Tittle: Pozzolana as Non OPC binder materials

Abstract

Complementary materials may be naturally occurring, manufactured or natural waste. Various types of
pozzolanic materials that improve cement properties have been used in cement industry for a long time.
Alkali-activated natural pozzolan (AANP) concretes develop moderate-to-high mechanical strength with
a high modulus of elasticity and a shrinkage much lower than with OPC. Partial replacement percentages
of pozzolan are considered 10%, 20%, 30% and 40%. The results revealed that the non-OPC binder, the
FA=HL mix (FA=HL ¼ 90:10 by weight) with the NaOH content of 3.5% wt by dry aggregate mass,
provided the most effective mechanical properties an entire network of gel and needles-sharp
cementitious products. The results reveal that Non-cem mortar gains compressive strength of 42.84
MPa (93.36% of OPC) at 28 days. Strength and resistivity both are jointly considered a sound and
balanced quantification of the pozzolanic reactivity is achieved. Water transport properties can be
improved through increasing the strength. Better resistance to sulphate and acid attacks and less
chloride ions penetration also enhanced durability. Durability was also enhanced as better sulfate, acid
and chloride ions penetration resistances were proved. The results and analysis could help decision
makers select sustainable and cost-effective binders for concrete production.

Keyword

Pozzolana, Fly ash, Rice husk, Silica fumes, Bamboo leaf ash, Compressive Strength, Acid resistance,
Chloride penetration, Water absorption, Tensile strength.

Introduction

Strict environmental legislations, cement manufacturing plants, ready-mix plants and pre-cast concrete
plants, to cope with the alarming threat of global warming, climatic changes and ozone layer depletion
due to high greenhouse gasses emission and excessive energy involved in its manufacturing process.
Concrete production contributes 5% of the annual global CO2 emissions [13]. 1 m3 which uses a huge
amount of cement, a primary construction material. Globally, cement plants are responsible for about
3.5% to 5% of total anthropogenic carbon dioxide (CO2) discharge with an intensity of 222 kg/ton of
cement production. It is further reported that cement industries are estimated to discharge up to 1.5
billion tons per year of CO2 into the atmosphere and each year it will remain increasing at the rate of
almost 6% from 1988 to 2015[04]. In cement industries, continuous attempts are being made (i) to
reduce the cost of production of Portland cement, (ii) to reduce the consumption of the raw materials,
(iii) to protect the environment and (iv) to enhance the quality of cement[18].Construction practice in
these three common ways: (1) partially replacing OPC with one or more supplementary cementitious
materials (SCMs) that includes agro-industrial solid wastes such as palm oil fuel ash (POFA), rice husk ash
(RHA), date palm ash (DPA), fly ash (FA) rice husk ash (RHA), natural pozzolan (NP), silica fume (SF),
ground granulated blast furnace slag (GGBFS), super pozzolanas (SP) and metakaolin (MK); (2)
developing alternative binder known as geopolymer concrete that may made of one or more SCMs using
alkaline activators and require elevated temperature curing; (3) developing hybrid cement binder.
There are other techniques being also adopted for minimizing the CO2 emission by concrete industries
such as capturing CO2, use of alternate fuel source or modifying process of clinker manufacturing at
cement plant, however, substitution of clinker by alternate SCMs is the most effective and economical
solutions that can be easily applicable to the ready-mix plan. Since traditional cement is one of the
major cause for depleting natural resources, emitting CO2 into the atmosphere and consuming large
amount of energy during the entire phase of its production, there is a vast scope and promising future of
locally available agro-industrial waste that may offer economical and sustainable construction along
with improved durability as compared to traditional cement construction. [04]. Pozzolans improves
concrete durability by being more resistant in aggressive environments. [13] Cement is a material that
can bind solid particles e.g. gravel, sand, aggregate etc. within a compact structure [12]. In the design of
concrete structures, engineers use or assume a number of mechanical or engineering properties of
hardened concrete, but there is little knowledge about the behavior of concrete made with activated
natural pozzolans as a geopolymer cement. Therefore, it is worthwhile to study the properties of
concrete constructed with an alkali-activated pozzolan binder [01]. In the concrete industry Portland
cement have the ability to set and harden in the presence of water. Pozzolanic cement is a ground
product of a mixture containing 20-40% natural pozzolan and 60-80% Portland cement clinker with the
addition of a small amount of gypsum. Increase in the natural pozzolan content of cement would reduce
the permeability of the paste with the implication of a high resistance to chemical attack i.e. increase in
durability [12]. The most often used mineral admixture in the concrete industry is pozzolan. A
"pozzolan" is defined as "a siliceous or siliceous and aluminous material, which in itself possesses little or
no cementing property, but will in a finely divided form – and in the presence of moisture - chemically
react with calcium hydroxide at ordinary temperatures to form compounds possessing cementitious
properties (Malhotra and Mehta, 1996). Examples of pozzolanic materials are volcanic ash, pumice,
opaline shales, burnt clay and fly ash. Fly ash was very popular, with 20% of companies using it in
concrete. Companies noted that FA is a great substitute for cement and it is cost effective. The rice-husk
ash (RHA) has no useful application, is usually dumped into water streams and causes pollution and
contamination of springs. As a result, the use of rice-husk ash has aroused great interest in Uruguay.
Rice-husk ash is a mineral admixture for concrete; the behavior of cementitious products varies with the
source of RHA [3,4]. The basic aim of this study is to investigate the influence of residual RHA from the
rice paddy milling industry [14]. Some companies mentioned slag (12%) and silica fume (9%) for special
projects, varying use according to the engineer from job to job bases [02]. The use of FA in construction
can reduce GHG emissions by replacing OPC. FA is a suitable cementitious material but requires
integration with functional materials to generate a new binder without OPC [03]. Chi and Huang They
noted that fly ash/ slag ratio and the dosage of Na 2 O as the influential factors control ling the binding
mechanism and overall performance. Among the twelve different mix pro portions, author observed
a significant compressive strength and mechanical prop er ties of the pre pared mor tar specimens by
using 2.5 M NaOH solution for AAB - 1 (42% slag, 28% POFA and 30% RHA) and AAB - 2 (42% slag, 28%
FA and 30% RHA) at 28 days curing period [10]. the use of ternary cements, present more advantages
compared to both binary cements or OPC. The objective of this paper is to present the optimization of
the compressive strength in ternary blended cement containing natural pozzolana and silica fume [15].
The study highlighted that replacing 20–25% of OPC by bottom ash can achieve comparable mechanical
and durability performance, but with higher environmental savings. Lifecycle assessment (LCA)
technique was employed to evaluate the CO2 emissions, energy consumption, and other environmental
impacts of concrete produced with industrial SCMs globally [06]. A wide range of studies were con
ducted in the field of alkali activated binders (AAB) by using slag and FA that were activated with NaOH,
KOH and Ca (OH) 2 separately or in com bi nation with sodium/ potassium silicate. Many re searchers
reported that AAB containing slag show an effective strength and mechanical prop er ties along with
improved durability properties[15].Their chief advantage lies in slow hydration and therefore low rate of
heat development. The objectives of the study are to know the compressive and tensile strength of
mortar with different percentages of natural pozzolan as cement replacement and to evaluate
experimentally the effects of partial replacement of cement with pozzolan on the compressive strength
of concrete. [07]

Materials; -

1. Fly Ash
Twelve coal-burning power stations are currently operating in Turkey, producing roughly 15
million ton of fly ash annually. There are two kinds of fly ashes that adhere to ASTM C 618 for
mineral admixtures in Portland cement concrete: Class F is created by burning bituminous coal
and has a higher final strength, while Class C is created by burning sub-bituminous coal and has
a faster rate of strength gain. the chemical make-up of various FA types. Between 20 and 35% of
the mass of cementitious material can be replaced with Class C fly ash instead of cement. To
lessen the consequences of the alkali silica reaction, class C fly ash must replace at least 25% of
the Portland cement. Class F fly ash can replace 20 to 30 percent of the mass of cementitious
material when combined with Portland cement[02]

2. Silica Fume; -
When high-purity quartz is reduced in an electric arc furnace with coal, coke, and wood chips to
create silicon metal or ferrosilicon alloys, silica fume is produced as a by-product. The
amorphous silicon dioxide content of the silica fume, which condenses from the gases leaving
from the furnaces, is quite high and it is made up of very small, spherical particles. Nominal
silicon concentrations for ferrosilicon alloys range from 61 to 98 percent. The product is known
as silicon metal rather than ferrosilicon when the silicon content reaches 98 percent. The
amount of SiO2 in the silica fume will rise as the alloy's silicon concentration does as well [02].
3. Bamboo leaf ash; -
Bamboo leaves were dried in sun, burnt in an open air for 2 hours to have bamboo leaf ash. The
ash showed a gray colour [11]. Bamboo leaf ash is a good pozzolanic material which reacts with
calcium hydroxide forming calcium silicate hydrate. The pozzolanic activity of bamboo leaf ash
increases with increase of time and temperature [18].
4. Rice husk ash; -
Rice-husk ash is a mineral admixture for concrete ; the behavior of cementitious products varies
with the source of RHA[14]. Controlled incineration of rice husks between 500 0 C and 800C 0
produces non-crystalline amorphous RHA (Mehta and Monteiro, 1993; Mehta and Folliard,
1995). RHA is whitish or gray in color. The particles of RHA occur in cellular structure with a very
high surface fineness. They have 90% to 95% amorphous silica (Mehta and Folliard, 1995). Due
to high silica content, RHA possesses excellent pozzolanic activity. The physical properties of
RHA largely depend on burning conditions [01].
5. Mortar and concrete show different characteristics in the interfacial transition zone and
tortuosity of flow path due to variation of their constituent ingredients. durability of concrete
cannot be quantified by studying mortar only [05].
Test of specimen; -
1. Compressive strength test; -
To determine the compressive strength of geopolymer concrete, each mixture was prepared
as 3.94 x 3.94 x 3.94 in. (100 x 100 x 100 mm) cubes and the compressive strength for these
samples were tested according to BS EN 12390- 3:2009. Details of casting and curing are
described in the previous section [01].
The compressive strength results of concrete using activated natural pozzolans and control
Portland cement mixtures are presented in Fig. 2 with a logarithmic x-axis. In all cases, the
strengths of the concretes increased with age. The rate of strength gain is high at early ages
and gradually decreases at longer ages [01]
It is well known that curing greatly affects the strength development in OPC concrete [01].
Compressive strength was determined on 50 mm cubic specimens, according to ASTM C
109. Mortar specimens were taken out from water tank at 3, 7 and 28 days of curing and
compressive strength was measured at constant loading rate. At each age, four specimens
were tested from each batch and their average values were reported [04]
e. It is observed from Figure 4 and Table 4 that compressive strength decreases with
increase in percent of bamboo leaf ash. The compressive strength of BLA5, BLA10 and BLA10
was lesser than that of control mix by 11%, 21% and 41% respectively.
: Portland cement – bamboo leaf ash composite cements were mixed with sand in 1:3 ratio
and then mixed with water (I S: 4031 part 4, 1988). The mortars were placed in steal moulds
of 70.6 mm 3 dimension [18]
2. Tensile strength test; -
At an early age, ATAF2 showed lower tensile strength results than the OPC control mixture
—0.25 ksi (1.7 MPa) compared to 0.29 ksi (2.03 MPa)—whereas the ATAF1 mixture gave
0.52 ksi (3.57 MPa) after 28 days, higher than the corresponding OPC control mixture at 0.39
ksi (2.67 MPa). The results show that the long-term tensile strengths of activated Taftan
geopolymer concrete mixtures are higher than those of OPC control mixtures—0.54 and
0.44 ksi (3.69 and 3.0 MPa) after 180 days compared to CM1 and CM2 at 0.41 and 0.29 ksi
(2.81 and 1.99 MPa)— respectively. For ACSH and ARSH mixtures, the tensile strength after
180 days is 0.28 and 0.19 ksi (1.96 and 1.3 MPa), respectively.[01]
3. Specific gravity test; -
Specific gravity of any materials is one of the prime parameter to understand the relative
density and weight of the material. Specific gravity of Non-cem was calculated based on the
test results of specific gravity of raw materials used (i.e., slag, POFA and RHA).[05]
4. Chloride penetration test;
Chloride ion penetration test was carried out according to Japanese Industrial Standard (JIS
A6203) for the prism specimens of size 40 mm *40 mm *160 mm. Specimens were tested
for chloride ion penetration test at the age of 28 days. Before immersing the specimens in
sodium chloride (NaCl) solution, the two smooth surfaces and two ends of the dry mortar
specimens were coated with epoxy resin paint. The specimens were then immersed in 2.5%
NaCl solution at 20 C for 14 and 28 days for chloride ion penetration test. After the desired
immersion period (14 and 28 days), the specimens were split, and the split cross-sections
 were sprayed with 0.1 N silver nitrate (AgNO3) solution, chloride penetration of Non-cem
mortar seems to be normal. [05]

5. Water absorption test; -

Water absorption of the mortar prism specimens (40 mm 40 mm * 160 mm) was carried
out according to ASTM C642 (1997) standard. Prism specimens (at the desired age of 14, 28,
and 90 days) were dried until weight of specimen became constant (Wd). The specimens
were then immersed in clean water for 30 min for 1, 3, 6, 24, 48, and 72 h. After the desired
immersion period, the specimens were taken out and surfaces were wiped quickly with a
wet cloth then weighed (Wa) immediately. Therefore, water absorption of the mortar
specimen was determined as 100(Wa*Wd)/Wd in percentage. Finally, water absorption of
the mortar was taken as the average value of six specimens [05]
6. Acid Resistance test;-
The test for acid resistance is done by mixing 5% sulphuric acid solution in distilled water.
The weight loss of control mix, BLA5, BLA10 and BLA15 was 0.6%, 3%, 0.5% and 2.2%
respectively.[11]

Result and discussion;

The lower C/S provided a higher compressive strength than the larger ratio at the same water
content. The optimum calcium content ensured the composites' adequate mechanical properties,
leading to the pozzolanic reaction with an additional aluminosilicate material. The compressive
strengths significantly rose after three and seven days.[03] The compressive strength results of
concrete using activated natural pozzolans and control Portland cement mixtures are presented
with a logarithmic x-axis. In all cases, the strengths of the concretes increased with age. The rate of
strength gain is high at early ages and gradually decreases at longer ages. It is well known that curing
greatly affects the strength development in OPC concrete.[01] The F8L2S1 exhibited the highest
compressive strength value of the tested ages of the F8L2 variants.[03] At early time of hydration
the lower values of compressive strength in the case of bamboo leaf ash blended cement may be
due to lower pozzolanic reactivity.[18] These results indicate that the addition of 3.5% of NaOH
attained efficient strength improvement for this hybrid material.[03]
The tensile strength after 180 days is 0.28 and 0.19 ksi (1.96 and 1.3 MPa), respectively.[1]
Slightly lower compressive strength of AAB mortar specimens compared to OPC mortar specimens
can be observed at the same ages of curing period. This lower compressive strength is due to porous
microstructure of both AAB - 1 and AAB - 2. SEM image of RHA also reveals highly porous.
microstructure. Therefore, porous microstructure of AAB mortar may lead to pass greater amount
of water content [10]. The partial replacement of OPC by volcanic ash (VA) powder can decrease the
water absorption.[06]Qureshi and Ghosh [147] displayed a better connection between apparent
porosity and water absorption of AAS paste and SiO2 content. The water absorption increased due
to the use of FA as an AA in cement mortars. [17]
The increase in CaO content in the AAB solution increased the resistance against organic acid.[17]
It is observed as percent of BLA increases, the resistance to chloride increases but the optimum
percent of BLA is 10%.[11]
 RHA presents less specific gravity than the cement Portland.[14] Specific gravity of bamboo leaf ash
was lesser than that of ordinary Portland cement by 12%.[11] Specific gravity of OPC, FA was 3.15,
2.10 respectively.[04]

Conclusion; -

the addition of 3.5% NaOH gained the effective strength enhancement compared to the mixtures
without NaOH.[03]

. FA enhanced spread due to the ball bearing effect provided by the smooth and spherical particles while
addition of DPA in mixture reduced the flow because of its non-uniform and irregular texture.[05]

Water absorption of Non-cem mortar (e.g., 8.1% at 28 days) was found slightly higher compared to that
of OPC (e.g., 6.2% at 28 days) mortar. Water absorption of Non-cem mortar can be minimized by
improving its compressive strength.[05]

Chloride penetration of Non-cem mortar was found as 11.3 mm, whereas OPC showed 10.1 mm at 28
days, and these results were very close. Chloride penetration of Non-cem mortar seems to be
reasonable compared to OPC. Corrosion resistance of Non-cem mortar was found very well when
evaluated against OPC mortar [05].

The highest 28-day compressive strength was found for OPC-based concrete,[06]

It is observed that (10%) pozzolan replacement in concrete at 28 days compressive strength is nearly
65% of pure cement concrete strength.[07]

The water absorption of both AAB mortar was found a slightly higher than the reference OPC mortar. •
The water absorption of AAB - 1 and AAB - 2 increased 25% and 52%, respectively, than the OPC at 270
days curing period.[10]

The compressive strength of concrete decreases with increase in percent of bamboo leaf ash.[11]

residual RHA provides a positive effect on the compressive strength of concretes at early ages, but in the
long term, the behavior of the concretes with RHA produced by controlled incineration was more
significant.[14]

Reference; -

1. Dali Bondar, Engineering Properties of Alkali Activated Natural Pozzolan Concrete, ACI Materials
Journal.
2. Assist. Prof. Dr. Ibrahim A. S AL-Jumailya , Nahla Najib , Qays Kareem, An overview on the Influence
of Pozzolanic Materials on Properties of Concrete, International Journal of Enhanced Research in
Science Technology & Engineering, ISSN: 2319-7463 Vol. 4 Issue 3, March-2015, pp: (81-92), Impact
Factor: 1.252.
3. Thanon Bualuang a , Peerapong Jitsangiam b,* , Teewara Suwan b , Ubolluk Rattanasak c , Napat
Jakrawatana d , Nanticha Kalapat e , Hamid Nikraz , Non-OPC binder based on a hybrid material
concept for sustainable road base construction towards a low-carbon society, journal of materials
research and technology 2021;14:374 e391.
4. Walid Al-Kutti a , Muhammad Nasir a,b,⇑ , Megat Azmi Megat Johari b , A. B. M. Saiful Islam a ,
Abdullah A. Manda c , Nawaf I. Blaisi d, An overview and experimental study on hybrid binders
containing date palm ash, fly ash, OPC and activator composites, Construction and Building
Materials 159 (2018) 567–577.
5. M.R. Karim a,b,⇑ , M.M. Hossain a,⇑ , M.F.M. Zain a,⇑ , M. Jamil a , F.C. Lai c, Durability properties of
a non-cement binder made up of pozzolans with sodium hydroxide, Construction and Building
Materials 138 (2017) 174–184.
6. Md. Uzzal Hossain a , Jin-Cheng Liu a , Dongxing Xuan b , S. Thomas Ng c,* , Hailong Ye a , Safaa J.
Abdulla d, Designing sustainable concrete mixes with potentially alternative binder systems:
Multicriteria decision making process, Journal of Building Engineering 45 (2022) 103587.
7. Tin Ni Ni Koa* , Dr. Nilar Ayeb, Experimental Research on Natural Pozzolan as Cement Replacement,
American Scientific Research Journal for Engineering, Technology, and Sciences (ASRJETS) ISSN
(Print) 2313-4410, ISSN (Online) 2313-4402 © Global Society of Scientific Research and Researchers.
8. Mahipal Kasaniya a,* , Anfal Alaibani b , Michael D.A. Thomas a , Kyle A. Riding b, Exploring the
efficacy of emerging reactivity tests in screening pozzolanic materials, Construction and Building
Materials 325 (2022) 126781.
9. Md Maruf Hossain a , * , Md Rezaul Karim b , ** , Md Manjur A Elahi c , Muhammad Fauzi Mohd
Zain d, Water absorption and sorptivity of alkali - activated ternary blended composite binder,
Journal of Building Engineering 31 (2020) 101370.
10. P. Asha, A. Salman, R. Arun Kumar, Experimental Study on Concrete with Bamboo Leaf Ash,
International Journal of Engineering and Advanced Technology (IJEAT) ISSN: 2249 – 8958, Volume-3
Issue-6, August 2014.
11. İ. ALP1**, H. DEVECI1 , Y.H. SÜNGÜN2 , A. O.YILMAZ1 , A. KESİMAL1 AND E. YILMAZ1, POZZOLANIC
CHARACTERISTICS OF A NATURAL RAW MATERIAL FOR USE IN BLENDED CEMENTS, Iranian Journal of
Science & Technology, Transaction B, Engineering, Vol. 33, No. B4, pp 291-300 Printed in The Islamic
Republic of Iran, 2009.
12. *Opeyemi Joshua, Danladi S. Matawal et.al, DEVELOPMENT OF A FULLY POZZOLANIC BINDER FOR
SUSTAINABLE CONSTRUCTION: WHOLE CEMENT REPLACEMENT IN CONCRETE APPLICATIONS,
International Journal of Civil Engineering and Technology (IJCIET) Volume 9, Issue 2, February 2018,
pp. 1–12, Article ID: IJCIET_09_02_001, ISSN Print: 0976-6308 and ISSN Online: 0976-6316.
13. Gemma Rodrı´guez de Sensale, Strength development of concrete with rice-husk ash, Cement &
Concrete Composites 28 (2006) 158–160.
14. Mohamed Ghrici, Said Kenai, Mohamed Said-Mansour & El-Hadj Kadri, Some Engineering Properties
of Concrete Containing Natural Pozzolana and Silica Fume, Journal of Asian Architecture and
Building Engineering ISSN: 1346-7581 (Print)1347-2852 (Online) Journal homepage:
https://www.tandfonline.com/loi/tabe20.
15. M. Ghrici a , S. Kenai b,*, M. Said-Mansour c, Mechanical properties and durability of mortar and
concrete containing natural pozzolana and limestone blended cements, Cement & Concrete
Composites 29 (2007) 542–549.
16. Bassam A. Tayeh a , Hussein M. Hamada b,* , Ibrahim Almeshal c,d , B.H. Abu Bakar d, Durability and
mechanical properties of cement concrete comprising pozzolanic materials with alkali-activated
binder: A comprehensive review, Case Studies in Construction Materials 17 (2022) e01429.
17. V.N. Dwivedi a , N.P. Singh b , S.S. Das a and N.B. Singh a*,A new pozzolanic material for cement
industry: Bamboo leaf ash, International Journal of Physical Sciences Vol. 1 (3), pp. 106-111,
 November, 2006 Available online at http://www.academicjournals.org/IJPS ISSN 1992 - 1950 ©
2006 Academic Journals.
18. C. Shi, Studies on Several Factors Affecting Hydration and Properties of LimePozzolan Cements, J.
Mater. Civ. Eng. 13 (6) (2001) 441–445.
19. McGrath. P. 1996. Development of Test Methods for Predicting Chloride Penetration into High
Performance Concrete. Ph.D Thesis. Department of Civil Engineering, University of Toronto.
20. Siddique R (2008) “Waste Material and By-Product in Concrete”. Thapar Institute of Engineering &
Technology (Deemed University), Patiala, India. ISBN 978-3-540-74294-4.
21. Papadakis, V. G. & Tsimas, S. (2002). Supplementary materials in concrete. Part I: Efficiency and
design. Cement and Concrete Research, Vol. 32, pp. 1035-1041.
22. Jamrozy, Z. (1997). Use of silica fume for concrete. Cement Wapno Beton, Vol. 2, No. 4, pp. 140-143.
23. Mehta, P.K. (1987). "Natural pozzolans: Supplementary cementing materials in concrete". CANMET
Special Publication 86: 1–33.
24. Islam, G. S., Rahman, M. H., & Kazi, N. (2017). Waste glass powder as partial replacement of cement
for sustainable concrete practice. International Journal of Sustainable Built Environment. 6(1), 37-
44.