporation. The specimens were demoulded after 24 hours of
casting. They were then left at ambient room temperature in sealed plastic for curing until the
testing days. Then the geopolymer specimen’s cubes were tested in an Automatic
Compression Testing Machine (AIMIL COMPTEST 2000, India). The GP0(X) samples were
polished in order to uniformalise the shape before the test. The triplet test was used for each
specimen. The compressive strength at failure is calculated using the Equation (2.3).
Ultimate compressive load

Compressive Strength  (2.3)
Area of sec tion of speciment
II.4.7. Bulk density, water absorption and apparent porosity
The water absorption (WA) test was determined in agreement to ASTM C-642[91].
The procedure consisted of drying the 28 days aged specimens in an oven at a temperature of
65oC for 24 hours. After each specimen was removed from the oven, it was allowed to cool in
37
dry air to a temperature of 22±3 oC and then weighed (Wd). The specimens were then
immersed in water at 22 ± 3oC for 24 hours. The test specimens soaked in water were
removed from the immersion container and dried using a towel to eliminate surface moisture.
The specimens were then weighed immediately. The final surface dry mass after immersion
was designated Ws. The water absorption (WA) was thus calculated using the relationship
below.
Ws  Wd 
WA  *100 (2.4)
Wd
The bulk density (BD) and apparent porosity (AP) of the alkaline activated specimens
were determined according to Archimedes principle in accordance to ASTM C-20 with water
as immersion medium. The specimens were dried in a ventilated oven at 65°C for 48 hours
and their weight was recorded as Wd. The specimen was then immersed in water at room
temperature (28°C) for a minimum of 48 hours. The specimen was then weighed while
suspended by a thin wire and completely submerged in water and Wi recorded. The
specimens were then removed from water and allowed to drain off by placing them on a wire
mesh. Visible surface water was cleaned with the aid of a damp cloth. The specimens were
then weighed and their saturated weight recorded as Ws. The bulk density and apparent
porosity were then calculated from relation (5) and (6) respectively:

BD Kg 
m3 
Wd
Wd  Wi
*100 (2.5)
Ws  Wd 
AP %   *100 (2.6)
WS  Wi 
II.4.8. Thermal analysis (DTG/DTA)
Simultaneous DTA and TGA measurements were performed on HITACHI STA 7300
DTA/TGA equipment with platinum sample crucibles. The powder was heated in Nitrogen
(purge rate of 200 mL/mn) at 10˚C/mn. The change in the weight of the substance was
recorded as a function of temperature or time. The temperature increased at a constant rate for
known initial weight of the substance and changes in weight were recorded as a function of
temperature at different time intervals.
38
II.4.9. Leaching test characterization
The Toxicity Characteristic Leaching Procedure (TCLP) was designed to determine

the mobility of heavy metals present in hardened alkaline activated pastes cured for 28 days.
It is a method that simulates what happens when alkaline activated cements are disposed in
the nature and is utilized to determine if the alkaline activated cements comply with the
environment standards. The USEPA 1311 protocol was used for TCLP[92]. The cube
samples were dried at 105 oC, crushed and sieved at 10 mm aperture size. The samples (10g)
were then extracted with an amount of TCLP extraction fluid (acid nitric, pH= 3.2±2) equal
to 20 times the weight of the solid phase for 18 hours on the Millipore Rotary Agitaror (Y132
ORA HW-India) at the mixing speed of 30 ± 2 r·min-1. The TCLP extract was separated from
the solid phase by filtering through a 0.6 micron filter via Millipore. The TCLP extract was
combined with any liquid from the initial separation and the sample was analysed of TCLP
metals by using ICP-OES. Figure 10 depicts the different equipment used for leaching test.
Figure 10. TCPL equipment (a) Millipore Rotary Agitaror (Y132 ORA HW-India), (b)
Millipore filter, (c) Inductively Coupled Plasma – Optical Emission Spectrometer (ICP-OES)
(Made by Varian)
II.5. Durability test
The durability test involved immerging the alkaline activated mortars cured for 28
days in an aggressive media. Sulfuric acid (2% and 4%) and sea water were chosen as
aggressive. The procedure followed is depicted on the Figure 11.
39
Figure 11. Different steps handle, and analyses used to study the durability of alkaline
activated mortars.
II.5.1. Artificial sea water resistance
The use of sea artificial sea water can be justified, firstly by the fact that littoral is
situated in a coastal area and it is close to sea water and secondly because the artificial sea
water contains Chlorine, sulphate, alkaline and alkaline earth metals which are harmful for
the geopolymer. The test consisted of immersion of samples aged for 28 days into artificial
sea water (pH=7.5) for 60 days. The solution was renewed weekly in order to keep the pH
constant. The weight loss and residual compressive strength were then tested after 0, 7, 14, 28
and 60 days of immersion.
II.5.2. Sulphuric acid resistance
The sulphuric acid resistance test consisted of immersion of samples aged for 28 days
into 2 and 4 wt. % H2SO4 solution for 60 days. The solution was renewing weekly in order to
keep the pH constant. The weight loss and residual compressive strength were then tested
after 0, 7, 14, 28 and 60 days of immersion.
40
Microstructural and structural characterization techniques (XRD, FTIR and FEG-
SEM/EDS) were all performed on samples immerged for 60 days using the same instruments
and conditions as described in previous sections II.3.3 and II.3.5. Figure 12 presents the
samples immerged in artificial sea water and sulphuric acid.
2.5% sulphuric 5% sulphuric acid Artificial sea water

acid
Figure 12. Alkaline activated samples into sulphuric acid and artificial sea water.
41
Chapter III: Results and discussion
The results and detailed discussions of the analyses described in chapter 2 are outlined
in this chapter. The statement of novelty in the field of alkaline activated materials synthesis
of different parts of this thesis i.e the improved reactivity of volcanic ash using municipal
solid incinerator fly ash for alkali-activated cement synthesis, the supplement of Al and Si in
MSWI-FA by the addition of VA for alkali-activated cement synthesis and the resistance
study of alkaline activated mortars from VA+MSWI-FA matrices in sulphuric acid and
artificial water media are also reported. The chapter presents the alkaline activated pavement
blocks developed from VA+MSWI-FA matrices.
III.1. Characterization of raw materials
III.1.1. Physical properties
The physical properties of MSWI-FA and volcanic ash are presented in Table 1.
Figure 13 represents the density distribution and cumulative distribution of MSWI-FA and
volcanic ash. The both materials have roughly the same median diameter 11.52 and 11.14 µm
for MSWI-FA and VA, respectively. The d10, d50 and d90 particle diameters are 0.34, 11.52,
56.91 and 0.31, 11.14, 59.93 µm in MSWI-FA and VA, respectively. Both materials are
heterogeneous; this can be explained by the bimodal mode’s nature of density distribution
curves. They are fine and suitable for polymerisation/polycondensation. The B.E.T surface
area of MSWI-FA (7.4 m2/g) is higher than VA (3.6 m2/g) surface area. Thus both materials
will not have the same behaviour when mixed with activator liquor. This difference could
affect the workability of the cement at a given L/S ratio and the degree of alkalinisation and
strength development over long periods of time, among other factors. Bulk density and
specific gravities are 0.71 and 1.51, 2.86 and 1.90 g/cm3 for VA and MSWI-FA respectively.
These parameters will have the impact on the weight of the product.
42
Table 2. Physical properties of municipal solid waste fly ash and volcanic ash
Physical properties
MSWI-FA VA
Median diameter (µm) 11.52 11.14
Bulk density (g/cm3) 0.71 1.51
BET (m2/g) 7.4 3.6
d10( µm) 0.34 0.31,
d50( µm) 11.14 11.14
d90( µm) 56.91 59.93
Figure 13. The density distribution and cumulative distribution of municipal solid waste fly
ash and volcanic ash.
III.1.2. Chemical composition
The chemical composition of volcanic ash and MSWI-FA are listed in Table 3. The
samples were analysed using the XRF and ICP-OES method. The result display that the main
constituents in volcanic ash are SiO2, Al2O3 and Fe2O3 constituting 75.98% and in MSWI-FA
43
are CaO (26%) followed by SiO2, Cl and SO3. They also contain considerable amount of
alkalies such as Na2O, K2O and MgO. If we consider the potential reactivity of the volcanic
oxides, it is judged appropriate for design of AAM [93]. The VA can also be used as adjuvant
in order to supplement the deficiency of Al and Si in material which has the potentiality for
the synthesis of alkali activated material. The amount of CaO (26%) in MSWI-FA means it
can be used in alkali-activated cement as additive. The amount of SiO2, Al2O3 (13.81%) is too
less than 80%; so its use as the feedstock in the synthesis of alkali-activated materials
requires the addition of a supplementary material rich in SiO2 and Al2O3. The both samples
contain the heavy metals. The amount of heavy metals in VA is less than the amount fixed by
the United States Environmental Protection Agency (USEPA). The amount of some heavy
metals in the MSWI-FA such as Pb (23.84 mg/L˃5.00 mg/L), Cr (12.50 mg/L˃5.00 mg/L),
Hg (18.50 mg/L˃5.00 mg/L), Se (6.18 mg/L˃1.00 mg/L), Ag (6.00 mg/L˃1.00 mg/L) and Cd
(15.00 mg/L˃1.00 mg/L) exceeds the amount fixed by the USEPA. This shows that the
MSWI-FA is considered as the toxic waste.
Table 3. Chemical composition of volcanic ash and municipal solid waste fly ash.
XRF analysis
Oxides SiO2 Al2O3 CaO Fe2O3 Na2O K2O MgO Cl SO3 LOI
MSWI-FA (%) 10.46 3.35 26.00 1.72 2.46 3.32 2.65 11.84 8.10 28.3
VA (%) 47.74 15.36 8.25 12.88 3.62 1.11 6.45 - - 0.66
ICP-OES analysis
Heavy metals Pb Cr Hg Zn Ba Se Ag Cd
MSWI-FA(mg/L) 23.84 12.50 18.50 12.07 9.22 6.18 6.00 15.00
VA (mg/L) 0.0103 0.0004 0.0170 0.0373 0.9792 0.0713 NF NF
III.1.3. Mineralogical properties of VA and MSWI-FA
Figure 14 depicts the XRD diffraction patterns of MSWI-FA and VA. The XRD
patterns show the featureless ‘hump’ located at 25-37o 2ϴ (MSWI-FA) and at 21-38 o
2ϴ
(VA). The X-ray diffractogram shows that the volcanic ash is predominantly made of
crystalline phases that include Anorthite (Na(AlSi3O8), PDF#01-073-6461), Feldspar
(NaAlSi3O8, PDF#01-083-6911), Nepheline (K0.48Na3.48(Al0.99Si0.01O4), PDF#01-073-6265),
Maghemite (Fe2O3, PDF#00-001-0551) and Diopside (Ca (Mg,Fe,Al)(Si,Al)2O6,PDF#01-
44
071-0994). Although some crystalline minerals dispersed into the amorphous matrices, these
materials are found suitable for alkali activated cement. The MSWI-FA is mostly composed
of glassy phases and Anhydrite (CaSO4, PDF#00-003-0368), Bassanite (CaSO4.0.5H2O,
PDF#00-041-0224), Gypsum (CaSO4.2H2O PDF#04-009-3817), Calcite (CaCO3, PDF#00-
005-0586), Quartz (SiO2, PDF# 00-029-0085) and Halite (NaCl, PDF#00-005-0628) as the
crystalline phases. In the view of these diffractogramms the main constituents in MSWI-FA
are amorphous, this shows that these constituents, especially CaO, SiO2 and Al2O3 are easy to
transform during alkaline attack. However, less constituents (glassy phases) are easy to attack
in VA. These facts reveal that the MSWI-FA is reactive in alkaline medium than VA [43].
Figure 14. XRD patterns of volcanic ash and municipal solid waste fly ash
III.1.4. Structural characterization
III.1.4.1. FTIR
Both spectra (Figure 15) exhibited the bond characteristic of the asymmetric
stretching vibrations of Si-O-T (T= Si or Al) with peaks at around 1030 cm-1 and 1161 cm-1
for VA and MSWI-FA, respectively [94,95]. The peaks appearing at 579 cm-1 (VA) and 675
cm-1 (MSWI-FA) correspond to Si-O bonding vibration of quartz [96] and the peak at 472
45
cm-1 for VA represents the vibration of Si-O-Fe bond [14]. The characteristic bonds of the
silanol group and water molecules are situated at 3421 cm-1 and 1643 cm-1 for VA; 3436 cm-1
and 1621 cm-1 for MSWI-FA. The peak at 1446 cm-1 characterizes the C-O bond, which
confirms the presence of calcite highlighted in XRD analysis.
Figure 15. FTIR spectra of volcanic ash and municipal solid waste fly ash
III.1.4.2. TG/DTA characterization
Figure 16 depict the TG/DTA graphs of MSWI-FA and VA, respectively. The curves
characterizing mass losses as a function of heating temperature (TG curves) are as follows: (i)
The first zone of decline between 27-400oC, symbolizing the evaporation of absorbed and
structural water. This loss is greater on the MSWI-FA curve. This is justified by the fact that
several minerals observed in the XRD analysis are hydrated and the high intensity of O-H in
MSWI-FA (Figure 16.a). This fact also shows that VA is a low hydrated aluminosilicate
material. (ii) The second loss zone between 550-800oC which is almost non-existent on the
VA curve. This second loss is due to the carbonation of organic matter and calcium
carbonate. Its absence on the VA curve is consistent with the results of LOI, which showed
that VA contains low amount of organic matter.
46
The DTA curves show the thermal reactions that occur when powders are heated.
Dehydration reactions are characterized by the endothermic peak (I). Carbonation reactions
are characterized by exothermic peaks (II) (Figure 16.b). In the view of these weight loss at
temperature up to 800o, it can be concluded that both materials present good thermal stability
at this range of temperature especially VA.
(a)
(b)
Figure 16. TG-DTA curves of volcanic ash and municipal solid waste fly ash; (a) MSWI-FA
(b) VA
47
III.1.5. Microstructure characterization
Figure 17 depicts the micrographs of FEG-SEM analysis and the EDS of crystalline
phases found of the raw materials. MSWI-FA particles have irregular shapes (2a) and
spherical shapes (1a and 3a). EDS analysis show that the crystalline phases on MSWI-FA’s
spot are: calcium chloride (1a), silicate (2a) and calcium carbonate. Based on the XRD
analysis, the silicate phase is attributed to quartz and the calcium phase is attributed to calcite.
Calcium chlorine was not found in the XRD analysis this could be due to its low amount. The
aluminosilicates phases are not prominent; this assigns that 3% of alumina in MSWI-FA is
quasi-amorphous. The VA’s SEM image show only the aluminosilicates irregular shapes
(Figure 17.b). This is consistent with the XRD results which reveal the prominence of
aluminosilicates phases such as Anorthite, Feldspar, Nepheline and Diopside.
Figure 17. FEG-SEM/EDS of raw materials. (a) MSWI-FA; (a) VA and (c) EDS of
crystalline phases.
48
III.2. Workability and Consistency of the Paste
Workability is one of the early salient factors which can affect the final properties of
alkaline activated. The workability was manually checked on each batch mixing to limit this
effect.
III.2.1. Workability and Consistency of the Paste of alkaline activated based

MSWI-FA
All the pastes obtained with these ratios especially the paste from unamended MSWI-
FA presented high workability and the workability increased with the rise of ratio. When the
ratio 1.0 was choose the workability became manageable. This ratio was fixed on all the
mixing. The paste prepared from unamended MSWI-FA required a high amount of alkaline
solution (ratio liquid/solid = 0.75) to have good workability. However, when 50% volcanic
ash was incorporated in the MSWI-FA, good workability at the ratio 0.5 was achieved. This
is traceable to the difference in specific surface area (7.5m2/g and 3.6 m2/g for MSWI-FA and
VA, respectively) of these materials.
III.2.2. Workability and Consistency of the Paste of alkaline activated based VA
Good workability was achieved with pastes made only with VA at all these ratios and
the suitable ratio of solid/liquid was 0.25. When the MSWI-FA was added the ratio 1.5, 2 and
2.5 accomplished less workability and the ratio 3.0 and 3.5 achieved high workability and the
ratios of solid/liquid increased from 0.25 to 0.3, 0.35, 0.4 and 0.45 for 5, 10, 15 and 20,
respectively. The difference of alkaline liquor’s demand can be explained by the difference in
bulk density (0.71 g/cm3 and 1.51 g/cm3 for MSWI-FA and VA, respectively) and specific
surface area (7.5 m2/g and 3.6 m2/g for MSWI-FA and VA, respectively) of these materials.
The poor workality is due to high amount of fast reactive SiO2 and CaO which precipitate to
form calcium silcate phases in the early age. This causes the fast setting (‘’flash setting’’).
III.3. Study of cement alkalinization

The isothermal conduction calorimetry was used to monitor the polymerisation/
polycondensation reaction during the addition of MSWI-FA in VA based alkali activated
cement and the addition of VA in MSWI-FA based alkali activated cement at the respective
silicate moduli at early age (48h). The heat released and the kinetic parameters of each batch
mixing were also evaluated.
49
III.3.1. Alkaline activated based VA
Figure 18 and 19 represent the heat evolution rates and the total heats released respectively,
from the alkalinization of VA and VA - MSWI-FA systems at different activator modulus.
The reaction studied here is an exothermic process and involves different stages depending
on the batch mixing. Only the mixings with silica modulus of 1.0 were selected to show the
effect of the incorporation of MSWI-FA on the reaction evolution rates. The rapid first stage
of reaction (I), which is the uppermost exothermic process, characterises the absorption of
alkaline solution on the surface of raw materials particles and the succeeding dissolution of
the glassy phases [97]. The intensity of this peak increases with the incorporation of MSWI-
FA. That is due to high specific area and glassy nature of MSWI-FA. The first stage is
followed by the stage (II) (dissolution/precipitation). The sample without MSWI-FA shows
no prominent peak after the initial dissolution and the heat released is insignificant, this
indicates that the VA operates as low reactive phases under alkali activation at room
temperature. However the intensity and the surface area (0.54, 0.56, 0.90 and 1.2 u.a for 5,
10, 15 and 20%, respectively) of the peaks at this stage increases with the incorporation of
MSWI-FA. In fact the dissolution of the MSWI-FA in the alkaline medium releases the
calcium, silicate and small aluminate ions into the system, which precipitate from the early
age to form C-S(A)-H gel. The deceleration after the stage (II) indicates that the first
precipitation reaction is slowing down, but these reactions still continue during the curing.
This fact can be justified by the small heat released during stage (III). On diffusion period
(III), the Si-O and Al-O bonds in volcanic ash broke down slowly to form aluminosilicates
oligomers on going to the polymerisation of alkaline activated gel. The aforementioned heat
released is also attributed to the substitution of Si by Al and Na by Ca, Mg in C-S-H and
alkaline activated gel, respectively [98,99]. The effect of Ms was not studied on heat
evolution rates, because the mixing with Ms=1.2 and 1.4 did not present prominent peaks
after the step (I). However, the total heat released allows the study of this effect. From the
analysis of Figure 5, it emerges that the total heat released increases with the incorporation of
MSWI-FA, increases also with Ms from 1.0 to 1.2 and decreases from 1.2 to 1.4. The
possible explanation of this increase may be due to the availability of more silicate which
raises the reaction of precipitation (exothermic process). The decrease is due to the excessive
silica content which leads to the condensation between silicate species and inhibits further
dissolution and slows down alkalinization [100,101]. In fact sodium silicate provides soluble
silicate species, which are necessary for the initiation of oligomers (monomers, dimmers,
50
trimers and tetramers) formation, according to the polycondensation of silicate, but the high
amount of silicate is detrimental to this reaction. The excess of sodium silicate rapidly
hardens the paste, but this hardening is due to the precipitation and coagulation of sodium
silicate. The rapid setting could also affect the mechanical properties of the alkali activated.
Figure 18. ICC plots of VA and VA-MSWI-FA alkaline activated at different silicate moduli
(Ms=1.0, 1.2 and 1.4)
Figure 19. The total heat released at 48h during alkalinisation of alkali activated cements at
different alkali moduli (Ms=1.0, 1.2 and 1.4)
51
Table 4 illustrates the values of the kinetic parameters. It can be seen from this table
that the rate constant (KN) values increase with incorporation and the silicic modulus from
1.0 to 1.2. The reduction of these values from 1.2 to 1.4 is due to the excess silicate which
upholds a rapid setting by precipitation of C-S-H, limiting geopolymerization. The values of
N in GP0 are less than 0.5 and those of GP5, GP10, GP15 and GP20 are greater than 1,
showing that the reactions in samples without MSWI-FA are different from those containing
MSWI-FA. These observations corroborated with the facts underlined above.
Table 4. Kinetic parameter values of alkali activated cements at different alkali moduli
(Ms=1.0, 1.2 and 1.4)
GP0 GP5 GP10 GP15 GP20

1.0
Q(J/g) 14.09 19.36 12.62 26.53 32.65
N 0.37 1.17 1.38 1.33 1.37
KN (10-2) 3.39 4.48 4.49 4.60 4.60
R2 0.15 0.90 0.90 0.86 0.89
1.2
Q(J/g) 11.65 27.53 29.21 31.63 36.41
N 0.04 1.88 1.60 2.03 1.46
KN (10-1) 2.93 4.38 4.33 4.65 4.25
R2 0.00 0.76 0.77 0.96 0.71
1.4
Q(J/g) 10.62 11.78 11.85 14.09 15.32
N 0.18 1.43 1.53 1.92 1.78
KN (10-3) 3.12 4.54 4.51 4.76 4.53
R2 0.04 0.74 0.83 0.89 0.73
III.3.2. Alkaline activated based MSWI-FA
On the ICC plots of MSWI-FA and MSWI-FA-VA three steps of reaction have been
identified (I, II and III, Figure 20). The rapid exothermal peak (I) corresponds mainly to the
physical phenomenon (wetting) and the first chemical phenomenon, dissolution of the glassy
phases in the alkaline medium via the rupture of Si-O-T (T: Si or Al) and Ca-O bonds in
MSWI-FA and VA. The peak (I) in 6 M medium is broad compared to 8M and 10M media
which are narrows. In 6M medium the peak (I) slows down till the heat flow is less than 2.5
mw, while in 8M and 10M media the peak (I) slows down till heat flow is less than 6 mw.
These differences can be assigned to the high dissolution of glassy phases in high alkali
medium, which promotes the rapid precipitation. This rapid phenomenon is followed by the
52
second exothermal peak (II) which characterizes the dissolution and precipitation period.
Generally the step (I) and (II) are separated by an induction period. The induction period is
almost non-existent here; this can be explained by the high reactivity of one of the raw
materials. During steps (I) and (II) the dissolution of calcium and silicate phases form two C-
S-H precipitates called “outer C-S-H gel” and “inner C-S-H gel”, respectively [30]. The
intensities of peak (I) and (II) decrease with the addition of VA. This fact reveals that the VA
has low reactivity in alkali medium at room temperature. The last step (III) is the diffusion
period. During this step, fairly small amount of heat continues to be generated even after 24h.
This heat is attributed to the ongoing reactions namely: dissolution of low reactivity phase,
diffusion of Ca and Al ions across the cementitious matrix and the modification of the
composition of different gels (N-A-S-H to N(C)-A-S-H and C-S-H to C-(A)-S-H or C-A-S-H
gel) [3].
Figure 21 represents the cumulated heat plot of selected samples, released during the
aforementioned steps of reaction. This cumulated heat is attributed mainly to the dissolution
and precipitation phenomenon. The total heat released (Q. J/g) after 48 h of reaction of all
samples is depicted in Table 5. In the view of these results, the heat released increases with
the rise of the concentration of alkali medium and diminishes with the addition of VA. This
fact is consistent with the isothermal conduction calorimetry study. One of the things
responsible for the high heat released here is the precipitation of Ca(OH)2 due to the
emergence of Ca2+ and HO- species in high alkaline media. The precipitation of Ca(OH)2 is
detrimental to the properties of alkaline activated cement. The values of different kinetic
parameters illustrates in Table 3 decrease with the substitution of MSWI-FA by VA and
increase with the substitution of VA by MSWI-FA in the matrices. This fact confirms the
high reactivity of MSWI-FA in alkaline medium comparing with VA.
The Table 5 illustrating the kinetic parameters shows that the values of the reaction’s
constant (KN) decrease with the incorporation of VA and the concentration of the activating
solution. These phenomena show that the alkalinization reaction emerges with the reduction
of the concentration. The values of N show that reactions in GP0 do not depend on
concentration but are different from reactions in GP50.
53
(III)
Figure 20. ICC plots of MSWI-FA and MSWI-FA-VA alkaline activated with different
alkali concentrations at 27 oC (a) 6M, (b) 8M, (c) 10M
54
Figure 21. Cumulated heat plot of GP0(6), GP30(6), GP50(6), GP50(8) and GP50(10)
Table 5. Kinetic parameter values of alkali activated cements at different concentration (6, 8
and 10M)
GP0 GP10 GP30 GP50

6M
Q(J/g) 52.82 48.098 41.85 22.42

N 1 0.911 0.792 0.424
K (10-2) 9.55 8.76 8.12 7.00
R2 0.91 0.88 0.84 0.72
8M
Q(J/g) 59.93 59.26 50.41 41.26

N 1 0.98 0.84 0.68
K (10-4) 2.00 2.00 2.00 2.00
R2 0.89 0.89 0.89 0.84
10M
Q(J/g) 64.03 61.70 57.34 48.00

N 1 0.96 0.89 0.74
K (10-7) 2.103 6.00 6.00 6.00
R2 0.76 0.78 0.82 0.89
55
III.3.2. Conclusion
This part consisted to study at the early age (48h) the behaviour of alkalinisation
reaction when the different matrices were mixed with activator solutions. In the view of the
aforementioned result, it can be concluded that the early reactions are mainly prompted by
MSWI-FA and the concentration and silicate modulus of alkaline activated solution impact
these reactions. The VA reacted in the diffusion period which can extend up to 28 days.
III.4. Characterization of alkaline activated binders

III.4.1. Improved reactivity of volcanic ash using municipal solid incinerator fly
ash for alkali-activated cement synthesis
Knowing that volcanic ash (VA) is one of the most potential raw materials for alkali-
activated synthesis due to its amorphous aluminosilicate content. However, its low reactivity
in alkaline medium limits its utilization in the alkali-activated field. This part proposes
municipal waste incinerator fly ash (MSWI-FA) as additive to enhance the properties of
alkali-activated matrices from low reactive VA contributing to recycle a hazardous waste i.e.
MSWI-FA as supplementary cementitious material. This solution could appear energy-
efficient and sustainable for the production of green building materials.
III.4.1.1. Visual aspect of cement after demoulding
It has been observed that (Figure 22), the samples (GP5, GP10, GP15 and GP20) after
demoulding during 24h do not show any significant deformation to the naked eye. However,
alkaline activated without incorporation of MSWI-FA (GP0(1.0), GP0(1.2) and GP0(1.4))
after 7-day demoulding show remarkable physical deformation. This change of shape can be
explained by the evaporation of water before curing, which leads to a strong linear shrinkage
before curing. The other samples also have a linear shrinkage but this is done after the paste
has hardened and does not affect the physical deformation of the sample. In fact, water
mainly provides a medium to facilitate the alkalinization reaction [102]. But when the
reaction is slow, the system would lose the main water and the alkalinization and the
shrinkage will be affected.
56
Figure 22. Visual aspect of alkaline activated samples after demoulding.
III.4.1.3. Phases evolution (FTIR and XRD)
The phase evolution in the formulation of alkali-activated materials with different

amount of MSWI-FA and at different Ms is presented in Figure 23 and 24.
Comparing the FTIR spectrum of volcanic ash to alkali-activated cements spectra,

several differences were observed (Figure 23 (a)): (i) The Si-O-T (T=tetrahedral Si or Al)
asymmetric stretching vibrations band appearing at around 1033 cm-1 and 570 cm-1 in the
FTIR spectrum of VA, shift to lower frequencies (1016-1000 cm-1and 467-460 cm-1 ) in the
FTIR spectra of alkali-activated cements and the shift is less in high Ms. (ii) The broadness of
the bands at around 1000 cm-1 decreases with the incorporation of MSWI-FA. (iii) The alkali-
activated samples exhibit a band at around 1430 cm-1, which was assigned to stretching
vibrations of the O–C–O related to the unreacted calcite from MSWI-FA and the product of
the carbonation of Ca(OH)2 [103]. The bond located at around 1000 cm-1 and 1400 cm-1 in
VA-MSWI-FA matrix are also attributed to S-O and S=O bonds. The bands appearing in all
FTIR spectra in the region of 3500 and 1600 cm-1 are assigned to –OH stretching and H-O-H
bending vibrations bond of water molecules, which are surface absorbed or chemically bound
to the polymer network increase with the addition of MSWI-FA. The shift of the principal
band of the volcanic ash from 1022 cm-1 to 1016-1000 cm-1 is explained with the
incorporation of Ca into the alkali activated material network. An increase in the silica
modulus from 1.0 to 1.2 induces the shift of the principal alkaline activated band to relatively
high wavelength Figure 23 (b), a situation that is in accordance with the literature [78,104] in
the presence of additional soluble and reactive silica, which improve the polymerization and
polycondensation. The contradiction from 1.2 to 1.4 could be explained by the fast reaction
between reactive Si and Ca. The aforementioned changes can induce the formation of new
minerals.
57
The XRD analysis was used to check the minerals after alkalinisation. Comparing the
alkali-activated cement patterns to XRD pattern of VA (Figure 25), all the crystalline phases
originally in VA are present. The hump characteristic of the amorphous (glassy) phase in
volcanic ash is centred at 28o and no conspicuous shift was observed after alkalinization. The
formation of new minerals after alkalinization in VA-MSWI-FA alkali-activated cements is
evidenced, namely: C-A-S-H (Margarite, CaAl2(Al2Si2)O10(OH)2, PDF#04-013-3004)),
Mordernite-(Ca) (Ca,Na2,K2) (Al2Si10O24) .7H2O, PDF#00-011-0155) and Thernadite
(Na2SO4, PDF#01-074-2036). The intensity value of each peak located at 28o is represented
on its right reduces with the addition of MSWI-FA and increase with the rise of Ms. The
behaviour of the new alkali activated materials is contrary to the behaviour of pure
aluminosilicate based alkaline activated materials which promotes the shift of hump after
alkalinisation [78,105]. This could be explained by the low reactivity of the volcanic ash used
as observed in the calorimetric study. The C-S-H rarely formed in calcium aluminosilicates
precursors at alkalinity higher than 8M [98,99,106]. Its presence here could be due to the
prominence of reactive calcium in VA after addition of MSWI-FA. This fact was also
reported by Djobo et al [16] in Oyster Shell-Volcanic Ash system at high alkalinity (15M).
The presence of C-S-H and Mordernite-(Ca) and Thernadite is supplemented by the results of
FTIR analysis. The peak at 28o is mainly characterizing the Anorthite in VA and Anorthite
with C-S-H in VA-MSWI-FA matrices. When the VA is substituted by MSWI-FA, the
intensities of this mineral reduce. However, the rise of Ms augments the amount of reactive
silicate species which promotes the precipitation of C-S-H phases.
58
Figure 23. FTIR spectra of VA and VA-MSWI-FA based alkali-activated cements obtained
at 27 oC with different values of silica modulus (Ms)
Figure 24. XRD diffractogram of VA and VA-MSWI-FA based alkali-activated cements

obtained at 27 oC with different values of silica modulus (Ms)
59
III.4.1.4. Compressive strength, water absorption, bulk density and apparent
porosity analyses
The results of compressive strength, water absorption, apparent porosity and bulk
density of the alkali-activated cements are summarized in Figure 25 and Table 6,
respectively. The compressive strength increases with the rise of MSWI-FA up to 10% of
MSWI-FA. The apparent porosity increases with an increase in MSWI-FA while the bulk
density drops (Table 3). The behaviour of the compressive strength contrasts with the
increase of the water absorption. This can be explained with significant change in the phase
evolution. In fact, the alkaline activated with VA is essentially made with N-A-S-H, having
low porosity compared to GP10 where an important fraction of C-(N-A-)S-H is present the
matrix with the residue of CO2 or metallic ions [107]. This can also be justified by the
difference of B.E.T surface area of MSWI-FA (7.4 m2/g) and VA (3.6 m2/g). In this interval,
there was no significant change of the bulk density particularly when the Ms 1.2 were used.
In fact, the silica modulus of 1.2 increases the content of soluble and reactive silica into the
matrix improving therefore the polycondensation. The low silica modulus promotes the
dissolution of glassy phase in the precursor, but inhibits the precipitation reaction which is
responsible for the formation of the different gels that give strength to the material [74,97].
Na2SiO3 favours the polymerization process leading to a reaction product with more Si and
higher mechanical strength [18]. However, depending on the precursors, the surplus Na2SiO3
contributes to the decrease in compressive strength since excessive alkali content retards the
alkalinisation reaction [101,108]. Above 10% of MSWI-FA, the compressive strength drops
from ⁓20 MPa to 11 MPa. It is observed that the silica modulus does not affect the
compressive strength in this range of formulation. The water absorption remains high 32.15%
(GP20) and the bulk density drops to 1.56 g/cm2 when 20% of MSWI-FA is applied.
Considering the chemical composition of the MSWI-FA, it appears that, the substitution of
VA by MSWI-FA leads to significant reduction of the SiO2 and Al2O3 with an increase of
CaO. This means a change in the total amount of SiO2 + Al2O3 affects the alkaline activated
matrix which needs to be near 80 wt% for a good alkaline activated matrix while in the
volcanic ash is only ⁓60 wt%. Further reduction of SiO2 + Al2O3 in the case of GP20 affects
negatively the compressive strength.
60
Figure 25. Compressive strength of the alkali-activated cements cured at room temperature
during 28 days.
Table 6. Water absorption, apparent porosity and bulk density analyses of the alkali-activated
cements based VA and VA+MSWI-FA cured at room temperature during 28 days
Samples Water absorption Apparent porosity Bulk density

(%) (%) (g/cm3)
GP5(1.0) 12.66 22.16 1.77
GP10(1.0) 15.49 25.99 1.68
GP15(1.0) 17.46 28.35 1.58
GP20(1.0) 19.21 30.03 1.57
GP5(1.2) 11.68 20.16 1.78
GP10(1.2) 14.57 24.45 1.69
GP15(1.2) 17.75 28.54 1.59
GP20(1.2) 19.09 29.31 1.63
GP5(1.4) 12.02 21.76 1.79
GP10(1.4) 15.36 25.86 1.69
GP15(1.4) 18.91 28.28 1.59
GP20(1.4) 20.34 32.15 1.56
III.4.1.5. Microstructure
The microstructural features of the VA and VA-MSWI-FA alkaline activated cements

are presented in Figures 26 and 27, respectively. In the micrographs of Figure 26, it can be
observed that typical volcanic ash based alkaline activated cement (Figure 26 (a)) is a matrix
61
with apparent densification but with high volume of microcracks. These microcracks are due
to the poor level of polymerization/polycondensation due to poor dissolution of VA particles.
This explains the relative low compressive alkaline activated based VA compared to matrices
with MSWI-FA (Figure 26 (b) and (c)). When the MSWI-FA is present, it is observed that,
there is an improvement of particle packing with significant reduction of the micro cracks,
particularly for the formulations with 5 and 10 wt% of MSWI-FA. Although a few large
capillary pores do appear, the mechanical properties improved and the density remained
constant (Table 7). Microstructural features agreed with the phase evolution. The detailed
investigations of the micrographs demonstrate that up to 10 wt% of MSWI-FA there is a
good integration of the MSWI-FA into the matrix of VA based alkaline activated composites.
This is confirmed with the formation of complex mix of N-A-S-H and C-(N-A)-S-H. At high
magnification (Figure 27) there is a good level of homogeneity of the matrices of GP0 with
alkaline activated phases that cover the particles of quartz and other crystalline phases. Once
again the relative low mechanical strength of GP0 is from the poor reactivity that reduces the
bond strength.
Considering the variation of the density, water absorption and porosity, the typical
microstructure of high strength MSWI-FA and VA based alkaline activated cement is a
combination of C-(N-A)-S-H inserted into the N-A-S-H gels that constitute a binder
combining grains particles (Figure 28). The thermal history of MSWI-FA with residues of
metallic particles and gas explains some exothermic reactions that accompany the formation
of the complex gel made from N-A-S-H and C-(N-A)-S-H and are responsible for the larger
capillary pores dispersed into the microstructure.
62
Figure 26. Low magnification microstructures features of VA and VA-MSWI-FA based
alkaline activated at high magnification: (a) GP0(1.2); (b) GP10(1.2); (c) GP20(1.2).
63
(c)
Figure 27. High magnification microstructures features of VA and VA-MSWI-FA based

alkaline activated at high magnification: (a) GP0(1.2); (b) GP10(1.2); (c) GP20(1.2)
64
Figure 28. Microstructures features of VA-MSWI-FA based alkaline activated with 10%wt
of MSWI-FA at Ms=1.2
III.4.1.6. Thermal analysis of binders
DTG curves illustrate on Figure 29 (a) show two significant peaks and in 27-200oC (I)
and 600-800oC (II) ranges respectively. The peak (I) characterises the first mass loss. This
transformation is caused by the losses of physical adsorbed water inside the AA matrix, in
AA and C-S-H structures [81,105]. The weight losses in this range increase with the addition
of MSWI-FA and no significant change with the variation of alkali activator modulus. In fact
the addition of MSWI-FA increases the amount of reactive Ca and silicate, which lead to the
formation of C-S-H, AA gel and the modified AA gel (N-(C)-A-H. The high mass loss in
GP20(Y) may also be attributed to the prominence of the pore which increases the water in
the AA. The second peak (II) in 600-800oC is attributed to the alteration of silicate structure
and the carbonation of calcite [16]. The percentage of weight loss as a function of
temperature and the value of weight loss in different ranges of temperature are shown in
Figure 29 (b) and Table 7. The weights losses in this range rise with the addition of MSWI-
65
FA and decrease with an increase in the alkaline activator ratio. Indeed the alkalinisation of
MSWI-FA leads to the formation of calcite and the increase of Ms promotes the silicate
phases. The total mass loss in this two aforementioned ranges is small than the total mass loss
in 27-800oC. This shows that the mass loss in some transformations happened in 200-600 oC
range despite the presence of prominent peak in this range. This mass is assigned to the
ongoing dehydratation of the reaction products because water in different bonding status in
gels structure has different bonding energy and it discharges at different temperatures, thus
resulting in the continuous cascade form of the mass loss. GP10 (1.2) has the highest mass
loss in this range which can be attributed to high formation of AA and C-S-H gels.
(a)
66
(b)
Figure 29. DTG/TG curves of alkaline activated cement cured at room temperature during
28 days. (a) DTG curves and (b) TG curves
Table 7. Mass loss of alkaline activated cement pastes occurring at different temperature
ranges during heating
Temperature zone GP10(1.0) GP20(1.0) GP10(1.2) GP20(1.2) GP10(1.4) GP20(1.4)

27-200oC 4.51 5.51 4.56 5.65 4.47 5.65
200-600oC 2.57 3.25 4.17 3.34 2.47 3.35
600-800oC 1.05 1.52 0.72 1.1 0.53 1.3
Total weight loss 8.13 10.28 8.01 10.09 7.47 10.30
III.3.2.7. Toxicity
The result of leaching test of selected AAC cured at room temperature for 28 days are
presented in Table 8. The amount of heavy metal leach after digestion is less than the limit
values fixed by USEPA. This shows that all the samples are suitable for the environment. The
low value of leaching in AAC without MSWI-FA could be related to the low values of heavy
metal in VA. It is also observed that, when toxic waste (MSWI-FA) is added, the leaching of
heavy metals is still low. This fact confirmed the potential of AAM to encapsulate heavy
metals. The immobilization is also prominent in these matrices, due to the presence of iron in
VA which participates on alkalinization to form amorphous zeolite (polyferosialate). This
67
corroborates with the literature which shows that the impregnation of zeolite or charcoal
improves the absorption of heavy metals [109].

activated and landfill limit of leach metal
Samples GP0 GP5 GP10 GP20 GP5 GP10 GP20 GP5 GP10 GP20 USEPA
(1.0) (1.0) (1.0) (1.0) (1.2) (1.2) (1.2) (1.4) (1.4) (1.4) limit
Pb NF NF 0.145 0.180 NF 0.170 0.020 NF 0.24 0.184 5.000
Cr NF 0.040 0.030 0.030 0.050 0.038 0.025 0.040 0.400 0.029 5.000
Cd NF NF 0.007 NF NF NF NF NF NF 0.013 1.000
Zn 0.100 0.110 0.086 NF 0.180 0.046 0.074 0.130 0.223 0.180 100.000
Cu 0.090 0.080 0.107 0.115 0.110 0.144 0.108 0.090 0.184 0.168 5.000
Ba 0.150 0.070 0.033 0.034 0.130 0.034 0.033 0.070 0.143 0.064 100.000
III.3.2.8. Conclusion
In this part, municipal solid waste incinerator fly ash (MSWI-FA) was used as
precursor to improve the reactivity of volcanic ash (VA) for alkali-activated cement
synthesised. The effects of various proportions of MSWI-FA (0, 5, 10, 15 and 20%) on the
final properties of the inorganic polymer cement are reported. This part has proven that the
MSWI-FA can be used to improve the reactivity and mechanical properties of raw volcanic
ash for the synthesis of alkali-activated cement. However, the amount of MSWI-FA added
should be controlled together with modulus of alkaline activator solution. The study on the
effects of incorporation of 0, 5, 10, 15 and 20% of MSWI-FA by mass and the silica modulus
(SiO2/Na2O molar ratio) 1.0, 1.2 and 1.4 were the sustenance of the work. The different
analyses carried out revealed that:
 The low shift of Si-O-T bonds in VA-MSWI-FA system compared to VA system and
the emergence of new peak in XRD pattern of alkali-activated sample based VA-
MSWI-FA system showed the formation of new crystalline phases namely:Margarite,
CaAl2 (Al2Si2)O10(OH)2, PDF#04-013-3004), Mordernite-(Ca) (Ca, Na2 ,K2) (Al2 Si10
O24) .7H2O, PDF#00-011-0155), PDF#00-011-0155) and Thernadite (Na2SO4, PDF #
01-074-2036)
 They exhibited the coexistence of C-S(-N-A)-H and N-A-S-H gels in binary system of
alkali-activated cement.
68
 The alkali-activated cements synthesised by adding 10%MSWI-FA with Ms=1.2
exhibited the best mechanical properties (21.07 MPa).
These results indicated the possibility to use VA and MSWI-FA to synthesize room
temperature alkali-activated matrices applicable in the manufacture of structural and
functional materials. MSWI-FA appears energy-efficient and a sustainable solution for the
improvement of the volcanic ash based alkaline activated materials.
III.4.2. Incorporation of VA in binder based MSWI-FA
Notice that the municipal solid waste incinerator fly ash (MSWI-FA) is one of the
potential materials for alkaline activated synthesis due to its pozzolanic nature. However the
percentage of alkaline activated ingredients (Al, Si) in this hazardous waste is less to produce
construction material. The novelty of this part is to use volcanic ash, for the first time to
supplement the Al and Si deficiency in MSWI-FA in order to promote alkali activation and
enhance the stability of heavy metal content in MSWI-FA. The effects of concentration of the
activating solution on the microstructure and properties of MSWI-FA based alkaline
activated system is also reported, so that suitable applications should be envisaged. The work
promotes utilization of blends of volcanic ash and MSWI fly ash for eco-cement production.
III.4.2.1. Phases evolution (XRD and FTIR)
Relative to the X-ray patterns of the raw MSWI-FA (Figure 30), prominent
differences are evident. The glassy hump centred at around 2ϴ= 34o in MSWI-FA shifted to
around 2ϴ = 29o, which denotes the structural changes occurring during the reaction with
concomitant formation of new crystalline phases [21]. The amorphous hump shift was also
reported by Kumar et al [77]. They observed that the shift is associated with change in Si/Al
and Na/Al ratio. It is noteworthy that after the reaction, the peaks (2ϴ = 31.3, 22.8, 29.5o)
corresponding to calcium sulphate phases, namely gypsum, anhydrite and basanite,
previously present in MSWI-FA were significantly diminished. The reaction of calcium
sulphate phases in alkaline medium promoted the formation of a crystalline phase namely
Thernadite (Na2SO4PDF#02-0805) as per equation 1.
𝑪𝒂𝑺𝑶4. 𝟐𝑯2𝑶 + 𝟐𝑵𝒂𝑶𝑯 ⟶ 𝑪𝒂(𝑶𝑯)2 + 𝑵𝒂2𝑺𝑶4 + 𝟐𝑯2𝑶 (𝟏)
There is also the formation of new minerals such as hydrocalumite (PDF# 31-0245
Ca4Al2O6(CO3)0.67(SO3)0.33), calcium silicate hydrate (C-S-H) (PDF# 31-0301) and faujasite-
69
Na (Na2Ca)0.075(Al0.3Si0.7)O2(H2O)0.22, PDF# 76-0843). Faujasite-Na belongs to zeolite group
and was also observed earlier, during alkali activation of volcanic ash with calcium source by
hydrothermal treatment (60 and 80 oC) [16]. In this study, zeolitic phases were obtained at
room temperature due to the rapid dissolution of glassy MSWI-FA which promoted the
formation of crystalline and amorphous alumina-silicates phase [110]. The peak intensity and
width of calcium silicate hydrate and thernadite at 2ϴ = 30o varied inversely and directly with
increase in alkalinity, respectively. This is due to the fact that low alkalinity promote the C-S-
H phase [111] and the high alkalinity promotes poorly crystalline C-(A)-S-H phase owing to
the prominence of substitution of Si in C-S-H phase by Al and N-A-S-H phases [112]. The
decrease of peak at 2ϴ = 30o with the increase in VA content is attributed to the co-existence
of C-S-H and N-A-S-H phases resulting from increase of Si/Al ratio. The formation of such
crystalline phases could also be justified by a change in the degree of crystallinity after
alkalinisation. The intensity of the calcite peak increased with an increase in the
–
concentration of alkali. Obviously, the presence of high amount of OH promoted the
formation of calcium hydroxide which underwent the carbonation reaction as depicted by
equation 2 [113]. Moreover, due to the high content in Na+ ion formation of sodium
carbonate is generally expected and observed in alkali-activated cement and alkaline
activateds [111]. However, sodium carbonate revealed very low intensities, this can be
attributed to the precautions taken to limit the carbonation of sodium after hardening.
𝑪𝒂(𝑶𝑯)2 + 𝑪𝑶𝟐 ⟶ 𝑪𝒂𝑪𝑶𝟐 + 𝑯𝟐 𝑶 (𝟐)
The bands located at 951-968 cm-1 range are assigned to the Si-O-T (T=Al, Si)
asymmetric stretching vibrations characteristic of aluminosilicates and calcium silicate
hydrate phases (Figure 31) [98,114]. The left shoulder of this band is attributed to asymmetric
stretching of T–O bonds originating from individual tetrahedral [115] suggesting the presence
of zeolite phase [116]. The presence of zeolitic phase is hitherto confirmed by the XRD
analysis. The series of bands in the 450–650 cm-1 range is assigned to Si–O–T deformation
vibrations [78,117]. The peaks at around 1420 cm-1 and the one at 872 cm-1 attributed to
carbonate bond from calcite or Na2CO3 [117]. The bands at 3477-3466 cm-1 and 1645-1648
cm-1 range are attributed to the stretching vibration and deformation of O-H bonds and H-O-
H, respectively. The wave number of these characteristic bands are indicated in Table 9.
Comparing these values to the same characteristic bands of MSWI-FA several changes are
observed. The first is a shift of Si-O-T vibrational and deformation bands to high and low
values, respectively. This is due to change in the microstructure during alkaline activation
70
reaction [118]. The vibrational wave numbers not only increase after alkaline activation of
MSWI-FA but also are observed to decrease with rise in alkalinity. This phenomenon has
been previously reported during alkaline activation of calcium-silica rich systems
[18,104,119]. Low concentration of alkali and high content of reactive calcium favour the
formation of C-S-H phase. On the contrary, high alkali concentration is detrimental for C-S-
H formation due to the precipitation of Ca(OH)2. The shift of Si-O-T bands is more
pronounced in the alkali-activated MSWI-FA-VA system than in those without VA, implying
the extent of reaction is higher in the former than in the latter. The incorporation of VA
promotes the substitution of silicate in this gel by Al to form the C-S (A)-H gel and growth of
aluminosilicate phases via dissolution of VA’s glassy phase. GP50(6) revealed the highest
shift in wave number possibly due to the coexistence of C-S-H gel and alkaline activated in
this system after equilibration of the alkalinisation and geopolymerization reactions. This is
in agreement with the results by Yip et al [98] which demonstrated that the coexistence of
these two gels occurs only in a system which contains sufficient amount of calcium source
(20 wt%) at low alkalinity (NaOH˂7.5M). The wave number of band C-O also increases in
the alkali-activated cement relative to MWSI-FA consistent with formation of calcite in high
alkalinity medium. Higher wave numbers denote higher force constant which means greater
bond strength in VA-impregnated alkaline activated.
Figure 30. X-ray diffractogram of alkali-activated cement without VA and alkali-activated

cement with VA.
71
Figure 31. FTIR spectra for the alkali-activated cement without volcanic ash and alkali-
activated cement based MSWI-FA +VA system
Table 9. IR Characteristic bands of alkali-activated MSWI-FA and MSWI-FA-VA
Bonds ‫ע‬Si-O-T δSi-O-T ‫ע‬T-O(TO4); ‫ע‬C-O ‫(ע‬O-H; H-O-H)

(cm-1) (cm-1) (cm-1) (cm-1) (cm-1)
MSWI-FA 876 567 1164 1639 1462; (3753-2946)
VA 1026 568 - 1643 1481(3691-3051)
GP0(6) 970 463 1118 1646 1444; (3682-3278)
GP0(8) 968 474 1128 1656 1452; (3662-3294)
GP0(10) 960 472 1130 1656 1444; (3699-3232)
GP30(6) 978 484 1146 1641 1473; (3662-3290)
GP30(10) 970 451 1142 1640 1440; (3695-3147)
GP50(6) 1003 465 1149 1648 1467(3696-3201)
GP50(10) 978 457 1151 1658 1458; (3672-3277)
III.4.2.2. Thermal analysis of cement pastes
The results of the thermogravimetric tests obtained at a temperature rate of 5oC/min

are summarized in Figure 32 (a). The TGA curves show that all the sample present a mass
72
loss. The weight losses decrease with the incorporation of VA and the increase of
concentration of alkaline solution. This show that the incorporation of VA improved the
thermal stability of MSWI-FA based AA. On the DTG curves (Figure 32 (b)) three rapid
weight losses occur. The first weight loss, located between 100 and 200oC, is the result of the
evaporation of moisture and free water present in pores of AA gels, dehydration reactions of
several hydrates observed on XRD and SEM analyses. The second major weight loss,
observed at 350–500oC, corresponds to the dehydroxylation of portlandite, another hydration
product. The third weight loss appears at 550- 750oC and corresponds to the decarbonation of
calcium carbonate, NaCl and organic compounds. The results display that alkaline activated
with VA resist better towards the fire and elevated temperature than alkaline activated
without VA. Thus its advantageous to use VA like supplementary material.
73
Figure 32. TGA-DTG curves of cements without VA and alkali-activated cement based
MSWI-FA +VA system. (a) TG curves and (b) DTA curves
III.4.2.3. Microstructure characterization
The microstructure of samples GPX(6) and GPX(10) are presented in Figure 33. The
densification of the microstructure increase with the incorporation of VA (spots (a) and (b))
and the prominence of cracks increases with the concentration of activator solution [95]. In
the view of micrographs (c), the cracks are prominent in GP(10), this fact is due to the
migration of free Na+, and K+ ions outside the alkaline activated and can also be attributed to
the negative effect of some crystalline compounds . The second group (d and e) exhibits the
different gels formed during reaction. These features were found in all the samples used for
microstructural analyses. The micrograph (d) presents the C-S-H gel. The addition of VA and
the concentration of alkali medium lead to the modification of this gel. The ratio of
(Ca+Mg)/Si, (Na+K)/Si and Si/Al calculated for all the samples via EDS result, range
between 0.47-6.09, 0.644-1.16 and 8.26-3 respectively. The morphology of micrographs (f)
presented the N-A-S-H gel which is more dense in alkali-activated cement with high amount
of VA and high concentration of alkali solution (GP50(10)). The ratio of (Ca+Mg)/Si,
74
(Na+K)/Si and Si/Al ranges from 0.33-1.14 ((Ca+Mg)/Si), 0.64-3.15((Na+K)/Si) and 2.34-
2.61 (Si/Al). The last group represents the crystalline phases and the unreacted particles
found. From these spots, the crystalline phases and unreacted particles are embedded in the
different gels. The microstructure and EDS analysis reveals the presence of C-S-H, halite and
Faujasite-Na corroborating the XRD results. C-S-H results from the precipitation of Ca2+ and
silicate ions. The EDS patterns reveals a 0.65 Ca/Si ratio for C-S-H. This value is slightly
lower than that of natural C-S-H (0.67-1.5) possibly due to the substitution of some Si by Al
to form Al-C-S-H. This imbues the material with better heavy metal encapsulation capacity.
Halite was prominent in alkaline activated synthesized with 10 M as shown in Figure 33 (i).
This can be explain by the increase of free sodium ion which lead to the precipitation with
choride ion available in the system. Zeolite is fractured Figure 33 (e).
The Si/Al molar ratio of zeolite in the different alkaline activated samples is 5. This
classifies the zeolite as ‘intermediate zeolite silica’. According to this classification the
mineral name and their framework codes is Na-Y faujasite which correlates with the XRD
and FTIR results [120,121] . The EDS analysis of the different phases formed after reaction,
highlight that their respective compositions are constantly modified according to the
composition and the alkaline medium of the synthesis. In this study, (M(II),M(I))-(A)-S-H
and (M(I), M(II))-A-S-H was formed resulting from the C-S-H and N-A-S-H respectively
which M(II)=Ca, Mg and (M(I)=Na, K. The heterogeneityof gel is due to the high reactivity
of its ingredients gel [122].
75
Figure 33. FEG-SEM/EDS analysis of GPX (6) and GPX (10).
II.4.2.3. Mechanical and Physical properties
III.4.2.3.1. Compressive strength
The compressive strength of alkaline activated samples are depicted on Figure 34. In
general, the compressive strength was lower than the many reported values because: (a)
25mm size samples were used for testing, and (b) the test was conducted on hardened paste
samples. Note that the compressive strength decreases with an increase in alkali and is
directly proportional to the VA content. The percentages of strength gained for alkaline
76
activateds synthesised at 6M from 14 days to 28 days are 13.04% GP0 (6), 52.83% GP 30(6)
and 45.83% GP 50(6). These percentages decrease with the raise of concentration.
Considering the VA content, the concentration of alkaline solution and 28 days compressive
strengths, the optimal addition dosage of MSWI-FA is 50 wt% at 6M (10.5 MPa). This
behaviour is due to the fact that, the high alkalinity (10M) promotes not only the dissolution
of glassy phases in precursor, but also inhibits the reaction of precipitation which is
responsible for the formation of different gels responsible for the material’s strength [97].
The high alkalinity of activator solution also promotes the excess of alkali ions. The excess of
alkali causes the diffusion of the alkali ions out of the matrix, which increases the formation
of crack throughout the structure [123] with concomitant precipitation of halite with low
mechanic properties. At 6M concentration, the quantity of OH- is sufficient to simultaneously
generate the precipitation of the C-S-H and alkalinisation gels without a remarkable free
alkali. The coexistence of these two phases is beneficial for the strength. The substitution of
MSWI-FA by VA densifies the structure, introduces supplementary Si4+, Al3+ ions thus leads
to the formation of the aluminosilicates phases and enhances modification of C-S-H which
increases the strength [124].
77
Figure 34. Compressive strength of alkaline activated samples cured at 14 days (a) and 28
days (b)
III.4.2.3.2. Water absorption, apparent porosity and bulk density
The water absorption (WA), apparent porosity (AP) and bulk density (BD) of alkaline
activated with and without VA at different concentrations of alkaline solution are displayed
on Figure 35. The results show that the incorparition of VA really affected the physical
properties of alkaline activated. The values of water absorption and apparent porosity dimish
with the VA incorporation and increase with the alkalinity of activator solution. Apart from
the porous nature of the raw materials, the presence of unreactive species in these materials,
the type of gels formed (densified and porous gels), the expulsion of waters that have not
participated in alkalinization is also responsible for the water absorption and porosity of the
alkaline activated material. During this expulsion, voids are created. This justifies the high
water absorption and apparent porosity of alkaline activateds synthesised at 6M compared to
10M. The results also show that VA emerge the densified gel than MSWI-FA. According to
ASTMC216, the water absorption values of construction materials must be less than 15%.
Only GP50 (X) have the values close to this threshold. The absence of water absorption value
78
and the apparent porosity of GP0 (10) is because after drying these samples in order to obtain
a constant mass before immersion in water, the alkaline activated showed cracks and once
immersed in the water it became crumbled. This corroborates with the above microstructural
analysis, which showed the prominence of high alkalinity cracks. Bulk density increases
slightly with the incorporation of VA. But these values are in the inversion of light weigtht
materials, so broadens the scope of application of these materials.
Figure 35. Water absorption (WA), apparent porosity (AP) and bulk density (BD) of alkaline
activated with and without VA at different concentrations of alkaline solution; (a) Water
absorption; (b) apparent porosity; (c) bulk density
II.4.2.4. Toxicity
The leaching concentration (mg·L-1) of MSWI-FA, MSWI-FA-VA based alkaline

activated and landfill limit of leach metal are shown in Table 10. The leaching metals of the
alkaline activated samples were far much lower than the maximum concentration of each
contaminant stipulated by USEPA for toxicity characteristics. This confirms the efficiency of
79
the developed alkaline activated material to stabilize heavy metals. The concentration of Cd
released was less than the instrumental detection limit for all alkaline activated samples. This
depicts high stabilisation of Cd after alkalinization due to the very low solubility of Cd(OH)2
and is in agreement with previous reports [19,51,125]. Noteworthy, the encapsulation
phenomenon was most prominent in alkaline activated synthesized at 6M medium. It is
conceivable that the reduced leachability in alkaline activated samples prepared in 6M media
was due to emergence of in situ absorbents such as zeolite, Al-C-S-H, AFm, C-S-H gel and
alkaline activated gel.

activated, landfill limit and percentage of leach metal.
Heavy Pb Cr Hg Zn Ba Se Ag Cd
metals
MSWI-FA 23.84 12.50 18.50 12.07 9.22 6.18 6.00 15.00
GP0(6) 7.5072 4.3701 6.521 7.0852 3.0814 2.1453 1.3 3.200
GP30(6) 0.0074 0.0651 0.00218 0.0962 0.042 0.197 ND ND
GP50(6) 0.00133 0.0146 ND 0.0602 0.0334 0.1471 ND ND
GP0(10) 9.530 6.2268 7.320 7.478 4.616 3.2449 1.990 4.023
GP30(10) 0.124 0.2268 ND 0.1458 0.0353 0.2427 ND ND
GP50(10) 0.113 0.2045 ND 0.1105 0.0281 0.2121 ND ND
USEPA 5.0 5.0 5.0 100.00 100 1.0 5.0 1.0
limit
III.4.2.5. Conclusion
This part involved the addition of VA for the first time to compensate the low alumina
and silica content in MSWI-FA in order to synthesize eco-friendly cement (alkali-activated),
thus contributing to the recycling via stabilization/solidification of this toxic waste. Studies of
the incorporation of VA and the alkalinity of the activating solution were the varying
parameters. The following conclusions can be drawn from the study:
 The incorporation of VA reduces the Liquid/Solid (L/S) ratio required to obtain a

good workability of cement paste from 0.75 for MSWI-FA system to 0.5 for MSWI-
FA-50% VA system. It also enhances the coexistence of AA gel and C-S-H gel in the
matrix, thus improving the mechanical properties and encapsulation efficiency of the
heavy metals present in MSWI-FA.
80
 A high alkalinity of the activating solution (10 M, Ms=0.36) reduces the mechanical
properties of the cement obtained and the low alkalinity (6M, Ms=0.66) led to the best
mechanical property (10.5 MPa for the 50% MSWI-FA-50%VA system).
 Due to the moderated mechanical properties of the products obtained, this alkaline
activated cement based on the MSWI-FA-VA system can be used in the manufacture
of non-structural materials such as bricks and paving blocks, after studying the
durability of cement.
This part thus shows the possibility of using VA as an adjuvant to MSWI-FA based
alkali-activated cement in the same way as calcined clays, fly ash, slag, red mud etc.
III.5. Durability of alkali activated mortars

Volcanic ash and MSWI-FA can be used in synergy for alkali activated cement
synthesis. However the durability test is primordial to know in which media this cement can
be used. This part gives rise to the study of the mortars from the best formulation of the
above part of synthesis of alkaline activated material in aggressive media. The effect of these
aggressive media on the physical, structural, mechanical and microstructural of alkali
activated mortars will be discussed. This part will also point the differences between acid
attack and sea water attack on the aforementioned properties.
III.5.1. Visual inspection
The appearance of mortar specimens exposed in 2 and 4% sulphuric acid and sea
water after 56 days are depicted on Figure 36. The samples exposed in sea water do not show
any significant degradation. However the white layer is formed on its surfaces. This displays
that the aggression is only structural. The degradation is prominent in sulphuric acid. The
degradation is more significant on GP50 (6) than GP10 (1.2). This shows that the binder is
stronger in GP10 (1.2) than GP50 (6). The GP10 (1.2) do not show a colour change on the
surface. However, after breaking, there is internal colour change on some surfaces, which
shows the corrosive aspect of sulphuric acid. The change in colour was not observed in
internal layer of mortars immersed in sea water. After 56 days of samples immersed in sea
water they became broken (Figure 37). In the view of this results, GP10 (1.2) and GP50 (6)
could be considered as suitable candidate as resistant mortars in sea water and only GP10
(1.2) as suitable resistant mortars in sulphuric acid (less than 5%) to be used in civil structure.
81
Figure 36. Appearance of mortars specimens exposed in 2 and 4% sulphuric acid and sea
water after 56 days
82
Figure 37. Visual aspect of broken alkaline activated mortar immersed in sulphuric acid after
56 days
III.5.2. Residual compressive strength and weight loss evolution of alkaline

activated mortar after exposure to aggressive media
III.5.2.1. Weight loss evolution
The percentage of weight loss with exposure time in aggressive medium is shown in
Figure 38. The mass change was calculated according to ASTM C267. The GP10 (1.2)
mortars in aggressive media have low mass loss, less than 6%. The mass loss in sea water is
very low (less than 2%). The GP50 (6) mortar, on the contrary, experienced significant
deterioration, losing up to 8% in sulphuric acid, but still less in sea water medium. This
observation substantiates with the visual inspection, which showed that sea water is less
corrosive than sulphuric acid. However this will not avoid the possibility of sea water to
affect the structure of alkaline activated. The mass loss in acid could be attributed to the
physical deterioration and the probable exchange of cations (Na, K) in polymers by hydrogen
or hydronium ions. Concerning the mass loss in sea water, this is due to the leaching of
alkaline ion, chlorine and the unreacted particles which are not embedded in alkaline
activated system.
83
(((b)
Figure 38. Percentage of weight loss of alkali activated mortars immersed in aggressive
media: (a) GP10 (1.2) mortars; (b) GP50 (6) mortars
III.5.2.2. Residual compressive strength
The compressive strengths of GP10 (1.2) and GP50 (6) mortars as a function of
exposure time in aggressive media are represented on Figure 39. The decrease after 56 days
for GP10 (1.2) was 9.10%, 22.08%, 32.5% and for GP50 (6) 12.6 %, 47.94%, 76.71% in sea
84
water, 2% H2SO4, 4% H2SO4; respectively. The drop is observed in both acidic environments
and seawater. Once the sample is in acid, its infiltration causes attack breakage of the Si–O–
Al bonds, increased number of Si–OH and Al–OH groups in AAs (depolymerization) and an
increased amount of silicic acid ions and dimers in solution. Therefore, this process affects
the strength of the AAM. This depolymerization increases over time, because the longer the
sample remains in acid, the more its penetration improves. Acid also contributes to the
disintegration of the C-S-H gel. In fact this phase reacts with sulphate ions in the presence of
Ca(OH)2 to form ignite and gypsum, which in turn cause expansion and degradation of the
cement into a non-cohesive granular mass [126]. This justifies the emergency of mechanical
property’s loss of GP50 which contains more C-S-H gel. The loss of mechanical property by
samples immersed in seawater is not predominantly due to depolymerization, but rather to
saturation of alkaline and chloride ions. Once seawater infiltrates in AAM; the high
popularity of alkaline ions, chloride and sulphate is achieved. The mobility of these chemical
species cause cracks between gels and pores. The immersion of seawater also slightly affects
internal porosity because of Na ions being replaced by Mg ions in the gel microstructure, thus
resulting in highlighted loss of mass and a decline in mechanical strength. We can resume
that when the samples are immersed in sea water three effects are produced: (i) the diffusion
of alkaline ions and chlorine into the matrix until saturation, (i) the leaching of these species
out of the alkaline activated matrix and (iii) the exchanging of Na ions by Mg ions in the gel
microstructure. These losses could also be justified by the formation of new minerals which
have a low mechanical property. The names of these minerals will be checked on XRD
analyses. The decrease in seawater is higher in GP50 (6) than in AAC GP50 (1.2), this is
attributed to a high percentage of chloride in MSWI-FA.
85
(a)
(b)
Figure 39. Compressive strength change of alkali activated mortars immersed in aggressive
media: (a) GP10(1.2) mortars; (b) GP50(6) mortars.
86
III.5.3. Structuring and microstructuring of alkaline activated mortar before
and after exposure to aggressive media
III.5.3.1. FTIR analysis
The FTIR spectra of alkali activated mortars (GP50 (6) (1) and GP10 (1.2) (2))
before and after immersion in aggressive media for 56 days are denoted on Figure 40. The
spectrum of alkali activated mortars present the band of H-O- bonds at ̴ 3500 and 1450 cm-1,
band of carbonate at ̴ 1650 cm-1 and the principal bands of aluminosilicates (Si-O-T) at ̴1000
and 500 cm-1. In the view of these spectra, the samples immersed in sea water present all
these aforementioned bands practically at the same position. Though, the samples immersed
in acid media present relevant differences: (i) the band at ̴ 1450 cm-1 disappears, (ii) The Si-
O-T bonds shift to high values and the intensity increases with the increase of the percentage
of acid and (iii) the Si-O-T becomes narrow. In fact the band at ̴ 1450 cm-1 mainly
characterize the structural link O-H, previously mentioned (section 3.2.2) that the infiltration
of acid in alkali activated matrix causes the breakage of the Si–O–Al bonds to form Si–OH
and Al–OH. In these species the –O-H bond is not strongly linked, this justifies the quasi-
disappearing of band at ̴ 1450 cm-1. The shift of Si-O-T and the reduction of broad implement
this prominent deopolymerization in acid medium and the depolymerisation emerges with the
rise of percentage of acid. This depolymerisation is due to the rupture of aluminosilicate
bonds accompanied to the substitution of Al by H+. The figure 40 illustrates this undesired
phenomenon. The residues of this depolymerisation could be lead to the formation of new
minerals which will be found in XRD section.
Figure 40. Illustration of depolymerisation of geopolymer gel in acid medium
87
Figure 41. FTIR spectra of alkaline activated mortars before and after immersion in
aggressive media for 56 days: (a) GP10 (1.2) mortars; (b) GP50 (6) mortars.
88
III.5.3.2. XRD
The diffractogram of alkaline activated mortars before and after immersion in

aggressive media for 56 days are represented on Figure 41 (a) and (b) below. No prominent
differences are observed when the diffractogram of mortars and mortars immersed in sea
water are compared. This fact implements the absence of modification of alkali activated
structure in sea water mentioned in above sections. Yet, the prominent differences are
observed between the alkaline activated mortars and the alkaline activateds immersed in acid
media. This is mainly the formation of new peaks at ̴14.5, 49 and 55o and the increase of the
intensity of the peaks at̴ 22.14, 30 and 31.7°. These facts characterize the formation of new
phases namely calcium sulphate Hydrate at 49, 30, 31 and 14.5°, Sodium Aluminium
Hydride at 55 and 36° and Hydrogen Silicate at 25.5 and 22.8°. The last two minerals are the
products of aforementioned depolymerisation. The first mineral resulted from the
precipitation of calcium (free calcium in the matrix and the calcium leach after acid attack)
and the sulphate from acid. The formations of these minerals explain the loss of strength after
the immersion in acid. So far, the different results do not really show the effect of acid attack
on the structure of alkaline activator mortars. This fact could be revealed by the
microstructural analysis.
89
Figure 42. XRD diffractograms of alkali activated mortars before and after immersion in
aggressive media for 56 days: (a) GP10 (1.2) mortars; (b) GP50 (6) mortars
90
III.5.3.2. Microstructure analysis
The microstructure feature of alkali activated mortars before and after immersion in
aggressive media for 56 days are depicted on Figures 42 to 43. It is seen that the alkali
activated mortars present dense structure with coexistence of alkaline activated gel and C-(N-
A-)S-H gel. The samples immersed in sea water present the cracks on its feature and the
samples immersed in sea water presented the formation of new phases and the intermittence
of gels. These facts show that the sea water improves the cracks in the matrix of alkali-
activated mortar and the acid destroys the alkaline activated matrix. In the view of the
composition of sea water there are prominence of water, alkali ions and chlorine ion, when
the sample is immersed in sea water. In fact the infiltration of sea water provides these
species throughout the matrix and the depth of infiltration improves with the time until the
equilibrium of infiltration is achieved. After the equilibrium, the matrix is saturated of these
aforementioned species. It is noticed that the alkaline activated have the potentiality to leach
these species out its matrix. This diffusion causes the formation of cavities or cracks
throughout the matrix. These cracks are responsible for the strength loss when the samples
are immersed in sea water. This crack is also observed at low scale (figure 43). Figure 42
shows that the gels are affected by the microcracks. In acid medium the destruction of the
matrix is due to the transformation of N-A-S-H gel to N-A(H)-S-H gel which leads to the
depolymerisation. XRD already announced the formation of new crystalline phases after
immersion in acid. Only the calcium sulphate was found throughout the matrix (Figure 43).
The absence of the feature can be due to the fact that the depolymerisation is a slow reaction
and the formation of the products of this reaction is not present everywhere into the matrix.
The fraction used for microstructure analysis would not contain these products whereas the
fraction used for XRD contains these products.
91
Figure 43. Microstructures features of alkali activated mortars before and after immersion in
aggressive media for 56 days: (a) alkali activated mortar; (b) mortar immersed in sea water;
(c) mortar immersed in acid
Figure 44. Microstructure feature presenting the effect of sea water on gel structure
92
Figure 45. Microstructure feature presenting the effect of acid on the structure of alkaline
activated mortars
III.5.4. Conclusion
This last part consisted to study the behaviour of alkaline activated mortars in
aggressive media, because during their life cycle, different aggressive species will attack
these materials and can affect their properties. Based on the above result, both alkali activated
materials have the potentiality to resist in sea water, whereas some modification of structure.
However the GP50 (6) presents less resistance in acid medium and the GP10 (1.2) present
appreciable behaviour in acid media. The results also reveal that the leaching of alkaline
species and chlorine can infiltrate in the matrices when the samples are immersed in
aggressive medium and are responsible to the loss of the properties of alkali activated mortars
particularly the samples immersed in sea water, although, the depolymerisation followed by
the formation of new crystalline phases are responsible for the loss of the properties of the
samples immersed in acid media. These losses are prominent when the acid is more
concentrated.
93
III.6. Development of VA+MSWI-FA matrix based alkaline activated
pavement blocks.
The paving tiles developed from VA+MSWI-FA matrices are shown in Figure 45.
The use of these paving tiles in a specific construction area depends primarily on the
compressive strength and durability in the environment in which they will be exposed. For
paving tiles made from the 50% MSWI-FA+50%VA matrix, compressive strength is around
15 MPa and they also have a low durability in the aggressive environments considered. They
can be used in an environment where they will not be subjected to the compression of heavy
objects and also where there is low humidity. As for the paving stones based on the
90%VA+10% MSWI-FA matrix, they have a compressive strength of around 25 MPa and a
good durability in the environments considered. These paving tiles can be used for road
construction in equatorial environments. However, the reinforcement of these mechanical
properties by the addition of standardized aggregates of coarse particles and the increase in
thickness are prescribed. The cost of these paving tiles per unit is affordable if the ingredients
of the activating solution, namely soda and water glass, are produced locally compared to
paving stones produced from ordinary cement.
94
(a)
Figure 46. Paving tiles developed from VA+MSWI-FA matrices (a) 50% MSWI-
FA+10%VA; (b) 90% VA+10% MSWI-FA
95
GENERAL CONCLUSION AND PERSPECTIVE
The objective of this work was to study the possibility of combining volcanic ash and
MSWI-FA for the synthesis of alkali-activated cements. The synthesis of these cements
required several steps: characterization of the raw materials, study of the workability of the
different formulations, kinetic study of the formulations, determination of some
characteristics of the synthesized products, studies on the toxicity of the cements obtained
and study of the durability of better formulations.
The characterizations of the raw materials collected in the Littoral Region of

Cameroon reveal that volcanic ashes are good prospective ingredients for the synthesis of
alkali activated materials (SiO2+Al2O3=63.1%) despite their low reactivity in alkaline
medium as revealed by the kinetic study. In contrast, MSWI-FA has a good reactivity in
alkaline medium, a high percentage of amorphous calcium (26%) but a low proportion of
SiO2 and Al2O3 (13.81%). These distinctives show that the MSWI-FA can be used as additive
to enhance the properties of alkali-activated matrices from low reactive VA and volcanic ash
can be used to supplement the alumina and silicon deficiency in MSWI-FA.
The sustenance of the volcanic ashes based cements was to study the effects of
incorporation of 0, 5, 10, 15 and 20% of MSWI-FA by mass and the silica modulus
(SiO2/Na2O molar ratio) 1.0, 1.2 and 1.4 on the properties of the cements obtained. The
different analyses carried out revealed that: (i) The low shift of Si-O-T bonds in VA-MSWI-
FA system compared to VA system and the emergence of new peak in XRD pattern of VA-
MSWI-FA based alkali-activated system attested to the formation of new crystalline phases
namely: Margarite, CaAl2 (Al2Si2)O10(OH)2, PDF#04-013-3004), Mordernite (Ca)
(Ca,Na2,K2)(Al2Si10O24).7H2O, PDF#00-011-0155), PDF#00-011-0155) and Thernadite
(Na2SO4, PDF#01-074-2036). (ii) The binary system of alkali-activated cement displayed the
coexistence of C-S (-N-A)-H and N-A-S-H gels. (iii) The alkali-activated cements
synthesized by adding 10% MSWI-FA with Ms=1.2 exhibited the best mechanical properties
(21.07 MPa). These results indicated that VA and MSWI-FA are prospective sources for the
room temperature synthesis of alkali-activated matrices applicable in the manufacture of
structural and functional materials. MSWI-FA appears to be an energy-efficient and
sustainable solution for the improvement of the volcanic ash based alkaline activated
materials.
96
The cement synthesized using MSWI-FA as feedstock focused on the study of the
incorporation of 0, 10 30 and 50%VA at different alkalinities (6, 8 and 10M) of the activating
solution. The following conclusions can be drawn from the study: (i) The incorporation of
VA reduces the liquid/solid (L/S) ratio required to obtain a good workability of cement paste
from 0.75 for MSWI-FA system to 0.5 for MSWI-FA-50% VA system. (ii) It also enhances
the coexistence of alkaline activated gel and C-S-H gel in the matrix, thus improving the
mechanical properties and encapsulation efficiency of the heavy metals present in MSWI-FA.
(iii) A high alkalinity of the activating solution (10 M, Ms=0.36) reduces the mechanical
properties of the cement obtained and the low alkalinity (6M, Ms=0.66) led to the best
mechanical property (10.5 MPa for the 50% MSWI-FA-50%VA system). Due to the
moderated mechanical properties of the products obtained, this alkaline activated cement
based on the MSWI-FA-VA system can be used in the manufacture of non-structural
materials such as bricks and paving blocks, subject to durability studies. This part thus shows
the possibility of using VA as an adjuvant to MSWI-FA based alkali-activated cement in the
same way as calcined clays, fly ash, slag, red mud etc.
The results of the study on the behaviour of alkaline activated mortars in aggressive
media disclose that both alkali activated materials have the potentiality to resist in sea water,
with concomitant modification of structure. Noteworthy, the alkaline activated sample based
on 50%MSWI-FA+50%VA presented the least resistance in acid medium while the other one
based on 90%VA+10%MSWI-FA exhibited appreciable behaviour in acid media. The results
also reveal that the leaching of alkaline species and chlorine when the samples are immersed
in aggressive medium are responsible for the loss of the compressive strength of alkali
activated mortars particularly the samples immersed in sea water. Although the
depolymerisation followed by the formation of new crystalline phases are responsible for the
loss of the properties of the samples immersed in acid media, these losses are prominent
when the acid concentration is increased. Based on these observations, the alkaline activated
material from 90%VA + 10% MSWI-FA can be used in humid environments, whereas the
alkaline activated materials from 50%MSWI-FA+50%VA should not be used in such
environments.
For future studies, we intend to improve the mechanical properties of these different
products by the incorporation of organic polymer from Hevea. The supplementary
investigations of durability such as carbonation and wet-dry cycles will be carried out to
really control the use of these green inorganic polymer materials.
97
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Annex
Publications from the dissertation
1) S. Tome, M.-A. , Etoh, J. Etame, K. Sanjay, Improved Reactivity of Volcanic Ash

using Municipal Solid Incinerator Fly Ash for Alkali-Activated Cement Synthesis,
Waste and Biomass Valorization. 0 (2019) 0. doi:10.1007/s12649-019-00604-1.
2) S. Tome, M. Etoh, J. Etame, K. Sanjay, Characterization and Leachability Behaviour

of Geopolymer Cement Synthesised from Municipal Solid Waste Incinerator Fly Ash
and Volcanic Ash Blends, Recyling. (2018). doi:10.3390/recycling3040050.
3) S. Tome, M.-A. , Etoh, J. Etame, K. Sanjay, Resistance of alkali-activated mortar

from volcanic ash + MSWI-FA matrice in sulphuric acid and artificial sea water
media (under publication)
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REPUBLIC OF CAMEROON REPUBLIQUE DU CAMEROUN

UNIVERSITY OF DOUALA. UNIVERSITE DE DOUALA.

Synergistic use of municipal solid waste

A thesis submitted in total fulfillment of the requirements for the

Pr Jacques ETAME Pr Marie Annie ETOH Dr Sanjay Kumar

REPUBLIC OF CAMEROON UNIVERSITY OF DOUALA

ACADEMIC YEAR 2019/2020

Updated : 20 June 2020

1. DEPARTEMENT OF BIOLOGY AND ANIMAL PHYSIOLOGY (BA) (23)

N° Noms et Prénoms Grade Observations

2 2 MANDENGUE Samuel Honoré Professor Full Time

3 3 AKONO NTONGA Patrick Associate Professor Full Time

10 10 MISSOUP Alain Didier Senior Lecturer Full Time

11 11 ENDOUGOU EFFA Anne Marie Senior Lecturer Full Time

12 12 KOJI Ernest Senior Lecturer Full Time

Senior Lecturer Head of Departement

14 14 TCHAMADEU Marie Claire Senior Lecturer Full Time

15 15 WANKEU NYA Modeste Senior Lecturer Full Time

16 16 AHMADOU Senior Lecturer Full Time

17 17 KOJI Ernest Senior Lecturer Full Time

18 18 Aïcha De NKAINSA LINDOUX II Assistant Lecturer Full Time

2. DEPARTEMENT OF BIOLOGY AND PLANT PHYSIOLOGY (BV) (19)

24 1 NGO NKOT Laurette épse EKOUE Associate Professor Head of Departement

30 7 FANKEM Henri Associate Professor Full Time

31 8 PRISO Richard Associate Professor Vice Dean

32 9 NDIANG Zenabou Senior Lecturer Full Time

34 11 SIMO Claude Senior Lecturer Full Time

TCHIAZE OFOUE Alice Virginie

3. DEPARTEMENT OF BIOCHEMISTRY (BC) (27)

43 1 NGONO NGANE Rosalie Annie Professor Head of Departement

46 4 KANA MARIE Modestine épse SOP Associate Professor Full Time

KOANGA MOGTOMO Martin Associate Professor

48 6 SAMEZA Modeste Lambert Associate Professor Full Time

Associate Professor Chief of service of

50 8 MINYAKA Emile Associate Professor Chief DFI – IUT

51 9 NDOMOU Mathieu Associate Professor Full Time

Senior Lecturer Chief of service

53 11 LENG Marlyse Solange Associate Professor Full Time

54 12 NJINKOUE Jean Michel Senior Lecturer Full Time

55 13 EBELLE ETAME Rebecca Senior Lecturer S.G MINRESI

57 15 TCHAMENI NGUEMZI Severin Senior Lecturer Full Time

58 16 NOAH MBOENE Alexandre Assistant Lecturer Full Time

4. DEPARTEMENT OF CHEMISTRY (CH) (31)

70 1 ETOH Marie Annie Associate Professor Head of Departement

74 5 AZEBAZE Anatole Guy Blaise Associate Professor Vice Dean / DPSAA

75 6 NDOM Jean Claude Associate Professor Vice Dean / DRC

76 7 KAMDEM WAFFO Alain Associate Professor Full Time

77 8 NGUEFA HAPPI Emmanuel Associate Professor Full Time

DIKA MANGA Joseph Marchand Associate Professor

79 10 NASSI Achille Associate Professor Full Time

82 13 AKONE Hervé Sergi Senior Lecturer Full Time

BASSOMO Monique Yolande épse Senior Lecturer

84 15 BIKELE MAMA Désiré Associate Professor Full Time

85 16 CONDE Mariam épse ASSENG Senior Lecturer Full Time

86 17 DINA David John Daniel Senior Lecturer Full Time

87 18 KEDE Charles Melea Senior Lecturer Full Time

88 19 KENMOGNE Sidonie épse TAVEA Senior Lecturer Full Time

89 20 LOBE SONGUE Jules Senior Lecturer Full Time

90 21 MAKOTA Suzanne épse NDI Senior Lecturer Full Time

TOME PhD's Thesis

TOME PhD's Thesis

TOME PhD's Thesis